JP2000160479A - Textile-processing agent, production of fibrous structure and textile material for industrial material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a textile-processing agent improved in adhesiveness and suitable for industrial fibrous material by including an adhesiveness-improving component comprising a coupling agent in a supercritical fluid or a fluid similar to it. SOLUTION: This textile-processing agent is prepared by including an adhesiveness-improving component (e.g. a silane coupling agent) comprising a compound having at least one group selected from hydroxyl group, amino one and carboxyl one in a supercritical fluid (e.g. carbon dioxide) or a fluid similar to it. The textile-processing agent is applied to an industrial fibrous material such as a tire cord.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber treatment agent using a supercritical fluid or a similar fluid, which is suitable for processing for improving the adhesiveness of a fiber structure, and a method for producing a fiber structure using the same. Further, the present invention relates to a fiber material for industrial materials having improved adhesion.

[0002]

2. Description of the Related Art Hitherto, in order to improve the adhesiveness of a fiber structure, a processing agent having a functional group and a crosslinking component has been applied to the surface of the fiber structure. Such a method is indispensable when a fiber structure is used for an industrial material such as a tire cord, but stronger adhesiveness is continuously required. Here, one of the factors that cause the adhesiveness to be insufficient when the above-mentioned processing agent is used is that, in such a method, the functional group is present only on the surface of the fiber structure and not on the surface of the fiber structure. In some cases, the adhesion between the product and the processing agent interface was weak.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to a fiber treating agent capable of obtaining an adhesiveness superior to conventional processing agents in a process for improving the adhesiveness of a fiber structure, and a fiber structure using the same. An object of the present invention is to provide a method for manufacturing a product. A further object of the present invention is to provide a fiber material for industrial materials having improved adhesion by such a production method.

[0004]

Means for Solving the Problems A fiber treating agent, a method for producing a fiber structure and a fiber material for industrial materials of the present invention have the following constitutions.

[0005] That is, the fiber treating agent of the present invention comprises an adhesiveness improving component contained in a supercritical fluid or a fluid similar thereto.

[0006] The method for producing a fibrous structure of the present invention comprises:
The fibrous structure is treated using a treating agent in which the adhesion improving component is contained in a supercritical fluid or a fluid similar thereto.

[0007] Further, the fiber material for industrial materials of the present invention comprises:
The fiber structure obtained by the above-mentioned production method is used.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, an adhesiveness improving component is present near the surface of a fiber structure to improve the adhesion between the fiber structure and an adhesive, resin, rubber, film, film, or the like. Refers to components in general. Examples include compounds containing functional groups such as hydroxyl groups, amino groups, carboxyl groups, coupling agents, aziridine-based crosslinking agents, blocked isocyanate-based crosslinking agents, low-molecular crosslinking agents such as carbodiimides,
Examples thereof include a polymer crosslinking agent such as a maleic anhydride copolymer, a resorcin-formalin resin, a melamine resin, a glyoxal resin, and an epoxy resin.

In the present invention, as an adhesiveness improving component,
It is preferable to use a compound containing at least one functional group among a hydroxyl group, an amino group and a carboxyl group.
The reason for this is that the hydroxyl, amino and carboxyl groups can react with the reactive functional groups contained in the adhesive to form a covalent bond. Examples of the compound containing a hydroxyl group include polyvinyl alcohol or derivatives thereof, triols such as glycerol, diols such as ethylene glycol and propylene glycol, compounds having a single hydroxyl group such as higher alcohols, phenol and tannic acid. Compounds having a single amino group such as polyamines such as polyethyleneimine, diamines such as ethylenediamine, compounds having a single amino group such as dodecylamine, and amino groups such as aniline. Aromatic compounds containing one or more, such as carboxyl group-containing compounds such as polycarboxylic acids such as polyacrylic acid, dicarboxylic acids such as adipic acid, compounds having a single carboxyl group such as lauric acid, benzoic acid A carboxyl group and the like aromatic compounds containing one or more.

