JPH0764277A - Photosensitive resin letterpress material - Google Patents

Abstract

PURPOSE:To make it possible to take matrix without chipping of the projecting parts of an original plate and distorting of the recessed parts of a matrix by applying a photosensitive resin having a specific elastic modulus in compression to application for matrix taking. CONSTITUTION:The elastic modulus in compression in photoset parts at 150 deg.C measured by a heating tensile testing machine 'RTM-100(R)' produced by TOYO BALDWIN, is specified >=4kg/cm<2>%, more preferably the elastic modulus in compression is specified to >=6kg/cm<2>% and more particularly preferably the elastic modulus in compression is specified to >=9kg/cm<2>%. The photosensitive letterpress material to be used is formed by providing the surface of a substrate consisting of steel, aluminum, polyester film, etc., subjected to an adhesive treatment with the photosetting photosensitive resin. The photosensitive resin is exemplified by solid photosensitive resins formed by compounding photoset materials with carrier polymers of polyamide, completely saponified polyvinyl acetate, partially saponified polyvinyl acetate, satd. polyester, etc., or solid photosensitive resins, etc., formed by introducing unsatd. groups to the side chains, etc., of the respective polymers to impart photosensitivity thereto.

Description

Detailed Description of the Invention

[0001]

The present invention relates to various relief plates for printing, relief masks for sandblasting, displays,
The present invention relates to a name plate, a relief printing plate, and the like, and particularly to a photosensitive resin relief printing plate material suitable for fields requiring excellent high-temperature physical properties and hardness, such as a master printing plate material and hot stamping. Of these, the mother plate relief material is used when manufacturing a rubber plate.

[0002]

2. Description of the Related Art Conventionally, in order to manufacture a rubber plate (such as a seal), it is first necessary to make a rubber mold, that is, a mother mold. For this, a matrix board in which a phenol resin powder or a cardboard board is coated with a phenol resin The one that is hardened is used. In this case, in order to manufacture the master mold,
20 kg / cm ^{2 of the} above-mentioned phenol powder or matrix board at 130 to 150 ° C. is used by using a relief obtained by etching a metal plate or a photosensitive resin as a father mold.
It had to go through a complicated process of pressing at a high temperature and high pressure of -50 Kg / cm ² to cure the phenol and make a mold.

Therefore, the father type is conventionally 0.5 to 4
The ones with etched zinc of mm thickness were often used, but recently there are problems of waste liquid and handling.
The relief of 4 mm thick photosensitive resin has been shifting. As the photosensitive resin relief plate used here, an alcohol development type and a water development type are known, and this is mainly used as a relief printing plate material for a mother die.

[0004] When a mother resin is used to make a mold with a relief plate for a photosensitive resin master, a very high temperature and high pressure load is applied to the relief plate for the photosensitive resin master at the time of removing the master mold. No deformation, destruction, etc. is necessary to create a defect-free matrix matrix with accurate reproducibility.

[0005]

However, in practice, when the original plate is not a metal plate but a relief plate material for a photosensitive resin master plate, the convex parts of the master plate are chipped, especially the concave parts of the master block are wavy or distorted. Problem occurs. The present invention has found an appropriate compressive elastic modulus at high temperature in order to improve the drawbacks of the prior art, and by providing it, it provides a photosensitive resin relief printing plate material that can be favorably molded. is there.

[0006]

The object of the present invention is as follows.
Toyo Baldwin Co., Ltd., Heat Tensile Tester RTM-1
The compression elastic modulus of the photo-cured part at 4 ° C / cm ² % or more at 150 ° C. measured at 100 ° C. is desirably 6 kg / cm ²
cm ² % or more, particularly preferably a compression elastic modulus of 9 kg / cm ² %
This is achieved by the photosensitive resin relief plate material having the above characteristics.

The photosensitive resin relief material used in the present invention comprises a photocurable photosensitive resin provided on a substrate such as steel, aluminum or polyester film which has been subjected to an adhesion treatment. As the photosensitive resin, the compression modulus of the light-cured portion at 150 ° C. measured by a heat tension tester RTM-100 manufactured by Toyo Baldwin Co., Ltd. is 4 kg.
Everything can be used as long as it is not less than / cm ² %.
Specific examples include the following.

That is, polyamide, fully saponified polyvinyl acetate, partially saponified polyvinyl acetate, saturated polyester,
Polyurethane, polyurea, or a solid photosensitive resin prepared by mixing a photocured product with a carrier polymer such as a copolymer thereof.
Alternatively, a solid photosensitive resin to which photosensitivity is imparted by introducing an unsaturated group into a side chain or the like of these polymers, and a liquid photosensitive resin containing unsaturated polyester, unsaturated polyurethane or the like as a main component. . In particular, a mixture of polyether urea urethane and a polyfunctional crosslinking agent is preferably used because it has high crystallinity and excellent properties at high temperatures. The thickness of the photosensitive layer formed of these photosensitive resins is usually 0.7 to
The range is 1.5 mm.

