JP3047464B2 - Photopolymer topographic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photosensitive resin relief printing plate material having a very good relief retention property and having a hardened layer having a high resistance to ink and washing oil. It is.

(Problems to be Solved by Conventional Techniques and Inventions) Conventionally, photosensitive resin letterpress materials are plastic films,
It is often a laminate in which an adhesive layer is provided on a support such as a steel plate or an aluminum plate, and a photosensitive resin layer is laminated thereon. The letterpress for printing should be obtained by overlaying a negative film on the above-mentioned photosensitive resin letterpress material, exposing it to actinic rays, subjecting it to a developing treatment to remove unexposed parts with an appropriate solvent, drying and post-exposure. Adjusted for printing. However, when the adhesive strength between the relief and the adhesive layer or between the adhesive layer and the support is insufficient, a problem often occurs that the relief falls off the support in the plate making process or the printing process. Furthermore, in the printing process, the ink is damaged by the printing ink during printing, and the relief comes off.During printing, after printing, when washing off the attached ink, or during storage of the printing plate from which the ink has been washed, Troubles in which the relief drops off when immersed in oil often occur.

In order to prevent such troubles, a method using a crosslinked polyester polyurethane resin layer obtained by reacting a linear polyester and a polyvalent isocyanate on the surface of a support or a crosslinked polyester obtained by reacting a linear polyester polyurethane with a polyvalent isocyanate A method using a polyurethane resin layer has been proposed (JP-A-49-133102). However, in these methods, it is necessary to appropriately adjust the degree of cross-linking in order to sufficiently exert the adhesive force. However, if the degree of cross-linking is low, the printing ink or the washing oil of the printing ink (which is generally used in general) (E.g., halogen-based solvents, ester-based solvents, and ketone-based solvents), and the relief tends to fall off. On the other hand, if the degree of cross-linking is increased, adhesion to the relief will be insufficient, causing the relief to fall off. Management is very difficult. Therefore, in order to improve the adhesive force with the relief with a highly crosslinked adhesive layer, a system in which a photopolymerizable ethylenically unsaturated bond compound is introduced into the adhesive layer, that is, a system of a linear polyester polyurethane and a polyvalent isocyanate. An adhesive layer having a photopolymerizable ethylenically unsaturated compound added thereto has been proposed (JP-A-49-135702). However, the polyester polyurethane is easily attacked by a washing oil containing a halogen-based solvent, an ester-based solvent, a ketone-based solvent or the like, which has a strong affinity for the polyester polyurethane, and a satisfactory result has not been obtained. Further, these adhesive layers have a problem in tackiness of a non-image portion of a printing plate due to migration of a (meth) acrylate-based photopolymerizable monomer often used for a photosensitive resin layer.

As a method for solving the above problems, a so-called back exposure method in which a small amount of the entire surface is exposed from the support side before or simultaneously with the image exposure in the plate making process, and the photosensitive layer on the support side is partially photo-cured is also performed. However, it has the drawbacks that it is very difficult to control the amount of back exposure, and it cannot be applied at all when the support is an opaque aluminum plate or steel plate.

(Means for Solving the Problems) The present inventors have conducted intensive studies on a photosensitive resin relief printing plate having no disadvantages of the above-described conventional technology, and as a result, have finally completed the present invention.

That is, the present invention provides a photosensitive resin relief printing plate material obtained by laminating a photosensitive resin layer on a support subjected to an adhesive treatment, wherein a thickness obtained by photocuring between the support and the photosensitive resin layer. A photosensitive resin relief printing plate characterized by having a barrier layer having a resistance to printing ink of 3 μm or more and less than 100 μm or a washing oil of the printing ink.

The photocured barrier layer, which is a feature of the photosensitive resin relief printing material of the present invention, is composed of a highly crosslinked resin layer, and printing ink or a washing oil of the printing ink penetrates the adhesive layer, and the adhesive layer And plays an important role of preventing the relief from falling off from the support by the obstacle layer. In addition, only the thin layer of 0.5 to 10 μm from the surface of the photo-cured obstacle layer on the adhesive layer is impeded by photo-curing due to oxygen existing at the time of photo-curing. Therefore, the photosensitive resin layer laminated on the obstacle layer is extremely strongly optically bonded to a light-uncured portion on the surface of the obstacle layer by image exposure and post-exposure in a normal plate making process. It is presumed that, by this, the relief is firmly held by the support, and the relief is prevented from falling off.

