Positive-type photosensitive resin composition and cured film prepared therefrom

Abstract

To provide a positive-type photosensitive resin composition that is capable of forming a cured film having excellent film retention rates and pattern adhesiveness with time, and a cured film prepared therefrom.SOLUTION: The present invention relates to a positive-type photosensitive resin composition which comprises (A) an acrylic copolymer; (B) a siloxane copolymer; (C) a 1,2-quinonediazide compound; and (D) a solvent, and the solvent (D) comprises a nonpolar organic solvent having a boiling point of 155 to 200°C at 25°C and 1 atm.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a positive photosensitive resin composition capable of forming a cured film having excellent film retention over time and pattern adhesion, and to a cured film prepared from the composition and used in liquid crystal displays, organic EL displays, etc. [Background technology]

[0002] Generally, in LCDs or OLED displays, a transparent planarization film is formed on the substrate of the thin film transistor (TFT) to prevent contact between the transparent electrode and the data line. Through the transparent pixel electrode located near the data line, the aperture ratio of the panel can be increased, and high brightness and high resolution can be achieved.

[0003] To form such a transparent planarization film, several processing steps are employed to impart a specific pattern profile, and in this process, positive-type photosensitive resin compositions are widely adopted because they require fewer processing steps. In particular, as the size of LCD panels increases, the demand for positive-cured films free of stitch mura and lens mura increases.

[0004] In relation to conventional positive-type photosensitive resin compositions, techniques have been introduced that use polysiloxane resins, acrylic resins, and the like as raw materials.

[0005] Compared to polysiloxane resins rich in silanol groups, acrylic resins have a problem of lower sensitivity than polysiloxane resins due to a limited content of carboxyl groups involved in development. To compensate for this, photosensitive resin compositions using polysiloxane resins and acrylic resins together, thereby exhibiting excellent sensitivity and adhesion, and cured films prepared therefrom have been proposed (see Patent Document 1).

[0006] However, the sensitivity has not yet been improved to a satisfactory level. Furthermore, in the prior art in which polysiloxane resin and acrylic resin are used as binders, a diol compound is generated by the reaction between the epoxy group in the acrylic resin and the HO molecule in the polysiloxane resin, which causes a new problem of poor pattern and deterioration of adhesion to the substrate.

[0007] In recent years, attempts have been made to solve this problem by adjusting the binder content or adding additives, but in most of these techniques, the properties of the cured film were evaluated to be improved only immediately after its preparation, and the stability over time could not be demonstrated. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent No. 5,099,140 Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, an object of the present invention is to provide a positive photosensitive resin composition that uses a mixed binder containing an acrylic copolymer and a siloxane copolymer, in which the generation of diol compounds is suppressed, thereby maintaining an appropriate level of developability when a cured film is prepared, thereby not only improving pattern adhesion, resolution, and sensitivity but also providing a cured film that has excellent stability over time at room temperature and low temperatures, and a cured film prepared from the composition that is used in liquid crystal displays, organic EL displays, etc. [Means for solving the problem]

[0010] In order to achieve the above object, the present invention provides a positive photosensitive resin composition comprising (A) an acrylic copolymer, (B) a siloxane copolymer, (C) a 1,2-quinonediazide compound, and (D) a solvent, wherein solvent (D) comprises a nonpolar organic solvent having a boiling point of 155 to 200°C at 25°C and 1 atm.

[0011] To achieve another object, the present invention provides a cured film prepared from a photosensitive resin composition. [Effects of the Invention]

[0012] The positive photosensitive resin composition of the present invention contains a non-polar organic solvent, which suppresses the reactivity of the epoxy group in the composition and reduces the production of diol compounds. When a cured film is prepared from the composition, an appropriate level of developability is maintained, and pattern adhesion, resolution, and sensitivity can be further improved.

[0013] Furthermore, since the composition of the present invention has a small difference in film retention rate between room temperature and low temperature, the composition can be stable over time. [Brief explanation of the drawings]

[0014] [Figure 1] 1 is a photomicrograph showing the line patterns remaining after development of the cured films prepared in Examples 1 to 11. [Figure 2] 1 is a photomicrograph showing line patterns remaining after development of the cured films prepared in Comparative Examples 1 to 4. [Figure 3] 1 is a photomicrograph showing various line patterns formed on a cured film, indicating a rating scale for assessing adhesion. DETAILED DESCRIPTION OF THE INVENTION

[0015] The present invention is not limited to the following description, but can be modified in various ways without departing from the spirit of the present invention.

[0016] Throughout this specification, when a portion is referred to as "comprising" an element, it is understood that other elements may be included, rather than excluding other elements, unless otherwise specified. Additionally, all numbers and expressions relating to ingredient quantities, reaction conditions, and the like used herein should be understood to be modified by the term "about," unless otherwise specified.

[0017] The present invention provides a positive-type photosensitive resin composition comprising (A) an acrylic copolymer, (B) a siloxane copolymer, (C) a 1,2-quinonediazide compound, and (D) a solvent. In this specification, the solvent (D) comprises a nonpolar organic solvent having a boiling point of 155 to 200°C at 25°C and 1 atm.

[0018] The composition may optionally further comprise (E) a multifunctional monomer, (F) an epoxy compound, (G) a surfactant, (H) an adhesion aid, and / or (I) a silane compound.

[0019] As used herein, the term "(meth)acrylic" means "acrylic" and / or "methacrylic", and the term "(meth)acrylate" means "acrylate" and / or "methacrylate".

