JP3219299B2 - Recorded body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording medium, and more particularly, to selectively or selectively and reversibly form a liquid-adhesive area (latent image area) on the surface of a recording medium having high liquid repellency. If necessary, a recording agent (e.g., used in the form of a solution or dispersion such as a liquid ink) is supplied to this area to form an image, or after the supply of the liquid ink, The present invention relates to a recording medium suitable for transferring the image to plain paper to obtain a copy image.

[0002]

2. Description of the Related Art A lithographic printing plate precursor without water (fountain solution) is used as a typical means for dividing a surface into a liquid-adhesive area and a non-liquid-adhesive area for image formation. An offset printing method can be used. Research on forming non-image areas with an ink-repellent material and eliminating the supply of water (fountain solution) from lithographic printing has been undertaken from an early stage (U
SP3,632,375; USP3,677,178; JP-B-44-23042).

[0003] Since the late 1960's, ink repellency-imparting components have been broadly classified into silicone-based and fluorine-based components.
(Masao Iwamoto: Separate volume polymer processing,
6, (1984)).

[0004] Examples of currently available waterless lithographic printing original plates include a waterless printing original plate manufactured by Toray Industries, Inc. This master has a structure in which a photosensitive layer and a silicone layer are provided on an aluminum substrate serving as a base. In plate making printing, an image is formed with the help of the photosensitive layer.

In the case of the positive type, there are complicated steps of raw plate (original plate) → image exposure → development → printing plate → printing. Particularly, in the developing process, a special developing machine and chemicals are required. Since this offset printing method requires the above-described steps, it is difficult to incorporate the plate making process from the original plate to the printing plate (printing plate) and the printing process from the printing plate into one apparatus, and the plate making Miniaturization of printing apparatuses has become difficult. For example, even in a relatively small office offset plate making press, the plate making device and the printing device are usually separated from each other due to the complexity of the plate making process.

[0006] In order to eliminate such a defect of the offset printing method, a liquid-adhesive area and a non-liquid-adhesive area corresponding to image information can be formed, and can be used repeatedly (reversible). A recording method or apparatus using a recording medium has been proposed. Some of them are as follows.

(1) Aqueous development system After applying a charge to the hydrophobic photoconductor layer from the outside, it is exposed to light to form a pattern having a hydrophobic part and a hydrophilic part on the surface of the photoconductor layer, Aqueous developer is adhered only to the paper and transferred to paper, etc. (Japanese Patent Publication No. 40-18992, Japanese Patent Publication No. 40-18993)
JP-B-44-9512 and JP-A-63-264392).

(2) A method utilizing photochemical reaction of photochromic material A layer containing a material such as spiropyran or azo dye is irradiated with ultraviolet rays, and these photochromic compounds are hydrophilized by the photochemical reaction. Volume 37 4
Issue, p. 287 (1980)].

(3) A method utilizing the action of internal biasing force An amorphous state and a crystalline state are formed by physical change,
Constructing the area where liquid ink adheres and adheres (Japanese Patent Publication No. 54-419)
02 publication).

According to the method (1), after the aqueous ink is transferred to paper or the like, the hydrophilic portion is erased by static elimination, and another image information can be recorded. That is, it is possible to repeatedly use one master (photoconductor). However, since this method is based on the electrophotographic process, charging → exposure →
It requires a long process of development → transfer → discharge, and has drawbacks in that it is difficult to reduce the size and cost of the apparatus and to make maintenance free.

According to the method (2), hydrophilicity and hydrophobicity can be freely and reversibly controlled by selectively changing the irradiation of ultraviolet light and visible light, but the reaction time is low due to poor quantum efficiency. It has the drawbacks of being extremely long, slow in recording speed, and lacking stability, and has not yet reached a practical level.

Further, according to the method (3), the information recording member used there is stable after recording, but may have a physical structural change due to a temperature change before recording. However, there is still a problem in storage stability. In addition, since a means for applying a heat pulse and then quenching for erasing the recorded information pattern is employed, there is an inconvenience that repetitive image formation cannot avoid the complexity.

The present inventors firstly selectively or selectively and reversibly apply a desired pattern to the surface of a member (liquid repellent molded product) having a strong repulsive force against a liquid by a simple means. Proposed a method and apparatus capable of forming a liquid adherent region
(JP-A-3-178478). By using this method and apparatus, a good image can be obtained if, for example, liquid ink is supplied to the above-mentioned liquid-adhesive area, and after supplying the liquid ink, this is transferred to plain paper or the like. A clear image with gradation is obtained. Further, by using a material having excellent storage stability and stability regardless of before and after recording, it is possible to further form a reversible liquid-adhesive region.

The present inventors have further proposed the following recording medium (1) or (2). (1) The surface of the recording medium (A), and a contact material (B) selected from a liquid or a vapor and a solid that generates a liquid or a vapor at or below the receding contact angle decrease starting temperature indicated by the recording medium (A). By selectively heating the surface of the recording medium (A), or by contacting the surface of the recording medium (A) with the contact material (B) while selectively heating the surface of the recording medium (A). A recording method wherein at least the surface of the recording medium (A) used in a recording method for forming a region for reducing a receding contact angle with a recording agent contains a compound containing a fluorine atom in a side chain. body. (2) By selectively heating the surface of the recording material (A) and the contact material (B) in contact with each other, or by using the recording material (A)
After the surface of the recording medium (A) is contacted with the contact material (B) while the surface of the recording medium (A) is selectively heated to form a latent image area having a reduced receding contact angle with the recording agent, A recording agent is supplied to the area to visualize the area, and then this visible image is transferred to an object to be transferred, and the recording medium (A) is heated in the absence of the contact material (B) to clean the area. A recording material characterized in that at least the surface of the recording material (A) used in a recording method having reversibility to be eliminated contains a compound containing a fluorine atom in a side chain.

However, the recording mediums (1) and (2) still have some room for improvement. That is, in a high-density thermal head such as 400 dpi, the thermal element is easily heated because the thermal element interval is small, and the independence of the heated portion and the non-heated portion (that is, the latent image portion and the non-latent image portion) tends to deteriorate. When the surface of the support of the recording medium is particularly excellent in smoothness, a copolymer having a fluorine atom in a side chain or an acrylic acid-based monomer having no fluorine atom is used as a recording layer material. In the case of a copolymer, if the ratio of monomer units having a fluorine atom is not large, the characteristics are not exhibited, and the copolymer must be naturally treated with a Freon-regulated product such as Freon 113, or a fluorine-based product. Materials tend to be costly. In the method of dissolving the recording layer material in an appropriate solvent to form a film, when the recording medium is formed into a cylindrical shape, peeling of the recording medium or the recording layer from the substrate, generation of cracks, and poor adhesion to paper are also caused. A good image may not be obtained.

[0016]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned disadvantages and to provide a recording medium capable of obtaining a high quality image on plain paper.

[0017]

SUMMARY OF THE INVENTION A first aspect of the present invention is to provide a recording layer having a surface in which the receding contact angle is reduced when heated and in contact with a liquid; By selectively heating in contact with a contact material selected from solids that are liquid or vapor or liquid or vapor below the receding contact angle decrease start temperature,
Alternatively, a recording medium used in a recording method for forming a region having a receding contact angle according to a heating temperature on the surface of the recording layer by contacting the surface of the recording layer with the contact material in a state of being selectively heated. The recording medium has a projection, and the projection contains a compound containing a fluorine atom in a side chain.

In the second aspect of the present invention, the surface of the recording layer having a surface in which the receding contact angle decreases when heated and brought into contact with a liquid, the liquid, the vapor, and the start of the decrease in the receding contact angle in the recording layer By selectively heating in a state of contacting with a contact material selected from a solid which forms a liquid or a vapor or a liquid at a temperature not higher than the temperature, or the contact in a state where the surface of the recording layer is selectively heated. A recording medium used in a recording method for forming a region having a receding contact angle according to a heating temperature on the surface of the recording layer by bringing the recording layer into contact with a material, wherein the recording medium is a material obtained by blending two or more polymers. And at least one of the polymers comprises a compound containing a fluorine atom in a side chain.

