Low-temperature thermosetting resin composition

Abstract

The low-temperature thermosetting resin composition includes an epoxy acrylic resin represented by the following Chemical Formula 1, a thermosetting agent, a curing accelerator, and a remainder of a solvent. As a result, an excellent organic film can be formed from the low-temperature heat-curable resin composition by a low-temperature heat-curing process (Chemical Formula 1).

Description

TECHNICAL FIELD

[0001] Embodiments of the present application relate to a low-temperature thermal curing resin composition. In more detail, embodiments of the present application relate to a low-temperature thermal curing resin composition which is cured at a low temperature as a relatively low temperature and also has a relatively flexible property after curing. BACKGROUND

[0002] In recent years, with the development of the display industry, many metal electrodes are used as bus electrodes in LCDs, OLEDs, and TSPs. However, when the metal electrode is exposed to air, the surface of the metal electrode can undergo an oxidation reaction. With respect to the oxidation reaction, when the surface of the metal electrode is exposed to air, an oxidation reaction occurs, causing atoms on the surface thereof to bind with oxygen. As a result, a binary compound of a metal element bound with oxygen, i.e., an oxide film, is formed, thereby causing corrosion and a problem of a decrease in electrical resistance as an electrical property of the metal electrode or damage to the metal electrode due to overcurrent. In recent years, to prevent the surface of the metal electrode from binding with oxygen, the surface of the metal electrode is inhibited from being exposed to air by coating an organic film on the surface of the metal electrode formed on a glass substrate, thereby inhibiting the occurrence of an oxidation reaction. However, with the transition from a glass substrate used in the past to a flexible substrate, when a metal electrode is formed on the flexible substrate and an organic film is additionally coated to cover the metal electrode, the organic film composed of an organic substance having a relatively low flexibility can be cracked. In addition, the flexible substrate employs a thin film of a plastic or polymer type. However, the thin film constituting the flexible substrate has a problem of poor heat resistance. Therefore, research into a low-temperature thermal curing resin which can improve the flexibility of an organic film formed after thermal curing while being capable of thermal curing at a relatively low temperature, thereby being capable of inhibiting thermal shock to the flexible thin film having low heat resistance and inhibiting cracking of the organic film coated on the flexible substrate, is actively being conducted. SUMMARY

[0003] TECHNICAL PROBLEM

[0004] Embodiments of the present application aim to provide a low-temperature thermal curing resin composition which is capable of inhibiting the formation of an oxidation film of a metal electrode while being capable of curing at a relatively low temperature.

[0005] TECHNICAL SOLUTION

[0006] To achieve the above-described object of the present application, a low-temperature thermal curing resin composition according to embodiments of the present application includes an epoxy acrylate resin represented by the following Chemical Formula 1, a thermal curing agent, a curing accelerator, and a residual solvent.

[0007] [Chemical Formula 1]

[0008]

[0009] In Chemical Formula 1, n is an integer of 1 to 20,

[0010] R1and R 12 are each represented by the following Chemical Formula 1-1,

[0011] [Chemical Formula 1-1]

[0012]

[0013] In the Chemical Formula 1-1, R 13 and R 14 are each any one of hydrogen, a hydrocarbon group having a carbon atom number of 1 to 20, and a polar group,

[0014] In the Chemical Formula 1, R2is represented by the following Chemical Formula 1-2,

[0015] [Chemical Formula 1-2]

[0016]

[0017] In the Chemical Formula 1-2, R3includes (i) a hydrocarbon chain substituted with or without halogen, hydroxyl, sulfone group, nitro group, or cyano group or (ii) a hetero chain in which a part of a carbon skeleton is substituted with nitrogen (N), oxygen (O), or sulfur (S) or (iii) a structure in which an aromatic ring or a polycyclic aromatic ring is connected by a single bond or fused,

[0018] In the Chemical Formula 1, R4, R5, R6, and R7are each represented by the following Chemical Formula 1-3,

[0019] [Chemical Formula 1-3]

[0020]

[0021] In the Chemical Formula 1, R8, R9, R 10 and R 11 are each represented by the following Chemical Formula 1-4,

[0022] [Chemical Formula 1-4]

[0023] ;

[0024] wherein, represents a binding site.

