CN104744923A - Resin Composition For Laser Engraving, Flexographic Printing Plate Precursor For Laser Engraving And Process For Producing Same, And Process For Making Flexographic Printing Plate - Google Patents

Resin Composition For Laser Engraving, Flexographic Printing Plate Precursor For Laser Engraving And Process For Producing Same, And Process For Making Flexographic Printing Plate Download PDF

Info

Publication number
CN104744923A
CN104744923A CN201410822185.4A CN201410822185A CN104744923A CN 104744923 A CN104744923 A CN 104744923A CN 201410822185 A CN201410822185 A CN 201410822185A CN 104744923 A CN104744923 A CN 104744923A
Authority
CN
China
Prior art keywords
composition
printing plate
laser
resin composition
laser engraving
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410822185.4A
Other languages
Chinese (zh)
Inventor
菅崎敦司
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of CN104744923A publication Critical patent/CN104744923A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
    • B41C1/00—Forme preparation
    • B41C1/02—Engraving; Heads therefor
    • B41C1/04—Engraving; Heads therefor using heads controlled by an electric information signal
    • B41C1/05—Heat-generating engraving heads, e.g. laser beam, electron beam
    • 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

Abstract

The present invention provides a flexographic printing plate precursor for laser engraving, a process for producing same, and a process for making the flexographic printing plate which can obtain the excellent engraving offscourings, image quality and ink transitivity, and provides a resin composition for laser engraving which is suitable for the printing plate precursor. The resin composition for laser engraving comprises (Component A) a binder polymer comprising an ethylenically unsaturated bond in at least one part selected from the group consisting of a main chain interior, a main chain terminal, and a side chain, (Component B) a polymerization initiator, and (Component C) a foaming agent, Component A comprising a plastomer selected from the group consisting of a polybutadiene structure-containing polymer, a polyisoprene structure-containing polymer, and a urethane (meth)acrylate, and Component A having a content of at least 50 mass% relative to the total mass of the composition. The flexographic printing plate precursor for laser engraving is characterized by comprising a crosslinking relief block forming layer formed by foaming and crosslinking the layers containing the resin composition for laser engraving.

