Printing gravure, method for producing same, and printing method

Abstract

A printing gravure plate provided with a resin layer constituting a plate surface, the resin layer having a Shore A hardness of 30-90 degrees inclusive, the resin layer having a surface free energy of 10-35 mN / m inclusive, the resin layer being provided with cells on the plate surface, and the coefficient of variation of the cell volume of the cells for printing at the same ink concentration being 0.2 or less.

Description

Technical Field

[0001] The invention relates to a printing gravure plate and a manufacturing method thereof, and a printing method. Background Art

[0002] Gravure printing has been used for printing high-quality photographs, etc. A commonly used printing plate (gravure cylinder) for gravure printing is a printing plate made of a hard copper plate, a diamond blade or the like is used to carve recessed portions on the surface of the copper plate, and the surface of the printing plate is plated with a hard metal such as chrome.

[0003] The depth of the concave portion can be freely controlled. Recently, a method of engraving with a laser or etching metal by patterning a photoresist using photolithography is sometimes used in forming the concave portion. By accumulating ink in the concave portion thus formed and transferring it to the printed object, a high-quality printed object can be formed in which the shade is expressed by the film thickness of the ink.

[0004] In recent years, the small-batch and multi-variety printing of printed materials has been developing continuously, and gravure printing is also required to cope with the small-batch and multi-variety printing. In addition, the environmental adaptability of printing technology and printed materials has also attracted attention. However, the metallic gravure used in gravure printing is made of metal, so it is not suitable for small-batch and multi-variety printing. In addition, metal waste liquid is generated during its manufacturing process, which cannot meet the environmental adaptability.

[0005] Therefore, a resin gravure plate that can cope with both the small-lot and multi-variety production and environmental adaptability is required. As a resin gravure plate, for example, as disclosed in Patent Document 1, a cylindrical printing original plate that can be laser engraved is known.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2005-254696 Summary of the invention

[0009] Problem that the invention aims to solve

[0010] However, conventional resin gravure plates have the following problems: the volume of cells used for printing with the same ink concentration varies greatly, and the transfer stability of ink from the cells to the substrate deteriorates, especially in the highlight area. In addition, conventional resin gravure plates cannot achieve the same ink concentration in the solid area as metal gravure plates.

[0011] The present invention has been made in view of the above problems, and its object is to provide a printing gravure plate and a method for manufacturing the same, as well as a printing method, etc., wherein the printing gravure plate can improve both the ink transfer stability to the highlight area and the ink adsorption to the solid area.

[0012] Solutions for solving problems

[0013] The present inventors have conducted intensive studies to solve the above problems and have found that the above problems can be solved by adjusting the Shore A hardness, surface free energy and coefficient of variation of unit volume of the resin layer in a resin gravure plate, thereby completing the present invention.

[0014] That is, the present invention is as follows. [1]

[0016] A printing gravure plate, comprising a resin layer constituting a plate surface,

[0017] The Shore A hardness of the resin layer is 30 degrees or more and 90 degrees or less.

[0018] The surface free energy of the resin layer is 10 mN / m or more and 35 mN / m or less,

[0019] The resin layer includes cells on the plate surface, and a coefficient of variation of a cell volume of the cells for printing at the same ink concentration is 0.200 or less. [2]

[0021] The printing gravure according to [1], wherein the concentration of the same ink is 0.50 or less. [3]

[0023] The printing gravure according to [1] or [2], wherein the resin layer contains at least one selected from the group consisting of a photosensitive resin and a thermosetting resin. [4]

[0025] The printing gravure according to any one of [1] to [3], wherein the resin layer contains 0.10 parts by mass or more and 15.0 parts by mass or less of the organosilicon compound based on the total amount. [5]

[0027] The printing gravure according to any one of [1] to [4], wherein the depth of the cell is 0.10 μm or more and 100 μm or less. [6]

[0029] The printing gravure according to any one of [1] to [5], comprising a cylinder,

[0030] The cylindrical resin layer is disposed on the surface of the drum. [7]

[0032] The printing gravure according to [6], wherein a support layer is provided between the drum and the cylindrical resin layer. [8]

[0034] The method for producing a printing gravure according to any one of [1] to [7], comprising a processing step of forming recessed portions in a resin layer using a laser. [9]

[0036] The method for producing a printing gravure according to [8], wherein the oscillation wavelength of the laser light is greater than or equal to 100 nm and less than or equal to 800 nm.

[10]

[0038] The method for producing a printing gravure according to [8] or [9], wherein the laser is a pulsed laser.

[0039] The pulse width of the pulsed laser light is not less than 1 fs and 1 ns.

[11]

[0041] The method for producing a printing gravure according to

[10] , wherein the pulse energy of the laser light is 1.00 μJ or more and 1.00 mJ or less.

[12]

[0043] The method for producing a printing gravure according to

[10] or

[11] , wherein the overlap rate of the laser light in the processing step is 50.0% or more and 99.9% or less.

[13]

[0045] The method for producing a printing gravure plate according to any one of [8] to

[12] , wherein the spot diameter of the laser light is 1.0 μm or more and 20 μm or less.

[14]

[0047] The method for producing a printing gravure plate according to any one of [8] to

[13] , wherein in the processing step, the resin layer is directly irradiated with the laser beam.

[15]

[0049] The method for manufacturing a printed concave portion according to any one of [8] to

[13] , wherein the processing step includes: a step of forming the concave portion after arranging the resin layer on a roller, or a step of forming the concave portion in the resin layer in advance and then arranging it on a roller.

[16]

[0051] A printing method, comprising:

[0052] A coating step of filling ink into cells of the printing gravure plate described in any one of [1] to [7]; and

[0053] The transfer step is to transfer the ink filled in the cell to the surface of the substrate to obtain a printed matter.

[17]

[0055] A printed matter produced by gravure printing according to any one of [1] to [7], wherein the ink concentration of a solid area is 2.10 or more.

[18]

[0057] A printed matter, wherein the transfer rate of the highlight area is 90% or more,

[0058] The ink concentration of the highlight area is 0.50 or less.

[0059] Effects of the Invention

[0060] According to the present invention, it is possible to provide a printing gravure plate and a method for producing the same, a printing method, and the like, wherein the printing gravure plate achieves both improvement in ink transfer stability to a highlight area and improvement in ink adsorption to a solid area. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] Figure 1A This is a perspective view showing one form of the printing intaglio plate of the present embodiment.

[0062] Figure 1B Yes means Figure 1A A cross-sectional view and a top view of one embodiment of the printed surface of area S1.

[0063] Figure 1C It is a perspective view showing another form of the printing intaglio plate of the present embodiment.

[0064] Figure 1D , (a) is an example of a top view showing a defect that may occur in a highlighted area, and (b) is an example of a top view in a non-highlighted area.

[0065] Figure 2A This is a schematic diagram showing a conventional method for producing a metal intaglio plate.

[0066] Figure 2B This is a schematic diagram showing one form of the method for producing a printing gravure plate according to the present embodiment.

[0067] Figure 2C This is a schematic diagram showing one form of the method for producing a printing gravure plate according to the present embodiment.

[0068] Figure 2D This is a schematic diagram showing one form of the method for producing a printing gravure plate according to the present embodiment.

[0069] Figure 2E This is a schematic diagram showing one form of the method for producing a printing gravure plate according to the present embodiment.

[0070] Figure 3This is a schematic diagram showing one form of a printing method using the printing gravure plate of the present embodiment.

[0071] Figure 4 It is a schematic diagram showing a part of the manufacturing process of the printing gravure plate in the example.

[0072] Figure 5 It is a cross-sectional view and a top view which show the unit shape of the printing gravure plate in Example. DETAILED DESCRIPTION

[0073] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail with reference to the accompanying drawings as needed, but the present invention is not limited thereto and various modifications can be made without departing from the main purpose thereof. It should be noted that in the accompanying drawings, the same reference numerals are used to mark the same elements and repeated descriptions are omitted. In addition, the positional relationships such as up, down, left, and right are based on the positional relationships shown in the accompanying drawings unless otherwise specified. Furthermore, the dimensional ratios of the accompanying drawings are not limited to the ratios shown in the drawings.

[0074] 1. Printing gravure

[0075] The printing gravure of this embodiment has a resin layer constituting a plate surface, the Shore A hardness of the resin layer is greater than 30 degrees and less than 90 degrees, the surface free energy of the resin layer is greater than 10 mN / m and less than 35 mN / m, the resin layer has units on the plate surface, and the coefficient of variation of the unit volume of the units used for printing with the same ink concentration is less than 0.200.