A third aspect of the present invention is that the surface of the recording layer having a surface in which the receding contact angle decreases when heated and brought into contact with a liquid, the liquid, the vapor and the start of the decrease in the receding contact angle in the recording layer. By selectively heating in contact with a contact material selected from a solid that becomes liquid at or below the temperature and / or generates liquid or vapor, or in a state where the surface of the recording layer is selectively heated. A recording material used in a recording method for forming a region having a receding contact angle according to a heating temperature on the surface of the recording layer by bringing the recording material into contact with the contact material. It is characterized in that it has a structure in which fine particles are arranged, and that the fine particles contain a compound containing a fluorine atom in a side chain.

According to the use of such a recording medium, the above-mentioned problem can be sufficiently achieved.

The compounds containing a fluorine atom in the side chain include those represented by the following general formulas (I), (II), (III), (IV) and (V). Copolymers containing at least one monomer component are exemplified.

[0022] [However, R¹Is hydrogen or -CH_ThreeR represents a group^TwoIs-
(CH_Two) NR^Three(N is an integer of 1 to 10, R^ThreeIs carbon number 3
Up to 21 linear or branched perfluoroalkyl
Group), -CH_TwoCF_TwoCHFCF_Three, (However, -Ph- represents a paraphenylene group.
), -CH (CF_Three)_Two,A branched perfluoroalkyl group) or -CH [CH_TwoO
CF (CF_Three)_Two]_TwoRepresents ]

[0023] [However, R¹Is hydrogen or -CH_ThreeR represents a group⁶Is-
(CF_Two) NF (n is an integer of 1, 3 to 17),-(C
H_Two) NR⁷(N is an integer of 1 to 10, R⁷Is 3 to 2 carbon atoms
1 linear or branched perfluoroalkyl
Group) or -R⁸N (R⁹) SO_TwoR^Ten(R⁸Is carbon number 1 to 1
Two alkylene groups, R⁹Is hydrogen or C 1-6
A linear or branched alkyl group, R^TenHas 4 or more carbon atoms
12 linear or branched perfluoroalkyl
Group). ]

[0024] [However, R¹Is hydrogen or -CH_ThreeR represents a group¹¹Is -P
h-F, -SCH_TwoCH_TwoR¹²(R¹²Is 5 to 13 carbon atoms
Linear or branched perfluoroalkyl group)
Is -CH_TwoRepresents F. ]

[0025] [However, R¹Is hydrogen or -CH_ThreeR represents a group¹³Is -P
h-F, (n⁸Represents an integer of 1 to 18). ]

[0026] [However, R¹Is hydrogen or -CH_ThreeR represents a group¹⁴Is -C
H_TwoCF_TwoH, -CH_TwoCF_TwoCH_Three, -CHCF_Three,-(C
H_Two)_ThreeCF_ThreeOr-(CH_TwoCF_TwoH)_TwoRepresents ]

That is, the present invention provides a liquid repellent material as a material for forming the recording medium (A) of the first and third inventions (strictly speaking, a material for forming a surface layer of the recording medium (A)). By using a strong “compound having a fluorine atom in the side chain”, the contact material (B) is brought into contact with the surface of the recording medium (A) and heated, or the surface of the recording medium (A) is heated. Contact material
(B) and a region where the receding contact angle with the recording liquid is reduced can be easily formed on the surface of the recording medium (A).

On the other hand, the material for forming the recording medium (A) of the second invention of the present invention (strictly speaking, the material for forming the surface layer of the recording medium (A)) is the side chain described above. In this method, a compound obtained by blending a compound containing a fluorine atom as at least one of polymers is used, thereby obtaining a low-cost and reliable recording medium.

In the surface layer of the recording medium (A) in the present invention, the area where the receding contact angle is reduced by the above method is used as the contact material.
The receding contact angle can be recovered by heating in the absence of (B), and by repeating such a process, it is possible to easily form a region where the receding contact angle changes easily and reversibly. In other words, it is possible to provide a recording medium [recording medium (A)] that can reversibly control wettability with a liquid.

In the first recording medium according to the present invention, it is possible to provide a recording layer material on the substrate of the support, and it is also possible to constitute the recording medium using only the recording layer material itself. Here, the state of the projections is as follows: (a) When providing the base material of the support, a support having projections is used, a recording layer material is provided thereon, and projections are provided on the surface of the recording layer as a whole recording body.
(b) (c) No projection is provided on the substrate of the support, and the projection is provided on the recording layer on the surface. If no support substrate is provided,
(d) A recording medium is formed only from the recording layer material, and a projection is formed on the surface of the recording medium. In any case, a shape having projections on the surface of the recording medium is finally formed (FIGS. 4A, 4B, 4C, and 4D). In the figure, 1 indicates a substrate, and 2 indicates a recording layer.

There is a close relationship between the size of the protrusion and the interval between dots when printing with the thermal head. When the size of one dot is n (dpi), one side is (2
5.4 / n) × 1000 μm square. As the projections of the recording material, when the state of the surface is represented by a repeating unit of a concave portion and a convex portion in order to clearly express a dot, 1
It is desirable that there be one dot. Here, the “projection” is not a sharp state but a state in which the plane of the recording medium is divided.

Regarding the formation of the protrusions and the treatment of the surface, the protrusions can be formed by covering the recording layer with an appropriate mask or the like, heating, compressing, and then removing the mask. . Further, in the case of forming the recording layer material, a method of forming the material using a mold having appropriate irregularities on the surface is also possible. Furthermore, the surface may be scratched by an appropriate method, or a groove may be formed by using a knife or the like.However, the surface is not sharpened by heat treatment, compression treatment, etc. It is important that the division and the projection are flat. Also, the shape of the projection need not be limited to a square as shown in FIG.

In the second recording medium according to the present invention, it is considered that the outermost surface of the recording layer of the recording medium is involved in the development of the properties of the material, and the material having a fluorine atom in the side chain is selectively applied to the surface. It is important that they exist preferentially. On the other hand, there is a blending method as a method for transferring and concentrating a polymer having a specific molecular structure on an interface, that is, a recording layer surface. From these facts, it is effective to blend two or more kinds of polymers in order to selectively and preferentially make these exist on the surface of the recording medium by adding a small amount of a material having a fluorine atom in the side chain. is there. For polymer blending and film formation, two or more polymers are mechanically mixed, powders are mixed, or uniformly dissolved or dispersed in the same solvent system. In the latter case, the substrate is impregnated and sprayed on the substrate, or a film is formed by spin coating or the like. Further, it is also possible to form a recording body using only a recording layer material without providing a substrate. When blending, a third component such as a compatibilizer may be added. Accordingly, this type of recording medium is the same except that two or more polymers are blended, assuming that no projection is provided on the surface.

In the third recording body according to the present invention, an elastic body (elastic body layer) containing or not containing the fine particles of the recording layer material is provided on the substrate 1, and the recording layer 2a of the fine particles is further provided thereon.
Or a single-layered recording medium in which the elastic body itself containing the fine particles of the recording layer material is used as the recording layer (FIGS. 5A, 5B, 5C and 5C). d)). The state of the fine particles may be contained in the entire elastic body, or may be selectively present on the surface in contact with the ink. When it is entirely contained, it may be mixed with the elastic material of the matrix by a ball mill or the like, and when it is selectively present on the surface, fine particles of the recording layer material are attached or embedded after the surface of the elastic body is softened by heating or the like. A method may be employed. The third recording body according to the present invention may have a two-layer structure of an elastic body containing fine particles of a substrate and a recording layer material or a one-layer structure containing fine particles of a recording layer material. Express. At this time, the recording medium has a Young's modulus of 1 ×
^{10 6 ~9.9 × 10 9 N ·} m- 2 is preferred, between the recording medium itself is flexible size of the transferred image because it has stability and the transfer and the recording material is less than this It may cause misalignment. On the other hand, if the value is more than this, it is necessary to apply a linear pressure more than necessary at the time of transfer.

