JPH05177950A - Transparent recording material - Google Patents

Abstract

PURPOSE:To provide a transparent recording material wherein a precise fine image can be recorded directly with semiconductor laser beams, a stock space is small, and a miniaturized fine image can be simply confirmed by amplifying projection. CONSTITUTION:A solution wherein a developer in which a hydroxide group having a developing function is blocked with-(C=0) NH-R1 group, or-(C=0) O-R2 group (herein, R1, R2 represent a substituted or non-substituted alkyl group, a cycloalkyl group, an aryl group, an allyl group, a vinyl group, a benzyl group, a naphthyl group, etc.), an iron salt of an organic acid or a leuco dye, a near infrared beam absorbent, and a binder are dissolved uniformly in an organic solvent of MEK or the like is prepared as a spreading solution. The coating solution is spread to be dried on a base material of transparent plastics or the like so that a transparent recording layer of a 3-8mum thickness is obtained, which is enabled to record a precise fine visible image directly with semiconductor laser beams.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent recording material which can directly obtain a recording having absorption in a visible portion by heat or light.

[0002]

2. Description of the Related Art Heretofore, the following recording media are known as recording media for directly obtaining recording having absorption in the visible region by heat or light.

A heat-sensitive recording material used in a facsimile or the like is obtained by dispersing and mixing a colorless or light-colored electron-donating dye (leuco dye) and a color developer in an aqueous solution in which a water-soluble binder is dissolved to form fine particles. The obtained coating liquid is applied to an opaque support such as paper. On the other hand, it is a transparent thermosensitive recording medium prepared by coating a solution of a dye and a color developer in an organic solvent on a transparent support, and is a nitrogen-based or sulfur-based onium as a color developer and a heat activator. Those utilizing a compound are disclosed in JP-A 1-294088 and JP-A-63-45087. In these methods, recording is performed by direct heating in which a thermal head is brought into contact with a recording medium to heat it.

On the other hand, a recording material and a recording method for recording by irradiation of near infrared light without using a direct heating method are disclosed in JP-A-58-94494, JP-A-59-2880 and JP-A-58.
-42994 publication. JP-A-58-94494 discloses an optical recording material obtained by coating a support with a coating solution in which a near-infrared absorber is dispersed in a water-soluble binder in addition to a dye and a color developer. JP-A-58-42994 discloses an optical recording material in which a dye, a developer and a near-infrared absorbing agent are laminated on a substrate by vacuum vapor deposition, and JP-A-58-209594 discloses a base material. An isolation layer is formed by applying a solution of a near-infrared absorber on the two-layer interface between a coating layer in which a coloring agent such as a leuco dye is dissolved in an organic solvent and a developer coating layer provided on the material. Disclosed is a transparent thermosensitive recording medium which is provided to prevent fog.

[0005]

However, the recording layer of an ordinary heat-sensitive recording material comprising an electron-donating colorless dye and a color developer is
Since a dispersion coating solution prepared by adding a finely divided dye to a water system and a developer, an auxiliary agent and a filler is opaque and cannot be used for a transparent recording material. If the dye, the color developer and the auxiliary agent are simply dissolved in an organic solvent, the dye and the color developer react with each other to develop a color, so that the recording coating solution cannot be obtained.

On the other hand, even if an onium compound is dissolved as a color developer together with a dye in an organic solvent, the onium salt does not react with the dye and does not develop color in a normal state, so that a coating solution for a transparent thermosensitive recording medium can be obtained. However, onium salts have a slow reaction of decomposing by receiving heat energy, and a thermal head or a semiconductor laser does not cause a rapid and sufficient decomposition reaction at a heat energy of light-heat conversion, making it a sensitive and practical recording material. There was a drawback that could not be done. Moreover, the onium salt as a counter anion
Since antimony fluoride, phosphorus hexafluoride, arsenic hexafluoride, etc. must be bonded, there is a problem in material safety.

Further, a dispersion of a dye, a developer and a near infrared absorber together with a binder is opaque and cannot be used as a recording layer of a transparent recording material. Further, the method of vacuum-depositing each of the dye, the color developer and the near infrared absorber on the substrate is not suitable as a method for obtaining a general transparent recording material from the viewpoint of the transparency of the recording layer and the cost.

Further, in the transparent thermosensitive recording medium in which a separating layer of a near-infrared absorber is provided between the dye layer and the developer layer on the boundary surface of the two layers, each layer is slightly mixed with each other when the respective layers are coated. Is likely to occur, and since the layer structure is at least 3 layers,
There was a problem in cost and mass production.

