JPS63206747A - Color image forming material - Google Patents

Abstract

PURPOSE:To facilitate the stripping of the supporting body of a color image forming material after the transfer of a formed color image to a surface for transfer by incorporating a specified cellulose deriv. into the releasing layer. CONSTITUTION:The titled material is a color sheet for a color proof and is obtd. by forming a color recording layer contg. a photosensitive compsn. and a colorant or a photosensitive compsn. layer and a colorant layer on a supporting body with a releasing layer in-between. The releasing layer contains one or more among butyl-, hydroxyethyl-, carboxymethyl- and cyanoethylcelluloses, cellulose (tri)acetate, cellulose acetate butyrate and hydroxypropylmethylcellulose (hexahydro)phthalate. A layer which is melt-bonded by heating may be formed between the releasing layer and the color recording layer. The support can be easily stripped without leaving a formed color image on the supporting body.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a colored image forming material, and more specifically, to a color sheet for color proofing (color proof) for transferring a colored image onto a transfer surface. The present invention relates to a colored image-forming material whose support can be easily peeled off after coloring.

[Conventional technology]

It is well known in the art that color sheets for color proofing (also called color proofs) are used to save time and effort in proof printing, which is performed as a pre-printing step in multicolor printing.

Examples of methods for creating a multicolor transfer image using a color sheet for color proofing include the so-called direct transfer method, which is described in Japanese Patent Laid-Open No. 47-41830, in which a colored image is directly transferred and laminated onto a final image-receiving paper; JP-A No. 59-97140 describes a method in which a colored image is temporarily transferred and laminated onto a temporary image-receiving sheet, and then transferred again onto a final image-receiving sheet.
So-called indirect transfer method % formula % [Problems to be solved by the invention] However, in any of the above conventional methods, the releasability between the support and the colored image is insufficient, and the peeling operation of the support must be carefully performed. If this is not done, a part of the colored image may not be transferred onto the transfer surface and may remain on the support side when the support is peeled off.

The main object of the present invention is to provide a colored image-forming material whose support can be easily peeled off after a colored image has been transferred onto a transfer surface.

[Means for solving problems]

The above object provides a colored recording layer containing a photosensitive composition and a colorant on a support via a release layer, or a colored image forming material having a photosensitive composition layer and a colorant layer;
The release layer contains one or more cellulose derivatives of butyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, cyanoethyl cellulose, cellulose acetate, cellulose triacetate, cellulose acetate butyrate, hydroxypropyl methyl cellulose phthalate, or hydroxypropyl methyl cellulose hexahydrophthalate. It is achieved by doing.

[Specific structure of the invention]

The present invention will be explained in more detail below.

The colored image forming material of the present invention has a colored recording layer containing a photosensitive composition and a colorant, or a photosensitive composition layer and a colorant layer on a support via a release layer, and has a color separation layer. After imagewise exposure through a mask, it is developed to form a colored image.

The obtained colored image is either directly transferred and laminated onto the final image-receiving paper (direct transfer method), or temporarily transferred and laminated onto a temporary image-receiving sheet, and then transferred again onto the final image-receiving paper (indirect transfer method). In order to efficiently perform the transfer onto the surface to be transferred (transfer method), it is preferable to provide a heat-fusible layer between the release layer and the colored recording layer. Furthermore, when the colored recording layer is divided into two layers, a photosensitive composition layer and a colorant layer, it does not matter which layer is present on the heat-fusible layer side.

As the transparent support for the colored image-forming material used in the present invention, polyester films, especially two-wheel stretched polyethylene terephthalate films are preferred from the viewpoint of dimensional stability against water and heat, but acetate films, polyvinyl chloride films, and polystyrene films are preferred. , polypropylene film, polyethylene film may also be used.