[0020] The weight average molecular weight (g / mole or Da) of each component listed below is determined by gel permeation chromatography (GPC, eluent: tetrahydrofuran) relative to polystyrene standards.

[0021] (A) Acrylic copolymer The positive photosensitive resin composition of the present invention may contain an acrylic copolymer (A) as a binder.

[0022] The acrylic copolymer may contain (a-1) structural units derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid anhydride, or a combination thereof; (a-2) structural units derived from an unsaturated compound containing an epoxy group; and (a-3) structural units derived from an ethylenically unsaturated compound different from the structural units (a-1) and (a-2).

[0023] The acrylic copolymer is an alkali-soluble resin that provides developability in the development step, and also serves as a base for forming a film when coated and a structure for forming the final pattern.

[0024] (a-1) Structural units 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.

[0025] The ethylenically unsaturated carboxylic acid, ethylenically unsaturated carboxylic acid anhydride, or a combination thereof is a polymerizable unsaturated compound containing at least one carboxyl group in its molecule. It may be at least one selected from 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 divalent or higher polycarboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate. Among these, (meth)acrylic acid is preferred from the viewpoint of developability.

[0026] 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, film pattern formation can be achieved while maintaining favorable developability.

[0027] (a-2) Structural units derived from unsaturated compounds containing epoxy groups The structural unit (a-2) can be derived from an unsaturated monomer containing at least one epoxy group.

[0028] Specific 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, and combinations thereof.

[0029] The amount of the structural unit (a-2) derived from an 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.

[0030] (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).

[0031] Examples of ethylenically unsaturated compounds other than the structural units (a-1) and (a-2) include 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;Unsaturated carboxylic acid esters, 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-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytripropyl Pyrene 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 dicyclopentenyloxyethyl (meth)acrylate; N-vinyl tertiary amines containing an N-vinyl group, such as N-vinylpyrrolidone, N-vinylcarbazole, and N-vinylmorpholine; unsaturated ethers, such as vinyl methyl ether and vinyl ethyl ether; and unsaturated imides, such as N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, and N-cyclohexylmaleimide.

[0032] The structural unit (a-3) is represented by the following formula 1: [ka] In the above formula 1, R1 may be C 1~4 It is alkyl.

[0033] Specifically, the functional group in the structural unit (a-3-1) can freely rotate in the polymer, which allows the developer to penetrate during development. Thus, the coating film is more easily developed during development after exposure to light, thereby ensuring excellent sensitivity.

[0034] The content of the structural unit (a-3-1) may be 1 to 30 wt %, or 2 to 20 wt %, based on the total weight of the acrylic copolymer (A). Within the above range, it is possible to achieve a coating film pattern with excellent sensitivity.

[0035] The structural unit (a-3) is represented by the following formula 2: [ka] In the above formula 2, R2 and R3 each independently represent C 1~4 It is alkyl.

[0036] The acrylic copolymer (A) contains both the structural unit (a-3-1) and the structural unit (a-3-2), which is advantageous in that it maintains film retention while improving sensitivity.

[0037] 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).

[0038] 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 film retention while improving sensitivity.

[0039] The amount of the structural unit (a-3) may be 0 to 90 mol % or 50 to 70 mol % based on the total number of moles of the structural units constituting the acrylic copolymer (A). Within the above amount range, it is possible to adjust the reactivity of the acrylic copolymer (i.e., alkali-soluble resin) and improve its solubility in an alkaline aqueous solution, thereby significantly improving the coating properties of the photosensitive resin composition and forming a film pattern with good developability.

[0040] The acrylic copolymer can be prepared by blending the compounds providing the structural units (a-1), (a-2), and (a-3), adding a molecular weight regulator, a polymerization initiator, a solvent, etc., and then introducing nitrogen into the mixture and slowly stirring it to polymerize. The molecular weight regulator can be, but is not limited to, a mercaptan compound such as butyl mercaptan, octyl mercaptan, lauryl mercaptan, etc., or α-methylstyrene dimer.

[0041] The polymerization initiator may be, but is not limited to, 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-butyl peroxypivalate; 1,1-bis(t-butylperoxy)cyclohexane, etc. The polymerization initiator may be used alone or in combination of two or more thereof.

[0042] Furthermore, the solvent may be any solvent commonly used in the preparation of acrylic copolymers, which may preferably be methyl 3-methoxypropionate (MMP) or propylene glycol monomethyl ether acetate (PGMEA).

[0043] In particular, by maintaining milder reaction conditions during the polymerization reaction while keeping the reaction time longer, it is possible to reduce the amount of residual unreacted monomer.

[0044] 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, for example, room temperature to 60°C or room temperature to 65°C. Then, the reaction time is maintained until a sufficient reaction occurs.

[0045] When the acrylic copolymer is prepared by the above process, it is possible to reduce the residual amount of unreacted monomer in the acrylic copolymer to a very small level.

[0046] As used herein, the term "unreacted monomer" (or residual monomer) of an acrylic copolymer 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 a copolymer chain).

[0047] Specifically, the amount of unreacted monomer of the acrylic copolymer (A) remaining in the photosensitive resin composition of the present invention may 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).

[0048] As used herein, the term solids content refers to the amount of the composition excluding the solvent.

[0049] 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.

[0050] The acrylic copolymer (A) can be used in an amount of 10 to 90 wt %, 30 to 80 wt %, or 45 to 65 wt %, based on the total weight of the photosensitive resin composition based on the solid content excluding the solvent. Within the above ranges, the developability is properly controlled, which is advantageous in terms of film retention.

