CN1030113C - Positive-working radiation-sensitive coating solution - Google Patents
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- CN1030113C CN1030113C CN 85105070 CN85105070A CN1030113C CN 1030113 C CN1030113 C CN 1030113C CN 85105070 CN85105070 CN 85105070 CN 85105070 A CN85105070 A CN 85105070A CN 1030113 C CN1030113 C CN 1030113C
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Abstract
The present invention relates to a coating liquid sensitive to positive radiation, which contains the basic components of a compound sensitive to radiation, such as 1, 2-naphthoquinione diazide, or a composition of compounds sensitive to radiation, such as a composition composed of a compound having at least one C-O-C bond which can be schizolysed by acid and a compound which can be formed into strong acid by radiation, and an organic solvent or the mixture of organic solvents. The mixture of organic solvents is at least mostly composed of the single C1 to single C4 alkyl ether of 1, 2-propanediol. Compared with known positive photoresist liquid, the coating liquid of the present invention has little toxin and good coating layer homogenization quality.
Description
The invention relates to the positive-working radiation-sensitive coating solution that is suitable for preparing photoresist layer specially.
Known positivity photoresist liquid, principal ingredient contains naphthoquinone two azide, perhaps contains by can and forming the composition that the compound of strong acid is formed after the actinic radiation effect by the compound of acid cleavage.These positivity photoresist liquid are widely used in chemical etching etc. in producing P.e.c. and microelectronic element.
In these applications, provide photosensitive coating liquid by manufacturing plant usually, by the user it is coated on the suitable layering holder then, for example be coated on the silicon chip or the copper laminated plate of certain insulating material on, make the coating drying then.With industrial when being generally used for producing PS galley or dry film photoresist continuously the process of coating Endless holder compare, this monolithic rubbing method is more difficult certainly to carry out easier going wrong.The user is when coating monolithic holder, and the coating condition strictness that is difficult to maintain the standard is constant.These problems that occur in actual coating process, not only kind and the quantity owing to solid constituent in the coating causes, and also is because type of organic solvent commonly used is caused to a great extent.Owing to only be coated with many users of a small amount of holder, do not possess recovery or dispose the facility of solvent vapour, so only allow to use the solvent harmless to health at environmentally safe.Recently, owing to the standard of the organic solvent that has proposed to use in many permissions laboratory, so the selection of organic solvent has been subjected to considerable restraint.On the other hand, when this solution is dry, under temperature and drying condition various situations all inequality, all wishes as far as possible all protective seams of even no streak of acquisition even.For reaching the various trials that this purpose is done, typically use the solvent mixture of forming by several components, and it is different to form each solvent of this solvent mixture, and has different dissolving poweies for each composition in the coating.
Evaporation number is also different, so that use the solidification process of coating to take place gradually in dry run, with the unevenness of avoiding causing because of each single component premature disengagement.Owing to these reasons, the photoresist liquid of the actual use that major part can have been bought from the market all contains certain solvent mixture.
United States Patent (USP) 3,634, in 082, proposed to be suitable for 1, the 2-quinone di-azido compound is that all kinds of solvents material that the positivity photoresist liquid of base-material is used has: glycol monomethyl methyl ether, ethylene glycol monomethyl ether, aliphatic ester (for example butyl acetate), aliphatic ketone (for example methyl isobutyl ketone and acetone), diox, dimethylbenzene, halogenated aromatic compound (for example xylene chloride), benzene and toluene.
These solvents are used for basically with can be by the positivity photoresist potpourri of the compound of sour institute cracking as base-material, about this point for example at United States Patent (USP) 4,101,323 and european patent application disclose in 42,562 and once introduced.
The principal ingredient of process level photoresist solution, normally for example ethylene glycol derivative such as glycol monoethyl ether and ethylene glycol monoethyl ether, the ether of corresponding diglycol or ethylene glycol ether ester.The characteristics of these solvents are, have fine solubility for whole coating compositions of routine, and its boiling point and evaporation number are suitable, and reasonable price.But it is not all flawless in all cases adopting the resulting coating of these compositions.And from the concentration this point that they can allow the laboratory environment air, its use value reduces recently.
Therefore, the objective of the invention is to propose a kind of photoresist liquid, the employed solvent of this solution is exactly that all the solvent with selected so far is suitable in aspects such as boiling point, vapor pressure, dissolving power and price, but but be improved by the coating quality that it obtains, also less to the injury of human body.
