TWI424270B - Positive-type photosensitive resin composition, and interlayer insulator and microlens produced from the composition - Google Patents

Description

Positive photosensitive resin composition and resulting interlayer insulating film and microlens

The present invention relates to a positive photosensitive resin composition. More specifically, it relates to a positive photosensitive resin composition suitable for use as a display material.

Generally, in a display element such as a thin film transistor (TFT) type liquid crystal display element or an organic EL element, an electrode protective film, a planarizing film, an insulating film, or the like is formed. As a material for forming these films, there is a feature that the number of steps for obtaining a necessary pattern shape is small, and sufficient flatness is exhibited, and a photosensitive resin composition is widely used. Therefore, for these films, step resistance such as heat resistance, solvent resistance, long-term calcination resistance, and the adhesion to the underlying layer are required, and the width of the pattern can be formed under various conditions for the purpose of use. Process margin, plus high sensitivity, high transparency, and fewer film spots after imaging.

In order to impart "photosensitivity" to the above-mentioned required characteristics, a 1,2-quinonediazide compound is often added. The sensitizer used in the interlayer insulating film and the microlens material requires less load on the earth environment and the working environment such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, or ethyl lactate, and is safely dissolved in a solvent and visible light. The transmittance after ultraviolet irradiation is high.

Moreover, one of the required characteristics of the material is to increase the sensitivity. The increase in sensitivity has led to a significant reduction in production time in industrial production, and it has become one of the most important characteristics of the recent demand for liquid crystal displays. However, in the past, materials were not satisfactory in terms of sensitivity. Although the sensitivity of the polymer in the material to the alkaline developing solution is improved, the sensitivity is also improved, but the method also has a limit, and also causes dissolution of the unexposed portion, and the residual film rate is lowered, and has a large substrate. Disadvantages related to the cause of the film spot.

To date, several patents with high sensitivity have been filed. For example, a radiation sensitive resin composition containing at least one of an alkali-soluble resin and a specific polyhydroxy compound and a derivative thereof has been proposed (for example, refer to Patent Document 1). However, due to the high degree of symmetry of the sensitizer, there are problems such as preservation stability. Further, a positive-type radiation-sensitive resin composition containing an alkali-soluble phenol resin and a radiation-sensitive compound (for example, refer to Patent Document 2), and a positive-type photosensitive film containing a specific alkali-soluble resin and a quinonediazide compound have been proposed. The resin composition (for example, refer to Patent Document 3). Since a novolac resin is used for a binder polymer, it has a problem in transparency and stability in the case of baking for a long time. As described above, it has been very difficult to develop a resin composition satisfying other characteristics and high sensitivity, which is difficult in the simple combination of the prior art.

[Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei.

An object of the present invention is to provide a coating film which is excellent in storage stability, can form a high sensitivity, and has a small degree of film thinning at the time of development, and has high transparency of a cured film which is heat-treated by the coating film. A positive photosensitive resin composition. Further, an interlayer insulating film and a microlens using the positive photosensitive resin composition are provided.

The present inventors have made efforts to achieve the above object and have completed the present invention. That is, a positive photosensitive resin composition characterized by containing the following (A) component, (B) component, and solvent (A) component: at least one of unsaturated carboxylic acids is a polymerization which must be copolymerized. At least one alkali-soluble resin (B) component selected from the group consisting of: 1,2-quinonediazide compound represented by formula (1) (wherein D ₁ to D ₃ are each independently a hydrogen atom or an organic group having a 1,2-quinonediazide group. However, at least one of D ₁ to D ₃ has a 1,2-quinoned stack A nitrogen-based organic group. Further, n is an integer representing from 1 to 3, and R is a monovalent organic group.

2. The positive photosensitive resin composition according to the above 1, wherein the component (B) is 5 to 100 parts by mass based on 100 parts by mass of the component (A).

3. The positive photosensitive resin composition according to the above 1 to 2, wherein the number average molecular weight of the alkali-soluble resin of the component (A) is 2,000 to 30,000 in terms of polystyrene.

4. The positive photosensitive resin composition according to any one of the above 1 to 3, wherein the component (A) is one in which at least one of the unsaturated carboxylic acids and the N-substituted maleimide are copolymerized. At least one alkali-soluble resin selected from the polymer.

5. The positive photosensitive resin composition according to any one of the above 1 to 4, wherein n of the formula (1) of the component (B) is an integer of from 1 to 3, and R is a methyl group or an ethyl group.

6. The positive photosensitive resin composition according to any one of the above 1 to 4, wherein n of the formula (1) of the component (B) is 2, and R is a methyl group.

7. The positive photosensitive resin composition according to any one of the above 1 to 6, which contains the crosslinkable compound represented by the following formula (2) as the component (C). (wherein k is an integer of 2 to 10, m is an integer of 0 to 4, and R ¹ is a k-valent organic group).

8. The positive photosensitive resin composition according to any one of the above 1 to 7, wherein the solvent is propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, ethyl lactate, butyl lactate, and At least one solvent selected from cyclohexanone.

9. The positive photosensitive resin composition according to any one of the above 1 to 8, wherein the solvent is a mixed solvent of at least one solvent having a boiling point of 200 to 250 ° C in combination.

A coating film of a pattern, which is obtained by applying the positive photosensitive resin composition according to any one of the above 1 to 9 to a substrate, exposing it through a mask, and developing the image.

A cured film obtained by the positive photosensitive resin composition according to any one of the above 1 to 9.

