JPH0381782A - Recording method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method of recording on another base material using a toner image formed on an electrostatic recording medium. Especially CA D (Computer Aided Qesig)
n) technology, and CG (Computer Graphics)
The present invention relates to a method of recording a graphic image created using a p-hics technology on an electrostatic recording medium and then recording it on a base material such as cloth, nonwoven fabric, or synthetic resin film.

(Prior art) When recording a desired pattern, design, or image information on fabric, it is necessary to change the thread color or weaving method during weaving, or add a thickening agent to a solution of colorants, resist dyes, etc. There was a method in which viscous printing paste was selectively attached to fabric using a rotary printing machine or a screen printing machine to color or bleach the fabric. but,
This method is convenient when producing a large amount of the same product, but when producing only a small amount or on a trial basis, there are problems such as high cost and time.

On the other hand, CAD and CG technologies have been developed to use computers and scanners to design clothing, umbrellas, bags, poster catalogs, flyers, wrapping paper, etc. - Outputting has the advantage that large, clear records can be obtained quickly, easily, and at low cost.

It was considered to create an electrostatic recording medium using cloth as a support and record it with a color electrostatic plotter (Japanese Patent Application No. 1983-
327694), there were problems such as loss of flexibility and texture of the fabric and lack of water resistance.

Furthermore, when recording a color image using a thermal transfer recording method, equal-sized four-color ink donor films (black, cyan, magenta, and yellow) are required, resulting in high costs. Also, the recording size is A-3.
There was a problem that only the size smaller than the size could be recorded.

(Problems to be Solved by the Invention) The present invention is particularly applicable to dyeing a small number of fabrics when a design created using CAD and CG technology is woven or dyed into fabric using a loom or a printing machine. The aim is to solve problems that are time consuming and costly.

Further, in thermal transfer recording, the present invention aims to solve the problem of high cost caused by ink donor films and to enable recording of large sizes exceeding A-3 size.

In addition, as a method to solve the above problem, a mirror image of the design created using CAD and CG technology is recorded using a color electrostatic plotter with color toner containing sublimable dye, and then the mirror image of the design created using CAD and CG technology is recorded with color toner containing sublimable dye. A method has been devised in which a substrate made of synthetic resin or synthetic resin-coated paper is contacted and heated to dye the substrate with a sublimable dye, but the sublimable dye dyes the electrostatic recording medium. This is an attempt to solve the problem that the dyes adhere to the substrate, lower the dyeing efficiency of the substrate, and reduce the dyeing density.

(Means for Solving the Problems) The present inventors have proposed a method for transferring a design created using CAD and CG technology to a base material made of fabric, nonwoven fabric, synthetic resin, synthetic resin coated paper, etc. As a result of intensive study, we have completed the present invention.

That is, the present invention provides a mirror image of a design created using CAD, CG technology, etc. on an electrostatic recording material in which a conductive layer, a dye barrier layer, and a heat-resistant dielectric layer are sequentially provided on at least one side of a heat-resistant support. After recording using a color electrostatic plotter and developing with toner containing sublimable dye, electrostatic recording is performed by contacting a substrate made of fabric, nonwoven fabric, synthetic resin film, or synthetic resin coated paper. This is a method of dyeing a substrate with a sublimable dye by heating from the back side of the body or from the substrate side to a temperature higher than the sublimation temperature (150 to 200° C.) of the dye.

In order to prevent the electrostatic recording material from softening, deforming, or adhering to a heating device due to heating, it is necessary to use a heat-resistant support.

As the heat-resistant support, for example, papers such as high-quality paper and medium-quality paper, and heat-resistant films such as polyethylene terephthalate film and polycarbonate film can be used.

Furthermore, in order to prevent the dielectric layer resin from softening due to heating and adhering to the substrate to be transferred, it is necessary to use a heat-resistant dielectric layer resin or to increase the pigment ratio in the dielectric layer. The dielectric layer has a thin film thickness of 1 to 10 μm, and the higher the pigment ratio, the higher the air permeability, so dye molecules sublimated by heating pass through the dielectric layer and dissipate toward the conductive support, causing damage to the base material. It has the disadvantage of reducing dyeing efficiency. The present invention provides a dye barrier layer between the conductive layer and the heat-resistant dielectric layer to prevent further dissipation of dye molecules that have passed through the dielectric layer, thereby increasing the dyeing efficiency of the substrate.

