JPH03184897A - Method for applying fluorcarbon finishing agent - Google Patents

Abstract

PURPOSE: To enhance fiber properties of water repellency, oil repellency and dry staining resistance by adding a layer containing at least one kind of a fluorocarbon resin capable of being transferred to a fiber material finished from a flexible substrate by heat and pressure. CONSTITUTION: An aq. emulsion of a fluorocarbon resin and sebacic acid are ground within a ball mill to obtain a coating compsn. This compsn. is applied to silicone coated release paper by a roll bar and dried to obtain a layer with a thickness of 2-100 μm and a softening range of 70-140 deg.C. Next, this layer is transferred by a transfer printing calender to obtain a chair lining fabric. A low viscosity molten soln. of a dye penetrates into the fabric without changing the appearance or touch of the fabric. Thereafter, the fabric is washed to be dried.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the finishing of textile fabrics by thermal transfer. The present invention relates to flexible two-dimensional, usually web-like auxiliary supports, particularly for finishing textile fabrics, and special methods for the production of such auxiliary supports, as well as to the preparation of finishing agents using the auxiliary supports of the invention. The present invention relates to a method for finishing textile fabrics by a thermal transfer method based on transfer from an auxiliary support to textile fabrics.

When referring to "textile finishing" below, this term will be used as follows:
It is intended to include any treatment or manufacturing method or finished product for end use that enhances the utility of the textile fabric. For example, the term also includes box dyeing and printing.

Thermal transfer printing of polyester knitted and woven fabrics is covered by French Patent No. F.
R-Mu-1,233,330 and 1.585,
119. This method is currently used in routine operation with great success.

One of the advantages of heat transfer printing is the absence of environmental pollution.

A by-product of conventional finishing processes is large amounts of water charged with various forms and amounts of staining agents that require special treatment.

The only major by-product of the thermal transfer process is paper, which can be easily removed by incineration.

Despite various efforts, to date, thermal transfer printing has been limited to polyester fabrics, but it was not until now that this excellent printing method could be extended to other fibers, especially mainline, silk, and wool. Recently.

Conventional thermal transfer printing of polyester fabrics is based on the transfer of dyes from an auxiliary support to textile fabrics by sublimation. Intensive research has shown that it is not possible to select from a group of dyes that sublimate at atmospheric pressure for thermal transfer printing of the most important mainline natural fibers giving prints with satisfactory washfastness.

European Patent No. KP-0,146,509 describes several processes for thermal transfer printing of fibers of cellulose or mixtures of cellulose and polyester.

This patent specification describes a process which is based on the transfer of the printed image from an auxiliary support to a textile fabric by fusing, in which simultaneous sublimation is not excluded.

This method relies on a flexible auxiliary support or carrier coated with a special non-polymeric impregnating agent.

The coated side of the carrier substrate can be printed by any known printing technique, such as powder gravure, rotary screen, flat screen or offset.

During the thermal transfer process, the impregnating agent melts and transfers the impression to the woven fabric. Examples of such impregnating agents are amides of organic acids such as 1-caprolactam, nicotinic acid amide, innicotinic acid amide, urea, zolopylene urea, ethylene urea, glyoxal monourein, 5,5-dimethylhydantoin, imidazole, 2-methylimidazole, N-methylpyrrolidone, N-hydroxysuccinimide, biuret, dicyandiamide, benzamide, toluenesulfonamide, and long chain organic acids such as hippuric acid, suberic acid, azelaic acid, sebacic acid.

These products melt at about 100°C to 250°C.

A detailed description can be found in European Patent Publication No. BP-A-0,146,504.

Commercially available thermal transfer calendars can be used for this purpose, and there is no need to apply other dye fixation methods, such as steaming, after printing. However, after transfer, it is necessary to remove the impregnating agent by washing with water at 40°C.

A significant difference between the traditional thermal transfer printing method based on sublimation, i.e. vapor phase transfer, and the new method based on melting, i.e. liquid phase transfer, concerns the binder.

For the sublimation method, all the binder remains on the auxiliary paper, whereas for the melting method, at least a partial transfer of the binder to the textile takes place.

Experts consider the transfer of binder during thermal transfer to be disadvantageous, and this is very clearly pointed out in many patent publications involving thermal transfer printing. The authors discuss ways to reduce the effect of binders on textiles when binder transfer is unavoidable.

The purpose of the present invention is to show how the transfer of resin from an auxiliary support to textile fabrics can be used to obtain finished resins with properties that meet commercial needs.

A further object of the invention is the special finishing problem, namely the treatment of natural and synthetic fibers with fluorocarbon resins.

These types of finishes have been known for many years.

Many fluorocarbon resins are generally fully or partially fluorinated olefins.

To date, aqueous emulsions of fluorocarbon resins are commonly used alone or in combination with other resins.

