CN117440891A - Seamless lithographic printing plate precursor, seamless lithographic printing plate, cylindrical support regeneration method, method for producing seamless lithographic printing plate precursor, and composition for forming easily releasable primer layer - Google Patents
Seamless lithographic printing plate precursor, seamless lithographic printing plate, cylindrical support regeneration method, method for producing seamless lithographic printing plate precursor, and composition for forming easily releasable primer layer Download PDFInfo
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- CN117440891A CN117440891A CN202280040763.1A CN202280040763A CN117440891A CN 117440891 A CN117440891 A CN 117440891A CN 202280040763 A CN202280040763 A CN 202280040763A CN 117440891 A CN117440891 A CN 117440891A
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- primer layer
- printing plate
- seamless
- layer
- lithographic printing
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- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/055—Thermographic processes for producing printing formes, e.g. with a thermal print head
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/06—Lithographic printing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
- B41N1/14—Lithographic printing foils
Abstract
The purpose of the present invention is to obtain a seamless lithographic printing plate precursor and a seamless lithographic printing plate that have excellent image reproducibility and are necessary for obtaining a high-definition seamless lithographic printing material. Further, it is intended to obtain a seamless lithographic printing plate precursor and a seamless lithographic printing plate which are easy to regenerate a cylindrical support. The present invention is a seamless lithographic printing plate precursor having an easily peelable primer layer and an ink repellent layer, each of which is continuous in this order, on the outer peripheral surface of a cylindrical support.
Description
Technical Field
The present invention relates to a seamless lithographic printing plate precursor, a seamless lithographic printing plate, a method for regenerating a cylindrical support, a method for producing a seamless lithographic printing plate precursor, and a composition for forming an easily releasable primer layer.
Background
Printing is performed by various methods such as relief printing, intaglio printing, stencil printing, and offset printing, and by taking advantage of the characteristics of each method. Among them, offset printing is advantageous over other printing methods in that a highly fine print can be obtained.
In the field of flexible package printing, etc., seamless printing is performed in which intermittent patterns or continuous patterns are repeatedly formed on a long (long) print medium, and printing for seamless printing has been proposed: a method of manufacturing a lithographic printing member in which a 1 st polymer layer and a silicon layer are coated on a hollow plate cylinder with radiation-sensitive material (for example, refer to patent document 1), a method of applying a coating layer having affinity for oil and water by conversion treatment on a cylindrical surface and curing the coating layer, and the like (for example, refer to patent document 2). As a method for attaching a printing plate to a sleeve, a method has been proposed which includes a protective layer forming step of forming a protective layer for protecting the outer peripheral surface of the sleeve on the outer peripheral surface of the sleeve, and a printing plate bonding step of bonding the printing plate to the surface of the adhesive layer, and a heat-shrinkable film is described as the protective layer (for example, refer to patent document 3).
Prior art literature
Patent document 1 Japanese patent laid-open No. 7-309001
Patent document 2 Japanese patent laid-open No. 9-99535
Patent document 3 Japanese patent laid-open No. 2006-231758
Disclosure of Invention
Problems to be solved by the invention
As a support for a seamless lithographic printing plate, for example, a cylindrical support such as a plate cylinder or a plate cylinder sleeve is useful. In addition to being expensive, it is also desirable from the standpoint of environmental impact to reproduce a cylindrical support from a seamless lithographic printing plate after printing, and to repeatedly manufacture a seamless lithographic printing plate using the reproduced cylindrical support.
The seamless lithographic printing plates described in patent documents 1 and 2 can obtain a highly precise seamless printed matter, but since the support/ink repellent layer and the support/adhesive layer are firmly bonded by chemical bonds, a wet process such as cleaning with a solvent and a complicated operation such as polishing of the outer peripheral surface of the support are required for regenerating the support.
The seamless lithographic printing plate described in patent document 3 has the following advantages: to obtain a seamless printed matter with high definition, and the heated heat shrinkage film is peeled off by a dry process to obtain a renewable sleeve. However, since a single sheet-like planographic printing plate is wound around a sleeve and a seam is present between a plate head portion and a plate tail portion, a seamless printing product of a continuous pattern cannot be obtained.
Accordingly, an object of the present invention is to provide a seamless lithographic printing plate precursor which can easily regenerate a cylindrical support and can obtain a high-definition continuous pattern.
Means for solving the problems
In order to solve the above problems, the present invention is as follows.
[1] A seamless lithographic printing plate precursor comprising a cylindrical support, on the outer peripheral surface of which there are successively provided an easily peelable primer layer and an ink repellent layer.
[2] The seamless lithographic printing plate precursor according to [1], wherein the adhesion force of the cylindrical support and the easily releasable primer layer is smaller than the film strength of the easily releasable primer layer.
[3] The seamless lithographic printing plate precursor according to [1] or [2], wherein the adhesion force of the cylindrical support to the easily releasable primer layer is 10 to 2000N/m.
[4] The seamless lithographic printing plate precursor according to any one of [1] to [3], wherein the elongation at break of the easily releasable primer layer is 10 to 1000%.
[5] The seamless lithographic printing plate precursor according to any one of [1] to [4], wherein the average thickness of the easily releasable primer layer is 15 to 500 [ mu ] m.
[6] The seamless lithographic printing plate precursor according to any one of [1] to [5], wherein the releasable primer layer contains a compound having a functional group with an aggregation energy of 20 to 60 kJ/mol.
[7] The seamless lithographic printing plate precursor according to any one of [1] to [6], wherein the releasable primer layer has no covalent bond with the outer peripheral surface of the cylindrical support.
[8] The seamless lithographic printing plate precursor according to [6] [ wherein the compound having a functional group with an aggregation energy of 20 to 60kJ/mol contains polyurethane.
[9] The seamless lithographic printing plate precursor according to any one of [1] to [8], wherein the ink repellent layer is a silicone layer.
[10] The seamless lithographic printing plate precursor according to any one of [1] to [9], wherein an ink-applied layer is continuously provided between the easily releasable primer layer and the ink-repellent layer or further outside the ink-repellent layer.
[11] The seamless lithographic printing plate precursor according to [10], wherein the inking layer is a photosensitive layer or a thermosensitive layer.
[12] A seamless lithographic printing plate obtained by plate-making the seamless lithographic printing plate precursor of any one of [1] to [11].
[13] A method for recycling a cylindrical support, wherein the releasable primer layer is peeled into a film form by a dry process from the outer peripheral surface of the cylindrical support of the seamless lithographic printing plate precursor of any one of [1] to [11] or the seamless lithographic printing plate of [12].
[14] A method for producing a seamless lithographic printing plate precursor, comprising sequentially and continuously forming an easily peelable primer layer and an ink repellent layer on the outer peripheral surface of the cylindrical support regenerated by the method described in [13].
[15] A method for producing a seamless lithographic printing plate precursor according to any one of [1] to [11], wherein the composition for forming an easily releasable primer layer is applied to the outer peripheral surface of a cylindrical support and dried under heating or non-heating, thereby forming the easily releasable primer layer.
[16] A method for producing a seamless lithographic printing plate precursor according to any one of [1] to [11], wherein the composition for forming an easily releasable primer layer is applied to the outer peripheral surface of a cylindrical support, and the composition for forming an easily releasable primer layer is cured by irradiation with an active energy ray, whereby the easily releasable primer layer is formed.
[17] The method for producing a seamless lithographic printing plate precursor according to [15] or [16], wherein the cylindrical support regenerated by the method according to [13] is used as the cylindrical support.
[18] A composition for forming an easily releasable primer layer, which comprises a compound having a functional group with an aggregation energy of 20-60 kJ/mol.
[19] The composition for forming an easily releasable primer layer according to [18], wherein the compound having a functional group with an aggregation energy of 20 to 60kJ/mol contains a compound having a urethane bond and/or a hydroxyl group.
[20] The composition for forming an easily releasable primer layer of [18] or [19], wherein the compound having a functional group with an aggregation energy of 20 to 60kJ/mol further has an ethylenically unsaturated double bond in the molecule.
[21] The composition for forming an easily releasable primer layer of [19], wherein the compound having a functional group with an aggregation energy of 20 to 60kJ/mol contains polyurethane.
[22] The composition for forming an easily releasable primer layer of any one of [18] to [21], further comprising inorganic particles.
Effects of the invention
According to the present invention, a seamless lithographic printing plate precursor having a cylindrical support, which can be easily regenerated and can have a high-definition continuous pattern, can be obtained.
Drawings
Fig. 1 is a schematic diagram showing a difference between an intermittent pattern and a continuous pattern in seamless printing.
Fig. 2 is a schematic cross-sectional view showing an example of a method for producing a seamless printed product.
Detailed Description
The seamless lithographic printing plate precursor according to the present invention is a printing plate precursor for seamless printing, which has an easily peelable primer layer and an ink repellent layer successively in this order on the outer peripheral surface of a cylindrical support. Hereinafter, the seamless lithographic printing plate precursor may be referred to as "original".
The seamless printing in the present invention refers to a method of repeatedly printing the same pattern or design on a long print medium, and by this printing method, a seamless printed matter in which intermittent design or continuous design is repeatedly formed on the print medium can be obtained. The lithographic printing plate used for seamless printing is referred to as a seamless lithographic printing plate, and from the seamless lithographic printing plate precursor, a seamless lithographic printing plate can be obtained by, for example, a method described later. Hereinafter, the seamless lithographic printing plate may be referred to as "printing plate".
Here, the difference between the intermittent pattern and the continuous pattern in the seamless printing according to the present invention will be described with reference to fig. 1. Fig. 1 is a schematic diagram showing the difference between the intermittent pattern a and the continuous pattern B in the seamless printing. The left and right sides of fig. 1 show a seamless planographic printing plate E used in seamless printing of an intermittent pattern and a continuous pattern, and a seamless printed matter F obtained by performing seamless printing using the seamless planographic printing plate E, respectively. The seamless planographic printing plate E has an ink-attached line drawing portion 1 and an ink-unattached non-line drawing portion 2, and the line drawing portion 1 (pattern) is intermittently arranged with respect to the printing direction D in the case of an intermittent pattern, and the line drawing portion 1 (pattern) is continuously arranged with respect to the printing direction D in the case of a continuous pattern. In the seamless printing, the ink adhering to the line drawing portion 1 is transferred to the printing medium 3 directly or via a blanket, thereby forming a transfer pattern 4.
In the printing plate described in japanese patent application laid-open No. 2006-231758, which is exemplified as prior art patent document 3, or the printing plate described in comparative example 3, which will be described later, a single sheet-like planographic printing plate is wound around the outer peripheral surface of a cylindrical support, and an ink repellent portion (non-line drawing portion) is formed by curing an ink repellent layer forming composition in the gap between the head and the tail. Therefore, by disposing the pattern so that the ink repellent portion (non-line drawing portion) of the gap between the head and the tail coincides with the portion where the pattern is interrupted in the intermittent pattern, a seamless printed product of the intermittent pattern can be obtained. However, since the line drawing portion cannot be formed in the ink repellent portion in the gap between the head and the tail, a seamless printed matter having no continuous pattern in which the interruption portion does not exist in the pattern cannot be obtained.
In the master of the present invention, the easily releasable primer layer or the ink repellent layer, and the other functional layers are continuously provided without any gap in the circumferential direction or the axial direction of the master. Therefore, a printing plate having a continuous line drawing portion without gaps in the circumferential direction can be produced, and a seamless printed matter having a continuous pattern in which no interruption portion exists in the pattern can be obtained. Here, continuous refers to a state in which each functional layer is provided on the master without any gap in the circumferential direction or the axial direction.
