JPS5931943A - Image forming material - Google Patents

Abstract

PURPOSE:To obtain an image forming material having a mask layer enhanced in resistance in org. solvents, by incorporating a colorant, a polymer soluble in a developing soln., and an inorg. binder in the mask layer on a support. CONSTITUTION:The mask layer formed on the support of the image forming material contains a colorant, a polymer soluble in a developing soln., and an inorg. binder. The colorant has an absorption band, preferably, within 300-400nm or 400-600nm wavelength region in exposure to light of a light source, like examples of carbon black, graphite, iron black, or aniline black. Said polymer soluble in the developing soln. means polymers soluble in water or aq. solns, such as cellulose derivs. like methyl or hydroxyethyl cellulose, polymethacylate, addition polymers having carboxyl groups on the side chains like (meth)acrylate copolymers. The inorg. binder is incorporated in the mask layer in order to give resistance to org. solvents.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to improvements in imaging materials. Correction 7-11
This article describes a novel photosensitive material for image formation in which the organic solvent resistance of the first mask layer is improved by containing a specific substance in the first layer.

Conventionally, image-forming materials suitable for halftone images and plots have been mainly used for lithium film (lithium film produced by silver halide emulsion), ρ-genization Ginsha (silver copy) has been used as a material, but in recent years, printing materials have been used.
) Y: As an i9J in the industry to the 1st floor, it is a work! For safety reasons, it is desired to move to a bright room where the entire P8 plate is treated with just one salt, and it is not possible to solve the above problems by using non-silver salt photosensitive materials. , limited resources σ
? It is also highly desired by people who make effective use of it.

In an image forming method using a non-salt photosensitive dye, for example, a mask layer having absorption to visible light or an exposure light source when used as a manuscript is provided on a support, and on the above 1. When exposed to light, a change in solubility in the developing solution occurs between the unexposed area and the exposed area, and one of the areas is imagewise exposed to a stripping agent having fumetresist M that remains after development, and then the vagina photoresist layer is developed. At the same time or after developing,
The remaining hardened portions of the photoresist layer are dissolved and the mask layer is treated with a molten iL that can dissolve the mask J, thereby dissolving and removing the portions of the mask layer where the photoresist layer has eluted. There is a way to form

On the other hand, in the field of photosensitive materials for printing, in order to obtain a printing plate, in the process of preparing a manuscript, a film with an image of a certain character or pattern is placed on top of a film with an image of another character or pattern, such as a stripping film. There is a process called ``pasting'', and after pasting, the stripping film is fixed with something called stripping cement I to prevent it from moving. Stripping cement (:1, e.g. methanol, -r
-Solvents such as tanol are used, so it's impossible! J) The film to which the soaking film is pasted must not be exposed to the above-mentioned solvents, etc. J) must also have solvent resistance.

Striso pink cement is made to suit silver salt photosensitive materials, so there is no need to worry about silver salt photosensitive materials being soaked in the solvent of IJ plating cement, but non-silver salt photosensitive materials can be used with the above-mentioned image forming method. For example, in the case of JP-A-52-
As shown in the publication No. 89916, the mask l on the support
, I current f
There are quite a few that have a J/5 IQ and are affected by solvents such as ethanol. In this way, the fact that the binder polymer of the mask layer is easily soaked by the above-mentioned solvents means that the stripping film cannot be used with stripping cement.
When "pasting" is performed on a photosensitive material, non-GJ [images on the photosensitive material may be damaged].

The present inventors have proposed an imaging material having a mask layer on a support and a photoresist layer on the J-layer, in which both ear-forming agents apply surface 1 organic solvent properties to the mask layer. (Research is focused on the first development.) Also, as a result, the mask layer contains a colorant,
Schiff discovered that the intended purpose could be achieved by containing a developer-compatible 711 polymer and an inorganic binder, and thus completed the present invention.

An object of the present invention is to provide an image forming material having a mask layer with improved organic solvent resistance.

Another object of the present invention is to provide an image forming material having improved physical properties, having solubility in an image solution and resistance to organic solvents.

