WO1993016414A1 - Composition photosensible destinee aux plaques flexographiques - Google Patents

Composition photosensible destinee aux plaques flexographiques Download PDF

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Publication number
WO1993016414A1
WO1993016414A1 PCT/JP1993/000152 JP9300152W WO9316414A1 WO 1993016414 A1 WO1993016414 A1 WO 1993016414A1 JP 9300152 W JP9300152 W JP 9300152W WO 9316414 A1 WO9316414 A1 WO 9316414A1
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Prior art keywords
rubber
gen
group
weight
photopolymerizable
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PCT/JP1993/000152
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English (en)
Japanese (ja)
Inventor
Kazunori Kanda
Hidefumi Kusuda
Hisao Sato
Chitoshi Kawaguchi
Yusuke Ninomiya
Sadayoshi Nakatsukasa
Toshihiro Fujii
Original Assignee
Nippon Paint Co., Ltd.
Hayakawa Rubber Co. Ltd.
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Application filed by Nippon Paint Co., Ltd., Hayakawa Rubber Co. Ltd. filed Critical Nippon Paint Co., Ltd.
Publication of WO1993016414A1 publication Critical patent/WO1993016414A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

Definitions

  • the present invention relates to a photosensitive composition for a flexographic plate material and a flexographic plate material obtained therefrom.
  • a rubber component is compounded together with the polymerizable monomer as a resin composition for the printing plate.
  • U.S. Pat.No. 3,674,486 and U.S. Pat.No. 4,332,636 and Japanese Patent 1,004,932 have an elastomeric block copolymer as a rubber component.
  • a photosensitive flexographic printing plate material is disclosed. However, since the elastomer itself does not cross-link at the time of photocuring, the resulting plate material has poor solvent resistance.
  • Japanese Patent Application Laid-Open Nos. Sho 62-165643 and Japanese Patent Application No. 2-208131 disclose a photopolymerizable oligomer for improving the crosslinkability of the composition and the above-mentioned elastomer component. Have been proposed. However, the compatibility between the oligomer and the rubber may be insufficient, and the resulting plate material becomes opaque and image reproducibility decreases. In addition, although the physical properties and chemical resistance are improved by the cross-linking of the oligomer, the solvent resistance of the obtained printing plate is still insufficient. Solvent ink resistance of the obtained plate material is still insufficient.
  • the present invention relates to (l) (a)
  • R is an alkylene group or a polyoxyalkylene group having 2 to 8 carbon atoms, is H or CH 3 group, and R 2 and R 3 are a part obtained by removing a dicocyanate group from a diisocyanate compound, and R 4 is a molecular weight.
  • R 5 is an alkylene group having 2-8 carbon atoms in the formula, and polyoxyalkylene groups, R e and R 7 are H, CH 3, or (meth) ⁇ methacryloyl Ruo Kin group, certain stomach Ariruokishi group X) is a residue excluding the hydroxyl group of the dihydric alcohol represented by the following formula, X is a portion of the diene liquid rubber having a hydroxyl group, excluding the hydroxyl group, is an integer of 1 to 4, 1 m 4, n is 1 to: I indicates an integer of 6)
  • a photopolymerization initiator relates to a photosensitive composition for flexographic printing plate materials containing 0.1 to 20% by weight.
  • a photopolymerizable gen-based urethane-modified acrylate (a) represented by the general formula (1) is reacted with a gen-based elastomer (b) and further a liquid rubber (c). It has been found that the resulting photopolymerizable composite rubber (or simply the composite rubber) has extremely excellent manufacturability, image quality, printing plate physical properties, and chemical resistance as a binder resin for flexographic printing plate materials.
  • the compounded rubber shown in the present invention is a compounded rubber having a new function, and is obtained by simply mixing components (a) and (b), and furthermore, component (c) as conventionally performed. Flexographic plates consisting of uncomposited compositions are not It has excellent performance and its manufacture is relatively easy.
  • a photopolymerizable rubber in which a photopolymerizable group is introduced into a polymer rubber molecule can be produced.
  • a dissolving or desolvating agent can be used. It is a simple process that does not require a process.
  • the complexing reaction must be performed while controlling the gelling reaction.
  • the resulting photopolymerizable composite rubber is Even afterwards, since it has sufficient photopolymerizability, it has the characteristic of giving a plate with excellent physical properties and chemical properties when used for flexographic plate materials.
  • the photopolymerizable gen-based urethane-modified acrylate oligomer (photopolymerizable oligomer) component (a) used in the present invention is represented by the general formula (1).
