JP2005126872A - Fluorine resin coating fabric having high friction fastness and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a product having an increased friction fastness and a processing method therefor in colored knitted or woven fabric made of cellulose fiber and colored artificial leather that has been thought that the satisfactory increase of the friction fastness is difficult. <P>SOLUTION: On the surface 5 of dyed cloth, flat scale-jointing parts are partially formed by using microfine flat scale pieces of almost pure PTFE. By the partial existence of the flat scale pieces-jointing parts, gaps are formed between the surface of the dyed cloth and the body to be rubbed and their contact is inhibited thus the migration of microfine color substance into the rubbed body is prohibited. Thus, the product having increased friction fastness and the processing method therefor has been provided. In addition, the increase of friction fastness becomes possible by this process in the cloths of which the friction fastness is regarded as to be difficult and the friction fastness in dark color dyed cloth in which improvement of the fastness is difficult also has attained the sufficient increase of the fastness. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a colored fiber cloth, a colored synthetic leather cloth, or an artificial leather cloth that exhibits a high degree of friction fastness, in which a fine color substance of the colored cloth is hardly transferred to a friction partner material as a contaminant.

Colored fabrics such as knitted fabrics and non-woven fabrics, or synthetic leather fabrics and artificial leather fabrics are frequently used as materials constituting finished products such as outer garments, bags and chair upholstery.
When the colored cloth is used as, for example, a chair upholstery, the chair upholstery and the partner's clothing come into contact with each other and rub against each other, and the fine color substance of the colored fabric is detached to the partner clothing. There is a possibility that the transfer clothes adhere and contaminate the partner clothing.
In particular, contamination is conspicuous when the garment or the like, which is a friction object, is white or light-colored.
Also, the chair upholstery that is a friction body and the partner's clothing that is a friction body are in a mutual relationship, and the position may be reversed.
Furthermore, a woven or non-woven fabric of cellulose (fibre) fibers, or a colored fabric such as a synthetic leather fabric or an artificial leather fabric using a flexible elastic resin may significantly contaminate the friction partner material.

The frictional movement between the colored cloth and the friction mating material constituting the outer garment, bag, chair upholstery, etc. is based on the frictional movement of both the colored cloth and the friction mating material, and one of the stationary materials. Is one of the cases caused by the other frictional operation.
However, in the present invention, which is actively operated in the frictional motion, the friction counterpart material is referred to as a friction object with respect to the colored cloth.

It is a requirement for the performance of the colored fabrics that the fine color substance on the colored fabric side is transferred to and adhered to the friction target body and contaminates the friction target body, and is an important item among the requirements.
In the Japanese Industrial Standard, this is referred to as “dye fastness to friction”, but in the present invention, the fine color substance may be other than dyed cloth, and this is referred to as “friction fastness”.
Such a colored fabric is naturally required to have high frictional fastness.

On the other hand, various techniques for increasing the frictional fastness of fabrics are disclosed.
JP 2000-136484 A JP 7-173772 A JP-A-6-255030 It should be noted that the quoted text from the cited document and the explanation thereof use the expression of the quoted text as it is.

“Patent Document 1” is a disclosure relating to a cellulosic fabric that is resin-processed simultaneously with dyeing, has excellent color developability and fastness to dyeing, has no reduction in strength, and has excellent antifungal properties and shrinkage resistance.
Paragraph No. “0018” of “Patent Document 1” includes “Friction fastness: Friction tester type II is used according to JIS L-0849”, and the dye fastness includes the friction fastness. It is.
Paragraph No. “0005” of “Patent Document 1” discloses “by using two specific catalysts for a glyoxal resin in a specific blending ratio in the simultaneous processing of dyeing resin” as the catalyst, Cellulose characterized by using a mixed catalyst of an amine hydrochloride (A) and a borofluoride compound (B) and having a pure concentration ratio (A) / (B) of 95/5 to 60/40 Fabric processing method ".

In Table 1 of paragraph number “0030” of “Patent Document 1”, the dry / wet series of the friction fastness of the cellulose fabric obtained by the processing method is shown, and when the processing method is adopted, It is disclosed that the frictional fastness is improved by about 1 to 2 grades as compared with the case of not.
That is, “Patent Document 1” is a disclosure of a method for improving the friction fastness by a method in which the dye is not detached from the colored cloth and is not transferred to the friction object by a method of firmly capturing the dye with a resin.

“Patent Document 2” is a document related to a fluororesin for water / oil repellent processing of a fiber cloth. As disclosed in paragraph “0005” of “Patent Document 2”, In addition, the present invention provides a water-dispersed fluorine-based water- and oil-repellent agent capable of obtaining a processed cloth having high dyeing fastness and a soft texture, and a method for producing a water-dispersed fluorine-based water- and oil-repellent agent.
The said fastness to dyeing is the fastness to friction based on the description of “[Dyeing fastness evaluation method] JIS-L0849” in paragraph “0050” of “Patent Document 2”.

  In paragraph No. “0006” of “Patent Document 2”, “a polymer containing a polymerization unit of a polymerizable monomer containing a polyfluoroalkyl group and a polymerization unit of another polymerizable monomer, and It provides a water-dispersed fluorine-based water- and oil-repellent agent comprising 1 to 20 parts by weight of glycols per 100 parts by weight.

