JPH0461348B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image forming method for forming a color image on a plastic film using electrophotography or the like.

[Conventional technology]

Generally, images such as drawings or characters are formed on film using an electrophotographic copying machine, etc., and the image is enlarged and projected using an overhead projector (OHP), which is widely used in education or conferences. There is. Conventionally, it has been mainstream to express images in black on transparent film, but in recent years there has been a strong demand for expression in color.

Broadly speaking, the demands for colorization can be divided into two: the desire to simply color OHP films and classify them according to their purpose in an easy-to-understand manner; the desire to form a color negative image (white blank image on a color background) to make it easier to see; Furthermore, there are various demands such as the desire to express drawings, characters, etc. in color positive images.

[Problem that the invention seeks to solve]

Methods for colorizing images include an electrophotographic method using color toner, an inkjet recording method, and a thermal transfer recording method.
Translucent substrates such as those for OHP generally have poor ink absorption or do not absorb ink at all, which has traditionally made it difficult to create transmissive images using inkjet recording methods or thermal transfer recording methods. gender has been pointed out. Also, in the electrophotographic method using color toner, it is easy to create a positive image, but in order to form a negative image, a negative original is required, and in terms of toner adhesion, it is difficult to create a clear negative image. Images are difficult.

[Means for solving problems]

In response to these demands, the present inventors have proposed the above-mentioned
A photosensitive layer consisting mainly of a colorant and a photopolymer is provided on one side of a plastic film with a heat resistance temperature of 100°C or higher, and on the photosensitive layer or on the opposite side, the film is transparent, suitable for electrophotographic copying, and removable. Using a photosensitive film provided with a peel layer, a step of forming a toner image on the peel layer using an electrophotographic copying device, irradiating actinic light from the toner image side to expose the photosensitive layer in the area where there is no toner image. A color negative image or a positive image that can be used as an OHP film is produced by the following steps: peeling off and removing the peel layer on which the toner image has been formed; and developing the exposed photosensitive layer to form an image. I found it easy to obtain.

[Function and effects of the present invention]

According to the present invention, by selecting the photopolymer to be used, for example, in the case of a negative type photopolymer, an image that is reversed from a positive original to a negative can be obtained;
Further, in the case of a positive type photopolymer, a positive color image can be obtained from a positive original. Furthermore, if used with a black image formed on the peel layer using an electrophotographic copying machine, the black image will be formed on the colored background.
It becomes an OHP film. As described above, the photosensitive film of the present invention satisfies various requirements for colorizing OHP films.

The present invention will be explained in more detail below. The plastic film used in the present invention with a heat-resistant temperature of 100° C. or higher is not particularly limited as long as it can withstand heat during electrophotographic copying or OHP projection. Generally, for this purpose, a biaxially stretched polyester film (polyethylene terephthalate film) or the like is preferably used.

Next, the photopolymer contained in the photosensitive layer applied to the present invention is polymerized, crosslinked, and
Causes changes such as dimerization, bridge rupture, decomposition, and rearrangement,
It is a photosensitive material that has the property of increasing or decreasing its solubility in a solvent, and is also conventionally called an organic or inorganic photosensitive agent for plate making, a photosensitive resin, a photoresist, etc. Examples include the following:

1. Photosensitive ferric salts that provide ferrous ions upon exposure, such as ferric ammonium citrate, ferric ammonium oxalate, and ferric oxalate soda, and hydrophilic polymers such as gelatin and glue. A composition consisting of

2 Hydrophilic polymers such as gelatin, fish glue, gum arabic, polyvinyl alcohol, polyacrylamide, carboxymethyl cellulose, hydroxyethyl cellulose, copolymers of polyvinyl methyl ether and anhydrous maleic, and p-aminodiphenylamine, benzidine, dianidine, toluidine, etc. A composition comprising a diazo resin obtained by condensing a tetrazonilam salt of a diamino compound or p-diazophenylamine with paraformaldehyde.

3. A composition comprising a diazo resin obtained by condensing a diazo compound such as p-diazophenylamine with paraformaldehyde.

4 4,4'-Diazidostilbene-2,2' Sodium disulfonate, 1,5-Diazidonaphthalene-
Sodium 3,7-disulfonate, 3'-azido-4-4-azidobenzalacetophenone
Sodium 2-sulfonate, Sodium 4,4'-diazidostilbene-α-carboxylate, Di(4-amido-2'-hydroxybenzal)acetone-
2-sodium sulfonate, 4-azidobenzalacetophenone-2-sodium sulfonate, 4,
Azide compounds such as sodium 4'-diazide diphenyl-3,3'-disulfonate, polyacrylamide, polyvinylpyrrolidone, polyacrylic acid, gelatin, casein, albumin, gum arabic, CMC, hydroquine ethyl cellulose, soluble nylon, etc. A composition consisting of a polymer.