In the present invention, it is equally preferable to use a coupling agent as an adhesiveness improving component. Here, the coupling agent is a general term for compounds having a function of binding two kinds of compounds having two or more parts and having different properties. The coupling agent interacts with both the fiber structure and the component to be bonded, and has the effect of increasing the adhesiveness between the two. Usually, a silane coupling agent is used as the coupling agent. Examples of silane coupling include vinyl group-containing compounds such as vinyltrichlorosilane and vinyltrimethoxysilane, methacryloyl group-containing compounds such as γ- (methacryloyloxypropyl) trimethoxysilane, and glycidyl such as γ-glycidyloxypropyltrimethoxysilane. Group-containing compounds, and amino group-containing compounds such as γ-aminopropyltriethoxysilane.

In the present invention, the supercritical fluid refers to a fluid at a temperature and pressure exceeding a critical temperature and a critical pressure. This state does not belong to either the gaseous phase or the liquid phase, and has the same mobility as gas, though the density is similar to liquid. For this reason, various drugs can be dissolved in a supercritical fluid in the same way as a liquid,
There is also an advantage that it can easily penetrate into the details of the fiber structure. Further, the supercritical fluid becomes a gas by lowering the pressure, and there is an advantage that a dissolved substance can be easily separated by utilizing the phenomenon.

Further, the fluid similar to the supercritical fluid in the present invention refers to a fluid in a gas or liquid state at a high pressure, for example, 1 Mpa or more, which is sufficiently higher than the pressure of an apparatus used in ordinary fiber processing. . The fluid in such a high pressure state can dissolve various drugs like the supercritical fluid, and easily penetrates into the details of the fibrous structure.
In the present invention, it has the same action as the supercritical fluid.

Examples of the substance used in the present invention in the state of a supercritical fluid or a similar fluid, that is, a supercritical fluid or a similar fluid include carbon dioxide, nitrogen, water, ethanol, and the like. It is most preferable to use carbon dioxide from the viewpoint of easiness of conditions for setting a state of a critical fluid and safety. Another advantage of using this substance is that a large amount of carbon dioxide is exhausted by the fibrous structure and has a large effect of swelling the fibrous structure. The critical temperature of carbon dioxide is 31.1 ° C. and the critical pressure is 7.2 Mpa.

In the present invention, the phrase "adhesion-improving component is contained in a supercritical fluid or a similar fluid" means that the adhesion-improving component is dissolved, dispersed, emulsified, or the like in a supercritical fluid or a similar fluid. Say. In the present invention, a supercritical fluid containing the adhesion improving component or a fluid similar thereto is used particularly as a fiber treatment agent.

Next, a method for producing a fibrous structure using the fiber treating agent will be described. In the method for producing a fiber structure according to the present invention, the fiber structure is treated using the fiber treating agent.

As the fiber structure in the present invention, filaments, spun yarns, woven fabrics, knitted fabrics, non-woven fabrics and the like made of at least one of natural fibers, regenerated fibers, semi-synthetic fibers and synthetic fibers can be used. Cotton as natural fiber,
Regenerated fibers such as animal hair fiber, silk, hemp, etc. Regenerated fibers such as rayon (viscose rayon) and cupra (copper ammonia rayon), and semi-synthetic fibers such as acetate (triacetate) as cellulosic semi-synthetic fibers Examples of the synthetic fibers include various fibers such as polyester, nylon, acrylic, and aramid.

Among them, polyester fibers or nylon fibers are most important in practical use among general-purpose fibers for which an improvement in adhesiveness is required. Therefore, it is more effective to use a fiber structure containing these fibers. As the fiber structure containing polyester fiber or nylon fiber, in addition to those composed of only polyester fiber or nylon fiber, cotton, natural fibers such as wool, semi-synthetic fibers such as acetate, regenerated fibers such as rayon, nylon and the like It includes a blend of at least one of synthetic fibers and a polyester fiber or a nylon fiber, or a twist, a weave, a weave, or the like.

Further, due to the recent demand for higher performance of fibers for industrial materials, which are not general-purpose fibers, it has become important to improve the adhesiveness of fiber structures containing aramid fibers, polyphenylene sulfide fibers, fluorine fibers and the like. Because
It is equally effective to use a fiber structure containing these fibers.