In view of the above situation, the present invention uses a coating material containing all the necessary materials dissolved in one liquid to contain a transparent record which is directly absorbed by heat or light in a precise visible region. The challenge was to provide a recording medium.

[0010]

Means for Solving the Problems The above-mentioned problems are the color development represented by the following general formula (1) in which at least one of phenolic hydroxyl groups having a color development function is blocked on a transparent substrate. This is achieved by providing a transparent recording layer by coating an agent and a solution containing a metal salt of an organic acid or a leuco dye that develops a color by reacting with the developer in an organic solvent.

R (OR _A ) m (OH) nm (1) (wherein R is a substituted or unsubstituted aryl group, R _A
Is an N-substituted carbamoyl group (-(C = O) NHR < ₁ >)
Alternatively, an O-substituted oxycarbonyl group (-(C = O) O
R ₂ ) group, R ₁ and R ₂ represent a substituted or unsubstituted alkyl group, cycloalkyl group, vinyl group, allyl group, aryl group, benzyl group, naphthyl group, mesyl group and tosyl group. n and m are integers of 1 to 3 and m ≤ n.
When n is 2 or more, R ₁ or R ₂ may be the same or different. ) Further, as the developer represented by the general formula (1), a developer represented by the following general formula (2) or (3) is more preferable.

[0012]

[Chemical 2] (Here, R _A , n and m are the same as those in the general formula (1). X is C (═O) O, C (═O) N
H, SO ₂ , and Z are alkyl groups, alkoxyphenyl groups, and benzyl groups, and Y is C (CH ₃ ) ₂ , CHR _B , and C.
H ((C = O) OR B), S, SO 2, S-R C -S,
_{O-R C -O, (C} = O) O-R C -O (C = O), S
—R _C —O—R _C —O—R _C —S and R _B represent an alkyl group, an aryl group, and R _C represents an alkylene group. )

Further, a light absorbing agent which absorbs light and converts it into heat is dissolved and contained in the transparent recording layer,
It is possible to obtain a transparent and highly sensitive optical recording material.

A solvent-soluble developer in which at least one hydroxyl group having a color developing function is blocked by an N-substituted carbamoyl group, in other words, an N-substituted carbamate type developer is represented by the following formula ( The compound shown in 4) or (5) is preferable.

[0015]

[Chemical 3] (Here, R ₁ , n and m are the same as those in the general formula (1), and X, Y and Z are the same as those in the general formula (2) or (3).)

Examples of the N-substituted carbamoyl group are as follows. Phenylcarbamoyl group Naphthylcarbamoyl group Cyclohexylcarbamoyl group Halogenated phenylcarbamoyl group p-Toluenesulfonylcarbamoyl group 3,4-Dichlorophenylcarbamoyl group m-Isopropenyl-α, α-dimethylbenzylcarbamoyl group α, α-Dimethylbenzylcarbamoyl group α -Methylbenzylcarbamoyl group m-Methyl-α, α-dimethylbenzylcarbamoyl group m-Ethyl-α, α-dimethylbenzylcarbamoyl group m-Propyl-α, α-dimethylbenzylcarbamoyl group Benzylcarbamoyl group Methylcarbamoyl group Ethylcarbamoyl group n-Propylcarbamoyl group iso-Propylcarbamoyl group n-Butylcarbamoyl group tert-Butylcarbamoyl group n-Octadecylcarbamoyl group Chloromethylcarbamoyl group 2-Chloroethyl group A carbamoyl group m- toluylene-carbamoyl p- toluylene-carbamoyl 2-methoxy-phenylcarbamoyl group 4-methoxy-phenylcarbamoyl group allylcarbamoyl group

Examples of the block group having two N-substituted carbamoyl groups include 3,3'-dichlorodiphenyl 4,4'-dicarbamoyl group, hexamethylene 1,6-dicarbamoyl group and toluene 2,4- A dicarbamoyl group can be exemplified.

As a method for introducing a carbamoyl group into the phenolic hydroxyl group, a method of adding an isocyanate compound to the phenolic hydroxyl group in the presence of an acid or a base and a method of adding the phenol compound to chloroformic acid A method is known in which the aryl chloroformate compound and the amine are condensed in the presence of a base after the conversion to the aryl compound.

As a result of investigating the method for producing the block developing agent represented by the formula (4) or the formula (5) having an N-substituted carbamoyl group as a blocking group, the former method, that is, an isocyanate compound / base system was investigated. Was found to be suitable, and it was found to be particularly effective to use benzene as the solvent.

For example, when n-propyl gallate and phenyl isocyanate are reacted with triethylamine as a base, the reaction proceeds if pyridine or ethyl acetate, which is a general solvent for esterification reaction, is used. After completion of the reaction, it is necessary to carry out post-treatment to isolate and purify the desired product, while using benzene as a solvent,
Since the target substance precipitates as the reaction progresses, only filtration is required, which is industrially very advantageous.

