JP4391260B2 - Cylindrical printing original plate with circumference adjustment layer - Google Patents

Description

  The present invention relates to the creation of relief images for flexographic printing plates by laser engraving, the formation of patterns for surface processing such as embossing, the formation of relief images for printing such as tiles, the pattern printing of conductors, semiconductors and insulators in the formation of electronic circuits, optical Pattern formation of functional materials such as anti-reflective coatings for parts, color filters, (near) infrared cut filters, and alignment films, base layers, light-emitting layers, and electronics in the manufacture of display elements such as liquid crystal displays or organic electroluminescent displays The present invention relates to a cylindrical printing original plate suitable for forming a coating layer / pattern for a transport layer and a sealing material layer, and a method for producing the same.

  Flexographic printing used for packaging materials such as cardboard, paper containers, paper bags, flexible packaging films, wallpaper materials, decorative materials such as decorative boards, and label printing has increased its specific gravity among various printing methods. For the production of the printing plate used for this, a photosensitive resin is usually used, and a liquid resin or a solid resin plate formed into a sheet shape is used, a photomask is placed on the photosensitive resin, and the mask is used. A method of irradiating light through the substrate to cause a crosslinking reaction and then washing off the non-crosslinked portion 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 light non-irradiated portion was washed away with a developing solution, and its adoption has been promoted due to the effect of improving the efficiency of printing plate production. However, this technique also requires exposure and development steps as in the conventional printing plate manufacturing method. Further, as a method capable of omitting the exposure and development steps, a method of forming a concavo-convex pattern by directly engraving a printing original plate by irradiating laser light has been proposed.

  When performing flexographic printing using a sheet-like printing plate, it is necessary to align the sheet-like printing plate on the plate cylinder of a printing press and fix it using a double-sided tape. In order to omit it, a cylindrical printing original plate in which a photosensitive resin layer is formed on a cylindrical support has been developed. However, the plate cylinder diameter of the printing press varies depending on the printing press, and the repeat length of the printed matter (repeated unit length of the printed matter: the circumferential length of the cylindrical printing plate) is also very different, so there are a wide variety of cylinders. In reality, it is necessary to prepare a cylindrical support. For this reason, a hard rubber is wound on a cylindrical support corresponding to a certain plate cylinder diameter, and processing such as cutting and polishing is performed to adjust the thickness according to the repeat length of the printed matter and to adjust the circumferential length of the cylindrical printing plate. Is generally done. Conventionally, the material used for matching the circumference of the cylindrical printing plate is a rubber-based material. In general, rubber secures mechanical strength by vulcanization treatment, and it takes much time for thermal crosslinking and stabilization of the crosslinked product in the vulcanization treatment. Therefore, the present situation is that a long time is required for the process of molding the rubber-based material with a certain thickness. Therefore, a system that can easily adjust the circumference of the cylindrical printing plate is desired.

A seamless sleeve printing plate structure in which a sleeve core layer, a cushion layer, a rigid layer and a seamless printing relief layer are arranged in this order is described in Patent Document 1 (Japanese Patent Laid-Open No. 2003-025749). However, in this patent, the cushion layer is wound around and fixed to the sleeve core layer via an adhesive, and the manufacturing process is not simple. There is no description about the layer which adjusts the perimeter of a printing plate.
Various cylindrical printing originals have been proposed so far. However, a material that can easily adjust the circumference has not been known.
JP 2003-025749 A

  An object of the present invention is to provide a cylindrical printing original plate having good plate thickness accuracy and dimensional accuracy and capable of easily adjusting the circumference.

The present inventors diligently studied and laminated on the cylindrical support (A) in the order of the peripheral length adjusting layer (B), the cushion layer (C), and the resin layer (D) capable of forming an uneven pattern on the surface. Among the circumference adjustment layer (B) and the resin layer (D), at least the circumference adjustment layer (B) is made of a cured photosensitive resin, and the circumference adjustment layer (B) thickness 0.01mm or less than 100mm, and I Shore D hardness der than 30 degrees of the peripheral length adjusting layer (B), the peripheral length adjusting layer (B) is a photosensitive resin having a bubble in the layer It can solve the above problems by using a cured product layer der Ru cylindrical printing original plate, thereby completing the present invention. That is, the technical idea of the present invention is to form at least the circumference adjusting layer (B) of the circumference adjusting layer (B) and the resin layer (D) by photocuring the photosensitive resin composition. . By using the photosensitive resin, it is possible to form a structure including the peripheral length adjusting layer (B) within an extremely short time. Furthermore, the cylindrical printing original plate corresponding to arbitrary circumferences can be manufactured by providing a circumference adjustment layer (B). In addition, since printing can be performed simply by installing a cylindrical printing plate having a concavo-convex pattern formed on the surface of the cylindrical printing original plate of the present invention on a printing press, a printing plate alignment process on a plate cylinder that has been conventionally performed The printing plate fixing process can be omitted, and the process can be greatly simplified.

The present invention is as follows.
1. A structure in which a circumferential length adjusting layer (B), a cushion layer (C), and a resin layer (D) capable of forming a concavo-convex pattern on the surface are laminated on a cylindrical support (A) in this order. Of the adjustment layer (B) and the resin layer (D), at least the circumference adjustment layer (B) is composed of a cured product obtained by photocuring the liquid photosensitive resin composition (a) by light irradiation at 20 ° C. The thickness of the length adjustment layer (B) is 0.01 mm or more and 100 mm or less, and the Shore D hardness of the circumference adjustment layer (B) is 30 degrees or more, and the circumference adjustment layer (B) is in the layer. A cylindrical printing original plate, which is a cured photosensitive resin layer having air bubbles.
2. The photosensitive resin composition (a) comprises at least one kind of binder (a), at least one kind of polymerizable unsaturated group-containing organic compound (b), and at least one kind of photopolymerization initiator (c). It is characterized by containing 1. The cylindrical printing original plate described in 1.
3. 1. The resin layer (D) is a photosensitive resin cured product layer (E) obtained by photocuring a photosensitive resin composition, and the photosensitive cured product layer is capable of laser engraving. 2. A cylindrical printing original plate according to any one of the above.
4). The photosensitive resin cured product layer (E) is a resin (d) having a number average molecular weight of 1000 or more and 200,000 or less, an organic compound (e) having a number average molecular weight of less than 1000 and having a polymerizable unsaturated group in the molecule, inorganic porous 2. A cured product layer containing the material (f) and obtained by photocuring a liquid photosensitive resin composition at 20 ° C. A cylindrical printing original plate capable of laser engraving as described in 1.
5. The inorganic porous body (f) has an average pore diameter of 1 nm to 1000 nm, a pore volume of 0.1 ml / g to 10 ml / g, a specific surface area of 10 m ² / g to 1500 m ² / g, and an oil absorption amount. 3. 10 ml / 100 g or more and 2000 ml / 100 g or less The cylindrical printing original plate as described.
6). 5. 20 wt% or more of the total amount of the organic compound (e) is at least one alicyclic or aromatic derivative. The cylindrical printing original plate described in 1.
7). Of the circumference adjustment layer (B), the resin layer (D), and the cushion layer (C), at least the circumference adjustment layer (B) is a seamless layer. To 6. A cylindrical printing original plate according to any one of the above.
8). A rigid film layer (F) having a thickness of 1 μm or more and 300 μm or less is further present between the cushion layer (C) and the resin layer (D), and the linear thermal expansion coefficient of the rigid film layer (F) is 1. It is -10 ppm / ° C. or more and 150 ppm / ° C. or less when measured in a temperature range of 20 ° C. to 80 ° C. using a measurement method (TMA). To 7. A cylindrical printing original plate according to any one of the above.
9. 1. The resin layer (D) is a photosensitive resin layer that can be photocured by a mask exposure method or a high energy beam scanning exposure method to form a latent image of an uneven pattern. 2. A cylindrical printing original plate according to any one of the above.
10. In the method for producing a cylindrical printing original plate, (i) a step of applying a liquid photosensitive resin composition (a) on a cylindrical support at 20 ° C. and laminating a photosensitive resin layer; (Iii) adjusting the film thickness of the obtained cured product layer, adjusting the film thickness to a thickness of 0.01 mm to 100 mm and a Shore D hardness of 30 degrees or more. (B) forming step, (iv) laminating the cushion layer (C) on the circumference adjusting layer, (v) resin layer (D) capable of forming an uneven pattern on the cushion layer (C) A step of heating the photosensitive resin layer for forming the circumference adjusting layer (B) to 60 to 250 ° C. to expand the expandable microcapsules existing inside the photosensitive resin layer, Before the step of curing the photosensitive resin layer by light irradiation It includes after,
A method for producing a cylindrical printing original plate, wherein the step of curing the photosensitive resin layer is performed in the air.
11. The resin layer (D) formed on the cushion layer (C) is a cured photosensitive resin layer (E) capable of forming a concavo-convex pattern by laser engraving, and the cured cured resin layer ( E) is a method of forming a photosensitive resin layer by applying a photosensitive resin composition (c) on the cushion layer (C), a step of irradiating the photosensitive resin layer with light and curing it, 9. A step of adjusting the film thickness of the cured product layer obtained is included. The manufacturing method of the cylindrical printing original plate as described in 1 ..
12 The step of forming the cushion layer (C) on the circumference adjustment layer (B) is (viii) the step of applying the photosensitive resin (ii) on the circumference adjustment layer (B) and laminating the photosensitive resin layer, (Ix) including a step of forming a cured product layer by irradiating the photosensitive resin layer with light, and (x) adjusting a film thickness of the obtained cured product layer to form a cushion layer (C). 10 characterized by 11. The manufacturing method of the cylindrical printing original plate in any one of.
13.3. To 6 . A laser engraving printing plate obtained by irradiating a laser beam onto the surface of a cylindrical flexographic printing plate capable of laser engraving according to any one of the above to form a concavo-convex pattern.
14.1. 2. A method of forming a concavo-convex pattern on the surface of the resin layer (D) using the cylindrical printing original plate according to any one of the above, wherein the photosensitive resin layer is irradiated with light by a mask exposure method or a high energy beam scanning exposure method and photocured A method for producing a cylindrical printing plate, comprising: a step of forming a latent image by a step; and a step of removing an uncured portion by a development process.

