KR20170012923A - Photo-sensitive Composition, Cured Film Prepared Therefrom, and Device Incoporating the Cured Film - Google Patents
Photo-sensitive Composition, Cured Film Prepared Therefrom, and Device Incoporating the Cured Film Download PDFInfo
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- KR20170012923A KR20170012923A KR1020150105567A KR20150105567A KR20170012923A KR 20170012923 A KR20170012923 A KR 20170012923A KR 1020150105567 A KR1020150105567 A KR 1020150105567A KR 20150105567 A KR20150105567 A KR 20150105567A KR 20170012923 A KR20170012923 A KR 20170012923A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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Abstract
Description
A photosensitive resin composition, a cured film formed therefrom, and a device having the cured film.
In order to realize a more precise and high resolution in a liquid crystal display, an organic EL display, etc., the aperture ratio of a display device must be increased. This is because a transparent planarizing film is provided as a protective film on the TFT substrate to overlap the data lines and the pixel electrodes, do.
Therefore, a low dielectric constant, high heat resistance, high transparency, and chemical resistance are required as the required characteristics of a material for forming an organic insulating film for a TFT substrate. Conventionally, a photosensitive resin composition comprising an acrylic resin and a quinone diazide compound is mainly used Has come. However, the acrylic-based material decomposes at a high temperature of 200 DEG C or higher to lower the film thickness, and the transparent film is colored due to insufficient heat resistance as the substrate is processed at a high temperature, thereby lowering the transmittance.
In addition, silsesquioxane is known as a material having high heat resistance and high transparency. In particular, a photosensitive composition comprising an acrylic copolymer and a quinone diazide compound in which a silsesquioxane compound having an acrylic group added to a specific silsesquioxane, an unsaturated compound containing an unsaturated carboxylic acid and an epoxy group, and an olefinically unsaturated compound are copolymerized Has been proposed. However, since these compounds also have a high content of organic compounds, they have a problem of heat resistance which is colored and yellow after being cured after being cured at a high temperature of 250 ° C. or higher and have a low permeability. Since the residual film ratio after development is low, a flat film is not formed or NMP the chemical resistance to a solvent such as pyrrolidone, tetramethylammonium hydroxide (TMAH) solution and 10% NaOH is also reduced.
One embodiment provides a photosensitive resin composition having a high retention rate, mechanical strength, and chemical resistance, and having high transmittance, heat resistance, and low dielectric constant properties even after high temperature curing.
Another embodiment provides a cured film obtained by curing the composition.
Another embodiment provides an element comprising the cured film.
One embodiment provides a photosensitive resin composition comprising a siloxane compound represented by the following formula (1):
[Chemical Formula 1]
(R 1 R 2 R 3 SiO 1/2) M (R 4 R 5 SiO 2/2) D (R 6 SiO 3/2) T1 (O 3/2 -Y-SiO 3/2) T2 (SiO 4 / 2 ) Q
In Formula 1,
R 1 to R 6 are each independently selected from the group consisting of hydrogen, hydroxy, halogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, A substituted or unsubstituted C1 to C30 arylalkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 heteroaryl group, a substituted or unsubstituted C2 A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 alkoxy group, R (C = O) - Or an unsubstituted or substituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group), or combinations thereof,
Y is a single bond, oxygen, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 hetero A substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, or a combination thereof,
0 < 0.5 < 0.5, 0.5 <
M + D + T1 + T2 + Q = 1.
In the formula (1), M, D and Q are all 0, and 0.8 < T1 < 1, and 0 <
In the formula (1), M, D and Q are all 0, 0.85? T1 <1, and 0 <T2? 0.15.
In the general formula (1), M, D and Q are all 0, 0.9? T1 <1, and 0 <T2? 0.1.
In the formula (1), M, D and Q are all 0, 0.95? T1 <1, and 0 <T2? 0.05.
In Formula (1), at least one of R 1 to R 6 includes a substituted or unsubstituted C6 to C30 aryl group, and at least one of R 1 to R 6 may include a substituted or unsubstituted C1 to C30 alkyl group have.
In Formula (1), Y may be a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, or a substituted or unsubstituted C6 to C30 arylene group.
