CN101907827B - Positive-type photosensitive resin composition and protrusion for liquid crystal orientation control prepared from same - Google Patents
Positive-type photosensitive resin composition and protrusion for liquid crystal orientation control prepared from same Download PDFInfo
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- CN101907827B CN101907827B CN2009101461199A CN200910146119A CN101907827B CN 101907827 B CN101907827 B CN 101907827B CN 2009101461199 A CN2009101461199 A CN 2009101461199A CN 200910146119 A CN200910146119 A CN 200910146119A CN 101907827 B CN101907827 B CN 101907827B
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Abstract
The invention relates to a positive-type photosensitive resin composition for liquid crystal display elements, in particular to the positive-type photosensitive resin composition for a protrusion for liquid crystal orientation control, which has the advantages of good sensitivity and no blur. The composition comprises a novolac resin (A), a naphthoquinonediazido sulfonate ester photosensitizer (B) and a solvent (C), wherein the molecular weight of the novolac resin (A) detected by gel permeation chromatography is lower than 150,000; when the total integral area of resin signals with the molecular weight between 200 and 150,000 is taken as 100 weight percent, the resin signals with the molecular weight between 200 and 400 account for less than 6 weight percent, and the resin signals with the molecular weight between 10,000 and 30,000 account for over 12 weight percent; and the novolac resin (A) is analyzed by a thermogravimetric analyzer at 230 DEG C for 30 minutes, the thermogravimetric loss is less than 10 weight percent.
Description
Technical field
The present invention relates to a kind of positive-type photosensitive resin composition, the sensitivity of utilizing this positive-type photosensitive resin composition to prepare is good, the liquid crystal aligning of no ghost phenomena is controlled the preparation method with projection and this projection, also comprises the liquid crystal display cells that utilizes this projection prepared.
Background technology
Liquid crystal display cells in flat-panel screens now by the most widely-used, in recent years along with universalnesses such as office equipments such as PC, word processor, LCD TV, for the display quality of the LCD (TFT-LCD) of membrane transistor, its performance requirement is also day by day harsh.
Among the TFT-LCD, being used mode at present at most is TN (Twisted Nematic) type LCD.This TN type LCD is in recent years because of technique improvement, the CRT that can match in excellence or beauty such as positive contrast, color reprodubility, or on it.Yet TN type LCD has the too narrow problem in visual angle.
For solving this problem, industry thereby develop MVA (Multi-domain VerticallyAlignmented) type LCD (vertical orientation type LCD).Among the MVA type LCD, desire to make liquid crystal in certain picture element zone can become the region method of plural orientation direction, can be in this picture element zone slit (slit) be set on the electrode of light incident side, simultaneously on the electrode base board that shows side in the same picture element zone, on the position of staggering with electrode narrow slit, form and have the projection (for example: triangle taper, semi-convex lens shape etc.) on inclined-plane.
Owing to this projection is that the orientation of controlling liquid crystal forms, therefore be referred to as liquid crystal aligning control projection.This liquid crystal aligning ties up to along its surface local with projection provides the directed state of liquid crystal molecule to reach inclination, even the time with respect to oblique observation of LCD face, and identical show state in the time of also obtaining with top view, thus reach the purpose at the angle of broadening one's vision.
Openly specially permit communique for this technology such as TOHKEMY 2002-122858 number and disclose, use novolaks (phenol novolac) resin as forming the technology of liquid crystal aligning control with projection.Yet projection is used in this type of liquid crystal aligning control, still has problems such as easy generation ghost phenomena when LCD shows for a long time.
Summary of the invention
The object of the present invention is to provide a kind of used for liquid crystal display element positive-type photosensitive resin composition, provide particularly that a kind of sensitivity is good, the control of the liquid crystal aligning of no ghost phenomena is with the projection positive-type photosensitive resin composition.
