JPH02210069A - Production of fiber structure - 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] (Field of Application of the Invention) The present invention has excellent effects such as fastness to rubbing, fastness to sublimation, fastness to light, fastness to washing, fastness to dye migration and sublimation, and prevention of additive bleeding. The present invention relates to a method for manufacturing a fibrous structure.

(Prior art) It has been widely practiced to add additives or dyes to fibers for the purpose of modifying or dyeing them. The problem is that the worse the condition, the more the additive or dye will bleed onto the fiber surface, reducing the consumption performance of the product.

For example, the deeper the color of polyester dyed materials using disperse dyes, and the smaller the molecular weight of the dye, the easier the dye will migrate to the fiber surface, and the faster the colorfastness will be when dry or wet, the faster it will be due to sublimation. Sublimation fastness is reduced, and there are many problems with staining and discoloration.

In the case of dyed polyester products coated or laminated with urethane, acrylic, rubber, PVC, silicone, etc., the dye is highly compatible with the coating resin, so it migrates into the resin over an hour and becomes colored. However, this can cause problems such as color transfer and staining on coatings or laminates.

These problems are unique to disperse dyes, and polyester triacetate poses a particularly serious problem, not nylon.

In addition, there is a technology to manufacture antistatic yarn by kneading polyethylene glycol etc. into polyester in order to impart antistatic properties, etc. However, polyethylene glycol and polyester have relatively poor compatibility, and polyethylene glycol is applied to the fiber surface. bleed into the product, reducing the light fastness of the product. In order to prevent bleeding, an antistatic polymer is placed in the core and a regular polymer is placed in the sheath, and even if the thread is made of core/sheath composite gold thread, bleeding into the sheath still occurs and no solution to the problem has yet been reached.

For example, Japanese Patent Application Laid-open No. 59-82469 discloses a method for preventing staining due to dye migration in coating materials.
This method involves forming a crosslinked film on the dyed material using melamine resin, which has the problem of hardening the texture of the product. However, the effect of preventing dye transfer was insufficient because the melamine resin treatment could not be applied uniformly to the fiber surface.

By the way, Japanese Patent Application Laid-Open No. 62-28484 discloses that it is possible to prevent dye transfer by treating dyed items with melamine resin and then subjecting them to low-temperature plasma treatment. Under plasma treatment conditions, it is difficult to uniformly and sufficiently crosslink both the resin surface and the fiber surface at the same time.

Simultaneous crosslinking of the resin surface and fiber surface can only occur under certain limited plasma conditions. Furthermore, depending on the processing gas used for crosslinking, the resin film may be etched rather than forming a crosslinked structure. Therefore, prevention of dye migration and sublimation is not complete.

Mana, Japanese Patent Application Laid-Open No. 59-106588 describes that a dyed product is treated with a finishing agent and then subjected to low-temperature plasma treatment to increase the abrasion fastness and washing durability of the finishing agent.
There is no description of the migration sublimation prevention effect, and the plasma treatment conditions here do not include any description or limitation of the resin and plasma crosslinking conditions necessary to prevent dye migration and sublimation. Therefore, crosslinking of the fiber surface and the resin surface does not occur, and the effect of preventing dye transfer is quite low.

JP-A No. 61-97467 states that if the surface of the 1/lIi fiber is cross-linked with a waterfall of low-temperature plasma, dye migration will not occur even if coating or laminating with Fretan 0 silicone, rubber, acrylic e-PVC is applied thereto. Although it is disclosed that the dye transfer and sublimation fastness is good in a dry state, it has the disadvantage that it is less effective under high temperature and high humidity conditions.

(Problems to be Solved by the Present Invention) As a result of many years of research into the crosslinking of fibers and various resins by low-temperature plasma, the present inventors have found that only under limited low-temperature plasma conditions can crosslinking occur in the fiber substrate and the resin itself. Furthermore, it was discovered that among cross-linked products, only the cross-linked structure within a specific range is effective in preventing the migration of additives, dyes, etc. In other words, the present invention is effective in preventing the bleed-out of additives, etc. The aim is to obtain a product with sufficient durability without hardening the texture of the product through a simple process.
A surprising effect has been discovered by simultaneously crosslinking a fiber matrix and a crosslinkable resin using low temperature plasma treatment.

