WO2014051027A1 - Relief form film and method for manufacturing same, relief printing plate original and method for manufacturing same, and relief printing plate and plate-forming method for same - Google Patents

Relief form film and method for manufacturing same, relief printing plate original and method for manufacturing same, and relief printing plate and plate-forming method for same Download PDF

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Publication number
WO2014051027A1
WO2014051027A1 PCT/JP2013/076207 JP2013076207W WO2014051027A1 WO 2014051027 A1 WO2014051027 A1 WO 2014051027A1 JP 2013076207 W JP2013076207 W JP 2013076207W WO 2014051027 A1 WO2014051027 A1 WO 2014051027A1
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Prior art keywords
relief
printing plate
resin composition
film
forming film
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PCT/JP2013/076207
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French (fr)
Japanese (ja)
Inventor
田代　宏
優介 畠中
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富士フイルム株式会社
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Publication of WO2014051027A1 publication Critical patent/WO2014051027A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation

Definitions

  • the present invention relates to a relief forming film, a method for producing a relief forming film, a relief printing plate precursor and a production method thereof, and a relief printing plate and a plate making method thereof.
  • direct engraving CTP methods have been proposed in which a relief forming layer is directly engraved with a laser to make a plate.
  • the relief printing plate precursor is directly irradiated with a laser to cause thermal decomposition and volatilization by photothermal conversion, thereby forming recesses.
  • the direct engraving CTP method can freely control the relief shape. For this reason, when an image such as a letter is formed, the area is engraved deeper than other areas, or the fine halftone dot image is engraved with a shoulder in consideration of resistance to printing pressure, etc. Is also possible.
  • Patent Document 1 includes (1) a step of preparing a reactive resin composition, (2) a step of casting the reactive resin composition on a release body, and (3) drying the casting film from the release body.
  • a method for producing a flexographic printing plate precursor for laser engraving, which includes at least a step of peeling and forming an independent sheet, is disclosed.
  • the present invention is excellent in ink inking property, suppressed adhesion of paper dust and the like, further excellent in peelability from the base material during production, and relief forming film in which the base material residue is suppressed, and a method for producing the same, It is an object of the present invention to provide a relief printing plate precursor and a manufacturing method thereof, and a relief printing plate and a plate making method thereof.
  • ⁇ 1> Contains a binder polymer, has an arithmetic average surface roughness Ra of 0.05 ⁇ m to 0.80 ⁇ m, a steepness ⁇ a of 0.01 deg to 0.08 deg, and a surface area ratio ⁇ s of 1.0.
  • Relief-forming film characterized by being -4.5 ⁇ 2>
  • the relief forming film according to ⁇ 1> comprising a cured product of heat or a photocurable resin composition
  • ⁇ 3> The relief forming film according to ⁇ 1> or ⁇ 2>, comprising a cured product of a thermosetting resin composition
  • ⁇ 4> The relief forming film according to any one of ⁇ 1> to ⁇ 3>, which contains a photothermal conversion agent, ⁇ 5>
  • Tg glass transition temperature
  • a relief printing plate precursor having the relief forming film according to any one of ⁇ 1> to ⁇ 5> on a support, ⁇ 7> (a) An application step of applying a heat or photocurable resin composition on a substrate, and (b) forming the cured film by curing the heat or photocurable resin composition with heat or light.
  • a cured film forming step and (c) a cured film peeling step for peeling the cured film from the substrate, and the arithmetic average roughness Ra of the surface of the substrate on which the heat or photocurable resin composition is applied
  • the relief forming film is characterized in that 0.06 ⁇ m to 0.90 ⁇ m, the steepness ⁇ a is 0.01 deg to 0.10 deg, and the surface area ratio ⁇ s is 1.0 to 5.0.
  • Production method ⁇ 8> The method for producing a relief-forming film according to ⁇ 7>, wherein the cured film forming step is a step of forming a cured film by forming a crosslinked structure by heating the thermosetting resin composition, ⁇ 9> The method for producing a relief forming film according to ⁇ 7> or ⁇ 8>, wherein the substrate is a resin film, ⁇ 10> The method for producing a relief forming film according to any one of ⁇ 7> to ⁇ 9>, wherein the heat or photocurable resin composition contains a binder polymer and a photothermal conversion agent, ⁇ 11> The method for producing a relief forming film according to ⁇ 10>, wherein the photothermal conversion agent is carbon black, ⁇ 12> The method for producing a relief forming film according to ⁇ 11>, wherein the carbon black is a carbon black having an oil absorption of less than 150 mL / 100 g.
  • ⁇ 13> The surface of the relief forming film obtained by the method for producing a relief forming film according to any one of ⁇ 7> to ⁇ 12>, the surface opposite to the surface that is in contact with the substrate, and the support And a method for producing a relief printing plate precursor including an adhesion step for adhering, ⁇ 14>
  • the ink forming property is excellent, the adhesion of paper dust and the like is suppressed, the releasability from the base material at the time of manufacture is excellent, and the base material residue is suppressed, and the production thereof.
  • lower limit to upper limit representing the numerical range represents “lower limit or higher and lower limit or lower”
  • upper limit to lower limit represents “lower limit or higher and lower limit or higher”. That is, it represents a numerical range including an upper limit and a lower limit.
  • step a a coating step in which a heat or photocurable resin composition is applied onto a substrate
  • step a a coating step in which a heat or photocurable resin composition is applied onto a substrate
  • step % by mass are synonymous with “parts by weight” and “% by weight”, respectively.
  • a combination of preferable embodiments in the following description is a more preferable embodiment.
  • the relief forming film of the present invention contains a binder polymer, has an arithmetic average roughness Ra of 0.05 ⁇ m to 0.80 ⁇ m, a steepness ⁇ a of 0.01 deg to 0.08 deg, and a surface area ratio. ⁇ s is 1.0 to 4.5.
  • the manufacturing method of the relief forming film of the present invention includes (a) an application step of applying a heat or photocurable resin composition on a substrate, and (b) heat or photocurable resin composition. A cured film forming step of curing by light to form a cured film; and (c) a cured film peeling step of peeling the cured film from the substrate, and applying the heat or photocurable resin composition.
  • the arithmetic average roughness Ra of the surface of the substrate on the side is 0.06 ⁇ m to 0.90 ⁇ m, the steepness ⁇ a is 0.01 deg to 0.10 deg, and the surface area ratio ⁇ s is 1.0 to 5. It is 0.
  • the relief forming film of the present invention is particularly suitable as a relief forming film for laser engraving. That is, it is particularly suitable as a relief forming film for a direct-drawing relief printing plate precursor using a laser.
  • a relief forming film for laser engraving, a relief printing plate precursor for laser engraving and a manufacturing method thereof, and a plate making method of a relief printing plate by laser engraving will be described, but the present invention is not limited thereto. Needless to say, it can be used for purposes other than laser engraving.
  • the ink inking property is the surface shape of the relief upper part, that is, the original not engraved (printing plate precursor) It was found that it greatly depends on the plate surface shape. Appropriate irregularities are imparted to the plate surface to facilitate ink retention, thereby improving the inking property. Furthermore, it has been found that by setting the uneven shape of the plate surface to a specific range, adhesion of paper dust, dust and the like is suppressed, and as a result, generation of defects and stains in the printed image is suppressed.
  • the inventors of the present invention have improved the peelability of the relief-forming film, which is a cured film, from the substrate surface in the production of the relief-forming film by setting the uneven shape of the substrate surface to a specific range.
  • the inventors have found that the generation of residues on the substrate is also suppressed.
  • the relief forming film of the present invention is not particularly limited except for the relief forming layer application of the relief printing plate precursor subjected to laser engraving or the like, and can be widely applied to other applications.
  • the relief forming layer of the printing plate precursor that forms the convex relief described in detail below by laser engraving but also other products that form irregularities and openings on the surface, such as intaglio, stencil, stamp, etc.
  • the present invention can be applied to the formation of various printing plates and various molded articles on which images are formed by laser engraving. Especially, it is a preferable aspect to apply to formation of the relief forming layer provided on a suitable support body.
  • the relief printing plate precursor it is a layer having a flat surface as an image forming layer used for laser engraving or the like, and the layer formed by the relief forming film is referred to as a relief forming layer.
  • a layer having unevenness formed on the surface thereof is referred to as a relief layer.
  • the relief-forming film of the present invention (hereinafter also simply referred to as a relief-forming film) contains a binder polymer, has an arithmetic average roughness Ra of 0.05 ⁇ m to 0.80 ⁇ m, and a steepness ⁇ a. It is 0.01 deg to 0.08 deg, and the surface area ratio ⁇ s is 1.0 to 4.5.
  • the surface having the arithmetic average roughness Ra, the steepness ⁇ a, and the surface area ratio ⁇ s may be one surface of the relief forming film or both surfaces, but is preferably one surface from the viewpoint of manufacturing. It is preferable that the surface (image forming surface) on which laser engraving is applied has the above-described surface shape.
  • the arithmetic average roughness Ra, the steepness ⁇ a, and the surface area ratio ⁇ s may be provided on at least a part of one surface, but the entire one surface has the arithmetic average roughness Ra, the steepness ⁇ a, and It is preferable to have a surface area ratio ⁇ s.
  • the arithmetic mean roughness Ra of the relief forming film surface is 0.05 ⁇ m to 0.80 ⁇ m.
  • the arithmetic average roughness Ra is less than 0.05 ⁇ m, the contact area with dust or the like adhering to the plate surface increases, so that contamination due to adhesion of dust or the like on the plate surface becomes a problem.
  • it exceeds 0.80 ⁇ m the unevenness becomes excessive, the ink deposition property is deteriorated, and the obtained image quality is also lowered.
  • the arithmetic average height is preferably 0.10 ⁇ m to 0.70 ⁇ m, and more preferably 0.15 ⁇ m to 0.60 ⁇ m.
  • the arithmetic average roughness Ra ( ⁇ m) is one of surface shape indices, and is calculated according to JIS B 0601-2001.
  • FIG. 1 is an explanatory diagram showing the definition of arithmetic average roughness.
  • Arithmetic average roughness Ra is measured by Surfcom 130A (manufactured by ACCRETECH (Tokyo Seimitsu Co., Ltd.)), and is measured at a cutoff value of 0.8 mm, a measurement length of 10 mm, and a feed speed of 0.3 mm / sec.
  • the steepness ⁇ a of the relief forming film surface is 0.01 deg to 0.08 deg. If the steepness ⁇ a (deg) is less than 0.01 deg, the contact area with dust adhering to the plate surface increases, so that contamination due to adhesion of dust etc. on the plate surface becomes a problem. On the other hand, if it exceeds 0.08 deg, the residue on the surface of the base material increases, and a portion where the shape transfer to the plate surface is not performed normally occurs, resulting in a decrease in yield at the time of manufacture. When the steepness ⁇ a is within the above range, it is preferable because the ink deposition property is excellent, the adhesion of paper dust and the like is suppressed, and the peelability from the substrate surface is excellent.
  • the steepness ⁇ a is preferably 0.015 deg to 0.07 deg, and more preferably 0.02 deg to 0.06 deg.
  • the steepness ⁇ a is also called a local inclination, and is one of surface shape indices.
  • FIG. 2 is an explanatory diagram showing the definition of the steepness ⁇ a.
  • the steepness ⁇ a is obtained by extracting only the reference length L from the roughness curve, differentiating the extracted portion to obtain an inclination curve, and obtaining the absolute value of the inclination, the arithmetic average value of the numerous absolute values is obtained.
  • ⁇ a is a large value, it indicates that the minute inclination of the surface is steep, and when it is a small value, it indicates that the minute inclination of the surface is gentle.
  • the steepness ⁇ a is measured by Surfcom 575A (manufactured by Tokyo Seimitsu Co., Ltd.), and is measured at a cutoff value of 0.8 mm, a measurement length of 10 mm, and a feed speed of 0.3 mm / sec.
  • the surface area ratio ⁇ s of the relief forming film surface is 1.0 to 4.5.
  • the theoretical lower limit of the surface area ratio ⁇ s is 1.0. Further, if the surface area ratio ⁇ s exceeds 4.5, contamination due to adhesion of dust or the like on the plate surface becomes a problem. It is preferable for the surface area ratio ⁇ s to be in the above-mentioned range since the ink inking property is excellent and adhesion of paper dust and the like is suppressed.
  • the surface area ratio ⁇ s is preferably 1.0 to 4.0, and more preferably 1.2 to 3.8.
  • the surface area ratio ⁇ s is one of surface shape indices.
  • FIG. 3 is an explanatory diagram showing the definition of the surface area ratio ⁇ s.
  • the surface area ratio ⁇ s is measured as follows.
  • (I) Measurement of surface shape with atomic force microscope First, the surface shape is measured with an atomic force microscope (AFM) to obtain three-dimensional data (f (x, y)).
  • the measurement can be performed, for example, under the following conditions. That is, using a SEIKO SPA-400 AFM equipped with a SEIKO SPI-3800N probe station, the substrate or the plate is cut into a 1 cm square size and set on a horizontal sample stage on a piezo scanner, and the cantilever is placed on the sample surface. When the region reaches the region where the atomic force is applied, scanning is performed in the XY direction, and the unevenness of the sample is captured by the displacement of the piezo in the Z direction.
  • AFM atomic force microscope
  • a piezo scanner that can scan 150 ⁇ m in the XY direction and 10 ⁇ m in the Z direction is used.
  • the cantilever having a resonance frequency of 120 to 400 kHz and a spring constant of 12 to 90 N / m (for example, SI-DF20, manufactured by Seiko Instruments Inc .; NCH-10, manufactured by NANOSENSORS Inc .; or AC-160TS, manufactured by Olympus Corporation) Measured in DFM mode (Dynamic Force Mode). Further, the reference plane is obtained by correcting the slight inclination of the sample by approximating the obtained three-dimensional data by least squares. At the time of measurement, 516 ⁇ 256 points are measured on a 100 ⁇ m ⁇ 100 ⁇ m square of the surface.
  • the relief-forming film contains a binder polymer and is made of a cured product of a heat or photocurable resin composition (hereinafter also simply referred to as “curable resin composition” or “resin composition”). Is more preferable, and it is more preferably a cured product of the thermosetting resin composition.
  • curable resin composition suitably used in the present invention will be described later.
  • the method for producing a relief-forming film of the present invention comprises: (a) an application step of applying a heat or photocurable resin composition on a substrate; and (b) the heat or photocurable resin composition.
  • the arithmetic average roughness Ra of the surface of the substrate on the side on which the material is applied is 0.06 ⁇ m to 0.90 ⁇ m
  • the steepness ⁇ a is 0.01 deg to 0.10 deg
  • the surface area ratio ⁇ s is 1. It is 0 to 5.0.
  • the manufacturing method of the relief forming film of this invention includes the process of peeling a cured film from a base material, after apply
  • the curable resin composition is cured and the cured film is peeled off, the surface shape of the substrate is transferred to the cured film.
  • the arithmetic average roughness Ra of the surface is 0.05 ⁇ m to 0.80 ⁇ m
  • the steepness A cured film (relief forming film) having ⁇ a of 0.01 deg to 0.08 deg and a surface area ratio ⁇ s of 1.0 to 4.5 is obtained.
  • the relief forming film having the arithmetic average roughness Ra, the steepness ⁇ a, and the surface area ratio ⁇ s is excellent in ink depositing property as described above, and further, adhesion of paper dust and the like is suppressed. Furthermore, it is excellent in the peelability from the base material of a cured film, and the force required for peeling is suppressed.
  • the arithmetic average roughness Ra of the substrate surface is 0.06 ⁇ m to 0.90 ⁇ m.
  • the arithmetic average roughness Ra of the substrate surface is less than 0.06 ⁇ m, shape transfer to the plate surface is not sufficiently performed, and contamination due to dust adhesion on the plate surface becomes a problem. If the thickness exceeds 0.90 ⁇ m, the anchor effect with the coating film is manifested, and there are many residues on the substrate, causing contamination due to dust adhesion on the plate surface (because dust enters the recesses on the fine plate surface). It is considered that the force required to peel the cured film from the base material is increased.
  • the arithmetic average roughness Ra of the substrate surface is preferably 0.11 ⁇ m to 0.80 ⁇ m, and more preferably 0.16 ⁇ m to 0.70 ⁇ m.
  • the steepness ⁇ a of the substrate surface is 0.01 deg to 0.10 deg. If the steepness ⁇ a of the substrate surface is less than 0.01 deg, shape transfer to the plate surface is not sufficiently performed, and contamination due to dust adhesion on the plate surface becomes a problem. Moreover, when it exceeds 0.10 deg, the anchor effect with a coating film will express and the residue on a base material will increase. If the steepness ⁇ a of the substrate surface is within the above range, the cured film is excellent in releasability from the substrate, the ink forming property of the resulting relief forming film is good, and further, such as paper dust Adhesion is suppressed.
  • the steepness ⁇ a of the substrate surface is preferably 0.016 deg to 0.08 deg, and more preferably 0.03 deg to 0.07 deg.
  • the surface area ratio ⁇ s of the substrate surface is 1.0 to 5.0.
  • the theoretical lower limit of the surface area ratio ⁇ s is 1.0.
  • the anchor effect with the coating film is more manifested and there are many residues on the substrate, causing contamination due to dust adhesion on the plate surface (plate This is thought to be because dust enters the recesses on the fine surface.
  • the surface area ratio ⁇ s of the substrate surface is within the above range, the cured film is excellent in releasability from the substrate, the ink forming property of the resulting relief forming film is good, and further, such as paper dust Adhesion is suppressed.
  • the surface area ratio ⁇ s of the substrate surface is preferably 1.1 to 4.1, and more preferably 1.3 to 3.9.
  • the material of the base material is not particularly limited, and any material may be used.
  • Preferred resin films include polyethylene films, polypropylene films, polyvinyl chloride films, polyvinylidene chloride films, polycarbonate films, polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).
  • PET and PEN are preferable, and PET is particularly preferable.
  • a metal plate is mentioned as another preferable form of the base material which apply
  • Preferable materials include iron, aluminum, copper, stainless steel, and more preferably stainless steel.
  • the shape of the substrate is not particularly limited, and may be a plate shape or an endless belt shape. Among these, when manufacturing industrially, an endless belt shape is preferable.
  • the treatment method of the substrate is not particularly limited, and either mechanical treatment or chemical treatment is performed. It may be used, and a plurality of treatments may be used in combination, and is not particularly limited. Moreover, you may provide desired surface uneven
  • the mechanical treatment and the chemical treatment include a sand blast method, a chemical wash method, and a transfer method. More specifically, a resin film serving as a base material is placed on a transfer material such as a surface roughened aluminum plate or PET film, and the surface shape of the resin film is changed by pressing using a press. A method of transferring is exemplified. In this method, the arithmetic average roughness Ra tends to increase when the pressing pressure and the pressing temperature are increased, and the arithmetic average roughness Ra tends to decrease when the pressing speed is increased.
  • the steepness ⁇ a tends to increase when the press pressure and the press temperature are increased, and the steepness ⁇ a tends to decrease as the press speed is increased.
  • the surface area ratio ⁇ s tends to increase when the pressing pressure and the pressing temperature are increased, and the surface area ratio ⁇ s tends to decrease when the pressing speed is increased. When it is increased, the surface area ratio ⁇ s tends to increase.
  • the surface shape may be controlled by using a flat press roll as the press roll or using an embossed press roll. In the case of sandblasting, the arithmetic average roughness Ra tends to increase if the amount of abrasive used is large.
  • a curable resin composition prepared in advance is applied on a substrate, and a curable resin composition sheet (wet Film).
  • the curable resin composition is also preferably discharged through a die designed to spread the composition uniformly in the width direction. Examples of such a die include a T die, a coat hanger die, a fishtail die, and a slit.
  • a coater is exemplified. In this case, in order to obtain a uniform film thickness accuracy in the flow direction, it is preferable to transport the substrate or the die at a constant speed.
  • coat on a base material by casting a curable resin composition in the state which installed the spacer (frame) in the edge of the base material.
  • the film thickness to be applied is not particularly limited, but the film thickness of the obtained cured film (relief forming film) is preferably 0.05 mm to 10 mm. From the standpoint of printing durability of the printing plate and ease of laser engraving, it is more preferably from 0.1 mm to 7 mm.
  • the heat or photocurable resin composition used in the present invention will be described in detail.
  • the heat or photocurable resin composition is not particularly limited as long as it contains a binder polymer and is cured by heat or light, but it is more preferably cured by heat.
  • the curing reaction can proceed simultaneously while removing the solvent, which is preferable because a light irradiation device is not required.
  • a curable resin composition having low light transmittance is used, such as when containing a black pigment, it can be sufficiently cured.
  • the curable resin composition contains (Component A) a binder polymer, and preferably contains (Component B) a crosslinking agent and (Component C) a crosslinking catalyst. Furthermore, it is preferable to contain a (component D) photothermal conversion agent.
  • (Component A) Binder polymer The binder polymer is a polymer component contained in the curable resin composition, and a general polymer compound is appropriately selected, and one kind is used alone, or two or more kinds are used. Can be used together. In particular, when the curable resin composition is used for a printing plate precursor, it is preferable to select in consideration of various performances such as laser engraving property, ink acceptability, and engraving residue dispersibility.
  • binder polymer polystyrene resin, polyester resin, polyamide resin, polysulfone resin, polyethersulfone resin, polyimide resin, hydrophilic polymer containing hydroxyethylene unit, acrylic resin, acetal resin, epoxy resin, polycarbonate resin, rubber, thermoplastic It can be used by selecting from an elastomer or the like.
  • a polymer containing a partial structure that is thermally decomposed by exposure or heating is preferable.
  • Preferred examples of such a polymer include those described in paragraph 0038 of JP2008-163081A.
  • a soft resin or a thermoplastic elastomer is selected, which is described in detail, for example, in paragraphs 0039 to 0040 of Japanese Patent Laid-Open No. 2008-163081. ing. Furthermore, it is also preferable to use a hydrophilic or alcoholic polymer from the viewpoint of easy preparation of the curable resin composition and improvement in resistance to oil-based ink in the obtained relief printing plate.
  • a hydrophilic polymer those described in detail in paragraph 0041 of JP-A-2008-163081 can be used.
  • a polymer having an ethylenically unsaturated bond in the molecule is preferably used.
  • examples of such a polymer include an ethylenically unsaturated bond in the main chain, such as polybutadiene, SB (polystyrene-polybutadiene), SBS (polystyrene-polybutadiene-polystyrene), SIS (polystyrene-polyisoprene-polystyrene), SEBS (polystyrene-polyethylene / polybutylene-polystyrene) and the like.
  • an ethylenically unsaturated group such as an allyl group, an acryloyl group, a methacryloyl group, a styryl group, or a vinyl ether group is introduced into the side chain of the binder polymer described later.
  • the method for introducing an ethylenically unsaturated group into the side chain of the binder polymer is as follows: (1) copolymerizing a structural unit having a polymerizable group precursor formed by bonding a protective group to a polymerizable group to remove the protective group.
  • a polymer compound having a plurality of reactive groups such as a hydroxyl group, an amino group, an epoxy group, and a carboxyl group, and a group that reacts with these reactive groups and an ethylenic group.
  • Known methods such as a method of introducing a compound having an unsaturated group by a polymer reaction can be employed. According to these methods, the amount of ethylenically unsaturated groups introduced into the polymer compound can be controlled.
  • the binder polymer is preferably a binder polymer having a reactive functional group such as a hydroxy group, a silanol group, and a hydrolyzable silyl group.
  • a reactive functional group such as a hydroxy group, a silanol group, and a hydrolyzable silyl group.
  • the binder polymer when the curable resin composition contains Component B-1 described later, it is more preferable that the binder polymer contains a binder polymer having the reactive functional group, and the binder polymer having a hydroxy group. It is still more preferable to contain.
  • the reactive functional group may be present anywhere in the polymer molecule, but is preferably present in the side chain of the chain polymer.
  • polymers examples include vinyl copolymers (copolymers of vinyl monomers such as polyvinyl alcohol and polyvinyl acetal and derivatives thereof), acrylic resins (copolymers of acrylic monomers such as hydroxyethyl (meth) acrylate), and the like. Derivatives) can be preferably exemplified.
  • the method for introducing the reactive functional group into the binder polymer is not particularly limited, and is a method of addition (co) polymerization or polycondensation of a monomer having a reactive functional group, a polymer having a group derivable to the reactive functional group. And a method of deriving the polymer into a reactive functional group by a polymer reaction.
  • the binder polymer preferably has a glass transition temperature (Tg) of 20 ° C. or higher. When combined with the optional component (component D) photothermal conversion agent, engraving sensitivity is improved by setting the glass transition temperature (Tg) of the binder polymer to 20 ° C. or higher.
  • the binder polymer having such a glass transition temperature is also referred to as “non-elastomer”.
  • limiting in the upper limit of the glass transition temperature of a binder polymer it is preferable from a viewpoint of handleability that it is 200 degrees C or less, and it is more preferable that it is 25 degreeC or more and 120 degrees C or less.
  • a binder polymer having a glass transition temperature of room temperature (20 ° C.) or higher is used, the binder polymer takes a glass state at room temperature. For this reason, the thermal molecular motion is considerably suppressed as compared with the rubber state.
  • the heat generated by the function of the (component D) photothermal conversion agent used in combination is transmitted to the binder polymer present in the surrounding area. It is presumed that it is thermally decomposed and dissipated, resulting in engraving and forming a recess.
  • a binder polymer having a glass transition temperature of 20 ° C. or higher is used, if a photothermal conversion agent is present in a state where thermal molecular motion of the polymer is suppressed, heat transfer to the polymer and thermal decomposition occur effectively. It is presumed that the engraving sensitivity was further increased by such an effect.
  • the glass transition temperature of the binder polymer is preferably 20 ° C. or higher.
  • the glass transition temperature can be measured, for example, by differential scanning calorimetry (DSC measurement).
  • component A a binder polymer having a hydroxy group is particularly preferably used. This will be described below.
  • Component A-1) Binder polymer having a hydroxy group
  • a binder polymer having a hydroxy group (hereinafter also referred to as “specific polymer”) is preferable. This specific polymer is preferably insoluble in water and soluble in an alcohol having 1 to 4 carbon atoms.
  • a curable resin composition that provides a relief-forming film that has both water-based ink suitability and UV ink suitability, and has high engraving sensitivity and good film formability, includes polyvinyl acetal and its derivatives, side chains. Preferred examples include an acrylic resin having a hydroxy group and an epoxy resin having a hydroxy group in the side chain.
  • Non-elastomer polymer preferably used in the present invention are listed below.
  • Polyvinyl acetal and derivatives thereof Polyvinyl acetal is a compound obtained by cyclic acetalization of polyvinyl alcohol (obtained by saponifying polyvinyl acetate). Further, the polyvinyl acetal derivative is obtained by modifying the polyvinyl acetal or adding another copolymer component.
  • the acetal content in the polyvinyl acetal and its derivatives is preferably 30 to 90%, more preferably 50 to 85%. Preferably, 55 to 78% is particularly preferable.
  • the vinyl alcohol unit in the polyvinyl acetal and derivatives thereof is preferably 10 to 70 mol%, more preferably 15 to 50 mol%, particularly preferably 22 to 45 mol%, based on the total number of moles of the raw vinyl acetate monomer.
  • the polyvinyl acetal and derivatives thereof may have vinyl acetate units as other components, and the content thereof is preferably 0.01 to 20 mol%, more preferably 0.1 to 10 mol%.
  • the polyvinyl acetal derivative may further have other copolymer units. Examples of the polyvinyl acetal include polyvinyl butyral, polyvinyl propylal, polyvinyl ethylal, and polyvinyl methylal.
  • polyvinyl butyral derivative is preferable.
  • Polyvinyl butyral is usually a polymer obtained by converting polyvinyl alcohol into butyral.
  • a polyvinyl butyral derivative may also be used.
  • Examples of polyvinyl butyral derivatives include acid-modified PVB in which at least part of the hydroxyl group is modified to an acid group such as a carboxyl group, modified PVB in which part of the hydroxyl group is modified to a (meth) acryloyl group, and at least part of the hydroxyl group is an amino group Modified PVB, modified PVB in which ethylene glycol, propylene glycol, or a multimer thereof is introduced into at least a part of the hydroxyl group.
  • the molecular weight of polyvinyl acetal and its derivatives is preferably 5,000 to 800,000 as the weight average molecular weight, and preferably 8,000 to 500,000 from the viewpoint of maintaining a balance between engraving sensitivity and film property. More preferred. Further, from the viewpoint of improving the rinse property of engraving residue, it is particularly preferably 50,000 to 300,000.
  • polyvinyl butyral and derivatives thereof will be described as a particularly preferable example of polyvinyl acetal and derivatives thereof, but the invention is not limited thereto.
  • the structure of polyvinyl butyral is as shown below, and includes these structural units.
  • the butyral content (value of 1 in the above formula) in polyvinyl butyral and its derivatives is preferably 30 to 90 mol%, more preferably 40 to 85 mol%, particularly preferably 45 to 78 mol%.
  • the weight average molecular weight of polyvinyl butyral and its derivatives is preferably 5,000 to 800,000, more preferably 8,000 to 500,000, and the rinse property of engraving residue is improved. In view of the above, 50,000 to 300,000 is particularly preferable.
  • PVB and its derivatives are also available as commercial products, and preferred specific examples thereof include, from the viewpoint of alcohol solubility (especially ethanol), “ESREC B” series, “ESREC” manufactured by Sekisui Chemical Co., Ltd. “K (KS)” series and “Denkabutyral” manufactured by Denki Kagaku Kogyo Co., Ltd. are preferable. More preferably, from the viewpoint of alcohol solubility (especially ethanol), “S Lec B” series manufactured by Sekisui Chemical Co., Ltd. and “Denka Butyral” manufactured by Denki Kagaku Kogyo Co., Ltd. are preferred.
  • the acrylic resin that can be used as the specific polymer may be an acrylic resin obtained by using a known acrylic monomer and has a hydroxy group in the molecule.
  • the acrylic monomer used for the synthesis of the acrylic resin having a hydroxy group for example, (meth) acrylic acid esters, crotonic acid esters, (meth) acrylamides having a hydroxy group in the molecule are preferable. .
  • Specific examples of such a monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
  • “(meth) acryl” is a term including one or both of “acryl” and “methacryl”
  • “(meth) acrylate” means “acryl” and It is a term that includes either “methacrylic” or both.
  • acrylic monomers other than the acrylic monomer which has the said hydroxyl group can also be included as a copolymerization component.
  • acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-Butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (Meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, cycl
  • a modified acrylic resin comprising an acrylic monomer having a urethane group or a urea group can also be preferably used.
  • alkyl (meth) acrylates such as lauryl (meth) acrylate and (meth) acrylates having an aliphatic cyclic structure such as t-butylcyclohexyl methacrylate are particularly preferable from the viewpoint of water-based ink resistance.
  • novolak resin which is resin which condensed phenols and aldehydes on acidic conditions
  • Preferred novolak resins include, for example, novolak resins obtained from phenol and formaldehyde, novolak resins obtained from m-cresol and formaldehyde, novolak resins obtained from p-cresol and formaldehyde, novolak resins obtained from o-cresol and formaldehyde, and octylphenol.
  • These novolak resins preferably have a weight average molecular weight of 800 to 200,000 and a number average molecular weight of 400 to 60,000. It is also possible to use an epoxy resin having a hydroxy group in the side chain as the specific polymer.
  • an epoxy resin obtained by polymerizing an adduct of bisphenol A and epichlorohydrin as a raw material monomer is preferable.
  • These epoxy resins preferably have a weight average molecular weight of 800 to 200,000 and a number average molecular weight of 400 to 60,000.
  • polyvinyl butyral derivatives are particularly preferable from the viewpoints of rinsing properties and printing durability when used as a relief-forming film.
  • the hydroxy group content contained in the specific polymer in the present invention is preferably 0.1 to 15 mmol / g, more preferably 0.5 to 7 mmol / g in any of the above-described polymers. .
  • Component A-2 Hydrophilic Polymer
  • a hydrophilic polymer means a polymer that dissolves or swells in water.
  • Hydrophilic resins are generally resistant to oil-based inks and are preferably used. Examples of such resins include hydrophilic polymers containing hydroxyethylene, polysaccharides having hydrophilic functional groups such as cellulose, and salt structures and amino groups neutralized with acidic functional groups such as sodium polyacrylate. Examples thereof include acrylic resins containing a neutralized salt structure and onium structure, polyamide resins having a hydrophilic group introduced such as polyethylene oxide, and gelatin.
  • a polar group-containing acrylic resin and polyamide resin such as acid group / sulfonic acid group / sulfuric acid group and a salt structure in which these are neutralized are preferred.
  • More preferred are hydrophilic polymers containing hydroxyethylene, polar groups-containing acrylic resins such as amino groups or carboxylic acid groups / sulfonic acid groups / sulfuric acid groups and salt structures in which these are neutralized, and polyamide resins, particularly preferred.
  • Polyvinyl alcohols and polyamide resins Particularly preferred are polyvinyl alcohol derivatives (PVA derivatives).
  • the hydrophilic polymer a PVA derivative is preferable.
  • the PVA derivative is a copolymer containing 0.1 to 100 mol%, preferably 1 to 98 mol%, more preferably 5 to 95 mol% of a hydroxyethylene unit. It means a polymer or a polymer and a modified product thereof. Therefore, polyvinyl alcohol itself is also included.
  • the monomer for forming the copolymer can be appropriately selected from known copolymerizable monomers. Examples of the modified body include those described below.
  • Particularly preferred examples of the PVA derivative include polyvinyl alcohol and vinyl alcohol / vinyl acetate copolymer (partially saponified polyvinyl alcohol), and these modified products also fall under this category.
  • a single polymer may be used as the hydrophilic polymer, or a plurality of types may be mixed and used.
  • the hydrophilic polymer it is particularly preferable to use a PVA derivative and a hydrophilic polymer not containing a hydroxyethylene unit in combination.