In addition, paragraph number “0063” of “Patent Document 2” discloses an example in which a water-dispersible fluorine-based water and oil repellent agent is specifically applied to a polyester cloth. In paragraph number “0064”, “ As Table 6 ”, the results of Examples 1 to 4 are disclosed as performance after 5 washes, and the applied polyester fabric of the water and oil repellent agent exhibits a high friction fastness compared to Comparative Examples 1 and 2 that are not applied. It is disclosed to show.
Thus, “Patent Document 2” is a disclosure of a fluorine-based water and oil repellent that captures a dye firmly with a resin. When the water and oil repellent is applied, the dye is difficult to be detached from a colored cloth, and is applied to a friction object. It is disclosed that it is difficult to make a transition.

“Patent Document 3” relates to a surface material such as a building material as described in paragraph “0001” as “a surface material provided on an inner wall, a ceiling, a door or the like in a building or the like in addition to a vehicle such as a train or an aircraft”. It is a disclosure relating to the provision of a surface material having an improved flameproof property of a glass fiber cloth and an excellent colorant fastness to friction.
In paragraph number “0002” of “Patent Document 3”, “to date, as this surface material, a material made by attaching a cloth made of wool, acrylic or the like on a resin plate is known”. Instead, as disclosed in paragraph No. “0005” of “Patent Document 3”, “a surface material characterized in that a colorant is attached to a surface of a glass fiber cloth using a fluororesin as a binder” Disclosure has been made.

  Further, paragraph number “0007” of “Patent Document 3” states that “as the colorant 2, an organic pigment is suitable because it has good dispersibility, weather resistance, and heat resistance. It is also possible to use inorganic pigments such as graphite and metal compounds, or to use dyes. "

  In addition, in paragraph number “0008” of “Patent Document 3”, “the fluororesin for binder for attaching the colorant to the glass fiber cloth 1 includes tetrafluoroethylene resin (PTFE), perfluoro-alkoxy resin”. (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoroethylene-ethylene copolymer resin (ETFE), vinylidene fluoride resin (PVDF), etc. ".

  Also, paragraph number “0009” of “Patent Document 3” states that “as a method of attaching a colorant to the glass fiber cloth 1, an aqueous dispersion obtained by dispersing a fluororesin and a colorant or a fluororesin solution is colored. It is disclosed that the glass fiber cloth 1 is coated with a liquid obtained by adding an agent and mixed, or the glass fiber cloth 1 is immersed in this liquid and then dried.

“Patent Document 3” is a disclosure in which a mixture of a colorant such as a pigment and a fluororesin is used as a colored binder, and the binder itself is a colored surface material.
In other words, “Patent Document 3” is a surface material for building materials in which softness, texture and the like are not important. Instead of the conventional colored surface material made of wool or acrylic, which is a fiber material, pigment and dye itself, and fluororesin This disclosure relates to a coloring material having a high degree of frictional fastness by making it a hard material that is a mixture with a binder.
The above is the description of the cited document as the background art.

There are the following two kinds of fine color substances that are rubbed with the colored cloth and transfer and adhere from the colored cloth to the friction object.
(B) When the fine color substance to be transferred is a dye or pigment itself.
(B) When the fine color substance to be transferred is a composite strip of a dye or pigment and a cloth material.
The frictional fastness improving techniques disclosed in “Patent Document 1”, “Patent Document 2”, and “Patent Document 3” are classified as (a), and the transition color substances are all dyes and pigments. This is a disclosure of a technique for improving the fastness to friction, which suppresses the dropping of the dye or pigment itself and the transfer to the friction object even when it comes into contact with the friction object.

The colored woven or non-woven fabric of cellulose fiber yarns may significantly contaminate the object to be rubbed, and the frictional fastness may be so low that it cannot be practically used.
If the fine color material is only the dye itself, the reason why the frictional fastness is low is that the frictional fastness should be improved by dyeing with a reactive dye that binds firmly to the fiber.
However, woven fabrics and non-woven fabrics of cellulose fibers that are dyed with reactive dyes often have low frictional fastness.

The reason why the frictional fastness is low is that the cellulose fiber has a relatively low strength and the surface of the cloth is easily fuzzy, etc. This is because the substance is a composite strip of a dye or pigment and a cloth material.
In particular, the cotton fiber cloth is made by spinning short fibers with very short cotton yarn, so that the surface of the cloth has a lot of fluff and some fluff is loose, which further reduces the frictional fastness.
Thus, when a colored cloth made of dyed cellulose fibers is rubbed against the object to be rubbed, the transition color substance is classified as (b), although there is a part of the dye itself classified as (b). It can be said that there are many cases of fine color substances that are a composite of a dye and a part of a cloth material.
The fine color substance, which is a composite of the dye classified into the latter (b) and a part of the cloth material, is covered with the fine pieces of the colored fiber of the colored cloth that has already been released from the main body fiber, or the colored cloth. These are fine pieces released from the main body fibers of the colored cloth by an external force when rubbed against the friction body.

On the other hand, a colored synthetic leather cloth or artificial leather cloth using a flexible elastic resin may significantly contaminate a friction target body and have a low frictional fastness so as not to be practically used.
The synthetic leather cloth and artificial leather cloth using the flexible elastic resin can be colored by a method of kneading a pigment or a dye into the flexible elastic resin, or by dyeing the dyeable resin after making it into a product. To do.
Such a colored flexible elastic resin constitutes a surface portion in a synthetic leather cloth and a matrix in an artificial leather cloth.
The colored flexible elastic resin such as polyurethane resin used for a synthetic leather cloth or an artificial leather cloth generally has a low inclusion force of pigments and dyes and a low strength.
As described above, the fine color substance that migrates and adheres when the colored synthetic leather cloth or the artificial leather cloth is rubbed against the friction object, although there is a part of the inclusion pigment or dye itself classified as (b) above, It can be said that there are many cases of the fine color substance of the colored flexible elastic resin that is a composite with a part of the cloth material classified as (b).