This constituent comprises the carboxylate emulsion (B) and the solvent (C) of novolac resin (A), adjacent naphthoquinones two nitrine sulfonic acid classes; Wherein, the molecular weight that this novolac resin (A) records with gel permeation chromatography is less than 150,000, and with molecular weight between 200～150, when the total integral area of 000 resin signals was used as 100 weight %, less than 6 weight %, molecular weight was between 10 between 200～400 proportions for its molecular weight, 000～30,000 proportions are greater than 12 weight %; And this novolac resin (A) is analyzed with thermogravimeter, and under 230 ℃, 30 minutes conditions, its thermogravimetric amount loss is less than 10 weight %.
Below one by one each composition of the present invention is described in detail:
Novolac resin (A)
Novolac resin of the present invention (A) generally by aromatic hydroxy compound and aldehyde (aldehyde) class, gets through condensation reaction in the presence of acidic catalyst.Aromatic hydroxy compound wherein, for example: phenol (phenol) ,-cresols (m-cresol), p-Cresol (p-cresol), neighbour-cresols (o-cresol), 2,3-xylenols (2,3-xylenol), 2, the 5-xylenols (2,5-xylenol), 3,5-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-ethylphenol), 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-tert-butyl phenol (4-tert-butyl phenol), 3-tert-butyl phenol (3-tert-butylphenol), 2-tert-butyl phenol (2-tert-butyl phenol), the 2-tert-butyl group-4-methylphenol (2-tert-butyl-4-methylphenol), the 2-tert-butyl group-5-methylphenol (2-tert-butyl-5-methylphenol), the alkyl benzene phenols (alkyl phenol) of the 6-tert-butyl group-3-methylphenol (6-tert-butyl-3-methylphenol) etc.; Right-metoxyphenol (p-methoxy phenol) ,-metoxyphenol (m-methoxy phenol), right-thanatol (p-ethoxy phenol) ,-thanatol (m-ethoxy phenol), to propoxyl group phenol (p-propoxy phenol) ,-the alkoxy benzene phenols (alkoxy phenol) of propoxyl group phenol (m-propoxy phenol) etc.; The isopropenylbenzene phenols (isopropenylphenol) 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-isopropenyl phenol) etc.; The aryl phenol class (aryl phenol) of phenylphenol (phenyl phenol); 4,4 '-dihydroxybiphenyl (4,4 '-dihydroxybiphenyl), bisphenol-A (bisphenol A) ,-benzenediol (resorcinol), right-benzenediol (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 aldehyde of the present invention and aromatic hydroxy compound condensation (aldehyde) class concrete example is as formaldehyde (formal dehyde), paraformaldehyde (paraformal dehyde), trioxymethylene (tri oxane), acetaldehyde (acetaldehyde), propionic aldehyde (propionaldehyde), butyraldehyde (butylaldehyde), trimethyl-acetaldehyde (trimethyl acetal dehyde), acryl aldehyde (acrolein), crotonaldehyde (crotonaldehyde), hexamethylene aldehyde (cyclohexanealdehyde), furtural (furfural), furylacrolein (furylacrolein), benzaldehyde (benzaldehyde), terephthalaldehyde (terephthalaldehyde), phenylacetaldehyde (phenylacetaldehyde), 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.
Acidic catalyst of the present invention, concrete example is as hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid etc.
The novolac resin of this condensation reaction gained (A), available good solvent is dissolved, and injects poor solvent and then and is precipitated, and repeats above-mentioned steps and is handled.
The molecular weight that novolac resin novolac resin of the present invention (A) records with gel permeation chromatography is less than 150,000, and with molecular weight between 200～150, when the total integral area of 000 resin signals is used as 100 weight %, its molecular weight accounts for below the 6 weight % between 200～400, be preferably 5～0.05 weight %, be more preferred from 4～0.05 weight %; Molecular weight is between 10,000～30, and 000 account for more than the 12 weight %, are preferably 12～50 weight %, are more preferred from 12～35 weight %.Particularly when molecular weight between 400～10,000 account for 35～75 weight %, and molecular weight is between 30,000～150,000 when accounting for 1～10 weight %, purpose of the present invention and effect are better for reaching.
