JP2010076387A - Apparatus for molding cylindrical original plate for printing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus for molding a cylindrical original plate for printing which manufactures a cylindrical original plate for printing with a high productivity and with a high thickness accuracy by sticking a sheet-like resin on a cylindrical substrate. <P>SOLUTION: The apparatus for molding the cylindrical original plate for printing is for sticking the sheet-like resin on the cylindrical substrate (a). The apparatus for molding the cylindrical original plate for printing includes: (1) a mechanism which holds the cylindrical substrate (a) having a photo-curable adhesive layer on the surface and rotates it circumferentially; (2) a mechanism which has a plate-like article or a cylindrical article with a light beam permeable slit and changes an interval between it and the surface of the cylindrical substrate (a); (3) a light source which irradiates it with the light through the light beam permeable slit and is arranged in the mechanism (2); (4) an optical system which pinches the sheet-like resin between the plate-like article or the cylindrical article and the cylindrical substrate (a), and condenses the light from the light source on the photo-curable adhesive layer existing between the sheet-like resin and the cylindrical substrate (a) through the plate-like article or the cylindrical article. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a cylindrical printing original plate forming apparatus. Specifically, the present invention relates to a cylindrical printing original plate forming apparatus that adheres a sheet-like resin onto a cylindrical support (a) using light.

In recent years, when manufacturing resin relief printing such as flexographic printing, dry offset printing, and letter press printing, or when performing surface processing such as embossing, the resin portion irradiated with laser light is irradiated on the resin layer surface. A laser engraving method for forming a concavo-convex pattern on the surface by being removed has come to be used.
The printing plate material applied to the laser engraving method is obtained by curing a vulcanized rubber, a photosensitive resin cured product obtained by photocuring a photosensitive resin composition, and a thermosetting resin composition. A thermosetting resin cured product is used. In particular, in recent years, a technique for laser engraving a cured photosensitive resin has been increasing from the viewpoint of shortening the processing time.

  Patent Document 1 describes a method of manufacturing a cylindrical printing original plate by winding a sheet-like photosensitive resin around a cylindrical support and welding the ends. In this method, since the sheet-shaped photosensitive resin is in an uncured state during a series of operations, the thickness of the sheet-shaped photosensitive resin can be reduced by touching the surface or contacting the sheet-shaped photosensitive resin with other objects during the operation. There is a reduction in accuracy. Further, after forming into a cylindrical shape in order to ensure the thickness accuracy, a further surface adjustment step is required in which the surface is subjected to thermal calendering or polishing. Especially in the field of printing technology, it is extremely important to ensure the thickness accuracy of the printing plate.

Japanese Patent No. 2846954

There has been a strong demand for an apparatus for manufacturing a cylindrical printing original plate with high productivity and high thickness accuracy by adhering a sheet-like resin onto the cylindrical support (a). Did not exist.
The problem to be solved by the present invention is to provide a cylindrical printing original plate forming apparatus for producing a cylindrical printing original plate by adhering a sheet-like resin on a cylindrical support with high productivity and high thickness accuracy. There is.

  As a result of intensive studies to solve the above problems, the present inventors have found that a cylindrical printing original plate molding apparatus for adhering a sheet-like resin onto a cylindrical support (a) is (1) a photocurable adhesive. A mechanism for holding the cylindrical support (a) having a layer on its surface and rotating it in the circumferential direction; and (2) a plate-like object or a cylindrical object having a light transmitting slit, and the cylindrical support (A) a mechanism for changing the distance from the surface; (3) a light source that irradiates light through the light transmitting slit and disposed in the mechanism (2); and (4) the plate-like object or The sheet-shaped resin is sandwiched between a cylindrical object and the cylindrical support (a), and is present between the sheet-shaped resin and the cylindrical support (a) through the plate-shaped object or cylindrical object. An optical system for condensing the light from the light source on the photocurable adhesive layer. By obtaining, it can solve the above problems, and completed the present invention.

The present invention is as follows.
1.
A cylindrical printing original plate molding apparatus for adhering a sheet-like resin on a cylindrical support (a),
(1) A mechanism for holding the cylindrical support (a) having a photocurable adhesive layer on the surface and rotating it in the circumferential direction;
(2) a mechanism having a plate-like object or a cylindrical object having a light-transmitting slit, and changing a distance from the surface of the cylindrical support (a);
(3) irradiating light through the light transmissive slit, and a light source disposed in the mechanism (2);
(4) The sheet resin is sandwiched between the plate or cylinder and the cylindrical support (a), and the sheet resin and the cylindrical support are passed through the plate or cylinder. An optical system for condensing light from the light source on the photocurable adhesive layer existing between (a) and a cylindrical printing original plate forming apparatus.
2.
The light source is a light source that emits light having a wavelength of 200 nm to 400 nm. The cylindrical printing original plate forming apparatus described in 1.
3.
1. The width of the light transmissive slit is 0.5 mm or more and 20 mm or less. Or 2. The cylindrical printing original plate forming apparatus described in 1.
4).
The cylindrical support (a) is a hollow cylindrical support made of fiber reinforced plastic or metal,
The mechanism (1) has a cylindrical body made of at least one material selected from the group consisting of metal, rubber, and plastic. To 3. The cylindrical printing original plate forming apparatus of any one of these.
5).
The optical system (4) has a condensing lens and a mechanism for changing the distance between the condensing lens and the surface of the cylindrical support (a). To 4. The cylindrical printing original plate forming apparatus of any one of these.
6).
The plate or cylinder is made of quartz glass, and the light transmittance at a wavelength of 350 nm is 80% or more and 100% or less. To 5. The cylindrical printing original plate forming apparatus of any one of these.
7).
The cylindrical support (a) and the plate-like object or cylindrical object move synchronously,
1. The cylindrical support (a) and the sheet-like resin have a part that is always in contact, and the contacted part is irradiated with light. To 6. The cylindrical printing original plate forming apparatus of any one of these.
8).
1. To 7. The cylindrical printing original plate manufactured using the cylindrical printing original plate forming apparatus of any one of these.
9.
A method for producing a cylindrical printing original plate having a cylindrical support (a) and a sheet-like resin bonded on the cylindrical support (a),
(I) forming a photocurable adhesive layer on the surface of the cylindrical support (a);
(Ii) installing the sheet-like resin on the photocurable adhesive layer;
(Iii) sandwiching the sheet-like resin between a plate-like object or a cylindrical object having a light-transmitting slit and the cylindrical support (a);
(Iv) irradiating the photocurable adhesive layer with light through the light transmissive slit;
(V) rotating the cylindrical support (a) and irradiating light at a position different from that in the step (iv).
10.
8. The sheet-like resin is made of at least one material selected from the group consisting of a thermoplastic resin, a photosensitive resin composition, and a thermosetting resin composition. The manufacturing method of the cylindrical printing original plate as described in 1 ..
11.
8. The sheet-like resin is a sheet-like printing original plate in which a photosensitive resin cured product or a thermosetting resin cured product is laminated on a sheet-like support made of a thermoplastic resin. Or 10. The manufacturing method of the cylindrical printing original plate as described in 1 ..
12
The photosensitive resin composition or thermosetting resin composition is polyamide, polyimide, polyurethane, polyester, polycarbonate, polyether polyol, polyvinyl alcohol, vinyl alcohol-vinyl acetate copolymer, styrene-butadiene copolymer, and styrene. -Containing at least one resin selected from the group consisting of isoprene copolymers; Or 11. The manufacturing method of the cylindrical printing original plate as described in 1 ..
13.
8. The cylindrical printing original plate is a cylindrical printing original plate or a cylindrical printing plate used in flexographic printing, dry offset printing, or gravure printing, To 12. The method for producing a cylindrical printing original plate according to any one of the above.
14
12. The cylindrical printing original plate is a cylindrical printing original plate for laser engraving, The manufacturing method of the cylindrical printing original plate as described in 1 ..

  According to the present invention, it is possible to provide a cylindrical printing original plate forming apparatus for manufacturing a cylindrical printing original plate with high productivity and high thickness accuracy by adhering a sheet-like resin on the cylindrical support (a). it can.

  Hereinafter, the best mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

[Outline of cylindrical printing plate forming equipment]
The cylindrical printing original plate forming apparatus of the present embodiment is an apparatus for adhering a sheet-like resin on a cylindrical support (a),
(1) A mechanism for holding the cylindrical support (a) having a photocurable adhesive layer on the surface and rotating it in the circumferential direction;
(2) a mechanism having a plate-like object or a cylindrical object having a light-transmitting slit, and changing a distance from the surface of the cylindrical support (a);
(3) irradiating light through the light transmissive slit, and a light source disposed in the mechanism (2);
(4) The sheet resin is sandwiched between the plate or cylinder and the cylindrical support (a), and the sheet resin and the cylindrical support are passed through the plate or cylinder. (A) It is a cylindrical printing original plate forming apparatus provided with the optical system for condensing the light from the said light source in the said photocurable adhesive bond layer existing between.

  The cylindrical printing original plate forming apparatus of the present embodiment has a cylindrical shape by placing a sheet-like resin on a cylindrical support (a) and irradiating light to a photocurable adhesive layer present at the interface. It is an apparatus for bonding the support (a) and the sheet-like resin.

