JP2010069836A - Method for manufacturing laser-engraved printing original plate, and method for manufacturing laser-engraved printing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture a laser-engraved printing original plate and a laser-engraved printing plate which can highly accurately control engraving depth of a minute pattern near its surface in a laser engraving process. <P>SOLUTION: The laser-engraved printing original plate is manufactured by the following processes (1) to (4). (1) A process for forming a curable resin composition layer (α) on a sheet-shaped support or a cylindrical support. (2) A process for curing the curable resin composition layer (α) to form a resin cured material layer (β) which has 10 to 100% transmissivity to near infrared light at a 700 nm to 1.6 μm wavelength region. (3) A process for forming on the resin cured material layer (β) a curable resin composition layer (γ) which absorbs the near infrared light. (4) A process for curing the curable resin composition layer (γ) to form a resin cured material layer (δ). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a laser engraving printing original plate corresponding to an engraving method using two kinds of lasers, and a method for producing a laser engraving printing plate for forming a pattern by an engraving method using two kinds of lasers.

Conventionally, a laser engraving method that forms a concavo-convex pattern on the surface by irradiating with laser light is known in a resin relief plate manufacturing process used for flexographic printing, dry offset printing, letter press printing, and surface processing processes such as embossing. ing.
In this laser engraving method, a curable rubber or a photosensitive resin composition obtained by photocuring a photosensitive resin composition, or a thermosetting resin cured product obtained by thermosetting a thermosetting resin composition is used as an original plate. ing.
In particular, in recent years, from the viewpoint of shortening the processing time, a material obtained by photocuring a photosensitive resin composition, that is, a photosensitive resin cured product, is frequently used in the laser engraving method.

  As such a laser engraving method, a printing original plate made of a material obtained by adding carbon black to a photosensitive resin composition mainly made of a thermoplastic elastomer is conventionally used with a YAG laser that emits near infrared rays or a carbon dioxide gas laser that emits infrared rays. A technique for engraving is disclosed (for example, see Patent Document 1).

Japanese Patent No. 2846954

By the way, since the near infrared laser has a wavelength of about 700 nm to 3 μm, the beam diameter can be narrowed down and it is suitable for engraving a fine pattern. On the other hand, there is a drawback that the engraving speed is slow.
On the other hand, a carbon dioxide laser is a typical laser for an infrared laser, but since the wavelength is as long as 10.6 μm, even if the beam diameter is narrowed down, the limit is 25 μm to 30 μm, which is not suitable for engraving fine patterns. Since the output is large, there is an advantage that the engraving speed is fast.

For this reason, a technique for engraving and manufacturing a high-performance printing plate having both a fine pattern and a rough pattern quickly and with high accuracy has been required.
The fine pattern is shallow near the surface of the printing plate and is formed by precisely controlling the depth, so that the thickness of the printing pattern can be accurately controlled.

  However, since the energy of the laser is not completely constant and fluctuates with time, it is difficult to accurately control and form the depth of a very shallow fine pattern.

  Therefore, in the present invention, in view of the problems in the conventional technology, the laser engraving technology can control the depth of the fine pattern with high accuracy and can form both the fine pattern and the rough pattern. It was decided to provide a method for producing a printing original plate and a method for producing a laser engraving printing plate using a laser engraving printing original plate produced by the production method.

  The invention of claim 1 is a method for producing a laser engraving printing original plate, wherein (1) a step of forming a curable resin composition layer (α) on a sheet-like or cylindrical support; ) The curable resin composition layer (α) is cured to form a cured resin layer (β) having a transmittance of 10% to 100% for near-infrared laser light in a wavelength region of 700 nm to 1.6 μm. And (3) forming a curable resin composition layer (γ) that absorbs near-infrared rays on the cured resin layer (β), and (4) the curable resin composition layer (γ And a step of forming a cured resin layer (δ), and a method for producing a laser engraving printing original plate.

  In the invention of claim 2, after the step (2) and before the step (3), (5) the surface of the cured resin layer (β) is irradiated with an electron beam or light having a wavelength of 100 nm to 200 nm. The manufacturing method of the laser-engraving printing original plate of Claim 1 which has the process to perform.

  In invention of Claim 3, after the said process (2), before the said process (3), it has the process of adjusting the thickness and surface roughness of the said resin hardened | cured material layer ((beta)), 3. The method for producing a laser engraving printing original plate according to claim 1, further comprising: (7) adjusting the thickness and surface roughness of the cured resin layer (δ) after the step (4).

  In the invention of claim 4, in the step (6) and the step (7), the method for adjusting the thickness and the surface roughness of the cured resin layer is selected from the group consisting of cutting, grinding and polishing. The method for producing a laser engraving printing original plate according to claim 3, which is at least one kind of method.

  In the invention of claim 5, the thickness of the cured resin layer (β) is from 0.1 mm to 10 mm, and the thickness of the cured resin layer (δ) is from 0.5 μm to less than 100 μm. The manufacturing method of the laser-engraving printing original plate as described in any one of Claims 1 thru | or 4 is provided.

  In the invention of claim 6, the support is a hollow cylindrical support, and the thickness of the hollow cylindrical support is 0.1 mm or more and 2 mm or less. The manufacturing method of the laser-engraving printing original plate described in 1. is provided.

  According to a seventh aspect of the present invention, there is provided the method for producing a laser engraving printing original plate according to the sixth aspect, wherein the hollow cylindrical support is a metal sleeve or a fiber reinforced plastic sleeve.

  In the invention of claim 8, the fiber-reinforced plastic sleeve is selected from the group consisting of polyester fiber, polyamide fiber, polyimide fiber, polyurethane fiber, cellulose fiber, glass fiber, carbon fiber, metal fiber, and ceramic fiber. The manufacturing method of the laser-engraving printing original plate of Claim 7 containing at least 1 type of fiber is provided.

  According to a ninth aspect of the present invention, there is provided the method for producing a laser engraving printing original plate according to any one of the second to eighth aspects, wherein in the step (5), the electron beam acceleration voltage is set to 50 keV or more and 300 keV or less.

  In invention of Claim 10, in the said process (5), the manufacturing method of the laser-engraving printing original plate as described in any one of Claim 2 thru | or 9 which irradiates an electron beam in inert gas atmosphere is provided.

  In the invention of claim 11, in the step (5), light having a wavelength of 100 nm or more and 200 nm or less is irradiated in the atmosphere in the atmosphere, and the distance between the cured resin layer (β) and the light source is 0.1 mm or more and 5 mm or less. A method for producing a laser engraving printing original plate according to any one of claims 2 to 9 is provided.

  In invention of Claim 12, the said curable resin composition layer ((gamma)) contains the near infrared laser absorptive dye or pigment, The laser engraving printing as described in any one of Claims 1 thru | or 11 A method for producing an original plate is provided.

  In invention of Claim 13, The laser-engraving printing original plate as described in any one of Claims 1 thru | or 12 which has the process of forming a cushion layer between the said support body and resin hardened | cured material layer ((delta)). A manufacturing method is provided.

  In the invention of claim 14, the cushion layer contains a thermosetting resin and / or a photocurable resin, and is formed by a step of curing the thermosetting resin and / or the photocurable resin. A method for producing the described laser engraving printing original plate is provided.

In invention of Claim 15, it is a manufacturing method of the laser-engraving printing plate using the laser-engraving printing original plate manufactured by the method of Claims 1 thru | or 14, Comprising: (8) On the resin hardened | cured material layer ((delta)) surface, A step of irradiating a near-infrared laser having a beam diameter of 1 μm or more and less than 10 μm to form a recess (ε); η) to form a recess (ζ);
A method for producing a laser engraving printing plate having:

  In invention of Claim 16, the depth of the said recessed part (epsilon) is 0.5 micrometer or more and less than 20 micrometers, and the depth of the said recessed part (ζ) is 20 micrometers or more and 1 mm or less, Laser engraving printing of Claim 15 A method for producing a plate is provided.

  According to a seventeenth aspect of the present invention, there is provided the method for producing a laser engraving printing plate according to the fifteenth or sixteenth aspect, wherein a surface opening size of the concave portion (ε) is 1 μm or more and less than 10 μm.

  In invention of Claim 18, the said recessed part ((epsilon)) is formed by regular arrangement | positioning, and the arrangement pitch is 2 micrometers or more and less than 20 micrometers, Manufacture of the laser engraving printing plate as described in any one of Claims 15 thru | or 17 Provide a method.

  In the invention of claim 19, the near-infrared laser is a pulsed laser, the oscillation frequency is 1 kHz or more and 500 MHz or less, and the half time width of the pulse time is 10 femtoseconds or more and 50 nanoseconds or less. The manufacturing method of the laser engraving printing plate as described in any one of 18 is provided.

  In the invention of claim 20, the resin cured product layer (β) contains at least one photocured product of a photosensitive resin composition, wherein the laser engraving printing plate according to claim 15 is manufactured. Provide a method.

  In invention of Claim 21, a conductor, a semiconductor, an insulator, and an optical material using the laser engraving printing plate produced by the manufacturing method of the laser engraving printing plate according to any one of Claims 15 to 20 A method of manufacturing an element for performing pattern printing by at least one selected from the group consisting of:

  In the invention of claim 22, the element is any one selected from the group consisting of an organic electroluminescent element, an organic solar cell, an organic semiconductor, an antenna circuit, a liquid crystal display element, and a plasma light emitting element. A method of manufacturing the described device is provided.

  According to a twenty-third aspect of the present invention, there is provided the element manufacturing method according to the twenty-first aspect, wherein the element is a microlens array or an optical waveguide.

  According to the present invention, in the laser engraving process, a laser engraving printing original plate manufacturing method capable of controlling the engraving depth of a fine pattern near the surface with high accuracy and a laser engraving printing original plate produced by the manufacturing method are used. A plate manufacturing method can be provided.

  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 description, In the range of the summary, various deformation | transformation can be implemented.

[Laser engraving printing plate manufacturing method]
The manufacturing method of the laser engraving printing original plate in the present embodiment,
(1) forming a curable resin composition layer (α) on a sheet-like or cylindrical support;
(2) The cured curable resin composition layer (α) is cured, and the cured resin layer (β) has a transmittance of 10% to 100% for near-infrared laser light in a wavelength region of 700 nm to 1.6 μm. Forming a step;
(3) forming a curable resin composition layer (γ) that absorbs near infrared rays on the resin cured product layer (β);
(4) A method for producing a laser engraving printing original plate, comprising: a step of curing the curable resin composition layer (γ) to form a cured resin layer (δ).

In addition, it is preferable to perform the process of irradiating the surface of the cured resin layer (β) with (5) the surface of the cured resin layer (β) with an electron beam or light with a wavelength of 100 nm to 200 nm.
By this step, the adhesive strength at the contact interface between the cured resin layer (β) and the cured resin layer (δ) can be secured.
The electron beam may be either a low-energy electron beam or a high-energy electron beam, but a low-energy electron beam is preferable in consideration of the device scale, process complexity, price, and the like.
The acceleration voltage of the low energy electron beam is preferably from 50 keV to 300 keV, more preferably from 50 keV to 200 keV, and even more preferably from 50 keV to 100 keV.

