JPH05195441A - Textile-treating agent - Google Patents

Abstract

PURPOSE:To provide a textile-treating agent containing a mixture of two specific diorganopolysiloxane components containing amino group and capable of imparting textile products with excellent flexibility and durable smoothness, stretch recovery, etc. CONSTITUTION:The objective textile-treating agent capable of imparting durable crease-resistance, etc., to fiber can be produced by compounding (A) 100 pts.wt. of a diorganopolysiloxane containing one amino group or substituted amino group in one molecule and expressed by formula I [R<1> is 1-20C univalent hydrocarbon group; R<2> is (CH2)a(NHCH2CH2)b-NHR<4> (R<4> is H or univalent hydrocarbon group; (a) is 1-10; (b) is 0-10); R<3> is R<1>, R<2>, OH or 1-20C alkoxy; (m) is 0-2,000; (n) is 0 or >=1] with (B) 0.1-30 pts.wt. of a diorganopolysiloxane containing one amino group, etc., in one molecule and expressed by formula II [R<5> is methyl; a part of R<5> may be vinyl or phenyl; R<6> is (CH2)c(NHCH2CH2)d- NHR<8> (R<8> is H or univalent hydrocarbon group; (c) is 1-10; (d) is 0-10); R<7> is R<5>, R<6>, OH or 1-20C alkoxy; (p) is 2,000-20,000; (q) is 0 or >=1].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber treating agent, and more particularly to an organopolysiloxane type fiber treating agent capable of imparting excellent flexibility, smoothness, elongation recovery and wrinkle resistance to a fiber product. .

[0002]

2. Description of the Related Art As a treating agent for imparting flexibility, smoothness, elongation recovery, wrinkle resistance and the like to textiles, conventionally, waxes and fatty acids such as fatty acids and long chain alkyl groups have been contained. The quaternary ammonium salt and the like are widely used. Also, as a fiber treatment agent, a certain type of organopolysiloxane is known, and the water repellency of the fiber,
The use of dimethylpolysiloxane, amino group-containing polysiloxane, epoxy group-containing polysiloxane, etc. has been proposed for improving flexibility, smoothness and repulsion (Japanese Patent Publication No. 48-1480 and Japanese Patent Publication No. 54-54-). See 43617).

[0003]

However, the fiber-treating agent using the fats and oils or the quaternary ammonium salt does not give the fiber a satisfactory softening effect, and the dimethylpolysiloxane gives the fiber good smoothness. However, imparting flexibility is not satisfactory. Furthermore, although the epoxy group-containing polysiloxane imparts smoothness and flexibility to the fiber, it tends to be inferior in the effect of imparting flexibility to the amino group-containing polysiloxane, and the amino group-containing polysiloxane also has a smoothness and flexibility to the fiber. Although it can be durable, it can impart greater flexibility and smoothness to this fiber treatment, as well as wrinkle resistance, compression recovery and stretch. The emergence of super softeners with excellent recoverability is desired.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a fiber treating agent which solves the above-mentioned problems, which is a) the following general formula (1)

[Chemical 3] [Here, R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ² is a formula-
(CH ₂ ) _a- (NHCH ₂ CH ₂ ) _b -NHR ⁴ (wherein R ⁴ is a hydrogen atom or a monovalent hydrocarbon group, a is an integer of 1 to 10 and b is an integer of 0 to 10) Group, R ³ is R ¹ , R ² , a hydroxyl group or 1 carbon atom
To 20 alkoxy groups, m is a positive integer of 0 to 2,000, n is 0 or an integer of 1 or more] 100 parts by weight of diorganopolysiloxane having at least one amino group or substituted amino group in one molecule. , B) The following general formula (2)

[Chemical 4] [Wherein R ⁵ is a methyl group, a part of which may be a vinyl group or a phenyl group, R ⁶ is a group represented by the formula:-(CH ₂ ) _c- (NHCH ₂ CH ₂ ) _d -NHR ⁸
(Wherein R ⁸ is a hydrogen atom or a monovalent hydrocarbon group, c is 1 to 1
An integer of 0, d is an integer of 0 to 10), R ⁷ is R ⁵ , R
⁶ , a hydroxyl group or an alkoxy group having 1 to 20 carbon atoms, p is 2,
An integer of 000 to 20,000, q is 0 or an integer of 1 or more] and 0.1 to 30 parts by weight of a diorganopolysiloxane having at least one amino group or substituted amino group in one molecule. To do.

