WO2021193423A1 - Cylindrical printing plate and method for manufacturing printed matter - Google Patents

Abstract

The present invention provides a cylindrical printing plate that prevents printed matter from being stained with ink and has excellent durability. The present invention relates to a method for manufacturing a cylindrical printing plate, the method including: a step of winding a lithographic printing plate or a lithographic printing plate original plate around a cylindrical support body and filling an ink repellent composition into a gap between ends of the lithographic printing plate or the lithographic printing plate original plate.

Description

Cylindrical printing plate and printed matter manufacturing method

The present invention relates to a method for manufacturing a cylindrical printed plate and a printed matter.

In the printing market, the packaging material and label fields are growing under the influence of the expansion of the beverage / lunch market, the progress of high-mix / small-lot production, and the diversification of designs. In these fields, printed matter is mainly produced by continuous printing by a roll-to-roll method, and gravure printing, flexographic printing, resin letterpress printing and the like are generally used.

Waterless lithographic printing, which has a short plate-making process time and enables higher-definition printing, has also been proposed in the packaging materials and label fields. However, since the waterless lithographic printing plate is in the form of a sheet, when the lithographic printing plate is attached in the circumferential direction of the printing press cylinder, if the lithographic printing plate is shorter than the outer peripheral length of the cylinder, a margin is created between the patterns printed on the original fabric. Therefore, there is a problem that post-processing such as trimming becomes complicated. On the other hand, the lithographic printing plate is longer than the outer circumference of the cylinder, and when the printing plate is held and fixed in the cylinder gap (groove), ink adheres to the gap in the grip, resulting in a linear shape that imitates the gap. There was a problem of causing stains on printed matter.

In response to these problems, for example, in Patent Document 1, a silicone resin layer is seamlessly formed on a cylindrical base material so that a gap to which ink adheres is not formed in the first place, and an ink-carrying resist pattern portion is formed on the silicone resin layer. A provided silicone underlayer type cylindrical waterless printing plate is disclosed.

International Publication No. 2017/07782

However, in the silicone lower layer type cylindrical waterless printing plate as disclosed in Patent Document 1, since the ink inking property pattern is resist-formed on the silicone resin layer having low surface free energy, the silicone resin is formed during printing. There is a problem that peeling easily occurs at the interface between the layer and the ink inking property pattern, and the durability in the production of printed matter is low.

Therefore, an object of the present invention is to provide a method for producing a cylindrical printing plate, which suppresses ink stains on printed matter and has excellent durability.

In the method for producing a cylindrical printing plate according to the present invention, a lithographic printing plate or a lithographic printing plate original plate is wound around a cylindrical support, and an ink repulsive composition is formed in a gap between the ends of the lithographic printing plate or the lithographic printing plate original plate. It is a method of manufacturing a cylindrical printing plate having a step of filling. Further, the method for producing a printed matter according to the present invention includes a step of adhering ink to the surface of a cylindrical printing plate obtained by the method of the present invention and a step of transferring the ink directly or via a blanket to a printed matter. It is a manufacturing method of a printed matter including.

According to the present invention, it is possible to obtain a cylindrical printing plate which suppresses ink stains on printed matter and has excellent durability.

It is a schematic cross-sectional view which shows an example of the shape of the planographic printing plate original plate. It is a schematic cross-sectional view which shows an example of the shape of (A) the lithographic printing plate original plate formed into a cylinder, and (B) the shape of the cylindrical printing plate original plate which filled the gap with an ink repulsion composition.

Hereinafter, a mode for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be variously modified and implemented according to an object and an application.

(Cylindrical printing plate original)
The cylindrical printing plate original plate in the present invention is a cylindrical printing plate original plate in which at least a base material and an ink inking / repulsion functional layer are provided in this order, and is produced by molding a lithographic printing plate original plate into a cylindrical shape. be able to. Hereinafter, the original cylindrical printing plate according to the present invention will be described with reference to the drawings.

As shown in FIG. 1, the planographic printing plate original plate 100 has at least a base material 1 and an ink inking / repulsion functional layer 4 in this order. Optionally, an organic layer 2 and / or a heat-sensitive layer 3 may be provided between the base material 1 and the ink inking / repulsion functional layer 4. If the lithographic printing plate original plate 100 is a waterless lithographic printing plate original plate, the ink inking / repulsion function layer 4 is ink repulsive, and any of the base material 1, the organic layer 2, and the heat sensitive layer 3 is inked. Has sex. On the other hand, in the case of the lithographic printing plate original plate with water, the ink-embedded / repulsive functional layer 4 is ink-embedded, and any of the base material 1, the organic layer 2, and the heat-sensitive layer 3 received the dampening water. Sometimes it develops ink resilience.

As shown in FIG. 2 (A), the end portion of the lithographic printing plate original plate 100 is curved toward the base material 1, and the ink inking / repulsion functional layers 4 at the curved end portion of the lithographic printing plate original plate 100 are adjacent to each other. Alternatively, they come into contact with each other and formed into a cylindrical shape so as to form a gap 5, to prepare a lithographic printing plate original plate 200 formed into a cylindrical shape, and then, as shown in FIG. 2 (B), the gap 5 has an ink repulsive composition. By filling with the material 6, the cylindrical printing plate original plate 300 can be produced.

In the cylindrical printing plate original plate of the present invention, the existing lithographic printing plate original plate can be used as compared with the conventional cylindrical printing plate original plate manufactured by providing an ink inking / repulsion functional layer on each cylindrical base material one by one. Therefore, it is preferable in terms of productivity.

In the production of the cylindrical printing plate original plate 300, the lithographic printing plate original plate 100 is wound around an exposure machine, a plate cylinder provided in the printing machine, and a cylindrical support such as a metal and plastic cylinder to form a cylindrical shape. It is preferable to produce the molded planographic printing plate original plate 200 from the viewpoint of handleability.

It is preferable that the ink inking / repulsion function layer 4 and the ink repulsion composition layer 6 are continuously present on the outermost surface of the cylindrical printing plate original plate 300. "Continuously present" means that the ink inking / repulsion function layer 4 or the ink repulsion composition layer 6 is present without interruption on the outermost surface of the cylindrical printing plate original plate. Here, the outermost surface refers to the surface of the outermost layer in the entire cylindrical printing plate original plate.

It is preferable that the ink inking / repulsion function layer 4 and the ink repulsion composition layer 6 are continuously present on the outermost surface of the cylindrical printing plate original plate 300. When the printed matter is produced using the cylindrical printing plate original plate by continuously presenting the ink inking / repulsion function layer 4 and the ink repulsive composition layer 6 on the outermost surface of the cylindrical printing plate original plate 300. It is possible to suppress the accumulation of ink in the gaps of the printing plate and further suppress the ink stains on the printed matter. Further, it is more preferable that the cylindrical printing plate original plate 300 has at least a portion where the base material 1, the ink inking / repulsion function layer 4, and the ink repulsion composition layer 6 are laminated in this order.

(Cylindrical printing plate)
The cylindrical printing plate in the present invention is a cylindrical printing plate in which at least a base material and an ink inking / repulsion functional layer are provided in this order, and an image portion and a non-image portion are formed on the cylindrical printing plate original plate. It is a thing. Hereinafter, the cylindrical printing plate in the present invention will be described with reference to the drawings.

The cylindrical printing plate in the present invention is produced by forming an image on the above-mentioned cylindrical printing plate original plate 300 by ablation with a carbon dioxide laser, an excimer laser, a YAG laser, physical cutting with a metal / diamond bite, or the like. be able to. In the lithographic printing plate original plate 100 as shown in FIG. 1, any one of the organic layer 2, the heat sensitive layer 3, and the ink inking / repulsion function layer 4 has a function of being exposed to near infrared light to form an image. In this case, since the image can be formed by a general-purpose semiconductor laser having an emission wavelength region in the vicinity of the near infrared region, it is preferable in that the plate making speed is high.

Further, after the lithographic printing plate original plate 100 is exposed or exposed and developed to form an image, the end portion of the lithographic printing plate 100 is bent toward the base material 1, and the ink filling / repulsion function of the bent end portion of the lithographic printing plate is performed. By forming a lithographic printing plate 200 formed into a cylindrical shape so that the layers 4 are adjacent to each other or in contact with each other to form a gap 5, the gap 5 is filled with the ink repulsive composition 6. , Cylindrical printing plate 300 can also be manufactured.

When the printed matter is produced using the cylindrical printing plate by the ink inking / repulsion function layer 4 and the ink repulsion composition layer 6 being continuously present on the outermost surface of the cylindrical printing plate 300, the printed matter is printed. Ink accumulation can be suppressed in the gaps between the two, and ink stains on printed matter can be further suppressed.

Further, it is more preferable to have at least a portion where the base material 1, the ink inking / repulsion function layer 4, and the ink repulsion composition layer 6 are laminated in this order.

In the cylindrical printing plate original plate and the cylindrical printing plate in the present invention, the base material, the organic layer, the heat sensitive layer, and the ink inking / repulsion functional layer are common. Each will be described below.

(Base material)
Examples of the substrate include known papers, metals, films, etc., which are conventionally used for printing plates and have little dimensional change in the printing process. The substrate in the present invention preferably has ink inking property. Specifically, paper, paper laminated with plastic (polyethylene, polypropylene, polystyrene, etc.), metal plates such as aluminum (including aluminum alloy), zinc, copper, cellulose acetate, polyethylene terephthalate, polyethylene, polyester, polyamide, Plastic film such as polyimide, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, paper with metal such as aluminum (including aluminum alloy), zinc, copper, or aluminum (including aluminum alloy), zinc, copper, etc. Examples include a plastic film in which metal is laminated or vapor-deposited. The plastic film may be transparent or opaque. From the viewpoint of plate readability, an opaque film is preferable.

Of these substrates, the aluminum plate is particularly preferable because it has little dimensional change in the printing process and is inexpensive. Further, as a flexible substrate for light printing, a polyethylene terephthalate film is particularly preferable. The thickness of the substrate is not particularly limited, and the thickness corresponding to the printing machine may be selected.

(Organic layer)
An organic layer can be optionally provided between the base material and the ink inking / repulsion functional layer. The organic layer in the present invention preferably has ink inking property. The characteristics of the organic layer are that, in a waterless printing plate, it imparts flexibility, has good adhesion to a base material or a heat-sensitive layer, and has high resistance to a developing solution or a solvent used during printing. For example, an organic layer containing a metal chelate compound disclosed in JP-A-2004-199016, JP-A-2004-334025, etc. is preferably used, but the present invention is not limited to this.

