JPH11138698A - Transfer sheet, image forming method, transfer method, image forming body - Google Patents

Abstract

(57) [Problem] To provide a transfer sheet capable of forming an image having excellent blocking resistance and excellent image uniformity. SOLUTION: An electrophotographic copying sheet having at least a release layer and an image forming layer sequentially on a support,
A transfer sheet, wherein the image forming layer contains a copolymer resin containing carboxylic acid as a constituent unit and / or a copolymer resin containing dicarboxylic acid anhydride as a constituent unit.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention enables a color image or pattern to be once copied by a color copying machine and then printed and decorated with heat on paper such as cloth for clothing and paper and textiles on campus. The present invention relates to a thermal transfer type transfer sheet, an image forming method, a transfer method, and an image forming body.

[0002]

2. Description of the Related Art Conventionally, screen printing, gravure printing, and the like have been used as a method of printing cloth for clothing and decorating paper, plastic, and glass such as signboards and show windows. With these printing methods, it is difficult to cope with small-lot production, and coping with these methods leads to a considerable increase in cost.

Further, in the conventional method, it takes a long time to prepare an original plate, so that it is not possible to quickly respond to a delivery date. In terms of image quality, the conventional image also lacks reproducibility of the original considerably due to the unevenness of the material on the transfer side. In the conventional printing method, the working environment was not good because a solvent was used.

On the other hand, recently, in addition to the above-described printing method, there is a method in which an image of a color copying machine is subjected to copy printing on a transfer sheet, and the image is transferred by heat together with an EVA resin serving as a transfer layer. This has advantages such as reproducibility of originals, shortening of preparation time, cost at the time of production of a small lot, and elimination of solvent as compared with printing such as screen printing.

However, when an EVA-based resin is used as the transfer material, the adhesion to the material on the transfer side and the adhesion to the pigment toner are insufficient, and it has been difficult to use the resin for a long time. In addition, a resin other than the EVA-based resin having good adhesion to the material on the transfer-receiving side and adhesion to the pigment toner was used.

Japanese Patent Publication No. 20204/1984 discloses a method using a polymer material having a hydroxy group and a blocked isocyanate crosslinking agent. However, in the case of a thermosetting image forming layer, The molecular weight increases due to a crosslinking reaction at the fixing temperature of a copying machine or a heat source at the time of thermal transfer, the solubility decreases, the image forming layer becomes cloudy, or a polymer material containing a carboxylic acid in a molecule such as vinyl acetate or the like. On the other hand, the image forming layer has a problem that the surface of the image forming layer becomes cloudy due to a foaming phenomenon due to carbon dioxide gas or the like during the crosslinking reaction, the surface layer becomes crater-like, and the surface becomes rough.

[0007] Japanese Patent Publication No. 61-3272 discloses the curing by irradiation with actinic rays and electron beams. Similarly, after the cross-linking reaction proceeds, the molecular weight of the polymer increases and the hot-melt bonding temperature rises. However, for example, a toner image formed on the image forming layer sometimes has a problem that an unfixing failure occurs.

Japanese Patent Application Laid-Open No. Hei 8-11420 discloses a method in which a non-crosslinked thermoplastic acrylic resin which is a radiation-curable resin and an acryloyl group or a methacryloyl group in a molecule are used. Although excellent in elongation and flexibility, transfer is difficult unless the Tg of the resin is high and the thermal transfer temperature is as high as 200 ° C. or higher.

Further, it is not preferable for a copy copy transfer system because it requires a high heat resistance of the transfer sheet.

In Japanese Patent Application Laid-Open No. 8-267901, a colorless extender is added to an image forming layer to improve transportability for the purpose of blocking resistance of a heat fixing portion of a copying machine. I can't say that.

[0011]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a thermal transfer type transfer sheet, an image forming method, a transfer method, and an image forming body in which an image obtained by transfer is highly uniform.

A second object of the present invention is to provide a thermal transfer type transfer sheet excellent in blocking resistance, an image forming method, a transfer method, and an image forming body.

A third object of the present invention is to provide a thermal transfer type transfer sheet having excellent transportability, an image forming method, a transfer method, and an image forming body.

A fourth object of the present invention is to provide a thermal transfer type transfer sheet, an image forming method, a transfer method, and an image forming body in which an image obtained by transfer is excellent in glossiness.

In the material of the image forming layer, if a copolymer resin having a specific structural unit is used, an image obtained by transfer is highly uniform, and if the copolymer resin satisfies specific conditions, a sheet is formed. Is excellent in anti-blocking properties, and it is excellent in transportability if a specific substance is added to the image forming layer, and if the smoothness of the release layer is constant, the image obtained by transfer is excellent in glossiness. I found that.

