Flexographic printing plate with improved cure efficiency

Abstract

A method of making a relief image printing element comprising a plurality of relief printing dots. The method includes the steps of: (a) providing at least one photocurable layer disposed on the backing layer, the at least one photocurable layer being capable of being selectively crosslinked and cured upon exposure to actinic radiation, (b) imagewise exposing the at least one photocurable layer to actinic radiation to selectively crosslink and cure portions of the at least one photocurable layer; and (c) developing the relief image printing element to separate and remove uncrosslinked and uncured portions of the at least one photocurable layer to reveal the relief image therein. The at least one photocurable layer comprises (i) an ethylenically unsaturated monomer; (ii) a binder; and (iii) a photoinitiator exhibiting a quantum yield of initiation (Qi) of more than 0.05 at a 365 nm wavelength.

Claims

1. A method of making a relief image printing element comprising a plurality of relief printing dots, the method comprising the steps of: a) providing at least one photocurable layer disposed on a backing layer, the at least one photocurable layer being capable of being selectively crosslinked and cured upon exposure to actinic radiation, the at least one photocurable layer comprising: i) an ethylenically unsaturated monomer; ii) a binder; and iii) a photoinitiator, the photoinitiator exhibiting a quantum yield of initiation (Qi) of more than 0.05 at a 365 nm wavelength; b) imagewise exposing the at least one photocurable layer to actinic radiation to selectively crosslink and cure portions of the at least one photocurable layer; and c) developing the relief image printing element, to separate and remove uncrosslinked and uncured portions of the at least one photocurable layer to reveal a relief image therein, wherein the relief image comprises the plurality of relief printing dots, and wherein the plurality of relief printing dots exhibit an edge sharpness of the dots such that the ratio of the radius of curvature at the intersection of the shoulder and the top surface of the dot, r.sub.e, to the width of the top of the dot, p, is less than 5%; and wherein the step of imagewise exposing the at least one photocurable layer to actinic radiation is conducted in the presence of atmospheric oxygen.

2. The method according to claim 1, wherein the photoinitiator exhibits a quantum yield of initiation (Qi) greater than 0.075 at the 365 nm wavelength.

3. The method according to claim 2, wherein the photoinitiator exhibits a quantum yield of initiation (Qi) greater than 0.08 at the 365 nm wavelength.

4. The method according to claim 1, wherein an extinction coefficient of the photoinitiator is greater than 300 1.Math.cm.sup.−1.Math.mol.sup.−1 at a 365 nm wavelength.

5. The method according to claim 4, wherein the extinction coefficient of the photoinitiator is greater than 400 1.Math.cm.sup.−1.Math.mol.sup.−1 at the 365 nm wavelength.

6. The method according to claim 5, wherein the extinction coefficient of the photoinitiator is greater than 500 1.Math.cm.sup.−1.Math.mol.sup.−1 at the 365 nm wavelength.

7. The method according to claim 1, wherein the photoinitiator is selected from the group consisting of 1-butanone-2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl], 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and combinations of one or more of the foregoing.

8. The method according to claim 1, wherein the photoinitiator is present in the at least one photocurable layer at a concentration of between 1.5 and 5.0 percent by weight.

9. The method according to claim 8, wherein the photoinitiator is present in the at least one photocurable layer at a concentration of between 2.0 and 3.5 percent by weight.

10. The method according to claim 1, wherein the step of imagewise exposing the at least one photo curable layer to actinic radiation is conducted without altering of a type, power or incident angle of radiation during the exposure step.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIGS. 1A-1I depict printing dots produced in accordance with the present invention using different photoinitiators.

(2) In all FIGS. 1A-1I, the photopolymer composition was held constant except that the photoinitiator used was selected from one of the three compounds indicated in the far left hand column of FIGS. 1A-1I.

(3) FIG. 1A indicates that 5% dots were not held (i.e., the dots did not form as dots) using 2,2-Dimethoxy-1,2-diphenylethan-1-one.

(4) FIG. 1B indicates that 10% dots yielded 0.9% dots on the plate using 2,2-Dimethoxy-1,2-diphenylethan-1-one.

