Thermosetting protective film composition having excellent coating and recoating
By using a combination of a thermosetting adhesive resin containing an acid component and a silicon-based compound, the problems of coatability and recoatability on large substrates of liquid crystal display devices are solved, a cured film with high surface energy is formed, and a balance between coatability and recoatability is achieved, which is suitable for liquid crystal display devices with large substrates.
Patent Information
- Application Number
- CN202511119410.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-11
- Publication Date
- 2025-10-10
AI Technical Summary
In the prior art, there are problems with the coatability and recoatability of the color filter protective film of liquid crystal display devices on large substrates. In particular, in the non-spin coating method, the viscosity of the coating liquid is reduced, resulting in coatability and spot problems, and the amount of surfactant used is limited, making it difficult to simultaneously ensure coatability and recoatability in subsequent processes.
A thermosetting binder resin containing an acid component is used, and substrate affinity is improved through epoxy and amine-based silicon-based compounds. Combined with an alkali-soluble acrylate resin, a cross-linking monomer, and a silicon-based surfactant, a cured film with high surface energy is formed to ensure coating and recoating properties.
The coating performance is ensured in low-viscosity materials while maintaining high surface energy, which improves the subsequent process operability of the cured film, solves the trade-off between coating and recoating performance, and forms a protective film with excellent uniformity and flatness.
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Abstract
Description
Technical Field
[0001] The present invention relates to a thermosetting resin composition for an LCD color filter protective film. More specifically, the present invention relates to a thermosetting resin composition capable of forming a cured film having not only excellent heat resistance, acid resistance, alkali resistance, and other chemical resistances but also excellent substrate coating properties and excellent recoatability in subsequent processes, and a cured film formed using the composition. Background Art
[0002] Color liquid crystal display devices (CLDs) are processed using solvents, acidic or alkaline solutions during the manufacturing process, or when a transparent electrode layer is formed by sputtering, the device surface is locally subjected to high temperature treatment.
[0003] Depending on the circumstances, when the transparent electrode layer is etched into the desired pattern, the device is also exposed to harsh conditions such as acid and alkaline solutions. In order to prevent these treatments from causing damage to the pixels (Pixel) by heat or chemicals, a protective film formed by a resistant film is formed. With the trend of large-scale display devices such as liquid crystal displays (LCDs), the size of the substrates used is also getting larger. Currently, the 10.5th generation substrate production line has been installed, and with the large-scale substrate, the coating method used when applying the photoresist composition is also changing synchronously.
[0004] Although a coating method called slit and spin is used on glass substrates of the fourth generation size, in which a photoresist composition is applied to the substrate through a slit and then rotated, it is difficult to rotate the substrate for substrates of the fifth generation or above with a substrate size exceeding 1000mm×1000mm. Therefore, a spinless coating method is used, which only performs a coating process without rotating. The spinless coating is a method of coating a large substrate by spraying a coating composition onto the substrate through a nozzle and scanning it in a certain direction. When the existing spin coating method is used, although a uniform thin film can be coated, the consumption of the composition solution used for spin coating is large, and there are limitations when rotating a large area. On the contrary, in the spinless coating method, in order to ensure the uniformity of the thickness within the substrate, the viscosity of the coating liquid is reduced compared to the existing spin coating method, so the overall solid content is reduced and the solvent content is increased, which shows a trend of deterioration in coating properties and spots.
