TWI286269B - Positive photoresist composition for manufacturing system LCD, manufacturing method for the positive photoresist and formation method of resist pattern - Google Patents

Abstract

A positive photoresist composition is provided which has a high sensitivity and a high thermal resistance and is favorable for manufacturing LCD having integrated circuits and liquid crystal display portions on a substrate. The positive photoresist composition contains (A) an alkali soluble resin, (B) a quinonediazido group-containing compound, wherein the (A) component is a novolak resin synthesized by a condensation reaction between a mixed phenol containing a phenol compound (a1) represented by the following general formula (1) and a phenol compound (a2) represented by the following general formula (11), and an aldehyde.

Description

1286269 (1) Field of the Invention [Technical Field] The present invention relates to a positive-type photoresist composition for manufacturing a system LCD for forming an integrated circuit and a liquid crystal display portion on a substrate, and a photoresist pattern forming method . [Prior Art] Conventionally, a photoresist material for manufacturing a liquid crystal display element (LCD) such as a thin film transistor (TFT) is suitable for exposure of a ghi line (all light including a g line, an h line, and an i line). Because it is relatively inexpensive and highly sensitive, a phenolic enamel resin can be used as the alkali-soluble resin, and a naphthoquinonediazide-based compound is used as a photosensitive component (hereinafter, abbreviated as PAC), and a phenolic enamel-naphthoquinone quinone is stacked. Nitrogen-based photoresists are widely used (see, for example, Patent Documents 1 to 4). The photoresist generally forms only a very rough pattern (about 3 to 5 // m) in the pixel portion forming the display. However, in recent years, as the next generation LCD, the integrated circuit portion of the 'driver' DAC (digital-to-analog converter), image processor, video controller, RAM, etc. on one glass substrate can be formed simultaneously with the display portion, ki The development of the technical system of the functional LCD of the "system LCD" is underway (for example, please refer to the non-patent literature). Hereinafter, in the present specification, such an LCD which can form an integrated circuit and a liquid crystal display portion on one substrate is conveniently referred to as a system LCD. In the substrate of such a system LCD, recently, the low temperature polyaluminum oxide, -6- 1286269 (2), especially the low temperature polyfluorene formed by the low temperature treatment of 疋600 ° C or less, compared with the amorphous polyfluorene oxygen, Small resistance and high mobility are appropriate and can be highly

In the development of the system LCD, which is used for the low-temperature polyfluorination of the substrate, the development of the LCD is actively carried out. [Patent Document 1] 曰本特开2 0 〇〇 - 1 3 1 8 3 5 (Patent Document 2) Japanese Laid-Open Patent Publication No. 2000-181055 (Patent Document 4) JP-A-2000- 1 1 2 1 2 0 (Non-Patent Document 1)

Semiconductor FPD World 2001. 9, pp. 50-67 In system LCD manufacturing, the ability to form good shapes at the same time in the photoresist material, the fine pattern of the integrated circuit part and the rough pattern of the liquid crystal display part (linear The improvement, the high resolution, the improvement of the depth of focus (DOF) characteristics of the fine pattern, etc. are strictly required. ◎ In addition, in the manufacture of TFTs formed by low-temperature polyfluorene, the polymerization is performed on a glass substrate at a low temperature. After the formation of the oxygen film, P or B or the like is incorporated in the low-temperature polyfluorene oxide film, and the improvement in heat resistance of the so-called "implaniation step" is also desired. Further, in the manufacture of system LCDs, in order to form a fine pattern, instead of the gh i-line exposure, it is expected that the i-line (3 6 5 nm) exposure (3) 1286269 process is introduced. However, a material which is conventionally used for the production of L C D, for example, a material using a diphenyl ketone-based P AC is difficult to apply to an i-line exposure process, and therefore it is expected that a material suitable for i-line exposure is desired. In terms of materials suitable for i-line exposure, it is expected that a material using a non-diphenyl ketone-based PAC is appropriate. However, the use of a non-diphenylketone-based PAC material has difficulty in high sensitivity. The sensitivity of the photoresist material is reduced, and the system LCD' is not good in the manufacturing field of LCDs because it causes fatal production rate reduction. Further, in the heat treatment (post exposure baking) step or the injection step in forming the photoresist pattern, since the high temperature treatment can be performed, in the steps, the light is not deformed in the steps. Resistance materials, high heat resistance are also sought. Therefore, in terms of a photoresist material for system LCD manufacturing, a material having high sensitivity and high heat resistance is desired. In terms of the high sensitivity of the photoresist material, the type or mix ratio of the phenol which is one of the raw materials of the phenolic enamel resin can be considered. For example, in the case of phenol, in the case of using cresol, the higher the ratio of p-cresol, the higher 邻rth 优异 酌 淸 优异 优异 优异 优异 优异 , , , , , , , , , , , , , , , , , Poor tendency. Therefore, if the ratio of cresol in the phenol is increased, the sensitivity is increased. However, when the phenolic enamel paint is used to modulate the photoresist material to form a photoresist pattern, there is a problem that the residual film property after development is lowered and the resolution is also lowered. Further, the sensitivity is also improved by the increase in the ratio of cresol between the phenols. However, when the photoresist pattern prepared by the phenolic enamel paint is used to form the photoresist pattern, the edge roughness of the photoresist pattern after development is 1286269 (4) degrees, etc., and the faithful reproducibility of the mask pattern is lowered. problem. In addition, in the other techniques of high sensitivity, although the use of low molecular weight phenolic enamel paint is considered, according to this method, the heat resistance of the resist pattern may be impaired, so any arbitrary technique is actually It is difficult to apply. [Problems to be Solved by the Invention] The present invention has been made in view of the above problems, and an object of the present invention is to provide a positive resistive composition which is suitable for use in system LCD manufacturing because of its high sensitivity and high heat resistance. [Means for Solving the Problems] The present invention provides a positive-type photoresist composition for LCD manufacturing which can form an integrated circuit and a liquid crystal display portion on a substrate, which comprises (A) an alkali-soluble resin and (B) A positive-type photoresist composition of a quinone diazide compound, wherein the component (A) contains the following general formula (I);

