JP2009282308A - Photosensitive resin composition containing sulfonic acid compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition, having high transparency and high sensitivity, excels in solvent resistance when formed into a cured film, and substantially avoids changes in pattern shape, and the like, due to the difference in post-bake temperature over a wide temperature range, and to provide a cured film obtained from the composition. <P>SOLUTION: The positive photosensitive resin composition comprises (A) an alkali-soluble acrylic polymer having an aliphatic hydroxyl group in a side chain, (B) a 1,2-quinonediazide compound, (C) a sulfonic acid compound and (D) a solvent. The cured film obtained using the composition and a liquid crystal display element containing the cured film are also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a positive photosensitive resin composition and a cured film obtained therefrom. More specifically, the present invention relates to a positive photosensitive resin composition suitable for use in display materials, a cured film thereof, and various materials using the cured film.

In general, in an optical device such as a thin film transistor (TFT) type liquid crystal display element, an organic EL (electroluminescent) element, and a solid-state imaging element, various cured films such as a protective film, a planarizing film, and an insulating film are used depending on the application. ing.
For example, the protective film provided to prevent the element surface from being exposed to a solvent or heat during the manufacturing process has not only high adhesion to the substrate to be protected and high solvent resistance, but also transparency, heat resistance, Is required to have good performance such as dimensional stability.
In addition, when such a protective film is used as a protective film for a color filter used in a color liquid crystal display device or a solid-state imaging device, generally the performance of flattening the color filter or black matrix resin of the underlying substrate, that is, flat It is also required to have performance as a chemical film.

In the production of various films for such various electronic materials, acrylic resins having the property of imparting heat resistance and solvent resistance by thermosetting or photocuring are widely used.
As a general thermosetting method, a method of adding an epoxy-based cross-linking agent to an acrylic resin containing a carboxyl group is well known. A method of curing (see Patent Document 1) has also been proposed.

The optical device is also provided with a patterned electrode protective film, planarization film, insulating film, and the like. As a material for forming a cured film patterned in this way, the photosensitive resin composition having a feature that the number of steps for obtaining a required pattern shape is small and has sufficient flatness, Widely used than before.
These films have excellent process resistance such as heat resistance, solvent resistance, long-time firing resistance, and metal sputtering resistance, good adhesion to the substrate, and various processes according to the purpose of use. Various characteristics such as having a wide process margin capable of forming a pattern under conditions, high sensitivity and high transparency, and less film unevenness after development are required.

From the viewpoint of such required characteristics, conventionally, resins containing a naphthoquinone diazide compound have been widely used as the photosensitive resin composition. For example, an epoxy compound is generated from a naphthoquinone diazide compound by light irradiation during baking. There is a proposal of a radiation-sensitive resin composition for microlenses (Patent Document 2) that utilizes a mechanism of thermosetting by reacting with carboxylic acid.
JP 2000-103937 A JP-A-4-352101

As described above, in various applications for various electronic materials, the cured film obtained is widely used by utilizing the mechanism of thermal curing (crosslinking) by the reaction of carboxylic acid (carboxyl group) and epoxy compound during post-baking. Has been.
However, the resin composition (solution) containing an epoxy crosslinking system has a problem of high reactivity at room temperature, that is, low storage stability. Moreover, the pattern shape tends to change depending on the baking temperature during post-baking, and precise temperature control is required.

  The present invention has been made in view of the above circumstances, maintains high transmittance, is highly sensitive, and changes in the pattern shape and the like due to the difference in temperature occur mostly in a wide post-bake temperature range. The object is to provide a positive photosensitive resin composition.

