JPH0782234B2 - Image forming material - Google Patents

Description

The present invention relates to a negative or positive type image forming material used for printing plates, return films, color test prints, color proofs, dry film resists and the like. .

"Prior Art" Image forming materials conventionally used in various fields such as printing, photography and fine processing of metal are basically called a support (in transfer type image forming materials, also called a temporary support). And a photosensitive resin layer made of a photopolymer provided thereon.

For example, a transfer type image forming material (photosensitive transfer sheet) having such a configuration is used for color proofing. A color proofing sheet for color proofing is formed by exposing and developing an image forming material through a decomposition mesh film for each color plate to form a decomposed image on a photosensitive resin layer, and observing this sheet as it is or by decomposing it. It can be obtained by transferring an image onto an arbitrary support (image-receiving surface). A multicolor image can also be obtained by repeating the step of transferring a separated image of another color onto the support.

Further, in order to simplify the transfer process, an image forming material having a release layer provided between a support and a photosensitive resin layer is also known (Japanese Patent Publication No. 49-441 and Japanese Patent Publication No. 47-47). (See No. 41830, etc.).

In any case, the image-forming material essentially consists of a support and a photosensitive resin layer, and if necessary, a protective layer is provided on the photosensitive resin layer. Be seen. That is, after coating a coating solution for the photosensitive resin layer (hereinafter, abbreviated as photosensitive solution) on a support made of a long sheet of polyethylene terephthalate or the like, it is heated and dried at a constant temperature (drying step), It is manufactured by continuously winding as it is (winding step). When the protective layer is provided, it is manufactured by winding the film once and then applying a coating solution for the protective layer onto the photosensitive resin layer and drying. Further, the wound image forming material is subjected to post-processing such as cutting into a desired standard size (processing step) and commercialized.

When exposing the image forming material, it is usual to use ultraviolet rays. When the ultraviolet light incident on the image forming material is scattered to the unirradiated portion, in the case of the negative type image forming material, the image portion is thick or defective development is not made in the high dot portion (shadow area), and the positive type image forming material. In this case, the image portion becomes thin, or the dot jump phenomenon occurs in the highlight portion. As a countermeasure for this, a method of providing an anti-halation layer on the lower side of the photosensitive photoresist composition layer or on the back side of the support and adding an ultraviolet absorber and, in some cases, a dye or a pigment is considered, but the number of layers is increased. There is a drawback that the manufacturing cost is high. As another measure, there is a method of adding an ultraviolet absorber to the photosensitive photoresist composition layer, but in the conventional ultraviolet absorber, the sensitivity is greatly reduced when it is added so as to prevent halation, which is a photosensitive photoresist. There are problems that the composition is transferred to the surface of the composition layer and the effect is lost, or that the ultraviolet absorber itself has absorption in the visible portion and is colored.

"Problems to be Solved by the Present Invention" It is an object of the present invention to provide an image forming material which is inexpensive, has little reduction in sensitivity, and has a sufficient antihalation effect.

"Means for Solving Problems" The object of the present invention is to coat a photosensitive photoresist composition layer containing a dye or pigment on a support, or to form a coloring material layer containing the dye or pigment. In a photosensitive image-forming material formed by laminating a photosensitive photoresist composition layer, the photosensitive photoresist composition layer contains an ultraviolet absorber represented by the following formula (1). Achieved by the forming material.

2- [2-hydroxy-3,5-bis (α, α'-dimethylbenzyl) phenyl] -2H-benzotriazole Molecular weight: 447.6 Melting point: 135-143 ° C Specific gravity (20 ° C): 1.22
Vapor pressure (20 ° C.): 2.1 × 10 ⁻¹⁰ Pa Maximum absorption wavelength: 346 nm Trade name: TINUVIN 234 The following are ultraviolet absorbers (2) to (6) having similar structures as comparative compounds.