A release layer is provided on the surface of the support, and the release layer includes methyl cellulose 1. Butyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, cyanoethyl cellulose, cellulose acetate, cellulose triacetate, cellulose acetate butyrate, hydroxypropyl methyl cellulose phthalate, hydroxypropyl methyl cellulose hexahydrophthalate, or mixtures thereof, etc. can be used, but
Particularly suitable are hydroxypropyl methylcellulose phthalate and hydroxypropyl methylcellulose hexahydrophthalate.

The thickness of the release layer is suitably in the range of 0.01 μm to 10 μm, particularly preferably in the range of 0.1 μm to 5 μm.

The heat-fusible layer used in the present invention is transparent and non-adhesive at room temperature, but is preferably one that can be heat-fusible in the temperature range of 80°C to 160°C.

For this purpose, the following film-forming thermoplastic resins having a softening point of 70°C to 140°C are used. For example, olefin (co)polymer, vinyl chloride (co)polymer, vinylidene chloride (co)polymer, vinyl acetate (co)polymer, (meth)acrylic acid ester (co)polymer, styrene/(meth)polymer Acrylic ester copolymers, polyesters, vinyl butyral resins, chlorinated rubber, cellulose derivatives, preferably styrene/(meth)acrylic ester copolymers, polyesters, etc., which may be used alone or in combination; may be used in combination with other resins or plasticizers.

The thickness of the heat-fusible layer is suitably in the range of 1 to 20 μm, particularly preferably in the range of 2 to 8 μm. The thickness of the heat-fusible layer formed on the heat-fusible layer should be equal to or greater than the combined thickness of the colored recording layer or colorant layer and photosensitive composition layer described below. When a colored image is heated, pressurized, and transferred onto the surface of an image-receiving material, even minute non-image areas, that is, even the heat-fusible layer in a narrow area surrounded by large image areas, are effectively transferred to the surface of the image-receiving material. It is possible to fuse and obtain a uniform and good transferred image.

The colored recording layer or the coloring agent layer and the photosensitive composition layer are removed in an imagewise manner by development following imagewise exposure to form a colored image.

As the binder constituting these layers, a polymer compound that is film-forming, solvent-soluble, and soluble or swellable in a developer is used.

Specific examples of this polymer compound include acrylic acid, methacrylic acid and their alkyl esters or sulfoalkyl esters, phenol resins, polyvinyl butyral, polyacrylamide, ethyl cellulose,
Cellulose derivatives such as cellulose acetate/butyrate, cellulose acetate/propionate, cellulose acetate, benzyl cellulose, cellulose propionate, other polystyrene, polyvinyl chloride, chlorinated rubber, polyisobutylene,
Polybutadiene, polyvinyl acetate, and their copolymers, cellulose acetate, cellulose propionate,
Examples include cellulose acetate phthalate.

Dyes and pigments are added to the colored recording layer as coloring substances. In particular, when used for color proofing, pigments and dyes with tones matching the usual colors required for that purpose, such as yellow, magenta, cyan, and black, are required, as well as other metal powders,
White pigments and fluorescent pigments are also used. The following examples are some of the many pigments and dyes known in the art. (C.

■ means color index).

Victoria Pure Blue (C, I 42595) Auramine (C, I 41000) Catilon Brilliant Flavin (C,!Basic 13)
) Rhodamine 6 [, CP (C, I 45160) Rhodamine B (C, I 45170) Safranin 0K70:100 (C, I 50240) Erioglaucine X (C, I 42080) Fast Black HB (C, I 26150) 1201 Lionor Yellow (C, r 21090) Lionor Yellow GRO (C, I 21090) Shimla Fast Yellow 8GP (C, I 21105) Benzidine Yellow 4T-5640 (C, I 21095) Shimla Fast Red 4015 (C, I 12355 ) Lionol Red 7B4401 (C, I 15830) First Gen Blue TGR-L (C, I 74160) Lionol Blue SM (C, I 26150) Mitsubishi Carbon Black MA-100 Mitsubishi Carbon Black 130.140. #50 The colorant/binder ratio of the colored recording layer used in the present invention can be determined by a method known to those skilled in the art, taking into consideration the target optical density and the removability of the colored recording layer to a developer.

