CA1212856A - Process for the production of images - Google Patents
Process for the production of imagesInfo
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- CA1212856A CA1212856A CA000445940A CA445940A CA1212856A CA 1212856 A CA1212856 A CA 1212856A CA 000445940 A CA000445940 A CA 000445940A CA 445940 A CA445940 A CA 445940A CA 1212856 A CA1212856 A CA 1212856A
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- General Physics & Mathematics (AREA)
- Epoxy Resins (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
PROCESS FOR THE PRODUCTION OF IMAGES
ABSTRACT
A layer of a liquid composition containing (A) a heat-activated latent polymerising agent for 1,2-epoxides with (B) a light-sensitive compound having in the same molecule at least one 1,2-epoxide group and at least one chalcone or cinnamate group, or with a mixture of (C) a compound containing at least one 1,2-epoxide group together with (D) a compound containing at least one chalcone or cinnamate group, is heated so that the layer solidifies due to thermal polymerisation through the 1,2-epoxide group, remaining, however, photocrosslinkable. The solidified layer is exposed in a predetermined pattern to actinic radiation, the parts so exposed becoming photocrosslinked through the chalcone or cinnamate unit(s) and hence insoluble. An image is produced which can be developed by means of suitable solvents.
An example of a suitable latent polymerising agent (A) is boron trichloride-N-methylpiperidine complex, and a suitable light-sensitive compound (B) is 1-(p-(glycidyloxy)phenyl)-5-phenyl-penta-1,4-dien-3-one.
ABSTRACT
A layer of a liquid composition containing (A) a heat-activated latent polymerising agent for 1,2-epoxides with (B) a light-sensitive compound having in the same molecule at least one 1,2-epoxide group and at least one chalcone or cinnamate group, or with a mixture of (C) a compound containing at least one 1,2-epoxide group together with (D) a compound containing at least one chalcone or cinnamate group, is heated so that the layer solidifies due to thermal polymerisation through the 1,2-epoxide group, remaining, however, photocrosslinkable. The solidified layer is exposed in a predetermined pattern to actinic radiation, the parts so exposed becoming photocrosslinked through the chalcone or cinnamate unit(s) and hence insoluble. An image is produced which can be developed by means of suitable solvents.
An example of a suitable latent polymerising agent (A) is boron trichloride-N-methylpiperidine complex, and a suitable light-sensitive compound (B) is 1-(p-(glycidyloxy)phenyl)-5-phenyl-penta-1,4-dien-3-one.
Description
Case 3-14301/AP.L 334/l~Z/~
-- 1 ~
PROCESS FOR THI~ PRODUCTION OF IMAGES
, This invention relates to a process for the production of images by heating followed by exposure ~o actinic radiation.
Conventionally, production of an image by means of photopolymerisation is achi~ed by coating a support with a solution in a volatile organic solvent of a photopolymerisable substance, causing or allowing the solvent to evaporate so leaving a film of the p~otopolymerisable substance, irradiating the film with actinic radiation as through a negative whereby the parts of the film struck by the irradiation become photopolymerised Cand less soluble~ while those parts shielded ~rom the irradiation remain substantially una.fected, then dissolving away the unirradiated, unphotopolymerised parts of the film by means of a suitable solvent which does not dissolve the irradiated, photopolymerised parts. This last stage is conventionally known as "development".
It would ~e desirable to have a process in which a layer of a photopolymerised substance were applied to a support and this layer were converted into a substantially solid, non-tacky state, ready for irradiation, without the use of organic solvents.
Not only would, in this stage, the use be avoided of solvents which might present problems of toxicity and fl = a~ility and also cause expense in their recovery, but the production on a continuous basis of coated supports, ready for irradiation, would be facilitated.
We have found that this object can be achieved by the use of certain liquid compositions which contain two kinds of groups through which respectively thermal polymerisation and photocrosslinking can occur. These two types of groups may form part of the same molecule, or they may form part of different molecules. The groups are chosen so that thermal polymerisation of a layer of a liquid composition occurs rapidly to form a solid, essentially tack-free layer, which is, however, still soluble in certain solvents. When desired, a part or parts of the layer are subjected to actinic radiation and photocrosslinking takes place through the other type of group in the already thermally polymerised molecules of the layer, the parts of the layer which undergo photocrosslinking becoming much more resistant-to solution in the solvent.
United States Patent No. 4 291 118 relates to a method fDr forming relief images from a film o~ a liquid photopolymerisable ma~erial, c~mprising exposing the film to chemical hardening treatment sufficient to solidify it, then treating the solidified film in a pattern in a manner differentiating the chemical condition of the film in the pattern as distinct from the chemical condition of thP solidified mass not in the pattern, and then selectively removing the portion of the mass in one of the chemical conditions leaving that portion of the mass in the other chemical condition to for~ a relief image. To bring about the differentiation in chemical condition actinic radiation is used in all the embodiments described, although the disclosure contains the remark "Heat could aïso ~y extension be used".
rn the process described in the United States Patent, therefore, the film of liquid ~aterial is exposed to actinic radiation and then the solidified film is re-exposed to actinic radiation in the form of a pattern so ~hat a part or parts of it become less easily removed 6y a solvent, and finally the image is developed by washing aw~ wit~ the solvent the more readily removed part or parts, i.e., those wfiich were not re~exposed.
The conditions of e~posure have to be carefully controlled;
if the first exposure is insu~ficient, the solidified material remains tacky and inconvenient to handle whereas if it is excessive, images of poor definition are o~tained.
Only the use of p~otopolymerisable polyene-polythiol compositions is described. These have the disadvantage that the polymerisation w~ich is initiated on exposure to actinic radiation continues when such exposure is interrupted. It follows that if images of good quality are to be obtained the second irradiation stage must be performed wlthout delay, This is a constraint on industrial utilisation of the process.
It has r.ow been found that the disadvantages of the prior art processes can be overcome by use of compositions containing both 1,2-epoxide groups and chalcone and/or cinnamate groups on the same or different molecules.
Compounds containing one or more epoxide groups, and those containing one or more chalcone or cinnamate groups, are well 5~;
- 4 ~
known and are commercially available. Compounds containing, in the same molecule, 60th at least one 1,2-epo~ide and at least one chalcone or cinnamate group, are also kno~m from United States Patent Specifications Nos. 3 ~09 593 3 ~97 353, and 3 539 343. As descrihed in thDse Specifications it is also known to form homopolymers or copolymers from t~ese compounds through ring-opening of the epQ3ide groups by means of ionic catalysts7 and to apply these homopolymers or copolymers to a suhstrate to form a light-sensitiYe reproduction layer. The ionic catalysts are usually anionic, viz., an aluminium, zinc, or-magnesium alkyl, such as aluminium triethyl, and polymerisation is carried out at from 20 to 100C, normally at 60 to 70C. In one case, however (US 3 539 343~ use of a cationic catalyst such as boron trifluoride or an ether complex thereof is described, with the observation that polymerisation temperatures should be as low as possible, typically from -5 to ~60C: in the sole Example, a temperature of 15 to 22 C is used.
These homopolymers and copolymers are usually solids and have to be applied as solutions in chloroform or benzene, ~hich, as already pointed out, is disadvantageous.
We have surprisingly found that liquid compositions containing at least one epoxy group and at least one chalcone or cinnamate group can be thermally polymerised using latent catalysts on a carrier such 2S a copper-clad laminate, without the need to 5l?~s~
u~e ~ 901vent, to for3 a ~olld but atill croD~linkabla layar ~hich can thQn b~ exposed i~age~i~0 to ac~inic r~diatlon to cro~llnk th~
expo~ad areaD~ leaving the unexpo~ed are~ ~oluble ln 8 ~olv~nt d0v~10per .
One ~apect of thll inYention accordingly pro~lde~ a proce0a fo~
th0 production of an lm~ge whlch coDprise~
(l) heating a l~yer, auppDrtad on a carrl~r, of a llquld co~posi~ion containing (A3 a heat-actlvat~d la~ent poly~rlsing ~gent for 1,2-opoxtde3 ~lth (B) ~ llght ~ensitive compo~nd having ln th0 a8~a ~olecu1e lea~t ona 1,2-epo~lde group of for2ula -C~
and ~t lea~t one chslcona or cinnamate group of for~l~
- Ar - X - II
wh~ra Ar 19 a bcn~ene rin~ or a benz~ne rln~ sub~titu~ad by alkylD
cycloal~yl, alk~Dnyl9 ~l~oxy, alkoxycarbonyl, esch of thea~ ~roups h~ing a ~qxl~u~ of nlne carbon ~to~s, balogen, hydroxy, a prl~ary, aQcondary or tertlary a~lno group, nltro, a carboxyl, ~lfonlc or phoDphorlc acid gro~p or a ~slt ~hereof9 and X l~ 8 chain of for~uls t~ co ~ D c or -CO-C-CH ~ R4 ~=C-CO- IV
or --CH=C-C~O' C=C~l-- V
or R3 -CE--C~C~O~ VI
Rl and R2 indi~idually denote a hydrogen at~m, an alkyl group of 1 to 4 carbon atoms, or conjointly denote a poly~ethylene chain of 2 to 4 ~ethylene groups?
R3 and R4 each denote a hydrogen atom, an alkyl group of 1 to 4 carbon a~oms, or a phenyl group, and a and ~ each denote zero, 1, or 2 wi.h the pro~iso that they do not both deno~e zero, or with a ~o~ re of CC) a comDound contai~ing at least one 1,2-epo~ide group of formula I9 together with (D) a com~ou~d co~taining at lesst one chalcone or cinnamate group of formuIa II, or with a ~xture of a light sensitiYe compound CB~ with a compound (C~ and¦or (D) as herein defined, - such that the layer solidifies hy thermal polymerisation and becomes essentially non-tacky ~ut remains photocrosslinkable, 8S~;
and subsequently, (ii) exposing the solidified layer to actinic radiation in a predetermined pattern such tnat exposed parts of the layer are crosslinked and ciii~ removing those parts of the layer which have not become substantially crosslinked hy treatment with a solvent therefor.