2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole Molecular weight: 323.4 Melting point: 152-156 ° C Specific gravity (20 ° C): 1.18
Vapor pressure (20 ° C): 7.2 × 10 ^-6 Pa Maximum absorption wavelength: 345 nm Product name TINUVIN 320 Sumisorb 320 Viosorb 582 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole Molecular weight: 315.8 Melting point: 137-141 ° C Specific gravity (20 ° C): 1.32
Vapor pressure (20 ℃): 7.5 × 10 ^-7 Pa Maximum absorption wavelength: 353 nm Product name TINUVIN 326 Sumisorb 300 Viosorb 550 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole Molecular weight: 357.9 Melting point: 154-158 ° C Specific gravity (20 ° C): 1.26
Vapor pressure (20 ℃): 1.1 × 10 ^-6 Pa Maximum absorption wavelength: 352 nm Product name TINUVIN 327 Viosorb 580 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole Molecular weight: 351.5 Melting point: 80 ℃ or more Specific gravity (20 ℃): 1.17 Vapor pressure (20 ℃): 4.7 × 10 ^-6 Pa Maximum Absorption wavelength: 346 nm Product name TINUVIN 328 Sumisorb 350 Viosorb 591 Vapor pressure (20 ℃): Approx. 10 ^-5 to 10 ^-6 Pa Product name Sumisorb 340 Viosorb 583 The preferred addition amount of this ultraviolet absorber is 0.1 to 1 m ²
1000 mg, more preferably 2-500 mg, even more preferably 20
~ 200 mg. Preferably, it is added so that the ultraviolet transmittance of the photosensitive photoresist layer is 50% to 59%. The greater the amount of ultraviolet light transmitted, the smaller the decrease in sensitivity.
It is desirable that the amount of the absorbent added is as small as possible, and when a photosensitive photosensitive photoresist layer is used, it is preferably 0.01 to 10000% of the photopolymerization initiator.

A typical image forming material of the present invention is a photosensitive photoresist composition layer containing a dye or a pigment coated on a transparent support, or a coloring material layer containing a dye or a pigment and a photosensitive photoresist composition. However, the present invention is not limited to this. For example, a back layer and / or a protective layer may be provided, and the support and the photosensitive photoresist layer may be combined with each other. The structure may be such that various intermediate layers are provided between them. The image forming material of the present invention having the above constitution can be produced, for example, by the method described below.

As the material of the support, a substance that is chemically and thermally stable and has flexibility is used. It may be actinic light transmissive if necessary. Specifically, polyethylene, polypropylene and other polyolefins, polyvinyl chloride, polyvinylidene chloride and other polyvinyl halides, cellulose acetate, nitrocellulose, cellophane and other cellulose derivatives, polyamides, polystyrene, polycarbonate, polyimides. Examples include polyester. Of these, particularly preferred is a biaxially stretched polyethylene terephthalate film which is excellent in dimensional stability and transparency.

A back layer can be provided on the surface of this support opposite to the side where the photopolymerizable photosensitive resin layer is provided. An example of the back layer is a layer in which a matting agent is contained and supported in a dispersed state in acetyl cellulose. Examples of acetyl cellulose include monoacetyl cellulose, diacetyl cellulose, triacetyl cellulose, and acetylbutyl cellulose. Acetylcellulose has a degree of acetylation (degree of acetylation) of 40 to 60%.
It is preferable that the average degree of polymerization is 50 to 400.
It is preferably within the range.

As the matting agent, for example, silicon dioxide (including colloidal silica), aluminum oxide, aluminum silicate, aluminum hydroxide, titanium dioxide, calcium carbonate, fine particles of inorganic compounds such as zinc oxide, and insoluble in solvents such as cross-linked polystyrene Examples of the organic polymer include the fine particles. The average particle size of these matting agents varies depending on the layer thickness of the backing layer, but is 0.005-10 μm.
It is preferably in the range of m. The matting agents may be used alone or in combination of two or more kinds.