A common material that lowers the frictional fastness due to the phenomenon that fine color substances are often composite strips of dyes and pigments and cloth materials, and is synthesized with cellulose fiber cloth. It is leather or artificial leather.
The disclosures of “Patent Document 1”, “Patent Document 2”, and “Patent Document 3” are all in the case where the former transition color substance is a dye or a pigment itself, and the dye or pigment is in contact with a friction target. It is a disclosure relating to suppressing the dropout of itself and the transition to the friction object.
That is, “Patent Documents 1 to 3” include technical contents corresponding to the suppression of contamination to the friction object when the fine color substance is a fine piece of colored cloth material, which is classified in (b) above. Not.

With regard to the colored fabric of the woven or non-woven fabric of cellulose fiber yarn, or the synthetic leather fabric or artificial leather fabric using a flexible elastic resin such as polyurethane resin, the transition color substance to the friction object is At present, there is no effective technique for improving the fastness to friction in the case of a composite strip of a dye or pigment to be classified and a part of a cloth material.
In other words, even if the fabric material and the dye or pigment itself are firmly bonded by resin processing, etc., the fine color in which the transition color substance to the friction object is a colored composite of the dye or pigment and a part of the fabric material In the case of a substance, contamination due to transfer to the friction object cannot be prevented.
It is desired for those skilled in the art to provide colored cellulose fiber yarn knitted fabric or colored cellulose fiber nonwoven fabric, or colored synthetic leather fabric or colored artificial leather colored fabric having high friction fastness.

  In consideration of the above-described conventional problems, the present invention provides a high degree of friction resistance including the case where the fine color substance that contaminates the friction target is a fine piece of a composite of a dye or pigment and a part of the cloth material. It is an object of the present invention to provide a colored woven or non-woven fabric of cellulose fibers, a colored synthetic leather cloth or an artificial leather cloth.

As a result of intensive studies in view of the above-mentioned object, the inventors have surprisingly found that when a substantially pure PTFE (polytetrafluoroethylene) fine flat scale piece is partially bonded to the surface of a colored cloth, the frictional fastness is high. I found it to be a colored cloth.
The reason for paying attention to the PTFE fine flat scale is that the form is a fine flat scale, and thus the cover property is good. On the other hand, the conventionally known fine spherical PTFE has a low cover property because it is spherical. .
In addition, since it is in the shape of a PTFE fine flat scale, it enters the gap of the cloth and gets entangled, so it does not necessarily require a binder resin for bonding with the cloth, and has the property of bonding to the cloth surface without the binder resin, On the other hand, fine spherical PTFE has a spherical shape, and therefore a binder resin is essential for bonding.
The almost pure PTFE referred to in the present invention means a substance that is mostly PTFE even if both ends of the PTFE molecule are non-fluorinated molecules, such as PTFE telomer (low molecular weight polymer). Point to.

Thus, the inventors have reached the following invention.
As shown in FIG. 1, an enlarged model schematic view of a fluororesin-coated colored cloth in a woven or non-woven fabric of cellulose fibers, or a synthetic leather cloth or artificial leather cloth using a flexible elastic resin, as shown in FIG. The surface 5 of the cloth is partially a scale joint 6 made of almost pure PTFE fine flat scales.
The diameter of the longest part of the fine flat scale is about 2 to 10 μm, and the ratio of the total area of the scale joint 6 to the total surface area of the cloth 5 is about 15 to 50%. Invented a fluororesin-coated colored fabric characterized by the following.

  In addition, in the scale joint portion 6 by the PTFE fine flat scale on the surface 5 of the cloth, a binder resin is interposed between the fine flat scale and the surface of the cloth 5. The invention is a fluororesin-coated colored cloth.

  Furthermore, the cellulosic fiber cloth such as the knitted fabric or the non-woven fabric is made of cotton fiber, and is a fluororesin-coated colored fabric.

  In the synthetic leather cloth or the artificial leather cloth using the flexible elastic resin, the flexible elastic resin is a polyurethane-based resin, and is a fluororesin-coated colored cloth.

  In addition, as a solvent, IPA (isopropyl alcohol) or water, or a liquid in which PTFE fine flat scales are dispersed in IPA and water, cellulose fiber cloth such as woven fabric or nonwoven fabric, or flexible elastic resin is used. In the invention of the processing method to obtain the fluororesin-coated colored cloth, which is obtained by applying to the surface of the synthetic leather cloth or artificial leather cloth which has been in liquid form, and being diffused by drying the solvent. is there.

