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WO2014119907A1 - Silicone resin and method of preparing the same - Google Patents

Silicone resin and method of preparing the same 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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Prior art keywords
group
silicone resin
chemical formula
carbon atoms
weight
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PCT/KR2014/000808
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French (fr)
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WO2014119907A9 (en
Inventor
Ok Tak Kwon
Kyung Keun Yoon
Seok Gi Kim
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Kolon Industries Inc
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Kolon Industries Inc
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Publication of WO2014119907A9 publication Critical patent/WO2014119907A9/en
Anticipated expiration legal-status Critical
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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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Abstract

This invention relates to a silicone resin and a method of preparing the same, wherein the silicone resin is maintained in high hardness even upon low-temperature curing while overcoming limitations of properties (heat resistance/light resistance, hardness and adhesion at high temperature and high humidity) of an organic resin (an acryl-epoxy resin) for displays and semiconductors requiring high specifications, thus achieving cost savings, favorably protecting the device from scratching in subsequent processes in the presence of a layer formed thereby, and keeping high adhesion to a substrate even at high temperature and high humidity, ultimately making it useful to manufacture a protective layer for displays and semiconductor devices.

Description

SILICONE RESIN AND METHOD OF PREPARING THE SAME
The present invention relates to a silicone resin and a method of preparing the same.
In the case of currently useful materials of insulating layers (passivations) for displays and semiconductors, liquid materials using a coating process which is beneficial in processing, instead of a deposition process of inorganic materials (SiNx), are being vigorously developed.
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.
Accordingly, 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.
In order to accomplish the above objects, 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.
<Chemical Formula 1>
R1(n)SiX(4-n)
<Chemical Formula 2>
R2(n)SiX(4-n)
<Chemical Formula 3>
SiX4
<Chemical Formula 4>
R1(n)MeX(4-n)
<Chemical Formula 5>
R2(n)MeX(4-n)
<Chemical Formula 6>
MeX4
In Chemical Formulas 1 to 6, R1 is each independently an organic group having 2 to 10 carbon atoms with at least one unsaturated bond or a mercapto group; R2 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, and n is an integer of 1 ~ 3.
In a preferred embodiment of the present invention, R1 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.
In a preferred embodiment of the present invention, 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.
<Chemical Formula 1>
R1(n)SiX(4-n)
<Chemical Formula 2>
R2(n)SiX(4-n)
<Chemical Formula 3>
SiX4
<Chemical Formula 4>
R1(n)MeX(4-n)
<Chemical Formula 5>
R2(n)MeX(4-n)
<Chemical Formula 6>
MeX4
In Chemical Formulas 1 to 6, R1 is each independently an organic group having 2 to 10 carbon atoms with at least one unsaturated bond or a mercapto group; R2 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, and n is an integer of 1 ~ 3.
In a preferred embodiment of the present invention, R1 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.
In a preferred embodiment of the present invention, Me is selected from the group consisting of aluminum, zirconium, titanium, zinc, manganese, cobalt, tungsten and vanadium.
In a preferred embodiment of the present invention, 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.
In a preferred embodiment of the present invention, the condensation reaction is performed at a temperature ranging from room temperature to 150℃ 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.
In a preferred embodiment of the present invention, the silicone resin composition is cured at 100 ~ 300℃.
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.
<Chemical Formula 7>
Figure PCTKR2014000808-appb-I000001
In Chemical Formula 7, R1 is each independently an organic group having 2 to 10 carbon atoms with at least one unsaturated bond or a mercapto group; R2 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,
Figure PCTKR2014000808-appb-I000002
is represented by Chemical Formula 8 below, and n is 10 or less.
<Chemical Formula 8>
Figure PCTKR2014000808-appb-I000003
In a preferred embodiment of the present invention, R1 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.
In a preferred embodiment of the present invention, Me is selected from the group consisting of aluminum, zirconium, titanium, zinc, manganese, cobalt, tungsten and vanadium.
According to the present invention, 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.
Unless otherwise defined, all the technical and scientific terms used herein have the same meanings as those typically understood by those skilled in the art to which the present invention belongs. Generally, the nomenclature used herein is well known in the art and is of typical.
Throughout the specification, when any part “includes” any element, it means that the other elements are not excluded but may be further included, unless otherwise stated.
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.
