Photosensitive resin composition and method for forming pattern using same

Abstract

The present disclosure relates to a photosensitive resin composition, a photoresist film and a substrate protective film manufactured using same, and a method for forming a pattern using same. The photosensitive resin composition according to an embodiment has excellent adhesion to a substrate and chemical resistance, and, at the same time, can achieve a high resolution when forming a pattern. In addition, a film formed using the photosensitive resin composition according to an embodiment has excellent physical properties and can achieve an ultra-fine pattern, and thus is useful for a display device such as a flat panel display.

Description

Photosensitive resin composition and method for forming a pattern using the same

[0001] The present disclosure relates to a photosensitive resin composition and a method for forming a pattern using the same.

[0002] Flat panel displays are widely used in smartphones, tablet PCs, and televisions, and are classified into liquid crystal displays (LCDs), organic light-emitting displays (OLEDs), plasma display panels (PDPs), and electrophoretic displays depending on their light-emitting method. In the manufacturing process of these flat panel displays, a photo process is applied to form patterns, and a photosensitive resin composition is used at this time.

[0003] Photosensitive resins are representative functional polymer materials used in the production of various precision electronic and information industry products. These polymer compounds undergo chemical changes in their molecular structure upon light irradiation, resulting in changes in physical properties such as solubility in specific solvents, coloration, and curing. Photosensitive resins enable micro-precision processing, significantly reduce energy and raw material consumption compared to thermal reaction processes, and offer the advantages of rapid and accurate work in a small installation space.

[0004] Photosensitive resin compositions containing such photosensitive resins are classified into positive and negative types depending on the solubility of the exposed portion in the developing solution. Positive photoresists are those in which the exposed portion dissolves in the developing solution, while negative photoresists are those in which the exposed portion does not dissolve in the developing solution and the unexposed portion dissolves to form a pattern. Positive and negative photoresists differ in the binder resin, cross-linking agent, etc. used.

[0005] Meanwhile, with the recent advancements in electronic devices, such as high integration and micropatterning, there is a growing demand for photosensitive resins that can minimize defect rates and enhance processing efficiency and resolution. To address this issue, a method using a photosensitive resin containing polyimide has been introduced. Polyimide is a polymer with a hetero-imidine ring in its main chain, manufactured by condensation polymerization of tetracarboxylic acid and diamine. Polyimide exhibits excellent light transmittance, mechanical properties, thermal characteristics, and excellent substrate adhesion.

[0006] However, polyamide is easily hydrolyzed by water in the air, etc., so it has insufficient preservation and stability, and it has low adhesion to the substrate to which it is applied, and there is a problem that the physical properties of electrical wiring or substrates are deteriorated due to high temperature application. In addition, other types of photosensitive resins also have insufficient chemical resistance, heat resistance, and electrical properties in the final cured state, and especially, there is a problem that the adhesion to metal substrates is insufficient, so there is a problem of peeling from the substrate during the development or curing process.

[0007] Furthermore, the photosensitive composition must not only exhibit photosensitivity, but also be capable of low-temperature curing, exhibit reliability even with a short curing time, and exhibit enhanced light transmittance for superior lithographic performance. Furthermore, a positive-type photosensitive composition should preferably minimize the generation of developing waste products, as the exposed portion is soluble in an alkaline solution. Therefore, a new photosensitive resin composition that overcomes the shortcomings of conventional photosensitive resins and exhibits improved performance is needed.

[0008] One embodiment is to provide a photosensitive resin composition that has excellent adhesion to a substrate and chemical resistance, and at the same time can achieve high resolution when forming a pattern.

[0009] Another embodiment is to provide a photoresist film and a substrate protective film manufactured using the photosensitive resin composition.

[0010] Another embodiment provides a method for forming a pattern using the photosensitive resin composition.

[0011] One embodiment provides a photosensitive resin composition comprising a photosensitive resin including a polysiloxane structure having a bonding structure represented by the following chemical formula 1.

[0012] [Chemical Formula 1]

[0013]

[0014] In the above chemical formula 1,

[0015] X is a substituent containing one or more carbon-carbon unsaturated bonds.

[0016] Another embodiment provides a photoresist film and a substrate protective film manufactured using the photosensitive resin composition according to the above embodiment.

[0017] Another embodiment provides a method for forming a pattern, comprising: a step of applying a photosensitive resin composition according to the above embodiment onto a substrate to produce a photoresist film; a step of exposing the photoresist film; and a step of developing the exposed photoresist film using a developer.

[0018] The present disclosure relates to a photosensitive resin composition, a photoresist film and a substrate protective film manufactured using the same, and a method for forming a pattern using the same. According to one embodiment, the photosensitive resin composition exhibits excellent adhesion to a substrate and chemical resistance, and simultaneously enables high resolution during pattern formation. Furthermore, a film formed using the photosensitive resin composition according to one embodiment exhibits excellent physical properties while also enabling the implementation of an ultra-fine pattern, making it useful for application to display devices such as flat panel displays.

[0019] The embodiments described in this specification may be modified in many different forms, and thus the technology according to one implementation is not limited to the embodiments described below. Furthermore, throughout the specification, the terms "comprising," "including," "containing," "includes," or "having" a component do not exclude other components unless specifically stated to the contrary, but rather mean that other components may be included, and do not exclude additional elements, materials, or processes that are not listed.

[0020] The numerical ranges used herein include the lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of the upper and lower limits of numerical ranges defined in different shapes. For example, if the content of a composition is defined as 10% to 80% or 20% to 50%, the numerical ranges of 10% to 50% or 50% to 80% should also be interpreted as being described herein. Unless otherwise specified herein, values ​​outside the numerical range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0021] Unless otherwise specifically defined herein, “about” may be considered a value within 30%, 25%, 20%, 15%, 10%, 5%, 3%, 2%, 1% or 0.5% of the stated value.

[0022] The term "alkylene group" as used herein refers to a straight or branched carbon-carbon saturated bond diradical, which may be substituted with any substituent. The term "alkenylene group" as used herein refers to a straight or branched carbon-carbon chain diradical containing one or more carbon-carbon unsaturated bonds (double bonds), which may be substituted with any substituent. The term "alkynylene group" as used herein refers to a straight or branched carbon-carbon chain diradical containing one or more carbon-carbon unsaturated bonds (triple bonds), which may be substituted with any substituent.

