WO2017170391A1 - 平版印刷版原版及びその積層体並びに平版印刷版原版の製造方法 - Google Patents
平版印刷版原版及びその積層体並びに平版印刷版原版の製造方法 Download PDFInfo
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- WO2017170391A1 WO2017170391A1 PCT/JP2017/012374 JP2017012374W WO2017170391A1 WO 2017170391 A1 WO2017170391 A1 WO 2017170391A1 JP 2017012374 W JP2017012374 W JP 2017012374W WO 2017170391 A1 WO2017170391 A1 WO 2017170391A1
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- WIPO (PCT)
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- coating
- printing plate
- lithographic printing
- plate precursor
- layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/12—Printing plates or foils; Materials therefor non-metallic other than stone, e.g. printing plates or foils comprising inorganic materials in an organic matrix
- B41N1/14—Lithographic printing foils
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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
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
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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
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
- B41C1/1016—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials characterised by structural details, e.g. protective layers, backcoat layers or several imaging layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/04—Printing plates or foils; Materials therefor metallic
- B41N1/08—Printing plates or foils; Materials therefor metallic for lithographic printing
- B41N1/086—Printing plates or foils; Materials therefor metallic for lithographic printing laminated on a paper or plastic base
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2201/00—Location, type or constituents of the non-imaging layers in lithographic printing formes
- B41C2201/06—Backcoats; Back layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N1/00—Printing plates or foils; Materials therefor
- B41N1/04—Printing plates or foils; Materials therefor metallic
- B41N1/08—Printing plates or foils; Materials therefor metallic for lithographic printing
- B41N1/083—Printing plates or foils; Materials therefor metallic for lithographic printing made of aluminium or aluminium alloys or having such surface layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N3/00—Preparing for use and conserving printing surfaces
Definitions
- the present invention relates to a lithographic printing plate precursor, a laminate thereof, and a method for producing the lithographic printing plate precursor, and more particularly to a technique for making the lithographic printing plate precursor less interleaving paper.
- a lithographic printing plate precursor is often stored and transported as a laminate in which a plurality of lithographic printing plate precursors are stacked.
- a laminate of lithographic printing plate precursors usually, 1) prevention of abrasion between the lithographic printing plate precursors, 2) prevention of adhesion between the lithographic printing plate precursors, 3) plate making by taking out the lithographic printing plate precursors one by one from the laminate 4) Insert paper between the stacked lithographic printing plate precursors for the purpose of imparting plate separation to prevent multiple feeding in the process, and 4) preventing scratches on the recording layer side surface of the lithographic printing plate precursor Is done.
- an organic polymer layer containing crosslinked polymer particles having a number average particle diameter of 1 to 100 ⁇ m is formed on the surface of the support opposite to the surface having the recording layer.
- a lithographic printing plate precursor having the same is known (Patent Document 1). Also known is a lithographic printing plate precursor (Patent Document 2) having a photosensitive layer containing polymer fine particles on one side of a support and a backcoat layer containing an organic polymer compound on the opposite side. .
- Patent Document 3 a lithographic printing plate precursor having a protective layer containing organic polymer fine particles surface-coated with a hydrophilic polymer and silica as the uppermost layer on the recording layer side of the support, and having a back coat layer made of an organic resin on the opposite side.
- Patent Documents 4 to 7 propose a paper-less printing plate precursor using a method different from the methods described in Patent Documents 1 to 3.
- Patent Document 4 realizes the elimination of interleaving paper by forming a dot-shaped or line-shaped convex discontinuous pattern on the back side of a support for a lithographic printing plate by inkjet, screen printing, gravure printing, etc. Propose to do.
- Patent Document 5 proposes forming a linear polymer layer arranged in a plurality of rows spaced apart from each other in the width direction on the surface opposite to the recording layer of the support.
- Patent Document 6 has a recording layer that includes a water-insoluble and alkali-soluble resin and an infrared absorber on one side of a support, and can form an image by infrared irradiation.
- an organic polymer layer having an arithmetic average surface roughness Ra in the range of 0.05 to 0.40 ⁇ m is provided on the opposite side.
- a matting agent is added on or in the organic polymer layer (hereinafter referred to as “matte”). It is referred to as “agent addition method”).
- the arithmetic mean roughness of the surface of a support having a non-radiation sensitive back coat layer is set to at least 0.1 ⁇ m (usually 0.1 ⁇ m to 0.4 ⁇ m), or a matting agent is contained.
- a lithographic printing plate having a surface roughness formed on the backcoat layer is disclosed.
- JP 2007-148040 A JP 2008-249851 A JP 2008-15503 A WO2014 / 202519A1 JP 2008-64778 A JP 2007-122003 A US2011 / 0287365A1
- the glass transition temperature Tg of the layer composed of the crosslinked polymer particles and the organic polymer is too high, the generation of scratches may not be sufficiently prevented.
- polymer fine particles are contained in the photosensitive layer.
- the photosensitive layer is a layer that greatly affects the performance of the lithographic printing plate prepared from the lithographic printing plate precursor. Therefore, it is essential that the performance of the lithographic printing plate precursor, in particular, the image formability is not affected and the fine particles do not fall off.
- the width of the photosensitive layer design is extremely limited.
- Patent Document 3 when the technique described in Patent Document 3 is applied to an on-machine development type lithographic printing plate precursor having a remarkably thin protective layer as compared with a conventional wet development type lithographic printing plate precursor, a sufficient effect is obtained. I can't. This seems to be because the organic resin fine particles are not sufficiently retained and fall off from the protective layer. In addition, if the fine particles fall off, another lithographic printing plate precursor is damaged.
- the layers cannot hold the particles depending on the combination of materials, and the production / processing line, the user's exposure machine, and printing can be performed by dropping the particles. There is a risk of contaminating the machine.
- a convex discontinuous pattern of dot shape or line shape is formed on the back surface of the support of the lithographic printing plate precursor, so that the lithographic printing plate is laminated.
- the back surface of the uncoated portion of the support in the discontinuous pattern rubs against the photosensitive layer on the surface of the support, and the lithographic printing plate precursor is easily damaged.
- the method of roughening the surface of the backcoat layer by, for example, brushing has a drawback that the surface of the backcoat layer tends to become dirty.
- the method of adjusting the surface roughness of the support and reflecting the roughness on the surface of the backcoat layer is possible when the surface roughness required for the backcoat layer is small, but when it is large difficult.
- the present invention has been made in view of such circumstances, and by forming a novel surface roughness structure in the backcoat layer, the lithographic printing plate precursors are prevented from being scraped off, and the lithographic printing plate precursors are prevented from being bonded to each other.
- An object of the present invention is to provide a lithographic printing plate precursor, a laminate thereof, and a method for producing the lithographic printing plate precursor that can satisfy all of the above problems.
- the lithographic printing plate precursor according to the present invention is a lithographic printing plate precursor having a polymer layer on the surface of a support, and has an arithmetic average due to a surface roughness structure in which a thin film portion and a thick film portion are continuously formed on the back surface of the support.
- the back coat layer has a height Sa of 0.5 ⁇ m or more.
- the arithmetic average height Sa of the backcoat layer is preferably 0.5 ⁇ m or more and 24 ⁇ m or less. Furthermore, it is preferably 1.5 ⁇ m or more and 8.0 ⁇ m or less.
- the arithmetic average height Sa of the back surface of the support is preferably 0.3 ⁇ m or less.
- the back coat layer preferably has a Beck smoothness (Beck second) of 200 seconds or less.
- the backcoat layer preferably contains at least one non-alkali availability resin.
- the surface roughness structure is preferably a stripe coating film in which strip-shaped thick film portions are arranged on a planar thin film portion.
- the surface roughness structure is preferably a dot coating film in which dot-like thick film portions are scattered on a planar thin film portion.
- the surface roughness structure is preferably a broken-line coating film in which broken-line thick film parts are arranged on a planar thin-film part.
- the width W of the thick film part is preferably 0.5 mm or more and 50 mm or less.
- the pitch ⁇ between the thick film portions is preferably 0.5 mm or more and 50 mm or less.
- the ratio Zt / ⁇ between the thickness difference Zt and the pitch ⁇ is preferably 0.10 or less.
- the ratio Zt / W between the thickness difference Zt and the width W of the thick film part is preferably 0.10 or less.
- the backcoat layer preferably contains at least one non-photocurable resin having a weight average molecular weight of 3000 or less.
- the backcoat layer comprises phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, mp-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, or m- / p -Any of mixed)
- Novolak resin such as mixed formaldehyde resin, resol resin, pyrogallol, acetone resin, epoxy resin, saturated copolymer polyester resin, phenoxy resin, polyvinyl acetal resin, vinylidene chloride copolymer resin, polybutene, polybutadiene, polyamide , Unsaturated copolymerized polyester resin, polyurethane, polyurea, polyimide, polysiloxane, polycarbonate, epoxy resin, chlorinated polyethylene, alkylphenol aldehyde condensation tree , Polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylic resin copolyzed
- the polymer layer is preferably a positive image recording layer containing an infrared absorber.
- the polymer layer is preferably a negative image recording layer containing an infrared absorber, a polymerization initiator, or a polymerizable compound.
- the polymer layer is a lithographic printing plate precursor for a treated and discarded plate comprising a non-photosensitive layer.
- the polymer layer is a lithographic printing plate precursor for an untreated plate composed of either a water-soluble layer or a water-dispersible layer.
- the polymer layer is a lithographic printing plate precursor for an untreated discard plate composed of either a water-soluble layer or a water-dispersible layer.
- the water-dispersible layer preferably contains fine polymer particles.
- the laminate of the present invention has a polymer layer on the surface of the support, and an arithmetic average height Sa of 0.5 ⁇ m or more due to a surface roughness structure in which a thin film portion and a thick film portion are continuously formed on the back surface of the support.
- a plurality of planographic printing plate precursors having a backcoat layer are laminated.
- the method for producing a lithographic printing plate precursor according to the present invention is a method for producing a lithographic printing plate precursor having a polymer layer on the surface of a support, the surface having a thin film portion and a thick film portion continuously formed on the back surface of the support.
- coats and forms the coating film of roughness structure, and the drying process which dries a coating film and forms the backcoat layer whose arithmetic mean height Sa is 0.5 micrometer or more by the surface roughness structure were provided.
- the difference in thickness between the adjacent thin film portion and the thick film portion is 1 ⁇ m or more and 50 ⁇ m or less in the coating step.
- the viscosity of the coating liquid is 0.3 mPa ⁇ s to 100 mPa ⁇ s
- the surface tension is 20 mN / m to 40 mN / m
- the contact angle between the coating liquid and the support is
- the coating solution is applied to the support under the coating conditions of 10 ° or more and 90 ° or less to form a coating film having a wet surface roughness structure, and in the drying process, when the formed wet coating film is dried, It is preferable that the drying point t is dried under a drying condition that satisfies the following equations 1 and 2.
- t is the time from the start of drying to the drying point
- the unit is s
- X is the initial average film thickness
- the unit is m
- ⁇ is the viscosity of the coating solution for the stripe coating
- the unit is Pa ⁇ s
- ⁇ is the stripe
- the unit is m
- Z 0 is the initial film thickness difference
- the unit is m
- Z t is the film thickness difference in the dry film
- the unit is m
- ⁇ is the surface tension of the coating solution for the stripe coating film.
- the unit is N / m
- Pe is the Peclet number and a constant of 1.5 ⁇ 10 ⁇ 6
- W is the stripe width
- the unit is m.
- the coating process it is preferable to coat and form a coating film by any one of a bar coating method, an inkjet printing method, a gravure printing method, a screen printing method, and a spray coating method.
- the coating film having a surface roughness structure is preferably a stripe coating film in which strip-shaped thin film portions and strip-shaped thick film portions are alternately and continuously arranged.
- the coating film having a surface roughness structure is preferably a dot coating film in which dot-like thick film portions are scattered on the surface of the flat thin film portion.
- the coating film having a surface roughness structure is preferably a broken-line coating film in which broken-line thick film portions are continuously arranged on the surface of a flat thin film portion.
- the grooved portion where the groove is formed and the grooveless portion where the groove is not formed are alternately formed in the axial direction. It is preferable to apply the coating liquid with a coating bar using a bar coating apparatus having a bar.
- the coating bar has a pitch length between adjacent concave portions or convex portions, and a depth of the concave portion between the concave portions and the convex portions constituting the groove of the grooved portion.
- D is the opening width of the recess
- P is 0.25 mm or more
- D / P is 0.49 or less
- h / D is 0.01 or more and 0.55 or less.
- a coating bar is used to continuously apply a coating liquid to a traveling belt-like support, and the diameter of the coating bar is 6 mm or more and 50 mm or less. It is preferable that the relationship of the following formula 3 is satisfied when the rotation speed of the bar is r and the unit is rpm, and the viscosity of the coating solution is ⁇ and the unit is mPa ⁇ s.
- a drying air is blown on the surface of the coating film, and a parallel wind component of the drying air on the coating film surface is a relative wind speed of 30 m / s or less.
- the coating process includes a first coating process in which a flat thin film part is coated by coating the coating liquid on the support, and a flat thin film part. It is preferable to have a second coating step in which a thick film portion is coated by coating the coating liquid in a dot shape with a screen printing apparatus.
- the coating process includes a first coating process in which a flat thin film portion is coated by coating the coating liquid on the support, and a flat thin film portion. It is preferable to include a second coating step in which a thick film portion is coated by coating the coating liquid in a broken line shape with a screen printing apparatus.
- the lithographic printing plate precursors are prevented from being scraped off, the lithographic printing plate precursors are not adhered to each other, and the lithographic printing plate precursor from the laminate. Satisfying all of the problems for imparting plate separation to prevent multiple feeding in the plate-making process for taking out the sheets one by one, and for preventing slippage on the recording layer side surface of the planographic printing plate precursor it can.
- Explanatory drawing of the back coat layer having the surface roughness structure of the stripe coating film Longitudinal sectional view taken along line aa in FIG. 1 explaining the thick film portion and the thin film portion of the stripe coating film
- Explanatory drawing of the backcoat layer having the surface roughness structure of the dot coating 3 is a longitudinal sectional view taken along the line bb in FIG. 3 for explaining the thick film portion and the thin film portion of the dot coating film.
- Explanatory drawing of the back coat layer which has the surface roughness structure of a broken-line coating film 5 is a longitudinal sectional view taken along the line cc of FIG. 5 for explaining the thick film portion and the thin film portion of the broken line coating film.
- Table for explaining the first embodiment Explanatory diagram of the basis for the constants in Equation 1 Schematic diagram schematically showing a stripe coating film having a square projection in the first embodiment measured with a contact-type film thickness meter. Schematic diagram schematically showing a stripe coating film having another angular protrusion in the first embodiment measured with a contact-type film thickness meter. Schematic diagram schematically showing a stripe coating film having no angular protrusions measured with a contact-type film thickness meter in the first embodiment. Schematic diagram schematically showing a stripe coating film having no angular protrusions measured with a contact-type film thickness meter in the first embodiment. Table for explaining the second embodiment Table for explaining the third embodiment Table for explaining the fourth embodiment Explanatory drawing of a backcoat layer on which a coating film having a disordered surface roughness structure is formed
- the lithographic printing plate precursor according to the embodiment of the present invention has a polymer layer on the surface of a support, and has an arithmetic average height by a surface roughness structure in which a thin film portion and a thick film portion are continuously formed on the back surface of the support.
- the thickness Sa is configured to have a back coat layer of 0.5 ⁇ m or more.
- the surface roughness structure in which the thin film portion and the thick film portion are continuously formed means that the thin coating portion and the thick coating portion are formed in a continuous state on the coating film surface. It means a structure having surface roughness. That is, it is not intended to form a surface roughness structure using a matting agent as in the prior art.
- the term “lithographic printing plate precursor” includes both a strip-shaped plate before cutting into a predetermined size and a sheet-shaped plate cut into a predetermined size.
- the polymer layer in the present embodiment is a negative image recording layer containing a photosensitive layer composed of a positive image recording layer containing an infrared absorber, an infrared absorber, a polymerization initiator, and a polymerizable compound.
- a photosensitive layer composed of a positive image recording layer containing an infrared absorber, an infrared absorber, a polymerization initiator, and a polymerizable compound.
