TW201040665A - Compound of positive photosensitive resin and protrusion formed by the same for liquid crystal alignment control - Google Patents

Abstract

The invention relates to a kind of compound of positive photosensitive resin for a liquid crystal display element, especially providing a kind of compound of positive photosensitive resin and protrusion formed by the same for liquid crystal alignment control with better photosensation and without residual images phenomena. The compound contains phenol novolac resin(A), ester photosensitive agent for naphthoquinone 2-azide sulfamic acid, and solvent; wherein, the phenol novolac resin(A) has a molecular weight measured small than 150,000 by gel-permeation chromatography method, if the total integral area of the resin signal with molecular weight value between 200 to 150,000 is set as one hundred percentage weight, the percentage with molecular weight value between 200 to 400 is lower than 6, but that of molecular weight value between 10,000 to 30,000 is greater than 12; furthermore, the weight loss analyzed by thermogravimetric Analyzer under 230DEG C condition for 30 minutes is smaller than 10 percentage.

Description

[Technical Field] The present invention relates to a positive photosensitive resin composition for a liquid crystal display element. In particular, a positive photosensitive resin composition for a projection for liquid crystal alignment control which is excellent in sensitivity and has no image sticking phenomenon is provided. [Prior Art] The liquid crystal display element is the most widely used user in today's flat panel displays. In recent years, with the popularization of office equipment such as personal computers and word processors, LCD TVs, etc., liquid crystal displays (TFTs for thin film transistors) -LCD) In terms of display quality, its performance requirements are becoming more stringent. Among the TFT-LCDs, the TN (Twisted Nematic) type LCD is currently used at the most. This TN-type LCD has been improved in technology in recent years, and the contrast of front, color reproducibility, etc. are comparable to or above CRT. However, the TN type LCD has a problem that the viewing angle is too narrow. q In order to solve this problem, the industry has developed MVA (MUlti-d〇main)

Vertically A1 ignmented type lcd (vertical alignment type liquid crystal display type), in order to make the liquid crystal in the region of the pixel area become a region of the fine-direction direction, a slit can be provided on the electrode on the light incident side in the one-pixel region (slit), at the same time in the same pixel region on the electrode substrate on the display side, at the position shifted from the electrode slit, a bevel having a slope (4) such as a double pyramid shape or a semiconvex lens shape is formed. Since the protrusion is formed by controlling the alignment of the liquid crystal, it is called 3 201040665

^ Protrusion control protrusions. The liquid crystal alignment protrusion is inclined at an alignment (four) axis which partially supplies liquid crystal molecules along the surface thereof, and the enlarged display angle is achieved even when viewed obliquely with respect to the LCD surface. purpose. Such a technique is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 2002-122858, the use of a clar var lac resin as a technique for forming protrusions for liquid crystal alignment control. However, such a liquid crystal alignment control protrusion has a problem that a residual image phenomenon occurs in the material when it is long. SUMMARY OF THE INVENTION An object of the present invention is to provide a positive photosensitive resin composition for a liquid crystal display element. The system provides a positive-type photosensitive resin composition for the projection of the liquid crystal alignment control. The composition comprises a novolak resin (A), an o-naphthoquinonediazide sulfonic acid sensitizer (8), and a solvent (6); wherein the secret varnish resin (A) is a molecule measured by osmium penetrant chromatography. #余15M00以下' and the molecular weight is between 〜15G, and the total integrated area of the GGG is 100% by weight. The molecular weight is between 2〇〇4 and 4%, and the molecular weight is between 10, 〇〇〇~30,000 accounted for 12% by weight or more; and the novolac resin (A) was analyzed by a thermogravimetric analyzer, and its thermal weight loss was below 10% by weight under 23 (rc3〇min conditions) The following is a detailed description of each composition of the present invention: Novolac resin (A) 201040665 The novolac resin (A) of the present invention is generally composed of an aromatic hydroxy compound and an aldehyde in the presence of an acidic catalyst. Specific examples of the aromatic hydroxy compound: phenol (phen〇1), m-cresol, p-Cresol, o-cresol , 2, 3-xylenol (2, 3-xylenol), 2, 5-diphenylphenol (2, 5-xylenol), 3 , xylenol