[0025] In one embodiment of the present application, the content of the epoxy acrylate resin can be 20 to 70 parts by weight, based on 100 parts by weight of the low-temperature heat-curable resin composition.

[0026] In one embodiment of the present application, the two or more epoxy groups contained in Chemical Formula 1 can include at least one selected from the group of multifunctional epoxy acrylate resins consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy acrylate resin, phenol novolac type epoxy resin, and cresol novolac type epoxy acrylate resin.

[0027] In one embodiment of the present application, the curing accelerator can include 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, or derivatives thereof.

[0028] In one embodiment of the present application, the thermal curing agent includes phenol novolac, cresol novolac, bisphenol A novolac, naphthalene type, etc., which can be used alone or in a mixture of two or more.

[0029] Thus, a metal electrode structure in which a metal electrode is covered can be easily formed using the low-temperature thermal curing type resin composition.

[0030] Technical Effects

[0031] The low-temperature thermal curing type resin composition thus prepared according to the embodiment of the present application is disposed to cover a metal electrode formed on a flexible substrate or a glass substrate, so that the formation of an oxide film on the metal electrode due to a reaction with oxygen can be inhibited, and a composition having excellent moisture resistance and chemical resistance can be obtained.

[0032] Further, by using a low-temperature thermal curing type resin, the flexibility after curing is excellent, and the moisture resistance and chemical resistance are excellent, so that the oxidation of a metal electrode formed on a flexible substrate or a glass substrate can be inhibited. DETAILED DESCRIPTION

[0033] Hereinafter, the low-temperature thermal curing type resin composition according to the embodiment of the present application will be described in detail with reference to synthesis examples, examples, and tables.

[0034] The terms first, second, etc. can be used to describe various components, but the components should not be limited by the terms. The terms are used only to distinguish one component from another component. For example, a first component can be named a second component without departing from the scope of the present application, and similarly, a second component can be named a first component.

[0035] The terminology used in this application is for describing specific embodiments only and is not intended to limit the invention. Unless the context clearly specifies otherwise, singular expressions include plural expressions. In this application, it should be understood that terms such as "comprising" or "having" are intended to specify the presence of features, steps, functions, components, or combinations thereof described in the specification, and do not presuppose the presence or additional possibilities of other features, steps, functions, components, or combinations thereof.

[0036] Furthermore, unless otherwise defined, all terms used in this specification, including technical or scientific terms, shall have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Terms such as those defined in common dictionaries shall be interpreted as having a meaning consistent with their meaning in the context of the relevant art, and shall not be interpreted in an ideal or overly formal sense unless expressly defined in this application.

[0037] Low-temperature thermosetting resin composition

[0038] The low-temperature thermosetting resin composition according to an embodiment of the present invention comprises an epoxy acrylate resin represented by the following chemical formula 1, a thermosetting agent, a curing accelerator, and the balance being a solvent.

[0039] [Chemical Formula 1]

[0040]

[0041] In the chemical formula 1, n is an integer from 1 to 20.

[0042] R1 and R 12 They are represented by the following chemical formulas 1-1,

[0043] [Chemical Formula 1-1]

[0044]

[0045] In the chemical formula 1-1, R 13 and R 14 They are, respectively, any one of hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, and a polar group.

[0046] In the chemical formula 1, R2 is represented by the following chemical formulas 1-2.

[0047] [Chemical Formula 1-2]

[0048]

[0049] In the chemical formulas 1-2, R3 includes (i) a hydrocarbon chain substituted or unsubstituted with halogen, hydroxyl, sulfone, nitro or cyano groups; (ii) a heterochain in which a portion of the carbon skeleton is substituted with nitrogen (N), oxygen (O) or sulfur (S); or (iii) an aromatic ring or polycyclic aromatic ring linked or fused together by a single bond.

[0050] In the aforementioned chemical formula 1, R4, R5, R6, and R7 are represented by the following chemical formulas 1-3, respectively.