The molecular weight of the compound of formula (1) may be about 1,000 to 500,000 in terms of the weight average molecular weight (Mw) in terms of a polystyrene standard sample measured by Gel Permeation Chromatography (GPC).
The composition may further comprise a solvent.
The composition may be a negative type photosensitive resin composition.
According to another embodiment, there is provided a cured film obtained by curing the composition.
The cured film may be used as a flattening film for a thin film transistor (TFT) substrate of a liquid crystal display element or an organic EL display element, a protective film or insulating film of a touch panel sensor element, an interlayer insulating film of a semiconductor element, a flattening film for a solid- Or a core or a clad material of an optical waveguide of an optical semiconductor device .
According to another embodiment, there is provided an element comprising the cured film.
The light-sensitive resin composition containing the siloxane compound represented by Formula 1 has a high residual film ratio, mechanical strength, and chemical resistance, and has high transmittance, heat resistance, and low dielectric constant characteristics even after high temperature curing, ) Planarizing film for a substrate, an interlayer insulating film of a semiconductor device, and the like.
Hereinafter, exemplary embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
Unless otherwise defined herein, "substituted" means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, A thio group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkenyl group, a C2 to C20 alkenyl group, A C 1 to C 30 arylalkyl group, a C 7 to C 30 arylalkyl group, a C 1 to C 30 alkoxy group, a C 1 to C 20 heteroalkyl group, a C 3 to C 20 heteroarylalkyl group, a C 3 to C 30 cycloalkyl group, a C 3 to C 15 cycloalkenyl group, C6 to C15 cycloalkynyl groups, C3 to C30 heterocycloalkyl groups, and combinations thereof.
Also, unless otherwise defined herein, 'hetero' means containing at least one heteroatom selected from N, O, S, and P.
Unless otherwise specified herein, 'combination' means mixing or copolymerization.
Hereinafter, the photosensitive resin composition according to one embodiment will be described.
The photosensitive resin composition according to one embodiment includes a siloxane compound represented by the following Formula 1:
[Chemical Formula 1]
(R 1 R 2 R 3 SiO 1/2) M (R 4 R 5 SiO 2/2) D (R 6 SiO 3/2) T1 (O 3/2 -Y-SiO 3/2) T2 (SiO 4 / 2 ) Q
In Formula 1,
R 1 to R 6 are each independently selected from the group consisting of hydrogen, hydroxy, halogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, A substituted or unsubstituted C1 to C30 arylalkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 heteroaryl group, a substituted or unsubstituted C2 A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 alkoxy group, R (C = O) - Or an unsubstituted or substituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group), or combinations thereof,
Y is a single bond, oxygen, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 hetero A substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, or a combination thereof,
0 < 0.5 < 0.5, 0.5 <
M + D + T1 + T2 + Q = 1.
As shown in the above formula (1), the siloxane compound contains at least 0.5 or more structural units represented by (R 6 SiO 3/2 ) in the compound, and (O 3/2 -Y-SiO 3/2 ) May be contained in an amount of less than 0.2.
(O 3/2 -Y-SiO 3/ 2) when including a structural unit represented by the above-described range, the photosensitive resin composition comprising a compound represented by the above formula (1), when cured dense structure with a sufficient cross-linking , It can have high mechanical strength, chemical resistance, and high retention rate.
In addition, (O 3/2 -Y-SiO 3 /2) structural unit represented by the cross-linking agent, and a role in the compound represented by the formula (1), therefore, by including appropriately adjusted within the range of the structural unit , The hardness of the coating film can be easily controlled and the hardness of the coated film can be improved. In addition, the coated film having a high hardness can effectively prevent the penetration of the organic solvent, thereby solving the problem of the residual film ratio, An organic insulating film excellent in chemical resistance after curing can be realized.
In one embodiment, T1 is selected such that 0.6? T1 <1, for example 0.65 T1 <1, eg 0.7 T1 <1, eg 0.75 T1 <1, eg 0.8 T1 1, for example, 0.85? T1 <1, for example, 0.9? T1 <1, for example, 0.95? T1 <1.