For example, in the case where the easily peelable primer layer has inking properties, in the case where an inking layer is continuously provided between the easily peelable primer layer and the ink repellent layer, or further outside the ink repellent layer, a continuous line drawing portion may be formed on the printing plate. Further, the ink repellent layer is modified to be ink-receptive by pattern irradiation of active energy rays or the like, or the ink-repellent layer is sprayed with a composition for forming an ink-receptive portion in a pattern and cured, whereby a continuous line drawing portion can be formed on the printing plate.
First, the original plate of the present invention will be described.
The master of the present invention has an easily releasable primer layer and an ink repellent layer sequentially and continuously on the outer peripheral surface of a cylindrical support. Here, continuous refers to a state in which the easily releasable primer layer and the ink repellent layer are disposed without any gap in the circumferential direction or the axial direction in the master. As described above, by continuously providing the easily releasable primer layer, the ink repellent layer, and the other functional layers in the circumferential direction or the axial direction of the original plate, it is possible to form a pattern of an intermittent pattern or a continuous pattern on the printing plate, and thus it is possible to perform seamless printing in which the pattern of the intermittent pattern or the continuous pattern is repeatedly formed on a long print medium.
The material constituting the cylindrical support is preferably a dimensionally stable metal, plastic, or the like, and examples thereof include metals such as aluminum, iron, zinc, and copper, and alloys containing these metals as a main component, epoxy resins, phenolic resins, ester resins, vinyl ester resins, amide resins, and imide resins, and fiber-reinforced plastics containing these plastics and fibers such as glass fibers, carbon fibers, aramid fibers, polyethylene fibers, zylon fibers, and boron fibers. From the viewpoint of light weight and easy handling, aluminum alloy or fiber reinforced plastic is preferable.
The cylindrical support is preferably a plate cylinder of a printing machine from the viewpoint that printing can be performed immediately after the printing plate is manufactured from the original plate. In particular, the cylindrical support is a plate cylinder sleeve that is detachable from the plate cylinder shaft, and is more preferable from the viewpoint that a series of steps before printing plate production, and operations such as regenerating the cylindrical support after printing can be performed outside the printing machine.
As the size of the cylindrical support, an appropriate diameter or width may be selected as the plate cylinder of the printing press used.
The releasable primer layer in the present invention is a layer that can be released from the outer peripheral surface of the cylindrical support by a dry process into a film shape and is directly, i.e., adjacently laminated on the outer peripheral surface of the cylindrical support. Since the easily peelable primer layer and each functional layer provided on the outer peripheral surface thereof can be peeled into a film form from the outer peripheral surface of the cylindrical support by a dry process, the cylindrical support can be easily regenerated without requiring a complicated operation such as a wet process such as cleaning using chemicals or polishing of the outer peripheral surface of the support.
The adhesion force between the cylindrical support of the master of the present invention and the releasable primer layer is preferably 10 to 2000N/m. By setting the adhesion to 10N/m or more, the printing plate can be stably held during printing, and the printing resistance can be improved. The adhesion force is more preferably 30N/m or more. On the other hand, when the adhesion force is 2000N/m or less, the peeling of the easily peelable primer layer becomes easier, and the cylindrical support can be regenerated more easily. The adhesion force is preferably 1000N/m or less, more preferably 800N/m or less.
Examples of the method for setting the adhesion force in the above range include a method for forming an easily releasable primer layer using an easily releasable primer layer forming composition described later.
The adhesion force between the cylindrical support and the easily peelable primer layer can be obtained by measuring the force required to peel the easily peelable primer layer having a predetermined width from the outer peripheral surface of the cylindrical support by a load cell. Specifically, a razor is used at a position randomly selected from the easily peelable primer layers provided on the outer peripheral surface of the cylindrical support body, so as to have a width: 0.1m, length: 0.1m of a stripe-shaped scratch was scored, and the force [ N/0.1m ] at 0.05m of the peel-off primer layer peeled from the cylindrical support along the longitudinal direction was measured with a load cell. By setting the peeling force [ N/0.1m ] to 10 times, the adhesion force [ N/m ] between the cylindrical support and the easily peelable primer layer can be obtained.
The adhesion force between the cylindrical support of the master of the present invention and the easily releasable primer layer is preferably smaller than the film strength of the easily releasable primer layer. By making the adhesion force between the cylindrical support and the easily peelable primer layer smaller than the film strength of the easily peelable primer layer, peeling of the easily peelable primer layer becomes easier, and the cylindrical support can be regenerated more easily. More preferably, the film strength of the easily releasable primer layer is 1.5 times or more the adhesion force between the cylindrical support and the easily releasable primer layer.
Examples of the method for setting the relationship between the film strength of the easily releasable primer layer and the adhesion force between the cylindrical support and the easily releasable primer layer within the above-described range include a method for setting the average thickness of the easily releasable primer layer within a preferable range described later, a method for forming the easily releasable primer layer using the easily releasable primer layer forming composition described later, and the like.
Film strength of easy-to-peel primer layerThe tensile strength of the easily peelable primer layer and the average thickness of the easily peelable primer layer can be determined. Specifically, the tensile Strength of the easily peelable primer layer [ N/mm ] 2 ]Average thickness of the primer layer with easy peelability [ mm ]]The product of (a) is the film strength of the easily peelable primer layer [ N/mm ] ]. By making the film strength of the resulting easily peelable primer layer [ N/mm ]]1000 times, the unit is set as [ N/m ]]Adhesion force [ N/m ] between the cylindrical support and the easily releasable primer layer]The relationship between the two is easier to grasp because the units are consistent.
The tensile strength of the easily releasable primer layer can be measured by the method specified in JIS K6251:2017.
The average thickness of the easily releasable primer layer can be obtained by cross-sectional SEM observation or cross-sectional TEM observation. More specifically, after the release primer layer is released from the master, the resin is embedded in the film, and then the cross section of the sample produced by the microtome is observed by SEM or TEM magnification. In the vertical cross-sectional image, the thickness was measured for 10 sites randomly selected from the releasable primer layer, and the number average value was calculated, whereby the average thickness was obtained. Further, since the thickness of the easily releasable primer layer does not change in the step of producing a printing plate from the original plate, the average thickness of the easily releasable primer layer can be obtained from the printing plate in the same manner as the original plate.
The elongation at break of the easily releasable primer layer of the master of the present invention is preferably 10 to 1000%. By setting the elongation at break to 10% or more, the peeling of the easily peelable primer layer becomes easier, and the cylindrical support can be regenerated more easily. The elongation at break is more preferably 20% or more. On the other hand, when the elongation at break is 1000% or less, deformation of the release film is suppressed, and peeling of the easily releasable primer layer becomes easier, so that the cylindrical support can be regenerated more easily. The elongation at break is more preferably 800% or less.
Examples of the method for forming the easily releasable primer layer include a method for forming the easily releasable primer layer using a composition for forming an easily releasable primer layer described later.
The elongation at break of the easily releasable primer layer can be measured by a method specified in JIS K6251:2017.
The average thickness of the easily releasable primer layer of the master of the present invention is preferably 15 to 500. Mu.m. By setting the average thickness to 15 μm or more, peeling of the easily peelable primer layer becomes easier, and the cylindrical support can be regenerated more easily. In addition, the film strength of the easily peelable primer layer can be appropriately improved. The average thickness is more preferably 20 μm or more. On the other hand, by setting the average thickness to 500 μm or less, the drying efficiency of the easily releasable primer layer can be improved, and the residual stress or residual strain of the easily releasable primer layer after drying or curing can be reduced. More preferably, the average thickness is 300 μm or less. The average thickness of the easily releasable primer layer can be determined by the method described.
The master of the present invention preferably contains a compound having a functional group with an aggregation energy of 20 to 60kJ/mol in the easily releasable primer layer. By containing this compound, the adhesion force to the cylindrical support and the film strength can be improved, and the preferable range can be easily adjusted. Further, it is preferable that the easily peelable primer layer does not have a covalent bond with the outer peripheral surface of the cylindrical support. By having no covalent bond, the adhesion force with the cylindrical support can be appropriately suppressed, and the easily releasable primer layer can be easily released from the outer peripheral surface of the cylindrical support into a film shape by a dry process. That is, the adhesion force with the cylindrical support can be easily adjusted to the above-described preferable range.
Examples of the functional group having a condensation energy of 20 to 60kJ/mol include a carboxyl group (23.4 kJ/mol), a hydroxyl group (24.3 kJ/mol), an isourea bond (27.7 kJ/mol), a urethane bond (36.8 kJ/mol), an allophanate bond (38.9 kJ/mol), a urea bond (41.8 kJ/mol), and a biuret bond (58.5 kJ/mol). These may contain 2 or more. In addition, the respective condensation energies are calculated values calculated from values used in a derivative algorithm based on a solubility parameter of a molecular structure as set forth in Fedors (R.F.Fedors, polym.Eng.Sci.,14147 (1974).
As the compound having a functional group with a coagulation energy of 20 to 60kJ/mol, polyurethane is preferable. I.e.The master of the present invention preferably contains polyurethane as the compound having a functional group with an aggregation energy of 20 to 60 kJ/mol. Since polyurethane has urethane bonds with high aggregation energy in the molecule, the adhesion force to the cylindrical support and the film strength can be improved, and the preferable range can be easily adjusted. Further, since the molecule has a soft segment such as polyether or polyester, the elongation at break of the easily releasable primer layer can be improved and easily adjusted to the above-mentioned preferable range. Among them, a film having a high tensile strength after drying is preferable, and examples thereof include "craftsman" (registered trademark) 8966, 9004 (both manufactured by DIC (inc.). Further, polyurethane emulsion in which polyurethane particles having high tensile strength of the dried film are dispersed in a dispersion medium such as water may be used, and examples thereof include "us-you-brand" (registered trademark) series (manufactured by first industry pharmaceutical Co., ltd.), and more specifically "us-you-brand" 150 (tensile strength: 45N/mm) 2 First manufactured by first industry pharmaceutical Co., ltd.) and the like. The polyurethane preferably has a carboxyl group or a hydroxyl group, so that the adhesion force to the cylindrical support or the film strength can be improved, and the preferable range can be easily adjusted. In addition, the adhesion to the layer on the easily peelable primer layer can be improved. Examples of the polyurethane having a hydroxyl group include "trian" (registered trademark) IB series (manufactured by san chemical industry co., ltd.) and the like.
The easily releasable primer layer may contain inorganic particles. Since a stronger film can be obtained by the filling effect of the inorganic particles, the primer layer having easy peelability can be thinned.
The inorganic particles are preferably carbon black or silica particles, and silica particles are more preferable from the viewpoint of the plate-checking property. Examples of the silica particles include "AEROSIL" (registered trademark) series (manufactured by japan industrial and scientific).
The average particle diameter of the inorganic particles is preferably 0.1 to 2. Mu.m, more preferably 0.2 to 1. Mu.m, from the viewpoint of dispersibility.
Examples of the ink repellent layer of the original plate of the present invention include an addition reaction type, a condensation reaction type, an addition reaction-condensation reaction combined type silicone layer or a fluororesin layer disclosed as an ink repellent layer for a waterless lithographic printing plate, a hydrophilic layer disclosed as an ink repellent layer for a horizontal plate, and the like. The master of the present invention is preferably an ink repellent layer that is a silicone layer.
