CN115298040A - Cylindrical printing plate and method for manufacturing printed matter - Google Patents
Cylindrical printing plate and method for manufacturing printed matter Download PDFInfo
- Publication number
- CN115298040A CN115298040A CN202180021947.9A CN202180021947A CN115298040A CN 115298040 A CN115298040 A CN 115298040A CN 202180021947 A CN202180021947 A CN 202180021947A CN 115298040 A CN115298040 A CN 115298040A
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- Prior art keywords
- printing plate
- ink
- cylindrical
- cylindrical printing
- manufacturing
- Prior art date
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41F—PRINTING MACHINES OR PRESSES
- B41F27/00—Devices for attaching printing elements or formes to supports
- B41F27/12—Devices for attaching printing elements or formes to supports for attaching flexible printing formes
-
- 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
-
- 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
- B41N1/16—Curved printing plates, especially cylinders
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Printing Plates And Materials Therefor (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention provides a cylindrical printing plate which can inhibit ink pollution of printed matters and has excellent durability. The present invention is a method for manufacturing a cylindrical printing plate, comprising the steps of: and a step of winding the lithographic printing plate or the lithographic printing plate precursor around a cylindrical support and filling the gap between the ends of the lithographic printing plate or the lithographic printing plate precursor with an ink-repellent composition.
Description
Technical Field
The present invention relates to a cylindrical printing plate and a method for manufacturing a printed matter.
Background
In the printing market, the field of packaging materials and labels has grown under the influence of expansion of the beverage/lunch market, progress of various types/small batches, diversification of designs, and the like. In these fields, printed matters are mainly produced by continuous printing using a roll-to-roll method, and gravure printing, flexography, resin letterpress printing, and the like are generally used.
Waterless lithography, which has a short plate making process time and enables higher-definition printing, is also proposed in the field of packaging materials and labels. However, the following problems are encountered: since the waterless planographic printing plate is a sheet, when the planographic printing plate is mounted in the circumferential direction of the cylinder of the printing press, if the planographic printing plate is shorter than the outer circumferential length of the cylinder, margins are formed between the patterns printed on the blank (japanese text: original reverse), and post-processing such as cutting becomes complicated. On the other hand, when the lithographic printing plate is longer than the outer circumferential length of the cylinder and is fixed by being sandwiched between the cylinder gaps (grooves), ink adheres to the gaps of the sandwiched portions, and there is a problem that linear contamination imitating the gaps occurs in the printed matter.
In order to solve these problems, for example, patent document 1 discloses a cylindrical waterless printing plate of a silicone underlayer type in which a silicone resin layer is seamlessly formed on a cylindrical base material and an ink-receptive resist pattern portion is provided thereon so that a gap where ink adheres cannot be originally formed.
Documents of the prior art
Patent document
Patent document 1: international publication No. 2017/077825
Disclosure of Invention
Problems to be solved by the invention
However, the cylindrical waterless printing plate of the silicone underlayer type disclosed in patent document 1 has a problem that peeling is likely to occur at the interface between the silicone resin layer and the inked pattern during printing, and the durability in the production of the printed matter is low, because the inked pattern is formed on the silicone resin layer having a low surface free energy.
Accordingly, an object of the present invention is to provide a method for producing a cylindrical printing plate which suppresses ink contamination of a printed matter and has excellent durability.
Means for solving the problems
The method for manufacturing a cylindrical printing plate according to the present invention comprises the steps of: and a step of winding the lithographic printing plate or the lithographic printing plate precursor around a cylindrical support and filling the gap between the ends of the lithographic printing plate or the lithographic printing plate precursor with an ink-repellent composition. The method for producing a printed matter according to the present invention includes the steps of: a step of attaching ink to the surface of the cylindrical printing plate obtained by the method according to the present invention; and transferring the ink to a printing object directly or via a blanket.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a cylindrical printing plate which suppresses ink contamination of a printed matter and has excellent durability can be obtained.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of the shape of a lithographic printing plate precursor.
Fig. 2 (a) is a schematic cross-sectional view showing an example of the shape of a cylindrical lithographic printing plate precursor formed into a cylindrical shape, and (B) is a schematic cross-sectional view showing the shape of a cylindrical printing plate precursor in which the gap is filled with an ink repellent composition.
Detailed Description
The mode for carrying out the present invention will be described in detail below. However, the present invention is not limited to the following embodiments, and can be carried out by being variously modified depending on the purpose and the application.
(Cylinder printing original plate)
The cylindrical printing plate precursor in the present invention is a cylindrical printing plate precursor in which at least a base material and an ink-attracting/ink-repelling functional layer are provided in this order, and can be produced by molding a lithographic printing plate precursor into a cylindrical shape. Hereinafter, the cylindrical printing plate precursor of the present invention will be described based on the drawings.
As shown in fig. 1, the lithographic printing plate precursor 100 has at least a substrate 1 and an ink-attracting/ink-repellent functional layer 4 in this order. An organic layer 2 and/or a thermosensitive layer 3 may also be optionally provided between the substrate 1 and the ink-attracting/ink-repellent functional layer 4. If the lithographic printing plate precursor 100 is a waterless lithographic printing plate precursor, the ink-attracting/repellent functional layer 4 is ink-repellent, and any of the substrate 1, the organic layer 2, and the heat-sensitive layer 3 has ink-attracting properties. On the other hand, in the case of a water-containing lithographic printing plate precursor, the ink-attracting/ink-repellent functional layer 4 has ink-attracting properties, and any of the substrate 1, the organic layer 2, and the thermosensitive layer 3 exhibits ink-repellent properties when it receives a fountain solution (japanese original: wet 12375water).
As shown in fig. 2 (a), the end portion of the lithographic printing plate precursor 100 is bent toward the substrate 1, the ink-strike/repellent functional layer 4 at the bent end portion of the lithographic printing plate precursor 100 is formed into a cylindrical shape so as to form a gap 5, and after the lithographic printing plate precursor 200 formed into a cylindrical shape is produced, as shown in fig. 2 (B), the gap 5 is filled with the ink-repellent composition 6, whereby the cylindrical printing plate precursor 300 can be produced.
The cylindrical printing plate precursor of the present invention is preferable in view of productivity because it can use a conventional lithographic printing plate precursor as compared with a conventional cylindrical printing plate precursor produced by providing 1 cylindrical base material with an ink repellent functional layer.
In the production of the cylindrical printing plate precursor 300, it is preferable from the viewpoint of workability that the lithographic printing plate precursor 200 molded into a cylindrical shape is produced by winding the lithographic printing plate precursor 100 around a cylindrical support such as an exposure machine, a plate cylinder provided in a printing machine, and a metal or plastic cylinder.
The ink-attracting/ink-repellent functional layer 4 and the ink-repellent composition layer 6 are preferably present continuously on the outermost surface of the cylindrical printing plate precursor 300. The term "continuously present" means that the ink-attracting/repellent functional layer 4 or the ink-repellent composition layer 6 is present on the outermost surface of the cylindrical printing plate precursor without interruption. Here, the outermost surface refers to a surface of an outermost layer in the entire cylindrical printing plate precursor.
The ink-attracting/ink-repellent functional layer 4 and the ink-repellent composition layer 6 are preferably present continuously on the outermost surface of the cylindrical printing plate precursor 300. By continuously forming the ink application/repellent functional layer 4 and the ink repellent composition layer 6 on the outermost surface of the cylindrical printing plate precursor 300, it is possible to suppress the deposition of ink in the gap between the printing plates and further suppress the ink contamination of the printed matter when the printed matter is produced using the cylindrical printing plate precursor. Further, the cylindrical printing plate precursor 300 more preferably has at least a position where the substrate 1, the ink-attracting/ink-repellent functional layer 4, and the ink-repellent composition layer 6 are sequentially laminated.
(Cylinder type printing plate)
The cylindrical printing plate of the present invention is a cylindrical printing plate comprising at least a base material and an ink-attracting/repelling functional layer in this order, and an image portion and a non-image portion are formed on the cylindrical printing plate precursor. The cylindrical printing plate of the present invention is explained below based on the drawings.
The cylindrical printing plate of the present invention can be produced by forming an image on the cylindrical printing plate precursor 300 by ablation using a carbon dioxide laser, an excimer laser, a YAG laser, physical cutting using a metal/diamond blade, or the like. In the lithographic printing plate precursor 100 as shown in fig. 1, when any of the organic layer 2, the heat-sensitive layer 3, and the ink-attracting/ink-repelling functional layer 4 has a function of forming an image by being sensitized with near-infrared light, it is preferable in terms of high plate-making speed because the image can be formed by a general-purpose semiconductor laser having an emission wavelength region in the vicinity of the near-infrared region.
Further, after the lithographic printing plate precursor 100 is image-formed by exposure or exposure and development, the end portion of the lithographic printing plate 100 is bent toward the substrate 1, the ink-attracting/ink-repellent functional layers 4 of the bent end portion of the lithographic printing plate are adjacent to or in contact with each other to form a gap 5 into a cylindrical shape, the lithographic printing plate 200 formed into a cylindrical shape is manufactured, and then the gap 5 is filled with the ink-repellent composition 6, whereby the cylindrical printing plate 300 can be manufactured.
By the presence of the ink-attracting/ink-repellent functional layer 4 and the ink-repellent composition layer 6 continuously on the outermost surface of the cylindrical printing plate 300, it is possible to suppress the accumulation of ink in the gap between the printing plates and further suppress the ink contamination of the printed matter when the printed matter is produced using the cylindrical printing plate.
Further, it is more preferable to have at least a position where the substrate 1, the ink-attracting/ink-repellent functional layer 4, and the ink-repellent composition layer 6 are sequentially laminated.
In the cylindrical printing plate precursor and the cylindrical printing plate according to the present invention, the base material, the organic layer, the heat-sensitive layer, and the ink-attracting/ink-repellent functional layer are common. Each will be described below.
(substrate)
Examples of the substrate include known paper, metal, and film that have been used for printing plates in the past and have little dimensional change in the printing process. The substrate in the present invention preferably has ink-staining properties. Specifically, there are paper, paper laminated with plastic (polyethylene, polypropylene, polystyrene, etc.), a metal plate of aluminum (also containing an aluminum alloy), zinc, copper, etc., a film of plastic such as cellulose acetate, polyethylene terephthalate, polyethylene, polyester, polyamide, polyimide, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., paper deposited with aluminum (also containing an aluminum alloy), zinc, copper, etc., or a plastic film deposited with aluminum (also containing an aluminum alloy), zinc, copper, etc., or the like. The plastic film may be transparent or opaque. From the viewpoint of plate detectability, an opaque film is preferable.
Among these substrates, an aluminum plate is particularly preferable because it is inexpensive and has little dimensional change in the printing process. In addition, as a flexible substrate for light printing, a polyethylene terephthalate film is particularly preferable. The thickness of the substrate is not particularly limited as long as the thickness corresponding to the printer is selected.
(organic layer)
Between the substrate and the ink-attracting/ink-repellent functional layer, an organic layer may optionally be provided. The organic layer in the present invention preferably has ink-staining properties. The properties of the organic layer are such that flexibility is imparted to the waterless printing plate, the organic layer has good adhesion to a substrate or a heat-sensitive layer, and the organic layer has high resistance to a developer or a solvent used in printing. For example, the organic layer containing a metal chelate compound disclosed in Japanese patent application laid-open Nos. 2004-199016 and 2004-334025 is preferably used, but not limited thereto.