The phrase "exposing in a predeter~ined pattern" includes both exposure through an image~bearing transparency and exposure to a laser beam moved as directed by a computer to form an image.
Usually the compound CC~ contains one or two groups of formula r, and the compound CD2 contains 2 to 20 groups of formula II. Generally (B~, CC) 9 and (D2 have a molecular weight of at most 20,000. Prefera~ly the group or groups of formula I are either directly attached to a cycloaliphatic ring through both indicated free valencies, or form part of a 2,3-epogypropyl group directly attached to an atGm of oxygen, nitrogen, or sulphur.
Preferred compounds CB2 are those ~hich contain 1 or 2 groups of formula I and 1 to 20 groups of formula II. These groups may be attached o aliphatic, aromatic, araliphatic, cycloaliphatic or he~erocyclic molecules. Par~icularly preferred com2ounds CB) are those in which the group -Ar-X- is a cinnamoylo~y group or forms part of a group of formula 8~6 (R5)c \ ,1 R6 VII
(R5) ~ xl_R7_ ~'III
~her~
X denotes a group of formula III, IV or V, each R5 represents a ~alogen atG~, such as a chlori~e or br~mine atQm, an alkyl, cycloalkyl, alkenyl, alko~y or alk~2y~-carbonyl group containing ~p to 9 car~on atoms, sucn as a ~ethyl, metho~y, cyclohe~yl, allyl, or etfi~ycarbonyl group, a hydro~y group, a pr;~mary, secondary or tertiary amino group, a nitro group9 a carboxyl, sulphonic or phosphoric acid group or a salt thereof, especially a sod;um, potassium, or tetramethylammonium salt, each c r~presents zero or an integer of 1 to 4, preferably zero, 1 or 2, R6 denotes an alkyl group of 1 to 6 carbon atoms, &n alkenyl group of 2 to 6 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms, an aryl group of 6 to 15 carbon atoms or an alkaryl or aralkyl group of 7 to 10 carbon atoms, said group being optionally substituted by one or more hydroxyl groups9 such g as a methyl, 2-hydroxyethyl~ phenyl, 4-hydro~ybutyl, allyl, cyclohexyl, tolyl or 6enzyl group and R7 denotes an-alkylene group of 1 to 6 carbon atoms, an alkenylene group of 2 to 6 car~on atoms, a cyclolalkylene group OL- 3 to 6 carbon at~ms, an arylene group of 6 to 15 carbon atoms or an alkarylene or aralkylene group of 7 to 10 carbon atoms, such as a methylene, 2-butenylene, cyclohexenylene, phenylene, and l-phenylethylene groups.
Especially preferred groups of formula VII are those in which R denotes a group of for~ula (R ~c r ~
IX
.
or a ~et~yl or etfiyl gro~p, Especially preferred groups of formula ~IIr are those in whic~ R denotes a group of formula (R )c where R5 and c are as ~erein~efore defined, The compound Cg~ ~ay, for e~a~ple, ~e a glycidyl ester of a cinnamic acid, a partial ester foTmed ~y reaction of an epoxide ., ~
s~
-- 10 '`
resin with less than one equiyalent of a cinna~ic acid, or a glycidyl ether of a-mono~ydric or di~ydric phenol containing a chalcone unit, especially one of formula R5)C
\ ' _~ Xl-R8 . -~[
(R5) (~5) C~2 ~ CH-CH20 ~ Xl ~ XII
~r CH2 ~E-CH20 ~ xl _~OCH'2C~l-CE~2 XIII
where R8 de~otes a ~ethyl or ethyl group and R5, ~land c are as hereinhefore defined, glycidyl ethers prepared by ad~ancing diglycidyl ethers containing chalcone units witfi bisphenols such as 2,2~isC4-~ydr~yphenyl~-propane C~isphenol A~, ~isC4~hydro~yphenyl~met~ane or 2,2-~isC3,s-dibromo-4-hydroxyphenyl)propane. (tetrabromobisphenol A), or with hydantoins such as 5,5-dimethylhydantoin or 5,5-pentamethylenehydantoin, and glycidylderivativespreparedby advancing diglycidylderivativesof such bisphenols or ~ydantoins with hydro~ry-~suhstituted chalcones.
Particularly preferred c~mpounds CB2 are glycidyl cinnamate, partial reaction products of cinnamic acid with epo~idised novolaks or diglycidyl ethers of ~isphenol A? and compounds of formula CH2--C~-CE~20 _~CH=C~-U -CH=CHR8 CH2--CH--CH20 ~ ~=CEIC CH=C~l ~ XV' and CH2-~C~ ~ 0 ~ ~CE~C-CE~CE ~
~here R8 is as herein~efore defined and R9 ~epresents- a hydr~gen at~m or a ~drQ~y gro~p, glycidyl et~ers prepaEed hy adyancement of a fiisphenol A
diglycidyl ether Wlt~ 2~4~? 2 ~4~? 2 ?4 ~7 2 ?3~? 2~5 ., 2~2 p 4,4t_, or 3,4'-dihydro~ychalcone, or 1?5 -~is(p-hydr~yphenyl2penta-1,4-dien-3-one, gly~idyl deri~ati~es preparea ~y ad~ancing N,~'~
diglycidyl-5,5-d~methyl hydantoin wit~ l?5~is~p-hydrQ~yphenyl2 penta 1,4-dien-3~one, 4,4t~diglycIdylQ~ychalcone, 1,4~bisC3-C4 glycidyloxyphenyl2-3~o~o-l~p~openyl2~enzene, 4,4'~diglycidyl--2,6-3C~
dimethylchalcone, l-(p-glycidyloxyphenyl)hexa-1,4-dien-3~one, l-(p-glycidyloxyphenyl~-5-phenylpenta-1,4-dien-3-one, l-(p-glycidyloxyphenyl)-5-Cp-hydroxyphenyl)penta-1,4-dien-3 one, or 1,5-~is ~-glycidyloxyphenyl~penta-1,4-dien-3~one.
Typical compounds CC~ are mono or polyglycidyl esters obtainable by reaction of a compound containing one or more carboxylic acid groups per molecule with epichlorohydrin or glycerol dichlorohydrin in the presence of an alkali. Such glycidyl esters are preferably deriYed from aliphatic mono and polycarboxylic acids, e,g., acetic and propionic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, or di~erised or trimerised linoleic acid; from cycloaliphatic mono and polycarboxylic acids such as tetrahydrophthalic acid, cyclohexane carboxylic acid, 4-methyl-tetrahydropht~alic acid, hexahydrophthalic acid, and 4-methyl-hexahydrophthalic acid; and from aromatic ~ono and polycarboxylic acids such as benzoic acid~ phthalic ~cid, isophthalic acid, and terephthalic acid.
Further examples are mono and polyglycidyl ethers obtainable by reaction of a compound containing one or more free alcoholic hydroxyl andlor phenolic hydroæyl groups per molecule with epichlorohydrin under alkaline conditions or, alternatively, in the presence of an acidic catalyst and subsequent treatment with alkali. These ethers may be made from acyclic alcohols such as butanol and other monohydric alcohols having from 1 to 8 carbon ;
atoms, ethylene glycol, poly(oxyethylene~glycols, propane-1,2-diol, polyCoxypropylene2 glycols, propane-1,3-diol, butane-1,4-diol, poly(oxytetramethylene2 glycols, glycerol, pentaerytnritol, and poly(epichlorohydrin2. Or they may be made from mononuclear phenols, such as phenol itself, cresol, resorcinol and from polynuclear phenols, such as ~isC4-hydroxyphenyl)methane, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl) sulphone, 1,1,2,2-tetrakis(4-hydro~yphenyl~ethane, 2,2~bisC4-hydro~yphenyl2propane Cotherwise known as bisphenol A~, 2,2~bisC3,5-dibromo-4-hydroxy-phenyl~propane, and novolaks formed from aldehydes such as fo~maldehyde with phenol, Other suitable compounds cc2 are poly(N-glycidyl) compounds including, for example, those obtained by dehydrochlorination of the reaction products of epichlorohydrin with amines containing at least two amino~hydrogen atoms, such as aniline, n-butylamine, and bis(4-aminophenyl2methane; triglycidyl isocyanurate; and N,N'-diglycidyl derivatives of cyclic alkylene ureas, such as ethyleneurea, and of hydantoins such as 5,5-~dimethylhydantoin.
Epoxide resins in which some or all of the epoxide groups are not terminal may also be employed, such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, 4-oxa-tet~acyclo ~.2.1.02~7.03~5]undec-9~yl glyci~yl ether, the bis(4-oxatetracyclo [6.2.1.02'7.0 '5]undec-9-yl2 ether of ethylene s~;
glycol, 3,4-epoxycyclohexylmethyl 3~,4'-epoxycyclohexane-carboxylate and its 6,6'~dimethyl de~i~ative, the bis(3,4-epoxy-cyclohexanecarboxylate2 of ethylene glycol, 3-~3,4-epoxycyclohexyl)-8,9-epoxy-2,4-dioxaspiro¦5,53undecane, and epoxidised butadienes or copolymers of 6utadiene with ethylenic compounds such as styrene and vinyl acetate. If desired a mixture of compounds (C~ may be used.
Especially preferred compounds tc2, used in the process of this invention are 2,2,4-trimethylpentyl glycidyl ether, phenyl glycidyl ether,butylglycidylether, diglycidylethers of dihydric phenols such as 2,2-bis(4-hydroxyphenyl~propane and bisC4-hydroxyphenyl)methane and of dihydric alcohols such as of butane-1,4-diol, and N,N'-derivatives of hydantoins, such as 1,3-diglycidyl 5,5-dim~thyl-hydantoin.