[0076] 1.1. Resin layer

[0077] Figure 1A 1 is a perspective view showing one mode of printing gravure of this embodiment. Figure 1A As shown, the printing gravure plate 10 of this embodiment includes a resin layer 11 constituting a plate surface 12. The printing gravure plate of this embodiment can be Figure 1A The illustrated embodiment is cylindrical, but may also be flat, or may be other shapes. The printing gravure plate of this embodiment is preferably a printing gravure plate used for gravure printing.

[0078] 1.1.1. Unit

[0079] The resin layer 11 has cells 13 on the plate surface 12. The cells 13 are recessed portions formed in the resin layer 11. As described later, in a printing gravure plate used for gravure printing, ink 22 is retained in the cells 13, and the ink 22 retained in the cells 13 is transferred to the substrate 20, thereby performing printing (see Figure 3 ).

[0080] Figure 1B The figure shows that it is formed in Figure 1ACross-sectional view and top view of a unit 13 in region S1 in one way. As Figure 1B shown, the amount of ink held in unit 13 varies according to the volume of unit 13. The amount of ink held in a unit 13 is related to the amount of ink transferred to each point on the substrate 20. Therefore, the larger the volume of unit 13, the higher the ink concentration. Thus, in intaglio printing, a high-quality printed matter with the density represented by the film thickness of the ink can be formed.

[0081] In the present embodiment, the "solid area" refers to an area where relatively large units 13 are arranged on the surface of the resin layer (printing surface). The solid area is, for example, an area where the ink concentration represented by the following formula is 2.0 or more.

[0082] Ink concentration = log 10 (Incident light intensity / Reflected light intensity)

[0083] In the embodiment, the "highlight area" refers to an area where relatively small units are arranged on the surface of the resin layer (printing surface). The highlight area is, for example, an area where the ink concentration represented by the above formula is 0.50 or less.

[0084] However, as unit 13 becomes smaller, there may be a phenomenon that the transferability of the ink 22 held in unit 13 to the substrate 20 decreases. If the transferability decreases, a defect 16 as shown in Figure 1C (a) of occurs. Such a phenomenon is called low transfer stability. As shown in Figure 1C (b) of, as the size of unit 13 becomes larger, such a defect 16 does not occur.

[0085] On the other hand, as unit 13 becomes larger, there may be a phenomenon that the amount of transferred ink does not increase in accordance with the increase in the volume of unit 13. If the amount of transferred ink does not increase as desired, the target density performance cannot be achieved in the obtained printed matter. Such a phenomenon is called poor ink adhesion.

[0086] In addition, the portion other than the unit 13 on the printing surface 12 is called the bank portion 13a. No ink 22 is held in the bank portion 13a, and the ink 22 attached to the bank portion 13a is removed by a doctor blade 24 or the like. Moreover, when transferring the ink 22 to the substrate 20, the bank portion 13a and the substrate 20 are pressed, whereby the ink 22 held in the unit 13 is transferred to the substrate 20.

[0087] Although it also depends on the target printed matter, the depth of unit 13 is preferably 0.10 μm or more and 100 μm or less, 0.75 μm or more and 80 μm or less, 1.0 μm or more and 75 μm or less, 2.5 μm or more and 50 μm or less. It should be noted that the depth of unit 13 in the solid area is preferably 20 μm or more and 100 μm or less, 25 μm or more and 80 μm or less, 30 μm or more and 60 μm or less. In addition, the depth of unit 13 in the high-gloss area is preferably 0.10 μm or more and less than 20 μm, 1.0 μm or more and 15 μm or less, 2.5 μm or more and 10 μm or less.

[0088] Although it also depends on the target printed matter, the major axis when looking down on unit 13 is preferably 5 μm or more and 500 μm or less, 15 μm or more and 400 μm or less, 25 μm or more and 300 μm or less. It should be noted that the major axis when looking down on unit 13 in the solid area is preferably 100 μm or more and 500 μm or less, 125 μm or more and 400 μm or less, 150 μm or more and 300 μm or less. In addition, the major axis when looking down on unit 13 in the high-brightness area is preferably 5 μm or more and less than 100 μm, 15 μm or more and 90 μm or less, 25 μm or more and 80 μm or less.

[0089] Here, the major axis refers to the major axis when drawing an ellipse circumscribing a unit of any shape.

[0090] The shape of unit 13 is not particularly limited, and examples thereof include circular shapes such as circles and ellipses; polygons such as triangles and quadrilaterals.

[0091] The thickness of the resin layer 11 is preferably 250 μm or more and 10,000 μm or less, 500 μm or more and 7,500 μm or less, 1,000 μm or more and 5,000 μm or less.

[0092] 1.1.2. Physical properties

[0093] The Shore A hardness of the resin layer 11 is 30 degrees or more and 90 degrees or less, preferably 32 degrees or more and 85 degrees or less, 35 degrees or more and 80 degrees or less, 40 degrees or more and 80 degrees or less, 45 degrees or more and 80 degrees or less, 50 degrees or more and 80 degrees or less. By making the Shore A hardness 30 degrees or more, when removing the excess ink 22 using the doctor blade 24, damage to the resin layer 11 is suppressed. In addition, since deterioration of the resin layer 11 due to repeated printing can be suppressed, there is a tendency for the product life of the printing intaglio 10 to be further improved. Furthermore, by making the Shore A hardness 90 degrees or less, there is a tendency for the followability of the printing intaglio 10 to the substrate 20 to be further improved. Therefore, in any unit such as a solid area or a highlight area, there is a tendency for the transferability of the ink from the unit to the substrate to be further improved. By the Shore A hardness being 90 degrees or less, particularly in the highlight area, the stability of ink transfer is further improved, and in the solid area, the ink adhesion is further improved.

[0094] The Shore A hardness of the resin layer 11 can be adjusted by selecting the types and amounts of the components constituting the resin layer 11. For example, the Shore A hardness can be adjusted by the types and amounts of the thermoplastic elastomer and plasticizer described later. In addition, the Shore A hardness of the resin layer 11 can be measured by the method described in the examples.

[0095] The surface free energy of the resin layer 11 is 10 mN / m or more and 35 mN / m or less, preferably 15 mN / m or more and 33 mN / m or less, 20 mN / m or more and 33 mN / m or less, 25 mN / m or more and 33 mN / m or less. By making the surface free energy 10 mN / m or more, the affinity between the resin layer 11 and the ink 22 is further improved, the resin layer 11 is less likely to repel the ink 22, and the ink filling property into the unit 13 is further improved. Thereby, for example, the ink adhesion in the solid area is improved, and the expression of the density is further improved. In addition, by the surface free energy being 35 mN / m or less, the affinity between the resin layer 11 and the ink 22 is further reduced, and the resin layer 11 is likely to repel the ink 22. Thereby, for example, in any unit such as a solid area or a highlight area, the transferability of the ink from the unit to the substrate is further improved. In other words, the ink 22 is less likely to partially remain in the unit 13, and the ink 22 is easily transferred to the substrate 20.

[0096] The surface free energy of the resin layer 11 can be adjusted by selecting the types and amounts of the components constituting the resin layer 11. For example, the surface free energy can be adjusted by the types and amounts of the silicone compounds described later. In addition, the surface free energy of the resin layer 11 can be measured by the contact angle method described in the examples.

[0097] The cells 13 formed in the resin layer 11 are preferably formed in the designed size. However, the size of the cells 13 may actually vary from the designed value. In this embodiment, in order to define the degree of this variation, the "coefficient of variation of the cell volume of the cells for printing with the same ink concentration" (hereinafter also referred to as "coefficient of variation of the cell volume") is used.

[0098] The coefficient of variation of the unit volume is 0.200 or less, preferably 0.010 or more and 0.200 or less, 0.010 or more and 0.180 or less, or 0.010 or more and 0.150 or less. When the coefficient of variation of the unit volume is 0.200 or less, it is difficult to produce differences in the reception and transfer of the ink in each unit 13, and it is difficult to produce "defects" in areas where the ink is not transferred, such as highlight areas (see Figure 1D ).

[0099] The coefficient of variation of the unit volume can be adjusted by using an ultrashort wave pulse laser or the like in the manufacturing method described later. For example, by controlling the oscillation wavelength, pulse width, pulse energy, overlap rate, and spot diameter of the pulsed oscillation laser, the coefficient of variation of the unit volume can be controlled to be smaller. In addition, by optimizing the composition of the resin layer, the coefficient of variation of the unit volume can also be controlled. In addition, the coefficient of variation of the unit volume is defined using the following formula. A small coefficient of variation of the unit volume means that a unit according to the designed value can be constructed. It should be noted that the specific measurement method can be according to the method described in the embodiment.

[0100] Coefficient of variation of unit volume = standard deviation of unit volume / arithmetic mean of unit volume

[0101] In particular, from the viewpoint of improving transfer stability in highlight areas, the concentration of the same ink used as a target in the calculation of the coefficient of variation of the unit volume is preferably 0.50 or less, and may be 0.50.

