JP3199609B2 - Fiber treatment composition - 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 treatment composition, and more particularly to a fiber treatment composition capable of imparting excellent flexibility and water absorption to fibers and having very little yellowing due to heat and ultraviolet rays. .

[0002]

2. Description of the Related Art Conventionally, various organopolysiloxanes such as dimethylpolysiloxane, epoxy group-containing polysiloxane, aminoalkyl group-containing polysiloxane and the like have been used as treatment agents for imparting flexibility and smoothness to various fiber products. Aminoalkyl group-containing polysiloxanes are most often used because they are widely used and can give particularly good flexibility. However, when an aminoalkyl group-containing polysiloxane is used, the aminoalkyl group is oxidized by heat, ultraviolet rays, or the like, and thus has a serious disadvantage that the color tone of the processed product changes to yellow.

In order to improve the above drawbacks, for example, aminoalkyl group-containing polysiloxanes may be replaced with organic acid anhydrides or chlorides (see JP-A-57-101076) and higher fatty acids (see JP-A-1-306683). ), Carbonate (see Japanese Patent Application Laid-Open No. 2-47371) and the like to modify an aminoalkyl group. However, in these cases, although improvement in discoloration is recognized as compared with the aminoalkyl group-containing polysiloxane before modification, the effect is still insufficient, and smoothness is imparted to the treated fiber. There is a disadvantage that the properties inherent in the aminoalkyl group-containing polysiloxane are impaired.

[0004] Further, since a treated product with an aminoalkyl group-containing polysiloxane generally becomes water repellent, even fibers that originally have water absorbency show hydrophobicity after being treated,
For example, there is also a disadvantage that the sweat absorbing action during sweating is almost lost. This point can be improved by, for example, including an aminoalkyl group and a polyoxyalkylene group in the same polysiloxane molecule (see Japanese Patent Application Laid-Open No. 599-179887). Therefore, there is a disadvantage that flexibility and smoothness are greatly reduced. Further, in order to improve the above drawbacks, it has been proposed to modify an aminoalkyl group by reacting an aminoalkyl group-containing polysiloxane with a polyoxyalkylene glycidyl ether compound (see Japanese Patent Publication No. 64-1588). . However, also in this case, when the number of polyoxyalkylene groups is increased in order to make the resulting modified organopolysiloxane an aqueous solution, water absorption becomes good but flexibility becomes insufficient, and conversely, polyoxyalkylene groups are reduced. For these products, an emulsifier for dispersion is required, in which case the flexibility becomes insufficient, and both properties have not been satisfied.

[0005]

As described above, a fiber treatment composition having good flexibility, water absorption and low yellowing has not yet been known. Therefore, the present invention
It is an object of the present invention to provide a fiber treating agent having the characteristics of imparting flexibility, water absorption, and low yellowing to fibers.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, a fiber treatment composition obtained by dispersing an organopolysiloxane having a limited structure in an acidic aqueous solution is extremely excellent. And reached the present invention. That is, fiber treatment agent composition of the present invention has solved the above problems, the milk organopolysiloxane this fiber treatment agent composition represented by the following general formula 1
It is obtained by dispersing in an acidic aqueous solution having a pH of 1 to less than 7 without using an agent .

Embedded image

In the formula, R is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and A is a general formula 2-R ^1- (NR ² -R ³ ) _a -NR ⁴ R ^5. In the formula, R ¹ is a divalent hydrocarbon group having 1 to 8 carbon atoms,
R ² , R ⁴ and R ⁵ are a hydrogen atom directly connected to a nitrogen atom or a general formula 3-CH ₂ CH (OH) CH ₂ (OC ₂ H ₄ ) _b (OC ₃ H ₆ ) _c OR ^6. In the formula, R ⁶ is a hydrogen atom or a monovalent organic group selected from a monovalent hydrocarbon group having 1 to 8 carbon atoms and an acyl group;
Is an integer of 2 to 20, and c is an integer of 0 to 10. ) A monovalent group represented by the group represented by R ^2, R ⁴ and the sum in formula 3 of R ⁵ is at least 30 mol%, R ³ is 2 to 4 carbon atoms
A is an integer of 0 to 4; ] Is a monovalent group represented by, X is represented R, (wherein, R ⁷ is a monovalent hydrocarbon group having 1 to 8 carbon hydrogen atom or a carbon.) A or Formula -OR ⁷ with 1 M is a positive number from 5 to 500, n is a positive number from 0 to 100, provided that when n = 0, at least one of X is A. ｝

