Polysiloxane-containing photosensitive resin composition

Abstract

The present invention relates to a photosensitive resin composition comprising: a polysiloxane resin; a binder resin including a (meth) acrylic copolymer resin; an acrylic polyfunctional monomer having different acrylics having two or more functions; a photoinitiator which is at least one type selected from the group consisting of an O-acyl oxime-based photoinitiator, an acetophenone-based photoinitiator, and a benzophenone-based photoinitiator; the additive comprises at least one of a silane coupling agent, a leveling agent, an epoxy curing agent and a curing accelerator; and a solvent. The photosensitive resin composition has the characteristics of improved insulativity and heat resistance and very low moisture absorption rate because of containing polysiloxane, and is particularly used as a PDL (Pixel Defined Layer) layer which divides and insulates the boundaries between pixels of an OLED display device and a planarization layer which is formed flat on the lower part of the PDL layer and has insulation characteristics.

Description

Technical Field

[0001] Embodiments of the present invention relate to a photosensitive resin composition, and more particularly, to a photosensitive resin composition containing polysiloxane for forming an insulating film applied to a display device, wherein the insulating film has not only insulating properties but also heat resistance and high resolution characteristics. Background Art

[0002] Recently in the display industry, OLED display devices that display images through self-luminous organic light-emitting layers without the backlight unit in liquid crystal display devices (LCDs) that display images through an additional light source such as a backlight unit have attracted much attention. In particular, the OLED display devices have recently shown a trend of being used in large electronic devices such as televisions instead of small electronic devices such as smartphones. In addition, since the OLED display devices can use the mother substrate on which the organic light-emitting layer is deposited as a flexible substrate, they have attracted much attention as display devices that can be bent.

[0003] This OLED display device includes a pixel definition layer (PDL) that divides the boundaries between pixels constituting the pixels and electrically insulates the pixels, and a planarization layer that is evenly formed at the bottom of the PDL layer and has insulating properties. Here, the PDL layer is precisely patterned by a photolithography process. As a material for forming the PDL layer, a photosensitive resin composition containing only an acrylic compound with excellent photosensitivity has been used in the past.

[0004] However, the photosensitive resin composition containing only the acrylic compound is unstable under a temperature condition of about 250° C. or higher. Moreover, since the photosensitive resin composition containing only the acrylic compound has an excessively high dielectric constant, it is somewhat difficult to use it as an insulating film such as the PDL layer. In particular, the photosensitive resin composition containing only the acrylic compound has a high moisture absorption rate of absorbing moisture that is fatal to the driving of the LED, and therefore it can be regarded as a material that cannot be used as an insulating film of the OLED. Summary of the invention

[0005] Technical issues

[0006] Embodiments of the present invention provide a photosensitive resin composition including polysiloxane and a binder resin, wherein the polysiloxane has excellent electrical insulation, improved heat resistance and improved moisture absorption, and the binder resin includes a (meth)acrylic copolymer resin.

[0007] Technical Solution

[0008] The photosensitive resin composition according to an embodiment of the present invention comprises: a polysiloxane resin represented by Chemical Formula 1; a binder resin including a (meth) acrylic copolymer resin represented by Chemical Formula 7; an acrylic multifunctional monomer having different difunctional or higher acrylic acid esters; a photoinitiator, which is at least one selected from the photoinitiator group including O-acyl oxime photoinitiators, acetophenone photoinitiators and benzophenone photoinitiators; an additive, which includes at least one of a silane coupling agent, a leveler, an epoxy curing agent, and a curing accelerator; and a solvent.

[0009] [A-1] Polysiloxane resin

[0010]

Chemical formula 1

[0011]

[0012] Here, k, l, m and n are each a natural number greater than or equal to 1. In addition, R5 to R8 are hydrogen or ethoxy groups.

[0013] Herein, R1 may include a residue represented by the following Chemical Formula 2.

[0014]

Chemical formula 2

[0015]

[0016] The residue represented by Chemical Formula 2 is formed to open the epoxy portion so that other functional groups can be connected to the opened epoxy portion. Therefore, when the polysiloxane-containing photosensitive resin composition is used to form a PDL layer or a planarization layer, it can function to connect an initiator or a curing accelerator as one of the functional groups included in the additive, or to adjust the curing rate through the opened double bond portion to improve the residual film rate and chemical resistance.

[0017] Furthermore, a PDL layer or a planarization layer formed using the photosensitive resin composition having R1 represented by the Chemical Formula 2 not only has improved adhesion on an electrode or a substrate but also may have excellent acid resistance characteristics to a strong acid etching solution in a photolithography process.

