Positive photosensitive resin composition and cured film prepared therefrom

Abstract

To provide a positive-type photosensitive resin composition and a cured film prepared therefrom.SOLUTION: The present invention relates to a positive-type photosensitive resin composition and a cured film prepared therefrom. The positive-type photosensitive resin composition introduces a multifunctional monomer into a positive-type photosensitive resin composition comprising a mixed binder, in which a siloxane copolymer is added to an acrylic copolymer, whereby the penetration of a developer into the binder can be facilitated at the time of development of a pre-baked film to increase the solubility in the developer, thereby further enhancing the pattern developability and sensitivity. Further, a cured film prepared from the composition has excellent appearance characteristics without a rough surface of the film and a scum or the like at the bottom of the film during development.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a positive photosensitive resin composition capable of forming a cured film excellent in sensitivity, film retention rate, and appearance characteristics, and a cured film prepared therefrom and used in a liquid crystal display, an organic EL display, and the like.

Background Art

[0002] Generally, in a liquid crystal display or an organic EL display, a transparent planarization film is formed on a substrate of a thin film transistor (TFT) for the purpose of insulation to prevent contact between a transparent electrode and a data line. It is possible to increase the aperture ratio of the panel through a transparent pixel electrode located in the vicinity of the data line, and high brightness / high resolution can be achieved.

[0003] In order to form such a transparent planarization film, several processing steps are adopted to impart a specific pattern profile, and in this process, a positive photosensitive resin composition is widely adopted because fewer processing steps are required. In particular, as the size of the LCD panel increases, the demand for a positive cured film without stitch mura and lens mura is increasing.

[0004] Regarding conventional positive photosensitive resin compositions, techniques using polysiloxane resins, acrylic resins, etc. as raw materials have been introduced.

[0005] Compared with a polysiloxane resin rich in silanol groups, an acrylic resin has a problem of lower sensitivity than a polysiloxane resin because the content of carboxyl groups involved in development is limited. To compensate for this, a photosensitive resin composition having excellent sensitivity and adhesion, and a cured film prepared therefrom have been proposed (see Patent Document 1). However, the sensitivity has not been improved to a satisfactory level yet.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] Therefore, in the present invention, a polyfunctional monomer is introduced into a positive photosensitive resin composition containing both a siloxane copolymer and an acrylic copolymer, thereby promoting the penetration of a developer into the composition during development and enhancing pattern developability and sensitivity. Moreover, a cured film having excellent surface characteristics without scum and thermal fluidity can be provided. An object of the present invention is to provide a positive photosensitive resin composition, and a cured film prepared therefrom and used in a liquid crystal display, an organic EL display, etc.

Means for Solving the Problems

[0008] In order to achieve the above object, the present invention provides a positive photosensitive resin composition containing (A) an acrylic copolymer, (B) a siloxane copolymer, (C) a 1,2-quinonediazide compound, (D) a polyfunctional monomer, and (E) a solvent.

[0009] In order to achieve another object, the present invention provides a cured film formed from the positive photosensitive resin composition.

Effects of the Invention

[0010] The positive photosensitive resin composition of the present invention introduces a polyfunctional monomer into a positive photosensitive resin composition containing a mixed binder, where a siloxane copolymer is added to an acrylic copolymer, thereby promoting the penetration of a developer into the binder when developing a pre-baked film and improving the solubility in the developer, thereby further enhancing the pattern developability and sensitivity. Furthermore, when this composition is used, a cured film with almost no thermal fluidity can be obtained. Furthermore, the cured film prepared from this composition has excellent appearance characteristics such as a rough surface of the film and no scum or the like at the bottom of the film during development.

Brief Description of the Drawings

[0011]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0012] The present invention is not limited to what is described below. Rather, the present invention can be modified into various forms unless the gist of the present invention is changed.

[0013] Throughout this specification, when a certain part is referred to as including an element, unless otherwise specified, it is understood that other elements can be included rather than excluding other elements. In addition, all numbers and expressions regarding component amounts, reaction conditions, etc. used in this specification should be understood to be modified by the term "about" unless otherwise specified.

[0014] The present invention provides a positive photosensitive resin composition containing (A) an acrylic copolymer, (B) a siloxane copolymer, (C) a 1,2-quinonediazide compound, (D) a polyfunctional monomer, and (E) a solvent.

[0015] This may further optionally contain (F) an epoxy compound, (G) a surfactant, (H) an adhesion aid, and / or (I) a silane compound.

[0016] As used herein, the term “(meth)acrylic” means “acrylic” and / or “methacrylic”, and the term “(meth)acrylate” means “acrylate” and / or “methacrylate”.

[0017] The weight average molecular weight (g / mol or Da) of each component described below is measured by gel permeation chromatography (GPC, eluent: tetrahydrofuran) based on the polystyrene standard.

[0018] (A) Acrylic copolymer The positive photosensitive resin composition of the present invention may contain an acrylic copolymer (A) as a binder.

[0019] The acrylic copolymer may contain a structural unit derived from (a-1) an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof; a structural unit derived from (a-2) an unsaturated compound containing an epoxy group; and a structural unit derived from (a-3) an ethylenically unsaturated compound different from the structural units (a-1) and (a-2).

[0020] The acrylic copolymer is an alkali-soluble resin for embodying developability in the developing step, and also serves as a base for forming a film when coated and a structure for forming a final pattern.

[0021] (a-1) A structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof The structural unit (a-1) can be derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof.

[0022] Ethylenically unsaturated carboxylic acids, ethylenically unsaturated carboxylic anhydrides, or combinations thereof are polymerizable unsaturated compounds containing at least one carboxyl group in their molecules. These include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids and their anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; unsaturated polycarboxylic acids having a valence of 3 or more and their anhydrides; and mono[(meth)acryloyloxyalkyl] esters of polycarboxylic acids having a valence of 2 or more such as mono(2-(meth)acryloyloxyethyl) succinate and mono(2-(meth)acryloyloxyethyl) phthalate. However, it is not limited thereto. Among the above, (meth)acrylic acid is preferred from the viewpoint of developability.

[0023] The amount of the structural unit (a-1) may be 5 to 50 mol%, preferably 10 to 40 mol%, based on the total number of moles of the structural units constituting the acrylic copolymer. Within the above range, pattern formation of the film can be achieved while maintaining favorable developability.

[0024] (a-2) A structural unit derived from an unsaturated compound containing an epoxy group The structural unit (a-2) can be derived from an unsaturated monomer containing at least one epoxy group.

[0025] Specific examples of the unsaturated monomer containing at least one epoxy group include glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 5,6-epoxyhexyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 2,3-epoxycyclopentyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, N-(4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl)acrylamide, N-(4-(2,3-epoxypropoxy)-3,5-dimethylphenylpropyl)acrylamide, allyl glycidyl ether, 2-methylallyl glycidyl ether, and combinations thereof.

[0026] The amount of the structural unit (a-2) derived from the unsaturated compound containing at least one epoxy group may be 1 to 45 mol%, preferably 3 to 30 mol%, based on the total number of moles of the structural units constituting the acrylic copolymer. Within the above range, the storage stability of the composition can be maintained, and the film retention rate after post-baking can be advantageously improved.