  The atmosphere in which the electron beam is irradiated may be in the air or an inert gas atmosphere, but an inert gas atmosphere is preferable from the viewpoint of extending the lifetime of the reactive chemical species formed on the surface. Examples of the inert gas include nitrogen, helium, and argon.

As a light source for irradiating light with a wavelength of 100 nm or more and 200 nm or less, an excimer lamp is preferable from the viewpoint of handling.
The wavelength of the irradiation light is more preferably 150 nm or more and 180 nm or less.
In the excimer lamp, the wavelength of irradiation light varies depending on the type of gas to be sealed. For example, NeF (108 nm), Ar ₂ (126 nm), Kr ₂ (146 nm), F ₂ (154 nm), ArBr (161 nm), Xe (172 nm), ArCl (175 nm), KrI (191 nm), ArF (193 nm) Can be mentioned.
Moreover, it is preferable that the distance of a resin cured material layer ((beta)) and a light source is 0.1 mm or more and 5 mm or less from a viewpoint of the illumination intensity ensuring on the resin cured material layer ((beta)) surface.
From the viewpoint of ensuring good workability, 0.5 mm or more and 5 mm or less are more preferable.

Compounds and resins having alkoxysilyl groups, isocyanate groups, amino groups and polymerizable unsaturated groups in the molecule that react with functional groups such as hydroxyl groups and carboxyl groups formed on the surface after irradiation with light having a wavelength of 100 nm to 200 nm It is preferable to contact the surface of the cured product layer (β).
This is because, by irradiating light with a wavelength of 100 nm or more and 200 nm, a hydroxyl group or a carboxyl group is generated on the surface. Therefore, an alkoxysilyl group, an isocyanate group, an amino group, and a polymerizable unsaturated group that react with these functional groups are formed. In order to improve the adhesive force with the curable resin composition layer (γ) laminated on the resin cured product layer (β) by bringing the compound having the resin into contact with the resin cured product layer (β) to form a chemical bond. is there.

Between the step (2) and the step (3), (6) a step of adjusting the thickness and surface roughness of the cured resin layer (β) is performed, and after the step (4), ( 7) It is preferable to perform a step of adjusting the thickness and surface roughness of the cured resin layer (δ).
In these steps (6) and (7), the method of adjusting the thickness and surface roughness of the cured resin layer is at least one method selected from the group consisting of cutting, grinding, and polishing. And

The laser engraving printing original plate produced by the method in the present embodiment has at least two layers of cured resin.
That is, a laminate comprising a cured resin layer (β) having a transmittance of 10% to 100% for near infrared rays in a wavelength region of 700 nm to 1.6 μm and a cured resin layer (δ) that absorbs near infrared rays. Have a body.
The cured resin layer (δ) present on the laser processed surface side can be engraved using a near infrared laser to absorb near infrared rays, and the cured resin layer (β) present on the lower layer side is Can not engrave with near infrared laser because it transmits near infrared rays. The cured resin layer (β) can be engraved with a laser other than the near infrared laser.
The laser engraving printing original plate produced by the method in the present embodiment is characterized in that only a cured resin layer existing on the surface side can be engraved with a near infrared laser.
Thereby, a fine pattern is formed in the vicinity of the surface layer by using a near infrared laser with a narrowed beam diameter. At this time, the depth of the concave pattern to be formed can be accurately and easily controlled by controlling the thickness of the cured resin layer present on the surface side.
Further, the entire upper layer and lower layer are engraved to engrave a large concave pattern to form a convex pattern serving as an ink carrier on the plate surface. That is, in the final laser engraving printing plate, a fine concave pattern is formed on the surface of the convex pattern which is an ink carrier.
In order to achieve such a configuration, the printing original plate is assumed to have a multilayer structure having different absorption wavelengths, and the original plate is engraved using a plurality of types of lasers having different wavelengths.

The cured resin layer (β) preferably has a thickness of 0.1 mm to 10 mm, and the cured resin layer (δ) preferably has a thickness of 0.5 μm to less than 100 μm.
By setting the thickness of the cured resin layer (β) and the cured resin layer (δ) in the above range, it can be applied to printing such as flexographic printing, dry offset printing, gravure printing, and printing that requires fine pattern formation. It can cope with the usage sufficiently.

  The resin cured product layer (β) (lower layer) has a transmittance of near infrared laser in the wavelength region of 700 nm to 1.6 μm of 10% or more and 100% or less. The transmittance is preferably 50% or more and 100% or less, and more preferably 70% or more and 100% or less. It was confirmed that engraving with a near infrared laser on the cured resin layer (β) would be extremely difficult if the light transmittance was in the above range.

  The cured resin layer (δ) (upper layer) has high absorbability with respect to the near-infrared laser. For this reason, the curable resin composition layer (γ), which is the resin cured product layer (δ) (upper layer), contains a near-infrared absorber such as a dye or a pigment having absorption characteristics at wavelengths in the near-infrared region. Is preferred.

In addition, according to the use laser wavelength which performs laser engraving, the kind of near-infrared absorber contained in the resin cured material layer (δ) (upper layer) is selected.
In general, since dyes and pigments made of organic compounds and metal oxides have relatively sharp light absorption characteristics due to their molecular structure, it is preferable to select a compound corresponding to the laser wavelength to be used.
In addition, carbon-based pigments such as carbon black, activated carbon, graphite, carbon nanotubes, and fullerene have a wide range of light absorption characteristics, so that the range of lasers that can be used for engraving is widened.
Moreover, it is preferable to adjust the density | concentration of a near-infrared absorber according to the average output and peak output of the laser to be used.
Specifically, when the average output or peak output of the laser is large, the concentration of the near-infrared absorber can be lowered, and in the opposite case, the concentration of the near-infrared absorber needs to be increased. In particular, in the case of a photocuring system, the film thickness that can be cured can be increased when the concentration of the near-infrared absorbing agent (many substances having strong light absorption characteristics in the ultraviolet region) are low.
In the curable resin composition layer (γ), the concentration of the near-infrared absorber in the cured resin layer (δ) constituting material is preferably 0.5% by mass or more and 20% by mass or less, and more preferably 0.8% by mass or more. 15 mass% or less is more preferable, and 1 mass% or more and 10 mass% or less are more preferable. If it is the said density | concentration range, near infrared rays will be fully absorbed and the engraving with a near infrared laser will be attained.

[Method of forming curable resin composition layer]
A conventionally known method can be applied as a method of forming the curable resin composition layer.
For example, a casting method, a method of extruding resin from a nozzle or a die with a pump or an extruder, adjusting the thickness with a blade, a method of calendering with a roll to make a thickness, spraying using a spray, etc. Methods and the like. In addition, in the process of forming a layer, you may carry out, heating in the temperature range which can avoid thermal decomposition of curable resin composition. Moreover, you may perform a rolling process, a grinding process, etc. as needed.

[Curing method of curable resin composition layer]
(Photocuring method)
When the curable resin composition layer is made of a photosensitive resin composition, it is crosslinked by light irradiation to obtain a cured resin product. Moreover, you may bridge | crosslink by light irradiation, shaping | molding.
Examples of the light source include a high pressure mercury lamp, an ultra high pressure mercury lamp, an ultraviolet fluorescent lamp, a germicidal lamp, a carbon arc lamp, a xenon lamp, and a metal halide lamp.
The irradiation light with respect to the photosensitive resin composition layer is preferably light having a wavelength of 200 nm to 300 nm. In particular, when the above-described hydrogen abstraction type photopolymerization initiator is used, the photosensitive resin cured product layer surface can be sufficiently cured because it has a strong light absorption in the wavelength region.
Although the said light source may be one type, since hardening of resin may be aimed at by making it harden using two or more types of light sources from which a wavelength differs, it is preferred to use two or more types of light sources suitably. .
(Thermosetting method)
When the curable resin composition layer is formed of a thermosetting resin composition, the resin is cured by heat treatment.
Examples of the heat treatment 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.

[Materials constituting the laser engraving printing original plate]
The laser engraving printing original plate is composed of a curable resin composition described later, a support, and other arbitrary functional layers.

(Curable resin composition)
The curable resin composition may be solid or liquid at 20 ° C., but is preferably liquid at 20 ° C. to ensure ease of moldability.
In addition, liquid means a polymer that has the property of being easily fluidly deformed and solidified into a deformed shape by cooling, and when an external force is applied, it deforms instantaneously according to the external force, And when external force is removed, it is a term for an elastomer having the property of restoring its original shape in a short time.
In the present embodiment, the curable resin composition layer (α) and the curable resin composition layer (γ) are formed using the curable resin composition.
These curable resin compositions preferably contain a resin (a) and an organic compound (b) which will be described later. In the curable resin composition layers (α) and (γ), the resin (a) and the organic compound are used. The compounds (b) may be the same or different, but from the viewpoint of securing adhesive strength, it is preferable that they have a similar composition.

The curable resin composition is a photosensitive resin composition or a thermosetting resin composition.
From the viewpoint of curing speed, a photosensitive resin composition is preferable, and in the case of a system having a low light transmittance and containing a dye or pigment at a high concentration, a thermosetting resin composition is preferable.
Since the cured resin layer (β) is preferably a thicker film than the cured resin layer (δ), the cured resin layer (β) is a photocured product of at least one photosensitive resin composition. It is preferable to include.

The curable resin composition preferably has a viscosity at 20 ° C. of 10 Pa · s to 10 kPa · s, and more preferably 50 Pa · s to 5 kPa · s.
If the viscosity is 10 Pa · s or more, as will be described later, the mechanical strength of the cured resin can be sufficiently ensured, and the shape can be easily maintained even when molded into a cylindrical shape, and can be easily processed. .
If the viscosity is 10 kPa · s or less, it is easily deformed even at room temperature, can be easily processed, can be easily formed into a sheet-like or cylindrical resin cured product, and the process is simple.
In particular, in order to obtain a cured cylindrical resin with high thickness accuracy, when the liquid curable resin layer is formed on the cylindrical support, the curable resin composition may cause a phenomenon such as dripping due to gravity. It is desirable that the curable resin composition has a relatively high viscosity with a viscosity of 100 Pa · s or higher, more preferably 200 Pa · s or higher, and even more preferably 500 Pa · s or higher so as not to occur.

<Resin (a)>
The resin (a) is preferably a liquid resin at 20 ° C. Thereby, the curable resin composition also becomes liquid at 20 ° C.
The number average molecular weight of the resin (a) is preferably from 1,000 to 300,000, more preferably from 2,000 to 200,000, and even more preferably from 5,000 to 100,000.
If the number average molecular weight of the resin (a) is 1000 or more, a practically sufficient strength can be obtained when the cured curable resin is obtained by cross-linking in a later step, and durability as a printing substrate or the like. Sex is obtained.
The upper limit of the number average molecular weight of the resin (a) is 300,000 or less as described above. If it is 300,000 or less, the viscosity of the curable resin composition does not increase excessively, and a complicated processing method is not necessary when producing a sheet-like or cylindrical resin-cured product. To preferred.
The number average molecular weight is a value measured by gel permeation chromatography, calibrated with polystyrene having a known molecular weight, and converted.