Examples of the addition reaction type, condensation reaction type, and addition reaction-condensation reaction combination type ink repellent silicone layer include a layer exemplified by a layer containing diorganosiloxane units in japanese unexamined patent publication No. 2021-66175, a layer exemplified by a silicone rubber layer in international publication No. 2019/203261, and a layer exemplified by a 1 st silicone layer in international publication No. 2019/203263.
In order to improve the adhesion between the easily releasable primer layer and the ink repellent layer and between the easily releasable primer layer and the ink receptive layer, which will be described later, an adhesive layer may be further provided continuously between the easily releasable primer layer and the ink repellent layer and between the easily releasable primer layer and the ink receptive layer. Here, continuous means a state in which the adhesive layer is provided without any gap in the circumferential direction or the axial direction in the master.
Examples of the adhesive layer include a layer described as a heat insulating layer in JP-A-2004-199016, JP-A-2004-334025, JP-A-2006-276385, and the like.
The average thickness of the adhesive layer is preferably 0.1 μm or more, from the viewpoint of improving the scratch resistance and printing resistance of the printing plate, and from the viewpoint of easy volatilization of the diluting solvent and excellent productivity, it is preferably 30 μm or less. More preferably 0.2 to 20. Mu.m.
As described above, since the original plate of the present invention can form a continuous line drawing portion on the printing plate, it is preferable that the original plate has an ink layer continuously between the easily releasable primer layer and the ink repellent layer or further outside the ink repellent layer. Here, the term "continuously" refers to a state in which the original plate is provided with the ink layer without any gap in the circumferential direction or the axial direction.
The master of the present invention may be in the form of:
(1) The outer peripheral surface of the cylindrical support body is provided with a continuous easily-strippable primer layer and an ink-repellent layer in sequence;
(2) The outer peripheral surface of the cylindrical support body is provided with a continuous form of an easily strippable primer layer, an ink repellent layer and an ink-applying layer in sequence;
(3) The outer peripheral surface of the cylindrical support body is provided with a continuous form of an easily strippable primer layer, an ink-applying layer and an ink-repellent layer in sequence;
etc.
In the embodiment (2), as the ink layer, for example, an ink-forming silicone layer exemplified as the 2 nd silicone layer in international publication No. 2019/203263, or the like can be used. In another embodiment of (2), the ink repellent layer may be a hydrophilic layer disclosed as an ink repellent layer for a lithographic printing plate having water, and the ink repellent layer may be an ink repellent layer disclosed as a photosensitive layer or a thermosensitive layer for a lithographic printing plate having water.
In the embodiment of (3), as the ink layer, an ink layer disclosed as a photosensitive layer or a thermosensitive layer for a waterless lithographic printing plate can be used.
Next, a method for producing the original plate will be described. The original plate of the present invention is obtained by providing an easily peelable primer layer and an ink repellent layer on the outer peripheral surface of a cylindrical support in this order without any gaps in the circumferential direction or in the axial direction. As the cylindrical support, a support regenerated by a method for regenerating a cylindrical support of the present invention described later is preferably used. That is, in one embodiment of the method for producing a master according to the present invention, the easily releasable primer layer and the ink repellent layer are sequentially formed on the outer peripheral surface of the cylindrical support regenerated by the method for regenerating a cylindrical support according to the present invention.
Examples of the method for forming the releasable primer layer include a method in which a composition for forming the releasable primer layer described later is continuously applied to the outer peripheral surface of a cylindrical support, and dried under heating or under non-heating. For the purpose of promoting drying, a known hot air drying device or an infrared drying device is preferably used, and the drying is preferably performed by heating at a temperature of 50 to 180℃for 30 seconds to 10 minutes. That is, one embodiment of the method for producing a master according to the present invention is a method for producing a master according to the present invention, wherein the composition for forming an easily releasable primer layer is applied to the outer peripheral surface of a cylindrical support, and the composition is dried under heating or non-heating to form the easily releasable primer layer. As the cylindrical support, a support regenerated by a method for regenerating a cylindrical support of the present invention described later is preferably used. Further, as another method for forming the releasable primer layer, for example, a method of continuously applying a composition for forming the releasable primer layer described later to the outer peripheral surface of the cylindrical support and curing the composition for forming the releasable primer layer by irradiation with an active energy ray may be mentioned. That is, one embodiment of the method for producing a master of the present invention is a method for producing a master of the present invention, wherein the composition for forming an easily releasable primer layer is applied to the outer peripheral surface of a cylindrical support, and the composition for forming an easily releasable primer layer is cured by irradiation with an active energy ray to form the easily releasable primer layer. As the cylindrical support, a support regenerated by a method for regenerating a cylindrical support of the present invention described later is preferably used. The active energy ray may be, for example, visible light, ultraviolet (UV), electron Beam (EB), X-ray, or particle beam, and ultraviolet rays are preferable from the viewpoint of ease of handling of the source, etc., and the active energy ray irradiation device may be, for example, a high-pressure mercury lamp, a xenon lamp, or a metal halogen lamp, and an ultraviolet irradiation device such as LED-UV is preferable.
Examples of the method for forming the ink repellent layer include a method in which a composition for forming an ink repellent layer described later is continuously applied to the outer peripheral surface of the easily releasable primer layer, and dried/cured under heating or non-heating. In order to promote drying and curing, it is preferable to heat at a temperature of 50 to 180℃for 30 seconds to 10 minutes.
As another method for sequentially providing the respective continuous easily releasable primer layer and ink repellent layer on the outer peripheral surface of the cylindrical support, for example, there may be mentioned a method in which the composition for forming an easily releasable primer layer described later is continuously applied on the outer peripheral surface of the cylindrical support, and further, after the composition for forming an ink repellent layer described later is continuously applied on the outer peripheral surface thereof, any one of the following methods is performed:
<1> a method of curing an easily releasable primer layer-forming composition by irradiation of active energy rays from the side of the ink repellent layer-forming composition, and then drying/curing the ink repellent layer-forming composition under heating or non-heating,
<2> a method for curing a composition for forming an easily releasable primer layer by irradiation of active energy rays from the ink repellent layer side after drying/curing the composition for forming an ink repellent layer under heating or non-heating,
<3> simultaneous: a method of curing the composition for forming the easily releasable primer layer by irradiation of active energy rays from the ink repellent layer side and drying/curing the composition for forming the ink repellent layer under heating or non-heating,
Etc.
In each of the methods 1 > - < 3 >, it is preferable to heat at a temperature of 50 to 180 ℃ for 30 seconds to 10 minutes in order to promote drying or curing of the composition for forming an ink repellent layer after coating.
Examples of the method for applying the composition for forming an easily releasable primer layer and the composition for forming an ink repellent layer include dipping, spraying, and cylindrical slit die coating.
When the adhesive layer or the ink layer is formed continuously as needed, examples of the coating method include a dipping method, a spraying method, and a cylindrical slit die coating method. In order to promote drying, a known hot air drying device or an infrared drying device is preferably used, and the drying is preferably performed by heating at a temperature of 50 to 180℃for 30 seconds to 10 minutes.
Next, the composition for forming an easily releasable primer layer and the composition for forming an ink repellent layer which are preferably used in the embodiment of (1) will be described. The composition for forming an easily releasable primer layer in the present invention means a composition for forming an easily releasable primer layer, and similarly, the composition for forming an ink repellent layer in the present invention means a composition for forming an ink repellent layer.
The composition for forming the easily releasable primer layer preferably contains a compound having a functional group with an aggregation energy of 20 to 60 kJ/mol. Examples of the functional group having an aggregation energy of 20 to 60kJ/mol include carboxyl groups, hydroxyl groups, isourea bonds, urethane bonds, allophanate bonds, urea bonds, biuret bonds, and the like.
Examples of the form of the composition for forming an easily releasable primer layer include: (a) Containing a tensile strength of 25N/mm 2 The composition for forming a solvent-based easily releasable primer layer containing the polymer having a high tensile strength of less than 25N/mm 2 And (c) a composition for forming a photocurable releasable primer layer, and the like.
The compound having a functional group with an aggregation energy of 20 to 60kJ/mol in the form of (a) is preferably polyurethane, and examples of the compound include a polyurethane having a high tensile strength in the explanation of the easily releasable primer layer.
In the embodiment of (b), the compound having a functional group with an aggregation energy of 20 to 60kJ/mol is preferably polyurethane, but the tensile strength of the film after drying may not necessarily be high because of the filler effect of the inorganic particles. The polyurethane preferably has a carboxyl group or a hydroxyl group, so that the adhesion force to the cylindrical support or the film strength can be improved and the preferable range can be easily adjusted. In addition, the adhesion to the layer on the easily peelable primer layer can be improved. Examples of the polyurethane having a hydroxyl group include a polyurethane exemplified as a polyurethane having a hydroxyl group in the description of the easily releasable primer layer.
The inorganic particles are preferably carbon black or silica particles, and silica particles are more preferable from the viewpoint of the plate-checking property. Examples of the silica particles include silica particles exemplified as silica particles in the explanation of the releasable primer layer.
In the embodiment of (a) or (b), the solvent is preferably a solvent capable of dissolving polyurethane, and examples thereof include N, N-dimethylformamide, N-dimethylacetamide, cyclohexanone, cyclopentanone, γ -butyrolactone, tetrahydrofuran, 2-butanone, ethyl acetate, 2-propanol, toluene, and the like. These may contain 2 or more. From the viewpoint of leveling property of the coating liquid, the boiling point of the solvent at 1 atmosphere is preferably 50 ℃ or higher, more preferably 70 ℃ or higher. On the other hand, from the viewpoint of quick-drying property, the boiling point of the solvent at 1 atmosphere is preferably 160 ℃ or less, more preferably 140 ℃ or less.
Examples of the compound having a functional group with an aggregation energy of 20 to 60kJ/mol in the form of (c) include a compound having a urethane bond and an ethylenically unsaturated double bond in the molecule and a compound having a hydroxyl group and an ethylenically unsaturated double bond in the molecule. These may contain 2 or more. From the viewpoint of high-speed curability, an acryl group is preferable as the ethylenically unsaturated double bond.
As the compound having a urethane bond and an acryl group in the molecule, urethane acrylate may be mentioned. As the urethane acrylate to be commercially available, there are a cartridge and a KRM (both of which are made by cartridge) and a cartridge the "ALC" series (DIC) and "NK-wire" U series UA series (manufactured by the chemical industry of new middle village), yu taro brand, AH series, UA series, UF series (manufactured by the chemical industry of co-ro corporation), purple series (manufactured by the chemical industry of mitsubishi corporation), and the like. These may contain 2 or more. Among them, urethane acrylate oligomers such as "UF 399-BA, -AM, -HX (all manufactured by co-grong corporation) and" violet "(registered trademark) UV-2000B, -3000B, -3200B, 3300B-, -3500B, -3500BA, -3520EA, -3700B (all manufactured by mitsubishi chemistry corporation) are preferable, and particularly, solvent-free" yu mountain "that does not contain volatile solvents in terms of being able to suppress the load on the human body and the environment, UV 399-AM, -HX (all manufactured by co-grong corporation) and" violet "(registered trademark) UV-2000B, -3000B, -3200B, -3300B, -3700B (all manufactured by mitsubishi corporation) are more preferable.