such as 5-, 5-xylenol, 3,4-xylenol, etc.; m-ethyl phenol , p-ethyl phenol, o-ethyl phenol, 2,3,5-trimethyl phenol, 2 , 3,5-triethyl phenol, 4-tert-butyl phenol, 3-tert-butyl phenol, 3-tert-butyl Phenol), 2-tert-butyl phenol, 2-tert-buty 1-4-methylphenol, 2-third Butyl-5-mercaptobenzene expectant (2-士61*1:-1}11士71-5-11^1±71 口11611〇1), 6-t-butyl-3-mercaptobenzene (6_tert-biityl_3-inethylphenol) and the like alkyl phenol; p-methoxy phenol, m-methoxy phenol, p-ethoxy benzene P-ethoxy phenol, m-ethoxy phenol, p-PrP〇P〇xy phenol, m-propoxy phenol, etc. Alkoxy phenol; o-isopropyl benzene 5 201040 665 (o-isopropenyl phenol), p-isopropenyl phenol, 2-meth-4-isopropenyl phenol, 2-ethyl-4 Isopropenyl phenol such as 2-e thy 1 -4- i sopropeny 1 pheno 1; aryl phenol of phenyl phenol 4,4'-dihydroxybiphenyl, bisphenol A, m-phenylene (1' 01'〇丨11〇1), p-phenylene 17 (11'〇91^11〇116), polyhydroxyphenol such as pyrogallor. These compounds may be used singly or in combination of two or more. And in the above aromatic hydroxy compound, o-cresol, m-cresol, p-cresol, 2, 5-xylene, 3, 5-dibenzene, 2, 3, 5-trimethylphenol It is better. The Q of the aldehyde type of the present invention condensed with an aromatic mercapto compound is specifically, for example, formic acid, paraformaldehyde, trioxane, acetaldehyde, propionic acid. (pr〇pi〇naidehyde), butylaldehyde, trimethyl acetaldehyde, acrium (acr〇iein), crotonaldehyde, CyCi〇hexaneaidehyde, D Furfural, furfuryl, awakening: (furyiacr〇iein), benzoquinone (benzaldehyde), terephthalaldehyde, benzene 6 201040665 acetaldehyde (Phenylacetaldehyde), α-benzene Propionaldehyde ("-phenylpropylaidehyde", phen- phenylpropionaldehyde (Phenylpropylaldehyde), o-hydroxybenzaldehyde, m-benzoyl disk, p-hydroxybenzoic acid, o-methyl albino, inter- Methyl benzoic acid, p-benzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-benzophenone, cinnamyl, etc. The above-exemplified acids may be used alone or in combination; Formaldehyde is preferred. The present invention & sexual touch Specific examples are: hydrochloric acid, sulfuric acid, formic acid, _acid, oxalic acid, p-toluenesulfonic acid, etc. The varnished wax (4) obtained by the condensation reaction can be dissolved in a good solvent, and then re-injected into a poor solvent to precipitate, and the above is repeated. The step of treating the novolac resin novolak resin (A) has a molecular weight of less than 15 〇, 〇〇〇 below, and a molecular weight of 2 GG to 150, which is measured by gel permeation chromatography. When the total integrated area of the resin signal is (10)% by weight, the molecular weight thereof is 200 to 400% by weight or less, preferably 5 to 〇. 05% by weight, more preferably 4 to 〇. G5 by weight; molecular weight Between 1 (), coffee ~ 3 〇 ' 000 accounted for 12% by weight or more, preferably 12 to 5 〇 wt%, more preferably secret ~ 35 wt%. Especially when the molecular weight is between 400~10, 〇〇〇 It accounts for 35 to 75 wt% 'and the molecular weight is between 讥 〜 ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ ～ When 6 wt% or more, the liquid crystal alignment control formed by 7 201040665 When the protrusion is used in a liquid crystal display, the image sticking problem is liable to occur; when the molecular weight is between 10,000 and 30,000 and less than 12% by weight, the positive photosensitive resin composition formed is too sensitive and easily exposed. The shape of the pattern formed is not good. The varnish touch (A) of the present invention is analyzed by thermal weight (four) and heated at 230 C for 30 minutes. The thermal weight loss is 10% by weight or less, preferably 8 to 0.2% by weight. 〇. 2% by weight or less. When heat weight loss

When it is 1% by weight or more, the formed liquid crystal alignment control protrusion is used in a liquid crystal display, and the image sticking problem easily occurs. 4 Qin drive a group of rats continued acid type g (b) to do the invention of the sense substance, money chat Wei Wei Wei acid vinegar (8), the ester compound is not particularly limited, can be used by regular users, where ' The preferred ones are: o-fine two money + two, o-quinonediazide + rhein, ortho-di- azide + two ortho-naphthoquinone di- Wei and two-based compounds, preferably the above neighbors _ Dioxane and multi-component red _ compounds. The above compounds may be pharmaceutically or partially hydrated. The types of hydroxy compounds are listed below. (-) benzoquinones, for example: 2,3,4_tri-benzole, 2,4,4'-tris-benzophenone, 2,4,6-tri-benzophenone, 2,3,4,4,—tetramyl benzoquinone, 2, 2,, “, ~ tetram- benzophenone, 2, 3, 4, 4, 6-five, stupid f_, 2, 2, , 3, 4, 4, _ five-way armor, 2, 2, 3, 4, 5, - five-base, scorpion, sputum, 2, 3, 4, 5, 5, 5, 8 201040665 hydroxybenzophenone, 2 , 3,3,,4, 4,,5,-hexahydroxybenzophenone, etc. (1) General formula (I)

