JPH11119424A - Self-color forming type photosensitive and pressure sensitive recording material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent frictional staining due to improvident pressing or friction during storage by forming a photosensitive and pressure sensitive recording layer having photosensitive microcapsules and a developer on a transparent substrate and an opaque layer on the recording layer. SOLUTION: The photosensitive and pressure sensitive recording material has a photosensitive and pressure sensitive recording layer having photosensitive microcapsules contg. a dye precursor, a photoinitiator and a polymerizable compd. and a developer in a single-layered or laminated state on the transparent substrate and an opaque layer on the recording layer. A plastic or glass sheet is useful as the transparent substrate. The opaque layer is preferably formed from an aq. coating compsn. contg. a pigment and a water-soluble high molecular compd. and/or a water-dispersible high molecular compd. The water-soluble high molecular compd. is, e.g. starch or a polyvinyl compd. and the water- dispersible high molecular compd. is, e.g. a styrenebutadiene copolymer. The coating weight of the opaque layer is 2-20 g/m<2> , preferably 3-15 g/m<2> on dry basis.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a self-coloring type photosensitive pressure-sensitive recording material using photosensitive microcapsules and an image forming method, and more particularly to a method for preventing rubbing caused by careless pressurization or friction during storage. The present invention relates to a self-colored photosensitive pressure-sensitive recording material and an image forming method which prevent the self-coloring.

[0002]

2. Description of the Related Art Image forming systems using microcapsules sensitive to radiation including visible light are described in U.S. Pat. Nos. 4,399,209 and 4,419,966. . These image forming systems include an image sheet having a layer containing microcapsules containing a photocurable or photosoftenable photosensitive composition,
After exposing imagewise to harden or soften the microcapsules imagewise, pressure is applied to break the microcapsules imagewise. This image forming system takes a form in which an image forming sheet and an image receiving sheet are peeled after pressure development. U.S. Pat. No. 4,440,846 describes a self-coloring type image forming system. This self-coloring type image forming system has an advantage that it does not require a step of superimposing the image receiving materials, applying pressure to break the microcapsules and then peeling off the image receiving materials, and does not generate waste. This self-coloring type photosensitive pressure-sensitive recording material can form an image on one sheet, but has a problem that capsules are destroyed and stains are generated due to careless pressurization or friction during storage.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a self-coloring photosensitive pressure-sensitive material which prevents rubbing caused by careless pressurization or friction during storage, and an image forming method.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
On a transparent support, there is provided a photosensitive microcapsule containing a dye precursor, a photoinitiator and a polymerizable compound, and a photosensitive pressure-sensitive recording layer having a developer in a single layer or a laminated state, and an opaque layer thereon. A self-coloring type photosensitive pressure-sensitive recording material having
In addition, the self-coloring type photosensitive pressure-sensitive recording material was imagewise exposed from the transparent support side, and then developed under pressure to achieve the image forming method.

[0005] As the transparent support used in the present invention, a plastic sheet or a glass sheet is useful. Examples of plastics include polyester, polyethylene, polypropylene, cellulose esters (eg, acetylcellulose), polyvinyl acetal, polystyrene,
Examples thereof include polycarbonate, polyethylene terephthalate, and polyimide. The opaque layer of the invention is preferably formed from an aqueous coating composition comprising a pigment, a water-soluble polymer compound and / or a water-dispersible polymer compound. Examples of the pigment include inorganic pigments such as calcium carbonate, talc, silica, clay, barium sulfate, magnesium carbonate, lead sulfate, zinc white, white silk, titanium oxide, mica, gypsum, aluminum hydroxide, polystyrene, polyvinyl toluene, and styrene. Finely divided organic pigments such as divinylbenzene copolymer, polymethyl methacrylate, and urea-formaldehyde polymer.

The water-soluble polymer compounds include starches, alginic acid compounds, cellulose derivatives, casein,
Examples include natural polymer compounds such as gelatin and gum arabic, polyvinyl compounds such as completely saponified polyvinyl alcohol and pyrrolidone-modified polyvinyl alcohol, polyacrylamide, polyacrylic acid, and vinylpyrrolidone-maleic acid copolymer. . Examples of the water-dispersible polymer compound include styrene-butadiene copolymer, styrene-maleic anhydride copolymer, butadiene-methacrylate copolymer, vinyl acetate-vinyl chloride-ethylene copolymer, methacrylate-butadiene copolymer, A latex in which a vinylidene chloride-acrylonitrile copolymer or the like is dispersed in water can be used.