Examples of the compounds having a hydroxyl group and an acryl group in the molecule include terminal hydroxyl polyalkylene glycol monoacrylate such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1, 4-cyclohexanedimethanol monoacrylate, 2-acryloyloxyethyl-2-hydroxyethyl-phthalate, 2-hydroxy-3-methacryloylpropyl acrylate, pentaerythritol triacrylate, "AE-90U, -200, -400 (all manufactured by Nitro oil Co., ltd.), terminal hydroxyl polypropylene glycol monoacrylate such as" Gecko "(registered trademark) AP-200, -400D, -550, -800, -1000D (all manufactured by Nitro oil Co., ltd.), and the like. These may contain 2 or more.
For the purpose of improving the physical properties of the cured film, other acrylate monomers or oligomers may be used in combination in addition to the urethane acrylate or the acrylate having a hydroxyl group in the molecule. For example, it is effective to use 3 to 6 functional acrylate monomers or oligomers for the improvement of tensile strength, and it is effective to use 1 to 2 functional acrylates of polyethylene glycol or polypropylene glycol for the improvement of elongation at break.
The composition for forming a photocurable releasable primer layer of (c) preferably contains a conventionally known photoradical generator (sometimes referred to as a polymerization initiator) such as an organic halide, a carbonyl compound, an organic peroxide, an azo compound, an azide compound, a metallocene compound, a hexaarylbisimidazole compound, an organoboron compound, a disulfone compound, an oxime ester compound, or an onium salt compound. By containing the photoradical generator, the composition for forming the easily releasable primer layer after application can be cured instantaneously by irradiation with active energy rays.
Examples of the composition for forming an ink repellent silicone layer include a composition exemplified as a composition for forming a layer containing diorganosiloxane units in JP-A2021-66175, a composition exemplified as a composition for forming a silicone rubber layer in International publication No. 2019/203261, an addition reaction type, a condensation reaction type, and a combination of addition reaction and condensation reaction type, and an ink repellent silicone layer forming composition exemplified as a composition for forming a 1 st silicone layer in International publication No. 2019/203263.
Next, the composition for forming an easily releasable primer layer, the composition for forming an ink repellent layer, and the composition for forming an ink receptive layer, which are preferably used in the embodiment of (2), will be described.
The composition for forming the easily releasable primer layer and the composition for forming the ink repellent layer may be the compositions exemplified in the form of (1), respectively. As the composition for forming an ink-adhesive silicone layer, the composition described in international publication No. 2019/203263 can be used.
In addition, as another embodiment of (2), a known hydrophilic layer forming composition disclosed so far as a hydrophilic layer for a horizontal plate printing plate is used as the ink repellent layer forming composition, and a known photosensitive layer forming composition or a thermosensitive layer forming composition disclosed so far as a photosensitive layer or a thermosensitive layer for a horizontal plate printing plate may be used as the ink receptive layer forming composition.
Next, the composition for forming an easily releasable primer layer, the composition for forming an ink layer, and the composition for forming an ink repellent layer, which are preferably used in the embodiment of (3), will be described.
The composition for forming the easily releasable primer layer and the composition for forming the ink repellent layer may be the compositions exemplified in the form of (1), respectively. As the composition for forming an ink layer, a photosensitive layer forming composition or a thermosensitive layer forming composition disclosed so far as a photosensitive layer or a thermosensitive layer for a waterless lithographic printing plate can be used.
Next, a method of manufacturing a printing plate will be described. The printing plate of the present invention is obtained by plate making of the original plate of the present invention. An original plate having a continuous releasable primer layer and an ink repellent silicone layer on the outer peripheral surface of a cylindrical support will be described as an example. For example, a printing plate can be manufactured by the following two methods.
The first production method includes the method described in international publication No. 2019/203261. Specifically, the method is a method of ejecting the composition for forming an inking portion in a pattern on the ink repellent silicone layer of the master and curing the composition.
The second production method is described in Japanese patent application laid-open No. 2021-66175. Specifically, the method is a method of irradiating an original ink repellent silicone layer pattern with active energy rays to change the irradiation part to inking property.
As a method for producing a printing plate from a master having an easily releasable primer layer, an ink repellent silicone layer, and an ink receptive silicone layer, which are successively provided on the outer peripheral surface of a cylindrical support, there is a method described in international publication No. 2019/203263. Specifically, the method is a method of exposing the ink repellent silicone layer by pattern-irradiating the ink repellent silicone layer of the irradiation part with a high-output laser beam from the ink repellent silicone layer side of the master.
As a method for producing a printing plate from a master having a releasable primer layer, a hydrophilic layer, a photosensitive layer, or a thermosensitive layer, which are continuous in this order, on the outer peripheral surface of a cylindrical support, there is a method in which pattern exposure is performed from the photosensitive layer or thermosensitive layer side, and development is performed using water or a liquid or a developer containing water as a main component.
As a method for producing a printing plate from a master having a continuous easily releasable primer layer, a photosensitive layer or a thermosensitive layer, and an ink repellent silicone layer in this order on the outer peripheral surface of a cylindrical support, there is a method in which pattern exposure is performed from the ink repellent silicone layer side, and development is performed using water or a liquid or a developer containing water as a main component.
Next, a method for producing a seamless printed product will be described.
As a method for producing a seamless printed matter, the above-mentioned printing plate, ink and printing medium are preferably used. In the case where the printing plate is a lithographic plate having water, the printing plate, the wet water, the ink, and the printing medium are preferably used. Specifically, it is preferable to include a step of inking the surface of the inking unit of the printing plate and a step of transferring the ink adhering to the surface of the inking unit to a printing medium directly or via a blanket.
Fig. 2 is a schematic cross-sectional view of one embodiment of a method for producing a seamless printed product. In the following, an example of using the blanket cylinder 8 is described, but the present invention is not limited to this, and the ink may be directly transferred onto the printing medium 9 after the ink is applied from the ink roller 5 to the surface of the ink application portion of the seamless planographic printing plate 7 without using the blanket cylinder 8. In the following, an example of supplying ink from above the printing medium 9 is described, but ink may be supplied from below the printing medium 9.
First, ink is supplied to the ink roller 5. The ink supplied to the ink roller 5 adheres to the inking portion of the seamless lithographic printing plate 7 at the junction with the seamless lithographic printing plate 7. The ink adhering to the inking portion surface of the seamless lithographic printing plate 7 is transferred onto the surface of the blanket cylinder 8 at the junction with the blanket cylinder 8. The ink adhering to the blanket cylinder 8 is transferred to the printing medium 9 at a contact point with the printing medium 9 disposed on the impression cylinder 10. The ink-transferred printing medium 9 is dried as necessary, thereby obtaining a printed matter. In addition, in the case where the printing plate is a lithographic printing plate having water, the dampening water is supplied to the dampening water roller 6 before the ink is supplied to the ink roller 5. The wetting water supplied to the wetting water roller 6 adheres to the surface of the ink repellent portion (hydrophilic layer exposed portion) of the seamless lithographic printing plate 7 at the contact point with the seamless lithographic printing plate 7. The method after supplying ink to the ink roller 5 is the same as the above method. The rotational speeds of the ink roller 5, the dampening water roller 6, the seamless lithographic printing plate 7, the blanket cylinder 8, and the impression cylinder 10 are not particularly limited, and may be appropriately set according to the quality required for the printed matter, the nature of the ink, and the like.
As a printer used for producing a seamless printed matter, a known direct printing machine or an offset printing machine can be used, but an offset printing machine is preferable from the viewpoint of obtaining a larger number of printed matters by suppressing damage to a printing plate at the time of printing. The offset printing machine is composed of a paper feeding part, a printing part and a conveying part. The printing section includes at least an ink supply section, a plate cylinder, a blanket cylinder, and an impression cylinder.
As the offset printing press, an offset printing press having a cooling mechanism on the oscillating roller and/or the plate cylinder is preferable from the viewpoint of improving the resistance to medium contamination.
In the case of printing using an oil-soluble or water-soluble oxidative polymerization type ink, the ink transferred onto the printing medium can be dried and/or cured by natural drying or heat treatment, thereby obtaining a printed matter.
On the other hand, in the case of printing with an oil-soluble or water-soluble active energy ray-curable ink, the ink transferred onto the printing medium is cured instantaneously by active energy rays from an active energy ray irradiation device, and a printed matter is obtained, which is preferable.
The active energy rays include visible rays, ultraviolet rays (UV), electron rays (EB), X-rays, particle rays, and the like, but ultraviolet rays or electron rays are preferable in view of ease of handling of the radiation source, and the like.
In the case of curing the resin composition by ultraviolet rays, it is preferable to use an ultraviolet irradiation device such as a high-pressure mercury lamp, a xenon lamp, a metal halogen lamp, or an LED, for example, in the case of using a metal halide lamp, and it is preferable to use a resin composition having a concentration of 80 to 150W/cm from the viewpoint of productivity 2 The lamp with illumination is solidified at the conveying speed of the conveyor within the range of 50-150 m/min. In particular, when a plastic film or a metal-containing medium to be printed is used as the medium to be printed, the medium to be printed is easily stretched by heat generation of active energy rays, and thus an electron beam or an ultraviolet irradiation device (LED-UV) of an LED with less heat generation can be preferably used.
When the cured product is cured by an electron beam, an electron beam irradiation device having an energy beam of 100 to 500eV is preferably used.
The ink that can be preferably used in the present invention includes, but is not limited to, the following ink.
< ink-1 > oil-soluble oxidative polymerization type ink
Examples of the oil-soluble oxidative polymerization type ink include known oil-soluble oxidative polymerization type inks which can be washed with an oily washing liquid as disclosed in, for example, japanese patent application laid-open No. 48-004107 and Japanese patent application laid-open No. 01-306482. In addition, soybean oil ink, vegetable oil ink, and environmental low-load type ink called Non-VOC ink, etc., which are disclosed in japanese patent application laid-open publication nos. 2005-336301, 2005-126579, 2011-144295, 2012-224823, etc., in which a solvent component is replaced with a vegetable oil component from a conventional mineral oil (petroleum) component, are also included in the oil-soluble oxidative polymerization type ink.
< ink-2 > Water-soluble oxidative polymerization type ink
Examples of the water-soluble oxidative polymerization type ink include known water-soluble oxidative polymerization type inks which can be washed with water or an aqueous washing liquid as disclosed in, for example, japanese patent application laid-open publication No. 2009-57461 and japanese patent No. 4522094.
< ink-3 > oil-soluble active energy ray-curable ink
Examples of the oil-soluble active energy ray-curable ink include known active energy ray-curable inks which can be cleaned with an oil-based cleaning liquid, as disclosed in, for example, japanese patent application laid-open No. 5158274 and japanese patent application laid-open No. 2012-211230. In addition, the active energy ray-curable ink further contains a high-sensitivity UV ink for power-saving (light-reducing) UV printing or LED-UV printing.
< ink-4 > Water-soluble active energy ray-curable ink
Examples of the water-soluble active energy ray-curable ink include known water-soluble active energy ray-curable inks which are washable with water or an aqueous washing liquid as disclosed in japanese unexamined patent publication No. 2017-52817, international publication No. 2017/047817, international publication No. 2017/090663, and the like.