As a result of intensive studies to solve the above problems, the present inventors have found the present invention.
That is, as a 1st viewpoint, it is related with the positive photosensitive resin composition containing the following (A) component, (B) component, (C) component, and (D) solvent.
(A) component: an alkali-soluble acrylic polymer having an aliphatic hydroxyl group in the side chain;
(B) component: 1,2-quinonediazide compound,
(C) component: a sulfonic acid compound,
(D) Solvent.
As a 2nd viewpoint, it is related with the positive photosensitive resin composition as described in a 1st viewpoint whose number average molecular weight of the alkali-soluble acrylic polymer of (A) component is 2,000 thru | or 30,000 in polystyrene conversion.
As a third aspect, the positive photosensitive resin according to the first aspect or the second aspect, which contains 5 to 100 parts by mass of the component (B) with respect to 100 parts by mass of the component (A). The present invention relates to a resin composition.
As 4th viewpoint, 0.1 thru | or 30 mass parts (C) component is contained with respect to 100 mass parts of (A) component, It is any one among the 1st viewpoint thru | or 3rd viewpoint characterized by the above-mentioned. The positive photosensitive resin composition described in the item.
As a fifth aspect, as the component (E), the surfactant is further contained in an amount of 1.0% by mass or less in the positive photosensitive resin composition, according to any one of the first aspect to the fourth aspect. The present invention relates to a positive photosensitive resin composition.
As a sixth aspect, as the component (F), 0.1 to 20 parts by mass of an adhesion promoter is further contained in the positive photosensitive resin composition, as described in any one of the first to fifth aspects. To a positive photosensitive resin composition.
As a seventh aspect, the present invention relates to a cured film obtained using the positive photosensitive resin composition according to any one of the first aspect to the sixth aspect.
As an 8th viewpoint, it is related with the liquid crystal display element which has a cured film as described in a 7th viewpoint.
As a ninth aspect, the present invention relates to an array flattening film for a liquid crystal display comprising the cured film described in the seventh aspect.
As a 10th viewpoint, it is related with the interlayer insulation film which consists of a cured film as described in a 7th viewpoint.

  The positive photosensitive resin composition of the present invention has sufficiently high sensitivity, is so small that the film loss in the unexposed area can be ignored during development, and has excellent transparency. It is excellent in resistance, and in particular, the effect that the change in shape due to the difference in curing temperature is small is obtained.

  Further, according to the present invention, a cured film obtained by using such a positive photosensitive resin composition becomes a cured film that is excellent in solvent resistance and hardly changes in shape due to a change in curing temperature. The effect that it is suitable also for the use of various film materials in the liquid crystal or organic EL display such as the array flattening film of the element, and the use of the micro lens or the like is obtained.

The photosensitive resin composition of the present invention comprises an alkali-soluble acrylic polymer having an aliphatic hydroxyl group in the side chain of the following component (A), a quinonediazide compound of component (B), a sulfonic acid compound of component (C), and (D) It is a composition containing a solvent and optionally containing a surfactant as the component (E), an adhesion promoter as the component (F), and other additives.
Hereinafter, details of each component will be described.

<(A) component>
The component (A) has a side chain having an aliphatic hydroxyl group (hereinafter also simply referred to as a specific side chain) in the structure of the acrylic polymer, and has a polystyrene-equivalent number average molecular weight (hereinafter referred to as a number average molecular weight). Is an alkali-soluble acrylic polymer (hereinafter also simply referred to as an acrylic polymer) having a molecular weight of 2,000 to 30,000.

In the present invention, the acrylic polymer means acrylic monomers such as acrylic acid and methacrylic acid, and salts and esters thereof (acrylic acid ester, methacrylic acid ester, etc.), and a monomer having an unsaturated double bond such as styrene if necessary. Used to refer to a polymer obtained by homopolymerization or copolymerization.
The alkali-soluble acrylic polymer of the component (A) may be any acrylic polymer having such a structure and soluble in alkali, and the main chain skeleton of the polymer constituting the acrylic polymer and the specific side chain. There are no particular restrictions on the types of side chains that may be present.