(〇H)a (1) (R)b wherein R represents an alkyl group having 1 to 3 carbon atoms, an alkoxypropyl group having 1 to 3 carbon atoms, or an aryl group; a represents an integer of 2 to 4 , the phenol compound (a ]) shown by b, or the integer of 1 to 2, and the following general formula ( -9 - (5) 1286269 Π)

(R)c OH ·· ( H ) wherein R represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an allyl group or an aryl group; and C represents 1 to 3 A phenolic enamel resin synthesized by a condensation reaction of a phenol compound (a2) represented by an integer number of phenols with an aldehyde. The present invention further provides a method for forming a photoresist pattern, comprising the steps of: (1) coating a positive photoresist composition according to any one of claims 1 to 5 on a substrate to form a coating. a step of filming, (2) a step of forming a photoresist film on the substrate by heat treatment (prebaking) of the substrate formed with the coating film, and (3) using a photoresist having a thickness of 2.0/im or less with respect to the photoresist film. The pattern forming mask pattern and the photoresist pattern exceeding 2.0# m form a mask for the selective exposure by the masks depicted by both of the mask patterns, (4) after the selective exposure The photoresist film is subjected to a heat treatment (post exposure baking) step, (5) after the above heat treatment, and a 7t resist film is subjected to development processing using the aqueous solution on the substrate to make the pattern size 2.0. // The photoresist pattern for integrated circuits below m and the step of forming a photoresist pattern for the liquid crystal display portion of more than 2.0 m, which constitutes the composition [invention] -10 - (6) 1286269 The invention will be described in detail. <The positive-type photoresist composition for system LCD manufacturing> The positive-type photoresist composition of the present invention, the component (A) is obtained by using a phenol compound containing at least two specific types, and the alkali obtained by mixing and mixing the phenol can be used. The lacquer resin is characterized by it. <(Α)Component&gt; (A) component contains a mixture of a phenol compound (al) ' represented by the general formula (I) and a phenol compound (A2) represented by the general formula (II), and an aldehyde An alkali-soluble phenolic enamel resin synthesized by a condensation reaction. In the general formula (I), in the case of R, there are an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group or the like; an alkoxy group having a carbon number of 1 to 3 such as a methoxy group; An aryl group or the like, wherein an alkyl group having 1 to 3 carbon atoms is preferred. The phenol compound (a 1 ) represented by the general formula (I) may, for example, be 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene or 1,2,3-tri a polyhydroxybenzene such as hydroxybenzene, 1,2,4-trihydroxybenzene or trihydroxybenzene, and an R substituent in which a part of a hydrogen atom of the polyhydroxybenzene is substituted by R or the like. Among them, 1,3 -dihydroxybenzene is preferred because of its high reaction rate in the synthesis of the phenolic enamel resin and good reactivity, so that the uniformity of the condensation reaction is not good. In the general formula (Π), in the same manner as described above, there are, for example, an alkyl group having 1 to 3 carbon atoms; an alkoxy group having 1 to 3 carbon atoms; an allyl group; an aryl group and the like, wherein the carbon number is 1 to 3 The base of 3 is better. -11 - (7) 1286269 In the case of the phenol compound (A2) represented by the general formula (II), there are cresols such as m-cresol, o-cresol, p-cresol, etc.; 2,5-xylenol, 3 , 4-dimethylbenzene, etc., such as dimethyl phenols; trialkyl phenols such as 2,3,5-trimethylphenol; and the like. The compounding ratio of the benzene compound (a 1 ) to the phenol compound (A2) is preferably 1:99 to 50:50 (mole ratio), more preferably 5:95 to 30:70. When the benzoquinone compound (a1) is blended in an amount of 1 mol% or more based on the total of the phenol compound (a) and the phenol compound (a2), the effect of high sensitivity can be sufficiently obtained, and on the other hand, it is 50 mol. When it is less than or equal to %, the residual film property after the development treatment is excellent, and a high-resolution photoresist pattern can be formed. The aldehyde is not particularly limited, and an aldehyde used in the production of a conventional phenolic enamel resin can be used, and a mixture of formaldehyde (Π) and an aldehyde other than oxime (mixed aldehyde) can be used, but Further, the preparation of the photoresist material having excellent heat resistance is appropriate. The aldehyde () is not particularly limited, but an aldehyde having a bulky substituent such as acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde or vanillin is preferred. Among them, propionaldehyde and salicylaldehyde are preferred, and propionaldehyde is preferred. By using the aldehyde and formaldehyde (f 1 ), the main chain of the phenolic lacquer resin and the rotational potential energy of the side chain can be improved by the steric hindrance in the molecule of the obtained phenolic enamel resin (P 01e 111 ia 1 energy ) 'Inhibition of free rotation, excellent effect of heat resistance improvement 1 ° Mixing ratio of formaldehyde (f 1 ) and wake-up (f2) in mixed aldehydes is preferably 5〇: 50~95 : 5 (Wu Erbi) 'better for 60: 40~90: 10 . Further, the aldehydes (f2)' may be used alone or in combination of two types of -12-(8) 1286269. The mixing ratio of the mixed phenols to the aldehydes is preferably 1: 〜·5 to 1:1 (mole ratio), more preferably 1:0.6 to 1: 0.95° (A). The component can be produced according to a conventional method, and can be synthesized, for example, by mixing a phenol and an aldehyde, and performing a condensation reaction in the presence of an acidic catalyst. The polystyrene-converted mass average molecular weight (hereinafter, simply referred to as Mw) due to the gel permeation chromatography of the component (A) may be determined according to the type thereof, but in terms of sensitivity or pattern formation It is appropriate to be 2000 to 100000, preferably 3 0 0 0 to 3 0 0 0 0. &lt;(B) Component&gt; The component (B) is a compound containing a quinonediazide group. (B) The component is generally used in the positive-type resist composition, and is not particularly limited as the user of the photosensitive component (PAC), and may be used singly or in combination of two or more. Among them, an esterification reaction product of a non-diphenylketone-based phenolic hydroxy compound and a 1,2-naphthoquinonediazidesulfonyl compound (non-diphenylketone-based PAC) is suitable for use. The light of the i-line is lithographic, so it is better. Further, even in the case of low NA, the resolution is excellent, and it is appropriate to form a resist pattern in a good shape. Also, the point of linearity or D 0 F is also good. In the case of a 1,2-naphthoquinonediazidesulfonyl compound, a 1,2-naphthoquinonediazide-4-sulfonyl compound and/or 1,2-caioxadiazide-5- Sulf-13-(9) 1286269 mercapto compounds are preferred. The non-monoketone-based phenolic hydroxy compound may, for example, be exemplified by the following general formula (III) (H0)d.