That is, as a result of various investigations by the present inventors to develop a fiber treatment agent capable of imparting excellent flexibility to a fiber product, the average molecular weight represented by the above general formula (1) is
When a textile product is treated with a mixture of an amino group-containing organopolysiloxane of 150,000 or less and a high molecular weight amino group-containing organopolysiloxane represented by the general formula (2) and having an average molecular weight of 150,000 or more, this textile product is obtained. It has been found that excellent flexibility is imparted, and that this flexibility is also durable, and at the same time that it is imparted with smoothness, elongation recovery, and wrinkle resistance. The present invention has been completed by conducting research on the type of polysiloxane, the combination thereof, the blending amount, and the like. This will be described in more detail below.

[0006]

The present invention relates to a fiber treating agent, which comprises (a) 100 parts by weight of the amino group-containing organopolysiloxane represented by the general formula (1), and (b) the above general formula.
Amino group-containing organopolysiloxane represented by (2)
0.1 to 30 parts by weight, which gives the advantage of treating the fiber product with good flexibility and smoothness, elongation recovery and wrinkle resistance.

The amino group-containing organopolysiloxane as the component (a) constituting the fiber treating agent of the present invention is represented by the above-mentioned general formula (1), wherein R ¹ is a methyl group or ethyl group. Groups, propyl groups, butyl groups, pentyl groups, and other alkyl groups, vinyl groups, allyl groups, and other alkenyl groups, phenyl groups, tolyl groups, and other aryl groups, or hydrogen atoms bonded to carbon atoms of these groups. Unsubstituted or substituted monovalent C1-20 carbon atoms selected from chloromethyl, partially or wholly substituted with halogen, cyano, etc., 3,3,3-trifluoropropyl, cyanoethyl, etc. Of the hydrocarbon groups, the methyl group is most commonly used, but it may be a combination of the methyl group and other groups.

Further, R ² has the formula-(CH ₂ ) _a- (NHCH ₂ CH ₂ ) _b -N
Shown in HR ^4, a monovalent hydrocarbon group R ⁴ is exemplified by an aryl group such as an alkyl group, a phenyl group, such as a hydrogen atom or a methyl group, an ethyl group, a propyl radical, a is 1
10 integer, b is 0 integer, in particular are assumed to be 0 or _{1, - (CH 2) a} - The group _{-CH 2 -, -CH 2 CH 2} -, -CH
₂ CH ₂ CH _2- , alkylene groups such as-(CH ₂ ) _4- are exemplified, but R ³ is the same group as R ¹ or R ² , or a hydroxyl group or a methoxy group, an ethoxy group, a propoxy group, It is selected from the alkoxy groups having 1 to 20 carbon atoms exemplified by the phenoxy group and the like.

Note that this m is an integer from 0 to 2,000, and n is 0.
Or, since it is an integer of 1 or more, the average molecular weight is 150,000 or less, but when m + n is less than 10, the effect of imparting flexibility and smoothness is poor, and this is
If it exceeds 1,000, emulsification becomes difficult, so this m + n is 1
The amino group-containing organopolysiloxane as the component A) is synthesized by the method described in JP-B-53-98499, although it may be in the range of 0 to 1,000, and more preferably in the range of 50 to 500. can do.

Next, b) which constitutes the fiber treating agent of the present invention
The amino group-containing organopolysiloxane as a component is represented by the above-mentioned general formula (2).
R ⁵ is a methyl group, a part of which may be a vinyl group or a phenyl group, and this vinyl group or phenyl group is combined with a methyl group if necessary, and this R ⁶ has the same formula as R ² described above. - (CH _{2) c} - indicated by _{(NHCH 2 CH 2) d -NHR} 8, R 8 is a hydrogen atom or a methyl group, an ethyl group, an alkyl group such as propyl, are exemplified by an aryl group such as a phenyl group 1
In a valent hydrocarbon group, c is an integer of 1 to 10 and d is an integer of 0 to 10, and-(CH ₂ ) _c -group is -CH _2- , -CH ₂ CH _2- , -CH ₂ CH.
_{2 CH 2 -, - (CH} 2) 4 - it is those exemplified.

Further, R ⁷ is selected from R ⁵ , R ⁶ or a hydroxyl group or an alkoxy group having 1 to 20 carbon atoms, which is exemplified by a methoxy group, an ethoxy group, a propoxy group and a phenoxy group. Since p is 2,000 to 20,000 and q is an integer of 0 or 1 or more, it is considered to be a high molecular weight compound with an average molecular weight of 150,000 or more, but this p + q is less than 2,000. The effect of imparting the adsorptivity and durability to the fiber becomes poor, and when it exceeds 20,000, the compatibility with the above-mentioned component A) becomes poor, so this p + q is in the range of 2,000 to 20,000, preferably
It is good to set it in the range of 3,000 to 10,000.