- Constructed photosensitive layer, non-photosensitive layer key plate, water-soluble layer or non-processed version of water-dispersible layer (developing lithographic printing plate precursor), water-soluble layer or water-dispersible layer The unprocessed discarded version of
- the discarded plate is a lithographic printing plate precursor to be attached to a plate cylinder that is not used, for example, when printing a part of paper in single color or two colors in color newspaper printing.
- the water-soluble compound that forms the water-soluble layer may be any compound as long as it is a compound that can dissolve 0.5 g or more in 100 g of water at 20 ° C.
- the water-dispersible compound that forms the water-dispersible layer may be any compound as long as it is a compound that is uniformly dispersed in water.
- the water dispersible layer may contain polymer fine particles.
- the back coat layer in the present embodiment is formed so that the arithmetic average height Sa by the surface roughness structure in which the thin film portion and the thick film portion are continuously formed is 0.5 ⁇ m or more.
- the arithmetic average height Sa is preferably 1 ⁇ m or more and 24 ⁇ m or less, and more preferably 1.5 ⁇ m or more and 8 ⁇ m or less.
- the back coat layer preferably has a Beck smoothness (Beck seconds) of 200 seconds or less.
- the surface roughness structure in which the thin film portion and the thick film portion constituting the back coat layer having an arithmetic average height Sa of 0.5 ⁇ m or more are continuously formed, a stripe coating film, a dot coating film, a dashed coating film Can be mentioned. However, it is not limited to these forms.
- the arithmetic average height Sa conforms to ISO 25178 (ISO: “International” Organization “for” Standardization).
- FIG. 1 is a view of a stripe coating 64 as seen from above as an example of the surface roughness structure of the backcoat layer 70
- FIG. 2 is a longitudinal sectional view taken along line aa of FIG.
- the strip coating 64 has a strip-shaped thick film portion 62 arranged on the back surface of the strip-shaped support 12 on the thin film portion 60 on the surface.
- the surface roughness structure in which the strip-shaped thin film portions 60 and the strip-shaped thick film portions 62 are parallel and alternately arranged in parallel to the longitudinal direction of the strip-shaped support 12 (synonymous with the traveling direction of the support in the manufacturing method). Is formed.
- the stripe coating 64 is formed on the entire back surface of the belt-like support 12 so as not to have an uncoated portion.
- edge part 12A which is the both ends of the strip
- the contact area ratio of the thick film portion 62 of the thin film portion 60 and the thick film portion 62 is preferably 5% or more and 90% or less, more preferably 30% or more and 80% or less, and 50% or more and 75%.
- the following is particularly preferable (hereinafter referred to as “thick film portion contact area ratio”).
- the thick film portion contact area ratio is 5% or more, printing stains are unlikely to occur.
- it is 90% or less the air release property is good when the planographic printing plate precursors are laminated, and the plates do not stick to each other.
- the thick film portion contact area ratio is an area ratio specified by a prescale manufactured by Fuji Film Co., Ltd., which is a film capable of measuring pressure and pressure distribution.
- a prescale is sandwiched between the prepared stripe coating film having a measurement target area and a smooth plate, and left standing. The whole surface was pressurized for 2 minutes at 0.59 MPa (6 kgf / cm 2 ) from the top and bottom, and the area ratio with respect to the area to be measured at the place where color development of 0.59 MPa or more was observed on the prescale was defined as the contact area ratio. .
- the stripe coating 64 preferably has a thickness difference Zt between the adjacent thick film portion 62 and the thin film portion 60 of 1 ⁇ m or more and 50 ⁇ m or less (hereinafter referred to as “thickness difference Zt”). .
- a more preferable range of the thickness difference Zt is 1 ⁇ m or more and 20 ⁇ m or less, and particularly preferably 2 ⁇ m or more and 10 ⁇ m or less.
- the thickness difference Z 0 is the thickness difference in the wet state immediately after the coating liquid for forming the stripe coating 64 is applied to the back surface of the belt-like support 12.
- the width W of the thick film portion 62 is preferably 0.5 mm or more and 50 mm or less (hereinafter referred to as “thick film portion width W”).
- the width W of the thick film portion 62 is 0.5 mm or more, the plates are misaligned when stacked, and are difficult to be damaged. Moreover, if it is 50 mm or less, the air release property is good.
- the pitch ⁇ between the thick film portions 62 is preferably 0.5 mm or more and 50 mm or less (hereinafter referred to as “thick film portion distance ⁇ ”).
- the pitch length ⁇ between the thick film portions 62 is 0.5 mm or more, the air release property when laminated is good, and the plates do not stick to each other. Moreover, if it is 50 mm or less, printing stains are eliminated.
- the ratio Zt / ⁇ of the thickness difference Zt between the adjacent thin film portion 60 and the thick film portion 62 and the pitch ⁇ is 0.10 or less.
- the ratio Zt / W between the thickness difference Zt and the width W of the thick film portion 62 is preferably 0.10 or less.
- FIG. 3 is a view of a dot coating 72 as an example of the surface roughness structure of the backcoat layer 70
- FIG. 4 is a longitudinal sectional view taken along the line bb of FIG.
- the dot coating film 72 has a surface roughness structure in which dot-like thick film portions 62 are dotted on the thin film portion 60 on the back surface of the belt-like support 12. is there.
- 3 and 4 show the case where the dot-like thick film portions 62 are regularly scattered, but may be irregularly (randomly) scattered. That is, on the back surface of the belt-like support 12, a planar thin film portion 60 is formed on the entire surface so as not to have an uncoated portion, and dot-like thick film portions 62 are scattered on the thin film portion 60. . However, the ear
- the “thick film portion contact area ratio” and the “thickness difference Zt”, “thick film portion width W”, and “thick film portion distance ⁇ ” in FIG. This is the same as the coating film 64.
- FIG. 5 is a view of a broken-line coating film as an example of the surface roughness structure of the backcoat layer 70
- FIG. 6 is a longitudinal sectional view taken along the line cc of FIG.
- the broken-line coating film 74 has a surface roughness structure in which a broken-line thick film part 62 is formed on the back surface of the belt-like support 12 on the planar thin film part 60. is there.
- FIG. 5 and 6 show the case where the broken-line thick film portion 62 is regularly formed, but it may be irregularly (randomly) formed. That is, on the back surface of the belt-like support 12, a planar thin film portion 60 is formed on the entire surface so as not to have an uncoated portion, and a broken-line thick film portion 62 is formed on the thin film portion 60. However, the ear
- the lithographic printing plate precursor according to the embodiment of the present invention forms a new surface roughness structure different from the conventional one on the back coat layer 70.
- the back coat layer 70 having a novel surface roughness structure such as a stripe coating film in which the thin film portion 60 and the thick film portion 62 are continuously formed is formed on the back surface of the belt-like support 12, FIGS. As shown in FIG. 5, there is a tendency that the angular protrusion 62A is easily formed on the thick film portion 62.
- FIG. 7 shows a case where a stripe coating film 64 or a broken-line coating film 74 is formed by the thin film portion 60 and the thick film portion 62, and angular projections at both ends in the width direction (short width direction) of the thick film portion 62.
- the part 62A is easily formed.
- FIG. 8 shows the case of the dot coating film 72, and the angular protrusions 62 ⁇ / b> A are easily formed on the peripheral edge of the dot-like thick film part 62. If the square protrusion 62A is formed, it causes printing stains.
- an arithmetic operation is performed with a surface roughness structure in which the thin film portion 60 and the thick film portion 62 are continuously formed.
- the back coat layer 70 having an average height Sa of 0.5 ⁇ m or more, it is also necessary to solve the prevention of the formation of the square protrusions 62A.
- the back coat layer 70 having an arithmetic average height Sa of 0.5 ⁇ m or more can be formed by the surface roughness structure in which the thin film portion 60 and the thick film portion 62 are continuously formed, and the angular protrusion 62A is formed.
- a method for producing a lithographic printing plate precursor according to the present invention capable of preventing the above will be described.
- the method for producing a lithographic printing plate precursor includes a backcoat layer 70 having a surface roughness structure of the stripe coating 64 among the stripe coating 64, the dot coating 72, and the broken coating 74 described above. This will be described in detail below.
- the present invention can be applied to both the case of manufacturing using a sheet-like support (substrate) and the case of manufacturing using a belt-like support.
- the case of the body 12 will be described.
- FIG. 9 is a schematic diagram illustrating the overall configuration of a manufacturing apparatus for manufacturing a lithographic printing plate precursor.
- the planographic printing plate precursor manufacturing apparatus 10 includes a polymer layer coating machine 14 for continuously coating a polymer layer coating solution on the surface of a belt-like support 12, and a wet polymer applied.
- a polymer layer dryer 16 for drying the layer
- a support cooling means 25 for cooling the strip-shaped support 12 before the coating liquid for the strip coating is applied
- coat this coating liquid, and the drying apparatus 20 for stripe coatings which dry the applied stripe coating film of the wet state are provided.
- Examples of the belt-like support 12 in the embodiment of the present invention include paper, a polyester film, or an aluminum plate.
- an aluminum plate that has been roughened and anodized by a known method is preferred.
- the aluminum plate has good dimensional stability, is relatively inexpensive, and can provide a surface excellent in hydrophilicity and strength by surface treatment as required.
- a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film is also preferable.
- the arithmetic average height Sa of the back surface of the belt-like support 12 having the back coat layer 70 and not subjected to the roughening treatment is 0.30 ⁇ m or less. This is because the arithmetic average height Sa of the backcoat layer does not achieve 0.5 ⁇ m or more due to the surface roughness of the back surface of the belt-like support 12 in the method for producing a lithographic printing plate precursor according to the present embodiment.
- the coating solution for polymer layer is applied to the surface of the belt-like support 12 on which the roughening treatment and, if necessary, the undercoat layer are applied, by the polymer layer coating machine 14.
- Each component constituting the various polymer layers described above is dispersed or dissolved in a known volatile solvent to prepare a coating solution for the polymer layer, and this is coated on the belt-like support 12 that is continuously conveyed.
- a slide bead type coating machine shown in FIG. 9 can be used as the polymer layer coating machine 14. Besides this coating machine, a known coating machine such as a bar coating machine or an extrusion type coating machine can be used. .
- the coating liquid supplied to the pocket portion 14A of the applicator main body flows through the slit 14B and is discharged to the slide surface 14C, and flows through the slide surface 14C to bead (apply) It is applied to the belt-like support 12 via a liquid reservoir.
- Reference numeral 32 denotes a pass roller that conveys the belt-like support 12.
- the polymer layer dryer 16 can employ various drying methods such as a hot air method in which hot air is blown to the polymer layer, a heater heating method using a heater such as infrared rays, and a heating roll method in which a heating roll is brought into contact with a belt-like support.
- the hot air method is particularly preferable.
- drying with heated air having a temperature of 100 ° C. or higher and a dew point of 5 to 20 ° C. is preferable.
- the belt-like support 12 on which the polymer layer is formed cools the temperature of the belt-like support 12 raised by the drying heat of the polymer layer dryer 16 by the support cooling means 25.
- one cooling unit may be used, but it is preferable that the first and second cooling units 29 and 31 are configured in consideration of the purpose and the cooling efficiency.
- the first cooling means 29 is intended to prevent transfer to the transport pass rollers 32, 32... Due to stickiness of the polymer layer and to prevent distortion and scratches of the belt-like support 12, and the temperature of the belt-like support 12 is, for example, 30.degree. Cool rapidly to about °C.
- a coating solution for stripe coating described later is applied so as not to change the viscosity of the coating solution for stripe coating applied to the back surface of the belt-like support 12 in the next step. Cool to the same temperature range as. In general, cool to about room temperature.
- the belt-like thick film portion 62 and the belt-like thin film portion 60 shown in FIG. 1 are parallel to the running direction of the belt-like support 12 and A stripe coating 64 having a thickness difference between adjacent thick film portions 62 and thin film portions 60 of 1 ⁇ m or more and 50 ⁇ m or less is formed as follows. That is, an entire surface coating film having no uncoated portion is formed on the back surface of the belt-like support 12. However, the ear
- the coating liquid F for the stripe coating can be prepared by dispersing or dissolving each component such as a resin component constituting the composition of the stripe coating 64 in a known volatile solvent.
- the resin component and the solvent of the stripe coating 64 a resin component and a solvent for forming a backcoat layer of a lithographic printing plate can be preferably used.
- the resin component contains an organic polymer as the base polymer that constitutes the backcoat layer 70 in the embodiment of the present invention.
- Organic polymers include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, or m- / p-mixed) It may be selected from the group consisting of novolak resins such as mixed formaldehyde resins, resol resins, pyrogallol acetone resins, and epoxy resins.
- novolak resins such as mixed formaldehyde resins, resol resins, pyrogallol acetone resins, and epoxy resins.
- a saturated copolymerized polyester resin a phenoxy resin, a polyvinyl acetal resin, a vinylidene chloride copolymer resin, or the like can be used.
- novolak resins resol resins, pyrogallol acetone resins, epoxy resins, polystyrene resins, and the like are preferably used from the viewpoint of heat resistance, chemical resistance, and cost.
- the content of the organic polymer contained in the total solid content of the back coat layer 70 is preferably 99.7 to 40% by mass, more preferably 99 to 60% by mass, and 98 to 80% by mass. Is particularly preferred.
- the content of the crosslinking agent used in the organic polymer layer is preferably 0.3 to 30% by mass in terms of solid content, more preferably 1 It is in the range of ⁇ 20% by mass.
- the back coat layer 70 preferably contains at least one non-alkali soluble resin.
- the backcoat layer 70 preferably contains at least one non-photocurable resin having a weight average molecular weight of 3000 or less.
- filler When an epoxy resin or a resol resin is used as the organic polymer in the present invention, various fillers can be added within a range that does not impair the effects of the present invention.
- the filler include calcium carbonate powder, silica powder, wood powder, and pulp.
- the content of the filler is preferably in the range of 1 to 50% by mass, more preferably 5 to 30% by mass in terms of solid content.
- these fillers are premised on not impairing the effects of the present invention, and when they are impaired, the type and amount of the filler are adjusted.
- the back coat layer 70 needs a plasticizer, a surfactant, and other additives within a range that does not impair the effects of the present invention, for the purpose of imparting flexibility, adjusting the slipperiness, and improving the coated surface. Can be added.
- plasticizer examples include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diallyl phthalate, and the like.
- phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diallyl phthalate, and the like.
- Glycol esters such as glycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, triethylene glycol dicaprylate, phosphate esters such as tricresyl phosphate, triphenyl phosphate , Diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl seba Over DOO, dioctyl azelate, aliphatic, such as dibutyl maleate dibasic acid esters, polyglycidyl methacrylate, triethyl citrate, glycerin triacetyl ester, and butyl laurate is effective.
- phosphate esters such as tricresyl phosphate, triphenyl phosphate , Diisobutyl adipate, dioctyl adipate,
- the amount of plasticizer added to the backcoat layer 70 varies depending on the type of organic polymer used in the backcoat layer 70, but is preferably added within a range where the glass transition temperature does not become 60 ° C or lower.
- surfactant examples include anionic, cationic, nonionic and amphoteric surfactants. Specific examples include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters , Pentaerythritol fatty acid partial esters, propylene glycol mono fatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerin fatty acid moieties Esters, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acid diethanolamine , N, N-bis-2-hydroxyalkylamines, non
- those having polyoxyethylene can be read as polyoxyalkylenes such as polyoxymethylene, polyoxypropylene, polyoxybutylene, and these surfactants are also included.
- a more preferred surfactant is a fluorosurfactant containing a perfluoroalkyl group in the molecule.
- fluorosurfactants include perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, anionic types such as perfluoroalkyl phosphates, amphoteric types such as perfluoroalkyl betaines, and perfluoroalkyltrimethylammonium salts.
- the surfactant can be used alone or in combination of two or more, and is preferably added to the back coat layer 70 in the range of 0.001 to 10% by mass, more preferably 0.01 to 5% by mass. it can.
- the back coat layer 70 further includes a dye for coloring, a silane coupling agent for improving adhesion to the belt-like support 12, a diazo resin composed of a diazonium salt, an organic phosphonic acid, an organic phosphoric acid, a cationic polymer, and the like.
- a dye for coloring e.g., a silane coupling agent for improving adhesion to the belt-like support 12
- a diazo resin composed of a diazonium salt, an organic phosphonic acid, an organic phosphoric acid, a cationic polymer, and the like.
- waxes usually used as slipping agents higher fatty acids, higher fatty acid amides, silicone compounds composed of dimethylsiloxane, modified dimethylsiloxane, polyethylene powder and the like can be added as appropriate.
