JPH04152182A - Recording device - Google Patents

Abstract

PURPOSE:To grasp fluctuation of the liquid level of a recording agent easily and suppress liquid level fluctuation as low as possible hence to prevent fluctuation in the size of liquid drop of the recording agent from generating by providing a lequid surface position detecting means on a recording agent feeding means. CONSTITUTION:At a peeling boundary area 23 between a recording body 7 and a recording agent 3a which comes into contact with the recording body 7, the liquid level is easily subjected to external vibration, etc., and there is inclination that a good transfer image connot be obtained because a favorable development of image is not performed due to the fluctuation in the size of liquid drop of the recording agent 3a to be adhered. In order to prevent such a condition from happening previously, a means 9, which detects the liquid level of the recording agent 3a at the peeling boundary area 23 where the recording body 7 comes into contact with the recording agent 3a, is provided. This means always monitors condition of the liquid level, and controls the title recording device in response to the condition. For the liquid level detecting means 9, an optical detecting means, which detects reflection intensity change or transmitted light intensity change due to the liquid level change, is adopted. The detecting means performs the control of the liquid level or decision of image printing, and display for the user of the device. As a control method of the liquid level, there is a method in which a plate shaped member 901 is brought into contact with the liquid level at the time of liquid level change detection and so forth.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a new recording device, and more specifically, the present invention relates to a new recording device, and more particularly, to the surface of a recording medium whose surface has specific properties, selectively or selectively and reversibly, A latent image is formed by forming a region exhibiting a receding contact angle according to the heating temperature, and then or simultaneously with the formation of the latent image, a recording agent containing a color developer is supplied to the latent image to develop it. The present invention relates to a recording apparatus which transfers the image onto recording paper after converting the image into a digitized image.

[Conventional technology]

A typical method for dividing the surface into a liquid-adhesive area and a non-liquid-adhesive area for image formation is an offset printing method using a lithographic printing plate without water (dampening water). It will be done. But.

The key to this offset printing method is that it incorporates the plate-making process from the original plate and the printing process from the printing plate (printing plate) into one device, and the miniaturization of plate-making and printing devices is becoming more and more solid. ing.

For example, even in relatively compact office offset plate making and printing machines, the plate making device and the printing device are usually separate.

In order to eliminate such defects of the offset printing method, we have developed a method that can form liquid-adhesive areas and non-liquid-adhesive areas according to image information, and can be used repeatedly (
Reversible recording methods and devices have been proposed. Some of them are as follows.

(1) Aqueous development method After applying an electric charge to the hydrophobic photoconductor layer from the outside, it is exposed to light to form a pattern on the surface of the photoconductor layer that has a hydrophobic part and a hydrophilic part. An aqueous developer is applied and the image is transferred to paper or the like (Japanese Patent Publications No. 40-18992, Japanese Patent Publication No. 18993-1973, Japanese Patent Publication No. 9512-1982, Japanese Patent Application Laid-Open No. 63-264392, etc.).

(2) Method using photochemical reactions of photochromic materials A layer containing materials such as spiropyran and azo dyes is irradiated with ultraviolet rays, and these photochromic compounds are made hydrophilic by the photochemical reaction [e.g., R-Kobunshi Papers, No. 37
Vol. 4, p. 287 (1980)).

(3) Method using the effect of internal biasing force Forms an amorphous state and a crystalline state through physical changes to form areas to which liquid ink adheres and to which it does not adhere (Japanese Patent Publication No. 41902/1982).

According to the method (1) above, after the aqueous ink is transferred to paper or the like, the hydrophilic portion is erased by static electricity removal, making it possible to record other image information. That is, one original plate (photoconductor) can be used repeatedly. However, since this method is based on an electrophotographic process, it requires a long process of charging, exposing, developing, transferring, and removing static electricity, and has the disadvantage that it is difficult to miniaturize the device, reduce costs, and make it maintenance-free. .

According to method (2) above, hydrophilicity and hydrophobicity can be freely and reversibly controlled by selectively changing the irradiation with ultraviolet rays and visible light, but the reaction time is extremely long due to poor quantum efficiency. However, it has disadvantages such as slow recording speed and lack of stability, and the reality is that it has not yet reached a practical level.

Furthermore, according to the method (3) above, the information recording member used therein is stable after recording, but before recording there is a risk that physical structural changes may occur due to temperature changes. There are still problems with storage stability. In addition, since a method of applying a heat pulse and then rapidly cooling is employed to erase the recorded information pattern, repeated image formation is unavoidably complicated.

[Problem to be solved by the invention]

An object of the present invention is to provide a member (
selectively or selectively and reversibly forming a desired pattern area on the surface of the recording medium (A)),
The object of the present invention is to provide an apparatus that visualizes this image and transfers it to plain paper or the like.

Another object of the present invention is to form and erase a desired pattern area;
To provide a new recording device that can reversibly perform the above steps multiple times by using a recording medium (A) with excellent preservability and stability in all steps such as visualization and transfer. It is.

Still other objects of the present invention are to enable miniaturization, cost reduction, and maintenance-free operation, and to enable recording material (
The present invention provides a recording device that can obtain high-quality transferred images by preventing as much as possible disturbances in image quality due to fluctuations and movement of the liquid level of ink (ink liquid, etc.).

[Means to solve the problem]

The recording device of the present invention can be produced by selectively heating the following recording body (A) while in contact with the following contact material (B), or by contacting the recording body (A) with the surface of the recording body (A) selectively heated. A contact material (B) that forms a latent image area showing a receding contact angle depending on the heating temperature (amount of heating energy) on the surface of the recording material (A) by contacting with the material (B) is applied to the recording material (A).
A) A means for supplying the recording agent to the surface, a means for heating the surface of the recording medium (A), a recording agent applying means for making the latent image area visible, and a recording agent attached to the surface of the recording medium (A). A means for transferring onto a recording paper, and a recording medium (A) including the recording agent (ink liquid, etc.)
The present invention is characterized in that it is provided with means for detecting the position of the recording agent liquid level at the peeling boundary portion which is in contact with the peeling boundary portion.