As the mechanism (1) for holding the cylindrical support (a) and rotating it in the circumferential direction, it is preferable to have a cylindrical object made of at least one material selected from the group consisting of metal, rubber, and plastic.
Examples of the cylindrical member include an air cylinder and a jig such as an air shaft having a mechanism for changing the outer diameter of the cylinder when the cylindrical support (a) is a hollow cylindrical support. The cylindrical support (a) is held using the jig. The jig preferably has a shaft for rotating the hollow cylindrical support in the circumferential direction, and preferably holds the shaft and rotates the hollow cylindrical support in the circumferential direction.
It is preferable that the jig has a shaft portion such as a journal, and the cylindrical printing original plate forming apparatus includes a rotation mechanism for holding and rotating the shaft portion. An example of the rotating mechanism is a stepping motor having an encoder in order to ensure positional accuracy.

The cylindrical printing original plate forming apparatus has a plate-like object or a cylindrical object having a light-transmitting slit, and the cylindrical support (a) is in contact with the cylindrical support (a) and the sheet-like resin. A mechanism (2) for changing the distance between the surface and the plate or cylindrical object is provided.
By being sandwiched between the cylindrical support (a) and a plate-like or cylindrical object, the surface (photocurable adhesive layer) of the cylindrical support (a) and the sheet-like resin can be brought into contact with each other. .
The cylindrical printing original plate forming apparatus includes a mechanism that can change the distance between the surface of the cylindrical support (a) and the plate or cylindrical object from the viewpoint of workability. By reducing the distance between the surface of the cylindrical support (a) and the plate or cylindrical object, the cylindrical support (a) and the plate or cylindrical object are reduced. The sheet resin sandwiched between the objects can contact the cylindrical support (a).

  In the cylindrical printing original plate forming apparatus, since light is irradiated through the light transmissive slit, a portion where the cylindrical support (a) and the sheet-like resin are in contact can be photocured. The light-transmitting slit forms a slit generally parallel to the long axis of the cylindrical support (a), and rotates the cylindrical support (a), thereby rotating the cylindrical support (a) on the cylindrical surface. It can be photocured entirely.

The plate-like or cylindrical object having a light-transmitting slit preferably has a light transmittance of 80% or more and 100% or less at a wavelength of 350 nm. The light transmittance at 350 nm of the plate-like or cylindrical support is more preferably 90% or more and 100% or less, and still more preferably 95% or more and 100% or less.
If the light transmittance is within the above range, it can be ensured in the photocurable resin layer without losing the energy of the irradiated light, and the efficiently irradiated light can be converted into the cylindrical support (a). It can be used for adhesion with a sheet-like resin.
The cylindrical object is preferably a hollow cylinder, and the thickness of the plate or cylinder is preferably 0.1 mm or more and 50 mm or less. The thickness of the plate-like object or cylindrical object is more preferably 0.5 mm or more and 10 mm or less, and further preferably 1 mm or more and 5 mm or less.
If the thickness of the plate-like object or the cylindrical object is within the above range, the mechanical strength can be sufficiently secured, and the plate-like object or the cylindrical object can be used without being excessively heavy.
The material of the plate or cylinder is preferably quartz glass.

The material to be used for the light shielding part with a light transmissive slit formed on the plate or cylindrical object is not particularly limited as long as it has a light shielding property.
Examples of the material for the light-shielding portion with a light transmissive slit include organic thin films containing metal thin films such as chromium and aluminum, or black pigments such as carbon black and graphite, from the viewpoint of ensuring high light-shielding properties.
In the case of a plate-shaped object, it is preferable that the light-shielding part with a light-transmitting slit is installed on the surface not in contact with the sheet-like resin. When the cylindrical support (a) and the plate-like object move in synchronization, the position of the light-transmitting slit also moves if the light-transmitting slit is fixed to the surface of the plate-like object. The light transmissive slit is arranged separately from the plate-like material so that light can be applied to the light transmissive resin layer in the portion where the cylindrical support (a) and the sheet-like resin are in contact with each other. It is preferably fixed.
In the case of a cylindrical object, it is preferable that the light-shielding part with a light transmissive slit is installed inside the cylindrical object. Further, the cylindrical object may be a complete cylinder or a semi-cylindrical shape including a part of the circumference of the cylinder.

  The width of the light transmissive slit is preferably 0.5 mm or more and 20 mm or less, more preferably 0.5 mm or more and 10 mm or less, and further preferably 0.5 mm or more and 5 mm or less.

The cylindrical printing original plate forming apparatus includes a light source (3) that irradiates light through a light transmissive slit and is disposed in a mechanism (2).
Although it does not specifically limit as a light source (3), A photocurable adhesive can be photocured and a cylindrical support body (a) and sheet-like resin can be adhere | attached, Wavelength of 200 nm or more A light source that emits light of 400 nm or less is preferred.
Examples of the light source (3) include a metal halide lamp, a xenon lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a chemical lamp, and a germicidal lamp.
The light source may be a continuous light source or a pulsed light source. It is preferable that the illuminance at a wavelength of 350 nm is 10 mW / cm ² or more and 2 W / cm ² or less, more preferably 50 mW / cm ² or more and 500 mW / cm ^{2 on the} surface of the sheet-like resin of light irradiated on the photocurable adhesive. or less, still more preferably 80 mW / cm ² or more 300 mW / cm ² or less.
When a light source with high output is used, the cylindrical printing original plate forming apparatus may be provided with an intake / exhaust mechanism or a water cooling mechanism so as not to accumulate heat.

The cylindrical printing original forming apparatus sandwiches a sheet-shaped resin between a plate-shaped object or a cylindrical object and a cylindrical support (a), and passes the sheet-shaped resin or the cylindrical support through the plate-shaped object or the cylindrical object. Is provided with an optical system (4) for condensing light from the light source.
The optical system (4) preferably has a condensing lens and a mechanism for changing the distance between the condensing lens and the surface of the cylindrical support (a). The optical system (4) may be disposed in the light source or may be installed on the surface of the light source.

  Since it is preferable to focus the light near the contact interface between the photocurable adhesive layer on the surface of the cylindrical support (a) and the sheet-like resin, the distance of the condenser lens of the optical system (4) is changed. It is preferable to control the distance between the surface of the cylindrical support (a) and the condensing lens by the mechanism for changing the position of the cylindrical support (a) and the mechanism (2) for changing the position of the cylindrical support (a).

The number of locations where the cylindrical support (a) and the sheet-like resin are bonded is preferably plural, more preferably the entire surface.
When light emitted from a lamp that is long in the long axis direction of the cylindrical support (a) is condensed by a condenser lens and irradiated through a light-transmitting slit, the entire surface can be obtained by rotating the cylindrical support (a). Can be photocured.

The cylindrical printing original plate forming apparatus preferably includes a mechanism for moving a position to irradiate light. When the light source is a point light source, the condensing lens is generally disposed at the end of the optical system. Therefore, as a mechanism for moving the position of irradiating light, a mechanism for moving the position of this lens in the long axis direction of the cylindrical support (a), a galvanometer mirror or a polygon mirror for scanning light rays before the condenser lens The mechanism etc. which arrange | position can be mentioned.
The light does not need to move exactly along the major axis, but may be moved in the major axis direction. The cylindrical support (a) can be rotated to change the position where light is irradiated in the circumferential direction. The location where the light is irradiated may be performed without any gap in the cylindrical surface, or may be performed with a short gap.

In the present embodiment, it is preferable that the light-transmissive plate-like object or cylindrical object and the cylindrical support (a) move synchronously. Since the cylindrical support (a) and the sheet-shaped resin can always be brought into contact with each other by moving both in synchronization, a void is formed between the cylindrical support (a) and the sheet-shaped resin. Can be prevented.
In the present embodiment, it is preferable that the cylindrical support (a) and the sheet-like resin have a part that is always in contact, and the contacted part is irradiated with light. Since the cylindrical resin (a) and the sheet resin are always in contact, the sheet resin can be bonded onto the cylindrical support with high thickness accuracy.

  By using the cylindrical printing original plate forming apparatus of the present embodiment, the sheet-like resin can be bonded onto the cylindrical support (a). In the present embodiment, it is preferable to use a cylindrical support (a) and a sheet-like resin described below.

[Cylindrical support (a)]
Examples of the cylindrical support (a) include a metal, rubber, or plastic cylinder, and a hollow cylindrical support such as a metal, plastic, or fiber-reinforced plastic sleeve. From the viewpoint of weight and handling, a hollow cylindrical support is preferable.
Examples of the material constituting the metallic cylinder or the metallic sleeve include materials such as aluminum, nickel, and iron.
Examples of the material constituting the plastic cylinder or the plastic sleeve include materials such as polyester, polyimide, polyamide, polyphenylene ether, polyphenylene thioether, polysulfone, and epoxy resin.
Examples of the fiber material constituting the fiber reinforced plastic sleeve include materials such as polyester fiber, polyimide fiber, polyamide fiber, polyurethane fiber, cellulose fiber, glass fiber, metal fiber, ceramic fiber, and carbon fiber.
Examples of the material constituting the rubber cylinder include materials such as EPDM rubber, fluorine rubber, silicone rubber, SB rubber, and urethane rubber.