[0023] The term "alkyl group" as used herein refers to a straight or branched chain radical of carbon-carbon saturated bonds, and may be substituted with any substituent. The term "alkenyl group" as used herein refers to a straight or branched chain carbon chain radical containing one or more carbon-carbon unsaturated bonds (double bonds), and may be substituted with any substituent. The term "alkynyl group" as used herein refers to a straight or branched chain carbon chain radical containing one or more carbon-carbon unsaturated bonds (triple bonds), and may be substituted with any substituent.

[0024] The term "aryl" as used herein is not limited to a bridged ring, a spiro ring, or a fused ring. For example, the aryl may be benzene, naphthalene, fluorene, anthracene, phenanthrene, bibenzene, triphenylene, pyrene, or chrysene.

[0025] Each substituent described herein has the same alphabet (X, R 1 , a, etc.), they are independent of each other in each chemical formula and may therefore be different from each other.

[0026] Hereinafter, the present disclosure will be described in detail (with reference to the attached drawings). However, this is merely exemplary and the present disclosure is not limited to the specific embodiments described as examples.

[0027]

[0028] One embodiment relates to a photosensitive resin composition comprising a photosensitive resin comprising a polysiloxane structure capable of radically reacting with an initiator by including at least one carbon-carbon unsaturated bond. The photosensitive resin composition according to one embodiment has excellent mechanical properties while easily forming ultra-fine patterns, has excellent developability and adhesion to a substrate, and has excellent resistance to chemicals used in the panel manufacturing process, thereby ensuring post-process stability.

[0029] In addition, the photosensitive resin composition according to one embodiment has high heat resistance, high transparency, excellent chemical resistance, crack resistance, and low dielectric constant properties, while allowing for a wide range of exposure, and is not affected by oxygen, making it easy to form a thin film.

[0030] Specifically, a photosensitive resin composition according to one embodiment includes a photosensitive resin including a polysiloxane structure having a bonding structure represented by the following chemical formula 1.

[0031] [Chemical Formula 1]

[0032]

[0033] In the above chemical formula 1,

[0034] X is a substituent containing one or more carbon-carbon unsaturated bonds.

[0035] In one embodiment, in the above chemical formula 1, X is not particularly limited as long as it includes a substituent containing a carbon-carbon unsaturated bond (e.g., C=C). For example, it may be a substituent containing a vinyl group, an acrylate group, or a methacrylate group, and may be an alkenyl group or an alkynyl group, and may be a substituent containing 2 to 20, 2 to 15, 2 to 10, or 2 to 5 carbon atoms. Specifically, for example, C 2-10 Alkenyl group, C 2-15 Alkenyl group, C 2-10 Alkenyl group, C 2-5 It may be an alkenyl group (in which case the carbon-carbon double bond of the alkenyl group may be directly connected to Si, connected to Si via an alkylene group, or positioned at the end), a vinyl group (-CH=CH2), an acrylate group (-COCHCH2), or a methacrylate group (-OCOCHCH2), or a substituent of a combination thereof.

[0036] In one embodiment, the polysiloxane including the bonding structure represented by the above chemical formula 1 may include a repeating unit such as the following chemical formula 11 or chemical formula 12.

[0037] [Chemical Formula 11]

[0038]

[0039] [Chemical Formula 12]

[0040]

[0041] In the above chemical formulas 11 and 12, x and y are real numbers satisfying 0 < x < 1 and 0 < y < 1, and A is a substituent.

[0042] According to one embodiment, a photosensitive resin may be manufactured by hydrolysis and condensation reactions of a polysiloxane having a bonding structure represented by the above chemical formula 1 and a dihydrosiloxane compound represented by the following chemical formula 2 or chemical formula 3.

[0043] [Chemical Formula 2]

[0044]

[0045] In the above chemical formula 2,

[0046] R 21 , R 22 , R 23 , and R 24 are each independently C 1-20 Alkyl group, C 6-20 Aryl group, or C 1-20 It is an alkoxy group,

[0047] [Chemical Formula 3]

[0048]

[0049] In the above chemical formula 3,

[0050] R 31 , R 32 , R 33 , and R 34 are each independently C 1-20 Alkyl group, C 6-20 Aryl group, or C 1-20 It is an alkoxy group,

[0051] a and b are each independently integers greater than or equal to 0, and a:b is 1:1 to 1:20.

[0052] In one embodiment, in the above formula 2, R 21 , R 22 , R 23 , and R 24 are each independently C 1-10 Alkyl group, C 6-10 Aryl group, or C 1-10 An alkoxy group, or C 1-15 Alkyl group, C 1-8 Alkyl group, C 1-5 Alkyl group, C 1-3 Alkyl group, -CH3, C 6-8 Aryl group, -Ph(phenyl), C 1-15 Alkoxy group, C 1-8 Alkoxy group, C 1-5 Alkoxy group, C 1-3An alkoxy group, or -OCH3. In this case, R 21 , R 22 , R 23 , and R 24 At least two, three, or all of these are C 1-15 Alkyl group, C 1-10 Alkyl group, C 1-8 Alkyl group, C 1-5 Alkyl group, C 1-3 An alkyl group, or -CH3. In this case, R 21 , R 22 , R 23 , and R 24 If two or three of the above substituents are alkyl groups, the remaining substituents are C 6-10 Aryl group, C 6-8 It can be an aryl group, or -Ph(phenyl). Specifically, for example, R 21 , R 22 , R 23 , and R 24 All are alkyl, or R 21 and R 22 are each independently the alkyl group (C 1-10 alkyl group), and R 23 and R 24 are each independently the aryl group (C 6-10 It can be an aryl group. More specifically, for example, the compound represented by the chemical formula 2 above or It could be.

[0053] In one embodiment, the repeating unit of the chemical formula 3 [] a and [] bIn the dihydrosiloxane compound including, the repeating units may be combined in an alternating manner, in a block, or in a random manner, but are represented as in Chemical Formula 3 for convenience. Accordingly, the dihydrosiloxane represented by Chemical Formula 3 may be an alternating copolymer, a block copolymer, a random copolymer, a graft copolymer, a gradient copolymer, a branched copolymer, or a crosslinked copolymer.