<Chemical Formula 1>
R1(n)SiX(4-n)
<Chemical Formula 2>
R2(n)SiX(4-n)
<Chemical Formula 3>
SiX4
<Chemical Formula 4>
R1(n)MeX(4-n)
<Chemical Formula 5>
R2(n)MeX(4-n)
<Chemical Formula 6>
MeX4
In Chemical Formulas 1 to 6, R1 is each independently an organic group having 2 to 10 carbon atoms with at least one unsaturated bond or a mercapto group; R2 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, and 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.
<Chemical Formula 1>
R1(n)SiX(4-n)
<Chemical Formula 2>
R2(n)SiX(4-n)
<Chemical Formula 3>
SiX4
<Chemical Formula 4>
R1(n)MeX(4-n)
<Chemical Formula 5>
R2(n)MeX(4-n)
<Chemical Formula 6>
MeX4
In Chemical Formulas 1 to 6, R1 is each independently an organic group having 2 to 10 carbon atoms with at least one unsaturated bond or a mercapto group; R2 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, and 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.
<Chemical Formula 7>
Figure PCTKR2014000808-appb-I000004
In Chemical Formula 7, R1 is each independently an organic group having 2 to 10 carbon atoms with at least one unsaturated bond or a mercapto group; R2 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,
Figure PCTKR2014000808-appb-I000005
is represented by Chemical Formula 8 below, and n is 10 or less.
<Chemical Formula 8>
Figure PCTKR2014000808-appb-I000006
In Chemical Formulas 1 to 7, 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.
Also, in Chemical Formulas 1 to 7, the case where R1 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 groupis preferable in terms of forming a crosslinkageby radical reaction with an additive.
Also, in Chemical Formulas 1 to 7, the case where Me is selected from the group consisting ofaluminum, zirconium, titanium, zinc, manganese, cobalt, tungsten and vanadium is preferable in terms of reactivity.
According to the present invention, the silicone resin includes -OH group in addition to the functional groups represented by R1 and R2 in the polymer chain thereof, and thus may have self-condensing properties when heated. Hence, a composition containing such a silicone resin may have low-temperature curing properties which enable curing at low temperature (100 ~ 150℃).
Also, 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.
In Chemical Formula 7, 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.
Specifically, 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.
<Chemical Formula 7>
Figure PCTKR2014000808-appb-I000007
In Chemical Formula 7, R1, R2, Me,
Figure PCTKR2014000808-appb-I000008
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.
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℃ for 1 ~ 48 hr, and preferably 40 ~ 80℃ for 1 ~ 12 hr.
If the 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℃ or for a period of time longer than 48 hr, excessive condensation may occur, undesirably causing gelling upon formation of a polymer.
In the reaction scheme according to the present invention, the reactants (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) 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.
According to the present invention, 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℃) 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.
In the present invention, 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.
Upon applying the composition, spin coating, bar coating, dipping or the like may be implemented, and the coating conditions preferably vary depending on the desired thickness.
It is preferable that PRB conditions are selected depending on the boiling point of the solvent used, and PRB is performed at 50 ~ 150℃, and preferably 80 ~ 130℃, for 10 ~ 200 sec, and preferably 30 ~ 150 sec. If this process is performed at a temperature lower than 50℃ 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℃ 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/cm2(i-g-h line), and preferably 30 ~ 500 mJ/cm2(i-g-h line). If the dose is less than 10 mJ/cm2(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/cm2(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℃ for a curing time of 1 ~ 3 hr, and preferably 100 ~ 250℃ for a curing time of 30 min ~ 2 hr. If these curing conditions are less than 100℃ 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℃ and 3 hr, cracking may occur or transmittance may decrease.
A better understanding of the present invention may be obtained through the following examples and comparative examples which are set forth to illustrate, but are not to be construed as limiting the present invention.
<Example 1>
1-1: Preparation of silicone resin
In a reactor equipped with a cooling tube and a stirrer, 100 parts by weight of propyleneglycol monomethylether acetate as a solvent, 5 parts by weight (0.2 mol) of vinyltriethoxy silane (in Chemical Formula 1, R1 is a vinyl group, X is ethoxy, and n is 1) and 60 parts by weight (0.8 mol) of tetraethoxy silane (in Chemical Formula 3, X is ethoxy) were mixed at room temperature, and 5 parts by weight of 0.01 N HCl was slowly added dropwise and hydrolysis was carried out for 1 hr. To this reaction mixture, 55 parts by weight (0.5 mol) of zirconium (IV) butoxide (in Chemical Formula 6, Me is zirconium, and X is butoxy) was slowly added dropwise over 30 min, after which the reaction was carried out at 70℃ for 5 hr. The resulting reaction product was cooled to room temperature and stabilized for 10 hr, and 80 parts by weight of propyleneglycol monomethylether acetate was further added. To remove byproducts such as water, alcohol, etc. produced during the reaction, vacuum evaporation was performed at 60℃, yielding 178 g of a silicone resin (in Chemical Formula 7, R1 is a vinyl group, R2 is a hydroxyl 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 4,725 g/mol.
