KR101229381B1 - Positive photosensitive resin composition, and interlayer dielectrics and microlenses made therefrom - Google Patents

Abstract

assignment

Provided are a highly sensitive positive photosensitive resin composition, and an interlayer insulating film and microlens obtained thereby without generating foreign matters and reducing other characteristics such as transparency and residual film ratio.

Solution

It is achieved by the positive photosensitive composition characterized by containing the following (A) component, (B) component, and a solvent.

(A) Component: At least 1 alkali-soluble resin chosen from the polymer copolymerized using unsaturated carboxylic acid and its derivative (s) as an essential monomer species.

(B) Component: 1,2-quinonediazide compound represented by Formula (1)

[Formula 1]

(In the formula, D ₁ ~ D ₃ each independently represents an organic group having a hydrogen atom or a 1,2-quinonediazide. However, D ₁ ~ D ₃ At least one is an organic group which has a 1, 2- quinonediazide group. In addition, n is an integer of 1-3 and R represents a monovalent organic group.)

Positive Photoreceptor, Interlayer Insulator, Micro Lens

Description

Positive photosensitive resin composition and interlayer insulating film and microlens obtained thereby {POSITIVE PHOTOSENSITIVE RESIN COMPOSITION, AND INTERLAYER DIELECTRICS AND MICROLENSES MADE THEREFROM}

The present invention relates to a positive photosensitive resin composition. More particularly, the present invention relates to positive type photosensitive resin compositions suitable for display material applications.

In general, display elements, such as thin film transistor (TFT) type liquid crystal display elements and organic EL elements, are provided with an electrode protective film, a planarization film, an insulating film, etc. with a pattern formed thereon. As the material for forming these films, a photosensitive resin composition having a feature of having a small number of steps and sufficient flatness for obtaining a pattern shape is widely used. In addition, these films should have a wide process margin so as to form patterns under various process conditions in accordance with process resistance, adhesiveness with the base, and purpose of use such as heat resistance, solvent resistance, and long-term plastic resistance, and high sensitivity and high transparency. And various properties such as less film unevenness after development are required.

1, 2-quinonediazide compound is often added to the said film forming material as a photosensitizer for "photosensitive" impartation. When used as an interlayer insulating film and a microlens material, the photosensitizer should be dissolved in a safe solvent having a low load on the global environment and working environment such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethyl lactate. It is required that the transmittance after irradiation is high.

On the other hand, one of the important characteristics is the sensitivity. Since the improvement of sensitivity is connected with the drastic reduction of the production time in industrial production, it has become one of the very important characteristics with the recent increase of the demand of the liquid crystal display. However, satisfactory sensitivity could not be obtained with conventional materials. It is also possible to improve the sensitivity by increasing the solubility of the polymer in the material into the alkaline developer, but this method also has a limitation, and further, dissolution of the non-exposed part occurs, resulting in a decrease in the residual film ratio, which causes film unevenness in large substrates. There is a drawback to it.

Until now, several patents for the purpose of high sensitivity have been applied. For example, the radiation sensitive resin composition containing alkali-soluble resin, a specific polyhydroxy compound, and at least one of its derivatives is proposed (for example, refer patent document 1). However, there existed a problem, such as storage stability at the height of the symmetry of the photosensitizer. Moreover, the positive photosensitive resin composition containing alkali-soluble phenol resin and a radiation sensitive compound (for example, refer patent document 2), and the positive photosensitive resin composition containing specific alkali-soluble resin and a quinonediazide compound (See Patent Document 3, for example). Since novolak resin is used for a binder polymer, these have a problem with transparency and stability at the time of baking for a long time. As described above, it is very difficult to develop a highly sensitive resin composition while satisfying other characteristics, which is impossible with a simple combination of the prior art.

[Patent Document 1] Japanese Unexamined Patent Publication No. 4-211255

[Patent Document 2] Japanese Patent Application Laid-Open No. 9-006000

[Patent Document 3] Japanese Unexamined Patent Publication No. 8-044053

An object of the present invention is to provide a positive type photosensitive film which is free of foreign matters, has excellent storage stability, can form a coating film with high sensitivity and a small film reduction degree at development, and has high transparency of the cured film obtained by heat treatment of the coating film. To provide a resin composition. Another object of the present invention is to provide an interlayer insulating film and a microlens obtained by using the positive photosensitive resin composition.

MEANS TO SOLVE THE PROBLEM This inventor came to complete this invention as a result of earnestly researching in order to achieve the said objective. In other words,

1. Positive type photosensitive resin composition containing following (A) component, (B) component, and a solvent,

(A) component: At least 1 sort (s) of alkali-soluble resin which consists of a polymer copolymerized with at least 1 sort (s) of unsaturated carboxylic acid and its derivative (s) as an essential monomer,

(B) component: The 1, 2- quinonediazide compound represented by Formula (1).

(In the formula, D ₁ ~ D ₃ each independently represents an organic group having a hydrogen atom or a 1,2-quinonediazide. However, D ₁ ~ D ₃ At least one is an organic group which has a 1, 2- quinonediazide group. In addition, n is an integer of 1-3 and R represents a monovalent organic group.)

