JPH01205149A - Image forming material - Google Patents

Abstract

PURPOSE:To obtain an approximately same transfer as a printed matter as a prepressed print for color proofing by incorporating a specified org. dye deriv. into a photosensitive layer. CONSTITUTION:0.1-30pts.wt. org. dye deriv. expressed by formula I per 100pts. wt. pigment is incorporated into a photosensitive layer. In formula I, Q is an org. dye residue; each X1 and X2 is H atom., halogen atom. If X2 is halogen atom., (j) is >=2; each (i) and (j) is 1-4, independently. By this constitution, an image forming material providing stably reproduced transferred picture images, generating no unevenness in reflection density of transferred picture images nor periodical pattern, nor generating fine directional pattern, but having high color reproducibility is obtd.

Description

Detailed Description of the Invention [Objective of the Invention] (Industrial Application Field) The present invention relates to the formation of two images, and more particularly, to the formation of two images, and more specifically, to The present invention relates to an image forming material that uses monochrome or multicolor superimposition, and is capable of obtaining a transferred product similar to a printed matter as a prepress proof for two-color proofing.

(Prior Art) Conventionally, in the field of printing industry, it has been known to utilize pre-press proofing or off-press proofing as a means for checking the finished two-tone etc. of the final printed matter before printing. There are two types of prepress proofs: an overlay method and a subprint method, which are used depending on the final image quality and the purpose of use in the plate-making and printing processes.

In the overlay method, each transparent base film is provided with a photosensitive layer corresponding to each color separation (color separation) image, and each film obtained through the actinic ray irradiation and development process is visually checked for the registration of the 9 color separations. overlay. Although this method is very simple, it is affected by the light reflected from the films when three layers are stacked.

It has drawbacks that are significantly different from the quality of actual printed matter.

The server print method is 9 For example, US Patent No. 3060023
As disclosed in Japanese Patent No. 3,060,024 and No. 3,060,025, several color-separated images are sequentially formed by overlapping several photosensitive layers on a single support. For coloring, there are a simple transfer method and a method using powder color toner, but the transfer method has the advantage of being easy to operate. On the other hand, in the method using powder color toner, due to the powder, consideration must be given to the working environment.

The quality of a prepress proof requires a copy that is close to a printed matter, but the transfer method cannot necessarily be said to be sufficiently close to the printed matter in terms of gloss, halftone reproducibility, etc. Also, in the method using powder color toner.

Since printing is a separate process, it is difficult to make it closely resemble the actual printed material.

Furthermore, in the transfer method disclosed in U.S. Pat. No. 3,060,023, etc., a photosensitive layer and an image receptor are brought into close contact with each other under pressure in a plane, heated, and then peeled off. . With this method, the reproduction of the transferred image is unstable, resulting in non-uniform reflection density, minute periodic patterns, and even minute directional patterns, resulting in 9-color reproduction, etc. Accuracy is significantly reduced.

Also, Japanese Patent Application Publication No. 59-97410, 61-18
No. 8537 discloses a proofing system that can be used for both the overlay method and the subprint method. In this proofing system.

(1) Release layer 1 colored photosensitive layer on polyester support.

A color sheet made of sequentially laminated protective layers and an image receiving film made of an image receiving layer and a protective film on a polyester support are prepared.

(2) Two images are formed by bringing the emulsion side of the color sheet and the halftone negative into close contact, and then the unexposed areas are eluted with a mixture of soda carbonate, butyl cellosolve, and water. After drying, it is also effective as an overlay type proofing.

(3) What about proofing as a server print method?

After sequentially transferring black, cyan, magenta, and yellow to the image-receiving film at a temperature of 110° C., a pressure of 2 bar, and a speed of 60 cm/min, registration was performed visually or by punching.

(4) After transferring to a receptor, which is a transfer target, to obtain a normal image, a film that has been subjected to a matting treatment is transferred to obtain proofing in order to reduce the reflective gloss of the transfer layer and the colored layer.

In either method, pigments are often used in the photosensitive layer, and although this may be due to the dispersion of the pigments, 1) the formed color image has 2 reflections, which are usually small in the actual printed matter. Uneven density or periodic patterns.

There is a problem in that fine directional patterns may be produced, making it impossible to obtain an image that resembles a printed matter, which is the purpose of forming one image. Further, there were problems in that the density and gloss were different from the original printing, and the finished quality was not sufficient.

