TWI663477B - Positive photosensitive resin composition - Google Patents

Abstract

An object of the present invention is to provide a positive-type photosensitive resin composition which has very high sensitivity, high transparency, and can form a cured film with a small shape change in a wide baking temperature range during post-baking.

The solution is a positive-type photosensitive resin composition containing the following (A) component, (B) component, (C) component, (D) component, and (E) solvent.

(A) alkali-soluble acrylic polymer, (B) component: 1,2-quinonediazide compound, (C) component: compound having an isocyanurate skeleton and two or more polymerizable unsaturated double bonds (D) component: a crosslinkable compound having two or more substituents selected from alkoxymethyl and hydroxymethyl, and (E) a solvent.

Description

Positive photosensitive resin composition

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-type photosensitive resin composition and a cured film thereof suitable for use in a display material, and various materials using the cured film.

Generally, display elements such as a thin film transistor (TFT) liquid crystal display element and an organic EL (electroluminescent) element are provided with an electrode protection film, a planarization film, an insulating film, and the like formed in a pattern. As materials for forming such films, among the photosensitive resin compositions, photosensitive resin compositions having a small number of steps required to obtain a necessary pattern shape and having sufficient flatness have been widely used.

In addition, the above-mentioned films require excellent process resistance in addition to process resistance such as heat resistance, solvent resistance, long-term firing resistance, and metal sputtering resistance, and adhesion to the substrate, which can still be used under various process conditions for the purpose of use. Form a wide process margin of the pattern, and more demand for high sensitivity and transparency, and the non-uniform film after development Various characteristics. Therefore, from the viewpoint of the required characteristics, as the above-mentioned photosensitive resin composition, a resin containing a naphthoquinonediazide compound has been widely used in the past.

It has been proposed that by adding an epoxy cross-linking agent to these materials, and by including a carboxyl group and an epoxy group in an acrylic resin, the formed pattern is thermally cross-linked and hardened (Patent Document 1 and 2). However, when such a resin is used, sufficient sensitivity cannot be obtained, which results in a reduction in the throughput during the manufacture of the display. In addition, due to the baking temperature during post-baking, the shape of the pattern is easy to change, and precise temperature control is necessary.

In addition, it has also been proposed that an epoxy group be introduced into an acrylic resin, and a compound having at least one ethylenically unsaturated bond and having an isotricyanate skeleton be used in combination to heat the formed pattern. Crosslinked and hardened (Patent Document 3). However, the document 3 does not describe the improvement of the dimensional stability of the pattern shape and the heat resistance after metal sputtering by using a crosslinkable compound having a specific structure in combination.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2000-103937

[Patent Document 2] Japanese Unexamined Patent Publication No. 4-352101

[Patent Document 3] Japanese Patent Laid-Open No. 2010-134422

The present invention has been made in view of the above circumstances, and provides a positive-type photosensitive resin composition capable of forming a pattern with high sensitivity while maintaining adhesion during development, and maintaining a cured film at a high level. In the state of the step flattening performance, the shape change during post-baking is small, and a hardened film with high metal sputtering resistance can be formed.

The present inventors have completed the present invention as a result of careful research in order to solve the above-mentioned problems. That is, this invention relates to the following.

A positive-type photosensitive resin composition comprising the following components (A), (B), (C), (D), and (E) a solvent.

(A) alkali-soluble acrylic polymer, (B) component: 1,2-quinonediazide compound, (C) component: compound having an isocyanurate skeleton and two or more polymerizable unsaturated double bonds (D) component: a crosslinkable compound having two or more substituents selected from alkoxymethyl and hydroxymethyl, and (E) a solvent.

2. The positive-type photosensitive resin composition according to the above 1, wherein the (A) component coefficient is an alkali-soluble acrylic polymer having an average molecular weight of 2,000 to 30,000 in terms of polystyrene.

3. The positive-type photosensitive resin composition according to 1 or 2 above, wherein the phase The component (B) is 5 to 100 parts by mass for 100 parts by mass of the (A) component.

4. The positive-type photosensitive resin composition according to any one of the above 1 to 3, wherein the (C) component is 5 to 60 parts by mass with respect to 100 parts by mass of the component (A).

5. The positive-type photosensitive resin composition according to any one of 1 to 3 above, wherein the (D) component is 5 to 50 parts by mass with respect to 100 parts by mass of the component (A).

6. The positive-type photosensitive resin composition according to any one of the above 1 to 4, wherein 100 parts by mass of the positive-type photosensitive resin composition further contains 0.01 to 1.0 part by mass of a surfactant as a component (F). .

7. The positive-type photosensitive resin composition according to any one of the above 1 to 5, wherein the positive-type photosensitive resin composition further contains (G) as a component with respect to 100 parts by mass of the (A) component. The adhesion promoter is 0.1 to 20 parts by mass.

8. A cured film obtained by using the positive-type photosensitive resin composition according to any one of 1 to 7 above.