Specifically, a developer compound such as n-propyl gallate, n-stearyl gallate, bisphenol A, benzyl P-hydroxybenzoate and phenyl isocyanate, cyclohexyl isocyanate, octadecyl isocyanate. An isocyanate compound such as is added to benzene. A base such as pyridine, dimethylaminopyridine or triethylamine is added to the reaction mixture, and the mixture is reacted for a predetermined time and filtered to obtain the desired product. Alternatively, the developer compound and the base may be mixed with benzene and then the isocyanate compound may be added to the reaction mixture. As benzene, it is preferable to use dry benzene or anhydrous benzene in order to suppress the production of a urea compound as a by-product.

The reaction temperature is the melting point temperature of benzene (5 ° C.)
To the boiling temperature (80 ° C), but it is preferably between 60 ° C and 80 ° C to accelerate the reaction. The reaction time depends on the precipitation time of the precipitate, and since the precipitation time varies depending on each reaction, it has to be appropriately determined. Further, when the precipitation of the precipitate is very slow, it may be necessary to concentrate the reaction solution.

The isocyanate compound is preferably used in the range of 1.0 to 20.0 equivalents with respect to the phenolic hydroxyl group of the color developer, but the urea compound which is a by-product from the isocyanate compound. 1.0 to suppress the generation of
A range of 3.0 equivalents is good.

The following compounds can be exemplified as the developer obtained by blocking with the N-substituted carbamoyl group thus obtained.

[0025]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18]

[Chemical 19]

[Chemical 20]

[Chemical 21]

[Chemical formula 22]

[Chemical formula 23]

Further, as a color developer in which at least one hydroxyl group having a color developing function is blocked by an O-substituted oxycarbonyl group, in other words, a carbonate type color developer, the following formula (6) or ( The compound shown in 7) is preferable.

[0027]

[Chemical formula 24] (Here, R ₂ , n and m are the same as those in the general formula (1), and X, Y and Z are the same as those in the general formula (2) or (3).)

As the O-substituted oxycarbonyl group, the following can be exemplified. - (C = O) O- CH 3 methoxycarbonyl group - (C = O) O- C 2 H 5 ethoxycarbonyl group - (C = O) O- n-C 3 H 7 n- pro Polo alkoxycarbonyl group - ( C = O) O-n- C 4 H 9 n- butyloxycarbonyl group - (C = O) O- iso-C 4 H 9 iso- butyloxycarbonyl group - (C = O) O- tert- C 4 H ₉ tert-butyloxycarbonyl group — (C═O) On—C ₁₆ H ₃₃ n-hexadecyloxycarbonyl group — (C═O) O—CH ₂ CH═CH ₂ aryloxycarbonyl group — (C = O) O-CH = CH 2 vinyloxy group - (C = O) O- CH 2 C 6 H 5 benzyloxycarbonyl group - (C = O) O- C 6 H 5 phenylene butyloxycarbonyl group - (C _{= O) O-C 10 H} 7 naphthoquinone Ciro alkoxycarbonyl group - (C = O) O- CH 2 CH 2 CCl 3 2,2,2- trichloroethoxycarbonyl Carbonyl group - (C = O) O- CH 2 CH 2 Si (CH 3) 3 2- ( trimethylsilyl) ethoxycarbonyl group

As a method for introducing an O-substituted oxycarbonyl group into a phenolic hydroxyl group, alkyl chloroformate,
Alternatively, a method of reacting aryl chloroformate with a phenol compound in the presence of a base, a method of reacting a dicarbonate compound with a phenol compound in the presence of a base, and the like are known, and the above-mentioned general formula (6) ) Or (7) block developer can also be produced by these methods.

The following compounds can be exemplified as specific compounds of the carbonate type block developing agent.

[0031]

[Chemical 25]

[Chemical formula 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

[Chemical 30]

[Chemical 31]

[Chemical 32]

[Chemical 33]

[Chemical 34]

[Chemical 35]

[Chemical 36]

[Chemical 37]

[Chemical 38]

[Chemical Formula 39]

[Chemical 40]

In the present invention, when there are a plurality of hydroxyl groups having a color developing function, N-substituted carbamoyl groups and O-substituted oxycarbonyl groups may be mixed to block the hydroxyl groups.

The organic acid of the metal salt of an organic acid used in the present invention is preferably an ortho-position or meta-position-substituted benzoic acid, o-benzoylbenzoic acid o-alkyl-substituted benzoylbenzoic acid o-, m- Alkyl benzoic acid o-toluyl benzoic acid m-toluyl benzoic acid o-halogen benzoic acid m-halogen benzoic acid.