The organic layer preferably comprises a pigment. By including the pigment, the light transmittance of the organic layer can be set to 15% or less for all wavelengths of 400 to 650nm, and thus, the plate detection property by mechanical reading can be provided. As the pigment, inorganic white pigments such as titanium oxide, zinc oxide, and lithopone, and inorganic yellow pigments such as chrome yellow, cadmium yellow, iron oxide yellow, ochre, and titanium yellow are preferably used. Among these pigments, titanium oxide is particularly preferably used in view of hiding power and coloring power. The content of the pigment in the organic layer is preferably 2% by volume or more from the viewpoint of obtaining good concealing properties. On the other hand, from the viewpoint of obtaining good coating performance, it is preferably 30% by volume or less in the organic layer.
(Heat-sensitive layer)
Between the substrate and the ink-receptive/repellent functional layer, a heat-sensitive layer may optionally be provided. The thermosensitive layer in the present invention preferably has ink-receptive properties. The thermosensitive layer preferably has a function of converting a laser beam used for drawing into heat (photothermal conversion), and further, the generated heat decomposes at least the surface of the thermosensitive layer, improves the solubility in a developer, or reduces the adhesion to the ink repellent layer. Such a thermosensitive layer may contain, for example, the following composition.
(a) A composition comprising a polymer having active hydrogen, an organic complex compound, and a photothermal conversion substance.
(b) A composition comprising a polymer having active hydrogen, a crosslinking agent, and a photothermal conversion material.
(c) A composition comprising a polymer having active hydrogen with self-reactivity, and a photothermal conversion substance.
The heat-sensitive layer is irradiated with laser light, whereby the crosslinked structure composed of the polymer having active hydrogen and the organic complex is decomposed by heat generated from the photothermal conversion substance in the composition shown in (a). In the composition shown in (b), the crosslinked structure composed of the polymer and the crosslinking agent is decomposed by heat generated from the photothermal conversion substance by irradiation with laser light. In the composition shown in (c), the crosslinked structure formed by the self-reaction of the polymer is decomposed by the heat generated from the photothermal conversion substance by irradiation with laser light.
Examples of the polymer having active hydrogen preferably used for the thermosensitive layer include polymers having a structural unit having active hydrogen. Examples of the structural unit having active hydrogen include-OH, -SH, and-NH 2 、-NH-、-CO-NH 2 、-CO-NH-、-OC(＝O)-NH-、-NH-CO-NH-、-CO-OH、-CS-OH、-CO-SH、-CS-SH、-SO 3 H、-PO 3 H 2 、-SO 2 -NH 2 、-SO 2 -NH-、-CO-CH 2 -CO-, etc.
Examples of the polymer having active hydrogen that can be suitably used in the compositions (a) and (b) include acrylic resins, polyurethanes, polyureas, polyamides, epoxy resins, polyalkylene imines, novolac resins, cellulose derivatives, and the like, which have a carboxyl group or a hydroxyl group.
Examples of the self-reactive polymer having active hydrogen that can be suitably used in the composition (c) include resoles and melamine resins.
The content of the polymer having active hydrogen in the heat-sensitive layer is preferably 20 mass% or more, and more preferably 30 mass% or more, from the viewpoint of thermally decomposing the surface of the heat-sensitive layer or from the viewpoint of promoting development by changing to be easily soluble in a developer. In addition, from the viewpoint of toughness of the thermosensitive layer, it is preferably 95% by mass or less, and more preferably 80% by mass or less.
The organic complex compound contained in the composition (a) contains a metal and an organic compound. Which acts as a crosslinking agent for polymers having active hydrogen. Examples of such organic complex compounds include organic complex salts in which an organic ligand is coordinated to a metal, organic and inorganic complex salts in which an organic ligand and an inorganic ligand are coordinated to a metal, and metal alkoxides in which a metal and an organic molecule are covalently bonded via oxygen.
Preferred as the main metal forming the organic complex are Al (III), ti (IV), mn (II), mn (III), fe (II), fe (III), co (II), co (III), ni (II), ni (IV), cu (I), cu (II), zn (II), ge, in, sn (II), sn (IV), zr (IV) and Hf (IV). Al (III) is particularly preferable in terms of easily obtaining the sensitivity-improving effect, and Ti (IV) is particularly preferable in terms of easily exhibiting resistance to printing ink and ink cleaning agent.
Examples of the ligand include compounds having a ligand having oxygen, nitrogen, sulfur, or the like as a donor atom. Specific examples of the ligand include, as oxygen donor atoms, OH (alcohol, enol, and phenol), -COOH (carboxylic acid), > C = O (aldehyde, ketone, quinone), -O- (ether), -COOR (ester, R: represents aliphatic or aromatic hydrocarbon), -N = O (nitroso compound), -NO 2 (nitro compounds), > N-O (N-oxides), -SO 3 H (sulfonic acid), -PO 3 H 2 (phosphorous acid) and the like, and examples of the donor atom of nitrogen include-NH 2 (primary amine, hydrazine), > NH (secondary amine, hydrazine), > N- (tertiary amine), -N = N- (azo compound, heterocyclic compound), = N-OH (oxime), -NO 2 Examples of the "nitro compound", "N = O (nitroso compound), > C = N- (schiff base, heterocyclic compound), > C = NH (aldehyde, ketimine, enamine), and" NCS (isothiocyanate) include, as a donor atom, sulfur, -SH (thiol), -S- (thioether), > C = S (thione, thioamide), = S- (heterocyclic compound), "-C (= O) -SH, -C (= S) -OH, -C (= S) -SH (thiocarboxylic acid), and" SCN (thiocyanate).
Among the organic complexes composed of a metal and a ligand as described above, preferable examples of the compound to be used include acetylacetone complexes and acetoacetate complexes of Al (III), fe (II), fe (III), ti (IV) and Zr (IV).
Specific examples of such compounds include the following compounds.
Aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum tris (propylacetoacetate), aluminum tris (butylacetoacetate), aluminum bis (ethylacetoacetate) mono (acetylacetonate), aluminum bis (acetylacetonate) mono (ethylacetoacetate), aluminum bis (propylacetoacetate) mono (acetylacetonate), aluminum bis (butylacetoacetate) mono (acetylacetonate), aluminum bis (propylacetoacetate) mono (ethylacetoacetate), aluminum bis (butylacetoacetate) mono (ethylacetoacetate), aluminum dibutanol mono (acetylacetonate), aluminum diisopropanol mono (ethylacetoacetate), titanium diisopropanol bis (acetylacetonate), titanium dibutanol bis (acetylacetonate), titanium diisopropanol bis (ethylacetoacetate), titanium dibutanol mono (ethylacetoacetate), titanium tri-n-butanol mono (ethylacetoacetate), titanium triisopropanol mono (methacryloyloxyethylacetoacetate), titanium bis (acetylacetonate), titanium oxide bis (acetylacetonate), zirconium tetrakis (acetylacetonate), iron (III) acetate. These may be contained in 2 or more kinds.
Such organic complex compounds function as crosslinking agents for polymers. The amount thereof is preferably 0.5 mass% or more in the thermosensitive layer. Further, it is preferably 50% by mass or less in view of maintaining the durability of the waterless planographic printing plate.
Examples of the crosslinking agent contained in the composition (b) include polyfunctional compounds having a plurality of functional groups reactive with the active hydrogen of the polymer. Examples thereof include polyfunctional isocyanates, polyfunctional blocked isocyanates, polyfunctional epoxy compounds, polyfunctional (meth) acrylate compounds, polyfunctional aldehydes, polyfunctional mercapto compounds, polyfunctional alkoxysilyl compounds, polyfunctional amine compounds, polyfunctional carboxylic acids, polyfunctional vinyl compounds, polyfunctional diazo compounds
Salts, polyfunctional azido compounds, hydrazines, and the like.
The photothermal conversion substance that can be contained in the compositions (a) to (c) is preferably a substance having a function of converting light energy into kinetic energy of atoms/molecules by absorbing laser light, instantaneously generating heat of 200 ℃ or higher on the surface of the thermosensitive layer, and thermally decomposing the crosslinked structure of the thermosensitive layer. Particularly, pigments and dyes that absorb infrared rays or near infrared rays are preferable. Examples thereof include black pigments such as carbon black, carbon graphite, aniline black and cyanine black, phthalocyanine and naphthalocyanine green pigments, inorganic compounds containing crystal water, metal powders such as iron, copper, chromium, bismuth, magnesium, aluminum, titanium, zirconium, cobalt, vanadium, manganese and tungsten, sulfides, hydroxides, silicates, sulfates, phosphates, diamine compound complexes, dithiol compound complexes, phenol thiol compound complexes and mercapto phenol compound complexes of these metals.
Further, as the dye that absorbs infrared rays or near infrared rays, cyanine dyes that are dyes for electronics and recording and have a maximum absorption wavelength in the range of 700nm to 1500nm, azulene, and the like are preferably used
Dye series and squaric acid
Dye series, ketone
Examples of the dye include azo dyes, azo disperse dyes, bisazo stilbene dyes, naphthoquinone dyes, anthraquinone dyes, perylene dyes, phthalocyanine dyes, naphthalocyanine metal complex dyes, polymethine dyes, dithiol nickel complex dyes, indoaniline metal complex dyes, intermolecular CT dyes, benzopyran spiropyrans, and nigrosine dyes.
Among these dyes, those having a large molar absorption coefficient ε are preferably used. Specifically,. Epsilon.is preferably 1X 10 4 L/(mol · cm) or more, more preferably 1X 10 5 L/(mol cm) or more. If ε is 1X 10 4 When L/(mol. Cm) or more, the initial sensitivity can be further improved. The coefficients here are for the active energy rays to be irradiated. It is preferable to look at 780nm, 830nm or 1064nm if a specific wavelength is displayed.
These photothermal conversion substances may be contained in 2 or more kinds. By containing 2 or more kinds of photothermal conversion substances having different absorption wavelengths, it is possible to respond to 2 or more kinds of laser light having different emission wavelengths.
Among them, carbon black and infrared or near-infrared absorbing dyes are preferable from the viewpoints of a photothermal conversion rate, economy and workability.
The content of these photothermal conversion substances in the thermosensitive layer is preferably 0.1 to 70 mass%, more preferably 0.5 to 40 mass%. By setting the content of the photothermal conversion substance to 0.1 mass% or more, the sensitivity to laser light can be further improved. On the other hand, by being 70% by mass or less, the high durability of the waterless printing plate can be maintained.
(ink-attracting/ink-repellent functional layer)
If the lithographic printing plate precursor is an anhydrous lithographic printing plate precursor, the ink-attracting/ink-repellent functional layer is preferably ink-repellent and contains an organic silicon compound. Among them, a silicone rubber layer is preferable. Examples of the silicone rubber layer include a layer obtained by applying an addition reaction type silicone rubber layer composition, a condensation reaction type silicone rubber layer composition, or a silicone rubber layer composition containing both an addition reaction type and a condensation reaction type, or a layer obtained by applying and drying a solution of these compositions.
On the other hand, if the lithographic printing plate precursor has water, the ink-attracting/ink-repellent functional layer is preferably ink-attracting, and contains a light/heat-polymerizable compound and a light/heat-polymerization initiator. The light/heat polymerizable compound is not particularly limited, and acrylic resin, phenol resin, melamine resin, or the like can be used. The photo/thermal polymerization initiator may be preferably a known commercially available product. From the viewpoint of productivity, it is preferable to perform curing by exposure using a general-purpose semiconductor laser having an emission wavelength region in the vicinity of the near-infrared region, and on the other hand, it is more preferable that unexposed portions can be easily removed by physical stimulation. Examples thereof include (1) a method of removing unexposed portions by rubbing with a rotating brush while applying water and a solvent, and (2) a method of removing unexposed portions by the viscosity of ink supplied after swelling with fountain solution.
