CN101013263B - Photosensitive resin composition suitable for irrational and slit mold coating method - Google Patents

Photosensitive resin composition suitable for irrational and slit mold coating method Download PDF

Info

Publication number
CN101013263B
CN101013263B CN200710001223XA CN200710001223A CN101013263B CN 101013263 B CN101013263 B CN 101013263B CN 200710001223X A CN200710001223X A CN 200710001223XA CN 200710001223 A CN200710001223 A CN 200710001223A CN 101013263 B CN101013263 B CN 101013263B
Authority
CN
China
Prior art keywords
photosensitive resin
resin composition
phenolics
methyl
emulsion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN200710001223XA
Other languages
Chinese (zh)
Other versions
CN101013263A (en
Inventor
岛仓纯一
高桥修一
张勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
AZ Electronic Materials Japan Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by AZ Electronic Materials Japan Co Ltd filed Critical AZ Electronic Materials Japan Co Ltd
Publication of CN101013263A publication Critical patent/CN101013263A/en
Application granted granted Critical
Publication of CN101013263B publication Critical patent/CN101013263B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/022Quinonediazides
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/0045Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/022Quinonediazides
    • G03F7/023Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G03F7/0236Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

Abstract

The present invention provides a radiation sensitive resin composition suitable for spinless, slit coating and having high coating film thickness uniformity. The radiation sensitive resin composition is characterized in that it includes alkali soluble formaldehyde-phenol resin, sensitizer and ester of fatty acid and lower alcohol. The invention also provides a method for manufacturing resists base plate by the composition and a manufactured resists base plate thereby.

