JP2006069120A - Manufacturing method for electronic circuit or optical member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for an electronic circuit or an optical member, which has a high-definition pattern with a uniform film thickness. <P>SOLUTION: This manufacturing method for the electronic circuit or the optical member, which has the high-definition pattern with the uniform film thickness, is characterized by comprising: a step of forming a photosensitive resin composition layer on a sheet-like or cylindrical substrate; a step of curing the formed photosensitive resin composition layer by irradiating it with light; a step of forming the pattern by using laser light; and a printing step of transferring ink, containing at least one kind selected from among an insulator, a semiconductor and a conductor, onto a base material to be printed, by using an obtained printing plate. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for manufacturing an electronic circuit or an optical member, and further, a conductor, semiconductor, insulator, pattern formation, optical component antireflection film, color filter, and (near) infrared cut filter for an electronic circuit or optical member. For pattern formation of functional materials such as liquid crystal displays or organic electroluminescence displays, etc. For the formation of coating films and patterns for alignment films, underlayers, light emitting layers, electron transport layers, sealing material layers, etc. It relates to a suitable laser engraving printing plate.

As a technique for forming a pattern with high accuracy in an insulating film of a semiconductor element, a liquid crystal display panel, etc., a method of combining material application by spin coating and photolithography is generally used, but pattern formation is to be performed in a large area. Then, there is a problem that the cost becomes high in photolithography. On the other hand, as a pattern formation technique, a method of forming a pattern with a large area with high accuracy by using printing techniques such as a screen printing method, an offset printing method, a flexographic printing method, and a gravure printing method is considered. The printing method is suitable for forming a large number of patterns on a substrate, and is advantageous over photolithography in terms of reduction in the amount of material used and cost.
In recent years, ink jet printing methods have been applied to this field and are being developed.

However, current problems include clogging of inkjet nozzles, fine patterning, printing speed, and the like.
From the viewpoint of printing speed, printing methods such as a flexographic printing method, an offset printing method, a gravure printing method, and a screen printing method are applied and studied. Among them, flexographic printing is a method that uses a resin relief plate, and the ink is transferred to the surface of the convex part, and the convex part comes into contact with the surface of the printing material, so that the printing part is not stained. It is the method which has.

  The flexographic printing method is used for packaging materials such as cardboard, paper containers, paper bags, and flexible packaging films, wallpaper materials, building materials such as decorative boards, and label printing. Photosensitive resins are often used for the production of printing plates used in flexographic printing, and a negative film is formed on the photosensitive resin using a liquid resin or a solid resin plate formed into a sheet. A method using photolithography in which light is irradiated through a negative film to cause a crosslinking reaction and then a non-crosslinked portion is washed away with a developer has been used. In recent years, a thin light-absorbing layer called a black layer has been provided on the surface of a photosensitive resin, and this is irradiated with laser light to form a mask image directly on the photosensitive resin plate, and then light is irradiated through the mask to cause a crosslinking reaction. Later, a technique called so-called flexo CTP was developed in which the non-crosslinked portion of the non-irradiated portion of the light was washed away with a developer, and a higher definition pattern could be formed.

However, this technique is also a method using photolithography in which a pattern is formed through exposure and development processes. In the photosensitive resin plate that forms a pattern using photolithography, the thickness of the central portion of the photocured pattern is reduced due to curing shrinkage in the exposure process and extraction of uncured components into the developer in the development process. There are problems of unevenness in the thickness of the plate due to the cupping and warping of the plate where the outer periphery of the plate is warped. When a printing plate with low thickness accuracy is used, the film thickness of the pattern obtained by printing becomes non-uniform, and the performance of the obtained electronic component or optical member also becomes non-uniform.
Therefore, in the system using the photosensitive resin plate, it has been a big problem to ensure the thickness accuracy of the obtained printing plate.

  As a specific example of application of the photosensitive resin plate to printing of an optical member, an alignment film made of a polyimide resin is printed on the surface of a glass substrate using a photosensitive resin relief plate. In the photosensitive resin relief printing plate, a negative film, a cover film, a liquid photosensitive resin, and a base film are sandwiched between two glass plates, an irradiation crosslinking reaction is caused by light through the negative film, and then a non-crosslinked portion is washed away with a developer. The method has been used. The photosensitive resin relief printing plate produced by such a method has a cupping phenomenon due to photocuring shrinkage in photolithography in which the thickness of the convex portion is not sufficiently uniform and the peripheral portion of the convex portion is thicker than the central portion. is doing.

  In Japanese Patent No. 3496086, a pressure-sensitive adhesive layer having a substantially uniform thickness is provided on the back surface (back surface of the base film layer) of a laminate composed of a photosensitive resin relief printing body and a base film layer. , A method of reducing the cupping phenomenon of the photosensitive resin relief plate body by bonding and laminating and laminating a flat metal plate or synthetic resin plate is described, but the process is complicated, There is a problem that air bubbles are involved and the thickness accuracy of the printing plate is lowered. Further, this patent document does not describe any laser engraving printing plate.

  In addition, the solvent component in the ink used to form conductors, semiconductors, and insulators of electronic circuits and optical members causes the printing plate to swell, the constituents in the printing plate are extracted, and the physical properties greatly change. Therefore, ensuring solvent resistance was a major issue. In the photosensitive resin plate using photolithography, the function of forming a fine pattern is particularly important. Therefore, it is an important requirement that the dissolution or dispersion characteristics of the uncured resin in the developer used in the development process be good, and there are limitations on materials that can be selected in the design of the photosensitive resin composition. Therefore, it cannot be said that the solvent resistance characteristics with respect to various solvent components in the ink are sufficient.

Forming a printing plate using a laser engraving method that eliminates the phenomenon of cupping, which is a problem with photosensitive resin plates, by irradiating the resin plate with laser light and melting or decomposing the irradiated resin. A method has been proposed. Application of natural rubber, synthetic rubber, plastic, and the like as a material for forming a laser engraving printing plate has been attempted.
For example, US Pat. No. 3,549,733 discloses the use of polyoxymethylene or polychloral. Japanese Patent Publication No. 10-512823 (German Patent No. A19625749) describes the use of a silicone polymer or a silicone fluoropolymer. In the case of silicone rubber, the solvent tends to swell, and the usable solvent is limited.

  On the other hand, Japanese Patent Nos. 2846954 and 2846955 (U.S. Pat. Nos. 5,798,202 and 5,804,353) use mechanically, photochemically, and thermochemically reinforced materials such as SBS, SIS, and SEBS. It is disclosed. When thermoplastic elastomer is used, engraving with a laser having an oscillation wavelength in the infrared region melts even the resin where the laser beam diameter deviates greatly due to heat, thus forming a high-resolution engraving pattern Difficult to do. In addition, the edge portion rises due to melting in the relief, the fine powder residue is fused to the edge portion, the edge portion becomes unclear, and the halftone dot shape is broken.

None of the laser engraving printing plate patents mentions examples of application to electronic circuit or optical member manufacturing, and is important for these applications. There is no mention of how to make it happen.
Japanese Patent No. 3496086 US Pat. No. 3,549,733 Japanese National Patent Publication No. 10-512823 Japanese Patent No. 2846954 Japanese Patent No. 2846955

  An object of this invention is to provide the manufacturing method of an electronic circuit or an optical member which has a high-definition and uniform film thickness pattern.

  The present inventors have intensively studied, and by using a laser engraving printing plate that is free from cupping phenomenon due to curing shrinkage at the time of exposure and has high plate thickness accuracy and high solvent resistance, an electronic circuit having a high-definition and uniform film thickness pattern Or it discovered that manufacture of an optical member was possible and came to complete this invention.

The present invention is as follows.
1. (A) A step of irradiating a photosensitive resin composition layer formed into a sheet shape or a cylindrical shape to form a cured photosensitive resin layer to form a printing original plate, (b) applying a laser beam to the formed printing original plate Irradiation to produce a flexographic printing plate with a convex pattern on the surface or a gravure printing plate with a concave pattern, or a screen printing plate with a hole pattern penetrating a cured photosensitive resin layer (C) using at least one kind of printing plate selected from the obtained flexographic printing plate, gravure printing plate and screen printing plate, and containing at least one kind selected from an insulator, a semiconductor and a conductor A printing process in which the ink to be transferred is transferred onto the substrate to be printed, (d) the liquid medium in the formed ink is removed by drying, or the ink is irradiated with light to be cured and fixed; m, and including a step of forming a thin film of 10 μm or less, the plate thickness accuracy of the printing original plate is 30 μm or less, and when the resistance to the liquid medium in the ink used in the printing step is evaluated by an immersion swelling test, A method of manufacturing an electronic circuit or an optical member, characterized in that a weight change rate (hereinafter referred to as swelling rate) before and after immersion in a liquid medium is 10 wt% or less.

2. The liquid medium in the ink is at least one solvent component selected from an ester solvent, an ether solvent, a hydrocarbon solvent, a halogen solvent, and a nitrogen-containing hydrocarbon solvent. 1. It is characterized by containing. The manufacturing method of the electronic circuit or optical member as described in any one of.
3. 1. As a printing plate for forming a thin film containing at least one selected from an insulator, a semiconductor, and a conductor using a flexographic printing method, When the convex pattern described in (1) has an outermost surface dimension of 200 μm square and a height of 500 μm, the height difference between the central part and the edge part of the convex pattern is 30 μm or less, and the laser for printing an electronic circuit or optical member Engraving printing plate.
4). 2. A cushion layer having a Shore A hardness of 10 to 70 degrees is provided between the cylindrical support or sheet-like support and the printing plate. A laser engraving printing plate for printing an electronic circuit or an optical member according to 1.

