JP2887337B2 - Fiber treatment agent - Google Patents

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, particularly a fiber treating agent containing organopolysiloxane as a main component, for imparting excellent flexibility and hydrophilicity to various fibers such as natural fibers and synthetic fibers. It is about.

[0002]

2. Description of the Related Art Various treating agents for imparting flexibility and smoothness to textile products have been known in the art, such as dimethylpolysiloxane, epoxy-containing polysiloxane, aminosiloxane and the like. Alkyl group-containing polysiloxanes and the like have been proposed (JP-B-48-1480, JP-B-54-43617).
And JP-B-59-26707), among them, aminoalkyl group-containing polysiloxanes are widely used because they are excellent in imparting flexibility to fibers.

[0003] However, when treated with this aminoalkyl group-containing polysiloxane, the treated fabric exhibits water repellency, so that the nature of natural fibers, such as natural fibers, is impaired. There is a point. Also,
In order to impart hydrophilicity to the fibers, it is known that the fibers are treated with a polyether group-containing polysiloxane.
In this case, flexibility is considerably inferior to the above-mentioned aminoalkyl group-containing polysiloxane.

[0004]

Therefore, various proposals have been made for a method of improving the flexibility, for example, an organopolysiloxane containing a polyether group and an aminoalkyl group in one molecule. It has been proposed to use siloxane (JP-B-61-472).
Japanese Patent Application Laid-Open No. 2-276824) discloses an organic polysiloxane which has a large decrease in flexibility and which binds a segment of poly (N-acylalkyleneimine). This has a problem such as insufficient flexibility due to the method of introducing the organopolysiloxane (structure of the bonding group), and a fiber treatment agent satisfying both the properties of flexibility and hydrophilicity has not yet been obtained.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a fiber treating agent which solves such disadvantages, and comprises a general formula:

Embedded image [Where R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ²
Is the expression

Embedded image (Where R ⁵ has 1 to 10 carbon atoms which may contain an ether bond)
R ⁶ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, m is 2 or 3, n is an integer of 1 to 100), a poly (N-acylalkyleneimine) group represented by R ³ is the formula

Embedded image (Where R ⁷ and R ⁹ are divalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁸ , R ¹⁰ and R ¹¹ are each a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and p is 0 to 10) An integer of 6), R ⁴ is R ¹ , R ² , R ³ or a hydroxyl group, a group selected from alkoxy groups having 1 to 6 carbon atoms,
a, b, and c are each an integer of 0 or 1 or more, provided that
and when b is 0, at least one of R ⁴ is a group represented by R ² ].

That is, the present inventors have conducted various studies to develop a fiber treatment agent capable of simultaneously imparting both flexibility and hydrophilic properties to a fiber product.
When a compound obtained by introducing an (acylalkyleneimine) group into an organopolysiloxane via a divalent hydrocarbon group which may contain an ether bond is applied to a fiber treatment agent, both the properties of flexibility and hydrophilicity, which have been unsatisfactory, have been simultaneously obtained, and The present invention was found to be greatly improved, and it was confirmed that introduction of an aminoalkyl group into this organopolysiloxane could further improve the flexibility, thereby completing the present invention. This is described in more detail below.

[0007]

The present invention relates to a fiber treating agent capable of simultaneously imparting both flexibility and hydrophilic properties to a fiber product. The agent comprises an organopolysiloxane represented by the aforementioned general formula (1) as a main component. It is characterized by becoming.

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

Embedded image It is assumed that R in this general formula (1)
¹ is an alkyl group such as methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, alkenyl group such as vinyl group, allyl group, cycloalkyl group such as cyclohexyl group, cycloheptyl group, phenyl group, naphthyl group, etc. An unsubstituted or substituted 1-20 carbon atom selected from an aryl group, or a group in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom or any organic group; It is a valent hydrocarbon group, particularly preferably a methyl group.

The R ² is represented by the following formula (A)

Embedded image In the formula, R ⁵ represents — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, or —C 1 to 10 carbon atoms which may contain an ether bond.
_{H 2 CH (CH 3) -} , - (CH 2) 6 -, - (CH
₂ ) ₃ O (CH ₂ ) ₂ -,-(CH ₂ ) ₃ O (CH ₂ C
_{H 2 O) 2 (CH 2} ) 2 - 2 divalent hydrocarbon group represented by like, R ⁶ is a monovalent hydrocarbon group of similar having 1 to 20 carbon atoms and R ^1, m is 2 or 3, preferably An integer that is 2, n
Is a poly (N-acylalkyleneimine) group which is an integer of 1 to 100, preferably 5 to 20.