(Silicone rubber layer)
The silicone rubber used for the silicone rubber layer is preferably an addition reaction type silicone rubber composition in view of the excellent curing rate and the improvement of productivity. The addition reaction type silicone rubber composition preferably contains at least a vinyl group-containing organopolysiloxane, an SiH group-containing compound having a plurality of hydrosilyl groups, and a curing catalyst. Further, a reaction inhibitor may be contained.
The vinyl group-containing organopolysiloxane has a structure represented by the following general formula (α), and has a vinyl group at a terminal of a main chain or in the main chain. Among them, those having a vinyl group at the end of the main chain are preferable. May contain 2 or more of them.
-(SiR 1 R 2 -O-) n - (α)
In the general formula (α), n represents an integer of 2 or more. R 1 And R 2 Represents a saturated or unsaturated hydrocarbon group having 1 to 50 carbon atoms. The hydrocarbon group may be linear, branched or cyclic, and may contain an aromatic ring. R 1 And R 2 May be the same or different. In the polysiloxane of formula (. Alpha.) there are a plurality of R's present 1 May be the same or different from each other. Furthermore, a plurality of R's in the polysiloxane of the formula (. Alpha.) are present 2 May be the same or different from each other. In the above general formula (. Alpha.), R 1 And R 2 It is preferable that 50% or more of the total of (A) is methyl from the viewpoint of ink repellency of the waterless lithographic printing plate. In addition, the weight average molecular weight of the vinyl group-containing organopolysiloxane is preferably 30,000 or more and 200,000 or less from the viewpoint of fineness and scratch resistance.
Examples of the SiH group-containing compound include an organohydrogenpolysiloxane and an organic polymer having a diorganohydrogensilyl group, and the organohydrogenpolysiloxane is preferable. May contain 2 or more of them. The organohydrogenpolysiloxane may have a linear, cyclic, branched, or network molecular structure.
The SiH group-containing compound which is a copolymer of siloxane structural units represented by the following general formulae (i) and (ii) is preferable in terms of cost because the paste start temperature increases.
-SiH(CH 3 )-O- (i)
-Si(CH 3 ) 2 -O- (ii)
In the present invention, the content ratio ((i)/((i) + (ii)) × 100) of the siloxane structural unit represented by the general formula (i) in the SiH group-containing compound to 100 mol% of the total of the siloxane structural unit represented by the general formula (i) and the siloxane structural unit represented by the general formula (ii) is preferably 50 mol% or more, more preferably 60 mol% or more, in terms of the amount of the functional group that can react per 1 molecule and the crosslinking density can be increased. The content ratio of the siloxane structural unit represented by the general formula (i) may be 100 mol%, but is preferably 99 mol% or less in order to prevent brittleness due to an excessive number of crosslinking points.
Examples of the reaction inhibitor include nitrogen-containing compounds, phosphorus-based compounds, unsaturated alcohols, and the like, and an alcohol containing an ethynyl group is preferably used. May contain 2 or more of them. By containing these reaction inhibitors, the curing speed of the silicone rubber layer can be adjusted. The content of the reaction inhibitor in the silicone rubber layer composition is preferably 0.01 mass% or more, and more preferably 0.1 mass% or more, from the viewpoint of stability of the silicone rubber layer composition or its solution. From the viewpoint of curability of the silicone rubber layer, the silicone rubber layer composition preferably contains 20 mass% or less, and more preferably contains 15 mass% or less.
The curing catalyst may be selected from known substances. Preferred are platinum-based compounds, and specific examples thereof include a platinum simple substance, platinum chloride, chloroplatinic acid, olefin-coordinated platinum, an alcohol-modified complex of platinum, and a methyl vinyl polysiloxane complex of platinum. These may be contained in 2 or more kinds. From the viewpoint of curability of the silicone rubber layer, the content of the curing catalyst in the silicone rubber layer composition is preferably 0.001% by mass or more, and more preferably 0.01% by mass or more. From the viewpoint of stability of the silicone rubber layer composition or the solution thereof, the silicone rubber layer composition preferably contains 20 mass% or less, and more preferably contains 15 mass% or less. Note that the distribution and content of the platinum catalyst can be estimated by scanning electron microscope/energy dispersive X-ray spectroscopy (SEM/EDX) analysis.
In addition to these components, the rubber composition may contain an organopolysiloxane having a hydroxyl group, a silane having a hydrolyzable functional group or a siloxane having such a functional group, a known filler such as silica for the purpose of improving rubber strength, and a known silane coupling agent for the purpose of improving adhesiveness. The silane coupling agent is preferably an alkoxysilane, an acetoxysilane, a ketoximosilane, or the like, and is preferably a substance in which a vinyl group or an allyl group is directly bonded to a silicon atom.
The thickness of the silicone rubber layer is preferably 2.0 μm or more, more preferably 3.0 μm or more, and even more preferably 4.0 μm or more, from the viewpoint of further improving the ink repellency and durability. Further, from the viewpoint of improving the fineness, it is preferably 7.0 μm or less, and more preferably 6.0 μm or less. The thickness of the silicone rubber layer can be confirmed by embedding a cut piece of an anhydrous lithographic printing plate with a resin, making a cross section by the CP method, and observing the cross section by a field emission scanning electron microscope (FE-SEM).
In order to further improve the ink repellency, the silicone rubber layer in the present invention may contain silicone oil.
The content of the silicone oil in the silicone rubber layer is preferably 10 mass% or more in view of sufficiently extruding the silicone rubber layer surface and significantly improving the ink repellency. In addition, the content in the silicone rubber layer is preferably 30% by mass or less, more preferably 25% by mass or less, from the viewpoint of maintaining the film strength of the silicone rubber layer.
The amount of silicone oil in the silicone rubber layer can be confirmed by immersing the cut silicone rubber layer in hexane and measuring the mass of the extracted silicone oil.
The silicone oil in the present invention means a free polysiloxane component which does not participate in the crosslinking of the silicone rubber layer. Thus, examples thereof include modified silicone oils in which various organic groups have been introduced into a part of the methyl group in the molecule, such as terminal dimethyl polydimethylsiloxane, cyclic polydimethylsiloxane, terminal dimethyl-polydimethyl-polymethylphenylsiloxane copolymer, terminal dimethyl-polydimethyl-polydiphenylsiloxane copolymer and the like, alkyl-modified silicone oils, fluorine-modified silicone oils, polyether-modified silicone oils, alcohol-modified silicone oils, amino-modified silicone oils, epoxy-polyether-modified silicone oils, phenol-modified silicone oils, carboxyl-modified silicone oils, mercapto-modified silicone oils, amide-modified silicone oils, palm wax (12459\125231249690).
The molecular weight of these silicone oils can be measured by Gel Permeation Chromatography (GPC) using polystyrene as a standard, and is preferably 1000 to 10 ten thousand in weight average molecular weight Mw.
(ink repellent composition and ink repellent composition layer)
The ink repellent composition may be a one-component system or a two-component or more system that is cured by mixing, but is preferably a one-component system in view of handling. The curing method is not limited, and the curing may be performed naturally at room temperature or by heating. The heat curing is preferable in terms of improving the film strength of the ink repellent composition layer formed by curing the ink repellent composition and improving the durability of the cylindrical printing plate.
In the case where the lithographic printing plate is an anhydrous lithographic printing plate, the ink repellent composition preferably contains an organosilicon compound.
The ink repellent composition containing an organosilicon compound preferably has a binder polymer. Examples of the binder polymer of the ink repellent composition include silicone polymers, fluorosilicone polymers, silicone/acrylic copolymers, and the like. May contain 2 or more of them. Among them, a silicone polymer can be preferably used from the viewpoint of cost.
Addition type having a vinyl group and condensation type having a silanol group can be used in the silicone polymer. Among them, the condensed type silicone polymer is preferable in that it is easily a one-component system because it is reacted/cured by moisture in the air.
Examples of the crosslinking agent for the addition-type silicone polymer include SiH group-containing compounds such as organohydrogenpolysiloxane and diorganohydrosilyl-containing organic polymer. As the crosslinking agent of the condensation-type silicone polymer, a known silane coupling agent can be used.
As the crosslinking agent of the condensation type silicone polymer, a silane coupling agent can be preferably used, and compounds such as alkoxysilanes, acetoxysilanes, ketoximosilanes, and 4-functional hydrolyzable groups, and ketoximosilanes having a 3-functional hydrolyzable group are preferable. In the case of a compound having a 3-functional hydrolyzable group, a compound in which a vinyl group or an allyl group is directly bonded to a silicon atom is preferable in view of curing speed.
The content of the silane coupling agent in the ink repellent composition containing the condensed type silicone polymer is preferably 3% by mass or more, and more preferably 5% by mass or more, from the viewpoint of curing speed. The amount of the ink repellent composition layer is preferably 15% by mass or less, and more preferably 10% by mass or less, from the viewpoint of suppressing brittleness of the ink repellent composition layer.
When a silane coupling agent having a 3-functional hydrolyzable group and a silane coupling agent having a 4-functional hydrolyzable group are used in combination, the content of the silane coupling agent having a 4-functional hydrolyzable group is preferably 5% by mass or more, and more preferably 10% by mass or more, based on the total amount of the silane coupling agents in the ink repellent composition, from the viewpoint of improving the curing rate. On the other hand, in terms of storage stability, the total amount of the silane coupling agent in the ink repellent composition is preferably 50% by mass or less, and more preferably 30% by mass or less.
The ink repellent composition containing the condensed type silicone polymer preferably contains a compound represented by the general formula (I) and a compound represented by the general formula (II).
R-Si-(A) 3 (I)
Si-(B) 4 (II)
In the general formula (I) and the general formula (II), R represents a non-hydrolyzable organic group, and A and B represent hydrolyzable groups. Specific examples of R include vinyl, chloromethyl, methyl, ethyl, phenyl, propyl, cyclohexyl and the like. Examples of A include acetoxy, oximino, methoxy, ethoxy and the like. Examples of B include acetoxy, oximino, methoxy, ethoxy and the like.
The compound represented by the general formula (II) contained in the ink repellent composition is preferably 5 to 50% by mass based on the total of the compound represented by the general formula (I) and the compound represented by the general formula (II). The film strength of the ink repellent composition layer can be increased to further improve the durability of the cylindrical printing plate, and is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. On the other hand, from the viewpoint of suppressing brittle fracture of the ink repellent composition layer and maintaining durability, it is preferably 50% by mass or less, and more preferably 30% by mass or less.
The ink repellent composition layer formed by curing the ink repellent composition as described above preferably contains SiO 4/2 A structural unit. That is, it is preferable that the organosilicon compound contains SiO 4/2 A structural unit. Including SiO in the ink repellent composition layer 4/2 The structural units may pass through a solid 29 Si NMR analysis. The organosilicon compound comprises SiO 4/2 The structural units can also be confirmed by the same method.
Further, siO in the ink repellent composition layer 4/2 Content ratio of structural unit to R 3 SiO 1/2 Structural unit, R 2 SiO 2/2 Structural unit, RSiO 3/2 Structural unit and SiO 4/2 The total of the structural units is preferably 0.8 to 2.5%. I.e. SiO contained in the organosilicon compound 4/2 Content ratio of structural unit to R 3 SiO 1/2 Structural unit, R 2 SiO 2/2 Structural unit, RSiO 3/2 Structural unit and SiO 4/2 Structural sheetThe total of the elements is preferably 0.8 to 2.5%.