  • the photopolymerizable oligomer is obtained mainly by reacting a gen-based liquid rubber having a hydroxyl group, an ethylenically unsaturated monomer having a monovalent hydroxyl group, a dihydric alcohol and a diisocyanate compound. It is something that can be done.
  • Examples of the gen-based liquid rubber having a hydroxyl group include, for example, 1.2-polybutadiene, 1,4-polybutadiene, 1,2-pentadiene, polyisoprene, chloroprene, styrene-butadiene copolymer having a hydroxyl group in the molecule, There are acrylonitrile-butadiene copolymer and the like, and these can be used alone or in combination.
  • the number average molecular weight of the polymer of the gen-based liquid rubber having a hydroxyl group is from 1000 to 100,000, and the hydroxyl valence in the molecule (is 1 ⁇ m ⁇ 4.
  • the crosslink density is low, the solid state maintainability of the photocured product is not satisfied, and if m> 4, the composition becomes too hard and the elasticity is reduced, so that the desired rubber elasticity cannot be obtained.
  • Examples of the above-mentioned ethylenically unsaturated monomers having a monovalent hydroxyl group include 2-hydroxyhexyl acrylate and 2-hydroxyxethyl methacrylate. And 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and polypropylene glycol mono (meth) acrylate, and at least one of these can be used.
  • diisocyanate compound examples include, for example, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and methylene bis (4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate and the like.
  • At least one compound is compounded in an amount of 5 to 190 parts by weight based on 10 parts by weight of the liquid rubber.
  • R 5 represents an alkylene group having 2 to 8 carbon atoms and a polyoxyalkylene group
  • R 6 and R 7 represent H, CH 3 , or (meth) acryloyloxy group or aryloxy group
  • a dihydric alcohol having a skeleton represented by R in the above formula ⁇ ⁇ and a dihydric alcohol having a photopolymerizable ethylenically unsaturated group can be used.
  • the dihydric alcohol of the above formula (1) include, for example, ethylene glycol, ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1.3-butanediol, and 1,4-butanediol. , 1,5-pentanediol, 1,6-hexanediol, and the like.
  • examples of the dihydric alcohol having a photopolymerizable ethylenically unsaturated group include trimethylolpropane monoacrylate, trimethylolprono, Monomethacrylate, glycerol ⁇ -monoallyl ether and the like. At least one of these dihydric alcohols can be used.
  • the blending ratio of the above components is as follows. Assuming that the repeating unit of the urethane bond is n, the molecular weight is not more than 2000 with respect to 1 mol of a gen-based liquid rubber having a hydroxyl group valence of m (1 14;) in one molecule.
  • the dihydric alcohol having a molecular weight of 300 or less is mx n mol
  • the diisocyanate compound is nx (n + 1) mol
  • the monohydric ethylenically unsaturated monomer having a hydroxyl group is mmol.
  • the n part means the length of the part forming the hard segment with respect to the rubber molecular chain (soft segment).
  • the long hard segment is formed of a series of urethane bonds having high polarity and cohesion, and causes microscopic phase separation with a rubber molecule chain (soft segment) having low polarity and cohesion.
  • the photopolymerizable gen-based urethane-modified acrylate used in the present invention or the photopolymerizable oligomer alone can give a high-strength, high-elongation photocured product by irradiation with an active energy ray.
  • a dihydric alcohol containing R 4 having a molecular weight of 2000 or more phase separation between the hard segment and the soft segment becomes difficult to occur, and the desired purpose cannot be achieved, and therefore, R 4 is contained.
  • the molecular weight of the dihydric alcohol is preferably 2000 or less, particularly preferably 300 or less. Such a dihydric alcohol having a molecular weight of 2000 or less is introduced into the skeleton of the hard segment component.
  • the photopolymerizable oligomer includes a hard segment composed of a repeating urethane bond formed from the above formula (1) and a diisocyanate compound, and a soft segment composed of the X part of the above formula (1), that is, a skeleton of a gen-based liquid rubber. of It consists of two segments.
  • the synthesis of the photopolymerizable oligomer will be specifically described.
  • dibutyltin dilaurate, tin octoate, triethylamine, and triethylenediamine are added to a diisocyanate compound [ ⁇ ( ⁇ + 1)] mole.
  • a small amount of a dihydric alcohol (nixn) having a molecular weight of 2,000 or less is added and reacted in the presence of a catalyst such as min to obtain a compound having isocyanate groups at both ends.
  • the reaction temperature in this case is 10-120, preferably 40-80. Should be C.