Further, this R ³ is represented by the following formula (B)

Embedded image In the formula, R ⁷ and R ⁹ are the same divalent hydrocarbon groups having 1 to 10 carbon atoms as R ⁵ described above, R ⁸ , R ¹⁰ , and R ¹¹
Is a hydrogen atom or a carbon number 1 to 4 similar to R ¹ described above.
20 is a monovalent hydrocarbon group, p is an aminoalkyl group having an integer of 0 to 6, and R ⁴ is R ¹ , R ² , R ³ or a hydroxyl group;
One or two groups selected from alkoxy groups having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group, and an n-butyroxy group, and a, b and c are each an integer of 0 or 1 And when b is 0, at least one of R ⁴ is a group represented by R ² .

As a method for introducing a poly (N-acylalkyleneimine) group represented by R ² into the organopolysiloxane, the following general formula (2)

Embedded image Wherein R ¹ , R ⁵ , a and b are the same as above, and R ¹² is a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, R ¹ or —R
One or two groups selected from ^5- OH groups,
Is 0, an organopolysiloxane containing an alcoholic hydroxyl group in which at least one of R ¹² is a group represented by an —R ⁵ —OH group is subjected to sulfonic acid esterification using a sulfonic acid or a sulfonic acid derivative, , The following equation (3)

Embedded image And a cyclic iminoether compound in which R ⁶ and m are the same as described above, for example, 2-oxazolines and 2-oxazines are added, and the ring-opening polymerization can be carried out.

In this case, the n value of the poly (N-acylalkylenimine) group can be arbitrarily determined by adjusting the amount of the cyclic iminoether compound added thereto. Since the terminal of the group is formed as a sulfonate, such an acid radical can be removed by using a suitable hydroxyl group type ion exchange resin if necessary.

The aminoalkyl group represented by R ³ includes — (CH ₂ ) ₃ NH ₂ , — (CH
₂ ) ₃ NH (CH ₂ ) ₂ NH ₂ ,

Embedded image

Embedded image

Embedded image

Embedded image —CH ＝ CHCH ₂ NH (CH ₂ ) ₂ NH _{2 and the} like. Examples of a method for introducing this aminoalkyl group into an organopolysiloxane include a poly (N-acylalkylenimine) group obtained by the above-described method. And an organopolysiloxane containing the following formula (4)

Embedded image Wherein R ¹ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and p are as described above and q is an integer of 3 to 10 and an aminoalkyl group-containing cyclic siloxane in the presence of an alkaline catalyst An equilibration reaction may be performed below.

In the general formula (1), R ⁴ is R ¹ , R ² , R ³ , a hydroxyl group or a group having 1 carbon atom as described above.
And a group selected from the group consisting of a,
b and c are 0 or an integer of 1 or more. In order to provide good flexibility and hydrophilicity using this fiber treating agent, a is 50 to 1000, b is 0 to 50, c is preferably 0 to 50, and when b is 0, R ⁴
Is required to be a group represented by R ² . The organopolysiloxane represented by the general formula (1) may have a hydroxyl group or an alkoxy group introduced into a siloxane terminal, and the introduction of the hydroxyl group or the alkoxy group may be performed, for example, by adding water or alkoxysilane.
The equilibration reaction may be performed in the presence of an alkali catalyst.

The fiber treating agent of the present invention contains the organopolysiloxane represented by the above-mentioned general formula (1) as a main component. The addition of a flame retardant, an anti-wrinkle agent, a penetrant or the like is optional.

In treating various fiber products with the fiber treating agent of the present invention, the fibers are diluted and dissolved with water or a suitable solvent to adjust to a desired concentration, or a surfactant is added as necessary. After emulsifying and dispersing in water to form an emulsion, dilute with water, adjust to the desired concentration, and attach the organopolysiloxane of the above formula (1) to the fiber by means of dipping, roll coating, spraying, etc. And then drying. In this case, the amount of adhesion is not particularly limited, but usually about 0.1 to 5% by weight based on the cloth is sufficient.

The surfactant used when emulsifying the organopolysiloxane includes anionic surfactants such as sodium alkyl sulfate and sodium alkylbenzene sulfonate, polyoxyethylene alkyl phenyl ether, polyoxyethylene, and the like. Nonionic surfactants such as alkyl ethers, cationic surfactants such as quaternary ammonium salts, and amphoteric surfactants such as alkyl betaine can be used as emulsifiers.