Other details of the method for synthesizing fine particles and the like are as follows. (1) Fine particle synthesis method: precipitation polymerization, dispersion polymerization, suspension polymerization,
It can be synthesized by emulsion polymerization or the like. As the polymerization initiator, various polymerization initiators such as an organic peroxide, an azo compound, and a persulfate can be employed. Organic solvents such as PVP and PVA or water-soluble polymer dispersants, stabilizers, and various anionic, cationic, or nonionic emulsifiers can also be used. (2) Particle size: The term “fine particle size” as used herein means 0.01 μm to 100 μm, preferably 0.1 μm in consideration of the resolution of a latent image.
If the particle size is too large, the thermal sensitivity increases, which is not preferable. If the particle size is less than the volume occupied by one polymer molecule, it is considered to be ineffective. (3) Dispersion method: a ball mill, a paint shaker, an ultrasonic homogenizer, a sand mill or the like can be applied. (4) Coating method: It may be sprayed on the substrate by an applicator, spray coater, bar coater, dip coater, doctor blade, or the like, or may be pelletized or formed by itself. It is also effective to uniformly cut the surface in order to increase the effect of the fine particles on the surface.Since the surface condition is not generally good just by coating on a substrate such as paper, the surface is treated with a calender or the like to smooth the coated surface. It is also effective to improve the performance.

Here, the recording material (A) of the present invention, in which a region having a reduced receding contact angle is formed by applying heat to the surface of the recording material (A) with the contact material (B) interposed therebetween,
The (1) substrate and (2) recording layer material will be described in this order.

(1) Substrate A resin film such as polyimide or polyester, glass, metal or the like can be employed.

(2) Recording Layer Material As the monomer units constituting the polymer (including the copolymer) forming the recording layer, various types of conventionally known or well-known compounds are not particularly limited. Although it is possible, the compounds of the general formulas (I) to (V) are particularly preferable.

As a specific example of the general formula (I), CH
_Two= C (CH_Three) COO (CH_Two)_Two(CF_Two)₈F, CH_Two
= CHCOOCH_TwoCH_Two(CF_Two)₇CF_Three, CH_Two= C
(CH_Three) COOCH_Two(CF_Two)_FourCF_Three, CH_Two= CHC
OO (CH_Two)_Three(CF_Two)₆CF (CF_Three)_Two, CH_Two= C
HCOO (CH_Two)_Three(CF_Two)₈CF (CF_Three)_Two, CH_Two
= CHCOO (CH_Two)_Three(CF_Two)_TenCF (CF_Three)_Two,
CH_Two= C (CH_Three) COO (CH_Two)_Two(CF_Two)₆C
F_Three, CH_Two= CHCOO (CH_Two)_Two(CF_Two)_FiveCF (C
F_Three)_Two, CH_Two= CHCOO (CH_Two)_Four(CF_Two)₇CF
(CF_Three)_Two, CH_Two= CHCOOCH_TwoCH (OH) CH
_Two(CF_Two)₆CF (CF_Three)_Two, CH_Two= CHCOO (CH
_Two)_TwoN (CH_Three) SO_Two(CF_Two)₇CF_Three, CH_Two= CHC
OO (CH_Two)_TwoN (C_TwoH_Five) SO_Two(CF_Two)₇CF_Three, C
H_Two= C (CH)_ThreeCOOCH_TwoCH (OCOCH_Three) CH
_Two(CF_Two)₆CF (CF_Three)_Two, CH_Two= CHCO (CF_Two)₇CF (CF_Three)_Two, CH_Two= CHCOOCH
[CH_TwoOCF (CF_Three)_Two]_Two, CH_Two= C (CH_Three) CO
OCH_TwoCF_TwoCHFCF_ThreePerfluoroalkyl such as
Acrylate or methacrylate containing groups
You.

As a specific example of the general formula (II), CH
₂ = CHOCOC ₃ F ₇ , CH ₂ = CHOCOCF ₃ , CH ₂ CHOCO (CH ₂ ) ₁₀ C ₈ F ₁₇ , CH ₂ =
CHOCOCH ₂ N (C ₂ H ₅ ) SO ₂ C ₈ F ₁₇ , CH ₂ = CHOCO (CH ₂ ) ₁₀ N (CH ₃ ) SO ₂ C
_{8 F 17, CH 2 = CHOCOCH} 2 NHSO fluorine-containing vinyl ester type monomers such as ₂ C ₈ F ₁₇ and the like. Of these, for example, CH ₂ =
CHOCO (CH ₂ ) ₁₀ N (C ₂ H ₅ ) SO ₂ C ₈ F ₁₇ is synthesized and polymerized by the method described in US Pat. No. 2,841,573.

Specific examples of the general formula (III) include:
_{CH 2 = CHCO-Ph-F} , CH 2 = C (CH 3) CO
SCH ₂ CH ₂ (CF ₂ ) ₆ CF (CF ₃ ) ₂ , CH ₂ ＣＨCH
Fluorine-containing vinyl ketone derivatives such as COCH ₂ F are exemplified. Among them, for example, CH ₂ ＣC (CH ₃ ) COSC
H ₂ CH ₂ (CF ₂ ) ₆ CF (CF ₃ ) ₂ is synthesized and polymerized by the method described in BP1, 211,034.

As a specific example of the general formula (IV), C
_{H 2 = CHOCF (CF 3)} 2, CH 2 = CHO-Ph-
F, CH ₂ ＣＨCHOCF ₃ , CH ₂ ＣＨCHOCH ₂ CF ₃ ,
CH ₂ ＣＨCHOCH ₂ CH ₂ CH ₂ F, CH ₂ ＣＨCHOCH ₂
CF ₂ CF ₃ , CH ₂ ＣＨCHOCH ₂ CH ₂ CH ₂ CH ₂ F,
CH ₂ ＣＨCHOCH ₂ (CF ₂ ) ₂ CF ₃ , CH ₂ ＣＨCHOC
H ₂ (CF ₂ ) ₄ CF ₃ , CH ₂ ＣＨCHO (CH ₂ ) ₂ (C
Fluorine-containing vinyl ether derivatives such as F ₂ ) ₉ CF ₃ . Among them, for example, CH ₂ ＣＨCHOCH ₂ (CF
₂ ) ₂ CF ₃ is U.S.A. S. Synthesized and polymerized by the method described in P2,732,370.

Specific examples of the general formula (V) include:
CH ₂ ＣC (CH ₃ ) CONHCH ₂ CF ₂ H, CH ₂ ＣC
(CH ₃ ) CONHCH ₂ CF ₂ CH ₃ , CH ₂ ＣC (C
H ₃ ) CONHCH ₂ CF ₃ , CH ₂ ＣC (CH ₃ ) CON
H (CH ₂ ) ₃ CF ₃ , CH ₂ ＣC (CH ₃ ) CON (CH ₂
Fluorinated acrylamide derivatives such as CF ₂ H) ₂ . Among them, for example, CH ₂ ＣC (CH ₃ ) CONC
H ₂ CF ₃ is U. S. Synthesized and polymerized by the method described in P2,521,902.

In addition to the fluoroalkyl group-containing polymerizable compounds (including the active hydrogen group-containing monomer) represented by the above general formulas (I) to (V), For example, a methacryloyl group (CH ₂ ＣC
(CH) ₃ CO-) or a high-molecular monomer (macromonomer), and further, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, acrylamide, methacrylamide, styrene, α-methylstyrene, p -Methyl styrene, alkyl esters of acrylic or methacrylic acid, benzyl acrylate or methacrylate, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, cyclohexyl acrylate or methacrylate, maleic anhydride,
It is also possible to copolymerize one or more of various polymerizable compounds such as butadiene, isoprene, chloroprene, a hydrophilic group-containing monomer and a fluorine-containing monomer as constituent units of the copolymer.

This suggests that a copolymer comprising a monomer having a polyfluorinated group in the recording layer material and a macromonomer which is a high molecular weight monomer can also be used. By using such a material, it is possible to provide a recording medium with higher performance such as improved rigidity, toughness, weather resistance, and gloss.

