WO2018056370A1 - Matériau de revêtement dur résistant aux rayures - Google Patents

Matériau de revêtement dur résistant aux rayures Download PDF

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Publication number
WO2018056370A1
WO2018056370A1 PCT/JP2017/034143 JP2017034143W WO2018056370A1 WO 2018056370 A1 WO2018056370 A1 WO 2018056370A1 JP 2017034143 W JP2017034143 W JP 2017034143W WO 2018056370 A1 WO2018056370 A1 WO 2018056370A1
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group
mass
poly
curable composition
meth
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PCT/JP2017/034143
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English (en)
Japanese (ja)
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将幸 原口
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日産化学工業株式会社
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Priority to CN201780057803.2A priority Critical patent/CN109715685B/zh
Priority to KR1020197005643A priority patent/KR20190055071A/ko
Priority to JP2018540300A priority patent/JPWO2018056370A1/ja
Publication of WO2018056370A1 publication Critical patent/WO2018056370A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G

Definitions

  • the present invention relates to a curable composition useful as a material for forming a hard coat layer applied to the surface of various display elements such as a touch panel display and a liquid crystal display.
  • a large number of products in which a touch panel is mounted on a flat panel display such as a personal computer, a mobile phone, a mobile game machine, and an ATM have been commercialized.
  • a touch panel is mounted on a flat panel display such as a personal computer, a mobile phone, a mobile game machine, and an ATM.
  • smartphones and tablet PCs the number of capacitive touch panels having a multi-touch function is rapidly increasing.
  • Thin tempered glass is used on the surface of these touch panel displays, and a protective film is attached to the display surface in order to prevent the glass from scattering. Since the protective film uses a plastic film, it is more likely to be scratched than glass, and it is necessary to provide a hard coat layer having excellent scratch resistance on the surface.
  • a method is adopted in which a highly crosslinked structure is formed, that is, a crosslinked structure with low molecular mobility is formed to increase the surface hardness and provide resistance to external force. It is done.
  • polyfunctional acrylate materials currently used as hard coat layer forming materials are monomers that are liquid at room temperature, and are three-dimensionally cross-linked by radicals generated from a photopolymerization initiator.
  • the acrylate system is cured by ultraviolet rays (UV), and the time of UV irradiation is very short and energy saving, and is characterized by high productivity.
  • a means for forming a hard coat layer on the surface of the plastic film for example, a solution containing a polyfunctional acrylate, a photopolymerization initiator and an organic solvent is coated on the plastic film by gravure coating, etc. Then, a means for forming a hard coat layer is employed. In order to express functions such as hardness and scratch resistance in the formed hard coat layer at a level having no practical problem, the hard coat layer is usually formed with a thickness of 1 to 15 ⁇ m.
  • the capacitive touch panel is operated by touching it with a human finger. For this reason, fingerprints are attached to the surface of the touch panel every time an operation is performed, causing problems that the visibility of the image on the display is remarkably impaired and the appearance of the display is impaired.
  • the fingerprint contains moisture derived from sweat and oil derived from sebum, and it is strongly desired to impart water repellency and oil repellency to the hard coat layer on the display surface in order to prevent both of them from adhering. ing. From such a viewpoint, the touch panel display surface is desired to have antifouling properties against fingerprints and the like.
  • a method for imparting antifouling properties to the surface of the hard coat layer a method of adding a small amount of a fluorine-based surface modifier to the coating solution for forming the hard coat layer has been used.
  • the added fluorine-based compound is segregated on the surface of the hard coat layer due to its low surface energy, and imparts water repellency and oil repellency.
  • an oligomer having a number average molecular weight of about 1,000 to 5,000 called a perfluoropolyether having a poly (oxyperfluoroalkylene) chain is used from the viewpoint of water repellency and oil repellency. .
  • perfluoropolyether since perfluoropolyether has a high fluorine concentration, it is usually difficult to dissolve in an organic solvent used in a coating solution for forming a hard coat layer. Moreover, aggregation is caused in the formed hard coat layer.
  • a technique of adding an organic moiety to the perfluoropolyether is used.
  • a method of bonding active energy ray-curable sites represented by (meth) acrylate groups is used.