  The cylindrical printing original plate of the present invention has good plate thickness accuracy and dimensional accuracy, and can easily adjust the circumference.

Hereinafter, the present invention will be described in detail, particularly focusing on preferred embodiments thereof.
A feature of the present invention is that a layer for adjusting the circumference of a cylindrical printing plate can be easily formed using a photosensitive resin composition. The circumference of the printing plate varies widely depending on the printed matter to be produced. Conventionally, in order to adjust the circumferential length, a method in which a hard rubber is wound on a cylindrical support, and vulcanization cross-linking, surface polishing, and cross-linking stabilization processes are performed over a considerable period of time is generally used. It was. Alternatively, it was necessary to prepare and store a large number of types of cylindrical supports that match the circumference. The present invention has solved these problems all at once.

  In addition to the function of adjusting the peripheral length of the printing plate, the peripheral length adjusting layer of the present invention also has a function of smoothing irregularities on the surface of the cylindrical support. For example, in the case of a commonly used cylindrical support made of glass fiber reinforced plastic, the surface irregularities are extremely large, and a hard rubber is wound on this to produce a cylindrical support with rubber. The process of polishing the surface of the cylindrical support requires an additional work to increase the smoothness, which not only requires time but also has the disadvantage of significantly increasing the production cost. In the circumference adjusting layer of the present invention, particularly when prepared using a liquid photosensitive resin, the surface of the cylindrical support is polished because the followability to the irregularities on the surface of the cylindrical support is very good. There is no need.

  The cylindrical printing original plate of the present invention is a cylindrical printing original plate having a peripheral length adjusting layer (B), and a photosensitive resin composition is used for forming the peripheral length adjusting layer (B). The hardness of the cured product obtained by photocuring the photosensitive resin composition is 20 degrees or more, more preferably 30 degrees or more, and further preferably 40 degrees or more in Shore D hardness. If Shore D hardness is 20 degree | times or more, the dimensional stability of the thickness direction at the time of printing can fully be ensured.

  It is preferable that the thickness of the circumference adjusting layer (B) of the present invention can be arbitrarily changed. The photosensitive resin composition that can be used may be a photosensitive resin composition that is solid at 20 ° C., but it is liquid from the viewpoint that the thickness of the circumference adjusting layer (B) can be arbitrarily changed. The photosensitive resin composition is particularly preferred. A solvent may be contained in the liquid photosensitive resin composition, but since a solvent removal step is required, a solvent-free liquid photosensitive resin composition is more preferable. When the liquid photosensitive resin composition is used, a seamless layer having a uniform film thickness can be formed. The preferable viscosity of the liquid photosensitive resin composition is 10 Pa · s or more and 10 kPa · s or less, more preferably 500 Pa · s or more and 5 kPa · s or less at 20 ° C. In order to form a thick film, dripping may occur due to gravity and the film thickness may change, so the viscosity range as described above is preferable. Further, when the film thickness to be molded is very thin, it is desirable to keep the viscosity low. As a method of reducing the viscosity, a method of adding a solvent can also be used as a simple method.

  The method of forming the circumference adjusting layer (B) of the present invention includes a step of applying the photosensitive resin composition (a) on the cylindrical support (A), a step of photocuring by irradiating light, A step of adjusting the thickness of the obtained photosensitive resin cured product layer is included. The method for applying the photosensitive resin composition (A) on the cylindrical support (A) is not particularly limited, but is a spray coating method, a blade coating method, a gravure coating method, a reverse roller coating method, a kiss touch coating method. Commonly used coating methods such as a construction method and a high-pressure air knife coating method can be listed. It is effective for uniform application to rotate the cylindrical support (A) around the axis during application of the photosensitive resin composition. Furthermore, the light source used for photocuring the formed photosensitive resin layer is preferably one that generates a light beam including light of 200 nm to 450 nm. Although it does not specifically limit, a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a chemical lamp, a germicidal lamp, etc. can be mentioned. The light irradiation can be performed simultaneously with the application of the photosensitive resin composition, or the light irradiation may be performed after the application. The thickness of the photosensitive resin cured product layer obtained by light irradiation is adjusted by using a cutting tool such as a lathe tool, a cutting method using a rotating polishing wheel, or a polishing method using a polishing cloth. It can be implemented in combination. Of course, the treatment can be performed while rotating around the axis of the cylindrical support (A).

  Moreover, the surface of a cylindrical support body (A) can be processed, and adhesiveness with a circumference adjustment layer (B) can also be raised. For example, a method of forming a thin adhesive layer on the surface of the cylindrical support (A), a method of forming an adhesion improving primer layer, or a method of physical or chemical treatment can be used. Examples of the physical treatment method include a method of irradiating with a high energy beam such as plasma, light in a vacuum ultraviolet region, an electron beam or an ion beam, or exposing to an atmosphere of a high energy beam. As a method that can be easily carried out, a method of irradiating an excimer UV (wavelength 172 nm) lamp can be mentioned. Further, as a chemical treatment method, there is a method of oxidizing the cylindrical support surface with a chemical solution. Specific examples of the adhesion improving primer layer include forming a thin layer with a silane coupling agent, a titanium coupling agent, a silicone-based adhesion aid or the like.

  In the present invention, the seamless circumferential length adjusting layer (B) containing bubbles can be easily formed on the cylindrical support (A). By providing air bubbles in the circumference adjusting layer (B), the cylindrical printing original plate can be reduced in weight. The bubbles contained in the layer may be open cells, but closed cells are more preferable from the viewpoint of mechanical strength. Open cells can be formed by a method of mixing a gas such as air in the photosensitive resin composition, a method of mixing a compound that generates nitrogen by heat or light, and the like. The closed cells can be formed using hollow fine particles. Examples thereof include inorganic hollow fine particles such as hollow glass fine particles and hollow silica fine particles, or microcapsule-like organic fine particles. In particular, among organic fine particles, it is preferable to use a microcapsule having a thermal expansion property that expands when heated. Since this type of thermally expandable microcapsule contains a volatile organic liquid inside, when mixed with a photosensitive resin composition, it is possible to ensure a light transmittance that does not hinder photocurability. Therefore, by carrying out a combination of curing of the photosensitive resin by light irradiation and thermal expansion of the heat-expandable microcapsules by heating, photocuring with a thick film becomes possible. When hollow fine particles are mixed in the photosensitive resin composition, the mixture is generally clouded because there is a large difference in refractive index between the air layer inside and the photosensitive resin composition. However, even with such a white turbid resin, a thick-film photocured product can be obtained by repeatedly performing the process of coating in a thin film state and photocuring while coating.

  It describes about the case where the circumference adjustment layer (B) which contains a closed cell in a layer using the photosensitive resin composition containing the said thermally expansible microcapsule is produced. The thickness of the circumferential length adjusting layer (B) formed by thermal expansion is preferably 1.1 to 100 times, more preferably 1.1 to 50 times the thickness before the thermal expansion microcapsule is expanded. Range. If it is 1.1 times or more, the weight reduction of a circumference adjustment layer (B) can be ensured, and if it is 100 times or less, the mechanical strength of a circumference adjustment layer (B) can be obtained. The thickness of the circumference adjusting layer (B) is preferably observed using a scanning electron microscope or an optical microscope while exposing the cross section.

It is preferable that the average diameter of the bubbles having partition walls present in the circumference adjusting layer (B) is 0.5 μm or more and 500 μm or less. If it is 0.5 μm or more, the circumferential length adjusting layer (B) can be reduced in weight, and if it is 500 μm or less, mechanical properties can be secured even in the circumferential length adjusting layer (B) having a thickness of several mm. is there. It is preferable to observe the size of the bubbles in the circumference adjusting layer (B) using an optical microscope or a laser confocal microscope.
The average thickness of the partition walls is preferably 0.05 μm or more and 10 μm or less. If it is 0.05 μm or more, bubbles can be retained, and if it is 10 μm or less, it is possible to ensure weight reduction of the circumferential length adjusting layer (B). The thickness of the partition wall can be evaluated by cutting the circumference adjusting layer (B) and observing the cross section with a high-resolution scanning electron microscope.

  The thermally expandable microcapsule is a fine particle containing a thermoplastic elastomer as a partition and containing a volatile organic liquid therein, preferably 60 to 250 ° C., more preferably 100 to 200 ° C., and volume expansion. Examples of the thermoplastic elastomer usually used include polyvinylidene chloride, polyacrylonitrile, polymethyl methacrylate and the like. Examples of the volatile organic liquid include hydrocarbons such as butane, isobutane, butene, isobutene, pentane, isopentane, neopentane, hexane, and heptene. By using a thermally expandable microcapsule, closed cells having a relatively uniform particle diameter can be formed when thermally expanded. Moreover, the partition may be coated with inorganic fine particles. Examples of inorganic fine particles include silica, calcium carbonate, titanium oxide and the like.

A preferable density range of the circumferential length adjusting layer (B) is 0.1 g / cm ³ or more and 0.9 g / cm ³ or less, more preferably 0.3 g / cm ³ or more and 0.7 g / cm ³ or less. If it is 0.1 g / cm ³ or more, the mechanical strength of the circumference adjusting layer (B) can be ensured, and if it is 0.9 g / cm ³ or less, the weight of the circumference adjusting layer (B) can be reduced. Can be secured.

  When the photosensitive resin composition (a) contains a thermally expandable microcapsule, it is difficult to thermally expand the microcapsule if the photosensitive resin composition is completely photocured. Adjusting the amount of energy of light to be irradiated so that the photosensitive resin composition is in a semi-cured state, then performing heat treatment to expand the thermally expandable microcapsules, and further irradiating with light, the photosensitive resin composition The object is completely cured. Alternatively, when the content of the thermally expandable microcapsule is high, the photosensitive resin composition is thinly coated on the cylindrical support (A), and the microcapsule is thermally expanded, and then irradiated with light. By repeatedly performing the operation of completing photocuring, the circumferential length adjusting layer (B) having a predetermined thickness can be formed.