The aqueous coating composition for forming the opaque layer may further comprise a curing agent such as methylol melamine and boric acid, a lubricant such as stearic acid amide and wax, other surfactants, an ultraviolet absorber, and the like. Auxiliary agents such as a fluorescent dye, an antistatic agent, an anti-blocking agent, and a preservative may be appropriately added. The coating amount of the opaque layer is not particularly limited, but is usually ^{2 to 20} g / m ² by dry weight,
Preferably it is in the range of ^{3 to} 15 g / m ² . The self-coloring type photosensitive pressure-sensitive recording material of the present invention may have a constitution in which a photosensitive microcapsule layer, a color developer layer and an opaque layer are formed on a transparent support, or a transparent support, a photosensitive microcapsule and a color developer. , And an opaque layer.

The photosensitive microcapsules used in the present invention can be produced according to the methods disclosed in the aforementioned US Pat. Nos. 4,399,209 and 4,419,966. . That is, the photosensitive microcapsules contain a photoinitiator and a polymerizable compound in the internal phase. They are typically photopolymerizable materials, photocrosslinkable materials, which thicken or cure upon exposure. Further, in addition to the photosensitive material, a dye precursor is contained. The polymerizable compound used in the present invention is preferably a material curable by radical addition polymerization or ionic polymerization, but is not particularly limited thereto.

A typical polymerizable compound is an ethylenically unsaturated organic compound. These compounds are preferably liquid and contain at least one terminal ethylene group per molecule. Further preferred examples of the photocurable material are ethylenically unsaturated compounds containing two or more ethylene groups per molecule. Representative examples of these compounds are ethylenically unsaturated acid esters of polyhydric alcohols such as trimethylolpropane triacrylate or dipentaerythritol hydroxypentaacrylate. Further, as another example, an acrylate prepolymer obtained by a partial reaction between pentaerythritol and acrylic acid or an acrylate ester, and further, US Pat. No. 3,783,151 and US Pat.
Examples thereof include isocyanate-modified acrylic acid esters, methacrylic acid esters, and itaconic acid esters of polyhydric alcohols disclosed in the specifications of U.S. Pat.

The photoinitiator absorbs actinic radiation and generates free radicals which can initiate free radical polymerization of the polymerizable or crosslinkable compound. As the photoinitiator of the present invention, use may be made of ionic dye-counter ion compounds described in JP-A-62-150242, JP-A-60-60606, JP-A-3-20260 and JP-A-3-116043. Is preferred. A preferred ionic dye-counter ion is the cationic dye borate, which is a compound of general formula (I).

[0011]

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Wherein D ⁺ is a cationic dye moiety, R ₁ ,
R ₂ , R ₃ and R ₄ are an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alkenyl group, an alkynyl group,
Represents a cycloalkyl group or an allyl group. R ₁ , R ₂ ,
R ₃ and R ₄ may be the same or different. Useful dyes form photoreducible complexes with borate anions and are cationic methine, polymethine, triarylmethane, indoline, thiazine, oxazine and acridine dyes. More preferably, the dyes are cationic cyanine, carbocyanine, hemicyanine, rhodamine and azomethine dyes. Useful cationic dyes have the general formula (I)
It is a cyanine dye of I).

[0013]

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In the formula, n is 0, 1, 2, 3, R ₅ is an alkyl group, Y is CH ＝ CH, N—CH ₃ , C (CH ₃ ) ₂ ,
O, S, Se are represented. Borate anions
It is preferable that at least 1 to 3 or less of R ₁ , R ₂ , R ₃ and R ₄ are alkyl groups. As the alkyl group, up to 20 carbon atoms, more preferably 1 to 1 carbon atoms
7 Preferably, R ₁ , R ₂ , R ₃ and R ₄ are a combination of an alkyl group and an aryl group or an aralkyl group, and a combination of three aryl groups and one alkyl group (for example, triphenylbutyl borate, etc.) It is even more preferred.

Another example is disclosed in Japanese Patent Application Laid-Open No. 5-224426.
As disclosed in the publication, diaryl ketone derivative, polycyclic quinone, benzoin alkyl ether, alkoxyphenyl ketone, o-acylated oxyimino ketone, phenanthrenequinone, benzophenone, substituted benzophenone, xanthone, thioxanthone, halogenated compound,
For example, chlorosulfonyl and chloromethyl polynuclear aromatic compounds, chlorosulfonyl and chloromethyl heterocyclic compounds, chlorosulfonyl and chloromethylbenzophenone, fluorenone, haloalkane and the like can be mentioned.