Hereinafter, the present invention will be described in detail. As described above, the fiber treating agent composition of the present invention can be prepared by adding the organopolysiloxane represented by the general formula 1 to an aqueous solution having a pH of 1 without using an emulsifier.
It is dispersed in an acidic aqueous solution of less than ~ 7,
This organopolysiloxane can be easily obtained by reacting an organopolysiloxane represented by the following general formula 4 with a polyoxyalkylene glycidyl ether represented by the following general formula 5.

Embedded image [Wherein, R is the same as described above, and B is a general formula 6-R ^1- (NH-R ³ ) _a -NH ₂ ... 6 (wherein R ¹ , R ³ and a are the same as those described above) Wherein Z is R, B or -OR ⁷ (wherein R ⁷ is the same as defined above), and m and n are the same as defined above. However, when n = 0, at least one of Z is B. ]

Embedded image (In the formula, R ⁶ , b, and c are the same as described above.)

In general formula 1 or general formula 4, R
Specific examples of a methyl group, an ethyl group, a propyl group,
Butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tetradecyl group, alkyl group such as octadecyl group, alkenyl group such as vinyl group and allyl group, cycloalkyl group such as cyclopentyl group and cyclohexyl group Examples include a group, an aryl group such as a phenyl group, a tolyl group, and a naphthyl group, or a group in which a hydrogen atom bonded to a carbon atom of these groups is partially substituted with a halogen atom. Among these groups, a methyl group is particularly preferred. Further, among the general formula 1 X is R ⁷ when it is -OR ⁷ in, monovalent hydrocarbon groups include methyl group Specific examples of the ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl Group, phenyl group and the like. When m in the general formula 1 is smaller than 5, the flexibility becomes insufficient, and when it is larger than 500, the water absorption becomes insufficient. Preferably 10-100
It is. If n is larger than 100, the flexibility is insufficient, so that it is set to 0 to 100, preferably 0.5 to 10.

In the general formula 2 or the general formula 6, R ¹
As a methylene group, a dimethylene group, a trimethylene group, an alkylene group such as a tetramethylene group is preferable,
Among them, a trimethylene group is preferable. Specific examples of R ³ include a methylene group, a dimethylene group, a trimethylene group,
Examples include an alkylene group such as a tetramethylene group,
Particularly, a dimethylene group is preferable. Further, if a is 5 or more in the general formula 2 or 6, the production becomes difficult, and therefore a is 0 to 4. Further, in order to improve the water absorption of the object, R ² , R ⁴ and
In the total of R ^5, the group represented by the general formula 3 is at least 30 mol%, preferably at least 50 mol%.

In the general formula 3 or the general formula 5, R ⁶
Specific examples of a hydrogen atom or a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Heptyl group, alkyl group such as octyl group, acetyl group,
An acyl group such as a benzoyl group is exemplified, and a methyl group, a butyl group, and an acetyl group are particularly preferable. If b in the formula is less than 2, the water absorption becomes insufficient, and if it is more than 20, the flexibility becomes insufficient. Preferably it is 3-10. On the other hand, if c is larger than 10, water absorption becomes insufficient, so that c is set to 0-10. Preferably it is 0-5.

The following are specific examples of the organopolysiloxane represented by the general formula 4 used in the present invention, but are not limited thereto.

Embedded image (In the formula, m and n are the same as described above.)

The following are specific examples of the polyoxyalkylene glycidyl ether represented by the general formula 5 used in the present invention, but are not limited thereto.

Embedded image (In the formula, b and c are the same as described above.)

