JPS63127243A - Transfer image forming method - Google Patents

Abstract

PURPOSE:To enable transcribing the image, without necessity of post exposure at a low temperature by forming a colored image on an image forming material which is applied a color recording layer having a photosensitive property on a substrate body having a surface capable of peeling, followed by transferring the obtd. colored image on an image receiving layer contg. a thermoplastic resin having a <=150 deg.C softening point. CONSTITUTION:The colored image is formed by using the image forming material which is formed by applying and providing the colored recording layer having the photosensitive property on the substrate having the surface capable of peeling, and by image-wisely exposing the obtd. image forming material, followed by processing it. The obtd. colored image is transferred on the image receiving sheet having the image receiving layer contg. the thermoplastic resin having <=150 deg.C the softening point. Said thermoplastic resin is one kind of the resin selected from the group comprising polyamide, polyester, polyurethane, ethylene-vinylacetate copolymer, styrene-butadiene copolymer, acrylonitrile- butadiene copolymer, styrene-isoprene copolymer, buty rubber and polyacrylic resin. Thus, the colored image can be transferred at the low temp. of <=150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a transfer image forming method, and more particularly to a colored image forming method useful as a color sheet for color proofing.

[Conventional technology]

When printing in color, the half-tone method is used whether it is lithograph, letterpress or gravure.
Color-separated halftone positive or negative plates are required. It is well known in the art that color sheets for color proofing (also referred to as color proofs) are used to save the labor and time of proof printing prior to actual printing.

JP-A No. 59-97140 discloses that after imagewise exposure to an image-receiving layer containing a photopolymerizable composition through a color separation mask,
A method is disclosed in which the developed image is transferred and then cured by providing sufficient post-exposure.

[Problem that the invention seeks to solve]

According to the above method, it can be used for both the overlay method and the sublin method for color calibration using photopolymers, but it requires post-exposure in addition to imagewise exposure, and if this is not done, the film strength will be weak. However, it has the disadvantage that it is not easy to peel off the support after transfer.

An object of the present invention is to provide a transfer image forming method that allows transfer at a relatively low temperature, does not require post-exposure, and has excellent film strength.

[Means for solving problems]

To summarize the present invention, the present invention relates to a method for forming a transfer image. After exposure, development is carried out to form a colored image, which is made of polyamide, polyester, polyurethane, ethylene-vinyl acetate μ copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, etc. with a softening point of 150°C or less. Polymer, styrene-isoprene copolymer, butyμ
It is characterized in that it is transferred onto an image-receiving layer containing one type of thermoplastic resin selected from the group consisting of rubber and polyacrylic resin.

As the image-receiving layer support according to the present invention, any transparent film base can be used. Specifically, cellulose diacetate,
=Plastic films such as cellulose butyrate, heptalose propionate, cellulose butyrate, cellulose acetate/butyrate, heptalose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, and polyvinyl acetal are preferred.

These supports can be subjected to chemical treatment, electrical discharge treatment, flame treatment, ultraviolet treatment, high frequency glow discharge treatment, activated Buchsma treatment,
It is preferable that the surface be treated by one or a combination of two or more such as silicone mold release treatment.

The resin used in the image-receiving layer of the present invention is preferably a resin that is hard at low temperatures and becomes sticky when heated.

If a thermoplastic resin with a softening point exceeding 150° C. is used in the image-receiving sheet, image transfer from the image-forming material to the image-receiving sheet and from the image-receiving sheet to white paper will not be sufficiently performed.

In order to perform 100-inch transfer and obtain a good image, it is necessary to raise the transfer temperature to a higher temperature than 150°C.

In that case, the support of the image forming material, the support of the image receiving sheet, and the white paper are likely to be distorted due to heat. For this purpose, a resin that softens at a temperature of 10° C. to 100° C. higher than room temperature is preferred.

Among these thermoplastic resins, polyamides such as nylon 12, polyester μ, and ethylene-vinyl acetate copolymers are preferred from the viewpoint of strength at low temperatures and tackiness at high temperatures.

Furthermore, when using the above thermoplastic resin in the form of a film,
Particularly preferred from the viewpoint of film strength.

The releasable surface in the present invention may be the surface of the support itself, or may be coated with some kind of coating thereon.

As the support for the photosensitive image-forming material used in the present invention, polyester μ film, particularly biaxially oriented polyethylene terephthalate film, is preferred in terms of dimensional stability against water and heat, but acetate film, polyvinyl chloride film, Polystyrene film, polypropylene film may also be used. Furthermore, although these supports may be used as they are, they may be coated with a release treatment using a suitable oil-repellent material, or may be coated with an undercoat in order to improve the transferability of the image after image formation.