  • the hydrophilic polymer containing no hydroxyethylene unit is also referred to as a non-PVA derivative.
  • the hydrophilic polymer refer to paragraphs 0039 to 0044 of JP-A-2009-226946.
  • the content of the component A in the curable resin composition is preferably 5 to 90% by mass, more preferably 15 to 85% by mass, and more preferably 30 to 80% by mass with respect to the total solid content. More preferably.
  • solid content of a composition means what remove
  • the curable resin composition preferably contains (Component B) a crosslinking agent.
  • a crosslinking agent includes (Component B-1) a compound having a hydrolyzable silyl group and / or silanol group, (Component B-2) a polyfunctional ethylenically unsaturated compound, or (Component B-3) It is preferable to include a compound having two or more cyclic structures selected from the group consisting of epoxy rings, oxetane rings and five-membered ring carbonates.
  • Component B-1 As the compound having a hydrolyzable silyl group and / or silanol group, various compounds conventionally known as silane coupling agents can be used.
  • the component (B-2) polyfunctional ethylenically unsaturated compound can be appropriately selected from compounds having at least two terminal ethylenically unsaturated groups. Such compound groups are widely known in the industrial field, and these can be used without particular limitation in the present invention.
  • the (component B-2) polyfunctional ethylenically unsaturated compound the description in paragraphs 0055 to 0074 of JP2012-116008A can be referred to.
  • (Component B) the crosslinking agent (Component B-3) a compound having two or more cyclic structures selected from the group consisting of an epoxy ring, an oxetane ring and a five-membered carbonate may be used.
  • Component B may be used alone or in combination of two or more. Also, for example, two or more types of component B-1 can be used, or two or more types that form different crosslinking systems, such as one type of component B-1 and one type of component B-2, can be used in combination. May be.
  • the component B preferably contains the component B-1 and / or the component B-2, and more preferably contains at least the component B-2.
  • the content of the component B in the curable resin composition is preferably 0.1 to 80% by mass, more preferably 1 to 40% by mass, and more preferably 5 to 30% by mass with respect to the total solid content. More preferably it is.
  • the curable resin composition preferably contains (Component C) a crosslinking catalyst.
  • the (Component C) crosslinking catalyst that can be used in the present invention include (Component C-1) an alcohol exchange reaction catalyst, (Component C-2) a polymerization initiator, or (Component C-3) and a component B-3.
  • a curing agent that can react to form a crosslinked structure is preferably exemplified.
  • Component B-1 a compound having a hydrolyzable silyl group and / or silanol group is used as Component B
  • an alcohol exchange reaction catalyst is preferably contained.
  • the alcohol exchange reaction catalyst can be applied without limitation as long as it is a reaction catalyst generally used in a silane coupling reaction.
  • examples of the alcohol exchange reaction catalyst include an acidic catalyst or a basic catalyst, and a metal complex catalyst.
  • the description in paragraphs 0098 to 0110 of JP2012-116008A can be referred to.
  • (Component B-2) a polyfunctional ethylenically unsaturated compound is contained as Component B, it is preferable to contain (Component C-2) a polymerization initiator.
  • the polymerization initiator is preferably a radical polymerization initiator, and is preferably a thermal polymerization initiator.
  • Preferred radical polymerization initiators include (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, (f) keto Oxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) metallocene compounds, (j) active ester compounds, (k) compounds having a carbon halogen bond, (l) azo compounds, and the like. From the viewpoint of engraving sensitivity and a good relief edge shape when applied to a relief forming film of a relief printing plate precursor, (c) an organic peroxide and (l) an azo compound are more preferred, (c) Organic peroxides are particularly preferred.
  • the polymerization initiator for example, the descriptions in paragraphs 0111 to 0118 of JP2012-116008A can be referred to.
  • component B contains (component B-3) a compound having two or more cyclic structures selected from the group consisting of epoxy ring, oxetane ring and five-membered carbonate, (component C-3) reacts with component B-3 It is preferable to contain a curing agent that can form a crosslinked structure.
  • Component C-3 is a compound having at least one functional group selected from the group consisting of a primary amino group and an acid anhydride group from the viewpoint of having a high reaction rate and obtaining a high-strength film, or A compound having two or more functional groups selected from the group consisting of secondary amino groups, mercapto groups, carboxyl groups, phenolic hydroxy groups and hydroxy groups is preferred.
  • component C-3 for example, the description in paragraphs 0119 to 0130 of JP2012-116008A can be referred to.
  • Component C may be used alone or in combination of two or more. It is preferable to appropriately select component C according to the component B to be used.
  • the content of component C is preferably 0.01 to 40% by mass, more preferably 0.05 to 30% by mass, based on the total solid content of the curable resin composition. More preferably, it is ⁇ 20% by mass.
  • the curable resin composition preferably contains (Component D) a photothermal exchange agent, (Component E) a plasticizer, and (Component F) a solvent in addition to the above components A to C.
  • (Component D) Photothermal Exchanger In the present invention, the curable resin composition preferably contains (Component D) a photothermal conversion agent.
  • the photothermal conversion agent is considered to promote thermal decomposition of relief formation during laser engraving by absorbing laser light and generating heat. For this reason, it is preferable to select a photothermal conversion agent that absorbs light having a laser wavelength used for engraving.
  • a component that serves as an infrared absorber when a laser (YAG laser, semiconductor laser, fiber laser, surface emitting laser, etc.) emitting infrared rays of 700 nm to 1,300 nm is used as a light source for laser engraving
  • Preferably D is used.
  • Component D is believed to absorb the laser beam and generate heat to promote thermal decomposition of the relief forming film of the printing plate precursor, and improve the sensitivity of the relief printing plate precursor of the present invention in laser engraving. Therefore, as the component D, a compound having an absorption wavelength at 700 nm to 1,300 nm is preferable, and a compound having a maximum absorption wavelength at 700 nm to 1,300 nm is more preferable.
  • the specific compound of component D preferably contains at least one selected from the group consisting of pigments and dyes that absorb light having a wavelength of 700 nm to 1,300 nm, and contains light having a wavelength of 700 nm to 1,300 nm. It is more preferable to have a pigment.
  • Preferred examples of the dye include those described in paragraphs 0263 to 0274 of JP2010-100047A.
  • Examples of the pigment used in the present invention include commercially available pigments and color index (CI) manual, “Latest Pigment Handbook” (edited by Japan Pigment Technology Association, published in 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986), “Printing Ink Technology”, CMC Publishing, 1984) can be used.
  • pigments examples include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes.
  • quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used.
  • carbon black is particularly preferable.
  • the surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered.
  • a reactive substance eg, silane coupling agent, epoxy compound, polyisocyanate, etc.
  • the photothermal conversion agent when used in a combination (condition) in which the thermal decomposition temperature of the binder polymer is equal to or higher than the thermal decomposition temperature of the binder polymer, the engraving sensitivity tends to be higher, which is preferable.
  • the photothermal conversion agent used in the present invention include cyanine dyes such as heptamethine cyanine dyes, oxonol dyes such as pentamethine oxonol dyes, indolium dyes, benzindolinium dyes, and benzothiazolium. And phthalide compounds reacted with a colorant, a quinolinium colorant, and a developer. Not all cyanine dyes have the light absorption characteristics described above. The light absorption characteristics vary greatly depending on the type of substituent and position in the molecule, the number of conjugated bonds, the type of counterion, the surrounding environment in which the dye molecule is present, and the like.
  • laser dyes such as supersaturated absorbing dyes, and near infrared absorbing dyes
  • trade marks “ADS740PP”, “ADS745HT”, “ADS760MP”, “ADS740WS”, “ADS765WS”, “ADS745NH”, “ADS790NH”, “ADS800NH” of American Dye Source (Canada), Trademarks “NK-3555”, “NK-3509”, and “NK-3519” manufactured by Hayashibara Biochemical Laboratories, Inc. can be mentioned.
  • phthalide compound reacted with the developer those described in Japanese Patent No. 3271226 can be used.
  • a phosphoric acid ester metal compound for example, a complex of a phosphoric acid ester and a copper salt described in JP-A-6-345820 and WO99 / 10354 can be used.
  • fine particles having a volume average particle diameter having light absorption characteristics in the near infrared region are preferably 0.3 ⁇ m or less, more preferably 0.1 ⁇ m or less, and particularly preferably 0.08 ⁇ m or less.
  • metal oxides such as yttrium oxide, tin oxide and / or indium oxide, copper oxide, and iron oxide, or metals such as gold, silver, palladium, and platinum can be used.
  • metal ions such as copper, tin, indium, yttrium, chromium, cobalt, titanium, nickel, vanadium, and rare earth elements are contained in particles such as glass having a volume average particle diameter of 5 ⁇ m or less, more preferably 1 ⁇ m or less. What was added can also be used. It can also be contained in microcapsules. In that case, the volume average particle diameter of the capsule is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and still more preferably 1 ⁇ m or less.
  • the ion exchanger particles may be resin particles or inorganic particles.
  • the inorganic particles include amorphous zirconium phosphate, amorphous zirconium silicophosphate, amorphous zirconium hexametaphosphate, layered zirconium phosphate, reticulated zirconium phosphate, zirconium tungstate, zeolite, and the like.
  • the resin particles include commonly used ion exchange resins and ion exchange cellulose.
  • carbon black can be particularly preferably mentioned from the viewpoint of stability and photothermal conversion efficiency.
  • Carbon black is usually used for various applications such as for color, rubber, and dry batteries, as long as there is no problem with dispersion stability in the composition forming the relief forming film, as well as products with standards classified by ASTM. Any carbon black used can be preferably used.
  • the carbon black here includes, for example, furnace black, thermal black, channel black, lamp black, acetylene black, and the like.
  • black colorants such as carbon black use a dispersant as necessary, and as a color chip or color paste previously dispersed in nitrocellulose or a binder, the curable resin composition
  • a dispersant such as carbon black
  • a color chip or color paste previously dispersed in nitrocellulose or a binder
  • the curable resin composition Such chips and pastes can be easily obtained as commercial products.
  • Examples of suitable commercially available carbon blacks include Printex U (registered trademark), Printex A (registered trademark) or Specialschwarz 4 (registered trademark) (both manufactured by Degussa), Seast 600 ISAF-LS (Tokai Carbon Co., Ltd.) Asahi # 70 (N-300), Asahi # 80 (N-220) (Asahi Carbon Co., Ltd.) and the like.
  • carbon black having an oil absorption of less than 150 ml / 100 g is preferred from the viewpoint of dispersibility in the resin composition.
  • carbon black for example, “Carbon Black Handbook” edited by Carbon Black Association can be referred to. It is preferable to use carbon black having an oil absorption of less than 150 ml / 100 g because good dispersibility can be obtained in the relief forming film.
  • carbon black having an oil absorption of 150 ml / 100 g or more is used, the dispersibility in the relief forming layer coating solution (curable resin composition) tends to deteriorate, and the carbon black aggregates. Since it tends to occur, non-uniformity of sensitivity occurs, which is not preferable. In order to prevent aggregation, it is necessary to enhance the dispersion of carbon black when preparing the coating solution.
  • dispersing component D As a method for dispersing component D, known dispersion techniques used for ink production, toner production, and the like can be used.
  • the disperser include an ultrasonic disperser, a paint shaker, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a Dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).
  • the content of component D varies depending on the molecular extinction coefficient inherent to the molecule, but is preferably 0.1 to 15% by mass, more preferably 0.1 to 15% by mass with respect to the total solid content of the resin composition.
  • the amount is 10% by mass, more preferably 0.1 to 5% by mass.
  • the volume average particle diameter of component D is preferably in the range of 0.001 ⁇ m to 10 ⁇ m, more preferably in the range of 0.05 ⁇ m to 10 ⁇ m, and particularly in the range of 0.1 ⁇ m to 7 ⁇ m. Is preferred.
  • the volume average particle size of Component D can be measured using a laser scattering type particle size distribution measuring device.
  • the curable resin composition preferably contains (Component E) a plasticizer from the viewpoint of imparting flexibility as a flexographic plate.
  • a plasticizer those known as polymer plasticizers can be used, and are not limited. For example, described in pages 211 to 220 of Polymer Dictionary (First Edition, published by Maruzen Co., Ltd., 1994).
  • an adipic acid derivative, a citric acid derivative, and a phosphoric acid derivative are preferable from the viewpoint of the effect of lowering the glass transition temperature.
  • adipic acid derivative dibutyl adipate and 2-butoxyethyl adipate are preferable.
  • citric acid derivative tributyl citrate is preferable.
  • phosphoric acid derivatives include tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, t-butylphenyl phosphate, 2-ethylhexyl phosphate And diphenyl.
  • plasticizer reference can be made to paragraphs 0145 to 0146 in JP2012-116008A.
  • the curable resin composition may use only one type of component E or two or more types in combination.
  • the content of the component E in the curable resin composition is 1 in terms of the solid content in terms of the total mass of the curable resin composition as 100% by mass from the viewpoint of lowering the glass transition temperature to room temperature or lower. Is preferably 60 to 60% by mass, more preferably 10 to 50% by mass, and still more preferably 20 to 45% by mass.
  • the curable resin composition may contain a solvent.
  • the solvent include an aprotic organic solvent and a protic solvent, and it is preferable to select them appropriately in consideration of the solubility of various components including a binder.
  • hydrophilic polyvinyl alcohol is used as a binder, it is preferable to select a protic organic solvent, and when using polyvinyl butyral which is hydrophobic compared to polyvinyl alcohol, It is preferable to mainly use a protic organic solvent.
  • aprotic organic solvent examples include acetonitrile, tetrahydrofuran, dioxane, toluene, propylene glycol monomethyl ether acetate, methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethyl lactate, N, N-dimethylacetamide. N-methylpyrrolidone and dimethyl sulfoxide.
  • protic solvent examples include water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, ethylene glycol, diethylene glycol, and 1,3-propanediol. .
  • the curable resin composition may contain other components in addition to the above components A to F.
  • a polymerization inhibitor for example, a filler, a colorant, Examples include co-sensitizers, fragrances, monofunctional ethylenically unsaturated compounds, and the like.
  • paragraphs 0147 to 0156 and 0179 to 0180 of JP2012-116008A can be referred to.
  • the preparation of the heat or photocurable resin composition may be carried out by a conventional method. For example, after component A is dissolved in a solvent, other components may be added, or all components may be dissolved in the solvent at the same time. Good. Moreover, it is also preferable to add and mix the reactive polyfunctional polymerizable compound and the polymerization initiator at the final stage of preparation. Preparation of the curable resin composition may be performed while heating. For example, when component A is dissolved in a solvent, the component B-2 and component C-2 having reactivity are added after heating. Is preferably about 90 ° C. or less from the viewpoint of preventing thermal polymerization.
  • (b) heat or light curable resin composition after (a) coating step It is preferable to have a cured film forming step of forming a cured film obtained by curing an object with heat or light.
  • the solvent contained in the curable resin composition is volatilized and dried, and is cured by introducing crosslinking into the curable resin composition.
  • the solvent is volatilized and dried by heat and a crosslinking reaction is caused by heat.
  • the relief formed after laser engraving becomes sharp, and secondly, there is an advantage that adhesion of engraving residue generated during laser engraving is suppressed.
  • a curable resin composition is photocurable, it is preferable to heat and dry after drying a certain amount of solvent.
  • the solvent is preferably dried at a temperature lower than the boiling point of the solvent. Since generation
  • the curing temperature (the solvent is also volatilized at the same time) depends on the solvent used and the decomposition temperature of the thermal polymerization initiator, but considering the heat resistance and film formability of the substrate, It is preferably 60 to 150 ° C.
  • the heating means include a method of heating the curable resin composition for a predetermined time in a hot air oven or a far infrared oven, and a method of contacting a heated roll for a predetermined time.
  • the curable resin composition contains a photopolymerization initiator
  • the relief forming film is crosslinked (cured) by irradiating light (hereinafter also referred to as “active light”) that triggers the photopolymerization initiator. )can do.
  • active light irradiating light
  • the light irradiation is generally performed on the entire surface of the curable resin composition sheet.
  • the light includes visible light, ultraviolet light, and electron beam, but ultraviolet light is the most common. If the substrate side is the back surface, the surface may only be irradiated with light.
  • the substrate is a transparent film that transmits actinic rays
  • the irradiation from the surface may be performed while the protective film is provided, or may be performed after the protective film is peeled off. Since polymerization inhibition may occur in the presence of oxygen, actinic rays may be irradiated after evacuating the curable resin composition sheet with a vinyl chloride sheet.
  • the curing step it is not necessary to completely cure the curable resin composition, as long as the solvent is removed and cured (crosslinked) to such an extent that it can be peeled off as an independent film.
  • post-heating or post-light irradiation may be performed to completely cure.
  • the volatilization of the solvent is performed only on the surface opposite to the base material, and the volatilization efficiency is low on the base material, it is also preferable to keep the curing step to such an extent that the cured film can be peeled off.
  • the manufacturing method of a relief forming film has a cured film peeling process which peels a cured film from a base material.
  • the cured film does not need to be completely cured and dried, and may be cured and / or dried to such an extent that it can be peeled as an independent film.
  • the strength of the cured film at the time of peeling is preferably 0.5 N / cm or more, and more preferably 1.0 N / cm or more. By setting the cured film strength at the time of peeling within the above range, the fracture of the cured film and the occurrence of defects are suppressed.
  • the peeling speed and the peeling temperature are not particularly limited, and may be appropriately selected as long as the cured film can be prevented from being broken or defective.
  • the post-curing step at least one selected from the group consisting of additional solvent removal, curing by additional heating, and curing by additional light irradiation is performed. These may be performed alone or in combination of two or more.
  • the first embodiment of the relief printing plate precursor of the present invention has a relief forming layer comprising the relief forming film of the present invention.
  • the 2nd embodiment of the relief printing plate precursor of this invention has the relief forming film obtained by the manufacturing method of the relief forming film of this invention as a relief forming layer.
  • a “relief printing plate” is produced by laser engraving the relief printing plate precursor.
  • the “relief layer” refers to a layer engraved with a laser or the like on a relief printing plate, that is, the relief forming layer after forming image-like irregularities.
  • the relief forming layer is preferably provided on the support.
  • the relief printing plate precursor may further have an adhesive layer between the support and the relief forming layer, if necessary, and a slip coat layer and a protective film on the relief forming layer.
  • the relief forming layer is a layer comprising the relief forming film of the present invention.
  • the relief forming layer is usually provided on a support which will be described later.
  • the relief forming layer can be directly formed on the surface of a member such as a cylinder provided in an apparatus for plate making and printing, or can be arranged and fixed there. It does not necessarily require a support.
  • a material having flexibility and excellent dimensional stability is preferably used as the support, for example, polyethylene terephthalate film (PET), polyethylene naphthalate film (PEN), polybutylene terephthalate film. Or a polycarbonate can be mentioned preferably.
  • the thickness of the support is preferably 50 ⁇ m or more and 350 ⁇ m or less, more preferably 100 ⁇ m or more and 250 ⁇ m or less, from the viewpoint of mechanical properties of the original plate, shape stability, or handling properties during plate making.
  • a known adhesive conventionally used for this type of purpose may be provided on the surface in order to improve the adhesion between the support and the relief-forming resin layer.
  • the adhesiveness with a relief forming layer or an adhesive bond layer can be improved by performing a physical and chemical treatment on the surface of the support used in the present invention.
  • the physical treatment method include a sand blast method, a wet blast method for spraying a liquid containing 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 manufacturing method of a relief printing plate precursor includes the adhesion process which adhere
  • an adhesive layer may be provided for the purpose of enhancing the adhesive force between the relief forming film and the support.
  • a material (adhesive) that can be used for the adhesive layer for example, I.I. Those described in the edition of Skeist, “Handbook of Adhesives”, the second edition (1977) can be used.
  • a protective film may be provided on the surface of the relief forming layer for the purpose of preventing scratches and dents on the surface of the relief forming layer.
  • the thickness of the protective film is preferably 25 to 500 ⁇ m, more preferably 50 to 200 ⁇ m.
  • a polyester film such as PET, or a polyolefin film such as PE (polyethylene) or PP (polypropylene) can be used.
  • the surface of the film may be matted.
  • the protective film is preferably peelable.
  • a cushion layer made of a resin or rubber having cushioning properties can be formed between the support and the relief forming layer, or between the adhesive layer and the relief forming layer.
  • a method of sticking the cushion layer with the adhesive layer on one side with the adhesive layer side facing the support is simple.
  • the surface can be cut and polished for shaping.
  • the cushion layer composition for forming the cushion layer may be applied to the support with a certain thickness and cured to form the cushion layer. Further, the surface of the cushion layer may be formed by cutting, polishing, or the like.
  • Relief printing plate and plate making method The plate making method of the relief printing plate of the present invention preferably includes an engraving step of laser engraving a relief printing plate precursor having the relief forming film of the present invention as a relief forming layer.
  • ⁇ Conditions for 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 can 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.
  • 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, etc.
  • an ultraviolet 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.
  • Laser engraving is performed in an oxygen-containing gas, generally in the presence of air or in an air stream, but can also be performed in carbon dioxide or nitrogen gas.
  • the powdery or liquid substance slightly generated on the relief printing plate surface is washed by 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. Further, it may have a cleaning step (rinsing step) for removing using a method of irradiating high-pressure steam.
  • the relief printing plate precursor or relief printing plate of the present invention is used for patterning of a printing plate relief image, stamps / signs, embossing design rolls, insulators, resistors, and conductor pastes used for electronic component creation. It can be applied and used in various applications such as relief images, relief images for ceramics mold materials, relief images for displays such as advertisements and display boards, and prototypes and mother dies for various molded products.
  • a modified layer on the surface of the relief layer on which the concavo-convex pattern is formed, tackiness on the printing plate surface can be reduced and ink wettability can be improved.
  • the modified layer include a film treated with a compound that reacts with a surface hydroxyl group such as a silane coupling agent or a titanium coupling agent, or a polymer film containing porous inorganic particles.
  • a widely used silane coupling agent is a compound having in its molecule a functional group highly reactive with the surface hydroxyl group of the substrate. Examples of such a functional group include a trimethoxysilyl group and a triethoxysilyl group.
  • the silane coupling agent is at least selected from acryloyl group, methacryloyl group, active hydrogen-containing amino group, epoxy group, vinyl group, perfluoroalkyl group, and mercapto group as reactive functional groups in the molecule.
  • the coupling agent molecule immobilized on the surface has a polymerizable reactive group in particular, it is possible to obtain a stronger film by irradiating light, heat, or electron beam and crosslinking after immobilization on the surface. .
  • the surface treatment solution is prepared by diluting the above coupling agent with water-alcohol or acetic acid water-alcohol mixed solution as necessary.
  • concentration of the coupling agent in the treatment liquid is preferably 0.05% by mass or more and 10.0% by mass or less.
  • the coupling agent treatment method will be described.
  • the treatment liquid containing the above coupling agent is used by being applied to the printing plate precursor or the surface of the printing plate after laser engraving.
  • the method for applying the coupling agent treatment liquid is not particularly limited, and for example, an immersion method, a spray method, a roll coating method, a brush coating method, or the like can be applied.
  • the coating treatment temperature and the coating treatment time are not particularly limited, but are preferably 5 ° C. or more and 60 ° C. or less, and the treatment time is preferably 0.1 seconds or more and 60 seconds or less. Furthermore, it is preferable to dry the treatment liquid layer on the surface of the resin plate under heating.
  • the coupling agent can be immobilized at a high density.
  • the layer containing inorganic porous particles when the layer containing inorganic porous particles is exposed on the printing plate surface, it is treated in a high-energy atmosphere such as plasma, and the organic layer on the surface is slightly etched away to remove minute particles on the printing plate surface. Unevenness can be formed.
  • the effect of improving the ink wettability can be expected by reducing the tack of the printing plate surface by this treatment and making the inorganic porous particles exposed on the surface easy to absorb the ink.
  • Rinsing step a step of rinsing the engraved surface of the relief layer after engraving with water or a liquid containing water as a main component.
  • Drying step a step of drying the engraved relief layer.
  • Post-crosslinking step a step of imparting energy to the relief layer after engraving and further crosslinking the relief layer.
  • a rinsing step of rinsing the engraving residue by rinsing the engraving surface with water or a liquid containing water as a main component may be added.
  • a means of rinsing there is a method of washing with tap water, a method of spraying high-pressure water, and a known batch type or conveying type brush type washing machine as a photosensitive resin relief printing machine.
  • a rinsing liquid to which soap or a surfactant is added may be used.
  • the rinsing process for rinsing the engraving surface it is preferable to add a drying process for drying the engraved relief forming layer and volatilizing the rinsing liquid. Furthermore, you may add the post-crosslinking process which further bridge
  • the pH of the rinsing solution that can be used in the present invention is preferably 9 or more, more preferably 10 or more, and still more preferably 11 or more.
  • the pH of the rinsing liquid is preferably 14 or less, more preferably 13.5 or less, still more preferably 13.2 or less, and particularly preferably 12.5 or less. Handling is easy in the said range. What is necessary is just to adjust pH using an acid and / or a base suitably in order to make a rinse liquid into said pH range, and the acid and base to be used are not specifically limited.
  • the rinsing liquid that can be used in the present invention preferably contains water as a main component.
  • the rinse liquid may contain water miscible solvents, such as alcohol, acetone, tetrahydrofuran, etc. as solvents other than water.
  • the rinse liquid contains a surfactant.
  • a surfactant that can be used in the present invention, a carboxybetaine compound, a sulfobetaine compound, a phosphobetaine compound, an amine oxide compound, or from the viewpoint of reducing engraving residue removal and influence on the relief printing plate, Preferred are betaine compounds (amphoteric surfactants) such as phosphine oxide compounds.
  • surfactant examples include known anionic surfactants, cationic surfactants, and nonionic surfactants. Furthermore, fluorine-based and silicone-based nonionic surfactants can be used in the same manner. Surfactant may be used individually by 1 type, or may use 2 or more types together. The amount of the surfactant used is not particularly limited, but is preferably 0.01 to 20% by mass, and more preferably 0.05 to 10% by mass with respect to the total mass of the rinsing liquid.
  • the relief forming layer coating solution 2 prepared on the PET film shown in Table 1 below was molded into a 1.5 mm thick sheet to obtain a relief forming resin layer.
  • the light that emerges from the metal halide tamps (trade name “M056-L21” manufactured by iGraphics Co., Ltd.) is irradiated from the surface where the photosensitive resin layer is exposed in the atmosphere to form the relief forming resin layer. Cured.
  • a relief forming film 2 obtained by curing the relief forming resin layer was produced.
  • the amount of energy irradiated was 4,000 mJ / cm 2 . This energy amount is a value obtained by integrating the illuminance measured with the UV-35-APR filter over time.
  • a transfer material A was produced by processing in combination with the following steps.
  • A Mechanical surface roughening treatment While supplying a suspension of abrasive (silica sand) having a specific gravity of 1.12 and water as a polishing slurry liquid to a surface of an aluminum plate, it is mechanically rotated by a roller-like nylon brush. Roughening was performed. The average particle size of the abrasive was 8 ⁇ m, and the maximum particle size was 50 ⁇ m.
  • the material of the nylon brush was 6 ⁇ 10 nylon, the hair length was 50 mm, and the hair diameter was 0.3 mm.
  • the nylon brush was planted so as to be dense by making a hole in a stainless steel tube having a diameter of 300 mm. Three rotating brushes were used. The distance between the two support rollers ( ⁇ 200 mm) at the bottom of the brush was 300 mm. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW plus with respect to the load before the brush roller was pressed against the aluminum plate. The rotating direction of the brush was the same as the moving direction of the aluminum plate. The rotation speed of the brush was 200 rpm.
  • (C) Desmutting treatment The desmutting treatment was performed by spraying with a 1% by mass aqueous solution of nitric acid at a temperature of 30 ° C. (containing 0.5% by mass of aluminum ions), and then washed with water by spraying.
  • the nitric acid aqueous solution used in the desmut was the waste liquid from the step of electrochemical surface roughening using alternating current in an aqueous nitric acid solution.
  • Electrochemical roughening treatment An electrochemical roughening treatment was carried out continuously using an alternating voltage of 60 Hz.
  • the electrolytic solution at this time was a nitric acid 10.5 g / liter aqueous solution (aluminum ion 5 g / liter) at a temperature of 50 ° C.
  • the AC power supply waveform has an electrochemical surface roughening treatment using a carbon electrode as a counter electrode using a trapezoidal rectangular wave alternating current with a time TP of 0.8 msec until the current value reaches a peak from zero, a DUTY ratio of 1: 1. went. Ferrite was used for the auxiliary anode.
  • the electrolytic cell used was a radial cell type.
  • the current density was 30 A / dm 2 at the peak current value, and the amount of electricity was 220 C / dm 2 in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Thereafter, washing with water was performed using well water.
  • the aluminum plate was sprayed with a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass at 32 ° C. to dissolve the aluminum plate by 3.2 g / m 2 ,
  • the smut component mainly composed of aluminum hydroxide generated when electrochemical surface roughening was used was removed, and the edge portion of the generated pit was melted to smooth the edge portion. Thereafter, washing with water was performed using well water.
  • Desmut treatment by spraying was performed with a 15% by weight aqueous solution of nitric acid at a temperature of 30 ° C. (including 4.5% by weight of aluminum ions), and then washed with water using well water.
  • the nitric acid aqueous solution used in the desmut was the waste liquid from the step of electrochemical surface roughening using alternating current in an aqueous nitric acid solution.
  • Electrochemical surface roughening treatment An electrochemical surface roughening treatment was performed continuously using an alternating voltage of 60 Hz.
  • the electrolytic solution at this time was a hydrochloric acid 7.5 g / liter aqueous solution (containing 5 g / liter of aluminum ions) at a temperature of 35 ° C.
  • the AC power supply waveform was a rectangular wave, and an electrochemical surface roughening treatment was performed using a carbon electrode as a counter electrode. Ferrite was used for the auxiliary anode.
  • the electrolytic cell used was a radial cell type.
  • the current density was 25 A / dm 2 at the peak current value, and the amount of electricity was 50 C / dm 2 in terms of the total amount of electricity when the aluminum plate was the anode. Thereafter, washing with water was performed using well water.
  • (H) Alkaline etching treatment An aluminum plate is etched by spraying at 32 ° C. with a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass, and the aluminum plate is dissolved at 0.10 g / m 2 , so The smut component mainly composed of aluminum hydroxide generated during the electrochemical surface roughening treatment was removed, and the edge portion of the generated pit was melted to smooth the edge portion. Thereafter, washing with water was performed using well water.
  • Desmut treatment A desmut treatment by spraying was performed with a 25% by mass aqueous solution of sulfuric acid at a temperature of 60 ° C. (containing 0.5% by mass of aluminum ions), and then water washing by spraying was performed using well water.
  • PET substrate having a desired surface was obtained by placing PET (Lumirror 100, manufactured by Toray Industries, Inc.) on the treated surface of the transfer material A and pressing it using a press.
  • PET Limirror 100, manufactured by Toray Industries, Inc.
  • a PET base material having a desired surface shape is obtained by changing the temperature, pressing roll pressure (pressure) and speed at the time of pressing with a press roller using a sandblasted PET as a transfer material.
  • a press roller having a flat surface or a press roller having an embossed surface was used.
  • sand blasting PET-1 was prepared by increasing the amount of sand (No. 7 cinnabar) as an abrasive used when sand blasting a PET film.
  • Sandblasted PET-2 was produced by reducing the amount of dredged sand (No. 7 dredged sand) used for sandblasting a PET film, and the surface shape Ra was 0.3 ⁇ m.
  • sandblasted PET-3 was prepared by further reducing the amount of dredged sand (No. 7 dredged sand) to be used, and the surface shape was Ra 0.2 ⁇ m.
  • the press roller whose surface was embossed had an arithmetic average roughness Ra of the roller surface of 1.0 ⁇ m.
  • the roll type press machine made from Marukyokyoken was used.
  • the surface area ratio ⁇ s was measured as follows.
  • (I) Measurement of surface shape with atomic force microscope First, the surface shape was measured with an atomic force microscope (AFM) to obtain three-dimensional data (f (x, y)). The measurement was performed under the following conditions. That is, using a SEIKO SPA-400 AFM equipped with a SEIKO SPI-3800N probe station, the substrate or plate is cut to a 1 cm square size and set on a horizontal sample stage on a piezo scanner, and the cantilever is placed on the sample surface. Then, when the region where the atomic force was applied was reached, scanning was performed in the XY direction, and the unevenness of the sample was captured by the displacement of the piezo in the Z direction.
  • AFM atomic force microscope
  • a piezo scanner that can scan 150 ⁇ m in the XY direction and 10 ⁇ m in the Z direction was used.
  • the cantilever having a resonance frequency of 120 to 400 kHz and a spring constant of 12 to 90 N / m (for example, SI-DF20, manufactured by Seiko Instruments Inc .; NCH-10, manufactured by NANOSENSORS Inc .; or AC-160TS, manufactured by Olympus Corporation)
  • the measurement was performed in DFM mode (Dynamic Force Mode). Further, the reference plane was obtained by correcting the slight inclination of the sample by least-square approximation of the obtained three-dimensional data. At the time of measurement, 516 ⁇ 256 points were measured on a 100 ⁇ m ⁇ 100 ⁇ m square of the surface.
  • ⁇ Substrate residue> The base material (coating film) after peeling the relief forming film (cured film) was observed with a microscope, and the amount of residue adhered on the base material (coating film) was measured. The number of residues of 10 ⁇ m or more was measured.
  • C Residue amount; 50 pieces / mm 2 or more .
  • the relief printing plate was attached to the plate cylinder of flexographic printing machine ITM-4 type (manufactured by Iyo Machine Co., Ltd.) with double-sided tape DuploFlex 5.1+, printing ink UV flexo 500 indigo (TOKA), anilox roller (number of lines) 900 lpi), printing was performed under normal printing pressure (conditions in which the impression cylinder was pushed into the 40 ⁇ m plate side from the distance between the plate surface and the printing paper), and the ink adhesion on the solid portion was visually observed and evaluated.
