JPS59154442A - Photosensitive film for forming picture image - Google Patents

Abstract

PURPOSE:To prevent deformation of picture image by the aqueous development in a photosensitive layer contg. a specified modified polyvinyl alcohol as a photosensitive resin component by providing said photosensitive layer to a base film with a hydrophobic adhesive. CONSTITUTION:Modified polyvinyl alcohol having a stilbazolium group or a styrylquinolinium group expressed by the formulas I and II as a group for adding photosensitive component is contained as a photosensitive resin component in a photosensitive layer provided to one side of a base film by adhering with a hydrophobic adhesive. Suitable hydrophobic adhesive is one prepd. by drying an aq. dispersion. In the formulas, R1 and R2 are H or alkyl independently to each other, respectively. Y<-> is a conjugate basic ion of an acid; (m) is an integer 1-6; (n) is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a photosensitive film for image formation, and more specifically, it has a photosensitive layer containing photosensitive modified polyvinyl alcohol as a photosensitive resin component,
The present invention relates to a photosensitive film for image formation that does not cause distortion in images when treated with an aqueous developer.

The backbone of the invention is that when the support film layer is transparent, the image forming film including the support film layer and the photosensitive layer is used. In the case of a gold q evaporated film, there are cases where the film is used by cutting it off or peeling it off after forming an image to avoid dust, such as a display.

To form an image on such an image forming film,
The photosensitive layer is subjected to the desired light irradiation (photography) treatment,
Afterwards, it is necessary to visualize this.

In this plastic treatment, it is preferable to use an aqueous cultivating agent, taking into account the harmfulness of the developing agent to the human body, its flammability, and the ease of disposal. Examples of this aqueous "imaging agent" include alkaline aqueous solutions and aqueous solutions containing low-f-4 H,4 solvents, but the most preferred "imaging agent" is water alone and does not contain any other additives. It is something.

As mentioned above, a water-soluble photosensitive material capable of clear image rT with just water and 1
7 is known to be a manure.

(1) s? IJ Consisting of vinyl alcohol and a diazo compound or a chromium compound.

(2) One consisting of polyvinyl alcohol or water-soluble nylon and a water-soluble vinyl polymerizable monomer.

and so on. However, the photosensitive materials of group (1) have poor storage stability and may cause pollution problems when discarded. In addition, the group (
The photosensitive dye (2) has disadvantages such as poor thermal stability and being susceptible to the effects of oxygen during exposure. For this reason, the photosensitive materials of groups (1) and (2) are still unsatisfactory.

In addition, as water-soluble photosensitive materials, there are
No. 62, Japanese Patent Publication No. 56-5761, and Japanese Patent Publication No. 56-56
Modified polyvinyl alcohols to which styrylpyridinium or styrylquinolinium groups have been added, as known from No. 11906, are known. Further, an image forming film using these modified polyvinyl alcohols is disclosed in JP-A-55-135834.

However, in image-forming films containing modified polyvinyl alcohol as a photosensitive material as described above, the adhesion of the photosensitive layer is poor, so when such a film is developed with water, the adhesive strength of the photosensitive layer is poor. The drawback is that the image is wrinkled and distorted. In fact, in the above-mentioned modified polyvinyl photosensitive resin, the absorbance of the styryl zonium group and the styryl quinolinium group is large, and the photoreaction is of the dimerization type, so that the thickness of the photosensitive layer can be reduced. If the grain size is relatively large and the exposure is from the front side of the photosensitive layer, insufficiently cured portions may occur on the back side of the photosensitive layer (supporting film side).

For this reason, it becomes difficult to hold an image with a cut angle on the support film 7 during the water image. For the reasons described in , and F, image-forming films using photosensitive modified polyvinyl alcohol as a photosensitive material have also been unsatisfactory in practice.

OBJECTS OF THE INVENTION It is an object of the present invention to provide an imaging film that does not exhibit any wrinkling or distortion during treatment with an aqueous plasticizer.