[0018] Herein, R2 may include a residue represented by any one of the following Chemical Formulas 3 and 4.

[0019]

Chemical formula 3

[0020]

[0021]

Chemical formula 4

[0022]

[0023] The residues represented by the chemical formulae 3 and 4 are formed to open some double bond portions so that other functional groups can be connected thereto. Therefore, when a PDL layer or a planarization layer is formed using a photosensitive resin composition comprising a polysiloxane including R2 represented by any one of the chemical formulae 3 and 4, it can function as a functional group connection initiator or curing accelerator included in an additive, or improve the residual film rate by adjusting the molecular weight through the opened double bond portion.

[0024] Herein, R3 of the Chemical Formula 1 may include a residue represented by the following Chemical Formula 5.

[0025]

Chemical formula 5

[0026]

[0027] In chemical formula 5, R9 is OH, R 10 and R 11 It is CH3 or CF3.

[0028] The dielectric constant of a PDL layer or a planarization layer formed using the polysiloxane-containing photosensitive resin composition having R3 represented by the Chemical Formula 5 may be reduced, thereby having improved insulation characteristics.

[0029] In particular, the more trifluoromethyl groups (CF3) there are in the residue represented by the chemical formula 5, the lower the dielectric constant is, thereby further improving the insulation properties.

[0030] In addition, the hydroxyl group (OH) in the residue represented by the chemical formula 5 may also function as a functional group for improving developability in a photolithography process.

[0031] Herein, R4 of Chemical Formula 1 may include a residue represented by the following Chemical Formula 6.

[0032]

Chemical formula 6

[0033]

[0034] The photosensitive resin composition including the polysiloxane having the residue (R4) represented by Chemical Formula 6 may have improved transparency. Therefore, when the PDL layer or the planarization layer is formed by a photolithography process, more precise patterning may be performed by increasing sensitivity to light.

[0035] In particular, the trifluoromethyl group (CF3) in the residue (R4) represented by the chemical formula 6 further reduces the dielectric constant and moisture absorption rate of the PDL layer or the planarization layer, thereby enabling the OLED to operate in a more stable state without moisture while improving the insulation characteristics.

[0036] [A-2] (Meth)acrylic acid copolymer resin

[0037] The (meth)acrylic copolymer resin may include a copolymer represented by Chemical Formula 7 below.

[0038]

Chemical formula 7

[0039]

[0040] In the chemical formula 7, j, k, l, m, and n are integers from 1 to 90, and R 12 , R 13 , R 14 , R 15 , R 16 and R 18 are any one selected from the group consisting of hydrogen, methyl and hydroxymethyl, R 17 is hydrogen or a group forming a carboxylic anhydride or amide structure, X is methyl or cyclohexyl, Y is selected from the group consisting of an alkyl ester having 1 to 12 carbon atoms, an alkyl ester having 2 to 6 carbon atoms substituted with 1 to 2 hydroxy groups, an alkoxy polyalkylene having 1 to 3 carbon atoms, a glycol ester having 2 to 3 carbon atoms, and an alkyl ester having 1 to 6 carbon atoms substituted with a phenyl group, and the symbol * is a bonding point.

[0041] The (meth)acrylic copolymer resin can be used in the preparation of the photosensitive resin composition in the form of a solution, or can be separated from the solution and used in the preparation of the photosensitive resin composition.

[0042] The (meth)acrylic copolymer resin is a functional polymer that plays a major bonding function in forming a film and pattern, and can exhibit various properties such as chemical resistance, heat resistance, developability, adhesion, resolution, etc. according to the type and content of monomers and molecular weight.

[0043] In addition, when preparing the photosensitive resin composition, two or more (meth)acrylic copolymer resins may be mixed and used to complement the characteristics of the respective copolymers.

[0044] On the other hand, the (meth) acrylic copolymer resin may be a polymer or copolymer formed from one or more (meth) acrylic monomers or oligomers. Specifically, the (meth) acrylic copolymer resin may include a copolymer comprising a vinyl repeating unit substituted or unsubstituted with an aromatic functional group and at least one (meth) acrylic repeating unit.

[0045] In one embodiment of the present invention, the (meth)acrylic copolymer resin may have a weight average molecular weight (Mw) ranging from 1000 to 50000 g / mol. As mentioned above, it is preferably a weight average molecular weight (Mw) ranging from 2000 to 20000 g / mol.

[0046] When the weight average molecular weight is less than 1000 g / mol, the film loss increases due to the fast development speed of the developer in the light treatment, and the film flattening also becomes uneven. In addition, when the weight average molecular weight is 50000 g / mol or more, the pattern formation slows down due to the slow development speed of the developer in the light treatment, the process time increases, and the batch production yield decreases.