[0005] Thus, with the increase in the size of the substrate and the change in the coating method, the change in the coating fluid composition used is also essential. Although there is a method of increasing the amount of surfactant added in the components of the composition to ensure coatability, since coatability becomes a problem in subsequent processes, the amount added is subject to considerable restrictions. Therefore, it is necessary to develop a composition that can ensure coatability in a composition with the same surface tension. In addition, with the application of the spin-free coating method on large substrates, the coating film formed by the coating fluid composition should have uniformity (uniformity) and there should be no spots on the coating film. For display devices such as in-plane switching (IPS) mode liquid crystal display devices, in order to make the liquid crystal layer uniformly filled, there should be no thickness deviation and it is important to maintain the liquid crystal layer gap (cell gap), so a protective film with excellent flatness is required. In the prior art, in order to ensure coating properties and flatness, a silicon-based surfactant with a significant surface tension reduction effect is usually used. However, when added in excess, the surface energy of the resulting coating film after curing shows a significantly reduced value. Since the recoating property of the cured film deteriorates when a coating is further formed on the surface of the cured film, there is a disadvantage of reduced recoating properties in the subsequent coating process. In addition, in terms of the process, bubbles are generated in the pipeline, which becomes a cause of various adverse reactions, so its usage is limited. Most importantly, depending on the type of polymer constituting the material, there are sometimes situations that cannot be solved by surfactants. The coating properties of the composition used to form a protective film (outer coating, OC) and the recoating properties in the subsequent process after the protective film is formed are in a trade-off relationship, so it is necessary to develop a technology that improves both properties at the same time. Summary of the Invention
[0006] Technical issues
[0007] The present invention aims to address the coatability and recoatability issues of thermosetting resin compositions used in protective films for color filters of liquid crystal display devices, as described above. The present invention aims to provide a thermosetting binder resin that significantly improves coatability while simultaneously increasing surface energy, thereby providing a cured film with improved subsequent processability (recoatability). Furthermore, the present invention aims to provide a thermosetting resin composition containing the thermosetting binder resin and a cured film formed therefrom.
[0008] Technical Solution
[0009] In the present invention, by using a thermosetting binder resin containing an acid component as the epoxy-containing alkali-soluble acrylate resin component, the affinity of the epoxy groups and acid components contained in the thermosetting binder resin for the substrate is increased, resulting in excellent coating performance even up to the edge of the color filter (underlayer film) constituting the bare glass, thereby improving coating properties. Furthermore, even when the surface energy of the formed film is higher than that of conventional resins and a surfactant with a significant surface tension-reducing effect is used, subsequent processing is simplified, thereby resolving various problems in the prior art.
[0010] In the thermosetting resin composition, an alkali-soluble acrylate resin containing a polymer composed of the following chemical formula 1 is mixed with each other, a crosslinking monomer having at least two acrylic double bonds, an adhesion additive silicon-based compound containing epoxy and amine groups, a silicon-based surfactant, and a solvent are included.
[0011] [Chemical Formula 1]
[0012]
[0013] In the Chemical Formula 1, n is a natural number ranging from 1 to 10. In the Chemical Formula 1, R1 and R2 are each independently an epoxy group.
[0014] In one embodiment of the present invention, the composition may include: a) 10 to 60 wt% of the alkali-soluble acrylate resin; b) 10 to 40 wt% of the cross-linking monomer; c) 0.0001 to 5 wt% of the adhesion additive silicon-based compound; d) 0.0001 to 5 wt% of the surfactant silicon-based compound; and e) the remainder of the solvent.
[0015] The solid content of the thermosetting resin composition as a whole may be 10 to 50 wt %.
[0016] In one embodiment of the present invention, the resin having the Chemical Formula 1 may have a weight average molecular weight ranging from 1,500 to 7,000.
[0017] In one embodiment of the present invention, the resin of Chemical Formula 1 may have 50 wt % alone.
[0018] In one embodiment of the present application, the cross-linkable monomer can be one or more selected from the group consisting of 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, ethylene glycol diacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivatives, trimethylolpropane triacrylate, dipentaerythritol polyacrylate, and methacrylates thereof.
[0019] In one embodiment of the present application, the adhesion additive silicon-based compound can be one or more selected from the group consisting of (3-glycidyloxypropyl)trimethoxysilane, (3-glycidyloxypropyl)triethoxysilane, (3-glycidyloxypropyl)methyldimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, (3-glycidyloxypropyl)dimethylethoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and aminopropyltrimethoxysilane.
[0020] In one embodiment of the present application, the surfactant can use a silicon-based surfactant.