In the production process of the organopolysiloxane represented by the general formula 1, the organopolysiloxane represented by the general formula 4 and the polyoxyalkylene glycidyl ether represented by the general formula 5 are reacted by the following reaction formula 1.
(Ring opening reaction of epoxy group).

Embedded image The hydroxyl group generated by the ring-opening reaction of the epoxy group imparts water absorbency to the organopolysiloxane together with the polyoxyalkylene group.

As described above, in order to improve the water absorption of the object to be treated, the group represented by the general formula 3 in the total of R ² , R ⁴ and R ⁵ in the general formula 2 is preferably 30 mol% or more, more preferably Is 50 mol% or more, so that the polyoxyalkylene glycidyl ether represented by the general formula 5 is 30 mol% or more, preferably 50 mol% or more, based on all NH groups in the organopolysiloxane represented by the general formula 4. It is necessary to make it react so that The reaction between the NH group-containing organopolysiloxane and the polyoxyalkylene glycidyl ether is carried out in the absence of a solvent or in a solvent such as a lower alcohol, toluene, or xylene.
Performing at 00 ° C for 1 to 10 hours is sufficient.

The organopolysiloxane represented by the general formula 1 is as described above, but the organopolysiloxane is dispersed uniformly in an acidic aqueous solution without using an emulsifier, whereby the fiber treating agent composition of the present invention is obtained. Get things. To this end, the organopolysiloxane may be charged and stirred in an acidic aqueous solution in which 0.5 to 1.5 equivalents of an acid substance is dissolved with respect to the nitrogen atoms in the organopolysiloxane, and the acidic aqueous solution may be stirred even if the pH of the acidic aqueous solution is less than 1. Even if it is 7 or more, the obtained composition becomes unstable, so that 1 to less than 7 is required. Preferably it is 2-5. As the acid substance, an organic acid such as acetic acid, malonic acid, and citric acid, or an inorganic acid such as hydrochloric acid, sulfuric acid, and nitric acid can be used. To the fiber treatment composition of the present invention, other fiber agents, for example, a wrinkle-preventing agent, a flame retardant, an antistatic agent, etc. may be added as long as their properties are not impaired.

In treating various fiber products using the fiber treatment composition of the present invention, the fibers are diluted with water so as to have a desired concentration, and are adhered to the fibers by means of dipping, spraying, roll coating or the like. It may be dried. There is no particular limitation on the amount of adhesion in this case, but usually about 0.1 to 5.0% by dry weight of the fiber is sufficient. The fibers or fiber products treated with the fiber treatment composition of the present invention are not particularly limited, and include natural fibers such as cotton, silk, hemp, and wool, as well as synthetic fibers such as polyester, nylon, and acrylic, and It is effective for textile products using these.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described by way of examples, but the present invention is not limited thereto. In the examples,% represents% by weight, and part represents parts by weight. Example 1 In a separable flask having a capacity of 500 ml equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube, 61.7 g of an aminoalkyl group-containing organopolysiloxane (molecular weight 2,056) represented by the following formula a, 36.4 g of polyoxyalkylene glycidyl ether represented by b (molecular weight: 404)
(100 mol% based on the total NH in the aminoalkyl group-containing organopolysiloxane) and isopropyl alcohol
0 g, and stirring at 80 ° C. while introducing nitrogen gas.
A time reaction was performed. After the reaction is completed, under reduced pressure of 10 mmHg, 100
The low boiling point fraction was removed at 1 ° C for 1 hour.
92.8 g of an oily substance represented by the following formula c of 90 cP was obtained.

Embedded image

5 g of the obtained oily substance was dispersed in 20 g of a 0.9% aqueous acetic acid solution (pH 2.9) (1 equivalent of acetic acid / nitrogen atom) to prepare a 20% aqueous solution. The resulting aqueous solution was pale yellow and transparent, and no change was observed after standing at room temperature for one month. The above 20% aqueous solution was diluted to 1% with water, and a T / C broad cloth, a polyester knit cloth, and a cotton broad cloth having been subjected to a fluorescent treatment were immersed in the diluted solution.
Squeeze with a roll at 100% condition, then 2 at 100 ° C
Heat treatment at 150 ° C. for 2 minutes.