9. A display element having the cured film according to 8 above.

10. An array flattening film for a display, comprising a cured film as described in 8 above.

11. An interlayer insulating film comprising a hardened film as described in 8 above.

The positive-type photosensitive resin composition of the present invention can form a pattern with a high sensitivity while maintaining the adhesion during development, and can form a small change in shape over a wide baking temperature range during post-baking, and Hardened film with high resistance to metal sputtering.

The photosensitive resin composition of the present invention is a positive-type photosensitive resin composition containing the following (A) component, (B) component, (C) component, (D) component, and (E) a solvent.

(A) alkali-soluble acrylic polymer, (B) component: 1,2-quinonediazide compound, (C) component: compound having an isocyanurate skeleton and two or more polymerizable unsaturated double bonds (D) component: a crosslinkable compound having two or more substituents selected from alkoxymethyl and hydroxymethyl, and (E) a solvent.

The details of each component are described below.

<(A) component>

The component (A) is an alkali-soluble acrylic polymer.

In the present invention, an acrylic polymer refers to homopolymerization or copolymerization using an unsaturated double bond monomer such as acrylic acid, methacrylic acid, acrylate, methacrylate, styrene, and maleimide. The resulting polymer.

The alkali-soluble acrylic polymer of the component (A) may be an alkali-soluble acrylic polymer, and the type of the backbone and side chains of the polymer main chain constituting the acrylic polymer is not particularly limited.

However, if the alkali-soluble acrylic polymer of the component (A) is an excessively large number average molecular weight of more than 30,000, the flattening performance with respect to the step difference is lowered. On the other hand, when the number-average molecular weight is less than 2,000, the average It may become insufficiently hardened during thermal curing and may reduce solvent resistance. Therefore, the number average molecular weight is in the range of 2,000 to 30,000.

As described above, as a method for synthesizing the alkali-soluble acrylic polymer as the component (A), it is relatively simple to use a monomer having any of a carboxyl group, an acid anhydride group, and a phenolic hydroxyl group, and a base such as maleimide. Method for copolymerizing soluble monomers.

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

Examples of the monomer having an acid anhydride group include anhydrous maleic acid and anhydrous itaconic acid.

Examples of the monomer having a phenolic hydroxyl group include p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, and N-hydroxyphenylpropenylamine. , N-hydroxyphenylmethacrylamide, 4-hydroxyphenylmethacrylate, and the like.

In the present invention, when obtaining an alkali-soluble acrylic polymer, a monomer that can be copolymerized with a monomer having an alkali-soluble group may be used in combination.

Specific examples of such a monomer include an acrylate compound, a methacrylate compound, an N-substituted maleimide compound, an acrylamide compound, acrylonitrile, a styrene compound, and a vinyl compound.

Although specific examples of the above-mentioned monomers are exemplified below, they are not limited thereto.

Examples of the acrylate compound include methacrylate, ethacrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methacrylate, and benzene. Acrylate, epoxy acrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isofluorenyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxy Butyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8- Ethyl-8-tricyclodecyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, diethylene glycol Alcohol monoacrylate, caprolactone 2- (propenyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, 5-propenyloxy-6-hydroxyl Ene-2-carboxylic-6-lactone and the like.

Examples of the methacrylate compound include For example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methylformate Acrylate, phenylmethacrylate, epoxypropylmethacrylate, phenoxyethylmethacrylate, 2,2,2-trifluoroethylmethacrylate, tert-butylmethacrylate Ester, cyclohexyl methacrylate, isofluorenyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethylmethyl Acrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ- Butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclic Decyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methyl Acrylate, diethylene glycol monomethacrylate, caprolactone 2- (methacryl) oxy) ethyl ester, poly (ethylene glycol) ethyl ether methacrylate, 5-methacryl Oxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone and the like.

Examples of the acrylamide compound include N-methacrylamide, N-methacrylamide, N, N-dimethylacrylamide, and N, N-dimethylmethyl Acrylamide, N-methoxymethacrylamide, N-methoxymethylmethacrylamine, N-butoxymethacrylamide, N-butoxymethylmethacrylamine Amine, etc.

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

Examples of the styrene compound include styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide Wait.

Moreover, it is preferable that the alkali-soluble acrylic polymer used in the present invention does not have an epoxy group or has a small amount even if it has an epoxy group from the viewpoint of storage stability.

The method for obtaining the alkali-soluble acrylic polymer used in the present invention is not particularly limited. For example, an alkali-soluble monomer, a copolymerizable monomer other than the alkali-soluble monomer, and a polymerization initiator as required may be used. It is obtained by performing a polymerization reaction in a solvent at a temperature of 50 to 110 ° C. In this case, the solvent to be used is not particularly limited as long as it is capable of dissolving the monomer constituting the alkali-soluble acrylic polymer and the acrylic polymer having a specific functional group. Specific examples include solvents described in the (E) solvent described later.