The organic layer preferably contains a pigment. By including the pigment, the light transmittance of the organic layer can be set to 15% or less with respect to all wavelengths of 400 to 650 nm, and thus plate inspection property by machine reading can be imparted. As the pigment, it is preferable to use an inorganic white pigment such as titanium oxide, zinc flower, or lithopone, or an inorganic yellow pigment such as chrome yellow, cadmium yellow, yellow iron oxide, ocher, or titanium yellow. Among these pigments, titanium oxide is particularly preferably used from the viewpoint of hiding power and coloring power. The content of the pigment is preferably 2% by volume or more in the organic layer from the viewpoint of obtaining good hiding performance. On the other hand, 30% by volume or less is preferable in the organic layer from the viewpoint that good coating performance can be obtained.

(Thermal layer)
A heat-sensitive layer can be optionally provided between the base material and the ink inking / repulsion functional layer. The heat-sensitive layer in the present invention preferably has ink inking property. The heat-sensitive layer has a function of converting laser light used for drawing into heat (photothermal conversion), and further, at least the surface of the heat-sensitive layer is decomposed by the generated heat, or solubility in a developing solution. It is preferable that the ink repellent layer is increased or the adhesive force with the ink repellent layer is decreased. Such a heat-sensitive layer can contain, for example, the following composition.
(A) A composition containing a polymer having active hydrogen, an organic complex compound, and a photothermal converting substance.
(B) A composition containing a polymer having active hydrogen, a cross-linking agent, and a photothermal converter.
(C) A composition containing a self-reactive polymer having active hydrogen and a photothermal converter.

The heat-sensitive layer has a crosslinked structure composed of a polymer having active hydrogen and an organic complex compound in the composition shown in (a) due to heat generated from a photothermal converting substance by irradiating with laser light. Is disassembled. In the composition shown in (b), by irradiating with laser light, the crosslinked structure composed of the polymer and the crosslinking agent is decomposed by the heat generated from the photothermal converting substance. In the composition shown in (c), by irradiating with laser light, the crosslinked structure formed by the self-reaction of the polymer is decomposed by the heat generated from the photothermal converting substance.

Examples of the polymer having active hydrogen preferably used for the heat-sensitive layer include a polymer having a structural unit having active hydrogen. Structural units having active hydrogen include, for example, -OH, -SH, -NH ₂ , -NH- _{, -CO-NH 2} , -CO-NH-, -OC (= O) -NH-, and -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- and the like can be mentioned.

Examples of the polymer having active hydrogen that can be suitably used in the compositions (a) and (b) include acrylic resins having a carboxyl group or a hydroxyl group, polyurethanes, polyureas, polyamides, epoxy resins, and polyalkyleneimines. , Novolac resins, cellulose derivatives and the like.

Further, examples of the polymer having active hydrogen having self-reactivity that can be suitably used in the above composition (c) include resole resins and melamine resins.

The content of the polymer having active hydrogen is preferably 20% by mass or more in the heat-sensitive layer from the viewpoint of decomposing the surface of the heat-sensitive layer by heat or accelerating development by changing the solubility in a developing solution. , 30% by mass or more is more preferable. Further, in terms of toughness of the heat-sensitive layer, 95% by mass or less is preferable, and 80% by mass or less is more preferable.

The organic complex compound contained in the composition (a) contains a metal and an organic compound. It acts as a cross-linking agent to polymers with active hydrogen. Examples of such an organic complex compound include an organic complex salt in which an organic ligand is coordinated to a metal, an organic-inorganic complex salt in which an organic ligand and an inorganic ligand are coordinated to a metal, and a metal and an organic molecule via oxygen. Examples thereof include metal alkoxides that are covalently bonded.

The main metals forming the organic complex compound are Al (III), Ti (IV), Mn (II), Mn (III), Fe (II), Fe (III), Co (II) and Co (III). ), Ni (II), Ni (IV), Cu (I), Cu (II), Zn (II), Ge, In, Sn (II), Sn (IV), Zr (IV), Hf (IV). Is preferable. Al (III) is particularly preferable because it is easy to obtain a sensitivity improving effect, and Ti (IV) is particularly preferable because it is easy to develop resistance to printing inks and ink cleaners.

Further, examples of the ligand include a compound having a coordinating group having oxygen, nitrogen, sulfur or the like as a donor atom. Specific examples of coordinating groups include -OH (alcohol, enol and phenol), -COOH (carboxylic acid),> C = O (aldehyde, ketone, quinone) and -O as those having oxygen as a donor atom. -(Ether), -COOR (ester, R: representing aliphatic or aromatic hydrocarbons), -N = O (nitroso compound), -NO ₂ (nitro compound),> NO (N-oxide), -SO ₃ H (sulfonic acid), - such as _PO 3 _{H 2} (phosphorous acid), as nitrogen is a donor atom, _-NH 2 (1 amine, hydrazine),> NH (2 amines, hydrazines ),> N- (tertiary amine), -N = N- (azo compound, heterocyclic compound), = N-OH (oxime), -NO ₂ (nitro compound), -N = O (nitroso compound), > C = N- (Schiff base, heterocyclic compound),> C = NH (aldehyde, ketoneimine, enamines), -NCS (isothiocianato), etc., which use sulfur as a donor atom, -SH (thiol), -S- (thioether),> C = S (thioketone, thioamide), = S- (heterocyclic compound), -C (= O) -SH, -C (= S) -OH, -C (= S) -SH (thiocarboxylic acid), -SCN (thiocyanate) and the like can be mentioned.

Among the organic complex compounds formed from the above metals and ligands, preferably used compounds are Al (III), Fe (II), Fe (III), Ti (IV), Zr (IV). Examples include the acetylacetone complex and the acetoacetate ester complex.

Specific examples of such compounds include the following compounds.

Aluminum Tris (Acetylacetate), Aluminum Tris (Ethylacetacetate), Aluminumtris (propylacetacetate), Aluminumtris (Butylacetate), Aluminumbis (Ethylacetacetate) Mono (Acetylacetate), Aluminumbis (Acetyl) Acetonate) mono (ethylacetacetate), aluminum bis (propylacetacetate) mono (acetylacetonate), aluminum bis (butylacetate) mono (acetylacetonate), aluminum bis (propylacetacetate) mono (ethylacetacetate) ), Aluminum bis (butyl acetoacetate) mono (ethyl acetoacetate), aluminum dibutoxide mono (acetyl acetonate), aluminum diisopropoxide mono (acetyl acetonate), aluminum diisopropoxide mono (ethyl acetoacetate), Titanium diisopropoxidebis (acetylacetonate), titaniumdi-n-butoxidebis (acetylacetonate), titaniumdiisopropoxidebis (ethylacetacetate), titaniumdi-n-butoxidebis (ethylacetoacetate), Titanium tri-n-butoxide mono (ethyl acetoacetate), titanium triisopropoxide mono (methacryloxyethyl acetoacetate), titanium oxamidebis (acetyl acetonate), zirconium di-n-butoxide bis (acetyl acetonate) , Zirconite tetrakis (acetylacetonate), iron (III) acetylacetonate, acetoacetate iron (III), iron (III). Two or more of these may be contained.

Such an organic complex compound acts as a cross-linking agent for the polymer. The amount is preferably 0.5% by mass or more in the heat-sensitive layer. Further, 50% by mass or less is preferable from the viewpoint of maintaining the durability of the waterless planographic printing plate.

Examples of the cross-linking agent contained in the composition (b) include a polyfunctional compound having a plurality of functional groups reactive with the active hydrogen of the polymer. For example, polyfunctional isocyanate, polyfunctional blocked isocyanate, polyfunctional epoxy compound, polyfunctional (meth) acrylate compound, polyfunctional aldehyde, polyfunctional mercapto compound, polyfunctional alkoxysilyl compound, polyfunctional amine compound, polyfunctional carboxylic acid, Examples thereof include a polyfunctional vinyl compound, a polyfunctional diazonium salt, a polyfunctional azide compound, and hydrazine.

The photothermal conversion substances that can be contained in the compositions (a) to (c) include, by absorbing laser light, light energy is converted into kinetic energy of atoms and molecules, and 200 is instantaneously generated on the surface of the heat sensitive layer. Those having a function of thermally decomposing the crosslinked structure of the heat-sensitive layer by generating heat of ° C. or higher are preferable. In particular, pigments and dyes that absorb infrared rays or near infrared rays are preferable. For example, black pigments such as carbon black, carbon graphite, aniline black, cyanine black, phthalocyanine, naphthalocyanine-based green pigments, crystalline water-containing inorganic compounds, iron, copper, chromium, bismuth, magnesium, aluminum, titanium, zirconium, cobalt. , Vanadium, manganese, tungsten and other metal powders, or sulfides, hydroxides, silicates, sulfates, phosphates, diamine compound complexes, dithiol compound complexes, phenolthiol compound complexes, mercaptophenol compound complexes, etc. of these metals. Can be mentioned.

The dyes that absorb infrared rays or near-infrared rays are dyes for electronics and recording, and have a maximum absorption wavelength in the range of 700 nm to 1500 nm, such as cyanine dyes, azulenium dyes, squarylium dyes, croconium dyes, and azo. Disperse dyes, bisazostilben dyes, naphthoquinone dyes, anthraquinone dyes, perylene dyes, phthalocyanine dyes, naphthalocyanine metal complex dyes, polymethine dyes, dithiol nickel complex dyes, indoaniline metal complex dyes, molecules Intermittent CT dyes, benzothiopyran-based spiropyran, niglosin dyes and the like are preferably used.

Among these dyes, those having a large molar extinction coefficient ε are preferably used. Specifically, ε is ^{preferably 1 × 10 4} L / (mol · cm) or more, and more preferably 1 × 10 ⁵ L / (mol · cm) or more. When ε is 1 × 10 ⁴ L / (mol · cm) or more, the initial sensitivity can be further improved. The coefficient here is for the active energy ray to be irradiated. If a specific wavelength is shown, attention should be paid to 780 nm, 830 nm or 1064 nm.

Two or more of these photothermal conversion substances may be contained. By containing two or more types of photothermal conversion substances having different absorption wavelengths, it is possible to correspond to two or more types of lasers having different transmission wavelengths.

Among these, a dye that absorbs carbon black, infrared rays, or near infrared rays is preferable from the viewpoint of photothermal conversion rate, economy, and handleability.

The content of these photothermal conversion substances is preferably 0.1% by mass to 70% by mass, and more preferably 0.5% by mass to 40% by mass in the heat-sensitive layer. By setting the content of the photothermal conversion substance to 0.1% by mass or more, the sensitivity to laser light can be further improved. On the other hand, when it is 70% by mass or less, the high durability of the waterless printing plate can be maintained.

(Ink inking / repulsion function layer)
If the lithographic printing plate original plate is a waterless lithographic printing plate original plate, the ink inking / repulsion functional layer is ink repulsive and preferably contains a silicone compound. Above all, a silicone rubber layer is preferable. The silicone rubber layer is 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 the silicone rubber layer composition. Examples thereof include a layer obtained by applying and drying a solution of these compositions.