Description

The graphic arts process of resin composition for laser engraving, laser sculpture type flexible printing plate originals and method for making and flexible printing plate
Technical field
The present invention relates to the method for platemaking of resin composition for laser engraving, laser sculpture type flexible printing plate originals and manufacture method and flexible printing plate.
Background technology
Propose more multiplex laser straight and connect engraving relief printing plate form layers and so-called " the direct engraving CTP mode " of making a plate.In which, to flexible master direct irradiation laser, produce thermolysis and volatilization by photothermal deformation, form recess.Direct engraving CTP mode is formed different from using the relief printing plate of former figure film, and it can freely control relief printing plate shape.Therefore, when forming the image as hollow out word, this region deeper can be carved with the region than other, or in fine halftone dot image, considering impedance squeegee pressure, carry out the engraving etc. being with shoulder (shoulder).The laser used in which uses the carbon dioxide laser of high-output power usually.When carbon dioxide laser, all organic compound all absorb irradiation energy and can be converted into heat.On the other hand, developing cheap and small-sized semiconductor laser, but these laser are visible ray and near infrared light, therefore, need absorb this laser and convert heat to.
As existing flexible printing plate, there will be a known the flexible printing plate recorded in such as Japanese Unexamined Patent Application Publication 2007-520379 publication, Japanese Unexamined Patent Publication 2002-3665 publication and Japanese Unexamined Patent Publication 2002-103539 publication.
Summary of the invention
Invent problem to be solved
Problem to be solved by this invention is, provides the laser sculpture type flexible printing plate originals of flexible printing plate and the method for platemaking of manufacture method and flexible printing plate thereof of washability excellence, image quality and the black liquid transitivity excellence that can obtain engraving dregs.
In addition, other problems to be solved by this invention is to provide the resin composition for laser engraving being suitable for such printing plate precursor.
For the scheme of dealing with problems
The problems referred to above of the present invention are solved by the means described in following <1>, <8>, <9>, <16> or <18>.Together be described below with as <2> ~ <7> preferred embodiment, <10> ~ <15> and <17>.
<1> resin composition for laser engraving, it is characterized in that, main chain inside is being selected from containing (composition A), the part of at least 1 in main chain terminal and side chain has the binder polymer of ethylenic unsaturated bond, (composition B) polymerization starter, and (composition C) whipping agent, composition A is selected from the polymkeric substance with polybutadiene configuration, there is the polymkeric substance of polyisoprene structure, and the plastomer in (methyl) propenoic methyl carbamate, the content of composition A is more than 50 quality % relative to the total mass of composition,
The resin composition for laser engraving of <2> according to <1>, wherein, composition A be polyhutadiene, polyisoprene or at least make the multipolymer of divinyl and/or isoprene copolymer;
The resin composition for laser engraving of <3> according to <1> or <2>, wherein, composition A is polyhutadiene or polyisoprene;
The resin composition for laser engraving of <4> according to any one of <1> ~ <3>, wherein, composition B is organo-peroxide;
The resin composition for laser engraving of <5> according to any one of <1> ~ <4>, wherein, composition C is chemical foaming agent;
The resin composition for laser engraving of <6> according to any one of <1> ~ <5>, it is also containing (components D) polymerizable compound;
The resin composition for laser engraving of <7> according to any one of <1> ~ <6>, photothermal deformation agent that it contains (composition E);
<8> laser sculpture type flexible printing plate originals, it has makes the layer of the resin composition for laser engraving comprised according to any one of <1> ~ <7> carry out the crosslinked relief printing plate form layers foaming and be cross-linked;
<9> laser sculpture type flexible printing plate originals, it is characterized in that, it has the crosslinked relief printing plate form layers that the layer making to comprise resin composition for laser engraving carries out foaming and being cross-linked, wherein said resin composition for laser engraving contains (composition A) and is being selected from main chain inside, the part of at least 1 in main chain terminal and side chain has the binder polymer of ethylenic unsaturated bond, (composition B) polymerization starter, and (composition C) whipping agent, composition A is selected from the polymkeric substance with polybutadiene configuration, there is the polymkeric substance of polyisoprene structure, and the plastomer in (methyl) propenoic methyl carbamate, the content of composition A is more than 50 quality % relative to the total mass of composition,
The laser sculpture type flexible printing plate originals of <10> according to <9>, wherein, composition A be polyhutadiene, polyisoprene or at least make the multipolymer of divinyl and/or isoprene copolymer;
The laser sculpture type flexible printing plate originals of <11> according to <9> or <10>, wherein, composition A is polyhutadiene or polyisoprene;
The laser sculpture type flexible printing plate originals of <12> according to any one of <9> ~ <11>, wherein, composition B is organo-peroxide;
The laser sculpture type flexible printing plate originals of <13> according to any one of <9> ~ <12>, wherein, composition C is chemical foaming agent or pneumatogen;
The laser sculpture type flexible printing plate originals of <14> according to any one of <9> ~ <13>, wherein, above-mentioned resin composition for laser engraving is also containing (components D) polymerizable compound;
The laser sculpture type flexible printing plate originals of <15> according to any one of <9> ~ <14>, wherein, above-mentioned resin composition for laser engraving is also containing (composition E) photothermal deformation agent;
The manufacture method of the laser sculpture type flexible printing plate originals of <16> according to any one of <8> ~ <15>, it comprises following operation:
Form the operation comprising the layer of resin composition for laser engraving, wherein said resin composition for laser engraving contains (composition A) and is being selected from main chain inside, the binder polymer at least partially with ethylenic unsaturated bond in main chain terminal and side chain, (composition B) polymerization starter, and (composition C) whipping agent, composition A is selected from the polymkeric substance with polybutadiene configuration, there is the polymkeric substance of polyisoprene structure, and the plastomer in (methyl) propenoic methyl carbamate, the content of composition A is more than 50 quality % relative to the total mass of composition, and
Make the layer comprising above-mentioned resin composition for laser engraving carry out foaming and being cross-linked and form the crosslinked cambial operation of relief printing plate;
The manufacture method of the laser sculpture type flexible printing plate originals of <17> according to <16>, wherein, above-mentioned foaming and crosslinked simultaneously to carry out at least partially;
The method for platemaking of a <18> flexible printing plate, it comprises the operation of the laser sculpture type flexible printing plate originals prepared according to any one of <8> ~ <15>; And laser sculpture is carried out and the engraving operation of formation relief layer to above-mentioned crosslinked relief printing plate form layers.
Invention effect
According to the present invention, the laser sculpture type flexible printing plate originals of flexible printing plate and the method for platemaking of manufacture method and flexible printing plate thereof of washability excellence, image quality and the black liquid transitivity excellence that can obtain engraving dregs can be provided.
In addition, according to the present invention, the resin composition for laser engraving being suitable for such printing plate precursor can be provided.
Embodiment
Below, for content of the present invention, be described in detail.For the explanation of the constitutive requirements of following record, sometimes carry out based on the embodiment that represents of the present invention, but the present invention is not limited to such embodiment.
In addition, in the present invention, " ~ " refers to comprise the numerical value recorded before and after it and uses as the meaning of lower value and higher limit.
In addition, in the present invention, also by " (composition A) is being selected from the binder polymer at least partially with ethylenic unsaturated bond in main chain inside, main chain terminal and side chain " etc. referred to as " composition A " etc.
Further, in the mark of the group (atomic group) in this specification sheets, unmarked replacement and comprise without the mark replaced and not there is substituent group also comprise there is substituent group.Such as " alkyl " not only comprises and does not have substituent alkyl (without substituted alkyl), also comprise and have substituent alkyl (substituted alkyl).
In the present invention, " mass parts " and " quality % " is equivalent in meaning with " weight part " and " % by weight " respectively.
In addition, in the present invention, preferred form be combined as preferred form.
(resin composition for laser engraving)
Resin composition for laser engraving of the present invention is (hereinafter simply referred to as " resin combination " or " composition ".), it is characterized in that, it contains (composition A) is being selected from the binder polymer at least partially with ethylenic unsaturated bond in main chain inside, main chain terminal and side chain, (composition B) polymerization starter and (composition C) whipping agent, composition A is selected from the plastomer in the polymkeric substance with polybutadiene configuration, the polymkeric substance with polyisoprene structure and (methyl) propenoic methyl carbamate, relative to the total mass of composition, the content of composition A is more than 50 quality %.
In addition, resin composition for laser engraving of the present invention preferably has foaminess and bridging property.
The present inventor furthers investigate, found that: by containing composition A ~ composition C at resin composition for laser engraving, the image quality of flexible printing plate and the resin composition for laser engraving of black liquid transitivity excellence of the washability of the engraving dregs occurred during laser sculpture excellence, gained can be provided.
Although detailed mechanism is indefinite, but can estimate as follows: by (composition B) polymerization starter and (composition C) whipping agent, making to comprise (composition A) being selected from the resin combination at least partially with the binder polymer of ethylenic unsaturated bond in main chain inside, main chain terminal and side chain produces foaming and crosslinked, can be formed in the alveolate relief layer of tool in specific resin structure thus, in addition, also can produce the recess from bubble on relief layer surface, improve black liquid transitivity.
In addition, if the Young's modulus of the relief layer of flexible printing plate is too high, although then the black liquid transitivity of high image quality is deteriorated, if Young's modulus is too low, although then the high image quality of black liquid transitivity is deteriorated, the present inventor has found the relation of antinomy as above.But, in the present invention, estimate as follows: fully can guarantee black liquid transitivity according to above-mentioned effect, and, bubble gives flexibility, matrix part beyond bubble is ad hoc structure, for while high Young's modulus being the relief layer due to bubble with flexibility, thus can take into account black liquid transitivity and image quality.In addition, also presumption is due to following reason: when having the hollow-particle in shell portion disclosed in use Japanese Unexamined Patent Application Publication 2007-520379 publication, ink liquid transitivity and image quality are deteriorated simultaneously, but fully can not produce the flexibility of above-mentioned recess and relief layer.
Further, although detailed mechanism is indefinite, but think and use resin composition for laser engraving of the present invention and the flexible printing plate that obtains owing to having the alveolate relief layer of tool in specific resin structure, the generation thus carving dregs is few, washability is excellent.
In addition, in this specification sheets, about the explanation of flexible printing plate originals, be smooth layer containing mentioned component A and composition B and for the surface of the image formation layer of laser sculpture, and uncrosslinked bridging property layer is called relief printing plate form layers, carry out crosslinked layer by making above-mentioned relief printing plate form layers and be called crosslinked relief printing plate form layers, define concavo-convex layer on surface by carrying out laser sculpture to it and be called relief layer.In addition, when using pneumatogen as composition C, after formation relief printing plate form layers or crosslinked relief printing plate form layers, it can also be made to be included in relief printing plate form layers or crosslinked relief printing plate form layers by impregnating.
Below, composition contained in resin composition for laser engraving of the present invention is described.
(composition A) has olefinic in main chain inside, main chain terminal and side chain at least partially being selected from the binder polymer of unsaturated link(age)
Resin composition for laser engraving of the present invention contains (composition A) and is being selected from the binder polymer at least partially with ethylenic unsaturated bond in main chain inside, main chain terminal and side chain, composition A be selected from the polymkeric substance with polybutadiene configuration, the polymkeric substance with polyisoprene structure and, plastomer in (methyl) propenoic methyl carbamate, relative to the total mass of composition, the content of composition A is more than 50 quality %.
In addition, composition A is preferably non-water-soluble binder polymer.
Composition A has ethylenic unsaturated bond in main chain inside, main chain terminal and side chain at least partially being selected from, preferably at least partially there is ethylenic unsaturated bond in the inner and main chain terminal of main chain being selected from, be more preferably and at least partially there is ethylenic unsaturated bond in main chain inside.
In addition, in the present invention, " main chain " refers to and forms bonding chain the longest comparatively speaking in the molecule of the macromolecular compound of resin, and " side chain " refers to the carbochain of branch from main chain, can comprise heteroatoms in side chain.
In addition; as the ethylenically unsaturated group that composition A can have; be not particularly limited; preferably from ethylenic unsaturated bond or (methyl) acryl of divinyl or isoprene; more preferably from ethylenic unsaturated bond or (methyl) acryloxy of divinyl or isoprene, the preferred ethylenic unsaturated bond from divinyl or isoprene further.
In addition, as the ethylenic unsaturated bond from divinyl or isoprene, can be by 1,4-addition and the ethylenic unsaturated bond of the main chain inside formed, by 1,2-addition or 3,4-addition and the ethylenic unsaturated bond of side chain formed and the ethylenic unsaturated bond of these ethylenic unsaturated bond stereoisomers, composition A preferably has by divinyl or the Isosorbide-5-Nitrae-addition of isoprene and the ethylenic unsaturated bond of the main chain inside formed.
Composition A is selected from the polymkeric substance with polybutadiene configuration, there is the polymkeric substance of polyisoprene structure, and the plastomer in (methyl) propenoic methyl carbamate, composition A is preferably selected from polyhutadiene, polyisoprene, at least make the multipolymer of divinyl and/or isoprene copolymer, and the plastomer in (methyl) propenoic methyl carbamate, be more preferably and be selected from polyhutadiene, polyisoprene, and the plastomer at least making in the multipolymer of divinyl and/or isoprene copolymer, more preferably be selected from the plastomer in polyhutadiene and polyisoprene, be particularly preferably polyhutadiene and for plastomer.If above-mentioned form, then can obtain printing resistance and the more excellent flexible printing plate of black liquid transitivity, in addition, the washability of engraving dregs is more excellent.
Composition A is plastomer at 20 DEG C.
Under using the elastomeric situation such as rubber, thermoplastic elastomer as composition A, intensity and flexibility cannot be had concurrently, in addition, do not have mobility thus cannot be cross-linked fully when carrying out crosslinked, the washability of the printing resistance of flexible printing plate and image quality and engraving dregs is deteriorated.
In the present invention, " plastomer " refers to, as polymer association compiles in " new edition polymer dictionary " (Japan, towards storehouse bookstore, distribution in 1988) and records, there is easily flow deformation and the polymer body of the such character of shape can be solidified into distortion by cooling after by heating.Plastomer (has following character: when applying external force relative to elastomerics, corresponding to this external force instantaneous deformation, and when removing external force, the short period of time resiles shape) word, do not show the recoverable deformation as elastomerics and easily viscous deformation.
In the present invention, plastomer refers to, can it be made to be deformed into 200% with less external force under room temperature (20 DEG C), even if remove this external force, also can not return to less than 130% when life size being set to 100%.Less external force refers to, specifically, tensile strength is the external force of 1 ~ 100MPa.In more detail, refer to polymkeric substance as described below: the stretching permanent strain based on JIS K6262-1997 is tested, tension test can be utilized at 20 DEG C it can not to be made to rupture from stretching 2 times the distance between bench marks before the stretching of the test film of dumbbell shaped No. 4 shapes specified based on JIS K6251-1993, and, distance between bench marks before being stretched to stretching from 2 times afterwards keep 60 minutes, then, removing stretching external force, back draft permanent strain in 5 minutes is more than 30%.In addition, in the present invention, except test film being set to the dumbbell shaped that specifies in JISK6251 and making the hold-time be 60 minutes and make the temperature of testing laboratory be except 20 DEG C, all based on the stretching permanent strain test method of JIS K6262-1997.
In addition, when the polymkeric substance of said determination cannot be carried out, that is, in tension test, even if the polymkeric substance not applying to apply less external force when stretching external force also can produce distortion and cannot return to polymkeric substance or the said determination of original shape and rupture is equivalent to plastomer.Such as, at 20 DEG C aqueous polymkeric substance is plastomer.
Further, plastomer can be less than 20 DEG C according to the second-order transition temperature of polymkeric substance (Tg) and judges.When having the polymkeric substance of more than 2 Tg, all Tg are less than 20 DEG C.In addition, the Tg of polymkeric substance can be measured (DSC) method and measures by means of differential scanning calorimetry.
As there is the polymkeric substance of polybutadiene configuration or there is the polymkeric substance of polyisoprene structure, it can be the homopolymer of divinyl or isoprene, also can for the multipolymer making divinyl and/or isoprene carry out copolymerization, can also for making the polymkeric substance of their modifications.
In addition, as long as the polymkeric substance with polybutadiene configuration or there is polyisoprene structure polymkeric substance main chain mainly using isoprene or divinyl as the polymkeric substance of monomeric unit, its a part can hydrogenation and be converted into saturated bond.In addition, in the main chain of polymkeric substance or end can, by modifications such as acid amides, carboxyl, hydroxyl, (methyl) acryls, can also be epoxidation.
As can the monomer of copolymerization, be not particularly limited, such as vinylbenzene, alpha-methyl styrene, o-methyl styrene, p-methylstyrene, vinyl cyanide, methacrylonitrile, vinylchlorid, vinylidene chloride, acrylamide, Methacrylamide, Methacrylamide vinyl acetate, acrylate, methacrylic ester, vinylformic acid, methacrylic acid etc. can be listed.