When the cylindrical support (a) is a hollow cylindrical support, the thickness of the hollow cylindrical support is preferably 0.2 mm or more and 2 mm or less. The thickness of the intermediate cylindrical support is more preferably 0.3 mm or more and 1.5 mm or less, and further preferably 0.4 mm or more and 1 mm or less.
If the thickness of the hollow cylindrical support is within the above range, it can be easily mounted on the mechanism (1), and sufficient mechanical strength can be ensured without being broken or cracked.

[Sheet resin]
The sheet-like resin is preferably made of at least one material selected from the group consisting of a thermoplastic resin, a photosensitive resin composition, and a thermosetting resin composition.
As a sheet-like resin, a photosensitive resin cured product or a thermosetting resin cured product on a sheet-like support made of a thermoplastic resin from the viewpoint of ensuring laser engraving property, image forming property, flexibility, and mechanical strength. It is preferable that it is a sheet-like laminated body with which is laminated | stacked.

In the present embodiment, the cured photosensitive resin is a cured resin obtained by photocuring the photosensitive resin composition, and the cured thermosetting resin is obtained by thermosetting the thermosetting resin composition. (Hereinafter simply referred to as “photosensitive resin composition and thermosetting resin composition”, “resin composition”, “photosensitive resin cured product and thermosetting resin cured product”, “resin curing”) May be described as "thing").
The resin composition is selected from the group consisting of polyamide, polyimide, polyurethane, polyester, polycarbonate, polyether polyol, polyvinyl alcohol, vinyl alcohol-vinyl acetate copolymer, styrene-butadiene copolymer, and styrene-isoprene copolymer. It is preferable to contain at least one kind of resin.

When the cylindrical printing original plate is for flexographic printing, the resin composition may be a polyurethane having a relatively low hardness, such as polyurethane, polyester, polycarbonate, polyether polyol, styrene-butadiene copolymer, and styrene-isoprene copolymer. It is preferable to contain a material.
When the cylindrical printing original plate is for dry offset printing or gravure printing, the resin composition is made of a material such as polyamide, polyimide, polyvinyl alcohol, vinyl alcohol-vinyl acetate copolymer, and polycarbonate having a relatively high hardness. It is preferable to contain.

The sheet-like support preferably has a thickness of 10 μm or more and 500 μm or less from the viewpoints of dimensional stability, lightness, flexibility, and flatness. The thickness of the sheet-like support is more preferably from 50 μm to 300 μm, still more preferably from 50 μm to 200 μm.
Examples of the material for the sheet-like support include metals such as nickel, aluminum, and iron, and a thermoplastic resin that is at least one selected from the group consisting of polyester, polyamide, and polyimide.

  The sheet-like resin is preferably a material that transmits the light to be used, and the light transmittance of the sheet-like resin at the wavelength of the light to be used is preferably 50% or more and 100% or less, more preferably 70% or more. 100% or less, more preferably 80% or more and 100% or less.

The thickness of the sheet-like resin is preferably from 0.1 mm to 5 mm.
If the thickness of the sheet-like resin is within this range, it can be used for printing applications such as flexographic printing, dry offset printing, and gravure printing.

  In the present embodiment, the resin composition preferably contains a resin (b) and an organic compound (c).

[Resin (b)]
The number average molecular weight of the resin (b) is preferably 1000 or more and 300,000 or less, more preferably 2000 or more and 200,000 or less, and further preferably 5000 or more and 150,000 or less.
If the number average molecular weight of the resin (b) is 1000 or more, the cured resin obtained by crosslinking later maintains strength, and can be used repeatedly when used as a printing substrate or the like.
If the number average molecular weight of the resin (b) is 300,000 or less, the melt viscosity of the resin composition does not rise excessively during extrusion molding, and a sheet-like resin cured product can be produced.

  In the present embodiment, the number average molecular weight means a value measured by gel permeation chromatography, calibrated with polystyrene having a known molecular weight, and converted.

The resin (b) may have a polymerizable unsaturated group in the molecule.
Preferred examples of the resin (b) include compounds having an average number of polymerizable unsaturated groups of 0.7 or more per molecule.
If the average number of polymerizable unsaturated groups is 0.7 or more per molecule, the cured resin has excellent mechanical strength and good durability, and can withstand repeated use, particularly as a printing substrate. It is preferable.
From the viewpoint of the mechanical strength of the cured resin, the number of polymerizable unsaturated groups in the resin (b) is preferably 0.7 or more per molecule, more preferably 1 or more, more preferably 1 or more. 10 or less, more preferably 1 or more and 5 or less.
The upper limit of the number of polymerizable unsaturated groups per molecule of the resin (b) is not particularly limited, but the number of polymerizable unsaturated groups per molecule is preferably 20 or less. If the number of polymerizable unsaturated groups per molecule of the resin (b) is 20 or less, shrinkage during curing can be suppressed to a low level, and occurrence of cracks in the vicinity of the surface can also be suppressed.

  In the present embodiment, having a polymerizable unsaturated group in the molecule means that the polymerizable unsaturated group is directly in the end of the polymer main chain, the end of the polymer side chain, in the polymer main chain, and in the polymer side chain. This includes cases where groups are attached.

Examples of the resin (b) include compounds having a polymerizable unsaturated group in the molecule with a polymer as shown below as a skeleton.
Examples of polymers include polyolefins such as polyethylene and polypropylene; polydienes such as polybutadiene and polyisoprene; polyhaloolefins such as polyvinyl chloride and polyvinylidene chloride; polystyrene, polyacrylonitrile, polyvinyl alcohol, polyvinyl acetate, polyvinyl acetal , Polymers having hetero atoms in the main chain such as polyacrylic acid, poly (meth) acrylic acid esters, poly (meth) acrylamide, polyester, polycarbonate, polyacetal, polyurethane, polyamide, polyurea, polyether polyol, and polyimide, One or two selected from the group consisting of vinyl alcohol-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer and the like It may be used or more polymers. When using a plurality of polymers, either a copolymer or a blend may be used.

When a flexible relief image is required as in flexographic printing plate applications, as part of the resin (b), a liquid resin having a glass transition temperature of 20 ° C. or lower, preferably a liquid resin having a glass transition temperature of 0 ° C. or lower. Can also be added.
Liquid resins include, for example, hydrocarbons such as polyethylene, polybutadiene, hydrogenated polybutadiene, polyisoprene, and hydrogenated poisoprene; polyesters such as adipate and polycaprolactone; polyethylene such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol Examples include ethers; aliphatic polycarbonates; silicones such as polydimethylsiloxane; polymers of (meth) acrylic acid and / or derivatives thereof, and mixtures and copolymers thereof.
The content of the liquid resin is preferably 30% by mass to 100% by mass with respect to the entire resin (b).
As the liquid resin, unsaturated polyurethanes having a polycarbonate structure are preferable from the viewpoint of weather resistance. Examples of the unsaturated polyurethane include a resin having a polymerizable unsaturated group such as an acrylate group or a methacrylate group at the end of the polyurethane molecular chain, and a resin having a double bond in the polyurethane molecular chain.

As a method of introducing a polymerizable unsaturated group into the molecule of the resin (b), for example, a method of directly polymerizing using a monomer having a polymerizable unsaturated group introduced into the molecular end or molecular chain thereof. Can be mentioned.
As another method, a method in which a resin (polymer) and a compound having a polymerizable unsaturated group are reacted to introduce a polymerizable unsaturated group into the terminal of the resin can also be mentioned. Specifically, it has a plurality of reactive groups such as a hydroxyl group, amino group, epoxy group, carboxyl group, acid anhydride group, ketone group, hydrazine residue, isocyanate group, isothiocyanate group, cyclic carbonate group, and ester group. The compound is allowed to react with a binder having a plurality of functional groups capable of binding to a reactive group (for example, when the reactive group is a hydroxyl group or an amino group, examples of the binder include polyisocyanate), and the molecular weight. The resin obtained by the reaction is reacted with a compound having a functional group capable of reacting with the terminal binding group of the resin and a polymerizable unsaturated group. Then, a polymerizable unsaturated group is introduced into the terminal of the resin.

When the cured resin is used as a printing substrate for laser engraving, it is preferable to use a polymer having high thermal decomposability as the resin (b). For example, polymers having α-methylstyrene, methacrylic acid ester, and acrylic acid ester units, or a carbonate bond and a carbamate bond in the molecule are known as highly thermally decomposable compounds.
As an index of thermal decomposability, thermogravimetric data obtained by measuring weight loss when a sample is heated in an inert gas atmosphere can be used.
The temperature at which the weight of the resin (b) is halved is preferably in the range of 150 ° C. or higher and 450 ° C. or lower. The temperature at which the weight of the resin (b) is halved is more preferably in the range of 250 ° C. or higher and 400 ° C. or lower, and still more preferably in the range of 250 ° C. or higher and 380 ° C. or lower.

  As the resin (b), a compound in which thermal decomposition occurs in a narrow temperature range is preferable. As an indicator that thermal decomposition occurs in a narrow temperature range, in thermogravimetric analysis, the difference between the temperature at which the weight decreases to 80% of the initial weight and the temperature at which the weight decreases to 20% of the initial weight is 100 ° C. or less. It is preferable that The temperature difference is more preferably 80 ° C. or less, and further preferably 60 ° C. or less.