[0051] (B) Siloxane copolymer The positive photosensitive resin composition of the present invention may contain a siloxane copolymer as a binder.

[0052] Siloxane copolymers have complex net-shape chemical structures. The Si-O bond in siloxane copolymers has a higher decomposition energy than the C-C bond in acrylic copolymers. Siloxane copolymers with these structural characteristics can suppress the thermal mobility of other low-molecular-weight components in the composition, such as linear acrylic copolymers or multifunctional monomers, when a cured film is formed. Furthermore, the silanols in the siloxane copolymers improve bonding to lower substrates, thereby improving adhesion. This also improves the efficiency of inhibition by photoactive compounds (PACs), thereby helping to improve film retention.

[0053] The siloxane copolymer contains a condensate of a silane compound and / or a hydrolysis product thereof. In such cases, the silane compound or the hydrolysis product thereof may be a monofunctional to tetrafunctional silane compound.

[0054] As a result, the siloxane copolymer may comprise siloxane structural units selected from the following Q, T, D, and M types: Q-type siloxane structural unit: a siloxane structural unit comprising a silicon atom and four adjacent oxygen atoms, which may for example be derived from a tetrafunctional silane compound having four hydrolyzable groups or from the hydrolysis product of a silane compound. - T-type siloxane structural unit: a siloxane structural unit comprising a silicon atom and three adjacent oxygen atoms, which may for example be derived from a trifunctional silane compound having three hydrolyzable groups or from the 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, for example, from a difunctional silane compound having two hydrolyzable groups or from the hydrolysis product of a silane compound. M-type siloxane structural unit: a siloxane structural unit containing a silicon atom and one adjacent oxygen atom, which may for example be derived from a monofunctional silane compound having one hydrolyzable group or from the hydrolysis product of a silane compound.

[0055] For example, the siloxane copolymer may include structural units 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 a hydrolysis product thereof. [Formula 3] (R4) n Si(OR5) 4-n

[0056] In the above formula 3, n is an integer of 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, heteroalkyl, heteroalkenyl, and heteroaryl groups each independently have at least one heteroatom selected from the group consisting of O, N, and S.

[0057] Examples of structural units (wherein R4 has a heteroatom) include ethers, esters, and sulfides.

[0058] The compound can be a tetrafunctional silane compound (where n is 0), a trifunctional silane compound (where n is 1), a difunctional silane compound (where n is 2), or a monofunctional silane compound (where n is 3).

[0059] Specific examples of silane compounds include, for example, tetrafunctional silane compounds such as tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, and tetrapropoxysilane; and trifunctional silane compounds such as 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-hydroxypropyltrimethoxysilane 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;Bifunctional silane compounds include dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, dibutyldimethoxysilane, dimethyldiethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3-chloropropyl and monofunctional silane compounds such as trimethylsilane, tributylsilane, trimethylmethoxysilane, tributylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, and (3-glycidoxypropyl)dimethylethoxysilane.

[0060] 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 difunctional silane compounds, preferred are dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldiphenoxysilane, dibutyldimethoxysilane, and dimethyldiethoxysilane.

[0061] These silane compounds may be used alone or in combination of two or more thereof.

[0062] The conditions for obtaining the hydrolysis product or condensation product of the silane compound of the above formula 3 are not particularly limited.For example, the silane compound of the formula 3 is optionally diluted with a solvent such as ethanol, 2-propanol, acetone, butyl acetate, etc., and water and an acid (such as hydrochloric acid, acetic acid, nitric acid, etc.) or a base (such as 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, thereby obtaining the desired hydrolysis product or its condensation product.

[0063] The weight-average molecular weight of the condensate (i.e., siloxane copolymer) obtained by hydrolysis polymerization of the silane compound of the above formula 3 is preferably in the range of 500 to 50,000 Da. Within the above range, this is more preferable in terms of film-forming characteristics, solubility in a developer, dissolution rate, etc.

[0064] The type and amount of the solvent or acid or base catalyst are not particularly limited. Furthermore, the hydrolysis polymerization reaction can be carried out at a low temperature of 20° C. or less. Alternatively, the reaction can be accelerated by heating or refluxing.

[0065] The required reaction time can be adjusted depending on the type and concentration of the silane structural unit, the reaction temperature, etc. For example, the reaction usually takes 15 minutes to 30 days to proceed until the molecular weight of the resulting condensate reaches approximately 500 to 50,000 Da. However, this is not limited thereto.

[0066] The siloxane copolymer may contain linear siloxane structural units (i.e., D-type siloxane structural units). The linear siloxane structural units may be derived from a difunctional silane compound, such as 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, the cured film may have flexibility while maintaining a specific level of hardness, thereby further improving crack resistance to external stress.

[0067] 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.

[0068] Furthermore, considering the hardness, sensitivity, and retention of the cured film, it is preferable that the siloxane copolymer 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-naphthoquinone diazide compound is excellent, which can achieve better transparency of the cured film while preventing excessive reduction in sensitivity. The structural units derived from a silane compound having an aryl group may be a structural unit derived from a silane compound of the above formula 3 (wherein R4 is an aryl group), preferably a silane compound of the above formula 3 (wherein n is 1 and R4 is an aryl group), particularly a structural unit derived from a silane compound of the above formula 3 (wherein n is 1 and R4 is a phenyl group) (i.e., a T-phenyl type siloxane structural unit).

[0069] The siloxane copolymer may contain structural units (i.e., Q-type structural units) derived from the silane compound represented by the above formula 3 (wherein n is 0). Preferably, the siloxane copolymer may contain structural units 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 decrease in solubility or a dramatic increase in the solubility of the composition.