An interlayer insulating film obtained by the positive photosensitive resin composition according to any one of the above 1 to 9.

A microlens obtained by the positive photosensitive resin composition according to any one of the above 1 to 9.

The positive photosensitive resin composition of the present invention can form a coating film having high sensitivity and high residual film ratio, and the cured film obtained by heat-treating the coating film has high transparency. The positive photosensitive resin composition of the present invention is characterized in that it has no foreign matter and has excellent storage stability.

Therefore, a material for the interlayer insulating film and the microlens can be suitably used.

(Best form of implementing the invention)

Hereinafter, the positive photosensitive resin composition of the present invention will be specifically described.

The positive photosensitive resin composition of the present invention is characterized by containing the following component (A), component (B) and a solvent.

(A) component: an alkali-soluble resin (B) component in which at least one of unsaturated carboxylic acids is at least one selected from copolymerized polymers: 1,2-quinonediazide represented by formula (1) Base compound (wherein D ₁ to D ₃ are each independently a hydrogen atom or an organic group having a 1,2-quinonediazide group. However, at least one of D ₁ to D ₃ has a 1,2-quinoned stack A nitrogen-based organic group. Further, n is an integer representing from 1 to 3, and R is a monovalent organic group.

<Component (A): alkali-soluble resin> The alkali-soluble resin used in the positive-type photosensitive resin composition of the present invention is a polymer which is copolymerized by at least one of unsaturated carboxylic acids (hereinafter, referred to as specific copolymerization) At least one alkali-soluble resin selected.

That is, the alkali-soluble resin used in the present invention has a property of being soluble in an alkaline solution in a specific copolymer. The component (A) is one or more kinds of alkali-soluble resins selected from specific copolymers having such a soluble substance in an alkaline solution.

The specific copolymer must have a number average molecular weight (hereinafter referred to as a number average molecular weight) of 2,000 to 30,000. It is preferably 2,500 to 15,000, more preferably 3,000 to 10,000.

When the number average molecular weight is 2,000 or less, the shape of the obtained pattern is poor, and the residual film ratio of the pattern is lowered, and the heat resistance of the pattern is lowered. On the other hand, in the case where the number average molecular weight is more than 30,000, the coating property of the photosensitive resin composition is poor, the developability is lowered, and the peeling development is caused, and the shape of the obtained pattern is poor, and the organic solvent is not bad. Solubility sometimes decreases. Further, in the case where the number average molecular weight is more than 40,000, a residual film exists between the patterns of 50 μm or less and the resolution is lowered.

The monomer to obtain the specific copolymer is not particularly limited to the unsaturated carboxylic acid, and specific examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.

In the present invention, at least one of the unsaturated carboxylic acids is required as the monomer to obtain the specific copolymer, but two or more kinds thereof may be used in combination.

The ratio of the unsaturated carboxylic acid is preferably from 1 to 30% by mass, more preferably from 3 to 25% by mass, most preferably from 5 to 20% by mass, based on the total amount of the monomer species used for obtaining the specific copolymer. When the amount is less than 1% by mass, the solubility in the alkali developing solution is insufficient. When the amount is more than 30% by mass, the solubility in the alkaline developing solution is too high, so that the unexposed portion is also dissolved and the residual film ratio is high. Reduced.

Further, as the monomer species for obtaining a specific copolymer, an unsaturated carboxylic acid derivative may be used in combination with the unsaturated carboxylic acid. Specific examples thereof include alkyl methacrylate, ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate, and butyl methacrylate, alkyl acrylate, and acrylic acid. a cyclic alkyl ester such as an alkyl ester such as isopropyl ester, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentyloxyethyl methacrylate or isobornyl methacrylate a diester of a carboxylic acid such as phenyl methacrylate or benzyl methacrylate, diethyl maleate, diethyl fumarate or diethyl itaconate A hydroxyalkyl ester such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate or 2-hydroxyethyl methacrylate.

There may be mentioned bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclol [2.2.1] Hept-2-ene, 5-carboxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyl Ethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5 , 6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1 ???hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2- Alkene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethyl Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2- Alkene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2. 1] Hept-2-ene anhydrate (Hymic Acid anhydrate), 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2 - alkene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-di ( a bicyclic unsaturated compound such as cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene.

Further, examples thereof include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and acrylic-3,4. -butyl butyl acrylate, 3,4-epoxybutyl methacrylate, propylene-6,7-epoxyheptyl ester, -6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6 7-epoxyheptyl ester, benzyl-vinyl benzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.

Among them, glycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl shrinkage An epoxy group-containing unsaturated carboxylic acid ester such as glyceryl ether or the like is preferably used for alleviating the scaling of the cured film.

In the present invention, one or more of the unsaturated carboxylic acid derivatives may be used in combination as a monomer for obtaining a specific copolymer.

Further, as the monomer species for obtaining a specific copolymer, an ethylenic compound copolymerizable with an unsaturated carboxylic acid and a derivative thereof may be used in combination. Specific examples of such an ethylenic compound include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, styrene, and α-methylbenzene. Ethylene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, p-hydroxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, propylene Indoleamine, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like. These ethylenic compounds can be introduced for the purpose of adjusting the solubility, water repellency, and the like of a specific copolymer, and controlling molecules. Among them, N-substituted Malayan, such as cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, etc., from the viewpoint of heat resistance Amine is preferred.