- carboxymethylcellulose etc. can be added suitably as a thickener.
- volatile components are preferable, and examples thereof include methyl ethyl ketone, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, and ⁇ -butyllactone.
- the present invention is not limited to this. These solvents are used alone or in combination.
- the solid content concentration of the coating solution is preferably 1 to 50% by mass.
- the coating liquid F for the stripe coating film flows through the pipe 36 by the pump 34 and is sent to the stripe coating film coating machine 18, and is applied by the coating liquid cooling means 22 provided in the middle of the pipe 36.
- the temperature is adjusted so that the set temperature of the coating solution is obtained.
- the striped coating film coating machine 18 is used so that the thickness difference between the thick film portion 62 and the thin film portion 60 adjacent to the back surface of the belt-like support 12 is 1 ⁇ m or more and 50 ⁇ m or less. 1 to form a wet striped coating film 64 having the surface roughness structure shown in FIG.
- the thickness of the adjacent thick film portion 62 and thin film portion 60 in the wet striped coating film 64 before drying It is preferable to apply so that the difference is 1 ⁇ m or more and 50 ⁇ m or less.
- the viscosity of the coating liquid F is 0.3 mPa ⁇ s to 100 mPa ⁇ s (hereinafter referred to as “viscosity condition”), and the surface tension of the coating liquid F is 20 mN / m to 40 mN / m (hereinafter referred to as “surface tension condition”). ”), And the coating liquid and the belt-like support 12 are applied under application conditions where the contact angle is 10 ° or more and 90 ° or less (hereinafter referred to as“ contact angle condition ”).
- the above three application conditions of “viscosity condition”, “surface tension condition”, and “contact angle condition” are two, “formation of stripe coating” and “prevention of formation of angular projections”.
- the preconditions for achieving the above are defined, and coating under three coating conditions is a prerequisite for the method for producing a lithographic printing plate precursor according to the present invention.
- the viscosity of the coating liquid F exceeds 100 mPa ⁇ s
- the problem that the angular protrusion 62A occurs in the thick film portion 62 does not occur in the first place.
- the method of forming the stripe coating 64 on the belt-like support 12 is not limited to the bar coating machine 24, and any one of an inkjet printing method, a gravure printing method, a screen printing method, a spray coating method, and a slot die coating method. It is possible to apply and form a coating film by this method.
- the bar coater (bar coater) 24 is a coating bar for the belt-like support 12 that is guided by the upstream guide roller 26 and the downstream guide roller 27 and travels.
- the coating liquid F is applied by a coating head 30 including 28.
- the upstream guide roller 26 and the downstream guide roller 27 are arranged such that the belt-like support 12 travels close to the coating bar 28.
- the upstream guide roller 26 and the downstream guide roller 27 are supported in a state parallel to the coating bar 28.
- the coating bar 28 is driven to rotate as indicated by the arrow in FIG.
- the rotation direction of the coating bar 28 is preferably a forward rotation direction with respect to the transport direction of the belt-like support 12, and the peripheral speed is preferably set to be the same as the speed of the belt-like support 12. Note that application in a direction opposite to the rotation direction shown in FIG. 10, that is, application by driving in the reverse direction with respect to the transport direction, or application without rotation drive can be adopted depending on application conditions.
- the coating head 30 is mainly composed of a coating bar 28, a backup member 38, and coater blocks 40 and 42.
- the coating bar 28 is rotatably supported by the backup member 38.
- Manifolds 44 and 46 and slots 48 and 50 are formed between the backup member 38 and the coater blocks 40 and 42, and the coating liquid F for stripe coating is supplied to the manifolds 44 and 46.
- the coating solution F supplied to the manifolds 44 and 46 is uniformly pushed out in the width direction of the belt-like support 12 through narrow slots 48 and 50.
- the upstream application bead 52 is formed on the upstream side in the feed direction of the belt-like support 12 with respect to the coating bar 28, and the downstream application bead 54 is formed on the downstream side.
- the coating liquid F is applied to the back surface of the traveling belt-like support 12 via these coating beads 52 and 54.
- the coating liquid F supplied excessively from the manifolds 44 and 46 overflows into the space between the coater blocks 40 and 42 and the belt-like support 12 and is collected through a side groove (not shown).
- the supply of the coating liquid F to the manifolds 44 and 46 may be performed from the central part of the manifolds 44 and 46 or from the end part.
- FIG. 11 is an overall view of the coating bar 28, and FIG. 12 is a partial cross-sectional view of the coating bar 28.
- FIG. 13 is a partially enlarged sectional view in which the vicinity of the bar surface of the coating bar 28 of FIG. 12 is enlarged.
- a grooved portion A in which grooves are formed in the circumferential direction of the bar and a grooveless portion B in which grooves are not formed are applied on the surface of the cylindrical coating bar 28 .
- the bars 28 are alternately arranged in the axial direction (the width direction of the belt-like support 12).
- the both ends C of the coating bar 28 may be formed with a groove or may not be formed with a groove, in this embodiment, the case where no groove is formed will be described.
- the groove of the grooved portion A is composed of a concave portion 56 and a convex portion 58, and the groove shape is formed in a trapezoidal shape.
- the groove shape is not limited to a trapezoidal shape but may be a sine wave shape.
- the diameter D 1 of the non-grooved portion B is preferably not be less than the bar diameter (diameter of the coating bar) D 3 in the recess 56 of the groove there site A.
- the diameter D 1 of the groove-free portion B is larger than the bar diameter D 3 of the concave portion 56 of the grooved portion A and smaller than the average value D 2 of the bar diameters of the concave portion 56 and the convex portion 58. Is more preferable.
- the pitch length between the adjacent concave portions 56 or between the convex portions 58 is P
- P is 0.25 mm or more
- h / D is 0.01 or more and 0.55 or less
- D / P is 0.49 or less.
- the upper limit of the pitch length P is determined by the length of the thick film portion 62 or the thin film portion 60 of the stripe coating 64 to be formed, but is preferably 10 mm or less.
- the concave portion 56 and the convex portion 58 constituting the groove of the grooved portion A satisfy the above-mentioned P of 0.25 mm or more, h / D of 0.01 or more and 0.55 or less, and D / P of 0.49 or less.
- the stripe coating film 64 with less unevenness (coating unevenness) can be formed on the coating film surface.
- the stripe coating film 64 shown in FIG. 1 is applied by forming the coating bar 28 of the bar coating machine 24 with the grooved portion A and the grooveless portion B having the above-described conditions. be able to.
- a groove comprising a shallow grooved portion A1 and a deep grooved portion A2 is provided. It is also possible to employ two types of grooved portions A having different depths. In other words, the depth h 1 of the recess 56 of the portion A1 there shallow groove of the groove is shallower than the depth h 2 of the recess 56 of the part A2 there deep grooves of the groove. Further, the convex portion 58 of the shallow grooved portion A1 and the convex portion 58 of the deep grooved portion A2 are flush with each other.
- the depths of the two types of grooves, the shallow grooved portion A1 and the deep grooved portion A2 can be set according to the film thickness of the thin film portion 60 and the thick film portion 62 to be formed.
- the method for forming the groove on the surface of the coating bar 28 is not particularly limited, and various processing methods can be employed. For example, cutting processing, rolling processing, laser processing, and the like can be preferably employed.
- the coating liquid F for the stripe coating is applied by using the coating bar 28 having a diameter D 0 (see FIG. 11) of 6 mm or more and 50 mm or less and the rotation speed r of the coating bar 28 and the coating described above. It is preferable that the relationship with the viscosity ⁇ of the liquid F satisfies the following formula (3).
- the diameter D 0 of the coating bar 28 is more preferably 6 mm or more and 20 mm or less.
- FIG. 15 shows the experimental results of examining how the relationship between the rotational speed r of the coating bar 28 and the viscosity ⁇ of the coating liquid F affects the entrainment of bubbles.
- region below the bubble mixing limit curve E is an area
- region) in which a bubble is entrained is an area
- the wet striped coating film 64 formed on the back surface of the belt-like support 12 is dried by the striped coating film dryer 20 to dry the striped coating film 64 (hereinafter sometimes referred to as “dry film”). Form.
- the dryer 20 for a stripe coating film is a hot air system that blows hot air on the wet stripe coating film 64, a heater heating system that uses a heater such as infrared rays, a heating roll system that makes the heating roll contact the belt-like support 12, and a condenser plate Various drying methods such as a condensing drying method using a hot air method can be adopted.
- FIG. 16 shows an example of a hot-air striped film dryer 20 and the casing of the dryer is not shown.
- a rectangular nozzle 66 is provided in the vicinity of the film surface of the stripe coating 64 applied to the back surface of the belt-like support 12.
- the nozzle 66 is connected to a pipe 68 connected to a drying air supply device (not shown) that blows hot air, and the belt-like support body is parallel to the film surface of the stripe coating 64 from the slit-shaped air outlet 66A.
- the drying air is blown out in the direction opposite to the conveying direction of 12 or the conveying direction.
- the drying air flows in parallel to the thick film portion 62 and the thin film portion 60 of the stripe coating film 64, so that the coating film surface is uneven. It is possible to dry in a short time without generating (dry unevenness).
- the parallel wind component of the dry wind blown from the nozzle 66 to the coating film surface is preferably a relative wind speed of 30 m / s or less.
- the parallel wind component of the dry wind on the coating film surface exceeds the relative wind speed of 30 m / s, unevenness (drying unevenness) easily occurs on the coating film surface of the stripe coating film 64.
- the relative wind speed is a wind speed viewed in a relative relationship with the conveyance speed of the belt-like support 12.
- the drying point (t) when the stripe coating 64 in the wet state is dried to form the stripe coating 64 in the dry state satisfies the following formulas 1 and 2. is required.
- the drying point refers to a point in time when a dry state is reached at which no change is observed in the surface gloss of the stripe coating 64 applied to the belt-like support 12, and the drying time from the start of drying to the drying point can be known.
- the drying point is a critical point for transition from the constant rate drying period to the decreasing rate drying period, and the viscosity of the stripe coating 64 becomes 1 Pa ⁇ s or more, and the thin film portion 60 constituting the stripe coating 64 The time when the shape with the thick film part 62 is fixed is said.
- each parameter of Formula 1 is as follows, and some parameters will be described with reference to FIG.
- “initial” means a drying start time, and the stripe coating 64 is in a wet state.
- the “dry film” means the striped coating film 64 which is dried and dried.
- Viscosity B-type viscometer.
- Width of stripe optical microscope.
- the above formula 1 utilizes the Orchard leveling formula for leveling of the coating solution, and when the wet striped coating film 64 is applied and formed on the belt-like support 12, the thick film portion 62, the thin film portion 60, Is a formula for obtaining a stripe coating film 64 having a film thickness difference in a dry state to be formed (hereinafter referred to as “stripe coating film”). Forming conditions ").
- the parameters (X, ⁇ , Z 0 ) related to the shape of the stripe coating film 64 in the wet state, the physical properties ( ⁇ , ⁇ ) of the coating solution, and the film thickness difference of the stripe coating film 64 in the dry state to be formed ( Z t ) is substituted into the right side of Equation 1.
- the leveling of the thick film part 62 and the thin film part 60 proceeds, and the drying time until the film thickness difference to be formed disappears can be obtained. Therefore, from the inequality of Equation 1, the drying time until the drying point (t) at which the shapes of the thin film portion 60 and the thick film portion 62 constituting the stripe coating 64 are fixed is shorter than the obtained drying time. If so, it is possible to obtain a stripe coating 64 having a difference in film thickness to be formed.
- Equation 1 the constant 0.033 used in Equation 1 is different from the Orchard leveling equation constant because fitting was performed from the experiment so as to satisfy the parameter conditions.
- Equation 2 Equation 2
- Pe is a numerical value obtained by dividing the drying rate by the diffusion coefficient of the coating solution, and the Peclet number constant of 1.5 ⁇ 10 ⁇ 6 is based on the experimental results.
- Equation 2 The basis of the constant of 3.3 ⁇ 10 9 in Equation 2 was obtained from experimental data and will be described in detail in the following examples.
- Formula 2 defines the conditions for forming the angular protrusions 62A at both ends in the width direction of the thick film portion 62, and the relationship between the three formulas of the left side formula, the central formula, and the right side formula is an inequality. (Hereinafter referred to as “conditions for preventing the formation of angular projections”).
- FIG. 17A shows the thick film portion 62 of the wet striped coating film 64 immediately after being applied on the belt-like support 12.
- the thick film portion 62 immediately after application has a rectangular shape since leveling has not yet occurred.
- the rectangular thick film portion 62 is leveled over time, and has a mountain shape with an expanded hem as shown in FIG. 17B.
- the concentration of the hem portion at both ends in the width direction of the thick film portion 62 becomes higher than the concentration in the central portion due to the surface tension gradient generated in the thick film portion 62.
- a portion having a high concentration is shown in a net shape. As a result, as shown in FIG.
- the relation of the expression on the left side ⁇ the expression on the center is that (a) the resistance during movement of the liquid even if the driving force (the expression on the right side) that collects the liquid in the thick film portion 62 at the end works. Is large, (b) if the driving force itself is small, or (c) if the movable time is short, it indicates that the angular protrusion is not generated.
- the stripe coating film 64 is dried to the drying point (t) by at least one of the above-described actions (a) to (c) before the square protrusion 62A is generated by the driving force of the right side equation.
- the angular protrusions 62 ⁇ / b> A are not generated at both ends in the width direction of the band-shaped thick film portion 62.
- the square projection 62A is generated by the driving force and dried to a dry point in a short time, the square projection 62A does not occur.
- the stripe coating film applicator 18 and the stripe coating film drying machine 20 shown in FIG. 9 are preferable to dispose the stripe coating film applicator 18 and the stripe coating film drying machine 20 shown in FIG. 9 as close as possible to rapidly dry the coating film.
- the stripe coating 64 can be dried so that the angular protrusions 62A are not formed at both ends in the width direction of the strip-shaped thick film portion 62.
- drying time of the stripe coating 64 is preferably 20 seconds or less, more preferably 10 seconds or less, after satisfying the formulas 1 and 2 in consideration of productivity.
- the above-mentioned “viscosity conditions” and “surfaces” which are preconditions for generating the problems of the present invention.
- the strip-shaped thin film portions 60 and the strip-shaped thick film portions 62 are alternately and continuously arranged on the strip-shaped support body 12, and the surface roughness structure of the stripe coating film 64 is obtained.
- the back coat layer 70 having an arithmetic average height Sa of 0.5 ⁇ m or more that does not generate the angular protrusions 62A at both ends in the width direction.
- a planographic printing plate precursor having a back coat layer 70 having an arithmetic average height Sa of 0.5 ⁇ m or more can be produced depending on the structure.
- a first coating process is performed in which the coating liquid F is solid-coated on the entire back surface of the belt-like support 12 to form a flat (flat) thin film portion 60.
- belt-shaped support body 12 may be uncoated.
- the coating device for applying the coating liquid F in a solid state various coating devices such as a slot coating method, an extrusion coating method, a slide bead coating method, and a roll coating method can be used.
- a second coating process is performed in which the same coating liquid F as that of the thin film portion 60 is applied in the form of dots as shown in FIG. Do.
- coating is performed such that the difference in thickness between the thin film portion 60 and the thick film portion 62 is 1 ⁇ m or more and 50 ⁇ m or less to form the wet dot coating film 72.
- an ink jet printing method or a screen printing method can be suitably used, and a screen printing method is particularly preferable.
- the application conditions for forming the dot coating film 72 are the same “viscosity condition”, “surface tension condition”, and “contact angle condition” as in the case of forming the stripe coating film 64.
- drying conditions for drying the dot coating film 72 are the same as in the case of drying the stripe coating film 64, under the conditions satisfying the above-described formulas 1 and 2 and the relative wind speed of the drying wind.
- a planographic printing plate precursor having a back coat layer 70 having an arithmetic average height Sa of 0.5 ⁇ m or more can be produced depending on the structure.
- the first coating process is performed in which the coating liquid F is solid-coated on the entire back surface of the belt-like support 12 to form a flat (flat) thin film portion 60.
- belt-shaped support body 12 may be uncoated.
- the coating device for applying the coating liquid F in a solid state various coating devices such as a slot coating method, an extrusion coating method, a slide bead coating method, and a roll coating method can be used.