The oil-based substances include, for example, silicone resins, fluororesins, and fluorosurfactants, and the undercoat layers include, for example, Aco-soluble polyamide, Aco-soluble nylon, styrene and maleic anhydride. Blends of partially esterified copolymers of methoxymethacrylate and methoxy methacrylic nylon, polyvinyl acetate, polyacrylate, copolymers of polymethacrylate and acrylate, polyvinyl chloride, vinyl chloride and acetic acid Copolymers, polyvinyl butyral, cellulose acetate phthalate, methylcellulose, ethylcellulose, cellulose diacetate, cellulose triacetate, and polyvinyl μalcohol, which have weak adhesion to the transparent support, can be mentioned.

The colored recording layer of the present invention is removed imagewise by development following imagewise exposure to form a colored image.

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

Specific examples of the polymer compounds suitably used for the colored recording include acrylic acid, methacrylic acid, their alkyl esters, sulpho7/l/kyl esters, and phenol.
fi/resin, polyvinylbutylene, polyacrylamide, ethylose, cellulose acetate/butyrate, acetic acid e
Cellulose derivatives of propionate cellulose, cellulose acetate, bendi-μ cellulose, propionate cellulose nato, other polystyrene, polyvinyl chloride, chlorinated rubber, polyisobutylene, polybutadiene, polyvinyl acetate, and their copolymers, cellulose Examples include acetate fugrate.

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 that match the usual colors required, i.e., yellow, magenta, cyan, and black, are required, but in addition, metal powders, white pigments, fluorescent pigments, etc. are also required. used. The following examples are some of the many pigments and dyes known in the art. (C, I means color index) Victoria Viewap μ-(C, I 42595) Auramine O
(C,I 41000) Cathylone Prilliantofurapine (C,I Bentzk 13) Rhodamine 6C) CP (C, I 45160) Rhodamine B (C, I 45170) Safranin 0K70:1
GG(C,l5024Q)Erioglaucine X(C,I
42080) Fastfutsk HB (C, I26150
) 41201 Lionor Yellow (C, Two Fast Red 4015 (C, Engineering 1 2 3 5 5) Rio No! Red 7B4401 (C, 1158S O) Fast Gemp μm TGR-L (c, I 74160) Lionorp μm SM (C, I26150) Mitsubishi car pump hook MA-1Ω〇Mitsubishi carbon black ÷ 301φ40. 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 account the target optical density and the removability of the colored recording layer to a developer. can. For example, in the case of dye, its content ranges from 5% to 75% by weight,
In the case of pigments, the content is suitably 51s to 9 (1%) by weight.

Furthermore, a white powder such as a white pigment, white metal powder, or white polymer compound having an average particle size (diameter) of 1 to 20 μm is added to the colored recording layer in a weight ratio of 1 to 201% based on the colorant in the layer. By doing this, it is possible to generate pseudo white voids in the solid areas and halftone dots on the colored image, and the image quality of door to page printing can be made to be more similar to the image quality of planographic printing. Become.

Further, the film thickness of the colored recording layer of the present invention has a target optical density,
Depending on the type of colorant (dye, pigment, carbon black) used in the colored recording layer and its content 1) it can be determined by a method known to those skilled in the art; The thinner the film thickness, the higher the developing power and the better the image quality.

Furthermore, a photosensitive component can also be added to this colored recording layer within a range that does not impair film-forming properties. As the photosensitive component that can be added, there is used one that can cause a difference in solubility or swelling property in a developer between exposed areas and unexposed areas when irradiated with actinic rays. The so-called negative-positive type, in which the solubility or swelling property in the developing solution decreases in the area exposed to actinic rays, includes photo-crosslinkable photosensitive resins typified by polyvinyl alcohol esterified with cinnamic acid; Examples include diazonium salts, condensates thereof, and aromatic amide compounds, and photosensitive resins using photoradical polymerization and photoionic polymerization can also be used. On the other hand, naphthoquinonediazide compounds and the like are examples of so-called positive-positive type materials in which the portion exposed to actinic rays has high solubility or swelling property in a developing solution.

The image forming material according to the present invention is preferably constructed by providing a photosensitive layer made of a photosensitive composition on a colored recording layer. Note that this photosensitive layer is essential when the above-mentioned photosensitive component is not added to the colored recording layer.

