JP2719565B2 - Photographic type for printing - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photographic printing mold, and more particularly to a photographic printing mold comprising a photosensitive resin image using a one-part photosensitive emulsion.

[Prior Art] Two-part photosensitive emulsions have been mainly used as a method for producing a photographic printing die, and use of a one-part photosensitive emulsion has recently been considered.

The two-part light-sensitive emulsion is first represented by a light-sensitive emulsion (a light-sensitive emulsion obtained by mixing a diazo-based light-sensitive agent and a dichromate in an emulsion mainly composed of a polyvinyl alcohol / vinyl acetate emulsion as the light-sensitive emulsion). After forming a photosensitive resin image on the screen mesh on the frame by photoengraving using a photoengraving method, a urethane resin (polyester resin and isocyanate as a hardener Compound)
Is applied to both sides of the screen with a rubber roller or a brush, then the urethane resin adhering to the openings other than the image is removed by a suction machine, and dried by heating to produce a printing dies for printing. The photographic mold for printing obtained in this way reads the area ratio of the image and the opening with a computer, finds the area of the opening, calculates the printing area by multiplying it by the printing quantity, and according to the printing area. The amount of glue is adjusted.

The disadvantages of the two-part photosensitive emulsion are as follows: (1) Two steps of an image forming step and a reinforcing liquid applying step are required.

(2) Clogging due to the reinforcing liquid is likely to occur.

(3) Fine line images cannot be formed.

(4) The film thickness is not constant.

(5) Toxicity of isocyanate compounds and environmental pollution by pollutants.

As a result, the development of one-pack type photosensitive emulsion has been remarkable. One-part photosensitive emulsions have the following advantages in that the above-mentioned reinforcing liquid is not used. (1) The image forming step and the curing liquid coating step can be performed continuously.

(2) There is no clogging due to the reinforcing liquid, and a thin line image can be formed.

(3) The film thickness is constant.

(4) It does not contain pollutants that may be particularly problematic.

And so on.

However, the one-part photosensitive emulsion is required to have high sensitivity because the thickness of the photosensitive resin (emulsion) itself is larger than that of the two-part photosensitive emulsion by the amount of the reinforcing film.

Recently, stilbazolium-based emulsions, diazo-based emulsions, and acrylic-based emulsions have been used as high-sensitivity emulsions. It became possible to obtain.

[Problems of the Invention] One of the drawbacks of the one-part photosensitive emulsion is that it is more difficult to read an image and an opening with a computer used for adjusting the amount of glue than the two-part photosensitive emulsion. In particular, in the case of a two-part light-sensitive emulsion, the above reading is easy because the surface has a black color or a color close to it (for example, brown) due to the colorant contained in the reinforcing liquid. Normally, in the case of photographic type for textile printing, the plate is stored for at least 3 years after the first printing, so the plate may be exposed to sunlight at the time of storage, and it may be considerably deteriorated in actual conditions. is expected.

That is, by providing the photosensitive resin image surface necessary for reading the image and the area ratio of the opening with a computer for the one-part photosensitive emulsion, the above-mentioned problem of the two-part photosensitive emulsion is solved. At the same time, it becomes possible to obtain a photographic printing mold utilizing the features of the one-pack type photosensitive emulsion.

[Means for Solving the Problems] The present inventors have conducted intensive studies in order to solve the above problems, and as a result, added a light absorbing material to the photosensitive resin image (in the photosensitive layer) to obtain a reflectance of 3 to 10 By forming a surface within the range of%, it was found that the problem could be solved, and the present invention was completed.

That is, the present invention relates to a printing photographic mold obtained by forming a photosensitive resin image on a screen mesh spread on a frame,
The present invention relates to a photographic printing mold using a one-part photosensitive emulsion, characterized in that the surface of the photosensitive resin image has a reflectance of at least 3 to 10%.

[Operation] When the reflectance is 10% or more, reading of the amount of glue is easily influenced by external conditions (the external conditions can include the environment, the quality of the plate, etc.), and it is difficult to determine. is there.
When the reflectance is 3% or less, reading is easy, but at the time of image formation, the irradiation time of ultraviolet rays is extremely long, so that a problem occurs and the cost is low.

Within the range of the reflectance of 3 to 10% of the present invention, it can be said that the one-pack type photosensitive emulsion can be most stably used as a photographic printing type. More preferably, the surface has a reflectivity in the range of 4-5%.

Reflectivity The reflectivity ρ is the reflected radiant flux φ [w] and the incident radiant flux φ ₀ [w] when the incident radiant flux is reflected on the surface of the object.
Is defined as the reflectance.