In the formula, 1^~^2 is a hydrogen atom or a lower alkyl group (&11^1), 1^1^9 is a hydrogen atom, a _ atom, a lower alkyl group, a lower alkoxy group (alkoxy) , lower alkenyl (alkenyl) and cycloalkyl, R1. And R" is a hydrogen atom, a halogen atom, and a lower alkyl group, X, y, and z are integers of 1 to 3, and η is 0 or 1. Specific examples of the above formula via a aryl compound: tris(4-phenylphenyl) brothel, bis(4-hydroxy-3, 5-dimethylphenyl)-4-hydroxyphenylmethane, bis (4) - hydrazino- 3, 5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3, 5-dimercapto)-2-hydroxy stupidinyl, bis ( 4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4- Hydroxy-2, 5-dimercaptophenyl)-2-hydroxyphenylmethyl, bis(4-hydroxy-3, 5-dimethylphenyl)-3, 4-dihydroxyphenylmethane, double ( 4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenyl decane, bis(4-amino-3, 5-dimethylphenyl)-2,4-dihydroxy Phenyl decane, bis(4-hydroxy-2, 5-dimercaptophenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxybenzene 9 201040665 yl)-3-methoxy-4 -hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxyphenyl)-2-hydroxyphenyldecane, double (3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylnonane, bis(3-cyclohexyl-4-hydroxy-6-methylaryl)-2-hydroxyphenylmethane, double (3-cyclohexyl-4-hydroxy-6-mercaptophenyl)-3-hydroxyphenylmethane, bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)-4-phenylphenyl Methyl, bis(3~cyclohexyl-4-hydroxy-6-methylphenyl)-3,4-dihydroxyphenyl decane, bis(3-cyclohexyl -6-hydroxyphenyl)-3 -hydroxyphenyl decane, bis(3-cyclohexyl-6-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-6-hydroxyphenyl)_2-hydroxyl-based fluorene, double (3-cyclohexyl-6-carbyl-4-mercaptophenyl)-2-phenylphenylmethane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-4-hydroxyphenyl Methane, bis(3-cyclohexyl-6-hydroxy-4-methylphenyl)-3,4-dihydroxyphenylmethane, 1-[1-(4-hydroxyphenyl)isopropyl]-^[丨,丨-bis-hydroxyphenyl)ethyl]benzene, 1-indole-(3-methyl-4-hydroxyphenyl)isopropylbupro, bis-Q (3-methylhydroxyphenyl) Ethyl]benzene. (3) General (Π)

(Π) where R and R are hydrogen atoms or lower-grade yards, χ, and 〆 are integers of 卜3. Specific examples of the (p-phenyl) hydrocarbons of the above formula: 2_(2, 3, 4 - 3 woven 201040665 phenyl)-2-(2,3',4'-trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4,-hydroxyphenyl)propane, Bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, and the like. (4) Other aromatic hydroxy compounds, such as phenol, p-methoxybenzoquinone, dimethyl benzene, benzodiazepine, Shuangyi, Cai Ling (Qinghhh), and neighboring ones ( Pyrocatechol), 1,2, 3-benzenetrimethyl ether (pyrogallol 0 (tetra) gal 1 ether), 1,2, 3-phenyltris-1,3-dimethyl ether (pyrogallol-1,3-dimethyl) Ether), 3,4,5-trihydroxybenzoic acid, partially esterified or partially etherified 3,4,5-trihydroxybenzoic acid, and the like. The above hydroxy compound is preferably 2,3,4-trihydroxybenzophenone or 2,3,4,4-tetrahydroxyoxybenzophenone. The above hydroxy compounds may be used singly or in combination of several kinds. The ester material of the ortho-naphthoquinone diazidosulfonate oxime (B) in the resin composition of the present invention may be a compound containing a quinonediazide group, for example, o-naphthoquinonediazide-4 (or 5) The sulfonic acid halide salt and the hydroxy compound of the above (1) to (4) are subjected to a condensation reaction to be completely esterified or partially esterified, and the condensation reaction is usually carried out in dioxane, N. It is preferably carried out in an organic solvent of N-pyrrolidone or acetamide, and in the presence of a base condensing agent such as triethanolamine, metal carbonate or alkali metal hydrogencarbonate. At this time, the total amount of hydroxyl groups in the hydroxy compound is 1% mol% and 201040665 « . Preferably, it is 50 moles, and the most ant fine molars are condensed with the neighboring broccoli diazide _4 (or 5) acid from the salt, and the acetylation degree is more than 50%, preferably More than 6〇%. The ester of the o-cai-monoazide-acid acid ester (β) of the present invention is used in an amount of 1 to 1 part by weight, preferably 10 to 50 parts by weight, per 100 parts by weight of the varnish resin (A). More preferably, it is 20 to 40 parts by weight. Solvent (C) D The solvent used in the present invention requires an organic solvent which is more soluble in other organic components. The solvent (c) of the photosensitive resin composition of the present invention is used in an amount of 700 to 2,000 parts by weight, preferably 800 to 1,800 parts by weight, more preferably 100 parts by weight based on 100 parts by weight of the novolak resin. 