  • a mole of an ethylenically unsaturated monomer having a monovalent hydroxyl group is gradually added and reacted to obtain a compound having an isocyanate group at one terminal, and then a divalent hydroxyl group is added thereto. 1 mol of the gen-based liquid rubber is gradually added. Hydroquinone, t-butylcatechol, 0-dinitrophenol, m-dinitrophenol, p-ditrophenol, 2,4-dinitrophenol are used in this synthesis reaction as necessary to suppress thermal polymerization.
  • a photopolymerizable oligomer represented by the above formula (1) having a rubber skeleton structure and having an acryloyloxy group, a methacryloyloxy group or a mixture thereof can be synthesized.
  • the gen-based elastomer (b) in which at least one Tg compounded in the composition for a photosensitive flexographic printing plate material of the present invention has a conjugated genomonomeric content of at least 30 ° C. or less in one molecule is used. (Preferably at least 40%), a molecular weight of 5,000 to 1,000,000 (preferably 10,000 to 500,000) and at least one glass transition.
  • Typical elastomers include, for example, polymers of conjugated gen-based compounds and copolymers of conjugated or conjugated gen-based compounds with monoolefinic unsaturated compounds. These are prepared according to polymerization techniques known to those skilled in the art.
  • An elastomer having at least one Tg of less than or equal to o ° c refers to an elastomer having at least one Tg below 0 °, and includes one Tg such as a general elastomer. And that is o. c) or less, 2) Includes thermoplastic elastomers that have two or more Tg, one of which is 0 ° C or less and the other is 0 or more.
  • the Tg of the elastomer varies depending on the measurement method, but can be easily determined by the DSC method, the TMA method, the DMA method, the viscoelasticity measurement method, or the like.
  • Examples of the conjugated diene compound used for the preparation of the elastomer (b) include butadiene, isoprene, and chloroprene. One or more of these may be used.
  • Examples of the monoolefinic unsaturated compound include styrene, -methylstyrene, 0-methylstyrene, in-methylstyrene, p-methylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, Examples include acrylates and methacrylates. In the combination of a conjugated gen-based compound and a monoolefin-unsaturated compound, one having a block copolymer structure is desirable.
  • the gen-based elastomer (b) in which at least one of the Tg is 0 ° C. or lower include a butadiene polymer, an isoprene polymer, Natural rubber, 1,2-boributadiene rubber, butyl rubber, pentadiene rubber, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-chloroprene copolymer, acryl nitrile-butadiene copolymer, acryloni Tris-isoprene copolymer, acrylonitrile-chloroprene copolymer, methyl methacrylate butadiene copolymer, methyl methacrylate isoprene copolymer, methyl methacrylate-chloroprene copolymer, methyl butyl acrylate Copolymer, methyl acrylate-isoprene copolyly
  • the two components described above are mixed with a gen-based liquid rubber (c) as necessary, and a compounding reaction is carried out under conditions that do not cause gelation.
  • the diene-based liquid rubber (c) include polyisoprene, 1,2-polybutadiene, 1,4-polybutadiene, 1,2-1 pentadiene, ethylene-butadiene copolymer, acrylonitrile-tagenecopoly-1, and modified products thereof.
  • At least one compound selected from the group consisting of a liquid at room temperature and having a molecular weight of 500 to 2000 is exemplified.
  • the gel fraction is controlled to 0.5% or less, preferably 0.2% or less by reacting under conditions where gelation does not occur.
  • conditions under which complexation occurs but three-dimensional cross-linking does not occur are merely expressed in terms of gel fraction, and a desirable condition of substantially zero can be naturally included. If the gel fraction is larger than 0.5%, it will be difficult to handle when used as a resin for flexographic plate materials, it will be difficult to develop and dissolve, and the target plate material performance will not be obtained. Cause problems.
  • the conditions under which gelation does not occur may be performed under any conditions.
  • the reaction may be performed at a low temperature for a long time so that the reaction can be controlled.
  • such a condition is satisfied by reacting at a temperature of 100 to 200 and a pressure of 5 to 200 kg / cm 2 in the presence of a gelling inhibitor. I can do it.
  • Examples of typical anti-gelling agents include amines (for example, naphthylamine, diphenylamine, phenylenediamine, etc.), quinoline (for example, a polymer of 2,2.4-trimethyl-1,2-dihydroquinoline, 6 —Ethoxy-1,2,2,4-trimethyl-1,2-dihydroquinoline, etc., hydroquinone derivatives (eg, 2,5-di (t-amyl) hydroquinone, 2,5-di-t-butylhydroquinone, hydroquinone monomethyl ether Etc.), monophenols (eg, 1-hydroxy-13-methyl-4-isopropylbenzene, 2,6-dibutyl phenol), bis-1, tris, or triphenols (eg, 2, 2 ' Ethylene-bis-1-methyl-6-t-butylphenol), 2,2-methylenebis (4-methyl-16-cyclohexylphenol), etc.
