KR102369410B1 - Photosensitive resin composition and cured film prepared therefrom - Google Patents

Abstract

The present invention relates to a photosensitive resin composition and a cured film prepared therefrom, wherein the photosensitive resin composition includes a siloxane polymer, a 1,2-quinonediazide-based compound, and a solvent, and the siloxane polymer is a linear siloxane structural unit. By including 2 to 15 mol% based on the number of moles of Si atoms, high heat resistance and high transparency, which are the advantages of a composition containing a siloxane polymer, and improving crack resistance at the same time, curing excellent stability even in the post process A film or a planarization film may be provided.

Description

Photosensitive resin composition and cured film prepared therefrom

The present invention relates to a photosensitive resin composition and a cured film prepared therefrom. More specifically, the present invention relates to a positive photosensitive resin composition containing linear siloxane, and a cured film prepared therefrom and used for liquid crystal display devices, organic EL display devices, and the like.

In general, in a liquid crystal display device or an organic EL display device, a transparent planarization film is used on the upper part of a thin film transistor (TFT) substrate as an insulating purpose to prevent cross-talk between a transparent electrode and a data line. Accordingly, a transparent pixel located near the data line Since the aperture ratio of the panel can be improved through the electrode, high luminance/high resolution can be realized. Several steps are applied to the transparent planarization film to have a specific pattern shape. Among them, a positive photosensitive resin composition with a small number of steps is widely used. In particular, as a material having high heat resistance, high transparency, and low dielectric constant, a positive photosensitive resin composition using a siloxane polymer is known.

As a conventional siloxane-based composition for realizing high heat resistance, high transparency and high resolution, a 1,2-quinonediazide-based compound in a siloxane polymer in which a T-type siloxane structural unit having a phenyl moiety and a Q-type siloxane structural unit are combined A composition containing For example, Korean Patent Application Laid-Open No. 2006-59202 discloses a siloxane polymer having a phenolic hydroxyl group of 20 mol% or less, a quinonediazide-based compound having a structure without a methyl group at the ortho or para position of the phenolic hydroxyl group (0.1 to 10% by weight) ), and a composition containing a compound having an alcoholic hydroxyl group and/or a cyclic compound having a carbonyl group as a solvent, wherein a cured film made by the composition satisfies a transmittance of 95% or more and a specific chromaticity coordinate.

On the other hand, after forming a transparent planarization film from such a composition, a process of forming an inorganic film by chemical vapor deposition, sputtering, etc. is performed. At this time, the film surface is locally exposed to heat or UV, causing a problem of cracking on the planarization film. can For example, when the conventional compositions exemplified above are formed to be thicker than a general planarization film (2 to 3 μm) according to process necessity, the stiffness of the film also increases. A cracking problem occurs.

Accordingly, there is a demand for a siloxane-based photosensitive resin composition that exhibits excellent crack resistance while maintaining high heat resistance and high transparency in subsequent high-temperature treatment even when a thick planarization film is formed from the composition.

Korean Patent Laid-Open Publication No. 2006-59202 (Toray Corporation) 2006.06.01.

Accordingly, an object of the present invention is to provide a photosensitive resin composition exhibiting excellent crack resistance while maintaining high heat resistance and high transparency, and a cured film prepared therefrom and used for liquid crystal display devices, organic EL display devices, and the like.

In order to achieve the above object, the present invention provides (A) a siloxane polymer comprising at least one structural unit derived from a silane compound represented by the following formula (1), (B) a 1,2-quinonediazide-based compound, and (C) ) a solvent, and the siloxane polymer (A) comprises a structural unit derived from a silane compound having n = 2 in the following formula (1) in an amount of 2 to 15 mol% based on the number of moles of Si atoms, providing a photosensitive resin composition do:

[Formula 1]

(R ¹ ) _n Si(R ² ) _4-n

In Formula 1, R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, or an alkylaryl group having 7 to 12 carbon atoms, A plurality of R ¹ may each be the same or different; R ² is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, an amino group, an acyloxy group having 2 to 12 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms, and a plurality of R ² may be the same or different from each other. there is; n is an integer from 0 to 3.

The photosensitive resin composition maintains high heat resistance and high transparency, which are advantages of a composition containing a conventional siloxane polymer, and at the same time improves crack resistance, thereby providing a cured film or a planarization film with excellent stability even in a post-process.

The photosensitive resin composition according to the present invention comprises (A) a siloxane polymer, (B) a 1,2-quinonediazide-based compound and (C) a solvent, and optionally, (E) a surfactant, and/or (F ) may further include other ingredients.

Hereinafter, the photosensitive resin composition will be described in detail for each component.

As used herein, "(meth)acryl" means "acryl" and/or "methacrylic", and "(meth)acrylate" means "acrylate" and/or "methacrylate".

(A) siloxane polymer

The siloxane polymer (polysiloxane) includes a silane compound and/or a condensate of a hydrolyzate thereof.

In this case, the silane compound or a hydrolyzate thereof may be a 1 to tetrafunctional silane compound.

As a result, the siloxane polymer may include siloxane constituent units selected from the following Q, T, D and M types:

- Q-type siloxane structural unit: refers to a siloxane structural unit including a silicon atom and four oxygen atoms adjacent thereto, for example, derived from a hydrolyzate of a tetrafunctional silane compound or a silane compound having four hydrolyzable groups can be

- T-type siloxane structural unit: refers to a siloxane structural unit including a silicon atom and three oxygen atoms adjacent thereto, for example, derived from a hydrolyzate of a trifunctional silane compound or a silane compound having three hydrolyzable groups can be

- D-type siloxane structural unit: refers to a siloxane structural unit (that is, a linear siloxane structural unit) containing a silicon atom and two oxygen atoms adjacent thereto, for example, a bifunctional silane compound or two hydrolyzable groups It can be derived from a hydrolyzate of a silane compound having

- M-type siloxane structural unit: means a siloxane structural unit including a silicon atom and one oxygen atom adjacent thereto, for example, derived from a hydrolyzate of a monofunctional silane compound or a silane compound having one hydrolyzable group can be

For example, the siloxane polymer (A) includes at least one structural unit derived from a silane compound represented by the following formula (1), for example, the siloxane polymer is a silane compound represented by the following formula (1) and/or its It may be a condensate of a hydrolyzate.