(Problem to be solved by the invention) No matter which method is used, the texture will be different from the actual printed matter from this machine, so it has been used mainly for checking the process between plate making and printing. Even if it was used as a substitute for printed matter, it was recognized that the quality was different.

Therefore, the reflection density of the image formed is constant.

A method that can form fine images has been desired. -An object of the present invention is to provide an image forming material that can form an image having an image quality equivalent to that of a single-machine print. In other words,
The reproduction of the transferred image is stable, and the transferred image has uneven reflection density and periodic patterns.

It is a material that excels in three-color reproduction without creating fine directional patterns.

In other words, the present invention is based on the discovery that the quality of images obtained is stable in terms of density and the like by providing a photosensitive layer with excellent pigment dispersibility.

According to the present invention, the result of superimposing multicolored images is.

The density is stable, there is no transfer unevenness, and quality similar to that of a printed image can be obtained. Furthermore, for example, when a plurality of multicolor images are obtained from the same document, a constant finish quality and a constant density can be obtained.

[Structure of the invention]

(Means for Solving the Problems) The present invention involves forming a photosensitive layer containing a pigment on a support, exposing it to light for one image, and forming an image by development, or exposing the photosensitive layer to light. This causes a difference in tackiness during transfer between the exposed area and the unexposed area.

In an image forming material for transferring an image to an image receptor such as paper, the photosensitive layer contains 0.1 to 30 parts by weight of an organic dye derivative represented by the general formula (1) per 100 parts by weight of a pigment. be.

[In the formula, Q is an organic dye residue, XI and X are different from each other, and are a hydrogen atom and a halogen atom (when ) or the substituents + ilj shown below each independently represent an integer of 1 to 4.

-C○OM/1゜ 13o, M/l.

R8 R2゜ R.

or.

(In the formula, Y is a hydrogen atom, a halogen atom, -No□.

-NH, or -So, H, M are hydrogen atoms or metal atoms, A is -(CHz)n- or -CH
□NHCOCHz, R+, Rz are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or R1 and R2
to form a heterocycle, R3, Ra, Rs, R
h is a hydrogen atom (R1, R,, R1i+ R.

(except when all of are hydrogen atoms) or carbon number 1~
30 alkyl groups are integers of 1 to 4, Il is the valence of M, and m and n are integers of 1 to 8).

Furthermore, the photosensitive layer is an image forming material containing a photopolymerizable compound and a non-photopolymerizable organic polymer binder, and the non-photopolymerizable organic polymer binder is a diallyl phthalate resin. It is a forming material.

The present invention is a material that can produce color proofs easily, quickly, and stably with the same texture as actual printed matter even in the subprint method. Of course, this method can also be applied to the overlay method. In other words, the present invention is a material that can produce color proofs of stable quality that have almost the same texture as printed matter produced by this machine.

The image-forming material of the present invention has the following characteristics:
There are no fine periodic patterns or fine directional patterns),
The color image obtained by development can be transferred to art paper, etc., which is the ink receptor for printing with this machine, or it can be directly transferred to art paper, etc., and it is photosensitive in the same state as printing with this machine. By transferring the layers, it is possible to obtain a reproduction that closely resembles the actual print. It is also a material that can stably transfer even minute images.

The image-forming material according to the present invention usually has a structure of a support/a plurality of photosensitive N/protective films including a colored photosensitive layer, as described below.

As the support, a material that is stable to heat, chemicals, light, etc., and that transmits actinic rays is suitable. For example, cellulose acetate polystyrene.

Films or sheets made of polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyimide, polypropylene, etc. Particularly preferred is a polyethylene terephthalate film or sheet from the viewpoints of transparency, thermal stability, one-dimensional stability, and the like.

Furthermore, these supports may be used as they are.

It is also possible to perform mold release treatment using a suitable oil-repellent substance. These oil-repellent substances include silicone resin.

Examples include things like fluororesins.

Examples of the protective film include, but are not limited to, polyethylene film, polyethylene terephthalate film, and acetate film. Furthermore, what is a protective film?

It is a film that is removed after image exposure and is not present at the time of transfer to the image receptor. Therefore, the support is present at the time of transfer.

The photosensitive layer according to the present invention may have two or more layers, but at least one layer contains a pigment.

As a photosensitive layer.

(a) Photopolymerizable compounds, pigments and organic dye derivatives (b)
) It consists of a photopolymerizable compound, a thermoplastic resin, a pigment, an organic dye derivative, etc., and a photopolymerization initiator and a thermal polymerization inhibitor are usually used in combination.

