JPS59216977A - Adhesion of fine particle good in durability - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for adhering fine particles to fiber surfaces with good durability, and its purpose is to impart excellent functions and performance to fibers or products thereof.

Although various synthetic and natural fibers have been widely used in the past, they have many drawbacks and there is a strong need for improvements to better fibers.

One method is to mix fine particles into a polymer matrix, but this may cause aggregation of particles in the polymer, increase in the viscosity of the polymer melt or solution, decomposition and deterioration of the fine particles themselves and the polymer during the manufacturing process, and formation of molded fibers. There are drawbacks such as decreased physical properties. Furthermore, this method is difficult to apply to natural fibers.

Therefore, attempts have been made to attach fine particles to the fiber surface, but the attached particles tend to fall off during subsequent processes or when the textile product is used, or the quality of the textile product deteriorates due to the adhesion treatment, or the adhesion treatment process There were drawbacks such as high cost.

For example, with the method of applying fine particles to the fiber surface together with an adhesive resin, it may be difficult to uniformly disperse the fine particles into the adhesive resin or its composition, or the adhesiveness between the resin and the fibers may be poor and the particles may peel off together with the resin. It may fall off, or the original function and texture of the fiber base material may change or deteriorate due to difficulty in controlling the coating thickness.
Disadvantages include that the attachment process is complicated and expensive.

In order to solve these difficulties, the present inventors, as a result of a little grinding, dispersed a cloth-like material in a sol form with an average particle diameter of 100 millimicrons (mμ) or less when attaching fine particles to the fiber surface. The fibers are introduced into a dyeing bath, a washing bath, or a pad bath to which fine particles have been added, and 0.0.
001 to 10% by weight of fine particles are adsorbed or attached,
It has been found that by subsequently drying and then irradiating the particles with low-temperature plasma, the durability of the adsorbed or adhered fine particles is significantly improved and the various problems mentioned above can be solved.

Although it is known that the fiber surface is modified by low-temperature plasma irradiation, it is not known at all that the adhesion durability of adhering fine particles is significantly improved as in the present invention. The reason for this great improvement in durability is not clear, but because the particle size of the fine particles is small, the particles adsorbed or attached to the fibers in the bath or during the subsequent heating process such as drying. Fine particles may penetrate to some extent into the fiber matrix, a cross-linked layer may be formed on the surface by plasma irradiation, the particles may be decomposed, and the volatilized carbon and rimer components may repolymerize on the fiber surface to form a coating layer. Although it is conceivable that some kind of bond or interaction may occur between the polymer substrate and the polymer substrate, these are merely speculations after the fact, and the present invention is not limited by these reasons.

Fibers subject to non-invention include polyester, polyamide,
These include synthetic fibers such as acrylic and polyurethane fibers, natural fibers such as wool, cotton, linen, and silk, semi-synthetic fibers such as acetate, and Nyu fibers such as rayon. The synthetic fibers may be copolymerized polymers, polymer blends, those containing modifiers, pigments, etc., or composite spun fibers.

In the present invention, the fiber aggregate to which the fine particles are attached is in the form of a cloth such as a woven fabric, a knitted fabric, or a nonwoven fabric.

It is most reasonable to carry out the process in the form of a cloth in terms of handling and applicability to the current process.

In the present invention, the step of adding fine particles is carried out in a dyeing bath, washing bath or pad bath. If done in these baths,
It is advantageous in that there is no need to add another step, and the equipment in the current process can be used as is.

The fine particles in the present invention have an average particle size I Q Q ma
t or less, more preferably 70' mμ or less. If it is more than 100 rnμ, it is difficult to disperse it in sol form, the adhesion to the fiber surface is poor, and even if it adheres once, the durability is not good or it has a negative effect on the quality of the textile product, so it is not recommended. Not chewy.

