JPS5837639A - Image forming material - Google Patents

Abstract

PURPOSE:To improve the shelf stability of the photosensitive layer and to obtain a high density and high contrast image by water development by forming a photosensitive layer contg. a specified amount of a halogenated Lewis acid salt of diazo resin in liq. epoxy resin on a colored mask layer formed on a support. CONSTITUTION:A photosensitive layer contg. a halogenated Lewis acid salt such as FF6<-> or BF4<-> of the condensate of p-diazodiphenylamine with H2CO in epoxy resin which is liq. at 25 deg.C such as glycidyl ether of bisphenol-A or phenol novolak type epoxy resin by 0.2-2.5pts.wt. per 1 part epoxy resin is formed on a colored mask layer contg. a water soluble or water softenable resin and a coloring dye or pigment formed on a support. The resulting photosensitive material is imagewise exposed to acitve rays such as ultraviolet rays, immersed in water, softly rubbed with sponge or the like to remove the unexposed part. Thus, a clear colored image with high durability is obtd.

Description

[Detailed description of the invention] In the actual ψ conversion 11, a different color ζi' + yt-dye is generally applied to one layer of the pigment-containing mask layer to give imagewise side light to this photosensitive layer. It relates to an image-forming material that has good storage stability and that can be obtained by forming an image with a high density of 1/7 by subjecting it to water treatment after treatment with water.

Since then, the lithographic printing tsumugi 11Jv', the non-silver salt photosensitive layer used as the draft, and the photosensitive resin layer that carries the q'1 part and the face 11 are 11.1 Jv'. Noon='3j4i'
Some of these are disclosed in 1982-62427, 1982-2520, and the like.

Is this method a high-density image? r? ! ! Trying to
When the amount of dyes and pigments in the photosensitive resin layer is increased, the dyes and pigments absorb the active light rays that promote the photosensitization of the photosensitive resin, so the sensitivity increases. .

Examples of the type in which a relief image is formed with a twisted photosensitive resin layer and/or dyed after the relief image is formed are disclosed in Kuzu Kaimei No. 49-22929 and No. 49-22930.

This method requires a special dyeing bath treatment containing a dye, and furthermore, it is necessary to closely control the dyeing conditions in order to achieve a suitable concentration.

Further, the main method of providing a mask layer (r) in advance and depositing a photosensitive resin N thereon is described in %Kokai No. 48-65927 and JP-A No. 50-139720.

Is this method a gold-like mask layer? In the method used, a special acid or -r alkali is required for the elongation of the gold layer to form an image from the buds that have been given imagewise mist. Due to sweat stability and pollution, labor (, l'i
/4 I don't like the problem with 10.

-Sword, 1 opening/closing No. 47-1.6124, No. 52-8
Publication No. 9916'I discloses a method of providing a photosensitive 4Vl RF layer on a mask layer in which dyes and pigments (r-containing or pigments) are dispersed in a polymeric binder.

In this -Ji method, in order to develop the entire photosensitive layer, /lr constant I1 (stage solvent and alkaline liquid are required, and there are problems for industrial hygienists due to pollution),6Y-!l, <No.

To Nagisa et al.', 10N1: In order to solve the problem or inconvenience, 1) r);
As a result, the present invention was completed.

According to the present invention, 1, photosensitive diazo compounds IJ]i
1 (Diazoniuno, Shiaimono and CalTl-nyl group association)
Using a halogenated Lewis acid salt of a condensed TII' compound with Iso condensation cutting) and an epoxy resin (J7), it is developable with water, and moreover, the photosensitive layer has a very high stability. The object of the present invention is to provide high-quality image formation in which a high-density, high-contrast Iij+i image can be produced stably.

1 of the book) is applied to the potting soil close to the support (from III, (a) Vy color mask layer and (b) 2
An epoxy resin that is liquid at 5°C and the epoxy resin i i
ir The halogenated rusu acid of diazo (condensate of diazonilla 1 fat and carbonyl, 4-containing organic condensate ^ 11) with O95 to 2.5 parts by weight. j! [
In the above, the halogenated Lewis acid salts of diazo resins are omitted. Image formation 4 characterized by the following:
Achieved by AI.