The ratio of acetyl cellulose to matting agent is preferably adjusted so that the content ratio of matting agent to acetyl cellulose is in the range of 1 to 60% by weight. If the content ratio of the matting agent exceeds this range, the adhesion between the backing layer and the support may become insufficient. In forming the backing layer, first, the acetyl cellulose and the matting agent are mixed using a suitable solvent to prepare a coating solution. Examples of the solvent in this case include acetone, methyl ethyl ketone,
Examples thereof include ketones such as cyclohexane; acetic acid esters such as methyl acetate and ethyl acetate; ethers such as methyl cellosolve, dioxane and tetrahydrofuran; and methylene chloride and diacetone alcohol.
These may be used alone or as a mixed solvent of two or more kinds.

The backing layer can be formed by coating the coating solution on the support using a conventional method and drying.

If necessary, an etching agent such as resorcin or an anti-halation agent may be added to the coating liquid for the purpose of enhancing the adhesion to the polyethylene terephthalate (support).

The layer thickness of the back layer is generally preferably in the range of 0.01 to 5 μm, particularly preferably in the range of 0.1 to 0.5 μm.

Next, a photosensitive photoresist composition layer is provided on the other side of the support. When the photosensitive photoresist composition layer is a photopolymerizable photosensitive resin layer, it is usually 15 at normal pressure.
A monomer compound such as a polyfunctional vinyl monomer or vinylidene compound having a boiling point of 0 ° C. or higher and capable of forming a photopolymer by at least one addition polymerization, an organic polymer binder, and photopolymerization activated by actinic rays. It consists of an initiator, and a thermal polymerization inhibitor is added if necessary.

The vinyl monomer or vinylidene compound that can be used to form the photopolymerizable photosensitive resin layer is preferably, for example, an unsaturated ester of polyol, particularly an ester of acrylic acid or methacrylic acid. Specific examples include ethylene glycol diacrylate, glycerin triacrylate, polyacrylate, ethylene glycol dimethacrylate, 1,
3-propanediol dimethacrylate, polyethylene glycol dimethacrylate, 1,2,4-butanetriol trimethacrylate, trimethylolethane triacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol Diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, 1,3-propanediol diacrylate, 1,5-pentanediol dimethacrylate, 200
Mention may be made of bisacrylates, bismethacrylates and similar compounds of polyethylene glycol having a molecular weight in the range from to 400.

An unsaturated amide can also be used as the monomer compound, and examples thereof include unsaturated amides of acrylic acid and methacrylic acid having α, ω-diamine, and ethylenebismethacrylamide. The alkylene chain of the unsaturated amide may be opened by carbon atoms. However, the photopolymerizable monomer is not limited to these compounds.

Examples of the photopolymerization initiator include benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, Aromatic ketones such as 2-ethylanthraquinone, phenanthraquinone, and other aromatic ketones; Benzoin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; 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- (o-methoxyphenyl) -4,5-diphenylimidazole dimer , 2- (p-methoxyphenyl)-
4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer,
2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer, and U.S. Pat. No. 3,479,185. No. 3,784,557, British Patent 1,047,56
Mention may be made of 2,4,5-triacrylimidazole dimers as described in the respective specifications of No. 9.

As the organic polymer binder, vinyl polymer materials are particularly preferable from the viewpoint of compatibility with the above-mentioned monomer compound and photopolymerization initiator. Examples of vinyl-based polymer substances include:
Various substances such as polyvinyl chloride, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polymethacrylic acid, polymethyl methacrylate, polyvinyl ether, polyvinyl acetal and their copolymers are listed. However, the present invention is not limited to these.

Here, the mixing ratio of the monomer compound and the organic polymer binder, the appropriate ratio also varies depending on the combination of the monomer compound and the organic polymer binder used, but generally 1:
A range of 10 to 2: 1 (weight ratio) is preferable. Also at this time,
The addition amount of the photopolymerization initiator is preferably 0.01 to 20% by weight based on the weight of the monomer compound used.

Examples of the thermal polymerization inhibitor include p-methoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, tert-butylcatechol, pyrogallol, naphthylamine, β-naphthol, phenathiazine, pyridine, nitrobenzene, o-toluquinone, arylphosphite. However, the present invention is not limited to these.