By treating such a fibrous structure with a treating agent containing an adhesion improving component in a supercritical fluid or a similar fluid, the fibrous structure is bonded to the inside of the fibrous structure or to the surface thereof. Adds a property improving component. This treating agent contains at least an adhesion improving component and a supercritical fluid or a similar fluid. In the method for producing a fibrous structure according to the present invention, the treating agent containing the adhesiveness improving component contained in a supercritical fluid or a similar fluid is used particularly for the fibrous structure, so that the adhesiveness improving component is added to the fibrous structure. Has the advantage that it is also exhausted to the inside of the fiber structure and a stronger bond with the fibrous structure is obtained. It is considered that the reason is that the supercritical fluid or a similar fluid is swollen due to the supercritical fluid or the similar fluid being exhausted in a large amount by the polymer constituting the fibrous structure and the structure is relaxed.

The supercritical fluid or a similar fluid can easily change the solubility and dispersibility of the compound contained therein by changing the temperature and pressure.
By utilizing this property, the adhesiveness improving component can be more efficiently applied to the fiber structure. That is, at the beginning of the processing step, a condition is used in which as much of the adhesion improving component as possible can be contained in the supercritical fluid or a similar fluid. Change to difficult conditions. Examples of such a method include reducing the pressure in the late stage of the treatment process from the initial stage to reduce the solubility and dispersibility of the adhesiveness improving component in a supercritical fluid or a similar fluid, thereby reducing the fiber structure. There are ways to promote internal migration. Furthermore, if the pressure drop is performed rapidly, the adhesion improving component remaining in the supercritical fluid or a similar fluid is instantaneously deposited on the surface of the fiber structure, and the fiber structure is efficiently and efficiently treated with the adhesion improving component. It can be completely coated.

In the present invention, a dye may be contained in the fiber treating agent of the present invention, and an adhesiveness improving component may be imparted to the fiber structure simultaneously with the dyeing. By using this method, the process of treating the fibrous structure can be further shortened, which is very advantageous in terms of improving production efficiency and reducing energy consumption.

In the present invention, the form in which the fibrous structure is treated with the treatment agent is a method in which the fibrous structure is filled into an apparatus, and a substance to be used in the state of a supercritical fluid or a similar fluid is injected into the apparatus and the pressure is increased. And the temperature may be adjusted, and the adhesion-improving component may be contained in the same supercritical fluid or a fluid similar thereto and introduced into the state. It is preferable to provide another tank in addition to the processing tank in order to include the adhesion improving component in a supercritical fluid or a similar fluid.

In the present invention, in order to more efficiently provide the adhesiveness improving component, the apparatus for filling the fibrous structure is a facility for circulating a supercritical fluid or a similar fluid, and a facility for circulating the fibrous structure. , Or both. Here, in order to circulate a supercritical fluid or a fluid similar thereto, a pipe for injecting a medium into and a pipe for discharging the medium into a container filled with a fibrous structure may be attached, and these may be connected by a pump and driven. Also,
In order to circulate the fibrous structure, a supercritical fluid or a similar fluid may be caused to flow in a container filled with the fibrous structure to rotate the fibrous structure.

When carbon dioxide is used as a substance used in the state of a supercritical fluid or a similar fluid, the pressure is preferably 10 Mpa or more, and the temperature is preferably 40 ° C. or more. The reason for this is that when the pressure is lower than this, the solubility of the adhesion improving component in a supercritical fluid or a similar fluid is low. If the temperature is lower than this, the rate of exhaustion of the component for improving the adhesion to the fiber structure is low.

In the present invention, the fiber structure obtained by such a production method is used as a fiber material for industrial materials. Examples of fiber materials for industrial materials include tire cords, base materials such as power transmission belts and hoses, membrane materials and sheet products used for tents and dome ceilings, nursing care products, filters, fishing nets, geotextiles, Medical materials and the like can be mentioned.

Among them, in the present invention, it is more effective to use the fiber structure obtained by such a production method as a tire cord. The reason for this is that the tire cord receives a severe deformation force in a state of being bonded to the rubber, so that a very strong bonding force is required. ADVANTAGE OF THE INVENTION According to the manufacturing method of the fiber structure of this invention, higher adhesiveness can be obtained compared with the conventional thing.