The fine particles are added to the bath in the form of a sol-like dispersion. Powder powder or an insufficiently dispersed state is not preferable because adhesion, durability after adhesion, quality of textile products, etc. are poor. The fine particle sol may be one that is dispersed in the form of a sol during the process of producing fine particles, or it may be one that is once obtained as a powder and then converted into a sol by an appropriate means. Needless to say, the dispersion state must be good even in the above bath, and it is necessary to distribute the particles in the bath, coexisting substances, etc. to prevent agglomeration of the fine particles.

Although there are no particular restrictions on the type of fine particles used in the present invention, it is necessary to select appropriate particles depending on the purpose of improving cloth or textile products. Examples of fine particles that can be used include:
Inorganic colloids such as silica, alumina, titanium, antimony oxide, calcium carbonate, titanium phosphate, aluminum hydroxide, barium titanate, magnetic iron powder, lithium silicate, sodium hectorite, Co-Fe alloy, Fe
-Ni alloy, Ni, Ag, AI, Cu,
Examples include ultrafine metal powder such as Au, carbon black, polytetrafluoroethylene dispersion, and emulsion polymerized fine particle polymer latex.

Further, the adsorption or adhesion of the fine particles of the present invention is from 0.001 to 10% by weight, preferably 0.0% by weight, based on the weight of the fiber.
0.03 to 8% by weight, more preferably 0.01 to 6% by weight. o, ooi weight There is no improvement effect due to the adhesion of fine particles above and below the weight, and the id durability is improved when the weight exceeds 10 weight.
Textile products; 1 (etc.) deteriorate, so it is not preferable.

Drying is required before the low-temperature plasma irradiation of the present invention, and if drying is insufficient, durability may decrease, and solvents such as water may have an adverse effect during plasma treatment.

The plasma treatment conditions in the present invention depend on the type of target fiber base material, the type and amount of fine particles, and the content and level of textile product improvement, such as the type and shape of the equipment, the type of gas,
It is necessary to select the flow, vacuum degree, output, processing time, etc.

Complex reactions such as crosslinking, etching, and generation of active sites for polymerization occur during low-temperature plasma treatment, and the ease with which each reaction occurs depends on the type of plasma-generating gas, the type of fiber base material,
Affected by processing conditions, etc.

Although the cause of the improvement in the durability of adhered fine particles is not clear, it is thought that these reactions interact in a complex manner to exert a comprehensive effect.

In the present invention, low-temperature plasma generating gases include argon, helium, neon, nitrogen, hydrogen, carbon oxide, oxygen,
Common materials such as air, ammonia or a mixture thereof are used.

Furthermore, although the plasma treatment effect of the present invention generally extends over the entire area of the fabric, it is not necessarily necessary to extend over all of the surface layer, interior layer, and back layer. In some cases, it may be better to treat only the surface layer, or to treat only a specific portion of the surface layer, so plasma treatment conditions are selected depending on the purpose.

Furthermore, in order to further enhance the effect of the present invention, when attaching the fine particles, a substance capable of radical polymerization can be made to coexist, and then low-temperature plasma irradiation can be performed. A radically polymerizable substance is dispersed or dissolved in a deposition bath, and adsorbed or attached to the sub-material together with fine particles.

Substances that can be radically polymerized include not only those conventionally used for radical polymerization, such as those having carbon-carbon double bonds, but also those that can be polymerized by plasma irradiation. However, so-called unsaturated/Fa compounds are the most common because of their high radical polymerization efficiency. Examples of substances that can be used in a chemical dish include acrylic acid, methacrylic acid,
and 7i Shira no ester, vinyl trienal silane,
Styrene, vinylpyridine, acrylonitrile, vinyl acetate, triethoxy 7 di/etc.

In addition, it is possible to attach fine particles and irradiate them with low-temperature plasma, and then conduct radical polymerization in a gaseous or active state. can. The compound is vaporized under appropriate conditions, and 7 is dissolved as a gas or as a bath liquid in a single liquid or solvent.
Contact δ7 with the 411-like object after plasma irradiation.