In one embodiment, T2 is selected from the group consisting of 0 < T2 < 0.2, e.g. 0 <T2 0.17, for example 0 <T2 0.15, For example, 0 < T0 < = 0.0, for example 0 & ? 0.06, for example, 0 <T2? 0.05, for example, 0 <T2? 0.03.
In one embodiment, M, D, and Q in formula (1) are all 0, and 0.8 <T1 <1, and 0 <T2 <0.2.
In another embodiment, M, D, and Q in Formula 1 are all 0, 0.85 < T1 < 1, and 0 <
In another embodiment, M, D, and Q in formula (1) are all 0, 0.9 < T1 < 1, and 0 <
In another embodiment, M, D, and Q in formula (1) are all 0, 0.95? T1 <1, and 0 <T2? 0.05.
In Formula (1), at least one of R 1 to R 6 includes a substituted or unsubstituted C6 to C30 aryl group, and at least one of R 1 to R 6 may include a substituted or unsubstituted C1 to C30 alkyl group have.
In Formula 1, Y may be a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, or a substituted or unsubstituted C6 to C30 arylene group.
The compound represented by the formula (1) is, for example, R 1 R 2 R 3 SiZ 1 , A monomer represented by R 4 R 5 SiZ 2 Z 3 and a monomer represented by R 6 SiZ 4 Z 5 Z 6 , A monomer represented by SiZ 7 Z 8 Z 9 Z 10 , and a monomer represented by Z 11 Z 12 Z 13 Si-Y-SiZ 14 Z 15 Z 16 by hydrolysis and condensation polymerization. Wherein the definitions of R 1 to R 6 are as defined above, and Z 1 to Z 16 are each independently a C 1 to C 6 alkoxy group, a hydroxy group, a halogen, a carboxyl group, or a combination thereof.
The hydrolysis and polycondensation reaction for preparing the compound represented by the formula (1) can be carried out by a general method well known to those skilled in the art. For example, adding a solvent, water and, if necessary, a catalyst to the above mixture of monomers and stirring at a temperature of 50 ° C to 150 ° C, for example, 90 ° C to 130 ° C for 0.5 hours to 100 hours do. During the stirring, the hydrolysis by-products (alcohol such as methanol) and condensation by-products can be distilled and removed by distillation, if necessary.
The reaction solvent is not particularly limited, but usually the same solvent as that contained in the photosensitive resin composition containing the compound of Formula 1 can be used.
The amount of the solvent to be added may be 10 to 1000 parts by weight based on 100 parts by weight of the total weight of the monomers. The amount of water to be used for the hydrolysis reaction may be in the range of 0.5 to 3 mol per 1 mol of the hydrolyzable group.
The catalyst to be added is not particularly limited, but an acid catalyst, a base catalyst and the like can be used. The amount of the catalyst to be added may be in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the total weight of the monomers.
The compound represented by the formula (1) may be used alone or in combination of two or more.
The photosensitive resin composition may further comprise a solvent.
The compound represented by Formula 1 may be in a solid or liquid state, and in the case of a solid, the compound may be used in a state dissolved in a solvent. In addition, even when the compound is a liquid, the viscosity of the composition can be easily controlled by diluting it in a solvent.
The molecular weight of the compound of formula (I) is preferably about 1,000 to about 500,000, for example, about 1,000 to about 100,000, for example, about 1,000 to about 500,000 in terms of a polystyrene standard sample measured by Gel Permeation Chromatography (GPC) 2,000 to 50,000.
When the weight average molecular weight of the compound is 1,000 or more, cracks do not occur on the surface during curing, and a preferable thickness of the cured film can be realized. When the weight average molecular weight is 500,000 or less, the surface flatness can be improved by maintaining the viscosity required for coating.
The photosensitive resin composition may be a negative or positive photosensitive resin composition.
When the photosensitive resin composition is used as a negative type photosensitive resin composition, the negative type photosensitive resin composition may be prepared by dissolving the composition in a solvent so as to have a proper viscosity A coating film is formed on the substrate by a known method, and a cured film formed from the photosensitive resin composition is obtained by irradiating the coating film with light such as visible light, ultraviolet light or deep ultraviolet light.
