WO2014119907A1 - Résine de silicone et son procédé de préparation - Google Patents

Résine de silicone et son procédé de préparation Download PDF

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Publication number
WO2014119907A1
WO2014119907A1 PCT/KR2014/000808 KR2014000808W WO2014119907A1 WO 2014119907 A1 WO2014119907 A1 WO 2014119907A1 KR 2014000808 W KR2014000808 W KR 2014000808W WO 2014119907 A1 WO2014119907 A1 WO 2014119907A1
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group
silicone resin
chemical formula
carbon atoms
weight
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PCT/KR2014/000808
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English (en)
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WO2014119907A9 (fr
Inventor
Ok Tak Kwon
Kyung Keun Yoon
Seok Gi Kim
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Kolon Industries, Inc.
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Publication of WO2014119907A1 publication Critical patent/WO2014119907A1/fr
Publication of WO2014119907A9 publication Critical patent/WO2014119907A9/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/58—Metal-containing linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the present invention relates to a silicone resin and a method of preparing the same.
  • Such liquid materials are largely classified into acryl-epoxy-based organic insulating layer materials and silicon-acrylic organic-inorganic hybrid insulating layer materials including an organopolysiloxane structure.
  • the organic insulating layer composition is advantageous in terms of forming a pattern using UV exposure and alkaline developing or of adhesion to a substrate, dielectric constant and chemical resistance, but is disadvantageous in terms of light resistance/heat resistance or transmittance, hardness and so on, and thus the preparation of silicon-based materials able to supplement such properties is under active study.
  • an object of the present invention is to provide a silicone resin and a method of preparing the same, wherein the silicone resin has superior heat resistance/light resistance and hardness, compared to acryl-epoxy-based organic resins.
  • Another object of the present invention is to provide a silicone resin and a method of preparing the same, wherein the silicone resin has superior adhesion at high temperature and high humidity, and low-temperature curing properties, and thus processing costs may be reduced, compared to acryl-epoxy-based organic resins.
  • a further object of the present invention is to provide a silicone resin composition including the silicone resin as above, and a cured product using the silicone resin composition.
  • an embodiment of the present invention provides a silicone resin, which is a condensation reaction product of at least one compound selected from among compounds represented by Chemical Formulas 1 to 3 below and at least one compound selected from among compounds represented by Chemical Formulas 4 to 6 below, and has a weight average molecular weight of 1,000 ⁇ 100,000 g/mol.
  • R 1 is each independently an organic group having 2 to 10 carbon atoms with at least one unsaturated bond or a mercapto group
  • R 2 is each independently a hydroxyl group, a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 2 to 10 carbon atoms, an epoxy group or a phenylene group
  • X is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acetate group or a halogen group
  • Me is a metal
  • n is an integer of 1 ⁇ 3.
  • R 1 is each independently selected from the group consisting of a vinyl group, a methacryl group, a methacryloxy group, an acetate group, an acryl group, an acryloxy group and a mercapto group.
  • Me is selected from the group consisting of aluminum, zirconium, titanium, zinc, manganese, cobalt, tungsten and vanadium.
  • Another embodiment of the present invention provides a method of preparing a silicone resin, comprising subjecting at least one compound selected from among compounds represented by Chemical Formulas 1 to 3 below and at least one compound selected from among compounds represented by Chemical Formulas 4 to 6 below to condensation reaction to give a silicone resin having a weight average molecular weight of 1,000 ⁇ 100,000 g/mol.
  • R 1 is each independently an organic group having 2 to 10 carbon atoms with at least one unsaturated bond or a mercapto group
  • R 2 is each independently a hydroxyl group, a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 2 to 10 carbon atoms, an epoxy group or a phenylene group
  • X is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acetate group or a halogen group
  • Me is a metal
  • n is an integer of 1 ⁇ 3.
  • R 1 is each independently selected from the group consisting of a vinyl group, a methacryl group, a methacryloxy group, an acetate group, an acryl group, an acryloxy group and a mercapto group.
  • Me is selected from the group consisting of aluminum, zirconium, titanium, zinc, manganese, cobalt, tungsten and vanadium.
  • the silicone resin is prepared by condensing at least one compound selected from among compounds represented by Chemical Formulas 1 to 3 and at least one compound selected from among compounds represented by Chemical Formulas 4 to 6 at a molar ratio of 100:1 ⁇ 100.
  • the condensation reaction is performed at a temperature ranging from room temperature to 150°C for 1 ⁇ 48 hr.
  • Still another embodiment of the present invention provides a silicone resin composition, comprising 1 ⁇ 70 wt% of the silicone resin as above, and a cured product formed using the silicone resin composition as above.
  • the silicone resin composition is cured at 100 ⁇ 300°C.
  • Yet another embodiment of the present invention provides a silicone resin, having a repeating unit represented by Chemical Formula 7 below and a weight average molecular weight of 1,000 ⁇ 100,000 g/mol.
  • R 1 is each independently an organic group having 2 to 10 carbon atoms with at least one unsaturated bond or a mercapto group
  • R 2 is each independentlya hydroxyl group, a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 2 to 10 carbon atoms, an epoxy group or a phenylene group
  • Me is a metal
  • n is 10 or less.
