GB2031442A - Positive-acting photoresist composition - Google Patents
Positive-acting photoresist composition Download PDFInfo
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- GB2031442A GB2031442A GB7930761A GB7930761A GB2031442A GB 2031442 A GB2031442 A GB 2031442A GB 7930761 A GB7930761 A GB 7930761A GB 7930761 A GB7930761 A GB 7930761A GB 2031442 A GB2031442 A GB 2031442A
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- resin
- novalac
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- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 229920002120 photoresistant polymer Polymers 0.000 title abstract description 30
- 239000003822 epoxy resin Substances 0.000 claims abstract description 22
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 22
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 11
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 7
- 239000005011 phenolic resin Substances 0.000 claims abstract description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 6
- 150000002118 epoxides Chemical class 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract 3
- 229920005989 resin Polymers 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 11
- 229920000728 polyester Polymers 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 7
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 5
- 125000005442 diisocyanate group Chemical group 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 6
- 229920003986 novolac Polymers 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 28
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 230000005855 radiation Effects 0.000 description 8
- 238000011161 development Methods 0.000 description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- -1 diisocyanate compound Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 4
- 229940105324 1,2-naphthoquinone Drugs 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- NIKBCKTWWPVAIC-UHFFFAOYSA-N butyl benzenesulfonate Chemical compound CCCCOS(=O)(=O)C1=CC=CC=C1 NIKBCKTWWPVAIC-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 101150017296 ddi-1 gene Proteins 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011090 industrial biotechnology method and process Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000009824 pressure lamination Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
- G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Materials For Photolithography (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
A positive-acting light-sensitive composition having excellent utility as a photoresist, comprising: (a) a crosslinked urethane resin formed by a catalyzed crosslinking of a non-heat reactive novolac phenolic resin and a polyisocyanate compound; (b) an epoxy resin having an epoxide equivalent weight of less than about 400 and a curing agent therefor; and (c) a positive-acting photosensitizer. Upon applying to a substrate and drying, the epoxy resin cures, resulting in a film useful as a photoresist or in the formation of lithographic printing plates.
Description
SPECIFICATION
Positive-acting photoresist composition
In the manufacture of dry photosensitive elements such as lithographic plates, photoresists, and the like, photosensitive compositions are utilized which are either negative-acting or positiveacting. Negative-acting systems are those which become insolubilized in an imagewise fashion upon exposure thereof to actinic radiation. Since the exposed areas are rendered relatively insoluble, selected developing solutions can dissolve or otherwise remove the unexposed portions of the composition while leaving the exposed areas intact. Therefore, the resulting image corresponds to the reverse of the original in terms of contrast, i.e., a negative image.
Conversely, with positive-acting systems, exposed portions thereof are rendered more soluble or developable upon exposure to actinic radiation, and as such these portions can be removed with selected developing solutions, the unexposed portions remaining intact. Imgae formation in this instance yields an image corresponding to the original image in terms of contrast, i.e., yields a positive image.
In the specific area of photoresist manufacture, a photoresist is typically utilized to promote image formation on substrates by imagewise protecting the substrate material from subsequent chemical or physical manufacturing processes, such as chemical etching, vacuum metalization, and electrolytic deposition. In other words, upon exposure and development of the photoresist material, the underlying substrate upon which the photoresist is place can be exposed to subsequent physical processing in an imagewise fashion, the processing affecting only in areas not protected by the resist material. In the manufacture of copper-clad circuit boards, a photoresist is typically applied to the circuit board surface, and is followed by imaging and development.Subsequent to such initial processing, an etching solution typically is sprayed under high pressure downward onto the substrate, the etchant removing the copper metal which is unprotected by the photoresist, thereby providing an imaged metal circuit configuration after removal of the balance of the photoresist.
In order to accurately reproduce circuit geometries, it is necessary that a photoresist have high adhesion to the substrate to which it is applied and high internal strength. Adhesion is required to prevent excessive undercutting of the resist by the etchant, thereby decreasing image resolution, and internal strength is necessary to maintain proper circuit geometries. Dry film resists should have reasonable flexibility, ability for heat and pressure lamination, reasonably fast exposure capability, excellent development characteristics with moderate pressure sprays of developer solutions, excellent coating quality (i.e., free from physical defects), capability of rapid chemical stripping or removal of the photoresist after use, and the production of a visible image upon exposure thereof to actinic radiation.