The resin (a) may have a polymerizable unsaturated group in the molecule. Particularly preferred is a polymer having an average of 0.7 or more polymerizable unsaturated groups per molecule. If the polymerizable unsaturated group is 0.7 or more on an average per molecule, the cured resin obtained from the curable resin composition has excellent mechanical strength, particularly for repeated use as a printing substrate. Durability is obtained. Considering the mechanical strength of the cured resin, the polymerizable unsaturated group of the resin (a) is preferably 0.7 or more per molecule, more preferably more than 1.
The upper limit of the number of polymerizable unsaturated groups per molecule is not particularly limited, but is preferably 20 or less. If it is 20 or less, the shrinkage | contraction at the time of hardening can be reduced and generation | occurrence | production of the crack etc. in the surface vicinity can also be suppressed.
The term “intramolecular” as used herein includes the case where a polymerizable unsaturated group is directly attached to the end of the polymer main chain, the end of the polymer side chain, the polymer main chain, or the side chain. It is.

Specific examples of the resin (a) include the following polymers as a skeleton.
For example, 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, polyacrylic acid, One selected from the group consisting of polymers having a hetero atom in the main chain such as poly (meth) acrylic acid esters, poly (meth) acrylamide, polyester, polycarbonate, polyacetal, polyurethane, polyamide, polyurea, polyimide, or the like, or Two or more types may be mentioned. In the case of using these plural polymers, either a copolymer or a blend may be used.

When using the laser engraving printing original plate produced by the method according to the present embodiment as a flexible relief image, particularly for flexographic printing plate use, a part of the resin (a) described above, It is preferable to contain a liquid resin having a glass transition temperature of 20 ° C. or lower, more preferably a liquid resin having a glass transition temperature of 0 ° C. or lower.
Examples of such a liquid resin include hydrocarbons such as polyethylene, polybutadiene, hydrogenated polybutadiene, polyisoprene, and hydrogenated poisoprene, polyesters such as adipate and polycaprolactone, and polymers such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples thereof include silicones such as ethers, aliphatic polycarbonates and polydimethylsiloxane, polymers of (meth) acrylic acid and / or derivatives thereof, and mixtures and copolymers thereof.
The content of these liquid resins is preferably 30% by mass or more and 100% by mass or less with respect to the entire resin (a). In particular, unsaturated polyurethanes having a polycarbonate structure are preferred from the viewpoint of weather resistance.

A method for introducing the polymerizable unsaturated group described above into the compound constituting the resin (a) will be described.
For example, it is possible to directly use a polymerizable unsaturated group introduced into the molecular end or molecular chain. Alternatively, a hydroxyl group, amino group, epoxy group, carboxyl group, acid anhydride group, ketone A compound having a plurality of functional groups capable of bonding to the reactive group (for example, a hydroxyl group or an amino group) A functional group that reacts with the terminal binding group of the compound obtained by the reaction after adjusting the molecular weight and converting it to a terminal binding group. And a method in which a compound having a polymerizable unsaturated group is reacted to introduce a polymerizable unsaturated group at the terminal is suitable.

The resin (a) is preferably a compound having high thermal decomposability.
For example, compounds having α-methylstyrene, methacrylic acid ester, acrylic acid ester, carbonate bond, carbamate bond and the like in the molecule are known as highly thermally decomposable compounds.
As an index of thermal decomposability, thermogravimetric analysis data obtained by measuring weight loss when a sample is heated in an inert gas atmosphere is used.
Specifically, the temperature at which the weight is reduced by half is preferably in the range of 150 ° C. or higher and 450 ° C. or lower. A more preferable range is 250 ° C. or higher and 400 ° C. or lower, and further preferably 250 ° C. or higher and 380 ° C. or lower.
Also preferred are compounds that undergo thermal decomposition in a narrow temperature range. As the index, in the thermogravimetric analysis, the difference between the temperature at which the weight is reduced to 80% of the initial weight and the temperature at which the weight is reduced to 20% of the initial weight is preferably 100 ° C. or less. More preferably, it is 80 degrees C or less, More preferably, it is 60 degrees C or less.

<Organic compound (b)>
The organic compound (b) is a compound having an unsaturated bond that contributes to a radical polymerization reaction or a ring-opening polymerization reaction, and the number average molecular weight is 1000 or less considering the ease of dilution with the resin (a). Is preferred.
Examples of the organic compound (b) include olefins such as ethylene, propylene, styrene and divinylbenzene, acetylenes, (meth) acrylic acid and derivatives thereof, haloolefins, unsaturated nitriles such as acrylonitrile, (meth) Acrylamide and its derivatives, allyl compounds such as allyl alcohol and allyl isocyanate, unsaturated dicarboxylic acids such as maleic anhydride, maleic acid, fumaric acid and itaconic acid and their derivatives, vinyl acetates, N-vinylpyrrolidone, N-vinyl Examples thereof include carbazole and cyanate esters. In particular, derivatives such as (meth) acrylic acid and (meth) acrylic acid ester are preferable from the viewpoint of variety, price, and the like.
The various derivatives include alicyclic compounds 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. Aromatic compounds having alkyl groups, alkyl groups, halogenated alkyl groups, alkoxyalkyl groups, hydroxyalkyl groups, aminoalkyl groups, tetrahydrofurfuryl groups, compounds having functional groups such as glycidyl groups, alkylene glycols, polyoxyalkylene glycols, ( Alkyl / allyloxy) polyalkylene glycols and ester compounds of polyhydric alcohols such as trimethylolpropane.

The organic compound (b) having a polymerizable unsaturated group described above may be used alone or in combination of two or more depending on the purpose of the laser engraving printing original plate produced by the method in the present embodiment. Good.
For example, when used as a printing plate, as the organic compound used to suppress swelling with respect to an organic solvent such as alcohol or ester which is a solvent for printing ink, at least one kind of long-chain aliphatic, alicyclic or aromatic derivative is used. It is preferable to have it.
In order to increase the mechanical strength of the cured product obtained from the curable resin composition, the organic compound (b) has at least one compound having an alicyclic or aromatic substituent. Is preferred. In this case, the compound having an alicyclic or aromatic substituent 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 (b). It is below mass%.

<Photopolymerization initiator>
When using the photosensitive resin composition as a curable resin composition mentioned above, it is preferable to contain a photoinitiator.
As irradiation light, high energy rays such as ultraviolet rays, visible rays, electron beams, and X-rays can be used. In particular, when photocuring with ultraviolet rays or visible rays, the photopolymerization initiator is highly effective.
As the photopolymerization initiator, a hydrogen abstraction type photopolymerization initiator (d) and / or a decay type photopolymerization initiator (e) is preferable.

Although it does not specifically limit as a hydrogen abstraction type photoinitiator (d), An aromatic ketone is preferable. Aromatic ketone is efficiently converted into an excited triplet state by photoexcitation, and a chemical reaction mechanism has been proposed in which this excited triplet state generates a radical by extracting hydrogen from the surrounding medium. This is because the generated radical participates in the photocrosslinking reaction.
In the present embodiment, 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 the surrounding medium through an excited triplet state.
Examples of the aromatic ketone include benzophenones, Michler ketones, xanthenes, thioxanthones, and anthraquinones, and at least one compound selected from these groups is preferable.
The benzophenones are benzophenone and derivatives thereof, specifically 3,3 ′, 4,4′-benzophenone tetracarboxylic anhydride, 3,3 ′, 4,4′-tetramethoxybenzophenone and the like.
Michler ketones are Michler ketone and its derivatives.
Xanthenes are derivatives substituted with xanthene and an alkyl group, phenyl group, or halogen group.
Thioxanthones are derivatives substituted with thioxanthone and an alkyl group, a phenyl group, or a halogen group, and examples thereof include ethylthioxanthone, methylthioxanthone, and chlorothioxanthone.
Anthraquinones refer to anthraquinone and derivatives substituted with alkyl groups, phenyl groups, halogen groups, and the like.
The addition amount of the hydrogen abstraction type photopolymerization initiator described above is preferably 0.3% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less of the total amount of the photosensitive resin composition. When the addition amount is within this numerical range, when the photosensitive resin composition is photocured in the atmosphere, the cured surface of the cured product can be sufficiently secured, and cracks and the like do not occur on the surface during long-term storage. , Can ensure fading.

The decay type photopolymerization initiator (e) is a compound that generates an active radical by generating a cleavage reaction in the molecule after light absorption, and is not particularly limited.
Specific examples include benzoin alkyl ethers, 2,2-dialkoxy-2-phenylacetophenones, acetophenones, acyloxime esters, azo compounds, organic sulfur compounds, acylphosphine oxides, diketones and the like. It is preferable to use at least one compound selected from these groups.
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, 2,2-diethoxyacetophenone, and the like.
Examples of acyl oxime 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 methyl benzoyl formate.
The addition amount of the collapsible photopolymerization initiator is preferably 0.3% by mass or more and 10% by mass or less, and more preferably 0.5% by mass or more and 5% by mass or less of the total amount of the photosensitive resin composition. When the addition amount is within this numerical 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 may be used as the photopolymerization initiator. Examples of such compounds include α-aminoacetophenones, such as 2-methyl-1- (4-methylthiophenyl) -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1 And compounds such as-(4-morpholinophenyl) -butanone.
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 mass of the total amount of the photosensitive resin composition. % To 10% by mass is preferable, and 0.5% to 3% by mass is more preferable. If the addition amount is within this numerical range, the mechanical properties of the cured product can be sufficiently secured even when the photosensitive resin composition is photocured in the atmosphere.

As the photopolymerization initiator, a photoacid generator or a photobase generator can also be applied.
This is a compound that generates an acid or a base by light irradiation, and has a function of ring-opening polymerization of a compound having a functional group that undergoes a ring-opening polymerization reaction, such as an epoxy compound or an oxetane compound.

<Thermal polymerization initiator>
When using a thermosetting resin composition as the curable resin composition, it is preferable to include a thermal polymerization initiator in the resin.
A compound suitable as a thermal polymerization initiator is a thermal polymerization initiator that can be used in radical polymerization reactions and ring-opening polymerization reactions. Examples of thermal polymerization initiators used in radical polymerization reactions include organic peroxides, inorganic peroxides, organic silicon peroxides, hydroperoxides, azo compounds, thiol compounds, phenol resins, amino resins, halogen compounds, aldehyde compounds Etc. Moreover, as a thermal polymerization initiator used for the ring-opening polymerization reaction, it is preferable to select a latent thermal polymerization initiator in which a thermal polymerization initiator is put in a microcapsule.
The thermal polymerization initiator is preferably liquid at 20 ° C. from the viewpoint of easy mixing with the resin (a) or the organic compound (b).
The content of the thermal polymerization initiator is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 5% by mass or less, and more preferably 1% by mass or more with respect to the total amount of the thermosetting resin composition. 5 mass% or less is more preferable.
If the content rate of a thermopolymerization initiator is this numerical range, a thermosetting resin composition can fully be hardened and the adhesiveness of the surface of a thermosetting material can be reduced.