2. Positive type photosensitive resin composition of said 1 whose (B) component is 5-100 weight part with respect to 100 weight part of (A) component,

3. Positive type photosensitive resin composition of said 1 or 2 whose number average molecular weights of alkali-soluble resin of (A) component are 2,000-30,000 in polystyrene conversion,

4. Any of the above 1 to 3, wherein (A) component is at least one alkali-soluble resin comprising at least one of unsaturated carboxylic acid and derivatives thereof and a polymer copolymerized with N-substituted maleimide as an essential monomer species. Positive type photosensitive resin composition of one,

5. Positive type photosensitive resin composition in any one of said 1-4 in which (B) component shows the integer of 1-3 in n in Formula (1), and R represents a methyl group or an ethyl group,

6. Positive type photosensitive resin composition in any one of said 1-4 in which (B) component represents n in Formula (1), and R represents a methyl group,

7. The positive photosensitive resin composition according to any one of the above 1 to 6, wherein the component (C) contains a crosslinkable compound represented by the following Formula (2):

(In formula, k represents an integer of 2-10, m represents the integer of 0-4, R <^1> represents a k-valent organic group.)

8. The solvent includes the positive photosensitive resin composition according to any one of 1 to 7, wherein the solvent is at least one selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate and cyclohexanone,

9. Positive type photosensitive resin composition in any one of said 1-8 which is a mixed solvent which uses a solvent together with at least 1 type of solvent whose boiling point is 200 degreeC-250 degreeC,

10. The coating film with a pattern obtained by apply | coating the positive photosensitive resin composition in any one of said 1-9 on a board | substrate, exposing through a mask, and developing,

11. Cured film obtained from positive type photosensitive resin composition in any one of said 1-9;

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

13. Microlens obtained from the positive photosensitive resin composition according to any one of 1 to 9 above,

.

The positive photosensitive resin composition of the present invention can form a coating film with a high sensitivity and a small film reduction degree upon development, and the cured film obtained by heat treatment of the coating film has high transparency. In addition, the positive photosensitive resin composition of the present invention has the property of generating no foreign matter and excellent storage stability.

For this reason, the composition of this invention can be used suitably as a material for interlayer insulation films and microlenses.

Carrying out the invention  Optimal form for

Hereinafter, the positive photosensitive resin composition of this invention is demonstrated concretely.

The positive photosensitive resin composition of this invention contains the following (A) component, (B) component, and a solvent, It is characterized by the above-mentioned.

(A) component: At least 1 alkali-soluble resin which consists of a polymer copolymerized by making at least 1 sort (s) of unsaturated carboxylic acid and its derivative (s) as an essential monomer species,

(B) component: The 1, 2- quinonediazide compound represented by Formula (1).

(In the formula, D ₁ ~ D ₃ each independently represents an organic group having a hydrogen atom or a 1,2-quinonediazide. However, D ₁ ~ D ₃ At least one is an organic group which has a 1, 2- quinonediazide group. In addition, n is an integer of 1-3 and R represents a monovalent organic group.)

<(A) component: Alkali-soluble resin>

The alkali-soluble resin used for the positive photosensitive resin composition of this invention is at least 1 sort (s) which consists of a polymer (Hereinafter, it is called a specific copolymer.) Copolymerized by making at least 1 sort (s) of unsaturated carboxylic acid and its derivative (s) as an essential monomer species. Alkali-soluble resin.

That is, alkali-soluble resin used for this invention has the property which is soluble in an alkaline solution in a specific copolymer. (A) component consists of 1 type or multiple types of alkali-soluble resin chosen from the specific copolymer soluble in alkaline solution.

This specific copolymer is a polymer whose polystyrene conversion number average molecular weight (henceforth a number average molecular weight.) Is 2,000-30,000. Preferably it is 2,500-15,000, More preferably, it is 3,000-10,000.

When a number average molecular weight is 2,000 or less, the pattern shape obtained may be bad, a pattern residual film ratio may fall, or pattern heat resistance may fall. On the other hand, when the number average molecular weight exceeds 30,000, the applicability of the photosensitive resin composition is poor, the developability is lowered, peeling occurs, the pattern shape obtained is poor, or the solubility in organic solvents is lowered. There is a case. Moreover, when a number average molecular weight exceeds 40,000, a residual film may arise between patterns of 50 micrometers or less, and resolution may fall.

Although unsaturated carboxylic acid is not specifically limited as a monomer type for obtaining this specific copolymer, As a specific example, acrylic acid, methacrylic acid, itaconic acid, mulleinic acid, fumaric acid, etc. are mentioned.

In this invention, although at least 1 type of these unsaturated carboxylic acids is essential as a monomer type for obtaining a specific copolymer, you may use 2 or more types together.

The proportion of this unsaturated carboxylic acid is preferably 1 to 30% by weight, more preferably 3 to 25% by weight, and most preferably 5 to 20% by weight of the total amount of monomer species used to obtain a specific copolymer. to be. When the amount is less than 1% by weight, the solubility is insufficient in the alkaline developer, and when it exceeds 30% by weight, the solubility in the alkaline developer is too high, so that dissolution of the non-exposed part may occur and the residual film ratio may decrease.

Moreover, as a monomer type for obtaining a specific copolymer, in addition to unsaturated carboxylic acid, an unsaturated carboxylic acid derivative can be used or used together. Specific examples thereof include alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate, methyl acrylate and isopropyl acrylate. Cyclic alkyl esters such as alkyl esters, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyloxyethyl methacrylate, isoboroyl methacrylate, phenyl methacrylate, benzyl methacrylate Aryl esters such as acrylate, diethyl mullein acid, diethyl fumarate, diethyl itaconate, dihydroxy acid methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl Hydroxyalkyl esters, such as methacrylate, are mentioned.

And bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydrate Hydroxybicyclo [2.2.1] hepto-2-ene, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2-ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2 -Ene, 5,6-dihydroxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene, 5,6-di (hydroxy Methyl) bicyclo [2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-dimethoxybicyclo [ 2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methyl ratio Cyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2 -Ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hymic acid anhydride), 5-t-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5 -Cyclohexyloxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-di (t-butoxycarbonyl) And bicyclounsaturated compounds such as bicyclo [2.2.1] hepto-2-ene and 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene.

As other unsaturated carboxylic acid derivatives, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycidyl (alpha)-n-propyl acrylate, the glycidyl (alpha)-n-butyl acrylate, and acrylic acid -3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl , o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like.

Among them, epoxy groups such as glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether Containing unsaturated carboxylic acid ester etc. can alleviate shrinkage | contraction of a cured film, and it is preferable.

In the present invention, an ethylenic compound copolymerizable with an unsaturated carboxylic acid and its derivative can also be used in combination as a monomer species for obtaining a specific copolymer. Specific examples of such ethylenic compounds include cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-meth Oxy styrene, p-hydroxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl- 1, 3- butadiene etc. are mentioned. These ethylenic compounds can be introduce | transduced in order to adjust the solubility, hydrophobicity, etc. of a specific copolymer, and to control molecular weight. Among these, N-substituted maleimide, such as cyclohexyl maleimide, phenyl maleimide, methyl maleimide, and ethyl maleimide, is preferable from a heat resistant viewpoint.

In this invention, the ratio which an ethylenic compound occupies becomes like this. Preferably it is 5-50 weight%, More preferably, it is 15-45 weight%, More preferably, 20-in the total amount of the monomer species used for obtaining a specific copolymer. 40 wt%. When an ethylenic compound is 5 weight% or less, the film | membrane reduction at the time of image development is large, and the film shrinkage by the thermal decomposition of a cured film may become large. Moreover, when an ethylenic compound is 50 weight% or more, the residue at the time of image development may increase.

Preferable specific copolymer is 1-30 weight% of unsaturated carboxylic acid, and the remainder is unsaturated carboxylic acid derivative in the total amount of the monomer species used in order to obtain a specific copolymer, 1-30 weight% of unsaturated carboxylic acid, ethylenic The compound is 5-50 weight%, and the remainder is an unsaturated carboxylic acid derivative.

The method of obtaining the specific copolymer used for this invention is not specifically limited. Generally, the monomer mixture containing the monomer species used for obtaining the above-mentioned specific copolymer is produced by radical polymerization in a polymerization solvent. Moreover, you may superpose | polymerize a monomer mixture in the state which protected the functional group of a specific monomer as needed, and may perform a deprotection process after that.

At this time, the polymerization temperature is not particularly limited as long as the monomer is polymerized, preferably the temperature is 50 ° ~ 110 ° C.

Examples of the polymerization solvent include alcohols such as methanol, ethanol, propanol and butanol, ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene and xylene; N, N-dimethylformamide; , Polar solvents such as N-methyl-2-pyrrolidone, esters such as ethyl acetate, butyl acetate and ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate and ethyl 3-methoxypropionate, 2 Alkoxy esters such as ethyl methoxy propionate, ethyl 3-ethoxy propionate and ethyl 2-ethoxy propionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, (Di) glycol dialkyl ethers such as propylene glycol dimethyl ether and dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol (Di) glycol monoalkyl ethers such as nomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether, and propylene glycol mono And ketones such as glycol monoalkyl ether esters such as methyl ether acetate, carbitol acetate, and ethyl serosol acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. These polymerization solvents can be used individually or in combination of 2 or more types.

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

Moreover, it is preferable that (A) component (alkali-soluble resin) used for the positive photosensitive resin composition of this invention has little content of a residual monomer. Residual monomer here means the unreacted substance which consists of each monomer species remaining after copolymerizing each monomer species and obtaining a specific copolymer. The residual amount of these residual monomers can be represented by the residual monomer ratio, and the residual monomer ratio can be expressed by the total mass ratio (weight%) of each residual monomer to the total mass of each monomer used in the copolymerization reaction. In addition, when (A) component is alkali-soluble resin which consists of several specific copolymer, about specific mass of several specific copolymers with respect to the total mass of the monomer species used for copolymerization of each specific copolymer, It can represent with the total mass ratio (weight%) of a residual monomer.

As a residual amount analysis method of a residual monomer, for example, it can confirm by analyzing the copolymerized reaction liquid using liquid chromatography etc.

As residual monomer ratio, 2.5 weight% or less is preferable, More preferably, it is 2.0 weight% or less, More preferably, it is 1.5 weight% or less. When the residual monomer ratio exceeds 2.5% by weight, the electrical characteristics of the display element may decrease.

The method of reducing the residual monomer rate in alkali-soluble resin is not specifically limited, For example, the method of performing purification, such as reprecipitation which is generally known in polymer synthesis, or raising the reaction temperature in the final stage of superposition | polymerization Can be heard.

<(B) component: 1,2-quinone diazide compound>

(B) component used for the positive photosensitive resin composition of this invention is a 1, 2- quinonediazide compound which has a specific structure, and is represented by Formula (1).