[Formula 1]

(R ¹ ) _n Si(R ² ) _4-n

In Formula 1, R ¹ is a non-hydrolyzable organic group having 1 to 12 carbon atoms, R ² is a hydrolyzable group, and n is an integer of 0 to 3.

Examples of the non-hydrolyzable organic group represented by R ¹ include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, and an arylalkyl group having 7 to 12 carbon atoms. and alkylaryl groups, which may be linear, branched or cyclic, and when a plurality of R ¹ are present in the same molecule, each R ¹ may be the same or different from each other. R ¹ may contain a structural unit having a hetero atom, and examples of the structural unit include ether, ester, and sulfide. The non-hydrolyzability required for R ¹ may mean a property that can stably exist under conditions in which hydrolyzable R ² is hydrolyzed.

The hydrolyzable group represented by R ² is generally heated at 25° C. to 100° C. without a catalyst in the presence of excess water, thereby being hydrolyzed to form a silanol group or a group capable of forming a condensate. Examples of such a hydrolyzable group include a hydrogen atom, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, an amino group, an acyloxy group having 2 to 12 carbon atoms, and an aryloxy group having 6 to 12 carbon atoms, and a plurality of R ² is When present in the same molecule, each R ² may be the same as or different from each other.

The silane compound represented by Formula 1 is, for example, a silane compound substituted with four hydrolysable groups (ie, n=0), and a silane compound substituted with one non-hydrolyzable group and three hydrolysable groups (ie, n=1) , a silane compound substituted with two non-hydrolysable groups and two hydrolysable groups (ie n=2), or a silane compound substituted with three non-hydrolysable groups and one hydrolysable group (ie n=3).

As a specific example of such a silane compound, it is a silane compound substituted by four hydrolysable groups, for example, tetrachlorosilane, tetraaminosilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane. , tetraphenoxysilane, tetrabenzyloxysilane and tetrapropoxysilane; As a silane compound substituted with one non-hydrolysable group and three hydrolysable groups, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxy Silane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, d ³ -Methyltrimethoxysilane, nonafluorobutylethyltrimethoxysilane, trifluoromethyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxy Propyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane , 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltriethoxysilane, 3, 3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrie Toxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, [(3-ethyl-3-oxetanyl)methyl oxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-trimethoxysilylpropylsuccinic acid; As a silane compound substituted with two non-hydrolysable groups and two hydrolysable groups, dimethyldichlorosilane, dimethyldiaminosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyl Diphenoxysilane, dibutyldimethoxysilane, dimethyldiethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, 3-(2-aminoethylamino ) Propyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, 3-mercaptopropyldimethoxymethylsilane, cyclohexyldimethoxymethylsilane, diethoxymethylvinylsilane, dimethoxy methylvinylsilane and dimethoxydi-p-tolylsilane; Trimethylchlorosilane, hexamethyldisilazane, trimethylsilane, tributylsilane, trimethylmethoxysilane, tributylethoxysilane, (3-glycidoxy propyl) dimethyl methoxysilane and (3-glycidoxy propyl) dimethyl ethoxy silane, and the like.

Among these, tetramethoxysilane, tetraethoxysilane and tetrabutoxysilane are preferable as the silane compound substituted with four hydrolysable groups; As a silane compound substituted with one non-hydrolysable group and three hydrolysable groups, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrime Preference is given to oxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane and butyltrimethoxysilane; Dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, dibutyldimethoxysilane and dimethyldiethoxysilane as silane compounds substituted with two non-hydrolysable groups and two hydrolysable groups This is preferable.

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

Conditions for obtaining a hydrolyzate of the silane compound of Formula 1 or a condensate thereof are not particularly limited. For example, the silane compound of Formula 1 is diluted in a solvent such as ethanol, 2-propanol, acetone, butyl acetate, etc. as needed. After adding water necessary for the reaction and an acid (hydrochloric acid, acetic acid, nitric acid, etc.) or a base (ammonia, triethylamine, cyclohexylamine, tetramethylammonium hydroxide, etc.) as a catalyst, stirring to complete the hydrolysis polymerization reaction It is possible to obtain a hydrolyzate or a condensate thereof.

The weight average molecular weight of the condensate (siloxane polymer) obtained by hydrolysis polymerization of the silane compound of Formula 1 is preferably 500 to 50,000, and when it is within the above range, the film-forming properties, solubility and dissolution rate in the developer, etc. can be advantageous

The type or amount of the solvent, acid or base catalyst used herein may be arbitrarily selected without limitation. Although the hydrolysis polymerization reaction proceeds even at a low temperature of 20°C or less, the reaction can be accelerated by heating or reflux operation. In order to proceed with the reaction until about 500 to 50,000, it usually requires a time of 15 minutes to 30 days. However, the reaction time is not limited to this range.

The siloxane polymer (A) contains a linear siloxane structural unit (ie, a D-type siloxane structural unit) in an amount of 2 to 15 mol% based on the number of moles of Si atoms. The linear siloxane structural unit may be derived from a bifunctional silane compound, for example, may be derived from a silane compound having n=2 in Formula 1 above. Specifically, the siloxane polymer (A) contains a structural unit derived from a silane compound having n=2 in Formula 1 in an amount of 0.5 to 30 mol%, preferably 2 to 15 mol%, based on the number of moles of Si atoms. . When within the preferred content range, the cured film can exhibit a flexible characteristic while maintaining a certain hardness, crack resistance to external stress (stress) can be further improved.