  In the step of thermally expanding the semi-cured photosensitive resin layer (g) containing the thermally expandable microcapsules formed on the cylindrical support (A), a certain distance from the cylindrical support (A) is set. The photosensitive resin layer (g) is rotated by rotating the cylindrical support (A) while heating the photosensitive resin layer (g) between the plate-like or roll-like object (h) placed apart. Is preferably passed as contacting the object (h) as a method for forming the circumference adjusting layer (B) having a uniform thickness. Examples of the heating method include a method of blowing hot air, a method of irradiating infrared rays, a method of heating a plate-shaped or roll-shaped object (h) using a heater, and the like, and these methods are used in combination. You can also Examples of a method for rapidly stopping foaming due to heating include a method of cooling by blowing cold air, or a method of contacting a cooling roll or a cooling plate.

  The photosensitive resin composition (a) for forming the circumference adjusting layer (B) of the present invention comprises at least one binder (a) and an organic compound having at least one polymerizable unsaturated group ( b) A compound having at least one photopolymerization initiator (c) is preferred. Moreover, it is preferable that it is liquid at 20 degreeC from a viewpoint of a moldability, and can form the seamless layer with a uniform film thickness. Further, when the film thickness to be molded is very thin, it is desirable to keep the viscosity low. As a method of reducing the viscosity, a method of adding a solvent is simple.

  A known polymer compound can be used as the binder (a). Specifically, rubber-based polymer compounds having rubber elasticity such as synthetic rubbers and thermoplastic elastomers, thermoplastic resins having a high elastic modulus such as a solid resin at 20 ° C, or polymerizable unsaturated groups in the molecule. Examples of preferable polymer compounds include resins that are liquid at 20 ° C., such as unsaturated polyurethane, unsaturated polyester, and liquid polybutadiene. As the rubber polymer compound, natural rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, polybutadiene rubber, polyisoprene rubber, ethylene propylene rubber, a polymer of monovinyl substituted aromatic hydrocarbon and a conjugated diene monomer are preferable. As the monovinyl substituted aromatic hydrocarbon monomer, styrene, α-methyl styrene, p-methyl styrene, p-methoxy styrene and the like are used. As the conjugated diene monomer, butadiene, isoprene and the like are used. Specific examples include styrene-butadiene block copolymers and styrene-isoprene block copolymers. Examples of the thermoplastic resin having a high elastic modulus include polycarbonate, polysulfone, polyethersulfone, polyetheretherketone, polyamide, polyamic acid, polyester, and polyphenylene ether. In the case of a solid resin at 20 ° C., those that can be dissolved in a solvent are particularly preferred. The preferable range of the number average molecular weight of the binder (a) is 1000 or more and 300,000 or less, more preferably 5000 or more and 100,000 or less, and still more preferably 7000 or more and 50,000 or less. The number average molecular weight of the present invention is a value measured by gel permeation chromatography (GPC method) and converted based on polystyrene having a known molecular weight.

Based on the total weight of the non-volatile components of the photosensitive resin composition (a), the binder (a) component is preferably in the range of 10 to 90 wt%, more preferably 20 to 80 wt%, still more preferably 30 to 69 wt%. It is.
The organic compound (b) having a polymerizable unsaturated group contained in the photosensitive resin composition (a) is a compound that undergoes a radical polymerization reaction, an addition polymerization reaction, and a ring-opening addition polymerization reaction, and a known compound may also be used. There is no particular limitation.

  As radical reactive compounds, olefins such as ethylene, propylene, styrene and divinylbenzene, acetylenes, (meth) acrylic acid and derivatives thereof, unsaturated nitriles such as haloolefins and acrylonitrile, (meth) acrylamide and derivatives thereof , Unsaturated dicarboxylic acids such as maleic anhydride, maleic acid, fumaric acid and their derivatives, vinyl acetates, N-vinylpyrrolidone, N-vinylcarbazole, etc. (Meth) acrylic acid and its derivatives are preferred examples. Examples of the derivative of the compound include alicyclic such as cycloalkyl-, bicycloalkyl-, cycloalkene-, bicycloalkene-, aromatic such as benzyl-, phenyl-, phenoxy-, fluorene-, alkyl-, halogen Alkyl-, alkoxyalkyl-, hydroxyalkyl-, aminoalkyl-, tetrahydrofurfuryl-, allyl-, glycidyl-, alkylene glycol-, polyoxyalkylene glycol-, (alkyl / allyloxy) polyalkylene glycol- and trimethylolpropane Examples thereof include esters of polyhydric alcohols such as polydimethylsiloxane and compounds having a polysiloxane structure such as polydiethylsiloxane. Moreover, you may be a heteroaromatic compound containing elements, such as nitrogen and sulfur.

  Examples of the polymerizable unsaturated group having addition polymerization reactivity include compounds having a cinnamoyl group, a thiol group, and an azide group. Further, polymerizable unsaturated groups having ring-opening addition reactivity include epoxy groups, oxetane groups, cyclic ester groups, dioxirane groups, spiroorthocarbonate groups, spiroorthoester groups, bicycloorthoester groups, cyclosiloxane groups, and cyclic imino groups. The compound which has an ether group etc. can be mentioned. Particularly useful compounds having epoxy groups As compounds having epoxy groups, compounds obtained by reacting various polyols such as diols and triols with epichlorohydrin, epoxy compounds obtained by reacting peroxy acids with ethylene bonds in the molecule, etc. Can be mentioned. Specifically, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene Glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A diglycidyl ether, hydrogenated bisphenol A Diglycidyl ether, bisphenol A Diglycidyl ether, polytetramethylene glycol diglycidyl ether, poly (propylene glycol adipate) diol diglycidyl ether, poly (ethylene glycol adipate) diol diglycidyl ether, poly (caprolactone) diol di of compounds with addition of lenoxide or propylene oxide Examples thereof include epoxy compounds such as glycidyl ether and epoxy-modified silicone oil (trade name “HF-105” manufactured by Shin-Etsu Chemical Co., Ltd.).

In order to increase the mechanical strength of the circumference adjusting layer (B) of the present invention, the organic compound (b) preferably has at least one alicyclic or aromatic derivative. In this case, the organic compound ( It is preferable that it is 20 wt% or more of the whole quantity of b), More preferably, it is 50 wt% or more. The aromatic derivative may be an aromatic compound having an element such as nitrogen or sulfur.
The ratio of the binder (a) and the organic compound (b) in the photosensitive resin composition (a) of the present invention is usually 5 to 200 weight percent of the organic compound (b) with respect to 100 weight parts of the binder (a). Part is preferable, and the range of 20 to 100 parts by weight is more preferable.

  As the photopolymerization initiator (c) contained in the photosensitive resin composition (a), a known photopolymerization initiator can be used. For example, known radical polymerization initiators such as aromatic ketones and benzoyl ethers can be used. For example, it can be used from among benzophenone, Michler ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylol benzoin methyl ether, α-methoxybenzoin methyl ether, 2,2-dimethoxyphenylacetophenone, etc. Can also be used in combination. In particular, when photocuring in the air, a combination of a hydrogen abstraction type photopolymerization initiator such as benzophenone and a decay type photopolymerization initiator such as 2,2-dimethoxyphenylacetophenone is particularly preferable. Furthermore, even if the same compound having a site that acts as a hydrogen abstraction type polymerization initiator and a site that acts as a decay type photopolymerization initiator in the molecule is used, an effect can be seen in atmospheric photocuring. Examples include photocationic polymerization initiators such as aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts that absorb light to generate an acid, and polymerization initiators that absorb light to generate a base. The addition amount of the polymerization initiator is preferably in the range of 0.01 to 10 wt% of the total amount of the binder (a) and the organic compound (b).

  Furthermore, the circumference adjusting layer (B) can also contain at least one type of reinforcing material selected from the group of organic fibers, inorganic fibers, organic fine particles, and inorganic fine particles. Examples of the organic fibers include woven or non-woven fabrics such as aramid fibers, polyimide fibers, and polyester fibers, or non-woven fabrics composed of nanometer-sized cellulose fibers produced by bacteria. In addition, examples of the inorganic fibers include woven fabrics and nonwoven fabrics such as glass fibers and carbon fibers. Examples of the organic fine particles include fine particles such as polyimide, polyamide, polyester, polymethyl methacrylate, polystyrene, and polydimethylsiloxane. Furthermore, examples of the inorganic fine particles include ceramic fine particles such as silica, zeolite, alumina, silicon nitride and boron nitride, and clay minerals. In addition, nanometer-sized fine particles can be used as the fine particles, and the shape of the fine particles may be any shape such as a spherical shape, a needle shape, a flake shape, and a polyhedral shape.

In the present invention, a laminate in which a cushion layer (C) having cushioning properties is formed between the circumferential length adjusting layer (B) and the resin layer (D) may be used.
The cushion layer (C) formed on the circumference adjustment layer (B) is a method of bonding a cushion tape with an adhesive layer to the circumference adjustment layer (B) with the adhesive layer facing, B) A method in which rubber is pasted on and cured by thermal crosslinking, a photosensitive resin composition layer is formed on the circumference adjusting layer (B), and a rubber elastic cushion layer is formed by photocuring. It can be formed by a method or the like. A simple method for forming a seamless cushion layer is a method of photocuring the photosensitive resin composition (A). Of course, as described in the place of the circumference adjusting layer (B), open cells and closed cells can be contained. When the cushion layer is formed of a cured product of the photosensitive resin composition, the hardness is preferably less than 20 degrees in Shore D hardness, and more preferably 60 degrees or less in Shore A hardness.

  The photosensitive resin composition (A) is not particularly limited as long as the photocured cured product has rubber elasticity. Those having a polymer component, a monomer component having a polymerizable unsaturated group, and a photopolymerization initiator are preferred. In particular, in the process of forming into a cylindrical shape, a photosensitive resin composition that can be photocured in the atmosphere and is liquid at 20 ° C. is preferable.