[0047] In one embodiment of the present invention, the polysiloxane resin may have a weight average molecular weight (Mw) in the range of 1,000 to 20,000 g / mol.

[0048] When the weight average molecular weight of the polysiloxane resin is less than 1000 g / mol, the loss of the developer during the photoprocessing increases, resulting in a decrease in the residual film rate. On the contrary, when the weight average molecular weight exceeds 20000 g / mol, the sensitivity and resolution are reduced. Therefore, it is preferred to have a weight average molecular weight (Mw) in the range of 2000 to 10000 g / mol.

[0049] In one embodiment of the present invention, the polysiloxane resin may be in the range of 10 to 100 weight % based on 100 parts by weight of the (meth)acrylic copolymer resin.

[0050] For 100 parts by weight of the (meth)acrylic copolymer resin, when the polysiloxane resin is less than 10% by weight, there is no influence of the polysiloxane resin, so the resolution and sensitivity are not improved. When it exceeds 100% by weight, the polysiloxane having a weight average molecular weight less than that of the (meth)acrylic copolymer resin is relatively excessive, so there are disadvantages such as increased loss of developer in the developing process, resulting in a decrease in the residual film rate, and over-curing leading to a decrease in adhesion.

[0051] The photosensitive resin composition according to the embodiment of the present invention can be applied to LCD and OLED, and in particular, can form a PDL (Pixel Defined Layer) that divides the boundaries between pixels of an active OLED display device and insulates each other through a photolithography process, or a planarization layer that is evenly formed under the PDL layer and has insulating properties.

[0052] As described above, the photosensitive resin composition including the (meth)acrylic copolymer resin and the polysiloxane has a structure in which siloxane is connected to the main chain as shown in Chemical Formula 1, thereby having a reduced dielectric constant, thereby significantly improving the main function of the PDL layer or the planarization layer, namely, insulation.

[0053] In addition, compared with the photosensitive resin composition containing only acrylic compounds described in the background art, the photosensitive resin composition containing the polysiloxane has a structure in which siloxane having excellent heat resistance is connected as the main chain, and thus can have better heat resistance. Specifically, the photosensitive resin composition containing only acrylic compounds in the background art is unstable at a high temperature of about 250°C, while the photosensitive resin composition containing polysiloxane of the present invention can have heat resistance characteristics that does not cause morphological deformation even at a high temperature of about 400°C.

[0054] In addition, since the siloxane as the main chain has the property of poor hygroscopicity, the photosensitive resin composition containing polysiloxane has a relatively low moisture absorption rate. Therefore, when the PDL layer or planarization layer of OLED is formed using the photosensitive resin composition containing polysiloxane, the OLED can be protected from fatal damage that immediately causes light emission failure when in contact with moisture.

[0055] In addition, since the siloxane as the main chain has strong acid resistance to acidic substances, when the PDL layer or planarization layer of the OLED is formed by a photolithography process using the polysiloxane-containing photosensitive resin composition, the pattern can be well protected from the strong acid etching solution used at this time, thereby being able to form the PDL layer or planarization layer having a pattern with a more precise and stable thickness.

[0056] In addition, due to another characteristic of siloxane, the photosensitive resin composition containing polysiloxane can make it easy to discharge the gas that may be generated by high heat such as plasma used in the entire process of manufacturing the OLED to the outside when formed into the PDL layer or the planarization layer. Therefore, it is possible to fundamentally prevent the generated gas from reacting with the OLED to cause malfunction.

[0057] [B] Acrylic multifunctional monomer

[0058] The photosensitive resin composition according to an embodiment of the present invention may further include an acrylic multifunctional monomer having different difunctional or higher-functional acrylic esters.

[0059] The acrylic multifunctional monomer is not particularly limited, but difunctional or trifunctional or higher-functional (meth)acrylates are preferred because of their good polymerizability and improved strength of the resulting insulating film. In particular, trifunctional or higher-functional (meth)acrylates are preferred.

[0060] Examples of the difunctional (meth)acrylates include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, bisphenoxyethanolfluorenedimethacrylate, and the like.

[0061] In addition, examples of the trifunctional or higher (meth) acrylates include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tris(2-acryloyloxyethyl)phosphate, tris(2-methacryloyloxyethyl)phosphate, etc. In addition, monofunctional, difunctional or trifunctional or higher (meth) acrylates may be used alone or in combination of two or more.