In addition, the siloxane polymer (A) may include a structural unit (ie, a T-type unit) derived from a silane compound having n=1 in Formula 1 above. Preferably, the siloxane polymer (A) contains 40 to 85 mol%, more preferably 65 to 80 mol% of the structural unit derived from the silane compound having n=1 in Formula 1, based on the number of moles of Si atoms. may include When it is within the preferred content range, accurate pattern formation may be more advantageous.

Moreover, it is preferable from a viewpoint of the hardness of a cured film, a sensitivity, and a remaining film rate that the said siloxane polymer (A) contains the structural unit derived from the silane compound which has an aryl group. For example, the siloxane polymer (A) may contain 30 to 70 mol%, more preferably 35 to 50 mol%, of a structural unit derived from a silane compound having an aryl group, based on the number of moles of Si atoms. When it is within the preferred content range, the siloxane polymer and the 1,2-naphthoquinonediazide compound have excellent compatibility, which is more advantageous in terms of transparency of the cured film and can prevent the sensitivity from being too slow. The structural unit derived from the silane compound having an aryl group is, for example, a silane compound in which R ¹ is an aryl group in the above formula (1), preferably a silane compound in which n=1 and R ¹ is an aryl group in the above formula (1), particularly the above formula In 1, n=1 and R ¹ may be a structural unit derived from a silane compound having a phenyl group (ie, a T-phenyl type unit).

The siloxane polymer (A) may include a structural unit (ie, a Q-type unit) derived from a silane compound having n=0 in Formula 1 above. Preferably, the siloxane polymer (A) contains 10 to 40 mol%, preferably 15 to 30 mol%, of a structural unit derived from a silane compound having n=0 in Formula 1, based on the number of moles of Si atoms. can do. When the content is within the preferred range, the solubility of the photosensitive resin composition in the aqueous alkali solution is maintained at an appropriate level during pattern formation, thereby preventing the occurrence of defects or excessive increase in solubility due to lowering of the solubility.

Here, "mol% based on the number of moles of Si atoms" means a percentage of the number of moles of Si atoms contained in a specific constituent unit to the total number of moles of Si atoms contained in all constituent units constituting the siloxane polymer.

The molar content of siloxane units in the siloxane polymer (A) can be measured by combining Si-NMR, ¹ H-NMR, ¹³ C-NMR, IR, TOF-MS, elemental analysis, batch measurement, and the like. For example, to measure the molar content of a siloxane unit having a phenyl group, Si-NMR analysis is performed on the entire siloxane polymer, and then the peak area of Si to which the phenyl group is bonded and the peak area of Si to which the phenyl group is not bonded are analyzed. After that, it can be calculated from the ratio between them.

The photosensitive resin composition of the present invention may include the siloxane polymer (A) in an amount of 50 to 95% by weight, preferably 65 to 90% by weight, based on the total weight of the solid content excluding the solvent thereof. Developability is appropriately adjusted within the above preferred range, so that the remaining film formation and pattern resolution are excellent.

(B) 1,2-quinonediazide-based compound

The photosensitive resin composition according to the present invention includes a 1,2-quinonediazide-based compound (B).

As the 1,2-quinonediazide-based compound, a compound used as a photosensitizer in the photoresist field may be used.

Examples of the 1,2-quinonediazide-based compound include an ester of a phenol compound and 1,2-benzoquinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5-sulfonic acid, a phenol compound and 1 ,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid ester, a compound in which the hydroxyl group of a phenol compound is substituted with an amino group, and 1,2-benzoquinonediazide Sulfonamide of -4-sulfonic acid or 1,2-benzoquinonediazide-5-sulfonic acid, a compound in which the hydroxyl group of a phenol compound is substituted with an amino group, and 1,2-naphthoquinonediazide-4-sulfonic acid or 1 and sulfonamides of ,2-naphthoquinonediazide-5-sulfonic acid. The above substances may be used alone or in combination of two or more.

Here, examples of the phenol compound include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3 ,3',4-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, Tri(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3 ,4-trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-[4-[1-] [4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3 '-Tetramethyl-1,1'-spirobindene-5,6,7,5',6',7'-hexanol, 2,2,4-trimethyl-7,2',4'-trihydro Roxyflavan etc. are mentioned.

More specific examples of the 1,2-quinonediazide-based compound include an ester of 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinonediazide-4-sulfonic acid, 2,3,4- Ester of trihydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl] Ester of phenyl]ethylidene]bisphenol and 1,2-naphthoquinonediazide-4-sulfonic acid, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl and esters of ]phenyl]ethylidene]bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid.

These may be used alone or in combination of two or more.

When these preferred compounds are used, the transparency of the positive photosensitive resin composition can be improved.

The 1,2-quinonediazide-based compound (B) may be included in the photosensitive resin composition in an amount of 2 to 30 parts by weight based on 100 parts by weight of the siloxane polymer (A) based on the solid content excluding the solvent, and preferably 6 to 25 parts by weight. It may be included in parts by weight. Within the preferred content range, pattern formation may be easier, and the problem that the surface of the coating film becomes rough after formation of the coating film or that a pattern shape such as scum occurs at the lower end during development can be suppressed.

(C) solvent

The photosensitive resin composition of the present invention may be prepared as a liquid composition in which the above components are mixed with a solvent. The solvent may be, for example, an organic solvent.

The content of the solvent in the photosensitive resin composition according to the present invention is not particularly limited, but for example, the solid content is 10 to 70% by weight, preferably 15 to 60% by weight, more preferably based on the total weight of the photosensitive resin composition. may include a solvent in an amount of 20 to 40% by weight. The solid content means a composition component excluding a solvent in the resin composition of the present invention. When the content of the solvent is within the above preferred range, it is possible to easily coat and maintain an appropriate level of flowability.

The solvent of the present invention is not particularly limited as long as it can dissolve each component and is chemically stable, for example, alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl Ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, ketone, ester, etc. are mentioned.