(A) A recording material having a surface whose receding contact angle decreases when brought into contact with a liquid in a heated state.

(B) A liquid, a vapor, or a solid that becomes a liquid or generates a liquid or vapor at a temperature below the temperature at which the receding contact angle begins to decrease in the recording material (A).

In the apparatus of the present invention, the latent image can be erased by heating the surface of the recording medium (A) on which the latent image is formed in the absence of the contact material (B), and image formation can be performed reversibly. It is possible.

The inventors of the present invention have conducted extensive research and study on new recording methods to eliminate the defects described in the prior art. As a result, a member whose surface has the function of being heated in contact with liquid and having a low receding contact angle even after cooling, and having a high receding contact angle when heated in the absence of liquid, is useful as a recording medium. I found that. A recording medium (A) having such a function has a surface that is (1) a member containing an organic compound having a surface self-alignment function of hydrophobic groups, or (2) a member containing an organic compound having a hydrophobic group and having a surface self-alignment function. It was also confirmed that it was a member with oriented on the surface.

The "surface self-orientation function" referred to in (1) means that when a solid formed of a certain compound on a support or a solid made of the compound itself is heated in air, the hydrophobic groups on the surface move toward the air side (
This means that it has the property of being oriented toward the free surface side. This also applies to (2). Generally, in organic compounds, hydrophobic groups tend to face toward a hydrophobic atmosphere. This is a phenomenon that occurs because the interfacial energy of the solid-air interface tends to become lower. Furthermore, this phenomenon tends to occur as the molecular length of the hydrophobic group increases, and this is because the longer the molecular length, the higher the mobility of the molecule during heating.

More specifically, if the molecule has a hydrophobic group at the end (i.e., lowers the surface energy), it is likely that the surface will be oriented toward the air side (free surface side).
In a linear molecule containing , the 1+CH, CH, +- portions have a planar structure, and the molecular chains are easily oriented with respect to each other. Furthermore, the -10+- portion of the molecule containing -eo+- has a planar structure, and the molecular chains tend to align with each other. In particular, linear molecules containing highly electronegative elements such as fluorine have high self-aggregation properties, and the molecular chains tend to align with each other.

Summarizing these study results, it is more preferable to use linear molecules that contain molecules with high self-aggregation or molecules that have a planar structure and have a hydrophobic group at the end, or such linear molecules. It can be said that the compound containing this compound has a high surface self-alignment function.

As is clear from the above description, there is a relationship between the surface self-alignment state and the receding contact angle, and there is also a relationship between the receding contact angle and liquid adhesion. That is, the adhesion of a liquid on a solid surface is mainly caused by tacking of the liquid on the solid surface. This tacking can be thought of as a type of frictional force when a liquid slides on a solid surface. Therefore, the "receding contact angle" θr in the present invention has the following formula: (γ: surface tension of solid in vacuum γS: solid -
The following relational expression holds true: liquid interfacial tension πe: equilibrium surface tension γ; frictional tension γS: surface tension of a solid without an adsorption layer) (Saito, Kitabata, et al., “Japan Adhesive Association Journal JVoQ
, 22, PkL12. &1986).

Therefore, when the value of θr decreases, the value of γ increases.

That is, the liquid becomes difficult to slide on the solid surface, and as a result, the liquid adheres to the solid surface.

As can be inferred from these mutual relationships, the liquid adhesion depends on the receding contact angle θr, and the receding contact angle θr is determined by the addition of a member having a surface self-alignment function to the surface. Therefore, in the apparatus of the present invention, the recording medium (A) necessarily includes a member having a surface self-alignment function on its surface because it is necessary to form a desired pattern area on its surface and/or to form an original image with a recording agent. It must be selected.

As described above, the recording medium (A) used in the apparatus of the present invention has "a surface whose receding contact angle θr decreases when it is heated and comes into contact with a liquid."

The recording medium (A) may have any shape as long as its surface has the properties described above. Therefore, recording body (A)
It may be in the form of a film, or another coating film having the above-mentioned surface properties may be provided on a suitable support or molded body.

The molded body itself may be used, but its surface must have the properties described above.

Depending on the type of contact material (B), the liquid-adhesive portion in the latent image area of this recording medium (A) is either lipophilic or hydrophilic. Any of the ink recording agents can be used as needed.

Here, an example of classifying members or materials into several types that form a surface whose receding contact angle θr decreases when brought into contact with a liquid in a heated state is shown in Fig. 1 (a). is an example of a compound having a self-orientation function, which is a compound having a hydrophobic group in the side chain of a high molecular weight polymer, and the main chain and the hydrophobic group R are bonded through a bonding group J.

FIG. 1(b) is an example of a member in which the hydrophobic group is oriented on the surface of an organic compound having a hydrophobic group. This is a member formed with compound O. Figure 1 (c
) is an example of a member made only of the organic compound O having a hydrophobic group shown in FIG. 1(b).

Figure 1(d) is an example in which a linear molecule is on the side chain of a polymer, and the molecule is connected to the main chain by a bonding group J.

It is a compound in which a molecular chain N having a self-aggregating or planar structure with a hydrophobic group R at the end is located in the middle.

In the examples shown in FIGS. 1(a) and 1(d), the main chain of the polymer compound may be linear or have a mesh structure.

In the example of FIG. 1(b), the hydrophobic group-containing compound 0 may be further laminated on the hydrophobic group-containing compound O, like a cumulative LB film, and in the example of FIG. 1(c), , it has a structure consisting only of a hydrophobic group-containing compound 0 without having a main chain (L) or bonding to an organic/inorganic material (A).