As the photopolymerizable compound, at least one selected from monomers, oligomers, and prepolymers is used.

Furthermore, other additives can also be used in combination.

Although the photopolymerizable compound is not particularly limited, it is preferably a compound that can plasticize a thermoplastic resin at room temperature.

For the photosensitive layer, a photopolymerizable compound is used so that it can be mixed with a pigment (coloring agent) and cured by exposure to light.

A photosensitive layer is formed on the top of the support, and a protective film (cover sheet) is further provided on the photosensitive layer.

The photosensitive layer can be developed using a development method, or a dry peeling method that creates a difference in tackiness during transfer between exposed and unexposed areas of the photosensitive layer through image exposure and allows the image to be transferred to an image receptor such as paper. A developing method.

Although any type may be used, a dry peeling development method is preferred from the viewpoint of workability. In this dry type, development and transfer to an image receptor can be performed simultaneously by simply transferring.

Furthermore, in this peeling development method.

It is preferable to select a photosensitive layer that peels off one layer during transfer. In other words, since this photosensitive layer is photopolymerizable, the hardened portion loses its adhesion to the image receptor after 9-image exposure, and the moderate internal collective force of the unexposed portion allows creation of fine image reproduction. It has the advantage that it can be easily transferred onto an image receptor by peeling. Here, having an appropriate internal focusing force means that the image formed on the image receptor is not transferred at least in its entire thickness. Namely.

Causes delamination. Note that "one-layer peeling" means rupture and peeling within one layer.

The appropriate internal cohesive force of the photosensitive layer can be selected from among various types depending on the type and/or blending ratio of the photopolymerizable compound, pigment, etc. used in the photosensitive layer. moreover.

It also varies depending on the type of image receptor or support.

2 Usually to cause peeling between the eyebrows in the photosensitive layer.

Although the difference in softening points is utilized, it is not limited to this.

As the photopolymerizable compound that can be used in the present invention, ethylenic unsorated compounds are preferable2.For example, (meth)acrylic acid, methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, dimethylaminoethyl (meth) Acrylate, benzyl (
meth)acrylate, carpitol (meth)acrylate 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylate Acrylamide, N-methylol(meth)acrylamide, styrene, acrylonitrile, N-vinylpyrrolidone, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol di(meth)acrylate polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate,
Neopentyl glycol di(meth)acrylate, 1.
4-butanediol diacrylate, 1,6-hexanethiol di(meth)acrylate, pen erythritol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate.

Dipentaerythritol hexaacrylate, phenoxyethyl acrylate, nonylphenoxyacrylate, tetrahydrofurfuryloxyacrylate, caprolactone-modified tetrahydrofurfuryl acrylate, ethylene oxide (E O)-modified methacrylate, phenoxydiethylene glycol acrylate, EO-modified phthalic acid acrylate.

(Meth)acrylate of alkylene oxide adduct of phenol, caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate.

Low molecular weight photopolymerizable compounds such as dicyclopentanyl diacrylate, or epoxy acrylate.

Urethane acrylate, polyester acrylate.

These are high molecular weight photopolymerizable compounds such as alkyd acrylates, acrylate modified products of petroleum resins, and unsaturated polyesters. One or a mixture of two or more of these may be used.

As the thermoplastic resin (organic polymer binder), a thermoplastic, non-photopolymerizable polymer that has excellent compatibility with photopolymerizable compounds can be used. For example, polyvinyl chloride,
Poly(meth)acrylic acid, poly(meth)acrylic ester, polyvinyl ether, polyvinyl acecool, urethane resin, epoxy resin.

Polyamide, polyester, vinylidene chloride-acrylonitrile copolymer, vinylidene chloride-methacrylate copolymer, vinylidene chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, cellulose 8M4 (e.g. methylcellulose, ethylcellulose, cellulose acetate) ), polyolefins (e.g. chlorinated polyethylene)
, synthetic rubbers such as butadiene-acrylonitrile copolymers, diallyl phthalate resins (eg, diallyl isophthalate polymers, diallyl orthophthalate polymers, water additives thereof), and the like.

In addition, in image formation using a developer, 2 usually an alkaline aqueous solution is used, so thermoplastic resins that can be developed with an alkaline aqueous solution, such as resins having carboxyl groups, styrene-maleic anhydride copolymer resins, alkyl acrylates, etc. Ester-(meth)acrylic acid copolymer resins, partially esterified products thereof, etc. are used.