The conductive layer includes an ion conductive type conductive agent, such as a cationic conductive agent such as polyvinylbenzyltrimethylammonium chloride, polydimethyldiallylammonium chloride, or styrene-acrylic acid trimethylaminoethylammonium chloride copolymer, on at least one side of the heat-resistant support. Or a conductive paint containing an anionic conductive agent such as polystyrene sulfonate, polyacrylate, polyvinyl phosphate, etc. and, if necessary, a pigment and an adhesive, or a breath bottom mold with a pressure of 150 kg/cm2. Conductive powder with a measured volumetric electrical resistance value of 10-5 to 103 Ω·cm, such as zinc oxide doped with aluminum,
A metal oxide powder such as antimony-doped stannic oxide, or a powder in which the stannic oxide is deposited on the surface of an inorganic pigment such as mica, titanium dioxide, and calcium carbonate, or a metal powder such as silver powder, A conductive paint containing an electron conductive powder such as cuprous oxide powder and a heat-resistant adhesive, such as a water-soluble adhesive such as starch, methyl cellulose, or hydroxypropyl cellulose, or a thermosetting heat-resistant resin. It can be obtained by coating so that the coating amount after drying is 0.5 to 20 g/m2.

Coating is done by the usual coating methods, such as air knife coating method, Meyer bar coating method, blade coating method, reverse roll coating method, slit die coating method, comma roll coating method, and size press coating method. You can do it.

The coating amount is such that the surface electrical resistance value of the conductive layer is 1×105 to 1×1.
It is necessary to adjust it so that it becomes 0BΩ. The dye barrier layer is made of a water-soluble resin such as methylcellulose, polyvinyl alcohol, polyacrylic acid, gelatin, butyl methacrylate grafted gelatin, ethyl acrylate grafted gelatin, ethyl methacrylate grafted gelatin, cellulose monoacetate, polyacrylamide, polyisopropylacrylamide, etc. It can be obtained by coating alone or in combination of two or more types so that the coating amount after drying is 0.1 to 2 g/m2. The coating method can be the same as that used for coating the conductive layer.

Di9-layer resin and volume electrical resistance value of 1011Ω・cm or more,
Desirably, it is 1012 Ω・cm or more, has a high melting point,
If necessary, hardening agents such as cyanate esters, diamines, and acid anhydrides can be added to resins that cannot be dyed with sublimable dyes, such as phenol resins, urea resins, melamine resins, epoxy resins, urethane resins, silicone resins, and acrylic resins. It is possible to use resins that are added to make them thermosetting.

Linear saturated polyester resins such as polyethylene terephthalate, nylon 66 resins, and the like are not preferred because they are dyed with sublimable dyes and reduce the dyeing efficiency of the substrate.

Heat-resistant resin and inorganic pigment such as calcium carbonate, clay, aluminum hydroxide, titanium dioxide, or heat-resistant organic pigment such as starch particles, urea resin beads, benzoguanamine resin beads, etc. in a ratio of 100/25 to 100/150. A heat-resistant dielectric layer can be formed by coating the mixed coating material on a conductive support so that the coated amount after drying is 2.0 to 7.0 g/m2.

As the coating method, usual coating methods such as a Meyer bar coating method, a gravure roll coating method, a reverse roll coating method, a blade method, a slit die coating method, a comma roll coating method, etc. can be used.

As the sublimable toner used in the present invention, a liquid toner in which a coloring agent consisting of a disperse dye or a basic dye, a coating agent, and an additive are dispersed in a carrier liquid can be used.

The sublimable dye used as a coloring agent is a monoazo dye represented by the general formula %, where R1 is a methyl group, an ethyl group, a trifluoromethyl group, a linear or branched propyl group, or a butyl group; It represents a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, and R2 represents a methyl group, an ethyl group, a methoxy group, or an ethoxy group.

Anthraquinone dye represented by the general formula 1111. R2 represents a methyl group, an ethyl group, a straight or branched propyl group, or a butyl group.

In the naphthoquinone dye formula represented by the general formula, R1 and R2 represent a methyl group, an ethyl group, a linear or branched propyl group, or a butyl group.

In the styryl dye formula represented by the general formula, R represents an allyl group, a methyl group, an ethyl group, a linear or branched propyl group, or a butyl group, and X represents a hydroxy group, a cyano group, or a chlorine atom.

The general formula represents a syl group, a trifluoromethyl group, or a phenyl group optionally substituted with a halogen atom, and R represents a lower alkyl group, a lower alkoxyalkyl group, or an allyl group.

In the thiadiazole dye formula represented by the general formula, R, R', and R' represent an allyl group, a lower alkyl group, or a lower alkoxyalkyl group, and X is a methyl group,
Represents an acetylamino group or a formylamino group.

In the quinophthalone dye formula represented by the general formula, Ar represents a phenylene group or a naphthylene group, and X represents a hydrogen atom, a chlorine atom, or a bromine atom.

The general formula represents a doxy group, a hydroxyalkyl group, a trifluoromethyl group, a nitro group, or a phenyl group substituted with a halogen atom, and B represents an alkylene group optionally substituted with an alkoxyalkyl group or an allyloxyalkyl group.

etc. can be used.

