JPS607069B2 - Resin processed fiber structure and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel resin processing for the purpose of imparting abrasion-resistant color development to a fibrous structure.

Polyester fibers are widely used as general clothing materials because of their excellent functionality.

However, when compared with other textile materials for clothing, the low color development of polyester fibers remains the biggest drawback, and many studies have been made to improve this problem. Considering that the main cause of the low color development of polyester fibers is the high refractive index of polyester polymers, covering the fiber surface with a low refractive index compound has traditionally been considered as the most direct solution. Ta.

However, when applying a low refractive index compound, such as a silicone compound or a fluorine compound, by a method such as padding, uniformity comparable to dyeing is required, and various studies have been made. Possible methods for applying these low refractive index compounds include immersion treatment, a steam treatment method using steam heating after padding, and a pad dry method using dry heat heating after padding, which is the most common method for resin processing.
The first two methods are suitable for covering the entire surface of the single fibers constituting Futonomi with a uniform resin film, but the Yunaka treatment method has a low affinity between the fibers and the resin, so the resin utilization efficiency is extremely poor; However, the steam heat treatment method has difficult problems such as dripping inside the treatment equipment and the occurrence of "scratching" due to contact with the seal/part at the entrance of the equipment. On the other hand, it is conventional wisdom that the pad dry method makes it extremely difficult to cover the entire surface of single fibers with resin in a film-like manner due to the migration of resin components that occurs during the drying process. Even if treated with the conventional pad dry method, a high effect of improving color development cannot be obtained.On the other hand, as another method for improving color development, the entire surface of the single fiber can be treated by treatment methods such as alkali reduction or plasma etching. In recent years, attempts have been made to reduce the amount of light reflected on the fiber surface by forming a phase.

An example of the former is JP-A No. 54-120728, and an example of the latter is Hakama Kai No. 52-99400 and JOURNAL.
OF THE SOCIETY OF DYERS A
ND COLOURISTS Vol. There are 88 Pa connections 113 to 117, all of which disclose forming fine irregularities on the fiber surface. However, such fibers have a serious drawback in that the rough surface structure of the entire single fiber surface disappears even with slight friction with a fingernail, resulting in so-called shine. This shine can be improved to a practically acceptable level by covering the entire surface of the single fiber with a low-friction resin such as silicone or fluorine compound to weaken the effect of friction, but in this case as well, the above-mentioned As with the case where the purpose is to improve color development, it is important to uniformly cover the single fiber surface. Therefore, the inventors of the present invention have conducted various studies on methods for covering the surface of single fibers with a uniform film that can be implemented industrially, and as a result they have arrived at the present invention. That is, the present invention has the following configuration. '1} It is composed of roughened polyester fibers, and the fiber surface is coated with a thin film of a low refractive index polymer having a refractive index of 1.5 or less and containing inert inorganic fine particles. Resin processed fiber structure.

(2) A resin-processed fibrous structure according to claim 1, wherein the inert inorganic fine particles have a refractive index of 1.8 or less.

2. The resin-processed fibrous structure according to claim 1, wherein the adhesive polymer is a polymer mainly composed of a silicone-based polymer and/or a fluorine-based polymer.

{4; The resin-treated fiber structure according to claim 1, wherein the fiber structure is darkly colored.

[5] After adding inert inorganic fine particles to a fiber structure composed of a phase-faced polyester-based woven material, a polymer having a low refractive index of 1.5 or less, a prepolymer or its monomer is added. 1. A method for producing a resin-treated fiber structure, which comprises applying one or more of - and then heating.

'6} A fiber structure composed of assembled polyester fibers is coated with a polymer having a low refractive index of 1.5 or less, a prepolymer, or one or more of these monomers and inert inorganic fine particles. A method for producing a resin-treated fiber structure, which comprises applying a mixture and then heating it.

{7' The method for producing a resin-processed fibrous structure according to claim 5 or 6, wherein the inert inorganic fine particles have a refractive index of 1.8 or less. [81] The method for producing a resin-treated fiber structure according to claim 5 or 6, wherein the heating is a dry heat treatment.

That is, the present invention relates to a fiber structure in which the entire surface of a single fiber is coated with a resin layer containing a mixture of fine inert inorganic particles and a low refractive index polymer having a refractive index of 1.5 or less.

Here, the fine inert inorganic particles are used for the purpose of preventing migration of the resin component in a fluid state when forming a resin film on the entire surface of the single binding.