- a second coating step is performed in which the same coating liquid F as that of the thin film portion 60 is applied in a broken line shape on the thin film portion 60 applied in a flat manner to form the thick film portion 62 as shown in FIG. Do.
- coating is performed so that the difference in thickness between the thin film portion 60 and the thick film portion 62 is 1 ⁇ m or more and 50 ⁇ m or less to form a wet-shaped broken film 74.
- an inkjet printing method or a screen printing method coating device can be suitably used as in the case of the dot coating film 72, and a screen printing method is particularly preferable.
- the application conditions for forming the broken-line coating film 74 are the same “viscosity conditions”, “surface tension conditions”, and “contact angle conditions” as in the case of forming the stripe coating film 64.
- drying conditions for drying the dot coating film 72 are the same as in the case of drying the stripe coating film 64, under the conditions satisfying the above-described formulas 1 and 2 and the relative wind speed of the drying wind.
- a planographic printing plate precursor having a back coat layer 70 having an arithmetic average height Sa of 0.5 ⁇ m or more can be produced depending on the structure.
- the laminate according to the embodiment of the present invention has a surface roughness in which a polymer layer is provided on the support surface, and strip-shaped thin film portions 60 and strip-shaped thick film portions 62 are alternately and continuously arranged on the back surface of the support. It is formed by laminating a plurality of planographic printing plate precursors having a structure and having a back coat layer 70 having an arithmetic average height Sa of 0.5 ⁇ m or more. In this state, the laminate is packaged and delivered to the user.
- the lithographic printing plate precursor according to the embodiment of the present invention laminated has a surface roughness structure (component A) in which a thin film portion 60 and a thick film portion 62 are continuously formed on the back surface of the belt-like support 12; Due to the surface roughness structure, the arithmetic average height Sa of the backcoat layer satisfies two components of 0.5 ⁇ m or more (component B).
- planographic printing plate precursors according to the embodiments of the present invention are laminated to form a laminate, 1) prevention of abrasion between the planographic printing plate precursors and 2) planographic printing plate precursors are required. 3) Prevention of scratching of the surface of the lithographic printing plate precursor on the recording layer side 4) Prevention of multiple plate feeding in the plate making process for taking out the lithographic printing plate precursor one by one from the laminate Can satisfy all the issues. This will be described in detail in the fourth embodiment in the column of the embodiment.
- the lithographic printing plate precursor produced by the lithographic printing plate precursor according to the embodiment of the present invention can realize a paper-less process.
- the above-described method for producing a lithographic printing plate precursor according to an embodiment of the present invention is not limited to the production of a lithographic printing plate precursor, but a coating having a functional layer on the support surface and a backcoat layer on the back surface of the support. Any film structure can be applied.
- the coating film structure refers to a structure in which a support and a coating film formed on the support are combined.
- the present invention has the effect described above.
- the striped coating film 64 without the angular protrusion 62A can be formed by satisfying the above-described formulas 1 and 2.
- the arithmetic average height of the backcoat layer is changed by changing the type of polymer layer on the support surface and the resin type and surface roughness structure of the backcoat layer on the backside of the support.
- adheresiveness Prevention of adhesion between planographic printing plate precursors
- plate spreading giving plate separation to prevent multiple feeding in the plate making process in which lithographic printing plate precursors are taken out from the laminate one by one (hereinafter referred to as “plate spreading”).
- a coating liquid for a stripe coating is applied on the back surface of a belt-like support 12 having a polymer layer for an untreated plate formed on the surface under the following conditions, followed by drying and a planographic printing plate An original plate was produced.
- the polymer layer for the untreated plate was formed as follows as a three-layer structure of an undercoat layer, an image recording layer, and a protective layer.
- Undercoat layer coating solution having the following composition was applied to the surface of the belt-like support 12 so that the dry coating amount was 20 mg / m 2 to form an undercoat layer.
- Undercoat layer compound (UC-1) (Formula 1) 0.18 g ⁇ Hydroxyethyliminodiacetic acid 0.05g ⁇ Surfactant (Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 0.03g ⁇ Water 28.0g
- An image recording layer coating solution having the following composition was bar coated on the undercoat layer and then oven-dried at 100 ° C. for 60 seconds to form an image recording layer having a dry coating amount of 1.0 g / m 2 .
- the image recording layer coating solution was obtained by mixing and stirring the following photosensitive solution and microgel solution immediately before coating.
- aqueous phase component 40 g of a 4% by mass aqueous solution of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-205) was prepared.
- the oil phase component and the aqueous phase component were mixed and emulsified for 10 minutes at 12,000 rpm using a homogenizer.
- the obtained emulsion was added to 25 g of distilled water, stirred at room temperature for 30 minutes, and then stirred at 50 ° C. for 3 hours.
- the microgel solution thus obtained was diluted with distilled water so that the solid content concentration was 15% by mass to prepare a microgel.
- the average particle size of the microgel measured by the light scattering method was 0.2 ⁇ m.
- a protective layer coating solution having the following composition is bar-coated on the image recording layer, it is oven-dried at 120 ° C. for 60 seconds to form a protective layer having a dry coating amount of 0.15 g / m 2 to produce a lithographic printing plate precursor did.
- ⁇ Coating liquid composition of protective layer >> ⁇ Inorganic layered compound dispersion (see details below) 1.5g ⁇ Hydrophilic polymer (Chemical Formula 5 below, Mw: 30,000) (solid content) 0.03 g ⁇ Polyvinyl alcohol 0.10g 6 mass% aqueous solution (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., CKS50, sulfonic acid modification, saponification degree 99 mol% or more, polymerization degree 300) ⁇ Polyvinyl alcohol 0.03g 6% by mass aqueous solution (manufactured by Kuraray Co., Ltd., PVA-405, saponification degree 81.5 mol%, polymerization degree 500) ⁇ Surfactant (Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 0.86g (Formula 5: 1% by mass aqueous solution) ⁇ Ion-exchanged water 6.0g
- the back coat layer 70 was formed as follows.
- Viscosity of 0.5 mPa ⁇ s, 1 mPa ⁇ s, 6 mPa ⁇ s, 30 mPa ⁇ s, 80 mPa can be obtained by changing the solid content concentration of the coating liquid F for stripe coating described above between 4 mass% and 36 mass%. -The coating liquid of 5 levels of s was adjusted. Moreover, the surface tension of the coating liquid F was performed at four levels of 25 mN / m, 27 mN / m, 30 mN / m, and 35 mN / m.
- Strip support As the belt-like support 12, an aluminum plate of JIS A 1050 (JIS: Japan Industrial Standards) having a thickness of 0.30 mm and a width of 1030 mm was used. This belt-like support 12 was carried out in two levels with respect to the coating solution F, when the contact angle was 30 ° and 90 °.
- the coating bar 28 has a grooved portion A and a grooveless portion B described in FIGS. 11 to 13 alternately arranged in the axial direction of the coating bar 28 and has a diameter of 10 mm. did.
- condition range (0.3 mPa ⁇ s or more and 100 mPa ⁇ s or less) of the viscosity ( ⁇ ), which is the premise for the above-mentioned problem occurrence, the condition range (20 mN / m or more and 40 mN / m or less) of the surface tension ( ⁇ ), and The application was performed by changing the numerical value in the contact angle condition range (10 ° to 90 °).
- the initial film thickness difference (Z 0 ) was performed at three levels of 10 ⁇ m, 20 ⁇ m, and 40 ⁇ m.
- the number of rotations of the coating bar 28 was three levels of 300 rpm, 1270 rpm, and 1500 rpm.
- the preferred conditions for the grooves of the coating bar 28 are P 0.25 mm or more, D / P 0.49 or less, and h / D 0.01 to 0.55 by investigating numerical values. It was.
- the relative wind speed of the parallel wind component on the coating surface of the dry wind is 0.1 m / s, 0.2 m / s, 3 m / s, 4 m / s, 5 m / s, 10 m / s, 20 m / s, 30 m. / S and 9 levels of 35 m / s.
- the table in FIG. 18A shows numerical values of parameters (viscosity, surface tension, etc.) and test results for Examples 1 to 22 and Comparative Examples 1 to 8.
- the viscosity condition range (0.3 mPa ⁇ s to 100 mPa ⁇ s), the surface tension ( ⁇ ) range (20 mN / m to 40 mN / m), and the contact angle condition range (10 ° to 90 °).
- Below ° is a premise for the occurrence of the problem in the present invention as described above, and therefore, when assigning numerical values of parameters, the upper and lower numerical values were not particularly particular.
- a bar coating having a coating bar 28 composed of a grooved portion A and a grooveless portion B described with reference to FIGS. Machine 24 was used as a stripe coating film applicator 18 for applying a stripe coating film. Therefore, what is the effect on P that defines the groove shape of the coating bar 28 is 0.25 mm or more, D / P is 0.49 or less, and h / D is 0.01 or more and 0.55 or less? I also investigated. Furthermore, the relationship between the rotation speed of the coating bar 28 and the entrainment of bubbles in the coating solution F was also examined.
- Test result 1 evaluated whether or not the stripe coating film 64 was formed and whether or not the formation of the angular protrusion 62A could be prevented.
- A was defined as the case where the stripe coating 64 was formed and there was no angular protrusion 62A. Moreover, it was set as B when the stripe coating film 64 was not formed or there existed the square-shaped projection part 62A.
- stripe coating film 64 Whether stripe coating film 64 is formed, a film thickness difference Z t in dry films with thick portions 62 and thin portions 60 adjacent measured with a contact-type film thickness meter, the stripe coating if 1 ⁇ m or more It was determined that the film 64 was formed. Whether or not the formation of the square protrusion 62A could be prevented was measured by measuring the profile of the stripe coating film with an electron microscope, and the film thickness at the end of the thick film part 62 was 0.5 ⁇ m compared to the film thickness at the central part. When it is larger than the above, it is determined that the angular protrusion 62A is present.
- “Foam entrainment” is a visual observation of the produced lithographic printing plate precursor, and A is the case where there is no entrainment of bubbles, B is the case where entrainment of bubbles is part of the thick film portion 62, The case where there was an entrainment was defined as C.
- “unevenness of the stripe coating” refers to A when the produced lithographic printing plate precursor is visually observed and there is almost no color difference, and B when a slight color difference is observed. The case where a clear color difference was observed was designated as C.
- Examples 1 to 22 are “viscosity conditions”, “surface tension conditions”, “contact angle conditions”, “stripe coating film formation conditions” of Formula 1, and “angles” of Formula 2. All of the five conditions of the “prevention condition for forming the protruding portion” are satisfied.
- Comparative Examples 1 to 8 do not satisfy at least one of the “striped coating film forming condition” of Expression 1 and the “prevention condition of forming a square protrusion” of Expression 2 among the above five conditions.
- the stripe coating film 64 could be formed, and the angular protrusions did not occur at both ends in the width direction of the thick film part, and the evaluation was A.
- Comparative Examples 1 to 8 Comparative Examples 1 and 7 were unable to form a stripe coating film, and were evaluated as B. That is, in Comparative Examples 1 and 7, the difference in film thickness between the thick film portion 62 and the thin film portion 60 disappeared due to leveling of the coating film in the drying process, and a flat coating film was obtained.
- FIG. 19 is a schematic diagram schematically showing a result of measuring Comparative Example 2 in which square protrusions 62A are generated at both ends in the width direction of the thick film part 62 using a contact-type film thickness meter.
- FIG. 20 is a schematic view schematically showing a result of measuring Comparative Example 5 in which square protrusions 62A are generated at both ends in the width direction of the thick film part 62 using a contact-type film thickness meter.
- 19 and 20 show a vertical magnification of 1000 times and a horizontal magnification of 10 times.
- angular protrusions 62 ⁇ / b> A are generated at both ends in the width direction of all thick film portions 62. Further, in FIG. 20, angular protrusions 62 ⁇ / b> A are generated at both ends in the width direction of the thick film portion 62 in the right half of the drawing.
- FIG. 21 is a schematic view schematically showing the result of measuring Example 1 with a contact-type film thickness meter in which the angular protrusions 62A did not occur at both ends in the width direction of the thick film part 62.
- FIG. 22 is a schematic view schematically showing the result of measuring Example 2 with a contact-type film thickness meter in which the angular protrusions 62A were not generated at both ends in the width direction of the thick film part 62.
- FIG. 21 shows a vertical magnification of 5000 times and a horizontal magnification of 30 times.
- FIG. 22 shows a vertical magnification of 2000 times and a horizontal magnification of 10 times.
- the angular protrusions 62 ⁇ / b> A are not generated at both ends in the width direction of the thick film portion 62.
- the lithographic printing plate precursor produced by the method for producing a lithographic printing plate precursor according to the present invention is not damaged when printing a plurality of laminated plates to form a laminate, and printing stains are suppressed. Paperless can be realized.
- Equation 2 the basis of the constant 3.3 ⁇ 10 9 in Equation 2 will be described.
- FIG. 18B is a plot of the examples and comparative examples in the table of FIG. 18A with the time to the drying point on the vertical axis and Z 0 ⁇ ⁇ ⁇ W / ⁇ on the horizontal axis.
- the plots of the examples are indicated by ⁇ (circles), and the plots of the comparative examples are indicated by x (X).
- a dotted line S that is a boundary line between the ⁇ region and the ⁇ region can be expressed by the following equation.
- Test result 2 is a test result obtained by testing the shape and rotation speed of the coating bar 28 and the relative wind speed of the parallel wind component on the coating surface of the dry wind during drying.
- P defining the groove shape of the coating bar 28 is 0.25 mm or more, D / P is 0.49 or less, and h / D is 0.01 or more and 0.55 or less.
- Examples and Comparative Examples in Examples 2, 9, 11, 13, 17, 18 and Comparative Example 2, unevenness occurred occasionally, and B was evaluated.
- Example 17 in which the parallel wind component on the coating surface of the drying wind was a relative wind speed of 35 m / s, unevenness (drying unevenness) was observed in the stripe coating film 64. In Example 13, weak scratches were observed.
- Example 17 in which the viscosity of the coating liquid F is 30 mPa ⁇ s and the rotational speed is 1500 rpm
- Example 18 in which the viscosity of the coating liquid is 30 mPa ⁇ s and the rotational speed is 1270 rpm.
- the foam was entrained and B was evaluated. This is consistent with the bubble mixing limit curve of FIG.
- the lithographic printing plate samples of the example of the table of FIG. 18A and the comparative example were laminated without sandwiching the interleaf between the produced 20 lithographic printing plates to form a first laminate.
- the 2nd laminated body in which the surface of the polymer layer faced up was previously set in the cassette which sets a laminated body.
- the first laminate is stacked on the second laminate already set in the cassette while being shifted by 5 cm from the edge, and then pushed in the horizontal direction to be the uppermost planographic printing plate of the second laminate.
- the polymer layer was pushed into the cassette while rubbing the surface of the polymer layer side.
- the lithographic printing plate whose surface on the polymer layer side was rubbed was visually observed to see if there were any scratches, and A was designated as having no scratches, and B was designated as having scratches.
- Example 23 in the table of FIG. 23 is the same as Example 1 of the table in FIG. 18A. That is, the striped coating film 64 of the embodiment of FIG. 3 is a whole surface coating in which the strip-shaped thick film portion 62 and the strip-shaped thin film portion 60 are continuously arranged on the back surface of the strip-shaped support 12.
- Comparative Example 9 assuming the prior art WO2014 / 202519A1, striped discontinuous partial coating having an uncoated portion on the back surface of the belt-like support 12 was performed.
- Comparative Example 10 assuming the prior art WO2014 / 202519A1, dot-like discontinuous partial coating having an uncoated portion on the back surface of the belt-like support 12 was performed.
- the stripe coating film 64 was formed by applying the coating liquid F for the stripe coating film in the same manner as in Example 1, and then the thin film portion 62 and the thin film portion 60 of the stripe coating film 64 were thin. By partially removing only the portion 60 by suction, a partially uncoated portion was intentionally formed.
- Example 23 was evaluated as A with no scratches, but all Comparative Examples were evaluated as B. Therefore, in order to prevent the lithographic printing plate from being damaged, it is necessary that the strip-shaped thick film portion 62 and the strip-shaped thin film portion 60 be applied on the entire surface continuously arranged on the back surface of the strip-shaped support 12. It was proved to be.