Examples of the terminal functional group of the macromer include a general addition polymerization type double bond, a polycondensation / polyaddition type hydroxyl group,
Examples of the carboxylic acid group and the functional group include an epoxy group, an isocyanate group, and an amino group. Further, a bifunctional one such as a reactive macromonomer and a crosslinkable macromonomer is also included. Examples of the monomer constituting the macromonomer segment include styrene, methyl methacrylate, ethylene oxide, hexamethylcyclotrisiloxane, β-propiolactone, and the like. Among these high molecular weight macromonomers, especially those having a methacryloyl group in the terminal group and having styrene or methyl methacrylate or styrene / acrylonitrile as the main component of the segment, are not compatible. Improvement, improvement of rigidity, improvement of toughness,
Furthermore, it has good radical polymerizability, solution polymerization, suspension polymerization,
It is also excellent in that a polymer can be obtained under normal pressure and under a nitrogen stream by emulsion polymerization.

The recording medium of the present invention has at least its surface
By appropriately selecting these appropriate polymerizable compounds and forming them by polymerization or copolymerization, by heating the surface having a high receding contact angle with the liquid with the contact material (B) interposed therebetween, Appropriately improve various materials such as dry soil resistance, abrasion resistance, selective dissolution, flexibility, tactile sensation, and soil release properties, in addition to the properties that form the area where the receding contact angle with liquid decreases. Can be done.

As described above, there are various possible purposes for copolymerization. However, by using a copolymer of a fluorine-containing monomer and a general-purpose monomer, a fluorine-containing polymer which is often treated with a solvent subject to the regulation of chlorofluorocarbons can be used. It is possible to treat with a solvent, and it is possible to deal with environmental problems such as ozone layer destruction. For example, when a copolymer of a fluorine-based monomer such as a fluorine-containing methacrylate containing a perfluoroalkyl group and a monomer of a constituent unit of a polymer dissolved in a general-purpose solvent such as a polyalkyl methacrylate is used, hexane It dissolves in a general-purpose solvent as described above, and exhibits the effect as a recording medium. (The copolymers of Synthesis Examples 3 to 6 could be treated with a general-purpose solvent such as hexane. Further, the effects as in Example 3 were exhibited.)

The copolymer used in the present invention controls the thermoreversible temperature, the thermoreversible transition temperature, and the dynamic contact angle before and after heat is applied via the contact material (B) depending on the composition. Can be changed.

In order to obtain the above-mentioned polymers and copolymers used in the present invention, various polymerization reactions and conditions can be arbitrarily selected, and bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, Any of various polymerization systems such as radiation polymerization and photopolymerization can be employed. As the polymerization initiator, an organic peroxide,
Azo compounds, various polymerization initiators such as persulfates, and further γ
-Ionizing radiation such as radiation may also be employed. In addition, as a surfactant for emulsifying in water in the presence of a surfactant or the like and performing polymerization and copolymerization with stirring, almost all of various anionic, cationic or nonionic emulsifiers can be used.

Further, in the process using the recording medium of the present invention, the heating at the time of forming the latent image can be performed not only from the recording layer material side but also from the substrate side. (Place the liquid on the recording layer side and heat from the substrate side: see the section of the heating means described below) In this case, since the recording material is directly heated to the substrate material, deterioration of the recording material due to heat is assumed, In order to address these problems, it is effective to provide a heat-resistant back layer on the substrate side. For the back layer, a thermosetting resin or a high softening heat resistant resin is employed. It is also effective to include a highly lubricious inorganic pigment in these back layers. The inorganic pigment referred to here refers to a fine powder such as talc, mica powder, fine silica powder, molybdenum disulfide, and as a resin material, a silicone resin, a fluorine resin, an epoxy resin, a melamine resin, a phenol resin, a polyimide resin, Resins such as nitrocellulose are effective. Furthermore,
It is also possible to dissolve the polymerizable compound in a suitable organic solvent and perform solution polymerization by the action of a polymerization initiator.

(3) Other Recording Layer Forming Means Common to obtaining the recording layers of the first, second and third recording materials of the present invention is to dissolve a polymer or copolymer. It can be obtained as a solution dissolved in a possible solvent or as an emulsion, or by heating and melting, by coating or covering with known techniques, or by molding itself. Coating
(Coating) methods such as impregnation, dipping, spraying,
It is obtained by laminating directly or with an intermediate layer on the substrate by brush coating, spin coating, or bar coating. As the intermediate layer, a material having compatibility or interaction with both the substrate and the recording layer, a porous film, or the like can be used. Further, in the process using the recording medium of the present invention, the heating at the time of forming the latent image can be performed not only from the recording layer material side but also from the substrate side.
(Put the liquid on the recording body side and heat from the substrate side: see the heating means below) In this case, since the recording material is directly heated to the substrate material, deterioration of the recording body due to heat is assumed. In order to cope with the above problem, it is effective to provide a heat-resistant back layer on the substrate side. A thermosetting resin or a heat-resistant resin having a high softening point is employed for the back layer. It is also effective to include a highly lubricious inorganic pigment in these back layers. The inorganic pigment referred to here refers to a fine powder such as talc, mica powder, fine silica powder, molybdenum disulfide, and as a resin material, a silicone resin, a fluorine resin, an epoxy resin, a melamine resin, a phenol resin, a polyimide resin, Resins such as nitrocellulose are effective.

Next, the contact material (B) and the heating means will be described. Examples of the contact material (B) include, in addition to water, an aqueous solution containing an electrolyte, an alcohol such as ethanol and n-butanol, a polyhydric alcohol such as glycerin and ethylene glycol, and a polar liquid such as a ketone such as methyl ethyl ketone; Non-polar liquids such as linear hydrocarbons such as -nonane and n-octane, cyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as m-xylene and benzene. Various dispersions and liquid inks can also be used.

As a heating means, in addition to contact heating of a heater, a thermal head, and the like, electromagnetic waves (light rays from a light source such as a laser light source and an infrared lamp are condensed by a lens).
There is non-contact heating. In addition, electron beam irradiation and light (UV light)
The method of heating can be achieved also by irradiation.

Next, the properties of the recording medium of the present invention, the formation of a latent image and the formation of a visible image using the recording medium of the present invention will be described with reference to the accompanying drawings.

FIG. 1 shows that when the film (recording layer) 2 is formed on a substrate 1 and a contact material (for example, liquid 3) is present on the film surface, the film 2 is heated. Shows remarkable wetting and a decrease in receding contact angle. Furthermore,
When the film having a decreased receding contact angle with the liquid is heated again in air, in a vacuum, or in an inert gas atmosphere, the surface of the film 2 again exhibits liquid repellency, that is, an increased receding contact angle. In the figure, reference numeral 4 denotes a heater. Generally, when the receding contact angle is a high value of 90 ° or more, the surface shows liquid repellency, and when the receding contact angle is a low value of 90 ° or less, the surface shows liquid adhesion.

The heating temperature of the surface of the recording medium (A) in contact with the contact material (B) is preferably in the range of 50 ° C. to 250 ° C., more preferably 80 ° C. to 150 ° C. The heating time is about 0.1 ms to 1 second, desirably 0.5 ms to 2 ms. As for the timing of heating, if a latent image is formed,
After heating the surface of the recording medium (A), before contacting the material
The recording material (A) may be heated while the contact material (B) is in contact with the surface of the recording material (A). On the other hand, if the latent image is to be erased,
The surface of the recording medium (A) may be heated to 50 to 300C, preferably 100 to 180C in the absence of (B). The heating time in each case is about 1 ms to 10 seconds, preferably 10 ms to 1 second.