Among these inks, the oil-soluble or water-soluble active energy ray-curable ink is preferable because it is cured instantaneously by irradiation of active energy rays after transfer onto a printing medium, and thus has an advantage that it is not possible to immediately perform back-side printing or post-processing, which is the case with the conventional oxidative polymerization type ink. However, unlike conventional oxidative polymerization type inks, the active energy ray-curable ink has a disadvantage that the ink contains no or only a very small amount of contamination preventing component, and thus is liable to cause contamination during printing. Since the printing plate of the present invention has high ink repellency, the oil-soluble active energy ray-curable ink and the water-soluble active energy ray-curable ink can be used favorably. In addition, when cleaning ink adhering to various rollers, blankets, printing plates, and the like of a printing machine, an organic solvent having high volatility and being harmful is used for oil-soluble ink such as oil-soluble oxidative polymerization type ink or oil-soluble active energy ray-curable ink, so that the load on human body and environment is large. On the other hand, since water-soluble inks such as water-soluble oxidative polymerization type inks and water-soluble active energy ray-curable inks can be washed with water alone or with a washing liquid containing water as a main component, there is no need to use an organic solvent which is highly volatile and harmful, and this is preferable in view of being able to significantly suppress the load on the human body or the environment. In particular, a water-soluble active energy ray-curable ink can be more suitably used.
Examples of the printing medium include: examples of the material include, but are not limited to, papers such as fine papers, coated papers, cast papers, synthetic papers, and papers for newspapers, metals such as aluminum or aluminum alloy, iron, steel, zinc, and copper, plastic films such as polyethylene terephthalate, polyethylene, polyester, polyamide, polyimide, polystyrene, polypropylene, polycarbonate, and polyvinyl acetal, and composites of these papers, metals, and plastic films (papers or plastic films deposited or laminated with metals, papers or metals laminated with plastic films, and metals or plastic films laminated with papers).
In the method for producing a seamless printed matter of the present invention, the surface to be printed is made of a metal or plastic film, and synthetic paper, metal, plastic film, or metal-deposited or metal-laminated paper or plastic film is suitably printed on a printing medium which is non-absorbent in ink components such as plastic film-laminated paper or metal.
Among the above, the surface to be printed is made of a plastic film, and a surface to be printed of a synthetic paper, a plastic film, a paper laminated with a plastic film, a metal, or the like may be subjected to surface treatments such as primer resin application, corona discharge treatment, plasma treatment, or the like from the viewpoint of improving adhesion.
As the shape of the printing medium, a long printing medium in a roll shape is preferably used. By using the printing plate and the long and long printing medium in a roll form of the present invention, a high-definition seamless printed matter having no seam on the motif pattern can be mass-produced by printing by a roll-to-roll method.
The thickness of the ink coating film (ink cured film) on the print medium is preferably 0.1 to 50 μm. By setting the thickness of the ink coating film within the above range, the ink cost can be reduced while maintaining good printing quality.
Next, a method of regenerating a cylindrical support from an original plate or a printing plate will be described.
Since the master or printing plate of the present invention has the easily releasable primer layer continuously adjacent to the outer peripheral surface of the cylindrical support, the cylindrical support can be easily regenerated without requiring complicated operations such as wet treatment such as cleaning with chemicals or polishing of the outer peripheral surface of the cylindrical support, by peeling the easily releasable primer layer together with each functional layer provided on the outer peripheral surface thereof from the master or printing plate into a film by a dry process. That is, the method for regenerating a cylindrical support of the present invention is to peel the easily peelable primer layer into a film shape by a dry process from the outer peripheral surface of the original plate of the present invention or the cylindrical support of the printing plate of the present invention.
The master can be repeatedly produced by continuously providing the easily peelable primer layer, the ink repellent layer, and the other functional layers again on the outer peripheral surface of the cylindrical support regenerated by peeling the easily peelable primer layer and the functional layers provided on the outer peripheral surface thereof together into a film by a dry process. The cylindrical support body is economically advantageous because it can be reused.
Next, the composition for forming an easily releasable primer layer of the present invention will be described. The composition for forming the easily releasable primer layer is defined as described above. The composition for forming an easily releasable primer layer of the present invention contains a compound having a functional group with a cohesive energy of 20 to 60 kJ/mol. As the compound having a functional group with an aggregation energy of 20 to 60kJ/mol, a compound having a urethane bond and/or a hydroxyl group is preferable, and polyurethane is more preferable. In addition, as the compound having a functional group with a coagulation energy of 20 to 60kJ/mol, a compound having an ethylenically unsaturated double bond is preferable, and urethane acrylate is more preferable.
The composition for forming an easily releasable primer layer of the present invention preferably further contains inorganic particles.
Examples of the composition for forming an easily releasable primer layer of the present invention include a composition exemplified as a composition for forming an easily releasable primer layer preferably used in the method for producing a master.
Examples
Hereinafter, the present invention will be described in more detail with reference to examples.
The evaluation in each example and comparative example was performed by the following method.
< evaluation methods in examples and comparative examples >
(1) Evaluation of primer layer
(1-1) ease of regeneration of the plate cylinder sleeve (ease of stripping of primer layer)
For the original plates produced in each of examples and comparative examples, the release primer layer was peeled off from the outer peripheral surface of the plate cylinder sleeve by a dry process, and the ease of recycling of the plate cylinder sleeve was evaluated. The ease of regeneration of the plate cylinder sleeve is scored as follows.
A: the plate cylinder sleeve was very easy to recycle (the easily releasable primer layer could be easily released in film form by a dry process.)
B: the plate cylinder sleeve was easy to regenerate (the easily releasable primer layer was releasable by a dry process, but the easily releasable primer layer was broken during the release process.)
C: the plate cylinder sleeve cannot be regenerated (the bottom layer cannot be peeled off by a dry process).
(1-2) adhesion of the plate Cylinder Sleeve to the strippable primer layer
In each of examples and comparative examples, a razor was used to apply a width at a randomly selected position from among the easily peelable primer layers formed on the outer peripheral surface of the plate cylinder sleeve: 0.1m, length: strip cut in 0.1m, using a digital load cell: ZTA-500N (manufactured by Deku-Co.) was measured for the force [ N/0.1m ] when the releasable primer layer was peeled from the plate cylinder sleeve in the longitudinal direction by 0.05m, and the resultant peeling force [ N/0.1m ] was multiplied by 10 times to calculate the adhesion force [ N/m ] between the plate cylinder sleeve and the releasable primer layer.
(1-3) film Strength of the easily strippable primer layer
According to the tensile strength [ N/mm ] of the easily peelable primer layer obtained by the method of (1-3-1) below 2 ]And the average thickness [ mm ] of the easily releasable primer layer obtained by the method of (1-3-2) below]The product of (a) was used to determine the film strength [ N/mm ] of the easily peelable primer layer]. In order to easily grasp the relationship between the adhesion force of the plate cylinder sleeve and the easily peelable primer layer, the film strength of the easily peelable primer layer [ N/mm]1000 times the total unit of [ N/m ]]。
(1-3-1) tensile Strength of the easily peelable primer layer
In the above (1-1), the tensile strength of the releasable primer layer was measured by the method defined in JIS K6251:2017 using the releasable primer layer released from the plate cylinder sleeve. In the measurement, a tensile tester was used: "Teflon" (registered trademark) RTF-1350 (manufactured by Depsida corporation), an air motor was used for sandwiching the sample.
(1-3-2) average thickness of the easily peelable primer layer
In the above (1-1), after embedding the resin in the releasable primer layer released from the plate cylinder sleeve, a scanning electron microscope is used: SU3900 (hitachi) magnifies the cross section of the sample prepared by the microtome. In the vertical cross-sectional image, the thickness was measured for 10 sites randomly selected from the easily peelable primer layer, and the number average value thereof was calculated, thereby obtaining the average thickness of the easily peelable primer layer.
(1-4) elongation at break of the easily peelable primer layer
In the above (1-1), the elongation at break of the releasable primer layer was measured by the method defined in JIS K6251:2017 using the releasable primer layer released from the plate cylinder sleeve. In the measurement, a tensile tester was used: "Ten" (registered trademark) RTF-1350, an air motor was used for sandwiching the sample.
(2) Printing evaluation
The printing plates obtained by the methods described in examples and comparative examples were mounted on an EB offset printing press: printing was performed up to 100000m under the printing conditions shown below on the plate cylinder axis of OFFSET CI/8 (manufactured by COMEXI Co.).
< printing Condition >
Ink roller: #8000 (Minghe rubber industry Co., ltd.)
Cylinder blanket: EPDM furin (strain) manufactured by jinyang corporation
Water-soluble EB ink: offset EB ink F type FE1908 process 4 color (Sanxingjiki Co., ltd.)
Wetting water: purified water (used only in example 16 using seamless horizontal plate printing)
Non-absorptive printed media for ink components: "Eten" (registered trademark) PTM-12 (roll biaxially stretched PET film, thickness: 12 μm, print surface: easy adhesion treatment, manufactured by Equ corporation)
Layout temperature: 25-28 DEG C
Printing speed: 100 m/min
< ink curing Condition >
EB dose: 40kGy
EB irradiation atmosphere: in a nitrogen atmosphere.
(2-1) possibility of seamless printing
The printed matter was visually observed, and whether or not seamless printing of intermittent patterns and continuous patterns was possible was evaluated. The score of the seamless printing availability is as follows.
A: can be printed without seam (printed matter is not confirmed with pattern seam)
B: no seamless printing (confirming the presence of a pattern seam on the print) was possible.
(2-2) image reproducibility
About 5000 meters of printed matter was cut out from the beginning of printing, placed on a 5-piece superimposed OK box コ (registered trademark) +and the dot portion was observed with a magnification of 50 times using a magnifying glass. The score of the image reproducibility is as follows.
A, reproducing 1-99% of the dots of AM screening 175lpi (resolution: 2400 dpi).
(2-3) printing resistance
Printing was performed up to 100000m at the maximum, and the ultimate print length [ m ] for which good prints were continuously obtained was evaluated as print resistance. In addition, brackets in the print resistance column of table 1 indicate the following.
(P): printing limit due to peeling of primer layer (P layer)
(S): printing limit due to peeling of silicone layer (S layer)
(F) The method comprises the following steps Printing limits caused by damage to the filled (rubbing) silicone part between the head and the tail.
Example 1
The following composition-1 for forming an easily peelable primer layer was applied to the outer peripheral surface of an aluminum alloy plate cylinder sleeve by using a cylindrical slit die coater (manufactured by ruan dwin, ltd.) and heated at 170 ℃ for 10 minutes, whereby a continuous easily peelable primer layer having an average thickness of 25 μm was provided.
< composition for Forming easily strippable primer layer-1 >
The following components (a-1) and (b-1) were added to a container and stirred and mixed until the components were uniform, thereby obtaining a composition-1 for forming an easily releasable primer layer.
(a-1) solvent: n, N-dimethylformamide (boiling point at 1 atm: 153 ℃ C.). 500.0 parts by mass
(b-1) polyurethane solution: "UK" (registered trademark) 9004 (solid content concentration: 20 mass%, solvent: N, N-dimethylformamide/2-butanone (boiling point at 1 atmosphere: 80 ℃ C.), hydroxyl group in polyurethane molecule: none, DIC Co.): 500.0 parts by mass.
Next, the following composition-1 for forming an ink repellent silicone layer was applied to the outer peripheral surface of the easily releasable primer layer by using a cylindrical slit die coater, and heated at 150 ℃ for 5 minutes to provide a continuous ink repellent silicone layer having an average thickness of 20 μm, thereby obtaining a master.
< composition for Forming ink repellent Silicone layer-1 >
The following components (a-2), (b-2) and (c-2) were put into a vessel and stirred and mixed until the components were uniform. The resulting solution was bubbled with dry nitrogen for 20 minutes to remove moisture from the solution. To the resulting solution was added component (d-2), and the mixture was stirred and mixed for 10 minutes. The component (e-2) was added immediately before coating, and the mixture was stirred and mixed to obtain an ink repellent silicone layer-forming composition-1.