The alkali-soluble acrylic polymer thus obtained is usually in a solution state dissolved in a solvent.

As the alkali-soluble monomer or other copolymerizable monomers, the monomer having an epoxy group is not used at all, or even if the monomer having an epoxy group is used, the amount used is based on the amount used for polymerization. 100% Mo For ears, it is better to preset it to 10 mol or less.

Therefore, the alkali-soluble acrylic polymer used in the present invention is obtained by using no monomer having epoxy groups at all, or using a monomer having a small amount of epoxy groups (100 moles relative to all monomers used for polymerization). Ears are less than 10 moles).

In addition, the solution of the alkali-soluble acrylic polymer obtained by the above-mentioned implementation is put into diethyl ether or water under stirring to reprecipitate, and the resulting precipitate is filtered and washed, and then the mixture is washed at normal pressure or It can be made into powder of alkali-soluble acrylic polymer by drying at room temperature or heating under reduced pressure. With this operation, a polymerization initiator or an unreacted monomer coexisting with the alkali-soluble acrylic polymer can be removed. As a result, a powder of the purified alkali-soluble acrylic polymer can be obtained. When one operation does not fully purify, it is only necessary to re-dissolve the obtained powder in a solvent and repeat the above operation.

In the present invention, the powder of the alkali-soluble acrylic polymer may be used as it is, or the powder may be redissolved in a solvent such as the component (E) described later and used as a solution.

In the present invention, the acrylic polymer of the component (A) may be a mixture of a plurality of alkali-soluble acrylic polymers.

<(B) component>

As the 1,2-quinonediazide compound of the component (B), a compound having any one of a hydroxyl group or an amine group, or a compound having both a hydroxyl group and an amine group, and these hydroxyl or amine groups (in For both hydroxyl and amine groups, it is Among these total amounts), preferably 10 to 100 mole%, and particularly preferably 20 to 95 mole% are esterified with 1,2-quinonediazidesulfonic acid, or amidolated compounds.

Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, and galactose. Ethyl acetate, 1,3,3-ginseng (4-hydroxyphenyl) butane, 4,4-isopropylidene diphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1 -Bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxyphenylphosphonium, 4,4-hexafluoroisopropylidene diphenol, 4,4 ', 4 "-p-hydroxyphenylethyl Alkane, 1,1,1-phenylhydroxyphenylethane, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylene ] Bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4 , 4'-tetrahydroxybenzophenone, 2,2 ', 3,4,4'-pentahydroxybenzophenone, 2,5-bis (2-hydroxy-5-methylbenzyl) methyl, etc. Phenol compounds, ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2- Aliphatic alcohols such as methoxypropanol, 2-butoxypropanol, ethyl lactate, and butyl lactate.

Examples of the amine group-containing compound include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, and o- Phenylene diamine, m-phenylene diamine, p-phenylene diamine, 4,4'-diaminophenylmethane, 4,4'-diaminodiphenyl ether, etc. Class, amino cyclohexane.

Examples of the compound containing both a hydroxyl group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, and 4-amino group. Resorcinol, 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- Aminophenols such as bis (4-amino-3-carboxy-5-hydroxyphenyl) propane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) hexafluoropropane, Alkanolamines such as 2-aminoethanol, 3-aminopropanol, and 4-aminocyclohexanol.

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 mass, and more preferably 8 to 50 parts by mass relative to 100 parts by mass of the (A) component. More preferably, it is 10 to 40 parts by mass. If the content is less than 5 parts by mass, the difference in the dissolution rate of the developing solution between the exposed portion and the unexposed portion of the positive-type photosensitive resin composition becomes small, and it may be difficult to perform patterning from development. In addition, when it exceeds 100 parts by mass, the 1,2-quinonediazide compound cannot be sufficiently decomposed by exposure in a short period of time, so sensitivity may be reduced, or (B) component may absorb light and cause transparency of the cured film. Sexual decline.

<(C) component>

Examples of the compound having a component (C) having an isotricyanate skeleton and two or more polymerizable unsaturated double bonds include trimethylallyl isotricyanate, and ginseng (2-propylene Ethoxyethyl) isotricyanate, ginseng (2-methacryloxyethyl) isotricyanate, and the like.

These compounds can be used alone or in combination of two or more.

The content of the component (C) in the positive-type photosensitive resin composition of the present invention is preferably 5 to 60 parts by mass, and more preferably 10 to 50 parts by mass, relative to 100 parts by mass of the component (A). If it is less than 5 parts by mass, the adhesion at the time of development may be insufficient, or the step flatness may become small. Moreover, when it exceeds 60 mass parts, sensitivity may fall or a residue may generate | occur | produce after development.

<(D) component>

(D) A crosslinkable compound having two or more substituents selected from the group consisting of alkoxymethyl and hydroxymethyl is a cross-linking reaction due to dehydration condensation reaction when exposed to high temperature during heat curing . Examples of such compounds include compounds such as alkoxymethylated acetylene urea, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast-based compounds.

