CA1304532C - Radiation sensitive acrylate composition - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Radiation sensitive compositions comprising acrylic or methacrylic acid esters with decreased oxygen inhibition attained by use of minor amounts of N,N'-diorgano dicarboxamide additives. The acrylated ester compositions are suitable for ultraviolet curable coatings.

Description

~304532 ~IMPROVED RADIATION SENSITIVE ACRYLATE COMPOSITION"

This application relates to radiation-~ensitive compo~itions and more particularly to ~uch compositions comprising acrylated esters.
AB ufied in thi~ specification, the term "acrylated esters" refers to either acrylic or methacrylic acid re~ins. U.S. Patent No. 4,171,974 describe~ photosensitive re~ins that are styrene solutions of methacrylate esters o~ epoxy resin6 available as Epocryl (TM) 321 and 322 reoins from the Shell Chemical Corporation. A1BO disclosed are diacrylate esters o~ liquid Bi~phenol A epoxy resins available a~ Epocryl DRH-302 and 303. Other ~uitable acrylate esterc are prepared from polyepoxy compound~ derived from phenol-formaldehyde novolacs of un~aturated functionality up to 3. 3.
In U. S. Patent No. 4, 174, 307 there are described radiation ~ensitive compo0itions which are based on diacrylated oligourethane6.
An ultraviolet curable resin now available is a nonvolatile acrylated urethane ba~ed on aliphatic isocyanate and ~old as CMD 8800*UV/EB
Curable Resin by the Celanese Corporation.
Such acrylated re~ins are e~pecially uoed in rapid curing ultra-violet light curable coatings. There are a variety o potential uses for these coating~ including wood topcoat~, coatings for rigid and flexible pla~tic~, floor tile coatings, ~creen ink coatings and clear coatings, coatings for magnetic tape or di~c. An important potential u~e i~ as a light-~ensitive coating on lithographic plates.

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A major drawback in using the~e radiation-~encitive acrylated ester~ has been the inhibition to ultraviolet curing in the pre~ence of oxygen, e. g., when carried out in the pre~ence o~ air. It will be understood therefore tllat certain commercial linlitation~ ari~e becau~e of the deleteriou6 ef~ect oxygen has on ultraviolet light curing.

In accordance with the present invention it has now been ~ound that a ~igniicant decrea6e in oxygen i~hibition of light curable radiation ~en~itive compo6ition~, compri~ing un~aturated oliomers and polymers, can be attained by incorporati~lg minor amo~ts o~ N, N' -diorgano dicarboxamides such a~ N,N'-dialkyl tartardiamide, N,N'-dioctyl tartardiamide, N,N'-dihexyl malondiamide, N,N'-dipropyl ~uccindiamide.
The radiation composition will generally contain a solvent or ~olvent~, one or more conventional additive6 ~uch as photoinitiators, photoactivators, dye~, polymer6, pla~ticizer6 and unfiaturated monomers, oligomer~ and polymer~.
Accordingly, a radiation sensitive composition is provided comprising an acrylic or methacrylic acid ester, a photoinitiator, and an anti-oxygen inhibitory amount of a N,N'-diorgano dicarboxamide selected from the group consisting of N,N'-diallyl tartardiamide N,N'-dibutyl tartardiamide N,N'-dioctyl tartardiamide N,N'-dihexyl tartardiamide N,N'-diisoamyl tartardiamide N,N'-dibutyl succindiamide -2a-N,N'~ihexyl malondiamide N,N'-dicyclopropyl tartaramide N,N'~ibenzyl tartardiamide.
The radiation sen~itive compo6ition6 of thi~ invention will combine ac e6sential components unfiaturated oligomer6 and polymers and a minor amount o~ N,N'-diorgano dicarboxamide6 dis601ved in a solvent for bo~h component6; and as mentioned, conventional additive~
such a6 photoinitiator6, photoactivator6, and the like, al60 in minor amount6. Other additive~ such a6 dyes, polymeric re6ino ~nd pla6ticizers may be utilized depending upon the end use of the radiation sen6itive compo6ition .