In order to produce the fiber material for a tire cord of the present invention, a resorcinol-formalin-based adhesive ordinarily used for a tire cord is applied to the fiber structure produced by the production method of the present invention, followed by drying and drying. Heat treatment may be performed. A tire is manufactured by embedding the tire cord provided with the adhesive or the like in rubber.

[0028]

EXAMPLES The present invention will be described below more specifically with reference to examples.

The measurements in the examples and comparative examples were performed by the following methods. <Measurement of Drug Application Rate> The absolute dry weight of the sample before and after the treatment was measured and calculated by the following equation.

Drug application rate (%) = 100 × (W1-W0) / W0 W0: Absolute dry weight of sample before treatment (g) W1: Absolute dry weight of sample after treatment (g) <Adhesion to rubber Test> Using an unvulcanized rubber composition having the following composition, 3
Zero tire cords are aligned in parallel and a thickness of 1
mm rubber sheet, 30 tire cords are similarly arranged on the rubber sheet, and a rubber sheet having a thickness of 2 mm is layered again, and then vulcanized at 150 ° C. for 30 minutes to form a rubber / cord composite. Obtained. Next, using a peeling tester, speed 5
The peeling force between the two layers of tire cord was measured at 0 mm / min. (Composition of unvulcanized rubber composition) NR (nitrile rubber) 60 parts by weight SBR (styrene butadiene rubber) 40 parts by weight ZnO 4 parts by weight Stearic acid 1.5 parts by weight Antioxidant 1 part by weight Carbon black 60 Parts by weight Aromatic oil 8 parts by weight Sulfur 3 parts by weight Flow promoter 1.5 parts by weight [Example 1] Two polyester multifilaments composed of 1500 denier / 250 filaments are combined,
An untreated tire cord was obtained by twisting 10 times / 10 cm.

The 50 g of this tire cord is filled with an inner volume of 500 m.
After filling into a 1 l high pressure vessel, the temperature was raised to 40 ° C. while injecting carbon dioxide into the vessel. Further, carbon dioxide was continuously injected while maintaining the temperature, and the pressure was increased to 20 Mp.
a.

Next, 0.5 g of tannic acid as an adhesiveness improving component was charged into another high-pressure vessel having an internal volume of 100 ml connected to the high-pressure vessel, and the temperature was similarly set to 40 ° C. and the pressure was set to 20 Mpa. Thereafter, the valve between the high-pressure container filled with the fibrous structure and the high-pressure container filled with tannic acid is opened, and a circulating pump connected to the two containers is activated to further fill the fibrous structure with tannic acid. Introduced into the container.

Then, the temperature was raised to 130 ° C., and after maintaining the condition for 30 minutes, carbon dioxide was gradually discharged in the next 30 minutes. Thereafter, the drug application rate to the sample was measured and found to be 0.83%.

Next, a 5% by weight resorcinol-formalin-based adhesive having the following composition was applied to the tire cord to which the adhesiveness improving component had been applied, and dried at 100 ° C. for 1 minute.
Heat treatment was performed at 40 ° C. for 2 minutes. (Blending of resorcinol-formalin adhesive) 52.3 parts by weight of soft water 2.3 parts by weight of 10% aqueous NaOH solution 4.9 parts by weight of Sumikanol 700 (manufactured by Sumitomo Chemical: resorcinol / formaldehyde initial condensate) 37% aqueous solution of formalin 7 parts by weight Nipol 2518FS 36.8 parts by weight (manufactured by ZEON Corporation: polymer latex) (solid content: 20%) The peel strength of the treated tire cord in the above-mentioned adhesion test is 18.7 kgf / 25 mm, and However, the peel strength was greatly improved as compared with 7.5 kgf / 25 mm. Example 2 Example 2 was repeated except that γ-aminopropyltriethoxysilane was used as an adhesion improving component.

As a result, the drug application rate was 0.75%, and the peeling force was 21.4 kgf / 25 mm, which was significantly improved as compared with the untreated one. [Comparative Example 1] The same tire cord as in Example 1 was immersed in 1000 ml of an aqueous solution containing 0.5 g of tannic acid and 0.1 g of sodium laurylbenzenesulfonate as a dispersant, and was subjected to a dyeing tester (Labmat: manufactured by Mathis). At 130
It processed at 30 degreeC for 30 minutes.