[0021] In one embodiment of the present application, the solvent is selected according to solubility, coatability, and the like, and specifically, propylene glycol monoethyl ether acetate, ethoxyethyl acetate, butyl acetate, 3-methoxypropyl methyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3-methoxypropyl ethyl acetate, or 3-ethoxypropyl methyl acetate, or the like can be used, and in particular, one or more selected from the group consisting of propylene glycol monoethyl ether acetate, 3-methoxypropyl methyl acetate, and diethylene glycol methyl ethyl ether.
[0022] Technical Effects
[0023] According to the present application, even in a low viscosity material, the coatability of a protective film (overcoating (OC)) can be ensured by adding a relatively small amount of a surfactant. Furthermore, although a surfactant having a significant surface tension reduction effect is used, the surface energy of the cured film remains at a high level, and thus the operability (recoatability) of a subsequent re-coating process is easy. DETAILED DESCRIPTION
[0024] Hereinafter, embodiments of the present application will be described in detail. However, the present application is not necessarily constituted as defined in the embodiments, and can be embodied in various other forms.
[0025] The following examples are provided to enable full understanding of the present application and are provided to sufficiently convey the scope of the present application to those having ordinary skill in the art.
[0026] In the embodiments of the present application, when an element is described as being configured or connected to another element, the element can be directly configured or connected to the other element, or other elements can be interposed therebetween. In contrast, when an element is described as being directly configured or connected to another element, no other element is interposed therebetween. Although terms such as first, second, third, etc. are used to describe various items, components, regions, layers, and / or parts, etc., the items are not limited by the terms.
[0027] The professional terms used in the embodiments of the present application are used only for the purpose of illustrating specific embodiments and do not serve to limit the present application. In addition, unless otherwise defined, all terms including technical and scientific terms have the same meaning as commonly understood by those having ordinary skill in the art of the present application. The terms defined in a general dictionary should be interpreted to have the same meaning as the meaning consistent with the context of relevant technology and the present application, and should not be interpreted in an idealized or overly formal sense.
[0028] The thermosetting resin composition according to the embodiments of the present application is represented by the following Chemical Formula 1 and the alkali-soluble acrylate resin used alone, a crosslinkable monomer having two or more acrylic acid groups, an adhesion additive silicon-based compound including an epoxy group and an amine group, a silicon-based surfactant, and a solvent.
[0029] [Chemical Formula 1]
[0030]
[0031] In the Chemical Formula 1, n is a natural number in the range of 1 to 10.
[0032] In the Chemical Formula 1, R1 and R2 are each independently an epoxy group.
[0033] The alkali-soluble acrylate resin used in the present application is preferably used alone.
[0034] The alkali-soluble acrylate resin has a weight average molecular weight in the range of 1500 to 7000, and more preferably 3000 to 5000.
[0035] When the weight average molecular weight of the alkali-soluble acrylate resin is in the above range, coating uniformity is good, outgassing is reduced, and excellent chemical resistance is obtained.
[0036] When the content of the cross-linkable acrylic monomer is less than 10 wt%, the degree of curing decreases, causing problems with adhesion and chemical resistance. Conversely, when it exceeds 50 wt%, unreacted cross-linking agent causes problems with adhesion and, among chemical resistance, solvent resistance.
[0037] The cross-linkable acrylic monomer containing at least two double bonds can use 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, ethylene glycol diacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivatives, trimethylolpropane triacrylate, dipentaerythritol polyacrylate or their methacrylates.
[0038] Preferably, the cross-linking monomer having at least two acrylic double bonds is contained in the resin composition in an amount of 10 to 40 wt %.
[0039] When the content is less than 10 wt %, the curing degree of the thermosetting resin composition may be problematic, and when it exceeds 40 wt %, the curing degree may be reduced, coating uniformity may be deteriorated, and excessive volatile gas may be released during the process.
[0040] The silicon-based compound containing epoxy groups and amino groups can use one or more selected from (3-glycidyloxypropyl)trimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, (3-glycidyloxypropyl)dimethylepoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and aminopropyltrimethoxysilane.