  • the perfluoropolyether compound described in Patent Document 1 is highly soluble in the coating liquid, but segregates at the gas-liquid interface of the coating liquid, greatly reduces the surface tension of the coating liquid, and a large number of bubbles are present in the coating liquid. appear.
  • the air bubbles become defective, resulting in poor appearance of the coating film. Therefore, in order to eliminate the generated bubbles, it is necessary to leave for a long time, and the problem is that productivity deteriorates.
  • a curable composition comprising an anti-foaming agent comprising a perfluoropolyether having an active energy ray-polymerizable group and a fluorosilicone compound via an alkylene) group and one urethane bond has excellent defoaming properties.
  • the inventors have found that a hard coat layer having excellent scratch resistance and a uniform appearance can be formed, and the present invention has been completed.
  • the present invention provides the first aspect as follows: (A) 100 parts by mass of an active energy ray-curable polyfunctional monomer, (B) Active energy rays through a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bond in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group 0.1 to 10 parts by mass of a perfluoropolyether having a polymerizable group, (C) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, (D) 0.0001 to 0.004 mass of an antifoaming agent comprising a fluorosilicone compound having a weight average molecular weight measured in terms of polystyrene of 10,000 to 200,000 and a fluorine content of 31 mass% or more.
  • a curable composition containing an organic solvent As a 2nd viewpoint, it is related with the curable composition as described in a 1st viewpoint whose fluorine content of the said fluoro silicone compound is 35 mass% or more.
  • the organic solvent of the said component (e) is related with the curable composition as described in a 1st viewpoint or a 2nd viewpoint which is alkylene glycol monoalkyl ether.
  • the organic solvent of the said component (e) is related with the curable composition as described in a 3rd viewpoint which is ethyl cellosolve or propylene glycol monomethyl ether.
  • the present invention relates to the curable composition according to any one of the first aspect to the fourth aspect, in which the total concentration of the components (e) excluding the organic solvent is 30 to 40% by mass.
  • the poly (oxyperfluoroalkylene) group is a group having — [OCF 2 ] — and — [OCF 2 CF 2 ] — as repeating units. It relates to the curable composition according to any one of the above.
  • the curability according to any one of the first to sixth aspects, in which the poly (oxyalkylene) group is a poly (oxyalkylene) group having 5 to 12 repeating units. Relates to the composition.
  • the present invention relates to the curable composition according to any one of the first aspect to the seventh aspect, in which the poly (oxyalkylene) group is a poly (oxyethylene) group.
  • the present invention relates to the curable composition according to any one of the first to eighth aspects, wherein the active energy ray polymerizable group is a group having at least two active energy ray polymerizable moieties.
  • the polyfunctional monomer of the component (a) is at least one selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound. It relates to the curable composition as described in any one of viewpoints.
  • the present invention relates to a hard coat film including a hard coat layer on at least one surface of a film base material, wherein the hard coat layer is formed of the cured film described in the eleventh aspect.
  • a thirteenth aspect relates to the hard coat film according to the twelfth aspect, wherein the hard coat layer has a thickness of 1 to 15 ⁇ m.
  • a method for producing a hard coat film comprising a hard coat layer on at least one surface of a film base material, wherein the curable composition according to any one of the first aspect to the tenth aspect is used. It is related with the manufacturing method of a hard coat film including the process of apply
  • ADVANTAGE OF THE INVENTION it is useful for formation of the cured film and hard-coat layer which are excellent in abrasion resistance, and is excellent in an external appearance, and can provide the curable composition excellent in defoaming property.
  • a method capable of efficiently producing a hard coat film including a coat layer can be provided.
  • the curable composition of the present invention includes: (A) 100 parts by mass of an active energy ray-curable polyfunctional monomer, (B) Active energy rays through a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bond in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group 0.1 to 10 parts by mass of a perfluoropolyether having a polymerizable group, (C) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays, (D) 0.0001 to 0.004 mass of an antifoaming agent comprising a fluorosilicone compound having a weight average molecular weight measured in terms of polystyrene of 10,000 to 200,000 and a fluorine content of 31 mass% or more. And (e) a curable composition containing an organic solvent.
  • the active energy ray-curable polyfunctional monomer refers to a monomer that is cured by a polymerization reaction that proceeds by irradiation with an active energy ray such as ultraviolet rays.
