JPH06184946A - Composition for treating fiber - Google Patents

Abstract

(57) [Summary] [Object] To provide a treatment composition capable of imparting a good balance of flexibility, hydrophilicity and yellowing resistance to a fiber. [Structure] An amino group-containing polysiloxane represented by the following chemical formula 1, an epoxy compound represented by the following chemical formula 2, and CH = CR ⁷ -COO-R ⁸ (meth)
Acrylic ester (wherein R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms) and the epoxy compound and (meth). Molar ratio with acrylic ester / 10 /
It is 90 to 90/10 and is obtained by reacting such that the total amount of the epoxy compound and the (meth) acrylic acid ester is 50 mol% or more with respect to all NH groups contained in the amino group-containing polysiloxane. A fiber treatment composition comprising a reactant as a main component. [Chemical 1] [Chemical 2]

Description

Detailed Description of the Invention

[0001]

This invention relates to fiber treatment compositions,
In particular, the present invention relates to a fiber treatment composition capable of imparting excellent flexibility and hydrophilicity to fibers and having extremely 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, amino group-containing polysiloxane and the like have been widely used as a treating agent for imparting flexibility and smoothness to various textile products. Among them, amino group-containing polysiloxanes are most often used because they can impart particularly good flexibility.

However, when an amino group-containing polysiloxane is used, the amino group is oxidized by heat, ultraviolet rays, and the like, which has a serious drawback that the color tone of the treated product changes. In order to improve the above-mentioned drawbacks, for example, amino group-containing polysiloxane, organic acid anhydride or chloride (JP-A-57-101076), higher fatty acid (JP-A-1-306683), carbonate (JP-A-2-30683). 47371) and the like,
It has been proposed to modify the amino group.

However, in these cases, although improvement in discoloration is recognized as compared with the amino group-containing polysiloxane before modification, the effect is still insufficient, and the treated fiber has flexibility and smoothness. There is a drawback in that the inherent properties of the amino group-containing polysiloxane, such as imparting properties, tend to be impaired. Therefore, it is possible to suppress the decrease in flexibility by reacting the amino group-containing polysiloxane and the (meth) acrylic acid ester compound in a specific range (Japanese Patent Laid-Open No. 4-11).
9174), however, there is a drawback that the flexibility decreases when the reaction amount is increased for the purpose of improving yellowing.

Further, in general, a treated product with an amino group-containing polysiloxane becomes water-repellent, so that even fibers which are originally hydrophilic exhibit hydrophobicity after being treated, and for example, they have almost no sweat absorbing action during sweating. It also had the drawback of being lost. This point can be improved by, for example, incorporating an amino group and a polyoxyalkylene group in the same polysiloxane molecule (JP-A-57-17).
1768), however, contains a polyoxyalkylene group, resulting in a drawback that flexibility and smoothness are significantly reduced.

As a method of imparting hydrophilicity together with the above-mentioned improvement of yellowing, there is a method of reacting an amino group-containing polysiloxane with a monoepoxy compound.
9-179887), which again has the disadvantage that the flexibility of the treated fibers is reduced, as in the case of the various methods mentioned above.

[0007]

As described above, a fiber treatment composition which is excellent in flexibility and hydrophilicity and has very little yellowing of treated fibers has not been known yet. Therefore, the present inventors have made diligent studies on a fiber treating agent that imparts flexibility and hydrophilicity to the fiber and has very little yellowing of the treated fiber. As a result, an amino group-containing polysiloxane, an epoxy compound, and ( The present invention has been accomplished by finding that a fiber treating agent containing a reaction product with a (meth) acrylic acid ester as a main component is extremely excellent. Therefore, an object of the present invention is to provide a fiber treating agent which can impart flexibility and hydrophilicity to the fiber and which is less likely to cause yellowing of the fiber after being treated with heat or ultraviolet rays.

[0008]

The above objects of the present invention are as follows.
An amino group-containing polysiloxane represented by the following chemical formula 3,
Epoxy compound represented by the following chemical formula 4 and CH =
Represented by CR ⁷ -COO-R ⁸ (meth) acrylic acid ester (wherein, R ⁷ in the formula is a hydrogen atom or a methyl group,
R ⁸ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms), and the molar ratio of the epoxy compound and the (meth) acrylic acid ester is 10/90 to 90 /
In addition to 10, the reaction product obtained by reacting the epoxy compound and the (meth) acrylic acid ester in a total amount of 50 mol% or more based on all NH groups of the amino group-containing polysiloxane is mainly used. Achieved with the fiber treatment composition as an ingredient.