  • the evaluation index is as follows. The plates of the examples were all engraved. A: Ink is uniformly attached to the entire plate surface B: Ink is partially attached unevenly C: There are many portions where ink is not attached If there is an evaluation B or higher, there is no practical problem.
  • Table 2 shows the results of evaluating the relief-forming film 1 by changing the base material.
  • Table 3 shows the results of evaluating the relief forming film 2 while changing the base material
  • Table 4 shows the results of evaluating the relief forming film 3 by changing the base material.
  • each plate material By making the surface shape of each plate material within the range of the physical property values of the present invention, not only the paper powder adhesion and ink inking properties, which are the performance of the plate material, are improved, but also the releasability from the substrate at the time of film production is The residue could be reduced well.
  • the relief forming film 1 it can be expected that the peelability of the viscous coating film is improved.

Abstract

The purpose of the present invention is to provide a relief form film and a method for manufacturing the same, a relief printing plate original and a method for manufacturing the same, and a relief printing plate and a plate-forming method for the same, in which ink deposition performance is excellent, adhesion of paper dust or the like is minimized, separation performance with respect to the base material during manufacture is excellent, and base material residue is minimized. This relief form film is characterized in containing a binder polymer, having a surface having an arithmetic average roughness (Ra) of 0.05 μm to 0.80 μm, a steepness (Δa) of 0.01 deg to 0.08 deg, and a surface area ratio (Δs) of 1.0 to 4.5.

Description

レリーフ形成膜及びその製造方法、レリーフ印刷版原版及びその製造方法、並びに、レリーフ印刷版及びその製版方法Relief-forming film and method for producing the same, relief printing plate precursor and method for producing the same, relief printing plate and method for making the plate
　本発明は、レリーフ形成膜、レリーフ形成膜の製造方法、レリーフ印刷版原版及びその製造方法、並びに、レリーフ印刷版及びその製版方法に関する。 The present invention relates to a relief forming film, a method for producing a relief forming film, a relief printing plate precursor and a production method thereof, and a relief printing plate and a plate making method thereof.
　レリーフ形成層をレーザーにより直接彫刻し製版する、いわゆる「直彫りＣＴＰ方式」が多く提案されている。この方式では、レリーフ印刷版原版に直接レーザーを照射し、光熱変換で熱分解及び揮発を生じさせ、凹部を形成する。直彫りＣＴＰ方式は、原画フィルムを用いたレリーフ形成と異なり、自由にレリーフ形状を制御することができる。このため、抜き文字の如き画像を形成する場合、その領域を他の領域よりも深く彫刻する、又は、微細網点画像では、印圧に対する抵抗を考慮し、ショルダーをつけた彫刻をする、なども可能である。
　特許文献１には、（１）反応性樹脂組成物を調製する工程、（２）反応性樹脂組成物を離型体上にキャスティングする工程、（３）キャスティング膜を乾燥して離型体から剥離し、独立したシートを形成する工程、を少なくとも含むレーザー彫刻用フレキソ印刷版原版の製造方法が開示されている。 Many so-called “direct engraving CTP methods” have been proposed in which a relief forming layer is directly engraved with a laser to make a plate. In this method, the relief printing plate precursor is directly irradiated with a laser to cause thermal decomposition and volatilization by photothermal conversion, thereby forming recesses. Unlike the relief formation using the original film, the direct engraving CTP method can freely control the relief shape. For this reason, when an image such as a letter is formed, the area is engraved deeper than other areas, or the fine halftone dot image is engraved with a shoulder in consideration of resistance to printing pressure, etc. Is also possible.
Patent Document 1 includes (1) a step of preparing a reactive resin composition, (2) a step of casting the reactive resin composition on a release body, and (3) drying the casting film from the release body. A method for producing a flexographic printing plate precursor for laser engraving, which includes at least a step of peeling and forming an independent sheet, is disclosed.
特開２０１０－２３４６３６号公報JP 2010-234636 A
　本発明は、インキの着肉性に優れ、紙粉等の付着が抑制され、更に、製造時の基材との剥離性に優れ、基材残渣が抑制されたレリーフ形成膜及びその製造方法、レリーフ印刷版原版及びその製造方法、並びに、レリーフ印刷版及びその製版方法を提供することを目的とする。 The present invention is excellent in ink inking property, suppressed adhesion of paper dust and the like, further excellent in peelability from the base material during production, and relief forming film in which the base material residue is suppressed, and a method for producing the same, It is an object of the present invention to provide a relief printing plate precursor and a manufacturing method thereof, and a relief printing plate and a plate making method thereof.
　本発明の上記課題は、以下の＜１＞、＜６＞、＜７＞、＜１３＞～＜１５＞及び＜１７＞に記載の手段により解決された。好ましい実施態様である＜２＞～＜５＞、＜８＞～＜１２＞及び＜１６＞と共に以下に記載する。
　＜１＞　バインダーポリマーを含有し、表面の算術平均粗さＲａが０．０５μｍ～０．８０μｍであり、急峻度Δａが０．０１ｄｅｇ～０．０８ｄｅｇであり、かつ、表面積比Δｓが１．０～４．５であることを特徴とするレリーフ形成膜、
　＜２＞　熱又は光硬化性樹脂組成物の硬化物からなる、＜１＞に記載のレリーフ形成膜、
　＜３＞　熱硬化性樹脂組成物の硬化物からなる、＜１＞又は＜２＞に記載のレリーフ形成膜、
　＜４＞　光熱変換剤を含有する、＜１＞～＜３＞のいずれか１つに記載のレリーフ形成膜、
　＜５＞　バインダーポリマーのガラス転移温度（Ｔｇ）が２０℃以上である、＜１＞～＜４＞のいずれか１つに記載のレリーフ形成膜、
　＜６＞　支持体上に＜１＞～＜５＞のいずれか１つに記載のレリーフ形成膜を有する、レリーフ印刷版原版、
　＜７＞　（ａ）熱又は光硬化性樹脂組成物を基材上に塗布する塗布工程と、（ｂ）該熱又は光硬化性樹脂組成物を熱又は光により硬化して硬化膜を形成する硬化膜形成工程と、（ｃ）該硬化膜を基材から剥離する硬化膜剥離工程と、を含み、熱又は光硬化性樹脂組成物を塗布する側の基材の表面の算術平均粗さＲａが０．０６μｍ～０．９０μｍであり、急峻度Δａが０．０１ｄｅｇ～０．１０ｄｅｇであり、かつ、表面積比Δｓが１．０～５．０であることを特徴とする、レリーフ形成膜の製造方法、
　＜８＞　硬化膜形成工程が、熱硬化性樹脂組成物に加熱により架橋構造を形成させて硬化膜を形成する工程である、＜７＞に記載のレリーフ形成膜の製造方法、
　＜９＞　基材が樹脂フィルムである、＜７＞又は＜８＞に記載のレリーフ形成膜の製造方法、
　＜１０＞　熱又は光硬化性樹脂組成物が、バインダーポリマー及び光熱変換剤を含有する、＜７＞～＜９＞のいずれか１つに記載のレリーフ形成膜の製造方法、
　＜１１＞　光熱変換剤がカーボンブラックである、＜１０＞に記載のレリーフ形成膜の製造方法、
　＜１２＞　カーボンブラックが、吸油量が１５０ｍＬ／１００ｇ未満のカーボンブラックである、＜１１＞に記載のレリーフ形成膜の製造方法、
　＜１３＞　＜７＞～＜１２＞のいずれか１つに記載のレリーフ形成膜の製造方法により得られたレリーフ形成膜の基材と接触していた面とは反対側の面と、支持体と、を接着する接着工程を含むレリーフ印刷版原版の製造方法、
　＜１４＞　＜１３＞に記載の製造方法により得られたレリーフ印刷版原版、
　＜１５＞　＜６＞又は＜１４＞に記載のレリーフ印刷版原版をレーザー彫刻し、レリーフ層を形成する彫刻工程、を含むレリーフ印刷版の製版方法、
　＜１６＞　彫刻工程が、波長が７００ｎｍ～１，３００ｎｍのファイバー付き半導体レーザーを用いた走査露光により彫刻する工程である、＜１５＞に記載のレリーフ印刷版の製版方法、
　＜１７＞　＜１５＞又は＜１６＞に記載のレリーフ印刷版の製版方法により製造されたレリーフ層を有するレリーフ印刷版。 The above-mentioned problems of the present invention have been solved by means described in the following <1>, <6>, <7>, <13> to <15> and <17>. It is described below together with <2> to <5>, <8> to <12> and <16> which are preferred embodiments.
<1> Contains a binder polymer, has an arithmetic average surface roughness Ra of 0.05 μm to 0.80 μm, a steepness Δa of 0.01 deg to 0.08 deg, and a surface area ratio Δs of 1.0. Relief-forming film characterized by being -4.5
<2> The relief forming film according to <1>, comprising a cured product of heat or a photocurable resin composition,
<3> The relief forming film according to <1> or <2>, comprising a cured product of a thermosetting resin composition,
<4> The relief forming film according to any one of <1> to <3>, which contains a photothermal conversion agent,
<5> The relief-forming film according to any one of <1> to <4>, wherein the glass transition temperature (Tg) of the binder polymer is 20 ° C. or higher.
<6> A relief printing plate precursor having the relief forming film according to any one of <1> to <5> on a support,
<7> (a) An application step of applying a heat or photocurable resin composition on a substrate, and (b) forming the cured film by curing the heat or photocurable resin composition with heat or light. A cured film forming step; and (c) a cured film peeling step for peeling the cured film from the substrate, and the arithmetic average roughness Ra of the surface of the substrate on which the heat or photocurable resin composition is applied The relief forming film is characterized in that 0.06 μm to 0.90 μm, the steepness Δa is 0.01 deg to 0.10 deg, and the surface area ratio Δs is 1.0 to 5.0. Production method,
<8> The method for producing a relief-forming film according to <7>, wherein the cured film forming step is a step of forming a cured film by forming a crosslinked structure by heating the thermosetting resin composition,
<9> The method for producing a relief forming film according to <7> or <8>, wherein the substrate is a resin film,
<10> The method for producing a relief forming film according to any one of <7> to <9>, wherein the heat or photocurable resin composition contains a binder polymer and a photothermal conversion agent,
<11> The method for producing a relief forming film according to <10>, wherein the photothermal conversion agent is carbon black,
<12> The method for producing a relief forming film according to <11>, wherein the carbon black is a carbon black having an oil absorption of less than 150 mL / 100 g.
<13> The surface of the relief forming film obtained by the method for producing a relief forming film according to any one of <7> to <12>, the surface opposite to the surface that is in contact with the substrate, and the support And a method for producing a relief printing plate precursor including an adhesion step for adhering,
<14> A relief printing plate precursor obtained by the production method according to <13>,
<15> A method for making a relief printing plate, comprising engraving a laser engraving the relief printing plate precursor according to <6> or <14> to form a relief layer,
<16> The method for making a relief printing plate according to <15>, wherein the engraving step is a step of engraving by scanning exposure using a semiconductor laser with a fiber having a wavelength of 700 nm to 1,300 nm,
<17> A relief printing plate having a relief layer produced by the method for making a relief printing plate according to <15> or <16>.
　本発明によれば、インキの着肉性に優れ、紙粉等の付着が抑制され、更に、製造時の基材との剥離性に優れ、基材残渣が抑制されたレリーフ形成膜及びその製造方法、レリーフ印刷版原版及びその製造方法、並びに、レリーフ印刷版及びその製版方法が提供された。 According to the present invention, the ink forming property is excellent, the adhesion of paper dust and the like is suppressed, the releasability from the base material at the time of manufacture is excellent, and the base material residue is suppressed, and the production thereof There are provided a method, a relief printing plate precursor and a production method thereof, and a relief printing plate and a plate making method thereof.
算術平均粗さＲａの定義を示す説明図である。It is explanatory drawing which shows the definition of arithmetic mean roughness Ra. 急峻度Δａの定義を示す説明図である。It is explanatory drawing which shows the definition of steepness degree (DELTA) a. 表面積比Δｓの定義を示す説明図である。It is explanatory drawing which shows the definition of surface area ratio (DELTA) s. 実施例で使用した製版装置（レーザー彫刻機）の概念図である。It is a conceptual diagram of the plate making apparatus (laser engraving machine) used in the Example.
　以下、本発明について詳細に説明する。
　なお、本発明において、数値範囲を表す「下限～上限」の記載は、「下限以上、上限以下」を表し、「上限～下限」の記載は、「上限以下、下限以上」を表す。すなわち、上限及び下限を含む数値範囲を表す。また、「（ａ）熱又は光硬化性樹脂組成物を基材上に塗布する塗布工程」等を単に「工程ａ」等ともいう。
　また、「質量部」及び「質量％」は、それぞれ、「重量部」及び「重量％」と同義である。
　更に、本発明において、以下の説明における好ましい態様の組み合わせは、より好ましい態様である。 Hereinafter, the present invention will be described in detail.
In the present invention, the description of “lower limit to upper limit” representing the numerical range represents “lower limit or higher and lower limit or lower”, and the description of “upper limit to lower limit” represents “lower limit or higher and lower limit or higher”. That is, it represents a numerical range including an upper limit and a lower limit. In addition, “(a) a coating step in which a heat or photocurable resin composition is applied onto a substrate” or the like is simply referred to as “step a” or the like.
Further, “parts by mass” and “% by mass” are synonymous with “parts by weight” and “% by weight”, respectively.
Furthermore, in the present invention, a combination of preferable embodiments in the following description is a more preferable embodiment.
　本発明のレリーフ形成膜は、バインダーポリマーを含有し、表面の算術平均粗さＲａが０．０５μｍ～０．８０μｍであり、急峻度Δａが０．０１ｄｅｇ～０．０８ｄｅｇであり、かつ、表面積比Δｓが１．０～４．５であることを特徴とする。
　また、本発明のレリーフ形成膜の製造方法は、（ａ）熱又は光硬化性樹脂組成物を基材上に塗布する塗布工程と、（ｂ）該熱又は光硬化性樹脂組成物を熱又は光により硬化して硬化膜を形成する硬化膜形成工程と、（ｃ）該硬化膜を上記基材から剥離する硬化膜剥離工程と、を含み、上記熱又は光硬化性樹脂組成物を塗布する側の上記基材の表面の算術平均粗さＲａが０．０６μｍ～０．９０μｍであり、急峻度Δａが０．０１ｄｅｇ～０．１０ｄｅｇであり、かつ、表面積比Δｓが１．０～５．０であることを特徴とする。
　本発明のレリーフ形成膜は、レーザー彫刻用レリーフ形成膜として特に好適である。すなわち、レーザーによる直描式のレリーフ印刷版原版のレリーフ形成膜として特に好適である。以下の説明において、レーザー彫刻用のレリーフ形成膜、レーザー彫刻用のレリーフ印刷版原版及びその製造方法、並びに、レーザー彫刻によるレリーフ印刷版の製版方法について説明するが、本発明はこれに限定されず、レーザー彫刻用以外にも使用できることはいうまでもない。 The relief forming film of the present invention contains a binder polymer, has an arithmetic average roughness Ra of 0.05 μm to 0.80 μm, a steepness Δa of 0.01 deg to 0.08 deg, and a surface area ratio. Δs is 1.0 to 4.5.
Moreover, the manufacturing method of the relief forming film of the present invention includes (a) an application step of applying a heat or photocurable resin composition on a substrate, and (b) heat or photocurable resin composition. A cured film forming step of curing by light to form a cured film; and (c) a cured film peeling step of peeling the cured film from the substrate, and applying the heat or photocurable resin composition. The arithmetic average roughness Ra of the surface of the substrate on the side is 0.06 μm to 0.90 μm, the steepness Δa is 0.01 deg to 0.10 deg, and the surface area ratio Δs is 1.0 to 5. It is 0.
The relief forming film of the present invention is particularly suitable as a relief forming film for laser engraving. That is, it is particularly suitable as a relief forming film for a direct-drawing relief printing plate precursor using a laser. In the following description, a relief forming film for laser engraving, a relief printing plate precursor for laser engraving and a manufacturing method thereof, and a plate making method of a relief printing plate by laser engraving will be described, but the present invention is not limited thereto. Needless to say, it can be used for purposes other than laser engraving.
　本発明者等は鋭意検討した結果、特にレーザーによる直彫りでレリーフ形状を作製し印刷する方式においては、インキの着肉性はレリーフ上部の表面形状、すなわち彫刻していない元（印刷版原版）の版表面形状に大きく依存することを見出した。版表面に適度な凹凸を付与し、インキを保持しやすくすることにより着肉性が良化する。更に、版表面の凹凸形状を特定の範囲とすることにより、紙粉や埃等の付着が抑制され、その結果、印刷画像の欠陥や汚れの発生が抑制されることを見出した。
　また、本発明者等は、基材表面の凹凸形状を特定の範囲とすることによって、レリーフ形成膜の製造において、硬化膜であるレリーフ形成膜の基材表面からの剥離性が改良され、また、基材への残渣の発生をも抑制されることを見出した。 As a result of diligent study, the inventors of the present invention, in particular, in the method of producing and printing a relief shape by direct engraving with a laser, the ink inking property is the surface shape of the relief upper part, that is, the original not engraved (printing plate precursor) It was found that it greatly depends on the plate surface shape. Appropriate irregularities are imparted to the plate surface to facilitate ink retention, thereby improving the inking property. Furthermore, it has been found that by setting the uneven shape of the plate surface to a specific range, adhesion of paper dust, dust and the like is suppressed, and as a result, generation of defects and stains in the printed image is suppressed.
In addition, the inventors of the present invention have improved the peelability of the relief-forming film, which is a cured film, from the substrate surface in the production of the relief-forming film by setting the uneven shape of the substrate surface to a specific range. The inventors have found that the generation of residues on the substrate is also suppressed.
　本発明のレリーフ形成膜は、レーザー彫刻等が施されるレリーフ印刷版原版のレリーフ形成層用途以外にも、特に限定なく、他の用途にも広範囲に適用することができる。例えば、以下に詳述する凸状のレリーフ形成をレーザー彫刻により行う印刷版原版のレリーフ形成層のみならず、表面に凹凸や開口部を形成する他の製造物、例えば、凹版、孔版、スタンプ等、レーザー彫刻により画像形成される各種印刷版や各種成形体の形成に適用することができる。
　中でも、適切な支持体上に設けられるレリーフ形成層の形成に適用することが好ましい態様である。 The relief forming film of the present invention is not particularly limited except for the relief forming layer application of the relief printing plate precursor subjected to laser engraving or the like, and can be widely applied to other applications. For example, not only the relief forming layer of the printing plate precursor that forms the convex relief described in detail below by laser engraving, but also other products that form irregularities and openings on the surface, such as intaglio, stencil, stamp, etc. The present invention can be applied to the formation of various printing plates and various molded articles on which images are formed by laser engraving.
Especially, it is a preferable aspect to apply to formation of the relief forming layer provided on a suitable support body.
　なお、本明細書では、レリーフ印刷版原版の説明に関し、レーザー彫刻等に供する画像形成層としての、表面が平坦な層であり、レリーフ形成膜による層をレリーフ形成層と称し、これをレーザー彫刻等して表面に凹凸を形成した層をレリーフ層と称する。 In this specification, with respect to the description of the relief printing plate precursor, it is a layer having a flat surface as an image forming layer used for laser engraving or the like, and the layer formed by the relief forming film is referred to as a relief forming layer. A layer having unevenness formed on the surface thereof is referred to as a relief layer.
１．レリーフ形成膜
　本発明のレリーフ形成膜（以下、単にレリーフ形成膜ともいう。）は、バインダーポリマーを含有し、表面の算術平均粗さＲａが０．０５μｍ～０．８０μｍであり、急峻度Δａが０．０１ｄｅｇ～０．０８ｄｅｇであり、かつ、表面積比Δｓが１．０～４．５であることを特徴とする。上記の算術平均粗さＲａ、急峻度Δａ、及び表面積比Δｓを有する表面は、レリーフ形成膜の一面でもよく、両面でもよいが、製造上の観点から一面であることが好ましい。レーザー彫刻等が施される面（画像形成面）が上記の表面形状を有することが好ましい。
　上記の算術平均粗さＲａ、急峻度Δａ及び表面積比Δｓを一面の表面の少なくとも一部に有していればよいが、一面の表面の全体が上記の算術平均粗さＲａ、急峻度Δａ及び表面積比Δｓを有することが好ましい。 1. Relief-forming film The relief-forming film of the present invention (hereinafter also simply referred to as a relief-forming film) contains a binder polymer, has an arithmetic average roughness Ra of 0.05 μm to 0.80 μm, and a steepness Δa. It is 0.01 deg to 0.08 deg, and the surface area ratio Δs is 1.0 to 4.5. The surface having the arithmetic average roughness Ra, the steepness Δa, and the surface area ratio Δs may be one surface of the relief forming film or both surfaces, but is preferably one surface from the viewpoint of manufacturing. It is preferable that the surface (image forming surface) on which laser engraving is applied has the above-described surface shape.
The arithmetic average roughness Ra, the steepness Δa, and the surface area ratio Δs may be provided on at least a part of one surface, but the entire one surface has the arithmetic average roughness Ra, the steepness Δa, and It is preferable to have a surface area ratio Δs.
　レリーフ形成膜表面の算術平均粗さＲａは、０．０５μｍ～０．８０μｍである。算術平均粗さＲａが０．０５μｍ未満であると、版表面に付着するゴミ等との接触面積が多くなるため、版表面のゴミ等の付着による汚染が問題となる。また、０．８０μｍを超えると、凹凸が過剰となり、インキ着肉性が悪化すると共に、得られる画質も低下する。
　算術平均粗さＲａが上記範囲内であると、インキ着肉性に優れ、また、紙粉等の付着が抑制されるので好ましい。
　算術平均高さは、０．１０μｍ～０．７０μｍであることが好ましく、０．１５μｍ～０．６０μｍであることがより好ましい。 The arithmetic mean roughness Ra of the relief forming film surface is 0.05 μm to 0.80 μm. When the arithmetic average roughness Ra is less than 0.05 μm, the contact area with dust or the like adhering to the plate surface increases, so that contamination due to adhesion of dust or the like on the plate surface becomes a problem. On the other hand, if it exceeds 0.80 μm, the unevenness becomes excessive, the ink deposition property is deteriorated, and the obtained image quality is also lowered.
It is preferable for the arithmetic average roughness Ra to be in the above-mentioned range since the ink inking property is excellent and adhesion of paper dust and the like is suppressed.
The arithmetic average height is preferably 0.10 μm to 0.70 μm, and more preferably 0.15 μm to 0.60 μm.
　本発明において、算術平均粗さＲａ（μｍ）とは、表面形状指標の１つであり、ＪＩＳ　Ｂ　０６０１－２００１に従って算出される。図１は、算術平均粗さの定義を示す説明図である。
　算術平均粗さは、粗さ曲線から、その平均線の方向に基準長さだけ抜き取り、その抜き取り部分の平均線から測定曲線までの偏差の絶対値を合計し、平均した値である。すなわち、平均線の方向にＸ軸を、それと直交する方向にＹ軸を取り、粗さ曲線をｙ＝ｆ（ｘ）で表したときに、下記式で表される。 In the present invention, the arithmetic average roughness Ra (μm) is one of surface shape indices, and is calculated according to JIS B 0601-2001. FIG. 1 is an explanatory diagram showing the definition of arithmetic average roughness.
The arithmetic average roughness is a value obtained by extracting a reference length from the roughness curve in the direction of the average line, and adding up the absolute values of deviations from the average line of the extracted portion to the measurement curve. That is, when the X-axis is taken in the direction of the average line, the Y-axis is taken in the direction perpendicular thereto, and the roughness curve is represented by y = f (x), it is expressed by the following formula.
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000001
　算術平均粗さＲａは、サーフコム　１３０Ａ（ＡＣＣＲＥＴＥＣＨ（（株）東京精密）製）により測定され、カットオフ値０．８ｍｍ、測定長さ１０ｍｍ、送りスピード０．３ｍｍ／ｓｅｃにて測定される。 Arithmetic average roughness Ra is measured by Surfcom 130A (manufactured by ACCRETECH (Tokyo Seimitsu Co., Ltd.)), and is measured at a cutoff value of 0.8 mm, a measurement length of 10 mm, and a feed speed of 0.3 mm / sec.
　レリーフ形成膜表面の急峻度Δａは０．０１ｄｅｇ～０．０８ｄｅｇである。急峻度Δａ（ｄｅｇ）が０．０１ｄｅｇ未満であると、版表面に付着するゴミ等との接触面積が多くなるため、版表面のゴミ等の付着による汚染が問題となる。また、０．０８ｄｅｇを超えると、基材表面への残渣が多くなり、版表面への形状転写が正常に行われない部分が発生し、製造時の得率を低下させてしまう。
　急峻度Δａが上記範囲内であると、インキ着肉性に優れ、また、紙粉等の付着が抑制され、更に、基材表面からの剥離性に優れるので好ましい。
　急峻度Δａは、０．０１５ｄｅｇ～０．０７ｄｅｇであることが好ましく、０．０２ｄｅｇ～０．０６ｄｅｇであることがより好ましい。 The steepness Δa of the relief forming film surface is 0.01 deg to 0.08 deg. If the steepness Δa (deg) is less than 0.01 deg, the contact area with dust adhering to the plate surface increases, so that contamination due to adhesion of dust etc. on the plate surface becomes a problem. On the other hand, if it exceeds 0.08 deg, the residue on the surface of the base material increases, and a portion where the shape transfer to the plate surface is not performed normally occurs, resulting in a decrease in yield at the time of manufacture.
When the steepness Δa is within the above range, it is preferable because the ink deposition property is excellent, the adhesion of paper dust and the like is suppressed, and the peelability from the substrate surface is excellent.
The steepness Δa is preferably 0.015 deg to 0.07 deg, and more preferably 0.02 deg to 0.06 deg.
　本発明において、急峻度Δａは、局部傾斜とも呼ばれ、表面形状指標の１つである。図２は、急峻度Δａの定義を示す説明図である。
　急峻度Δａは、粗さ曲線から、基準長さＬだけを抜き取り、この抜き取り部分を微分し、傾き曲線を得、その傾きの絶対値を求めたとき、この多数の絶対値の算術平均値をいう。下記式で表される。
　Δａが大きい値であると、表面の微小な傾斜が急峻であることを示し、小さな値であると、表面の微小な傾斜がなだらかであることを示す。 In the present invention, the steepness Δa is also called a local inclination, and is one of surface shape indices. FIG. 2 is an explanatory diagram showing the definition of the steepness Δa.
The steepness Δa is obtained by extracting only the reference length L from the roughness curve, differentiating the extracted portion to obtain an inclination curve, and obtaining the absolute value of the inclination, the arithmetic average value of the numerous absolute values is obtained. Say. It is represented by the following formula.
When Δa is a large value, it indicates that the minute inclination of the surface is steep, and when it is a small value, it indicates that the minute inclination of the surface is gentle.
Figure JPOXMLDOC01-appb-M000002
Figure JPOXMLDOC01-appb-M000002
　急峻度Δａは、サーフコム　５７５Ａ（（株）東京精密製）により測定され、カットオフ値０．８ｍｍ、測定長さ１０ｍｍ、送りスピード０．３ｍｍ／ｓｅｃにて測定される。 The steepness Δa is measured by Surfcom 575A (manufactured by Tokyo Seimitsu Co., Ltd.), and is measured at a cutoff value of 0.8 mm, a measurement length of 10 mm, and a feed speed of 0.3 mm / sec.
　レリーフ形成膜表面の表面積比Δｓは、１．０～４．５である。表面積比Δｓの理論上の下限は１．０である。また、表面積比Δｓが４．５を超えると、版表面のゴミ等の付着による汚染が問題となる。
　表面積比Δｓが上記範囲内であると、インキ着肉性に優れ、また、紙粉等の付着が抑制されるので好ましい。
　表面積比Δｓは、１．０～４．０であることが好ましく、１．２～３．８であることがより好ましい。 The surface area ratio Δs of the relief forming film surface is 1.0 to 4.5. The theoretical lower limit of the surface area ratio Δs is 1.0. Further, if the surface area ratio Δs exceeds 4.5, contamination due to adhesion of dust or the like on the plate surface becomes a problem.
It is preferable for the surface area ratio Δs to be in the above-mentioned range since the ink inking property is excellent and adhesion of paper dust and the like is suppressed.
The surface area ratio Δs is preferably 1.0 to 4.0, and more preferably 1.2 to 3.8.
　本発明において、表面積比Δｓとは、表面形状指標の１つである。図３は、表面積比Δｓの定義を示す説明図である。
　表面積比Δｓは、平滑面に対して凹凸により増加した面積の比を意味する。すなわち、図３中の平滑面の表面積をａ、測定試料の表面積をｂとしたとき、下記式で表される。
　　Δｓ＝ｂ／ａ In the present invention, the surface area ratio Δs is one of surface shape indices. FIG. 3 is an explanatory diagram showing the definition of the surface area ratio Δs.
The surface area ratio Δs means the ratio of the area increased by unevenness to the smooth surface. That is, when the surface area of the smooth surface in FIG. 3 is a and the surface area of the measurement sample is b, it is expressed by the following formula.
Δs = b / a
　表面積比Δｓは、以下のようにして測定される。
　（ｉ）原子間力顕微鏡による表面形状の測定
　まず、原子間力顕微鏡（Ａｔｏｍｉｃ Ｆｏｒｃｅ Ｍｉｃｒｏｓｃｏｐｅ：ＡＦＭ）により表面形状を測定し、３次元データ（ｆ（ｘ，ｙ））を求める。
　測定は、例えば、以下の条件で行うことができる。すなわち、ＳＥＩＫＯ　ＳＰＩ－３８００Ｎプローブステーションを具えたＳＥＩＫＯ　ＳＰＡ－４００　ＡＦＭを用いて、基材又は版を１ｃｍ角の大きさに切り取って、ピエゾスキャナー上の水平な試料台にセットし、カンチレバーを試料表面にアプローチし、原子間力が働く領域に達したところで、ＸＹ方向にスキャンし、その際、試料の凹凸をＺ方向のピエゾの変位でとらえる。ピエゾスキャナーは、ＸＹ方向について１５０μｍ、Ｚ方向について１０μｍ、走査可能なものを使用する。カンチレバーは共振周波数１２０～４００ｋＨｚ、バネ定数１２～９０Ｎ／ｍのもの（例えば、ＳＩ－ＤＦ２０、セイコーインスツルメンツ社製；ＮＣＨ－１０、ＮＡＮＯＳＥＮＳＯＲＳ社製；又は、ＡＣ－１６０ＴＳ、オリンパス社製）を用い、ＤＦＭモード（Ｄｙｎａｍｉｃ Ｆｏｒｃｅ Ｍｏｄｅ）で測定する。また、求めた３次元データを最小二乗近似することにより試料のわずかな傾きを補正し基準面を求める。
　計測の際は、表面の１００μｍ×１００μｍ四方を５１６×２５６点測定する。ＸＹ方向の分解能は０．１μｍ、Ｚ方向の分解能は０．１５ｎｍ、スキャン速度は５０μｍ／ｓｅｃとする。
　（ｉｉ）表面積比ΔＳの算出
　上記（ｉ）で得られた３次元データ（ｆ（ｘ，ｙ））を用い、隣り合う３点を抽出し、その３点で形成される微小三角形の面積の総和を求め、実面積Ｓxとする。表面積比Δｓは、得られた実面積Ｓxと、幾何学的測定面積Ｓ0とから、式（１）により求められる。
　　Δｓ＝Ｓx／Ｓ0　　　　　　（１） The surface area ratio Δs is measured as follows.
(I) Measurement of surface shape with atomic force microscope First, the surface shape is measured with an atomic force microscope (AFM) to obtain three-dimensional data (f (x, y)).
The measurement can be performed, for example, under the following conditions. That is, using a SEIKO SPA-400 AFM equipped with a SEIKO SPI-3800N probe station, the substrate or the plate is cut into a 1 cm square size and set on a horizontal sample stage on a piezo scanner, and the cantilever is placed on the sample surface. When the region reaches the region where the atomic force is applied, scanning is performed in the XY direction, and the unevenness of the sample is captured by the displacement of the piezo in the Z direction. A piezo scanner that can scan 150 μm in the XY direction and 10 μm in the Z direction is used. The cantilever having a resonance frequency of 120 to 400 kHz and a spring constant of 12 to 90 N / m (for example, SI-DF20, manufactured by Seiko Instruments Inc .; NCH-10, manufactured by NANOSENSORS Inc .; or AC-160TS, manufactured by Olympus Corporation) Measured in DFM mode (Dynamic Force Mode). Further, the reference plane is obtained by correcting the slight inclination of the sample by approximating the obtained three-dimensional data by least squares.
At the time of measurement, 516 × 256 points are measured on a 100 μm × 100 μm square of the surface. The resolution in the XY direction is 0.1 μm, the resolution in the Z direction is 0.15 nm, and the scan speed is 50 μm / sec.
(Ii) Calculation of surface area ratio ΔS Using the three-dimensional data (f (x, y)) obtained in (i) above, three adjacent points are extracted, and the area of the micro triangle formed by the three points is calculated. The sum is obtained and set as the actual area S x . The surface area ratio Δs is obtained from the obtained real area S x and the geometric measurement area S 0 according to the equation (1).
Δs = S x / S 0 (1)
　本発明において、レリーフ形成膜は、バインダーポリマーを含有し、熱又は光硬化性樹脂組成物（以下、単に「硬化性樹脂組成物」、「樹脂組成物」ともいう。）の硬化物からなることが好ましく、熱硬化性樹脂組成物の硬化物からなることがより好ましい。本発明に好適に使用される硬化性樹脂組成物については後述する。 In the present invention, the relief-forming film contains a binder polymer and is made of a cured product of a heat or photocurable resin composition (hereinafter also simply referred to as “curable resin composition” or “resin composition”). Is more preferable, and it is more preferably a cured product of the thermosetting resin composition. The curable resin composition suitably used in the present invention will be described later.
