JP2967531B2 - Recorded body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for forming a liquid-adhesive area (latent image area) selectively or selectively and reversibly on the surface of a recording medium having a strong liquid repellency. Accordingly, a recording agent (e.g., liquid ink) is supplied to this area to form an image, or after supplying the liquid ink, it is suitable for transferring it to plain paper or the like to obtain a copied image. Regarding the recording medium.

[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)).

Further, as a waterless planographic printing plate currently commercially available, there is a waterless printing 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 a positive type, a raw plate (original plate) → exposed image →
There is a complicated process of development → printing plate → printing. Particularly, in the developing process, a special developing machine and chemicals are required. Since this offset printing method requires such a process, it is difficult to incorporate the plate making process and the printing process from the printing plate until obtaining a printing plate (printing plate) from the original plate into one apparatus,
It has been difficult to reduce the size of plate making and printing apparatuses. 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 article) having a strong repulsive force against a liquid. A method and an apparatus capable of forming such a liquid-adhering region have been proposed (Japanese Patent Application No. 43599/1990). 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.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to selectively or selectively and reversibly apply a simple means to the surface of a member (liquid repellent molded article) having a strong repulsion force against a liquid. A good image can be obtained by forming a liquid-adhesive region having a desired pattern and further supplying, for example, a liquid ink (recording liquid) to the liquid-adhesive region. It is an object of the present invention to provide a recording medium which can be suitably used for a method and an apparatus for obtaining a clear image with gradation by transferring to a paper or the like. Another object of the present invention is to provide a recording medium having excellent storage stability and stability before and after recording.

[0015]

That is, the present invention provides the following:
It is the recording body of (1) or (2). (1) The surface of the recording body (A) and a contact material (B) selected from liquid or vapor and a solid that emits a liquid or a vapor at a temperature lower than the receding contact angle lowering start temperature indicated by the recording body (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). Recording wherein at least the surface of the recording medium (A) used in the recording method for forming a region for reducing the receding contact angle with a recording liquid 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)
The surface of the recording medium (A) is contacted with the contact material (B) while the surface of the recording medium is selectively heated to form a latent image area having a reduced receding contact angle with the recording liquid on the surface of the recording medium (A). The recording liquid is supplied to the area to visualize the area, and then this visible image is transferred to a transfer object, and the recording medium (A) is heated in the absence of the contact material (B) to clear 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.

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.

[0018] Wherein R ₁ represents hydrogen or a —CH ₃ group, and R ² represents —
(CH ₂ ) nR ³ (n is an integer of 1 to 10, and R ³ has ³ carbon atoms)
To 21 straight-chain or branched perfluoro alkyl _{group), - CH 2 CF 2 CHFCF} 3, (However, -Ph- represents a paraphenylene group; the same applies hereinafter), -CH (CF ₃ ) ₂ , 岐状perfluoroalkyl group), or -CH [CH ₂ O
CF (CF ₃ ) ₂ ] ₂ . ]

[0019] Wherein R ¹ represents hydrogen or a —CH ₃ group, and R ⁶ represents —
(CF ₂₎ nF (n is an integer of 1,3~17), - (C
H ₂ ) nR ⁷ (n is an integer of 1 to 10; R ⁷ is 3 to 2 carbon atoms)
One linear or branched perfluoroalkyl group), or ^{-R 8 N (R 9) SO} 2 R 10 (R 8 is a carbon number 1 to 1
Two alkylene groups, R ⁹ is hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms, and R ¹⁰ is a carbon atom having 4 to 4 carbon atoms.
12 linear or branched perfluoroalkyl groups). ]

[0020] [However, R ₁ represents hydrogen or a —CH ₃ group, and R ¹¹ represents —P
_{h-F, -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. ]

[0021] [However, R ₁ represents hydrogen or a —CH ₃ group, and R ¹³ represents —P
h-F, (n ⁸ is 1 to 18 integer) represent. ]

[0022] 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} . ]

That is, the present invention relates to a material for forming the recording medium (A) (strictly speaking, a material for forming a surface layer of the recording medium (A)).
As a liquid repellent, by using a "compound having a fluorine atom in a side chain", the contact material (B) is brought into contact with the surface of the recording material (A) and heated, or the recording material ( The recording material (A) is brought into contact with the contact material (B) while the surface of (A) is heated.
A region in which the receding contact angle with the recording liquid has been reduced can be easily formed on the surface.

Furthermore, the receding contact angle can be recovered by heating the region in which the receding contact angle has been reduced by the above method in the absence of the contact material (B). It is possible to form a region in which the receding contact angle changes reversibly, in other words, a recording medium [recording medium] capable of reversibly controlling wettability with a liquid.
(A)] can be provided.