Specific examples of the alkoxymethylated acetylene urea include, for example, 1,3,4,6-methyl (methoxymethyl) acetylene urea, and 1,3,4,6-methyl (butoxy (Methyl) acetylene urea, 1,3,4,6- (Hydroxymethyl) acetylene urea, 1,3-bis (hydroxymethyl) urea, 1,1,3,3- (Butoxymethyl) ) Urea, 1,1,3,3-trimethyl (methoxymethyl) urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3- Bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone and the like. Examples of commercially available products include acetylene urea compounds (trade name: Cymel (registered trademark)) made by Mitsui Cytec (stock). 1170, Powderlink (registered trademark) 1174), methylated urea resin (trade name: UFR (registered trademark) 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin (high condensation type, trade name: Beckamine (registered trademark) J-300S, same P-955, same N) made by Dainippon Ink Chemical Industry Co., Ltd.

Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like. Examples of commercially available products include Mitsui Cytec (trade name) (trade name: Cymel (registered trademark) 1123), Sanyo Chemical Co., Ltd. (trade name: Nikalac (registered trademark)) BX-4000, and the same BX- 37. Same as BL-60, same as BX-55H).

Specific examples of the alkoxymethylated melamine include hexamethoxymethylmelamine and the like. Examples of commercially available products include methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, same 301, same 303, and 350) made by Mitsui Cytec (stock), butoxymethyl type Melamine compounds (trade names: Mycoat (registered trademark) 506, same as 508), methoxymethyl melamine compounds (trade names: Nikalac (registered trademark) MW-30, same MW-22, same MW- 11. Same as MW-100LM, same as MS-001, same as MX-002, same as MX-730, same as MX-750, and same as MX-035), butoxymethyl melamine compound (trade name: Nikalac (registered trademark) MX-45, same as MX-410, same as MX-302) and so on.

The component (D) may be a melamine compound or a urea compound in which the hydrogen atom of the amine group is replaced by a methylol group or an alkoxymethyl group. A compound obtained by condensing a substance, an acetylene urea compound, and a benzoguanamine compound. For example, a high molecular weight compound produced from a melamine compound and a benzoguanamine compound described in US Patent No. 6323310 can be mentioned. Examples of commercially available products of the melamine compound include, for example, trade names: Cymel (registered trademark) 303 (Mitsui Cytec), and examples of commercially available products of the benzoguanamine compound include: Cymel (registered trademark) 1123 (made by Mitsui Cytec).

Specific examples of the phenol resin compound include, for example, 2,6-bis (hydroxymethyl) phenol, 2,6-bis (hydroxymethyl) cresol, and 2,6-bis (hydroxymethyl)- 4-methoxyphenol, 3,3 ', 5,5'-methyl (hydroxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis (2-hydroxy-5) -Methylbenzyl alcohol), 4,4 '-(1-methylethylene) bis [2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis [2-methyl -6-hydroxymethylphenol], 4,4 '-(1-methylethylene) bis [2,6-bis (hydroxymethyl) phenol], 4,4'-methylenebis [2, 6-bis (hydroxymethyl) phenol], 2,6-bis (methoxymethyl) phenol, 2,6-bis (methoxymethyl) cresol, 2,6-bis (methoxymethyl) Phenyl) -4-methoxyphenol, 3,3 ', 5,5'-methyl (methoxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis ( 2-methoxy-5-methylbenzyl alcohol), 4,4 '-(1-methylethylene) bis [2-methyl-6-methoxymethylphenol], 4,4'- Methylenebis [2-methyl-6-methoxymethylphenol], 4,4 '-(1-methylethylene) bis [2,6-bis (methoxymethyl) phenol] , 4,4'-methylenebis [2,6-bis (methoxymethyl) phenol] and the like. It can also be obtained as a commercial product. As specific examples, 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA (Above, Asahi Organic Materials Industry (shares) system).

In addition, as the component (D), N-hydroxymethacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethacrylamide, and N-butoxy can also be used. A polymer made of acrylamide compound or methacrylamide compound substituted by hydroxymethyl or alkoxymethyl, such as methacrylamide.

Examples of such a polymer include poly (N-butoxymethacrylamide), a copolymer of N-butoxymethacrylamide and styrene, and N-hydroxymethylmethacryl Copolymer of fluorene and methmethacrylate, copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and N-butoxymethacrylamide and benzyl Copolymers of methacrylate and 2-hydroxypropyl methacrylate, etc. The weight average molecular weight of such a polymer is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

These crosslinkable compounds can be used alone or in combination of two or more.

The content of the component (D) in the positive-type photosensitive resin composition of the present invention is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, with respect to 100 parts by mass of the component (A). If it is less than 5 parts by mass, the heat resistance after metal sputtering may be reduced, or the leveling flatness may be reduced. Moreover, when it exceeds 50 mass parts, the adhesiveness at the time of image development may fall, or sensitivity may fall.