２．レリーフ形成膜の製造方法
　本発明のレリーフ形成膜の製造方法は、（ａ）熱又は光硬化性樹脂組成物を基材上に塗布する塗布工程と、（ｂ）該熱又は光硬化性樹脂組成物を熱又は光により硬化して硬化膜を形成する硬化膜形成工程と、（ｃ）該硬化膜を上記基材から剥離する硬化膜剥離工程と、を含み、上記熱又は光硬化性樹脂組成物を塗布する側の上記基材の表面の算術平均粗さＲａが０．０６μｍ～０．９０μｍであり、急峻度Δａが０．０１ｄｅｇ～０．１０ｄｅｇであり、かつ、表面積比Δｓが１．０～５．０であることを特徴とする。 2. Method for Producing Relief-Forming Film The method for producing a relief-forming film of the present invention comprises: (a) an application step of applying a heat or photocurable resin composition on a substrate; and (b) the heat or photocurable resin composition. A cured film forming step of forming a cured film by curing the product with heat or light, and (c) a cured film peeling step of peeling the cured film from the substrate, wherein the heat or photocurable resin composition The arithmetic average roughness Ra of the surface of the substrate on the side on which the material is applied is 0.06 μm to 0.90 μm, the steepness Δa is 0.01 deg to 0.10 deg, and the surface area ratio Δs is 1. It is 0 to 5.0.
　本発明のレリーフ形成膜の製造方法は、特定の表面凹凸形状を有する基材に硬化性樹脂組成物を塗布し硬化させた後、基材から硬化膜を剥離する工程を含む。
　算術平均粗さＲａが０．０６μｍ～０．９０μｍであり、急峻度Δａが０．０１ｄｅｇ～０．１０ｄｅｇであり、かつ、表面積比Δｓが１．０～５．０である基材上で硬化性樹脂組成物を硬化させ、硬化膜を剥離させると、基材の表面形状が硬化膜に転写され、結果として、表面の算術平均粗さＲａが０．０５μｍ～０．８０μｍであり、急峻度Δａが０．０１ｄｅｇ～０．０８ｄｅｇであり、かつ、表面積比Δｓが１．０～４．５である硬化膜（レリーフ形成膜）が得られる。上記の算術平均粗さＲａ、急峻度Δａ及び表面積比Δｓを有するレリーフ形成膜は、上述のようにインキ着肉性に優れ、更に、紙粉等の付着が抑制される。
　更に、硬化膜の基材からの剥離性に優れ、剥離に必要とされる力が抑制される。その結果、剥離時の硬化膜の破断が抑制される。また、剥離時に基材に残留する硬化膜（基材残渣）が抑制され、基材の汚染が抑制されると共に、所望の表面形状を有するレリーフ形成膜が得られる。 The manufacturing method of the relief forming film of this invention includes the process of peeling a cured film from a base material, after apply | coating and hardening a curable resin composition to the base material which has a specific surface uneven | corrugated shape.
Cured on a substrate having an arithmetic average roughness Ra of 0.06 μm to 0.90 μm, a steepness Δa of 0.01 deg to 0.10 deg, and a surface area ratio Δs of 1.0 to 5.0. When the curable resin composition is cured and the cured film is peeled off, the surface shape of the substrate is transferred to the cured film. As a result, the arithmetic average roughness Ra of the surface is 0.05 μm to 0.80 μm, and the steepness A cured film (relief forming film) having Δa of 0.01 deg to 0.08 deg and a surface area ratio Δs of 1.0 to 4.5 is obtained. The relief forming film having the arithmetic average roughness Ra, the steepness Δa, and the surface area ratio Δs is excellent in ink depositing property as described above, and further, adhesion of paper dust and the like is suppressed.
Furthermore, it is excellent in the peelability from the base material of a cured film, and the force required for peeling is suppressed. As a result, breakage of the cured film at the time of peeling is suppressed. Moreover, the cured film (base material residue) which remains on the base material at the time of peeling is suppressed, contamination of the base material is suppressed, and a relief forming film having a desired surface shape is obtained.
　基材表面の算術平均粗さＲａは、０．０６μｍ～０．９０μｍである。基材表面の算術平均粗さＲａが０．０６μｍ未満であると、版表面への形状転写が十分に行われず、版表面のゴミ付着による汚染が問題となる。０．９０μｍを超える場合は、塗布膜とのアンカー効果が発現してしまい基材上の残渣が多く、版表面のゴミ付着による汚染が問題となり（版微細表面の凹部にゴミが入り込んでしまうためと考えられる。）、硬化膜の基材からの剥離に必要とされる力が大きくなってしまう。
　基材表面の算術平均粗さＲａが上記範囲内であると、硬化膜の基材からの剥離性に優れ、また、得られるレリーフ形成膜のインキ着肉性が良好であり、更に、紙粉等の付着が抑制される。
　基材表面の算術平均Ｒａは０．１１μｍ～０．８０μｍであることが好ましく、０．１６μｍ～０．７０μｍであることがより好ましい。 The arithmetic average roughness Ra of the substrate surface is 0.06 μm to 0.90 μm. When the arithmetic average roughness Ra of the substrate surface is less than 0.06 μm, shape transfer to the plate surface is not sufficiently performed, and contamination due to dust adhesion on the plate surface becomes a problem. If the thickness exceeds 0.90 μm, the anchor effect with the coating film is manifested, and there are many residues on the substrate, causing contamination due to dust adhesion on the plate surface (because dust enters the recesses on the fine plate surface). It is considered that the force required to peel the cured film from the base material is increased.
When the arithmetic average roughness Ra of the substrate surface is within the above range, the cured film is excellent in releasability from the substrate, and the ink forming property of the resulting relief forming film is good. Etc. are suppressed.
The arithmetic average Ra of the substrate surface is preferably 0.11 μm to 0.80 μm, and more preferably 0.16 μm to 0.70 μm.
　基材表面の急峻度Δａは、０．０１ｄｅｇ～０．１０ｄｅｇである。基材表面の急峻度Δａが０．０１ｄｅｇ未満であると、版表面への形状転写が十分に行われず、版表面のゴミ付着による汚染が問題となる。また、０．１０ｄｅｇを超える場合は、塗布膜とのアンカー効果が発現してしまい基材上の残渣が多くなる。
　基材表面の急峻度Δａが上記範囲内であると、硬化膜の基材からの剥離性に優れ、また、得られるレリーフ形成膜のインキ着肉性が良好であり、更に、紙粉等の付着が抑制される。
　基材表面の急峻度Δａは、０．０１６ｄｅｇ～０．０８ｄｅｇであることが好ましく、０．０３ｄｅｇ～０．０７ｄｅｇであることがより好ましい。 The steepness Δa of the substrate surface is 0.01 deg to 0.10 deg. If the steepness Δa of the substrate surface is less than 0.01 deg, shape transfer to the plate surface is not sufficiently performed, and contamination due to dust adhesion on the plate surface becomes a problem. Moreover, when it exceeds 0.10 deg, the anchor effect with a coating film will express and the residue on a base material will increase.
If the steepness Δa of the substrate surface is within the above range, the cured film is excellent in releasability from the substrate, the ink forming property of the resulting relief forming film is good, and further, such as paper dust Adhesion is suppressed.
The steepness Δa of the substrate surface is preferably 0.016 deg to 0.08 deg, and more preferably 0.03 deg to 0.07 deg.
　基材表面の表面積比Δｓは、１．０～５．０である。表面積比Δｓの理論的下限は１．０である。また、基材表面の表面積比Δｓが５．０を超える場合は、塗布膜とのアンカー効果がより発現してしまい基材上の残渣が多く、版表面のゴミ付着による汚染が問題となり（版微細表面の凹部にゴミが入り込んでしまうためと考えられる。）、硬化膜の基材からの剥離に必要とされる力が大きくなってしまう。
　基材表面の表面積比Δｓが上記範囲内であると、硬化膜の基材からの剥離性に優れ、また、得られるレリーフ形成膜のインキ着肉性が良好であり、更に、紙粉等の付着が抑制される。
　基材表面の表面積比Δｓは、１．１～４．１であることが好ましく、１．３～３．９であることがより好ましい。 The surface area ratio Δs of the substrate surface is 1.0 to 5.0. The theoretical lower limit of the surface area ratio Δs is 1.0. In addition, when the surface area ratio Δs of the substrate surface exceeds 5.0, the anchor effect with the coating film is more manifested and there are many residues on the substrate, causing contamination due to dust adhesion on the plate surface (plate This is thought to be because dust enters the recesses on the fine surface.
When the surface area ratio Δs of the substrate surface is within the above range, the cured film is excellent in releasability from the substrate, the ink forming property of the resulting relief forming film is good, and further, such as paper dust Adhesion is suppressed.
The surface area ratio Δs of the substrate surface is preferably 1.1 to 4.1, and more preferably 1.3 to 3.9.
　なお、基材の材質は特に限定されず、いかなるものでもよいが、好ましい形態の１つは樹脂フィルムである。好ましい樹脂フィルムとしては、ポリエチレンフィルム、ポリプロピレンフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリカーボネートフィルム、ポリエチレンテレフタレート（ＰＥＴ）やポリエチレンナフタレート（ＰＥＮ）といったポリエステルフィルムが挙げられる。これらの中でも、ＰＥＴ及びＰＥＮが好ましく、ＰＥＴが特に好ましい。
　また、硬化性樹脂組成物を塗布する基材の別の好ましい形態として、金属板が挙げられる。金属の材質としてはいかなるものでもよく、表面がめっき、或いはコーティング処理をされていてもよい。好ましい材質としては、鉄、アルミニウム、銅、ステンレス等が挙げられ、より好ましくはステンレスである。
　基材の形状は特に限定されず、板状でもよいし、無端ベルト状でもよい。これらの中でも、工業的に製造する場合には、無端ベルト状であることが好ましい。 In addition, the material of the base material is not particularly limited, and any material may be used. Preferred resin films include polyethylene films, polypropylene films, polyvinyl chloride films, polyvinylidene chloride films, polycarbonate films, polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). Among these, PET and PEN are preferable, and PET is particularly preferable.
Moreover, a metal plate is mentioned as another preferable form of the base material which apply | coats curable resin composition. Any metal material may be used, and the surface may be plated or coated. Preferable materials include iron, aluminum, copper, stainless steel, and more preferably stainless steel.
The shape of the substrate is not particularly limited, and may be a plate shape or an endless belt shape. Among these, when manufacturing industrially, an endless belt shape is preferable.
　塗布用基材に所望の表面凹凸形状を付与する方法について説明する。
　本発明において、基材に所望の算術平均粗さＲａ、急峻度Δａ及び表面積比Δｓを付与することができれば、基材の処理方法は特に限定されず、機械的処理及び化学的処理のいずれを使用してもよく、また、複数の処理を併用してもよく特に限定されない。また、シリカ等の微粒子を樹脂に練り込み延伸させて樹脂フィルムを作製することで、所望の表面凹凸形状を付与してもよい。更に、平坦なフィルム上にシリカ等の微粒子と樹脂を混合したものを塗布、乾燥して所望の表面凹凸形状を有するフィルムを得てもよい。
　機械的処理及び化学的処理としては、サンドブラスト法、ケミカルウォッシュ法、転写法が例示される。
　より具体的には、表面粗面化処理をしたアルミニウム板やＰＥＴフィルム等の転写材上に基材となる樹脂フィルムを載置し、プレス機を用いてプレスすることで樹脂フィルムに表面形状を転写する方法が例示される。この方法では、プレス圧及びプレス温度を大きくすると算術平均粗さＲａが大きくなる傾向にあり、プレス速度を大きくすると算術平均粗さＲａが小さくなる傾向にある。また、転写材及びプレスロールの形状にもよるが、プレス圧及びプレス温度を大きくすると急峻度Δａが大きくなる傾向にあり、プレス速度を大きくすると急峻度Δａが小さくなる傾向にある。更に、転写材及びプレスロールの形状にもよるが、プレス圧及びプレス温度を大きくすると表面積比Δｓが大きくなる傾向にあり、プレス速度を大きくすると表面積比Δｓが小さくなる傾向にあり、プレス回数を大きくすると表面積比Δｓが大きくなる傾向にある。
　また、プレスロールとして平坦なプレスロールを使用したり、エンボス加工したプレスロールを使用することにより、表面形状を制御してもよい。
　また、サンドブラスト処理する場合には、使用する研磨剤の量が多いと、算術平均粗さＲａが大きくなる傾向にある。
　以下、それぞれの工程について詳述する。 A method of imparting a desired surface irregularity shape to the coating substrate will be described.
In the present invention, as long as the desired arithmetic average roughness Ra, steepness Δa, and surface area ratio Δs can be imparted to the substrate, the treatment method of the substrate is not particularly limited, and either mechanical treatment or chemical treatment is performed. It may be used, and a plurality of treatments may be used in combination, and is not particularly limited. Moreover, you may provide desired surface uneven | corrugated shape by kneading and extending | stretching fine particles, such as a silica, to resin, and producing a resin film. Furthermore, you may apply | coat and dry what mixed fine particles, such as a silica, and resin on a flat film, and obtain the film which has a desired surface uneven | corrugated shape.
Examples of the mechanical treatment and the chemical treatment include a sand blast method, a chemical wash method, and a transfer method.
More specifically, a resin film serving as a base material is placed on a transfer material such as a surface roughened aluminum plate or PET film, and the surface shape of the resin film is changed by pressing using a press. A method of transferring is exemplified. In this method, the arithmetic average roughness Ra tends to increase when the pressing pressure and the pressing temperature are increased, and the arithmetic average roughness Ra tends to decrease when the pressing speed is increased. Depending on the shape of the transfer material and the press roll, the steepness Δa tends to increase when the press pressure and the press temperature are increased, and the steepness Δa tends to decrease as the press speed is increased. Furthermore, depending on the shape of the transfer material and the press roll, the surface area ratio Δs tends to increase when the pressing pressure and the pressing temperature are increased, and the surface area ratio Δs tends to decrease when the pressing speed is increased. When it is increased, the surface area ratio Δs tends to increase.
Further, the surface shape may be controlled by using a flat press roll as the press roll or using an embossed press roll.
In the case of sandblasting, the arithmetic average roughness Ra tends to increase if the amount of abrasive used is large.
Hereinafter, each process is explained in full detail.
（ａ）熱又は光硬化性樹脂組成物を基材上に塗布する塗布工程
　塗布工程では、予め調製した硬化性樹脂組成物を、基材上に塗布して、硬化性樹脂組成物シート（ウェット膜）を形成する。レリーフ形成膜の膜厚制御の観点から、膜厚精度の高い硬化性樹脂組成物シートを形成することが好ましい。
　硬化性樹脂組成物は、幅方向に組成物が均一に広がるように設計された口金を介して吐出することも好ましく、このような口金としては、Ｔダイ、コートハンガーダイ、フィシュテールダイ、スリットコーターが例示される。この場合、流れ方向に均一な膜厚精度を得るため、基材又は口金を一定速度で搬送することが好ましい。
　また、基材の端にスペーサー（枠）を設置した状態で、硬化性樹脂組成物を流延することで基材上に塗布してもよい。 (A) Application step of applying a heat or photocurable resin composition on a substrate In the application step, a curable resin composition prepared in advance is applied on a substrate, and a curable resin composition sheet (wet Film). From the viewpoint of controlling the thickness of the relief forming film, it is preferable to form a curable resin composition sheet with high film thickness accuracy.
The curable resin composition is also preferably discharged through a die designed to spread the composition uniformly in the width direction. Examples of such a die include a T die, a coat hanger die, a fishtail die, and a slit. A coater is exemplified. In this case, in order to obtain a uniform film thickness accuracy in the flow direction, it is preferable to transport the substrate or the die at a constant speed.
Moreover, you may apply | coat on a base material by casting a curable resin composition in the state which installed the spacer (frame) in the edge of the base material.
　塗布する膜厚は特に限定されないが、得られる硬化膜（レリーフ形成膜）の膜厚が０．０５ｍｍ～１０ｍｍであることが好ましい。印刷版の耐刷性とレーザー彫刻のしやすさから、より好ましくは０．１ｍｍ～７ｍｍである。 The film thickness to be applied is not particularly limited, but the film thickness of the obtained cured film (relief forming film) is preferably 0.05 mm to 10 mm. From the standpoint of printing durability of the printing plate and ease of laser engraving, it is more preferably from 0.1 mm to 7 mm.
（熱又は光硬化性樹脂組成物）
　本発明において使用される熱又は光硬化性樹脂組成物（硬化性樹脂組成物）について詳述する。
　本発明において、熱又は光硬化性樹脂組成物は、バインダーポリマーを含有し、熱又は光により硬化するものであれば特に限定されないが、熱により硬化することがより好ましい。熱により硬化させることにより、溶剤除去しながら同時に硬化反応を進行させることができ、光照射装置を必要としない点から好ましい。また、黒色顔料を含有する場合等、光透過性が低い硬化性樹脂組成物を使用した場合であっても、十分に硬化させることができる。 (Heat or photo-curable resin composition)
The heat or photocurable resin composition (curable resin composition) used in the present invention will be described in detail.
In the present invention, the heat or photocurable resin composition is not particularly limited as long as it contains a binder polymer and is cured by heat or light, but it is more preferably cured by heat. By curing with heat, the curing reaction can proceed simultaneously while removing the solvent, which is preferable because a light irradiation device is not required. Further, even when a curable resin composition having low light transmittance is used, such as when containing a black pigment, it can be sufficiently cured.
　硬化性樹脂組成物は、（成分Ａ）バインダーポリマー、を含有し、（成分Ｂ）架橋剤、及び（成分Ｃ）架橋触媒を含有することが好ましい。更に、（成分Ｄ）光熱変換剤を含有することが好ましい。
（成分Ａ）バインダーポリマー
　バインダーポリマーは、硬化性樹脂組成物に含有される高分子成分であり、一般的な高分子化合物を適宜選択し、１種を単独使用するか、又は、２種以上を併用することができる。特に、硬化性樹脂組成物を印刷版原版に用いる際は、レーザー彫刻性、インキ受与性、彫刻カス分散性などの種々の性能を考慮して選択することが好ましい。
　バインダーポリマーとしては、ポリスチレン樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリイミド樹脂、ヒドロキシエチレン単位を含む親水性ポリマー、アクリル樹脂、アセタール樹脂、エポキシ樹脂、ポリカーボネート樹脂、ゴム、熱可塑性エラストマーなどから選択して用いることができる。
　例えば、レーザー彫刻感度の観点からは、露光或いは加熱により熱分解する部分構造を含むポリマーが好ましい。このようなポリマーは、特開２００８－１６３０８１号公報の段落００３８に記載されているものが好ましく挙げられる。また、例えば、柔軟で可撓性を有する膜形成が目的とされる場合には、軟質樹脂や熱可塑性エラストマーが選択され、例えば、特開２００８－１６３０８１号公報の段落００３９～００４０に詳述されている。更に、硬化性樹脂組成物の調製の容易性、得られたレリーフ印刷版における油性インクに対する耐性向上の観点から、親水性又は親アルコール性ポリマーを使用することも好ましい。親水性ポリマーとしては、特開２００８－１６３０８１号公報の段落００４１に詳述されているものを使用することができる。 The curable resin composition contains (Component A) a binder polymer, and preferably contains (Component B) a crosslinking agent and (Component C) a crosslinking catalyst. Furthermore, it is preferable to contain a (component D) photothermal conversion agent.
(Component A) Binder polymer The binder polymer is a polymer component contained in the curable resin composition, and a general polymer compound is appropriately selected, and one kind is used alone, or two or more kinds are used. Can be used together. In particular, when the curable resin composition is used for a printing plate precursor, it is preferable to select in consideration of various performances such as laser engraving property, ink acceptability, and engraving residue dispersibility.
As binder polymer, polystyrene resin, polyester resin, polyamide resin, polysulfone resin, polyethersulfone resin, polyimide resin, hydrophilic polymer containing hydroxyethylene unit, acrylic resin, acetal resin, epoxy resin, polycarbonate resin, rubber, thermoplastic It can be used by selecting from an elastomer or the like.
For example, from the viewpoint of laser engraving sensitivity, a polymer containing a partial structure that is thermally decomposed by exposure or heating is preferable. Preferred examples of such a polymer include those described in paragraph 0038 of JP2008-163081A. For example, when the purpose is to form a soft and flexible film, a soft resin or a thermoplastic elastomer is selected, which is described in detail, for example, in paragraphs 0039 to 0040 of Japanese Patent Laid-Open No. 2008-163081. ing. Furthermore, it is also preferable to use a hydrophilic or alcoholic polymer from the viewpoint of easy preparation of the curable resin composition and improvement in resistance to oil-based ink in the obtained relief printing plate. As the hydrophilic polymer, those described in detail in paragraph 0041 of JP-A-2008-163081 can be used.
　加えて、加熱や露光により硬化させ、強度を向上させる目的に使用する場合には、分子内にエチレン性不飽和結合をもつポリマーが好ましく用いられる。このようなポリマーとして、主鎖にエチレン性不飽和結合を含むポリマーとしては、例えば、ポリブタジエン、ＳＢ（ポリスチレン－ポリブタジエン）、ＳＢＳ（ポリスチレン－ポリブタジエン－ポリスチレン）、ＳＩＳ（ポリスチレン－ポリイソプレン－ポリスチレン）、ＳＥＢＳ（ポリスチレン－ポリエチレン／ポリブチレン－ポリスチレン）等が挙げられる。側鎖にエチレン性不飽和結合をもつポリマーとしては、後記のバインダーポリマーの骨格に、アリル基、アクリロイル基、メタクリロイル基、スチリル基、ビニルエーテル基のようなエチレン性不飽和基を側鎖に導入することにより得られる。バインダーポリマー側鎖にエチレン性不飽和基を導入する方法は、（１）重合性基に保護基を結合させてなる重合性基前駆体を有する構成単位をポリマーに共重合させ、保護基を脱離させて重合性基とする方法、（２）水酸基、アミノ基、エポキシ基、カルボキシル基などの反応性基を複数有する高分子化合物を作製し、これらの反応性基と反応する基及びエチレン性不飽和基を有する化合物を高分子反応により導入する方法など、公知の方法をとることができる。これらの方法によれば、高分子化合物中へのエチレン性不飽和基の導入量を制御することができる。 In addition, when used for the purpose of curing by heating or exposure and improving the strength, a polymer having an ethylenically unsaturated bond in the molecule is preferably used. Examples of such a polymer include an ethylenically unsaturated bond in the main chain, such as polybutadiene, SB (polystyrene-polybutadiene), SBS (polystyrene-polybutadiene-polystyrene), SIS (polystyrene-polyisoprene-polystyrene), SEBS (polystyrene-polyethylene / polybutylene-polystyrene) and the like. As a polymer having an ethylenically unsaturated bond in the side chain, an ethylenically unsaturated group such as an allyl group, an acryloyl group, a methacryloyl group, a styryl group, or a vinyl ether group is introduced into the side chain of the binder polymer described later. Can be obtained. The method for introducing an ethylenically unsaturated group into the side chain of the binder polymer is as follows: (1) copolymerizing a structural unit having a polymerizable group precursor formed by bonding a protective group to a polymerizable group to remove the protective group. (2) A polymer compound having a plurality of reactive groups such as a hydroxyl group, an amino group, an epoxy group, and a carboxyl group, and a group that reacts with these reactive groups and an ethylenic group. Known methods such as a method of introducing a compound having an unsaturated group by a polymer reaction can be employed. According to these methods, the amount of ethylenically unsaturated groups introduced into the polymer compound can be controlled.
　バインダーポリマーは、ヒドロキシ基、シラノール基及び加水分解性シリル基等の反応性官能基を有するバインダーポリマーであることが好ましい。
　また、本発明において、硬化性樹脂組成物が後述する成分Ｂ－１を含有する場合、バインダーポリマーとして、上記反応性官能基を有するバインダーポリマーを含有することがより好ましく、ヒドロキシ基を有するバインダーポリマーを含有することが更に好ましい。
　上記反応性官能基は、ポリマー分子中のいずれかに存在すればよいが、鎖状ポリマーの側鎖に存在することが好ましい。このようなポリマーとしては、ビニル共重合体（ポリビニルアルコールやポリビニルアセタールなどのビニルモノマーの共重合体及びその誘導体）やアクリル樹脂（ヒドロキシエチル（メタ）アクリレートなどのアクリル系モノマーの共重合体及びその誘導体）が好ましく例示できる。 The binder polymer is preferably a binder polymer having a reactive functional group such as a hydroxy group, a silanol group, and a hydrolyzable silyl group.
In the present invention, when the curable resin composition contains Component B-1 described later, it is more preferable that the binder polymer contains a binder polymer having the reactive functional group, and the binder polymer having a hydroxy group. It is still more preferable to contain.
The reactive functional group may be present anywhere in the polymer molecule, but is preferably present in the side chain of the chain polymer. Examples of such polymers include vinyl copolymers (copolymers of vinyl monomers such as polyvinyl alcohol and polyvinyl acetal and derivatives thereof), acrylic resins (copolymers of acrylic monomers such as hydroxyethyl (meth) acrylate), and the like. Derivatives) can be preferably exemplified.
　バインダーポリマーに反応性官能基を導入する方法は特に限定されず、反応性官能基を有する単量体を付加（共）重合又は重縮合する方法、反応性官能基に誘導可能な基を有するポリマーを合成した後、このポリマーを高分子反応により反応性官能基に誘導する方法が含まれる。
　バインダーポリマーは、ガラス転移温度（Ｔｇ）が２０℃以上であることが好ましい。任意成分である（成分Ｄ）光熱変換剤と組み合わせた場合に、バインダーポリマーのガラス転移温度（Ｔｇ）を２０℃以上とすることにより、彫刻感度が向上する。このようなガラス転移温度を有するバインダーポリマーを以下、「非エラストマー」ともいう。バインダーポリマーのガラス転移温度の上限には制限はないが、２００℃以下であることが取り扱い性の観点から好ましく、２５℃以上１２０℃以下であることがより好ましい。
　ガラス転移温度が室温（２０℃）以上のバインダーポリマーを用いる場合、該バインダーポリマーは常温ではガラス状態をとる。このためゴム状態をとる場合に比較して、熱的な分子運動はかなり抑制された状態にある。レーザー彫刻においては、レーザー照射時に、赤外線レーザー等が付与する熱に加え、所望により併用される（成分Ｄ）光熱変換剤の機能により発生した熱が、周囲に存在するバインダーポリマーに伝達され、これが熱分解、消散して、結果的に彫刻されて凹部が形成されると推定される。
　ガラス転移温度が２０℃以上のバインダーポリマーを用いた場合、ポリマーの熱的な分子運動が抑制された状態の中に光熱変換剤が存在すると、ポリマーへの熱伝達と熱分解が効果的に起こるものと考えられ、このような効果によって彫刻感度が更に増大したものと推定される。特に、後述する（成分Ａ－１）ヒドロキシ基を有するバインダーポリマーを使用する場合には、該バインダーポリマーのガラス転移温度が２０℃以上であることが好ましい。
　ガラス転移温度は、例えば、示差走査熱量測定（ＤＳＣ測定）により測定することができる。 The method for introducing the reactive functional group into the binder polymer is not particularly limited, and is a method of addition (co) polymerization or polycondensation of a monomer having a reactive functional group, a polymer having a group derivable to the reactive functional group. And a method of deriving the polymer into a reactive functional group by a polymer reaction.
The binder polymer preferably has a glass transition temperature (Tg) of 20 ° C. or higher. When combined with the optional component (component D) photothermal conversion agent, engraving sensitivity is improved by setting the glass transition temperature (Tg) of the binder polymer to 20 ° C. or higher. Hereinafter, the binder polymer having such a glass transition temperature is also referred to as “non-elastomer”. Although there is no restriction | limiting in the upper limit of the glass transition temperature of a binder polymer, it is preferable from a viewpoint of handleability that it is 200 degrees C or less, and it is more preferable that it is 25 degreeC or more and 120 degrees C or less.
When a binder polymer having a glass transition temperature of room temperature (20 ° C.) or higher is used, the binder polymer takes a glass state at room temperature. For this reason, the thermal molecular motion is considerably suppressed as compared with the rubber state. In laser engraving, in addition to the heat imparted by an infrared laser or the like during laser irradiation, the heat generated by the function of the (component D) photothermal conversion agent used in combination is transmitted to the binder polymer present in the surrounding area. It is presumed that it is thermally decomposed and dissipated, resulting in engraving and forming a recess.
When a binder polymer having a glass transition temperature of 20 ° C. or higher is used, if a photothermal conversion agent is present in a state where thermal molecular motion of the polymer is suppressed, heat transfer to the polymer and thermal decomposition occur effectively. It is presumed that the engraving sensitivity was further increased by such an effect. In particular, when a binder polymer having a hydroxy group (component A-1) described later is used, the glass transition temperature of the binder polymer is preferably 20 ° C. or higher.
The glass transition temperature can be measured, for example, by differential scanning calorimetry (DSC measurement).
　成分Ａとしては、特に、（成分Ａ－１）ヒドロキシ基を有するバインダーポリマーが好ましく用いられる。以下に説明する。
（成分Ａ－１）ヒドロキシ基を有するバインダーポリマー
　硬化性樹脂組成物におけるバンインダーポリマーとしては、（成分Ａ－１）ヒドロキシ基を有するバインダーポリマー（以下、「特定ポリマー」ともいう。）が好ましい。この特定ポリマーは、水不溶であって、かつ、炭素数１～４のアルコールに可溶であることが好ましい。成分Ａ－１として、水性インキ適性とＵＶインキ適性を両立しつつ、かつ彫刻感度が高く皮膜性も良好であるレリーフ形成膜を与える硬化性樹脂組成物には、ポリビニルアセタール及びその誘導体、側鎖にヒドロキシ基を有するアクリル樹脂、及び、側鎖にヒドロキシ基を有するエポキシ樹脂等が好ましく挙げられる。 As component A, (Component A-1) a binder polymer having a hydroxy group is particularly preferably used. This will be described below.
(Component A-1) Binder polymer having a hydroxy group As the vaninder polymer in the curable resin composition, (Component A-1) a binder polymer having a hydroxy group (hereinafter also referred to as “specific polymer”) is preferable. This specific polymer is preferably insoluble in water and soluble in an alcohol having 1 to 4 carbon atoms. As component A-1, a curable resin composition that provides a relief-forming film that has both water-based ink suitability and UV ink suitability, and has high engraving sensitivity and good film formability, includes polyvinyl acetal and its derivatives, side chains. Preferred examples include an acrylic resin having a hydroxy group and an epoxy resin having a hydroxy group in the side chain.
　本発明において好ましく用いられる非エラストマーであるポリマーの具体例を以下に挙げる。
（１）ポリビニルアセタール及びその誘導体
　ポリビニルアセタールは、ポリビニルアルコール（ポリ酢酸ビニルを鹸化して得られる。）を環状アセタール化することにより得られる化合物である。また、ポリビニルアセタール誘導体は、上記ポリビニルアセタールを変性したり、他の共重合成分を加えたものである。
　ポリビニルアセタール及びその誘導体中のアセタール含量（原料の酢酸ビニルモノマーの総モル数を１００％とし、アセタール化されるビニルアルコール単位のモル％）は、３０～９０％が好ましく、５０～８５％がより好ましく、５５～７８％が特に好ましい。
　ポリビニルアセタール及びその誘導体中のビニルアルコール単位としては、原料の酢酸ビニルモノマーの総モル数に対して、１０～７０モル％が好ましく、１５～５０モル％がより好ましく、２２～４５モル％が特に好ましい。
　また、ポリビニルアセタール及びその誘導体は、その他の成分として、酢酸ビニル単位を有していてもよく、その含量としては０．０１～２０モル％が好ましく、０．１～１０モル％が更に好ましい。ポリビニルアセタール誘導体は、更に、その他の共重合単位を有していてもよい。
　ポリビニルアセタールとしては、ポリビニルブチラール、ポリビニルプロピラール、ポリビニルエチラール、ポリビニルメチラールなどが挙げられる。中でも、ポリビニルブチラール誘導体（ＰＶＢ）が好ましい。
　ポリビニルブチラールは、通常、ポリビニルアルコールをブチラール化して得られるポリマーである。また、ポリビニルブチラール誘導体を用いてもよい。
　ポリビニルブチラール誘導体の例として、水酸基の少なくとも一部をカルボキシル基等の酸基に変性した酸変性ＰＶＢ、水酸基の一部を（メタ）アクリロイル基に変性した変性ＰＶＢ、水酸基の少なくとも一部をアミノ基に変性した変性ＰＶＢ、水酸基の少なくとも一部にエチレングリコールやプロピレングリコール及びこれらの複量体を導入した変性ＰＶＢ等が挙げられる。
　ポリビニルアセタール及びその誘導体の分子量としては、彫刻感度と皮膜性のバランスを保つ観点で、重量平均分子量として５，０００～８００，０００であることが好ましく、８，０００～５００，０００であることがより好ましい。更に、彫刻カスのリンス性向上の観点からは、５０，０００～３００，０００であることが特に好ましい。 Specific examples of the non-elastomer polymer preferably used in the present invention are listed below.
(1) Polyvinyl acetal and derivatives thereof Polyvinyl acetal is a compound obtained by cyclic acetalization of polyvinyl alcohol (obtained by saponifying polyvinyl acetate). Further, the polyvinyl acetal derivative is obtained by modifying the polyvinyl acetal or adding another copolymer component.
The acetal content in the polyvinyl acetal and its derivatives (the total number of moles of the raw vinyl acetate monomer being 100%, the mole% of vinyl alcohol units to be acetalized) is preferably 30 to 90%, more preferably 50 to 85%. Preferably, 55 to 78% is particularly preferable.
The vinyl alcohol unit in the polyvinyl acetal and derivatives thereof is preferably 10 to 70 mol%, more preferably 15 to 50 mol%, particularly preferably 22 to 45 mol%, based on the total number of moles of the raw vinyl acetate monomer. preferable.