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, (2) recording layer, and (3) recording layer forming method will be described in order.

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

(2) Recording Layer The monomer unit constituting the polymer (including the copolymer) forming the recording layer is not particularly limited and may be any of various known compounds such as conventionally known or well-known compounds. However, those of the general formulas (I) to (V) are particularly desirable.

For example, as a specific example of the general formula (I), CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ (CF ₂ )
₈ F, CH ₂ ＣＨCHCOOCH ₂ CH ₂ (CF ₂ ) ₇ CF ₃ ,
CH ₂ ＣC (CH ₃ ) COOCH ₂ (CF ₂ ) ₄ CF ₃ , CH
₂ = CHCOO (CH ₂ ) ₃ (CF ₂ ) ₆ CF (CF ₃ ) ₂ ,
_{CH 2 = CHCOO (CH 2)} 3 (CF 2) 8 CF (CF 3)
₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₃ (CF ₂ ) ₁₀ CF (C
F ₃ ) ₂ , CH ₂ ＣC (CH ₃ ) COO (CH ₂ ) ₂ (C
F ₂ ) ₆ CF ₃ , CH ₂ ＣＨCHCOO (CH ₂ ) ₂ (CF ₂ ) ₅
CF (CF ₃ ) ₂ , CH ₂ ＣＨCHCOO (CH ₂ ) ₄ (C
F ₂ ) ₇ CF (CF ₃ ) ₂ , CH ₂ ＣＨCHCOOCH ₂ CH
(OH) CH ₂ (CF ₂ ) ₆ CF (CF ₃ ) ₂ , CH ₂ ＣＨCH
COO (CH ₂ ) ₂ N (CH ₃ ) SO ₂ (CF ₂ ) ₇ CF ₃ ,
CH ₂ ＣＨCHCOO (CH ₂ ) ₂ N (C ₂ H ₅ ) SO ₂ (CF
₂ ) ₇ CF ₃ , CH ₂ ＣC (CH) ₃ COOCH ₂ CH (OC
OCH ₃ ) CH ₂ (CF ₂ ) ₆ CF (CF ₃ ) ₂ , CH ₂ ＣC
HCO OOCF (CF ₃ ) ₂ , CH ₂ ＣC (CH ₃ ) COOCF
(CF ₃ ) ₂ , CH ₂ = C (CF ₂ ) ₇ CF (CF ₃ ) ₂ , CH ₂ ＣＨCHCOOCH
[CH ₂ OCF (CF ₃ ) ₂ ] ₂ , CH ₂ ＣC (CH ₃ ) CO
An acrylate or methacrylate containing a perfluoroalkyl group such as OCH ₂ CF ₂ CHFCF ₃ is mentioned.

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.

Specific examples of the general formula (IV) include 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) of the above-mentioned (I) to (V), the copolymer forming the recording layer of the present invention may be, for example, A methacryloyl group (CH ² ＣC (CH) ³ C
O-)-containing high molecular monomers (macromonomers), and further ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, acrylamide, methacrylamide, styrene, α-methylstyrene, p-methylstyrene, Alkyl esters of acrylic acid or methacrylic acid, benzyl acrylate or methacrylate, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, cyclohexyl acrylate or methacrylate, maleic anhydride, butadiene,
It is also possible to copolymerize one or more of various polymerizable compounds such as isoprene, chloroprene, a hydrophilic group-containing monomer and a fluorine-containing monomer as constituent units of the copolymer.

This suggests that a copolymer consisting of a monomer having a polyfluorinated group in the recording layer material and a macromonomer which is a high molecular weight monomer can 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 the copolymerization. However, by using a copolymer of a fluorine-containing monomer and a general-purpose monomer, a fluorine-containing polymer which is generally treated with a solvent subject to the regulation of fluorocarbons 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 polymer or copolymer 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) Recording layer forming means In order to obtain the recording layer of the recording medium of the present invention, a polymer or copolymer is dissolved in a solvent capable of dissolving, or as an emulsion, and further heated and melted. Coating or covering with known techniques,
Alternatively, it can be obtained by molding itself. The coating (coating) method can be obtained by, for example, impregnation, dipping, spraying, brushing, spin coating, or bar coating, and directly or via an intermediate layer on the substrate. 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, an electromagnetic wave (a light beam from a light source such as a laser light source or an infrared lamp is focused 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. 1A shows a state in which the above-mentioned film (recording layer) 2 is formed on a substrate 1 and a contact material (for example, liquid 3) is present on the film surface. In this state, as shown in FIG. 2, when the film 2 is heated, it is recognized that the surface of the film 2 shows significant wetting and the receding contact angle decreases. Furthermore, when the film having a reduced receding contact angle with the liquid is heated again in air, in a vacuum, or in an inert gas atmosphere (FIG. 1 (b)), the surface of the film 2 is again liquid repellent, that is, has a receding contact angle. An increase is observed. FIG. 3 shows an example of the change in the contact angle of the aqueous solution before and after the heating of the film 2 under the contact with the aqueous solution, and the change of the contact angle of the aqueous solution when the film 2 is further heated in the air. FIG.
In the graph, ○ indicates a forward contact angle, and △ indicates a receding contact angle. 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
(B). Either heating the surface of the recording medium (A) in a state where the contact material (B) is in contact with the surface of the recording medium (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.