5 From azide compounds such as 4,4'-diazidostilbene, 4,4'-diazidochalcone, 4,4'-diazidodibenzalacetone, and cyclized rubber, synthetic rubber, and polymers soluble in organic solvents. composition.

6. A composition of a quinone diazide compound such as naphthoquinone-1,2-diazide sulfonic acid ester or sulfonic acid and an alkali-soluble resin.

7. A composition comprising a polymer in which a cinnamic acid group is introduced into the molecule, such as cinnamic acid ertel of polyvinyl alcohol, and a sensitizer such as 5-nitroacenaphthene, 1,2-benzanthraquinone, Micheler's ketone, etc. .

8 Acrylic acid or ester obtained from α-alkyl acrylic acid and polyglycols,
A composition comprising a polymerization initiator such as 9,10-anthraquinone and a filler.

9 Acrylamide, calcium acrylate,
Ethylenically unsaturated compounds such as N,N'-methylenebisacrylamide, photosensitive ferric salts such as ferric ammonium citrate, ferric sodium oxalate, and ferric ammonium oxalate, gelatin, and polyvinyl alcohol. A composition comprising a hydrophilic polymer such as a hydrophilic polymer.

10 Photoreduction of ethylenically unsaturated monomers such as acrylamide, methacrylamide, acrylic acid and ethylene blue, rose bengal, phloxine, erythrosin, eosin, fluorescein, acriflavin, thionin, riboflavin, chlorophyll, brilliant green, methylene green, etc. and a hydrophilic polymer such as gelatin, polyvinyl alcohol, polyacrylamide, and CMC. Calcium acrylate, N, if necessary
A composition that serves as a crosslinking material such as N'-methylenebisacrylamide.

11 A positive photosensitive agent having an 0-nitrobenzanedehyde group such as bis-(3-aldehyde-4-nitrophenyl)-phthalate and 3-aldehyde-4-nitrophenyl carbonate.

Although typical examples have been described above, the present invention is not limited to these, and various known methods can be used for image formation.

Various pigments and dyes can be used as the coloring agent contained in the photosensitive layer. Especially when used for OHP, various color tones are required. Therefore, pigments and dyes may be selected depending on the desired color tone and the photopolymer used. As the pigment, inorganic pigments, organic pigments, etc. are used in the form of water dispersion or solvent dispersion. Various oil-soluble dyes, water-soluble dyes, spirit dyes, disperse dyes, etc. are used depending on the purpose. Furthermore, OHP
When used for commercial purposes, turbidity during image projection may become a problem, so it is best to select a coloring agent that is as transparent and sharp as possible.

In the present invention, the transparent and peelable peel layer to be provided on the photosensitive layer or on the opposite side includes:
Polystyrene, polyvinyl acetate, polyacrylate, copolymer of methyl methacrylate and acrylate, copolymer of methyl methacrylate and vinyl acetate, polyvinyl chloride, copolymer of vinyl chloride and vinyl acetate, polyvinylidene chloride, vinylidene chloride and vinyl acetate copolymers, polyvinyl butyrate, cellulose acetate phthalate,
Depending on the type of support and photosensitive layer, it can be appropriately selected from film-forming polymeric substances such as natural rubber, cyclized rubber, synthetic isoprene rubber, polyvinyl formal, polyester, and nylon, and can be used alone or in combination. . Furthermore, we have developed products that are suitable for electrophotographic copying machines, that is, they have excellent adhesion with toner, high image density, no double feeding, good running performance, and no problems caused by static electricity. It is further effective to appropriately add a resin with good adhesiveness, a matting agent, an antistatic agent, etc. to the peel layer.

Resins that have good adhesion to toner include organic solvent-soluble polyester resins, acrylic ester resins, methacrylic ester resins, or copolymers of styrene and acrylic esters, or styrene and metal acrylic esters, which are the same as the toner. If a resin of the composition is added and mixed to the peel layer, the toner will adhere more firmly during heat fixing. or,
Matifying agents include talc, clay, charcoal,
Inorganic pigments such as silica and titanium, polyethylene,
There are organic polymer powders such as polypropylene, polystyrene, polyamide, polyester, phenol resin, urea resin, melamine resin, epoxy resin, and phenoxy resin. The particle size and addition amount of the matting agent are selected in consideration of transparency and surface condition.

When applying the photosensitive layer and peel layer, they are applied in a state of being dissolved or dispersed in water or a solvent, and coating methods include bar coating,
Any known coating method such as blade coating, roll coating, spinner coating, curtain coating, or gravure coating may be used, and the solvent used is appropriately selected depending on the types of the photosensitive layer and peel layer.