As the multipolymer at least making divinyl and/or isoprene carry out copolymerization, specifically, styrene-butadiene copolymer can be listed, styrene-isoprene polymer, acrylonitrile butadiene copolymer, acrylonitrile-isoprene multipolymer, acrylate-butadiene multipolymer, acrylate-isoprene copolymer, acrylate-chloroprene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene isoprene styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer, end (methyl) acrylate modified polyhutadiene, end (methyl) acrylate modified polyisoprene, the acrylate modified hydrogenation polyhutadiene of end (methyl), end (methyl) acrylate modified hydrogenation polyisoprene etc.
These polymkeric substance with polybutadiene configuration and the polymkeric substance with polyisoprene structure can be manufactured by letex polymerization, in addition, can also be manufactured by solution polymerization.
In the present invention, the polymkeric substance with polybutadiene configuration and the polymkeric substance with polyisoprene structure are preferably more than 80mol% from the ratio that the monomeric unit of aliphatic hydrocarbon (isoprene, divinyl or their hydrogenation thing) is shared in main chain.If the ratio shared in main chain from the monomeric unit of aliphatic hydrocarbon is more than 80mol%, then because washability is good, therefore preferably.Content from the monomeric unit of aliphatic hydrocarbon is more preferably more than the 90mol% of whole monomeric units of the main chain of constituent A, more preferably more than 95mol%, be particularly preferably more than 99mol%.
Namely, such as with regard to having the polymkeric substance of polyisoprene structure, isoprene and the ratio from the monomeric unit of the hydrogenation thing of isoprene amount to and are preferably more than 80mol%, are more preferably more than 90mol%, more preferably more than 95mol%, are particularly preferably more than 99mol%.
Similarly, with regard to the polymkeric substance with polybutadiene configuration, the ratio from the monomeric unit of the hydrogenation thing of divinyl and divinyl amounts to and is preferably more than 80mol%, is more preferably more than 90mol%, more preferably more than 95mol%, is particularly preferably more than 99mol%.
In addition, when using isoprene or butadienecopolymer as composition A, isoprene, divinyl and the monomeric unit from their hydrogenation thing are amounted to containing more than 80mol%, more preferably containing more than 90mol%, further preferably containing more than 95mol%, particularly preferably containing more than 99mol%.
With regard to isoprene, it is known that according to catalyzer, reaction conditions, utilize 1,2-, 3,4-or Isosorbide-5-Nitrae-addition be polymerized, the present invention can for the polyisoprene be polymerized by above-mentioned arbitrary addition.In the middle of these, from the view point of the mooney viscosity obtaining expectation, preferably contain cis Isosorbide-5-Nitrae-polyisoprene as main component.In addition, the content of cis Isosorbide-5-Nitrae-polyisoprene be preferably more than 50 quality %, be more preferably more than 65 quality %, more preferably more than 80 quality %, be particularly preferably more than 90 quality %.
In addition, as polyisoprene, polyisoprene on the market can be used, such as, can exemplify NIPOL IR series (Japanese Zeon (strain) system).
With regard to divinyl, it is known that according to catalyzer, reaction conditions, be polymerized by 1,2-or Isosorbide-5-Nitrae-addition, but the present invention can for the polyhutadiene being undertaken being polymerized by above-mentioned arbitrary addition.In the middle of these, from the view point of the mooney viscosity obtaining expectation, more preferably 1，4-polybutadiene is main component.
In addition, the content of 1，4-polybutadiene be preferably more than 50 quality %, be more preferably more than 65 quality %, more preferably more than 80 quality %, be particularly preferably more than 90 quality %.
In addition, the content of cis body and trans body is not particularly limited, as long as suitably select in the viscosity of expectation or the scope of mooney viscosity, from the view point of crosslinked and foaming rear performance caoutchouc elasticity, preferred cis body and preferably the content of cis 1，4-polybutadiene be more than 50 quality %, be more preferably more than 65 quality %, more preferably more than 80 quality %, be particularly preferably more than 90 quality %.
As polyhutadiene, commercially available product can be used, such as NIPOL BR series (Japanese Zeon (strain) system), UBEPOL BR series (the emerging product in space portion (strain) system) etc. can be exemplified.
As aqueous polyhutadiene, commercially available product can be illustrated, KurapreneLBR-305 ((strain) Kuraray system), Ricon (Sartomer society system) can be listed.
In addition, as aqueous polyisoprene, Kuraprene LIR-30, LIR-50 ((strain) Kuraray system) etc. can be listed.
As having (methyl) acrylate-based polyisoprene, the polyisoprene (Kuraprene US-203, UC-102, (strain) Kuraray system) such as importing methacrylic ester can be listed.
In addition, there is as end the polyhutadiene of ethylenically unsaturated group, can list and such as import (methyl) acrylate-based polyhutadiene (NISSO-PBTEAI-1000, EA-3000, Japanese Cao Da (strain) system).
In the middle of these, as there is the polymkeric substance of polybutadiene configuration and there is the polymkeric substance of polyisoprene structure, preferred polyisoprene, polyhutadiene, styrene isoprene styrene block copolymer (SIS) or styrene-butadiene-styrene block copolymer, particularly preferably polyisoprene or polyhutadiene further.
In addition, as composition A, from the view point of the printing resistance of flexible printing plate, the washability carving dregs, process, preferred polyhutadiene or polyisoprene, particularly preferably polyhutadiene.
(methyl) propenoic methyl carbamate is the urethane resin at main chain inside, main chain terminal or side chain with (methyl) acryloxy, can list fatty family (methyl) propenoic methyl carbamate, fragrant family (methyl) propenoic methyl carbamate etc.In detail, can refer to oligopolymer handbook (Gu Chuan pure two supervises, (strain) chemical industry day newspaper office) (オ リ go マ mono-Ha Application De ズ Star Network (pure two Prison of Gu Chuan repair, (strain) chemical industry day Reported society)).
(methyl) propenoic methyl carbamate preferably also has at least a kind of key be selected from carbonic acid ester bond and ester bond in molecule.By (methyl) propenoic methyl carbamate, there is above-mentioned key, improve press plate to the black liquid clean-out system containing ester series solvent used in printing or the patience of black liquid clean-out system containing hydrocarbon system solvent.
As having the diatomic alcohol compounds with carbonic acid ester bond used in the manufacture of the urethane resin of hydroxyl, such as 4 can be listed, the Aliphatic Polycarbonatediols etc. such as 6-zinc-containing solid catalyst glycol, 8,9-zinc-containing solid catalyst glycol, 5,6-zinc-containing solid catalyst glycol.In addition, the polycarbonate diol with aromatic nucleus can be used.
By making hydroxyl and the tolylene diisocyanate of the end of these compounds, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, tetramethylxylene diisocyanate, Xylene Diisocyanate, naphthalene diisocyanate, trimethyl hexamethylene diisocyanate, to phenylene vulcabond, cyclohexylene diisocyanate, lysinediisocyanate, the diisocyanate cpds such as triphenylmethane diisocyanate, triphenylmethane triisocyanate, 1-methylbenzene-2, 4, 6-triisocyanate, naphthalene-1, 3, 7-triisocyanate, xenyl-2, 4, the polyisocyanate compounds such as tri-isocyanate compound such as 4 '-triisocyanate carry out condensation reaction, amino-formate bond can be imported.
For (methyl) propenoic methyl carbamate, as commercially available product, can obtain such as purple light series UV-3200, UV-3000B, UV-3700B, UV-3210EA, UV-2000B, UV-3630ID80 (more than, Japan synthetic chemistry (strain) system), EBECRYL230, EBECRYL9227EA (more than, Daicel-Cytec (strain)), AU-3040, AU-3050, AU-3090, AU-3110, AU-3120 of Hi-Coap AU series (more than, (strain) TOKUSHIKI system).
As the additive method obtaining (methyl) propenoic methyl carbamate etc., aforesaid polyisocyanate compound is made to carry out polyaddition reaction with the diatomic alcohol compounds with (methyl) acryloxy and generate the method etc. of urethane in addition.
As the preferred example with the diatomic alcohol compounds of (methyl) acryloxy now used, DA-212, DA-250, DA-721, DA-722, DA-911M, DA-920, DA-931, DM-201, DM-811, DM-832, DM-851 etc. of " Denacolacrylate " series that Blemmer GLM, Nagase ChemteX (strain) that day oil (strain) makes make can be listed.
The molecular weight of composition A, in weight-average molecular weight (GPC, polystyrene conversion), is preferably 1, more than 000, is more preferably 3, more than 000, more preferably 10, more than 000, be particularly preferably 25, and more than 000, most preferably be 80, more than 000.In addition, the molecular weight of composition A, in weight-average molecular weight (GPC, polystyrene conversion), is preferably 3,000, less than 000, is more preferably 2,000, less than 000, more preferably 1,500, less than 000.If above-mentioned scope, then the processing of resin composition for laser engraving becomes easy, and in addition, the printing resistance of the flexible printing plate obtained becomes more excellent.
In the present invention, weight-average molecular weight and number-average molecular weight are measured by gel permeation chromatography (GPC), and carry out converting with polystyrene standard and try to achieve.Specifically, such as GPC is as described below: use HLC-8220GPC (eastern Cao (strain) system), and use TSK geL Super HZM-H, TSKgeL Super HZ4000,3 of TSK geL Super HZ2000 (eastern Cao (strain) system, 4.6mmID × 15cm) as post, use THF (tetrahydrofuran (THF)) as elutriant.In addition, as condition, making that sample solution concentration is 0.35 quality %, flow velocity is 0.35ml/min, sample injection rate is 10 μ l, measuring temperature is 40 DEG C, and uses IR detector to carry out.In addition, typical curve utilizes eastern Cao (strain) to make " standard test specimen TSK standard, polystyrene ": 8 samples of " F-40 ", " F-20 ", " F-4 ", " F-1 ", " A-5000 ", " A-2500 ", " A-1000 ", " n-proplbenzene " make.
In the present invention, the mooney viscosity of composition A is not particularly limited, and from the angle of process accessibility when solvent solubility, mixing, is preferably less than 90, is more preferably less than 70, more preferably less than 60.In addition, the lower value of mooney viscosity is not particularly limited, and such as composition A can be aqueous or the state such as syrupy shape.
In the present invention, mooney viscosity is carry out measuring the value obtained based on JIS K6300-1.Specifically, carrying out forming cylindric space between temperature controlled mould as sample chamber, simultaneously at the central part configuration rotor of this sample chamber, determined sample is filled in sample chamber, under the state that this temperature is remained on specified temperature, with the rotating speed of regulation, rotor is rotated, utilize load cell (loadcell) to detect the counter torque of the rotor produced by the viscous resistance of the sample after melting, measure mooney viscosity thus.In addition, the value of the mooney viscosity used in the present invention uses L-type rotor and obtains, wherein 1 minute warm up time, rotor rotational time 4 minutes, the mooney viscosity of rubbery sample represents that at the 100 DEG C interval warming up period chien shih rotor of 1 minute rotates, after 4 minutes mooney viscosity (ML 1+4).
Relative to the total mass of resin composition for laser engraving, the content of composition A is more than 50 quality %, is preferably 50 ~ 95 quality %, is more preferably 55 ~ 90 quality %, more preferably 65 ~ 90 quality %, is particularly preferably 70 ~ 85 quality %.If the content of composition A is above-mentioned scope, then can obtain the relief layer of the washability excellence of engraving dregs, black liquid transitivity excellence.
Resin composition for laser engraving of the present invention can containing the binder polymer (resinous principle) except composition A.As the binder polymer except composition A, the binder polymer etc. recorded in the paragraph 0009 ~ 0030 of the inelastic body recorded in Japanese Unexamined Patent Publication 2011-136455 publication, the polymkeric substance containing unsaturated group recorded in Japanese Unexamined Patent Publication 2010-208326 publication, Japanese Unexamined Patent Publication 2012-45801 publication can be illustrated.
Resin composition for laser engraving of the present invention is when containing other binder polymers except composition A, relative to the total mass of resin composition for laser engraving, be preferably below 30 quality %, be more preferably below 10 quality %, more preferably below 5 quality %, be particularly preferably below 2 quality %, most preferably be 0 quality %, namely do not contain.If above-mentioned scope, then can obtain the relief layer of the washability excellence of engraving dregs, black liquid transitivity excellence.
As the binder polymer except composition A, preferably can illustrate ethylene-propylene-diene copolymer, more preferably can illustrate ethylene-propylene-5-ethylidene-2-norbornene multipolymer.
(composition B) polymerization starter
Resin composition for laser engraving of the present invention contains (composition B) polymerization starter.
Polymerization starter can use ad lib and well known to a person skilled in the art polymerization starter.Below, preferred polymerization starter and radical polymerization initiator are described in detail, but the present invention is not subject to the restriction that these describe.
As polymerization starter, preferred radical polymerization initiator.
In addition, as polymerization starter, be preferably thermal polymerization, be more preferably hot radical polymerization starter.
In the present invention, as preferred polymerization starter, (a) aromatic series ketone can be listed, compound, (1) Azo etc. that (b) salt compound, (c) organo-peroxide, (d) thio-compounds, (e) six aryl united imidazole, (f) ketooxime ester compounds, (g) boric acid ester compound, (h) azines, (i) Metallocenic compound, (j) active ester compound, (k) have carbon-halogen bond.Below can list above-mentioned (a) ~ the object lesson of (1), but the present invention is not limited to these compounds.
In the present invention, from the view point of carving sensitivity and making relief printing plate edge shape become good when being applicable to the relief printing plate form layers of flexible printing plate originals, more preferably as thermal polymerization, (c) organo-peroxide and (1) Azo, particularly preferably (c) organo-peroxide.
There is as above-mentioned (a) aromatic series ketone, (b) salt compound, (d) thio-compounds, (e) six aryl united imidazole, (f) ketooxime ester compounds, (g) boric acid ester compound, (h) azines, (i) Metallocenic compound, (j) active ester compound and (k) compound of carbon-halogen bond, the compound enumerated in the paragraph 0074 ~ 0118 of Japanese Unexamined Patent Publication 2008-63554 publication can be preferably used in.
In addition, as (c) organo-peroxide and (1) Azo, compound preferably shown below.
(c) organo-peroxide
Preferred (c) organo-peroxide as polymerization starter operable in the present invention, is preferably 3,3 ', 4,4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 3,3 ', 4,4 '-four (t-amyl peroxy carbonyl) benzophenone, 3,3 ', 4,4 '-four (tertiary hexyl peroxidation carbonyl) benzophenone, 3,3 ', 4,4 '-four (tertiary octyl group peroxidation carbonyl) benzophenone, 3,3 ', 4,4 '-four (cumyl peroxidation carbonyl) benzophenone, 3,3 ', 4,4 '-four (p-isopropyl cumyl peroxidation carbonyl) benzophenone, di-t-butyl diperoxy isophthalic ester, di-t-butyl diperoxy isophthalic ester, tert butyl peroxy benzoate, tert-butyl hydroperoxide-3-methyl benzoic acid ester, tert-butyl hydroperoxide laurate, t-butylperoxy pivarate, tert-butyl hydroperoxide-2-ethylhexanoate, tert-butyl hydroperoxide-3,5,5 Trimethylhexanoic acid ester, the new heptanoate of tert-butyl hydroperoxide, tert-butyl hydroperoxide neodecanoic acid ester, tert-butyl hydroperoxide acetic ester, α, α '-two (tert-butyl hydroperoxide) diisopropyl benzene, tert-butyl cumyl peroxide, ditertiary butyl peroxide, t-butylperoxyisopropyl monocarbonate, tert-butyl hydroperoxide-2-ethylhexyl monocarbonate, and the peroxyester system such as dicumyl peroxide.
(1) Azo
As preferred (1) Azo of polymerization starter operable in the present invention, can 2 be listed, 2 '-azobis isobutyronitrile, 2,2 '-azo is propionitrile in pairs, 1,1 '-azo two (hexanaphthene-1-formonitrile HCN), 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2,4-methyl pentane nitrile), 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile), 4,4 '-azo two (4-cyanopentanoic acid), 2,2 '-azobisisobutylonitrile dimethyl phthalate, 2,2 '-azo two (2-methyl propanamide oxime), 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-base) propane], 2,2 '-azo two { 2-methyl-N-[two (the methylol)-2-hydroxyethyl of 1,1-] propionic acid amide }, 2,2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionic acid amide], 2,2 '-azo two (N-butyl-2-methyl propanamide), 2,2 '-azo two (N-cyclohexyl-2-methyl propanamide), 2,2 '-azo two [N-(2-propenyl)-2-methyl propanamide], 2,2 '-azo two (2,4,4-trimethylpentane) etc.
In addition, in the present invention, from the view point of bridging property and the engraving sensitivity raising of film (relief printing plate form layers), particularly preferably above-mentioned (c) organo-peroxide is as the polymerization starter in the present invention.
From the view point of engraving sensitivity, the form that (c) organo-peroxide and (composition E) described later photothermal deformation agent combine particularly preferably will be somebody's turn to do.
This is because at use organo-peroxide when making relief printing plate form layers solidify by heat cross-linking, the unreacted organo-peroxide having neither part nor lot in free radical generation remains, but residual organo-peroxide plays the effect of the additive of self-reactive, generate heat when laser sculpture and decompose.Consequently, be estimated to be the laser energy irradiating generation and add that thus heating part is carved sensitivity and uprised.
In addition, be described in detail in the explanation of photothermal deformation agent, but its effect is more remarkable when using carbon black as photothermal deformation agent.This is considered to because also pass to (c) organo-peroxide from the heat of carbon black generation, and result not only carbon black but also organo-peroxide is also generated heat, and what thus should be used for the thermal energy of the decomposition of composition A etc. brings the effect be multiplied.
In the present invention, composition B only can use a kind, and also two or more kinds may be used.
Relative to the total mass of resin combination, the content of composition B contained in resin composition for laser engraving of the present invention is preferably more than 0.01 quality %, is more preferably more than 0.1 quality %, more preferably more than 0.5 quality %.In addition, the upper limit of the content of composition B is not particularly limited, but from the view point of the use level of other compositions, is preferably below 30 quality %, is more preferably below 20 quality %, more preferably below 10 quality %.If content is above-mentioned scope, then can obtain printing resistance and the more excellent flexible printing plate of black liquid transitivity, in addition, the washability of engraving dregs is more excellent.
(composition C) whipping agent
Resin composition for laser engraving of the present invention contains (composition C) whipping agent.
As whipping agent, can use known whipping agent, can be chemical foaming agent, also can be pneumatogen, but from as the treatability of resin combination or conservatory viewpoint, be preferably chemical foaming agent.
As chemical foaming agent, can be mineral compound, also can for organic compound, can also and use two or more.
As organic chemistry whipping agent, the azo-compounds, 4 such as nitrosamine compound, Cellmic C 121 (ADCA) such as such as dinitrosopentamethylene tetramine (DPT) can be listed, the hydrazine compounds etc. such as 4 '-oxygen biphenyl disulfonic acid hydrazides (OBSH) or hydrazo-dicarbonamide (HDCA).
As inorganic chemical foaming agent, the combination etc. of supercarbonate, carbonate, supercarbonate and the organic acid salts such as such as sodium bicarbonate can be listed.
Wherein, preferably have chemical machine whipping agent, be more preferably nitrosamine compound, azo-compound and hydrazine compound, more preferably azo-compound, be particularly preferably Cellmic C 121.
