JPH0685078B2 - Relief forming method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a new relief forming method using a water-soluble photosensitive resin, and relief forming to obtain a fine and delicate negative relief image by using recording with an aqueous ink. It is about the method. As a field of application of the relief image obtained by the practice of the present invention, in addition to decorative relief, it is used as a printing plate (relief plate, intaglio plate, planographic plate, stencil plate), and as a mold for making a flexo rubber plate by pouring rubber into the recesses. It can be used as an OHP (overhead projector) film or a slide substitute by dyeing a photosensitive resin, or as a resist for electric circuit boards, printed matter for blind persons, stereoscopic images and the like.

[Prior art]

Recently, using relief images by surface irregularities, in addition to ornaments, printing plates, flexo rubber plate original plates, three-dimensional images, books for blinds, and various other uses have been developed.

Heretofore, as a relief forming method, there have been used a method of directly engraving on a substrate with a knife and a method of using a photosensitive material by hand. As a method of using a photosensitive material, a photosensitive material is coated on a substrate, dried, exposed to a negative film, exposed to light, and developed with a developing solution to wash away the non-photocured photosensitive material to obtain a relief image. Alternatively, after the development, the substrate is subjected to etching treatment, and then the photocured photosensitive film is removed to obtain a relief image.

[Problems to be Solved by the Present Invention]

However, the conventional relief forming methods such as those mentioned above have the drawbacks that the carving is troublesome and poor in reproducibility, and it is difficult to obtain a precise image, and the method using a photosensitive material also has a very high relief forming process. It is cumbersome, cumbersome, poor in mass productivity, expensive, and includes an exposure process with a negative film applied.Therefore, fine printing and thick plates have a limited light diffraction index, and relief cannot be obtained properly. However, the reality is that there are naturally limits to the uses.

[Means for solving problems]

The present inventors simplified the above conventional relief forming method,
The present invention has been completed as a result of intensive studies on a method of forming reliefs more easily, accurately and cheaply.

That is, the present invention, after coating the water-soluble photosensitive resin on the substrate and dried, recording with a water-based ink, then irradiated with radiation to cure the resin other than the water-based ink recording portion, The present invention relates to a relief forming method, which comprises developing with water or alkaline water to flow away a resin in a recording portion of an aqueous ink to form a relief.

The principle is that the portion recorded with the water-based ink on the water-soluble photosensitive resin coating does not transmit light when irradiated with radiation to cure the resin, or is cured because the resin is in a low curing state. By utilizing the fact that the pattern is removed by dissolving the water-based ink-recorded portion in water or alkaline water by developing it with water or alkaline water without forming a relief image.

[Structure of Invention]

The present invention is a water-soluble anionic synthetic resin of a radiation-curable type or a water-soluble anionic synthetic resin of this type and a radiation-curable type derivative obtained from a natural product such as casein, gelatin, starch and cellulose on a substrate. Of a photosensitive resin whose main component is a mixture of 50% by weight or less of a water-based resin, and after drying, recording is performed with an aqueous ink, and then radiation is applied to cure the resin other than the recording portion of the aqueous ink. The present invention relates to a relief forming method, characterized in that the resin in a recording portion of an aqueous ink is removed by developing with water or alkaline water to form a relief.

The radiation-curable water-soluble photosensitive resin used in the practice of the present invention will be described.

The radiation-curable water-soluble photosensitive resin referred to in the present invention is a resin in which a functional group of a polymerizable double bond that is cross-linked and cured by irradiation with radiation is introduced into the water-soluble resin. ). It is a resin that has good printability with water-based ink, (2). After coating and drying on the base material, it is a resin that is crosslinked and cured by irradiation with radiation and does not cause a film change such as swelling or elution with water or alkaline water, (3). The portion that has not been radiation-cured is a resin having good solubility in water or alcal water, (4). A resin that has a good ink-flowing property during development with water or alkaline water (5). When coating on a substrate, there is no stickiness, no cracking, no cissing, and good surface smoothness of the coating film. Although a curable water-soluble photosensitive resin can be used, a radiation curable water-soluble anionic synthetic resin is particularly preferable in terms of performance.

The resin having good printability with the water-based ink referred to here is (1). Absorption rate of water-based ink is fast, and it has excellent drying property.
In addition, it should be a resin that absorbs a large amount of ink and prevents the colors that will be recorded later from flowing out when the ink colors overlap.

(2). The water-based ink should be a resin that penetrates well into the water-soluble photosensitive resin coating layer.

(3). It is a resin that satisfies the required performance, such as a recording shape with water-based ink that is sharp and does not spread such as bleeding.

Examples of the radiation-curable water-soluble anionic synthetic resin include (a) a polymerizable double bond, and (b) an anionic group selected from a carboxyl group, a sulfonic acid group, a sulfuric acid ester group, and a phosphoric acid ester group, and / or A resin containing a polymerizable resin having a functional salt of the neutralization salt as a main component can be used. Examples thereof include the following (I) to (IV).