[0062] The amount of the acrylic multifunctional monomer used may be in the range of 20 to 300 parts by weight, more preferably 40 to 250 parts by weight, and most preferably 80 to 120% by weight per 100 parts by weight of the polysiloxane resin. When the amount is in this range, a photosensitive resin composition having high elasticity and high sensitivity can be manufactured, the film thickness of the obtained photosensitive resin can be easily controlled, and a photosensitive resin having excellent strength and adhesion can be provided.

[0063] [C] Photoinitiator

[0064] According to an embodiment of the present invention, the photosensitive resin composition may further include a photoinitiator, wherein the photoinitiator is at least one selected from the group consisting of O-acyl oxime photoinitiators, acetophenone photoinitiators and benzophenone photoinitiators.

[0065] Examples of O-acyl oxime compounds as photoinitiators include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl oxime), 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl oxime), -4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl]-9.H.-carbazole-3-yl]-1-(O-acetyloxime)), 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-1,2-nonane-2-oxime-O-benzoate, 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-1,2-nonane-2

[0066] -oxime-O-acetate, 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-1,2-pentane-2-oxime-O-acetate, 1-[9-ethyl-6-benzoyl-9.H.-carbazole-3-yl]-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-one oxime-O-acetate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9.H.-carbazole-3-yl]-ethane-1-one oxime-O-benzoate, etc.

[0067] For the O-acyl oxime photoinitiator, other photoinitiators can be added in the range of 100 to 500 weight % of the total weight of the photoinitiator for use. For example, acyloins, acyloin ethers, acetophenones, benzophenones, quinones, halogen compounds, acylphosphine oxides and peroxides can be added for use.

[0068] As for other photoinitiators, specifically, for example, there are benzyl alcohol (benzyl), diacetyl, benzoin, o-xylene (o-Toluene), p-xylene (p-Toluene), anisole, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetophenone, p-dimethylaminoacetophenone, α,α'-dimethoxyacetoxybenzophenone, 4,4-bis-(diethylamino)-benzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p- Methoxyacetophenone, 2-methyl-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, anthraquinone, 1,4-naphthoquinone, phenacyl chloride, tribromomethylphenyl sulfone, tris(trichloromethyl)-s-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, benzoyl peroxide, di-tert-butyl peroxide, etc.

[0069] Regarding the amount of the photoinitiator used in the present invention, it is preferably 0.1 to 20.0 parts by weight, more preferably 1.0 to 15.0 parts by weight, relative to 100 parts by weight of the polysiloxane resin. For example, the photoinitiator may include 3 to 6.0% by weight of an O-acyl oxime photoinitiator and 5 to 10% by weight of at least one of an acetophenone and a benzophenone photoinitiator relative to 100 parts by weight of the polysiloxane resin.

[0070] When used within this range, a photosensitive resin composition having a good balance between the heat resistance and solvent resistance of the photosensitive resin and the controllability of the pattern shape after development is provided.

[0071] [D] Additives

[0072] The photosensitive resin composition according to an embodiment of the present invention may further include at least one of a silane coupling agent, a leveling agent, an epoxy curing agent and a curing accelerator as an additive.

[0073] [D-1] Silane coupling agent

[0074] A silane coupling agent can be used in the photosensitive composition containing polysiloxane according to one embodiment of the present invention to improve the adhesion to the substrate. Examples thereof include silane coupling agents having reactive functional groups such as carboxyl, methacryloyl, isocyanate, and epoxy groups. More specifically, they can be trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyl triethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2-(3',4'-epoxycyclohexyl)ethyltrimethoxysilane, and the like. The silane coupling agent may be used alone or in combination of two or more thereof. The silane coupling agent may be adjusted to a ratio of 1 wt % or less based on the entire photosensitive resin composition.

[0075] [D-2] Leveling agent

[0076] The photosensitive resin composition according to an embodiment of the present invention may further include a leveler.

[0077] According to one embodiment of the present invention, a leveling agent may be further added to the photosensitive resin composition as a flattening material for improving coating properties. Therefore, as commercially available products of the leveling agent, for example, R-08, R-475, R-30 (manufactured by DIC Corporation), BM-1000, BM-1100 (manufactured by BM CHEMIE Corporation), FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431 (manufactured by Sumitomo 3M Co., Ltd.), SAFLON S-112, SAFLON S-113, SAFLON S-131, SAFLON S-141, SAFLON S-145, SAFLON S-382, SAFLON SC-101, SAFLON SC-102, SAFLON SC-103, SAFLON SC-104, SAFLON SC-105, SAFLON Fluorine-based or silicon-based surfactants such as SC-106 (manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, and DC-190 (manufactured by TORAY SILICON Co., Ltd.). These leveling agents may be used alone or in combination of two or more. The amount of the leveling agent may be within a range of 1% by weight or less based on the entire photosensitive resin composition.