(In the formula, D ₁ ~ D ₃ each independently represents an organic group having a hydrogen atom or a 1,2-quinonediazide. However, D ₁ ~ D ₃ At least one is an organic group which has a 1, 2- quinonediazide group. In addition, n is an integer of 1-3 and R represents a monovalent organic group.)

In formula (1), n is an integer of 1-3, R represents monovalent organic group. Although R is not specifically limited, For example, the alkyl group which has a branched structure, such as linear alkyl groups, such as a methyl group, an ethyl group, and a propyl group, isopropyl, isobutyl, sec-butyl, tert- butyl, etc. is mentioned. . In these, a C1-C10 aliphatic group is preferable, More preferably, it is a C1-C4 alkyl group.

D ₁ to D ₃ are each independently an organic group having a hydrogen atom or a 1,2-quinonediazide group, and D ₁ to D _3. At least one is an organic group which has a 1, 2- quinonediazide group. In Formula (1), although the organic group which has a 1, 2- quinone diazide group is not specifically limited, For example, a 1, 2- benzoquinone diazide- 4-sulfonyl group and a 1, 2- naphthoquinone diazide -5-sulfonyl group, a 1, 2- naphthoquinone diazide-4- sulfonyl group, etc. are mentioned. Among them, from the viewpoint of transparency of the cured film, a 1,2-naphthoquinone diazide-5-sulfonyl group and a 1,2-naphthoquinone diazide-4-sulfonyl group are preferable.

Although the (B) component used for this invention will not be specifically limited if it is a 1, 2- quinonediazide compound represented by Formula (1), From a viewpoint of the solubility, sensitivity, resolution, residual film rate, and transparency to the solvent mentioned later, A compound in which R represents a methyl group or an ethyl group and n is 1 or 2 is preferable. More preferably, R is a compound represented by following formula (3) which represents a methyl group and n is 2.

(In the formula, D ₁ ~ D ₃ each independently represents an organic group having a hydrogen atom or a 1,2-quinonediazide. However, D ₁ ~ D ₃ At least one is an organic group which has a 1, 2- quinonediazide group. )

The method of obtaining the 1, 2- quinonediazide compound represented by Formula (1) used for this invention is not specifically limited. In general, the following formula (4)

It can obtain by making the compound represented by and reacting the compound which has a 1, 2- quinonediazide group. As the latter compound, chlorides having 1,2-quinonediazide groups are generally used widely.

For example, the compound represented by Formula (4) and 1,2-, such as 1,2-naphthoquinone diazide-5-sulfonyl chloride and 1,2-naphthoquinone diazide-4-sulfonyl chloride, etc. By esterification with quinone diazide sulfonyl halide, a 1,2-quinone diazide compound represented by formula (1) is obtained.

At this time, some or all hydroxyl groups of the compound represented by the formula (4) react with the compound having the 1,2-quinonediazide group. In order to obtain sufficient sensitivity in the present invention, the average condensation ratio of the esterification reaction [( Number of esterified phenolic hydroxyl groups / number of phenolic hydroxyl groups before reaction) x 100] is required to be 5 to 100%. This average condensation rate becomes like this. Preferably it is 10 to 98%, More preferably, it is 20 to 95%. In the case where the average condensation ratio of the esterification reaction is 5% or less, the solubility difference with respect to the alkaline developer between the exposed portion and the non-exposed portion cannot be sufficiently obtained, and therefore, a pattern having a high resolution may not be obtained.

In the positive photosensitive resin composition of the present invention, the content of the component (B) is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight, further preferably 100 parts by weight of the component (A). Is 10 to 30 parts by weight. When less than 5 weight part, the difference in solubility with respect to the developing solution of the exposed part of a positive photosensitive resin composition and a non-exposed part may become small, and patterning by image development may become difficult. Moreover, when it exceeds 100 weight part, a 1, 2- quinonediazide compound may not fully decompose | disassemble by short time exposure, a sensitivity may fall, or (B) component may absorb light and may reduce transparency of a cured film.

<Solvent>

The solvent used for this invention will not be specifically limited if it melt | dissolves (A) component, (B) component, (C)-(F) component etc. which are mentioned later.

Specific examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl vertical solbu acetate, ethyl vertical solbu acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, and propylene glycol mono Methyl 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, cyclohexanone, 2-hydroxy Ethyl propionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl hydroxy acetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, pyruvic acid , There may be mentioned ethyl acetate, butyl acetate, ethyl lactate, lactic acid butyl, and 2-heptanone. These solvents can be used individually or in combination of 2 or more types.

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

In addition, at least one of the solvent of the boiling point 200 ° ~ 250 ° C. may be used in addition to the solvent. At this time, the boiling point of the solvent of 200 ° C. to 250 ° C., 1 to 50% by weight of all the solvent contained in the positive photosensitive resin composition, more preferably 5% to 40% by weight. If it is 50 weight% or more, the favorable leveling property of a coating film may be difficult to be acquired, and at 1 weight% or less, the said effect may not be acquired.

In addition, a boiling point in this specification means the standard boiling point at 1 atmosphere.

Specific examples of solvents having a boiling point of 200 ° C. to 250 ° C. include N-methylpyrrolidone, γ-butyrolactone, diethylene glycol monoethyl ether (ethylcarbitol), diethylene glycol monobutyl ether (butyl carbitol), Acetamide, benzyl alcohol, etc. are mentioned.

<(C) component: a crosslinkable compound>

The positive photosensitive resin composition of this invention can contain the crosslinkable compound represented by Formula (2) as (C) component.