5. 2. The cured photosensitive resin layer contains at least one kind of fine particles selected from inorganic fine particles and inorganic / organic composite fine particles. 4. A laser engraving printing plate for printing an electronic circuit or an optical member according to any one of the above.
6). The step of applying a liquid photosensitive resin composition on a cylindrical support at 20 ° C., the step of photocuring the applied liquid photosensitive resin composition to form a photosensitive resin cured product layer, and the resulting photosensitivity Surface adjustment process of smoothing the surface of the cured resin layer while rotating, further irradiating the photosensitive resin cured layer with laser light, and removing the resin at the portion irradiated with the laser light to form a pattern The manufacturing method of the laser engraving printing plate for electronic circuits or optical member printing characterized by including the process performed.
7). Before the step of applying the liquid photosensitive resin composition, the method includes a step of winding and fixing a sheet-like support on a cylindrical support, and applying the liquid photosensitive resin composition on the sheet-like support And a step of cutting the printing original plate and removing it from the cylindrical support after the surface adjustment step. 2. A method for producing a laser engraving printing plate for printing an electronic circuit or an optical member according to 1.

  According to the present invention, it is possible to provide a method of manufacturing an electronic circuit or an optical member having a high-definition and uniform film thickness pattern.

Hereinafter, preferred embodiments of the present invention will be described in more detail.
In a method of manufacturing an electronic circuit or an optical member, a pattern formed using a laser engraving method is used as a method of transferring a thin film containing at least one selected from an insulator, a semiconductor, and a conductor onto a substrate to be printed. A flexographic printing method, a screen printing method, and a gravure printing method, which are carried out using a printing plate having the same, are preferable. In particular, the flexographic printing method is particularly preferable because the printing pressure on the substrate to be printed is low and only the convex portion having ink on the surface contacts the substrate to be printed. The printing plate forms a photosensitive resin cured product layer by irradiating light to the photosensitive resin composition layer formed into a sheet shape or a cylindrical shape, and rotates the surface of the obtained photosensitive resin cured product layer. However, after forming a printing original plate by smoothing, a resin is removed by melting or decomposing the irradiated resin by irradiating a laser beam, and a pattern is preferably formed.

An electronic circuit refers to an electronic circuit formed by patterning a thin film containing at least one selected from an insulator, a semiconductor, and a conductor. Although not particularly limited, specifically, a conductor pattern for forming a coil, antenna, electrode, wiring, etc., a dielectric such as a capacitor, an interlayer insulating film, an insulating pattern for forming an alignment film for a liquid crystal display, etc. And organic semiconductor patterns for forming a light emitting layer, a charge transfer layer, a charge injection layer, and the like of a transistor, a diode, and an organic electroluminescence element. Examples of the optical member include thin film optical components such as an antireflection film, a filter film, a polarizing film, and a light guide plate.
The printing original plate comprises a photosensitive resin cured product layer obtained by photocuring a photosensitive resin composition.

The depth of the pattern formed on the printing original plate surface by laser engraving varies depending on the printing method, but is preferably 1 μm or more and 1000 μm or less. More preferably, they are 5 micrometers or more and 700 micrometers or less, More preferably, they are 20 micrometers or more and 500 micrometers or less. If it is 1 μm or more, the ink can be held, and if it is 1000 μm or less, the pattern is not deformed or destroyed during the printing process.
The plate thickness accuracy of the printing original plate is 30 μm or less. Preferably it is 20 micrometers or less, More preferably, it is 10 micrometers or less. If it is 30 μm or less, printing with high accuracy and low printing pressure is possible. In the plate thickness accuracy, 30 μm means ± 15 μm with respect to the average value of thickness measurement. Thickness measurement shall be carried out in the XY direction at intervals of 3 cm.

  The thickness of the print pattern that can be printed on the substrate to be printed in the printing method is 1 nm or more and 10 μm or less after the solvent component in the ink is removed by drying. Preferably they are 5 nm or more and 5 micrometers or less, More preferably, they are 10 nm or more and 1 micrometers or less. If the film thickness is 1 nm or more, the functions of an insulator, a semiconductor, and a conductor can be expressed, and if it is 10 μm or less, the solvent component in the ink can be easily removed. The photosensitive resin composition includes a prepolymer (A) having a number average molecular weight of 1,000 or more and 500,000 or less, a reactive monomer (B) having a polymerizable reactive group having a number average molecular weight of less than 1,000, a photopolymerization initiator (C), And a filler (D).

The photosensitive resin composition may be liquid or solid at 20 ° C., but is preferably liquid at 20 ° C. for ease of moldability.
The prepolymer (A) may be liquid or solid at 20 ° C., but is preferably a liquid resin at 20 ° C. from the viewpoint of moldability. The liquid resin here means a polymer that has the property of being easily deformed by flow and solidified into a deformed shape by cooling. When an external force is applied, the liquid resin is instantly deformed according to the external force. However, when external force is removed, the term is compared with an elastomer having a property of restoring the original shape in a short time. When the prepolymer (A) is a liquid resin at 20 ° C., the photosensitive resin composition also becomes a liquid at 20 ° C., and when the printing original plate obtained therefrom is molded into a sheet or cylinder, a good plate Thickness accuracy and dimensional accuracy can be obtained. When the liquid photosensitive resin is used, the viscosity of the photosensitive resin composition is preferably 10 Pa · s or more and 10 kPa · s or less at 20 ° C. More preferably, it is 50 Pa · s or more and 5 kPa · s or less. If the viscosity is 10 Pa · s or more, the mechanical strength of the produced printing original plate is sufficient, and the shape can be easily maintained and processed even when it is formed into a cylindrical printing original plate. If the viscosity is 10 kPa · s or less, it is easy to be deformed and processed easily without increasing the temperature. It is easy to form into a sheet or cylindrical printing original, and the process is simple. In particular, in order to obtain a cylindrical printing original plate with high plate thickness accuracy, it is preferable to form a liquid photosensitive resin layer on a cylindrical support, and the photosensitive resin composition causes a phenomenon such as liquid dripping due to gravity. The viscosity is preferably 100 Pa · s or more, more preferably 200 Pa · s or more, and still more preferably 500 Pa · s or more.

  The number average molecular weight of the prepolymer (A) is preferably from 1,000 to 500,000, more preferably from 5,000 to 200,000, and even more preferably from 10,000 to 100,000. If the number average molecular weight of the prepolymer (A) is 1000 or more, the printing original plate produced by crosslinking later maintains strength, and the relief image formed from this printing original plate is strong. Can withstand use. Moreover, if it is 500,000 or less, the viscosity of the photosensitive resin composition will not increase excessively, and a complicated processing method such as heat extrusion is not necessary when producing a sheet-like or cylindrical printing original plate. . The number average molecular weight referred to here is a value measured by gel permeation chromatography, calibrated with polystyrene having a known molecular weight, and converted.

  When the printing original plate is irradiated with laser light, it is preferable that the printing original plate is easily liquefied or easily decomposed. Therefore, it is desirable that the prepolymer (A) or the reactive monomer (B) that is a raw material of the cured photosensitive resin has a component that is easily decomposed. The components that are easily decomposed include styrene, α-methylstyrene, α-methoxystyrene, acrylic esters, methacrylic esters, ester compounds, ether compounds, nitro compounds, carbonates as monomer units that are easily decomposed into the molecular chain. Preferably, compounds, carbamoyl compounds, hemiacetal ester compounds, oxyethylene compounds, aliphatic cyclic compounds, and the like are included. Especially polyethers such as polyethylene glycol, polypropylene glycol, polytetraethylene glycol, aliphatic polycarbonates, aliphatic carbamates, polymethyl methacrylate, polystyrene, nitrocellulose, polyoxyethylene, polynorbornene, polycyclohexadiene hydrogenated product Alternatively, a polymer having a molecular structure such as a dendrimer having many branched structures is a representative example of those that are easily decomposed.

  A polymer containing a large number of oxygen atoms in the molecular chain is preferred from the viewpoint of degradability. Among these, a compound having a carbonate group, a carbamate group, and a methacryl group in the polymer main chain is preferable because of its high thermal decomposability. For example, polyesters and polyurethanes synthesized from (poly) carbonate diol and (poly) carbonate dicarboxylic acid as raw materials, polyamides synthesized from (poly) carbonate diamine as raw materials, and the like can be cited as examples of polymers having good thermal decomposability. . These polymer main chains and side chains may contain a polymerizable unsaturated group. In particular, when a reactive functional group such as a hydroxyl group, an amino group, or a carboxyl group is present at the terminal, it is easy to introduce a polymerizable unsaturated group at the terminal of the main chain.

  The prepolymer (A) may have a polymerizable unsaturated group in the molecule. Preferred examples include polymers having an average of 0.7 or more per molecule, and more preferred polymers having one or more polymerizable unsaturated groups. If the average is 0.7 or more per molecule, the printing original plate obtained from the photosensitive resin composition is excellent in mechanical strength, and the relief image is not easily broken during laser engraving. Furthermore, its durability is good and it can withstand repeated use, which is preferable. The upper limit of the number of polymerizable unsaturated groups per molecule is not particularly limited, but is preferably 20 or less. More preferably, it is 10 or less. The abundance ratio of the polymerizable unsaturated group in the prepolymer (A) can be quantified using a high-resolution nuclear magnetic resonance spectrum method (NMR method). The term “intramolecular” as used herein includes the case where a polymerizable unsaturated group is directly attached to the terminal of the polymer main chain, the terminal of the polymer side chain, the polymer main chain, or the side chain. The polymerizable unsaturated group of the present invention is defined as a polymerizable unsaturated group involved in a radical or addition polymerization reaction.

  Preferable examples of the polymerizable unsaturated group involved in the radical polymerization reaction include a vinyl group, an acetylene group, an acrylic group, and a methacryl group. Preferred examples of the polymerizable unsaturated group involved in the addition polymerization reaction include cinnamoyl group, thiol group, azide group, epoxy group that undergoes ring-opening addition reaction, oxetane group, cyclic ester group, dioxirane group, spiroorthocarbonate group, spiro An ortho ester group, a bicyclo ortho ester group, a cyclic imino ether group and the like can be mentioned.