As the metal of the metal salt, iron, silver, vanadium and cobalt are preferable, and iron is the most preferable.

The leuco dye that can be used in the present invention includes
Conventionally, all electron-donating colorless dyes known in the field of thermal recording paper can be used. Typical examples are shown below. Crystal violet lactone 3-diethylamino-6-methyl-7-anilinofluorane 3-diethylamino-benzo [C] fluorane 3,6-di (n-dimethylamino) -fluorane-9-spiro-3
-(6-Dimethylamino) phthalide 3-dibutylamino-6-methyl-7-anilinofluorane 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluorane 3- (4 -Diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide 3- (N-ethyl-N-cyclohexylamino) -6-methyl-7
-Anilino Fluoran

The above-mentioned color developer, leuco dye or metal salt of an organic acid is toluene, methyl ethyl ketone (ME
Dissolve with a binder in a solvent suitable for solvent coating such as K), acetone or chloroform.

When a conventional leuco dye and a color developer, which are heat-sensitive color developing materials, are dissolved in a solvent together with a binder and used, many binders are desensitized, and in extreme cases, there is a possibility that the color is not developed. Therefore, the choice of binder is limited.

On the other hand, the use of a color developing agent in which at least one of the phenolic hydroxyl groups having color developing ability represented by the general formula (1) of the present invention is used, the restriction is remarkably alleviated. In particular, in the case of a combination with an organic acid metal salt, there is an advantage that various binders can be selected in a wide range without any concern.

The binder usable in the present invention includes:
Polystyrene, polyvinyl butyral, polyester,
Styrene-butadiene-acrylic copolymer, silicone varnish, EB, and UV curable resin can be preferably used.

In the case of an optical recording material, a light absorbing material is dissolved together with the above-mentioned components and contained in the transparent recording layer. Specific examples of the light absorber that can be preferably used when a semiconductor laser beam is used as a recording light source include immonium or diimmonium compounds such as IRG002 (trade name) and IRG022 (trade name) manufactured by Nippon Kayaku, and dithiol nickel. Complexes, 1,1,5,5-tetrakis (p-dimethylaminophenyl) -3-methoxy-1,4-pentadiene Toluene and other cyanine dyes, squarylium dyes, naphthoquinone dyes, phthalocyanines and naphthalocyanines is there.

As the support, glass, polyester resin, polymethylmethacrylate resin, polyethylene resin,
Films, sheets and plates such as polycarbonate resin and polystyrene resin, which have heat resistance and high transparency, are preferable.

The composition of the material for obtaining the recording layer of the transparent recording material of the present invention is about 3 to 30 parts of a block developer, 3 to 30 parts of an organic acid metal salt or leuco dye, 20 parts of a binder,
A light absorbing agent (1 to 10 parts), which is dissolved in a solvent so that the solid content is about 10 to 20%, is applied onto a transparent support and dried to obtain a transparent optical recording material.

The transparent recording material of the present invention thus obtained is useful as a sheet for OHP or a film for sliding, or as a photomask for printing by recording.

Recording on the transparent recording material of the present invention is preferably performed by a laser rather than by a thermal head. As a laser, a semiconductor laser of several tens of mW enables clear recording.

[0045]

When a soluble block developer represented by the general formula (1) and a leuco dye or an organic acid metal salt are dissolved in an organic solvent, a transparent uncolored recording coating solution is obtained. Even if the coating solution is applied onto a transparent substrate and dried, a color reaction does not occur and an almost colorless and transparent coating layer is formed. When the coating layer is heated with a thermal head or the like, the block group is released and the function as a developer appears.
It reacts immediately and a color image is obtained. However, in thermal recording with a thermal head, it is difficult to obtain a clear recorded image in high-speed recording, probably because the block group is not easily cut.
On the other hand, in a transparent recording material having a recording layer in which a near-infrared absorber is dissolved and added, when the laser light is irradiated, the light energy of the laser is converted into heat energy, so that the blocking group is Since a hydroxyl group having a color-developing ability is efficiently generated, a high-density recording can be obtained at a higher speed than a thermal head.