Next, the means for actually recording image information on the surface of the recording medium (A) will be described in more detail. One is a recording layer (A) according to an image signal in a liquid or vapor atmosphere
Heats the surface to form a liquid-attached area on the surface of the recording layer (A)
(Latent image formation), and thereafter, a recording agent is adhered to the latent image portion by means of contacting the latent image portion with the recording agent (development), and thereafter, this recording is directly applied to the surface of the recording medium (A). This is a fixing method (direct recording method). The other is to heat the surface of the recording medium (A) in response to an image signal in a liquid or vapor atmosphere to form a liquid adhesion area on the surface of the recording medium (A) (latent image formation)
Thereafter, the recording liquid is applied to the latent image portion by means of bringing the recording liquid into contact with the latent image portion (development).
This is a method of transferring a visible image composed of the recording liquid on the surface of the recording medium (A) to (plain paper or the like) (indirect recording method). Further, in the above method, if a means for bringing the recording liquid into contact with the latent image portion again after transferring the recording liquid is performed, a printing method using the recording body (A) as a printing plate is obtained. Further, in the above method, after transferring the recording liquid, by heating the surface of the recording medium (A) having formed a latent image in the absence of liquid or vapor to erase the latent image, the recording medium (A) It becomes a reproducible recording method.

Examples of synthesis of the polymers (including copolymers) used in the present invention and examples as recording media are shown below.

Synthesis Example 1 1H, 1H, 2H, 2H-Heptadecafluorodecyl methacrylate
Polymerization of (Biscoat 17FM) A thermometer was attached to a three-necked eggplant flask, 1,1,1-trichloroethane 50 g, 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate (Osaka Organic Chemical Industry Co., Ltd.
M) 50 g, azoisobutyronitrile (AIBN) 0.15 g
After performing nitrogen replacement while stirring for 30 minutes, polymerization was performed at 70 ° C. for 5 hours while stirring under a nitrogen stream to obtain a white viscous body. 100 ml of methanol was added to the white viscous substance, and after stirring, a white solid portion not dissolved in methanol was separated, pulverized with a pestle, and further washed with 100 ml of methanol. The obtained white powder is dried under reduced pressure to obtain 47.5 g of the intended product.
(95% yield).

Synthesis Example 2 Polymerization of 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate (Biscoat 17F) A thermometer was attached to a three-necked eggplant flask, and 100 g of 1,1,1-trichloroethane, 1H, 1H, 2H, 2H- Heptadecafluorodecyl methacrylate (Viscoat 17 manufactured by Osaka Organic Chemical Industry Co., Ltd.)
F) 100 g and 0.3 g of azobisisobutyronitrile (AIBN) were charged and nitrogen replacement was carried out with stirring for about 30 minutes, and then polymerization was carried out at 70 ° C. for 5 hours while stirring under a nitrogen gas stream for 1,1,1-. The product separated into trilichloroethane was obtained. This product was purified by dissolving in Freon 113 and precipitating in methanol. The precipitate was further dried under reduced pressure at 100 to 120 ° C. to obtain 35 g of the desired product.

Synthesis Example 2 '(Synthesis of Fine Particle Recording Layer Material) 5.12 g of polyvinylpyrrolidone was dissolved in 115.2 g of methanol, and the mixture was stirred for 30 minutes under a nitrogen stream. Further, 50.0 g of 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate (Biscoat 17F, manufactured by Osaka Organic Chemical Industry Co., Ltd.) is added and heated to 65 ° C. There 0.92 g of azobisisobutyronitrile (AIBN)
A very small amount of 13.8 g of a methanol solution in which is dissolved is added, and after stirring for 30 minutes, the methanol solution of AIBN described above is added. Thereafter, the reaction is carried out with stirring at 65 ° C. for 5 hours. After returning to room temperature and stopping the reaction, the fine particles generated in a precipitated state were filtered, cleaned with methanol, and dried under reduced pressure at room temperature for 24 hours to obtain fine particles having a diameter of several μm.

Synthesis Example 3 Polymerization of Stearyl Methacrylate A thermometer was attached to a three-necked eggplant flask, and 32 g of 1,1,1-trichloroethane, 32 g of stearyl methacrylate, and 0.15 g of azobisisobutyronitrile (AIBN) were charged and stirred for about 30 minutes. After purging with nitrogen, polymerization was carried out at 70 ° C. for 5 hours while stirring under a nitrogen stream to obtain a transparent viscous body. This viscous body was purified by dissolving in n-hexane and precipitating in methanol. After further filtering the precipitate, 100-120
Drying under reduced pressure at 1 ° C. gave 11.9 g of the desired product.

Synthesis Example 4 Synthesis of a copolymer of 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate and stearyl methacrylate (SMA) A thermometer was attached to a three-necked eggplant flask, 82 g of 1,1,1-trichloroethane, 1H , 1H, 2H, 2H-heptadecafluorodecyl methacrylate (Osaka Organic Chemical Industry Co., Ltd.
M) 50 g, commercially available SMA 31.9 g, AIBN (azoisobutyronitrile) 0.3 g, nitrogen replacement was performed while stirring for about 30 minutes, and then polymerization was performed at 70 ° C. for 5 hours while stirring under a nitrogen stream. A viscous body swollen in 1,1,1-trichloroethane was obtained.
This reaction solution was purified by dissolving in hexane and precipitating in methanol. Further, the precipitate was dried under reduced pressure at 100 to 120 ° C. to obtain 78 g (yield 63%) of the desired product.

Synthesis Examples 5 to 18 Copolymerization was carried out according to the method of Synthesis Example 1 at the following charging ratio. Purification of polymers that do not show solubility in organic solvents
The good solvent was a fluorine-based solvent Freon TF (manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd.), and the poor solvent was methanol. Synthesis conditions Initiator / monomer = 1/100 (mol) Molimer / solvent = 1/1 (weight) Solvent: 1,1,1-trochloroethane Initiator: azobisisobutyronitrile Reaction time: 5 hours Reaction temperature: 70 ° C

[Table 1] (Note 1) 17F: 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate (Osaka Organic Chemical Industry Co., Ltd.)
MMA: methyl methacrylate EMA: ethyl methacrylate nBMA: n-butyl methacrylate nHMA: n-hexyl methacrylate 2EHMA: 2-ethylhexyl methacrylate LMA: lauryl methacrylate SMA: stearyl methacrylate nBA: n-butyl acrylate SA: stearyl acrylate (Note 2) Organic The “organic solvent” in the solvent solubility is tetrahydrofuran, n-hexane.

Synthesis Example 19 Polymerization of N-ethyl-N-perfluorooctanesulfonyl-3-aminoethane acid vinyl ester CH ₂ ＣＨCHOCOCH ₂ N (C ₂ H ₅ ) S in an ampoule tube
1.5 g of O ₂ C ₈ F ₁₇ and 0.01 of acetyl peroxide
And 5 g are dissolved in 0.060 g of dimethyl phthalate.
After removing oxygen, the vinyl ester monomer is dissolved by heating. Thereafter, the ampule tube was frozen with liquid oxygen and sealed under reduced pressure. The reaction was performed at 60 ° C. for 15.5 hours in a water bath. After the reaction, the content was dissolved in xylene hexafluoride. This solution was poured into excess methanol to precipitate the polymer. Thereafter, the mixture was filtered and dried under reduced pressure at room temperature.
95 g (yield 64%) of the polymer was obtained. This polymer exhibited a softening point of 70 ° C.

Synthesis Example 20 Polymerization of 2- (perfluoro-7-methyloctylethylthiol methacrylate) A solution prepared by dissolving 2.5 g of 2- (perfluoro-7-methyloctylethylthiol methacrylate) in 1.6 g of acetone was placed in a flask. In addition, 0.1 g of 60% methylolamide, 7.5 g of water from which oxygen has been removed, a compound represented by the following chemical formula 1

Embedded image 0.012 g and 0.05 g of 2,2'-azodiisobutyramidine dihydrochloride are added. After filling the inside with nitrogen, it was put into a thermostat and reacted at 70 ° C. for 4 hours to obtain a latex polymer.

Synthesis Example 21 Polymerization of vinyl 1,1-dihydroperfluorobutyl ether In a ampoule tube, 0.45 g of vinyl 1,1-dihydroperfluorobutyl ether and 0.005 g of a boron trifluoride / ethyl ether complex were dissolved to give a 2% solution. The reaction was carried out at 25 ° C. for 24 hours, and the desired polymer was obtained.