(I). Carboxyl group-containing polymerizable monomer 10-90% by weight
And a copolymer resin of 90 to 10% by weight of another polymerizable monomer copolymerizable with the above, a polymerizable monomer having an epoxy group is added to the carboxyl group-containing polymerizable monomer of the copolymer resin. 0 of the quantity.
1-0.6 g equivalent to react with a part of the carboxyl group of the copolymer resin to form an ester bond, or if necessary, with the remaining carboxyl group in whole or in part alkali,
Resin neutralized with ammonia or a base such as amine.

This resin is a resin containing the following (c) group and (d) group in the molecule, and the (c) group and the (d) group are represented by the general formula [Wherein R ¹ , R ² and R ³ are H or CH ₃ and M is H, Li, N
a, K, NH ₄ or an amine residue. ] Those represented by are preferable.

Examples of the carboxyl group-containing polymerizable monomer include monoacrylic acids such as acrylic acid and methacrylic acid; polybasic acids such as maleic acid, itaconic acid, and citraconic acid, and acid anhydrides thereof.

Other polymerizable monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl. Alkyl acrylates, alkyl methacrylates such as methacrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate, stearyl methacrylate; benzyl acrylate, benzyl methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyp Pills acrylate, hydroxypropyl methacrylate, styrene, vinyl toluene, and vinyl acetate.

And as the polymerizable monomer having an epoxy group, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, styryl glycidyl ether,
Examples thereof include compounds having a vinyl group and an epoxy group such as glycidyl cinnamate.

As the base for neutralizing the carboxyl group, alkali hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonia water; primary amines such as alkylamine and ethanolamine; secondary amines such as dialkylamine and diethanolamine. And tertiary amines such as trialkylamine and triethanolamine.

(II). Carboxyl group-containing polymerizable monomer 10-90% by weight
And a copolymer resin with 90 to 10% by weight of another polymerizable monomer that can be copolymerized with a polymerizable monomer having a hydroxyl group, and a polymerizable monomer having a carboxyl group of the copolymer resin. Body 0.1 ~
By reacting with 0.6 g equivalent, a part of the carboxyl group of the copolymer resin is ester-bonded, or in some cases, all or part of the remaining carboxyl group is neutralized with a base such as alkali, ammonia, or amine. Resin.

The carboxyl group-containing polymerizable monomer, the other polymerizable monomer copolymerizable with the same, and the same base as (I) can be used, and the hydroxyl group-containing polymerizable monomer is hydroxyethyl acrylate or hydroxy. Examples thereof include ethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.

(III). Carboxyl group-containing polymerizable monomer 10 to 90% by weight and other copolymerizable monomer 90 to 10% by weight
And a halogenated polymerizable monomer in the copolymer resin with 0.1 to 0.6 of the carboxyl group-containing polymerizable monomer of the copolymer resin.
A dehydrohalogenation reaction is carried out with g equivalent to form a part of the carboxyl group of the copolymer resin through an ester bond, or in some cases, all or part of the remaining carboxyl group is treated with a base such as alkali, ammonia, or amine. Neutralized resin.

The resins (II) and (III) are resins containing the following groups (e) and (f) in the molecule, and the groups are preferably represented by the following general formula.

[Wherein R ¹ , R ² and R ³ are H or CH ₃ and M is H, Li, N
a, K, NH ₄ or an amine residue, and A is an alkylene group having 2 to 6 carbon atoms. The carboxyl group-containing polymerizable monomer, other polymerizable monomer copolymerizable with the same, and the same base as in (I) can be used, and the halogenated polymerizable monomer can be haloalkyl acrylate or haloalkyl. Methacrylate, halomethylstyrene, allyl halide and the like can be mentioned.

(IV). A resin having a carboxyl group and a vinyl group obtained by reacting an epoxy compound with an unsaturated polybasic acid, or in some cases, all or part of the carboxyl group of this resin is neutralized with a base such as alkali, ammonia, or amine. Resin.

Examples of the epoxy compound include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, novolak epoxy resin, cresol novolak resin, glycidyl acrylate, glycidyl methacrylate, or a resin copolymerized with a monomer copolymerizable therewith. Can be used.

As the unsaturated polybasic acid, itaconic acid, maleic acid, and other acid anhydrides can be used.

(V). A resin having a vinyl group and a carboxyl group obtained by esterifying a resin having a polybasic acid group (or an acid anhydride group thereof) and a polymerizable monomer having a hydroxyl group, or a residual carboxyl group in some cases. A resin in which all or part of the groups are neutralized with a base such as alkali, ammonia, or amine.

It is preferable that this resin contains the next group in the molecule.

[In the formula, R ¹ is H or CH ₃ , M is H, Li, Na, K, NH ₄ or an amine residue, and A is an alkylene group having 2 to 6 carbon atoms. Examples of the resin having a polybasic acid group (or an acid anhydride group thereof) include itaconic acid / acrylic acid ester copolymer resin, maleic anhydride / styrene copolymer resin, maleic anhydride graft polyethylene and the like.

As the polymerizable monomer having a hydroxyl group, the hydroxyl group-containing acrylate and hydroxyl group-containing methacrylate described in (II) can be used.

(IV). In the resins of (I) to (III), instead of the carboxyl group-containing polymerizable monomer, a part or all of it is styrene sulfonic acid, styrene sulfate, 2-hydroxyethyl acryloyl phosphate, 2-hydroxyethyl methacryloyl. Resin obtained by substituting a polymerizable monomer having a sulfonic acid group, a sulfuric acid ester group, or a phosphoric acid ester group such as phosphide.