  • the preferable (a) active energy ray-curable polyfunctional monomer is a monomer selected from the group consisting of a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound.
  • the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound.
  • (meth) acrylic acid refers to acrylic acid and methacrylic acid.
  • polyfunctional (meth) acrylate compound examples include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra.
  • pentaerythritol tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.
  • the polyfunctional urethane (meth) acrylate compound is a compound having a plurality of acryloyl groups or methacryloyl groups in one molecule and one or more urethane bonds (—NHCOO—).
  • the polyfunctional urethane (meth) acrylate compound is obtained by a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group, or a reaction between a polyfunctional isocyanate and a (meth) acrylate having a hydroxy group and a polyol.
  • the polyfunctional urethane (meth) acrylate compound that can be used in the present invention is not limited to such examples.
  • Examples of the polyfunctional isocyanate include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate.
  • Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth).
  • An acrylate, tripentaerythritol hepta (meth) acrylate, etc. are mentioned.
  • polyols examples include diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol; these diols, succinic acid, malein Examples include polyester polyols which are reaction products with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as acids and adipic acid; polyether polyols; polycarbonate diols and the like.
  • the (a) active energy ray-curable polyfunctional monomer one kind is selected from the group consisting of the polyfunctional (meth) acrylate compound and the polyfunctional urethane (meth) acrylate compound, or two or more kinds are used. Can be used in combination. From the viewpoint of scratch resistance of the resulting cured product, it is preferable to use a polyfunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound in combination. Moreover, it is preferable to use together 5 or more functional polyfunctional (meth) acrylate compound and 4 or less polyfunctional (meth) acrylate compound as said polyfunctional (meth) acrylate compound.
  • the polyfunctional urethane (meth) acrylate compound 20 with respect to 100 mass parts of polyfunctional (meth) acrylate compounds. It is preferable to use ⁇ 100 parts by mass, and it is more preferable to use 30 to 70 parts by mass. Furthermore, in the polyfunctional (meth) acrylate compound, when the polyfunctional (meth) acrylate compound having 5 or more functions and the polyfunctional (meth) acrylate compound having 4 or less functions are used in combination, the polyfunctional (meth) acrylate compound has 5 or more functions.
  • component (B) Active energy via a poly (oxyalkylene) group or a poly (oxyalkylene) group and one urethane bond in this order at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group Perfluoropolyether having a linear polymerizable group
  • component (b) a poly (oxyalkylene) group and one urethane bond are bonded to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group.
  • perfluoropolyether having an active energy ray polymerizable group (hereinafter, also referred to simply as “(b) perfluoropolyether having a polymerizable group at both ends”) is used.
  • the component (b) serves as a surface modifier in the hard coat layer to which the curable composition of the present invention is applied.
  • the number of carbon atoms of the alkylene group in the poly (oxyperfluoroalkylene) group is not particularly limited, but preferably 1 to 4 carbon atoms. That is, the poly (oxyperfluoroalkylene) group refers to a group having a structure in which a divalent fluorocarbon group having 1 to 4 carbon atoms and oxygen atoms are alternately connected, and the oxyperfluoroalkylene group is a carbon atom. This refers to a group having a structure in which a divalent fluorocarbon group of formulas 1 to 4 and an oxygen atom are linked.
  • — [OCF 2 ] (oxyperfluoromethylene group), — [OCF 2 CF 2 ] — (oxyperfluoroethylene group), — [OCF 2 CF 2 CF 2 ] — (oxyperfluoropropane) -1,3-diyl group) and-[OCF 2 C (CF 3 ) F]-(oxyperfluoropropane-1,2-diyl group).
  • the above oxyperfluoroalkylene groups may be used alone or in combination of two or more. In such a case, the bonds of plural types of oxyperfluoroalkylene groups are block bonds and random bonds. Any of these may be used.
  • — [OCF 2 ] (oxyperfluoromethylene group) and — [OCF 2 CF 2 ] are used. It is preferable to use a group having both of-(oxyperfluoroethylene group) as repeating units.
  • the bond of these repeating units may be either a block bond or a random bond.
  • the number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, more preferably in the range of 7 to 21, as the total number of repeating units.