Examples of specific solvents include methanol, ethanol, tetrahydrofuran, dioxane, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, Ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, dipropylene glycol methyl ether acetate, Propylene glycol butyl ether acetate, toluene, xylene, methyl ethyl ketone, 4-hydroxy-4-methyl-2-pentanone, cyclopentanone, cyclohexanone, 2-heptanone, γ-butyrolactone, 2-hydro Ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 2-methoxypropionate, methyl 3-methoxypropionate , 3-methoxyethyl propionate, 3-ethoxypropionate ethyl, 3-ethoxypropionate methyl, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylform amide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

Among these, ethylene glycol alkyl ether acetates, diethylene glycol, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, ketones, etc. are preferable, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, Dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, 2-methoxymethyl propionate, γ-butyrolactone, 4-hydroxy-4 -Methyl-2-pentanone, etc. are preferable.

The solvents exemplified above may be used alone or in combination of two or more.

(D) surfactant

The photosensitive resin composition of the present invention may further include a surfactant to improve the coating performance of the composition, if necessary.

Although the kind of such surfactant is not specifically limited, For example, a fluorochemical surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned.

Specific examples of the surfactant include FZ2122 of Dow Corning Toray, BM-1000 and BM-1100 of BM CHEMIE, Megapack F-142 D, F-172, and F-173 of Dainippon Ink Chemical Co., Ltd. and F-183, Florard FC-135, FC-170 C, FC-430 and FC-431 of Sumitomo 3M Limited, Suffron S-112, S-113, S-131 of Asahi Glass Co., Ltd.; S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105 and SC-106; fluorine-based and silicone-based surfactants such as EF352, SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC-190 manufactured by Toray Silicones Corporation; Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether , nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid-based copolymer polyflow No. 57 and 95 (manufactured by Kyoeisha Yuji Chemical Co., Ltd.); and the like. These can be used individually or in combination of 2 or more types.

The surfactant (D) may be included in the photosensitive resin composition in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the siloxane polymer (A) based on the solid content excluding the solvent, and more preferably from 0.05 to 2 parts by weight. there is. When the content of the surfactant is 0.05 parts by weight or more, applicability is improved and cracks do not occur on the coated surface, and when it is 2 parts by weight or less, thermal stability at high temperature is good and price is preferable.

(E) Adhesive Aids

The photosensitive resin composition of the present invention may further include an adhesion aid to improve adhesion to the substrate.

The adhesion aid may have at least one reactive group selected from the group consisting of a carboxyl group, a (meth)acryloyl group, an isocyanate group, an amino group, a mercapto group, a vinyl group, and an epoxy group.

The type of the adhesive aid is not particularly limited, but trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane At least one member selected from the group consisting of Silane or N-phenylaminopropyltrimethoxysilane may be used.

The amount of the adhesive aid (E) in the composition may be used in an amount of 0.001 to 5 parts by weight, preferably 0.01 to 2 parts by weight, based on 100 parts by weight (based on solid content) of the copolymer (A). Within the above preferred content range, it is possible to further improve adhesion to the substrate while preventing resolution degradation.

In addition, the photosensitive resin composition of the present invention may further include other additive components within a range that does not impair physical properties.

The photosensitive resin composition according to the present invention can be used as a positive photosensitive resin composition.

In particular, the composition of the present invention can maintain crack resistance even during a thick film process by including the linear siloxane constituent unit in a specific content range.

Specifically, the siloxane-based photosensitive resin composition of the present invention includes a D-type siloxane constituent unit in a specific content range in a siloxane polymer including a Q-type siloxane constituent unit and a T-type siloxane constituent unit. It is possible to exhibit flexible properties to external stresses by reducing the stiffness. As a specific example, the composition of the present invention may exhibit a permanent set rate of 3% to 20% when 1000mN is applied to a cured film (eg, thickness 5㎛) prepared therefrom, and more specifically 5% to 15% It can exhibit a permanent set, so it can exhibit the properties of a flexible cured film to external stimuli.

Therefore, the photosensitive resin composition maintains high heat resistance and high transparency, which are advantages of a composition containing a conventional siloxane polymer, and improves crack resistance at the same time, thereby providing a cured film or planarization film with excellent stability even in a post-process. .

In particular, unlike compositions using a siloxane polymer including a conventional linear siloxane structural unit (that is, a D-type siloxane structural unit), the composition of the present invention has reduced stiffness when manufactured into a cured film or a planarization film. By exhibiting flexibility, it can have crack resistance against external stress. Accordingly, even if the film is formed thicker than a general planarization film (2 to 3 μm) according to the necessity of the process, excellent crack resistance can be exhibited while maintaining high heat resistance and high transparency after the subsequent high temperature treatment process.

The present invention also provides a cured film prepared from the photosensitive resin composition.

The cured film may be manufactured by a method known in the art, for example, by coating the photosensitive resin composition on a substrate and then curing the cured film.

In this case, the application may be performed to a desired thickness, for example, 2 to 25 μm, using a method such as a spin coating method, a slit coating method, a roll coating method, a screen printing method, or an applicator method.

Specifically, the curing is performed by pre-bake the photosensitive resin composition applied on the substrate at, for example, 60 to 130° C. to remove the solvent, and then expose it to light using a photomask having a desired pattern formed thereon, and use a developer (eg, tetra A pattern can be formed on the coating layer by developing with a methylammonium hydroxide (TMAH) solution). In this case, the exposure may be performed at an exposure dose of 10 to 200 mJ/cm 2 based on 365 nm in a wavelength band of 200 to 500 nm. In addition, as a light source used for exposure (irradiation), a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. can be used, and in some cases, X-rays, electron beams, etc. can also be used.

Thereafter, if necessary, the patterned coating layer may be post-bake at 150 to 300° C. for 10 minutes to 5 hours to prepare a desired cured film.

The cured film thus prepared has excellent physical properties in terms of heat resistance, transparency, dielectric constant, solvent resistance, and chemical resistance.

Therefore, the cured film does not have a rough surface even by immersion, contact, or heat treatment using a solvent, acid, alkali solution, etc., and has a high light transmittance. It can be usefully used as a barrier rib of an EL display device, an interlayer insulating film of a semiconductor device, and a core or cladding material of an optical waveguide.