[0046]

【Example】

(Production of Block Developer) [Synthesis Example 1] 1.06 g (5 mM) of n-propyl gallate and 2.17 ml of phenyl isocyanate were placed in a dry eggplant-shaped flask.
(20mM) and 20ml of dry benzene, add 60
Heated to ° C. There, 0.1 ml of triethylamine (0.
7 mM) and stirred for 10 minutes under a nitrogen atmosphere. Then, a white precipitate was generated, which was filtered with benzene to obtain a product. The yield was 2.40g. The product is acetone /
Recrystallization was performed with a mixed solvent of benzene. It was confirmed that it was a block developer in which three hydroxyl groups of gallic acid were blocked by a phenylcarbamoyl group, by ¹ H-NMR, and that this developer was dissolved in a solvent (MEK) together with CVL and no color was developed. ¹ H-NMR data: 1.02 (3H, t, J = 7.0), 1.80 (2H, m), 4.31
(2H, t, J = 7.0), 7.00-8.00 (19H, m).

[Synthesis Example 2] n-propyl gallate 212 mg (1
To (mM), 0.51 ml (4 mM) of cyclohexyl isocyanate and dry benzene (4 ml) were added. Two drops of triethylamine were added to the reaction mixture, the mixture was stirred at 70 ° C. for 1 hour, and the reaction solution was filtered with benzene to obtain 455 mg of propyl gallate tri-N-cyclohexylcarbamate. The compound was identified by ¹ H-NMR. ¹ H-NMR data: 1.00 (3H, t, J = 7.0), 1.05-1.60 (17H,
m), 1.70-2.10 (18H, m), 4.25 (2H, t, J = 7.0), 5.20 (3H,
m), 7.78 (2H, s).

[Synthesis Example 3] In a dry eggplant-shaped flask,
1.06 g (5 mM) of monopropoxydiphenol sulfone, 2.17 ml (20 mM) of phenyl isocyanate and 20 ml of dry benzene were added, and the mixture was heated to 60 ° C on an oil bath. There,
0.1 ml (0.7 mM) of triethylamine was added, and the mixture was stirred under a nitrogen atmosphere for 10 minutes. Then a white precipitate was formed, so
This was filtered with benzene to obtain the product. Yield 1.47g
Met. The product was recrystallized with a mixed solvent of acetone / benzene. It was confirmed by ¹ H-NMR and that this developer was dissolved together with CVL in a solvent (MEK) and did not develop color, as a block developer in which a hydroxyl group of monopropoxydiphenol sulfone was blocked with a phenylcarbamoyl group. ¹ H-NMR data: 1.30 (3H, s), 1.32 (3H, s), 4.75 (1H,
m), 7.09-8.00 (14H, m).

[Synthesis Example 4] n-propyl gallate 1.06 g
(5 mM) was dissolved in ethyl acetate (20 ml), and to this was added 5.7 ml (25 mM) of ditert-butyl dicarbonate and pyridine (2 ml). The reaction solution was reacted under a nitrogen atmosphere at room temperature for 10 hours.
The reaction solution was concentrated and then purified with a silica gel column (developing solution: ethyl acetate / n-hexane (v / v = 1: 2)). Product ¹ H-
When confirmed by NMR, it was a compound in which a tert-butoxycarbonyl group (-C (= O) O-tert-butyl) was introduced into two of the three hydroxyl groups of n-propyl gallate. ¹ H-NMR data: 1.01 (3H, t, J = 7.0), 1.56 (18H, s), 1.7
7 (2H, m), 4.24 (2H, t, J = 7.0), 7.79 (2H, s).

Synthesis Example 5 n-propyl gallate 1.06 g
(5 mM) was dissolved in ethyl acetate (20 ml), methyl chloroformate 1.9 ml (25 mM) and pyridine (2 ml) were added thereto, and the mixture was reacted under a nitrogen atmosphere at 50 ° C. for 3 hours. The reaction mixture was diluted with ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous sodium sulfate, and concentrated. The oily substance obtained was applied to a silica gel column (developing solution: ethyl acetate / n-
Purified with hexane (v / v = 1: 2). When the product was confirmed by ¹ H-NMR, it was n-propyl trimethyl carbonate gallate. ¹ H-NMR data: 1.01 (3H, t, J = 7.4), 1.78 (2H, m), 3.92
(3H, s), 3.93 (6H, s), 4.28 (2H, t, J = 7.4), 7.91 (2H, s).

[Synthesis Example 6] 1.06 g (5 mM) of monopropoxydiphenol sulfone was dissolved in ethyl acetate (20 ml), and 3.5 ml (15 mM) of ditert-butyl dicarbonate and pyridine (2 ml) were added thereto. The reaction solution was reacted under a nitrogen atmosphere at 50 ° C. for 3 hours. The reaction solution was concentrated and then purified with a silica gel column (developing solution: ethyl acetate / n-hexane (v / v = 1: 2)). When the product was confirmed by ¹ H-NMR, it was a compound in which the hydroxyl group of monopropoxydiphenol sulfone was blocked with a tert-butoxycarbonyl group (-C (= O) O-tert-butyl). ¹ H-NMR data: 1.33 (3H, s), 1.35 (3H, s), 1.55 (9H,
s), 4.60 (1H, m), 6.92 (2H, dt, J = 8.5,3.0), 7.29 (2H, dt,
J = 8.5,3.0), 7.83 (2H, dt, J = 8.5,3.0), 7.94 (2H, dt, J = 8.
5,3.0).