<(E) Solvent>

The (E) solvent used in the present invention dissolves the (A) component, (B) component, (C) component, and (D) component, and dissolves the component (F) to (G) component mentioned later as needed as needed. If it is a solvent having such a dissolving energy, its type and structure are not particularly limited.

Examples of such (E) solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and diethylene glycol. Alcohol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, stubble, methyl ethyl ketone, Cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, 2-hydroxy Ethyl-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate , N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

These solvents may be used singly or in combination of two or more kinds.

Among these (E) solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, and propylene glycol propyl are, from the viewpoint of good coating properties and high safety. Ether acetate, ethyl lactate, butyl lactate and the like are preferred. These solvents are generally used as a photoresist material.

<(F) component>

(F) The component is a surfactant. In the positive-type photosensitive resin composition of the present invention, a surfactant may be further contained within the scope of not impairing the effect of the present invention for the purpose of improving the coatability thereof.

The surfactant of the component (F) is not particularly limited, and examples thereof include a fluorine-based surfactant, a polysiloxane-based surfactant, and a nonionic surfactant. As such a surfactant, commercially available products such as Sumitomo 3M Co., Ltd., DIC Co., Ltd., and AGC Kiyomi Chemical Co., Ltd. can be used. These commercially available products are convenient because they are easily available. Specific examples thereof include PolyFox (registered trademark) PF-136A, 151, 156A, 154N, 159, 636, 6320, 656, 6520 (manufactured by Omnova), Megafac (registered trademark) R30, R08, R40, R41, R43, F251, F477, F552, F553, F554, F555, F556, F557, F558, F559, F560, F561, F562, F563, F565, F567, F570 (DIC (share) system), FC4430, FC4432 (Sumitomo 3M (stock) system, Asahiguard (registered trademark) AG710, Surflon (registered trademark) S-386, S-611, S-651, (AGC Qingmei Chemical (stock) system), Ftergent (registered trademark) FTX-218, DFX-18, 220P, 251, 212M, 215M (made by Neos) and other fluorine-based surfactants, BYK-300, 302, 306, 307, 310, 313, 315, 320, 322, 323, 325, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455 (by BYK Japan), SH3746, SH3749, SH3771, SH8400, SH8410, SH8700, SF8428 (Toray Dow Corning. Polysilicone Co., Ltd.), KF-351, KF-352, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-618, KF-6011, KF-6015 (made by Shin-Etsu Chemical Industry Co., Ltd.) and other polysiloxane based surfactants.

The (F) component surfactant may be used alone or in combination of two or more.

When a surfactant is used, its content is usually 0.01 to 1.0 parts by mass, preferably 0.02 to 0.8 parts by mass, in 100 parts by mass of the positive-type photosensitive resin composition. Even if the usage-amount of the surfactant of (F) component exceeds 1.0 mass part, the improvement effect of the said coating property becomes slow, and it becomes uneconomical. When it is 0.01 part or less, there may be a case where the coating property improvement effect is not exhibited.

<(G) component>

The (G) component is an adhesion promoter. The positive photosensitive resin composition of the present invention is for the purpose of improving the adhesion to the substrate after development, and an adhesion promoter may be added. Specific examples of such adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane. , Trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxy Silane, vinyltrichlorosilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane Silane, γ-glycidoxypropyltriethoxysilane, γ- (N-pipeline (Pyridyl) propyltriethoxysilane, 3-ureidopropyltriethoxysilane, alkoxysilanes such as 3-ureidopropyltrimethoxysilane, hexamethyldisilazane, N , N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilyl imidazole and other silazane, benzotriazole, benzimidazole, indazole, imidazole Heterocyclic compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, ureaazole, thiouracil, mercaptoimidazole, mercaptopyrimidine, or 1,1-dimethyl Urea, urea, such as 1,3-dimethylurea, or thiourea compounds.

As the adhesion promoter, for example, Shin-Etsu Chemical Industry Co., Ltd., Momentive Performance Materials Worldwide Inc., or Toray Dow Corning. Compounds of commercially available products such as polysiloxane, and these commercially available products can be easily obtained.

One or two or more of the adhesion promoters may be used in combination as the (G) component.

Among these (G) components, from the viewpoint of obtaining good adhesion, alkoxysilanes (that is, silane coupling agents) are preferred.

The addition amount of these adhesion promoters is usually 0.1 to 20 parts by mass, and preferably 0.5 to 10 parts by mass, with respect to 100 parts by mass of the component (A). When 20 mass parts or more is used, sensitivity may fall, and when it is less than 0.1 mass part, sufficient effect of an adhesion promoter may not be acquired.

<Other additives>

Furthermore, the positive photosensitive resin composition of the present invention does not damage Within the scope of the effect of the present invention, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, or a dissolution accelerator such as a polyvalent phenol or a polyvalent carboxylic acid may be contained as necessary.