In the present invention, as the monomer species for obtaining a specific copolymer, one or more selected from the group consisting of ethylene compounds may be used in combination.

The total amount of the monomeric species used for obtaining the specific copolymer is preferably from 5 to 50% by mass, more preferably from 15 to 45% by mass, even more preferably from 20 to 40% by mass. When the amount of the vinyl compound is 5% by mass or less, the film thickness during development is large, and the film shrinkage is sometimes increased by thermal decomposition of the cured film. Further, when the amount of the ethylenic compound is 50% by mass, the residue at the time of development may increase.

The specific copolymer which is preferably selected is a total amount of the monomer species used for obtaining a specific copolymer, and the unsaturated carboxylic acid is 1 to 30% by mass, and the residual unsaturated carboxylic acid derivative or unsaturated carboxylic acid is 1 to 30% by mass, an ethylenic compound of 5 to 50% by mass, and a residual unsaturated carboxylic acid derivative.

The method for obtaining the specific copolymer used in the present invention is not particularly limited. In general, a monomer obtained by obtaining the monomer of the above specific copolymer can be produced by radical polymerization in a polymerization solvent. Further, if necessary, the monomer function is polymerized in a protected state, and thereafter, a deprotection treatment may be performed.

In this case, the polymerization temperature is not particularly limited as long as it can polymerize the monomer, and is preferably 50 to 110 ° C.

The above-mentioned polymerization solvent may, for example, be an alcohol such as methanol, ethanol, propanol or butanol, tetrahydrofuran or the like. An ether such as an alkane, an aromatic hydrocarbon such as benzene, toluene or xylene; a polar solvent such as N,N-dimethylformamide or N-methyl-2-pyrrolidone; ethyl acetate or butyl acetate; , esters of ethyl lactate, etc., methyl 3-methoxypropionate, 2-methoxypropenyl methyl ester, ethyl 3-methoxypropionate, ethyl 2-methoxyacrylate, 3-ethyl Alkoxylates such as ethyl oxypropionate and ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol (di)diethanol dialkyl esters such as ethyl ester, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol Alcohol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, etc. (b) glycol monoalkyl ethers, propylene glycol monomethyl ether acetate, carbitol acetate, B A ketone such as a glycol monoester ether ester such as acetate, a cyclohexanone, a methyl ethyl ketone, a methyl isobutyl ketone or a 2-heptanone. These polymerization solvents may be used alone or in combination of two or more.

Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethyl lactate are preferred from the viewpoint of safety in the global environment and the working environment.

Further, the component (A) (alkali-soluble resin) used in the positive photosensitive resin composition of the present invention preferably has a small residual monomer content. Here, the residual monomer is an unreacted product of each monomer type remaining after copolymerizing each monomer type to obtain a specific copolymer. The residual monomer is present in the residual monomer ratio, and the residual monomer ratio is expressed as a ratio (% by mass) of the total mass of each residual monomer relative to the total mass of each monomer used in the copolymerization reaction. . Further, when the component (A) is an alkali-soluble resin composed of a plurality of specific copolymers, the specific copolymers of the plurality of specific copolymers may be copolymerized with respect to the total mass of the monomer species used in the copolymerization of the specific copolymers. The ratio (% by mass) of the total mass of the residual monomers of the substance is expressed.

The analysis method of the residual monomer amount can be confirmed, for example, by analyzing the copolymerized reaction liquid using liquid chromatography or the like.

The residual monomer ratio is preferably 2.5% by mass or less, more preferably 2.0% by mass or less, still more preferably 1.5% by mass or less. In the case where the residual monomer ratio exceeds 2.5% by mass, the electrical characteristics of the display element sometimes decrease.

The method of reducing the residual monomer in the alkali-soluble resin is not particularly limited, and examples thereof include a method of performing refining such as generally known refining in polymer synthesis, or a method of increasing the reaction temperature in the final stage of polymerization.

<Component (B): 1,2-quinonediazide compound> The component (B) used in the positive photosensitive resin composition of the present invention is a 1,2-quinonediazide compound having a specific structure. It is represented by the formula (1).

(wherein D ₁ to D ₃ are each independently a hydrogen atom or an organic group having a 1,2-quinonediazide group. However, at least one of D ₁ to D ₃ has a 1,2-quinoned stack A nitrogen-based organic group. Further, n is an integer representing from 1 to 3, and R is a monovalent organic group.

In the formula (1), n is an integer of 1 to 3, and R is a monovalent organic group. R is not particularly limited, and specific examples thereof include a linear alkyl group such as a methyl group, an ethyl group, or a propyl group, an isopropyl group, an isobutyl group, a second butyl group, and a third butyl group. A branched alkyl group or the like. Among them, an aliphatic group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred.

Further, D ₁ to D ₃ are each independently a hydrogen atom or an organic group having a 1,2-quinonediazide group, and at least one of D ₁ to D ₃ has a 1,2-quinonediazide group. Organic base. In the formula (1), the organic group having a 1,2-quinonediazide group is not particularly limited, and specific examples thereof include 1,2-naphthoquinonediazide-4-sulfonyl group, and 2-naphthoquinonediazide-5-sulfonyl, 1,2-naphthoquinonediazide-4-sulfonyl and the like. Among them, from the viewpoint of transparency of the cured film, 1,2-naphthoquinonediazide-5-sulfonyl group and 1,2-naphthoquinonediazide-4-sulfonyl group are preferred.