- Platinum adsorptivity means that the three produced lithographic printing plate precursors were conditioned for 2 hours in an environment of a temperature of 25 ° C. and a humidity of 75% RH. A laminated body was formed by sequentially stacking without being sandwiched. This laminate was hermetically packaged with kraft paper having an aluminum laminate layer, and left under a 30 ° C. environment for 5 days under a load of 4 kg. And about the laminated body left to stand for 5 days, the adsorptivity between the surface by the side of the polymer layer of a lithographic printing plate and the back surface which has the stripe coating 64 of the lithographic printing plate precursor adjacent to the upper side was investigated.
- the evaluation of the adsorptivity is A when there is no adsorptivity between laminated lithographic printing plate precursors, and B when there is a slight adsorbability but no problem at a practical level, and the adsorptivity is large and practically impossible.
- the case was C.
- the thickness of the thick film portion is 15 mm and exceeds the upper limit of 10 mm, the plate is easily adsorbed and B evaluation is obtained.
- the upper plate stacked by adsorption may shift the lower plate.
- the thickness of the thick film portion is 0.2 mm, which is less than the lower limit of 0.25 mm, “stain on the plate surface” is slightly generated and B evaluation is obtained.
- the formed striped coating film 64 in the dry state has a thick film part contact area ratio of 5% to 90%, a thick film part width of 0.25 mm to 10 mm, and a thick film part distance of 0.5 mm or more. It is preferable that it is 30 mm or less.
- the test consists of the type of the polymer layer on the support surface, the resin type of the backcoat layer on the backside of the support, whether the backcoat layer is continuous or discontinuous, the shape of the surface roughness structure, and
- the lithographic printing plate precursors of Examples 35 to 55 satisfying the present invention by changing the five parameters of whether or not a matting agent was added and the lithographic printing plate precursors of Comparative Examples 12 to 19 not satisfying the present invention were produced.
- aluminum is an aluminum plate
- untreated is a polymer layer for an untreated plate
- negative is a polymer layer for a negative image recording layer
- positive is a positive image.
- processed discard plate means a polymer layer for treatment and discard plate
- unprocessed discard plate means the polymer layer for unprocessed and discard plate.
- “disordered irregularities” in the surface roughness structure means that random thick film portions 62 are randomly arranged on the thin film portion 60 solidly coated on the back surface of the belt-like support 12. It means that it is the back coat layer 70 formed in (1).
- composition of the polymer layer for the untreated plate is the same as that in the first embodiment.
- composition of the polymer layer for the negative image recording layer, the positive image recording layer, the treated discarded plate, and the untreated discarded plate is as follows.
- undercoat layer coating solution having the following composition was applied to the surface of the belt-like support 12 with a wire bar and dried at 90 ° C. for 30 seconds. The coating amount was 10 mg / m 2 .
- -High molecular compound A (following chemical formula 6) (weight average molecular weight: 30,000) 0.05 g ⁇ Methanol 27g ⁇ Ion exchange water 3g
- a protective layer coating solution having the following composition was applied with a wire bar, and dried at 125 ° C. for 75 seconds with a hot air dryer to form a protective layer.
- the coating amount after drying was 1.6 g / m 2 .
- An image recording layer comprising a lower layer and an upper layer was formed on the undercoat layer. That is, a lower layer coating solution having the following composition was coated with a bar coater so that the coating amount after drying was 0.85 g / m 2 , dried at 160 ° C. for 44 seconds, and immediately dried with 17 to 20 ° C. cold air in a belt-like support. The lower layer was formed by cooling until the temperature of 12 reached 35 ° C. Thereafter, an upper layer coating solution having the following composition was applied with a bar coater so that the coating amount after drying was 0.22 g / m 2 , dried at 148 ° C. for 25 seconds, and further slowly cooled with air at 20 to 26 ° C. The upper layer was formed.
- composition of the undercoat layer coating solution is as follows. ⁇ Polymer (13 below) 0.3g ⁇ Pure water 60.0g ⁇ Methanol 939.7g
- the composition of the coating solution for forming the non-photosensitive layer is as follows.
- -Binder polymer A 2.465g ⁇ Phosphoric acid (85% by weight aqueous solution) 0.08 g ⁇ Sulfophthalic acid (50wt% aqueous solution) 0.017g ⁇ Tricarballylic acid 0.017g ⁇ Coloring agent (VPB-Naps) 0.0014g (Victoria Pure Blue naphthalene sulfonate: manufactured by Hodogaya Chemical Co., Ltd.) ⁇ Fluorosurfactant (Megafac F-780-F) 0.009g (Dainippon Ink Chemical Co., Ltd., 30% by weight solution of MEK) ⁇ Methyl ethyl ketone (MEK) 7.93g ⁇ Methanol 6.28g ⁇ 2.01 g of 1-methoxy-2-propanol (MFG)
- the binder polymer A is a 16% by weight solution of
- M1, M2, and M3 each independently represent a hydrogen atom or a sodium atom.
- the number on the right side of the parenthesis represents the content (mol%) of each monomer unit with respect to the total monomer units of the polymer compound.
- a coating solution for component layer 2 having the following composition was applied onto the formed component layer 1 in a bar so that the dry coating amount was 1.8 mg / m 2, and a thermostat ph- 201 was dried at 125 ° C. for 75 seconds to form the constituent layer 2.
- a polymer layer for untreated discarded plate was formed.
- Synthetic mica 0.82g (Somasif ME-100, 8% aqueous dispersion, manufactured by Coop Chemical Co., Ltd.) ⁇ Polymer I-1 (see below) 0.52g ⁇ Carboxymethylcellulose (Serogen PR, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.22g ⁇ Low molecular weight hydrophilic compound G-7 (see below) 0.02g ⁇ Low molecular weight hydrophilic compound G-3 (see below) 0.04g ⁇ Low molecular weight hydrophilic compound G-1 (see below) 0.18 g ⁇ Ion-exchanged water 36.40g
- the polymer I-1 is polyvinyl alcohol (CKS-50, saponification degree 99 mol%, polymerization degree 300, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
- the low molecular weight hydrophilic compound G-7 is a nonionic surfactant (Pluronic P84, manufactured by BASF).
- the low molecular weight hydrophilic compound G-3 is a nonionic surfactant, C 12 H 25 — (OCH 2 CH 2 ) 10 —OH, Emalex 710, manufactured by Nippon Emulsion Co., Ltd.).
- the low molecular weight hydrophilic compound G-1 is an anionic surfactant, sodium 4- (2- (2- (2-ethylhexyloxy) ethoxy) ethoxy) butane-1-sulfonate, manufactured by Wako Pure Chemical Industries, Ltd.) It is.
- the resin types of the back coat layers tested include epoxy resin, polyvinyl acetal resin, polyester resin, acrylic copolymer, UV curable acrylic resin, polystyrene resin, and novolac resin. used.
- polyvinyl acetal resin As the polyvinyl acetal resin, KS-10 manufactured by Sekisui Chemical Co., Ltd. was used, and 25 g was dissolved in 100 g of methyl ethyl ketone.
- acrylic copolymer a methyl methacrylate / ethyl acrylate / acrylic acid (feed weight ratio: 65:20:15) copolymer was used.
- the component composition of the UV curable acrylic resin is as follows, and chemicals manufactured by Ciba Geigy (CIBA) or BASF (BASF) were used.
- the depth of the recess 56 in the grooved portion A of the coating bar 28 of the bar coating machine 24 was adjusted so that the arithmetic average height Sa of the backcoat layer was in the range of 0.5 ⁇ m to 24.0 ⁇ m.
- the depth of the recess 56 in the grooved portion A of the coating bar 28 of the bar coating machine 24 was adjusted so that the arithmetic average height Sa of the backcoat layer was 0.4 ⁇ m.
- Example 54 ⁇ Continuous dot coating> The continuous dot coating film formation of Example 54 was in accordance with the dot coating film forming method of the embodiment of the present invention described above.
- ⁇ Continuous disordered uneven coating> In order to form the back coat layer 70 of the continuous disordered uneven coating film shown in FIG. 26, first, a coating liquid is applied to the entire back surface of the belt-like support 12 to form a flat (flat) thin film portion 60. Then, the thick film portion 62 was applied and formed thereon by a spray coating type coating apparatus, and then dried.
- a particle-containing coating solution was prepared by adding techpolymer ARX-30 manufactured by Sekisui Chemical Co., Ltd. to the same coating solution as the above-described continuous flat coating film, This was applied to the entire back surface of the belt-like support 12 to form a mat coating film having an arithmetic average height Sa of 18 ⁇ m.
- Test result 4 is shown in the table of FIG.
- Examples 35 to 55 and Comparative Examples 12 to 19 four items of “scraping off”, “adhesiveness”, “scratching scratch”, and “giving plate separation” were evaluated by a 5-point full scale method. If all four items had an evaluation of 3 or more, it was determined as a passing line that satisfies the condition of slip-sheet-less as a comprehensive evaluation.
- ⁇ Arithmetic mean height Sa> The arithmetic average height Sa was measured according to the method described in ISO 25178. That is, using the Ryoka System Co., Ltd. micromap MM3200-M100, the magnification was adjusted so that at least the thick film portion and the thin film portion were included in the visual field. At this time, 10 places were selected from the same sample and measured, and the average value thereof was defined as the arithmetic average height Sa.
- peeling is not seen when observed visually, peeling can be confirmed slightly when observed with SEM.
- peeling is not seen when observed visually, peeling can be confirmed when observed with SEM.
- Partial peeling can be confirmed by visual observation, and peeling can be confirmed by SEM observation.
- Humidity was adjusted for 2 hours in an environment of 25 ° C. and 75% RH for 3 planographic printing plate precursors (10 cm ⁇ 10 cm), and the planographic printing plate precursors were sequentially stacked in the same direction with no interleaving paper sandwiched to form a laminate. .
- This laminate was hermetically packaged with kraft paper having an aluminum laminate layer, and left under a 30 ° C. environment for 5 days under a load of 4 kg. Thereafter, the lithographic printing plate precursor was peeled off, and the adhesion state between the polymer layer side surface of the lithographic printing plate precursor and the backcoat layer surface of the lithographic printing plate precursor that was adjacent to the top and bottom during lamination was visually observed.
- the evaluation was performed by sensory evaluation of 1 to 5, with 3 or more being a practical level and 2 or less being an unusable level.
- ⁇ Scratch> After conditioning the lithographic printing plate precursor in an environment of 25 degrees and 60% RH for 2 hours, the lithographic printing plate precursor is punched out to 2.5 cm x 2.5 cm, and a continuous weight type scratch strength test made by Shinto Kagaku Co., Ltd. Installed in the machine TYPE-18, set so that the back side of the lithographic printing plate precursor that has not been punched is in contact with the surface of the lithographic printing plate precursor that has not been punched, and at several points on the lithographic printing plate precursor with a load of 0 to 1500 gf Scratched.
- the scratched lithographic printing plate precursor was set on a Trend setter 3244 manufactured by Creo, and image exposure was performed at a resolution of 2400 dpi, an output of 7 W, an external drum rotational speed of 150 rpm, and a plate surface energy of 110 mJ / cm 2 .
- the lithographic printing plate precursor after image exposure is mounted on an offset rotary printing machine manufactured by Tokyo Machinery Co., Ltd., soiby KKST-S (red) manufactured by Inktec Co., Ltd. as printing ink for newspapers, and Sakata Inks (dampening water) Using Eco Seven N-1 manufactured by Co., Ltd., printing was performed on newsprint at a speed of 100,000 sheets / hour. In the printing process, the 1,000th printed material was sampled, and the degree of scratching due to scratches was visually observed.
- the lithographic printing plate precursor subjected to image exposure is developed at a conveyance speed (line speed) of 2 m / min using an automatic developing machine LP-1310HII manufactured by FUJIFILM Corporation. Development processing was performed at a temperature of 30 ° C.
- the developer is a 1: 4 water diluted solution of DH-N manufactured by Fuji Film
- the developer replenisher is a 1: 1.4 water diluted solution of FCT-421 manufactured by Fuji Film
- the finisher is Fuji Film ( A 1: 1 water dilution solution of HN-GV manufactured by KK was used.
- the exposed lithographic printing plate precursor is transferred to an automatic developing machine LP-940HII manufactured by Fuji Film Co., Ltd. and a developer DT manufactured by Fuji Film Co., Ltd. -2 was diluted 1: 8 with water, and developed with a development temperature of 32 ° C. and a development time of 12 seconds.
- the evaluation of scratches was a sensory evaluation of 1 to 5, with 3 or more being the practical level and 2 or less being the unusable level.
- a stack of 100 lithographic printing plate precursors was set on a CTP plate setter “AMZIsetter” manufactured by NEC Engineering Co., Ltd., and the operation of taking out the plates one by one from the top of the stack was performed 100 times continuously. .
- imparting plate separation was evaluated according to the following criteria. The evaluation was performed by sensory evaluation of 1 to 5, with 3 or more being a practical level and 2 or less being an unusable level.
- the surface of the stripe coating film having a polymer layer for an untreated plate on the support surface and a continuous thin film portion and thick film portion on the back surface of the support is a test section in which the arithmetic average height Sa of the backcoat layer was increased from 0.5 ⁇ m to 24.0 ⁇ m for the lithographic printing plate precursor having an epoxy resin backcoat layer having a roughness structure.
- a polyvinyl acetal resin having a surface roughness structure of a stripe coating film having a continuous thin film portion and a thick film portion on the back surface of the support has a polymer layer for an untreated plate on the support surface.
- the arithmetic average height Sa of the back coat layer was increased from 1.5 ⁇ m to 6.0 ⁇ m.
- Examples 46 to 48 a polyester resin back having a polymer layer for an untreated plate on the surface of the support, and a surface roughness structure of a stripe coating film in which a thin film portion and a thick film portion are continuous on the back surface of the support.
- the arithmetic average height Sa of the backcoat layer was increased from 1.5 ⁇ m to 6.0 ⁇ m.
- Example 49 is a back of an epoxy resin having a polymer layer for a negative type image recording layer on the support surface and a surface roughness structure of a stripe coating film in which a thin film portion and a thick film portion are continuous on the back surface of the support.
- the lithographic printing plate precursor having a coat layer is formed by forming the arithmetic average height Sa of the back coat layer to 4.5 ⁇ m.
- Example 50 is a back of an epoxy resin having a polymer layer for a positive type image recording layer on the support surface and a surface roughness structure of a stripe coating film in which a thin film portion and a thick film portion are continuous on the back surface of the support.
- the lithographic printing plate precursor having a coat layer is formed by forming the arithmetic average height Sa of the back coat layer to 4.5 ⁇ m.
- Example 51 is an epoxy resin backcoat having a surface roughness structure of a striped coating film having a continuous thin film portion and a thick film portion on the back surface of the support, having a polymer layer for a treated disposal plate on the support surface.
- the arithmetic average height Sa of the backcoat layer is 4.5 ⁇ m.
- Example 52 is an epoxy resin back coat having a surface roughness structure of a stripe coating film having a continuous thin film portion and a thick film portion on the back surface of the support, having a polymer layer for untreated discard plate on the support surface.
- the arithmetic average height Sa of the backcoat layer is 4.5 ⁇ m.
- Example 53 is an epoxy resin backcoat layer having a polymer layer for an untreated plate on the support surface, and having a surface roughness structure of a broken-line coating film in which a thin film portion and a thick film portion are continuous on the back surface of the support
- the arithmetic average height Sa of the backcoat layer is 5.0 ⁇ m.
- Example 54 is an epoxy resin backcoat layer having a surface roughness structure of a dot coating film having a continuous thin film portion and a thick film portion on the back surface of the support having a polymer layer for an untreated plate on the support surface.
- the arithmetic average height Sa of the backcoat layer is 5.0 ⁇ m.
- Example 55 is a back of an acrylic copolymer having a surface roughness structure of a disordered coating film in which a thin film portion and a thick film portion are continuous on the back surface of the support, having a polymer layer for an untreated plate on the support surface.
- a lithographic printing plate precursor having a coat layer is formed by forming the arithmetic average height Sa of the back coat layer to 3.0 ⁇ m.
- Comparative Example 12 has a polymer layer for an untreated plate on the support surface, and no backcoat layer was formed on the back surface of the support.
- the arithmetic average height Sa at this time is 0.2 ⁇ m, which is the surface roughness of the support surface.
- “rub-off” is evaluation 5
- “adhesiveness” is evaluation 2
- “scratch” and “applying plate separation” are evaluation 1
- overall evaluation is paper-free. Cannot be achieved.