9〇〇~1,600 parts by weight. The solvent (C) of the present invention is, for example, an ether type or an ester type. Among them, specific examples of ethers are: ethylene glycol monopropyl 〇ether, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol Ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether. The specific ester type is, for example, ethylene glycol monomethyl ether acetate, ethylene glycol 12 201040665, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether Acetate), propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and ethyl lactate. These solvents may be used alone or in combination of two or more. Among the above solvents, propylene glycol monoterpene ether acetate is preferably used as 0 and lactic acid. Additive (D) The positive-type photosensitive resin composition of the present invention may further contain an aromatic trans-based compound ' to adjust the sensitivity or viscosity of the composition. Specific examples of the aromatic hydroxy compound suitable for the present invention include: Japan Honshu Chemical Industry Co., Ltd. trade names TPPA-1000P, TPPA-1100-2C, TPPA-1100-3C, TPPA-1100-4C, TPPA-1200-24X, TPPA -1200-26X, 〇TPPA-130〇-235T, TPPA-1600-3M6C, ΤΡΡΑ-MF and other commercial products, of which the trade name TPPA-1600-3M6C, TPPA-MF is preferred, which can be used alone or Combined use. The weight of the scented compound is generally from 0 to 20 parts by weight, preferably from 5 to 18 parts by weight, more preferably from 1.0 to 15 parts by weight, based on 100 parts by weight of the novolac resin (A). Share. The positive photosensitive resin composition of the present invention may further contain an adhesion promoter, a surface leveling agent, a diluent, and a dye having good compatibility, and among them, it may be used as a clogging aid, for example, melamine (melamine). 13 201040665 A compound and a zephyr compound which acts to increase the adhesion between a positive photosensitive resin composition and an attached substrate, and specific examples of the melamine are: commercially available: Cymel-300, 303 (manufactured by Mitsui Co., Ltd.) , MW—3〇MH, 黯—3〇, MS-11, MS-001, MX-750, MX-706 (Sanhe chemical), etc. Specific examples of the si lane compound are, for example, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-decyloxyethoxy) decane, N-(2-amino group Ethyl)-3-aminopropylmethyldimethoxydecane, '(2-aminodecylethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3 -glycidylpropyltrimethoxydecane, 3-glycidylpropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysulfonate, 3- Gas propyl methyl monomethoxy sulphur, 3-chloropropyltrimethoxy sulphur, 3-methylpropoxy propyl trimethoxy oxy sylvestre, 3-thiol propyl tridecyloxy Decane and so on. 5〜18重量份,更。 The melamine melamine compound is used in an amount of 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Preferably, it is 〇15 parts by weight; the amount of the adhesion aid of the silane compound is generally 〇2 parts by weight, preferably 0.00M parts by weight, more preferably 0.005~〇.8 parts by weight. . The surface flattening agent which can be used in the present invention is, for example, a fluorine-based surfactant, a silicone-based surfactant, or the like. Specific examples of the fluorine-based surfactant include commercially available 3M Flourate FC-430, FC-431, Tochem product F top EF122A, 122B, 122C, 126, and BL20. The specificity of the silicone surfactant is, for example, the commercially available T〇ray Dow 201040665.

Corning Silicon's SF8427, SH29PA, etc. The surfactant is generally used in an amount of from 〇 to 1.2 parts by weight based on 100 parts by weight of the novolak resin (A), preferably 〇25 丨.〇 by weight, more preferably 〇〇. 5 〇〇. 8 parts by weight. The diluent which can be used in the present invention is a diluent of the trade name RE8 (U, RE802 (manufactured by Imperial Ink). The dyes which are compatible for use in the present invention are, for example, CUrcumin, coumarin (coumarin) Further, in the present invention, other additives such as a plasticizer, a stabilizer, etc. may be added as needed. <Method of Forming Protrusion for Liquid Crystal Alignment Control> Positive Type of the Invention The photosensitive resin composition contains a novolac resin (A), an ester of an o-naphthoquinonediazide sulfonic acid (β), and a solvent (c), and is uniformly mixed into a solution state in a stirrer, and may be simultaneously adhered thereto if necessary. 0 additives, surfactants, thinners, compatible dyes, plasticizers, stabilizers, etc. (D). Finally, roll coating, spin coating, cast coating inkjet (ink- The composition is applied onto a substrate by a method such as jet. After coating, the solvent is removed by prebake to form a photosensitive composition layer. The conditions of prebaking vary depending on the type of each component and the blending ratio. , usually for 1 minute at a temperature of 9 (Ml〇t: 1 minute. The film thickness of the salty composition after pre-baking is 1~3/zm. ~ After pre-baking, the photosensitive resin composition layer is between the specified masks 201040665 (mask) Advance exposure (such as Nikon 1755G7A), and then immersed in the developer at 23 ± 2 ° C for 3 sec _ 5 minutes for development, not