Among the disadvantages of the present invention, epoxy resin will be explained.

The fluidity characteristics of the epoxy resin used in the present invention can be defined by the method described in US Pat. No. 3,794,576. Methods that can be used to define the flowability limits of epoxy resins according to the invention include, for example, mercury
In this method, the melting point of epoxy (!71m) is considered to be the temperature at which the molten metal ↑Jlh reaches the maximum M point of mercury. M. Klein edition, published by Interscience, Inc., written by Niuta Ri, "Analytical Chemistry of Polymers", Part 1, pp. 155-3-156!l'sa) 1. I'm here. According to this measurement method, the t-gland of the epoxy position 1 used in the photosensitive layer of the present invention ^1<+? When used, it is a liquid epoxy μFIIJ1 with a melting point below 25°C.

- Detailed explanation of ``Evogishi☆F resin'' is published by Kobunshi Kagaku Kansai Kai, ``■ Edited by Uchihiro [JR construction and application of epoxy resins-
1. ! zuI] is there.

My preferred epoxy resins in this invention are cricidyl ether of bisphenol A and phenol 17I.
7-, cresol novolac type epoxy position, 1 fat. These h2 can be used alone or in combination of two or more. These (1) can be synthesized based on conventionally known synthesis methods, and commercially available products are also easily available.

Next, we will explain about the diazolemonosulfate salt which is included in the present invention.

No-logenyl of diazo selenium used for convenience in the present invention 1
Soric acid 1 bean has a reactivity with diazonilla L salt disclosed in US 1II Special W1-No. 2,063,631 and 4I So in Publication No. 2,667,415, such as aldol and acetal.
4- Reaction product with Ariiso condensation cutting containing all h carbonyl groups,
RFII, PF6-, 8iF6, SbF6 by the method disclosed in JP-A-54-98613
It is also a halogenated Lewis acid salt substituted with an anion component l"tBeFq-.

A particularly preferred diazo-I fat of the present invention is PF6, a condensate of p-dizodiphenylamine and formaldehyde.
-, BF4- is a halogenated Lewis acid salt having gold as an anion component.

Next, the "diazo resin/liquid epoxy resin" in which the photosensitive layer of the present invention is fully developed will be explained.

The diazo resin i' disclosed in JP-A-55-159433 is easily re-decomposed, for example, in an organic solvent and has unsatisfactory stability. The disadvantages of prophosphoric acid generated by photodissociation having low activity against the open #1 polymerization of epoxy resins and insufficient durability of resists can be overcome.

The activity of the diazo g111M of the present invention for the ring-opening polymerization of the epoxy resin of the Lewis acid halide, which is 6η based on photolysis of the Lewis acid salt rj1 of the diazo g111M,
It has a high W content, therefore high sensitivity, and has excellent storage stability because it has a strong salt bond.

The amount of the halogenated Lewis acid salt of the diazo Ht resin used in the photosensitive layer of the present invention is 1 L, which is liquid at 25°C.
At 4, the tackiness of the surface of the photosensitive layer is the same and the water boundary image I/1 is low.

The side part of the photosensitive layer of the present invention is 0.1 μm to 7 μm after coating and drying.
tinl, Ff- or preferably 0.5 pm to 4 nm.

Among the structures of the present invention, the colored mask layer will be explained.

The function of this colored mask layer is similar to that of a layer that is dissolved or removed (with the same solvent) or rubbed off in areas where the photosensitive layer has been dissolved and removed by the solvent to form a colored image entirely. The colored image forming layer is formed by dispersing, mixing or dissolving a dye or pigment as a coloring agent in a binder.
Pigments include organic pigments and inorganic pigments (Pigment Handbook: Edited by Japan Pigment Technology Association and Soil Bi3 Special
``Those described in published publications, etc.'' are used as desired to form a prescription.