  • the weight average molecular weight (Mw) of the poly (oxyperfluoroalkylene) group measured in terms of polystyrene by gel permeation chromatography is 1,000 to 5,000, preferably 1,500 to 2,000. .
  • the number of carbon atoms of the alkylene group in the poly (oxyalkylene) group is not particularly limited, but preferably 1 to 4 carbon atoms. That is, the poly (oxyalkylene) group refers to a group having a structure in which an alkylene group having 1 to 4 carbon atoms and oxygen atoms are alternately connected, and the oxyalkylene group is a divalent alkylene having 1 to 4 carbon atoms. A group having a structure in which a group and an oxygen atom are linked. Examples of the alkylene group include an ethylene group, a 1-methylethylene group, a trimethylene group, and a tetramethylene group. The oxyalkylene groups may be used singly or in combination of two or more.
  • the bonds of the plural oxyalkylene groups may be either block bonds or random bonds. May be.
  • the poly (oxyalkylene) group is preferably a poly (oxyethylene) group.
  • the number of repeating units of the oxyalkylene group in the poly (oxyalkylene) group is, for example, in the range of 1 to 15, and more preferably in the range of 5 to 12, for example, 7 to 12.
  • Examples of the active energy ray polymerizable group that bonds the poly (oxyalkylene) group or the poly (oxyalkylene) group and one urethane bond in this order include a (meth) acryloyl group and a urethane (meth) acryloyl group. And vinyl group.
  • the active energy ray polymerizable group is not limited to one having one active energy ray polymerizable portion such as a (meth) acryloyl moiety, and may have two or more active energy ray polymerizable portions,
  • the following structures A1 to A5 and structures in which the acryloyl group in these structures is substituted with a methacryloyl group can be mentioned.
  • A represents one of the structures represented by the formulas [A1] to [A5]
  • PFPE represents the poly (oxyperfluoroalkylene) group
  • n is independently selected. Represents the number of repeating units of the oxyethylene group, preferably a number of 1 to 15, more preferably a number of 5 to 12, and still more preferably a number of 7 to 12.
  • the (b) perfluoropolyether having a polymerizable group at both ends of the present invention has a poly (oxyalkylene) group and one urethane bond at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group.
  • a poly (oxyalkylene) group is bonded to both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group, and a urethane bond is bonded to each poly (oxyalkylene) group at both ends.
  • It is preferably a perfluoropolyether having one bonded and an active energy ray polymerizable group bonded to each urethane bond at both ends.
  • the active energy ray polymerizable group is preferably a perfluoropolyether which is a group having at least two active energy ray polymerizable moieties.
  • the perfluoropolyether having a polymerizable group at both ends is 0.1 to 10 parts by weight, preferably 100 parts by weight, preferably 100 parts by weight of the active energy ray-curable polyfunctional monomer. It is desirable to use at a ratio of 0.2 to 5 parts by mass.
  • the perfluoropolyether having a polymerizable group at both ends (b) is, for example, a compound having a hydroxy group at both ends of a poly (oxyperfluoroalkylene) group via a poly (oxyalkylene) group.
  • the curable composition of the present invention includes (b) a poly (oxyalkylene) group or one poly (oxyalkylene) group at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group.
  • a poly (oxyalkylene) group or one poly (oxyalkylene) group at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group.
  • the poly (oxyperalkylene) group is attached to one end of the molecular chain containing the poly (oxyperfluoroalkylene) group or the poly (oxyalkylene) group.
  • Perfluoropolyethers [not having an active energy ray-polymerizable group compound] may be contained that.
  • a polymerization initiator that generates radicals by a preferable active energy ray is, for example, active energy such as electron beam, ultraviolet ray, and X-ray. It is a polymerization initiator that generates radicals by irradiation with ultraviolet rays, in particular.
  • polymerization initiator (c) examples include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, benzophenones.
  • alkylphenones as the polymerization initiator (c) from the viewpoints of transparency, surface curability, and thin film curability.
  • alkylphenones By using alkylphenones, a cured film with improved scratch resistance can be obtained.
  • the polymerization initiator is used in a ratio of 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the above-mentioned (a) active energy ray-curable polyfunctional monomer. Is desirable.