The thickness of the obstacle layer used in the photosensitive resin relief printing plate of the present invention is preferably 3 μm or more and less than 100 μm, and particularly preferably 5 to 50 μm. When it is less than 3 μm, it is not preferable because harmful substances cannot enter the adhesive layer such as printing ink or printing ink washing oil sufficiently and cannot play a sufficient role as an obstacle layer. Further, it is not preferable to coat the barrier layer with a thickness of 100 μm or more, since the applied liquid film foams during drying and unevenness is generated on the surface, so that process control is extremely difficult and costly.

The composition of the obstacle layer used in the photosensitive resin relief printing plate of the present invention may be any composition having photosensitivity, that is, a composition comprising a binder polymer, a photopolymerizable unsaturated compound and a photopolymerization initiator.

Polymers that can be used as the binder polymer include alcohol-soluble polyamide, polyether polyamide urea, polyether urethane urea, polyether ester amide, partially saponified (or completely saponified) polyvinyl acetate, methyl vinyl ether / maleic anhydride copolymer and the like. Derivatives, styrene / arrayic anhydride copolymers and derivatives thereof, and the like.

The photopolymerizable unsaturated compound used with these binder polymers is ethylene glycol di (meth)
Polyhydric alcohols such as acrylate, neopentyl glycol di (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate (Meth) acrylates, addition products of polyhydric glycidyl ethers such as ethylene glycol diglycidyl ether and (meth) acrylic acid, reaction adducts of polyhydric carboxylic acids such as adipic acid and glycidyl (meth) acrylate, Examples thereof include polyunsaturated compounds such as an addition reaction product of a polyvalent amine such as propylene diamine and glycidyl (meth) acrylate.

Any known photopolymerization initiator can be used as the photopolymerization initiator used in the obstacle layer. Suitable photoassembly initiators include benzoin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, benzyl ketals such as dimethyl ketal and diethyl ketal, benzophenones, anthraquinones, and diacetyls. Can be

The obstruction layer used in the photosensitive resin relief printing plate of the present invention is obtained by applying and drying the above-described obstruction layer composition on an adhesive-treated support by the following method, and then irradiating active light in the presence of air. And photocured.

As a method of applying the obstacle layer, all known methods can be employed. For example, after applying the obstruction layer composition to the support having been subjected to the adhesive treatment using a gravure coater, a roll coater, a bar coater, a kiss coater, or the like, it is dried with a dryer to obtain a coating film having a thickness of 3 to 100 μm. After that, the obstacle layer is completed by irradiating with actinic rays immediately. As the actinic light source, a light source having a strong ultraviolet light energy distribution such as a chemical lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a halogen lamp is preferable.

As the support subjected to the adhesive treatment used for the photosensitive resin relief printing plate of the present invention, any known supports can be used. For example, a polyester film, a steel plate, an aluminum plate, or the like to which an adhesive has been applied in advance may be used.

As the photosensitive resin composition used in the photosensitive resin letterpress material of the present invention, all known photosensitive resin compositions can be used, and a binder polymer, a photopolymerizable unsaturated compound,
It is a composition containing a photopolymerization initiator, a plasticizer, a heat stabilizer and the like. In each composition, the binder, the photopolymerizable unsaturated compound, and the photopolymerization initiator used in the above-described obstacle layer can be used. Known plasticizers such as phthalic acid, esters, and alkyl sulfonic acid amides can all be used. As the thermal stabilizer, all thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, and phenathiazine can be used.

The photosensitive resin letterpress material of the present invention is completed by laminating the photosensitive resin composition on the support having the above-described obstacle layer by a known method. For example, a method of pouring a photosensitive resin composition solution onto a support having an obstacle layer and removing a solvent, and protecting a melt obtained by removing most of the solvent from the photosensitive resin composition solution with a support having an obstacle layer. A method in which a photosensitive resin sheet is prepared in advance by a casting method from a photosensitive resin composition solution, and is laminated on a support having a barrier layer by heating, for example, a method in which the film is poured into a sheet and sandwiched in a sandwich form with a film. Is applied.

(Examples) Hereinafter, the present invention will be specifically described with reference to Reference Examples and Examples.

REFERENCE EXAMPLE 1 On a chromium-plated steel sheet having a thickness of 200 μm, 0.1 g of U-CATSA102 (trade name of San-Apot), 100 g of commercially available linear polyester Byron RV-30SS (trade name of Toyobo KK), and Coronate L (trade name of Nippon Polyurethane Industry KK) Product name) A coating solution prepared by mixing 10.0 g in order is evenly applied using a bar coater, immediately put in a hot air dryer at 140 ° C, dried for 3 minutes, and an adhesive layer with a film thickness of about 20μ A support (I) having the following formula was obtained.