In other words, when fine inert inorganic particles are present on the entire surface of a single fiber, the resin component in a fluid state is fixed around the inert inorganic particles by surface tension, as in the case where there are no inert inorganic particles. A uniform resin film can be formed on the surface of single fibers without causing migration of resin-forming components. For this reason, the inert inorganic fine particles are required to have an appropriate particle size, preferably in the range of 0.01 micron or more.If the particle size of the inert inorganic fine particles is smaller than this range, they will flow together with the resin forming components. However, if the particle size is too large, the surface area of the particles will become small and the migration prevention effect will not be obtained, and the adhering particles will fall off and the texture of the product will change. , harmful effects such as pastelization of colors occur due to the diffused reflection of light caused by the attached particles.The particle diameter is preferably 1 French or less, particularly preferably 0.5 or less.Also, the diffused reflection of light caused by the attached particles also depends on the refractive index of the particles, with high refractive index (n:
2.5) is not suitable for the purpose in this case and has a refractive index of 1.8.
The following are preferred.

Examples of inert inorganic fine particles having a refractive index in this range include silicon oxide (refractive index n=1.47) and aluminum oxide (
n=1.76), kaolinite (n=1.56), talc (n=1.57-1.6), calcium carbonate (n=1
．． 66), calcium silicate (n=1.72), and magnesium oxide (n=1.73). In addition,
The particle size of these inert inorganic fine particles is determined by taking a photograph of the fine particles magnified 10 times with an electron microscope, measuring the longest diameter of each particle from the obtained image, and determining the value as the average of the ION solids. means. In addition, the particle size of the particles attached to the fiber surface was similarly determined from an electron micrograph of the fiber surface magnified 100,000 times.
The longest diameter of each particle was measured and taken as the average of 10 particles. In addition, the polymer used in combination with the inert inorganic fine particles is
Firstly, it is desirable that it is effective for improving the friction resistance properties of roughened polyester fibers, and secondly,
It is necessary that the improved coloring property is not inhibited, but rather that it is improved. Thirdly, it is preferable that the material is durable against washing or dry cleaning when used as a product. In addition to low friction and low refractive index, the properties of polymers that satisfy these purposes include crosslinking resin compounds, and polymers, prepolymers, or monomers of these properties alone or Mixtures can be used.

In order not to inhibit the color development of the fiber substrate, the refractive index of the polymer compound coating the fiber surface must be 1.5 or less. For example, a block or random copolymer of propylene oxide and ethylene oxide From ether diol and hexamethylene diisocyanate or xylene diisocyanate. Urethane polymer.

Alkyl or phenol ethers of polyoxyalkylene such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, and polyoxypropylene alkyl ether. Fluorine-containing compounds such as tetrafluoroethylene-hexafluoropropylene copolymer, polybentadecafluorooctyl acrylate, polytetrafluoroethylene, polytrifluoroethyl acrylate, polytrifluorochloroethylene, and polytrifluoroethyl methacrylate. Vinyl ether polymers such as polyvinyl isobutyl ether and polyvinyl ethyl ether. Acrylic ester polymers such as polybutyl acrylate, polyethyl acrylate, and polymethyl acrylate. Methacrylic acid ester polymers such as polytertiary butyl methacrylate, polyisobutyl methacrylate, poly n-propyl methacrylate, polyethyl methacrylate, and polymethyl methacrylate. Vinyl polymers such as polyvinyl acetate, polyvinyl formate, polyvinyl acetal, and polyvinyl alcohol. Examples include organic silicon compounds such as polydimethylsilane, polydimethylsiloxane, amine-modified dimethylpolysiloxane, and epoxy-modified dimethylpolysiloxane, and their polymers or monomers, reaction intermediates, etc. can be used as appropriate. On the other hand, in order to improve the frictional properties of fibers, it is necessary to make the resin-treated fiber surface low in friction, and for this purpose, among the low refractive index polymers, organic silicon compounds and fluorine-containing compounds, which can provide low friction, are used. It is desirable to use them alone or in combination with other polymers. In addition, in order to improve the washing resistance and dry cleaning resistance of the polymer film, reactive groups may be introduced into the polymer and crosslinked, or the above crosslinking-reactive prepolymers or monomers may be appropriately mixed and used. Examples of crosslinking-reactive prepolymers or monomers include silane compounds such as trimethylolvinylsilane and trimethylolmethylsilane. Examples include water-soluble urethane prepolymers in which free isocyanate groups are blocked with bisulfite. Here, in the method of the present invention, fine inert inorganic particles and polymers, prepolymers, or monomers thereof or a plurality thereof are applied simultaneously, or inert inorganic particles are applied alone in advance by a conventional method. It's okay to stay.