Light-absorbing material The light-absorbing material is composed of particles, and at least the ultraviolet / visible light absorption region (200 to 5) of the photosensitive material contained in the photosensitive resin.
Substance having absorbance at 00 nm): Examples of the substance include organic / inorganic colored pigments described in New Edition Pigment Handbook (edited by Japan Pigment Technical Association).

Examples of the pigment that can be used in the present invention include, for example, phthalocyanine, azo, quinacridone, dioxazine,
And carbon black.

The addition of the light-absorbing material does not require a general restriction, but is preferably 0.1 to 10 g / Kg with respect to the solid content of the photosensitive emulsion.

Since the reflectance varies depending on the pigment, as a reference, a substance which is added with a reflectance of 10% or less, has a low value of the reflectance even with a small amount of addition, and does not inhibit the photosensitivity is preferable.

Photosensitive emulsion The photosensitive emulsion that can be used in the present invention includes a water-soluble resin,
This is a water-containing emulsion containing a hydrophobic emulsion and a photosensitive agent as main components, and if necessary, a plasticizer, a thixotropic agent, a stabilizer and a solvent.

Examples of the water-soluble resin include saponified polyvinyl acetate (polyvinyl alcohol) and derivatives thereof;
Examples thereof include saponified polyvinyl acetate having carboxyl, styryl, and acryl groups, and polyvinylpyrrolidone.

Examples of the hydrophobic emulsion include latex, urethane emulsion, polyvinyl acetate, or a copolymerized emulsion thereof; such copolymers include ethylene, acrylic S, acrylamides, and the like.

Examples of the photosensitive agent include dichromates, diazo compounds, and photopolymerizable materials.

Examples of the diazo compound include a diphenylamine derivative such as 4-diazodiphenylamine sulfate, 4-diazo-3-methoxydiphenylamine sulfate, and 4-diazo-4'-methoxydiphenylamine sulfate, and a crosslinking agent (formalin, acetaldehyde, Aldehydes such as paraformaldehyde and aromatic aldehyde, and 4,4'-dimethoxymethyldiphenyl ether, etc.) in a strong acid.

As the photopolymerizable material, an ethylenically unsaturated compound,
In a photopolymerizable material comprising a photopolymerization initiator, as the ethylenically unsaturated compound, glycerin diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate polyester acrylate, an acrylate compound represented by urethane acrylate,
Alternatively, those methacrylate compounds may be mentioned.

Examples of the photopolymerization initiator include benzoyl or derivatives thereof, benzophenone or derivatives thereof, derivatives such as benzyldimethyl ketal, anthraquinone and thioxanthone, biimidazole compounds, and commercially available products represented by lusilyl, irgacure, and the like. These may be used alone or in combination.

The photosensitive agents used in the present invention may be used alone or in combination, and a combination of high sensitivity as a photosensitive emulsion is desirable.

In the photosensitive emulsion used in the present invention, the ratio of the water-soluble resin to the hydrophobic colloid is preferably in the range of 1:12 to 2: 8, and the added sensitizer is a solid of the water-soluble resin and the hydrophobic colloid. Minute
The amount is preferably 0.5 to 30 parts by weight with respect to 100 parts by weight, but if either the water-soluble resin or the hydrophobic colloid is self-photosensitive, it may not be added. The emulsion can be applied directly to a screen mesh (usually using a 50-300 mesh multi- or mono-fermentation screen) (direct method), or it can be applied to a polyester film in advance and then added to water or emulsion. Application using (direct method)
Then, a photosensitive film is formed.

Then, using a light source that generates ultraviolet rays abundantly (for example, a mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, and a chemical lamp), vacuum-adhering a positive film having a pattern for printing and dyeing to the photosensitive film, Irradiate with ultraviolet light. Usually, step baking (step baking) is performed using a chemical lamp, so that a high sensitivity of the photosensitive film is required. At least 20 meters from 100W chemical lamp
In cm, within 8 to 40 seconds is desirable.

After exposure, the phenomenon occurs due to water or warm water to form an image.
The image is dried or, if necessary, hardened with a curing liquid and then dried.

As the curing liquid, aldehydes (formaldehyde, acetaldehyde, glyoxal, glutaraldehyde, glutaric acid and the like can be mentioned as the aldehyde) and acids (hydrochloric acid, sulfuric acid, phosphoric acid,
A mixture of toluenesulfonic acid and the like).

[Effect] By using the photographic printing mold of the present invention, the use of the urethane resin, which has long been suffered for a long time, can be stopped, and a printed image with a precise image can be obtained. According to the present invention, it has become possible to respond to cleanliness and precision in the printing industry.

[Examples] Next, the present invention will be described in more detail with reference to Examples.

Example 1 A 150-mesh tetron screen (monofilament) is spread on an aluminum frame (900 × 1800 mm), and four sides are fixed with a rubber-based adhesive (for example, Konishi; Bond G-17).