[0070] 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 particular structural unit relative to the total number of moles of Si atoms contained in all of the structural units that make up the siloxane polymer.

[0071] The molar amount of siloxane units in the siloxane copolymer can be determined by Si-NMR, 1 H-NMR, 13 It can be measured by combining C-NMR, IR, TOF-MS, elemental analysis, ash measurement, etc. For example, to measure the molar amount of phenyl-containing siloxane units, 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. The molar amount can then be calculated from the peak area ratio between them.

[0072] Furthermore, if the siloxane copolymer dissolves too quickly in the developer during development, the adhesion of the pattern deteriorates due to rapid development, whereas if the dissolution is too slow, the sensitivity decreases.

[0073] Therefore, it is important that the siloxane copolymer has an appropriate level of dissolution rate in the developer. Specifically, when the siloxane copolymer dissolves in an aqueous solution of 1.5 wt % tetramethylammonium hydroxide at a pre-bake temperature of 105°C, it 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 to 10,000 Å / sec, 100 to 8,000 Å / sec, 100 to 5,000 Å / sec, 1,000 to 5,000 Å / sec, or 1,500 to 5,000 Å / sec. Within the above range, this is more advantageous in terms of sensitivity and resolution during development.

[0074] The photosensitive resin composition may contain the siloxane copolymer in an amount of 20 to 80 parts by weight, or 30 to 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 range, the developability is properly controlled, which is advantageous in terms of film retention and resolution.

[0075] (C) 1,2-quinone diazide compounds The positive photosensitive resin composition according to the present invention may contain a 1,2-quinonediazide-based compound (C).

[0076] The 1,2-quinonediazide-based compound can be a compound used as a sensitizer in the field of photoresists.

[0077] Examples of 1,2-quinone diazide-based compounds include esters of phenolic compounds and 1,2-benzoquinone diazide-4-sulfonic acid or 1,2-benzoquinone diazide-5-sulfonic acid; esters of phenolic compounds and 1,2-naphthoquinone diazide-4-sulfonic acid or 1,2-naphthoquinone diazide-5-sulfonic acid; sulfonamides of phenolic compounds (wherein the hydroxyl group is replaced with an amino group) and 1,2-benzoquinone diazide-4-sulfonic acid or 1,2-benzoquinone diazide-5-sulfonic acid; sulfonamides of phenolic compounds (wherein the hydroxyl group is replaced with an amino group) and 1,2-naphthoquinone diazide-4-sulfonic acid or 1,2-naphthoquinone diazide-5-sulfonic acid. The above compounds can be used alone or in combination of two or more thereof.

[0078] As used herein, 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(p-hydroxyphenyl)methane, ... (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'-spirobiindene-5,6,7,5',6',7'-hexanol, and 2,2,4-trimethyl-7,2',4'-trihydroxyflavan.

[0079] More specific examples of 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, and esters of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid.

[0080] The above compounds may be used alone or in combination of two or more thereof.

[0081] When the preferred compounds exemplified above are used, the transparency of the photosensitive resin composition can be enhanced.

[0082] The photosensitive resin composition may contain 2 to 50 parts by weight, or 5 to 30 parts by weight, of the 1,2-quinonediazide-based compound, based on 100 parts by weight of the acrylic copolymer (A) (based on the solid content). Within the above content range, patterns are more easily formed, defects such as a rough surface of the coated film due to the pattern formation and pattern shapes such as scum appearing in the lower part of the pattern due to development are prevented, and excellent transmittance can be ensured.

[0083] (D) 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.

[0084] To enhance developability and film retention when a cured film is prepared, the solvent of the present invention may include a non-polar organic solvent having a boiling point of 155-200° C. at 25° C. and 1 atm.

[0085] When the epoxy groups in the acrylic copolymer (A) and / or the epoxy compound (F) react with the HO molecules in the polysiloxane copolymer (B), a diol compound is generated. If the amount of the diol compound increases, the developability improves excessively, but the adhesion deteriorates (see Schemes 1 and 2). [ka]

[0086] The use of a nonpolar solvent makes it possible to maintain a relatively high activation energy for the transition state of the epoxy group in the composition compared to when a polar solvent is used. Reactivity with HO generated from the siloxane copolymer (B) is suppressed, making it possible to reduce the generation of diol compounds. To prevent an increase in developability and a decrease in adhesion due to an increase in diol compounds, a nonpolar solvent having a boiling point of 155 to 200°C, 160 to 200°C, or 160 to 190°C at 25°C and 1 atm may also be used.

[0087] The non-polar organic solvent may include a compound represented by Formula 4: [Formula 4] R6O(C m H 2m O)2R7 In the above formula 4, R6 and R7 are each independently hydrogen or C 1~4 alkyl, and m is 2 or 3.

[0088] The non-polar organic solvent may include at least one selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl propyl ether, diethylene glycol methyl isopropyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol methyl ether, and dipropylene glycol dimethyl ether. Specifically, it may be diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, or diethylene glycol dimethyl ether.

[0089] The solvent (D) may contain a nonpolar organic solvent in an amount of 1 to 30 wt %, 3 to 30 wt %, or 5 to 20 wt %, based on the total weight of the solvent (D). Within the above range, the nonpolar organic solvent may have an appropriate dissolution rate in the developer, thereby facilitating pattern formation and ensuring stable processing margins.

[0090] Furthermore, the composition of the present invention further comprises a solvent capable of dissolving the components of the composition and which is chemically stable. For example, the solvent may 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.