On the other hand, in the case of a lithographic printing plate original plate with water, the ink-embedded / repulsive functional layer is ink-embedded, and preferably contains a light / thermopolymerizable compound and a light / thermopolymerization initiator. As the light / thermopolymerizable compound, an acrylic resin, a phenol resin, a melamine resin, or the like can be used, and is not particularly limited. As the photo / thermal polymerization initiator, a known commercially available product can be preferably used. From the viewpoint of productivity, it is preferable to cure by exposure with a general-purpose semiconductor laser having an emission wavelength region near the near infrared region, while it is more preferable that the unexposed portion can be easily removed by physical stimulation. For example, (1) a method of removing the unexposed part by rubbing with a rotating brush while sprinkling water or a solvent, (2) removing the unexposed part by tacking the supplied ink after swelling with dampening water. How to do it.

(Silicone rubber layer)
As the silicone rubber used for the silicone rubber layer, an addition reaction type silicone rubber composition is preferable because it has an excellent curing rate and can be expected to improve productivity. The addition reaction type silicone rubber composition preferably contains at least a vinyl group-containing organopolysiloxane, a 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 the end of the main chain or in the main chain. Of these, those having a vinyl group at the end of the main chain are preferable. Two or more of these may be contained.
-(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 represent saturated or unsaturated hydrocarbon groups 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. R ¹ there are a plurality of polysiloxane represented by the formula (alpha) may be different even in the same mutually. The R ² there are a plurality of polysiloxane represented by the formula (alpha) may be different even in the same mutually. In the above general formula (α), ^{it is preferable that 50% or more of R 1} and R ² are methyl groups in terms of ink resilience of the waterless lithographic printing plate. Further, from the viewpoint of fineness and scratch resistance, the weight average molecular weight of the vinyl group-containing organopolysiloxane is preferably 30,000 or more and 200,000 or less.

Examples of the SiH group-containing compound include an organohydrogenpolysiloxane and an organic polymer having a diorganohydrogensilyl group, and an organohydrogenpolysiloxane is preferable. Two or more of these may be contained. Organohydrogenpolysiloxanes can have linear, cyclic, branched and reticulated molecular structures.

Further, a SiH group-containing compound which is a copolymer of siloxane structural units represented by the following general formulas (i) and (ii) is preferable from the viewpoint of improving the ground pollution start temperature and cost.
-SiH (CH ₃ ) -O- (i)
-Si (CH ₃ ) _2- O- (ii)
In the present invention, the SiH group-containing compound is represented by the general formula (i) with respect to a total of 100 mol% of the siloxane structural unit represented by the general formula (i) and the siloxane structural unit represented by the general formula (ii). The content ratio of the siloxane constituent unit ((i) / ((i) + (ii)) × 100) is 50 mol% or more from the viewpoint that the amount of functional groups that can react per molecule is large and the cross-linking density can be improved. It is preferably 60 mol% or more, and more preferably 60 mol% or more. The content ratio of the siloxane constituent 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 cross-linking points.

Examples of the reaction inhibitor include nitrogen-containing compounds, phosphorus-based compounds, unsaturated alcohols, and the like, and acetylene group-containing alcohols are preferably used. Two or more of these may be contained. By containing these reaction inhibitors, the curing rate of the silicone rubber layer can be adjusted. The content of the reaction inhibitor is preferably 0.01% by mass or more, more preferably 0.1% by mass or more in the silicone rubber layer composition from the viewpoint of stability of the silicone rubber layer composition and its solution. Further, from the viewpoint of curability of the silicone rubber layer, 20% by mass or less is preferable, and 15% by mass or less is more preferable in the silicone rubber layer composition.

The curing catalyst can be selected from known ones. It is preferably a platinum-based compound, and specific examples thereof include platinum alone, platinum chloride, platinum chloride acid, olefin-coordinated platinum, an alcohol-modified complex of platinum, and a methylvinyl polysiloxane complex of platinum. Two or more of these may be contained. The content of the curing catalyst is preferably 0.001% by mass or more, more preferably 0.01% by mass or more in the silicone rubber layer composition from the viewpoint of curability of the silicone rubber layer. Further, from the viewpoint of stability of the silicone rubber layer composition and its solution, 20% by mass or less is preferable, and 15% by mass or less is more preferable in the silicone rubber layer composition. The distribution and content of the platinum catalyst can be estimated by scanning electron microscopy / energy dispersive X-ray spectroscopy (SEM / EDX) analysis.

In addition to these components, hydroxyl group-containing organopolysiloxane, hydrolyzable functional group-containing silane, or siloxane containing this functional group, known fillers such as silica for the purpose of improving rubber strength, and adhesiveness are improved. A known silane coupling agent may be contained for the purpose of causing the silane coupling agent to be contained. As the silane coupling agent, alkoxysilanes, acetoxysilanes, ketoximinosilanes and the like are preferable, and those in which a vinyl group or an allyl group is directly linked to a silicon atom are preferable.

The film thickness of the silicone rubber layer is preferably 2.0 μm or more, more preferably 3.0 μm or more, and further preferably 4.0 μm or more in terms of further improving ink resilience and durability. Further, from the viewpoint of improving the fineness, 7.0 μm or less is preferable, and 6.0 μm or less is more preferable. The thickness of the silicone rubber layer can be confirmed by embedding a section of a waterless planographic printing plate with resin, preparing a cross section by the CP method, and observing it with a field emission scanning electron microscope (FE-SEM). can.

Silicone oil can be contained in the silicone rubber layer of the present invention for the purpose of further improving ink resilience.

The content of the silicone oil in the silicone rubber layer is preferably 10% by mass or more in that the silicone oil is sufficiently extruded onto the surface of the silicone rubber layer and the ink resilience is remarkably improved. Further, in terms of maintaining the film strength of the silicone rubber layer, the content in the silicone rubber layer is preferably 30% by mass or less, more preferably 25% by mass or less.

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 referred to in the present invention refers to a free polysiloxane component that is not involved in cross-linking of the silicone rubber layer. Therefore, dimethyl silicone oils such as terminal dimethylpolydimethylsiloxane, cyclic polydimethylsiloxane, terminal dimethyl-polydimethyl-polymethylphenylsiloxane copolymer, terminal dimethyl-polydimethyl-polydiphenylsiloxane copolymer, alkyl-modified silicone oil, and fluorine-modified Silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, epoxy polyether-modified silicone oil, phenol-modified silicone oil, carboxy-modified silicone oil, mercapto-modified silicone oil, amide-modified silicone oil , Carbana-modified silicone oil, higher fatty acid-modified silicone oil, and other modified silicone oils in which various organic groups are introduced into some of the methyl groups in the molecule.

The molecular weight of these silicone oils can be measured by gel permeation chromatography (GPC) using polystyrene as a standard, and those having a weight average molecular weight Mw of 1,000 to 100,000 are preferable.

(Ink repulsive composition and ink repulsive composition layer)
The ink-repulsive composition may be a one-component system or a two-component or more system that cures by mixing, but a one-component system is preferable from the viewpoint of handleability. The curing method is not limited, and it may be naturally cured at room temperature or heat-cured. Heat curing is preferable in terms of improving the film strength of the ink repulsive composition layer formed by curing the ink repulsive composition and improving the durability of the cylindrical printing plate.

When the lithographic printing plate is a waterless lithographic printing plate, the ink repellent composition preferably contains a silicone compound.

The ink-repulsive composition containing the silicone compound preferably has a binder polymer. Examples of the binder polymer of the ink-repulsive composition include silicone polymers, fluorosilicone polymers, and silicone-acrylic copolymers. Two or more of these may be contained. Among these, a silicone polymer can be preferably used in terms of cost.

As the silicone polymer, an addition type having a vinyl group and a condensation type having a silanol group can be used. Of these, the condensation type silicone polymer is preferable because it reacts and cures with the moisture in the air, so that it is easy to make a one-component system.

Examples of the cross-linking agent for the addition type silicone polymer include SiH group-containing compounds such as organohydrogenpolysiloxane and organic polymers having a diorganohydrogensilyl group. A known silane coupling agent can be used as the cross-linking agent for the condensed silicone polymer.

As the cross-linking agent for the condensed silicone polymer, a silane coupling agent can be preferably used, and alkoxysilanes having a trifunctional hydrolyzable group, acetoxysilanes, ketoximinosilanes, and tetrafunctional hydrolyzable. Compounds such as alkoxysilanes, acetoxysilanes, and ketoxyminosilanes having a group are preferable. In the case of a compound having a trifunctional hydrolyzable group, a compound in which a vinyl group or an allyl group is directly linked to a silicon atom is preferable in terms of curing rate.

The content of the silane coupling agent in the ink repulsive composition containing the condensed silicone polymer is preferably 3% by mass or more, more preferably 5% by mass or more in terms of the curing rate. 15% by mass or less is preferable, and 10% by mass or less is more preferable, because the brittleness of the ink-repulsive composition layer can be suppressed.

Further, when a silane coupling agent having a trifunctional hydrolyzable group and a silane coupling agent having a tetrafunctional hydrolyzable group are used in combination, the content of the silane coupling agent having a tetrafunctional hydrolyzable group is used. Is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total amount of the silane coupling agent in the ink repulsive composition, in terms of improving the curing rate. On the other hand, in terms of storage stability, it is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total amount of the silane coupling agent in the ink repulsive composition.

The ink-repulsive composition containing the condensed 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 a hydrolyzable group. Specifically, R includes a vinyl group, a chloromethyl group, a methyl group, an ethyl group, a phenyl group, a propyl group, a cyclohexyl group and the like. Examples of A include an acetoxy group, an oxime group, a methoxy group, an ethoxy group and the like. Examples of B include an acetoxy group, an oxime group, a methoxy group, an ethoxy group and the like.

Further, the compound represented by the general formula (II) contained in the ink repulsive composition is 5 with respect to the total of the compound represented by the general formula (I) and the compound represented by the general formula (II). It is preferably ~ 50% by mass. 5% by mass or more is preferable, 10% by mass or more is more preferable, and 20% by mass or more is preferable, in that the film strength of the ink repulsive composition layer can be improved and the durability of the cylindrical printing plate can be further improved. More preferred. On the other hand, 50% by mass or less is preferable, and 30% by mass or less is more preferable, in that brittle fracture of the ink repulsive composition layer can be suppressed and durability can be maintained.