Molecular weight accounts for 6 weight % when above between 200～400 among the present invention, and formed liquid crystal aligning control is used in the LCD with projection, and the ghost problem takes place easily; Molecular weight is between 10,000～30, and 000 account for 12 weight % when following, and the sensitivity of formed positive-type photosensitive resin composition is too high, overexposure easily, and formed pattern form is not good.
Novolac resin of the present invention (A) heated 30 minutes down in 230 ℃ with the thermogravimeter analysis, and its thermogravimetric amount is lost in below the 10 weight %, is preferably 8～0.2 weight %, is more preferred from below 6～0.2 weight %.When the thermogravimetric amount is lost in 10 weight % when above, formed liquid crystal aligning control is used in the LCD with projection, and the ghost problem takes place easily.
The carboxylate (B) of adjacent naphthoquinones two nitrine sulfonic acid classes
Photonasty material of the present invention, system uses the carboxylate (B) of adjacent naphthoquinones two nitrine sulfonic acid classes, this carboxylate has no particular limits, can select frequent user for use, wherein, the preferably has: the carboxylate of adjacent naphthoquinones two nitrine sulfonic acid such as adjacent naphthoquinones two nitrine-5-sulfonic acid, adjacent naphthoquinones two nitrine-4-sulfonic acid, adjacent naphthoquinones two nitrine-6-sulfonic acid and 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 formula
1～R
2Be hydrogen atom or low alkyl group (alkyl), R
3～R
9Be hydrogen atom, halogen atom, low alkyl group, lower alkoxy (alkoxy), rudimentary fat thiazolinyl (alkenyl) and naphthenic base (cycloalkyl), R
10And R
11Be hydrogen atom, halogen atom and low alkyl group, x, y and z are 1～3 integer, and n is 0 or 1.Following formula hydroxy aryl compound concrete example 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 formula
12And R
13Be hydrogen atom or low alkyl group, x ' and y ' are 1～3 integer.Following formula (hydroxy phenyl) hydro carbons concrete example 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 classes, for example: phenol, right-metoxyphenol, xylenol, p-dihydroxy-benzene, bisphenol-A, 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), 3,4,3,4 of 5-trihydroxybenzoic acid (gallicacid), part esterification or part etherificate, 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 ties up to dioxane (dioxane) usually, 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, for hydroxyl in the hydroxyl compound adds up to 100 moles of %, 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 novolac 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 10～50 weight portions, is more preferred from 20～40 weight portions.
Solvent (C)
The organic solvent that solvent used in the present invention need be selected for use easily and other organic principles dissolve mutually.
With 100 weight portion novolac resins (A) is benchmark, and the use amount of the solvent of photosensitive resin composition of the present invention (C) is 700～2,000 weight portion, is preferably 800～1,800 weight portions, is more preferred from 900～1,600 weight portions.
Solvent of the present invention (C) is for example: ethers or ester class.Wherein, the ethers concrete example is 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 (diethylene glycolmonoethyl ether), butyl carbitol (diethylene glycol monobutyl ether).And ester class concrete example is as glycol methyl ether acetate (ethylene glycol monomethyl etheracetate), ethylene glycol ether acetate (ethylene glycol monoethyl etheracetate), propylene glycol monomethyl ether acetate (propylene glycol monomethyl etheracetate), propylene-glycol ethyl ether acetate (propylene glycol ethyl ether acetate), propylene glycol propyl ether acetate (propylene glycol propyl ether acetate) and ethyl lactate (ethyl lactate) 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.