[0009]

[Chemical 3] R in the chemical formula ³ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and A is a formula —R ¹ — (NR ² —R ³ ) _a —
NHR ⁴ (wherein R ¹ and R ³ are substituted or unsubstituted divalent hydrocarbon groups having 1 to 8 carbon atoms, R ² and R ⁴ are hydrogen atoms, or substituted or unsubstituted having 1 to 20 carbon atoms) A monovalent hydrocarbon group, a is an integer of 0 to 4),
X is a group represented by R, A or -OR ⁵ (wherein R ⁵ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms), m is 10 to 1, 000, n is an integer of 0 to 100, and when n = 0, at least one X is A.

[0010]

[Chemical 4] R ^{6 in} Chemical formula 4 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain an ether bond.

Specific examples of R in the amino group-containing polysiloxane include methyl, ethyl, propyl, butyl,
Alkyl groups such as pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, octadecyl,
Alkenyl groups such as vinyl and allyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, aryl groups such as phenyl, tolyl and naphthyl, or groups in which these groups are partially substituted with a halogen atom or any organic group. I can name it.

R ¹ and R in the amino group represented by A
Examples of ³ include an alkylene group, an arylene group, an alkenylene group, and the like, and as R ² and R ⁴ ,
A hydrogen atom or a group similar to R can be exemplified. Specific examples of the amino group-containing polysiloxane used in the present invention include polysiloxanes represented by the following chemical formulas 5 to 10, but the present invention is not limited thereto.

[0013]

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

Specific examples of R ⁶ in the epoxy compound represented by the chemical formula 4 in the present invention include the same groups as those described above as specific examples of R in the amino group-containing polysiloxane, and polyoxyalkylene. Examples thereof include a group, and it is particularly preferable that R ⁶ is a hydrogen atom or a polyoxyethylene group from the viewpoint of improving hydrophilicity. Specific examples of the epoxy compound represented by the chemical formula 4 include compounds represented by the following chemical formulas 11 to 15.

[0015]

[Chemical 11]

[Chemical 12]

[Chemical 13]

[Chemical 14]

[Chemical 15]

Next, the (meth) acrylic acid ester represented by CH ₂ ═CR ⁷ —COO—R ⁸ will be described.
R ⁷ in the formula is a hydrogen atom or a methyl group, it R ⁸ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms are as described above, specific examples of R ⁸ Can be the same groups as R in the amino group-containing polysiloxane represented by Chemical formula 3.

Examples of such (meth) acrylic acid esters include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, 2-hydroxyethyl acrylate, and similar methacrylic acid esters. Can be illustrated.

In the composition of the present invention, the epoxy compound reacts with the amino group-containing polysiloxane as shown in the following chemical formula 16 to open the epoxy group. The hydroxyl group generated by this reaction imparts hydrophilicity to the reaction product.

[Chemical 16]

Further, the (meth) acrylic acid ester reacts with the amino group-containing polysiloxane represented by the chemical formula 3 as shown in the chemical formula 17 below, and has a unique slimy feel and flexibility to the fiber. It is possible to give. In particular, the characteristics of the epoxy compound represented by Chemical Formula 4 when reacted with the epoxy compound and the improvement of yellowing of the treated product are remarkable.

[Chemical 17]

From the viewpoint of reactivity with amino group-containing polysiloxane, R ⁷ is preferably a hydrogen atom.
Further, in order to extremely reduce the yellowing of the treated product, the total amount of the epoxy compound and the (meth) acrylic ester is 50 with respect to all the NH groups in the amino group-containing polysiloxane represented by Chemical formula 3. It is necessary to react at least mol%, and particularly preferably at least 80 mol%.

From the viewpoint of a synergistic effect when the epoxy compound represented by Chemical formula 4 and the above-mentioned (meth) acrylic acid ester are used in combination, the reaction ratio of the epoxy compound or the (meth) acrylic acid ester is However, the molar ratio is 10
/ 90 to 90/10, especially 30
It is preferably / 70 to 70/30. 10/90
If it is less than 90%, the hydrophilicity is lowered, and if it is more than 90/10, the flexibility is lowered.