The ink repulsive composition layer formed by curing the ink repulsive composition as described above _{preferably contains a SiO 4/2} structural unit. That is, it is preferable that the silicone compound contains a SiO _{4/2 structural unit. The inclusion of SiO 4/2} structural units in the ink repulsive composition layer can be confirmed by ^{solid 29 Si NMR analysis.} It can be confirmed by the same method that the silicone compound contains a SiO _{4/2 structural unit.}

_{The content of the SiO 4/2} structural unit in the ink repulsive composition layer is as follows: R ₃ SiO _1/2 structural unit, R ₂ SiO _2/2 structural unit, RSiO _3/2 structural unit and SiO _4/2 configuration. It is preferably 0.8 to 2.5% with respect to the total number of units. That is, the content of the _{SiO 4/2} structural unit contained in the silicone compound is that _{of the R 3} SiO _1/2 structural unit, the R ₂ SiO _2/2 structural unit, the RSiO _3/2 structural unit and the SiO _4/2 structural unit. It is preferably 0.8 to 2.5% with respect to the total.

The content of SiO _4/2 structural units included in the content and silicone compounds SiO _4/2 structural units of ink repellant composition layer, to improve the film strength of the ink repellant composition layer, cylindrical printing plate 0.8% or more is preferable, and 1.0% or more is more preferable, in that the durability of the ink can be further improved. On the other hand, 2.5% or less is preferable, and 1.5% or less is more preferable, from the viewpoint of suppressing brittle fracture due to the ink repulsive composition layer becoming harder than necessary. Here, R is an arbitrary organic substituent.

The content of the SiO _{4/2 structural unit is the peak area of the R 3} SiO _1/2 ^{structural unit obtained by solid-state 29} Si NMR analysis, the peak area of the R ₂ SiO _2/2 structural unit, and the RSiO _3/2 structural unit. peak area of, and can be determined from the ratio of the peak area of _{SiO 4/2} structural units to the sum of the peak of _{SiO 4/2} structural units. The content of SiO _4/2 structural units in the ink-repulsive composition layer is a measure of the cross-linking density in the ink-repulsive composition layer. The detailed measurement method of each peak area obtained by solid ²⁹ Si NMR analysis will be described in the column of Examples.

In addition, silicone oil may be contained in the ink-repulsive composition layer for the purpose of further improving the ink repulsion and further suppressing stains in the gaps between the edges of the waterless lithographic printing plate in the circumferential direction. can. As the silicone oil referred to here, the same silicone oil that can be contained in the silicone rubber layer can be used.

The content of the silicone oil in the ink repulsion composition layer is preferably 5% by mass or more, more preferably 10% by mass or more, in terms of significantly improving the ink repulsion. Further, 50% by mass or less is preferable, and 25% by mass or less is more preferable, from the viewpoint of maintaining the film strength of the ink repulsive composition layer.

The content of silicone oil in the ink repulsive composition layer can be confirmed by immersing the cut ink repulsive composition layer in hexane and measuring the mass of the extracted silicone oil.

On the other hand, when the lithographic printing plate is a lithographic printing plate with water, the ink repulsive composition can use a hydrophilic compound that develops ink repulsion when it comes into contact with dampening water. Here, the hydrophilic compound refers to a compound having a contact angle of less than 90 degrees when contacted with water, and a water-soluble resin that is more easily swelled because it swells with dampening water and acquires ink resilience. preferable.

The water-soluble resin may be any one that swells or dissolves in dampening water, for example, glycidyl-modified acrylic resin, resole-type phenol resin, polyurethane, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, polyacrylamide, carboxymethyl cellulose, gum arabic, starch. , Gelatin, casein and the like, and two or more of these may be contained.

Among such water-soluble resins, those having a vinyl group and / or a methylol group are capable of improving durability by light / thermosetting after filling the gap formed between the edges of a lithographic printing plate with water. preferable. For example, a glycidyl-modified acrylic resin, a resole-type phenol resin, or the like can be preferably used.

(Method of forming the ink repulsive composition layer)
The ink-repulsive composition layer is formed, for example, by forming a flat plate printing plate into a tubular shape so that the ink inking / repulsive function layer side is the surface, and (1) applying an ink-repulsive tape on the surface in the circumferential direction of the flat plate printing plate. Attached to the gap between the edges, (2) Ink repulsion by attaching a tape having an ink-repulsive composition layer to the gap between the edges in the circumferential direction of the plate printing plate, and then peeling off the release film. It can be formed by a method such as transferring the sex composition layer or (3) filling the gap between the edges of the plate printing plate in the circumferential direction with the ink repulsive composition.

Above all, it is preferable that the ink-repulsive composition is a tape having an ink-repulsive surface.

Further, the lithographic printing plate is formed into a tubular shape so that the ink inking / repulsive functional layer side is the surface, and (3) the ink repulsive composition is filled in the gap between the edges of the lithographic printing plate in the circumferential direction to make ink. It is preferable to form a repulsive composition layer. Further, the lithographic printing plate is formed into a tubular shape so that the ink repulsive composition layer side faces the surface, and (3) the ink repulsive composition is filled in the gap between the circumferential ends of the lithographic printing plate and then heated. It is more preferable to form the ink repellent composition layer by including the step of forming the ink repulsive composition layer.

In the present invention, the film thickness of the ink repulsive composition layer refers to the film thickness of the portion laminated on the ink inking / repulsion function layer. That is, as shown in FIG. 2B, the film thickness 6H of the ink repulsive composition layer 6 is defined by the height from the surface of the ink inking / repulsive functional layer to the surface of the ink repulsive composition layer. , Can be measured with a surface roughness / contour shape measuring machine.

The film thickness of the ink repulsion composition layer is preferably 1 μm or more, and more preferably 5 μm or more, in that the ink repulsion can be further improved. On the other hand, 100 μm or less is preferable, 50 μm or less is more preferable, and 10 μm or less is further preferable, from the viewpoint of suppressing a decrease in durability due to stress applied during printing and abrasion of the ink repulsive composition layer.

(Manufacturing method of cylindrical printing plate)
Next, a method of manufacturing a cylindrical printing plate using a cylindrical printing plate original plate will be described. The method for producing a cylindrical printing plate according to the present invention is a step of exposing a cylindrical printing plate original plate according to an image (exposure step), or in addition to an exposure step, a physical stimulus is given to the exposed cylindrical printing plate original plate. It is preferable to include a step of forming an image (development step).

First, the exposure process will be described. The above-mentioned cylindrical printing plate original plate is exposed according to an image. Examples of the light source used in the exposure step include those having an emission wavelength region in the range of 300 nm to 1500 nm. Among these, since it is widely used as the absorption wavelength of the heat-sensitive layer, a semiconductor laser or a YAG laser having an emission wavelength region near the near infrared region is preferably used. Specifically, from the viewpoint of heat conversion efficiency, laser light having wavelengths of 780 nm, 830 nm, and 1064 nm is preferably used for exposure.

Next, the development process will be described. By giving a physical stimulus to the original plate after exposure, the ink inking / repulsion functional layer in the exposed portion or the unexposed portion is removed. Examples of the method of giving physical stimulation include (I) a method of wiping the plate surface with a dry non-woven fabric, non-fat cotton, cloth, sponge, etc., and (II) a method of wiping the plate surface with a non-woven fabric impregnated with a developing solution, non-fat cotton, cloth, sponge, etc. Method, (III) Pretreatment of the plate surface with a developing solution and then rubbing with a rotating brush while showering tap water, (IV) Method of spraying high-pressure water, hot water, or water vapor onto the plate surface, (V) Developer solution Examples thereof include a method of immersing the plate surface in a rotating brush and rubbing the plate surface with a rotating brush, and a method of removing the exposed portion or the unexposed portion by tacking the supplied ink after swelling with (VI) dampening water.

For example, water, alcohol or paraffinic hydrocarbon can be used as the developing solution. Further, propylene glycol derivatives such as diglycolamine, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, and alkylene oxide adduct to polypropylene glycol, and a mixture of the above compound and water can also be used. Specific examples of the developing solution include HP-7N, WH-3, PP-1, PP-3, PP-F, PP-FII, PTS-1, CP-1, CP-Y, CP-X, and NP-. 1. DP-1 (both manufactured by Toray Industries, Inc.) and the like can be mentioned. In addition, for the purpose of improving the visibility of the image area and the measurement accuracy of halftone dots, the image area should be dyed at the same time as the development using a developer having a dye such as crystal violet, Victoria pure blue, or Astrazon red. You can also. Furthermore, after development, it can be dyed with a liquid containing the above dye.

The cylindrical printing plate can also be manufactured from a lithographic printing plate having an image area and a non-image area. A cylindrical printing plate can be manufactured by winding a lithographic printing plate around a cylindrical support and filling a gap between ends of the lithographic printing plate with an ink-repulsive composition. Here, the lithographic printing plate may be a lithographic printing plate without water or a lithographic printing plate with water. The gap formed between the edges of the lithographic printing plate is preferably 5 mm or less. If it is 5 mm or less, it can be uniformly filled with the ink-repulsive composition, and stains and deterioration of durability due to uneven coating can be suppressed.

It is preferable to include a step of flattening the ink repulsive composition and / or a step of heating the ink repulsive composition after filling the gap formed between the edges of the lithographic printing plate with the ink repulsive composition. .. The flattening process includes a method of mechanically applying pressure over the ink-repulsive composition filled in the gap formed between the edges of the lithographic printing plate, a method of flattening with a scraper or a hand roller, and the like. And so on. The arithmetic surface roughness Ra of the flattened ink-repulsive composition is preferably 0.3 μm or less. If it is 0.3 μm or less, it is possible to suppress stains and deterioration of durability due to uneven coating. Examples of the heating step include a method of bringing a heat source into contact with an ink repulsive composition filled in a gap formed between the edges of a lithographic printing plate, a method of applying hot air, and the like.

(Manufacturing method of printed matter using a cylindrical printing plate)
The method for producing a printed matter according to the embodiment of the present invention using the above-mentioned cylindrical printing plate includes at least (1) a step of adhering ink to the surface of the cylindrical printing plate, and (2) directly or blanketing the ink. It has a step of transferring onto a printed matter via.

The cylindrical printing plate is fixed directly to the cylindrical support or fixed to a sleeve that can be attached to and detached from the cylindrical support. When fixed to the sleeve, the material of the sleeve is preferably glass fiber and / or aluminum from the viewpoint of weight reduction.

The method for producing a printed matter according to the embodiment of the present invention using the above-mentioned cylindrical printing plate is, for example, the following method. An ink-repulsive liquid is applied to the surface of the cylindrical printing plate. The ink roller to which the ink is supplied is brought into contact with the surface of the cylindrical printing plate, the ink adheres to the image area, and the ink repels the non-image area. After that, the cylindrical printing plate to which the ink adheres to the image is directly contacted with the printed matter, or once brought into contact with the blanket, and then the blanket is brought into contact with the printed matter to cover the image-like ink. It can be transferred to a printed matter to produce a printed matter.

Here, the process of applying the ink-repulsive liquid to the surface of the cylindrical printing plate is indispensable for printing with water, and the ink-repulsive liquid refers to dampening water. It is optional for waterless printing, and the ink repellent liquid refers to a low-polarity solvent that can swell the silicone layer.