The polyvinyl acetal and derivatives thereof may have vinyl acetate units as other components, and the content thereof is preferably 0.01 to 20 mol%, more preferably 0.1 to 10 mol%. The polyvinyl acetal derivative may further have other copolymer units.
Examples of the polyvinyl acetal include polyvinyl butyral, polyvinyl propylal, polyvinyl ethylal, and polyvinyl methylal. Among these, polyvinyl butyral derivative (PVB) is preferable.
Polyvinyl butyral is usually a polymer obtained by converting polyvinyl alcohol into butyral. A polyvinyl butyral derivative may also be used.
Examples of polyvinyl butyral derivatives include acid-modified PVB in which at least part of the hydroxyl group is modified to an acid group such as a carboxyl group, modified PVB in which part of the hydroxyl group is modified to a (meth) acryloyl group, and at least part of the hydroxyl group is an amino group Modified PVB, modified PVB in which ethylene glycol, propylene glycol, or a multimer thereof is introduced into at least a part of the hydroxyl group.
The molecular weight of polyvinyl acetal and its derivatives is preferably 5,000 to 800,000 as the weight average molecular weight, and preferably 8,000 to 500,000 from the viewpoint of maintaining a balance between engraving sensitivity and film property. More preferred. Further, from the viewpoint of improving the rinse property of engraving residue, it is particularly preferably 50,000 to 300,000.
　以下、ポリビニルアセタール及びその誘導体の特に好ましい例として、ポリビニルブチラール（ＰＶＢ）及びその誘導体を挙げて説明するが、これに限定されない。
　ポリビニルブチラールの構造は、以下に示す通りであり、これらの構成単位を含んで構成される。 Hereinafter, polyvinyl butyral (PVB) and derivatives thereof will be described as a particularly preferable example of polyvinyl acetal and derivatives thereof, but the invention is not limited thereto.
The structure of polyvinyl butyral is as shown below, and includes these structural units.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　上記式中、ｌ、ｍ及びｎは上記式中のそれぞれの繰返し単位のポリビニルブチラール中における含有量（モル％）を表し、ｌ＋ｍ＋ｎ＝１００の関係を満たす。ポリビニルブチラール及びその誘導体中のブチラール含量（上記式中におけるｌの値）は、３０～９０モル％が好ましく、４０～８５モル％がより好ましく、４５～７８モル％が特に好ましい。
　彫刻感度と皮膜性とのバランスの観点から、ポリビニルブチラール及びその誘導体の重量平均分子量は、５，０００～８００，０００が好ましく、８，０００～５００，０００がより好ましく、彫刻カスのリンス性向上の観点からは、５０，０００～３００，０００が特に好ましい。 In the above formula, l, m and n represent the content (mol%) of each repeating unit in the above formula in polyvinyl butyral and satisfy the relationship of l + m + n = 100. The butyral content (value of 1 in the above formula) in polyvinyl butyral and its derivatives is preferably 30 to 90 mol%, more preferably 40 to 85 mol%, particularly preferably 45 to 78 mol%.
From the viewpoint of balance between engraving sensitivity and film property, the weight average molecular weight of polyvinyl butyral and its derivatives is preferably 5,000 to 800,000, more preferably 8,000 to 500,000, and the rinse property of engraving residue is improved. In view of the above, 50,000 to 300,000 is particularly preferable.
　ＰＶＢ及びその誘導体としては、市販品としても入手可能であり、その好ましい具体例としては、アルコール溶解性（特にエタノール）の観点で、積水化学工業（株）製の「エスレックＢ」シリーズ、「エスレックＫ（ＫＳ）」シリーズ、電気化学工業（株）製の「デンカブチラール」が好ましい。更に好ましくは、アルコール溶解性（特にエタノール）の観点で積水化学工業（株）製の「エスレックＢ」シリーズと電気化学工業（株）製の「デンカブチラール」である。これらのうち、特に好ましい市販品を、上記式中の、ｌ、ｍ、及びｎの値と、分子量と共に以下に示す。積水化学工業（株）製の「エスレックＢ」シリーズでは、「ＢＬ－１」（ｌ＝６１、ｍ＝３、ｎ＝３６、重量平均分子量：１．９万）、「ＢＬ－１Ｈ」（ｌ＝６７、ｍ＝３、ｎ＝３０、重量平均分子量：２．０万）、「ＢＬ－２」（ｌ＝６１、ｍ＝３、ｎ＝３６、重量平均分子量：約２．７万）、「ＢＬ－５」（ｌ＝７５、ｍ＝４、ｎ＝２１、重量平均分子量：３．２万）、「ＢＬ－Ｓ」（ｌ＝７４、ｍ＝４、ｎ＝２２、重量平均分子量：２．３万）、「ＢＭ－Ｓ」（ｌ＝７３、ｍ＝５、ｎ＝２２、重量平均分子量：５．３万）、「ＢＨ－Ｓ」（ｌ＝７３、ｍ＝５、ｎ＝２２、重量平均分子量：６．６万）が、また、電気化学工業（株）製の「デンカブチラール」シリーズでは「＃３０００－１」（ｌ＝７１、ｍ＝１、ｎ＝２８、重量平均分子量：７．４万）、「＃３０００－２」（ｌ＝７１、ｍ＝１、ｎ＝２８、重量平均分子量：９．０万）、「＃３０００－４」（ｌ＝７１、ｍ＝１、ｎ＝２８、重量平均分子量：１１．７万）、「＃４０００－２」（ｌ＝７１、ｍ＝１、ｎ＝２８、重量平均分子量：１５．２万）、「＃６０００－Ｃ」（ｌ＝６４、ｍ＝１、ｎ＝３５、重量平均分子量：３０．８万）、「＃６０００－ＥＰ」（ｌ＝５６、ｍ＝１５、ｎ＝２９、重量平均分子量：３８．１万）、「＃６０００－ＣＳ」（ｌ＝７４、ｍ＝１、ｎ＝２５、重量平均分子量：３２．２万）、「＃６０００－ＡＳ」（ｌ＝７３、ｍ＝１、ｎ＝２６、重量平均分子量：２４．２万）が、それぞれ挙げられる。
　ＰＶＢ又はその誘導体を特定ポリマーとして用いてレリーフ形成膜を製膜する際には、溶剤に溶かした溶液をキャストし乾燥させる方法が、膜表面の平滑性の観点で好ましい。 PVB and its derivatives are also available as commercial products, and preferred specific examples thereof include, from the viewpoint of alcohol solubility (especially ethanol), “ESREC B” series, “ESREC” manufactured by Sekisui Chemical Co., Ltd. “K (KS)” series and “Denkabutyral” manufactured by Denki Kagaku Kogyo Co., Ltd. are preferable. More preferably, from the viewpoint of alcohol solubility (especially ethanol), “S Lec B” series manufactured by Sekisui Chemical Co., Ltd. and “Denka Butyral” manufactured by Denki Kagaku Kogyo Co., Ltd. are preferred. Among these, particularly preferable commercial products are shown below together with the values of l, m, and n and the molecular weight in the above formula. In the “S REC B” series manufactured by Sekisui Chemical Co., Ltd., “BL-1” (l = 61, m = 3, n = 36, weight average molecular weight: 190000), “BL-1H” (l = 67, m = 3, n = 30, weight average molecular weight: 20,000), “BL-2” (l = 61, m = 3, n = 36, weight average molecular weight: about 27,000), “BL-5” (l = 75, m = 4, n = 21, weight average molecular weight: 32,000), “BL-S” (l = 74, m = 4, n = 22, weight average molecular weight: 230,000), “BM-S” (l = 73, m = 5, n = 22, weight average molecular weight: 53,000), “BH-S” (l = 73, m = 5, n = 22 and weight average molecular weight: 66,000), but in the “Denka Butyral” series manufactured by Denki Kagaku Kogyo Co., Ltd., “# 3000-1” (l = 71, m = 1, n = 28, weight average) Min Amount: 74,000), “# 3000-2” (l = 71, m = 1, n = 28, weight average molecular weight: 90000), “# 3000-4” (l = 71, m = 1, n = 28, weight average molecular weight: 17,000), “# 4000-2” (l = 71, m = 1, n = 28, weight average molecular weight: 152,000), “# 6000-C (L = 64, m = 1, n = 35, weight average molecular weight: 308,000), “# 6000-EP” (l = 56, m = 15, n = 29, weight average molecular weight: 38.1) ), “# 6000-CS” (l = 74, m = 1, n = 25, weight average molecular weight: 322,000), “# 6000-AS” (l = 73, m = 1, n = 26) , Weight average molecular weight: 242,000).
When forming a relief forming film using PVB or a derivative thereof as a specific polymer, a method of casting and drying a solution dissolved in a solvent is preferable from the viewpoint of the smoothness of the film surface.
（２）アクリル樹脂
　特定ポリマーとして用いることができるアクリル樹脂としては、公知のアクリル単量体を用いて得るアクリル樹脂であって、分子内にヒドロキシ基を有するものであればよい。
　ヒドロキシ基を有するアクリル樹脂の合成に用いられるアクリル単量体としては、例えば（メタ）アクリル酸エステル類、クロトン酸エステル類、（メタ）アクリルアミド類であって分子内にヒドロキシ基を有するものが好ましい。このような単量体の具体例としては例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等が挙げられる。
　なお、本発明において、「（メタ）アクリル」とは、「アクリル」及び「メタクリル」のいずれか一方、又は、その両方を含む語であり、「（メタ）アクリレート」とは、「アクリル」及び「メタクリル」のいずれか一方、又は、その両方を含む語である。 (2) Acrylic resin The acrylic resin that can be used as the specific polymer may be an acrylic resin obtained by using a known acrylic monomer and has a hydroxy group in the molecule.
As the acrylic monomer used for the synthesis of the acrylic resin having a hydroxy group, for example, (meth) acrylic acid esters, crotonic acid esters, (meth) acrylamides having a hydroxy group in the molecule are preferable. . Specific examples of such a monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
In the present invention, “(meth) acryl” is a term including one or both of “acryl” and “methacryl”, and “(meth) acrylate” means “acryl” and It is a term that includes either “methacrylic” or both.
　また、アクリル樹脂としては、上記ヒドロキシ基を有するアクリル単量体以外のアクリル単量体を共重合成分として含むこともできる。このようなアクリル単量体としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、アセトキシエチル（メタ）アクリレート、フェニル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、２－（２－メトキシエトキシ）エチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、ジエチレングリコールモノメチルエーテル（メタ）アクリレート、ジエチレングリコールモノエチルエーテル（メタ）アクリレート、ジエチレングリコールモノフェニルエーテル（メタ）アクリレート、トリエチレングリコールモノメチルエーテル（メタ）アクリレート、トリエチレングリコールモノエチルエーテル（メタ）アクリレート、ジプロピレングリコールモノメチルエーテル（メタ）アクリレート、ポリエチレングリコールモノメチルエーテル（メタ）アクリレート、ポリプロピレングリコールモノメチルエーテル（メタ）アクリレート、エチレングリコールとプロピレングリコールとの共重合体のモノメチルエーテル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリレート等が挙げられる。
　更に、ウレタン基やウレア基を有するアクリル単量体を含んで構成される変性アクリル樹脂も好ましく使用することができる。
　これらの中でも、水性インキ耐性の観点で、ラウリル（メタ）アクリレートなどのアルキル（メタ）アクリレート類、ｔ－ブチルシクロヘキシルメタクリレートなど脂肪族環状構造を有する（メタ）アクリレート類が特に好ましい。 Moreover, as an acrylic resin, acrylic monomers other than the acrylic monomer which has the said hydroxyl group can also be included as a copolymerization component. Examples of such acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-Butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (Meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, di Tylene glycol monoethyl ether (meth) acrylate, diethylene glycol monophenyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, Polyethylene glycol monomethyl ether (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, monomethyl ether (meth) acrylate of a copolymer of ethylene glycol and propylene glycol, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate Relate and the like.
Furthermore, a modified acrylic resin comprising an acrylic monomer having a urethane group or a urea group can also be preferably used.
Among these, alkyl (meth) acrylates such as lauryl (meth) acrylate and (meth) acrylates having an aliphatic cyclic structure such as t-butylcyclohexyl methacrylate are particularly preferable from the viewpoint of water-based ink resistance.
（３）ノボラック樹脂
　また、特定ポリマーとして、フェノール類とアルデヒド類を酸性条件下で縮合させた樹脂であるノボラック樹脂を用いてもよい。
　好ましいノボラック樹脂としては、例えばフェノールとホルムアルデヒドから得られるノボラック樹脂、ｍ－クレゾールとホルムアルデヒドから得られるノボラック樹脂、ｐ－クレゾールとホルムアルデヒドから得られるノボラック樹脂、ｏ－クレゾールとホルムアルデヒドから得られるノボラック樹脂、オクチルフェノールとホルムアルデヒドから得られるノボラック樹脂、ｍ－／ｐ－混合クレゾールとホルムアルデヒドから得られるノボラック樹脂、フェノール／クレゾール（ｍ－，ｐ－，ｏ－又はｍ－／ｐ－，ｍ－／ｏ－，ｏ－／ｐ－混合のいずれでもよい）の混合物とホルムアルデヒドから得られるノボラック樹脂などが挙げられる。
　これらのノボラック樹脂は、重量平均分子量が８００～２００，０００で、数平均分子量が４００～６０，０００のものが好ましい。
　特定ポリマーとして、ヒドロキシ基を側鎖に有するエポキシ樹脂を用いることも可能である。好ましい具体例としては、ビスフェノールＡとエピクロヒドリンの付加物を原料モノマーとして重合して得られるエポキシ樹脂が好ましい。
　これらのエポキシ樹脂は、重量平均分子量が８００～２００，０００であり、かつ、数平均分子量が４００～６０，０００のものが好ましい。 (3) Novolak resin Moreover, you may use the novolak resin which is resin which condensed phenols and aldehydes on acidic conditions as a specific polymer.
Preferred novolak resins include, for example, novolak resins obtained from phenol and formaldehyde, novolak resins obtained from m-cresol and formaldehyde, novolak resins obtained from p-cresol and formaldehyde, novolak resins obtained from o-cresol and formaldehyde, and octylphenol. Novolak resin obtained from aldehyde and formaldehyde, m- / p-mixed cresol and novolak resin obtained from formaldehyde, phenol / cresol (m-, p-, o- or m- / p-, m- / o-, o- / P-mixture) and a novolak resin obtained from formaldehyde.
These novolak resins preferably have a weight average molecular weight of 800 to 200,000 and a number average molecular weight of 400 to 60,000.
It is also possible to use an epoxy resin having a hydroxy group in the side chain as the specific polymer. As a preferable specific example, an epoxy resin obtained by polymerizing an adduct of bisphenol A and epichlorohydrin as a raw material monomer is preferable.
These epoxy resins preferably have a weight average molecular weight of 800 to 200,000 and a number average molecular weight of 400 to 60,000.
　特定ポリマーの中でも、レリーフ形成膜としたときのリンス性及び耐刷性の観点でポリビニルブチラール誘導体が特に好ましい。
　本発明における特定ポリマーに含まれるヒドロキシ基の含有量は、上記いずれの態様のポリマーにおいても、０．１～１５ｍｍｏｌ／ｇであることが好ましく、０．５～７ｍｍｏｌ／ｇであることがより好ましい。 Among the specific polymers, polyvinyl butyral derivatives are particularly preferable from the viewpoints of rinsing properties and printing durability when used as a relief-forming film.
The hydroxy group content contained in the specific polymer in the present invention is preferably 0.1 to 15 mmol / g, more preferably 0.5 to 7 mmol / g in any of the above-described polymers. .
（成分Ａ－２）親水性ポリマー
　本発明において、成分Ａとして、（成分Ａ－２）親水性ポリマーを使用することも好ましい。
　親水性ポリマーとは、水に溶解又は膨潤するポリマーを意味する。親水性の樹脂は概して油性インキに対して耐性があり、好ましく使用される。このような樹脂として、例えばヒドロキシエチレンを含む親水性ポリマー、セルロースをはじめとする親水性官能基を有する多糖類、ポリアクリル酸ナトリウムのような酸性官能基が中和された塩構造やアミノ基が中和された塩構造やオニウム構造を含むアクリル樹脂、ポリエチレンオキサイドの如き親水性基を導入したポリアミド樹脂、ゼラチンなどが挙げられる。
　良好な親水性を示す点で、ヒドロキシエチレンを含む親水性ポリマー、アミノ基又はカルボン酸基／スルホン酸基／硫酸基及びこれらが中和された塩構造などの極性基含有セルロース、アミノ基又はカルボン酸基／スルホン酸基／硫酸基及びこれらが中和された塩構造などの極性基含有アクリル樹脂、ポリアミド樹脂が好ましい。
　より好ましくは、ヒドロキシエチレンを含む親水性ポリマー、アミノ基又はカルボン酸基／スルホン酸基／硫酸基及びこれらが中和された塩構造などの極性基含有アクリル樹脂、ポリアミド樹脂が好ましく、特に好ましくはポリビニルアルコール類、ポリアミド樹脂である。特に好ましくはポリビニルアルコール誘導体（ＰＶＡ誘導体）である。 (Component A-2) Hydrophilic Polymer In the present invention, it is also preferable to use (Component A-2) a hydrophilic polymer as Component A.
A hydrophilic polymer means a polymer that dissolves or swells in water. Hydrophilic resins are generally resistant to oil-based inks and are preferably used. Examples of such resins include hydrophilic polymers containing hydroxyethylene, polysaccharides having hydrophilic functional groups such as cellulose, and salt structures and amino groups neutralized with acidic functional groups such as sodium polyacrylate. Examples thereof include acrylic resins containing a neutralized salt structure and onium structure, polyamide resins having a hydrophilic group introduced such as polyethylene oxide, and gelatin.
Hydrophilic polymer containing hydroxyethylene, polar group-containing cellulose such as amino group or carboxylic acid group / sulfonic acid group / sulfuric acid group and salt structure in which these are neutralized, amino group or carboxylic acid in terms of showing good hydrophilicity A polar group-containing acrylic resin and polyamide resin such as acid group / sulfonic acid group / sulfuric acid group and a salt structure in which these are neutralized are preferred.
More preferred are hydrophilic polymers containing hydroxyethylene, polar groups-containing acrylic resins such as amino groups or carboxylic acid groups / sulfonic acid groups / sulfuric acid groups and salt structures in which these are neutralized, and polyamide resins, particularly preferred. Polyvinyl alcohols and polyamide resins. Particularly preferred are polyvinyl alcohol derivatives (PVA derivatives).
　親水性ポリマーとしては、ＰＶＡ誘導体が好ましい。本発明において、ＰＶＡ誘導体とは、ヒドロキシエチレン単位を０．１モル％以上１００モル％以下、好ましくは１モル％以上９８モル％以下、更に好ましくは５モル％以上９５モル％以下含有する共重合体或いは重合体並びにそれらの変性体を意味する。従って、ポリビニルアルコール自体も包含する。該共重合体を形成するためのモノマーとしては、公知の共重合可能なモノマーから適宜選定することができる。該変性体としては、後述のものが例示される。
　ＰＶＡ誘導体としては、特に好ましくはポリビニルアルコール及びビニルアルコール／酢酸ビニル共重合体（部分鹸化ポリビニルアルコール）を例示することができ、これらの変性体もこれに該当する。
　親水性ポリマーとして単独のポリマーを用いてもよいし、複数種を混合して用いてもよい。
　親水性ポリマーとして、特にＰＶＡ誘導体とヒドロキシエチレン単位を含まない親水性ポリマーを併用することが好ましい。上記ヒドロキシエチレン単位を含まない親水性ポリマーを非ＰＶＡ誘導体とも記す。
　親水性ポリマーについては、特開２００９－２２６９４６号公報の段落００３９～００４４記載が参照される。 As the hydrophilic polymer, a PVA derivative is preferable. In the present invention, the PVA derivative is a copolymer containing 0.1 to 100 mol%, preferably 1 to 98 mol%, more preferably 5 to 95 mol% of a hydroxyethylene unit. It means a polymer or a polymer and a modified product thereof. Therefore, polyvinyl alcohol itself is also included. The monomer for forming the copolymer can be appropriately selected from known copolymerizable monomers. Examples of the modified body include those described below.
Particularly preferred examples of the PVA derivative include polyvinyl alcohol and vinyl alcohol / vinyl acetate copolymer (partially saponified polyvinyl alcohol), and these modified products also fall under this category.
A single polymer may be used as the hydrophilic polymer, or a plurality of types may be mixed and used.
As the hydrophilic polymer, it is particularly preferable to use a PVA derivative and a hydrophilic polymer not containing a hydroxyethylene unit in combination. The hydrophilic polymer containing no hydroxyethylene unit is also referred to as a non-PVA derivative.
Regarding the hydrophilic polymer, refer to paragraphs 0039 to 0044 of JP-A-2009-226946.
　成分Ａの硬化性樹脂組成物中の含有量は、全固形分に対して５～９０質量％であることが好ましく、１５～８５質量％であることがより好ましく、３０～８０質量％であることが更に好ましい。
　なお、組成物の固形分とは、組成物から溶剤等の揮発成分を除いたものを意味する。 The content of the component A in the curable resin composition is preferably 5 to 90% by mass, more preferably 15 to 85% by mass, and more preferably 30 to 80% by mass with respect to the total solid content. More preferably.
In addition, solid content of a composition means what remove | excluded volatile components, such as a solvent, from a composition.
（成分Ｂ）架橋剤
　本発明において、硬化性樹脂組成物は、（成分Ｂ）架橋剤を含有することが好ましい。架橋剤によりレリーフ形成膜に架橋構造が導入されることで、耐刷性に優れたレリーフ形成膜が得られる。
　（成分Ｂ）架橋剤としては、（成分Ｂ－１）加水分解性シリル基及び／又はシラノール基を有する化合物、（成分Ｂ－２）多官能エチレン性不飽和化合物、又は、（成分Ｂ－３）エポキシ環、オキセタン環及び五員環カーボネートよりなる群から選ばれた環状構造を２以上有する化合物を含むことが好ましい。
　（成分Ｂ－１）加水分解性シリル基及び／又はシラノール基を有する化合物としては、従来、シランカップリング剤として公知の各種の化合物を使用することができ、例えば、特開２０１２－１１６００８号公報の段落００２７～００５４の記載が参照できる。
　成分（Ｂ－２）多官能エチレン性不飽和化合物は、末端エチレン性不飽和基を少なくとも２つ有する化合物から適宜選択して用いることができる。このような化合物群は当該産業分野において広く知られており、本発明において、これらを特に制限なく用いることができる。（成分Ｂ－２）多官能エチレン性不飽和化合物としては、特開２０１２－１１６００８号公報の段落００５５～００７４の記載が参照できる。
　また、（成分Ｂ）架橋剤として、（成分Ｂ－３）エポキシ環、オキセタン環及び五員環カーボネートよりなる群から選ばれた環状構造を２以上有する化合物を使用してもよく、例えば、特開２０１２－１１６００８号公報の段落００７５～００９５が参照できる。 (Component B) Crosslinking Agent In the present invention, the curable resin composition preferably contains (Component B) a crosslinking agent. By introducing a crosslinked structure into the relief-forming film by the crosslinking agent, a relief-forming film having excellent printing durability can be obtained.
(Component B) Crosslinking agent includes (Component B-1) a compound having a hydrolyzable silyl group and / or silanol group, (Component B-2) a polyfunctional ethylenically unsaturated compound, or (Component B-3) It is preferable to include a compound having two or more cyclic structures selected from the group consisting of epoxy rings, oxetane rings and five-membered ring carbonates.
(Component B-1) As the compound having a hydrolyzable silyl group and / or silanol group, various compounds conventionally known as silane coupling agents can be used. For example, JP 2012-116008 A In paragraphs 0027 to 0054.
The component (B-2) polyfunctional ethylenically unsaturated compound can be appropriately selected from compounds having at least two terminal ethylenically unsaturated groups. Such compound groups are widely known in the industrial field, and these can be used without particular limitation in the present invention. As the (component B-2) polyfunctional ethylenically unsaturated compound, the description in paragraphs 0055 to 0074 of JP2012-116008A can be referred to.
Further, as (Component B) the crosslinking agent, (Component B-3) a compound having two or more cyclic structures selected from the group consisting of an epoxy ring, an oxetane ring and a five-membered carbonate may be used. Reference can be made to paragraphs 0075 to 0095 of JP2012-116008.
　成分Ｂは１種単独で使用してもよく、２種以上を併用してもよい。また、例えば、成分Ｂ－１を２種以上使用することもできるし、成分Ｂ－１を１種類と、成分Ｂ－２を１種類のように、異なる架橋系を形成する２種以上を併用してもよい。
　これらの中でも、成分Ｂとして成分Ｂ－１及び／又は成分Ｂ－２を含有することが好ましく、少なくとも成分Ｂ－２を含有することがより好ましい。
　成分Ｂの硬化性樹脂組成物中の含有量は、全固形分に対し０．１～８０質量％であることが好ましく、１～４０質量％であることがより好ましく、５～３０質量％であることが更に好ましい。 Component B may be used alone or in combination of two or more. Also, for example, two or more types of component B-1 can be used, or two or more types that form different crosslinking systems, such as one type of component B-1 and one type of component B-2, can be used in combination. May be.
Among these, the component B preferably contains the component B-1 and / or the component B-2, and more preferably contains at least the component B-2.
The content of the component B in the curable resin composition is preferably 0.1 to 80% by mass, more preferably 1 to 40% by mass, and more preferably 5 to 30% by mass with respect to the total solid content. More preferably it is.
（成分Ｃ）架橋触媒
　本発明において、硬化性樹脂組成物は、（成分Ｃ）架橋触媒を含有することが好ましい。本発明に用いることができる（成分Ｃ）架橋触媒としては、（成分Ｃ－１）アルコール交換反応触媒、（成分Ｃ－２）重合開始剤、又は、（成分Ｃ－３）成分Ｂ－３と反応して架橋構造を形成しうる硬化剤が好ましく例示される。
　成分Ｂとして（成分Ｂ－１）加水分解性シリル基及び／又はシラノール基を有する化合物を使用する場合、（成分Ｃ－１）アルコール交換反応触媒を含有することが好ましい。アルコール交換反応触媒は、シランカップリング反応において一般に用いられる反応触媒であれば、限定なく適用できる。アルコール交換反応触媒としては、酸性触媒又は塩基性触媒、及び、金属錯体触媒が挙げられ、例えば、特開２０１２－１１６００８号公報の段落００９８～０１１０の記載が参照できる。 (Component C) Crosslinking Catalyst In the present invention, the curable resin composition preferably contains (Component C) a crosslinking catalyst. Examples of the (Component C) crosslinking catalyst that can be used in the present invention include (Component C-1) an alcohol exchange reaction catalyst, (Component C-2) a polymerization initiator, or (Component C-3) and a component B-3. A curing agent that can react to form a crosslinked structure is preferably exemplified.
When (Component B-1) a compound having a hydrolyzable silyl group and / or silanol group is used as Component B, (Component C-1) an alcohol exchange reaction catalyst is preferably contained. The alcohol exchange reaction catalyst can be applied without limitation as long as it is a reaction catalyst generally used in a silane coupling reaction. Examples of the alcohol exchange reaction catalyst include an acidic catalyst or a basic catalyst, and a metal complex catalyst. For example, the description in paragraphs 0098 to 0110 of JP2012-116008A can be referred to.
　また、成分Ｂとして（成分Ｂ－２）多官能エチレン性不飽和化合物を含有する場合、（成分Ｃ－２）重合開始剤を含有することが好ましい。本発明において、重合開始剤はラジカル重合開始剤であることが好ましく、また、熱重合開始剤であることが好ましい。好ましいラジカル重合開始剤としては、（ａ）芳香族ケトン類、（ｂ）オニウム塩化合物、（ｃ）有機過酸化物、（ｄ）チオ化合物、（ｅ）ヘキサアリールビイミダゾール化合物、（ｆ）ケトオキシムエステル化合物、（ｇ）ボレート化合物、（ｈ）アジニウム化合物、（ｉ）メタロセン化合物、（ｊ）活性エステル化合物、（ｋ）炭素ハロゲン結合を有する化合物、（ｌ）アゾ系化合物等が挙げられ、彫刻感度と、レリーフ印刷版原版のレリーフ形成膜に適用した際にはレリーフエッジ形状を良好とするといった観点から、（ｃ）有機過酸化物及び（ｌ）アゾ系化合物がより好ましく、（ｃ）有機過酸化物が特に好ましい。
　重合開始剤については、例えば、特開２０１２－１１６００８号公報の段落０１１１～０１１８の記載が参照できる。 Further, when (Component B-2) a polyfunctional ethylenically unsaturated compound is contained as Component B, it is preferable to contain (Component C-2) a polymerization initiator. In the present invention, the polymerization initiator is preferably a radical polymerization initiator, and is preferably a thermal polymerization initiator. Preferred radical polymerization initiators include (a) aromatic ketones, (b) onium salt compounds, (c) organic peroxides, (d) thio compounds, (e) hexaarylbiimidazole compounds, (f) keto Oxime ester compounds, (g) borate compounds, (h) azinium compounds, (i) metallocene compounds, (j) active ester compounds, (k) compounds having a carbon halogen bond, (l) azo compounds, and the like. From the viewpoint of engraving sensitivity and a good relief edge shape when applied to a relief forming film of a relief printing plate precursor, (c) an organic peroxide and (l) an azo compound are more preferred, (c) Organic peroxides are particularly preferred.
As for the polymerization initiator, for example, the descriptions in paragraphs 0111 to 0118 of JP2012-116008A can be referred to.
　成分Ｂとして（成分Ｂ－３）エポキシ環、オキセタン環及び五員環カーボネートよりなる群から選ばれた環状構造を２以上有する化合物を含有する場合、（成分Ｃ－３）成分Ｂ－３と反応して架橋構造を形成しうる硬化剤を含有することが好ましい。成分Ｃ－３は、反応速度が速く、高強度の膜が得られる観点から、第一級アミノ基及び酸無水物基よりなる群から選ばれた官能基を少なくとも１つ有する化合物、又は、第二級アミノ基、メルカプト基、カルボキシル基、フェノール性ヒドロキシ基及びヒドロキシ基よりなる群から選ばれた官能基を２つ以上有する化合物であることが好ましい。成分Ｃ－３としては、例えば、特開２０１２－１１６００８号公報の段落０１１９～０１３０の記載が参照できる。 When component B contains (component B-3) a compound having two or more cyclic structures selected from the group consisting of epoxy ring, oxetane ring and five-membered carbonate, (component C-3) reacts with component B-3 It is preferable to contain a curing agent that can form a crosslinked structure. Component C-3 is a compound having at least one functional group selected from the group consisting of a primary amino group and an acid anhydride group from the viewpoint of having a high reaction rate and obtaining a high-strength film, or A compound having two or more functional groups selected from the group consisting of secondary amino groups, mercapto groups, carboxyl groups, phenolic hydroxy groups and hydroxy groups is preferred. As the component C-3, for example, the description in paragraphs 0119 to 0130 of JP2012-116008A can be referred to.
　成分Ｃは一種単独で使用してもよく、２種以上を併用してもよい。使用する成分Ｂに合わせて、成分Ｃを適宜選択することが好ましい。
　成分Ｃの含有量としては、硬化性樹脂組成物の全固形分量に対し、０．０１～４０質量％であることが好ましく、０．０５～３０質量％であることがより好ましく、０．１～２０質量％であることが更に好ましい。 Component C may be used alone or in combination of two or more. It is preferable to appropriately select component C according to the component B to be used.
The content of component C is preferably 0.01 to 40% by mass, more preferably 0.05 to 30% by mass, based on the total solid content of the curable resin composition. More preferably, it is ˜20% by mass.
　本発明において、硬化性樹脂組成物は、上記の成分Ａ～成分Ｃに加え、（成分Ｄ）光熱交換剤、（成分Ｅ）可塑剤、（成分Ｆ）溶剤を含有することが好ましい。
（成分Ｄ）光熱交換剤
　本発明において、硬化性樹脂組成物は、（成分Ｄ）光熱変換剤を含有することが好ましい。本発明において、光熱変換剤は、レーザーの光を吸収し発熱することで、レーザー彫刻時のレリーフ形成の熱分解を促進すると考えられる。このため、彫刻に用いるレーザー波長の光を吸収する光熱変換剤を選択することが好ましい。 In the present invention, the curable resin composition preferably contains (Component D) a photothermal exchange agent, (Component E) a plasticizer, and (Component F) a solvent in addition to the above components A to C.
(Component D) Photothermal Exchanger In the present invention, the curable resin composition preferably contains (Component D) a photothermal conversion agent. In the present invention, the photothermal conversion agent is considered to promote thermal decomposition of relief formation during laser engraving by absorbing laser light and generating heat. For this reason, it is preferable to select a photothermal conversion agent that absorbs light having a laser wavelength used for engraving.
　本発明のレリーフ印刷版原版において、７００ｎｍ以上１，３００ｎｍ以下の赤外線を発するレーザー（ＹＡＧレーザー、半導体レーザー、ファイバーレーザー、面発光レーザー等）を光源としてレーザー彫刻に用いる場合に、赤外線吸収剤として成分Ｄが用いられることが好ましい。成分Ｄは、上記レーザー光を吸収し、発熱して上記印刷版原版のレリーフ形成膜の熱分解を促進し、本発明のレリーフ印刷版原版のレーザー彫刻における感度を向上させると考えられる。従って、成分Ｄとしては、７００ｎｍ～１，３００ｎｍに吸収波長を有する化合物が好ましく、７００ｎｍ～１，３００ｎｍに極大吸収波長を有する化合物がより好ましい。
　成分Ｄの具体的化合物として、波長７００ｎｍ～１,３００ｎｍの光を吸収する顔料及び染料よりなる群から選択される少なくとも１つを含有することが好ましく、波長７００ｎｍ～１，３００ｎｍの光を含有する顔料を有することがより好ましい。 In the relief printing plate precursor of the present invention, a component that serves as an infrared absorber when a laser (YAG laser, semiconductor laser, fiber laser, surface emitting laser, etc.) emitting infrared rays of 700 nm to 1,300 nm is used as a light source for laser engraving Preferably D is used. Component D is believed to absorb the laser beam and generate heat to promote thermal decomposition of the relief forming film of the printing plate precursor, and improve the sensitivity of the relief printing plate precursor of the present invention in laser engraving. Therefore, as the component D, a compound having an absorption wavelength at 700 nm to 1,300 nm is preferable, and a compound having a maximum absorption wavelength at 700 nm to 1,300 nm is more preferable.