Adjuvant (D)
Positive-type photosensitive resin composition of the present invention can further add aromatic hydroxy compound, to adjust the sensitivity or the viscosity of constituent.Be suitable for aromatic hydroxy compound concrete example of the present invention as 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.Novolac 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 the good dyestuff of compatibility, wherein, the spendable adherence auxiliary agent of the present invention, for example: melamine (melamine) compound and silane based compound, effect is to increase the adherence between positive-type photosensitive resin composition and attaching substrates, wherein the melamine concrete example is 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.Novolac 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 interfacial agent, silicon (Silicon) are interfacial agent etc.Wherein fluorine is an interfacial agent, and concrete example is 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 (Sil icon) is the interfacial agent concrete example as SF8427, the SH29PA etc. of commercially available Toray Dow CorningSilicon.Novolac resin (A) with 100 weight portions is made benchmark, and the use amount of above-mentioned interfacial agent 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 commodity RE801, RE802 (Ink of kingdom system) by name.
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.
＜liquid crystal aligning control formation the method for projection 〉
Positive-type photosensitive resin composition of the present invention comprises the carboxylate (B) and the solvent (C) of novolac resin (A), adjacent naphthoquinones two nitrine sulfonic acid classes, in stirrer, be uniformly mixed into solution state, can add adjuvants (D) such as the good dyestuff of adherence auxiliary agent, interfacial agent, thinning agent, compatibility, plasticizer, stabilization agent in case of necessity simultaneously.With roller rubbing method, method of spin coating, curtain coating coating, ink-jet method methods such as (ink-jet) this constituent is coated on the 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.Photosensitive compoistion tunic after pre-the baking is thick to be 1～3 μ m.
After pre-roasting, this photosensitive resin composition layer is between between specified mask (mask), and (as Nikon 1755G7A) exposes with stepper, impregnated in developer solution in 23 ± 2 ℃ again and develops in 30 seconds～5 minutes, removes part not and forms pattern.The light that exposure is used: can be ultraviolet rays such as g line, h line, i line for good, and UV-device can be (surpassing) high mercury vapor lamp and metal halid lamp.
Aforesaid substrate for example means: be used for alkali-free glass, soda-lime glass, hard glass (Pai Lesi glass), quartz glass of liquid crystal indicator etc. or the like.
Moreover developer solution is to use as the Tetramethylammonium hydroxide of 0.1～5 weight % (tetra methylammonium hydroxide), sodium carbonate (Na
2CO
3), sodium bicarbonate (Na
2HCO
3), NaOH (NaOH), potassium hydroxide (KOH) etc.And it is when using the developer solution that these alkaline aqueous solutions constitute, generally clean to wash again after development.
Secondly, again with pressurized air or compressed nitrogen with pattern air-dry after, do back roasting (postbake) with heating arrangements such as heating plate or baking ovens and handle.Institute's fixed temperature is 100～250 ℃, and the heating plate of fixing time is 2 minutes～60 minutes, and baking oven is 2 minutes～90 minutes.
＜liquid crystal display cells 〉
Liquid crystal display cells of the present invention, lie in form nesa coating, oriented film on the colored filter substrate after, with the formation method of above-mentioned＜liquid crystal aligning control with projection〉formation liquid crystal aligning control projection, and forming interval body (spacer) afterwards, with be provided with membrane transistor (TFT, ThinFilm Transistor) driving substrate is fitted, and injects liquid crystal, seals filling orifice and constitutes liquid crystal structure cell (cell).Then, on the outside surface of liquid crystal structure cell, applying Polarizer and make liquid crystal display cells.
Embodiment
Cooperate the explanation of following examples and comparative example, can further understand technology contents of the present invention, characteristics and effect.
[synthesis example of novolac resin (A)]
Synthesis example A-1
On four cervical vertebra bottles of 1000 milliliters of volumes, nitrogen inlet, stirrer, well heater, condenser pipe and thermometer are set, and import nitrogen and add the feed composition thing according to consumption shown in the table 1, above-mentioned feed composition thing comprises :-formalin 52.8g (0.65 mole in formaldehyde), the oxalic acid 1.8g (0.02 mole) of cresols 75.7g (0.7 mole), p-Cresol 32.4g (0.3 mole), 37 weight %.When the content of four cervical vertebra bottles was stirred, the temperature of oil bath was promoted to 100 ℃.The temperature of reaction of polycondensation process is kept 100 ℃, 6 hours polycondensation time.After polycondensation is finished, be warming up to 180 ℃ of pressure and carry out drying under reduced pressure,, can get novolac resin (A-1) the solvent devolatilization with 10mmHg.The molecular weight distribution result that gained novolac resin (A-1) records with gel permeation chromatography, and be shown in table 2 with the thermogravimetric amount loss result that thermogravimeter records.