The dye precursor used in the present invention includes:
A colorless electron donating compound can be given. Representative examples of this compound include a substantially colorless compound having a lactone, lactam, sultone, spiropyran, ester, or amide structure in a partial skeleton.
For example, triarylmethane compounds, bisphenylmethane compounds, xanthene compounds, fluoran compounds, thiazine compounds, spiropyran compounds, and the like. Next, specific examples of the dye precursors that form yellow, magenta, and cyan will be described.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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The photosensitive microcapsules used in the present invention can be used as a sensitizer for improving photoresponsiveness, for example, as an autoxidizer described in JP-A Nos. 62-18537 and 64-91130. It is possible to use a disulfide compound such as mercaptobenzothiazole disulfide described in JP-A-2-291561, and a thiol compound described in JP-A-2-868, such as defined N, N-dialkylaniline. it can. The discontinuous wall microcapsules used for encapsulation of the internal phase of the present invention are manufactured using known encapsulation methods, including coacervation, interfacial polymerization, or polymerization of one or more monomers in oil. be able to.

Representative examples of suitable capsule wall formers include gelatin materials (US Pat. Nos. 2,730,456 and 2,800,457), including gum arabic, polyvinyl alcohol, carboxymethyl cellulose.
Resorcinol-formaldehyde capsule wall forming agent (US Pat. No. 3,755,190), isocyanate wall forming agent (US Pat. No. 3,914,511), isocyanate-polyol wall forming agent (US Pat. No. 379)
No. 6669), urea-resorcinol-formaldehyde (US Pat. No. 4,001,140) whose lipophilicity has been enhanced by the addition of urea-formaldehyde wall formers, especially resorcinol, or melamine-formaldehyde and hydroxypropylcellulose ( U.S. Pat. No. 4,025,455).

The average particle size of the microcapsules used in the present invention is preferably in the range of 1 to 25 microns. The size of the capsule is preferably small in particle size due to photographic characteristics such as resolving power, etc., but it is easy to burst by pressure,
Considering problems such as loss of holes or fibers in the support,
It is preferable to adjust the diameter to 3 to 15 microns, particularly 3 to 10 microns.

As the color developer, a color developer commonly used for carbonless paper is suitably used in the present invention. Specifically, for example, clay materials such as acid clay, activated clay, atavulgite, and zeolite; aromatic carboxylic acids such as benzoic acid, salicylic acid, 3,5-di- (α
-Methylbenzyl) salicylic acid and polyvalent metal salts thereof, such as zinc salts, aluminum salts, magnesium salts, etc., phenolic resins, such as phenol formaldehyde resins, phenol acetylene resins, and polyvalent metal salts of the phenolic resins, etc. Organic acidic substances can be mentioned. These developers may be used as a mixture of two or more.

The microcapsules and the developer used in the present invention can be used in a weight ratio of solid content of 2/8 to 8/2, preferably 4/6 to 6/4. Is the ratio of When applying the microcapsules and the developer on the transparent support, various auxiliary agents usually used for a pressure-sensitive recording material such as a binder can be appropriately added. Examples of the binder include starch, casein, gum arabic, carboxymethyl cellulose, polyvinyl alcohol, styrene-butadiene copolymer latex, and vinyl acetate-based latex.

In the present invention, the method of forming the self-coloring type photosensitive pressure-sensitive recording layer includes a blade coating method, an air knife coating method, a gravure coating method, a roll coating coating method, and the like.
Known coating methods such as a bar coating method and a falling curtain coating method can be used. Further, various known techniques in the field of producing a pressure-sensitive recording material, such as applying a back coat for preventing curling and conducting a conductive treatment for preventing jamming, can be added as necessary. Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to Examples.

【Example】

Example 1 I Synthesis of Photosensitive Microcapsules I-1 Synthesis of Magenta Microcapsules Photosensitive microcapsules were prepared with reference to the examples described in JP-A-2-298340.