The specific compound of component D preferably contains at least one selected from the group consisting of pigments and dyes that absorb light having a wavelength of 700 nm to 1,300 nm, and contains light having a wavelength of 700 nm to 1,300 nm. It is more preferable to have a pigment.
　染料としては、特開２０１０－１０００４７号公報の段落０２６３～０２７４に記載の染料が好ましく例示される。
　本発明において使用される顔料としては、市販の顔料及びカラーインデックス（Ｃ．Ｉ．）便覧、「最新顔料便覧」（日本顔料技術協会編、１９７７年刊）、「最新顔料応用技術」（ＣＭＣ出版、１９８６年刊）、「印刷インキ技術」ＣＭＣ出版、１９８４年刊）に記載されている顔料が利用できる。 Preferred examples of the dye include those described in paragraphs 0263 to 0274 of JP2010-100047A.
Examples of the pigment used in the present invention include commercially available pigments and color index (CI) manual, “Latest Pigment Handbook” (edited by Japan Pigment Technology Association, published in 1977), “Latest Pigment Application Technology” (CMC Publishing, 1986), “Printing Ink Technology”, CMC Publishing, 1984) can be used.
　顔料の種類としては、黒色顔料、黄色顔料、オレンジ色顔料、褐色顔料、赤色顔料、紫色顔料、青色顔料、緑色顔料、蛍光顔料、金属粉顔料、その他、ポリマー結合色素が挙げられる。具体的には、不溶性アゾ顔料、アゾレーキ顔料、縮合アゾ顔料、キレートアゾ顔料、フタロシアニン系顔料、アントラキノン系顔料、ペリレン及びペリノン系顔料、チオインジゴ系顔料、キナクリドン系顔料、ジオキサジン系顔料、イソインドリノン系顔料、キノフタロン系顔料、染付けレーキ顔料、アジン顔料、ニトロソ顔料、ニトロ顔料、天然顔料、蛍光顔料、無機顔料、カーボンブラック等が使用できる。これらの顔料のうち特に好ましいものはカーボンブラックである。 Examples of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used. Among these pigments, carbon black is particularly preferable.
　これら顔料は表面処理をせずに用いてもよく、表面処理を施して用いてもよい。表面処理の方法には、樹脂やワックスを表面コートする方法、界面活性剤を付着させる方法、反応性物質（例えば、シランカップリング剤、エポキシ化合物、ポリイソシアネート等）を顔料表面に結合させる方法等が考えられる。上記の表面処理方法は、「金属石鹸の性質と応用」（幸書房）、「印刷インキ技術」（ＣＭＣ出版、１９８４年刊）及び「最新顔料応用技術」（ＣＭＣ出版、１９８６年刊）に記載されている。 These pigments may be used without surface treatment or may be used after surface treatment. The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Shobobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.
　更に、これらの光熱変換剤の熱分解温度がバインダーポリマーの熱分解温度同等以上という組み合わせ（条件）で使用する場合に更に彫刻感度が高くなる傾向であり好ましい。 Furthermore, when the photothermal conversion agent is used in a combination (condition) in which the thermal decomposition temperature of the binder polymer is equal to or higher than the thermal decomposition temperature of the binder polymer, the engraving sensitivity tends to be higher, which is preferable.
　本発明で用いられる光熱変換剤の具体例としては、ヘプタメチンシアニン色素等のシアニン系色素、ペンタメチンオキソノール色素等のオキソノール系色素、インドリウム系色素、ベンズインドリウム系色素、ベンゾチアゾリウム系色素、キノリニウム系色素、顕色剤と反応させたフタリド化合物等を挙げることができる。全てのシアニン系色素が、前述した光吸収特性を有するものではない。置換基の種類及び分子内での位置、共役結合の数、対イオンの種類、色素分子の存在する周囲の環境などにより、光吸収特性が極めて大きく変化する。 Specific examples of the photothermal conversion agent used in the present invention include cyanine dyes such as heptamethine cyanine dyes, oxonol dyes such as pentamethine oxonol dyes, indolium dyes, benzindolinium dyes, and benzothiazolium. And phthalide compounds reacted with a colorant, a quinolinium colorant, and a developer. Not all cyanine dyes have the light absorption characteristics described above. The light absorption characteristics vary greatly depending on the type of substituent and position in the molecule, the number of conjugated bonds, the type of counterion, the surrounding environment in which the dye molecule is present, and the like.
　また、一般に市販されているレーザー色素、過飽和吸収色素、近赤外線吸収色素を使用することもできる。例えば、レーザー色素として、アメリカン・ダイ・ソース社（カナダ国）の商標「ＡＤＳ７４０ＰＰ」、「ＡＤＳ７４５ＨＴ」、「ＡＤＳ７６０ＭＰ」、「ＡＤＳ７４０ＷＳ」、「ＡＤＳ７６５ＷＳ」、「ＡＤＳ７４５ＨＯ」、「ＡＤＳ７９０ＮＨ」、「ＡＤＳ８００ＮＨ」、（株）林原生物化学研究所製の商標「ＮＫ－３５５５」、「ＮＫ－３５０９」、「ＮＫ－３５１９」を挙げることができる。また、近赤外線吸収色素として、アメリカン・ダイ・ソース社（カナダ国）商標「ＡＤＳ７７５ＭＩ」、「ＡＤＳ７７５ＭＰ」、「ＡＤＳ７７５ＨＩ」、「ＡＤＳ７７５ＰＩ」、「ＡＤＳ７７５ＰＰ」、「ＡＤＳ７８０ＭＴ」、「ＡＤＳ７８０ＢＰ」、「ＡＤＳ７９３ＥＩ」、「ＡＤＳ７９８ＭＩ」、「ＡＤＳ７９８ＭＰ」、「ＡＤＳ８００ＡＴ」、「ＡＤＳ８０５ＰＩ」、「ＡＤＳ８０５ＰＰ」、「ＡＤＳ８０５ＰＡ」、「ＡＤＳ８０５ＰＦ」、「ＡＤＳ８１２ＭＩ」、「ＡＤＳ８１５ＥＩ」、「ＡＤＳ８１８ＨＩ」、「ＡＤＳ８１８ＨＴ」、「ＡＤＳ８２２ＭＴ」、「ＡＤＳ８３０ＡＴ」、「ＡＤＳ８３８ＭＴ」、「ＡＤＳ８４０ＭＴ」、「ＡＤＳ８４５ＢＩ」、「ＡＤＳ９０５ＡＭ」、「ＡＤＳ９５６ＢＩ」、「ＡＤＳ１０４０Ｔ」、「ＡＤＳ１０４０Ｐ」、「ＡＤＳ１０４５Ｐ」、「ＡＤＳ１０５０Ｐ」、「ＡＤＳ１０６０Ａ」、「ＡＤＳ１０６５Ａ」、「ＡＤＳ１０６５Ｐ」、「ＡＤＳ１１００Ｔ」、「ＡＤＳ１１２０Ｆ」、「ＡＤＳ１１２０Ｐ」、「ＡＤＳ７８０ＷＳ」、「ＡＤＳ７８５ＷＳ」、「ＡＤＳ７９０ＷＳ」、「ＡＤＳ８０５ＷＳ」、「ＡＤＳ８２０ＷＳ」、「ＡＤＳ８３０ＷＳ」、「ＡＤＳ８５０ＷＳ」、「ＡＤＳ７８０ＨＯ」、「ＡＤＳ８１０ＣＯ」、「ＡＤＳ８２０ＨＯ」、「ＡＤＳ８２１ＮＨ」、「ＡＤＳ８４０ＮＨ」、「ＡＤＳ８８０ＭＣ」、「ＡＤＳ８９０ＭＣ」、「ＡＤＳ９２０ＭＣ」、山本化成（株）製、商標「ＹＫＲ－２２００」、「ＹＫＲ－２０８１」、「ＹＫＲ－２９００」、「ＹＫＲ－２１００」、「ＹＫＲ－３０７１」、有本化学工業（株）製、商標「ＳＤＯ－１０００Ｂ」、（株）林原生物化学研究所製、商標「ＮＫ－３５０８」、「ＮＫＸ－１１４」を挙げることができる。ただし、これらのみに限定されるものではない。 Also, commercially available laser dyes, supersaturated absorbing dyes, and near infrared absorbing dyes can be used. For example, as a laser dye, trade marks “ADS740PP”, “ADS745HT”, “ADS760MP”, “ADS740WS”, “ADS765WS”, “ADS745NH”, “ADS790NH”, “ADS800NH” of American Dye Source (Canada), Trademarks “NK-3555”, “NK-3509”, and “NK-3519” manufactured by Hayashibara Biochemical Laboratories, Inc. can be mentioned. In addition, as the near-infrared absorbing dyes, trade names “ADS775MI”, “ADS775MP”, “ADS775HI”, “ADS775PI”, “ADS775PP”, “ADS780MT”, “ADS780BP”, “ADS793EI”, trade names “ADS775MI”, “ADS775MP”, “ADS775HI” , “ADS798MI”, “ADS798MP”, “ADS800AT”, “ADS805PI”, “ADS805PP”, “ADS805PA”, “ADS805PF”, “ADS812MI”, “ADS815EI”, “ADS818HI”, “ADS818HT”, “ADS8” ADS830AT, ADS838MT, ADS840MT, ADS845BI, ADS905AM, ADS956BI, ADS1040T, “ADS1040P”, “ADS1045P”, “ADS1050P”, “ADS1060A”, “ADS1065A”, “ADS1065P”, “ADS1100T”, “ADS1120F”, “ADS1120P”, “ADS780WS”, “ADS785WS”, “ADS790WS”, “ADS790WS”, “ADS790WS” , ADS820WS, ADS830WS, ADS850WS, ADS780HO, ADS810CO, ADS820HO, ADS821NH, ADS840NH, ADS880MC, ADS890MC, Yamamoto Corporation Trademarks “YKR-2200”, “YKR-2081”, “YKR-2900”, “YKR-2100”, “YKR-3071” Industries Co., Ltd., trademark "SDO-1000B", (Ltd.) Hayashibara Biochemical Laboratories, Ltd., trademark "NK-3508", mention may be made of the "NKX-114". However, it is not limited only to these.
　また、顕色剤と反応させたフタリド化合物は、特許第３２７１２２６号公報に記載されているものを用いることもできる。また、リン酸エステル金属化合物、例えば特開平６－３４５８２０号公報、国際公開第９９／１０３５４号パンフレットに記載のあるリン酸エステルと銅塩との複合体を用いることもできる。更に、近赤外線領域に光吸収特性を有する体積平均粒子径が好ましくは０．３μｍ以下、より好ましくは０．１μｍ以下、特に好ましくは０．０８μｍ以下の微粒子を用いることもできる。例えば、酸化イットリウム、酸化錫及び／又は酸化インジウム、酸化銅、酸化鉄等の金属酸化物、或いは金、銀、パラジウム、白金等の金属などを挙げることもできる。更に、体積平均粒子径が５μｍ以下、より好ましくは１μｍ以下の、ガラス等の粒子中に銅、錫、インジウム、イットリウム、クロム、コバルト、チタン、ニッケル、バナジウム、希土類元素のイオン等の金属イオンを添加したものを用いることもできる。また、マイクロカプセル中に含有させることもできる。その場合、カプセルの体積平均粒子径は、１０μｍ以下が好ましく、より好ましくは５μｍ以下、更に好ましくは１μｍ以下である。イオン交換体粒子に銅、錫、インジウム、イットリウム、希土類元素等の金属イオンを吸着させたものを用いることもできる。イオン交換体粒子としては、樹脂粒子であっても無機粒子であっても構わない。無機粒子としては、例えば非晶質リン酸ジルコニウム、非晶質ケイリン酸ジルコニウム、非晶質ヘキサメタリン酸ジルコニウム、層状リン酸ジルコニウム、網状リン酸ジルコニウム、タングステン酸ジルコニウム、ゼオライト等を挙げることができる。樹脂粒子としては、通常使用されているイオン交換樹脂、イオン交換セルロース等を挙げることができる。 Further, as the phthalide compound reacted with the developer, those described in Japanese Patent No. 3271226 can be used. Further, a phosphoric acid ester metal compound, for example, a complex of a phosphoric acid ester and a copper salt described in JP-A-6-345820 and WO99 / 10354 can be used. Furthermore, fine particles having a volume average particle diameter having light absorption characteristics in the near infrared region are preferably 0.3 μm or less, more preferably 0.1 μm or less, and particularly preferably 0.08 μm or less. For example, metal oxides such as yttrium oxide, tin oxide and / or indium oxide, copper oxide, and iron oxide, or metals such as gold, silver, palladium, and platinum can be used. Furthermore, metal ions such as copper, tin, indium, yttrium, chromium, cobalt, titanium, nickel, vanadium, and rare earth elements are contained in particles such as glass having a volume average particle diameter of 5 μm or less, more preferably 1 μm or less. What was added can also be used. It can also be contained in microcapsules. In that case, the volume average particle diameter of the capsule is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 1 μm or less. What adsorb | sucked metal ions, such as copper, tin, indium, yttrium, and rare earth elements, can also be used for an ion exchanger particle. The ion exchanger particles may be resin particles or inorganic particles. Examples of the inorganic particles include amorphous zirconium phosphate, amorphous zirconium silicophosphate, amorphous zirconium hexametaphosphate, layered zirconium phosphate, reticulated zirconium phosphate, zirconium tungstate, zeolite, and the like. Examples of the resin particles include commonly used ion exchange resins and ion exchange cellulose.
　本発明における光熱変換剤としては、安定性、光熱変換効率の観点からカーボンブラックを特に好ましく挙げることができる。カーボンブラックは、レリーフ形成膜を構成する組成物中における分散安定性などに問題がない限り、ＡＳＴＭにより分類される規格の製品以外でも、カラー用、ゴム用、乾電池用などの各種用途に通常使用されるいずれのカーボンブラックも好ましく使用可能である。
　ここでいうカーボンブラックには、例えば、ファーネスブラック、サーマルブラック、チャンネルブラック、ランプブラック、アセチレンブラックなども包含される。なお、カーボンブラックなどの黒色着色剤は、分散を容易にするため、必要に応じて分散剤を用い、予めニトロセルロースやバインダーなどに分散させたカラーチップやカラーペーストとして、硬化性樹脂組成物の調製に使用することができ、このようなチップやペーストは市販品として容易に入手できる。
　本発明においては、比較的低い比表面積及び比較的低いＤＢＰ吸収を有するカーボンブラックや比表面積の大きい微細化されたカーボンブラックまでを使用することも可能である。
　好適なカーボンブラックの市販品の例としては、Ｐｒｉｎｔｅｘ　Ｕ（登録商標）、Ｐｒｉｎｔｅｘ　Ａ（登録商標）又はＳｐｅｚｉａｌｓｃｈｗａｒｚ　４（登録商標）（いずれもＤｅｇｕｓｓａ社製）、シースト６００　ＩＳＡＦ－ＬＳ（東海カーボン（株）製）、旭＃７０（Ｎ－３００）、旭＃８０（Ｎ－２２０）（旭カーボン（株）製）等が挙げられる。 As the photothermal conversion agent in the present invention, carbon black can be particularly preferably mentioned from the viewpoint of stability and photothermal conversion efficiency. Carbon black is usually used for various applications such as for color, rubber, and dry batteries, as long as there is no problem with dispersion stability in the composition forming the relief forming film, as well as products with standards classified by ASTM. Any carbon black used can be preferably used.
The carbon black here includes, for example, furnace black, thermal black, channel black, lamp black, acetylene black, and the like. In addition, in order to facilitate dispersion, black colorants such as carbon black use a dispersant as necessary, and as a color chip or color paste previously dispersed in nitrocellulose or a binder, the curable resin composition Such chips and pastes can be easily obtained as commercial products.
In the present invention, it is also possible to use carbon black having a relatively low specific surface area and relatively low DBP absorption and even finer carbon black having a large specific surface area.
Examples of suitable commercially available carbon blacks include Printex U (registered trademark), Printex A (registered trademark) or Specialschwarz 4 (registered trademark) (both manufactured by Degussa), Seast 600 ISAF-LS (Tokai Carbon Co., Ltd.) Asahi # 70 (N-300), Asahi # 80 (N-220) (Asahi Carbon Co., Ltd.) and the like.
　本発明においては、樹脂組成物中での分散性の観点から、吸油量１５０ｍｌ／１００ｇ未満のカーボンブラックが好ましい。
　このようなカーボンブラックの選択については、例えば、「カーボンブラック便覧」カーボンブラック協会編、を参考にすることができる。
　カーボンブラックの吸油量が１５０ｍｌ／１００ｇ未満のものを用いるとレリーフ形成膜中で良好な分散性が得られるため好ましい。一方、カーボンブラックの吸油量が１５０ｍｌ／１００ｇ以上のものを用いた場合には、レリーフ形成層用塗布液（硬化性樹脂組成物）への分散性が悪くなる傾向があり、カーボンブラックの凝集が生じやすくなるため、感度の不均一などが生じ、好ましくない。また、凝集防止のため、塗布液作製時に、カーボンブラックの分散を強化する必要がある。 In the present invention, carbon black having an oil absorption of less than 150 ml / 100 g is preferred from the viewpoint of dispersibility in the resin composition.
For such selection of carbon black, for example, “Carbon Black Handbook” edited by Carbon Black Association can be referred to.
It is preferable to use carbon black having an oil absorption of less than 150 ml / 100 g because good dispersibility can be obtained in the relief forming film. On the other hand, when carbon black having an oil absorption of 150 ml / 100 g or more is used, the dispersibility in the relief forming layer coating solution (curable resin composition) tends to deteriorate, and the carbon black aggregates. Since it tends to occur, non-uniformity of sensitivity occurs, which is not preferable. In order to prevent aggregation, it is necessary to enhance the dispersion of carbon black when preparing the coating solution.
　成分Ｄを分散する方法としては、インク製造やトナー製造等に用いられる公知の分散技術が使用できる。分散機としては、超音波分散器、ペイントシェーカー、サンドミル、アトライター、パールミル、スーパーミル、ボールミル、インペラー、デスパーザー、ＫＤミル、コロイドミル、ダイナトロン、３本ロールミル、加圧ニーダー等が挙げられる。詳細は、「最新顔料応用技術」（ＣＭＣ出版、１９８６年刊）に記載されている。 As a method for dispersing component D, known dispersion techniques used for ink production, toner production, and the like can be used. Examples of the disperser include an ultrasonic disperser, a paint shaker, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a Dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).
　成分Ｄの含有量は、その分子固有の分子吸光係数の大きさにより異なるが、樹脂組成物の全固形分に対し０．１～１５質量％であることが好ましく、より好ましくは０．１～１０質量％、更に好ましくは０．１～５質量％である。 The content of component D varies depending on the molecular extinction coefficient inherent to the molecule, but is preferably 0.1 to 15% by mass, more preferably 0.1 to 15% by mass with respect to the total solid content of the resin composition. The amount is 10% by mass, more preferably 0.1 to 5% by mass.
　成分Ｄの体積平均粒子径は、０．００１μｍ以上１０μｍ以下の範囲にあることが好ましく、０．０５μｍ以上１０μｍ以下の範囲にあることが更に好ましく、特に０．１μｍ以上７μｍ以下の範囲にあることが好ましい。
　成分Ｄの体積平均粒子径は、レーザー散乱式粒子径分布測定装置を用いて測定できる。　 The volume average particle diameter of component D is preferably in the range of 0.001 μm to 10 μm, more preferably in the range of 0.05 μm to 10 μm, and particularly in the range of 0.1 μm to 7 μm. Is preferred.
The volume average particle size of Component D can be measured using a laser scattering type particle size distribution measuring device.
（成分Ｅ）可塑剤
　本発明において、硬化性樹脂組成物は、フレキソ版としての柔軟性を付与するという観点から、（成分Ｅ）可塑剤を含有することが好ましい。可塑剤としては、高分子の可塑剤として公知のものを用いることができ、限定されないが、例えば、高分子大辞典（初版、１９９４年、丸善（株）発行）の第２１１～２２０頁に記載のアジピン酸誘導体、アゼライン酸誘導体、ベンゾイル酸誘導体、クエン酸誘導体、エポキシ誘導体、グリコール誘導体、炭化水素及び誘導体、オレイン酸誘導体、リン酸誘導体、フタル酸誘導体、ポリエステル系、リシノール酸誘導体、セバシン酸誘導体、ステアリン酸誘導体、スルホン酸誘導体、テルペン及び誘導体、トリメリット酸誘導体が挙げられる。これらの中でも、ガラス転移温度を低下させる効果の大きさという観点から、アジピン酸誘導体、クエン酸誘導体及びリン酸誘導体が好ましい。
　アジピン酸誘導体としては、アジピン酸ジブチル、アジピン酸２－ブトキシエチルが好ましい。クエン酸誘導体としては、クエン酸トリブチルが好ましい。リン酸誘導体としては、リン酸トリブチル、リン酸トリ２－エチルヘキシル、リン酸トリブトキシエチル、リン酸トリフェニル、リン酸クレジルジフェニル、リン酸トリクレジル、リン酸ｔ－ブチルフェニル、リン酸２－エチルヘキシルジフェニル等が挙げられる。
　可塑剤については、特開２０１２－１１６００８号公報の段落０１４５～０１４６の記載が参照できる。
　本発明において、硬化性樹脂組成物は、成分Ｅを１種のみ用いてもよく、２種以上併用してもよい。
　本発明において、硬化性樹脂組成物における成分Ｅの含有量は、ガラス転移温度を室温以下に低下させるという観点から、固形分換算で、硬化性樹脂組成物の総質量を１００質量％として、１～６０質量％が好ましく、１０～５０質量％がより好ましく、２０～４５質量％が更に好ましい。 (Component E) Plasticizer In the present invention, the curable resin composition preferably contains (Component E) a plasticizer from the viewpoint of imparting flexibility as a flexographic plate. As the plasticizer, those known as polymer plasticizers can be used, and are not limited. For example, described in pages 211 to 220 of Polymer Dictionary (First Edition, published by Maruzen Co., Ltd., 1994). Adipic acid derivatives, azelaic acid derivatives, benzoyl acid derivatives, citric acid derivatives, epoxy derivatives, glycol derivatives, hydrocarbons and derivatives, oleic acid derivatives, phosphoric acid derivatives, phthalic acid derivatives, polyesters, ricinoleic acid derivatives, sebacic acid derivatives , Stearic acid derivatives, sulfonic acid derivatives, terpenes and derivatives, trimellitic acid derivatives. Among these, an adipic acid derivative, a citric acid derivative, and a phosphoric acid derivative are preferable from the viewpoint of the effect of lowering the glass transition temperature.
As the adipic acid derivative, dibutyl adipate and 2-butoxyethyl adipate are preferable. As the citric acid derivative, tributyl citrate is preferable. Examples of phosphoric acid derivatives include tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, t-butylphenyl phosphate, 2-ethylhexyl phosphate And diphenyl.
Regarding the plasticizer, reference can be made to paragraphs 0145 to 0146 in JP2012-116008A.
In the present invention, the curable resin composition may use only one type of component E or two or more types in combination.
In the present invention, the content of the component E in the curable resin composition is 1 in terms of the solid content in terms of the total mass of the curable resin composition as 100% by mass from the viewpoint of lowering the glass transition temperature to room temperature or lower. Is preferably 60 to 60% by mass, more preferably 10 to 50% by mass, and still more preferably 20 to 45% by mass.
（成分Ｆ）溶剤
　本発明において、硬化性樹脂組成物は、溶剤を含有していてもよい。
　本発明において、硬化性樹脂組成物を調製する際に用いる溶剤は、各成分の溶解性の観点から選択すればよい。溶剤としては、非プロトン性の有機溶剤及びプロトン性の溶剤が例示され、バインダーを始めとする各種成分の溶解性を考慮して適宜選択することが好ましい。具体的には、例えばバインダーとして親水性のポリビニルアルコールを使用した場合には、プロトン性有機溶剤を選択することが好ましく、ポリビニルアルコールに比べて疎水的であるポリビニルブチラールを使用する場合には、非プロトン性の有機溶剤を主として使用することが好ましい。
　非プロトン性の有機溶剤の好ましい具体例としては、アセトニトリル、テトラヒドロフラン、ジオキサン、トルエン、プロピレングリコールモノメチルエーテルアセテート、メチルエチルケトン、アセトン、メチルイソブチルケトン、酢酸エチル、酢酸ブチル、乳酸エチル、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン、ジメチルスルホキシドが挙げられる。
　プロトン性溶剤の好ましい具体例としては、水、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、１－メトキシ－２－プロパノール、エチレングリコール、ジエチレングリコール、１，３－プロパンジオールが挙げられる。 (Component F) Solvent In the present invention, the curable resin composition may contain a solvent.
In this invention, what is necessary is just to select the solvent used when preparing curable resin composition from a soluble viewpoint of each component. Examples of the solvent include an aprotic organic solvent and a protic solvent, and it is preferable to select them appropriately in consideration of the solubility of various components including a binder. Specifically, for example, when hydrophilic polyvinyl alcohol is used as a binder, it is preferable to select a protic organic solvent, and when using polyvinyl butyral which is hydrophobic compared to polyvinyl alcohol, It is preferable to mainly use a protic organic solvent.
Preferable specific examples of the aprotic organic solvent include acetonitrile, tetrahydrofuran, dioxane, toluene, propylene glycol monomethyl ether acetate, methyl ethyl ketone, acetone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethyl lactate, N, N-dimethylacetamide. N-methylpyrrolidone and dimethyl sulfoxide.
Preferable specific examples of the protic solvent include water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, ethylene glycol, diethylene glycol, and 1,3-propanediol. .
（成分Ｇ）その他の成分
　本発明において、硬化性樹脂組成物は、上記の成分Ａ～成分Ｆに加え、その他の成分を含有してもよく、例えば、重合禁止剤、充填剤、着色剤、共増感剤、香料、単官能エチレン性不飽和化合物等が例示される。
　これらの添加剤については、特開２０１２－１１６００８号公報の段落０１４７～０１５６、０１７９～０１８０が参照できる。 (Component G) Other components In the present invention, the curable resin composition may contain other components in addition to the above components A to F. For example, a polymerization inhibitor, a filler, a colorant, Examples include co-sensitizers, fragrances, monofunctional ethylenically unsaturated compounds, and the like.
Regarding these additives, paragraphs 0147 to 0156 and 0179 to 0180 of JP2012-116008A can be referred to.
　熱又は光硬化性樹脂組成物の調製は、常法により行えばよく、例えば、成分Ａを溶剤に溶解した後に、その他の成分を添加してもよく、全成分を同時に溶剤に溶解させてもよい。また、反応性を有する多官能重合性化合物や、重合開始剤を調製の最後の段階で添加、混合することも好ましい。
　硬化性樹脂組成物の調製は、加温しながら行ってもよく、例えば成分Ａを溶剤に溶解する際には加温し、反応性を有する成分Ｂ－２や成分Ｃ－２を添加した後は、熱重合を防止する観点から、９０℃以下程度とすることが好ましい。 The preparation of the heat or photocurable resin composition may be carried out by a conventional method. For example, after component A is dissolved in a solvent, other components may be added, or all components may be dissolved in the solvent at the same time. Good. Moreover, it is also preferable to add and mix the reactive polyfunctional polymerizable compound and the polymerization initiator at the final stage of preparation.
Preparation of the curable resin composition may be performed while heating. For example, when component A is dissolved in a solvent, the component B-2 and component C-2 having reactivity are added after heating. Is preferably about 90 ° C. or less from the viewpoint of preventing thermal polymerization.
（ｂ）熱又は光硬化性樹脂組成物を熱又は光により硬化して硬化膜を形成する硬化膜形成工程
　本発明において、（ａ）塗布工程の後に、（ｂ）熱又は光硬化性樹脂組成物を熱又は光により硬化した硬化膜を形成する硬化膜形成工程を有することが好ましい。
　硬化膜形成工程では、硬化性樹脂組成物が含有する溶剤を揮発させて乾燥させると共に、硬化性樹脂組成物に架橋を導入することで硬化させることが好ましい。硬化膜形成工程は、熱により溶剤を揮発させて乾燥させると共に、熱により架橋反応を生起させることが特に好ましい。
　硬化させることで、第１にレーザー彫刻後形成されるレリーフがシャープになり、第２にレーザー彫刻の際に発生する彫刻カスの粘着性が抑制されるという利点がある。
　なお、硬化性樹脂組成物が光硬化性である場合には、加熱してある程度の溶剤を乾燥させた後に光の照射を行うことが好ましい。
　溶剤の乾燥は、溶剤の沸点未満の温度で行うことが好ましい。溶剤の突沸によるシート中の気泡の発生が抑制されるので好ましい。 (B) Cured film forming step of curing a heat or light curable resin composition with heat or light to form a cured film In the present invention, (b) heat or light curable resin composition after (a) coating step. It is preferable to have a cured film forming step of forming a cured film obtained by curing an object with heat or light.
In the cured film forming step, it is preferable that the solvent contained in the curable resin composition is volatilized and dried, and is cured by introducing crosslinking into the curable resin composition. In the cured film forming step, it is particularly preferable that the solvent is volatilized and dried by heat and a crosslinking reaction is caused by heat.
By curing, firstly, the relief formed after laser engraving becomes sharp, and secondly, there is an advantage that adhesion of engraving residue generated during laser engraving is suppressed.
In addition, when a curable resin composition is photocurable, it is preferable to heat and dry after drying a certain amount of solvent.
The solvent is preferably dried at a temperature lower than the boiling point of the solvent. Since generation | occurrence | production of the bubble in a sheet | seat by bumping of a solvent is suppressed, it is preferable.
　熱により硬化させる場合には、硬化温度（同時に溶剤の揮発も行われる）は、使用する溶剤、熱重合開始剤の分解温度に依存するが、基材の耐熱性及び成膜性を考慮すると、６０～１５０℃であることが好ましい。
　加熱手段としては、硬化性樹脂組成物を熱風オーブンや遠赤外オーブン内で所定時間加熱する方法や、加熱したロールに所定時間接する方法が挙げられる。 In the case of curing by heat, the curing temperature (the solvent is also volatilized at the same time) depends on the solvent used and the decomposition temperature of the thermal polymerization initiator, but considering the heat resistance and film formability of the substrate, It is preferably 60 to 150 ° C.
Examples of the heating means include a method of heating the curable resin composition for a predetermined time in a hot air oven or a far infrared oven, and a method of contacting a heated roll for a predetermined time.
　また、光重合開始剤等を使用し、重合性化合物を重合し架橋を形成するため、光による硬化を更に行ってもよい。
　硬化性樹脂組成物が光重合開始剤を含有する場合には、光重合開始剤のトリガーとなる光（以下、「活性光線」ともいう。）を照射することで、レリーフ形成膜を架橋（硬化）することができる。
　光の照射は、硬化性樹脂組成物シートの全面に行うのが一般的である。光としては可視光、紫外光、及び電子線が挙げられるが、紫外光が最も一般的である。基材側を裏面とすれば、表面に光を照射するだけでもよいが、基材が活性光線を透過する透明なフィルムであれば、更に裏面からも光を照射することが好ましい。表面からの照射は、保護フィルムが存在する場合、これを設けたまま行ってもよいし、保護フィルムを剥離した後に行ってもよい。酸素の存在下では重合阻害が生じる恐れがあるので、硬化性樹脂組成物シートに塩化ビニルシートを被せて真空引きした上で、活性光線の照射を行ってもよい。 Moreover, in order to form a bridge | crosslinking by polymerizing a polymeric compound using a photoinitiator etc., you may perform hardening by light.
When the curable resin composition contains a photopolymerization initiator, the relief forming film is crosslinked (cured) by irradiating light (hereinafter also referred to as “active light”) that triggers the photopolymerization initiator. )can do.
The light irradiation is generally performed on the entire surface of the curable resin composition sheet. The light includes visible light, ultraviolet light, and electron beam, but ultraviolet light is the most common. If the substrate side is the back surface, the surface may only be irradiated with light. However, if the substrate is a transparent film that transmits actinic rays, it is preferable to irradiate light from the back surface. When the protective film exists, the irradiation from the surface may be performed while the protective film is provided, or may be performed after the protective film is peeled off. Since polymerization inhibition may occur in the presence of oxygen, actinic rays may be irradiated after evacuating the curable resin composition sheet with a vinyl chloride sheet.
　なお、硬化工程において、硬化性樹脂組成物を完全に硬化させる必要はなく、独立膜として剥離可能な程度に溶剤の除去及び硬化（架橋）が行われていればよい。
　後述する剥離工程の後に、後加熱や、後光照射を行って、完全に硬化させてもよい。
　なお、溶剤の揮発は、基材とは反対側の面のみで行われ、基材上では揮発効率が低いことから、硬化工程を硬化膜が剥離可能な程度に留めることも好ましい。 In the curing step, it is not necessary to completely cure the curable resin composition, as long as the solvent is removed and cured (crosslinked) to such an extent that it can be peeled off as an independent film.
After the peeling step described later, post-heating or post-light irradiation may be performed to completely cure.
In addition, since the volatilization of the solvent is performed only on the surface opposite to the base material, and the volatilization efficiency is low on the base material, it is also preferable to keep the curing step to such an extent that the cured film can be peeled off.