Dry negative-acting film resists have of course been known for quite some time. One important feature necessary for any resist is resolution. Positive-acting resists have an inherently higher resolution capability than do their negative-acting counterparts. This difference is due, in part, to the generally necessary presence of an oxygen-impermeable barrier film required prior to and during negative resist exposure, since conventional negative-acting materials are usually oxygen-sensitive.
Some typical resolution requirements in the electronics industry are as follows: In the production of general purpose printed circuit boards, typically 10 mil lines with 10 mil spaces are required; in precision circuits, typically 1 mil lines with 1 mil spaces are necessary; and in the microelectronics industry, better than 0.1 mil lines and spaces are required.
At the present time, the dry film resist market consists of virtually only negative-acting resists.
This is essentially because positive-acting film photoresists have not been developed which achieve the criteria noted above. Positive film resists typically exhibit excessive brittleness which allows flaking off of the resist with even moderate flexing of the carrier sheet, coating defects, a lack of internal cohesive strength which causes the resist to fracture during etching, and poor adhesion of the photoresist to the substrate surface.
It has now been ascertained that a novel positive-acting photosensitive composition can be utilized to prepare a dry film photoresist which meets many of the foregoing criteria. In addition, the photosensitive composition, in its cured state, is oleophilic, i.e., ink-receptive, and can therefore be utilized as a coating on aluminum or stainless steel surfaces to provide lithographic printing plates, or in the manufacture of bimetallic printing plates.
In accordance with the invention, there is provided a positive-acting light-sensitive composition having excellent utility as a photoresist, comprising: (a) a crosslinked urethane resin formed by a catalyzed crosslinking of a non-heat reactive novalac phenolic resin and a diisocyanate compound; (b) an epoxy resin having an epoxide equivalent weight of less than about 400 and a curing agent therefore; and (c) a positive-acting photo-sensitizer.
Upon the preferred application of the composition to a substrate (which may be a temporary support layer and strippable film or a substrate on which the composition is coated prior to processing) and drying, the epoxy resin cures, and the resultant dry film has ideal utility as a dry film photoresist. In addition, the dry film is oleophilic, and therefore can be utilized as a printing plate surface.
In dry coated form, the positive-acting composition of our invention basically comprises two intermixed and intertwined polymeric resin networks. The first of these networks comprises a crosslinked urethane resin formed from crosslinking of a diisocyanate with a novalac phenolic resin, and the second comprises a heat-curable epoxy resin. The resin mixture contains a blended-in amount of a positive-acting photosensitizer to afford light sensitivity to the system.
The urethane resin is formed in solution by the catalyzed crosslinking reaction of a novalac phenolic resin with a polyisocyanate, preferably a tri- or diisocyanate, and most preferably a long-chain diisocyanate compound.
The components used in forming the urethane can be simply dissolved in a suitable solvent together with an appropriate catalyst, whereupon the crosslinking reaction will ensue. When the solution viscosity stabilizes, reaction is complete.
The novalac phenolic resin should typically comprises from about 40 to about 80 and preferably between 50 and 70 percent by weight of the composition, and should not be heatreactive. Non-heat reactive according to the present invention means that the resin should not substantially polymerize when heated alone. Substantial polymerization would occur when the average molecular weight increased by at least 10%. Preferably the average molecular weight should increase by less than 4% upon heating, if at all. Increasing novalac concentration may cause increased film brittleness and an undesirable increase in the solubility of the unexposed film areas, which can result in an insufficient solubility differential between exposed and unexposed film areas. Reduced concentrations may cause the film to fail to develop properly after imagewise exposure to actinic radiation.Preferred novalac resins include novalac pheno
lic/formaldehyde resins of from about 500 to 1000 molecular weight. These resins include those of U.S. Pat. No. 4,148,655 where a number of different phenolic components are used.
Polyisocyanates useful herein include conventional aromatic and aliphatic polyisocyanates.