In the resins of (I), (II), (III) and (VI), a carboxyl group-containing polymerizable monomer and / or a sulfonic acid group, a sulfuric acid ester group or a phosphoric acid for obtaining a precursor copolymer resin The polymerizable monomer having an ester group is 10 to 90
% By weight, preferably 20 to 80% by weight, and other polymerizable monomers copolymerizable with the resin are 90 to 10% by weight, preferably 80 to 80% by weight.
Used in a proportion of 20% by weight. When 0.5 to 80% by weight of the polymerizable monomer having a higher alkyl group having 8 to 18 carbon atoms is contained in the other polymerizable monomer which can be copolymerized, the water resistance of the film during water or alkaline water development is increased. The property is further improved. Further, with respect to the copolymer resin having a carboxyl group and / or a sulfonic acid group, a sulfuric acid ester group, or a phosphoric acid ester group, a polymerizable monomer having an epoxy group or a hydroxyl group or a halogenated polymerizable monomer is a carboxyl group. It is used in a proportion of 0.1 to 0.6 g equivalent, preferably 0.2 to 0.5 g equivalent of the polymerizable monomer having a group and / or a sulfonic acid group, a sulfuric acid ester group, or a phosphoric acid ester group.

Further, in the resin (IV), the epoxy compound is used in a ratio of 1 to 40 mol per 1 mol of polybasic acid.

Further, in the resin (V), the polybasic acid (or its acid anhydride), the hydrophobic resin, and the hydroxyl group-containing polymerizable monomer are
A carboxyl group-containing polymerizable monomer of the resin (II),
It is used in the same amount as the hydrophobic monomer, hydroxyl group-containing acrylate, or hydroxyl group-containing methacrylate.

If the ratio of the hydrophobic polymerizable monomer and the hydrophobic resin is less than the above amount, bleeding of the aqueous ink will occur and good recording cannot be obtained, and crosslinking obtained by photocuring the polymerizable resin will be impossible. The water resistance of the coating film of the resin layer becomes insufficient. On the other hand, if the amount of the hydrophobic resin is too large, the coating film becomes hydrophobic and the absorption of the aqueous ink becomes poor.

In addition, carboxyl group, sulfonic acid group, sulfate ester group,
If the amount of the phosphoric acid ester group-containing polymerizable monomer is too small, the absorption of the water-based ink will be insufficient, and if it is too large, the water-based ink will bleed and good recording cannot be obtained.

In the present invention, a part (50% by weight or less) of the radiation-curable water-soluble anionic synthetic resin (A) is composed of a radiation-curable derivative obtained from a natural product such as casein, gelatin, starch and cellulose. It can be used in place of the water-soluble resin (B). The radiation-curable water-soluble anionic synthetic resin (A) is a resin that does not have stickiness or cracks during coating and has very good coating properties such as surface smoothness and transparency. The relief can be formed very well and the relief can be formed very well. However, when the relief thus obtained is used as a printing plate for a long time, the aromatic, ketone, glycol, cellosolve An organic solvent such as carbitol, cellosolve acetate, ketone alcohol, or acetic acid ester may attack the relief surface, which may cause swelling or swelling. casein,
The water-soluble resin (B), which is a radiation-curable derivative obtained from a natural product such as gelatin, starch, or cellulose, has good solvent resistance to non-uniform solvents and is used in relief formation by water or alkaline water development. Also has good ink flow-off properties and produces a very good pattern. Therefore, a part (50% by weight or less) of the radiation-curable water-soluble anionic synthetic resin (A) was added to casein, gelatin,
When used in place of the water-soluble resin (B) consisting of a radiation-curable derivative obtained from a natural product such as starch or cellulose, the coating film state, water or alkaline water developability is good, and the organic solvent resistance is also good. A material useful as a printing plate can be obtained.

Water-soluble resins composed of radiation-curable derivatives obtained from natural products such as casein, gelatin, starch, and cellulose can be used as amino groups, imino groups, carboxyl groups, and hydroxyl groups contained in natural product derivatives. Obtained by a method of introducing a radiation-polymerizable double bond by modifying with a polymerizable monomer having a reactive group, or a method of grafting a polymer molecular chain having another radiation-polymerizable dimer bond. To be Specifically, for example, a derivative of a natural product such as casein, gelatin, starch, or cellulose is added with an epoxy group of a polymerizable vinyl / epoxy compound such as allyl glycidyl ether, styryl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, or glycidyl cinnamate. Method of reacting, method of reacting carboxyl group of polymerizable vinyl carboxylic acid such as acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, polymerization of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate Of reacting the hydroxyl groups of vinyl acetate hydroxide, N-methylol acrylamide, N
-Polymerizable vinyl N such as methylol methacrylamide-
Method for reacting methylol group of methylol compound, method for reacting halogen group of polymerizable vinyl halide such as allyl halide, halomethylstyrene, haloalkyl acrylate, haloalkyl methacrylate, polymerizable vinyl such as aziridinoalkyl acrylate, aziridinoalkyl methacrylate -A method of reacting an aziridine group of an aziridine compound, a method of reacting an aldehyde group of a polymerizable vinyl-aldehyde compound such as acronlein or methacrolein, and the like.