-3-i304S32 In general, the amount of acrylated resin in the final composition will range from about 2 to 95~o by weight, preferably from 10 to 75%, of nonvolatile components.
The N, N' -diorgano dicarboxamides suitable for decreasing the oxygen inhibition of the ultraviolet light radiation sen~itive acrylate compounds have the following struct~ral formula:
Rl - N - X - N - R2 where Rl and R2, which may be the same or different, contain from 2 to 20 carbon atoms and are alkyl, allyl, cycloalkyl, aryl, aralkyl groups. These groups may have substituents such as hydroxy, cyano, and halogen.
X is the hydroxy carboxylic acid radical or moiety derived from oxalic acid or O O

wherein R3 is an alkyl group having from 1 to 8 carbon atoms or an aryl group having from 6 to 12 carbon atoms. The alkyl and aryl groups may be substituted with, for example, hydroxyl groups.
Illustrative N,N'-diorgano carboxamides are:
N, N' -Diethyl tartardiamide N, N' -Dipropyl tartardiamide N, N' Dibutyl tartardiamide N,N'-Dioctyl tartardiamide N,N'-Diisopropyl tartardiamide N,N'-Diisobutyl tartardiamide ~4~ i304S32 N, N' -Neopentyl tartardiamide N, N' -Diisoamyl tartardiamide N, N' -Dicyclopropyl tartardiamide N, N' -Dicyclopentyl tartardiamide N, N' -Dicyclohexyl tartardiamide N, N' -Di(6-hydroxyhexyl) tartardiamide N,N'-Di(6-cyanohexyl) tartardiamide N, N' -Diphenyl tartaramide N, N' -Diallyl tartardiamide N, N' -Di(2, 2, 2-trifluoroethyl) tartardiamide N, N' -Dibenzyl tartardiamide N, N' -Diphenethyl tartardiamide N, N' -Di(4 -methoxybenzyl) tartardiamide N,N'-Dipropyl oxalyldiamide N,N'-Dibutyl oxalyldiamide N, N' -Dihexyl oxalyldiamide N, N' -Didodec yl oxalyldiamide N,N'-Dii~opropyl oxalyldiamide N, N' -Dicyclohexyl oxalyldiamide N,N'-Dibenzyl oxalyldiamide N,N'-Di(2-methylphenyl) oxalyldiamide N, N' -Dipropyl malondiamide N, N' -Dibutyl malondiamide N, N' -Dihexyl malondiamide , , !
N,N'-Dipropyl cuccindiamide N,N'-Dibutyl ~uccindiamide N, N' -Dipropyl malicdiamide N, N' -Dipropyl terephthalyldiamide ID general the amou~t of the N, N'-diorgano dicarboxamide employed will be at leaot l~o by weight of the total weight of the non-volatile portion o~ the total compocition In moct instanceo from about 1 to 10%, preferably 3 to 6rlo, by weight will l~o Eu~ficient to attain the de~ired re~ult~
Compoundo ouch a~ tartaric acid, tartaric acid diamide, 2, 3-dibenzoyl tartaric acid, tartaric acid dimethyl eoter, N,N'-diallyl acrylamide, diallyl urea, triallyl i~ocyanurate, N,N'-diallyl ethanolamine, bi~(diallylamino) methane, dimethyl diallyl ammonium chloride, citric acid and aocorbic acid werc found ineffective in ~ubotantially decreasing oxygen inhibition Solvertc which may be utilized in formulating the radiation cencitlve compooitionc include Methyl Cello~olve* alcoholo ouch ao mothanol and iooprop~nol; ketone~ ouch a~ methylethyl ketone ~d cyclohexanone, aromatice ouch a~ toluene, dimethyl formamide, tctrahydrofur~, methylene chloride, and the like The other additiveo may irclude photoinitiatoro nd photoacti~rator~, uoed in minor amounto ouch a- benzophenone, Michler'o Xetone; ioopropyl thioxanthone, 2-methyl-1-14-(methylthioJphenyl~-2-morpholino-propan-l-one, benzil dimethyl ketal, ioopropylbenzoin ether, ethyl4-dimethylamino benzoate, and wetophenone derivativoo * Trademark ....

~304S32 ~ he invention will be more fully underctood by reference to the following illustrative embodiment~ In the~e test~ the radiation curable compo6ition wa~ coated on a grained anodized ~d ~ilicated aluminum plate To mea6ure the curing rate a 21 tep Fogra Grey Scale Negative wa~ u~ed (described in Fogra praxis report No 24 Deutche Faschung-Ge~ell6chaft fur Druck und Reproduktion~ Technik E V
Copyright 1979 by FOGRA ) Oz e~fect wa6 te6ted by mea~uring change in gray ccale on expocure for 10 ~ec in a 5kw Berkey W light ource st 27 and 7 inch by vacuum After expocure the coating wa~ developed for 10 cec in Polychrome 972*developer rinsed and inked The grey ~cale inked tail wac recorded a6 a mea~ure of curing rate ~ cignificant increa~e in curing rate was noticed ecpeci~lly at low vacuum upon addition of carboxamide EXAMPLE I
(A) 5 6 gram~ of acrylated urethane cold under the trademark Celrad 3701 by the Cel nece Corp wa~ di~olved in 300 ml oi methyl cellocolve To the re~ulting colution 0 2 gram benzophenone and 0 2 gr-m Michlerc Ketone were added The recultlng radiation cen~itive compocition wa~ coated on a grained anodized and cilicated aluminum lithographic plate When the coated plate wac inked nd expoced at 27 u~d 7 p~i vacuum developed and inked u~ing a 5kw Berkey~amp a Fogra Grey Scale negative tail of 14 v- 5 wa~ obtained (B) When Run ~ wac repeated with the exception that 0 27 gram of N N'-diallyl tart~rdiamide wac employed aC an addltion-l component * Trade-mark ~30453Z