[Organic compound (c)]
The organic compound (c) is a compound having a polymerizable unsaturated group involved in radical polymerization reaction or ring-opening polymerization reaction, and the number average molecular weight is 1000 or less in consideration of easiness of dilution with the resin (b). It is preferable that
Examples of the organic compound (c) include olefins such as ethylene, propylene, styrene and divinylbenzene; acetylenes; (meth) acrylic acid and derivatives thereof; haloolefins; unsaturated nitriles such as acrylonitrile; (meth) acrylamide Allyl compounds such as allyl alcohol and allyl isocyanate; unsaturated dicarboxylic acids such as maleic anhydride, maleic acid, fumaric acid, and itaconic acid and their derivatives; vinyl acetates; N-vinylpyrrolidone; Carbazole; cyanate esters and the like.
As the organic compound (c), derivatives such as (meth) acrylic acid and (meth) acrylic acid ester are preferable from the viewpoint of variety and price.

  As the derivative, an alicyclic compound having a functional group such as a cycloalkyl group, a bicycloalkyl group, a cycloalkene group, and a bicycloalkene group; a functional group such as a benzyl group, a phenyl group, a phenoxy group, a methylstyryl group, and a styryl group An aromatic compound having a group; an ester compound or an amide compound such as a compound having a functional group such as an alkyl group, a halogenated alkyl group, an alkoxyalkyl group, a hydroxyalkyl group, an aminoalkyl group, a tetrahydrofurfuryl group, and a glycidyl group; And ester compounds of polyhydric alcohols such as alkylene glycol, polyoxyalkylene glycol, (alkyl / allyloxy) polyalkylene glycol and trimethylolpropane.

  The organic compound (c) having a polymerizable unsaturated group can be selected from one or more compounds depending on the purpose. For example, when a cylindrical printing original plate is used as a printing plate, a long-chain aliphatic, alicyclic, or aromatic is used as the organic compound (c) in order to suppress swelling with respect to an organic solvent such as alcohol or ester as a printing ink solvent. It is preferable to select at least one kind of group derivative.

  In order to increase the mechanical strength of the cured resin, it is preferable to select at least one compound having a substituent (functional group) such as an alicyclic group or an aromatic group as the organic compound (c). The compound having a substituent such as an alicyclic group or an aromatic group is preferably 20% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass with respect to the total amount of the organic compound (c). It is as follows.

  The sheet resin in the present embodiment may be a photosensitive resin composition or a photosensitive resin cured product, and preferably contains a photopolymerization initiator in the photosensitive resin composition.

[Photopolymerization initiator]
As light at the time of photocuring the photosensitive resin composition, high energy rays such as ultraviolet rays, visible rays, electron beams, and X-rays can be used.
When photocuring using ultraviolet rays or visible light, it is preferable to add a photopolymerization initiator to the photosensitive resin composition. Examples of the photopolymerization initiator include a hydrogen abstraction type photopolymerization initiator (d) and / or a decay type photopolymerization initiator (e).

[Hydrogen extraction type photopolymerization initiator (d)]
Although it does not specifically limit as a hydrogen abstraction type photoinitiator (d), An aromatic ketone can be mentioned.
An aromatic ketone is efficiently brought into an excited triplet state by photoexcitation. As this excited triplet state, a chemical reaction mechanism has been proposed in which hydrogen is extracted from the surrounding medium to generate radicals. The generated radical is considered to be involved in the photocrosslinking reaction.

The hydrogen abstraction type photopolymerization initiator (d) is not particularly limited as long as it is a compound that generates radicals by extracting hydrogen from a surrounding medium through an excited triplet state.
Examples of aromatic ketones include benzophenones, Michler ketones, xanthenes, thioxanthones, and anthraquinones, and it is preferable to use at least one compound selected from the group consisting of the aforementioned compounds.

Examples of benzophenones include benzophenone and derivatives thereof. Specifically, 3,3 ′, 4,4′-benzophenone tetracarboxylic anhydride, 3,3 ′, 4,4′-tetramethoxybenzophenone, etc. Can be mentioned.
Examples of Michler ketones include Michler ketone and derivatives thereof.
Examples of xanthenes include xanthene and derivatives substituted with an alkyl group, a phenyl group, or a halogen group.
Examples of thioxanthones include thioxanthone and derivatives substituted with an alkyl group, a phenyl group, and a halogen group. Specific examples include ethylthioxanthone, methylthioxanthone, and chlorothioxanthone.
Examples of anthraquinones include anthraquinone and derivatives substituted with an alkyl group, a phenyl group, or a halogen group.

The addition amount of the hydrogen abstraction type photopolymerization initiator (d) is preferably 0.3% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 5% by mass with respect to the total amount of the photosensitive resin composition. % Or less.
If the addition amount of the hydrogen abstraction type photopolymerization initiator (d) is within the above range, when the photosensitive resin composition is photocured in the atmosphere, the curability of the cured product surface can be sufficiently secured, and As a cured product, cracks and the like are not generated on the surface during long-term storage, and weather resistance can be ensured.

"Collapse photopolymerization initiator (e)"
The collapsible photopolymerization initiator (e) means a compound that generates an active radical by generating a cleavage reaction in the molecule after light absorption, and is not particularly limited.
Specifically, benzoin alkyl ethers, 2,2-dialkoxy-2-phenylacetophenones, acetophenones, acyloxime esters, azo compounds, organic sulfur compounds, acylphosphine oxides, diketones, etc. Can be mentioned.
As the collapsible photopolymerization initiator (e), it is preferable to use at least one compound selected from the group consisting of the aforementioned compounds.

Examples of benzoin alkyl ethers include benzoin isopropyl ether and benzoin isobutyl ether.
Examples of 2,2-dialkoxy-2-phenylacetophenones include 2,2-dimethoxy-2-phenylacetophenone and 2,2-diethoxy-2-phenylacetophenone.
Examples of acetophenones include acetophenone, trichloroacetophenone, 1-hydroxycyclohexylphenylacetophenone, and 2,2-diethoxyacetophenone.
Examples of acyloxime esters include 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime.
Examples of the azo compound include azobisisobutyronitrile, diazonium compound, and tetrazene compound.
Examples of diketones include benzyl and methylbenzoyl formate.

The addition amount of the collapsible photopolymerization initiator (e) is preferably 0.3% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 5% by mass based on the total amount of the photosensitive resin composition. It is as follows.
If the addition amount of the collapsible photopolymerization initiator (e) is within the above range, when the photosensitive resin composition is photocured in the air, the curability inside the cured product can be sufficiently secured. .

A compound having a site functioning as a hydrogen abstraction type photopolymerization initiator and a site functioning as a decay type photopolymerization initiator in the same molecule can also be used as the photopolymerization initiator.
Examples of the photopolymerization initiator include α-aminoacetophenones.
Examples of α-aminoacetophenones include 2-methyl-1- (4-methylthiophenyl) -2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone etc. can be mentioned.

The addition amount of the photopolymerization initiator having a site functioning as a hydrogen abstraction type photopolymerization initiator and a site functioning as a decay type photopolymerization initiator in the same molecule is 0.3% by mass of the total amount of the photosensitive resin composition. The content is preferably 10% by mass or less, more preferably 0.5% by mass or more and 3% by mass or less.
If the addition amount of the photopolymerization initiator is within the above range, the mechanical properties of the cured product can be sufficiently ensured even when the photosensitive resin composition is photocured in the atmosphere.

[Photoacid generator, photobase generator]
A photoacid generator or photobase generator that generates an acid or a base by light irradiation can be used as a photopolymerization initiator.
By using a photoacid generator or a photobase generator, a compound having a functional group that undergoes a ring-opening polymerization reaction, such as an epoxy compound or an oxetane compound, can be subjected to ring-opening polymerization.

  The sheet resin in the present embodiment may be a thermosetting resin composition or a thermosetting resin cured product, and preferably contains a thermal polymerization initiator in the thermosetting resin composition.

[Thermal polymerization initiator]
As thermal polymerization initiators, suitable compounds are all thermal polymerization initiators that can be used in radical polymerization reactions or ring-opening polymerization reactions.
Examples of the thermal polymerization initiator used in the radical polymerization reaction include organic peroxides, inorganic peroxides, organic silicon peroxides, hydroperoxides, azo compounds, thiol compounds, phenol resins, amino resins, halogen compounds, and aldehydes. A compound etc. can be mentioned.
Examples of the thermal polymerization initiator used in the ring-opening polymerization reaction include a latent thermal polymerization initiator in which a thermal polymerization initiator is placed in a microcapsule.

The thermal polymerization initiator is preferably liquid at 20 ° C. from the viewpoint of easy mixing with the resin (b) or the organic compound (c).
The content of the thermal polymerization initiator is preferably 0.1% by mass or more and 10% by mass or less with respect to the total amount of the thermosetting resin composition. The content of the thermal polymerization initiator is more preferably 0.5% by mass or more and 5% by mass or less, and further preferably 1% by mass or more and 5% by mass or less.
If the content of the thermal polymerization initiator is within the above range, the thermosetting resin composition can be sufficiently cured, and the tackiness of the surface of the thermosetting product can be reduced.