Selection of a suitable thermal polymerization initiator is important for carrying out the method in the present embodiment.
The thermal stability of the thermal polymerization initiator is usually determined by the method with a 10-hour half-life temperature of 10 h-t1 / 2, i.e. 50% of the initial amount of thermal polymerization initiator decomposes after 10 hours to free radicals. Is indicated by the temperature at which Further details on this are given in “Encyclopedia of Polymer Science and Engineering”, Vol. 11, page 1 onwards, John Wiley & Sons, New York, 1988.
Particularly suitable thermal polymerization initiators usually have a 10 h-t1 / 2 of preferably at least 60 ° C, more preferably at least 70 ° C. Especially preferably, it is 10 h-t1 / 2 of 80 to 150 degreeC.
As the thermopolymerization initiator, an organic peroxide is preferable from the viewpoint of thermosetting and compatibility with the thermosetting resin composition. Specific examples include peroxyesters such as t-butyl peroctanoate, t-amyl peroctanoate, t-butyl peroxyisobutyrate, t-butyl peroxymaleate, t-amyl perbenzoate, diperoxyphthal. Di-t-butyl acid, t-butyl perbenzoate, t-butyl peracetate and 2,5-di (benzoylperoxy) -2,5-dimethylhexane, certain diperoxyketals such as 1,1- Di (t-amylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (t-butylperoxy) butane and ethyl 3,3-di (t-butylperoxy) butyrate Some dialkyl peroxides, such as di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide Sid and 2,5-di (t-butylperoxy) -2,5-dimethylhexane, certain diacyl peroxides such as dibenzoyl peroxide and diacetyl peroxide, certain t-alkyl hydroperoxides such as t-butylhydro Peroxides, t-amyl hydroperoxide, pinane hydroperoxide and cumyl hydroperoxide. Moreover, an azo compound is mentioned as a preferable thing when forming the cushion layer containing a bubble. For example, 1- (t-butylazo) formamide, 2- (t-butylazo) isobutyronitrile, 1- (t-butylazo) cyclohexanecarbonitrile, 2- (t-butylazo) -2-methylbutanenitrile, 2, 2'-azobis (2-acetoxypropane), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutanenitrile), etc. It is this compound.

<Fine particles>
To the curable resin composition described above, inorganic fine particles, organic fine particles, and organic-inorganic composite fine particles may be added.
Addition of these fine particles improves the mechanical properties of the cured resin obtained by photocuring, improves the wettability of the surface of the cured resin, or adjusts the viscosity of the curable resin composition, viscoelasticity of the cured resin The characteristics can be adjusted.
The material of the inorganic fine particles and the organic fine particles is not particularly limited, and known materials are 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.
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 are preferable. Furthermore, for the purpose of improving the solvent resistance of the obtained cured resin, it is preferable to add inorganic fine particles or organic fine particles formed of a material having good swelling characteristics in the solvent used.
In addition, an inorganic porous material with excellent adsorption and removal characteristics for viscous liquid residues generated during laser engraving for the purpose of forming a pattern penetrating the surface of the cured resin layer or the cured photosensitive resin by the laser engraving method described below. Fine particles may be added. Examples of such inorganic porous fine particles include porous silica, mesoporous silica, silica-zirconia porous gel, porous alumina, and porous glass.

  The fine particles described above preferably have a number average particle diameter of 0.01 to 100 μm. When using fine particles in the range of this number average particle diameter, it is possible to avoid inconveniences such as increase in viscosity, entrainment of bubbles, and generation of a large amount of dust when mixing with the resin (a) and the organic compound (b), Unevenness can be prevented from occurring on the surface of the cured resin. The number average particle diameter of the fine particles is more preferably 1 to 10 μm. The number average particle size of the fine particles can be measured using a laser scattering type particle size distribution measuring apparatus.

The shape of the fine particles described above is not particularly limited, and may be any of a spherical shape, a flat shape, a needle shape, an amorphous shape, or a particle having protrusions on the surface. In particular, spherical particles are preferable from the viewpoint of wear resistance.
Alternatively, the surface of the fine particles may be coated with a silane coupling agent, a titanium coupling agent, or other organic compound and subjected to a surface modification treatment to make the particles more hydrophilic or hydrophobic.
These fine particles may be used alone or in combination of two or more.

In the curable resin composition, the ratio of the resin (a), the organic compound (b), and the fine particles described above is usually 5 to 200 parts by mass of the organic compound (b) with respect to 100 parts by mass of the resin (a). Is preferable, and 20-100 mass parts is more preferable. The fine particles are preferably 1 to 100 parts by weight, more preferably 2 to 50 parts by weight, and even more preferably 2 to 20 parts by weight.
When the ratio of the organic compound (b) is in the above range, it is easy to balance the hardness and tensile strength / elongation of the resulting curable resin cured product, the shrinkage during curing is within a small range, and thickness accuracy can be secured. .

<Other additives>
In addition, the curable resin composition may contain other additives such as a polymerization inhibitor, an ultraviolet absorber, a lubricant, a surfactant, a plasticizer, and a fragrance depending on the purpose and purpose.

(Support)
The support constituting the laser engraving master is assumed to be a sheet or a cylinder.
Examples of the sheet-like support include plastics such as polyester, polyimide, polyamide, polyolefin, polyphenylene ether, and polyphenylene thioether, and sheet materials made of metal such as nickel, aluminum, and iron. The thickness of the sheet-like support is preferably 50 μm or more and 500 μm or less, and more preferably 100 μm or more and 200 μm or less.
Examples of the cylindrical support include hollow cylindrical materials such as metal, rubber, and plastic cylinders, plastic, metal, fiber reinforced plastic sleeves, and film reinforced plastic sleeves. From the viewpoint of handleability and weight, a hollow cylindrical material made of fiber-reinforced plastic is preferable. The fiber reinforced plastic preferably contains at least one kind of fiber selected from glass fiber, polyamide fiber, polyimide fiber, polyester fiber, polyurethane fiber, cellulose fiber, carbon fiber, metal fiber, and ceramic fiber.
The thickness of the cylindrical support is preferably from 0.1 mm to 2 mm, more preferably from 0.3 mm to 1.5 mm, and even more preferably from 0.4 mm to 0.8 mm. When the thickness is within these numerical ranges, a practically sufficient mechanical strength can be secured, and weight reduction can also be achieved.

(Cushion layer)
A cushion layer made of an elastomer may be formed between the support and the cured resin layer (β).
The cushion layer is preferably an elastomer layer having a Shore A hardness of 10 to 70 degrees, or an ASKER-C hardness of 20 to 85 degrees as measured with an ASKER-C hardness meter. When the Shore A hardness is 10 degrees or more, or the ASKER-C hardness is 20 degrees or more, it deforms moderately, so that a good printing plate can be obtained.
Moreover, if Shore A hardness is 70 degrees or less or ASKER-C hardness is 85 degrees or less, it can serve as a cushion layer. A more preferable range of Shore A hardness is 20 to 60 degrees, and an 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 elastomer constituting the cushion layer is not particularly limited, and any one may be used as long as it has rubber elasticity, such as a thermoplastic elastomer, a photocurable elastomer, and a thermosetting elastomer. In particular, from the viewpoint of processability to a sheet-like or cylindrical printing plate, it is convenient and preferable to use a material that contains a thermosetting resin and / or a photocurable resin and is made into an elastomer by a curing step. .
The cushion layer preferably contains a cured photosensitive resin and contains bubbles and organic fine particles. In addition, it is preferable to use organic microparticles that are hollow microcapsules and that have inorganic microparticles attached to the surface of the hollow microcapsules.
The organic fine particles preferably have an average particle diameter of 1 μm to 500 μm, more preferably 10 μm to 300 μm, and still more preferably 80 μm to 200 μm.

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 0.4 g / cm ³ or more and 0.000 or less. More preferably 6 g / cm ³ or less.
When the density of the cushion layer is within the above range, it was confirmed that when printing was performed using the printing plate produced by the method in the present embodiment, the impact on the plate could be sufficiently absorbed.

Examples of the thermoplastic elastomer include styrene thermoplastic elastomers such as SBS (polystyrene-polybutadiene-polystyrene), SIS (polystyrene-polyisoprene-polystyrene), SEBS (polystyrene-polyethylene / polybutylene-polystyrene), etc. Examples thereof include elastomers, urethane-based thermoplastic elastomers, ester-based thermoplastic elastomers, amide-based thermoplastic elastomers, silicon-based thermoplastic elastomers, and fluorine-based thermoplastic elastomers.
Examples of the photocurable elastomer include those obtained by mixing a photopolymerizable monomer, a plasticizer, a photopolymerization initiator, and the like with the thermoplastic elastomer, and a liquid photosensitive resin obtained by mixing a photopolymerizable monomer, a photopolymerization initiator, and the like with a liquid resin. Examples thereof include compositions.
In addition, non-sulfur cross-linked rubber using a compound such as sulfur cross-linked rubber, organic peroxide, phenol resin initial condensate, quinone dioxime, metal oxide, thiourea as a cross-linking agent is also applicable. Furthermore, an elastomer obtained by three-dimensional crosslinking using a curing agent that reacts with a telechelic liquid rubber can also be used.
Furthermore, it may be a cushion layer made of a material such as polyurethane foam or polyethylene foam, having independent or open cells in the layer, or a commercially available cushion material or cushion tape may be used.

[Laser engraving printing plate manufacturing method]
The method for producing a laser engraving printing plate in the present embodiment uses the laser engraving printing original plate produced by the method of claims 1 to 14, and (8) a beam diameter of 1 μm or more and 10 μm on the surface of the cured resin layer (δ). A step of irradiating a near-infrared laser of less than that and forming regularly arranged concave portions (ε) in the irradiated portions; and (9) a beam diameter of 10 μm or more on the surface of the printing original plate on which the concave portions (ε) are formed. A step of irradiating a laser (η) of 100 μm or less and engraving the cured resin layer (δ) and the cured resin layer (β) to form a recess (ζ) in the irradiated portion.
That is, engraving is performed using laser beams having different wavelengths in order to form a fine pattern on the convex pattern surface that is the ink carrier of the laser engraving printing plate finally obtained.

(Laser engraving method)
Laser engraving on the cured resin layer (δ) constituting the laser engraving printing original plate is performed by using a computer as digital data and producing a relief image by operating a laser device using digital data.
The engraving of the fine pattern can be performed using a near infrared laser having a wavelength of 700 nm to 1.6 μm. Specifically, a semiconductor laser, a semiconductor laser-excited solid laser (YAG, YVO ₄ , YLF laser, etc.), a titanium sapphire laser, an alexandrite laser, a fiber laser doped with Er or Yb, or the like is used. These may be continuous wave lasers or pulsed lasers. A pulsed laser having a large peak output even when the average output of the laser is small is particularly preferable. The oscillation frequency is preferably 1 kHz to 500 MHz, more preferably 10 kHz to 100 MHz, and still more preferably 20 kHz to 100 MHz. Further, the half width of the pulse time is preferably 10 femtoseconds or more and 50 nanoseconds or less, and more preferably 1 picoseconds or more and 20 nanoseconds or less.
As described above, by making the laser oscillate in the pulse and setting the above numerical range, the energy per pulse can be large (the peak output is large), the damage caused by heat can be reduced, and the fine pattern can be reduced. Suitable for formation.