[0054] In one embodiment, in the above chemical formula 3, R 31 , R 32 , R 33 , and R 34 are each independently C 1-10 Alkyl group, C 6-10 Aryl group, or C 1-10 An alkoxy group, or C 1-15 Alkyl group, C 1-8 Alkyl group, C 1-5 Alkyl group, C 1-3 Alkyl group, -CH3, C 6-8 Aryl group, -Ph(phenyl), C 1-15 Alkoxy group, C 1-8 Alkoxy group, C 1-5 Alkoxy group, C 1-3 An alkoxy group, or -OCH3. In this case, R 31 , R 32 , R 33 , and R 34 At least two, three, or all of these are C 1-15 Alkyl group, C 1-10 Alkyl group, C 1-8 Alkyl group, C 1-5 Alkyl group, C 1-3 An alkyl group, or -CH3. In this case, R 31 , R 32 , R 33 , and R 34If two or three of the above substituents are alkyl groups, the remaining substituents are C 6-10 Aryl group, C 6-8 It can be an aryl group, or -Ph(phenyl). Specifically, for example, R 31 , R 32 , R 33 , and R 34 All are alkyl, or R 31 and R 32 are each independently the alkyl group (e.g., C 1-10 alkyl group), and R 33 and R 34 are each independently selected from the group consisting of the aryl group (e.g., C 6-10 It may be an aryl group. More specifically, for example, the compound represented by the above chemical formula 3 may be a compound represented by the following chemical formula 3-1 or chemical formula 3-2.

[0055] [Chemical Formula 3-1]

[0056]

[0057] [Chemical Formula 3-2]

[0058]

[0059] In one embodiment, the photosensitive resin composition may further include a thermal polymerization initiator, and the thermal polymerization initiator may be, for example, a peroxide-based compound. Specifically, for example, the thermal polymerization initiator may be a peroxydicarbonate-based compound, a peroxyester-based compound, or a peroxycyclohexane-based compound, but is not particularly limited as long as it is a peroxide-based initiator compound that reacts with a carbon-carbon unsaturated bond contained in polysiloxane. Specifically, for example, the thermal polymerization initiator may be 1,1-bis(t-butylperoxy)-3,3,5-trimethyl cyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-amylperoxy)cyclohexane, 1,1-bis(thexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, It may be 2,2-di(t-butylperoxy)butane, or butyl 4,4-di(tbutylperoxy)valerate.

[0060] In one embodiment, in the chemical formula 3, a:b may be 1:1 to 1:10, or 1:1 to 1:9.

[0061] In one embodiment, the weight average molecular weight of the polysiloxane may be, but is not necessarily limited to, 500 g / mol to 5,000 g / mol, 1,000 g / mol to 5,000 g / mol, 1,000 g / mol to 3,000 g / mol, or 2,000 g / mol to 3,000 g / mol.

[0062] In one embodiment, the weight average molecular weight of the photosensitive resin may be, but is not necessarily limited to, 1,000 g / mol to 200,000 g / mol, 5,000 g / mol to 200,000 g / mol, 10,000 g / mol to 100,000 g / mol, or 10,000 g / mol to 50,000 g / mol. By satisfying the weight average molecular weight, cracks do not occur on the surface during curing, and a desirable thickness of the cured film can be implemented.

[0063] In one embodiment, the polysiloxane including the bonding structure represented by the above chemical formula 1 may be prepared by hydrolysis and condensation reactions of alkoxysilane compounds represented by the following chemical formulas 1-1, 1-2, and 1-3.

[0064] [Chemical Formula 1-1]

[0065] X-Si(OR 11 )3

[0066] [Chemical Formula 1-2]

[0067] R 12 -Si(OR 13 )3

[0068] [Chemical Formula 1-3]

[0069] Si(OR 14 )4

[0070] In the above chemical formulas 1-1 to 1-3,

[0071] The above X is a substituent containing one or more carbon-carbon unsaturated bonds,

[0072] R 11 , R 12 , R 13 , and R 14 are each independently C 1-20 Alkyl group or C 6-20 It is an aryl group.

[0073] The above X can be applied in the same manner as the description for X in the above chemical formula 1.

[0074] In one embodiment, the R 11 , R 12 , R 13 , and R 14 are each independently C 1-15 Alkyl group, C 1-10 Alkyl group, C 1-8 Alkyl group, C 1-5 Alkyl group, C 1-3 Alkyl group, -CH2CH3, -CH3, C 6-15 Aryl group, C 6-10 Aryl group, C 6-8 An aryl group, or -Ph may be used. For example, the compound represented by the above chemical formula 1-1 may be vinyltrimethoxysilane, vinyltriethoxysilane, or vinyltripropoxysilane, the compound represented by the above chemical formula 1-2 may be methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, or phenyltributoxysilane, and the compound represented by the above chemical formula 1-3 may be tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, or tetrapropoxysilane. Specifically, for example, the compound represented by the chemical formula 1-1 may be CH2CH-Si-(OCH2CH3)3, the compound represented by the chemical formula 1-2 may be CH3-Si(OCH2CH3)3, and the compound represented by the chemical formula 1-3 may be Si(OCH2CH3)3.

[0075] In one embodiment, the photosensitive resin composition may further include a polysiloxane having a bonding structure represented by the following chemical formula 4.

[0076] [Chemical Formula 4]

[0077]

[0078] In the above chemical formula 4,

[0079] Y is a substituent containing one or more carbon-carbon unsaturated bonds.

[0080] In one embodiment, in the above chemical formula 4, Y is not particularly limited as long as it includes a substituent containing a carbon-carbon unsaturated bond (e.g., C=C). For example, it may be a substituent containing a vinyl group, an acrylate group, or a methacrylate group, and may be an alkenyl group or an alkynyl group, and may be a substituent containing 2 to 20, 2 to 15, 2 to 10, or 2 to 5 carbon atoms. Specifically, for example, C 2-10 Alkenyl group, C 2-15 Alkenyl group, C 2-10 Alkenyl group, C 2-5 It may be an alkenyl group (in which case the carbon-carbon double bond of the alkenyl group may be directly connected to Si, connected to Si via an alkylene group, or positioned at the end), a vinyl group (-CH=CH2), an acrylate group (-COCHCH2), or a methacrylate group (-OCOCHCH2), or a substituent of a combination thereof.

[0081] In one embodiment, the polysiloxane including the bonding structure represented by the above chemical formula 4 may be prepared by hydrolysis and condensation reactions of alkoxysilane compounds represented by the following chemical formulas 4-1, 4-2, and 4-3.

[0082] [Chemical Formula 4-1]

[0083] Y-Si(OR 41 )3

[0084] [Chemical Formula 4-2]

[0085] R 42 -Si(OR 43 )3

[0086] [Chemical Formula 4-3]

[0087] Si(OR 44 )4

[0088] In the above chemical formulas 4-1 to 4-3,

[0089] The above Y is a substituent containing one or more carbon-carbon unsaturated bonds,

[0090] R 41 , R 42 , R 43 , and R 44 are each independently C 1-20 Alkyl or C 6-20 It's Aryl.