The recording method using the water-based ink used in the present invention includes handwriting with a commercially available water-based ink pen, recording with a normal dot printer, recording with an XY plotter, recording with an ink jet printer, and water-soluble dye. Any recording method such as heat-sensitive recording and pressure-sensitive recording using a water-soluble dye can be used. However, in order to form a relief image satisfactorily, a water-based ink or water-based dye is a water-soluble photosensitive resin coating layer. It is preferable that the resin penetrates well into the interior to prevent crosslinking and curing of the resin by radiation. From this point, recording with an ink jet is particularly suitable for this purpose. In the ink-jet recording method, since ink droplets are jet-jetted from nozzles and adhered to the recording material, the amount of ink adhering to one point on the recording material is larger than other recording methods, and the ink droplets are recorded on the recording material. When it is absorbed into the recording material, it penetrates deep into the inside of the recording material, and when it is irradiated with radiation later, the light does not penetrate to the inside, and the pattern is removed well during development with water or alkaline water.

Water or alkaline water can be used for developing the water-soluble photosensitive resin according to the present invention. As the alkaline water used,
Lithium hydroxide, sodium hydroxide, potassium hydroxide,
Ammonia water, ethanolamine water, trimethylamine water, triethanolamine water, etc. can be used.

The present invention, in addition to the radiation-curable water-soluble photosensitive resin, in order to improve the state of the coating film, higher alkyl ethoxylates, polyalkylene glycol acrylate,
Specially polymerizable monomers such as diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, wetting agents, other electrolyte polymers, additives (transparent pigments, small amounts of clay, fillers such as charcoal,
There is no problem in adding an antifoaming agent) to the water-soluble photosensitive resin.

The present invention is to apply a radiation-curable water-soluble photosensitive resin on a substrate, dry it, and then record with an aqueous ink, and then irradiate radiation to cure the resin, and then use water or an alkaline water solution. The present invention relates to a relief forming method and a resin for forming a relief, which are characterized in that a relief is formed by developing with. The radiation used in the present invention includes X-rays, deep ultraviolet rays, ultraviolet rays, visible rays, infrared rays,
Far infrared rays and the like can be used, but ultraviolet rays and electron beams are particularly preferable, and in the case of ultraviolet rays, a photoreaction in which the water-soluble photosensitive resin according to the present invention absorbs ultraviolet rays to generate radicals and initiates polymerization. An initiator (optionally in combination with a small amount of amine) must be added, but in the case of an electron beam, it is not necessary to add a new photoreaction initiator. Examples of the photoreaction initiator include benzophenone, methyl -benzoylbenzoate, 4,4'-bisdimethylaminobenzophenone, 4,4 '.
Benzophenones such as bisdiethylaminobenzophenone, benzoin alkyl ethers such as benzoinmethyl and benzoinethyl, ketals such as acetophenone diethyl ketal and benzyldimethyl ketal, thioxanthones such as chlorothioxanthone, methylthioxanthone and isopropylthioxanthone, Dibenzyls and the like can be used, and as the amine used in combination, triethanolamine, diethanolamine, ethanolamine, trialkylamine, dialkylamine, alkylamine and the like can be used. The photoreaction initiator and amines are used in an amount of 0.5 to 5 parts by weight with respect to 100 parts by weight of the radiation-curable resin component.
Amine 0.001 to 100 parts by weight of radiation curable resin component
It is used in a proportion of 3 parts by weight.

Further, a thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butyl hydroquinone, catechol and other phenols, benzoquinone, diphenylbenzoquinone and other quinones, phenothiazines, copper and the like is added to 100 parts by weight of the radiation curable resin component. For 0.0001 to 1
You may mix | blend a weight part.

Examples of an ultraviolet ray source that generates ultraviolet rays include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and sunlight, and an electron beam source that generates an electron beam is, for example, Kokkucroft. Electron beams accelerated by accelerators such as neutron accelerators, van de Graaff accelerators, linac selectors, betatrons, and cyclotrons are the most industrially convenient and economical to use, but other radioactive isotopes and atoms are also used. Radiation such as γ-rays, X-rays, α-rays, β-rays, neutron rays and proton rays emitted from furnaces can also be used.

The radiation-curable water-soluble photosensitive resin coating according to the present invention includes air knife coating, blade coating, bar coating, gravure coating, curtain coating, roll coating,
Plastic film such as polyester, synthetic paper, paper with adjusted size, air permeability, smoothness, etc. by spray coating method, and resin coating of barrier coating layer, or extrusion coating of thermoplastic resin, etc. It is performed on a substrate such as a paper processed product, resin-impregnated paper, metal plate such as aluminum plate, copper plate, etc. In some cases, an anchor coat may be applied to the base material in order to improve the adhesiveness of the radiation-curable water-soluble photosensitive resin. The coating thickness of the radiation-curable water-soluble photosensitive resin is in the range of 0.1 to 20 μm, preferably 0.5 to 10 μm. After coating and solvent drying, recording with a water-based ink, followed by irradiation to cure the resin,
After development with water or alkaline water and drying, a relief image is obtained, but after development and drying, further post-exposure can be performed to enhance curability.