The above-mentioned hydrophobic group is preferably -CH at the terminal of the molecule.
3, -CF, -CF, Hl-CFH2, -C(CF
a) i, -C(CH3)3, etc., and those with a long molecular length are more preferable in terms of high single molecule mobility. Among them, the hydrophobic group is a substituted alkyl group having one or more -F and/or -CΩ (-CF, CF
, CFCF2CF, NoyotoQ) or an unsubstituted alkyl group, preferably one having 4 or more carbon atoms. Both fluorine-substituted and chlorine-substituted ones can be used, but fluorine-substituted ones are more effective. In these materials, in terms of the relationship between the number of carbon atoms in the alkyl group and the function, if the number of carbon atoms is 3 or less, the function suitable for a recording device will be low.

The principle of this functional expression has not yet been completely clarified, and therefore there are many unknown points, but the following is assumed.

First, it is considered that the surface of the recording medium (A) formed from the above compound is a surface in which the hydrophobic groups are considerably oriented. Therefore, this surface has liquid repellency (because hydrophobic groups have low surface energy). In this state, when the surface of the recording medium (A) comes into contact with the contact material (B) and is heated, the molecular movement of the hydrophobic groups becomes active due to the heating.
And upon interaction with the contact material (B), the recording body (
A) The orientation (alignment) state of at least a portion of the surface changes to another state (ie, another orientation state or a disordered orientation state).

This seems to be to maintain the different state even after cooling.

Note that heating the recording medium (A) with the surface of the recording medium (A) in contact with the contact material (B) may mean that the surface of the recording medium (A) is heated, depending on the form of the contact material (B). The liquid will come into contact with the

Before this heating, the hydrophobic groups are aligned (orientated) on the surface, so the surface energy of the recording medium (A) is extremely low.

However, heating the material in contact with the contact material (B) disturbs the orientation state and increases the surface energy. The receding contact angle θr depends on the type of liquid and is determined by the balance of surface energy between the solid and the liquid. Therefore, if the surface energy of the solid increases, the receding contact angle or will decrease regardless of the type of liquid. Therefore, the adhesion to liquids will increase.

Furthermore, the surface of the recording medium (A) is in a different state (a "different orientation state" different from the original orientation state or a "disturbed orientation state").
When heated in the absence of contact material (B), no interaction with contact material (B) occurs.

It seems that the original alignment (orientation) state is restored.

Therefore, the presence of the contact material (B) is not simply for rapidly cooling the surface of the recording medium (A) after heating, but it is for causing some kind of interaction with the compound on the surface of the recording medium (A). , it is only after this interaction that another state I
A change to II (another orientation state or a state with disordered orientation) appears to occur.

As mentioned above, when an alkyl group or a fluorine- or chlorine-substituted alkyl group is employed as the hydrophobic group of the member (compound) forming the surface of the recording medium (A), the number of carbon atoms in the alkyl group is 4 or more. It is desirable to have a recording medium (A
) This is thought to be due to the number of alkyl groups required to align (orient) to a certain extent on the surface and to cause active molecular movement when heated. In addition, the contact material (B) is the recording medium (^
) When the surface of the recording medium (A) is heated, molecules of the contact material (B) may be incorporated into molecules on the surface of the recording medium (A). Furthermore, when highly electronegative fluorine or chlorine is present in the alkyl group, the interaction with liquids, particularly polar liquids, increases, resulting in a greater change in adhesion than with compounds containing only hydrogen alkyl groups. In addition, fluorine-containing alkyl groups have strong self-aggregation properties, so they have a high surface self-alignment function, and furthermore, because they have low surface energy,
It is excellent in preventing skin stains.

Yet again. The surface of the recording medium (A) has liquid repellency, but when this is described in terms of the surface energy of a solid, the inventors have found that it is desirable for the recording device to have a surface energy of 50 dyn/c- or less. .

If the value is higher than this, the surface of the recording medium (A) may sometimes become wet with the recording agent, which may cause the background to become smeared.

Here, details of the compound forming the surface of the recording medium (A) will be described. First, for the types shown in FIGS. 1(a) and 1(d), compounds having an alkyl group (including fluorine and/or chlorine) in the vinyl polymer side chain are considered.

Specifically, formula (I) (II) (III) (IV) (V
) (VI) and (■) Rnee H1-CH3, -C,H,, -CF□ or -C,
F.

Rf: a C4 or higher alkyl group, a group containing a fluorine- or chlorine-substituted alkyl group, or -4 in the molecular chain
: CF No. 1, + CH2+ Hydrophobic group having a or -0- (Q≧4) A polymer in which the monomer is an integer of n'=1 or more can be mentioned.

Other polymers include formulas (■) (■) and (X)
Examples include the ones shown below.

R knee H1-CH3, -C, H-CF, or -C,F
.

Rf: C, a group containing an alkyl group or more or a fluorine- or chlorine-substituted alkyl group, or a group containing 1+ in the molecular chain
cFz) a, -+CHz+m or -〇- containing hydrophobic group (
a≧4) n: an integer of 10 or more In more detail, Rf in these specific examples can be exemplified by the following (1) to (20).

(1) -CH, CF, CHFCF3 (s) CHI (cFs)t. H (7) (CF, h-0-CF, CF.

(8) −+cH−τNH−CF2CF3(9) +CF
*) rCFa Qo) −+cut) x. C1F17 (13) -CH,NH30,C,F.

(14) -+cFt4ΣF (15) C-8-CH,CH,-(CF, ), CF(
CF3)2(16) -CHBCF,CF,CF3(1
7) -CH,CH,CH,CH,F(18) -CH
,(CF,),CF.

(19) -GHz (CF2) scFi (2 CH,
)3CF.

Among these compounds, especially The use of materials is advantageous.

The following (X[) [However, R1: Hydrogen, -CnLn+z or -CnF! n+1(n
= 1 or an integer of 2 or more) R”: (CH, (・ (Integer of P≧1) or -(CH,
(N (R”) So, -(R3 is -CH, or -C
2H,, an integer of q≧1) - an integer of 26 or more. ] Therefore, the most preferable specific compounds for the member on the surface of the recording medium (A) in the present invention include the following.