Thereafter, the drug application rate was measured in the same manner as in Example 1 and found to be 0.56%. The peeling force of the tire cord after the same adhesive application treatment in the above-mentioned adhesion test was 10.5 kgf / 25 mm, which was improved as compared with the peeling force of the untreated tire cord. It did not improve as much as it did. [Comparative Example 2] The same operation as in Comparative Example 1 was carried out except that γ-aminopropyltriethoxysilane was used as the adhesiveness improving component.

As a result, the drug application rate was 0.51% and the peeling force was 11.7 Kgf / 25 mm, which was also higher than the peeling force of the untreated one, but was treated with a supercritical fluid. Did not improve as much. Example 3 The same operation as in Example 1 was performed except that the same denier nylon filament was used instead of the polyester multifilament, and the treatment temperature was 90 ° C.

As a result, the drug application rate was 0.85%, and the peeling force was 25.6 kgf / 25 mm, which was much higher than the peeling force of the untreated product of 10.3 kgf / 25 mm. [Example 4] The same operation as in Example 1 was carried out except that γ-aminopropyltriethoxysilane was used as an adhesiveness improving component.

As a result, the drug application rate was 0.79%, and the peeling force was 29.0 kgf / 25 mm, which was significantly improved as compared with the untreated one. Comparative Example 3 The same tire cord as that of Example 3 was immersed in 1000 ml of an aqueous solution containing 0.5 g of tannic acid and 0.1 g of sodium laurylbenzenesulfonate as a dispersant, and was subjected to a dyeing tester (Labmat: manufactured by Mathis). At 90 ° C,
Treated for 30 minutes.

Thereafter, when the drug application rate was measured in the same manner as in Example 3, it was 0.54%. The peeling force of the tire cord after the same adhesive application treatment in the above-mentioned adhesiveness test was 12.9 kgf / 25 mm, which was higher than the peeling force of the untreated tire cord. It did not improve as much as it did. [Comparative Example 4] The same operation as in Comparative Example 3 was carried out except that γ-aminopropyltriethoxysilane was used as the adhesiveness improving component.

As a result, the drug application rate was 0.44%, and the peeling force was 14.0 Kgf / 25 mm, which was also higher than the peeling force of the untreated one, but was treated with a supercritical fluid. Did not improve as much.

[0042]

According to the fiber treating agent and the method for producing a fibrous structure of the present invention, the adhesiveness improving component is contained in the supercritical fluid or a fluid similar thereto, so that the adhesiveness improving component is contained inside the fiber. And the adhesiveness can be greatly improved.

Further, by using the fiber structure manufactured by this manufacturing method as an industrial material such as a tire cord, a fiber product having higher adhesiveness than before can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 3B154 AA07 AB03 BA60 BB02 BB32 BB66 BD14 BD16 BD17 BE04 DA08 4L033 AB01 AB09 AC11 BA11 BA28 BA96 CA34 CA68 CA70 DA07 4L036 MA05 MA33 PA21 PA26 PA46 UA25

Claims (10)

[Claims] 1. A fiber treating agent, wherein the adhesion improving component is contained in a supercritical fluid or a similar fluid. 2. The fiber treating agent according to claim 1, wherein the supercritical fluid or a similar fluid uses carbon dioxide as a medium. 3. The fiber treating agent according to claim 1, wherein the adhesiveness improving component is a compound containing at least one of a hydroxyl group, an amino group and a carboxyl group. 4. The fiber treating agent according to claim 1, wherein the adhesiveness improving component is a coupling agent. 5. A method for producing a fibrous structure, comprising treating the fibrous structure with a fiber treating agent containing an adhesion improving component in a supercritical fluid or a similar fluid. 6. The method for producing a fibrous structure according to claim 5, wherein said supercritical fluid or a similar fluid uses carbon dioxide as a medium. 7. The method according to claim 5, wherein the adhesion improving component is a compound containing at least one of a hydroxyl group, an amino group and a carboxyl group. 8. The method for producing a fibrous structure according to claim 5, wherein the adhesiveness improving component is a coupling agent. 9. A fibrous material for industrial materials, characterized by using a fibrous structure obtained by the production method according to any one of claims 5 to 8. 10. The fiber material for industrial materials according to claim 9, which is used for tire cords.