JPH0788626B2 - Textile treatment agent - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is a fiber treating agent, and in particular, has improved hydrophilicity.
The present invention relates to a fiber treating agent that is useful for imparting hydrophilicity.

[0002]

2. Description of the Related Art Various processing agents for imparting flexibility and smoothness to textiles have been known to date, and various organopolysiloxanes have heretofore been known, such as dimethylpolysiloxane, epoxy group-containing polysiloxane, Aminoalkyl group-containing polysiloxanes and the like have been proposed (Japanese Patent Publication No. 48-1480 and Japanese Patent Publication No. 54-41367).
JP-B-59-26707), among them, aminoalkyl group-containing polysiloxanes are widely used because they are very excellent in imparting flexibility to fibers.

[0003]

However, when a fiber is treated with this aminoalkyl group polysiloxane, the treated cloth exhibits water repellency, so that the characteristics of natural fibers such as natural fibers are impaired. There is a problem that it will be lost. Further, in order to impart hydrophilicity to the fiber, it is known to treat with a polyether group-containing polysiloxane, but this is considerably higher than the above-mentioned aminoalkyl group-containing polysiloxane in terms of flexibility. It has the disadvantage of being inferior. Therefore, various proposals have been made to improve the flexibility, and for example, polysiloxane having a polyether group and an aminoalkyl group in one molecule (see Japanese Patent Publication No. 61-472) is known. However, this causes a large decrease in flexibility due to the polyether group, and therefore a fiber treating agent satisfying both the characteristics of flexibility and hydrophilicity has not yet been obtained.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a fiber treating agent which has solved such disadvantages, and it has the following general formula (1):

[Chemical 2] [Here, R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ²
Is the formula —R ⁵ — (NR ⁶ R ⁷ ) _d —NR ⁸ R ⁹ (A) (wherein R ⁵ and R ⁷ are divalent hydrocarbon groups having 1 to 8 carbon atoms,
R ^6, R ^8, R ⁹ is a monovalent hydrocarbon group, group d is represented by an integer) of 0-4 C1-8 hydrogen or C, R ³ is the formula -R ¹⁰ -OCH [CH ₂ OCH ₂ CH (OH) -CH ₂ (OH)] ₂ (B) (wherein R ¹⁰ is a divalent hydrocarbon group having 2 to 8 carbon atoms), R ⁴ is a group represented by the formula —OR ¹¹ (R ¹¹ is a hydrogen atom or a group represented by a monovalent hydrocarbon group having 1 to 4 carbon atoms), or R
¹ , one or two kinds of groups selected from the groups represented by formulas (A) and (B), a, b and c are each 0 or an integer of 1 or more, and when b is 0, R ^At least one of ⁴ is a group represented by the formula (A), and when c is 0, at least one of R ⁴ is a group represented by the formula (B)]. It is characterized by that.

That is, the present inventors have conducted various studies to develop a fiber treating agent capable of imparting both softness and hydrophilicity to fibers, and as a result, the polyether group in the conventionally known one was replaced. It has been found that hydrophilicity can be imparted without reducing flexibility by introducing a triglycerin group with an organopolysiloxane as a fiber treating agent containing an aminoalkyl group and a triglycerin group. It was confirmed that treating the fiber with this can impart both flexibility and hydrophilicity to the fiber at the same time, and research on the kind of this organopolysiloxane and the fiber treatment method using the same was carried out. Was completed. This will be described in more detail below.

[0006]

The present invention relates to a fiber treating agent capable of imparting flexibility and hydrophilicity to a fiber, which contains an organopolysiloxane represented by the general formula (1) as a main component. Is.

The fiber treating agent of the present invention has the following general formula (1):

[Chemical 3] Is indicated by. Here, R ¹ is an alkyl group such as a methyl group, an ethyl group, a butyl group, a dodecyl group or an octadecyl group, an alkenyl group such as a vinyl group or an allyl group, a cycloalkyl group such as a cyclohexyl group or a cycloheptyl group,
A phenyl group, an aryl group such as a naphthyl group or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms in which a hydrogen atom of these groups is partially substituted with a halogen atom, any organic group, etc., and preferably It is a methyl group.

R ² is represented by the following formula (A) —R ⁵ — (NR ⁶ R ⁷ ) _d —NR ⁸ R ⁹ (A), where R ⁵ and R ⁷ are a methylene group and ethylene. Groups, divalent hydrocarbon groups such as propylene group and butylene group,
R ⁶ , R ⁸ and R ⁹ are hydrogen atoms or the same monovalent hydrocarbons as R ¹ and are aminoalkyl groups in which d is an integer of 0 to 4, and such aminoalkyl groups include-(CH
₂ ) ₃ NH ₂ ,-(CH ₂ ) ₃ NH (CH ₂ ) ₂ NH
₂ ,

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7] Can be exemplified _{-CH = CHCH 2 NH (CH 2} ) 2 NH 2 and the like.