In the present embodiment, selection of a thermal polymerization initiator is important in order to perform thermal polymerization suitably. The thermal stability of the thermal polymerization initiator is usually free by the 10 hour half-life temperature (10 h-t1 / 2), ie 50% of the initial amount of thermal polymerization initiator decomposes after 10 hours. Indicated at the temperature at which the radical is formed.
Details regarding the 10-hour half-life temperature are given in “Encyclopedia of Polymer Science and Engineering”, Volume 11, p. 1 and later, John Wiley & Sons, New York, 1988.
The 10-hour half-life temperature of the thermal polymerization initiator is preferably at least 60 ° C, more preferably at least 70 ° C, and even more preferably 80 ° C to 150 ° C.

As the thermal polymerization initiator, an organic peroxide is particularly preferable from the viewpoint of thermosetting and compatibility with the thermosetting resin composition.
Examples of the thermal polymerization initiator include t-butyl peroctanoate, t-amyl peroctanoate, t-butyl peroxyisobutyrate, t-butyl peroxymaleate, t-amyl perbenzoate, di-peroxyphthalate di- Peroxyesters such as t-butyl, t-butyl perbenzoate, t-butyl peracetate, and 2,5-di (benzoylperoxy) -2,5-dimethylhexane; 1,1-di (t-amylperoxy) ) Diperoxyketals such as cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (t-butylperoxy) butane, and ethyl 3,3-di (t-butylperoxy) butyrate; Di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, and 2,5-di (t-butyl peroxide) Dialkyl peroxides such as dibenzoyl peroxide and diacetyl peroxide; t such as t-butyl hydroperoxide, t-amyl hydroperoxide, pinane hydroperoxide, and cumyl hydroperoxide -Alkyl hydroperoxides can be mentioned.

As a thermopolymerizable initiator, an azo compound may be mentioned as a preferable compound when forming a cushion layer containing bubbles.
Examples of the azo compound include 1- (t-butylazo) formamide, 2- (t-butylazo) isobutyronitrile, 1- (t-butylazo) cyclohexanecarbonitrile, 2- (t-butylazo) -2-methylbutane. Nitriles, 2,2′-azobis (2-acetoxypropane), 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (isobutyronitrile), and 2,2′-azobis (2- Methylbutanenitrile) and the like.

[Fine particles]
Inorganic fine particles, organic fine particles, and / or organic-inorganic composite fine particles can be added to the resin composition. Improvement of mechanical properties of cured resin obtained by curing by adding these fine particles, improvement of wettability of resin cured product surface, adjustment of viscosity of resin composition, viscoelastic properties of cured resin Adjustment and the like are possible.
The material of the inorganic fine particles or organic fine particles is not particularly limited, and known fine particles can be used.
Examples of the organic / inorganic composite fine particles include fine particles in which an organic layer or organic fine particles are formed on the surface of inorganic fine particles, or fine particles in which an inorganic layer or inorganic fine particles are formed on the surface of organic fine particles.

As the fine particles, for the purpose of improving the mechanical properties of the cured resin, inorganic fine particles having high rigidity such as silicon nitride, boron nitride, and silicon carbide, or organic fine particles such as polyimide can be used.
In order to improve the solvent resistance of the obtained resin cured product, inorganic fine particles or organic fine particles formed of a material having a good swelling property in the solvent to be used can be added.

  For the purpose of forming a pattern that penetrates the surface of the resin cured product layer or the resin cured product by laser engraving, inorganic porous fine particles with excellent adsorption and removal characteristics of viscous liquid residue generated during laser engraving can be added. Good.

  The fine particles are not particularly limited, and examples thereof include porous silica, mesoporous silica, silica-zirconia porous gel, porous alumina, and porous glass.

  It is preferable that the number average particle diameter of the fine particles is 0.01 to 100 μm. The number average particle diameter of the fine particles is preferably 0.1 to 20 μm, more preferably 1 to 10 μm. When fine particles having a number average particle size within the above range are used, there are inconveniences such as increase in viscosity, entrainment of bubbles, and generation of a large amount of dust when mixing with the resin (b) and the organic compound (c). As a result, unevenness does not occur on the surface of the cured resin.

  In the present embodiment, the average particle size of the fine particles means a value measured using a laser scattering type particle size distribution measuring device.

  The particle shape of the fine particles is not particularly limited, and as the fine particles, spherical, flat, needle-shaped, amorphous, or particles having protrusions on the surface can be used, and from the viewpoint of wear resistance, Spherical particles are preferred.

The surface of the fine particles can be coated with a silane coupling agent, a titanium coupling agent, and other organic compounds and subjected to a surface modification treatment to use finer particles that are made more hydrophilic or hydrophobic.
In the present embodiment, one kind or two or more kinds of these fine particles can be selected.

[Composition ratio of resin composition]
The ratio of the resin (b), the organic compound (c), and the fine particles in the resin composition is preferably 5 to 200 parts by mass of the organic compound (c) with respect to 100 parts by mass of the resin (b). More preferably, it is 100 parts by mass.
The fine particles are preferably 1 to 100 parts by mass, more preferably 2 to 50 parts by mass, and further preferably 2 to 20 parts by mass with respect to 100 parts by mass of the resin (b).
When the ratio of the organic compound (c) is within the above range, it is easy to balance the hardness and tensile strength / elongation of the resulting resin cured product, and the shrinkage at the time of curing is within a small range to ensure thickness accuracy. Can do.

  A polymerization inhibitor, an ultraviolet absorber, a lubricant, a surfactant, a plasticizer, a fragrance, and the like can be added to the resin composition according to the use and purpose.

[Method for producing sheet-like resin]
As a method for producing the sheet-like resin, an existing resin molding method can be used.
Sheet resin production methods include, for example, a casting method, a method of extruding a resin from a nozzle or a die with a machine such as a pump or an extruder, a method of adjusting the thickness with a blade, a method of adjusting a thickness by calendaring with a roll, a spray, and the like The method of spraying using can be mentioned.
When the sheet-like resin is molded, it is possible to perform the molding while heating in a range that does not cause thermal decomposition, and rolling treatment, grinding treatment, and the like may be performed as necessary.

[Photocuring method]
The molded photosensitive resin composition is crosslinked by light irradiation to form a cured photosensitive resin.
While forming the photosensitive resin composition, it can be crosslinked by irradiation with light to form a cured photosensitive resin.
Examples of the light source used for photocuring include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet fluorescent lamp, a germicidal lamp, a carbon arc lamp, a xenon lamp, and a metal halide lamp.
The light irradiated to the photosensitive resin composition preferably has light having a wavelength of 200 nm to 400 nm.
Since many hydrogen abstraction type photopolymerization initiators have strong light absorption in this wavelength region, when having light with a wavelength of 200 nm to 400 nm, sufficiently ensure the curability of the surface of the photosensitive resin cured product. Can do. The light source used for photocuring may be one type, but since the curability of the resin may be improved by curing using two or more types of light sources having different wavelengths, two or more types of light sources may be used. preferable.

[Thermosetting method]
When the curable resin composition is a thermosetting resin composition, a thermosetting resin cured product is obtained by heat treatment.
Examples of the heating method include a method of irradiating infrared rays, a method of exposing to an atmosphere heated by an oven, a method of contacting an object such as a heated metal, and the like. The heating temperature is selected according to the type of thermal polymerization initiator.

[Cushion layer]
In the present embodiment, the photo-curable adhesive layer may also serve as a cushion layer, and a cushion layer made of an elastomer is formed in the lower part of the sheet-like resin (the side in contact with the cylindrical support (a)). You can also. In addition, a cushion layer may be formed on the surface of the cylindrical support (a).
The cushion layer is preferably an elastomer layer having a Shore A hardness of 10 or more and 70 degrees or less, or an ASKER-C hardness of 20 degrees or more and 85 degrees or less measured with an ASKER-C type hardness tester.
When the Shore A hardness is 10 degrees or more, or the ASKER-C hardness is 20 degrees or more, the print quality can be ensured because it is appropriately deformed.
When the Shore A hardness is 70 degrees or less or the ASKER-C hardness is 85 degrees or less, it can serve as a cushion layer.
It is preferable that the Shore A hardness is 20 to 60 degrees or the ASKER-C hardness is 45 to 75 degrees. The Shore A hardness and the ASKER-C hardness are preferably selected depending on the material used for the cushion layer. The difference between the two types of hardness stems from the difference in the shape of the pushers of the hardness meter used for measurement. In the case of a uniform resin composition, it is preferable to use Shore A hardness, and in the case of a non-uniform resin composition such as a foamable base material such as foamed polyurethane and foamed polyethylene, it is preferable to use ASKER-C hardness. ASKER-C hardness is a measuring method based on JIS K7312 standard.

The material for the cushion layer is not particularly limited, and examples thereof include elastomers having rubber elasticity such as thermoplastic elastomers, photocurable elastomers, and thermosetting elastomers.
From the viewpoint of processability to a cylindrical printing plate, it is convenient and preferable to use a liquid photosensitive resin composition that is cured by light and to use a material that becomes an elastomer after curing.

  The cushion layer preferably contains a cured resin and contains bubbles or organic fine particles. It is preferable to use organic microparticles that are hollow microcapsules, in which inorganic microparticles are attached to the surface of the hollow microcapsules. The average particle diameter of the organic fine particles is preferably 1 μm or more and 500 μm or less, more preferably 10 μm or more and 300 μm or less, and further preferably 80 μm or more and 200 μm or less.