Preferably, the polyisocyanates are of long chain length, i.e., where the isocyanate groups are connected by linkages of from about 10 to about 40 or 50 carbon atoms. Both smaller (e.g., 6 carbon atoms) and larger chain aromatic and aliphatic diisocyanates would of course still be useful in the practice of the present invention. For example, isophoronediisocyanate, toluene diisocyanate and any other diisocyanates are particularly useful. The polyisocyanate should preferably be present in a concentration of from about 6 to about 12 parts by weight per 100 parts of novalac resin present, depending upon the molecular weight or isocyanate equivalent weight of the polyisocyanate. In general, the weight percent should not exceed a range of from about 3 to 20 percent by weight of the novolac resin.Increasing amounts tend to cause the resultant film to be excessively brittle, to have insufficient internal strength, and, in the case of photoresists, to exhibit reduced adhesion to the substrate to which the film is laminated.
Reduced amounts tend to cause the film to fail to laminate properly and clean out in exposed areas during development. Any catalyst known to be useful in the catalysis of urethane formation may be used. The most preferred catalysts includes tertiary amines, examples of which include 1,4 diaza-bicyclo-(2, 2,2)-octane, and 2,4,6-tris(dimethylaminomethyl) phenol.
Catalyst concentration is not critical, as long as a sufficient amount is present to incure crosslinking. Typically, greater than about 0.05 parts by weight per 100 parts of novalac resin is more than sufficient to insure complete crosslinking, although as little at 0.01 parts can be sufficient.
Once the urethane formation is complete, a polymerizable epoxy resin having an epoxide equivalent weight of less than about 400 is added to the solution, along with a curing agent therefor. A typical and preferred epoxy resin is diglycidyl ether of bisphenol A. Epoxy resin concentrations should be from about 20 to about 40 parts by weight per 100 parts of novalac resin. Increased concentrations tend to increase the flexibility of the resultant dry photosensitive film, but the capability of imagewise exposure and development is reduced. Decreasing concentrations tend to reduce the adhesion and handling characteristics of the resultant dry film.
Exemplary epoxy curing agents include aliphatic or aromatic amines, aliphatic or aromatic anhydrides, disulfones, nitriles, and other known epoxy curing agents. Any of these and other curing agents may be used in practice of the present invention. Preferred curing agents include phthalic anhydride, diamino diphenyl-sulphone or a combination thereof. Typically, from about 5 to about 50 parts of curing agent per 100 parts of epoxy resin are sufficient to insure curing of the epoxy.
Without inclusion of the epoxy curing agent or successful curing of the epoxy resin, the resultant film tends to be brittle and lacks the internal cohesive strength necessary for photoresist performance. Conversely, when the epoxy is satisfactorily cured, the resultant film has significantly greater flexibility and cohesive strength so as to be extremely useful as a photoresist.
The positive-acting photosensitizer is conveniently added by thorough mixing to the solution containing the urethane, polymerizable epoxy resin, and epoxy curing agent. Exemplary photosensitizers include diazo oxides, as known in the art, e.g., naphthoquinone-1,2-diazide-(2)- 5-sulphonic-p-methylphenyl ester, as in U.S. Patent Nos. 3,046,120; 3,046,121; and 3,211,553, and diazo sulfones as known in the art, e.g., in U.S. Patent Nos. 2,465,760; 3,113,865; and 3,661,573; and U.K. Patent No. 1,277,428. The photosensitizers should be soluble in the solvent utilized for the coating solution applications.A particularly useful photosensitizer which is commercially available under the tradename Diazo LL," is a naphtho quinone-( 1 , 2)-diazide-sulfonic-(5)-naphthadiester, available from the Molecular Rearrangement
Company. The positive acting photosensitizers of U.S. Patent No. 4,148,654 are also useful in the present invention. A positive acting photosensitizer according to the present invention is a material which when struck by radiation, preferably actinic radiation, decomposes into a material which is more acidic than the photosensitizer. Preferably the original photosensitizer is neutral or basic to provide the greatest change in pH. The photosensitizer component need not provide any structural integrity by itself as it is blended into the mixture of urethane, polymerizable epoxy resin, and curing agent.
Concentration of the photosensitizer can be from about 10 parts by weight per 100 parts of novalac resin up to solution saturation.
Solvents utilized in the formation of the photosensitive solutiion are a matter of choice and convenience and include, for example, methyl isobutyl ketone, methyl ethyl ketone, etc.