Furthermore, the present invention provides an electronic component including the cured film as a protective film.

Hereinafter, the present invention will be described in more detail by way of Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

The weight average molecular weight described in the following synthesis example is a polystyrene conversion value measured by gel permeation chromatography (GPC).

Synthesis Example 1: Synthesis of siloxane polymer (a)

In a reactor equipped with a reflux cooling device, 28 parts by weight of phenyltrimethoxysilane, 18 parts by weight of methyltrimethoxysilane, 19 parts by weight of tetraethoxysilane, 0.7 parts by weight of dimethyldimethoxysilane, 19.3 parts by weight of ethylene glycol monoethyl ether parts, and 15 parts by weight of pure water, stirred under reflux for 7 hours under 0.1 parts by weight of an oxalic acid catalyst, and then cooled. As a result, a siloxane polymer having a weight average molecular weight of about 3,000 to 5,000 Da was synthesized, and propylene glycol monomethyl ether was added so that the solid content was 40% by weight.

Synthesis Example 2: Synthesis of siloxane polymer (b)

In a reactor equipped with a reflux cooling device, 28 parts by weight of phenyltrimethoxysilane, 17 parts by weight of methyltrimethoxysilane, 19 parts by weight of tetraethoxysilane, 1.3 parts by weight of dimethyldimethoxysilane, 19.7 parts by weight of ethylene glycol monoethyl ether parts, and 15 parts by weight of pure water, stirred under reflux for 7 hours under 0.1 parts by weight of an oxalic acid catalyst, and then cooled. As a result, a siloxane polymer having a weight average molecular weight of about 3,000 to 5,000 Da was synthesized, and propylene glycol monomethyl ether was added so that the solid content was 40% by weight.

Synthesis Example 3: Synthesis of siloxane polymer (c)

In a reactor equipped with a reflux cooling device, 29 parts by weight of phenyltrimethoxysilane, 16 parts by weight of methyltrimethoxysilane, 18 parts by weight of tetraethoxysilane, 2 parts by weight of dimethyldimethoxysilane, 20 parts by weight of ethylene glycol monoethyl ether parts, and 15 parts by weight of pure water, and stirred under reflux for 7 hours under 0.1 parts by weight of an oxalic acid catalyst, followed by cooling. As a result, a siloxane polymer having a weight average molecular weight of about 3,000 to 5,000 Da was synthesized, and propylene glycol monomethyl ether was added so that the solid content was 40% by weight.

Synthesis Example 4: Synthesis of siloxane polymer (d)

In a reactor equipped with a reflux cooling device, 33 parts by weight of phenyltrimethoxysilane, 11 parts by weight of methyltrimethoxysilane, 17 parts by weight of tetraethoxysilane, 4.5 parts by weight of dimethyldimethoxysilane, 19.5 parts by weight of ethylene glycol monoethyl ether parts, and 15 parts by weight of pure water, and stirred under reflux for 7 hours under 0.1 parts by weight of an oxalic acid catalyst, followed by cooling. As a result, a siloxane polymer having a weight average molecular weight of about 3,000 to 5,000 Da was synthesized, and propylene glycol monomethyl ether was added so that the solid content was 40% by weight.

Synthesis Example 5: Synthesis of siloxane polymer (e)

In a reactor equipped with a reflux cooling device, 22 parts by weight of phenyltrimethoxysilane, 1 part by weight of methyltrimethoxysilane, 35 parts by weight of tetraethoxysilane, 6 parts by weight of dimethyldimethoxysilane, 21 parts by weight of ethylene glycol monoethyl ether parts, and 15 parts by weight of pure water, and stirred under reflux for 7 hours under 0.1 parts by weight of an oxalic acid catalyst, followed by cooling. As a result, a siloxane polymer having a weight average molecular weight of about 3,000 to 5,000 Da was synthesized, and propylene glycol monomethyl ether was added so that the solid content was 40% by weight.

Synthesis Example 6: Synthesis of siloxane polymer (f)

In a reactor equipped with a reflux cooling device, 30 parts by weight of phenyltrimethoxysilane, 25 parts by weight of methyltrimethoxysilane, 8 parts by weight of tetraethoxysilane, 1.3 parts by weight of dimethyldimethoxysilane, 20.7 parts by weight of ethylene glycol monoethyl ether parts, and 15 parts by weight of pure water, and stirred under reflux for 7 hours under 0.1 parts by weight of an oxalic acid catalyst, followed by cooling. As a result, a siloxane polymer having a weight average molecular weight of about 3,000 to 5,000 Da was synthesized, and propylene glycol monomethyl ether was added so that the solid content was 40% by weight.

Synthesis Example 7: Synthesis of siloxane polymer (g)

In a reactor equipped with a reflux cooling device, 27 parts by weight of phenyltrimethoxysilane, 3 parts by weight of methyltrimethoxysilane, 37 parts by weight of tetraethoxysilane, 2 parts by weight of dimethyldimethoxysilane, 16 parts by weight of ethylene glycol monoethyl ether parts, and 15 parts by weight of pure water, and stirred under reflux for 7 hours under 0.1 parts by weight of an oxalic acid catalyst, followed by cooling. As a result, a siloxane polymer having a weight average molecular weight of about 3,000 to 5,000 Da was synthesized, and propylene glycol monomethyl ether was added so that the solid content was 40% by weight.

Synthesis Example 8: Synthesis of siloxane polymer (h)

In a reactor equipped with a reflux cooling device, 21 parts by weight of phenyltrimethoxysilane, 21 parts by weight of methyltrimethoxysilane, 15 parts by weight of tetraethoxysilane, 4.5 parts by weight of dimethyldimethoxysilane, 18.5 parts by weight of ethylene glycol monoethyl ether parts, and 20 parts by weight of pure water, and then cooled under reflux stirring for 7 hours under 0.1 parts by weight of an oxalic acid catalyst. As a result, a siloxane polymer having a weight average molecular weight of about 3,000 to 5,000 Da was synthesized, and propylene glycol monomethyl ether was added so that the solid content was 40% by weight.

