KR20150136930A - Transparent Composite Composition and Protective Layer Prepared by the Same - Google Patents
Transparent Composite Composition and Protective Layer Prepared by the Same Download PDFInfo
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- KR20150136930A KR20150136930A KR1020140064669A KR20140064669A KR20150136930A KR 20150136930 A KR20150136930 A KR 20150136930A KR 1020140064669 A KR1020140064669 A KR 1020140064669A KR 20140064669 A KR20140064669 A KR 20140064669A KR 20150136930 A KR20150136930 A KR 20150136930A
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Abstract
Description
The present invention relates to a transparent composite composition and a protective film made therefrom, and it is an object of the present invention to provide a transparent composite composition and a protective film therefor which can satisfy the conventionally required characteristics such as prevention of deterioration of the substrate and planarization of the substrate, A composite composition and a protective film made therefrom.
An optical device such as a liquid crystal display device (LCD) is immersed in an organic solvent, an acid, an alkali solution or the like during the manufacturing process, or the wiring electrode layer is subjected to severe treatment such as being subjected to high temperature locally heated by sputtering . Therefore, in these devices, a protective film may be provided on the surface thereof in order to prevent deterioration at the time of manufacturing.
The protective film of the optical device serves to protect the colored layer and to flatten the color filter. Therefore, the protective film must be able to withstand such a severe treatment as described above, and must have good adhesion to the substrate or the underlayer, and is required to have excellent heat resistance and light resistance without deterioration such as high smoothness, surface hardness, transparency and coloration, yellowing, do. Further, it is required to have excellent chemical resistance such as solvent resistance, acid resistance, alkali resistance, and water resistance and the like. Also, when such a protective film is applied to a color filter of a color liquid crystal display device, it is preferable that a step of a general color filter can be flattened as a substrate.
The protective film composition is prepared in the form of a curable resin composition so as to satisfy the above-mentioned conditions, and can increase the crosslinking density, and is excellent in mechanical properties and heat resistance.
On the other hand, a glass fiber impregnated substrate, which is a type of flexible substrate, has been developed to improve the physical properties of a substrate made of a substrate material of an optical device such as an organic device including a plate glass, a plastic, a composite resin and a siloxane system, When the curable resin composition used for forming the protective film of the substrate of the present invention is applied to a protective film for a glass fiber impregnated substrate having a large amount of curvature on the surface in comparison with the above-mentioned general substrate, the hardness, flatness, moisture permeability, .
Since the surface properties of the glass fiber impregnated substrate are generally very rough, the substrate is required to have excellent flatness, low water permeability and high hardness, heat resistance, chemical resistance, adhesion and transparency. There is a problem that such a performance can not be obtained when a protective film is formed.
It is an object of the present invention to provide a glass fiber-impregnated substrate protective film which satisfies the characteristics required conventionally as a protective film of a substrate and which further improves the flatness and hardness of the substrate at a low curing temperature, To provide a composite composition.
Another object of the present invention is to provide a low-temperature curable protective film made of a transparent composite composition for forming a glass fiber-impregnated substrate protective film.
(A2) an epoxy group-containing unsaturated compound and (a3) an olefinically unsaturated compound; [A] a copolymer of an unsaturated carboxylic acid or an anhydride thereof, At least one curing compound [B] selected from the group represented by the formula (1); And a polyfunctional thiol curing agent [C].
≪ Formula 1 >
In Formula 1, R is selected from the group represented by the following Formula 2, and n is an integer of 1 to 3 in Formula 2 below.
(2)
In the present invention, the curable compound [B] and the polyfunctional thiol curing agent [C] are each contained in an amount of 1 to 10 parts by weight and 1 to 10 parts by weight based on 100 parts by weight of the copolymer [A].
In the present invention, the transparent composite composition may further comprise 1 to 100 parts by weight of the urethane acrylate oligomer [D] based on 100 parts by weight of the copolymer [A].
The present invention also provides a protective film for an optical device or an optical device substrate formed from the transparent composite composition.
The transparent composite composition of the present invention satisfies the properties required to prevent deterioration of the substrate as a protective film of the substrate and to planarize the substrate while improving the flatness and hardness of the substrate, And has advantages suitable for substrate protection.
Hereinafter, the present invention will be described in more detail.
In one preferred embodiment of the present invention, a copolymer [A] of (a1) an unsaturated carboxylic acid or an anhydride thereof, (a2) an epoxy group-containing unsaturated compound and (a3) an olefinically unsaturated compound; At least one curing compound [B] selected from the group represented by the formula (1); And a polyfunctional thiol curing agent [C].