[Synthesis Example 7] 228 mg (1 mM) of bisphenol A
Was dissolved in ethyl acetate (2 ml), and ditert-butyl dicarbonate (0.69 ml, 3 mM) and pyridine (0.1 ml) were added. The reaction solution was reacted under a nitrogen atmosphere at 50 ° C. for 3 hours. The reaction solution was concentrated and then purified with a silica gel column (developing solution: ethyl acetate / n-hexane (v / v = 1: 2)). Product ¹ H-NM
When confirmed by R, the tert-butoxycarbonyl group (-C
It was a compound in which the hydroxyl group of bisphenol A was blocked with (= O) O-tert-butyl). ¹ H-NMR data: 1.55 (18H, s), 1.65 (6H, s), 7.05 (4H, d
t, J = 8.5,2.5), 7.21 (4H, dt, J = 8.5,2.5).

(Manufacturing method of transparent recording material) [Example 1] A solvent (MEK) was dissolved in a solvent (MEK) according to the following formulation so that the solid content was 20%. Synthetic Example 1 block developer 20 parts Soluble iron salt: o-benzoylbenzoic acid iron salt 20 parts Binder: Polyvinyl butyral 20 parts Light absorber: IRG002 (Nippon Kayaku) 1 part This recording coating solution is transparent Apply it with a Mayer bar to a coating amount of 5 g / m ² on a smooth polyester film,
It was air dried at room temperature to obtain a transparent recording sheet. When this transparent recording medium was scanned with a semiconductor laser beam having an output of 30 mW at an operating speed of 40 mm / sec, a black recording line having a line width of 50 μm was obtained.
Further, in the 60 ° C. heat resistance test, no change in background color was observed. When this recording film was mounted on a slide and projected, a black line could be clearly enlarged. Further, even when this recording film was projected by OHP, a black line could be clearly enlarged.

[Example 2] The light absorber of Example 1 was replaced with 1,1,5,
Example 1 except that 0.2 parts of 5-tetrakis (p-dimethylaminophenyl) -3-methoxy-1,4-pentadiene was used
A transparent recording sheet was obtained in the same manner as in. When scanning this transparent recording medium with a semiconductor laser beam with an output of 30 mW at an operating speed of 40 mm / sec, a black recording line with a line width of 50 μm was obtained.

Example 3 Example 1 was repeated except that the light absorber of Example 1 was replaced with 10 parts of toluenedithiol nickel complex.
A transparent recording sheet was obtained in the same manner as in. When scanning this transparent recording medium with a semiconductor laser beam with an output of 30 mW at an operating speed of 40 mm / sec, a black recording line with a line width of 45 μm was obtained.

[Example 4] A recording coating liquid was prepared in the same manner as in Example 1 except that the binder of the recording coating liquid of Example 1 was replaced with 20 parts of the UV curable resin GRANDIC UV5020 (Dainippon Ink and Chemicals, Inc.). Got Apply this coating solution to a transparent polyester film with a Mayer bar to a coating amount of 5 g / m, then move it at a conveyor speed of 5 m / min while UV
U is irradiated with UV rays from a distance of 12 cm from the surface of the coating layer using an irradiation device (Igraphic, light output 3 KW 1 lamp).
The V resin was cured to obtain a transparent recording sheet. A semiconductor laser beam with an output of 30 mW is operated on this transparent recording medium at an operating speed of 40 mm / sec.
When scanned with, a recording line having a line width of 50 μ was obtained.

Example 5 A solvent (toluene) was dissolved in the following composition so that the solid content was 20%. Block developer of Synthesis Example 1 5 parts Soluble iron salt: o-benzoylbenzoic acid iron salt 5 parts Binder: Polystyrene 20 parts Light absorber: IRG002 (Nippon Kayaku Co., Ltd.) 1 part This recording coating solution is transparent. Apply it on the polyester film with a Mayer bar so that the amount applied is 5 g / m ² .
It was air dried at room temperature to obtain a transparent recording sheet. When this transparent recording medium was scanned with a semiconductor laser beam having an output of 30 mW at an operation speed of 40 mm / sec, a black recording line having a line width of 45 μ was obtained.