partially removed to form a pattern. Light used for exposure: can be g line, h line The ultraviolet rays of the i-line and the like are good, and the material line 4 can be a (super) high water metal and a metal tooth lamp. The above substrate is, for example, an alkali-free glass or a soda-lime glass for a liquid crystal display device or the like. Hard glass (Pyrus glass), quartz glass, etc. 0 Further, the developer is used as a tetramethyl ammonium hydroxide, sodium carbonate (% 〇 1% by weight) 3), sodium hydrogen hydride (Na2HCO 〇, sodium hydroxide (% 〇Η), potassium hydroxide (koh), etc.. When using a developer composed of such an alkaline aqueous solution, generally after development and then water Wash. Then, after drying the pattern with compressed air or compressed nitrogen, add it to a hot plate or oven. The hot device is post-baked (p〇stbake;). The fixed temperature is 0 1GG~25G °C 'The hot plate is 2 minutes to 60 minutes, and the oven is 2 minutes to 90 minutes. &lt;Liquid crystal display element&gt; In the liquid crystal display device of the invention, after the transparent conductive film and the alignment film are formed on the color filter substrate, the above-described method for forming a liquid crystal alignment control protrusion is formed, and a spacer for forming a liquid crystal alignment control is formed, and a spacer is formed. After that, it is bonded to a driving substrate provided with a thin film transistor (TFT, TFT), and liquid crystal is injected to seal the injection hole to form a liquid crystal cell. Then, a polarizing plate was attached to the outer surface of the liquid crystal cell to prepare a liquid crystal display element. [Embodiment] The technical contents, features and effects of the present invention will be apparent from the following description of the embodiments and the comparative examples. [Synthesis Example of Novolak Resin (A)] Synthesis Example A-1. A nitrogen inlet, a stirrer, a heater, a condenser and a thermometer were placed on a four-necked flask of 1000 ml volume, and nitrogen gas was introduced and the feed composition was added with hydrazine as shown in Table 1. The above-mentioned feed composition includes:曱 曱 75 75. 7g (0.7 moles), p-cresol 32. 4g (〇. 3 moles), 37% by weight of aqueous formaldehyde solution 52.8g (A 65 moles), oxalic acid i, 8g ( 〇. 〇2 Moer When the contents of the four-necked flask are stirred, the temperature of the oil bath is raised to 1〇〇c. The polycondensation is over (4) The reaction temperature is fine G〇c, which is the hour of heterozygosity. After the completion of the mixture, the temperature W8 (rcm() mmHg was dried under reduced pressure, and the solvent was devolatilized to obtain a varnish resin (Α_υ. The obtained varnish resin (Α-1) was measured by gel permeation chromatography). The results of the molecular weight distribution 'and the thermal weight loss measured by the thermogravimetric analyzer are shown in Table 2. Synthesis Example Α-2~Α-4 The same procedure as in the synthesis example Α-1, except that the aromatic hydroxy group was changed. The type and amount of the compound, the amount of the aldehyde, the amount of the acidic catalyst, and the reaction temperature are shown in the table. The results of the molecular weight distribution measured by the gel permeation chromatography method and the thermal weight loss measured by the thermogravimetric analyzer are shown in Table 2. Synthesis Example A-5 Synthesis Example 1 The obtained novolac resin (Ai) is dissolved in 3 parts by weight of the solvent propylene glycol monoterpene ether acetate, and is continuously added to the element at room temperature, and then injected into Ethylbenzene. Among the 2000 parts by weight, while stirring was continued for 30 minutes, the precipitate was taken out, and the solvent was devolatilized to obtain a novolak resin (A-5). The obtained novolak resin (a-5) was gel-penetrated. The results of the molecular weight distribution measured by the analytical method and the thermal weight loss measured by the thermogravimetric analyzer are shown in Table 2. Synthesis Example A-6 The novolak resin (A_2) obtained in Synthesis Example 2 was dissolved in 1 part by weight. Solvent propylene monohydric glycerol vinegar vinegar vinegar weight part in the 'continuous drop at room temperature to the king cold solution. After injection of cumene (Is〇pr〇pylbenzene) delete 0 weight injury 'at the same time After mixing for 30 minutes, remove the precipitate and devolade the solvent. After the 'clear varnish resin (A-6). The obtained secret varnish resin (A-6) measured by the gel permeation chromatography method, and the thermogravimetric I analysis of the thermal weight loss results Table II. Synthesis Example A-7 The varnish resin (A-3) obtained in Synthesis Example 3 is dissolved in 300 parts by weight of solvent propylene glycol monomethyl acetacetacetate, and