Furthermore, these formulas (1) (II) (III) (m
V) In addition to (V) (VI) (■) and (copolymer of two or more monomers), other monomers such as ethylene, vinyl chloride, styrene, butadiene, isoprene , chloroprene, vinyl alkyl ethers, vinyl acetate, vinyl alcohol, etc. are also suitable as the above compounds.

Furthermore, a monomer of formula (X[) and a polymerizable monomer having a functional group, such as CH, =C(CH3)COO(CH,), 0HCH2
=C(CH3)C00CH, CH(OH)CH.

Either create a copolymer with one or more of CH,=CHC00C)I, CH(O)l)C, F, etc. and introduce many functional groups into the polymer, or copolymerize with a monomer of formula (X[) and functional A copolymer with a polymerizable monomer having a group is made, and then,
Crosslinkable polymers produced by crosslinking copolymers containing a large number of functional groups using a crosslinking reagent are also excellent materials. Crosslinking reagents include formaldehyde and dialdehyde.

Examples include tomethylol compounds, dicarboxylic acids, dicarboxylic acid chlorides, bishalogen compounds, bisepoxides, bisaziridines, diisocyanates, and the like. An example of the crosslinked polymer thus obtained is shown below.

In the above formula, the A block is an alkyl group that brings about the aforementioned change in thermal properties, while the B block is a site that is crosslinking the linear polymer (crosslinked using diisocyanate as a crosslinking reagent). be.

To obtain a crosslinked film, a solution containing the above-mentioned copolymer and a crosslinking reagent is applied as a coating liquid onto a substrate, and a crosslinked polymer film is obtained by heating, electron beam irradiation, or light irradiation. do it.

In addition, in order to obtain a polymer from the above monomer, solution polymerization,
Electrolytic polymerization, emulsion polymerization, photopolymerization, radiation polymerization, plasma polymerization, graft polymerization, plasma initiated polymerization, vapor deposition polymerization, etc.
An appropriate method is selected depending on the material.

Next, the compound shown in FIG. 1(b) will be described.

Here, materials Rf-C○○H...(xn) R5-CH...(xm) Rf(CH2+TSIX...(xrv) shown in formulas (Xll), (xm), and (XIV)
) (Rf: a group containing an alkyl group having 4 or more carbon atoms or a fluorine- or chlorine-substituted alkyl group, or a hydrophobic group containing (cF2+-a, (CHz + sr or -■-) in the molecular chain (Q≧ 4)) Materials in which n: an integer of 1 or more, (Surface energy is approximately 50 dyn
/c+s or less) is desirable.

Specific examples of formulas (Xll) (Xm) and (XIV) include CF3-(CF2 juice C0OH).

CF, -+CF, soup C○○H2 CF□Rin CF2 soup (CH, soup OH.

H-+CF2 stone-COOH.

H-+CF, after CH20H2 F-4CF, )rcH2CH, -8i(CH,)2C4
.

CF, CM(CF3)CF(CF,)sCOOH.

CF□ (CF2)? (CH2) Z S x C and the like.

Examples of the compound shown in FIG. 1(C) include structures made only of materials of formula (x n ), formula (xm), and formula (XIV).

Next, a recording medium (A) using the above compound will be described.

The structure of the recording medium (A) includes a support (heat resistant temperature 50~
300° C.) on which the surface member is formed. Therefore, the shape of the recording medium (A) may be cylindrical or endless belt-like.
In the apparatus of the present invention, forming a mixture of the surface forming material of the recording medium (A) and other members such as a hydrophobic polymer or a hydrophobic inorganic material on the support is excellent in preventing background staining during printing. There is. Further, in order to increase thermal conductivity, metal powder may be mixed into the above compound. Furthermore, a primer layer may be provided between the support and the compound in order to improve the adhesion between the support and the compound. Heat-resistant supports include resin films such as polyimide and polyester, glass, Ni, AQ, Cu, Cr,
Metals such as Pt, metal oxides, etc. are preferable.

These supports may be smooth, rough or porous.

Next, the contact material (B) will be explained.

The contact material (B) is as described above, but to put it simply, it is a liquid or vapor from the beginning, or
It is a solid that eventually forms a liquid at a temperature below the temperature at which the receding contact angle or, referred to in the recording medium (A), begins to decrease. At least a part of the vapor here condenses to produce a liquid on or near the surface of the recording medium (A), and the liquid is formed on the recording medium (A).
Any material that can wet the surface of A) is sufficient. On the other hand, the solid here becomes a liquid, generates a liquid, or generates a vapor below the temperature at which the receding contact angle θr starts to decrease. As in the above case, the vapor generated from the solid condenses on or near the surface of the recording medium (A) to form a liquid.

More specifically, these contact materials (B) are as follows.

That is, in addition to water, liquids that are one of the contact materials (B) include aqueous solutions containing electrolytes, alcohols such as ethanol and n-butanol, polyhydric alcohols such as glycerin and ethylene glycol, and ketones such as methyl ethyl ketone. Examples include polar liquids such as, linear hydrocarbons such as n-nonane and n-octane, cyclic hydrocarbons such as cyclohexane, and nonpolar liquids such as aromatic hydrocarbons such as xylene and benzene. . Moreover, a mixture of these may be used, or even a polar liquid may be used.

In addition to water vapor, any liquid vapor of the contact material (B) can be used as the vapor, which is one of the other contact materials (B), but in particular, vapors of organic compounds such as ethanol vapor and ■-xylene vapor can be used. (including those in a spray state).

The temperature of this organic compound vapor must be below the melting point or softening point of the compound forming the surface of the recording medium (A).

Other solids used as the contact material (B) include higher fatty acids, low molecular weight polyethylene, polymer gels (polyacrylamide gel, polyvinyl alcohol gel), silica gel, and compounds containing water of crystallization.

As will become clearer from what will be described later, when a recording material "containing a color developer" such as the liquid ink described above is used as the contact material (B), the latent image is formed and developed at the same time. It will be done.

Next, the heating means will be explained.