For the photo-cured portion, a circular blank negative having a diameter of 4.7 mm was brought into close vacuum contact with an unexposed raw plate and irradiated with ultraviolet rays in an amount necessary for image exposure, and then the unexposed portion was washed off with water and a brush. After drying with hot air of 70 ° C. for 30 minutes, ultraviolet rays of 3 times the amount necessary for image exposure are applied. The substrate having this circular image portion in the center is cut into a square of about 1.2 cm square to obtain a sample. The exposure was made by Anderson and Breeland UV573 unit (illumination 8 measured by Ushio UV meter UV365 under PVC mat sheet).
0 w / m ² ) and the time is 2 minutes.

[0010] After polishing the cut surface of the sample horizontally on the lower stand of the Toyo Baldwin Heat Tensile Tester RTM-100, a stainless steel cylinder having a diameter of 1.5 cm and a length of 45 cm was set, and the sample was placed thereon. Put.
Also, as a compression jig, the cut surface is horizontally polished and the diameter is 8 m.
A stainless steel cylinder having a length of m and a length of 55 cm is attached to the load cell for use. The above set is mounted together with the sample in a constant temperature dome heated to 150 ° C., left for 2 minutes and 30 seconds, and compressed at a speed of 0.5 mm / min for recording. About 2
A tangent line is drawn on the chart at the point of being pressed by 00 μm, and the value is divided by the area of the circle of the sample and the percentage of the pressed portion with respect to the thickness of the image portion to obtain the compression elastic modulus. Generally, the hardness measured by a Shore-D hardness meter or a Barcol hardness meter, which is used to easily measure the physical properties, is the puncture property of a needle and does not necessarily correspond to the actual usage situation.

In order to form a master block having good reproducibility by using a relief plate material for a photosensitive resin master block, generally, a master block 130 is used.
It is necessary that the letterpress plate for the photosensitive resin mother die has high physical properties so as not to be deformed or destroyed under use conditions of high temperature of up to 150 ° C., high temperature of ^{20 to} 50 kg / cm ² , and high pressure. With Toyo Baldwin's heated tensile tester RTM-100,
Compressive modulus of light-cured part at 150 ℃ is 4kg / cm ²
If a relief plate for a photosensitive resin master block that does not satisfy the physical properties of not less than 100% is used, the master block is deformed during master block fabrication and the recesses of the master block obtained are distorted, so that a master block with good reproducibility cannot be obtained. Further, the relief of the relief plate for the photosensitive resin mother die is peeled off from the adhesive layer due to the deformation at the time of mother die making, which makes it impossible to repeatedly carry out the mother die making, which cannot be put to practical use. For this reason, the compressive elastic modulus of the photo-cured part at 150 ° C is 4 kg /
It must be at least cm ² %.

Plate making of the photosensitive resin relief plate material of the present invention is performed in the same manner as in conventional printing applications. First, a negative film is produced from an original by a photographic method or the like. A negative film is vacuum-adhered to the surface of the photosensitive layer of this film, and then the unexposed and uncured portions are dissolved in a developing solution to obtain a relief on the substrate. After this is dried to remove the developing solution, the entire surface is exposed to 3 times the amount required for image exposure to sufficiently perform the photocuring reaction.

A release agent such as silicon is applied to the plate material thus obtained, that is, the relief printing plate for mother die, and a stopper is installed on the lower platen of the press machine whose temperature is set to 150 ° C. Place the coated matrix board, and place the master plate relief on it so that the relief surface touches the matrix board. Then, lightly touch the top platen to the base surface of the mother-plate relief plate, leave it unpressurized for about 1.5 to 2 minutes, then take 30 seconds between the top and bottom plates to reach 30 to 50 kg / cm ^2. Apply pressure gradually and hold for about 8 minutes. At this time, a spacer may be sandwiched between the upper and lower platens in order to keep the floor thickness of the completed matrix board mother die constant. After that, the press machine is depressurized and the matrix board master mold that has been molded and cured is taken out to obtain a good master mold.

[0014]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the examples, parts are parts by weight.

Examples 1 and 3 and Comparative Example 1 First, 55 parts of ε-caprolactam and N, N'-bis (γ-
Aminopropyl) piperazine-adipate 50 parts of a polyamide having a specific viscosity of 2.50 obtained from 45 parts, an acrylic acid reaction product of ethylene glycol diglycidyl ether 35
Parts, 1 part of benzoin methyl ether and 3 parts of methacrylic acid were dissolved by heating in 200 parts of methanol. The additives shown in Table 1 were added to this polymer solution to obtain a uniform transparent solution.

[0016]

This solution was cast on a Teflon sheet, and the methanol was air-dried in the dark, and then further depressurized at 40 ° C.
And dried for 16 hours. The sheet of the uniform transparent photosensitive resin composition thus obtained was provided with an adhesive layer to give a thickness of 188.
Thermal adhesion on a 100 μm polyester film to a thickness of 100
A photosensitive resin plate having a photosensitive resin layer of 0 μm was prepared. In order to prepare a sample for a tensile test, a photosensitive resin composition sheet is sandwiched between polyester films having a thickness of 188 μm, and heated and rolled using a hot press set at 90 ° C. so that the photosensitive layer has a thickness of 1000 μm. did.