continuously mixed at room temperature until completely After dissolving, it is injected into a batch of _ parts by weight, and after stirring for 30 minutes at 201040665, the precipitate is taken out, and the solvent is devolatilized to obtain a novolak resin (A-7). The results of the molecular weight distribution measured by the gel permeation chromatography method of the obtained novolac resin (A-7) and the thermal weight loss measured by a thermogravimetric analyzer are shown in Table 2. Synthesis Example A-8 The novolak resin (A-4) obtained in Synthesis Example 4 was dissolved in 3 parts by weight of a solvent of propylene glycol monoterpenoid acetate, and was continuously wrinkled to completely dissolve at room temperature. . Thereafter, the mixture was poured into 1500 parts by weight of ethylbenzene, and after stirring for 30 minutes, the precipitate was taken out, and after the solvent was devolatilized, the above-mentioned steps of dissolution, precipitation, and devolatilization were repeated once to obtain a novolak resin. The results of the molecular weight distribution measured by gel permeation chromatography of the obtained novolac resin (A-8) and the thermal weight loss measured by a thermogravimetric analyzer are shown in Table 2. Synthesis Example A-9 0 The novolak resin (A-3) obtained in Synthesis Example 3 was dissolved in 300 parts by weight of a solvent of propylene glycol monoterpene acetate, and was continuously searched at room temperature until completely dissolved. Thereafter, the mixture is poured into 1000 parts by weight of cumene, and after stirring for 30 minutes, the precipitate is taken out, and after the solvent is devolatilized, the steps of the above-mentioned /glutination, /children's plate and devolatilization are repeated twice, and then the mixture can be obtained. The varnish resin (A-9) obtained from the novolac resin (A-9) by the gel permeation chromatography method, and the thermal weight loss measured by the thermogravimetric analyzer is shown in Table 2. The weight average molecular weight of the resin was 9,8 〇 (). . 201040665 Synthesis Example A-10 100 parts by weight of the novolak resin (A-4) obtained in Synthesis Example 3 was dissolved in 300 parts by weight of the solvent propylene glycol monomethyl ether acetate, and was continuously disturbed to complete dissolution at room temperature. Then, it is poured into a co-solvent of 1 part by weight of ethylbenzene/1 part by weight of isopropylidene, and stirring is continued for 3 minutes, and then the precipitate is taken out, and the solvent is devolatilized to obtain a novolak resin ( A-10). The molecular weight distribution of the obtained novolac resin (A-10) as measured by gel permeation chromatography and the thermal weight loss measured by a thermogravimetric analyzer are shown in Table 2. [Examples and Comparative Examples of Photosensitive Resin Composition] Example 1 Novolak Resin A-7 100 parts by weight, 2,3,4-tris-dibenzophenone and 1,2-naphthalene An ester of quinonediazide-5-sulfonic acid (average degree of acetification is 85°/. 'hereinafter referred to as B-1) 25 parts by weight, 2, 3, 4, 4'-tetrahydroxybenzophenone and 1 , 2-naphthoquinonediazide-5-sulfonic acid ester (average degree of esterification 0 85% 'hereinafter referred to as B-2) 10 parts by weight and surfactant (trade name: SF8427, manufactured by Toray Dow Corning Silicone)0 A positive photosensitive resin composition can be obtained by dissolving 3 parts by weight in a solvent of 11 parts by weight of propylene glycol acetate-acetic acid vinegar. Each measurement evaluation method described below was evaluated, and the results obtained are shown in Table 3. [Evaluation method] (I) Determination of the molecular weight distribution of the novolak resin (A) The acid varnish resin (A) was determined according to the gel permeation color of the Waters Company 201040665 layer analysis method GPC, and was determined according to the following conditions: Column: GP- 501/502/503/504 (manufactured by Polymer Laboratories) Detector: Waters RI-2410 Mobile phase: tetrahydrofuran (flow rate: 〇ml/min) Polystyrene of standard molecular weight was used as a measurement standard. The molecular weight of the resin referred to in the present invention is determined by GPC, that is, in the measurement range of GPC ,, the molecular weight is between 2 〇〇 and 15 〇, and the total integrated area of the resin signal of 〇〇〇 is regarded as 100%. Among them, the molecular weight is determined to be 200 to 400, and the molecular weight is 1 〇, and 〇〇〇 〜 30,000 is the content (% by weight) of the total resin. (Thermai Gravimetric Analysis) of the varnish resin (A). The varnish resin (A) is a thermogravimetric analyzer (Model: 2850, manufactured by τα Instruments Q) under nitrogen atmosphere, 23 (The thermal weight loss (% by weight) was measured at TC for 30 minutes. (III) Sensitivity The photosensitive resin composition was spin-coated on a 6 吋 Si wafer substrate, and then at a temperature of 、.5. Pre-baked in a minute to form a pre-baked film with a film thickness of 1. 