According to the present invention, a kind of coating liquid of positive-working radiation-sensitive has been proposed, this solution contains the compound compositions of the compound or the radiation-sensitive of radiation-sensitive, and certain organic solvent or solvent mixture (major part is made up of certain glycol ethers at least) are as basis.
The characteristics of coating liquid of the present invention are: said glycol ethers is 1, (the C of 2-propylene glycol
1-C
4) monoalky lether.Preferred glycol ethers is its single C
1Alkyl ether or single C
2Alkyl ether.Especially preferentially select 1 for use, the 2-propylene glycol monomethyl ether.
Said alkylether radicals can be positioned on the 1-position or 2-position of propylene glycol.For its monomethyl ether, ordinary priority is selected easier 1-methoxypropanol [2] of having bought for use.Also can use two kinds of methyl mixture of isomers and (perhaps) propylene glycol list C
1Alkyl ether is to single C
4The potpourri of alkyl ether.
The above-mentioned solvent of mentioning can have been bought on market.These solvents allow the Cmax of existence in the plant laboratory ambiance, be higher than the Cmax of employed those glycol ethers so far.The very big advantage of another of these solvents is: compare (especially when these solvents are the unique solvent that uses in coating) with the ethers of corresponding ethylene glycol, the coating liquid of being made by them has more consistent spreading, and can obtain more uniform coating.When replacing, the advantageous property of this solution is still protected by other secondary solvent commonly used (for example ketone such as hydro carbons such as ester class, dimethylbenzene, acetone or butanone such as butyl acetate etc., alcohols or acetate-some alkoxy alkyl class such as 3-methoxyl butyl ester) when the part propylene-glycol monoalky lether.As the time need, can change wettability, flowability and evaporation characteristic under the different situations in such a way.The addition of these added solvent by weight under any circumstance should be less than 50%.With the 0-35% that is equivalent to this solvent mixture weight for well, best 0-20%.Therefore, solvent of the present invention or solvent mixture contain 1 of 65-100% by weight, 2-propylene glycol C
1-C
4Monoalky lether preferentially selects 1 for use, 2-propylene glycol monomethyl ether and (perhaps) 1,2-propylene glycol list ethylether.Also can increase the pliability of this coating by more high boiling alcohol of adding or ether, a spot of high-boiling point alcohol or ether after drying (approximately 1-2%) remain among the coating.If necessary, can also add certain than low boiling point solvent (for example sec-butyl alcohol) to accelerate evaporation rate.
In known manner, for example dip-coating, extrusion coated (Slot-die-coating), get rid of be coated with, method such as spraying, roller coat or the showering of curtain formula, this photoresist liquid is coated on the holder.
Under most of situation, preferably only use the alkoxy propyl alcohol as solvent.
% meter by weight, solid amount in the solution of the present invention generally between 10 to 50, changes between being preferably in 15 to 35, its concrete numerical value depend in each case the light-sensitive compound that uses and the type of bonding agent and the purposes of expection.
Coating liquid of the present invention also contains radiation-sensitive compound or light-sensitive compound, the compound compositions of radiation-sensitive or the composition of light-sensitive compound.Positive compounds, i.e. exposure makes it soluble compound, is suitable for purpose of the present invention.This compound comprises 1,2-quinone-diazide and photodissociation acid donor with can be by the composition of the compound of acid cleavage (for example former carboxylic acid compound and acetal compound).
1,2-quinone-diazide is a known substances, and in for example Deutsches Reichs-Patent 938,233 and 1,543,271, and the Deutsches Reichs-Patent application discloses 2,331, does introduction on 377,2,547,905 and 2,828,037 file such as grade.Preferred 1,2-quinone-diazide is naphthoquinones-(1,2)-diazide-(2)-4-sulphonic acid ester or acid amides, or naphthoquinones-(1,2)-diazide-(2)-5-sulphonic acid ester or acid amides.In these materials, what override was selected for use is ester, especially sulphonic acid ester.1,2-quinone-diazide is with respect to the amount of non-volatile component in this potpourri, and % calculates and is generally 3-50 by weight, and preferred value is 7-35.