Next, a one-pack type photosensitive emulsion having the following composition is applied to both sides of the screen using a bucket, and dried with warm air at 40 to 45 ° C for 20 minutes.

Further, after a single coating on the printing surface side, the coating is dried in the same manner to obtain a photosensitive plate having a surface film thickness of 10 μm.

A positive film having a pattern for printing and dyeing is vacuum adhered to the photosensitive plate, and irradiated with a chemical lamp (100 w, distance 20 cm) for 15 seconds.

After washing with water at 20 to 25 ° C and developing, apply a curing liquid of the following composition, dry with warm air at 40 to 45 ° C for 20 minutes, and reflectivity
A 4.9% printing photographic mold is obtained. When the printing paste was printed on the fabric after calculating the area using the printing photographic mold thus obtained, a clear printed matter was obtained with the calculated results.

One-part emulsion 1. * 10 wt% of a reaction product of stilbazolium salt and polyvinyl alcohol consisting of γ-picoline and terephthalaldehyde
54 parts by weight of aqueous solution and 50% by weight of polyvinyl acetate emulsion
Photosensitive emulsion consisting of 46 parts by weight of aqueous solution ··· 988.0 g * Carbazole dioxazine violet ··· 2.4 g * Water ··· 9.6 g Curing solution * Glyoxal 40 wt% aqueous solution ··· 10.0 g * HCl 3 wt% Aqueous solution ... 500.0 g * water ... 90.0 g Example 2 Instead of the one-part photosensitive emulsion of Example 1, a one-part photosensitive emulsion having the following composition was used in a bucket, After coating on both sides, dry with warm air at 40-45 ° C for 20 minutes. The same treatment as in Example 1 is performed to obtain a printing photographic mold having a reflectance of 4.8%.

After calculating the area in the same manner as in Example 1, when printing paste was printed on the fabric, a clear printed matter was obtained as calculated.

One-part emulsion 2. * 15 wt% aqueous solution of carboxylic acid-modified polyvinyl alcohol,
Degree of polymerization 1700 ・ ・ ・ ・ 247.6g ＊ SBR latex emulsion ・ ・ ・ ・ 700.0g ＊ Trimethylolpropane triacrylate ・ ・ ・ ・ 4
5.0 g * Benzyl dimethyl ketal ... 2.5 g * Benzophenone ... 2.5 g * Phthalocyanine blue ... 2.4 g Example 3 Example 1 Instead of the light absorbing material of the one-part photosensitive emulsion,
One-part photosensitive emulsions were prepared using the light absorbing materials shown below, and processed in the same manner as in Example 1 to form an image. The reflectance was measured. The following table was obtained.

Example 4 One-part photosensitive emulsion 3. * 15 wt% aqueous solution of partially saponified polyvinyl acetate, degree of polymerization 2400 ... 234.1 g * Polyvinyl acetate emulsion ... 700.0 g * Trimethylolpropane triacrylate ... 45.0g * Benzyl dimethyl ketal ··· 2.5g * Benzophenone ···· 2.5g * Phthalocyanine blue ··· 2.4g * Condensation product of 4-diazo-3-methoxydiphenylamine sulfate and paraformaldehyde (in phosphoric acid) ..4.5 g The above one-part photosensitive emulsion 3. was mixed with a polyester film (for example, ICI: Melinex 542 Film 7).
5 μ), dried to a thickness of 40 μ, and using the same screen as in Example 1.1, the film was placed on the printing surface with the film surface aligned, and the one-part photosensitive emulsion 3. Is applied and the film is dried after bonding.

The same procedures as in Example 1 were carried out to obtain a photographic printing mold having a reflectance of 5.3%. After calculating the area in the same manner as in Example 1, when printing paste was printed on the fabric, a clear printed matter was obtained as calculated.

Example 5 In the case where the photographic printing mold of the present invention was manufactured using the one-part photosensitive emulsion of Example 1 and it took about 40 minutes, the photographic printing mold was manufactured using the two-part photosensitive emulsion. If it took about 80 minutes. In addition, when the resolution of both was examined, the printing photographic mold composed of a one-part photosensitive emulsion had a clear gap of 100 μm between lines, but the printing photographic mold composed of a two-part photosensitive emulsion had
The space between 300 μm lines was almost clogged.

Comparative Example When Example 1 was performed using a commonly used two-part photosensitive emulsion instead of the one-part photosensitive emulsion of Example 1, the reflectance of the obtained plate was 12%. No reading was possible.

Claims (1)

(57) [Claims] In a photographic printing press obtained by forming a photosensitive resin image on a screen mesh spread on a frame, the photosensitive resin image surface has at least 3 to 10%.
A photographic type for printing using a one-pack type photosensitive emulsion characterized by having a reflectance in the range of (1).