The proportion of composing of the synthesis example of table 1 novolac resin (A)
The molecular weight distribution of the synthesis example of table 2 novolac resin (A), and thermogravimetric amount loss result
Synthesis example A-2～A-4
With the method for operating of synthesis example A-1, difference is to change the kind of aromatic hydroxy compound and mix consumption, the consumption of aldehydes, the consumption of acidic catalyst, and temperature of reaction, and its prescription and reaction conditions are stated from table 1.The molecular weight distribution result that the gained novolac resin records with gel permeation chromatography, and be shown in table 2 with the thermogravimetric amount loss result that thermogravimeter records.
Synthesis example A-5
Gained novolac resin (A-1) 100 weight portions are dissolved in solvent propylene glycol monomethyl ether acetate 300 weight portions in the synthesis example 1, continue stirring until dissolving fully under room temperature.Flow into afterwards among ethylbenzene (Ethylbenzene) 2000 weight portions, continue simultaneously to stir after 30 minutes, take out sediment, after the solvent devolatilization, can get novolac resin (A-5).The molecular weight distribution result that gained novolac resin (A-5) records with gel permeation chromatography, and be shown in table 2 with the thermogravimetric amount loss result that thermogravimeter records.
Synthesis example A-6
Gained novolac resin (A-2) 100 weight portions are dissolved in solvent propylene glycol monomethyl ether acetate 300 weight portions in the synthesis example 2, continue stirring until dissolving fully under room temperature.Inject afterwards among the 1500 weight portion isopropyl benzenes (Isopropylbenzene), continue simultaneously to stir after 30 minutes, take out sediment, after the solvent devolatilization, can get novolac resin (A-6).The molecular weight distribution result that gained novolac resin (A-6) records with gel permeation chromatography, and be shown in table 2 with the thermogravimetric amount loss result that thermogravimeter records.
Synthesis example A-7
Gained novolac resin (A-3) 100 weight portions are dissolved in solvent propylene glycol monomethyl ether acetate 300 weight portions in the synthesis example 3, continue stirring until dissolving fully under room temperature.Inject afterwards among the 3000 weight portion ethylbenzene, continue simultaneously to stir after 30 minutes, take out sediment, after the solvent devolatilization, can get novolac resin (A-7).The molecular weight distribution result that gained novolac resin (A-7) records with gel permeation chromatography, and be shown in table 2 with the thermogravimetric amount loss result that thermogravimeter records.
Synthesis example A-8
Gained novolac resin (A-4) 100 weight portions are dissolved in solvent propylene glycol monomethyl ether acetate 300 weight portions in the synthesis example 4, continue stirring until dissolving fully under room temperature.Inject 1500 weight portion ethylbenzene afterwards, continue to stir simultaneously after 30 minutes, take out sediment, after the solvent devolatilization, repeat once above-mentioned dissolving, precipitation, devolatilization step after, can get novolac resin (A-8).The molecular weight distribution result that gained novolac resin (A-8) records with gel permeation chromatography, and be shown in table 2 with the thermogravimetric amount loss result that thermogravimeter records.
Synthesis example A-9
Gained novolac resin (A-3) 100 weight portions are dissolved in solvent propylene glycol monomethyl ether acetate 300 weight portions in the synthesis example 3, continue stirring until dissolving fully under room temperature.Inject 1000 weight portion isopropyl benzenes afterwards, continue to stir simultaneously after 30 minutes, take out sediment, after the solvent devolatilization, repeat twice above-mentioned dissolving, precipitation, devolatilization step after, can get novolac resin (A-9).The molecular weight distribution result that gained novolac resin (A-9) records with gel permeation chromatography, and be shown in table 2 with the thermogravimetric amount loss result that thermogravimeter records, the weight average molecular weight of this resin is 9,800.