These emulsions typically have a solids content of about 30%
Contains. These are diluted and then applied to the fibrous material, for example by pad mangle with a loading of 0.3% solid fluorocarbon to 0 weight of fabric. Application is followed by drying at approximately 80° to 120°C and then 15°C.
Condensation occurs at 0°C to 180°C. Fluorocarbon resin is
Applicable to virtually all natural and synthetic fibers.

Finishing with fluorocarbon resins helps improve the following fiber properties:

1. Water Resistance 2. Bowl Oil Resistance 6. Dry Stain Resistance The amount of water resistance is usually analyzed in at least two different aspects: 1. Resistance of the fiber surface to water absorption (e.g. Bunclesman D Engineering N 53'88
Rainfall test using No. 8). This test is important for example in the clothing industry.

2. Resistance to water penetration through the fibers of the treated textile upon application of a certain water pressure. The quality of the finish is measured by the highest water pressure that can be applied without water penetration through the fabric (D Engineering N53'886)Q This property is important for example in awnings and tents.

The oil-grinding properties of textile surfaces are evaluated by examining their resistance to wetting by liquid hydrocarbons of various surface tensions.

The combination of oil resistance and water resistance results in stain resistance of Finish 0 fabrics. Fluorocarbon finished fabrics also exhibit increased resistance to dry stains.

A further object of the invention is to improve the possibilities of conventional finishing methods and to obtain effects that are not or difficult to obtain by conventional means.

To obtain this, the present invention is based on European Patent No. BP-A-0
．． Based on No. 146,504.

The purpose discussed above is to have a layer of a thermally transferable finish on a flexible substrate, particularly paper, about 2 micrometers to 100 micrometers thick and hydrophobic, the main component of which is a fluorocarbon. Obtained by the auxiliary support of the present invention, which is a resin.

A particular embodiment of this support, which can be combined with one another, exhibits the following properties: 1. The base paper and the waste containing the finishing agent may be separated by a release film.

2. The layer containing one or more fluorocarbon resins may further contain other polymers that are transferred to the woven fabric at least in part during thermal transfer.

6. The layer may contain one or more impregnating agents to help improve the speed and efficiency of the transfer process.

4. The auxiliary support may carry other agents, especially dyes and pigments, which improve the results of the thermal transfer process.

The transcription method of the present invention is further defined in an independent frame combined with dependent images for special applications.

Furthermore, the present invention relates to a new and useful method for producing auxiliary supports, which are the subject of dependent frames as well as other independent frames.

Various applications of the invention will now be discussed in detail.

Textile fabrics that can be treated according to the invention include natural or synthetic fibers or mixtures thereof, such as silk, woven or non-woven fabrics such as cotton, linen, silk, wool, rayon, polyester, polyamide, polyolefin, acrylic, polyurethane, etc. include.

According to one embodiment of the invention, the auxiliary support contains at least one impregnating agent for fibrous materials in a layer of finishing agent. A suitable impregnating agent is European Patent No. FP-A-0.146.50
In Specification No. 4, in particular, penzuabad, nicotinamide, urea and its 8-conductor, p-)luenesulfonamide, 5,5-dimethylhydantoin, dicyandiamide, hippuric acid, suberic acid, azelaic acid, p- and sebacic acid. and mixtures thereof. In this embodiment of the auxiliary support, the impregnating agent has at least a dual function. These reach the transfer temperature, forming a melt with low viscosity and effecting the transfer of the finishing agent from the surface of the auxiliary support into the fiber structure. Although the method of the present invention is not a "reverse coating" as used in polyurethane coatings, after transfer virtually no film remains on the treated surface of the fiber material and the fiber structure is similar to that of traditional finishing methods with aqueous emulsions. It is important to know that the molten product is processed in the following manner.

6 Impregnating agents also facilitate the paper coating process. because,
This is because the coated surface shows no blocking after drying.

Commercially available fluorocarbon resins generally include a mixture of several different fluorocarbon resins.

Among these, resins with a low temperature softening range can be found. One of these, for example, has a melting point range of 70℃~
140°C.
TheO (lor Rotta GmbH & Co.

KG), Divorito, Mannheim, Germany
pOlit) 451.

This type of resin is one type of "internal" for other aspects of the invention.
It is an impregnating agent.

They can be used alone or in mixtures with other knitting layers, high melting point fluorocarbon resins or other polymers to form coatings that can be melted and transferred from release papers into fabrics without the addition of conventional impregnating agents. can be given. A distinct advantage of this embodiment of the invention is that the impregnating agent does not need to be removed after transfer.

Additionally, the fabric was padded with water and then 16 minutes after transfer.
Drying at 0° is recommended.

This system requires - a higher contact pressure, e.g.
MPa to 1 MPa is recommended.