Hereinafter, a synthesis example of the polymer copolymer used in the present invention and an example as a recording medium will be described.

Synthesis Example 1 Polymerization of poly (1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate) A thermometer was attached to a three-necked eggplant flask, 50 g of 1,1,1-trichloroethane, 1H, 1H, 2H, 2H-hepta. Decafluorodecyl methacrylate (Viscoat 17F manufactured by 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 Synthesis of poly (1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate) Instead of 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate, 1H, 1H, 2H, 2H-hepta Except that decafluorodecyl acrylate was used, the procedure was carried out in the same manner as in Example 1 to obtain the desired product.

Synthesis Example 3 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 4 to 17 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 (manufactured by Osaka Organic Chemical Industry Co., Ltd., Biscoat 17F) 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) The “organic solvent” in the organic solvent solubility is tetrahydrofuran and n-hexane.

Synthesis Example 18 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 19 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, an additional 60% methylolamide 0.1 g, oxygen-free water 7.5 g,

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 20 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 21 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 22 A thermometer was attached to a three-necked eggplant flask, and toluene 40 was used.
g, 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate (Osaka Organic Chemical Industry Co., Ltd., Biscoat 17FM) 19.5 g, macromonomer (Toa Gosei Chemical Industry Co., Ltd., AA-6) 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 23 A three-necked eggplant flask was equipped with a thermometer and toluene 45
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 mocromonomer 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.

FIG. 7 is a graph showing the change in the heating temperature in liquid and the contact angle in the above several synthesis examples.
F is for Viscote 17F, S is for SMA
(It is stearyl acrylate. As can be seen from this figure, a decrease in the receding contact angle reduction temperature was confirmed with an increase in the charged SMA amount.

[0061]

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

Example 1 The polymer of Synthesis Example 1 was dissolved in Freon TF (manufactured by Mitsui Fluorochemicals Co., Ltd.) to a concentration of 7% by weight, and then dissolved on a polyimide film (Kapton 200V, manufactured by Toray Dupont Co., Ltd.). After coating, it was dried at 90 ° C. for 2 hours to produce a film having a thickness of about 1 μm.
Thereafter, as shown in FIG. 2, heating was performed from the side of the polyimide film 1 with the ceramic heater 4 in a state where the liquid (pure water) 3 was 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 polymer film 2 before and after the heating was observed, and it was found that the surface was made liquid-adhesive (FIG. 4). Further, the liquid adhesion was maintained even if left as it was.

Example 2 Preparation of the polymer film of Synthesis Example 2 and heat treatment were performed in the same manner as in Example 1. As a result, as in Example 1, a remarkable decrease in the receding contact angle of the surface of the polymer film 2 before and after heating was observed, and it was found that the surface was made liquid-adhesive. Further, this film was rolled and wrapped around an aluminum cylinder having a diameter of 100 mm and a length of 100 mm to produce a recording medium, and the surface of the film 2 was brought into contact with liquid ink instead of pure water as a liquid, as shown in FIG. As described above, the heating section of the thermal head 43 for thermal transfer printing was installed in contact with the film 2 surface. As the liquid ink 3a, a phthalocyanine-based cyan ink (dye concentration 1% by weight, solvent: NaOH having a concentration of 0.05 mol)
Aqueous solution). When an appropriate symbol was sent to the thermal head 43 and heated, the ink adhered only to the heated portion. Further, as shown in FIG. 5, recording paper (NM coated paper manufactured by Mitsubishi Paper Mills) 61
Was transported in contact with the cylindrical polyimide film 2, and the attached ink 3b was transferred to paper. This ink-attached portion (latent image S) exhibited ink-adhesiveness even when left as it was, and functioned as a printing machine.

