JPH0770946A - Method for producing polyester coated fabric - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a method for producing a polyester-coated cloth having an excellent effect of preventing disperse dyes of a base cloth from migrating and contaminating a coating layer of a polyurethane resin or a polyamino acid urethane resin. [Structure] A polyester fiber cloth dyed with a disperse dye is coated with a coating resin solution of polyurethane resin or polyamino acid urethane resin containing an electron beam crosslinkable monomer to form a coating film, and then the coating film is oxygen-containing. Irradiate with an electron beam in an atmosphere with a concentration of 500 ppm or less. [Effect] A coating film made of a versatile polyurethane resin or polyamino acid urethane resin is used as a coating film without using a melamine derivative that causes hand-curing and without performing treatment under high vacuum. Dispersion of the disperse dye to the polyester-coated cloth having excellent anti-staining performance can be produced.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyester-coated cloth having an excellent effect of preventing dye transfer contamination.

[0002]

2. Description of the Related Art Conventionally, a coating process for imparting functions such as water / oil repellency and moisture / water resistance to a cloth mainly composed of nylon fibers has been performed, and it has been used as sports clothes, rain clothes, and industrial materials. However, for nylon-based fiber cloth,
There is a problem that the light fastness, wet fastness, and chlorine fastness of the dye are low, and there are also drawbacks such as poor mechanical properties such as dimensional stability and wrinkle resistance.

In recent years, there has been a tendency to use polyester fibers, which have excellent physical properties and are inexpensive, as a coating base fabric. However, polyester fiber cloths are usually dyed with disperse dyes, so when coating is applied to them, the disperse dyes used over time migrate to the coating film and contaminate the coating film. There was a fatal drawback.

In order to solve such a problem, in Japanese Patent Laid-Open No. 62-28484, a melamine derivative is steamed and then subjected to plasma treatment to crosslink the melamine derivative to form a film. A method of preventing migration, as seen in JP-A-3-14677,
After forming a polymerized film on the fiber surface by low-temperature plasma treatment in a polymerization gas atmosphere such as ethylene or tetrafluoroethylene, low-temperature plasma treatment is performed in a non-polymerization gas atmosphere such as argon or helium. Methods such as cross-linking the membrane have been proposed.

However, the former has a problem that the film of the melamine derivative hardens the texture, and the latter has a complicated process and requires treatment under a high vacuum, so that the sample is in an absolutely dry state. There were problems such as having to

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of such a situation as described above, and it is possible to perform the treatment under a high vacuum without using the melamine derivative which causes the hand-hardening. The purpose of the present invention is to obtain a polyester-based coated cloth having excellent performance of preventing dye migration and contamination by using a polyurethane resin or a polyamino acid urethane resin in the coating film.

[0007]

SUMMARY OF THE INVENTION The present invention achieves the above object and has the following configuration. That is, the present invention is a coating film obtained by applying a coating resin solution composed of a polyurethane resin or a polyamino acid urethane resin-based synthetic polymer containing an electron beam crosslinkable monomer to a polyester fiber cloth dyed with a disperse dye. The present invention is directed to a method for producing a polyester-based coated cloth, which comprises irradiating the coating film with an electron beam in an atmosphere having an oxygen concentration of 500 ppm or less after forming the film.

The present invention will be described in detail below.

In the present invention, a polyester fiber cloth dyed with a disperse dye is used as an object of coating processing.

The polyester fiber cloth referred to here is
A woven fabric, a knitted fabric, a non-woven fabric, etc., which is mainly composed of polyethylene terephthalate fiber or polybutylene terephthalate fiber, and nylon, cotton, wool, rayon, etc. are knitted, knitted, or mixed-spun within a range that does not affect the effect of the present invention. , May be used by means such as mixed fiber.

The disperse dye is a known disperse dye that can diffuse into ordinary polyester fibers, and the dyeing method may be carried out under the conditions conventionally used.