[0091] In one embodiment, the R 41 , R 42 , R 43 , and R 44 are each independently C 1-15 Alkyl group, C 1-10 Alkyl group, C 1-8 Alkyl group, C 1-5 Alkyl group, C 1-3 Alkyl group, -CH2CH3, -CH3, C 6-15 Aryl group, C 6-10 Aryl group, C 6-8 It can be aryl, or -Ph. For example, the compound represented by the above chemical formula 4-1 may be vinyltrimethoxysilane, vinyltriethoxysilane, or vinyltripropoxysilane, the compound represented by the above chemical formula 4-2 may be methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, or phenyltributoxysilane, and the compound represented by the above chemical formula 4-3 may be tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, or tetrapropoxysilane. Specifically, for example, the compound represented by the above chemical formula 4-1 may be It may be CH2CH-Si-(OCH2CH3)3, the compound represented by the above chemical formula 4-2 may be CH3-Si(OCH2CH3)3, and the compound represented by the above chemical formula 4-3 may be Si(OCH2CH3)3.

[0092] A photosensitive resin composition according to one embodiment has high transparency by including a polysiloxane compound and has high solubility in an alkaline aqueous solution during development, so that a patterned transparent film can be easily formed.

[0093] In one embodiment, the hydrolysis and condensation reactions can be carried out in the presence of an acidic catalyst or a basic catalyst. Water and an acid or basic catalyst can be used for the hydrolysis. Examples of acid catalysts include formic acid, acetic acid, trifluoroacetic acid, nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, boric acid, and a cation exchange resin. Examples of base catalysts include ammonia, triethylamine, monoethanolamine, diethanolamine, triethanolamine, sodium hydroxide, sodium nitrate, sodium bicarbonate, potassium hydroxide, and anion exchange resin. The polymerization temperature is not particularly limited, but may typically range from 10°C to 150°C. The polymerization time is also not particularly limited, but may typically be carried out for 1 hour to 48 hours. In addition, the polymerization reaction can be carried out under any pressure, including increased pressure, reduced pressure, or atmospheric pressure. After polymerization, low molecular weight components may be removed by distillation to stabilize the polysiloxane compound.

[0094] The molecular weight of the polysiloxane compound according to one embodiment may be 1,000 g / mol to 100,000 g / mol, or 5,000 g / mol to 10,000 g / mol, and when the molecular weight is satisfied, the viscosity required for coating is maintained, thereby improving surface flatness.

[0095] In one embodiment, the photosensitive resin composition may include, but is not limited to, 50 wt% to 90 wt%, 60 wt% to 80 wt%, or 70 wt% to 75 wt% of the photosensitive resin relative to the total weight.

[0096] In the polymerization reaction of the photosensitive resin according to one embodiment, an organic solvent may be used as needed. As an organic solvent, a hydrocarbon-based organic solvent such as toluene or xylene can be used. As a polymerization condition, the polymerization temperature is preferably 40 to 150°C, particularly 80 to 120°C. If the polymerization temperature is too low, it may take a long time to complete the polymerization, and conversely, if the polymerization temperature is too high, there is a concern that the catalyst may not be activated. In addition, the polymerization time depends on the type and amount of the polymer, but it is preferably completed within about 0.5 to 10 hours, particularly 0.5 to 5 hours, to prevent the intrusion of moisture into the polymerization system. In addition, since organic hydrosiloxanes are prone to disproportionation reactions, which are side reactions, and hydroxylation polymerization reactions are generally exothermic reactions, it is preferable to add the organic hydrosiloxanes dropwise.

[0097] In one embodiment, the photosensitive resin composition may include, but is not necessarily limited to, 5 wt% to 30 wt%, 5 wt% to 20 wt%, or 10 wt% to 20 wt% of a polysiloxane having a bonding structure represented by the chemical formula 4 based on the total weight.

[0098] In one embodiment, the photosensitive resin composition may further include a surfactant, an adhesive aid, a photoinitiator, a photosensitizer, a solvent, and the like.

[0099] The solvent is not particularly limited, but may be an organic solvent selected from solvents capable of uniformly dissolving or dispersing each component of the photosensitive resin composition. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate (propylene glycol-1-monomethyl ether-2-acetate), propylene glycol monoethyl ether acetate (PGMEA), and propylene glycol monopropyl ether acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; and alcohols such as isopropanol and propanediol. These solvents can be used alone or in combination of two or more, and the content varies depending on the coating method and the required thickness of the coating film.

[0100] The photosensitizer is most preferably a 1,2-quinonediazide compound (DNQ), and the 1,2-quinonediazide compound can be a compound used as a photosensitizer in the resist field, for example. Specific examples include an ester of a phenol compound and 1,2-benzoquinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5-sulfonic acid; an ester of a phenol compound and 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid; a sulfonamide of a compound in which a hydroxyl group of a phenol compound is substituted with an amino group and 1,2-benzoquinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5-sulfonic acid; Or, compounds in which the hydroxyl group of a phenol compound is substituted with an amino group, and sulfonamides such as 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid may be mentioned. The above substances may be used alone or in combination of two or more.

[0101] The above phenol compounds are 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'-spirobiindene-5,6,7,5',6',7'-hexanol, and 2,2,4-trimethyl-7,2',4'-trihydroxyflavan.

[0102] The above 1,2-quinonediazide compound may be an ester of 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinonediazide-4-sulfonic acid, an ester of 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid, an ester of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinonediazide-4-sulfonic acid, or an ester of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid. These can be used alone or in combination of two or more, and these materials can improve the transparency of the positive photosensitive resin composition.

[0103] The photosensitive resin composition according to one embodiment may be a positive photosensitive resin composition.

[0104] The photosensitive resin composition according to one embodiment may further include one or more additives to improve resolution, coating uniformity, developability, or adhesiveness. Examples of such additives include a dispersant including an acrylic, styrene, polyethyleneimine, or urethane polymer; anionic, cationic, nonionic, or fluorine-based surfactants; coating improvers such as silicone resins; adhesion improvers (adhesion aids) such as silane coupling agents; ultraviolet absorbers such as alkoxybenzophenones; coagulation inhibitors such as sodium polyacrylate; thermal crosslinking agents such as epoxy compounds, melamine compounds, or bisazide compounds; and alkaline solubility accelerators such as organic carboxylic acids.