Since the radiation-curable water-soluble photosensitive resin according to the present invention has an anionic group, a hydrophilic group, etc., it has antistatic performance when coated on a substrate, and especially when a film substrate is used, dust is not generated. It also has the feature that it does not adhere and there is no electrostatic damage.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. The parts and% in the examples are based on weight.

Example 1 A flask was charged with 50 parts of methacrylic acid (0.58 g equivalent), 20 parts of methyl methacrylate, 30 parts of lauryl methacrylate, 100 parts of isopropanol, and 0.5 parts of 2,2'-azobisisobutyronitrile under a nitrogen atmosphere. The polymerization reaction was carried out at 80 ° C for 6 hours.

Next, 29.4 parts of glycidyl acrylate (0.23 g equivalent)
And tetramethylammonium bromide 0.9 part were added to 70
After stirring for 4 hours at ℃, water-cooled, 20.2 parts of potassium hydroxide (0.36g equivalent), 220 parts of water was added dropwise and stirred for 1 hour.
The resin (1) was obtained by stirring at 3 ° C. for 3 hours. This resin (1)
Is Is included in the molecular chain.

Next, water / isopropanol (1/1 weight ratio) 15 of a composition containing 3 parts of the resin (1), a photoinitiator (trade name: VICURE55) manufactured by Stoffer Co. in a solid content ratio of 15 parts, was added. %
Solid coating using a bar coater on a polyester film (thickness of 100 microns) that has been previously treated with an anchor treatment agent (trade name: Under-Lacker RU, 0.5g / m ² ) manufactured by Toyo Ink Co., Ltd. It was applied so that the amount of work would be 10 g / m ² .

Then, after drying, ink jet recording was carried out using Sharp Co., Ltd. (trade name: Color Image Printer I0-0700). The ink absorption and drying were fast, and Iku was inside the coating layer. The ink recorded shape was sharp and no spreading such as bleeding was observed.

In addition, UV irradiation device (Nippon Battery Co., Ltd .; lamp strength)
(80 W / cm) was cured with ultraviolet light at a conveyor speed of 10 m / min, then dipped in running water at 20 ° C, lightly rubbed the surface with a sponge to develop, and dried. Only the part where ink / jet recording was performed It was beautifully eluted and the coating layer had disappeared, no ink remained, and the edges of the image were sharp. No elution or swelling was observed in the coating film cured by ultraviolet rays, and cracks, cissing, and
The film was in a film state with very good surface smoothness without stickiness. Further, post-exposure was carried out 3 times under the same UV irradiation conditions, and a relief image having a very good finish could be obtained on the polyester film.

For comparison, after ink / jet recording, water development was performed without UV irradiation, and the water resistance of the area other than the ink / jet recording area was insufficient. I couldn't get the image.

In addition, after ink-jet recording on a polyester film obtained by coating in the same manner without adding a photoreaction initiator,
Using an electron beam irradiation device (Electro Curtain, Energy Science Co., Ltd.), accelerating voltage 150KV, current 2.0mA, electron beam irradiation amount 1.0Mrad, water development, same as UV curing. A good relief image could be obtained.

The relief image on the polyester film obtained as described above was subjected to desensitization treatment, and was then printed on a rotary press to give a good print finish and good reproducibility even in fine areas. It was

Also, when the relief image on the polyester film obtained as described above was dyed blue with a rubber roll, only the convex portions became blue, and the concave portions were transparently transparent. When applied to an ecto, a slide alternative film with a resolution equal to or better than that of the blue slide was obtained.

Example 2 As in Example 1, 50 parts of acrylic acid (0.69 g equivalent), 40 parts of n-butyl acrylate, 10 parts of stearyl acrylate,
150 parts of 1,4-dioxane and 0.5 part of 2,2'-azobisisobutyronitrile were charged to carry out a polymerization reaction.

Next, add 16.2 parts (0.14 g equivalent) of hydroxyethyl acrylate and 0.5 part of paratoluene sulfonic acid, and add 4 at 80 ° C.
The mixture was stirred for a time to obtain a resin (2).

This resin (2) Is included in the molecular chain.

Next, 1,4-dioxane / isopropanol (1/1) of a composition containing 3 parts of the resin (2) in a solid content ratio of 3 parts by photopolymerization initiator (trade name: VICURE55) manufactured by Stoffer
(Weight ratio) A 15% diluted solution was applied onto a polyester film in the same manner as in Example 1, ink jet recording was performed, ultraviolet irradiation curing was performed, and then development was performed with a 10% aqueous sodium hydroxide solution. As a result, it was possible to obtain a relief image in which the coating film was in a very good state and the edge portion of the image was sharp. This relief image is a three-dimensional image for decoration,
Further, as in Example 1, it was useful as a slide substitute film for an overhead projector by dyeing a printing plate.

Example 3 As in Example 1, 70 parts of methacrylic acid (0.81 g equivalent), 30 parts of stearyl methacrylate, 100 parts of isopropanol
And 0.5 part of 2,2'-azobisisobutyronitrile were charged to carry out the polymerization reaction.