<Positive photosensitive resin composition>

The positive photosensitive resin composition of the present invention is an alkali-soluble acrylic polymer of the component (A), a 1,2-quinonediazide compound of the component (B), and isocyanuric acid having the component of (C) A compound having an ester skeleton and two or more polymerizable unsaturated double bonds, and a crosslinkable compound having two or more substituents selected from the group consisting of alkoxymethyl and hydroxymethyl in the component (D) are dissolved in the solvent (E), and In addition, one or more components of the surfactant (F), the adhesion promoter of the (G) component, and other additives may be further contained as required.

Among them, preferred examples of the positive-type photosensitive resin composition of the present invention are as follows.

[1]: 5 to 100 parts by mass of the (B) component, 5 to 60 parts by mass of the (C) component, 5 to 50 parts by mass of the (D) component based on 100 parts by mass of the (A) component, and these The component is a positive-type photosensitive resin composition obtained by dissolving in a (E) solvent.

[2]: In the composition of the above [1], based on 100 parts by mass of the component (A), the positive photosensitive resin composition further contains 0.01 to 1.0 part by mass of the component (F).

[3]: In the composition of the above [1] or [2], based on 100 parts by mass of the (A) component, and further containing 0.1 to 20 parts by mass of the (F) component, a positive-type photosensitivity Resin composition.

The proportion of the solid content in the positive-type photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in a solvent, for example, it is 1 to 80% by mass, for example, 5 to 60% by mass. Or 10 to 50% by mass. Here, the solid content refers to a case where the (E) solvent is removed from all the components of the positive photosensitive resin composition.

The method for preparing the positive photosensitive resin composition of the present invention is not particularly limited, and examples of the method for preparing the positive photosensitive resin composition include dissolving the component (A) (alkali-soluble acrylic polymer) in the solvent (E), and In this solution, (B) the 1,2-quinonediazide compound of the component, the (C) component of the compound having an isotricyanate skeleton and two or more polymerizable unsaturated double bonds, and (D ) A method of preparing a homogeneous solution of a crosslinkable compound having two or more substituents selected from alkoxymethyl and hydroxymethyl, or, in an appropriate stage of the preparation method, add ( F) A method of mixing the component (surfactant), (G) component (adhesion promoter) and other additives.

When preparing the positive-type photosensitive resin composition of the present invention, a solution of a copolymer (alkali-soluble acrylic polymer) obtained by polymerization in a solvent (E) can be directly used. In this case, it is the same as above. When (B) component, (C) component, (D) component and the like are added to the solution of component (A) to make a homogeneous solution, for the purpose of adjusting the concentration, an (E) solvent may be additionally added. At this time, the (E) solvent used in the formation of the above-mentioned copolymer may be the same as the (E) solvent used to adjust the concentration when preparing the positive photosensitive resin composition. Can be different.

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

<Coated film and cured film>

The positive photosensitive resin composition of the present invention is a semiconductor substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate covered with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, ITO substrate, etc.), coating is performed by spin coating, cast coating, roll coating, slit coating, slit coating followed by spin coating, inkjet coating, etc. The coating film can be formed by pre-drying with a hot plate or an oven. Thereafter, this coating film is heat-treated to form a positive-type photosensitive resin film.

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

The film thickness of the positive-type photosensitive resin film formed from the positive-type photosensitive resin composition is, for example, 0.1 to 30 μm, for example, 0.2 to 10 μm, and further, for example, 0.3 to 8 μm.

On the obtained coating film, a mask having a predetermined pattern was mounted, and light such as ultraviolet rays was irradiated, and development was performed with an alkali developing solution. After the exposed portion was washed away, a undulating pattern with a clear end surface was obtained.

Examples of the usable alkaline developing solution include aqueous solutions of alkali metal hydroxides such as sodium carbonate, potassium carbonate, potassium hydroxide, and sodium hydroxide, tetramethylammonium hydroxide, and tetraethyl hydroxide. Aqueous solutions of ammonium, choline and other quaternary ammonium hydroxides, alkaline aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. A surfactant or the like may be added to these developing solutions.

Among the above, as a developing solution for photoresist, a tetraethylammonium hydroxide 0.1 to 2.38% by mass aqueous solution is generally used. In the photosensitive resin composition of the present invention, the use of this basic developing solution does not cause Problems such as swelling can cause good development.

As the developing method, any one of a liquid holding method, a dipping method, and a shaking dipping method can be used. The development time at this time is usually 15 to 180 seconds.

After the development, the positive-type photosensitive resin film is washed with flowing water for, for example, 20 to 120 seconds, and then air-dried using compressed air or compressed nitrogen or by rotation to remove moisture on the substrate, and then obtain the formed film. Graphic film.

Next, the pattern-forming film is baked after being subjected to thermosetting. Specifically, by using a heating plate, an oven, or the like, heat resistance, transparency, flatness, low water absorption, Films with good undulations, such as excellent chemical resistance.