Wherein R to R8 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms; ; R1G, R1] represents a respective hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R9 may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; in this case, Q] is a hydrogen atom, and the carbon number is 1 ~6 of the hospital base or the following chemical formula (IV) R 12

(wherein R, 2 and R13 are each independently a hydrogen atom 'halogen atom, a group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkane having 3 to 6 carbon atoms. a group; f represents a residue represented by an integer of 1 to 3 or Q] is bondable to the end of R9 'in this case' Q represents a carbon between R9 and 'Q1 - 14- 1286269 (10) and R9 Atom, at the same time, represents a cycloalkyl group having a carbon chain of 3 to 6; d, e represents an integer of 1 to 3; g represents an integer of 0 to 3; and when d, e or g is 3, each is free of R3, R6 or R8 η represents an integer from 0 to 3. The compound shown. Further, in the case where the carbon atom between Q] and R9 and Q1 and R9 is in the form of a cycloalkyl group having a carbon chain of 3 to 6, Q 1 and R 9 are bonded to form an olefin group having a carbon number of 2 to 5. . The phenol compound of the general formula (III) may, for example, be tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis ( 4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis ( 4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4- Hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy- 2,5-Dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxyl -2,5-dimethylphenyl)-3,4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis ( 4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane, bis(5-cyclohexylfluorene-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(5-ring Hexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, double (5 -cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenyl a trisphenol type compound such as methane; -15- 1286269 (11) 2; 4-bis(3,5-dimethyl-4-hydroxybenzyl)-5-hydroxyphenyl, 2,6-bis (2, Linear 3-nuclear phenol compound such as 5-dimethyl-4-hydroxybenzyl)-4-methylphenol; 1J-bis[3-(2-hydroxy-5-methylbenzyl)-4-hydroxyl -5-cyclohexylphenyl]isopropane, bis[2,5-dimethyl-3-(4-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane, bis[2,5- Dimethyl-3-(4-hydroxybenzyl)-4-hydroxyphenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-methyl Phenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, bis[3-(3,5-dimethyl) 4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, bis[3-(3, 5-diethyl-4-hydroxybenzyl)-4-benzyl)-5- a linear 4-nuclear phenol compound such as methane or bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane; 4- [2-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol, 2,4-bis[4-hydroxy-3-(4-hydroxybenzyl)-5 -methylbenzyl]-6-cyclohexylphenol, 2,6-bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxybenzyl]-4 a linear polyphenol compound such as a linear 5-nuclear phenol compound such as methylphenol; bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, 2 ,3,4-trihydroxyphenylhydroxyphenylmethane, 2-(2,3,cardiotrihydroxyphenyl)-2-(2,34,-trihydroxyphenyl)propanine, 2- (2,4 -dihydroxyphenyl)-2-(2-4^dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4-hydroxyphenyl)propane, 2-(3-fluoro-4- Hydroxyphenyl)-2-(3'-fluoro-4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-( 2,3;4-trihydroxyphenyl)-2-(4'-hydroxy-16-(12) 1286269-phenyl)propane '2-(2,3,4-trihydroxyphenyl)-2-( a bisphenol type compound such as 4,-hydroxy-3',5'-dimethylphenyl)propane; 1-[Bu(4-hydroxyphenyl)isopropyl]-4·[151 -Bis(4-hydroxyphenyl)ethyl]benzene, 1-[1-(3-methyl-4-hydroxyphenyl))isopropyl)_4_[ 1, bis(3-methylhydroxyphenyl) a polynuclear branched multinuclear branched compound such as ethyl benzene; a condensed phenol compound such as bis(4-hydroxyphenyl)cyclohexane; These may be used in combination of one type or two or more types. Among them, a trisphenol type compound is preferred, and it is preferable in terms of high sensitivity and resolution, especially bis(5-cyclohexyl-[hydroxy-2-methylphenyl)-3,4. - Dihydroxyphenylmethane (hereinafter referred to as (B1,)). ], bis(4-transyl-2,3trimethylphenyl)-2-hydroxyphenylmethane [hereinafter abbreviated as (B 3 '). ] is better. In the case of a photoresist composition having excellent resolution, such as resolution, sensitivity, heat resistance 'DOF characteristics, linearity, and the like, the linear polyphenol compound and the bisphenol type compound can be multinucleated. The compound of the formula, the condensed phenol compound, and the like are preferably used together with the above-mentioned trisphenol type compound, particularly a bisphenol type compound, wherein bis(2,4-dihydroxyphenyl)methane (hereinafter referred to as (B2, ). 〕 When used, it can adjust the photoresist composition with excellent total balance. Further, in the following, the respective naphthalene S-quinonediazide esters of (Bl,), (B2,) and (B3,) are simply referred to as (b I ) , ( B2 ), (B3 ). In the case of using (B)) and (B3), the amount of the component (b) is preferably 5% by mass or more, and more preferably 5% by mass or more. Further, (13) 1286269 may each be 90% by mass or less, preferably 85% by mass or less. Further, in the case where the effects (B1), (B2) and (B3) are completely used, the respective amounts (B1) are 50 to 90% by mass, preferably 60 to 80% by mass, (B2). The compounding amount is 5 to 25% by mass, preferably 1 to 5% by mass, and the amount of (B3) is 5 to 25% by mass, preferably 1 to 15% by mass. The method of esterifying all or a part of the phenolic hydroxyl group of the compound of the above formula (III) with a naphthoquinonediazidesulfonate can be carried out according to a conventional method. For example, a naphthoquinonediazidesulfonyl chloride can be obtained by condensing a compound represented by the above general formula (III). Specifically, for example, the compound represented by the above general formula (III) and naphthoquinone-1,2-indolyl-4-(5)-sulfonyl chloride are in hexane, n-methyl An organic solvent such as pyrrolidone, dimethylacetamide or tetrahydrofuran is dissolved in a quantitative amount, and one or more alkaline catalysts such as triethylamine, triethanolamine, pyridine, alkali carbonate, and hydrogencarbonate are added thereto. The resulting product was washed with water and dried to prepare a solution. In the component (B), as described above, in addition to the preferred naphthoquinonediazide esters exemplified above, other naphthoquinonediazide esters may be used, and for example, polyhydroxydiphenyl may be used. An esterification reaction product of a phenol compound such as a ketone or an alkyl gallate or a naphthoquinonediazidesulfonic acid compound. The amount of the other naphthoquinone diazide ester compound used is preferably 80% by mass or less, particularly 50% by mass or less, based on the photosensitive component (B), and the effect of the present invention can be improved. . -18- (14) 1286269 The compounding amount of the component (B) in the photoresist composition is 20 to 70% by mass, preferably 25 to 60% by mass based on the total amount of the component (a) and the component (C) below. %. When the blending amount of the component (B) is at least the above lower limit ,, a faithful image of the pattern can be obtained, and the transfer property can be improved. When the upper limit is not more than 上述, the deterioration of the sensitivity can be prevented, and the homogeneity of the formed photoresist film can be improved, and the resolution can be improved. &lt;(C) Component&gt; The positive resist composition of the present invention contains, in addition to the above components (A) and (B), further, (C) a phenol having a molecular weight of 1 000 or less in terms of a solubilizer. A hydroxy compound is preferred. Since the component (C) is excellent in sensitivity improvement, it is suitable for LCD by the use of the component (C), during the exposure process under the condition of low να (numerical aperture), 13⁄4 sensitivity 'local resolution' The material to be manufactured, in turn, is preferably a material suitable for a system LCD excellent in linearity. The molecular weight of the component (C) is preferably 1,000 or less, preferably 7 or less, and substantially 200 or more, preferably 300 or more, and the above effects are preferred. (C) In terms of strength, the material of the sensitization, or the benzene-containing perfluoro-based compound generally used for the photoresist composition in the case of a solubilizing agent, preferably in the case of satisfying the above molecular weight conditions, is not particularly Qualified, g ^ is arbitrarily selected for one or two or more types. Moreover, among them, the following general formula (V) ‘19- (15) 1286269

