Polysiloxane-containing photosensitive resin composition

Abstract

Disclosed are compositions comprising a polysiloxane resin; a binder resin including a (meth) acrylic copolymer resin; a photosensitizer composed of a 1, 2-quinonediazide compound; comprising at least one of a sensitizer, a silane coupling agent and a leveling agent; and a solvent. Since the photosensitive resin composition contains polysiloxane, the photosensitive resin composition can be used as a PDL (Pixel Defined Laye r) 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 by using the characteristics of improved insulation and heat resistance and very low moisture absorption rate.

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 insulation, improves heat resistance and has improved moisture absorption rate, 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 includes: a polysiloxane resin represented by Chemical Formula 1; a binder resin including a (meth) acrylic copolymer resin represented by Chemical Formula 7; a photosensitizer composed of a 1,2-quinone diazide compound; an additive including at least one of a sensitizer, a silane coupling agent and a leveler; and a solvent.

[0009] [A-1] Polysiloxane resin

[0010]

Chemical formula 1

[0011]

[0012] Here, k, l, m, and n are natural numbers greater than or equal to 1. 5 To R 8 It is hydrogen or ethoxy group.

[0013] Among them, R 1 A residue represented by the following Chemical Formula 2 may be included.

[0014]

Chemical formula 2

[0015]

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

[0017] In addition, using R represented by the chemical formula 2 1 The PDL layer or planarization layer formed by the photosensitive resin composition not only has improved adhesion on an electrode or a substrate, but also has excellent acid resistance to a strong acid etching solution in a photolithography process.

[0018] Among them, R 2 A residue represented by any one of the following Chemical Formulae 3 and 4 may be included.

[0019]

Chemical formula 3

[0020]

[0021]

Chemical formula 4

[0022]

[0023] The residues represented by the chemical formulae 3 and 4 are formed by opening some double bond portions so that other functional groups can be attached thereto. Therefore, when using a residue comprising R represented by any one of the chemical formulae 3 and 4, 2 When the photosensitive resin composition containing polysiloxane is used to form a PDL layer or a planarizing layer, it can function as a functional group connection initiator or a curing accelerator, or can improve the residual film rate by adjusting the molecular weight through the opened double bond part.

[0024] Wherein, R of the chemical formula 1 3 A residue represented by the following Chemical Formula 5 may be included.

[0025]

Chemical formula 5

[0026]

[0027] In chemical formula 5, R 9 For OH, R 10 and R 11 CH 3 or CF 3 .

[0028] The use of R represented by the chemical formula 5 can reduce 3 The dielectric constant of the PDL layer or the planarization layer formed by the photosensitive resin composition containing polysiloxane can be increased, thereby having improved insulation properties. In particular, R 3 The residue having a trifluoromethyl group (CF 3 ) The more there are, the lower the dielectric constant will be, thus further improving the insulation properties.

[0029] In addition, the hydroxyl group (OH) in the residue represented by the chemical formula 5 can not only improve the developability in the photolithography process, but also play the role of a functional group to which the added photoacid generator (PAC) can be attached.

[0030] Among them, R in chemical formula 1 4 A residue represented by the following Chemical Formula 6 may be included.

[0031]

Chemical formula 6

[0032]

[0033] The residue (R 4 ) can have improved transparency. Therefore, when the PDL layer or the planarization layer is formed by a photolithography process, it can be patterned more accurately by increasing the sensitivity to light. In particular, the residue (R 4 ) in trifluoromethyl (CF 3) 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 properties.

[0034] [A-2] (Meth)acrylic acid copolymer resin

[0035] The (meth)acrylic copolymer resin may include a copolymer represented by Chemical Formula 7 below.

[0036]

Chemical formula 7

[0037]

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] [B] Photosensitizer

[0056] The photosensitive resin composition according to one embodiment of the present invention may further include a photosensitizer composed of diazonaphthoquinone compounds represented by the following Chemical Formulas 8 to 13.

[0057]

Chemical formula 8

[0058]

[0059]

Chemical formula 9

[0060]

[0061]

Chemical formula 10

[0062]

[0063]

Chemical formula 11

[0064]

[0065]

Chemical formula 12

[0066]

[0067]

Chemical formula 13

[0068]

[0069] In the above Chemical Formulae 8 to 13, D is any one selected from hydrogen, and substituents of the following Chemical Formulae 14 and 15.