[0102] 1.1.3. Composition

[0103] The resin layer may be a composition comprising a thermoplastic resin, a composition comprising a thermosetting resin, a composition comprising a photosensitive resin, and may further comprise a cured product after photocuring or heat curing. Wherein, the resin layer preferably comprises a cured product after photocuring or heat curing, and more preferably comprises a cured product formed by curing a photosensitive resin with light such as ultraviolet rays, and a cured product formed by heat curing a thermosetting resin. Thus, even if it contacts with a scraper during printing, there is a tendency to suppress the defect of the resin layer and to easily maintain the shape of the gravure. It should be noted that in the above-mentioned curing, it is preferably cured by full-surface exposure.

[0104] It should be noted that in the present embodiment, whether the terms "photosensitive resin" and "thermosetting resin" refer to the resin before curing or the resin after curing can be distinguished according to whether an operation such as curing is performed in the context. Assuming that it is used in a context without an accompanying curing operation, the resin before curing and the resin after curing are not distinguished, and it can be understood to mean the resin in the state before curing, or it can be understood to mean the resin in the state after curing.

[0105] The constituent components of such a resin layer 11 are not particularly limited, and examples thereof include constituent components containing a polymer component, a monomer component, a polymerization initiator, a polymerization inhibitor, a plasticizer, and a silicone compound. In addition, in the resin layer 11, the polymerizable monomer may also be a substance polymerized by a polymerization initiator. Hereinafter, each component will be described.

[0106] Examples of the polymer component include resins, elastomers, and rubbers that are solid at normal temperature. The resin is not particularly limited, and examples thereof include thermoplastic resins such as polyolefins, polyvinyl chlorides, polystyrenes, polyurethanes, acrylic resins, polyamides, polycarbonates, polyesters, and thermoplastic polyimides; and thermosetting resins such as phenolic resins, epoxy resins, melamine resins, urea resins, unsaturated polyesters, polyurethanes, and thermosetting polyimides.

[0107] The elastomer is not particularly limited, and examples thereof include styrene-based thermoplastic elastomers such as styrene-butadiene block copolymers, styrene-isoprene block copolymers, and SEBS (polystyrene-polyethylene / polybutene-polystyrene); olefin-based thermoplastic elastomers; urethane-based thermoplastic elastomers; ester-based thermoplastic elastomers; amide-based thermoplastic elastomers; silicone-based thermoplastic elastomers; and fluorine-based thermoplastic elastomers.

[0108] Among them, as the polymer component, an elastomer is preferred, and a styrene-based thermoplastic elastomer is more preferred. By using such a polymer component, there is a tendency to further improve the ink transfer stability to the highlight area and the ink adhesion to the solid area.

[0109] The content of the polymer component is preferably 40 parts by mass or more and 95 parts by mass or less, 50 parts by mass or more and 90 parts by mass or less, 60 parts by mass or more and 85 parts by mass or less with respect to the total amount of 100 parts by mass of the resin layer 11. By making the content of the polymer component within the above range, there is a tendency to further improve the ink transfer stability to the highlight area and the ink adhesion to the solid area.

[0110] The number average molecular weight (Mn) of the polymer component is preferably 1.0×10 4 or more and 100×10 4 or less, 3.0×104 above and 75×10 4 below, 5.0×10 4 above and 50×10 4 below. By making the number-average molecular weight (Mn) within the aforementioned range, there is a tendency to further improve the ink transfer stability to the highlighted area and the ink adhesion to the solid area. The number-average molecular weight (Mn) can be measured by a known method using gel permeation chromatography.

[0111] As the monomer component, there is no particular limitation, and examples thereof include olefins such as ethylene, propylene, styrene, and divinylbenzene; acetylenes; acrylic acids such as (meth)acrylic acid and (meth)acrylic esters; halogenated olefins; unsaturated nitriles such as acrylonitrile; (meth)acrylamide and its derivatives; allyl compounds such as allyl alcohol and allyl isocyanate; unsaturated dicarboxylic acids such as maleic anhydride, maleic acid, fumaric acid, and itaconic acid and their derivatives; vinyl acetates; N-vinylpyrrolidone; N-vinylcarbazole; cyanate esters, etc.

[0112] As the (meth)acrylate, there is no particular limitation, and examples thereof include (meth)acrylates containing an aromatic group such as phenoxyethyl methacrylate; (meth)acrylates containing an alkylene glycol group such as alkoxypolyalkylene glycol (meth)acrylate; polyfunctional (meth)acrylates such as alkylene diacrylate and trimethylolpropane trimethacrylate.

[0113] Among them, acrylic acids are preferred, and polyfunctional (meth)acrylates are more preferred. By using such monomer components, there is a tendency to further improve the ink transfer stability to the highlighted area and the ink adhesion to the solid area.

[0114] The content of the monomer component is preferably 0.1 part by mass or more and 10 parts by mass or less, 0.5 part by mass or more and 7.5 parts by mass or less, 1.0 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total amount of the resin layer 11. By making the content of the monomer component within the above range, there is a tendency to further improve the ink transfer stability to the highlighted area and the ink adhesion to the solid area.

[0115] As the polymerization initiator, there is no particular limitation, and examples thereof include photo radical generators such as benzophenones, xanthenes, thioxanthones, anthraquinones, benzoin alkyl ethers, acetophenones, acyl oxime esters, azo compounds, organic sulfur compounds, diketones, etc.; thermal radical generators such as organic peroxides, inorganic peroxides, organosilicon peroxides, hydrogen peroxide, azo compounds, mercaptan compounds, phenolic resins, amino resins, halogen compounds, aldehyde compounds, etc.; photoacid generators such as aromatic sulfonium salts, aromatic iodonium salts, aromatic phosphonium salts, aromatic sulfoxide salts, etc.; photobase generators such as benzil type photodeprotection type compounds, amine imide type compounds, carbamate oxime type compounds, alkyl oxime type compounds, coumaric acid amide type compounds, 2-aminocycloheptatrienone type compounds, etc.

[0116] The content of the polymerization initiator is preferably 1.0 part by mass or more and 15 parts by mass or less, 2.0 parts by mass or more and 10 parts by mass or less, 3.0 parts by mass or more and 7.5 parts by mass or less with respect to 100 parts by mass of the total amount of the resin layer 11.

[0117] As the plasticizer, there is no particular limitation, and examples thereof include liquid rubbers such as liquid butadiene rubber, liquid isoprene rubber, liquid styrene-butadiene rubber, liquid acrylic rubber, liquid nitrile rubber, etc.; liquid paraffin, etc.

[0118] The content of the plasticizer is preferably 2.5 parts by mass or more and 40 parts by mass or less, 5.0 parts by mass or more and 30 parts by mass or less, 7.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of the resin layer 11. By making the content of the plasticizer within the above range, there is a tendency to further improve the ink transfer stability to the highlight area and the ink adhesion to the solid area.

[0119] As the polymerization inhibitor, there is no particular limitation, and examples thereof include phenolic compounds such as hydroquinone, 2,6-di-tert-butyl-p-cresol, etc.; thioethers such as phenothiazine, distearyl thiodipropionate, etc.; amine compounds such as p-phenylenediamine, etc.; nitroso compounds such as N-nitrosodiphenylamine, etc.

[0120] The content of the polymerization inhibitor is preferably 0.10 part by mass or more and 10 parts by mass or less, 0.25 part by mass or more and 7.5 parts by mass or less, 0.50 part by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the total amount of the resin layer 11.

[0121] The resin layer 11 may contain an organosilicon compound. Thereby, there is a tendency to further improve the ink transfer stability to the highlight area and the ink adhesion to the solid area.

[0122] The silicone compound is not particularly limited, and examples thereof include unmodified silicone oils such as dimethyl silicone oil and methylphenyl silicone oil; modified silicone oils such as methanol-modified silicone oil, amino-modified silicone oil, polyether-modified silicone, aralkyl-modified silicone, fluoroalkyl-modified silicone, and long-chain alkyl-modified silicone.

[0123] The content of the silicone compound is preferably 0.01 part by mass or more and 20.0 parts by mass or less, 0.01 part by mass or more and 15.0 parts by mass or less, 0.05 part by mass or more and 10.0 parts by mass or less, 0.10 part by mass or more and 5.0 parts by mass or less, 0.10 part by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the total amount of the resin layer 11. By making the content of the silicone compound within the above range, the adhesiveness and surface frictional resistance of the plate surface 12 are reduced, and there is a tendency that ink stains during printing are further suppressed. In addition, by making the content of the silicone compound within the above range, there is a tendency that the ink transfer stability to the highlight area and the ink adhesion to the solid area are further improved.