(5) FIG. 1C indicates that 50% dots yielded 32.6% dots on the plate using 2,2-Dimethoxy-1,2-diphenylethan-1-one.

(6) FIG. 1D indicates that 5% dots yielded 1.8% dots on the plate using 2-Dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one.

(7) FIG. 1E indicates that 10% dots yielded 5.4% dots on the plate using 2-Dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one.

(8) FIG. 1F indicates that 50% dots yielded 40.3% dots on the plate using 2-Dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one.

(9) FIG. 1G indicates that 5% dots yielded 1.6% dots on the plate using 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide.

(10) FIG. 1H indicates that 10% dots yielded 5.5% dots on the plate using 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide.

(11) FIG. 1I indicates that 50% dots yielded 37.9% dots on the plate using 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(12) The inventors of the present invention have found that the use of particular photoinitiators in a photocurable printing plate composition produces print dots having desired geometric characteristics without the need for additional process steps. Thus, the photocurable compositions described herein produce relief image printing plates having printing dots with the desired geometric characteristics without the need for a barrier layer. In addition, the process described herein can also be conducted in the presence of atmospheric oxygen.

(13) To that end, in one embodiment, the present invention relates generally to a method of making a relief image printing element, the method comprising the step of: a) providing at least one photocurable layer disposed on the backing layer, the at least one photocurable layer being capable of being selectively crosslinked and cured upon exposure to actinic radiation, the at least one photocurable layer comprising: i) an ethylenically unsaturated monomer; ii) a binder; iii) a photoinitiator, the photoinitiator exhibiting a quantum yield of initiation (Qi) of more than 0.05 at a 365 nm wavelength; b) imagewise exposing the at least one photocurable layer to actinic radiation to selectively crosslink and cure portions of the at least one photocurable layer; and c) developing the relief image printing element to separate and remove uncrosslinked and uncured portions of the at least one photocurable layer to reveal the relief image therein;

(14) wherein the relief image comprise a plurality of relief image printing dots, wherein the plurality of relief image printing dots exhibit an edge sharpness of the dots such that the ratio of the radius of curvature at the intersection of the shoulder and the top surface of the dot, r.sub.e, to the width of the top of the dot, p, is less than 5%.

(15) The present invention also relates generally to a photocurable composition for producing a relief image printing element, the photocurable composition comprising: a) an ethylenically unsaturated monomer; b) a binder; c) a photoinitiator, the photoinitiator exhibiting a quantum yield of initiation (Qi) of more than 0.05 at a 365 nm wavelength.

(16) The inventors of the present invention have found that the inclusion of particular photoinitiators into the photocurable composition having a higher quantum yield of initiation produces a printing element with finer and sharper printing dots. In one embodiment, these photoinitiators may comprise certain α-aminoketones.

(17) The initiation rate of polymerization (Ri) was measured to evaluate the suitability of various photoinitiators, which can be done by real-time FTIR or RTIR.

(18) Ri is described by Equation 1:
Ri=I.sub.a.Math.Q.sub.i  (1)

(19) I.sub.a is the absorbed intensity (mW) and is calculated as set forth below in Equation 2.

(20) Q.sub.i is the quantum yield of initiation and is defined as the number of initiated polymerizing chains per absorbed photon. Q.sub.i is influenced by all the photochemical/physical phenomena that can affect an excited molecule after absorption of one photon.
I.sub.a=I.sub.0.Math.(1−10.sup.−OD)  (2)
OD=ε.Math.[PI].Math.L  (3)
Wherein:

(21) I.sub.0=Incident intensity (mW)

(22) ε=Extinction coefficient

(23) [PI]=Photoinitiator concentration (mol/l)

(24) L=Thickness (cm)

(25) Q.sub.i is calculated via an experimental determination of the rate of polymerization (R.sub.p) and by the use of the propagation and termination constants (k.sub.p and k.sub.t) for acrylate monomers that are found in the literature.