[0105] In one embodiment, the photosensitizer may be included in an amount of 0.1 wt% to 20 wt% based on the total weight of the photosensitive resin composition.

[0106] Specific examples of the above silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, etc., and these may be used alone or in combination of two or more. Preferably, in terms of film residue rate and adhesion to the substrate, γ-isocyanatopropyltriethoxysilane and / or N-phenyl-3-aminopropyltriethoxysilane may be used. The content of the silane coupling agent of the present invention is preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, based on 100 parts by weight (based on solid content) of the polysiloxane compound. When the content of the silane coupling agent is 0.01 parts by weight or more, adhesion to a substrate is improved, and when it is 10 parts by weight or less, thermal stability at high temperatures is improved, and the phenomenon of staining occurring after development can be prevented.

[0107] The above surfactants include, for example, BM-1000, BM-1100 (manufactured by BM CHEMIE), Megapack F142 D, Megapack F172, Megapack F173, Megapack F183, F-470, F-471, F-475, F-482, F-489 (manufactured by Dainippon Ink & Kagaku Kogyo Co., Ltd.), Florard FC-135, Florard FC-170C, Florard FC-430, Florard FC-431 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (manufactured by Asahi Glass Co., Ltd.), F-Top EF301, F-Top 303, F-Top 352 (manufactured by Shin-Akita Kasei Co., Ltd.), SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Silicone Co., Ltd.), DC3PA, DC7PA, SH11PA, SH21PA, SH8400, GE, FZ-2100, FZ-2110, FZ-2122, FZ-2222, FZ-2233 (manufactured by Dow Corning Toray Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, Examples thereof include fluorine-based and silicone-based surfactants such as TSF-4460, TSF-4452 (manufactured by Toshiba Silicone Co., Ltd.), and BYK-333 (manufactured by BYK Co., Ltd.); nonionic surfactants such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether, and polyoxyethylene nonylphenyl ether; and polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic acid copolymer Polyflow No. 57, 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.).These can be used alone or in combination of two or more. The surfactant is preferably used in an amount of 0.05 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, per 100 parts by weight (based on solid content) of the polysiloxane compound. When the content of the surfactant is 0.05 parts by weight or more, the applicability is improved and cracks do not occur on the applied surface, and when it is 10 parts by weight or less, it is advantageous in terms of price.

[0108] The photosensitive resin composition according to one embodiment has properties such as high solvent resistance, high water resistance, high acid resistance, high alkali resistance, high heat resistance, high transparency, and high adhesion to a substrate, which are generally required for patterned transparent films and insulating films, for example.

[0109] According to one embodiment, the photosensitive resin composition has excellent solvent resistance, acid resistance, alkali resistance, heat resistance, and transparency, so that transparent films, insulating films, display elements, etc. using the positive type photosensitive resin composition do not cause surface roughness in the resin film even when immersion, contact, or heat treatment is performed using a solvent, acid, or alkaline solution in the post-manufacturing process. Therefore, since the transparent film, etc. using the positive type photosensitive resin composition according to the present invention has high light transmittance, the display element, etc. using the same can improve the display quality of the product.

[0110] Another embodiment provides a photoresist film manufactured using the photosensitive resin composition according to the above embodiment.

[0111] Another embodiment provides a substrate protective film manufactured using the photosensitive resin composition according to the above embodiment.

[0112] Another embodiment provides a display device including a substrate protective film according to the above embodiment.

[0113] Another embodiment provides a method for forming a pattern, comprising: a step of applying a photosensitive resin composition according to the above embodiment onto a substrate to produce a photoresist film; a step of exposing the photoresist film; and a step of developing the exposed photoresist film using a developer.

[0114] Light sources used in the investigation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and argon gas lasers. In some cases, X-rays and electron beams can also be used. The exposure dose varies depending on the type and mixing amount of each component of the composition and the dry film thickness, but when using a high-pressure mercury lamp, it is 500 mJ / cm. 2 (by 365nm sensor) may be less than or equal to:

[0115] A photosensitive resin composition according to one embodiment has excellent surface hardness and excellent adhesion to a substrate, so that it can be easily used in the manufacture of a substrate protective film, and a substrate protective film manufactured therefrom has excellent physical properties.

[0116] In a method for manufacturing a substrate protective film using a photosensitive resin composition according to one embodiment, the temperature and time for curing may be any temperature and time within a range that can be recognized by a person skilled in the art.

[0117]

[0118] Hereinafter, specific examples and experimental examples are provided to illustrate the present invention. However, the examples and experimental examples described below are merely illustrative of some embodiments of one implementation, and therefore, the technology described in this specification should not be construed as being limited thereto.

[0119]

[0120] Dihydrosiloxane compounds were synthesized through the following Synthesis Examples 1 to 5.

[0121] <Synthesis Example 1> Synthesis of dihydrosiloxane compound 1

[0122] 1,3-dihydro-1,1,3,3-tetramethyldisiloxane and 1,3-dihydro-1,1,3,3-tetraphenoldisiloxane were added to a 3,000 mL three-necked round flask at a molar ratio of 8:2 to prepare dihydrosiloxane compound 1 having a molecular weight of 1,350 g / mol.

[0123] <Synthesis Example 2> Synthesis of dihydrosiloxane compound 2

[0124] Dihydrosiloxane compound 2 having a molecular weight of 1,280 g / mol was prepared in the same manner as in Synthesis Example 1, except that 1,3-dihydro-1,1,3,3-tetramethyldisiloxane and 1,3-dihydro-1,1,3,3-tetraphenoldisiloxane were added in a molar ratio of 9:1.

[0125] <Synthesis Example 3> Synthesis of dihydrosiloxane compound 3

[0126] Dihydrosiloxane compound 3 having a molecular weight of 1,520 g / mol was prepared in the same manner as in Synthesis Example 1, except that 1,3-dihydro-1,1,3,3-tetramethyldisiloxane and 1,3-dihydro-1,1,3,3-tetraphenoldisiloxane were added in a molar ratio of 6:4.

[0127] <Synthesis Example 4> Synthesis of dihydrosiloxane compound 4

[0128] Dihydrosiloxane compound 4 having a molecular weight of 1,620 g / mol was prepared in the same manner as in Synthesis Example 1, except that 1,3-dihydro-1,1,3,3-tetramethyldisiloxane and 1,3-dihydro-1,1,3,3-tetraphenoldisiloxane were added in a molar ratio of 5:5.