[0041] The content of the silicon-based compound containing an epoxy group and an amine group in the alkali-soluble acrylate resin composition is preferably 0.0001 to 5 wt %, more preferably 0.1 to 1.0 wt %.
[0042] When the content is less than 0.0001 wt %, the adhesion is reduced, and there is a problem of the coating film peeling due to the reduced adhesion. When the content exceeds 5 wt %, storage stability problems may occur, and there is a problem of the coating film peeling due to excessive use.
[0043] As the surfactant, a silicon-based surfactant may be used.
[0044] The content of the silicon-based surfactant in the alkali-soluble acrylate resin composition is preferably 0.0001 to 5% by weight, more preferably 0.1 to 1.0% by weight.
[0045] When the content thereof is less than 0.0001% by weight, coating uniformity is reduced, and coating spots can be generated, and when the content exceeds 5% by weight, the surface energy of the cured coating film shows a significantly low value, thus there is a disadvantage in that re-coatability is reduced when further forming a coating layer on the cured film in a subsequent process, and in terms of the process, bubbles are generated in the pipe, becoming a cause of various malfunctions, thus the use amount thereof is limited.
[0046] The solvent is selected depending on solubility, coatability, etc., and specifically, propylene glycol monoethyl ether acetate, ethoxyethyl propionate, butyl acetate, 3-methoxypropyl methyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, ethyl 3-methoxypropionate, or methyl 3-ethoxypropionate, etc. can be used, and particularly, propylene glycol monoethyl ether acetate, 3-methoxypropyl methyl acetate, or diethylene glycol methyl ethyl ether is preferably used.
[0047] The solvent can vary in content depending on viscosity or total solid content in the composition, and thus can be contained in an amount other than the solid content used in the thermosetting resin composition of the present application, and particularly, it is preferable that propylene glycol monoethyl ether acetate be used in an amount of 50 to 80% by weight with respect to the total amount of the solvent used, and when the content of the solvent is within the above range, thickness deviation cannot be overcome, thus there is a problem in that uniformity of the thermosetting resin composition is reduced.
[0048] In addition, the thermosetting resin composition of the present application can use a curing accelerator, a pigment, or the like as an additive as needed.
[0049] The content of the additive is preferably 2% by weight with respect to the total weight of the thermosetting resin composition, and when the content exceeds 2% by weight, there is a problem in that a residual film is generated or stability is reduced, and a phenomenon in which ions, impurities are eluted into a liquid crystal can occur.
[0050] In addition, the present application relates to a thermosetting resin composition for a color filter protective film, characterized by using a thermosetting resin composition containing the above-described components, and more specifically, a cured film forming method having excellent heat resistance, and excellent chemical resistance such as acid resistance, alkali resistance, and the like, and excellent coatability with respect to a substrate and excellent re-coatability with respect to a subsequent process is as follows.
[0051] First, the thermosetting resin composition of the present invention is applied on the surface of the substrate by spin coating, slit spin (FAS, Slit & Spin) coating, slit coating, etc. After removing the solvent in a vacuum process, the residual solvent is removed by pre-baking to form a coating film. At this time, the pre-baking (Pre-bake) can be performed at a temperature of 70~110°C for 1~5 minutes. In addition, the post-baking (Post-bake) is usually performed at a temperature range of 150~250°C for 10 minutes to 2 hours. In addition, the pre-baking and post-baking can be performed in one step or a combination of more than one step. In the post-baking step, the epoxy group in the thermosetting binder resin reacts with the decomposed acid to form a cured film with a network structure.
[0052] As shown in the following examples, the surface energy of the cured film can be in the range of 58 to 61 mN / m.
[0053] Furthermore, the cured film exhibits not only excellent flatness but also high surface hardness and excellent chemical resistance, including heat resistance, acid resistance, and alkali resistance, making it suitable for use as a color filter protective film material. The present invention also provides a color filter including the protective film and a liquid crystal display device including the color filter. The liquid crystal display device includes a black matrix and a color filter and can be manufactured according to conventional methods known in the art.