(1) When the colored woven fabric or synthetic leather is rubbed against the friction object, the fine color substances that contaminate the friction object are dyes and pigments, and part of the cloth material and dyes and pigments. There was almost no technology for improving the frictional fastness in the latter case.
The fluororesin-coated cloth of the present invention uses a colored woven or non-woven fabric of cellulose fiber yarn, or a colored synthetic leather cloth or flexible elastic resin having a flexible elastic resin as a matrix, which has been particularly difficult to improve the friction fastness. We were able to provide products with a high degree of frictional fastness for colored artificial leather fabrics.
(2) As a method for suppressing the migration of a fine color substance of a composite of a part of a cloth material and a dye or pigment, a method by forming a resin on the cloth surface, which has been conventionally known, It was a method for improving the frictional fastness that significantly impairs the functions such as the feel and breathability of the fabric.
On the other hand, the present invention is a system in which the friction object is hardly brought into contact with the original cloth surface portion by partially forming a scale joint portion with PTFE fine flat scales on the cloth surface.
Therefore, it is possible to improve the frictional fastness without substantially impairing the original texture, feel, breathability, hue, or gloss of the fabric.
(3) Conventionally, such a product that is difficult to improve the frictional fastness has been taken as a measure to avoid being colored in dark color, but application of the present invention has made it possible to provide a dark colored product.
(4) A conventionally known surface treatment of a fluororesin having a small fluororesin component, such as addition of a fluoroalkyl group, could not be expected to lower the friction coefficient.
On the other hand, in the present invention, since the PTFE scale joint, which is a substantially pure fluororesin having a very low friction coefficient, is present on the cloth surface, the structure becomes highly slippery and the friction object is easy to slide. In this way, the object to be rubbed is less likely to come into contact with the original cloth surface, which also contributes to the improvement of the frictional fastness.
(5) When using the cloth to which the present invention is applied, since the cloth has a low critical surface tension, it is difficult for dirt to adhere to it, and since the coefficient of friction is low, it is difficult to be subjected to frictional breakage, thereby improving the durability of the product. .

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described based on examples with reference to the drawings.
In order to clarify the operation mechanism of the present invention, the dimensions and ratios of the drawings are exaggerated and may be different from the actual ones.

FIG. 1 is a schematic diagram of a fluororesin-coated cloth according to the present invention.
In FIG. 1, a schematic plan view 1 is shown in the upper part of FIG. 1, and a cross-sectional schematic diagram of the very surface layer of the AA cross section of the schematic plan view 1 is shown in the lower part of FIG. The cross-sectional structure of the action part of a fluororesin coating cloth is shown.
FIG. 1 is a schematic plan view of FIG. 1, which is an example of a model sketch drawn by dividing a part of a scanning electron micrograph of the surface of the fluororesin-coated cloth of the present invention. The degree of enlargement corresponds to a length B of 20 μm. To do.

In the schematic plan view 1 of FIG. 1, the scale joint 6 is partially joined on the surface 5 of the colored cloth 3 as if it were a fish scale group.
In the schematic plan view of FIG. 1, the PTFE fine flat scale forming the scale joint portion 6 is not clearly defined in its size boundary, but is about 2 μm or so when it is small when viewed from the long diameter part of the scale. It is about 10 μm.

In the schematic cross-sectional view 2 of FIG. 1, a cross section is shown in which the scale joint portion 6 made of the PTFE fine flat scale is formed on the surface 5 of the colored cloth 3.
The colored cloth 3 can be colored by a dyeing method or a kneading method of a pigment or a dye.
The scale joint portion 6 on the AA line in the schematic plan view of FIG. 1 and the scale joint portion 6 in the cross-sectional schematic view 2 correspond in positional relationship.
As shown in FIG. 1, in the fluororesin-coated fabric of the present invention, the surface portion 5 of the fabric is partially a scale joint portion 6 such as a fish scale group made of the PTFE fine flat scale.

FIG. 2 is a schematic cross-sectional view showing a state in which the surface 12 of the friction object 11 such as a white cloth is in contact with the fluororesin-coated cloth of the present invention.
2 is a cellulose fiber cloth such as a knitted fabric or a non-woven fabric, or a synthetic leather fabric or an artificial leather fabric using a flexible elastic resin.
The colored cloths 3 rub against each other by alternating motion or the like as indicated by arrows 13 with respect to the stationary friction object 11.
However, since the scale joining portion 6 by the PTFE fine flat scale is partially joined to the colored cloth surface 5 in a scale shape, the surface 12 of the friction object 11 can hardly contact the surface 5 of the colored cloth 3. .
Therefore, there is almost no migration of the fine color substance from the colored cloth surface 5 on the surface 12 of the friction object 11, and the surface 12 of the friction object 11 is not contaminated.

FIG. 3 is an enlarged schematic view of the broken-line circle 14 portion of FIG. 2, and is an enlarged view of a portion showing the surface 5 of the colored cloth 3, the scale joint portion 6 of the PTFE fine flat scale, and the surface 12 of the friction object 11.
As illustrated in FIG. 3, a gap 20 is formed due to the presence of the fine flat scale 6, and the surface 12 of the friction object 11 cannot contact the surface 5 of the colored cloth 3.
Further, since the scale joint portion 6 is made of substantially pure PTFE fine flat scale having a very low friction coefficient, the contact portion between the surface 12 of the friction object 11 and the scale joint portion 6 is easy to slip, and therefore the friction object. Therefore, the surface 12 of the rubbed body is more difficult to come into contact with the original surface 5 of the colored cloth 3.
The fluororesin-coated cloth according to the present invention is an action that makes it difficult for the friction object to come into contact with the surface of the colored cloth in the action of improving the friction fastness. This is different from the action that does not contaminate even when contact friction occurs.