Liquid toners can be produced by mixing a colorant and a coating agent in a suitable solvent, drying, pulverizing, and dispersing the mixture together with additives in a carrier liquid.

The coating material is a polar acrylic resin that imparts a charge to the colorant, such as acrylic acid, methacrylic acid, maleic acid, glycidyl acrylate, α-ethylglycidyl acrylate, hydroxyethyl methacrylate, methoxyethyl methacrylate, butoxyethyl Homopolymers or copolymers of methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, styrene-maleic acid copolymers, styrene-butadiene copolymers, and non-polar acrylic acid to adjust toner fixability and development speed. Ester resins, such as methyl methacrylate, butyl acrylate, inbutyl-α-
Ethyl methacrylate isobutyl methacrylate, 2-
Use a mixture of homopolymers or copolymers of ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl-α-ethyl acrylate, lauryl methacrylate, lauryl acrylate, stearyl methacrylate, and stearyl acrylate. be able to.

Additives are used to adjust the resistance and improve the dispersibility of the toner, and include naphthenic acid, octenoic acid, or stearic acid, calcium, barium, manganese, cobalt, nickel,
Polyvalent metal soaps such as copper, zinc, lead, and zircon can be used.

The carrier liquid is preferably one that has a high flash point, low toxicity, quick drying properties, and has a swelling or dissolving effect on the coating material, such as isoparaffinic hydrocarbons such as Isopar 61 Isopar H manufactured by Esso. can be used.

Since the liquid toner dispersed in the carrier liquid has a positive charge, it adheres to the negative charge on the dielectric layer and adheres to the dielectric layer by removing the carrier liquid and drying it.

The substrate for receiving the toner image may be any material as long as it can be dyed with disperse dyes or basic dyes, such as cloth, nonwoven fabric, synthetic resin film, and synthetic resin coated paper.

It is preferable that the fabric be woven from fibers such as polyester, acetate, and nylon that are easily dyed with disperse dyes and basic dyes. Fabrics blended with animal fibers such as fibers, silk, and wool can also be used.

In order for the heated and sublimated dye to fix well on the fabric, a smooth surface is desirable.

The thickness can range from as thin as about 50 μm to as thick as about 400 μm.

Non-woven fabrics include polyester, acetate, nylon,
In addition to fibers such as acrylic, rayon, and vinylon, we also manufacture olefin fibers such as polyethylene and polypropylene from a few mm thick.
It is possible to use a material cut into lengths of several tens of mm, mixed, formed into a sheet by a dry or wet method, and then strengthened with an adhesive or the like. Furthermore, a nonwoven fabric produced by a spunbond method in which ultrafine filaments coming out of a spinning nozzle are immediately dispersed and accumulated and bonded with an adhesive or heat can be used.

In order to improve dyeability with sublimation dyes, we increase the amount of fibers such as polyester, acetate, and nylon.
It is desirable that the thickness be 30 to 400 μm.

Examples of synthetic resins for synthetic resin films or synthetic resin-coated papers include polyolefin resins such as polyethylene and polypropylene, halogenated resins such as polyvinyl chloride and polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetate, and polyacrylic acid esters. vinyl resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene resins, polyamide resins, cellulose resins such as cellulose diacetate and cellulose triacetate, but in particular, films made of polyester resins or films thereof. It is preferable to use paper, nonwoven fabric, cloth, etc. laminated with polyester resin paint, or paper, nonwoven fabric, cloth, etc. coated with polyester resin paint.

Hereinafter, the present invention will be further explained in detail with reference to Examples.

Parts in the examples indicate parts by weight.

Example 1 On one side of a high-quality paper with a basis weight of 45 g/m2, 147 parts of a cationic conductive resin (Chemistat) 6300H1 solid content 34% (manufactured by Sanyo Chemical Industry Co., Ltd.) and calcium carbonate (Softon 2200 average particle size 1 .00μm, Bihoku Funka Kogyo Co., Ltd.
A paint consisting of 40 parts of vinyl acetate resin (Movinyl 50M, solid content 50%, manufactured by Hoechst Synthesis Co., Ltd.), and 78 parts of water was applied so that the coating amount after drying was 8.0 g/rn2. This was used as a conductive layer. The same paint was applied to the opposite side so that the coating amount after drying was 3.5 g/m'.

A 2% aqueous solution of methyl cellulose (Metrose 5M-25, manufactured by Shin-Etsu Chemical Co., Ltd.) was coated on the conductive layer so that the coating amount after drying was 0.3 g/m' to form a dye barrier layer.

Smoothing treatment was performed using a super calender, and the Bekk smoothness of the paint barrier layer was set to 500 seconds.