[0054] The present invention will be described in more detail below with reference to the following examples, but the present invention is not limited to these examples. The weight parts in the examples are based on 100 parts by weight of the thermosetting binder resin.
[0055] Preferred examples are provided below to help understanding the present invention. However, the following examples are only used to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
[0056] [Synthesis example 1]
[0057] In a 1 L jacketed reactor equipped with a cooling tube and a stirrer, 1,1,2,2-tetrakis(p-hydroxyphenyl)ethane [Sigma-Aldrich], 3-chloropropylmethacrylate [3-Chloropropylmethacrylate], acrylic acid, and 4,4'-diphthalic anhydride were added in a weight ratio of 30:10:30:30. A polymerization initiator, 2,2'-azobis(2,4-dimethylvaleronitrile; V-65) was added at 1% of the total weight. TM ) and 2% by weight of the polymerization inhibitor tert-Butylhydroquinone.
[0058] In addition, propylene glycol methyl ether acetate was added as a solvent, and the solvent was used in a weight ratio of 60% of the total weight, and stirring was started after nitrogen substitution. The stirring speed was preferably 80 rpm. In addition, after the reaction solution was warmed to 60°C, the temperature was maintained for 6 hours, thereby obtaining the polymer resin of Chemical Formula 1 as an alkali-soluble acrylate resin.
[0059] At this time, the weight average molecular weight (Mw) of the polymer resin of Chemical Formula 1 was analyzed by GPC, and the result was measured as 6700 g / mol.
[0060] [Synthesis Example 2]
[0061] In a 1L jacketed reactor equipped with a cooling tube and a stirrer, 1,1,2,2-tetra(p-hydroxyphenyl)ethane [Sigma-Aldrich], 3-chloropropyl methacrylate, acrylic acid, and 4,4'-diphthalic anhydride were added in a weight ratio of 30:10:30:30, and a polymerization initiator V-65 accounting for 1% of the total weight and a polymerization inhibitor tert-butyl hydroquinone accounting for 3% of the total weight were added. In addition, propylene glycol methyl ether acetate was added as a solvent, and the solvent was used in a weight ratio of 60% of the total weight, and stirring was started after nitrogen substitution. The stirring speed was preferably 80 rpm. In addition, after the reaction solution was warmed to 60°C, the temperature was maintained for 6 hours, thereby obtaining the polymer resin of Chemical Formula 1 as an alkali-soluble acrylate resin.
[0062] At this time, the weight average molecular weight (Mw) of the polymer resin of Chemical Formula 1 was analyzed by GPC, and the result was measured as 4000 g / mol.
[0063] [Synthesis Example 3]
[0064] In a 1L jacketed reactor equipped with a cooling tube and a stirrer, 1,1,2,2-tetra(p-hydroxyphenyl)ethane [Sigma-Aldrich], 3-chloropropyl methacrylate, acrylic acid, and 4,4'-diphthalic anhydride were added in a weight ratio of 30:10:30:30, and a polymerization initiator V-65 accounting for 1% of the total weight and a polymerization inhibitor tert-butyl hydroquinone accounting for 4% of the total weight were added. In addition, propylene glycol methyl ether acetate was added as a solvent, and the solvent was used in a weight ratio of 60% of the total weight, and stirring was started after nitrogen substitution. The stirring speed was preferably 80 rpm. In addition, after the reaction solution was warmed to 60°C, the temperature was maintained for 6 hours, thereby obtaining the polymer resin of Chemical Formula 1 as an alkali-soluble acrylate resin.
[0065] At this time, it was confirmed that the weight average molecular weight (Mw) of the polymer resin of Chemical Formula 1 was 1600 g / mol as a result of GPC analysis.