（ｃ）硬化膜を基材から剥離する硬化膜剥離工程
　本発明において、レリーフ形成膜の製造方法は、（ｃ）硬化膜を基材から剥離する硬化膜剥離工程を有することが好ましい。
　硬化膜は、上述するように、完全に硬化及び乾燥が行われている必要はなく、独立膜として剥離可能な程度に硬化及び／又は乾燥が行われていればよい。剥離時における硬化膜の強度は、０．５Ｎ／ｃｍ以上であることが好ましく、１．０Ｎ／ｃｍ以上であることがより好ましい。剥離時の硬化膜強度を上記範囲内とすることにより、硬化膜の破断や欠陥の発生が抑制される。
　剥離スピードや剥離温度は特に限定されず、硬化膜の破断や欠陥の発生が抑制できる範囲で、適宜選択すればよい。 (C) Cured film peeling process which peels a cured film from a base material In this invention, it is preferable that the manufacturing method of a relief forming film has a cured film peeling process which peels a cured film from a base material.
As described above, the cured film does not need to be completely cured and dried, and may be cured and / or dried to such an extent that it can be peeled as an independent film. The strength of the cured film at the time of peeling is preferably 0.5 N / cm or more, and more preferably 1.0 N / cm or more. By setting the cured film strength at the time of peeling within the above range, the fracture of the cured film and the occurrence of defects are suppressed.
The peeling speed and the peeling temperature are not particularly limited, and may be appropriately selected as long as the cured film can be prevented from being broken or defective.
（その他）
　本発明において、硬化膜剥離工程の後に、更に、後硬化工程を有していてもよい。後硬化工程では、追加の溶剤除去、追加の加熱による硬化、及び、追加の光照射による硬化よりなる群から選択される少なくとも１つが行われる。これらは単独で行ってもよいし、２つ以上を組合わせて行ってもよい。 (Other)
In this invention, you may have a postcure process further after the cured film peeling process. In the post-curing step, at least one selected from the group consisting of additional solvent removal, curing by additional heating, and curing by additional light irradiation is performed. These may be performed alone or in combination of two or more.
３．レリーフ印刷版原版及びその製造方法
（レリーフ印刷版原版）
　本発明のレリーフ印刷版原版の第１の実施態様は、本発明のレリーフ形成膜からなるレリーフ形成層を有する。
　また、本発明のレリーフ印刷版原版の第２の実施態様は、本発明のレリーフ形成膜の製造方法により得られたレリーフ形成膜をレリーフ形成層として有する。
　上記レリーフ印刷版原版をレーザー彫刻等することにより「レリーフ印刷版」が作製される。
　また、本発明において「レリーフ層」とは、レリーフ印刷版におけるレーザーによる彫刻等がされた層、すなわち、画像様の凹凸を形成後の上記レリーフ形成層をいう。 3. Relief printing plate precursor and manufacturing method thereof (relief printing plate precursor)
The first embodiment of the relief printing plate precursor of the present invention has a relief forming layer comprising the relief forming film of the present invention.
Moreover, the 2nd embodiment of the relief printing plate precursor of this invention has the relief forming film obtained by the manufacturing method of the relief forming film of this invention as a relief forming layer.
A “relief printing plate” is produced by laser engraving the relief printing plate precursor.
Further, in the present invention, the “relief layer” refers to a layer engraved with a laser or the like on a relief printing plate, that is, the relief forming layer after forming image-like irregularities.
　レリーフ形成層は、支持体上に設けられることが好ましい。
　レリーフ印刷版原版は、必要により更に、支持体とレリーフ形成層との間に接着層を、また、レリーフ形成層上にスリップコート層、保護フィルムを有していてもよい。 The relief forming layer is preferably provided on the support.
The relief printing plate precursor may further have an adhesive layer between the support and the relief forming layer, if necessary, and a slip coat layer and a protective film on the relief forming layer.
＜レリーフ形成層＞
　レリーフ形成層は、上記本発明のレリーフ形成膜からなる層である。
　レリーフ形成層は、通常、後述する支持体上に設けられるが、製版、印刷用の装置に備えられたシリンダーなどの部材表面に直接形成したり、そこに配置して固定化したりすることもでき、必ずしも支持体を必要としない。 <Relief forming layer>
The relief forming layer is a layer comprising the relief forming film of the present invention.
The relief forming layer is usually provided on a support which will be described later. However, the relief forming layer can be directly formed on the surface of a member such as a cylinder provided in an apparatus for plate making and printing, or can be arranged and fixed there. It does not necessarily require a support.
＜支持体＞
　本発明において、支持体は、可撓性を有し、かつ、寸法安定性に優れた材料が好ましく用いられ、例えば、ポリエチレンテレフタレートフィルム（ＰＥＴ）、ポリエチレンナフタレートフィルム（ＰＥＮ）、ポリブチレンテレフタレートフィルム、又はポリカーボネートを好ましく挙げることができる。支持体の厚みが好ましくは５０μｍ以上３５０μｍ以下、より好ましくは１００μｍ以上２５０μｍ以下であると、原版の機械的特性、形状安定性又は印刷版製版時の取り扱い性等から好ましい。また、必要により、支持体とレリーフ形成樹脂層との接着を向上させるために、この種の目的で従来から使用されている公知の接着剤を表面に設けてもよい。
　また、本発明で用いる支持体の表面に物理的、化学的処理を行うことにより、レリーフ形成層或いは接着剤層との接着性を向上させることができる。物理的処理方法としては、サンドブラスト法、粒子を含有した液体を噴射するウエットブラスト法、コロナ放電処理法、プラズマ処理法、紫外線或いは真空紫外線照射法などを挙げることができる。また、化学的処理方法としては、強酸・強アルカリ処理法、酸化剤処理法、カップリング剤処理法などである。 <Support>
In the present invention, a material having flexibility and excellent dimensional stability is preferably used as the support, for example, polyethylene terephthalate film (PET), polyethylene naphthalate film (PEN), polybutylene terephthalate film. Or a polycarbonate can be mentioned preferably. The thickness of the support is preferably 50 μm or more and 350 μm or less, more preferably 100 μm or more and 250 μm or less, from the viewpoint of mechanical properties of the original plate, shape stability, or handling properties during plate making. If necessary, a known adhesive conventionally used for this type of purpose may be provided on the surface in order to improve the adhesion between the support and the relief-forming resin layer.
Moreover, the adhesiveness with a relief forming layer or an adhesive bond layer can be improved by performing a physical and chemical treatment on the surface of the support used in the present invention. Examples of the physical treatment method include a sand blast method, a wet blast method for spraying a liquid containing 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.
（レリーフ印刷版原版の製造方法）
　本発明において、レリーフ印刷版原版の製造方法は、レリーフ形成膜の上記基材と接触していた面とは反対側の面と、支持体と、を接着する接着工程を含むことが好ましい。
　すなわち、剥離工程にて基材から剥離された硬化膜を、必要に応じて後硬化したのち、基材と接触していた面とは反対側の面が支持体と接するように積層（ラミネート）することが好ましい。
　レリーフ形成層を支持体上に形成する場合、レリーフ形成膜と、支持体との接着力を強化する目的で、接着層を設けてもよい。
　接着層に使用し得る材料（接着剤）としては、例えば、Ｉ．Ｓｋｅｉｓｔ編、「Ｈａｎｄｂｏｏｋ　ｏｆ　Ａｄｈｅｓｉｖｅｓ」、第２版（１９７７）に記載のものを用いることができる。 (Relief printing plate precursor manufacturing method)
In this invention, it is preferable that the manufacturing method of a relief printing plate precursor includes the adhesion process which adhere | attaches the surface on the opposite side to the surface which was contacting the said base material of the relief forming film, and a support body.
That is, the cured film peeled off from the substrate in the peeling step is post-cured as necessary, and then laminated so that the surface opposite to the surface in contact with the substrate is in contact with the support. It is preferable to do.
When the relief forming layer is formed on the support, an adhesive layer may be provided for the purpose of enhancing the adhesive force between the relief forming film and the support.
As a material (adhesive) that can be used for the adhesive layer, for example, I.I. Those described in the edition of Skeist, “Handbook of Adhesives”, the second edition (1977) can be used.
＜保護フィルム、スリップコート層＞
　レリーフ形成層表面への傷や凹み防止の目的で、レリーフ形成層表面に保護フィルムを設けてもよい。保護フィルムの厚さは、２５～５００μｍが好ましく、５０～２００μｍがより好ましい。保護フィルムは、例えば、ＰＥＴのようなポリエステル系フィルム、ＰＥ（ポリエチレン）やＰＰ（ポリプロピレン）のようなポリオレフィン系フィルムを用いることができる。またフィルムの表面はマット化されていてもよい。保護フィルムは、剥離可能であることが好ましい。 <Protective film, slip coat layer>
A protective film may be provided on the surface of the relief forming layer for the purpose of preventing scratches and dents on the surface of the relief forming layer. The thickness of the protective film is preferably 25 to 500 μm, more preferably 50 to 200 μm. As the protective film, for example, a polyester film such as PET, or a polyolefin film such as PE (polyethylene) or PP (polypropylene) can be used. The surface of the film may be matted. The protective film is preferably peelable.
＜その他の層＞
　本発明では、支持体とレリーフ形成層との間、又は接着層とレリーフ形成層との間にクッション性を有する樹脂又はゴムからなるクッション層を形成することができる。支持体とレリーフ形成層との間にクッション層を形成する場合、片面に接着剤層の付いたクッション層を、接着剤層側を支持体に向けて貼り付ける方法が簡便である。クッション層を貼り付けた後、表面を切削、研磨して整形することもできる。また、クッション層を形成するクッション層用の組成物を支持体上に一定厚みで塗布し、これを硬化させてクッション層を形成してもよい。更に、クッション層の表面を切削、研磨等により成形してもよい。　 <Other layers>
In the present invention, a cushion layer made of a resin or rubber having cushioning properties can be formed between the support and the relief forming layer, or between the adhesive layer and the relief forming layer. When a cushion layer is formed between the support and the relief forming layer, a method of sticking the cushion layer with the adhesive layer on one side with the adhesive layer side facing the support is simple. After the cushion layer is applied, the surface can be cut and polished for shaping. Alternatively, the cushion layer composition for forming the cushion layer may be applied to the support with a certain thickness and cured to form the cushion layer. Further, the surface of the cushion layer may be formed by cutting, polishing, or the like.
４．レリーフ印刷版及びその製版方法
　本発明のレリーフ印刷版の製版方法は、本発明のレリーフ形成膜をレリーフ形成層として有するレリーフ印刷版原版をレーザー彫刻する彫刻工程、を含むことが好ましい。 4). Relief printing plate and plate making method The plate making method of the relief printing plate of the present invention preferably includes an engraving step of laser engraving a relief printing plate precursor having the relief forming film of the present invention as a relief forming layer.
＜レーザー彫刻の条件＞
　レーザー彫刻においては、形成したい画像をデジタル型のデータとしてコンピューターを利用してレーザー装置を操作し、原版上にレリーフ画像を作成する。
　レーザー彫刻に用いるレーザーは、原版が吸収を有する波長を含むものであればどのようなものを用いてもよいが、彫刻を高速度で行うためには出力の高いものが望ましく、炭酸ガスレーザー、ＹＡＧレーザー、半導体レーザー、ファイバーレーザー等の赤外線或いは近赤外線領域に発振波長を有するレーザーが好ましいものの一つである。また、紫外線領域に発振波長を有する紫外線レーザー、例えばエキシマレーザー、第３或いは第４高調波へ波長変換したＹＡＧレーザー、銅蒸気レーザー等は、有機分子の結合を切断するアブレージョン加工が可能であり、微細加工に適する。フェムト秒レーザーなど極めて高い尖頭出力を有するレーザーを用いることもできる。また、レーザーは連続照射でも、パルス照射でもよい。 <Conditions for laser engraving>
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 can 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, etc., can be ablated to break the bonds of 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.
　レーザーによる彫刻は酸素含有ガス下、一般には空気存在下又は気流下に実施するが、炭酸ガス、窒素ガス下でも実施できる。彫刻終了後、レリーフ印刷版面にわずかに発生する粉末状又は液状の物質は適当な方法、例えば溶剤や界面活性剤の入った水等で洗いとる方法、高圧スプレー等により水系洗浄剤を照射する方法、高圧スチームを照射する方法などを用いて除去する洗浄工程（リンス工程）を有してもよい。 Laser engraving is performed in an oxygen-containing gas, generally in the presence of air or in an air stream, but can also be performed in carbon dioxide or nitrogen gas. After engraving is finished, the powdery or liquid substance slightly generated on the relief printing plate surface is washed by 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. Further, it may have a cleaning step (rinsing step) for removing using a method of irradiating high-pressure steam.
　本発明のレリーフ印刷版原版又はレリーフ印刷版は、印刷版用レリーフ画像の他、スタンプ・印章、エンボス加工用のデザインロール、電子部品作成に用いられる絶縁体、抵抗体、導電体ペーストのパターニング用レリーフ画像、窯業製品の型材用レリーフ画像、広告・表示板などのディスプレイ用レリーフ画像、各種成型品の原型・母型など各種の用途に応用し利用できる。 The relief printing plate precursor or relief printing plate of the present invention is used for patterning of a printing plate relief image, stamps / signs, embossing design rolls, insulators, resistors, and conductor pastes used for electronic component creation. It can be applied and used in various applications such as relief images, relief images for ceramics mold materials, relief images for displays such as advertisements and display boards, and prototypes and mother dies for various molded products.
＜レーザー彫刻後の表面処理＞
　また、本発明において、凹凸パターンを形成したレリーフ層表面に改質層を形成させることにより、印刷版表面のタックの低減、インク濡れ性の向上を行うこともできる。改質層としては、シランカップリング剤或いはチタンカップリング剤等の表面水酸基と反応する化合物で処理した被膜、或いは多孔質無機粒子を含有するポリマーフィルムを挙げることができる。広く用いられているシランカップリング剤は、基材の表面水酸基との反応性の高い官能基を分子内に有する化合物であり、そのような官能基とは、例えばトリメトキシシリル基、トリエトキシシリル基、トリクロロシリル基、ジエトキシシリル基、ジメトキシシリル基、ジモノクロロシリル基、モノエトキシシリル基、モノメトキシシリル基、モノクロロシリル基を挙げることができる。また、これらの官能基は分子内に少なくとも１つ以上存在し、基材の表面水酸基と反応することにより基材表面に固定化される。更にシランカップリング剤を構成する化合物は、分子内に反応性官能基としてアクリロイル基、メタクリロイル基、活性水素含有アミノ基、エポキシ基、ビニル基、パーフルオロアルキル基、及びメルカプト基から選ばれた少なくとも１個の官能基を有するもの、或いは長鎖アルキル基を有するものを用いることができる。表面に固定化したカップリング剤分子が特に重合性反応基を有する場合、表面への固定化後、光、熱、或いは電子線を照射し架橋させることにより、より強固な被膜とすることもできる。 <Surface treatment after laser engraving>
Further, in the present invention, by forming a modified layer on the surface of the relief layer on which the concavo-convex pattern is formed, tackiness on the printing plate surface can be reduced and ink wettability can be improved. Examples of the modified layer include a film treated with a compound that reacts with a surface hydroxyl group such as a silane coupling agent or a titanium coupling agent, or a polymer film containing porous inorganic particles. A widely used silane coupling agent is a compound having in its molecule a functional group highly reactive with the surface hydroxyl group of the substrate. Examples of such a functional group include a trimethoxysilyl group and a triethoxysilyl group. Group, trichlorosilyl group, diethoxysilyl group, dimethoxysilyl group, dimonochlorosilyl group, monoethoxysilyl group, monomethoxysilyl group, monochlorosilyl group. Further, at least one of these functional groups exists in the molecule, and is immobilized on the surface of the base material by reacting with the surface hydroxyl group of the base material. Furthermore, the compound constituting the silane coupling agent is at least selected from acryloyl group, methacryloyl group, active hydrogen-containing amino group, epoxy group, vinyl group, perfluoroalkyl group, and mercapto group as reactive functional groups in the molecule. Those having one functional group or those having a long-chain alkyl group can be used. When the coupling agent molecule immobilized on the surface has a polymerizable reactive group in particular, it is possible to obtain a stronger film by irradiating light, heat, or electron beam and crosslinking after immobilization on the surface. .
　表面処理液は、上記のカップリング剤を、必要に応じ、水－アルコール、或いは酢酸水－アルコール混合液で希釈して調製する。処理液中のカップリング剤の濃度は、０．０５質量％以上１０．０質量％以下が好ましい。 The surface treatment solution is prepared by diluting the above coupling agent with water-alcohol or acetic acid water-alcohol mixed solution as necessary. The concentration of the coupling agent in the treatment liquid is preferably 0.05% by mass or more and 10.0% by mass or less.
　カップリング剤処理法について説明する。上記のカップリング剤を含む処理液は、印刷版原版、或いはレーザー彫刻後の印刷版表面に塗布して用いられる。カップリング剤処理液を塗布する方法に特に限定はなく、例えば浸漬法、スプレー法、ロールコート法、或いは刷毛塗り法等を適応することができる。また、被覆処理温度、被覆処理時間についても特に限定はないが、５℃以上６０℃以下であることが好ましく、処理時間は０．１秒以上６０秒以下であることが好ましい。更に樹脂版表面上の処理液層の乾燥を加熱下に行うことが好ましく、加熱温度としては５０℃以上１５０℃以下が好ましい。 The coupling agent treatment method will be described. The treatment liquid containing the above coupling agent is used by being applied to the printing plate precursor or the surface of the printing plate after laser engraving. The method for applying the coupling agent treatment liquid is not particularly limited, and for example, an immersion method, a spray method, a roll coating method, a brush coating method, or the like can be applied. The coating treatment temperature and the coating treatment time are not particularly limited, but are preferably 5 ° C. or more and 60 ° C. or less, and the treatment time is preferably 0.1 seconds or more and 60 seconds or less. Furthermore, it is preferable to dry the treatment liquid layer on the surface of the resin plate under heating.
　カップリング剤で印刷版表面を処理する前に、キセノンエキシマランプ等の波長が２００ｎｍ以下の真空紫外線領域の光を照射する方法、或いはプラズマ等の高エネルギー雰囲気に曝すことにより、印刷版表面に水酸基を発生させ高密度にカップリング剤を固定化することもできる。 Before treating the printing plate surface with a coupling agent, a method of irradiating light in a vacuum ultraviolet region having a wavelength of 200 nm or less, such as a xenon excimer lamp, or exposing to a high energy atmosphere such as plasma, a hydroxyl group on the printing plate surface. And the coupling agent can be immobilized at a high density.
　また、無機多孔質体粒子を含有する層が印刷版表面に露出している場合、プラズマ等の高エネルギー雰囲気下で処理し、表面の有機物層を若干エッチング除去することにより印刷版表面に微小な凹凸を形成させることができる。この処理により印刷版表面のタックを低減させること、及び表面に露出した無機多孔質体粒子がインクを吸収しやすくすることによりインク濡れ性が向上する効果も期待できる。 In addition, when the layer containing inorganic porous particles is exposed on the printing plate surface, it is treated in a high-energy atmosphere such as plasma, and the organic layer on the surface is slightly etched away to remove minute particles on the printing plate surface. Unevenness can be formed. The effect of improving the ink wettability can be expected by reducing the tack of the printing plate surface by this treatment and making the inorganic porous particles exposed on the surface easy to absorb the ink.
＜リンス工程、乾燥工程、後架橋工程＞
　本発明のレリーフ印刷版の製版方法では、彫刻工程に次いで、更に、必要に応じて下記リンス工程、乾燥工程、及び／又は、後架橋工程を含んでもよい。
　リンス工程：彫刻後のレリーフ層表面を、水又は水を主成分とする液体で彫刻表面をリンスする工程。
　乾燥工程：彫刻されたレリーフ層を乾燥する工程。
　後架橋工程：彫刻後のレリーフ層にエネルギーを付与し、レリーフ層を更に架橋する工程。
　上記彫刻工程を経た後、彫刻表面に彫刻カスが付着しているため、水又は水を主成分とする液体で彫刻表面をリンスして、彫刻カスを洗い流すリンス工程を追加してもよい。リンスの手段として、水道水で水洗する方法、高圧水をスプレー噴射する方法、感光性樹脂凸版の現像機として公知のバッチ式又は搬送式のブラシ式洗い出し機で、彫刻表面を主に水の存在下でブラシ擦りする方法などが挙げられ、彫刻カスのヌメリがとれない場合は、石鹸や界面活性剤を添加したリンス液を用いてもよい。
　彫刻表面をリンスするリンス工程を行った場合、彫刻されたレリーフ形成層を乾燥してリンス液を揮発させる乾燥工程を追加することが好ましい。
　更に、必要に応じてレリーフ形成層を更に架橋させる後架橋工程を追加してもよい。追加の架橋工程である後架橋工程を行うことにより、彫刻によって形成されたレリーフをより強固にすることができる。 <Rinse process, drying process, post-crosslinking process>
In the method for making a relief printing plate of the present invention, following the engraving step, the following rinsing step, drying step, and / or post-crosslinking step may be included as necessary.
Rinsing step: a step of rinsing the engraved surface of the relief layer after engraving with water or a liquid containing water as a main component.
Drying step: a step of drying the engraved relief layer.
Post-crosslinking step: a step of imparting energy to the relief layer after engraving and further crosslinking the relief layer.
Since the engraving residue is attached to the engraving surface after the engraving step, a rinsing step of rinsing the engraving residue by rinsing the engraving surface with water or a liquid containing water as a main component may be added. As a means of rinsing, there is a method of washing with tap water, a method of spraying high-pressure water, and a known batch type or conveying type brush type washing machine as a photosensitive resin relief printing machine. For example, when the engraving residue cannot be removed, a rinsing liquid to which soap or a surfactant is added may be used.
When the rinsing process for rinsing the engraving surface is performed, it is preferable to add a drying process for drying the engraved relief forming layer and volatilizing the rinsing liquid.
Furthermore, you may add the post-crosslinking process which further bridge | crosslinks a relief forming layer as needed. By performing a post-crosslinking step, which is an additional cross-linking step, the relief formed by engraving can be further strengthened.
　本発明に用いることができるリンス液のｐＨは、９以上であることが好ましく、１０以上であることがより好ましく、１１以上であることが更に好ましい。また、リンス液のｐＨは、１４以下であることが好ましく、１３．５以下であることがより好ましく、１３．２以下であることが更に好ましく、１２．５以下であることが特に好ましい。上記範囲であると、取り扱いが容易である。
　リンス液を上記のｐＨ範囲とするために、適宜、酸及び／又は塩基を用いてｐＨを調整すればよく、使用する酸及び塩基は特に限定されない。
　本発明に用いることができるリンス液は、主成分として水を含有することが好ましい。
　また、リンス液は、水以外の溶剤として、アルコール類、アセトン、テトラヒドロフラン等などの水混和性溶剤を含有していてもよい。 The pH of the rinsing solution that can be used in the present invention is preferably 9 or more, more preferably 10 or more, and still more preferably 11 or more. The pH of the rinsing liquid is preferably 14 or less, more preferably 13.5 or less, still more preferably 13.2 or less, and particularly preferably 12.5 or less. Handling is easy in the said range.
What is necessary is just to adjust pH using an acid and / or a base suitably in order to make a rinse liquid into said pH range, and the acid and base to be used are not specifically limited.
The rinsing liquid that can be used in the present invention preferably contains water as a main component.
Moreover, the rinse liquid may contain water miscible solvents, such as alcohol, acetone, tetrahydrofuran, etc. as solvents other than water.
　リンス液は、界面活性剤を含有することが好ましい。
　本発明に用いることができる界面活性剤としては、彫刻カスの除去性、及び、レリーフ印刷版への影響を少なくする観点から、カルボキシベタイン化合物、スルホベタイン化合物、ホスホベタイン化合物、アミンオキシド化合物、又は、ホスフィンオキシド化合物等のベタイン化合物（両性界面活性剤）が好ましく挙げられる。 It is preferable that the rinse liquid contains a surfactant.
As the surfactant that can be used in the present invention, a carboxybetaine compound, a sulfobetaine compound, a phosphobetaine compound, an amine oxide compound, or from the viewpoint of reducing engraving residue removal and influence on the relief printing plate, Preferred are betaine compounds (amphoteric surfactants) such as phosphine oxide compounds.
　また、界面活性剤としては、公知のアニオン界面活性剤、カチオン界面活性剤、ノニオン界面活性剤等も挙げられる。更に、フッ素系、シリコーン系のノニオン界面活性剤も同様に使用することができる。
　界面活性剤は、１種単独で使用しても、２種以上を併用してもよい。
　界面活性剤の使用量は特に限定する必要はないが、リンス液の全質量に対し、０．０１～２０質量％であることが好ましく、０．０５～１０質量％であることがより好ましい。 Examples of the surfactant include known anionic surfactants, cationic surfactants, and nonionic surfactants. Furthermore, fluorine-based and silicone-based nonionic surfactants can be used in the same manner.
Surfactant may be used individually by 1 type, or may use 2 or more types together.
The amount of the surfactant used is not particularly limited, but is preferably 0.01 to 20% by mass, and more preferably 0.05 to 10% by mass with respect to the total mass of the rinsing liquid.
　以下、実施例により本発明を更に詳細に説明するが、本発明はこれら実施例に限定されるものではない。
　なお、実施例中の添加量の「部」及び「％」は、特に断りのない限り、「質量部」及び「質量％」を表している。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
In addition, “parts” and “%” of the addition amounts in the examples represent “parts by mass” and “% by mass” unless otherwise specified.
（レリーフ形成膜１の作製）
１．樹脂組成物（硬化性樹脂組成物）の調製
　撹拌羽及び冷却管をつけた３つ口フラスコ中に、（成分Ａ）バインダーポリマーとして「デンカブチラール＃３０００－２」（電気化学工業（株）製、ポリビニルブチラール誘導体、Ｍｗ＝９万）４０質量部、（成分Ｆ）溶剤としてプロピレングリコールモノメチルエーテルアセテート４７質量部を入れ、撹拌しながら７０℃で１２０分間加熱しポリマーを溶解させた。その後、溶液を４０℃にし、更に重合性化合物（２官能）としてトリシクロデカンジメタノールジメタクリレート１５質量部、重合性化合物（単官能体）としてブレンマーＬＭＡ（日油（株）製）８質量部、（成分Ｃ）架橋触媒（重合開始剤）としてパーブチルＺ（日油（株）製）１．６質量部、（成分Ｄ）光熱変換剤としてカーボンブラック（ショウブラック　Ｎ１１０、キャボットジャパン（株）製、ＤＢＰ吸油量１１５ｍｌ／１００ｇ）１．５質量部、を添加して３０分間撹拌した。その後、Ｓ－１５（以下に、構造を示す。商品名、ＫＢＥ－８４６として信越化学工業（株）より入手可能）１５質量部及び触媒としてリン酸０．４質量部を添加し、４０℃で１０分間撹拌した。この操作により、流動性のあるレリーフ形成膜用塗布液１（硬化性樹脂組成物）を得た。 (Preparation of relief forming film 1)
1. Preparation of Resin Composition (Curable Resin Composition) In a three-necked flask equipped with a stirring blade and a cooling tube, (Component A) “Denkabutyral # 3000-2” (manufactured by Denki Kagaku Kogyo Co., Ltd.) as a binder polymer Polyvinyl butyral derivative, Mw = 90,000) 40 parts by mass, (Component F) 47 parts by mass of propylene glycol monomethyl ether acetate as a solvent were added and heated at 70 ° C. for 120 minutes with stirring to dissolve the polymer. Thereafter, the solution was brought to 40 ° C., and further 15 parts by mass of tricyclodecane dimethanol dimethacrylate as the polymerizable compound (bifunctional), and 8 parts by mass of Bremer LMA (manufactured by NOF Corporation) as the polymerizable compound (monofunctional). (Component C) 1.6 parts by mass of perbutyl Z (manufactured by NOF Corporation) as a crosslinking catalyst (polymerization initiator), (Component D) carbon black (show black N110, manufactured by Cabot Japan Co., Ltd.) as a photothermal conversion agent And 1.5 parts by mass of DBP oil absorption 115 ml / 100 g) was added and stirred for 30 minutes. Thereafter, 15 parts by weight of S-15 (shown below is the structure. Product name, available from Shin-Etsu Chemical Co., Ltd. as KBE-846) and 0.4 parts by weight of phosphoric acid as a catalyst were added, and the mixture was heated at 40 ° C. Stir for 10 minutes. By this operation, a fluid relief-forming film coating solution 1 (curable resin composition) was obtained.
Figure JPOXMLDOC01-appb-I000004
Figure JPOXMLDOC01-appb-I000004
２．レリーフ形成膜の作製
　下記の表１のＰＥＴ基板上に所定厚のスペーサー（枠）を設置し、上記より得られたレリーフ形成膜用塗布液１をスペーサー（枠）から流出しない程度に静かに流延し、９０℃のオーブン中で３時間乾燥させて、厚さが約１ｍｍのレリーフ形成層を設け、レリーフ形成膜１を作製した。 2. Preparation of relief forming film A spacer (frame) having a predetermined thickness is placed on the PET substrate shown in Table 1 below, and the relief forming film coating solution 1 obtained as described above is gently flowed so as not to flow out of the spacer (frame). Then, it was dried in an oven at 90 ° C. for 3 hours to provide a relief forming layer having a thickness of about 1 mm, and a relief forming film 1 was produced.
（レリーフ形成膜２の作製）
１．樹脂組成物（硬化性樹脂組成物）の調製
　撹拌羽及び冷却管をつけた３つ口フラスコ中に、（成分Ａ）バインダーポリマーとしてＮｉｐｏｌ　ＢＲ１２２０Ｌ（日本ゼオン（株）製、ブタジエンゴム）５０質量部、溶剤としてテトラヒドロフラン４７質量部を入れ、撹拌し、ポリマーを溶解させた。その後、重合性化合物（２官能体）として１，６－ヘキサジオール－ジアクリレート１０質量部、重合開始剤としてパーブチルＺ（日油（株）製）１．６質量部、光熱変換剤としてカーボンブラック（ショウブラックＮ１１０、キャボットジャパン（株）製、ＤＢＰ吸油量１１５ｍｌ／１００ｇ）１．０質量部を添加して３０分間撹拌した。この操作により、流動性のあるレリーフ形成膜用塗布液２（硬化性樹脂組成物）を得た。 (Preparation of relief forming film 2)
1. Preparation of Resin Composition (Curable Resin Composition) In a three-necked flask equipped with a stirring blade and a cooling tube, (Component A) Nipol BR1220L (made by Nippon Zeon Co., Ltd., butadiene rubber) as a binder polymer 50 parts by mass Then, 47 parts by mass of tetrahydrofuran as a solvent was added and stirred to dissolve the polymer. Thereafter, 10 parts by mass of 1,6-hexadiol-diacrylate as a polymerizable compound (bifunctional), 1.6 parts by mass of perbutyl Z (manufactured by NOF Corporation) as a polymerization initiator, and carbon black as a photothermal conversion agent 1.0 part by mass (Show Black N110, manufactured by Cabot Japan Co., Ltd., DBP oil absorption 115 ml / 100 g) was added and stirred for 30 minutes. By this operation, a fluid coating solution 2 for a relief forming film (curable resin composition) was obtained.
２．レリーフ形成膜の作製
　下記の表１のＰＥＴフィルム上に調製したレリーフ形成層用塗布液２を厚さ１．５ｍｍのシート状に成形し、レリーフ形成用樹脂層を得た。次いで、メタルハライドタンプ（アイグラフィックス（株）製、商標「Ｍ０５６－Ｌ２１」）から出てくる光を、大気中で感光性樹脂層が露出している面から照射してレリーフ形成用樹脂層を硬化させた。こうして、レリーフ形成用樹脂層を硬化させてなるレリーフ形成膜２を作製した。照射したエネルギー量は、４，０００ｍＪ／ｃｍ2であった。なお、このエネルギー量は、ＵＶ－３５－ＡＰＲフィルターで測定した照度を時間積分した値である。 2. Preparation of Relief Forming Film The relief forming layer coating solution 2 prepared on the PET film shown in Table 1 below was molded into a 1.5 mm thick sheet to obtain a relief forming resin layer. Next, the light that emerges from the metal halide tamps (trade name “M056-L21” manufactured by iGraphics Co., Ltd.) is irradiated from the surface where the photosensitive resin layer is exposed in the atmosphere to form the relief forming resin layer. Cured. Thus, a relief forming film 2 obtained by curing the relief forming resin layer was produced. The amount of energy irradiated was 4,000 mJ / cm 2 . This energy amount is a value obtained by integrating the illuminance measured with the UV-35-APR filter over time.
（レリーフ形成膜３の作製）
１．樹脂組成物（硬化製樹脂組成物）の調製
　カーボンブラック（オリエント化学工業（株）製、ＣＷ１）０．８質量部、ポリビニルアルコール（日本合成化学工業（株）ゴーセノールＧＨ－２３、熱分解開始温度２２０℃、極限酸素指数２２．５）４０質量部、ポリエチレングリコール＃４００　２０質量部、及び水４０質量部の分散物を作製し、この分散物よりなるレリーフ形成膜用塗布液３（硬化性樹脂組成物）を得た。 (Preparation of relief forming film 3)
1. Preparation of resin composition (cured resin composition) Carbon black (manufactured by Orient Chemical Co., Ltd., CW1) 0.8 parts by mass, polyvinyl alcohol (Nippon Gosei Chemical Co., Ltd. Gohsenol GH-23, thermal decomposition start temperature A dispersion of 220 ° C., limiting oxygen index 22.5) 40 parts by mass, polyethylene glycol # 400 20 parts by mass, and water 40 parts by mass was prepared, and a relief forming film coating solution 3 (curable resin) comprising this dispersion Composition) was obtained.