Next, R ³ is a triglycerin group represented by the following formula (B) —R ¹⁰ —OCH [CH ₂ OCH ₂ CH (OH) —CH ₂ (OH)] ₂ (B) R ¹⁰ is an ethylene group, a propylene group, a butylene group, — (CH ₂ ) ₃ CH ₂
CH ₂ CH ₂ — group,

[Chemical 8]

[Chemical 9] Is a divalent hydrocarbon group having 2 to 8 carbon atoms. Further, R ⁴ in the formula (1) is represented by the formula OR ¹¹ , and R ¹¹ is a hydrogen atom or a monovalent hydrocarbon having 1 to 4 carbon atoms, such as a hydroxyl group, a methoxy group, an ethoxy group and a t-butyl group. A selected group, or the R ¹ group described above,
One or two groups selected from the groups represented by formula (A) and formula (B).

In the above formula (1), a, b, and c are each an integer of 0 or an integer of 1 or more. The organopolysiloxane represented by the formula (1) is used to impart good flexibility to the fiber. In order to impart hydrophilicity, it is preferable that a has a numerical value of 50 to 1,000, b has a numerical value of 0 to 50, and c has a numerical value of 0 to 100, but when b is 0, R ⁴ is at least one of them. Is required to be represented by the formula (A), and when c is 0, at least one R ⁴ is required to be represented by the formula (B).

The organopolysiloxane containing an aminoalkyl group and a triglycerin group represented by the general formula (1) is first prepared by the following formula (2).

[Chemical 10] In indicated, Q has the formula -CH = CH ₂ in the formula, -CH ₂ CH
_{= CH 2, -CH 2 C (} CH 3) = CH 2, -CH 2 C
_{H 2 CH = CH 2, -} (CH 3) 3 CH 2 CH = CH
_{2, -CH (CH 3) CH} = CH 2, -CH 2 -C (C
_{H 3) 2 -CH = CH 2} , -C (CH 3) 2 CH = CH
Unsaturated triglycerol derivative which is monovalent hydrocarbon of 2 to 8 carbon atoms having a double bond in molecular chain terminal exemplified ₂ etc., the following formula (3)

[Chemical 11] R ¹ is the same as the above, R ¹² is a hydrogen atom or the same monovalent hydrocarbon as R ¹ , and e and f are 0 respectively.
When f is 0 in the above integers, at least one of R ¹² is a hydrogen atom, and an organohydrogenpolysiloxane is subjected to an addition reaction in the presence of a platinum catalyst.

This addition reaction yields an organopolysiloxane containing a triglycerin derivative, which requires the subsequent introduction of an aminoalkyl group. )

[Chemical 12] And R ¹ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the formula
Is the same group as described above, and an aminoalkyl group-containing cyclic siloxane in which n = 3 to 10 may be equilibrated in the presence of an alkaline catalyst.

According to this reaction, the organopolysiloxane is made to contain an aminoalkyl group and a triglycerin derivative, which is then added with an acid such as hydrochloric acid or acetic acid and water, under weak acidic water conditions. Preferably 5
When heated to 0 to 100 ° C., deacetonation is carried out to release the blocking of the hydroxyl group of the triglycerin derivative. Therefore, the organopolysiloxane containing the aminoalkyl group and triglycerin group represented by the above formula (1) is released. However, in this case, it is also effective to add ethanol, isopropanol or the like to this system for the purpose of improving contact between water and the modified silicone compound.

The organopolysiloxane obtained in this manner is usually assumed to have its terminal blocked with a trimethylsilyl group. The trimethylsilyl group is obtained by introducing a silanol group or an alkoxy group by a known method. Good. The fiber treating agent of the present invention is mainly composed of the thus obtained organopolysiloxane containing an aminoalkyl group and a triglycerin group. Textile-treating agents such as anti-wrinkle agents, penetrants, flame retardants and the like may be added.

In treating various fiber products with the fiber treating agent of the present invention, the fiber treating agent is diluted with an appropriate solvent and adjusted to a desired concentration, or a surfactant is used to dissolve it in water. Emulsified and dispersed in the above to obtain an emulsion form, diluted with water, adjusted to a desired concentration, adhered to the fiber by the means such as dipping, roll coating or spraying, and then the organopolysiloxane of the formula (1), and then A method of drying can be adopted. In this case, the adhered amount is not particularly limited, but it is usually 0.1 to 5% by weight with respect to the cloth.
The degree is enough.