[0091] Specific examples of 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, and 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.

[0092] Among the above, preferred are ethylene glycol alkyl ether acetate, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, ketone, etc. Particularly preferred are propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, methyl 3-methoxypropionate, 4-hydroxy-4-methyl-2-pentanone, etc.

[0093] The amount of solvent in the positive photosensitive resin composition according to the present invention is not particularly limited. For example, the solvent may be used so that the solid content is 10 to 90 wt %, 15 to 85 wt %, or 20 to 80 wt %, based on the total weight of the composition.

[0094] 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.

[0095] (E) Polyfunctional Monomer The positive photosensitive resin composition of the present invention may further contain a polyfunctional monomer (E).

[0096] The polyfunctional monomer is a monomer having a small molecular weight and a double bond. Specifically, it 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, it may preferably be a trifunctional to octafunctional compound.

[0097] The polyfunctional monomers include 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 tetra(meth)acrylate, It may be at least one selected from the group consisting of erythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, a monoester of dipentaerythritol penta(meth)acrylate and succinic acid, caprolactone-modified dipentaerythritol hexa(meth)acrylate, pentaerythritol triacrylate-hexamethylene diisocyanate (a reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, and ethylene glycol monomethyl ether acrylate.

[0098] 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) tri- or higher functional (meth)acrylates, such as Aronix Examples of suitable amines include 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 Ltd.).

[0099] The polyfunctional monomer is generally used mainly in the negative state, where it acts as a crosslinker by light during exposure to light, whereas in the positive state of the present invention, it acts to improve developability, thereby increasing sensitivity.

[0100] Specifically, the polyfunctional monomer may have a relatively small molecular weight compared to the binder (i.e., the acrylic copolymer (A) and the siloxane copolymer (B)). The polyfunctional monomer having a relatively small molecular weight compared to the binder is sandwiched between the binder to facilitate penetration of the developer during development, thereby improving sensitivity.

[0101] The photosensitive resin composition may contain the 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 solids content).

[0102] Within the above range, the developability can be properly adjusted to ensure good sensitivity, and when the coating film is formed, the surface of the coating film is not rough, and no scum occurs at the bottom of the film during development.If it is used in an amount less than the above range, the sensitivity cannot be sufficiently improved.If it is used in excess, the thermal fluidity in the composition during hard baking will be increased, thereby deteriorating the resolution of the pattern.

[0103] (F) Epoxy compounds The positive photosensitive resin composition according to the present invention may further contain an epoxy compound, which can increase the internal density of the binder, specifically the siloxane copolymer, thereby enhancing the chemical resistance of the cured film formed therefrom.

[0104] The epoxy compound can be a homo- or hetero-oligomer of unsaturated monomers containing at least one epoxy group.

[0105] 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, and α-ethylglycidyl acrylate. glycidyl ether, 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, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and mixtures thereof.

[0106] The epoxy compounds may be synthesized by any method known in the art.

[0107] Examples of epoxy compounds may include glycidyl methacrylate homopolymer, and 3,4-epoxycyclohexylmethyl methacrylate homopolymer.

[0108] The epoxy compound may further include the following structural units:

[0109] Specific examples thereof include styrene; styrenes having alkyl substituents, such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; styrenes having halogens, such as fluorostyrene, chlorostyrene, bromostyrene, and iodostyrene; styrenes having alkoxy substituents, such as methoxystyrene, ethoxystyrene, and propoxystyrene; acetylstyrenes, 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-hydroxypropyl methyl acrylate, methyl ... butyl (meth)acrylate, glycerol (meth)acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate, butyl α-hydroxymethyl acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, poly(ethylene glycol) (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 dicyclopentenyloxyethyl (meth)acrylate; tertiary amines containing N-vinyl groups, such as N-vinylpyrrolidone, N-vinylcarbazole and N-vinylmorpholine; unsaturated ethers, such as vinyl methyl ether and vinyl ethyl ether;The epoxy compound may contain any structural unit derived from an unsaturated imide, such as N-phenylmaleimide, N-(4-chlorophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, or N-cyclohexylmaleimide. The structural unit derived from the above-exemplified compounds may be contained alone in the epoxy compound, or in a combination of two or more of these.

[0110] Among the above compounds, styrene-based compounds may be more preferable in view of their polymerizability.

[0111] In particular, with regard to chemical resistance, it is more preferable that the epoxy compound does not contain a carboxyl group by not using a structural unit derived from a monomer containing a carboxyl group among the above.

[0112] The structural unit may 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 in terms of film strength.

[0113] The weight-average molecular weight of the epoxy compound is preferably 100 to 30,000 Da. Its weight-average molecular weight is more preferably 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 can be more favorable. When it is 30,000 Da or less, the cured film can have a uniform thickness, which is suitable for smoothing any step thereon.

[0114] The photosensitive resin composition may contain the 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.

[0115] (G) Surfactants The positive photosensitive resin composition of the present invention may further contain a surfactant to enhance its coating properties, if necessary.

[0116] The type of surfactant is not particularly limited, but examples thereof include fluorine-based surfactants, silicon-based surfactants, and nonionic surfactants.

[0117] Specific examples of surfactants include fluorine- and silicon-based surfactants, 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 Ltd., 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., and Shinakida Kasei Co., Ltd., Eftop EF301, EF303, and EF352 supplied by Toray Silicon 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.). These may be used alone or in combination of two or more.

[0118] The photosensitive resin composition may contain the 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 composition may exhibit good coating and leveling properties.