Compounds CD~ include full and partial esters of cinnamic acid with aliphatic glycols and polyols such as triethylene glycol, tetraethylene glycol, and pentaerythritol and epoxide resins that have 6een fully esterified by a cinnamic acid, especially epoxidised novolaks and diglycidyl ethers of bisphenol A which have been thus esterified.
Also suitable as compound(D3are chalcones of formula or ~X ~ X II
3~i~
~c ~ ~ y ~ XVIII
where R5, Xl and c have the ~eanings previously assigned, and Y
denotes an oxygen or sulphur atom, and epoxide resins that have been advanced to negligible epoxide content by reaction with a chalcone of for~ula ~VII or X~TIII in which one or two groups R
denote hydroxy, carboxyl, or primary or secondary amino groups.
Preferred compo~nds D are 1,5~bis(4~hydroxyphenyl)penta-1,4-dien-3-one, bisphenol A diglycidyl ether advanced to negligible epoxide content with 1,5-bis(4-hydroxyphenyl)penta-1,4-dien-3-one, tetrabromobisphenol A diglycidyl ether advanced to a negligible epoxide content ~ith 1,5-bis(b-hydroxyphenyl)penta-1,4-dien-3-one, 1,3-bis(4-hydroxyphenyl)prop-1-en~3~one ? 1-(2-furyl)-3-(4-hydro~y-phenyl)prop-l-en-3-one, and 2,6-bis(4-hydroxybenzylidenyl) cyclohexanone.
The polymerising agent (A2 is one having little or no effect on the epoxide group of (B) and (C) if present, below a certain 'threshold tem~erature' but which causes rapid polymerisation through the epoxide ring once the temperature of the mixture rises above that threshold temperature~ The threshold temperature is preferably at least 100 C, so that (A) has a significant heat-polymerising effect on CB) and (C) only at temperatures above 100C.
S~,i Preferably the layer is heated at 120 C to 200 C for from 2 to 20 minutes.
Suitable polymerising agents (A? include complexes of boron trichloride or of boron trifluoride, chelates of boron difluoride, for example with.a diketone, dicyandiamide or an imidazole.
Suitable boron difluoride chelates such as difluoroboron-acetoacetanilide are described in United States Patent Specification No. 3 424 6~9. Suitable imidazoles include 2-methyl-imidazole, 2-phenylimidazole, l~benzyl~2~methylimidazole and l-cyanoethyl-2~methylimidazole.
Preferred polymerising agents CA~ are complexes of boron trichloride with a tertiary amine, or o~ boron trifluoride with a triaryl phosphine, with.piperidîne~ or with.a primary amine, these pri~ary and tertiary amines b.eing alip~atic, cycloaliphatic or heterocyclic. An example of a sui~able ~oron trichloride-tertiary amine complex is ~oron trichloride~trimethylamine complex; other suitable boron trichloride~tertiary amine co~plexes are described in United Statas Patent Specification No. 3 784 647, an especially preferred such complex being boron trichloride-octyldimethylamine complex. Examples of suitable boron trifluoride complexes are those with triphenylphosphine, isophoronediamine, benzylamine, cyclohexylamine and tetramethylhexamethylenediamine. A-Q especially preferred boron tri~luoride complex is that with ethylamine.
The compounds (B), (C) and (D) may be liquids or solids, but as stated above, the compositions are applied in a liquid form to a carrier. The viscosity of the composition prefer~bly lies within the range 0.1 to 15 Pa s. To render solid materials into the liquid form, and to meet this desired range of viscosity without the addition of volatile solvents, it may be necessary to use mixtures of compounds (B) and (D), or (B) and (C) or (B), (C), and (D). It is particularly advantageous to include, as an epoxide-functional material (C), a monoepoxide, either alone or in admixture with other epoxide functional materials (B) and (C). Particularly preferred monoepoxides include n-butyl glycidyl ether and phenyl glycidyl ether.
The amount of polymerising agent (A) used is generally from 1 to 10 parts by weight per 100 parts in total of compound (B) and/or (C~; 2 to 5 parts by ~eight of (A~ per 100 parts by weight of (B) and/or ~C~ is particularly preferred, It is possible to add to the ~ixture of (A) and (B) and/or (A~ and CC~ and CD) small amounts of sensitisers which reduce the exposure time or permit the use of light sources of lower output.
The liquid c~mposition can be applied to suitable carriers by the customary techniques, such as spray coating, whirler coating, roller coating, cascade coating, and especially curtain coating. Typically, the carrier is coated such that the layer ; of the composition is 1 to 250 ~m thick. The carrier may be of, for e~ample, copper, aluminium or other metal, paper, synthetic resin, or glass.
In the pho~ocrosslinking stage of the process of thi invention actinic radiation of wavelenoth 200-600 n~ is preferably used. Suitable sources of actinic radiation include carbon arcs, mercury vapour arcs, fluorescent lamps with phosphors emitting ultraviolet light, argon and ~enon glow lamps, tungsten lamps, and photographic flood lamps. Of these, mercury vapour arcs, particularly sun lamps, fluorescent sun lamps, and metal halide lamps are most suitable. The times required for the exposure will depend upon a variety of factors which include, for example, the individual compound used, the type of light shource, and the distance of that source from the irradiated co~position.
Suita~le times may be readily determined by those familiar with photocrosslinking techniques.
~ uitable solYents for development of the image are readily found by routine testing and include cyc]ohe~anone, trimethyl-cyclohexanone, 2-ethoxyethanol, l,l,l-trichloroethane, chloroform, and mi~tures thereof. The action of the solvent ~ay ~eed to be assisted by agitation or by gentle brushing. ~nen the carrier has a layer of a suitable electrically~conducting metal, usually copper or silver, i~mediately in contact with the composition, after e~posure the no~-photocrosslinked polymer can be removed to expose the metal. Metal so exposed ~ay then be etched away ~n the non-image areas, so forming a printed circuit, by means of etching fluids such as ferric chloride or ammonium persulphate solutions.
The invention will now be illustrated by reference to the ~, ,, S~;
following Examples in which all parts and percentages are b;
weight.
The compounds that are not commercially available used in these E~mpless are prepared as follows:
4-(p-~ydroxyphenyl)but-3-en-2-one (16.2 g) is dissolved in ethanol (50 ml) and slowly treated with sodium hydroxide (4.2 g) in water (58 ml). The mixture is cooled to 10 C and p-(glycidyloxy)-benzaldehyde ~17.8 g) in ethanol (S0 ml) is added slowly, keeping the temperature below 10C. The mixture is stirred for a further
-- 1 ~
PROCESS FOR THI~ PRODUCTION OF IMAGES
, This invention relates to a process for the production of images by heating followed by exposure ~o actinic radiation.
Conventionally, production of an image by means of photopolymerisation is achi~ed by coating a support with a solution in a volatile organic solvent of a photopolymerisable substance, causing or allowing the solvent to evaporate so leaving a film of the p~otopolymerisable substance, irradiating the film with actinic radiation as through a negative whereby the parts of the film struck by the irradiation become photopolymerised Cand less soluble~ while those parts shielded ~rom the irradiation remain substantially una.fected, then dissolving away the unirradiated, unphotopolymerised parts of the film by means of a suitable solvent which does not dissolve the irradiated, photopolymerised parts. This last stage is conventionally known as "development".
It would ~e desirable to have a process in which a layer of a photopolymerised substance were applied to a support and this layer were converted into a substantially solid, non-tacky state, ready for irradiation, without the use of organic solvents.
Not only would, in this stage, the use be avoided of solvents which might present problems of toxicity and fl = a~ility and also cause expense in their recovery, but the production on a continuous basis of coated supports, ready for irradiation, would be facilitated.
We have found that this object can be achieved by the use of certain liquid compositions which contain two kinds of groups through which respectively thermal polymerisation and photocrosslinking can occur. These two types of groups may form part of the same molecule, or they may form part of different molecules. The groups are chosen so that thermal polymerisation of a layer of a liquid composition occurs rapidly to form a solid, essentially tack-free layer, which is, however, still soluble in certain solvents. When desired, a part or parts of the layer are subjected to actinic radiation and photocrosslinking takes place through the other type of group in the already thermally polymerised molecules of the layer, the parts of the layer which undergo photocrosslinking becoming much more resistant-to solution in the solvent.
United States Patent No. 4 291 118 relates to a method fDr forming relief images from a film o~ a liquid photopolymerisable ma~erial, c~mprising exposing the film to chemical hardening treatment sufficient to solidify it, then treating the solidified film in a pattern in a manner differentiating the chemical condition of the film in the pattern as distinct from the chemical condition of thP solidified mass not in the pattern, and then selectively removing the portion of the mass in one of the chemical conditions leaving that portion of the mass in the other chemical condition to for~ a relief image. To bring about the differentiation in chemical condition actinic radiation is used in all the embodiments described, although the disclosure contains the remark "Heat could aïso ~y extension be used".
rn the process described in the United States Patent, therefore, the film of liquid ~aterial is exposed to actinic radiation and then the solidified film is re-exposed to actinic radiation in the form of a pattern so ~hat a part or parts of it become less easily removed 6y a solvent, and finally the image is developed by washing aw~ wit~ the solvent the more readily removed part or parts, i.e., those wfiich were not re~exposed.
The conditions of e~posure have to be carefully controlled;
if the first exposure is insu~ficient, the solidified material remains tacky and inconvenient to handle whereas if it is excessive, images of poor definition are o~tained.
Only the use of p~otopolymerisable polyene-polythiol compositions is described. These have the disadvantage that the polymerisation w~ich is initiated on exposure to actinic radiation continues when such exposure is interrupted. It follows that if images of good quality are to be obtained the second irradiation stage must be performed wlthout delay, This is a constraint on industrial utilisation of the process.
It has r.ow been found that the disadvantages of the prior art processes can be overcome by use of compositions containing both 1,2-epoxide groups and chalcone and/or cinnamate groups on the same or different molecules.