For example, in the case of dye, its content is 5% to 75% by weight.
In the case of pigment, the content is suitably 5% to 90% by weight.

Further, the thickness of the colored recording layer can be determined by a method known to those skilled in the art based on the target optical density, the type of colorant M (dye, pigment, carbon black) used in the colored recording layer, and its content. However, within the allowable range, the thinner the colored recording layer is, the higher the resolution will be.
Image quality is good. Therefore, the film thickness is l g /
Usually, it is used in the range of 2 to 5 g/m''.

The colorant used in this colored recording layer is also used as a colorant layer.

Various photosensitive compositions can be used as the photosensitive composition contained in the colored recording layer or the photosensitive composition layer, but it is preferable to use a photosensitive composition that can be developed with an alkali. Examples of photosensitive compositions include compositions obtained by blending an azide photosensitizer such as 2,6-di(4'-azidobenzal)cyclohexane with a phenol novolac resin, and benzyl methacrylate and methacrylic acid (for example, a molar ratio of There is a photopolymerizable photosensitive composition in which a polyfunctional monomer such as trimethylolpropane triacrylate and a photopolymerization initiator such as Michler's ketone are blended using a copolymer of 7:3) as a binder. In addition, as a positive working type, for example, there is a photosensitive resin composition using 0-quinonediazide as a photosensitizing agent, and furthermore, it contains i) a compound that can generate an acid when irradiated with actinic rays, and ii) a bond that can be decomposed by an acid. It is also possible to use photosensitive resin compositions containing a novolak resin containing at least one compound and 1ii) two or three different phenols.

When the colored image forming material of the present invention is used in a direct transfer method, after development following imagewise exposure, the obtained colored image is directly transferred and laminated onto a transfer surface such as art paper or coated paper. When using the indirect transfer method, the obtained colored image is temporarily transferred and laminated onto a temporary image-receiving sheet, and then transferred again.
The image-receiving sheet used in the zero-indirect transfer method for transferring onto a transfer surface such as art paper or coated paper is one in which an image-receiving layer containing a thermoplastic organic polymer is provided on a support, or one in which an image-receiving layer containing a thermoplastic organic polymer is provided on a support. An image-receiving layer having an image-receiving layer can be used.

Various materials can be used as the support for forming the image-receiving sheet, but for example, a polyester film, particularly a two-wheel stretched polyethylene terephthalate film, is preferable in terms of dimensional stability against water and heat; Acetate films, polyvinyl chloride films, polystyrene films, polypropylene films may also be used.

The thermoplastic organic polymer used in the image-receiving layer of the image-receiving sheet is preferably a resin that is hard at low temperatures and becomes sticky when heated. For this purpose, a resin that softens at a temperature of 10° C. to 150° C. higher than room temperature is preferred.

Examples of such materials include polyolefins such as polyethylene and polypropylene, copolymers of these polyolefins and α,β-unsaturated carboxylic acids, and ionomer resins that are metal ion bound products of these copolymers. There is. Others include polyvinylidene chloride and its copolymers, polyacrylonitrile, poly-N-vinylcarbazole, polyvinyl acecool, poly-N-vinylpyrrolidone, polyvinyl chloride, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, Examples include polybutyl acrylate, polymethacrylic acid, polymethyl methacrylate, polyvinyl ether, polyvinyl acecool, polyamide, polyester, and copolymers thereof.

Furthermore, the image-receiving layer may contain other non-photosensitive additives such as plasticizers and surfactants, if necessary. The minimum thickness of the image-receiving layer is sufficient to embed and transfer the four-color image after image formation, and the appropriate coating amount varies depending on the thickness of the color image. is 4 g
/m" to 40 g/m" is suitable.