Synthesis example A-10
Gained novolac resin (A-4) 100 weight portions are dissolved in solvent propylene glycol monomethyl ether acetate 300 weight portions in the synthesis example 3, continue stirring until dissolving fully under room temperature.Inject the cosolvent of ethylbenzene 1000 weight portions/isopropyl benzene 1000 weight portions afterwards, continue simultaneously to stir after 30 minutes, take out sediment, after the solvent devolatilization, can get novolac resin (A-10).The molecular weight distribution result that gained novolac resin (A-10) records with gel permeation chromatography, and be shown in table 2 with the thermogravimetric amount loss result that thermogravimeter records.
[embodiment of photosensitive resin composition and comparative example]
Embodiment 1
Novolac resin A-7100 weight portion shown in the table 2,2,3,4-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) 25 weight portions, 2,3,4,4 '-tetrahydroxybenzophenone and 1, carboxylate (the average esterification degree 85% of 2-naphthoquinones two nitrine-5-sulfonic acid, hereinafter to be referred as B-2) 10 weight portions and interfacial agent (trade name SF8427, Toray Dow Corning Silicone system) 0.3 weight portion be dissolved in propylene glycol monomethyl ether acetate 1100 parts by weight solvent, can make positive-type photosensitive resin composition.Utilize following each evaluation of measuring mode to estimate, the gained result is as shown in table 3.
The proportion of composing of table 3 photosensitive resin composition embodiment and comparative example and evaluation result
Annotate:
B-1:2,3,4-trihydroxybenzophenone and 1,2-naphthoquinones two is the carboxylate of nitrogen-5-sulfonic acid repeatedly
B-2:2,3,4,4 '-tetrahydroxybenzophenone and 1,2-naphthoquinones two is the carboxylate of nitrogen-5-sulfonic acid repeatedly
C-1: 1-Methoxy-2-propyl acetate (PGMEA, propylene glycol methyl ether acetate)
C-2: ethyl lactate (EL, ethyl lactate)
D-1: interfacial agent-1, trade name SF8427, Toray Dow Corning Silicone system
D-2: interfacial agent-2, trade name BL-20, Tochem product system
D-3: adherence auxiliary agent, trade name Cymel-303, Mitsui's system
[evaluation method]
The molecular weight distribution determination of novolac resin (A)
Novolac resin (A) is according to the gel permeation chromatography GPC of Waters Company, and measures according to following condition:
Tubing string: GP-501/502/503/504 (polymer laboratories corporate system)
Detector: Waters RI-2410
Mobile phase: tetrahydrofuran (flow velocity 1.0ml/min)
With the polystyrene of standard molecular weight as bioassay standard.
Molecular resin amount of the present invention is measured and is got by GPC, promptly in the measurement range of GPC, molecular weight is between 200～150, the total integral area of 000 resin signals (intensity) is used as 100%, wherein, the difference determining molecular weight is between 200～400, and molecular weight is between 10,000～30,000 account for the content (weight %) of all resins.
The thermogravimetry of novolac resin (A) (Thermal Gravimetric Analysis)
Novolac resin (A) is with thermogravimeter (TA Instruments corporate system, model: 2850) measured its thermogravimetric amount in 230 ℃, 30 minutes under nitrogen environment and lose (weight %).
Sensitivity
With the mode of photosensitive resin composition with rotary coating, be coated on 6 o'clock Si wafer substrates, carry out roastingly in advance then with 110 ℃ of temperature, 1.5 minutes time, can form pre-roasting the filming of a thickness 1.5 μ m.After re-using step-by-step exposure machine (Nikon 1755G7A) and shining at interval, impregnated in again in 23 ℃ the developer solution and developed 1 minute, exposed portion on the substrate is removed, clean with pure water with 1ms.Sensitivity be evaluated as that (0.5cm * 0.5cm) can show fully and opens the required time shutter (millisecond, ms) expression with each exposure region.