The fiber or fiber product treated with the fiber treating agent of the present invention is variously selected. Natural fibers or fiber products such as cotton, hemp, silk and wool, and synthetic fibers or fibers such as polyester, nylon and acrylic Examples include products, which are not particularly limited, and are effective for all fibers and fiber products.

Next, synthesis examples of organopolysiloxanes used in Examples and Comparative Examples of the present invention, and Examples and Comparative Examples using the same will be given. (Synthesis Example 1) A 500-ml flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with the formula

Embedded image 85.6 g (0.05 mol) of an alcoholic hydroxyl group-containing organopolysiloxane represented by the following formula:
After mixing and dissolving 00 ml and 100 ml of pyridine, 51.6 g of p-toluenesulfonic acid chloride was obtained.
(0.25 mol) while maintaining the reaction temperature at 10 ° C. or lower, and further stirred at room temperature for 5 hours to carry out a sulfonic acid esterification reaction.

Then, the reaction solution was filtered to remove pyridine hydrochloride, and chloroform and excess pyridine were distilled off under reduced pressure. As a result, a viscous sulfonic acid ester of organopolysiloxane was obtained. (0.
03 mol) and acetonitrile 150 ml, 2-ethyl-
74.3 g (0.75 mol) of 2-oxazoline was charged into a flask similar to the above, and a ring-opening polymerization reaction was carried out under acetonitrile reflux under a nitrogen atmosphere for 5 hours. The reaction was stopped because the reaction time was as theoretical. After cooling, the sulfonate group was removed with a hydroxyl-type ion exchange resin, and acetonitrile was further distilled off under reduced pressure to obtain a pale yellow, translucent solid. So
Elemental analysis, IR and NMR analysis of this product showed that

Embedded image It was confirmed that a in shown are poly (N- acylalkyleneimine) group-containing organopolysiloxane (hereinafter siloxane A ₁ hereinafter).

Next, the obtained poly (N-acylalkylenimine) group-containing organopolysiloxane 125.6 is obtained.
g, octamethylcyclotetrasiloxane 421.8
g, formula

Embedded image 19. an aminoalkyl group-containing cyclic siloxane represented by the formula:
2 g and 0.06 g of KOH as a catalyst were charged into a flask having a capacity of 1 liter in the same manner as above, and an equilibration reaction was carried out at 150 ° C. for 6 hours with stirring in a nitrogen atmosphere.
After cooling to 00 ° C., 0.4 g of ethylene chlorohydrin was added, and the catalyst was neutralized at 100 ° C. for 2 hours. As a result, a yellow solid product was obtained. This one has the average structural formula

Embedded image In shown, the poly (N- acylethyleneimine) (hereinafter abbreviated as Siloxane A ₂₎ organopolysiloxane containing groups and aminoalkyl groups was confirmed.

Synthesis Example 2 Poly (N) obtained in Synthesis Example 1
-Equilibration reaction in the same manner as in Synthesis Example 1 using 251.2 g of an organopolysiloxane having an (acylethyleneimine) group, 177.6 g of octamethylcyclotetrasiloxane, and 9.6 g of the cyclic siloxane having an aminoalkyl group used in Synthesis Example 1 To give a pale yellow solid product, which was analyzed and found to have the average structural formula

Embedded image Is confirmed to be an organopolysiloxane containing a poly (N-acylethyleneimine) group and an aminoalkyl group (hereinafter abbreviated as siloxane B).

(Synthesis example 3) Formula

Embedded image Using 76.5 g (0.01 mol) of an alcoholic hydroxyl group-containing organopolysiloxane represented by the following formula and 4.1 g (0.02 mol) of paratoluenesulfonic acid, a sulfonic acid esterification reaction was carried out in the same reaction as in Synthesis Example 1. After that, the sulfonic acid ester of this organopolysiloxane 7
A ring-opening polymerization reaction was performed in the same manner as in Synthesis Example 1 using 9.9 g (0.01 mol) and 17.0 g (0.2 mol) of 2-methyl-2-oxazoline. When a solid was obtained, which was analyzed, it was found that the average structural formula was

Embedded image In shown, the poly (N- acylethyleneimine) group-containing organopolysiloxane (hereinafter abbreviated siloxane C ₁ and) was confirmed.