Description

Be applicable to the photosensitive resin composition of irrotationality, slit die coating process
Technical field
The present invention relates to irrotationality, slit die applies and uses photosensitive resin composition; More particularly, relating to a kind of irrotationality, slit die of filming than the better resist of film thickness uniformity in the past of can forming when applying through irrotationality, slit die coating process applies and uses photosensitive resin composition.
Background technology
In the manufacturing of SIC (semiconductor integrated circuit) element, color filter, liquid crystal display cells etc., in order to carry out retrofit, adopted lithography technique in the past, developing the technology that can carry out the microfabrication of submicron degree in recent years.In this lithography technique, after forming antireflection film on the substrate, apply eurymeric or negative type photo-sensitive resin combination as required, form the photosensitivity resist film after the prebake.Then, this photosensitivity resist film is carried out for example developing behind the pattern exposure with various rays such as ultraviolet ray, far ultraviolet, electron beam, X ray, form the resist pattern.
As the coating method of photosensitive resin composition, known spin-coating method, rolling method, the flat the whole bag of tricks such as method (ラ Application De コ one ト method), curtain coating coating process, knife coating, dip coating method that are coated with.Specifically, in the manufacturing of SIC (semiconductor integrated circuit) element or liquid crystal display cells, as the material of resist film, adopt the positive type photosensitive resin combination mostly, and adopt spin-coating method mostly as coating method.In addition, in the manufacturing of liquid crystal display cells,, generally also adopt rolling method when adopting spin-coating method as coating method.
But; When adopting spin-coating method as the method that photosensitive resin composition is coated on the substrate; Drop in resist solution on the substrate along with the centrifugal force of substrate rotation after substrate peripheral direction curtain coating; Most of resist solution becomes superfluous resist solution and is dispersed by the substrate periphery and to remove, and these resist solution of removing that disperse go out of use.This spin-coating method can easily form the resist film with homogeneous film thickness, but on the other hand, and the amount of above-mentioned discarded resist is more, has the high shortcoming of cost.By contrast, rolling method be owing to can making used most of resist utilize as resist film, thereby can cost degradation, produces the shortcoming that striated or shaddock skin shape etc. apply spots but when applying photosensitive resin composition, have.For example, have in the liquid crystal display cells that the resist film of this coating spot makes, the brightness disproportionation of light occurs, cause the tendency that descends as commodity value, therefore also proposed the rolling method (patent documentation 1) of improvement in use.
In addition, for adapting to the maximization of substrate size in recent years, the slit die coating process becomes the main stream approach that replaces spin-coating method.Even under the situation of using this coating method, the composition of composition also is identical usually.For example; Make known former being generally of photosensitive resin composition that flat-panel monitor uses with phenolics and quinone two nitrine emulsion photosensitive resin composition as principal ingredient; Even forming under the situation of filming, also be to use most this composition that needs to regulate viscosity through the slit die coating process.But in general slit die coating process (for example the coating speed of photosensitive resin composition is that 100mm/ is about second), it is higher that the end of applicator surface produces the tendency that expands, and must eliminate the thicker end of film thickness, causes yield rate lower.Consider from the angle of yield-power; Apply in (for example the coating speed of photosensitive resin composition is that 150mm/ is about second) in the high-velocity scanning that further improves coating speed; This tendency further improves, and therefore need with irrotationality, slit die coating process the time, can access the very photosensitive resin composition of homogeneous film thickness.
[patent documentation 1] TOHKEMY 2000-267270 communique
Summary of the invention
The purpose of this invention is to provide a kind of photosensitive resin composition, the shortcoming of the problem before it does not have to produce in irrotationality, slit die coating process.Specifically, provide a kind of and can prevent membrane thickness unevenness when applying, apply the high photosensitive resin composition of film thickness uniformity through irrotationality, slit die coating process.