Zero: 25≤time shutter≤50
*: time shutter≤25
Ghost
With the mode of photosensitive resin composition with rotary coating, be coated on the colored filter glass substrate with oriented film and nesa coating, carry out baking in advance with 110 ℃ of temperature, 1.5 minutes time then, can form thickness is pre-roasting the filming of 1.5 μ m.Should bake in advance and film between between specified mask (mask), with stepper (Nikon 1755G7A) 20mJ/cm
2Light quantity irradiation after, impregnated in again in 23 ℃ the developer solution and developed 1 minute, the part of exposing on the substrate is removed, clean with pure water, toasted in roasting 30 minutes with 230 ℃, back again, can on substrate, form liquid crystal aligning control projection (protrusion).Be coated with hot pressing glue on the prepared colored filter glass substrate with above-mentioned steps, the driving glass substrate that another sheet has a membrane transistor is spilt the interval body (spacer) of 4 μ m, and two sheet glass are fitted.After injecting nematic crystal, seal liquid crystal injecting port with ultraviolet light (UV) sclerosis glue again, promptly can be made into liquid crystal structure cell (cell).
Prepared liquid crystal structure cell applied after 48 hours the 10 volt DC voltages,, have or not ghost to take place with visualization display frame when this voltage applies when removing.
Zero: no ghost phenomena takes place.
*: there is ghost phenomena to take place.
Embodiment 2
With the method for operating of embodiment 1, difference is to change the kind and the consumption of the kind of novolac resin (A) and consumption, adjuvant (D), and its prescription and evaluation result are stated from table 3.
Embodiment 3
Method of operating with embodiment 1, difference is to change the consumption of the carboxylate (B) of the kind of novolac resin (A) and consumption, adjacent naphthoquinones two nitrine sulfonic acid classes, the kind of solvent (C), the kind and the consumption of adjuvant (D), and its prescription and evaluation result are stated from table 3.
Embodiment 4
Method of operating with embodiment 1, difference is to change the kind of the kind of consumption, solvent (C) of the carboxylate (B) of the kind of novolac resin (A) and consumption, adjacent naphthoquinones two nitrine sulfonic acid classes and consumption, adjuvant (D), and its prescription and evaluation result are stated from table 3.
Embodiment 5
With the method for operating of embodiment 1, difference is to change the kind of novolac resin (A), and its prescription and evaluation result are stated from table 3.
Embodiment 6
With the method for operating of embodiment 1, difference is to change the kind and the consumption of the kind of novolac resin (A) and consumption, adjuvant (D), and its prescription and evaluation result are stated from table 3.
Embodiment 7
Method of operating with embodiment 1, difference is to change the kind and the consumption of the kind of the kind of carboxylate (B) of the kind of novolac resin (A) and consumption, adjacent naphthoquinones two nitrine sulfonic acid classes and consumption, solvent (C) and consumption, adjuvant (D), and its prescription and evaluation result are stated from table 3.
Embodiment 8
Method of operating with embodiment 1, difference is to change the consumption of the kind of carboxylate (B) of the kind of novolac resin (A) and consumption, adjacent naphthoquinones two nitrine sulfonic acid classes and consumption, solvent (C), and not adding adjuvant (D), its prescription and evaluation result are stated from table 3.
Comparative example 1
With the method for operating of embodiment 1, difference is to change the kind of novolac resin (A), and its prescription and evaluation result are stated from table 3.
Comparative example 2
With the method for operating of embodiment 1, difference is to change the kind of novolac resin (A), the kind and the consumption of adjuvant (D), and its prescription and evaluation result are stated from table 3.
Comparative example 3
Method of operating with embodiment 1, difference is to change the kind and the consumption of the kind of the kind of carboxylate (B) of the kind of novolac resin (A), adjacent naphthoquinones two nitrine sulfonic acid classes and consumption, solvent (C) and consumption, adjuvant (D), and its prescription and evaluation result are stated from table 3.