The SiO in the ink repellent composition layer can improve the film strength of the ink repellent composition layer and further improve the durability of the cylindrical printing plate 4/2 Content ratio of structural units and SiO contained in the organosilicon compound 4/2 The content of the structural unit is preferably 0.8% or more, more preferably 1.0% or more. On the other hand, from the viewpoint of suppressing brittle fracture due to excessive hardening of the ink repellent composition layer, it is preferably 2.5% or less, and more preferably 1.5% or less. Here, R is an arbitrary organic substituent.
SiO 4/2 The content of the structural units can be determined by passing through a solid 29 SiO obtained by Si NMR analysis 4/2 Peak area of structural unit relative to R 3 SiO 1/2 Peak area of structural Unit, R 2 SiO 2/2 Peak area of structural Unit, RSiO 3/2 Peak area of structural unit, and SiO 4/2 The ratio of the total of peaks of the structural units. SiO in ink repellent composition layer 4/2 The content ratio of the structural unit becomes a criterion of the crosslink density in the ink repellent composition layer. By means of solids 29 The detailed measurement method of each peak area obtained by Si NMR analysis is described in the column of examples.
Further, the ink repellent composition layer may contain silicone oil for the purpose of further improving the ink repellency and further suppressing contamination of the gap between the circumferential ends of the waterless planographic printing plate. The silicone oil used here may be the same as the silicone oil that the silicone rubber layer may contain.
The content of the silicone oil in the ink repellent composition layer is preferably 5% by mass or more, and more preferably 10% by mass or more, from the viewpoint of significantly improving the ink repellency. In addition, from the viewpoint of maintaining the film strength of the ink repellent composition layer, it is preferably 50% by mass or less, and more preferably 25% by mass or less.
The content of the silicone oil in the ink repellent composition layer can be confirmed by immersing the cut ink repellent composition layer in hexane and measuring the mass of the extracted silicone oil.
On the other hand, in the case where the lithographic printing plate is a lithographic printing plate having water, a hydrophilic compound which exhibits ink repellency by contact with a fountain solution can be used as the ink repellent composition. Here, the hydrophilic compound is a compound having a contact angle of less than 90 degrees when contacted with water, and is preferably a water-soluble resin which swells more easily because it swells with a fountain solution to obtain ink repellency.
The water-soluble resin may be swollen or dissolved in the fountain solution, and examples thereof include glycidyl-modified acrylic resin, resol-type phenol resin, polyurethane, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, polyacrylamide, carboxymethyl cellulose, gum arabic, starch, gelatin, casein, and the like, and 2 or more of them may be contained.
Among such water-soluble resins, those having a vinyl group and/or a hydroxymethyl group are preferable in terms of improving durability by photo/thermal curing after filling a gap formed between the edges of a lithographic printing plate having water. For example, glycidyl group-modified acrylic resin, resol type phenol resin, and the like can be preferably used.
(method of Forming ink repellent composition layer)
The ink repellent composition layer can be formed, for example, by the following method: the ink repellent functional layer is formed into a cylindrical shape so that the ink repellent functional layer side becomes the surface, (1) a tape having an ink repellent property on the surface is attached to a gap between circumferential ends of the lithographic printing plate, (2) a tape having an ink repellent composition layer is attached to a gap between circumferential ends of the lithographic printing plate, and then the release film is peeled off to transfer the ink repellent composition layer, (3) the ink repellent composition is filled in the gap between circumferential ends of the lithographic printing plate, and the like.
Among them, the ink repellent composition is preferably a tape having an ink repellent surface.
Preferably, the lithographic printing plate is formed in a cylindrical shape such that the ink-applied/ink-repellent functional layer side becomes the surface, and (3) the ink-repellent composition is filled in the gap between the circumferential ends of the lithographic printing plate to form the ink-repellent composition layer. More preferably, the ink repellent composition layer is formed by (1) forming the lithographic printing plate into a cylindrical shape so that the ink repellent composition layer side becomes a surface, and (3) filling the ink repellent composition into a gap between circumferential ends of the lithographic printing plate, and then heating the filled ink repellent composition.
In the present invention, the film thickness of the ink repellent composition layer refers to the film thickness at the position laminated on the ink-applying/ink repellent functional layer. That is, as shown in fig. 2 (B), the film thickness 6H of the ink repellent composition layer 6 is defined by the height from the surface of the ink application/repellent functional layer to the surface of the ink repellent composition layer, and can be measured by a surface roughness/profile shape measuring machine.
The film thickness of the ink repellent composition layer is preferably 1 μm or more, more preferably 5 μm or more, from the viewpoint of further improving the ink repellency. On the other hand, from the viewpoint of suppressing the decrease in durability caused by abrasion of the ink repellent composition layer due to stress applied at the time of printing, it is preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 10 μm or less.
(method for manufacturing cylindrical printing plate)
Next, a method for manufacturing a cylindrical printing plate using the cylindrical printing plate precursor will be described. The method for producing a cylindrical printing plate according to the present invention preferably includes a step of exposing the cylindrical printing plate precursor according to an image (exposure step) or a step of forming an image by applying a physical stimulus to the exposed cylindrical printing plate precursor other than the exposure step (development step).
First, the exposure process will be described. The cylindrical printing plate precursor is exposed to light in accordance with an image. Examples of the light source used in the exposure step include a light source having an emission wavelength region in the range of 300nm to 1500 nm. Among them, a semiconductor laser or YAG laser having an emission wavelength region near the near infrared region is preferably used because it is widely used as an absorption wavelength of the thermosensitive layer. Specifically, from the viewpoint of the efficiency of conversion to heat, it is preferable to use laser beams having wavelengths of 780nm, 830nm, and 1064nm for the exposure.
Next, the developing step will be explained. The ink-repellent functional layer in the exposed or unexposed portion is removed by applying a physical stimulus to the original plate after exposure. Examples of methods for applying the physical stimulation include (I) a method of wiping off the surface of a printing plate with a dried nonwoven fabric, absorbent cotton, cloth, sponge, or the like, (II) a method of wiping off the surface of a printing plate with a nonwoven fabric, absorbent cotton, cloth, sponge, or the like impregnated with a developing solution, (III) a method of wiping off the surface of a printing plate with a rotary brush while spraying tap water or the like after pretreating the surface of a printing plate with a developing solution, (IV) a method of spraying high-pressure water, warm water, or water vapor onto the surface of a printing plate, (V) a method of wiping off the surface of a printing plate with a rotary brush by impregnating the surface of a printing plate with a developing solution, and (VI) a method of removing exposed portions or unexposed portions by the viscosity of ink supplied after swelling the surface of a printing plate with a fountain solution.
As the developer, for example, water, alcohol, and paraffin can be used. Further, a mixture of a propylene glycol derivative such as diglycolamine, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, and an alkylene oxide adduct to polypropylene glycol, or the above compound with water may be used. Specific examples of the developer include HP-7N, WH-3, PP-1, PP-3, PP-F, PP-FII, PTS-1, CP-Y, CP-X, NP-1, and DP-1 (all manufactured by Chinese imperial corporation, 1252450). Further, for the purpose of improving visibility of the line portion and measurement accuracy of halftone dots, the line portion may be dyed simultaneously with development using a developer containing a dye such as crystal violet, victoria pure blue, or astrasone red. Further, dyeing may also be performed by a liquid containing the above dye after development.
The cylindrical printing plate may be produced from a lithographic printing plate having a picture line portion and a non-picture line portion. The cylindrical printing plate can be produced by winding the lithographic printing plate around a cylindrical support and filling the gap between the ends of the lithographic printing plate with an ink-repellent composition. Here, the planographic printing plate may be either an anhydrous planographic printing plate or a watery planographic printing plate. The gap formed between the ends of the planographic printing plate is preferably 5mm or less. When the thickness is 5mm or less, the ink repellent composition can be uniformly filled, and contamination due to uneven application and reduction in durability can be suppressed.
Preferably, the method further comprises a step of flattening the ink repellent composition and/or a step of heating the ink repellent composition after filling the gap formed between the edges of the lithographic printing plate with the ink repellent composition. Examples of the flattening step include a method of mechanically applying pressure from an ink repellent composition filled in a gap formed between edges of a lithographic printing plate; a method of flattening the surface flat with a squeegee or a hand roller, and the like. The arithmetic surface roughness Ra of the planarized ink repellent composition is preferably 0.3 μm or less. When the thickness is 0.3 μm or less, contamination due to uneven application and deterioration in durability can be suppressed. Examples of the heating step include a method of bringing a heat source into contact with an ink repellent composition filled in a gap formed between the edges of the lithographic printing plate, a method of applying hot air, and the like.
(method of producing printed matter Using cylindrical printing plate)
The method for manufacturing a printed matter according to an embodiment of the present invention using the cylindrical printing plate includes at least the steps of: (1) A step of adhering ink to the surface of the cylindrical printing plate; and (2) transferring the ink to a printing object directly or via a blanket.
The cylindrical printing plate is directly fixed to the cylindrical support or is fixed to a sleeve that is detachable from the cylindrical support. When the sleeve is fixed, the material of the sleeve preferably includes glass fiber and/or aluminum from the viewpoint of weight reduction.
The method of manufacturing a printed matter according to the embodiment of the present invention using the cylindrical printing plate is, for example, as follows. An ink repellent liquid is applied to the surface of a cylindrical printing plate. An ink roller to which ink is supplied is brought into contact with the surface of the cylindrical printing plate, and the ink adheres to the portions to be drawn and repels the ink at the portions not to be drawn. Then, the cylindrical printing plate having the ink attached thereto in the form of an image is directly contacted with the object to be printed, or is contacted with the blanket once, and then the blanket is contacted with the object to be printed, whereby the ink in the form of an image can be transferred to the object to be printed, thereby producing a printed material.
Here, the step of applying the ink repellent liquid to the surface of the cylindrical printing plate is essential if water printing is performed, and the ink repellent liquid is a fountain solution. Optional if it is waterless printing, ink repellent liquid refers to a low polarity solvent capable of swelling the silicone layer.
In the step of transferring the ink to the printing object via the blanket, the ink transferred to the blanket may be heated for the purpose of improving adhesion to the printing object due to an increase in ink fluidity.
The cylindrical printing plate of the present invention can be suitably used for printing a packaging material. In post-processing such as a lamination process, a bag-making process, and the like, the printed body is preferably conveyed in a roll-to-roll manner in terms of availability of existing equipment.
Examples of the object to be printed include films, papers, and metal foils. Specific examples thereof include kraft paper, glazing kraft paper, high-quality paper, medium-quality paper, newspaper paper, chemical fiber paper, and paper, coated paper, polypropylene, polyethylene terephthalate, polyester, polyamide, polyimide, polystyrene, polycarbonate, polyvinyl acetal, cellulose acetate, aluminum foil (which may also include an aluminum alloy), zinc foil, copper foil, and a laminate in which any of the above is combined. The print target is preferably a film in view of its light weight and high versatility such that it can package a liquid.
After the image-like ink is transferred to the printing object, a step of heating, ultraviolet (UV) irradiation, or Electron Beam (EB) irradiation may be included for curing the ink. In order to avoid the migration of residual solvents and low-molecular components and to cope with food packaging, it is more preferable to use EB ink including a step of irradiating with Electron Beams (EB).