[0070]

Chemical formula 14

[0071] 1,2,4-diazonaphthoquinone diazide

[0072]

[0073]

Chemical formula 15

[0074] 1,2,5-Diazonaphthoquinonediazide

[0075]

[0076] In addition, for the above-described photosensitizer, it is preferred to use a 1,2-quinonediazide compound as the photosensitive compound. Specific examples of the 1,2-quinonediazide compound include 1,2-quinonediazide 4-sulfonate, 1,2-quinonediazide 5-sulfonate, 1,2-quinonediazide 6-sulfonate, etc. This quinonediazide compound is obtained by reacting a naphthoquinonediazidesulfonic acid halogen compound and a phenol compound in the presence of a weak base. Here, specific examples of the phenolic compound include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2' or 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy 4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy 3'-methoxybenzophenone, 2,3,4,2' or 2,3,4,6'-pentahydroxybenzophenone, 2,4,6,3', 2,4,6,4' or 2,4,6,5'-hexahydroxybenzophenone, 3,4,5,3', 3,4,5,4' or 3,4,6'-tetrahydroxybenzophenone. ,4,5,5'-hexahydroxybenzophenone, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1,1,1-tris(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]benzene]ethylidene]bisphenol, bis(2,5-dimethyl 4-hydroxyphenyl)-2-hydroxyphenylmethane, etc., which can be used alone or in combination of two or more.

[0077] When synthesizing the polymer as described above, the degree of esterification is preferably about 50% to 85%. When the degree of esterification is less than about 50%, the residual film rate may tend to deteriorate, and when it exceeds about 85%, the storage stability may tend to decrease.

[0078] In addition, regarding the 1,2-quinonediazide compound, it is preferred to use about 5 to 100 parts by weight, and more preferably 10 to 50 parts by weight, for 100 parts by weight of the acrylic copolymer. When the amount of the 1,2-quinonediazide used is less than about 5 parts by weight, the difference in solubility between the exposed part and the non-exposed part becomes small, so it is difficult to form a pattern; when it exceeds about 100 parts by weight, a large amount of unreacted 1,2-quinonediazide remains when light is irradiated for a short time, resulting in too low solubility in an alkaline aqueous solution, which may make it difficult to develop.

[0079] In addition, the photosensitizer is a diazide compound, which can be prepared by the esterification reaction of trihydroxybenzophenone with 2-diazo-1-naphthol-5-sulfonic acid to form 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonate and the esterification reaction of tetrahydroxybenzophenone with 2-diazo-1-naphthol-5-sulfonic acid to form 2,3,4,4'-tetrahydroxybenzophenone-1,2

[0080] -naphthoquinone diazide-5-sulfonate (2,3,4,4'tetrahydroxybenzophenone-1,2-naphthoquinone diazide-5-sulfonate) can be used alone or in combination. Here, the diazide photosensitive compound can be prepared by reacting polyhydroxybenzophenone with diazide compounds such as 1,2-naphthoquinone diazide and 2-diazo-1-naphthol-5-sulfonic acid.

[0081] [D] Additives

[0082] According to an embodiment of the present invention, the photosensitive resin composition may further include at least one of a sensitizer, a silane coupling agent and a leveler as an additive.

[0083] [D-1] Sensitizer

[0084] The photosensitive resin composition of the present invention may further include a sensitizer for improving sensitivity. As the sensitizer, a sensitizer including a hydroxyphenyl group may be cited. For example, a sensitizer including a hydroxyphenyl group as at least one of the chemical formulas 7 to 12 may be used alone or in combination of two or more.

[0085] [D-2] Silane coupling agent

[0086] In addition, 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.

[0087] [D-3] Leveling agent

[0088] 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.

[0089] [E] Solvent

[0090] 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.

[0091] Technical Effects

[0092] 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

[0093] The following is a detailed description of the polysiloxane-containing photosensitive resin composition according to the embodiment of the present invention with reference to the synthesis examples, embodiments and diagrams. The present invention can be subjected to various modifications and can have various forms, and specific embodiments are illustrated in the figures and described in detail in the text. However, this is not intended to limit the present invention to a specific disclosure method, and it should be understood that it includes all modifications, equivalents and even substitutes included in the concept and technical scope of the present invention.

[0094] [Synthesis Example 1: Synthesis of (meth)acrylic copolymer resin (A1)]

[0095] 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 dicyclopentyl 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 temperature of the solution was raised to 60° C. while slowly stirring, and the temperature was maintained for 6 hours to allow polymerization to obtain a solution of a copolymer [A-1] represented by the following [Chemical Formula 6]. The weight average molecular weight of the copolymer [A-1] was 7000 g / mol.

[0096] [Synthesis Example 2: Synthesis of Siloxane Resin (A2)]

[0097] In a 1L three-necked flask, 83.53 g (0.3 mol) of glycidoxypropyltriethoxysilane for forming the residue represented by the chemical formula 2, 83.53 g (0.3 mol) of r-acryloyloxypropyltriethoxysilane for forming the residue represented by the chemical formula 3, and 83.53 g (0.3 mol) of r-acryloyloxypropyltriethoxysilane for forming the residue represented by the chemical formula 4 were added. 1,1,1,3,3,3-hexafluoro-2-((6-(2-(triethoxysilyl)ethyl)decahydro-1,4:5,8-dimethanonaphthalen-2-yl)methyl)propan-2-ol) 157.78 g (0.3 mol) for forming the residue represented by the chemical formula 6; 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) 157.78 g (0.3 mol) 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 0.89g 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 (A1) solution. The solid content concentration of the polysiloxane (A1) solution obtained in this way was 23% by weight, and the weight average molecular weight of the polysiloxane (A1) was 3400.