[0016]

According to the present invention, first, in an electrophotographic copying sheet having at least a release layer and an image forming layer on a support in order, a carboxylic acid is added to the image forming layer. A transfer resin comprising a copolymer resin containing as a constituent unit and / or a copolymer resin containing an anhydride of dicarboxylic acid as a constituent unit. Secondly, vinyl chloride-acrylic acid is added to the image forming layer. Wherein the alkyl copolymer resin comprises 20 to 80 parts by weight based on the copolymer resin containing carboxylic acid as a constituent unit and / or the copolymer resin containing dicarboxylic acid anhydride as a constituent unit. Third, the transfer sheet according to 1,
The transfer sheet according to the above 1-2, wherein a back layer is provided on the opposite side of the image forming layer of the support, and fourthly, the transfer sheet according to the above-mentioned 1-3 by electrophotography. Fifth, an image forming method is characterized in that a toner image formed on the third transfer sheet is transferred onto an image receiving medium by heat pressing. Sixth, there is provided an image forming body obtained by transferring the three toner images onto an image receiving medium.

In order to obtain high image quality by copying an image from an electrophotographic image to a transfer sheet, the electrostatic characteristics of the electrophotographic method are dominant and depend on the dielectric constant and capacitance of the image forming layer. Specifically, the electrostatic characteristic is a large characteristic in which the intensity of the potential of the electrostatic latent image is related to high image quality. The specific resin of the present invention was selected from the above-described electrophotographic electrostatic characteristics, that is, electrostatic characteristics such as volume resistivity, dielectric constant, and time constant.

Further, it has been found that the blending of the specific resin of the present invention shows excellent results in the plasticization rate and tackiness during heating with respect to the adhesion and fixing of the toner.

The transfer sheet according to the present invention has at least a release layer and an image forming layer in this order on a support, and a copolymer resin containing a carboxylic acid as a structural unit in the image forming layer and / or a dicarboxylic acid. A copolymer resin containing an acid anhydride as a constituent unit is included.

This is effective in preventing the so-called blocking phenomenon in which the image layer and the transfer sheet adhere to each other when the transfer sheets are stored in an overlapped state.

When a part of the copolymer resin is a hydrophilic base, the image layer is uniformly coated, and the resulting image obtained by transfer is highly uniform.

The Tg of the copolymer resin is from -10.degree.
Outside this range, which is preferably lower than 0 ° C, for example,
When the temperature is lower than 0 ° C, blocking tends to occur in the image forming layer. If the temperature is higher than 30 ° C., the resin tends to be hard and cracks tend to affect the image quality.

Then, a copolymer resin containing a carboxylic acid or a dicarboxylic anhydride as a constitutional unit is obtained.
Styrene-acrylic acid copolymer, isobutylene-maleic anhydride copolymer, and styrene-maleic anhydride copolymer are more effective in preventing the blocking phenomenon. Also,
The molecular weight is preferably from 1500 to 30,000.
The copolymer resin containing carboxylic acid or dicarboxylic anhydride as a constitutional unit can be given water solubility by forming a salt with a basic substance for the purpose of giving water solubility.

In addition, if an ammonium salt is selected from the basic materials of the copolymer resin, it is more effective in preventing the blocking phenomenon.

The features will be described below. In the case of a coating solution, the ammonium salt is dissolved in an aqueous solution as an ammonium salt of a copolymer containing carboxylic acid or dicarboxylic anhydride as a constitutional unit, but becomes ammonia gas after being coated and dried on a substrate. Since the resin is eliminated, the resin becomes a coating film having poor water solubility.

However, other base materials remain water-soluble because they remain as salts in the resin molecules, and do not satisfy the object of the present invention.

Next, the vinyl chloride-alkyl acrylate copolymer resin of the present invention has excellent electrophotographic electrostatic characteristics.
Particularly, the feature is that the charge of the electrostatic latent image increases. It is expected that the properties that dominate the characteristics depend on the dielectric constant and capacitance of the resin layer. In the invention, a vinyl chloride-alkyl acrylate copolymer resin is preferably used in combination with the above-mentioned copolymer resin in the image forming layer. The vinyl chloride-alkyl acrylate copolymer resin has an alkyl group having 6 to 16 carbon atoms, which is more effective in preventing the blocking phenomenon.

If the number of carbon atoms is 6 or less, it is difficult to obtain a characteristic electrostatic characteristic. If the number of carbon atoms is 16 or more, the fixability of the toner tends to be unfavorably reduced.

The chemical formula of the vinyl chloride-alkyl acrylate copolymer resin typically used in the present invention is described below.

[0030]

Embedded image

The Tg of the vinyl chloride-alkyl acrylate copolymer is not limited, and can be adjusted by the length of the alkyl group.