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). The corresponding polymer was dissolved in tetrahydrofuran to have a concentration of 1 wt% and then fed in an amount of 20 ㎕ 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℃. Two Plgel mixed D columns and one Plgel guard column were connected in series. The detector was Waters 2414 RI Detector.
1-2: Preparation of silicone resin composition
50 g of a 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).
1-3: Formation of insulating layer
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 ㎛, prebaking the glass having the coating layer on a hot plate at 100℃ for 90 sec, and then post-baking it in a convection oven at 150℃ for 30 min.
<Example 2>
2-1: Preparation of silicone resin
185 g of a silicone resin (in Chemical Formula 7, R1 is a vinyl group, R2 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, R2 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.
2-2: Preparation of silicone resin composition
50 g of a 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).
2-3: Formation of insulating layer
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 ㎛, prebaking the glass having the coating layer on a hot plate at 100℃ for 90 sec, and then post-baking it in a convection oven at 150℃ for 30 min.
<Example 3>
3-1: Preparation of silicone resin
168 g of a silicone resin (in Chemical Formula 7, R1 is an acetate group, R2 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, R1 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.
3-2: Preparation of silicone resin composition
50 g of a 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).
3-3: Formation of insulating layer
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 ㎛, prebaking the glass having the coating layer on a hot plate at 100℃ for 90 sec, and then post-baking it in a convection oven at 150℃ for 30 min.
<Comparative Example 1>
1-1: Preparation of acryl-epoxy resin
In a reactor equipped with a cooling tube and a stirrer, 2.5 parts by weight of 2,2'-azobisisobutyronitrile was dissolved in 100 parts by weight of diethyleneglycol dimethylether. Subsequently, 5 parts by weight of styrene, 7.5 parts by weight of methacrylic acid, 27.5 parts by weight of glycidyl methacrylate and 10 parts by weight of dicylcopentenyloxyethyl methacrylate were added, followed by nitrogen purging and stirring. The temperature of this reaction mixture was increased to 80℃ and the reaction was carried out for 6 hr, yielding 355 g of an acryl-epoxy resin having a solid content of 39 wt%. The weight average molecular weight of the acryl-epoxy resin was 7,500 g/mol.
1-2: Preparation of acryl-epoxy resin composition
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).
1-3: Formation of insulating layer
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 ㎛, prebaking the glass having the coating layer on a hot plate at 100℃ for 90 sec, and then post-baking it in a convection oven at 150℃ for 30 min.
<Comparative Example 2>
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.
<Comparative Example 3>
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, R1 is a vinyl group, R2 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. 50 g of 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.
<Comparative Example 4>
A silicone resin (in Chemical Formula 7, R1 is a vinyl group, R2 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.
The properties of the thermosetting compositions of comparative Example 4 could not be measured and evaluated due to its gelation.
The properties of the 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.
(1) Measurement of changes in pencil hardness at different curing temperatures
The 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 ㎛, followed by prebaking on a hot plate at 100℃ for 90 sec and curing in a convection oven at 150℃, 180℃, 200℃ and 230℃ 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.
(2) Measurement of transmittance upon exposure to high temperature/UV
The 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 ㎛, followed by prebaking on a hot plate at 100℃ for 90 sec and curing in a convection oven at 200℃ 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℃, 90 min). The results are shown in Table 1 below.
(3) Measurement of changes in color upon exposure to high temperature/UV
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.
(4) Measurement of adhesion at high temperature and high humidity and chemical resistance
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℃ for 90 sec and curing in a convection oven at 150℃ for 30 min. The layer thus cured was exposed to 120℃ and 100%RH for 6 hr, after which adhesion thereof was observed (Table 3). Also, the layer was immersed at 40℃ 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.