In addition, as the azo-compound being used as whipping agent, the free radical produced when preferably decomposing is amino radical (NH 2) etc. the compound of the low free radical of polymerization initiating power.
As pneumatogen, the inactive gas such as nitrogen, carbonic acid gas or volatile organic compounds etc. can be listed.Wherein, preferably use inactive gas, preferably use supercritical carbon dioxide, nitrogen or their mixture.
When using chemical foaming agent, being preferably mixed in resin combination, making relief printing plate form layers or crosslinked relief printing plate form layers, utilizing heat to make it foam.
When using pneumatogen, at normal pressure or pressure can be added, being mixed in resin combination, make relief printing plate form layers or crosslinked relief printing plate form layers, make it foam; Also can make relief printing plate form layers or crosslinked relief printing plate form layers, pneumatogen be impregnated in these layers, make it foam.
In addition, be particularly preferably after making relief printing plate form layers, foaming and crosslinkedly simultaneously carrying out at least partially of being caused by polymerization starter.
As foaming method, be not particularly limited, specifically, the method such as foaming, extruding foaming method, normal pressure foaming, normal pressure two steps foaming in batches can be listed.
In addition, as whipping agent, foaming method, can refer to Japanese Unexamined Patent Publication 11-106543 publication or the basis of the new edition rubber technology " change version (new edition go ム Ji Intraoperative Ji Foundation changes Order version) ", whipping agent that Japan rubber association records in compiling and foaming method.
Polymerization starter in resin composition for laser engraving of the present invention and the combination of whipping agent preferably at the same temperature, the combination of the decomposition of the generation that the polymerization produced from polymerization starter causes kind and whipping agent.
In addition, as the combination of the polymerization starter in resin composition for laser engraving of the present invention and whipping agent, preferably as organo-peroxide and the combination as the organic blowing agent of whipping agent of polymerization starter, be more preferably the organo-peroxide as polymerization starter and the nitrosamine compound as whipping agent, the combination of azo-compound or hydrazine compound, more preferably as the organo-peroxide of polymerization starter and as the nitrosamine compound of whipping agent or the combination of azo-compound, be particularly preferably the combination of the organo-peroxide as polymerization starter and the dinitrosopentamethylene tetramine as whipping agent or Cellmic C 121.If above-mentioned form, then easily make the cambial foaming of relief printing plate and be cross-linked as carrying out at least partially simultaneously, in addition, can obtain image quality and the more excellent flexible printing plate of black liquid transitivity, in addition, the washability of engraving dregs is more excellent.
In addition, except organo-peroxide and organic blowing agent, also preferably combine (composition F) described later frothing aid further.
Whipping agent can only use a kind, and also two or more kinds may be used, can also also with chemical foaming agent and pneumatogen.
Relative to the total mass of resin combination, the content of composition C contained in resin composition for laser engraving of the present invention is preferably 0.1 ~ 30 quality %, is more preferably 0.5 ~ 20 quality %, more preferably 1 ~ 15 quality %, be particularly preferably 2 ~ 10 quality %.If content is above-mentioned scope, then can obtain image quality and the more excellent flexible printing plate of black liquid transitivity, in addition, the washability of engraving sensitivity and engraving dregs is more excellent.
(components D) polymerizable compound
Resin composition for laser engraving of the present invention, in order to promote that crosslinking structure is formed, preferably also contains (components D) polymerizable compound.By containing components D, crosslinking structure is formed and is promoted, and the printing resistance of the flexible printing plate of gained is excellent.
In addition, components D is the polymerizable compound except composition A.
Further, components D is preferably molecular weight and is less than 3, the compound of 000, is more preferably molecular weight and is less than 2, the compound of 000, is more preferably less than molecular weight 1, the compound of 000.
Components D is preferably free-radical polymerised compound, in addition, is preferably alefinically unsaturated compounds.
In the present invention, operable polymerizable compound is preferably multifunctional polymerizable compound, is more preferably multifunctional alefinically unsaturated compounds.If above-mentioned form, then the solidified nature of resin combination is excellent, in addition, can obtain the flexible printing plate that printing resistance is more excellent.
In addition, in the present invention, operable multifunctional alefinically unsaturated compounds preferred molecular weight (or weight-average molecular weight) is less than 2,000.
Multifunctional alefinically unsaturated compounds refers to the compound with more than 2 ethylenically unsaturated groups.Multifunctional alefinically unsaturated compounds can be used alone a kind, also two or more kinds may be used.
In addition, the compound group belonging to alefinically unsaturated compounds is the material be widely known in the art, can be not particularly limited to use them in the present invention.They have such as monomer, prepolymer and dipolymer, trimer and oligopolymer or the chemical form such as these multipolymer and these mixture.
As above-mentioned multifunctional alefinically unsaturated compounds, preferably use polyfunctional monomer.The molecular weight of these polyfunctional monomers (being weight-average molecular weight when having molecular weight distribution) is preferably more than 200 and is less than 2,000, is more preferably 200 ~ 1,000, and more preferably 200 ~ 700.
As polyfunctional monomer, preferably there is the compound of 2 ~ 20 terminal ethylenic unsaturated groups.
As the example of polyfunctional monomer, unsaturated carboxylic acid (such as vinylformic acid, methacrylic acid, methylene-succinic acid, β-crotonic acid, iso-crotonic acid, toxilic acid etc.), its ester class, amides can be listed, preferably use the amides of the ester of unsaturated carboxylic acid and aliphatic polybasic alkylol cpd, unsaturated carboxylic acid and aliphatic polybasic amine compound.In addition, be also applicable to using there is the esters of unsaturated carboxylic acids of the nucleophilic substitution such as hydroxyl, amino base, amides and polyfunctional isocyanate's class, the addition reaction of epoxies, and the dehydration condensation thing etc. of polyfunctional carboxylic acid.In addition, preferably there is the addition reaction of the substituent esters of unsaturated carboxylic acids of electrophilicity, amides and the simple functions such as isocyanato-base, epoxy group(ing) or polyfunctional alcohols, amine, have that the detachment such as halogen radical, tosyloxy is substituent, esters of unsaturated carboxylic acids, amides and simple function or polyfunctional alcohols, amine substituted reactant.In addition, as other example, vinyl compound, allylic cpd, unsaturated phosphonic acids, vinylbenzene etc. also can be used to instead of above-mentioned unsaturated carboxylic acid and the compound group obtained.
From reactive viewpoint, ethylenically unsaturated group contained in above-mentioned polyfunctional monomer is preferably each residue of acrylate, methacrylic ester, vinyl compound, allylic cpd, is particularly preferably acrylate, methacrylic ester.
As the object lesson of the monomer of the ester of aliphatic polybasic alkylol cpd and unsaturated carboxylic acid, as acrylate, glycol diacrylate can be listed, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethyleneglycol diacrylate, 1,3 butyleneglycol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, polypropyleneglycol diacrylate, neopentylglycol diacrylate, 1,6 hexanediol diacrylate, Isosorbide-5-Nitrae-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, polytetramethylene glycol diacrylate, 1,8-ethohexadiol diacrylate, 1,9-nonanediol diacrylate, decamethylene-glycol diacrylate, Tricyclodecane Dimethanol diacrylate, Viscoat 295, trimethylolpropane tris (acryloxypropyl) ether, two trimethylolpropane tetra-acrylate, methylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetracrylate, diacrylate dipentaerythritol ester, dipentaerythritol acrylate, Sorbitol Powder triacrylate, Sorbitol Powder tetraacrylate, Sorbitol Powder five acrylate, Sorbitol Powder six acrylate, three (acryloyl-oxyethyl) isocyanuric acid ester, polyester acrylate oligomers etc.
As methacrylic ester, tetramethylene glycol dimethacrylate can be listed, ethylene glycol dimethacrylate, dimethacrylate, TEGDMA, polyethylene glycol dimethacrylate, dimethacrylate, dipropylene, tripropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate methacrylic ester, 1,3 butylene glycol dimethacrylate, HDDMA, 1,8-ethohexadiol dimethacrylate, 1,9-nonanediol dimethacrylate, decamethylene-glycol dimethacrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythritol tetramethylacrylate, Dipentaerythritol dimethacrylate, Dipentaerythritol hexamethacrylate, Sorbitol Powder trimethacrylate, Sorbitol Powder tetramethyl-acrylate, two (to (3-methacryloxy-2-hydroxy propyloxy group) phenyl) dimethylmethane, two (to (methacroyloxyethoxy) phenyl) dimethylmethane etc.
As the example of other esters, record in the ester with aromatic series pastern bone frame recorded in the fatty alcohol system ester class recorded in applicable use such as No. 46-27926, Japanese Patent Publication, No. 51-47334, Japanese Patent Publication, Japanese Laid-Open Patent Publication No. 57-196231 each publication or No. 59-5240, Japanese Laid-Open Patent Publication, No. 59-5241, Japanese Laid-Open Patent Publication, Japanese Unexamined Patent Publication No. 2-226149 each publication, Japanese Unexamined Patent Publication 1-165613 publication containing amino ester etc.
Above-mentioned ester monomer can also be used as mixture.
In addition, as the object lesson of the amide monomer of aliphatic polybasic amine compound and unsaturated carboxylic acid, methylene-bisacrylamide, methylenebismethacrylamide, 1 can be listed, 6-hexa-methylene is two-acrylamide, the two Methacrylamide of 1,6-hexa-methylene, diethylenetriamine three acrylamide, xylylene bisacrylamide, the two Methacrylamides of xylylene etc.
As the example of other preferred acid amides system monomers, the acid amides system monomer with cyclohexylene structure recorded in Japanese Patent Publication 54-21726 publication can be listed.
In addition, use the addition reaction of isocyanic ester and hydroxyl and the carbamate system addition polymerization compound that manufactures also is preferred, as its object lesson, the vinyl carbamate compound etc. making 1 molecule have the vinyl monomer containing hydroxyl shown in the polyisocyanate compound of the isocyanate group of more than 2 and following formula (i) to carry out containing the polymerizable vinyl of more than 2 in 1 molecule of addition recorded in such as Japanese Patent Publication 48-41708 publication can be listed.
CH 2＝C(R)COOCH 2CH(R’)OH (i)
(wherein, R and R ' represents H or CH respectively 3.)
In addition, the carbamate compounds class with oxyethane pastern bone frame recorded in the such urethane acrylate class recorded in No. 51-37193, Japanese Laid-Open Patent Publication, No. 2-32293, Japanese Patent Publication, Japanese Patent Publication No. 2-16765 each publication, No. 58-49860, Japanese Patent Publication, No. 56-17654, Japanese Patent Publication, No. 62-39417, Japanese Patent Publication, Japanese Patent Publication No. 62-39418 each publication is also preferred.
Further, by using that record in No. 63-277653, Japanese Laid-Open Patent Publication, No. 63-260909, Japanese Laid-Open Patent Publication, Japanese Unexamined Patent Publication No. 1-105238 each publication, that there is in molecule amino structure addition polymerization compounds, the resin combination solidified at short notice can be obtained.
As other examples, polyfunctional acrylate or the methacrylic esters such as the Epoxy Acrylates can list in No. 48-64183, Japanese Laid-Open Patent Publication, No. 49-43191, Japanese Patent Publication, Japanese Patent Publication No. 52-30490 each publication and record such polyester acrylate class, epoxy resin and (methyl) vinylformic acid being reacted.In addition, the specific unsaturated compound recorded in No. 46-43946, Japanese Patent Publication, No. 1-40337, Japanese Patent Publication, Japanese Patent Publication No. 1-40336 each publication, the vinyl phosphonate based compound etc. recorded in Japanese Unexamined Patent Publication 2-25493 publication can also be listed.In addition, in some cases, be applicable to using the structure containing perfluoroalkyl recorded in Japanese Laid-Open Patent Publication 61-22048 publication.And then, also can use with the compound of light solidified monomer and oligopolymer introduction in " Japan is association's will (Japan is Li Hui Chi then) then " vol.20, No.7,300th ~ 308 pages (1984).
As the simple function polymerizable compound only with 1 ethylenically unsaturated group, the polymerizable compound such as the unsaturated carboxylic acid classes such as vinylformic acid, methacrylic acid, methylene-succinic acid, β-crotonic acid, iso-crotonic acid, toxilic acid and their salt, the anhydrides with ethylenically unsaturated group, (methyl) esters of acrylic acid, (methyl) acrylic amide, (methyl) vinyl cyanide, styrenic and various unsaturated polyester resin, unsaturated polyester ether resin, unsaturated polyester amide resins, unsaturated urethane resin can be listed.
In addition, also can use there is the esters of unsaturated carboxylic acids of the nucleophilic substitution bases such as hydroxyl, amino, sulfydryl or the addition reaction of amides and isocyanates or epoxies and the dehydration condensation thing etc. with simple function or polyfunctional carboxylic acid.
Further, there is the addition reaction of the substituent esters of unsaturated carboxylic acids of electrophilicity such as isocyanato-base, epoxy group(ing) or amides and alcohols, amine, thio-alcohol, so have that the detachment such as halogen radical, tosyloxy is substituent, esters of unsaturated carboxylic acids or amides and alcohols, amine, thio-alcohol substituted reactant be also applicable to using.
In addition, as other example, unsaturated phosphonic acids, vinylbenzene, vinyl ether etc. also can be used to instead of above-mentioned unsaturated carboxylic acid and the compound group obtained.
As polymerizable compound, except using above-mentioned illustrative compound, known various compound can also be used without particular limitation, such as, compound etc. described in Japanese Unexamined Patent Publication 2009-204962 publication.
Further, as simple function alefinically unsaturated compounds, preferably can use (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, 2-ethylhexyl (methyl) acrylate, 2-hydroxyethyl (methyl) acrylate, butoxyethyl group (methyl) acrylate, (methyl) ethoxy ethoxyethylacrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, N-methylol (methyl) acrylamide, (methyl) acrylic acid derivatives such as (methyl) acrylic acid epoxy ester, NVP, the N-vinyl compound classes such as N-caprolactam, glycidyl allyl ether, Phthalic acid, diallyl ester, the derivative of the allylic cpds such as benzene tricarboxylic acid triallyl.
In the middle of these, as multifunctional alefinically unsaturated compounds, be preferably simple function (methyl) acrylic compound (simple function (methyl) acrylate).
In the middle of these, components D is preferably acrylate (acrylic compound) or methacrylic ester (methacrylate compound), is particularly preferably the ester of aliphatic polyol and acrylic or methacrylic acid.Components D is preferably in 1 molecule has 2 ~ 20 (methyl) acryloxies, more preferably has 2 ~ 8, preferably has 2 ~ 6 further, particularly preferably have 2 ~ 4.
In the middle of these, components D preferably comprises at least 1 compound be selected from two (methyl) vinylformic acid hexylene glycol ester, two (methyl) vinylformic acid decanediol ester, Tricyclodecane Dimethanol two (methyl) acrylate, four (methyl) acrylate, pentaerythritol and six (methyl) vinylformic acid dipentaerythritol ester.
Relative to the total mass of resin combination, the content of components D contained in resin composition for laser engraving is preferably 1 ~ 50 quality %, is more preferably 3 ~ 40 quality %, more preferably 5 ~ 30 quality %.If above-mentioned scope, then the cambial printing resistance of relief printing plate comprising resin composition for laser engraving is excellent.
In addition, from the view point of the generation improving printing resistance and suppression engraving dregs, relative to the total mass of resin combination, the content of components D contained in resin composition for laser engraving is preferably 10 ~ 50 quality %.
(composition E) photothermal deformation agent
Resin composition for laser engraving of the present invention is preferably also containing (composition E) photothermal deformation agent.That is, the photothermal deformation agent in the present invention is considered to be generated heat by the light of absorbing laser, thus the thermolysis of cured article when promoting laser sculpture.Therefore, the photothermal deformation agent of the light of optical maser wavelength of preferred Selective absorber for carving.
To the laser sculpture type flexible printing plate originals of resin composition for laser engraving manufacture of the present invention used to send 700 ~ 1, the ultrared laser (YAG laser, semiconductor laser, fibre laser, surface light emitting laser etc.) of 300nm as light source for laser sculpture when, as photothermal deformation agent, be preferably used in the compound that 700 ~ 1,300nm has maximum absorption wavelength.
As the photothermal deformation agent in the present invention, various dyestuff or pigment can be used.
In photothermal deformation agent, as dyestuff, the known dyestuff recorded in the commercially available dye well such as document such as " dyestuff brief guide " (Synthetic Organic Chemistry association edits, Showa 45 annual) can be utilized.Specifically, can list 700 ~ 1, there is under 300nm the dyestuff of maximum absorption wavelength, preferably can list the dyestuff such as azoic dyestuff, metal complex azo dyes, pyrazolone azoic dyestuff, naphthoquinone dyestuff, anthraquinone dye, phthalocyanine pigment, carbon (Carbonium) dyestuff, Diimmonium compound, quinonimine dye, methine dyes, cyanine dyes, side sour cyanines (squarylium) pigment, pyranium salt, metal thiolate complex.As the dyestuff preferably used in the present invention, the dyestuff recorded in the paragraph 0124 ~ 0137 of oxonols system pigment, phthalocyanine system pigment and the Japanese Unexamined Patent Publication 2008-63554 publication such as the cyanine system pigments such as cyanine methinecyanines pigment, five methyne oxonols pigments can be listed.
In the photothermal deformation agent used in the present invention, as pigment, commercially available pigment and Colour Index (C.I.) brief guide can be utilized, " up-to-date pigment brief guide " (Japanese pigment technology association compiles, 1977 annuals), " up-to-date pigment applications technology " (CMC publishes, 1986 annuals), " printing ink liquid technology " CMC publish, 1984 annuals) in the pigment recorded.In addition, as pigment, the pigment recorded in the paragraph 0122 ~ 0125 of Japanese Unexamined Patent Publication 2009-178869 publication can be illustrated.
In these pigment, preferably carbon black.
As long as the dispersiveness in carbon black composition etc. are stablized, then except the classification utilizing ASTM, no matter purposes (such as color with, rubber with, used for dry cell etc.), any one all can use possibility.Such as furnace black, thermals, thermally oxidized black, dim, acetylene black etc. is comprised in carbon black.In addition, the black colorants such as carbon black are owing to disperseing easily, and thus can be used as to use dispersion agent as required, be dispersed in the colour atla in Nitrocellulose or tackiness agent etc. or mill base in advance, such card or slurry easily can obtain as commercially available product.In addition, as carbon black, the carbon black recorded in the paragraph 0130 ~ 0134 of Japanese Unexamined Patent Publication 2009-178869 publication can be illustrated.
Photothermal deformation agent in resin combination of the present invention can only use a kind, also and use two or more.