[0078] [D-3] Epoxy curing agent

[0079] The photosensitive resin composition according to an embodiment of the present invention may further include an epoxy curing agent.

[0080] In the photosensitive resin composition of the present invention, as the epoxy curing agent, amines, acid anhydrides, imidazoles, isocyanines, thiol compounds, etc. can be used, and more specifically, amine compounds such as diethylenetriamine (DETA), triethylenetetramine (TETA), triethylenepentamine (TEPA), diaminodiphenylmethane (DDM), diaminodiphenyl sulfone (DDS), polyamide amine, dicyandiamide, etc. can be used; polyamide resin, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. can be used. anhydride), methylhydrophthalic anhydride and other anhydride compounds; 2MZ, 2E4MZ and other imidazole compounds; isocyanine compounds; and thiol compounds such as polythiol, etc. These can be used alone or in combination of two or more.

[0081] Regarding the content of the epoxy curing agent, in order to further improve the heat resistance and adhesion strength and prevent the curing of the insulating layer from causing a decrease in molding characteristics such as bendability (bending processability) and stamping processability, it is preferably in the range of 0.1 to 10 parts by weight relative to 100 parts by weight of the acrylic copolymer.

[0082] [D-4] Curing accelerator

[0083] The photosensitive resin composition according to an embodiment of the present invention may further include a curing accelerator.

[0084] Examples of the curing accelerator include amine complexes of boron trifluoride, imidazole derivatives, organic acids such as phthalic anhydride and trimellitic anhydride, but are not limited thereto. Preferably, examples of the curing accelerator include imidazole derivative curing accelerators, specifically 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and derivatives thereof. Examples of the derivatives include cyanoethyl derivatives, carboxylic acid derivatives, hydroxymethyl derivatives, but are not limited thereto. Such curing accelerators can be used alone or in combination of two or more.

[0085] The content of the curing accelerator is preferably in the range of 0.1 to 10 parts by weight relative to 100 parts by weight of the polysiloxane resin.

[0086] [E] Solvent

[0087] The photosensitive resin composition according to one embodiment of the present invention may further include a solvent.

[0088] The photosensitive resin composition according to one embodiment of the present invention includes a solvent. The solvent may include one or a mixture of two or more of tetrahydropyran, xylene, dichlorobenzene, propylene glycol methyl ether, propylene glycol monomethyl ether, γ-butyrolactone, etc., in addition to dimethylformamide, N-methylpyrrolidone, dimethylacetamide, and dimethyl disulfoxide. In addition, ethyl lactate or 4-butoxyethanol may be added to improve coating properties.

[0089] Technical Effects

[0090] The photosensitive resin composition containing polysiloxane according to the present invention prepared in this way utilizes the characteristics of siloxane such as low dielectric constant, excellent insulating properties, heat resistance that can maintain a stable form to about 400° C., moisture absorption rate that is not easy to absorb moisture, acid resistance that can withstand strong acidic substances, etc. to form a PDL layer that divides the boundaries between the pixels of the OLED display device and insulates them, or a planarization layer that is evenly formed at the bottom of the PDL layer and has insulating properties. It can not only form a basically very stable pattern, but also prevent fatal defects caused by moisture when the OLED is working. DETAILED DESCRIPTION

[0091] The following is a detailed description of the photosensitive resin composition containing polysiloxane according to the embodiment of the present invention with reference to the synthesis examples, embodiments and tables. The present invention can be subjected to various changes and can have various forms, which are described in detail herein. However, this is not intended to limit the present invention to a specific disclosure mode, and it should be understood that it includes all changes, equivalents and even substitutes included in the concept and technical scope of the present invention.

[0092] [Synthesis Example 1: Synthesis of (meth)acrylic copolymer resin (A1)]

[0093] In a flask equipped with a cooling tube with a drying tube and a stirrer, 2 parts by weight of octane mercaptan, 2 parts by weight of 2,2'-disazo-(2,4-dimethylvaleronitrile), 200 parts by weight of propylene glycol monomethyl ether acetate, 25 parts by weight of 2-carboxyethyl acrylate, 20 parts by weight of acrylic acid, 25 parts by weight of dicyclopentany l methacrylate, 10 parts by weight of styrene monomer, and 20 parts by weight of 2-methyl-acrylic acid 4-(2-methyl-acryloyloxymethyl)-cyclohexyl ester were added, and the air in the flask was replaced with nitrogen. The solution temperature was raised to 60° C. while slowly stirring, and the temperature was maintained for 6 hours to polymerize to obtain a solution of a copolymer [A-1] represented by the following [Chemical Formula 6]. The weight average molecular weight of the copolymer resin [A-1] was 7000 g / mol.