Wherein R21 to R2 8 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms; R3(), R31 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and R29 may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; in this case, Q2 is a hydrogen atom and has a carbon number of 1; a residue of 1-6 or a residue represented by the following chemical formula (VI)

(〇H)j (wherein R32 and R33 represent each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a carbon atom number of 3 to 6; a cycloalkyl group; j is an integer of 〇~3), and Q2 may be bonded to the terminal of R29. In this case, Q2 represents R29 and, together with carbon atom t between Q2 and R29, represents carbon bond 3~6.环院基;h' i表不~ an integer of 3; k represents an integer of 〇~3; when h, i or k is 3, there is no R23, R26 or R 2 8 ; m represents an integer of 0~3] The phenol compound shown is preferably one which exhibits the above characteristics in a good manner. -20- (16) 1286269 Specifically, for example, exemplified in the above component (B), a bis(3-methyl-4-pyridylphenyl) group can be suitably used in addition to the compound represented by the general formula (111). -4-isopropylphenylmethane, bis(3-methyl-4-hydroxyphenyl)-phenylmethane, bis(2-methyl-4-hydroxyphenylphenylmethane, bis(methyl-2) -hydroxyphenyl)-phenylmethane, bis(3,5-dimethylhydroxyphenylphenylmethane, bis(3-ethyl-4-hydroxyphenyl)-phenylmethane, bis(2-methyl a triphenyl type compound such as -4-hydroxyphenyl)-phenylmethane or bis(2-tert-butyl-4,5-dihydroxyphenyl)-phenylmethane can be suitably used. -methyl-4-hydroxyphenyl)-phenylmethane, [·[ h (4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl] The amount of the component (C) is preferably from 10 to 70% by mass, preferably from 20 to 60% by mass, based on the component (a). The organic solvent &gt; The positive photoresist composition of the present invention further contains an organic solvent. The organic solvent is in the photoresist group. The general use of the material is not particularly limited, and one or two or more kinds may be used, and propylene glycol monoalkyl ether acetate and/or 2-heptanone may be used, and the coating property is excellent, and it is on a large glass substrate. It is preferable that the film thickness uniformity of the upper photoresist film is excellent. Further, both propylene glycol monoalkyl ether acetate and 2 · heptanone may be used, and they may be used alone or in combination with other organic solvents. It is preferable that the film thickness uniformity at the time of coating by spin coating or the like is more than 21 - (17) 1286269 propylene glycol monoalkyl ether acetate is contained in an all organic solvent, and contains 5 〜 〜 0 0 mass. % is preferably propylene glycol monoalkyl ether acetate, for example, a linear or branched alkyl group having a carbon number of 1 to 3, wherein propylene glycol monomethyl ether acetate (hereinafter, abbreviated as PGMEA), It is particularly preferable that the film thickness of the photoresist film on the large-sized glass substrate is excellent. On the one hand, 2-heptanone is not particularly limited, and the above-mentioned (Β) component and the non-diphenylketone-based photosensitive layer are not particularly limited. The combination of sexual components is a suitable solvent. 2-heptanone, compared with PGMEA It is excellent in heat resistance and has a property of imparting a property of reducing the composition of the photoresist to the dross. It is a very good solvent. When 2-heptanone is used alone or in combination with other organic solvents, in an all organic solvent, It is preferred to contain 50 to 100% by mass. Further, in these preferred solvents, it may be mixed with other solvents, for example, a lactic acid such as methyl lactate, ethyl lactate or the like (preferably ethyl lactate). In the case of an alkyl ester, a photoresist pattern having excellent film thickness uniformity and excellent shape can be formed. When propylene glycol monoalkyl ether acetate is mixed with an alkyl lactate, it is compared with a propylene glycol monoalkyl group. The mass ratio of the ether acetate is preferably from 1 to 1 Torr, preferably from 1 to 5 times the amount of the alkyl lactate. An organic solvent such as r-butyrolactone or propylene glycol monobutyl ether may also be used. In the case of using 7 - butyrolactone, the mass ratio of the propylene glycol monoalkyl ether ethylene-22-1286269 (18) acid ester is 0.01 to 1 times, preferably 0.05 to 0.5 times the amount of the mixture. Hope. Further, specific examples of other organic solvents that can be blended include, for example, the following. That is, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate , diethylene glycol monoacetate, or such polyols as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether, and derivatives thereof; epoxy Hexane-like cyclic ethers; and esters of methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc. Classes, etc. In the case of using these solvents, in the total organic solvent, it is expected to be below 50% by mass. &lt;Other components&gt; The positive-type photoresist composition of the present invention may contain a compatible additive as needed, for example, to improve the performance of the photoresist film, etc., without departing from the object of the present invention. Addition resin, plasticizer, storage stabilizer 'surfactant, so that the image of the image is further visualized as a coloring material, thereby enhancing the sensitizing effect of the solubilizing agent or halation preventing dye, adhesion Enhancer, etc. Conventional additives. In terms of the dye-preventing dye, an ultraviolet absorber (for example, 2,2'4,4,-tetrahydroxydiphenyl ketone, cardiomethylamino-2',4'-dihydroxydiphenyl) can be used. Ketone, 5-amino-3-methyl-buphenyl-4-(cardiohydroxyphenylazo-23-(19) 1286269) pyrazole, 4-dimethylamino 4'-hydroxyazobenzene , 4-diethylamino-4,-ethoxy azoben' 4-ethylamino azobenzene, curcumin, etc.). For example, a surfactant can be added to prevent the use of the embossing, for example, Furolite FC-4 3 0 ^ FC4 3 1 (trade name, manufactured by Sumitomo 3M Co., Ltd.), EF-TOP EF 1 22A, EF 122B, EF 122C, EF 126 can be used. (trade name, manufactured by Tokem Products Co., Ltd.), etc., a fluorine-based surfactant, etc., Megafuck R-〇8 (trade name, manufactured by Dainippon Ink Chemicals Co., Ltd.). &lt;Preparation method of positive-type photoresist&gt; The positive-type photoresist composition of the present invention, for example, the components (A) to (C) and other components are dissolved in an organic solvent and filtered to prepare. Further, the amount of the organic solvent to be used is preferably such that the components (A) to (C) and other components are dissolved to obtain a uniform positive resist composition. The concentration of the solid component [(A) to (C) component and other components] is preferably from 1 to 5 % by mass, preferably from 20 to 35% by mass. In the positive-type resist composition of the present invention, Mw (hereinafter referred to as "resistance molecular weight") contained in the solid content of the photoresist composition is preferably adjusted in the range of 5 〇〇〇 to 3 0000. Good Mw is 6000~ 10000. When the molecular weight of the photoresist is in the above range, high heat resistance and high resolution without deteriorating the sensitivity can be achieved, and a positive resist composition excellent in linearity and D 0 F characteristics can be obtained. -24 - 1286269 (20) When the molecular weight of the photoresist is smaller than the above range, the heat resistance, resolution, linearity and DOF characteristics are insufficient. When the above range is exceeded, the sensitivity is significantly reduced, which may damage the positive light. The coating properties of the composition are hindered. In the method of modulating the molecular weight of the photoresist to the above-mentioned appropriate range, for example, 'the operation is performed separately with respect to the component (A) before mixing, and the Mw after mixing all the components is in the above range, and the Mw of the component (A) is adjusted in advance. A suitable range of methods is to prepare a plurality of components (A) in which Mw is different, and to appropriately mix them, and to adjust the Mw of the solid component to the above range. Further, the following aspects of the molecular weight of the photoresist in the present specification are measured using the following GP C system. Device name: SYSTEM 1 1 (product name, manufactured by Showa Denko)

Pre-column: KF-G (product name, manufactured by Shodex) column : KF- 8 05, KF-803, KF- 8 02 (product name,