That is, the inert inorganic fine particles can be deposited on the fiber surface by applying a colloidal dispersion thereof to the fiber by padding, spraying, imprinting, etc., and then drying it. Alternatively, after applying the emulsion to the fibers in the same manner as above, the resinization reaction is promoted by methods such as dry heat, steaming, heat treatment with superheated steam, or leaving the fibers at a relatively low temperature for a long period of time to form a resin coating on the fiber surface. The reason why the inert inorganic fine particles are added before or at the same time as the resin-forming component is that, as mentioned earlier, the inert inorganic fine particles are used as cores to form the resin-forming component. This is to prevent migration on the fiber surface.The effects of the present invention are most preferably exhibited when applied to polyester fibers, which have the lowest color development among textile materials for clothing. Yes, especially Tokusho 54-154681
, or when applied to polyester fibers or structures manufactured in accordance with Japanese Patent Application No. 54-3922, etc., in which color development has been improved by forming fine irregularities in the order of the wavelength of light on the fiber surface, the present invention can be applied. The effects are synergistically exhibited, making it possible to provide a new clothing material with excellent color development and improved abrasion resistance.

The present invention will be further explained below based on Examples.

Example 1 The particle size dispersed in ethylene glycol during polymerization was 2
A polyester polymer containing 1% by weight of French dirica sol was spun and drawn, and 75 denier 36 filament long polyester fibers were strongly twisted (wrap number 250 m/M).
) A georgette fabric was created using the yarn obtained.

This is done according to the usual method,
After heating at 80° C. and 3% sand, the specimens were immersed in an aqueous solution containing 9% and 0% caustic soda, and subjected to an alkali weight reduction process of 25% by weight based on the weight before treatment. D this
ianixBlackRN-SE (Disperse dye made by Mitsubishi Kasei ■) 130o in Liang Yuchu with Yu ratio 1:30 containing 10% oM
After dyeing with o for 60 minutes, reduction cleaning was carried out according to a conventional method, followed by washing with water and drying. This black dyed material was mixed with inert inorganic fine particles having the following various particle types and particle sizes at 1.5% by weight in an aqueous solution of polyvinyl acetate (refractive index 1.48).
After immersing the fabric in a treatment liquid dispersed by weight%, applying a treatment liquid of 90% of the weight of the fabric using a mangle, drying at a temperature of 130qo, and setting it at 160q0 for 3 seconds. I looked into it. The black color development was compared using the L value measured with a digital side various difference calculator (manufactured by Suga Test Instruments ■). Here, the L value represents the visual density of a color, and the smaller the L value, the darker the color. As a result, it was found that those to which only polyvinyl acetate was applied without adding particles, those to which titanium oxide with a high refractive index was added and processed with resin, and those whose particle diameters were outside the range of the present invention had color development ( The L value) did not improve compared to the dyed product, or it became defective.

Example 2 The same polyester black beam georgette fabric as in Example 1 was made of NK Guard FP280 (manufactured by NICCA CHEMICAL, fluorine-based water repellent, refractive index 1.38, active ingredient 20%) and Toray Silicone SM8702 (manufactured by Toray Industries, Ltd.). Made of silicone, amine-modified dimethylpolysiloxane, refractive index 1.4 (active ingredient 40%),
Toray Silicon SH6070 (manufactured by Toray Silicon ■, silane monomer, refractive index 1.48 active ingredient 100%), KK
-2000 (manufactured by Ichisha Yushi Kogyo ■, polyvinyl acetate resin, refractive index 1.49, active ingredient 40%), Sumitekus Resin M-3 (manufactured by Sumitomo Chemical, melamine finishing agent, refractive index 1.6, effective Using 5 types of processing agents (component: 80%),
When used alone or in combination, the total concentration is 0 in terms of pure content.
．． Particle size 0.1 is added to the treatment solution adjusted to give 5 g/
Soaked in a treatment solution containing 1% by weight of Buddha's silicon oxide,
After applying a treatment liquid of 90% of the weight of the fabric with a mangle,
The same heat treatment as in Example 1 was performed, and the L value abrasion resistance of the fabric was measured.

The abrasion resistance of textiles is determined using a JISL0849 (friction tester type n), and after rubbing the same type of fabric 100 times, the degree of shine of the test fabric attached to the friction element is determined by the color change and fading test. Grades were determined using gray scale.