Resist is in the past formed through irrotationality, the coating of slit die coating process the time; Be considered to substrate end-face film thickness uniformity existing problems; Present inventors find, in the photosensitive resin composition of the emulsion through making the alkali soluble resin that comprises alkali-soluble phenolics etc. and naphthoquinones two triazo-compounds etc., contain fatty acid esterification and obtain specific compound in alcohol; Thereby can obtain to have the photosensitive resin composition of good coating characteristic, accomplish the present invention thus.That is, photosensitive resin composition of the present invention is characterised in that containing fatty acid and the carbon number that alkali-soluble phenolics, emulsion and carbon number are 10-20 is the ester of the alcohol of 1-5.
In addition, the manufacturing approach of resist substrate of the present invention is characterised in that and comprises through the slit die coating process above-mentioned photosensitive resin composition is coated on the substrate, and resist substrate of the present invention is characterised in that through this method manufacturing.
The photosensitive resin composition that is applicable to irrotationality, slit die coating of the application of the invention; Can form and apply more excellent in the past the filming of film thickness uniformity ratio; When making liquid crystal display cells etc. with it, can make the high-quality goods that do not have luminance brightness uneven at low cost.
Embodiment
Photosensitive resin composition of the present invention with the ester of alkali-soluble phenolics, emulsion and fatty acid and alcohol as must composition.Explanation to these each compositions is following.
Used alkali-soluble phenolics is the novolac type phenol resin that is obtained by the aldehyde condensation polymer of at least a phenols and formalin etc. in the photosensitive resin composition of the present invention.
As the used phenols of this alkali-soluble phenolics of preparation, can enumerate for example toluene phenols such as o-cresol, p-cresol and m-cresol; 3,5-xylenol, 2,5-xylenol, 2,3-xylenol, 3, dimethyl benzene phenols such as 4-xylenol; 2,3,4-pseudocuminol, 2,3,5-pseudocuminol, 2,4,5-pseudocuminol, 3,4, trimethylbenzene phenols such as 5-pseudocuminol; Tert-butyl phenols such as 2-tert-butyl phenol, 3-tert-butyl phenol, 4-tert-butyl phenol; 2-metoxyphenol, 3-metoxyphenol, 4-metoxyphenol, 2,3-syringol, 2,5-syringol, 3, methoxybenzene phenols such as 5-syringol; 2-ethyl-phenol, 3-ethyl-phenol, 4-ethyl-phenol, 2,3-diethyl phenol, 3,5-diethyl phenol, 2,3,5-triethyl phenol, 3,4, ethyl phenols such as 5-triethyl phenol; Neighbour-chlorophenol ,-chlorophenol, right-chlorophenol, 2, chlorobenzene phenols such as 3-chlorophenesic acid; Resorcinol classes such as resorcinol, 2-methylresorcinol, cresorcinol, oreinol diphenol; Catechols such as 5-methyl pyrocatechol; Pyrogallol classes such as 5-methyl pyrogallol; Bisphenols such as bisphenol-A, B, C, D, E, F; 2,6-dihydroxymethyl-right-methylolation cresols classes such as cresols; Aphthols such as alpha-Naphthol, betanaphthol etc.They can use separately or with multiple potpourri.
In addition, as aldehydes, except formalin, can also enumerate salicylide, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxy benzaldehyde, chloroacetaldehyde etc., they can use separately or with multiple potpourri.
As alkali-soluble phenolics used herein, can use and separate the alkali-soluble phenolics of removing low molecular weight compositions.As the method that low molecular weight compositions is removed in separation, method of for example can enumerate the liquid-liquid separating method of separation resin in having different deliquescent two kinds of solvents, removing through the centrifuging low molecular weight compositions or thin-film distillation method etc.
As emulsion, preferably can enumerate the emulsion that contains the quinone diazido.Contain the emulsion of quinone diazido as this, any one in the known emulsion of in quinone two nitrine-phenolic resist, using before can using.As this emulsion, preferably with naphthoquinones two nitrine sulfonic acid chlorides or benzoquinones two nitrine sulfonic acid chlorides etc. with have the reaction of low molecular compound or macromolecular compound and the compound that obtains that can carry out the functional group of condensation reaction with these chloride things.Here, can enumerate hydroxyl, amino etc. with the functional group of chloride thing condensation, and hydroxyl is particularly suitable for.As hydroxyl can with the compound of chloride thing condensation, can enumerate for example p-dihydroxy-benzene, resorcinol, 2,4-hydroxy benzophenone, 2,3,4-trihydroxy benzophenone, 2,4; 6-trihydroxy benzophenone, 2,4,4 '-trihydroxy benzophenone, 2,3,4,4 '-tetrahydroxybenzophenone, 2; 2 ', 4,4 '-tetrahydroxybenzophenone, 2,2 ', 3,4; Hydroxy phenyl alkanes, 4 such as hydroxy benzophenone classes, two such as 6 '-pentahydroxybenzophenone (2, the 4-dihydroxy phenyl) methane, two (2,3,4-trihydroxy phenyl) methane, two (2, the 4-dihydroxy phenyl) propane, 4 '; 3 ", 4 "-tetrahydroxy-3,5,3 ', 5 '-tetramethyl triphenyl methane, 4,4 '; 2 ", 3 ", 4 "-penta hydroxy group-3,5, hydroxyl triphenylmethanes such as 3 ', 5 '-tetramethyl triphenyl methane etc.They can use separately, and also can make up use more than 2 kinds.