  • amines for example, naphthylamine
  • Obisphenols for example, 4,4'-thiobis (6-t-butyl-3.3-methylphenol)
  • hindered phenols for example, 4,4'-thiobis (6-t-butyl-3.3-methylphenol)
  • hindered phenols phosphites, ditroso, aniline point of 40 to 9
  • examples include a naphthenic process oil containing a naphthene component at 5 ° C as a main component, a coumarone indene resin, a rosin resin, a phenol resin, and a petroleum hydrocarbon resin.
  • These anti-gelling agents are generally known as anti-aging agents, and are listed in “Rubber Rubber Plastic E-Chemicals (Latest Version)”, Rubber Dignist Co., Ltd., published March 30, 1989. Pp. 68-127 and 481-484.
  • the temperature of the internal reactant is raised to 100 to 200 ° C while the frictional heat is generated by mixing and kneading the above-described raw materials and simultaneously using a heating device, and the pressure applied to the internal reactant is increased by 5 ° C.
  • the machine is set and operated so that the shearing force acts as a high shearing force on the reactant in the working section of the rotary kneading device while adjusting to ⁇ 20 O kg / cin 2 to perform the compounding reaction.
  • the complexing reaction is usually carried out by a kneader such as a hot roll, a pressure kneader, an extruder, a planetary mixer, a Banbury mixer and a mixer.
  • a closed kneader is particularly suitable.
  • the most important reaction conditions are temperature control and internal pressure control.
  • the temperature it is necessary to employ a kneading method and apparatus in which the content reactants have a uniform temperature distribution. It is thought that the conjugation reaction is mainly caused by the reaction between gen bonds between molecules.
  • the reaction temperature is 110 to 200, preferably 100 to 180 ° 0; and more preferably 100 to 150.
  • Another control factor is the control of the pressure on the internal reactants. It is necessary to adjust the pressure to 5 to 200 kg / cm 2 , preferably 15 to 200 kg / cm 2 , more preferably 30 to 190 kg / cm 2 .
  • the pressure In order to efficiently react the photopolymerizable gen-based urethane-modified acrylate (a) with the gen-based elastomer (1), it is necessary to make the components uniformly and well compatible with each other and to make the reaction sites close to each other. When these (a) and (b) have different viscosities or have insufficient compatibility, it is difficult to achieve a sufficiently uniform state by the ordinary kneading method.
  • a raised closed kneader is preferably used.
  • the degree of the reaction of the composite reaction product of the present invention can also be confirmed by measuring the molecular weight and viscosity of the obtained rubber.
  • the reactants are dissolved in an organic solvent before the complexation reaction, and the molecular weight and molecular weight distribution are measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • Photopolymerizable gen-based urethane modified resin In the acrylate (a) and high molecular weight regions, peaks due to the gen-based elastomer (b) are observed.
  • the peak of (a) disappears, so that the conjugation of the oligomer to the rubber can be confirmed.
  • the photopolymerizable composite rubber for the flexographic printing plate material one having the peak (a) disappeared and having a gel fraction of 0 is preferable.
  • the viscosity is determined by measuring the resin viscosity with a viscometer, such as a M-212 viscometer or a flow tester.
  • a viscometer such as a M-212 viscometer or a flow tester.
  • a method of reading a change in the current value of the kneading drive section flowing into the kneader is preferable.
  • a mastication accelerator or a peptizer may be added.
  • the compounding reaction can be facilitated by enhancing the effect of mastication and obtaining the effect of the mastication solution.
  • a peptizer that is effective at both high temperature and high temperature, and it is possible to add sulphide or aromatic sulfur compounds such as 2-benzamide thiophenol for low-temperature use, and lysyl mercaptan for high-temperature use. .
  • tackifiers such as alkylphenol formaldehyde resins and modified resins thereof, alkylphenol acetylene resins, cumarone Indene resin, xylene formaldehyde resin, petroleum hydrocarbon resin, polybutene, hydrogenated rosin, and processed products thereof may be combined.
  • a ⁇ -phenylenediamine compound, a fuynol compound, a paraffinic compound or the like may be added.
  • another elastomer (2) is compounded as a binder in addition to the composite rubber.