[0129] <Synthesis Example 5> Synthesis of dihydrosiloxane compound 5

[0130] Dihydrosiloxane compound 5 having a molecular weight of 1,980 g / mol was prepared in the same manner as in Synthesis Example 1, except that 1,3-dihydro-1,1,3,3-tetramethyldisiloxane and 1,3-dihydro-1,1,3,3-tetraphenoldisiloxane were added in a molar ratio of 8:2.

[0131]

[0132] Polysiloxane compounds were synthesized through the following Synthesis Examples 6 and 7.

[0133] <Synthesis Example 6> Synthesis of polysiloxane compound 1

[0134] 190.3 g of vinyltriethoxysilane, 178.3 g of methyltriethoxysilane, 208.3 g of tetraethoxysilane, and 1 L of butyl acetate were placed in a three-necked flask with a volume of approximately 2 L, and a solution of 2 mL of 1 mol / L nitric acid and 180 mL of purified water was added dropwise over 30 minutes using a dropping funnel installed therein while vigorously stirring the contents of the flask. As a result, an exothermic reaction occurred in the contents of the flask, and initially, the solution was white and cloudy, but as the stirring continued, it became a colorless and transparent solution. After neutralizing the mixture, 1,000 mL of toluene and 1,000 mL of water were added, and the mixture was separated into two layers. The separated organic layer was concentrated under reduced pressure to remove the solvent. The molecular weight of the obtained polysiloxane compound was measured, and the weight average molecular weight was confirmed to be 2,500 g / mol.

[0135] <Synthesis Example 7> Synthesis of polysiloxane compound 2

[0136] 190.3 g of phenyltriethoxysilane, 178.3 g of methyltriethoxysilane, 208.3 g of tetraethoxysilane, and 1 L of butyl acetate were placed in a three-necked flask with a volume of about 2 L, and a solution of 2 mL of 1 mol / L nitric acid and 180 mL of purified water was added dropwise over 30 minutes using a dropping funnel installed therein while vigorously stirring the contents of the flask. As a result, an exothermic reaction occurred in the contents of the flask, and initially it was a white, cloudy solution, but as the stirring continued, it became a colorless, transparent solution. After neutralizing the mixture, 1,000 mL of toluene and 1,000 mL of water were added, and the mixture was separated into two layers. The separated organic layer was concentrated under reduced pressure to remove the solvent. The molecular weight of the obtained polysiloxane compound was measured, and the weight average molecular weight was confirmed to be 55,000 g / mol.

[0137]

[0138] A photosensitive resin was manufactured through the following Examples 1 to 6 and Comparative Example 1.

[0139] <Example 1> Synthesis of photosensitive resin 1

[0140] In a 3,000 mL three-necked round flask, 54 g of the polysiloxane compound 1 synthesized in Synthesis Example 6, 70 g of toluene, and 0.1 g of chloroplatinic acid were added, and the temperature was raised to 80°C. Then, 13.4 g of 1,3-dihydro-1,1,3,3-tetramethyldisiloxane was added dropwise into the flask. After the addition, the mixture was stirred at 100°C for 1 hour, and toluene was removed to obtain 54 g of a solid product.

[0141] As a result of checking the IR (infrared ray) spectrum for the above product, it was confirmed that the hydroxylation reaction was completed because no absorption peak derived from the hydroxyl group was confirmed. Also, 1,050 cm -1It had an absorption peak derived from the siloxane bond. In addition, the molecular weight was measured by GPC (gel permeation chromatography) and the weight average molecular weight was 12,000 g / mol in polystyrene conversion.

[0142] <Examples 2 to 6> Synthesis of photosensitive resins 2 to 6

[0143] Photosensitive resins 2 to 6 were synthesized in the same manner as in Example 1, except that the dihydrosiloxane compounds prepared in Synthesis Examples 1 to 5 were used in that order instead of 1,3-dihydro-1,1,3,3-tetramethyldisiloxane in Example 1. As a result of measuring the molecular weights in the same manner as in Example 1, the weight average molecular weights were 30,000 g / mol, 15,000 g / mol, 25,000 g / mol, 30,000 g / mol, and 40,000 g / mol, respectively.

[0144] <Comparative Example 1> Synthesis of Photosensitive Resin 7

[0145] In Example 1, a photosensitive resin 7 was synthesized in the same manner as in Example 1, except that 50.8 g of the polysiloxane compound 2 synthesized in Synthesis Example 7 was used instead of the polysiloxane compound 1 synthesized in Synthesis Example 6. The molecular weight was measured in the same manner as in Example 1, and the weight average molecular weight was 40,000 g / mol.

[0146]

[0147] A positive photosensitive resin composition was prepared through the following Examples 7 to 12, Comparative Examples 2 and 3.

[0148] <Example 7> Preparation of photosensitive resin composition 1

[0149] 11.24 g of the photosensitive resin 1 synthesized in Example 1, 2.46 g of the polysiloxane compound 1 synthesized in Synthesis Example 6, 1.5 g of a quinonediazide compound (TPPA-520) from Miwon, 0.042 g of a leveling surfactant (BYK 333 silicone surfactant) from BYK, 0.084 g of an adhesive aid (KBE-9007 from Shin-Etsu), and 0.5 g of 1,1-bis(t-butylperoxycyclohexane) as a thermal polymerization initiator were added to 8.2 g of propylene glycol-1-monomethyl ether-2-acetate and stirred to prepare a positive type photosensitive resin composition 1.

[0150] <Example 8> Preparation of photosensitive resin composition 2

[0151] 8.24 g of the photosensitive resin 2 synthesized in Example 2, 1.5 g of the quinonediazide compound (TPPA-520) from Miwon, 15 g of the polysiloxane compound synthesized in Synthesis Example 6, 0.35 g of a photoinitiator (TPO) from BASF, 0.042 g of a leveling surfactant (BYK 333 silicone surfactant) from BYK, 0.084 g of an adhesion aid (KBE-9007 from Shin-Etsu), and 0.5 g of 1,1-bis(t-butylperoxycyclohexane) as a thermal polymerization initiator were added to 8.2 g of propylene glycol-1-monomethyl ether-2-acetate and stirred to prepare a positive-type photosensitive resin composition 2.

[0152] <Examples 9 to 12> Preparation of photosensitive resin compositions 3 to 6

[0153] Positive type photosensitive resin compositions 3 to 6 were manufactured in the same manner as in Example 7, except that photosensitive resins 3 to 6 manufactured in Examples 3 to 6 were used in order instead of photosensitive resin 1 in Example 7.