When the image forming material of the present invention is used for lithographic printing once a month, it is particularly preferable to use carbon black as a total colorant. This is because the covering power is high.
This is due to the fact that it helps in obtaining the W'r and the image reproducibility is good.

Next, various polymer binders are used for the binding amount of 711 in the colored mask 1 of the present invention, but any water-soluble or water-softening polymer additive can be used. . tit as a water-soluble polymer compound.

For example, natural polymer compounds such as casein, albumin, gelatin, gum arabic, etc., such as methylcellox,
Carboxymethyl cellulose, hydroxyethyl cellulose x1 Hydroxyethylmena A Cell o -X Nato cD Water-soluble cellulose ethers, such as polyacrylic acid, polymethacrylic acid, polyacrylamide, ? Lipinyl pyrrolidone, porindium-L-glumemate, water-soluble polyvinyl butyral, polyvinyl alcohol, copolymer of vinyl alcohol and maleic acid, copolymer of vinyl alcohol and acrylamide, co-Mr base of vinyl pyrrolidone and vinyl acetate , a copolymer of (meth)acrylic acid Nisder and (meth)acrylic acid, acytb-L
/ Synthetic water-soluble polymer compound of latin (for example, heptalated gelatin, maleated gelatin) is sludged and used alone or in combination of two or more types. Ru.

Examples of water-softening polymer compounds include methylcellulose, ethylcellulose, methylcellulose, agar oxyethylcellulose, carboxymethylcellulose,
Shea/ethercellulose, cellulose acetate, cellulose triacetate, cellulose acetate) phthalate, cellulose acetate tumerate, hydroxypropyl methylcellulose heptatalate, hydroxybrobyl methylcellulose hexahydrotumerate, polyacrylic acid ester, polymethacrylic acid ester, polyvinyl butyral , polymethylvinylketone, nylon 66, polyamide, polyvinylmethoxyacecool, polyvinyl acetate, epoxy resin, polyamide, etc. 10Fft, 'S, C, in cellulose derivatives
(5ubs, tU, t-, r-nt: ), +3.8. (
West January ee of'δυtεbtυt)〇5) is determined within the scope of the definition of water softening property described aboveC):h9゜In addition to this, 1(1(additional 1F addition) having a carboxylic group in the 41111 chain , for example, methacrylic acid copolymer, acrylic acid copolymer 1f, imeconic acid copolymer, partially esterified male 1
These include chloric acid copolymer, maleic acid (polymerized product), chloric acid copolymerized product, etc.

Additives having a hydroxyl group, carbamoyl group, or dimethylamino group in the side chain are also used, such as vinyl alcohol copolymers, vinyl aryl/1. Alcohol Jj i
ij polymer, lf dienyl malonate copolymer (reduced product), maleic anhydride co-11f adduct (reduced product), acrylamide copolymer, methacrylamide copolymer, N,
N-dimethyl merinomenalme methacrylate consortium, N
, N-dimethylamizenal acrylate copolymer, N,N-dimenalaminoethyl methacrylate copolymer, and the like. In addition to these, vinylpyrrolidone copolymers and the like are also useful.

The molar ratio of the carboxyl group, hydroxyl group, carbamoyl group, and dimethylamino group in the above co-Mf coalescence varies depending on the type of other co-Mf coalescence components, and the molar ratio is determined in the above-mentioned definition of water softening property [71]. Ru.

Such polymerized accessories are published individually or in two or more buildings once a month (IJ).

In Book 31', a method known to those skilled in the art is revised based on the target optical α degree and the removability of the mask layer against water in the ratio of cylindrical polishing/cutting of the mask layer. It can be determined accordingly.

The support on which the mask layer of the present invention and the photosensitive layer consisting of epoxy position 4 fatty acid and diazo resin (halogenated Lewis salt) are coated may be a laminate of paper, glass stick (for example, polyethylene, polypropylene, polystyrene, etc.). For example, cellulose acetate, polyethylene telemerate, polypropylene, polystyrene, vinylidene chloride, etc. are used.