[0051] [Chemical Formulas 1-3]

[0052]

[0053] In the chemical formula 1, R8, R9, R 10 and R 11 They are represented by the following chemical formulas 1-4 respectively.

[0054] [Chemical Formulas 1-4]

[0055] ;

[0056] in, Indicates the binding site.

[0057] (A) Low-temperature thermosetting resin

[0058] The composition contains an epoxy acrylate resin to improve the flexibility (flexibility) and adhesion of the insulation layer without causing cohesive failure of the insulation layer itself, and to improve adhesion, heat resistance, and moisture resistance. This epoxy acrylate resin can be used alone or in combination with two or more other resins. The epoxy acrylate resin has the following chemical formula: 1.

[0059] [Chemical Formula 1]

[0060]

[0061] In the chemical formula 1, n is an integer from 1 to 20.

[0062] R1 and R 12 They are represented by the following chemical formulas 1-1,

[0063] [Chemical Formula 1-1]

[0064]

[0065] In the chemical formula 1-1, R 13 and R 14 They are, respectively, any one of hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, and a polar group.

[0066] R2 is represented by the following chemical formula 1-2,

[0067] [Chemical Formula 1-2]

[0068]

[0069] In the chemical formulas 1-2, R3 includes (i) a hydrocarbon chain substituted or unsubstituted with halogen, hydroxyl, sulfone, nitro or cyano groups; (ii) a heterochain in which a portion of the carbon skeleton is substituted with nitrogen (N), oxygen (O) or sulfur (S); or (iii) an aromatic ring or polycyclic aromatic ring linked or fused together by a single bond.

[0070] In the aforementioned chemical formula 1, R4, R5, R6, and R7 are represented by the following chemical formulas 1-3, respectively.

[0071] [Chemical Formulas 1-3]

[0072]

[0073] In the chemical formula 1, R8, R9, R 10 and R 11 They are represented by the following chemical formulas 1-4 respectively.

[0074] [Chemical Formulas 1-4]

[0075] ;

[0076] in, Indicates the binding site.

[0077] (B) Thermosetting agent

[0078] Thermosetting agents can be appropriately selected based on the type of epoxy acrylic resin. Examples of thermosetting agents include phenolic curing agents, acid anhydride curing agents, dicyandiamide curing agents, and thermosetting acrylic monomers containing at least two double bonds. Phenolic curing agents are preferred as they can further improve heat resistance and adhesion. Examples of phenolic curing agents include phenolic varnishes, cresol varnishes, bisphenol A varnishes, and naphthalene-based varnishes, which can be used alone or in combination of two or more. Furthermore, thermosetting acrylic monomers containing at least two double bonds cure quickly and exhibit excellent moisture resistance and acid resistance. Examples of the thermosetting acrylic monomers include 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, polydipentaerythritol acrylate, or their methacrylate derivatives. The crosslinking monomer having at least two acrylate double bonds is preferably included in the resin composition at a content of 10 to 40% by weight. If its content is less than 10% by weight, there are problems with the curing degree of the thermosetting resin composition; if it exceeds 40% by weight, the curing degree decreases, and the coating uniformity decreases, resulting in a large amount of air venting.

[0079] The content of the thermosetting agent can be appropriately adjusted according to the content of the epoxy acrylate resin. However, in order to further improve heat resistance and adhesion strength, and at the same time prevent the decrease in molding properties such as flexibility (flexibility) and stamping processability due to the hardening of the insulation layer, it is advisable to use the thermosetting agent and epoxy acrylate resin in a weight ratio of 10~40:20~70.

[0080] (C) Curing accelerator

[0081] In this invention, the curing accelerator can be appropriately selected based on the type of epoxy acrylate resin and the thermosetting agent. Examples of the curing accelerator include amine complexes of boron trifluoride, imidazole derivatives, phthalic anhydride, and trimellitic anhydride, etc., but are not limited thereto. Preferably, examples of the curing accelerator include imidazole derivative curing accelerators, specifically including 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and their derivatives. Examples of the derivatives include cyanoethylated derivatives, carboxylic acid derivatives, hydroxymethyl derivatives, etc., but are not limited thereto. These curing accelerators can be used alone or in mixtures of two or more. Based on 100 parts by weight of a mixture of epoxy acrylate resin and curing agent, the content of the curing accelerator is preferably in the range of about 0.05 to 0.1 parts by weight.