(26) In order for a photoinitiator to react effectively, it must first effectively absorb the service wavelength, which means a high I.sub.a, and thus a high ε value. Then, the absorbed energy must be converted in a high number of initiating radicals, which results in a high Q.sub.i ratio.

(27) In order to compare various photoinitiators, ε and Q.sub.i were determined for three photoinitiators at 365 nm and the results are depicted in Table 1.

(28) TABLE-US-00001 Photoinitiator ε.sub.365nm (1 .Math. cm.sup.−1) .Math. mol.sup.−1) Q.sub.i-365nm 2,2-dimethoxy-2-phenylacetophenone 141 0.014 1-butanone-2-(dimethylamino)-2-[(4- 1247 0.081 methylphenyl)methyl]-1-[4-(4- morpholinyl)phenyl] Diphenyl(2,4,6- 518 0.118 trimethylbenzoyl)phosphine oxide

(29) Printing plate formulations were prepared using the photoinitiators described in Table 1 at the concentrations set forth in Table 2. Table 2 also lists a range of concentration values that may be used for each ingredient of the sample photocurable composition.

(30) Once the photocurable compositions were prepared using the photoinitiators described above, the photocurable compositions were imagewise exposed to actinic radiation and then developed using solvent development to remove uncured photopolymer.

(31) TABLE-US-00002 TABLE 2 Sample Photocurable Composition Example 1 Range (Wt. %) (Wt. %) Kraton ® D1114 (Rubber) 67.0 60-80 PB B-1000 13.0 10-20 HDDA 15.0 10-20 BHT 1.92 0.5-5.0 Tinuvin 1130 0.075 0.02-0.20 Dye 0.01 0.005-0.05  Photoinitiator 3.0 1.5-5.0

(32) Based on the results, it was determined that a Quantum yield of initiation (Qi) higher than about 0.05 at the 365 nm wavelength, more preferably higher than about 0.075 at the 365 nm wavelength, and most preferably higher than about 0.08 at the 365 nm wavelength was capable of producing a printing plate having printing dots with the desired geometric characteristics as illustrated in FIGS. 1A-1I.

(33) A high extinction coefficient is also necessary but is not sufficient in and of itself for good initiation. Indeed, after the light absorption, the photoinitiator is promoted to its singlet then triplet states from which it can undergo different reactions, including the generation of radicals, quenching by the monomer, oxygen inhibition and thermal deactivation. At this stage, there is already a risk that the effectiveness of the photoinitiator is reduced, even for a high extinction coefficient molecule. Assuming that everything goes well and the radicals production is dominant, the type of radicals produced may still have different sensitivities towards oxygen depending on their reactivities. Again, a high coefficient of extinction would not necessarily be enough if these radicals have a long enough lifetime, making them too sensitive to oxygen and thus reducing their effectiveness in initiating the crosslinking reaction.

(34) Thus, it is desirable that the extinction coefficient be higher than about 300 l.Math.cm.sup.−1.Math.mol.sup.−1 at the 365 nm wavelength, more preferably higher than about 400 l.Math.cm.sup.−1.Math.mol.sup.−1 at the 365 nm wavelength, and most preferably higher than about 500 l.Math.cm.sup.−1.Math.mol.sup.−1 at the 365 nm wavelength.

(35) Based on the values of Qi and ε shown in Table 1, both 1-butanone-2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl] and Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide are faster photoinitiators than 2,2-dimethoxy-2-phenylacetophenone. This accounts for the smaller and sharper dots that were obtained using these products as shown in FIGS. 1D-1F and 1G-1I. In addition, although Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide has a slightly larger Qi than 1-butanone-2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl], the much higher absorptivity of the latter allowed it to offset this difference and yield sharper dots. Thus, even though both 1-butanone-2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl] and Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide yield good results, 1-butanone-2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]seems to be faster than Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.

(36) As can be seen from FIGS. 1D-1F and 1G-1I, 1-butanone-2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl] and Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide yield flat and fine dots because of their high initiation rate due to their high absorptivity and quantum yield of initiation. It is expected that a similar behavior would also result from other photoinitiators that exhibit comparable properties.