Can being that the coating liquid of base-material also is known, and for example be recorded among United States Patent (USP) 3,779,778 and 4,101,323, Deutsches Reichs-Patent 2,718,254 and the West Germany's prospectus 2,829,512 and 2,829,511 by the compound of acid cleavage.As can be by the compound of sour institute cracking, these coating liquid contain the ethers or the acylimino carbonic ester of former carboxylic acid derivates, acetal or poly-acetal, enol.As to radiation-sensitive with offset the compound of disacidify sensitivity, they mainly contain the halogenated organic compound, s-triazine or 2-three chloromethanes-1,3 that replaced by groups such as halogenated methyls especially, 4-diazoles.At United States Patent (USP) 4,101, in 323 in the former carboxylic acid derivates of record, especially preferentially select the two-1 of aliphatic dihydroxy alcohol for use, 3-diox-2-base ethers.In the polyacetals of describing in the Deutsches Reichs-Patent instructions 2,718,254, preferentially select the polyacetal that contains aliphatic aldehyde unit and diol units for use.
In addition, some very compounds suitable for use in West Germany's prospectus 2,928,636, have been put down in writing.In this literary composition, the polymerization ortho esters conduct of having described the ortho acid ester group that has repetition on main chain can be by the compound of acid cleavage.These groups are to have 1 of five-membered ring or hexatomic ring, the 2-alkyl ether of 3-dioxane alkane.Particularly preferred material is to have 1, the polymkeric substance of 3-dioxane hexyl-2-alkyl ether repetitive, and in this repetitive, said alkylether radicals can be separated by ether oxygen atom, and this alkylether radicals preferably is bonded on the 5-position of adjacent ring.
Can be by the ratio of the compound of acid cleavage in photosensitive mixtures, the percent by weight with respect to the non-volatile component of this potpourri is between the 8-65 usually, preferably is between the 14-44.Eliminate the compound amount of acid, the % meter is between the 0.1-10 by weight, preferably is between 0.2 and 5.
Coating composition of the present invention can also contain the dimeric molecule bonding agent except that containing above-mentioned photosensitive component.The polymer binder of preferentially selecting for use is insoluble in water, but but dissolves or swelling in alkaline aqueous solution.Can in alkaline medium, dissolve or the suitable adhesive of swelling comprises: the natural resin of shellac and rosin and so on, styrene and maleic anhydride multipolymer, acrylic acid or methacrylic acid copolymer especially with synthetic resin such as the multipolymer of acrylate or methacrylate and particularly novolaks.In the novolaks condensation resin, contain the phenol of replacement and the more highly condensed resin of formaldehyde condensation, proved particularly suitable.The type of alkali soluble resin and quantity, different with the purposes of expection; The ratio of these resins in the total solid material is with 30-90%(weight) for well, 55-85%(weight especially).Adopting poly-(4-vinyl-phenol) type phenol resin to replace novolaks, also is favourable as a composition that contains the potpourri of novolaks perhaps.And can use many other resins jointly, and that preferentially selects for use has a polyvinyl, for example polyvinyl acetate, polyacrylate, polyvingl ether and polyvinyl pyrrolidone etc., and these materials still can be with copolymer-modified.The best ratio of these resins depends on technological requirement and to the influence of required development conditions.This ratio generally is no more than about 20% of alkali soluble resin weight.In order to satisfy for example pliability, adhesion, gloss or the like specific (special) requirements, in this photosensitive mixtures, can also add a small amount of other material, for example polyglycol, cellulose derivative (as ethyl cellulose), surfactant, dyestuff, fine-grannular pigment and ultraviolet light absorber etc. in case of necessity.
Solution of the present invention can be coated in the photoresist technology on the various support material commonly used, for example the copper laminated plate of insulating material, photogravure with copper roller, serigraphy with on the silicon that uses in nickel roller, aluminium sheet, glass plate and the microelectronics, silicon nitride and the silica surface.For example being coated with coating liquid of the present invention on zine plate, brass-chromium plate, Solder for Al-Cu Joint Welding-chromium plate, aluminium sheet or the steel plate, also can make typographic printing version and hectographic printing version by the present invention.
The photochromics that is coated with exposes by means of conventional light source, and the radiation peak of this conventional light source is in the shortwave scope of the long-wave limit of ultraviolet light or visible light.Also can utilize electron beam, X-ray beam or laser beam imaging.
The alkaline aqueous solution of development usefulness has the alkalescence of calibration, that is to say that its pH value preferably is between 10 and 14, and wherein also can contain a small amount of organic solvent or surfactant.Utilize this alkaline aqueous solution to remove and penetrate the copy coating area that shone by light, thus produce preimage just as.