  • Such elastomers have a molecular weight of 1000 to 1, 000, 0000, preferably 50,000 to 500, 000. Further, at least one of these elastomers has a glass transition temperature of at most 110, preferably at most 130 ° C.
  • Good compatibility includes not only the fact that the appearance does not cause turbidity due to mixing, but also the good physical performance of a film.
  • elastomer component (2) examples include butadiene polymer, isoprene polymer, chlorobrene polymer, styrene butadiene copolymer, styrene-isoprene copolymer, styrene-chloroprene copolymer, Acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, acrylonitrile-chlorobrene copolymer, methyl methacrylate butadiene copolymer, methyl methacrylate-isoprene copolymer, methyl methacrylate-chloroprene copolymer, Methyl butadiene acrylate copolymer, methyl acrylate-isoprene copolymer, methyl acrylate-chloroprene copolymer, acrylonitrile-butadiene-styrene copolymer,
  • Examples of the polymerizable compound (3) having at least one addition-polymerizable group in the molecule include a carboxyl group ⁇ sulfone group-containing monomer: (meth) acrylic acid, styrene-p-sulfonic acid, Hydroxyl group-containing monomers; for example, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, aryl alcohol , Methallyl alcohol, N- (4-hydroxyphenyl) acrylamide or N- (4-hydroxyphenyl) methacrylamide, o-, m-, p-hydroxystyrene, 0-, m-, p-hydroxyphenyl Two acrylates or one methacrylate, alkyl acrylate Or methacrylate; for example, methyl (meth) acrylate, ethyl (meth)
  • Examples of compounds having at least two groups capable of addition polymerization include trimethylolpropane di (meth) acrylate, trimethylolpropanetri
  • the photopolymerizable initiator (4) is a compound having a function of initiating addition polymerization by light irradiation. Examples of such a compound include benzoin ethers (for example, benzoin isopropyl ether, benzoin isobutyl).
  • Benzophenones eg, benzophenone, methyl-10-benzoinbenzoate, 4,4'-bis (dimethylamino) -benzophenone
  • xanthones eg, xanthone, thioxanthone, 2-cloxantoxanthone
  • Acetofphenones eg, acetofphenone, trichloroacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-1-2-funyulasetofenone
  • These may be used alone or in combination.
  • the photosensitive resin composition of the present invention may also optionally contain conventional additives, for example, a heating weight of 0.001% to 2.0% based on the weight of the total photosensitive resin composition without solvent.
  • Inhibitors can be included.
  • Suitable polymerization inhibitors include, for example, hydroquinone, hydroquinone monomethyl ether, mono-t-butyl hydroquinone, catechol, p-t-butyl catechol, 2,6-di-t-butyl-p-cresol, benzoquinone, 2, 5-diphenyl p-benzoquinone, p-methoxyphenol, t-butyl pyrocatechol, pyrogallol,
  • the photosensitive resin composition of the present invention is further improved by incorporating an appropriate amount of a well-known well-compatible antioxidant and / or antiozonant in order to prevent polymerization inhibition by oxygen, ozone, and the like.
  • Antioxidants useful in the present invention include alkylated phenols, such as 2,6-di-t-butyl-4-methylphenol, alkylated bisphenols, such as 2.2-methylenebis (4-methyl-6-t-butylphenol), 3,5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2--4-hydroxy-3,5-di-tert-butylanilino-1,6-bis (n —S-octylthio) -1,3,5-triazine, polymerized trimethyldihydroquinone and dilaurylthiodibutone pionate.
  • antiozonants useful in the present invention include microcrystalline wax and paraffin wax, dibutylthiourea, 1,1.3,3-tetramethyl-2-thiourea, “antisozonant” AFD (a product of Naphton), norbornane, and 5-Norbornene 2-methyl adipate, G 5-Nonorne Bornene 2-methyl maleate, G 5-Norbornene 2-methyl terephthalate, Ozone Protector 80 (a product of Reichhold Chemical Co.), N-Fuji Lu 2-naphthylamine, unsaturated vegetable oils (eg, rapeseed oil, linseed oil, safflower oil), polymers and resins (eg, ethylene / vinyl acetate copolymer resin, chlorinated polyethylene, chlorosulfonated polyethylene, chlorine) Chemical modified Tylene / methacrylic acid copolymer, polyurethane, polypropylene Nantagen, polybutadiene, furfural
  • the photosensitive resin composition also includes an immiscible polymeric or non-polymeric organic or essentially non-scattering actinic radiation that is essentially transparent at the wavelengths used to expose the photosensitive resinous material.
  • an immiscible polymeric or non-polymeric organic or essentially non-scattering actinic radiation that is essentially transparent at the wavelengths used to expose the photosensitive resinous material.