[0098] [Synthesis Example 3: Synthesis of Siloxane Resin (A3)]

[0099] 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.

[0100] [Examples 1-16 and Comparative Examples 1-8: Preparation of Photosensitive Resin Compositions Containing Polysiloxane]

[0101] 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.

[0102]

Table 1

[0103]

[0104] 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 layer, 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 80 mJ / cm through a photomask with a pattern. 2 Then, the film was developed with a 2.38 wt % aqueous solution of tetramethylammonium hydroxide at 25° C. for 60 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.

[0105] Next, various evaluations were performed in the following manner.

[0106] (1) Evaluation of sensitivity

[0107] 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 pattern size and the pattern mask (based on 20 μm) were used as the exposure sensitivity in a ratio of 1:1. When the exposure was lower than 120 mJ / cm 2 The sensitivity can be considered good when the sensitivity is . The sensitivity evaluation criteria are as follows.

[0108] ≤1000mJ / cm 2 :◎,100mJ / cm 2 <○≤120mJ / cm 2 , 120mJ / cm 2 <△≤150mJ / cm 2 ,>150mJ / cm 2 :X

[0109] (2) Resolution evaluation

[0110] 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.

[0111] ≤5μm: ◎, 5μm<○≤10μm, 10μm<△≤15μm, >15μm: X

[0112] (3) Evaluation of dielectric constant

[0113] 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.

[0114] ≤3.2: ◎, 3.2<○≤3.6, 3.6<△≤4.2, X>4.2

[0115] (4) Evaluation of heat resistance

[0116] 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.

[0117] >350: ◎, 350≥○>330, 330≥△>300, 300≥X

[0118] (5) Evaluation of residual film rate

[0119] After the photosensitive resin composition of the embodiment and the comparative example was coated on a glass substrate to form a thin 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 70%. The residual film rate evaluation criteria were as follows.

[0120] ≥85%: ◎, 85%>○≥80%, 80%>△≥70%, 70%>X

[0121] (6) Evaluation of adhesion

[0122] After forming a cured film in the same manner as the pattern formation except that no photomask was used, the adhesion between the cured film and the glass substrate was tested by a cross-cut test.

[0123] 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.

[0124]

Table 2

[0125] 100 ≥80 ≥60 ≥40 ≥20 ≥0％ Classification 5B 4B 3B 2B 1B 0 determination ◎ ○ △ X X X

[0126] The evaluation results of the examples and comparative examples with respect to the items (1) to (6) are shown in Table 3 below.

[0127]

Table 3

[0128] 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 △ △ ○ ◎ △ △ Embodiment 13 △ △ △ △ △ ◎ Embodiment 14 ○ ○ ○ ○ ○ ◎ Embodiment 15 △ △ ○ ○ △ ○ Example 16 △ △ ○ ◎ △ △ Comparative Example 1 × × × △ △ △ Comparative Example 2 △ △ ○ ◎ × × Comparative Example 3 × × × △ △ △ Comparative Example 4 △ △ ○ ◎ × × Comparative Example 5 × × × △ △ △ Comparative Example 6 △ △ ○ ◎ × × Comparative Example 7 × × × △ △ △ Comparative Example 8 △ △ ○ ◎ × ×

[0129] ◎: Very good, ○: Good, △: Average, ×: Poor

[0130] 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 comprising a (meth)acrylic copolymer resin represented by the following Chemical Formula 7; a photosensitizer consisting of a 1,2-quinonediazide compound; An additive comprising at least one of a sensitizer, a silane coupling agent and a leveler; and Solvents, 【Chemical formula 1】 in, k, l, m, and n are natural numbers greater than or equal to 1, R5 to R8 are 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 photosensitizer is composed of a naphthoquinone compound represented by any one of the following chemical formulas 8 to 13: [Chemical Formula 8] 【Chemical formula 9】 【Chemical formula 10】 【Chemical formula 11】 【Chemical formula 12】 【Chemical formula 13】 In the chemical formulae 8 to 13, D is any one selected from hydrogen, and substituents of the following chemical formulae 14 and 15, 【Chemical formula 14】 1,2,4-Diazonaphthoquinonediazide 【Chemical formula 15】 1,2,5-Diazonaphthoquinonediazide 6. The photosensitive resin composition according to claim 1, characterized in that: The (meth)acrylic copolymer resin includes 20 to 25 weight % of the photosensitizer based on 100 weight % of the (meth)acrylic copolymer resin.

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