JPH09240148A - Polar reversible medium and printing method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To overcove environmental resistance by applying light and/or heat to a polar reversible medium and reversibly coverting the hydrophilicity- hydrophobicity on the polar reversible medium. SOLUTION: A latent image to be formed is obtained by once making the surface of a polar reversible medium 1 hydrophobic by an erasing means 10 and applying heat thereto corresponding to an image signal from a recording means 3 to form a hydrophilic part on the surface of the medium. The latent image is converted to a visible image by ink 4 by using the developing roller 6 immersed in an ink reservoir 5. The visible image formed on the polar reversible medium 1 on a drum 2 is fed to the position of a transfer roller 7 by the rotation of the drum 2 and transferred to a synchronously fed transfer material 8. The residual ink on the polar reversible medium 1 is removed by a cleaning means 9. The latent image completed in printing is erased by the erasing means to prepare the polar reversible medium for the next formation of an image.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel printing technique applicable to printers, copying machines, facsimiles, etc. More specifically, it is a polar reversible device capable of controlling reversible hydrophilic-hydrophobic conversion by light and / or heat. Using a medium, transfer hydrophilic ink or hydrophobic ink to the transfer body,
The present invention relates to a printing method capable of obtaining an image.

[0002]

2. Description of the Related Art In recent years, printers have been required to meet the requirements for plain paper, high speed, high image quality, and low price, and various printers have been proposed and commercialized. Typical of these are thermal recording, ink jet, and electrophotography, but laser printers that use electrophotography have excellent functions such as high speed, high image quality, and low noise, and have the same impact as conventional ones. It has evolved into an output device for general-purpose large-scale computers in place of printers, and now laser printers are used as typical non-impact printers along with transfer-type thermal printers and inkjet printers. However, the electrophotographic method has disadvantages that it has a complicated process for charging and fixing, requires a large amount of consumable materials, and consumes a large amount of power and is expensive. There is also a problem in terms of environmental friendliness because it is charged by corona discharge, ozone is generated in the charging process, and a harmful substance such as selenium is used for the photoconductor.

[0003]

As one of the problems, the conventional electrophotographic apparatus has a complicated process for charging and fixing, which requires many consumable materials and consumes a lot of power. Has the disadvantages of high cost and high cost of the device. Two of the problems are environmental resistance such as charging using corona discharge and generation of ozone in the charging process.

[0004]

According to the present invention, a thermo-photoresponsive group is introduced into a polymer side chain, or a polar reversible medium dispersed in a polymer is irradiated with light and / or heat is applied.
Recording and erasing means for reversibly converting hydrophilicity-hydrophobicity on the polar reversible medium by reverse photochromism of the responsive group, developing means for developing the polar reversible medium using liquid ink, and By providing a means for transferring the developed ink to the transfer body, it is possible to provide a printing method which can be simplified as compared with the electrophotographic apparatus and which has environmental resistance.

[0005]

1 is a block diagram showing an embodiment of a recording apparatus adopting the method of the present invention. In this recording device, a polar reversible medium 1 whose polarity is selectively reversibly converted by light and heat is coated on the surface of a drum 2. Drum 2
Rotates in synchronization with print information. At the bottom of drum 2,
A recording unit 3 is provided which forms a latent image by applying heat according to an image signal. The ink 4 is stored in the ink reservoir 5 and is transferred via the developing roller 6 onto the polar reversible medium 1 on which the latent image is formed. The transfer body 8 is conveyed between the drum 2 and the transfer roller 7. Further, on the left side of the drum 2, a cleaning means 9 and an erasing means 10 for converting a hydrophilic part to a hydrophobic part on the polar reversible medium 1 are provided. The operation of the recording apparatus configured as described above will be described below. The latent image to be formed is obtained by temporarily making the polar reversible medium 1 hydrophobic by the erasing means 10 and then applying heat from the recording means 3 in accordance with an image signal to form a hydrophilic portion on the surface. Ink reservoir 5
The latent image is visualized with the ink 4 on the developing roller 6 dipped in. The polar reversible medium 1 formed on the drum 2 as a visible image is conveyed to the position of the transfer roller 7 by the rotation of the drum 2, and is transferred to the transfer body 8 which is conveyed in synchronization.
Then, the residual ink on the polar reversible medium 1 is removed by the cleaning means 9. The latent image for which printing has been completed is erased by the erasing means 10 and is prepared for the next image formation.