Summary of the Invention The photosensitive film for image formation of the present invention includes a support film layer, and is formed on one surface of the support film, and has the following general formula (I
) and (II); 2...(II) [However, in the above formula, R and R2 each independently represent a hydrogen atom or an alkyl group, and if Yes, conjugation of an acid represents a basic ion, m represents an integer of 1 to 6,
Contains as a photosensitive resin component a modified polyvinyl alcohol having at least one type of stilbazolium group represented by the formula "n represents O or 1" and a styrylquinolinium group as a photosensitive component addition group. The photosensitive layer is characterized in that a hydrophobic adhesive layer is formed between the support film layer and the photosensitive layer to bond them together.

The photosensitive film for image formation of the present invention includes a support film layer, a photosensitive layer containing a photosensitive resin component, and a hydrophobic adhesive layer formed between and bonding these two layers. It consists of

The materials forming the support film layer used in the present invention are:
There are no particular limitations as long as they do not impede the achievement of the objects of the present invention. Synthetic paper whose main component is a polymer, metal-deposited film, etc. are used.

The photosensitive resin contained in the photosensitive layer of the present invention is a modified polyvinyl alcohol, and has a styryl didinium@tilbazolium group represented by the above formula (I) and/or a styryl group represented by the above formula (n). It contains a quinolinium group as a photosensitive component addition group. This addition is
Polyvinyl alcohol or water-soluble partially saponified polyvinyl alcohol, styrylkyrinium compound and/or
or an acetalization reaction with a styrylquinolium compound,
Alternatively, it is carried out by an acetal exchange reaction.

Such photosensitive degeneration? Rivinyl alcohol can be produced using the method described in Japanese Patent Publication Nos. 5761 and 5762 and 11906/1983.

In the photosensitive addition group of formulas (1) and (II),
The alkyl group represented by R1 and R2 is 1 to 4
carbon atoms, such as methyl, ethyl,
The conjugate basic ions of the acid represented by Yo are preferably n-propyl, n-butyl groups, etc. 1d p -) Tokara can be selected as luenesulfonic acid ion.

Such photosensitive modified polyvinyl alcohol is applied by a conventional method onto an adhesive layer formed on one side of a support film together with other suitable binders, colorants, fillers, etc., if necessary. The thickness of the photosensitive layer formed is
It is generally in the range of 0.1μ to 500μ.

In the present invention, prior to forming the photosensitive layer, a hydrophobic adhesive is applied on one side of the support film and dried to form an adhesive layer. Examples of such hydrophobic adhesives include polyvinyl acetate, polyacrylic ester, and polymethacrylic ester.

PVC, 7F! Vinylidene chloride, yf! Listyrene, polybutadiene, silicone resin r: r-f
V-vinyl acetate copolymer, ethylene-acrylonitrile copolymer, acrylonitrile-vinyl acetate copolymer, acrylonitrile-vinylidene chloride copolymer, SB
R, NBR, etc. can be used as main components. These adhesives are used in the form of an aqueous emulsion or an aqueous modified emulsion.

Adhesive 1d, in the form of an aqueous emulsion, is applied to the surface of the support film and is dried and rolled to form an adhesive layer. In addition to the above-mentioned main components of the adhesive, if desired, water-soluble resin, coloring agents such as dyes, types, inorganic powders, and fillers may be added in an amount that does not impede the achievement of the purpose of the adhesive layer. It may also contain an agent. Generally the dried adhesive layer is 0.01μ
It is preferable to have a thickness t in the range of ~50μ.