[0066] [Example]
[0067] (Example 1)
[0068] A liquid thermosetting resin composition was prepared using 50 wt % of the polymer of Chemical Formula 1 of Synthesis Example 3 as the alkali-soluble acrylate resin alone, 10 wt % each of pentaerythritol tetraacrylate and dipentaerythritol polyacrylate as the cross-linking monomer having at least two acrylic double bonds, 0.1 wt % each of 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and aminopropyltrimethoxysilane as the adhesion additive silicon-based compound containing epoxy and amine groups, 0.1 wt % of a silicon-based surfactant, and 46.8 wt % of propylene glycol methyl ether acetate as the solvent.
[0069] (Example 2)
[0070] A liquid thermosetting resin composition was prepared by using the polymer of Chemical Formula 1 of Synthesis Example 2 alone as an alkali-soluble acrylate resin, 10 wt % each of pentaerythritol tetraacrylate and dipentaerythritol polyacrylate as cross-linking monomers having at least two acrylic double bonds, 0.1 wt % each of 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and aminopropyltrimethoxysilane as adhesion additive silicon-based compounds containing epoxy and amine groups, 0.1 wt % of a silicon-based surfactant, and 46.8 wt % of propylene glycol methyl ether acetate as a solvent.
[0071] (Example 3)
[0072] A liquid thermosetting resin composition was prepared by using the polymer of Chemical Formula 1 of Synthesis Example 1 alone as an alkali-soluble acrylate resin, 10 wt % each of pentaerythritol tetraacrylate and dipentaerythritol polyacrylate as cross-linking monomers having at least two acrylic double bonds, 0.1 wt % each of 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and 0.1 wt % of aminopropyltrimethoxysilane as adhesion additive silicon-based compounds containing epoxy and amine groups, 0.1 wt % of a silicon-based surfactant, and 46.8 wt % of propylene glycol methyl ether acetate as a solvent.
[0073] In the case of Example 1, Example 2, Example 3, and Comparative Examples 1 to 4, a liquid thermosetting resin composition was prepared by the same method as in Example 1 except that the components and composition ratios shown in Table 1 below were used in Example 1. At this time, the units of Table 1 are weight %. In Table 1 below, R of Chemical Formula 1 was an epoxy group, and the substances of Synthesis Example 3 (1600), Synthesis Example 2 (4000), and Synthesis Example 3 (6700) each having a different weight average molecular weight were used, and pentaerythritol tetraacrylate and dipentaerythritol polyacrylate were used as the cross-linkable acrylic monomer.
[0074] [Table 1]
[0075]
[0076] Using the thermosetting resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 4, the OC coating property, surface energy of the OC film, surface hardness, adhesion, light transmittance, acid resistance, alkali resistance, and solvent resistance properties were evaluated in the following manner.
[0077] 1-1. OC coating property
[0078] The thermosetting resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were each coated on a glass substrate by a spin coating method and a non-rotation coating method (TOK, TR45 non-rotation), and then VCD and prebake were performed, and the curling of the outer coating (OC) liquid from the edge of the substrate was observed to evaluate the coating property. At this time, a record of no curling at all was good (O), and a record of curling of 10 mm or more from the edge was bad (X), and the results thereof are shown in Table 2 below.
[0079] 1-2. Surface energy of the outer coating film
[0080] The surface energy was measured to confirm the subsequent processability properties of the cured film. The contact angles (KRUSS DSA100) with respect to DI water and CH2I2 were measured, and then the surface energy obtained from the two contact angles is shown in Table 2.
[0081] 1-3. Surface hardness
[0082] The pencil hardness of the cured film was measured according to the method of ASTM-D3363, and the results thereof are shown in Table 2 below.
[0083] 1-4. Adhesion
[0084] According to the method of ASTM-D3359, 100 grids were formed on the cured film using a cutter by the grid tape method, and then peeled off with tape. At this time, the number of peeled grid patterns among the 100 grid patterns was measured, and the adhesion was evaluated according to the following standards and shown in Table 2 below.