Detector: UV41 (product name, manufactured by Shodex Co., Ltd.), measured at 280 Nm. Solvent, etc.: Tetrahydrofuran was passed through at a flow rate of 1 · 〇 m / min, and it was measured at 3 5 . In the measurement sample preparation method, the photo-resist composition to be measured was adjusted so that the solid content concentration was 30% by mass, and this was diluted with tetrahydrofuran to prepare a measurement sample having a solid content concentration of 0% by mass. The 2^/L of the 1^: measured δ-type material was thrown into the above device for measurement. The positive-type photoresist composition of the present invention described above is a phenolic enamel resin obtained by mixing a specific benzene-25-(21) 1286269 phenol, thereby improving heat resistance and sensitivity. Therefore, it is appropriate to manufacture a system LCD which is necessary for high heat resistance and high sensitivity. Further, the resolution is excellent, or the residual film property after development is excellent, and the DOF characteristic, the linearity, and the like are also excellent, and the like is a more suitable material for system LCD manufacturing. Among them, in the case of the component (B), in the case of using a non-diphenyl ketone-based PAC, the sensitivity can be improved, and the DOF characteristic with high resolution can be made in the exposure process under low NA conditions, linearity, etc. The photoresist characteristics are further improved. Further, in the manufacture of the system LCD, as described above, it is expected to use an i-line (3 6 5 nm) having a shorter wavelength than that of the conventional LCD manufacturing user, and in the positive resist composition of the present invention, (B) In the case of the component (C), when the non-diphenylketone-based compound represented by the general formulae (III) and (V) is used, the component (B) and the component (C) can be suppressed. Absorption, so the i-line exposure process is the appropriate material, which can achieve high resolution. <<Method for Forming Photoresist Patterns>> Hereinafter, an example of a method for forming a photoresist pattern of the present invention will be described. First, the positive-type photoresist composition of the present invention is applied to a substrate by a rotator or the like to form a coating film. . A glass substrate is preferred for the substrate. In the field of a glass substrate, in the field of a system LCD which is generally used for non-crystalline vermiculite, a glass substrate formed by a low-temperature polyoxygenated layer -26-(22) 1286269 is preferable. In terms of the glass substrate, the positive resist composition of the present invention is excellent in resolution under low NA conditions, and can be used at 500 mm X 60 mm or more, and in particular, 5 5 0 mm x 6 5 0 can be used. Large substrate above ni m. Next, the glass substrate on which the coating film is formed is heated (prebaked) at, for example, 1 00 to 1 40 ° C to remove the residual solvent to form a photoresist film. In terms of the prebaking method, it is preferred to carry out the adjacent baking of the gap between the hot plate and the substrate. Furthermore, the mask pattern formed by the photoresist pattern corresponding to the above-mentioned photoresist film corresponding to 2·0 // m of the integrated circuit portion and the photoresist corresponding to the liquid crystal display portion exceeding 2·0#ηι The pattern forming masks depicted by both sides of the mask pattern are used for selective exposure. In terms of the light source, it is preferable to use an i-line (3 6 5 N m ) in order to form a fine pattern. Further, the exposure process employed in the exposure is preferably 3 3 or less, preferably 0 or less, more preferably 〇. The exposure process of the lower Ν Α condition of 15 or less is preferred. Next, heat treatment (post exposure baking: PEB) is carried out with respect to the photoresist film after selective exposure. In terms of PEB temperature, it is preferably from 90 to 150 ° C, more preferably from 1 to 120 ° C. Further, in the PEB method, adjacent baking can be used to maintain a gap (gap) between the hot plate and the substrate. Or any one of direct baking that does not maintain a gap between the hot plate and the substrate, and in particular, it is preferable to use the two. Among them, it is preferred to perform direct baking after performing adjacent baking. More -27-100 1286269 (23) Specifically, 90~] 50°C, more preferably 100~I20t, 5~ seconds, more preferably 〇~50 seconds, clearance is 0.05~5mm, more { 〇·]~1 mm After performing adjacent baking, it is 90~150°C, more ί100~120 °C, 5~200 seconds, more preferably 30~80 seconds, into the f gap 0mm Direct baking is expected. The exposed portion is