  • (D) Antifoaming agent comprising a fluorosilicone compound having a weight average molecular weight measured in terms of polystyrene of 10,000 to 200,000 and a fluorine content of 31% by mass or more
  • component (d) a fluoropolymer having a weight average molecular weight of 10,000 to 200,000 as measured by gel permeation chromatography (GPC) in terms of polystyrene and a fluorine content of 31% by mass or more.
  • GPC gel permeation chromatography
  • An antifoaming agent composed of a silicone compound hereinafter also simply referred to as “(d) antifoaming agent” is used.
  • the fluorosilicone compound in the antifoaming agent (d) used in the present invention has a weight average molecular weight measured in terms of polystyrene of 10,000 to 200,000 and a fluorine content of 31% by mass or more.
  • the structure is not limited.
  • the fluorosilicone compound in the antifoaming agent (d) used in the present invention has a weight average molecular weight measured in terms of polystyrene of 10,000 to 200,000, preferably 20,000 to 150,000, more preferably 30,000. 000 to 100,000.
  • the fluorosilicone compound in the antifoaming agent used in the present invention has a fluorine content of 31% by mass or more, preferably 35% by mass or more.
  • (d) antifoaming agent examples include, for example, Floren AO-82, AO-98, AO-106, AO-108 [above, manufactured by Kyoeisha Chemical Co., Ltd.], AF 98/1000, AF 98/10000 [above, Asahi Kasei Wacker Silicone Co., Ltd.], FS 1265 [Toray Dow Corning Co., Ltd.], Shin-Etsu Silicone (registered trademark) FA-600, FA-630 [above, Shin-Etsu Chemical ( Co., Ltd.], BYK (registered trademark) -063, 065, 066N, 067A [above, manufactured by Big Chemie Japan Co., Ltd.], etc., but is not limited thereto. Of these, Floren AO-82 and AO-106 are preferred.
  • the antifoaming agent is 0.0001 to 0.004 parts by mass, preferably 0.001 to 0.004 parts per 100 parts by mass of the aforementioned (a) active energy ray-curable polyfunctional monomer. It is desirable to use at a ratio of parts by mass.
  • the antifoaming agent (d) is composed of a fluorosilicone compound having a weight average molecular weight measured in terms of polystyrene within the above-described range, and a fluorine content equal to or higher than the above-described numerical value, and within the above-described range.
  • the curable composition of the present invention exhibits further superior defoaming properties and coating properties.
  • aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, and cyclohexane
  • Halogens such as methyl chloride, methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate , Ethyl cellosolve acetate, propylene glycol monomethyl ether acetate Esters such as carbonates or ester ethers; diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve
  • the amount of these (e) organic solvents used is not particularly limited.
  • the organic solvent is used at a concentration such that the solid content in the curable composition of the present invention is 1 to 70% by mass, preferably 30 to 40% by mass.
  • the solid content concentration also referred to as non-volatile content concentration
  • the solid content concentration means the solid content relative to the total mass (total mass) of the components (a) to (e) (and other additives as required) of the curable composition of the present invention. The content of (all solvent components are removed) is expressed.
  • additives that are generally added as necessary, for example, polymerization inhibitors, photosensitizers, leveling agents, surface activity, unless the effects of the present invention are impaired.
  • An agent, an adhesion-imparting agent, a plasticizer, an ultraviolet absorber, an antioxidant, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, a dye, and the like may be appropriately blended.
  • the curable composition of this invention can form a cured film by apply
  • the cured film is also an object of the present invention.
  • the hard coat layer in the hard coat film mentioned later can consist of this cured film.
  • the base material in this case examples include various resins (polycarbonate, polymethacrylate, polystyrene, polyester such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, Acetyl cellulose, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene resin, etc.), metal, wood, paper, glass, slate, and the like.
  • the shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.
  • the coating method on the base material is a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a spray coating method, a bar coating method, a die coating method, an ink jet method, a printing method (a relief plate, an intaglio plate).
  • Lithographic printing, screen printing, etc. can be selected as appropriate, and in particular, it can be used for a roll-to-roll method, and from the viewpoint of thin film coating, a relief printing method, particularly a gravure coating method is used. It is desirable. It is preferable that the curable composition is filtered in advance using a filter having a pore diameter of about 0.2 ⁇ m or the like and then used for coating.