[0082] (D) Solvent

[0083] In this invention, the solvent can be appropriately selected based on the type of epoxy acrylate resin and the curing agent. Examples of such solvents include:

[0084] (1) Hydrocarbons: aliphatic hydrocarbons (gasoline, kerosene, n-hexane), alicyclic hydrocarbons (cyclohexanol, methylcyclohexanol), aromatic hydrocarbons (benzene, toluene, xylene);

[0085] (2) Halogenated hydrocarbons: Aliphatic chlorinated hydrocarbons (dichloromethane, chloroform, dichloroethane, trichloroethane, tetrachloroethane, dichloroethylene, trichloroethylene, tetrachloroethylene);

[0086] (3) Alcohols: butanol, dibutanol, isobutanol, isoamyl alcohol, isopropanol;

[0087] (4) Ethers: diethyl ether, dioxane, tetrahydrofuran;

[0088] (5) Esters: Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate;

[0089] (6) Ethylene glycol ethers: ethylene glycol monomethyl ether acetate (EGMEA), ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, etc., but not limited to these.

[0090] These solvents can be used alone or in mixtures of two or more. Based on 100 parts by weight of epoxy acrylate resin, the solvent content is preferably in the range of about 20 to 80 parts by weight. Furthermore, if necessary, the low-temperature thermosetting resin may further comprise a monofunctional epoxy resin having one intramolecular epoxy group as a reactive diluent. Such a monofunctional epoxy resin preferably has a C6-C28 alkyl group, and specific examples may include one or more selected from C6-C28 alkyl glycidyl ethers, C6-C28 alkyl glycidyl esters, C6-C28 phenolic glycidyl ethers, etc., but is not limited thereto.

[0091] In particular, chemical resistance is improved when a methyl group is attached to R1, flexibility is enhanced when an ethyl group is attached, curing speed is accelerated when an epoxy group is attached to R2, and flexibility is enhanced when a urethane group is attached.

[0092] Based on 100 parts by weight of a low-temperature thermosetting resin composition, the content of the epoxy acrylate resin is preferably 20 to 70 parts by weight. If the monofunctional epoxy resin exceeds 70 parts by weight, the reliability may deteriorate due to a decrease in bonding strength.

[0093] Synthesis example 1

[0094] After preparing a flask equipped with a mechanical stirrer, thermometer and cooling jacket, add 240g of propylene glycol monomethyl ether as a solvent and 100g of bisphenol fluorene containing epoxy group represented by chemical formula 2 under a nitrogen gas flow, heat to 40°C and stir.

[0095] 315.2 g of epichlorohydrin (represented by chemical formula 3) was added to the reaction solution, heated to 100 °C, and stirred for 1 hour. Then, 33.8 g of methacrylic acid was added to the reaction solution, and the temperature was raised to 110 °C and reacted for 3 hours. Afterward, the precipitate was dissolved in tetrahydrofuran (THF) solution and precipitated in water. Then, it was dissolved in propylene glycol methyl ether acetate as a solvent and precipitated in hexane to obtain 120 g of a pale yellow precipitate.

[0096] 100g of propylene glycol methyl ether acetate was added to dissolve it. After heating to 140°C, 100g of dianhydride (represented by chemical formula 4) and 25g of phthalic anhydride (represented by chemical formula 5) were added dropwise over 1 hour. After reacting for 5 hours, a polymer resin [CB-1] with a weight-average molecular weight of 5800 was obtained.