  However, if the alkali-soluble acrylic polymer (A) has an excessive number average molecular weight exceeding 30,000, development residues are likely to occur, and the sensitivity is greatly reduced, while the number average molecular weight is low. If it is less than 2,000 and is too small, curing may be insufficient at the time of thermal curing and solvent resistance may be reduced, or a considerable amount of film loss may occur at the unexposed area during development, resulting in insufficient curing.

The method for obtaining the acrylic polymer having the specific side chain as described above (component (A)) is not particularly limited. For example, the monomer having an aliphatic hydroxyl group and the alkali-soluble substituent can be obtained by a polymerization method such as radical polymerization. A method of copolymerizing the monomers having is simple. Here, any of the monomer having an aliphatic hydroxyl group and the monomer having an alkali-soluble substituent may be an acrylic monomer, or both may be an acrylic monomer.
Examples of the alkali-soluble substituent include a carboxyl group and a phenolic hydroxyl group. In the present invention, a monomer having a carboxyl group as an alkali-soluble substituent can be particularly preferably used.

  Examples of the monomer having an aliphatic hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2, 3 -Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, Poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyl Shi-6-hydroxy-norbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxy-norbornene-2-carboxylic-6-lactone and the like.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl). ) Maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.

In the present invention, when an acrylic polymer having a specific side chain is obtained, a monomer having a non-reactive functional group that can be copolymerized with the monomer having the specific side chain and the monomer having a carboxyl group is used in combination. can do.
Specific examples of the monomer having a non-reactive functional group include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
Hereinafter, although the specific example of the said monomer is given, it is not limited to these.

  Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate. Tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2 -Methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate Rate, 8-methyl-8-tricyclodecyl acrylate, and the like 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate. Tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2 -Methyl-2-adamantyl methacrylate Over DOO, .gamma.-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate.

  Examples of the acrylamide compound include N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, and the like.

  Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy- Examples include 5-hexene and 1,7-octadiene monoepoxide.

  Examples of the styrene compound include styrene, hydroxystyrene, methylstyrene, chlorostyrene, bromostyrene, and the like.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N- (hydroxyphenyl) maleimide, and N-cyclohexylmaleimide.

As described above, the method for obtaining the acrylic polymer having a specific side chain used in the present invention is not particularly limited. For example, a monomer having a specific side chain, a monomer having a carboxyl group, and other copolymerizable non-reactive properties. It can be obtained by carrying out a polymerization reaction at a temperature of 50 to 110 ° C. in a solvent in which a monomer having a functional group and, if desired, a polymerization initiator coexist. In that case, the solvent used will not be specifically limited if the monomer which comprises the acrylic polymer which has a specific side chain, and the acrylic polymer which has a specific side chain are dissolved. As a specific example, the solvent described in the (D) solvent mentioned later is mentioned.
The acrylic polymer having a specific side chain thus obtained is usually in a solution state dissolved in a solvent.

In addition, the acrylic polymer solution having a specific side chain obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the generated precipitate is filtered and washed. Acrylic polymer powder having a specific side chain can be obtained by drying at room temperature or under heat under reduced pressure or reduced pressure. By such an operation, the polymerization initiator and unreacted monomer coexisting with the acrylic polymer having a specific side chain can be removed, and as a result, a purified acrylic polymer powder having the specific side chain can be obtained. . If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
In the present invention, the acrylic polymer powder having the specific side chain may be used as it is, or the powder may be redissolved in a solvent (D) described later and used as a solution. .
In the present invention, the acrylic polymer as the component (A) may be a mixture of acrylic polymers having a plurality of types of specific side chains.

<(B) component>
The 1,2-quinonediazide compound as component (B) is a compound having either a hydroxyl group or an amino group, or a compound having both a hydroxyl group and an amino group, and these hydroxyl groups or amino groups (hydroxyl groups). 10 to 100 mol%, particularly preferably 20 to 95 mol% of the total amount) is esterified or amidated with 1,2-quinonediazidesulfonic acid. Compounds can be used.

Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 1,3,3-tris (4-hydroxyphenyl). Butane, 4,4-isopropylidene diphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxyphenylsulfone, 4,4- Hexafluoroisopropylidenediphenol, 4,4 ', 4'
'-Trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4'-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 3 , 4,4′-pentahydroxybenzophenone, phenol compounds such as 2,5-bis (2-hydroxy-5-methylbenzyl) methyl, ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, Diethylene glycol, dipropylene glycol, 2-methoxy ester Mention may be made of aliphatic alcohols such as butanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate and butyl lactate.

Examples of the compound containing an amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine. , Anilines such as 4,4′-diaminophenylmethane and 4,4′-diaminodiphenyl ether, and aminocyclohexane.

  Furthermore, examples of the compound containing both a hydroxyl group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, 2,4-diaminophenol, 4,4′-diamino-4 ″ -hydroxytriphenylmethane, 4-amino-4 ′, 4 ″ -dihydroxytriphenylmethane, bis (4-amino-3-carboxy-5-hydroxyphenyl) ether, bis (4-amino-3-carboxy-5-hydroxyphenyl) methane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) propane, 2,2-bis (4-amino-3-carboxy) Aminophenols such as -5-hydroxyphenyl) hexafluoropropane, 2-aminoethano Le, 3-aminopropanol, mention may be made of alkanolamines, such as 4-amino-cyclohexanol.

  These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

  The content of the component (B) in the positive photosensitive resin composition of the present invention is preferably 5 to 100 parts by weight, more preferably 8 to 50 parts by weight, more preferably 100 parts by weight of the component (A). The amount is preferably 10 to 40 parts by mass. When the amount is less than 5 parts by mass, the difference in dissolution rate between the exposed portion and the unexposed portion of the positive photosensitive resin composition in the developer becomes small, and patterning by development may be difficult. When the amount exceeds 100 parts by mass, the 1,2-quinonediazide compound is not sufficiently decomposed by exposure in a short time, so that the sensitivity is reduced, or the component (B) absorbs light and the transparency of the cured film. May be reduced.

<(C) component>
In the positive photosensitive resin composition of the present invention, by using a sulfonic acid ester compound as the component (C), it is possible to promote thermal crosslinking between the polymers and to prevent the pattern from reflowing during post-baking. .
Examples of the sulfonic acid compound as component (C) include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfone. Acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 1H , 2H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, and the like.

  The content of the component (C) in the positive photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts per 100 parts by mass of the component (A). Part by mass, more preferably 1 to 10 parts by mass. When the amount is less than 0.1 parts by mass, thermosetting does not proceed and the solvent resistance is insufficient, or the pattern size after firing may increase. On the other hand, if it exceeds 30 parts by mass, partial curing may start during pre-baking, and a residual film may be generated in the exposed area, or the pattern after curing may shrink and become smaller.

<(D) Solvent>
The (D) solvent used in the present invention dissolves the (A) component, the (B) component, and the (C) component, and dissolves the (E) component and / or the (F) component, which will be added as required. As long as the solvent has such solubility, the type and structure thereof are not particularly limited.
Examples of such a solvent (D) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol. Monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 2-hydroxypropion Ethyl acetate, ethyl 2-hydroxy-2-methylpropionate, ethoxy vinegar Ethyl, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, pyruvate Examples include ethyl, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

These solvents can be used singly or in combination of two or more.
Among these (D) solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. have good coating properties and safety Is preferable from the viewpoint of high. These solvents are generally used as solvents for photoresist materials.

<(E) component>
Component (E) is a surfactant. The positive photosensitive resin composition of the present invention can further contain a surfactant for the purpose of improving the coating properties as long as the effects of the present invention are not impaired.