Table 1
Ex.1 Ex.2 Ex.3 C.Ex.1 C.Ex.2 C.Ex.3
Pencil Hardness(at Temp.) Curing(150℃, 20 min) 3H 3H 3H 1H HB 3H
Curing(180℃, 20 min) 6H 5H 5H 2H H 5H
Curing(200℃, 20 min) 7H 6H 6H 3H 3H Not measured(cracked)
Curing(230℃, 20 min) 7H 7H 6H 5H 4H Not measured(cracked)
Transmittance(%, 400nm) Curing(200℃, 20 min) 99.79 99.89 99.81 98.82 98.51 Not measured(cracked)
UV Exposure(60J) 99.34 99.31 99.22 82.82 90.74 Not measured(cracked)
High Temp.Exposure(240℃, 90min) 99.29 99.25 99.10 77.50 68.21 Not measured(cracked)
As is apparent from Table 1, the silicone resin compositions of Examples 1 to 3 were cured at lower temperature and exhibited superior pencil hardness at lower temperature, compared to the acryl-epoxy compositions of Comparative Examples 1 and 2.
Furthermore, the 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.
Whereas the cured layer of Comparative Example 3 was cracked at a temperature of 200℃ or more, the layers of Examples 1 to 3 were not cracked and thus exhibited superior crack resistance.
Table 2
L a b YI
Ex.1 Curing (150℃, 20 min) 97.42 -0.02 0.17 0.12
UV Exposure(60J) 97.38 -0.03 0.24 0.23
High Temp.Exposure(240℃, 90min) 97.20 -0.06 0.25 0.24
Ex.2 Curing (150℃, 20 min) 97.45 -0.03 0.19 0.15
UV Exposure (60J) 97.40 -0.03 0.23 0.21
High Temp. Exposure(240℃, 90min) 97.25 -0.05 0.25 0.27
Ex.3 Curing (150℃, 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℃, 90min) 97.18 -0.06 0.27 0.26
C.Ex.1 Curing (150℃, 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℃, 90min) 95.61 -0.90 5.78 8.53
C.Ex.2 Curing (150℃, 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℃, 90min) 95.34 -0.98 7.85 10.21
C.Ex.3 Curing (150℃, 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℃, 90min) Not measured(cracked) Not measured(cracked) Not measured(cracked) Not measured(cracked)
As is apparent from Table 2, the silicone resin composition of Examples 1 to 3 had no changes in color upon exposure to UV and high temperature, compared to the acryl-epoxy compositions of Comparative Examples 1 and 2.
Table 3
Ex.1 C.Ex.1
High Temp. High Humidity Adhesion(120℃, 100%RH) Optical Microscopic Image (× 200)
Figure PCTKR2014000808-appb-I000009
Figure PCTKR2014000808-appb-I000010
Separation(Delamination) No Separation No Separation
As is apparent from Table 3, adhesion to a substrate at high temperature/high humidity was superior without separation in both of Example 1 and Comparative Example 1.
Table 4
Thickness(㎛)
NMP 5% HCl 5% TMAH
Before After Variation Before After Variation Before After Variation
Ex.1 2.177 2.182 0.580% 2.139 2.141 1.002% 2.215 2.172 -1.292%
2.104 2.108 2.453 2.508 2.231 2.205
2.241 2.270 2.175 2.186 2.175 2.159
Mean 2.174 2.187 2.256 2.278 2.207 2.179
C.Ex.1 2.447 2.461 1.321% 2.432 2.447 0.828% 2.371 2.386 0.516%
2.388 2.456 2.399 2.427 2.293 2.296
2.431 2.446 2.415 2.430 2.307 2.326
Mean 2.422 2.454 2.415 2.435 2.324 2.336
As is apparent from Table 4, in the case of chemical resistance in Example 1 and Comparative Example 1, changes in thickness were in the range of -5 ~ +5, and thus chemical resistance was superior in both of Example 1 and Comparative Example 1.
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.
<Example 4>
4-1: Preparation of silicone resin
In a reactor equipped with a cooling tube and a stirrer, 100 parts by weight of propyleneglycol monomethylether acetate as a solvent, 45 parts by weight (0.35 mol) of 3-methacryloxypropyltrimethoxy silane (in Chemical Formula 1, R1 is a methacryl group, X is a methoxy group, and n is 1), 4 parts by weight (0.05 mol) of methyltrimethoxy silane (in Chemical Formula 2, R2 is a methyl group, X is a methoxy group, and n is 1) and 60 parts by weight (0.6 mol) of tetraethoxy silane (in Chemical Formula 3, X is an ethoxy group) were mixed at room temperature, after which 5 parts by weight (alkoxy equivalent) of 0.01% acrylic acid was slowly added dropwise and hydrolysis was carried out for 1 hr. To this reaction mixture, 55 parts by weight (0.5 mol) of zirconium (IV) acetate (in Chemical Formula 6, Me is zirconium, and X is an acetate group) was slowly added dropwise over 30 min, after which the reaction was carried out at 70℃ for 5 hr. The reaction product was then cooled to room temperature and stabilized for 10 hr, after which 80 parts by weight of propyleneglycol monomethylether acetate was further added. Subsequently, vacuum evaporation was conducted at 60℃ to remove byproducts such as water, alcohol, etc. produced during the reaction, yielding 178 g of a silicone resin (in Chemical Formula 7, R1 is a methacryl group, R2 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.