[0085] ○: The number of peeled grid patterns is 5 or less
[0086] △: The number of peeled grid patterns is 6 to 49
[0087] X: The number of stripped grid patterns is 50 or more
[0088] 1-5. Light Transmittance
[0089] Ultraviolet light having a wavelength of 400 nm was allowed to pass through each of the glass substrates on which the cured films were formed, and the light transmittance was measured using a UV-Vis spectrophotometer. The results are shown in Table 2 below.
[0090] 1-6. Acid resistance
[0091] Glass substrates with cured films formed thereon were immersed in a 5.0 wt% aqueous HCl solution at 30°C for 30 minutes, then removed and observed for changes in the appearance of the cured films to evaluate acid resistance. No change in appearance was scored as good (O), while peeling or whitening was scored as poor (X). The results are shown in Table 2.
[0092] 1-7. Alkali resistance
[0093] The glass substrates with the cured films formed thereon were immersed in a 5.0 wt% NaOH aqueous solution at 30°C for 30 minutes, then removed and observed for changes in the appearance of the cured films to evaluate alkali resistance. No change in appearance was scored as good (O), while peeling or whitening was scored as poor (X). The results are shown in Table 2.
[0094] 1-8. Solvent resistance
[0095] Glass substrates with cured films formed thereon were immersed in a 40°C NMP solution for 10 minutes, and the thickness change of the cured films was observed to evaluate solvent resistance. A thickness change of 3% or less was rated as good (O), while a change exceeding 3% was rated as poor (X). The results are shown in Table 2 below.
[0096] [Table 2]
[0097]
[0098] As shown in Table 2, the thermosetting resin composition according to Example 2 of the present invention has excellent coating properties, surface energy of the OC film, surface hardness, adhesion, light transmittance, acid resistance, alkali resistance, and solvent resistance.
Claims
1. A thermosetting resin composition, which is an alkali-soluble acrylate resin composition containing epoxy groups for a color filter protective film, characterized in that: Include: a) an alkali-soluble acrylate resin represented by the following Chemical Formula 1 and used alone; b) a crosslinking monomer having at least two acrylic double bonds; c) heterogeneous silicone-based adhesion promoters containing epoxy and amine groups, respectively; and d) silicon-based surfactants; e) solvents, Wherein, the chemical formula 1 is formed by polymerization of 1,1,2,2,-tetrakis(p-hydroxyphenyl)ethane, 3-chloropropyl methacrylate, acrylic acid and 4,4'-diphthalic anhydride. [Chemical Formula 1] In the chemical formula 1, n is a natural number ranging from 1 to 10, In the Chemical Formula 1, R1 and R2 are each independently an epoxy group.
2. The thermosetting resin composition according to claim 1, characterized in that Include: a) 10 to 50 wt % of the alkali-soluble acrylate resin; b) 10 to 20% by weight of the crosslinking monomer; c) 0.0001 to 5 wt % of the heterogeneous silicon-based adhesion enhancer; d) 0.0001 to 5 wt% of a silicon-based surfactant; and e) Remaining amount of solvent.
3. The thermosetting resin composition according to claim 2, characterized in that The solid content of the entire thermosetting resin composition is 10 to 50% by weight.
4. The thermosetting resin composition according to claim 1, characterized in that The resin having the Chemical Formula 1 has a weight average molecular weight (Mw) ranging from 1500 to 7000 g / mol.
5. The thermosetting resin composition according to claim 2, characterized in that The content of the resin of Chemical Formula 1 is 50 wt % relative to the total weight of the thermosetting resin composition.
6. The thermosetting resin composition according to claim 1, characterized in that The crosslinking monomer is one or more selected from the following multifunctional acrylate group: 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, ethylene glycol diacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivatives, trimethylolpropane triacrylate and dipentaerythritol polyacrylate.
7. The thermosetting resin composition according to claim 1, characterized in that The silicon-based compound is one or more selected from (3-glycidyloxypropyl)trimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, (3-glycidyloxypropyl)dimethylepoxysilane, 3,4-epoxybutyltrimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and aminopropyltrimethoxysilane.