JPH01192877A - Production of animal hair fiber adsorbing ceramic - Google Patents

Abstract

PURPOSE:To obtain the title supple fiber rich in crispiness, by adding a specific resin having cationic groups to an aqueous dispersion of fine ceramic particles, charging the above-mentioned fine particles into cationic charged particles and adsorbing the resultant cationic particles on anionic charged animal hair fibers. CONSTITUTION:A resin having cationic groups and film-forming ability, e.g., amino acrylic copolymer or polyamide epichlorohydrin resin, is added to an aqueous dispersion of fine ceramics particles, such as silicic acid or alumina based particles, having 0.01-20mu particle diameter to include the afore-mentioned fine particles in the above-mentioned resin and charge the particles to provide cationic charged particles. The resultant particles are then exhausted and adsorbed on animal hair fibers pretreated with an oxidizing agent, such as hypochlorite, and having anionic charged fiber surfaces thereof, dried and heat- treated to afford the aimed animal hairs adsorbing the ceramic, having flaxen crispiness and soft feeling and suitable as underwear. An aliphatic amide of a tertiary amine having polyoxyethylene group is preferred as a dispersing agent for dispersing the fine ceramics particles.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing ceramic-adsorbed animal hair fibers by exhaustively adsorbing ceramic fine particles onto animal hair fibers.

(Prior Art) When attaching ceramic fine particles to fibers, a method has conventionally been used in which an acrylic resin is used as a binder and the ceramic fine particles are mainly attached to synthetic fiber fabrics. However, in this method, a relatively large amount of resin must be used to attach the ceramic fine particles to the fibers, and the general properties of the acrylic resin used cause the problem that the texture of the fibers becomes very poor. The durability of the texture was also poor. Moreover, when the fibers to be processed are in the form of yarn, sliver, or loose wool, adhesion occurs between the fibers, making defibration difficult, and in the end, the applicable fiber forms are limited to fabrics.
It could not be applied to anything other than fabric.

(Problem to be solved by the invention) The present invention was made in view of the current situation, and
Despite the fact that ceramic fine particles are attached to animal hair fibers in the form of parahair, sliver, fabric, etc., it not only has a linen-like crisp texture but also a soft texture that can be applied to underwear with good durability. The object of the present invention is to obtain a method for producing ceramic-adsorbed animal hair fibers that can be used as a ceramic-adsorbed animal hair fiber.

(Means for Solving the Problems) The present invention achieves the above-mentioned objects and has the following configuration.

That is, in the present invention, a resin having a cationic group and film-forming ability is added to a dispersion liquid in which ceramic fine particles are dispersed in water using a dispersant, and the ceramic fine particles are covered with the resin and cationically charged. The gist is a method for producing ceramic-adsorbed animal hair fibers, which is characterized in that the animal hair fibers are subjected to exhaustion adsorption on animal hair fibers whose surfaces are anionically charged through oxidation treatment, and then the animal hair fibers are subjected to dry heat treatment. be.

Two aspects of the present invention will be described in detail below.

In the present invention, animal hair fiber is used as the processed fiber. The term "animal hair fiber" as used herein refers to natural keratin fibers obtained from animals such as wool, albaca, mohair, angora, and cashmere, and the fiber forms include hair, sliver, yarn, and two-knit woven fabrics.

It may be in any form such as non-woven fabric.

In the present invention, it is necessary to oxidize the above-mentioned animal hair fiber in advance to anionize the fiber surface.

The conditions for this oxidation treatment should be adjusted depending on the type of animal hair.1Usually, it varies depending on the type of oxidizing agent and the amount used, but generally 1 to 10% of the weight of the fiber is used when carried out in a batch method.
o, II1. After immersion treatment at room temperature for 10 to 30 minutes at room temperature, it is recommended to raise the temperature to 30 to 50°C and perform treatment for 10 to 40 minutes.If continuous method is used, 3 to 10% o, w
, f for about 3 to 15 seconds at room temperature, and after squeezing the liquid at 100% pickup, it is preferable to let it stay at room temperature for about 3 to 5 minutes.

These processing temperatures and processing times are just a guideline, and
It is not necessarily limited to this.