In addition, as sulfonic acid chlorides such as naphthoquinones two nitrine sulfonic acid chlorides or benzoquinones two nitrine sulfonic acid chlorides, for example preferably can enumerate 1,2-naphthoquinones two nitrine-5-sulfonic acid chloride, 1,2-naphthoquinones two nitrine-4-sulfonic acid chloride etc.The combined amount that contains the emulsion of quinone diazido, per 100 weight portion alkali soluble resins are generally the 5-50 weight portion, are preferably the 10-40 weight portion.If also lack than this amount, then can not obtain enough susceptibilitys as photosensitive resin composition, on the other hand,, then can produce the problem that becomes to analyze if more than this amount, therefore should be noted that.
Photosensitive resin composition of the present invention contains fatty acid and pure ester.The fatty acid here is that carbon number is carboxylic acid, particularly monocarboxylic acid or the dicarboxylic acids of the chain hydrocarbon of 10-20, preferred 14-18, and it can be a saturated fatty acid, also can be unsaturated fatty acid, and hydrocarbon can also have side chain.In addition, in the scope of not damaging effect of the present invention, can also be by replacements such as hydroxyl, amino.Alcohol can use the lower alcohol of carbon number as 1-5, preferred 1-3, preferred especially monohydroxy alcohol.Through these fatty acid and alcohol are reacted, can obtain ester used in the photosensitive resin composition of the present invention under common enzymatic synthesis condition.
Object lesson as preferred ester in the photosensitive resin composition of the present invention; For example; Polyunsaturated fatty acid ester can be enumerated methyl laurate, ethyl laurate, methyl myristate, ethyl myristate, soft-methyl ester, soft-ethyl ester, methyl stearate, ethyl stearte, and unsaturated fatty acid ester can be enumerated methyl oleate, ethyl oleate, castor oil acid methyl esters, castor oil acid ethyl ester, methyl linoleate, ethyl linoleate, methyl linolenate, ethyl linolenate etc.These esters can separately or mix more than 2 kinds and use as required.
The addition of ester, the total weight with respect to 100 weight portion phenolics and emulsion is generally the 1-20 weight portion, is preferably the 1-10 weight portion.If the content of ester also lacks than this amount, then can not fully show effect of the present invention, promptly can damage the homogeneity that applies thickness; In addition, if more than this amount, the tendency that then exists susceptibility to descend; Thereby can not obtain enough susceptibilitys, therefore should be noted that.
Photosensitive resin composition of the present invention can contain solvent as required.Solvent generally includes the solvent that above-mentioned each composition and following adjuvant are dissolved.As operable solvent; Can enumerate lactone such as amide-types such as ketone, DMAC N,N, N-Methyl pyrrolidone, gamma-butyrolacton class such as lactic acid esters such as propylene-glycol monoalky lether acetate esters, methyl lactate, ethyl lactate, toluene, xylene etc. such as propylene-glycol monoalky lether class, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetates such as ethylene glycol monoalkyl ether acetate class, propylene glycol monomethyl ether, dihydroxypropane single-ethers such as ethylene glycol monoalkyl ether class, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetates such as glycol monoethyl ether, ethylene glycol monoethyl ether are aromatic hydrocarbon based, methyl ethyl ketone, 2-heptanone, cyclohexanone etc.These solvents can separately or mix more than 2 kinds and use.
Photosensitive resin composition of the present invention can also contain surfactant as required.When being coated on photosensitive resin composition on the base material, the surface is gone up and can be produced flakey texture (below be called " fuzzy inequality "), and through in photosensitive resin composition of the present invention, using surfactant, can suppress this fuzzy inequality.Especially preferably use nonionic class surfactant in the photosensitive resin composition of the present invention.As nonionic class surfactant, comprise fluorine class surfactant, silicon class surfactant, hydrocarbon-surfactant etc., especially preferably use fluorine class surfactant.The combined amount of these surfactants with respect to the total amount of 1 weight portion alkali soluble resin and emulsion, is added 200-10000ppm usually.If the content of surfactant is too much, then can cause problems such as poor visualization, therefore should be noted that.