  In the present invention, when a cylindrical printing original plate capable of laser engraving is formed, it is generated in the laser engraving process by including the inorganic porous body (f) in the photosensitive resin cured material layer (E) capable of laser engraving. The liquid residue is absorbed and removed. The photosensitive resin composition (c) before photocuring is a resin (d) having a number average molecular weight of 1000 or more and 200,000 or less, an organic compound (e) having a number average molecular weight of less than 1000 and having a polymerizable unsaturated group in the molecule. And the inorganic porous material (f) is preferably contained.

  The type of the resin (d) may be an elastomer or a non-elastomer, and may be a solid polymer or a liquid polymer at 20 ° C. Moreover, when using a thermoplastic resin, 30 wt% or more of a polymer total weight is preferable, More preferably, it is 50 wt% or more, More preferably, it is 70 wt% or more. If the content of the thermoplastic resin is 30 wt% or more, the resin is sufficiently fluidized by laser beam irradiation and is absorbed by the inorganic porous body described later. However, when a resin having a softening temperature exceeding 300 ° C. is used, the temperature at which the resin is molded into a cylindrical shape is naturally high, and there is a concern that other organic substances may be denatured and decomposed by heat. It is preferable to apply and use it in a dissolved state.

In particular, it is preferable to use a liquid polymer at 20 ° C. as the resin (d) from the viewpoint of ease of processing into a cylindrical resin plate and ease of decomposition with respect to heat. When a liquid polymer is used as the resin (d) at 20 ° C., the formed photosensitive resin composition is also in a liquid state and can be molded at a low temperature.
The number average molecular weight of the resin (d) used in the present invention is preferably in the range of 1000 to 200,000. A more preferable range is 5000 to 100,000. When the number average molecular weight is in the range of 1,000 to 200,000, the mechanical strength of the printing original plate can be secured, and the resin can be sufficiently melted or decomposed during laser engraving. The number average molecular weight of the present invention is measured using gel permeation chromatography (GPC) and evaluated against a polystyrene preparation with a known molecular weight.

  As a technical feature of a preferred embodiment of the present invention, it is possible to absorb and remove the liquefied residue by laser beam irradiation using an inorganic porous material. As the cured photosensitive resin to be used, a resin that is easily liquefied or a resin that is easily decomposed is preferable. Examples of resins 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 in 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.

  Although it does not specifically limit as a thermoplastic elastomer used by this invention, SBS (polystyrene-polybutadiene-polystyrene), SIS (polystyrene-polyisoprene-polystyrene), SEBS (polystyrene-polyethylene / polybutylene-) which are styrenic thermoplastic elastomers. Polystyrene), olefin-based thermoplastic elastomers, urethane-based thermoplastic elastomers, ester-based thermoplastic elastomers, amide-based thermoplastic elastomers, silicone-based thermoplastic elastomers, and the like. In order to further improve the thermal decomposability, it is also possible to use a polymer in which an easily decomposable functional group such as a carbamoyl group or a carbonate group having a high decomposability is introduced into the main chain in the molecular skeleton. Further, it may be used by mixing with a polymer having higher thermal decomposability. Since the thermoplastic elastomer is fluidized by heating, it can be mixed with the inorganic porous material used in the present invention. A thermoplastic elastomer is a material that flows by heating and can be molded in the same manner as ordinary thermoplastics and exhibits rubber elasticity at room temperature. The molecular structure consists of soft segments such as polyether or rubber molecules, and hard segments that prevent plastic deformation at around room temperature, as with vulcanized rubber. The hard segments include frozen phase, crystalline phase, hydrogen bonding, and ionic crosslinking. There are various types.

Depending on the application of the printing plate, the type of thermoplastic elastomer can be selected. For example, urethane, ester, amide, and fluorine thermoplastic elastomers are preferred in fields where solvent resistance is required, and urethane, olefin, ester, and fluorine heat are required in fields where heat resistance is required. A plastic elastomer is preferred. Moreover, hardness can be changed greatly with the kind of thermoplastic elastomer. For normal printing plate applications, a relatively hard material is required for embossing applications that form surface irregularities of paper, film, and building materials in areas where the Shore A hardness is 20 to 75 degrees, and Shore D The hardness is in the range of 30 to 80 degrees.
The thermoplastic resin is not particularly limited as a non-elastomeric one, but is not limited to polyester resin, unsaturated polyester resin, polyamide resin, polyamideimide resin, polyurethane resin, unsaturated polyurethane resin, polysulfone resin, polyethersulfone resin, Polyimide resin, polycarbonate resin, wholly aromatic polyester resin and the like can be mentioned.

  The softening temperature of the thermoplastic resin of the present invention is preferably 50 ° C. or higher and 300 ° C. or lower. As a more preferable range, it is 80 degreeC or more and 250 degrees C or less, More preferably, they are 100 degreeC or more and 200 degrees C or less. If the softening temperature is 50 ° C. or higher, it can be handled as a solid at room temperature, and a sheet or cylinder processed can be handled without deformation. When the softening temperature is 300 ° C. or lower, it is not necessary to heat to a very high temperature when processing into a cylindrical shape, and it is not necessary to alter or decompose other compounds to be mixed. The measurement of the softening temperature of the present invention is defined by the first temperature at which the viscosity changes greatly (the slope of the viscosity curve changes) when the temperature is increased from room temperature using a dynamic viscoelasticity measuring device. To do.

  The resin (d) of the present invention may be a solvent-soluble resin. Specific examples include polysulfone resins, polyether sulfone resins, epoxy resins, alkyd resins, polyolefin resins, polyester resins, and the like.

  The resin (d) of the present invention usually does not have a highly reactive polymerizable unsaturated group, but may have a highly reactive polymerizable unsaturated group at the end or side chain of the molecular chain. I do not care. When a polymer having a highly reactive polymerizable unsaturated group is used, a printing original plate having extremely high mechanical strength can be produced. In particular, in polyurethane-based and polyester-based thermoplastic elastomers, it is possible to introduce a highly reactive polymerizable unsaturated group into the molecule relatively easily. 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. For example, it is possible to directly use a polymerizable unsaturated group introduced at the molecular end. Alternatively, a hydroxyl group, amino group, epoxy group, carboxyl group, acid anhydride group, ketone group, hydrazine residue can be used. A binder having a plurality of groups capable of binding to a reactive group having a molecular weight of about several thousand having a plurality of reactive groups such as an isocyanate group, an isothiocyanate group, a cyclic carbonate group, and an ester group (for example, a hydroxyl group or an amino group) Polyisocyanate, etc.) in the case of (2), reacting with an organic compound having a polymerizable unsaturated group and a group that reacts with the terminal binding group after the molecular weight is adjusted and converted to the terminal binding group. And a method such as a method of introducing a polymerizable unsaturated group at the terminal.

  The organic compound (e) is a compound having a radical or an unsaturated bond involved in an addition polymerization reaction, and the number average molecular weight is preferably less than 1000 in view of easiness of dilution with the resin (d). Preferred examples of the functional group having an unsaturated bond involved in the radical polymerization reaction include a vinyl group, an acetylene group, an acrylic group, a methacryl group, and an allyl group. The functional group having an unsaturated bond involved in the addition polymerization reaction includes a cinnamoyl group, a thiol group, an azide group, an epoxy group that undergoes a ring-opening addition reaction, an oxetane group, a cyclic ester group, a dioxirane group, a spiro ortho carbonate group, Examples include a spiro ortho ester group, a bicyclo ortho ester group, a cyclosiloxane group, and a cyclic imino ether group.

  Specific examples of the organic compound (e) 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, etc. Among them, (meth) acrylic acid and its derivatives are preferable examples from the viewpoints of abundant types, price, decomposability upon laser light irradiation, and the like. Examples of the derivative of the compound include alicyclic such as cycloalkyl-, bicycloalkyl-, cycloalkene-, bicycloalkene-, aromatic such as benzyl-, phenyl-, phenoxy-, fluorene-, alkyl-, halogen Alkyl-, alkoxyalkyl-, hydroxyalkyl-, aminoalkyl-, tetrahydrofurfuryl-, allyl-, glycidyl-, alkylene glycol-, polyoxyalkylene glycol-, (alkyl / allyloxy) polyalkylene glycol- and trimethylolpropane And esters of polyhydric alcohols such as Moreover, you may be a heteroaromatic compound containing elements, such as nitrogen and sulfur.

  In addition, as a compound having an epoxy group that undergoes a ring-opening addition reaction, a compound obtained by reacting a polyol such as various diols or triols with epichlorohydrin, an epoxy compound obtained by reacting a peracid with an ethylene bond in the molecule, etc. Can be mentioned. Specifically, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene Glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A diglycidyl ether, hydrogenated bisphenol A Diglycidyl ether, bisphenol A Diglycidyl ether, polytetramethylene glycol diglycidyl ether, poly (propylene glycol adipate) diol diglycidyl ether, poly (ethylene glycol adipate) diol diglycidyl ether, poly (caprolactone) diol di of compounds with addition of lenoxide or propylene oxide A glycidyl ether etc. can be mentioned.

  In this invention, the organic compound (e) which has these polymerizable unsaturated bonds can select the 1 type (s) or 2 or more types according to the objective. For example, when used as a printing plate, at least one long-chain aliphatic, alicyclic or aromatic derivative is used as the organic compound (e) used to suppress swelling with respect to an organic solvent such as alcohol or ester which is a solvent for printing ink. It is preferable to have the above.

In order to increase the mechanical strength of the printing original plate obtained from the resin composition of the present invention, the organic compound (e) preferably has at least one alicyclic or aromatic derivative, and in this case, the organic compound It is preferable that it is 20 wt% or more of the whole quantity of (e), More preferably, it is 50 wt% or more. The aromatic derivative may be an aromatic compound having an element such as nitrogen or sulfur.
In order to increase the rebound resilience of the printing plate, for example, a methacrylic monomer as described in JP-A-7-239548 can be used, or it can be selected using the technical knowledge of known photosensitive resins for printing.