As the surfactant used for emulsification, anionic surfactants such as sodium alkylsulfate and sodium alkylbenzenesulfonate, polyoxyethylene alkylphenyl ether,
A nonionic surfactant such as polyoxyethylene alkyl ether, a cationic surfactant such as quaternary ammonium salt, and a zwitterionic surfactant such as alkyl betaine may be used as an emulsifier.

Various kinds of fibers or fiber products to be treated with the fiber treatment agent of the present invention are selected. Natural fibers or fiber products such as cotton, hemp, silk and wool, synthetic fibers or fibers such as polyester, nylon and acrylic. Examples thereof include products, which are not particularly limited, and the treatment with the fiber treatment agent of the present invention provides an advantage that excellent flexibility and hydrophilicity can be imparted to these fibers and fiber products. .

Next, synthetic examples of the organopolysiloxane used in the examples of the present invention and comparative examples, and examples and comparative examples of the present invention will be given.

Synthesis Example 1 Capacity 500 equipped with a stirrer, a thermometer, and a reflux condenser
c. c. In a flask

[Chemical 13] Methylhydrogenpolysiloxane 60.
1g, formula

[Chemical 14] 90.0 g of an unsaturated triglycerin derivative represented by: 150 g of isopropyl alcohol, 10% of potassium acetate
Charge 1.0 g of an ethanol solution and 0.1 g of a 2% isopropyl alcohol solution of chloroplatinic acid as a catalyst,
The reaction was carried out under reflux of isopropyl alcohol for 5 hours with stirring.

After completion of the reaction, ≡Si-remaining in the reaction solution.
When the amount of H group was examined, it was confirmed that this reaction proceeded 97%. Therefore, when this reaction solution was treated under reduced pressure of 10 mmHg at 100 ° C. for 2 hours to remove the low boiling point, , An oil having a viscosity (25 ° C.) of 980 cS and a refractive index of 1.438 was obtained. As a result of elemental analysis, IR, and NMR analysis of this oil, the average structural formula was

[Chemical 15] Was confirmed to be an organopolysiloxane containing a triglycerin derivative.

Then, in a flask having a capacity of 1 liter equipped with a stirrer, a thermometer and a reflux condenser, 86.4 g of the organopolysiloxane obtained above, 404.4 g of octamethylcyclotetrasiloxane, the following formula:

[Chemical 16] Aminoalkyl group-containing cyclic siloxane represented by 9.2
g and 0.05 g of KOH as a catalyst were charged, an equilibration reaction was carried out at 150 ° C. for 6 hours with stirring, and then 1
The mixture was cooled to 00 ° C., 0.4 g of ethylene chlorohydrin was added, and the catalyst was neutralized at 100 ° C. for 2 hours. The viscosity was 2,600 cS, 150 ° C., and the volatile residue after 30 minutes was 88. An oil was obtained which was 7%.

Then, 200 g of the above-obtained oil, 200 g of isopropyl alcohol, and 0.1 g were added to a 1-liter flask equipped with a stirrer, a thermometer, and a reflux condenser.
After charging 100 g of 1N hydrochloric acid water and carrying out a deacetonation reaction for 5 hours under the reflux of isopropyl alcohol,
When the low boiling point was removed by heating at 120 ° C. for 2 hours under a reduced pressure of 10 mmHg, the viscosity was 33,000 cp.
Since an oil with a volatile residue content of 95.6% was obtained,
Analysis of this oil showed that the average structural formula was

[Chemical 17] Was confirmed to be an organopolysiloxane containing an aminoalkyl group and a triglycerin group (hereinafter abbreviated as organopolysiloxane A).

Synthesis Example 2 To 245.2 g of the organopolysiloxane containing the triglycerin derivative obtained in Synthesis Example 1, 241.8 g of octamethylcyclotetrasiloxane and 13.1 g of the aminoalkyl group-containing siloxane used in Synthesis Example 1 were added. Was added, and an equilibration reaction and a deacetone reaction were carried out in the same manner as in Synthesis Example 1. As a result, an oil having a viscosity of 7,400 cp and a volatile residue of 97.5% was obtained. However, the average structural formula of this one is

[Chemical 18] Was confirmed to be an organopolysiloxane containing an aminoalkyl group and a triglycerin group (hereinafter abbreviated as organopolysiloxane B).

Synthesis Example 3 Unsaturated triglycerin derivative 50. used in Synthesis Example 1
4g and formula

[Chemical 19] Methylhydrogenpolysiloxane 22 represented by
When 8.0 g was used to perform an addition reaction in the same manner as in Synthesis Example 1, an oil having a viscosity of 40 cS and a refractive index of 1.415 was obtained. The following formula

[Chemical 20] Was confirmed to be an organopolysiloxane containing a triglycerin derivative.