In practice, the solution can be simply coated by any known means onto a support material, followed by drying at a temperature sufficient to cure the epoxy resin. In the case of a photoresist applied from a transfer film, the film backing should contain a release agent thereof, such as methyl cellulose, polyvinyl pyrrolidone, and copolymers of methyl vinyl ether and maleic anhydride to allow easy removal of the film backing, e.g., polyester from the photoresist layer.
Following drying, the photoresist composition can be simply laminated by means of heat and pressure to a variety of substrates such as metals including copper, stainless steel, and gold, ceramics, glass, silicon dioxide, and organic polymers such as polyimide, epoxy, resin, and polysiloxanes and polyester.
Furthermore, the liquid photosensitive solution can be coated onto stainless steel for the purpose of manufacturing bimetallic printing plates by means of electrode deposition subsequent to imaging and development of the light sensitive material, or can be applied onto aluminum and silicated aluminum to manufacture printing plates, since the dry composition is oleophilic in nature.
Prior to coating onto a support, materials such as epoxy or amine functionalized alkoxy silane coupling agents can be added to the solution to promote the adhesion to substrates such as glass, silicon dioxide or other surfaces. Examples of such materials include y-aminopropyltriethoxy silane and y-glycidoxypropyl-trimethoxy silane.
Exposure can be undertaken by conventional techniques, e.g., carbon arc, etc., depending upon the radiation to which the photosensitizer is sensitive. Development of the image is undertaken using developers such as weak alkaline solutions, etc., which are conventional with the sensitizers utilized.
Our invention will now be more specifically described by the aid of the following non-limiting examples, wherein all parts are by weight unless otherwise specified.
Example 1
a positive-acting composition was prepared by mixing the following components at room temperature:
Methyl ethyl ketone 27.6
Resinox, tradename for a phenol/formaldehyde resin commercially available from Monsanto Company 11.0
246-tris(dimethylaminomethyl)phenol 0.23
DDI-1410, tradename for an aliphatic (approximately
36 carbon atom bridging group) diisocyanate commercially available from General Mills Chemicals, Inc. 1.00
The solution containing the above components was mixed until the solution viscosity (measured with a conventional Brookfield viscometer with a No. 2 spindle) stabilized at about
17 centipoise, after which the following were added::
Methyl ethyl ketone 11.0
DER 331, tradename for diglycidyl ether of bisphenol A having an epoxy equivalent weight of 186 to 192, commercially available from the Dow Chemical Company 3.31
Phthalic anhydride 0.26
Diaminodiphenylsulfone 0.13 1,2-naphthoquinone diazide-5-p-tert-butylphenylsulfonate 3.6
After thorough mixing, the solution was knife coated onto 2 mil thick polyester sheeting which had been precoated with 50 milligrams per square foot of methyl cellulose, the photosensitive coating then being dried at 18Q F for 4 minutes. During drying, the epoxy resin was cured.
The resulting film was sufficiently flexible to withstand moderate flexing of the support without breaking away. The film was laminated to sheet copper using a heated roll laminator at 100 C. The polyester backing was stripped from the photoresist following lamination and the resist exposed through an original to a carbon arc for 50 seconds. The exposed resist was then developed by spraying the resist with a 1 % aqueous sodium hydroxide solution for 2 minutes.
The exposed copper could then be etched or electroplated in accordance with normal industrial techniques.
Example 2
A positive-acting composition was prepared by mixing the following:
Methyl ethyl ketone 27.7
Resinox 11.0 1,4-diazabicyclo(2,2,2)octane 0.01 DDI-1 410 1.23 until the viscosity of the solution stabilized at about 50 centipoise.
Following the completion of the urethane formation, the following components were added to the solution:
DER 331 3.0
Phthalic anhydride 0.3 1 , 2-naphthoquinone diazide-5-p-tert-butylphenylsulfonate 3.0
After coating, exposing and developing as per Example 1, the film displayed excellent flexibility and photoresist properties.
Example 3
A positive-acting composition was prepared by mixing:
Methyl ethyl ketone 27.7
Resinox 11.0 1,4-diazabicyclo(2,2,2)octane 0.06
DDI-1410 1.18 until the viscosity of the solution stabilized.
The following components were then added to the solution:
DER 331 2.15
Diaminodiphenylsulfone 0.40 1 , 2-naphthoquinone diazide-s-p-tert-butylphenylsulfonate 3.0
After coating, drying, exposing and developing as per Example 1, the film displayed good flexibility and photoresist properties.