Next, 61.9 parts (0.46 g equivalent) of chloroethyl acrylate and 36 parts of pyridine were added, and the mixture was stirred at 50 ° C for 4 hours, cooled with water, 14 parts of sodium hydroxide (0.35 g equivalent) and 350 parts of water were added dropwise, and the mixture was stirred for 1 hour. And further stirred at 40 ° C. for 3 hours to obtain a resin (3).

Is included in the molecular chain.

Using this resin (3), a polyester film was coated in the same manner as in Example 1 and subjected to ultraviolet irradiation curing and water development, and a good relief image could be obtained.

Example 4 30 parts of glycidyl methacrylate (0.21
g equivalent), n-butylmethacrylate 50 parts, laurylmethacrylate 20 parts, isopropanol 100 parts and dimethylvaleronitrile 0.5 part were charged and the polymerization reaction was carried out.

Next, itanconic acid 27.3 parts (0.42 g equivalent) and tetramethylammonium bromide 0.8 part were added, and the mixture was stirred at 60 ° C. for 8 hours and then cooled with water, sodium hydroxide 8.3 parts (0.21 g equivalent),
150 parts of water was added dropwise, the mixture was stirred for 1 hour, and further stirred at 40 ° C. for 3 hours to obtain a resin (4).

This resin (4) The group of is included in the molecular chain.

This resin (4) was applied onto a polyester film in the same manner as in Example 1 and subjected to ultraviolet irradiation curing and water development to obtain a good relief image.

Example 5 As in Example 1, 49 parts (1 g equivalent) of maleic anhydride, 51 parts of styrene, 150 parts of methyl ethyl ketone and 0.5 parts of 2,2'-azobisisobutyronitrile were charged and a polymerization reaction was carried out.

Next, hydroxyethyl acrylate 38.7 parts (0.33 g
Equivalent), 1.2 parts of pyridine were added, and the mixture was stirred at 80 ° C for 4 hours,
After cooling with water, 37.7 parts of potassium hydroxide (0.67 g equivalent) and 250 parts of water were added dropwise, and the mixture was stirred for 1 hour and further stirred at 40 ° C. for 3 hours, then, while adding 150 parts of water at 40 ° C. under reduced pressure, methyl ethyl ketone 1
The resin (5) was obtained by distilling off 50 parts. This resin (5) The group of is included in the molecular chain.

When this resin (5) was applied on a polyester film in the same manner as in Example 1 and subjected to ultraviolet irradiation curing and water development, a good relief image could be obtained.

Example 6 As in Example 1, 50 parts styrene sulfonic acid (0.27 g equivalent), 50 parts styrene, 150 parts isopropanol and 2,2 '.
-The polymerization reaction was carried out with 0.5 part of azobisisobutyronitrile, then 12.1 parts of glycidyl acrylate (0.09 g eq.), Tetramethylammonium bromide 0.4 part
Parts, sodium hydroxide 7.0 parts (0.18 g equivalent), and water 100 parts to obtain a resin (6).

When this resin layer (6) was applied onto a polyester film in the same manner as in Example 1 and subjected to ultraviolet irradiation curing and water development, a good relief image could be obtained.

Example 7 As in Example 1, 50 parts of styrene sulphate (0.25 g
Equivalent), 50 parts of styrene, 150 parts of isopropanol and 2,
The polymerization reaction was carried out using 0.5 parts of 2'-azobisisobutyronitrile, and then 11.8 parts of glycidyl acrylate (0.09 g equivalent) and tetramethylammonium bromide 0.4
And 8.8 parts of potassium hydroxide (0.16 g equivalent) and 100 parts of water were modified to obtain a resin (7).

When this resin (7) was applied onto a polyester film in the same manner as in Example 1 and subjected to ultraviolet irradiation curing and water development, a good relief image could be obtained.

Example 8 55 parts (0.56 g equivalent) of 2-hydroxyethyl acryloyl phosphate and methyl acrylate 20 were prepared in the same manner as in Example 1.
Part, tridecyl acrylate 25 parts, isopropanol 15
A polymerization reaction was carried out using 0 part and 0.5 part of 2,2′-azobisisobutyronitrile, and then 28.7 parts (0.22 g equivalent) of glycidyl acrylate, 0.9 part of tetramethylammonium bromide and 13.4 parts of sodium hydroxide ( Resin (8) was obtained by modification with 150 parts of water.

When this resin (8) was applied onto a polyester film in the same manner as in Example 1 and subjected to ultraviolet irradiation curing and water development, a good relief image could be obtained.

Example 9 100 parts of casein made from New Zealand and 300 parts of a water / isopropanol (4/1 weight ratio) mixed solvent were charged into a flask and stirred at 60 ° C., and 4 parts of potassium hydroxide and water were added to this.
Add 50 parts dropwise and stir for an additional 1 hour, then add 30 parts glycidyl methacrylate and tetramethylammonium chloride.
0.9 part was added and the mixture was stirred at 60 ° C. for 10 hours to obtain a resin (9). This resin (9) Is included in the molecular chain.