Compounds containing one or more epoxide groups, and those containing one or more chalcone or cinnamate groups, are well 5~;
- 4 ~
known and are commercially available. Compounds containing, in the same molecule, 60th at least one 1,2-epo~ide and at least one chalcone or cinnamate group, are also kno~m from United States Patent Specifications Nos. 3 ~09 593 3 ~97 353, and 3 539 343. As descrihed in thDse Specifications it is also known to form homopolymers or copolymers from t~ese compounds through ring-opening of the epQ3ide groups by means of ionic catalysts7 and to apply these homopolymers or copolymers to a suhstrate to form a light-sensitiYe reproduction layer. The ionic catalysts are usually anionic, viz., an aluminium, zinc, or-magnesium alkyl, such as aluminium triethyl, and polymerisation is carried out at from 20 to 100C, normally at 60 to 70C. In one case, however (US 3 539 343~ use of a cationic catalyst such as boron trifluoride or an ether complex thereof is described, with the observation that polymerisation temperatures should be as low as possible, typically from -5 to ~60C: in the sole Example, a temperature of 15 to 22 C is used.
These homopolymers and copolymers are usually solids and have to be applied as solutions in chloroform or benzene, ~hich, as already pointed out, is disadvantageous.
We have surprisingly found that liquid compositions containing at least one epoxy group and at least one chalcone or cinnamate group can be thermally polymerised using latent catalysts on a carrier such 2S a copper-clad laminate, without the need to 5l?~s~
u~e ~ 901vent, to for3 a ~olld but atill croD~linkabla layar ~hich can thQn b~ exposed i~age~i~0 to ac~inic r~diatlon to cro~llnk th~
expo~ad areaD~ leaving the unexpo~ed are~ ~oluble ln 8 ~olv~nt d0v~10per .
One ~apect of thll inYention accordingly pro~lde~ a proce0a fo~
th0 production of an lm~ge whlch coDprise~
(l) heating a l~yer, auppDrtad on a carrl~r, of a llquld co~posi~ion containing (A3 a heat-actlvat~d la~ent poly~rlsing ~gent for 1,2-opoxtde3 ~lth (B) ~ llght ~ensitive compo~nd having ln th0 a8~a ~olecu1e lea~t ona 1,2-epo~lde group of for2ula -C~
and ~t lea~t one chslcona or cinnamate group of for~l~
- Ar - X - II
wh~ra Ar 19 a bcn~ene rin~ or a benz~ne rln~ sub~titu~ad by alkylD
cycloal~yl, alk~Dnyl9 ~l~oxy, alkoxycarbonyl, esch of thea~ ~roups h~ing a ~qxl~u~ of nlne carbon ~to~s, balogen, hydroxy, a prl~ary, aQcondary or tertlary a~lno group, nltro, a carboxyl, ~lfonlc or phoDphorlc acid gro~p or a ~slt ~hereof9 and X l~ 8 chain of for~uls t~ co ~ D c or -CO-C-CH ~ R4 ~=C-CO- IV
or --CH=C-C~O' C=C~l-- V
or R3 -CE--C~C~O~ VI
Rl and R2 indi~idually denote a hydrogen at~m, an alkyl group of 1 to 4 carbon atoms, or conjointly denote a poly~ethylene chain of 2 to 4 ~ethylene groups?
R3 and R4 each denote a hydrogen atom, an alkyl group of 1 to 4 carbon a~oms, or a phenyl group, and a and ~ each denote zero, 1, or 2 wi.h the pro~iso that they do not both deno~e zero, or with a ~o~ re of CC) a comDound contai~ing at least one 1,2-epo~ide group of formula I9 together with (D) a com~ou~d co~taining at lesst one chalcone or cinnamate group of formuIa II, or with a ~xture of a light sensitiYe compound CB~ with a compound (C~ and¦or (D) as herein defined, - such that the layer solidifies hy thermal polymerisation and becomes essentially non-tacky ~ut remains photocrosslinkable, 8S~;
and subsequently, (ii) exposing the solidified layer to actinic radiation in a predetermined pattern such tnat exposed parts of the layer are crosslinked and ciii~ removing those parts of the layer which have not become substantially crosslinked hy treatment with a solvent therefor.
The phrase "exposing in a predeter~ined pattern" includes both exposure through an image~bearing transparency and exposure to a laser beam moved as directed by a computer to form an image.
Usually the compound CC~ contains one or two groups of formula r, and the compound CD2 contains 2 to 20 groups of formula II. Generally (B~, CC) 9 and (D2 have a molecular weight of at most 20,000. Prefera~ly the group or groups of formula I are either directly attached to a cycloaliphatic ring through both indicated free valencies, or form part of a 2,3-epogypropyl group directly attached to an atGm of oxygen, nitrogen, or sulphur.
Preferred compounds CB2 are those ~hich contain 1 or 2 groups of formula I and 1 to 20 groups of formula II. These groups may be attached o aliphatic, aromatic, araliphatic, cycloaliphatic or he~erocyclic molecules. Par~icularly preferred com2ounds CB) are those in which the group -Ar-X- is a cinnamoylo~y group or forms part of a group of formula 8~6 (R5)c \ ,1 R6 VII
(R5) ~ xl_R7_ ~'III
~her~
X denotes a group of formula III, IV or V, each R5 represents a ~alogen atG~, such as a chlori~e or br~mine atQm, an alkyl, cycloalkyl, alkenyl, alko~y or alk~2y~-carbonyl group containing ~p to 9 car~on atoms, sucn as a ~ethyl, metho~y, cyclohe~yl, allyl, or etfi~ycarbonyl group, a hydro~y group, a pr;~mary, secondary or tertiary amino group, a nitro group9 a carboxyl, sulphonic or phosphoric acid group or a salt thereof, especially a sod;um, potassium, or tetramethylammonium salt, each c r~presents zero or an integer of 1 to 4, preferably zero, 1 or 2, R6 denotes an alkyl group of 1 to 6 carbon atoms, &n alkenyl group of 2 to 6 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms, an aryl group of 6 to 15 carbon atoms or an alkaryl or aralkyl group of 7 to 10 carbon atoms, said group being optionally substituted by one or more hydroxyl groups9 such g as a methyl, 2-hydroxyethyl~ phenyl, 4-hydro~ybutyl, allyl, cyclohexyl, tolyl or 6enzyl group and R7 denotes an-alkylene group of 1 to 6 carbon atoms, an alkenylene group of 2 to 6 car~on atoms, a cyclolalkylene group OL- 3 to 6 carbon at~ms, an arylene group of 6 to 15 carbon atoms or an alkarylene or aralkylene group of 7 to 10 carbon atoms, such as a methylene, 2-butenylene, cyclohexenylene, phenylene, and l-phenylethylene groups.
Especially preferred groups of formula VII are those in which R denotes a group of for~ula (R ~c r ~
IX
.
or a ~et~yl or etfiyl gro~p, Especially preferred groups of formula ~IIr are those in whic~ R denotes a group of formula (R )c where R5 and c are as ~erein~efore defined, The compound Cg~ ~ay, for e~a~ple, ~e a glycidyl ester of a cinnamic acid, a partial ester foTmed ~y reaction of an epoxide ., ~
s~
-- 10 '`
resin with less than one equiyalent of a cinna~ic acid, or a glycidyl ether of a-mono~ydric or di~ydric phenol containing a chalcone unit, especially one of formula R5)C
\ ' _~ Xl-R8 . -~[
(R5) (~5) C~2 ~ CH-CH20 ~ Xl ~ XII
~r CH2 ~E-CH20 ~ xl _~OCH'2C~l-CE~2 XIII
where R8 de~otes a ~ethyl or ethyl group and R5, ~land c are as hereinhefore defined, glycidyl ethers prepared by ad~ancing diglycidyl ethers containing chalcone units witfi bisphenols such as 2,2~isC4-~ydr~yphenyl~-propane C~isphenol A~, ~isC4~hydro~yphenyl~met~ane or 2,2-~isC3,s-dibromo-4-hydroxyphenyl)propane. (tetrabromobisphenol A), or with hydantoins such as 5,5-dimethylhydantoin or 5,5-pentamethylenehydantoin, and glycidylderivativespreparedby advancing diglycidylderivativesof such bisphenols or ~ydantoins with hydro~ry-~suhstituted chalcones.
Particularly preferred c~mpounds CB2 are glycidyl cinnamate, partial reaction products of cinnamic acid with epo~idised novolaks or diglycidyl ethers of ~isphenol A? and compounds of formula CH2--C~-CE~20 _~CH=C~-U -CH=CHR8 CH2--CH--CH20 ~ ~=CEIC CH=C~l ~ XV' and CH2-~C~ ~ 0 ~ ~CE~C-CE~CE ~
~here R8 is as herein~efore defined and R9 ~epresents- a hydr~gen at~m or a ~drQ~y gro~p, glycidyl et~ers prepaEed hy adyancement of a fiisphenol A
diglycidyl ether Wlt~ 2~4~? 2 ~4~? 2 ?4 ~7 2 ?3~? 2~5 ., 2~2 p 4,4t_, or 3,4'-dihydro~ychalcone, or 1?5 -~is(p-hydr~yphenyl2penta-1,4-dien-3-one, gly~idyl deri~ati~es preparea ~y ad~ancing N,~'~
diglycidyl-5,5-d~methyl hydantoin wit~ l?5~is~p-hydrQ~yphenyl2 penta 1,4-dien-3~one, 4,4t~diglycIdylQ~ychalcone, 1,4~bisC3-C4 glycidyloxyphenyl2-3~o~o-l~p~openyl2~enzene, 4,4'~diglycidyl--2,6-3C~
dimethylchalcone, l-(p-glycidyloxyphenyl)hexa-1,4-dien-3~one, l-(p-glycidyloxyphenyl~-5-phenylpenta-1,4-dien-3-one, l-(p-glycidyloxyphenyl)-5-Cp-hydroxyphenyl)penta-1,4-dien-3 one, or 1,5-~is ~-glycidyloxyphenyl~penta-1,4-dien-3~one.