As the post-baking, a heating temperature selected from the range of 140 ° C. to 270 ° C. is generally used, and the method is performed for 5 to 30 minutes on a hot plate and for 30 to 90 minutes in an oven.

Then, by this post-baking, a desired hardened film having a good pattern shape can be obtained.

As described above, with the positive photosensitive resin composition of the present invention, it is possible to form a coating film having a high storage stability, a sufficient high sensitivity, and an unexposed portion reduced during the development to a very small size, and a fine pattern. .

In addition, the cured film obtained from the coating film has the characteristics of being excellent in heat resistance and solvent resistance after metal sputtering, and having high leveling flatness. Therefore, various films in a liquid crystal display or an organic EL display can be suitably used, for example, as an interlayer insulating film, a protective film, an insulating film, and the like, and can also be suitably used for applications such as an array flattening film of a TFT type liquid crystal element.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples.

[Omitted Symbols Used in Examples]

The meaning of the omitted symbols used in the following examples is as follows.

MAA: methacrylic acid

MMA: methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

CHMI: N-cyclohexylmaleimide

AIBN: Azobisisobutyronitrile

PGMEA: propylene glycol monomethyl ether acetate

QD: by 1 mol of α, α, α'-shen (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene and 1,2-naphthoquinone-2-diazide-5-sulfofluorene Compounds synthesized by condensation reaction of 1.5 mol of chlorine

TAIC: Ginseng (2-propenyloxyethyl) isocyanurate

HMM: hexamethoxymethyl melamine

CEL-2021P: 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate

DPHA: Dipentaerythritol penta / hexaacrylate

MPTS: γ-methacryloxypropyltrimethoxysilane

R30: Megafac R-30 (trade name) manufactured by Dainippon Ink Chemical Industry Co., Ltd.

TMAH: Tetramethylammonium hydroxide

[Measurement of number average molecular weight and weight average molecular weight]

The number-average molecular weight and weight-average molecular weight of the alkali-soluble acrylic polymer and the specific crosslinked product obtained according to the following synthesis examples were obtained using a GPC device (Shodex (registered trademark) column KF803L and KF804L) manufactured by JASCO Corporation. Tetrahydrofuran which precipitated the solvent was measured under the conditions that the flow rate was 1 ml / min in a column (column temperature 40 ° C) to dissolve it. The 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 conversion values.

<Synthesis example 1>

As monomer components constituting the alkali-soluble acrylic polymer, MAA 10.9 g, CHMI 35.3 g, HEMA 25.5 g, and MMA 28.3 g are used, and AIBN 5 g is used as a radical polymerization initiator, and these are made into a solvent PGMEA In 150 g, a polymerization reaction was performed at a temperature of 60 ° C. to 100 ° C. to obtain a solution of the (A) component (alkali-soluble acrylic polymer) of Mn 3,800 and Mw 6,700 (alkali-soluble acrylic polymer concentration: 40.0% by mass). (P1)

<Example 1 to Example 2 to Example 3 and Comparative Example 1 to Comparative Example 2 to Comparative Example 3>

According to the composition shown in Table 1 below, (A) component solution (B) component, (C) component, and (D) component, (E) solvent, and (F) component and (G) The components were stirred at room temperature for 3 hours to prepare a homogeneous solution, and the positive photosensitive resin compositions of the examples and each comparative example were prepared.

For each of the positive photosensitive resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3, the sensitivity of individual coating films, adhesion during development, and pattern during thermal curing were measured separately. The dimensional change, leveling flatness of the cured film, and heat resistance after metal sputtering were evaluated.

[Evaluation of sensitivity]

After the positive-type photosensitive resin composition was coated on a silicon wafer using a spin coater, pre-baking was performed on a hot plate at a temperature of 120 ° C. for 120 seconds to form a coating film having a thickness of 4.0 μm. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was irradiated with ultraviolet light having a light intensity of 5.5 mW / cm ² at 365 nm for a certain period of time by a UV irradiation device PLA-600FA made by Canon. Thereafter, it was immersed in a 0.4% by mass TMAH aqueous solution for 90 seconds for development, and then washed with ultrapure water for 20 seconds. The minimum exposure amount (mJ / cm ² ) that eliminates the dissolution residue in the exposure section is set as the sensitivity.

[Evaluation of adhesion]

After the positive photosensitive resin composition was applied on a silicon wafer using a spin coater, pre-baking was performed on a hot plate at a temperature of 120 ° C for 120 seconds to form a coating film. Via a mask, this coating film was irradiated with ultraviolet light having a light intensity of 5.5 mW / cm ² at 365 nm for a certain period of time to form a pattern of 10 μm × 10 μm. Thereafter, development was performed by immersing in a 0.4% by mass TMAH aqueous solution for 90 seconds, and then washing with ultrapure water was performed for 90 seconds. When there is no film peeling and all the patterns remain, the adhesion is judged to be good (○), and when the film is peeled and no patterns remain, the adhesion is judged to be poor (×).