The content of the photothermal deformation agent in resin composition for laser engraving has a great difference according to the size of the intrinsic molecule specific absorbance of its molecule, but relative to the total mass of resin combination, be preferably 0.01 ~ 30 quality %, be more preferably 0.05 ~ 20 quality %, be particularly preferably 0.1 ~ 10 quality %.
(composition F) frothing aid
Resin composition for laser engraving of the present invention is preferably also containing (composition F) frothing aid.By using frothing aid, the decomposition temperature of whipping agent and the size etc. of bubble easily can be adjusted.
As frothing aid, known material can be used, cause kind of an occurrence temperature (decomposition temperature), as long as be suitable for selecting kind or usage quantity according to the kind of used whipping agent and/or the polymerization of polymerization starter that uses.
As frothing aid, the organic acid compounds such as zn cpds, Whitfield's ointment, phthalic acid, stearic acid and oxalic acid, trolamine, the titanium whites etc. such as the Urea Series such as urea and urea derivative compound, the flowers of zinc (zinc oxide), zinc carbonate and Zinic stearas can be listed.
Wherein, preferred use Urea Series compound, zn cpds and/or organic acid compound, more preferably use Urea Series compound, preferably also use Urea Series compound, zn cpds and organic acid compound further.
Frothing aid only can use a kind, also two or more kinds may be used.
Relative to the total mass of resin combination, the content of frothing aid contained in resin composition for laser engraving of the present invention is preferably 0.1 ~ 20 quality %, is more preferably 0.5 ~ 15 quality %, more preferably 1 ~ 10 quality %, be particularly preferably 2 ~ 10 quality %.If content is above-mentioned scope, then can obtain image quality and the more excellent flexible printing plate of black liquid transitivity, in addition, the washability of engraving sensitivity and engraving dregs is more excellent.
Below, for except composition A ~ composition F, the various compositions that resin composition for laser engraving of the present invention can contain, are described.
< solvent >
When preparing resin composition for laser engraving of the present invention, can solvent be used, but preferably not use.
As solvent, preferably with an organic solvent.
As the preferred object lesson of non-proton organic solvent, acetonitrile, tetrahydrofuran (THF), diox, toluene, propylene glycol methyl ether acetate, methylethylketone, acetone, methyl iso-butyl ketone (MIBK), ethyl acetate, N-BUTYL ACETATE, ethyl lactate, N,N-dimethylacetamide, N-Methyl pyrrolidone, methyl-sulphoxide can be listed.
As the preferred object lesson of protic organic solvent, methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 1-methoxy-2-propanol, ethylene glycol, Diethylene Glycol, 1,3-PD can be listed.
In the middle of these, particularly preferably can illustrate propylene glycol methyl ether acetate.
As the content of the solvent in resin composition for laser engraving of the present invention, resin-phase, for the total mass of composition, is preferably below 10 quality %, is more preferably below 1 quality %, more preferably below 0.1 quality %, is particularly preferably and does not contain.
Other additives of < >
The known various additive of the suitable cooperation of the scope of effect of the present invention can not hindered in resin composition for laser engraving of the present invention.Can list such as fluidizer, weighting agent, paraffin, process oil, metal oxide, prevent ozone-decomposing agent, antiaging agent, stopper, tinting material etc., these can be used alone or two or more kinds may be used.
(laser sculpture type flexible printing plate originals and manufacture method thereof)
1st embodiment of laser sculpture type flexible printing plate originals of the present invention has the relief printing plate form layers comprising resin composition for laser engraving of the present invention.
In addition, the 2nd embodiment of laser sculpture type flexible printing plate originals of the present invention has the crosslinked relief printing plate form layers that the layer making to comprise resin composition for laser engraving of the present invention carries out foaming and being cross-linked.
In the present invention, " laser sculpture type flexible printing plate originals " refers to, the relief printing plate form layers with foaminess and bridging property comprising resin composition for laser engraving be foaming and crosslinked before state and foam by light and/or heat and crosslinked state both or any one.
In the present invention, " relief printing plate form layers " refers to, the layer of foaming and the state before being cross-linked, that is, for comprising the layer of resin composition for laser engraving of the present invention, can carry out drying as required.
By carrying out laser sculpture to having the cambial printing plate precursor of crosslinked relief printing plate, make " flexible printing plate ".
In the present invention, " crosslinked relief printing plate form layers " refers to, makes above-mentioned relief printing plate form layers carry out the layer foaming and be cross-linked.Above-mentioned foaming and crosslinked can be undertaken by hot and/or light.In addition, as long as the reaction that above-mentioned crosslinked resin combination is cured just is not particularly limited, the crosslinking structure caused by the reaction etc. of composition A and composition B can be illustrated.Above-mentioned foaming is the foaming caused by composition C, and the crosslinked relief printing plate form layers of gained has bubble.
In addition, in the present invention, " relief layer " refers to, the layer carved by laser in flexible printing plate, that is, the above-mentioned crosslinked relief printing plate form layers after laser sculpture.
Laser sculpture type flexible printing plate originals of the present invention have the resin composition for laser engraving comprised containing mentioned component relief printing plate form layers, make the layer of the resin composition for laser engraving comprised containing mentioned component carry out the crosslinked relief printing plate form layers foaming and be cross-linked.Relief printing plate form layers and crosslinked relief printing plate form layers are preferably arranged on supporter.
Laser sculpture type flexible printing plate originals can also have bonding coat as required between supporter and relief printing plate form layers or crosslinked relief printing plate form layers, in addition, can have smooth coating layer, protective membrane on relief printing plate form layers or crosslinked relief printing plate form layers.
< relief printing plate form layers >
Relief printing plate form layers is the layer of the resin composition for laser engraving comprising the invention described above, is preferably the layer of heat cross-linking.
As the making form of flexible printing plate utilizing laser sculpture type flexible printing plate originals, preferably relief printing plate form layers is made to carry out foaming and being cross-linked and after making and having the cambial flexible printing plate originals of crosslinked relief printing plate, by carrying out laser sculpture to crosslinked relief printing plate form layers (the relief printing plate form layers of hard), form the form that relief layer makes flexible printing plate.By making relief printing plate form layers be cross-linked, the wearing and tearing of relief layer when printing can be prevented, in addition, the flexible printing plate of the relief layer with clear shape can be obtained after laser sculpture.
Relief printing plate form layers is by being shaped to sheet by the resin composition for laser engraving with mentioned component of relief printing plate form layers or cannula-like is formed.Relief printing plate form layers is arranged on aftermentioned supporter usually, but also can be formed directly in or be configured in plate-making, the parts surface such as the rotating cylinder that possesses of device of printing makes it fix, and necessarily do not form supporter.
Below, be mainly illustrated for situation relief printing plate form layers being formed as sheet.
< supporter >
The raw material used in the supporter of laser sculpture type flexible printing plate originals is not particularly limited, the raw material that preferred size stability is high, can list such as, the metals such as steel, stainless steel, aluminium, the Plastic Resins such as polyester (such as PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PAN (polyacrylonitrile)) or polyvinyl chloride, the synthetic rubber such as styrene butadiene rubbers, the Plastic Resin (epoxy resin or resol etc.) with glass fiber reinforcement.As supporter, preferred PET film or steel substrate.The form of supporter can be sheet or cannula-like decides according to relief printing plate form layers.
< bonding coat >
When relief printing plate form layers is formed on supporter, the bonding coat of the cohesive force between can arranging between for strengthening layer.
As the material that can use in bonding coat (binding agent), the material recorded in such as I.Skeist volume, " Hand book of Adhesives ", the 2nd edition (1977) can be used.
< protective membrane, smooth coating (slip coat) layer >
In order to prevent causing damage on relief printing plate form layers surface or crosslinked relief printing plate form layers surface or form depression, protective membrane can be set on relief printing plate form layers surface or crosslinked relief printing plate form layers surface.The thickness of protective membrane is preferably 25 ~ 500 μm, is more preferably 50 ~ 200 μm.Protective membrane can use the polyester mesentery of such as PET and so on, the polyolefine mesentery of PE (polyethylene) or PP (polypropylene) and so on.In addition, delustring process also can be carried out in the surface of film.Protective membrane preferred peelable.
Situation about peeling off can not be carried out at protective membrane or under being difficult to be bonded in the cambial situation of relief printing plate on the contrary, also smooth coating layer can be set at two interlayers.The material preferably polyethylene alcohol, polyvinyl acetate, partly-hydrolysed polyvinyl alcohol, hydroxy alkyl cellulose, alkylcellulose, polyamide resin etc. that use in smooth coating layer are being dissolvable in water water or are being scattered in water and the low resin of binding property is main component.
There is no particular limitation for the manufacture method of laser sculpture type flexible printing plate originals, can list and such as prepare resin composition for laser engraving, as required from this laser sculpture with coating fluid composition except after desolventizing, the method that supporter melt extrudes.Also can be by resin composition for laser engraving curtain coating on supporter, then it is dry in stove, except the method for desolventizing from resin combination.
Wherein, the manufacture method of laser sculpture type flexible printing plate originals of the present invention preferably include formed comprise the layer of resin composition for laser engraving of the present invention operation and on make to comprise the layer stating resin composition for laser engraving carry out foaming and be cross-linked and formed be cross-linked the cambial operation of relief printing plate.
Then, as required, can at relief printing plate form layers upper strata voltage protection film.Lamination by with the stack etc. after heating protective membrane and relief printing plate to be formed lamination mode or surface infiltrate a small amount of solvent relief printing plate form layers on protective membrane is adhered to mode carry out.
When using protective membrane, first stacked relief printing plate form layers on protective membrane can be adopted, then by the method for supporter lamination.
When bonding coat is set, deal with by using the supporter being coated with bonding coat.When arranging smooth coating layer, deal with by the protective membrane being coated with smooth coating layer.
< layer formation process >
The manufacture method of laser sculpture type flexible printing plate originals of the present invention preferably includes: form the cambial layer formation process of relief printing plate comprising resin composition for laser engraving of the present invention.
As the cambial formation method of relief printing plate, can preferably illustrate following method: prepare resin composition for laser engraving of the present invention and rubber extruding to the method on supporter; Prepare resin composition for laser engraving of the present invention, after removing desolventizing as required from this resin composition for laser engraving, melt extrude to the method on supporter; Or prepare resin composition for laser engraving of the present invention, by resin composition for laser engraving curtain coating of the present invention on supporter, then by its dry method except desolventizing in stove.
Resin composition for laser engraving is by by such as following methods manufacture: such as mixing element A ~ composition C, further the method for mixing element D etc. successively arbitrarily again; Mixing element A and composition B, further any mixing element D etc. and prepare resin combination successively again, make composition C mix or the method for dipping afterwards; Make composition A ~ composition C and any composition etc. be dissolved or dispersed in suitable solvent, then, the method for any mixing element D etc., does not preferably use the method for solvent.Solvent composition preferably nearly all removes in the stage of manufacturing flexible printing plate precursor, thus as solvent, volatile low mass molecule alcohol (such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propylene glycol monomethyl ether) etc. is held in preferred use, and is suppressed to less by the total addition level of solvent after carrying out temperature adjustment etc. as far as possible.
The cambial thickness of (being cross-linked) relief printing plate in laser sculpture type flexible printing plate originals, in crosslinked front and back, is preferably more than 0.05mm below 10mm, is more preferably more than 0.05mm below 7mm, more preferably more than 0.05mm below 3mm.
< cross-linking process step >
The manufacture method of laser sculpture type flexible printing plate originals of the present invention is comprise the layer making to comprise resin composition for laser engraving to carry out foaming and being cross-linked and the manufacture method forming the crosslinked cambial cross-linking process step of relief printing plate.
Cross-linking process step preferably utilizes heat to carry out foaming and being cross-linked, or utilizes heat to carry out foaming, utilizing light to be cross-linked, and more preferably utilizes heat to carry out foaming and being cross-linked.
In addition, the foaming in cross-linking process step and crosslinked can simultaneously to carry out, also can carry out respectively, preferably carry out crosslinked after, to foam, or foaming and crosslinkedly simultaneously to carry out at least partially, more preferably foam and crosslinkedly to carry out at least partially simultaneously.When foam and crosslinked be when utilizing heat to carry out at least partially simultaneously, the method for carrying out under can listing the temperature of also decomposing at contained thermal polymerization and whipping agent.In addition, when utilize the foaming of heat and utilize light crosslinked be carry out at least partially simultaneously, limit can be listed and be heated to the method that the light that Photoepolymerizationinitiater initiater decomposes is irradiated on temperature limit that whipping agent decomposes.
Heating temperature in cross-linking process step can set arbitrarily according to the decomposition temperature of polymerization starter and whipping agent, be preferably 90 DEG C ~ 250 DEG C, be more preferably 100 DEG C ~ 180 DEG C, more preferably 100 DEG C ~ 160 DEG C, be particularly preferably 120 DEG C ~ 160 DEG C.If above-mentioned form, then easily can make the foaming of utilization heat and be cross-linked to carry out simultaneously.
As the heater means in cross-linking process step, can list printing plate precursor is heated in hotblast stove or far-infrared oven the specified time method, contact the method for specified time with the roller after heating.
In addition, the irradiation of the light in cross-linking process step is generally carried out the cambial whole face of relief printing plate.As light (also referred to as " active ray ".), visible ray, UV-light and electron beam can be listed, most preferably UV-light.If the substrate side being used for by the cambial supporter of relief printing plate etc. making relief printing plate form layers fixing is as the back side, then only effects on surface irradiates light, but if supporter is can the transparent film of transmission active ray, then preferred further from back side illuminaton light.When there is protective membrane, can carry out under the state that protective membrane is set when irradiating from surface, also can carry out after stripping protective membrane.In the presence of oxygen, likely hinder polymerization, therefore, vinylchlorid sheet can be covered on relief printing plate form layers, and the irradiation of active ray is carried out on evacuated basis.
The crosslinked relief printing plate form layers obtained through cross-linking process step has bubble by foaming on inner and surface.
Bubble in above-mentioned crosslinked relief printing plate form layers can be separated foam structure, can be also continuous air bubbles structure, from the view point of printing resistance and image quality, and preferred separated foam structure.
From the view point of printing resistance and image quality, the volume frothing percentage of the relief printing plate form layers in the present invention, crosslinked relief printing plate form layers or relief layer is preferably 10 ~ 200% respectively, is more preferably 50 ~ 180%, more preferably 70 ~ 140%.
Volume frothing percentage can measure the volume change before and after foaming, also can by crosslinked relief printing plate form layers after expanding or relief layer, and the cumulative volume of bubble portion calculates.
In addition, the volume mean diameter of the bubble in above-mentioned crosslinked relief printing plate form layers is preferably 0.1 ~ 20 μm, is more preferably 0.5 ~ 15 μm, more preferably 1 ~ 10 μm.If above-mentioned scope, then black liquid transitivity and image quality more excellent.
As the measuring method of the volume mean diameter of bubble in above-mentioned crosslinked relief printing plate form layers, can list and be cross-linked the cambial cross section of relief printing plate by optics or electron microscope observation and carry out method for measuring and take above-mentioned cross section and the method etc. of carrying out image procossing and calculating.
In addition, in cross-linking process step, from the view point of adjustment, the smoothness of the cambial frothing percentage of crosslinked relief printing plate of gained, can foam under the state by supporter or the cambial two sides of the substrate clamping such as supporter and heating device surface relief printing plate.In addition, from the view point of adjustment, the smoothness of the cambial frothing percentage of crosslinked relief printing plate of gained, the foaming under above-mentioned clamp position is preferably carried out under executing stressed state from least one face.
Further, can after cross-linking process step, supporter is peeled off from crosslinked relief printing plate form layers, in addition, from the view point of intensity, smoothness, after preferably supporter set during cross-linking process step being peeled off from crosslinked relief printing plate form layers, crosslinked relief printing plate cambial be provided with above-mentioned supporter face opposite side face on other supporters are set.
(flexible printing plate and method for platemaking thereof)
The method for platemaking of flexible printing plate of the present invention preferably includes: prepare flexible printing plate originals of the present invention preparatory process and to the engraving operation there is the cambial flexible printing plate originals of above-mentioned crosslinked relief printing plate carrying out laser sculpture.
Flexible printing plate of the present invention is the flexible printing plate with the relief layer that the layer making to comprise resin composition for laser engraving of the present invention carries out foaming and be cross-linked and laser sculpture obtains, the flexible printing plate that the method for platemaking preferably by flexible printing plate of the present invention is made a plate.