Typical compounds CC~ are mono or polyglycidyl esters obtainable by reaction of a compound containing one or more carboxylic acid groups per molecule with epichlorohydrin or glycerol dichlorohydrin in the presence of an alkali. Such glycidyl esters are preferably deriYed from aliphatic mono and polycarboxylic acids, e,g., acetic and propionic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, or di~erised or trimerised linoleic acid; from cycloaliphatic mono and polycarboxylic acids such as tetrahydrophthalic acid, cyclohexane carboxylic acid, 4-methyl-tetrahydropht~alic acid, hexahydrophthalic acid, and 4-methyl-hexahydrophthalic acid; and from aromatic ~ono and polycarboxylic acids such as benzoic acid~ phthalic ~cid, isophthalic acid, and terephthalic acid.
Further examples are mono and polyglycidyl ethers obtainable by reaction of a compound containing one or more free alcoholic hydroxyl andlor phenolic hydroæyl groups per molecule with epichlorohydrin under alkaline conditions or, alternatively, in the presence of an acidic catalyst and subsequent treatment with alkali. These ethers may be made from acyclic alcohols such as butanol and other monohydric alcohols having from 1 to 8 carbon ;
atoms, ethylene glycol, poly(oxyethylene~glycols, propane-1,2-diol, polyCoxypropylene2 glycols, propane-1,3-diol, butane-1,4-diol, poly(oxytetramethylene2 glycols, glycerol, pentaerytnritol, and poly(epichlorohydrin2. Or they may be made from mononuclear phenols, such as phenol itself, cresol, resorcinol and from polynuclear phenols, such as ~isC4-hydroxyphenyl)methane, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl) sulphone, 1,1,2,2-tetrakis(4-hydro~yphenyl~ethane, 2,2~bisC4-hydro~yphenyl2propane Cotherwise known as bisphenol A~, 2,2~bisC3,5-dibromo-4-hydroxy-phenyl~propane, and novolaks formed from aldehydes such as fo~maldehyde with phenol, Other suitable compounds cc2 are poly(N-glycidyl) compounds including, for example, those obtained by dehydrochlorination of the reaction products of epichlorohydrin with amines containing at least two amino~hydrogen atoms, such as aniline, n-butylamine, and bis(4-aminophenyl2methane; triglycidyl isocyanurate; and N,N'-diglycidyl derivatives of cyclic alkylene ureas, such as ethyleneurea, and of hydantoins such as 5,5-~dimethylhydantoin.
Epoxide resins in which some or all of the epoxide groups are not terminal may also be employed, such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, 4-oxa-tet~acyclo ~.2.1.02~7.03~5]undec-9~yl glyci~yl ether, the bis(4-oxatetracyclo [6.2.1.02'7.0 '5]undec-9-yl2 ether of ethylene s~;
glycol, 3,4-epoxycyclohexylmethyl 3~,4'-epoxycyclohexane-carboxylate and its 6,6'~dimethyl de~i~ative, the bis(3,4-epoxy-cyclohexanecarboxylate2 of ethylene glycol, 3-~3,4-epoxycyclohexyl)-8,9-epoxy-2,4-dioxaspiro¦5,53undecane, and epoxidised butadienes or copolymers of 6utadiene with ethylenic compounds such as styrene and vinyl acetate. If desired a mixture of compounds (C~ may be used.
Especially preferred compounds tc2, used in the process of this invention are 2,2,4-trimethylpentyl glycidyl ether, phenyl glycidyl ether,butylglycidylether, diglycidylethers of dihydric phenols such as 2,2-bis(4-hydroxyphenyl~propane and bisC4-hydroxyphenyl)methane and of dihydric alcohols such as of butane-1,4-diol, and N,N'-derivatives of hydantoins, such as 1,3-diglycidyl 5,5-dim~thyl-hydantoin.
Compounds CD~ include full and partial esters of cinnamic acid with aliphatic glycols and polyols such as triethylene glycol, tetraethylene glycol, and pentaerythritol and epoxide resins that have 6een fully esterified by a cinnamic acid, especially epoxidised novolaks and diglycidyl ethers of bisphenol A which have been thus esterified.
Also suitable as compound(D3are chalcones of formula or ~X ~ X II
3~i~
~c ~ ~ y ~ XVIII
where R5, Xl and c have the ~eanings previously assigned, and Y
denotes an oxygen or sulphur atom, and epoxide resins that have been advanced to negligible epoxide content by reaction with a chalcone of for~ula ~VII or X~TIII in which one or two groups R
denote hydroxy, carboxyl, or primary or secondary amino groups.
Preferred compo~nds D are 1,5~bis(4~hydroxyphenyl)penta-1,4-dien-3-one, bisphenol A diglycidyl ether advanced to negligible epoxide content with 1,5-bis(4-hydroxyphenyl)penta-1,4-dien-3-one, tetrabromobisphenol A diglycidyl ether advanced to a negligible epoxide content ~ith 1,5-bis(b-hydroxyphenyl)penta-1,4-dien-3-one, 1,3-bis(4-hydroxyphenyl)prop-1-en~3~one ? 1-(2-furyl)-3-(4-hydro~y-phenyl)prop-l-en-3-one, and 2,6-bis(4-hydroxybenzylidenyl) cyclohexanone.
The polymerising agent (A2 is one having little or no effect on the epoxide group of (B) and (C) if present, below a certain 'threshold tem~erature' but which causes rapid polymerisation through the epoxide ring once the temperature of the mixture rises above that threshold temperature~ The threshold temperature is preferably at least 100 C, so that (A) has a significant heat-polymerising effect on CB) and (C) only at temperatures above 100C.
S~,i Preferably the layer is heated at 120 C to 200 C for from 2 to 20 minutes.
Suitable polymerising agents (A? include complexes of boron trichloride or of boron trifluoride, chelates of boron difluoride, for example with.a diketone, dicyandiamide or an imidazole.
Suitable boron difluoride chelates such as difluoroboron-acetoacetanilide are described in United States Patent Specification No. 3 424 6~9. Suitable imidazoles include 2-methyl-imidazole, 2-phenylimidazole, l~benzyl~2~methylimidazole and l-cyanoethyl-2~methylimidazole.
Preferred polymerising agents CA~ are complexes of boron trichloride with a tertiary amine, or o~ boron trifluoride with a triaryl phosphine, with.piperidîne~ or with.a primary amine, these pri~ary and tertiary amines b.eing alip~atic, cycloaliphatic or heterocyclic. An example of a sui~able ~oron trichloride-tertiary amine complex is ~oron trichloride~trimethylamine complex; other suitable boron trichloride~tertiary amine co~plexes are described in United Statas Patent Specification No. 3 784 647, an especially preferred such complex being boron trichloride-octyldimethylamine complex. Examples of suitable boron trifluoride complexes are those with triphenylphosphine, isophoronediamine, benzylamine, cyclohexylamine and tetramethylhexamethylenediamine. A-Q especially preferred boron tri~luoride complex is that with ethylamine.
The compounds (B), (C) and (D) may be liquids or solids, but as stated above, the compositions are applied in a liquid form to a carrier. The viscosity of the composition prefer~bly lies within the range 0.1 to 15 Pa s. To render solid materials into the liquid form, and to meet this desired range of viscosity without the addition of volatile solvents, it may be necessary to use mixtures of compounds (B) and (D), or (B) and (C) or (B), (C), and (D). It is particularly advantageous to include, as an epoxide-functional material (C), a monoepoxide, either alone or in admixture with other epoxide functional materials (B) and (C). Particularly preferred monoepoxides include n-butyl glycidyl ether and phenyl glycidyl ether.
The amount of polymerising agent (A) used is generally from 1 to 10 parts by weight per 100 parts in total of compound (B) and/or (C~; 2 to 5 parts by ~eight of (A~ per 100 parts by weight of (B) and/or ~C~ is particularly preferred, It is possible to add to the ~ixture of (A) and (B) and/or (A~ and CC~ and CD) small amounts of sensitisers which reduce the exposure time or permit the use of light sources of lower output.
The liquid c~mposition can be applied to suitable carriers by the customary techniques, such as spray coating, whirler coating, roller coating, cascade coating, and especially curtain coating. Typically, the carrier is coated such that the layer ; of the composition is 1 to 250 ~m thick. The carrier may be of, for e~ample, copper, aluminium or other metal, paper, synthetic resin, or glass.
In the pho~ocrosslinking stage of the process of thi invention actinic radiation of wavelenoth 200-600 n~ is preferably used. Suitable sources of actinic radiation include carbon arcs, mercury vapour arcs, fluorescent lamps with phosphors emitting ultraviolet light, argon and ~enon glow lamps, tungsten lamps, and photographic flood lamps. Of these, mercury vapour arcs, particularly sun lamps, fluorescent sun lamps, and metal halide lamps are most suitable. The times required for the exposure will depend upon a variety of factors which include, for example, the individual compound used, the type of light shource, and the distance of that source from the irradiated co~position.
Suita~le times may be readily determined by those familiar with photocrosslinking techniques.
~ uitable solYents for development of the image are readily found by routine testing and include cyc]ohe~anone, trimethyl-cyclohexanone, 2-ethoxyethanol, l,l,l-trichloroethane, chloroform, and mi~tures thereof. The action of the solvent ~ay ~eed to be assisted by agitation or by gentle brushing. ~nen the carrier has a layer of a suitable electrically~conducting metal, usually copper or silver, i~mediately in contact with the composition, after e~posure the no~-photocrosslinked polymer can be removed to expose the metal. Metal so exposed ~ay then be etched away ~n the non-image areas, so forming a printed circuit, by means of etching fluids such as ferric chloride or ammonium persulphate solutions.
The invention will now be illustrated by reference to the ~, ,, S~;
following Examples in which all parts and percentages are b;
weight.