5#m. After irradiation with a stepwise exposure machine (Nikon 1755G7A) at intervals of lms, then immersed in a developing solution of 23 C After minute development, the exposed portion of the substrate 201040665 was removed and washed with pure water. The sensitivity was evaluated as the exposure time (milliseconds, ms) required for each exposure region (0.5 cm x 0.5 cm) to be fully developed. 〇: 25$ exposure time 50 X each: exposure time $25 (4) Afterimage, the photosensitive resin composition is applied by spin coating on a color filter glass substrate having an alignment film and a transparent conductive film. Then pre-baked with /jdl degree 110 C, time 1.5 minutes, can form Pre-baked coating with a film thickness of 1.5/zm. The pre-baked film is placed between the specified masks, irradiated with a light meter of 20mJ/cm2 by a stepper (Nikon 1755G7A), and then impregnated at 23°. The developing solution of c is developed for 1 minute, the exposed portion of the substrate is removed, washed with pure water, and baked at 23 〇 c»c and then baked for 30 minutes to form a liquid crystal alignment control Q protrusion on the substrate. The color filter glass substrate obtained by the above steps is coated with a thermocompression adhesive, and another spacer having a thin germanium transistor is sprinkled with m spacers, and two sheets of glass are attached. After injecting the nematic liquid crystal, the liquid crystal cell is formed by sealing the liquid crystal injection port with ultraviolet (UV) hardening glue. The liquid crystal cell is made with a DC voltage of 1 volt, 48. After the application of the hour, when the voltage application is released, it is visually observed that there are 22 201040665 without image sticking. 〇: no image sticking occurs. X: There is a phenomenon of image sticking. Example 2 Operation of the same as Example 1. Method, the difference is to change the type and amount of novolak resin (A), add The type and amount of the additive (D), the formulation and the evaluation results are shown in Table 3. 〇Example 3 The same as the operation method of Example 1, except that the type and amount of the novolak resin (A) were changed, and the naphthyl naphthene was changed. The amount of the ester of the quinonediazide sulfonic acid (B), the kind of the solvent (C), the type and amount of the additive (D), the formulation and the ° parity result are shown in Table 3. Example 4 Same as Example 1. The method of operation differs in the type and amount of the novolak resin (A), the amount of the ester of the o-naphthoquinone diazide sulfonic acid (B), the type and amount of the solvent (C), and the additive (D). The type, formula and horse results are shown in Table 3. Example 5 The same procedure as in Example 1 was carried out except that the type of the novolak resin (A) was changed, and the formulation and evaluation results are shown in Table 3. Example 6 The operation method of the same embodiment 1 is to change the surface of the varnish resin 23 201040665 (A), the type and amount of the additive (9), and the formulation and evaluation results are shown in Table 3. Example 7 The operation method of the example 1 is the same as the method of changing the amount of the varnish resin (A), the type of the adjacent fine weiwei miscellaneous material (8), and the use of the inside and/or reading (G). The type and amount of the lion and the amount of the additive (9) are shown in Table 3. 〇Example 8 The same operation method as in Example 1, except that the type and amount of the secret varnish resin (A), the type and amount of the acetaminophen (8) of the naphthoquinone diazide, and the amount (La) (C) are changed. The dosage and the additive (9) were not added, and the formulation and evaluation results are shown in Table 3. Comparative Example 1 The same procedure as in Example 1 was carried out except that the type of the novolac resin Q (A) was changed, and the formulation and evaluation results are shown in Table 3. Comparative Example 2 The same procedure as in Example 1 was carried out except that the type of the novolak resin (A) and the type and amount of the additive were changed. The formulation and evaluation results are shown in Table 3. Comparative Example 3 Same as Example 1 The method of operation differs in that the type of the novolac resin (A), the type of the ester of the o-naphthoquinonediazide sulfonic acid (β), and the amount and amount of the use of the 24 201040665 i: a胄KG) The types and amounts of additives (8), their formulations and evaluation results are shown in Table 3. Comparative Example 4 The same operation method as in Example 1 'Individually similar to the type of varnish resin (A), the type and amount of the naphthoquinone-based azide acid (8), and the solvent (C) The formulation and evaluation results of the amount 'and the additive (9) are shown in Table 3. Comparative Example 5 The difference from the operation method of Example 1 was that the type of the secret varnish resin (A) was changed, and the formulation and evaluation results are shown in Table 3. The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the present invention and the contents of the invention are as follows. All should remain within the scope of the invention patent. 