Examples of the oxidizing agent used here include hypozincate, chlorite, dichloroisocyanurate, permanganate, hydrogen peroxide, monopersulfuric acid, and salts thereof.

Oxidized animal hair fibers are thoroughly washed with water.

A reducing agent is used to remove the oxidizing agent remaining inside the fiber and at the same time anionize the surface of the animal hair fiber. As the reducing agent, sodium bisulfite, sodium sulfite, sodium metabisulfite, etc. can be used, and the amount used is 3 to 8% o, w, f,
The degree is appropriate.

In the present invention, the animal hair fibers charged with anions are covered with a resin having a cationic group and capable of forming a film, so that the cationically charged ceramic fine particles are absorbed and adsorbed thereon.

The ceramic fine particles used here are fine powders whose particle size ranges from 0.01 to 20 μm in diameter.

The ceramics used include silicic acid-based, alumina-based, zirconium-based, and titanium-based ceramics, and more specifically, silicic acid-based silicon oxide SiO□1 alumina-based aluminum oxide Ajl! 20. .

Examples include zirconium-based zirconium oxide Zr0z and titanium-based titanium oxide TiO□.

In addition, aluminosilicate 812, which is a composite of these
20i ・5IOz+Zircon ZrCl2・S+Oz+
Aluminum titanate A' 203TiO□ and cordierite 2Mg0・2A #203・5SiO□
Zeolite MeO・8β203・asio represented by
Examples include □・nil□0 (Me is an alkali metal or alkaline earth metal).

Here, a method for exhaustively adsorbing ceramic fine particles onto animal hair fibers will be explained below. Naturally, even if ceramic fine particles are added to an aqueous solution and stirred, only a white suspension will result.If the solution is left to stand for 5 to 30 minutes, the supernatant liquid of the solution will become transparent and the ceramic fine particles will settle to the bottom. Therefore, a dispersant is required to uniformly disperse ceramic fine particles in an aqueous solution.

In general, dispersants are used to maintain a uniform and stable dispersion state of things that exist as fine particles in water, such as disperse dyes and pigments, but most of these can be broadly classified into dispersants. It is a dispersant having an anionic charge, such as a β-naphthalene sulfonic acid formaldehyde condensate, polyoxyethylene alkylphenol ether, or its sulfuric ester salt. Even if these dispersants are used, the effect of improving the aqueous dispersibility of ceramic fine particles is poor. As the dispersant used in the present invention, a compound represented by the following chemical formula (I) is recommended because it has excellent emulsifying performance and dispersion performance for ceramic fine particles.

(However, m and n are integers of 1 to 15, R represents an aliphatic group,
) such a dispersant (aliphatic amide of tertiary amine having polyoxyethylene group) at 2 to 10% o, w, f
, the aqueous dispersibility of ceramic fine particles was significantly improved. In the present invention, there is no need to be particularly limited to this dispersant as long as it has good monodispersibility.

Next, a resin having a cationic group is used to contain the aqueous dispersed ceramic fine particles, and the particles are charged with cations.

It is essential that the resin used here has a cationic group that can react with anionized animal hair fibers and has a film-forming ability.

Such resins include aminoacrylic copolymers represented by the following chemical formula (II), polyamide epichlorohydrin resins represented by the following chemical formula (III), amino-modified silicone resins represented by the following chemical formula (IV), and amino-modified silicone resins represented by the following chemical formula (V). Examples include cationic urethane resins.

CH2C1-(I) DAYHOH KAICIl □ It(J \ ・ ,,,, -NN・・□１□,・・・□・−□I□゛・−
1□・per□...“v'w□・・□,...□・J) l) (However, R, R', R″, and R″′ are all alkyl groups.

X is a halogen atom) By adding and mixing these resins to an aqueous dispersion of ceramic fine particles, the ceramic fine particles are covered with the resin and cationically charged. In this case, a dispersion of ceramic fine particles encapsulated in a resin and cationically charged may be prepared as a dispersion separate from the treatment bath (this will be added to the treatment bath later); A dispersion liquid in which only fine particles are dispersed with a dispersant is added to the treatment bath in advance.