The flexibility of the T / C broad cloth after the treatment was evaluated by touch, and it was found that the T / C broad cloth had a slimy feeling and had a good texture rich in flexibility. In addition, a water drop of about 50 μl was placed on the treated polyester knit cloth with a dropper, and the water absorption was evaluated by measuring the time until the water drop was absorbed by the cloth. 0.1 second, which proved that the water absorption was extremely good. Further, the B value (indicating the yellowness; the larger the value, that is, the closer the negative value is to 0, the stronger the yellowness) was measured with a color difference meter for the treated cotton broad cloth.
8.1. Next, the cotton broad after this treatment is
For 5 minutes, and the B value was measured to be -6.3, indicating almost no yellowing. The results of these characteristic evaluations are summarized in Table 1. However, the symbols of flexibility are: ：: slimy texture, extremely flexible texture, △: almost slimy texture, slightly coarse and firm core remaining, ×: coarse and hardly flexible Texture.
Also in the following Examples 2 to 6 and Comparative Examples 1 to 4, the characteristics were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 2 61.7 g of the aminoalkyl group-containing organopolysiloxane of the formula a used in Example 1 and 24.2 g of the polyoxyalkylene glycidyl ether of the formula b (total in the aminoalkyl group-containing organopolysiloxane) 6 for NH
7mol%) and 170cP oil 81.
0 g was obtained. 5 g of this oily substance was added to a 1.2% aqueous acetic acid solution (pH
2.8) Dispersed in 20 g (1 equivalent of acetic acid / nitrogen atom). The resulting aqueous solution was pale yellow and transparent, and no change was observed even after being left at room temperature for one month.

Example 3 51.4 g of the aminoalkyl group-containing organopolysiloxane represented by the formula a used in Example 1 and a polyoxyalkylene glycidyl ether represented by the following formula d (molecular weight: 650) 4
The reaction was carried out using 8.8 g (100 mol% based on the total NH in the aminoalkyl group-containing organopolysiloxane) to obtain 91.0 g of an oily substance. 5 g of the obtained oily substance was dispersed in 20 g of an aqueous 0.8% acetic acid solution (pH 2.9) (1 equivalent of acetic acid / nitrogen atom). The resulting aqueous solution was pale yellow and transparent,
No change was observed after standing for a month.

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Example 4 29.2 g of an aminoalkyl group-containing organopolysiloxane represented by the following formula e and 48.5 g of the polyoxyalkylene glycidyl ether represented by the formula b used in Example 1 (in the aminoalkyl group-containing organopolysiloxane) For all NH
(100 mol%) to obtain 75.0 g of an oily substance. 4 g of this oily substance was added to a 0.2% acetic acid aqueous solution (pH 3.4)
16 g (1 equivalent of acetic acid / nitrogen atom). The resulting aqueous solution was pale yellow and transparent, and no change was observed even after being left at room temperature for one month.

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Example 5 5 g of the oily substance represented by the formula c used in Example 1
20% aqueous solution of citric acid (pH 2.1) (1 equivalent of citric acid / nitrogen atom) to prepare a 20% aqueous solution. The resulting aqueous solution was pale yellow and transparent, and no change was observed even after being left at room temperature for one month.

Example 6 5 g of the oily substance of the formula c used in Example 1 was
20% aqueous phosphoric acid solution (pH 2.0)
(Equivalent / nitrogen atom), a 20% aqueous solution was prepared. The obtained solution was a white emulsion, and no change was observed even after being left at room temperature for one month.

Comparative Example 1 5 g of the oily substance represented by the formula c obtained in Example 1 was charged into 20 g of purified water, and the mixture was stirred, but was not uniformly dispersed. Therefore, the nonionic emulsifier 8.5 parts
And 20 parts of phase inversion water, and primary emulsification was performed by high-speed rotation with a homomixer. Then, dilute with 46.5 parts of dilution water,
After secondary emulsification under a pressure of 300 kg / cm ^{2 with} a high-speed homogenizer, 0.17 parts of acetic acid was added, and the mixture was heated and aged at 70 to 80 ° C. for 1 hour to prepare an emulsion.