As the preparatory process in the method for platemaking of flexible printing plate of the present invention, preferably can list above-mentioned layer formation process and cross-linking process step, these operations are the operation identical with the layer formation process in the manufacture method of above-mentioned laser sculpture type flexible printing plate originals and cross-linking process step, and preferred scope is also identical.
< carves operation >
The method for platemaking of flexible printing plate of the present invention comprises the engraving operation to having the cambial flexible printing plate originals of above-mentioned crosslinked relief printing plate and carry out laser sculpture.
Engraving operation is carry out to crosslinked relief printing plate form layers crosslinked in above-mentioned cross-linking process step the operation that laser sculpture forms relief layer.Specifically, carve preferably by irradiating the laser light corresponding with the image expected to the crosslinked relief printing plate form layers after crosslinked, thus formation relief layer.In addition, preferably list to expect that the numerical data of the image formed is as foundation, computerized control laser probe, carries out scanning the operation of irradiating to crosslinked relief printing plate form layers.
The preferred infrared laser of this engraving operation.After having irradiated infrared laser, the molecule in crosslinked relief printing plate form layers produces molecular vibration, produces heat.As infrared laser, during the laser using the height of carbon dioxide laser or YAG laser and so on to export, laser irradiating part branch produces a large amount of heat, and molecule can occur the molecule in crosslinked relief printing plate form layers cuts off or ionization and optionally being removed, that is, engraving is realized.The advantage of laser sculpture can set carving depth arbitrarily, therefore, and can dimensionally control texture.Such as, during the part of the site of printed with fine, carve with regard to more shallow or band shoulder, like this would not relief printing plate overturning under the effect of squeegee pressure, when printing the ditch part of tiny hollow out word, just dark some engraving, like this, black liquid is just difficult to bury ditch thus hollow out word can be suppressed to be destroyed.
Wherein, when carving with the infrared laser of the absorbing wavelength corresponding to photothermal deformation agent, sensitivity that can be higher optionally removes crosslinked relief printing plate form layers, thus obtains having the relief layer of image clearly.
As can in the engraving operation infrared laser that use, from the viewpoint of productivity, cost, preferably carbon dioxide laser (CO 2laser) or semiconductor laser.Particularly preferably use the semiconductor infrared line laser (FC-LD) with fiber.Usually, semiconductor laser compares CO 2the efficiency of its laser generation of laser is high and can realize miniaturization cheaply.In addition, owing to being small-sized, therefore, easy array.And then, also can control shape of beam by fiber treatment.
As semiconductor laser, optimal wavelength is the laser of 700 ~ 1,300nm, more preferably the laser of 800 ~ 1,200nm, further preferably 860 ~ 1,200nm laser, the particularly preferably laser of 900 ~ 1,100nm.
In addition, the semiconductor laser of band fiber can be tieed up by installing optical fibres and Output of laser light effectively, is thus effective in engraving operation in the present invention.Further, by the process of fiber, shape of beam can be controlled.Such as, beam profile can form silk hat shape, stably can apply energy to the space of a whole page.Semiconductor laser at " laser handbook the 2nd edition (Japanese: レ mono-ザ mono-Ha Application De Block Star Network the 2nd edition) ", laser optics can be compiled, " practical laser technology (Japanese: real レ mono-ザ mono-skill Intraoperative) " electronic communication association compile etc. on the books.
In addition, use in the method for platemaking of the flexible printing plate of flexible printing plate originals of the present invention the automatic platemaker with the semiconductor laser of band fiber that can be applicable to using to be recorded in detail in Japanese Unexamined Patent Publication 2009-172658 publication and Japanese Unexamined Patent Publication 2009-214334 publication, also can use it for the plate-making of the flexible printing plate that the present invention relates to.
In the method for platemaking of flexible printing plate of the present invention, after engraving operation, then, further, following flushing operation, drying process and/or rear cross-linking process step can also be comprised as required.
Rinse operation: by the operation of the relief layer surface water after engraving or liquid wash sculpture surface using water as main component.
Drying process: dry operation is carried out to the relief layer after engraving.
Rear cross-linking process step: give energy to the relief layer after engraving, make relief layer carry out the operation be cross-linked further.
After above-mentioned operation, engraving dregs can be adhered at sculpture surface, therefore, also can add with water or take water as the liquid wash sculpture surface of main component, rinse the flushing operation of engraving dregs.As the method for rinsing, can list carry out washing with tap water method, spray injection high pressure water method, be used as the known batch-type of the developing machine of light-sensitive resin relief printing plate or the brush type washing machine of conveyance formula, sculpture surface is carried out under the existence mainly containing water the method etc. of scrubbing, when carve dregs not easily landing, also can use the washing fluid that with the addition of soap or tensio-active agent.
When carrying out the flushing operation of rinsing sculpture surface, preferably add the drying process that the relief printing plate form layers after dry engraving makes washing fluid volatilize.
In addition, the rear cross-linking process step making relief printing plate form layers crosslinked further can also be added as required.By carrying out the cross-linking process step i.e. rear cross-linking process step added, can make by carving the relief printing plate formed more firm.
In the present invention, operable washing fluid is preferably the washing fluid of pH8 ~ 14.If above-mentioned form, then the washability of the engraving dregs produced during laser sculpture is more excellent.
In addition, in the present invention the pH of operable washing fluid be more preferably more than 9, more preferably more than 10, be particularly preferably more than 11.In addition, the pH of washing fluid is more preferably less than 13.5, more preferably less than 13.2.If above-mentioned scope, then process becomes easy, and in addition, the washability of the engraving dregs produced during laser sculpture is more excellent.
In order to make washing fluid be above-mentioned pH scope, as long as suitably use acid and/or alkali adjustment pH, the acid used and alkali are not particularly limited.From viewpoints such as costs, as alkali, the oxyhydroxide of basic metal or alkaline-earth metal preferably can be listed.
In the present invention, operable washing fluid is preferably the water system washing fluid containing water as main component.
In addition, washing fluid can contain alcohols, acetone, tetrahydrofuran (THF) etc. water Combination solvent as solvent in addition to water.
Washing fluid is preferably containing tensio-active agent.
As the tensio-active agent that can use in the present invention, from the view point of the engraving removability of dregs and few on the impact of flexible printing plate, the betaine compounds (amphoterics) such as carboxybetaine compound, sulfobetaines alkali cpd, phosphorus base betaine compound, amine oxide or phosphine oxide preferably can be listed.
In addition, as tensio-active agent, known anion surfactant, cats product, nonionogenic tenside etc. can be listed.And then, also can use fluorine system, silicone-based nonionogenic tenside equally.
Tensio-active agent can be used alone or two or more kinds may be used.
The usage quantity of tensio-active agent there is no need to be particularly limited, and relative to the total mass of washing fluid, is preferably 0.01 ~ 20 quality %, is more preferably 0.05 ~ 10 quality %.
Thus, the flexible printing plate at arbitrary substrate surfaces such as supporters with relief layer is obtained.
From the view point of meeting the so various printabilities of wear resistant, black liquid transitivity, the thickness of the relief layer that flexible printing plate has is preferably more than 0.05mm below 10mm, is more preferably more than 0.05mm below 7mm, is particularly preferably more than 0.05mm below 3mm.
In addition, the Xiao A hardness of relief layer that flexible printing plate has is preferably more than 50 ° less than 90 °.If the Xiao A hardness of relief layer is more than 50 °, then the meticulous site formed by engraving would not be subject to the strong squeegee pressure of relief press and overturning damages, thus can print normally.In addition, when the Xiao A hardness of relief layer is below 90 °, even if then squeegee pressure is the printing style of calligraphy characterized by hollow strokes (patchy) that the flexible printing touched also can prevent part on the spot.
In addition, Xiao A hardness in this specification sheets is by 25 DEG C, clamp-oning pressure (also referred to as pressing or pressure head) on the surface of determination object makes it be out of shape, measure its deflection (the extruding degree of depth), and carried out the value that measures by the hardness tester (spring loaded durometer) quantized.
Flexible printing plate of the present invention is particularly suitable for utilizing the printing based on the aqueous ink of flexible printing machine, even if when use based on relief printing plate printing press aqueous ink, oiliness ink liquid and UV ink liquid in arbitrary black liquid also can print, in addition, the printing of the UV ink liquid utilized based on flexible printing machine can also be carried out.The washability of flexible printing plate of the present invention is excellent, engraving dregs can not remain, and the elasticity of the relief layer of gained is excellent, even thus aqueous ink transitivity and printing resistance excellent and long-term between also can implement printing, and there is no the worry that the viscous deformation of relief layer or printing resistance reduce.
Embodiment
Following illustrative embodiments and comparative example, carry out more specific description to the present invention.Wherein, the present invention is not subject to the restriction of these embodiments.In addition, " part " in below recording, when being not particularly limited, represents " mass parts ", " % " expression " quality % ".In addition, in table 1 described later, the unit of each numerical value is mass parts.
In addition, the number-average molecular weight (Mn) of the polymkeric substance in embodiment and weight-average molecular weight (Mw), as long as no when being particularly limited to, represent the value after utilizing GPC method to measure.
Described in being described in detail as follows of the composition used in each embodiment and comparative example.
< binder polymer >
UV-3000B: main chain terminal have acryloxy urethane acrylate (Mw:18,000, Tg:-39 DEG C, Japanese synthetic chemistry (strain) purple light processed UV-3000B, aqueous polymkeric substance, be thus plastomer.)
UV-3630ID80: main chain terminal has the urethane acrylate of acryloxy, and (thus Japanese synthetic chemistry (strain) purple light processed UV-3630ID80, aqueous polymkeric substance are plastomer.)
IR2200L: polyisoprene (mooney viscosity (ML 1+4, 100 DEG C): 70, Mw:135 ten thousand, Mn:472,000, Tg: about-60 DEG C, stretching permanent strain: 53%, Japanese Zeon (strain) NIPOLIR2200L processed)
BR150L: polyhutadiene (mooney viscosity (ML 1+4, 100 DEG C): 43, Mw:467,000, Mn:243,000, Tg: about-103 DEG C, stretching permanent strain: 63% space portion emerging product (strain) UBEPOLBR150L processed)
LBR305: aqueous polyhutadiene (Mn:26,000, Mw:2.8 ten thousand, (strain) Kuraray Kuraprene LBR-305, aqueous polymkeric substance, be thus plastomer.)
EPDM505: ethylene-propylene-5-ethylidene-2-norbornene multipolymer (is not equivalent to the binder polymer of composition A, mooney viscosity (ML 1+4, 125 DEG C): 59, Sumitomo Chemical (strain) EspreneEPDM505 processed)
D-1102: styrene-butadiene-styrene block copolymer (SBS resin, the binder polymer not being equivalent to composition A, Mw:10 ten thousand, stretching permanent strain: 0%, Kraton society KratonD-1102)
< polymerization starter >
PCD-40: dicumyl peroxide (organo-peroxide, day oil (strain) Percumyl D-40 processed, containing dicumyl peroxide 40%, 10 hr half-life temperature: 116.4 DEG C)
Irgacure651: Photoepolymerizationinitiater initiater, 2-phenyl-2,2-dimethoxy-acetophenone (IRGACURE651, Ciba-Geigy Ltd. system)
< whipping agent >
ADCA (Cellmic C 121, Tokyo change into industry (strain) system)
DPT (dinitrosopentamethylene tetramine, Tokyo change into industry (strain) system)
< frothing aid >
Urea (pharmaceutical worker industry (strain) system pure with light)
Zinc oxide (pharmaceutical worker industry (strain) system pure with light)
Stearic acid (pharmaceutical worker industry (strain) system pure with light)
< polymerizable compound >
HDDA: hexanediol diacrylate (Tokyo changes into industry (strain) system)
< photothermal deformation agent >
#45L: carbon black #45L (Mitsubishi Chemical's (strain) system, particle diameter: 24nm, specific surface area: 125m 2/ g, DBP oil number: 45ml/100g)
< additive >
ExpancelDU930-170 (thermal expansion microcapsule, particle diameter 28 ~ 38 μm, Japan Fillite Co., Ltd. system)
(embodiment 1 ~ 7)
The making > of < laser sculpture type flexible printing plate originals
The raw material recorded in table 1 beyond whipping agent, urea, zinc oxide, stearic acid and polymerization starter and table 2 described later will be removed in the composition recorded from table 1 described later, utilize LaboPlastomill ((strain) Toyo Seiki makes made) to carry out mixing (60 DEG C 20 minutes).Then, add whipping agent, urea, zinc oxide, stearic acid and polymerization starter, further mixing (80 DEG C 5 minutes), obtain resin composition for laser engraving.Utilize rubber forcing machine to be configured as the sheet of thickness 1mm the resin combination of gained, put it in process furnace, heat 80 minutes at 140 DEG C, make it carry out being cross-linked and foaming thus, obtain laser sculpture type flexible printing plate originals.
The making > of < flexible printing plate
For the resin composition layer (crosslinked relief printing plate form layers) after crosslinked, following 2 kinds of following laser are utilized to carve.
Use high-quality CO 2laser MARKER ML-9100 series (Keyence Corp. system), as carbon dioxide laser engraving machine, carries out the engraving utilizing laser radiation.With carbon dioxide laser engraving machine in output rating: 12W, probe speed: under the condition of 200mm/ second, spacing setting: 2,400DPI, the on the spot part square to 1cm carries out grating engraving.
As semiconductor laser engraving machine, use the laser recorder being equipped with semiconductor laser (FC-LD) SDL-6390 (JDSU Inc., wavelength 915nm) of the band fiber of peak power output 8.0W.With semiconductor laser engraving machine in laser power: 7.5W, probe speed: carry out grating engraving to the part on the spot that 1cm is square under the condition of 409mm/ second, spacing setting: 2,400DPI.
The engraving machine used is shown in table 2.In addition, " FC-LD " represents use semiconductor laser engraving machine, " CO 2" represent use carbon dioxide laser engraving machine.
(embodiment 8)
The raw material recorded in table 1 beyond whipping agent, urea, zinc oxide, stearic acid and polymerization starter and table 2 described later will be removed in the composition recorded from table 1 described later, use LaboPlastomill ((strain) Toyo Seiki makes made) to carry out mixing (60 DEG C 20 minutes).Then, add whipping agent, urea, zinc oxide, stearic acid and polymerization starter, further mixing (80 DEG C 5 minutes), obtain resin composition for laser engraving.The resin combination rubber forcing machine of gained is configured as the sheet of thickness 1mm, by its lateral dominance ultraviolet (UV) exposure machine being arranged at hot-plate, heat 80 minutes at 100 DEG C, while carry out ultraviolet exposure, make its crosslinked and foaming thus, obtain laser sculpture type flexible printing plate originals.
By carrying out laser sculpture to the laser sculpture type flexible printing plate originals of gained similarly to Example 1, obtain flexible printing plate thus.
(comparative example 1 ~ 3)
Except not foaming, all according to the step identical with embodiment 1, make laser sculpture type flexible printing plate originals except the raw material for recording in table 1 described later and table 2 and composition.
By carrying out laser sculpture to the laser sculpture type flexible printing plate originals of gained similarly to Example 1, obtain flexible printing plate thus.
-evaluation of laser sculpture type flexible printing plate originals and flexible printing plate-
By following project, carry out the performance evaluation of laser sculpture type flexible printing plate originals or the flexible printing plate obtained in embodiment and comparative example.Evaluation result is recorded in table 2 in the lump.
< carves sensitivity evaluation >
As described below, the crosslinked relief printing plate form layers measured flexible printing plate originals has carries out laser sculpture and " carving depth " of the relief layer obtained.Here, when " carving depth " refers to the cross section observing relief layer, the difference of the position (highly) after engraving and uncut position (highly).The cross section that " carving depth " in the present embodiment observes relief layer by ultra-deep look 3D measuring shape microscope VK9510 ((strain) Keyence system) measures.Carving depth refers to that greatly engraving is highly sensitive.
Engraving dregs amount residual in < version evaluates >
For the version after laser sculpture, by the presence or absence of the dregs in the surface of observation by light microscope relief layer, carry out relative evaluation.
< washability evaluates >
Version after laser sculpture be impregnated in water, by toothbrush (Lion (strain) system, the CLINICA TOOTHBRUSH FLAT) grooming 10 times of engraving portion.Then, the surface by opticmicroscope confirmation relief layer has and there is no dregs.Although do not have the A of being evaluated as dreggy, substantially do not have the B of being evaluated as dreggy on a small quantity residual dregs but practical no problem level be evaluated as C, fully cannot remove dregs be evaluated as D.
< ink liquid transitivity evaluates >
The flexible printing plate of gained is positioned over printing press (ITM-4 type, (strain) she to give machinery production made), as black liquid, use undiluted aqueous ink Aqua SPZ16 red (Japan's ink liquid manufacture (strain) system), as printing paper, use Full Color Form M70 (Nippon Paper (strain) system, thickness 100 μm), proceed printing, confirm highlighted 1 ~ 10% with print.
Start from printing, the degree of adhesion of the black liquid partly on the spot on the print of visual 1,000m also compares.
Metewand is as described below: evenly do not have density unevenness and have a small amount of gloss (to have gloss to refer to, the index that black liquid firmly shifts with corresponding thickness (amount).) be evaluated as A, evenly and do not have density unevenness be evaluated as B, entirety have uneven be evaluated as D, part has density unevenness is evaluated as C.More than B is evaluated as practical no problem level.
< quality evaluation >
Use FC-LD, press plate makes 130,150,3 of 1751pi engraving relief images, implement the UV ink liquid printing (UV ink liquid flexible 500CF, (strain) T & K TOKA system) of 10km, the print of observation by light microscope when 10km, will can reproduce the image quality of margin line number as this embodiment of carved image (line number) as print.Such as carve relief image made 130,150,3 images of 1751pi, as print, although can reproduce well at 1301pi and 1501pi, but cannot reproduce as carved relief printing plate when 1751pi, quality evaluation is 1501pi.
< printing resistance >
The flexible printing plate of gained is positioned over printing press (ITM-4 type, (strain) she to give machinery production made).As black liquid, use solvent inkjet ink liquid (XS-716 507 primary color blue (DIC GRAPHICSCORPORATION system)).As printing paper, use Full Color Form M70 (Nippon Paper (strain) system, thickness 100 μm), proceed printing, confirm highlighted 1 ~ 10% with print.The position creating the site that cannot print is set to be completed for printing, by until the length (km) of paper printed when being completed for printing is set to index.Numerical value is larger, is evaluated as printing resistance more excellent.
Table 1
Table 2