[0124] The content of the photosensitive resin source is preferably 20 parts by mass or more and 99 parts by mass or less, 30 parts by mass or more and 99 parts by mass or less, 35 parts by mass or more and 99 parts by mass or less with respect to 100 parts by mass of the total amount of the resin layer 11. The "photosensitive resin source" refers to both the photosensitive resin before light irradiation and the photosensitive resin after light irradiation. Thus, in the gravure for gravure printing, it is possible to balance the ease of forming when manufacturing a sleeve or a sheet and the hardness as a gravure for printing.

[0125] 1.2. Cylinder

[0126] The gravure printing plate of the present embodiment may further include a cylinder 14. In this case, as Figure 1A shown, a cylindrical resin layer 11 is disposed so as to cover the outer periphery of the cylinder 14. The cylinder 14 may also be a cylinder included in a printing press.

[0127] The material of the cylinder 14 is not particularly limited, and examples thereof may include metals such as aluminum, nickel, and iron; resins such as polyester, polyimide, polyamide, polyphenylene ether, polyphenylene sulfide, polysulfone, and epoxy resin; or rubbers such as EPDM, silicone, urethane, SB rubber, and fluororubber.

[0128] 1.3. Support layer

[0129] The gravure printing plate of the present embodiment may also include a support layer 15 between the cylinder 14 and the cylindrical resin layer 11. Figure 1C The manner of including the support layer 15 is shown in

[0130] The material of the support layer 15 is not particularly limited, and examples thereof include polyolefins such as polyethylene and polypropylene, polyhaloolefins such as polyvinyl chloride and polyvinylidene chloride, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyvinyl acetate, polyvinyl acetal, polyacrylic acid, poly(meth)acrylates, poly(meth)acrylamides, polyvinyl ethers, polyethers such as polyphenylene ether, polysulfides such as polyphenylene sulfide, polyesters such as polyethylene terephthalate, polycarbonate, polyacetal, polyurethane, polyamide, polyurea, polyimide, and the like.

[0131] 2. Manufacturing method of intaglio printing plate

[0132] First, Figure 2A FIG. shows a schematic diagram of a method for manufacturing a conventional metal intaglio printing plate. Conventionally, intaglio printing plates have been used for printing high-quality photographs and the like. In the manufacturing method of a conventional metal intaglio printing plate, for example, the following multi-stage processes are required: forming a copper plating layer on a cylinder, applying a photoresist layer to the copper plating layer, further forming a pattern on the photoresist layer, etching the copper plating layer by means of the photoresist pattern to form cells, and then performing plating with a hard metal such as chromium. However, in the manufacture of such metal intaglio printing plates, since waste liquid containing a large amount of metal is generated, there is a problem from the viewpoint of environmental load.

[0133] In addition, currently, due to the diversification of printing demands, intaglio printing plates for small-batch printing are required. The conventional manufacturing method of metal intaglio printing plates has a problem that it is not suitable for manufacturing intaglio printing plates for such small-batch printing from the viewpoints of cost and environmental load.

[0134] In contrast, as Figure 2B to Figure 2E shown, the manufacturing method of the intaglio printing plate 10 of the present embodiment has a processing step of forming recesses in the resin layer by using a laser. Thereby, an intaglio printing plate having cells formed in the resin layer can be obtained. According to such a manufacturing method, waste liquid containing a large amount of metal is not generated, and an intaglio printing plate can be manufactured by a relatively simple process. Therefore, it is possible to reduce the environmental load and manufacture an intaglio printing plate for small-batch printing at low cost.

[0135] 2.1. Resin layer forming step

[0136] The manufacturing method of the intaglio printing plate of the present embodiment may also have a resin layer forming step of forming a resin layer before the processing step. Hereinafter, Figure 2B to Figure 2D the shown manufacturing method is the same for the processing step of forming recesses (cells), and different manufacturing methods in the resin layer 11 forming step.

[0137] In Figure 2B , for example, a resin composition is applied to the side surface of the cylinder 14 to form a resin layer 11. Thereby, the resin layer 11 can be formed relatively simply.

[0138] In addition, in Figure 2C , the resin composition is cast into the space 17a of the mold 17 that houses the roller 14, thereby forming the resin layer 11. Thus, compared with the methods such as Figure 2B , it is possible to avoid the resin layer sagging before curing, etc., and the resin layer 11 can be formed with good formability.

[0139] Furthermore, in Figure 2D , the resin composition is coated on the surface of the support layer 15, thereby forming the resin layer 11. Then, the laminate of the support layer 15 and the resin layer 11 is sleeved and disposed on the surface of the roller 14. Thus, compared with the methods such as Figure 2B , it is possible to avoid the resin layer sagging before curing, etc., and the resin layer 11 can be formed simply and with good formability.

[0140] 2.2. Curing process

[0141] In the method for manufacturing the intaglio printing plate of the present embodiment, when the resin composition used is photosensitive or thermosetting, it may further include a curing process of curing the resin composition by exposure or heat to form the resin layer 11. In addition, the curing process can be carried out as post-curing after the processing process described later.

[0142] The exposure curing method is not particularly limited. For example, light can be irradiated on the photosensitive resin layer to crosslink monomer components, etc., to form a cured product. In addition, it is also possible to crosslink while coating the resin composition by light irradiation. The light source used in exposure curing is not particularly limited, and examples thereof include a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, an ultraviolet fluorescent lamp, a germicidal lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, etc.

[0143] The light irradiated on the resin layer preferably has a wavelength of 200 nm to 400 nm. In particular, most hydrogen abstraction type photoinitiators have strong light absorption in this wavelength region. Therefore, in the case of light having a wavelength of 200 nm to 400 nm, the curability on the surface of the photosensitive resin cured product layer can be sufficiently ensured. The light source used in photocuring can be one type, or the curability of the resin can be improved by curing it using two or more light sources having different wavelengths.

[0144] In addition, the thermal curing method is not particularly limited, and examples thereof include a method of irradiating infrared rays, a method of exposing to an atmosphere heated by an oven, etc., and a method of contacting with a heated object such as a metal. The heating temperature can be selected according to the type of thermal polymerization initiator.

[0145] 2.3. Processing process

[0146] The method for manufacturing the intaglio printing plate 10 of the present embodiment has a processing process of forming recesses in the resin layer using a laser. Figure 2B to Figure 2D This indicates a method of forming a recess in the cylindrical resin layer 11 by laser imaging. In contrast, Figure 2E shows a method of forming a recess in the laminate of the support layer 15 and the resin layer 11 using a laser in a flat state. As Figure 2E shown, by forming a recess using a laser in a flat state, the recess can be formed more simply.

[0147] In the processing step, the image to be formed is used as digital data to operate a laser device by a computer, and a relief image is produced on the master. Any laser can be used as long as the laser used for laser engraving includes a wavelength that the master absorbs. However, in order to perform engraving at high speed, a laser with a high output power is preferred, and infrared or infrared-emitting solid lasers such as carbon dioxide lasers, YAG lasers, and semiconductor lasers are one of the preferred lasers. In addition, the second harmonic of a YAG laser having an oscillation wavelength in the visible light region, a copper vapor laser, an ultraviolet laser having an oscillation wavelength in the ultraviolet region, such as an excimer laser, and a YAG laser whose wavelength is converted to the third or fourth harmonic can perform ablation processing for breaking the bonds of organic molecules and are suitable for microfabrication.

[0148] In addition, the laser can be continuously irradiated or pulse-irradiated. Laser processing generally easily causes thermal damage to the workpiece (resin layer). The shape and the like of the unit processed under such thermal damage are likely to deviate. In contrast, in the present embodiment, it is preferable to adopt direct processing using an ultrashort pulse laser in unit processing. Thereby, the thermal influence on the resin layer can be reduced during the processing step, and thus higher-precision and higher-fineness unit processing can be performed.

[0149] In the processing step, the laser can be directly irradiated onto the resin layer or indirectly irradiated. Here, direct irradiation means irradiating the laser onto the resin layer without using a photomask or the like, and indirect irradiation means irradiating the laser onto the resin layer with the aid of a photomask or the like.

[0150] The oscillation wavelength of the laser is preferably 100 nm or more and 800 nm or less, 200 nm or more and 800 nm or less, 300 nm or more and 700 nm or less, 300 nm or more and 600 nm. By making the oscillation wavelength of the laser 100 nm or more, there is a tendency to easily obtain an improvement effect on the ablation processing efficiency. In addition, by making the oscillation wavelength of the laser 800 nm or less, there is a tendency to obtain an ablation processing quality with little thermal influence.