The component (B) used in the present invention is not particularly limited as long as it is a 1,2-quinonediazide compound represented by the formula (1), but solubility, sensitivity, resolution, residual film ratio, and transparency to a solvent described later are transparent. From the viewpoint of the nature, a compound wherein R is a methyl group or an ethyl group and n is 1 or 2 is preferred. More preferably, the compound represented by the following formula (3) wherein R is a methyl group and n is 2 is preferable.

(wherein D ₁ to D ₃ are each independently a hydrogen atom or an organic group having a 1,2-quinonediazide group. However, at least one of D ₁ to D ₃ has a 1,2-quinoned stack Nitrogen-based organic group).

The method for obtaining the 1,2-quinonediazide compound represented by the formula (1) used in the present invention is not particularly limited. Generally, a compound represented by the following formula (4) is used. It can be obtained by reacting with a compound having a 1,2-quinonediazide group. In general, chlorides having a 1,2-quinonediazide group are widely used.

For example, a compound represented by the formula (4) and 1,2-naphthoquinonediazide-5-sulfonyl chloride and 1,2-naphthoquinonediazide-4-sulfonyl chloride are 1,2- The esterification reaction of the quinonediazidesulfonium halide can obtain the 1,2-quinonediazide compound represented by the formula (1).

In this case, a part or all of the hydroxyl group of one of the compounds represented by the formula (4) is reacted with a compound having a 1,2-quinonediazide group, and the average condensation rate of the above esterification reaction is obtained in the present invention with sufficient sensitivity. (The number of phenolic hydroxyl groups esterified / the number of phenolic hydroxyl groups before the reaction) × 100] is 5 to 100%, preferably 10 to 98%, more preferably 20 to 95%. When the average condensation ratio of the esterification reaction is 5% or less, the exposed portion and the unexposed portion do not have sufficient solubility difference with respect to the alkaline developing solution. Therefore, a pattern having a good resolution may not be obtained.

In the positive photosensitive resin composition of the present invention, the content of the component (B) is preferably from 5 to 100 parts by mass, more preferably from 10 to 50 parts by mass, per 100 parts by mass of the component (A). It is 10 to 30 parts by mass. When the amount is less than 5 parts by mass, the difference in solubility between the exposed portion and the unexposed portion of the positive photosensitive resin composition for the developing solution is small, and it may be difficult to form a pattern by development. In addition, when it exceeds 100 parts by mass, the sensitivity of the 1,2-quinonediazide compound is not sufficiently decomposed in a short exposure, and the component (B) absorbs light and makes the cured film transparent. Reduced situation.

<Solvent> The solvent used in the present invention is not particularly limited as long as it dissolves the component (A), the component (B), and the components (C) to (F) described later.

Specific examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, and diethylene glycol alone. Ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol monobutyl ether, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, ring Hexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3 Methyl methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, acetic acid Ethyl ester, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, and the like. These solvents may be used alone or in combination of two or more.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, ethyl lactate, butyl lactate and cyclohexanone are preferred for improving the coating property of the coating film.

Further, at least one of the solvents of 200 ° to 250 ° C may be used in combination. In this case, the solvent having a boiling point of 200 to 250 ° C is preferably from 1 to 50% by mass, and more preferably from 5% to 40% by mass, based on the total solvent contained in the positive photosensitive resin composition. When the amount is 50% by mass or more, it may be difficult to obtain a good coating property of the coating film, and when it is 1% by mass or less, the above effects may not be obtained.

The term "boiling point" as used in this specification means a standard boiling point in 1 atmosphere.

Specific examples of the solvent having a boiling point of 200 to 250 ° C include N-methylpyrrolidone, γ-butyrolactone, diethylene glycol monoethyl ether (ethyl carbitol), and diethylene glycol monobutyl ether (butyl card). Alcohol) - acetamide, benzyl alcohol, and the like.

<Component (C): Crosslinkable Compound> The positive photosensitive resin composition of the present invention may contain the crosslinkable compound represented by the formula (2) as the component (C).

(wherein k is an integer of 2 to 10, m is an integer of 0 to 4, and R ¹ is a k-valent organic group.) The component (C) is a cyclohexene oxide structure represented by the formula (2). The compound is not particularly limited. Specific examples thereof include the following formulas C1 and C2, and commercially available products shown below.

Commercially available products include Epolid GT-401, GT-403, GT-301, GT-302, Geroxide 2021, Geroxide 3000 (trade name manufactured by Diacel Chemical Industry Co., Ltd.), and Denacol of alicyclic epoxy resin. EX-252 (trade name of Nagase Chemtex), CY175, CY177, CY179 (above, trade name of CIBA-GEIGY AG), Ararudite CY-182, same CY-192, and CY-184 (above, CIBA- GEIGY AG product name), Epiclione 200, same 400 (above, Dainippon Ink Chemical Industry Co., Ltd. product name), Epicoat 871, 872 (above, oiled Shell Epoxy (stock) product name), ED- 5661, ED-5662 (above, the trade name of Seraneeds Coating).

Further, these crosslinkable compounds may be used alone or in combination of two or more.

Among them, the compound represented by the cyclohexene oxide structure or the C1 and the formula C2, Epolide GT-, is resistant to the step resistance and the transparency from the viewpoints of heat resistance, solvent resistance, long-term calcination resistance, and the like. 401, with GT-403, with GT-301, with GT-302, Seroxide 2021, Seroxide 3000 is better.