Comparative example 4
Method of operating with embodiment 1, difference is to change the consumption of the kind of carboxylate (B) of the kind of novolac resin (A), adjacent naphthoquinones two nitrine sulfonic acid classes and consumption, solvent (C), and not adding adjuvant (D), its prescription and evaluation result are stated from table 3.
Comparative example 5
With the method for operating of embodiment 1, difference is to change the kind of novolac resin (A), and its prescription and evaluation result are stated from table 3.
The above person of thought, it only is preferred embodiment of the present invention, can not limit practical range of the present invention with this, promptly the simple equivalent of being done according to the present patent application claim and description of the invention content generally changes and modifies, and all should still belong to covering scope of the present invention.
Claims (4)
1. a positive-type photosensitive resin composition comprises: the carboxylate emulsion (B) and the solvent (C) of novolac resin (A), adjacent naphthoquinones two nitrine sulfonic acid classes; It is characterized in that, described novolac resin (A) is lower than 150 with the molecular weight that gel permeation chromatography records, 000, and with molecular weight between 200～150, when the total integral area of 000 resin signals was used as 100 weight %, less than 6 weight %, molecular weight was between 10 between 200～400 resin proportion for its molecular weight, 000～30,000 resin proportion is greater than 12 weight %; And after analyzing by thermogravimeter, described novolac resin (A) is under 230 ℃, 30 minutes conditions, and its thermogravimetric amount loss is less than 10 weight %; With respect to the described novolac resin (A) of 100 weight portions, the use amount of the carboxylate (B) of described adjacent naphthoquinones two nitrine sulfonic acid classes is 1～100 weight portion.
2. projection is used in a liquid crystal aligning control, it is characterized in that this projection is formed by the described positive-type photosensitive resin composition of claim 1.
3. liquid crystal aligning control is characterized in that with the manufacture method of projection, and the described positive-type photosensitive resin composition of claim 1 is controlled and used projection in form described liquid crystal aligning on the substrate through coating, exposure, the back of developing.
4. a liquid crystal display cells is characterized in that, has liquid crystal aligning control projection as claimed in claim 2.
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| CN102346372A (en) * | 2010-07-30 | 2012-02-08 | 奇美实业股份有限公司 | Positive photosensitive resin composition and method for forming patterns by using same |
| CN104391428B (en) * | 2014-11-20 | 2018-06-19 | 京东方科技集团股份有限公司 | Emulsion, photoetching compositions and preparation method containing diazonium groups |
| CN107615171A (en) * | 2015-05-28 | 2018-01-19 | 富士胶片株式会社 | Manufacture method, circuit layout, input unit and the display device of circuit layout |
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| CN1412243A (en) * | 2001-10-15 | 2003-04-23 | 奇美实业股份有限公司 | Positive photosensitive resin composition |
| JP2003195496A (en) * | 2001-12-26 | 2003-07-09 | Tokyo Ohka Kogyo Co Ltd | Positive photoresist composition for manufacture of liquid crystal display device and method for forming resist pattern |
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| EP1418047A2 (en) * | 2002-11-08 | 2004-05-12 | Fuji Photo Film Co., Ltd. | Planographic printing plate precursor |
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| JP2004233846A (en) * | 2003-01-31 | 2004-08-19 | Tokyo Ohka Kogyo Co Ltd | Positive photoresist composition for fabricating lcd and method of forming resist pattern |
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| TW554252B (en) * | 2001-02-27 | 2003-09-21 | Chi Mei Corp | Positively photosensitive resin composition |
| CN1412243A (en) * | 2001-10-15 | 2003-04-23 | 奇美实业股份有限公司 | Positive photosensitive resin composition |
| JP2003195496A (en) * | 2001-12-26 | 2003-07-09 | Tokyo Ohka Kogyo Co Ltd | Positive photoresist composition for manufacture of liquid crystal display device and method for forming resist pattern |
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