When forming a fine pattern, it is preferable to irradiate with a condensing lens with a laser beam diameter of 1 μm or more and less than 10 μm.
The laser beam diameter is measured by measuring the diameter of the recess formed by irradiation. Specifically, if the laser beam diameter is reduced to a minimum, the energy at the center of the beam becomes very high, so the damage to the light receiving element is large and it is difficult to directly measure the diameter. The diameter of the recess (β) is measured at 20 locations, and the average value of the hole diameters is defined as the laser beam diameter.
In addition, it is preferable to use a scanning electron microscope or a laser microscope for the measurement of the diameter of a recessed part.

It is preferable that the concave portions (ε) formed on the surface of the cured resin layer (δ) are regularly arranged.
The depth of the recess (ε) is preferably 0.5 μm or more and less than 20 μm. The dimensions of the openings of the recesses (ε) are preferably 1 μm or more and less than 10 μm, and the arrangement pitch of the regularly arranged recesses (ε) is preferably 2 μm or more and less than 20 μm.
The cured resin layer (δ) is the surface of the printing plate, and ink is transferred from the ink transfer roll in the printing process.
In this way, the convex surface for forming the printing pattern is formed with concave portions having the above-mentioned numerical range of depth, opening size, and arrangement pitch, thereby increasing the amount of ink received and making the convex surface flat. It was confirmed that thick film printing is possible compared to the case of the surface.

In the method for producing a laser engraving printing plate in the present embodiment, after forming the concave portion (ε) which is a fine pattern as described above, a coarser pattern (concave portion (ζ)) is formed.
This pattern is formed by lasers other than near infrared lasers, such as carbon dioxide lasers, second harmonics of solid lasers such as YAG having an oscillation wavelength in the visible light region, copper vapor lasers, and ultraviolet lasers having an oscillation wavelength in the ultraviolet region. For example, it can be performed using an excimer laser, a solid laser such as YAG wavelength-converted to the third or fourth harmonic.
The laser beam diameter is preferably 10 μm or more and 100 μm or less by a condenser lens. The beam diameter can be measured by measuring the minimum width of the pattern formed on the surface other than the convex pattern surface or the concave pattern obtained by irradiating a laser (γ) at one point with 20 scanning electron microscopes or laser microscopes. One of the average values measured for.

  The depth of the recess (ζ) is preferably 20 μm or more and 1 mm or less, and more preferably 100 μm or more and 500 μm or less.

The above-mentioned engraving by laser irradiation is carried out under an oxygen-containing gas, generally in the presence of air or an air stream, but can also be carried out under carbon dioxide gas or nitrogen gas.
After the engraving by laser irradiation is completed, the powdery or liquid substance slightly generated on the plate surface is cleaned with a predetermined method, for example, a method of cleaning with water containing a solvent or a surfactant, an aqueous cleaning agent by high pressure spraying, etc. It can be removed by an irradiation method, a high-pressure steam irradiation method, or the like.

After engraving by laser irradiation, after removing powdery or viscous liquid residue remaining on the plate surface, post-exposure may be performed by irradiating the surface with light having a wavelength of 200 nm to 450 nm.
Thereby, tack removal of the surface is performed.
This post-exposure may be performed in any environment such as air, inert gas atmosphere, and water.
In particular, it is effective when a hydrogen abstraction type photopolymerization initiator is contained in the photosensitive resin composition.
Further, before the post-exposure step, the printing plate surface may be previously treated with a treatment liquid containing a hydrogen abstraction type photopolymerization initiator.
Furthermore, you may expose in the state which immersed the printing plate in the process liquid containing a hydrogen drawing type photoinitiator.

[Uses of laser engraving printing plates]
The laser engraving printing plate produced by this embodiment is used for flexographic printing, dry offset printing, and gravure printing. In particular, narrow webs such as label printing for flexographic printing, which require highly accurate printed matter, and curved surface printing such as dry offset printing such as can printing and tube printing are preferable applications.
When the ink contains an aliphatic hydrocarbon and / or aromatic hydrocarbon in dry offset printing, polycarbonate, polyurethane, polyamide, polyvinyl alcohol, vinyl alcohol-vinyl acetate copolymer is contained as a constituent resin of the printing plate. It is preferable. This is because these resin materials have high resistance to the solvent.
Examples of the aliphatic hydrocarbon include compounds such as hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, cyclooctane, cyclodecane, dipentene, rubber volatile oil, mineral spirit, and high boiling point petroleum solvent (ink oil). It is done.
Examples of the aromatic hydrocarbon include compounds such as toluene, xylene, dimethylbenzene, dichlorobenzene, solvent naphtha, and tetralin.
Using the laser engraving printing plate produced according to the present embodiment, formation of a conductor, semiconductor, insulator, or optical element of an electronic element can be performed by printing. For example, an organic electroluminescent element, an organic solar cell, an organic semiconductor, an antenna circuit, a liquid crystal display element, a plasma light emitting element etc. are mentioned as an electronic element. Examples of the optical element include a microlens array and an optical waveguide.

  Hereinafter, specific examples and comparative examples will be specifically described, but the present invention is not limited thereto.

First, a laser engraving method applied in the following Examples and Comparative Examples and various physical property measuring methods will be described.
[(1) Laser engraving method]
(Formation of fine patterns with regularly arranged surfaces)
As a first method, a semiconductor laser excitation solid-state laser (manufactured by Spectra Physics, USA, trademark “HIPPO 106QW”, wavelength 1064 nm, oscillation frequency: 100 kHz, average output: 17 W) was used. While rotating the cylinder, the laser head was moved in the long axis direction of the cylinder, and pattern engraving was performed on the surface of the cured resin material to be patterned. The irradiation laser energy was controlled using an acousto-optic element (AO modulator).
As a second method, a laser drawing apparatus (trade name “Spark 4260”, manufactured by Escographics, Germany) equipped with a fiber laser (continuous oscillation laser, wavelength: 1064 nm), average laser output: 63 W, energy: 12 J / cm ² ), a sheet-like printing original plate was stuck on a cylinder, and a fine pattern was formed on the surface while rotating the cylinder at 200 rpm.
(Rough pattern formation)
The rough pattern is obtained using a carbon dioxide laser engraving machine (trademark: ZED-mini-1000, UK, manufactured by ZED, USA, coherent, 250 W output carbon dioxide laser, laser oscillation wavelength is 10.6 μm). went.
For engraving, a pattern in which a halftone dot pattern (120 lines / inch, area ratio 10%) and a square pattern having a size of 10 mm × 10 mm were regularly arranged in the XY direction at a pitch of 20 mm was created.
The linear speed of rotation of the cylinder was 10 m / sec.

[(2) Viscosity measurement method]
The viscosity of the following photosensitive resin composition and the organic compound (b) was measured under a condition of 20 ° C. using a B-type viscometer (trademark, B8H type; manufactured by Tokyo Keiki Co., Ltd., Japan).

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

[(4) Measuring method of near infrared laser beam diameter]
As the laser beam diameter, 20 diameters of the recesses formed on the surface of the cured resin were selected and measured with a laser microscope (trademark “OPTELICS, H1200” manufactured by Lasertec Corporation), and an average value was calculated.

[(5) Measuring method of beam diameter other than near infrared laser]
The laser beam diameter other than near-infrared laser is the minimum width of the pattern formed on the surface other than the convex pattern surface, or the size of the concave pattern obtained by irradiating the laser to one point. Laser microscope (trade name “OPTELICS” , H1200 "), and measured at 20 points, and set one of these average values.

[(6) Measuring method of surface roughness]
Using a surface roughness measuring machine “SE500” (trademark) manufactured by Kosaka Laboratory, stylus R (radius of curvature) 2 μm, cutoff λc = 0.8 mm, measuring length 4 mm, feeding speed 0.5 m / The measurement was performed under the condition of seconds, and the center line average roughness Ra was evaluated.

[Example 1]
(Preparation of resin (a))
To a 1 L separable flask equipped with a thermometer, a stirrer, and a reflux condenser, 447.24 g of polycarbonate diol (trade name “PCDL L4672” (number average molecular weight 1990, OH number 56.4, manufactured by Asahi Kasei Co., Ltd.) and tolylene diisocyanate After adding 30.83 g of natto and heating to 80 ° C., the reaction was allowed to proceed for about 3 hours.
Thereafter, 14.83 g of 2-methacryloyloxyisocyanate was added, and the reaction was further continued for about 3 hours. The terminal was a methacryl group (average number of polymerizable unsaturated groups in the molecule was about 2 per molecule), and the number average molecular weight. Produced approximately 10,000 resin (a).
This resin was in the shape of a syrup at 20 ° C., flowed when an external force was applied, and did not recover its original shape even when the external force was removed.

(Preparation of photosensitive resin composition)
Resin (a): Resin prepared as described above 70 parts by weight Organic compound (b): Phenoxyethyl methacrylate (molecular weight 190) 10 parts by weight
Polypropylene glycol monomethacrylate (molecular weight 400) 10 parts by weight porous fine powder silica (Fuji Silysia Chemical Co., Ltd., trade name “Cyrossphere C-1504” (hereinafter abbreviated as C-1504, number average particle diameter 4.5 μm, ratio) Surface area 520 m ² / g, average pore diameter 12 nm, pore volume 1.5 ml / g, loss on ignition 2.5% by mass, oil absorption 290 mL / 100 g) 5 parts by mass,
Photopolymerization initiator: 0.5 parts by mass of benzophenone, 0.6 parts by mass of 2,2-dimethoxy-2-phenylacetophenone Stabilizer: 0.5 parts by mass of 2,6-di-t-butylacetophenone A photosensitive resin composition was prepared.
This photosensitive resin composition was liquid at 20 ° C. The viscosity measured using a B-type viscometer was 1200 Pa · s at 20 ° C.

(Preparation of thermosetting resin composition)
Resin (a): Resin prepared as described above 70 parts by weight Organic compound (b): Phenoxyethyl methacrylate (molecular weight 190) 10 parts by weight
Polypropylene glycol monomethacrylate (molecular weight 400) 10 parts by weight Near infrared absorber: Carbon black (trade name “TB # A700F” manufactured by Tokai Carbon Co., Ltd.) 5 parts by weight Thermal polymerization initiator: t-butylperoxy-2-ethylhexyl carbonate ( Nippon Oil & Fats Co., Ltd. Trademark “Perbutyl E”) 1 part by weight stabilizer: 2,6-di-t-butylacetophenone 0.5 part by weight The above materials are mixed by adjusting the viscosity using tetrahydrofuran as a solvent, A thermosetting resin composition was prepared.