(E) Although it does not restrict | limit especially as surfactant of a component, For example, a fluorine-type surfactant, a silicone type surfactant, a nonionic surfactant etc. are mentioned. As this type of surfactant, for example, commercially available products such as those manufactured by Gemco Co., Ltd., Sumitomo 3M Co., Ltd., Dainippon Ink Chemical Co., Ltd., or Asahi Glass Co., Ltd. can be used. These commercial products are convenient because they can be easily obtained. Specific examples thereof include F-top EF301, EF303, EF352 (manufactured by Gemco Co., Ltd.), MegaFac R30, R08, R90, BL20, R61, F171, F173, F471, F475, F479, F474, F477, F480. F482, F483, F484 (Dainippon Ink Chemical Co., Ltd.), Florard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, Fluorosurfactants such as SC106 (Asahi Glass Co., Ltd.) can be used.
(E) The surfactant of a component can be used individually by 1 type or in combination of 2 or more types.
When the surfactant is used, the content thereof is usually 1.0% by mass or less, preferably 0.5% by mass or less, in 100% by mass of the positive photosensitive resin composition. Even when the amount of the surfactant (E) used is set to an amount exceeding 1.0% by mass, the effect of improving the coating property becomes dull and not economical.

<(F) component>
Component (F) is an adhesion promoter. The positive photosensitive resin composition of the present invention may contain an adhesion promoter for the purpose of improving the adhesion to the substrate after development. Specific examples of such adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, Alkoxysilanes such as diphenyldimethoxysilane and phenyltriethoxysilane, hexamethyldisilazane, N, N′-bis (trimethylsilyl) urea, silazanes such as dimethyltrimethylsilylamine, trimethylsilylimidazole, vinyltrichlorosilane, γ-aminopropyltri Ethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (N-piperidini ) Silanes such as propyltriethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, etc. Examples thereof include cyclic compounds, urea such as 1,1-dimethylurea and 1,3-dimethylurea, and thiourea compounds.

As the adhesion promoter, for example, commercially available compounds such as those manufactured by Shin-Etsu Chemical Co., Ltd., GE Toshiba Silicone Co., Ltd., and Toray Dow Corning Co., Ltd. can be used. It is readily available.
As the component (F), one or two or more of the adhesion promoters can be used.
The addition amount of these adhesion promoters is usually 20 parts by mass or less, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A). is there. If it exceeds 20 parts by mass, the heat resistance of the coating film may be reduced, and if it is less than 0.1 parts by mass, sufficient effects of the adhesion promoter may not be obtained.

<Other additives>
Furthermore, as long as the positive photosensitive resin composition of the present invention does not impair the effects of the present invention, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, or a polyhydric phenol, A dissolution accelerator such as a polyvalent carboxylic acid can be contained.

<Positive photosensitive resin composition>
The positive photosensitive resin composition of the present invention comprises an alkali-soluble alkali polymer having an aliphatic hydroxyl group in the side chain of component (A), a 1,2-quinonediazide compound of component (B), and a sulfonic acid of component (C). A composition containing a compound and (D) solvent, and optionally further comprising at least one of a surfactant of component (E), an adhesion promoter of component (F), and other additives. It is a thing.

Among these, preferred examples of the positive photosensitive resin composition of the present invention are as follows.
[1]: Based on 100 parts by mass of component (A), 5 to 100 parts by mass of component (B) and 0.1 to 30 parts by mass of component (C) are contained, and these components are used as solvent (D). A dissolved positive photosensitive resin composition.
[2]: The positive photosensitive resin composition further containing 1.0% by mass or less of the component (E) based on 100 parts by mass of the component (A) in the composition of the above [1].
[3] A positive photosensitive resin composition further comprising 0.1 to 20 parts by mass of the component (F) based on 100 parts by mass of the component (A) in the composition of the above [1] or [2].

  The ratio of the solid content in the positive photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, and is, for example, 1 to 80% by mass. It is 5 to 60% by mass, or 10 to 50% by mass. Here, solid content means what remove | excluded the (D) solvent from all the components of the positive photosensitive resin composition.