[0094] [Synthesis Example 2: Synthesis of Siloxane Resin (A2)]

[0095] In a 1L three-necked flask, 47.22 g (0.2 mol) of glycidoxypropyltriethoxysilane for forming the residue represented by the chemical formula 2, 47.22 g (0.2 mol) of r-acryloyloxypropyltriethoxysilane for forming the residue represented by the chemical formula 3, and 47.22 g (0.2 mol) of r-acryloyloxypropyltriethoxysilane for forming the residue represented by the chemical formula 4 were added. 69.10 g (0.25 mol) of 1,1,1,3,3,3-hexafluoro-2-((6-(2-triethoxysilyl)ethyl)decahydro-1,4:5,8-dimethylnaphthalen-2-yl)methyl)propan-2-ol for forming the residue represented by the chemical formula 5, 266.12 g (0.5 mol) of triethoxy(2-(4-(trifluoromethyl)cyclohexyl)ethyl)silane for forming the residue represented by the chemical formula 6 y(2-(4-(trifluoromethyl)cyclohexyl)ethyl)silane) 68.5g (0.2mol), diacetone alcohol 224.64g, and a phosphoric acid aqueous solution in which 0.129g of phosphoric acid was dissolved in 53g of water were added over 10 minutes while stirring at room temperature. After that, the flask was immersed in a 45°C oil bath and stirred for 40 minutes under a nitrogen atmosphere of 0.05L per minute, and the oil bath was heated to 120°C within 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and at this time, heating and stirring were carried out for 2 hours (internal temperature was 110 to 120°C) to obtain a polysiloxane (A2) solution. The solid content concentration of the polysiloxane (A2) solution obtained in this way was 25% by weight, and the weight average molecular weight of the polysiloxane (A2) was 6200.

[0096] [Synthesis Example 3: Synthesis of Siloxane Resin (A3)]

[0097] In a 1L three-necked flask, 139.21 g (0.5 mol) of glycidoxypropyltriethoxysilane for forming the residue represented by the chemical formula 2, 69.1 g (0.25 mol) of r-acryloyloxypropyltriethoxysilane for forming the residue represented by the chemical formula 3, and 1,1,1,3,3,3-hexafluoro-2-((6-(2-triethoxysilyl)ethyl)decahydro-1,4:5,8-dimethanonaphthalen-2-yl)methyl)propan-2-ol for forming the residue represented by the chemical formula 5 were added. hyl)propan-2-ol) 157.78 g (0.3 mol), triethoxy (2- (4- (trifluoromethyl) cyclohexyl) ethyl) silane (triethoxy (2- (4- (trifluoromethyl) cyclohexyl) ethyl) silane) 68.5 g (0.2 mol) for forming the residue represented by the chemical formula 6, and diacetone alcohol 255.55 g, while stirring at room temperature, 0.146 g (0.04 wt% based on the input monomer) of phosphoric acid dissolved in 59 g of water was added over 10 minutes. After that, the flask was immersed in a 45°C oil bath and stirred for 40 minutes under a nitrogen atmosphere of 0.05 L per minute, and the oil bath was heated to 120°C within 30 minutes. One hour after the start of the temperature increase, the internal temperature of the solution reached 100°C, and at this time, heating and stirring were carried out for 2 hours (the internal temperature was 110 to 120°C) to obtain a polysiloxane (A3) solution. The solid content concentration of the polysiloxane (A3) solution thus obtained was 21% by weight, and the weight average molecular weight of the polysiloxane (A3) was 3,800.

[0098] [Examples 1-16 and Comparative Examples 1-4: Preparation of Photosensitive Resin Compositions Containing Polysiloxane]

[0099] The components shown in Table 1 below were mixed and stirred for 5 hours to prepare polysiloxane-containing photosensitive resin compositions of the respective Examples and Comparative Examples.

[0100]

Table 1

[0101]

[0102] *Silane coupling agent: γ-glycidoxypropyltrimethoxysilane

[0103] *Leveling agent: BYK-307

[0104] *Epoxy curing agent: triethylenepentamine (TEPA)

[0105] *Curing accelerator: 2-ethyl 4-methylimidazole

[0106] The photosensitive resin composition solution obtained from the examples and comparative examples was subjected to a photolithography process to form a pattern. That is, a glass substrate was used as a transparent substrate for forming a pattern, the composition was coated into a 3.0 μm film, heated (pre-baked) at 100° C. for 90 seconds, and then exposed to ultraviolet light of mixed wavelengths of g, h, and i-line at 60 mJ / cm through a photomask with a pattern. 2 Thereafter, the film was developed with a 0.042 wt % aqueous solution of potassium hydroxide at 25° C. for 80 seconds, and then washed with pure water for 1 minute and heated in an oven at 250° C. for 30 minutes to form a pattern.