- Comparative Example 13 has a polymer layer for an untreated plate on the support surface, and a flat back coat layer coated with an epoxy resin on the back surface of the support.
- the arithmetic average height Sa of the back coat layer at this time was 0.1 ⁇ m.
- “rub-off” is evaluation 5
- “adhesiveness” is evaluation 1
- “scratch” is evaluation 4
- “plate separation imparting” is evaluation 1
- the overall evaluation is good. Cannot achieve paperless.
- Comparative Example 14 is a lithographic printing plate precursor having a backcoat layer of an epoxy resin having a surface roughness structure of a continuous stripe coating film on the back surface of the support having a polymer layer for an untreated plate on the support surface.
- the arithmetic average height Sa of the backcoat layer is 0.4 ⁇ m, which is less than 0.5 ⁇ m of the present invention.
- the “rub-off” was evaluated as 5
- the “adhesiveness” was evaluated as 3
- the “rubbing scratch” was evaluated as 4
- the “applied plate separation” was evaluated as 2.
- Comparative Example 15 is a lithographic printing having a backcoat layer of a UV curable acrylic resin having a polymer layer for an untreated plate on the support surface and a surface roughness structure of a discontinuous stripe coating film on the back surface of the support
- the arithmetic average height Sa of the backcoat layer is 4.5 ⁇ m. That is, Comparative Example 15 has an uncoated portion on the back surface of the support.
- “rub-off” is evaluation 2
- “adhesiveness” is evaluation 5
- “scratch” is evaluation 1
- “applied plate separation” is evaluation 5
- the overall evaluation is good. Cannot achieve paperless.
- Comparative Example 16 has a polymer layer for a positive type image recording layer on the support surface, and a flat back coat layer coated with a polystyrene resin on the back surface of the support.
- the arithmetic average height Sa of the back coat layer at this time was 0.3 ⁇ m.
- Comparative Example 17 is a lithographic printing plate having a polymer layer for a positive type image recording layer on the support surface and a polystyrene resin backcoat layer having a surface roughness structure of a discontinuous stripe coating on the back surface of the support.
- the arithmetic average height Sa of the backcoat layer is 5.0 ⁇ m. That is, Comparative Example 17 has an uncoated portion on the back surface of the support.
- “rub-off” is evaluation 2
- “adhesiveness” is evaluation 5
- “scratch” is evaluation 1
- plate separation imparting” is evaluation 4
- the overall evaluation is good. Cannot achieve paperless.
- Comparative Example 18 has a negative image recording layer polymer layer on the support surface, and a flat backcoat layer coated with a novolac resin on the back surface of the support.
- the arithmetic average height Sa of the back coat layer at this time was 0.2 ⁇ m.
- “rub-off” is evaluation 5
- “adhesiveness” is evaluation 2
- “scratch” is evaluation 4
- “plate separation imparting” is evaluation 1
- the overall evaluation is good. Cannot achieve paperless.
- Comparative Example 19 has a polymer layer for an untreated plate on the support surface and a back coat layer coated with an epoxy resin containing a matting agent on the back surface of the support.
- the arithmetic average height Sa of the back coat layer at this time was 18.0 ⁇ m.
- “rub-off” is evaluation 2
- “adhesiveness” is evaluation 5
- “scratch” is evaluation 3
- “applied plate separation” is evaluation 4
- the overall evaluation is good. Cannot achieve paperless.
- the arithmetic average height Sa of the back coat layer having the surface roughness structure in which the thin film portion and the thick film portion are continuously formed is 0.
- the comprehensive evaluation was able to achieve no interleaving paper regardless of the type of polymer layer, the type of resin of the backcoat layer, and the type of shape of the surface roughness structure.
- the arithmetic average height Sa of the back coat layer having a surface roughness structure in which the thin film portion and the thick film portion are continuously formed is preferably 0.5 ⁇ m or more and 24 ⁇ m or less, more preferably 1.5 ⁇ m or more and 8. 0 ⁇ m or less.
- the arithmetic average height Sa is less than 0.5 ⁇ m, and Comparative Examples 12, 13, 16, 18 and the arithmetic average height Sa are 0.5 ⁇ m or more.
- Comparative Examples 15 and 17 having a discontinuous surface roughness structure and Comparative Example 19 to which a matting agent was added the “rubbing” and “adhesiveness” were observed regardless of the type of the polymer layer and the resin type of the backcoat layer.
- the evaluation of at least one item of “scratch”, “scratch scratching”, and “applying plate separation” was 3 or less, and the overall evaluation could not achieve interleaf separation.
- the planographic printing plate precursor of the present invention has a surface roughness structure (component A) in which a thin film portion and a thick film portion are continuously formed on the back surface of the belt-like support, and its surface roughness.
- component A surface roughness structure
- component B arithmetic average height of the backcoat layer satisfies the two components of 0.5 ⁇ m or more (component B), and this two components is a problem of eliminating slip sheets. It was proved that all the above 1) to 4) were satisfied.
- the type of the polymer layer on the support surface and the resin type of the back coat layer on the back surface of the support change. Even if the arithmetic average height Sa is 1.5 ⁇ m or 4.5 ⁇ m, the Beck seconds are different.
- the surface hardness of the polymer layer and the backcoat layer varies depending on the type of polymer layer on the support surface and the resin type of the backcoat layer on the backside of the support. It is presumed that when the layer is in contact with the layer, there is a difference in the air release property of the contact surface. The difference in Beck seconds particularly affects “adhesion” and “giving plate separation”.
- the arithmetic average height Sa is the same at 5.0 ⁇ m, and the type of polymer layer and back It can be seen that if the resin type of the coat layer is the same, the difference in the surface roughness structure hardly affects the Beck seconds.
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Abstract
Description
本発明の製造方法においては、乾燥工程では、塗膜の面に乾燥風を送風し、乾燥風の塗膜面への平行風成分が相対風速30m/s以下であることが好ましい。
本発明の実施の形態の平版印刷版原版は、支持体の表面にポリマー層を有し、支持体の裏面に、薄膜部と厚膜部とが連続形成された表面粗さ構造により算術平均高さSaが0.5μm以上のバックコート層を有して構成される。
図1はバックコート層70の表面粗さ構造の一例として、ストライプ塗膜64を上から見た図であり、図2は図1のa-a線に沿った縦断面図である。これら図1及び図2に示すように、ストライプ塗膜64は、帯状支持体12の裏面に、面上の薄膜部60の上に帯状の厚膜部62が配列される。これにより、帯状の薄膜部60と帯状の厚膜部62とが帯状支持体12の長手方向(製造方法における支持体の走行方向に同義)に平行で且つ交互に連続配列された表面粗さ構造が形成される。即ち、帯状支持体12の裏面には、未塗布部分を有しないようにストライプ塗膜64が全面に形成される。ただし、帯状支持体12の両端部である耳部12Aは未塗布でもよい。
図3はバックコート層70の表面粗さ構造の一例として、ドット塗膜72を上から見た図であり、図4は図3のb-b線に沿った縦断面図である。これら図3及び図4に示すように、ドット塗膜72は、帯状支持体12の裏面に、面状の薄膜部60の上にドット状の厚膜部62が点在した表面粗さ構造である。
図5はバックコート層70の表面粗さ構造の一例として、破線塗膜を上から見た図であり、図6は図5のc-c線に沿った縦断面図である。これら図5及び図6に示すように、破線塗膜74は、帯状支持体12の裏面に、面状の薄膜部60の上に破線状の厚膜部62が形成された表面粗さ構造である。
本発明の実施の形態の平版印刷版原版の製造方法は、上述したストライプ塗膜64、ドット塗膜72、破線塗膜74のうち、ストライプ塗膜64の表面粗さ構造を有するバックコート層70の例で以下に詳細説明する。
先ず、ポリマー層用塗布機14によって、粗面化処理及び必要に応じて下塗り層が塗布された帯状支持体12の表面にポリマー層用の塗布液を塗布する。
次に、ポリマー層用乾燥機16により、ポリマー層用の塗布液が帯状支持体12に塗布形成されたウエット状態のポリマー層の乾燥を行う。ポリマー層用乾燥機16は、ポリマー層に熱風を吹き付ける熱風方式、赤外線等のヒータを用いたヒータ加熱方式、帯状支持体に加熱ロールを接触させる加熱ロール方式等の各種の乾燥方式を採用できるが、熱風方式が特に好ましい。熱風方式の場合、例えば温度100℃以上、露点5~20℃の加熱空気で乾燥することが好ましい。
次に、ポリマー層が形成された帯状支持体12は、ポリマー層用乾燥機16の乾燥熱によって上昇した帯状支持体12の温度を、支持体冷却手段25によって冷却する。この場合、1基の冷却手段でもよいが、目的及び冷却効率を考えると第1及び第2の2基の冷却手段29及び31で構成することが好ましい。第1の冷却手段29は、ポリマー層のべたつきによる搬送パスローラ32、32…への転写防止及び帯状支持体12の歪みや傷の防止を目的とし、帯状支持体12の温度が例えば30℃~40℃程度になるまで急速冷却する。
ストライプ塗膜用の塗布液Fは、ストライプ塗膜64の組成を構成する樹脂成分等の各成分を、公知の揮発性の溶剤に分散又は溶解して調製することができる。
本発明における有機ポリマーとしてエポキシ樹脂やレゾール樹脂を用いた場合、種々の充填剤を本発明の効果を損なわない範囲で添加することができる。充填剤としては、例えば、炭酸カルシウム粉末、シリカ粉末、木紛、パルプなどが挙げられる。充填剤の含有量は、固形分換算で好ましくは1~50質量%、より好ましくは5~30質量%の範囲である。ただし、これらの充填剤は、本発明の効果を損なわないことを前提としたものであり、損なう場合には充填剤の種類や添加量を調整する。
バックコート層70には、可撓性の付与、すべり性の調整や塗布面状を改良する目的で、可塑剤、界面活性剤、その他の添加物を、本発明の効果を損ねない範囲で必要により添加できる。