Example 4
A photosensitive composition was prepared by mixing the following:
The reaction product of "Resinox" and DDI-1410 given in Example 1 100
DER 331 9
Diaminodiphenylsulfone 1.7 ''Diazo LL'', tradename for a naphthoquinone(1 ,2)-diazide- (1 )-sulfonic-(5)-naphtho-diester sold by
Molecular Rearrangement, Inc. 11.6 y-aminopropyltriethoxysilane 0.26
The solution was coated onto silicated aluminum and dried at 180 F. The resulting composition was used as a printing plate, i.e., it was exposed to actinic radiation in an image-wise manner, developed, and inked. It was found that the film took ink and was functional as a printing plate.
Example 5
The present example shows the desirability of curing the epoxy resin in the presence of the polyurethane to form an interlocking dual polymer network.
A positive-acting composition was prepared by mixing the following components at room temperature:
Acetone 27.6
Resinox, tradename for a phenol/formaldehyde resin commercially available from Monsanto Company 11.0 2,4, 6-tris(dimethylaminomethyl) phenol 0.23
DDI-1410, tradename for an aliphatic diisocyanate commercially available from General Mills Chemicals, Inc. 1.00
The solution containing the above components was mixed until the solution viscosity, measured with a conventional Brookfield viscometer stabilized at about 15 centipoise.This solution was combined with another one which had been prepared in the following way:
Acetone 11.0
Epon 828, tradename for a diglycidyl ether of bisphenol A having an epoxy equivalent weight of 186 to 192 commercially available from the Shell Chemical Company 3.31
Phthalic anhydride 0.26
Diaminodiphenylsulfone 0.13
These components of the second solution were boiled under reflux for 20 hours. To the combined solutions was added: 1,2-naphthoquinone diazide-5-p-tert butylphenylsulfonate 3.6
After thorough mixing, the combined solution was knife coated onto 2 mil polyester sheeting which had been precoated with a 50 milligram per square foot methyl cellulose coating or precoated with a 50 milligram per square foot hydrolyzed copolymer formed from methylvinylether and malaic anhydride. The photosensitive coating was dried at 180 F for 4 minutes.
The film was laminated to a sheet of copper using a heated roll laminator at 100 C. The polyester backing was stripped from the photoresist following lamination and the resist exposed through a photomask to UV light. The exposed portion of the resist was developed by spraying it with a 1 % aqueous solution of sodium hydroxide.
The resists made in this manner were inferior to those made in the manner of Examples 1-4.
Stripping of the polyester backing was difficult. Image quality was poorer and some bleeding of material from the unexposed resist image was noted. The resist also was more brittle than coatings described in the Examples 1-4. These coatings were still as good as many others used commercially.
Claims (20)
1. A positive-acting light sensitive composition comprising: (a) a crosslinked urethane resin formed by a catalyzed crosslinking of a non-heat-reactive novalac phenolic resin and a polyisocyanate compound; (b) an epoxy resin having an epoxide equivalent weight of less than about 400 and a curing agent therefor; and (c) a positive-acting photosensitizer.
2. The composition of claim 1 wherein said novalac resin comprises from about 40 to 80 weight percent of said composition, said polyisocyanate concentration is from about 6 to about 12 parts by weight per 100 parts of said novalac resin, said epoxy resin concentration is from about 20 to about 40 parts by weight per 100 parts of said novalac resin, and said photosensitizer concentration is at least about 10 parts by weight per 100 parts of said novalac resin.
3. The composition of claim 2 wherein said novalac resin comprises from about 50 to 70 weight percent of said composition.
4. The composition of claim 1 wherein said novalac resin is a novalac phenolic/formaldehyde resin.
5. The composition of claim 4 wherein said novalac resin has a molecular weight of from about 500 to about 1000.
6. The composition of claim 1 wherein said epoxy resin is a diglycidyl ether of bisphenol A.
7. The composition of claim 1 wherein said curing agent is selected from the group consisting of phthalic anhydride, diamino diphenylsulfone, and mixtures thereof.
8. A positive-acting light sensitive article comprising a substrate having coated on the surface thereof a light-sensitive composition comprising (a) a urethane resin formed by a catalyzed crosslinking of a non-heat-reactive novalac phenolic resin and a polyisocyanate compound; (b) a cured epoxy resin, said epoxy resin having an epoxide equivalent weight of less than about 400; and (c) a positive-acting photosensitizer.