  Although the preparation method of the positive photosensitive resin composition of this invention is not specifically limited, As the preparation method, (A) component (acrylic polymer which has a specific side chain) is melt | dissolved in (D) solvent, for example. (B) component (1,2-quinonediazide compound) and (C) component (sulfonic acid compound) are mixed in this solution at a predetermined ratio to obtain a uniform solution, or an appropriate stage of this preparation method. In the method, there may be mentioned a method in which (E) component (surfactant), (F) component (adhesion promoter) and other additives are further added and mixed as necessary.

  In the preparation of the positive photosensitive resin composition of the present invention, (D) a solution of an acrylic polymer having a specific side chain obtained by a polymerization reaction of the acrylic polymer having a specific side chain in a solvent is used as it is. In this case, when the component (B), the component (C), etc. are added to the solution of the component (A) in the same manner as described above to obtain a uniform solution, the solvent (D) is further added for the purpose of adjusting the concentration. Additional inputs may be made. At this time, the solvent (D) used in the process of forming the acrylic polymer having a specific side chain is the same as the solvent (D) used for adjusting the concentration when preparing the positive photosensitive resin composition. It may be different or different.

Thus, the prepared positive photosensitive resin composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

<Coating film and cured film>
The positive photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, or an ITO substrate. Etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit, ink jet coating, etc., and then pre-drying in a hot plate or oven etc. to form a coating film can do. Then, a positive photosensitive resin film is formed by heat-treating this coating film.

  As conditions for this heat treatment, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C. to 160 ° C. and a time of 0.3 to 60 minutes are employed. The heating temperature and heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes.

  The film thickness of the positive photosensitive resin film formed from the positive photosensitive resin composition is, for example, 0.1 to 30 μm, is, for example, 0.2 to 10 μm, and is further, for example, 0.2 to 5 μm. It is.

  On the coating film obtained above, a mask having a predetermined pattern is mounted, irradiated with light such as ultraviolet rays, and developed with an alkali developer, so that the exposed portion is washed out and a sharp relief pattern on the end face Is obtained.

  Examples of the alkaline developer that can be used include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline. Alkaline aqueous solutions such as amine aqueous solutions such as ethanolamine, propylamine, and ethylenediamine. Further, a surfactant or the like can be added to these developers.

  Among the above, a tetraethylammonium hydroxide 0.1 to 2.38 mass% aqueous solution is generally used as a photoresist developer, and the alkaline developer is also used in the photosensitive resin composition of the present invention. It can be developed satisfactorily without causing problems such as swelling.

  Further, as a developing method, any of a liquid piling method, a dipping method, a rocking dipping method, and the like can be used. The development time at that time is usually 15 to 180 seconds.

  After the development, the positive photosensitive resin film is washed with running water, for example, for 20 to 90 seconds, and then air-dried with compressed air or compressed nitrogen or by spinning to remove moisture on the substrate, and A patterned film is obtained.

  Subsequently, the pattern forming film is subjected to post-baking for thermosetting, specifically by heating using a hot plate, an oven, etc., thereby providing heat resistance, transparency, and flatness. In addition, a film having a good relief pattern with excellent water absorption and chemical resistance can be obtained.

  The post-bake is generally processed at a heating temperature selected from the range of 140 ° C. to 250 ° C. for 5 to 30 minutes when on a hot plate and 30 to 90 minutes when in an oven. The method is taken.

  Thus, such a post-bake can provide a target cured film having a good pattern shape.

  As described above, with the positive photosensitive resin composition of the present invention, it is possible to form a coating film that has sufficiently high sensitivity and has a very small unexposed area during development and a fine pattern. it can.

  Moreover, the cured film obtained from this coating film has the characteristics that it is excellent in heat resistance and solvent resistance, and is highly transparent. For this reason, it can be suitably used in applications such as an array flattening film of a TFT type liquid crystal element together with various films in a liquid crystal display and an organic EL display such as an interlayer insulating film, a protective film, and an insulating film.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these Examples.