[0119] (H) Adhesion aid The positive photosensitive resin composition of the present invention may further contain an adhesion aid that enhances adhesion to a substrate.

[0120] 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.

[0121] The type of adhesion aid is not particularly limited and 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.

[0122] Preferred are γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, or N-phenylaminopropyltrimethoxysilane, which can increase the film retention rate and adhesion to the substrate.

[0123] The photosensitive resin composition may contain an adhesion aid 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, adhesion to the substrate can be further improved.

[0124] (I) Silane compounds The positive photosensitive resin composition of the present invention contains at least one silane compound represented by the following formula 5, particularly a T-type and / or Q-type silane monomer, which, in combination with an epoxy compound, such as an epoxy oligomer, reduces highly reactive silanol groups (Si—OH) in the siloxane copolymer, thereby improving chemical resistance during post-processing. [Formula 5] (R8) l Si(OR9) 4-n

[0125] In the above formula 5, l is an integer of 0 to 3, and each R8 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 R9 is independently hydrogen, C 1~6 Alkyl, C 2~6 Acyl, or C 6~15 Aryl, heteroalkyl, heteroalkenyl, and heteroaryl groups each independently have at least one heteroatom selected from the group consisting of O, N, and S.

[0126] Examples of structural units (wherein R8 has a heteroatom) include ethers, esters, and sulfides.

[0127] According to the present invention, the compound can be a tetrafunctional silane compound (wherein l is 0), a trifunctional silane compound (wherein l is 1), a difunctional silane compound (wherein l is 2) or a monofunctional silane compound (wherein l is 3).

[0128] Specific examples of the silane compounds include, for example, tetrafunctional silane compounds such as tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, and tetrapropoxysilane; and trifunctional silane compounds such as 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-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane triethoxysilane, 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, diphenyldi Phenoxysilane, dibutyldimethoxysilane, dimethyldiethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, 3-mercaptopropyldimethoxymethylsilane, cyclohexyldimethoxymethylsilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, and dimethoxydi-p-tolylsilane;and monofunctional silane compounds such as trimethylsilane, tributylsilane, trimethylmethoxysilane, tributylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, and (3-glycidoxypropyl)dimethylethoxysilane.

[0129] 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.

[0130] These silane compounds may be used alone or in combination of two or more thereof.

[0131] The photosensitive resin composition may contain the 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 cured film formed can be further improved.

[0132] 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.

[0133] Furthermore, the present invention also provides a cured film formed from the positive photosensitive resin composition.

[0134] The cured film can be formed by a method known to those skilled in the art, for example, by coating a photosensitive resin composition on a substrate and then curing it.

[0135] More specifically, in the curing step, the photosensitive resin composition coated on the substrate is prebaked, for example, at a temperature of 60 to 130°C to remove the solvent, and then exposed to light using a photomask with the desired pattern. The coating layer is then developed using a developer, such as a tetramethylammonium hydroxide (TMAH) solution, to form a pattern on the coating layer. If necessary, the patterned coating layer is then postbaked, for example, at a temperature of 150 to 300°C for 10 minutes to 5 hours to prepare the desired cured film. The exposure to light is in the wavelength range of 200 to 500 nm, with a wavelength of 365 nm as the reference, at 10 to 200 mJ / cm. 2 or 10 to 300 mJ / cm 2 According to the process of the present invention, it is possible to easily form a desired pattern from a process standpoint.

[0136] The photosensitive resin composition can be coated onto a substrate to a desired thickness of 2 to 25 μm by spin coating, slit coating, roll coating, screen printing, applicator, or other methods. Furthermore, light sources used for exposure (irradiation) include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and argon gas lasers. X-rays, electron beams, and other sources can also be used as needed.

[0137] On the other hand, after exposure, the photosensitive resin composition is 2 or 500 to 1,500 mJ / cm 2Alternatively, the composition may be photobleached with an energy of 1000 kJ / cm 2 and developed to obtain a more transparent cured film. Specifically, the composition can be coated on a substrate, subjected to exposure and development, and subsequently subjected to photobleaching and hard baking to form a cured film. The photobleaching process removes the N2 bond of a 1,2-quinone diazide-based compound, which is one of the main components of positive-type photosensitive resin compositions, thereby forming a transparent cured film. If hard baking is performed without the photobleaching process, a reddish cured film is obtained, which results in a decrease in transmittance in the 400 to 600 nm region, for example.

[0138] The positive photosensitive resin composition of the present invention can form a cured film having excellent pattern adhesion and film retention upon development. Furthermore, the composition of the present invention can form a cured film having excellent resolution and sensitivity.

[0139] Specifically, the cured film is capable of introducing a line pattern having a thickness of 2.1 μm and having fine critical dimensions (i.e., small critical dimensions) (i.e., excellent adhesion) even upon development, and good film retention of 5% or less, 4% or less, 0.1-5%, or 0.1-4% (see Evaluation Examples 1 and 2).

[0140] As described above, the positive-type photosensitive resin composition contains a nonpolar organic solvent, which suppresses the reactivity of the epoxy groups in the composition and reduces the generation of diol compounds. When a cured film is prepared from the composition, an appropriate level of developability is maintained, further improving pattern adhesion, resolution, and sensitivity. Furthermore, since the composition of the present invention has a small difference in film retention rate between room temperature and low temperature, the composition can be stable over time. Therefore, the cured film prepared therefrom can be advantageously used in liquid crystal displays, organic electroluminescence displays, and the like.