The fiber treatment agent of the present invention is produced by mixing the above-mentioned components (a) and (b). The mixing ratio is such that the mixing amount of the (b) component is 100 parts by weight of the (a) component.
If it is less than 0.1 parts by weight, the addition effect is not obtained because it is too small, and if it is more than 30 parts by weight, the viscosity becomes too high and it becomes difficult to emulsify it. Although required, this preferred range is 1 to 10 parts by weight.

Various kinds of organopolysiloxanes, organosilanes, organohydrogenpolysiloxanes and oxyalkylene group-containing polysiloxanes which have been conventionally used as fiber treating agents may be added to the fiber treating agent of the present invention. In addition, inorganic fine powders such as mica, talc and silica, and conventionally known additives such as antistatic agents, softening agents, anti-wrinkling agents, heat-resistant agents and flame retardants may be used in combination.

The treatment of the fiber product with the fiber treatment agent of the present invention is carried out by using the above-mentioned mixture of the components (a) and (b). The mixture of the components (a) and (b) is toluene, It may be diluted with a solvent such as xylene, benzene, n-hexane, heptane, or perchlorethylene to adjust the concentration to a desired level, and this may also be used by using a surfactant. The mixture may be emulsified and dispersed in water, or the a) and b) components may be separately emulsified to form an emulsion and then diluted with water before use.
In addition, the processing of textile products by this, spray, roller, this mixed solution, solvent diluent or emulsion diluent.
The fiber may be treated by a means such as dipping to deposit the siloxane component on the fiber and then dried. The amount of deposition is not particularly limited, but is usually about 0.1 to 5% by weight with respect to the cloth. Good.

There are no particular restrictions on the surfactant used in the emulsification described above, and examples thereof include sulfate ester salts of higher alcohols, alkylbenzene sulfonates, higher alcohol polyoxyalkylene adducts, and higher fatty acid polyoxys. Examples thereof include alkylene adducts, alkylphenol polyoxyalkylene adducts, higher fatty acid sorbitan esters, and quaternary ammonium salts.

The fiber material treated with the fiber treatment agent of the present invention is, in terms of material, natural fiber such as wool, silk, hemp, cotton, asbestos, regenerated fiber such as rayon and acetate, polyester, Polyamide, vinylon, polyacrylonitrile, polyethylene, polypropylene,
Synthetic fibers such as spandex, glass fibers, carbon fibers, silicon carbide fibers, etc. are exemplified, and in terms of shape, they may be any of stable, filament, tow, yarn, woven fabric, knitted fabric, non-woven fabric, resin-treated fabric, etc. ,
Sheets such as knits, non-woven fabrics, and futons can be processed continuously, which is efficient.

[0017]

EXAMPLES Examples and comparative examples of the present invention will be given below.
Parts in the examples are parts by weight, and the viscosity is the value measured at 25 ° C. Example 1, Comparative Example 1 Formula

[Chemical 5] And a viscosity of 1,000 cS is added to 100 parts of the amino group-containing organopolysiloxane as a component, the formula

[Chemical 6] , The viscosity when dissolved in toluene at 10% is 300 cS
1 part, 5 parts or 10 parts of the amino group-containing organopolysiloxane as the high molecular weight component b) is added, and the mixture is stirred until it is dissolved uniformly to obtain siloxanes A), B),
C) was prepared, and for comparison, the amino group-containing organopolysiloxane oil alone as the above-mentioned component a) was used as siloxane D).

Next, each 100 of these siloxanes A) to D)
Emulsified and dispersed in 220 parts of water by using 10 parts of polyoxyethylene nonylphenyl ether as a surfactant in 20 parts of water and emulsions A, B, C and D corresponding to siloxanes A to D.
After making each, add 1% by weight of siloxane to each of them with water.
Soak the cotton broad cloth and polyester / wire (65/35) blended cloth broad cloth in this diluted solution, squeeze with a roll to a squeezing ratio of 100%, then dry at 100 ° C for 2 minutes, and then It heat-processed at 150 degreeC for 2 minutes.