[0027] (a-3) A structural unit derived from an ethylenically unsaturated compound different from the structural units (a-1) and (a-2) The structural unit (a-3) can be derived from an ethylenically unsaturated compound different from the structural units (a-1) and (a-2).

[0028] Ethylenically unsaturated compounds different from structural units (a-1) and (a-2) are ethylenically unsaturated compounds having an aromatic ring, such as phenyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, p-nonylphenoxypolyethylene glycol (meth)acrylate, p-nonylphenoxypolypropylene glycol (meth)acrylate, tribromophenyl (meth)acrylate, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene, fluorostyrene, chlorostyrene, bromostyrene, iodostyrene, methoxystyrene, ethoxystyrene, propoxystyrene, p-hydroxy-α-methylstyrene, acetylstyrene, vinyltoluene, divinylbenzene, vinylphenol, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, and p-vinylbenzyl methyl ether;An unsaturated carboxylic acid ester, for example, (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, methyl α-hydroxymethylacrylate, ethyl α-hydroxymethylacrylate, propyl α-hydroxymethylacrylate, butyl α-hydroxymethylacrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, tetrafluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, and dicyclopentenyl oxyethyl (meth)acrylate; an N-vinyl tertiary amine containing an N-vinyl group, for example, N-vinylpyrrolidone, N-vinylcarbazole, and N-vinylmorpholine; an unsaturated ether, for example, vinyl methyl ether and vinyl ethyl ether; and an unsaturated imide, for example, N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, and N-cyclohexylmaleimide, may be at least one selected from the group consisting of.;

[0029] The structural unit (a-3) is represented by the following formula 1: [Chemical formula] may contain a structural unit (a-3-1) represented by the following formula, and in the above formula 1, R1 is C 1~4 alkyl.

[0030] Specifically, the functional group in the structural unit (a-3-1) can rotate freely in the polymer, which realizes the penetration of the developer during development. Thus, the coating film can be more easily developed during development after exposure to light, thereby ensuring excellent sensitivity.

[0031] The content of the structural unit (a-3-1) may be 1 to 30% by weight, or 2 to 20% by weight based on the total weight of the acrylic copolymer (A). Within the above range, it is possible to achieve a pattern of a coating film having excellent sensitivity.

[0032] The structural unit (a-3) is represented by the following formula 2: [Chemical formula] may contain a structural unit (a-3-2) represented by the following formula, and in the above formula 2, R2 and R3 are each independently C 1~4 alkyl.

[0033] Since the acrylic copolymer (A) contains the structural unit (a-3-1) and the structural unit (a-3-2) simultaneously, it is advantageous to maintain the film retention rate while improving the sensitivity.

[0034] The content of the structural unit (a-3-2) may be 1 to 30% by weight, or 2 to 20% by weight based on the total weight of the acrylic copolymer (A).

[0035] The structural unit (a-3-1) and the structural unit (a-3-2) may have a content ratio of 1:99 to 80:20, preferably 5:95 to 40:60. Within the above range, it is advantageous to maintain the film retention rate while improving the sensitivity.

[0036] The amount of the structural unit (a-3) may be 0 to 90 mol% or 50 to 75 mol% based on the total number of moles of the structural units constituting the acrylic copolymer (A). Within the above range of the amount, it is possible to adjust the reactivity of the acrylic copolymer (i.e., the alkali-soluble resin) and improve their solubility in an alkaline aqueous solution. As a result, the coating property of the photosensitive resin composition can be significantly enhanced, and it is possible to form a pattern of a film having good developability.

[0037] The acrylic copolymer can be prepared by blending each of the compounds providing the structural units (a-1), (a-2), and (a-3), adding a molecular weight regulator, a polymerization initiator, a solvent, etc. thereto, subsequently introducing nitrogen into it, and slowly stirring and polymerizing the mixture. The molecular weight regulator can be a mercaptan compound such as butyl mercaptan, octyl mercaptan, lauryl mercaptan, etc., or α-methylstyrene dimer, but it is not particularly limited thereto.

[0038] The polymerization initiator can be an azo compound such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); or benzoyl peroxide; lauryl peroxide; t-butylperoxypivalate; 1,1-bis(t-butylperoxy)cyclohexane, etc., but it is not limited thereto. The polymerization initiator can be used alone or in combination of two or more thereof.

[0039] Furthermore, the solvent may be any solvent generally used for the preparation of the acrylic copolymer. This may preferably be methyl 3-methoxypropionate (MMP) or propylene glycol monomethyl ether acetate (PGMEA).

[0040] In particular, by maintaining the reaction conditions milder and the reaction time longer during the polymerization reaction, it is possible to reduce the residual amount of unreacted monomers.

[0041] The reaction conditions and reaction time are not particularly limited. For example, the reaction temperature can be adjusted to a temperature lower than the conventional temperature, such as room temperature to 60 °C or room temperature to 65 °C. Then, the reaction time is maintained until a sufficient reaction occurs.

[0042] When the acrylic copolymer is prepared by the above process, it is possible to reduce the residual amount of unreacted monomers in the acrylic copolymer to a very low level.

[0043] In this specification, the term "unreacted monomer" (or residual monomer) of the acrylic copolymer used herein refers to the amount of a compound (i.e., monomer) that is intended to provide the structural units (a-1) to (a-3) of the acrylic copolymer but does not participate in the reaction (i.e., does not form the copolymer chain).

[0044] Specifically, the amount of unreacted monomer of the acrylic copolymer (A) remaining in the photosensitive resin composition of the present invention can be 2 parts by weight or less, preferably 1 part by weight or less, based on 100 parts by weight of the copolymer (based on the solid content).

[0045] Here, the term "solid content" refers to the amount of the composition excluding the solvent.

[0046] The weight average molecular weight (Mw) of the acrylic copolymer (A) can be in the range of 5,000 to 20,000 Da, preferably 8,000 to 13,000 Da. Within the above range, the adhesion to the substrate is excellent, the physical and chemical properties are good, and the viscosity is appropriate.

[0047] The acrylic copolymer (A) can be used in an amount of 10 to 90% by weight, 30 to 80% by weight, or 45 to 65% by weight based on the total weight of the photosensitive resin composition excluding the solvent. Within the above range, the developability is properly controlled, which is advantageous in terms of film retention.

[0048] (B) Siloxane copolymer The positive photosensitive resin composition of the present invention may contain a siloxane copolymer as a binder.

[0049] The siloxane copolymer has a complex network-shaped chemical structure. The Si-O bond in the siloxane copolymer has a greater decomposition energy than the C-C bond in the acrylic copolymer. The siloxane copolymer having such structural characteristics can suppress the thermal fluidity of other low-molecular-weight components in the composition, such as linear acrylic copolymers or polyfunctional monomers, when a cured film is formed. Furthermore, the silanol in the siloxane copolymer improves the bonding to a lower substrate, thereby improving the adhesion thereto. This also improves the efficiency of inhibition by the photoactive compound (PAC), thereby helping to improve the film retention rate.

[0050] The siloxane copolymer contains a condensate of a silane compound and / or its hydrolysis product. In such a case, the silane compound or its hydrolysis product can be a monofunctional to tetrafunctional silane compound.