  • inorganic fillers or scavengers such as polystyrene, internally three-dimensional microresin particles (microgels), organophilic silica, bentonite, silica, powdered glass, colloidal carbon, and various types of dyes and pigments Can be.
  • Such materials are used in various amounts depending on the desired properties of the elastomeric composition. Fillers improve the strength of the elastic layer, reduce tack (stickiness), and are also useful as colorants.
  • a plasticizer having good compatibility may be used in the photosensitive resin layer to lower the glass transition temperature of the binder and facilitate selective development.
  • the plasticizer must be compatible with the polymer.
  • common plasticizers that can be used are dialkyl phthalates, alkyl phosphates, polyethylene glycols, polyethylene glycol esters and polyethylene glycol ethers.
  • the composite rubber (1) is 5 to 98% by weight, preferably 10 to 95% by weight, more preferably 15 to 90% by weight, 1 to 80% by weight, preferably 5 to 50% by weight, more preferably 5 to 30% by weight of the elastomer (2) other than the component (1), and 1 to 50% by weight of the polymerizable compound (3).
  • % Preferably 2 to 40% by weight, more preferably 5 to 25% by weight, and the photoinitiator (4) is 0.1 to 20% by weight, 0.1 to 10% by weight, more preferably 0.2 to 5% by weight (when the total composition is 100%).
  • the composite rubber (1) is less than the above range!
  • the physical properties of the plate material cannot be obtained, and the printability cannot be obtained. If the amount is larger than the above range, the developability is reduced. If the amount of the elastomer component (2) other than the component (1) is less than 1% by weight, the balance between the developability and the physical properties of the plate material is difficult, and it is difficult to manufacture the plate material. If the amount is more than 80% by weight, sufficient physical properties of the plate material cannot be obtained, and the printability is not satisfied. If the content of component (3) is less than 1% by weight, sufficient image quality cannot be obtained. If it exceeds 50% by weight, the plate will lack elasticity and will not be suitable for flexographic printing.
  • the amount of the photopolymerization initiator is less than 0.1% by weight, sufficient image quality cannot be obtained and the sensitivity is lowered. If it exceeds 20% by weight, the crosslink density and the hardness of the plate will increase, making it unsuitable for flexographic printing.
  • the above-described photosensitive resin composition of the present invention can be used for producing a resin plate for flexographic printing. That is, the resin for flexographic printing of the present invention is obtained by subjecting the photosensitive resin composition obtained above to a suitable state (for example, sheet or blade) in a molten state by a conventional method, for example, extrusion molding or extrusion molding. It is obtained by calender molding on a support material to a thickness of 200 to 2 Omm.
  • the support material include a plastic plate, a plastic sheet, a rubber sheet, a foamed olefin sheet, a foamed rubber sheet, a foamed urethane sheet, a metal plate, and a metal sheet.
  • a resin plate for flexographic printing can be obtained by appropriately applying an adhesive to these supports as required.
  • a mat layer is formed on these flexographic printing resin plates in order to improve the vacuum adhesion of the negative during exposure and to enhance the peelability of the negative film after exposure. Therefore, as a desirable structure, the above-mentioned photosensitive resin composition of the present invention is formed on a flexible support via an adhesive layer, and further has a flexible mat thereon.
  • the resin for flexographic printing obtained as described above is exposed through a negative film having an appropriate image to cause photopolymerization on the exposed portion. To get a latent image.
  • light used for exposure For example, ultraviolet light is used.
  • the flexographic printing plate of the present invention having excellent image reproducibility, water resistance, rubber elasticity and mechanical strength can be obtained.
  • the flexographic printing plate is particularly suitable for commercial flexographic printing because of its excellent developability and durability.
  • the ozone resistance of the manufactured flexographic printing plate can also be improved by annealing it at high temperature before use.
  • a flexographic plate material physical properties as a flexographic plate material are obtained by using a photopolymerizable composite rubber, that is, a composite rubber obtained by subjecting a gen-based urethane-modified acrylate having a photopolymerizable functional group to a conjugated reaction with a gen-based rubber.
  • a photopolymerizable composite rubber that is, a composite rubber obtained by subjecting a gen-based urethane-modified acrylate having a photopolymerizable functional group to a conjugated reaction with a gen-based rubber.
  • chemical properties, especially the solvent resistance and the ink resistance of flexo solvent inks with low alcohol content are improved. It is also easy to form a flexographic plate material.