Next, the organopolysiloxane 44
The following formula for 7.2 g

[Chemical 21] 52. Aminoalkyl group-containing cyclic siloxane represented by
When 8 g was added and an equilibration reaction and a deacetonization reaction were carried out in the same manner as in Synthesis Example 1, the viscosity was 5,3.
An oil having a volatilization residue of 97.8% was obtained at 00 cp. The oil was analyzed, and its average structural formula was as follows:

[Chemical formula 22] Was confirmed to be an organopolysiloxane having an aminoalkyl group and a triglycerin group (hereinafter abbreviated as organopolysiloxane C).

Comparative Synthesis Example 1 Octamethylcyclotetrasiloxane 479.4 g, aminoalkyl group-containing cyclic siloxane 10.5 g used in Synthesis Example 1 and decamethyltetrasiloxane 10.1.
An equilibration reaction was carried out using g in the same manner as in Synthesis Example 1. The viscosity was 450 cS and the volatile residue was 98.5%.
Was obtained, which was analyzed,
The average structural formula is

[Chemical formula 23] Was confirmed to be an aminoalkyl group-containing organopolysiloxane (hereinafter abbreviated as organopolysiloxane D).

Comparative Synthesis Example 2

[Chemical formula 24] Methylhydrogenpolysiloxane 17 represented by
0.0 g, allyl glycidyl ether 2.5g and the formula _{CH 2 = CHCH 2 O- (CH} 2 CH 2 O) Synthesis Example 1 by using the polyether compound 27.5g represented by ₁₀ -H
After carrying out the addition reaction in the same manner as described above, 1.3 g of ethylenediamine (equimolar amount to epoxy group) was added,
The reaction was carried out at 70 ° C. for 2 hours, and then the low boiling point component was removed under reduced pressure in the same manner as in Synthesis Example 1, and the viscosity was 3,500 cS.
An oil with a volatile residue of 95.8% was obtained, but the oil was analyzed and the average structural formula was

[Chemical 25] Was confirmed to be an organopolysiloxane containing an aminoalkyl group and a polyether group (hereinafter abbreviated as organopolysiloxane E).

[0028]

EXAMPLES Examples 1 to 3, Comparative Examples 1 to 2 of the organopolysiloxanes A to C obtained in the above Synthesis Examples 1 to 3 and the organopolysiloxanes D and E obtained in the Comparative Synthesis Examples 1 and 2 150 g of each was emulsified and dispersed in 320 g of water using 30 g of polyoxyethylene nonylphenyl ether as an emulsifier to prepare an emulsion.

Then, this emulsion was diluted with water to 1% by weight.
After dipping in cotton and dipping it in cotton broad cloth, squeeze it with a roll at a squeezing ratio of 100%, then heat treatment at 100 ° C. for 2 minutes, then 150 ° C. for 2 minutes. When evaluated by touch, the results shown in Table 1 were obtained. Regarding the hydrophilicity, when 20 μL of small droplets were left still on the treated cloth with a measuring pipette and the time until the water droplets permeated was measured, the results shown in Table 1 were obtained. It was The flexibility was evaluated according to the following criteria. ◯: A very soft and good texture was exhibited. Δ: The texture was slightly hard and had a core remaining. X: Coarse and hard and showed no slip.

[0030]

[Table 1]

[0031]

INDUSTRIAL APPLICABILITY The present invention relates to a fiber treating agent, which contains an organopolysiloxane containing an aminoalkyl group and a triglycerin group represented by the general formula (1) as a main component. However, the treatment of fibers and textiles with this organopolysiloxane offers the advantage of simultaneously imparting both flexibility and hydrophilicity to the article to be treated.

Claims (1)

[Claims] 1. A general formula: [Here, R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ²
Is the formula —R ⁵ — (NR ⁶ R ⁷ ) _d —NR ⁸ R ⁹ (A) (wherein R ⁵ and R ⁷ are divalent hydrocarbon groups having 1 to 8 carbon atoms,
R ^6, R ^8, R ⁹ is a monovalent hydrocarbon group, group d is represented by an integer) of 0-4 C1-8 hydrogen or C, R ³ is the formula -R ¹⁰ -OCH [CH ₂ OCH ₂ CH (OH) -CH ₂ (OH)] ₂ (B) (wherein R ¹⁰ is a divalent hydrocarbon group having 2 to 8 carbon atoms), R ⁴ is a group represented by the formula —OR ¹¹ (R ¹¹ is a hydrogen atom or a group represented by a monovalent hydrocarbon group having 1 to 4 carbon atoms), or R
¹ , one or two kinds of groups selected from the groups represented by formulas (A) and (B), a, b and c are each 0 or an integer of 1 or more, and when b is 0, R ^At least one of ⁴ is a group represented by the formula (A), and when c is 0, at least one of R ⁴ is a group represented by the formula (B)]. A fiber treatment agent characterized in that