Subsequently, by adding a resin having a cationic group to this treatment bath, ceramic fine particles may be included in the resin in the treatment bath to form a dispersion of cationically charged ceramic particles. The latter is rather more reasonable.

Furthermore, among the above-mentioned resins having cationic groups used in the present invention, when an amino-modified silicone resin is used in combination with an aminoepoxy resin, the durability of the hand is further improved, so it is good to use them in combination as appropriate.

The amount of the resin having a cationic group to be used may be appropriately determined depending on the desired texture of the fiber.

Generally 1-10% for aminoacrylic copolymers
In the case of polyamide epichlorohydrin resin, 10 to 30% o, f, and in the case of amino-modified silicone resin, 1 to 10% o, w, f, are suitable. With aminoacrylic copolymer, it is possible to obtain a material with a rough and hard texture that is required for spring and autumn materials.
Polyamide epichlorohydride = IO- According to phosphorus resin, the beam required for inner and outer clothing,
With cationic urethane resin, it is possible to obtain a material with a moderate texture with firmness, and with cationic urethane resin, it is possible to obtain a material with the bulky yet soft texture required for the middle surface, and with amino-modified silicone resin, it is possible to obtain material with a moderate texture. The extremely soft texture required for underwear can be obtained.

The cationically charged ceramic fine particles covered with the above-mentioned resin are absorbed and adsorbed onto animal hair fibers which have been anionically charged in advance in the form of an aqueous dispersion.

In this exhaustion adsorption treatment, in the case of aminoacrylic copolymer, polyamide epichlorohydrin resin, and cationic urethane resin, the pH is 7.0 to 10.0. In the case of amino-modified silicone resin, the pH is adjusted to 4.0 to 7.0, and in any case, the pH is adjusted to 10 to 50 at 20 to 5°C.
By doing the processing for minutes.

Ceramic fine particles can be almost completely absorbed and adsorbed onto animal hair fibers.

The rate of exhaustion of ceramic fine particles into animal hair fibers depends on the type of resin used, the amount used per bath, the pH, treatment temperature, treatment time, etc., so it is recommended to set the conditions through experiments in advance. good.

The animal hair fibers having absorbed and adsorbed the ceramic fine particles in this way are then dehydrated and subjected to a drying heat treatment.

This dry heat treatment condition is used to form a film on the fibers and completely fix the resin used.

It is preferable to perform dry heat treatment at 80 to 120°C for 30 to 60 minutes.

(Function) Although the detailed mechanism by which water-insoluble ceramic fine particles are adsorbed to animal hair fibers is not clear, the inventor of the present invention conjectures as follows. First, after treating the animal hair fiber with an oxidizing agent,
When neutralized with a reducing agent, the disulfite bonds in animal hair are oxidized to produce sulfonic acid groups, and at the same time, the peptide bonds in the cuticle are cleaved to produce carboxyl groups and primary amines, and as a result, anions are formed on animal hair fibers. The seat becomes sexually charged. On the other hand, ceramic fine particles themselves are metal oxides (MeO□), which are insoluble in water and acids.
Some metal salt ions (Me
Although it becomes O2), it is not considered that this directly binds to animal hair fibers.

Therefore, the unpaired electrons of the oxygen in the ceramic fine particles (metal oxide) are chemically adsorbed by the cationic surfactant amine, which is a dispersant, resulting in a 9-element structure.

Insoluble ceramic particles are uniformly dispersed in an aqueous solution,
It becomes a stable aqueous dispersion, and when a resin having a cationic group such as an amino group is applied in this stable dispersion state, the ceramic fine particles are desorbed by the cationic surfactant, and at the same time, the oxygen contained in the ceramic fine particles is removed. A phenomenon occurs in which unpaired electrons are chemically adsorbed to the amine groups of the resin, and as a result, the resin becomes encapsulated in ceramic particles, and the resin itself becomes cationically charged.

Hence, to the anionized seat of animal hair fibers.

The resin molecules having cationic functional groups react, and the ceramic particles included in the resin are also exhausted and adsorbed onto the animal hair fibers. After the reaction, the resin is dried and cured to form a film on the animal hair fibers, which is presumed to improve the fiber adsorption durability of the ceramic fine particles.