It is possible to add polymers other than these thermoplastics to obtain desired physical properties. For example, adhesion to a support, adhesion to a receiver during transfer, and abrasion resistance can be improved. Suitable non-thermoplastic polymeric compounds include, for example, phenolic resins, melamine-formaldehyde resins, urethane resins, and the like. In addition, a small amount of filler may be included as a component of this photosensitive layer, examples of which include silica, mica, bentonite, etc.
It may be present in an appropriate amount depending on the properties required.

As the photopolymerization initiator, those with low absorption in the visible light region are more preferable, such as benzophenone, 4,
4-bis(diethylamino)benzophenone, 4-methoxy-4-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthraquinone, benzoin, benzoin methyl ether.

Benzoin phenyl ether, isobutyl benzoin ether, isopyropyl benzoin ether, benzoin ethyl ether, 2,2-jethoxyacetophenone,
2-Hydroxy-2-methylpropiophenone, 4'-
Isopropyl-2-hydroxy-2-methylpropiophenone, p-tertbutyltrichloroacetophenone, Michler's ketone, benzyl dimethyl ketal, 2.
2-dimethoxy-2-phenylacetophenone, hydroxycyclohexylphenyl ketone, benzophenone,
Azobisisobutylnitrile, 2-chlorothioxanzone, 2-methylthioxanzone, 2-ethylthioxanzone.

2-isoprobylthioxanzone and the like. These addition polymerization initiators may be used alone or in combination of two or more,
When using two or more types in combination, consideration should be given to the mutual influence on free radicals generated by light absorption. Furthermore, various sensitizers may be added to improve the addition polymerization rate.

In addition, examples of thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, and t-butylcatechol.

Pyrogallol, pyridine, arylphosphite, etc. can be used.

The thickness of the photosensitive layer may be about 0.5 to 5 μm.

The appropriate amount to apply varies depending on the pigment contained.

0°5 g/rd to 10 g/rrr is appropriate.

Although the coating of the present invention was carried out using a bar coater or the like, it is of course possible to use a spin coater or a similar coater, for example.

There are thermoplastic materials that are particularly effective in the present invention that can be used other than those mentioned above, but when combined with suitable ethylenically unsaturated compounds, polyacrylate polymer materials and diallylisophthalate polymers is suitable. The appropriate ratio of thermoplastic substance to ethylenically unsaturated compound varies depending on the materials used, but - the ratio of thermoplastic substance to ethylenically unsaturated compound in the membrane is between 40=60 and 90:10. If there is
The surface of the photosensitive layer can be slightly sticky or non-adhesive.

At this time, if any tackiness remains in the photosensitive layer, registration will be difficult, and moreover, dust and the like in the environment will adhere to the surface of the photosensitive layer, significantly reducing the image quality as a color proof. Furthermore, a small amount of thermal polymerization inhibitor may be added to prevent dark reactions over time.

As the pigment contained in the photosensitive layer, conventionally known pigments can be used. Generally, pigments with matching hues of four colors, yellow, magenta, cyan, and black, are required, and metal powders, white pigments, fluorescent dyes, etc. are also used. Yellow for color proofing.

There are red, indigo, and ink, and you can choose a pigment dye that matches these hues.

The following are some examples of known pigments. Azo series, phthalocyanine series, quinacridone series.

These include organic pigments such as anthraquinone-based, indigo-based, and methine-based pigments, or inorganic pigments. For example, Lionor Yellow GRO (C, 121090, manufactured by Toyo Ink Manufacturing ■),
Magnetic 1201 Lionor Yellow (〃).

t'h1206 Lionor Yellow (〃), Lionor Yellow-1208 (〃), 1305 Lionor Yellow (C, 121100), 1306 Lionor Yellow (〃), 11h1307 Lionor Yellow (〃)
, Lionor Yellow FGI 310 (〃).

Lionor Yellow FGN-T (C, I 21105
), 7100 Lionor Yellow (C, I21096
), Lionor Yellow NBR (C, 121108
), Brilliant Carmine 6BA (C, 115850
:1), Lionor Red 6B4201 (〃), Lionor Lend 7B4401 (〃), Brilliant Carmine 8BA (〃), Lionor Blue FG7
330 (C, l74160), Lionor Blue FG7351 (〃), Lionor Blue G
X-1 (〃), Mitsubishi Carbon Black MA-7. Mitsubishi carbon black MA-100 and the like are suitable.

As the coloring substance, these substances may be used alone or in combination of two or more.

These pigments can be easily incorporated into the photosensitive layer through appropriate means.