[0151] The laser is preferably a pulsed oscillating laser. Thereby, heat-induced damage can be reduced. Therefore, there is a tendency for unit processing to become more precise and finer. The pulse width of the pulsed oscillating laser is preferably 1 fs or more and 1 ns, 10 fs or more and 500 ps or less, and more preferably 10 fs or more and 100 ps or less. By setting the pulse width within the above range, even if the average output power of the laser is small, a high peak output power can be obtained, and a large amount of energy can be input in an extremely short time. Therefore, engraving of the printing original can be easily performed, and there is an effect of being able to suppress the influence of heat, and the deviation of the obtained pattern becomes smaller.

[0152] The pulse energy of the laser is preferably 1.00 μJ or more and 1.00 mJ or less, 1.00 μJ or more and 500 μJ or less, 1.00 μJ or more and 300 μJ or less. By making the pulse energy of the laser 1.00 μJ or more, laser engraving of the resin layer 11 can be easily performed, and there is a tendency for the edge shape of the obtained pattern to become clearer. In addition, by making the pulse energy of the laser 1.00 mJ or less, there is a tendency for the influence of heat on the resin layer 11 to be further reduced. Thereby, the resin layer 11 is not overly melted or removed, and there is a tendency to obtain a concave pattern with a width approximately equal to the laser beam diameter.

[0153] It should be noted that here, the pulse energy refers to the energy of each pulse of the ultrashort pulse oscillating laser used in the laser engraving process. In addition, in the energy of each pulse of the laser, the unit: J refers to the value obtained by dividing the average output power (unit: W) by the repetition frequency (unit: pulses / second).

[0154] The overlap rate of the laser in the processing step is preferably 50.0% or more and 99.9% or less, 60.0% or more and 99.0% or less, 70.0% or more and 99.0% or less. By making the overlap rate of the laser 50.0% or more, there is a tendency to ensure sufficient laser irradiation intensity. In addition, by making the overlap rate of the laser 99.0% or less, there is a tendency to further reduce the influence of heat on the resin layer 11. Thereby, the resin layer 11 is not overly melted or removed, and there is a tendency to obtain a concave pattern with a width approximately equal to the laser beam diameter.

[0155] It should be noted that the overlap rate of the laser can be calculated by the ratio of the repeated area or the repeated diameter of the laser irradiated on the printing original for each consecutive pulse.

[0156] The spot diameter of the laser is preferably 1.0 μm or more and 20 μm or less. Thereby, for example, a fine concave pattern with a width of 1.0 μm or more and less than 500 μm and a depth of 0.10 μm or more and less than 100 μm can be formed with high precision.

[0157] 3. Printing method

[0158] The printing method of the present embodiment includes: a coating step of filling ink into the cells of the printing intaglio plate of the present embodiment; and a transfer step of transferring the ink filled in the cells to the surface of a substrate to obtain a printed matter.

[0159] 3.1 Coating step

[0160] The coating step is a step of filling ink into the cells of the printing intaglio plate of the present embodiment. Specifically, the ink 22 is coated on the plate surface 12 of the printing intaglio plate 10 by means of a rubber furnisher 23. At this time, the ink 22 is coated on the cells 13 and the dam portions 13a. Then, the excess ink 22 coated on the dam portions 13a is removed by a doctor blade 24.

[0161] 3.2 Transfer step

[0162] The transfer step is a step of transferring the ink filled in the cells to the surface of a substrate to obtain a printed matter. Specifically, by pressing the plate surface 12 of the resin layer 11 and the substrate 20 using a cylinder 14 and an impression cylinder 21, the ink 22 filled in the cells 13 can be transferred to the surface of the substrate 20.

[0163] 4. Printed matter

[0164] The printed matter of the present embodiment is a printed matter printed by the printing intaglio plate of the present embodiment, and the ink concentration in the solid area is 2.10 or more. Alternatively, the transfer rate in the highlight area of the printed matter of the present embodiment is 90% or more, and the ink concentration in the highlight area is 0.50 or less.

[0165] The ink concentration in the solid area is 2.10 or more, preferably 2.20 or more and 10 or less. In addition, the transfer rate in the highlight area is 90% or more, preferably 95% or more and 100% or less.

[0166] Examples

[0167] Hereinafter, the present invention will be described more specifically using examples and comparative examples. The present invention is not limited by any of the following examples.

[0168] 1. Each measurement method

[0169] 1.1 Surface free energy

[0170] A sample of a smooth resin layer without formed units was prepared, and its contact angle was measured by the droplet method using a solid-liquid interface analysis device DropMaster501 (manufactured by Kyowa Interface Science Co., Ltd., trade name). Specifically, the sample was placed in a constant temperature and humidity chamber at a temperature of 23 degrees and a relative humidity of 50% for 1 day before measurement. Then, purified water, ethylene glycol, and diiodomethane (manufactured by Kanto Chemical Co., Inc.) were used as probe solutions, and the contact angle of the surface of the sample was measured. At this time, a stainless steel 22G needle (manufactured by Kyowa Interface Science Co., Ltd.) was used, and the values of the contact angle 15 seconds after the automatic measurement ejection time of 100 ms, ejection voltage of 4000 mV, and contact of each probe solution with the sample were obtained. Then, the surface free energy of the sample was automatically calculated according to the calculation formula of Kitazaki-Hata embedded in the analysis software (FAMAS).

[0171] 1.2. Shore hardness

[0172] A sample of a smooth resin layer without formed units was prepared. Specifically, the sample was placed in a constant temperature and humidity chamber at a temperature of 23 degrees and a relative humidity of 50% for 1 day before measurement. Then, using a Teclock automatic hardness tester (Shore A GS0719G), the sample was placed on the specimen stage with a load of 1 kg, the hardness tester was lowered, and the value measured for 15 seconds was used as the Shore A hardness. It should be noted that for Comparative Example 3, the value of the Shore A hardness exceeded 90 degrees, so the value of the Shore D hardness was measured.

[0173] 1.3. Coefficient of variation of cell volume

[0174] A sample of a resin layer with formed units was prepared. Then, using a laser microscope (KEYENCE CORPORATION VK-X100), at an observation magnification of 20 times and a scanning pitch in the depth direction of 0.75 μm, the cell volumes of cells with the same ink concentration in the bright areas at 20 randomly measured points were measured. Based on the cell volumes at the obtained 20 points, the coefficient of variation was calculated according to the following formula.

[0175] Coefficient of variation of cell volume = standard deviation of cell volume / arithmetic mean of cell volume

[0176] 2. Production example

[0177] 2.1. Printing original 1

[0178] 2.1.1. Production of the support

[0179] 93 g of ethylene glycol, 374 g of neopentyl glycol, and 382 g of phthalic acid were subjected to a condensation reaction for 6 hours under reduced pressure of 1330 Pa at a reaction temperature of 180°C in an air atmosphere. Then, 125 g of 4,4-diphenylmethane diisocyanate was added, and the reaction was further carried out at 80°C for 5 hours to obtain a resin. A 10% aqueous solution of this resin was coated on a polyethylene terephthalate film having a thickness of 125 μm, and after coating, biaxial stretching was performed to obtain a polyethylene terephthalate film having an undercoat. The thickness of the undercoat was 0.05 μm.

[0180] Next, 624 g of neopentyl glycol, 93 g of ethylene glycol, 485 g of sebacic acid, and 382 g of isophthalic acid were subjected to a condensation reaction for 6 hours under reduced pressure of 1330 Pa at a reaction temperature of 180°C in an air atmosphere. Then, 87 g of trimethylene diisocyanate was added, and the reaction was further carried out for 5 hours to obtain a polyol. 1 part by mass of xylylene diisocyanate was added to 15 parts by mass of this polyol and dissolved in ethyl acetate to obtain a uniform urethane-based adhesive solution.

[0181] Then, the prepared urethane-based adhesive solution was coated on the above undercoat using a knife coater and dried at 80°C for 3 minutes to form an adhesive layer having a thickness of 10 μm. Thus, a support (hereinafter, simply referred to as "support") of a polyethylene terephthalate film having a thickness of 135 μm including the thickness of the adhesive layer was obtained.

[0182] 2.1.2. Fabrication of Resin Layer 1

[0183] Using a kneader heated to 180°C, 85 parts by mass of a thermoplastic elastomer (styrene-butadiene block copolymer, trade name "KX-405", manufactured by KRATON POLYMERS JAPAN LTD., number average molecular weight (Mn) 10×10 4 , styrene content 24% by mass), 10 parts by mass of a liquid rubber elastomer as a plasticizer (liquid polybutadiene polymer, trade name "LBR-352", manufactured by KURARAY CO., LTD., number average molecular weight (Mn) 6200), 3 parts by mass of 1,9-nonanediyl dimethacrylate as a photopolymerizable monomer (trade name "NMDA", manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of 2,2-dimethoxy-2-phenylacetophenone as a photoinitiator, 1 part by mass of 2,6-di-tert-butyl-p-cresol as a polymerization inhibitor, and 0.15 part by mass of methanol-modified silicone oil (trade name "KF-6000", manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly kneaded to obtain a photosensitive resin composition 1.