The amount of the component (C) added is 3 to 50 parts by mass, preferably 7 to 40 parts by mass, more preferably 10 to 30 parts by mass, per 100 parts by mass of the component (A). When the content of the crosslinkable compound is small, the crosslinking density formed by the crosslinkable compound is insufficient, and heat resistance, solvent resistance, resistance to long-term calcination, and the like may not be obtained. Effect. On the other hand, in the case of more than 50 parts by mass, there is a crosslinkable compound which is not crosslinked, and the heat resistance, solvent resistance, resistance to long-term calcination, etc. after forming a pattern are lowered, and sometimes The storage stability of the photosensitive resin composition is deteriorated.

<Component (D): Surfactant> The positive photosensitive resin composition of the present invention may be added with a surfactant for the purpose of improving coatability. Such a surfactant is not particularly limited as long as it is a fluorine-based surfactant, a polyoxyalkylene-based surfactant, a nonionic surfactant, or the like. For example, commercially available products such as Sumitomo 3M (share) system, Dainippon Ink Chemical Industry Co., Ltd., and Asahi Glass Co., Ltd. can be used, and such commercial products can be easily obtained.

The component (D) may be one or a combination of two or more of the above surfactants.

Among these surfactants, a fluorine-based surfactant is preferred in terms of the coating improving effect.

Specific examples of the fluorine-based surfactant include Efutop EF301, EF303, EF352 (trade name, manufactured by Tochem Products), Megafac F171, F173, and R-30 (trade name of Dainippon Ink Chemicals Co., Ltd.) Floride FC430 FC431 (commodity name of Sumitomo 3M Co., Ltd.), Asahiguard AG710, Surflow S-382, SC101, SC102, SC103, SC104, SC105, SC106 (product name of Asahi Glass Co., Ltd.), etc., but is not limited thereto.

The amount of the component (D) to be added to the positive photosensitive resin composition of the present invention is 0.01 to 5 parts by mass, preferably 0.01 to 3 parts by mass, more preferably 0.01 based on 100 parts by mass of the component (A). ~2 parts by mass. When the amount of the surfactant added is more than 5 parts by mass, the coating film is liable to cause unevenness in the coating film, and in the case of less than 0.01 part by mass, the coating property improving effect cannot be obtained.

<(E) component: adhesion promoter> The positive photosensitive resin composition of the present invention may be added with a adhesion promoter for the purpose of improving the adhesion to the substrate after development. Specific examples of such a viscosity-immobilizing agent include chlorodecanes such as trimethylchlorodecane, dimethylvinylchlorodecane, methylbiphenylchlorodecane, and chloromethyldimethylchlorodecane. Dimethyl methoxy decane, dimethyl diethoxy decane, methyl dimethoxy decane, dimethyl vinyl ethoxy decane, biphenyl dimethoxy decane, phenyl triethoxy decane Alkoxy decanes, hexamethyldioxane, N,N'-bis(trimethylformamido)urea, dimethyltrimethylformamidineamine, trimethylformamimidazole Isoazane, vinyltrichlorodecane, γ-chloropropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-methylpropenyloxypropyltrimethoxydecane, γ - decanes such as glycidyloxypropyltrimethoxydecane, γ-(N-piperidinyl)propyltrimethoxydecane, benzotriazole, benzimidazole, oxazole, imidazole, 2-hydrogenthio Benzimidazole, 2-hydrothiobenzothiazole, 2-hydrothiobenzoate a heterocyclic compound of oxazole, urazol, thiouracil, hydrothioimidazole, thiopyrimidine or the like, and urea, or thiourea such as 1,1-dimethylurea or 1,3-dimethylurea Compound.

As the above-mentioned adhesion promoter, for example, a commercially available compound such as Shin-Etsu Chemical Co., Ltd., GE Toshiichi Silicone Co., Ltd., and Toray Dowconing Co., Ltd. may be used, and these commercially available compounds are easily used. Acquired.

The (E) component may be one or a combination of two or more of the above-mentioned dense adhesion promoters.

The amount of the adhesion promoter to be added is usually 20 parts by mass or less, preferably 0.01 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the component (A). When the amount is 20 parts by mass or more, the heat resistance of the coating film may be lowered, and if it is less than 0.1 part by mass, the sufficient effect of the adhesion promoter may not be obtained.

<Component (F): Other Additives> Further, the positive photosensitive resin composition of the present invention may be added with a pigment, a dye, a storage stabilizer, an antifoaming agent, and a multivalent content as long as the effects of the present invention are not impaired. A dissolution promoter such as a phenol or a polyvalent carboxylic acid.

<Positive Photosensitive Resin Composition> The positive photosensitive resin composition of the present invention is characterized by containing the component (A), the component (B), and a solvent. In other words, it is a positive photosensitive resin composition containing one or more of (A) component, (B) component, and solvent, or the component (C)-(F) as needed.

In the present invention, a specific example of the positive photosensitive resin composition is preferably composed of [1] (A) component (100 parts by mass), (B) component 5 to 100 parts by mass, and a positive photosensitive resin composed of a solvent. And [2] a positive photosensitive resin composition comprising 3 to 50 parts by mass of the above [1] and (C) components, and [3] 0.01 to 5 parts by mass of the above [2] and (D) components. a positive photosensitive resin composition, [4] a positive photosensitive resin composition comprising 20 parts by mass or less of the above [3] and (E) components, [5] with respect to 100 parts by mass of the alkali-soluble resin composition, 1 The 2-quinonediazide compound is 10 to 30 parts by mass, and the crosslinkable compound containing two or more epoxy groups is a positive photosensitive resin composition composed of 10 to 30 parts by mass.