Synthesis Example 9: Synthesis of siloxane polymer (i)

In a reactor equipped with a reflux cooling device, 31 parts by weight of phenyltrimethoxysilane, 21 parts by weight of methyltrimethoxysilane, 22 parts by weight of tetraethoxysilane, 6 parts by weight of propylene glycol monomethyl ether acetate, and 20 parts by weight of pure water After stirring under reflux for 7 hours under 0.1 parts by weight of an oxalic acid catalyst, the mixture was cooled. As a result, a siloxane polymer having a weight average molecular weight of about 5,000 to 7,000 Da was synthesized, and propylene glycol monomethyl ether was added so that the solid content was 40% by weight.

Synthesis Example 10: Synthesis of siloxane polymer (j)

In a reactor equipped with a reflux cooling device, 24 parts by weight of phenyltrimethoxysilane, 12 parts by weight of methyltrimethoxysilane, 33 parts by weight of tetraethoxysilane, 11 parts by weight of propylene glycol monomethyl ether acetate, and 20 parts by weight of pure water After stirring under reflux for 7 hours under 0.1 parts by weight of an oxalic acid catalyst, the mixture was cooled. As a result, a siloxane polymer having a weight average molecular weight of about 5,000 to 7,000 Da was synthesized, and propylene glycol monomethyl ether was added so that the solid content was 40% by weight.

Synthesis Example 11: Synthesis of siloxane polymer (k)

In a reactor equipped with a reflux cooling device, 29 parts by weight of phenyltrimethoxysilane, 17 parts by weight of methyltrimethoxysilane, 19 parts by weight of tetraethoxysilane, 0.7 parts by weight of dimethyldimethoxysilane, 19.3 parts by weight of ethylene glycol monoethyl ether parts, and 15 parts by weight of pure water, and stirred under reflux for 7 hours under 0.1 parts by weight of an oxalic acid catalyst, followed by cooling. As a result, a siloxane polymer having a weight average molecular weight of about 3,000 to 5,000 Da was synthesized, and propylene glycol monomethyl ether was added so that the solid content was 40% by weight.

Synthesis Example 12: Synthesis of siloxane polymer (l)

In a reactor equipped with a reflux cooling device, 30 parts by weight of phenyltrimethoxysilane, 11 parts by weight of methyltrimethoxysilane, 17 parts by weight of tetraethoxysilane, 8 parts by weight of dimethyldimethoxysilane, 19 parts by weight of ethylene glycol monoethyl ether , and 15 parts by weight of pure water, and then cooled under reflux stirring for 7 hours under 0.1 parts by weight of an oxalic acid catalyst. As a result, a siloxane polymer having a weight average molecular weight of about 3,000 to 5,000 Da was synthesized, and propylene glycol monomethyl ether was added so that the solid content was 40% by weight.

Examples and Comparative Examples: Preparation of photosensitive resin composition

The photosensitive resin compositions of the following Examples and Comparative Examples were prepared using the compounds prepared in Synthesis Example.

In the following Examples and Comparative Examples, the following compounds were used as other components:

- 1,2-quinonediazide-based compound: TPA-523, Miwon Trading Co., Ltd.

- Adhesion aid: 3-glycidoxypropyltrimethoxysilane, GPTMS, Sigma-Aldrich

- Surfactant: silicone Leveling surfactant, FZ-2122, Dow Corning Toray

- Solvent: propylene glycol monomethyl ether acetate, PGMEA

Example 1 : 24.64 g of the siloxane polymer (a) solution of Synthesis Example 1, 1.10 g of a 1,2-quinonediazide-based compound, 0.22 g of an adhesion aid, and 0.22 g of a surfactant were uniformly mixed and dissolved in 23.82 g of a solvent. This was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution having a solid content of 22 wt%.

Example 2 : 24.64 g of the siloxane polymer (b) solution of Synthesis Example 2, 1.10 g of a 1,2-quinonediazide-based compound, 0.22 g of an adhesion aid, and 0.22 g of a surfactant were uniformly mixed and dissolved in 23.82 g of a solvent. This was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution having a solid content of 22 wt%.

Example 3 : 24.64 g of the siloxane polymer (c) solution of Synthesis Example 3, 1.10 g of a 1,2-quinonediazide-based compound, 0.22 g of an adhesion aid, and 0.22 g of a surfactant were uniformly mixed and dissolved in 23.82 g of a solvent. This was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution having a solid content of 22 wt%.

Example 4 : 24.64 g of the siloxane polymer (d) solution of Synthesis Example 4, 1.10 g of a 1,2-quinonediazide-based compound, 0.22 g of an adhesion aid, and 0.22 g of a surfactant were uniformly mixed and dissolved in 23.82 g of a solvent. This was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution having a solid content of 22 wt%.

Example 5 : 23.27 g of the siloxane polymer (b) solution of Synthesis Example 2, 1.65 g of a 1,2-quinonediazide-based compound, 0.22 g of an adhesion aid, and 0.22 g of a surfactant were uniformly mixed and dissolved in 24.65 g of a solvent. This was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution having a solid content of 22 wt%.

Example 6 : 24.64 g of the siloxane polymer (e) solution of Synthesis Example 5, 1.10 g of a 1,2-quinonediazide-based compound, 0.22 g of an adhesion aid, and 0.22 g of a surfactant were uniformly mixed and dissolved in 23.82 g of a solvent. This was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution having a solid content of 22 wt%.

Example 7 : 24.64 g of the siloxane polymer (f) solution of Synthesis Example 6, 1.10 g of a 1,2-quinonediazide-based compound, 0.22 g of an adhesion aid, and 0.22 g of a surfactant were uniformly mixed and dissolved in 23.82 g of a solvent. This was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution having a solid content of 22 wt%.