In the present invention, by using an organic dye derivative, it is possible to improve pigment dispersion, etc., and to form an image having quality similar to that of printed matter produced by an actual printing machine, which is important as the image forming material of the present invention. It is. In other words, the reproduction of the transferred image is stable.

Moreover, it is possible to provide a material that is excellent in one-color reproduction without producing nonuniform reflection density, periodic patterns, or fine directional patterns in transferred images.

Organic dye derivatives include azo, phthalocyanine,
8% of organic pigments such as quinacridone series, anthraquinone series, indigo series, perylene series, perinone series, etc. 4 bodies and 1
For example, monocarboxylic acids, dicarboxylic acids, monophthalimidomethylated products, cyphthalimidomethylated products of organic dyes,
Di(4,5-dichlorophthalimidomethyl) compound, mono(4-nitrophthalimidomethyl) compound, barium salt of di(0-carboxybenzamidomethyl) compound, mono(0-carboxybenzamidomethyl) compound, monosulfonic acid, disulfonic acid , mono (N,N-dimethyl-1,
3-propanediaminosulfonyl) compound, di(N,N-
diethyl-1,3-propanediaminosulfonyl) compound, mono(N,N-diethyl-1,3-propanediaminoacetaminomethyl) compound, di(N,N-diethyl-1
, 3-propanediaminoacetamicamethyl) compound, monosulfonic acid laurylamine salt, monosulfonic acid dimethyl distearylamine salt, mono (dimethylaminomethyl) compound, trichloride, tetrachloride, and the like.

Note that the pigment and the organic dye that is the base material of the organic dye derivative may be different as long as there is no problem in terms of two hues or the like. In addition to the usual method of mixing organic dye derivatives, it is also possible to use a method called mixed campling, as seen in the case of azo pigments.

The organic dye derivative should be used in an amount of 0°1 to 100 parts by weight of the pigment.
30 parts by weight are used. If it is less than 0.1 part by weight, effects such as dispersion will not be sufficient and the reproduction of the transferred image as an image forming material in the present invention will be stable.

In addition, a sufficient effect on two-color reproducibility cannot be expected without causing nonuniform reflection density, periodic patterns, or fine directional patterns in the transferred image. Moreover, even if it exceeds 30 parts by weight, an effect commensurate with the amount used cannot be expected, and furthermore, it depends on the type of organic dye derivative.

Due to the possibility of adverse effects due to organic dye derivatives,
Undesirable.

The organic pigment derivative can be added by mixing the pigment with the pigment in advance using a device such as a Nauta mixer (manufactured by Micron for wires), and then adding and dispersing this mixture into the photosensitive shoe fluid. A method of mixing pigment derivatives, preparing a concentrate of the pigment with this mixture and a photosensitive layer solution, and adding this by diluting it to a desired concentration; This is carried out by method 1, etc., in which they are added simultaneously or separately when producing.

The amount of pigment added in the photosensitive layer is 2-5% of the total solid content.
0% (by weight) is appropriate; if it is less than 32%, the amount of coating will be too large to obtain the required density, and the transferred image will tend to deteriorate; if it exceeds 50%, actinic light does not penetrate sufficiently, causing background stains. Also,
The coating amount of the photosensitive layer is 0.5 g/m ~ 10 g/m
m, preferably Ig/m to 5 g/rrr. Image exposure is done after removing the protective film.

There are two possible methods: one in which the photosensitive layer and the mask are brought into close contact with each other and exposed to light, and one in which exposure is carried out from the support side.

When exposing the image by directly contacting the photosensitive layer and mask,
The coating amount of the photosensitive layer may be 10 g/rrr or more.

The orientation of the resulting layers is reversed, making it extremely difficult to observe images that include a single character or the like.

In addition, it is also effective to provide a suitable matte treatment to the photosensitive layer in order to obtain a good texture if necessary.

On the other hand, when performing three-image exposure from the support side.

The resulting image is a normal image, but the amount of photosensitive layer applied is limited.

If it exceeds 10 g/rd, the transferred image tends to be smeared.

Furthermore, a protective film (cover sheet) is layered on the photosensitive layer, and a suitable material for the protective film is a polyethylene film as described in JP-A-48-31323. It serves as a suitable cover sheet because its adhesive properties are weaker than base supports such as polyethylene terephthalate film. It is also known that in photopolymerization systems, the polymerization rate changes due to oxygen in the air, and to prevent this, a coating film such as polyvinyl alcohol is created on the colored photosensitive layer. ,
Either method of coating with a protective film is effective, but when creating a coating, if the thickness of the coating becomes 5 μ or more, it will adversely affect the quality of the transferred image. , a method in which a protective film is laminated is more preferred.