  • R 1 is each independently selected from the group consisting of a vinyl group, a methacryl group, a methacryloxy group, an acetate group, an acryl group, a mercapto group and an acryloxy group.
  • Me is selected from the group consisting of aluminum, zirconium, titanium, zinc, manganese, cobalt, tungsten and vanadium.
  • a silicone resin can overcome limitations of properties (heat resistance/light resistance, hardness, adhesion at high temperature and high humidity) of an organic resin (an acryl-epoxy resin) currently useful for displays and semiconductors, thereby achieving cost savings, advantageously protecting a device from scratching in subsequent processes in the presence of a layer formed thereby, and maintaining high adhesion to a substrate even at high temperature and high humidity. Therefore, this resin can be efficiently employed in manufacturing protective layers for displays and semiconductor devices.
  • An aspect of the present invention addresses a silicone resin, which is a condensation reaction product of at least one compound selected from among compounds represented by Chemical Formulas 1 to 3 below and at least one compound selected from among compounds represented by Chemical Formulas 4 to 6 below, and has a weight average molecular weight of 1,000 ⁇ 100,000 g/mol.
  • R 1 is each independently an organic group having 2 to 10 carbon atoms with at least one unsaturated bond or a mercapto group
  • R 2 is each independently a hydroxyl group, a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 2 to 10 carbon atoms, an epoxy group or a phenylene group
  • X is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acetate group or a halogen group
  • Me is a metal
  • n is an integer of 1 ⁇ 3.
  • Another aspect of the present invention addresses a method of preparing a silicone resin, comprising subjecting at least one compound selected from among compounds represented by Chemical Formulas 1 to 3 below and at least one compound selected from among compounds represented by Chemical Formulas 4 to 6 below to condensation reaction to give a silicone resin having a weight average molecular weight of 1,000 ⁇ 100,000 g/mol.
  • R 1 is each independently an organic group having 2 to 10 carbon atoms with at least one unsaturated bond or a mercapto group
  • R 2 is each independently a hydroxyl group, a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 2 to 10 carbon atoms, an epoxy group or a phenylene group
  • X is a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an acetate group or a halogen group
  • Me is a metal
  • n is an integer of 1 ⁇ 3.
  • Still another aspect of the present invention addresses a silicone resin composition comprising 1 ⁇ 70 wt% of the silicone resin, and a cured product formed from the silicone resin composition.
  • Yet another aspect of the present invention addresses a silicone resin having a repeating unit represented by Chemical Formula 7 below and a weight average molecular weight of 1,000 ⁇ 100,000 g/mol.
  • R 1 is each independently an organic group having 2 to 10 carbon atoms with at least one unsaturated bond or a mercapto group
  • R 2 is each independentlya hydroxyl group, a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 2 to 10 carbon atoms, an epoxy group or a phenylene group
  • Me is a metal
  • n is 10 or less.
  • the organic group may be selected from the group consisting of a vinyl group, a methacryl group, a methacryloxy group, an acetate group, an acryl group and an acryloxy group.
  • R 1 is selected from the group consisting of a vinyl group, a methacryl group, a methacryloxy group, an acetate group, an acryl group, an acryloxy group and a mercapto group is preferable in terms of forming a crosslinkageby radical reaction with an additive.
  • Me is selected from the group consisting ofaluminum, zirconium, titanium, zinc, manganese, cobalt, tungsten and vanadium is preferable in terms of reactivity.
  • the silicone resin includes -OH group in addition to the functional groups represented by R 1 and R 2 in the polymer chain thereof, and thus may have self-condensing properties when heated.
  • a composition containing such a silicone resin may have low-temperature curing properties which enable curing at low temperature (100 ⁇ 150°C).
  • the silicone resin has a weight average molecular weight of 1,000 ⁇ 100,000 g/mol. If the weight average molecular weight thereof is less than 1,000 g/mol, the coating layer may be decreased in flatness or developability. In contrast, if the weight average molecular weight thereof 100,000 g/mol, hardness may decrease or gelling may occur.
  • n represents an average degree of polymerization, and n is 10 or less, and is preferably in the range of 1 ⁇ 8.
  • the silicone resin is prepared by condensing at least one compound selected from among compounds represented by Chemical Formulas 1 to 3 and at least one compound selected from among compounds represented by Chemical Formulas 4 to 6. Compared to the case where condensation is performed using only the compound represented by Chemical Formulas 1 to 3, the case where it is condensed with at least one compound selected from among compounds represented by Chemical Formulas 4 to 6 may enhance hardness and adhesion at high temperature and high humidity, ultimately improving adhesion to a coating substrate.
  • the silicone resin as above is difficult to specify by a structural formula, but it may be prepared in the form of a polymer represented by Chemical Formula 7 below in which at least one compound selected from among compounds represented by Chemical Formulas 1 to 3 and at least one compound selected from among compounds represented by Chemical Formulas 4 to 6 are randomly irregularly arranged.
  • R 1 , R 2 , Me, and n are defined as above.