A. Preparation of internal phase. Trimethylolpropane triacrylate (TMP
TA) 105 g and dipentaerythritol hydroxypentaacrylate (D
(PHPA) 45 g to a beaker and added at about 105 ° C. for 30
Heated for minutes. . While stirring, 20 g of the dye precursor (M-1) was added and dissolved. After heating and stirring at 105 ° C for 30 minutes,
It was cooled to ° C. . 0.5 g of a photoinitiator (1,1'-di-n-heptyl-3.3,3 ', 3',-tetramethylindocarbocyanine triphenyl-n-butyl borate) with stirring
Was added, and the mixture was further stirred at 70 ° C. for 30 minutes. . While stirring, 1.0 g of DIDMA (2,6-diisopropyl-N, N-dimethylaniline) was added, and the mixture was stirred for 5 minutes. . 2-mercaptobenzothiazole disulfide
5 g was added and the mixture was stirred for 20 minutes. . 10 g of duranate 24A-90PX (a polyisocyanate manufactured by Asahi Kasei) was added and the temperature was maintained at 70 ° C.

B. Preparation of external phase 430 g of water was added to the beaker, and the mixture was stirred with an overhead mixer at 500 rpm. . 8.0 g of VarsaTL-502 (sulfonated polystyrene manufactured by National Starch) was slowly added, and the mixture was further stirred at 500 rpm for 15 minutes. . 12.65 g of pectin and sodium bicarbonate 0.
24 g were mixed, added at a stirring speed adjusted to 1500 rpm, and further stirred at 1500 rpm for 2 hours. . The pH was adjusted to 6.0 with NaOH, and then 3
The mixture was stirred at 000 rpm for 10 minutes. C. Emulsification of the inner phase within the outer phase. In about 30 seconds, the internal phase was gradually added to the external phase. . Emulsion stirring was performed at 3000 rpm for 15 minutes to form an emulsion.

D. Formation of melamine formaldehyde outer wall. 250 g of water was added to the beaker, and 22.2 g of melamine was gradually added with stirring. . 36.5 g of 37% formaldehyde were slowly added. . Heat to 60 ° C in about 30 minutes and cure at 60 ° C for 60 minutes (formation of melamine-formaldehyde precondensate). . The stirring speed of the emulsification was adjusted to 1500 rpm, and the melamine-formaldehyde precondensate was injected into the emulsion of C. . The pH was adjusted to 6.0 using H ₃ PO ₄ . . Subsequently, the mixture was cured at 70 ° C. for 60 minutes to form internal phase-containing microcapsules. . 46.2 g of a 25% aqueous urea solution was added and cured for 60 minutes. . The stirring speed was set to 500 rpm and 20% NaOH 10
g was added and cooled to room temperature. . The mixture was further stirred at room temperature overnight to obtain a microcapsule dispersion liquid (A). The particle size of the obtained microcapsules was 2 to 12 µ, most of which was 6 to 7 µ.
Further, the solid content was measured by an electronic moisture meter manufactured by Shimadzu Corporation and found to be 25.2% by weight.

I-2 Synthesis of Cyan Microcapsules In the description of synthesis of I-1 magenta capsules, 30 g of C-3 was added in place of the dye precursor M-1, and a photoinitiator was further added with 1,1'-di- n-heptyl-3,3,3 ', 3'-
Tetramethylindodicarbocyanine-triphenyl-
Microcapsule dispersion liquid (B) was obtained by changing to 0.85 g of n-butyl borate. The obtained microcapsules (B) have a particle size of 2 to 12 μm and a solid concentration of 26.
3%.

I-3 Synthesis of Yellow Microcapsules In the description of the synthesis of I-1 magenta capsules, 0.80 g of Y-1 was added instead of the dye precursor M-1, and the photoinitiator was 3,3- Dimethyl-1-heptylindo-
The microcapsule dispersion liquid (C) was obtained by changing to 3 g of 3′-heptylthiocyanine-triphenyl-n-butyl borate. The particle size of the obtained microcapsules (C) was 5 to 10 μm, most was 6 to 8 μm, and the solid content concentration was 27.5%. II Preparation and Coating of Photosensitive Solution The microcapsule dispersion obtained by I and the developer HRJ-4250 (Schenettad) described in JP-A-1-168484 and JP-A-2-95884.
y Chemical Co. Was manufactured by mixing as shown below to prepare a photosensitive solution (I).