  The inorganic porous material (f) is an inorganic particle having fine pores or fine voids in the particles. It is an additive for absorbing and removing viscous liquid residue generated in a large amount in laser engraving, and also has an effect of preventing tackiness of the plate surface. In addition to being not melted even when irradiated with a laser, the material is not particularly limited. However, when photocuring is performed using ultraviolet rays or visible light, the addition of black fine particles allows light transmission into the photosensitive resin composition. Therefore, black fine particles such as carbon black, activated carbon and graphite are not suitable as the inorganic porous material (f) of the present invention.

  The pore volume of the inorganic porous material (f) 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.

  The average pore diameter of the inorganic porous material (f) 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 since the liquid debris is viscous, it is estimated that it is difficult to enter the micropores. The average pore diameter of 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 present invention preferably employs a resin having a relatively low molecular weight so that it can be easily cleaved by laser irradiation. Therefore, a large amount of low molecular weight monomers and oligomers are generated when the molecule is cleaved. The greatest feature lies in the introduction of a new concept that does not exist at all in the conventional technical idea that the removal of scum is performed using a porous inorganic absorbent. In order to effectively remove viscous liquid residue, physical properties such as number average particle diameter, specific surface area, average pore diameter, pore volume, loss on ignition, and oil supply amount of the inorganic porous material are important factors. .

  The inorganic porous body (f) preferably has a number average particle diameter of 0.1 to 100 μm. When a material having a number smaller than the number average particle size is used, dust is likely to fly when the original plate obtained from the resin composition of the present invention is engraved with a laser, contaminating the engraving apparatus, resin (d) and organic When mixing with the compound (e), an increase in viscosity, entrainment of bubbles, generation of dust, etc. are likely to occur. On the other hand, when a particle having a size larger than the above-mentioned number average particle size is used, the relief image tends to be defective when laser engraved, and the fineness of the printed matter tends to be impaired. 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 inorganic porous material used in the present invention can be measured using a laser scattering particle size distribution measuring device.

A new concept of porosity is introduced to evaluate the properties of porous bodies. The porosity is the ratio of the specific surface area P to the surface area S per unit weight calculated from the average particle diameter D (unit: μm) and the density d (unit: g / cm ³ ) of the substance constituting the particles, It is defined by P / S. The surface area per particle is πD ² × 10 ⁻¹² (unit: m ² ), and the weight of one particle is (πD ³ d / 6) × 10 ⁻¹² (unit: g). The surface area S per weight is S = 6 / (Dd) (unit: m ² / g). As the specific surface area P, a value measured by adsorbing nitrogen molecules on the surface is used.

The porosity of the inorganic porous body (f) is preferably 20 or more, more preferably 50 or more, and still more preferably 100 or more. If the porosity is 20 or more, it is effective for removing adsorbed liquid residue. Since the specific surface area P increases as the particle diameter decreases, the specific surface area alone is not suitable as an index indicating the characteristics of the porous body. Therefore, considering the particle size, porosity was taken as a dimensionless index. For example, carbon black widely used as a reinforcing material such as rubber has a very large specific surface area of 150 m ² / g to 20 m ² / g, but the average particle diameter is extremely small, usually 10 nm to 100 nm. Therefore, when the porosity is calculated by setting the density to 2.25 g / cm ³ of graphite, it becomes a value in the range of 0.8 to 1.0, and is estimated to be a nonporous body having no porous structure inside the particle. The Since carbon black is generally known to have a graphite structure, the value of graphite was used for the density. On the other hand, the porosity of the porous silica used in the present invention is a high value well over 500.

The inorganic porous material of the present invention preferably has a specific specific surface area and an oil absorption amount in order to obtain better adsorbability.
The range of the specific surface area of the inorganic porous body (f) 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. If the specific surface area is 10 m ² / g or more, removal of liquid residue during laser engraving is sufficient, and if it is 1500 m ² / g or less, the 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 a BET type | formula from the adsorption isotherm of nitrogen in -196 degreeC.

  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. The preferred range of the oil absorption amount of the inorganic 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, more preferably 200 ml / 100 g or more and 800 ml / 100 g or less. . If the oil absorption is 10 ml / 100 g or more, there is an effect in removing liquid debris generated during laser engraving, and if it is 2000 ml / 100 g or less, the mechanical strength of the inorganic porous material can be sufficiently secured. The oil absorption is preferably measured according to JIS-K5101.

The inorganic porous material (f) 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 body is not particularly limited, and spherical, flat, needle-shaped, amorphous, or particles having protrusions on the surface can be used. Among these, spherical particles are particularly preferable from the viewpoint of wear resistance of the printing plate. It is also possible to use particles having hollow inside particles, 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, mesoporous molecular sieve, porous alumina, porous glass, etc. can be mentioned.

In addition, since pore diameters cannot be defined for those having a gap of several nm to 100 nm between layers, such as a layered clay compound, in the present invention, voids existing between layers, that is, surface spacing, are defined as pore diameters. . The total amount of space existing between the layers is defined as the pore volume. These values can be obtained from the nitrogen adsorption isotherm.
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 maximum value D ₁ of the circle that completely enters the projection figure when the particle is projected to the minimum value D ₂ of the circle that completely enters the projection 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, it is preferable to take a picture at a magnification at which at least 100 particles enter the monitor screen. The D ₁ and D ₂ are measured based on a photograph, but it is preferable to process the photograph using a digitizing device such as a scanner and then process the data using image analysis software.

Moreover, the surface of the inorganic porous body can be coated with a silane coupling agent, a titanium coupling agent, or other organic compounds, and subjected to a surface modification treatment to make particles more hydrophilic or hydrophobic.
In the present invention, these inorganic porous bodies (f) can be selected from one type or two or more types, and by adding the inorganic porous body (f), generation of liquid debris during laser engraving and relief Improvements such as tack prevention of the printing plate are effectively performed.

The ratio of the resin (d), the organic compound (e), and the inorganic porous body (f) in the photosensitive resin composition of the present invention is usually the organic compound (e) with respect to 100 parts by weight of the resin (d). Is preferably 5 to 200 parts by weight, and more preferably 20 to 100 parts by weight. The inorganic porous material (f) is preferably 1 to 100 parts by weight, and more preferably 2 to 50 parts by weight. A more preferable range is 2 to 20 parts by weight.
If the ratio of the organic compound (e) is within the above range, it is easy to balance the hardness and tensile strength / elongation of the printing plate to be obtained, shrinkage at the time of cross-linking curing is reduced, and thickness accuracy is ensured. Can do.
Further, if the amount of the inorganic porous body (f) is in the above range, the effect of preventing the tackiness of the plate surface and the effect of suppressing the generation of engraving liquid debris when laser engraving is sufficiently exhibited, and the printing plate The mechanical strength can be ensured, and transparency can be maintained. Moreover, especially when using as a flexographic plate, it can suppress so that hardness may not become high too much. When a photosensitive resin composition is cured using light, particularly ultraviolet rays, to prepare a laser engraving printing original plate, light transmittance affects the curing reaction. Therefore, it is effective to use a material having a refractive index close to that of the photosensitive resin composition.

  The photosensitive resin composition (c) of the present invention is crosslinked by light irradiation to develop physical properties as a printing plate, and a polymerization initiator can be added at that time. The polymerization initiator can be selected from those commonly used. For example, initiators for radical polymerization, cationic polymerization, and anionic polymerization exemplified in “Polymer Data Handbook-Basics” edited by the Society of Polymer Science, published in 1986 by Fufukan. Etc. can be used. In addition, crosslinking by photopolymerization using a photopolymerization initiator is useful as a method for producing a printing original plate with good productivity while maintaining the storage stability of the resin composition of the present invention, and is used in that case. Known initiators can also be used, for example, benzoin alkyl ethers such as benzoin and benzoin ethyl ether, 2-hydroxy-2-methylpropiophenone, 4′-isopropyl-2-hydroxy-2-methylpropiophenone. Acetophenones such as 2,2-dimethoxy-2-phenylacetophenone and diethoxyacetophenone; 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1- ON, methyl phenylglyoxylate, benzophenone, benzyl, In addition to photo radical polymerization initiators such as acetyl, diphenyl sulfide, eosin, thionine, and anthraquinones, photo cationic polymerization starts such as aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts that absorb light and generate acids. And a polymerization initiator that absorbs light and generates a base. The addition amount of the polymerization initiator is preferably in the range of 0.01 to 10 wt% of the total amount of the resin (d) and the organic compound (e).

In addition, a polymerization inhibitor, an ultraviolet absorber, a dye, a pigment, a lubricant, a surfactant, a plasticizer, a fragrance and the like may be added to the photosensitive resin composition (c) of the present invention depending on the purpose and purpose. it can.
An existing resin molding method can be used as the method for molding the photosensitive resin composition (c) of the present invention into a cylindrical shape. 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, and adjusting the thickness by calendering with a roll can be exemplified. In that case, it is also possible to perform the 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. In addition, a cylindrical printing original plate in which a laser light source for laser engraving is incorporated in an apparatus that irradiates light and cures and solidifies the photosensitive resin composition after coating the photosensitive resin composition on a cylindrical support. A printing plate can also be formed using a molding / engraving device. When such an apparatus is used, it is possible to form a printing plate by laser engraving immediately after forming a cylindrical printing original plate, which is considered to be a conventional rubber sleeve that required a period of several weeks for molding processing. Short time machining can be realized. In the step of producing the cylindrical printing original plate, the cylindrical printing original plate can be produced in a very short time by using the photosensitive resin composition.

  The cylindrical support (A) used in the present invention may be rigid or flexible, but the rigid cylindrical support is more stable in the printing process at a higher speed. To preferred. The role of the cylindrical support used in the present invention 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 a liquid crystal resin made of an aromatic polyester resin, a wholly aromatic polyamide resin, an epoxy resin, and a metal. Further, these resins can be laminated and used.

  Examples of a method for reducing the linear thermal expansion coefficient of the cylindrical support 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. it can. 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. In addition, porous fine particles, fine particles having cavities inside, microcapsule particles, and layered compound particles in which a low molecular compound intercalates can be used. In particular, organic products such as alumina, silica, titanium oxide, zeolite and other metal oxide fine particles, latex fine particles made of polystyrene / polybutadiene copolymer, highly crystalline cellulose, organically produced organic crystals such as highly crystalline cellulose nanofibers System fine particles, fibers and the like are useful. Materials such as fiber reinforced plastic (FRP) are particularly useful as cylindrical supports.