The compounds that are not commercially available used in these E~mpless are prepared as follows:
4-(p-~ydroxyphenyl)but-3-en-2-one (16.2 g) is dissolved in ethanol (50 ml) and slowly treated with sodium hydroxide (4.2 g) in water (58 ml). The mixture is cooled to 10 C and p-(glycidyloxy)-benzaldehyde ~17.8 g) in ethanol (S0 ml) is added slowly, keeping the temperature below 10C. The mixture is stirred for a further
2 hours at 10C and then filtered.
The precipitate is dissolved in water, adjusted to pH 7 with dilute hydrochloric acid, and the product is extracted into chloroform. The extract is dried over magnesium sulphate, filtered, and evaporated under reduced pressure to give l-(p-(glycidylo~y)-phenyl~-S~Cp hydroxyphenyl)penta~1,4~dien 3-one having an epoxide content of 2.82 equiv.¦kg Ctheoretical value 3.11 equiv./kg) as a viscous yellow liquid, When the 4-Cp-hydroxyphenyl~but-3-en-2-one is replaced by an equivalent quantity of 4~phenylbut-3-en-2-one the resultant product is l-(p-Cglycidyloxy~phenyl)-S~phenylpenta-1,4-dien-3-one having an epoxide content of 3.19 equiv./kg. (theoretical value
The precipitate is dissolved in water, adjusted to pH 7 with dilute hydrochloric acid, and the product is extracted into chloroform. The extract is dried over magnesium sulphate, filtered, and evaporated under reduced pressure to give l-(p-(glycidylo~y)-phenyl~-S~Cp hydroxyphenyl)penta~1,4~dien 3-one having an epoxide content of 2.82 equiv.¦kg Ctheoretical value 3.11 equiv./kg) as a viscous yellow liquid, When the 4-Cp-hydroxyphenyl~but-3-en-2-one is replaced by an equivalent quantity of 4~phenylbut-3-en-2-one the resultant product is l-(p-Cglycidyloxy~phenyl)-S~phenylpenta-1,4-dien-3-one having an epoxide content of 3.19 equiv./kg. (theoretical value
3.27 equiv./kg), a yellow solid, m.pt. 62-64C.
Resin I
This denotes a light-sensitive epoxide resin based on 1,5-bis(4-glycidyloxyphenyl~penta-1,4-dien-3-one, bisphenol A, and tetrabromobisphenol A, having a molecular weight of 3000-3500, and an epo~ide content of 0.8 to l.0 equivalents/kg.
Resin I1 A mixture of an epoxy novolak resin (100 parts) having an epoxide content of 5.61 equiv. per kg. and being a polyglycidyl ether ~ade from a phenol-formaldehyde novolak of average molecular weignt 420, 2,6-di-t-butyl-p-cresol (0.2 part) and cnromium III
tris octanoate (0.1 part) is heated to 120C and cinnamic acid (83 parts) is added over a period of 1 hour. H~ating is continued for a further 31 hours at 120C and the mixture is then allowed to cool. The product becomes solid at room temperature and has a negligible ep~ide content.
Resin III
2,2-Bis(4-glycidylo~yphenyl)propane having an epoxide content of 5.2 equiYs./kg C52,8 g~, 1,4~bis(3-(4-hydroxyphenyl)-3-oxo-l-propenyl~benzene (44.4 g), 2~etho~yethyl acetate (97.2 g) and tetraethylammonium bromide t0-4 g) are heated to 140 C for 31 hours.
The solvent is evaporated to gi~e a resin having an epoxide content of 0.48 equi~s./kg.
Resin IV
Resin III (48.8 g~ is dissolved in 2-ethoxyethyl acetate (50 g~ and acetic acid (1.4 g) added. The ~ixture is heated at 100C for 71 hours, then evaporated, leaving a resin having a negligible epoxide content.
8~;
EXA~LE 1 A mixture of l-(p-(glycidyloxy)phenyl~-5-phenylpenta-1,4-dien-3-one (75 parts), n-butyl glycidyl ether (25 parts~, and boron trichloride/N-methylpiperidine complex (3 parts) is applied as a coating 10 ~m thick onto a copper-cla~ laminate. It is heated for 5 minutes at 150 C, allowed to cool, and then the solidified layer is irradiated through a negative ~ith a 5000w metal halide lamp at a diseance of 75 cm for 10 minutes. On development ~ith cyclohexanone a good ir~ge is obtained.
The same mixture is prepared as in Example 1, Its viscosity at 25C is 0.345 Pa s. The composition is stored at 25C for 2 months in the dark, at which time its viscosity at 20C is 0.360 Pa s. A portion of this stored composition is applied to a copper-clad laminate as in Example l and heated, irradiated and developed under the same conditions, A good image is likewise obtained.
The process of Example 1 is repeated, using 50 parts of the phenylpentadienone and 50 parts of n-butyl glycidyl ether. The layer is heated for 15 minutes at 160C, then irradiated for 1 minute Development under the same conditions gives a good image.
The process of Example l is repeated, using 10 parts of the phenylpen~adienone and 25 parts of n-butyl glycidyl ether, but 1 part of boron trichloride/N,N-dimethylcyclohexylamine complex. The coated la~inate is heated f or 10 ~inutes at 150C
and the solidified layer is irradiated through a negative for 10 minutes. On development with cyclohexanone a good image is obtained.
EXA~LE S
A mixture of l-(p-(glycidyloxy)phenyl)~S-(p-hydroxyphenyl)- -penta-1,4-dien-3-one (100 parts) and boron trichloride¦octyldimethyl-amine complex (4 parts) is applied as a coating 15 ym thick onto a copper-clad laminate. It is heated for 20 minutes at 150C, allowed to cool, and the solidified layer is irradiated for 20 minutes through a negative as described in Example 1.
A good image is developed using cyclohe~anone with gentle brushing.
- EX~u~PLE 6 Resin I (100 g~ is dissolved in l,4-butanediol diglycidyl ether (50 g) and borontrifluoride monoethylamine complex (4.5 g) is added. The resultant mi~ture is coated at 40 C on~o a copper-clad laminate to a thic~ness of 20 ~m. The laminate is heated at 120C for 5 minutes, which solidifies the coating. It is then irradiated through a negative for 30 seconds, as described in Examp1e 1. Development in cyclohexanone gives a good image.
E~AMPLE 7 Resin II Clo g) is dissolved in butyl glycidyl ether (5 g~
and the boron trifluoride complex of triphenyl phosphine ~0.2 g~
s~
and 4,4'~6is~dxmethylamino~enzophenone C0.2 g~ is added. The resultant solution is coated to a thickness of 35 ~m onto a copper~
clad laminate. The laminate is heated at 120C ~or 5 minutes which so]idifies the coating. It is then irradiated through a negative for 15 ~inutes, as descri~ed in Example 1. Deyelopment in chloroform gives a good image.
E~AMPLE 8 Resin III (20 parts~ is dissolyed in ~utyl glycidyl ether ~10 parts~ and boron trichloride trimethylamine complex C0,6 part2 is added. This solution is coated onto a copper-clad laminate to give a coating 20 pm thick. The laminate is heated at 120C
for 10 minutes to give a tack-free surface. This is irradiated through a negative, as descrihed in Example 1, for 5 minutes.
~evelopmen~ in cyclohexanone gives a good image.
EXAMPLE ~
Resin IV C20 parts~ is dissolved in hutyl glycidyl ether (10 parts~, and 1,4 butane diol diglycidyl ether Clo parts~, Boron trichloride octyldimethyl~mine complex C2 parts~ is then added and the resultant solution is coated onto a copper-clad ~laminate to give a coating 40 ~m thick. This is heated at 120C
for 15 ~inutes, to give a tack~free coating. The coating is ~irradiated for 5 minutes through a negative, as described in E~ample 1. Development in cyclohexanone gives a good image.
....
- 24 - ~ 6 ~ rPLE 10 Resin I C10 parts~ is dissolved in phenyl ~lycidyl ether (lO parts~ to which is added difluoro~oron-acetoacetanilide ~0.1 part~. The solution is coated onto a copper-clad laminate as a layer 35 pm thick, then heated at 120C for 10 ~inutes to solidify the coating. The coating is then irradiated for 1 minute through a nègative as described in E~ample 1. Development in cyclohe~anone gives a good image,
Resin I
This denotes a light-sensitive epoxide resin based on 1,5-bis(4-glycidyloxyphenyl~penta-1,4-dien-3-one, bisphenol A, and tetrabromobisphenol A, having a molecular weight of 3000-3500, and an epo~ide content of 0.8 to l.0 equivalents/kg.
Resin I1 A mixture of an epoxy novolak resin (100 parts) having an epoxide content of 5.61 equiv. per kg. and being a polyglycidyl ether ~ade from a phenol-formaldehyde novolak of average molecular weignt 420, 2,6-di-t-butyl-p-cresol (0.2 part) and cnromium III
tris octanoate (0.1 part) is heated to 120C and cinnamic acid (83 parts) is added over a period of 1 hour. H~ating is continued for a further 31 hours at 120C and the mixture is then allowed to cool. The product becomes solid at room temperature and has a negligible ep~ide content.
Resin III
2,2-Bis(4-glycidylo~yphenyl)propane having an epoxide content of 5.2 equiYs./kg C52,8 g~, 1,4~bis(3-(4-hydroxyphenyl)-3-oxo-l-propenyl~benzene (44.4 g), 2~etho~yethyl acetate (97.2 g) and tetraethylammonium bromide t0-4 g) are heated to 140 C for 31 hours.
The solvent is evaporated to gi~e a resin having an epoxide content of 0.48 equi~s./kg.
Resin IV
Resin III (48.8 g~ is dissolved in 2-ethoxyethyl acetate (50 g~ and acetic acid (1.4 g) added. The ~ixture is heated at 100C for 71 hours, then evaporated, leaving a resin having a negligible epoxide content.