Such purpose is to form an image 4. with a photoresist layer on the mask layer 4 on the support. At t 1・'1, ^
11.Image where 'l''iR' indicates that the mask layer contains a colorant, a developer-used polymer, and a non-binding agent.
] Even achieved by W-component materials.

According to a preferred embodiment (2) of the present invention, the inorganic binding agent is nolumina or a sorcerous binder. Also, according to another preferred embodiment, an aqueous solution or an aqueous binder is used. There are some things that need to be developed.

Now, the present invention will be explained in detail.

Picture 11 of the present invention! Support 1r1. in former T1.
It is a material with self-supporting properties, and by having self-supporting properties, it can support rli1 to 3 layers such as the mask layer provided on the body without stretching. 7 meanings. For example, there are glass temporary, plastic film, paper, etc., but from the viewpoint of handling during work, plastic film and paper are self-supporting and flexible ((
Something with sexuality is better. Examples include polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, cellulose triacetate, baryta paper, resin coated paper, and the like. Further, the coating material used as the support may be colored for the purpose.

In the present invention, a mask layer is provided on a support, but in order to improve the coatability, adhesion, etc. of the mask layer on the support, the support may be subjected to flame treatment or corona radiation treatment. Alternatively, a subtractor 1i+5 may be provided between the two. The subbing layer is formed by coating a solution of a suitable polymeric e-composition onto the support. An example of water used for the subbing layer is hynylidene chloride-acrypnitrile-
Itaconic acid copolymer, glycidyl acrylate or V
, F, polymer or copolymer of glycidyl methacrylate, acrylic acid or methacrylic acid ester polymer with 7-acrylic acid amide or methacrylic acid amide (1), vinyl chloride-vinyl acetate-maleic anhydride polymer, fatty acid vinyl ester, phthalic acid Or ester copolymer of isophthalic acid and glyfurs, suchty-copolymer, acrylonitrile copoly-z-1
It is effective as a material for folding and folding. For information on how to provide a subbing layer, see Photo Manufacturing J'! 4) Well-known techniques can be applied) 1) They can be applied.

Generally, a 51% polymer is applied to the R+ armpit with water or an organic swamp 11^. Cloth method 1
2) Coating sulfur on the support.

J-, 1Is L, and the support 1 contain a colorant, present 1
E, τ) - A mask layer containing a soluble polymer and a blocking agent is provided. Or, it is included in the mask RtI for the purpose of increasing L5 by adding 1 degree to the ++1ii fT part so that it can be printed on the printing plate, and the concentration of the mask layer becomes 10 or more in the ultraviolet or visible "0" region. It is preferable to leave it in.

The coloring agent used in the present invention is a dye or a pigment.The color of the G agent is not particularly limited, but after the image acid honey composition 1 is formed, When an n-light original is used at ℃, it is necessary to absorb at least 3 (1 (1 to 4 (10
n rn or Vj, be(1(1~6 (l On m
It is preferable to have Absorption in Master and En.

Examples of JI filter foil colorants used in the present invention include carbon black (including pre-moon white or grafted carbon flux), lead, iron black, aniline black,
Cyanine black, cobalt purple, manganese purple, Fast Bio L/t 13, Medill Bio Lesotho 1. - Ki,
Geo・■-Rinpoi Ulet, Ultramarine, Sousei, Cobalt Glue, Cerulean Blue, 7.11 Caribbean/1-1-
'-8. Phthalocyanine blue, indigo aluminum powder, copper powder, etc. can be mentioned.

Choose as appropriate from Other Layers, Pigments of Knowledge, and Dyeing 1 to create Zuruko 2. These coloring agents are good to use, but
2 or more) You may use this.