In the present invention, the above-mentioned fiber cloth may be used which has been previously treated with a water repellent agent. This is one means for preventing the penetration of the coating resin solution into the fabric.
In this case, the water repellent may be a known one such as a paraffin water repellent, a polysiloxane water repellent, or a fluorine water repellent, and the treatment thereof may be a padding method, a spray method or the like which is generally performed. A known method may be used. If particularly good water repellency is required, use a fluorine-based water repellent, for example, after padding Asahi Guard 730 (Asahi Glass Co., Ltd., fluorine-based water repellent emulsion) with a 5% aqueous dispersion. The heat treatment may be performed at 160 ° C. for 1 minute.

In the present invention, a coating film is formed by coating the above polyester fiber cloth with a coating resin solution made of a synthetic polymer mainly composed of a polyurethane resin or a polyamino acid urethane resin containing an electron beam crosslinkable monomer.

The electron beam crosslinkable monomer used here is
By irradiating the monomer with an electron beam, it is ionized or excited to cause addition of monomers or bond between radicals to form a crosslinked film. Specifically, 1.4-butane is a monomer. Examples include monomers such as diol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, and trisacryloyloxyethyl phosphate.

The polyurethane resin used here is a reaction product containing a polyol having hydroxyl groups at both ends, an organic diisocyanate, and a chain extender.

Examples of the polyol component include polyether polyol, polyester polyol, a mixture or copolymer of these, and the polyether polyol includes polyethylene glycol,
Polypropylene glycol, polytetramethylene glycol, etc. may be mentioned, and as the polyester polyol, diols such as ethylene glycol, propylene glycol, hexamethylene glycol and dibasic acids such as adipic acid, sebacic acid, maleic acid and terephthalic acid are used. Examples thereof include polycondensates and ring-opening polymers such as caprolactone and lactone acid.

As the organic diisocyanate component, aromatic diisocyanate, resinous diisocyanate and alicyclic diisocyanate may be used alone or in a mixture thereof.・
6-hexane diisocyanate, 1,4-cyclohexane diisocyanate and the like can be mentioned.

As the chain extender, ethylene glycol,
Examples thereof include compounds having active hydrogen such as diols such as propylene glycol and hexamethylene glycol and diamines such as ethylenediamine, metaphenylenediamine and naphthylenediamine.

The synthetic polymer mainly composed of the polyamino acid urethane resin used in the present invention is a synthetic polymer containing 70 to 100% of the polyamino acid urethane resin (of course, 100% of the polyamino acid urethane resin may be used). ，
Other synthetic polymers may include, for example, a block copolymer of poly-γ-alkyl glutamate and butadiene or a block copolymer of poly-γ-alkyl glutamate and leucine in an amount of less than 30%.

The polyamino acid urethane resin (hereinafter referred to as PAU resin) used in the present invention is a copolymer composed of amino acid and polyurethane, and the amino acids include DL-alanine, L-aspartic acid and L-cystine. , L-glutamic acid, glycine, L-lysine, L-methionine, L-leucine and derivatives thereof. When synthesizing a polyamino acid, an amino acid N-carboxylic acid anhydride obtained from an amino acid and phosgene (hereinafter N-carboxylic acid anhydride is referred to as NCA), but an optically active γ-alkyl glutamate-NCA is preferably used particularly from the viewpoint of film performance, and among them, γ-methyl- L-glutamate-NCA or γ-methyl-D-glutamate-NC
Often, A is advantageously selected as the amino acid component of the PAU resin.

On the other hand, as the polyurethane, a urethane prepolymer having an isocyanate group at the terminal, which is obtained by reacting an isocyanate and a polyol under the condition of an equivalent ratio NCO / OH> 1, is used. As the isocyanate component, aromatic diisocyanate, aliphatic diisocyanate and alicyclic diisocyanate may be used alone or in a mixture thereof.
4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexane diisocyanate, 1
-4-cyclohexane diisocyanate etc. are mentioned. As the polyol component, polyether polyol, polyester polyol, etc. are used. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like, and as the polyester polyol, a reaction between a diol such as ethylene glycol and propylene glycol and a dibasic acid such as adipic acid and sebacic acid. Examples thereof include products and ring-opening polymers such as caprolactone.

As amines used in the copolymerization of amino acid and polyurethane, hydrazine, ethylenediamine, diethylamine, triethylamine, ethanolamine and the like are used.