≪ Formula 1 >
In Formula 1, R is selected from the group represented by the following Formula 2, and n is an integer of 1 to 3 in Formula 2 below.
(2)
The copolymer [A] is obtained by a conventionally known polymerization method as a binder resin, that is, the compounds (a1), (a2) and (a3) can be synthesized by performing a radical polymerization in a solvent in the presence of a polymerization initiator have.
The copolymer [A] preferably contains 5 to 40% by weight, more preferably 10 to 30% by weight, of the constituent unit derived from the compound (a1). When the content of the constituent unit is less than 5% by weight, heat resistance, chemical resistance and surface hardness of the protective film to be produced later tend to decrease. When the content exceeds 40% by weight, the storage stability is deteriorated. Examples of the compound (a1) include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids. One of these dicarboxylic acids may be used alone, or two or more dicarboxylic acids may be used in combination. Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are mainly used because they are excellent in copolymerization reactivity and heat resistance and are easily available.
The copolymer [A] preferably contains 10 to 70% by weight, more preferably 20 to 60% by weight, of the constituent unit derived from the compound (a2). When the content of the constituent unit is less than 10% by weight, heat resistance and surface hardness of the protective film produced later tends to be lowered, and when it exceeds 70% by weight, the storage stability tends to decrease. Examples of the compound (a2) include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate, glycidyl? -N-butyl acrylate, Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl,? -Ethylacrylic acid-6,7-epoxyheptyl, o Vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, or a combination of two or more thereof, and the copolymerization reactivity and the heat resistance and hardness of the obtained protective film are increased Is preferably used.
The copolymer [A] preferably contains 10 to 70% by weight, more preferably 20 to 50% by weight, of the constituent unit derived from the compound (a3). When the content of the constituent unit is less than 10% by weight, storage stability tends to decrease. When the content exceeds 70% by weight, heat resistance and surface hardness of a protective film produced later tend to decrease. Examples of the compound (a3) include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate; Alkyl acrylate esters such as methyl acrylate and isopropyl acrylate; Methacrylic acid cycloalkyl esters such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate and isobornyl methacrylate; Acrylic acid cycloalkyl esters such as cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, and isobornyl acrylate; Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; Hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; And styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, or a combination of two or more thereof. Of these, styrene, t-butyl methacrylate, dicyclopentenyl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, and 1,3-butadiene are preferred from the viewpoint of copolymerization reactivity and heat resistance.
The copolymer [A] used in the present invention has a carboxyl group and / or a carboxylic acid anhydride and an epoxy group, and can be easily cured by heating even without using a special curing agent. However, the curing compound [B] The crosslinking density can be sufficiently increased.
The molecular weight of the copolymer [A] is not particularly limited, but is appropriately selected depending on the thickness of the film to be formed, the solution application conditions of the curable composition, the purpose, and the like. The number average molecular weight of the copolymer [A] is preferably in the range of 3,000 to 100,000, more preferably 3,000 to 50,000 in view of the surface smoothness of the protective film to be produced later.
Examples of the solvent used for the synthesis of the copolymer [A] include alcohols such as methanol and ethanol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; And propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate and the like, or a combination of two or more thereof.
As the polymerization initiator used in the synthesis of the copolymer [A], those generally known as radical polymerization initiators can be used. Azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy- Dimethylvaleronitrile); and the like; Organic peroxides such as benzoyl peroxide, t-butyl peroxypivalate, and 1,1'-bis- (t-butylperoxy) cyclohexane; And hydrogen peroxide. When a peroxide is used as a radical polymerization initiator, the peroxide can be used as a redox type initiator together with a reducing agent.
The curable compound [B] functions as a curing agent for the copolymer [A] and is selected from the group represented by the following formula (1) in consideration of the adhesion strength, moisture permeability, substrate flatness, transparency, hardness, And may be one or more selected compounds.
≪ Formula 1 >
In Formula 1, R is selected from the group represented by the following Formula 2, and n is an integer of 1 to 3 in Formula 2 below.
(2)
Specific examples of the compound selected from the group consisting of the compounds represented by Chemical Formulas 1 and 2 as the curable compound [B] include OXT-101, OXT-212, OXT-121 and OXT-221 of Toagosei, EHO, OXBP, OXMA , HBOX, and the like.
Further, the curable compound [B] improves the adhesion of the protective film as an organic-inorganic hybrid compound and forms an organic nanocomposite upon curing, so that the moisture permeability of the protective film can be reduced. In addition, it has the function of improving the substrate flatness, transparency and hardness.