(Means for Solving the Problems) That is, the present invention is characterized in that a crosslinkable resin is attached to at least one fiber surface of a fiber structure, and a low-temperature plasma is applied to at least one surface of the resin-processed surface at an energy of 1 to 400 Wa.
/ca, the moisture content of the treated product is 0.05 to 2%, the treatment gas is an inert gas, and the resin surface and 11! The present invention relates to a method for producing a fiber structure characterized by forming a crosslinked structure on the surface of a wire.

The fiber structure of the present invention refers to two-dimensional products such as woven/knitted fabrics, nonwoven fabrics, and sheet products made of synthetic, natural fibers, regenerated fibers, etc.
However, it is especially effective for polyester, triacetate, etc. dyed with disperse dyes.

The crosslinkable resin refers to a material that forms a crosslinked structure, and may be one that can be crosslinked by both heat and plasma treatment. Examples of thermally crosslinkable resins include monomers containing vinyl groups such as acrylic acid, methacrylic acid, methacrylate, and methyl methacrylate, and hepchromer. Examples of both crosslinkable resins include melamine monomers, macromers or derivatives thereof, urea, glyoxal, and triazine ring derivatives. Among these, it is desirable to use resins that are poorly compatible with dyes, especially melabam monomers and macromers. The amount of resin attached is preferably 0.1 to 5 weight based on the weight of the fiber.

If it is less than 0.1%, dye migration onto the surface of the film cannot be prevented. Moreover, if the amount exceeds 5% by weight, dye migration onto the film can be prevented, but there is a drawback that the texture of the fibrous structure becomes hard.

In order to crosslink the resin and fiber base material surfaces by simultaneous treatment for the purpose of preventing additive bleeding or dye migration in low-temperature plasma treatment, all of the following conditions must be met.

First, energy is (high frequency power supply input power (W) ×
It is expressed as number of processing seconds (sea)/electrode area (square centimeters). This value is 1~4 Q Q Ws/cr
A is preferable. If it is less than l Ws /-, not only will the crosslinking process take a long time, but it will also be difficult to create a uniform crosslinked structure on both the resin surface and the fiber base material surface. Also, 400W8
If it exceeds /-, etching takes priority on the resin surface and fiber surface, and the crosslinking effect is not sufficient.

Next, the moisture content of the treated material is the moisture content that the fiber base material has during plasma treatment, and is preferably 0.05 to 2%.

It is more preferable if it is less than the lower limit of O, OS*, but in order to achieve this state, a vacuum pump with a large evacuation capacity is required, and the evacuation time until plasma processing is performed becomes long, which is not desirable from a cost standpoint. do not have. Moreover, if SZ* is exceeded, water in the fiber base material comes out during plasma treatment, making the discharge unstable and making it difficult to create a uniform crosslinked structure on the resin surface and the fiber base material surface. Furthermore, it may become impossible to maintain the processing vacuum level. Although the reason is not clear in this range, reproducibility is good.

Generally, inorganic gases (oxygen, argon, nitrogen, carbon oxide, etc.) are used as processing gases, but the inventors have investigated a wide range of gases and found that among them, Inert gases (nitrogen, argon, helium, neon, xenon, etc.) that have a small amount of carbon dioxide and easily form a dense crosslinked structure are the most effective for causing crosslinking.
The effect of preventing dye migration is also very good. Among the inorganic gases, oxygen, air, etc. are reactive, so they etch the resin or fiber base material during plasma treatment, reducing the degree of dye transfer and sublimation resistance.

Crosslinking occurs even when the processing vacuum is 0.01 to 50 Torr, but according to the results of the study by the present inventors, it is 0.05 to I T
A range of orr is desirable.