30 parts of the above resin (9) and 70 parts of the resin (1) obtained in Example 1 per 100 parts of a photosensitive resin, 3 parts by weight of a solid component photoinitiator (product) Name: VICURE5
A 10% water / isopropanol (1/1 weight ratio) dilution of the composition containing 5) was applied to an aluminum sheet in the same manner as in Example 1 so that the solid coating amount was 5 g / m ² . Applied to.

Then, after drying, ink jet recording was carried out, and after ultraviolet ray curing was carried out, water development was carried out. As a result, it was possible to obtain a relief image in which the coating film state was very good and the image edge portion was sharp. After drying, post-exposure was further performed, and then desensitization treatment was performed to obtain a lithographic plate.

Using this flat plate, printing was carried out over a long period of time with an ink containing glycol and cellosolve acetate, but there was no change in the plate surface and good printed matter was obtained.

Example 10 Gelatin manufactured by Nitta Gelatin Co., Ltd. (trade name: P
2115) 100 parts, 1,4-dioxane 200 parts were charged and stirred at 60 ° C., 15 parts of heacrylic acid and 0.5 part of paratoluenesulfonic acid were added thereto, and the mixture was further stirred for 20 hours, and then 150 parts of water was added. Added resin (10) was obtained.

A solid content ratio of 3 parts per 100 parts of a photosensitive resin consisting of a mixture of 20 parts of this resin (10) and 80 parts of the resin (2) obtained in Example 2.
Part Stoufar's photoreaction initiator (trade name: VICURE55)
When a 10% diluted solution of water / isopropanol (1/1 weight ratio) of the composition containing the above was applied to an aluminum sheet in the same manner as in Example 9 to perform ultraviolet irradiation curing and water development,
A good relief image could be obtained.

Example 11 A flask was charged with 100 parts of hydroxyethylated potato starch (trade name: Abelex 2530) manufactured by Abebe Co., and 400 parts of a mixed solvent of water / isopropanol (3/2 weight ratio), and the mixture was heated to 50 ° C.
The mixture was stirred in the above manner, 10 parts of heglycidyl acrylate and 0.3 part of tetramethylammonium chloride were added thereto, and the mixture was further stirred for 15 hours to obtain a resin (11).

The solid component ratio was 3 per 100 parts of the photosensitive resin consisting of a mixture of 10 parts of this resin (11) and 90 parts of the resin (4) obtained in Example 4.
Part Stoufar's photoreaction initiator (trade name: VICURE55)
A composition containing 10% of water / isopropanol (1/1 weight ratio) was applied onto a polyester film in the same manner as in Example 1 to carry out ultraviolet irradiation curing and water development. It was possible to obtain a good relief image.

Example 12 100 parts of carboxymethyl cellulose manufactured by Sanyo Kokusaku Pulp Co., Ltd. in a flask, water / isopropanol (1/1 weight ratio)
Charge 900 parts of mixed solvent and stir at 40 ° C. Add 5 parts of sodium hydroxide to the mixture and stir for 30 minutes, then add 20 parts of 3-chloro-2-hydroxypropyl acrylate and 60 ° C.
The temperature was raised to 0, and the mixture was further stirred for 25 hours to obtain a resin (12).

3 parts by weight of the solid component ratio per 100 parts of the photosensitive resin consisting of a mixture of 40 parts of this resin (12) and 60 parts of the resin (6) obtained in Example 6.
Double Stoufar photoinitiator (trade name: VICURE55)
A composition containing 10% of water / isopropanol (1/1 weight ratio) was applied onto a polyester film in the same manner as in Example 1 to carry out ultraviolet irradiation curing and water development. It was possible to obtain a good relief image.

Comparative Example 1 As in the example, 36 parts of methacrylic acid (0.42 g equivalent), 35 parts of methyl methacrylate, 29 parts of n-butyl methacrylate were used.
Part, isopropanol 100 parts and 2,2′-azobisisobutyronitrile 0.5 part were used to carry out a polymerization reaction, and then glycidyl acrylate 1.5 parts (0.01 g equivalent), tetramethylammonium bromide 0.05 part, and hydroxylation. Comparative resin (A) was obtained by denaturing with 11.8 parts of sodium (0.30 g equivalent) and 200 parts of water.

When this resin (A) was coated on a polyester film in the same manner as in Example 1 and cured by ultraviolet irradiation and water development, the water resistance was insufficient and the crosslinked film swelled and eluted. It was not possible to obtain a good relief image.

Comparative Example 2 As in Example 1, 90 parts of methacrylic acid (1.05 g equivalent), n
-Polymerization reaction was carried out using 10 parts of butyl methacrylate, 150 parts of isopropanol and 0.5 parts of 2,2'-isobisisobutyronitrile, and then glycidyl acrylate.
89.3 parts (0.70 g equivalent), tetramethylammonium bromide 2.7 parts, and sodium hydroxide 14 parts (0.35 g equivalent),
It was modified with 400 parts of water to obtain a comparative resin (B).

When this resin (B) was applied onto a polyester film in the same manner as in Example 1 and cured by ultraviolet irradiation and water development, cross-linking proceeded excessively and the pattern was not completely removed, resulting in a good relief image. I couldn't get it.