The curable compound [B] is preferably contained in an amount of 1 to 100 parts by weight, more preferably 10 to 50 parts by weight, per 100 parts by weight of the copolymer [A]. If the content of the curable compound [B] is less than 1 part by weight based on 100 parts by weight of the copolymer [A], there is a problem that the protective film to be produced has a low adhesive force, substrate flatness, transparency and hardness, If the amount is more than 100 parts by weight, a large amount of the unreacted curing compound [B] tends to remain in the film of the protective film to be produced, and as a result, the properties of the protective film become unstable or the adhesiveness tends to deteriorate.
The multifunctional thiol curing agent [C] is a form in which the thiol group is multifunctionally bound, and serves to lower the curing temperature of the protective film and to increase the epoxy curing density.
The polyfunctional thiol curing agent [C] is preferably contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the copolymer [A]. If the content of the polyfunctional thiol curing agent [C] is less than 1 part by weight, the curing temperature of the protective film can not be sufficiently lowered and the epoxy curing degree can not be improved. If the content is more than 10 parts by weight, .
The urethane acrylate oligomer [D] is a component which can be further included in the transparent composite composition in order to improve the substrate flatness when applied to a substrate as a protective film to be produced.
The urethane acrylate oligomer [D] may be selected from urethane oligomers having a number average molecular weight of 1000 to 5000 and having an acryl group as an end group. When the number average molecular weight is less than 1000, it is difficult to obtain a cured film having a sufficient cured density, and there is a problem that the surface hardness, heat resistance, and UV resistance may deteriorate. When the number average molecular weight exceeds 5000, there is a problem that the compatibility with other components is insufficient and it is difficult to obtain a cured film having a sufficient cured density and the surface hardness, heat resistance, and UV resistance may also decrease. In the absence of an acrylic reactive group at the terminal end, a curing reaction can not be caused, so that it is difficult to obtain a cured film having a sufficient curing density, and the surface hardness, heat resistance, and UV resistance may also deteriorate.
Specific examples of such acryl-terminated urethane oligomers include EB-1290, EB-9260, EB-230, EB-6700 and EB-8800 commercially available from SK-UCB.
The content of the urethane acrylate oligomer [D] is preferably 1 to 100 parts by weight based on 100 parts by weight of the copolymer [A]. When the content of the urethane acrylate oligomer [D] is less than 1 part by weight, the flatness of the substrate to which the protective film is applied is not sufficiently improved. When the content of the urethane acrylate oligomer is more than 100 parts by weight, , And the transparency tends to deteriorate.
Further, the transparent composite composition of the present invention may further contain a thermal radical polymerization initiator, and it is contained in an amount of 20 parts by weight or less, more preferably 15 parts by weight or less, based on 100 parts by weight of the copolymer [A]. If the amount of the thermal radical polymerization initiator exceeds 20 parts by weight, the heat resistance and planarizing property of the protective film, which will be obtained later, are liable to be lowered.
As the thermal radical polymerization initiator, those generally known as radical polymerization initiators can be used, and a polymerization initiator used for the polymerization of the copolymer [A] described above can be used.
The transparent composite composition according to the present invention is obtained by dissolving a urethane acrylate oligomer [D] and a thermal radical polymerization initiator together with the copolymer [A], the curing compound [B] and the polyfunctional thiol curing agent [C] Can be manufactured. At this time, the solvent is used which does not react with any one component. Specifically, the solvent includes alcohols such as methanol and ethanol; Ethers such as tetrahydrofuran and diethylene glycol dimethyl ether; And propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate. Of these solvents, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and propylene glycol methyl ether acetate may be preferably used in terms of solubility, reactivity with each component, and ease of coating film formation.
It is also possible to use a high boiling point solvent together with the above-mentioned solvent. Examples of the high boiling point solvent which can be used in combination include N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, And benzyl ethyl ether. When such a high boiling point solvent is used in combination, it is preferable that the mixing ratio with the solvent is "the solvent: high boiling point solvent = 50 to 100: 50 to 0 ".
The transparent composite composition of the present invention may contain other components as necessary insofar as the object of the present invention is not impaired.
Other components herein include surfactants for improving the coating properties, for example. As the surfactant, a fluorine or silicone surfactant can be used, and it can be used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When a surfactant is used in an amount exceeding 5 parts by weight based on 100 parts by weight of the copolymer [A], there is a problem that bubbles easily occur during application.
The composition solution prepared as described above can be used after filtration using a filter having a pore size of about 0.1 to 5 탆.
The transparent composite composition according to the present invention can form a protective film, for example, by the following method.