In history, masks! An undercoat layer may be provided to improve adhesion. - Synthetic resins suitable for the coating layer include acrylic acid ester (vinylidene resin),
1 Fuhua vinylidene-acrylic "J21 Lyru-itaconic acid copolymer resin, vinyl chloride-vinyl acetate-maleic anhydride J
ξ Polymer resin, acrylic acid amide × means memethacrylic acid amide derivative, acrylic acid deficiency means alkyl ester of memethacrylic acid, copolymer resin with styrene or acrylonitrile, fumeric acid or 1j isophthalic acid and glyfurs. Polyester resins, polymers or copolymers of glycidyl acrylate [or glycidyl memethacrylate], and sludged gelatin are also useful as the coating layer component. ]・In addition to the above-mentioned components, many synthetic resins are known for forming the coating layer, and methods for adjusting the coating liquid and coating methods are well known in the photographic materials manufacturing industry covered by the present invention. Since these are well-known techniques, they can be applied as appropriate. In general, the above-mentioned synthesis process is carried out by forming a solution using a solvent, and then forming a solution using a solvent. Coat on the support 45 using cloth methods such as Kura-Giesser coating, roll coating, air knife coating, and spray coating.

To specifically describe the method for manufacturing the image forming material of the present invention, the mask layer binder and the photosensitive layer are generally made of acetone, methanol, ethanol, methyl ethyl ketone, methyl 1-butyl ketone, cyclohexanone, β-hydroxyethyl methyl ether (methyl Selonrubu), β-acetoxyethyl methyl ether, methyl cellosolve acetate, dimethylpormamide, hexamep luphosphonamide,
TE) 7 Humans It is soluble in solvents such as chlorbenzene, chlorbenzene, and tri-aryendarylcol. Therefore, select an appropriate solvent from the above solvents (llh alone or a mixed solvent containing two or more organic solvents). Then, adjust the coating solution by adding 4M solution into it.

The coating solution thus prepared has a viscosity that can be applied to various coating techniques known in the art.

Along the coating process, the well-known boiler coating, tip coating, 1
Coating on a transparent support by a method selected from coating methods such as cloth, roll coating, '()L'-coating, F12-knife coating, and L/F-knife coating. be done.

To describe the effects of the present invention, the image forming force method using the image forming material of the present invention is as follows: -1J:
8fii image formation H material, sweets activity 111. The image area is illuminated by the light beam. Various light sources can be used as the light source, such as a mercury lamp, a tungsten lamp, a mercury lamp, a xenon lamp, a CnT light source, and a laser light source.

In the photosensitive layer imagewise exposed to actinic light such as ultraviolet rays, the diazo resin (halogenated Lewis acid) has activity against boxy resin opening JJ1 polymerization of the halogenated Lewis acid generated by photodissociation in the swallow-shaped epoxy resin. The reaction proceeds with high sensitivity and becomes insoluble in water.

Since the light-irradiated surface has strengthened adhesion, when the image-forming material after exposure is immersed in water and formed into a water-oil image, the unexposed areas of the image are easily developed by rubbing and rubbing to darken the image-forming material. This and 'f!
The unexposed area of the photosensitive layer and the mask I fin of the 1F layer corresponding to that area are removed, and a positive negative film image is formed.

Although 11 examples of the present invention are described in JuT, the actual guns of the present invention are not limited to the following HI3 cases.

(Example 1) Apply a solution having a composition of 1 to a piece 7111 of a polyethylene terephthalate film with a thickness of 1 (10 μIn) so that the film thickness after drying is 1 μN1, dry it, and attach it. Seven eyebrows were formed on the heel.

On this colored mask layer, "F" (b) of the present invention, IIC photoliquid A1 and comparative photosensitive liquid B were coated so that the a-portion after drying was 1 .mu.m to obtain image forming materials A and B.

(b) (Photosensitive liquid A) (Photosensitive liquid B) Top #i: Each of the two types of image forming materials 1. After applying the l' charge, it was stored in an atmosphere of 40° C. and 80% humidity. ? 1 image forming material to memelhalite lamp idol fin 2
000 [manufactured by Iwasaki Electric ■] for 30 seconds from a distance of 80 z, and then immersed in water at 30° C. for 1 minute, and then lightly rubbed with a sponge to perform the present f#IIL treatment.