(In formula, k represents an integer of 2-10, m represents the integer of 0-4, R <^1> represents a k-valent organic group.)

(C) component will not be specifically limited if it is a compound which has a cyclohexene oxide structure represented by Formula (2). Specific examples thereof include the following formulas C1 and C2 or commercial products shown below.

As a commercial item, it is epoxide GT-401, copper GT-403, copper GT-301, copper GT-302, ceroxide 2021, ceroxide 3000 (trade name of Daicel Chemical Industries, Ltd.), alicyclic epoxy resin Denacol EX-252 (brand name made by Nagase ChemteX Co., Ltd.), CY175, CY177, CY179 (more than brand name made by CIBA-GEIGY AG), Araldide CY-182, copper CY-192, copper CY-184 (more than , Brand name made by CIBA-GEIGY AG), epicron 200, copper 400 (more than Dainippon Inky Chemical Co., Ltd. brand name), epicoat 871, copper 872 (above, brand name made by Yucca Epoxy Co., Ltd.), ED -5661, ED-5662 (above, a brand name made by Ceranie Coatings Co., Ltd.), etc. are mentioned.

In addition, these crosslinkable compounds can be used individually or in combination of 2 or more types.

Among these, compounds represented by the formulas C1 and C2, epoxides GT-401 and GT-403, which have a cyclohexene oxide structure in terms of process resistance and transparency, such as heat resistance, solvent resistance, and internal temporal resistance, etc. GT-301, GT-302, ceroxide 2021, and ceroxide 3000 are preferable.

The addition amount of the said (C) component is 3-50 weight part with respect to 100 weight part of (A) component, Preferably it is 7-40 weight part, More preferably, it is 10-30 weight part. When the content of the crosslinkable compound is small, the density of crosslinking formed by the crosslinkable compound is not sufficient, and thus the effect of improving heat resistance, solvent resistance, resistance to long-time firing, etc. after pattern formation may not be obtained. . On the other hand, when it exceeds 50 weight part, an uncrosslinked crosslinking | crosslinked compound exists, the heat resistance, solvent resistance, resistance to long-time baking after pattern formation, etc. fall, and the storage stability of the photosensitive resin composition may worsen. .

<(D) component: Surfactant>

The positive photosensitive resin composition of this invention may add surfactant for the purpose of improving applicability | paintability. Such surfactants are not particularly limited to fluorine-based surfactants, silicone-based surfactants and nonionic surfactants. For example, commercial items, such as those manufactured by Sumitomo 3M Co., Ltd., Dainippon Inkki Chemical Co., Ltd., and Asahi Glass Co., Ltd., may be used, and these commercial items can be easily obtained.

As (D) component, it can use combining 1 type (s) or 2 or more types in the said surfactant.

Among these surfactants, fluorine-based surfactants are preferable in that the applicability improving effect is remarkable.

Specific examples of the fluorine-based surfactants include F-Top EF301, EF303, and EF352 (trade name of Tochem Products Co., Ltd.), Megapak F171, F173, R-30 (trade name of Dainippon Inky Chemical Co., Ltd.), Flora FC430 And FC431 (trade name of Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Saffron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (trade name of Asahi Glass Co., Ltd.). It is not limited to.

In the positive photosensitive resin composition of the present invention, the amount of the component (D) added is 0.01 to 5 parts by weight, preferably 0.01 to 3 parts by weight, more preferably 0.01 to 2 parts by weight based on 100 parts by weight of the component (A). Parts by weight When the amount of the surfactant added is more than 5 parts by weight, staining occurs easily on the coating film, and when it is lower than 0.01 part by weight, the effect of improving applicability may not be obtained.

<(E) component: adhesion promoter>

The positive type photosensitive resin composition of this invention may add an adhesion promoter for the purpose of improving adhesiveness with the board | substrate after image development. Specific examples of such adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane and chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, Alkoxysilanes such as dimethylvinylethoxysilane, diphenyldimethoxysilane and phenyltriethoxysilane, hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimida Silazanes such as sol, vinyl trichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane silanes such as γ- (N-piperidinyl) propyltrimethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-melcaptobenzimidazole, 2-melcaptobenzothiazole, 2- Melcapto Heterocyclic compounds, such as a oxazole, a urasol, thiouracil, melcaptoimidazole, and a mercaptopyrimidine, urea, such as 1, 1- dimethyl urea and 1, 3- dimethyl urea, or thiourea compound, are mentioned. have.

The adhesion promoter may be, for example, a compound of a commercially available product such as manufactured by Shin-Etsu Chemical Co., Ltd., GE Toshiba Silicone Co., Ltd., or Tole Dow Corning Co., Ltd., and these commercially available compounds may be easily obtained. Can be.

As the component (E), one or two or more kinds of the adhesion promoters may be used in combination.

The addition amount of these adhesion promoters is 20 weight part or less normally with respect to 100 weight part of (A) component, Preferably it is 0.01-10 weight part, More preferably, it is 0.5-10 weight part. When it uses 20 weight part or more, the heat resistance of a coating film may fall, and when less than 0.1 weight part, sufficient effect of an adhesion promoter may not be acquired.

<(F) component: Other additives>

In the positive photosensitive resin composition of the present invention, pigments, dyes, preservative stabilizers, antifoaming agents, dissolution accelerators such as polyhydric phenols and polycarboxylic acids, etc. may be added, if necessary, as long as the effects of the present invention are not reduced. Also good.