The solid content concentration of the positive photosensitive resin composition of the present invention is not particularly limited as long as the components can be uniformly dissolved. Usually, a range of 1 to 50% by mass is generally used. Further, for the purpose of adjusting the film thickness and the conditions of the coating device, it may be adjusted to an appropriate solid component concentration by solvent dilution.

The positive photosensitive resin composition of the present invention can be easily mixed with one or more of the components (A) and (B), or the like (C) to (F), if necessary, in a solvent. modulation. In this case, the component (A) may be a reaction solution obtained by copolymerizing a specific copolymer as it is.

The preparation method of the positive photosensitive resin composition is not particularly limited, and for example, the component (A) (alkali-soluble resin) is dissolved in a solvent, and the component (B) (1, 2-醌2) is contained in the solution. The azido compound), the component (C) (crosslinkable compound), the component (D) (surfactant), and the component (E) (adhesion promoter) are mixed at a predetermined ratio to prepare a homogeneous solution. Further, a mixed (F) component may be added as needed.

Further, as long as the uniformity of the positive photosensitive resin composition and the effects of the present invention are not impaired, the mixture may be heated or mixed, or may be partially heated during the mixing. At this time, the temperature of the solution is preferably at most the boiling point of the solvent.

The positive photosensitive resin composition obtained in this manner is preferably used after filtration using a filter paper having a pore diameter of about 0.5 μm.

The positive photosensitive resin composition of the present invention is excellent in storage stability in suppressing generation of foreign matter.

<Coating film and cured film> The positive photosensitive resin composition of the present invention is a substrate such as a glass substrate, a germanium wafer, an oxide film, a nitride film, a substrate coated with a metal such as aluminum, molybdenum or chromium, or the like. Then, it is applied by spin coating, flow coating, roll coating, slit coating, slit, followed by spin coating, inkjet coating, etc., and then pre-dried by a hot plate, an oven, or the like. A coating film is formed. In this case, the pre-drying is preferably carried out at a temperature of 80 to 130 ° C for 30 to 600 seconds, and an appropriate condition may be selected as needed.

On the coating film obtained above, a reticle having a predetermined pattern is attached and irradiated with ultraviolet light or the like to develop an image in an alkaline developing solution, and the exposed portion is washed to obtain a embossed pattern having a clear end face. In this case, the developing solution to be used is not particularly limited as long as it is alkaline water-soluble. Specific examples thereof include an aqueous solution of an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, potassium carbonate or sodium carbonate, or a hydrogenated quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline. An aqueous solution of an aqueous solution, ethanolamine, propylamine, ethylenediamine or the like.

The alkaline developing solution is generally an aqueous solution of 10% by mass or less, preferably an aqueous solution of 0.1 to 3.0% by mass or the like. Further, an alcohol and a surfactant may be added to the above-mentioned developing solution, and it is preferably 0.05 to 10 parts by mass per 100 parts by mass of the developing solution.

Among them, an aqueous solution of tetraethylammonium hydroxide in an amount of 0.1 to 2.38 mass% is generally used as a developing solution for a photoresist, and the photosensitive resin composition of the present invention can be developed without using problems such as swelling.

Further, as the development method, any of a liquid discharge method, a dipping method, a shaking dipping method, or the like can be used. At this time, the development time is usually 15 to 180 seconds. After the image is developed, it is washed with running water for 20 to 90 seconds, and air-dried with compressed air, compressed nitrogen, or spin, to remove moisture on the substrate, thereby obtaining a coating film of a pattern. Then, the coating film having the pattern formed thereon is irradiated with ultraviolet rays such as a high-pressure mercury lamp, and the (B) component (1,2-quinonediazide compound) remaining in the pattern-like coating film is completely completed. Decomposition can improve the transparency of the coating film. Then, by heating with a hot plate, an oven, or the like, the coating film can be cured (hereinafter referred to as post-baking) to obtain heat resistance, and transparency, flatness, low water absorption, and chemical resistance are excellent. And has a good embossed pattern of the coating film.

The conditions for hot baking are as follows: temperature 140 ° ~ 250 ° C, if it is on the hot plate for 5 to 30 minutes, in the oven for 30 to 90 minutes. By this treatment, a cured film having a patterned shape can be obtained. Further, the desired microlens can be obtained by selecting the shape of the pattern.

As described above, the positive-type photosensitive resin composition of the present invention is a coating film which can form a very high sensitivity and which has a very small film thickness at the time of development and has a fine pattern. The cured film obtained by the coating film is excellent in heat resistance, solvent resistance, and transparency.

Therefore, the cured film is suitably used for an interlayer insulating film, various insulating films, various protective films, and the like, and can be suitably used as a microlens in a selected pattern shape.

[Examples]

The invention will be described in more detail below by way of examples, but the invention is not limited thereto.

A shorthand description of the embodiment.