Heating means for forming a latent image include contact heating using a heater thermal head or the like, as well as non-contact heating using electromagnetic waves (light beams from a light emitting source such as a laser light source or an infrared lamp are focused with a lens).

In FIG. 2(a), a film 2 of the compound constituting the surface of the recording medium (A) is formed on the support 1, and a liquid 3 of the contact material (B), for example, is present on this film surface. It shows the state of being. In this state, when the film 2 is heated, the receding contact angle θr of the surface of the film 2 decreases, exhibits significant wetting, and is observed to have liquid adhesion. Furthermore, this liquid-adhesive membrane 2 is heated again in the absence of the contact material (B), that is, in air, vacuum, or an inert gas atmosphere (
As shown in FIG. 2(b)), it is observed that the receding contact angle θr increases on the surface of the film 2, and it again exhibits liquid repellency.

As a phenomenon somewhat similar to this one,
There is a method described in the above-mentioned Japanese Patent Publication No. 54-41902. However, the method disclosed herein differs mechanically in that it provides a layer of memory material in the recording material that is substantially disordered and generally amorphous. That is, in the present invention, no change in state can occur on the surface of the recording medium (A) without the presence of the contact material (B).
In the method described in Japanese Patent No. 902, reversibility cannot be obtained with a simple operation.

As shown in Fig. 3 (a), heat is applied to the membrane 2 in contact with the liquid 3 according to the image information (as shown in Fig. 3 (b-t) (b-z), heat is applied to the membrane 2 in the absence of liquid. The same is true even if the membrane 2 is brought into contact with the liquid while being heated according to the image information)
As a result, the surface of the membrane 2 in the heated portion becomes liquid-adhesive. In the figure, 4 is a heater, and 31 is a liquid supply port.

41 represents an infrared lamp, 5 a lens, and 6 a shutter.

3(a) shows an example in which the membrane 2 is heated through the support 1, but in the examples shown in FIGS. 3(b-1) and (b-2), the membrane 2 is heated directly. This is an example.

FIG. 4 shows an example of the variation in the contact angle of the aqueous solution before and after heating the film 2 in contact with the aqueous solution, and the variation in the contact angle of the aqueous solution when this membrane 2 is further heated in air. In FIG. 4, 0 represents the advancing contact angle and Δ represents the receding contact angle.

In general, if the receding contact angle is high, such as 90' or more, the surface is liquid repellent; if the receding contact angle is low, such as 90° or less,
Its surface exhibits liquid adhesion.

The heating temperature of the recording body (A) surface in contact with the contact material (B) is preferably in the range of 50°C to 250°C,
More preferably, the temperature is 80°C to 150°C. The heating time is about 0.1 msec to 1 second, preferably 0.5 msec to 2 seconds.
It is m seconds. As for the timing of heating, ■Recording body (A
) After heating the surface, bring it into contact with the contact material (B) before it cools; ■Heating the surface of the recording medium (A) while the contact material (B) is in contact with the surface of the recording medium (A). let,
Either one is fine.

On the other hand, in latent image erasing, the surface of the recording medium (A) is heated at 50 to 300°C, preferably at 10°C in the absence of the contact material (B).
What is necessary is just to heat it to 0-180 degreeC. Heating time is 11 seconds to 1
It is about 0 seconds, preferably 101 seconds to 1 second.

Next, the means for actually recording image information on the surface of the recording medium (A) will be explained in more detail.

One is to heat the surface of the recording medium (A) in accordance with an image signal in a liquid or vapor atmosphere to form a liquid adhering area (latent image formation) on the surface of the recording medium (A), and then to remove this latent image. A method in which a recording agent is attached to a latent image area by means of bringing the recording agent into contact with the image area (development), and then the recording agent on the surface of the recording body (A) is transferred to recording paper (indirect recording method). Furthermore, in this method, if the recording agent is brought into contact with the latent image area again after the recording agent is transferred, a printing method using the recording medium (A) as a printing plate can be obtained. In the above method, after the recording material is transferred to the recording paper, the surface of the recording material (A) on which the latent image has been formed is heated in the absence of liquid or vapor to erase the latent image, thereby forming a recording material ( A) is a reproducible recording method. FIG. 5(aL(b)) shows typical processes of an indirect recording method (printing method) and a reversible recording method (repetitive recording method) of a recording medium.

Next, the configuration of the apparatus of the present invention including the recording medium (A) will be described.

The recording body (A) has a surface (sometimes referred to as "film 2" or "recording body (A) surface") that reduces the receding contact angle when brought into contact with a liquid in a heated state. Any material may be used as long as it is on a support.

When a resin is used as the support for the recording medium (A), it cannot be said to be a good conductor of heat, so if heating is performed from the support side, the surface of the recording medium (A) will be heated and the liquid will not adhere. It takes some time to achieve this. Therefore,
It may be conceivable to use a good thermal conductor throughout the support or in parts on the support 1.

FIG. 6(a) shows that if a good thermal conductor such as a metal is used as a support (metal substrate 11), an organic thin film 12 is deposited on it, and then a film 2 is formed on top of it. directional heat conduction speed is improved. Examples of the organic thin film 12 here include polyimide, polyester, and phthalocyanine. This configuration is sufficient when the printing dots can be relatively large, but it is not suitable when the goal is higher density printing because the area with liquid adhesion expands due to heat diffusion in the surface direction. . For this reason, FIG. 6(b) shows a structure in which good heat conductor parts are divided and provided on the support 1 to prevent heat diffusion in the surface direction and to miniaturize the part 2a that has liquid adhesion. In FIG. 6(b), lla represents a minute metal film.

Next, a latent image forming means by heating and a recording agent applying means (visualizing means) will be described. As described above, the heating source is preferably a contact heating source such as a heater or a thermal head, or a non-contact heating source using electromagnetic waves such as a laser or an infrared lamp, and as the recording agent, those listed below are used.