  By performing a physical and chemical treatment on the surface of the cylindrical support (A) used in the present invention, the adhesion with the circumferential length adjusting layer (B) can be improved. Similarly, the adhesion between the circumference adjusting layer (B) and the photosensitive resin cured product layer (E) capable of laser engraving 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. The chemical treatment method includes a strong acid / strong alkali treatment method, an oxidant treatment method, a coupling agent treatment method, and the like.

  The molded photosensitive resin composition (c) is cross-linked by irradiation with light or an electron beam to form a printing original plate capable of laser engraving. Moreover, it can bridge | crosslink by irradiation of light or an electron beam, shape | molding. The method of crosslinking using light is preferable because it has advantages such as simple equipment and high thickness accuracy. Examples of the light source used for curing include a high-pressure mercury lamp, an ultra-high pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, and a xenon lamp, and the curing can be performed by other known methods. Moreover, you may irradiate the light of a several kind of light source. When the photosensitive resin composition is cured with light, the surface may be covered with a transparent cover film and irradiated with light in a state where oxygen is blocked. The cover film can also be used to protect the surface of the printing original plate. However, it is peeled off during laser engraving. The atmosphere in which the photosensitive resin composition layer is irradiated with light is preferably a gas atmosphere, particularly an air atmosphere. This is because there is no need to install a cover film covering mechanism for blocking oxygen, an oxygen deficiency preventing mechanism when using an inert gas, or the like.

In the present invention, a rigid film layer (F) having a thickness of 1 μm or more and 300 μm or less may exist between the cushion layer (C) and the resin layer (D). A preferable range of the linear thermal expansion coefficient of the rigid film layer (F) is −10 ppm / ° C. or more and 150 ppm / ° C. or less when measured in a temperature range of 20 ° C. to 80 ° C. using a thermomechanical measurement method (TMA method). More preferably, it is 0 ppm / ° C. or more and 100 ppm / ° C. or less.
If the linear thermal expansion coefficient is within this range, an effect can be seen in suppressing ink adhesion failure of fine lines and fine letters during printing.
The thickness of the photosensitive resin cured product layer (E) capable of laser engraving may be arbitrarily set depending on the purpose of use, but when used as a printing plate, it is preferably in the range of 0.1 to 7 mm. is there. In some cases, a plurality of materials having different compositions may be stacked.

  The resin layer (D) used in the present invention has a mask exposure method or a high energy beam scanning exposure method, and a portion irradiated with light is photocured to form a latent image, and an uncured portion is formed by a subsequent development process. It may be a photosensitive resin layer to be removed. Also, a thin layer containing a black pigment such as carbon black called a black layer is formed on the surface of the photosensitive resin layer, and then a pattern is formed using a near infrared laser, and this pattern is used as an exposure mask. You can also. In the development step, a developer in which the uncured resin is dissolved or dispersed can be used, and a heat development method in which the developer is melted with heat and sucked with a nonwoven fabric without using the developer can be used. The mask exposure method is a method in which a photosensitive resin is irradiated with a light beam including light in a wavelength region of 200 nm to 450 nm through a negative film having a light shielding pattern. The high energy beam scanning exposure method is a method of irradiating a photosensitive resin by scanning a beam energy beam such as an ultraviolet laser beam or an electron beam using an optical system such as a galvanometer mirror or an electron lens.

  The circumference adjusting layer (B) of the present invention is formed by photocrosslinking and curing a photosensitive resin composition. Therefore, a three-dimensional cross-linked structure is formed by the reaction of the polymerizable unsaturated group of the organic compound (b) or the polymerizable unsaturated group of the binder (a) with the organic compound (b). It becomes insoluble in organic, aromatic, etheric, alcoholic and halogenated solvents. This reaction occurs between the organic compounds (b), between the binders (a), or between the binder (a) and the organic compound (b), and the polymerizable unsaturated group is consumed. In addition, when the photopolymerization initiator is used for crosslinking and curing, the photopolymerization initiator is decomposed by light. Therefore, the cross-linked cured product is extracted with a solvent, and mass-separated by GC-MS (gas chromatography). Analysis method), LC-MS method (method for mass spectrometry of those separated by liquid chromatography), GPC-MS method (method for separation and mass spectrometry by gel permeation chromatography), LC-NMR method (liquid chromatography) By analyzing using the method of analyzing the product separated in (1) by nuclear magnetic resonance spectrum, unreacted photopolymerization initiator and decomposition products can be identified. Furthermore, by using the GPC-MS method, LC-MS method, and GPC-NMR method, the unreacted binder (a), the unreacted organic compound (b), and the polymerizable unsaturated group in the solvent extract are changed. Relatively low molecular weight products obtained by reaction can also be identified from analysis of solvent extracts. For the high molecular weight component insoluble in the solvent in which the three-dimensional cross-linked structure is formed, by using the pyrolysis GC-MS method, the site formed by the reaction of the polymerizable unsaturated group is formed as a component constituting the high molecular weight body. It is possible to verify whether it exists. For example, it can be estimated from the mass spectrometry spectrum pattern that there is a site where a polymerizable unsaturated group such as a methacrylate group, an acrylate group, or a vinyl group has reacted. The pyrolysis GC-MS method is a method in which a sample is thermally decomposed and a generated gas component is separated by gas chromatography and then mass spectrometry is performed. The decomposition product derived from the photopolymerization initiator and the unreacted photopolymerization initiator are detected together with the unreacted polymerizable unsaturated group or the site obtained by the reaction of the polymerizable unsaturated group in the crosslinked cured product. Then, it can be concluded that the photosensitive resin composition was obtained by photocrosslinking and curing.

  Components can be analyzed for the cushion layer (C), the photosensitive resin cured product layer (E), and the resin layer (D) by the same method. Furthermore, the amount of inorganic porous fine particles present in the crosslinked cured product can be obtained by heating the crosslinked cured product in the air to burn off the organic component and measuring the weight of the residue. In addition, the presence of inorganic porous fine particles in the residue is due to morphological observation with a field emission type high resolution scanning electron microscope, particle size distribution with a laser scattering type particle size distribution measuring device, and nitrogen adsorption method. It can be identified from the measurement of pore volume, pore diameter distribution and specific surface area.

  In laser engraving, a relief image is created on an original by operating a laser device using a computer as an image to be formed as digital data. Any laser may be used for the laser engraving as long as the original plate includes a wavelength having absorption. However, in order to perform engraving at a high speed, a laser with a high output is desirable. A laser having an oscillation wavelength in the infrared or near-infrared region, such as a YAG laser, a semiconductor laser, or a fiber laser, is preferable. 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. A laser having an extremely high peak output such as a femtosecond laser can also be used. The laser may be continuous irradiation or pulse irradiation. In general, since resin has absorption in the vicinity of 10 μm of a carbon dioxide laser, it is not essential to add a component that assists in absorption of laser light. YAG lasers, semiconductor lasers, and fiber lasers have an oscillation wavelength around 1 μm, but there are not many organic substances that absorb light in this wavelength region. In that case, it is necessary to add dyes and pigments, which are components that assist in the absorption of these. Examples of such dyes include poly (substituted) phthalocyanine compounds and metal-containing phthalocyanine compounds; cyanine compounds; squarylium dyes; chalcogenopyrylarylidene dyes; chloronium 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, and iron oxide, metal powders such as iron, aluminum, copper, and zinc, and Si, Mg , P, Co, Ni, Y and the like doped. These dyes and pigments may be used alone, in combination of a plurality, or in any form such as a multilayer structure. However, when the photosensitive resin composition is cured using ultraviolet rays or visible light, it is preferable to keep the amount of the dye or pigment that is absorbed in the light beam region used low in order to cure the interior of the printing original plate.

Laser engraving is carried out in an oxygen-containing gas, generally in the presence of air or an air stream, but can also be carried out in the presence of carbon dioxide or nitrogen gas. After engraving is finished, the powdery or liquid substance slightly generated on the relief printing plate surface is washed with an appropriate method such as water containing a solvent or a surfactant, or a water-based cleaning agent is irradiated by a high-pressure spray or the like. Alternatively, it may be removed using a method of irradiating high-pressure steam.
The original plate of the present invention is a relief image for printing plates, stamps and seals, design rolls for embossing, relief images for patterning insulators, resistors and conductor pastes used in the production of electronic components, and ceramic mold products. It can be applied to various uses such as relief images, relief images for displays such as advertisements and display boards, and prototypes / mothers of various molded products.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not restrict | limited by these.
(1) Laser engraving Laser engraving is performed using a carbon dioxide laser engraving machine (trademark “ZED-mini-1000” manufactured by ZED, UK), and the engraving pattern is a halftone dot, a line drawing of 500 μm wide convex lines, And the pattern containing the 500 micrometers width | variety white line was created and implemented. If the engraving depth is set to be large, the area of the top portion of the fine halftone dot pattern cannot be secured, and the shape is broken and unclear, so the engraving depth is set to 0.55 mm.

(2) Number of residue wiping off and residue remaining rate After laser engraving, the residue on the relief printing plate was wiped off using a nonwoven fabric impregnated with ethanol or acetone (trademark “BEMCOT M-3” manufactured by Asahi Kasei Corporation). The weights of the printing original plate before laser engraving, the printing plate immediately after laser engraving, and the relief printing plate after wiping were measured, and the residue rate at the time of engraving was determined by the formula (1).
(Weight of plate immediately after engraving-Weight of plate after wiping) ÷ (Weight of original plate before engraving-Weight of plate after wiping) x 100
(1)
The residue rate of the excellent printing plate is 15 wt% or less, preferably 10 wt% or less.
After the residue remaining on the relief was removed, post-exposure was performed by irradiating the printing plate surface with ultraviolet rays. The light used for post-exposure was ultraviolet fluorescent lamp (chemical lamp, center wavelength: 370 nm) and germicidal lamp (germisidal lamp, center wavelength: 253 nm).