Radin J Le Wataru-8'Mueno72 klL mer is:
Generally, carbon-carbon double bonds are used, and I'ilt C is used as a radical with a chain 4A structure. Examples of radically polymerizable monomers include acrylic acid, methacrylic acid, esters thereof, vinylsilane compounds, fluorine compounds such as hexafluoroethylene, vinylpyridine, styrene, acrylonitrile, and acrylamide.

A particularly noteworthy feature of the present invention is that by selecting the type of fine particles, etc., it can be adapted to various purposes of improving the quality and functionality of fibers or products thereof. For example, it can be applied for purposes such as improving color tone, gloss, texture, etc., and imparting durable and strong properties such as antistatic properties, conductivity, magnetism, flame retardance, water contact, and oil resistance. It is a point.

Next, the present invention will be explained with reference to examples, but the present invention is not limited to the following examples.

In the examples, the durability of the adhered fine particles was determined by measuring the content of fine particle components before and after the durability test, and expressed as the residual mass after the test.

Friction durability is measured by rubbing cloth against each other 100 times under a load of 3002, and washing durability is measured at 40°C with 12/l of neutral detergent.
The laundry was washed for 100 minutes using a washing machine using a washing machine.

Example 1 Water-based colloidal silica having an average particle size of 15 mμ was added to a dyeing bath for a Kasitos fabric made of ordinary polyethylene terephthalate, and 1.0 weight percent of the colloidal silica was deposited on the fabric. After drying this silica-adhered fabric, an internal electrode type plasma device (
A mixed gas of 90 mol of argon and 10 mol of oxygen was used as the introduced gas in an electrode area of 50 cr/l.
Low-temperature plasma irradiation was performed for 2 minutes at Torr and output cuff of 0 watts. The sample after plasma irradiation had good friction durability of 96% and washing durability of 98%.

Comparative Example 1 A sample treated in the same manner as in Example 1 except that plasma irradiation was not performed had poor friction durability of 33 inches and poor washing durability of 42%.

Example 2 An average particle size of 7 was added to the soaping bath after dyeing polyester fabric.
mμ of aqueous colloidal silica is added to the fabric to
．． After drying this silica-adhered fabric,
Plasma irradiation was performed at 0.4 Torr for 2 minutes using air as the introduced gas.The friction durability of this sample was 96.
The tear and washing durability was 97cm.

Comparative Example 2 A sample treated in the same manner as in Example 2 except that plasma irradiation was not performed had a friction durability of 30% and a washing durability certificate of 4.
It was 3%.

Example 3 An average particle size of 30 m was added to the pad bath of polyester fabric after dyeing.
A sol-like dispersion of titanium oxide of μ was added and deposited at a weight of 1.0. After drying this titanium oxide-attached fabric, it was subjected to plasma irradiation at 0.5 Torr for 2 minutes using nitrogen as an introduced gas. The friction durability of this sample is 9
Washing durability was 97%.

Comparative Example 3 A sample treated in the same manner as in Example 3 except that plasma irradiation was not performed had a friction durability of 37% and a washing durability of 45%.
I ran into a problem with the article.

Example 4 Silica sol with an average particle size of 15 mμ and 2-dimethylaminoether methacrylate were added to a dye bath for polyester fabric, and 1.0% by weight of silica and 3.0% by weight of 2-dimethylamine ethyl methacrylate were deposited. After drying this adhered fabric, plasma irradiation was performed in the same manner as in Example 1. The friction durability of this sample was 99%, and the washing durability was also 99%.

Example 5 After performing the fine particle adhesion treatment and plasma irradiation treatment in the same manner as in Example 1, the sample was exposed to methyl methacrylate gas.The friction 2 and washing durability of this sample were both 1.
It was 00%.

Example 6 An alumina sol having an average particle diameter of 30 mμ was added to a saw pink bath of a dyed polyester fabric, and was deposited at a weight of 1.0. After drying this alumina-adhered fabric, plasma irradiation was performed at 0.5'rorr for 2 minutes using air as the introduced gas.The friction durability of this sample was 96 inches, the washing durability was 98%, and it was 7'C.