By the way, in FIG. 7, for example, the drum-shaped recording body 7 is covered with recording material (
This figure shows a typical example of how a latent image is formed and simultaneously visualized using colored ink, etc.) 3a. Here, a part of the rotating recording body 7 is immersed in the ink liquid 3a (recording agent) and is in contact with the thermal head 42, and the latent image (S) is formed and visualized at the same time. , and the ink liquid (adhered ink liquid) 38' adhering to the recording body 7
3 in figure 0, which shows how is transferred to the recording paper P.
a' is a transferred image (recorded image), 3b is an ink liquid storage container, 8 is a pressure roller, and 41a is an erasing heat source.

In such a visualization means, as shown in FIG. 8, the separation boundary (rear boundary) 23 of the recording agent 3a in contact with the recording medium 7 is caused by external vibration or the like, and the liquid level is increased. It is easy to vibrate, and the droplets of the recording material 3a to be deposited vary, making it difficult to develop a good image.Therefore, there is sometimes a tendency that a good quality transferred image cannot be obtained. In addition, if the recording device is left unused for a long period of time, the solvent in the recording agent 3a may evaporate and the liquid level may move, resulting in a decrease in the amount of attached ink droplets. It is not inconceivable that this would become impossible.

In order to prevent such an inconvenient situation from occurring in the apparatus of the present invention, "means 9 for detecting the liquid level position of the recording agent 3a at the peeling boundary portion 23 where the recording medium 7 contacts the recording agent 3a" is provided. (Figure 9).

This means constantly monitors the state of the liquid level and controls the recording device based on the state.

Several means can be considered for the liquid level position detection means 9.

FIG. 10 shows an example in which the detection means is arranged at a part or multiple locations of the peeling boundary 23, such as a change in reflected light intensity (FIG. 10(a)) and a change in transmitted light intensity (FIG. 10(a)) due to a change in the liquid level. Figure (b
)) are employed. FIG. 10(b) is an example in which the support of the recording medium (A) is transparent.

Figures 11 (a) and (b) employ electrical detection methods such as changes in resistance between electrodes (Figure 11 (a)) and changes in capacitance (Figure 11 (b)) as the liquid level changes. This is an example.

The method shown in FIGS. 11(a) and (b)
This method is superior to the methods shown in Figures (a) and (b).

These detection means control the liquid level, judge image printing, and display information to the device user based on liquid level vibration and position information.As a method of controlling the liquid level, a plate-shaped There is a method of bringing the member 901 into contact with the liquid surface when detecting a liquid level change. In addition, when a liquid level change is detected or the liquid level moves due to evaporation, etc., the system makes a 0N10FF judgment for image printing, such as stopping the device without sending an image printing signal, or displays an abnormality in the liquid level position to the device user. , equipment maintenance, etc. It is sufficient that the device has at least one of these mechanisms.

In addition, in FIG. 10, FIG. 11, and FIG. 12, 91 is a light source;
92 is a light receiving element, 93 is an electrode, 901 is a plate member, 90
2 is an electromagnetic actuator, and 903 is an arm.

In the apparatus of the present invention, as mentioned above, formation of a latent image and development (visualization) on the recording medium 7 are performed by applying an image signal to the surface of the recording medium 7 while the surface of the recording medium 7 is in contact with the colored ink liquid 3a. It is desirable that heating is performed by the thermal head 42 or the like according to the amount of time, so that latent image formation and development operations are performed at the same time. Of course,
After the latent image is formed, this latent image may be visualized.

The erasing of the latent image is as described above, but the recording medium (
Considering that the latent image is formed again on A), the recording medium (A) heated by the latent image erasing operation is substantially cooled while being moved to the point where it is heated for forming the latent image. It is necessary to provide a latent image erasing means (non-contact or direct heating) at a location where the latent image is removed. Further, the actual heating temperature required for erasing varies depending on the material of the film 2, but it is preferably a temperature above the starting temperature at which the receding contact angle of the film 2 becomes low and below the decomposition point.

As the recording paper (subject to be transferred), transparent or opaque resin film, plain paper, inkjet recording paper, type paper, etc. are suitable.

Next, the recording medium will be described.

In order to obtain a visible image on the surface of the recording medium (A) in the recording apparatus of the present invention, a recording agent used in a conventional printing recording method such as writing ink, inkjet recording ink, printing ink, or electrophotographic toner is used. Among the recording materials that came,
It can be selected and used as appropriate.

To give a more specific example, for example, water-based inks include water-soluble inks containing water, a wetting agent, and dyes, or water;
Water-based pigment dispersion inks containing pigments, dispersing polymer compounds, and wetting agents as main components, emulsion inks in which pigments or dyes are dispersed in water using surfactants, and the like are used. Wetting agents used in water-based inks include the following water-soluble organic liquid compounds.

Monohydric alcohols such as ethanol, methanol, propatool; ethylene glycol, diethylene glycol,
triethylene glycol, tetraethylene glycol,
Polyhydric alcohols such as polyethylene glycol, propylene glycol, dipropylene glycol, glycerin; ethylene glycol monobutyl ether, diethylene glycol 7-methyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, propylene glycol 7-methyl ether, ethylene glycol, diethylene glycol Ethers of polyhydric alcohols such as heptanoethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol monoethyl ether, propylene glycol monoethyl ether; N-methyl-2-pyrrolidone,
Heterocyclic compounds such as 1,3-dimethylimidazolidinone and ε-caprolactam; amines such as monoethanolamine, jetanolamine, triethanolamine, monoethylamine, diethylamine, and triethylamine;