[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
MAA: methacrylic acid MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate CHMI: N-cyclohexylmaleimide PTSA: p-toluenesulfonic acid CAMSA: camphorsulfonic acid PSA: propylsulfonic acid AIBN: azobisisobutyronitrile PGMEA: propylene glycol Monomethyl ether acetate QD: Condensation of α, α, α′-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene 1 mol and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride 1.5 mol A compound synthesized by reaction.
CL1: Epolide GT-401 (alicyclic epoxy resin) manufactured by Daicel Chemical Industries, Ltd.
MPTS: γ-methacryloxypropyltrimethoxysilane R30: manufactured by Dainippon Ink & Chemicals, Inc. Megafax R-30 (trade name)

[Measurement of number average molecular weight and weight average molecular weight]
The number average molecular weight and weight average molecular weight of the acrylic polymer having a specific side chain obtained in accordance with the following synthesis example were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation. Tetrahydrofuran was flowed through the column at a flow rate of 1 ml / min (column temperature: 40 ° C.) for elution. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

<Synthesis Example 1>
MAA 10.9 g, CHMI 35.3 g, HEMA 25.5 g, MMA 28.3 g are used as monomer components constituting an acrylic polymer having a specific side chain, and AIBN 5 g is used as a radical polymerization initiator. Was subjected to a polymerization reaction at a temperature of 60 ° C. to 100 ° C. in 150 g of a solvent PGMEA to obtain a solution of (A) component (copolymer concentration: 40.0% by mass) as Mn 3,800 and Mw 6,700. (P1)

<Synthesis Example 2>
MAA 12.9 g, CHMI 35.3 g, HEMA 25.5 g, MMA 26.3 g are used as monomer components constituting an acrylic polymer having a specific side chain, and AIBN 5 g is used as a radical polymerization initiator. Was subjected to a polymerization reaction at a temperature of 60 ° C. to 100 ° C. in 150 g of a solvent PGMEA to obtain a solution of (A) component (copolymer concentration: 40.0% by mass) as Mn 4,100 and Mw 6,900. (P2)

<Examples 1 to 4 and Comparative Examples 1 to 3>
According to the composition shown in the following Table 1, (B) component and (C) component, (D) solvent, and further (E) component and (F) component are mixed in a predetermined ratio to the solution of component (A), By stirring at room temperature for 3 hours to obtain a uniform solution, positive type photosensitive resin compositions of Examples and Comparative Examples were prepared.

For each of the obtained positive photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3, the sensitivity of the coating film, film reduction (in the unexposed area), change in pattern dimensions during thermosetting,
The solvent resistance of each cured film was measured and evaluated.

[Evaluation of sensitivity]
The positive photosensitive resin composition was applied on a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 90 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5.5 mW / cm ² for a predetermined time by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Thereafter, development was performed by immersing in a 0.4% by mass tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution for 60 seconds, followed by washing with running ultrapure water for 20 seconds. The lowest exposure amount (mJ / cm ² ) at which no undissolved portion remained in the exposed area was defined as sensitivity.

[Evaluation of film reduction]
The positive photosensitive resin composition was applied on a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 90 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. This membrane was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds and then washed with running ultrapure water for 20 seconds. Subsequently, the thickness of this film was measured to evaluate the degree of film reduction in the unexposed area due to development. The film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.

[Evaluation of solvent resistance]
The positive photosensitive resin composition was applied on a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 90 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. This coating film was post-baked by heating at 230 ° C. for 30 minutes to form a cured film having a thickness of 2.1 μm. This coating film was immersed in NMP for 1 minute at room temperature. A film having no change in film thickness before and after immersion was marked with ◯, and a film with a decrease in film thickness was marked with x.