  As a method for introducing a polymerizable unsaturated group into the prepolymer (A) molecule, for example, a method in which a polymerizable unsaturated group is directly introduced into the molecular end may be used. Alternatively, a hydroxyl group, Compounds having a plurality of reactive groups such as amino groups, epoxy groups, carboxyl groups, acid anhydride groups, ketone groups, hydrazine residues, isocyanate groups, isothiocyanate groups, cyclic carbonate groups, ester groups, and their reactive groups It is obtained by reacting with a binder having a plurality of reactive groups capable of binding to (for example, polyisocyanate in the case of a hydroxyl group or an amino group), adjusting the molecular weight, and converting to a terminal binding group. Of introducing a polymerizable unsaturated group into a terminal by reacting the obtained compound with an organic compound having a reactive group capable of reacting with the terminal binding group and a polymerizable unsaturated group Etc. can be suitably raised.

  In particular, when a flexible relief image is required as in flexographic printing plate applications, a part of the prepolymer (A) is a liquid resin having a glass transition temperature of 20 ° C. or lower, more preferably a glass transition temperature of 0 ° C. or lower. It is preferable to use a liquid resin. Examples of such liquid resins 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 include ethers, aliphatic polycarbonates, silicones such as polydimethylsiloxane, polymers of (meth) acrylic acid and / or derivatives thereof, and mixtures and copolymers thereof. The content is preferably 30 wt% or more and 100 wt% or less with respect to the entire prepolymer (A). In particular, unsaturated polyurethanes having a polycarbonate structure are preferred from the viewpoint of weather resistance.

  The reactive monomer (B) preferably has a number average molecular weight of 1000 or less in consideration of easiness of dilution with the prepolymer (A), and is preferably a compound having a polymerizable unsaturated group in the molecule. The polymerizable unsaturated group is a functional group that contributes to radical polymerization reaction and addition polymerization reaction. Preferable examples of the polymerizable unsaturated group involved in the radical polymerization reaction include a vinyl group, an acetylene group, an acrylic group, and a methacryl group. Preferred examples of the polymerizable unsaturated group involved in the addition polymerization reaction include cinnamoyl group, thiol group, azide group, epoxy group that undergoes ring-opening addition reaction, oxetane group, cyclic ester group, dioxirane group, spiroorthocarbonate group, spiro An ortho ester group, a bicyclo ortho ester group, a cyclic imino ether group and the like can be mentioned. Examples of the reactive monomer (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 derivatives thereof, allyl compounds such as allyl alcohol and allyl isocyanate, unsaturated dicarboxylic acids such as maleic anhydride, maleic acid and fumaric acid and derivatives thereof, vinyl acetates, N-vinylpyrrolidone, N-vinylcarbazole, cyanate esters However, (meth) acrylic acid and its derivatives are preferable examples from the viewpoints of the abundance of the types and the price.

The derivatives include alicyclics such as cycloalkyl-, bicycloalkyl-, cycloalkene-, bicycloalkene-, aromatics such as benzyl-, phenyl-, phenoxy-, alkyl-, halogenated alkyl-, alkoxyalkyl-, Esters of polyhydric alcohols such as hydroxyalkyl-, aminoalkyl-, tetrahydrofurfuryl-, allyl-, glycidyl-, alkylene glycol-, polyoxyalkylene glycol-, (alkyl / allyloxy) polyalkylene glycol- and trimethylolpropane Can be given.
In the present invention, one or two or more reactive monomers (B) having a polymerizable unsaturated bond can be selected according to the purpose. For example, when used as a printing plate, organic compounds used to suppress swelling of organic solvents such as ester solvents, ether solvents, hydrocarbon solvents, halogen solvents, and nitrogen-containing hydrocarbon solvents that are solvents for solvent-based inks It is preferable to have at least one kind of derivative such as long chain aliphatic, alicyclic or aromatic.

  A method for measuring the number average molecular weight (Mn) of the reactive monomer (B) will be described. It dissolves in the solvent in which the reactive monomer (B) dissolves, analyzes by gel permeation chromatography (GPC method), and calculates Mn in terms of standard polystyrene with a known molecular weight. This method is used for compounds having a wide molecular weight distribution. As a measure for the molecular weight distribution, the ratio of Mn to the weight average molecular weight (Mw) calculated simultaneously with Mn, that is, polydispersity (Mw / Mn) is used. When the polydispersity is 1.1 or more, the number average molecular weight determined by the GPC method is adopted on the assumption that the molecular weight distribution is wide. In addition, those having a polydispersity of less than 1.1 have a very narrow molecular weight distribution, so that molecular structure analysis is possible, and the molecular weight calculated using nuclear magnetic resonance spectroscopy (NMR method) or mass spectrometry is the number average. The molecular weight.

In order to increase the mechanical strength of the printing original plate, the reactive monomer (B) preferably has at least one alicyclic or aromatic derivative. In this case, the total amount of the reactive monomer (B) It is preferably 20 wt% or more and 100 wt% or less, more preferably 50 wt% or more and 100 wt% or less.
In order to increase the rebound resilience of the printing original plate, for example, a methacrylic monomer as described in JP-A-7-239548 can be used, or it can be selected by utilizing technical knowledge of a known printing photosensitive resin.

  When the photosensitive resin composition layer is crosslinked by irradiation with light, that is, ultraviolet rays or visible rays, or an electron beam, to express physical properties as a printing original plate, but in this case, when photocured using ultraviolet rays or visible rays Can be added with a photopolymerization initiator. The photopolymerization initiator can be selected from those commonly used. For example, radical polymerization, cation polymerization, anion polymerization and the like exemplified in “Polymer Data Handbook-Fundamentals” edited by the Society of Polymer Science, published in 1986 by Fufukan. A photopolymerization initiator can be used. As a photopolymerization initiator for inducing a radical polymerization reaction, a hydrogen abstraction type photopolymerization initiator and a decay type photopolymerization initiator are used as particularly effective photopolymerization initiators.

  Although it does not specifically limit as a hydrogen abstraction type photoinitiator, It is preferable to use an aromatic ketone. Aromatic ketones efficiently become excited triplet states by photoexcitation, and this excited triplet state has been proposed a chemical reaction mechanism that draws hydrogen from the surrounding medium to generate radicals, and the generated radicals undergo photocrosslinking reactions. It is considered to be involved. As the hydrogen abstraction type photopolymerization initiator used in the present invention, any compound may be used as long as it is a compound capable of generating hydrogen by extracting hydrogen from the surrounding medium through an excited triplet state. Examples of aromatic ketones include benzophenones, miherer ketones, xanthenes, thioxanthones, and anthraquinones, and it is preferable to use at least one compound selected from these groups. Benzophenones refer to benzophenone or derivatives thereof, and specifically include 3,3 ', 4,4'-benzophenone tetracarboxylic anhydride, 3,3', 4,4'-tetramethoxybenzophenone, and the like. Miherer ketones refer to miherer ketone and its derivatives. Xanthenes refer to derivatives substituted with xanthene and alkyl groups, phenyl groups, and halogen groups. Thioxanthones refer to thioxanthone and derivatives substituted with an alkyl group, a phenyl group, a halogen group, and the like, and examples thereof include ethylthioxanthone, methylthioxanthone, and chlorothioxanthone. Anthraquinones are anthraquinone and derivatives substituted with an alkyl group, a phenyl group, a halogen group, or the like. The addition amount of the hydrogen abstraction type photopolymerization initiator is preferably 0.3 wt% or more and 10 wt% or less, more preferably 0.5 wt% or more and 5 wt% or less of the total amount of the photosensitive resin composition. If the addition amount is within this range, when the liquid photosensitive resin composition is cured in the air, the curability of the surface of the cured product can be sufficiently secured, and the weather resistance can be secured.

  The decay type photopolymerization initiator refers to a compound in which an active radical is generated 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, acylphosphine oxides, azo compounds, organic sulfur compounds, and diketones. 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 organic sulfur compounds include aromatic thiols, mono- and disulfides, thiuram sulfides, dithiocarbamates, S-acyl dithiocarbamates, thiosulfonates, sulfoxides, sulfinates, dithiocarbonates, and the like. Examples of diketones include benzyl and methylbenzoyl formate. The addition amount of the collapsible photopolymerization initiator is preferably 0.1 wt% or more and 10 wt% or less, more preferably 0.3 wt% or more and 3 wt% or less of the total amount of the photosensitive resin composition. When the addition amount is within this range, when the photosensitive resin composition is photocured in the air, the curability inside the cured product can be sufficiently secured.

  In particular, in the case of a radical polymerization type photosensitive resin composition to be photocured in an atmosphere having an oxygen concentration of 5 vol% or more, a combination of a hydrogen abstraction type photopolymerization initiator and a decay type photopolymerization initiator as a photopolymerization initiator. Alternatively, it is preferable to use a photopolymerization initiator having both a site functioning as a hydrogen abstraction type photopolymerization initiator and a site functioning as a decay type photopolymerization initiator in the same molecule.

  The prepolymer (A) or the reactive monomer (B) is directly bonded to a sulfur atom such as a thiol compound, a compound having a hydrogen atom existing in the α position with respect to an oxygen atom or a nitrogen atom present in the molecular chain. It is preferable to contain at least 20 wt% or more and 100 wt% or less of the compound having a hydrogen atom or the like with respect to the total amount of the photosensitive resin composition. More preferably, it is 40 wt% or more and 100 wt% or less. Examples of the atomic group derived from the oxygen atom include alcohols, ethers, esters, and carbonates, and examples of the atomic group derived from the nitrogen atom include urethane, urea, and amide. Although the detailed reaction mechanism is not clear, hydrogen that is directly bonded to the α-position hydrogen or sulfur atom existing in the molecule of the prepolymer (A) or the reactive monomer (B) is extracted with a hydrogen. This is probably because radical species are generated by a reaction in which the excited triplet state is efficiently extracted, and the generated radical species contribute to the crosslinking reaction. Many hydrogen abstraction type photopolymerization initiators exhibit strong light absorption in the wavelength range of 200 nm to 300 nm, and these lights are attenuated rapidly inside the photosensitive resin composition layer. It is estimated to be.