〔Example〕

The present invention will be explained below with reference to examples, but the present invention is not limited to the following examples. All parts refer to parts by weight.

Example (1) In a solution of 20 g (parts) of gelatin, 6.3 g (parts) of ferric ammonium oxalate, and 400 g (parts) of water, 5 g (parts) of Phthalocyanine Blue, 5 g (parts) of Phthalocyanine Blue, and 45 g (parts) of water were added in a ball mill. A photosensitive solution is prepared by adding the dispersion produced by the processing, and this is coated on a 100 micron transparent polyester film and dried to create a 2 micron thick photosensitive layer. Vinyl chloride-vinyl acetate copolymer 15 (Vinyrite VYHH, manufactured by UCC) A peel layer consisting of 45 parts of methyl ethyl ketone and 40 parts of toluene was coated and dried on the photosensitive layer so that the thickness after drying was 6 μm. Black characters were copied onto the peel layer of the photosensitive film thus obtained using Xerox 3500 (Fuji Xerox Co., Ltd.).

Thereafter, the printed text was exposed to light for about 3 minutes from a 30 ampere arc lamp at a distance of 60 cm. After exposure, peel off the peel layer and store in 1% H2 at 18℃ _.
The exposed portions of the photosensitive layer were immersed in an O ₂ aqueous solution for 1 minute to make them fully insoluble in water, and then immersed in water at 37°C to dissolve and remove the uncured portions of the photosensitive layer, resulting in a cyan negative image. I made it. When this negative image was projected on OHP, blank white letters were projected onto a bright cyan background.

Example 2 Polyvinyl alcohol (degree of polymerization 1700-2400, degree of saponification 98.5±0.5) 10% aqueous solution 100 parts p-diazodiphenylamine-formaldehyde condensate 0.8 parts Permanent carmine FB 20% aqueous dispersion 4 parts Water 100 parts Isopro A magenta photosensitive solution consisting of 10 parts alcohol was applied and dried on a 100μ transparent polyester film to form a 2 micron thick photosensitive layer, followed by 15 parts formal resin (Denka Formal #30 manufactured by Denki Kagaku Co., Ltd.) and 25 methanol. A peel layer consisting of 75 parts of toluene was coated and dried on the photosensitive layer so that the thickness after drying was 6 μm. Black characters were copied onto the peel layer of the photosensitive film thus obtained using Ricopy DT5700Rb (Ricoh). Thereafter, the photosensitive layer was exposed to light by passing it through Ricopy SD-100 (Ricoh) so that it was exposed to light from the side of the copied characters, and then the peel layer was peeled off and the photosensitive layer was developed with water. After drying, magenta negative characters were obtained. When projected using an OHP, the blank white letters appeared clearly on a magenta background.

Example 3 10 parts of alkali-soluble cresol novolak resin 5 parts of a condensate of 1,2-naphthoquinonediazide-(2)-5-sulfonyl chloride and alkali-soluble phenol novolak resin Dye Varifxt Blue 1605 (manufactured by Orient Chemical Co., Ltd.) ) A positive photosensitive liquid consisting of 2 parts methyl ethyl ketone 60 parts ethyl cellosolve acetate 30 parts and butyl acetate 10 parts was coated on a 100μ transparent polyester film and dried to form a 2μ thick photosensitive layer, followed by vinyl chloride/vinyl acetate copolymer. A peel layer consisting of 15 parts of combination (Vinyrite VYHH, manufactured by UCC), 45 parts of methyl ethyl ketone, and 40 parts of toluene was applied to the opposite side of the photosensitive layer so that the thickness after drying was 10 μm. Black characters were copied onto the peel layer of the photosensitive film thus obtained using Xerox 3500 (Fuji Xerox). After exposure for 50 seconds from the black character side using a bright room printer P-607 (Dainippon Screen Manufacturing Co., Ltd.), the peel layer was peeled off and the photosensitive layer was developed with a 0.5% NaOH aqueous solution. After drying, a 20-second secondary exposure using a similar printer produced a clear blue character image. (In this case, the peel layer may be removed after development or after secondary exposure.)

Claims (1)

[Claims] 1. A photosensitive layer consisting mainly of a colorant and a photopolymer is provided on one side of a plastic film with a heat resistance temperature of 100°C or higher, and on the photosensitive layer or on the opposite side, a film that is transparent and suitable for electrophotographic copying is provided. A step of forming a toner image on the peel layer using an electrophotographic copying device using a photosensitive film provided with a peelable layer that can be peeled off, and irradiating active light from the toner image side to expose areas without the toner image. An image forming method comprising: exposing a layer to light; peeling and removing a peel layer on which a toner image is formed; and developing an exposed photosensitive layer to form an image.