(Example) Next, the two methods of the present invention will be specifically explained using examples.

Example 1 Prepare a general wool yarn (count 2/32) for knitting.

Using a jet dyeing machine, add the liquid so that the bath ratio is 1:15, and add the penetrating agent Tergifol TMN (manufactured by UCC, USA, nonionic activator) 0.5% o, w, f at room temperature. After operating for 5 to 10 minutes and thoroughly moistening the raw material,
Sodium hypochlorite in effective chlorine amount 5.0% o, w, f,
Add and circulate for 10 minutes, then add 2 to 2~2 pl+ with concentrated sulfuric acid.
The temperature was maintained at 30°C for 20 minutes. Next, 5.0% sodium sulfite was added and the temperature was 35℃ for 15 minutes.
After dechlorinating and neutralizing for a minute, wash with water.

I added new fluid.

Here, 2.0% O, W, F of zirconium silicate ( After adding Ceramic 2 (a product of Kinsei Kogyo Co., Ltd.) and uniformly dispersing it, this was added to the treatment bath and the treatment bath was operated for 10 minutes.

Next, 6.0% o
When w and f were added to the treatment bath and treated at 50°C for 40 minutes, the initially suspended solution became colorless and transparent, and the ceramic fine particles were completely absorbed into the fibers. .

Thereafter, after dehydration using a conventional method, a dry heat treatment was performed at 90° C. for 60 minutes to obtain a ceramic-adsorbed wool yarn according to the method of the present invention. This wool yarn had a soft texture that could be used for underwear. 11 using this wool
When we made a prototype of the fi volume and conducted a wearing test, we found that there was no change in the texture even after one season of wear, and the texture was excellent in durability.

Example 2 A wool sweater made of Australian merino seed material with a diameter of 21.5 μm was prepared, and sodium dichloroin cyanurate was added to it at a bath ratio of 1:30 using a paddle machine at an effective chlorine amount of 4.0% o. w, f, plus 25 at 25℃
After soaking for a minute and washing with water, sodium sulfite3. Oo, w,
After treatment at 30° C. for 15 minutes in a bath of acidic sodium sulfite 3.0% o, y, f, it was thoroughly washed with water. Here, add Esomin T/15 (dispersant, Lion Akzo ■ product) to a solution of 3.0% O, W, F, well dissolved in boiling water.
Zeorum (zeolite).

Toyo Soda Kogyo ■ product) 4.0% O, W, F was added and sufficiently dispersed, and then added to the treatment bath.

Next, 5.0% O, W, F of Chemitylene GU-2 (cationic urethane resin, Sanyo Kasei product) was added.

When added to a sufficiently diluted post-treatment bath and treated at 50°C for 30 minutes, the solution became clear.

After the treatment, it was dehydrated using a centrifugal dehydrator, and then subjected to dry heat treatment at 80° C. for 15 minutes using a tumble dryer.

When the fibers constituting the treated sweater were observed under a microscope, it was confirmed that ceramic fine particles were adsorbed onto the animal hair fibers. This sweater was both bulky and soft.

When this sweater was tried on, it was found that there was no change in texture even after one season of wear, and the texture was excellent in durability.

(Effects of the Invention) The present invention has a structure in which a resin having a cationic group and film-forming ability contains ceramic fine particles, is cationically charged, and is adsorbed to animal hair fibers that have been previously anionized by oxidation treatment. death.

According to the method of the present invention having such a structure, ceramic fine particles are completely bonded to animal hair fibers, and the type of resin is selected to create not only a linen-like crisp texture but also a soft texture that can be applied to underwear. In particular, it is very durable (animal hair fibers can have it).

Claims (1)

[Claims] (1) A resin having a cationic group and film-forming ability is added to a dispersion liquid in which ceramic fine particles are dispersed in water using a dispersant, the ceramic fine particles are covered with the resin, cationically charged, and this is oxidized in advance. 1. A method for producing a ceramic-adsorbed animal hair fiber, which comprises making the fiber surface absorb and adsorb onto an anionically charged animal hair fiber, and then subjecting the animal hair fiber to a dry heat treatment.