Reference Example 2 A commercially available linear polyester Byron RU-30SS (trade name of Toyobo KK) 10 was placed on a 250 µm thick polyester film.
0 g, u-CAT SA102 0.2 g, coronate L10.0 g coating solution formed by mixing sequentially using a roll coater to apply uniformly,
Pass it through a hot air dryer at 120 ° C for 3 minutes,
The support (II) having an adhesive layer of μ was obtained.

Example 1 65 parts by weight of Ultraamide-IC (trade name of BASF) on the support (I) subjected to the adhesion treatment obtained in Reference Example 1,
35 parts by weight of trimethylolpropane triglycidyl ether / triacrylate, dimethylbenzyl ketal 0.3
A 25% methanol solution containing 0.1 parts by weight of hydroquinone monomethyl ether by weight is applied using a roll coater, dried with a 90 ° C. hot air drier for 3 minutes, and immediately 80 w / cm
Activated light was irradiated in the presence of air for 30 seconds at a position 30 cm directly below the ultra-high pressure mercury lamp to obtain a support (III) having an obstacle layer having a thickness of about 20 μm. Next, ε-caprolactam / NN′bis (3-aminopropyl) piperazine / 1,1,2 in an autoclave.
3-bisaminomethylcyclohexane / adipic acid (50 /
(25/5/21 weight ratio), 440 g of a copolymerized polyamide is dissolved in 700 g of methanol, and trimethylolpropane triglycidyl ether, 280 g of triacrylate, and methacrylic acid are dissolved.
25 g of N-methyl P-toluenesulfonic acid amide, 25 g of dimethylbenzyl ketal and 1.6 g of hydroquinone monomethyl ether were added and uniformly dissolved to remove about 650 g of methanol from a photosensitive resin solution obtained. The reactive resin was extruded into a sheet having a thickness of about 700 μm on the support (III) provided with the obstacle layer obtained above, and a 125 μm polyester film was laminated. After being left at room temperature to sufficiently solidify, it was subjected to a heat treatment by hot air drying at 90 ° C. for 3 minutes, and then left again at room temperature to obtain a photosensitive resin relief printing plate having excellent photosensitive characteristics.

The polyester film was peeled off from the thus obtained photosensitive resin relief printing plate, a test negative film was adhered to the film in vacuum, and a chemical lamp was exposed thereon for 5 minutes. After washing out the exposed photosensitive resin letterpress material, the unexposed part was washed out using a brush-type washing machine containing water,
After drying at 70 ° C. for 10 minutes, the entire surface was exposed with a chemical lamp for 5 minutes. In the obtained relief image, an independent point having a diameter of 200 μ and a fine line having a line width of 40 μm were faithfully reproduced. This relief image was immersed in acetone ethyl acetate and trichlene for 10 hours, but no change was observed in both the image area and the non-image area, indicating that the resistance to these solvents was very high.

Comparative Example 1 In order to compare with the photosensitive resin relief plate material of Example 1, the support (III) provided with the obstacle layer used in Example 1 was replaced with
All the procedures were performed in the same manner as in Example 1 except that the support (I) having the adhesive layer obtained in Reference Example 1 was used.
An independent point of μ and a thin line with a line width of 40μ were reproduced. Next, when the obtained relief image was immersed in ethyl acetate acetone and trichlene for 10 hours in the same manner as in Example 1, the relief immersed in any solvent swelled around the non-image area and the image area, and the relief support was The adhesive force with the adhesive significantly decreased.

From the above, it was confirmed that the obstacle layer has an excellent effect of preventing the solvent from entering the adhesive layer, swelling the adhesive layer, reducing the adhesive force between the relief and the support, and preventing the relief from falling off. Was.

Comparative Example 2 In order to compare with the photosensitive resin letterpress material of Example 1, a relief image was obtained in the same manner as in Example 1 except that the thickness of the obstacle layer was about 2 μm. The obtained relief image was dissolved in ethyl acetate and tricrene in the same manner as in Example 1.
After immersion for 10 hours, the relief immersed in any of the solvents swelled in the non-image area and the periphery of the image area, and the adhesive strength of the relief to the support was significantly reduced.