[0107] Next, various evaluations were performed in the following manner.

[0108] (1) Evaluation of sensitivity

[0109] The photosensitive resin compositions of the embodiments and comparative examples were coated on a glass substrate to form a film with a thickness of 3.0 μm and subjected to a photolithography process. The pattern size and the pattern mask (based on 10 μm) were set to form a 1:1 exposure as the sensitivity. When the exposure is less than 60 mJ / cm 2 The sensitivity can be considered good when the sensitivity is . The sensitivity evaluation criteria are as follows.

[0110] ≤40mJ / cm 2 :◎,40mJ / cm 2 <○≤60mJ / cm 2 , 60mJ / cm 2 <△≤80mJ / cm 2 ,>80mJ / cm 2 :X

[0111] (2) Resolution evaluation

[0112] The photosensitive resin compositions of the examples and comparative examples were subjected to the photolithography process to confirm the formation of micropatterns. Here, when a line pattern of 10 μm or less was formed, it was considered good. The resolution evaluation criteria were as follows.

[0113] ≤5μm: ◎, 5μm<○≤10μm, 10μm<△≤15μm, >15μm: X

[0114] (3) Evaluation of dielectric constant

[0115] The photosensitive resin composition of the embodiment and the comparative example was coated on a substrate with ITO electrodes to form a film with a thickness of 3.0 μm and subjected to a photolithography process. Platinum was deposited on the film and electrodes were connected to measure the dielectric constant. A dielectric constant of 3.6 to 3.8 was considered good. The dielectric constant evaluation criteria were as follows.

[0116] ≤3.2: ◎, 3.2<○≤3.6, 3.6<△≤4.2, X>4.2

[0117] (4) Evaluation of heat resistance

[0118] Except that a photomask is not used, the photosensitive resin composition of the embodiment and the comparative example is used as the object, and the same photolithography process is implemented to form a cured film, and the weight loss of the obtained sample is measured by TGA analysis equipment. Here, the temperature at which the weight loss relative to the initial weight is 5% is 330 or above, which is considered good. The heat resistance evaluation standard is as follows.

[0119] >350: ◎, 350≥○>330, 330≥△>300, 300≥X

[0120] (5) Evaluation of residual film rate

[0121] After the photosensitive resin composition of the embodiment and the comparative example was coated on a glass substrate to form a film with a thickness of 3.0 μm and subjected to a photolithography process, the residual film rate was determined by measuring the thickness before and after development using a contact thickness gauge (DEKTAK 6M, manufacturer VECCO, USA). The residual film rate was considered good when it was above 80%. The residual film rate evaluation criteria were as follows.

[0122] ≥85%: ◎, 85%>○≥80%, 80%>△≥70%, 70%>X

[0123] (6) Evaluation of adhesion

[0124] After forming a cured film in the same manner as the pattern formation except that no photomask is used, the adhesion between the cured film and the flexible substrate is tested by a cross-cut test.

[0125] The cured film was subjected to the checkerboard scale tape method according to the ATSM-D3359 method, and 100 checkerboard scales were formed on the cured film with a cutter, and then peeled off with 3M tape. The number of checkerboard scales peeled off among the 100 was measured, and the adhesion was considered good if it was 4B. The standards are shown in Table 2 below.

[0126]

Table 2

[0127] 100 ≥80 ≥60 ≥40 ≥20 ≥0％ Classification 5B 4B 3B 2B 1B 0 determination ◎ ○ △ X X X

[0128] The evaluation results of the examples and comparative examples with respect to the items (1) to (6) are shown in Table 3 below.