In addition, photosensitive resin composition of the present invention can also contain phenoloid as required.Through in photosensitive resin composition of the present invention, using phenoloid, the effect of the susceptibility that can be improved.This phenoloid is the compound of for example formula (I) expression:
Figure G07101223X20070116D000071
(in the formula, R 1, R 2, R 3, R 4, R 5, R 6And R 7Represent H, C independently of one another 1-C 4Alkyl perhaps
Figure G07101223X20070116D000072
(R here, 8Be H, C 1-C 4Alkyl), m and n are the integer of 0-2 independently of one another, a, b, c, d, e, f, g and h be for satisfying a+b≤5, c+d≤5, e+f≤5, the integer of the 0-5 of g+h≤5, i are the integer of 0-2).
As the object lesson of this phenoloid, can enumerate o-cresol, m-cresol and p-cresol, 2,4-xylenol, 2,5-xylenol, 2; 6-xylenol, bisphenol-A, B, C, E, F and G, 4,4 ', 4 "-and methine triphenol, 2,6-two [(2-hydroxy-5-methyl base phenyl) methyl]-4-methylphenol, 4; 4 '-[1-[4-[1-(4-hydroxy phenyl)-1-Methylethyl] phenyl] ethylidene] bis-phenol, 4,4 '-[1-[4-[2-(4-hydroxy phenyl)-2-propyl group] phenyl] ethylidene] bis-phenol, 4,4 ', 4 "-ethylidine triphenol, 4-[two (4-hydroxy phenyl) methyl]-2-thanatol, 4; 4 '-[(2-hydroxy phenyl) methylene] two [2, the 3-xylenol], 4,4 '-[(3-hydroxy phenyl) methylene] two [2, the 6-xylenol], 4; 4 '-[(4-hydroxy phenyl) methylene] two [2, the 6-xylenol], 2,2 '-[(2-hydroxy phenyl) methylene] two [3, the 5-xylenol], 2; 2 '-[(4-hydroxy phenyl) methylene] two [3, the 5-xylenol], 4,4 '-[(3, the 4-dihydroxy phenyl) methylene] two [2; 3,6-pseudocuminol], 4-[two (3-cyclohexyl-4-hydroxyl-6-aminomethyl phenyl) methyl]-1,2-benzenediol, 4,6-two [(3; 5-dimethyl-4-hydroxy phenyl) methyl]-1,2,3-benzenetriol, 4,4 '-[(2-hydroxy phenyl) methylene] two [3-methylphenols], 4; 4 ', 4 " triphenol, 4-(3-methyl isophthalic acid-dichloropropionanilide-3-time base (イ リ ジ Application)), 4 ', 4 "; 4 " '-(1,4-benzene two methines) four phenol, 2,4,6-three [(3; 5-dimethyl-4-hydroxy phenyl) methyl]-1,3-benzenediol, 2,4; 6-three [(3,5-dimethyl-2-hydroxy phenyl) methyl]-1,3-benzenediol, 4; 4 '-[1-[4-[1-[4-hydroxyl-3,5-two [(hydroxy-3-methyl phenyl) methyl] phenyl]-1-Methylethyl] phenyl] ethylidene] two [2,6-two (hydroxy-3-methyl phenyl) methyl] phenol etc.And, can enumerate 4,4 '; 4 as preferred compound "-methine triphenol, 2; 6-two [(2-hydroxy-5-methyl base phenyl) methyl]-4-methylphenol, 4,4 '-[1-[4-[1-(4-hydroxy phenyl)-1-Methylethyl] phenyl] ethylidene] bis-phenol, 4,4 '-[1-[4-[2-(4-hydroxy phenyl)-2-propyl group] phenyl] ethylidene] bis-phenol, 4; 4 ', 4 "-the ethylidine triphenol etc.
In this phenoloid, preferred especially formula (Ia) or compound (Ib).
Figure G07101223X20070116D000091
The addition of phenoloid under the situation of adding, with respect to 100 weight portion alkali-soluble phenolics and emulsion, is generally the 1-25 weight portion, is preferably the 1-20 weight portion.
Photosensitive resin composition of the present invention obtains by containing above-mentioned each composition, and its proterties is solution or dispersion liquid.Usually, be modulated into the coating condition that viscosity is suitable for applying said composition, the preferred dynamic viscosity of photosensitive resin composition of the present invention under 25 ℃ is 2-10cSt, more preferably 2-5cSt.If dynamic viscosity drops on this beyond scope, no matter be too high or low excessively, all can damage the homogeneity that applies thickness, therefore should be noted that.
The present invention is described as follows according to embodiment.
Embodiment 1
Phenolics: weight-average molecular weight is about 10000 phenolics with polystyrene conversion.
Emulsion: average esterification yield be 75% 2,3,4,4 '-tetrahydroxybenzophenone and 1, the ester compounds of 2-naphthoquinones nitrine-5-sulfonic acid chloride adds 25 weight portions with respect to 100 weight portion phenolics.
Activating agent: fluorine class surfactant メ ガ Off ア Star Network (the chemical society of big Japanese ink produces), with respect to all solids composition, add 6000ppm.
All solids composition 100 weight portions with respect to above-mentioned composition; After adding 10 parts of methyl stearates; Stirring and dissolving adopts キ ヤ ノ Application Off エ Application ス ケ automatic viscometer (manufacturing of clutch society of Co., Ltd.) once more, regulates solids content concn; Making its dynamic viscosity under 25 ℃ is 4cSt, obtains composition.
Embodiment 2
Phenolics: weight-average molecular weight is about 10000 phenolics with polystyrene conversion.