  • the silicone resin is prepared by condensing at least one compound selected from among compounds represented by Chemical Formulas 1 to 3 and at least one compound selected from among compounds represented by Chemical Formulas 4 to 6 at a molar ratio of 100:1 ⁇ 100, and preferably 100:10 ⁇ 80.
  • the silicone resin Upon preparation of the silicone resin, if the molar ratio of at least one compound selected from among compounds represented by Chemical Formulas 1 to 3 and at least one compound selected from among compounds represented by Chemical Formulas 4 to 6 falls outside the above range, it is difficult to form a polymer due to high reactivity of alkoxide of a metal other than silicon, or it is difficult to increase hardness due to the addition of metal alkoxide or to enhance adhesion at high temperature and high humidity.
  • the condensation between at least one compound selected from among compounds represented by Chemical Formulas 1 to 3 and at least one compound selected from among compounds represented by Chemical Formulas 4 to 6 may be carried out at a temperature ranging from room temperature to 150°C for 1 ⁇ 48 hr, and preferably 40 ⁇ 80°C for 1 ⁇ 12 hr.
  • condensation reaction is performed at a temperature lower than room temperature or for a period of time less than 1 hr, the reaction is not progressed. In contrast, if the reaction is performed at a temperature higher than 150°C or for a period of time longer than 48 hr, excessive condensation may occur, undesirably causing gelling upon formation of a polymer.
  • the reactants themselves are preferably used as a solvent, but the other reaction solvent may be used.
  • the reaction solvent is not particularly limited so long as it has the kind and amount which do not impede the reaction, and examples thereof may include alcohols such as methanol, ethanol, etc.; ethers such as tetrahydrofuran, diethyleneglycol dimethylether, diethyleneglycol diethylether, etc.; propyleneglycol alkylether acetates, such as propyleneglycol methylether acetate, propyleneglycol ethylether acetate, propyleneglycol propylether acetate, propyleneglycol butylether acetate, etc.
  • alcohols such as methanol, ethanol, etc.
  • ethers such as tetrahydrofuran, diethyleneglycol dimethylether, diethyleneglycol diethylether, etc.
  • propyleneglycol alkylether acetates such as propyleneglycol methylether acetate, propyleneglycol ethylether a
  • the silicone resin composition includes the silicone resin as above, and is thus superior in heat resistance/light resistance, hardness and curing properties at low temperature (100 ⁇ 150°C) and thus exhibits higher durability and cost savings, compared to conventional thermosetting and photocuring organic compositions including acryl-epoxy resin. If the amount of the silicone resin is less than 1 wt% based on the total amount of the composition, the effect of the addition of the silicone resin is insignificant. In contrast, if the amount thereof exceeds 70 wt%, storage stability may deteriorate due to curing properties.
  • the silicone resin composition may further include, in addition to the silicone resin, an additive and a solvent depending on purpose.
  • the additive is not particularly limited so long as it is typically useful in the art, and may include, for example, a surfactant, a leveling agent, an adhesion enhancer, a silane coupling agent, a chelating agent, a curing accelerator, etc.
  • the additive may be used in an amount of 5 ⁇ 50 parts by weight, and preferably 10 ⁇ 30 parts by weight, based on 100 parts by weight of the silicone resin. If the amount of the additive is less than 5 parts by weight, adhesion or leveling properties may become insignificant. In contrast, if the amount thereof exceeds 50 parts by weight, it is difficult to attain original properties of the composition.
  • the silicone resin composition according to the present invention includes a solvent.
  • the solvent may be used in an amount of 100 ⁇ 1,000 parts by weight, and preferably 150 ⁇ 700 parts by weight, based on 100 parts by weight of the silicone resin.
  • Specific examples of the solvent may include, but are not limited to, alcohols such as methanol, ethanol, etc.; ethers such as tetrahydrofuran, diethyleneglycol dimethylether, diethyleneglycol diethylether, etc.; propyleneglycol alkylether acetates, such as propyleneglycol methylether acetate, propyleneglycol ethylether acetate, propyleneglycol propylether acetate, propyleneglycol butylether acetate, etc.
  • a cured product such as a protective layer (an overcoat) for an optical device, an insulating layer for a semiconductor, etc. may be manufactured by applying the silicone resin composition as above, and performing prebaking (PRB) to evaporate the solvent, exposure, developing, and post-baking (PSB) to cure the coating.
  • PRB prebaking
  • PSB post-baking
  • the coating conditions preferably vary depending on the desired thickness.
  • PRB conditions are selected depending on the boiling point of the solvent used, and PRB is performed at 50 ⁇ 150°C, and preferably 80 ⁇ 130°C, for 10 ⁇ 200 sec, and preferably 30 ⁇ 150 sec. If this process is performed at a temperature lower than 50°C or for a period of time less than 30 sec, the solvent is not completely dried, which may affect the properties. In contrast, if this process is performed at a temperature higher than 150°C or for a period of time longer than 200 sec, the solvent contained in the composition may be rapidly dried, undesirably deteriorating coatability.