Next, 467.5 g of this poly (N-acylethyleneimine) group-containing organopolysiloxane and the formula

Embedded image 10. An aminoalkyl group-containing cyclic siloxane represented by
An equilibration reaction was carried out in the same manner as in Synthesis Example 1 using 7 g of the compound. As a result, a pale yellow translucent solid was obtained.

Embedded image In shown, the poly (N- acylethyleneimine) (hereinafter abbreviated as Siloxane C ₂₎ organopolysiloxane containing groups and alkylamine groups was confirmed.

(Synthesis Example 4) The same as in Synthesis Example 1 using 479.4 g of octamethylcyclotetrasiloxane, 10.5 g of the aminoalkyl group-containing cyclic siloxane used in Synthesis Example 1 and 10.1 g of decamethyltetralasiloxane. When the equilibrium reaction was carried out by the method, a colorless and transparent oil was obtained. As a result of analysis, it was found that the average structural formula was

Embedded image Is confirmed to be an aminoalkyl group-containing organopolysiloxane (hereinafter abbreviated as siloxane D).

(Synthesis example 5) Formula

Embedded image Methyl hydrogen polysiloxane 17 represented by the formula:
Using 0.0 g, 2.5 g of allyl glycidyl ether and 27.5 g of a polyether compound represented by the formula CH ₂ ＣＨCHCH ₂ O (CH ₂ CH ₂ O) ₁₀ H, an addition reaction was carried out in the same manner as in the synthesis example. After the reaction, 1.3 g of ethylenediamine (equimolar amount to the epoxy group) was added, and 7 g of ethylenediamine was added.
The reaction was carried out at 0 ° C. for 2 hours, and then the low-boiling components were removed under reduced pressure in the same manner as in Synthesis Example 1. As a result, a pale yellow, slightly turbid oil was obtained.

Embedded image Is confirmed to be an organopolysiloxane containing an aminoalkyl group and a polyether group (hereinafter abbreviated as siloxane E).

[0027]

EXAMPLES Examples 1 to 3 and Comparative Examples 1 and 2 The siloxanes A ₁ and A obtained in Synthesis Examples 1 to 5 described above.
100 g each of ₂ , B, C ₁ , C ₂ , D and E were used as an emulsifier for polyoxyethylene nonyl phenyl ether 1
An emulsion was prepared by emulsifying and dispersing 0 g in 390 g of water. Next, this emulsion was diluted and dissolved with water so that the siloxane content was 1% by weight, and a cotton broad cloth was immersed in the diluted solution. Then, it was squeezed with a roll at a squeezing ratio of 100%, and was then squeezed at 100 ° C for 2 minutes and further at 150 ° C. When the heat treatment was performed for 2 minutes, and the flexibility of these treated cloths was evaluated by touch, the results shown in Table 1 were obtained.

Further, with respect to this treated cloth, a water drop of 20 μl was allowed to stand on the treated cloth using a pipette, and the time required for the water drop to penetrate was measured to determine the hydrophilicity. The results were as shown.

[0029]

[Table 1] From the above results, poly (N-acylalkyleneimine)
It has been confirmed that the fiber treating agent of the present invention comprising an organopolysiloxane containing a group or an aminoalkyl group and this group satisfies both the properties of flexibility and hydrophilicity, which have heretofore been said to be contradictory. .

[0030]

The present invention relates to a fiber treating agent, which comprises, as described above, a poly (N-acylalkyleneimine) group represented by the general formula (1) or an organo-containing aminoalkyl group. Although it is mainly composed of polysiloxane, if a fiber product is treated with this fiber treating agent, it is possible to simultaneously impart both properties of flexibility and hydrophilicity, which were previously considered impossible, to the fiber product. Advantages are given.

Continuation of front page (58) Field surveyed (Int.Cl. ⁶ , DB name) D06M 13/00-15/72

Claims (1)

(57) [Claims] 1. A compound of the general formula [Where R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ²
Is the formula (Where R ⁵ has 1 to 10 carbon atoms which may contain an ether bond)
R ⁶ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, m is 2 or 3, n is an integer of 1 to 100), a poly (N-acylalkyleneimine) group represented by R ³ is the formula (Where R ⁷ and R ⁹ are divalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁸ , R ¹⁰ and R ¹¹ are each a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and p is 0 to 10) An integer of 6), R ⁴ is R ¹ , R ² , R ³ or a hydroxyl group, a group selected from alkoxy groups having 1 to 6 carbon atoms,
a, b, and c are each an integer of 0 or 1 or more, provided that
and when b is 0, at least one of R ⁴ is a group represented by R ² ].