In addition, a polymerization inhibitor, an ultraviolet absorber, a dye, a pigment, a lubricant, a surfactant, a plasticizer, a fragrance, and the like can be added to the photosensitive resin composition depending on the application and purpose.
To the photosensitive resin composition, inorganic fine particles or inorganic organic composite fine particles can be added as a filler. A porous body is particularly preferable. A porous body is a fine particle having fine pores or fine voids in a particle, and is an additive for absorbing and removing viscous liquid debris generated in large quantities in laser engraving. It also has an anti-tacking effect. An inorganic porous body or an inorganic organic composite porous body is added for the purpose of removing viscous liquid residue, and has a number average particle diameter, specific surface area, average pore diameter, pore volume, loss on ignition, etc. The performance is greatly affected.

The inorganic porous body or the inorganic / organic composite porous body preferably has a number average particle diameter of 0.1 to 100 μm. When the number average particle diameter is 0.1 μm or more, dust can be prevented from flying when the printing original plate is engraved with a laser, and an increase in viscosity can be suppressed when mixing the liquid photosensitive resin. On the other hand, when the number average particle size is 100 μm or less, a good relief image is obtained when laser engraving is performed, and the fineness of the printed matter can be maintained. A more preferable range of the average particle diameter is 0.5 to 20 μm, and a further preferable range is 3 to 10 μm. The average particle size of the porous inorganic absorbent of the present invention is a value measured using a laser scattering type particle size distribution measuring device.
The range of the specific surface area of the inorganic porous body or the inorganic / organic composite porous body is preferably 10 m ² / g or more and 1500 m ² / g or less. A more preferable range is 100 m ² / g or more and 800 m ² / g or less. When the specific surface area is 10 m ² / g or more, removal of the liquid residue during laser engraving is sufficient, and when the specific surface area is 1500 m ² / g or less, an increase in the viscosity of the photosensitive resin composition is suppressed, and thixotropic properties are obtained. Can be suppressed. The specific surface area of this invention is calculated | required based on the BET method from the adsorption isotherm of nitrogen in -196 degreeC.

The average pore diameter of the inorganic porous body or the inorganic / organic composite porous body of the present invention greatly affects the amount of liquid residue absorbed during laser engraving. A preferable range of the average pore diameter is 1 nm to 1000 nm, more preferably 2 nm to 200 nm, and still more preferably 2 nm to 50 nm. If the average pore diameter is 1 nm or more, the absorbability of liquid debris generated during laser engraving can be ensured, and if it is 1000 nm or less, the specific surface area of the particles is large and the amount of liquid debris absorbed can be sufficiently ensured. When the average pore diameter is less than 1 nm, the reason why the amount of absorbed liquid debris is small is not clear, but because liquid debris is viscous, it is estimated that it is difficult to enter the micropores and the amount of absorption is small. is doing.
The average pore diameter referred to in the present invention is a value measured using a nitrogen adsorption method. Those having an average pore diameter of 2 to 50 nm are particularly called mesopores, and the ability of porous particles having mesopores to absorb liquid waste is extremely high. The pore size distribution of the present invention is determined from the nitrogen adsorption isotherm at -196 ° C.

The pore volume of the inorganic porous material or the inorganic / organic composite porous material is preferably 0.1 ml / g or more and 10 ml / g or less, more preferably 0.2 ml / g or more and 5 ml / g or less. When the pore volume is 0.1 m / g or more, the amount of viscous liquid residue absorbed is sufficient, and when it is 10 ml / g or less, the mechanical strength of the particles can be ensured. In the present invention, a nitrogen adsorption method is used to measure the pore volume. The pore volume of the present invention is determined from an adsorption isotherm of nitrogen at −196 ° C.
There is an oil absorption amount as an index for evaluating the liquid residue adsorption amount. This is defined by the amount of oil absorbed by 100 g of the inorganic porous body or inorganic-organic composite porous body. The preferred range of oil absorption of the inorganic porous material or inorganic organic composite porous material used in the present invention is 10 ml / 100 g or more and 2000 ml / 100 g or less, more preferably 50 ml / 100 g or more and 1000 ml / 100 g or less. If the oil absorption is 10 ml / 100 g or more, the removal of liquid debris generated during laser engraving is sufficient, and if it is 2000 ml / 100 g or less, the mechanical strength of the inorganic porous body or inorganic-organic composite porous body is increased. Enough can be secured. The oil absorption was measured according to JIS-K5101.

The inorganic porous body or inorganic-organic composite porous body of the present invention preferably retains its porosity without being deformed or melted by laser light irradiation in the infrared wavelength region. The loss on ignition when treated at 950 ° C. for 2 hours is preferably 15 wt% or less, more preferably 10 wt% or less.
The particle shape of the inorganic porous material or inorganic organic composite porous material is not particularly limited, and spherical, flat, needle-shaped, amorphous, or particles having protrusions on the surface can be used. In particular, spherical particles are preferable from the viewpoint of wear resistance. It is also possible to use particles having a hollow inside, spherical granules having a uniform pore diameter such as silica sponge, and the like. Although it does not specifically limit, For example, porous silica, mesoporous silica, silica-zirconia porous gel, porous alumina, porous glass, etc. can be mentioned. Further, inorganic organic composite porous particles such as fine particles obtained by coating an organic thin film on the surface of an inorganic porous material, fine particles obtained by attaching inorganic porous particles to the surface of organic fine particles, and the like can also be used. Moreover, since the pore diameter cannot be defined for a layer having a gap of several to 100 nm such as a layered clay compound, in the present invention, the gap between the layers is defined as the pore diameter.

Furthermore, organic pigments such as pigments and dyes that absorb light of the wavelength of the laser beam can be incorporated into these pores or voids.
Sphericality is defined as an index that defines spherical particles. The sphericity used in the present invention is the ratio (D ₁ / D) of the diameter D ₁ of the largest circle that completely enters the projected figure when the particle is projected to the diameter D ₂ of the smallest circle that completely enters the projected figure. ₂ ). In the case of a true sphere, the sphericity is 1.0. The sphericity of preferred spherical particles used in the present invention is 0.5 or more and 1.0 or less, more preferably 0.7 or more and 1.0 or less. If it is 0.5 or more, the wear resistance as a printing plate is good. The sphericity of 1.0 is an upper limit value of sphericity. As spherical particles, it is desirable that 70% or more, more preferably 90% or more of the particles have a sphericity of 0.5 or more. As a method of measuring the sphericity, a method of measuring based on a photograph taken using a scanning electron microscope can be used. At that time, photography is performed at a magnification at which at least 100 particles or more enter the monitor screen. Further, D ₁ and D ₂ are measured based on a photograph, and the photograph is processed using a scanner device, and then data processing is performed using image analysis software.

In the present invention, these inorganic porous bodies or inorganic organic composite porous bodies can be selected from one type or two or more types, and by adding the selected ones, generation of liquid debris during laser engraving and printing can be performed. Improvements such as tack prevention of the plate are effectively performed.
As a method of molding the liquid photosensitive resin into a sheet or cylinder, an existing resin molding method can be used. For example, a casting method, a method of extruding a resin from a nozzle or a die with a machine such as a pump or an extruder, adjusting the thickness with a blade, or adjusting the thickness by calendering with a roll can be exemplified. In that case, it is also possible to perform molding while heating within a range that does not deteriorate the performance of the resin. Moreover, you may perform a rolling process, a grinding process, etc. as needed. Usually, it is often formed on an underlay called a back film made of a material such as PET or nickel, but it may be formed directly on a cylinder of a printing machine. The role of the back film is to ensure the dimensional stability of the printing original plate. Therefore, it is preferable to select one having high dimensional stability. When evaluated using the linear thermal expansion coefficient, the upper limit value of a preferable material is 100 ppm / ° C. or less, more preferably 70 ppm / ° C. or less.

  Specific examples of materials include polyester resin, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, polybismaleimide resin, polysulfone resin, polycarbonate resin, polyphenylene ether resin, polyphenylene thioether resin, polyethersulfone resin, all Examples thereof include liquid crystal resins composed of aromatic polyester resins, wholly aromatic polyamide resins, and epoxy resins. Further, these resins can be laminated and used. For example, a sheet or the like in which layers of polyethylene terephthalate having a thickness of 50 μm are laminated on both surfaces of a 4.5 μm thick wholly aromatic polyamide film may be used.

  In addition, a porous sheet, for example, a cloth formed by knitting fibers, a nonwoven fabric, a film in which pores are formed, or the like can be used as a back film. When a porous sheet is used as the back film, the photosensitive resin cured product layer is integrated with the back film by photocuring after impregnating the photosensitive resin composition into the pores, so that high adhesion is obtained. be able to. The fibers forming the cloth or nonwoven fabric include glass fibers, alumina fibers, carbon fibers, alumina / silica fibers, boron fibers, high silicon fibers, potassium titanate fibers, inorganic fibers such as sapphire fibers, natural materials such as cotton and hemp Examples include fibers, semi-synthetic fibers such as rayon and acetate, and synthetic fibers such as nylon, polyester, acrylic, vinylon, polyvinyl chloride, polyolefin, polyurethane, polyimide, and aramid. In addition, cellulose produced by bacteria is a highly crystalline nanofiber, and is a material that can produce a thin nonwoven fabric with high dimensional stability.

  Examples of a method for reducing the linear thermal expansion coefficient of the back film include a method of adding a filler, a method of impregnating or coating a resin on a mesh cloth such as wholly aromatic polyamide, or a glass cloth. As the filler, generally used organic fine particles, inorganic fine particles such as metal oxide or metal, organic / inorganic composite fine particles, and the like can be used. Moreover, porous fine particles, fine particles having cavities inside, microcapsule particles, layered compound particles in which a low molecular compound is intercalated, and the like can also be used. In particular, metal oxide fine particles such as alumina, silica, titanium oxide, and zeolite, latex fine particles made of polystyrene / polybutadiene copolymer, and natural organic organic fine particles such as highly crystalline cellulose are useful.