<Positive Photosensitive Resin Composition>

The positive photosensitive resin composition of this invention contains (A) component, (B) component, and a solvent, It is characterized by the above-mentioned. In other words, this invention is a positive photosensitive resin composition containing (A) component, (B) component and a solvent, or these, and 1 or more types of (C)-(F) component as needed.

In the present invention, specific examples of preferred positive photosensitive resin compositions include

[1] Positive type photosensitive resin composition which consists of 100 weight part of (A) component, 5-100 weight part of (B) component, and a solvent,

[2] a positive photosensitive resin composition containing [1] and (C) the component in an amount of 3 to 50 parts by weight,

[3] a positive photosensitive resin composition comprising the above [2] and (D) components in an amount of 0.01 to 5 parts by weight,

[4] a positive photosensitive resin composition comprising the above [3] and (E) components at 20 parts by weight or less;

[5] The crosslinkable compound component (C) containing 10 to 30 parts by weight of the 1,2-quinonediazide compound component (B) and two or more epoxy groups, based on 100 parts by weight of the alkali-soluble resin component (A) Positive type photosensitive resin composition which consists of 10-30 weight part,

And the like.

The solid content concentration of such a positive photosensitive resin composition of this invention is not specifically limited as long as each component is melt | dissolving uniformly. Usually, it is common to use in 1 to 50weight% of a range. In addition, it can also be diluted with a solvent and adjusted to an appropriate solid content concentration for the purpose of adjusting the film thickness and applying it to the conditions of an application apparatus.

Positive type photosensitive resin composition of this invention is easily prepared by mixing (A) component and (B) component, or these and 1 or more types of (C)-(F) component uniformly with a solvent as needed. can do. Under the present circumstances, (A) component may use the reaction solution which copolymerized the specific copolymer as it is.

Although the preparation method of a positive photosensitive resin composition is not specifically limited, For example, (A) component (alkali-soluble resin) is melt | dissolved in a solvent and (B) component (1, 2- quinonediazide compound) in this solution. And (C) component (crosslinkable compound), (D) component (surfactant), and (E) component (adhesion promoter) are mixed in a predetermined ratio, and the method of making a uniform solution is mentioned. Moreover, you may add and mix (F) component as needed.

In addition, as long as the uniformity of a positive photosensitive resin composition and the effect of this invention are not impaired, you may mix each heated component or you may heat partly during mixing. At this time, it is preferable that solution temperature is below the boiling point of a solvent.

It is preferable to use the mixed-form positive type photosensitive resin composition after filtering using a filter etc. which have a pore size of about 0.5 micrometer.

The positive photosensitive resin composition of this invention obtained by such a method suppresses generation | occurrence | production of a foreign material, and is excellent in storage stability.

<Coating film and its cured film>

The positive photosensitive resin composition of the present invention is a spin coating, a spill coating, a roll coating, a slit coating, a slit on a substrate such as a glass substrate, a silicon wafer, an oxide film, a nitride film, a substrate coated with a metal such as aluminum, molybdenum or chromium. After coating by spin coating, inkjet coating, etc., it can preliminarily dry by hotplate, oven, etc., and can form a coating film. At this time, the pre-drying, it is preferable to set the conditions for 30 to 600 seconds at a temperature of 80 ° ~ 130 ° C., it is possible to select suitable conditions as needed.

Subsequently, by attaching a mask having a predetermined pattern onto the coating film obtained above, irradiating light such as ultraviolet rays and developing with an alkali developer, the exposed portion is washed away to obtain a sharp relief pattern of a cross section. At this time, the developing solution used will not be specifically limited if it is aqueous alkali solution. Specific examples thereof include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, ethanolamine, propylamine and ethylene. Amine aqueous solutions, such as diamine, are mentioned.

It is common that the said alkaline developing solution is 10 weight% or less aqueous solution, Preferably 0.1-3.0 weight% aqueous solution etc. are used. Furthermore, alcohol and surfactant can also be added and used to the said developing solution, These are respectively 0.05-10 weight part with respect to 100 weight part of developing solutions.

Among these, tetraethylammonium hydroxide 0.1-2.38 weight% aqueous solution is generally used as a photoresist developing solution, The photosensitive resin composition of this invention can also be developed using this solution, without causing problems, such as swelling.

As the developing method, any of a liquid dipping method, a dipping method and a fluid deposition method may be used. At this time, the developing time is usually 15 to 180 seconds. After the development, washing with running water for 20 to 90 seconds, followed by air drying with compressed air, compressed nitrogen, or spin removes moisture on the substrate, thereby obtaining a coating film having a pattern. Thereafter, the coating film on which the pattern is formed is irradiated with light such as ultraviolet light using a high pressure mercury lamp on the entire surface to completely decompose the component (B) (1,2-quinonediazide compound) remaining in the pattern coating film. This improves the transparency of the coating film. Subsequently, it heats using a hotplate, oven, etc., and hardens a coating film (henceforth a post-baking), and is excellent in heat resistance, transparency, planarization property, low water absorption, chemical resistance, and favorable relief. A coating film having a pattern can be obtained.

Post-baking conditions, at a temperature of 140 ° ~ 250 ° C., 5-30 minutes on a hot plate, in the oven 30 to 90 minutes. In this way, the cured film which has the favorable pattern shape made into the objective can be obtained. In addition, the desired microlens can be obtained by selecting the pattern shape.