[0097] [Chemical Formula 2]

[0098]

[0099] [Chemical Formula 3]

[0100]

[0101] Epichlorohydrin

[0102] [Chemical Formula 4]

[0103]

[0104] Benzophenone-α- 13 C-3,3′,4,4′-Tetracarboxylic dianhydride (Benzophenone-α-) 13 C-3,3′,4,4′-tetracarboxylic dianhydride)

[0105] [Chemical Formula 5]

[0106]

[0107] Phthalic anhydride

[0108] Synthesis example 2

[0109] After preparing a flask equipped with a mechanical stirrer, thermometer, and cooling jacket, 240 g of propylene glycol monomethyl ether as a solvent and 100 g of bisphenol fluorene (represented by chemical formula 2), containing an epoxy group, were added under a nitrogen gas flow. The mixture was heated to 40°C and stirred. 315.2 g of epichlorohydrin (represented by chemical formula 3) was added to the reaction mixture, and the mixture was heated to 100°C and stirred for 1 hour. 33.8 g of methacrylic acid was added to the reaction mixture, and the temperature was raised to 110°C and the reaction was carried out for 3 hours. The precipitate was then dissolved in tetrahydrofuran (THF) solution and precipitated in water. Afterward, it was dissolved in propylene glycol methyl ether acetate as a solvent and precipitated in hexane to obtain 120 g of a pale yellow precipitate. 100g of propylene glycol methyl ether acetate was added to dissolve it. After heating to 140°C, 70g of dianhydride (represented by chemical formula 4) and 15g of phthalic anhydride (represented by chemical formula 5) were added dropwise over 1 hour. After reacting for 5 hours, a polymer resin [CB-2] with a weight-average molecular weight of 3300 was obtained.

[0110] Synthesis example 3

[0111] After preparing a flask equipped with a mechanical stirrer, thermometer, and cooling jacket, 240 g of propylene glycol monomethyl ether as a solvent and 100 g of bisphenol fluorene (represented by chemical formula 2), containing an epoxy group, were added under a nitrogen gas flow. The mixture was heated to 40°C and stirred. 315.2 g of epichlorohydrin (represented by chemical formula 3) was added to the reaction mixture, and the mixture was heated to 100°C and stirred for 1 hour. 33.8 g of methacrylic acid was added to the reaction mixture, and the temperature was raised to 110°C and the reaction was carried out for 3 hours. The precipitate was then dissolved in tetrahydrofuran (THF) solution and precipitated in water. Afterward, it was dissolved in propylene glycol methyl ether acetate as a solvent and precipitated in hexane to obtain 120 g of a pale yellow precipitate. 100g of propylene glycol methyl ether acetate was added to dissolve it. After heating to 140°C, 320g of dianhydride (represented by chemical formula 4) and 45g of phthalic anhydride (represented by chemical formula 5) were added dropwise over 1 hour and reacted for 5 hours to obtain a high molecular weight resin [CB-3] with a weight average molecular weight of 22300.

[0112] Synthesis example 4

[0113] After preparing a flask equipped with a mechanical stirrer, thermometer, and cooling jacket, 240 g of propylene glycol monomethyl ether as a solvent and 100 g of bisphenol fluorene (represented by chemical formula 2), containing an epoxy group, were added under a nitrogen gas flow. The mixture was heated to 40°C and stirred. 315.2 g of epichlorohydrin (represented by chemical formula 3) was added to the reaction mixture, and the mixture was heated to 100°C and stirred for 1 hour. 33.8 g of methacrylic acid was added to the reaction mixture, and the temperature was raised to 110°C and the reaction was carried out for 3 hours. The precipitate was then dissolved in tetrahydrofuran (THF) solution and precipitated in water. Afterward, it was dissolved in propylene glycol methyl ether acetate as a solvent and precipitated in hexane to obtain 120 g of a pale yellow precipitate. 100g of propylene glycol methyl ether acetate was added and heated to 140°C. Then, 45g of dianhydride (represented by chemical formula 4) and 35g of phthalic anhydride (represented by chemical formula 5) were added dropwise over 1 hour and reacted for 5 hours to obtain a polymer resin [CB-4] with a weight-average molecular weight of 2100.