Removal of unexposed areas of the mask image obtained by <1,7+!
When we examined the number of days for the ability to deteriorate from a practical standard as a measure of shelf life, we obtained the results shown in Table 1. %
Hi.

Comparing the image characteristics of the 1+ black mask image, there are more Bevin holes in (A) than in (A). In (B), by increasing the exposure time, the pinhole becomes smaller by 6&i as in (A). That is, it can be seen that (A) has higher sensitivity than (B).

As a result, it was confirmed that the image forming material according to the present invention has excellent sensitivity and storage stability.

Indeed, Example 2: On the same colored mask layer as in Case 1, the photosensitive liquid of the present invention described in 'F' was applied and the film thickness after drying was 1.0 μm1'I.
Sea urchin nuclide.

(b) IT-like epoxy resin (Aral manufactured by C1ba)
dite 6030) 17- When exposed and developed in the same manner as in Actual Example 1, a clear black mask image was obtained.

Patent applicant: Konishiroku Shajiko Co., Ltd. Agent: Patent attorney: Nobuaki Sakaguchi (#1 or 1 person) Seishakuura Masashi (self-motivated) October 1980 711 Cow 1. Fraud agency "Q attack f'i Sugi Aio + 1
1 F'l's No. 3 Show (U 56 Te 1 Special ¥1 Application No. 119333
No. 2 Invention and 1811'll Image IFF Formation'';
M='13 i city 1 niro -4' name 1 kui 1 connection 1. Ministry of Patent Issue II, Q'i Person II
111i Mr. '(, C' (sub 1,) (1,271 Roku Konishi Co., Ltd. 4, agent 〒105 ``i Number of inventions increased by cuffs 7, sleeve 1 [- sentence] Elephant Gate 1il119'f (Detailed explanation column) 8 Contents of sleeve 11 As per the attached sheet, Irda 1 1 in line 10 and line 17 on page 9 of the middle part of the specification 1 methyl cellulose...Methyl cell [1-Suftale-1
・, ) is 1 methyl cellulose (S, C, = 3 ~ 1
0%), cellulose (D, S, -0.5~0.
7,2,2.3,31, butyl cellulose, hydroxyethylyl V1-su(s, c, =<ao%, n55%
), carboxymethylcellulose (S, C,, =5~
10%, >30%), cyanoethyl cellulose (No. 1,
C, = 8~1296 + > 50%), cellulose acetate-l- (+1. Sf = 1.3~1.7, 2
, 2.3), cellulose acetacetate 1-, cell 1
]-suacetate butyrate 1-, cellulose acetate-1
- to phthalate 1, hydroxypropyl methyl cellulose phthalate 1- (methoxyl group = 12 to 38 wt%, hydrogen 1-1 poxyl! = 2 to 15 wt%, carbo A-siben no (I) (= 12 to 50 wt%) %),
Correct it to -1.

2 On page 10, lines 3 to 6, [10 cells lll-s...... are determined. ] 1. : f
f1. ! :1. 'Among single molecule compounds, for ρ11 component Y compounds other than cellulose derivatives, the average molecule is 9
Selected in the range k 1,000-10(M)00 no 1-. ” he corrected.

3 In the 6th line of the 11th column, the phrase ``determined.'' is corrected to ``determined, and the average molecular weight ID is selected within the range of 00 to 100,000.'' -1.

4. In line 150, line 12 of the same, the phrase "phthalyl group" is corrected to read "carbogycibenzoyl group."

I"2 2-

Claims (1)

[Claims] Add (a) a colored mask layer and (1+) an oily epoxy layer 1 at 25°C to the support pot soil from the U'rlA side to the support 1.
0.5 per part of the moon and the 1x LiX part of the Evogishi resin
An image-forming material having a photosensitive layer containing 2.57 parts by weight to 2.57 parts by weight to 11 parts by weight of a diazo resin halogenated Lewis E and gold, which is characterized by /P1.