The reaction method of the amino group-containing polysiloxane with the epoxy compound and the (meth) acrylic acid ester is as follows:
Usually, either the epoxy compound or the (meth) acrylic acid ester may be reacted with the amino group-containing polysiloxane first, and then the other may be reacted, but in either case, at 1 to 10 at 50 to 100 ° C. It is enough to react for a time.

The fiber treatment composition of the present invention is as described above.
The main component is a reaction product of an amino group-containing polysiloxane with an epoxy compound and a (meth) acrylic acid ester.
There is no problem even if other fiber agents such as anti-wrinkle agents, flame retardants, antistatic agents, etc. are added.

In treating various fiber products with the fiber treatment composition of the present invention, the composition is diluted with a suitable solvent and adjusted to a desired concentration, or a surfactant is used to dissolve the composition in water. It may be emulsified and dispersed in the above to form an emulsion, and then diluted with water to adjust to a desired concentration, adhered to the fibers by means of dipping, spraying, roll coating, etc., and dried.

The amount of adhesion in this case is not particularly limited, but usually about 0.1 to 5.0% by weight with respect to the cloth is sufficient. The surfactants used for emulsification include anionic surfactants such as sodium alkylsulfate and sodium alkylbenzenesulfonate; polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers, sorbitan fatty acid esters and the like. Nonionic surfactants; cationic surfactants such as quaternary ammonium salts and the like can be used.

The fiber or fiber product treated with the fiber treatment composition of the present invention is also not particularly limited,
It is effective not only for natural fibers such as cotton, silk, hemp, and wool, but also for synthetic fibers such as polyester, nylon, and acrylic, and fiber products using these. Furthermore, the composition of the present invention can be used as a mold releasing agent, a polish, and the like.

[0027]

As described above in detail, the fiber treatment composition of the present invention can not only impart hydrophilicity to the object to be treated by the hydroxyl group formed by ring opening of the epoxy group but also contain an amino group. A unique slimy feeling and flexibility due to the reaction of the polysiloxane and the (meth) acrylic acid ester can be imparted to the object to be treated, and since it is stable to heat and ultraviolet rays, yellowing due to these is less. That is, the fiber treating agent of the present invention can simultaneously satisfy all the requirements that could not be satisfied at the same time in the past.

[0028]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

Example 1. In a flask having a volume of 1 liter equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube, 390.4 g of amino group-containing polysiloxane represented by the following chemical formula 18 and 15.0 g of ethyl acrylate (total NH group) 50 mol%) and isopropyl alcohol 10
Charge 0.0 g, while introducing nitrogen gas, with stirring,
After reacting at 80 ° C. for 5 hours, disappearance of ethyl acrylate was confirmed by gas chromatography.

[Chemical 18]

Next, 11.1 g (50 mol% based on all NH groups) of the epoxy compound represented by the following chemical formula 19 was added to the flask and reacted under stirring at 60 ° C. for 5 hours. The disappearance of the unreacted epoxy compound in the flask was confirmed by gas chromatography.

[Chemical 19]

After completion of the reaction, the pressure was reduced to 80 mmHg at 80 mm.
When the low boiling point fraction was removed at 2 ° C for 2 hours, the viscosity was 2,400 cp (25 ° C) and the refractive index was 1.4120 (2
5 ° C.) oil was obtained. 300 g of oil obtained
Using 50 g of polyoxyethylene nonyl phenyl ether (HLB = 13.2) as an emulsifier, the mixture was emulsified and dispersed in 650 g of water using a homomixer to prepare an emulsion.

Water was added to the obtained emulsion to dilute it to 1%, and the cotton broad cloth treated with the fluorescent dye was dipped, and then squeezed using a roll under the condition of a squeezing ratio of 100%, and then 100 ° C. For 2 minutes and further at 150 ° C. for 2 minutes. When the flexibility of the obtained treated cloth was evaluated by touch, it was found to have a slimy feel, was extremely flexible, and had a good texture.