in formulating the radiation sensitive compo6ition, a Grey Scale tail of 158 was obtained uI~der the same test conditions.
EXAMPLE II
A serie6 of radiation 6en~itive compositions wa~ formulated utilizing the following component~:
Amount DV-530~an acrylated urethane oligmer sold by Polychrome Corp. ~
U. S. P. 4, 233, 390 O. 85 gram Benzophenone 0 . 033 gram Michler~ Ketone 0. 033 gram Diorgano dicarboxamide additive (except in Reference Comp. ) O . 05 gram Methyl Cellosolve 50 ml A6 in Example I (R~ A), each of the re6ulting radiation ~en6itive compo~ition~ wa~ coated on grained, anodized and ~ilicated aluminum lithographic plate6, developed, inked and ~ubjected to identical expo6ure6 at 7 p6i and 27 p6i vacuum, and the Grey Scale tail ~nked, wa~ ob6erved.
The re~ult~ are tabulated below:

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~ 1304S32 TABLE A
Grey Scale-Inked Vacuum, 1~8 i Additive Z7 7 _ _ _ 1) Re~erence (no additive) . 14 5 2) N, N'-Diethyl tartardiamide 17 11 3) N, N'-Dipropyl tartardiamide 17 11 4) N,N'-Dibutyl tartardiamide 18 12 5) N,N'-Dioctyl tartardiamide 19 12 6) N,N'-Dii~opropyl tartardiamide 14 7 7) N,N'-Diisobutyl tartardiamide 16 8 8) N,N'-Neopentyl tartardiamide 15 8 9) N,N'-Diicoamyl tartardiamide 17 10 10) N,N'-Dicyclopropyl tartardiamide 17 9 11) N, N'-Dicyclopentyl tartardiamide 15 8 12) N,N'-Dicyclohexyl tartardiamide 15 7 13) N, N'-Di(6-hydroxyhexyl)tartardiamide 14 7 14) N,N' Di(6-cyanohexyl)tartartiamide 14 6 15) N,N'-Diallyl tartardiamide 17 11 16) N, N' -Dibenzyltartardiamide 16 1 1 17) N,N'-Diphenethyltartardiamide 16 10 18) N,N'-Di(4-methoxybenzyl)tartardiamide 16 8 19) N,N'-Dipropyloxalyldiamide 14 8 20) N,N'-Dibutyloxalyldiamide 15 9 21) N,N'-Dihexyloxalyldiamide 15 8 22) N,N'-Didodecyloxalyldiamide 14 6 23) N,N'-Dii~opropyloxalyldiamide 14 7 -9- 13045~Z
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TABLE A (Cont'd?

24) N,N'-Dicyclohexyloxalyldiamide 14 6 25) N,N'-Dibenzyloxalyldiamide 14 6 26) N, N' -Di(2-methylphenyl)oxalyldiamide 16 8 27) N, N'-Dipropylmalondiamide 16 8 28) N, N' -Dibutylmalondiamide 16 9 29) N, N'-Dihexylmalondiamide 17 11 30) N,N'-Dipropylsuccindiamide 16 ~ 9 31) N,N'-Dibutylsuccindiamide 17 10 32) N,N'-Diphenyl Tartardiamide 17 10 33) N,N'-Dipropylmalicdiamide 15 8 34) N,N'-Dipropyl terephthalyldiamide 16 8 EXAMPLE III
Using the procedures of Example I the following radiation sen~itive compositions were formulated and tested for their Grey Scale tails after being coated on grained, anodized and silicated aluminum lithographic plates, then exposed, developed and with subsequent inking: Amount Celrad CMD 8800 (a nonvolatile acrylated urethane based on an aliphatic isocyanate) ~old by Celanese Corp . 0 . 85 gram Benzophenone 0 . 033 gram Michler'~ Ketone 0.033 gram Additive (except Ref. comp. ) 0. 05 gram Methyl Cello~olve 50 ml The results are 6et forth below:

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i304532 TABLE B

Vacuum, psi Additive 2 35) Re~erence Comp. (no additive) ll 4 36) N,N'-Dipropyl tartardiamide 17 ll 37) N,N'-Dioctyl tartardiamide l6 lO