(a-2) isoparaffinic solvent: one (registered trademark) E (one) of the urous groups and a cover member manufactured by cover company): 295.00 parts by mass
(b-2) a siloxane compound having 2 or more vinyl groups in the molecule (both terminal dimethylvinylsiloxane-polydimethylsiloxane): DMS-V35 (manufactured by GELEST Inc.: weight average molecular weight: 49500, number of vinyl groups in molecule: 2.0): 91.00 parts by mass
(c-2) a siloxane compound having 3 or more SiH groups in the molecule (a trimethylsiloxy-methylhydrosiloxane-dimethylsiloxane copolymer at both ends): HMS-301 (produced by GELEST Inc., weight average molecular weight: 1950, H group concentration derived from SiH groups: 0.41 mass%, siH groups within the molecule: 8.0): 6.0 parts by mass
(d-2) silane coupling agent and reaction inhibitor: vinyl tris (methyl ethyl ketoxime) (Vinyltris (methylethylketoximino) silane) silane: 3.0 parts by mass
(e-2) reaction catalyst (platinum mixture): XC94-C4326 (end) docking station; the cover is manufactured by super contract company, concentration of solid content: 1 mass%): 5 parts by mass.
Using an F2 excimer laser drawing apparatus (wavelength: 157 nm), on the ink repellent silicone layer of the master, an exposure amount was set in vacuum: 300mJ/cm 2 Ultraviolet ray drawing is performed to plate the original plate, thereby obtaining a printing plate.
Example 2
A printing plate was obtained in the same manner as in example 1, except that the composition-1 for forming an easily releasable primer layer was changed to the composition-2 for forming an easily releasable primer layer described below.
< composition for Forming easily strippable primer layer-2 >
The following components (a-3) and (b-3) were added to a container and stirred and mixed until the components were uniform, thereby obtaining a composition-2 for forming an easily releasable primer layer.
(a-3) solvent: n, N-dimethylformamide: 666.7 parts by mass
(b-3) polyurethane solution: "crassin" (registered trademark) 8966 (solid content concentration: 30 mass%, solvent: N, N-dimethylformamide, hydroxyl group in polyurethane molecule: none, manufactured by DIC Co.): 333.3 parts by mass.
Example 3
A printing plate was obtained in the same manner as in example 1, except that the composition-1 for forming an easily releasable primer layer was changed to the composition-3 for forming an easily releasable primer layer described below.
< composition for Forming easily strippable primer layer-3 >
The following components (a-4) and (b-4) were added to a container and stirred and mixed until the components were uniform, thereby obtaining a composition-3 for forming an easily releasable primer layer.
(a-4) solvent: n, N dimethylformamide: 600.0 parts by mass
(b-4) polyurethane solution: "packing" (registered trademark) LQ-T1333 (solid content: 25% by mass, solvent N, N dimethylformamide, hydroxyl group in polyurethane: none, sanyo chemical industry Co., ltd.): 400.0 parts by mass.
Example 4
A printing plate was obtained in the same manner as in example 3, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 15 μm.
Example 5
A printing plate was obtained in the same manner as in example 3, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 12 μm.
Example 6
A printing plate was obtained in the same manner as in example 1, except that the composition-1 for forming an easily releasable primer layer was changed to the composition-4 for forming an easily releasable primer layer, the heating temperature was lowered from 170℃to 80℃and the average thickness of the easily releasable primer layer was increased from 25 μm to 30. Mu.m.
< composition for Forming easily strippable primer layer-4 >
The following components (a-5) and (b-5) were added to a container and stirred and mixed until the components were uniform, thereby obtaining a composition-4 for forming an easily releasable primer layer.
(a-5) solvent: solvent: 2-butanone: 666.7 parts by mass
(b-5) polyurethane solution: "packing" (registered trademark) IB-1700D (solid content concentration: 30 mass%, solvent: 2-butanone/2-propanol (boiling point at 1 atmosphere: 83 ℃) =45/1 mass parts, hydroxyl group in polyurethane molecule: available from san-ken chemical industry (ltd.)): 333.3 parts by mass.
Example 7
A printing plate was obtained in the same manner as in example 1, except that the composition-1 for forming an easily releasable primer layer was changed to the composition-5 for forming an easily releasable primer layer described below, and the heating temperature was changed from 170 ℃ to 80 ℃.
< composition for Forming easily strippable primer layer-5 >
After being filled with zirconia balls: 1600.0 parts by mass of a sealing glass standard bottle (phi 1mm, toshi) of a ball mill (registered trademark) was charged with the following components (a-6), (b-6) and (c-6) and sealed, and the mixture was placed on a small ball mill rotating frame (Shishi) and dispersed at a rotational speed of 0.4 m/sec for 7 days to obtain a composition-5 for forming an easily releasable primer layer.
(a-6) solvent: 2-butanone: 712.7 parts by mass
(b-6) polyurethane solution: "part by mass" IB-1700D:233.3 part by mass
(c-6) inorganic particles: "AEROSIL" (registered trademark) RX200 (fumed silica surface-modified with trimethylsilyl group, manufactured by japan ethylene group) is: 54.0 parts by mass.
Example 8
A printing plate was obtained in the same manner as in example 1, except that the composition-1 for forming an easily releasable primer layer was changed to the composition-6 for forming an easily releasable primer layer described below, and the heating temperature was changed from 170 ℃ to 120 ℃.
< composition for Forming easily strippable primer layer-6 >
The following components (a-7) and (b-7) were added to a container and stirred and mixed until the components were uniform, thereby obtaining a composition-6 for forming an easily releasable primer layer.
(a-7) purified water (boiling point at 1 atm: 100 ℃ C.): 500.0 parts by mass
(b-7) aqueous polyurethane dispersion: "tap-tap" (registered trademark) 150 (solid content: 30 mass%, nonreactive, hydroxyl group in polyurethane molecule: none, manufactured by first industry pharmaceutical Co., ltd.): 500.0 parts by mass.
Example 9
A printing plate was obtained in the same manner as in example 8, except that the drying condition of the easily releasable primer layer was changed from heating at 170 ℃ for 10 minutes to heating at 30 ℃ for 3 hours.
Example 10
The following composition-7 for forming an easily peelable primer layer was applied to the outer peripheral surface of the aluminum alloy plate cylinder sleeve by using an LED-type line UV irradiator in addition to the cylindrical slit die coater: a printing plate was obtained in the same manner as in example 1, except that UD90 (manufactured by UpBur et al, wavelength: 385 nm) was irradiated with ultraviolet light for 1 minute to cure the printing plate, and a continuous releasable primer layer having an average thickness of 25 μm was provided.
< composition for Forming easily strippable primer layer-7 >
The following components (a-8) and (b-8) were added to a container and stirred and mixed until the components were uniform, thereby obtaining a composition-7 for forming an easily releasable primer layer.
(a-8) polyester urethane acrylate oligomer: UF-3999AM (30% by mass dilution of acryloylmorpholine, hydroxyl group in polyester urethane acrylate oligomer molecule: none, manufactured by Kyowa Co., ltd.): 960.0 parts by mass
(b-8) a photoradical generator: an "irku" (registered trademark) 184 (manufactured by BASF Japan corporation): 40.0 parts by mass
Example 11
A printing plate was obtained in the same manner as in example 10, except that the composition for forming an easily releasable primer layer-7 was changed to the composition for forming an easily releasable primer layer-8 described below.
< composition for Forming easily strippable primer layer-8 >
The following components (a-9) and (b-9) were added to a container and stirred and mixed until the components were uniform, thereby obtaining a composition-8 for forming an easily releasable primer layer.
(a-9) NK-APG-700 (polypropylene glycol diacrylate, manufactured by Xinzhou chemical Co., ltd.): 660.0 parts by mass
(b-9) "a sleeve" (registered trademark) PE-3A (pentaerythritol triacrylate, manufactured by co-company chemical corporation): 300.0 parts by mass
(c-9) a photoradical generator: an "irku" (registered trademark) 184 (manufactured by BASF Japan corporation): 40.0 parts by mass
Example 12
A printing plate was obtained in the same manner as in example 1, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 50 μm.
Example 13
An original plate was obtained in the same manner as in example 1, except that the ink repellent silicone layer-forming composition-1 was changed to the ink repellent silicone layer-forming composition-2 described below.
< composition for Forming ink repellent Silicone layer-2 >
The following components (a-10), (b-10), (c-10) and (d-10) were put into a vessel and stirred and mixed until the components were uniform. The resulting solution was bubbled with dry nitrogen for 20 minutes to remove moisture from the solution. To the resulting solution was added the component (e-10), and the mixture was stirred and mixed for 10 minutes. The component (f-10) was added immediately before coating, and the mixture was stirred and mixed to obtain an ink repellent silicone layer-forming composition-2.
(a-10) "A sleeve" (registered trademark) E:895.0 parts by mass
(b-10) a siloxane compound having 2 or more vinyl groups in the molecule (trimethicone-vinylmethylsiloxane-dimethylsiloxane copolymer at both ends): VDT-954 (produced by GELEST Inc., weight average molecular weight: 225000, vinyl concentration: 4.29% by mass, vinyl number in molecule: 357.2): 62.0 parts by mass
(c-10) a liquid having a surface tension of 30mN/m or less at 25 ℃: KF-96-50cs (Dimethicone, weight average molecular weight: 3780, surface tension at 25 ℃ C.: 20.8mN/m, mass reduction rate after heating at 150 ℃ C. For 24 hours under 1 atmosphere pressure: 0.1 mass%, manufactured by Xinyue chemical Co., ltd.): 20.0 parts by mass
(d-10) a siloxane compound having 3 or more SiH groups in the molecule (trimethicone-methylhydrosiloxane-dimethylsiloxane copolymer at both ends): HMS-064 (produced by GELEST Inc., weight average molecular weight: 55000, H group concentration from SiH groups: 0.08 mass%, siH groups in the molecule: 44.4): 15.0 parts by mass
(e-10) vinyltris (methylethylketoxime) silane (Vinyltris (methylethylketoximino) silane): 3.0 parts by mass
(f-10) XC94-C4326:5.0 parts by mass.
Next, using a Sub-femto ink jet processing device (SIJ, inc.) under the condition that the ejected droplet volume was 2 nanoliters, the following composition-1 pattern for forming an inking portion was ejected onto the ink repellent silicone layer, and heated at 150 ℃ for 5 minutes, thereby obtaining a printing plate.
< composition for Forming inking portion-1 >
The following components (a-11), (b-11), (c-11) and (d-11) were put into a vessel and stirred and mixed until the components were uniform. The resulting solution was bubbled with dry nitrogen for 20 minutes to remove moisture from the solution. The component (e-11) was added immediately before application, and the mixture was stirred and mixed to obtain an ink-applied portion-forming composition-1.
(a-11) "A sleeve" (registered trademark) C:95.0 parts by mass
(b-11) VDT-954:70.0 parts by mass
(c-11) HMS-993:30.0 parts by mass
(d-11) 2-methyl-3-butyn-2-ol: 1.5 parts by mass
(e-11) XC94-C4326:3.5 parts by mass.
Example 14
The composition-1 for forming an easily peelable primer layer was applied to the outer peripheral surface of an aluminum alloy plate cylinder sleeve by a cylindrical slit die coater, and heated at 170℃for 10 minutes, thereby providing a continuous easily peelable primer layer having an average thickness of 25. Mu.m.