  By performing physical and chemical treatments on the surface of the back film, the adhesion with the photosensitive resin composition layer or the adhesive layer can be improved. Examples of the physical treatment method include a sand blast method, a wet blast method for injecting a liquid containing fine particles, a corona discharge treatment method, a plasma treatment method, an ultraviolet ray or vacuum ultraviolet ray irradiation method, and the like. Examples of chemical treatment methods include strong acid / strong alkali treatment methods, oxidant treatment methods, and coupling agent treatment methods.

  The molded photosensitive resin composition layer is crosslinked by light irradiation to form a cured photosensitive resin layer. It can also be cross-linked by light irradiation while forming. Examples of the light source used for curing include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an ultraviolet fluorescent lamp, a germicidal lamp, a carbon arc lamp, a xenon lamp, and a metal halide lamp. The light applied to the photosensitive resin composition layer preferably has a wavelength of 200 nm to 300 nm. In particular, since many hydrogen abstraction type photopolymerization initiators have strong light absorption in this wavelength region, when having light with a wavelength of 200 nm to 300 nm, sufficient curability of the surface of the cured photosensitive resin layer is ensured. be able to. Although the light source used for curing may be one type, the curability of the resin may be improved by curing using two or more types of light sources having different wavelengths, so two or more types of light sources may be used. There is no problem.

  A method for producing a sheet-shaped printing original plate or a cylindrical printing original plate having a particularly high plate thickness accuracy will be described. A photosensitive resin composition layer is formed by coating a liquid photosensitive resin composition at 20 ° C. on a cylindrical support, and then photocuring is performed by irradiating the photosensitive resin composition layer with light. Then, a cured photosensitive resin layer is formed. Furthermore, a cylindrical printing original plate can be formed through a process of smoothing the surface of the cured cured resin layer by a method such as polishing and adjusting the plate thickness. A sheet-shaped printing original plate having extremely high plate thickness accuracy can be obtained by cutting at least one portion of the cylindrical printing original plate thus obtained and peeling it off from the cylindrical support.

The thickness of the printing original plate is preferably in the range of 0.1 to 7 mm when used as a printing plate. Further, if necessary, rolling treatment, grinding treatment, etc. may be performed so that the plate thickness accuracy of the printing original plate after photocuring is 30 μm or less. When the plate thickness accuracy of the printing original plate after photocuring is 30 μm or less, the film thickness becomes uniform when printing is performed.
In some cases, the printing original plate may be formed by laminating a plurality of materials having different compositions. For example, a layer that can be engraved using a laser having an oscillation wavelength in the near infrared region such as the outermost surface YAG laser, fiber laser, or semiconductor laser is formed, and an infrared laser such as a carbon dioxide laser or visible light is formed under the layer. It is also possible to form a layer that can be laser engraved using an ultraviolet laser or the like. By forming such a laminated structure, a relatively high-power carbon dioxide laser is used to deeply engrave a relatively rough pattern, and a very fine pattern near the surface is used using a near-infrared laser such as a YAG laser or fiber laser. Can be engraved. Since an extremely fine pattern may be engraved relatively shallowly, the thickness of the layer sensitive to the near infrared laser is preferably in the range of 0.01 mm to 0.5 mm.

  Thus, by laminating a layer sensitive to the near infrared laser and a layer sensitive to the infrared laser, the depth of the pattern engraved using the near infrared laser can be accurately controlled. This is because a layer that is sensitive to an infrared laser utilizes a phenomenon that is difficult to engrave with a near infrared laser. The difference in the fineness of the engraving pattern is caused by the difference in oscillation wavelength unique to the laser apparatus, that is, the difference in the diameter of the laser beam that can be narrowed. When laser engraving is performed in this way, engraving can be performed using separate laser engraving equipment equipped with infrared laser and near infrared laser, and laser engraving equipment equipped with both infrared laser and near infrared laser can be used. It is also possible to use.

In the present invention, a cushion layer made of an elastomer can be formed below the layer to be laser engraved. In general, since the thickness of the layer to be laser engraved is 0.1 to several mm, the other lower layers may be made of materials having different compositions. The cushion layer is preferably an elastomer layer having a Shore A hardness of 10 to 70 degrees. When the Shore A hardness is 10 degrees or more, the print quality can be ensured because the film is appropriately deformed. Moreover, if it is 70 degrees or less, it can play the role as a cushion layer.
The cushion layer is not particularly limited, and any cushion layer may be used as long as it has rubber elasticity, such as a thermoplastic elastomer, a photocurable elastomer, and a thermosetting elastomer. It may be a porous elastomer layer having nanometer-level micropores. In particular, from the viewpoint of processability to a sheet-like or cylindrical printing original plate, it is convenient and preferable to use a liquid photosensitive resin composition that is cured by light and to use a material that becomes elastomer after curing.

  Specific examples of the thermoplastic elastomer used for the cushion layer include SBS (polystyrene-polybutadiene-polystyrene), SIS (polystyrene-polyisoprene-polystyrene), SEBS (polystyrene-polyethylene / polybutylene-polystyrene), which are styrenic thermoplastic elastomers, and the like. Olefin-based thermoplastic elastomer, urethane-based thermoplastic elastomer, ester-based thermoplastic elastomer, amide-based thermoplastic elastomer, silicon-based thermoplastic elastomer, fluorine-based thermoplastic elastomer, and the like.

  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 composition obtained by mixing a photopolymerizable monomer, a photopolymerization initiator, etc. with a plastomer resin. Can be mentioned. In the present invention, unlike the design concept of the photosensitive resin composition, in which the function of forming a fine pattern is an important element, it is not necessary to form a fine pattern using light, and by curing by overall exposure, Since it is sufficient to ensure a certain level of mechanical strength, the degree of freedom in selecting a material is extremely high.

Moreover, non-sulfur cross-linked rubbers such as sulfur cross-linked rubber, organic peroxide, phenol resin initial condensate, quinone dioxime, metal oxide, and thiourea can also be used.
Furthermore, it is also possible to use a three-dimensionally crosslinked elastomer obtained by using a curing agent that reacts with a telechelic liquid rubber.
In the case of multilayering in the present invention, the position of the back film may be any position below the cushion layer, that is, at the lowermost part of the printing original plate or at the central part of the printing original plate.

The photosensitive resin cured product layer preferably contains one or more kinds of fine particles composed of inorganic fine particles and inorganic / organic composite fine particles. Examples of inorganic fine particles include light calcium carbonate, heavy calcium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc hydroxide, zinc sulfide, zinc carbonate, hydrotalcite, aluminum silicate. Diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, alumina, colloidal amine, pseudoboehmite, aluminum hydroxide, lithopone, zeolite and the like.
The inorganic organic composite fine particles are composite fine particles that are made more hydrophilic or hydrophobic by coating the surface of the inorganic fine particles with a silane coupling agent, a titanium coupling agent, other organic substances, etc., and modifying the surface.

  The solvent in the solvent-based ink is determined by the solubility of the polymer component in the solvent-based ink and the drying property in the printing process, but the ester solvent, ether solvent, hydrocarbon solvent, halogen solvent, It is preferable that at least one solvent component selected from nitrogen-containing hydrocarbon solvents is contained in an amount of 20 wt% to 100 wt% of the total amount of the solvent. If the content rate of the said solvent component is 20 to 100 wt%, the aromatic compound used for an electronic material use can fully be melt | dissolved or disperse | distributed.

  In the laser engraving printing plate, it is possible to design a cured photosensitive resin having resistance to the solvent contained in the ink to be used. In the ink for forming the electronic circuit or optical member of the present invention, as a solvent for dissolving or dispersing the functional compound, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl benzoate, ethyl benzoate, tetrahydrofuran Ether solvents such as oxirane and dibutyl ether, hydrocarbon solvents such as hexane, heptane, octane, toluene and xylene, halogen solvents such as chloroform, dichloroethane, tetrachloroethylene, chlorobenzene and dichlorobenzene, methylpyrrolidone and pyridine. Examples thereof include nitrogen hydrocarbon solvents. The solvent resistance to the solvent contained in the ink of the laser engraving printing plate is evaluated by a solvent immersion swelling test, and the swelling ratio before and after immersion in the solvent is 10 wt% or less. Preferably it is 5 wt% or less. The solvent immersion swelling test in the present invention is performed by immersing a test sample in a solvent at room temperature for 24 hours. If the swelling rate is 10 wt% or less, the dimensional change of the laser engraving printing plate is small, so that not only fine pattern printing and uniform coating of a thin film are possible, but also dimensional stability of the printing plate can be ensured, printing The durability of the plate is also good and it can withstand repeated printing processes.

  As a guideline for designing a material for a laser engraving printing plate having high solvent resistance, it is preferable to select a material having a large difference in solubility parameter between the main portion constituting the prepolymer (A) to be used and the solvent. The solubility parameter (hereinafter, abbreviated as SP) is also called a solubility factor, and is an index indicating the polarity of a substance and is an index of affinity. The solubility parameter is also described in the Dictionary of Chemistry (Tokyo Chemical Dojinsha, published in 1989). In general, the closer the SP values of the two, the easier it is to melt together, and when one is solid, it is easy to get wet, and it is used as one standard for selecting an adhesive or a solvent. In the present invention, since it is necessary for the printing plate to have resistance to the solvent contained in the ink used, the difference in solubility parameter between the main part constituting the prepolymer (A) to be used and the solvent is It is preferable to select a larger one.

  For example, for hydrocarbon solvents such as hexane, heptane, octane, cyclohexane, kerosene, linseed oil, soybean oil, toluene, xylene, etc., select a prepolymer having a hydrocarbon-based polybutadiene skeleton, polyisoprene skeleton, etc. The unsaturated polyurethane using unsaturated polyester, polyester polyol, polycarbonate diol or the like is more preferable. For nitrogen-containing hydrocarbon solvents such as methylpyrrolidone, pyridine, acetonitrile, and dimethylformamide, ketone solvents such as acetone and methyl ethyl ketone, and γ-butyrolactone, polybutadiene and other poly A prepolymer having an alkylene skeleton is preferred. For butoxyethanol and ethoxyethanol, unsaturated polyurethane and polymers having a polyalkylene skeleton are preferred. Unsaturated polyesters are preferred for halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene. For ester solvents such as benzoic acid esters, ethyl acetate, propyl acetate and butyl acetate, unsaturated polyurethanes having an unsaturated polyester, polycarbonate diol or the like as a skeleton are preferable.