  • the exposure process indicates UV exposure at a dose of 10 ⁇ 1000 mJ/cm 2 (i-g-h line), and preferably 30 ⁇ 500 mJ/cm 2 (i-g-h line). If the dose is less than 10 mJ/cm 2 (i-g-h line), radical curing via exposure does not completely occur, and thus the coating layer may be washed off upon developing. In contrast, if the dose exceeds 1000 mJ/cm 2 (i-g-h line), pattern properties may become poor, and adhesion may decrease due to excessive curing.
  • the developing process indicates developing using an alkaline developer, and the developer is not limited to any one type.
  • the developing time may be set to 1 sec ⁇ 10 min, and preferably 20 sec ⁇ 5 min. If the developing time is less than 1 sec, a non-cured portion may not be washed off, making it difficult to form an appropriate pattern. In contrast, if the developing time exceeds 10 min, the pattern may be lost or only the developer may be used excessively, and thus the pattern properties do not change.
  • PSB may be performed at 100 ⁇ 300°C for a curing time of 1 ⁇ 3 hr, and preferably 100 ⁇ 250°C for a curing time of 30 min ⁇ 2 hr. If these curing conditions are less than 100°C and 30 min, complete curing does not take place, and thus hardness or adhesion may become poor. In contrast, if the curing conditions exceed 300°C and 3 hr, cracking may occur or transmittance may decrease.
  • the weight average molecular weight was determined from higher and lower molecular weights, in terms of polystyrene standards, by gel permeation chromatography (GPC) (Waters E2695).
  • GPC gel permeation chromatography
  • the corresponding polymer was dissolved in tetrahydrofuran to have a concentration of 1 wt% and then fed in an amount of 20 ⁇ l for GPC.
  • the mobile phase of GPC was tetrahydrofuran and was introduced at a flow rate of 1 mL/min, and analysis was performed at 40°C.
  • Two Plgel mixed D columns and one Plgel guard column were connected in series.
  • the detector was Waters 2414 RI Detector.
  • thermosetting silicone resin composition having a solid content of 16.8 wt% was prepared by mixing 100 parts by weight of the silicone resin obtained in Example 1-1, 150 parts by weight of propyleneglycol monomethylether acetate as a solvent, and, as additives, 10 parts by weight of 3-glycidyloxypropyltriethoxy silane (a silane coupling agent) and 0.5 parts by weight of a silicone surfactant (B-302, BYK) (2.5% diluted).
  • An insulating layer was formed by applying the thermosetting silicone resin composition obtained in Example 1-2 onto the surface of glass using spin coating at 450 rpm for 12 sec to thus form a coating layer having a thickness of 2 ⁇ m, prebaking the glass having the coating layer on a hot plate at 100°C for 90 sec, and then post-baking it in a convection oven at 150°C for 30 min.
  • a silicone resin in Chemical Formula 7, R 1 is a vinyl group, R 2 is an epoxy group (a 3-glycidyloxypropyl group), Me is zirconium, and n is 1) was prepared in the same manner as in Example 1-1, with the exception that 5 parts by weight (0.2 mol) of 3-glycidyloxypropyltrimethoxy silane (in Chemical Formula 2, R 2 is an epoxy group (a 3-glycidyloxypropyl group), X is methoxy, and n is 1) was used instead of vinyltriethoxy silane.
  • the weight average molecular weight of the silicone resin was 5,018 g/mol.
  • thermosetting silicone resin composition having a solid content of 17.1 wt% was prepared by mixing 100 parts by weight of the silicone resin obtained in Example 2-1, 150 parts by weight of propyleneglycol monomethylether acetate as a solvent, and, as additives, 10 parts by weight of 3-glycidyloxypropyltrimethoxy silane (a silane coupling agent) and 0.5 parts by weight of a silicone surfactant (B-302, BYK) (2.5% diluted).
  • An insulating layer was formed by applying the thermosetting silicone resin composition obtained in Example 2-2 onto the surface of glass using spin coating at 450 rpm for 12 sec to thus form a coating layer having a thickness of 2 ⁇ m, prebaking the glass having the coating layer on a hot plate at 100°C for 90 sec, and then post-baking it in a convection oven at 150°C for 30 min.
  • Example 1-1 168 g of a silicone resin (in Chemical Formula 7, R 1 is an acetate group, R 2 is a hydroxyl group, and Me is zirconium) was prepared in the same manner as in Example 1-1, with the exception that 5 parts by weight (0.5 mol) of zirconium (IV) acetate hydroxide (in Chemical Formula 4, R 1 is an acetate group, X is a hydroxyl group, and n is 1) was used instead of 0.5 mol zirconium (IV) butoxide.
  • the weight average molecular weight of the silicone resin was 5,210 g/mol.
  • thermosetting silicone resin composition having a solid content of 17.4 wt% was prepared by mixing 100 parts by weight of the silicone resin obtained in Example 3-1, 150 parts by weight of propyleneglycol monomethylether acetate as a solvent, and, as additives, 10 parts by weight of 3-glycidyloxypropyltrimethoxy silane (a silane coupling agent) and 0.5 parts by weight of a silicone surfactant (B-302, BYK) (2.5% diluted).