[0184] Next, using a hot press at 120 °C, the above photosensitive resin composition 1 was sandwiched between the above support and a polyethylene terephthalate film (surface protection film), and formed with an overall thickness of 1 mm. Then, the surface protection film was peeled off to obtain a laminate having a resin layer 1 before exposure formed on the support.

[0185] Next, using an exposure device, the resin layer 1 before exposure was exposed from the support side such that the exposure amount became 500 mJ / cm 2 and from the printing surface side such that the light amount became 8000 mJ / cm 2 to obtain a laminate having a resin layer 1 after exposure formed on the support. The size of the resin layer 1 was 150 mm × 400 mm.

[0186] It should be noted that as the exposure device, an AFP-1321EHQ type plate-making machine (manufactured by Asahi Kasei Corporation, trade name) equipped with an 80 W ultraviolet fluorescent lamp having a central wavelength region at a wavelength of 370 nm was used. The above exposure amount was calculated using a UV-35 filter (manufactured by ORC MANUFACTURING CO., LTD., trade name) of UV-MO2. In addition, measurement was performed using a UV-35 filter (manufactured by ORC MANUFACTURING CO., LTD., trade name) of an ultraviolet ray measuring device UV-MO2 (manufactured by ORC MANUFACTURING CO., LTD., trade name), and as a result, the light irradiation intensity directly below the light source of the exposure device was 12.0 mW / cm 2 .

[0187] 2.1.3. Production of printing original plate 1

[0188] The laminate obtained as described above was wound around the side surface of a drum with the resin layer 1 on the outside and fixed with tape to obtain printing original plate 1.

[0189] 2.2. Printing original plate 2

[0190] In the production of the resin layer, a photosensitive resin composition 2 in which the amount of methanol-modified silicone oil (trade name "KF-6000" manufactured by Shin-Etsu Chemical Co., Ltd.) used was 2 parts by mass was used to form a resin layer 2 after exposure, and printing original plate 2 was obtained in the same manner as the manufacturing method of printing original plate 1 except for this.

[0191] 2.3. Printing original plate 3

[0192] Using a kneader heated to 180 °C, a thermoplastic elastomer (styrene-butadiene block copolymer, trade name "KX-405" manufactured by KRATON POLYMERS JAPAN LTD., number average molecular weight (Mn) 10 × 10 4, 60 parts by mass of styrene content 24% by mass), 24 parts by mass of liquid paraffin as a plasticizer (product name "SMOIL P350P" manufactured by MORESCO Corporation, number average molecular weight (Mn) 483), 5 parts by mass of a liquid rubber elastomer as a plasticizer (liquid polybutadiene polymer, product name "LBR-352" manufactured by KURARAY CO., LTD., number average molecular weight (Mn) 6200), 1 part by mass of 1,9-nonamethylene dimethacrylate as a photopolymerizable monomer (product name NMDA manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of 2,2-dimethoxy-phenylacetophenone as a photoinitiator, 1 part by mass of 2,6-di-tert-butyl-p-cresol as a polymerization inhibitor, and 0.15 part by mass of amino-modified silicone oil (product name "KF-8000" manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly kneaded to obtain a photosensitive resin composition 3.

[0193] Then, in the production of the resin layer, the photosensitive resin composition 3 was used instead of the photosensitive resin composition 1 to form the exposed resin layer 3, and the printing original plate 3 was obtained in the same manner as the manufacturing method of the printing original plate 1 except for this.

[0194] 2.4. Printing original plate 4

[0195] In the production of the resin layer, the exposed resin layer 4 was formed using the photosensitive resin composition 4 in which the amount of amino-modified silicone oil (product name "KF-8000" manufactured by Shin-Etsu Chemical Co., Ltd.) used was 1 part by mass, and the printing original plate 4 was obtained in the same manner as the manufacturing method of the printing original plate 3 except for this.

[0196] 2.5. Printing original plate 5

[0197] Using a kneader heated to 160°C, a thermoplastic elastomer (styrene-isoprene block copolymer, product name "D-1161" manufactured by KRATON POLYMERS JAPAN LTD., number average molecular weight (Mn) 18×10 4 , styrene content 15% by mass) 77 parts by mass, 5 parts by mass of liquid polybutadiene as a plasticizer (product name "B2000" manufactured by Nippon Soda Co., Ltd.), 3 parts by mass of 1,9-nonamethylene dimethacrylate as a photopolymerizable monomer, 10 parts by mass of 2,2-dimethoxy-2-phenylacetophenone as a photoinitiator, 5 parts by mass of 2,6-di-tert-butyl-p-cresol as a polymerization inhibitor, and 0.2 part by mass of methanol-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., product name "KF-6000") were uniformly kneaded to obtain a photosensitive resin composition 5.

[0198] Then, in the production of the resin layer, a photosensitive resin composition 5 is used instead of the photosensitive resin composition 1 to form the exposed resin layer 5, and in other respects, a printing original plate 5 is obtained in the same manner as the manufacturing method of the printing original plate 1.

[0199] 2.6. Printing original plate 6

[0200] In the production of the resin layer, a photosensitive resin composition 6 in which the usage amount of methanol-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KF-6000”) is set to 1 part by mass is used to form the exposed resin layer 6, and in other respects, a printing original plate 6 is obtained in the same manner as the manufacturing method of the printing original plate 5.

[0201] 2.7. Printing original plate 7

[0202] In the production of the resin layer, exposure is not performed, and the resin layer 1 before exposure (hereinafter referred to as “resin layer 7”) is used, and in other respects, a printing original plate 7 is obtained in the same manner as the manufacturing method of the printing original plate 1.

[0203] 2.8. Printing original plate 8

[0204] 2 parts by mass of (3-mercaptopropyl)triethoxysilane (manufactured by Wako Pure Chemical Industries, Ltd.), 15 parts by mass of dipentaerythritol hexaacrylate (manufactured by Daicel-Cytec Co., Ltd.), 28 parts by mass of polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd.), 25 parts by mass of dibutoxyethyl adipate (manufactured by Wako Pure Chemical Industries, Ltd.), 4 parts by mass of carbon black, and 20 parts by mass of propylene glycol monomethyl ether acetate (manufactured by Wako Pure Chemical Industries, Ltd.) are added to a three-necked flask equipped with a stirring blade and a cooling tube, and the mixture is heated and dissolved at 70 °C for 120 minutes while stirring. After the temperature of the solution is adjusted to 40 °C, 8 parts by mass of an organosilaneoxy oligomer (manufactured by Shin-Etsu Chemical Co., Ltd.) and PERBUTYL Z (manufactured by NOF Corporation) are added, and the mixture is further stirred for 10 minutes to prepare a thermosetting resin composition 8 having fluidity.

[0205] Next, the above thermosetting resin composition 8 is coated on a glass fiber-reinforced plastic cylindrical support having an inner diameter of 126.388 mm, a width of 150 mm, and a thickness of 2.00 mm using a doctor blade. Then, it is protected with a PET film so that the coated material does not leak, and the coated material is placed in an oven, held at 90 °C for 1 hour, and then further heated at 85 °C for 3 hours to form a resin layer 8, thereby obtaining a printing original plate 8.

[0206] 2.9. Printing original plate 9

[0207] Add 2 parts by mass of (3-mercaptopropyl)trimethoxysilane (manufactured by Wako Pure Chemical Industries, Ltd.), 15 parts by mass of dipentaerythritol hexaacrylate (manufactured by Daicel-Cytec Co., Ltd.), 28 parts by mass of polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd.), 25 parts by mass of dibutoxyethyl adipate (manufactured by Wako Pure Chemical Industries, Ltd.), 4 parts by mass of carbon black, and 20 parts by mass of propylene glycol monomethyl ether acetate (manufactured by Wako Pure Chemical Industries, Ltd.) into a three-necked flask equipped with a stirring blade and a cooling tube, and heat and dissolve at 70°C for 120 minutes while stirring. After the temperature of the solution reaches 40°C, add 8 parts by mass of an organosilaneoxy oligomer (manufactured by Shin-Etsu Chemical Co., Ltd.) and PERBUTYL Z (manufactured by Nippon Oil Co., Ltd.), and further stir for 10 minutes to prepare a thermosetting resin composition 9 with fluidity.

[0208] Next, use the obtained thermosetting resin composition 9 to form a resin layer 9. In addition, through the same operations as those for the above printing original plate 8, a printing original plate 9 is obtained.