(Preparation of cured resin layer (β))
The liquid photosensitive resin composition produced as described above was applied to a thickness of 1.5 mm on 100 μm-thick polyethylene terephthalate (PET) placed on a glass plate.
Thereafter, UV light from a chemical lamp was irradiated at 4000 mJ / cm ² from the upper and lower surfaces to obtain a sheet-like photosensitive resin cured product.
The photosensitive resin cured product (β) had a light transmittance of 90% or more at a wavelength of 1064 nm.
Next, the surface of the photosensitive cured resin was irradiated with a low energy electron beam in a nitrogen atmosphere. As an electron beam irradiation apparatus, a trademark “ESI CB175 / 015 / 180L” manufactured by Iwasaki Electric Co., Ltd. was used, and an acceleration voltage was set to 100 keV and an output current was set to 10 mA.

(Preparation of cured resin layer (δ))
The thermosetting resin composition was spray-coated on the surface of the cured resin layer (β) formed as described above so as to have a thickness of 20 μm. After the solvent was removed by drying, it was sandwiched between PET cover films having a thickness of 100 μm on the surface, and was heat-pressed and cured using a hot press machine heated to 130 ° C. to form a cured resin layer (δ).
The transmittance of the cured resin layer (δ) with respect to light having a wavelength of 1064 nm was less than 1%.

(Formation of regularly arranged fine patterns by near infrared laser)
The PET cover film was peeled off, and laser drawing was performed using a laser drawing apparatus equipped with a fiber laser (trade name “Spark 4260” manufactured by Escographics, Germany) to form a circular recess (ε).
When the openings of the recesses (ε) were measured using a laser microscope, the dimensions were 9 μm, depth 20 μm, and array pitch 15 μm.

(Formation of rough pattern with carbon dioxide laser)
A sheet with a fine pattern regularly arranged on the surface was attached to a cylinder of a carbon dioxide laser engraving machine to form a rough pattern (concave portion (ζ)). The depth of the halftone dot portion was 80 μm, and the depth of the deepest portion was 0.5 mm.
Separately, a linear concave pattern was spirally formed for measuring the laser beam diameter. The width of the concave pattern for measurement was measured at 20 points with a laser microscope and found to be 30 μm.
Using the laser engraving printing plate obtained as described above, printing was performed on a glass plate with a precision printing machine (trademark “JSC-m60.60-M” manufactured by JEOL Ltd.). At this time, the thickness of the conductor pattern obtained by using silver nanopaste (trademark “NPS-J” manufactured by Harima Chemicals Co., Ltd.) containing aliphatic hydrocarbon as a solvent and removing the solvent by drying was 5 μm. It was.

[Example 2]
The same photosensitive resin composition and thermosetting resin composition as Example 1 mentioned above were prepared.
Next, a hollow cylindrical support was prepared in which an epoxy resin sleeve reinforced with 0.4 mm thick aramid fiber was attached to an air cylinder.
Next, a photosensitive resin composition obtained by removing porous fine powder silica from the same photosensitive resin composition as in Example 1 was prepared, and an adhesive having a thickness of 0.1 mm was formed on the surface of the hollow cylindrical support. A layer was formed.
By removing the porous fine powder silica, the adhesiveness with the hollow cylindrical support can be increased.
On the adhesive layer, the photosensitive resin composition produced in Example 1 was applied to a thickness of 1.3 mm using a doctor blade, and a metal halide lamp (manufactured by Nordson, USA) was rotated while the air cylinder was rotated. Light was irradiated at 4000 mJ / cm ² (integrated light amount at a wavelength of 350 nm) to form a cured resin layer (β).
Thereafter, the air cylinder is rotated, the surface is ground and polished, the film thickness and the surface roughness are adjusted, and the cured cylindrical resin having a thickness of 1.1 mm, a surface roughness Ra of 0.1 μm, and a thickness accuracy of ± 5 μm. Got.
The surface of the cylindrical resin cured product was irradiated with light having a wavelength of 172 nm at a distance of 2 mm from the light source using an Xe excimer lamp.
Further, an ethanol solution containing 2% by mass of methacryl-modified triethoxysilane was applied to the surface that had been subjected to the light irradiation treatment, and dried in an oven adjusted to a temperature of 70 ° C.
Thereafter, the thermosetting resin composition produced in Example 1 was spray-coated, a black thin film (cured resin layer (δ)) having a thickness of 10 μm after drying was laminated, and the temperature was adjusted to 130 ° C. The oven was installed in an air cylinder and thermally cured. At this time, in order to prevent liquid dripping, the air cylinder was installed on a cart equipped with a rotatable mechanism and was thermoset. A cylindrical laser engraving printing original plate was obtained by the operation described above.
Using this laser engraving printing original plate, in the same manner as in Example 1 described above, a laser drawing apparatus (trademark “Spark 4260”, manufactured by Esco Graphics Inc., Germany) equipped with a fiber laser was used. A regularly arranged circular fine concave pattern (concave (ε)) was formed on the entire surface of the black thin film (cured resin layer (δ)).
When this fine concave pattern was measured with a laser microscope, the opening diameter was 6 μm, the depth was 10 μm, and the arrangement pitch was 12 μm.
When the variation in the depth of the 50 fine concave patterns was investigated, the standard deviation of the depth was about 2 μm, and the variation in the thickness of the cured resin layer (δ) was confirmed to be extremely uniform. It was.
Next, in the same manner as in Example 1 described above, a coarse pattern (concave portion (ζ)) is formed using a carbon dioxide laser engraving machine (trademark ZED-mini-1000 manufactured by ZED, UK), and cylindrical laser engraving printing is performed. Got a version.
The cylindrical laser engraving printing plate obtained as described above is mounted on a flexographic printing machine (trade name “ITM-III” manufactured by Iyo Machinery Co., Ltd.), and a cyan monochrome solvent ink (solvent component) on a polyethylene film. : 20% by volume of ethyl acetate, 80% by volume of isopropyl alcohol), and printing at 2000 m was performed at a printing speed of 200 m / min.
Printing was performed by mounting a high hardness cushion bridge sleeve on an air cylinder and setting a cylindrical laser engraving printing plate thereon.
In the printing process, each layer of the cylindrical laser engraving printing plate was not peeled off, and a printed matter in a good state was obtained. The ink film thickness after drying the printed material was 2 μm.

Example 3
(Preparation of photosensitive resin composition)
Resin (a): Polycarbonate polyurethane having a number average molecular weight of about 100,000 (manufactured by Dainichi Seika Co., Ltd., trademark “Rezamin P890”) 70 parts by mass Organic compound (b): Phenoxyethyl methacrylate (molecular weight 190) 30 parts by mass
1 part by weight of trimethylolpropane triacrylate (molecular weight 338) 5 parts by weight of porous fine powder silica (trade name “Cyrossphere C-1504” manufactured by Fuji Silysia Chemical Ltd.) Photopolymerization initiator: 0.5 part by weight of benzophenone
2,2-dimethoxy-2-phenylacetophenone 0.6 parts by weight Stabilizer: 2,6-di-t-butylacetophenone 0.5 parts by weight The above materials are mixed at 130 ° C. using a kneader, and photosensitive resin is obtained. The composition was adjusted.

(Preparation of thermosetting resin composition)
Resin (a): Polycarbonate polyurethane having a number average molecular weight of about 100,000 (manufactured by Dainichi Seika Co., Ltd., trademark “Rezamin P890”) 70 parts by mass Organic compound (b): Phenoxyethyl methacrylate (molecular weight 190) 30 parts by mass
1 part by weight of trimethylolpropane triacrylate (molecular weight 338) near infrared absorber: 1 part by weight of phthalocyanine pigment (trade name “SIR-132” manufactured by Yamamoto Kasei Co., Ltd.) Stabilizer: 2,6-di-t-butylacetophenone 0. 5 parts by mass The above materials were mixed at a temperature of 130 ° C. using a kneader.
To the resulting mixture, 50 parts by mass of toluene as a solvent was added to prepare a liquid resin.
Further, 1 part by mass of t-butyl peroxy-2-ethylhexyl carbonate (trade name “Perbutyl E” manufactured by NOF Corporation) is added as a thermal polymerization initiator, and a liquid thermosetting resin composition containing a solvent is obtained. It was.
The obtained thermosetting resin composition is spray-coated on a 50 μm thick PET film whose surface has been subjected to a release treatment, and the solvent is removed by drying to obtain a 20 μm thick sheet-like thermosetting resin composition. Obtained.

(Preparation of sheet-like photosensitive resin composition)
The photosensitive resin composition produced as described above is heated on a PET film having a thickness of 100 μm on which the adhesive is thinly applied to a surface by heating to 130 ° C. using a biaxial extruder, and is extruded from a die. The thickness was laminated to 1.1 mm.
Further, the sheet was sandwiched between cover sheets having a thickness of 50 μm that had been subjected to silicon release treatment to form a sheet-like photosensitive resin composition. This sheet-like photosensitive resin composition was solid at 20 ° C.
The cover sheet is peeled off, the sheet-like thermosetting resin composition having a thickness of 20 μm is laminated on the surface of the sheet-like photosensitive resin composition, and heat-pressed at 150 ° C. using a hot press machine. And the thermosetting resin composition was thermoset to obtain a laminate.
The prepared laminate was placed on a glass flat plate, and irradiated with ultraviolet rays at 4000 mJ / cm ² (integrated light quantity at 350 nm) from both the upper and lower surfaces with a chemical lamp (trademark “10R” manufactured by Philips, The Netherlands). A cured resin was formed.
Separately, a sheet made of a photosensitive resin composition not laminated with a thermosetting resin composition was prepared and photocured using the chemical lamp to obtain a cured resin layer (β). The transmittance of the cured resin layer (β) with respect to light having a wavelength of 1064 nm was 90% or more.
Thereafter, a fine circular concave pattern (recess (ε) is formed on the surface by using a semiconductor laser excitation solid-state laser (trade name “HIPPO 106QW” manufactured by Spectra Physics, USA, wavelength 1064 nm, oscillation frequency: 100 kHz, average output: 17 W). )) Formed.
The depth of the recess (ε) was 20 μm, the opening size was 9 μm, and the arrangement pitch was 20 μm.
Next, a rough pattern (concave portion (ζ)) was formed using a carbon dioxide laser engraving machine (trademark ZED-mini-1000 manufactured by ZED, UK), and a sheet-like laser engraving printing plate was obtained.
The laser engraving printing plate of this sheet was treated in the same manner as in Example 1 by using a precision printing machine (trademark “JSC-m60.60-M” manufactured by JEOL Ltd.) and silver nanopaste (trademark manufactured by Harima Kasei Co., Ltd.). The conductor pattern was printed on the glass substrate using “NPS-J”). The thickness of the conductor pattern after drying was 3 μm.