The photosensitive resin composition may be a positive photosensitive resin composition in which an exposed portion is developed. The positive photosensitive resin composition generally further comprises a naphthoquinone diazide compound so that the exposed portion can be removed by the developer. Therefore, when a naphthoquinone diazide compound is added to the above photosensitive resin composition to form a coating film on a substrate, and then a light such as visible light, ultraviolet light or deep ultraviolet light is irradiated thereto, the exposed portion is developed by the developer, The unexposed portion can be formed in a desired pattern. At this time, a photomask having a desired pattern may be disposed on the coating film to obtain a desired pattern.
In one embodiment, the photosensitive resin composition may be a negative photosensitive resin composition, wherein the composition is at least one selected from the group consisting of propylene glycol methyl ether acetate (PGMEA), 4-hydroxy- Acetyl lactate, ethyl cellosolve-acetate, gamma-butyrolactone, 2-methoxyethyl acetate, ethyl-beta-ethoxypropionate, normal propyl acetate, n-butyl acetate and And a mixture thereof. For example, the solvent may be at least one selected from propylene glycol methyl ether acetate (PGMEA), 4-hydroxy-4-methyl-2-pentanone, propylene glycol methyl ether, and ethyl acetoacetate, It does not.
The solvent may be contained so that the solid content is 10 to 50% by weight based on the total weight of the photosensitive resin composition. The solid content means a composition component excluding the solvent in the resin composition of the present invention.
The photosensitive resin composition according to the above embodiments may further contain additional components commonly used in the photosensitive resin composition, for example, a silane coupling agent, a surfactant, and the like, if necessary.
The silane coupling agent is added in order to improve the adhesion between the cured film to be formed and the substrate. As the known silane coupling agent, a functional silane compound having a reactive substituent can be used. Examples of the reactive substituent include a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group.
Specific examples of the silane-based coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and preferably at least one selected from the group consisting of Gamma -glycidoxypropyltriethoxysilane and / or gamma -glycidoxypropyltrimethoxysilane having an epoxy group can be used in view of adhesion between the residual film ratio and the substrate, but the present invention is not limited thereto Do not.
The silane coupling agent may be contained in the photosensitive composition in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight based on 100 parts by weight (based on the solid content) of the compound represented by the formula (1). When the content of the silane coupling agent is 0.01 parts by weight or more, the adhesion to the substrate is improved. When the amount is 10 parts by weight or less, the thermal stability is improved at a high temperature, and the occurrence of unevenness after development can be prevented.
The photosensitive resin composition according to the present invention may further include a surfactant to improve the coating performance. Examples of such surfactants include fluorine surfactants, silicone surfactants, nonionic surfactants, and other surfactants.
Examples of the surfactant include FZ2122 (Dow Corning Toray Corporation), BM-1000, BM-1100 (manufactured by BM CHEMIE), Megafac F142D, Copper F172, Copper F173, Copper F183 S-113, S-131 (manufactured by Sumitomo 3M Limited), Florad FC-135, FC-170C, FC-430 and FC-431 , S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105 and SC-106 (Asahi Garasu Co., SH-193, SZ-6032, SF-8428, DC-57, DC (available from Shin-Aichi Kasei Kogyo Co., Ltd.) -190 (manufactured by Toray Silicone Co., Ltd.); 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 , Polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, and other nonionic surfactants; (Manufactured by Shin-Etsu Chemical Co., Ltd.) or (meth) acrylic acid-based copolymer polyflow No. 57,95 (manufactured by Kyoeisha Chemical Co., Ltd.) And can be used in parallel.
The surfactant may be used in an amount of 0.05 to 10 parts by weight, for example, 0.1 to 5 parts by weight based on 100 parts by weight (based on the solid content) of the compound represented by Formula 1. When the content of the surfactant is 0.05 parts by weight or more, the coatability is improved and cracks are not generated on the coated surface, and when the content is 10 parts by weight or less, it is advantageous in terms of cost.
In addition to the above components, the photosensitive resin composition according to one embodiment may further include additional components that are conventionally used in the thermosetting resin composition and / or the photosensitive resin composition, if necessary.
In another embodiment, the present invention provides a cured film made from the photosensitive resin composition.