[0209] 2.10. Printing original plate 10

[0210] Add 2 parts by mass of 3-mercaptopropylmethyldimethoxysilane (manufactured by Wako Pure Chemical Industries, Ltd.), 15 parts by mass of dipentaerythritol hexaacrylate (manufactured by Daicel-Cytec Co., Ltd.), 28 parts by mass of polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd.), 25 parts by mass of dibutoxyethyl adipate (manufactured by Wako Pure Chemical Industries, Ltd.), 4 parts by mass of carbon black, and 20 parts by mass of propylene glycol monomethyl ether acetate (manufactured by Wako Pure Chemical Industries, Ltd.) into a three-necked flask equipped with a stirring blade and a cooling tube, and heat and dissolve at 70°C for 120 minutes while stirring. After the temperature of the solution reaches 40°C, add 8 parts by mass of an organosilaneoxy oligomer (manufactured by Shin-Etsu Chemical Co., Ltd.) and PERBUTYL Z (manufactured by Nippon Oil Co., Ltd.), and further stir for 10 minutes to prepare a thermosetting resin composition 10 with fluidity.

[0211] Next, use the obtained thermosetting resin composition 10 to form a resin layer 10. In addition, through the same operations as those for the above printing original plate 8, a printing original plate 10 is obtained.

[0212] 2.11. Printing original plate 11

[0213] 4,4,13,13 - tetraethoxy - 3,14 - dioxo - 8,9 - dithia - 4,13 - disilahexadecane (manufactured by Wako Pure Chemical Industries, Ltd.): 2 parts by mass, dipentaerythritol hexaacrylate (manufactured by Daicel - Cytec Co., Ltd.): 15 parts by mass, polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd.): 28 parts by mass, dibutoxyethyl adipate (manufactured by Wako Pure Chemical Industries, Ltd.): 25 parts by mass, carbon black: 4 parts by mass, and propylene glycol monomethyl ether acetate (manufactured by Wako Pure Chemical Industries, Ltd.): 20 parts by mass were added to a three - necked flask equipped with a stirring blade and a cooling tube, and heated with stirring at 70 °C for 120 minutes to dissolve. After the temperature of the solution was adjusted to 40 °C, 8 parts by mass of an organosilane - oxy oligomer (manufactured by Shin - Etsu Chemical Co., Ltd.) and PERBUTYL Z (manufactured by Nippon Oil Co., Ltd.) were added, and further stirred for 10 minutes to prepare a thermosetting resin composition 11 having fluidity.

[0214] Next, the obtained thermosetting resin composition 11 was used to form a resin layer 11. Otherwise, by the same operation as the above - mentioned printing original plate 8, a printing original plate 11 was obtained.

[0215] 2.12. Printing original plate 12

[0216] Using a kneader heated to 180 °C, 85 parts by mass of a thermoplastic elastomer (styrene - butadiene block copolymer, trade name “KX - 405” manufactured by KRATON POLYMERS JAPAN LTD., number - average molecular weight (Mn) 10×10 4 , styrene content 24% by mass), 10 parts by mass of a liquid rubber elastomer as a plasticizer (liquid polybutadiene polymer, trade name “LBR - 352” manufactured by KURARAY CO., LTD., number - average molecular weight (Mn) 6200), 3 parts by mass of 1,9 - nonamethylene diacrylate as a photopolymerizable monomer (trade name NMDA manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of 2,2 - dimethoxy - 2 - phenylacetophenone as a photoinitiator, and 1 part by mass of 2,6 - di - tert - butyl - p - cresol as a polymerization inhibitor were uniformly kneaded to obtain a photosensitive resin composition 12.

[0217] Then, in the production of the resin layer, the photosensitive resin composition 12 was used instead of the photosensitive resin composition 1 to form an exposed resin layer 12. Otherwise, a printing original plate 12 was obtained in the same manner as the manufacturing method of the printing original plate 1.

[0218] 2.13. Printing original plate 13

[0219] Using a kneader heated to 180 °C, 75 parts by mass of a thermoplastic elastomer (styrene-butadiene block copolymer, trade name “KX-405” manufactured by KRATON POLYMERS JAPAN LTD., number-average molecular weight (Mn) 10×10 4 , styrene content 24% by mass), 9 parts by mass of a liquid polybutadiene polymer as a plasticizer, i.e., a liquid rubber elastomer (trade name “LBR-352” manufactured by KURARAY CO., LTD., number-average molecular weight (Mn) 6200), 3 parts by mass of 1,9-nonanediyl dimethacrylate as a photopolymerizable monomer (trade name NMDA manufactured by Kyoeisha Chemical Co., Ltd.), 5 parts by mass of 2,2-dimethoxy-2-phenylacetophenone as a photoinitiator, 1 part by mass of 2,6-di-tert-butyl-p-cresol as a polymerization inhibitor, and 12 parts by mass of methanol-modified silicone oil [KF-6000: manufactured by Shin-Etsu Chemical Co., Ltd.] were uniformly kneaded to obtain a photosensitive resin composition 13.

[0220] Then, in the production of the resin layer, the photosensitive resin composition 13 was used instead of the photosensitive resin composition 1 to form the exposed resin layer 13, and other than this, the printing original plate 13 was obtained in the same manner as the manufacturing method of the printing original plate 1.

[0221] 2.14. Printing original plate 14

[0222] 447.24 g of polycarbonate diol (number-average molecular weight (Mn) 1990, trade name “PCDL L4672” manufactured by Asahi Kasei Corporation, OH value 56.4 mg / KOHg) and 30.83 g of tolylene diisocyanate were added to a 1 L detachable flask equipped with a thermometer, a stirrer, and a reflux condenser. After reacting at 80 °C for about 3 hours, 14.83 g of 2-methacryloyloxyisocyanate was added and further reacted for about 3 hours to produce a resin that was liquid at 20 °C and had methacryloyl groups at its terminals (about 2 polymerizable unsaturated groups per molecule on average) (number-average molecular weight (Mn) 10000).

[0223] 100 parts by mass of the obtained resin, 59 parts by mass of a monomer component (a mixture of 35 parts by mass of phenoxyethyl methacrylate, 14 parts by mass of butoxy diethylene glycol methacrylate, and 10 parts by mass of trimethylolpropane trimethacrylate), 1.5 parts by mass of a silicone compound (manufactured by Shin-Etsu Chemical Co., Ltd., methylstyryl-modified silicone oil (trade name "KF-410", refractive index: 1.480, number average molecular weight: having two peaks of 7890 and 700, with a ratio of 4.3:1, so allocated by area ratio, the number average molecular weight is set to 6530, and it is liquid at 20 °C)), 1.5 parts by mass of methanol-modified silicone oil (trade name "X-22-160AS", refractive index: 1.420, number average molecular weight: 750, liquid at 20 °C), porous fine powder silica as an inorganic porous body (manufactured by FUJI SILYSIA CHEMICAL LTD., trade name "SYLOSPHERE C") - 1504, number average particle diameter 4.5 μm, specific surface area 520 m 2 / g, average pore diameter 12 nm, pore volume 1.5 ml / g, ignition loss 2.5 wt%, oil absorption 290 ml / 100 g) 7.7 parts by mass, 2.4 parts by mass of a photopolymerization initiator (0.9 parts by mass of 2,2-dimethoxy-2-phenylacetophenone and 1.5 parts by mass of benzophenone), and 0.5 parts by mass of 2,6-di-tert-butylacetophenone were mixed to obtain a photosensitive resin composition 14.

[0224] It should be noted that benzophenone (BP) is a hydrogen abstraction type photopolymerization initiator (d), and 2,2-dimethoxy-2-phenylacetophenone (DMPAP) is a disintegration type photopolymerization initiator.

[0225] Next, the photosensitive resin composition 14 was applied onto a cylindrical support made of glass fiber-reinforced plastic with an inner diameter of 126.388 mm, a width of 150 mm, and a thickness of 2.00 mm using a doctor blade. Then, while rotating the cylinder at a speed of 0.2 revolutions per second, light emitted from the opening (opening size: 40 mm × 310 mm) of a metal halide lamp (manufactured by EYE GRAPHICS COMPANY, trade name "M056-L21") was irradiated onto the photosensitive resin composition 14 in the atmosphere to form a cured resin layer 14. According to the value obtained by time integration of the illuminance measured with a UV-35-APR filter, the irradiation energy was 4000 mJ / cm 2 . In addition, the lamp illuminance on the irradiation surface was measured using a UV meter (manufactured by ORC MANUFACTURING CO., LTD., trade name "UV-M02"). The lamp illuminance measured using the trade name "UV-35-APR filter" (manufactured by ORC MANUFACTURING CO., LTD.) was 100 mW / cm 2, the lamp illuminance measured using the trademark "UV-25 filter" (manufactured by ORC MANUFACTURING CO., LTD.) is 14 mW / cm 2 . The film thickness of the obtained photosensitive resin cured product layer was adjusted to about 1 mm, and a super-hard turning tool was used for cutting so that the circumference of the cylindrical printing original plate became 400 mm. After rough planing with a grinding machine, precision grinding was performed using a thin film with minute abrasives on the surface to produce the printing original plate 14.