  • TDI 2,4-Tolylene diisocyanate
  • H EMA 2-hydroxyshethyl methacrylate
  • a solution prepared by dissolving 100 g of liquid rubber (JSR-HTPB (manufactured by Nippon Synthetic Rubber Co., Ltd., average molecular weight: 2120, hydroxyl group content: 0.93)) in 300 g of dioxane was put into another 1000 ml reactor and stirred with nitrogen.
  • the above reactants were added dropwise under stirring.
  • the reaction solution was kept at 75-80, and after the completion of the dropwise addition, the reaction was continued at the same temperature for 6 hours.
  • the infrared absorption spectrum was used to confirm that the absorption of the isocyanate group (225 Ocir 1 ) had disappeared. Finished.
  • the reaction solution was pale yellow and transparent and had a viscosity of 450 cps (30 BH type viscometer).
  • the reaction solution was gradually dropped into a beaker containing 5400 ml of n-hexane to obtain a white precipitate.
  • the sludge was dried in a vacuum drier for 2 days after removing the solvent layer by a gradient method. After drying, a solid urethane acrylate was obtained.
  • the yield of the polymer was 162 g (92% yield).
  • Bae click preparative le in SSOOcnr ⁇ 292 Ocm ' ⁇ 1710cm' 1. 1640cm "1 specific absorption was observed.
  • the molecular weight determination by Gelber permeation chromatography Chillon chromatography (G PC) the number The average molecular weight was 3400.
  • Perethane acrylate was produced in the same manner as in Example 1 except that the types of the liquid rubber and the dihydric alcohol having a molecular weight of 2000 or less used in Synthesis Example 1 were changed. Table 1 shows the mixing ratio and the physical properties of the obtained urethane acrylate. Table 1 also shows examples of formulations in which the number n of hard segment repeating units is increased. The weight of the liquid rubber used here is 100 g. table 1
  • a part of the composite chemical composition 11 obtained in Synthesis Example 15 was reacted in the same manner for another hour while raising the composite temperature and maintaining the temperature at 160 ° C, and the composite chemical reaction was performed. Obtained.
  • the gel fraction of this elastomer measured by the same method was 1.0%.
  • the resulting mixture is further extruded into a sheet by a 350 single-screw extruder equipped with a double-armed extruder, and is a 130-thick polyester coated with a black mouth-prene adhesive (Hitachi Chemical Co., Ltd. A 2.8 m ⁇ photosensitive resin layer was formed on the film.
  • a PET film coated with a coating solution for forming a matting layer consisting of a toluene solution of a polyamide resin and a fine silica powder was layered thereon, and the matting layer was transferred to the plate for photosensitive flexographic printing plates. I got it.
  • a back exposure was performed from the back of the plate using an exposing machine consisting of a 60W ultraviolet lamp.
  • a negative film having an appropriate image was brought into close contact with the vacuum and then irradiated for 12 minutes to perform the main exposure.
  • development was carried out with 20 ml of trichlorethane for 5 minutes using a dissolution machine 1215 system manufactured by DuPont to obtain a negative 1.2 faithful relief 1.2M printing plate.
  • the obtained plate material has a Shore hardness A of 47 degrees, has sufficient elasticity, is strong, and has an alcohol content of 800 at a printing speed of 500 feet / minute with a stack type two-color flexographic printing press.
  • Printing was performed on a 70-thick milk-white treated polyethylene film using flexo ink of at least%. No change was observed on the surface of the printing plate even after printing 200,000 passes.
  • the plate was immersed in hexane and ethyl acetate, allowed to stand for 6 hours, removed, and the attached solvent was removed. It was 82% for xanth and 86% for ethyl acetate.
  • a practical toughness check of the obtained printing plate was performed by a coin scratch method. Although scratching was performed five times, no scratch was found and it was confirmed that the steel had good toughness.
  • Example 11 the photopolymerizable gen-based urethane modification obtained in Synthesis Example 1 was used.
  • a composition for photosensitive flexographic printing plate material is obtained in the same manner except that the compounding reaction is not performed instead of the compounding reaction in place of (5), and the photosensitive layer is formed by forming a resin layer on a polyester film in the same manner.
  • a flexographic printing plate was obtained.
  • Exposure and development were performed in the same manner to form a relief to obtain a printing plate.
  • the resulting plate material had a Shore hardness A of 45 degrees, and printing was performed on a 70-thick milky-white polyethylene film using a flexoink containing an alcohol component of at least 80% at a printing speed of 500 feet / minute. Although printing was performed for 100,000 copies, the fine lines of the printing plate were slightly missing.