In a pattern formed using a laser engraving method on a printing original plate, when a convex pattern having an outermost surface dimension of 200 μm square and a height of 500 μm is formed, the height difference between the central part and the edge part of the convex pattern is 30 μm. The following is preferable.
If the height difference between the central portion and the edge portion of the convex pattern is 30 μm or less, printing can be performed with a low printing pressure, and the printed film thickness becomes uniform. The cupping phenomenon that has been a problem with conventional photosensitive resin plates, that is, the phenomenon in which the film thickness at the center of the pattern becomes thin due to photocuring shrinkage can be solved by patterning the printing original plate by laser engraving.
Further, by forming a modified layer on the surface of the laser engraving printing plate, it is possible to reduce the tack of the printing plate surface and improve the ink wettability. Examples of the modified layer include a film treated with a compound that reacts with a surface hydroxyl group such as a silane coupling agent or a titanium coupling agent, or a polymer film containing porous inorganic particles.

  A widely used silane coupling agent is a compound having in its molecule a functional group highly reactive with the surface hydroxyl group of the substrate. Examples of such a functional group include a trimethoxysilyl group and a triethoxysilyl group. Group, trichlorosilyl group, diethoxysilyl group, dimethoxysilyl group, dimonochlorosilyl group, monoethoxysilyl group, monomethoxysilyl group, monochlorosilyl group and the like. In addition, it is preferable that at least one of these functional groups exists in the molecule and is immobilized on the surface of the base material by reacting with the surface hydroxyl group of the base material. Further, the compound constituting the silane coupling agent of the present invention includes an acryloyl group, a methacryloyl group, an active hydrogen-containing amino group, an epoxy group, a vinyl group, a perfluoroalkyl group, and a mercapto group as reactive functional groups in the molecule. Those having at least one selected functional group or those having a long-chain alkyl group or the like can be used.

  Examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (di-tridecyl phosphite) titanate, Tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (octylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyl Dimethacrylisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropylisostearoyl diacryl titanate Over DOO, isopropyl tri (dioctyl sulfate) titanate, isopropyl tricumylphenyl titanate, tetraisopropyl bis (dioctyl phosphite) may include compounds such as titanates.

When the coupling agent molecule immobilized on the surface has a polymerizable reactive group in particular, it is possible to obtain a stronger coating by irradiating light, heat, or an electron beam and crosslinking after immobilization on the surface. .
In the present invention, the above-mentioned coupling agent is prepared by diluting with a water-alcohol or acetic acid water-alcohol mixture as necessary. The concentration of the coupling agent in the treatment liquid is preferably 0.05 to 10.0 wt%.

The coupling agent treatment method in the present invention will be described. The treatment liquid containing the coupling agent is applied to the printing plate surface. The method for applying the coupling agent treatment liquid is not particularly limited, and for example, an immersion method, a spray method, a roll coating method, or a brush coating method can be applied. Further, the coating treatment temperature, the coating treatment time, and the like are not particularly limited, but are preferably 5 to 60 ° C., and the treatment time is preferably 0.1 to 60 seconds. Furthermore, it is preferable to dry the treatment liquid layer on the printing plate surface under heating, and the heating temperature is preferably 50 to 150 ° C.
Before treating the printing plate surface with a coupling agent, a method of irradiating light in a vacuum ultraviolet region with a wavelength of 200 nm or less, such as a xenon excimer lamp, or by exposing it to a high energy atmosphere such as plasma, And the coupling agent can be immobilized at a high density.
When the layer containing inorganic porous particles or organic / inorganic composite porous particles is exposed on the printing plate surface, it is treated under a high energy atmosphere such as plasma, and the organic layer on the surface is removed by etching. As a result, minute irregularities can be formed on the surface of the printing plate. By this treatment, the effect of improving the ink wettability can be expected by reducing the tack of the printing plate surface and making the inorganic porous particles exposed on the surface easy to absorb the ink.

  In laser engraving, a relief image is created on a printing original plate by operating a laser device using a computer as an image to be formed as digital data. Any laser can be used for the laser engraving as long as the printing original plate includes a wavelength having absorption. However, in order to perform engraving at a high speed, a laser with a high output is desirable. Infrared or infrared emitting solid lasers such as YAG laser and semiconductor laser are preferred. In addition, an ultraviolet laser having an oscillation wavelength in the ultraviolet region, such as an excimer laser, a YAG laser wavelength-converted to the third or fourth harmonic, a copper vapor laser, and the like, can be ablated to cut bonds between organic molecules, Suitable for fine processing. The laser may be continuous irradiation or pulse irradiation. In general, resin has absorption in the vicinity of 10 μm of carbon dioxide laser, so it is not essential to add a component that helps the absorption of laser light, but YAG laser has a wavelength in the vicinity of 1.06 μm. There is not much that has. In that case, it is preferable to add a dye or a pigment, which is a component that assists in the absorption thereof.

  Examples of such dyes include: poly (substituted) phthalocyanine compounds and metal-containing phthalocyanine compounds; cyanine compounds; squarylium dyes; chalcogenopyrylarylidene dyes; chloronium dyes; metal thiolate dyes; Indolizine dyes; bis (aminoaryl) polymethine dyes; merocyanine dyes; and quinoid dyes. Examples of pigments include dark inorganic pigments such as carbon black, graphite, copper chromite, chromium oxide, cobalt chrome aluminate, iron oxide, and metal powders such as iron, aluminum, copper, and zinc, and Si, Examples include those doped with Mg, P, Co, Ni, Y, and the like. These dyes and pigments may be used alone, in combination of a plurality, or in any form such as a multilayer structure.

Laser engraving is carried out in an oxygen-containing gas, generally in the presence of air or an air stream, but can also be carried out in the presence of carbon dioxide or nitrogen gas. After engraving is finished, the powdery or liquid substance slightly generated on the printing plate surface is washed by an appropriate method, for example, a method of washing with water containing a solvent or a surfactant, a method of irradiating a water-based cleaning agent by high pressure spraying, You may remove using the method of irradiating a high pressure steam.
When the printing original plate is irradiated with laser light to form a concave pattern, the surface of the printing original plate can be heated to assist laser engraving. Examples of the method for heating the printing original plate include a method of heating a sheet or cylindrical surface plate of a laser engraving machine using a heater, and a method of directly heating the surface of the printing original plate using an infrared heater. This heating step can improve the laser engraving property. The degree of heating is preferably in the range of 50 ° C to 200 ° C, more preferably in the range of 80 ° C to 200 ° C, and still more preferably in the range of 100 ° C to 200 ° C.

After forming a pattern by laser engraving and producing a laser engraving printing plate, the surface of the obtained laser engraving printing plate may be irradiated with ultraviolet rays to remove the stickiness of the surface. Examples of the atmosphere for irradiating with ultraviolet rays include air, an inert gas atmosphere, and water.
The printing plate is a relief image for patterning insulators, resistors, and conductor pastes used to create electronic components, optical component antireflection films, color filters, pattern formation of functional materials such as (near) infrared absorption filters, In addition to the alignment film, underlayer, light emitting layer, electron transport layer, coating film / pattern formation of sealant layer in the manufacture of display elements such as liquid crystal displays or organic electroluminescence displays, relief images for printing plates, stamps / stamps, Design rolls for embossing, relief images for mold materials of ceramic products, relief images for displays such as advertisements and display boards, and various applications such as prototypes and master molds for various molded products.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not restrict | limited by these.
(1) Measurement of number average molecular weight The number average molecular weight of the prepolymer (A) was determined by conversion to polystyrene having a known molecular weight using a gel permeation chromatography method (GPC method). Using a high-speed GPC apparatus (trade name HLC-8020, manufactured by Tosoh Corporation, Japan) and a polystyrene-filled 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 wt% was prepared, and the injection amount was 10 μl. As a detector, an ultraviolet absorption detector was used. Since the prepolymer (A) used in the examples or comparative examples of the present invention had a polydispersity (Mw / Mn) determined by the GPC method of greater than 1.1, the number average molecular weight Mn determined by the GPC method It was adopted.

(2) Laser engraving Laser engraving was performed using a carbon dioxide laser engraving machine (trademark: ZED-mini-1000, UK, manufactured by ZED, USA, coherent, output 250 W carbon dioxide laser). The engraving was performed by producing a pattern including a 200 μm square pattern, a line drawing with a 100 μm wide convex line, and a 100 μm wide white line. The engraving depth was 0.50 mm.

[Example 1]
(Prepolymer production)
In a 1 L separable flask equipped with a thermometer and a stirrer, 51 parts by weight of polyoxyethylene (EO) -polyoxypropylene (PO) block copolymer diol having a number average molecular weight of 2500 (EO / PO molar ratio 1/4) , 33.9 parts by weight of poly (3-methyl-1,5-pentanediol adipate) having a number average molecular weight of 3000, 0.003 parts by weight of dibutyltin tin dilaurate as a catalyst, and 2,6-di-tert-butyl-4-methylphenol 0.1 part by weight was added and stirred and mixed. The water content in the system was adjusted to 400 ppm. Next, 6 parts by weight of tolylene diisocyanate was added dropwise with stirring at an external temperature of 40 ° C., and then the external temperature was gradually raised and reacted at 80 ° C. for 5 hours. Further, 4 parts by weight of 2-hydroxypropyl methacrylate was added and reacted for 2 hours to obtain an unsaturated polyurethane (a). The number average molecular weight in terms of polystyrene by GPC was 22500.