In the case of water printing, since the fountain solution and the ink may be mixed to deteriorate the adhesion to the printing object and leave a solvent on the printing object, the cylindrical printing plate of the present invention is preferably formed of a waterless lithographic printing plate.
Examples
The present invention will be described in further detail below with reference to examples.
(1) Measurement of film thickness of ink repellent composition layer
Using a surface roughness/profile shape measuring machine SURFCOM 1400D (manufactured by tokyo corporation), the surface roughness/profile shape was measured at a measuring speed according to the test method of JIS B0601-2001: 0.3mm/s, measurement distance: the surface of each of the ink-attracting/ink-repellent functional layer and the ink-repellent composition layer of the cylindrical printing plate precursor was allowed to fall within the measurement range under the condition of 6mm, and the difference in level between the ink-attracting/ink-repellent functional layer and the ink-repellent composition layer was measured. The measurement was performed at any 5 points, and the average value thereof was taken as the film thickness of the ink repellent composition layer.
(2) Flexible package printing
Supplying ink of EB OFFSET ink "stearebaam" (manufactured by imperial corporation) (124525231124611256186) to an ink roller using a flexible packaging printer "OFFSET CI8" (manufactured by COMEXI corporation), and supplying ink to a cylindrical printing plate in such a manner that a full-thickness concentration of 12412561124881241254003647 installed on the plate cylinder becomes 1.8. The cylindrical printing plate is brought into contact with the blanket, and ink is transferred from the cylindrical printing plate to the blanket. Subsequently, offset printing was performed in which the ink on the blanket was transferred to a polypropylene film "P2111" (manufactured by toyobo co., ltd.).
(3) Determination of contaminant concentration in the gap
In the printing of (2) and (8), the printed matter obtained at the time of printing 1,000m was sampled, and the color filter was printed using a reflection spectrophotometer "SpectroEye" (manufactured by X-rite corporation) in the following manner: the concentration of the contaminated part of the gap was measured under black conditions. The measurement was performed at 5, and the average value thereof was defined as the concentration of the contaminant in the gap. If the reflection concentration is 0.1 or less, it is judged that there is no problem in practice, and it is preferably 0.05 or less, more preferably 0.01 or less.
(4) Measurement of paste Start temperature
In the printing in (2) and (8), printing was performed while controlling the plate surface temperature using a cooler. The plate surface temperature of the cylindrical printing plate was measured with a non-contact thermometer, and the paste of the non-drawn portion was confirmed for each temperature. The temperature at the time when pasting was confirmed was set as the pasting start temperature. When the paste start temperature is 28 ℃ or higher, it is judged that there is no problem in practice, and from the viewpoint of enabling more stable printing, it is preferably 30 ℃ or higher, and more preferably 35 ℃ or higher.
(5) Evaluation of durability
In the printing in the above (2) and (8), the ink-attracting/ink-repellent functional layer or the ink-repellent composition layer of the cylindrical printing plate is worn away, and the number of times (shot number) of contact between the cylindrical printing plate and the blanket at the time when the ink adheres to the non-drawn area region is set as the durability of the cylindrical printing plate. The durability of the cylindrical printing plate is 4,000shot or more, which is judged to have no practical problem, and is preferably 6,000shot or more, and more preferably 10,000shot or more.
(6) Evaluation of Productivity
The ease of production of the printing plate precursor was evaluated. In the application of the organic layer composition solution, the thermosensitive layer composition solution, and the silicone rubber layer composition solution, which will be described later, a was evaluated as a in the case where the coating could be continuously applied to a substrate without edge curling (124951247212461).
(7) SiO in ink repellent composition layer 4/2 Calculation of content of structural Unit
SiO in ink repellent composition layer 4/2 The content of the structural unit may be determined by solid state 29 Si NMR analysis. The ink repellent composition layer was cut off, and by the DD/MAS method using AVANCE400 (manufactured by Bruker corporation), the ratio of the number of the ink repellent composition layer in the measurement core: 29 si, spectral width: 40kHz, pulse width: 4.2 μ sec, pulse repetition time: ACQTM 0.02049 seconds, PD 140 seconds, observation point: 8192, reference substance: hexamethylcyclotrisiloxane (external reference: -9.66 ppm), temperature: 22 ℃, sample rotation speed: carried out under the condition of 4kHz 29 Si NMR measurement.
Subjecting the obtained 29 Peaks near chemical shifts 5-10ppm of the Si DD/MAS NMR spectrum are ascribed to R 3 SiO 1/2 Structural unit, the peak near 10-25ppm is attributed to R 2 SiO 2/2 Structural unit, the peak near 50-75ppm is assigned to RSiO 3/2 Structural unit, the peak near 85-125ppm is assigned to SiO 4/2 A structural unit.The peak area of each structural unit was measured to determine SiO 4/2 The ratio of the peak area of the structural unit to the total of the peak areas of the structural units was used to calculate the SiO content in the ink repellent composition layer 4/2 The content of the structural unit.
(8) Printing on flexible package with water
After a dampening solution was supplied to the plate surface of the cylindrical printing plate using a flexible packaging printer "OFFSET CI8" (manufactured by comixi corporation), ink of EB OFFSET ink "stearebaam" (manufactured by imperial corporation) was attached to the cylindrical printing plate so that the full plate concentration became 1.8. Next, the cylindrical printing plate is brought into contact with the blanket, and ink is transferred from the cylindrical printing plate to the blanket. Subsequently, offset printing was performed in which the ink on the blanket was transferred to a polypropylene film "P2111" (manufactured by toyobo co., ltd.).
(9) Surface roughness measurement
The surface roughness (arithmetic surface roughness Ra) of the ink repellent composition layer was measured by using a laser microscope "VK-9510" (manufactured by KEYENCE). The 200 × 200 μm region of the ink repellent composition layer filling the gap formed between the edges of the lithographic printing plate was measured using a 20-fold objective lens, and the average value at 10 was taken as the surface roughness.
[ example 1]
An anhydrous planographic printing plate-1 was produced by the following method. The organic layer composition solution was applied to a degreased aluminum substrate having a thickness of 0.30mm by a bar coater, and dried at 200 ℃ for 90 seconds to form an organic layer having a thickness of 10.0. Mu.m. The organic layer composition solution was obtained by mixing the following components at room temperature (20 to 28 ℃) with stirring.
< organic layer composition solution >
(a) Polymer with active hydrogen: epoxy resin: \\124566712540\ (registered trademark) 1010 (1257212515\\1249712531711252472125 (manufactured by strain) 125711252457: 35 parts by mass
(b) Polymer with active hydrogen: polyurethane: \\12469: 375 parts by mass
(c) \\ 1245011\\ 124611252488: \\ 12450501251112461\\ 1252488 (manufactured by Chuanchao 1250112412412412412412412412412412412412412412412412559 (manufactured by Sakawa 12511241241252312459: 10 parts by mass
(d) Leveling agent: \12487 (manufactured by Nanshenghua Nippon Kaisha) (manufactured by Tanzhiyama Kaisha, 10 mass percent of solid component): 1 part by mass
(e) Titanium oxide: v, N-dimethylformamide dispersion (titanium oxide 50 mass%) of "124792, \\ 12452061254063" (registered trademark) CR-50 (manufactured by shiyuensis industries, ltd.): 60 parts by mass
(f) N, N-dimethylformamide: 730 parts by mass
(g) Methyl ethyl ketone: 250 parts by mass.
Subsequently, the thermosensitive layer composition solution was coated on the organic layer by a bar coater, and dried by heating at 140 ℃ for 90 seconds, to provide a thermosensitive layer having a thickness of 1.5 μm. The thermosensitive layer composition solution was obtained by mixing the following components at room temperature (20 to 28 ℃) with stirring.
< thermosensitive layer composition solution >
(a) Infrared absorption dye (cyanine dye): NK5559 (manufactured by Rinko Co., ltd., maximum absorption wavelength: 774 nm): 16.0 parts by mass
(b) An organic complex compound: n-butyl bis (acetylacetonato) titanium: "124901254075\\12512," (registered trademark) titanium (manufactured by japan chemical industry, ltd. At a concentration of 73 mass%, n-butanol contained as a solvent: 27 mass%): 15.0 parts by mass
(c) Phenol formaldehyde novolac resin: \\ 124731121\\ 1245212488125247212531195 (registered trademark) (suma) PR53195 (sumo 125051254012463v/1245212488 (manufactured by strain) 125211251255212488: 60 parts by mass
(d) Polyurethane: \12491 (manufactured by Nippon patent Nos. \\ 1250922 (registered trademark) 5196 (manufactured by Nippon patent Nos. \\ 12522125791257912531 (manufactured by Nippon patent No.: 125247930% by mass) and containing 35% by mass of methyl ethyl ketone and 35% by mass of cyclohexanone as solvents: 25 parts by mass
(e) Tetrahydrofuran (tetrahydrofuran): 1044 parts by mass.
Subsequently, the silicone rubber layer composition solution-1 prepared immediately before coating was coated on the heat-sensitive layer by a bar coater, heated at 140 ℃ for 80 seconds, and provided with a silicone rubber layer having an average film thickness of 5.0 μm to obtain a waterless lithographic printing plate precursor. The silicone rubber layer composition solution-1 was obtained by mixing the following ingredients at room temperature with stirring.
< Silicone rubber layer composition solution-1 >
(a) α, ω -divinyl polydimethylsiloxane: DMS-V35 (weight average molecular weight 49,500, manufactured by GELEST Inc.): 86.26 parts by mass
(b) Methyl hydrogen siloxane-dimethyl siloxane copolymer RD-1 ((i)/((i) + (ii)) x 100=50 mol%, china jawed 125248012454\\124671259112512512591: 4.93 parts by mass
(c) Vinyltris (methylethylketoximino) silane: 2.64 parts by mass
(d) Platinum catalyst SRX212 (manufactured by jieyao 125242480\12454124671254091, 1253112464: 6.17 parts by mass
(e) \12450507797: 900 parts by mass
Here, the silicone rubber layer of the waterless lithographic printing plate precursor-1 is an ink-attracting/ink-repellent functional layer.
Further, as the ink repellent composition layer to be stuck to the gap of the waterless lithographic printing plate precursor-1, an ink repellent ribbon-1 was produced by the following method.
A prepared ribbon-1 repellent composition solution immediately before coating was coated on a bar coater in a range of # 12469850,12540125861254012512588647,12503647 (thickness: 0.1mm, manufactured by Saikagaku corporation) at 140 ℃ for 80 seconds to provide a silicone rubber layer having an average film thickness of 5.0 μm, thereby obtaining a ribbon-1. The ribbon-repellent ink-1 composition solution was obtained by stirring and mixing the following components at room temperature (20 to 28 ℃).
< ink repellent ribbon-1 composition solution >
(a) α, ω -divinyl polydimethylsiloxane: DMS-V35 (weight average molecular weight 49,500, manufactured by GELEST Inc.): 86 parts by mass
(b) Methyl hydrogen siloxane-dimethyl siloxane copolymer RD-1 ((i)/((i) + (ii)) x 100=50 mol%, china jawed 125248012454\\124671259112512512591: 5 parts by mass
(c) Vinyltris (methylethylketoximino) silane: 3 parts by mass
(d) Platinum catalyst SRX212 (manufactured by jieyao 125242480\12454124671254091, 1253112464: 6 parts by mass
(e) \12450507797: 900 parts by mass.