[0154] <Comparative Example 2> Preparation of photosensitive resin composition 7

[0155] A positive photosensitive resin 7 was manufactured in the same manner as in Example 7, except that the photosensitive resin 7 manufactured in Comparative Example 1 was used instead of the photosensitive resin 1 in Example 7.

[0156] <Comparative Example 3> Preparation of photosensitive resin composition 8

[0157] A positive photosensitive resin 8 was manufactured in the same manner as in Example 7, except that a thermal polymerization initiator was not used.

[0158]

[0159] Table 1 below summarizes the content of the thermal polymerization initiator included in the photosensitive resin compositions of Examples 7 to 12, Comparative Examples 2 and 3, the molar ratio of the methyl group and the phenyl group of the dihydrosiloxane compound used in the production of the photosensitive resin, and whether the photosensitive resin contains a vinyl group.

[0160] Content of thermal polymerization initiatorMethyl group:phenyl group (molar ratio)Contains vinyl group of photosensitive resinExample 70.5 gMethyl group 100%○Example 80.5 g8:2○Example 90.5 g9:1○Example 100.5 g6:4○Example 110.5 g5:5○Example 120.5 g8:2○Comparative example 20.5 gMethyl group 100%×Comparative example 3-Methyl group 100%○

[0161]

[0162] <Experimental Example>

[0163] 1. Forming a video pattern

[0164] The photosensitive resin compositions of Examples 7 to 12, Comparative Examples 2 and 3 were applied to a substrate that had undergone a predetermined pretreatment using a spin coating method to a thickness of 4 μm, and then heated at a temperature of 90° C. for 2 minutes to remove the solvent, thereby forming a coating film.

[0165] In order to form the required pattern on the obtained film, a mask of a predetermined shape was inserted, and then an active line of 365 nm was irradiated using a high-pressure mercury lamp (30 mJ / cm2 ) Then, an alkaline aqueous solution was used as a developer to dissolve and remove unnecessary parts, leaving only the exposed portion to form a pattern. After the image pattern obtained by development was cooled to room temperature, it was post-baked at 230°C for 20 minutes in a hot air circulation dryer to obtain an image pattern.

[0166] 2. Surface hardness evaluation

[0167] The surface hardness of the cured film was measured using the method described in ASTM-D3363 using the substrate manufactured through the above 1. image pattern formation. A Mitsubishi pencil was brought into contact with the substrate using a pencil hardness tester, and then a 500 g weight was placed on top of the pencil pencil to increase the load. The surface was scratched at a speed of 50 mm / sec and the surface was observed to measure the hardness. The measurement standard was evaluated based on the observation of no wear, peeling, tearing, or scratching of the surface at a level corresponding to the pencil hardness.

[0168] 3. Resolution Evaluation

[0169] In order to measure the resolution of the image pattern of the substrate manufactured through the above 1. image pattern formation, the resolution was measured by observing the minimum size of the contact hole formed using a micro-optical microscope.

[0170] 4. Sensitivity Evaluation

[0171] In order to evaluate the sensitivity of the above composition, a mask having a circle type contact hole shape of 10 μm in size was used in the exposure process among the substrate methods manufactured through the formation of the image pattern in the above 1. The substrate on which the composition was formed was exposed to an exposure dose of 10 mJ to 50 mJ, and a development process was performed with an alkaline aqueous developer, and an image pattern was obtained by post-baking at 230°C for 20 minutes in a hot air circulation drying oven. The sensitivity was evaluated by confirming the exposure dose at which the image pattern was formed to be 10 μm in size, which is the same as the mask size.

[0172] 5. Evaluation of substrate adhesion

[0173] In order to measure the substrate adhesion characteristics of the image pattern of the substrate manufactured through the above 1. image pattern formation, a cross-cut test was performed according to the method described in ASTM D3359, and the adhesive strength was evaluated according to the following criteria.

[0174] OB: Broken into flakes and more than 65% detached

[0175] 1B: The area of ​​the cut area where the ends and grids fall off is greater than 35% and less than 65%.

[0176] 2B: A small area falls off at the intersection of the cut area, and the area is more than 15% and less than 35%.

[0177] 3B: A small area falls off at the intersection of the cut area, with the area exceeding 5% and not exceeding 15%.

[0178] 4B: The area is less than 5% of the intersection of the cut area.

[0179] 5B: The ends of the cut portion are smooth and there is no grid falling off.

[0180] 6. Chemical resistance evaluation

[0181] The substrate manufactured through the above 1. image pattern formation was immersed in etchant and stripper solutions under the following conditions to check the degree of damage to the coating film on the upper part of the substrate from the etchant and stripper solutions. The immersion conditions are as follows: immersed in BOE (buffered oxide etchant) etchant at room temperature for 3 hours, and the thickness and surface were checked using a non-contact thickness measuring device (ellipsometer) and the surface condition through an optical microscope, and then immersed in LGS-900 stripper at 60 ℃ for 10 minutes to check the thickness and surface. If surface damage was confirmed, it was evaluated as ○, and if no damage was confirmed, it was evaluated as ×. In addition, the thickness before and after BOE immersion and before and after LGS-900 immersion were calculated, and the change rate was calculated. At this time, the smaller the thickness deviation and the less surface damage, the better the chemical resistance.

[0182]

[0183] The results of the above evaluation are shown in Table 2 below.

[0184] Hardness Resolution (μm) Sensitivity (mJ) Substrate Adhesion Chemical Resistance (Thickness Change / Damage) BOELGS900 Example 76H5355B95% / ×102% / × Example 87H2305B94% / ×104% / × Example 97H3305B96% / ×104% / × Example 107H3305B96% / ×103% / × Example 116H4305B93% / ×104% / × Example 126H3305B93% / ×103% / × Comparative Example 25H11504B No film 113% / ○ Comparative Example 34H6805B No film 111% / ○

[0185] As can be confirmed through the above Table 2, the substrates formed with patterns using the photosensitive resin composition according to the examples, which are prepared by polymerizing a dihydrosiloxane compound containing a methyl group and a polysiloxane containing a vinyl group, and by thermal polymerization of the polysiloxane containing a vinyl group, all exhibited superior properties compared to the comparative examples in the physical property evaluations conducted through 2. to 6. above. Specifically, when the photosensitive resin did not include a reactive group capable of reacting with a thermal polymerization initiator, such as a vinyl group (Comparative Example 2), or when the photosensitive resin was not additionally thermally polymerized with the polysiloxane compound (Comparative Example 3), the surface hardness, resolution, and sensitivity of the substrates formed with patterns using the photosensitive resin composition were all inferior to those of the examples, and in particular, when immersed in BOE etchant, the coating film was completely dissolved and not observed (No film). Additionally, damage to the surface was observed when immersed in LGS-900 stripper, and the thickness deviation was large compared to the examples.