What following embodiment put down in writing is the preferred embodiments of the invention.Unless otherwise indicated, otherwise used ratio and percentage number average refer to unit of weight.Parts by weight (P.b.w.) and volume umber (P.b.v.) with gram and centimetre
3Expression.
Embodiment 1
What this embodiment illustrated is to use electrochemical plating, produces the printing yarn fabric with taking turns commentaries on classics nickel wire reticulated printing template.
Prepare coating liquid with following material:
Butanols, 15p.b.w.,
1-methoxyl-propyl alcohol-2(Dowanol PM, The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640) 45p.b.w.,
The softening point temperature scope is cresols-formaldehyde novolac (meeting DIN3,181) 28p.b.w. of 105-120 ℃,
Polyvingl ether (Lutonal A25) 3.5p.b.w.,
The polyacetal 8.3P.6W of 2-ethyl butyraldehyde and triethylene glycol,
2-(6-methoxyl-naphthyl-2)-4,6-pair-trichloromethyl-s-triazine 0.2p.b.w., and
Crystal violet alkali 0.01p.b.w.,
Having on the light of conduction peel ply, the contractile slightly nickel roller, coating liquid in the coating forms the good coating of surface quality, and thickness reaches 60 μ m to 75 μ m.Coating process is finished in two steps, promptly utilizes pressurized air to spray, and is dry then, sprays once more thereafter.Then this was taken turns transfer roller fully dry 30 minutes with infrared radiator.This solution can change with the method that reduces butanone content in this solution until the thickness of required homogenizing time of bone dry and this coating.Do not contain butanone in this solution even, can obtain the good coating of surface quality yet.
When using by the butanone of 40p.b.w., acetate β-ethoxy ethyl ester of 15p.b.w and 2-(β-ethoxy-ethoxy of 5p.b.w) potpourri formed of ethanol, during as the solvent of aforementioned coating composition, coating quality is also fine.But, in fact, when only using in these solvents a kind of solvent, can not make the second best in quality coating.
Make the nickel roller that was coated with then, desiring appropriateness exposure under the positivity masterplate that is printed, the silk screen that 32 row are arranged in utilizing every centimetre, make the tone value of positivity masterplate be transformed into imaging unit with different visible density, with 1,2-naphthalene roller diazide is that base-material, its thickness are half positivity coating of above-mentioned coating thickness, and the time shutter that needs is above-mentioned four times.The solution that use is made up of following material develops:
0.5% NaOH,
0.8% sodium metasilicate (nonahydrate) and
1.0% ethylene glycol mono-n-butyl ether and
97.7% deionized water.
During development, will be through the roller of overexposure, immerse in rotating condition suitable size, wherein fill among the container that accounts for half amount development liquid of its volume.The anti-overdevelop ability of this coating is good, therefore can form the straight resist layer in edge, and this roller was rotated in developer solution 6 minutes, removes dipper then, washes this roller with water, then at air drying.
At the exposed region of this roller core, electro-deposition thickness reaches 0.1mm nickel.This roller core is shunk, with acetone this anti-corrosion masterplate is peeled off, from then on roller core draws it and removes, so made a kind of flexible rotary printing masterplate.Take turns many apertures on the revolving die version by this, printing ink is painted on the yarn fabric that desire printed according to the pattern of imaging.
When the polyacetal that uses n-Heptaldehyde and tetraethylene glycol during, obtained similar result as chemical combination that can cracking.
Embodiment 2
This embodiment explanation when the high image resolution printed circuit board (PCB) of preparation, is coated with coating solution of the present invention with roll coater.In order to prepare solids content is 30% coating liquid, with following substance dissolves in 1-methoxypropanol-2:
The novolaks 64p.b.w. of embodiment 1,
Polyvinyl methyl ether (Lutonal M40) 11p.b.w.,
2-ethyl butyraldehyde and hexane-1, the polyacetal 15p.b.w. of 6-glycol,
3-methoxyl methane and 5-oxo-7, the poe 9.5p.b.w. of 7-dihydroxy-methyl-nonyl alcohol-1,
2-acenaphthene base-5-base-4,6-pair-trichloromethyl-s-triazine 0.4p.b.w., and
Crystal violet alkali 0.1p.b.w,
Make a kind of viscosity and be approximately 90mm
2The coating liquid of/S.Solids content is 40% respective coatings liquid, and viscosity is approximately 200mm
2/ S.If use 1-ethoxy-propyl alcohol-2(ethoxy propyl alcohol EP, Deutsch BPChemie GmbH) replace 1-methoxypropanol-2, then the viscosity of 40% coating liquid is approximately 320mm
2/ S.