The printing process will be described in detail with reference to FIG. The polar reversible medium 1 is obtained by introducing a spirobenzopyran derivative, which is a thermo-photoresponsive group, into a polymer side chain, or by dispersing the spirobenzopyran derivative in a polymer. It may be an inverse photochromic compound that reversibly converts hydrophilicity and hydrophobicity by isomerization. Polarity reversible medium 1 to Cote _Lee ring to the support 11 (2.1). After irradiating 15 the polar reversible medium with visible light to once make it a hydrophobic part, when heat 12 is applied according to the image signal, the part to which heat is applied is selectively changed from the hydrophobic part to the hydrophilic part on the polar reversible medium 1. Is converted to (2.2). Next, the hydrophilic ink 13 or the hydrophobic ink 14 is attached to the hydrophilic portion or the hydrophobic portion on the polar reversible medium, and transferred to a transfer body to obtain a character / image (2.3).

Thereafter, the polar reversible medium 1 is irradiated with visible light 15
Hydrophobicity is reproduced (2.5) by batch conversion of hydrophilic parts (2.4).

FIG. 3 is a block diagram showing an embodiment of a recording apparatus adopting the method of the present invention. In this recording apparatus, a belt member 16 having a surface coated with a polar reversible medium 1 whose polarity is selectively reversibly converted by light has a pair of conveying rollers 17, 1.
It is in tension at 8 and rotates in synchronization with the print information. A recording unit 3 that forms a latent image by applying heat according to an image signal is installed below the belt member 16.
Ink 4 is stored in the ink reservoir 5, and the developing roller
The latent image is transferred via 6 onto the polar reversible medium 1. The transfer body 8 is transported between the transport roller 18 side and the transfer roller 7. Further, a cleaning unit 9 and an erasing unit 10 for converting a hydrophilic portion to a hydrophobic portion on the polar reversible medium 1 are provided on the belt member 16. The operation of the recording apparatus configured as described above will be described below. The latent image formed by the erasing means 10 is a polar reversible medium 1
Is once made into a hydrophobic part, and then heat is applied from the recording means 3 in accordance with an image signal to form a hydrophilic part on the surface. A latent image is visualized with the ink 4 on the developing roller 7 dipped in the ink reservoir 5. The polar reversible medium 1 on the belt member 16 made into a visible image is conveyed to the position of the transfer roller 7 by the conveying rollers 17 and 18,
It is transferred to the transfer body 8 that is conveyed in synchronization. Then, the residual ink on the polar reversible medium 1 is removed by the cleaning means 9. The latent image for which printing has been completed is erased by the erasing means 10 and is prepared for the next image formation.

Next, the polar reversible medium will be described in detail.

[0010]

Embedded image

The polar reversible medium using a spirobenzopyran derivative as a photoresponsive group is isomerized from a ring-opened form to a ring-closed form of the above-mentioned thermo-photoresponsive group of the spiropyran derivative by irradiation with visible light, as shown in Chemical formula 2. And the hydrophobicity is manifested by the dipole moment reduction due to the spiro structure. On the other hand, when heat is applied to this, the spirobenzopyran derivative of the responsive group undergoes reverse isomerization from a ring-closed form to a ring-opened form, and hydrophilicity is manifested by an increase in dipole moment due to the dipole ionic structure.

The synthesis of the spirobenzopyran derivative will be described in detail. (Example 1) Synthesis of 4-bromonaphthylhydrazine hydrochloride (2)

[0013]

Embedded image

4-Bromoaminonaphthalene (1) 10.0 g
(45.0 mmol) was added to 20 ml of concentrated hydrochloric acid and cooled to 0 ° C.
An aqueous solution (20 ml) of 3.1 g (45.0 mmol) of sodium nitrite was slowly added to this solution, and the mixture was stirred at 0 ° C. for 30 minutes.
Thereafter, a solution of stannous chloride dihydrate (30.5 g, 135 mmol) in hydrochloric acid (40 ml) was slowly added, and the mixture was cooled overnight in a refrigerator. This was filtered and dried to obtain 11.0 g (yield 88%) of 4-bromonaphthylhydrazine hydrochloride (2). This reaction formula is shown in (Chemical Formula 3).