Example 3 The polymers of Synthesis Examples 3 to 7 were formed into a film on a polyimide substrate.
The production of the film on the polyimide substrate was performed under the same conditions as in Example 1. Further, in the same manner as in Example 1, the film was heated in contact with the liquid to make the film surface liquid-adhesive. As shown in FIG. 6, the surface of the recording medium was heated at 130 ° C. for about 1 second by the infrared lamp 41 in the air, as shown in FIG. At this time, as a result of the liquid adhesion and the recovery of the liquid repulsion , as shown in FIG. 3, the receding contact angle reduced by the heating in the liquid is found to have returned to the original value by the heating in the air. Was. That is, it can be seen that the liquid repellency has been restored. From the result of this series of operations, storage and deletion of image information could be confirmed. Further, the temperature at which the receding contact angle decreases changes in accordance with the endothermic temperature of the copolymer due to DTA.

Example 4 The same operation as in Example 2 was performed except that the polymer of Synthesis Example 18 was dissolved in xylene hexafluoride, and the pattern of the ink-attached portion was erased by uniform heating with a ceramic heater. In this way, various patterns of character information could be printed on the A4 size recording paper.

Example 5 A latex solution of the polymer of Synthesis Example 19 was cast on an acrylic resin plate to form a film having a thickness of about 10 μm. Semiconductor laser (LN9 manufactured by Matsushita Electric Co., Ltd.)
850, 50 mW). A phthalocyanine-based cyan ink (solvent: NaOH aqueous solution having a concentration of 0.05 mol) was used as a liquid ink, the ink was applied to the entire surface of the film, and laser light focused by a lens was irradiated from the acrylic plate side. Thereafter, when the ink was removed, adhesion of the ink was observed only in the portion irradiated with the laser beam.

Example 6 The polymer of Synthesis Example 20 was dissolved in diethyl ether to form a film. After the operation of Example 1 was carried out, the adhered ink was removed by washing with water, and the film surface was dried and then dried in air. The irradiated part was irradiated with the semiconductor laser again. After a few seconds, the ink was applied again on the entire surface of the film, and the ink was removed. As a result, no ink adhered to the irradiated portion. That is, erasure of the stored information was confirmed.

Example 7 The polymer of Synthesis Example 21 was dissolved in ethyl acetate to a concentration of 7% by weight, coated on a polyimide film 1 (Kapton 200v manufactured by Du Pont-Toray Co.), and dried at 90 ° C. for 2 hours. As a result, a film having a thickness of about 1 μm was formed. Further, this film was rolled and wrapped around an aluminum cylinder having a diameter of 100 mm and a length of 100 mm to prepare a recording medium, and the surface of the film 2 was brought into contact with liquid ink instead of pure water as a liquid, as shown in FIG. As described above, the heating part of the thermal head for a thermal transfer printer was placed in contact with the film 2 surface. As the liquid ink, a phthalocyanine-based cyan ink (dye temperature: 1% by weight, solvent: NaOH aqueous solution having a concentration of 0.05 mol)
Was used. When an appropriate symbol was sent to the thermal head and heated, the ink adhered only to the heated portion. Further, as shown in FIG. 5, when the recording paper (NM coated paper manufactured by Mitsubishi Paper Mills) 61 was conveyed in contact with the cylindrical polyimide film 2, the adhered ink 3b was transferred to the paper. The ink-attached portion (latent image S) showed ink-adhesiveness even when left as it was.

Example 8 A film was formed and evaluated in the same manner as in Example 7 using the polymer synthesized in Synthesis Example 22. The results were the same as in Example 7.
When an appropriate symbol was sent to the thermal head and heated, the ink adhered only to the heated portion. Further, as shown in FIG. 5, the recording paper (NM coated paper manufactured by Mitsubishi Paper Mills) 61 was conveyed in contact with the cylindrical polyimide film 2, and the adhered ink 3b
Was transferred to paper. The ink-attached portion (latent image S) showed ink-adhesiveness even when left as it was.

[0070]

According to the method and apparatus using the recording medium of the present invention, a liquid-attached area and a non-liquid-adhered area can be easily formed on a liquid-repellent molded article. It is easy to return the area that was
For example, it is advantageous for application to plate making and the like.

[Brief description of the drawings]

FIG. 1 is a diagram for explaining the configuration and properties of a recording medium according to the present invention.

FIG. 2 is another diagram for explaining the configuration and properties of a recording medium according to the present invention.

FIG. 3 is a diagram showing a change in receding contact angle θr observed on the surface of a recording medium of the present invention when the recording medium surface is heated in a state where the liquid is in contact with the surface.