9. The article of claim 8 wherein said novalac resin comprises from about 40 to about 80 weight percent of said composition, said polyisocyanate concentration is from about 6 to about 12 parts by weight per 100 parts of said novalac resin, said epoxy resin concentration is from about 20 to about 40 parts by weight per 100 parts of said novalac resin, and said photosensitizer concentration is at least about 10 parts by weight per 100 parts of said novalac resin.
10. The article of claim 9 wherein said novalac resin comprises from 50 to 70 weight percent of said composition.
11. The article of claim 18 wherein said novalac resin is a novalac phenolic/formaldehyde resin.
12. The article of claim 18 wherein said novalac resin has a molecular weight of from about 500 to about 1000.
13. The article of claim 18 wherein said epoxy resin is a diglycidyl ether of bisphenol A.
14. The article of claim 18 wherein said substrate is a polyester.
15. The article of claim 18 wherein said substrate is aluminum.
16. The article of claim 18 wherein said substrate comprises a flexible backing having a release coating thereon.
17. The article of claim 18 wherein said substrate is stainless steel.
18. The article of claim 8 wherein said polyisocyante comprises a diisocyanate having from 10 to 50 carbon atoms.
19. A positive-acting light sensitive composition substantially as herein described with reference to any one of the Examples.
20. A positive-acting light sensitive article substantially as herein described with reference to any one of the Examples.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US93998978A | 1978-09-06 | 1978-09-06 |
Publications (2)
Publication Number | Publication Date |
---|---|
GB2031442A true GB2031442A (en) | 1980-04-23 |
GB2031442B GB2031442B (en) | 1982-11-10 |
Family
ID=25474042
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB7930761A Expired GB2031442B (en) | 1978-09-06 | 1979-09-05 | Positive acting photoresist composition |
Country Status (9)
Country | Link |
---|---|
JP (1) | JPS5546746A (en) |
BR (1) | BR7905714A (en) |
CA (1) | CA1119447A (en) |
DE (1) | DE2935904A1 (en) |
FR (1) | FR2435741B1 (en) |
GB (1) | GB2031442B (en) |
IT (1) | IT1162658B (en) |
LU (1) | LU81652A1 (en) |
NL (1) | NL7906588A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4680346A (en) * | 1985-12-13 | 1987-07-14 | Ppg Industries, Inc. | Flexible primer composition and method of providing a substrate with a flexible multilayer coating |
US6105500A (en) * | 1995-11-24 | 2000-08-22 | Kodak Polychrome Graphics Llc | Hydrophilized support for planographic printing plates and its preparation |
US6138568A (en) * | 1997-02-07 | 2000-10-31 | Kodak Polcyhrome Graphics Llc | Planographic printing member and process for its manufacture |
US6182571B1 (en) | 1996-11-21 | 2001-02-06 | Kodak Polcyhrome Graphics Llc | Planographic printing |
US6293197B1 (en) | 1999-08-17 | 2001-09-25 | Kodak Polychrome Graphics | Hydrophilized substrate for planographic printing |
US6357351B1 (en) | 1997-05-23 | 2002-03-19 | Kodak Polychrome Graphics Llc | Substrate for planographic printing |
US6427596B1 (en) | 1997-05-23 | 2002-08-06 | Kodak Polychrome Graphics, Llc | Method for making corrections on planographic printing plates |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56140342A (en) * | 1980-04-02 | 1981-11-02 | Tokyo Ohka Kogyo Co Ltd | Image forming composition and formation of resist image |
JPS58152236A (en) * | 1982-03-05 | 1983-09-09 | Toray Ind Inc | Photosensitive composition |
JPS6120939A (en) * | 1984-07-10 | 1986-01-29 | Fuji Photo Film Co Ltd | Photosensitive composition |