8~;
EXA~LE 1 A mixture of l-(p-(glycidyloxy)phenyl~-5-phenylpenta-1,4-dien-3-one (75 parts), n-butyl glycidyl ether (25 parts~, and boron trichloride/N-methylpiperidine complex (3 parts) is applied as a coating 10 ~m thick onto a copper-cla~ laminate. It is heated for 5 minutes at 150 C, allowed to cool, and then the solidified layer is irradiated through a negative ~ith a 5000w metal halide lamp at a diseance of 75 cm for 10 minutes. On development ~ith cyclohexanone a good ir~ge is obtained.
The same mixture is prepared as in Example 1, Its viscosity at 25C is 0.345 Pa s. The composition is stored at 25C for 2 months in the dark, at which time its viscosity at 20C is 0.360 Pa s. A portion of this stored composition is applied to a copper-clad laminate as in Example l and heated, irradiated and developed under the same conditions, A good image is likewise obtained.
The process of Example 1 is repeated, using 50 parts of the phenylpentadienone and 50 parts of n-butyl glycidyl ether. The layer is heated for 15 minutes at 160C, then irradiated for 1 minute Development under the same conditions gives a good image.
The process of Example l is repeated, using 10 parts of the phenylpen~adienone and 25 parts of n-butyl glycidyl ether, but 1 part of boron trichloride/N,N-dimethylcyclohexylamine complex. The coated la~inate is heated f or 10 ~inutes at 150C
and the solidified layer is irradiated through a negative for 10 minutes. On development with cyclohexanone a good image is obtained.
EXA~LE S
A mixture of l-(p-(glycidyloxy)phenyl)~S-(p-hydroxyphenyl)- -penta-1,4-dien-3-one (100 parts) and boron trichloride¦octyldimethyl-amine complex (4 parts) is applied as a coating 15 ym thick onto a copper-clad laminate. It is heated for 20 minutes at 150C, allowed to cool, and the solidified layer is irradiated for 20 minutes through a negative as described in Example 1.
A good image is developed using cyclohe~anone with gentle brushing.
- EX~u~PLE 6 Resin I (100 g~ is dissolved in l,4-butanediol diglycidyl ether (50 g) and borontrifluoride monoethylamine complex (4.5 g) is added. The resultant mi~ture is coated at 40 C on~o a copper-clad laminate to a thic~ness of 20 ~m. The laminate is heated at 120C for 5 minutes, which solidifies the coating. It is then irradiated through a negative for 30 seconds, as described in Examp1e 1. Development in cyclohexanone gives a good image.
E~AMPLE 7 Resin II Clo g) is dissolved in butyl glycidyl ether (5 g~
and the boron trifluoride complex of triphenyl phosphine ~0.2 g~
s~
and 4,4'~6is~dxmethylamino~enzophenone C0.2 g~ is added. The resultant solution is coated to a thickness of 35 ~m onto a copper~
clad laminate. The laminate is heated at 120C ~or 5 minutes which so]idifies the coating. It is then irradiated through a negative for 15 ~inutes, as descri~ed in Example 1. Deyelopment in chloroform gives a good image.
E~AMPLE 8 Resin III (20 parts~ is dissolyed in ~utyl glycidyl ether ~10 parts~ and boron trichloride trimethylamine complex C0,6 part2 is added. This solution is coated onto a copper-clad laminate to give a coating 20 pm thick. The laminate is heated at 120C
for 10 minutes to give a tack-free surface. This is irradiated through a negative, as descrihed in Example 1, for 5 minutes.
~evelopmen~ in cyclohexanone gives a good image.
EXAMPLE ~
Resin IV C20 parts~ is dissolved in hutyl glycidyl ether (10 parts~, and 1,4 butane diol diglycidyl ether Clo parts~, Boron trichloride octyldimethyl~mine complex C2 parts~ is then added and the resultant solution is coated onto a copper-clad ~laminate to give a coating 40 ~m thick. This is heated at 120C
for 15 ~inutes, to give a tack~free coating. The coating is ~irradiated for 5 minutes through a negative, as described in E~ample 1. Development in cyclohexanone gives a good image.
....
- 24 - ~ 6 ~ rPLE 10 Resin I C10 parts~ is dissolved in phenyl ~lycidyl ether (lO parts~ to which is added difluoro~oron-acetoacetanilide ~0.1 part~. The solution is coated onto a copper-clad laminate as a layer 35 pm thick, then heated at 120C for 10 ~inutes to solidify the coating. The coating is then irradiated for 1 minute through a nègative as described in E~ample 1. Development in cyclohe~anone gives a good image,
Claims (24)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the production of an image which comprises (i) heating a layer, supported on a carrier, of a liquid composition containing (A) a heat-activated latent polymerising agent for 1,2-epoxides with (B) a light-sensitive compound having in the same molecule at least one 1,2-epoxide group of formula I
and at least one chalcone or cinnamate group of formula - Ar - X - II
where Ar is a benzene ring or a benzene ring substituted by alkyl, cycloalkyl, alkenyl, alkoxy, alkoxycarbonyl, each of these groups having a maximum of nine carbon atoms, halogen, hydroxy, a primary, secondary or tertiary amino group, nitro, a carboxyl, sulfonic or phosphonic acid group or a salt thereof, and X is a chain of formula III
or IV
or v or VI
R1 and R2 individually denote a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, or conjointly denote a polymethylene chain of 2 to 4 methylene groups, R3 and R4 each denote a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, or a phenyl group, and a and b each denote zero, 1, or 2 which the proviso that they do not both denote zero, or with a mixture of (C) a compound containing at least one 1,2-epoxide group of formula I, together with (D) a compound containing at least one chalcone or cinnamate group of formula II, or with a mixture of a light sensitive compound (B) with a compound (C) and/or (D) as herein defined, such that the layer solidifies by thermal polymerisation and becomes essentially non-tacky but remains photocrosslinkable, and subse-quently (ii) exposing the solidified layer to actinic radiation in a predetermined pattern such that exposed parts of the layer are crosslinked and (iii) removing those parts of the layer which have not become substantially crosslinked by treatment with a solvent therefor.
and at least one chalcone or cinnamate group of formula - Ar - X - II
where Ar is a benzene ring or a benzene ring substituted by alkyl, cycloalkyl, alkenyl, alkoxy, alkoxycarbonyl, each of these groups having a maximum of nine carbon atoms, halogen, hydroxy, a primary, secondary or tertiary amino group, nitro, a carboxyl, sulfonic or phosphonic acid group or a salt thereof, and X is a chain of formula III
or IV
or v or VI
R1 and R2 individually denote a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, or conjointly denote a polymethylene chain of 2 to 4 methylene groups, R3 and R4 each denote a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, or a phenyl group, and a and b each denote zero, 1, or 2 which the proviso that they do not both denote zero, or with a mixture of (C) a compound containing at least one 1,2-epoxide group of formula I, together with (D) a compound containing at least one chalcone or cinnamate group of formula II, or with a mixture of a light sensitive compound (B) with a compound (C) and/or (D) as herein defined, such that the layer solidifies by thermal polymerisation and becomes essentially non-tacky but remains photocrosslinkable, and subse-quently (ii) exposing the solidified layer to actinic radiation in a predetermined pattern such that exposed parts of the layer are crosslinked and (iii) removing those parts of the layer which have not become substantially crosslinked by treatment with a solvent therefor.
2. A process according to claim 1, in which the group of formula I
forms part of a 2,3-epoxypropyl group.
forms part of a 2,3-epoxypropyl group.
3. A process according to claim 2, in which the 2,3-epoxypropyl group is directly attached to an atom of oxygen, nitrogen, or sulphur.
4. A process according to claim 1, in which the group -Ar-X- is a cinnamoyloxy group or forms part of a group of formula VII or VIII
where X1 denotes a group of formula III, IV or V, each R5 represents a halogen atom, an alkyl, cycloalkyl, alkenyl, alkoxy, or alkoxy-carbonyl group containing up to 9 carbon atoms, a hydroxy group, a primary, secondary or tertiary amino group, a nitro group, a carboxyl, sulfonic, or phosphoric acid group or a salt thereof, each c represents zero or an integer of 1 to 4, R6 denotes an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms, an aryl group of 6 to 15 carbon atoms or an alkaryl or aralkyl group of 7 to 10 carbon atoms, or each of said groups being substituted by one or more hydroxyl groups, and R7 denotes an alkylene group of 1 to 6 carbon atoms, an alkenylene group of 2 to 6 carbon atoms, a cycloalkylene group of 3 to 6 carbon atoms, an arylene group of 6 to 15 carbon atoms, or an alkarylene or aralkylene group of 7 to 10 carbon atoms.
where X1 denotes a group of formula III, IV or V, each R5 represents a halogen atom, an alkyl, cycloalkyl, alkenyl, alkoxy, or alkoxy-carbonyl group containing up to 9 carbon atoms, a hydroxy group, a primary, secondary or tertiary amino group, a nitro group, a carboxyl, sulfonic, or phosphoric acid group or a salt thereof, each c represents zero or an integer of 1 to 4, R6 denotes an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, a cycloalkyl group of 3 to 6 carbon atoms, an aryl group of 6 to 15 carbon atoms or an alkaryl or aralkyl group of 7 to 10 carbon atoms, or each of said groups being substituted by one or more hydroxyl groups, and R7 denotes an alkylene group of 1 to 6 carbon atoms, an alkenylene group of 2 to 6 carbon atoms, a cycloalkylene group of 3 to 6 carbon atoms, an arylene group of 6 to 15 carbon atoms, or an alkarylene or aralkylene group of 7 to 10 carbon atoms.
5. A process according to claim 4, in which R6 denotes a group of formula IX
or a methyl or ethyl group, in which R5 and c are as defined in claim 4.
or a methyl or ethyl group, in which R5 and c are as defined in claim 4.
6. A process according to claim 4 in which R7 denotes a group of formula X
in which R5 and c are as defined in claim 4.
in which R5 and c are as defined in claim 4.