As photosensitive compositions for forming such a photosensitive layer, various materials have been known and commercially available products are also readily available. When the photosensitive composition used is irradiated with actinic rays, its molecular structure undergoes a chemical change in a short period of time, and its solubility changes in a solvent. In some cases, all compounds such as polymers, prepolymers, and polymers that are dissolved away in exposed or unexposed areas are included. Examples of photosensitive compositions that can be used include photocrosslinking, which is a so-called negative-positive type composition in which the solubility of exposed areas decreases, such as polyvinyl μ-co-co-esterified with cinnamic acid. type photosensitive resin systems, systems in which diazonium salts and their condensates are mixed with polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, etc., and systems in which aromatic azide compounds are used as photocrosslinking agents and mixed with binders such as cyclized rubber. In addition, photosensitive resins using photoradical polymerization or photoionic polymerization can also be used. Further, as a so-called positive-positive type resin that increases solubility in exposed areas, there is a photo-soluble resin system typified by a combination of naphthoquinone diazide and novolak resin.

Commercial products of such photosensitive compositions include "KPR", "KOR", and "KOR" manufactured by East Lamp Duck Co., Ltd. in the United States.
KMER”, “AZ-340” manufactured by γGray in the United States,
"AZ-119", AZ-1350", Tokyo Ohkasha m!
ITPR”% Tsuba Okare Resist 1, manufactured by Fuji Pharmaceutical Co., Ltd. 7F
PPR'' etc., all of these can be used.

In order to produce the image forming material according to the present invention, the above-mentioned colored recording layer components may be dissolved in a suitable solvent and applied sequentially or simultaneously onto the support having the above-mentioned releasable surface.

As a solvent, water, methanol, ethanol, acetone, ethyl acetate 1 methyl cellulose, ethyl cello,
dioxane, methyl ethyl ketone, cyclohexanone,
Diethylene rv:! Examples include -rumonomethiμ ether, r-petithualocton, tetrahydrofuran, methylene chlorophyte, ethylene chlorophyte, methylμ sulfoxide, dimethyμ foam amide, etc., which may be used alone or in combination.
Can be used in combination with more than one species.

The image forming material according to the present invention produced in this manner is first imagewise exposed to actinic light.

Various light sources are used for imagewise exposure, such as an ultra-high pressure mercury lamp, a tungsten lamp, a mercury lamp, a xenon lamp, a fluorescent lamp, a CRT light source, and a laser light source.

The image-forming material imagewise exposed in this way is treated with a solvent that does not dissolve the colored recording layer and the image area of the photosensitive layer but dissolves the non-image area, thereby removing the non-image area of the photosensitive layer. , by forming a resist image, and using as a developer a solvent that dissolves or swells the colored recording layer and does not dissolve the resist image on the photosensitive layer, the photosensitive layer is removed and the colored recording layer is removed. Either the exposed portion is dissolved or rubbed away, or the image area of the photosensitive layer is not dissolved, but the non-image area of the photosensitive layer and the colored recording layer are treated with a solvent that can dissolve and/or swell both the non-image area and the colored recording layer. Alternatively, the photosensitive layer and the non-image area of the colored recording layer may be simultaneously dissolved or rubbed off to form an image.

Although the selection of solvents is important for developing the photosensitive layer and the colored recording layer, the present invention can be carried out by applying conventionally known techniques in both cases.

Next, the obtained colored image is transferred to an image receiving sheet. When using an image receiving sheet having an image receiving layer according to the present invention, 150
It is possible to transfer at low temperatures below ℃. Specifically, the colored image and the image-receiving layer of the image-receiving sheet are superimposed and passed through a laminator under heat and pressure. The colored image is embedded in the image-receiving layer and transferred by heating and pressure during the passage.

When creating a multicolor proof sheet, the above exposure, development, and
Repeat the transfer process as many times as necessary. More preferably, the image-receiving layer to which the colored image has been transferred is superimposed so as to be in contact with a white paper, and the multicolored image is transferred to the white paper by passing it through a laminator under heat and pressure, thereby forming a colored image on the plain paper. You can also.

〔Example〕

Examples will be given below, but the present invention is not limited thereto.

Example 1 An undercoat layer coating solution having the following composition was coated on a polyethylene terephthalate film to prepare a support having a releasable surface.

Torezin F'-50 (alcohol-soluble nylon, manufactured by Toshisha Co., Ltd.) 10g methanol/L'
Next, four colored recording layer dispersions having the following compositions were prepared and coated to give a dry film thickness of 3 μm.

Photosensitive resin having the following structure 1.54 g Phenol resin having the following structure &469 (m:n=4:
, 6 average molecular weight 2000) H3 The following pigments 5g ethyl cellosolve 1oag (pigment) Black Nikar Pump Hookna 5° (manufactured by Mitsubishi Kasei) Yellow: Chromophthal Yellow 8G (manufactured by Ciba Geigy) Magenta Nichrome Phthal Red A (〃) Cyan Nichrome lid μb A/-4ON (〃) Furthermore, the following photosensitive composition was coated as an image forming layer on the colored recording layer so that the dry film thickness was 3 μm.