The waterless lithographic printing plate precursor-1 was wound around a plate cylinder of a flexible packaging printing press "OFFSET CI8" (manufactured by comixi) to form a cylindrical shape, and the ink repellent ribbon-1 was attached to the gap to obtain a cylindrical printing plate precursor. The productivity was A and the film thickness of the ink repellent composition layer was 105 μm as a result of evaluation by the methods (1) and (6).
A part of an ink application/repellent functional layer of the cylindrical printing plate precursor is pasted with a folder 1246912512461a folder 1241258612512512503647 (manufactured by Temple GmbH, ltd.) to form an ink application part, thereby obtaining the cylindrical printing plate.
The cylindrical printing plate thus obtained was evaluated by the methods (3) to (5) above, and as a result, the gap contamination was 0.1, which was practically no problem, the paste start temperature was 28 ℃, and the durability was 4,000shot.
[ example 2]
An anhydrous lithographic printing plate precursor-2 was obtained in the same manner as in example 1, except that the silicone rubber layer composition solution-1 was changed to the following silicone rubber layer composition solution-2. Here, the silicone rubber layer of the waterless lithographic printing plate precursor-2 is an ink-attracting/ink-repellent functional layer.
< Silicone rubber layer composition solution-2 >
(a) α, ω -divinyl polydimethylsiloxane: DMS-V35 (weight average molecular weight 49,500, manufactured by GELEST Inc.): 67.80 parts by mass
(b) Silicone oil: KF-96-50cs (weight average molecular weight: 3,780, surface tension: 20.8mN/m, boiling point: 150 ℃ C., manufactured by shin-Etsu chemical Co., ltd.): 20.0 parts by mass
(c) Methyl hydrogen siloxane-dimethyl siloxane copolymer RD-1 ((i)/((i) + (ii)) x 100=50 mol%, china jawed 125248012454\\124671259112512512591: 3.39 parts by mass
(d) Vinyltris (methylethylketoximino) silane: 2.64 parts by mass
(e) Platinum catalyst SRX212 (manufactured by jieyao 125242480\12454124671254091, 1253112464: 6.17 parts by mass
(f) \12450507797: 900 parts by mass
Further, as the ink repellent composition layer to be stuck to the gap of the waterless lithographic printing plate precursor-2, an ink repellent ribbon-2 was produced by the following method.
A ribbon-repellent ribbon-2 composition solution prepared immediately before coating was coated on a bar coater in a range of # 12469850, \\ 1246140882, \\ 124881254003647 (thickness: 0.1mm, manufactured by Saikagaku corporation), heated at 140 ℃ for 80 seconds, and provided with a silicone rubber layer having an average film thickness of 5.0 μm to obtain a ribbon-repellent ribbon 2. The repellent ribbon-2 composition solution was obtained by stirring and mixing the following components at room temperature (20 to 28 ℃).
< ink repellent ribbon-2 composition solution >
(a) α, ω -divinyl polydimethylsiloxane: DMS-V35 (weight average molecular weight 49,500, manufactured by GELEST Inc.): 82.9 parts by mass
(b) Silicone oil: KF-96-50cs (weight average molecular weight: 3,780, surface tension: 20.8mN/m, boiling point: 150 ℃ C., manufactured by shin-Etsu chemical Co., ltd.): 4 parts by mass of
(c) Methyl hydrogen siloxane-dimethyl siloxane copolymer RD-1 ((i)/((i) + (ii)) x 100=50 mol%, envoy 125248012454\\\1246712591: 4.1 parts by mass
(d) Vinyltris (methylethylketoximino) silane: 3 parts by mass
(e) Platinum catalyst SRX212 (yu er 125242454\12480124671254091; 6.0 mass% of platinum catalyst): 6 parts by mass
(f) \12450507797: 900 parts by mass
A cylindrical printing plate precursor and a cylindrical printing plate were obtained in the same manner as in example 1, except that the ink repellent ribbon-1 was changed to the ink repellent ribbon-2. The obtained cylindrical printing plate precursor was evaluated by the methods (1) and (6) above, and as a result, the productivity was a and the film thickness of the ink repellent composition layer was 105 μm.
The cylindrical printing plate thus obtained was evaluated by the methods (3) to (5) above, and as a result, the gap contamination was 0.05, the paste start temperature was 30 ℃, and the durability was 4,000shot.
[ example 3]
A cylindrical printing plate precursor and a cylindrical printing plate were obtained in the same manner as in example 2, except that the ink repellent ribbon-2 composition solution was changed to the following ink repellent ribbon-3 composition solution.
< ink repellent ribbon-3 composition solution >
(a) α, ω -divinyl polydimethylsiloxane: DMS-V35 (weight average molecular weight 49,500, manufactured by GELEST Inc.): 39 parts by mass
(b) Silicone oil: KF-96-50cs (weight average molecular weight: 3,780, surface tension: 20.8mN/m, boiling point: > 150 ℃ C., manufactured by shin-Etsu chemical industries, ltd.): 50 parts by mass
(c) Methyl hydrogen siloxane-dimethyl siloxane copolymer RD-1 ((i)/((i) + (ii)) x 100=50 mol%, envoy 125248012454\\\1246712591: 2 parts by mass of
(d) Vinyltris (methylethylketoximino) silane: 3 parts by mass
(e) Platinum catalyst SRX212 (manufactured by jieyao 125242480\12454124671254091, 1253112464: 6 parts by mass
(f) \\1245050507754: 900 parts by mass
The obtained cylindrical printing plate precursor was evaluated by the method (1) above, and the film thickness of the ink repellent composition layer was 105 μm.
The cylindrical printing plate thus obtained was evaluated by the methods (3) to (5) above, and as a result, there was no contamination with a gap, the paste start temperature was 35 ℃, and the durability was 4,000shot.
[ example 4]
A cylindrical printing plate precursor and a cylindrical printing plate were obtained in the same manner as in example 2 except that the thickness of \124699.
< ink repellent ribbon-4 composition solution >
(a) α, ω -divinyl polydimethylsiloxane: DMS-V35 (weight average molecular weight 49,500, manufactured by GELEST Inc.): 39 parts by mass
(b) Silicone oil: KF-96-50cs (weight average molecular weight: 3,780, surface tension: 20.8mN/m, boiling point: > 150 ℃ C., manufactured by shin-Etsu chemical industries, ltd.): 50 parts by mass
(c) Methyl hydrogen siloxane-dimethyl siloxane copolymer RD-1 ((i)/((i) + (ii)) x 100=50 mol%, envoy 125248012454\\\1246712591: 2 parts by mass
(d) Vinyltris (methylethylketoximino) silane: 3 parts by mass
(e) Platinum catalyst SRX212 (manufactured by jieyao 125242480\12454124671254091, 1253112464: 6 parts by mass
(f) \\1245050507754: 900 parts by mass
The obtained cylindrical printing plate precursor was evaluated by the method (1) above, and the film thickness of the ink repellent composition layer was 85 μm.
The cylindrical printing plate thus obtained was evaluated by the methods (3) to (5) above, and as a result, there was no contamination with a gap, the paste start temperature was 35 ℃ C., and the durability was 4,000shot.
[ example 5]
A cylindrical printing plate precursor and a cylindrical printing plate were obtained in the same manner as in example 2 except that the ink repellent ribbon-2 composition solution was changed to the following ink repellent ribbon-5 composition solution by a method of (124124124124124) 12412586 (125034) (thickness: 0.1mm, manufactured by Temple, inc.).
< ink repellent ribbon-5 composition solution >
(a) α, ω -divinyl polydimethylsiloxane: DMS-V35 (weight average molecular weight 49,500, manufactured by GELEST Inc.): 67.6 parts by mass
(b) Silicone oil: KF-96-50cs (weight average molecular weight: 3,780, surface tension: 20.8mN/m, boiling point: 150 ℃ C., manufactured by shin-Etsu chemical Co., ltd.): 20 parts by mass
(c) Methyl hydrogen siloxane-dimethyl siloxane copolymer RD-1 ((i)/((i) + (ii)) x 100=50 mol%, envoy 125248012454\\\1246712591: 3.4 parts by mass
(d) Vinyltris (methylethylketoximino) silane: 3 parts by mass
(e) Platinum catalyst SRX212 (manufactured by jieyao 125242480\12454124671254091, 1253112464: 6 parts by mass
(f) \\1245050507754: 900 parts by mass
The obtained cylindrical printing plate precursor was evaluated by the method (1) above, and the film thickness of the ink repellent composition layer was 40 μm.
The cylindrical printing plate thus obtained was evaluated by the methods (3) to (5) above, and as a result, there was no contamination with a gap, the paste start temperature was 35 ℃ and the durability was 10,000shot and good.
[ example 6]
The ink repellent transfer tape-5 was obtained by applying a solution of the ink repellent ribbon-5 composition prepared immediately before application to polyethylene terephthalate "v 12523112521125409" (registered trademark) F99 (manufactured by imperial society, manufactured by imperial society of china, 125242450) by a bar coater and heating at 100 ℃ for 10 seconds to provide a semi-cured silicone rubber layer having an average film thickness of 5.0 μm.
An ink repellent transfer belt 5 was attached to the gap between the cylindrical waterless lithographic printing plate precursor-2 so as to fill the gap on the silicone rubber layer side, and the silicone rubber layer was cured by heating at 160 ℃ for 60 seconds from above F99 using a trowel-shaped heater. Then, F99 was peeled off to obtain a cylindrical printing plate precursor.
The film thickness of the ink repellent composition layer was 5 μm as a result of evaluation by the method (1).
A '647' (thickness: 0.1mm, manufactured by tomb corporation) of 1246912540\124611258812586125125031254. The cylindrical printing plate thus obtained was evaluated by the methods (3) to (5) above, and as a result, contamination with a gap was not caused, the paste start temperature was 35 ℃ and the durability was 20,000shot, which was very good.
[ example 7]
A cylindrical printing plate precursor and a cylindrical printing plate were obtained in the same manner as in example 2, except that the ink repellent ribbon-2 was attached to the gap of the waterless lithographic printing plate precursor-2 formed in a cylindrical shape, and the following ink repellent composition-1 was filled in the gap and cured at room temperature.
< ink repellent composition-1 >
(a) α, ω -both terminal silanol-based polydimethylsiloxane: DMS-S33 (weight average molecular weight 43,500, manufactured by GELEST Inc.): 35.72 parts by mass
(b) Methyl triacetoxysilane: 3 parts by mass
(c) Tetrakis (methylethylketoximino) silane: 1 part by mass
(d) Dibutyl tin diacetate: 0.28 part by mass
(e) \124505070 (1247797, (registered trademark) E (manufactured by 124561248377: 60 parts by mass
The content of the compound represented by the general formula (III) was 25% by mass based on the total of the compound represented by the general formula (II) and the compound represented by the general formula (III).
The obtained cylindrical printing plate precursor was evaluated by the method (1) above, and the film thickness of the ink repellent composition layer was 5 μm.
The cylindrical printing plate thus obtained was evaluated by the methods (3) to (5) above, and as a result, the gap contamination was 0.1, which was practically no problem, and the paste start temperature was 28 ℃ and the durability was 20,000shot, which was very good.
[ example 8]
A cylindrical printing plate precursor and a cylindrical printing plate were obtained in the same manner as in example 2, except that the ink repellent ribbon-2 was attached to the gap of the waterless planographic printing plate-2 formed in a cylindrical shape, and the following ink repellent composition-2 was filled in the gap and cured at room temperature.