In the present invention, an image forming method in which image exposure is performed from the support (mostly transparent) side is preferred.

This method significantly improves the positional relationship such as the orientation of the nine images, and provides a method that does not require a special intermediate image receptor for the purpose of correcting the orientation of the two images.

In the present invention, in the case of an image forming material having a protective film, the transparent support refers to a material that is peeled off after being pressed onto an image receptor, and the image exposure is performed from the transparent support side.

The protective film provided as necessary prevents staining of the photosensitive layer from adhering to the exposure device, etc. when exposing the support for image formation, and reduces the effects of oxygen on the photosensitive layer. be.

In the color proofing work of printed matter to which the present invention is applied,
Highly accurate image reproduction from the original film, etc. is required. At the same time, there is also a need to shorten the time required for color calibration work. To meet these demands and ensure stable finish quality.

Regarding the accuracy of the reproduced image position and the correspondence between the two front and back sides, it is preferable to use a simple working process, that is, to perform exposure from the transparent support side.

Hereinafter, one example of the process of using the present invention as an image forming material for color proofing, for example, will be explained step by step.

(The 11-color separation image mask and the image forming material are provided with holes for register pins. Furthermore, if the image receptor is paper or the like, holes for register pins are also provided in these image receptors.

(2) imagewise exposure, that is, exposing the photosensitive layer to a color separation mask image using actinic radiation, such as ultraviolet radiation, sufficient to cure the imaging material;

(3) Next, peel off the protective film of the second image forming material.

The image receptor and the surface of the peeled colored photosensitive layer are placed so as to face each other, and transfer is performed under pressure and/or heat.

(4) By holding one end of the support and peeling it off, the image formed on the photosensitive layer is transferred to the image receptor, and 1/3 or an appropriate amount in the film thickness direction is supported by the preset internal concentration force. It is left on the body, forming a transferred image.

(5) Post-exposure is performed for the purpose of strengthening the adhesion to the entire surface of the transferred image and eliminating viscosity on the surface of the transferred image.

The above steps (11 to (5)) are repeated two times, for example, four times (yellow, magenta, cyan, black) for color proofing to obtain a four-color reproduced image.

Incidentally, the receptor mentioned above includes art, coated paper, etc., which are the materials used for proof stamps.

These examples are not intended to limit the invention.

In the present invention, as the step (3) above, it is also possible to press and bring them into close contact with each other in a two-dimensional manner depending on the conditions.

Preferably, transfer is performed between rollers or by a manual printing machine. This transfer method allows for quick and stable contact, transfer and peeling.

Furthermore, temperature unevenness during heating is less than when transferring on a flat surface.

Transfer is usually performed by applying pressure and heating, but only applying pressure may be used. In addition, when heating, it is preferable to heat to such an extent that the image receptor used does not expand or contract significantly. For example, heating the roller to a surface temperature of about 50 to 150°C, preferably about 60 to 100°C, gives preferable results by increasing the transfer speed and improving the reproduction accuracy of fine images.

As a device for performing the transfer, a conventional laminator or the like may be used to perform the transfer and peeling in the present invention.

In addition, in the method using a developer, sodium hydroxide,
Basic aqueous developers such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium phosphate, and triethanolamine are used.

A photosensitive layer that can be developed with this developer is selected. blue.

After development, the film is usually washed with water and dried.

The present invention will be explained below with reference to Examples. In the examples, 2 parts means parts by weight, and 1% means % by weight.

Example 1 Nine photosensitive layer liquids having the following composition were dispersed and mixed.

It was adjusted.

Diallylisophthalate prepolymer 21.23 parts (Osaka Soda-Daiso Isodap M n 45000)
dipentaerythritol hexaacrylate DPHA (
(manufactured by Nippon Kayaku ■) 7.08 parts Addition polymerization initiator Hensiphenone 0.5 parts 4
．． 4 Bis-diethylaminobenzophenone (manufactured by EAB Hodogaya Chemical ■) O, 1.7 parts Hydroquinone 0.001 part Carbon blank MA-7 (manufactured by Mitsubishi Chemical Corporation 11) 5
．． 0 parts di(N,N-dimethyl-1,3-propanediaminosulfonyl)copper phthalocyanine 0.5 =
n Toluene 38.0 parts Methyl ethyl ketone 40.0 parts Also. Carbon black and di(N.