The reason for forming the scale joints of almost pure PTFE fine flat scales on the surface of cellulose fiber knitted fabrics and nonwoven fabrics, or synthetic leather fabrics and artificial leather fabrics using flexible elastic resin, is the gap between the fabric surfaces. It is thought that the van der Waals force is also acting because it is easy to get in and entangle with the surface structure of the cloth and difficult to peel off.
In addition, the scale joint part by the PTFE fine flat scale has a high cloth cover efficiency due to the scale shape, and exhibits an efficient cover effect with a small amount of the PTFE fine flat scale. Does not impair characteristics such as touch, breathability, hue, or gloss.
On the other hand, in the case of conventionally known fine spherical PTFE, even if it can enter the surface portion of the cloth, it cannot be present in a form that is difficult to peel off because it is spherical, and the cover efficiency of the cloth is low, If the cover efficiency is to be increased, a large amount of material is required as compared with the case of the above-mentioned fine flat scale, and therefore, in the processed cloth, the original characteristics of the cloth such as texture are impaired.

Even in the case of bonding with a binder resin interposed, in the case of the fine spherical PTFE, since the contact portion has a small spherical shape, a large amount of binder resin is required and the cloth surface is covered with a large amount of binder resin. The feel and breathability are impaired.
On the other hand, in the scale joint portion by the PTFE fine flat scale of the present invention, since the contact portion with the processed cloth is large because of the flat scale shape, a slight binder resin may be used, and the original texture, feel, breathability, It is possible to form a stronger scale joint without substantially impairing the hue or gloss, and to further improve the frictional fastness.

As shown in FIG. 1, in the fluororesin-coated cloth of the present invention, the surface 5 of the colored cloth 3 is partially a scale joint portion 6 like a fish scale group by the PTFE fine flat scale.
In FIG. 1, for the area of the partial scale joint 6, the appropriate condition is that the ratio of the total area of the scale joint 6 to the total surface area of the colored cloth 3 is about 15 to 50%. I understood.
As an example of the ratio measurement method, an arbitrary section of a scanning electron micrograph is sketched on a paper, and the ratio of the mass of the paper in the arbitrary section and the total mass of the paper from which the scale joint is cut off is calculated. Desired. Of course, other measurement methods may be used.
Moreover, since the partial scale joint part can be observed with an optical microscope, it can be used for quality control.

If the ratio is less than about 15%, improvement in the frictional fastness is insufficient, and if it is about 50% or more, the texture of the fabric is considerably changed and becomes hard, and the feel and breathability are impaired.
Therefore, the range in which the frictional fastness can be improved without substantially impairing the original texture, feel, breathability, hue, or gloss of the cloth is the ratio of the total area of the scale joints to the total surface area. It was found to be about 15-50%.

Next, materials for obtaining the fluororesin coated fabric of the present invention will be described.
In the present invention, almost pure PTFE refers to a substance having both ends of a PTFE molecule such as PTFE telomer, which is a non-fluorine molecule, but very few as a polymer, and most of which is PTFE. ing.
The stock solution is obtained by dispersing the PTFE fine flat scale group in water or IPA as a solvent, and further diluting the stock solution to obtain a working solution.

PTFE itself is a telomer having a molecular weight of 1000 to 100,000, and a polymer, and one size of the PTFE fine flat scale is approximately 2 to 10 μm in the longest diameter of the flat scale surface, and the fine flat scale piece If it is strong about the shape, it is an oval shape.
In the stock solution in which the PTFE fine flat scale group is dispersed, when the solvent is water, a surfactant is added to stabilize and make the dispersion state uniform, and the solid content is about 20%.
When the solvent is IPA, a very small amount of surfactant is added, the solid content is about 25%, and both are white translucent liquids. In use, water or IPA, or water and IPA are used. Dilute with etc. to make the machining fluid.
The above is description about the undiluted | stock solution and process liquid which can be applied to this invention.

The fabric applicable to the present invention is applicable to both natural fibers including wool and synthetic fibers.
However, the present invention is directed to a colored woven fabric or nonwoven fabric of cellulose fibers, or a colored synthetic leather fabric or artificial leather fabric using a flexible elastic resin, which has a high need for improvement in friction fastness.
This is because these cloths have a common feature that the fine color substance transferred to the friction object is often a composite strip of a dye or pigment and a cloth material.
Cellulose fibers include natural fibers such as cotton and hemp, and chemical fibers include viscose rayon and cupra.
Cellulose fiber coloring methods include dyeing and printing for dyed fabrics, and printing includes pigment dyeing in which a pigment is fixed with a resin.
In the case of chemical fibers, raw material coloring using pigments and dyes is also applied.
Moreover, it is applicable also to the cloth which deform | transformed the surface of cloth by physical processing etc., such as a raising cloth and an electric flocking cloth.

Synthetic leather cloth is a leather-like material in which a flexible elastic resin layer is bonded to a woven fabric or non-woven fabric base fabric by a wet method or a dry method (coating method) to form a surface layer portion. .
Artificial leather cloth is a leather-like material having a structure conforming to the collagen structure of natural leather and enclosing with a flexible elastic resin as a matrisk with a gap in a bundle of ultrafine fiber aggregates.
Coloring is generally carried out by kneading a pigment or dye into the flexible elastic resin, but a dyeing method may be employed.
Synthetic leather and artificial leather have a surface structure with a silver surface (skin-like, grained), and a leather with a back leather like nubuck (a leather-polished leather of cowhide) or suede. Is also applicable.

