JPH11119423A - 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 substrate and a protective 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 substrate and at least one protective layer on the recording layer. The protective layer is formed from an aq. coating compsn. preferably based on a water-soluble resin and/or a water-dispersible resin. The water-soluble resin is, e.g. a water-soluble synthetic resin such as perfectly saponified PVA or a water-soluble natural resin such as gelatin. The water-dispersible resin is, e.g. a styrene-butadiene copolymer emulsion. The coating weight of the protective 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 support, a photosensitive pressure-sensitive recording layer having a single layer or a laminated layer of a photosensitive microcapsule containing a dye precursor, a photoinitiator and a polymerizable compound and a developer, and at least one layer thereon. This was achieved by a self-coloring type photosensitive pressure-sensitive recording material having a protective layer, and an image forming method in which the self-coloring type photosensitive pressure-sensitive recording material was imagewise exposed from the protective layer side and then developed under pressure.

[0005] The protective layer of the present invention comprises an aqueous coating composition, and the aqueous composition preferably contains a water-soluble resin and / or a water-dispersible resin as a main component. As a water-soluble resin,
Completely saponified polyvinyl alcohol, acetoacetylated polyvinyl alcohol, a reaction product of polyvinyl alcohol with a polycarboxylic acid such as fumaric acid, phthalic anhydride, or an esterified product of these reaction products, further, carboxy-modified polyvinyl alcohol, sulfonic acid Modified polyvinyl alcohol, olefin-modified polyvinyl alcohol,
Nitrile-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, polyvinyl alcohols such as pyrrolidone-modified polyvinyl alcohol, polyvinyl pyrrolidone,
Polyacrylic acid, polyacrylamide, isobutylene-
Water-soluble synthetic resin composed of maleic anhydride copolymer, polyvinylbenzene sulfonic acid and salts thereof, cellulose derivatives such as methylcellulose and carboxymethylcellulose, starches such as gelatin, casein, gum arabic, oxidized starch and dialdehyde starch And the like.

The water-dispersible resins include styrene-butadiene copolymer emulsion, vinyl acetate-vinyl chloride-
Examples include an ethylene copolymer emulsion, a methacrylate-butadiene copolymer emulsion, and a vinylidene chloride-acrylonitrile copolymer emulsion. Further, to the aqueous coating composition, pigments such as inorganic pigments such as silicon dioxide, kaolin, aluminum hydroxide and colloidal silica, and organic pigments such as styrene microballs, nylon powder, and polyethylene powder can be added as necessary. . The structure of the protective layer may be a single layer or a multilayer as required. The coating amount of the protective layer is not particularly limited, but is usually in a range of ^{2 to 20} g / m ² , preferably 3 to 15 g / m ² by dry weight.

Examples of the support used in the present invention include general papers such as glassine paper, woodfree paper, and art paper; plastic sheets such as polyethylene, polypropylene, polyethylene terephthalate and polyamide; and synthetic papers made of these synthetic fibers. Non-woven fabric, laminated paper with synthetic resin laminated on one or both sides of paper, metal foil, metal foil and paper, vapor-deposited paper, opaque sheet with hologram treatment, product laminated with synthetic film, mica paper, crow paper, etc. Can be used. These plastic sheets and synthetic resins can be made opaque with inorganic or organic pigments. The self-coloring type photosensitive pressure-sensitive recording material of the present invention may have a constitution of a photosensitive microcapsule layer, a color developer layer and a protective layer on a support, or a mixture of a support, a photosensitive microcapsule and a color developer. It may have a configuration of a layer and a protective 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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[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.

Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to the 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) and 105 g of dipentaerythritol hydroxypentaacrylate (DPHPA) were added to a beaker and heated at about 105 ° C. for 30 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 (A) 5.6 g Microcapsule Dispersion (B) 4.9 g Microcapsule Dispersion (C) 4.7 g HRJ-4250 15.8 g H ₂ O 9.0 g Prepared photosensitive solution ( I) was applied to one surface of synthetic paper (trade name: YUPO, manufactured by Oji Yuka Synthetic Paper Co., Ltd.) using a # 26 Meyer bar. The coated amount after drying was 10.2 g / m ² . An 8% aqueous solution of polyvinyl alcohol (trade name: Poval PVA-117, manufactured by Kuraray Co., Ltd.) was applied thereon so that the coating amount after drying was 10 g / m ² , a protective layer was provided, and the sample (I ) Was prepared. A sample (II) was prepared in the same manner as the sample (I) except that the protective layer was not provided.

A full-color original image is taken into a personal computer, and a printer (trade name: DPD-200, Aztec Systems Co., Ltd.) is used.
LTD)), and image-wise exposed and pressure-developed the samples (I) and (II). As a result, good full-color images, both close to the original images, were obtained.

Next, the sample (I) was placed on a paper-slipped desk with the protective layer side down, and a 1 kg weight was placed on it and moved for 1 m. Then, the optical density was measured using a Macbeth densitometer. Was measured, and the difference in color density between before and after the movement (blue: D _B , green: D _G , red: D _R ) was determined. The same test was performed on the sample (II) with the coloring surface down. 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 protective layer 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 (14)

[Claims] 1. A support comprising 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. A self-coloring photosensitive pressure-sensitive recording material having at least one protective layer thereon. 2. The self-coloring photosensitive pressure-sensitive recording material according to claim 1, wherein the protective layer comprises an aqueous coating composition. 3. The self-coloring photosensitive pressure-sensitive recording material according to claim 2, wherein the aqueous coating composition is a water-soluble resin and / or a water-dispersible resin. 4. The self-coloring photosensitive pressure-sensitive recording material according to claim 1, wherein the polymerizable compound is a radical addition polymer. 5. 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. 6. 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. 7. 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. 8. A support comprising 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. An image forming method, comprising: exposing a self-coloring photosensitive pressure-sensitive recording material having at least one protective layer thereon to an image from the protective layer side and developing by pressure. 9. The image forming method according to claim 8, wherein the protective layer comprises an aqueous coating composition. 10. The image forming method according to claim 9, wherein the aqueous coating composition is a water-soluble resin and / or a water-dispersible resin. 11. The image forming method according to claim 8, wherein the polymerizable compound is a radical addition polymer. 12. The image according to claim 8, wherein the photoinitiator is an initiator that absorbs actinic radiation to generate a free radical capable of initiating free radical polymerization of a polymerizable or crosslinkable compound. Forming method. 13. A dye precursor comprising a lactone in a partial skeleton,
9. The image forming method according to claim 8, wherein the image forming method is a substantially colorless electron donating compound having a lactam, sultone, spiropyran, ester or amide structure. 14. The image forming method according to claim 8, wherein the 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.