  • Example 1 a composition for a photosensitive flexographic printing plate material was obtained in exactly the same manner as in Example 1, except that the one obtained in Synthesis Example 12 was used as the composite chemical elastomer, and a flexographic printing plate was similarly produced. Manufactured.
  • a composition for photosensitive flexographic printing plate material was obtained in the same manner with the composition shown in Table 3, and a printing plate was obtained in the same manner. Each plate had good image quality and printing performance. It also had good performance in the solvent resistance test.
  • Synthetic example of the photopolymerizable composite elastomer (1) having exactly the same composition as in Example 1 was used instead of Synthetic Example 1-5 instead of Synthetic Example 1-9, 110, -11, and 1-6.
  • a composition for a photosensitive flexographic printing plate material was obtained, and a printing plate was prepared and evaluated. All had good performance.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention porte sur une composition photosensible permettant de fabriquer une plaque flexographique dotée de propriétés satisfaisantes en tant que plaque et d'une bonne résistance aux solvants et aux encres tout en permettant une productivité élevée. Cette composition photosensible comprend: (1) 5 à 98 % en poids d'un caoutchouc composite photopolymérisable doté d'une fraction de gel de 0,5 % ou moins qu'on prépare avec (a) un acrylate photopolymérisable modifié par diène ou uréthane et représenté par la formule générale (I): où R représente C2-C8 alkylène ou polyoxyalkylène; R1 représente H ou CH3; R2 et R3 représentent chacun le résidu d'un composé diisocyanate; R4 représente le résidu d'un dialcool d'un poids moléculaire de 2000 ou moins et représenté par la formule générale (II): où R5 représente C2-C8 alkylène ou polyoxyalkylène, et R6 et R7 représentent chacun H, CH3, (méth)acryloyloxy ou alkyloxy; X représente une partie non hydroxylée d'un caoutchouc liquide à base de diène hydroxylé; l représente un nombre entier allant de 1 à 4; 1 < m « 4; et n représente un nombre entier allant de 1 à 6; on fait réagir (a) avec (b) un élastomère diène dont au moins un Tg est à 0 °C ou moins; (2) 1 à 80 % en poids d'un élastomère autre que (1); (3) 1 à 50 % en poids d'un composé photopolymérisable comprenant dans sa molécule au moins un groupe photopolymérisable; et (4) 0,1 à 20 % en poids d'un initiateur de photopolymérisation.
PCT/JP1993/000152 1992-02-06 1993-02-05 Composition photosensible destinee aux plaques flexographiques WO1993016414A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP4021095A JPH05216225A (ja) 1992-02-06 1992-02-06 フレキソ版材用感光性組成物
JP4/21095 1992-02-06

Publications (1)

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WO1993016414A1 true WO1993016414A1 (fr) 1993-08-19

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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6555292B1 (en) * 1996-09-24 2003-04-29 Misty Huang Liquid photopolymer useful in fabricating printing plates which are resistant to solvent based ink
JP4868920B2 (ja) * 2006-04-07 2012-02-01 旭化成イーマテリアルズ株式会社 フレキソ印刷用感光性樹脂組成物
JP5420290B2 (ja) * 2009-03-27 2014-02-19 旭化成イーマテリアルズ株式会社 感光性樹脂組成物、フレキソ印刷版、及びフレキソ印刷版の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5137702A (en) * 1974-09-14 1976-03-30 Basf Ag Reriifuinsatsuban narabini sonoseizoyotasoban
JPS53137132A (en) * 1977-05-04 1978-11-30 Hercules Inc Engraving resin
JPS5492402A (en) * 1977-12-28 1979-07-21 Asahi Chemical Ind Photosensitive resin relief printing and fabrication
JPS54102393A (en) * 1978-01-04 1979-08-11 Hercules Inc Photosensitive resin composition for printing plate
JPS5694352A (en) * 1979-12-26 1981-07-30 Uniroyal Inc Multilayerrtype print plate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5137702A (en) * 1974-09-14 1976-03-30 Basf Ag Reriifuinsatsuban narabini sonoseizoyotasoban
JPS53137132A (en) * 1977-05-04 1978-11-30 Hercules Inc Engraving resin
JPS5492402A (en) * 1977-12-28 1979-07-21 Asahi Chemical Ind Photosensitive resin relief printing and fabrication
JPS54102393A (en) * 1978-01-04 1979-08-11 Hercules Inc Photosensitive resin composition for printing plate
JPS5694352A (en) * 1979-12-26 1981-07-30 Uniroyal Inc Multilayerrtype print plate

Also Published As

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JPH05216225A (ja) 1993-08-27

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