  • the coating film is pre-dried with a hot plate or an oven as necessary to remove the solvent (solvent removal step).
  • the heat drying conditions at this time are preferably 40 to 120 ° C. and about 30 seconds to 10 minutes, for example.
  • the coating film is cured by irradiating active energy rays such as ultraviolet rays. Examples of active energy rays include ultraviolet rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable.
  • a light source used for ultraviolet irradiation sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED, or the like can be used. Furthermore, after that, polymerization may be completed by performing post-baking, specifically by heating using a hot plate, an oven or the like.
  • the thickness of the formed cured film is usually 0.01 to 50 ⁇ m, preferably 0.05 to 20 ⁇ m after drying and curing.
  • a hard coat film provided with a hard coat layer on at least one surface (surface) of a film substrate can be produced using the curable composition of the present invention.
  • the hard coat film and the method for producing the hard coat film are also objects of the present invention, and the hard coat film is suitably used for protecting the surface of various display elements such as a touch panel and a liquid crystal display.
  • the hard coat layer in the hard coat film of the present invention comprises a step of applying the curable composition of the present invention on a film substrate to form a coating film, and irradiating the coating film with active energy rays such as ultraviolet rays. It can be formed by a method including a step of curing the coating film.
  • various transparent resin films that can be used for optical applications among the substrates mentioned in the above-mentioned ⁇ cured film> are used.
  • a resin selected from polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, triacetyl cellulose, etc.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • polycarbonate polymethacrylate
  • polystyrene polyolefin
  • polyamide polyamide
  • polyimide polyimide
  • the process of drying this coating film and removing a solvent as needed can be included after a coating-film formation process.
  • the drying method (solvent removal process) of the coating film quoted to the above-mentioned ⁇ cured film> can be used.
  • the thickness of the hard coat layer thus obtained is preferably 1 to 15 ⁇ m, more preferably 1 to 10 ⁇ m.
  • Bar coat application device PM-9050MC manufactured by SMT Co., Ltd.
  • Bar OSG Systems Products A-Bar OSP-25, maximum wet film thickness 25 ⁇ m (corresponding to wire bar # 10)
  • Application speed 4 m / min
  • Oven Equipment Dust dryer DRC433FA manufactured by Advantech Toyo Co., Ltd.
  • UV curing device CV-110QC-G manufactured by Heraeus Co., Ltd.
  • Lamp Heraeus high pressure mercury lamp H-bulb
  • GPC Gel permeation chromatography
  • Equipment HLC-8220GPC manufactured by Tosoh Corporation Column: Shodex (registered trademark) GPC KF-804L, GPC KF-805L manufactured by Showa Denko K.K.
  • PFPE1 Perfluoropolyether having a hydroxy group via a poly (oxyalkylene) group (repeating unit number 8 to 9) at both ends
  • BEI 1,1-bis (acryloyloxymethyl) ethyl isocyanate
  • DOTDD Dioctyltin dineodecanoate
  • MSCAT-05 manufactured by Nippon Chemical Industry Co., Ltd.
  • DPHA Dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate mixture
  • PETA Pentaerythritol triacrylate / pentaerythritol tetraacrylate mixture [Shin-Nakamur
  • NK ester A-TMM-3LM-N] UA 6-functional aliphatic urethane acrylate oligomer
  • EBECRYL registered trademark
  • I2959 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one
  • IRGACURE registered trademark
  • FS1 Fluorosilicone-based antifoaming agent [Kyoeisha Chemical Co., Ltd., Floren AO-82, active ingredient concentration 1.8 mass% butyl acetate / hexane solution]
  • FS2 fluorosilicone-based antifoaming agent [Kyoeisha Chemical Co., Ltd., Floren AO-106, active ingredient concentration 2 mass% butyl acetate / hexane solution]
  • FS3 fluorosilicone-based antifoaming agent (Shin
  • the weight average molecular weight Mw measured by GPC of the obtained SM1 in terms of polystyrene was 3,400, and the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) was 1.1.
  • the fluorine content calculated from the F1 quantitative analysis of SM1 was 36% by mass.