Example 8 : 24.64 g of the siloxane polymer (g) solution of Synthesis Example 7, 1.10 g of a 1,2-quinonediazide-based compound, 0.22 g of an adhesion aid, and 0.22 g of a surfactant were uniformly mixed and dissolved in 23.82 g of a solvent. This was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution having a solid content of 22 wt%.

Example 9 : 24.64 g of the siloxane polymer (h) solution of Synthesis Example 8, 1.10 g of a 1,2-quinonediazide-based compound, 0.22 g of an adhesion aid, and 0.22 g of a surfactant were uniformly mixed and dissolved in 23.82 g of a solvent. This was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution having a solid content of 22 wt%.

Example 10 : 26.02 g of the siloxane polymer (b) solution of Synthesis Example 2, 0.55 g of a 1,2-quinonediazide-based compound, 0.22 g of an adhesion aid, and 0.22 g of a surfactant were uniformly mixed and dissolved in 23.00 g of a solvent. This was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution having a solid content of 22 wt%.

Example 11 : 21.89 g of the siloxane polymer (b) solution of Synthesis Example 2, 2.20 g of a 1,2-quinonediazide-based compound, 0.22 g of an adhesion aid, and 0.22 g of a surfactant were uniformly mixed and dissolved in 25.47 g of a solvent. This was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution having a solid content of 22 wt%.

Comparative Example 1 : 24.64 g of the siloxane polymer (i) solution of Synthesis Example 9, 1.10 g of a 1,2-quinonediazide-based compound, 0.22 g of an adhesion aid, and 0.22 g of a surfactant were uniformly mixed and dissolved in 23.82 g of a solvent. This was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution having a solid content of 22 wt%.

Comparative Example 2 : 24.64 g of the siloxane polymer (j) solution of Synthesis Example 10, 1.10 g of a 1,2-quinonediazide-based compound, 0.22 g of an adhesion aid, and 0.22 g of a surfactant were uniformly mixed and dissolved in 23.82 g of a solvent. This was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution having a solid content of 22 wt%.

Comparative Example 3 : 24.64 g of the siloxane polymer (k) solution of Synthesis Example 11, 1.10 g of a 1,2-quinonediazide-based compound, 0.22 g of an adhesion aid, and 0.22 g of a surfactant were uniformly mixed and dissolved in 23.82 g of a solvent. This was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution having a solid content of 22 wt%.

Comparative Example 4 : 24.64 g of the siloxane polymer (1) solution of Synthesis Example 12, 1.10 g of a 1,2-quinonediazide-based compound, 0.22 g of an adhesion aid, and 0.22 g of a surfactant were uniformly mixed and dissolved in 23.82 g of a solvent. This was filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a composition solution having a solid content of 22 wt%.

The configurations of the above Examples and Comparative Examples are summarized in Table 1 below.

division siloxane
polymer
type 1,2-quinone
diazide
compound* Content per unit in siloxane polymer (mol%) T-phenyl
type D type T type Q type



Example One a
10 38.2 2.0 73.8 24.6 2 b 38.6 3.0 72.8 24.3 3 c 39.1 4.5 71.6 23.9 4 d 45.0 10.0 67.5 22.5 5 b 15 38.6 3.0 72.8 24.3 6 e
10 33.0 15.0 35.0 50.0 7 f 39.0 3.0 87.0 10.0 8 g 38.0 5.0 45.0 50.0 9 h 28.0 10.0 70.0 20.0 10 b 5 38.6 3.0 72.8 24.3 11 b 20 38.6 3.0 72.8 24.3
comparative example One It's
10 37.5 0.0 75.0 25.0 2 j 33.0 0.0 57.0 43.0 3 k 40.1 1.7 73.8 24.6 4 l 39.4 18.2 60.6 21.2 * The content of the 1,2-quinonediazide-based compound is in weight percent based on the solid content in the composition.

Test Example 1: Evaluation of permanent set

Each composition obtained in Examples and Comparative Examples was spin-coated on a chromium substrate and then pre-cured for 120 seconds on a high-temperature plate maintained at 120°C. After applying a mask having a square hole pattern with a size of 2 μm to 25 μm to the obtained pre-cured film, using an aligner (model name MA6) emitting a wavelength of 200 nm to 450 nm, based on 365 nm Exposure was carried out for a certain period of time so as to be 200 mJ/cm 2 , and development was performed through a spray nozzle at 23° C. with a 2.38 wt% tetramethylammonium hydroxide aqueous developer. The resulting developing film was heated in a convection oven at 230° C. for 60 minutes to obtain a cured film having a thickness of 5.0 μm.

In order to measure mechanical properties of the cured film, that is, compressive displacement and permanent set, a bulk portion of the cured film was determined as a basic measurement position. Compressive displacement and permanent set were measured according to ASTM E 2546 using a microhardness tester (HM2000LT, FISCHER). Specifically, a 50 μm diameter flat indenter was used, and a load-unload method was performed under the conditions of an applied load of 1000 mN, a load speed of 5 mN/sec, and a holding time of 5 seconds. After removing the load, after 10 minutes of restoration time, the permanently deformed thickness (ie, the depth permanently depressed by the load) (㎛) by subtracting the recovery displacement from the measured compressive displacement using a 3D thickness measuring device ) was found.

Using these measurements, the permanent set (%) was calculated according to the following equation:

Permanent set (%) = [ (Permanent deformation thickness (㎛) / Initial cured film thickness (㎛)) x 100 ]

Test Example 2: Crack resistance evaluation

Each of the compositions obtained in Examples and Comparative Examples was coated, pre-cured, exposed and developed on a chrome substrate in the same manner as in Test Example 1. The resulting developing film was heated in a convection oven at 230° C. for 60 minutes to obtain a cured film having a thickness of 5.0 μm.

Cracks generated in a 1 cm x 1 cm area at a designated location in the center of the cured film were observed and evaluated according to the following criteria.