As described above, the positive photosensitive resin composition of the present invention can form a coating film having a very fine sensitivity with a very high sensitivity and a very small film reduction during development. And the cured film obtained by this coating film is excellent in heat resistance, solvent resistance, and transparency.

For this reason, this cured film can be used suitably for an interlayer insulation film, various insulating films, various protective films, etc., and can also be used suitably also as a micro lens by selecting a pattern shape.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Explanation of Abbreviations Used in the Examples.

(Monomer)

AA: acrylic acid

MAA: methacrylic acid

MMA: Methyl methacrylate

BMA: benzyl methacrylate

NBMA: n-butyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

HPMA: 2-hydroxypropyl methacrylate

CHMI: N-cyclohexylmaleimide

EMI: ethyl maleimide

PHMI: N-phenylmaleimide

(Polymerization initiator)

AIBN: azobisisobutylonitrile

(solvent)

PGMEA: Propylene glycol monomethyl ether acetate

EL: ethyl sulfate

GBL: γ-butyrolactone

MAK: 2-heptanone

<Synthesis example 1> Specific copolymer solution (P1)

As a monomer component constituting the specific copolymer, MAA13.5g, CHMI35.3g, HEMA25.5g, MMA25.7g were used, and AIBN5g was used as the radical polymerization initiator, in a temperature of 60 ° C to 100 ° C in 200g of solvent PGMEA. It was made to react, and the specific copolymer whose number average molecular weight (henceforth Mn.) Is 4,100 and a weight average molecular weight (henceforth Mw.) Is 7,600 was obtained. The same solvent as the solvent used in the polymerization reaction was added thereto to obtain a solution (P1) having a specific polymer concentration of 27% by weight. The results are shown in Table 1. The measurement of Mn and Mw was performed by Jasco Corporation's room temperature gel permeation chromatography (GPC) apparatus (Shodex® column (1 KF803L and 1 KF804L), and THF was used as the elution solvent. 1 ml / min was measured under the condition that the column temperature was 40 ° C. On the other hand, Mn and Mw were in terms of polystyrene.

<Synthesis example 2-4> Specific copolymer solution (P2-P4)

The specific copolymer obtained by changing the monomer component and the solvent of the synthesis example 1 to the monomer component and the solvent of the synthesis examples 2-4 of Table 1, and carrying out similarly to the synthesis example 1, and obtaining specific copolymer solution (P2-P4). Mn and Mw were measured. The results are shown in Table 1.

<Synthesis example 5> Specific copolymer solution (P5)

As the monomer component constituting the specific copolymer, AA13.5g, PHMI35.3g, HEMA25.5g, MMA23.7g were used, and AIBN5g was used as the radical polymerization initiator, and in a temperature of 60 ° C to 70 ° C in 150g of solvent PGMEA. The reaction was carried out to obtain a solution (P5) having a concentration of 40.0% by weight of the specific copolymer having Mn of 5,400 and Mw of 10,200. The results are shown in Table 1. In addition, Mn and Mw were measured similarly to the synthesis example 1.

* 1: solvent used for polymerization of a specific copolymer

<Examples 1-11>

1,2-quinone diazide compound (Hereinafter, it is called a photosensitive agent) in an alkali-soluble resin solution, 1 or more types chosen from specific copolymer solution (P1-P4) obtained by the method similar to the said synthesis examples 1-5. After adding the crosslinking | crosslinked compound, surfactant, adhesion | attachment adjuvant, and a solvent, it stirred at room temperature for 8 hours, and prepared the positive photosensitive composition of the composition shown to Table 2 and Table 3.

The photosensitizer, crosslinking | crosslinked compound, surfactant, and adhesive adjuvant used here are as follows.

[Photosensitive agent]

VIID: A compound synthesized by a condensation reaction of 1 mol of trisphenol and 2.5 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride represented by the following structure.

 [Crosslinkable Compound]

The compound represented by following formula C1 or C2.

delete

 [Surfactants]

R30: Megapak R-30 (brand name) made by Dainippon Inky Chemical Industry Co., Ltd.

[Adhesive preparation]

MPTS: γ-methacryloxypropyltrimethoxysilane

<Comparative Example 1>

Alkali-soluble resin solution, 70.8 g of a specific copolymer (P1) solution obtained in Synthesis Example 1 above, by condensation reaction of 1 mmol of a methyl ester methyl ester and 2.5 mmol of 1,2-naphthoquinone diazide-5-sulfonyl chloride After adding 3.7 g of compound (XD2) synthesize | combined, 5.2 g of crosslinkable compound C1, 0.01 g of R30, 0.9 g of MPTS, and 0.4 g of PGMEA2, were added, and it stirred at room temperature for 8 hours, and prepared the positive photosensitive composition. This result is also shown in Table 3.

Table 4 shows the results of the sensitivity, film reduction degree, transparency, and foreign matter generation evaluation of the positive photosensitive resin compositions of Examples 1 to 11 and Comparative Example 1 shown in Tables 2 and 3, respectively.

The evaluation was performed in the following manner.

 [Sensitivity evaluation]

The positive photosensitive composition was applied onto a silicon 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. The film thickness was measured using Dektak 3ST manufactured by ULVAC. The coating film was irradiated with ultraviolet light having a light intensity of 5.5 mW / cm ² at 365 nm for a predetermined period of time through a test mask by Canon UV irradiation apparatus PLA-600FA, followed by 0.4% tetramethylammonium hydroxide (hereinafter, After developing by immersing in an aqueous solution for 60 seconds, it washed with running water for 20 seconds with pure water, and formed the positive pattern. The formed pattern was observed with an optical microscope, and the sensitivity was set as the minimum exposure amount (mPa / cm <^2> ) in which the line-and-space pattern from 3.0 micrometers to 50 micrometers was formed without the residue which melted in the exposure part.