Comparative Example 2 20.6 g of the aminoalkyl group-containing organopolysiloxane of the formula a used in Example 1 and a polyoxyalkylene glycidyl ether of the following formula f (molecular weight 1,180)
The reaction was carried out using 35.3 g (100 mol% based on the total NH in the aminoalkyl group-containing organopolysiloxane) to obtain 53 g of an oily substance represented by the following formula g. This oily substance 5
g was dispersed in 20 g of purified water, and the aqueous solution obtained was pale yellow and transparent, and no change was observed at all even after standing at room temperature for one month.

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Comparative Example 3 1,028 g of the aminoalkyl group-containing organopolysiloxane represented by the formula a used in Example 1 and 111 g of glycidyl alcohol (molecular weight: 74) represented by the following formula h (in the aminoalkyl group-containing organopolysiloxane) 100mol to total NH
%) And an oily substance represented by the following formula i
1,130 g were obtained. This oily substance was emulsified in the same manner as in Comparative Example 1 to prepare an emulsion.

Embedded image

Comparative Example 4 The aminoalkyl group-containing organopolysiloxane represented by the formula a used in Example 1 was emulsified in the same manner as in Comparative Example 1 without reacting to prepare an emulsion.

[0030]

[Table 1]

As can be seen from Table 1, in Examples, flexibility, water absorption and yellowing resistance are all good.
Comparative Examples 1 and 2 have good water absorption and yellowing resistance, but poor flexibility. Comparative Example 3 has good flexibility and yellowing resistance but insufficient water absorption. In Comparative Example 4, although flexibility was good, water absorption and yellowing resistance were extremely poor.

[0032]

The fiber treating composition of the present invention can impart not only water absorbency to the object to be treated, but also excellent flexibility to the object to be treated. Further, yellowing due to heat or ultraviolet rays is minimized. That is, the fiber treatment composition of the present invention can simultaneously satisfy these demands which could not be simultaneously satisfied conventionally.

────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Masaki Tanaka 2-6-1 Otemachi, Chiyoda-ku, Tokyo Shin-Etsu Chemical Co., Ltd. Headquarters (56) References JP-A-2-284959 (JP, A) JP-A-61-296184 (JP, A) JP-A-58-1749 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D06M 15/00-15/715

Claims (1)

(57) [Claims] 1. A fiber treatment composition comprising an organopolysiloxane represented by the following general formula 1 dispersed in an acidic aqueous solution having a pH of 1 to less than 7 without using an emulsifier . Embedded image In the formula, R is a monovalent hydrocarbon group having 1 to 20 carbon atoms;
Is a general formula 2-R ^1- (NR ² -R ³ ) _a -NR ⁴ R ⁵ ... 2 wherein R ¹ is a divalent hydrocarbon group having 1 to 8 carbon atoms;
² , R ⁴ and R ⁵ are a hydrogen atom directly bonded to a nitrogen atom or a general formula 3-CH ₂ CH (OH) CH ₂ (OC ₂ H ₄ ) _b (OC ₃ H ₆ ) _c OR ^6. Wherein R ⁶ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms, or a monovalent organic group selected from acyl groups;
Is an integer of 2 to 20, and c is an integer of 0 to 10. ) A monovalent group represented by the group represented by R ^2, R ⁴ and the sum in formula 3 of R ⁵ is at least 30 mol%, R ³ is 2 to 4 carbon atoms
A is an integer of 0 to 4; ] Is a monovalent group represented by, X is represented R, (wherein, R ⁷ is a monovalent hydrocarbon group having 1 to 8 carbon hydrogen atom or a carbon.) A or Formula -OR ⁷ with 1 M is a positive number from 5 to 500, n is a positive number from 0 to 100, provided that when n = 0, at least one of X is A. ｝