4-2: Preparation of silicone resin composition
50 g of 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).
4-3: Formation of insulating layer
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 ㎛, prebaking the glass having the coating layer on a hot plate at 100℃ for 90 sec, followed by exposure at 80mJ/cm2(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℃ for 30 min.
<Example 5>
5-1: Preparation of silicone resin
185 g of a silicone resin (in Chemical Formula 7, R1 is a mercapto group, R2 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, R1 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.
5-2: Preparation of silicone resin composition
50 g of 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).
5-3: Formation of insulating layer
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 ㎛, prebaking the glass having the coating layer on a hot plate at 100℃ for 90 sec, followed by exposure at 80 mJ/cm2(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℃ for 30 min.
<Example 6>
6-1: Preparation of silicone resin
188 g of a silicone resin (in Chemical Formula 7, R1 is a methacryl group, R2 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, R2 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.
6-2: Preparation of silicone resin composition
50 g of 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).
6-3: Formation of insulating layer
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 ㎛, prebaking the glass having the coating layer on a hot plate at 100℃ for 90 sec, followed by exposure at 80 mJ/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℃ for 30 min.
<Comparative Example 5>
5-1: Preparation of acryl-epoxy resin
In a reactor equipped with a cooling tube and a stirrer, 2.5 parts by weight of 2,2'-azobisisobutyronitrile was dissolved in 100 parts by weight of diethyleneglycol dimethylether. Subsequently, 5 parts by weight of styrene, 7.5 parts by weight of methacrylic acid, 27.5 parts by weight of glycidyl methacrylate and 10 parts by weight of dicylcopentenyloxyethyl methacrylate were added, followed by nitrogen purging and stirring. The temperature of this reaction mixture was increased to 80℃ and the reaction was carried out for 6 hr, yielding 355 g of an acryl-epoxy resin having a solid content of 39 wt%. The weight average molecular weight of the acryl-epoxy resin was 7,500 g/mol.
5-2: Preparation of acryl-epoxy resin composition
50 g of 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).
5-3: Formation of insulating layer
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 ㎛, prebaking the glass having the coating layer on a hot plate at 100℃ for 90 sec, followed by exposure at 80 mJ/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℃ for 30 min.
<Comparative Example 6>
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.
<Comparative Example 7>
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. 50 g of 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.
The properties of the compositions of Examples 4 to 6 and Comparative Examples 5 to 7 were measured and evaluated. The results are given in Tables 5 and 6 below.
(1) Measurement of changes in pencil hardness at different curing temperatures
The 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 ㎛, followed by prebaking (PRB) on a hot plate at 100℃ for 90 sec, exposure (UV) at 80 mJ/cm2(i-g-h line), developing for 50 sec (2.38% TMAH) and post-baking (PSB) in a convection oven at 100℃, 120℃, 140℃ and 150℃ for 30 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 5 below.
(2) Measurement of transmittance upon exposure to high temperature
The 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 ㎛, followed by PRB on a hot plate at 100℃ for 90 sec, exposure (UV) at 80 mJ/cm2(i-g-h line), developing for 50 sec (2.38% TMAH) and curing in a convection oven at 150℃ 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℃, 90 min). The results are shown in Table 5 below.
(3) Measurement of adhesion at high temperature and high humidity
The 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 ㎛, followed by PRB on a hot plate at 100℃ for 90 sec, exposure (UV) at 80 mJ/cm2(i-g-h line), developing for 50 sec (2.38% TMAH) and curing in a convection oven at 150℃ for 30 min. The layer thus cured was exposed to 120℃ 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.