In the step of transferring the ink to the object to be printed via the blanket, the ink transferred to the blanket may be heated for the purpose of improving the adhesion to the object to be printed by increasing the ink fluidity.

The cylindrical printing plate in the present invention can be suitably used for printing on a packaging material. It is preferable that the printed material is transported in a roll-to-roll manner in that existing equipment can be used in post-processing such as laminating processing and bag making processing.

Examples of the object to be printed include film, paper, metal leaf, and the like. Specifically, kraft paper, single-gloss kraft paper, high-quality paper, medium-quality paper, newspaper paper, synthetic fiber paper, Japanese paper, coated paper, polypropylene, polyethylene, polyethylene terephthalate, polyester, polyamide, polyimide, polystyrene, polycarbonate, polyvinyl acetal , Cellulose acetate, aluminum foil (including aluminum alloy), zinc foil, copper foil, and a laminate obtained by combining any of the above, but the present invention is not limited to this. A film is preferable as the object to be printed because of its high versatility such as light weight and liquid packaging.

After transferring the image-like ink to the object to be printed, the steps of heating, ultraviolet (UV) irradiation, and electron beam (EB) irradiation may be included for curing the ink. It is more preferable to include an electron beam (EB) irradiation step using EB ink in that migration of residual solvent and small molecule components can be avoided and food packaging can be used.

In printing with water, since dampening water is mixed with the ink, the adhesion to the object to be printed deteriorates and the solvent may remain on the object to be printed. Therefore, the cylindrical printing plate in the present invention is used. , Preferably composed of a waterless lithographic printing plate.

Hereinafter, the present invention will be described in more detail with reference to Examples.

(1) Measurement of film thickness of ink-repulsive composition layer Using a surface roughness / contour shape measuring machine SURFCOM 1400D (manufactured by Tokyo Precision Co., Ltd.), the measurement speed is based on the test method of JIS B 0601-2001. Under the conditions of 0.3 mm / s and measurement distance: 6 mm, the surfaces of the ink inlay / repulsion function layer and the ink repulsion composition layer of the cylindrical printing plate original plate were made to fall within the measurement range, and the ink inking / The step between the repulsive function layer and the ink repulsive composition layer was measured. The measurement was carried out at any five points, and the average value was taken as the film thickness of the ink repulsive composition layer.

(2) Flexible packaging printing Using the flexible packaging printing machine "OFFSET CI8" (manufactured by COMEXI), the ink of EB offset ink "Starabem" (manufactured by Toyo Ink Co., Ltd.) is supplied to the ink roller and attached to the plate cylinder. Ink was supplied to the cylindrical printing plate so that the solid density of the circuit tape "647" on the cylindrical printing plate was 1.8. The cylindrical printing plate and the blanket were brought into contact with each other, and the ink was transferred from the cylindrical printing plate to the blanket. Subsequently, offset printing was performed to transfer the ink on the blanket to the polypropylene film "P2111" (manufactured by Toyobo Co., Ltd.).

(3) Measurement of stain density in the gap In the printing of (2) and (8), the printed matter obtained at the time of printing 1,000 m was sampled, and the density of the stain density in the gap was measured by the reflection spectrophotometer "SpectroEye". (Made by X-rite Co., Ltd.) was used, and the measurement was performed under the condition of color filter: black. The measurement was carried out at 5 points, and the average value was taken as the concentration of dirt in the gap. When the reflection density was 0.1 or less, there was no problem in practical use, and it was judged that 0.05 or less was preferable, and 0.01 or less was more preferable.

(4) Measurement of Ground Stain Start Temperature In the printing of (2) and (8), printing was performed while controlling the plate surface temperature using a chiller. The plate surface temperature of the cylindrical printing plate was measured with a non-contact thermometer, and ground stains on the non-image area were confirmed for each temperature. The temperature at the time when the ground pollution was confirmed was defined as the ground pollution start temperature. It was determined that if the ground fouling start temperature is 28 ° C. or higher, there is no problem in practical use and more stable printing can be performed. Therefore, 30 ° C. or higher is preferable, and 35 ° C. or higher is more preferable.

(5) Evaluation of Durability In the printing of (2) and (8) above, the ink inking / repulsion function layer or the ink repulsion composition layer of the cylindrical printing plate is worn, and ink is applied to the non-image area. The number of contacts (shots) between the cylindrical printing plate and the blanket at the time of adhesion was defined as the durability of the cylindrical printing plate. It was judged that the durability of the cylindrical printing plate is practically no problem as long as it is 4,000 shots or more, preferably 6,000 shots or more, and more preferably 10,000 shots or more.

(6) Evaluation of productivity Productivity was evaluated by the difficulty of manufacturing the original printing plate. In the coating of the organic layer composition solution, the heat-sensitive layer composition solution, and the silicone rubber layer composition solution, which will be described later, if continuous coating can be performed on the base material without cissing, A, cissing occurs when the base material is coated. The case was evaluated as C.

(7) the content of _{SiO 4/2} structural units in the ink repellent composition layer calculated ink repellant composition layer for the content of _{SiO 4/2} structural units in can be quantified by a solid ²⁹ Si NMR analysis. The ink repulsive composition layer was scraped off, and the measurement nucleus: ²⁹ Si, spectrum width: 40 kHz, pulse width: 4.2 μsec, pulse repetition time: ACQTM 0.02049 sec by the DD / MAS method using AVANCE400 (manufactured by Bruker). , PD 140 sec, observation point: 8192, reference substance: hexamethylcyclotrisiloxane (external standard: −9.66 ppm), temperature: 22 ° C., sample rotation speed: 4 kHz, solid ²⁹ Si NMR measurement was performed.

The peak around 5-10 ppm of the chemical shift of the obtained ²⁹ _{Si DD / MAS NMR spectrum is the R 3} SiO _1/2 constituent unit, and the peak around 10-25 ppm is the R ₂ SiO _2/2 constituent unit, around 50-75 ppm. The peak was _{assigned to the RSiO 3/2} constituent unit, and the peak near 85-125 ppm was assigned to the _{SiO 4/2 constituent unit.} The peak area of the respective structural units is measured, relative to the sum of the peak areas of the respective structural units, by determining the ratio of the peak area of SiO _4/2 structural units, SiO _4/2 configuration in ink repellant composition layer The unit content was calculated.

(8) Flexible packaging printing with water Using a flexible packaging printing machine "OFFSET CI8" (manufactured by COMEXI), after supplying dampening water to the plate surface of the cylindrical printing plate, EB offset ink "Sterabem" (Toyo Ink Co., Ltd.) Ink ink (manufactured by the company) was attached to a cylindrical printing plate so that the solid density was 1.8. Next, the cylindrical printing plate and the blanket were brought into contact with each other, and the ink was transferred from the cylindrical printing plate to the blanket. Subsequently, offset printing was performed to transfer the ink on the blanket to the polypropylene film "P2111" (manufactured by Toyobo Co., Ltd.).

(9) Surface Roughness Measurement The surface roughness (arithmetic surface roughness Ra) of the ink repulsive composition layer was measured using a laser microscope "VK-9510" (manufactured by KEYENCE). Using a 20x objective lens, the 200 × 200 μm region of the ink repulsive composition layer that filled the gap formed between the edges of the lithographic printing plate was measured, and the average value of 10 points was taken as the surface roughness.

[Example 1]
A waterless lithographic printing plate-1 was produced by the following method. The organic layer composition solution was applied on a degreased aluminum substrate having a thickness of 0.30 mm with a bar coater and dried at 200 ° C. for 90 seconds to provide an organic layer having a thickness of 10.0 μm. The organic layer composition solution was obtained by stirring and mixing the following components at room temperature (20 to 28 ° C.).

<Organic layer composition solution>
(A) Polymer having active hydrogen: Epoxy resin: "Epicoat" (registered trademark) 1010 (manufactured by Japan Epoxy Resin Co., Ltd.): 35 parts by mass (b) Polymer having active hydrogen: Polyurethane: "Samplen" (registered trademark) ) LQ-T1331D (manufactured by Sanyo Kasei Kogyo Co., Ltd., solid content concentration: 20% by mass): 375 parts by mass (c) Aluminum chelate: aluminum chelate ALCH-TR (manufactured by Kawaken Fine Chemicals Co., Ltd.): 10 parts by mass ( d) Leveling agent: "Disparon" (registered trademark) LC951 (manufactured by Kusumoto Kasei Co., Ltd., solid content: 10% by mass): 1 part by mass (e) Titanium oxide: "Tipeke" (registered trademark) CR-50 (Ishihara) N, N-dimethylformamide dispersion (50% by mass of titanium oxide) manufactured by Sangyo Co., Ltd .: 60 parts by mass (f) N, N-dimethylformamide: 730 parts by mass (g) Methylethylketone: 250 parts by mass.

Next, the heat-sensitive layer composition solution was applied onto the organic layer with a bar coater and dried by heating at 140 ° C. for 90 seconds to provide a heat-sensitive layer having a thickness of 1.5 μm. The thermal layer composition solution was obtained by stirring and mixing the following components at room temperature (20 to 28 ° C.).

<Thermal layer composition solution>
(A) Infrared absorbing dye (cyanine dye): NK5559 (manufactured by Hayashihara Co., Ltd., maximum absorbing wavelength: 774 nm): 16.0 parts by mass (b) Organic complex compound: Titanium-n-butoxide bis (acetylacetonate): " Narsem "(registered trademark) Titanium (manufactured by Nippon Kagaku Sangyo Co., Ltd., concentration: 73% by mass, including n-butanol: 27% by mass as a solvent): 15.0 parts by mass (c) Phenolic formaldehyde novolak resin:" Sumi Light Resin "(registered trademark) PR53195 (manufactured by Sumitomo Bakelite Co., Ltd.): 60 parts by mass (d) Polyurethane:" Nippon "(registered trademark) 5196 (manufactured by Nippon Polyurethane Co., Ltd., concentration: 30% by mass, methyl ethyl ketone as solvent) : 35% by mass, cyclohexanone: 35% by mass): 25 parts by mass (e) tetrahydrofuran: 1044 parts by mass.

Next, the silicone rubber layer composition solution-1 prepared immediately before coating was applied onto the heat-sensitive layer with a bar coater, heated at 140 ° C. for 80 seconds, and provided with a silicone rubber layer having an average thickness of 5.0 μm without water. A lithographic printing plate original plate was obtained. The silicone rubber layer composition solution-1 was obtained by stirring and mixing the following components at room temperature.