The density of the cushion layer is preferably 0.1 g / cm ³ or more and 0.9 g / cm ³ or less, more preferably 0.3 g / cm ³ or more and 0.7 g / cm ³ or less, and still more preferably 0. .4g / cm ³ or more 0.6g / cm ³ or less.
If the density of the cushion layer is within the above range, the impact applied to the laser engraving layer in the printing process can be sufficiently absorbed.

  Examples of the thermoplastic elastomer used for the cushion layer include styrene thermoplastic elastomers such as SBS (polystyrene-polybutadiene-polystyrene), SIS (polystyrene-polyisoprene-polystyrene), and SEBS (polystyrene-polyethylene / polybutylene-polystyrene), Examples include olefin-based thermoplastic elastomers, urethane-based thermoplastic elastomers, ester-based thermoplastic elastomers, amide-based thermoplastic elastomers, silicon-based thermoplastic elastomers, and fluorine-based thermoplastic elastomers.

  The photocurable elastomer used for the cushion layer is a composition in which a thermoplastic elastomer is mixed with a photopolymerizable monomer, a plasticizer, a photopolymerization initiator, etc., and a liquid resin is mixed with a photopolymerizable monomer, a photopolymerization initiator, etc. And the like.

  The elastomer used for the cushion layer may be a sulfur cross-linked rubber, organic peroxide, phenol resin initial condensate, quinone dioxime, metal oxide, and non-sulfur cross-linked rubber using a compound such as thiourea as a cross-linking agent. . It is also possible to use an elastomer obtained by three-dimensional crosslinking using a curing agent that reacts with telechelic liquid rubber.

  The cushion layer may be a cushion layer made of foamed polyurethane, foamed polyethylene or the like and having independent or open cells in the layer, and commercially available cushion materials and cushion tapes can also be used. An adhesive or a pressure-sensitive adhesive may be applied to one side or both sides of the layer.

By forming a modified layer on the surface of the photosensitive resin cured product of the present embodiment, tack on the surface of the printing substrate can be reduced and ink wettability can be improved. Examples of the modified layer include a film treated with a compound that reacts with a surface hydroxyl group such as a silane coupling agent or a titanium coupling agent, or a polymer film containing porous inorganic particles.
A widely used silane coupling agent is a compound having in its molecule a functional group highly reactive with the surface hydroxyl group of the substrate. Examples of such a functional group include a trimethoxysilyl group and a triethoxysilyl group. Groups, trichlorosilyl groups, diethoxysilyl groups, dimethoxysilyl groups, dimonochlorosilyl groups, monoethoxysilyl groups, monomethoxysilyl groups, and monochlorosilyl groups.
At least one of these functional groups exists in the molecule, and is immobilized on the surface of the substrate by reacting with the surface hydroxyl group of the substrate.

  The compound constituting the silane coupling agent is selected from the group consisting of acryloyl group, methacryloyl group, active hydrogen-containing amino group, epoxy group, vinyl group, perfluoroalkyl group, and mercapto group as reactive functional groups in the molecule. A compound having at least one functional group or a compound having a long-chain alkyl group can be used.

In the present embodiment, when the cured resin is used as a printing substrate on which a pattern is formed by using a laser engraving method, the laser engraving method uses a computer as a digital data to form an image to be formed. To create a relief image on the printing substrate. Any laser beam may be used for the laser engraving as long as the original plate includes a wavelength having absorption. However, in order to perform engraving at a high speed, a laser beam having a high output is preferable. And infrared or infrared emitting solid lasers such as YAG lasers and semiconductor lasers.
The second harmonic of a YAG laser having an oscillation wavelength in the visible light region, a copper vapor laser, an ultraviolet laser having an oscillation wavelength in the ultraviolet region, such as an excimer laser, and a YAG laser wavelength-converted to the third or fourth harmonic are organic Ablation processing that cuts the bond of molecules is possible, and it is suitable for fine processing. The laser may be continuous irradiation or pulse irradiation.

  Laser engraving is carried out in an oxygen-containing gas, generally in the presence of air or an air stream, but can also be carried out in the presence of carbon dioxide or nitrogen gas. After engraving is finished, the powdery or liquid substance slightly generated on the relief printing plate surface is washed with an appropriate method such as water containing a solvent or a surfactant, or a water-based cleaning agent is irradiated by a high-pressure spray or the like. Alternatively, it may be removed using a method of irradiating high-pressure steam.

  In this embodiment, after engraving to form a concave pattern by irradiating laser light, following the step of removing powdery or viscous liquid residue remaining on the plate surface, the printing plate surface on which the pattern is formed has a wavelength of 200 nm to Post-exposure by irradiating with 450 nm light can also be performed. This method is effective in removing tack on the surface. The post-exposure may be performed in any environment such as air, inert gas atmosphere, and water. This is particularly effective when the photosensitive resin composition used contains a hydrogen abstraction type photopolymerization initiator. Furthermore, before the post-exposure step, the printing plate surface may be treated and exposed to a treatment liquid containing a hydrogen abstraction type photopolymerization initiator. Moreover, you may expose in the state which immersed the printing plate in the process liquid containing a hydrogen drawing-type photoinitiator.

A method for producing a cylindrical printing original plate having a cylindrical support (a) of the present embodiment and a sheet-like resin bonded on the cylindrical support (a),
(I) forming a photocurable adhesive layer on the surface of the cylindrical support (a);
(Ii) installing the sheet-like resin on the photocurable adhesive layer;
(Iii) sandwiching the sheet-like resin between a plate-like object or a cylindrical object having a light-transmitting slit and the cylindrical support (a);
(Iv) irradiating the photocurable adhesive layer with light through the light transmissive slit;
(V) rotating the cylindrical support (a), and irradiating light at a position different from the step (iv).

[Step (i)]
In the step (i), a photocurable adhesive layer is formed on the surface of the cylindrical support (a).
The photocurable adhesive layer is made of a photocurable adhesive, and the photocurable adhesive may contain the resin (b), the organic compound (c), and a compound as described above as a photopolymerization initiator. Preferably, the photocurable adhesive may have a composition different from that of the sheet-like resin.

[Photocurable adhesive]
The photocurable adhesive may be liquid or solid at 20 ° C.
When it is liquid at 20 ° C., the viscosity is preferably 100 Pa · s or more and 10 kPa · s or less, more preferably 500 Pa · s or more and 5 kPa · s or less, and further preferably 1 kPa · s or more and 5 kPa · s or less. is there.
When the viscosity at 20 ° C. is within the above range, the shape can be maintained without causing dripping by resisting gravity when coated on the cylindrical support (a).

  When it is solid at 20 ° C., it is preferable to heat to a temperature at which the photocurable adhesive is softened when installing the sheet-like resin in the step (2). The photocurable adhesive that is solid at 20 ° C. is preferably dissolved in a solvent and applied using a method such as spray coating, blade coating, or roll coating, and then the solvent is removed by drying. A solventless type hot-melt photocurable adhesive may be applied in a heated state.

[Surface treatment of cylindrical support (a)]
By performing physical or chemical treatment on the surface of the cylindrical support (a), it is possible to improve the adhesion with the photocurable adhesive layer.
Examples of the physical treatment method include a sand blast method, a wet blast method for injecting a liquid containing fine particles, a corona discharge treatment method, a plasma treatment method, and an ultraviolet ray or vacuum ultraviolet ray irradiation method.
Examples of the chemical treatment method include a strong acid / strong alkali treatment method, an oxidant treatment method, and a coupling agent treatment method.

[Step (ii)]
In the step (ii), the sheet-like resin is placed on the photocurable adhesive layer.
Specifically, a sheet-like resin is placed on the photocurable adhesive layer on the surface of the cylindrical support (a) held by the mechanism (1) of the cylindrical printing original plate forming apparatus.

[Step (iii)]
In the step (iii), a sheet-like resin is sandwiched between a plate-like object or a cylindrical object having a light-transmitting slit and the cylindrical support (a).
Specifically, the distance between the plate-shaped object or cylindrical object and the surface of the cylindrical support (a) held by the mechanism (1) is changed by the mechanism (2), and the plate-shaped object or cylindrical object is changed. And a cylindrical support (a), a sheet-like resin is sandwiched between the sheet-like resin and the photocurable adhesive layer.

[Step (iv)]
In the step (iv), the light curable adhesive layer is irradiated with light through a light transmissive slit.
Specifically, light is irradiated from the light source (3) of the cylindrical printing original plate forming apparatus, and the light is condensed by the optical system (4) on the contact interface between the sheet-like resin and the photocurable adhesive layer. The sheet-like resin and the cylindrical support (a) are bonded together.

[Step (v)]
In the step (v), the cylindrical support (a) is rotated, and light is irradiated at a position different from that in the step (iv).
Specifically, the cylindrical support (a) is rotated by the mechanism (1), and in the step (iv), the sheet-shaped resin and the light other than the position where the sheet-shaped resin and the cylindrical support (a) are bonded. The sheet-like resin and the cylindrical support (a) are adhered by bringing the curable adhesive layer into contact and irradiating the contact interface with light from the light source (3).
By performing the step (v) a plurality of times, the sheet-like resin is bonded to the cylindrical support (a), and a cylindrical printing original plate can be produced.