The cured film may be prepared by a method known in the art, for example, a method in which the photosensitive resin composition is coated on a substrate and cured. Specifically, the curing is performed by pre-bake the photosensitive resin composition coated on the substrate, for example, at 60 ° C to 140 ° C to remove the solvent, and then exposing using a photomask in which a desired pattern is formed, For example, a pattern can be formed on the coating layer by developing with a known alkaline developer such as tetramethylammonium hydroxide (TMAH) solution. Thereafter, if necessary, the patterned coating layer may be post-baked at 180 ° C to 380 ° C for 10 minutes to 5 hours, for example, to produce a desired cured film. The exposure can be performed at an exposure amount of 10 mJ / cm 2 to 500 mJ / cm 2 at a wavelength range of 200 nm to 450 nm.
The cured film according to one embodiment thus produced has a light transmittance of 90% or more, for example, 92% or more, for example, 95% or more at a wavelength of 400 nm in the case of a 2 탆 thick cured film, And has a high film ratio of 70% or more, for example, 75% or more, for example, 80% or more.
The conventional acrylic insulating film has a problem that the transmittance is reduced due to yellowing at 250 DEG C or higher due to the low heat resistance property and the decomposition of the polymer degrades the chemical resistance due to yellowing. Silsesquioxane containing an acrylic group or an epoxy group has heat resistance But the transmittance is still lowered at a high temperature and the residual film ratio after the development is low.
A photosensitive resin composition comprising a silicon compound represented by Formula 1 according to the embodiment, the silicon compound in (O 3/2 -Y-SiO 3/ 2) structural unit represented by the so-called? Die podal (dipodal)? By acting as a crosslinker of the structural unit, it is easy to control the hardness of the cured film produced therefrom, so that it is possible to form a coating film having a high hardness, thereby effectively preventing organic solvents and the like from penetrating through the cured film. Accordingly, the cured film prepared by curing the composition has a problem that the film thickness after development is reduced to solve the problem of a residual film ratio that can not form a flat film, and is also excellent in chemical resistance after curing. In addition, it has higher heat resistance than silsesquioxane copolymerized with an existing acrylic copolymer or organic compound, so that it does not discolor even at a curing temperature of 350 ° C or higher.
The cured film may be a protective film or an insulating film such as a flattening film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, a touch panel sensor element, an interlayer insulating film of a semiconductor element, a flattening film for a solid- Pattern or a core or clad material of an optical waveguide such as an optical semiconductor device.
According to another embodiment, there is provided an element comprising the cured film.
The element may be a liquid crystal display element, an organic EL element, a semiconductor device, a solid-state image pickup element, or the like that includes the cured film as a flattening film of a TFT substrate, but is not limited thereto.
Hereinafter, embodiments of the present invention will be described in detail with reference to examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.
( Example )
Synthetic example 1 to 3 and comparison Synthetic example 1 to 3: Siloxane Preparation of compounds
Synthetic example 1: Siloxane Preparation of compounds
1 kg of a mixed solvent of water and PGMEA in a weight ratio of 1: 6 was introduced into a three-necked flask, and while maintaining the temperature at 10 캜, the respective monomers shown in the following Table 1 were added to the moles % Of the mixture was added dropwise over 2 hours. Stirring was continued for 4 hours after completion of the dropwise addition, toluene was added 1.5 times the weight of the initial PGMEA, stirred for 10 minutes, and the mixture was allowed to stand to remove the lower layer and purified ten times with water to remove chlorine as a reaction byproduct. In addition, the neutral polymer solution of toluene was distilled under reduced pressure to replace the toluene with PGMEA to obtain a solid content of 40% by weight to obtain a polysiloxane represented by the following formula (2). The molecular weight of the compound was measured by gel permeation chromatography (GPC). The molecular weight of the compound was 1,600 g / mole, which was converted into a polystyrene standard sample. The weight average molecular weight of the compound was analyzed by 1 H-NMR, Si- Structure. (Me = methyl, Ph = phenyl, Y = dipodal, Si = silicon)