The flexible elastic resin can be applied to soft PVC (polyvinyl chloride), soft PVDC (polyvinylidene chloride), thermoplastic elastomer, and the like.
Thermoplastic elastomers are resins that can be molded by flowing by heating and exhibit rubber elasticity at room temperature, but are TPU (urethane), SBC (styrene), TPO (olefin), TPVC (vinyl chloride), TPEE. There are (polyester) type, TPAE (polyamide) type, etc., any of which can be applied. The above is the description of the cloth that can be applied to the present invention.

Next, a method for obtaining the fluororesin-coated cloth of the present invention will be described.
As a processing method for obtaining the fluororesin-coated cloth of the present invention, an immersion method, a roll coating method or the like can be employed.
In the dipping method, a batch type Zicker dyeing machine, liquid dyeing machine, or the like can be used, and dehydration is performed by a roll-type squeezing method or a centrifugal dehydration method.
In the continuous method, a dipping / mangle drawing method, a roll coating method or the like is used.
The evaporation and drying of the solvent such as moisture and IPA may take a long time at a low temperature of about 100 ° C., but may be performed at a high temperature of about 150 to 170 ° C. in order to increase the drying efficiency. When a binder is not used in combination, baking heat treatment is not necessary.
When a binder is used in combination, a baking heat treatment for forming the binder into a resin is necessary.

Next, as a specific example, a description will be given of an example of a processing method in which a cloth is immersed in a diluted solution of PTFE fine flat scale group dispersion stock solution, which is a dipping / mangle squeezing method, and squeezed with a mangle and coated.
The stock solution of the stock solution of water or IPA is generally diluted with water, but in some cases, it may be diluted with IPA or IPA and water.
In order to stabilize the PTFE fine flat scale group to be dispersed, a slight amount of nonionic or anionic surfactant is added, and the concentration is diluted to about 3 to 10% with the stock solution.
As a guide, the mass of the pickup is about 3 to 7% in terms of the mass of the stock solution with respect to the mass of the work cloth.

In addition, in order to increase the durability of the scale joint portion by the PTFE fine flat scale, a binder such as polyurethane resin or acrylic resin may be used in combination.
When a binder is used in combination, baking at an appropriate processing temperature is required for converting the binder into a resin.
The above is description about the method of obtaining the fluororesin coating cloth of this invention.

Using a tricot knitted fabric of cupra long fiber yarn as a base fabric, a microporous layer of polyurethane resin is formed by a wet film-forming method using a blended solution in which a coloring pigment is added to a TPU thermoplastic elastomer and mixed with the tricot knitted fabric. Black and dark red synthetic leather cloths having a nubuck-like surface and obtained by coagulation, washing and drying were prepared on the cloth.
An IPA dispersion stock solution having a solid content of 25% of PTFE fine flat scales was diluted with water to obtain a processing solution.
The synthetic leather cloth was coated on the surface of the synthetic leather by the immersion / mangle drawing method, and the solvent was diffused and dried to obtain a fluororesin-coated synthetic leather cloth.

Specifically, as an IPA dispersion stock solution for the PTFE fine flat squad group, “Dry Film Fluorotelomer RA / IPA” (trade name, manufactured by DuPont), a stock solution with a solid content of 25%, and water with a slight addition of a nonionic active agent Was diluted stepwise by 1% with the undiluted solution, and 7 levels of processing solution of 1-7% were prepared.
The synthetic leather cloth was coated with a small immersion / mangle test machine.
For each of the dilutions, the immersion / mangle drawing method was performed in three levels, one to three times, and air diffused and dried at 150 ° C. to produce a total of 21 types of work cloths.

As shown in the schematic plan view of FIG. 1, a scanning electron micrograph of the surface of each of the obtained work cloths is taken, and the area of the scale joint portion by the PTFE fine flat scale against the surface area of the synthetic leather cloth. Regarding the ratio, the black processed cloth shows 9, 15, 26, 43, 51, 59, and 67%, and the red processed cloth shows 8, 14, 25, 44, 50, 58, and 70%. Seven types of processed cloth were selected.
Friction fastness was evaluated by assigning sample numbers of Sample B02 to Sample B08 in order for the black processed fabric and Sample R02 to Sample R08 in order of the red processed fabric.

The evaluation method of the friction fastness is JIS L0849-1996, 6.1. (2) When using the friction tester type II
FIG. 4 is a schematic side view of the operation unit of the friction tester II type.
The distance of the load arm 26 between the rotation fulcrum 27 and the center of the friction element 28 is 110 mm, and the load arm can freely move in the direction of the arrow 29 with the rotation fulcrum 27 as a rotation axis.
On the other hand, for the measurement cloth, a test piece 32 to be evaluated is attached to a convex test piece base 31.
On the other hand, a rubbing white cotton cloth 30 as a friction object is attached to the friction element 28, a load of 2N is applied, and the test piece base 31 is reciprocated between 100 mm of the test piece in the C direction as shown by the arrow direction 33 to 30 per minute. Reciprocates 100 times at a reciprocating speed.