(Monomer) AA: Acrylic acid MAA: Methacrylic acid MMA: Methyl methacrylate BMA: Benzyl methacrylate NBMA: n-butyl methacrylate HEMA: 2-hydroxyethyl methacrylate HPMA: methacrylic acid 2 -Hydroxypropyl ester CHMI: N-cyclohexylmaleimide EMI: Ethyl maleimide PHMI: N-phenylmaleimide (polymerization initiator) AIBN: azobisisobutyronitrile (solvent PGMEA: propylene glycol monomethyl ether acetate EL: ethyl lactate GBL: γ-butyrolactone MAK: 2-heptanone <Synthesis Example 1> Specific copolymer solution (P1) using MAA 13.5 g, CHMI 35.3 g, HEMA 25.5 25.7 g of gram and MMA are used as a monomer component constituting a specific copolymer, and 5 g of AIBN is used as a radical polymerization initiator, and 200 g of PGMEA as a solvent is reacted at a temperature of 60 to 100 ° C to obtain a number. The average molecular weight (hereinafter referred to as Mn) is a specific copolymer having 4,100 and a weight average molecular weight (hereinafter referred to as Mw) of 7,600. Thereto, a solvent similar to the solvent used in the above polymerization reaction was added to obtain a solution (P1) having a specific polymer concentration of 27% by mass. The results are shown in Table 1. The measurement of Mn and Mw is carried out by using a normal temperature gel permeation chromatography (GPC) apparatus (SSC-7200, Shodex (registered trademark) column (one KD803, one KD805), and a dissolution solvent. (Solvent name) The measurement was carried out under the conditions of a flow rate of 1 ml/min and a temperature of 55 ° C. Further, Mn and Mw were values in terms of polystyrene.

<Synthesis Examples 2 to 4> Specific copolymer solution (P2 to P4) The monomer component and solvent of Synthesis Example 1 were changed to the monomer components and solvents described in Synthesis Examples 2 to 4 of Table 1, and were processed in the same manner as in the synthesis example. Specific copolymer solution (P2 to P4), and Mn and Mw of the specific copolymer obtained were measured. The results are shown in Table 1.

<Synthesis Example 5> The specific copolymer solution (P5) used 13.3 g of AA, 35.3 g of PHMI, 25.5 g of HEMA, and 23.7 g of MMA as a monomer component constituting a specific copolymer, and 5 g of AIBN was used as a radical polymerization initiator. Further, in 150 g of PGMEA as a solvent, at a temperature of 60 to 70 ° C, a solution (P5) having a concentration of 40.0 mass% of a specific copolymer of Mn of 5,400 and Mw of 10,200 was obtained. The results are shown in Table 1. Further, Mn and Mw were measured in the same manner as in the first example.

<Examples 1 to 11>

One or more of the specific copolymer solutions (P1 to P4) obtained by the same treatments as in the above Synthesis Examples 1 to 5 are selected as the alkali-soluble resin solution, and a 1,2-quinonediazide compound (hereinafter referred to as a sensitizer) is added. After the crosslinking compound, the surfactant, the adhesion aid, and the solvent, the mixture was stirred at room temperature for 8 hours to prepare a positive photosensitive resin composition having the compositions shown in Tables 2 and 3.

The photosensitizer, crosslinkable compound, surfactant, and adhesion aid used herein are as follows.

[Sensitizer] QD: A compound synthesized by a condensation reaction of trisphenol 1 mol with 2.5 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride shown below.

[Crosslinking Compound] A compound represented by the following formula C1 or C2.

[Interfacial Agent] R30: Megafiac R-30 (trade name) [Compact Adhesive] MPTS: γ-Methyl propylene oxime propyl trimethoxy decane manufactured by Dainippon Ink Chemical Industry Co., Ltd.

<Comparative example>

In 70.8 g of the specific copolymer (P1) solution obtained in the above Synthesis Example 1 as an alkali-soluble resin solution, methyl gallate 1 mM and 1,2-naphthoquinonediazide-2-sulfonate were used. 3.7 g of the compound (QD2) synthesized by the condensation reaction of ruthenium chloride 2.5 mM, 5.2 g of the crosslinkable compound C1, 0.01 g of R30, 0.9 g of MPTS, and 20.4 g of PGMEA, and stirred at room temperature for 8 hours to adjust the positive type. Photosensitive composition. The results are also shown in Table 3.

Next, the results of evaluation of viscosity, sensitivity, film thinning degree, transparency, and foreign matter of each of the positive photosensitive resin compositions of Examples 1 to 11 and Comparative Example 1 shown in Tables 2 and 3 are shown in the table. 4.

The foregoing evaluation was carried out in the following manner.

[Evaluation of Sensitivity] The positive photosensitive composition was applied onto a tantalum wafer by a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C for 120 seconds to form a coating film having a film thickness of 1.75 μm. The film thickness was measured using a Dektak 3ST manufactured by ULVAC. The coating film was irradiated with ultraviolet light of a light intensity of 5.5 mW/cm ² at 365 nm for a certain period of time through a test reticle by a Cannon ultraviolet irradiation apparatus PLA-600FA, followed by 0.4% of tetramethylammonium hydroxide. (hereinafter, referred to as TMAH) aqueous solution was immersed for 60 seconds for development, and then washed with ultrapure water for 20 seconds to form a positive pattern. The pattern formed was observed by an optical microscope, and the line/space pattern from 3.0 μm to 50 μm was dissolved in the exposed portion without residue, and the minimum exposure amount (mJ/cm ² ) which forms this pattern was regarded as sensitivity.

[Evaluation of film thinning degree] The positive photosensitive composition was applied onto a tantalum wafer by a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C for 120 seconds to form a coating having a film thickness of 1.75 μm. membrane. The coating film was immersed in a 0.4% TMAH aqueous solution for 60 seconds, and then washed with ultrapure water for 20 seconds. Next, the thickness of the film was measured, and the degree of film thinning of the unexposed portion caused by the development was evaluated. The film thickness in this evaluation was measured using a Dektak 3ST manufactured by ULVAC.