dissolved and removed, and the exposed portion can be simultaneously formed on the substrate, with respect to the photoresist film after the PEB, and the developing solution, for example, an aqueous alkali solution of ~1% by mass of tetramethylammonium hydroxide aqueous solution. _ The photoresist pattern used in the circuit and the photoresist pattern used in the LCD part. Further, 'the liquid remaining on the surface of the resist pattern is washed with pure water or the like, and the photoresist pattern for the circuit of the pattern size of 2.0/zm or less can be formed on the substrate at the same time. A photoresist pattern of a portion of the liquid crystal display that exceeds 2 · 0 // m. [Embodiment] Hereinafter, the present invention will be described by way of examples and will be described in detail. (Synthesis Example)) A 1 L separable flask (separable nask) having a cooling tube 'Teflon (registered trademark) stirring blade, temperature 'dropping funnel, and the composition of the ear-to-ear ratio) is '153-dihydroxybenzene (a)/ - m-cresol (a2) / 3 a bismuth (a2) /2,3,5-trimethylbenzoquinone (a 2) =15/68/ϊ / 8 · 5 mixed phenols 1 In the ear, the concentration of the total amount of the all monomers (mixed oxime classification) is 40% by mass, and is added as the acid catalyst p-toluic acid dihydrate 〇·〇丨莫耳. Stir ί is ί: Between the user and the person (4:.5 Benzene -28 - 1286269 (24) Secondly, the temperature of the oil bath is set to 1 〇〇t. Secondly, it will be combined with propionaldehyde. 0·15旲 ear of 3 7 mass% formalin aqueous solution (formaldehyde content 〇.76 moler) wake up (f 1): a awake (f2) = 83.5: 16.5 (morbi) to drip funnel through 3 0 After a minute, it was slowly dripped. Thereafter, it was stirred at a temperature of 100 ° C for 12 hours. After the completion of the stirring, it was cooled to room temperature (2 51 ), washed with butyl acetate, and the upper layer was concentrated by an evaporator. not The resin solution was prepared by adding the resin solution to methanol in a separatory funnel, and the mixture was stirred with n-heptane, and then the mixture was allowed to stand, and the lower layer was peeled off, and PgMEA was added to obtain a resin solution (A1) obtained by concentration and purification. The mass average molecular weight (M w ) converted to ethylene is [〇5 〇〇. (Synthesis Example 2 to ό) In Synthesis Example 1, the composition of the phenol is mixed, the species of the aldehyde (f2), and the aldehyde ( f 1 ) / ( f2 ) The resin solutions (A2) to (A6) were obtained in the same manner as in Synthesis Example 1 except that the description was changed. In Table 1, the respective resins were V[w倂. The singular number in the table has the following meaning: 1,3-DHB: dihydroxybenzene mC: m-cresol 3,4-ΧΥ: 3,4-xylene 酣2 5 ^ 5 5 - Τ Μ Ρ · -Dimethylbenzene Discretion FA: Formaldehyde PA: Propionaldehyde SA: Salicylaldehyde-29- (25) 1286269 [Table 1] Composition of mixed phenols (Mohr ratio) (al/a2) Aldehydes (fl/β Mw Synthesis Example 1 l,3-DHB/mC/3,4-XY/2,3,5-TMP (15/68/8.5/8.5) 15/85 FA/PA (83.5/16.5) 10500 Synthesis Example 2 Same as above FA/SA (83.5/16.5) 10000 Synthesis Example 3 1,3-DHB/m -C/3,4-XY(l 5/68/17) Same as above FA/PA (83.5/16.5) 10500 Synthesis Example 4 l?3-DHB/mC/354-XY/2?3?5-TMP (15 /68/8.5/8.5) Same as above FA 10000 Synthesis Example 5 mC/354-XY/2?3?5 -IMP(68/8.5/8.5) -/100 FA/PA (83.5/16.5) 11000 Synthesis Example 6 Same as above FA 11000 • (Examples 1 to 4, Comparative Examples 1 to 2) The component (C) of the resin solution (A 1 ) to ( _ A6) obtained in the above Synthesis Examples 1 to 6 was mixed with bis (2). Methyl-4-hydroxyphenyl)-phenylmethane was 35 mass%. Next, in the component (B), the total mass of the mixed PAC of "(B1) / (B2) / (B3) = 6 / 1 / 1 (mass ratio) relative to the solid content of the above resin and the component (C)" Then, the blending amount is 30% by mass. Next, PGMEA was added, and the total solid content concentration was adjusted to 25 mass% to obtain a photoresist composition. The photoresist composition -30-(26) 1286269 was filtered through a 0.2 m filter to adjust the photoresist coating liquid. Table 2 shows the types of resin solutions used and the amount of photoresist molecules of each photoresist coating liquid. Further, the above (B 1 ) to (B 3 ) are as follows. (B1) bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane (Bl') 1 molar and 1,2-naphthoquinonediazide- 5-sulfonyl chloride (hereinafter, simply referred to as (5-NQD). 〕 2 molar esterification reaction product (82) bis(2,4-dihydroxyphenyl)methane (82 〇 1 molar and 5-NQD2 molar esterification reaction product (B3) bis (4- Hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane (B3') 1 molar and 5-NQD 2 molar esterification reaction product [Table 2]