Next, the following composition-3 for forming an ink repellent silicone layer was applied to the outer peripheral surface of the easily releasable primer layer by using a cylinder slit coater, and heated at 150 ℃ for 5 minutes to provide a continuous ink repellent silicone layer having an average thickness of 20 μm.
< composition for Forming ink repellent Silicone layer-3 >
The following components (a-12), (b-12) and (c-12) were put into a vessel and stirred and mixed until the components were uniform. The resulting solution was bubbled with dry nitrogen for 20 minutes to remove moisture from the solution. To the resulting solution was added component (d-12), and the mixture was stirred and mixed for 10 minutes. The component (e-12) was added immediately before coating, and the mixture was stirred and mixed to obtain an ink repellent silicone layer-forming composition-3.
(a-12) "A sleeve" (registered trademark) E:895.0 parts by mass
(b-12) VDT-954:82.0 parts by mass
(c-12) a siloxane compound having 3 or more SiH groups in the molecule (trimethicone-methylhydrosiloxane-dimethylsiloxane copolymer at both ends): HMS-064 (produced by GELEST Inc., weight average molecular weight: 55000, H group concentration from SiH groups: 0.08 mass%, siH groups in the molecule: 44.4): 15.0 parts by mass
(d-12) vinyltris (methylethylketoxime) silane: 3.0 parts by mass
(e-12) XC94-C4326, 5.0 parts by mass.
Next, the composition-1 for forming an ink-repellent silicone layer was applied onto the outer peripheral surface of the ink-repellent silicone layer by using a cylindrical slit die coater, and heated at 150 ℃ for 5 minutes to provide a continuous ink-repellent silicone layer having an average thickness of 0.4 μm, thereby obtaining a master.
ArF excimer pulse laser (wavelength: 193 nm) was used to irradiate energy density with laser: 150mJ/cm 2 Pulse repetition frequency: 10Hz, laser irradiation portion atmosphere: the original plate was subjected to pattern irradiation from the side of the obtained ink-receptive silicone layer of the original plate under nitrogen atmosphere conditions, and the entire ink-receptive silicone layer and the upper portion of the ink-repellent silicone layer of the laser irradiation section were ablated to plate the original plate, thereby obtaining a printing plate.
Example 15
The composition-1 for forming an easily peelable primer layer was applied to the outer peripheral surface of an aluminum alloy plate cylinder sleeve by a cylinder slit die coater and heated at 170℃for 10 minutes, whereby a continuous easily peelable primer layer having an average thickness of 25 μm was provided.
Next, the following hydrophilic layer-forming composition-1 was applied to the outer peripheral surface of the easily releasable primer layer by a cylinder slit coater, and heated at 150 ℃ for 5 minutes, to provide a continuous hydrophilic layer having an average thickness of 3 μm.
< composition for Forming hydrophilic layer-1 >
The following components (a-13), (b-13) and (c-13) were put into a vessel and stirred and mixed until the components were uniform, thereby obtaining a composition-1 for forming a hydrophilic layer.
(a-13) hydrophilic polymer obtained in the following Synthesis example 1: 10 parts by mass
(b-13) N-hydroxyethyl xylylenediamine: 1 part by mass
(c-13) purified water: 100 parts by mass.
Synthesis example 1
0.5g of benzoyl peroxide as a polymerization initiator was metered in to 60g of vinyl acetate and 40g of methyl acrylate, and they were dispersed in 300ml of water containing 3g of partially saponified polyvinyl alcohol as a dispersion stabilizer and 10g of NaCl:10 g. The resulting dispersion was stirred at 65℃for 6 hours, and suspension polymerization was carried out. 8.6g of the resulting copolymer was added to a mixture of methanol: 200 g/water: 10g/5N NaOH 40ml, stirring and suspending, at 25 ℃ for 1 hours saponification reaction, heating to 65 ℃ and further for 5 hours saponification reaction. The obtained saponification reaction product was sufficiently washed with methanol, and then freeze-dried to obtain a hydrophilic polymer.
Next, the following composition-1 for forming an ink-receptive thermosensitive layer was applied to the outer peripheral surface of the hydrophilic layer by a cylindrical slit die coater, and heated at 70 ℃ for 5 minutes, thereby providing a continuous ink-receptive thermosensitive layer having an average thickness of 3 μm, to obtain a master.
< composition for Forming an ink-receptive thermosensitive layer-1 >
The following components were put into a container and stirred and mixed until the components were uniform, thereby obtaining an ink-receptive thermosensitive layer-forming composition-1.
(a-14) "KAYASORB" (registered trademark) IR-820B (infrared absorbing dye, manufactured by japan chemical Co., ltd.): 5 parts by mass
(b-14) aluminum chelate D (aluminum ethylacetylacetonate diacetylacetate, manufactured by chuanmilf corporation): 20 parts by mass
(c-14) epoxy ester 80MFA (epoxy acrylate, co., ltd.): 40 parts by mass of (d-14) polyvinyl alcohol AL-06 (manufactured by Japanese synthetic chemical Co., ltd.): 10 parts by mass
(e-14) polyurethane emulsion "radial" R-5100 (manufactured by first industry pharmaceutical Co., ltd.): 40 parts by mass
(f-14) "Cataloid" (registered trademark) SI-30 (aqueous dispersion of colloidal silica fine particles having an average particle diameter of 0.01 to 0.014 μm, manufactured by catalyst chemical industry Co., ltd.): 10 parts by mass
(g-14) purified water: 700 parts by mass
(h-14) ethylene glycol monoethyl ether: 200 parts by mass.
Using a semiconductor laser (wavelength: 808 nm), the laser irradiation energy density: 200mJ/cm 2 Patterning from the side of the inking thermosensitive layer of the obtained master under the conditionAfter exposure, the surface was rubbed with cotton containing water to remove the ink-receptive heat-sensitive layer in the unexposed portion, and the master was plate-made to obtain a printing plate with the underlying ink-repellent hydrophilic layer exposed.
Example 16
The composition-1 for forming an easily peelable primer layer was applied to the outer peripheral surface of an aluminum alloy plate cylinder sleeve by a cylinder slit die coater, and heated at 170℃for 10 minutes, thereby providing a continuous easily peelable primer layer having an average thickness of 25. Mu.m.
Next, the following composition-2 for forming an ink-receptive thermosensitive layer was applied to the outer peripheral surface of the easily releasable primer layer by a cylinder slit coater, and heated at 150 ℃ for 5 minutes, thereby providing a continuous ink-receptive thermosensitive layer having an average thickness of 1 μm.
< composition for Forming an ink-receptive thermosensitive layer-2 >
The following components were put into a container and stirred and mixed until the components were uniform, thereby obtaining an ink-receptive thermosensitive layer-forming composition-2.
(a-15) phenol formaldehyde novolac resin: "stan resin" (registered trademark) PR53195 (manufactured by sumitomo brand corporation): 45.0 parts by weight
(b-15) polyurethane solution: "Potentin" (registered trademark) 5196 (manufactured by Potentin, japan, solid content concentration: 30% by weight): 62.5 parts by weight
(c-15) an infrared absorbing dye: PROJET 825LDI (available from Avecia): 12.0 parts by weight of (d-15) titanium di-n-butoxydi (acetylacetonate) solution: "Neu-y" (registered trademark) titanium (solid content concentration: 73% by weight, manufactured by Japanese chemical industries, ltd.): 28.5 parts by weight
(e-15) polyoxypropylene diamine/glycidyl methacrylate/3-glycidoxypropyl trimethoxysilane=1/3/1 molar reactant (solid content concentration: 50 wt%): 22.5 parts by weight
(f-15) tetrahydrofuran: 717.0 parts by weight
(g-15) ethanol: 112.5 parts by weight.
Next, the following composition for forming an ink repellent silicone layer-4 was applied to the outer peripheral surface of the ink repellent heat sensitive layer using a cylindrical slit die coater, and heated at 150 ℃ for 5 minutes, thereby providing a continuous ink repellent silicone layer having an average thickness of 3 μm, to obtain a master.
< composition for Forming ink repellent Silicone layer-4 >
The following components (a-16), (b-16) and (c-16) were put into a vessel and stirred and mixed until the components were uniform. The resulting solution was bubbled with dry nitrogen for 20 minutes to remove moisture from the solution. The (d-16), (e-16) and (f-16) components were added to the obtained solution, and the mixture was stirred and mixed for 10 minutes, after which the (g-16) component was added thereto, and further stirred and mixed for 10 minutes. The component (h-16) was added immediately before coating, and the mixture was stirred and mixed to obtain an ink repellent silicone layer-forming composition-4.
(a-16) A-B (registered trademark) E:894.05 parts by weight
(b-16) DMS-V35:73.68 parts by weight
(c-16) KF-96-50cs 2.00 weight portions
(d-16) SiH group-containing Compound (trimethicone-methyl hydrosiloxane-dimethylsiloxane copolymer at both ends): "HMS" -301 (manufactured by GELEST Inc.: weight average molecular weight: 1960, siH group equivalent: 245, siH groups in the molecule: 8): 2.27 parts by weight
(e-16) vinyltris (methylethylketoxime) silane: 1.00 parts by weight
(f-16) phenyltriacetoxysilane: 3.00 parts by weight
(g-16) reaction inhibitor: gamma-picoline: 1.00 parts by weight
(h-16) XC94-C4326:5.00 parts by weight.
Using a semiconductor laser (wavelength: 808 nm), the laser irradiation energy density: 200mJ/cm 2 After pattern exposure from the ink repellent silicone layer side of the obtained master, the surface was wiped with cotton containing water to remove the ink repellent silicone layer in the exposed portion, thereby making a plate from the master to obtain a printing plate.
Example 17
A printing plate was obtained in the same manner as in example 16, except that the composition-1 for forming an easily releasable primer layer was changed to the composition-3 for forming an easily releasable primer layer.
Example 18
A printing plate was obtained in the same manner as in example 17, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 15. Mu.m.
Example 19
A printing plate was obtained in the same manner as in example 17, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 12. Mu.m.
Example 20
A printing plate was obtained in the same manner as in example 16, except that the composition-1 for forming an easily releasable primer layer was changed to the composition-4 for forming an easily releasable primer layer, the heating temperature was lowered from 170 ℃ to 80 ℃, and the average thickness of the easily releasable primer layer was increased from 25 μm to 30 μm.
Example 21
A printing plate was obtained in the same manner as in example 16, except that the composition-1 for forming an easily releasable primer layer was changed to the composition-5 for forming an easily releasable primer layer, and the heating temperature was changed from 170 ℃ to 80 ℃.
Example 22
A printing plate was obtained in the same manner as in example 16, except that the composition-1 for forming an easily releasable primer layer was changed to the composition-6 for forming an easily releasable primer layer, and the heating temperature was changed from 170 ℃ to 120 ℃.
Example 23
A printing plate was obtained by the same method as in example 22, except that the drying condition of the easily releasable primer layer was changed from heating at 170 ℃ for 10 minutes to heating at 30 ℃ for 3 hours.
Example 24
In addition to applying the composition for forming an easily peelable primer layer-7 on the outer peripheral surface of the aluminum alloy plate cylinder sleeve using a cylindrical slot die coater, an LED-type line UV irradiator was used: a printing plate was obtained in the same manner as in example 16, except that UD90 was cured by irradiation of ultraviolet light for 1 minute, thereby providing a continuous releasable primer layer having an average thickness of 25. Mu.m.