38) N,N'-Dicyclopentyl tartardiamide 14 7 39) N,N'-Diallyl tartardiamide 18 13 40) N,N'-Dibenzyl tartardiamide 18 12 4l ) N, N' -Dihexyl oxalyldiamide 15 9 42) N,N'-Di(Z-methylphenyl)oxalyldiamide l4 8 43) N,N'-Dihexylmalondiamide 18 12 44) N,N'-Dipropyl ~uccindiamide 16 10 EXAMPLE IV
Another ~ories of radiation ~en~itive compositions was formulatèd utilizing the following components:
Amount DV-530* 0.~5 gram Irgacure 907*~2-methyl l-14-(methylthio) phenyl] - 2 -morpholino -propan -1 -one . 0 . 033 gram Quantacure ITX~I~opropyl-thioxanthone) 0. 004 gram Additive (except for Reference Comp. ) 0. 05 grarn Methyl Cello~olve 50 ml * Trade-mark .~ ~ ,~, ~.

1~04532 As in the preceding Examples, each of the resulting radiation sensitive compositions was coated on grained, anodized and ~ilicated aluminum lithographic plates, inked and subjected to the Grey Scale test.

TABLE C

Vacuum, psi Additive 27 7 45) Reference Comp. (no additive) 7 2 46) N, N'-Diethyl tartardiamide 10 5 47) N, N'-Dioctyl tartardiamide 10 5 48) N,N'-Dicyclopentyl tartardiamide 8 4 49) N,N'-Di~6-hydroxyhexyl)tartardiamide 10 3 50) N,N'-Diallyl tartardiamide 11 5 51 ) N, N' -Dibenzyl tartardiamide 1 1 5 52) N,N'-Dihexyl oxalyldiamide 9 4 53) N,N'-Di(2-methylphenyl~ oxalyldiamide 10 5 54) N, N'-Dihexyl malondi~mide 12 6 55) N,N'-Dipropyl succindiamide 11 5 In commercial operations for manufacturing lithographic printing plate~ the plate~ will be coated with a compo~ition compri~ed of the radiation-~en~itive components of this invention and conventional film-forming resin~ or polymers such as the known celluloses, epoxies, phenolics, acrylates, and the like. Typical proportions of the two major component~ will be utilized, and it will be understood that neither the particular film-forming material nor the amounts of the components are critical features of thi~ invention, ,., :

- 1 2 ~ 1304532 It will be further under6tood that the foregoing embodiments are intended to be illustrative only and that various changes and modifications may be made without departing from the broad scope of the invention, Thus, for example, the radiation sensitive compositions of this invention may be curable by an electron beam.

Claims (13)

1. A radiation sensitive composition comprising an acrylic or methacrylic acid ester, a photoinitiator, and an anti-oxygen inhibitory amount of a N,N'-diorgano dicarboxamide selected from the group consisting of N,N'-diallyl tartardiamide N,N'-dibutyl tartardiamide N,N'-dioctyl tartardiamide N,N'-dihexyl tartardiamide N,N'-diisoamyl tartardiamide N,N'-dibutyl succindiamide N,N'-dihexyl malondiamide N,N'-dicyclopropyl tartaramide N,N'-dibenzyl tartardiamide.

2. The radiation sensitive composition of claim 1 which is ultraviolet light curable.

3. The radiation sensitive composition of claim 1 wherein the acrylic or methacrylic acid ester is acrylated urethane.

4. The radiation sensitive composition of claim 1 wherein the amount of the N,N'-diorgano carboxamide ranges from about 1 to 10% by weight.

5. The radiation sensitive composition of claim 1 wherein the N,N'-diorgano carboxamide is N,N'-diallyl tartardiamide.

6. The radiation sensitive composition of claim 1 wherein the N,N'-diorgano carboxamide is N,N'-dibutyl tartardiamide.

7. The radiation sensitive composition of claim 1 wherein the N,N'-diorgano carboxamide is N,N'-dioctyl tartardiamide.

8. The radiation sensitive composition of daim 1 wherein the N,N'-diorgano carboxamide is N,N'-dihexyl tartardiamide.

9. The radiation sensitive composition of claim 1 wherein the N,N'-diorgano carboxamide is N,N'-diisoamyl tartaramide.

10. The radiation sensitive composition of claim 1 wherein the N,N'-diorgano carboxamide is N,N'-dibutyl succindiamide.

11. The radiation sensitive composition of claim 1 wherein the N,N'-diorgano carboxamide is N,N'-dihexyl malondiamide.

12. The radiation sensitive composition of claim 1 wherein the N,N'-diorgano carboxamide is N,N'-dicyclopropyl tartaramide.

13. The radiation sensitive composition of claim 1 wherein the N,N'-diorgano carboxamide is N,N'-dibenzyl tartardiamide.