As described above, the PAU resin is obtained by adding amines to the reaction system of various amino acids NCA and the urethane prepolymer having an isocyanate group at the terminal.

In the present invention, the electron beam crosslinkable monomer is contained in the above-mentioned synthetic polymer mainly composed of the polyurethane resin or the polyamino acid urethane resin, and the concentration of the electron beam crosslinkable monomer at this time has a target performance and a feeling. Although it may be appropriately determined in consideration, it is usually preferably about 0.5 to 20% by weight based on the weight of the coating resin film. If the concentration of the electron beam crosslinkable monomer is less than 0.5% by weight, the effect of preventing migration and staining of the dye, which is the object of the present invention, becomes insufficient.
If it exceeds 0% by weight, the texture of the fabric after processing becomes coarse and hard, which is not preferable.

A well-known method may be used to prepare a coating resin solution composed of a synthetic polymer mainly composed of a polyurethane resin or a polyamino acid urethane resin containing an electron beam crosslinkable monomer. 2,000 to 40,000 cp considering workability during coating
It is preferable that the temperature is adjusted to (25 ° C.) and further filtration with a 20 to 200 mesh filtration membrane is performed in order to remove the resin particles.

In order to form a coating film by applying the resin solution, the above-mentioned dyed cloth is coated with the polyurethane resin solution or the PAU resin solution by an ordinary coating method, for example,
After coating with a knife coater, comma coater, reverse coater, etc., it is immersed in water for wet coagulation, or a dry method in which a solvent-based, water-based or emulsion-based resin liquid is applied by the above coating method and then heat treated. be able to.

After forming the coating film, in the method of the present invention, the coating film is irradiated with an electron beam in an atmosphere having an oxygen concentration of 500 ppm or less. The electron beam irradiation at this time is 5
It is necessary to carry out at an oxygen concentration of 00 ppm or less. If the oxygen concentration exceeds 500 ppm, the radicals generated by electron beam irradiation will disappear within a short time, and the coating film will not be crosslinked and the dye Care must be taken because the effect of preventing migration and sublimation becomes poor. Oxygen concentration is 100pp
Even more preferable results are obtained when the value is m or less. The gas other than oxygen is not particularly limited, but it is preferable to use a gas that does not extinguish the radicals generated by the electron beam irradiation, and for example, argon, helium, nitrogen gas or the like can be preferably used.

The irradiation dose of the electron beam may be appropriately determined according to the desired performance, and the normal irradiation dose is appropriately about 1 to 30 megarads (hereinafter abbreviated as Mrad), preferably 5 ~ 20 Mrad. Irradiation dose is 1M
If it is less than rad, it is difficult to obtain sufficient cross-linking, and if it exceeds 30 Mrad, physical properties are deteriorated due to deterioration of the coating film and the fiber, which is not preferable.

The accelerating voltage may be appropriately selected depending on the thickness of the coating film to be treated, and is usually 150 to 300.
Kilovolt (hereinafter abbreviated as KV) is suitable.

By the above-mentioned method of the present invention, the effect of preventing dye migration contamination to the coating film is excellent without using a melamine derivative which causes a hand-hardening and without performing a treatment under high vacuum. It is possible to obtain a polyester-based coated fabric.

The present invention has the above configuration.

[0032]

[Working] As in the present invention, a coating film of polyurethane resin or polyamino acid urethane resin containing an electron beam crosslinkable monomer is formed on a polyester fiber cloth dyed with a disperse dye, and an electron beam is applied to the coating film. When irradiated, the electron beam crosslinkable monomer in the coating film is activated and cross-links and polymerizes to strongly crosslink the coating film, which prevents the disperse dye in the polyester fiber cloth from migrating to the coating film.
As a result, the polyester coated fabric of the present invention exhibits good dye transfer contamination prevention performance.

[0033]

EXAMPLES The present invention will be described in more detail below with reference to Examples. The method for measuring the dye transfer contamination prevention performance of the coated cloth in the Examples is JIS L-0854 "Dyeing fastness test against sublimation during storage". According to the method, coated fabrics of polyester fibers dyed in dark and light colors are left with their coated surfaces overlaid, and the dyes of the dark coated fabrics are transferred to the coated faces of the light coated fabric. The degree of contamination was evaluated on a gray scale.