Next, about 50 μl of water droplets were placed on the treated cloth with a dropper, and the time taken until the water droplets were absorbed by the cloth was measured to evaluate hydrophilicity. Was 5 seconds, demonstrating good hydrophilicity. The treated cloth was further heated at 200 ° C. for 5 minutes, and then the b value was measured with a colorimetric color difference meter (Model 1001DP manufactured by Nippon Denshoku Industries Co., Ltd.) to evaluate yellowing. The b value was -3.7, and it was proved that the heat treatment did not cause yellowing. It should be noted that the larger the value is on the + side of the b value, the greater the yellowing, and the larger the value on the one side, the less the yellowing is (blue (−) ← b value → (+) yellow).

Comparative Example 1. Oil 30 used in Example 1
The same procedure as in Example 1 was carried out except that 300 g of the amino group-containing polysiloxane used as the starting material in the reaction in Example 1 was used instead of 0 g, and the flexibility was the same as in Example 1. However, the water drop absorption time was 300 seconds or more, the hydrophilicity was poor, and the b value was +2.
It was 1 and it was confirmed that the yellowing was severe. The untreated sample had a water drop absorption time of 0 seconds and ab value of -3.8, which was extremely good in terms of hydrophilicity and yellowing, but was rough to the touch and lacked flexibility. The above results are summarized in Table 1.

[0035]

[Table 1]

Examples 2-3 and Comparative Examples 2-3. A fiber treatment composition was prepared and evaluated in exactly the same manner as in Example 1 except that the ratio of ethyl acrylate to epoxy compound was changed as shown in Table 2. The results are shown in Table 2.

Example 4. Instead of the amino group-containing polysiloxane represented by Chemical formula 18 used in Example 1, the amino group-containing polysiloxane represented by Chemical formula 20 below was used, and ethyl acrylate was changed to 2-ethylhexyl acrylate. A fiber treatment composition was obtained in exactly the same manner as in Example 1 except for the above. The evaluation results are as shown in Table 2.

[Chemical 20]

Example 5. Instead of the amino group-containing polysiloxane used in Example 1, an amino group-containing polysiloxane represented by the following chemical formula 21 was used, and ethyl acrylate was changed to methyl methacrylate to obtain the epoxy compound represented by the chemical formula 19. A fiber treatment composition was obtained in exactly the same manner as in Example 1 except that the epoxy compound represented by the following chemical formula 22 was changed. The evaluation results are as shown in Table 2.

[0039]

[Chemical 21]

[Chemical formula 22]

[0040]

[Table 2]

In the flexibility of Tables 1 and 2, ○
The mark is a very flexible texture with a slimy feel,
The mark Δ means a slightly coarse and slightly coreless feel with almost no slimy feel, and the mark × means a coarse and hard texture without any flexibility. From the results of the above Examples and Comparative Examples, it was demonstrated that by treating various fiber products with the fiber treatment agent of the present invention, each property of flexibility, hydrophilicity and yellowing resistance is imparted in a well-balanced manner. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location D06M 15/263

Claims (1)

[Claims] 1. An amino group-containing polysiloxane represented by the following chemical formula 1, and an epoxy compound represented by the following chemical formula 2,
And is represented by ^{CH = CR 7 -COO-R 8} ( meth) acrylic acid ester (wherein, R ⁷ in the formula is a hydrogen atom or a methyl group, R ⁸ is a substituted or unsubstituted 1 to 20 carbon atoms And a molar ratio of the epoxy compound and the (meth) acrylic acid ester is 10/90 to 90/10, and the total of the epoxy compound and the (meth) acrylic acid ester is A fiber treatment composition containing as a main component a reaction product obtained by reacting the amino group-containing polysiloxane in an amount of 50 mol% or more with respect to all NH groups. [Chemical 1] R in Chemical formula 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and A is a formula —R ¹ — (NR ² —R ³ ) _a—
NHR ⁴ (wherein R ¹ and R ³ are substituted or unsubstituted divalent hydrocarbon groups having 1 to 8 carbon atoms, R ² and R ⁴ are hydrogen atoms, or substituted or unsubstituted having 1 to 20 carbon atoms) A monovalent hydrocarbon group, a is an integer of 0 to 4),
X is a group represented by R, A or -OR ⁵ (wherein R ⁵ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms), m is 10 to 1, 000, n is an integer of 0 to 100, and when n = 0, at least one X is A. [Chemical 2] R ^{6 in} Chemical formula 2 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain an ether bond.