Resin solution photoresist molecular weight linear sensitivity (mJ) DOF (μηι) resolution (μηι) heat resistance Example 1 (A1) 5700 A 47.5 20 1.2 A Example 2 (A2) 5500 A 20 10 1.5 A Example 3 (A3) 5700 A 42.5 20 1.2 B Example 4 (A4) 5500 A 35 15 1.4 B Comparative Example] (A5) 6000 A 150 20 1.4 C Comparative Example 2 (A6) 6000 A 120 20 1.4 C About Example 1 4. The photoresist coating liquid obtained in Comparative Example ～2, -31 - (27) 1286269, was evaluated for linearity, sensitivity, DOF, resolution, and heat resistance in the following order. The results are summarized in Table 2. (Linear Evaluation) A photoresist coating apparatus (device name: TR 3 6 000 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used to apply a photoresist coating liquid to a glass substrate formed of a Ti film (550 mm X 6 5). After 0 mm), the temperature of the hot plate is 1 〇〇 °C by opening the adjacent imm interval for the first drying of 90 seconds, and then the temperature of the hot plate is 90 ° C by The second baking was performed for 90 seconds in the vicinity of the opening of 〇5 mm to form a photoresist film having a film thickness of / m. Secondly, the mask pattern of the 3·0 // m L &amp; S and 1. 5 # m L &amp; S photoresist pattern can be reproduced at the same time. Among them, an i-line exposure apparatus (device name: FXJ〇2 J, manufactured by Nikon Co., Ltd.; ΝΑ = 0.14) was used for selective exposure in an exposure amount (Εορ exposure amount) which can faithfully reproduce 1.5// m L&amp;S . Next, the temperature of the hot plate is made 1 2 0 ° C 'open 〇 · 5 mm interval, by adjacent baking, performing heat treatment for 30 seconds and then at the same temperature by direct baking without opening interval' The heat treatment was carried out for 60 seconds, and the development device having a slit coater nozzle (device name: TD-3900 display machine, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used, and 23 ° C, 2 · 38 mass was used. % TMA Η aqueous solution (product name "NMD-3" manufactured by Toki Chemical Co., Ltd.), from the end of the substrate X to Z (refer to Figure 1) 'after -32- (28) 1286269 1 〇 seconds on the substrate After filling for 5 5 seconds, it was washed with water for 30 seconds for spin-drying. Thereafter, the cross-sectional shape of the obtained photoresist pattern was observed by SEM (scanning electron microscope) photograph to evaluate the reproducibility of the photoresist pattern of 3 · 0 # m L &amp; S. Those whose dimensional change rate is ± 10% or less are A, more than 10% - those within 15% are B, and those exceeding 15% are indicated by C. (Sensitivity evaluation) The photoresist pattern of 1.5/5 m L &amp; S is expressed in an faithful reproduction amount (Eop) (mJ/cm 2 ). (DOF evaluation) In the above exposure amount (Eop), the DOF can be suitably moved up and down by 1.5. 5 // m L &amp; S is the range of the depth of focus obtained in the range of the dimensional change rate of ±10% (total depth width) ) is expressed in units of / / m. (Resolution Evaluation) The above exposure amount (Eop) is expressed by the limit resolution. (Evaluation of heat resistance) In the above Eop exposure amount, the substrate depicted by 3.〇# m L&amp;S was set to stand on a hot plate of 14 ° C for 300 seconds, and the cross-sectional shape was observed. . As a result, the dimensional change rate of 3.0//m L&amp;S was less than ±3%, and it was A in the range of 3 to 4% or -3 to -4%, and the excess was C. The phenol-containing phenol resin-containing photoresist composition was synthesized by using the specific phenols of Examples 1 to 4, and was excellent in heat resistance and sensitivity. Further, linearity, D 0 F, and resolution are also excellent, and the materials used for the system 1 C D are self-explanatory. Further, in Examples 1 to 3 used for the phenolic enamel resin synthesized by using a specific mixed aldehyde with respect to the aldehyde, compared with Example 4, heat resistance can be improved by using a mixed aldehyde. The photoresist composition is self-explanatory. On the other hand, the photoresist compositions of Comparative Examples 1 and 2 which did not use mixed phenols were inferior in heat resistance and sensitivity. [Effects of the Invention] As described above, the positive resist composition of the present invention has high sensitivity and high heat resistance, and is extremely suitable for system LCD manufacturing. [Simple description of the diagram] [Fig. 1] For the linear evaluation under low NA conditions, the positive photoresist composition is applied to a glass substrate to be baked and dried to expose the pattern, and then has a slit coater. An illustration of the purpose of the liquid leveling of the developing solution from the end portions X to Z of the substrate. SUMMARY OF THE INVENTION The present invention provides a high-sensitivity and high heat resistance, and a positive-type photoresist composition suitable for LCD production in which an integrated circuit and a liquid crystal display portion can be formed on one substrate. The positive resist composition comprises (A) an alkali-soluble resin and (B) a quinonediazide-based compound, and the component (A) contains a phenol compound represented by the following general formula (I) (a) 1) and a phenolic enamel resin synthesized by a condensation reaction of a phenol compound (A2) represented by the following general formula (II) with a phenol-34286628 (30).