Claims (19)

1. a resin composition for laser engraving, is characterized in that, it contains following composition, that is,
Composition A: be selected from the binder polymer at least partially with ethylenic unsaturated bond in main chain inside, main chain terminal and side chain;
Composition B: polymerization starter; And
Composition C: whipping agent,
Composition A is selected from the plastomer in the polymkeric substance with polybutadiene configuration, the polymkeric substance with polyisoprene structure and (methyl) propenoic methyl carbamate,
Relative to the total mass of composition, the content of composition A is more than 50 quality %.
2. resin composition for laser engraving according to claim 1, wherein, composition A is polyhutadiene, polyisoprene or at least make the multipolymer of divinyl and/or isoprene copolymer.
3. resin composition for laser engraving according to claim 1 and 2, wherein, composition A is polyhutadiene or polyisoprene.
4. resin composition for laser engraving according to claim 1 and 2, wherein, composition B is organo-peroxide.
5. resin composition for laser engraving according to claim 1 and 2, wherein, composition C is chemical foaming agent.
6. resin composition for laser engraving according to claim 1 and 2, it also contains polymerizable compound as components D.
7. resin composition for laser engraving according to claim 1 and 2, it also contains photothermal deformation agent as composition E.
8. a laser sculpture type flexible printing plate originals, it has makes the layer of the resin composition for laser engraving comprised described in claim 1 or 2 carry out the crosslinked relief printing plate form layers foaming and be cross-linked.
9. a laser sculpture type flexible printing plate originals, is characterized in that, it has the crosslinked relief printing plate form layers that the layer making to comprise resin composition for laser engraving carries out foaming and being cross-linked,
Described resin composition for laser engraving contains following composition, that is,
Composition A: be selected from the binder polymer at least partially with ethylenic unsaturated bond in main chain inside, main chain terminal and side chain;
Composition B: polymerization starter; And
Composition C: whipping agent,
Composition A is selected from the plastomer in the polymkeric substance with polybutadiene configuration, the polymkeric substance with polyisoprene structure and (methyl) propenoic methyl carbamate, and relative to the total mass of composition, the content of composition A is more than 50 quality %.
10. laser sculpture type flexible printing plate originals according to claim 9, wherein, composition A is polyhutadiene, polyisoprene or at least make divinyl and/or isoprene carry out the multipolymer of copolymerization.
11. laser sculpture type flexible printing plate originals according to claim 9 or 10, wherein, composition A is polyhutadiene or polyisoprene.
12. laser sculpture type flexible printing plate originals according to claim 9 or 10, wherein, composition B is organo-peroxide.
13. laser sculpture type flexible printing plate originals according to claim 9 or 10, wherein, composition C is chemical foaming agent or pneumatogen.
14. laser sculpture type flexible printing plate originals according to claim 9 or 10, wherein, described resin composition for laser engraving also containing polymerizable compound as components D.
15. laser sculpture type flexible printing plate originals according to claim 9 or 10, wherein, described resin composition for laser engraving also containing photothermal deformation agent as composition E.
The manufacture method of 16. laser sculpture type flexible printing plate originals according to claim 9 or 10, it comprises following operation:
Form the operation comprising the layer of resin composition for laser engraving, described resin composition for laser engraving contains and is being selected from main chain inside as composition A, the binder polymer at least partially with ethylenic unsaturated bond in main chain terminal and side chain, as the polymerization starter of composition B, and as the whipping agent of composition C, composition A is selected from the polymkeric substance with polybutadiene configuration, there is the polymkeric substance of polyisoprene structure, and the plastomer in (methyl) propenoic methyl carbamate, relative to the total mass of composition, the content of composition A is more than 50 quality %, and
Make the layer comprising described resin composition for laser engraving carry out foaming and being cross-linked and form the crosslinked cambial operation of relief printing plate.
The manufacture method of 17. laser sculpture type flexible printing plate originals according to claim 16, wherein, described foaming and crosslinked simultaneously to carry out at least partially.
The method for platemaking of 18. 1 kinds of flexible printing plates, it comprises following operation:
Prepare laser sculpture type flexible printing plate originals according to claim 8 operation and
Laser sculpture is carried out to described crosslinked relief printing plate form layers and the engraving operation of formation relief layer.
The method for platemaking of 19. 1 kinds of flexible printing plates, it comprises following operation:
Prepare the operation of the laser sculpture type flexible printing plate originals described in claim 9 or 10; And
Laser sculpture is carried out to described crosslinked relief printing plate form layers and the engraving operation of formation relief layer.
CN201410822185.4A 2013-12-27 2014-12-25 Resin Composition For Laser Engraving, Flexographic Printing Plate Precursor For Laser Engraving And Process For Producing Same, And Process For Making Flexographic Printing Plate Pending CN104744923A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013271094A JP2015123714A (en) 2013-12-27 2013-12-27 Resin composition for laser-engraving, original plate for laser-engravable flexographic printing plate and method for producing the same, and platemaking method for flexographic printing plate
JP2013-271094 2013-12-27