(Preparation of photosensitive resin composition)
65 parts by weight of unsaturated polyurethane (a), 13 parts by weight of diethylene glycol-2-ethylhexyl ether acrylate, 20 parts by weight of diethylene glycol monobutyl ether monomethacrylate, 2 parts by weight of trimethylolpropane trimethacrylate, photopolymerization initiator 2,2-dimethoxy- 2-phenylacetophenone 0.6 part by weight, benzophenone 1 part by weight, inorganic porous material C-1504 (manufactured by Fuji Sicilian Chemical Co., Ltd., porous fine powder silica, trademark “Cyrossphere C-1504”, number average particle 4.5 μm diameter, specific surface area 520 m ² / g, average pore diameter 12 nm, pore volume 1.5 ml / g, loss on ignition 2.5 wt%, oil absorption 290 ml / 100 g), polymerization inhibitor 2,6-di-t- Mix 0.05 parts by weight of butyl-4-methylphenol A photopolymer composition A was obtained.

(Preparation of printing master)
The produced photosensitive resin composition A was formed into a sheet having a thickness of 2.8 mm on a PET film, and a metal halide lamp (trade name “M056-L21” manufactured by Eye Graphics Co., Ltd.) was slid while opening ( Light emitted from the opening size (40 mm × 310 mm) was irradiated from the surface where the photosensitive resin layer was exposed in the atmosphere. The amount of energy irradiated was 4000 mJ / cm ² (a value obtained by integrating the illuminance measured with the UV-35-APR filter over time). The lamp illuminance on the irradiated surface was measured using a UV meter (trade name “UV-M02” manufactured by Oak Manufacturing Co., Ltd.). The lamp illuminance measured using a UV-35-APR filter (trade name, manufactured by Oak Manufacturing Co., Ltd.) was 100 mW / cm ² , and the lamp illuminance measured using a UV-25-filter (trade name, manufactured by Oak Manufacturing Co., Ltd.). Was 14 mW / cm ² .
The thickness of the obtained printing original plate a was uniform, and the plate thickness accuracy was 2.8 mm ± 10 μm. In addition, the thickness was measured at intervals of 3 cm using a trademark “Digimatic Indicator ID-C112” (manufactured by Mitutoyo Corporation) that can measure up to 1 μm.

(Laser engraving)
A pattern was engraved on the obtained printing original plate a under the above laser engraving conditions. As a result, a printing plate 1 having a height difference of ± 5 μm between the center and the edge of the 200 μm square pattern was obtained. The measurement was carried out under the trademark “System Electric Biological Microscope BX-61” (manufactured by Olympus Optical Co., Ltd.).

(Print evaluation)
Printing evaluation was carried out using the printing plate 1 produced by laser engraving. Polyethylene terephthalate whose surface is easy-adhesive treated by using a tabletop proofing machine (trademark “Flexiproof 100” manufactured by KR, UK) for printing, and the printing plate 1 is attached to the plate cylinder using a double-sided tape. Conductive ink in which ultrafine particles of silver (average particle diameter 7 nm) are dispersed on the easy-adhesion treated surface of a sheet (thickness: 100 μm), trademark “silver nanopaste” (manufactured by Harima Chemicals, solvent tetradecane, solvent content 30 wt% ), Printing, drying, and firing (temperature 150 ° C.) so that the film thickness of the ink after firing is 1 μm. As a result, a 200 μm square pattern, a 100 μm wide convex line, and a 100 μm wide white The film thickness after firing was uniform at 1 μm for both the drawn lines.

(Measurement of swelling rate)
The test sample was coated with the photosensitive resin composition A 10 mm × 50 mm in a thickness of 1 mm, and irradiated with energy of 1800 mJ / cm ² using Asahi Kasei Chemicals, flexo vending machine, and trademark “ALF plate making machine”. And prepared by curing.
The prepared test sample is immersed in tetradecane, which is a dilution solvent for the above “silver nanopaste”, at 20 ° C. for 24 hours, and then the droplets adhering to the surface are wiped off, and the weight increase is measured to determine the swelling ratio. It was. As a result, the swelling rate was 3.0 wt%.

[Example 2]
(Prepolymer production)
In a 2 L separable flask equipped with a thermometer and a stirrer, 212 parts by weight of diethylene glycol, 152 parts by weight of propylene glycol, 90 parts by weight of 1,4-butanediol, 511 parts by weight of adipic acid, 87 parts by weight of fumaric acid, tetrahydrophthalic anhydride 127 parts by weight and 1.2 parts by weight of p-methoxyphenol were reacted in a nitrogen atmosphere at normal pressure and 230 ° C. for 4 hours, and further reacted under reduced pressure of 13332 Pa for 4 hours to obtain an unsaturated polyester having an acid value of 23. .
560 parts by weight of this unsaturated polyester, 33.6 parts by weight of hexamethylene diisocyanate and 0.6 part by weight of 2,6-di-tert-butyl-4-methylphenol were mixed and reacted at 80 ° C. for 4 hours. Then, 43.2 parts by weight of hydroxypropyl methacrylate and 0.2 parts by weight of dibutyltin tin dilaurate were added, and the mixture was further reacted at 80 ° C. for 2 hours to obtain unsaturated polyester urethane (b). The polystyrene equivalent number average molecular weight of this product by GPC was 7000.

(Preparation of photosensitive resin composition)
Diethyl glycol dimethacrylate 16.63 parts by weight, diacetone acrylamide 8.28 parts by weight, diethylene glycol dimethacrylate 8.28 parts by weight, photopolymerization initiator 2,2- 0.6 parts by weight of dimethoxy-2-phenylacetophenone, 1 part by weight of benzophenone, inorganic porous material C-1504 (manufactured by Fuji Sicilian Chemical Co., Ltd., porous fine powder silica, trademark “Cyrossphere C-1504”, number average Particle size 4.5 μm, specific surface area 520 m ² / g, average pore diameter 12 nm, pore volume 1.5 ml / g, ignition loss 2.5 wt%, oil absorption 290 ml / 100 g) 5 parts by weight, polymerization inhibitors 2, 6 -Di-t-butyl-4-methylphenol 0.05 weight part was mixed and the photosensitive resin composition B was obtained.

(Preparation of printing master)
A printing original plate A was prepared in the same manner as in Example 1 except that the photosensitive resin composition B was used.
The thickness of the obtained printing original plate A was uniform, and the plate thickness accuracy was 2.8 mm ± 10 μm. The measurement was performed by the method described in Example 1.

(Laser engraving)
A pattern was engraved on the obtained printing original plate A under the above laser engraving conditions. As a result, a printing plate 2 having a height difference of ± 5 μm between the center portion and the end portion of the 200 μm square pattern was obtained. The measurement was carried out under the trademark “System Electric Biological Microscope BX-61” (manufactured by Olympus Optical Co., Ltd.).

(Print evaluation)
Printing evaluation of the organic high EL light emitting layer was performed using the printing plate 2 produced by laser engraving. For printing, a desktop proofing machine (trademark “Flexiproof 100” manufactured by KR, UK) was used, and the printing plate 2 was attached to the plate cylinder using a double-sided tape. As a non-printed body, an ITO film (anode) having a thickness of 0.1 μm is formed on the surface of a 0.7 mm thick glass substrate (soda lime glass) by a vacuum deposition method, and then subjected to UV-ozone cleaning to obtain an organic matter. After removing the deposits, etc., a coating liquid containing polyethylene dioxythiophene (polyethylenedioxythiophene-polystyrene sulfonate (PEDT / PEDT) as a hole transport material by spin coating on the surface of the ITO film side of the equipment. PSS), manufactured by Bayer, trade name “Baytron P”) was applied and dried at 70 to 80 ° C. to prepare a hole transport layer. Poly (9,9-dialkylfluorene (PDAF)) is used as the organic polymer light-emitting body, and it is dissolved in a solvent (xylene) so that the solid content concentration is 2 wt%. Used and printed. As a result, the thickness of the ink printed on the hole transport layer (before drying) was 6 μm, and the thickness of the light emitting layer after drying at 80 ° C. for 30 minutes was 0.12 μm and uniform.

(Measurement of swelling rate)
The test sample was coated with the photosensitive resin composition B in a size of 10 mm × 50 mm and a thickness of 1 mm, and irradiated with energy of 1800 mJ / cm ² using Asahi Kasei Chemicals, flexo vending machine, and trademark “ALF plate making machine”. And prepared by curing.
The prepared test sample is immersed in xylene, which is the solvent of the ink for forming the light emitting layer, at 20 ° C. for 24 hours, and then the droplet adhering to the surface is wiped off, and the weight increase is measured to determine the swelling rate. It was. As a result, the swelling rate was 1.1 wt%.

[Example 3]
(Prepolymer production)
Into a 1 L separable flask equipped with a thermometer and a stirrer, 100 parts by weight of a trademark “PCDL L4672” (number average molecular weight 1990, OH number 56.4), which is a polycarbonate diol manufactured by Asahi Kasei Chemicals Corporation, and 6. After adding 9 parts by weight and reacting at 80 ° C. for 3 hours with heating, 3.3 parts by weight of 2-methacryloyloxyisocyanate was added and the reaction was further continued for 3 hours to obtain unsaturated polyurethane (c). The polystyrene-reduced number average molecular weight of this product by GPC was about 10,000.

(Preparation of photosensitive resin composition)
For 100 parts by weight of unsaturated polyurethane (c), 25 parts by weight of benzyl methacrylate, 19 parts by weight of cyclomethacrylate, 6 parts by weight of butoxydiethylene glycol methacrylate, 0.6 parts by weight of photopolymerization initiator 2,2-dimethoxy-2-phenylacetophenone, 1 part by weight of benzophenone, inorganic porous material C-1504 (manufactured by Fuji Sicilian Chemical Co., Ltd., porous fine powder silica, trademark “Pyrospher C-1504”, number average particle diameter 4.5 μm, specific surface area 520 m ² / g, average pore diameter 12 nm, pore volume 1.5 ml / g, ignition loss 2.5 wt%, oil absorption 290 ml / 100 g) 5 parts by weight, polymerization inhibitor 2,6-di-t-butyl-4-methylphenol 05 weight part was mixed and the photosensitive resin composition C was obtained.