In addition, photosensitive compositions used in the photosensitive image-receiving layer include monomers, prepolymers, and polymers that undergo chemical changes in their molecular structure in a short period of time when irradiated with actinic rays. , but the molecular weight of at least one of the photowindowable components is sufficient to cause a change in the rheological and thermal behavior of the exposed portion, such as by irradiation with actinic radiation. Preferably, an increasing system is used.

Examples of photosensitive compositions that can be used include photocrosslinkable photosensitive resin systems, such as polyvinyl alcohol esterified with cinnamic acid, diazonium salts and their condensates, such as polyvinyl alcohol, polyvinylpyrrolidone, and There are systems in which acrylamide is condensed, systems in which an aromatic azide compound is used as a photocrosslinking agent and mixed with a binder such as cyclized rubber, and photosensitive resins that utilize photoradical polymerization or photoionic polymerization can also be used. can.

In particular, a) at least one polyfunctional vinyl or vinylidene compound capable of forming a photopolymer by addition polymerization, b)
A system consisting of an organic polymer binder, C) a photopolymerization initiator activated by actinic rays, and optionally containing a thermal polymerization inhibitor is preferred.

Polyfunctional vinyl or vinylidene compounds a) include, for example, unsaturated esters of polyols, in particular esters of acrylic acid or methacrylic acid, such as ethylene glycol diacrylate, glycerol triacrylate, ethylene glycol dimethacrylate, 1,3-propanediol. Dimethacrylate, polyethylene glycol dimethacrylate, 1,'2,4-butane trio-root trimethacrylate, trimethylolethane triacrylate,
pentaerythritol, tri- and tetramethacrylate, pentaerythritol-tri, tri- and tetraacrylate, dipentaerythritol-polyacrylate,
1,3-propanediol-diacrylate, 1,5-
Pentanedi-rouge methacrylate, 200-400
Bis-acrylates and bis-methacrylates of polyethylene glycol with a molecular weight of 0 and similar compounds,
There are unsaturated amides, especially those of acrylic acid and methacrylic acid and ethylene bis-methacrylamide, which present α,ω-diamines whose alkylene chains may be opened by carbon atoms.

As the organic polymer bond b), vinyl polymer substances are particularly suitable from the viewpoint of compatibility with the monomer compound and the photopolymerization initiator described below. Vinyl polymer substances include polyvinyl chloride, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate,
Various examples include, but are not limited to, polymethacrylic acid, polymethyl methacrylate, polyvinyl ether, polyvinyl acecool, and copolymers thereof. Here, the appropriate mixing ratio of the monomer compound and the organic polymer conjugate varies depending on the combination of the seven-mer mixture and the organic polymer conjugate used, but in general,
Monomer to binder ratio of 0.1:1.0 to 2.0:
1.0 (ii quantity ratio) is preferable.

As the photopolymerization initiator C), those with low absorption in the visible region are more preferable, such as benzophenone, Michler's ketone (4,4'-bis(dimethylamine)benzophenone), 4,4'-bis(diethylamino)benzophenone, Aromatic ketones such as 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthraquinone, and other aromatic ketones, benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoinphenyl. Benzoin ethers such as ethers, methylbenzoin, ethylbenzoin and other benzoins, and 2-(o
-chlorophenyl') -4,5-diphenylimidazole dimer, 2-(o-chlorophenyl) -4,5-
(m-methoxyphenyl)imidazole dimer, 2-
(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(0-methoxyphenyl)-4,5
-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer,
2゜4-di(p-methoxyphenyl)-5-phinylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimitasol dimer, 2-(p-methoxyphenyl)-5-phinylimidazole dimer,
-methylmercaptophenyl') -4,5-diphenylimidazole dimer and U.S. Pat. No. 3,479.18
2,4.5-1-lyacrylimidazole dimers such as similar dimers described in No. 5, British Patent No. 1,047,569 and U.S. Pat. No. 3,784,557. Examples include, but are not limited to, the body.