The dry test was performed in the standard state of the white cotton cloth for friction 30, and the wet test was performed by wetting the white cotton cloth for friction 30 with water to make it about 100% wet, and subjecting the test piece in the standard state to a predetermined friction test. Thereafter, it is dried at a temperature not exceeding 60 ° C. and then evaluated.
The degree of contamination of the rubbing white cotton cloth 30 was determined by the contamination gray scale defined in JIS L 0805-1998.
The color difference compared with the white cotton cloth for friction before the friction test is grade 5 based on the color difference ΔE ^* ab due to the standard light D of 6.1 (L ^* a ^* b ^* color difference based on the color system) of JIS Z 8730 The color difference is 0 (no difference), the 4th grade is the color difference 4.5, the 3rd grade is the color difference 9.0, the 2nd grade is the color difference 18.1, and the 1st grade is the color difference 36.2.
The results are shown in Table 1.

According to Table 1, the friction fastness of the black raw sample B01 and the red raw sample R01 not coated with fluororesin was evaluated to be grade 2 or lower in both wet and dry conditions.
On the other hand, in the sample having the scale joint portion of the fine flat scale, the sample having a frictional fastness of 3 or more in both dry and wet, the area ratio of the scale joint portion is the sample B03 for the black work cloth, the red processing Regarding the cloth, it was found that the effect of improving the friction fastness appears in the fluororesin-coated cloth of the present invention at about 15% or more of the sample R03.

On the other hand, on the surface of the texture, the texture from the sample B02 and the sample R02 up to about 51% of the sample B06 when the area ratio is black and about 50% of the sample R06 when the area ratio is red is unprocessed in each of the samples B01 and R01. It was almost the same as the sample.
When the area ratio is about 59% of sample B07, about 67% of B08, about 58% of sample R07, and about 70% of sample R08, the texture becomes hard and the original unprocessed synthetic leather cloth The texture characteristics have been lost.
Therefore, it was found that the ratio of the total area of the scale joints to the total surface area of the cloth was in the range of about 15 to 50%.

From the results of Example 1, the processing conditions of Sample B03 and Sample B04 were selected for the black sample, the processing conditions of Sample R03 and Sample R04 were selected for the red sample, examination in the case of using the binder resin together, and evaluation of water washing and dry washing Went.
The binder used is 10% of the urethane-based resin “Pacall V440” (trade name, manufactured by Meisei Chemical Industry Co., Ltd.) and an isocyanate-based crosslinking agent added to the processing liquid under the processing conditions, A binder combined working fluid was prepared.
Processed with the above-mentioned binder combined working solution according to Example 1, dried and baked at 160 ° C. to obtain a processed cloth in the case of using a binder resin together. For black, sample B09 corresponds to sample B03 and sample B04 Sample B10, and for red, sample R09 and sample R10 correspond to sample R03 and sample R04.
This was evaluated in terms of frictional fastness according to Example 1, and the results are shown in Table 2.
In addition, evaluation after washing of each processed cloth was based on the evaluation conditions defined in JIS for both water washing and dry washing in the washing method, and the corresponding JIS and the number of washings are shown in the lower column of Table 2.

According to Table 2, with respect to the frictional fastness, the sample with the binder had a better frictional fastness than the sample without the binder.
However, the effect of further improving grade 4-5 was not recognized.
Regarding the friction fastness of the sample after washing, the samples without binder were the same as before and after washing in the samples B03 and B04 for black and R03 for red, but for the sample R04 for red After both washings, wet friction was better than that before washing.
As for the sample used in combination with the binder, the black color is almost the same after both washings, and the red color is generally better after washing than before washing, but the evaluation exceeding 4-5 grade is not obtained. It was.

In addition to the above trial production, synthetic elastic cloth using TPO resin, TPVC resin, TPEE resin, and artificial leather cloth using TPU, which are thermoplastic elastomers, are also examined as actual product development. did.
From these results, it was found that the present invention can improve the frictional fastness, and it was confirmed that the present invention is also effective in synthetic leather cloth and artificial leather cloth other than the use of polyurethane resin.

We examined cotton heavy cloth for bags. The color was two colors, with black being directly dyed and red having a reactive dye color.
Using PTFE fine flat scale group of water dispersion stock solution, coating the surface of the cotton light heavy cloth for bag by dipping and mangle squeezing method with the processing solution diluted with water, and diffusing and drying the solvent A processed cloth was obtained.

A specific method is to use a stock solution of 20% solid content of “Dry Film Fluorotelomer RA / W” (trade name, manufactured by DuPont) as an aqueous dispersion stock solution of the PTFE fine flat scale group, and use a small amount of a nonionic active agent. Add and dilute with water to 3% and 4% with stock solution to prepare 2 levels of working fluid.
Coating of the processing liquid onto the cotton light heavy cloth uses a small dipping / mangle test machine, and the dipping / mangle squeezing liquid has three levels of one to three passes through each processing liquid. In accordance with Example 1, the solvent was diffused and dried to produce a 6-level fluoropolymer coated fabric.

  As a result of evaluation of each scanning electron micrograph of this sample, 17% and 28% of the work cloths are selected as the ratio of the area of the scale joints as the sample cloths B22 and B23. Samples R22 and R23 were selected by selecting 16% and 29% work cloths.

In addition, on the side of the binder combined processing fabric side, the binder used is 7% of urethane-based resin “PACALL V600B” (trade name, manufactured by Meisei Chemical Industry Co., Ltd.), and an isocyanate-based crosslinking agent is added to the processing liquid. A binder agent combined working fluid was prepared.
Using the binder agent combined working liquid, a binder combined working cloth was manufactured by the same processing method as that of the black sample B22 and sample B24 and the red sample R22 and sample R24.
The ratio of the area of the scale joints of the binder-combined processed cloth was observed to be 18% and 30% for the black binder-combined processed cloth, and these were designated as samples B23 and B25, respectively.
Moreover, about the red binder combined use processing cloth, it was observed as 17% and 32%, respectively, and this was made into sample R23 and R25, respectively.
The evaluation of the fastness to friction was measured according to Example 1. The results are shown in Table 3.