○: When cracks do not occur

△: When 1 or 2 cracks occur

X : In case of 3 or more cracks

Test Example 3: Resolution Evaluation

Each of the compositions obtained in Examples and Comparative Examples was coated, pre-cured, exposed and developed on a silicon nitride substrate in the same manner as in Test Example 1. The resulting developing film was heated in a convection oven at 230° C. for 30 minutes to obtain a cured film having a thickness of 2.5 μm.

In the above process, exposure energy in which 10.5 μm is realized as CD (critical dimension, line width, μm) of a hole pattern patterned through a mask having a rectangular hole pattern of 10 μm in size is obtained, and the resolution in the exposure energy is obtained. (μm) was calculated. It can be said that the smaller the numerical value of the resolution, the better.

Test Example 4: Measurement of residual film rate after development

Each of the compositions obtained in Examples and Comparative Examples was coated, pre-cured, exposed and developed on a silicon nitride substrate in the same manner as in Test Example 1. After measuring the film thickness in the above process, the residual film rate (%) after development was calculated according to the following equation:

Remaining film rate after development (%) = (thickness of developing film / thickness of pre-cured film) x 100.

Test Example 5: Measurement of residual film rate after heat curing

Each of the compositions obtained in Examples and Comparative Examples was coated, pre-cured, exposed and developed on a silicon nitride substrate in the same manner as in Test Example 1. The resulting developing film was heated in a convection oven at 230° C. for 30 minutes to obtain a cured film having a thickness of 2.5 μm.

After measuring the film thickness in the above process, the residual film rate (%) after development was calculated according to the following equation:

Remaining film rate (%) after thermal curing = (thickness of final thermal curing film / thickness of pre-curing film) x 100.

Test Example 6: Sensitivity evaluation

Each composition obtained in Examples and Comparative Examples was spin-coated on a silicon nitride substrate and then pre-cured for 120 seconds on a high-temperature plate maintained at 120° C. to form a dry film. After applying a mask having a square hole pattern with a size of 2 μm to 25 μm to this dry film, using an aligner (model name MA6) emitting a wavelength of 200 nm to 450 nm, 200 mJ/ It was exposed for a certain period of time so as to become cm 2 , and developed through a spray nozzle at 23° C. with a 2.38 wt% tetramethylammonium hydroxide aqueous developer. The obtained exposed film was heated in a convection oven at 230° C. for 30 minutes to obtain a cured film having a thickness of 2.5 μm.

In the above process, exposure energy (ie energy of optimum, EOP) in which 10.5 μm is realized as CD (critical dimension, line width, μm) of a hole pattern patterned through a mask having a square hole pattern of 10 μm in size ( mJ/cm2) was calculated.

The above test results are summarized in Table 2 below.

division Permanent deformation thickness (㎛) permanent deformation
rate (%) crack resistance
@ 5㎛ resolution
(μm) after development
Remaining film rate (%) after heat curing
Remaining film rate (%) Sensitivity
(mJ/cm2) Example 1 0.33 6.6 △ 4 89 83 30 Example 2 0.35 7 ○ 4 87 82 35 Example 3 0.44 8.8 ○ 4 88 82 35 Example 4 0.49 9.8 ○ 4 91 86 37.5 Example 5 0.33 6.6 ○ 4 90 87 40 Example 6 0.61 12.2 △ 7 83 80 50 Example 7 0.31 6.2 △ 7 86 82 45 Example 8 0.36 7.2 △ 7 87 84 37.5 Example 9 0.53 10.6 △ 7 79 76 14 Example 10 0.38 7.6 × 3 80 75 20 Example 11 0.26 5.2 × 7 95 90 50 Comparative Example 1 0.07 1.4 × 4 89 85 35 Comparative Example 2 0.04 0.8 × 6 92 89 50 Comparative Example 3 0.16 3.2 × 4 91 87 30 Comparative Example 4 0.85 17 × 6 85 81 40

As shown in Table 2, the compositions of Examples within the scope of the present invention all had a permanent set rate of 5% to 15%, excellent crack resistance, and were equally excellent in resolution, remaining film rate and sensitivity. On the other hand, the compositions of Comparative Examples that do not fall within the scope of the present invention showed poor results at any one or more of them.

Claims (6)

(A) a siloxane polymer comprising at least one structural unit derived from a silane compound represented by the following formula (1);
(B) a 1,2-quinonediazide-based compound, and
(C) a composition comprising a solvent,
The siloxane polymer (A) is, based on the number of moles of Si atoms, (i) 2 to 15 mol% of a structural unit derived from a silane compound having n=2 in the following formula (1), and (ii) n=0 in the following formula (1) It contains 10 to 40 mol% of a structural unit derived from a silane compound,
A photosensitive resin composition showing a permanent set of 5% to 15% when a load of 1000 mN is applied to a cured film having a thickness of 5 μm prepared from the composition:
[Formula 1]
(R ¹ ) _n Si(R ² ) _4-n
In Formula 1,
R ¹ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, or an alkylaryl group having 7 to 12 carbon atoms, and a plurality of R ¹ is each may be the same or different;
R ² is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 12 carbon atoms, an amino group, an acyloxy group having 2 to 12 carbon atoms, or an aryloxy group having 6 to 12 carbon atoms, and a plurality of R ² may be the same or different from each other. there is;
n is an integer from 0 to 3.
delete The method of claim 1,
The photosensitive resin composition, characterized in that the siloxane polymer (A) comprises 40 to 85 mol% of a structural unit derived from a silane compound having n=1 in Formula 1, based on the number of moles of Si atoms.
4. The method of claim 3,
The photosensitive resin composition, characterized in that the siloxane polymer (A) contains a structural unit derived from a silane compound having an aryl group in an amount of 30 to 70 mol% based on the number of moles of Si atoms.
The method of claim 1,
The photosensitive resin composition, characterized in that the 1,2-quinonediazide-based compound (B) is included in an amount of 6 to 25 parts by weight based on 100 parts by weight of the siloxane polymer (A) based on the solid content.
delete