Synthesis of indolenine (3)

[0016]

Embedded image

4-Bromonaphthylhydrazine hydrochloride (2) 11.0 g (40.0 mmol) and 3-methyl-2-butanone 5.
0 g (60.0 mmol) was heated to reflux in 200 ml of methanol overnight. After the methanol was distilled off, 200 ml of concentrated hydrochloric acid was added and the mixture was heated under reflux for 3 hours. After cooling to 0 ° C., the mixture was made alkaline with an aqueous sodium hydroxide solution and extracted with benzene. After distilling off benzene, the residue was distilled under reduced pressure to obtain 10.0 g of indolenine (3) (yield 8
7%). This reaction formula is shown in Chemical formula 4.

Synthesis of indoline (4)

[0019]

Embedded image

Indolenine (3) 10.0 g (34.5 mmol) and methyl iodide 10.0 g (69.0 mmol) were heated to reflux in 50 ml of chloroform overnight. After the chloroform was distilled off, the residue was washed with ether, and an aqueous sodium hydroxide solution was added to add 1
Stir for time and extract with benzene. After distilling off benzene, the residue was distilled under reduced pressure to obtain 10.0 g of indoline (4) (yield 95%).
I got This reaction formula is shown in Chemical formula 5.

Synthesis of spirobenzopyran derivative (SP1)

[0022]

[Chemical 6]

Indoline (4) 10.0 g (33.0 mmol) and 3,5-dinitrosalicylaldehyde (5) 7.0 g (33.0
(mmol) was heated to reflux in 70 ml of ethanol for 3 hours. The reaction mixture was cooled, filtered, separated and purified by column chromatography, and recrystallized from ethanol to obtain 15.0 g (yield 93%) of a spirobenzopyran derivative (SP1). This reaction formula is shown in (formula 6).

Spectral data of spirobenzopyran derivative Melting point 288 to 290 ° C Molecular weight measurement (EI) m / z 495 (M ⁺ ) Elemental analysis value C ₂₃ H ₁₈ BrN ₃ O ₅ Calculated value C, 55.66% H, 3.66% N, 8.47% Actual value C, 55.49% H, 3.60% N, 8.37% IR (KBr) ν 3100, 3080, 1612, 1528, 1460, 1439, 131
1, 1215, 1093, 1018,866, 748 cm ^{-1 1} H-NMR (400MHz, DMF-d7, 80 ℃) δ / ppm 1.96 (s, 6H), 4.6
4 (s, 3H), 7.67 ~ 7.78 (m, 2H), 7.89 (d, J = 7.9Hz, 1H), 8.
44 (s, H), 8.47 (d, J = 7.9Hz, 1H), 8.60 ((s, 1H), 8.61 (d, J =
15.5Hz, 1H), 8.81 (d, J = 15.5Hz, 1H), 8.83 (s, 1H) Fig. 4 shows the electron spectrum of the above-mentioned spirobenzopyran derivative (SP1) in a chloroform solution. . Absorption maximum wavelength (λ of spiropyran derivative (SP1)
_max ) was 593 nm and the solution exhibited a bluish purple color. When this solution was irradiated with visible light, it turned colorless and returned to the original bluish purple by heating or irradiation with ultraviolet light. Stable reverse photochromism due to such repetition was observed in the solution.

Preparation of Polar Reversible Medium A polar reversible medium can be obtained by dispersing the above-mentioned spirobenzopyran derivative (SP1) as a thermo-photoresponsive group in a polymer and laminating it on a support. However, as the type of polymer that disperses the heat-photoresponsive group, for example, polystyrene, polyethylene, polypropylene, polytetrafluoroethylene, polyvinyl butyral, polycarbonate, polyvinyl chloride, epoxy resin, phenol resin,
Also, a mixture or copolymer of the above resins can be used, but a resin other than the above may be used. As a support,
A heat conductive polymer such as polyaramid or polyamide can be used, but other heat conductive polymers may be used. As the liquid ink, a conventionally known ink can be used. For example, the ink used in an inkjet printer can be adopted as the hydrophilic ink. As the hydrophobic ink,
The ink used in waterless planographic printing can be used.