In addition, when the photosensitive photoresist composition layer is a photodissociation resin layer, it is disclosed in US Pat.
No. 8, and 3,647,443 orthoquinonediazide compounds, compounds having an orthoester group in the main chain described in JP-A-56-17345, JP-A-60-37549
And compounds having a silyl ether group in the main chain.

In this case, the organic polymer binder is not always necessary, but a novolak type phenol resin or the like can be used. The binder can be used in the range of about 40 to 90% by weight of the photodissociation resin layer.

The layer thickness of the photosensitive photoresist composition layer is generally 0.1 to 1.
It is in the range of 50 μm, preferably in the range of 0.5 to 100 μm.

For the details of the material for these photosensitive photoresist composition layers and the method for forming the same, see, for example, Japanese Examined Patent Publication No.
46-35682, JP-A-47-41830, 48-93337, 49
-441, 51-5101, 59-97140 and the like.

When a coloring substance is used, the coloring substance may be contained in the photosensitive resin layer, or a coloring material layer may be separately provided and contained therein. The color material layer can be provided on either the upper part or the lower part of the photosensitive photoresist composition layer, but from the viewpoint of the sensitivity (photopolymerization) of the photosensitive resin layer in the image exposure step, it is formed on the color material layer. It is preferred to provide a photosensitive photoresist composition layer. Known pigments and dyes can be used as the coloring substance. For details of the coloring substance and the coloring material layer, see, for example, JP-A-59
-97140 publication.

Further, the image forming material of the present invention may be provided with a protective layer having low oxygen permeability in order to prevent the sensitivity from being lowered by oxygen. The protective layer can be formed, for example, by applying a solution of a polymer substance such as polyvinyl alcohol, polyvinyl acetate, a copolymer of methyl vinyl ether / maleic anhydride, polyvinyl pyrrolidone, gelatin, gum arabic, and drying. The thickness of the protective layer
0.1-5 μm, preferably 0.2-3 μm, more preferably
0.2 to 2 μm.

If necessary, various matting agents, slip agents, antistatic agents and the like can be added to the protective layer.

In the present invention, the ultraviolet ray transmission amount is defined as follows. The absorption spectrum of 325 to 425 nm of the sample with strong ultraviolet absorption and the sample without strong ultraviolet absorption were measured, and the total transmission amount in this wavelength range of each sample was obtained.The transmission amount of the former when the transmission amount of the latter was 100. And

The degree of effect of the ultraviolet absorbent of the present invention depends on the type and amount of the coloring material used. That is, when a large amount of a coloring material having a large absorption in the above wavelength range is used, the coloring material itself exhibits the effect of the ultraviolet absorbent, and therefore the effect of the separately added ultraviolet absorbent of the present invention is notable. It does not appear.
On the other hand, the effect is more remarkable when the coloring material has a small absorption in this wavelength range, or when the absorption is large but the amount of the coloring material used is small.

The effect of adding the ultraviolet absorbent of the present invention is remarkable when the ultraviolet transmittance of the sample having the coloring material layer containing no ultraviolet absorbent is measured in the above wavelength range and the ultraviolet transmittance is about 5% or more. Appear in.

The present invention will be described below based on examples.

Example 1 A solution having the following composition was prepared as a coating liquid for forming a back layer.

Coating solution for backing layer Resorcin (Etching agent) 2.8Kg Diacetyl cellulose (Acetification degree: 55 ± 0.5%, Average degree of polymerization: 160 Acetate Flex V-AC, Daicel Corp.
0.3Kg Silicon dioxide (average particle size: 40nm, TT-600, manufactured by Nippon Aerosil Co., Ltd.) 0.1Kg Methanol 8Kg Methyl ethyl ketone 30Kg This coating solution is applied to polyethylene terephthalate film (support, thickness: 100μm, length: 2000m) ) Apply evenly on
After drying (drying temperature: 120 ° C.), a backing layer having a dry film thickness of 0.3 μm and substantially consisting of diacetyl cellulose and silicon dioxide was provided and then wound.