[0051] As a result, the siloxane copolymer may contain siloxane structural units selected from the following Q, T, D, and M types: - Q-type siloxane structural unit: A siloxane structural unit containing a silicon atom and four adjacent oxygen atoms, which can be derived from, for example, a tetrafunctional silane compound having four hydrolyzable groups or a hydrolysis product of a silane compound. - T-type siloxane structural unit: A siloxane structural unit containing a silicon atom and three adjacent oxygen atoms, which can be derived from, for example, a trifunctional silane compound having three hydrolyzable groups or a hydrolysis product of a silane compound. - D-type siloxane structural unit: A siloxane structural unit containing a silicon atom and two adjacent oxygen atoms (i.e., a linear siloxane structural unit) that can be derived from, for example, a bifunctional silane compound having two hydrolyzable groups or a hydrolysis product of a silane compound. - M-type siloxane structural unit: A siloxane structural unit containing a silicon atom and one adjacent oxygen atom that can be derived from, for example, a monofunctional silane compound having one hydrolyzable group or a hydrolysis product of a silane compound.

[0052] For example, the siloxane copolymer may contain a structural unit derived from a compound represented by the following formula 3. For example, the siloxane copolymer may be a condensate of a silane compound represented by the following formula 3 and / or its hydrolysis product. [Formula 3] (R4) n Si(OR5) 4-n

[0053] In the above formula 3, n is an integer from 0 to 3, and each R4 is independently C 1~12 alkyl, C 2~10 alkenyl, C 6~15 aryl, C 3~12 heteroalkyl, C 4~10 heteroalkenyl, or C 6~15 heteroaryl, and each R5 is independently hydrogen, C 1~6 alkyl, C 2~6 acyl, or C 6~15 aryl, and the heteroalkyl, heteroalkenyl, and heteroaryl groups each independently have at least one heteroatom selected from the group consisting of O, N, and S.

[0054] Examples of the structural unit (wherein R4 has a heteroatom) include ether, ester, and sulfide.

[0055] The compound can be a tetrafunctional silane compound (where n is 0), a trifunctional silane compound (where n is 1), a bifunctional silane compound (where n is 2), or a monofunctional silane compound (where n is 3).

[0056] Specific examples of silane compounds include, for example, as tetrafunctional silane compounds, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, and tetrapropoxysilane; as trifunctional silane compounds, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, 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-methacryloxypropyltriethoxysilane, 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-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, ((3-ethyl-3-oxetanyl)methoxy)propyltrimethoxysilane, ((3-ethyl-3-oxetanyl)methoxy)propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-trimethoxysilylpropylsuccinic acid;As bifunctional silane compounds, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, dibutyldimethoxysilane, dimethyldiethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, 3-mercaptopropyldimethoxymethylsilane, cyclohexyldimethoxymethylsilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane and dimethoxydi-p-tolylsilane; and as monofunctional silane compounds, trimethylsilane, tributylsilane, trimethylmethoxysilane, tributylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane and (3-glycidoxypropyl)dimethylethoxysilane may be mentioned.;

[0057] Among the tetrafunctional silane compounds, preferred are tetramethoxysilane, tetraethoxysilane and tetrabutoxysilane; among the trifunctional silane compounds, preferred are methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane and butyltrimethoxysilane; among the bifunctional silane compounds, preferred are dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, dibutyldimethoxysilane and dimethyldiethoxysilane.

[0058] These silane compounds can be used alone or in combination of two or more thereof.

[0059] The conditions for obtaining the hydrolysis product or condensate of the above silane compound of formula 3 are not particularly limited. For example, the silane compound of formula 3 is optionally diluted with a solvent such as ethanol, 2-propanol, acetone, butyl acetate, etc., and water and an acid (e.g., hydrochloric acid, acetic acid, nitric acid, etc.) or a base (e.g., ammonia, triethylamine, cyclohexylamine, tetramethylammonium hydroxide, etc.) that are essential for the reaction are added thereto as a catalyst, and then the mixture is stirred to complete the hydrolysis polymerization reaction, whereby the desired hydrolysis product or its condensate can be obtained.

[0060] The weight average molecular weight of the condensate (i.e., siloxane copolymer) obtained by the hydrolysis polymerization of the above silane compound of formula 3 is preferably in the range of 500 to 50,000 Da. Within the above range, this is more preferable with respect to characteristics of film formation, solubility in a developer, dissolution rate, etc.

[0061] The type and amount of the solvent or acid or base catalyst are not particularly limited. Further, the hydrolysis polymerization reaction can be carried out at a low temperature of 20 °C or lower. Alternatively, the reaction can be promoted by heating or refluxing.

[0062] The required reaction time can be adjusted according to the type and concentration of the silane structural unit, reaction temperature, etc. For example, usually, the reaction takes 15 minutes to 30 days for the molecular weight of the condensate thus obtained to generally reach 500 to 50,000 Da. However, this is not limited thereto.

[0063] The siloxane copolymer may contain linear siloxane structural units (i.e., D-type siloxane structural units). This linear siloxane structural unit may be derived from a bifunctional silane compound, for example, the compound represented by the above formula 3 (wherein n is 2). In particular, the siloxane copolymer may contain structural units derived from the silane compound of the above formula 3 (wherein n is 2) in an amount of 0.5 to 50 mol%, preferably 1 to 30 mol%, based on the number of moles of Si atoms. Within the above content range, while maintaining a specific level of hardness, it is possible for the cured film to have a flexible characteristic, thereby further enhancing the crack resistance to external stress.

[0064] Furthermore, the siloxane copolymer may contain structural units (i.e., T-type structural units) derived from the silane compound represented by the above formula 3 (wherein n is 1). Preferably, the siloxane copolymer may contain structural units derived from the silane compound of the above formula 3 (wherein n is 1) in an amount of 40 to 85 mol%, more preferably 50 to 80 mol%, based on the number of moles of Si atoms. Within the above content range, it is more advantageous to form an accurate pattern profile.

[0065] Furthermore, considering the hardness, sensitivity, and retention rate of the cured film, it is preferable for the siloxane copolymer to contain structural units derived from a silane compound having an aryl group. For example, the siloxane copolymer may contain structural units derived from a silane compound having an aryl group in an amount of 30 to 70 mol%, preferably 35 to 50 mol%, based on the number of moles of Si atoms. Within the above content range, the compatibility of the siloxane copolymer with the 1,2-naphthoquinonediazide compound is excellent, which can achieve a more preferable transparency of the cured film while preventing an excessive decrease in sensitivity. The structural units derived from a silane compound having an aryl group may be the structural units derived from the silane compound of the above formula 3 (wherein R4 is an aryl group), preferably the silane compound of the above formula 3 (wherein n is 1 and R4 is an aryl group), particularly the structural units derived from the silane compound of the above formula 3 (wherein n is 1 and R4 is a phenyl group) (i.e., T-phenyl type siloxane structural units).

[0066] The siloxane copolymer may contain a structural unit (i.e., Q-type structural unit) derived from the silane compound represented by the above formula 3 (wherein n is 0). Preferably, the siloxane copolymer may contain the structural unit derived from the silane compound represented by the above formula 3 (wherein n is 0) in an amount of 10 to 40 mol%, preferably 15 to 35 mol%, based on the number of moles of Si atoms. Within the above content range, the photosensitive resin composition can maintain its solubility in an alkaline aqueous solution at an appropriate level during pattern formation, thereby preventing any defects caused by a reduction in solubility or a drastic increase in the solubility of the composition.