[0129]

Table 3

[0130] Photosensitive resin Sensitivity Resolution Dielectric constant Heat resistance Residual film rate Adhesion Example 1 ○ ○ △ △ ○ ◎ Example 2 ◎ ◎ ○ ○ ◎ ◎ Example 3 ○ ○ ○ ○ ○ ○ Example 4 △ △ ○ ◎ △ △ Example 5 △ △ △ △ △ ◎ Example 6 ○ ○ ○ ○ ○ ◎ Example 7 △ △ ○ ○ △ ○ Example 8 △ △ ○ ◎ △ △ Example 9 ○ ○ △ △ ○ ◎ Example 10 ◎ ◎ ○ ○ ◎ ◎ Embodiment 11 ○ ○ ○ ○ ○ ○ Example 12 △ △ ○ ◎ △ △ Example 13 △ △ △ △ △ ◎ Embodiment 14 ○ ○ ○ ○ ○ ◎ Embodiment 15 △ △ ○ ○ △ ○ Example 16 △ △ ○ ◎ △ △ Comparative Example 1 × × × × △ △ Comparative Example 2 △ △ ○ ◎ × × Comparative Example 3 × × × × △ △ Comparative Example 4 △ △ ○ ◎ × ×

[0131] ◎: Excellent, ○: Good, △: Fair, ×: Poor

[0132] In the above detailed description of the present invention, reference is made to the preferred embodiments of the present invention, but it is to be understood that any skilled person in the technical field or an ordinary technician in the technical field can make various modifications and changes to the present invention without departing from the scope of the idea of ​​the present invention and the technical field as described in the appended claims.

Claims

1. A photosensitive resin composition comprising: A polysiloxane resin represented by the following Chemical Formula 1; a binder resin including a (meth)acrylic copolymer resin represented by Chemical Formula 7; Acrylic multifunctional monomers having different difunctional or higher acrylates; The photoinitiator is at least one selected from the group consisting of O-acyl oxime photoinitiators, acetophenone photoinitiators and benzophenone photoinitiators; An additive comprising at least one of a silane coupling agent, a leveling agent, an epoxy curing agent, and a curing accelerator; and Solvents, 【Chemical formula 1】 in, k, l, m, and n are natural numbers greater than or equal to 1, R5 to R8 are independently hydrogen or ethoxy, R1 of the chemical formula 1 includes a residue represented by the following chemical formula 2, 【Chemical formula 2】 R2 of the chemical formula 1 includes a residue represented by any one of the following chemical formulas 3 and 4, 【Chemical formula 3】 【Chemical formula 4】 R3 of the chemical formula 1 includes a residue represented by the following chemical formula 5, 【Chemical formula 5】 Wherein, R9 is OH, R 10 and R 11 is CH3 or CF3, R4 of the chemical formula 1 includes a residue represented by the following chemical formula 6, 【Chemical formula 6】 【Chemical formula 7】 In the chemical formula 7, j, k, l, m, and n are integers from 1 to 90, and R 12 , R 13 , R 14 , R 15 , R 16 and R 18 are any one selected from the group consisting of hydrogen, methyl and hydroxymethyl, R 17 is hydrogen or a group forming a carboxylic anhydride or amide structure, X is methyl or cyclohexyl, Y is selected from the group consisting of an alkyl ester having 1 to 12 carbon atoms, an alkyl ester having 2 to 6 carbon atoms substituted with 1 to 2 hydroxyl groups, an alkoxypolyalkylene having 1 to 3 carbon atoms, an ethylene glycol ester having 2 to 3 carbon atoms, and an alkyl ester having 1 to 6 carbon atoms substituted with a phenyl group, and the symbol * is a bonding point.

2. The photosensitive resin composition according to claim 1, characterized in that: The (meth)acrylic copolymer resin has a weight average molecular weight (Mw) ranging from 1,000 to 50,000 g / mol.

3. The photosensitive resin composition according to claim 1, characterized in that: The polysiloxane resin has a weight average molecular weight (Mw) ranging from 1,000 to 20,000 g / mol.

4. The photosensitive resin composition according to claim 1, characterized in that: The polysiloxane resin is in an amount ranging from 10 to 100 wt % based on 100 parts by weight of the (meth)acrylic copolymer resin.

5. The photosensitive resin composition according to claim 1, characterized in that: The acrylic multifunctional monomer includes a trifunctional group in a range of 80 to 120 wt % and a hexafunctional group in a range of 80 to 120 wt % based on 100 parts by weight of the (meth)acrylic copolymer resin.

6. The photosensitive resin composition according to claim 1, characterized in that: The photoinitiator includes at least one of 3 to 6.0 wt % of an O-acyl oxime photoinitiator, 5 to 10 wt % of an acetophenone photoinitiator and a benzophenone photoinitiator based on 100 parts by weight of the (meth)acrylic copolymer resin.

7. The photosensitive resin composition according to claim 1, characterized in that: Based on 100 parts by weight of the (meth)acrylic copolymer resin, 0.1 to 10% by weight of an epoxy curing agent is further included.

8. The photosensitive resin composition according to claim 1, characterized in that: The (meth)acrylic copolymer resin further includes 0.1 to 10% of a curing accelerator based on 100 parts by weight of the (meth)acrylic copolymer resin.

Images