Specifically, hexyl acrylate, cyclohexyl acrylate, 2-methyl-1-pentyl acrylate, 4-methyl-2-pentyl acrylate, heptyl acrylate, 2-heptyl acrylate, acrylic Acrylics such as octyl acrylate, 2-ethylhexyl acrylate, 2-octyl acrylate, nonyl acrylate, decyl acrylate, 5-ethyl-1-nonyl acrylate, dodecyl acrylate, tetradecyl acrylate, and hexadecyl acrylate It is a copolymer of vinyl chloride composed of an acid ester monomer and having an average molecular weight of 5000
About 50,000.

The amount used is suitably from 20 to 200% by weight, more preferably from 40 to 150% by weight, based on the copolymer resin containing the carboxylic acid or dicarboxylic anhydride as a constituent unit of the present invention. is there. If the amount is less than 20 parts by weight, there is no further effect of preventing the blocking phenomenon, and if the amount is more than 200 parts by weight, blocking tends to be easily generated at the time of fixing.

The coating thickness of the image forming layer is 5 to 50.
μm is appropriate, and more preferably 15 to 30 μm.

If a white pigment is added as an additive, the generation of static electricity in the electronic copying machine is suppressed, and the transportability is improved. Among them, magnesium silicate is preferable.

The chemical composition of magnesium silicate is M
g ₆ [Si ₈ O ₂₀ ] (OH ₄ ).

The white pigment referred to in the present invention is different from general talc and has a pyrophyllite type three-layer structure.
The layers are sandwiched between the SiO ₂ layers, and an (OH) layer exists between the two, and is chemically strongly bonded.

Also in this crystal structure, when the particles are formed into particles, the particles become flat and the surface of the particles is covered with the SO ₂ layer, so that various characteristics occur. For example, regarding the adhesiveness with the copolymer resin of the present invention, the magnesium silicate of the present invention is extremely excellent as compared with general extender pigments such as silica, calcium carbonate, talc, alumina white, titanium white titanium oxide, and the like. Also, since the hardness of the material properties is extremely low, there is no side effect on the abrasion resistance during transportation in a copying machine.

Further, since the hardness of the white pigment is extremely low, even when fixing the toner, it is possible to obtain a high-quality image with high uniformity without generating a white point as compared with general talc.

The magnesium silicate preferably has a whiteness of 86% to 99%.

When the whiteness is less than 86%, the function as a white pigment is not obtained, and the contrast of the finished image tends to be low.

The bulk specific volume is preferably in the range from 1.5 ml / g to 3.0 ml / g. This property is affected by the particle size of the particles, D ₅₀ is preferably 1.5Myu～3.2Myu, prone to compositional change caused precipitation in the coating solution to be larger than 3.0 ml / g. Conversely, when the amount is less than 1.5 ml / g, a tendency of aggregation is observed in the dispersion, which is not preferable.

These may be prepared by dispersing magnesium silicate alone in the copolymer resin of the present invention in an aqueous solution in advance or using 3% to 10% in the resin solution of the image forming layer of the present invention.
It can be used by mixing and dispersing at a ratio of weight%.

The smoothness of the laminate surface of the release layer is 40.
If the time is 0 second or longer, the finished image has excellent glossiness.

If the smoothness is less than 400 seconds, it is difficult for the image which is one of the high quality image of the copy transfer image to give gloss.
Further, the thickness of the image forming layers to be laminated becomes uneven, and the problem of blurring and lack of uniformity of the image is likely to occur.

In order to maintain the surface smoothness, for example, smoothing can be performed by calendering, and adjustment can be performed under pressurized conditions.

The smoothness of the peeling layer is measured by an Oken type smoothness tester.

The smoothness of the release layer can be measured not only in the state before the production where the image forming layer is not yet mounted but also after the use as a product because the image forming layer is peeled off by a heat press. .

Any material may be used as long as it has a releasable property. Specifically, silica, talc, alumina, titanium oxide, zinc oxide, various clay components, starches, and organic pigments include Powders of urea formalin resin, hollow particles of urethane resin particles or foams, methamine resin particles, epoxy resin particles, polyethylene resin, polypropylene resin, styrene resin, fatty acid waxes, silicone oil, rubber or resin, fluorine resin, etc. No. These compounds have no adhesive property or have no sticking property themselves and exhibit a releasing function.

In addition, any material such as an inorganic pigment or an organic pigment, or silicon or Teflon having high water repellency may be used as long as it has releasability.

The above-mentioned resin solution for the image forming layer is laminated and applied to the release layer and dried with hot air at a drying temperature of 90 ° C. to 110 ° C. to obtain the image forming layer of the present invention.