[Example 6] A solvent (MEK) was dissolved in the following composition so that the solid content was 20%. Block developer of Synthesis Example 1 20 parts Soluble iron salt: o-Chlorobenzoic acid iron salt 20 parts Binder: Polyvinyl butyral 20 parts Light absorber: NK-2014 (manufactured by Japan Photosensitive Dye Research Institute) 1 part For this recording Apply the coating solution on a transparent polyester film with a Mayer bar to a coating amount of 5 g / m ² ,
It was air dried at room temperature to obtain a transparent recording sheet. When scanning this transparent recording medium with a semiconductor laser beam with an output of 30 mW at an operating speed of 40 mm / sec, a black recording line with a line width of 50 μm was obtained.

Example 7 A transparent recording sheet was obtained in exactly the same manner as in Example 6 except that the soluble iron salt of Example 6 was replaced with 20 parts of iron o-benzoylbenzoate salt. When scanning this transparent recording medium with a semiconductor laser beam with an output of 30 mW at an operating speed of 40 mm / sec, a black recording line with a line width of 50 μm was obtained.

[Example 8] A solvent (MEK) was dissolved in the following composition so that the solid content was 20%. Block Developer of Synthesis Example 2 15 parts Soluble iron salt: o-benzoylbenzoic acid iron salt 25 parts Binder: Polyvinyl butyral 20 parts Light absorber: 1,1,5,5-tetrakis- (p-dimethylaminophenyl) ) -3-Methoxy-1,4-pentadiene 0.2 part This coating liquid for recording was coated on a transparent polyester film with a Mayer bar so as to have a coating amount of 5 g / m ² .
It was air dried at room temperature to obtain a transparent recording sheet. When scanning this transparent recording medium with a semiconductor laser beam with an output of 30 mW at an operating speed of 40 mm / sec, a black recording line with a line width of 50 μm was obtained.

[Example 9] A solvent (chloroform) was dissolved in the following formulation so that the solid content was 10%. Block developer of Synthesis Example 2 8 parts Soluble iron salt: o-benzoyl benzoic acid iron salt 12 parts Binder: Polyvinyl butyral 20 parts Light absorber: IRG002 (Nippon Kayaku Co., Ltd.) 1 part This recording coating solution is transparent Apply it with a Mayer bar to a coating amount of 5 g / m ² on a smooth polyester film,
It was air dried at room temperature to obtain a transparent recording sheet. When scanning this transparent recording medium with a semiconductor laser beam with an output of 30 mW at an operating speed of 40 mm / sec, a black recording line with a line width of 50 μm was obtained.
In the 60 ° C heat resistance test, no change in the background color was observed. When this recording film was mounted on a slide and projected, the blue line could be clearly enlarged.

Example 10 A solvent (a mixed solvent of chloroform / acetone (v / v = 1: 1)) was dissolved in the following formulation so that the solid content was 20%. Block developer of Synthesis Example 3 20 parts Leuco dye: Crystal violet lactone 20 parts Binder: Polystyrene 20 parts Light absorber: Toluenedithiol nickel complex 10 parts This recording coating solution is applied onto a transparent polyester film in an amount of 5 g. Apply with a Mayer bar so that it becomes / m ² ,
It was air dried at room temperature to obtain a transparent recording sheet. When scanning this transparent recording medium with a semiconductor laser beam with an output of 30 mW at an operating speed of 40 mm / sec, a blue recording line with a line width of 40 μm was obtained.
In the 60 ° C heat resistance test, no change in the background color was observed. When this recording film was mounted on a slide and projected, the blue line could be clearly enlarged.

Example 11 A transparent recording sheet was obtained in the same manner as in Example 10 except that the light absorber of Example 10 was replaced with 20 parts of bis (dithiobenzyl) nickel complex. A semiconductor laser beam with an output of 30 mW is operated at a speed of 40 mm on this transparent recording medium.
When scanned at / sec, a blue recording line with a line width of 45μ was obtained.

Example 12 A transparent recording material was prepared in the same manner as in Example 1, except that the block developer of Synthesis Example 4 was used as the developer. The transparent recording material was scanned with a semiconductor laser beam with an output of 30 mW at an operating speed of 40 mm / sec.
A recording line having a line width of μ was obtained. Further, in the 60 ° C. heat resistance test, no change in background color was observed. When this recording film was mounted on a slide and projected, a black line could be clearly enlarged. Further, even when this recording film was projected by OHP, a black line could be clearly enlarged.

[Example 13] A transparent recording material was prepared in the same manner as in Example 6 except that the block developer of Synthesis Example 4 was used as the developer. The transparent recording material was scanned with a semiconductor laser beam with an output of 30 mW at an operating speed of 40 mm / sec.
A recording line having a line width of μ was obtained.