[Evaluation of Transparency] The positive photosensitive composition was applied onto a quartz substrate by a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C for 120 seconds to form a coating film having a film thickness of 1.75 μm. The coating film was immersed in a 0.4% TMAH aqueous solution for 60 seconds, and then washed with ultrapure water for 20 seconds. Next, using a Condnct exposure machine (PLA-600S manufactured by Cannon Co., Ltd.), ultraviolet rays having a light intensity of 5.5 mW/cm ² at 365 nm were irradiated for 67 seconds (370 mJ/cm ² ) in the entire coating film. The coating film after the ultraviolet irradiation was post-baked by heating at a temperature of 230 ° C for 60 minutes to form a cured film having a film thickness of 1.5 μm. This cured film was measured at a wavelength of 200 to 800 nm using an ultraviolet visible light spectrophotometer (SIMADZU UV-2550) manufactured by Shimadzu Corporation. The film thickness in this evaluation was measured using a Dektak 3ST manufactured by ULVAC.

[Evaluation of foreign matter] After preparing a positive photosensitive resin composition, the mixture was stirred in a thermostatic chamber at 23 ° C for 50 hours, and then allowed to stand for 1 hour. This solution was applied onto a 4 Å wafer using a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C for 120 seconds to form a coating film having a film thickness of 1.75 μm, and visually observed whether or not foreign matter was present. Any foreign matter on the coating film is regarded as ○, and others are regarded as ×. For substances that were stored in the same temperature at -20 ° C for 3 months, and for the storage of six substances, the presence or absence of foreign matter was confirmed.

As shown in Table 4, the positive photosensitive resin composition using the photosensitive agent of the component (B) was stirred in a constant temperature room at 23 ° C for 50 hours and stored at a temperature of -20 ° C as shown in Examples 1 to 11. After 3 months, it was shown that the degree of film thinning was low with high sensitivity and high transmittance, and there was no excellent property of occurrence of foreign matter. Further, even if the positive photosensitive resin compositions of Examples 5 to 11 were stored at a temperature of -20 ° C for 6 months, no foreign matter was observed at all, and the storage stability was excellent.

[Industrial Applicability]

The positive photosensitive resin composition of the present invention can be used for producing a necessary cured film of a pattern, and has no foreign matter in the photosensitive resin solution, high transparency, high sensitivity, and good hardening of the film after development. membrane.

The positive-type photosensitive resin composition of the present invention is suitable as a material for forming a protective film, a planarizing film, an insulating film, or the like in a display such as a thin film transistor (TFT) liquid crystal display device or an organic EL device, and is particularly suitable for It is a material which forms an interlayer insulating film of a TFT, a protective film of a color filter, a flattening film, an uneven film under a reflective film of a reflective display, a microlens material, an insulating film of an organic EL element, and the like.

Claims (10)

A positive photosensitive resin composition comprising the following components (A) and (B) and dissolved in ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl ester Fibril 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, propylene glycol monobutyl ether, propylene glycol monobutyl ether acetate Ester, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, hydroxyl Ethyl acetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-B One or more solvents selected from the group consisting of methyl oxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, and 2-heptanone (A) Component: selected from the group consisting of at least one of unsaturated carboxylic acids and cyclohexylmaleimide, phenylmaleimide, methylmaleimide, and ethylmaleimide N-take An alkali-soluble resin which is at least one selected from the copolymerized polymers, and the number average molecular weight of the alkali-soluble resin of the component (A) is 2,000 to 30,000 in terms of polystyrene (B) Component: a 1,2-quinonediazide compound represented by the formula (1), and the component (B) is 5 to 100 parts by mass based on 100 parts by mass of the component (A). (wherein D ₁ to D ₃ are each independently a hydrogen atom or an organic group having a 1,2-quinonediazide group, but at least one of D ₁ to D ₃ has a 1,2-quinoned stack The nitrogen-based organic group, in addition, n is an integer representing from 1 to 3, and R is a monovalent organic group. The positive photosensitive resin composition of the first aspect of the invention, wherein n of the formula (1) of the component (B) is an integer of from 1 to 3, and R is a methyl group or an ethyl group. The positive photosensitive resin composition of claim 2, wherein n of the formula (1) of the component (B) is 2, and R is a methyl group. The positive photosensitive resin composition of the first aspect of the invention, which comprises the crosslinkable compound represented by the following formula (2) as the component (C) (wherein k is an integer of 2 to 10, m is an integer of 0 to 4, and R ¹ is a k-valent organic group). The positive photosensitive resin composition of claim 1, wherein the solvent is selected from propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, ethyl lactate, butyl lactate and cyclohexanone. At least one solvent. The positive photosensitive resin composition of claim 5, wherein the solvent is a mixed solvent of at least one solvent having a boiling point of 200 to 250 ° C in combination. A coating film formed with a pattern, which is characterized in that a positive photosensitive resin composition according to any one of claims 1 to 6 is applied to a substrate, exposed through a photomask, and developed. Got it. A cured film obtained by the positive photosensitive resin composition according to any one of claims 1 to 6. An interlayer insulating film obtained by the positive photosensitive resin composition according to any one of claims 1 to 6. A microlens characterized by being a positive photosensitive resin composition according to any one of claims 1 to 6.