Emulsion: average esterification yield be 75% 2,3,4,4 '-tetrahydroxybenzophenone and 1, the ester compounds of 2-naphthoquinones two nitrine-5-sulfonic acid chloride adds 25 weight portions with respect to 100 weight portion phenolics.
Activating agent: fluorine class surfactant メ ガ Off ア Star Network (the chemical society of big Japanese ink produces), with respect to all solids composition, add 6000ppm.
All solids composition 100 weight portions with respect to above-mentioned composition; After adding 10 parts of ethyl steartes, stirring and dissolving adopts キ ヤ ノ Application Off エ Application ス ケ automatic viscometer to regulate solids content concn once more; Making its dynamic viscosity under 25 ℃ is 4cSt, obtains composition.
Comparative example 1
Phenolics: weight-average molecular weight is about 10000 phenolics with polystyrene conversion.
Emulsion: average esterification yield be 75% 2,3,4,4 '-tetrahydroxybenzophenone and 1, the ester compounds of 2-naphthoquinones two nitrine-5-sulfonic acid chloride adds 25 weight portions with respect to 100 weight portion phenolics.
After making solid composite dissolving with solvent, adopt キ ヤ ノ Application Off エ Application ス ケ automatic viscometer to regulate solids content concn, making its dynamic viscosity under 25 ℃ is 4c St, obtains composition.
Comparative example 2
Phenolics: weight-average molecular weight is about 10000 phenolics with polystyrene conversion.
Emulsion: average esterification yield be 75% 2,3,4,4 '-tetrahydroxybenzophenone and 1, the ester compounds of 2-naphthoquinones two nitrine-5-sulfonic acid chloride adds 25 weight portions with respect to 100 weight portion phenolics.
Activating agent: fluorine class surfactant メ ガ Off ア Star Network (the chemical society of big Japanese ink produces), with respect to all solids composition, add 6000ppm.
After making solid composite dissolving with solvent, adopt キ ヤ ノ Application Off エ Application ス ケ automatic viscometer to regulate solids content concn, making its dynamic viscosity under 25 ℃ is 4cSt, obtains composition.
Embodiment 3
Phenolics: weight-average molecular weight is about 10000 phenolics with polystyrene conversion.
Emulsion: average esterification yield be 75% 2,3,4,4 '-tetrahydroxybenzophenone and 1, the ester compounds of 2-naphthoquinones two nitrine-5-sulfonic acid chloride adds 25 weight portions with respect to 100 weight portion phenolics.
With respect to all solids composition 100 weight portions of above-mentioned composition, add 10 parts of methyl stearates after, stirring and dissolving once more adopts キ ヤ ノ Application Off エ Application ス ケ automatic viscometer to regulate solids content concn, making its dynamic viscosity under 25 ℃ is 4cSt.
Embodiment 4
Phenolics: weight-average molecular weight is about 10000 phenolics with polystyrene conversion.
Emulsion: average esterification yield be 75% 2,3,4,4 '-tetrahydroxybenzophenone and 1, the ester compounds of 2-naphthoquinones two nitrine-5-sulfonic acid chloride adds 25 weight portions with respect to 100 weight portion phenolics.
(Honshu Chemical Ind produces phenoloid: TrisP-PA: general formula (Ia)) with respect to 100 weight portion phenolics and emulsion, add 5 weight portions.
Activating agent: fluorine class surfactant メ ガ Off ア Star Network (the chemical society of big Japanese ink produces), with respect to all solids composition, add 6000ppm.
All solids composition 100 weight portions with respect to above-mentioned composition; After adding 10 parts of methyl stearates, stirring and dissolving adopts キ ヤ ノ Application Off エ Application ス ケ automatic viscometer to regulate solids content concn once more; Making its dynamic viscosity under 25 ℃ is 4cSt, obtains composition.
Apply Evaluation for Uniformity
Adopt slit die applicator to be coated on that (substrate size 1100 * 1250mm), drying under reduced pressure carry out prebake through heating plate then, form the ultraviolet curable resin film of about 1.5 μ m on the glass substrate each photosensitive resin composition.
Adopt the blooming analyzer; On coating direction and vertical direction, measure 90 points to right-hand member from the substrate left end; Point except the 50mm of substrate end, except the 20mm, except the 15mm, except the 10mm is calculated average film thickness and maximal value, minimum value, obtain inner evenness (%) through following formula.
(maximal value-minimum value)/average film thickness/2 * 100
Then, difference less than 2% be evaluated as ◎, be the O that is evaluated as of 2% above less than 3%, 3% above less than 4% be evaluated as △, be evaluated as more than 4% *.The gained result lists in table 1.
Table 1
Figure G07101223X20070116D000131
The evaluation of coated surface proterties
In addition, the proterties that visual observations is filmed under sodium vapor lamp is estimated.The applicator surface of comparative example 1 sample is found fuzzy uneven, contains the embodiment 1,2 of ester and surfactant and the applicator surface of 4 sample and does not observe fuzzy inequality fully.