By providing a back layer on the surface opposite to the image forming layer, it is possible to further improve the blocking characteristics when stacked. Any material can be used as long as it has a releasable property. Specifically, silica, talc, alumina, titanium oxide, zinc oxide, various clay components, starches, and, as the organic pigment, urea formalin resin Examples include powder, urethane resin particles, foam hollow particles, methamine resin particles, epoxy resin particles, polyethylene resin, polypropylene resin, styrene resin, fatty acid waxes, silicone oil, rubber or resin, and fluorine resin. These compounds have no adhesive property or have no sticking property themselves and exhibit a releasing function. The release of inorganic pigments and organic pigments if any, or may repellent high silicon or Teflon, etc. anything, it is the range of 0.1g / m ² ~5.0g / m ² for usage. If the amount of use exceeds that, it is not preferable because it slips too much.

The image receiving sheet for receiving the transferred image according to the present invention may be not only paper but also any other material such as canvas or cloth or glass having a rough surface. Since a low canvas is mainly used, a clear image can be obtained by performing a filling process on the surface.

The release layer for the sealing sheet does not need to be smooth enough to be used for the image forming layer, and it is sufficient that the unevenness of the transferred object is concealed, and the high quality image is uniformly transferred to the transferred object. There is no particular limitation.

The support used for the filling layer may be a polyester resin film such as polyethylene terephthalate, polybutylene terephthalate, ethylene terephthalate or isophthalate copolymer, or a synthetic paper such as polyolefin such as polyethylene or polypropylene, or a general paper. Fine and medium quality paper can be used.

Specifically, if the resin described below is dried on the support with hot air at a drying temperature of 90 ° C. to 110 ° C., the sealing sheet of the present invention can be obtained.

[0057] Image forming layer resin of the present invention on a sheet provided with a releasable material text is described or ethylene, - a vinyl acetate copolymer resin by dry weight, the adhesion amount of 10g / m ² ~70g / m ² Laminate and apply within the range.

The image forming transfer sheet of the present invention is formed by sequentially laminating a base material having a peeling function.

The substrate may be a general release agent.

For example, as an inorganic pigment, silica, talc,
Alumina, titanium oxide, zinc oxide, various clay components, starches, and organic pigments include urea-formalin resin powder, urethane resin particles and foam hollow particles, melamine resin particles, epoxy resin particles, polyethylene resin, Examples include polypropylene resin, styrene resin, fatty acid waxes, silicone oil and rubber or resin, and fluororesin. These compounds have no adhesive property or have no sticking property themselves and exhibit a releasing function.

Further, coated paper or the like to which the above-mentioned release resin is applied is used.

These materials can be used not only as an image forming sheet but also as a release substrate of a sealing sheet (image fixing sheet).

A color image or a monochrome image is formed on the image forming sheet of the present invention by a commercially available copying machine or printer, and a mirror image is formed on the image forming sheet.

Specifically, the sheet on which the image was formed was superimposed on a commercially available campus ground, and the surface temperature was 130 ° C. to 160 ° C.
After pressure bonding with a hot press at a temperature of ℃, the mixture is allowed to cool to room temperature, and then the release paper is peeled off.

Then, the image is sandwiched between the transfer sheet and the image receiving sheet, and after being pressure-bonded by a hot press having a surface temperature of 150 ° C. to 160 ° C., is allowed to cool to room temperature.

In this case, a clear image can be obtained regardless of whether the transfer sheet or the image receiving sheet is on the upper side.

Thereafter, the release sheet of the image forming sheet is released.

At this time, in the case of hot pressing, if an air hole is previously formed in a perforation or the like, the image forming layer of the image forming sheet may be uniformly transferred. Hereinafter, the present invention will be specifically described based on examples. Naturally, the contents of the present invention are not limited by the present embodiment.

The number of parts in Examples and Comparative Examples represents parts by weight.

Example 1 The following stripping solution was dried at a drying temperature of 120 ° C. using a wire bar on a commercially available high quality paper (basis weight: 104.3 g / m ² ), and 2 g / m ^{2 was} attached by weight. A release sheet was formed. Next, the image forming resin liquid was applied at a dry weight of 30 g / m ² and dried at 110 ° C. for 2 minutes to form an image forming transfer sheet. The value of the smoothness of the sheet coated with the release liquid A and dried was 60 seconds.

[Release liquid A] Stearamide dispersion (20%) 50 parts PVA205 (Kuraray) 5 parts Water 45 parts [Image forming resin liquid A] Styrene-ammonium acrylate copolymer aqueous solution 45 parts (Johnson polymer J-743, solid content concentration 45%, Tg 30 ° C) PVC-ethylhexyl acrylate copolymer 45 parts (DK-120, manufactured by Denki Kagaku Co., Ltd.) Water 10 parts The image-forming transfer sheet obtained in Example 1 is colored. As a result of copying the transferred image with a copying machine Piuter 650 (manufactured by Ricoh Co., Ltd.), a clear color image was obtained.