(Preparation of printing master)
A printing original plate C was prepared in the same manner as in Example 1 except that the photosensitive resin composition C was used.
The thickness of the obtained printing original plate C was uniform, and the plate thickness accuracy was 2.8 mm ± 10 μm. The measurement was performed by the method described in Example 1.

(Laser engraving)
A pattern was engraved on the obtained printing original plate C under the above laser engraving conditions. As a result, a printing plate 3 having a height difference of ± 7 μm between the center and the edge of the 200 μm square pattern was obtained. The measurement was carried out under the trademark “System Electric Biological Microscope BX-61” (manufactured by Olympus Optical Co., Ltd.).

(Print evaluation)
Printing evaluation was performed in the same manner as in Example 1 except that the printing plate 3 was used. As a result, the film thickness after firing of a 200 μm square pattern, a 100 μm wide convex line, and a 100 μm wide white line was uniform at 1 μm.

(Measurement of swelling rate)
The test sample was coated with the photosensitive resin composition C to a size of 10 mm × 50 mm and a thickness of 1 mm, and irradiated with energy of 1800 mJ / cm ² using Asahi Kasei Chemicals, flexo vending machine, and trademark “ALF plate making machine”. And prepared by curing.
The prepared test sample is immersed in tetradecane, which is a dilution solvent for the above “silver nanopaste”, at 20 ° C. for 24 hours, and then the droplets adhering to the surface are wiped off, and the weight increase is measured to determine the swelling ratio. It was. As a result, the swelling rate was 0.9 wt%.

[Comparative Example 1]
(Preparation of printing master)
Using the same photosensitive resin composition A as in Example 1, on the glass surface of Asahi Kasei Chemicals Co., Ltd., flexo plate making machine, trademark “AWF plate making machine”, the number of thicknesses on one side of a transparent polyethylene terephthalate film having a thickness of 180 μm The base film for a photosensitive resin plate to which a μm adhesive was applied was placed so that the surface to which the adhesive layer was applied was facing up, and was brought into vacuum contact. On the base film, the photosensitive resin composition A was molded and spread using a carriage made by Asahi Kasei Co., Ltd. with a thickness of 2.62 mm and a transparent film with a thickness of 100 μm. The carriage is a traveling molding and spreading device having a laminate roller, a bucket (resin reservoir), a film, a guide, and the like, and a spacer along the glass surface (a rail that moves up and down to regulate the thickness of the plate). This is an apparatus for casting (coating) the photosensitive resin composition layer to a predetermined thickness while casting the photosensitive resin composition while running on top and feeding the film.
Next, the photosensitive resin composition A was cured by irradiating ultraviolet rays from the upper part of the obtained laminate with an exposure device provided in the plate making machine. After the exposure was completed, the polyethylene terephthalate film was peeled off to prepare a printing original plate D. When the thickness of the printing original plate was measured, the plate thickness accuracy was 2.8 mm ± 40 μm and was not uniform. The measurement was performed by the method described in Example 1.

(Laser engraving)
A pattern was engraved on the obtained printing original plate D under the above laser engraving conditions. As a result, a printing plate 4 having a height difference of ± 20 μm between the center and the edge of the 200 μm square pattern was obtained. The measurement was carried out under the trademark “System Electric Biological Microscope BX-61” (manufactured by Olympus Optical Co., Ltd.).

(Print evaluation)
Printing evaluation was performed in the same manner as in Example 1 except that the printing plate 4 was used. As a result, although the film thickness after firing was about 1 μm for both the 200 μm square pattern, the 100 μm wide convex line, and the 100 μm wide white line, it was non-uniform and uneven.

[Comparative Example 2]
(Preparation of printing master)
Using the same photosensitive resin composition A as in Example 1, on the glass surface of Asahi Kasei Chemicals Co., Ltd., flexo plate making machine, trademark “AWF plate making machine”, the number of thicknesses on one side of a transparent polyethylene terephthalate film having a thickness of 180 μm The base film on which the μm adhesive was applied was placed so that the surface on which the adhesive layer was applied was on top, and was brought into vacuum contact. On the base film, the photosensitive resin composition A was molded and spread to a thickness of 2.62 mm using a carriage manufactured by Asahi Kasei Corporation and a negative film for forming a convex pattern. The carriage is a traveling molding and spreading device having a laminate roller, a bucket (resin reservoir), a negative film, a guide, and the like. A spacer along the glass surface (a rail that moves up and down to regulate the thickness of the plate) ) A device that casts the photosensitive resin composition to a predetermined thickness while casting the photosensitive resin composition while running on top and feeding a negative film. On the negative film, a pattern including a 200 μm square pattern, a line drawing by a convex line having a width of 100 μm, and a white line having a width of 100 μm is produced.

  Next, the photosensitive resin composition A was cured by irradiating ultraviolet rays from the upper part of the obtained laminate with an exposure device provided in the plate making machine. After the exposure is completed, the negative film is peeled off, and the uncured portion that has not been irradiated with ultraviolet rays is scraped off with a spatula, and then the uncured portion is removed with a weak alkaline detergent (trade name “W-10” manufactured by Asahi Kasei Co., Ltd.). Completely removed. Furthermore, the printing plate 5 was obtained by irradiating ultraviolet rays in water to completely cure the printing original plate, and then removing moisture using a hot air dryer. That is, a printing plate 5 having a plate thickness of 2.8 mm and a convex pattern height of 0.5 mm was obtained. The difference in height between the center and the edge of the 200 μm square pattern of this printing plate 5 was ± 25 μm. The measurement was performed with the trademark “System Electric Biological Microscope BX-61” (manufactured by Olympus Optical Co., Ltd.).

(Print evaluation)
Printing evaluation was performed in the same manner as in Example 1 except that the printing plate 5 was used. As a result, although the film thickness after firing was about 1 μm for both the 200 μm square pattern, the 100 μm wide convex line, and the 100 μm wide white line, it was non-uniform, the pattern edge was thick, and the central part was thin. It was.

[Comparative Example 3]
(Print evaluation)
Printing evaluation was performed in the same manner as in Example 2 except that the printing plate 1 was used. As a result, both the 200 μm square pattern, the 100 μm wide convex line, and the 100 μm wide white line had poor pattern endurance every time the number of printed copies was repeated, and the durability was poor.

(Measurement of swelling rate)
The test sample was coated with the photosensitive resin composition A 10 mm × 50 mm in a thickness of 1 mm, and irradiated with energy of 1800 mJ / cm ² using Asahi Kasei Chemicals, flexo vending machine, and trademark “ALF plate making machine”. And prepared by curing.
The prepared test sample is immersed in xylene, which is the solvent of the ink for forming the light emitting layer, at 20 ° C. for 24 hours, and then the droplet adhering to the surface is wiped off, and the weight increase is measured to determine the swelling rate. It was. As a result, the swelling rate was 209 wt%.

  INDUSTRIAL APPLICABILITY The present invention can be suitably used in the field relating to the manufacture of electronic circuits or optical members having a high-definition and uniform film thickness pattern.

Claims (7)

  (A) A step of irradiating a photosensitive resin composition layer formed into a sheet shape or a cylindrical shape to form a cured photosensitive resin layer to form a printing original plate, and (b) irradiating the printing original plate with laser light. A step of producing a flexographic printing plate having a convex pattern on its surface or a gravure printing plate having a concave pattern, or a step of producing a screen printing plate having a hole pattern penetrating a cured photosensitive resin layer, (c) Using at least one kind of printing plate selected from the obtained flexographic printing plate, gravure printing plate and screen printing plate, an ink containing at least one kind selected from an insulator, a semiconductor and a conductor is printed (D) The liquid medium in the formed ink is removed by drying, or the ink is irradiated with light to be cured and fixed, and the thickness is from 1 nm to 10 μm. In the case where the plate thickness accuracy of the printing original plate is 30 μm or less and the resistance to the liquid medium in the ink used in the printing process is evaluated by an immersion swelling test, the immersion in the liquid medium A method of manufacturing an electronic circuit or an optical member, wherein the weight change rate before and after is 10 wt% or less.   The liquid medium in the ink is at least one solvent component selected from an ester solvent, an ether solvent, a hydrocarbon solvent, a halogen solvent, and a nitrogen-containing hydrocarbon solvent. The method for producing an electronic circuit or an optical member according to claim 1, comprising:   A printing plate for forming a thin film containing at least one kind selected from an insulator, a semiconductor, and a conductor using a flexographic printing method, wherein the convex pattern according to claim 1 has an outermost surface dimension of 200 μm square, A laser engraving printing plate for printing an electronic circuit or an optical member, wherein the height difference between the central part and the edge part of the convex pattern is 30 μm or less when the height is 500 μm.   4. The electronic circuit or optical member printing device according to claim 3, further comprising a cushion layer having a Shore A hardness of 10 degrees to 70 degrees between the cylindrical support body or the sheet-like support body and the printing plate. Laser engraving printing plate.   5. The laser engraving for printing an electronic circuit or an optical member according to claim 3, wherein the cured photosensitive resin contains at least one kind of fine particles selected from inorganic fine particles and inorganic / organic composite fine particles. Printed version.   The step of applying a liquid photosensitive resin composition on a cylindrical support at 20 ° C., the step of photocuring the applied liquid photosensitive resin composition to form a photosensitive resin cured product layer, and the resulting photosensitivity Surface adjustment process of smoothing the surface of the cured resin layer while rotating, further irradiating the photosensitive resin cured layer with laser light, and removing the resin at the portion irradiated with the laser light to form a pattern The manufacturing method of the laser engraving printing plate for electronic circuits or optical member printing characterized by including the process performed.   Before the step of applying the liquid photosensitive resin composition, the method includes a step of winding and fixing a sheet-like support on a cylindrical support, and the liquid photosensitive resin composition is applied on the sheet-like support. The method for producing a laser engraving printing plate for printing an electronic circuit or an optical member according to claim 6, further comprising a step of cutting the printing original plate after the surface adjustment step and removing it from the cylindrical support.