The present invention will be explained in more detail below with reference to Examples. Reference examples 1 to 4 show examples of the production method of the modified polyvinyl alcohol used in the present invention. , Reference Example-1 After heating and dissolving 100f of polyvinyl alcohol (11 degree: 1700, saponification degree: 88 degrees) in 900 ml of water, the liquid temperature was maintained at 70°C, and N-methyl-γ-(p-
forminostyryl) - bilinonium methosulfate 1
Heat and dissolve 07. After adding 85% IJ acid 42 to the mixture, it was allowed to react for 5 hours. Next, the reaction solution was cooled to room temperature and allowed to stand overnight. Drop this solution into acetone and separate the resulting precipitate by decant and wash twice with acetone.Furthermore, stir this precipitate in ethanol containing a small amount of ammonia for 30 minutes. 1 passed,
Dry. , 1! ) The yield of modified x9 ribinyl alcohol was 1012, and the addition rate was 1.08 molar.

Reference Example-2 Polyvinyl alcohol (m 2 o Oo, degree of saponification s 8%) 1. OOy was heated and dissolved in 900ml of water, and the temperature of the liquid was kept at 70℃, and N was added to it.
-Methyl-1-(p-(2,2-・zomethoxyethoxy)-styryl) -Hi! J Zinium p-toluene sulfate 152 was added and dissolved. Further, 85 thiphosphoric acid 42 was added to this, and after reacting for 4 hours, it was cooled to room temperature and aired all day and night 1-7.

Drop this solution into a large amount of acetone 17. Which one is reference example-1
Treated as described. , obtained odd 1′! The yield of polyvinyl alcohol was 'd99f, and the addition rate was 1.01 molar.

Reference Example-3 Polyvinyl alcohol (degree of polymerization 1,400, degree of saponification 88%) 100F was heated and dissolved in 9 ooml of water, and then the liquid temperature was maintained at 70°C. This Kl-methyl-4-(p
-formylstyryl) quinolinium methosulfate 1
22 was added and dissolved. This solution was treated in the same manner as described in Reference Example-2, and the solid modified polyvinyl alcohol 100%
? 'c'? 4LAc. The addition rate of styrylquinolinium groups was 0.85 mol.

Reference example-4 As polyvinyl alcohol, Cal+j? Oxygen-modified polyvinyl alcohol (polymerization degree 2000, saponification degree 88%)
) 100P and subjected it to the same treatment as in Yarn Example-1 to cause modification and j? Rivinyl alcohol solid 1031 was obtained. The addition rate of the styrylpyridinium group was 1.10 molar. .

Example-1 The photosensitive resin obtained in Reference Example-1 was dissolved in water for 10
1 to 1 with aqueous solution. - 100 parts by weight of the above aqueous solution and 3 parts by weight of carbon black were thoroughly mixed in a 4-indochaker. On the other hand, 75μ thick polyester film was coated with acrylic acid-modified snR latex (2, Pole 0X-
1007, manufactured by Nippon Zeon Co., Ltd.) was applied using a Meyer bar and dried by heating to form an adhesive layer with a thickness of 1 μm on the polyester film. On this adhesive layer, the photosensitive agent mixture described in Section 2 was coated using a Meyer bar and dried by heating to form a photosensitive layer with a thickness of 4 μm on the adhesive layer.

A negative original was brought into close contact with the black image-forming film thus obtained and exposed for 1 minute under a 2 kW ultra-ultra high pressure mercury lamp. Next, this was immersed in water, shaken, and developed to obtain a clear blurred black image. The transmission density of the black image area was measured using Macbeth TD-504 and was 3.20.
Met. 1, use this image as a manuscript 4? When the printing plate was printed on a di-type PS plate, a good printing plate was obtained.

Comparative Example-1 A photosensitive agent mixture similar to that in Example-1 was directly coated on the surface of a 75 μm thick polyester film to a thickness of 4 μm, and then heated and dried to produce a black image forming film. . When this was exposed to light under a 2 kW ultra-high pressure mercury lamp for 1 minute and then shaken and molded with water, part of the image peeled off from the polyester film. However, when the image remaining on the polyester film was dried, partial peeling occurred between the image film and the support film, resulting in L2 wrinkles.