〇 [Description of Schedule] Table 1: Composition ratio of each synthesis example of the novolak resin (A) of the present invention. Table 2: Molecular weight distribution of each of the synthetic examples of the novolak resin (A) of the present invention, and the results of thermogravimetric loss. Table 2. Composition and evaluation results of the respective examples and comparative examples of the photosensitive resin composition of the present invention. 25 201040665

Table 1. Composition ratio of synthesis examples of novolac resin (A) Synthesis example composition (molar number) Reaction degree (°C) Polycondensation time (hour) Aromatic hydroxy compound aldehyde acid catalyst o-cresol - cresol p-nonylphenol 2,5-dimethyl phenol aldehyde oxalic acid A-1 0.70 0.30 0.65 0.020 100 6 A-2 0.55 0. 45 0. 73 0.010 100 6 A-3 0.05 0.55 0.40 0.82 0.005 100 6 A-4 0.55 0.40 0.05 0.92 0.005 95 6 Chinese name English name Mw o-cresol o-cresol 108.14 g/mol m-cresol m-cresol 108.15 g/mol p-cresol p-cresol 108.16 g/mol 2, 5-diphenylphenol 2,5-xylenol 122.17 g/mol 3,5-diphenylphenol 3,5-xyIenol 122.17 g/mol formaldehyde formaldehyde 30.03 g/mol oxalic acid oxalic acid 90.03 g/mol Table II, novolak resin ( A) The molecular weight distribution of the synthesis example, and the thermal weight loss result. The molecular weight distribution of the synthesis example (weight « thermal weight loss (%) 200~400 10,000 〜30, 000 A-1 12 10 15 A-2 10 14 13 A-3 8 17 12 A-4 7 18 9 A-5 5 11 6 A-6 4 16 5 A-7 4 18 5 A-8 2 18 4 A-9 1 19 3 A-10 2 20 3 26 201040665 % B- 1 B-2 C-1 C丨2 D-1 D丨2 73 a hanging aD^SF8427, Toray Dow Corning silicone^ ^5o; gBLI20, Tochem product^ ^§o;gcymel-303, w 半冷别濉ο 2 ,3,4-w^:&amp;l· 舛fs^lv琳筠咖踔-5-条踝~st bud 23,4&quot;·-county r5s?2-琳搏w?-sisi 31卜现&quot; 81 kiss pain - (?02£&quot;^0 section-§6-乂813211-£&quot;|*8&amp;3&quot; -躁si (EL, ethyllactate) Evaluation result I Thermal weight loss (% by weight) Molecular weight distribution ( % by weight) Additive (D) (parts by weight) Solvent (C) (parts by weight) Ester of anthraquinone diazide sulfonic acid (B) (parts by weight) Novolak resin (A) (parts by weight) Sensitivity 〇〇 〜 200~400 ο CO 〒 to 〒 ο οο ο I-· 〒 CO CO Ι-χ* A-10 &gt;· ς〇&gt; 00 &gt; ―J &gt; 05 &gt; U1 &gt; - &gt; CO &gt;tN〇&gt;· 〇〇〇1 ο αο 1100 tmmt 〇K) tn CD Ο 1-« Example 〇〇►-* CO 〇CO 1100 C3 CND cn αι cn cn CO 〇〇U1 I -· 1 0.15 1 1 0.15 1 1 iloo 1 CJ1 27.5 δ g CO 〇〇 〇〇&lt;i〇•ο GO -* ◦ ο 1000 IN0 CJ1 1-· 〇〇CO S hk ο CO 1100 ο Ol 1-» ο cn S S OD Ο CO 1100 to tn cn C71 cn 05 〇〇CJ1 5Ξ 1 ιοοο 1 CD oo tn s -vj 〇〇σ» CD CO ο CO cn U1 Ol 00 XX ϋΐ Ο N~« tv〇CD CO 1100 tmmk ο ΪΌ Cn H-* oo μ-^ Comparative example l X 〇s Η»» Private o ο Οΰ 1100 C3 ro CJ1 o tsD X 〇ίο t—t 00 1000 1-» g OJ Ol h-· oo CO X 〇CO CO -J g ο CO CJ1 c=&gt;&lt;=} 〇X σ&gt; 1-1 cn ο οο lioo 1 1-k CO C71 g tn 27

Claims (1)

201040665 VII. Patent application scope: 1. A positive photosensitive resin composition comprising: novolak resin (A); an esterified sensitizer (B) of ortho-naphthoquinone acid; and solvent (C) Wherein, the novolac resin (A) has a molecular weight of less than 150,000 as measured by gel permeation chromatography, and a total integrated area of the resin signal having a molecular weight of from 2 〇〇 to 〇150,000 When it is 1% by weight, its molecular weight is between 200 and 400, accounting for 6% by weight or less, and the molecular weight is between 1, 000 and 30,000, and 12% by weight or more; and the varnish tree is intended to be A) Analysis by a thermogravimetric analyzer has a thermal weight loss of 10% by weight or less under conditions of 23 ° C for 3 Torr. 2. A projection for liquid crystal alignment control, which is characterized by being formed of a positive photosensitive resin composition as described in the patent specification. 3. A method for producing a liquid crystal alignment control protrusion, which is characterized in that, in the range of 1st, a positive-type silk tree, the money is formed on the substrate, exposed, and developed. A liquid crystal display element is characterized in that it has a liquid crystal alignment control protrusion as described in the patent application. 28 201040665 IV. Designation of Representative Representatives: _ (1) The representative representative of the case is: No (2) Simple description of the symbol of the representative figure: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. : No 0 2