JPH0654390B2 (en) * | 1986-07-18 | 1994-07-20 | 東京応化工業株式会社 | High heat resistance positive photoresist composition |
JPS6380254A (en) * | 1986-09-24 | 1988-04-11 | Fuji Photo Film Co Ltd | Photosensitive composition |
JPS6463856A (en) * | 1987-05-12 | 1989-03-09 | Sumitomo Metal Ind | Method and apparatus for automatic ultrasonic flaw detection of pipe end |
EP0413087A1 (en) * | 1989-07-20 | 1991-02-20 | International Business Machines Corporation | Photosensitive composition and use thereof |
DE3927631A1 (en) * | 1989-08-22 | 1991-02-28 | Basf Ag | IMPLEMENTATION PRODUCT, METHOD FOR THE PRODUCTION THEREOF AND THE PRODUCTABLE MIXTURE OF RADIATION |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1538320A (en) * | 1965-11-02 | 1968-09-06 | Ferrania Spa | Manufacturing process of presensitized dies for offset printing |
BE789196A (en) * | 1971-09-25 | 1973-03-22 | Kalle Ag | PHOTOSENSITIVE COPY MATERIAL |
CH576739A5 (en) * | 1972-08-25 | 1976-06-15 | Ciba Geigy Ag | |
AR205345A1 (en) * | 1973-06-20 | 1976-04-30 | Minnesota Mining & Mfg | PHOTOSENSITIVE ORGANOPHILIC COMPOSITION AND LITHOGRAPHIC PLATE PREPARED WITH THE SAME |
DE2617088A1 (en) * | 1975-04-29 | 1976-11-11 | Hoechst Co American | LIGHT-SENSITIVE COPY DIMENSIONS |
-
1979
- 1979-08-10 CA CA000333505A patent/CA1119447A/en not_active Expired
- 1979-09-03 NL NL7906588A patent/NL7906588A/en not_active Application Discontinuation
- 1979-09-05 GB GB7930761A patent/GB2031442B/en not_active Expired
- 1979-09-05 BR BR7905714A patent/BR7905714A/en not_active IP Right Cessation
- 1979-09-05 DE DE19792935904 patent/DE2935904A1/en active Granted
- 1979-09-05 LU LU81652A patent/LU81652A1/en unknown
- 1979-09-05 IT IT50175/79A patent/IT1162658B/en active
- 1979-09-05 FR FR7922164A patent/FR2435741B1/en not_active Expired
- 1979-09-06 JP JP11470279A patent/JPS5546746A/en active Granted
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4680346A (en) * | 1985-12-13 | 1987-07-14 | Ppg Industries, Inc. | Flexible primer composition and method of providing a substrate with a flexible multilayer coating |
US6105500A (en) * | 1995-11-24 | 2000-08-22 | Kodak Polychrome Graphics Llc | Hydrophilized support for planographic printing plates and its preparation |
US6182571B1 (en) | 1996-11-21 | 2001-02-06 | Kodak Polcyhrome Graphics Llc | Planographic printing |
US6138568A (en) * | 1997-02-07 | 2000-10-31 | Kodak Polcyhrome Graphics Llc | Planographic printing member and process for its manufacture |
US6357351B1 (en) | 1997-05-23 | 2002-03-19 | Kodak Polychrome Graphics Llc | Substrate for planographic printing |
US6427596B1 (en) | 1997-05-23 | 2002-08-06 | Kodak Polychrome Graphics, Llc | Method for making corrections on planographic printing plates |
US6293197B1 (en) | 1999-08-17 | 2001-09-25 | Kodak Polychrome Graphics | Hydrophilized substrate for planographic printing |
US6418850B2 (en) | 1999-08-17 | 2002-07-16 | Kodak Polychrome Graphics Llc | Hydrophilized substrate for planographic printing |
Also Published As
Publication number | Publication date |
---|---|
NL7906588A (en) | 1980-03-10 |
JPS6244256B2 (en) | 1987-09-18 |
CA1119447A (en) | 1982-03-09 |
FR2435741A1 (en) | 1980-04-04 |
IT1162658B (en) | 1987-04-01 |
FR2435741B1 (en) | 1986-10-03 |
BR7905714A (en) | 1980-05-13 |
LU81652A1 (en) | 1980-04-21 |
DE2935904C2 (en) | 1991-03-07 |
DE2935904A1 (en) | 1980-03-20 |
JPS5546746A (en) | 1980-04-02 |
GB2031442B (en) | 1982-11-10 |
IT7950175A0 (en) | 1979-09-05 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
PE20 | Patent expired after termination of 20 years |
Effective date: 19990904 |