Publications (1)

Publication Number Publication Date
CN104744923A true CN104744923A (en) 2015-07-01

Family

ID=52015964

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410822185.4A Pending CN104744923A (en) 2013-12-27 2014-12-25 Resin Composition For Laser Engraving, Flexographic Printing Plate Precursor For Laser Engraving And Process For Producing Same, And Process For Making Flexographic Printing Plate

Country Status (3)

Country Link
EP (1) EP2889138A1 (en)
JP (1) JP2015123714A (en)
CN (1) CN104744923A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107357135A (en) * 2016-04-25 2017-11-17 旭化成株式会社 Flexible printing plate photosensitive polymer combination, flexible printing plate photosensitive resin structure and flexible printing plate
CN115594919A (en) * 2022-10-19 2023-01-13 南京金陵塑胶化工有限公司（Cn） Polypropylene composite material and preparation method thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6494484B2 (en) * 2015-09-29 2019-04-03 住友理工株式会社 Flexographic printing plate precursor
DE102019119535A1 (en) * 2019-07-18 2021-01-21 Leonhard Kurz Stiftung & Co. Kg Method and device for transferring a transfer layer of a transfer film onto a substrate

Family Cites Families (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK125218B (en) 1967-11-09 1973-01-15 Kalle Ag Photosensitive recording material and photosensitive composition for use in the manufacture of the material.
DE2033769B2 (en) 1969-07-11 1980-02-21 Ppg Industries, Inc., Pittsburgh, Pa. (V.St.A.) Mixtures containing bis (2-acryloxyethyl) hexahydrophthalate and manufacturing processes
JPS4841708B1 (en) 1970-01-13 1973-12-07
DE2053683A1 (en) 1970-11-02 1972-05-10 Kalle Ag, 6202 Wiesbaden-Biebrich Photopolymerizable copying compound
DE2064079C2 (en) 1970-12-28 1982-09-09 Hoechst Ag, 6000 Frankfurt Photopolymerizable mixture
JPS5324989B2 (en) 1971-12-09 1978-07-24
JPS5230490B2 (en) 1972-03-21 1977-08-09
DE2361041C3 (en) 1973-12-07 1980-08-14 Hoechst Ag, 6000 Frankfurt Photopolymerizable mixture
JPS5311314B2 (en) 1974-09-25 1978-04-20
DE2822190A1 (en) 1978-05-20 1979-11-22 Hoechst Ag PHOTOPOLYMERIZABLE MIXTURE
DE2822189A1 (en) 1978-05-20 1980-04-17 Hoechst Ag PHOTOPOLYMERIZABLE MIXTURE
DE2952697A1 (en) 1979-12-29 1981-07-02 Hoechst Ag, 6230 Frankfurt POLYMERIZABLE MIXTURE BY RADIATION AND RADIATION-SENSITIVE COPY MATERIAL MADE THEREFOR
DE2952698A1 (en) 1979-12-29 1981-07-02 Hoechst Ag, 6230 Frankfurt PHOTOPOLYMERIZABLE MIXTURE AND PHOTOPOLYMERIZABLE COPY MATERIAL MADE THEREOF
DE3036694A1 (en) 1980-09-29 1982-06-03 Hoechst Ag, 6000 Frankfurt RUBBER-ELASTIC, ETHYLENICALLY UNSATURATED POLYURETHANE AND MIXTURE CONTAINING THE SAME BY RADIATION
DE3048502A1 (en) 1980-12-22 1982-07-22 Hoechst Ag, 6000 Frankfurt POLYMERIZABLE MIXTURE BY RADIATION AND RADIATION-SENSITIVE RECORDING MATERIAL MADE THEREOF
DE3120052A1 (en) 1981-05-20 1982-12-09 Hoechst Ag, 6000 Frankfurt POLYMERIZABLE MIXTURE BY RADIATION AND COPYING MATERIAL MADE THEREOF
JPS595241A (en) 1982-06-21 1984-01-12 ヘキスト・アクチエンゲゼルシヤフト Radiation polymerizable mixture
DE3223104A1 (en) 1982-06-21 1983-12-22 Hoechst Ag, 6230 Frankfurt PHOTOPOLYMERIZABLE MIXTURE AND PHOTOPOLYMERIZABLE COPY MATERIAL MADE THEREOF
DE3421511A1 (en) 1984-06-08 1985-12-12 Hoechst Ag, 6230 Frankfurt POLYMERIZABLE COMPOUNDS HAVING PERFLUORALKYL GROUPS, REPRODUCTION LAYERS CONTAINING THEM AND THEIR USE FOR WATERLESS OFFSET PRINTING
DE3710282A1 (en) 1987-03-28 1988-10-13 Hoechst Ag PHOTOPOLYMERIZABLE MIXTURE AND RECORDING MATERIAL MADE THEREOF
DE3710279A1 (en) 1987-03-28 1988-10-06 Hoechst Ag POLYMERIZABLE COMPOUNDS AND THIS CONTAINING MIXTURE MIXING BY RADIATION
DE3710281A1 (en) 1987-03-28 1988-10-06 Hoechst Ag PHOTOPOLYMERIZABLE MIXTURE AND RECORDING MATERIAL MADE THEREOF
DE3738864A1 (en) 1987-11-16 1989-05-24 Hoechst Ag POLYMERIZABLE COMPOUNDS AND THIS CONTAINING MIXTURE MIXING BY RADIATION
DE3817424A1 (en) 1988-05-21 1989-11-23 Hoechst Ag ALKENYLPHOSPHONE AND PHOSPHINIC ACID ESTER, METHOD FOR THE PRODUCTION THEREOF AND RADIATION POLYMERIZABLE MIXTURE THAT CONTAINS THESE COMPOUNDS
DE3843205A1 (en) 1988-12-22 1990-06-28 Hoechst Ag PHOTOPOLYMERISABLE COMPOUNDS, THIS CONTAINING PHOTOPOLYMERIZABLE MIXTURE, AND PRODUCED PHOTOPOLYMERIZABLE RECORDING MATERIAL THEREOF
JPH11106543A (en) 1997-08-02 1999-04-20 Bridgestone Corp Foamed rubber product
DE60124342T2 (en) * 2000-06-20 2007-05-31 Jsr Corp. Polymeric material for laser processing
JP2002103539A (en) 2000-09-29 2002-04-09 Jsr Corp Laminate for laser processing and flexography printing plate using it and their manufacturing method
JP2002003665A (en) 2000-06-20 2002-01-09 Jsr Corp Polymer material for laser beam machining and its flexographic printing plate and seal material
US6989220B2 (en) 2002-03-25 2006-01-24 Macdermid Printing Solutions, Llc Processless digitally imaged photopolymer elements using microspheres
WO2005070691A1 (en) 2004-01-27 2005-08-04 Asahi Kasei Chemicals Corporation Photosensitive resin composition for printing substrate capable of laser sculpture
JP2008063554A (en) 2006-08-11 2008-03-21 Fujifilm Corp Decomposable resin composition, pattern-forming material and pattern-forming method
JP2009172658A (en) 2008-01-25 2009-08-06 Fujifilm Corp Exposure apparatus
JP5241252B2 (en) 2008-01-29 2013-07-17 富士フイルム株式会社 Resin composition for laser engraving, relief printing plate precursor for laser engraving, relief printing plate and method for producing relief printing plate
JP5137618B2 (en) 2008-02-28 2013-02-06 富士フイルム株式会社 Resin composition for laser engraving, relief printing plate precursor for laser engraving, relief printing plate and method for producing relief printing plate
JP2009214334A (en) 2008-03-07 2009-09-24 Fujifilm Corp Printing plate making device and manufacturing method of printing plate
JP5451370B2 (en) 2009-12-28 2014-03-26 富士フイルム株式会社 Resin composition for laser engraving, relief printing plate precursor for laser engraving, method for producing relief printing plate precursor for laser engraving, plate making method for relief printing plate, and relief printing plate
JP2012045801A (en) 2010-08-26 2012-03-08 Fujifilm Corp Resin composition for laser engraving, relief printing plate precursor for laser engraving, method for producing relief printing plate, and relief printing plate
EP2602110A1 (en) * 2011-12-09 2013-06-12 Fujifilm Corporation Resin composition for laser engraving, flexographic printing plate precursor and process for its' production, flexographic printing plate and process for its' manufacture

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107357135A (en) * 2016-04-25 2017-11-17 旭化成株式会社 Flexible printing plate photosensitive polymer combination, flexible printing plate photosensitive resin structure and flexible printing plate
CN115594919A (en) * 2022-10-19 2023-01-13 南京金陵塑胶化工有限公司（Cn） Polypropylene composite material and preparation method thereof
CN115594919B (en) * 2022-10-19 2023-12-08 南京金陵塑胶化工有限公司 Polypropylene composite material and preparation method thereof

Also Published As

Publication number Publication date
JP2015123714A (en) 2015-07-06
EP2889138A1 (en) 2015-07-01

Similar Documents

Publication Publication Date Title
CN104049458A (en) Resin composition for laser engraving, flexographic printing plate precursor for laser engraving and process for producing same, and process for making flexographic printing plate
CN107249899B (en) Flexographic printing version
CN101398615B (en) Resin composition for laser engraving and resin printing plate precursor for laser engraving
CN101549597B (en) Relief printing plate precursor for laser engraving, relief printing plate, and method of manufacturing relief printing plate
EP3059091B1 (en) Flexo printing plate
CN104744923A (en) Resin Composition For Laser Engraving, Flexographic Printing Plate Precursor For Laser Engraving And Process For Producing Same, And Process For Making Flexographic Printing Plate
JP2010247527A (en) Relief printing plate original film for laser engraving, resin composition for laser engraving, relief printing plate, and method for manufacturing relief printing plate
CN101692150B (en) Method of manufacturing relief printing plate and printing plate precursor for laser engraving
CN107531071B (en) Flexographic printing version
CN102834273A (en) Original film for laser engraving type flexographic printing plate
CN104418982A (en) Resin composition for laser engraving, flexographic printing plate precursor for laser engraving and process for producing same, and flexographic printing plate and process for making same
CN107249900A (en) The manufacture method of flexographic printing version and flexographic printing version
CN103135345A (en) Resin composition for laser engraving, flexographic printing plate precursor for laser engraving and process for producing same, and flexographic printing plate and process for making same
EP2617773A1 (en) Resin composition for flexographic printing plate, laser-engraving type flexographic printing plate precursor and process for producing same, and flexographic printing plate and process for making same
CN102314080A (en) Laser engraving is with resin combination, laser engraving method for platemaking and the relief printing plate with letterpress plate originals, relief printing plate
CN104093572A (en) Resin composition for laser-engravable flexographic printing plate, original plate for laser-engravable flexographic printing plate and method for production thereof, and flexographic printing plate and method for production thereof
CN103376652A (en) Resin composition for laser engraving, flexible printing plate precursor, flexible printing plate, and process for making the flexible printing plate precursor and the flexible printing plate
CN102540712A (en) Resin composition for laser engraving, relief printing plate precursor for laser engraving and process for producing the same, and relief printing plate and process for making the same
CN104877289A (en) Resin Composition For Laser Engraving, Flexographic Printing Plate Precursor For Laser Engraving And Process For Producing Same, And Flexographic Printing Plate And Process For Making Same
CN102963110A (en) Process for producing flexographic printing plate precursor for laser engraving, and process for making flexographic printing plate
CN108698427B (en) Cylindrical printing plate, cylindrical printing plate precursor, and method for producing same
EP2738009A1 (en) Composition for laser engraving, relief printing original plate for laser engraving and production method therefor, production method for relief printing plate, and relief printing plate
CN104339821A (en) Process for producing flexographic printing plate precursor for laser engraving, flexographic printing plate precursor for laser engraving, process for making flexographic printing plate, and flexographic printing plate
CN102950870A (en) Process for producing flexographic printing plate precursor for laser engraving
JP5499144B2 (en) Resin composition for laser engraving, flexographic printing plate precursor for laser engraving and method for producing the same, and flexographic printing plate and method for making the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20150701

WD01 Invention patent application deemed withdrawn after publication