  Examples of the use of the cylindrical printing original plate produced by the cylindrical printing original plate forming apparatus of the present embodiment include a printing original plate or a printing plate used in printing techniques such as flexographic printing, dry offset printing, and gravure printing. Narrow webs such as flexographic label printing, which require a highly accurate printed matter, and curved offset printing such as can offset printing and tube printing are preferred applications.

In printing, when the ink contains an aliphatic hydrocarbon and / or an aromatic hydrocarbon, the sheet-like resin preferably contains a polycarbonate, polyurethane, polyamide, polyvinyl alcohol, or vinyl alcohol-vinyl acetate copolymer. These resin materials are preferable because they have resistance to the above-mentioned solvents.
Examples of aliphatic hydrocarbons include compounds such as hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, cyclooctane, cyclodecane, dipentene, rubber volatile oil, mineral spirits, and high boiling point petroleum solvent (ink oil). Can do.
Aromatic hydrocarbons include compounds such as toluene, xylene, dimethylbenzene, dichlorobenzene, solvent naphtha, and tetralin.

  Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to only these examples. The measurement method and the evaluation method used in this embodiment are as follows.

(1) Laser engraving Laser engraving is a carbon dioxide laser engraving machine (ZED-mini-1000, UK, manufactured by ZED, USA, coherent, equipped with a 250W carbon dioxide laser with an oscillation wavelength of 10.6 μm). Used. Engraving was performed by creating a dot pattern (120 lines / inch, area ratio 10%). The engraving depth was 0.55 mm.

(2) Viscosity The viscosity of the resin composition was measured at 20 ° C. using a B-type viscometer (trademark, B8H type; manufactured by Tokyo Keiki Co., Ltd., Japan).

(3) Measurement of number average molecular weight The number average molecular weights of the resin (b) and the organic compound (c) were determined by conversion with polystyrene having a known molecular weight using a gel permeation chromatography method (GPC method). Using a high-speed GPC apparatus (Japan, manufactured by Tosoh Corporation, HLC-8020) and a polystyrene-filled column (TSKgel GMHXL; manufactured by Tosoh Corporation, Japan), the measurement was performed using tetrahydrofuran. The column temperature was set to 40 ° C. As a sample to be injected into the GPC apparatus, a tetrahydrofuran solution having a resin (b) concentration of 1% by mass was prepared, and the injection amount was 10 μL. A differential refractometer was used as the detector.

(4) Measurement of light energy amount The amount of energy was calculated from illuminance and irradiation time. The illuminance was measured by attaching a sensor unit (Oak Seisakusho, “APR-350”) to an illuminance meter (Oak Seisakusho, “M02”).

Example 1
[Cylindrical printing plate making machine 1]
As a mechanism that can hold and rotate the air cylinder, a small lathe with a three-claw chuck and a core pushing tailstock was modified, and a stepping motor with an encoder was attached as a rotating mechanism to enable low-speed rotation. The fiber reinforced plastic sleeve and the metal sleeve can be mounted by ejecting air from the pores of the air cylinder and can be fixed by stopping the ejection of air.
As shown in FIG. 1, two rolls (16, 17) supporting the glass hollow cylinder 15 are installed on the upper part of the air cylinder 10, and the roll 16 can rotate in synchronization with the rotation of the air cylinder 10. Attached. The other roll 17 is a mechanism that supports it so that it can freely rotate in the circumferential direction. A quartz glass hollow cylinder 15 was held on the two rolls (16, 17). Further, the two rolls (16, 17) were each provided with a vertical movement mechanism that is driven by a stepping motor so as to be able to move up and down. The sheet-shaped resin 12 is placed on the cylindrical support (a) 11, and the position of the two rolls (16, 17) is set so that the quartz glass hollow cylinder 15 is in contact with the sheet-shaped resin 12 and does not move. Decide. The quartz glass hollow cylinder 15 has an inner diameter of 300 mm and a thickness of 5 mm. The quartz glass hollow cylinder 15 used had a light transmittance of 95% or more at a wavelength of 350 nm.
As the light source 14, a chemical lamp having an average output of 10 W / cm (“10R lamp” manufactured by Lankoku Philips Co., Ltd.) was used and installed inside a hollow cylinder 15 made of quartz glass.
As shown in FIG. 1, a metal cylindrical light-shielding portion 13 having a slit 24 (slit width: 3 mm) at the bottom is installed in a quartz glass hollow cylinder 15 to emit light from the chemical lamp from the slit portion. The light was condensed by a cylindrical lens 23 installed in the slit portion and irradiated onto the cylindrical support (a) 11.
The photocurable adhesive layer on the surface of the cylindrical support (a) 11 was photocured and adhered to the sheet-like resin 12. At the time of light irradiation, the photocurable adhesive layer and the sheet-like resin 12 were always brought into contact. The cylindrical support (a) 11 was rotated by a predetermined amount while being irradiated with a predetermined amount of energy, and another position was photocured. The rotation of the roll 16 was adjusted so that the quartz glass hollow cylinder 15 was rotated by the same amount in synchronization with the rotation of the cylindrical support (a) 11.
As shown in FIG. 1, the cylindrical support (a) 11 has a photocurable adhesive layer 25.

[Preparation of sheet resin]
As the resin (b), a polycarbonate polyurethane having a number average molecular weight of about 100,000 (manufactured by Dainichi Seika Co., Ltd., “Resamine (registered trademark) P890”) 70 parts by mass, and as the organic compound (c), phenoxyethyl methacrylate (molecular weight 190) 30 parts by mass and trimethylolpropane triacrylate (molecular weight 338) 1 part by mass, as fine particles, porous fine powder silica (manufactured by Fuji Silysia Chemical Co., Ltd., “Syrosphere (registered trademark) C-1504”) As a photopolymerization initiator, 0.5 part by mass of benzophenone and 0.6 part by mass of 2,2-dimethoxy-2-phenylacetophenone, and as a stabilizer, 0.5 part by mass of 2,6-di-t-butylacetophenone, Mixing at a temperature of 130 ° C. using a small-capacity pressure type kneader (“D1-5” manufactured by Moriyama Co., Ltd.), photosensitive resin A composition was prepared. Using the biaxial extrusion device (“KZW-TW”, manufactured by Technobel Co., Ltd.), the obtained photosensitive resin composition is a PET film having a thickness of 50 μm (manufactured by Toray Industries, Inc.) on which the urethane adhesive is thinly applied. The sheet-like resin was formed by sandwiching it with a PET cover sheet (manufactured by Fujimori Kogyo Co., Ltd.) having a thickness of 50 μm which was extruded with a thickness of 0.4 mm and further subjected to silicone release treatment. The photosensitive resin composition of sheet-like resin was solid at 20 ° C.
The obtained sheet-like resin was cut into a width of 180 mm and a length of 710 mm. Before winding on a hollow cylindrical support, it was photocured by irradiating 4000 mJ / cm ² (integrated light quantity at 350 nm) with ultraviolet rays emitted from a chemical lamp (Lanku, Philips, “10R”) on a glass plate. A sheet-like resin was obtained.

[Manufacture of cylindrical printing original plate]
On a sleeve made of glass fiber reinforced plastic (made by Polybest, Germany) with an inner diameter of 225 mm, a thickness of 1 mm, and a width of 200 mm mounted on an air cylinder, a photo-curing adhesive (manufactured by Notape Industries Co., Ltd., “Acrytac (registered trademark)” )) Was applied at a thickness of 0.1 mm, a sheet-like resin was wound thereon, and both were bonded using the cylindrical printing original plate manufacturing apparatus 1 to prepare a cylindrical printing original plate.
The outer diameter of the obtained cylindrical printing original plate was measured using a laser length measuring instrument (manufactured by Keyence Corporation, “LS-5120”) at 5 locations on the same circumference and 5 locations in the long axis direction. However, the portion where the joint portion of the cured resin sheet was not included was selected for measurement. The outer diameter accuracy was ± 15 μm.

(Example 2)
[Cylindrical printing plate making machine 1]
As shown in FIG. 2, an acrylic plate 18 having a thickness of 5 mm is installed on the cylindrical support (a) 11, and the sheet-like resin 12 is placed between the cylindrical support (a) 11 and the acrylic plate 18. A sandwiching device was used. The rolls 19 and 20 support the acrylic plate 18 and have a rotation mechanism so that the acrylic plate 18 can be moved to the left and right in accordance with the rotation of the cylindrical support (a) 11. Moreover, the roll 21 and the roll 22 are rolls for holding the acrylic plate 18 so as not to move upward, and are configured to freely rotate. The light transmittance of the acrylic plate 18 at a wavelength of 350 nm was 95% or more.
The same light source 14 as in Example 1 was used. The same chemical lamp as that of Example 1 was installed as the light source 14 in the metal cylindrical light-shielding portion 13 having a slit 24 (slit width: 3 mm) at the bottom. As shown in FIG. 2, the cylindrical support (a) 11 has a photocurable adhesive layer 25.