< ink repellent composition-2 >
(a) α, ω -both terminal silanol group polydimethylsiloxane: DMS-S33 (weight average molecular weight 43,500, manufactured by GELEST Inc.): 34.72 parts by mass
(b) Silicone oil: KF-96-50cs (weight average molecular weight: 3,780, surface tension: 20.8mN/m, boiling point: 150 ℃ C., manufactured by shin-Etsu chemical Co., ltd.): 20 parts by mass
(c) Methyl triacetoxysilane: 11.25 parts by mass
(d) Tetrakis (methylethylketoximino) silane: 3.75 parts by mass
(e) Dibutyl tin diacetate: 0.28 part by mass
(f) \124505070 (1247797, (registered trademark) E (manufactured by 124561248377: 30 parts by mass
The content of the compound represented by the general formula (III) was 25% by mass based on the total of the compound represented by the general formula (II) and the compound represented by the general formula (III).
The obtained cylindrical printing plate precursor was evaluated by the method (1) above, and the film thickness of the ink repellent composition layer was 5 μm.
The cylindrical printing plate thus obtained was evaluated by the methods (3) to (5) above, and as a result, contamination with a gap was not caused, the paste start temperature was 35 ℃ and the durability was 20,000shot, which was very good.
[ example 9]
A cylindrical printing plate precursor and a cylindrical printing plate were obtained in the same manner as in example 2 except that the following ink repellent composition-3 was charged into the gap of the waterless planographic printing plate-2 formed in a cylindrical shape instead of sticking the ink repellent ribbon-2, and the mixture was heated at 160 ℃ for 60 seconds to cure the ink repellent ribbon-3 by contact with a trowel-shaped heater.
< ink repellent composition-3 >
(a) α, ω -both terminal silanol group polydimethylsiloxane: DMS-S33 (weight-average molecular weight 43,500, manufactured by GELEST Inc.): 39.72 parts by mass
(b) Silicone oil: KF-96-50cs (weight average molecular weight: 3,780, surface tension: 20.8mN/m, boiling point: > 150 ℃ C., manufactured by shin-Etsu chemical industries, ltd.): 20 parts by mass
(c) Methyl triacetoxysilane: 7.5 parts by mass
(d) Tetrakis (methylethylketoximino) silane: 2.5 parts by mass
(e) Dibutyl tin diacetate: 0.28 part by mass
(f) \124505070 (1247797, (registered trademark) E (manufactured by 124561248377: 30 parts by mass
The content of the compound represented by the general formula (III) was 25% by mass based on the total of the compound represented by the general formula (II) and the compound represented by the general formula (III).
The obtained cylindrical printing plate precursor was evaluated by the method (1) above, and the film thickness of the ink repellent composition layer was 5 μm.
The cylindrical printing plate thus obtained was evaluated by the methods (3) to (5) above, and as a result, the plate had no contamination with a gap, the plate start temperature was 35 ℃ and the durability was 20,000shot, which was very good.
[ example 10]
A cylindrical printing plate precursor and a cylindrical printing plate were obtained in the same manner as in example 2, except that the following ink repellent composition-4 was filled in the gap of the waterless lithographic printing plate precursor-2 formed in a cylindrical shape instead of the ink repellent ribbon-2 being stuck and cured at room temperature.
< ink repellent composition-4 >
(a) α, ω -both terminal silanol-based polydimethylsiloxane: DMS-S33 (weight average molecular weight 43,500, manufactured by GELEST Inc.): 30.22 parts by mass
(b) Silicone oil: KF-96-50cs (weight average molecular weight: 3,780, surface tension: 20.8mN/m, boiling point: 150 ℃ C., manufactured by shin-Etsu chemical Co., ltd.): 20 parts by mass
(c) Methyl triacetoxysilane: 18 parts by mass of
(d) Tetrakis (methylethylketoximino) silane: 1.5 parts by mass
(e) Dibutyltin diacetate: 0.28 part by mass
(f) \12450505070 \\\\\ 1247797 (registered trademark) E (manufactured by (124561248377): 30 parts by mass
The content of the compound represented by the general formula (III) was 7.7% by mass based on the total of the compound represented by the general formula (II) and the compound represented by the general formula (III).
The obtained cylindrical printing plate precursor was evaluated by the methods (1) and (7), and as a result, the film thickness of the ink repellent composition layer was 5 μm, and SiO in the ink repellent composition layer 4/2 The content of the structural unit was 0.55%.
The cylindrical printing plate thus obtained was evaluated by the methods (3) to (5) above, and as a result, there was no contamination with a gap, the paste start temperature was 35 ℃ and the durability was 8,000shot and good.
[ example 11]
A cylindrical printing plate precursor and a cylindrical printing plate were obtained in the same manner as in example 2, except that the following ink repellent composition-5 was filled in the gap of the waterless planographic printing plate-2 formed in a cylindrical shape instead of sticking the ink repellent ribbon-2, and the mixture was cured at room temperature.
< ink repellent composition-5 >
(a) α, ω -both terminal silanol-based polydimethylsiloxane: DMS-S33 (weight-average molecular weight 43,500, manufactured by GELEST Inc.): 37.72 parts by mass
(b) Silicone oil: KF-96-50cs (weight average molecular weight: 3,780, surface tension: 20.8mN/m, boiling point: > 150 ℃ C., manufactured by shin-Etsu chemical industries, ltd.): 10 parts by mass
(c) Methyl triacetoxysilane: 19.8 parts by mass
(d) Tetrakis (methylethylketoximino) silane: 2.2 parts by mass
(e) Dibutyltin diacetate: 0.28 part by mass
(f) \124505070 (1247797, (registered trademark) E (manufactured by 124561248377: 30 parts by mass
The content of the compound represented by the general formula (III) was 10% by mass based on the total of the compound represented by the general formula (II) and the compound represented by the general formula (III).
The obtained cylindrical printing plate precursor was evaluated by the methods (1) and (7), and as a result, ink repellency was obtainedThe film thickness of the composition layer was 5 μm, and the SiO in the ink repellent composition layer 4/2 The content of the structural unit was 0.83%.
The cylindrical printing plate thus obtained was evaluated by the methods (3) to (5) above, and as a result, there was no contamination with a gap, the paste start temperature was 33 ℃, and the durability was good at 15,000shot, which was very good.
[ example 12]
A cylindrical printing plate was obtained in the same manner as in example 2, except that the following ink repellent composition-6 was filled in the gap of the waterless planographic printing plate-2 formed in a cylindrical shape instead of sticking the ink repellent ribbon-2, and the mixture was cured at room temperature.
< ink repellent composition-6 >
(a) α, ω -both terminal silanol group polydimethylsiloxane: DMS-S33 (weight average molecular weight 43,500, manufactured by GELEST Inc.): 44.72 parts by mass
(b) Silicone oil: KF-96-50cs (weight average molecular weight: 3,780, surface tension: 20.8mN/m, boiling point: > 150 ℃ C., manufactured by shin-Etsu chemical industries, ltd.): 10 parts by mass of
(c) Methyl triacetoxysilane: 12 parts by mass
(d) Tetrakis (methylethylketoximino) silane: 3 parts by mass
(e) Dibutyltin diacetate: 0.28 part by mass
(f) \12450505070 \\\\\ 1247797 (registered trademark) E (manufactured by (124561248377): 30 parts by mass
The content of the compound represented by the general formula (III) was 20% by mass based on the total of the compound represented by the general formula (II) and the compound represented by the general formula (III).
The obtained cylindrical printing plate precursor was evaluated by the methods (1) and (7), and as a result, the film thickness of the ink repellent composition layer was 5 μm, and SiO in the ink repellent composition layer 4/2 The content of the structural unit was 1.04%.
The cylindrical printing plate thus obtained was evaluated by the methods (3) to (5) above, and as a result, there was no contamination with a gap, the paste start temperature was 33 ℃ and the durability was 20,000shot, which was excellent.
[ example 13]
A cylindrical printing plate precursor and a cylindrical lithographic printing plate were obtained in the same manner as in example 2, except that the following ink repellent composition-7 was filled in place of the ink repellent ribbon-2 stuck to the gap of the waterless lithographic printing plate-2 formed in a cylindrical shape and cured at room temperature.
< ink repellent composition-7 >
(a) α, ω -both terminal silanol-based polydimethylsiloxane: DMS-S33 (weight average molecular weight 43,500, manufactured by GELEST Inc.): 33.72 parts by mass
(b) Silicone oil: KF-96-50cs (weight average molecular weight: 3,780, surface tension: 20.8mN/m, boiling point: > 150 ℃ C., manufactured by shin-Etsu chemical industries, ltd.): 20 parts by mass
(c) Methyl triacetoxysilane: 12 parts by mass
(d) Tetrakis (methylethylketoximino) silane: 4 parts by mass
(e) Dibutyl tin diacetate: 0.28 part by mass
(f) \12450505070 \\\\\ 1247797 (registered trademark) E (manufactured by (124561248377): 30 parts by mass
The content of the compound represented by the general formula (III) was 25% by mass based on the total of the compound represented by the general formula (II) and the compound represented by the general formula (III).
The obtained cylindrical printing plate precursor was evaluated by the methods (1) and (7) described above, and as a result, the film thickness of the ink repellent composition layer was 5 μm, and SiO in the ink repellent composition layer 4/2 The content of the structural unit was 1.41%.
The cylindrical printing plate thus obtained was evaluated by the methods (3) to (5) above, and as a result, contamination with a gap was not caused, the paste start temperature was 35 ℃ and the durability was 20,000shot, which was very good.
[ example 14]
A cylindrical printing plate precursor and a cylindrical printing plate were obtained in the same manner as in example 2, except that the following ink repellent composition-8 was filled in place of the ink repellent tape-2 stuck in the gap of the waterless planographic printing plate-2 formed in a cylindrical shape and cured at room temperature.
< ink repellent composition-8 >
(a) α, ω -both terminal silanol-based polydimethylsiloxane: DMS-S33 (weight average molecular weight 43,500, manufactured by GELEST Inc.): 35.72 parts by mass
(b) Silicone oil: KF-96-50cs (weight average molecular weight: 3,780, surface tension: 20.8mN/m, boiling point: 150 ℃ C., manufactured by shin-Etsu chemical Co., ltd.): 20 parts by mass
(c) Methyl triacetoxysilane: 7 parts by mass
(d) Tetrakis (methylethylketoximino) silane: 7 parts by mass
(e) Dibutyl tin diacetate: 0.28 part by mass
(f) \124505070 (1247797, (registered trademark) E (manufactured by 124561248377: 30 parts by mass
The content of the compound represented by the general formula (III) was 50% by mass based on the total of the compound represented by the general formula (II) and the compound represented by the general formula (III).
The obtained cylindrical printing plate precursor was evaluated by the methods (1) and (7), and as a result, the film thickness of the ink repellent composition layer was 5 μm, and SiO in the ink repellent composition layer 4/2 The content of the structural unit was 2.43%.
The cylindrical printing plate thus obtained was evaluated by the methods (3) to (5) above, and as a result, the plate had no contamination with a gap, the plate start temperature was 35 ℃, and the durability was 12,000shot, which was very good.
[ example 15]
A cylindrical printing plate precursor and a cylindrical printing plate were obtained in the same manner as in example 2, except that the following ink repellent composition-9 was filled in the gap of the waterless planographic printing plate-2 formed in a cylindrical shape instead of sticking the ink repellent ribbon-2, and the mixture was cured at room temperature.