From the above, it can be seen that a certain film thickness is necessary in order for the obstacle layer to prevent the solvent from entering the adhesive layer.

Example 2 50 parts by weight of methyl half ester of a methyl vinyl ether / maleic anhydride copolymer, 50 parts by weight of trimethylpropane triglycidyl ether triacrylate, 50 parts by weight of dimethyl, on the support (II) having been subjected to the adhesion treatment obtained in Reference Example 2 A 25% methanol solution containing 0.5 parts by weight of benzyl ketal is applied using a roll coater, dried with a hot air dryer at 70 ° C. for 3 minutes, and immediately activated at 30 cm under an 80 cm / w ultra-high pressure mercury lamp for 30 seconds. Irradiation with a light beam provided a support (IV) having an obstacle layer having a thickness of about 20 μm. Next, ε-caprolactam / NN′bis (3-aminopropyl) piperazine / 1,
3-bisaminomethylcyclohexane / adipic acid (50 /
(25/5/21 weight ratio), after dissolving 440 g of copolymerized polyamide in 700 g of methanol, 280 g of ethylene glycol diglycidyl ether dimethacrylate, and 25% of methacrylic acid
g, N-ethyl P-toluenesulfonic acid amide 25 g, dimethyl ketal 8 g and hydroquinone monomethyl ether
The photosensitive resin solution in which 1.6 g was added and uniformly dissolved was poured onto the support (IV) having the obstacle layer obtained by the above method,
After leaving methanol overnight to evaporate and remove methanol, a polyester film having a polyvinyl alcohol film was laminated and laminated under heat and pressure to obtain a photosensitive resin relief plate material. The polyester film was peeled off from the thus obtained photosensitive resin relief printing plate, and a test negative was adhered thereon by vacuum, and a chemical lamp was exposed thereon for 6 minutes. The exposed photosensitive resin letterpress material is developed using a brush-type washing machine containing water, and then subjected to 10 ° C at 70 ° C.
After being dried for a minute, the entire surface was post-exposed with a chemical lamp for 6 minutes. As a result, a thin line with a 200 μ diameter independent point and a line width of 30 μ was sharply reproduced. Further, a printing test was carried out using this relief image, but no trouble of the relief falling off during printing was found at all.

Example 3 Water-soluble photosensitive resin plate Milacron MF100H (Tokyo Ohka Kogyo Co., Ltd.)
KK trade name) was dissolved in water, and filtered using a cotton filter. The solution was cast on the support (III) having an obstacle layer used in Example 1, and then dried at 40 ° C. for one day.
A negative film for testing was superimposed on the obtained photosensitive resin plate material, and was exposed for 5 minutes with a chemical lamp. Develop the exposed plate using a brush-type washing machine.
After drying at 10 ° C. for 10 minutes, the film was exposed to light with a chemical lamp for 5 minutes. Fine lines with a diameter of 200μ and an independent dotted line width of 40μ were sharply reproduced. A printing test was performed using this relief image as a printing plate. As a result, it was confirmed that there was no occurrence of a problem that the relief dropped off during printing, and that the relief image was held on the support very well.

(Operation and Effect of the Present Invention) The photosensitive resin relief printing plate of the present invention has a barrier layer provided on an adhesive-treated support, so that the printing ink or the washing oil of the printing ink enters the adhesive layer. By eliminating the swelling of the adhesive layer, the relief of the relief from the support during the printing process and plate making is eliminated, so that the resistance of the printing ink and the printing ink to the washing oil is remarkably improved. In addition, since the obstruction layer has an uncured portion in a very small layer on the surface, adhesion with the photosensitive resin layer is achieved by light adhesion with a light uncured portion on the obstruction layer surface. It is presumed that the support for a photosensitive resin relief printing plate having an obstacle layer has a feature that the adhesive strength does not decrease even if it is stored for a long time until the photosensitive resin layer is laminated. Therefore, the letterpress material of the present invention can be stored for a long time, the production plan becomes very easy, and the loss of disposal of the support due to the decrease in the adhesive performance is completely eliminated.

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Claims (1)

(57) [Claims] 1. A photosensitive resin relief printing plate comprising a photosensitive resin layer laminated on a support having been subjected to an adhesive treatment, wherein a light-cured thickness is provided between the support and the photosensitive resin layer. 3μ
A photosensitive resin relief printing plate material having an obstacle layer having a resistance to printing ink or a washing oil of the printing ink having a length of m to less than 100 μm.