[0226] 3. Method for manufacturing a gravure printing plate

[0227] For the printing original plates 1 to 14 obtained as described above, laser engraving was performed using the following ultra-short pulse oscillating laser, and a gravure printing plate of Examples 1 to 18 and Comparative Examples 1 to 4 was obtained by forming a unit on the plate surface. Specifically, the laser beam was fixed, and while rotating the engraved printing original plates 1 to 14 in the circumferential direction, the XY stage was moved in the cylinder axis direction, thereby forming a diamond-shaped concave pattern composed of multiple processing lines. The M2 value representing the quality of the light beam is less than 1.8. In addition, the scanning speed in the cylinder axis direction was adjusted to perform processing at a 10-μm pitch according to the processing speed of the ultra-short pulse laser.

[0228] The dimensions of each unit are as described below. It should be noted that the relationship between the lateral width, longitudinal width, and depth of the unit is as Figure 5 shown.

[0229] Highlight area: Unit lateral width 30 μm / longitudinal width 60 μm / depth 6 μm

[0230] Solid area: Unit lateral width 140 μm / longitudinal width 185 μm / depth 35 μm

[0231] Line count: 175 lpi

[0232] The laser wavelength and the configuration of each oscillation device are as follows.

[0233] Laser wavelength 515 nm: Using AMPHOS2000 (manufactured by AMPHOS, trademark), processing was performed using the second harmonic of 515 nm.

[0234] Laser wavelength 1064 nm: Using the fundamental wave of 1064 nm of YAG laser "IceFyre 1064-50" (manufactured by Spectra-Physics, trademark), which is an end-pumped semiconductor laser-excited Q-switch solid laser, for processing.

[0235] Laser wavelength 343 nm: Using the disk-type ultra-short pulse semiconductor laser "TruMicro5380" (manufactured by TRUMPF, trademark), processing was performed using the third harmonic of 343 nm.

[0236] 4. Printing method

[0237] Use a CM type small calibrator made by Nissio.Co.JP (cylinder part: width 150 mm / circumference 400 mm), and print the OPP film at a printing speed of 40 m / minute using the ink composed as follows.

[0238] 4.1. Ink 1

[0239] Use a substance obtained by mixing 5 parts by mass of SUPERIOR (manufactured by SAKATA INX CORPORATION) and 1 part by mass of a diluting solvent (manufactured by SAKATA INX CORPORATION, trade name “SUPERIOR Solvent 2T”) as Ink 1. It should be noted that the viscosity of Ink 1 measured using a Zahn cup #3 is 15 s.

[0240] 4.2. Ink 2

[0241] Use a substance obtained by mixing 5 parts by mass of Rio Alpha (manufactured by Toyo Ink) and 1 part by mass of a diluting solvent (manufactured by Toyo Ink, trade name “LN102 Solvent”) as Ink 2. It should be noted that the viscosity of Ink 2 measured using a Zahn cup #3 is 17 s.

[0242] 5. Evaluation

[0243] 5.1. Transfer stability of the ink to the highlight area

[0244] Use a stereomicroscope SMZ18 (manufactured by Nikon Corporation) to observe the reflected light of the highlight area of the printed matter obtained by the above printing method at an observation magnification of 10 times. Then, measure the area of the ink actually transferred to the OPP film for each unit of the gravure printing plate. Set the area of the ink when all the ink in each unit of the gravure printing plate is transferred as 100 area%, and evaluate the area ratio of the transferred ink. Then, for each unit, it is judged as “transferred” when the area ratio of the transferred ink is 70 area% or more, and judged as “not transferred” when the area ratio of the transferred ink is less than 70 area%.

[0245] Perform the above judgment in the range of 100 mm × 100 mm in the highlight area part, and calculate the ratio of the units judged as transferred to the total number of units contained in this area as the ink transfer rate. Then, evaluate the transfer stability of the ink to the highlight area according to the following evaluation criteria.

[0246] (Evaluation criteria)

[0247] 5: The ink transfer rate is 95% or more

[0248] 4: The ink transfer rate is 90% or more and less than 95%

[0249] 3: The ink transfer rate is 85% or more and less than 90%

[0250] 2: The ink transfer rate is 80% or more and less than 85%

[0251] 1: The ink transfer rate is less than 80%

[0252] 5.2. Ink adhesion to the solid area

[0253] The ink density of the solid area of the printed matter obtained by the above printing method is measured using eXact (X-Rite Corporation, trademark). The measurement of the ink density is performed at 10 arbitrarily selected points in the solid area, and the arithmetic mean thereof is calculated as the "solid density". Then, the ink adhesion to the solid area is evaluated according to the following evaluation criteria.

[0254] (Evaluation criteria)

[0255] 5: The ink density of the solid area is 2.2 or more

[0256] 4: The ink density of the solid area is 2.1 or more and less than 2.2

[0257] 3: The ink density of the solid area is 2.0 or more and less than 2.1

[0258] 2: The ink density of the solid area is 1.9 or more and less than 2.0

[0259] 1: The ink density of the solid area is less than 1.9

[0260] [Table 1]

[0261]

[0262] Industrial applicability

[0263] The present invention has industrial applicability as a resin printing gravure plate for intaglio printing or the like.

[0264] Explanation of reference numerals

[0265] 10... Printing gravure plate, 11... Resin layer, 12... Plate surface, 13... Unit, 13a... Dam, 14... Cylinder, 15... Support layer, 16... Defect, 17... Mold, 17a... Space, 20... Substrate, 21... Impression cylinder, 22... Ink, 23... Rubber inking roller, 24... Doctor blade.

Claims

1. A gravure printing plate, which comprises a resin layer constituting the printing surface, the Shore A hardness of the resin layer is 30 degrees or more and 90 degrees or less, the surface free energy of the resin layer is 10 mN / m or more and 35 mN / m or less, the resin layer has cells on the printing surface, and the coefficient of variation of the cell volume of the cells for printing with the same ink concentration is 0.200 or less.

2. The gravure printing plate according to claim 1, wherein, the same ink concentration is 0.50 or less.

3. The gravure printing plate according to claim 1, wherein, the resin layer contains at least one selected from the group consisting of a photosensitive resin and a thermosetting resin.

4. The gravure printing plate according to claim 1, wherein, the resin layer contains 0.10 parts by mass or more and 15.0 parts by mass or less of a silicone compound based on the total amount.

5. The gravure printing plate according to claim 1, wherein, the depth of the cell is 0.10 μm or more and 100 μm or less.

6. The gravure printing plate according to claim 1, which comprises a cylinder, and the cylindrical resin layer is disposed on the surface of the cylinder.

7. The gravure printing plate according to claim 6, wherein, a support layer is provided between the cylinder and the cylindrical resin layer.

8. A method for manufacturing the gravure printing plate according to any one of claims 1 to 7, which has a processing step of forming recesses in the resin layer by using a laser.

9. The method for manufacturing the gravure printing plate according to claim 8, wherein, the oscillation wavelength of the laser is 100 nm or more and 800 nm or less.

10. The method for manufacturing the gravure printing plate according to claim 8, wherein, the laser is a pulsed oscillation laser, and the pulse width of the pulsed oscillation laser is 1 fs or more and 1 ns.

11. The method for manufacturing the gravure printing plate according to claim 10, wherein, the pulse energy of the laser is 1.00 μJ or more and 1.00 mJ or less.

12. The method for manufacturing the gravure printing plate according to claim 10, wherein, the overlapping rate of the laser in the processing step is 50.0% or more and 99.9% or less.

13. The method for manufacturing the gravure printing plate according to claim 8, wherein, the spot diameter of the laser is 1.0 μm or more and 20 μm or less.

14. The method for manufacturing the gravure printing plate according to claim 8, wherein, in the processing step, the laser is directly irradiated onto the resin layer.

15. The method for manufacturing the gravure printing plate according to claim 8, wherein, in the processing step, there is: a step of forming recesses after disposing the resin layer on the cylinder, or a step of disposing the resin layer on the cylinder after forming recesses in the resin layer in advance.

16. A printing method, which has: a coating step of filling ink into the cells of the gravure printing plate according to any one of claims 1 to 7; and a transfer step of transferring the ink filled in the cells onto the surface of a substrate to obtain a printed matter.

17. A printed matter, which is a printed matter printed by using the gravure printing plate according to any one of claims 1 to 7, and the ink concentration in the solid area is 2.10 or more.

18. A printed matter, wherein, the transfer rate of the highlighted area is more than 90%, and the ink concentration of the highlighted area is 0.50 or less.

Images