<Silicone rubber layer composition solution-1>
(A) α, ω-divinylpolydimethylsiloxane: DMS-V35 (weight average molecular weight 49,500, manufactured by GELEST Inc.): 86.26 parts by mass (b) Methylhydrogensiloxane-dimethylsiloxane copolymer RD-1 ((I) / ((i) + (ii)) × 100 = 50 mol%, manufactured by Toray Dow Corning Co., Ltd.): 4.93 parts by weight (c) Vinyltris (methylethylketooxyimino) silane: 2.64 Parts by weight (d) Platinum catalyst SRX212 (manufactured by Toray Dow Corning Co., Ltd., 6.0% by weight of platinum catalyst): 6.17 parts by weight (e) "Isoper" E (manufactured by Esso Chemical Co., Ltd.): 900 Parts by Weight Here, the silicone rubber layer of the waterless flat plate printing plate original plate-1 is the ink inlay / repulsion functional layer.

Further, an ink repulsive tape-1 was prepared as an ink repulsive composition layer to be attached to the gap of the waterless planographic printing plate original plate-1 by the following method.

On the circuit tape "647" (thickness: 0.1 mm, manufactured by Teraoka Seisakusho Co., Ltd.), apply the ink repulsion tape-1 composition solution prepared immediately before application with a bar coater, and heat at 140 ° C. for 80 seconds. An ink repellent tape-1 was obtained by providing a silicone rubber layer having an average film thickness of 5.0 μm. The ink repulsive tape-1 composition solution was obtained by stirring and mixing the following components at room temperature (20 to 28 ° C.).

<Ink repulsion tape-1 composition solution>
(A) α, ω-divinylpolydimethylsiloxane: DMS-V35 (weight average molecular weight 49,500, manufactured by GELEST Inc.): 86 parts by mass (b) Methylhydrogensiloxane-dimethylsiloxane copolymer RD-1 ((() i) / ((i) + (ii)) x 100 = 50 mol%, manufactured by Toray Dow Corning Co., Ltd .): 5 parts by weight (c) Vinyltris (methylethylketooxyimino) silane: 3 parts by weight (d) platinum Catalyst SRX212 (manufactured by Toray Dow Corning Co., Ltd., platinum catalyst 6.0% by weight): 6 parts by weight (e) "Isoper" E (manufactured by Esso Chemical Co., Ltd.): 900 parts by weight.

Cylindrical printing is performed by winding a waterless lithographic printing plate original plate-1 around the plate cylinder of the flexible packaging printing machine "OFFSET CI8" (manufactured by COMEXI) to form a cylindrical shape, and attaching an ink repellent tape-1 to the gap. I got the original version. When evaluated by the methods (1) and (6) above, the productivity was A and the film thickness of the ink repulsive composition layer was 105 μm.

Circuit tape "647" (thickness: 0.1 mm, manufactured by Teraoka Seisakusho Co., Ltd.) is attached to a part of the ink inking / repulsion function layer of the cylindrical printing plate original plate to form an ink inking part. A cylindrical printing plate was obtained.

When the obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, the stain in the gap was 0.1, which was no problem in practical use, the ground stain start temperature was 28 ° C, and the durability was high. It was 4,000 shots.

[Example 2]
A waterless lithographic printing plate original plate-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 planographic printing plate original plate-2 is the ink inking / repulsion function layer.

<Silicone rubber layer composition solution-2>
(A) α, ω-divinylpolydimethylsiloxane: 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: 20.8 mN / m, boiling point:> 150 ° C., manufactured by Shin-Etsu Chemical Co., Ltd.): 20.0 parts by weight (c) Methylhydrogensiloxane-dimethylsiloxane copolymer RD-1 ( (I) / ((i) + (ii)) × 100 = 50 mol%, manufactured by Toray Dow Corning Co., Ltd.): 3.39 parts by weight (d) Vinyltris (methylethylketooxyimino) silane: 2.64% by weight Part (e) Platinum catalyst SRX212 (manufactured by Toray Dow Corning Co., Ltd., platinum catalyst: 6.0% by weight): 6.17 parts by weight (f) "Isoper" E (manufactured by Esso Chemical Co., Ltd.): 900% by weight Further, an ink repulsive tape-2 was prepared as an ink repulsive composition layer to be attached to the gap between the waterless flat plate printing plate original plate-2 by the following method.

On the circuit tape "647" (thickness: 0.1 mm, manufactured by Teraoka Seisakusho Co., Ltd.), apply the ink repulsion tape-2 composition solution prepared immediately before application with a bar coater, and heat at 140 ° C. for 80 seconds. An ink repellent tape-2 was obtained by providing a silicone rubber layer having an average film thickness of 5.0 μm. The ink repulsive tape-2 composition solution was obtained by stirring and mixing the following components at room temperature (20 to 28 ° C.).

<Ink repulsion tape-2 composition solution>
(A) α, ω-divinylpolydimethylsiloxane: 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: 20.8 mN / m, boiling point:> 150 ° C., manufactured by Shin-Etsu Chemical Co., Ltd.): 4 parts by mass (c) Methylhydrogensiloxane-dimethylsiloxane copolymer RD-1 ((i) ) / ((I) + (ii)) × 100 = 50 mol%, manufactured by Toray Dow Corning Co., Ltd.): 4.1 parts by mass (d) Vinyltris (methylethylketooxyimino) silane: 3 parts by mass (e) Platinum catalyst SRX212 (manufactured by Toray Dow Corning Co., Ltd., platinum catalyst 6.0% by mass): 6 parts by mass (f) "Isoper" E (manufactured by Esso Chemical Co., Ltd.): 900 parts by mass Ink repulsion tape-1 A cylindrical printing plate original plate and a cylindrical printing plate were obtained in the same manner as in Example 1 except that the above was changed to the ink repellent tape-2. When the obtained cylindrical printing plate original plate was evaluated by the methods (1) and (6) above, the productivity was A and the film thickness of the ink repellent composition layer was 105 μm.

When the obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, the dirt in the gap was 0.05, the ground dirt start temperature was 30 ° C., and the durability was 4,000 shot. Met.

[Example 3]
A cylindrical printing plate original plate and a cylindrical printing plate were obtained in the same manner as in Example 2 except that the ink repulsive tape-2 composition solution was changed to the following ink repulsive tape-3 composition solution.

<Ink repulsion tape-3 composition solution>
(A) α, ω-divinylpolydimethylsiloxane: 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: 20.8 mN / m, boiling point:> 150 ° C., manufactured by Shin-Etsu Chemical Co., Ltd.): 50 parts by weight (c) Methylhydrogensiloxane-dimethylsiloxane copolymer RD-1 ((i) / ((I) + (ii)) × 100 = 50 mol%, manufactured by Toray Dow Corning Co., Ltd.): 2 parts by weight (d) Vinyltris (methylethylketooxyimino) silane: 3 parts by weight (e) Platinum catalyst SRX212 ( Toray Dow Corning Co., Ltd., platinum catalyst 6.0% by weight): 6 parts by weight (f) "Isopar" E (manufactured by Esso Chemical Co., Ltd.): 900 parts by weight The obtained cylindrical printing plate original plate As a result of evaluation by the method (1) above, the thickness of the ink-repulsive composition layer was 105 μm.

When the obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, there was no stain in the gap, the ground stain start temperature was very good at 35 ° C, and the durability was 4,000 shot. Met.

[Example 4]
The same as in Example 2 except that the thickness of the circuit tape “647” was changed from 0.1 mm to 0.08 mm and the ink repulsion tape-2 composition solution was changed to the following ink repulsion tape-4 composition solution. A cylindrical printing plate original plate and a cylindrical printing plate were obtained.

<Ink repulsion tape-4 composition solution>
(A) α, ω-divinylpolydimethylsiloxane: 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: 20.8 mN / m, boiling point:> 150 ° C., manufactured by Shin-Etsu Chemical Co., Ltd.): 50 parts by weight (c) Methylhydrogensiloxane-dimethylsiloxane copolymer RD-1 ((i) / ((I) + (ii)) × 100 = 50 mol%, manufactured by Toray Dow Corning Co., Ltd.): 2 parts by weight (d) Vinyltris (methylethylketooxyimino) silane: 3 parts by weight (e) Platinum catalyst SRX212 ( Toray Dow Corning Co., Ltd., platinum catalyst 6.0% by weight): 6 parts by weight (f) "Isopar" E (manufactured by Esso Chemical Co., Ltd.): 900 parts by weight The obtained cylindrical printing plate original plate As a result of evaluation by the method (1) above, the thickness of the ink-repulsive composition layer was 85 μm.

When the obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, there was no stain in the gap, the ground stain start temperature was very good at 35 ° C, and the durability was 4,000 shot. Met.

[Example 5]
The circuit tape "647" (thickness: 0.1 mm, manufactured by Teraoka Seisakusho Co., Ltd.) was changed to the Kapton tape "650S" (thickness: 0.035 mm, manufactured by Teraoka Seisakusho Co., Ltd.), and the ink repulsion tape-2 composition was used. Cylindrical printing plate original plate and cylindrical printing plate were obtained in the same manner as in Example 2 except that the solution was changed to the following ink repulsion tape-5 composition solution.

<Ink repulsion tape-5 composition solution>
(A) α, ω-divinylpolydimethylsiloxane: 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: 20.8 mN / m, boiling point:> 150 ° C., manufactured by Shin-Etsu Chemical Co., Ltd.): 20 parts by weight (c) Methylhydrogensiloxane-dimethylsiloxane copolymer RD-1 ((i) ) / ((I) + (ii)) × 100 = 50 mol%, manufactured by Toray Dow Corning Co., Ltd.): 3.4 parts by weight (d) Vinyltris (methylethylketooxyimino) silane: 3 parts by weight (e) Platinum catalyst SRX212 (manufactured by Toray Dow Corning Co., Ltd., platinum catalyst 6.0% by weight): 6 parts by weight (f) "Isoper" E (manufactured by Esso Chemical Co., Ltd.): 900 parts by weight Obtained cylindrical shape When the printing plate original plate was evaluated by the method (1) above, the thickness of the ink-repulsive composition layer was 40 μm.

When the obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, there was no stain in the gap, the ground stain start temperature was very good at 35 ° C, and the durability was 10,000 shot. Was good.

[Example 6]
Apply the above ink repulsion tape-5 composition solution prepared immediately before application to "Rumirror" (registered trademark) F99 (manufactured by Toray Industries, Inc.), which is polyethylene terephthalate, with a bar coater, and heat at 100 ° C. for 10 seconds. Then, an ink repulsion transfer tape-5 was obtained by providing a semi-cured silicone rubber layer having an average thickness of 5.0 μm.

Ink repulsion transfer tape-5 was attached to the gap between the cylindrical waterless planographic printing plate original plate-2 so that the silicone rubber layer side filled the gap, and from above F99, 160 ° C using a trowel heater. Was heated for 60 seconds to cure the silicone rubber layer. Then, F99 was peeled off to obtain a cylindrical printing plate original plate.