[0141] Modes of the Invention The present invention will be described in more detail below with reference to the following examples. However, these examples are provided for the purpose of illustrating the present invention and are not intended to limit the scope of the present invention. In the following preparation examples, the weight average molecular weight is determined by gel permeation chromatography (GPC, eluent: tetrahydrofuran) using polystyrene standards as reference. [Example]

[0142] Preparation Example 1: Synthesis of acrylic copolymer (A-1) A flask equipped with a condenser and a stirrer was charged with 200 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, and the solvent was slowly stirred while the temperature 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 to the mixture. Next, 3 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) as a radical polymerization initiator was added dropwise over 5 hours, and the polymerization reaction was carried out. The weight-average molecular weight of the resulting copolymer (solid content: 32% by weight) was 9,000-11,000 Da.

[0143] Preparation Example 2: Synthesis of Acrylic Copolymer (A-2) An acrylic copolymer (A-2) was prepared in the same manner as in Preparation Example 1, except that 200 parts by weight of methyl 3-methoxypropionate was used as the solvent. The weight-average molecular weight of the copolymer thus obtained (solid content: 32% by weight) was 9,000 to 11,000 Da.

[0144] Preparation Example 3: Preparation of Siloxane Copolymer (B) A reactor equipped with a reflux condenser was charged with 20 wt% phenyltrimethoxysilane (PhTMOS), 30 wt% methyltrimethoxysilane (MTMOS), 20 wt% tetraethoxysilane (TEOS), and 15 wt% deionized water (DI water), followed by 15 wt% PGMEA. The mixture was then refluxed for 0.1 hours with vigorous stirring in the presence of 0.1 wt% oxalic acid catalyst. The mixture was then cooled and diluted with PGMEA to a solids content of 30 wt%, thereby obtaining siloxane copolymer (B). The weight-average molecular weight of the resulting copolymer (solids content: 30 wt%) was 6,000-11,000 Da.

[0145] Furthermore, when the copolymer thus obtained was dissolved in a 1.5 wt % aqueous solution of tetramethylammonium hydroxide at about 110° C., the average dissolution rate (ADR) was 4,113 Å / sec.

[0146] Preparation Example 4: Preparation of epoxy compound (F) The three-neck flask was equipped with a condenser and placed on a thermostatic stirrer. 100 parts by weight of a monomer mixture consisting of 100 mol% 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 added to the flask, followed by nitrogen gas. The temperature of the solution was then raised to 80°C while slowly stirring, and the temperature was maintained for 5 hours. PGMEA was then added to a solids content of 20% by weight, resulting in an epoxy compound with a weight-average molecular weight of 3,000 to 6,000 Da.

[0147] Examples and Comparative Examples: Preparation of Positive Photosensitive Resin Composition The photosensitive resin compositions of the following Examples and Comparative Examples were each prepared using the compounds prepared in the above Preparation Examples.

[0148] The components used in the following examples and comparative examples are as follows:

[0149] [Table 1]

[0150] Example 1: Preparation of photosensitive resin composition A reactor was charged with 26 wt% of the acrylic copolymer (A-1) from Preparation Example 1, based on the total weight of the photosensitive resin composition excluding the remaining solvent. Furthermore, based on 100 parts by weight of the acrylic copolymer (A) (based on solids content), 57.5 wt% of the siloxane copolymer (B) from Preparation Example 3, 18.1 wt% and 7.6 wt% of the 1,2-quinone diazide compounds (C-1) and (C-2), respectively, and 6.6 wt% of the epoxy compound (F) from Preparation Example 4 were charged. Furthermore, 0.5 wt% of a surfactant was added, based on the total weight of the composition. Subsequently, 45.5 wt% of the solvent (D-1), 5.1 wt% of the solvent (D-2), and 10 wt% of the solvent (D-3) were mixed therewith to achieve a solids content of 18.5 wt%. 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 18.5% by weight.

[0151] Examples 2 to 11 and Comparative Examples 1 to 6: Preparation of Photosensitive Resin Compositions The photosensitive resin composition solutions were prepared in the same manner as in Example 1, except that the type and / or content of each component was changed as shown in Tables 2 and 3 below.

[0152] [Table 2]

[0153] [Table 3]

[0154] [Evaluation Example] Evaluation Example 1: Evaluation of film retention rate The compositions prepared in the examples and comparative examples were stored at -20°C and 25°C (i.e., room temperature) for 2 days, respectively. After 2 days, the compositions were coated onto glass substrates by spin coating. Subsequently, the films were prebaked for 105 seconds on a hot plate maintained at 105°C to form dry films. These films were developed with an aqueous developer of 2.38 wt% tetramethylammonium hydroxide via a paddle nozzle at 23°C for 85 seconds. The developed films were then irradiated with 200 mJ / cm2 of light at a wavelength of 365 nm using an aligner (model name: MA6) emitting light having a wavelength of 200 nm to 450 nm. 2 The film was then bleached by exposure for a fixed period of time at a dose rate of 1000 kJ / cm. The exposed film was then heated in a convection oven at 240°C for 20 minutes to prepare a cured film having a thickness of 2.1 μm. The film retention (FR, %) was calculated 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: [formula] Film retention rate (FR, %) = (film thickness after post-baking / film thickness after pre-baking) × 100

[0155] The higher the film retention, the better.

[0156] Furthermore, the difference in film retention rate between -20°C and 25°C (FR 25 -FR -20 ) is 5% or less, the change in film retention over time is small and therefore it is evaluated as stable.