As a high frequency power supply that applies voltage, 1 phantom L~13.56~
IHz is preferred, and internal electrodes are preferred from the viewpoint of crosslinking efficiency. Plasma treatment can be performed on only one side, both sides, or a portion of the crosslinkable resin surface, as required.

The object of the present invention can be fully achieved if the outermost surface of the fibers and resin located on the outer surface of the structure is treated.

A crosslinked structure means that a part of the fiber surface and resin surface has 1 to 10
It is sufficient that the film is in a cross-linked state with a thickness of 3 mμ.

To check whether the material is cross-linked, for example, in the case of polyester, when dissolved in triple oleoacetic acid, etc., the cross-linked portion does not completely dissolve and becomes an insoluble substance, but generally it is necessary to dissolve it in a polymer solvent. If insoluble matter remains, it is considered that crosslinking has occurred.

The weight ratio of the crosslinked structure to the fiber weight is 0.001 to 5.
%. If the weight ratio of the crosslinked structure is high, the characteristics of the fibers will be different from the original ones, the texture will be hard, and this will lead to an increase in operational costs, which is undesirable. f7'?
If it is too low, the effect of preventing migration and sublimation of the present invention will be reduced, which is not preferable.

In the present invention, a crosslinkable resin is attached to a fiber base material, a thermal crosslinking treatment is performed, and then a low temperature plasma treatment is performed.

This method increases the crosslinking density of the resin and at the same time crosslinks the fiber surfaces to which no resin is attached, resulting in an excellent dye migration prevention effect. In addition, plasma treatment improves the wettability and adhesion of the fiber and resin surfaces, resulting in improved adhesion between the coating/laminate resin and the base fabric.
is also significantly improved.

This remarkable effect of preventing migration and sublimation is estimated as follows. When processing cross-linked resins, the resin film formed on the fiber surface is attached in the form of blocks when viewed in microscopic units, so dye comes out onto the fiber surface from the unattached areas. Therefore, by performing plasma treatment after processing the crosslinkable resin, the non-adhered portions are also crosslinked, resulting in dye migration and sublimation fastness that is much better than that obtained by processing the crosslinkable resin alone.

In order to form a uniform crosslinked structure on the resin surface and the fiber surface, in order to form a uniform crosslinked structure on the resin surface and the fiber surface, this method simply attaches the crosslinkable resin to the fiber and plasma-treats it. Better dye migration and sublimation fastness can be obtained.

A major feature of this method is that it has excellent performance in preventing migration of dyes, etc. after laminating or coating with urethane, acrylic, rubber, vinyl chloride, and silicone resins after processing the crosslinkable resin.

Polyester base fabric and urethane, acrylic, rubber, PVC,
In the case of silicone-based combinations, the migration of dyes, etc. is very slow and has no commercial value, but by using the method of the present invention, the migration of dyes, etc. can be prevented during drying, high temperature and high humidity. Also, migration of dyes, etc. is completely eliminated.

(Example) A more detailed explanation will be given below according to examples.

However, each fastness measurement method in each table of Examples and Comparative Examples was performed in the following manner.

Dye migration sublimation (Dry): JIS L-085
4 Dye migration sublimation (Wet): JIS L-08
54.

The specific characteristics of dye transfer and sublimation properties when wet are specified in JIS.
A test piece made by the method of L-0854 was immersed in distilled water,
Wet the test piece completely and soak it for 30 minutes at room temperature, then pour out the distilled water and squeeze the test piece between two glass rods until the excess water does not drip off. Two stainless steel metal plates. Attach this to a sweat tester, apply a pressure of 4.5 kg, and place the sweat tester in a dryer at 120°C for 80 minutes with the test piece vertical. .

Judgment is based on grade judgment #) Remember to perform a 5-level evaluation. however,
A circle mark next to a grade determination number indicates that the grade is closer to that number. With this in mind, various polymers and fibers were obtained using conventional methods, and these were processed and dyed into plain weave fabrics. Processing of cross-linked resin is done using dip-nip method.
Plasma treatment was performed on only one side, and each fastness of the plasma treated side was measured. Of course, it can be seen that if plasma treatment is performed on both sides as necessary, the same tendency can be obtained on both the front and back sides.