When utilizing the roller coat device, for example AKL400 type forming roll is coated with device and (can have bought Messrs Buerkie on market, Freudenstadt, the product of the Federal Republic of Germany, this roller coat device is suitable for the bilateral coating, have the grovved roll of 48 to 64 linear groove/2.5cm), with the solution of preparing above, when being coated on the insulating material electro-coppering laminated plate with through hole, once after the coating, employed coating liquid, grovved roll and machine adjustments device can obtain the sub-coating that thickness is approximately 3-14 μ m during according to coating.According to required process length cycle length, suitably select 1-methoxyl-propyl alcohol-2,1-ethoxy-propyl alcohol-2 or its potpourri, also can change homogenizing time and drying time.Adopt described coating liquid can obtain good equal voltinism and drying property, the character that these performances are obtained when using the common solvent potpourri to dissolve same solid mixture is suitable.This solvent mixture commonly used is made up of acetate-β-ethoxy ethyl ester, dimethylbenzene and butyl acetate, wherein also can contain o-chloro-toluene arbitrarily and to the chlorotoluene potpourri.
After the drying, make this version at corresponding hole area, in the exposure down of negative preimage, then the developer with embodiment 1 washes these zones, and dry this version is 10 minutes under 80 ℃ of temperature, utilizes electrochemical plating to reinforce with copper then, and the electrotinning layer.This photoresist layer is exposed under positive light path primary image, and develop according to the method described above.With alkaline etching (selective electroplating technology) is fallen in exposed copper etch.
If under some occasion, need the lithography layer that consolidation is less, pliability is higher, then use 1-methoxypropanol-2 and 2-ethyl butanol content to be respectively 85% and 15% solvent mixture, the single solvent that replacement is adopted above.After drying, residual in coating have a small amount of (being no more than 2%) high boiling solvent, and its effect is just like flexibility agent.Add 10%3-methoxybutanol or 20% acetate-3-methoxyl butyl ester and obtained similar result.As mixing material, also can use 1-isobutoxy-propyl alcohol-2(iBP, the product of DeutscheBP-Chemie).
Embodiment 3
On electrostatic spraying apparatus, go up the solution that coating is made up of following material at the glass plate (oxide skin(coating) that one deck tin is arranged on it) of producing the LCD element:
The novolaks 1 of embodiment 1,2p.b.w,
The toluene solution 10p.b.w of 50% polyvinyl methyl ether,
4-(2-phenyl-propyl group-2) 1 of phenol, 2-naphthoquinone-2-diazide-4-sulphonic acid ester 4p.b.w., and
By equivalent 1-methoxyl-propyl alcohol-2 and 2-methoxypropanol-1(DowanolPM and Solvenon PM, BASF AG makes) the potpourri 74p.b.w that forms.
Coating process is as follows:
With spraying process by means of diameter be 60mm, the above-mentioned solution of the bell spray material port of high speed rotating and pump spraying ormal weight under 40,000 rev/mins of rotating speeds and 100 kilovar DC voltage.This bell spray material port is installed in apart from coating cloth deck 30 centimeters, above this coating cloth deck, by the glass plate guiding of ground connection.Under these conditions, electric current is less than 1mA.Rotating speed by in 0.8-2m/ divides scope, changing pace and pump (rev/min), dry coating thickness is reached between the 4-10 μ m.Be approximately 5 μ m if wish coating thickness, preferably by adding higher solution, coating solution concentration be adjusted to 15% in case of necessity.
After the drying, expose under positive preimage, this preimage is the several pipelines of advancing of a rotary calculator viewing area.Solution with embodiment 1 develops then, uses 5% hydrochloric acid at last, from exposed region indium-tin-oxide is removed.
Embodiment 4
According to embodiment 1 described mode, use the positive photoresist solution of forming by following material, high image resolution circuit pattern is transferred on the silicon chip:
1-methoxyl-propyl alcohol [2] 76p.b.w.,
The novolaks 13.6p.b.w. of embodiment 1,
1,3-pair-[2-(5-ethyl-5-butyl-1, the own oxygen base of 3-dioxane)]-2-ethyl-2-butyl propane 6.6p.b.w.,
The triazine 1.1p.b.w of embodiment 2 and
Polyvingl ether (Iutonal A25) 2.7p.b.w.