Next, as a coating liquid for forming a photosensitive photoresist layer,
A solution having the following composition was prepared. In this case, a color material dispersion liquid having the following composition was prepared separately and mixed.

Color material dispersion color material 9.8Kg benzyl methacrylate / methacrylic acid copolymer (molar ratio: 72/27, limiting viscosity of methyl ethyl ketone solution at 25 ° C: 0.12cps) 16.4Kg methyl ethyl ketone 36.9Kg methyl cellosolve acetate 36.9Kg where: As color materials, yellow: Seikafuast Yellow H-0755 (Dainichi Seika Co., Ltd.) Magenta: Seikafuast Carmine 1483 (Dainichi Seika Co., Ltd.) Cyan: Cyanine Blue 4920 (Dainichi Seika Co., Ltd.) Using.

The dispersion was prepared for 6 hours using a test disperser (Paint Shaker manufactured by Toyo Seiki Co., Ltd.).

The coating solution for photosensitive photoresist layer was subjected to ultrasonic dispersion for 10 minutes after stirring for 10 minutes.

Coating solution for photosensitive photoresist layer Methyl ethyl ketone 15Kg Methyl cellosolve acetate 7.4Kg Benzyl methacrylate / methacrylic acid copolymer (molar ratio: 72/27, 25 ° C methyl ethyl ketone solution intrinsic viscosity: 0.12cps) 4.5Kg pentaerythritol tetraacrylate 5.5Kg Michler's ketone 0.15Kg 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole 0.15Kg Silicon dioxide 0.4Kg (# 266, manufactured by Fuji Devison Co., Ltd.) Material dispersion 24Kg UV absorber 0.5Kg The photosensitive photoresist layer forming coating solution thus prepared is applied to the surface of the support opposite to the back layer and dried (drying temperature: 100 ° C). The dry film thickness is 2.4 μm
The photosensitive photoresist layer of was prepared and wound up.

Separately, a coating solution for forming a protective layer having the following composition was prepared, and the coating solution was applied on the photosensitive photoresist layer and dried (drying temperature: 100 ° C.) to give a dry film thickness of 1.5 μm. A protective layer was provided.

Coating solution for protective layer Polyvinyl alcohol 6Kg (GL-05H, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) Water 97Kg Methanol 3Kg The image-forming material thus obtained was evaluated by the following method.

(1) Thick image area When the Fuji Control step wedge (ΔOD = 0.15) is used and the exposure is twice as much as the standard exposure that gives 5 solid steps, the original is 10% halftone dot I compared the fatness of the part with the original manuscript in dot size. Overweight evaluation 1% or less A class 1% or more and 3% or less B class 3% or more and 5% or less C class 5% or more D class Practically C class or higher, preferably B class or higher, and more preferably A class Is good.

(2) Defective development in high-dot area A defect of 90% half-tone non-image area was examined when exposed and developed under the same conditions as in (1).

Failure evaluation 0% (completely missing) A class 0% to 1% or less B class 1% to 3% or less C class 3% or more D class Practically C class or more, preferably B class or more However, A class is more preferable.

(3) Fluctuation of sensitivity The fluctuation of sensitivity was examined from the fluctuation of the number of solid steps when exposed and developed under the same conditions as (1). Sensitivity fluctuation evaluation Within ± 1 step A class Within ± 2 steps B class Within ± 3 steps C class Over ± 3 steps D class Practically better than B class, more preferably A class.

Table 1 shows the evaluation results. From this, in the samples 1 to 3 according to the present invention, good performance is obtained as compared with the comparative samples 4 to 18 containing the ultraviolet absorbers (2) to (6) and the comparative samples 19 to 21 containing no ultraviolet absorber. I understand. The exposure light source used was a 2 Kw ultra-high pressure mercury lamp Jetlite 2000 (Oak Seisakusho), and the developer used had the following composition.