Claims (1)

1286269 (1) Pickup, Patent Application No. 1. A positive photoresist composition for LCD manufacturing which can form an integrated circuit and a liquid crystal display portion on a substrate, which is characterized by containing '(A) alkali-soluble resin and (B) a positive-type photoresist composition containing a quinonediazide compound, wherein the component (A) contains the following general formula (I) (〇H)a (I) (R)b [wherein R represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a dilute propyl group or an aryl group; and a represents 2 a phenol compound (ai) represented by an integer of ～4; b represents an integer of 0 or 1 to 2, and the following general formula (Π ΌΗ ... (H ) (R)c [wherein R represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an allyl group or an aryl group; and C represents an integer of 1 to 3 The phenolic enamel resin synthesized by the condensation reaction of the mixed phenols and aldehydes of the phenol compound (A2) shown. 2. The positive-type photoresist composition according to claim 1, wherein the ratio of the phenol compound (a) to the phenol compound (A 2 ) is -36 - 1286269 (2) 1:99 to 50 : 50 (Morbi). 3. A positive-type photoresist composition according to claim 1 or 2, wherein the aforementioned aldehyde system is a mixture of formaldehyde and propionaldehyde. 4. The positive-type photoresist composition of claim 1, wherein 'the above-mentioned (B) component contains a non-diphenylketone-based phenolic hydroxy compound and an anthracene, 2-naphthoquinonediazide group An esterification reaction product of a sulfonyl compound. 5. A positive-type photoresist composition according to the first aspect of the patent application, which further comprises (C) a phenol-containing hydroxy compound having a molecular weight of 1 Å or less. A method for forming a photoresist pattern, comprising the steps of: (1) coating a positive resist composition according to any one of claims 1 to 5 on a substrate to form a coating. a step of filming, (2) a step of heat-treating (pre-baking) the substrate on which the coating film is formed to form a photoresist film on the substrate, and (3) using light having a thickness of 2.0 // m or less with respect to the photoresist film. The mask pattern is formed by a mask pattern and a mask pattern of more than 2.0//m is formed to form a mask for the selective exposure of the mask pattern, and (4) the selective exposure is performed. Then, the photoresist film is subjected to a heat treatment (post exposure baking) step, and (5) the photoresist film after the heat treatment is subjected to development processing using an alkali aqueous solution, and the pattern size is 2.0# on the substrate. The photoresist pattern for integrated circuits below m and the step of forming a photoresist pattern for the liquid crystal display portion exceeding 2.0 Am are formed as such. 7. The method for forming a photoresist pattern according to claim 6, wherein the step of (3) selective exposure is performed by using an i-line at a light source -37-1286269 (3), and The exposure process under a low-lying condition of 0.3 or less is performed. -38-