Example 4
Resin (a): Resin (a) used in the photosensitive resin composition of Example 1 70 parts by weight Organic compound (b): Phenoxyethyl methacrylate (molecular weight 206) 20 parts by weight
Polypropylene glycol monomethacrylate (molecular weight 400) 10 parts by mass Thermal polymerization initiator: t-butyl peroxy-2-ethylhexyl carbonate (trade name “Perbutyl E” manufactured by NOF Corporation) 1 part by weight Stabilizer: 2,6-di- t-Butyl acetophenone 0.5 mass part These materials were mixed at 70 degreeC, and the thermosetting resin composition was prepared.
This thermosetting resin composition is applied to a PET cover film fixed on a metal plate to a thickness of 1.5 mm, and a 50 μm thick PET film is placed thereon, and further, a metal plate is applied thereon. Was placed in an oven adjusted to 150 ° C. and heated for 20 minutes to prepare a cured resin sheet.
The PET cover film was peeled off to expose the cured resin, and the surface was irradiated with a Xe excimer lamp having a wavelength of 172 nm (trade name “Xe excimer lamp” manufactured by M. D. Com.). Using a belt conveyor type exposure machine equipped with the lamp, the distance between the surface of the cured resin and the lamp was set to 2 mm, and light was irradiated in the air.
Thereafter, an ethanol solution containing 5% by mass of γ-methacryloxypropyltriethoxysilane was applied to the light-irradiated surface and dried in an oven at 80 ° C. for 20 minutes.
Thereafter, the thermosetting resin composition containing carbon black produced in Example 1 was spray-coated on a PET film that had been subjected to a release treatment with a thickness of 10 μm, and the solvent component was dried and removed in an oven set at 80 ° C.
A thermosetting resin composition (resin cured product layer (δ)) is laminated on the surface of the sheet-like cured resin product (resin cured product layer (β)) and heated using a heating press set at 150 ° C. Curing was performed to obtain a sheet-form laser engraving printing original plate.
The light transmittance of the cured resin layer (β) was measured by separately preparing the cured resin layer (β) as described below.
That is, a sheet made of only a thermosetting resin composition not laminated with a carbon black-containing thermosetting resin composition was prepared, and was thermally cured by heating in the oven to prepare a resin cured product layer (β). . The transmittance of the cured resin layer (β) with respect to light having a wavelength of 1064 nm was 90% or more.
On the surface of this sheet-shaped laser engraving printing original plate, using a laser drawing apparatus equipped with a fiber laser (trade name “Spark4260” manufactured by Escographics, Germany) in the same manner as in Example 1, an average laser output of 63 W, Laser drawing was performed at an energy of 12 J / cm ² to form a concave portion (ε) having a fine circular pattern.
The depth of the recess (ε) was 20 μm, the opening size was 5.0 μm, and the arrangement pitch was 10 μm.
Furthermore, a rough pattern (concave portion (ζ)) was formed using a carbon dioxide laser engraving machine (trademark ZED-mini-1000 manufactured by ZED, UK) to obtain a cylindrical laser engraving printing plate.
This sheet-shaped laser engraving printing plate is mounted on a flexographic printing machine (trade name “ITM-III” manufactured by Iyo Machinery Co., Ltd.), and water-based ink (trademark “HW571AQP process indigo” manufactured by Toyo Ink Co., Ltd.) is used for coated paper. Was printed.
The thickness of the printed pattern after drying was 2 μm.

Example 5
Resin (a): 70 parts by mass of styrene-butadiene-styrene block copolymer having a number average molecular weight of about 100,000 Organic compound (b): 10 parts by mass of hexamethylene diacrylate (molecular weight 254)
15 parts by mass of liquid polybutadiene having a number average molecular weight of 2000
Alicyclic hydrocarbon plasticizer 10 parts by weight Photopolymerization initiator: 2,2-dimethoxy-2-phenylacetophenone 0.6 part by weight Stabilizer: 2,6-di-t-butylacetophenone 0.5 part by weight The above materials Were mixed at a temperature of 130 ° C. using a kneader to prepare a photosensitive resin composition.
The obtained photosensitive resin composition was extruded at a thickness of 1.7 mm onto a 188 μm-thick PET film on which the adhesive was thinly applied on the surface using a biaxial extruder, and further a silicon release treatment The sheet-like photosensitive resin composition was formed by sandwiching between the cover sheets having a thickness of 15 μm. This sheet-like photosensitive resin composition was solid at 20 ° C. (cured resin layer (β)).
Also, 100 parts by mass of the photosensitive resin composition was mixed with 1 part by mass of copper oxide nanoparticle (trade name “NANOTEK CUO-C” manufactured by C-I Kasei Co., Ltd.) as a near-infrared absorber, and subjected to mold release treatment. A photosensitive resin composition having a thickness of 50 μm was formed into a sheet by extrusion molding on a film (cured resin layer (δ)).
The two types of sheet-shaped photosensitive resin compositions produced as described above were bonded together and welded with a vacuum press machine heated to 150 ° C.
The sheet-shaped photosensitive resin composition (two kinds of bonded sheets) produced as described above was placed on a glass flat plate, and a chemical lamp (trademark “10R”, manufactured by Philips, The Netherlands) from above and below. Ultraviolet rays were irradiated at 4000 mJ / cm ² (integrated light quantity at 350 nm) to prepare a sheet-like cured photosensitive resin.
The light transmittances of the cured resin layer (β) and the cured resin layer (δ) are obtained by separately preparing the cured resin layer (β) and the cured resin layer (δ) as follows. It was measured.
First, the sheet | seat which consists only of the photosensitive resin composition which does not contain the copper oxide nanoparticle was produced, and it photocured using the said chemical lamp, and obtained the resin cured material layer ((beta)). The transmittance of the cured resin layer (β) with respect to light having a wavelength of 1064 nm was 90% or more.
Next, a sheet made of the photosensitive resin composition containing copper oxide nanoparticles was prepared and photocured using the chemical lamp to obtain a cured resin layer (δ). The transmittance of the cured resin layer (δ) with respect to light having a wavelength of 1064 nm was less than 1%.

Thereafter, a fine circular concave pattern (recess (ε) is formed on the surface by using a semiconductor laser excitation solid-state laser (trade name “HIPPO 106QW” manufactured by Spectra Physics, USA, wavelength 1064 nm, oscillation frequency: 100 kHz, average output: 17 W). )) Formed.
The depth of the recess (ε) was 15 μm, the opening size was 5.0 μm, and the arrangement pitch was 10 μm.
Next, a rough pattern (concave portion (ζ)) was formed using a carbon dioxide laser engraving machine (trademark ZED-mini-1000 manufactured by ZED, UK), and a sheet-like laser engraving printing plate was obtained.
A large amount of liquid engraving residue was generated during laser engraving. After engraving, a cleaning process was performed to remove engraving residue remaining on the surface.
In this example, liquid engraving residue was generated because no porous fine particles were contained in the cured resin layer.
Using the laser engraving printing plate obtained as described above, printing was performed on a glass plate with a precision printing machine (trademark “JSC-m60.60-M” manufactured by JEOL Ltd.). At this time, the thickness of the conductor pattern obtained by using silver nanopaste (trademark “NPS-J” manufactured by Harima Chemicals Co., Ltd.) containing aliphatic hydrocarbon as a solvent and removing the solvent by drying was 5 μm. It was.

Example 6
Resin (a): 70 parts by mass of styrene-butadiene-styrene block copolymer having a number average molecular weight of about 100,000 Organic compound (b): 10 parts by mass of hexamethylene diacrylate (molecular weight 254)
15 parts by mass of liquid polybutadiene having a number average molecular weight of 2000
Alicyclic hydrocarbon plasticizer 10 parts by mass Photopolymerization initiator: 2,2-dimethoxy-2-phenylacetophenone 0.6 part by mass Near-infrared absorber: Copper oxide nano-particles (trade name “NANOTEK CUO— C ") 0.1 parts by mass Stabilizer: 2,6-di-t-butylacetophenone 0.5 parts by mass The above materials were mixed at a temperature of 130 ° C using a kneader to prepare a photosensitive resin composition.
The photosensitive resin composition produced as described above was extruded at a thickness of 1.7 mm onto a 188 μm-thick PET film on which the adhesive was thinly applied on the surface, using a biaxial extruder, and The sheet-like photosensitive resin composition was formed by sandwiching it with a cover sheet having a thickness of 15 μm subjected to silicon release treatment.
This photosensitive resin composition was solid at 20 ° C., and the light transmittance at a wavelength of 1064 nm was 15%.

Resin (a): 70 parts by mass of styrene-butadiene-styrene block copolymer having a number average molecular weight of about 100,000 Organic compound (b): 10 parts by mass of hexamethylene diacrylate (molecular weight 254)
15 parts by mass of liquid polybutadiene having a number average molecular weight of 2000
Aliphatic hydrocarbon plasticizer 10 parts by weight Near-infrared absorber: Carbon black (trade name “TB # A700F” manufactured by Tokai Carbon Co., Ltd.) 5 parts by weight The above materials are mixed, and toluene is further added by 50 parts by weight. A resin composition was prepared.
To this resin composition, 1 part by mass of t-butyl peroxy-2-ethylhexyl carbonate (trade name “Perbutyl E” manufactured by NOF Corporation) is added as a thermal polymerization initiator, and a liquid thermosetting resin containing a solvent is added. A resin composition was obtained.
This liquid thermosetting resin composition was spray-coated on a release-treated PET film, and toluene was removed by drying to obtain a sheet-like thermosetting resin composition having a thickness of 15 μm.

Two types of sheet-like resin compositions (sheet-like photosensitive resin composition and sheet-like thermosetting resin composition) obtained as described above are pressure-bonded at 130 ° C. using a vacuum heating press. did.
Next, this sheet-shaped resin composition is placed on a glass flat plate, and irradiated with ultraviolet rays of 4000 mJ / cm ² (integrated light quantity at 350 nm) from above and below by a chemical lamp (trademark “10R” manufactured by Philips, The Netherlands). A cured resin was obtained.

Thereafter, a concave pattern (concave portion (ε)) was formed on the surface of the cured resin (laser engraving printing original plate) using a fiber laser-mounted laser drawing apparatus (trade name “Spark 4260” manufactured by Escographics, Germany). .
The dimensions of the openings were 9.5 μm, the pitch was 20 μm, and the depth was 20 μm.
The bulge of the resin was not observed at the edge portion of the concave pattern, and the formation state was good.
Furthermore, as a result of observing the cross section of the recess with a scanning electron microscope, it was confirmed that the lower layer was not engraved with a fiber laser.
Subsequently, a rough pattern (concave portion (ζ)) was formed using a carbon dioxide laser engraving machine (trademark ZED-mini-1000 manufactured by ZED, UK), but no resin swell at the edge portion was observed.
This sheet-shaped laser engraving printing plate is mounted on a flexographic printing machine (trade name “ITM-III” manufactured by Iyo Machinery Co., Ltd.), and water-based ink (trademark “HW571AQP process indigo” manufactured by Toyo Ink Co., Ltd.) is used for coated paper. Was printed.
The thickness of the printed pattern after drying was 2 μm.

[Comparative Example 1]
Instead of the thermosetting resin composition produced in Example 1, the following resin composition was used.
(Preparation of resin composition)
Resin (a): 70 parts by mass of a styrene-butadiene-styrene block copolymer having a number average molecular weight of about 100,000 Organic compound (b): 10 parts by mass of phenoxyethyl methacrylate (molecular weight 190)
Polypyrene glycol monomethacrylate (molecular weight 400) 10 parts by mass Near infrared absorber: Carbon black (trade name “TB # A700F” manufactured by Tokai Carbon Co., Ltd.) The resin composition was prepared by adjusting the viscosity using.