NaOH 6 g Surfactant (Kao Atlas, Perex NBL) 100 g Distilled water 900 g Example 2 Mother liquors A and B for pigment dispersions having the following formulations were prepared.

Mother liquor A Copolymer of styrene and maleic anhydride 20 g Normal propanol 80 g Mother liquor B Methoxymethylated nylon 10 g (Toresin MF-30 Teikoku Kagaku) Methanol 90 g Next, using mother liquors A and B, a three-color pigment dispersion of the following composition Was prepared.

Dispersion was performed for 6 hours using a test disperser (Paint Shaker manufactured by Toyo Seiki Co., Ltd.). Next, a diluted pigment dispersion having the following formulation was prepared.

Diluted solution Normal propanol 40g Acetone 28g Fluorosurfactant 0.2g (Florard FC-430) Three color pigment dispersions are diluted with the above diluents in the weight ratios shown in the table below, then stirred for 10 minutes and ultrasonic dispersed for 10 minutes. Then, a coating material for the color material layer was obtained. After applying the color material layer coating solution on a Toyo Paper No. 63 filter, apply it on a biaxially stretched polyethylene terephthalate film with a thickness of 100 μm using a whaler, and apply 100
It dried at 2 degreeC for 2 minutes, and created the color material layer of each of three colors.

Hue Pigment Dispersion / Film Thickness Filter Optical Density Further, a positive type photosensitive solution having the following composition was applied on each color material layer of each of the three colors with a No. 63 filter after the error and dried at 100 ° C. for 2 minutes to prepare a colored photosensitive sheet for each of the three colors. .

Positive-working photosensitive solution 15 g of condensation product of acetone and pyrogallol (average degree of polymerization 3) and 2-diazo-1-naphthol-4-
Adduct with Sulfonyl Chloride Novolac-type phenol-form 30 g Aldehyde resin (Sumitomo Deyures Co., Ltd., PR-50904) Cyclohexanone 120 g n-Propyl acetate 280 g UV absorber 2.5 g Image formation thus obtained The material was evaluated by the following method.

(4) Image thinning Original when exposed and developed under the same conditions as (1)
The 10% halftone dot area was compared with the original manuscript by dot size. Fineness evaluation 1% or less A class 1% or more and 3% or less B class 3% or more and 5% or less C class 5% or more D class Practically C class or more, preferably B class or more, more preferably A class good.

(5) Sensitivity fluctuation Using the same control step wedge as in (1),
A variation in sensitivity was examined from a variation in the number of solid steps by giving an exposure amount three times as much as a standard exposure amount giving a number of clear steps of 5. Sensitivity fluctuation evaluation Within ± 1 step A class Within ± 2 steps B class Within ± 3 steps C class Over ± 3 steps D class Practically better than B class, preferably A class.

Table 2 shows the evaluation results. From this, in the samples 22 to 24 according to the present invention, the ultraviolet absorber ( It can be seen that good performance can be obtained as compared with Comparative Samples 25 to 39 containing 2) to (6) and Comparative Samples 40 to 42 containing no ultraviolet absorber.

Continuation of the front page (56) Reference JP 62-67531 (JP, A) JP 59-214847 (JP, A) JP 58-68741 (JP, A) JP 61-20024 (JP , A) JP 62-210443 (JP, A)

Claims (4)

[Claims] 1. A photosensitive photoresist composition layer containing a dye or a pigment is coated on a support, or a coloring material layer containing a dye or a pigment and a photosensitive photoresist composition layer are laminated. An image forming material comprising the compound (1) having the following structure in the photosensitive photoresist composition layer. 2. The image forming material according to claim 1, wherein the photosensitive photoresist layer is a photopolymerizable composition. 3. The image forming material according to claim 1, further comprising an ultraviolet absorber so that the ultraviolet transmittance of the photosensitive photoresist layer is 50% or more. 4. The image forming material according to claim 1, wherein the photosensitive photoresist layer is dry laminated with a cellulose acetate film, a polypropylene film or a polyester film.