Using this transfer sheet, a color copy image forming sheet was pressure-bonded for 10 seconds at a surface temperature of 160 ° C. under a pressure of 75 g / cm ² while facing the color copy image forming sheet to a 5 mm thick wood board. After leaving to cool at room temperature, the release sheet was peeled off, and a clear and textured copy image was formed on the wood board.

Next, the transfer sheet obtained in Example 1 was
A brush character was copied in a mirror image using Ricoh's Imagio MF530, and transferred to the above-described wooden board under the same conditions. As a result, a water-resistant nameplate was completed.

Example 2 A commercially available high quality paper (basis weight: 104.3 g / m ² ) was coated with the following stripper using a wire bar to obtain a dry weight adhesion of 2 g / m ^2.
m ^{2 was} adhered to form a release sheet.

[Release liquid B] 10 parts of room temperature crosslinking silicone rubber emulsion SE-1980 (solid content: 45%, manufactured by Dow Coating Silicon Co., Ltd.) 10 parts of water This release layer was pressed with a calender at 20 kg / cm ^2. Surface treated. At this time, the smoothness of the release layer was 450 seconds as measured by an Oken-type smoothness tester.

Next, the following image forming resin solution was applied and dried at the same amount and at the same drying temperature as in Example 1.

[Image-forming resin liquid B] Styrene-ammonium acrylate copolymer aqueous solution 40 parts (J-711 manufactured by Johnson Polymer Co., solid content concentration 45%, Tg 0 ° C) PVC-octyl acrylate copolymer 40 parts ( DK-120 Prototype manufactured by Denki Kagaku Co., Ltd. Solid content concentration 40%) Microace K-1 manufactured by Nippon Talc Co., Ltd. Whiteness 92-97% 10 parts Bulk specific volume 1.5-1.7 (ml / g) Water 10 Part The image forming transfer sheet of the present invention was obtained from the above steps.

Next, a filler layer was provided on the release sheet described in Example 1 by laminating a resin composition having the following composition with a wire bar and drying (dry weight: 60 g / m ² ).

[Filling resin liquid] Self-crosslinkable ethylene-vinyl acetate containing methylol component 40 parts Acrylic copolymer resin (EF-421 manufactured by Showa Polymer Co., Ltd., crosslinking temperature of 120 ° C. or more, solid content 45%) Methylol component Containing self-crosslinking ethylene-vinyl acetate 40 parts Acrylic copolymer resin (EF-250N manufactured by Showa Polymer Co., Ltd. Crosslinking temperature 120 ° C or higher, solid content 45%) Water 20 parts This sheet is hot-pressed on a commercially available cotton campus. Bonding to the desired transfer range under the conditions of a surface temperature of 160 ° C. and a pressure of 75 g / cm ² of a machine (manufactured by Mainichi Mark: rotary press) 1
Pressure bonding was performed for 0 seconds.

Thereafter, the sheet was allowed to cool at room temperature, and the release sheet was peeled off. Then, the color copy image forming sheet obtained in Example 1 was pressed against the surface at 160 ° C. for 10 seconds under the condition of a pressure of 75 g / cm ² while facing the same. Glued. Similarly, after allowing to cool at room temperature, the release sheet was peeled off, and a clear and textured copy image was formed on the cotton campus ground.

In such a process, the photographic image was also copied by the color copying machine with respect to the image forming transfer sheet of the second embodiment.
When the image was transferred to a commercially available cotton campus ground, a clear and glossy copy image was formed, which was as inferior to that of Example 1 due to the smoothing effect of the release layer. Example 3 Using the release layer formed in Example 1, the following image-forming resin liquid c was laminated on the release layer, dried with a wire bar, and applied with an adhesion amount of 3
The resultant was coated and dried so as to have a concentration of 0 g / m ² to provide an image forming transfer sheet.

[Image Forming Resin Liquid C] Styrene-ammonium acrylate copolymer aqueous solution 40 parts (J-511 manufactured by Johnson Polymer Co., solid content concentration 45%, Tg 9 ° C.) Isobutylene-maleic anhydride ammonium copolymer aqueous solution 40 parts (Kuraray Co., Ltd., Isoban SMA3000) Water 20 parts A transfer image was copied on the image-forming transfer sheet obtained in the same process as in Example 1 using a color copying machine Piuter 650. As a result, a clear color image was obtained. This transfer sheet 10 ° C 15% R
The sheet was allowed to stand for 1 week under a low temperature and low humidity of H, and the cracking property of the sheet was evaluated.