Under 6,000 rev/mins, utilization is got rid of the method for being coated with and is coated with above-mentioned solution, and dry in the drying by circulating air cupboard.Make the positivity PS silicon chip that can store in this way, compare with the positivity photoresist layer commonly used that with adjacent naphthoquinone two azide is the same thickness of base-material, its light sensitivity increases several times.Use the AZ1350J photoresist that to have bought on the market to do contrast test.The AZ1350J photoresist is a base-material with the o-quinone diazide, and it is widely used among the microelectronics field.The contrast test condition is identical with embodiment 1, but has been to use the optical filter of prolonging exposure time, and comparative test result is: the time shutter of non-diazonium coating is 3 seconds, and the diazonium coating is 20 seconds.Under 1 minute the condition of developing liquid developing of using embodiment 1,, preferably adopt this two kinds of time shutter in order to obtain about 3/2 times good image resolution up to the test of ITEK primary image.According to disclosed european patent application book 42,104 and 42,105 described methods, add polysiloxane and fluorine surfactant, can avoid the striped that may form in the process of being coated with because of getting rid of, it is identical that this situation is presented during with use AZ1350J photoresist.When using 1-ethoxy propyl alcohol-2 to replace 1-methoxypropanol-2, can obtain the coating of similar quality.
Embodiment 5
When preparation is used to produce the positivity photoresist liquid of xeroxing gravure copper roller, stir with following substance dissolves in 85p.b.w.1-methoxypropanol-2:
The novolaks 12p.b.w. of embodiment 1,
The copolymer 1 p.b.w that forms by 95% vinyl acetate and 5% butenoic acid,
By 1mole2,3,4-trihydroxy benzoyl benzene and 2molel, the quinone potpourri 2p.b.w. that 2-naphthoquinone-2-diazide-5-sulfonic acid chloride is condensed into, and
Crystal violet alkali 0.1p.b.w..
Prepare comparative solution by following material:
Above-mentioned novolaks 24p.b.w.,
Above-mentioned multipolymer 2p.b.w,
Above-mentioned ester admixture 4p.b.w.,
Crystal violet alkali 0.2p.b.w., and
Trichloroethanes 49p.b.w.,
Isopropyl alcohol 14p.b.w.,
Butyl acetate 7p.b.w. and
Cellosolvo 100p.b.w..
Change on the copper roller at the wheel that newly plated copper with spray gun for paint, these two kinds of coating solutions respectively are coated on half area, make coating thickness reach 4 μ m, utilize hot-air or infrared radiator to make this two layers of dryings then.Check this two coatings, find that coating that solution of the present invention produces is much more smooth, more even and spreading is also better than another coating.Desire in addition with having that the halftone negative of printed patterns exposes then, 0.8% sodium hydroxide solution is poured on the roller of slowly rotation, make the copper surface exposure present image with the method.Concerning these two kinds of coatings, this operation steps kept 2-4 minute.Use this roller of water rinse and in addition dry then, in operation, roller is further rotated with hot-air.
Before using this photogravure commonly used of liquor ferri trichloridi etching, utilize the mechanical correction method to repair the coating layer portion of these two desire contrasts by graver, make a mark and additional wire.With regard to these two coatings, this experiment has reached the good result that can contrast, because this two coating still contains about 1% residual solvent after drying, and mainly contains toxic cellosolvo among that layer of contrast.
Embodiment 6
The coating liquid of the present invention that is to use of this embodiment explanation is made the hectographic printing version.
Utilize rolling method to be coated on the aluminium base by the coating liquid that following material is formed, coating is before with the side hacking of wire brush with this aluminium base surface:
The novolaks 7p.b.w. of embodiment 1,
2-(naphthalene-2-oxygen base)-5,5-dimethyl-1,3-oxazolone-42p.b.w.,
2-(4-methoxyl-anthracene-1-yl)-4,6-is two-trichloromethyl-s-triazine 0.4p.b.w. and
4-lignocaine azo 0.1p.b.w., and
1-methoxypropanol-290.8p.b.w.
This aluminium surface is easily equably by this solution wetted, and before the coating bone dry, this coating keeps its uniform properties.In order to quicken dry run, can replace its alternative amount of 1-methoxypropanol-2 to be no more than 15% with sec-butyl alcohol.In order to slow down dry run, can replace all or part of 1-methoxypropanol-2 with 1-ethoxy propyl alcohol-2.