After removing the size and scouring the polyester fabric, it is dried and heat treated at 180°C for 1 minute. Next, Kayalon Black lO%owf
(135℃ x 60 minutes), and after reduction washing, washing with water and drying. Apply melamine resin (Sumitex Resin M-3) to the dyed cloth.
Two coats of catalyst (Catalyst Sumitex ACX) at a concentration of 1/1° to the resin were applied to the dyed cloth, followed by wet heat treatment and drying.

After this, the moisture retention rate of the fabric after resin processing is adjusted to 0.1 to 1.
0%, and the adjusted fabric was set in a low-temperature plasma treatment tank equipped with a power source of 13.56 kHz and parallel plate internal electrodes, and the pressure was reduced. After the internal pressure reaches 0.05 Torr, process gas is introduced at 30 cc/min to reduce the internal pressure to 0.3 Torr.
It was held at Torr. Then, K between the electrodes is 13.56
One side was subjected to low-temperature plasma treatment for 60 to 120 seconds by inputting energy of MHz 0.5 to 800 Ws/cn ty).

Thereafter, a urethane laminate was applied to the plasma-treated surface of the treated cloth, and the fastness to dye migration and sublimation of these K was evaluated. The results are 1f'! ″″′″r,
s-p*・bottom margin comparison example B
-1 is a dyed cloth coated with urethane, but the effect of preventing migration and sublimation is low.

In Comparative Examples B-2 to B-5, melamine resin was applied to dyed fabrics and then coated with urethane, but the effect of preventing migration and sublimation was small.

In Comparative Examples B-6 to B-9, dyed fabrics were subjected to plasma treatment for different times and then coated with urethane, but the effect of preventing migration and sublimation was small.

In Examples A-1, A-2, A-7, and A-8, after attaching melamine resin (2 wt%), energy was 1 and 0 Ws.
/ crA, moisture content of treated material 0.05-2%, plasma treated with inert gas, plasma energy 0.1 Ws / crA vs. 800 Ws/d, other plasma conditions are the same as above. Comparative example B-1 treated with
The effect of preventing migration and sublimation is greater than that of 0, B-11, B-12, and 8-13.

In Examples A-3, A-4, A-9, and A-10, energy 2QQws was applied after attaching melamine resin (2wt%).
/ffl, moisture content of treated material 0.05-2. Comparative Examples B-14, B-15, and B- were treated with plasma using an inert gas, but the moisture content of the treated material was 4.0 or 10%, and the other plasma conditions were the same as above. 16,B-
Compared to No. 17, the transfer sublimation prevention effect is dog.

In Examples A-3 and A-4, after attaching melamine resin (2wt), plasma treatment was performed using an energy of 200 Ws/aA, a moisture content of the treated material of 0.05%, and an inert gas. Comparative Example B-1'8. The treatment was carried out using oxygen or air as the processing gas and under the same plasma conditions. B-
Compared to No. 19, B-20, and B-21, the effect of preventing migration and sublimation is greater.

From the above, it can be seen that the effect of preventing the migration and sublimation of dyes, etc. is insufficient in the method using only simelamine resin processing, the method using plasma treatment after processing with melamine resin (including finishing agent), or the method using only plasma treatment. Forming a crosslinked structure on the fiber and resin surfaces for the purpose of preventing dye migration can only be done under special plasma treatment conditions. Naturally, if even one of the conditions d is off, the effect of preventing dye migration and sublimation will be greatly reduced.

Claims (1)

[Scope of Claims] A crosslinkable resin is attached to the fiber surface of at least one side of the fiber structure, and a low-temperature plasma is applied to at least one side of the resin-processed surface at an energy of 1 to 400 Ws/cm^2 and a moisture content of the treated material of 0. 05 to 2%, a process gas is an inert gas, and a crosslinked structure is formed on a resin surface and a fiber surface.