JP2885389B2 - Fiber treatment composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a fiber treatment composition,
In particular, the present invention relates to a fiber treatment composition capable of imparting excellent flexibility and hydrophilicity 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 and amino group-containing polysiloxane have been widely used as treatment agents for imparting flexibility and smoothness to various fiber products. Amino group-containing polysiloxane is most often used because it can provide particularly good flexibility.

However, when an amino group-containing polysiloxane is used, the amino group is oxidized by heat, ultraviolet rays, or the like, so that there is a serious disadvantage that the color tone of the processed product changes. In order to improve the above drawbacks, for example, an amino group-containing polysiloxane, an organic acid anhydride or chloride (JP-A-57-101076), a higher fatty acid (JP-A-1-306683), and a carbonate (JP-A-2-10683) 47371) and the like.
It has been proposed to modify amino groups.

[0004] However, in these cases, although the discoloration is improved 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 that properties inherent to amino group-containing polysiloxane tend to be impaired, such as imparting properties. Therefore, it is possible to suppress a decrease in flexibility by reacting the amino group-containing polysiloxane with the (meth) acrylate compound in a specific range (Japanese Patent Laid-Open No. 4-11).
9174), when the reaction amount is increased for the purpose of improving the yellowing, there is a disadvantage that the flexibility is reduced.

[0005] Further, in general, a treated product with an amino group-containing polysiloxane becomes water repellent, so that even fibers that are originally hydrophilic exhibit hydrophobicity after being treated, and, for example, have almost no sweat-absorbing action during perspiration. There was also the disadvantage of being lost. This point can be improved, for example, by including an amino group and a polyoxyalkylene group in the same polysiloxane molecule (Japanese Patent Application Laid-Open No. 57-17 / 1982).
1768) has the disadvantage that the inclusion of a polyoxyalkylene group greatly reduces flexibility and smoothness.

As a method of imparting hydrophilicity together with the improvement of the yellowing described above, there is a method of reacting an amino group-containing polysiloxane with a monoepoxy compound.
In this case, as in the case of the various methods described above, there is a disadvantage that the flexibility of the treated fiber is reduced.

[0007]

As described above, a fiber treatment composition which has good flexibility and hydrophilicity and has very little yellowing of the treated fiber has not yet been known. Then, the present inventors have given the fibers softness and hydrophilicity and studied the fiber treating agent with extremely little yellowing of the treated fibers. As a result, the amino group-containing polysiloxane, the epoxy compound and the ( The present inventors have found that a fiber treatment agent containing a reaction product with a (meth) acrylic ester as a main component is extremely excellent, and arrived at the present invention. Accordingly, an object of the present invention is to provide a fiber treating agent that can impart flexibility and hydrophilicity to fibers and that is less likely to cause yellowing of the fibers after treatment with heat, ultraviolet light, or the like.

[0008]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
An amino group-containing polysiloxane represented by the following formula 3,
An epoxy compound represented by the following formula 4 and CH =
(Meth) acrylic acid ester represented by CR ⁷ —COO—R ⁸ (where R ⁷ 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 to the (meth) acrylate ester is from 10/90 to 90 /
And a reaction product obtained by reacting the epoxy compound and the (meth) acrylate so that the total amount of the epoxy group and the (meth) acrylate is 50 mol% or more based on all NH groups of the amino group-containing polysiloxane. Achieved by the fiber treatment composition as a component.

[0009]

Embedded image R in Chemical Formula ³ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and A is a group represented by the formula -R ^1- (NR ² -R ³ ) _a-
NHR ⁴ (wherein R ¹ and R ³ are substituted or unsubstituted C 1-8 substituted or unsubstituted hydrocarbon groups, R ² and R ⁴ are hydrogen atoms, or substituted or unsubstituted C 1-20 carbon atoms) A is an integer of 0 to 4), a group represented by
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); 000 and n is an integer of 0 to 100. When n = 0, at least one of X is A.

[0010]

Embedded image 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 an arbitrary organic group. Can be mentioned.

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. As R ² and R ⁴ ,
Examples thereof include a hydrogen atom and the same groups as those described above for R. 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]

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In the present invention, specific examples of R ⁶ in the epoxy compound represented by Chemical Formula 4 include the same groups as those described above as specific examples of R in the amino group-containing polysiloxane, and polyoxyalkylene. R ⁶ is preferably a hydrogen atom or a polyoxyethylene group from the viewpoint of improving hydrophilicity. Specific examples of the epoxy compound represented by Chemical Formula 4 include, for example, compounds represented by Chemical Formulas 11 to 15.

[0015]

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Next, the (meth) acrylate represented by CH ₂ ＣＲCR 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 Examples include the same groups as R in the amino group-containing polysiloxane represented by Chemical Formula 3.

Examples of such (meth) acrylates include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, 2-hydroxyethyl acrylate, and the like, and similar methacrylates. Can be exemplified.

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

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The (meth) acrylic acid ester reacts with the amino group-containing polysiloxane represented by the chemical formula (3) as shown in the following chemical formula (3) to give the fiber a unique slimy feeling and flexibility. Can be granted. In particular, when the epoxy compound is reacted with the epoxy compound represented by Chemical formula 4, the properties thereof and the improvement in yellowing of the treated product are remarkable.

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From the viewpoint of the reactivity with the amino group-containing polysiloxane, R ⁷ is preferably a hydrogen atom.
In order to minimize the yellowing of the treated product, the epoxy compound and the (meth) acrylic acid ester are added in a total amount of 50 to the total NH groups in the amino group-containing polysiloxane represented by the chemical formula (3). It is necessary to react at least mol%, and it is particularly preferable to react at least 80 mol%.