(37) In addition, one or more antioxidants such as 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, butylated hydroxytoluene (BHT), alkylated phenols, e.g., 2-6-di-tert-butyl-4-methylphenol; alkylated bis-phenols, e.g., 2,2-methylene-bis-(4-methyl-6-tert-butylphenol); 2-(4-hydroxy-3,5-di-tert-butylanilino)-4,6-bis-(n-octyl thio)-1,3,5-triazine; polymerized trimethyldihydroquinone; and dilauryl thiopropionate can also be used in the compositions of the invention in combination with the above referenced additives to further tailor dot shapes in terms of dot angle, dot tops, etc. In one preferred embodiment, the antioxidant is 1,3,5-trimethyl-2,4,6-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, available from Albemarle under the tradename Ethanox 330.

(38) The photocurable composition of the present invention comprises one or more binders, monomers and plasticizers in combination with the one or more photo-initiators described above.

(39) The binder type is not critical to the photopolymer composition and most, if not all, styrenic copolymer rubbers are usable in the compositions of the invention. Suitable binders can include natural or synthetic polymers of conjugated diolefin hydrocarbons, including 1,2-polybutadiene, 1,4-polybutadiene, butadiene/acrylonitrile, butadiene/styrene, thermoplastic-elastomeric block copolymers e.g., styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, etc., and copolymers of the binders. It is generally preferred that the binder be present in at least an amount of 60% by weight of the photosensitive layer. The term binder, as used herein, also encompasses core shell microgels or blends of microgels and pre-formed macromolecular polymers.

(40) Non-limiting examples of binders that are usable in the compositions of the instant invention include styrene isoprene styrene (SIS), a commercial product of which is available from Kraton Polymers, LLC under the tradename Kraton® D1161; styrene isoprene butadiene styrene (SIBS), a commercial product of which is available from Kraton Polymers, LLC under the tradename Kraton® D1171; styrene butadiene styrene (SBS), a commercial product of which is available from Kraton Polymers, LLC under the tradename Kraton® DX405; and triblock copolymers based on styrene and isoprene, a commercial product of which is available from Kraton Polymers, LLC under the tradename Kraton® D1114.

(41) Monomers suitable for use in the present invention are addition-polymerizable ethylenically unsaturated compounds. The photocurable composition may contain a single monomer or a mixture of monomers which form compatible mixtures with the binder(s) to produce clear (i,e., non-cloudy) photosensitive layers. The monomers are typically reactive monomers especially acrylates and methacrylates. Such reactive monomers include, but are not limited to, trimethylolpropane triacrylate, hexanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol-200 diacrylate, tetraethylene glycol diacrylate, triethylene glycol diacrylate, pentaerythritol tetraacrylate, tripropylene glycol diacrylate, ethoxylated bisphenol-A diacrylate, trimethylolpropane triacrylate, di-imethylolpropane tetraacrylate, triacrylate of tris(hydroxyethyl)isocyanurate, dipentaerythritol hydroxypentaacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol-200 dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol-600 dimethacrylate, 1,3-butylene glycol dimethacrylate, ethoxylated bisphenol-A dimethacrylate, trimethylolpropane trimethacrylate, diethylene glycol dimethacrylate. 1,4-butanediol diacrylate, diethylene glycol dimethacrylate, pentaerythritol tetramethacrylate, glycerin dimethacrylate, trimethylolpropane dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol diacrylate, urethanemethacrylate or acrylate oligomers and the like which can be added to the photopolymerizable composition to modify the cured product. Monoacrylates including, for example, cyclohexyl acrylate, isobornyl acrylate, lauryl acrylate and tetrahydrofurfuryl acrylate and the corresponding methacrylates are also usable in the practice of the invention. Especially preferred acrylate monomers include hexanediol diacrylate (HDDA) and trimethylolpropane triacrylate (TMPTA). Especially preferred methacrylate monomers include hexanediol dimethacrylate (HDDMA) and triemethylolpropane trimethacrylate (TMPTA). It is generally preferred that the one or more monomers be present in at least an amount of 5% by weight of the photosensitive layer.