[Evaluation of membrane reduction]

After the positive photosensitive resin composition was applied on a silicon wafer by using a spin coater, prebaking was performed 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. This coating film was immersed in 0.4% TMAH aqueous solution for 60 seconds, and then washed with running water for 20 seconds with pure water. Subsequently, the thickness of this film was measured, and the film reduction degree of the non-exposed part by development was evaluated. In this evaluation, the film thickness was measured using Dektak 3ST manufactured by ULVAC.

[Transparency Evaluation]

After the positive photosensitive resin composition was applied on a quartz substrate using a spin coater, prebaking was performed 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. This coating film was immersed in 0.4% TMAH aqueous solution for 60 seconds, and then washed with running water for 20 seconds with pure water. Next, using the contact exposure machine (PLA-600S by Canon Corporation), the ultraviolet-ray with a light intensity of 5.5 mW / cm <^2> at 365 nm was irradiated to the whole coating film for 67 second (370 mPa / cm <^2> ). Post-baking was performed by coating the film after ultraviolet irradiation at a temperature of 230 ° C. for 60 minutes to form a cured film having a thickness of 1.5 μm. It measured at the wavelength of 200-800 nm using the ultraviolet visible spectrophotometer (SIMADZU UV-2550 by Shimadzu Corporation), and the transmittance | permeability of the said cured film was calculated | required and transparency was evaluated.

[Foreign Material Evaluation]

After preparing the positive photosensitive resin composition, the mixture was stirred for 50 hours in a constant temperature room at 23 ° C., and then allowed to stand for 1 hour. The solution was applied to a 4 inch 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. (Circle) and the thing which did not generate | occur | produce foreign matter in the coating film were made into x. In this way, the presence of foreign matters was stored for three months at the temperature of -20 ° C and for six months.

As shown in Table 4, the positive photosensitive resin composition using the photosensitive agent of component (B), as shown in Examples 1 to 11, was stirred in a constant temperature room at 23 ° C. after 50 hours and at 3 ° C. at −20 ° C. After storage for a month, all showed excellent properties of low film reduction, high sensitivity and transmittance, and no foreign matter. In addition, in the positive photosensitive resin composition of Examples 5 to 11, no foreign matter was observed at all after storage at a temperature of −20 ° C. for 6 months, and storage stability was excellent.

The positive photosensitive resin composition of the present invention is a cured film that requires pattern formation, and can be used to produce a cured film that is free of foreign matter in the photosensitive resin solution, has high transparency, high sensitivity, and has good film stain after development.

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

Claims (13)

The positive photosensitive resin composition containing the following (A) component, (B) component, and a solvent. (A) component: At least 1 alkali-soluble resin which consists of a polymer copolymerized using at least 1 type of unsaturated carboxylic acid and its derivative (s) as an essential monomer type, (B) component: The 1, 2- quinonediazide compound represented by Formula (1). [Formula 1]

(In formula, D <_1> -D <_3> is an organic group which respectively independently has a hydrogen atom or a 1, 2- quinonediazide group. However, at least _{1 of} D <_1> -D <_{3> has a 1} , 2- quinonediazide group. And n is an integer of 1 to 3, and R represents an aliphatic group having 1 to 10 carbon atoms.) The method of claim 1, Positive component photosensitive resin composition characterized by the above-mentioned (A) component with respect to 100 weight part of components (B) 5-100 weight part. The method of claim 1, The number average molecular weight of alkali-soluble resin of (A) component is 2,000-30,000 in polystyrene conversion, The positive type photosensitive resin composition characterized by the above-mentioned. The method of claim 1, Positive type photosensitive resin (A) component is at least 1 sort (s) of alkali-soluble resin which consists of a polymer copolymerized by including at least 1 type of unsaturated carboxylic acid and its derivative (s), and N-substituted maleimide as an essential monomer type. Composition. The method of claim 1, The positive photosensitive resin composition of (B) component whose n is an integer of 1-3 in Formula (1), and R is a methyl group or an ethyl group. The method of claim 1, The positive photosensitive resin composition of (B) component whose n is 2 in Formula (1), and R is a methyl group. The method of claim 1, The positive photosensitive resin composition which further contains the crosslinking | crosslinked compound represented by following formula (2) as (C) component. [Formula 2]

(In formula, k represents an integer of 2-10, m represents the integer of 0-4, R <^1> represents k-valent organic group.) The method of claim 1, The solvent is at least one selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, ethyl lactate, butyl lactate and cyclohexanone. The method of claim 1, Positive solvent photosensitive resin composition, characterized in that the solvent is a mixed solvent using at least one solvent having a boiling point of 200 ° ~ 250 ° C. The coating film with a pattern obtained by apply | coating the positive photosensitive resin composition of any one of Claims 1-9 to a board | substrate, exposing through a mask, and developing. The cured film obtained from the positive photosensitive resin composition of any one of Claims 1-9. The interlayer insulating film obtained from the positive photosensitive resin composition of any one of Claims 1-9. The microlens obtained from the positive photosensitive resin composition of any one of Claims 1-9.