[0067] The term "mol% based on the number of moles of Si atoms", as used herein, refers to the percentage of the number of moles of Si atoms contained in a specific structural unit with respect to the total number of moles of Si atoms contained in all of the structural units constituting the siloxane copolymer.

[0068] The molar amount of siloxane units in the siloxane copolymer can be measured by combining Si-NMR, 1 H-NMR, 13 C-NMR, IR, TOF-MS, elemental analysis, ash measurement, etc. For example, to measure the molar amount of a siloxane unit having a phenyl group, Si-NMR analysis is performed on the entire siloxane copolymer, followed by analysis of the phenyl-bonded Si peak area and the phenyl-unbonded Si peak area. Then, the molar amount can be calculated from the peak area ratio between these.

[0069] Furthermore, during development, if the siloxane copolymer dissolves too rapidly in the developer, a problem occurs in that the adhesion of the pattern deteriorates due to the rapid developability. If the dissolution is too slow, there is a problem of reduced sensitivity.

[0070] Therefore, it is important that the siloxane copolymer has an appropriate level of dissolution rate with respect to the developer. Specifically, when the siloxane copolymer dissolves in an aqueous solution of a 1.5 wt% tetramethylammonium hydroxide solution at a pre-bake temperature of 105 °C, this may have an average dissolution rate (ADR) of 50 Å / sec or more, 100 Å / sec or more, 1,500 Å / sec or more, 100 - 10,000 Å / sec, 100 - 8,000 Å / sec, 100 - 5,000 Å / sec, 1,000 - 5,000 Å / sec, or 1,500 - 5,000 Å / sec. Within the above ranges, this is more advantageous in terms of sensitivity and resolution in development.

[0071] The photosensitive resin composition may contain the siloxane copolymer in an amount of 20 - 80 parts by weight, or 30 - 60 parts by weight, based on 100 parts by weight of the acrylic copolymer (A) (based on the solid content excluding the solvent). Within the above ranges, the developability is properly controlled, which is advantageous with respect to film retention and resolution.

[0072] (C) 1,2 - quinonediazide compound The positive photosensitive resin composition according to the present invention may contain a 1,2 - quinonediazide - based compound (C).

[0073] The 1,2 - quinonediazide - based compound may be a compound used as a photosensitizer in the field of photoresists.

[0074] Examples of 1,2 - quinonediazide - based compounds include esters of phenolic compounds and 1,2 - benzoquinonediazide - 4 - sulfonic acid or 1,2 - benzoquinonediazide - 5 - sulfonic acid; esters of phenolic compounds and 1,2 - naphthoquinonediazide - 4 - sulfonic acid or 1,2 - naphthoquinonediazide - 5 - sulfonic acid; sulfonamides of phenolic compounds (where the hydroxyl group is substituted with an amino group) and 1,2 - benzoquinonediazide - 4 - sulfonic acid or 1,2 - benzoquinonediazide - 5 - sulfonic acid; sulfonamides of phenolic compounds (where the hydroxyl group is substituted with an amino group) and 1,2 - naphthoquinonediazide - 4 - sulfonic acid or 1,2 - naphthoquinonediazide - 5 - sulfonic acid. The above - mentioned compounds can be used alone or in combination of two or more of them.

[0075] In this specification, examples of phenolic compounds 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’ - spirobiinden - 5,6,7,5’,6’,7’ - hexanol, 2,2,4 - trimethyl - 7,2’,4’ - trihydroxyflavan, and the like.

[0076] More specific examples of the 1,2 - quinonediazide - based compounds include esters of 2,3,4 - trihydroxybenzophenone and 1,2 - naphthoquinonediazide - 4 - sulfonic acid, esters of 2,3,4 - trihydroxybenzophenone and 1,2 - naphthoquinonediazide - 5 - sulfonic acid, esters of 4,4'-(1-(4-(1-(4 - hydroxyphenyl)-1 - methylethyl)phenyl)ethylidene)bisphenol and 1,2 - naphthoquinonediazide - 4 - sulfonic acid, esters of 4,4'-(1-(4-(1-(4 - hydroxyphenyl)-1 - methylethyl)phenyl)ethylidene)bisphenol and 1,2 - naphthoquinonediazide - 5 - sulfonic acid, and the like.

[0077] The above - mentioned compounds can be used alone or in combination of two or more of them.

[0078] When the preferred compounds exemplified above are used, the transparency of the photosensitive resin composition can be enhanced.

[0079] The photosensitive resin composition may contain a 1,2 - quinonediazide - based compound in an amount of 2 to 50 parts by weight, or 5 to 30 parts by weight, based on 100 parts by weight of the acrylic copolymer (A) (based on the solid content excluding the solvent). Within the above content range, patterns can be formed more easily, and defects such as the rough surface when the coated film is formed, and pattern shapes such as scum that appears at the bottom of the pattern during development can be prevented, and excellent transmittance can be ensured.

[0080] (D) Polyfunctional monomer The positive - type photosensitive resin composition of the present invention may contain a polyfunctional monomer (D).

[0081] A polyfunctional monomer is a monomer having a small molecular weight and a double bond. In particular, this may contain at least one ethylenically unsaturated double bond. More specifically, the polyfunctional monomer may include a monofunctional or polyfunctional ester compound having at least one ethylenically unsaturated double bond. From the viewpoint of developability, this may preferably be a trifunctional to octafunctional compound.

[0082] The polyfunctional monomer may be at least one selected from the group consisting of ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,6 - hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, monoester of pentaerythritol tri(meth)acrylate and succinic acid, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, monoester of dipentaerythritol penta(meth)acrylate and succinic acid, caprolactone - modified dipentaerythritol hexa(meth)acrylate, pentaerythritol triacrylate - hexamethylene diisocyanate (reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, and ethylene glycol monomethyl ether acrylate.

[0083] Examples of commercially available polyfunctional monomers include (i) monofunctional (meth)acrylates such as Aronix M-101, M-111, and M-114 (manufactured by Toagosei Co., Ltd.), KAYARAD T4-110S and T4-120S (manufactured by Nippon Kayaku Co., Ltd.), and V-158 and V-2311 (manufactured by Osaka Organic Chemical Industry Co., Ltd.); (ii) difunctional (meth)acrylates such as Aronix M-210, M-240, and M-6200 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, and R-604 (manufactured by Nippon Kayaku Co., Ltd.), and V-260, V-312, and V-335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.); and (iii) polyfunctional (meth)acrylates having three or more functionalities such as Aronix M-309, M-400, M-403, M-405, M-450, M-7100, M-8030, M-8060, and TO-1382 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPHA-40H, T-1420, DPCA-20, DPCA-30, DPCA-60, and DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), and V-295, V-300, V-360, V-GPT, V-3PA, V-400, and V-802 (manufactured by Osaka Organic Chemical Industry Co., Ltd).