Table 5
Ex.4 Ex.5 Ex.6 C.Ex.5 C.Ex.6 C.Ex.7
Pencil Hardness (Hardness at Temp.) Curing(100℃, 30 min) H H H B or less B or less H
Curing(120℃, 30 min) H 2H H B or less B or less H
Curing(140℃, 30 min) 3-4H 3H 3-4H B or less B or less 3H
Curing(150℃, 30 min) 4-5H 4-5H 4-5H H H 3-4H
Transmittance(%, 400nm) Curing(150℃, 30 min) 99.7 99.8 99.7 98.4 98.1 99.5
High Temp. Exposure(240℃, 90 min) 98.5 98.2 98.9 85.1 79.8 98.1
As is apparent from Table 5, the silicone resin compositions of Examples 4 to 6 exhibited superior pencil hardness at lower temperature, compared to the acryl-epoxy compositions of Comparative Examples 5 and 6.
Also, in the silicone resin compositions of Examples 4 to 6, changes in transmittance upon exposure to high temperature were much smaller, compared to in the acryl-epoxy compositions of Comparative Examples 5 and 6.
Table 6
Optical Microscopic Image (× 200) Separation (Delamination)
Ex.4
Figure PCTKR2014000808-appb-I000011
 No Separation
Ex.5
Figure PCTKR2014000808-appb-I000012
 No Separation
Ex.6
Figure PCTKR2014000808-appb-I000013
 No Separation
C.Ex.5
Figure PCTKR2014000808-appb-I000014
 Partial Separation
C.Ex.6
Figure PCTKR2014000808-appb-I000015
 Partial Separation
C.Ex.7
Figure PCTKR2014000808-appb-I000016
 Complete Separation
As is apparent from Table 6, in the case of adhesion to a substrate (ITO Glass) at high temperature and high humidity, partial separation occurred in Comparative Examples 5 and 6 and complete separation taken place in Comparative Example 6, but excellent adhesion without separation was manifested in Examples 4 to 6.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims (14)

  1. 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:
    <Chemical Formula 1>
    R1(n)SiX(4-n)
    <Chemical Formula 2>
    R2(n)SiX(4-n)
    <Chemical Formula 3>
    SiX4
    <Chemical Formula 4>
    R1(n)MeX(4-n)
    <Chemical Formula 5>
    R2(n)MeX(4-n)
    <Chemical Formula 6>
    MeX4
    In Chemical Formulas 1 to 6, R1 is each independently an organic group having 2 to 10 carbon atoms with at least one unsaturated bond or a mercapto group; R2 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, and n is an integer of 1 ~ 3.
  2. The silicone resin of claim 1, wherein R1 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.
  3. The silicone resin of claim 1, wherein Me is selected from the group consisting of aluminum, zirconium, titanium, zinc, manganese, cobalt, tungsten and vanadium.
  4. 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:
    <Chemical Formula 1>
    R1(n)SiX(4-n)
    <Chemical Formula 2>
    R2(n)SiX(4-n)
    <Chemical Formula 3>
    SiX4
    <Chemical Formula 4>
    R1(n)MeX(4-n)
    <Chemical Formula 5>
    R2(n)MeX(4-n)
    <Chemical Formula 6>
    MeX4
    In Chemical Formulas 1 to 6, R1 is each independently an organic group having 2 to 10 carbon atoms with at least one unsaturated bond or a mercapto group; R2 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, and n is an integer of 1 ~ 3.
  5. The method of claim 4, wherein R1 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.
  6. The method of claim 4, wherein Me is selected from the group consisting of aluminum, zirconium, titanium, zinc, manganese, cobalt, tungsten and vanadium.
  7. The method of claim 4, wherein 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.
  8. The method of claim 4, wherein the condensation reaction is performed at a temperature ranging from room temperature to 150℃ for 1 ~ 48 hr.
  9. A silicone resin composition, comprising 1 ~ 70 wt% of the silicone resin of any one of claims 1 to 3.
  10. The silicone resin composition of claim 9, which is cured at 100 ~ 300℃.
  11. A cured product, formed using the silicone resin composition of claim 9.
  12. 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:
    <Chemical Formula 7>
    Figure PCTKR2014000808-appb-I000017
    in Chemical Formula 7, R1 is each independently an organic group having 2 to 10 carbon atoms with at least one unsaturated bond or a mercapto group; R2 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,
    Figure PCTKR2014000808-appb-I000018
    is represented by Chemical Formula 8 below, and n is 10 or less; and
    <Chemical Formula 8>
    Figure PCTKR2014000808-appb-I000019
    .
  13. The silicone resin of claim 12, wherein R1 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.
  14. The silicone resin of claim 12, wherein Me is selected from the group consisting of aluminum, zirconium, titanium, zinc, manganese, cobalt, tungsten and vanadium.
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