According to Table 3, the frictional fastness of Sample B21 and Sample R21 not processed with fluororesin coating is less than grade 3, whereas the area ratio of the scale joint is 17% for Samples B22 and 28% for black. Sample B24 of 16%, and in red, 16% of sample R22 and 29% of sample R24 were evaluated to show a grade 3-4 or higher that exceeded the third grade of the acceptable level.
Further, the black sample B23 and sample B25 used in combination with the binder, and the red sample R23 and sample R25 were all further improved in frictional fastness.

In addition to the above-mentioned trial manufacture, in addition to the above-mentioned cotton light heavy cloth, rayon spun yarn woven fabric, cupra yarn woven fabric, low-weight cotton woven fabric, etc. were examined as actual product development. It was confirmed.
Further, even when the present invention was applied to cotton jeans dyed with indigo dye, which is said to have low friction fastness, improvement in friction fastness was recognized.

The fine color substance that contaminates the object to be rubbed in the cloth material having low frictional fastness is both in the case of the pigment and dye itself and in the case of the composite fine piece of the pigment or dye and a part of the cloth material.
Although it has been difficult to improve the frictional fastness in the latter case, the present invention has made it possible to significantly improve the frictional fastness.
On the surface of the colored body, the present invention is not a conventionally known spherical PTFE, but a PTFE fine flat scale with good cover efficiency, and this is joined to the surface of the colored cloth as if it were a fish scale group. Thus, the working mechanism of the present invention that makes it difficult to contact the colored fabric surface and the object to be rubbed not only contributes to the improvement in the frictional fastness of the fabric material, but also provides suggestions to a wide range of industries.

Further, in the past, such a product that has been difficult to improve the frictional fastness has been a countermeasure against the dark color, but the application of the present invention has made it possible to provide a dark product.
Furthermore, in the surface processing of a fluororesin system that has been used for soil guard processing, for example, a fluororesin-based surface processing with a small amount of fluororesin such as addition of a fluoroalkyl group, a reduction in friction coefficient could not be expected.
In contrast, in the present invention, the PTFE scale joint, which is a substantially pure fluororesin having a very low friction coefficient, is present on the cloth surface, so that the surface has a highly slidable structure, and the friction object is easy to slide. The friction body is not distorted, and the rubbed body is less likely to come into contact with the original cloth surface, thereby contributing to an improvement in the frictional fastness.

Even when the binder resin is used in combination, since it is in the form of a fine scale of PTFE, the binder resin may be used in a small amount as compared with the case of spherical PTFE. There is.
In addition, since the critical surface tension of the surface of the fabric according to the present invention is reduced, the anti-fouling effect is exhibited, and the friction coefficient of the surface is reduced, so that the fabric is less susceptible to frictional destruction and the durability of the fabric is improved. And contributes to the effective use of materials.

  Magnified schematic diagram of fluoropolymer coated fabric   Schematic cross-sectional schematic view of the fluororesin-coated cloth and the object to be rubbed against each other   Expanded schematic cross-sectional view of the mutual friction part   Side view of the functional part of the friction tester

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Plane schematic drawing 2 AA section cross section schematic 3 Colored cloth 5 Colored cloth surface 6 Scale joint part by PTFE fine flat scale 11 Friction object cross section 12 Friction object surface 13 Friction direction arrow 14 Broken line which shows a part of mutual friction part Circle 20 Fine gap 26 Load arm 27 Rotating fulcrum 28 Friction element 29 Free rotation arrow 30 Friction white cotton cloth 31 Test piece base 32 Measurement test piece 33 Reciprocating direction arrow

Claims (5)

In a woven or non-woven fabric made of cellulose fiber, or a synthetic leather fabric or artificial leather fabric using a flexible elastic resin,
The surface of the cloth is partly a scale joint by a substantially pure polytetrafluoroethylene fine flat scale,
The fine flat scale has a longest diameter of about 2 to 10 μm,
A fluororesin-coated colored cloth, wherein the ratio of the total area of the scale joints to the entire surface area of the cloth is 15 to 50%. In the scale joint part by the polytetrafluoroethylene fine flat scale on the surface of the cloth,
2. The fluororesin-coated colored cloth according to claim 1, wherein a binder resin is interposed between the fine flat scale pieces and the surface of the cloth.   The fluororesin-coated colored fabric according to claim 1 or 2, wherein the knitted fabric or the non-woven fabric made of the cellulose fibers is made of cotton fibers. In the synthetic leather cloth or the artificial leather cloth using the flexible elastic resin,
The fluororesin-coated colored cloth according to claim 1 or 2, wherein the flexible elastic resin is a polyurethane resin. As a solvent, isopropyl alcohol or water, or a liquid in which the polytetrafluoroethylene fine flat scale group is dispersed in isopropyl alcohol and water,
It is applied to the surface of a woven or non-woven fabric made of cellulose fiber, or a synthetic leather cloth or artificial leather cloth using a flexible elastic resin, utilizing the fact that it is liquid,
The processing method which obtains the fluororesin coating colored cloth of Claim 1, 2, 3, and 4 obtained by aerating and drying the said solvent.

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