  • An insulating layer was formed by applying the thermosetting silicone resin composition obtained in Example 3-2 applied onto the surface of glass using spin coating at 450 rpm for 12 sec to thus form a coating layer having a thickness of 2 ⁇ m, prebaking the glass having the coating layer on a hot plate at 100°C for 90 sec, and then post-baking it in a convection oven at 150°C for 30 min.
  • 300 g of an acryl-epoxy resin composition having a solid content of 23% was prepared by mixing 100 parts by weight of the acryl-epoxy resin obtained in Comparative Example 1-2, 10 parts by weight of a urethane-based curing compound (UA-510I, Kyoeisha) and 10 parts by weight of an epoxy curing compound (E-103A, Arakawa).
  • a urethane-based curing compound U-510I, Kyoeisha
  • E-103A an epoxy curing compound
  • An insulating layer was formed by applying the acryl-epoxy resin composition obtained in Comparative Example 1-2 onto the surface of glass using spin coating at 450 rpm for 12 sec to thus form a coating layer having a thickness of 2 ⁇ m, prebaking the glass having the coating layer on a hot plate at 100°C for 90 sec, and then post-baking it in a convection oven at 150°C for 30 min.
  • 320 g of an acryl-epoxy resin composition having a solid content of 25% was prepared in the same manner as in Comparative Example 1, by mixing 100 parts by weight of the acryl-epoxy resin with 20 parts by weight of a urethane-based curing compound (UA-510I, Kyoeisha) and 20 parts by weight of an epoxy curing compound (E-103A, Arakawa). Also, an insulating layer was formed in the same manner as in Example 1.
  • a silicone resin composition was prepared in the same manner as in Example 1. Specifically, 150 g of a silicone resin (in Chemical Formula 7, R 1 is a vinyl group, R 2 is a hydroxyl group, and n is 1) was obtained, by carrying out the reaction without the use of zirconium (IV) butoxide. The weight average molecular weight of the silicone resin was 5,000 g/mol.
  • a silicone resin composition having a solid content of 17.4 wt% was prepared by mixing 100 parts by weight of the silicone resin as above, 150 parts by weight of propyleneglycol monomethylether acetate as a solvent, and, as additives, 10 parts by weight of 3-glycidyloxypropyltrimethoxy silane (a silane coupling agent) and 0.5 parts by weight of a silicone surfactant (B-302, BYK) (2.5% diluted). Also, an insulating layer was formed in the same manner as in Example 1.
  • a silicone resin (in Chemical Formula 7, R 1 is a vinyl group, R 2 is a hydroxyl group, Me is zirconium, and n is 1)was prepared in the same manner as in Example 1-1, with the exception that 165 parts by weight (1.5 mol) of zirconium (IV) butoxide was used instead of 0.5 mol zirconium (IV) butoxide.
  • thermosetting compositions of comparative Example 4 could not be measured and evaluated due to its gelation.
  • thermosetting compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were measured and evaluated. The results are given in Tables 1 to 5 below.
  • composition of each of Examples 1 to 3 and Comparative Example 1 to 3 was applied on glass using spin coating at 450 rpm for 12 sec to thus form a coating layer having a thickness of 2 ⁇ m, followed by prebaking on a hot plate at 100°C for 90 sec and curing in a convection oven at 150°C, 180°C, 200°C and 230°C for 20 min each.
  • the hardness of the layer thus cured was measured by pencil hardness under a load of 9.8 N using a pencil and a tester according to JIS-D5400. The results are shown in Table 1 below.
  • composition of each of Examples 1 to 3 and Comparative Example 1 to 3 was applied on glass using spin coating at 450 rpm for 12 sec to thus form a coating layer having a thickness of 2 ⁇ m, followed by prebaking on a hot plate at 100°C for 90 sec and curing in a convection oven at 200°C for 20 min.
  • the transmittance (%) of the layer thus cured was measured at a wavelength of 400 nm using a UV/Vis spectrometer to determine changes in transmittance after exposure to UV (60 J) and also changes in transmittance after exposure to high temperature (240°C, 90 min). The results are shown in Table 1 below.
  • the layer exposed to high temperature and UV as in (2) was measured for changes in color thereof using a colorimeter (CM-3500d, Konica Minolta). The results are shown in Table 2 below.
  • Example 1 The composition of each of Example 1 and Comparative Example 1 was applied on glass using spin coating at 450 rpm for 12 sec to thus form a coating layer, followed by prebaking on a hot plate at 100°C for 90 sec and curing in a convection oven at 150°C for 30 min.
  • the layer thus cured was exposed to 120°C and 100%RH for 6 hr, after which adhesion thereof was observed (Table 3).
  • the layer was immersed at 40°C for 30 min in chemicals (n-methyl-2-pyrrolidone (NMP), 5% HCl and 5% tetramethyl ammonium hydroxide (TMAH)), and thus changes in layer thickness were measured (Table 4). The measurement was repeated three times.
  • NMP n-methyl-2-pyrrolidone
  • TMAH tetramethyl ammonium hydroxide
  • silicone resin compositions of Examples 1 and 2 had no changes in transmittance upon exposure to UV and high temperature, compared to the acryl-epoxy compositions of Comparative Examples 1 and 2.