Example-2 Dissolve the photosensitive wax obtained in Reference Example-2 in water and prepare 10
The water volume was 7 volumes. 1-00 parts of the above aqueous solution and 3 parts of the phthalocyanine green pigment were sufficiently heated using an indwelling shaker. On the other hand, modified acrylic acid ester co-M coalescent emul, )-1I-Nippol LX814.
(manufactured by Nichifu Zeon Co., Ltd.) was applied onto one surface of a 96 μm thick oriented polypropylene film using a Meyer bar and dried by heating to form a 2 μm thick adhesive layer. This adhesive layer-
The above photosensitive mixture was applied to the film using a Mayer q-coat and dried by heating to form a photosensitive layer having a thickness of 4 μm.

A negative original was brought into close contact with the thus obtained green image-forming film and exposed for 1 minute at a power of more than 2 kW and a pressure of 1 m (vl) of mercury. This was immersed in water and shaken to form an image.A good positive green image was obtained. The transmission density of this green image area was measured with Macbeth TD-504 and the result 3
．． It was 05. When the image of the octopus was printed with 7Jl) type PSIiK as a manuscript, a good printing plate was obtained.

Comparative Example-2 A photosensitive mixture similar to Example-2 was directly applied to a 90μ thick oriented polypropylene film to a thickness of 4μ,
A green image forming film was obtained by heating and drying. When this was exposed for 11 minutes using a 2 kW ultra-high pressure mercury lamp and imaged by shaking with water, the resulting image had many fine wrinkles.

■Comparative Example-3 The same operation as in Comparative Example-2 was performed. However, only the exposure time was changed from 1 minute to 3 minutes.

At the same time as Comparative Example-2, countless wrinkles were generated in the obtained image (-7. A photosensitive mixture having the following composition was prepared using this aqueous solution.

iy, an acrylic mortar emulsion (Frimall WL-91, manufactured by Rohm and Haas Co., Ltd.)* was applied to a 75 μm thick polyester film using a Mayer par, and then heated and dried to form a 1 μm thick adhesive layer on the entire polyester film. To this, spin coat the above mixture (ii1 composition) to approximately 1.0μ
A thick photosensitive layer was obtained. A negative original was closely attached to the image forming film containing the green phosphor obtained in this manner, and exposed to light for 2 minutes under a 2 kW ultra-high pressure mercury lamp. This was immersed in water and shaken, and the details were water-sculpted with a Ssolley to obtain a bog image. By irradiating this image with an electron beam, 1. A good image was obtained that emitted fluorescent light when charged. 1. Comparative Example 4 The photosensitive mixed composition used in Example 3 was directly spin-coated onto a 75 μm thick polyester film [7, approx. 0
A photosensitive layer of the horn)' knee was obtained. Do this! A.J.
Similarly to Example 3, thin wrinkles were found on the exposed image surface.

Example 4 The same operation as in Actual Example 3 was performed. -, A[3] The photosensitive IQJ resin obtained in Reference Example 4 was used as the photosensitive mixture, and almost the same results as in Example 3 were obtained.

! 1 person with Frf Oji Paper Co., Ltd. ! 111 Permission 1. jR agent Patent attorney Akira Aomizu Patent attorney Kazuyuki Nishidate Patent attorney Akira Yamaguchi 25

Claims (1)

[Claims] 1. Support film) ¥? ! is formed on one side of this support film, and is formed by the following general formula (1
) and (■): t2...(n) [However, in the above formula, R1 and R2 each independently represent a hydrogen atom or an alkyl group, and Ye is a conjugate of an acid. At least one selected from stilbazolium groups representing basic ions, m (represents an integer of 1 to 6, and n represents 0 or 1), and styrylquinolinium groups, is photosensitive. It has a photosensitive layer containing modified polyvinyl alcohol having a component addition group and 1 to 1 as a photosensitive resin component, and a hydrophobic adhesive layer is provided between the support film layer and the photosensitive layer to bond them together. 2. A photosensitive film for uniform formation, characterized in that the hydrophobic adhesive layer is formed by dry-rolling an aqueous emulsion of a hydrophobic polymer. A photosensitive film according to scope 1.