Photosensitive resin having the following structure: 2.30 g Phenol resin having the following structure: 7.70 g (t:m:
n-48:32:20 Average molecular weight 7000) n-propy acetate/' 709 cyclohexanone 50g The obtained four-color image forming material was subjected to color separation rt? Superimposed with Sea vs. Sk,
After imagewise exposure from a distance of 50 cM using a 3KW Meta-μ Hafid Hump, the image was developed by immersing it in a 10-fold dilution of 8DP-1 (Sakura PS version developer: manufactured by Konishiroku Photo Industries Co., Ltd.) for 20 seconds to develop four colors. Got the image.

Nylon 1 to another polyethylene terephthalate film
2 Film (manufactured by Daicel Chemical Industries, Ltd., Diamid Film 2401, 30 μm thick) 1 heated to 130°C
An image receiving sheet was prepared by passing between a pair of nip rolls and laminating.

Bring the previously obtained yellow image into close contact with the image receiving sheet, and
The color image was transferred to an image-receiving sheet by passing between a pair of nip rolls heated to .degree. Subsequently, color images were transferred in the order of color, 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 multicolored image was transferred to white paper by passing it between a pair of nip rolls heated to 0°C. In this way, a multicolor color pattern in micrometers was obtained on white paper. The color proof obtained was very good and very similar to the printed material.

Comparative Example 1 A multicolor image was formed on an image-receiving sheet in exactly the same manner as in Example 1, except that the following composition was used for the image-receiving sheet.

Polymethyl methacrylate 9og bentaerythritome! Tetofacrylate michfuketone
151g benzophenone
518g methyμethyketone 220g The multicolor image on the image-receiving sheet was transferred to white paper in exactly the same manner as in Example 1, but when the support of the image-receiving sheet was peeled off, part of the image remained on the support. It was not possible to transfer 100 characters.

In order to perform good peeling, it was necessary to perform post-exposure for 20 seconds with a 3KW metal halide lamp from a distance of 5010M after transfer.

Example 2 An undercoat layer coating solution having the following composition was applied onto a polyethylene terephthalate film to prepare a support having a releasable surface.

CM-8000 (alcohol-soluble nylon, manufactured by Toshi Co., Ltd.) 0 g Methanol 90 g Next, colored recording layer dispersions of four colors having the following compositions were prepared and coated to give a dry film thickness of 2 μm.

Hydroxyphenyl methacrylate/acrylonitrile/L'-methyl methacrylate/maleic acid copolymer (30:40:25:5) 15g The following pigment 5g Methyl cellosolve 809 (pigment) Black: Carbon black MA-100 (Mitsubishi Kasei Corporation) ) Yellow: Rio No! Yellow GR (manufactured by Toyo Ink Co., Ltd.) Magenta: Fastgen Superade BN (manufactured by Dainippon Ink Co., Ltd.) Cyan: Lyonor μ/l/-NCB (manufactured by Toyo Ink Co., Ltd.) Further, apply a photosensitive layer coating liquid with the following composition to the photosensitive film thickness. It was applied to a thickness of 2 μm.

Trimethylo-ppropane triacrylate 4f
1 styrene-maleic anhydride copolymer 4,9 dimethylthioxanthone 1 g dimethylaminobenzoic acid isoamide/L/1 g methyl cellulose μ acetate 90 g The obtained four-color image forming material was overlaid with a color dispersion negative mask of each color, After image-wise exposure for 10 seconds from a distance of 50 crR using a 5Kw meta p-hatsoid pump, the film was immersed in a 10-fold diluted solution of 8DP-1 (described above) for 30 seconds and developed to obtain a four-color image.

Next, the following image-receiving layer coating solution was applied onto a polyethylene terephthalate film (manufactured by Toshi Co., Ltd.) whose surface had been subjected to a silicone release treatment so as to have a dry film thickness of 20 μm to prepare an image-receiving sheet.

50 g of polyester hot melt adhesive (Kemi, manufactured by Toshisha Co., Ltd. R-99, softening temperature: 100 DEG C.) 100 g of methyl ethyl ketone Subsequently, four color images were transferred to this image-receiving layer in the same manner as in Example 1. A color image consisting of four colors was formed on the image receiving sheet. The color proof obtained was very good and very similar to the printed material.