  • Exposure(240°C, 90min) 97.25 -0.05 0.25 0.27 Ex.3 Curing (150°C, 20 min) 97.40 -0.03 0.20 0.14 UV Exposure (60J) 97.29 -0.04 0.23 0.19 High Temp. Exposure(240°C, 90min) 97.18 -0.06 0.27 0.26 C.Ex.1 Curing (150°C, 20 min) 96.98 -0.03 0.25 0.25 UV Exposure (60J) 96.84 -0.36 1.50 2.10 High Temp.
  • Exposure(240°C, 90min) 95.61 -0.90 5.78 8.53 C.Ex.2 Curing (150°C, 20 min) 96.81 -0.05 0.29 0.33 UV Exposure (60J) 95.91 -0.40 2.10 3.01 High Temp. Exposure(240°C, 90min) 95.34 -0.98 7.85 10.21 C.Ex.3 Curing (150°C, 20 min) Not measured(cracked) Not measured(cracked) Not measured(cracked) Not measured(cracked) UV Exposure (60J) Not measured(cracked) Not measured(cracked) Not measured(cracked) Not measured(cracked) High Temp. Exposure(240°C, 90min) Not measured(cracked) Not measured(cracked) Not measured(cracked) Not measured(cracked) Not measured(cracked)
  • Acryl-epoxy-based materials are typically known to exhibit superior chemical resistance or adhesion to a substrate compared to silicon-based materials. As seen in the above results, however, the silicone resin according to the present invention exhibited superior durability (heat resistance/light resistance) or hardness while manifesting chemical resistance or adhesion equivalent to that of acryl-epoxy-based materials.
  • a silicone resin in Chemical Formula 7, R 1 is a methacryl group, R 2 is a methyl group, Me is zirconium, and n is 1) having a solid content of 39 wt%.
  • the weight average molecular weight of the silicone resin was 4,300 g/mol.
  • a photocuring silicone resin composition having a solid content of 17 wt% was prepared by mixing 100 parts by weight of the silicone resin obtained in Example 4-1, 150 parts by weight of propyleneglycol monomethylether acetate as a solvent, and, as additives, 1 part by weight of a photoinitiator (OXE-01, Ciba), 25 parts by weight of dipentaerythritol hexaacrylate (DPHA), 3 parts by weight of 3-glycidyloxypropyltrimethoxy silane and 0.3 parts by weight of a fluorine-based surfactant (RS-72K, DIC) (3.8% diluted).
  • a photoinitiator OXE-01, Ciba
  • DPHA dipentaerythritol hexaacrylate
  • RS-72K fluorine-based surfactant
  • An insulating layer was formed by applying the photocuring silicone resin composition obtained in Example 4-2 onto the surface of glass using spin coating at 450 rpm for 12 sec to thus form a coating layer having a thickness of 2 ⁇ m, prebaking the glass having the coating layer on a hot plate at 100°C for 90 sec, followed by exposure at 80mJ/cm 2 (i-g-h line), developing for 50 sec using 2.38% tetramethyl ammonium hydroxide (TMAH) as an alkaline developer, and then post-baking in a convection oven at 150°C for 30 min.
  • TMAH tetramethyl ammonium hydroxide
  • a silicone resin in Chemical Formula 7, R 1 is a mercapto group, R 2 is a methyl group, Me is zirconium, and n is 1) having a solid content of 40 wt% was prepared in the same manner as in Example 4-1, with the exception that 50 parts by weight (0.4 mol) of 3-mercaptopropyltrimethoxy silane (in Chemical Formula 1, R 1 is a mercapto group, X is a methoxy group, and n is 1) was added instead of 3-methacryloxypropyltrimethoxy silane.
  • the weight average molecular weight of the silicone resin was 5,200 g/mol.
  • a photocuring silicone resin composition having a solid content of 17 wt% was prepared by mixing 100 parts by weight of the silicone resin obtained in Example 5-1, 150 parts by weight of propyleneglycol monomethylether acetate as a solvent, and, as additives, 1 part by weight of a photoinitiator (OXE-01, Ciba), 25 parts by weight of dipentaerythritol hexaacrylate (DPHA), 3 parts by weight of 3-glycidyloxypropyltrimethoxy silane and 0.3 parts by weight of a fluorine-based surfactant (RS-72K, DIC) (3.8% diluted).
  • a photoinitiator OXE-01, Ciba
  • DPHA dipentaerythritol hexaacrylate
  • RS-72K fluorine-based surfactant
  • An insulating layer was formed by applying the photocuring silicone resin composition obtained in Example 5-2 onto the surface of glass using spin coating at 450 rpm for 12 sec to thus form a coating layer having a thickness of 2 ⁇ m, prebaking the glass having the coating layer on a hot plate at 100°C for 90 sec, followed by exposure at 80 mJ/cm 2 (i-g-h line)/cm2(i-g-h line), developing for 50 sec using 2.38% TMAH as an alkaline developer, and then post-baking in a convection oven at 150°C for 30 min.