The larger the number, the better the abrasion resistance. As a result, color development is improved only when the refractive index is 1.5 or less, and color development and abrasion resistance can be improved by using or in combination with low refractive and low friction silicone and fluorine treatment agents. I realized that I could improve myself at the same time.

Example 3 Using a 75-denier 36-filament semi-dull yarn (“Tetron” manufactured by Toray Industries, Inc.), a highly flammable decine was subjected to graining and alkali weight loss processing (weight loss rate 23%) according to a conventional method. Similar to 1, it was stained black.

This is mixed with silicon oxide fine powder with a particle size of 0.05 mm and KK-20.
When processing with 00, use the following three methods of giving L
The value was measured and the effect of improving color development was investigated.

■ A colloidal dispersion containing 1.5% by weight of silicon oxide was applied to the fibers and dried to deposit 0.3% of silicon oxide based on the weight of the fibers, then padded with an aqueous solution containing KK-200020g/g and heated to 13000g. Dry. 'B} After padding with an aqueous solution of KK-2000 containing 1.5% by weight of silicon oxide, it was dried at 130°C.

0 Silicon oxide and KK-2000 were applied in the completely opposite order.

The L value of the fabrics obtained by these three methods was 13.
5, [B} was 13.6, which was improved compared to 14.3 of the dyed product, but [q was 14.5, which was actually worse than the dyed product.

Comparative Example 1 The same fabric as in Example 1 was treated in the same manner, except that the alkali weight loss processing step was omitted.

The black color development of this georgette fabric was as follows.
As is clear from the table, due to the alkali loss, that is, the surface is not roughened, there is a difference of about 1 to 2 from the L value of Example 1, and it is not possible to show outstanding black color development. It turns out that there isn't.

Comparative Example 2* The same fabric as in Example 2 was subjected to the same treatment except that the alkali weight loss processing step was omitted.

The black color development and abrasion resistance of this Georgette fabric were measured. The results are shown below. From the table, it can be seen that a product that satisfies both abrasion resistance and color development cannot be obtained unless Arca IJ is reduced, that is, the surface is roughened.

Example 4 The black-dyed, highly twisted deshine used in Example 3 was subjected to low-temperature plasma etching treatment under the following conditions to make the fiber surface grainy and improve color development.

(Low-temperature plasma etching conditions) Gas: Oxygen Flow rate: 5 ratio c/min Pressure: 0.6 ron Applied voltage: Hina V Processing temperature: 10 k/min Observation of the fiber surface subjected to low-temperature plasma etching using a phase contrast electron microscope As a result, the surface has a period of 0.2
Fine irregularities of about 0.8 mm were observed, confirming that the surface was roughened.

Furthermore, when the L value of the dyed product was measured before and after the low-temperature plasma etching treatment, it was found that it had significantly improved from 14.3 to 11.9. This plasma-etched fabric was treated with the same resin as in Example 2, and the friction resistance performance of six types of resin coatings was evaluated.

The results are shown in the table below. As is clear from the table, only those treated with a treatment agent containing inert inorganic fine particles and a low refractive polymer satisfied both the properties of high color development and abrasion resistance.

Claims (1)

[Scope of Claims] 1. It is composed of roughened polyester fibers, and the fiber surface is coated with a thin film of a low refractive index polymer having a refractive index of 1.5 or less and containing inert inorganic fine particles. A resin-processed fiber structure characterized by: 2. The resin-processed fibrous structure according to claim 1, wherein the inert inorganic fine particles have a refractive index of 1.8 or less. 3. The resin-processed fibrous structure according to claim 1, wherein the polymer is a polymer mainly composed of silicone-based and/or fluorine-based polymers. 4. The resin-treated fiber structure according to claim 1, wherein the fiber structure is darkly colored. 5 After adding inert inorganic fine particles to a fiber structure composed of roughened polyester fibers, the refractive index is set to 1.
A method for producing a resin-treated fiber structure, which comprises applying a polymer, a prepolymer, or one or more monomers thereof having a low refractive index of 5 or less, and then heating. 6 A fiber structure composed of roughened polyester fibers is coated with a polymer having a low refractive index of 1.5 or less, a prepolymer, or a mixture of one or more of these monomers and inert inorganic fine particles. A method for producing a resin-treated fiber structure, the method comprising heating the resin-treated fiber structure after applying the resin. 7. The method for producing a resin-processed fibrous structure according to claim 5 or 6, wherein the inert inorganic fine particles have a refractive index of 1.8 or less. 8. The method for producing a resin-treated fiber structure according to claim 5 or 6, wherein the heating is a dry heat treatment.