As water-soluble dyes, dyes classified as acid dyes, direct dyes, basic dyes, and reactive dyes in the color index are used. Examples of typical dyes include C, I, Acid Yellow 17, 23, 42, 44,
79,142C,1, Acid Red 1,8,13,
14, 18, 26, 27, 35° 37.42, 52, 8
2,87,89,92,97゜106.111,114
,115,134,186°249.254,289 C,1, Acid Blue 9.29,45,92,24
9,890C, 1, Acid Black 1, 2, 7, 2
4,26,94C,1, Hood Yellow 3,4 C,1, Hood Red 7.9.14 C,1, Hood Black 2 C,1, Direct Yellow 1,12,24,26,
33,44,50゜142.144,865 C, 1, Direct Red 1, 4, 9, 13, 17,
20,28,31゜39.80,81,83,89,2
25°C, 1, Direct Orange 26, 29, 62
, 102C, 1, Direct Blue 1.2, 6, 15
,22,25,71,76°79.86,87,90,
98,163°165.202 C, 1, Direct Black 19, 22, 32, 38
,51,56°71.74,75,77.154,16
8C, 1, Basic Yellow 1, 2, 11, 13,
14,15,19゜21.23,24,25,2g,2
9゜32.36, 40, 41, 45, 49゜51.53
, 63, 65, 67.70° 73.77.87, 91 C, 1, Basic Red 2, 12, 13, 14, 1
5.1g, 22゜23.24,27,29,35,36
, 38° 39.46, 49, 51, 52, 54, 59°C, 1, basic 68.69, 70, 73, 78, 82, 102° 104
．． 109,112 Ri・Blue 1, 3, 5, 7, 9, 21, 22, 26, 3
5゜41.45,47,54,62,65,66゜67
．． 69,75,77.78,89,92゜93.105
,117,120,122゜124.129,137,
141,147° Basic Black 2.8, etc.

Pigments include organic pigments such as azo, phthalocyanine, anthraquinone, quinacridone, dioxazine, indigo, thioindigo, perinone, perylene, and isoindorenone.

Examples include aniline black, azomethine azo, carbon black, etc. Inorganic pigments include iron oxide, titanium oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, dark blue, cadmium red, chrome yellow, and metal powder. .

Pigment dispersing compounds include polyacrylamide, polyacrylic acid and its alkali metal salts, acrylic resins such as water-soluble styrene-acrylic resin, water-soluble styrene-maleic acid resin, water-soluble vinylnaphthalene-acrylic resin, and water-soluble vinylnaphthalene-maleic resin. , polyvinylpyrrolidone, polyvinyl alcohol, alkali metal salts of formalin condensates of β-naphthalenesulfonic acid, polymeric compounds containing salts of cationic functional groups such as quaternary ammonium and amino groups, proteins such as polyethylene oxide, gelatin, and casein; Examples include natural rubbers such as gum arabic and gum tragacanth, glucoxides such as saponin, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, and methylcellulose, ligninsulfonic acid and its salts, and natural polymer compounds such as ceramics.

Like water-based inks, oil-based recording materials include those in which oil-soluble dyes are dissolved in organic liquid compounds, pigments dispersed in organic liquid compounds, pigments or dyes emulsified in oil-based bases, etc. is used.

Representative examples of oil-based dyes include C,1, Acid Yellow 17,23,42,44,
79,142C,1, Acid Red 1,8,13,
14, 18, 26, 27, 35° 37.42, 52, 8
2,87,89,92,97゜106.111,114
,115,134,186°249.254,289 C,1, Acid Blue 9.29,45,92,24
9,890C, 1, Acid Black 1, 2, 7, 2
4, 26.94C, 1, Hood Yellow 3, 4 C, 1, Hood Red 7.9.14 C, 1, Hood Black 2 C, 1, Direct Yellow 1, 12, 24, 26,
33,44,50゜142.144,865 C, 1, Direct Red! ,4,9,13,17,
20.2g, 31°39.80,81,83,89,2
25°C, 1, Direct Orange 26.29,62
, 102C, 1, Direct Blue 1, 2, 6, 15
,22,25,71,76°79.86,87,90,
98,163°165.202 C, 1, Direct Black 19, 22, 32, 38
,51,56°71.74,75,77.154,16
8C, 1, Basic Yellow 1, 2, 11, 13,
14,15,19゜21.23,24,25,28,2
9゜32.36, 40, 41, 45, 49゜51.53
, 63, 65, 67.70° 73.77.87, 91 C, 1, Basic Red 2, 12, 13, 14, 1
5,18,22゜23.24,27,29,35,36
, 38° 39.46, 49, 51, 52, 54, 59° 6g, 69, 70, 73.7g, 82, 102° 104
．． 109,112 C, 1, Basic Blue 1, 3, 5, 7, 9, 21
,22,26,35°41.45,47,54,62,
65,66゜67.69,75,77.7g, 89,9
2゜93.105,117,120,122゜124.
Examples include 129, 137, 141, 147° Basic Black 2,8.

Pigments include organic pigments such as azo, phthalocyanine, anthraquinone, and quinacridone.

Dioxazine type, indigo type, thioindigo type, perinone type, perylene type, isoindorenone type, aniline black, azomethine azo type, carbon black, etc., and inorganic pigments include iron oxide, titanium oxide, calcium carbonate, barium sulfate, Aluminum hydroxide, barium yellow, dark blue.

Examples include cadmium red, chrome yellow, and metal powder.

Polyacrylamide as a compound for pigment dispersion.

Polyacrylic acid and its alkali metal salts, acrylic resins such as water-soluble styrene acrylic resin, water-soluble styrene maleic acid resin, water-soluble vinylnaphthalene acrylic resin,
Water-soluble vinyl naphthalene maleic acid resin, polyvinyl pyrrolidone, polyvinyl alcohol, alkali metal salts of β-naphthalene sulfonic acid formalin condensates, polymer compounds containing salts of cationic functional groups such as quaternary ammonium and amino groups, polyethylene oxide, Proteins such as gelatin and casein, natural rubbers such as gum arabic and gum tragacanth, glucoxides such as saponin, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, and methyl cellulose, lignin sulfonic acid and its salts, natural polymer compounds such as ceramics, etc. , etc.

Like water-based inks, oil-based recording materials include those in which oil-soluble dyes are dissolved in organic liquid compounds, pigments dispersed in organic liquid compounds, pigments or dyes emulsified in oil-based bases, etc. is used.