[0114] Example 1

[0115] 55.1 g of [CB-1] obtained in Synthesis Example 1, 15.5 g of thermosetting agent (Osaka Organic Chemical, BISCOTT#295 TMPTA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0116] Example 2

[0117] 55.1 g of [CB-1] obtained in Synthesis Example 1, 24.1 g of thermosetting agent (Osaka Organic Chemical, BISCOTT#295 TMPTA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0118] Example 3

[0119] 55.1 g of [CB-1] obtained in Synthesis Example 1, 14.5 g of thermosetting agent (Miwon, MIRAMER M420 PETA, South Korea), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0120] Example 4

[0121] 55.1 g of [CB-1] obtained in Synthesis Example 1, 23.5 g of thermosetting agent (Miwon, MIRAMER M420 PETA, South Korea), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0122] Example 5

[0123] 55.1 g of [CB-1] obtained in Synthesis Example 1, 15.5 g of thermosetting agent (Toa Synthetic, ARONIX M940DPHA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0124] Example 6

[0125] 55.1 g of [CB-1] obtained in Synthesis Example 1, 22.5 g of thermosetting agent (Toa Synthetic, ARONIX M940 DPHA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0126] Example 7

[0127] 54.4 g of [CB-2] obtained in Synthesis Example 2, 15.5 g of thermosetting agent (Osaka Organic Chemical, BISCOTT#295 TMPTA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0128] Example 8

[0129] 54.4 g of [CB-2] obtained in Synthesis Example 2, 24.1 g of thermosetting agent (Osaka Organic Chemical, BISCOTT#295 TMPTA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0130] Example 9

[0131] 54.4 g of [CB-2] obtained in Synthesis Example 2, 14.5 g of thermosetting agent (Miwon, MIRAMER M420 PETA, South Korea), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0132] Example 10

[0133] 54.4 g of [CB-2] obtained in Synthesis Example 2, 23.5 g of thermosetting agent (Miwon, MIRAMER M420 PETA, South Korea), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0134] Example 11

[0135] 54.4 g of [CB-2] obtained in Synthesis Example 2, 15.5 g of thermosetting agent (Toa Synthetic, ARONIX M940DPHA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0136] Example 12

[0137] 54.4 g of [CB-2] obtained in Synthesis Example 2, 22.5 g of thermosetting agent (Toa Synthetic, ARONIX M940DPHA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0138] Comparative Example 1

[0139] 55.1 g of [CB-1] obtained in Synthesis Example 1, 51.5 g of thermosetting agent (Osaka Organic Chemical, BISCOTT#295 TMPTA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0140] Comparative Example 2

[0141] 55.1 g of [CB-1] obtained in Synthesis Example 1, 5.7 g of thermosetting agent (Osaka Organic Chemical, BISCOTT#295 TMPTA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0142] Comparative Example 3

[0143] 55.1 g of [CB-1] obtained in Synthesis Example 1, 54.1 g of thermosetting agent (Miwon, MIRAMER M420 PETA, South Korea), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0144] Comparative Example 4

[0145] 55.1 g of [CB-1] obtained in Synthesis Example 1, 3.9 g of thermosetting agent (Miwon, MIRAMER M420 PETA, South Korea), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0146] Comparative Example 5

[0147] 55.1 g of [CB-1] obtained in Synthesis Example 1, 45.2 g of thermosetting agent (Toa Synthetic, ARONIX M940DPHA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0148] Comparative Example 6

[0149] 55.1 g of [CB-1] obtained in Synthesis Example 1, 8.7 g of thermosetting agent (Toa Synthetic, ARONIX M940DPHA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0150] Comparative Example 7

[0151] 54.4 g of [CB-2] obtained in Synthesis Example 2, 51.5 g of thermosetting agent (Osaka Organic Chemical, BISCOTT#295 TMPTA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0152] Comparative Example 8

[0153] 54.4 g of [CB-2] obtained in Synthesis Example 2, 5.7 g of thermosetting agent (Osaka Organic Chemical, BISCOTT#295 TMPTA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0154] Comparative Example 9

[0155] 54.4 g of [CB-2] obtained in Synthesis Example 2, 54.1 g of thermosetting agent (Miwon, MIRAMER M420 PETA, South Korea), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0156] [Comparative Example 10]

[0157] 54.4 g of [CB-2] obtained in Synthesis Example 2, 3.9 g of thermosetting agent (Miwon, MIRAMER M420 PETA, South Korea), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0158] Comparative Example 11