The change in hydrophilicity-hydrophobicity of this polar reversible medium due to heat-visible light irradiation was evaluated from the change in contact angle on the film. The spiropyran derivative (SP1) and polystyrene are dissolved in chloroform, laminated on a support, air-dried, and then sufficiently vacuum-dried. Heat of this film-When the contact angle θ of pure water before and after irradiation with visible light was measured with a contact angle measuring device, the change in contact angle was found to be the spirobenzopyran derivative (SP1).
Depending on the composition ratio of polystyrene in 95 ° to 105 °
A reversible change of about 50 ° to 60 ° hydrophilic was obtained. In addition to polystyrene, when the contact angle was measured using a polar reversible medium using polyethylene or polypropylene as a resin matrix, hydrophilicity of the same degree,
A reversible change in hydrophobicity was obtained.

The above-mentioned spirobenzopyran derivative (SP1)
Was dispersed in polystyrene and the polar reversible medium obtained by laminating it on a support and the above-mentioned known hydrophilic ink or hydrophobic ink were mounted on the recording apparatus having the configuration of FIG. 1 to perform printing. As a result, good recording was possible on plain paper.

[0028]

INDUSTRIAL APPLICABILITY As described above, in the present invention, as a thermo-photoresponsive group, a spirobenzopyran derivative whose dipole moment is changed by inverse photochromism is introduced into a polymer side chain,
Alternatively, the polar reversible medium dispersed in a polymer can control the hydrophilic-hydrophobic reversible conversion on the polar reversible medium, and it is possible to reduce the size, speed, cost, and power consumption, and it is highly reliable. An excellent printing technique can be provided.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of an embodiment of the present invention.

FIG. 2 is a schematic diagram of a printing process of the present invention.

FIG. 3 is a schematic configuration diagram of an embodiment of the present invention.

FIG. 4 shows an electronic spectrum of a spirobenzopyran derivative (SP1) in chloroform.

[Explanation of symbols]

 1 polar reversible medium 2 drum 3 recording means 4 ink 5 ink reservoir 6 developing roller 7 transfer roller 8 transfer body 9 cleaning means 10 erasing means 11 support 12 heat 13 hydrophilic ink 14 hydrophobic ink 15 light irradiation (550-650 nm) 16 Belt member 17 Conveyor roller 18 Conveyor roller

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03G 15/05 B41J 3/20 117A G03G 15/00 115

Claims (5)

[Claims] 1. A step of converting at least a polar reversible medium containing a thermo-photoresponsive group in a polymer from hydrophobic to hydrophilic on the polar reversible medium by reverse photochromism of the responsive group by applying heat. A step of developing the polar reversible medium with a liquid ink, a step of transferring the developed ink on the polar reversible medium to a transfer body, and the polarity based on the reverse isomerization of the responsive group by light irradiation. A printing method comprising a step of reversibly converting a reversible medium from hydrophilic to hydrophobic. 2. A recording in which a polar reversible medium containing at least a thermo-photoresponsive group in a polymer is converted from hydrophobic to hydrophilic on the polar reversible medium by reverse photochromism of the responsive group by application of heat. Means, a developing means for developing the polar reversible medium using a liquid ink, a means for transferring the developed ink on the polar reversible medium to a transfer body, and a means for reverse isomerization of the responsive group by light irradiation. A printing apparatus comprising an erasing unit for reversibly converting from hydrophilicity to hydrophobicity on the polar reversible medium. 3. The polar reversible medium according to claim 2, which is obtained by dispersing a thermo-photoresponsive group exhibiting reverse photochromism in a polymer. 4. The polar reversible medium according to claim 2, which is obtained by introducing a thermo-photoresponsive group exhibiting reverse photochromism into a polymer side chain. 5. A compound exhibiting reverse photochromism,
The thermo-photoresponsive group according to claim 2, which is a spirobenzopyran derivative represented by the general formula (Formula 1). Embedded image (However, R ₁ is an alkyl group having 1 to 11 carbon atoms, an aryl group having 1 to 20 carbon atoms, a methacryloxy group having a methylene chain having 1 to 6 carbon atoms, and a methacrylamide having a methylene chain having 1 to 6 carbon atoms. At least one of R ₂ , R ₃ , R ₄ and R ₅ is a substituent other than a hydrogen atom, and an alkyl group, a hydroxy group,
Amino group, alkylamino group, nitro group, halogen group,
It is a substituent of any one of an alkoxy group, a cyano group, a carbonyl group, a carboxyl group and an alkoxycarbonyl group. )