(3) Shape of halftone dot portion The shape of the halftone dot portion having an area ratio of about 10% at 80 lpi (Lines per inch) was observed with an electron microscope at a magnification of 200 to 500 times. In the case where the halftone dot is conical or pseudo-conical (a divergent shape obtained by cutting the vicinity of the apex of the cone with a plane parallel to the bottom of the cone), the printing plate is good.

(4) Pore volume, average pore diameter, and specific surface area of porous body and nonporous body 2 g of porous body or nonporous body was taken in a sample tube, and conditions of 150 ° C. and 1.3 Pa or less in a pretreatment device And dried under reduced pressure for 12 hours. The pore volume, average pore diameter, and specific surface area of the dried porous body or non-porous body were measured by adsorbing nitrogen gas in a liquid nitrogen temperature atmosphere using Autosoap 3MP (trademark) manufactured by Cantachrome, USA. Measured. Specifically, the specific surface area was calculated based on the BET equation. The pore volume and average pore diameter were calculated based on a pore distribution analysis method called BJH (Brrett-Joyner-Halenda) method, assuming a cylindrical model from the adsorption isotherm at the time of nitrogen desorption.

(5) Loss on ignition of porous body and nonporous body Record the weight of the porous body or nonporous body for measurement. Next, the measurement sample was placed in a high-temperature electric furnace (FG31 type; manufactured by Yamato Kagaku Co., Ltd., Japan) and treated for 2 hours in an air atmosphere at 950 ° C. The change in weight after treatment was defined as loss on ignition.

(6) Standard deviation in particle size distribution of porous body and nonporous body The particle size distribution of the porous body and nonporous body was measured by a laser diffraction type particle size distribution analyzer (SALD-2000J type; Japan, (Manufactured by Shimadzu Corporation). According to the specification of the apparatus, it is described in the catalog that a particle size range from 0.03 μm to 500 μm can be measured. Methyl alcohol was used as a dispersion medium, and ultrasonic waves were applied for about 2 minutes to disperse the particles to prepare a measurement solution.

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

(8) Measurement of number average molecular weight The number average molecular weights of the resin (d) and the organic compound (e) were determined by conversion with polystyrene having a known molecular weight using a gel permeation chromatography method (GPC method). Using a high-speed GPC device (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 the detector, for the resin (d), an ultraviolet absorption detector was used, and 254 nm light was used as monitor light. The organic compound (e) was detected using a parallax refractometer. Resins (d) and organic compounds (e) used in Examples , Comparative Examples and Reference Examples of the present invention have a polydispersity (Mw / Mn) determined by GPC method greater than 1.1. Therefore, the number average molecular weight Mn obtained by the GPC method was adopted.

(9) Measurement of the number of polymerizable unsaturated groups The average number of polymerizable unsaturated groups present in the molecule of the synthesized resin (d) was obtained by removing unreacted low-molecular components using liquid chromatography. Thereafter, molecular structure analysis was performed using a nuclear magnetic resonance spectrum method (NMR method).

(10) Measurement of Shore D Hardness The Shore D hardness of the circumference adjusting layer (B) was measured using a trademark “GS-720G Type D” manufactured by Teclock Corporation. The Shore D hardness of the circumferential length adjusting layer (B) formed on the cylindrical support (A) was measured while being cylindrical. The weight of the weight used for the measurement was 8 kg.
Resins (a) to (c) were produced as the resin (d) in the following Production Examples 1 to 3.

(Production Example 1)
A 1 L separable flask equipped with a thermometer, a stirrer, and a refluxer is a polycarbonate diol manufactured by Asahi Kasei Corporation. Trademark “PCDL L4672” (number average molecular weight 1990, OH number 56.4) 447.24 g and tolylene diisocyanate After adding 30.83 g and reacting at 80 ° C. for about 3 hours, 14.83 g of 2-methacryloyloxyisocyanate was added and further reacted for about 3 hours, and the terminal was a methacrylic group (intramolecular polymerization). A resin (A) having a number average molecular weight of about 10,000 having an average of about 2 unsaturated unsaturated groups per molecule) was produced. This resin was in the shape of a syrup at 20 ° C., flowed when an external force was applied, and did not recover its original shape even when the external force was removed.

(Production Example 2)
A 1 L separable flask equipped with a thermometer, a stirrer, and a refluxer is a polycarbonate diol manufactured by Asahi Kasei Corporation. Trademark “PCDL L4672” (number average molecular weight 1990, OH number 56.4) 447.24 g and tolylene diisocyanate After adding 30.83 g and reacting at 80 ° C. for about 3 hours, adding 7.42 g of 2-methacryloyloxyisocyanate and further reacting for about 3 hours, the terminal is a methacrylic group (intramolecular polymerization). A resin (I) having a number average molecular weight of about 10,000 having an average of about 1 unsaturated unsaturated group per molecule) was produced. This resin was in the shape of a syrup at 20 ° C., flowed when an external force was applied, and did not recover its original shape even when the external force was removed.

(Production Example 3)
A 1-L separable flask equipped with a thermometer, a stirrer, and a refluxer is a polycarbonate diol manufactured by Asahi Kasei Corporation. After adding 12.53 g and reacting at 80 ° C. for about 3 hours, 47.77 g of 2-methacryloyloxyisocyanate was added and further reacted for about 3 hours, and the terminal was a methacryl group (polymerization within the molecule). A resin (c) having a number average molecular weight of about 3000 having an average of about 2 unsaturated unsaturated groups per molecule) was produced. This resin was in the shape of a syrup at 20 ° C., flowed when an external force was applied, and did not recover its original shape even when the external force was removed.

( Reference Examples 1-5, Examples 6-7)
(Formation of circumference adjustment layer)
When there is an air cylinder with an outer shape of 213.384 mm and the circumference of the printing plate is designed to be 700 mm, the thickness of the circumference adjustment layer is determined by calculating backward from the thickness of the material used. For example, the thickness of the photosensitive resin cured product layer capable of laser engraving is 1.14 mm, the thickness of the cushion tape having the adhesive layer on both sides is 0.55 mm (the thickness of the adhesive layer is 25 μm on one side), If the thickness of the cylindrical support made of glass fiber reinforced plastic is designed to be 2.00 mm, the set value of the thickness of the circumferential length adjusting layer is 1.026 mm. On a cylindrical support made of glass fiber reinforced plastic having an inner diameter of 213.384 mm, a width of 300 mm, and a thickness of 2.00 mm, a liquid photosensitive resin (trade name “APR-G-42” manufactured by Asahi Kasei Chemicals Corporation) at 20 ° C. It was applied at a thickness of about 1.1 mm using a doctor blade, and then light from a metal halide lamp (trade name “M056-L21” manufactured by Eye Graphics Co., Ltd.) was 4000 mJ / cm ² (UV meter (manufactured by Oak Manufacturing Co., Ltd., Trademark “UV-M02”) and a filter (trade name “UV-35-APR filter” manufactured by Oak Seisakusho Co., Ltd., a value obtained by integrating the illuminance with time) were irradiated to obtain a cured photosensitive resin layer. The lamp illuminance on the surface of the photosensitive resin composition layer was measured using a UV meter (trade name “UV-M02” manufactured by Oak Manufacturing Co., Ltd.). Lamp illuminance measured using a UV-35-APR filter that transmits light in the vicinity of a wavelength of 350 nm is 100 mW / cm ² , a filter that transmits light in the vicinity of a wavelength of 250 nm (trademark “UV-25 filter, manufactured by Oak Manufacturing Co., Ltd.”). The lamp illuminance measured using “)” was 14 mW / cm ² . Then, it cut using the cemented carbide bite so that thickness might be set to 1.026 mm, and obtained the circumference adjustment layer ((alpha)). APR-G-42 is a resin containing an unsaturated polyurethane resin, an organic compound having several kinds of polymerizable unsaturated groups, and a photopolymerization initiator.

  In addition, 99 parts by weight of the liquid photosensitive resin composition (trade name “APR-G-42” manufactured by Asahi Kasei Chemicals Co., Ltd.), a thermally expandable capsule (manufactured by Matsumoto Yushi Seiyaku Co., Ltd., trademark “Matsumoto Microsphere F-30VS”). 1 part by weight of an optimum foaming temperature of 110 to 120 ° C. and a dry weight) was mixed to obtain a photosensitive resin composition (D).

A predetermined amount of the photosensitive resin composition is placed on a cylindrical support made of glass fiber reinforced plastic, which is a cylindrical support, and the sleeve is rotated about a central axis. It was possible to obtain a seamless resin layer by applying uniformly using the blade coating method. The thickness of the obtained resin layer was 50 μm. Thereafter, the resin layer was irradiated with 100 mJ / cm ² of light from a chemical lamp (energy amount integrated using a UV meter and a UV-35-APR filter) to obtain a cured product in a semi-cured state (constant hardness). An energy of at least 500 mJ / cm ² is required to reach this value). Then, it heated using the infrared lamp, rotating the semi-hardened resin layer, and heated to 150 degreeC. By this heat treatment, the thermally expandable microcapsules were expanded to obtain a circumferential length adjusting layer having a thickness of about 200 μm. Furthermore, 2000 mJ / cm ² (energy amount integrated using a UV meter and a UV-35-APR filter) was irradiated with light from a metal halide lamp, and post-exposure was performed. Then, it cut and shape | molded using the cemented carbide tool so that the thickness of the circumference adjustment layer might be 1.026 mm, and the circumference adjustment layer ((beta)) was obtained.

The peripheral length adjusting layer having closed cells obtained by thermal expansion was devitrified, and it was confirmed that the thermally expandable microcapsule was expanded. When the bubble diameter in the vicinity of the surface was observed using an optical microscope, 70% or more of bubbles entered the range of 30 to 60 μm in the obtained peripheral length adjusting layer, and the average value was 48 μm.
When the diameter of the produced support (β) with a circumference adjusting layer was measured at 10 locations, the accuracy was within 10 μm.
The Shore D hardness of the circumference adjusting layers (α) and (β) was 60 degrees and 58 degrees.