[0084] Polyfunctional monomers are generally mainly used in the negative type. In the negative type state, this acts as a crosslink by light during exposure to light. On the other hand, in the positive type state of the present invention, this acts to improve developability, thereby enhancing sensitivity, providing excellent surface characteristics, and removing scum.

[0085] Specifically, the polyfunctional monomer may have a relatively small molecular weight compared to the binder (i.e., acrylic copolymer (A) and siloxane copolymer (B)). The polyfunctional monomer having a relatively small molecular weight compared to the binder exists between the binders and promotes the penetration of the developer into the pre-baked film during development, thereby improving sensitivity. Furthermore, as a result, it becomes possible to ensure excellent surface characteristics and suppress scum because the developability near the holes is improved.

[0086] The photosensitive resin composition may contain a polyfunctional monomer in an amount of 1 to 30 parts by weight, or 3 to 20 parts by weight, based on 100 parts by weight of the acrylic copolymer (A) (based on the solid content excluding the solvent).

[0087] Within the above range, the developability can be appropriately adjusted to ensure excellent sensitivity. When the coating film is formed, the surface of the coating film is not rough, and scum does not occur at the bottom of the film during development. If it is used in an amount less than the above range, the sensitivity is not sufficiently enhanced. If it is used in excess, the thermal fluidity in the composition during hard baking is improved, thereby deteriorating the pattern resolution.

[0088] (E) Solvent The positive photosensitive resin composition of the present invention can be prepared in the form of a liquid composition in which the above components are mixed with a solvent. The solvent can be, for example, an organic solvent.

[0089] The amount of the solvent in the positive photosensitive resin composition according to the present invention is not particularly limited. For example, the solvent can be used such that the solid content is 10 to 70% by weight or 15 to 60% by weight based on the total weight of the composition.

[0090] The term solid content refers to the components constituting the composition excluding the solvent. When the amount of the solvent is within the above range, the composition can be easily coated, and its fluidity can be maintained at an appropriate level.

[0091] The solvent of the present invention is not particularly limited as long as it can dissolve the above components and is chemically stable. For example, the solvent can be 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.

[0092] Specific examples of the solvent 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, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 2-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

[0093] Among these, preferred ones are ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, ketones, etc. Particularly, 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, methyl 3-methoxypropionate, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, etc. are preferred.

[0094] The solvents exemplified above may be used alone or in combination of two or more of them.

[0095] (F) Epoxy compound The positive photosensitive resin composition according to the present invention may further contain an epoxy compound. The epoxy compound can increase the internal density of the binder, specifically the siloxane copolymer, thereby enhancing the chemical resistance of the cured film formed therefrom.

[0096] The epoxy compound can be a homo-oligomer or hetero-oligomer of an unsaturated monomer containing at least one epoxy group.

[0097] Examples of unsaturated monomers containing at least one epoxy group include glycidyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 5,6-epoxyhexyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 2,3-epoxycyclopentyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, α-ethylglycidyl acrylate, α-n-propylglycidyl acrylate, α-n-butylglycidyl acrylate, N-(4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl)acrylamide, N-(4-(2,3-epoxypropoxy)-3,5-dimethylphenylpropyl)acrylamide, allyl glycidyl ether, 2-methylallyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and mixtures thereof.

[0098] The epoxy compound can be synthesized by any method well known in the art.

[0099] Examples of epoxy compounds can include glycidyl methacrylate homopolymer, and 3,4-epoxycyclohexylmethyl methacrylate homopolymer.

[0100] The epoxy compound can further include the following structural units.

[0101] That specific example includes styrene; styrenes having an alkyl substituent, such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; styrenes having a halogen, such as fluorostyrene, chlorostyrene, bromostyrene, and iodostyrene; styrenes having an alkoxy substituent, such as methoxystyrene, ethoxystyrene, and propoxystyrene; acetylstyrene, such as p-hydroxy-α-methylstyrene; ethylenically unsaturated compounds having an aromatic ring, such as divinylbenzene, vinylphenol, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, and p-vinylbenzyl methyl ether;Unsaturated carboxylic acid esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, methyl α-hydroxymethylacrylate, ethyl α-hydroxymethylacrylate, propyl α-hydroxymethylacrylate, butyl α-hydroxymethylacrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, poly(ethylene glycol) methyl ether (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, p-nonylphenoxypolyethylene glycol (meth)acrylate, p-nonylphenoxypolypropylene glycol (meth)acrylate, tetrafluoropropyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, tribromophenyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate and dicyclopentenyl oxyethyl (meth)acrylate; Tertiary amines having an N-vinyl group, such as N-vinylpyrrolidone, N-vinylcarbazole and N-vinylmorpholine; Unsaturated ethers, such as vinyl methyl ether and vinyl ethyl ether;It may contain any structural unit derived from an unsaturated imide, such as N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, and N-cyclohexylmaleimide. The structural units derived from the compounds exemplified above may be contained alone in the epoxy compound or in a combination of two or more of them.;

[0102] Among the above compounds, styrene-based compounds may be more preferred considering polymerizability.

[0103] In particular, with respect to chemical resistance, it is more preferable that the epoxy compound does not contain a carboxyl group by not using the structural unit derived from the monomer containing a carboxyl group among the above.

[0104] The structural unit can be used in an amount of 0 to 70 mol%, preferably 10 to 60 mol%, based on the total number of moles of the structural units constituting the epoxy compound. Within the above content range, this may be more advantageous with respect to film strength.

[0105] The weight average molecular weight of the epoxy compound may preferably be 100 to 30,000 Da. Its weight average molecular weight may more preferably be 1,000 to 15,000 Da. When the weight average molecular weight of the epoxy compound is at least 100 Da, the hardness of the cured film may be more preferable. When this is 30,000 Da or less, the cured film may have a uniform thickness, which is suitable for planarizing any step thereon.

[0106] The photosensitive resin composition may contain an epoxy compound in an amount of 1 to 40 parts by weight, or 4 to 25 parts by weight, based on 100 parts by weight of the acrylic copolymer (A) (based on the solid content excluding the solvent). Within the above content range, chemical resistance and adhesion may be more preferable.

[0107] (G) Surfactant The positive photosensitive resin composition of the present invention may further contain a surfactant for enhancing its coating property, if necessary.

[0108] The type of the surfactant is not particularly limited, and examples thereof include fluorine-based surfactants, silicon-based surfactants, nonionic surfactants, and the like.

[0109] Specific examples of surfactants include surfactants based on fluorine and silicon, such as FZ-2122 supplied by Dow Corning Toray Co., Ltd., BM-1000 and BM-1100 supplied by BM CHEMIE Co., Ltd., Megapack F-142D, F-172, F-173 and F-183 supplied by Dainippon Ink and Chemicals, Inc., Florad FC-135, FC-170C, FC-430 and FC-431 supplied by Sumitomo 3M Limited, Sufron S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105 and SC-106 supplied by Asahi Glass Co., Ltd., Eftop EF301, EF303 and EF352 supplied by Shinakida Kasei Co., Ltd., SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57 and DC-190 supplied by Toray Silicon Co., Ltd.; nonionic surfactants, such as polyoxyethylene alkyl ethers including polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc.; polyoxyethylene aryl ethers including polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, etc.; and polyoxyethylene dialkyl esters including polyoxyethylene dilaurate, polyoxyethylene distearate, etc.; and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylate-based copolymers Polyflow No. 57 and No. 95 (manufactured by Kyoei Yuji Chemical Co., Ltd.), etc. They can be used alone or in combination of two or more.