[0186]

[0187] Above, although an embodiment has been described in detail through examples and experimental examples, the scope of an embodiment is not limited to a specific example, and should be interpreted in accordance with the appended patent claims.

Claims

1. A photosensitive resin composition comprising a photosensitive resin comprising a polysiloxane structure having a bonding structure represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, X is a substituent containing one or more carbon-carbon unsaturated bonds.

2. In paragraph 1, A photosensitive resin composition, wherein in the chemical formula 1, X is a substituent containing a vinyl group, an acrylate group, or a methacrylate group.

3. In paragraph 1, The photosensitive resin composition is prepared by hydrolysis and condensation reaction of a polysiloxane having a bonding structure represented by the chemical formula 1 and a dihydrosiloxane compound represented by the chemical formula 2 or 3 below: [Chemical formula 2] In the above chemical formula 2, R 21 , R 22 , R 23 , and R 24 are each independently C 1-20 Alkyl group, C 6-20 Aryl group, or C 1-20 It is an alkoxy group, [Chemical Formula 3] In the above chemical formula 3, R 31 , R 32 , R 33 , and R 34 are each independently C 1-20 Alkyl group, C 6-20 Aryl group, or C 1-20 It is an alkoxy group, a and b are each independently an integer greater than or equal to 0, and a:b is 1:1 to 1:

20.

4. In paragraph 3, In the chemical formula 2 above, R 21 , R 22 , R 23 , and R 24 are each independently C 1-10 Alkyl group, C 6-10 Aryl group, or C 1-10 A photosensitive resin composition comprising an alkoxy group.

5. In paragraph 4, In the chemical formula 2 above, R 21 , R 22 , R 23 , and R 24 At least two of them are C 1-10 Alkyl group, photosensitive resin composition.

6. In paragraph 3, In the above chemical formula 3, R 31 , R 32 , R 33 , and R 34 are each independently C 1-10 Alkyl group, C 6-10 Aryl group, or C 1-10 A photosensitive resin composition comprising an alkoxy group.

7. In paragraph 6, In the above chemical formula 3, R 31 , R 32 , R 33 , and R 34 At least two of them are C 1-10 Alkyl group, photosensitive resin composition.

8. In paragraph 3, In the above chemical formula 3, R 31 and R 32 are each independently C 1-10 is an alkyl group, and the above R 33 and R 34 are each independently C 6-10 Aryl group, photosensitive resin composition.

9. In paragraph 1, A photosensitive resin composition further comprising a thermal polymerization initiator.

10. In paragraph 8, A photosensitive resin composition wherein the thermal polymerization initiator comprises a peroxide-based compound.

11. In paragraph 3, A photosensitive resin composition, wherein in the chemical formula 3, a:b are 1:1 to 1:

10.

12. In paragraph 1, A photosensitive resin composition wherein the polysiloxane has a weight average molecular weight of 500 g / mol to 5,000 g / mol.

13. In paragraph 1, A photosensitive resin composition, wherein the photosensitive resin has a weight average molecular weight of 1,000 g / mol to 200,000 g / mol.

14. In paragraph 1, A photosensitive resin composition, wherein the polysiloxane including the bonding structure represented by the chemical formula 1 is prepared by hydrolysis and condensation reactions of alkoxysilane compounds represented by the chemical formulas 1-1, 1-2, and 1-3 below: [Chemical Formula 1-1] X-Si(OR 11 )3 [Chemical Formula 1-2] R 12 -Si(OR 13 )3 [Chemical Formula 1-3] Si(OR 14 )4 In the chemical formulas 1-1 to 1-3 above, The above X is a substituent containing one or more carbon-carbon unsaturated bonds, R 11 , R 12 , R 13 , and R 14 are each independently C 1-20 Alkyl group or C 6-20 It's an aryl group.

15. In paragraph 14, In the chemical formulas 1-1 to 1-3 above, R 11 , R 12 , R 13 , and R 14 are each independently C 1-10 Alkyl group, photosensitive resin composition.

16. In paragraph 1, The photosensitive resin composition further comprises a polysiloxane having a bonding structure represented by the following chemical formula 4: [Chemical Formula 4] In the above chemical formula 4, Y is a substituent containing one or more carbon-carbon unsaturated bonds.

17. In paragraph 16, A photosensitive resin composition, wherein the polysiloxane including the bonding structure represented by the chemical formula 4 is prepared by hydrolysis and condensation reactions of alkoxysilane compounds represented by the chemical formulas 4-1, 4-2, and 4-3 below: [Chemical Formula 4-1] Y-Si(OR 41 )3 [Chemical Formula 4-2] R 42 -Si(OR 43 )3 [Chemical Formula 4-3] Si(OR 44 )4 In the chemical formulas 4-1 to 4-3 above, The above Y is a substituent containing one or more carbon-carbon unsaturated bonds, R 41 , R 42 , R 43 , and R 44 are each independently C 1-20 Alkyl group or C 6-20 It's an aryl group.

18. In paragraph 17, In the chemical formulas 4-1 to 4-3 above, R 41 , R 42 , R 43 , and R 44 are each independently C 1-10 Alkyl group, photosensitive resin composition.

19. In paragraph 1, A photosensitive resin composition comprising 50 to 90 wt% of the photosensitive resin based on the total weight of the photosensitive resin composition.

20. In paragraph 16, The photosensitive resin composition comprises 5 to 30 wt% of polysiloxane having a bonding structure represented by the chemical formula 4 based on the total weight of the photosensitive resin composition.

21. A photoresist film manufactured using a photosensitive resin composition according to any one of claims 1 to 20.

22. A substrate protective film manufactured using a photosensitive resin composition according to any one of claims 1 to 20.

23. A step of manufacturing a photoresist film by applying a photosensitive resin composition according to any one of claims 1 to 20 onto a substrate; A step of exposing the above photoresist film; and A method for forming a pattern, comprising a step of developing the above-mentioned exposed photoresist film using a developer.

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