For many types of textile fabrics, especially flat constructions, conventional fiber calenders can be used in the inventive method instead of special thermal transfer calenders. In these cases, 160℃~210℃
Linear contact pressure at ℃ 5ON/mu~40ON/s
+x machining speed and fabric processing speed 10 m/min~10
0 m/min is recommended.

The method of the invention is of interest for all fibers. This is because it provides a quick and low risk method.

When processing by conventional finishing methods on fabric samples of unknown origin, there is always a risk that the entire finishing bath may be rendered unusable by colored or uncolored impurities released by hanging.

A further object of the invention is to finish the polyester fabric with a fluorocarbon resin (Trevira 5 O8, Hoechst) in order to impart flame retardancy to the polyester fabric.

"Flame retardant" refers to textile fibers that do not burn for longer than 6 seconds after the flame is extinguished after 15 seconds of exposure to a propane gas flame at a 45° angle with the fabric sample.

German Patent No. 2,236,037, German Patent No. 2,442,
No. 002, No. 2,328,343, No. 2,346
．． No. 787 discloses polyester flame retardant fibers in which about 5 mole percent to 15 mole percent of the acid component of the polyester is phosphorus-containing groups. The total phosphorus content of the polyester molecule is less than 1%.

From at least 1978 [for example, Dr. H. Zimmermann's ``C!
fasern / Textilindustrie
) J 28/80 (1978), 1054-10
60)], the flame retardancy of these fibers is not known to be degraded by fluorocarbon resin finishes when applied by any technique known prior to the method of the present invention. There is.

6. When a Trevira aS fabric is finished with a fluorocarbon resin according to the method of the invention, this Trevira aS fabric does not change its flame retardancy. It is now possible to apply finishes to Trevira aS fabrics that make them water-resistant, oil-resistant, dry-stain-resistant buttons, and watertight while preserving the flame retardant properties of the Trevira aS cloth.

Besides the fluorocarbon resin, the layer of the auxiliary support may contain other auxiliary agents such as polymeric softeners, dyes, pigments, etc. to impart special finishing properties to the knitted fabrics treated by the method of the invention. You may get it.

The following examples are presented solely for illustrative purposes only and do not delineate the scope of the invention.

Example 1 In a ball mill, fluorocarbon resin [Scotchgard (TM) FC-24]
A coating composition is prepared by grinding 72 parts of an aqueous emulsion of No. 7 (3M Company) with 28 parts of sebacic acid until the average particle size of the sebacic acid is 10 μm or less. 40
A silicone-coated release paper of g/1rL2 is coated with this composition 8θ/rrL2 by means of a roll bar and then dried. This layer was heated to 160°C and subjected to a thermal transfer printing calendar for 25 seconds under an increased contact pressure of 3.2 MPa.
A Trevira C day chair upholstery fabric having a basis weight of 650 g/rIL2 was obtained.

A low viscosity melt of paint penetrates the fabric without changing its appearance or texture. Thereafter, the fabric is washed with water at 40°C and then dried at 160°C.

3M has developed Scotchcard(TM) specifications and control methods for various applications of fluorocarbon finishes.
Scotchgard (TM) Fabric Protector
Quality Specifications for Home Furnishings, Technical Information Oshi 5M (Scotchgard (TM)
) Fabric Protector Qu (11i
tySpecifications for Home
Furnishings.

8 Technic (11Information of
3 M N January 10, 1988]).

In this example, the finished product has a vulcarocarbon content of 0.
351 (3M specification 0.3%-).

For oil grindability, a code 6 was observed (minimum value 4), and for dry sewage resistance, code 5 (minimum value 3) was observed.

The flame retardancy of this fabric was measured by D Tech 14102,
No difference was observed between the weight of the finished fabric and the unfinished fabric.

In both cases, i.e. untreated fabric and finished fabric, the sample burns less than 0.5 seconds after extinguishing the test flame;
Furthermore, the length of the destroyed fabric was the same for both samples.

Example 2 9 Basis weight 300. ! An awning fabric having a //- was constructed from Trevira C8 fibers.

Using the coated paper of Example 1, the fabric was treated in a thermal transfer printing calendar at 160 DEG C. with a contact pressure Q of 5 MPa and a contact time of 25 seconds. After heat transfer, this fabric was heated to 40°C.
of water and then dried at 180°C.

The fabric was then treated on a fiber calender (first cylinder surface, steel; second cylinder surface, compressed cotton).

Water resistance tests with D-Tech M53886 showed that the fabric treated in this way withstood a pressure of 250 mg of water without leaking.

The treated fabric passed the DIIT4102B1 flammability test.

Example 3 Aqueous fluorocarbon emulsion “Scotchgard T”
The second part of M FO-247J (3M)
Daibolito 451J, a low melting point fluorocarbon polymer from
The coating composition is prepared by mixing 1 part with 1 part.