[0110] The photosensitive resin composition may contain a surfactant in an amount of 0.001 to 5 parts by weight, or 0.05 to 2 parts by weight, based on 100 parts by weight of the acrylic copolymer (A) (based on the solid content excluding the solvent). Within the above content range, the coating and leveling properties of the composition can be improved.

[0111] (H) Adhesion promoter The positive photosensitive resin composition of the present invention may further contain an adhesion promoter for enhancing the adhesion to the substrate.

[0112] The adhesion promoter 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.

[0113] The type of the adhesion promoter is not particularly limited. It may be at least one selected from the group consisting of trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0114] Preferred are γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, or N-phenylaminopropyltrimethoxysilane, which can enhance the film retention rate and the adhesion to the substrate.

[0115] The photosensitive resin composition may contain an adhesion promoter in an amount of 0 to 5 parts by weight, or 0.001 to 2 parts by weight, based on 100 parts by weight of the acrylic copolymer (A) (based on the solid content excluding the solvent). Within the above content range, the adhesion to the substrate can be further enhanced.

[0116] (I) Silane compound The positive photosensitive resin composition of the present invention contains at least one silane compound represented by the following formula 4, particularly a T-type and / or Q-type silane monomer, and thereby, in combination with an epoxy compound, for example, an epoxy oligomer, by reducing the highly reactive silanol groups (Si-OH) in the siloxane copolymer, the chemical resistance can be enhanced during the processing in post-processing. [Formula 4] (R6) n Si(OR7) 4-n In the above formula 4, n is an integer from 0 to 3, R6 are each independently C 1~12 alkyl, C 2~10 alkenyl, C 6~15 aryl, C 3~12 heteroalkyl, C 4~10 heteroalkenyl, or C 6~15 heteroaryl, and R7 are each independently hydrogen, C 1~6 alkyl, C 2~6 acyl, or C 6~15 aryl, and the heteroalkyl, heteroalkenyl, and heteroaryl groups each independently have at least one heteroatom selected from the group consisting of O, N, and S.

[0117] Examples of structural units (wherein R6 has a heteroatom) include ether, ester, and sulfide.

[0118] According to the present invention, the compound can be a tetrafunctional silane compound (wherein n is 0), a trifunctional silane compound (wherein n is 1), a bifunctional silane compound (wherein n is 2), or a monofunctional silane compound (wherein n is 3).

[0119] Specific examples of silane compounds include, for example, as tetrafunctional silane compounds, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, and tetrapropoxysilane; as trifunctional silane compounds, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, d 3-Methyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxybenzoyloxy)pentyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, ((3-ethyl-3-oxetanyl)methoxy)propyltrimethoxysilane, ((3-ethyl-3-oxetanyl)methoxy)propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-trimethoxysilylpropionic acid; As bifunctional silane compounds, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, dibutyldimethoxysilane, dimethyldiethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3-mercaptopropyldimethoxymethylsilane, cyclohexyldimethoxymethylsilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane and dimethoxydi-p-tolylsilane;As the monofunctional silane compound, it may include trimethylsilane, tributylsilane, trimethylmethoxysilane, tributylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, and (3-glycidoxypropyl)dimethylethoxysilane.;

[0120] Among the tetrafunctional silane compounds, preferred are tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane; among the trifunctional silane compounds, preferred are methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; among the difunctional silane compounds, preferred are dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, dibutyldimethoxysilane, and dimethyldiethoxysilane.

[0121] These silane compounds can be used alone or in combination of two or more thereof.

[0122] The photosensitive resin composition may contain a silane compound in an amount of 0 to 50 parts by weight, or 3 to 12 parts by weight, based on 100 parts by weight of the acrylic copolymer (A) (based on the solid content excluding the solvent). Within the above content range, the chemical resistance of the formed cured film can be further enhanced.

[0123] In addition, the positive photosensitive resin composition of the present invention may contain other additives such as antioxidants and stabilizers as long as they do not adversely affect the physical properties of the colored photosensitive resin composition.

[0124] Furthermore, the present invention also provides a cured film formed from the positive photosensitive resin composition.

[0125] The cured film can be formed by a method known to those skilled in the art, for example, a method of coating the photosensitive resin composition on a substrate and then curing it.

[0126] More specifically, in the curing process, the photosensitive resin composition coated on the substrate is pre-baked at a temperature of, for example, 60 to 130 °C to remove the solvent, then exposed using a photomask having a desired pattern, and then developed using a developer, for example, a tetramethylammonium hydroxide (TMAH) solution, to form a pattern on the coating layer. Thereafter, if necessary, the patterned coating layer is post-baked at a temperature of, for example, 150 to 300 °C for 10 minutes to 5 hours to prepare a desired cured film. Exposure to light is carried out at an exposure rate of 10 to 200 mJ / cm 2 or 10 to 300 mJ / cm 2 with reference to a wavelength of 365 nm in the wavelength range of 200 to 500 nm. According to the process of the present invention, it is possible to easily form a desired pattern from the perspective of the process.

[0127] Coating of the photosensitive resin composition on the substrate can be carried out by, for example, spin coating method, slit coating method, roll coating method, screen printing method, applicator method, etc. at a desired thickness of 2 to 25 μm. Furthermore, as the light source used for exposure (irradiation), a low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, argon gas laser, etc. can be used. X-rays, electron beams, etc. can also be used as required.

[0128] On the other hand, after exposure, the photosensitive resin composition is exposed at 300 to 2,000 mJ / cm 2 or 500 to 1,500 mJ / cm 2It may be possible to obtain a more transparent cured film by subjecting it to photo-bleaching with energy, developing it. Specifically, the composition can be coated on a substrate, subjected to an exposure and development process, and then subjected to photo-bleaching and hard baking to form a cured film. The photo-bleaching process removes the N2 bond of a 1,2-quinonediazide-based compound, which is one of the main components of the positive photosensitive resin composition, thereby forming a transparent cured film. Without the photo-bleaching process, when hard baking is carried out, a reddish cured film is obtained, and therefore, for example, the transmittance in the region of 400 to 600 nm decreases.

[0129] The positive photosensitive resin composition of the present invention has almost no thermal fluidity, excellent appearance characteristics such as a rough surface and scum of the film, and can form a cured film with further enhanced sensitivity.

[0130] Specifically, the cured film has a thickness of 3.5 μm and a sensitivity of 50 to 140 mJ / cm 2 , 50 to 130 mJ / cm 2 , 60 to 130 mJ / cm 2 , or 70 to 130 mJ / cm 2 and may have such sensitivity.

[0131] Furthermore, as described above, when a positive photosensitive resin composition is coated on a substrate, dried by heat to form a dry film, and then developed and hard baked to prepare a cured film, the difference in the line dimension (i.e., CD dimension) of the hole pattern formed in the cured film before and after the hard baking process for a mask dimension of 11 μm can be 0.01 to 0.1 μm, 0.01 to 0.08 μm, or 0.05 to 0.08 μm. Within the above range, no heat flow occurs in the composition, so it becomes possible to achieve better pattern developability and sensitivity.