(Cushion layer formation)
A cushion tape having a thickness of 0.55 mm having a double-sided adhesive layer is applied on the circumference adjusting layers (α) and (β) obtained as described above with care so as not to contain air bubbles. On top of that, a PET film having a thickness of 100 μm with an adhesive layer on one side was attached so that the adhesive layer was exposed on the front side, and cushion layers (γ) and (δ) with PET were obtained.
The linear thermal expansion coefficient of the used PET film was 100 ppm / ° C. by a thermomechanical measurement method (TMA (trademark “TMA-50” manufactured by Shimadzu Corporation)).

(Preparation of cylindrical printing master)
Using the resins (a) to (c) obtained in the above production examples, as shown in Table 1, a polymerizable monomer, an inorganic porous material, manufactured by Fuji Silysia Chemical Ltd., is porous fine powder silica, Trademark “Cyrossphere C-1504” (hereinafter abbreviated as 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, loss on ignition 2.5 wt. %, Oil absorption 290 ml / 100 g), trademark “Cycilia 450” (hereinafter abbreviated as CH-450, number average particle diameter 8.0 μm, specific surface area 300 m ² / g, average pore diameter 17 nm, pore volume 1.25 ml / g) , Loss on ignition 5.0 wt%, oil absorption 200 ml / 100 g), trademark “Silicia 470” (hereinafter abbreviated as C-470, number average particle diameter 14.1 μm, specific surface area 300 m ² / g, average pore diameter 1) 7 nm, pore volume 1.25 ml / g, ignition loss 5.0 wt%, oil absorption 180 ml / 100 g), photopolymerization initiator and other additives were added to prepare a photosensitive resin composition. These photosensitive resin compositions were applied on the obtained cushion layer with PET (γ) or (δ) to a thickness of about 1.5 mm while rotating the support using a doctor blade, No photosensitive resin composition layer was formed. Further, after rotating the support on the resulting photosensitive resin composition layer, the metal halide lamp (trade name “M056-L21” manufactured by Eye Graphics Co., Ltd.) was irradiated with ultraviolet rays of 4000 mJ / cm ² (UV meter and UV-35). -A cylindrical printing original plate was produced by irradiation. Then, in order to adjust the thickness of the printing original plate, it cut | disconnected using the cemented carbide bite and grind | polished using the abrasive cloth, and formed the photosensitive resin hardened | cured material layer of thickness 1.14mm.

An uneven pattern was formed on the surface of the thus obtained cylindrical printing original plate using a carbon dioxide laser engraving machine. The evaluation results are shown in Table 2.
The number of wiping off the residue after engraving in Table 2 is the number of times of wiping treatment required to remove the viscous liquid residue generated after engraving. If this number is large, the amount of liquid residue is large. To do .
Among the double bond-containing organic compounds used in Examples and Reference Examples of the present invention, alicyclic and aromatic derivatives are BZMA, CHMA and PEMA.

( Reference Example 8)
60 parts by weight of styrene-butadiene copolymer (trade name “Tufprene A”, manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight: 73,000), liquid polybutadiene (trade name “B-2000”, manufactured by Nippon Petrochemical Co., Ltd.), number average molecular weight : 2000) 29 parts by weight, 1,9-nonanediol diacrylate (molecular weight: 268) 7 parts by weight, 2,2-dimethoxy-phenylacetophenone 2 parts by weight, 2,6-di-t-butyl-p-cresol 1 Part by weight was kneaded with a kneader, and 20 parts by weight of toluene was mixed with 10 parts by weight of the resulting kneaded product to obtain a highly viscous liquid photosensitive resin composition.

  The obtained liquid photosensitive resin composition was applied onto a cushion layer (γ) with PET using a doctor blade, and the toluene as a solvent was scattered and dried while slowly rotating the cylindrical support. A 1.14 mm seamless solid photosensitive resin layer was obtained. Next, a film-like exposure mask having a release layer on the surface was wound on the obtained solid photosensitive resin layer, and a chemical lamp was irradiated through the exposure mask to form a latent image. The film-like exposure mask was peeled off and developed using a hydrocarbon solvent to form a concavo-convex pattern on the surface, thereby producing a cylindrical printing plate. In the fine halftone dot pattern portion, a good conical pattern was formed.

  The present invention relates to the creation of relief images for flexographic printing plates by laser engraving, the formation of patterns for surface processing such as embossing, the formation of relief images for printing such as tiles, the pattern printing of conductors, semiconductors and insulators in the formation of electronic circuits, optical Pattern formation of functional materials such as anti-reflective coatings for parts, color filters, (near) infrared cut filters, and alignment films, base layers, light-emitting layers, and electronics in the manufacture of display elements such as liquid crystal displays or organic electroluminescent displays It is suitable for the cylindrical printing original plate used for coating layer and pattern formation of a transport layer and a sealing material layer, and its manufacturing method.

Claims (14)

A structure in which a circumferential length adjusting layer (B), a cushion layer (C), and a resin layer (D) capable of forming a concavo-convex pattern on the surface are laminated on a cylindrical support (A) in this order. Of the adjustment layer (B) and the resin layer (D), at least the circumference adjustment layer (B) is composed of a cured product obtained by photocuring the liquid photosensitive resin composition (a) by light irradiation at 20 ° C. length adjusting layer (B) of 0.01mm or more than 100mm thick, and I Shore D hardness der than 30 degrees of the peripheral length adjusting layer (B), the peripheral length adjusting layer (B) is a layer in cylindrical printing original plate to the cured photosensitive resin layer der characterized Rukoto with bubbles. The photosensitive resin composition (A) is at least one or more binders (a), organic compound having at least one or more polymerizable unsaturated groups (b), one or more even without less of the photopolymerization initiator ( cylindrical printing original plate according to 請 Motomeko 1 characterized in that it contains c). The resin layer (D) is a photosensitive resin cured product layer (E) obtained by photocuring a photosensitive resin composition, and the photosensitive cured product layer is capable of laser engraving. 2. The cylindrical printing original plate according to any one of 2 above. The photosensitive resin cured product layer (E) is a resin (d) having a number average molecular weight of 1000 or more and 200,000 or less, an organic compound (e) having a number average molecular weight of less than 1000 and having a polymerizable unsaturated group in the molecule, inorganic porous 4. The laser-engravable cylindrical printing original plate according to claim 3 , which is a cured product layer containing the mass (f) and photocured from a liquid photosensitive resin composition at 20 ° C. The inorganic porous body (f) has an average pore diameter of 1 nm to 1000 nm, a pore volume of 0.1 ml / g to 10 ml / g, a specific surface area of 10 m ² / g to 1500 m ² / g, and an oil absorption amount. 5. The cylindrical printing original plate according to claim 4, wherein the printing amount is 10 ml / 100 g or more and 2000 ml / 100 g or less. The cylindrical printing original plate according to claim 4 , wherein 20 wt% or more of the total amount of the organic compound (e) is at least one alicyclic or aromatic derivative. Peripheral length adjusting layer (B), of the resin layer (D), a cushion layer (C), at least the peripheral length adjusting layer (B) is one of claims 1, which is a seamless layer 6 of The cylindrical printing original plate according to crab. A rigid film layer (F) having a thickness of 1 μm or more and 300 μm or less is further present between the cushion layer (C) and the resin layer (D), and the linear thermal expansion coefficient of the rigid film layer (F) is The cylindrical shape according to any one of claims 1 to 7 , wherein the cylindrical shape is -10 ppm / ° C or higher and 150 ppm / ° C or lower when measured in a temperature range of 20 ° C to 80 ° C using a measurement method (TMA). Original printing. Resin layer (D) is, according to any one of claims 1, 2, characterized in that the photosensitive resin layer capable of forming a latent image of the uneven pattern is photocured by mask exposure system or a high energy beam scanning exposure method Cylindrical printing original plate. In the method for producing a cylindrical printing original plate, (i) a step of applying a liquid photosensitive resin composition (a) on a cylindrical support at 20 ° C. and laminating a photosensitive resin layer; (Iii) adjusting the film thickness of the obtained cured product layer, adjusting the film thickness to a thickness of 0.01 mm to 100 mm and a Shore D hardness of 30 degrees or more. (B) forming step, (iv) laminating the cushion layer (C) on the circumference adjusting layer, (v) resin layer (D) capable of forming an uneven pattern on the cushion layer (C) Including the step of laminating
The photosensitive resin layer for forming the circumference adjusting layer (B) is heated to 60 to 250 ° C. to expand the expandable microcapsules existing inside the photosensitive resin layer. Including before or after the step of curing by irradiation,
A method for producing a cylindrical printing original plate, wherein the step of curing the photosensitive resin layer is performed in the air. The resin layer (D) formed on the cushion layer (C) is a cured photosensitive resin layer (E) capable of forming a concavo-convex pattern by laser engraving, and the cured cured resin layer ( E) is a method of forming a photosensitive resin layer by applying a photosensitive resin composition (c) on the cushion layer (C), a step of irradiating the photosensitive resin layer with light and curing it, The method for producing a cylindrical printing original plate according to claim 10 , comprising a step of adjusting a film thickness of the cured product layer. The step of forming the cushion layer (C) on the circumference adjustment layer (B) is (viii) the step of applying the photosensitive resin (ii) on the circumference adjustment layer (B) and laminating the photosensitive resin layer, (Ix) including a step of forming a cured product layer by irradiating the photosensitive resin layer with light, and (x) adjusting a film thickness of the obtained cured product layer to form a cushion layer (C). The method for producing a cylindrical printing original plate according to any one of claims 10 and 11 . A laser engraving printing plate obtained by irradiating a surface of a cylindrical flexographic printing original plate capable of laser engraving according to any one of claims 3 to 6 with a laser beam to form a concavo-convex pattern.
A method for forming a concavo-convex pattern on the surface of the resin layer (D) using the cylindrical printing original plate according to any one of claims 1 and 2 , wherein light is applied to the photosensitive resin layer by a mask exposure method or a high energy beam scanning exposure method. And a step of forming a latent image by photocuring, and a step of removing an uncured portion by a development process.