The amount of photoinitiator added is 0.01 based on the monomer compound.
~20% by weight is preferred.

The thermal polymerization inhibitor added as necessary is, for example, p-
Methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, tert-butylcatechol,
Examples include, but are not limited to, pyrogallol, naphthylamine, β-naphthol, phenothiazine, pyridine, nitrobenzene, p-toluquinone, and arylphosphite.

゛ Furthermore, the image-receiving layer may contain other additives such as plasticizers and surfactants, if necessary.

The image-receiving layer should have a minimum thickness sufficient to embed and transfer the four-color image after image formation;
The appropriate coating amount varies depending on the film thickness of the color image, but is 4 g/m.
"~40g/m" is suitable.

When the colored image-forming material of the present invention is used in an indirect transfer method, an image-receiving sheet containing the above-mentioned thermoplastic organic polymer and having a non-photosensitive image-receiving layer or a photo-sensitive image-receiving layer, respectively. A support provided on a support can be used, but when a photosensitive image-receiving layer is used, a colored image is transferred and laminated onto the surface of the image-receiving layer, and then this is coated on art paper or coated paper. After being transferred onto a final image-receiving paper such as paper, the photosensitive image-receiving layer is cured by post-exposure to create releasability between the support of the image-receiving sheet and the image-receiving layer. In contrast, when using an image-receiving layer containing a thermoplastic organic polymer and not having photosensitivity, the support can be peeled off without the need for post-exposure. Therefore, from the viewpoint of ease of operation, when the colored image forming material of the present invention is used in an indirect transfer method, an image receiving sheet containing a thermoplastic organic polymer on a support and having no photosensitivity is recommended. It is preferable to use one provided with an image-receiving layer.

〔Example〕

<Example 1> A release layer solution having the following composition was applied onto a two-wheeled stretched polyethylene terephthalate film with a thickness of 75 μm using a wire bar so as to have a dry film thickness of 0.5 μm, and dried.

Next, a heat-fusible layer top liquid having the following composition was applied onto the release layer to a dry film thickness of 7 μm and dried.

Further, colored recording layer dispersions of four colors having the following compositions were prepared, and coated and dried on the heat-fusible layer so that each had a dry film thickness of 1.5 μm.

*Pigment A color separation mesh positive film of each color was superimposed on the polyethylene terephthalate film surface of the four-color colored image forming material obtained above, and image exposure was performed for 30 seconds from a distance of 50 am using a 2 kW ultra-high pressure mercury lamp, and sodium hydroxide was applied. 2
% aqueous solution for 30 seconds to obtain a four-color colored image.

Next, the image surface of the obtained yellow color image is brought into close contact with art paper, passed between a pair of F-brolls heated at 100°C, the color image is transferred onto the art paper, and the polyethylene terephthalate film on the image side is transferred. The 0-color image that was peeled off was completely transferred onto the art paper, and the polyethylene terephthalate film was easily peeled off.

Subsequently, color images were similarly transferred in the order of magenta, cyan, and black to obtain a multicolor proofing sheet on art paper. The obtained color proof was very close to the printed matter. Comparative Example 1 The same procedure as in Example 1 was carried out except that the release layer solution was changed to one with the following composition, and a four-color colored image was obtained. A forming material was created.

Next, imagewise exposure and development were performed in the same manner as in Example 1 to obtain a four-color colored image, and then the yellow image was transferred onto art paper and the polyethylene terephthalate film on the image side was peeled off. This was not easily carried out, and furthermore, a portion of the yellow image was not transferred onto the art paper and remained on the polyethylene terephthalate film side, making it impossible to obtain a complete transfer of the yellow image onto the art paper.

Subsequently, transfer was performed in the order of magenta, cyan, and black, but similarly, it was not possible to obtain a complete transferred image of each color on the art paper.

<Example 2> A release layer solution having the following composition was applied onto a biaxially stretched polyethylene terephthalate film with a thickness of 75 μm using a wire bar so as to have a dry film thickness of 0.5 μm, and dried.