When evaluated by the method (1) above, the film thickness of the ink-repulsive composition layer was 5 μm.

Circuit tape "647" (thickness: 0.1 mm, manufactured by Teraoka Seisakusho Co., Ltd.) is attached to a part of the ink inking / repulsion function layer of the cylindrical printing plate original plate to form an ink inking part. A cylindrical printing plate was obtained. When the obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, there was no stain in the gap, the ground stain start temperature was 35 ° C, and the durability was 20,000 shot, which was very good. rice field.

[Example 7]
Examples except that the following ink-repulsive composition-1 was filled and cured at room temperature instead of attaching the ink-repulsive tape-2 to the gap between the cylindrically formed waterless lithographic printing plate original plate-2. A cylindrical printing plate original plate and a cylindrical printing plate were obtained in the same manner as in 2.

<Ink Repulsive Composition-1>
(A) α, ω-both terminal silanol polydimethylsiloxane: DMS-S33 (weight average molecular weight 43,500, manufactured by GELEST Inc.): 35.72 parts by mass (b) Methyltriacetoxysilane: 3 parts by mass (c) Tetraxane (Methylethylketooxyimino) Silane: 1 part by weight (d) Dibutyltin diacetate: 0.28 parts by weight (e) "Isoper" (registered trademark) E (manufactured by Esso Chemical Co., Ltd.): 60 parts by weight General formula ( The content of the compound represented by III) was 25% by weight based on the total of the compound represented by the general formula (II) and the compound represented by the general formula (III).

When the obtained cylindrical printing plate original plate was evaluated by the method (1) above, the film thickness of the ink-repulsive composition layer was 5 μm.

When the obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, the stain in the gap was 0.1, which was no problem in practical use, the ground stain start temperature was 28 ° C, and the durability was high. It was very good at 20,000 shots.

[Example 8]
Example 2 Except that the following ink-repulsive composition-2 was filled and cured at room temperature instead of sticking the ink-repulsive tape-2 in the gap between the cylindrically formed waterless lithographic printing plates-2. In the same manner as above, a cylindrical printing plate original plate and a cylindrical printing plate were obtained.

<Ink Repulsive Composition-2>
(A) α, ω-both terminal silanol 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: 20.8 mN / m, Boiling point:> 150 ° C., manufactured by Shin-Etsu Chemical Industry Co., Ltd.): 20 parts by mass (c) Methyltriacetoxysilane: 11.25 parts by mass (d) Tetraxane (Methylethylketooxyimino) Silane: 3.75 parts by mass (e) Dibutyltin diacetate: 0.28 parts by mass (f) "Isoper" (registered trademark) E (manufactured by Esso Chemical Co., Ltd.): 30 parts by mass General formula The content of the compound represented by (III) was 25% by mass with respect to the total of the compound represented by the general formula (II) and the compound represented by the general formula (III).

When the obtained cylindrical printing plate original plate was evaluated by the method (1) above, the film thickness of the ink-repulsive composition layer was 5 μm.

When the obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, there was no stain in the gap, the ground stain start temperature was 35 ° C, and the durability was 20,000 shot, which was very good. rice field.

[Example 9]
Instead of sticking the ink repellent tape-2 in the gap between the cylindrically formed waterless lithographic printing plate-2, fill it with the following ink repellent composition-3, press a trowel heater, and at 160 ° C. A cylindrical printing plate original plate and a cylindrical printing plate were obtained in the same manner as in Example 2 except that they were heated and cured for 60 seconds.

<Ink Repulsive Composition-3>
(A) α, ω-both terminal silanol 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: 20.8 mN / m, Boiling point:> 150 ° C., manufactured by Shin-Etsu Chemical Industry Co., Ltd.): 20 parts by mass (c) Methyltriacetoxysilane: 7.5 parts by mass (d) Tetraxane (Methylethylketooxyimino) Silane: 2.5 parts by mass (e) Dibutyltin diacetate: 0.28 parts by mass (f) "Isopar" (registered trademark) E (manufactured by Esso Chemical Co., Ltd.): 30 parts by mass General formula The content of the compound represented by (III) was 25% by mass with respect to the total of the compound represented by the general formula (II) and the compound represented by the general formula (III).

When the obtained cylindrical printing plate original plate was evaluated by the method (1) above, the film thickness of the ink-repulsive composition layer was 5 μm.

When the obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, there was no stain in the gap, the ground stain start temperature was 35 ° C, and the durability was 20,000 shot, which was very good. rice field.

[Example 10]
Examples except that the following ink-repulsive composition-4 was filled and cured at room temperature instead of attaching the ink-repulsive tape-2 to the gap between the cylindrically formed waterless lithographic printing plate original plate-2. A cylindrical printing plate original plate and a cylindrical printing plate were obtained in the same manner as in 2.

<Ink Repulsive Composition-4>
(A) α, ω-both terminal silanol 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: 20.8 mN / m, Boiling point:> 150 ° C., manufactured by Shin-Etsu Chemical Industry Co., Ltd.): 20 parts by mass (c) Methyltriacetoxysilane: 18 parts by mass (d) Tetraxane (methylethylketo) Oxyimimino) Silane: 1.5 parts by mass (e) Dibutyltin diacetate: 0.28 parts by mass (f) "Isopar" (registered trademark) E (manufactured by Esso Chemical Co., Ltd.): 30 parts by mass General formula (III) The content of the compound represented by) was 7.7% by mass with respect to the total of the compound represented by the general formula (II) and the compound represented by the general formula (III).

When the obtained cylindrical printing plate original plate was evaluated by the methods (1) and (7) above, the film thickness of the ink repulsive composition layer was 5 μm, and SiO _{4/2 in the ink repulsive composition layer was obtained.} The content of the constituent units was 0.55%.

When the obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, there was no stain in the gap, the ground stain start temperature was very good at 35 ° C, and the durability was 8,000 shot. Was good.

[Example 11]
Example 2 Except that the following ink-repulsive composition-5 was filled and cured at room temperature instead of attaching the ink-repulsive tape-2 to the gaps between the cylindrically formed waterless lithographic printing plates-2. In the same manner as above, a cylindrical printing plate original plate and a cylindrical printing plate were obtained.

<Ink Repulsive Composition-5>
(A) α, ω-both terminal silanol 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: 20.8 mN / m, Boiling point:> 150 ° C., manufactured by Shin-Etsu Chemical Industry Co., Ltd.): 10 parts by mass (c) Methyltriacetoxysilane: 19.8 parts by mass (d) Tetraxane (Methylethylketooxyimino) Silane: 2.2 parts by mass (e) Dibutyltin diacetate: 0.28 parts by mass (f) "Isoper" (registered trademark) E (manufactured by Esso Chemical Co., Ltd.): 30 parts by mass General formula The content of the compound represented by (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).

When the obtained cylindrical printing plate original plate was evaluated by the methods (1) and (7) above, the film thickness of the ink repulsive composition layer was 5 μm, and SiO _{4/2 in the ink repulsive composition layer was obtained.} The content of the constituent units was 0.83%.

When the obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, there was no stain in the gap, the ground stain start temperature was good at 33 ° C, and the durability was very high at 15,000 shot. Was good.

[Example 12]
Example 2 except that the following ink-repulsive composition-6 was filled and cured at room temperature instead of attaching the ink-repulsive tape-2 to the gaps between the cylindrically formed waterless lithographic printing plates-2. A cylindrical printing plate was obtained in the same manner as above.

<Ink Repulsive Composition-6>
(A) α, ω-both terminal silanol 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: 20.8 mN / m, Boiling point:> 150 ° C., manufactured by Shin-Etsu Chemical Industry Co., Ltd.): 10 parts by mass (c) Methyltriacetoxysilane: 12 parts by mass (d) Tetraxane (methylethylketo) Oxyimimino) Silane: 3 parts by mass (e) Dibutyltin diacetate: 0.28 parts by mass (f) "Isopar" (registered trademark) E (manufactured by Esso Chemical Co., Ltd.): 30 parts by mass With the general formula (III) The content of the represented compound was 20% by mass with respect to the total of the compound represented by the general formula (II) and the compound represented by the general formula (III).

When the obtained cylindrical printing plate original plate was evaluated by the methods (1) and (7) above, the film thickness of the ink repulsive composition layer was 5 μm, and SiO _{4/2 in the ink repulsive composition layer was obtained.} The content of the constituent units was 1.04%.

When the obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, there was no stain in the gap, the ground stain start temperature was good at 33 ° C, and the durability was very high at 20,000 shot. Was good.

[Example 13]
Example 2 Except that the following ink-repulsive composition-7 was filled and cured at room temperature instead of attaching the ink-repulsive tape-2 to the gaps between the cylindrically formed waterless lithographic printing plates-2. In the same manner as above, a cylindrical printing plate original plate and a cylindrical lithographic printing plate were obtained.

<Ink Repulsive Composition-7>
(A) α, ω-both terminal silanol 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: 20.8 mN / m, Boiling point:> 150 ° C., manufactured by Shin-Etsu Chemical Industry Co., Ltd.): 20 parts by mass (c) Methyltriacetoxysilane: 12 parts by mass (d) Tetraxane (methylethylketo) Oxyimimino) Silane: 4 parts by mass (e) Dibutyltin diacetate: 0.28 parts by mass (f) "Isopar" (registered trademark) E (manufactured by Esso Chemical Co., Ltd.): 30 parts by mass With the general formula (III) The content of the represented compound 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).

When the obtained cylindrical printing plate original plate was evaluated by the methods (1) and (7) above, the film thickness of the ink repulsive composition layer was 5 μm, and SiO _{4/2 in the ink repulsive composition layer was obtained.} The content of the constituent units was 1.41%.

When the obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, there was no stain in the gap, the ground stain start temperature was 35 ° C, and the durability was 20,000 shot, which was very good. rice field.

[Example 14]
Example 2 Except that the following ink-repulsive composition-8 was filled and cured at room temperature instead of attaching the ink-repulsive tape-2 to the gaps between the cylindrically formed waterless lithographic printing plates-2. In the same manner as above, a cylindrical printing plate original plate and a cylindrical printing plate were obtained.

<Ink Repulsive Composition-8>
(A) α, ω-both terminal silanol 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: 20.8 mN / m, Boiling point:> 150 ° C., manufactured by Shin-Etsu Chemical Industry Co., Ltd.): 20 parts by mass (c) Methyltriacetoxysilane: 7 parts by mass (d) Tetraxane (methylethylketo) Oxyimimino) Silane: 7 parts by mass (e) Dibutyltin diacetate: 0.28 parts by mass (f) "Isopar" (registered trademark) E (manufactured by Esso Chemical Co., Ltd.): 30 parts by mass With the general formula (III) The content of the represented compound 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).