< ink repellent composition-9 >
(a) α, ω -both terminal silanol group polydimethylsiloxane: DMS-S33 (weight average molecular weight 43,500, manufactured by GELEST Inc.): 37.72 parts by mass
(b) Silicone oil: KF-96-50cs (weight average molecular weight: 3,780, surface tension: 20.8mN/m, boiling point: > 150 ℃ C., manufactured by shin-Etsu chemical industries, ltd.): 20 parts by mass
(c) Methyl triacetoxysilane: 3 parts by mass
(d) Tetrakis (methylethylketoximino) silane: 9 parts by mass
(e) Dibutyl tin diacetate: 0.28 part by mass
(f) \124505070 (1247797, (registered trademark) E (manufactured by 124561248377: 30 parts by mass
The content of the compound represented by the general formula (III) was 75% by mass based on the total of the compound represented by the general formula (II) and the compound represented by the general formula (III).
The obtained cylindrical printing plate precursor was evaluated by the methods (1) and (7), and as a result, the film thickness of the ink repellent composition layer was 5 μm, and SiO in the ink repellent composition layer 4/2 The content of the structural unit was 3.07%.
The cylindrical printing plate thus obtained was evaluated by the methods (3) to (5) above, and as a result, there was no contamination with a gap, the paste start temperature was 35 ℃ and the durability was 8,000shot and good.
[ example 16]
A cylindrical printing plate precursor and a cylindrical printing plate were obtained in the same manner as in example 13, except that the ink repellent composition-7 was filled, and then flattened with a squeegee, and cured by heating at 150 ℃ for 30 seconds using an electric iron. The obtained cylindrical printing plate precursor was evaluated by the method of (9) above, and as a result, the arithmetic surface roughness Ra of the planarized ink repellent composition-7 layer was 0.20 μm.
The cylindrical printing plate thus obtained was evaluated by the methods (3) and (5), and as a result, contamination with a gap was not caused, and the durability was very good at 25,000shot.
[ example 17]
A water-bearing lithographic printing plate SUPERIA ZP (manufactured by FUJIFILM) having a 200 × 200mm full-plate image portion provided at the center thereof was wound around a plate cylinder of a soft packing printing machine "OFFSET CI8" (manufactured by comixi) to form a cylindrical shape, and a gap formed between the ends of the water-bearing lithographic printing plate was filled with the ink repellent composition-10 described below prepared by stirring at room temperature, and dried at room temperature to produce a cylindrical printing plate. The evaluation was made by the method of (9) above, and as a result, the arithmetic surface roughness Ra of the ink repellent composition-10 layer was 0.52. Mu.m. Then, the water-containing flexible package printing of the above (8) was performed.
< ink repellent composition-10 >
(a) Water: 85% by mass
(b) Gum arabic (manufactured by japan powder medicine corporation): 10% by mass
(c) Benzyl alcohol: 2.5% by mass
(d) Hexametaphosphoric acid: 2% by mass
(e) Sodium dodecylbenzenesulfonate: 0.5% by mass
The results of the evaluation by the methods (3) and (5) above showed no contamination with a gap, and the durability was 25,000shot, which was very good.
[ example 18]
A cylindrical printing plate precursor and a cylindrical printing plate were obtained in the same manner as in example 17 except that the following ink repellent composition-11 prepared by stirring at room temperature was used instead of the ink repellent composition-10. The obtained cylindrical printing plate precursor was evaluated by the method of (9) above, and as a result, the arithmetic surface roughness Ra of the ink repellent composition-11 layer was 0.48 μm. Then, the water-containing flexible package printing of the above (8) was performed.
< ink repellent composition-11 >
(a) Water: 80% by mass
(b) A resol-type phenol resin (v/v) \\ 1250112455 (v/v) \ 124941241252112452124 (manufactured by DIC corporation): 19% by mass
(c) P-toluenesulfonic acid: 1% by mass
As a result of evaluation by the methods (3) and (5), the contamination of the gap was 0.1, which was not problematic in practical use, and the durability was 8,000shot, which was good.
[ example 19]
A cylindrical printing plate precursor and a cylindrical printing plate were obtained in the same manner as in example 18, except that the gap formed between the ends of the lithographic printing plate precursor was filled with the ink repellent composition-11 and heated at 150 ℃ for 30 seconds using an electric iron. The obtained cylindrical printing plate precursor was evaluated by the method of (9) above, and as a result, the arithmetic surface roughness Ra of the ink repellent composition-11 layer was 0.35 μm. Then, the water-containing flexible package printing of the above (8) was performed.
As a result of evaluation by the methods (3) and (5), the contamination of the gap was 0.05, and the durability was 15,000shot, which was very good.
[ example 20]
A cylindrical printing plate precursor and a cylindrical printing plate were obtained in the same manner as in example 18, except that the gap formed between the edges of the lithographic printing plate was filled with the ink repellent composition-11, flattened with a squeegee, and heated at 150 ℃ for 30 seconds using an electric iron. The obtained cylindrical printing plate precursor was evaluated by the method of (9) above, and as a result, the arithmetic surface roughness Ra of the planarized ink repellent composition-11 layer was 0.20 μm. Then, the water-containing flexible package printing of the above (8) was performed.
As a result of evaluation by the methods (3) and (5), contamination with a gap was not caused, and the durability was 20,000shot, which was very good.
Comparative example 1
A cylindrical printing plate precursor and a cylindrical printing plate were obtained in the same manner as in example 1, except that the ink repellent ribbon-1 was not stuck to the gap between the waterless planographic printing plate-1 formed in a cylindrical shape.
As a result of evaluation by the methods (3) to (5), the plate pasting starting temperature was 28 ℃ and the durability was 20,000shot, which were very good, but the contamination of the gap was 1.0, which resulted in a result that it was not practical.
Comparative example 2
A cylindrical printing plate precursor was produced in the same manner as in example 1, except that the silicone rubber layer composition solution-1 and the heat-sensitive layer composition solution were applied in this order to a degreased cylindrical aluminum substrate having a thickness of 0.30 mm. Here, the heat sensitive layer composition solution is applied so as to cover half in the width direction of a silicone rubber layer provided on a cylindrical aluminum substrate.
The cylindrical printing plate precursor is produced by coating 1 cylindrical aluminum substrate, and when a heat-sensitive layer composition solution is coated on a silicone rubber layer having a low surface free energy, edge curling often occurs, and thus productivity is significantly poor.
Using the obtained cylindrical printing plate precursor, a cylindrical printing plate was obtained in the same manner as in example 1. The obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, and as a result, the cylindrical printing plate was coated in a cylinder, and therefore, the plate was free from contamination with a gap, and the plate pasting start temperature was 28 ℃.
[ Table 1]
[ Table 2]
[ Table 3]
Description of the symbols
1. Substrate material
2. Organic layer
3. Thermosensitive layer
4. Ink-receptive/repellent functional layer
5. Gap between the two plates
6. Ink repellent composition or ink repellent composition layer
Film thickness of 6H ink repellent composition layer
100. Lithographic printing plate precursor or lithographic printing plate
200. Lithographic printing plate precursor formed into cylindrical shape or lithographic printing plate formed into cylindrical shape
300. A cylindrical printing plate precursor or a cylindrical printing plate.
Claims (22)
1. A method for manufacturing a cylindrical printing plate, comprising the steps of: and a step of winding the lithographic printing plate or the lithographic printing plate precursor around a cylindrical support and filling the gap between the ends of the lithographic printing plate or the lithographic printing plate precursor with an ink-repellent composition.
2. The method for manufacturing a cylindrical printing plate according to claim 1, wherein a length of the gap in a circumferential direction is 5mm or less.
3. The method for manufacturing a cylindrical printing plate according to claim 1 or 2, the ink repellent composition comprising an organosilicon compound.
4. The method for manufacturing a cylindrical printing plate according to any one of claims 1 to 3, wherein the ink repellent composition contains 5 to 50% by mass of silicone oil.
5. The method for manufacturing a cylindrical printing plate according to claim 3 or 4, the organosilicon compound comprising SiO 4/2 A structural unit.
6. The method for manufacturing a cylindrical printing plate according to claim 5, siO contained in the organosilicon compound 4/2 Structural unit relative to R 3 SiO 1/2 Structural unit, R 2 SiO 2/2 Structural unit, RSiO 3/2 Structural unit and SiO 4/2 The total of the structural units is 0.8 to 2.5 percent.
7. The method for manufacturing a cylindrical printing plate according to claim 1 or 2, the ink repellent composition comprising a hydrophilic compound.
8. The method for manufacturing a cylindrical printing plate according to claim 7, wherein the hydrophilic compound contains a water-soluble resin.
9. The method for manufacturing a cylindrical printing plate according to claim 8, the water-soluble resin having a vinyl group and/or a hydroxymethyl group.
10. The method for manufacturing a cylindrical printing plate according to any one of claims 1 to 9, comprising the following steps after the gap is filled with the ink repellent composition: a step of flattening the ink repellent composition and/or a step of heating the ink repellent composition.
11. The method for manufacturing a cylindrical printing plate according to any one of claims 1 to 9, wherein the ink repellent composition is a tape having an ink repellent surface.
12. The method for manufacturing a cylindrical printing plate according to any one of claims 1 to 11, wherein an ink repellent composition layer having a film thickness of 1 to 100 μm is formed using the ink repellent composition.
13. The method for manufacturing a cylindrical printing plate according to any one of claims 1 to 12, wherein an ink repellent composition layer having an arithmetic surface roughness Ra of 0.3 μm or less is formed using the ink repellent composition.
14. The method for manufacturing a cylindrical printing plate according to any one of claims 1 to 13, wherein the cylindrical support includes a detachable sleeve.
15. The method of manufacturing a cylindrical printing plate according to claim 14, the sleeve comprising glass fibers and/or aluminum.
16. A method for manufacturing a printed matter, comprising the steps of: a step of attaching ink to the surface of the cylindrical printing plate obtained by the method according to any one of claims 1 to 15; and a step of transferring the ink to a printing object directly or via a blanket.
17. The method of manufacturing a printed matter according to claim 16, comprising, before the step of adhering ink to the surface of the cylindrical printing plate, the steps of: and applying an ink repellent liquid to the surface of the cylindrical printing plate.
18. The method of manufacturing a printed matter according to claim 16 or 17, the cylindrical printing plate is constituted by at least a waterless planographic printing plate.
19. The method for manufacturing a printed matter according to any one of claims 16 to 18, wherein the step of transferring the ink to the object to be printed via a blanket comprises: and heating the ink transferred to the blanket.
20. The method for manufacturing a printed matter according to any one of claims 16 to 19, comprising, after the step of transferring the ink to the object to be printed directly or via a blanket, the steps of: and irradiating the ink transferred to the printing object with an electron beam.
21. The method for producing a printed matter according to any one of claims 16 to 20, wherein the printed matter is a film.
22. The method of manufacturing a printed matter according to any one of claims 16 to 21, wherein the object to be printed is transported in a roll-to-roll manner.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| JP2020-050592 | 2020-03-23 | ||
| JP2020050592 | 2020-03-23 | ||
| JP2020-184214 | 2020-11-04 | ||
| JP2020184214 | 2020-11-04 | ||
| PCT/JP2021/011353 WO2021193423A1 (en) | 2020-03-23 | 2021-03-19 | Cylindrical printing plate and method for manufacturing printed matter |
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| Country | Link |
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| JP (1) | JP7371684B2 (en) |
| CN (1) | CN115298040A (en) |
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| JPWO2021193423A1 (en) | 2021-09-30 |
| JP7371684B2 (en) | 2023-10-31 |
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