N-dimethyl-1,3-propanediaminosulfonyl)
Instead of copper phthalocyanine, use Onol Yellow FC; 1310 for yellow, barium salt of a coupling product of acetoaceto-toluidide (AAOT) and 3-nitro-4-aminobenzenesulfonic acid, and Onol Red for magenta. 78FG4412 and p-
Coupled products of aminobenzoic acid and aphthol AS, cyanide Onol Blue FG7330 and 2-carboxybenzamidomethyl copper phthalocyanine (the above,
Photosensitive layer liquids for yellow, red, and type were prepared using Toyo Ink Mfg. aI), respectively. The usage ratio of pigments in each photosensitive layer is 18% for yellow and 1% for red.
8% and indigo 18%.

This photosensitive layer solution was applied to a polyethylene film (thickness: 40 μm) as a protective film using a bar coater, and dried by irradiation for 30 seconds under an infrared lamp (3 parts W) to form a positive photosensitive layer. Created. The coating amount at this time was 2 μm (
dry film thickness).

Further, a polyethylene film was laminated on the photosensitive layer at 30° C. to obtain each image forming material.

Accurately align the image forming materials of each of the four colors and the corresponding color separation positive films using register pins, and heat them for 30 seconds (equivalent to 100 mj/cm2) using a 1.5 part W ultra-high pressure mercury lamp (manufactured by Ushio Inc.). Image exposure was performed.

Next, peel off the polyethylene film of the protective sheet 2
Art paper, which is an image receptor, and a photosensitive layer.

The rollers make contact and transfer at the nip between them.

After further peeling and post-exposure, the result was exactly the same as a normal print (printed by this machine). A faithful reproduction of 50 wood/mm was obtained, corresponding to the image on the color separation positive film.

In the imaging material, all of the colored photosensitive layer and a portion of the uncolored photosensitive layer, corresponding to about 9/10, were transferred to the image receptor.

The feeding speed was 50 cm/min, and the nip pressure between the rollers was 4.
Kg/cm2. The temperature of the upper roller is 48
℃.

The temperature at the bottom was 97°C.

Further, the diameter of the upper and lower rollers is 150 mm.

The Shore hardness A of the upper roller is 70. The width of the transferred object is 260 mm, the contact distance, and the contact interval is 10 m.
m, is.

In addition, when images were formed three times and the images were compared, they were all uniform and indistinguishable.

Example 2 When phthalimidomethyl copper phthalocyanine or tetrachlorocopper phthalocyanine was used as an organic dye derivative for the cyan pigment of Example 1, results almost similar to those of Example 1 were obtained.

Comparative Example 1 In Example 1, image forming materials were prepared in which the same pigment was used instead of the organic dye derivative in the photosensitive layer.

As for the photosensitive liquid, when Example 1 and Comparative Example 1 were compared, Example 1 had a low viscosity, and no increase in viscosity or pigment precipitation was observed over time (1 month). On the other hand, in Comparative Example 1, viscosity increase and pigment precipitation were observed after one week.

Using the image forming material of Comparative Example 1, imagewise exposure was carried out in the same manner,
After peeling off the protective film and superimposing the image on art paper as an image receptor, the image was transferred in the same manner.

Approximately two-thirds of the colored photosensitive layer is transferred and with the same imaging material. In the repeated image formation three times, the 1 coloring strength was reduced by about 10% compared to Example 1. Note that the resolution was 50 mm/mm.

Example 3 The image forming material of Example 1 was image exposed, the protective sheet was peeled off, it was fixed to a blanket cylinder, the blanket cylinder was rolled to overlap one image-receiving layer of art paper, and the image was transferred simultaneously. Using a flatbed proofing machine equipped with a heating device on a sheet surface plate, the temperature was 100°C and the pressure was 4 kg/
Cm2. Transfer was performed under conditions of a transfer time of 1 minute.

The finish was almost the same as the printed version.

Example 4 A photosensitive outer layer solution having the following composition was prepared.

Polyester (Vylon 300 manufactured by Toyobo) as a polymer, tetraethylene glycol diacrylate (A-4EC manufactured by Shin-Nakamura Chemical) as a monomer, trimethylolpropane triacrylate (ATMPT) as a monomer
(manufactured by Shin Nakamura Chemical) and 2-hydroxy-2-methyl-propiophenone (Procure 11F3, manufactured by Merck & Co., Ltd.) was used as an initiator.