[Evaluation of pattern size change]

The silicon wafer substrate prepared in the adhesion evaluation was baked at 230 ° C for 30 minutes using CLEAN OVEN PVHC-210 manufactured by Espec Corporation to form a hardened film having a thickness of about 4.0 μm. The pattern size of the pattern produced was measured by a Hitachi Denkai S-shaped scanning electron microscope S-4100. The dimensional stability is preferably maintained at 9.0 μm <pattern size <10.0 μm.

[Evaluation of heat resistance after metal sputtering]

After the positive photosensitive resin composition was coated on a silicon wafer using a spin coater, pre-baking was performed on a hot plate at a temperature of 120 ° C for 120 seconds to form a coating film.

An oven was used to bake the coating film at a temperature of 230 ° C. for 60 minutes to form a hardened film having a thickness of about 4.0 μm. An Al-Nd metal was sputtered with a thickness of 1000 Å using a reciprocating sputtering device on this hardened film. And, this hardened film with Al-Nd was heated at 230 ° C for 30 minutes using an oven. At this time, it was judged that the case where cracks did not occur on the metal surface was good in heat resistance after metal sputtering (镀), and the case where cracks occurred in metal surface was judged as poor heat resistance after metal sputtering (×).

[Evaluation of step flatness]

Using a spin coater, apply a positive photosensitive resin composition to a Cr-attached substrate (50 μm line width, 0.5 μm height, and 50 μm line spacing), and then pre-baked on a hot plate at 120 ° C. for 120 seconds. Bake to form a coating film. This coating film was baked in an oven at a temperature of 230 ° C. for 30 minutes to form a hardened film having a thickness of 4.0 μm. The film thickness is measured by using a stylus-type surface shape measuring device Dektak150 made by ULVAC. The film thickness difference between the coating film on the stepped substrate line and the coating film on the line pitch is measured. The flattening ratio (DOP) = 100 × {1- (film thickness difference (μm) of the coating film) / (height of the stepped substrate (0.5 μm)}) is used to obtain the flattening ratio.

[Result of Evaluation]

The results of the above evaluations are shown in Table 2 below.

As can be seen from the results shown in Table 2, the positive-type photosensitive resin compositions of Examples 1 to 3 are all highly sensitive and exhibit adhesiveness during development. Also sufficient. In addition, the dimensional change after pattern formation is small, the heat resistance of the cured film after metal sputtering is high, and the leveling flatness is also good. On the other hand, the pattern size of Comparative Example 1 to Comparative Example 2 changed greatly, the flatness of the step difference of Comparative Example 2 was low, and the heat resistance of Comparative Example 3 after metal sputtering was poor, all of which could not satisfy all the properties.

[Industrial availability]

The positive-type photosensitive resin composition of the present invention is suitable as a material for hardening films such as protective films, planarizing films, and insulating films in various displays such as thin-film transistor (TFT) liquid crystal display elements and organic EL elements. 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 concave-convex film under a reflective film of a reflective display, an insulating film of an organic EL element, and the like It is also suitable for various electronic materials such as micro lens materials.

Claims (11)

A positive-type photosensitive resin composition comprising the following components (A), (B), (C), (D), and (E) a solvent; (A) an alkali-soluble acrylic polymer, ( B) component: quinonediazide compound, (C) component: compound having an isocyanurate skeleton and two or more polymerizable unsaturated double bonds, (D) component: having two or more selected from alkoxy groups Crosslinkable compounds of methyl and hydroxymethyl substituents, (E) solvents. The positive-type photosensitive resin composition according to claim 1, wherein the (A) component coefficient is an alkali-soluble acrylic polymer having an average molecular weight of 2,000 to 30,000 in terms of polystyrene. For example, the positive photosensitive resin composition of claim 1 or claim 2 is 5 to 100 parts by mass with respect to 100 parts by mass of the component (A). For example, the positive-type photosensitive resin composition of claim 1 or claim 2, wherein the component (C) is 5 to 60 parts by mass relative to 100 parts by mass of the component (A). For example, the positive-type photosensitive resin composition of claim 1 or claim 2, wherein the component (D) is 5 to 50 parts by mass relative to 100 parts by mass of the component (A). For example, the positive photosensitive resin composition according to claim 1 or claim 2, wherein 100 parts by mass of the positive photosensitive resin composition further contains 0.01 to 1.0 part by mass of a surfactant as a component (F). For example, the positive-type photosensitive resin composition of claim 1 or claim 2, wherein the positive-type photosensitive resin composition contains an adhesion promoter as a component (G) with respect to 100 parts by mass of the component (A). 0.1 to 20 parts by mass. A cured film obtained by using the positive-type photosensitive resin composition according to any one of claim 1 to claim 7. A display element having a cured film as claimed in claim 8. An array flattening film for a display is composed of a cured film as claimed in claim 8. An interlayer insulating film composed of a hardened film as claimed in claim 8.