[0159] 54.4 g of [CB-2] obtained in Synthesis Example 2, 45.2 g of thermosetting agent (Toa Synthetic, ARONIX M940DPHA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0160] Comparative Example 12

[0161] 54.4 g of [CB-2] obtained in Synthesis Example 2, 8.7 g of thermosetting agent (Toa Synthetic, ARONIX M940DPHA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0162] Comparative Example 13

[0163] 55.1 g of [CB-3] obtained in Synthesis Example 3, 15.5 g of thermosetting agent (Osaka Organic Chemical, BISCOTT#295 TMPTA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0164] [Comparative Example 14]

[0165] 55.1 g of [CB-4] obtained in Synthesis Example 4, 15.5 g of thermosetting agent (Osaka Organic Chemical, BISCOTT#295 TMPTA, Japan), 0.007 g of curing accelerator (Ajinomoto Fine-Techno, VDH, Japan), 0.2 g of additive (BYK, BYK-066, Germany), and 149.7 g of solvent (propylene glycol monomethyl ether acetate, Chemtronics, South Korea) were mixed to prepare a low-temperature thermosetting resin composition.

[0166] The compositions of Examples 1 to 12 and Comparative Examples 1 to 14 are shown in Table 1 below.

[0167] [Table 1]

[0168]

[0169] The thermosetting epoxy resin composition solutions obtained in the examples and comparative examples were spin-coated to form films. Specifically, a glass substrate, COP (cyclic olefin polymer), and PI (polyimide film) were used as substrates for film formation. The composition was coated to a thickness of 2 μm, then soft-baked at 85°C for 3 minutes to evaporate the solvent, followed by thermosetting at 85°C for 30 minutes to form the coating. Next, the thermosetting resin compositions prepared in the examples and comparative examples were evaluated in various ways for the following criteria.

[0170] (1) Moisture-proof property

[0171] Regarding moisture resistance, after forming a 3μm organic film on the polyimide film using the process described above, the sample was left to stand at room temperature (25°C) for 10 minutes. Then, the weight of the thermocuted sample was measured using a balance (CAW320, CAS, Korea) with an accuracy of four decimal places. The thermocuted sample was then placed in 100°C water for 2 hours, removed, and the moisture was removed using an air gun before being weighed again. A weight change of 0.5% indicates excellent moisture resistance. The benchmarks are as follows:

[0172] ◎<0.5%, 0.5%≤○<2.0%, 3.0%≤X.

[0173] (2) Flexibility (Bending property)

[0174] Regarding flexibility, after forming a 3 μm organic film on a cyclic olefin polymer / polyimide film using the process described above, the film was allowed to stand at room temperature (25°C) for 10 minutes, and then the recovery rate after bending was measured. The recovery rate after bending can be obtained by (recovered radius of curvature - bent radius of curvature) / (initial radius of curvature - bent radius of curvature) × 100, and this recovery rate was measured after bending evaluation (10,000 cycles). A flexibility of 90% is considered excellent. The benchmarks are as follows:

[0175] ◎>90%, 90%≥○>80%, 80%≥△>70%, 70%≥X.

[0176] * Radius of curvature: The radius of the circle formed by the bent portion of a thin film when it is bent.

[0177] * The radius of curvature of the film was measured using a bending reference (Bending Tool, TouchScreen Panel Reliability Measure System, Vitron).

[0178] (3) Adhesion force

[0179] Regarding adhesion, after forming a 3μm organic film on the polyimide film using the process described above, it is allowed to stand at room temperature (25°C) for 10 minutes. Then, according to the method of ATSM-D3359, 100 grids are formed on the cured film using a cutter via grid tape, and then peeled off with tape. At this point, the number of grid patterns peeled off from the 100 grid patterns is measured. If the adhesion is 5B, it can be considered good.

[0180] The benchmarks are as follows:

[0181] 100%: 5B, 80%: 4B, 60%: 3B, 40%: 2B, 20%: 1B, 0%: 0B

[0182] ◎: 5B, 5B≥○>4B, 4B≥△>3B, ≤3B: X.