Example 4 Commercially available release paper (kp-8, manufactured by Lintec Corporation)
The following image forming resin liquid D was laminated on a release layer having a release surface smoothness of 7 g / m ² 650 seconds (Oken type smoothness meter), dried with a wire bar, and coated so as to have an adhesion amount of 30 g / m ² . After drying, an image forming transfer sheet was provided.

[Image Forming Resin Liquid D] Styrene-ammonium acrylate copolymer aqueous solution 40 parts (J-840 manufactured by Johnson Polymer Co., solid content concentration 45%, Tg 16 ° C.) Isobutylene-maleic anhydride ammonium aqueous solution 40 parts (Isoban SMA3000 manufactured by Kuraray Co., Ltd.) Microace L-1 (manufactured by Nippon Talc) Whiteness 92-96% 10 parts Bulk specific volume 1.5-1.7 (ml / g) Water 10 parts Same as Example 1 The image formed transfer sheet obtained in the process was copied with a color copying machine Piuter 650 to obtain a clear color image.

Next, the surface temperature of the hot press machine (manufactured by Mark Main Co., Ltd .: rotary press) was set to 16 while the image forming and transferring sheet was opposed to the filling process campus ground used in Example 2.
Under a condition of 0 ° C. and a pressure of 75 g / cm ² , they were adhered to a desired transfer range and pressure-bonded for 10 seconds. Thereafter, the sheet was allowed to cool at room temperature, and the release sheet was peeled off. As a result, a clear image was formed.

Example 5 Microace L used for image forming resin liquid D of Example 4
-1 (manufactured by Nippon Talc) Micro Ace P-2 (manufactured by Nippon Talc) instead of 92-96% whiteness 95-9
An image-forming transfer sheet of Example 5 was made in the same manner except that 9% and a bulk specific volume of 1.9 to 2.2 (ml / g) were used.

Example 6 Microace L used for the image forming resin liquid D of Example 4
-1 (manufactured by Nippon Talc) Microace P-3 (manufactured by Nippon Talc) instead of 92-96% whiteness 95-9
An image-forming transfer sheet of Example 6 was made in the same manner except that 9% and a bulk ratio volume of 2.2 to 2.6 (ml / g) were used.

Example 7 The image forming resin solution E was laminated on the release layer subjected to the smoothing treatment in Example 2, dried with the same wire bar, and applied in an amount of 30 g / m 2.
^The resultant was coated and dried so as to obtain an image forming transfer sheet.

[Image Forming Resin Liquid E] Styrene-ammonium acrylate copolymer aqueous solution 40 parts (J-711 manufactured by Johnson Polymer Co., solid content concentration 45%, Tg 0 ° C.) PVC-hexadecyl acrylate copolymer 50 parts ( DK-120 prototype manufactured by Denki Kagaku Co., Ltd. Solid content concentration 40%) Micro Ace LG manufactured by Nippon Talc Co., Ltd. Whiteness 89%-97% 10 parts Bulk specific volume 1.8-2.0 (ml / g) A back solution can be applied to the back surfaces of the image forming transfer sheets and the filling sheets of Examples 1 to 7 for the purpose of preventing curling.

Specifically, water is added in an amount of 10 g / m ^{2 to} 20 g /
It is effective to provide a coating amount of m ² . Next, the following back solution was applied to the back surface of the transfer sheet prepared in Example 7 at a dry weight of 2 g / m ² and dried to provide an image forming transfer sheet. This transfer sheet was used in Example 8
And

[Back solution] Stearamide dispersion (solid content concentration: 20%) 10 parts PVA205 (Kuraray Co., Ltd.) 5 parts Water 85 parts [Example 9] The following is described on the back surface of the transfer sheet prepared in Example 7. The back solution formulation was applied to a dry weight of 2 g / m ² to prepare an image transfer paper provided with a back layer.

(Back solution) Room temperature curing type silicone rubber emulsion 5-fold dilution 94 parts (SE-1980 Clear, manufactured by Dow Coating Silicon, Toray Co., Ltd., 1 part of solid content 45%, diluted with 4 parts of water) Silicon resin Emulsion 5-fold dilution 6 parts (SM-7706 Toray, Dow Coating, manufactured by Silicone Co., Ltd., solid content 35%, 1 part diluted with 4 parts of water) Next, a comparative example of the present invention will be described.

Comparative Example 1 The following image-forming resin solution was adhered on a release paper formed by using the release liquid A to the general high-quality paper used in the example, at a dry weight of 30 g / m ² , and dried at a drying temperature of 110 ° C. for 2 minutes. The image forming transfer sheet of Comparative Example 1 was prepared.