Example 3 A coating solution having the following composition was applied onto a silicone-treated polyethylene terephthalate film (trade name: Tuft Tsubu, manufactured by Toshi Co., Ltd.) to a dry film thickness of 30 μm to prepare an image-receiving sheet.

Ethylene-vinyl acetate copolymer 4g (trade name Evaflex EV-150 manufactured by Mitsui Bolichemica μ) Toluene
10 g MethiμEchip
Ketone 10g A multicolor cup proofing sheet was obtained on white paper in the same manner as in Example 1 except for the above image-receiving sheet. The color density μm7 obtained was very good and very close to that of the printed matter.

Example 4 A release layer coating solution having the following composition was applied onto a polyethylene V terephthalate film so that the dry film thickness was α6 μm.

CM-8000 (Aμ soluble nylon, Toshisha!
! 0 g methanol 90 g Next, a coating solution having the following composition was applied onto the release layer so that the dry film thickness was 30 μm to prepare an image-receiving sheet.

Styrene-butadiene copolymer 10g (trade name: Tuffprene, manufactured by Asahi Kasei Corporation) toluene
100g A multicolor proofing sheet was obtained on white paper in the same manner as in Example 1 except for the above image receiving sheet. The obtained color proof was very good and very similar to the printed material.

Example 5 A support having a releasable surface was prepared in the same manner as in Example 4.

Next, apply a coating solution with the following composition on the release layer until the dry film thickness is 30 μm.
An image-receiving sheet was prepared.

Styrene-isoprene copolymer 10g (trade name Kaliflex TR1107, manufactured by Shell Chemical Co., Ltd.) Toluene
100 g A multicolor proofing tart was obtained on white paper in the same manner as in Example 1 except for the above image-receiving sheet. The obtained color proof was very good and very similar to the printed material.

Example 6 A support having a releasable surface was prepared in the same manner as in Example 4.

Next, on the release layer, apply a coating solution with the following composition to a dry film thickness of 30 mm.
An image-receiving sheet was prepared by applying the film to a thickness of μm.

Polyacrylic resin 209 (trade name: Dyana 79BR107, manufactured by Mitsubishi Rayon Co., Ltd.) Toluene 100 g A multicolor proofing sheet was obtained on white paper in the same manner as in Example 1 except for the above image receiving sheet. The color blues obtained were of good quality and were very close to the printed matter.

Example 7 A support having a releasable surface was prepared in the same manner as in Example 4.

Next, on the release layer, apply a coating solution with the following composition to a dry film thickness of 30 mm.
An image-receiving sheet was prepared by applying the film to a thickness of μm.

Thermoplastic urethane resin 20g (trade name Sunblane LQ-3510, manufactured by Sanyo Chemical Industries, Ltd.) Toluene sag isopropyl μapco ~ 50g Multicolored color proofing was carried out on white paper in the same manner as in Example 1 except for the above image-receiving sheet. Got a sheet. The obtained color proof was very good and very similar to the printed material.

Example 8 A support having a releasable surface was prepared in the same manner as in Example 4.

Next, on the release layer, apply a coating solution with the following composition to a dry film thickness of 30 mm.
An image-receiving sheet was prepared by applying the film to a thickness of μm.

Acrylonitrile-butadiene copolymer 10g
(manufactured by Nippon Zeon Co., Ltd.) Methyl ethyl ketone 100 g A multicolor proofing sheet was obtained on white paper in the same manner as in Example 1 except for the above image-receiving sheet. Obtained cup size μm
The print quality was very close to that of printed matter.

Example 9 A support having a releasable surface was prepared in the same manner as in Example 4.

Next, on the release layer, apply a coating solution with the following composition to a dry film thickness of 30 mm.
An image-receiving sheet was prepared by applying the film to a thickness of μm.

Butyl rubber (manufactured by Nippon Butyl Co., Ltd.) 10g)/l/en
A multicolor proofing sheet was obtained on white paper in the same manner as in Example 1 except for the above image receiving y). The color proof obtained was very good and very similar to the printed material.

〔Effect of the invention〕

As explained above, according to the method of the present invention, (1) the film is strong and there is no image loss when creating a transferred image; (2) there is no surface tack at room temperature, making registration marks easy to align; This produces a remarkable effect.

Claims (1)

[Claims] 1. After imagewise exposure, an image-forming material consisting of a photosensitive colored recording layer coated on a support having a releasable surface is developed to form a colored image. 150
℃ or below, and selected from the group consisting of polyamide, polyester, polyurethane, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-isoprene copolymer, butyl rubber, and polyacrylic resin. 1. A method for forming a transferred image, characterized in that the image is transferred onto an image-receiving layer containing one type of thermoplastic resin.