The desired transparent protective film can be obtained by applying the transparent composite composition to a substrate and treating the film in an oven at 150 to 300 DEG C for 10 to 100 minutes. Here, the substrate is preferably a glass fiber impregnated substrate. As the coating method, roll coating, spin coating, micro gravure coating, slit coating and the like can be applied.
Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.
≪ Example 1 >
In a reaction vessel equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobisisobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were charged and replaced with nitrogen, followed by gentle stirring. The temperature of the solution was raised to 80 캜 and maintained at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-1]. The solid concentration of the obtained polymer solution was 33% by weight.
100 parts by weight (solid content) of the obtained copolymer [A-1] and OXT-221 (formula 1, R =
Thereafter, the solution was filtered with a filter having a pore diameter of 0.45 mu m to prepare a transparent composite composition solution.
The transparent composite composition solution was coated on the glass fiber-impregnated substrate using a roll coater so that the thickness of the transparent composite composition solution became 2 탆, and then baked in a clean oven at 220 캜 for 30 minutes to form a protective film on the substrate.
≪ Example 2 >
A transparent composite composition solution was prepared in the same manner as in Example 1, except that 10 parts by weight of EB-9260 (acrylic urethane resin, number average molecular weight 1500) of SK-UCB was used as the urethane acrylate oligomer [D] A protective film was formed on the glass fiber-impregnated substrate in the same manner.
≪ Example 3 >
As the curable compound [B] in Example 1, OXT-221 (formula (1), manufactured by Toagosei Co.,
<Example 4>
As the curable compound [B] in Example 1, OXT-221 (formula (1), manufactured by Toagosei Co.,
≪ Example 5 >
As the curable compound [B] in Example 1, OXT-221 (formula (1), manufactured by Toagosei Co.,
≪ Example 6 >
3 parts by weight of Showa Denko MT-PE1 as a polyfunctional thiol curing agent [C] and 10 parts by weight of EB-9260 (acrylic urethane resin, number average molecular weight 1500) of SK-UCB as a urethane acrylate oligomer [D] And a protective film was formed on the glass fiber-impregnated substrate in the same manner.
≪ Example 7 >
5 parts by weight of Showa Denko MT-PE1 as a polyfunctional thiol curing agent [C] in Example 1 and 10 parts by weight of EB-9260 (acrylic urethane resin, number average molecular weight 1500) of SK-UCB as a urethane acrylate oligomer [D] And a protective film was formed on the glass fiber-impregnated substrate in the same manner.
≪ Example 8 >
10 parts by weight of Showa Denko MT-PE1 as a polyfunctional thiol curing agent [C] in Example 1 and 10 parts by weight of EB-9260 (acrylic urethane resin, number average molecular weight 1500) of SK-UCB as a urethane acrylate oligomer [D] And a protective film was formed on the glass fiber-impregnated substrate in the same manner.
≪ Example 9 >
A transparent composite composition solution was prepared in the same manner as in Example 1, except that 1 part by weight of EB-9260 (acrylic urethane resin, number average molecular weight 1500) of SK-UCB was used as the urethane acrylate oligomer [D] A protective film was formed on the glass fiber-impregnated substrate in the same manner.
≪ Example 10 >
A transparent composite composition solution was prepared in the same manner as in Example 1 except that 50 parts by weight of EB-9260 (acrylic urethane resin, number average molecular weight: 1500) of SK-UCB was used as the urethane acrylate oligomer [D] A protective film was formed on the glass fiber-impregnated substrate in the same manner.
≪ Example 11 >
A transparent composite composition solution was prepared in the same manner as in Example 1, except that 100 parts by weight of EB-9260 (acrylic urethane resin, number average molecular weight 1500) of SK-UCB was used as the urethane acrylate oligomer [D] A protective film was formed on the glass fiber-impregnated substrate in the same manner.
≪ Comparative Example 1 &
A transparent composite composition solution was prepared in the same manner as in Example 3 except that the multifunctional thiol curing agent [C] was not used, and a protective film was formed on the glass fiber-impregnated substrate in the same manner.
≪ Comparative Example 2 &
A transparent composite composition solution was prepared in the same manner as in Example 4 except that the light polyfunctional thiol curing agent [C] was not used, and a protective film was formed on the glass fiber-impregnated substrate in the same manner.
≪ Comparative Example 3 &
A transparent composite composition solution was prepared in the same manner as in Example 2 except that the polyfunctional thiol curing agent [C] was not used, and a protective film was formed on the glass fiber-impregnated substrate in the same manner.
≪ Comparative Example 4 &
A transparent composite composition solution was prepared in the same manner as in Example 2 except that 10 parts by weight of MT-PE1 from Showa Denko Co. was used as the polyfunctional thiol curing agent [C], and a protective film was formed on the glass fiber- .