This composition is used to coat the base paper of Example 1 in a powder gravure machine. After drying, the basis weight of the coating is approximately 51/m
”I was disappointed.

180℃ thermal transfer printing calendar, contact pressure 1MPa
The paint was transferred to the upholstery fabric of Example 1 using k and a contact time of 25 seconds.

After transfer, the fabric was first padded with some water on a pad mangle, and then the fabric was dried at 160°C.

Finish values were essentially the same as those of Example 1. The treated fabric passed the combustion test according to D-Tech N4102, B1.

Example 4 1 was processed on a conventional fiber calender. Calendar 1
The drum had a steel side and a compressed cotton other side.

The paper and fabric were calendered at a line contact pressure >300 N/miK and at a speed of 20 m/min. The high pressure transferred 80% of the releasable paint from the paper to the fabric.

After washing with water at 40°C and drying at 160°C,
Substantial finishing parameters were obtained without any negative impact on the flame retardancy of the fabric.

Example 5 finishing The procedure of Example 4 was repeated using the paper of Example 3.

It was found that approximately 65% of the releasable paint was transferred from the paper to the fabric. After transfer, the fabric was treated with water as described in Example 5.

Excellent results were obtained in the final singing and combustion tests.

2

Claims (13)

[Claims] (1) A two-dimensional auxiliary support for finishing textile materials produced from natural or synthetic fibers or mixtures thereof by a thermal transfer method, said support comprising a flexible substrate and a flexible substrate on one surface thereof. a thickness of about 2 μm to 1 μm containing at least one fluorocarbon resin transferable by heat and pressure from a flexible substrate to a finished fibrous material
A two-dimensional auxiliary support for the finishing of textile materials, characterized in that it comprises a layer having a diameter of 0.00 μm. (2) The auxiliary support of claim 1, wherein the transferable layer is separated from the flexible substrate by a release layer. (3) The transferable layer is ε-caprolactam, nicotinamide, isonicotinamide, hippuric acid, suberic acid,
Azelaic acid, sebacic acid, urea, propylene urea, ethylene urea, glyoxal monourein, 5,5-dimethylhydantoin, imidazole, 2-methylimidazole, N-methylpyrrolidone, N-hydroxysuccinimide, biuret, dicyandiamide, benzamide , 1 selected from the group consisting of toluenesulfonamide
Claim 1 further comprising an impregnating agent for the textile material to be finished, consisting of one or more substances.
The auxiliary support according to item 1 or 2. (4) The transferable layer further comprises a polymeric binder that is at least partially transferable to the fibrous material during a thermal transfer process. The auxiliary support described in . (5) The auxiliary support according to any one of claims 1 to 3, wherein the layer contains a fluorocarbon resin having a softening range of 70°C to 140°C. (6) (a) providing a two-dimensional flexible substrate; (b) providing a liquid coating composition containing an aqueous emulsion of at least one fluorocarbon resin; and (c) providing the flexible substrate of step (a). coating a flexible substrate with the coating composition of step (b) such that after drying the layer of coating composition yields a coating layer having a thickness of 2 micrometers to 100 micrometers; death,
A method for producing an auxiliary support according to claim 1, characterized by the step of: (d) drying the coated flexible substrate. 7. The method of claim 6, wherein an impregnating agent selected from the substances defined in claim 3 is further incorporated into the liquid composition in step (b). 7. The method of claim 6, further comprising: (8) coating the flexible support of step (a) with a release layer. (9) In a thermal transfer printing calendar, the contact pressure between the fiber material and the auxiliary support is about 0.01 MPa to about 1 M at standard atmospheric pressure.
Pa, contact time about 5 seconds to about 100 seconds, temperature about 130℃ ~
consisting of natural or synthetic fibers or mixtures thereof, characterized in that the fibrous material is brought into contact with an auxiliary support according to any one of claims 1 to 5 at about 250°C. How to apply fluorocarbon finishes to textile materials. (10) In a fiber calender, at standard atmospheric pressure, the line contact pressure between the fiber material and the auxiliary support is from about 50 N/mm to about 5
00 N/mm and at a temperature of about 130°C to about 220°C, the fibrous material is brought into contact with the auxiliary support of any one of claims 1 to 5, or a mixture thereof. A method of applying a fluorocarbon finish to a fibrous material consisting of. (11) The method according to claim 9 or 10, wherein the textile fabric is manufactured from polyester fibers. (12) using the auxiliary support of claim 5, said layer being free of impregnating agents, and further padding the resulting finished fiber material with water and then heating the padded fiber material to about 160°C. 11. The method of claim 9 or claim 10, wherein the method is dried in a drying step. (13) A textile fabric finished by the method according to any one of claims 9 to 12.