When the obtained cylindrical printing plate original plate was evaluated by the methods (1) and (7) above, the film thickness of the ink repulsive composition layer was 5 μm, and SiO _{4/2 in the ink repulsive composition layer was obtained.} The content of the constituent units was 2.43%.

When the obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, there was no stain in the gap, the ground stain start temperature was 35 ° C, and the durability was 12,000 shot, which was very good. rice field.

[Example 15]
Example 2 Except that the following ink-repulsive composition-9 was filled and cured at room temperature instead of attaching the ink-repulsive tape-2 to the gaps between the cylindrically formed waterless lithographic printing plates-2. In the same manner as above, a cylindrical printing plate original plate and a cylindrical printing plate were obtained.

<Ink Repulsive Composition-9>
(A) α, ω-both terminal silanol 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: 20.8 mN / m, Boiling point:> 150 ° C., manufactured by Shin-Etsu Chemical Industry Co., Ltd.): 20 parts by mass (c) Methyltriacetoxysilane: 3 parts by mass (d) Tetraxane (methylethylketo) Oxyimimino) Silane: 9 parts by mass (e) Dibutyltin diacetate: 0.28 parts by mass (f) "Isopar" (registered trademark) E (manufactured by Esso Chemical Co., Ltd.): 30 parts by mass With the general formula (III) The content of the represented compound was 75% by mass with respect to the total of the compound represented by the general formula (II) and the compound represented by the general formula (III).

When the obtained cylindrical printing plate original plate was evaluated by the methods (1) and (7) above, the film thickness of the ink repulsive composition layer was 5 μm, and SiO _{4/2 in the ink repulsive composition layer was obtained.} The content of the constituent units was 3.07%.

When the obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, there was no stain in the gap, the ground stain start temperature was very good at 35 ° C, and the durability was 8,000 shot. Was good.

[Example 16]
Cylindrical printing plate in the same manner as in Example 13 except that the ink-repulsive composition-7 was filled, leveled flat with a scraper, and cured by heating at 150 ° C. for 30 seconds using an electric iron. An original plate and a cylindrical printing plate were obtained. When the obtained cylindrical printing plate original plate was evaluated by the method (9) above, the arithmetic surface roughness Ra of the flattened ink-repulsive composition-7 layers was 0.20 μm.

When the obtained cylindrical printing plate was evaluated by the methods (3) and (5) above, there was no dirt in the gap and the durability was very good at 25,000 shots.

[Example 17]
A lithographic printing plate SUPERIA ZP (manufactured by FUJIFILM) with a solid image part of 200 x 200 mm in the center is wound around the plate cylinder of the flexible packaging printing machine "OFFSET CI8" (manufactured by COMEXI) to form a cylindrical shape, and water is formed. A cylindrical printing plate was produced by filling the gap formed between the edges of the lithographic printing plate with the following ink-repulsive composition-10 prepared by stirring at room temperature and drying at room temperature. When evaluated by the method (9) above, the arithmetic surface roughness Ra of the ink repulsive composition-10 layer was 0.52 μm. Then, the above-mentioned (8) water-based flexible packaging printing was carried out.

<Ink Repulsive Composition-10>
(A) Water: 85% by mass
(B) Gum arabic (manufactured by Nippon Powder Chemicals Co., Ltd.): 10% by mass
(C) Benzyl alcohol: 2.5% by mass
(D) Hexametholic acid: 2% by mass
(E) Sodium dodecylbenzene sulfonate: 0.5% by mass
When evaluated by the methods (3) and (5) above, there was no dirt in the gap, and the durability was very good at 25,000 shots.

[Example 18]
Cylindrical printing plate original plate and cylindrical printing plate in the same manner as in Example 17 except that the following ink repulsive composition-11 prepared by stirring at room temperature was used instead of the ink repulsive composition-10. Got When the obtained cylindrical printing plate original plate was evaluated by the method (9) above, the arithmetic surface roughness Ra of the ink repulsive composition-11 layer was 0.48 μm. Then, the above-mentioned (8) water-based flexible packaging printing was carried out.

<Ink Repulsive Composition-11>
(A) Water: 80% by mass
(B) Resol type phenol resin Phenolite GG-1402 (manufactured by DIC Corporation): 19% by mass
(C) Paratoluenesulfonic acid: 1% by mass
When evaluated by the methods (3) and (5) above, the dirt in the gap was 0.1, which was not a problem in practical use, and the durability was as good as 8,000 shots.

[Example 19]
Cylindrical printing plate in the same manner as in Example 18 except that the ink repulsive composition-11 was used to fill the gap between the edges of the lithographic printing plate original plate and heated at 150 ° C. for 30 seconds using an electric iron. An original plate and a cylindrical printing plate were obtained. When the obtained cylindrical printing plate original plate was evaluated by the method (9) above, the arithmetic surface roughness Ra of the ink repulsive composition-11 layer was 0.35 μm. Then, the above-mentioned (8) water-based flexible packaging printing was carried out.

When evaluated by the methods (3) and (5) above, the dirt in the gap was 0.05, and the durability was very good at 15,000 shots.

[Example 20]
Same as in Example 18 except that the ink repulsive composition-11 was used to fill the gap between the edges of the lithographic printing plate, leveled flat with a scraper, and heated at 150 ° C. for 30 seconds using an electric iron. A cylindrical printing plate original plate and a cylindrical printing plate were obtained. When the obtained cylindrical printing plate original plate was evaluated by the method (9) above, the arithmetic surface roughness Ra of the flattened ink-repulsive composition-11 layer was 0.20 μm. Then, the above-mentioned (8) water-based flexible packaging printing was carried out.

When evaluated by the methods (3) and (5) above, there was no dirt in the gap, and the durability was very good at 20,000 shots.

[Comparative Example 1]
A cylindrical printing plate original plate and a cylindrical printing plate were obtained in the same manner as in Example 1 except that the ink repellent tape-1 was not attached to the gap between the waterless planographic printing plates-1 formed in a cylindrical shape. When evaluated by the above methods (3) to (5), the ground fouling start temperature was 28 ° C., and the durability was very good at 20,000 shots, but the fouling in the gap was 1.0. Therefore, the result was impractical.

[Comparative Example 2]
A cylindrical printing plate original plate was prepared 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 coated in this order on a degreased cylindrical aluminum base material having a thickness of 0.30 mm. bottom. Here, the heat-sensitive layer composition solution was applied so as to cover half of the silicone rubber layer provided on the cylindrical aluminum base material in the width direction.

The cylindrical printing plate original plate is manufactured by coating one by one on a cylindrical aluminum base material, and when a heat-sensitive layer composition solution is applied on a silicone rubber layer having a low surface free energy, it is repelled. Productivity was significantly inferior due to the frequent occurrence of.

Using the obtained cylindrical printing plate original plate, a cylindrical printing plate was obtained in the same manner as in Example 1. When the obtained cylindrical printing plate was evaluated by the methods (3) to (5) above, there was no stain in the gap due to the cylindrical coating, and the ground stain start temperature was 28 ° C., but silicone was used during printing. Peeling occurred at the interface between the layer and the heat-sensitive layer, and the durability was 2,000 shot, which was not practical.

1 Base material 2 Organic layer 3 Heat-sensitive layer 4 Ink inking / repulsive functional layer 5 Gap 6 Ink repulsive composition or ink repulsive composition layer 6H Thickness of ink repulsive composition layer 100 Flat plate printing plate Original plate or flat plate printing Plate 200 Flat plate printed plate molded into a cylindrical shape Original plate or flat plate printed plate molded into a cylindrical shape 300 Cylindrical printing plate Original plate or cylindrical printing plate

Claims (22)

1. A method for producing a lithographic printing plate, which comprises a step of winding a lithographic printing plate or a lithographic printing plate original plate around a cylindrical support and filling a gap between the ends of the lithographic printing plate or the lithographic printing plate original plate with an ink repulsive composition. ..
2. The method for manufacturing a cylindrical printing plate according to claim 1, wherein the length of the gap in the circumferential direction is 5 mm or less.
3. The method for producing a cylindrical printing plate according to claim 1 or 2, wherein the ink-repulsive composition contains a silicone compound.
4. The method for producing a cylindrical printing plate according to any one of claims 1 to 3, wherein the ink-repulsive composition contains 5 to 50% by mass of silicone oil.
5. The method for producing a cylindrical printing plate according to claim 3 or 4, wherein the silicone compound contains a SiO _{4/2 structural unit.}
6. _{The SiO 4/2} structural unit contained in the silicone compound is the total of _{the R 3} SiO _1/2 structural unit, the R ₂ SiO _2/2 structural unit, the RSiO _3/2 structural unit, and the SiO _{4/2 structural unit.} The method for manufacturing a cylindrical printing plate according to claim 5, which is 0.8 to 2.5%.
7. The method for producing a cylindrical printing plate according to claim 1 or 2, wherein the ink-repulsive composition contains a hydrophilic compound.
8. The method for producing a cylindrical printing plate according to claim 7, wherein the hydrophilic compound contains a water-soluble resin.
9. The method for producing a cylindrical printing plate according to claim 8, wherein the water-soluble resin has a vinyl group and / or a methylol group.
10. 7. How to make a cylindrical printing plate.
11. The method for producing a cylindrical printing plate according to any one of claims 1 to 9, wherein the ink-repulsive composition is an ink-repulsive tape on the surface.
12. The method for producing a cylindrical printing plate according to any one of claims 1 to 11, wherein an ink repulsive composition layer having a film thickness of 1 to 100 μm is formed from the ink repulsive composition.
13. The method for producing a cylindrical printing plate according to any one of claims 1 to 12, wherein an ink repulsive composition layer having an arithmetic surface roughness Ra of 0.3 μm or less is formed from the ink repulsive 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 for producing a cylindrical printing plate according to claim 14, wherein the sleeve contains glass fiber and / or aluminum.
16. A printed matter including a step of adhering ink to the surface of a 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 printed matter directly or via a blanket. Production method.
17. The method for producing a printed matter according to claim 16, further comprising a step of applying an ink-repulsive liquid to the surface of the cylindrical printing plate before the step of adhering ink to the surface of the cylindrical printing plate.
18. The method for producing a printed matter according to claim 16 or 17, wherein the cylindrical printing plate is composed of at least a waterless lithographic printing plate.
19. The method for producing a printed matter according to any one of claims 16 to 18, further comprising a step of heating the ink transferred to the blanket in the step of transferring the ink to the object to be printed via the blanket.
20. The printed matter according to any one of claims 16 to 19, which comprises a step of transferring the ink to a printed matter directly or via a blanket followed by a step of irradiating the ink transferred to the printed matter with an electron beam. Manufacturing method.
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 for producing a printed matter according to any one of claims 16 to 21, wherein the printed matter is conveyed in a roll-to-roll manner.

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