[0132] As described above, in the positive photosensitive resin composition, a polyfunctional monomer is introduced into the positive photosensitive resin composition containing a mixed binder, and here a siloxane copolymer is added to the acrylic copolymer, whereby when developing the pre-baked film, the penetration of the developer into the binder is promoted to improve the solubility in the developer, and thereby the pattern developability and sensitivity can be further enhanced. Further, when the composition is used, a cured film having almost no thermal fluidity can be obtained. Further, the cured film prepared from this composition can have excellent appearance characteristics such as a rough surface of the film and no scum at the bottom of the film during development. Therefore, the cured film prepared therefrom can be advantageously used in liquid crystal displays, organic EL displays, and the like. Embodiments of the present invention

[0133] Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are provided for the purpose of explaining the present invention, and the scope of the present invention is not limited thereto. In the following preparation examples, the weight average molecular weight is determined by gel permeation chromatography (GPC, eluent: tetrahydrofuran) with reference to polystyrene standards.

Examples

[0134] Preparation Example 1: Preparation of Acrylic Copolymer (A-1) 200 parts by weight of methyl 3-methoxypropionate (MMP) was charged as a solvent into a flask equipped with a cooling tube and a stirrer, and while the solvent was slowly stirred, the temperature of the solvent was raised to 70 °C. Subsequently, 19.8 parts by weight of styrene (Sty), 25.7 parts by weight of methyl methacrylate (MMA), 27.1 parts by weight of glycidyl methacrylate (GMA), 15.6 parts by weight of methacrylic acid (MAA) and 11.7 parts by weight of methyl acrylate (MA) were added thereto. Next, 3 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator was added dropwise thereto over 5 hours to conduct a polymerization reaction. The weight average molecular weight of the copolymer thus obtained (solid content: 32% by weight) was 9,000 to 11,000 Da.

[0135] Preparation Example 2 to 4: Preparation of Acrylic Copolymers (A-2 to A-4) The acrylic copolymers (A-2 to A-4) were prepared in the same manner as in Preparation Example 1, except that the types and / or contents of the monomers were changed as shown in Table 1 below.

[0136] [Table 1]

[0137] Preparation Example 1: Preparation of Siloxane Copolymer (B-1) 20% by weight of phenyltrimethoxysilane (PhTMOS), 30% by weight of methyltrimethoxysilane (MTMOS), 20% by weight of tetraethoxysilane (TEOS), and 15% by weight of deionized water (DI water) were added to a reactor equipped with a reflux condenser, and subsequently 15% by weight of PGMEA was added thereto. Subsequently, the mixture was vigorously stirred for 6 hours while refluxing in the presence of 0.1% by weight of an oxalic acid catalyst. Subsequently, the mixture was cooled and diluted with PGMEA so that the solid content became 30% by weight, thereby obtaining a siloxane copolymer (B-1). The weight average molecular weight of the copolymer thus obtained (solid content: 30% by weight) was 6,000 to 11,000 Da.

[0138] Furthermore, when the copolymer thus obtained was pre-baked at about 100 °C and then dissolved in an aqueous solution of 1.5 wt% tetramethylammonium hydroxide, the average dissolution rate (ADR) was 4,113 Å / sec.

[0139] Preparation Examples 6 to 9: Preparation of Siloxane Copolymers (B-2 to B-5) Siloxane copolymers (B-2 to B-5) were prepared in the same manner as in Preparation Example 1, except that the types and / or contents of the monomers were changed as shown in Table 2 below.

[0140] [Table 2]

[0141] Preparation Example 10: Preparation of Epoxy Compound (F) The three-necked flask was equipped with a condenser and placed on a stirrer equipped with a thermostat. 100 parts by weight of a monomer consisting of 100 mol% of cyclohexylmethyl methacrylate, 10 parts by weight of 2,2'-azobis(2-methylbutyronitrile), and 100 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was charged into the flask, and then nitrogen was introduced thereinto. Thereafter, the temperature of the solution was raised to 80 °C while slowly stirring the solution, and the temperature was maintained for 5 hours. Subsequently, PGMEA was added so that the solid content became 20 wt%, thereby obtaining an epoxy compound having a weight average molecular weight of 3,000 to 6,000 Da.

[0142] Examples and Comparative Examples: Preparation of Positive-Type Photosensitive Resin Compositions The photosensitive resin compositions of the following examples and comparative examples were each prepared using the compounds prepared in the above preparation examples.

[0143] The components used in the following examples and comparative examples are as follows.

[0144] [Table 3]

[0145] Example 1: Preparation of Photosensitive Resin Composition Into a reactor, 22.50% by weight and 28.32% by weight of the acrylic copolymers (A-1) and (A-2) of Preparation Examples 1 and 2 were respectively charged based on the total weight of the photosensitive resin composition excluding the remaining solvent. Further, thereto, based on 100 parts by weight of the acrylic copolymer (A) (based on the solid content), 57.33 parts by weight of the siloxane copolymer (B-1) of Preparation Example 5, 6.53 parts by weight of the epoxy compound (F) of Preparation Example 10, 5.90 parts by weight of the polyfunctional monomer (D-1), and 15.30 parts by weight and 11.36 parts by weight of the 1,2-quinonediazide compounds (C-1) and (C-2) were respectively charged. Further, 0.23% by weight of a surfactant was added based on the total weight of the composition. Subsequently, 45.24% by weight of the solvent (E-1), 24.96% by weight of the solvent (E-2), and 7.80% by weight of the solvent (E-3) were mixed therewith so that the solid content became 22% by weight. After 3 hours, the mixed solution was filtered through a membrane filter having a pore size of 0.2 μm to obtain a composition solution having a solid content of 22% by weight.

[0146] Examples 2 to 10 and Comparative Examples 1 to 4: Preparation of Photosensitive Resin Composition The photosensitive resin composition solutions were prepared in the same manner as in Example 1, except that the types and / or contents of the respective components were changed as shown in Tables 4 and 5 below.

[0147] [Table 4]

[0148] [Table 5]

[0149] [Evaluation Example] Evaluation Example 1: Film Retention Rate The compositions prepared in the examples and comparative examples were each coated on a glass substrate by spin coating. Subsequently, the coated substrate was pre-baked on a hot plate maintained at 105 °C for 105 seconds to form a dry film. This was then developed at 23 °C for 85 seconds with an aqueous developer of 2.38 wt% tetramethylammonium hydroxide via a paddle nozzle. Thereafter, the developed film was subjected to photobleaching by exposing it for a certain period of time at an irradiation dose rate based on a wavelength of 365 nm using an aligner (model name: MA6) that emits light having a wavelength in the range of 200 nm to 450 nm. The exposed film thus obtained was heated in a convection oven at 240 °C for 20 minutes to prepare a cured film with a thickness of 2.1 μm. The film retention rate (%) was obtained by calculating the ratio (percentage) of the thickness of the post-baked film to the thickness of the pre-baked film using a measuring instrument (SNU Precision) according to the following formula. The film retention rate was evaluated to be excellent at 70% or more and good at less than 60% to 70%. 2 The film retention rate was evaluated to be excellent at 70% or more and good at less than 60% to 70%. [Formula] Film retention rate (%) = (thickness of the film after post-baking / thickness of the film after pre-baking) × 100