[0157] Evaluation Example 2: Evaluation of pattern adhesion To evaluate the adhesion of the developed pattern, a cured film was formed on a substrate irradiated with extreme ultraviolet (EUV) rays by the following method, and then the adhesion of the pattern was evaluated.

[0158] First, the silicon nitride substrate was exposed to EUV light for 10 minutes using a UV lamp (model: UV-CB8x10) with an output of 8 W at wavelengths of 185 nm and 254 nm. Under these conditions, the distance between the exposure reference lamp and the substrate was 10 mm. Upon exposure to light, the substrate was washed for 10 seconds with a developer solution of 1.4 wt% tetramethylammonium hydroxide solution sprayed through a spray nozzle at 23°C, thereby preparing a treated silicon nitride substrate. Upon treatment with EUV light, the DI contact angle was within the range of 0 to 3 degrees.

[0159] Next, the compositions of the examples and comparative examples stored at 25°C (room temperature) for 2 days were each coated onto a glass substrate by spin coating. This was then pre-baked for 105 seconds on a hot plate maintained at 90°C, thereby forming a dry film. A photomask having six 1:3 line patterns spaced 1µm apart, each ranging from 1µm to 30µm, was placed on the dry film. The film was then irradiated with 400mJ / cm2 based on a wavelength of 365nm using an aligner (model name: MA6) emitting light with a wavelength of 200nm to 450nm. 2 The film was exposed to light for a certain period of time at a dose rate of 200 mJ / cm2. Under these conditions, the distance between the mask and the substrate was 25 μm. Upon exposure to light, the film was developed for 80 seconds with a developer of 2.38 wt % tetramethylammonium hydroxide in water through a paddle nozzle at 23°C. The developed film was then irradiated with light having a wavelength of 200 nm to 450 nm at a dose of 200 mJ / cm2, based on a wavelength of 365 nm, using an aligner (model name: MA6) that emits light having a wavelength of 200 nm to 450 nm. 2 The film was then subjected to photobleaching by exposure for a certain period of time at a dose rate of 1000 kJ / s. The exposed film was then heated in a convection oven at 230°C for 30 minutes to prepare a cured film having a thickness of 2 μm.

[0160] Next, the range of the smallest remaining line patterns among the 1 μm to 30 μm line patterns on the silicon nitride substrate was observed using a microscope. Specifically, during microscopic observation, the dimensions of the smallest remaining line patterns, which comprise the mask critical dimension (CD; μm), after the line patterns separated were measured and evaluated according to the following criteria. The smaller the dimension of the smallest remaining line pattern, the better the adhesion during development. [Grade] 1μm~7μm: A, More than 7μm ~ 14μm: B, More than 14μm ~ less than 21μm: C, More than 21μm: D

[0161] [Table 4]

[0162] As shown in Table 4, the cured films prepared from the compositions of the examples within the scope of the present invention had excellent film retention at both low and room temperatures. The difference between these was very small, less than 5%, indicating excellent stability over time. Furthermore, in the cured films prepared from the compositions of the examples, line patterns with small dimensions of less than 10 μm remained after development, indicating their excellent adhesion.

[0163] In contrast, in the cured films prepared from the comparative compositions, the difference in film retention between room temperature and low temperature was more than 5%, even up to 11.8%, indicating poor stability over time. The line patterns remaining upon development had dimensions of 16.5 to 30 μm, indicating that they were disadvantageous in terms of adhesion.

Claims

1. (A) acrylic copolymer; (B) a siloxane copolymer; (C) 1,2-quinone diazide compounds; and (D) a solvent, The solvent (D) contains an organic solvent having a boiling point of 155 to 200° C. at 1 atm, The organic solvent is represented by the following formula 4: [Formula 4] R ６ O(C ｍ H ２ｍ O) ２ R ７ In the above formula 4, R ６ and R ７ are each independently C １～４ m is an alkyl group and m is 2 or 3.

2. 2. The positive photosensitive resin composition according to claim 1, wherein the acrylic copolymer (A) comprises: (a-1) a structural unit derived from an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid 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).

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

4. The structural unit (a-3) is represented by the following formula 2: 【Chemistry 2】 In the above formula 2, R ２ and R ３ are each independently C １～４ The positive photosensitive resin composition according to claim 3, wherein the alkyl group is an alkyl group.

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

20.

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

7. 2. The positive photosensitive resin composition according to claim 1, comprising the siloxane copolymer (B) in an amount of 20 to 80 parts by weight based on 100 parts by weight of the acrylic copolymer (A).

8. 2. The positive photosensitive resin composition according to claim 1, wherein the organic solvent comprises at least one selected from the group consisting of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl propyl ether, diethylene glycol methyl isopropyl ether, diethylene glycol methyl ethyl ether, and dipropylene glycol dimethyl ether.

9. 2. The positive photosensitive resin composition according to claim 1, wherein the solvent (D) contains the organic solvent in an amount of 1 to 30% by weight based on the total weight of the solvent (D).

10. The positive photosensitive resin composition according to claim 1 , further comprising a polyfunctional monomer.

11. The positive photosensitive resin composition according to claim 10, wherein the polyfunctional monomer is a trifunctional to octafunctional compound.

12. The positive photosensitive resin composition according to claim 10, wherein the polyfunctional monomer contains an ethylenically unsaturated double bond.

13. 11. The positive photosensitive resin composition according to claim 10, comprising the polyfunctional monomer in an amount of 1 to 30 parts by weight based on 100 parts by weight of the acrylic copolymer (A).

14. The positive photosensitive resin composition according to claim 1 , further comprising an epoxy compound.

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