Representative examples of oil-based dyes include C,1, Solvent Yellow 1,2,3,4,5,6
,7,8,9゜10.11,12,14,16,17゜26.27,29,30,39,40゜46.49,5
0,51,56,61°80.86,87,89,96 C,1, Solvent Orange 12,23,31,43
, 51, 61C, 1, Solvent Red 1, 2, 3,
16,17,18,19,20゜22.24,25,2
6,40,52,59゜60.63,67.68,12
1 C, I, Solvent Violet 7.16.17C,
1, so/l//< :/to・bu/L/-2,6,11,
15, 20, 30, 31, 32° 35.36, 55, 5
8, 71, 72 C, 1, Solvent Brown 2, 10, 15, 21,
22C, 1, Solvent Black 3, 10, 11, 1
Examples include 2, 13, etc.

Oil bases for dissolving dyes and dispersing pigments include n-octane, n-decane, minerane spirit, ligroin, naphtha, benzene, toluene,
Hydrocarbons such as xylene; dibutyl ether, dibutyl ether, anisole.

Ethers such as phenetol and dibenzyl ether: Examples include alcohols such as methanol, ethanol, isopropyl alcohol, benzyl alcohol, ethylene glycol, diethylene glycol, and glycerin.

The pigments exemplified above can also be used in oil-based inks. Examples of oil-based pigment dispersants include polymethacrylic esters, polyacrylic esters, methacrylic ester-acrylic ester copolymers, polyvinyl acetate, vinyl chloride copolymers, polyvinylpyrrolidone, polyvinyl butyral, and other vinyl dispersants. cellulose resins such as ethyl cellulose and methyl cellulose, condensation polymer resins such as polyester, polyamide, and phenolic resins,
Natural resins such as rosin, ceramic, gelatin, casein, etc. are available.

〔Example〕

Example 1 The material for the membrane 2 was prepared by solution polymerization in 1,1,1-trichloroethane using perfluoromethyl methacrylate (Viscoat 17FM, manufactured by Osaka Organic Chemical Co., Ltd.) as a monomer. After this material was purified, it was dissolved in Freon 113 and the solution was cast onto a polyimide film.

This was used as a recording medium (A) and wound around a drum having a diameter of 100 mm to produce a recording device as shown in FIG. The thermal head used had a thermal element with a pitch of 8 dots/am. Furthermore, as shown in FIG. 10(a), the recording medium (A)
A light emitting diode and a photodiode were placed near the liquid surface with the liquid as a reflective surface.

When external vibrations were applied to the device, the output of the photodiode changed in response to the vibrations in the liquid level, making it possible to detect changes in the liquid level.

Example 2 With the same configuration as Example 1, a recording medium (
A resin board was placed close to A) (Fig. 12). Further, an electromagnetic actuator was connected to this plate material, and the electromagnetic actuator was driven in response to the liquid level position detection signal so that the plate material approached the recording medium (A). When external vibrations were applied to the device, the photodiode output changed in response to the liquid level vibrations, detecting liquid level fluctuations, and the electromagnetic actuator was driven to stop the liquid level fluctuations.

EXAMPLE With the same configuration as Example 1, a control circuit for determining image printing based on the output of the photodiode was provided in the image signal application circuit. An attempt was made to perform recording with this device after the ink was intentionally removed, but the control circuit was activated and the device did not move.

〔Effect of the invention〕

According to the apparatus of the present invention, since the recording agent supplying means is provided with the liquid level position detecting means, it is possible to easily grasp the vibration state of the recording agent liquid level. In addition, this behavior suppresses liquid surface vibration to the utmost, and a high-quality transferred image can be obtained without causing variations in the recording agent droplets to be deposited.

[Brief explanation of drawings]

FIG. 1 is a schematic four-sided view of a configuration having a surface self-alignment function. FIGS. 2 and 3 are diagrams for basically explaining the apparatus of the present invention. Figure 4 shows the receding contact angle observed on the surface of the recording medium (A) when the surface of the recording medium (A) used in the practice of the present invention is heated with a liquid in contact with the surface. FIG. 3 is a diagram showing changes in θr. FIG. 5 shows two embodiments in which the apparatus of the present invention is used. FIG. 6, FIG. 7, FIG. 8, FIG. 9, FIG. 10, FIG. 11, and FIG. 12 are diagrams for explaining how the apparatus of the present invention is implemented. 1...Substrate 2...Membrane 3...Liquid (
3a... Colored ink, 3a'... Adhesive ink liquid) 4
... Heater 5 ... Lens 6 ... Shutter 7 ... Recording body (A) 8 ... Pressure roller 9 ... Detection means 41 ... Infrared lamp (41a ... Latent image erasure heating source) 42... Thermal head 91... Light source 92... Light receiving element
93...Electrode 901...Plate member 902...Electromagnetic actuator 903...Arm Patent applicant Rico Co., Ltd.

Claims (3)

[Claims] (1) By selectively heating the surface of the recording body (A) below while in contact with the contact material (B) below, or by selectively heating the surface of the recording body (A) below, the contact material ( B
), a means for supplying a contact material (B) onto the surface of the recording medium (A) to form a latent image area showing a receding contact angle in accordance with the heating temperature on the surface of the recording medium (A); A means for heating the surface of the recording body (A), a recording agent applying means for making the latent image area visible, a means for transferring the recording agent attached to the surface of the recording body (A) onto a recording paper, A) A recording apparatus characterized in that A) means for detecting the position of the recording agent liquid level at the peeling boundary portion in contact with the recording agent. (A) A recording material having a surface whose receding contact angle decreases when brought into contact with a liquid in a heated state. (B) A liquid, a vapor, or a solid that becomes a liquid or generates a liquid or vapor at a temperature below the temperature at which the receding contact angle begins to decrease in the recording material (A). (2) The recording apparatus according to claim 1, wherein a recording agent is used as the contact material (B), so that the contact material (B) supplying means and the recording agent applying means are integrated. (3) The recording apparatus according to claim 1 or 2, further comprising a mechanism for controlling the recording agent liquid level position based on the detected liquid level position.