A sheet-shaped laser engraving printing original plate was produced in the same manner as in Example 1 except that this resin composition was used.
Using a laser drawing apparatus equipped with a fiber laser (trade name “Spark 4260” manufactured by Escographics, Germany), laser drawing is performed with a laser average output of 63 W and energy of 12 J / cm ² , and a concave portion (ε) of a fine circular pattern is formed. Formed.
The recess (ε) had a depth of 20 μm, an opening size of 5.0 μm, and an array pitch of 10 μm.
The concave pattern was melted by heat, and the swell of the resin was observed at the edge portion, and the precision of the fine pattern was practically inferior.
Using a carbon dioxide laser engraving machine (trademark ZED-mini-1000 manufactured by ZED, UK), the rough concave portions are controlled by controlling the energy so that the depth at the dot portion is 100 μm and the depth at the square pattern portion is 400 μm. Formation was performed.
Swelling of the resin was observed at the edge of the surface, and the pattern accuracy was practically inferior.
Printing was carried out in the same manner as in Example 1, but the ink was transferred only to the pattern edge portion, and the printed matter was embedded inside.
Printing was performed on a glass plate using a precision printing machine (trademark “JSC-m60.60-M” manufactured by JEOL Ltd.). A silver nanopaste (trademark “NPS-J” manufactured by Harima Kasei Co., Ltd.) containing an aliphatic hydrocarbon as a solvent was used.
The durability of the printing plate was also poor and the surface layer was observed to fall off.
In Comparative Example 1, a thermoplastic resin was used instead of the curable resin composition as described above. In other words, when it is easily deformed by heat and a laser (near infrared ray and infrared ray) is used, the edge portion in the pattern portion is deformed and raised due to the influence of thermal processing.

[Comparative Example 2]
Instead of the thermosetting resin composition produced in Example 1, the following thermosetting resin composition was used.
(Preparation of thermosetting resin composition)
A thermosetting resin composition was prepared by removing carbon black from the thermosetting resin composition of Example 1.
Resin (a): Resin prepared as described above 70 parts by weight Organic compound (b): Phenoxyethyl methacrylate (molecular weight 190) 10 parts by weight
Polypropylene glycol monomethacrylate (molecular weight 400) 10 parts by mass Thermal polymerization initiator: t-butyl peroxy-2-ethylhexyl carbonate (trade name “Perbutyl E” manufactured by NOF Corporation) Stabilizer: 2,6-di- t-Butyl acetophenone 0.5 mass part These materials were mixed, the viscosity was adjusted using tetrahydrofuran as a solvent, and the thermosetting resin composition was prepared.

A sheet-shaped laser engraving printing original plate was produced in the same manner as in Example 1 except that this thermosetting resin composition was used.
Using a laser drawing apparatus equipped with a fiber laser (trade name “Spark 4260” manufactured by Escographics, Germany), a pattern was formed on the surface of the laser engraving printing original plate with a laser average output of 63 W and an energy of 12 J / cm ² . A recess could not be formed.
In Comparative Example 2, carbon black was not added, so the near infrared laser could not be absorbed and engraving could not be performed.

[Comparative Example 3]
Styrene-butadiene-styrene block copolymer having a number average molecular weight of about 100,000 70 parts by mass Organic compound (b): Hexamethylene diacrylate (molecular weight 254) 10 parts by mass
15 parts by mass of liquid polybutadiene having a number average molecular weight of 2000
Aliphatic hydrocarbon plasticizer 10 parts by mass Near-infrared absorber: Carbon black (trade name “TB # A700F” manufactured by Tokai Carbon Co., Ltd.) 5 parts by mass, and further 50 parts by mass of toluene are added to form a liquid resin. A composition was prepared.
To this, 1 part by mass of t-butyl peroxy-2-ethylhexyl carbonate (trade name “Perbutyl E” manufactured by NOF Corporation) was added as a thermal polymerization initiator, and a liquid thermosetting resin composition containing a solvent was obtained. It was.

This liquid thermosetting resin composition was spray-coated on a PET film that had been subjected to an easy adhesion treatment and was further laminated with an adhesive layer. Thereafter, the process of drying and removing toluene was repeated 10 times to obtain a sheet-like thermosetting resin composition having a thickness of 500 μm.
Furthermore, a PET cover film that had been subjected to a release treatment was laminated thereon, and was cured by heating at 130 ° C. using a heating press machine to prepare a sheet-shaped laser engraving printing original plate.

This laser engraving printing original plate was subjected to laser drawing with a laser drawing apparatus equipped with a fiber laser (trade name “Spark 4260” manufactured by Escographics, Germany) with an average laser output of 63 W and an energy of 12 J / cm ^2. A concave pattern was formed in the same manner as in FIG. Although the opening size was 9.5 μm and the pitch was 15 μm, the variation was as large as 25 to 35 μm in depth, and the variation in depth could not be reduced.
Comparative Example 3 has a single layer structure containing carbon black. In this case, although a concave pattern can be formed using a near-infrared laser, the laser beam becomes unstable and the depth cannot be precisely controlled. That is, since there is a variation in the depth of the minute concave portions present on the surface of the convex pattern, the ink amount is affected, which causes uneven color.

  The manufacturing method of the present invention is a laser engraving that performs pattern formation of electronic elements, optical elements, specifically, organic electroluminescent elements, organic solar cells, organic semiconductors, antenna circuits, liquid crystal display elements, plasma light emitting elements, etc. by printing. It has industrial applicability as a printing plate manufacturing technology.

Claims (23)

A method for producing a laser engraving printing original plate,
(1) forming a curable resin composition layer (α) on a sheet-like or cylindrical support;
(2) The cured curable resin composition layer (α) is cured, and the cured resin layer (β) has a transmittance of 10% to 100% for near-infrared laser light in a wavelength region of 700 nm to 1.6 μm. Forming a step;
(3) forming a curable resin composition layer (γ) that absorbs near infrared rays on the resin cured product layer (β);
(4) A method for producing a laser engraving printing original plate, comprising: curing the curable resin composition layer (γ) to form a cured resin layer (δ). After the step (2) and before the step (3),
(5) The method for producing a laser engraving printing original plate according to claim 1, further comprising a step of irradiating the surface of the cured resin layer (β) with an electron beam or light having a wavelength of 100 nm to 200 nm. After the step (2) and before the step (3),
(6) having a step of adjusting the thickness and surface roughness of the cured resin layer (β),
After the step (4),
(7) The method for producing a laser engraving printing original plate according to claim 1 or 2, further comprising a step of adjusting a thickness and a surface roughness of the cured resin layer (δ).   In the step (6) and the step (7), the method of adjusting the thickness and surface roughness of the cured resin layer is at least one method selected from the group consisting of cutting, grinding, and polishing. Item 4. A method for producing a laser engraving printing original plate according to Item 3. The resin cured product layer (β) has a thickness of 0.1 mm to 10 mm,
5. The method for producing a laser engraving printing original plate according to claim 1, wherein the cured resin layer (δ) has a thickness of 0.5 μm or more and less than 100 μm. The support is a hollow cylindrical support;
The method for producing a laser engraving printing original plate according to any one of claims 1 to 5, wherein the hollow cylindrical support has a thickness of 0.1 mm to 2 mm.   The method for producing an original plate for laser engraving printing according to claim 6, wherein the hollow cylindrical support is a metal sleeve or a fiber reinforced plastic sleeve.   The fiber-reinforced plastic sleeve contains at least one type of fiber selected from the group consisting of polyester fiber, polyamide fiber, polyimide fiber, polyurethane fiber, cellulose fiber, glass fiber, carbon fiber, metal fiber, and ceramic fiber. The manufacturing method of the laser-engraving printing original plate of Claim 7.   The method for producing a laser engraving printing original plate according to any one of claims 2 to 8, wherein in the step (5), the acceleration voltage of the electron beam is set to 50 keV or more and 300 keV or less.   The method for producing a laser engraving printing original plate according to any one of claims 2 to 9, wherein in the step (5), the electron beam is irradiated in an inert gas atmosphere.   The said process (5) WHEREIN: The light of wavelength 100nm or more and 200nm or less is irradiated in air | atmosphere atmosphere, and the distance of resin hardened | cured material layer ((beta)) and a light source shall be 0.1 mm or more and 5 mm or less. The manufacturing method of the laser engraving printing original plate as described in any one of Claims.   The method for producing a laser engraving printing original plate according to any one of claims 1 to 11, wherein the curable resin composition layer (γ) contains a near-infrared laser-absorbing dye or pigment.   The method for producing a laser engraving printing original plate according to any one of claims 1 to 12, further comprising a step of forming a cushion layer between the support and the cured resin layer (β).   14. The laser engraving printing original plate according to claim 13, wherein the cushion layer contains a thermosetting resin and / or a photocurable resin, and is formed by a step of curing the thermosetting resin and / or the photocurable resin. Method. A method for producing a laser engraving printing plate using the laser engraving printing original plate produced by the method according to claim 1,
(8) A step of irradiating the surface of the cured resin layer (δ) with a near-infrared laser having a beam diameter of 1 μm or more and less than 10 μm to form a recess (ε);
(9) A step of irradiating a laser beam (η) having a beam diameter of 10 μm or more and 100 μm or less on the surface of the printing original plate on which the recesses (ε) are formed, thereby forming recesses (ζ);
A method for producing a laser engraving printing plate having:   The method for producing a laser engraving printing plate according to claim 15, wherein the depth of the recess (ε) is 0.5 μm or more and less than 20 μm, and the depth of the recess (ζ) is 20 μm or more and 1 mm or less.   The method for producing a laser engraving printing plate according to claim 15 or 16, wherein a surface opening size of the recess (ε) is 1 µm or more and less than 10 µm.   The method for producing a laser engraving printing plate according to any one of claims 15 to 17, wherein the recesses (ε) are formed in a regular arrangement, and the arrangement pitch is 2 μm or more and less than 20 μm.   The near-infrared laser is a pulsed laser, the oscillation frequency is 1 kHz or more and 500 MHz or less, and the half time width of the pulse time is 10 femtoseconds or more and 50 nanoseconds or less. Method of laser engraving printing plate.   The method for producing a laser engraving printing plate according to claim 15, wherein the cured resin layer (β) contains at least one photocured product of a photosensitive resin composition. Using the laser engraving printing plate produced by the method for producing a laser engraving printing plate according to any one of claims 15 to 20,
An element manufacturing method for performing pattern printing using at least one selected from the group consisting of a conductor, a semiconductor, an insulator, and an optical material.   The method for producing an element according to claim 21, wherein the element is any one selected from the group consisting of an organic electroluminescent element, an organic solar cell, an organic semiconductor, an antenna circuit, a liquid crystal display element, and a plasma light emitting element.   The method of manufacturing an element according to claim 21, wherein the element is a microlens array or an optical waveguide.