  • a silicone resin (in Chemical Formula 7, R 1 is a methacryl group, R 2 is an epoxy group, Me is zirconium, and n is 1) having a solid content of 48.9 wt% was prepared in the same manner as in Example 4-1, with the exception that 50 parts by weight (0.4 mol) of 3-glycidyloxypropyltrimethoxy silane (in Chemical Formula 2, R 2 is an epoxy group (a 3-glycidyloxypropyl group), X is a methoxy group, and n is 1) instead of methyltrimethoxy silane, and 53 parts by weight (0.5 mol) of zirconium (IV) butoxide (in Chemical Formula 6, X is a butoxy group, and Me is zirconium) instead of 0.5 mol zirconium (IV) acetate were added.
  • the weight average molecular weight of the silicone resin was 5,250 g/mol.
  • a photocuring silicone resin composition having a solid content of 17 wt% was prepared by mixing 100 parts by weight of the silicone resin obtained in Example 6-1, 150 parts by weight of propyleneglycol monomethylether acetate as a solvent, and, as additives, 1 part by weight of a photoinitiator (OXE-01, Ciba), 25 parts by weight of dipentaerythritol hexaacrylate (DPHA), 3 parts by weight of 3-glycidyloxypropyltrimethoxy silane and 0.3 parts by weight of a fluorine-based surfactant (RS-72K, DIC) (3.8% diluted).
  • a photoinitiator OXE-01, Ciba
  • DPHA dipentaerythritol hexaacrylate
  • RS-72K fluorine-based surfactant
  • An insulating layer was formed by applying the photocuring silicone resin composition obtained in Example 6-2 onto the surface of glass using spin coating at 450 rpm for 12 sec to thus form a coating layer having a thickness of 2 ⁇ m, prebaking the glass having the coating layer on a hot plate at 100°C for 90 sec, followed by exposure at 80 mJ/cm 2 (i-g-h line), developing for 50 sec using 2.38% TMAH as an alkaline developer, and then post-baking in a convection oven at 150°C for 30 min.
  • an acryl-epoxy resin composition having a solid content of 17 wt% was prepared by mixing 100 parts by weight of the acryl-epoxy resin obtained in Comparative Example 5-1, 150 parts by weight of propyleneglycol monomethylether acetate as a solvent, and, as additives, 1 part by weight of a photoinitiator (OXE-01, Ciba), 25 parts by weight of dipentaerythritol hexaacrylate (DPHA), 3 parts by weight of 3-glycidyloxypropyltrimethoxy silane and 0.3 parts by weight of a fluorine-based surfactant (RS-72K, DIC) (3.8% diluted).
  • a photoinitiator OXE-01, Ciba
  • DPHA dipentaerythritol hexaacrylate
  • SR-72K fluorine-based surfactant
  • An insulating layer was formed by applying the acryl-epoxy resin composition obtained in Comparative Example 5-2 onto the surface of glass using spin coating at 450 rpm for 12 sec to thus form a coating layer having a thickness of 2 ⁇ m, prebaking the glass having the coating layer on a hot plate at 100°C for 90 sec, followed by exposure at 80 mJ/cm 2 (i-g-h line), developing for 50 sec using 2.38% TMAH as an alkaline developer, and then post-baking in a convection oven at 150°C for 30 min.
  • 320 g of an acryl-epoxy resin composition having a solid content of 22.5% was prepared in the same manner as in Comparative Example 5, with the exception that 100 parts by weight of dipentaerythritol hexaacrylate (DPHA) and 20 parts by weight of an epoxy curing compound (E-103A, Arakawa) were further added based on 100 parts by weight of the acryl-epoxy resin. Also, an insulating layer was formed in the same manner as in Example 4.
  • DPHA dipentaerythritol hexaacrylate
  • E-103A epoxy curing compound
  • a photocuring silicone resin composition was prepared in the same manner as in Example 4 except for zirconium (IV) acetate. Specifically, 150 g of a silicone resin was prepared, by carrying out the reaction without the use of zirconium (IV) acetate. The weight average molecular weight of the silicone resin was 5,200 g/mol.
  • a photocuring silicone resin composition having a solid content of 17 wt% was prepared by mixing 100 parts by weight of the silicone resin as above, 150 parts by weight of propyleneglycol monomethylether acetate as a solvent, and, as additives, 1 part by weight of a photoinitiator (OXE-01, Ciba), 25 parts by weight of dipentaerythritol hexaacrylate (DPHA), 10 parts by weight of 3-glycidyloxypropyltrimethoxy silane, and 0.3 parts by weight of a fluorine-based surfactant (RS-72K, DIC) (3.8% diluted). Also, an insulating layer was formed in the same manner as in Example 4.
  • composition of each of Examples 4 to 6 and Comparative Examples 5 to 7 was applied on glass using spin coating at 450 rpm for 12 sec to thus form a coating layer having a thickness of 2 ⁇ m, followed by prebaking (PRB) on a hot plate at 100°C for 90 sec, exposure (UV) at 80 mJ/cm 2 (i-g-h line), developing for 50 sec (2.38% TMAH) and post-baking (PSB) in a convection oven at 100°C, 120°C, 140°C and 150°C for 30 min each.