Synthesis Example 22 A thermometer was attached to a three-necked eggplant flask, and toluene 40 was used.
g, 1,1,1-trichloroethane 40 g, 1H, 1
H, 2H, 2H-heptadecafluorodecyl methacrylate (Biscoat 17FM, Osaka Organic Chemical Industry Co., Ltd.) 1
9.5 g, 20 g of macromonomer (AS-6 manufactured by Toa Gosei Chemical Industry Co., Ltd.), azobisisobutyronitrile (AI
BN) was charged, and the atmosphere was replaced with nitrogen while stirring for about 30 minutes.
For 5 hours to obtain a cloudy, low-viscosity liquid.
Purification was performed by precipitating this reaction solution into a large excess of methanol. Further, the precipitate was dried under reduced pressure at 100 to 120 ° C. to obtain 24.0 g of a powdery target substance.

Synthesis Example 23 A three-necked eggplant flask was equipped with a thermometer and toluene 40
g, 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate (Osaka Organic Chemical Industry Co., Ltd. Biscoat 17FM) 19.5 g, macromonomer (AA-6 manufactured by Toa Gosei Chemical Industry Co., Ltd.) 20 g, azobisiso After charging 0.066 g of butyronitrile (AIBN) and performing nitrogen substitution while stirring for about 30 minutes, polymerization was performed at 70 ° C. for 5 hours while stirring under a nitrogen stream to obtain a cloudy, low-viscosity liquid. . Purification was performed by precipitating this reaction solution into a large excess of methanol. In addition, the precipitate is
Drying under reduced pressure at 20 ° C. gave 20.8 g of a powdery target product.

Synthesis Example 24 A thermometer was attached to a three-necked eggplant flask, and toluene 45 was used.
g, DMF (dimethylformamide) 45 g, 1H, 1
H, 2H, 2H-heptadecafluorodecyl methacrylate (Biscoat 17FM, Osaka Organic Chemical Industry Co., Ltd.) 1
9.5 g, macromonomer (AN-6 manufactured by Toa Gosei Chemical Industry Co., Ltd.) 20 g, azobisisobutyronitrile (AI
BN), and nitrogen replacement was performed while stirring for about 30 minutes.
Polymerization was performed at 5 ° C. for 5 hours to obtain a cloudy, low-viscosity liquid. Purification was performed by precipitating this reaction solution into a large excess of methanol. Further, the precipitate was dried under reduced pressure at 100 to 120 ° C. to obtain 22.0 g of a powdery target substance.

The properties of the above-mentioned macromonomer manufactured by Toa Gosei Chemical Industry Co., Ltd. are as follows. (Note): The terminal group structure of each of AS-6, AA-6, and AN-6 is a methacryloyl group.

[0073]

Next, the present invention will be described more specifically with reference to examples.

Embodiment 1 (Preparation of Recorded Body) 1. Recording material: Fluorine-containing acrylate material Biscoat 17FM (synthesized in Synthesis Example 1) (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 2. Recording substrate: polyimide (Kapton 300V, manufactured by Toray DuPont) Recording layer coating method Coating solution Freon 113 13g 17F 1g 1 g of 17FM was added to and dissolved in 13g of Freon 113, and the coating solution was placed on a polyimide film (Kapton 300V, manufactured by Toray Dupont Co., Ltd.) on which a grid-like mask of about 127 μm square was placed. ) Cast coat on top, 120 ℃
For 120 minutes. Thereafter, the mask was removed to obtain a recording medium having about 127 μm square grid-like projections on the surface. (Evaluation Method and Results) As shown in FIG. 1, the ceramic film 4 was heated from the polyimide film 1 side with the liquid (pure water) 3 in contact with the surface of the film 2 (heating temperature 120 ° C., time about 1 second). ). A remarkable decrease in the receding contact angle due to pure water on the surface of the polymer film 2 before and after the heating was recognized, and it was found that the surface was made liquid-adhesive. Further, the liquid adhesion was maintained even if left as it was.

Example 2 The evaluation method was changed in the same manner as in Examples 1 to 3 from 1 to 3. (Evaluation method and results) Instead of contacting pure water as a liquid on the surface of the film 2 by rolling the film prepared in Examples 1 to 3 and winding it around an aluminum cylinder of φ100 mm and length 100 mm to prepare a recording medium 5 The heating section of the thermal head 6 for a thermal transfer printer was placed in contact with the film surface as shown in FIG. As the liquid ink 7, an oil-based ink based on lauric acid (black dye: Spilon Black-MH manufactured by Hodogaya Chemical Co., Ltd.) was used. When an appropriate signal was sent to the thermal head 6 and heated, the ink adhered only to the heated portion (the liquid ink adhered to the latent image S 7a). Further, as shown in FIG. 2, when the recording paper (NM coated paper manufactured by Mitsubishi Paper Mills) P was conveyed in contact with the tubular polyimide film, the adhered ink 7a was transferred to the paper P and an image 7a 'was obtained. In addition, there was no blur due to heat diffusion, and a sharp transfer state was obtained. Further, the ink-attached portion (latent image S) showed ink-adhering property even when left as it was.

Example 3 The evaluation method was changed in the same manner as in Examples 1 and 2 from 1 to 3. (Evaluation Method and Results) FIG. 3 shows the recording materials prepared in Examples 1 and 2 to 1 to 3 (except for a belt-shaped recording material).
A device like that was created. The latent image was formed by giving appropriate information to the thermal head 6 with the water 3 interposed, and the development was performed with the liquid ink 7 as in the second embodiment. When an appropriate signal was sent to the thermal head 6 for heating and further development was performed, the liquid ink adhered only to the heated portion. Further, when the recording paper (NM coated paper manufactured by Mitsubishi Paper Mills) P was conveyed in contact with the ink, the ink was transferred to the paper, and an image 7a 'was obtained. In addition, there was no blur due to heat diffusion, and a sharp transfer state was obtained. Further, the ink-attached portion showed the ink-adhering property even when left as it was.

Example 4 The same procedure as in Example 3 was carried out except that the recording medium was prepared and the apparatus shown in FIG. 3 was used, and the latent image was formed by giving appropriate information to the thermal head with water interposed. However, development was carried out with an aqueous ink (dye: Direct Black 19) based on water and ethylene glycol. When an appropriate signal was sent to the thermal head for heating and further development was performed, ink adhered only to the heated portion. Further, when the recording paper (NM coated paper manufactured by Mitsubishi Paper Mills) was transported in contact with the recording paper, the ink was transferred to the paper. After that, when the surface of the recording medium 5 was heated by the infrared lamp 9 including the area showing the ink adhesion, the ink adhesion disappeared, and the receding contact angle returned to the state before heating with the liquid interposed.

Comparative Example 1 A recording medium was produced in the same manner as in Example 3 except that a lattice pattern was not provided without using a mask during film formation. As a result, some background soiling was observed, and slight blurring of the image due to heat diffusion was observed. Further, it took a little more time than in Example 4 to return the ink adhesion to the state before heating with the liquid interposed.

Example 5 The polymer of 1H, 1H, 2H, 2H-heptafluorodecyl acrylate and SMA synthesized in Synthesis Example 2 was 0.25 each.
g, weighed and dissolved in Freon 113 to produce polymer 0.0
The Freon 113 solution was adjusted to be 5% by weight. This Freon 113 solution was applied to polyimide film 1 (Toray
After coating on Dupont Kapton 200V), 90
The film was dried at 2 ° C. for 2 hours to form a film having a thickness of about 1 μm. Thereafter, as shown in FIG. 1, the ceramic film 4 was heated from the side of the polyimide film 1 while the liquid (pure water) 3 was in contact with the surface of the film 2. When the temperature was changed from normal temperature (25 ° C.) to 120 ° C., at 60 to 70 ° C., a remarkable decrease in the receding contact angle due to pure water on the surface of the recording medium 2 before and after heating was recognized, and it was found that the surface was made to be liquid adhering. Was.