In the mask layer of the present invention, there are 1. l-1
,,/cyst layer i'(+ It fact ti(i+' removed t
The developer solution used to remove the unexposed areas may be used to remove the unexposed areas due to certain safety concerns, pollution hazards, etc.
) Yes% (+'z It is better to use Q'l than fL, <
x <, using an aqueous solution such as an alkali <'J ()
iJ' Hikawakami Or 1.1. ＜、Water use is I
Red (, ζ preferred, 1 used in the discovery of 1) present gu ting (,
Soluble polymer iqi, concrete
2). Here, the water-based FD liquid is mainly composed of water.
-i) L・i? ';' In i, dlc Xiaodan is specifically Mizuchi 50 j+jj, fi! 5'5 or more 7Fh, remaining car, 1911, for example, charcoal ri2 water; bath quality with heptasodium, di-1 lium hydroxide, sodium metasilicate, or C14, for example, mekuno-1 habenge-I2'. - A typical water-miscible organic R+7 medium and, if necessary, a surface activator, etc., are also included. '0. It is a liquid.

Examples of polymers soluble in water or aqueous solutions include methyl cellulose, human r+ = f diethyl 137
+11-S, Carboxylic A-Method Lux, J-S, Human [7, Yasib (J Bilmetinot, -C Nodrosphthalate, Hydrogysobrobyl Methyl Cellulose Hexylhyde (+ Tutrate Capsule)] Cells (J-sulfur derivatives, polyacrylic branched esters, polymethacrylic esters, polyvinyl butyral, polymethylhinyl ketone, nylon 66, polyamide 1, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylmethoxyacecool, Vinyl acetate, eboxy resin, polyurethane, and side tablets
(Addition polymers containing carboxylic acids, such as methacrylic acid copolymers, acrylic acid copolymers, iconic acid copolymers, maleic acid copolymers, phosphoric acid copolymers,
4.7i'L can be used as a molecule, and the Ifll chain has a hydroxyl group, a carbamoyl group, and a dimethyl group.
L coalescence, hinyl allyl flucol copolymer, methylene diethyl malonate copolymer (reduced product), maleic anhydride copolymer (reduced product), acrylamide) copolymer, methacryl 7-mide copolymer, N , N-dimethylaminomethyl methacrylate copolymer, N,N-dimezo-aminomethyl acrylate copolymer, N,N-dimethylaminomethyl methacrylate copolymer, N,N-dimethylaminoethyl acrylate copolymer, N,N-dimethylaminoethyl acrylate copolymer, vinylpyrrolidone copolymer, etc. may be mentioned (1, for example, polyester, sulfonic acid, polyacrylic Acid, polymethacrylic acid, polyglutamic acid, styrene ma 1/inic acid co-nail combination 1.1, -
'M'f of polycations such as luphosphoric acid, algine I'l"l', 9's descending anion and poly7ine-septinium +: A++I'risulfonicum salt, polyphosphoniuno, ±ni, etc.
'F-type, etc. can be mentioned. This can also be used as a developer-soluble polymer, 2) or 2) or more than 2) even if it is used in the mask R/vacuum alone.

d, organic solvent resistance in the mask layer of the present invention! , : (1-
An inorganic binder is included for the purpose of The particle diameter is in the range of 1.+n/L to 1μ, and the particle size is in the range of 1.+n/L to 1μ. This is an inorganic substance that has the property of adhering to other solid materials. By incorporating this inorganic binder into the mask layer, the mask layer θ
,)li4. '+': It is thought that it improves the degree of li and, as a result, gives the mask layer resistance to sagging solvents. Examples of inorganic binders include alumina, silica, clay, and metal oxides. In particular, colloidal alumina and colloidal silica, in which particles similar to alumina and silica are dispersed in water, are generally well known and are preferably used in the present invention. The scorching binder is used in ll!+, Ijl (C
is also good, but it does not need to be used for 2μm f]
In addition, the mask layer of the present invention contains (extending pigments such as dilute barium acid, calcium carbonate, and clay) and white pigments such as zinc oxide, titanium oxide, and dimonium oxide (in combination with a recombinant f agent). It may also be contained.

The mask layer 1 of the present invention includes H.11. - Machine drying method 1 cutting and development HT-soluble polymer water bath solution, aqueous RD solution, organic bath solution, or a mixed bath solution of these are mixed, and the coloring agent is uniformly dissolved or Use the dispersed material as a coating liquid and use it as a coating liquid.
For example, it is formed by coating onto the above-mentioned support by coating with a raw cloth, air knife coating, slide hopper coating, C.