  • PRB prebaking
  • UV exposure
  • i-g-h line exposure
  • PSB post-baking
  • the hardness of the layer thus cured was measured by pencil hardness under a load of 9.8 N using a pencil and a tester according to JIS-D5400. The results are shown in Table 5 below.
  • composition of each of Examples 4 to 6 and Comparative Examples 5 to 7 was applied on glass using spin coating at 450 rpm for 12 sec to thus form a coating layer having a thickness of 2 ⁇ m, followed by PRB on a hot plate at 100°C for 90 sec, exposure (UV) at 80 mJ/cm 2 (i-g-h line), developing for 50 sec (2.38% TMAH) and curing in a convection oven at 150°C for 30 min.
  • the transmittance (%) of the layer thus cured was measured at a wavelength of 400 nm using a UV/Vis spectrometer (Evolution600, Thermo) to determine changes in transmittance after exposure to high temperature (250°C, 90 min). The results are shown in Table 5 below.
  • composition of each of Examples 4 to 6 and Comparative Examples 5 to 7 was applied on ITO glass using spin coating at 450 rpm for 12 sec to thus form a coating layer having a thickness of 2 ⁇ m, followed by PRB on a hot plate at 100°C for 90 sec, exposure (UV) at 80 mJ/cm 2 (i-g-h line), developing for 50 sec (2.38% TMAH) and curing in a convection oven at 150°C for 30 min.
  • the layer thus cured was exposed to 120°C and 100%RH for 6 hr, after which adhesion thereof was observed using an optical microscope (MM-400, Nikon) (Table 6). The measurement was repeated three times.

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  • Engineering & Computer Science (AREA)
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Abstract

Cette invention concerne une résine de silicone et un procédé de préparation de celle-ci, dans laquelle la résine de silicone est maintenue dans une dureté élevée même lors d'un durcissement à basse température tout en surmontant les limitations de propriétés (résistance à la chaleur/résistance à la lumière, dureté et adhérence à température élevée et humidité élevée) d'une résine organique (une résine acryl-époxy) pour des dispositifs d'affichage et des semi-conducteurs nécessitant des spécifications élevées, obtenant donc des économies, protégeant de façon favorable le dispositif des rayures dans des procédés subséquents en présence d'une couche formée ainsi, et maintenant une adhérence élevée à un substrat même à température élevée et humidité élevée, en la rendant en fin de compte utile pour fabriquer une couche de protection pour des dispositifs d'affichage et des dispositifs semi-conducteurs.
PCT/KR2014/000808 2013-01-31 2014-01-28 Résine de silicone et son procédé de préparation WO2014119907A1 (fr)

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US6368535B1 (en) * 1999-08-06 2002-04-09 Dow Corning Corporation Condensation reaction curable silsesquioxane resin composition and methods for the synthesis and cure thereof
US20040046632A1 (en) * 2001-10-05 2004-03-11 Tomoji Kumano Iron core exhibiting excellent insulating property at end face, and method for coating end face of iron core
KR100506584B1 (ko) * 2003-02-24 2005-08-05 주식회사 케이씨씨 실리콘 수지의 제조방법
KR20120079966A (ko) * 2011-01-06 2012-07-16 주식회사 동진쎄미켐 광학소자 봉지용 실리콘 수지 조성물

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JP2001335745A (ja) * 2000-05-29 2001-12-04 Jsr Corp 膜形成用組成物、膜の形成方法およびシリカ系膜
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WO2010001949A1 (fr) * 2008-07-02 2010-01-07 出光興産株式会社 Liquide de revêtement, film durci, corps multicouches de résine, procédé de fabrication du film durci et procédé de fabrication du corps multicouches de résine
JP5462603B2 (ja) 2009-11-26 2014-04-02 宇部エクシモ株式会社 素子分離材料用塗布液、素子分離材料用塗布液の作製方法、素子分離層用薄膜、素子分離層用薄膜の形成方法、基板、及び、基板の形成方法
CN103210041B (zh) * 2010-11-10 2014-06-11 横滨橡胶株式会社 热固化型有机硅树脂组合物、以及使用该组合物而得的含有有机硅树脂的结构体和光半导体元件密封体

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US6368535B1 (en) * 1999-08-06 2002-04-09 Dow Corning Corporation Condensation reaction curable silsesquioxane resin composition and methods for the synthesis and cure thereof
US20020037417A1 (en) * 2000-08-04 2002-03-28 Kazuharu Sato Coating composition and coated article
US20040046632A1 (en) * 2001-10-05 2004-03-11 Tomoji Kumano Iron core exhibiting excellent insulating property at end face, and method for coating end face of iron core
KR100506584B1 (ko) * 2003-02-24 2005-08-05 주식회사 케이씨씨 실리콘 수지의 제조방법
KR20120079966A (ko) * 2011-01-06 2012-07-16 주식회사 동진쎄미켐 광학소자 봉지용 실리콘 수지 조성물

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KR20140098704A (ko) 2014-08-08
TW201433593A (zh) 2014-09-01

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