可塑剤としては、例えば、ジメチルフタレート、ジエチルフタレート、ジブチルフタレート、ジイソブチルフタレート、ジオクチルフタレート、オクチルカプリルフタレート、ジシクロヘキシルフタレート、ジトリデシルフタレート、ブチルベンジルフタレート、ジイソデシルフタレート、ジアリルフタレートなどのフタル酸エステル類、ジメチルグリコールフタレート、エチルフタリールエチルグリコレート、メチルフタリールエチルグリコレート、ブチルフタリールブチルグリコレート、トリエチレングリコールジカプリル酸エステルなどのグリコールエステル類、トリクレジールホスフェート、トリフェニルホスフェートなどのリン酸エステル類、ジイソブチルアジペート、ジオクチルアジペート、ジメチルセバケート、ジブチルセバケート、ジオクチルアゼレート、ジブチルマレエートなどの脂肪族二塩基酸エステル類、ポリグリシジルメタクリレート、クエン酸トリエチル、グリセリントリアセチルエステル、ラウリン酸ブチルなどが有効である。
界面活性剤としては、アニオン系、カチオン系、ノニオン系及び両性界面活性剤が挙げられる。具体例としては、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンポリスチリルフェニルエーテル類、ポリオキシエチレンポリオキシプロピレンアルキルエーテル類、グリセリン脂肪酸部分エステル類、ソルビタン脂肪酸部分エステル類、ペンタエリスリトール脂肪酸部分エステル類、プロピレングリコールモノ脂肪酸エステル類、ショ糖脂肪酸部分エステル類、ポリオキシエチレンソルビタン脂肪酸部分エステル類、ポリオキシエチレンソルビトール脂肪酸部分エステル類、ポリエチレングリコール脂肪酸エステル類、ポリグリセリン脂肪酸部分エステル類、ポリオキシエチレン化ひまし油類、ポリオキシエチレングリセリン脂肪酸部分エステル類、脂肪酸ジエタノールアミド類、N,N-ビス-2-ヒドロキシアルキルアミン類、ポリオキシエチレンアルキルアミン、トリエタノールアミン脂肪酸エステル、トリアルキルアミンオキシドなどの非イオン性界面活性剤、脂肪酸塩類、アビエチン酸塩類、ヒドロキシアルカンスルホン酸塩類、アルカンスルホン酸塩類、ジアルキルスルホ琥珀酸エステル塩類、直鎖アルキルベンゼンスルホン酸塩類、分岐鎖アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキルフェノキシポリオキシエチレンプロピルスルホン酸塩類、ポリオキシエチレンアルキルスルホフェニルエーテル塩類、N-メチル-N-オレイルタウリンナトリウム塩、N-アルキルスルホ琥珀酸モノアミド二ナトリウム塩、石油スルホン酸塩類、硫酸化牛脂油、脂肪酸アルキルエステルの硫酸エステル塩類、アルキル硫酸エステル塩類、ポリオキシエチレンアルキルエーテル硫酸エステル塩類、脂肪酸モノグリセリド硫酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩類、ポリオキシエチレンスチリルフェニルエーテル硫酸エステル塩類、アルキルリン酸エステル塩類、ポリオキシエチレンアルキルエーテルリン酸エステル塩類、ポリオキシエチレンアルキルフェニルエーテルリン酸エステル塩類、スチレン/無水マレイン酸共重合物の部分鹸化物類、オレフィン/無水マレイン酸共重合物の部分鹸化物類、ナフタレンスルホン酸塩ホルマリン縮合物類などのアニオン界面活性剤、アルキルアミン塩類、第四級アンモニウム塩類、ポリオキシエチレンアルキルアミン塩類、ポリエチレンポリアミン誘導体などのカチオン性界面活性剤、カルボキシベタイン類、アミノカルボン酸類、スルホベタイン類、アミノ硫酸エステル類、イミタゾリン類などの両性界面活性剤が挙げられる。
バックコート層70には、更に、着色のための染料、帯状支持体12との密着向上のためのシランカップリング剤、ジアゾニウム塩からなるジアゾ樹脂、有機ホスホン酸、有機リン酸及びカチオン性ポリマー等、更には滑り剤として通常用いられるワックス、高級脂肪酸、高級脂肪酸アミド、ジメチルシロキサンよりなるシリコーン化合物、変性ジメチルシロキサン、ポリエチレン粉末等を適宜加えることができる。また、増粘剤として、カルボキシメチルセルロース等を適宜加えることができる。
これによって、塗工用バー28でストライプ塗膜用の塗布液Fを帯状支持体12に塗布したときに、塗工用バー28の回転による泡(気泡)の巻き込みを防止することができるので、綺麗なストライプ塗膜64を塗布形成することができる。
そして、泡混入限界曲線Eの下側の領域が泡の巻き込みがない領域(G領域)、泡混入限界曲線の上側の領域が泡の巻き込みがある領域(H領域)である。即ち、粘度η(横軸)が小さい場合は塗工用バー28の回転数r(縦軸)を大きくしても泡の巻き込みはなく、粘度ηが大きい場合は塗工用バー28の回転数rを小さくしないと泡の巻き込みがみられる。
次に、ストライプ塗膜用乾燥機20で帯状支持体12の裏面に形成されたウエット状態のストライプ塗膜64を乾燥してドライ状態のストライプ塗膜64(以下「乾膜」ということもある)を形成する。
X…初期平均膜厚(m)(図2の厚膜部62と薄膜部60との乾燥開始時点での平均膜厚)
η…ストライプ塗膜用の塗布液Fの粘度(Pa・s)
λ…ストライプ塗膜のピッチ(m)(図2の厚膜部62同士又は薄膜部60同士の乾燥開始時点での距離)
Z0…初期の膜厚差(m)(図2の厚膜部62と薄膜部60との乾燥開始時点での膜厚差)
Zt…乾膜での膜厚差(m)(図2の厚膜部62と薄膜部60とのドライ状態での膜厚差)
σ…ストライプ塗膜用の塗布液Fの表面張力(N/m)
また、上述の各パラメータは、例えば次の方法で測定することができる。
Pe(ペクレ数)…実験から1.5×10-6
W…ストライプの幅(m)である。
帯状支持体12の裏面に薄膜部60と厚膜部62とが連続形成されたドット塗膜72の表面粗さ構造のバックコート層70を形成する場合は次のように行う。
帯状支持体12の裏面に薄膜部60と厚膜部62とが連続形成された破線塗膜74の表面粗さ構造のバックコート層70を形成する場合は次のように行う。
上述の如く製造された帯状の平版印刷版原版は、所定サイズにカットされた後、複数枚(例えば100枚程度)が積層した本発明の実施の形態の積層体が形成される。
第1の実施例では、表面に無処理版用のポリマー層が形成された帯状支持体12の裏面に、以下の条件でストライプ塗膜用の塗布液を塗布してから乾燥して平版印刷版原版を製造した。
無処理版用のポリマー層は、下塗り層、画像記録層、及び保護層の3層構造として以下のように形成した。
帯状支持体12の表面に、下記組成の下塗り層塗布液を乾燥塗布量が20mg/m2になるように塗布して、下塗り層を形成した。
・下塗り層用化合物(UC-1)(下記化1) 0.18g
・ヒドロキシエチルイミノ二酢酸 0.05g
・界面活性剤(エマレックス710、日本エマルジョン(株)製)
0.03g
・水 28.0g
下塗り層の上に、下記組成の画像記録層塗布液をバー塗布した後、100℃で60秒オーブン乾燥し、乾燥塗布量1.0g/m2の画像記録層を形成した。
<感光液の組成>
・バインダーポリマー(下記化2) 0.240g
(重量平均分子量Mw:55,000、n(EO単位数):2
・赤外線吸収剤(下記化3) 0.020g
・ボレート化合物(テトラフェニルホウ酸ナトリウム) 0.010g
・重合開始剤(下記化3) 0.162g
・重合性化合物 0.192g
トリス(アクリロイルオキシエチル)イソシアヌレート(NKエステルA-9300、新中村化学(株)製)
・アニオン性界面活性剤(下記化3) 0.050g
・フッ素系界面活性剤(下記化3) 0.008g
・2-ブタノン 1.091g
・1-メトキシ-2-プロパノール 8.609g
<ミクロゲル液の組成>
・ミクロゲル 2.640g
・蒸留水 2.425g
油相成分として、下記化4の多官能イソシアナート(三井化学(株)製;75質量%酢酸エチル溶液)4.46g、トリメチロールプロパン(6モル)とキシレンジイソシアナート(18モル)を付加させ、これにメチル片末端ポリオキシエチレン(1モル、オキシエチレン単位の繰り返し数:90)を付加させた付加体(三井化学ポリウレタン(株)製;50質量%酢酸エチル溶液)10g、ペンタエリスリトールトリアクリレート(日本化薬(株)製、SR444)3.15g及びパイオニンA-41C(竹本油脂(株)製)0.1gを酢酸エチル17gに溶解した。水相成分としてポリビニルアルコール((株)クラレ製、PVA-205)の4質量%水溶液40gを調製した。油相成分及び水相成分を混合し、ホモジナイザーを用いて12,000rpmで10分間乳化した。得られた乳化物を、蒸留水25gに添加し、室温で30分攪拌後、50℃で3時間攪拌した。このようにして得られたミクロゲル液の固形分濃度を、15質量%になるように蒸留水を用いて希釈して、ミクロゲルを作製した。光散乱法により測定したミクロゲルの平均粒径は0.2μmであった。
画像記録層上に、下記組成の保護層塗布液をバー塗布した後、120℃で60秒オーブン乾燥し、乾燥塗布量0.15g/m2の保護層を形成して平版印刷版原版を作製した。
・無機層状化合物分散液(下記詳細参照) 1.5g
・親水性ポリマー(下記化5、Mw:30,000)(固形分)0.03g
・ポリビニルアルコール 0.10g
(日本合成化学工業(株)製、CKS50、スルホン酸変性、鹸化度99モル%以上、重合度300)の6質量%水溶液
・ポリビニルアルコール 0.03g
((株)クラレ製、PVA-405、鹸化度81.5モル%、重合度500)の6質量%水溶液
・界面活性剤(エマレックス710、日本エマルジョン(株)製)
0.86g
(下記化5:1質量%水溶液)
・イオン交換水 6.0g
イオン交換水193.6gに合成雲母ソマシフME-100(コープケミカル(株)製)6.4gを添加し、ホモジナイザーを用いて体積平均粒子径(レーザー散乱法)が3μmになるまで分散した。得られた分散粒子のアスペクト比は100以上であった。
バックコート層70は以下のように形成した。
・エポキシ樹脂(JER1009:ジャパンエポキシレジン(株)) 0.80g
・ロジンエステル(エステルガムHP:荒川化学構造(株)) 0.20g
・フッ素界面活性剤(メガファックF-780-F:大日本インキ化学(株))
0.005g
・メチルエチルケトン(MEK) 22.5g
・1-メトキシ-プロパノール 2.5g
(備考)フッ素界面活性剤は、MIBK(メチルイソブチルケトン)の30質量%溶液を使用した。
帯状支持体12として、厚さ0.30mm、幅1030mmのJIS A 1050(JIS: Japan Industrial Standards)のアルミニウム板を使用した。この帯状支持体12は塗布液Fに対して接触角が30°の場合と90°の場合の2水準で行った。
図10に示したバー塗布機24を使用し、帯状支持体12を搬送速度80m/分で連続搬送しながら塗布した。
ケーシング内を連続搬送されるストライプ塗膜64の膜面に近接して矩形状のノズル66を設けた図16の乾燥機20を使用し乾燥温度125℃で乾燥した。また、乾燥風の塗膜面への平行風成分の相対風速を0.1m/s、0.2m/s、3m/s、4m/s、5m/s、10m/s、20m/s、30m/s、35m/sの9水準で行った。
試験結果1は、ストライプ塗膜64が形成されたか否か、角状の突起部62Aの形成を防止できたか否かについて評価した。
<試験結果2>
試験結果2は、塗工用バー28の形状及び回転数、及び乾燥時における乾燥風の塗膜面への平行風成分の相対風速について試験した試験結果である。
・相対風速0.2m/s…実施例20と比較例5
・相対風速2m/s……実施例21と比較例6
・相対風速3m/s……実施例22と比較例8
・相対風速5m/s…実施例1と比較例3
・相対風速30m/s…実施例2と比較例1
この結果から分かるように、風速の数値が同じ実施例と比較例とにおいて、実施例では式1及び式2を満足するが、比較例は式1又は式2を満足しない。したがって、相対風速が35m/sを超えると乾燥ムラには影響するが、相対風速が35m/sを下回る領域であれば、乾燥ムラのみならずにストライプ塗膜64の形成及び角状の突起部62Aの発生防止に特に影響を及ぼさないと考察される。
第2の実施例では、平版印刷版原版を積層して積層体としたときに、形成されたストライプ塗膜と平版印刷版原版の傷の発生との関係を調べた。傷が発生するか否かの試験は次のように行った。
第3の実施例では、上述の如く形成したストライプ塗膜64について、上述の厚膜部接触面積比率、厚膜部幅、厚膜部間距離(ピッチ)を、実施例24~34の如く変えたときの平版印刷版原版同士の「版の吸着性」と「版表面の汚れ」への影響について調べた。
<試験結果3>
図24の表から分かるように、厚膜部接触面積比率が95%で上限90%を超えると、「版の吸着性」が少し見られてB評価となる。厚膜部接触面積比率が3%で下限5%を下回ると、「版表面の汚れ」が少し生じてB評価になる。
第4の実施例では、支持体表面のポリマー層や支持体裏面のバックコート層70の樹脂種類や表面粗さ構造を変えて、バックコート層70の算術平均高さSaと合紙レス化に必要な課題1)~4)との関係を試験した。
無処理版用のポリマー層の組成は、上記した第1の実施例と同様である。
<下塗り層の形成>
帯状支持体12の表面に、下記組成の下塗り層塗布液をワイヤーバーにて塗布し、90℃で30秒間乾燥した。塗布量は10mg/m2であった。
・高分子化合物A(下記化6)(重量平均分子量:3万) 0.05g
・メタノール 27g
・イオン交換水 3g
下記組成の画像記録層塗布液を、下塗り層上にワイヤーバーを用いて塗布した。乾燥は、温風式乾燥装置にて115℃で34秒間行った。乾燥後の被覆量は1.4g/m2であった。
・赤外線吸収剤(IR-1)(下記化8) 0.074g
・重合開始剤(OS-12)(下記化7) 0.280g
・添加剤(PM-1)(下記化8) 0.151g
・重合性化合物(AM-1)(下記化8) 1.00g
・バインダーポリマー(BT-1)(下記化8) 1.00g
・エチルバイオレット(C-1)(下記化8) 0.04g
・フッ素系界面活性剤 0.015g
(メガファックF-780-F DIC(株)製、 メチルイソブチルケトン(MIBK)30質量%溶液)
・メチルエチルケトン 10.4g
・メタノール 4.83g
・1-メトキシ-2-プロパノール 10.4g
画像記録層上に、下記組成の保護層塗布液をワイヤーバーで塗布し、温風式乾燥装置にて125℃で75秒間乾燥させたて保護層を形成した。乾燥後の塗布量は1.6g/m2であった。
・合成雲母 94g
(ソマシフME-100、8%水分散液、コープケミカル(株)製)
・ポリビニルアルコール 58g
(CKS-50:鹸化度99モル%、重合度300、日本合成化学工業(株)製)
・カルボキシメチルセルロース(セロゲンPR、第一工業製薬(株)製)
24g
・界面活性剤-1(プルロニックP-84、BASF社製) 2.5g
・界面活性剤-2(エマレックス710、日本エマルジョン(株)製)
5g
・純水 1364g
《ポジ型画像記録層用のポリマー層》
<下塗り層の形成>
帯状支持体12の表面に、下記組成の下塗り層塗布液をバーコーターで塗布し、80℃で15秒間乾燥し、乾燥後の塗布量が18mg/m2の下塗り層を形成した。
・高分子化合物 (下記化9) 0.3g
・メタノール 100g
下塗り層上に、下層と上層とからなる画像記録層を形成した。即ち、下記組成の下層塗布液を乾燥後の塗布量が0.85g/m2になるようにバーコーターで塗布し、160℃で44秒間乾燥し、直ちに17~20℃の冷風で帯状支持体12の温度が35℃になるまで冷却して下層を形成した。その後、下記組成の上層塗布液を乾燥後の塗布量が0.22g/m2になるようにバーコーターで塗布し、148℃で25秒間乾燥し、更に20~26℃の風で徐冷して上層を形成した。
・N-(4-アミノスルホニルフェニル)メタクリルアミド/アクリロニトリル/メタクリル酸メチル 2.1g
(36/34/30質量%:重量平均分子量50000、酸価2.65)
・m,p-クレゾールノボラック 0.1g
(m/p比=6/4、重量平均分子量4500、未反応クレゾール0.8質量%含有、Tg:75℃)
・シアニン染料A(下記化10) 0.13g
・4,4’-ビスヒドロキシフェニルスルホン 0.13g
・無水テトラヒドロフタル酸 0.19g
・p-トルエンスルホン酸 0.008g
・3-メトキシ-4-ジアゾジフェニルアミンヘキサフルオロホスフェート
0.032g
・エチルバイオレットの対イオンを6-ヒドロキシ-2-ナフタレンスルホン酸に変えた染料 0.078g
・フッ素系界面活性剤B(下記化11) 0.007g
・メチルエチルケトン 25.0g
・1-メトキシ-2-プロパノール 13.0g
・γ-ブチロラクトン 13.0g
・フェノール/m-クレゾール/p-クレゾールノボラック 0.35g
(モル比=5/3/2、重量平均分子量:5000、未反応クレゾール:1.2質量%含有、Tg:70℃)
・アクリル系樹脂C(下記化12) 0.042g
・シアニン染料A(上記化10) 0.019g
・アンモニウム化合物D(下記化12) 0.004g
・スルホニウム化合物G(下記化12) 0.032g
・フッ素系界面活性剤B(上記化11) 0.0045g
・フッ素系界面活性剤E(下記化12) 0.0033g
・フッ素系ポリマーF(下記化12) 0.018g
・メチルエチルケトン 10.0g
・1-メトキシ-2-プロパノール 20.0g
帯状支持体12の表面に、下記組成の下塗り層用塗布液を使用し、乾燥後の塗布量が1.5mg/m2になるように支持体上に塗布して、乾燥した。そして、非感光性層形成用塗布液を、ワイヤーバーを用いて乾燥重量が0.7g/m2となるように塗布した。乾燥は、温風式乾燥装置にて90℃で27秒間乾燥させた。また、非感光性層の表面に、親水性層形成用塗布液O-11をワイヤーバーで塗布し、温風式乾燥装置にて125℃で75秒間乾燥させて親水性層を形成した。この親水性層の全塗布量(乾燥後の被覆量)は1.8g/m2であった。
・ポリマー(下記化13) 0.3g
・純水 60.0g
・メタノール 939.7g
・バインダーポリマーA 2.465g
・リン酸(85重量%水溶液) 0.08g
・スルホフタル酸(50重量%水溶液) 0.017g
・トリカルバリル酸 0.017g
・着色剤(VPB-Naps) 0.0014g
(ビクトリアピュアブルーのナフタレンスルホン酸塩:保土ヶ谷化学(株)製)
・フッ素系界面活性剤(メガファックF-780-F) 0.009g
(大日本インキ化学工業(株)、MEKの30重量%溶液)
・メチルエチルケトン(MEK) 7.93g
・メタノール 6.28g
・1-メトキシ-2-プロパノール(MFG) 2.01g
なお、バインダーポリマーAは、MFG/MEK=1/1の16重量%溶液、重量平均分子量85,000、酸含有量1.64meq/g、下記(1)~(4)の4種類のモノマーの縮合反応物である。
(2)ヘキサメチレンジイソシアネート 12.5モル%
(3)2,2-ビス(ヒドロキシメチル)プロピオン酸 32.5モル%
(4)テトラエチレングリコール 17.5モル%
《無処理捨て版用のポリマー層》
帯状支持体12の表面に、下記組成の構成層1用塗布液を使用し、乾燥塗布量が1.5mg/m2になるように支持体上に塗布して、乾燥した。これにより構成層1を形成した。