From the viewpoint of a synergistic effect when the epoxy compound represented by the chemical formula (4) and the above (meth) acrylate are used in combination, the reaction ratio between the epoxy compound and the (meth) acrylate is considered. Has a molar ratio of 10
/ 90 to 90/10, especially 30
/ 70 to 70/30. 10/90
If it is smaller, the hydrophilicity decreases, and if it is larger than 90/10, the flexibility decreases.

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

The fiber treatment composition of the present invention comprises, as described above,
It is mainly composed of a reaction product of an amino group-containing polysiloxane with an epoxy compound and a (meth) acrylic acid ester.
It does not matter what other fibrous agents, for example, anti-wrinkle agents, flame retardants and antistatic agents are added.

In treating various fiber products with the fiber treatment composition of the present invention, the composition is diluted with a suitable solvent to adjust the concentration to a desired level, or water is treated with a surfactant. Then, after emulsifying and dispersing into an emulsion form, it is diluted with water, adjusted to a desired concentration, adhered to the fiber by means of dipping, spraying, roll coating or the like, 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. In addition, as the surfactant used at the time of emulsification, anionic surfactants such as sodium alkyl sulfate and sodium alkylbenzene sulfonate; polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, sorbitan fatty acid ester, etc. Nonionic surfactants; cationic surfactants such as quaternary ammonium salts and the like can be used.

The fibers or fiber products treated with the fiber treatment composition of the present invention are 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 textile products using these. Further, the composition of the present invention can be used as a mold release agent or a polishing agent for a mold.

[0027]

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

[0028]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

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

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

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After the completion of the reaction, the pressure was reduced to 80 under a reduced pressure of 10 mmHg.
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.). 300 g of obtained oil
Was emulsified and dispersed in 650 g of water using a homomixer using 50 g of polyoxyethylene nonylphenyl ether (HLB = 13.2) as an emulsifier to prepare an emulsion.

Water was added to the obtained emulsion to dilute it to 1%, and a cotton broad cloth treated with a fluorescent dye was immersed, squeezed using a roll at a squeezing rate of 100%, and then squeezed at 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 that the treated cloth had a slimy feeling, was extremely flexible, and had a good texture.

Next, a water drop of about 50 μl was placed on the treated cloth with a dropper, and the time required for the water drop to be absorbed by the cloth was measured to evaluate the hydrophilicity. Was 5 seconds, demonstrating good hydrophilicity. After the treated cloth was further heated at 200 ° C. for 5 minutes, the b value was measured by a colorimetric colorimeter (Model 1001DP, manufactured by Nippon Denshoku Industries Co., Ltd.) to evaluate yellowing. The b value was −3.7, which proved that the yellowing was not caused by the heat treatment. It should be noted that the yellowing is greater as the numerical value is larger on the positive side of the b value, and the yellowing is smaller as the numerical value is larger on one side (blue (−) ← b value → (+) yellow).

Comparative Example 1 Oil 30 used in Example 1
The procedure was the same as in Example 1 except that 300 g of the amino group-containing polysiloxane used as the starting material in Example 1 was used instead of 0 g. However, the water droplet absorption time was 300 seconds or more, which was poor in hydrophilicity, and the b value was +2.
It was confirmed that the yellowing was severe. The untreated product had a water droplet absorption time of 0 seconds and a b value of -3.8, and was extremely good in hydrophilicity and yellowing, but had a rough 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 and epoxy compound was changed as shown in Table 2. The results are as shown in Table 2.

Embodiment 4 FIG. In place of the amino group-containing polysiloxane represented by the formula (18) used in Example 1, an amino group-containing polysiloxane represented by the following formula (20) was used, and ethyl acrylate was changed to 2-ethylhexyl acrylate. Except for the above, a fiber treatment composition was obtained in exactly the same manner as in Example 1. The evaluation results are as shown in Table 2.

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

[0039]

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[0040]

[Table 2]

Incidentally, in the flexibility shown in Tables 1 and 2,
The seal has a slimy, extremely flexible texture,
The symbol “Δ” means a texture with almost no slimy feeling, slightly coarse and firm with a core remaining, and the symbol “X” means a texture with coarse hardness and no flexibility at all. 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 was imparted in a well-balanced manner. .

Continuation of front page (56) References JP-A-63-75184 (JP, A) JP-A-2-154076 (JP, A) JP-A-2-210073 (JP, A) (58) Fields investigated (Int) .Cl. ⁶ , DB name) D06M 13/00-15/72

Claims (1)

(57) [Claims] An amino group-containing polysiloxane represented by the following formula (1) and an epoxy compound represented by the following formula (2):
And (meth) acrylic acid ester represented by CHＣＨCR ⁷ —COO—R ⁸ (where R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is substituted or unsubstituted having 1 to 20 carbon atoms) And the molar ratio of the epoxy compound to the (meth) acrylate is 10/90 to 90/10, and the total of the epoxy compound and the (meth) acrylate is A fiber treatment composition comprising, as a main component, a reaction product obtained by reacting the amino group-containing polysiloxane so that the amount thereof is 50 mol% or more with respect to all NH groups contained in the amino group-containing polysiloxane. Embedded image R in Chemical Formula ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and A is a group represented by the formula -R ^1- (NR ² -R ³ ) _a-
NHR ⁴ (wherein R ¹ and R ³ are a substituted or unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, R ² and R ⁴ are a hydrogen atom, or substituted or unsubstituted having 1 to 20 carbon atoms) A is an integer of 0 to 4), a group represented by
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); 000, n is an integer of 0 to 100, and at least one of X is A when n = 0. Embedded image 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.