Claims (4)

1. photosensitive resin composition that is used for irrotationality, slit die coating process; It is characterized in that containing alkali-soluble phenolics, contain the emulsion that the quinone diazido is rolled into a ball; With carbon number be that the carboxylic acid and the carbon number of the chain hydrocarbon of 14-18 is the ester of the monohydroxy alcohol of 1-3; The combined amount of wherein said emulsion, per 100 weight portion alkali-soluble phenolics are the 5-50 weight portion, the dynamic viscosity of said resin combination under 25 ℃ is 2-10cSt.
2. the described photosensitive resin composition of claim 1 wherein also contains surfactant.
3. claim 1 or 2 described photosensitive resin compositions wherein further contain phenoloid.
4. the manufacturing approach of a resist substrate is characterized in that comprising each described photosensitive resin composition in the claim 1~3 is coated on the substrate through irrotationality, slit die coating process.
CN200710001223XA 2006-01-31 2007-01-04 Photosensitive resin composition suitable for irrational and slit mold coating method Expired - Fee Related CN101013263B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2006-023388 2006-01-31
JP2006023388 2006-01-31
JP2006023388A JP4813193B2 (en) 2006-01-31 2006-01-31 Photosensitive resin composition suitable for spinless and slit coating

Publications (2)

Publication Number Publication Date
CN101013263A CN101013263A (en) 2007-08-08
CN101013263B true CN101013263B (en) 2012-05-30

Family

ID=38485798

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200710001223XA Expired - Fee Related CN101013263B (en) 2006-01-31 2007-01-04 Photosensitive resin composition suitable for irrational and slit mold coating method

Country Status (4)

Country Link
JP (1) JP4813193B2 (en)
KR (1) KR101285574B1 (en)
CN (1) CN101013263B (en)
TW (1) TWI387849B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5090833B2 (en) * 2007-09-11 2012-12-05 東京応化工業株式会社 Positive photoresist composition and photosensitive film-coated substrate using the same
JP5329999B2 (en) * 2009-01-29 2013-10-30 AzエレクトロニックマテリアルズIp株式会社 Pattern formation method

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1314617A (en) * 2000-03-22 2001-09-26 富士胶片株式会社 Positive sensitive flat-plate printing plate
CN1518685A (en) * 2001-06-12 2004-08-04 ���Ͽع����޹�˾ Method for forming thick resist pattern