As mentioned above, the mask layer of the present invention contains a colorant, a developer-soluble polymer, and an inorganic binder. It is preferable that the pressure coloring agent is contained in the mask layer in an amount of 5 to 60% by weight, preferably 1 to 50% by weight. In addition, the polymer used for developer is IO~60% in the mask layer.
It is preferable that 1i15-5() contains 0% of electric light.
] (If it is less than 1%, it will be difficult to remove the eluted part of the photoresist layer, and if it is more than 1%, it will not be possible to improve the organic bath agent resistance, which is the original +31. Furthermore, the binder (41) is present in the mask 114 in an amount of 10 to 70% by weight, preferably L<20 to 60%.
It is better to contain 1% of heavy metals.
If the content is less than 10%, the organic solvent properties cannot be improved, which is contrary to the intended purpose of the present invention.

Mask J of the present invention! 'HJ:, e:＞To obtain a degree of 10 or more, 1ψ of 05μ or more is required, and 05 to 8
It is sufficient to have one σ input of about μ. Leftover mask In
When the image becomes thicker, masking during removal by the image; all Zide etching occurs, and faithful reproduction of the image width becomes difficult.
11. .

The mask layer of the present invention can increase its resistance to several solvents while retaining fJl, f'ff liquid M dissolution properties, and this allows the mask layer to be removed by stripping cement during "pasting". damage can be prevented.

In other words, organic solvent resistance can be imparted to the mask Jj.

The upper K of the mask layer of the present invention provided in this way
r, i, one layer of fumetres (4, made).

゛°Photo! What is 7.JIS11ζme°?
In the advertising industry, Vi is already known as f+ candy, but this #l IJ: I+' consists of a skin of light + 1L + ＼ forming substance, and the properties of the exposed and unexposed areas change when exposed to light. 1, for example, 1 Sho na Sorui! Either one can be removed from the layer by It/[, and the remaining one exhibits resist (non-fermentable) properties to the solvent. Examples of such photolayers include a silver halide photographic emulsion layer and a single layer of fluorocarbon polymer.When a single layer of fluorocarbon polymer is used, the unexposed portion is removed and a negative type film is formed. There are pan-doji-type pads in which the tip portion is removed. These can be used in the present invention.1 Examples of commercially available products include photopolymer “' AZ + 35 (1” manufactured by Nosozo 1/・r, USA;
Eastman Kotatsu Co., Ltd. Qliphoto Polymer-”K
P]t'', photopolymer manufactured by Tokyo Ohka (!1) °
“i' P R,” manufactured by Fuji Yakuhin” F P P I
t ”, Asahi Kasei n 剋” nee' r (:/ ko-)
Il+,? These elements (1 can be omitted, but from the viewpoint of work safety and pollution) Aton 1 are used as the first liquid of the present invention
．． The removal solution for the strike layer is water or t-1 (in the system, f-
) is preferred. Techniques for self-forming resists on these halogenated film A emulsion layers and photopolymer J/skin are known in the past, and can be utilized in the present invention.

The image-forming material according to the present invention thus prepared is subjected to image exposure from the photoresist layer side, then the photoresist layer is developed, and then the mask layer is removed from the photoresist layer or the part where the #l image has been removed. By removing the exposure, a negative or positive image is formed.

Various kinds of light sources such as high-pressure mercury lamps, metal halide lamps, tungsten lamps, fluorescent lamps for diazo-sensitive materials, iodine lamps, gysenon lamps, and laser light sources are used as the light source. Exposure method tJ5, Hara (?,
Even if the area is overlapped with close exposure, it can be enlarged and exposed, and it is also possible to use reflected light. In the case of a single layer of photopolymer, remove the non-resist area with a processing solution that dissolves the resist area 1 without dissolving the resist area. Remove, and then melt the mask + G and 6 of the non-resist part and fix the resist part with one layer of polymer. A desired image is formed by removing the %iλ image. Practically speaking, it is more preferable that the same processing solution be used to develop and remove the non-resist portion and the mask layer.