  • This curable composition was bar-coated on an A4-sized double-sided easy-adhesion treated PET film [Lumirror (registered trademark) U403, manufactured by Toray Industries, Inc., thickness 100 ⁇ m] to obtain a coating film.
  • This coating film was dried in an oven at 120 ° C. for 3 minutes to remove the solvent.
  • the obtained film was exposed to UV light having an exposure amount of 300 mJ / cm 2 in a nitrogen atmosphere to expose a hard coat film having a hard coat layer (cured film) having a thickness of about 6 ⁇ m.
  • perfluoropolyether SM1 having an acryloyl group via a poly (oxyalkylene) group and one urethane bond at both ends as a surface modifier in the hard coat layer, and FS1 as an antifoaming agent
  • the curable compositions of Examples 1 to 4 using a predetermined amount of FS2 have excellent defoaming properties and coating properties, and each hard coat film produced using these curable compositions is transparent. Excellent water and oil repellency and scratch resistance.
  • Comparative Example 5 using FS4 whose Mw of the fluorosilicone compound is 1,000 resulted in a greatly inferior defoaming property of the curable composition, and the curable composition even when the amount of FS4 used was 10 times.
  • the antifoaming property of the product was not different from that of Comparative Example 5 (Comparative Example 6).
  • any of the weight average molecular weight and F content measured in polystyrene conversion of the fluorosilicone compound used as the antifoaming agent, and the amount of the antifoaming agent used is within a predetermined numerical range. It is not possible to obtain a curable composition satisfying the defoaming property and coating property only by detachment, and only the curable composition of the present invention has excellent defoaming property and coating property, and transparency, repellency. A hard coat film satisfying all of water / oil repellency and scratch resistance can be formed.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

La présente invention aborde le problème consistant à fournir un matériau destiné à former une couche de revêtement dure, qui possède d'excellentes propriétés de faible moussage, tout en permettant d'atteindre une résistance élevée aux rayures. La solution selon l'invention porte sur une composition durcissable qui renferme (a) 100 parties en masse d'un monomère polyfonctionnel durcissable par un rayonnement d'énergie active, (b) 0,1 à 10 parties en masse d'un perfluoropolyéther qui possède un groupe polymérisable par un rayonnement d'énergie active aux deux extrémités d'une chaîne moléculaire renfermant un groupe poly(oxyperfluoroalkylène) par l'intermédiaire d'un groupe poly(oxyalkylène) ou par l'intermédiaire, dans cet ordre, d'un groupe poly(oxyalkylène) et d'une liaison uréthanne, (c) 1 à 20 parties en masse d'un amorceur de polymérisation qui produit des radicaux au moyen d'un rayonnement d'énergie active, (d) 0,0001 à 0,004 partie en masse d'un agent antimoussant, qui est composé d'un composé fluorosilicone possédant une teneur en fluor de 31 % en masse ou plus tout en possédant une masse moléculaire moyenne en masse de 10 000 à 200 000, exprimée en polystyrène, et (e) un solvant organique ; et un film de revêtement dur, qui comprend une couche de revêtement dure qui est composée d'un film durci formé à partir de cette composition.
PCT/JP2017/034143 2016-09-21 2017-09-21 Matériau de revêtement dur résistant aux rayures WO2018056370A1 (fr)

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WO2020162329A1 (fr) * 2019-02-06 2020-08-13 日産化学株式会社 Composition durcissable pour revêtement dur
WO2022034733A1 (fr) * 2020-08-13 2022-02-17 日産化学株式会社 Composition durcissable pour revêtement dur

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WO2019045096A1 (fr) * 2017-09-01 2019-03-07 日産化学株式会社 Composition durcissable pour revêtement extensible et résistant aux rayures
WO2020162329A1 (fr) * 2019-02-06 2020-08-13 日産化学株式会社 Composition durcissable pour revêtement dur
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KR20210124349A (ko) * 2019-02-06 2021-10-14 닛산 가가쿠 가부시키가이샤 하드코트용 경화성 조성물
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WO2022034733A1 (fr) * 2020-08-13 2022-02-17 日産化学株式会社 Composition durcissable pour revêtement dur

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KR20190055071A (ko) 2019-05-22

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