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3842446B2 (en) * 1997-09-25 2006-11-08 富士写真フイルム株式会社 Positive photosensitive composition for infrared laser
JP2004138995A (en) * 2002-08-21 2004-05-13 Fuji Photo Film Co Ltd Plate making method for planographic printing plate
JP4545553B2 (en) * 2004-03-12 2010-09-15 東京応化工業株式会社 Non-spin coating positive photoresist composition and resist pattern forming method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1314617A (en) * 2000-03-22 2001-09-26 富士胶片株式会社 Positive sensitive flat-plate printing plate
CN1518685A (en) * 2001-06-12 2004-08-04 ���Ͽع����޹�˾ Method for forming thick resist pattern

Also Published As

Publication number Publication date
CN101013263A (en) 2007-08-08
TW200739254A (en) 2007-10-16
TWI387849B (en) 2013-03-01
KR20070079028A (en) 2007-08-03
JP4813193B2 (en) 2011-11-09
JP2007206256A (en) 2007-08-16
KR101285574B1 (en) 2013-07-15

Similar Documents

Publication Publication Date Title
CN101071267B (en) Photoresist composition
CN101553758B (en) Pattern forming method and photosensitive resin composition used therefor
CN101013263B (en) Photosensitive resin composition suitable for irrational and slit mold coating method
TWI481952B (en) A method forming a pattern, a substrate for flat panel display and manufacturing method thereof
WO2010050592A1 (en) Phenol resin for photoresist, photoresist composition containing same, and method for producing same
JP4545553B2 (en) Non-spin coating positive photoresist composition and resist pattern forming method
CN1170205C (en) Photosensitive resin composition for roll coating and method of roll coating
JP2000214582A (en) Positive photosensitive resin composition
JP4209297B2 (en) POSITIVE PHOTORESIST COMPOSITION FOR DISCHARGE NOZZLE TYPE COATING METHOD AND METHOD FOR FORMING RESIST PATTERN
JP6140506B2 (en) Positive resist composition and resist pattern forming method
JP6031905B2 (en) Method for producing novolac type phenol resin, method for producing resin composition for photoresist, and method for producing liquid crystal device
TW200424764A (en) Positive photoresist composition for manufacturing LCD and method for forming resist pattern
JP2009192571A (en) Resin composition for photoresist
JP5720157B2 (en) Resin composition for photoresist
JPH0260915A (en) Removal of oligo-nuclear component of novolak resin
JP4405293B2 (en) POSITIVE PHOTORESIST COMPOSITION FOR DISCHARGE NOZZLE TYPE COATING METHOD AND METHOD FOR FORMING RESIST PATTERN
TW200928586A (en) Positive type radiation sensitive resin compound
JP3052330B2 (en) Radiation-sensitive resin composition for semiconductor production
JP7066038B1 (en) Method for manufacturing a resin composition and a substrate with a pattern resist film
CN1714315A (en) Applicability improver for photosensitive resin composition and photosensitive resin composition containing the same
JP2005097331A (en) Production method of phenol resin for photoresist, and photoresist composition
JP2010072323A (en) Photosensitive resin composition for slit coating
TWI760123B (en) Positive photosensitive resin composition for low-temperature process and method for manufacturing photoresist film
CN1212544C (en) Photosensitive resin composition
JP2005284115A (en) Radiation sensitive resin composition for slit spin coat and its usage

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C56 Change in the name or address of the patentee

Owner name: AZ ELECTRONIC MATERIALS IP (JAPAN) K.K.

Free format text: FORMER NAME: AZ ELECTRONIC MATERIALS (JAPAN) K.K.

CP01 Change in the name or title of a patent holder

Address after: Tokyo, Japan

Patentee after: AZ Electronic Materials (Japan) K. K.

Address before: Tokyo, Japan

Patentee before: AZ electronic materials (Japan) Co., Ltd.

ASS Succession or assignment of patent right

Owner name: MERCK PATENT GMBH

Free format text: FORMER OWNER: AZ ELECTRONIC MATERIALS IP (JAPAN) K.K.

Effective date: 20150420

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20150420

Address after: Darmstadt

Patentee after: Merck Patent GmbH

Address before: Tokyo, Japan

Patentee before: AZ Electronic Materials (Japan) K. K.

CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20120530

Termination date: 20210104

CF01 Termination of patent right due to non-payment of annual fee