[Image Forming Resin Liquid F] 40 parts of a methylol component-containing self-crosslinking ethylene-vinyl acetate acrylic resin (EF-421 manufactured by Showa Polymer Co., Ltd .; crosslink temperature: 120 ° C. or more; solid content: 45% Tg-21) 40 ° C) Methylol component-containing self-crosslinking ethylene-vinyl acetate 40 parts Acrylic copolymer resin (EF-250N manufactured by Showa Polymer Co., Ltd. Crosslinking temperature 120 ° C or higher, solid content 45% Tg20 ° C) Water 20 parts obtained here The transfer image was copied from the image-forming transfer sheet with a color copying machine Piuter 650 (manufactured by Ricoh Co., Ltd.), and as a result, a glossy color image was obtained. The reliability of this sheet was evaluated in the same manner as in the example.

Comparative Example 2 The following image forming resin solution was applied to the commercially available release paper used in Example 4 at a dry weight of 30 g / m ² , and the drying temperature was 110 ° C.
For 2 minutes to prepare an image forming transfer sheet of Comparative Example 2.

[Image Forming Resin Liquid G] Styrene-244 (manufactured by Fuji Devson) 10 parts Toluene 30 parts Isopropyl alcohol 20 parts of styrene-octyl methacrylate copolymer (Dianal LR-188 Tg at 5 ° C. manufactured by Mitsubishi Rayon Co., Ltd.) 20 copies of the image-forming transfer sheet obtained here were copied with a color copying machine PYTER 650 (manufactured by Ricoh Co., Ltd.) to obtain a glossy color image. The reliability of this sheet was evaluated in the same manner as in the example.

Comparative Example 3 30 g / m ^{2 of the following} image forming resin liquid was adhered by dry weight to the release paper formed by using the release liquid B on the general high-quality paper used in the examples, and dried at a drying temperature of 110 ° C. for 2 minutes. An image forming transfer sheet of Comparative Example 3 was prepared.

[Image Forming Resin Liquid H] Ethylene-vinyl acetate copolymer resin 40 parts (EVA latex 56 manufactured by Denki Kagaku, solid content 55% Tg-18) Calcium carbonate (manufactured by Shiraishi Chemical Co.) 10 parts Water 20 Part Comparative Example 4 30 g / m ^{2 of the following} image forming resin liquid was adhered by dry weight to a release paper formed using the release liquid B on the general high-quality paper used in the examples, and dried at a drying temperature of 110 ° C. for 2 minutes. An image forming transfer sheet of Example 4 was prepared.

[Image Forming Resin Liquid I] 40 parts of ethylene-vinyl acetate copolymer resin (40 parts of EVA latex 56 manufactured by Denki Kagaku Co., Ltd., solid content 56% Tg-18 ° C.) (EVA latex 60 manufactured by Denki Kagaku Co., Ltd., solid content 55% Tg 0 ° C.) Water 20 parts Comparative Example 5 The following image forming resin liquid was dried on a release paper formed by using a release liquid B on the general high-quality paper used in the examples. in 30 g / m ² adhered to, and dried for 2 minutes at a drying temperature of 110 ° C., to create an image forming transfer sheet of Comparative example 5.

[Image Forming Resin Liquid I] Ethylene-vinyl acetate-copolymer resin 40 parts (EVA latex 56 manufactured by Denki Kagaku Co., solid content 56% Tg-18 ° C.) Ethylene-vinyl acetate-copolymer resin 40 parts (EVA latex 60 manufactured by Denki Kagaku, solid content 55% Tg 0 ° C) Talc SWB (general-purpose product) Brightness 83% 10 parts Bulk specific volume 1.0-1.2 (ml / g) (manufactured by Nippon Talc) Water 10 parts Comparative Example 6 30 g / m ^{2 of the following} image forming resin liquid was adhered by dry weight to the release paper formed using the release liquid B on the general high-quality paper used in the examples, and dried at a drying temperature of 110 ° C. for 2 minutes. Then, an image forming transfer sheet of Comparative Example 6 was prepared.

[Image Forming Resin Liquid J] 40 parts of ethylene-vinyl acetate copolymer resin (EVA latex 56 manufactured by Denki Kagaku Co., Ltd., solid content 55% Tg-18 ° C.) 40 parts of ethylene-vinyl acetate copolymer resin (EVA latex 60 manufactured by Denki Kagaku Co., Ltd., solid content 55% Tg 0 ° C.) Talc SS (general-purpose product) Brightness 83% 10 parts Bulk specific volume 1.0-1.2 (ml / g) (manufactured by Nippon Talc) Table 1 shows the results of testing the image transfer sheet obtained with 10 parts or more of water by the following method.