Example 2 N, N'-bis (3-aminopropyl) piperazine 59
Parts and 1,3-bis (aminomethyl) cyclohexane 1
2 parts and 700 parts of methanol are dissolved, and 600 parts of polyethylene glycol (average molecular weight 600) and 370 parts of hexamethylene diisocyanate are reacted therewith to obtain substantially 300 parts of urethane oligomer having isocyanate groups at both ends. Was slowly added with stirring. Both reactions were completed in about 10 minutes. This solution was placed in a Teflon-coated petri dish, and the methanol was removed by evaporation, followed by vacuum drying.

50 parts of the polymer thus obtained was dissolved in 200 parts of methanol at 60 ° C., 2 parts of glycidyl methacrylate was added to this solution, and the mixture was stirred for 3 hours to react glycidyl methacrylate with the ends of the polymer.
3 parts of adipic acid (forms an ammonium salt with a basic nitrogen atom of the piperazine ring of the main chain of the polymer and a terminal amino group to solubilize the polymer) in this solution, dipentaerythritol, penta and hexa 40 parts of a mixture of acrylates (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), 0.1 part of hydroquinone monomethyl ether and 1.0 part of benzyl dimethyl ketal were added to obtain a solution of a photosensitive resin composition.
This was processed in the same manner as in Examples 1 and 3 to prepare a photosensitive resin plate.

The sample thus obtained had a diameter of 4.7.
A circular blank with a diameter of 0.3 mm is vacuum-contacted to an unexposed raw plate and irradiated with an amount of ultraviolet rays necessary for image exposure, and then the unexposed part is rinsed with a brush type developing device filled with tap water to 70 ° C.
After 30 minutes of drying with hot air, the amount of 3
A substrate having a circular image portion obtained by irradiating double ultraviolet rays in the center was cut into a square of about 1.2 cm square, which was used as a compression sample. Further, instead of the circular blank negative, a negative film having a solid portion of 4 cm square was processed in the same manner as above to obtain a sample for a master mold.

The compressive elastic modulus of the sample was measured as follows. A stainless steel cylinder having a diameter of 1.5 cm and a length of 45 cm, the cut surface of which is horizontally polished, is set on the lower stand of a heating and pulling tester RTM-100 manufactured by Toyo Baldwin Co., Ltd., and a sample is placed thereon. Further, as a compression jig, a stainless steel cylinder having a diameter of 8 mm and a length of 55 cm whose cut surface is polished horizontally is attached to a load cell for use. 1
The above set is mounted together with the sample in a constant temperature dome heated to 50 ° C., left for 2 minutes and 30 seconds, and then compressed at a speed of 0.5 mm / min for recording. A tangent line is drawn on the chart at a point of about 200 μm indentation, and the value is divided by the area of the sample circle and the percentage of the indented portion with respect to the thickness of the image area to obtain the compression elastic modulus.

The mastering was carried out as follows. First, Repelzit manufactured by ANCHOR / LITHKEMKO in the United States was applied onto the 4 cm square plate having a solid portion obtained by the above method.
Next, press machine (made by Toyota Shokai) whose temperature was set to 150 ° C
A stopper was installed on the lower platen, and a matrix board coated with phenol resin (K6 board manufactured by British Econo Co.) was placed on the plate, and a mother relief was placed on the matrix board so that the relief surface touched the matrix board.

Then, the upper platen is lightly touched on the base surface of the mother-plate relief plate, and it is allowed to stand without pressure for about 2 minutes, and then the upper and lower platens are gradually pressurized to 30 kg / cm ² for about 30 seconds. , Hold for about 8 minutes. At this time, in order to keep the floor thickness of the completed matrix board mold constant, 380
A 0 μm spacer is sandwiched between the upper and lower platens. afterwards,
The matrix board master mold which was molded and cured by depressurizing the press machine was taken out, and the master moldability of the master plate relief plate was examined. The results are shown in Table 2.

[0024]

[0025]

INDUSTRIAL APPLICABILITY According to the present invention, as described above, a photosensitive resin having a specific compression elastic modulus is applied to a mold making application, and the convex portion of the original plate is chipped or the concave portion of the mother mold is distorted. It is effective for performing mother molding without using. This is 15
This has been realized by finding a photosensitive resin relief plate material having a compression elastic modulus of 4 Kg / cm ² % or more at a photo-cured portion at 0 ° C. and applying it to this application.

Claims (1)

[Claims] 1. A photosensitive resin letterpress material having a compression elastic modulus of 4 kg / cm ² % or more at a photocured portion at 150 ° C. measured by a heat tension tester RTM-100 manufactured by Toyo Boardwin Co., Ltd.