(2)
(PhSiO 3/2 ) 0.45 (MeSiO 3/2 ) 0.50 (SiO 3/2- Y-SiO 3/2 ) 0.05
Synthetic example 2: Siloxane Preparation of compounds
The monomers were prepared in the same manner as in Synthesis Example 1, except that the monomers were mixed in accordance with the mole% ratio of Synthesis Example 2 shown in Table 1 below to obtain a polysiloxane having an average composition formula represented by the following Formula 3. The molecular weight was measured in the same manner as in Synthesis Example 1. As a result, the compound of Formula 3 had a weight average molecular weight of 2,000 g / mole, and the structure of Formula 3 was confirmed in the same manner as in Synthesis Example 1. (Me = methyl, Ph = phenyl, Y = dipodal, Si = silicon)
(3)
(PhSiO 3/2 ) 0.42 (MeSiO 3/2 ) 0.51 (SiO 3/2- Y-SiO 3/2 ) 0.07
Synthetic example 3: Siloxane Preparation of compounds
The monomers were prepared in the same manner as in Synthesis Example 1 except that the monomers were mixed in accordance with the molar ratio described in Synthesis Example 3 below to obtain a polysiloxane having an average composition formula represented by the following Formula 4. The molecular weight of the compound represented by the following formula (4) was 2,300 g / mole, and the structure of the following formula (4) was confirmed in the same manner as in Synthesis Example 1. (Me = methyl, Ph = phenyl, Y = dipodal, Si = silicon)
[Chemical Formula 4]
(PhSiO 3/2 ) 0.45 (MeSiO 3/2 ) 0.45 (SiO 3/2- Y-SiO 3/2 ) 0.10
compare Synthetic example 1: a compound represented by the formula (5) Siloxane Preparation of compounds
The monomers were prepared in the same manner as in Synthesis Example 1, except that the monomers were mixed in accordance with the molar ratio described in Comparative Synthesis Example 1 below to obtain a polysiloxane having an average composition formula represented by the following formula (5). The molecular weight was measured in the same manner as in Synthesis Example 1. As a result, the molecular weight of the compound of Formula 5 was 1,200 g / mole, and the structure of Formula 5 was confirmed in the same manner as in Synthesis Example 1. (Me = methyl, Ph = phenyl, Si = silicon)
[Chemical Formula 5]
(PhSiO 3/2 ) 0.40 (MeSiO 3/2 ) 0.40 (SiO 3/2- Y-SiO 3/2 ) 0.20
compare Synthetic example 2: Siloxane Preparation of compounds
Monomers were prepared in the same manner as in Synthesis Example 1, except that the monomers were mixed in accordance with the molar ratio described in Comparative Synthesis Example 2 shown in Table 1 below to obtain a polyphenylsiloxane having an average composition formula represented by the following formula (6). The molecular weight of the compound of Formula 6 was 1,200 g / mole, and the structure of Formula 6 was confirmed in the same manner as in Synthesis Example 1. (Me = methyl, Ph = phenyl, Vi = vinyl, Si = silicon)
[Chemical Formula 6]
(PhSiO 3/2) 0.50 ( MeSiO 3/2) 0.50
compare Synthetic example 3: Siloxane Preparation of compounds
The monomers were prepared in the same manner as in Synthesis Example 1, except that the monomers were mixed according to the molar ratio described in Comparative Synthesis Example 3 shown in Table 1 below to obtain a polyphenylsiloxane having an average composition formula represented by the following formula (7). The molecular weight was measured in the same manner as in Synthesis Example 1, and the molecular weight of the compound of Formula 7 was 2,300 g / mole. The structure of Formula 7 was confirmed in the same manner as in Synthesis Example 1.
(7)
(H 2 C = C (CH 3 ) CO 2 (CH 2 ) 3 SiO 3/2 ) 1.00
Synthesis Example 1
Synthesis Example 2
Synthesis Example 3
trimethoxysilane
(The content unit of each component is mol%)
Example 1 to 3 and Comparative Example 1 to 3: Preparation of photosensitive resin composition and use thereof Cured film Manufacturing and Evaluation
The siloxane compound and the solvent (PGMEA) prepared in Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 to 3 were mixed in the amounts (parts by weight) shown in the following Table 2 to obtain photosensitive members of Examples 1 to 3 and Comparative Examples 1 to 3 To prepare a resin composition. Then, the compositions according to Examples 1 to 3 and Comparative Examples 1 to 3 were each spin-coated on a glass substrate, prebaked on a hot plate at 100 DEG C for 1 minute to adjust the thickness to 2 mu m, Lt; 0 > C for 1 hour to obtain a polysiloxane cured film.