FIG. 4 is a diagram showing a change in receding contact angle θr observed on the surface of a recording medium when the recording medium surface is heated in a state in which a liquid is in contact with the surface of the recording medium of the present invention.

FIG. 5 is a diagram showing an embodiment of a recording medium of the present invention.

FIG. 6 is a diagram illustrating a relationship between a heating temperature of a recording layer in a liquid and a contact angle according to the present invention.

FIG. 7 is a diagram illustrating a relationship between a heating temperature in liquid and a contact angle of a recording layer.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Substrate 2 Film 3 Liquid (3a ... liquid ink, 2b ... adhered ink) 4 Heater (43 ... thermal head) 41 Infrared lamp

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Yasuo Katano 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company, Ltd. (56) References JP-A-49-36403 (JP, A) JP-A Sho JP-A-52-138203 (JP, A) JP-A-57-41998 (JP, A) JP-A-4-1633085 (JP, A) JP-A-3-178478 (JP, A) A) (58) Field surveyed (Int.Cl. ⁶ , DB name) B41N 1/14 B41M 1/06-1/08 B41C 1/055

Claims (8)

(57) [Claims] 1. A surface of a recording medium (A) and a contact material (B) selected from a liquid or a vapor and a solid that emits a liquid or a vapor at a temperature equal to or lower than the receding contact angle decrease start 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). At least the surface of the recording medium (A) used in the recording method for forming an area for reducing the receding contact angle with the recording liquid,
A recording medium comprising a compound containing a fluorine atom in a side chain. 2. A method in which the surface of the recording medium (A) is selectively heated while the surface of the recording medium (A) is in contact with the contact material (B), or the state in which the surface of the recording medium (A) is selectively heated. Forming a latent image area with a reduced receding contact angle with the recording liquid on the surface of the recording medium (A) by contact with the contact material (B) with Imaging, and then transferring this visible image to a transfer-receiving body, and heating the recording medium (A) in the absence of the contact material (B) to erase the latent image area. A recording material characterized in that at least the surface of the recording material (A) used in the method contains a compound containing a fluorine atom in a side chain. 3. The recording medium 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 (I). Wherein R ¹ represents hydrogen or a —CH ₃ group, and R ² represents —
(CH ₂ ) nR ³ (n is an integer of 1 to 10, and R ³ has ³ carbon atoms)
To 21 straight-chain or branched perfluoro alkyl _{group), - CH 2 CF 2 CHFCF} 3, H ₂ OCR ⁴ (R ⁴ is a linear or branched perfluoroalkyl group having 3 to 20 carbon atoms), (R ⁵ is a linear or branched perfluoroalkyl group having 1 to 8 carbon atoms) or —CH [CH ₂ OCF (C
F ₃ ) ₂ ] ₂ . ] 4. The recording medium 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). ] 5. The recording medium 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. ] 6. The recording medium 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 (IV). [However, R ₁ represents hydrogen or a —CH ₃ group, and R ¹³ represents —P
h-F (Ph is paraph ^{n 2} each are an integer of 0), - CF [CF (C
F ₃ ) ₂ ] ₂ , You. ] 7. The recording medium 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} . ] 8. The compound containing a fluorine atom in the side chain is represented by the following general formulas (I), (II), (III), (IV) and (V):
The recording material according to claim 1, wherein the recording material is a copolymer containing at least one of the compounds represented by the following as a monomer component. Wherein R ₁ represents hydrogen or a —CH ₃ group, and R ² represents —
(CH ₂ ) nR ³ (n is an integer of 1 to 10, and R ³ has ³ carbon atoms)
To 21 straight-chain or branched perfluoro alkyl _{group), - CH 2 CF 2 CHFCF} 3, (Ph represents a paraphenylene group), -CH (C
F ₃ ) ₂ , —CF (CF ₃ ) ₂ , Fluoroalkyl group), or -CH [CH ² OCF (C
F ₃ ) ₂ ] ₂ . ] Wherein R ¹ represents hydrogen or a —CH ₃ group, and R ⁶ represents —
(CF ₂₎ nF (n is an integer of _{1,3~17), - (CH 2)} n
R ⁷ (n is an integer of from 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 Linear or branched perfluoroalkyl group having 4 to 12 carbon atoms). ] [However, 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. ] [However, R ₁ represents hydrogen or a —CH ₃ group, and R ¹³ represents —P
h-F (Ph is paraph An integer of 0 to 10), -CF [CF (C
F ₃ ) ₂ ] ₂ , 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} . ]