The thickness of this coating is equivalent to 2 gram/rice
2
After the drying, make this plate exposure, develop, use water rinse, use 1% phosphoric acid wiping at last, prepare printing with adding the sodium phosphate aqueous solution (3.5%) of NaOH with pH regulator to 12.6 with positive primary image.Even this plate is when standing time is than long 12 times of required time in developer solution, imaging region in fact also is unlikely and defective occurs.After this, this version can be used for printing, and it is easy to accept printing ink.
Embodiment 7
Use with embodiment 1 in identical solid constituent, be dissolved in the 1-ethoxy propyl alcohol-2, make the solution of 40% concentration, the solution that this method is made is a kind of system that (20 centimetres of bell spray material port distances, high pressure is 80 kilovars) carries out electrostatic spraying under the condition similar to embodiment 3 that is suitable for.At first with this solution of 3-methoxybutanol-1 dilution, making wherein, solids content is adjusted to 26%(weight).After the drying, the weight of coating is approximately 5 gram/rice
2On for example aluminium or copper holder, this coating shows good spreading.
This coating liquid can use in spraying, can use under the situation that contains suitable high solid material even.Can use isobutoxy propyl alcohol simultaneously, and need not to change the spraying condition up to about 5%.
Claims (8)
1, positivity radiation-sensitive coating liquid, wherein contain:
A) the total solid material of 10-50% (weight), this total solid material contains the compound of 3%-50% (weight) radiation-sensitive or the compound compositions of radiation-sensitive with respect to the general assembly (TW) meter of this solid matter, said composition contains the compound of the radiation-curable formation acid of 0.1% to 10% (weight) and 8% to 65% (weight) can be by the compound of this acid cleavage, and
B) organic solvent or the ORGANIC SOLVENT MIXTURES of 90%-50% (weight), with respect to the general assembly (TW) meter of this solvent or solvent mixture, said solvent or solvent mixture contain 65-100% (weight) 1, the single C of 2-propylene glycol
1-C
4-alkyl ether.
2, the coating liquid of claim 1 radiation-sensitive of asking for protection, wherein said glycol ethers is 1, single C of 2-propylene glycol
1Or single C
2Alkyl ether.
3, the coating liquid of claim 1 radiation-sensitive of asking for protection, wherein said glycol ethers is 1, the monomethyl ether of 2-propylene glycol.
4, the coating liquid of each radiation-sensitive of asking for protection of claim 1 to 3 wherein also contains polymer binder, and said bonding agent is water insoluble, but is dissolved in the alkaline aqueous solution.
5, each the coating liquid of radiation-sensitive of claim 1 to 3, wherein contained light-sensitive compound is 1, the 2-naphthoquinone-2-diazide.
6, the coating liquid of each radiation-sensitive of asking for protection of claim 1 to 3, the compound compositions of wherein contained radiation-sensitive be by:
A) having one at least can be by the compound of the C-O-C key of acid cleavage, and
B) the radiant rays compound that can make it to form strong acid is formed.
7, the coating liquid of the radiation-sensitive of asking for protection in the claim 4, wherein said polymer binder is novolaks.
8, the coating liquid of the radiation-sensitive of asking for protection in the claim 1, wherein said 1,2-propylene glycol list-C
1-C
4Alkyl ether is 1,2-propylene glycol monomethyl ether and (perhaps) 1,2-dihydroxypropane single-ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85105070 CN1030113C (en) | 1984-06-07 | 1985-07-03 | Positive-working radiation-sensitive coating solution |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843421160 DE3421160A1 (en) | 1984-06-07 | 1984-06-07 | Positive-working radiation-sensitive coating solution |
| CN 85105070 CN1030113C (en) | 1984-06-07 | 1985-07-03 | Positive-working radiation-sensitive coating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85105070A CN85105070A (en) | 1986-12-31 |
| CN1030113C true CN1030113C (en) | 1995-10-18 |
Family
ID=25741837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85105070 Expired - Lifetime CN1030113C (en) | 1984-06-07 | 1985-07-03 | Positive-working radiation-sensitive coating solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1030113C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004347682A (en) * | 2003-05-20 | 2004-12-09 | Tokyo Ohka Kogyo Co Ltd | Positive photoresist composition for manufacturing system liquid crystal display and method for forming resist pattern |
-
1985
- 1985-07-03 CN CN 85105070 patent/CN1030113C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN85105070A (en) | 1986-12-31 |
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