[Example 14] A solvent (MEK) was dissolved in the following composition so that the solid content was 20%. Block developer of Synthesis Example 5 20 parts Soluble iron salt: o-chlorobenzoic acid iron salt 20 parts Binder: Polyvinyl butyral 20 parts Light absorber: 1,1,5,5-tetrakis- (p-dimethylaminophenyl) ) -3-Methoxy-1,4-pentadiene 0.3 part This recording coating solution is applied on a transparent polyester film with a Mayer bar so that the coating amount is 5 g / m ² .
It was air dried at room temperature to obtain a transparent recording sheet. When scanning this transparent recording medium with a semiconductor laser beam with an output of 30 mW at an operating speed of 40 mm / sec, a black recording line with a line width of 50 μm was obtained.

Example 15 A transparent recording material was prepared in the same manner as in Example 1, except that the block developer of Synthesis Example 5 was used as the developer. The transparent recording material was scanned with a semiconductor laser beam with an output of 30 mW at an operating speed of 40 mm / sec.
A recording line having a line width of μ was obtained.

Example 16 A transparent recording material was prepared in the same manner as in Example 10, except that the block developer of Synthesis Example 6 was used as the developer. This transparent recording medium was scanned with a semiconductor laser beam with an output of 30 mW at an operating speed of 40 mm / sec.
A recording line having a line width of μ was obtained.

Example 17 A transparent recording material was prepared in the same manner as in Example 11 except that the block developer of Synthesis Example 7 was used as the developer. This transparent recording medium was scanned with a semiconductor laser beam with an output of 30 mW at an operating speed of 40 mm / sec.
A recording line having a line width of μ was obtained.

[0070]

As described above, when the block developing agent of the present invention is used, no color develops in the solvent composition even when mixed and dissolved with the color developing agent, so that a transparent recording material can be efficiently produced by one coating. can do. Further, the transparent recording material of the present invention can directly record a fine image in a non-contact manner by irradiating light such as a laser beam. It can be greatly shortened. If the transparent recording material of the present invention is used as an output sheet of a printer, the OHP sheet can be immediately used.
There is an effect that it can be used as a copy or an original for copying.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akio Sekine 5-21-1 Oji, Kita-ku, Tokyo Inside the Product Development Laboratory, Jujo Paper Co., Ltd.

Claims (5)

[Claims] 1. A transparent support, on which at least one phenolic hydroxyl group having a color developing function is N-substituted carbamoyl group (— (C═O) NHR ₁ ), or O-substituted oxycarbonyl. It contained a developer represented by the following general formula (1) blocked with a group (-(C = O) OR ₂ ) and a metal salt of an organic acid or a leuco dye that develops color by reacting with the developer. A transparent recording body provided with a transparent recording layer. R (OR _A ) m (OH) nm (1) (wherein R is a substituted or unsubstituted aryl group, R _A
Is an N-substituted carbamoyl group (-(C = O) NHR < ₁ >)
Alternatively, an O-substituted oxycarbonyl group (-(C = O) O
R ₂ ) group, R ₁ and R ₂ represent a substituted or unsubstituted alkyl group, cycloalkyl group, vinyl group, allyl group, aryl group, benzyl group, naphthyl group, mesyl group and tosyl group. n and m are integers of 1 to 3 and m ≤ n.
When n is 2 or more, R ₁ or R ₂ may be the same or different. ) 2. The transparent recording material according to claim 1, wherein the developer has the following general formula (2) or (3). [Chemical 1] (Here, R _A , n and m are the same as those in the general formula (1) described in claim 1. X is C (═O) O,
C (= O) NH, SO 2, Z is an alkyl group, alkoxyphenyl group, a benzyl group, _{Y, C (CH 3) 2,} C
HR _B , CH ((C═O) OR _B ), S, SO ₂ , S-
_{R C -S, O-R C} -O, (C = O) O-R C -O (C
_{= O), S-R C} -O-R C -O-R C -S, R B is,
Alkyl group, aryl group and R _C represent an alkylene group. ) 3. A transparent optical recording material, wherein the transparent recording layer according to claim 1 or 2 contains a light absorber that absorbs light and converts it into heat. 4. The transparent optical recording material according to claim 3,
A transparent optical recording material, wherein the transparent recording layer contains an ultraviolet ray or electron beam effect resin. 5. A developer compound and an isocyanate compound are mixed with benzene, and a base is further added as a catalyst for reaction, or a developer compound and a base are mixed with benzene, and an isocyanate compound is added thereto. The method for producing a color developer, wherein the blocking group represented by the general formula (1) is an N-substituted carbamoyl group, which is additionally reacted.