Example 25
A printing plate was obtained in the same manner as in example 24, except that the composition for forming an easily releasable primer layer-7 was changed to the composition for forming an easily releasable primer layer-8.
Example 26
A printing plate was obtained in the same manner as in example 16, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 50. Mu.m.
Comparative example 1
A printing plate was obtained in the same manner as in example 1, except that the easily peelable primer layer was not provided.
Comparative example 2
A printing plate was obtained in the same manner as in example 1, except that the composition-1 for forming an easily releasable primer layer was changed to the composition-1 for forming a primer layer described below.
< composition for Forming primer layer-1 >
The following components (a-17) and (b-17) were added to a container and stirred and mixed until the components were uniform, thereby obtaining a composition 12 for forming a releasable primer layer.
(a-17) epoxy resin: "jER" (registered trademark) 828 (bisphenol a type liquid epoxy resin, mitsubishi chemical company, ltd.): 500.0 parts by mass
(b-17) a polyamine: "wound film" (registered trademark) T-403 (trimethylolpropane poly (oxypropylene) triamine, manufactured by the company furn): 500.0 parts by mass.
Comparative example 3
The heat shrinkage tube is disposed so as to cover the outer peripheral surface of the plate cylinder sleeve made of aluminum alloy: コ A (material: PET, thickness: 80 μm, manufactured by Sion Polymer Co., ltd.) was heated at 120℃for 5 minutes to heat-shrink the heat-shrinkable tube, and the heat-shrinkable tube was fixed to the outer peripheral surface of the plate cylinder sleeve. Next, a double-sided tape 777 (manufactured by temple) is attached to the outer peripheral surface of the heat-shrinkable tube after heat shrinkage, and then the single-page-shaped waterless lithographic printing plate precursor is wound and fixed: an anhydrous lithographic printing plate manufactured by TAC-VT4 (manufactured by Toli Co., ltd.). The ink repellent silicone layer forming composition-1 was partially filled in the gap (about 0.5 mm) between the head and the tail of the rolled single sheet-like waterless lithographic printing plate, and cured by heating at 150 ℃ for 5 minutes, to obtain a master.
Example 27
A printing plate was obtained in the same manner as in example 1, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 15. Mu.m, and the heating time of the easily releasable primer layer was changed from 10 minutes to 20 minutes.
Example 28
A printing plate was obtained in the same manner as in example 1, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 15. Mu.m, and the heating time of the easily releasable primer layer was changed from 10 minutes to 30 minutes.
Example 29
A printing plate was obtained in the same manner as in example 1, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 20. Mu.m, and the heating time of the easily releasable primer layer was changed from 10 minutes to 30 minutes.
Example 30
A printing plate was obtained in the same manner as in example 1, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 20. Mu.m, the heating temperature of the easily releasable primer layer was changed from 170℃to 185℃and the heating time of the easily releasable primer layer was changed from 10 minutes to 30 minutes.
Example 31
A printing plate was obtained in the same manner as in example 1, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 30. Mu.m, the heating temperature of the easily releasable primer layer was changed from 170℃to 185℃and the heating time of the easily releasable primer layer was changed from 10 minutes to 30 minutes.
Example 32
A printing plate was obtained in the same manner as in example 1, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 30. Mu.m, the heating temperature of the easily releasable primer layer was changed from 170℃to 200℃and the heating time of the easily releasable primer layer was changed from 10 minutes to 30 minutes.
Example 33
A printing plate was obtained in the same manner as in example 16, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 15. Mu.m, and the heating time of the easily releasable primer layer was changed from 10 minutes to 20 minutes.
Example 34
A printing plate was obtained in the same manner as in example 16, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 15. Mu.m, and the heating time of the easily releasable primer layer was changed from 10 minutes to 30 minutes.
Example 35
A printing plate was obtained in the same manner as in example 16, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 20. Mu.m, and the heating time of the easily releasable primer layer was changed from 10 minutes to 30 minutes.
Example 36
A printing plate was obtained in the same manner as in example 16, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 20. Mu.m, the heating temperature of the easily releasable primer layer was changed from 170℃to 185℃and the heating time of the easily releasable primer layer was changed from 10 minutes to 30 minutes.
Example 37
A printing plate was obtained in the same manner as in example 16, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 30. Mu.m, the heating temperature of the easily releasable primer layer was changed from 170℃to 185℃and the heating time of the easily releasable primer layer was changed from 10 minutes to 30 minutes.
Example 38
A printing plate was obtained in the same manner as in example 16, except that the average thickness of the easily releasable primer layer was changed from 25 μm to 30. Mu.m, the heating temperature of the easily releasable primer layer was changed from 170℃to 200℃and the heating time of the easily releasable primer layer was changed from 10 minutes to 30 minutes.
The evaluation results of examples 1 to 26 and comparative examples 1 to 3 are shown in table 1. The evaluation results of examples 27 to 38 are shown in table 2. In addition, since no primer layer was provided in comparative examples 1 and 3, the column "(1) evaluation of primer layer" in table 1 is blank. In comparative example 2, the primer layer could not be peeled from the plate cylinder sleeve by the dry process, so in table 1, the columns of the adhesion force, film strength, elongation at break of "(1) evaluation of the easily peelable primer layer" are blank.
TABLE 1
TABLE 2
Description of the drawings
A intermittent pattern
B continuous pattern
D printing direction
E seamless lithographic printing plate F seamless print
P printing
R1 printing plate week 1
R2 printing plate week 2
1 line drawing part
2 non-line drawing part
3 printed media
4 transfer printing pattern
5 ink roller
6 wetting roller
7 seamless lithographic printing plate
8 blanket cylinder
9 printed media
10 impression cylinder
Claims (22)
1. A seamless lithographic printing plate precursor comprising a cylindrical support and, on the outer peripheral surface thereof, a continuous layer of an easily peelable primer and an ink repellent layer.
2. The seamless lithographic printing plate precursor according to claim 1, wherein the adhesion force of the cylindrical support and the easily releasable primer layer is smaller than the film strength of the easily releasable primer layer.
3. The seamless lithographic printing plate precursor according to claim 1, wherein the adhesion force of the cylindrical support and the easily releasable primer layer is 10 to 2000N/m.
4. The seamless lithographic printing plate precursor according to claim 1, wherein the elongation at break of the easily releasable primer layer is 10 to 1000%.
5. The seamless lithographic printing plate precursor according to claim 1, wherein the average thickness of the easily releasable primer layer is 15 to 500 μm.
6. The seamless lithographic printing plate precursor according to claim 1, wherein the releasable primer layer contains a compound having a functional group with an aggregation energy of 20 to 60 kJ/mol.
7. The seamless lithographic printing plate precursor according to claim 1, wherein the easily releasable primer layer has no covalent bond with the outer peripheral surface of the cylindrical support.
8. The seamless lithographic printing plate precursor according to claim 6, which contains polyurethane as the compound having a functional group with an aggregation energy of 20 to 60 kJ/mol.
9. The seamless lithographic printing plate precursor according to claim 1, wherein the ink repellent layer is a silicone layer.
10. The seamless lithographic printing plate precursor according to claim 1, having an inking layer continuously between the easily releasable primer layer and the ink-repellent layer or further outside the ink-repellent layer.
11. The seamless lithographic printing plate precursor according to claim 10, wherein the inking layer is a photosensitive layer or a thermosensitive layer.
12. A seamless lithographic printing plate obtained by platemaking the seamless lithographic printing plate precursor according to any one of claims 1 to 11.
13. A method for recycling a cylindrical support, wherein the easily releasable primer layer is peeled into a film form by a dry process from the outer peripheral surface of the cylindrical support of the seamless lithographic printing plate precursor according to any one of claims 1 to 11 or the seamless lithographic printing plate according to claim 12.
14. A method for producing a seamless lithographic printing plate precursor, comprising sequentially and continuously forming an easily peelable primer layer and an ink repellent layer on the outer peripheral surface of a cylindrical support regenerated by the method according to claim 13.
15. A method for producing the seamless lithographic printing plate precursor according to any one of claims 1 to 11, wherein the composition for forming the easily releasable primer layer is applied to the outer peripheral surface of the cylindrical support and dried under heating or non-heating, thereby forming the easily releasable primer layer.
16. A method for producing the seamless lithographic printing plate precursor according to any one of claims 1 to 11, wherein the composition for forming the easily releasable primer layer is applied to the outer peripheral surface of the cylindrical support, and the composition for forming the easily releasable primer layer is cured by irradiation with active energy rays, thereby forming the easily releasable primer layer.
17. The method for producing a seamless lithographic printing plate precursor according to claim 15 or 16, wherein the cylindrical support regenerated by the method according to claim 13 is used as the cylindrical support.
18. A composition for forming an easily releasable primer layer, which comprises a compound having a functional group with an aggregation energy of 20-60 kJ/mol.
19. The composition for forming an easily releasable primer layer according to claim 18, wherein the compound having a functional group with an aggregation energy of 20 to 60kJ/mol contains a compound having a urethane bond and/or a hydroxyl group.
20. The composition for forming an easily releasable primer layer according to claim 18 or 19, wherein the compound having a functional group with an aggregation energy of 20 to 60kJ/mol further has an ethylenically unsaturated double bond in a molecule.
21. The composition for forming an easily releasable primer layer according to claim 19, wherein the compound having a functional group with an aggregation energy of 20 to 60kJ/mol contains polyurethane.
22. The composition for forming an easily releasable primer layer according to any one of claims 18 to 21, further comprising inorganic particles.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-139682 | 2021-08-30 | ||
| JP2021139682 | 2021-08-30 | ||
| PCT/JP2022/031827 WO2023032775A1 (en) | 2021-08-30 | 2022-08-24 | Seamless lithographic printing plate precursor, seamless lithographic printing plate, recycling method for cylindrical support body, seamless lithographic printing plate precursor production method, and composition for forming easily releasable primer layer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117440891A true CN117440891A (en) | 2024-01-23 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280040763.1A Pending CN117440891A (en) | 2021-08-30 | 2022-08-24 | Seamless lithographic printing plate precursor, seamless lithographic printing plate, cylindrical support regeneration method, method for producing seamless lithographic printing plate precursor, and composition for forming easily releasable primer layer |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN117440891A (en) |
| WO (1) | WO2023032775A1 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0621734Y2 (en) * | 1987-10-07 | 1994-06-08 | 住友ゴム工業株式会社 | Offset blanket |
| JP2006069137A (en) * | 2004-09-06 | 2006-03-16 | Konica Minolta Medical & Graphic Inc | Planographic printing plate material, printing method, and cutting method of planographic printing plate material |
| UA115253C2 (en) * | 2013-04-10 | 2017-10-10 | Майлен Груп | Lithographic printing plate comprising a laminated substrate |
| WO2019203261A1 (en) * | 2018-04-19 | 2019-10-24 | 東レ株式会社 | Ink adhesion layer forming composition, printing plate, and printed matter manufacturing method using same |
| JP7375271B2 (en) * | 2019-03-26 | 2023-11-08 | Ｔｏｐｐａｎホールディングス株式会社 | Primer layer forming composition, barrier film, wavelength conversion sheet, and method for producing wavelength conversion sheet |
-
2022
- 2022-08-24 WO PCT/JP2022/031827 patent/WO2023032775A1/en unknown
- 2022-08-24 CN CN202280040763.1A patent/CN117440891A/en active Pending
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| WO2023032775A1 (en) | 2023-03-09 |
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