Regarding image evaluation, a black-and-white image manufactured by Ricoh Co., Ltd. was evaluated by Imagio MF530, and a color image was evaluated by Pretail 650 by Ricoh Co., Ltd.

Next, as for the transfer sheet of Example 8, a heat press machine (manufactured by Mainichi Mark Co., Ltd.)
Using a rotary press) Surface temperature 160 ° C Pressure 75
After pressure bonding for 10 seconds under the condition of g / cm ^2, the film was similarly allowed to cool at room temperature, and then the peeling sheet was peeled off. As a result, a clear and textured copy image was formed on the canvas.

1. Image uniformity (variation in thickness of image forming layer) Using Ricoh's Pretates 650 color copier, copy it onto an image forming transfer sheet using a predetermined test pattern, paste it on polypropylene synthetic paper with an adhesive, and peel off the image forming layer Evaluation of abnormalities such as white spots, line breaks, and differences in image density after transfer. The occurrence of white spots and density unevenness is indicated by x, and the uniformity is indicated by o.

2. Blocking property of transfer sheet A load of 1 kg / A-4 was placed on the image forming sheet for 3 days in a thermostat at 50 ° C., and after five samples were left as a set,
Peeled and evaluated the noise and blocking.

3. Difference in coefficient of static friction due to moisture content of image transfer layer (operability) 20 ° C, 65% R with static friction coefficient measuring device (manufactured by Toyo Seiki Co., Ltd.)
After adjusting the humidity for 4 hours in an environment of H, 30 ° C. and 85% RH, the surface of the image forming layer of the transfer sheet is measured. If the difference in environment is large, or if the difference is extremely high, the paper jams during conveyance of the copier, causing troubles such as jams.

Example: 2 from the static friction coefficient value at 30 ° C. and 85% RH
If the difference between the static friction coefficient values at 0 ° C. and 65% RH is 1.0 or more, a jam occurs during conveyance of the copying machine. A rating of Δμ1.0 or more was indicated by ×, and an evaluation of Δμ1.0 or less was indicated by ○.

4. Transfer Paper Glossiness of Copy Image The surface of the transfer sheet on which an image is formed using a predetermined test pattern is measured with a gloss meter (Nippon Denshoku Industries Model 1001DP).
It is better to show a value with high glossiness.

[0109]

[Table 1]

Table 1 shows that the evaluation results of the examples and the comparative examples are generally inferior in image uniformity and blocking property.

Examples 2, 4, 5, 6, and 7 are Examples 1 and 3,
It can be seen that the glossiness of the image is larger than that of the above, and the effect of high image quality is exhibited.

Next, in Examples 1 and 3, unlike the other examples, since magnesium silicate was not used, the coefficient of static friction under high-temperature, high-humidity water content was large, and the transportability was hindered.

In addition, it is observed that the coefficient of static friction is large despite the use of general-purpose talc in Comparative Examples 4 and 5.

Next, in Examples 8 and 9, curling was excellent because the back layer was provided on the back surface of the transfer sheet, and the anti-blocking effect was also exhibited.

The image-forming sheet containing the vinyl chloride-alkyl acrylate copolymer of the present invention exhibits electrostatic properties indispensable for high image quality, exhibits excellent flexibility at low temperature and low humidity, and exhibits excellent effects when folded. No cracks or cracks were observed.

[0116]

As described above, according to the present invention,
A transfer sheet free from blocking can be obtained,
With this transfer sheet, an image having excellent image uniformity can be formed, and this high-quality image can be transferred onto an image receiving medium.

Claims (6)

[Claims] 1. An electrophotographic copying sheet having at least a release layer and an image forming layer sequentially on a support,
A transfer sheet characterized in that the image forming layer contains a copolymer resin containing a carboxylic acid as a constitutional unit and / or a copolymer resin containing a dicarboxylic acid anhydride as a constitutional unit. 2. An image forming layer, wherein a vinyl chloride-alkyl acrylate copolymer resin is used as a copolymer resin containing carboxylic acid as a constituent unit and / or a copolymer resin containing dicarboxylic acid anhydride as a constituent unit. 2. The transfer sheet according to claim 1, wherein the transfer sheet contains 20 to 80 parts by weight. 3. The transfer sheet according to claim 1, wherein a back layer is provided on a side of the support opposite to the image forming layer. 4. An image forming method, comprising: forming a toner image on the transfer sheet according to claim 1 by an electrophotographic method. 5. An image transfer method, wherein the toner image formed on the transfer sheet according to claim 3 is transferred onto an image receiving medium by a heat press. 6. An image forming body obtained by transferring the toner image of claim 3 onto an image receiving medium.