Example 6 The film prepared in Example 1 was rolled and wound around an aluminum cylinder having a diameter of 100 mm and a length of 100 mm to prepare a recording medium, and the surface thereof was contacted with liquid ink instead of contacting pure water as a liquid. In this state, the heating section of the thermal head 6 for a thermal transfer printer was placed in contact with the film surface as shown in FIG. As the liquid ink 7, an oil-based ink based on lauric acid (black dye: Spilon manufactured by Hodogaya Chemical Co., Ltd.)
Black-MN) was used. When an appropriate signal was sent to the thermal head 6 and heated, ink adhered only to the heated portion. Further, when recording paper (NM coated paper manufactured by Mitsubishi Paper Mills) was conveyed in contact with the cylindrical polyimide film, the ink was transferred to the paper.

Example 7 An apparatus as shown in FIG. 3 was prepared from the recording medium prepared in Example 1. The latent image was formed by giving appropriate information to a thermal head in the presence of water.
Performed with the same ink as When an appropriate signal was sent to the thermal head for heating and further development was performed, ink adhered only to the heated portion. In addition, recording paper (NM manufactured by Mitsubishi Paper Mills, Inc.)
(Coated paper) and the ink was transferred to the paper when the paper was conveyed.

Example 8 An apparatus as shown in FIG. 3 was prepared from the recording medium prepared in Example 5. Further, a latent image is formed in the same manner as in Example 3 except that a latent image is formed by giving appropriate information to a thermal head in the presence of water, but development is carried out with water and an ethylene glycol-based aqueous ink (dye: Direct Black 1).
9). When an appropriate signal was sent to the thermal head, heating was performed, and further development was performed, ink adhered only to the heated portion, and when the recording paper (NM coated paper, manufactured by Mitsubishi Paper Mills) was contacted and transported, the ink was transferred to the paper. .

Comparative Example 2 A copolymer of 1H, 1H, 2H, 2H-heptafluorodecyl methacrylate and SMA synthesized in Synthesis Example 4 was dissolved in hexane, and then polyimide film 1 (manufactured by Toray DuPont) as in Example 1. A coat was formed on Kapton 200V) to form a film. Further, the same operation as in Example 1 was performed as shown in FIG. As a result, in Example 1, 1H, 1H, 2H, 2H-
The molar ratio of the heptadecafluorodecyl methacrylate segment to the SMA segment is about 5: 8, whereas the copolymer of this comparative example has a molar ratio of about 5: 5, and the copolymer of the comparative example has more fluorine. Despite the high content of monomer segments, the temperature was lower than that of the material of Example 5 (30 ° C.).
), A remarkable decrease in receding contact angle was observed. In other words, the blending of Example 4 resulted in higher stability and reliability of the non-latent image (region having a high receding contact angle) due to the introduction of a small amount of the fluorine-containing segment.

Embodiment 9 (Preparation of Recorded Body) 1. Recording material: Fine particles of fluorine-containing acrylate material Biscoat 17F (Osaka Organic Chemical Industry Co., Ltd.) Synthesis: Synthesis Example 2'3. 3. Recording layer (same as in Example 1) Preparation liquid for preparing an elastic body containing fine particles of a recording layer material ・ 17 g fine particles 0.1 g ・ Elastic member KE103 (manufactured by Shin-Etsu Polymer Co., Ltd.) (main agent) 4.75 g ・ Catalyst Cat-103 (manufactured by Shin-Etsu Polymer Co., Ltd.) 4.) (curing agent) 0.25 g The above 4 is formed into a film on the above 3 A material of 4 is mixed, and a length of 300 mm, a width of 100 mm and a thickness of 2 mm
, And left at 25 ° C for 24 hours to mold. The molded product was cut into a length of 300 mm, a width of 100 mm and a thickness of 1 mm. 6. Appearance: As a result of coating, it became cloudy and rubbery. (Evaluation Method and Results) As shown in FIG. 1, the ceramic film 4 was heated from the polyimide film 1 side with the liquid (pure water) 3 in contact with the surface of the film 2 (heating temperature 120 ° C., time about 1 second). ). A significant decrease in the receding contact angle due to pure water on the surface of the recording medium 2 on which the polymer fine particles were arranged before and after the heating was observed, and it was found that the surface was made liquid-adhesive. Further, the liquid adhesion was maintained even if left as it was.

Example 10 Recording means were prepared in the same manner as in Examples 9 to 6 except that the evaluation method was changed. (Evaluation Method and Results) Instead of rolling a film formed by means 1 to 6 of Example 9 and winding it around an aluminum cylinder of φ100 mm and length 100 mm to form a recording medium and contacting the surface with pure water as a liquid. With the liquid ink 7 in contact, the heating section of the thermal head 6 for a thermal transfer printer was placed in contact with the film surface as shown in FIG. As the liquid ink 7, an oil-based ink based on lauric acid (black dye: Spilon Black-MH manufactured by Hodogaya Chemical Co., Ltd.) was used. When an appropriate signal was sent to the thermal head 6 and heated, the liquid ink adhered only to the heated portion. Further, as shown in FIG. 2, when the recording paper (NM coated paper manufactured by Mitsubishi Paper Mills) P was transported in contact with the cylindrical polyimide film, the ink was transferred to the paper. In addition, there was no blur due to heat diffusion, and a sharp transfer state was obtained.

Example 11 After the same procedure as in Examples 9 and 11 to 1 to 6 was performed, evaluation was performed in the following manner. (Evaluation Method and Results) An apparatus as shown in FIG. 3 was prepared from the recording materials prepared in 1 to 6 of Examples 1 and 2. The latent image was formed by giving appropriate information to a thermal head in the presence of water, and development was performed with the same liquid ink as in Example 10. When an appropriate signal was sent to the thermal head for heating and further development was performed, ink adhered only to the heated portion. Further, when the recording paper (NM coated paper manufactured by Mitsubishi Paper Mills) was transported in contact with the paper, the ink was transferred to the paper.
In addition, there was no blur due to diffusion of heat, and a sharp transfer state was obtained.

Example 12 An apparatus as shown in FIG. 3 was manufactured using the recording medium prepared in Example 9. Further, the latent image is formed in the same manner as in Example 11 except that the latent image is formed by giving appropriate information to the thermal head in the presence of water, but the development is carried out with water and an ethylene glycol-based aqueous ink (dye: Direct Black 19). ). When an appropriate signal was sent to the thermal head and heated, and further development was performed, ink adhered only to the heated part, and when the recording paper (manufactured by Mitsubishi Paper Industries, NM-coated paper) was contacted and transported, the ink was transferred to the paper. Was.

Comparative Example 3 KE103 of Example 9 and cat-103 were mixed at 1: 105
(Weight ratio) after mixing, length 300mm, width 10
After adjusting the thickness to 0 mm and the thickness to 2 mm, the molded product was left standing at 25 ° C. for 24 hours and then molded.
It was cut to a thickness of 1 mm. A solution prepared by dissolving 0.1 g of the Biscoat 17F polymer synthesized in Synthesis Example 2 in 2.0 g of Freon 113 was coated on the sheet thus formed, and dried at 120 ° C. for 2 hours. Roll this and turn the surface coated with 17F polymer outward to φ100
A recording medium was prepared by wrapping the recording medium around an aluminum cylinder of 100 mm or 100 mm, and the adhesion of the ink was investigated in the same manner as in Example 1. As a result, the recording medium was slightly cracked as compared with Example 1, which was insufficient for repeated use.

[0089]

According to the present invention, the following effects can be obtained. (1) Since the projections are formed on the recording medium, independence between the heated portion and the non-heated portion is maintained, and as a result, an image free from background smear can be obtained by high-density recording. (2) By blending two or more polymers with the material of the recording body surface, a low-cost and reliable recording body can be obtained. (3) Since the recording medium has a structure in which fine particles of a recording layer material are arranged on an elastic body, the recording layer does not peel off from the substrate, cracks do not occur, and adhesion to paper is further improved. Better and better images can be obtained.