Comparative Example 4 A sample treated in the same manner as in Example 6 except that plasma irradiation was not performed had a friction durability of 34 inches and a washing durability of 39 inches.
%Met.

Example 7 A sol-like dispersion of antimony pentoxide with an average particle size of 60 mμ and dodecyl methacrylate were added to a polyester fabric dyeing bath, and 1.0% by weight of antimony pentoxide and 2.5% by weight of dodecyl methacrylate were deposited. Ta. After drying this adhered fabric, using argon as the introduced gas, 0.
．． Plasma irradiation was performed at 5 Torr for 2 minutes. The friction durability of this sample was 97%, and the washing durability was 99%.

Comparative Example 5 A sample treated in the same manner as in Example 7 except that dodecyl methacrylate was not added to the dyeing bath and plasma irradiation was not performed had a friction durability of 30% and a washing durability of 3.
It was 7chi.

Example 8 Sobinda liquid of nylon tricot knitted fabric after dyeing,
A sol-like dispersion of magnetic iron powder having an average particle diameter of 30 mμ was added and deposited on an amount of 1.0% by weight. After drying this adhered knitted fabric, plasma irradiation was performed at 0.5 Torr for 2 minutes using argon as the introduced gas, and then immersed in an acrylic acid aqueous solution.The friction durability of this sample was 99 inches, and the washing durability was 100 cycles. Met.

Comparative Example 6 A test bond treated in the same manner as in Example 8 except that plasma irradiation was not performed and acrylic acid aqueous solution was not used. The friction durability was 27%, and the washing durability was 38 cm.

Example 9 A sol-like dispersion of calcium carbonate with an average particle size of 40 mμ was added to a dyeing solution for wool chilimen georgette A,
05 Weight section attached f? After drying this adhered fabric, plasma irradiation was performed for 2 minutes at 0.5 Torr using a mixed gas of 60 moles of Albod and 40 moles of -carbon oxide as the introduced gas.The friction durability of this sample was 96%.
The durability of the washbasin received 98 praises.

Comparative Example 7 Same as Example 9 except that plasma irradiation was not performed.
The friction durability of the treated sample was 34 inches, and the washing durability was 4 inches.
0He was arrogant.

Example 10 A sol-like dispersion of nickel with an average particle size of 10 mμ and glycidyl methacrylate were added to a soaping solution after dyeing a rayon chilimen georgette fabric.
4.0 weight of M-weight glycidyl methacrylate was attached. After drying this adhered fabric, plasma irradiation was performed for 2 minutes at 0.5 Torr using a mixed gas of 60 mol of argon and 40 mol of carbon oxide as the introduced gas. The friction durability of this sample is 98%, and the washing durability is 98%.
It was 9%.

Comparative Example 8 A sample treated in the same manner as in Example 10 except that glycidyl methacrylate was not added to the soaping liquid and plasma irradiation was not performed had a friction durability of 28 inches and a washing durability of 32%.

Patent applicant RiRashi Co., Ltd. Representative Patent Attorney Ken Honda

Claims (1)

[Claims] 1. When attaching fine particles to the fiber surface, a cloth-like material is introduced into a dyeing bath, a washing bath, or a pad bath to which fine particles dispersed in a sol state with an average particle size of 100 millimicrons or less are added. 2. A method for attaching fine particles to a cloth-like article with good durability, which comprises adsorbing or adhering fine particles of 0.001 to 10 weight per fiber weight to the cloth-like article, and then irradiating the cloth-like article with low-temperature plasma after drying. Claim 1, characterized in that a substance capable of radical polymerization is allowed to coexist in a treatment bath to which fine particles are added.
Method 3 of attaching fine particles to cloth-like materials with good durability as described in Section 3, adsorbing or adhering fine particles to cloth-like materials, then irradiating them with low-temperature plasma, and then exposing them to a gaseous or liquid radically polymerizable monomer. A method of adhering fine particles with good durability to a cloth-like article according to claim 1, characterized in that: