CN1584742A - Positive light sensitive resin composition - Google Patents
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- CN1584742A CN1584742A CN 03155152 CN03155152A CN1584742A CN 1584742 A CN1584742 A CN 1584742A CN 03155152 CN03155152 CN 03155152 CN 03155152 A CN03155152 A CN 03155152A CN 1584742 A CN1584742 A CN 1584742A
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Abstract
A positive photosensitive resin used for curtain coating on large scale baseplate is prepared from basic soluble resin, O-naphthoquinone diazidosulfoacid carboxylate and solvent. The resin has viscosity of 2.0-5.0 cps measured at 25 degree C, solid state content of 6-16 by wt.% and 25 degree or below contact angle of the resin to large scale baseplate.
Description
Technical field
The present invention relates to the positive-type photosensitive resin composition on the large substrate that a kind of mode that is suitable for the curtain coating coating is coated on LCD.Particularly provide to be coated with in a kind of coating back no linear residual trace (comprising linear residual trace of level and the residual trace of veritcal linearity), the residual trace of no cloud form, the face that homogeneity is good, edge thickness deviate is low, and positive-type photosensitive resin composition that can the alkaline-based developer development.
Background technology
LCD is on making, comprise thin film transistor (TFT) (TFT) and colored filter (Colorfilter), the substrate trend that always is inevitable that maximizes, be of a size of the first generation substrate of 320mm * 400mm from what is called, to the second generation substrate that is of a size of 370mm * 470mm, to the third generation substrate that is of a size of 550mm * 650mm, be of a size of 680mm * 880mm～730mm * 920mm the 4th generation substrate, its purpose will reduce manufacturing cost exactly.Now the main flow size of metacoxal plate has been defined as the length of side greater than the substrate more than the 5th generation of 1000mm, for example: 960mm * 1100mm, 1100mm * 1250mm, 1100mm * 1300mm, 1500mm * 1800mm, 1800mm * 2000mm etc., its productivity effect estimate than the 4th generation substrate high about one times.
When substrate size when 550mm * 650mm is following, if when being coated on the normal Photosensitive resin of TFT loop or chrome black colour moment battle array (Cr black matrix) usefulness on the substrate with the revolution coating method, with respect to the central part of substrate, the tendency that thickens is arranged partly around the substrate.The raw material availability of revolution coating simultaneously is extremely low, has the photoresist material more than 90% can be thrown off substrate approximately when the revolution coating, that is, use the mode of revolution coating easily to cause the waste of normal Photosensitive resin material, production capacity to reduce.
When substrate size is amplified to 730mm * 920mm, be to save unit area photoresist material usage, the coating method of photoresist changes " curtain coating-revolution is coated with " into by early stage " revolution coating ".Wherein " curtain coating-revolution coating " mode is earlier photoresist to be coated on the substrate in the mode of curtain coating coating (slit coating), and then allow photoresist be evenly distributed on (being curtain coating-revolution rubbing method, slit-spin process) on the substrate in the revolution mode.The advantage of this kind coating method is that the use amount of photoresist material can significantly reduce, utilization rate of raw materials can be by below 10% of revolution coating, be increased to about 20%, but the shortcoming of the residual extremely thick photoresist (edgebead) of substrate edges still can't be improved, the blocked up photoresist in substrate periphery manufacturing process for cleaning cleaning base plate edge need be set, so need increase equipment investment cost and cleaning fluid to purchase the material cost, and influence overall throughput.
And the substrate size length of side of using when LCD is during greater than 1000mm, for reducing the use cost of photoresist material, the coating method of photoresist has determined to change employing " non-rotating coating ", promptly only get final product with curtain coating rubbing method photosensitive resin coating, must be again through revolution coating (the promptly so-called curtain coating rubbing method that need not turn round coating, hereinafter to be referred as the curtain coating rubbing method, spinlessprocess), for example have among the 36th page of in November, the 2002 monthly magazine Display (japanese periodical) mention with the curtain coating coating produce maximize the 5th generation colored filter substrate manufacturing technology and device, and for example also have in the 107th page of in June, 2002 electronic material (japanese periodical) and mention that the curtain coating apparatus for coating is applied to the coating production of the substrate of flat-panel screens.Aforementioned curtain coating rubbing method does not need again through the revolution coating, its advantage is that the service efficiency of photoresist material is 100%, purchasing of photoresist material expects that cost can reduce, the no longer residual extremely thick photoresist material of substrate edges, must not add peripheral cleaning device during manufacturing again and buy cleaning fluid, so can effectively reduce manufacturing cost.
Yet adopt the curtain coating rubbing method, still have that linear residual trace, the residual trace of cloud form are too much, problems such as not good, the edge thickness deviate height of coating homogeneity exist in the face, particularly imagery coverages such as TV, personal computer increase recently, and this kind curtain coating coating method is difficult to guarantee the image quality homogeneity of giant display.
Summary of the invention
The object of the present invention is to provide in no level of a kind of formation and the residual trace of veritcal linearity, the residual trace of no cloud form, the face coating homogeneity good, and the low positive-type photosensitive resin composition of edge thickness deviate, this positive-type photosensitive resin composition are fit to be coated on the large substrate of LCD with the curtain coating rubbing method.
In the positive-type photosensitive resin composition described in the present invention, be by (A) alkali-soluble Trees fat; (B) carboxylate of adjacent naphthoquinones two nitrine sulfonic acid classes, and (C) solvent Suo Group becomes.
Wherein, between 2.0～5.0cps, Gu shape divides content between 6～16 weight %, and the contact angle of this photosensitive resin composition and large substrate is below 25 degree in 25 ℃ of measured viscosity for this photosensitive resin composition.
(A) alkali soluble resin
Alkali soluble resin used in the present invention (A) is for example: the condensate of novolaks (novolac) resin, phenolic aldehyde (resol) resin, acrylic acid series (acrylic) resin, polyvinyl alcohol (PVA) (polyvinylalcohol), styrene-propene acid copolymer (copolymer of styrene/acrylic acid), hydroxy styrenes (hydroxy styrene), tygon hydroxylphenyl ester (polyvinyl hydroxy benzoate) etc. wherein are preferably the alkali-soluble novolac resin.
Alkali-soluble novolac resin of the present invention generally is by aromatic hydroxy compound and aldehyde (aldehyde) class condensation and get.Wherein aromatic hydroxy compound is for example: phenol (phenol) ,-cresols (m-cresol), p-Cresol (p-cresol), neighbour-cresols (o-cresol), 2,3-xylenols (2,3-xylenol), 2,5-xylenols (2,5-xylenol), 3, the 5-xylenols (3,5-xylenol), 3, the 4-xylenols (3,4-xylenol) wait diformazan phenols (xylenol); Between-ethyl-phenol (m-ethyl phenol), right-ethyl-phenol (p-ethyl phenol), neighbour-ethyl-phenol (o-ethyl phenol), 2,3,5-pseudocuminol (2,3,5-trimethyl phenol), 2,3,5-triethyl phenol (2,3,5-triethyl phenol), 4-tributyl phenol (4-tert-butyl phenol), 3-tributyl phenol (3-tert-butyl phenol), 2-tributyl phenol (2-tert-butyl phenol), 2-the tributyl-4-methylphenol (2-tert-butyl-4-methylphenol), 2-the tributyl-5-methylphenol (2-tert-butyl-5-methylphenol), the alkyl benzene phenols (alkyl phenol) of 6-the tributyl-3-methylphenol (6-tert-butyl-3-methylphenol) etc.; Right-metoxyphenol (m-methoxy phenol) ,-metoxyphenol (m-methoxy phenol), right-thanatol (p-ethoxyphenol) ,-thanatol (m-ethoxy phenol), to propoxyl group phenol (p-propoxyphenol) ,-the alkoxy benzene phenols (alkoxyphenol) of propoxyl group phenol (m-propoxy phenol) etc.; The isopropenylbenzene phenols (isopropenyl phenol) of neighbour-isopropenyl phenol (o-isopropenyl phenol), right-isopropenyl phenol (p-isopropenyl phenol), 2-methyl-4-isopropenyl phenol (2-methyl-4-isopropenyl phenol), 2-ethyl-4-isopropenyl phenol (2-ethyl-4-isopropenylphenol) etc.; The aryl phenol class of phenylphenol (phenylphenol) (aryl phenol); 4,4 '-dihydroxybiphenyl (4,4 '-dihydroxyphenyl), bisphenol-A (bisphenol A), resorcinol (resorcinol), p-dihydroxy-benzene (hydroquinone), 1,2, the poly-Hydroxybenzenes (polyhydroxyphenol) of 3-benzenetriol (pyrogallorl) etc.Above-claimed cpd can use separately, or and with more than 2 kinds.And in the aforementioned aromatic hydroxy compound with neighbour-cresols ,-cresols, p-Cresol, 2,5-xylenols, 3,5-xylenols, 2,3,5-pseudocuminol etc. is preferable.
The concrete example of the aldehyde of the present invention and aromatic hydroxy compound condensation (aldehyde) class is as formaldehyde (formaldehyde), paraformaldehyde (paraformaldehyde), trioxymethylene (trioxane), acetaldehyde (acetaldehyde), propionic aldehyde (propionaldehyde), butyraldehyde (butylaldehyde), trimethyl-acetaldehyde (trimethyl acetaldehyde), acryl aldehyde (acrolein), crotonaldehyde (crotonaldehyde), hexamethylene aldehyde (cyclohexanealdehhyde), furtural (furfural), furylacrolein (furylacrolein), benzaldehyde (benzaldehyde), terephthalaldehyde (terephthalaldehyde), phenylacetaldehyde (phenylacetaldehhyde), α-hydrocinnamicaldehyde (α-phenylpropylaldehyde), the beta-phenyl propionic aldehyde (β-phenylpropylaldehyde), neighbour-hydroxy benzaldehyde, between-hydroxy benzaldehyde, p-hydroxybenzaldehyde, neighbour-tolyl aldehyde, between-tolyl aldehyde, right-tolyl aldehyde, neighbour-chlorobenzaldehyde, between-chlorobenzaldehyde, right-chlorobenzaldehyde, cinnamic acid etc.Above-mentioned aldehydes of giving an example can use or mix plural number separately and plant use, is preferable with formaldehyde wherein.
Aromatic hydroxy compound of the present invention and aldehydes are the products for condensation reaction, and in the presence of acidic catalyst with the technique known manufacturing, concrete acidic catalyst has: hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, para Toluic Acid etc.
The resin of this condensation reaction gained is dissolved with poor solvent, injects water and then and is precipitated.Employed poor solvent is for example: methyl alcohol (methanol), ethanol alcohols such as (ethanol); The ketone of acetone, MEK; Ethyl cellosolve acetate (ethylene glycol monoethylether acetate), tetrahydrofuran (tetrahydrofuran) etc.
The weight average molecular weight of alkali-soluble novolac resin of the present invention is generally 2,000～20,000, be preferably 2,500～12,000, be more preferred from 3,000～8,000, this molecular weight adjustment can be used single novolac resin, also can use the novolac resin of two or more different molecular weight to reach.
(B) carboxylate of adjacent naphthoquinones two nitrine sulfonic acid classes
The photonasty material of (B) composition of basic composition of the present invention, be to use the carboxylate of adjacent naphthoquinones two nitrine sulfonic acid, this carboxylate has no particular limits, can select frequent user for use, the preferably has: the adjacent naphthoquinones two nitrine sulfonic acid of adjacent naphthoquinones two nitrine-5-sulfonic acid, adjacent naphthoquinones two nitrine-4-sulfonic acid, adjacent naphthoquinones two nitrine-6-sulfonic acid etc. and the carboxylate of hydroxyl compound, better person is the carboxylate of above-mentioned adjacent naphthoquinones two nitrine sulfonic acid and multi-hydroxy compound.Above-claimed cpd is esterification or partly esterification fully, and the kind of aforementioned hydroxyl compound is following listed.
(1) Viosorb 110 class, for example: 2,3,4-trihydroxy benzene ketone, 2,4,4 '-trihydroxy benzene ketone, 2,4,6-trihydroxy benzene ketone, 2,3,4,4 '-tetrahydroxy benzene ketone, 2,2 ', 4,4 '-tetrahydroxy benzene ketone, 2,3 ', 4,4 ', 6-penta hydroxy group Benzophenone, 2,2 ', 3,4,4 '-penta hydroxy group Benzophenone, 2,2 ', 3,4,5 '-penta hydroxy group Benzophenone, 2,3 ', 4,5,5 '-penta hydroxy group Benzophenone, 2,3,3 ', 4,4 ', 5 '-hexahydroxybenzene ketone etc.
(2) general expression (I)
R in the following formula
4～R
6Be hydrogen atom or rudimentary alkyl (alkyl), R
7～R
12Be hydrogen atom, halogen atom, rudimentary alkyl, rudimentary alkoxy (alkoxy), rudimentary fat thiazolinyl (alkenyl) and naphthenic base (cycloalkyl), R
13And R
11Be hydrogen atom, halogen atom and rudimentary alkyl, x ', y ' and z ' are 1～3 integer, and n is 0 or 1.The concrete example of following formula hydroxy aryl compound is as three (4-hydroxy phenyl) methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-4-hydroxy phenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-3-hydroxy phenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-4-hydroxy phenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-3-hydroxy phenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-3,4-dihydroxy benzenes methylmethane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-3,4-dihydroxy benzenes methylmethane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-2,4-dihydroxy benzenes methylmethane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-2,4-dihydroxy benzenes methylmethane, two (4-hydroxy phenyl)-3-methoxyls-4-hydroxy phenyl methane, two (3-cyclohexyl-4-hydroxy phenyl)-3-hydroxy phenyl methane, two (3-cyclohexyl-4-hydroxy phenyl)-2-hydroxy phenyl methane, two (3-cyclohexyl-4-hydroxy phenyl)-4-hydroxy phenyl methane, two (3-cyclohexyl-4-hydroxyl-6-methyl aryl)-2-hydroxy phenyl methane, two (3-cyclohexyl-4-hydroxyl-6-aminomethyl phenyl)-3-hydroxy phenyl methane, two (3-cyclohexyl-4-hydroxyl-6-aminomethyl phenyl)-4-hydroxy phenyl methane, two (3-cyclohexyl-4-hydroxyl-6-aminomethyl phenyl)-3,4-dihydroxy benzenes methylmethane, two (3-cyclohexyl-6-hydroxy phenyl)-3-hydroxy phenyl methane, two (3-cyclohexyl-6-hydroxy phenyl)-4-hydroxy phenyl methane, two (3-cyclohexyl-6-hydroxy phenyl)-2-hydroxy phenyl methane, two (3-cyclohexyl-6-hydroxy-4-methyl phenyl)-2-hydroxy phenyl methane, two (3-cyclohexyl-6-hydroxy-4-methyl phenyl)-4-hydroxy phenyl methane, two (3-cyclohexyl-6-hydroxy-4-methyl phenyl)-3,4-dihydroxy benzenes methylmethane, 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene, 1-[1-(3-methyl-4-hydroxy phenyl) isopropyl]-4-[1, two (3-methyl-4-hydroxy phenyl) ethyls of 1-] benzene.
(3) general expression (II)
R in the following formula
15And R
16Be hydrogen atom or low alkyl group; x " and y " be 1～3 integer, the concrete example of (hydroxy phenyl) hydro carbons of following formula is as 2-(2,3; 4-trihydroxy phenyl)-2-(2 '; 3 ', 4 '-trihydroxy phenyl) propane, 2-(2, the 4-dihydroxy phenyl)-2-(2 '; 4 '-dihydroxy phenyl) propane, 2-(4-hydroxy phenyl)-2-(4 '-hydroxy phenyl) propane, two (2; 3,4-trihydroxy phenyl) methane, two (2, the 4-dihydroxy phenyl) methane etc.
(4) other aromatic hydroxy compound class for example: phenol, right-metoxyphenol, xylenol, p-dihydroxy-benzene, naphthols (naphthol), catechol (pyrocatechol), 1,2,3-benzenetriol methyl ether (pyrogallol monomethyl ether), 1,2,3-benzenetriol-1,3-dimethyl ether (pyrogallol-1,3-dimethyl ether), 3,4,5-trihydroxybenzoic acid (gallicacid), partly esterification or partly etherificate 3,4,5-trihydroxybenzoic acid etc.Aforementioned hydroxyl compound is with 2,3,4-trihydroxybenzophenone, 2,3,4, and 4 '-four hydroxyl oxygen base benzophenone are preferable.Aforementioned hydroxyl compound can use or mix several uses separately.
The carboxylate (B) of the adjacent naphthoquinones two nitrine sulfonic acid classes of the photonasty material in the resin combination of the present invention can use the compound that contains the quinone diazido, for example: adjacent naphthoquinones two nitrine-4 (or 5) sulfonic acid halogen and above-mentioned (one)～(fours') hydroxyl compound is through condensation reaction, esterification or partly esterification and getting fully, aforementioned condensation reaction is normally at dioxane (dioxane), N-pyrrolidone (N-pyrrolidone), carry out in the acetamide organic solvents such as (acetamide), simultaneously at triethanolamine (triethanolamine), carry out more favourable under base such as alkali carbonate or alkali metal hydrogencarbonate condensation agent exists.
At this moment, in hydroxyl compound, hydroxyl adds up to mole %, be preferably 50 moles more than the %, the best is to form carboxylate with the condensation of adjacent naphthoquinones two nitrine-4 (or 5) sulfonic acid halogen at 60 moles more than the %, that is esterification degree is more than 50%, preferably more than 60%.
With respect to the alkali soluble resin (A) of 100 weight portions, the use amount of the carboxylate (B) of adjacent naphthoquinones two nitrine sulfonic acid classes of the present invention is 1～100 weight portion, is preferably at 10～50 weight portions.
(C) solvent
The organic solvent that solvent used in the present invention need be selected for use easily and other organic principle dissolves mutually.This solvent is preferably below the 5.0mmHg in 25 ℃ of following saturated vapour pressures, is more preferred from below the 4.5mmHg, and the best is below the 4.0mmHg.If this solvent is below 25 ℃ of following saturated vapour pressure 5.0mmHg, then eurymeric sensing optical activity resin combination is after the large substrate coating, and the residual trace of cloud form is difficult for generating.
When measuring saturated vapour pressure, can use general common many methods, for the present invention, can correctly measure with the method for evapotranspiring (gas communication method).
With 100 weight portion alkali soluble resins (A) is benchmark, and the use amount of the solvent of photosensitive resin composition of the present invention (C) is preferably the 700-2000 weight portion, is more preferred from the 900-1800 weight portion.
Solvent of the present invention (C) can be selected from: ethers system or ester class system, wherein ethers system as: glycol propyl ether (ethylene glycol monopropyl ether), diethylene glycol dimethyl ether (diethyleneglycol dimethyl ether), ethylene glycol monomethyl ether (ethylene glycol monomethylether), ethylene glycol ethyl ether (ethylene glycol monoethyl ether), diethylene glycol methyl ether (diethylene glycol monomethyl ether), DGDE (diethyleneglycol monoethyl ether), butyl carbitol (diethylene glycol monobutylether).And ester class system as: acetate methoxyl ethyl ester (methyl cellosolve acetate), ethoxyethyl acetate(EA) (ethyl cellosolve acetate), propylene glycol monomethyl ether acetate (propylene glycol monomethyl ether acetate), propylene-glycol ethyl ether acetate (propylene glycol ethyl ether acetate), propylene glycol propyl ether acetate (propylene glycol propyl ether acetate) and ethyl lactate (ethyllactate) etc.Aforementioned solvents can a kind of independent use or and with more than 2 kinds or 2 kinds.In the aforementioned solvents, preferable with propylene glycol monomethyl ether acetate and ethyl lactate.
Positive-type photosensitive resin composition of the present invention can further add aromatic hydroxy compound, to adjust the sensitivity or the viscosity of constituent.The concrete example that is suitable for aromatic hydroxy compound of the present invention is for example: the Japanese trade name TPPA-1000P of Honshu Chemical Ind, TPPA-1100-2C, TPPA-1100-3C, TPPA-1100-4C, TPPA-1200-24X, TPPA-1200-26X, TPPA-1300-235T, commercially available products such as TPPA-1600-3M6C, TPPA-MF, wherein the commodity with trade name TPPA-1600-3M6C, TPPA-MF are preferable, and it can separately or merge use.Alkali soluble resin (A) with 100 weight portions is made benchmark, and the consumption of this aromatic hydroxy compound is generally 0～20 weight portion, is preferably 0.5～18 weight portion, is more preferred from 1.0～15 weight portions.
Positive-type photosensitive resin composition of the present invention, can further add adherence auxiliary agent, the agent that has an even surface, thinning agent and compatible good dyestuff, wherein, for example can be used as adherence auxiliary agent of the present invention: melamine (melamine) compound and silane based compound, effect is to increase the adherence between positive-type photosensitive resin composition and attaching substrates, wherein the instantiation of melamine as: commercially available: Cymel-300,303 (Mitsui's manufacturings), MW-30MH, MW-30, MS-11, MS-001, MX-750, MX-706 (three and chemical) etc.And silane (silane) based compound concrete example is as vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-epoxy prapanol propyl trimethoxy silicane, 3-epoxy prapanol propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, 3-metacryloxy propyl trimethoxy silicane, 3-mercapto propyl trimethoxy silicane etc.Alkali soluble resin (A) with 100 weight portions is made benchmark, and the use amount of the adherence auxiliary agent of melamine (melamine) compound is generally 0～20 weight portion, is preferably 0.5～18 weight portion, is more preferred from 1.0～15 weight portions; The use amount of the adherence auxiliary agent of silane (silane) based compound is generally 0～2 weight portion, is preferably 0.001～1 weight portion, is more preferred from 0.005～0.8 weight portion.
Can be used in and of the present inventionly for example have an even surface agent: fluorine is that surfactant, silicon (Silicon) are surfactant etc.Wherein fluorine is the surfactant concrete example as the FlourateFC-430 of commercially available 3M, FC-431, the F top EF122A of Tochem product, 122B, 122C, 126 and BL20 etc.And silicon (Silicon) is the surfactant concrete example as the SF8427 of commercially available Toray DowCorning Silicon, SH29PA etc.Alkali soluble resin (A) with 100 weight portions is made benchmark, and the use amount of above-mentioned surfactant is generally 0～1.2 weight portion, is preferably 0.025～1.0 weight portion, is more preferred from 0.050～0.8 weight portion.
Can be used in the thinning agent of thinning agent of the present invention such as trade name RE801, RE802 (Ink of kingdom system).
For example can be used in the good dyestuff of compatibility of the present invention: curcumin (curcumin), cumarin (coumarin) are, azo (azo) dyestuff etc., and in addition, the present invention also can add other adjuvant according to need again, for example: plasticizer, stabilization agent etc.
Positive-type photosensitive resin composition of the present invention, its viscosity scope under room temperature is preferably 2.2～4.8cps about 2.0～5.0cps, and the best is 2.5～4.5cps.When viscosity less than 2cps, coating back easily produces the residual trace of cloud form, and the coating homogeneity is not good in the face; If viscosity is greater than 5.0cps, the coating back easily produces linear residual trace.The mensuration mode of above-mentioned viscosity is that positive-type photosensitive resin composition is placed the 50ml beaker, beaker is placed 25 ℃ water-bath again, measures its viscosity number with vibration-type viscosity meter (mountain one motor system, model VM200T3) behind the constant temperature.Among the present invention, viscosity can be waited by the kind of the molecular weight of alkali soluble resin (A) and alkali soluble resin (A), solvent (C) or content and other adjuvant and adjust.
The solid shape branch scope of positive-type photosensitive resin composition of the present invention is 6～16 weight %, is preferably 7～15 weight %, is more preferred from 8～14 weight %.If solid shape is divided less than 6 weight %, the coating back easily produces the residual trace of cloud form, and the coating homogeneity is not good in the face; If solid shape is divided greater than 16 weight %, the coating back easily generates linear residual trace.The mensuration mode that above-mentioned solid shape is divided is to measure with heating.Solid shape is divided to be waited by the kind of the carboxylate (B) of solvent (C), adjacent naphthoquinones two nitrine sulfonic acid classes, alkali soluble resin (A) or content and adjuvant and is adjusted among the present invention.
The contact angle of positive-type photosensitive resin composition of the present invention and large substrate generally needs below 25 degree, and is preferable between 5～23 degree, better for 7～21 degree.If contact angle is poor because of coating greater than 25 degree, easily cause coating homogeneity variation in the face, edge thickness deviate is too high, especially in the scope of 7～21 degree, is difficult for producing the thin partially phenomenon of edge thickness.Above-mentioned measurement of contact angle method, be that constituent is dropped on the large-scale plain glass substrate, and, utilize the assay method of Sessile Drop Method in contact (the system CA-VP150 of consonance interface science incorporated company type contact angle meter), measure the contact angle after 30 seconds.The selection that this contact angle can be by solvent (C) among the present invention, the kind of alkali soluble resin (A) and add suitable surfactant or other adjuvant (as thinning agent) is adjusted.
During fabrication, the using method of positive-type photosensitive resin composition of the present invention, be that carboxylate (B), solvent (C) with alkali soluble resin (A), adjacent naphthoquinones two nitrine sulfonic acid classes is uniformly mixed into solution state in stirrer, can add adherence auxiliary agent, surfactant, thinning agent, compatible good dyestuff, plasticizer, stabilization agent etc. in case of necessity simultaneously.Mode with the curtain coating coating is coated on this constituent on the large substrate at last.The coating back forms the photosensitive compoistion layer in pre-roasting (prebake) mode with removal of solvents.Pre-roasting condition according to the kind of each composition, cooperates ratio and different, is generally temperature between 90～110 ℃, carries out 1 minute-10 minutes.After pre-roasting, this photosensitive resin composition layer is between between specified light shield (mask), and (as Nikon 1755G7A) exposes with stepper, impregnated in developer solution in 23 ± 2 ℃ again and develops in 30 seconds-5 minutes, and the part of not wanting is removed and formed pattern.The light that exposure is used: the ultraviolet ray that can be g line, h line, i line etc. is good, and UV-device can be (surpassing) high mercury vapor lamp and metal halid lamp.
Above-mentioned large substrate for example is meant: be used for the alkali-free glass, soda-lime glass, hard glass (Pai Lesi glass), quartz glass of liquid crystal indicator etc. and in this type of nesa coating that adheres on glass, or be used for photo-electric conversion device substrate (as silicon substrate) of solid-state image sensor etc. or the like.Large substrate of the present invention is meant: the length of side at least on one side of substrate is more than 800 centimetres or 800 centimetres, preferablely is meant that at least one length of side is more than 1000 centimetres or 1000 centimetres.
Moreover developer solution is to use as the Tetramethylammonium hydroxide of 0.1～5 weight % (tetramethyl ammonium hydroxide), sodium carbonate (Na
2CO
3), sodium bicarbonate (Na
2HCO
3), NaOH (NaOH), potassium hydroxide (KOH) etc.And when using the developer solution that these alkaline aqueous solutions constitute, generally be clean to wash again after video picture.Secondly, again with pressurized air or compressed nitrogen with pattern air-dry after, make last heat treated with heating arrangements such as hot plate or baking ovens again.Institute's constant temperature is 100～250 ℃, and the hot plate of fixing time is 2 minutes-60 minutes, and baking oven is 2 minutes～90 minutes.
[evaluation method]
(1) viscosity: positive-type photosensitive resin composition is placed the 50ml beaker, again beaker is placed 25 ℃ water-bath, measure its viscosity number with vibration-type viscosity meter (mountain one motor system, model VM200T3) behind the constant temperature.Unit is cps.
(2) solid shape branch: the positive-type photosensitive resin composition of 1g (smart scale) is placed in the aluminium dish, again the aluminium dish is placed 180 ℃ heat dish (hot plate) to go up heating weighing again after 2 hours, calculate its solid shape branch with weight difference.Unit is weight %.
(3) contact angle: positive-type photosensitive resin composition is dropped in large-size glass substrate after last 30 second, in the mensuration mode of contact angle (the system CA-VP150 of consonance interface science incorporated company type contact angle meter), Sessile Drop Method, measure angle again.Unit is degree.
(4) solvent vapour is pressed: measure with the method for evapotranspiring (gas communication method), measure 25 ℃ of temperature.Unit is mmHg.
(5) linear residual trace: be coated on positive-type photosensitive resin composition on the large-size glass substrate of 1100mm * 960mm with the curtain coating rubbing method, then 85 ℃ of pre-down baking 5 minutes, form pre-roasting filming, under sodium vapor lamp, whether visual examination has the phenomenon of " being coated with linear residual trace ".Linear residual trace can be divided into linear residual trace of level and the residual trace of veritcal linearity, its shape such as following shown in Figure 1.
Zero: do not have linear residual trace
△: linear residual trace is arranged a little, but not obvious
*: linear residual trace is arranged
(6) the residual trace of cloud form: photosensitive resin composition is coated on the large-size glass substrate of 1100mm * 960mm with the curtain coating rubbing method, under 85 ℃ of temperature, baked 5 minutes in advance then, form pre-roasting filming, under sodium vapor lamp, whether visual examination has the phenomenon of " the residual trace of coating cloud form ".Its shape as shown in Figure 1.
Zero: the residual trace of no cloud form
△: the residual trace of cloud form is arranged a little, but not obvious
*: the residual trace of cloud form is arranged
(7) coating homogeneity in the face: photosensitive resin composition is coated on the large-size glass substrate of 1100mm * 960mm with the curtain coating coating method, under 85 ℃ of temperature, baked 5 minutes in advance then, form pre-roasting filming, measure thickness, measuring point such as following shown in Figure 2 with Tencor α-step contact pin type analyzer again.
Thickness FT (avg) be following (x, y)=(240,275), (480,275), (720,275), (240,550), (480,550), (720,550), (240,825), (480,825), (720,825) mean value of totally 9 thickness.
(x, y) max is the maximal value of 9 thickness to thickness FT.
(x, y) min is the minimum value of 9 thickness to thickness FT.
The coating homogeneity can be judged by following formula in the face
Zero: be lower than 3%
△: between 3～5%
*: be higher than 5%
(8) edge thickness deviate: with coating homogeneity operation in (7) face
○：|(FT(edge)-FT(avg))/FT(avg)|×100％＜3％
△: | (FT (edge)-FT (avg))/FT (avg) | * 100% between 3～5%
×：|(FT(edge)-FT(avg))/FT(avg)|×100％＞5％
FT (edge) substrate edges thickness is (x, thickness y)=(10,550)
Description of drawings
Fig. 1 is the linear residual trace and the residual trace shape of the cloud form synoptic diagram of curtain coating coating;
Fig. 2 is the inhomogeneity measuring point synoptic diagram of coating in the measurement face.
Embodiment
Synthesizing of [synthesis example] alkali soluble resin
Synthesis example a
Will between-cresols and p-Cresol mixed with 50: 50 weight ratio, adds formaldehyde then, and with oxalic acid as catalyst, carry out the condensation polymerization reaction with well-established law, and adjust the suitable degree of polymerization, get final product to such an extent that weight average molecular weight is 5,230 alkali soluble resin a.
Synthesis example b
With the method for synthesis example a, do not exist together be with-weight ratio of cresols and p-Cresol is adjusted into 30: 70, can makes the alkali soluble resin b of weight average molecular weight 2,180.
Synthesis example c
With the method for synthesis example a, do not exist together be with-weight ratio of cresols and p-Cresol is adjusted into 70: 30, can makes the alkali soluble resin c of weight average molecular weight 8,450.
Synthesis example d
With neighbour-cresols ,-cresols and p-Cresol mixed with 5: 45: 50 weight ratio, adds formaldehyde then, and with oxalic acid as catalyst, carry out the condensation polymerization reaction with well-established law, and adjust the suitable degree of polymerization, can obtain weight average molecular weight and be 5,382 alkali soluble resin d.
Embodiment 1
(1) modulation of positive-type photosensitive resin composition
Alkali soluble resin a with 90 weight portions, the alkali soluble resin b of 10 weight portions, 27.5 2 of weight portion, 3,4-trihydroxybenzophenone and 1, (average esterification degree is 85% to the carboxylate of 2-naphthoquinones two nitrine-5-sulfonic acid, hereinafter to be referred as B-1), 7.5 2 of weight portion, 3,4,4 '-tetrahydroxybenzophenone and 1, carboxylate (the average esterification degree 85% of 2-naphthoquinones two nitrine-5-sulfonic acid, hereinafter to be referred as B-2), polyphenol compound (the trade name TPPA-1600-3M6C of 4 weight portions, Japan's Honshu chemical industry system) and surfactant (the trade name SF8427 of 0.3 weight portion, Toray Dow CorningSilicone system) is dissolved in propylene glycol monomethyl ether acetate (hereinafter to be referred as the PGMEA) solvent of 1100 weight portions, can makes positive-type photosensitive resin composition.
(2) estimate
After of the filtrator filtration of this photosensitive resin composition with 0.2 μ m, be coated on the curtain coating coating method on the large-size glass substrate of 1100 * 1250mm, can obtain filming of about 15 μ m, carry out baking (prebake) 90 seconds in advance with 100 ℃ then, get pre-roasting the filming of photosensitive resin composition, estimate.Again with after stepper (Nikon 755G7A) exposure irradiation, after developing 50 seconds with 2.38% Tetramethylammonium hydroxide developer solution then, the part of pattern exposure is removed.Secondly, again with pressurized air or compressed nitrogen with pattern air-dry after, at last make last heat treated with hot plate, institute's fixed temperature is 150 ℃, the hot plate of fixing time is 5 minutes, can form required pattern, fills a prescription and evaluation result is stated from table one.
Embodiment 2～7, comparative example 1～5
With the method for operating of embodiment 1, difference is the mixture ratio and the consumption of the carboxylate (B) that changes alkali soluble resin (A), adjacent naphthoquinones two nitrine sulfonic acid classes, solvent (C), adjuvant, and prescription and evaluation result are stated from table one.
The above, it only is preferred embodiment of the present invention, when can not limiting scope of the invention process with this, promptly every simple equivalent of doing according to the scope and the description of claims of the present invention changes and modifies, and all should still belong in the scope that patent of the present invention contains.
Table one: the composition of various embodiments of the present invention and comparative example and evaluation result.
Table one
| Composition (weight portion) | Embodiment | Comparative example | |||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 1 | 2 | 3 | 4 | 5 | ||
| Alkali soluble resin (A) | a | 90 | 90 | 100 | 80 | 90 | 90 | 90 | |||||
| b | 10 | 20 | 10 | 10 | 100 | 10 | 10 | ||||||
| c | 10 | 10 | 100 | 20 | |||||||||
| d | 90 | 90 | 80 | ||||||||||
| The carboxylate (B) of adjacent naphthoquinones two nitrine sulfonic acid classes | (B-1) | 27.5 | 25 | 25 | 35 | 35 | 27.5 | 25 | 35 | 27.5 | 35 | 35 | 27.5 |
| (B-2) | 7.5 | 10 | 10 | 7.5 | 10 | 7.5 | 7.5 | ||||||
| Solvent (C) | PGMEA | 1100 | 1000 | 100 | 900 | 1100 | 1100 | 1100 | 600 | 2500 | 300 | ||
| EL | 1300 | 100 | 1000 | ||||||||||
| nBA | 1100 | ||||||||||||
| Y-butyrolactone | 800 | ||||||||||||
| Adjuvant | Polyphenol compound-1 | 4 | 4 | 4 | 4 | ||||||||
| Surfactant-1 | 0.3 | 0.15 | 0.3 | ||||||||||
| Surfactant-2 | 0.15 | 0.3 | 0.3 | ||||||||||
| Adherence auxiliary agent-1 | 4 | 4 | |||||||||||
| Thinning agent-l | 0.5 | ||||||||||||
| Rerum natura | Viscosity (cps) | 3 | 3.1 | 3.2 | 2.7 | 3.6 | 3.7 | 3 | 7.3 | 1.8 | 8.1 | 1.5 | 4.2 |
| Gu shape branch (weight %) | 11.2 | 9.5 | 11 | 11.4 | 13.1 | 11.5 | 10.9 | 11.3 | 11.4 | 18.8 | 5.3 | 11.7 | |
| Contact angle (degree) | 19.2 | 19.6 | 194 | 20.8 | 19.3 | 18.8 | 19.3 | 20.2 | 19.6 | 20.1 | 19.4 | 28.2 | |
| Solvent saturated vapour pressure (mmHg) | 3.8 | 2.2 | 3.7 | 2.3 | 3.8 | 3.8 | 8.7 | 3.8 | 3.8 | 3.8 | 3.8 | 3.1 | |
| Evaluation result | Linear current mark | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | △ | × | △ | ○ |
| The cloud form current mark | ○ | ○ | ○ | ○ | ○ | ○ | △ | ○ | × | ○ | × | △ | |
| Coating homogeneity in the face | ○ | ○ | ○ | ○ | ○ | ○ | ○ | △ | × | △ | × | × | |
| Edge thickness deviate | ○ | ○ | ○ | ○ | ○ | ○ | ○ | △ | ○ | △ | ○ | × | |
(B-1) 2,3,4-trihydroxybenzophenone and 1, the carboxylate of 2-naphthoquinones two nitrine-5-sulfonic acid
(B-1) 2,3,4,4 '-tetrahydroxybenzophenone and 1, the carboxylate of 2-naphthoquinones two nitrine-5-sulfonic acid
PGMEA propylene glycol monomethyl ether acetate propylene glycol monomethyl ether acetate
EL ethyl lactate ethyl lactate
NBA n-butyl acetate n-butyl acetate
γ-butyrolactone butyrolactone
Polyphenol compound-1 trade name TPPA-1600-3M6C, Japanese Honshu chemical industry system
Surfactant-1 trade name SF8427, Toray Dow Corning Silicone system
Surfactant-2 trade name BL-20, Tochem product system
Adherence auxiliary agent-1 trade name Cymel-303, Mitsui's system
Thinning agent-1 trade name RE801, the INK of kingdom system
Claims (5)
1, a kind of positive-type photosensitive resin composition, it is to be coated on the LCD large substrate in the mode that curtain coating is coated with, and it is characterized in that this constituent comprises:
(1) alkali soluble resin (A);
(2) carboxylate (B) of adjacent naphthoquinones two nitrine sulfonic acid classes; And
(3) solvent (C);
Wherein, this photosensitive resin composition in 25 ℃ of measured viscosity between 2.0～5.0cps, Gu shape divides content between 6～16 weight %, and below the contact angle 25 of this photosensitive resin composition and the large substrate degree.
2, positive-type photosensitive resin composition according to claim 1 is characterized in that, solvent (C) is below the 5mm-Hg in 25 ℃ saturated vapour pressure.
3, positive-type photosensitive resin composition according to claim 1 is characterized in that, this photosensitive resin composition in 25 ℃ of measured viscosity between 2.2～4.8cps.
4, positive-type photosensitive resin composition according to claim 1 is characterized in that, its solid shape divides content between 7～15 weight %.
5, positive-type photosensitive resin composition according to claim 1 is characterized in that, the contact angle of this photosensitive resin composition and large substrate is between 5～23 degree.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031551521A CN100365509C (en) | 2003-08-22 | 2003-08-22 | Positive light sensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031551521A CN100365509C (en) | 2003-08-22 | 2003-08-22 | Positive light sensitive resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1584742A true CN1584742A (en) | 2005-02-23 |
| CN100365509C CN100365509C (en) | 2008-01-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107431020A (en) * | 2015-03-27 | 2017-12-01 | 东丽株式会社 | The effective photosensitive polymer combination of film crystal, cured film, thin film transistor (TFT), liquid crystal display device or organic el display, the manufacture method of cured film, the manufacture method of thin film transistor (TFT) and the manufacture method of liquid crystal display device or organic el display |
| JP2019179093A (en) * | 2018-03-30 | 2019-10-17 | 住友ベークライト株式会社 | Photosensitive resin composition, resin film and electronic device |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01235947A (en) * | 1988-03-16 | 1989-09-20 | Kanegafuchi Chem Ind Co Ltd | Positive type photoresist thin film |
| US5314782A (en) * | 1993-03-05 | 1994-05-24 | Morton International, Inc. | Deep UV sensitive resistant to latent image decay comprising a diazonaphthoquinone sulfonate of a nitrobenzyl derivative |
| JP3968177B2 (en) * | 1998-09-29 | 2007-08-29 | Ａｚエレクトロニックマテリアルズ株式会社 | Fine resist pattern forming method |
| CN1166737C (en) * | 2001-10-15 | 2004-09-15 | 奇美实业股份有限公司 | Positive photosensitive resin composition |
-
2003
- 2003-08-22 CN CNB031551521A patent/CN100365509C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107431020A (en) * | 2015-03-27 | 2017-12-01 | 东丽株式会社 | The effective photosensitive polymer combination of film crystal, cured film, thin film transistor (TFT), liquid crystal display device or organic el display, the manufacture method of cured film, the manufacture method of thin film transistor (TFT) and the manufacture method of liquid crystal display device or organic el display |
| CN107431020B (en) * | 2015-03-27 | 2020-07-24 | 东丽株式会社 | Photosensitive resin composition for thin film transistor, cured film, and thin film transistor |
| JP2019179093A (en) * | 2018-03-30 | 2019-10-17 | 住友ベークライト株式会社 | Photosensitive resin composition, resin film and electronic device |
| JP7056320B2 (en) | 2018-03-30 | 2022-04-19 | 住友ベークライト株式会社 | Photosensitive resin composition, resin film and electronic device |
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| Publication number | Publication date |
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| CN100365509C (en) | 2008-01-30 |
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