[Evaluation of pattern dimension change]
The positive photosensitive resin composition was applied on a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 90 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. The coating film by ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. is the light intensity at 365nm was 150 mJ / cm ² irradiation through a mask of a line and space pattern of 8μm with ultraviolet rays at 5.5 mW / cm ^2. Thereafter, development was performed by immersing in a 0.4 mass% TMAH aqueous solution for 60 seconds, followed by washing with running ultrapure water for 20 seconds to form a pattern. The prepared pattern was baked for 3 minutes on a 140 ° C. hot plate and then baked for 15 minutes on a 230 ° C. hot plate, and was baked for 15 minutes only at 230 ° C. without baking at 140 ° C. Each was observed with a scanning electron microscope (SEM), and the amount of change in the pattern line width due to the difference in firing time was measured.

[Evaluation of transmittance]
The positive photosensitive resin composition was applied on a quartz substrate using a spin coater and then pre-baked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a thickness of 2.5 μm. This coating film was irradiated with ultraviolet rays having a light intensity at 365 nm of 5.5 mW / cm ² for 120 seconds using an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. Thereafter, this film was post-baked on a hot plate at a temperature of 230 ° C. for 30 minutes to form a cured film. The cured film was measured for transmittance at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SHIMADSU UV-2550 model number, manufactured by Shimadzu Corporation).

[Evaluation results]
The results of the above evaluation are shown in Table 2 below.

  As can be seen from the results shown in Table 2, all of the positive photosensitive resin compositions of Examples 1 to 4 were highly sensitive, and the film loss in the unexposed areas was very small. Furthermore, a pattern with excellent solvent resistance after forming the cured film, a very small change in line width due to the difference in the firing temperature, and a cured film having high transmittance was obtained.

On the other hand, in Comparative Example 1 containing no sulfonic acid compound, thermosetting by post-baking did not occur, sufficient solvent resistance was not obtained, and the change in pattern line width was large.
For Comparative Examples 2 and 3, a cured film having sufficient solvent resistance and high transmittance can be obtained after post-baking, but the sensitivity is lower than that of the Examples, and the line width of the pattern is different due to the difference in the firing temperature. As a result, changes occurred.

  The positive photosensitive resin composition according to the present invention is suitable as a material for forming a cured film such as a protective film, a planarizing film, and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element. In particular, it is also suitable as a material for forming an interlayer insulating film of a TFT type liquid crystal element, a protective film for a color filter, an array flattening film, a concavo-convex film below a reflective film of a reflective display, an insulating film of an organic EL element, etc. Furthermore, it is also suitable as various electronic materials such as a microlens material.

Claims (10)

A positive photosensitive resin composition comprising the following component (A), component (B), component (C) and solvent (D).
(A) component: an alkali-soluble acrylic polymer having an aliphatic hydroxyl group in the side chain;
(B) component: 1,2-quinonediazide compound,
(C) component: a sulfonic acid compound,
(D) Solvent. The positive photosensitive resin composition according to claim 1, wherein the alkali-soluble acrylic polymer of component (A) has a number average molecular weight of 2,000 to 30,000 in terms of polystyrene. The positive photosensitive resin composition according to claim 1, comprising 5 to 100 parts by mass of the component (B) with respect to 100 parts by mass of the component (A). The positive component according to any one of claims 1 to 3, wherein 0.1 to 30 parts by mass of the component (C) is contained with respect to 100 parts by mass of the component (A). Type photosensitive resin composition. The positive photosensitive resin according to any one of claims 1 to 4, further comprising 1.0% by mass or less of a surfactant as a component (E) in the positive photosensitive resin composition. Composition. The positive photosensitive resin according to any one of claims 1 to 5, further comprising 0.1 to 20 parts by mass of an adhesion promoter as a component (F) in the positive photosensitive resin composition. Resin composition. The cured film obtained using the positive photosensitive resin composition as described in any one of Claims 1 thru | or 6. A liquid crystal display element having the cured film according to claim 7. An array planarizing film for a liquid crystal display comprising the cured film according to claim 7. An interlayer insulating film comprising the cured film according to claim 7.