[Sheet resin]
As the resin (b), a polycarbonate polyurethane having a number average molecular weight of about 100,000 (manufactured by Dainichi Seika Co., Ltd., “Resamine (registered trademark) P890”) 70 parts by mass, and as the organic compound (c), phenoxyethyl methacrylate (molecular weight 190) 30 parts by mass and trimethylolpropane triacrylate (molecular weight 338) 1 part by mass, as fine particles, porous fine powder silica (manufactured by Fuji Silysia Chemical Co., Ltd., “Cyrossphere (registered trademark) C-1504”) 5 parts by weight, stable As an agent, 0.5 part by mass of 2,6-di-t-butylacetophenone was mixed at a temperature of 130 ° C. using a small-capacity pressure type kneader (“Dri-5” manufactured by Moriyama Co., Ltd.), and then 70 ° C. Until it is cooled to t-butyl peroxy-2-ethylhexyl carbonate (Nippon Yushi Co., Ltd. Butyl E (registered trademark) ”) 1 part by mass was added to prepare a thermosetting resin composition. The obtained thermosetting resin composition is inserted between a 50 μm thick PET film (manufactured by Toray Industries, Inc.) whose surface is coated with a urethane adhesive and a silicone release-treated PET film (manufactured by Fujimori Kogyo Co., Ltd.). Then, it was hot-pressed with two metal plates. A metal spacer having a thickness of 0.5 mm was inserted between the two metal plates, and heat treatment was performed at 130 ° C. for 30 minutes to obtain a thermally cured sheet-like resin.

[Manufacture of cylindrical printing original plate]
An aramid fiber reinforced plastic (epoxy resin) sleeve having a thickness of 0.4 mm was used as the cylindrical support (a), and was mounted on a metal air cylinder. A photo-curing adhesive (manufactured by No-Tape Kogyo Co., Ltd., “Acrytac (registered trademark)”) is applied to the mounted sleeve with a thickness of 0.1 mm, and the sheet-shaped resin prepared thereon is placed thereon to form a cylindrical support. (A) is sandwiched between acrylic plates, and in the state where the sheet-shaped resin is in contact with the photocurable adhesive layer, light from a chemical lamp (Ranku, Philips, “10R”) is irradiated to form a cylindrical support ( While rotating a) at a low speed, the sheet-like resin was adhered to the cylindrical support (a) to produce a cylindrical printing original plate. The outer diameter accuracy of the obtained cylindrical printing original plate was within ± 15 μm.

[Manufacture and printing of cylindrical printing plates]
An uneven pattern was formed on the surface of the obtained cylindrical printing original plate at a linear velocity of 10 m / sec using a carbon dioxide laser engraving machine to obtain a cylindrical printing plate. Then, it mounted on the flexographic printing machine and printed on the polyethylene film using the solvent ink at a printing speed of 200 m / min. In the laser engraving process and the printing process, the sheet-like resin was not peeled off from the cylindrical support (a). Moreover, the printing quality of the halftone dot part of the obtained printed matter was also good.

(Example 3)
[Manufacture of cylindrical printing original plate]
The uncured sheet-shaped resin produced in Example 1 was placed on the photocurable adhesive layer used in Example 1, and photocured using the cylindrical printing original plate forming apparatus used in Example 1. At the same time as the photosensitive adhesive layer was photocured, the sheet-shaped resin was also photocured to prepare a cylindrical printing original plate. The amount of energy of the irradiated light was 8000 mJ / cm ² .
The outer diameter of the obtained cylindrical printing original plate was measured using a laser length measuring instrument (manufactured by Keyence Corporation, “LS-5120”) at 5 locations on the same circumference and 5 locations in the long axis direction. However, the portion where the joint portion of the cured resin sheet was not included was selected for measurement. The outer diameter accuracy was ± 20 μm.

(Comparative Example 1)
The quartz glass hollow cylinder was removed from the cylindrical printing original plate forming apparatus used in Example 1. The photocured sheet-shaped resin used in Example 1 was wound around a sleeve on which a photocurable adhesive layer was formed, and the ends were fixed with tape. Then, light was irradiated using the cylindrical printing original plate forming apparatus while rotating the sleeve at a low speed.
The outer diameter of the obtained cylindrical printing original plate was measured using a laser length measuring instrument (manufactured by Keyence Corporation, “LS-5120”) at 5 locations on the same circumference and 5 locations in the long axis direction. However, the portion where the joint portion of the cured resin sheet was not included was selected for measurement. The outer diameter accuracy was ± 100 μm.
Further, when the obtained cylindrical printing original plate was rotated at a high speed by a laser engraving machine at a linear velocity of 10 m / sec, the sheet-like resin dropped off from the sleeve.

INDUSTRIAL APPLICABILITY The present invention can provide a cylindrical printing original plate molding apparatus for manufacturing a cylindrical printing original plate with high productivity and high thickness accuracy by adhering a sheet-like resin on a cylindrical support.
The present invention has industrial applicability in printing fields such as flexographic printing, dry offset printing, and gravure printing.

The schematic side view of the cylindrical printing original plate forming apparatus of Example 1 is shown. The schematic side view of the cylindrical printing original plate forming apparatus of Example 2 is shown.

Explanation of symbols

1: Cylindrical printing original forming apparatus 10: Air cylinder 11: Cylindrical support (a)
12: Sheet resin 13: Metal cylindrical light shielding part 14: Light source 15: Cylindrical object (for example, quartz glass hollow cylinder)
16: Roll 17: Roll 18: Plate (for example, acrylic plate)
19: Roll 20: Roll 21: Roll 22: Roll 23: Cylindrical lens 24: Slit 25: Photocurable adhesive layer

Claims (14)

A cylindrical printing original plate molding apparatus for adhering a sheet-like resin on a cylindrical support (a),
(1) A mechanism for holding the cylindrical support (a) having a photocurable adhesive layer on the surface and rotating it in the circumferential direction;
(2) a mechanism having a plate-like object or a cylindrical object having a light-transmitting slit, and changing a distance from the surface of the cylindrical support (a);
(3) irradiating light through the light transmissive slit, and a light source disposed in the mechanism (2);
(4) The sheet resin is sandwiched between the plate or cylinder and the cylindrical support (a), and the sheet resin and the cylindrical support are passed through the plate or cylinder. An optical system for condensing light from the light source on the photocurable adhesive layer existing between (a) and a cylindrical printing original plate forming apparatus.   The cylindrical printing original plate forming apparatus according to claim 1, wherein the light source is a light source that emits light having a wavelength of 200 nm to 400 nm.   The cylindrical printing original plate forming apparatus according to claim 1 or 2, wherein a width of the light transmissive slit is 0.5 mm or more and 20 mm or less. The cylindrical support (a) is a hollow cylindrical support made of fiber reinforced plastic or metal,
The cylindrical printing original plate molding according to any one of claims 1 to 3, wherein the mechanism (1) has a cylindrical object made of at least one material selected from the group consisting of metal, rubber, and plastic. apparatus.   The said optical system (4) has a condensing lens and the mechanism in which the distance of this condensing lens and the surface of the said cylindrical support body (a) is changed, The any one of Claim 1 to 4 The cylindrical printing original plate forming apparatus described in 1.   The cylindrical printing original plate molding according to any one of claims 1 to 5, wherein the plate or cylinder is made of quartz glass and has a light transmittance of 80% or more and 100% or less at a wavelength of 350 nm. apparatus. The cylindrical support (a) and the plate-like object or cylindrical object move synchronously,
The cylindrical support body (a) and the sheet-like resin have a part that is always in contact, and the contacted part is irradiated with light. The cylindrical printing original plate forming apparatus described in 1.   The cylindrical printing original plate manufactured using the cylindrical printing original plate shaping | molding apparatus of any one of Claim 1 to 7. A method for producing a cylindrical printing original plate having a cylindrical support (a) and a sheet-like resin bonded on the cylindrical support (a),
(I) forming a photocurable adhesive layer on the surface of the cylindrical support (a);
(Ii) installing the sheet-like resin on the photocurable adhesive layer;
(Iii) sandwiching the sheet-like resin between a plate-like object or a cylindrical object having a light-transmitting slit and the cylindrical support (a);
(Iv) irradiating the photocurable adhesive layer with light through the light transmissive slit;
(V) rotating the cylindrical support (a) and irradiating light at a position different from that in the step (iv).   The method for producing a cylindrical printing original plate according to claim 9, wherein the sheet-like resin is made of at least one material selected from the group consisting of a thermoplastic resin, a photosensitive resin composition, and a thermosetting resin composition. .   The cylinder according to claim 9 or 10, wherein the sheet-shaped resin is a sheet-shaped printing original plate in which a photosensitive resin cured product or a thermosetting resin cured product is laminated on a sheet-shaped support made of a thermoplastic resin. A method for producing a letter printing original plate.   The photosensitive resin composition or the thermosetting resin composition is polyamide, polyimide, polyurethane, polyester, polycarbonate, polyether polyol, polyvinyl alcohol, vinyl alcohol-vinyl acetate copolymer, styrene-butadiene copolymer, and styrene. The method for producing a cylindrical printing original plate according to claim 10 or 11, comprising at least one resin selected from the group consisting of isoprene copolymers.   The cylindrical printing original plate according to any one of claims 9 to 12, wherein the cylindrical printing original plate is a cylindrical printing original plate or a cylindrical printing plate used in flexographic printing, dry offset printing, or gravure printing. Manufacturing method.   The method for producing a cylindrical printing original plate according to claim 13, wherein the cylindrical printing original plate is a cylindrical printing original plate for laser engraving.

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