The light transmittance, chemical resistance, residual film ratio and pencil hardness of the obtained cured film were measured by the methods described below, and the results are shown in Table 2 below.
(Aka PAC, DAITO)
(100 占 폚, 1 minute, 占 퐉)
(T% at 400 < 0 > C)
Change in thickness (? 占 퐉) RT, 30 minutes
Each measurement of the above Table 2 was measured by the following method.
(One) Light transmittance Measure
First, only the glass substrate was measured using MultiSpec-1500 (trade name, product of SHIMADZU Corporation), and the ultraviolet visible absorption spectrum thereof was taken as a reference. Subsequently, a cured film of the photosensitive resin composition was formed on the glass substrate (pattern exposure was not performed), and this sample was measured with a single beam to determine the light transmittance at a wavelength of 400 nm per 1 mu m, Light transmittance was determined.
(2) Chemical resistance measurement
The cured polysiloxane cured film on the glass substrate was immersed in each solvent (NMP and 2.37% TAMH) at room temperature (25 ° C) for 30 minutes, the solvent was filtered, and the thickness change was measured after drying at about 110 ° C for about 10 minutes .
(3) Residual film ratio Calculation
The film residual ratio was calculated according to the following formula.
(%) = [(Film thickness after development) / (film thickness after pre-baking)] x 100
(4) Pencil hardness measurement
A pencil was inserted at an angle of 45 ° using a Type 14FW (trade name, product of Heidon Corporation), and a load of 50 g was applied to the weight. After the cured film and the pencil lead were pressed, the plate was moved to scratch Were visually confirmed.
As can be seen from the above Table 2, the cured films obtained by curing the compositions according to Examples 1 to 3 containing the siloxane compound according to Formula 1 of this embodiment had a refractive index higher than that of Comparative Examples 2 and 3 Compared to the cured film obtained by curing the composition, the pencil hardness after curing at 350 ° C is higher than 4H. On the other hand, the photosensitive resin composition of Comparative Example 1 was obtained by curing a polysiloxane containing 0.2 mole of a die fofal structure. In this case, a crack occurred after curing.
In addition, the compositions according to Examples 1 to 3 are very high in light transmittance at 400 nm after curing at 350 캜, all of which are 95% or more.
In addition, the composition according to Examples 1 to 3 exhibited a high residual film ratio of not more than 80% after curing at 350 캜 divided by the film thickness after pre-baking (100 캜, 1 min) The residual film ratios of the cured films of Comparative Example 2 and Comparative Example 3 which do not include the vandal structure are as low as 60% or less.
In addition, the cured films obtained by curing the compositions according to Examples 1 to 3 are superior to the cured films obtained in Comparative Example 2 and Comparative Example 3 using a polysiloxane that does not include a die-fired structure, particularly in a solvent such as NMP and TMAH Chemical properties are excellent.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, And falls within the scope of the present invention.
Claims (13)
[Chemical Formula 1]
(R 1 R 2 R 3 SiO 1/2) M (R 4 R 5 SiO 2/2) D (R 6 SiO 3/2) T1 (O 3/2 -Y-SiO 3/2) T2 (SiO 4 / 2 ) Q
In Formula 1,
R 1 to R 6 are each independently selected from the group consisting of hydrogen, hydroxy, halogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, A substituted or unsubstituted C1 to C30 arylalkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30 heteroaryl group, a substituted or unsubstituted C2 A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 alkoxy group, R (C = O) - Or an unsubstituted or substituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group), or combinations thereof,
Y is a single bond, oxygen, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 hetero A substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, or a combination thereof,
0.5 < 0.5, 0.5? T1 <1, 0 <T2 <0.2, 0 <Q1 <0.5,
M + D + T1 + T2 + Q = 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200079838A (en) * | 2018-12-26 | 2020-07-06 | 삼성에스디아이 주식회사 | Polarizing plate and liquid crystal display apparatus comprising the same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200079838A (en) * | 2018-12-26 | 2020-07-06 | 삼성에스디아이 주식회사 | Polarizing plate and liquid crystal display apparatus comprising the same |
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