Example 1 Woven fabric taffeta made of polyethylene terephthalate fiber (yarn usage: warp 50d / 18f, weft 75d / 36f,
Density: 109 pieces / inch, weft 79 pieces / inch) was refined by a conventional method, and heat set at 180 ° C. for 1 minute. Next, using a blue disperse dye Miketone Blue FBL (manufactured by Mitsui Toatsu Dyes Co., Ltd.) as a dye for a dark dyeing cloth, 3
% Owf at a concentration of 1% owf at a concentration of 1% owf using a brightening agent Ubitex EBF (manufactured by Ciba-Geigy Co., Ltd.) as a dye for dyeing a light-colored cloth.
Dyeing was performed under the condition of 30 minutes. Here, the dark-colored dyed cloth is subjected to reduction cleaning by an ordinary method, and the light-colored dyed cloth is not subjected to reduction cleaning.
Heat setting was performed at ℃ for 1 minute.

Both these dyed cloths were padded with an Asahi Guard LS-317 (Asahi Glass Co., Ltd.) 8% aqueous solution which is a fluorine-based water repellent emulsion (squeeze ratio 38%).
After processing, dry at 80 ℃ for 5 minutes,
Heat treatment was performed at ℃ for 1 minute.

Then, using a calendering machine having a mirror surface roll, the temperature was 180 ° C., the pressure was 35 kg / cm ² , and the speed was 20.
After calendering under the condition of m / min and subsequently applying a coating resin solution containing an electron beam crosslinkable monomer shown in the following Formulation 1 at a coating amount of 100 g / m ² using a knife over roll coater. Then, it was dried at 80 ° C. for 2 minutes and further heat-treated at 150 ° C. for 1 minute to obtain a coated cloth.

Formulation 1 Heimlen X-3040 100 parts by weight (Dainichi Seika Kogyo Co., Ltd., polyurethane resin) Viscoat # 335HP 3 parts by weight (Osaka Organic Chemical Industry Co., Ltd. electron beam crosslinkable monomer) Methyl ethyl ketone 15 parts by weight Toluene 15 parts by weight Resamine X 2 parts by weight (Daisin Seika Kogyo KK, isocyanate compound) Water 40 parts by weight

The coated surface of the obtained coated cloth was irradiated with an electron beam under the conditions of an accelerating voltage of 200 KV, an irradiation dose of 100 Mrad and an oxygen concentration of 10 ppm, and a polyester coating cloth excellent in dye migration contamination prevention performance by the method of the present invention. Got

For comparison with the present invention, a work cloth for comparison (comparative example) was prepared in the same manner as in this example except that the biscoat # 335HP of formulation 1 was omitted and the electron beam irradiation step was omitted in this example. 1) was obtained. Further, a work cloth for comparison (Comparative Example 2) was obtained in the same manner as in this Example except that the electron beam irradiation step was omitted in this Example. Furthermore, for comparison with the present invention, a work cloth for comparison (Comparative Example 3) was obtained in the same manner as in this Example except that the oxygen concentration during electron beam irradiation was 600 ppm in this Example. .

The dye transfer stain prevention performance of the present invention and the comparative processed cloth were measured, and the results are shown in Table 1.

[Table 1]

As is clear from Table 1, the coated fabric produced by the method of the present invention had an excellent dye transfer stain prevention performance.

[0042]

EFFECTS OF THE INVENTION According to the present invention, a versatile polyurethane resin or polyamino acid urethane resin is coated without using a melamine derivative which causes hand-curing and without performing treatment under high vacuum. When used in a coating, it is possible to produce a polyester-based coated cloth having excellent anti-staining performance of dye migration to the coating.

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Claims (1)

[Claims] 1. A coating film is formed by applying a coating resin solution composed of a polyurethane resin or a polyamino acid urethane resin-based synthetic polymer containing an electron beam crosslinking monomer to a polyester fiber cloth dyed with a disperse dye. After the formation, the coating film is irradiated with an electron beam in an atmosphere having an oxygen concentration of 500 ppm or less.