(42) The photocurable layer also preferably contains a compatible plasticizer, which serves to lower the glass transition temperature of the binder and facilitate selective development. Suitable plasticizers include, but are not limited to, dialkyl phthalates, alkyl phosphates, polyethylene glycol, polyethylene glycol esters, polyethylene glycol ethers, polybutadiene, polybutadiene styrene copolymers, hydrogenated, heavy naphthenic oils, hydrogenated, heavy paraffinic oils, and polyisoprenes. Other useful plasticizers include oleic acid, lauric acid, etc. The plasticizer is generally present in an amount of at least 10% by weight, based on weight of total solids of the photopolymer composition. Commercially available plasticizers for use in compositions of the invention include 1,2-polybutadiene, available from Nippon Soda Co. under the tradename Nisso PB B-1000; Ricon 183, which is a polybutadiene styrene copolymer, available from Cray Valley; Nyflex 222B, which is a hydrogenated heavy naphthenic oil, available from Nynas AB; ParaLux 2401, which is a hydrogenated heavy paraffinic oil, available from Chevron U.S.A., Inc.; and Isolene 40-S, which is a polyisoprene available from Royal Elastomers.

(43) Various dyes and/or colorants may also optionally be used in the practice of the invention although the inclusion of a dye and/or colorant is not necessary to attain the benefits of the present invention. Suitable colorants are designated “window dyes” which do not absorb actinic radiation in the region of the spectrum that the initiator present in the composition is activatable. The colorants include, for example, CI 109 Red dye, Methylene Violet (CI Basic Violet 5), “Luxol.” Fast Blue MBSN (CI Solvent Blue 38), “Pontacyl” Wool Blue BL (CI Acid Blue 59 or CI 50315), “Pontacyl” Wool Blue GL (CI Acid Blue 102 or CI 50320), Victoria Pure Blue BO (CI Basic Blue 7 or CI 42595), Rhodamine 3 GO (CI Basic Red 4), Rhodamine 6 GDN (CI Basic Red I or CI 45160), 1,1′-diethyl-2,2′-cyanine iodide, Fuchsine dye (CI 42510), Calcocid Green S (CI 44090) and Anthraquinone Blue 2 GA (CI Acid Blue 58), etc. The dyes and/or colorants must not interfere with the imagewise exposure.

(44) Other additives including antiozonants, fillers or reinforcing agents, thermal polymerization inhibitors, UV absorbers, etc. may also be included in the photopolymerizable composition, depending on the final properties desired. Such additives are generally well known in the art.

(45) Suitable fillers and/or reinforcing agents include immiscible, polymeric or nonpolymeric organic or inorganic fillers or reinforcing agents which are essentially transparent at the wavelengths used for exposure of the photopolymer material and which do not scatter actinic radiation, e.g., polystyrene, the organophilic silicas, bentonites, silica, powdered glass, colloidal carbon, as well as various types of dyes and pigments. Such materials are used in amounts varying with the desired properties of the elastomeric compositions. The fillers are useful in improving the strength of the elastomeric layer, reducing tack and, in addition, as coloring agents.

(46) Thermal polymerization inhibitors include, for example, p-methoxyphenol, hydroquinone, and alkyl and aryl-substituted hydroquinones and quinones, tert-butyl catechol, pyrogallol, copper resinate, naphthalamines, beta-naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, butylated hydroxytoluene (BHT), oxalic acid, phenothiazine, pyridine, nitrobenzene and dinitrobenzene, p-toluquinone and chloranil. Other similar polymerization inhibitors would also be usable in the practice of the invention.

(47) Using the photoinitiators described herein, it is possible to produce printing plates having printing dots that exhibit desired geometric characteristics for printing, including planarity of a top surface of the dots and edge sharpness of the dots. Furthermore, these desired characteristics can be achieved without using an oxygen barrier layer in the process and without altering the type, power or incident angle of radiation during the exposure step. Finally, the method described herein may also be conducted in the presence of atmospheric oxygen.