Acrylic resin (Dianal LR-338 solid content 36%
Mitsubishi Rayon Co., Ltd.) 140 parts, calcium carbonate (
MS-400 average particle size 1.71 μm 1 Nitto Funka Kogyo (
Co., Ltd.) and 50 parts of an isocyanate curing agent (Coronate L).
2 parts of Nippon Polyurethane Industries Co., Ltd.) was added and mixed uniformly, and the coating amount after drying was 4.0 g/m.
2 on the dye barrier layer to obtain an electrostatic recording material.

Add 10 parts of styrene-maleic acid copolymer (monomer weight ratio styrene/maleic acid = 40/60) to 200 m of isopropyl alcohol (IPA), heat to 70°C, and stir to completely dissolve. To this was added 25 parts of a 2% IPA solution of a dye represented by the following formula (1), and the mixture was uniformly mixed and dissolved using an ultrasonic disperser. IPA was evaporated, dried and solidified at 100° C., and then ground into a pigment.

A mixture consisting of 5 parts of pigment, 20 parts of 2-ethylhexyl methacrylate, and 80 parts of Isopar G (manufactured by Esso) was kneaded in a ball mill for 72 hours to obtain a concentrated toner. Two parts of the concentrated toner was diluted with 100 parts of Isopar G to obtain a cyan solution toner (IC).

Instead of the dye of formula (1), (2> formula, (3) formula, (4>
Magenta toner (IM), yellow toner (IY), and black toner (1B) were prepared in the same manner except that the dye represented by the formula was used.

CH3 Versatic electrostatic plotter (IC) (LM)
(IY) (IB)) to perform color recording of a mirror image on the electrostatic recording medium. Thickness 120
A polyester fabric of μm is overlaid on the dielectric layer after recording,
Pressure was applied from the back side of the electrostatic recording material for 30 seconds using a hot plate at 230°C.

A clear record was transferred onto the fabric, and the flexibility and water resistance were also good.

Example 2.3 The dye barrier layer of Example 1 was made of gelatin (Kanto Kagaku Co., Ltd.).
Coating amount is 0.3 g/m2 (Example 2)
Alternatively, polyacrylate (Acrylon -162 manufactured by Arayo Kagaku Kogyo Co., Ltd.) was used and the coating layer was set at 0.3 g/m' (Example 3). A recording medium was prepared, and after recording with a color electrostatic plotter, the sublimation toner was transferred to polyester fabric by heating.

In all cases, clear records were transferred to the fabric, and the flexibility and water resistance were also good.

Example 4 On one side of a polyethylene terephthalate film with a thickness of 75 μm, an electronically conductive conductive agent (ELCOM P-2320 solid content 30%, manufactured by Catalyst Kasei Co., Ltd.) was applied in an amount of 1 after drying.
．． It was coated to give a conductive layer of 0 g/m2.

Polyvinyl alcohol (PVA117, saponification degree 98%, manufactured by Kuraray Co., Ltd.) is used as a paint barrier layer on the conductive layer.
A 2% aqueous solution of was applied so that the coating amount after drying was 0.2 g/m2.

The coating amount of the dielectric layer paint of Example 1 after drying was 3.0 g/m
2 to obtain an electrostatic recording material. Conductive paint containing carbon black is applied to both left and right ends of the electrostatic recording medium in a width of 3 mm, and the electrical resistance value after drying is 5.0 x 10'.
It was set as Ω・cm.

In the same manner as in Example 1, after recording with a color electrostatic plotter, the sublimation toner was transferred to a polyester fabric by heating.

A clear record was obtained on the fabric, and both flexibility and water resistance were good.

Comparative Examples 1 to 4 Electrostatic recording media were prepared in the same manner as in Examples 1 to 4, except that the dye barrier layer was not provided in Examples 1 to 4, and after recording with a color electrostatic plotter, the sublimable toner was replaced with polyester. Transferred to fabric by heating.

In all cases, the density on the fabric decreased and the appearance was inferior to Examples 1 to 4. The flexibility and water resistance were good.

(Effects of the Invention) According to the present invention, an electrostatic latent image formed on an electrostatic recording material in which a conductive layer, a dye barrier layer, and a heat-resistant dielectric layer are sequentially provided on at least one side of a heat-resistant support is developed with a sublimation toner. After that,
By bringing it into contact with another substrate and heating it, a water-resistant color image can be efficiently transferred to the substrate.

Claims (1)

[Claims] 1. An electrostatic latent image formed on an electrostatic recording material having a conductive layer, a dye barrier layer, and a heat-resistant dielectric layer sequentially provided on at least one side of a heat-resistant support is developed with a sublimable toner. A method for recording on a base material, which is characterized by contacting the base material with another base material and heating the base material. 2. The recording method according to claim 1, wherein the substrate on which the image is recorded is cloth, nonwoven fabric, synthetic resin film, or synthetic resin coated paper.