２．レリーフ形成膜の作製
　上記のように作製したレリーフ形成層用塗布液３を、バーコーターで表１のフィルム（厚さ１００μｍ）に塗布し、１００℃、１０分間乾燥して、水を蒸発させ、塗布膜（２０ｇ／ｍ2の塗布量）を得た。こうして、塗布膜よりなるレリーフ形成膜３を作製した。 2. Preparation of relief-forming film The relief-forming layer coating solution 3 prepared as described above was applied to the film shown in Table 1 (thickness: 100 μm) with a bar coater, dried at 100 ° C. for 10 minutes to evaporate water, A coating film (a coating amount of 20 g / m 2 ) was obtained. Thus, a relief forming film 3 made of a coating film was produced.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
（転写材Ａの作製）
　厚さ０．３ｍｍのＪＩＳ－Ａ－１０５０アルミニウム板を用いて、下記に示す工程を組み合わせて処理することで転写材Ａを作製した。
（ａ）機械的粗面化処理
　比重１．１２の研磨剤（ケイ砂）と水との懸濁液を研磨スラリー液としてアルミニウム板の表面に供給しながら、回転するローラ状ナイロンブラシにより機械的な粗面化を行った。研磨剤の平均粒径は８μｍ、最大粒径は５０μｍであった。ナイロンブラシの材質は６・１０ナイロン、毛長５０ｍｍ、毛の直径は０．３ｍｍであった。ナイロンブラシはφ３００ｍｍのステンレス製の筒に穴をあけて密になるように植毛した。回転ブラシは３本使用した。ブラシ下部の２本の支持ローラ（φ２００ｍｍ）の距離は３００ｍｍであった。ブラシローラはブラシを回転させる駆動モータの負荷が、ブラシローラをアルミニウム板に押さえつける前の負荷に対して７ｋＷプラスになるまで押さえつけた。ブラシの回転方向はアルミニウム板の移動方向と同じであった。ブラシの回転数は２００ｒｐｍであった。 (Preparation of transfer material A)
Using a JIS-A-1050 aluminum plate having a thickness of 0.3 mm, a transfer material A was produced by processing in combination with the following steps.
(A) Mechanical surface roughening treatment While supplying a suspension of abrasive (silica sand) having a specific gravity of 1.12 and water as a polishing slurry liquid to a surface of an aluminum plate, it is mechanically rotated by a roller-like nylon brush. Roughening was performed. The average particle size of the abrasive was 8 μm, and the maximum particle size was 50 μm. The material of the nylon brush was 6 · 10 nylon, the hair length was 50 mm, and the hair diameter was 0.3 mm. The nylon brush was planted so as to be dense by making a hole in a stainless steel tube having a diameter of 300 mm. Three rotating brushes were used. The distance between the two support rollers (φ200 mm) at the bottom of the brush was 300 mm. The brush roller was pressed until the load of the drive motor for rotating the brush became 7 kW plus with respect to the load before the brush roller was pressed against the aluminum plate. The rotating direction of the brush was the same as the moving direction of the aluminum plate. The rotation speed of the brush was 200 rpm.
（ｂ）アルカリエッチング処理
　上記で得られたアルミニウム板に温度７０℃のＮａＯＨ水溶液（濃度２６質量％、アルミニウムイオン濃度６．５質量％）をスプレーしてエッチング処理を行い、アルミニウム板を６ｇ／ｍ2溶解した。その後、井水を用いてスプレーによる水洗を行った。 (B) Alkali etching treatment The aluminum plate obtained above was sprayed with an aqueous NaOH solution (concentration: 26 mass%, aluminum ion concentration: 6.5 mass%) at a temperature of 70 ° C. to obtain an aluminum plate of 6 g / m. 2 dissolved. Thereafter, washing with water was performed using well water.
（ｃ）デスマット処理
　温度３０℃の硝酸濃度１質量％水溶液（アルミニウムイオンを０．５質量％含む。）で、スプレーによるデスマット処理を行い、その後、スプレーで水洗した。上記デスマットに用いた硝酸水溶液は、硝酸水溶液中で交流を用いて電気化学的な粗面化を行う工程の廃液を用いた。 (C) Desmutting treatment The desmutting treatment was performed by spraying with a 1% by mass aqueous solution of nitric acid at a temperature of 30 ° C. (containing 0.5% by mass of aluminum ions), and then washed with water by spraying. The nitric acid aqueous solution used in the desmut was the waste liquid from the step of electrochemical surface roughening using alternating current in an aqueous nitric acid solution.
（ｄ）電気化学的粗面化処理
　６０Ｈｚの交流電圧を用いて連続的に電気化学的な粗面化処理を行った。このときの電解液は、硝酸１０．５ｇ／リットル水溶液（アルミニウムイオンを５ｇ／リットル）、温度５０℃であった。交流電源波形は電流値がゼロからピークに達するまでの時間ＴＰが０．８ｍｓｅｃ、ＤＵＴＹ比１：１、台形の矩形波交流を用いて、カーボン電極を対極として電気化学的な粗面化処理を行った。補助陽極にはフェライトを用いた。使用した電解槽はラジアルセルタイプのものを使用した。電流密度は、電流のピーク値で３０Ａ／ｄｍ2、電気量はアルミニウム板が陽極時の電気量の総和で２２０Ｃ／ｄｍ2であった。補助陽極には電源から流れる電流の５％を分流させた。その後、井水を用いてスプレーによる水洗を行った。 (D) Electrochemical roughening treatment An electrochemical roughening treatment was carried out continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a nitric acid 10.5 g / liter aqueous solution (aluminum ion 5 g / liter) at a temperature of 50 ° C. The AC power supply waveform has an electrochemical surface roughening treatment using a carbon electrode as a counter electrode using a trapezoidal rectangular wave alternating current with a time TP of 0.8 msec until the current value reaches a peak from zero, a DUTY ratio of 1: 1. went. Ferrite was used for the auxiliary anode. The electrolytic cell used was a radial cell type. The current density was 30 A / dm 2 at the peak current value, and the amount of electricity was 220 C / dm 2 in terms of the total amount of electricity when the aluminum plate was the anode. 5% of the current flowing from the power source was shunted to the auxiliary anode. Thereafter, washing with water was performed using well water.
（ｅ）アルカリエッチング処理
　アルミニウム板をカセイソーダ濃度２６質量％、アルミニウムイオン濃度６．５質量％でスプレーによるエッチング処理を３２℃で行い、アルミニウム板を３．２ｇ／ｍ2溶解し、前段の交流を用いて電気化学的な粗面化を行ったときに生成した水酸化アルミニウムを主体とするスマット成分を除去し、また、生成したピットのエッジ部分を溶解してエッジ部分を滑らかにした。その後、井水を用いてスプレーによる水洗を行った。 (E) Alkali etching treatment The aluminum plate was sprayed with a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass at 32 ° C. to dissolve the aluminum plate by 3.2 g / m 2 , The smut component mainly composed of aluminum hydroxide generated when electrochemical surface roughening was used was removed, and the edge portion of the generated pit was melted to smooth the edge portion. Thereafter, washing with water was performed using well water.
（ｆ）デスマット処理
　温度３０℃の硝酸濃度１５質量％水溶液（アルミニウムイオンを４．５質量％含む。）で、スプレーによるデスマット処理を行い、その後、井水を用いてスプレーで水洗した。上記デスマットに用いた硝酸水溶液は、硝酸水溶液中で交流を用いて電気化学的な粗面化を行う工程の廃液を用いた。 (F) Desmut treatment Desmut treatment by spraying was performed with a 15% by weight aqueous solution of nitric acid at a temperature of 30 ° C. (including 4.5% by weight of aluminum ions), and then washed with water using well water. The nitric acid aqueous solution used in the desmut was the waste liquid from the step of electrochemical surface roughening using alternating current in an aqueous nitric acid solution.
（ｇ）電気化学的粗面化処理
　６０Ｈｚの交流電圧を用いて連続的に電気化学的な粗面化処理を行った。このときの電解液は、塩酸７．５ｇ／リットル水溶液（アルミニウムイオンを５ｇ／リットル含む。）、温度３５℃であった。交流電源波形は矩形波であり、カーボン電極を対極として電気化学的な粗面化処理を行った。補助アノードにはフェライトを用いた。電解槽はラジアルセルタイプのものを使用した。
　電流密度は電流のピーク値で２５Ａ／ｄｍ2、電気量はアルミニウム板が陽極時の電気量の総和で５０Ｃ／ｄｍ2であった。その後、井水を用いてスプレーによる水洗を行った。 (G) Electrochemical surface roughening treatment An electrochemical surface roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a hydrochloric acid 7.5 g / liter aqueous solution (containing 5 g / liter of aluminum ions) at a temperature of 35 ° C. The AC power supply waveform was a rectangular wave, and an electrochemical surface roughening treatment was performed using a carbon electrode as a counter electrode. Ferrite was used for the auxiliary anode. The electrolytic cell used was a radial cell type.
The current density was 25 A / dm 2 at the peak current value, and the amount of electricity was 50 C / dm 2 in terms of the total amount of electricity when the aluminum plate was the anode. Thereafter, washing with water was performed using well water.
（ｈ）アルカリエッチング処理
　アルミニウム板をカセイソーダ濃度２６質量％、アルミニウムイオン濃度６．５質量％でスプレーによるエッチング処理を３２℃で行い、アルミニウム板を０．１０ｇ／ｍ2溶解し、前段の交流を用いて電気化学的な粗面化処理を行ったときに生成した水酸化アルミニウムを主体とするスマット成分を除去し、また、生成したピットのエッジ部分を溶解してエッジ部分を滑らかにした。その後、井水を用いてスプレーによる水洗を行った。 (H) Alkaline etching treatment An aluminum plate is etched by spraying at 32 ° C. with a caustic soda concentration of 26% by mass and an aluminum ion concentration of 6.5% by mass, and the aluminum plate is dissolved at 0.10 g / m 2 , so The smut component mainly composed of aluminum hydroxide generated during the electrochemical surface roughening treatment was removed, and the edge portion of the generated pit was melted to smooth the edge portion. Thereafter, washing with water was performed using well water.
（ｉ）デスマット処理
　温度６０℃の硫酸濃度２５質量％水溶液（アルミニウムイオンを０．５質量％含む。）で、スプレーによるデスマット処理を行い、その後、井水を用いてスプレーによる水洗を行った。 (I) Desmut treatment A desmut treatment by spraying was performed with a 25% by mass aqueous solution of sulfuric acid at a temperature of 60 ° C. (containing 0.5% by mass of aluminum ions), and then water washing by spraying was performed using well water.
（ｊ）陽極酸化処理
　電解液としては、硫酸を用いた。電解液は、いずれも硫酸濃度１７０ｇ／リットル（アルミニウムイオンを０．５質量％含む。）、温度は４３℃であった。その後、井水を用いてスプレーによる水洗を行った。電流密度は共に約３０Ａ／ｄｍ2であった。最終的な酸化皮膜量は２．７ｇ／ｍ2であった。 (J) Anodizing treatment As the electrolytic solution, sulfuric acid was used. All electrolytes had a sulfuric acid concentration of 170 g / liter (containing 0.5 mass% of aluminum ions), and the temperature was 43 ° C. Thereafter, washing with water was performed using well water. Both current densities were about 30 A / dm 2 . The final oxide film amount was 2.7 g / m 2 .
（Ｎｏ．１～５、１７、１８、２０、２１）
　上記の転写材Ａの処理面にＰＥＴ（東レ（株）製、ルミラー１００）を載置し、プレス機を用いプレスすることで所望の表面を有する基材（ＰＥＴ基材）を得た。 (No. 1 to 5, 17, 18, 20, 21)
A substrate (PET substrate) having a desired surface was obtained by placing PET (Lumirror 100, manufactured by Toray Industries, Inc.) on the treated surface of the transfer material A and pressing it using a press.
（Ｎｏ．６～１１、１３～１６、１９）
　ＰＥＴ（東レ（株）製、ルミラー１００）をサンドブラスト法により所望のＲａの表面粗さとした。その後、サンドブラスト処理したＰＥＴを転写材として、プレス機を用い、プレスローラにて、プレス時の温度、プレスロール押し圧（圧力）及び速度を変えることで、所望の表面形状を有するＰＥＴ基材を作製した。なお、このとき、表１に示すように、表面が平坦なプレスローラ、又は、表面がエンボス加工されたプレスローラを使用した。 (No. 6-11, 13-16, 19)
PET (Lumirror 100, manufactured by Toray Industries, Inc.) was made to have a desired surface roughness of Ra by sandblasting. Thereafter, a PET base material having a desired surface shape is obtained by changing the temperature, pressing roll pressure (pressure) and speed at the time of pressing with a press roller using a sandblasted PET as a transfer material. Produced. At this time, as shown in Table 1, a press roller having a flat surface or a press roller having an embossed surface was used.
（Ｎｏ．１２）
　帝人（株）製、Ｕ４（フィラー練り込みＰＥＴ）を使用した。 (No. 12)
U4 (filler-kneaded PET) manufactured by Teijin Limited was used.
　なお、表１中、サンドブラスト処理ＰＥＴ－１とは、ＰＥＴフィルムをサンドブラスト処理するに際し、使用する研磨剤である硅砂（７号硅砂）の量を多くして作製したものであり、表面形状はＲａが０．６μｍであった。また、サンドブラスト処理ＰＥＴ－２とは、ＰＥＴフィルムをサンドブラスト処理するに際し、使用する硅砂（７号硅砂）の量を少なくして作製したものであり、表面形状はＲａが０．３μｍであった。同様に、サンドブラスト処理ＰＥＴ－３は、更に使用する硅砂（７号硅砂）の量を少なくして作製したものであり、表面形状はＲａが０．２μｍであった。
　また、表面がエンボス加工されたプレスローラは、ローラ表面の算術平均粗さＲａが１．０μｍであった。
　また、プレス機としては、（有）丸協技研製のロール型プレス機を使用した。 In Table 1, sand blasting PET-1 was prepared by increasing the amount of sand (No. 7 cinnabar) as an abrasive used when sand blasting a PET film. Was 0.6 μm. Sandblasted PET-2 was produced by reducing the amount of dredged sand (No. 7 dredged sand) used for sandblasting a PET film, and the surface shape Ra was 0.3 μm. Similarly, sandblasted PET-3 was prepared by further reducing the amount of dredged sand (No. 7 dredged sand) to be used, and the surface shape was Ra 0.2 μm.
The press roller whose surface was embossed had an arithmetic average roughness Ra of the roller surface of 1.0 μm.
Moreover, as a press machine, the roll type press machine made from Marukyokyoken was used.
（算術平均粗さＲａ（μｍ）、急峻度Δａ（ｄｅｇ）及び表面積比Δｓの測定）
　算術平均粗さＲａ（μｍ）及び急峻度Δａ（ｄｅｇ）は、以下のように測定した。
　　測定機器；サーフコム　５７５Ａ（（株）東京精密製）
　　測定条件
　　　測定速度；０．３ｍｍ／ｓｅｃ
　　　測定長；１０ｍｍ
　　　カットオフ；０．８ｍｍ (Measurement of arithmetic average roughness Ra (μm), steepness Δa (deg) and surface area ratio Δs)
The arithmetic average roughness Ra (μm) and the steepness Δa (deg) were measured as follows.
Measuring instrument: Surfcom 575A (manufactured by Tokyo Seimitsu Co., Ltd.)
Measurement conditions Measurement speed: 0.3 mm / sec
Measurement length: 10mm
Cut off: 0.8mm
　表面積比Δｓは、以下のようにして測定した。
（ｉ）原子間力顕微鏡による表面形状の測定
　まず、原子間力顕微鏡（Ａｔｏｍｉｃ Ｆｏｒｃｅ Ｍｉｃｒｏｓｃｏｐｅ：ＡＦＭ）により表面形状を測定し、３次元データ（ｆ（ｘ，ｙ））を求めた。
　測定は、以下の条件で行った。すなわち、ＳＥＩＫＯ　ＳＰＩ－３８００Ｎプローブステーションを具えたＳＥＩＫＯ　ＳＰＡ－４００　ＡＦＭを用いて、基材又は版を１ｃｍ角の大きさに切り取って、ピエゾスキャナー上の水平な試料台にセットし、カンチレバーを試料表面にアプローチし、原子間力が働く領域に達したところで、ＸＹ方向にスキャンし、その際、試料の凹凸をＺ方向のピエゾの変位でとらえた。ピエゾスキャナーは、ＸＹ方向について１５０μｍ、Ｚ方向について１０μｍ、走査可能なものを使用した。カンチレバーは共振周波数１２０～４００ｋＨｚ、バネ定数１２～９０Ｎ／ｍのもの（例えば、ＳＩ－ＤＦ２０、セイコーインスツルメンツ社製；ＮＣＨ－１０、ＮＡＮＯＳＥＮＳＯＲＳ社製；又は、ＡＣ－１６０ＴＳ、オリンパス社製）を用い、ＤＦＭモード（Ｄｙｎａｍｉｃ Ｆｏｒｃｅ Ｍｏｄｅ）で測定した。また、求めた３次元データを最小二乗近似することにより試料のわずかな傾きを補正し基準面を求めた。
　計測の際は、表面の１００μｍ×１００μｍ四方を５１６×２５６点測定した。ＸＹ方向の分解能は０．１μｍ、Ｚ方向の分解能は０．１５ｎｍ、スキャン速度は５０μｍ／ｓｅｃとした。
（ｉｉ）表面積比ΔＳの算出
　上記（ｉ）で得られた３次元データ（ｆ（ｘ，ｙ））を用い、隣り合う３点を抽出し、その３点で形成される微小三角形の面積の総和を求め、実面積Ｓxとする。表面積比Δｓは、得られた実面積Ｓxと、幾何学的測定面積Ｓ0とから、式（１）により求めた。
　　　　Δｓ＝Ｓx／Ｓ0　　　　　　（１） The surface area ratio Δs was measured as follows.
(I) Measurement of surface shape with atomic force microscope First, the surface shape was measured with an atomic force microscope (AFM) to obtain three-dimensional data (f (x, y)).
The measurement was performed under the following conditions. That is, using a SEIKO SPA-400 AFM equipped with a SEIKO SPI-3800N probe station, the substrate or plate is cut to a 1 cm square size and set on a horizontal sample stage on a piezo scanner, and the cantilever is placed on the sample surface. Then, when the region where the atomic force was applied was reached, scanning was performed in the XY direction, and the unevenness of the sample was captured by the displacement of the piezo in the Z direction. A piezo scanner that can scan 150 μm in the XY direction and 10 μm in the Z direction was used. The cantilever having a resonance frequency of 120 to 400 kHz and a spring constant of 12 to 90 N / m (for example, SI-DF20, manufactured by Seiko Instruments Inc .; NCH-10, manufactured by NANOSENSORS Inc .; or AC-160TS, manufactured by Olympus Corporation) The measurement was performed in DFM mode (Dynamic Force Mode). Further, the reference plane was obtained by correcting the slight inclination of the sample by least-square approximation of the obtained three-dimensional data.
At the time of measurement, 516 × 256 points were measured on a 100 μm × 100 μm square of the surface. The resolution in the XY direction was 0.1 μm, the resolution in the Z direction was 0.15 nm, and the scan speed was 50 μm / sec.
(Ii) Calculation of surface area ratio ΔS Using the three-dimensional data (f (x, y)) obtained in (i) above, three adjacent points are extracted, and the area of the micro triangle formed by the three points is calculated. The sum is obtained and set as the actual area S x . The surface area ratio Δs was determined by the formula (1) from the obtained real area S x and the geometric measurement area S 0 .
Δs = S x / S 0 (1)
　評価は、以下のようにして行った。
（評価）
＜剥離性＞
　レリーフ形成膜を基材（塗布用フィルム）ごと３ｃｍ幅にカットし、基材とレリーフ形成膜（硬化膜）との１８０°剥離の剥離力を測定した。
　　Ａ：剥離力が　０．８Ｎ／ｃｍ未満
　　Ｂ：剥離力が　０．８Ｎ／ｃｍ～１．０Ｎ／ｃｍ
　　Ｃ：剥離力が　１．０Ｎ／ｃｍより大きい
　評価Ｂ以上であれば実用上問題がない。 Evaluation was performed as follows.
(Evaluation)
<Peelability>
The relief forming film was cut to a width of 3 cm together with the substrate (coating film), and the peeling force for 180 ° peeling between the substrate and the relief forming film (cured film) was measured.
A: Peeling force is less than 0.8 N / cm B: Peeling force is 0.8 N / cm to 1.0 N / cm
C: Peeling force is greater than 1.0 N / cm.
＜基材残渣＞
　レリーフ形成膜（硬化膜）を剥離後の基材（塗布用フィルム）をマイクロスコープにて観察し、基材（塗布用フィルム）上に付着した残渣量を測定した。なお、１０μｍ以上の残渣の数を測定した。
　　Ａ：残渣量；１０個／ｍｍ2未満
　　Ｂ：残渣量；１０個／ｍｍ2以上５０個／ｍｍ2未満
　　Ｃ：残渣量；５０個／ｍｍ2以上
　評価Ｂ以上であれば実用上問題がない。 <Substrate residue>
The base material (coating film) after peeling the relief forming film (cured film) was observed with a microscope, and the amount of residue adhered on the base material (coating film) was measured. The number of residues of 10 μm or more was measured.
A: Residue amount; less than 10 pieces / mm 2 B: Residue amount; 10 pieces / mm 2 or more and less than 50 pieces / mm 2 C: Residue amount; 50 pieces / mm 2 or more .
＜紙粉付着性＞
　基材（塗布用フィルム）から剥離したレリーフ形成膜を５ｃｍ×５ｃｍのサイズにカットし、画像形成面（塗布用フィルム表面と接触していた面）に紙粉（日本画材）を付着させた前後の膜質量を測定した。なお、余分な紙粉を軽く払い落とした。紙粉付着前後の質量差を計算し紙粉付着量とした。
　　Ａ：紙粉付着量；１２ｇ／ｍｍ2未満
　　Ｂ：紙粉付着量；１２ｇ／ｍｍ2以上２０ｇ／ｍｍ2未満
　　Ｃ：紙粉付着量；２０ｇ／ｍｍ2以上
　評価Ｂ以上であれば実用上問題がない。 <Paper dust adhesion>
Before and after the relief forming film peeled off from the base material (coating film) was cut into a size of 5 cm x 5 cm and paper powder (Japanese painting material) was attached to the image forming surface (the surface that was in contact with the coating film surface) The film mass of was measured. The excess paper dust was lightly wiped off. The difference in mass before and after the paper dust adhesion was calculated and used as the paper dust adhesion amount.
A: Paper dust adhesion amount: less than 12 g / mm 2 B: Paper dust adhesion amount: 12 g / mm 2 or more and less than 20 g / mm 2 C: Paper dust adhesion amount: 20 g / mm 2 or more There is no.
＜インキ着肉性＞
　画像部の着肉性をみるため、図４に記載の製版装置を用いて製版を行った。
　彫刻条件は、最大出力８．０Ｗのファイバー付き半導体レーザー（ＦＣ－ＬＤ）ＳＤＬ－６３９０（ＪＤＳＵ社製、波長：９１５ｎｍ）を装備したレーザー記録装置を用いた。走査速度：１，３００ｍｍ／秒、ピッチ設定：２，４００ＤＰＩの条件で、１ｃｍ四方に巾１００μｍの凹線、凸線を１００μｍおきに彫刻した。その後、レリーフ印刷版をフレキソ印刷機ＩＴＭ－４型（（株）伊予機械製）の版胴に両面テープＤｕｐｌｏＦｌｅｘ　５．１＋で貼り付け、印刷インキＵＶフレキソ５００藍（ＴＯＫＡ）、アニロックスローラ（線数９００ｌｐｉ）を用い、通常印圧（版面と印刷用紙とが接触する距離から圧胴を４０μｍ版面側に押し込んだ条件）にて印刷を行いベタ部のインク付着を目視にて観察し、評価した。評価指標は以下の通りである。なお、実施例の版は、すべて彫刻ができていた。
　　Ａ：インキが版全面に均一に付着している
　　Ｂ：インキが一部不均一に付着している
　　Ｃ：インキが付着していない部分が多くある
　評価Ｂ以上であれば実用上問題がない。 <Ink fillability>
In order to check the inking property of the image portion, plate making was performed using the plate making apparatus shown in FIG.
As the engraving conditions, a laser recording device equipped with a fiber-coupled semiconductor laser (FC-LD) SDL-6390 (JDSU, wavelength: 915 nm) with a maximum output of 8.0 W was used. Under the conditions of scanning speed: 1,300 mm / sec and pitch setting: 2,400 DPI, concave lines and convex lines with a width of 100 μm were engraved every 100 μm in a 1 cm square. After that, the relief printing plate was attached to the plate cylinder of flexographic printing machine ITM-4 type (manufactured by Iyo Machine Co., Ltd.) with double-sided tape DuploFlex 5.1+, printing ink UV flexo 500 indigo (TOKA), anilox roller (number of lines) 900 lpi), printing was performed under normal printing pressure (conditions in which the impression cylinder was pushed into the 40 μm plate side from the distance between the plate surface and the printing paper), and the ink adhesion on the solid portion was visually observed and evaluated. The evaluation index is as follows. The plates of the examples were all engraved.
A: Ink is uniformly attached to the entire plate surface B: Ink is partially attached unevenly C: There are many portions where ink is not attached If there is an evaluation B or higher, there is no practical problem.
　レリーフ形成膜１について基材を変化させて評価した結果を以下の表２に示す。また、レリーフ形成膜２について基材を変化させて評価した結果を以下の表３に、レリーフ形成膜３について基材を変化させて評価した結果を以下の表４に示す。 Table 2 below shows the results of evaluating the relief-forming film 1 by changing the base material. In addition, Table 3 below shows the results of evaluating the relief forming film 2 while changing the base material, and Table 4 shows the results of evaluating the relief forming film 3 by changing the base material.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　各版材の表面形状を本発明の物性値範囲にすることで、版材の性能である紙粉付着性、インキ着肉性がよくなるだけでなく、膜作製時の基材との剥離性がよく残渣を少なくすることができた。
　特に、レリーフ形成膜１については、粘調な塗布膜の剥離性が良好になることが期待できる。 By making the surface shape of each plate material within the range of the physical property values of the present invention, not only the paper powder adhesion and ink inking properties, which are the performance of the plate material, are improved, but also the releasability from the substrate at the time of film production is The residue could be reduced well.
In particular, regarding the relief forming film 1, it can be expected that the peelability of the viscous coating film is improved.
１１　　　製版装置
２０　　　光源ユニット
２１　　　半導体レーザー
２２　　　光ファイバー
２３　　　アダプタ基板
２５　　　ＳＣ型光コネクタ
２７　　　ＬＤドライバー基板
２９　　　配線部材
３０　　　露光ヘッド
３２　　　コリメータレンズ
３３　　　開口部材
３４　　　結像レンズ
４０　　　露光ヘッド移動部
４１　　　ボールネジ
４２　　　レール
４３　　　副走査モータ
４４　　　ステージ
４６、４７　　　ベアリング
５０　　　ドラム
５１　　　主走査モータ
５２　　　軸線
５５　　　チャック部材
６０　　　ピント位置変更機構
６１　　　モータ
６２　　　ボールネジ
７０　　　光ファイバー
７１　　　光ファイバー端部
９０　　　間欠送り機構
９２　　　露光範囲
２８０　　　光出射部
２８２　　　Ｖ字溝
３００　　　光ファイバーアレイ
３０１　　　光ファイバー端部群
３０２　　　基台
５００　　　ファイバーアレイユニット光源
５０１、５０２、５０３、５０４　　　光ファイバーアレイユニット
Ｆ　　　レリーフ印刷版原版 DESCRIPTION OF SYMBOLS 11 Plate making apparatus 20 Light source unit 21 Semiconductor laser 22 Optical fiber 23 Adapter board 25 SC type optical connector 27 LD driver board 29 Wiring member 30 Exposure head 32 Collimator lens 33 Opening member 34 Imaging lens 40 Exposure head moving part 41 Ball screw 42 Rail 43 Secondary Scanning motor 44 Stages 46 and 47 Bearing 50 Drum 51 Main scanning motor 52 Axis 55 Chuck member 60 Focus position changing mechanism 61 Motor 62 Ball screw 70 Optical fiber 71 Optical fiber end 90 Intermittent feed mechanism 92 Exposure range 280 Light emitting part 282 V-shaped groove 300 Optical fiber array 301 Optical fiber end group 302 Base 500 Fiber array unit light source 501, 502, 503, 504 Light § Iba array unit F relief printing plate precursor

Claims (17)

  1. 　バインダーポリマーを含有し、
    　表面の算術平均粗さＲａが０．０５μｍ～０．８０μｍであり、急峻度Δａが０．０１ｄｅｇ～０．０８ｄｅｇであり、かつ、表面積比Δｓが１．０～４．５であることを特徴とする
    　レリーフ形成膜。     Contains a binder polymer,
    The arithmetic average roughness Ra of the surface is 0.05 μm to 0.80 μm, the steepness Δa is 0.01 deg to 0.08 deg, and the surface area ratio Δs is 1.0 to 4.5. Relief forming film.
  2. 　熱又は光硬化性樹脂組成物の硬化物からなる、請求項１に記載のレリーフ形成膜。 The relief forming film according to claim 1, comprising a cured product of a heat or photocurable resin composition.
  3. 　熱硬化性樹脂組成物の硬化物からなる、請求項１又は２に記載のレリーフ形成膜。 The relief forming film according to claim 1 or 2, comprising a cured product of a thermosetting resin composition.
  4. 　光熱変換剤を含有する、請求項１～３のいずれか１項に記載のレリーフ形成膜。 The relief forming film according to any one of claims 1 to 3, comprising a photothermal conversion agent.
  5. 　前記バインダーポリマーのガラス転移温度（Ｔｇ）が２０℃以上である、請求項１～４のいずれか１項に記載のレリーフ形成膜。 The relief forming film according to any one of claims 1 to 4, wherein the binder polymer has a glass transition temperature (Tg) of 20 ° C or higher.
  6. 　支持体上に請求項１～５のいずれか１項に記載のレリーフ形成膜を有する、レリーフ印刷版原版。 A relief printing plate precursor having the relief forming film according to any one of claims 1 to 5 on a support.
  7. 　（ａ）熱又は光硬化性樹脂組成物を基材上に塗布する塗布工程と、
    　（ｂ）該熱又は光硬化性樹脂組成物を熱又は光により硬化して硬化膜を形成する硬化膜形成工程と、
    　（ｃ）該硬化膜を前記基材から剥離する硬化膜剥離工程と、を含み、
    　前記熱又は光硬化性樹脂組成物を塗布する側の前記基材の表面の算術平均粗さＲａが０．０６μｍ～０．９０μｍであり、急峻度Δａが０．０１ｄｅｇ～０．１０ｄｅｇであり、かつ、表面積比Δｓが１．０～５．０であることを特徴とする、
    　レリーフ形成膜の製造方法。     (A) an application step of applying a heat or photocurable resin composition on a substrate;
    (B) a cured film forming step of curing the heat or photocurable resin composition with heat or light to form a cured film;
    (C) a cured film peeling step of peeling the cured film from the substrate,
    The arithmetic average roughness Ra of the surface of the substrate on the side on which the heat or photocurable resin composition is applied is 0.06 μm to 0.90 μm, and the steepness Δa is 0.01 deg to 0.10 deg. And the surface area ratio Δs is 1.0 to 5.0,
    Manufacturing method of relief forming film.
  8. 　前記硬化膜形成工程が、熱硬化性樹脂組成物に加熱により架橋構造を形成させて硬化膜を形成する工程である、請求項７に記載のレリーフ形成膜の製造方法。 The method for producing a relief forming film according to claim 7, wherein the cured film forming step is a step of forming a cured film by forming a crosslinked structure by heating the thermosetting resin composition.
  9. 　前記基材が樹脂フィルムである、請求項７又は８に記載のレリーフ形成膜の製造方法。 The method for producing a relief forming film according to claim 7 or 8, wherein the substrate is a resin film.
  10. 　前記熱又は光硬化性樹脂組成物が、バインダーポリマー及び光熱変換剤を含有する、請求項７～９のいずれか１項に記載のレリーフ形成膜の製造方法。 The method for producing a relief-forming film according to any one of claims 7 to 9, wherein the heat or photocurable resin composition contains a binder polymer and a photothermal conversion agent.
  11. 　前記光熱変換剤がカーボンブラックである、請求項１０に記載のレリーフ形成膜の製造方法。 The method for producing a relief-forming film according to claim 10, wherein the photothermal conversion agent is carbon black.
  12. 　前記カーボンブラックが、吸油量が１５０ｍＬ／１００ｇ未満のカーボンブラックである、請求項１１に記載のレリーフ形成膜の製造方法。 The method for producing a relief forming film according to claim 11, wherein the carbon black is carbon black having an oil absorption of less than 150 mL / 100 g.
  13. 　請求項７～１２のいずれか１項に記載のレリーフ形成膜の製造方法により得られたレリーフ形成膜の前記基材と接触していた面とは反対側の面と、支持体と、を接着する接着工程を含む
    　レリーフ印刷版原版の製造方法。     A surface of the relief forming film obtained by the method for producing a relief forming film according to any one of claims 7 to 12 opposite to the surface in contact with the substrate is bonded to the support. A method for producing a relief printing plate precursor comprising an adhering step.
  14. 　請求項１３に記載の製造方法により得られたレリーフ印刷版原版。 A relief printing plate precursor obtained by the production method according to claim 13.
  15. 　請求項６又は１４に記載のレリーフ印刷版原版をレーザー彫刻し、レリーフ層を形成する彫刻工程、を含むレリーフ印刷版の製版方法。 A method for making a relief printing plate, comprising engraving a step of laser engraving the relief printing plate precursor according to claim 6 or 14 to form a relief layer.
  16. 　前記彫刻工程が、波長が７００ｎｍ～１，３００ｎｍのファイバー付き半導体レーザーを用いた走査露光により彫刻する工程である、請求項１５に記載のレリーフ印刷版の製版方法。 The method for making a relief printing plate according to claim 15, wherein the engraving step is a step of engraving by scanning exposure using a semiconductor laser with a fiber having a wavelength of 700 nm to 1,300 nm.
  17. 　請求項１５又は１６に記載のレリーフ印刷版の製版方法により製造されたレリーフ層を有するレリーフ印刷版。 A relief printing plate having a relief layer produced by the method for making a relief printing plate according to claim 15 or 16.
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