In addition, as a pigment, yellow mmsu Onor Yellow PC,
1310 (manufactured by Toyo Ink Manufacturing Co., Ltd.), Onor Red 7BFG4412 for magenta (manufactured by Toyo Ink Manufacturing Co., Ltd.)
, Onor Blue FG7330 (manufactured by Toyo Ink Manufacturing) for cyan or Mitsubishi Carbon MA7 for black. And the organic dye derivatives shown in Example 1 were used for each pigment.

Dissolve the polymer in MEK (methyl ethyl ketone) (3 parts polymer, 7 parts solvent). This was left at room temperature for 72 hours or shaken for 48 hours to prepare a polymer solution.

The monomers are then mixed into the polymer solution. 1 part of A-4EG, 3 parts of ATMPT, 20 parts of polymer (
However, a photosensitive solution was prepared by adding an initiator (3% of the solute) and an initiator (no solvent was included).

How to mix pigment into the prepared photosensitive layer solution.

Repeat shaking with Red Devil 5 times. During this time, it is also preferable to add a solvent or the like to maintain appropriate fluidity.

The ratio of pigment used in the photosensitive layer is 18% for yellow when used as a color proofing material for printing.

They are 18% for magenta, 18% for cyan, and 9% for black. After kneading with Red Devil, each photosensitive layer was coated on a polyethylene film (40μ thick) using a bar coater and dried by irradiation for 30 seconds under an infrared lamp (3kW) to create a positive photosensitive layer. . The coating amount at this time was 2μ (dry film thickness).

The image forming materials of each of the four colors were subjected to image exposure in the same manner as in Example 1, and the polyethylene film was peeled off.

As in Example 1, the photosensitive layer was transferred between rollers so as to be in close contact with white paper, and then peeled off and post-exposed to form an image.

40 lines/corresponding to the image on color separation positive film
A faithfully reproduced image of mm was obtained. In addition, in the image forming material of Example 4, about 9/l O of the photosensitive layer was transferred.

Thereafter, the same process is performed for the other three colored photosensitive layers to sequentially form images of YM-C-K (yellow, magenta, cyan, and black).

We created an image with a texture that closely resembles that of commonly used printed matter.

Example 5 A photosensitive outer layer solution having the following composition was prepared.

Styrene-monobutyl maleate copolymer resin, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, benzophenone.

4.4-bis-diethylaminobenzophenone, 2゜2
-methylenebis (using 4-ethyl-6-t-butylphenol, benzotriazole, methyl ethyl ketone,
A solution was prepared using the same pigment and organic dye derivative as in Example 3.

Image-forming materials for each of the four colors consisting of polyethylene terrestrial film/photosensitive layer/polyethylene film were subjected to image exposure in the same manner as in Example 1, the polyethylene film was removed, and the material was developed with a 2% aqueous sodium carbonate solution.

The four-color image was transferred to art paper in the same manner as in Example 1.

Claims (1)

[Scope of Claims] 1. A photosensitive layer containing a pigment is formed on a support, and an image is formed by imagewise exposure and development, or an exposed area and an unexposed area of the photosensitive layer are formed. In an image forming material that causes a difference in tackiness during transfer and transfers an image to an image receptor such as paper, the photosensitive layer contains 0 of an organic dye derivative represented by the general formula [I] based on 100 parts by weight of pigment.
．． An image forming material comprising 1 to 30 parts by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, Q is an organic dye residue, X_1 and X_2 are different from each other, and hydrogen atoms and halogen atoms (when X_1 and X_2 are hydrogen atoms and halogen atoms, respectively) , j, which is the number of halogen atoms, is 2 or more) or the substituents shown below, i and j each independently represent an integer of 1 to 4. -COOM/l, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ -SO_3M/l, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Or, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Y is a hydrogen atom , halogen atom, -NO_2, -
NH_2 or -SO_3H, M is a hydrogen atom or a metal atom, A is -SO_2-, -(CH_2)_n- or -CH_2NHCOCH_2-, R_1, R_2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or R_1 and R_2 to form a heterocycle, R_3,
R_4, R_5, R_6 are hydrogen atoms (R_3, R_4,
R_5, R_6 are all hydrogen atoms) or an alkyl group having 1 to 30 carbon atoms, k is an integer of 1 to 4,
l is the valence of M, m and n are integers of 1 to 8]. 2. The image forming material according to claim 1, wherein the photosensitive layer contains a photopolymerizable compound and a non-photopolymerizable organic polymer binder.