Next, the flexibility of the thus treated cloth was evaluated using a Uenoyama type hand meter (manufactured by Uenoyama Kiko Co., Ltd.), and the results as shown in Table 1 below were obtained. However, this evaluation result shows the bending resistance of the cloth as the flexibility (g), and the larger the value is, the poorer the flexibility is. Regarding these treated cloths, the durability was evaluated by measuring the flexibility of the treated cloths after being washed 5 times with a household electric washing machine according to JIS L-0217 103 method. The results are shown in Table 1 below. The results were as shown. In addition, this emulsion A, B,
It was confirmed that the cloth treated with C was imparted with smoothness, wrinkle resistance, compression recovery and extension recovery.

Example 2 Formula

[Chemical 7] And a viscosity of 60 cS is added to 100 parts of the amino group-containing organopolysiloxane as component b), the formula:

[Chemical 8] The viscosity when dissolved in toluene at 10% is 100 cS
5 parts of a high molecular weight organopolysiloxane having a high molecular weight of b) was added and stirred until it was uniformly dissolved, and the resulting siloxane composition was named Siloxane E, which had the same interface as in Example 1. Emulsion E was prepared by emulsifying and dispersing with an activator.

Then, this emulsion E was diluted with water so that the siloxane content became 1% by weight, and the cotton broad cloth and the polyester / cotton blended broad cloth were treated with this to examine its flexibility and durability. As a result, the results as shown in Table 1 described later were obtained, and it was also confirmed that smoothness, wrinkle resistance, compression recovery property, and extension recovery property were imparted to this.

Comparative Example 2 The high molecular weight amino group-containing organopolysiloxane used as the component (b) in Example 1

[Chemical 9] In the same manner as in Example 1 except that 5 parts shown in Example 1 were used to prepare Emulsion F, which was used in the same manner as in Example 1 to treat cotton broad cloth and polyester / cotton blended cloth. When the flexibility and durability were examined, the results shown in Table 1 below were obtained.

[0023]

[Table 1]

Example 3 and Comparative Example 3 The emulsion stability of the emulsions A to F produced in Examples 1 and 2 and Comparative Examples 1 and 2 was evaluated for dilution stability and mechanical stability by the following methods. The result as shown in 2 was obtained. (Dilution stability) The emulsion is diluted 100 times with water and the surface state of the diluted solution after standing for 24 hours is visually observed. (Mechanical stability) The emulsion was diluted 100 times with water, and the surface condition of the liquid was visually observed after stirring for 5 minutes at 3,000 rpm using a homomixer [made by Tokushu Kika Kogyo Co., Ltd.].

[0025]

[Table 2]

[0026]

INDUSTRIAL APPLICABILITY The present invention relates to a fiber treating agent, which comprises, as described above, a) 100 parts by weight of an amino group-containing organopolysiloxane represented by the general formula (1) and having an average degree of polymerization of 250,000 or less. B) It is characterized by being mixed with 0.1 to 30 parts by weight of a high molecular weight amino group-containing organopolysiloxane represented by the general formula (2) having an average molecular weight of 250,000 or more. The (a) and (b) components have good compatibility with each other and have excellent emulsification properties. When the textile product is treated with this, the textile product has excellent flexibility, durability, smoothness, and elongation recovery. And the advantage that wrinkle resistance is imparted.

Claims (1)

[Claims] 1. A) General formula: [Here, R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ² is a formula-
(CH ₂ ) _a- (NHCH ₂ CH ₂ ) _b -NHR ⁴ (wherein R ⁴ is a hydrogen atom or a monovalent hydrocarbon group, a is an integer of 1 to 10 and b is an integer of 0 to 10) Group, R ³ is R ¹ , R ² , a hydroxyl group or 1 carbon atom
To 20 alkoxy groups, m is a positive integer of 0 to 2,000, n is 0 or an integer of 1 or more] 100 parts by weight of diorganopolysiloxane having at least one amino group or substituted amino group in one molecule. , B) General formula: [Wherein R ⁵ is a methyl group, a part of which may be a vinyl group or a phenyl group, R ⁶ is a group represented by the formula:-(CH ₂ ) _c- (NHCH ₂ CH ₂ ) _d -NHR ⁸
(Wherein R ⁸ is a hydrogen atom or a monovalent hydrocarbon group, c is 1 to 1
An integer of 0, d is an integer of 0 to 10), R ⁷ is R ⁵ , R
⁶ , a hydroxyl group or an alkoxy group having 1 to 20 carbon atoms, p is 2,
An integer of 000 to 20,000, q is 0 or an integer of 1 or more] having at least one amino group or substituted amino group in one molecule.
0.1 to 30 parts by weight, and a fiber treatment agent.