Front page continuation (72) Inventor Akira Yamashita 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Yuka Fine Co., Ltd. Research & Development Laboratory (56) References JP-A 52-136003 (JP, A) JP-A 50- 85404 (JP, A)

Claims (11)

[Claims] 1. A water-based ink is used for recording on a photosensitive resin layer formed on a base material, and the entire surface of the photosensitive resin layer is irradiated with radiation to cause a photo-curing reaction on a portion not recorded with the water-based ink. In the relief forming method, in which the photosensitive resin layer in the water-based ink recording portion is discharged to form a relief by developing with water or an alkaline water after insolubilization with water, the photosensitive resin used for the photosensitive resin layer is Radiation-curable water-soluble anionic synthetic resin (A) alone, or radiation-curable water-soluble anionic synthetic resin (A) and radiation-curable derivatives obtained from natural products such as casein, gelatin, starch, and cellulose. Relief forming method, characterized in that any one of a mixture of 50% by weight or less of a water-soluble resin (B) 2. A radiation-curable water-soluble anionic synthetic resin comprising an anionic resin selected from (a) a polymerizable double bond and (b) a carboxyl group, a sulfonic acid group, a sulfuric acid ester group and a phosphoric acid ester group. The relief forming method according to claim 1, which is a radiation-curable water-soluble anionic synthetic resin having a group and / or a functional group of a neutralized salt thereof. 3. A copolymer of a radiation-curable water-soluble anionic synthetic resin with 10 to 90% by weight of a carboxyl group-containing polymerizable monomer and 90 to 10% by weight of a polymerizable monomer. The resin is reacted with a polymerizable monomer having an epoxy group by reacting 0.1 to 0.6 g equivalent of the carboxyl group-containing polymerizable monomer of the copolymer resin to esterify a part of the carboxyl group of the copolymer resin. If necessary, the whole or a part of the remaining carboxyl groups may be combined with alkali, ammonia,
Alternatively, the relief forming method according to claim 1, which is a resin neutralized with a base such as an amine. 4. The radiation-curable water-soluble anionic synthetic resin is a resin containing a group (c) and a group (d) in the molecule, according to claim 3. Relief forming method. [Wherein R ¹ , R ² and R ³ are H or CH ₃ and M is H, Li, N
a, K, NH ₄ or an amine residue. ] 5. A radiation-curable water-soluble anionic synthetic resin is obtained by subjecting a resin having a polybasic acid group (or its acid anhydride group) and a polymerizable monomer having a hydroxyl group to an ester reaction. A resin with vinyl and carboxyl groups,
The relief forming method according to claim 1, wherein the resin is a resin in which all or part of the remaining carboxyl groups are optionally neutralized with a base such as alkali, ammonia, or amine. 6. The relief forming method according to claim 5, wherein the radiation-curable water-soluble anionic synthetic resin is a resin containing the following groups in the molecule. [In the formula, R ¹ is H or CH ₃ , M is H, Li, Na, K, NH ₄ or an amine residue, and A is an alkylene group having 2 to 6 carbon atoms. ] 7. A radiation-curable water-soluble anionic synthetic resin comprising 10 to 90% by weight of a carboxyl group-containing polymerizable monomer.
And a copolymer resin with 90 to 10% by weight of another polymerizable monomer that can be copolymerized with a polymerizable monomer having a hydroxyl group, and a polymerizable monomer having a carboxyl group of the copolymer resin. Body 0.1 ~
By reacting with 0.6 g equivalent, a part of the carboxyl group of the copolymer resin is ester-bonded, or if necessary, all or part of the remaining carboxyl group is neutralized with a base such as alkali, ammonia, or amine. The relief forming method according to claim 1, wherein the relief forming method is a resin. 8. A radiation-curable water-soluble anionic synthetic resin comprising a carboxyl group-containing polymerizable monomer in an amount of 10 to 90% by weight.
And a copolymer resin of 90 to 10% by weight of another polymerizable monomer that can be copolymerized with a halogenated polymerizable monomer, and a carboxyl group-containing polymerizable monomer of the copolymer resin. 0.1-0.6g
A dehydrohalogenation reaction is carried out with an equivalent amount to form an ester bond with a part of the carboxyl groups of the copolymer resin, or if necessary, a part or all of the remaining carboxyl groups are neutralized with a base such as alkali, ammonia, or amine. The relief forming method according to claim 1, wherein the relief forming method is a hydrated resin. 9. The radiation-curable water-soluble anionic synthetic resin according to claim 8, wherein the resin contains the following (e) group and (f) group in the molecule. Relief forming method. [Wherein R ¹ , R ² and R ³ are H or CH ₃ and M is H, Li, N
a, K, NH ₄ or an amine residue, and A is an alkylene group having 2 to 6 carbon atoms. ] 10. A radiation-curable water-soluble anionic synthetic resin, which is a resin having a carboxyl group and a vinyl group obtained by reacting an epoxy compound with an unsaturated polybasic acid, or optionally a carboxyl group of this resin. The method for forming a relief according to claim 1, wherein the resin is a resin obtained by neutralizing all or part of the above with a base such as alkali, ammonia, or amine. 11. The relief forming method according to claim 1, wherein the recording with the aqueous ink is recording with an ink jet.