・高分子化合物F-1(下記化14) 3.6g
・低分子親水性化合物G-3 0.1g
(非イオン性界面活性剤、C12H25-(OCH2CH2)10-OH、エマレックス710、日本エマルジョン(株)製)
・水 100.0g
・合成雲母 0.82g
(ソマシフME-100、8%水分散液、コープケミカル(株)製)
・ポリマーI-1(下記参照) 0.52g
・カルボキシメチルセルロース(セロゲンPR、第一工業製薬(株)製)
0.22g
・低分子親水性化合物G-7(下記参照) 0.02g
・低分子親水性化合物G-3(下記参照) 0.04g
・低分子親水性化合物G-1(下記参照) 0.18g
・イオン交換水 36.40g
上記ポリマーI-1は、ポリビニルアルコール(CKS-50、鹸化度99モル%、重合度300、日本合成化学工業(株)製)である。
図25の表に示すように、試験を行ったバックコート層の樹脂種類としては、エポキシ樹脂、ポリビニルアセタール樹脂、ポリエステル樹脂、アクリル共重合体、UV硬化性アクリル樹脂、ポリスチレン樹脂、及びノボラック樹脂を使用した。
1,6ヘキサンジオールジアクリレート 13.9g
混合物(4質量%メトキシフェノール+10質量%2,6-ジ-tert-ブチル-p-クレゾール+N-ニトロソ-N-フェニルヒドロキシルアミンアンモニウム)
9.2g
2-フェノキシエチルメタクリレート 13.9g
環状トリメチロールプロパンフォルマール 13.2g
モノファンクショナル・アクリレートエステル 2.3g
UV-光重合開始剤(イルガキュア819) 11.5g
UV-光重合開始剤(ルシリンTPOL) 0.7g
均染剤(EFKA3600N) 6.0g
トリメチロールプロパンEO付加トリアクリレート 6.0g
アクリル酸-2-フェノキシエチル 0.4g
(バックコート層の表面粗さ構造の形成方法)
<連続のストライプ塗膜>
実施例35~52及び比較例14の連続のストライプ塗膜の形成は、上記した本発明の実施の形態のストライプ塗膜の形成方法に準じた。即ち、バックコート層の算術平均高さSaが0.5μm~24.0μmの範囲になるように、バー塗布機24の塗工用バー28の溝有り部位Aの凹部56の深さを調整した。また、比較例14は、バックコート層の算術平均高さSaが0.4μmになるように、バー塗布機24の塗工用バー28の溝有り部位Aの凹部56の深さを調整した。
実施例53の連続の破線塗膜の形成は、上記した本発明の実施の形態の破線塗膜の形成方法に準じた。
実施例54の連続のドット塗膜の形成は、上記した本発明の実施の形態のドット塗膜の形成方法に準じた。
図26に示す連続の無秩序凹凸塗膜のバックコート層70を形成するには、先ず帯状支持体12の裏面全体に塗布液をベタ塗りして平坦状(フラット状)の薄膜部60を塗布形成し、その上にスプレー塗布方式の塗布装置で厚膜部62を塗布形成した後、乾燥した。
比較例12、13、16及び18の連続のフラット塗膜の形成は、帯状支持体12の裏面全体に塗布液をベタ塗りして平坦状(フラット状)の塗膜を形成した。
比較例15及び17の非連続のストライプ塗膜の形成は、従来技術のWO2014/202519A1に記載される方法に準じて行った。
比較例19の連続のマット塗膜の形成は、上記した連続のフラット塗膜と同じ塗布液に、積水化成(株)製のテクポリマーARX-30を含有させた粒子含有塗布液を調製し、これを帯状支持体12の裏面全体にベタ塗りして、算術平均高さSaが18μmのマット塗膜を形成した。
試験結果4を図25の表に示す。
算術平均高さSaの測定は、ISO 25178に記載の方法に準じて行った。即ち、菱化システム(株)製のマイクロマップMM3200-M100を用いて、視野中に、少なくとも厚膜部と薄膜部を含むように倍率を調整した。このとき、同一サンプルから10か所選択、測定し、それらの平均値を算術平均高さSaとした。
JIS P 8119(1998)に準拠して測定した。測定は、熊谷理機工業(株)製ベック平滑度試験機を用い、標準空気量の1/10、即ち1mLの空気量で測定した。図25の表において、ベック秒が小さいほど、平版印刷版原版を積層して積層体としたときに、上下に隣接する平版印刷版原版同士の接面のエア抜け性がよく、平版印刷版原版同士が接着しにくいことを示す。
平版印刷版原版を25度60%RHの環境下で2時間調湿後、平版印刷版原版を2.5cm×2.5cmに打ち抜き、新東科学(株)製の連続加重式引掻強度試験機TYPE-18に取り付け、打ち抜いていない平版印刷版原版の表面の上に、打ち抜いた平版印刷版原版の裏面が接触するようにセットし、0~1500gfの加重で平版印刷版原版の数箇所を擦った。擦った上述の裏面を目視および走査型電子顕微鏡(SEM)で観察し、バックコート層の剥がれレベルを以下の基準で評価した。評価は1~5の官能評価で行い、3以上が実用レベル、2以下は実用不可レベルとした。
平版印刷版原版(10cm×10cm)3枚を25℃75%RHの環境下で2時間調湿後、同方向に合紙の挟み込みのない状態で平版印刷版原版を順次重ねて積層体とした。この積層体を、アルミニウムラミネート層を有するクラフト紙で密閉包装し、4kgの荷重をかけた状態で、30℃環境下5日間放置した。その後、平版印刷版原版を剥がして、平版印刷版原版のポリマー層側の面と、積層時に上下に隣接していた平版印刷版原版のバックコート層の面との接着状態を目視で観察した。評価は1~5の官能評価で行い、3以上が実用レベル、2以下は実用不可レベルとした。
平版印刷版原版を25度60%RHの環境下で2時間調湿後、平版印刷版原版を2.5cm×2.5cmに打ち抜き、新東科学(株)製の連続加重式引掻強度試験機TYPE-18に取り付け、打ち抜いていない平版印刷版原版の表面の上に、打ち抜いた平版印刷版原版の裏面が接触するようにセットし、0~1500gfの加重で平版印刷版原版の数箇所に擦れ傷をつけた。擦れ傷をつけた平版印刷版原版をCreo社製Trendsetter3244にセットし、解像度2400dpiで出力7W、外面ドラム回転数150rpm、版面エネルギー110mJ/cm2で画像露光した。画像露光後の平版印刷版原版を、(株)東京機械製作所製オフセット輪転印刷機に装着し、新聞用印刷インキとしてインクテック(株)製ソイビーKKST-S(紅)、湿し水としてサカタインクス(株)製エコセブンN-1を用い、新聞用紙に100、000枚/時のスピードで印刷した。印刷過程において、1、000枚目の印刷物をサンプリングし、擦れ傷に起因するキズ汚れの程度を目視で観察した。
平版印刷版原版を100枚集積した積層体を、NECエンジニアリング(株)製のCTPプレートセッター「AMZIsetter」にセットし、積層体の最上部から版を1枚ずつ取りだす操作を100回連続で行った。その際の版さばき性付与を下記の基準で評価した。評価は1~5の官能評価で行い、3以上が実用レベル、2以下は実用不可レベルとした。
12 帯状支持体
12A 耳部
14 ポリマー層用塗布機
14A ポケット部
14B スリット
14C スライド面
16 ポリマー層用乾燥機
18 ストライプ塗膜用塗布機
20 ストライプ塗膜用乾燥機
22 塗布液冷却手段
24 バー塗布機
25 支持体冷却手段
26 上流側ガイドローラ
27 下流側ガイドローラ
28 塗工用バー
29 第1の冷却手段
30 塗布ヘッド
31 第2の冷却手段
32 パスローラ
34 ポンプ
36 配管
38 バックアップ部材
40,42 コーターブロック
44,46 マニホールド
48、50 スロット
52 上流側塗布ビード
54 下流側塗布ビード
56 塗工用バーの溝の凹部
58 塗工用バーの溝の凸部
60 ストライプ塗膜の薄膜部
62 ストライプ塗膜の厚膜部
62A 角状の突起部
64 ストライプ塗膜
66 ノズル
66A 吹出口
68 配管
70 バックコート層
72 ドット塗膜
74 破線塗膜
Claims (34)
- 支持体の表面にポリマー層を有する平版印刷版原版であって、
前記支持体の裏面に薄膜部と厚膜部とが連続形成された表面粗さ構造により算術平均高さSaが0.5μm以上のバックコート層を有する平版印刷版原版。 - 前記バックコート層の算術平均高さSaは0.5μm以上24μm以下である請求項1に記載の平版印刷版原版。
- 前記支持体の裏面の算術平均高さSaが0.3μm以下である請求項1又は2に記載の平版印刷版原版。
- 前記バックコート層のベック平滑度が200秒以下である請求項1から3の何れか1項に記載の平版印刷版原版。
- 前記バックコート層は少なくとも1種類の非アルカリ可溶性樹脂を含む請求項1から4の何れか1項に記載の平版印刷版原版。
- 前記表面粗さ構造は、面状の薄膜部の上に帯状の厚膜部が配列したストライプ塗膜である請求項1から5の何れか1項に記載の平版印刷版原版。
- 前記表面粗さ構造は、面状の薄膜部の上にドット状の厚膜部が点在したドット塗膜である請求項1から5の何れか1項に記載の平版印刷版原版。
- 前記表面粗さ構造は、面状の薄膜部の上に破線状の厚膜部が配列した破線塗膜である請求項1から5の何れか1項に記載の平版印刷版原版。
- 前記厚膜部の幅Wが0.5mm以上50mm以下である請求項1から8の何れか1項に記載の平版印刷版原版。
- 前記厚膜部同士のピッチλが0.5mm以上50mm以下である請求項1から9の何れか1項に記載の平版印刷版原版。
- 隣接する前記薄膜部と前記厚膜部との厚み差Ztと前記ピッチλとの比率Zt/λが0.10以下である請求項10に記載の平版印刷版原版。
- 前記厚み差Ztと前記厚膜部の幅Wとの比率Zt/Wが0.10以下である請求項11に記載の平版印刷版原版。
- 前記バックコート層が、平均分子量3000以下の非光硬化性樹脂を少なくとも1種含有する請求項1から12の何れか1項に記載の平版印刷版原版。
- 前記バックコート層が、フェノールホルムアルデヒド樹脂、m-クレゾールホルム、アルデヒド樹脂、p-クレゾールホルムアルデヒド樹脂、m-/p-混合クレゾールホルムアルデヒド樹脂、フェノール/クレゾール(m-,p-,又はm-/p-混合のいずれでもよい)混合ホルムアルデヒド樹脂等のノボラック樹脂やレゾール樹脂、ピロガロール、アセトン樹脂、エポキシ樹脂、飽和共重合ポリエステル樹脂、フェノキシ樹脂、ポリビニルアセタール樹脂、塩化ビニリデン共重合樹脂、ポリブテン、ポリブタジエン、ポリアミド、不飽和共重合ポリエステル樹脂、ポリウレタン、ポリウレア、ポリイミド、ポリシロキサン、ポリカーボネート、エポキシ樹脂、塩素化ポリエチレン、アルキルフェノールのアルデヒド縮合樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリスチレン、アクリル系樹脂共重合樹脂、ヒドロキシセルロース、ポリビニルアルコール、セルロースアセテート、カルボキシメチルセルロースからなる群より選択される少なくとも一種を含有する請求項1から13の何れか1項に記載の平版印刷版原版。
- 前記ポリマー層が、赤外線吸収剤を含有するポジ型画像記録層である請求項1から14の何れか1項に記載の平版印刷版原版。
- 前記ポリマー層が、赤外線吸収剤、重合開始剤、又は重合性化合物を含有するネガ型画像記録層である請求項1から14の何れか1項に記載の平版印刷版原版。
- 請求項1から14の何れか1項に記載の平版印刷版原版であって、前記ポリマー層が非感光性層で構成される有処理捨て版用の平版印刷版原版。
- 請求項1から14の何れか1項に記載の平版印刷版原版であって、前記ポリマー層が水溶性層又は水分散性層のいずれかで構成される無処理版用の平版印刷版原版。
- 請求項1から14の何れか1項に記載の平版印刷版原版であって、前記ポリマー層が水溶性層又は水分散性層のいずれかで構成される無処理捨て版用の平版印刷版原版。
- 前記水分散性層がポリマー微粒子を含む請求項18又は19に記載の平版印刷版原版。
- 支持体の表面にポリマー層を有し、前記支持体の裏面に薄膜部と厚膜部とが連続形成された表面粗さ構造により算術平均高さSaが0.5μm以上のバックコート層を有する平版印刷版原版を複数枚積層してなる積層体。
- 支持体の表面にポリマー層を有する平版印刷版原版の製造方法であって、
前記支持体の裏面に薄膜部と厚膜部とが連続形成された表面粗さ構造の塗膜を塗布形成する塗布工程と、
前記塗膜を乾燥し、前記表面粗さ構造により算術平均高さSaが0.5μm以上のバックコート層を形成する乾燥工程と、を備えた平版印刷版原版の製造方法。 - 前記塗布工程では、隣接する前記薄膜部と前記厚膜部との厚み差が1μm以上50μm以下である請求項22に記載の平版印刷版原版の製造方法。
- 前記塗布工程では、塗布液の粘度が0.3mPa・s以上100mPa・s以下及び表面張力が20mN/m以上40mN/m以下、前記塗布液と前記支持体との接触角が10°以上90°以下の塗布条件で前記塗布液を前記支持体に塗布してウエット状態の前記表面粗さ構造の塗膜を形成し、
前記乾燥工程では、前記形成したウエット状態の前記塗膜を乾燥したときに、乾燥点tが次の式1及び式2の不等式を満足する乾燥条件で乾燥する請求項23に記載の平版印刷版原版の製造方法。
- 前記塗布工程では、バー塗布方式、インクジェット印刷方式、グラビア印刷方式、スクリーン印刷方式、スプレー塗布方式のいずれかの方法によって前記塗膜を塗布形成する請求項23又は24に記載した平版印刷版原版の製造方法。
- 前記表面粗さ構造の塗膜は、帯状の前記薄膜部と帯状の前記厚膜部とが交互に連続配列されたストライプ塗膜である請求項23から25の何れか1項に記載の平版印刷版原版の製造方法。
- 前記表面粗さ構造の塗膜は、平坦状の前記薄膜部の面上にドット状の前記厚膜部が点在したドット塗膜である請求項23から25の何れか1項に記載の平版印刷版原版の製造方法。
- 前記表面粗さ構造の塗膜は、平坦状の前記薄膜部の面上に破線状の前記厚膜部が連続配列された破線塗膜である請求項23から25の何れか1項に記載の平版印刷版原版の製造方法。
- 前記ストライプ塗膜の場合、
前記塗布工程では、溝が形成された溝有り部位と溝が形成されていない溝無し部位とが軸芯方向に交互に形成された塗工用バーを有するバー塗布装置を用い、塗布液を前記塗工用バーにより塗布する請求項26に記載の平版印刷版原版の製造方法。 - 前記塗工用バーは、前記溝有り部位の溝を構成する凹部と凸部について、隣接する凹部同士又は凸部同士の間のピッチ長さをP、凹部の深さをh、凹部の開口幅をDとしたときに、Pが0.25mm以上、D/Pが0.49以下、及びh/Dが0.01以上0.55以下を満足する請求項29に記載の平版印刷版原版の製造方法。
- 走行する帯状の前記支持体に前記塗布液を塗布する前記塗工用バーにより連続塗布する方式であって、前記塗工用バーの直径が6mm以上50mm以下であり、前記塗工用バーの回転数はrで単位rpmとし、前記塗布液の粘度はηで単位はmPa・sとしたときに次の式3の関係を満足する請求項29又は30に記載の平版印刷版原版の製造方法。
r<65714×η-1.122…式3 - 前記乾燥工程では、前記塗膜の面に乾燥風を送風し、前記乾燥風の塗膜面への平行風成分が相対風速30m/s以下である請求項23から31の何れか1項に記載の平版印刷版原版の製造方法。
- 前記ドット塗膜の場合、
前記塗布工程は、
前記支持体に塗布液をベタ塗りして平坦状の前記薄膜部を塗布形成する第1塗布工程と、
前記平坦状の薄膜部の上に前記塗布液をスクリーン印刷装置でドット状に塗布して前記厚膜部を塗布形成する第2塗布工程と、を有する請求項27に記載の平版印刷版原版の製造方法。 - 前記破線塗膜の場合、
前記塗布工程は、
前記支持体に塗布液をベタ塗りして平坦状の前記薄膜部を塗布形成する第1塗布工程と、
前記平坦状の薄膜部の上に前記塗布液をスクリーン印刷装置で破線状に塗布して前記厚膜部を塗布形成する第2塗布工程と、を有する請求項28に記載の平版印刷版原版の製造方法。
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JP7055877B2 (ja) | 2018-07-31 | 2022-04-18 | 富士フイルム株式会社 | 平版印刷版原版 |
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CN112752656A (zh) * | 2018-09-28 | 2021-05-04 | 富士胶片株式会社 | 印刷用原版、印刷用原版层叠体、印刷版的制版方法及印刷方法 |
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JPWO2020067373A1 (ja) * | 2018-09-28 | 2021-09-02 | 富士フイルム株式会社 | 印刷用原版、及び印刷版の製版方法 |
CN112789178A (zh) * | 2018-09-28 | 2021-05-11 | 富士胶片株式会社 | 印刷用原版、印刷用原版层叠体、印刷版的制版方法及印刷方法 |
WO2020067374A1 (ja) * | 2018-09-28 | 2020-04-02 | 富士フイルム株式会社 | 印刷用原版、印刷用原版積層体、印刷版の製版方法、及び印刷方法 |
WO2020067373A1 (ja) * | 2018-09-28 | 2020-04-02 | 富士フイルム株式会社 | 印刷用原版、印刷用原版積層体、印刷版の製版方法、及び印刷方法 |
JP7309741B2 (ja) | 2018-09-28 | 2023-07-18 | 富士フイルム株式会社 | 印刷用原版、及び印刷版の製版方法 |
US11745531B2 (en) | 2018-09-28 | 2023-09-05 | Fujifilm Corporation | Printing plate precursor, printing plate precursor laminate, method for making printing plate, and printing method |
CN112789178B (zh) * | 2018-09-28 | 2023-10-20 | 富士胶片株式会社 | 印刷用原版、其层叠体、印刷版的制版方法及印刷方法 |
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EP3437894A1 (en) | 2019-02-06 |
JP6731043B2 (ja) | 2020-07-29 |
EP3437894B1 (en) | 2020-06-03 |
CN108778768B (zh) | 2020-04-03 |
BR112018070203A2 (pt) | 2019-01-29 |
US10377163B2 (en) | 2019-08-13 |
CN108778768A (zh) | 2018-11-09 |
US20190023052A1 (en) | 2019-01-24 |
EP3437894A4 (en) | 2019-04-10 |
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