[0183] (4) Acid resistance

[0184] Regarding acid resistance, after forming a 3 μm organic film on a glass substrate using the process described above, the film was left to stand at room temperature (25°C) for 10 minutes, then immersed in a 1.0% HCl aqueous solution at 30°C for 30 minutes. The changes in appearance and thickness were then evaluated. At this point, no change in appearance or thickness was recorded as good (O), while peeling, whitening, or changes in thickness were recorded as bad (X).

[0185] (5) Alkali resistance

[0186] Regarding alkali resistance, after forming a 3 μm organic film on a glass substrate using the process described above, the film was left to stand at room temperature (25°C) for 10 minutes, then immersed in a 2.38% TMAH aqueous solution at 25°C for 30 minutes. The changes in appearance and thickness were then evaluated. At this point, no change in appearance or thickness was recorded as good (O), while peeling, whitening, or changes in thickness were recorded as poor (X).

[0187] (6) Solvent resistance

[0188] Regarding solvent resistance, after forming a 3 μm organic film on a glass substrate using the process described above, the film was left to stand at room temperature (25°C) for 10 minutes, then immersed in a 25°C PGMEA solution for 30 minutes before being removed. Changes in appearance and thickness were then evaluated. At this point, no change in appearance or thickness was recorded as good (O), while peeling, whitening, or changes in thickness were recorded as bad (X).

[0189] The evaluation results of items (1) to (6) are shown in [Table 2].

[0190] [Table 2]

[0191]

[0192] ◎: Excellent, ○: Good, △: Average, X: Poor

[0193] Although the invention has been described in detail with reference to preferred embodiments, those skilled in the art or of ordinary skill in the art should understand that various modifications and alterations can be made to the invention without departing from the spirit and technical scope of the invention as described in this application.

Claims

1. A low-temperature thermosetting resin composition, comprising: Epoxy acrylic resin represented by chemical formula 1; Thermosetting agent; Curing accelerators; and The remaining solvent, [Chemical Formula 1] In chemical formula 1, n is an integer from 1 to 20. R1 and R 12 They are represented by the following chemical formulas 1-1, [Chemical Formula 1-1] In the chemical formula 1-1, R 13 and R 14 They are, respectively, any one of hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, and a polar group. R2 is represented by the following chemical formula 1-2, [Chemical Formula 1-2] In the chemical formulas 1-2, R3 includes (i) a hydrocarbon chain substituted or unsubstituted with halogen, hydroxyl, sulfone, nitro or cyano groups; (ii) a heterochain in which a portion of the carbon skeleton is substituted with nitrogen (N), oxygen (O) or sulfur (S); or (iii) an aromatic ring or polycyclic aromatic ring linked or fused together by a single bond. In the aforementioned chemical formula 1, R4, R5, R6, and R7 are represented by the following chemical formulas 1-3, respectively. [Chemical Formulas 1-3] In the chemical formula 1, R8, R9, R 10 and R 11 They are represented by the following chemical formulas 1-4 respectively. [Chemical Formulas 1-4] ； in, Indicates the binding site.

2. The low-temperature thermosetting resin composition according to claim 1, characterized in that, Based on 100 parts by weight of a low-temperature thermosetting resin composition, the content of the epoxy acrylate resin is 20 to 70 parts by weight.

3. The low-temperature thermosetting resin composition according to claim 1, characterized in that, The chemical formula 1 contains two or more epoxy groups, wherein the epoxy groups include at least one selected from the group of multifunctional epoxy acrylate resins composed of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD ​​type epoxy acrylate resin, phenolic varnish type epoxy resin and cresol varnish type epoxy acrylate resin.

4. The low-temperature thermosetting resin composition according to claim 1, characterized in that, The curing accelerator includes 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole or derivatives thereof.

5. The low-temperature thermosetting resin composition according to claim 1, characterized in that, The thermosetting agent includes at least one of phenolic varnish, cresol varnish, bisphenol A varnish, and naphthalene-type varnish.

6. A metal electrode structure configured to cover the metal electrode with the low-temperature thermosetting resin composition according to any one of claims 1 to 5.

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