Microcapsule dispersion liquid (A) 5.6 g Microcapsule dispersion liquid (B) 4.9 g Microcapsule dispersion liquid (C) 4.7 g HRJ-4250 15.8 g H ₂ O 9.0 g

The prepared photosensitive solution (I) was applied on a transparent PET film using a # 20 Meyer bar. The coated amount after drying was 10.2 g / m ² . in addition,
50 parts of titanium dioxide, acrylic emulsion (trade name;
Priming P-376, manufactured by Rohm and Haas Japan K.K.
The sample was applied so as to have a concentration of 0 g / m ² and an opaque layer was provided to prepare Sample (I). A sample (II) was prepared in the same manner as the sample (I) except that a white opaque PET film into which titanium oxide was kneaded was used instead of the transparent PET film, and the opaque layer was not provided.

[0035] Full-color original image on PC
Capture, Printer (Product name: DPD-200, AS
Tech System Co., Ltd. (AZTECH SYSTEMS)
 LTD)), the samples (I) and (II) were imaged.
Exposure and pressure development. As a result, both are original
A good full-color image close to the image was obtained. Then
Place the sample (I) on a transparent paper sheet on a desk with paper
With a 1kg weight on it and move it 1m
Optical density using a Macbeth densitometer
And the difference in color density before the movement (blue: D_B, Green: D_G,Red
Color: D _R). Sample (II) also has a colored surface
The same test was conducted with the sample number set downward. Table 1 shows the results.

[0036]

[Table 1]

From the results shown in Table 1, it can be seen that the sample (I) of the present invention has no coloring at all and has high anti-scratching property. On the other hand, it can be seen that the comparative sample (II) has rubbing stains.

According to the self-coloring photosensitive pressure-sensitive recording material of the present invention, a full-color image can be formed by imagewise exposing from the transparent support surface and then developing under pressure. Further, it was possible to prevent abrasion caused by careless pressurization and friction during storage and handling.

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[Submission date] June 26, 1998

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──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/26 521 B41M 5/12 112

Claims (12)

[Claims] 1. A transparent pressure-sensitive recording layer having, in a single layer or a laminated state, a photosensitive microcapsule containing a dye precursor, a photoinitiator and a polymerizable compound and a developer on a transparent support, A self-coloring type photosensitive pressure-sensitive recording material having an opaque layer thereon. 2. The self-coloring photosensitive pressure-sensitive recording material according to claim 1, wherein the opaque layer comprises a pigment, a water-soluble polymer compound and / or a water-dispersible polymer compound. 3. The self-coloring photosensitive pressure-sensitive recording material according to claim 1, wherein the polymerizable compound is a radical addition polymer. 4. The self-initiator according to claim 1, wherein the photoinitiator is an initiator that absorbs actinic radiation to generate free radicals capable of initiating free radical polymerization of the polymerizable or crosslinkable compound. Color-forming photosensitive pressure-sensitive recording material. 5. The self-propelled dye according to claim 1, wherein the dye precursor is a substantially colorless electron donating compound having a lactone, lactam, sultone, spiropyran, ester or amide structure in a partial skeleton. Color-forming photosensitive pressure-sensitive recording material. 6. The self-coloring photosensitive material according to claim 1, wherein the color developer is an aromatic carboxylic acid or a polyvalent metal salt thereof, a phenol resin or a polyvalent metal salt thereof, or a mixture thereof. Pressure recording material. 7. A transparent pressure-sensitive recording layer having a single layer or a stacked layer of a photosensitive microcapsule containing a dye precursor, a photoinitiator and a polymerizable compound and a developer on a transparent support, An image forming method, comprising exposing a self-coloring photosensitive pressure-sensitive recording material having an opaque layer thereon imagewise from the side of a transparent support, followed by pressure development. 8. The image forming method according to claim 7, wherein the opaque layer comprises a pigment, a water-soluble polymer compound and / or a water-dispersible polymer compound. 9. The image forming method according to claim 7, wherein the polymerizable compound is a radical addition polymer. 10. The image according to claim 7, wherein the photoinitiator is an initiator that generates actinic radiation to generate free radicals capable of initiating free radical polymerization of a polymerizable or crosslinkable compound. Forming method. 11. A dye precursor comprising a lactone in a partial skeleton,
The image forming method according to claim 7, wherein the image forming method is a substantially colorless electron donating compound having a lactam, sultone, spiropyran, ester or amide structure. 12. The image forming method according to claim 7, wherein the color developer is an aromatic carboxylic acid or a polyvalent metal salt thereof, a phenol resin or a polyvalent metal salt thereof, or a mixture thereof.