[Brief description of the drawings]

FIG. 1 is a diagram for explaining properties of a recording layer.

FIG. 2 is a diagram schematically illustrating the entirety of the apparatus of the present invention.

FIG. 3 is a diagram schematically illustrating another overall configuration of the apparatus of the present invention.

4 (a), (b), (c) and (d) are cross-sectional views showing a state in which the surface of the recording layer has a projection shape, and FIG. 4 (e) is a top view of the recording layer.

FIGS. 5 (a), (b), (c) and (d) are cross-sectional views of four other examples in which the surface is formed of fine particles of a fine recording layer material.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Recording layer 3 Pure water 4 Heater 5 Recording medium 6 Thermal head 7 Liquid ink 8 Pressure roller 9 Infrared lamp 10 Developing roller

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B41C 1/10 B41M 5/00

Claims (9)

(57) [Claims] 1. A surface of a recording layer having a surface in which a receding contact angle decreases when heated and brought into contact with a liquid, and a liquid, a vapor, and a liquid at a temperature not more than a temperature at which the receding contact angle in the recording layer starts to decrease. By selectively heating in contact with a contact material selected from the group consisting of: a liquid and a solid that generates vapor or vapor; or by contacting the surface of the recording layer with the contact material while being selectively heated. A recording medium used in a recording method for forming a region having a receding contact angle according to a heating temperature on the surface of the recording layer, wherein the recording medium has a projection, and the projection has a fluorine atom on a side chain. A recording medium comprising a compound containing: 2. A surface of a recording layer having a surface in which a receding contact angle decreases when heated and brought into contact with a liquid, and a liquid, a vapor, and a liquid at a temperature not more than a temperature at which the receding contact angle in the recording layer starts to decrease. By selectively heating in contact with a contact material selected from the group consisting of: a liquid and a solid that generates vapor or vapor; or by contacting the surface of the recording layer with the contact material while being selectively heated. Accordingly, a recording medium used in a recording method for forming a region showing a receding contact angle according to a heating temperature on the recording layer surface, wherein the recording medium contains a material obtained by blending two or more polymers. Further, a recording medium characterized in that at least one of the polymers contains a compound containing a fluorine atom in a side chain. 3. A surface of a recording layer having a surface in which a receding contact angle is reduced in a heated state and when brought into contact with a liquid, and a liquid, a vapor and a liquid at a temperature not more than a temperature at which the receding contact angle in the recording layer starts to decrease. Or by selectively heating the recording layer in contact with a contact material selected from liquids or solids that generate vapor, or by selectively heating the surface of the recording layer with the contact material. A recording medium used in a recording method for forming a region showing a receding contact angle according to a heating temperature on the recording layer surface, wherein the recording medium has a structure in which fine particles of a recording layer material are arranged on an elastic body, The recording medium is characterized in that the fine particles contain a compound containing a fluorine atom in a side chain. 4. The compound containing a fluorine atom in the side chain is
A polymer of the compound represented by the general formula (I).
Item 4. The recording medium according to Item 1, 2 or 3. [However, R¹Is hydrogen or -CH_ThreeR represents a group^TwoIs-
(CH_Two) NR^Three(N is an integer of 1 to 10, R^ThreeIs carbon number 3
Up to 21 linear or branched perfluoroalkyl
Group), -CH_TwoCF_TwoCHFCF_Three,H_TwoOCR^Four(R^FourIs a straight chain having 3 to 20 carbon atoms or
A branched perfluoroalkyl group),(R^FiveIs a linear or branched par having 1 to 8 carbon atoms.
Fluoroalkyl group) or -CH [CH_TwoOCF (C
F_Three)_Two]_TwoRepresents ] 5. The recording material according to claim 1, wherein the compound containing a fluorine atom in the side chain is a polymer of a compound represented by the following general formula (II). Wherein R ¹ represents hydrogen or a —CH ₃ group, and R ⁶ represents — (C
F ₂₎ nF (n is an integer of _{1,3~17), - (CH 2)} nR 7
(N is an integer of 1 to 10, R ⁷ is a linear or branched perfluoroalkyl group having 3 to 21 carbon atoms) or -R
⁸ N (R ⁹ ) SO ₂ R ¹⁰ (R ⁸ is an alkylene group having 1 to 12 carbon atoms, R ⁹ is hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ¹⁰ is a carbon atom. 4 to 12 linear or branched perfluoroalkyl groups). ] 6. The recording material according to claim 1, wherein the compound containing a fluorine atom in the side chain is a polymer of a compound represented by the following general formula (III). Wherein R ¹ represents hydrogen or a —CH ₃ group, and R ¹¹ represents —P
h-F (Ph represents a paraphenylene group), -SCH ₂
CH ₂ R ¹² (R ¹² is a perfluoroalkyl group having 5-13 straight-chain or branched carbon atoms) or -CH ₂ F. ] 7. The compound containing a fluorine atom in the side chain is
A polymer of the compound represented by the general formula (IV)
Item 4. The recording medium according to Item 1, 2 or 3.[However, R¹Is hydrogen or -CH_ThreeR represents a group¹³Is -P
h-F (Ph is paraph n^TwoIs an integer of 0 to 10), -CF [CF (C
F_Three)_Two]_Two, You. ] 8. The recording material according to claim 1, wherein the compound containing a fluorine atom in the side chain is a polymer of a compound represented by the following general formula (V). Wherein R ¹ represents hydrogen or a —CH ₃ group, and R ¹⁴ represents —C
_{H 2 CF 2 H, -CH 2} CF 2 CH 3, -CHCF 3, - (C
H _{2) 3} CF ₃ or - represents a _{(CH 2 CF 2 H) 2} . ] 9. The compound containing a fluorine atom in the side chain is
The general formulas (I), (II), (III), (IV) and (V)
At least one of the compounds represented by
The recording according to claim 1, 2 or 3, which is a copolymer containing as a component.
body. [However, R¹Is hydrogen or -CH_ThreeR represents a group^TwoIs-
(CH_Two) NR^Three(N is an integer of 1 to 10, R^ThreeIs carbon number 3
Up to 21 linear or branched perfluoroalkyl
Group), -CH_TwoCF_TwoCHFCF_Three, (Ph represents a paraphenylene group), -CH (C
F_Three)_Two, -CF (CF_Three)_Two,Fluoroalkyl group) or -CH [CH_TwoOCF (C
F_Three)_Two]_TwoRepresents ] [However, R¹Is hydrogen or -CH_ThreeR represents a group⁶Is-
(CF_Two) nF (n is an integer of 1, 3 to 17),-(CH_Two) n
R⁷(N is an integer of 1 to 10, R⁷Is a straight chain having 3 to 21 carbon atoms
Chain or branched perfluoroalkyl group) or-
R⁸N (R⁹) SO_TwoR^Ten(R⁸Is an alkyl having 1 to 12 carbons
Kylene group, R⁹Is hydrogen or a linear group having 1 to 6 carbon atoms
Or a branched alkyl group, R^TenIs a straight chain having 4 to 12 carbon atoms
(Chain or branched perfluoroalkyl group)
You. ] [However, R¹Is hydrogen or -CH_ThreeR represents a group¹¹Is -P
h-F (Ph represents a paraphenylene group), -SCH_Two
CH_TwoR¹²(R¹²Is a straight chain having 5 to 13 carbon atoms or
A branched perfluoroalkyl group) or -CH_TwoTable F
I forgot. ][However, R¹Is hydrogen or -CH_ThreeR represents a group¹³Is -P
h-F (Ph is paraph An integer of 0 to 10), -CF [CF (C
F_Three)_Two]_Two, [However, R¹Is hydrogen or -CH_ThreeR represents a group¹⁴Is -C
H_TwoCF_TwoH, -CH_TwoCF_TwoCH_Three, -CHCF_Three,-(C
H_Two)_ThreeCF_ThreeOr-(CH_TwoCF_TwoH)_TwoRepresents ]