[0150] Evaluation Example 2: Sensitivity The compositions prepared in the examples and comparative examples were each coated on a glass substrate by spin coating. Subsequently, the coated substrate was pre-baked on a hot plate maintained at 105 °C for 105 seconds to form a dry film. A mask having a pattern of square holes with dimensions in the range of 1 μm to 30 μm was placed on the dried film. Subsequently, the film was exposed for a certain period of time at a wavelength of 365 nm in the range of 0 to 200 mJ / cm² based on a wavelength of 365 nm using an aligner (model name: MA6) that emits light having a wavelength in the range of 200 nm to 450 nm. 2It was exposed at the exposure rate of. In this specification, an i-line optical filter was applied and the distance between the exposure reference lamp and the substrate was maintained at 20 μm. Subsequently, it was developed at 23°C for 85 seconds through a paddle nozzle using a developer which is a 2.38 wt% aqueous solution of tetramethylammonium hydroxide.

[0151] Thereafter, the developed film was subjected to photobleaching by exposing it for a certain period of time at an irradiation dose rate of 200 mJ / cm 2 with reference to a wavelength of 365 nm using an aligner (model name: MA6) that emits light having a wavelength in the range of 200 nm to 450 nm. The exposed film thus obtained was heated in a convection oven at 240°C for 20 minutes to prepare a cured film with a thickness of 3.5 μm (i.e., the hard bake process).

[0152] For the hole patterns formed for each mask dimension of 11 μm through the above procedure, the amount of exposure energy (mJ / cm 2 ) required to achieve a critical dimension (CD, unit: μm) of 10 μm was measured. The lower the exposure energy, the better the sensitivity.

[0153] Evaluation Example 3: Thermal fluidity A cured film was obtained in the same manner as in Evaluation Example 2.

[0154] Under such circumstances, the critical dimensions (CD, unit: μm) of the hole patterns formed for a mask dimension of 11 μm before and after curing were measured respectively. From this difference (i.e., the difference in the critical dimensions of the hole patterns formed in the cured film before and after the hard bake process), the thermal fluidity was evaluated according to the following criteria. - 0.1 μm or less: No thermal fluidity (excellent) - More than 0.1 μm to 0.3 μm: Slight thermal fluidity (good) - More than 0.3 μm: High thermal fluidity (poor)

[0155] Evaluation Example 4: Scum A cured film was obtained in the same manner as in Evaluation Example 2. This was exposed so that the critical dimension of the hole pattern formed for each mask dimension of 11 μm would be 10 μm. Subsequently, the cross-section of the hole pattern was observed by SEM to confirm the presence of scum. The less scum there is, the better. When no scum was present, it was marked as "×". When scum was present, it was marked as "○". When a large amount of scum was present, it was [Number] so marked.

[0156] Evaluation Example 5: Surface Roughness A cured film was obtained in the same manner as in Evaluation Example 2. The surface of the prepared cured film was observed by SEM, and the degree of defects such as irregularities and cracks on the surface was numerically evaluated from 1 to 5. The closer to 1, the better the surface roughness.

[0157] [Table 6]

[0158] As shown in Table 6, the cured film prepared from the composition of the examples included in the scope of the present invention has excellent sensitivity, and the difference in critical dimensions before and after curing is small, indicating that almost no heat flow occurred (i.e., excellent heat fluidity). Furthermore, no scum was found on the cross-section of the hole pattern, and since the surface roughness was good or excellent, the appearance characteristics were also excellent.

[0159] In contrast, in the cured films prepared from the compositions of Comparative Examples 1 and 2 (which do not contain a polyfunctional monomer), the sensitivity was inferior to that of the Examples. Scum was found on the cross-section of the hole pattern, and many defects such as irregularities and cracks were found on the surface, resulting in poor surface roughness. Further, in the cured film prepared from the composition of Comparative Example 3 (which does not contain a siloxane compound), the appearance characteristics (e.g., occurrence of scum and surface roughness) were equal to those of the Examples, but on the other hand, the thermal fluidity was large (i.e., poor thermal fluidity), and the sensitivity was lower than that of the Examples. Further, in the cured film prepared from the composition of Comparative Example 4 (which contains an epoxy monomer), the surface roughness was very poor, and in particular, a large amount of scum was found in the hole pattern. From the above, although the developability can be improved by introducing small monomers such as an epoxy monomer, it was confirmed that when an epoxy group was introduced as a functional group instead of a double bond, the surface roughness and the scum in the pattern could not be improved.

Claims

1. (A)An acrylic copolymer; (B)A siloxane copolymer; (C)A 1,2 - quinonediazide compound; (D)A polyfunctional monomer; and (E)A solvent, Based on 100 parts by weight of the acrylic copolymer (A), the polyfunctional monomer (D) is included in an amount of 1 to 30 parts by weight, The polyfunctional monomer (D) is a trifunctional to octafunctional ester compound having an ethylenically unsaturated double bond, The acrylic copolymer (A) contains (a - 1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic anhydride, or a combination thereof; (a - 2) a structural unit derived from an unsaturated compound containing an epoxy group; and (a - 3) a structural unit derived from an ethylenically unsaturated compound different from the structural units (a - 1) and (a - 2), a positive - type photosensitive resin composition.

2. The structural unit (a - 3) is represented by the following formula 1: 【Chemical 1】 including a structural unit (a-3-1) represented by, in the above formula (1), R １ is C １～４ alkyl, the positive photosensitive resin composition according to claim 1.

3. The structural unit (a - 3) is represented by the following formula 2: [Chemical 2] including the structural unit (a-3-2) represented by, in the above formula (2), R ２ and R ３ are each independently C １～４ alkyl, the positive photosensitive resin composition according to claim 2.

4. The structural unit (a - 3 - 1) and the structural unit (a - 3 - 2) have a content ratio of 1:99 to 80:20, the positive - type photosensitive resin composition according to Claim 3.

5. The siloxane copolymer (B) contains a structural unit derived from a silane compound represented by the following formula 3: [Formula 3] (R ４ ) ｎ Si(OR ５ ) ４－ｎ In the above formula 3, n is an integer from 0 to 3, R ４ is, independently of one another, C １～１２ alkyl, C ２～１０ alkenyl, C ６～１５ aryl, C ３～１２ heteroalkyl, C ４～１０ heteroalkenyl, or C ６～１５ heteroaryl, and R ５ is, independently of each other, hydrogen, C １～６ alkyl, C ２～６ acyl or C ６～１５ aryl, and The heteroalkyl, the heteroalkenyl, and the heteroaryl groups each independently have at least one heteroatom selected from the group consisting of O, N, and S, the positive - type photosensitive resin composition according to Claim 1.

6. Based on 100 parts by weight of the acrylic copolymer (A), the siloxane copolymer (B) is included in an amount of 20 to 80 parts by weight, the positive - type photosensitive resin composition according to Claim 1.

7. The positive - type photosensitive resin composition according to Claim 1, further comprising an epoxy compound.

8. A cured film prepared from the positive - type photosensitive resin composition according to Claim 1.

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