7. A process according to claim 4, in which (B) is a glycidyl ester of a cinnamic acid, a partial ester formed by reaction of an epoxide resin with less than one equivalent of a cinnamic acid, a glycidyl ether of a monohydric or dihydric phenol containing a chalcone unit, a glycidyl ether prepared by advancing a diglycidyl ether containing a chalcone unit with a bisphenol or with a hydantoin, or a glycidyl derivative prepared by advancing a diglycidyl derivative of a bisphenol or hydantoin with a hydroxy-substituted chalcone.
8. A process according to claim 4 in which (B) is a glycidyl ether of formula XI
or XII
or XIII
where R8 denotes a methyl or ethyl group, and X1, R5 and c are as defined in claim 4.
or XII
or XIII
where R8 denotes a methyl or ethyl group, and X1, R5 and c are as defined in claim 4.
9. A process according to claim 7 in which (B) is glycidyl cinnamate or a partial reaction product of cinnamic acid with an epoxidised novolak or a diglycidyl ether of bisphenol A.
10. A process according to claim 8 in which (B) is a compound of formula XIV
or XV
or XVI
where R8 denotes a methyl or ethyl group, and R9 represents a hydrogen atom or a hydroxy group.
or XV
or XVI
where R8 denotes a methyl or ethyl group, and R9 represents a hydrogen atom or a hydroxy group.
11. A process according to claim 7 in which (B) represents a glycidyl ether prepared by advancement of a bisphenol A diglycidyl ether with 2,4-, 2',4-, 2',4'-, 2',3-, 2,5'-, 2,2'-, 4,4'- or 3,4'-dihydroxychalcone, or 1,5-bis(p-hydroxyphenyl)penta-1,4-dien-3-one, a glycidyl derivative prepared by advancing N,N'-diglycidyl-5,5-dimethyl hydantoin with 1,5-bis(p-hydroxyphenyl)penta-1,4-dien-3-one, 4,4'-diglycidyloxychalcone, 1,4-bis(3-(4-glycidyloxyphenyl)-3-oxo-1-propenyl)benzene, 4,4'-diglycidyl-2,6-dimethylchalcone, 1-(p-glycidyloxyphenyl)hexa-1,4-dien-3-one, 1-(p-glycidyloxyphenyl)-5-phenylpenta-1,4-dien-3-one, 1-(p-glycidyloxyphenyl)-5-(p-hydroxy-phenyl)penta-1,4-dien-3-one, or 1,5-bis-(p-glycidyloxyphenyl)penta-1,4-dien-3-one.
12. A process according to claim 1, in which the compound (C) is a mono- or polyglycidyl ester, a mono- or polyglycidyl ether, or a poly(N-glycidyl) compound.
13. A process according to claim 12 in which the compound (C) is 2,2,4-trimethylpentyl glycidyl ether, phenyl glycidyl ether, butyl glycidyl ether, a diglycidyl ether of 2,2-bis(4-hydroxyphenyl)pro-pane, bis(4-hydroxyphenyl)methane or butane-1,4-diol, or 1,3-digly-cidyl-5,5-dimethylhydantoin.
14. A process according to any of claims 1, 2 and 4, in which compound (D) is a full or partial ester of cinnamic acid with an aliphatic glycol or polyol, or an epoxide resin that has been fully esterified by a cinnamic acid.
15. A process according to claim 4, in which the compound (D) is of formula or XVII XVIII
where X1, R5 and c are as defined in claim 4, and Y denotes an oxygen or sulphur atom.
where X1, R5 and c are as defined in claim 4, and Y denotes an oxygen or sulphur atom.
16. A process according to claim 4, in which the compound (D) is an epoxide resin that has been advanced to negligible epoxide content by reaction with a chalcone of formula XVII or XVIII in which one or two groups R5 are hydroxy, carboxyl, or primary or secondary amino groups.
17. A process according to claim 1, in which (A) has a significant heat-polymerising effect on (B) and (C) only at temperatures above 100°C.
18. A process according to claim 17, in which (A) is a complex of boron trichloride or of boron trifluoride, a chelate of boron difluoride, dicyandiamide, or an imidazole.
19. A process according to claim 18, in which (A) is a complex of boron trichloride with a tertiary amine or of boron trifluoride with a triaryl phosphine, with piperidine, or with a primary amine.
20. A process according to claim 19 in which (A) is boron trichlo-ride-octyldimethylamine complex or boron trifluoride-ethylamine complex.
21. A process according to claim 1, in which the said layer is heated at a temperature of 120° to 200°C.
22. A process according to claim 21, in which the said layer is heated for from 2 to 20 minutes.
23. A process according to any of claims 1, 2 and 4, in which the solidified layer is exposed to actinic radiation of wavelength 200-600 nm.
24. A support bearing an image produced by a process according to any of claims 1, 2 and 4.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8302160 | 1983-01-26 | ||
| GB838302160A GB8302160D0 (en) | 1983-01-26 | 1983-01-26 | Production of images |
| GB8323448 | 1983-09-01 | ||
| GB838323448A GB8323448D0 (en) | 1983-09-01 | 1983-09-01 | Production of images |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1212856A true CA1212856A (en) | 1986-10-21 |
Family
ID=26285031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000445940A Expired CA1212856A (en) | 1983-01-26 | 1984-01-24 | Process for the production of images |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4546067A (en) |
| EP (1) | EP0115471B1 (en) |
| CA (1) | CA1212856A (en) |
| DE (1) | DE3469324D1 (en) |
| ES (1) | ES8407599A1 (en) |
| HK (1) | HK70190A (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8402937D0 (en) * | 1984-02-03 | 1984-03-07 | Ciba Geigy Ag | Production of images |
| US5194365A (en) * | 1985-06-19 | 1993-03-16 | Ciba-Geigy Corporation | Method for forming images |
| CH678897A5 (en) * | 1986-05-10 | 1991-11-15 | Ciba Geigy Ag | |
| GB8822145D0 (en) * | 1988-09-21 | 1988-10-26 | Ciba Geigy Ag | Method |
| US5747223A (en) * | 1988-12-30 | 1998-05-05 | International Business Machines Corporation | Composition for photoimaging |
| US6180317B1 (en) | 1988-12-30 | 2001-01-30 | International Business Machines Corporation | Composition for photoimaging |
| US5026624A (en) * | 1989-03-03 | 1991-06-25 | International Business Machines Corporation | Composition for photo imaging |
| US5264325A (en) * | 1988-12-30 | 1993-11-23 | International Business Machines Corporation | Composition for photo imaging |
| US5439766A (en) * | 1988-12-30 | 1995-08-08 | International Business Machines Corporation | Composition for photo imaging |
| US5304457A (en) * | 1989-03-03 | 1994-04-19 | International Business Machines Corporation | Composition for photo imaging |
| US5426164A (en) * | 1992-12-24 | 1995-06-20 | The Dow Chemical Company | Photodefinable polymers containing perfluorocyclobutane groups |
| US5439779A (en) * | 1993-02-22 | 1995-08-08 | International Business Machines Corporation | Aqueous soldermask |
| ATE203553T1 (en) * | 1996-03-22 | 2001-08-15 | Vantico Ag | ONE-COMPONENT EPOXY RESIN PROCESSING MATERIAL |
| KR19980048361A (en) * | 1996-12-17 | 1998-09-15 | 손욱 | Photo-alignment composition, alignment film formed from this, and liquid crystal display element provided with this alignment film |
| US8232092B2 (en) * | 2005-08-09 | 2012-07-31 | Maxwell Sensors, Inc. | Apparatus and method for digital magnetic beads analysis |
| US7858307B2 (en) * | 2005-08-09 | 2010-12-28 | Maxwell Sensors, Inc. | Light transmitted assay beads |
| WO2010042745A1 (en) * | 2008-10-08 | 2010-04-15 | Applied Biocode Inc. | Biocompatible and photocurable polymers |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL283978A (en) * | 1961-10-05 | 1900-01-01 | ||
| DE1572061C3 (en) * | 1966-01-07 | 1974-11-07 | Kalle Ag, 6202 Wiesbaden-Biebrich | Photosensitive copy layer |
| DE1572062C3 (en) * | 1966-01-07 | 1974-11-07 | Kalle Ag, 6202 Wiesbaden-Biebrich | Photosensitive copy layer |
| DE1595581A1 (en) * | 1966-01-07 | 1970-04-30 | Hoechst Ag | Process for the production of polyethers |
| NL6809002A (en) * | 1967-07-06 | 1969-01-08 | ||
| GB1346768A (en) * | 1970-08-11 | 1974-02-13 | Ciba Geigy Uk Ltd | Curable epoxide resin compositions |
| US3726679A (en) * | 1971-06-30 | 1973-04-10 | Ibm | Light sensitive epoxy formulation |
| GB1512814A (en) * | 1975-08-13 | 1978-06-01 | Ciba Geigy Ag | Epoxide resins |
| US4291118A (en) * | 1979-12-26 | 1981-09-22 | W. R. Grace & Co. | Relief imaging liquids |
-
1984
- 1984-01-16 US US06/571,211 patent/US4546067A/en not_active Expired - Fee Related
- 1984-01-20 DE DE8484810037T patent/DE3469324D1/en not_active Expired
- 1984-01-20 EP EP84810037A patent/EP0115471B1/en not_active Expired
- 1984-01-24 CA CA000445940A patent/CA1212856A/en not_active Expired
- 1984-01-25 ES ES529130A patent/ES8407599A1/en not_active Expired
-
1990
- 1990-09-06 HK HK701/90A patent/HK70190A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0115471A2 (en) | 1984-08-08 |
| US4546067A (en) | 1985-10-08 |
| ES529130A0 (en) | 1984-10-01 |
| EP0115471A3 (en) | 1985-08-21 |
| DE3469324D1 (en) | 1988-03-17 |
| HK70190A (en) | 1990-09-14 |
| EP0115471B1 (en) | 1988-02-10 |
| ES8407599A1 (en) | 1984-10-01 |
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