Hereinafter, embodiments of the A-invention will be described, but the embodiments of the present invention are not limited to these.
Unless otherwise specified, "parts" of ingredient percentages are "parts".
'ri (4th part of knowledge)

Example 1 - 1 coating solution consisting of R1 composition of lower Wtr on a film with 7 liters of triacetate provided with F pull 'l, and dried to an Ig of about 3/l. A mask layer was provided.

[Coating liquid-I]

A photoresist layer having a thickness of about 3 microns was formed by applying and drying a photopolymerizable negative type shine coat photosensitive liquid (manufactured by Non-Chemical ■) to this -112 layer of soil. The image forming material-1 according to the present invention created in this way was superimposed on the original, and then printed using a light room printer [manufactured by Ueno Chemical Co., Ltd., [I P-6, <i KW
, metal halide lamp] for 45 seconds, then
0'C alkaline liquid ('ll liquid 5DP-1 (manufactured by Konishiroku Photography Co., Ltd.), a 20 times diluted solution of f11f (p liquid) for PS plate, and then 25°C tap water. I removed the 4-light part with water and obtained a negative image 9. On top of this homemade work,
I applied a stripping film (Zakura CUS) using stripping cement (manufactured by Konishiroku Photo Industry 6Kiku), but I did not suffer any damage (J%) from my homemade product.

Comparison F] A mask layer was formed using a coating liquid having the following composition instead of [Coating liquid-I] used for the mask layer of Example 1, and a comparative image W was prepared in the same manner as in Example 1 except for the following. A stripping material was prepared, and when it was washed with water and "pasted" at the same <tl as in Example 1, damage caused by 7. dripping was observed on both fψ. .

Example 2 [Coating liquid-■] consisting of the following composition was applied to 181! j Adjustment,
A mask layer having a thickness of about 2 μm was provided by coating and drying on a polyethylene terephthalate film provided with an undercoating layer of 1.7.

[Coating liquid-■]

On top of this mask IN, prepare a coating solution having the composition shown below, and apply and dry P10 (negative type with a thickness of about 2μ)]
A resist layer was provided.

The image-forming material according to the present invention thus prepared was image-formed It' for 40 seconds using a bright room printer (same as in Example 1).
< ) After that, soak it in tap water at 25°C (remove the base with a sponge).
I got a picture of Iga. [Passing] was carried out on this 111-sided image in the same manner as in Example 1, but the image 1 was not damaged in any way.

Comparative Example 2 A mask layer was provided using a coating liquid with the following composition instead of the [coating liquid-n] used for the mask layer in Example 2, and the other conditions were the same as in Example 2 (Comparison σ by method 5) Image create a forming material;
As in Example 2, perform exposure, development and removal, and "pasting"
When this process was carried out, damage caused by the stripping cement was observed in the images.

Example 3 The following noftl force ') force (application rib, -II
I, l vi+'Iyq t,, applied on a polyethylene terephthalate film provided with a subbing layer, dried,
-(l I A mask Jc'j with a height of about 4μ was provided.

[Coating liquid-m] A coating liquid having the following composition was applied on this mask layer.
A negative photoresist 111 having a height of about 371 cm was provided by applying a negative photoresist 111.

1ifii ('
9. Expose Y′+ in the same manner as in Example J, and set the current Vf.
J: Negative image 9 was obtained by washing with water. I performed "1-Paste" on top of this image in the same way as 513 Example 1, but
The image CQ did not receive any i:Q damage.

Special M'F Applicant: Konishiroku Photo Engineering Co., Ltd., Agent: Patent Attorney: Roin Akira Saka (and 1 other person)

Claims (1)

[Claims] (1) A mask layer is provided on a support, and the mask layer is provided on a support. Fumetresist j on the f layer! 4 and 1 to form a uTi+I ligation (in the material, the former N+E -v Suff J?4 contains a colorant, the present +"#7+k aJ'If'l, the image-forming material described in Patent F, Jl, in which the binding lubricant is Aluminum. The image forming material according to claim 1, wherein the agent (1) is silica.
The image forming material according to any one of items 1 to 3 of the desired range of NN. (5) The image-forming material according to any one of the claims 1 to 3 of the patent application, which is developed with water.