≪ Comparative Example 5 &
A transparent composite composition solution was prepared in the same manner as in Comparative Example 3, except that 150 parts by weight of EB-9260 (acrylic urethane resin, number average molecular weight 1500) of SK-UCB was used as the urethane acrylate oligomer [D] A protective film was formed on the glass fiber-impregnated substrate in the same manner.
≪ Comparative Example 6 >
1 part by weight of silica sol in which SiO 2 component was dispersed in MeOH in an amount of 50% in the form of silica sol instead of the polyfunctional thiol curing agent [C] in Example 1, and 1 part by weight of EB of SK-UCB as a urethane acrylate oligomer [D] -9,260 (acrylic urethane resin, number average molecular weight 1500) 10 parts by weight were added and mixed, and a protective film was formed on the glass fiber-impregnated substrate in the same manner as in Example 1 .
The evaluation methods of the protective film used in the present invention are as follows. The compositions used in the examples and comparative examples and the evaluation results of the protective film are shown in Tables 1 and 2, respectively.
(1) Flatness of the substrate
The surface irregularities of the protective film were irradiated using a surface profiler (KLA Tencor Alpha-Step (AS-500IQ)) and the step of the substrate was measured.
(2) Water permeability
The moisture permeability of the substrate having the protective film formed thereon was measured using a moisture permeability meter (WVTR meter, Mocon equipment).
(3) Hardness
The pencil hardness test was performed on the protective film according to the pencil hardness method (ASTM D3363) to evaluate the surface hardness of the protective film.
(4) Heat resistance
The protective film was heated in a clean oven at 240 DEG C for 60 minutes, and the transmission spectrum before and after heating was measured. The heat resistance of the protective film was evaluated according to the following criteria.
○: Change in transmission spectrum is within 5%
X: Change in transmission spectrum is not less than 5%
(5) Chemical resistance
The substrate having the protective film formed thereon was immersed in a 25% by weight hydrochloric acid aqueous solution and a 10% by weight aqueous solution of sodium hydroxide at 30 DEG C for 60 minutes, and then the change in appearance of the protective film was observed to evaluate the chemical resistance of the protective film.
○: Good appearance
X: Appearance defect (defect check)
(6) Adhesion
A checkerboard scale of 100 pieces was formed as a cutter knife on the protective film according to the checkerboard tape method (ASTM D3359), and the adhesion test was conducted. The number of peeled checker scales was measured, and the adhesion of the protective film was evaluated according to the following criteria.
○: Number of peeled checkered patterns No more than 5
B: Number of peeled checkered patterns 6 to 49
X: Number of peeled checkered patterns 50 or more
(7) Transparency
The transmittance of the protective film was measured at 400 to 700 nm using a spectrophotometer (UV-VIS spectrophotometer UV-3101PC, manufactured by SHIMADZU) and the transparency of the protective film was evaluated according to the following criteria.
○: Minimum transmittance exceeded 95%
?: Minimum transmittance: 90 to 95%
×: Minimum transmittance less than 90%
* Comparative Example 6 uses silica sol instead of polyfunctional thiol curing agent
From Table 2, it can be seen that when the protective film of the glass fiber impregnated substrate is formed using the transparent composite composition prepared in the examples, the substrate flatness, water permeability, hardness, heat resistance, chemical resistance, adhesion, .
As a result, by using the transparent composite composition according to the present invention, it is possible to provide a glass fiber impregnated substrate with excellent substrate flatness, low water permeability, high hardness, heat resistance, chemical resistance, adhesion, transparency It is possible to improve the physical properties of the polymer.
Claims (4)
At least one curing compound [B] selected from the group represented by the formula (1); And
A polyfunctional thiol curing agent [C].
≪ Formula 1 >
In Formula 1, R is selected from the group represented by the following Formula 2, and n is an integer of 1 to 3 in Formula 2 below.
(2)
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2020504207A (en) * | 2016-12-30 | 2020-02-06 | ドンジン セミケム カンパニー リミテッドＤｏｎｇｊｉｎ Ｓｅｍｉｃｈｅｍ Ｃｏ．， Ｌｔｄ． | Coating composition capable of realizing low curl and film produced therefrom |
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2014
- 2014-05-28 KR KR1020140064669A patent/KR20150136930A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020504207A (en) * | 2016-12-30 | 2020-02-06 | ドンジン セミケム カンパニー リミテッドＤｏｎｇｊｉｎ Ｓｅｍｉｃｈｅｍ Ｃｏ．， Ｌｔｄ． | Coating composition capable of realizing low curl and film produced therefrom |
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