Next, a heat-fusible layer solution having the following composition was applied onto the release layer to a dry film thickness of 7 μm and dried.

(Methyl ethyl ketone 100 g Next, four colors of coloring material layer dispersions having the following compositions were prepared, and each was applied to a dry film thickness of 2 μm.

The following pigment: 5 g Methyl cellosolve: 80 g (pigment) Further, a photosensitive composition layer solution having the following composition was coated to a dry film thickness of 2 μm.

Styrene-maleic anhydride copolymer 4g dimethylchexanthone 1g isoamyl dimethylaminobenzoate 1g methyl cellosolve acetate 90g A color separation negative mask of each color was superimposed on the photosensitive composition layer surface of the obtained four-color image forming material, and 3 After imagewise exposure for 10 seconds using a metal halide lamp from a distance of 50 am, the film was developed by immersing it in a 10-fold dilution of 5DP-1 (Sakura PS plate developer) for 30 seconds to obtain a four-color image.

Next, the image surface of the obtained yellow color image is brought into close contact with art paper, passed between a pair of nip rolls heated to 100°C, the color image is transferred onto the art paper, and the polyethylene terephthalate film on the image side is was peeled off. The color image was perfectly transferred onto the art paper and the polyethylene terephthalate film was easily peeled off.

Subsequently, color images were similarly transferred in the order of magenta, cyan, and black to obtain a multicolor proofing sheet on art paper. The color proof obtained was very good and very similar to the printed material.

<Example 3> A release layer solution having the following composition was applied onto a biaxially stretched polyethylene terephthalate film with a thickness of 75 μm using a wire bar so as to have a dry film thickness of 0.5 μm, and dried.

Next, a heat-fusible layer solution having the following composition was applied onto the release layer to a dry film thickness of 7 μm and dried.

Further, colored recording layer dispersions of four colors having the following compositions were prepared, and coated and dried on the heat-fusible layer so that each had a dry film thickness of 1.5 μm.

*Pigment A color separation mesh positive film of each color was superimposed on the colored recording layer surface of the four-color colored image forming material obtained above, and imagewise exposure was performed for 60 seconds from a distance of 50 cm+ using an ultra-high pressure mercury lamp. It was developed with a 2% aqueous sodium oxide solution for 30 seconds to obtain a four-color colored image.

Then on another polyethylene terephthalate film,
An image-receiving sheet was prepared by applying the following image-receiving layer coating solution to a dry film thickness of 20 μm.

water 1
0gThe yellow image surface obtained earlier is brought into close contact with the image receiving sheet,
The color image was transferred to an image receiving sheet by passing between a pair of nip rolls heated at 100° C., and the polyethylene terephthalate film on the color image side was peeled off. Subsequently, color images were transferred in the order of magenta, cyan, and black to form a color sheet consisting of four colors on the image-receiving sheet.

Next, the image side of the image receiving sheet is brought into close contact with white paper, and
The multicolor image was transferred to white paper by passing it between a pair of nip rolls heated to 0° C., and the polyethylene terephthalate film of the image receiving sheet was peeled off. In this way, a multicolor proofing sheet on white paper was obtained. The color proof obtained was very good and very similar to the printed material.

〔Effect of the invention〕

As described above, according to the present invention, the colored image portion of the colored image forming material can be easily peeled off from the support, and the colored image portion can be successfully transferred onto the transfer surface.

Claims (1)

[Claims] (1) In a colored image forming material having a colored recording layer containing a photosensitive composition and a colorant, or a photosensitive composition layer and a colorant layer on a support via a release layer; A colored image-forming material characterized by containing one or more of the following cellulose derivatives. Cellulose derivatives; butylcellulose, hydroxyethylcellulose, carboxymethylcellulose, cyanoethylcellulose, cellulose acetate, cellulose triacetate, cellulose acetate butyrate, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose hexahydrophthalate.