Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
  • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
  • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
  • Y10T428/31544—Addition polymer is perhalogenated
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31645—Next to addition polymer from unsaturated monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31645—Next to addition polymer from unsaturated monomers
  • Y10T428/31649—Ester, halide or nitrile of addition polymer

Definitions

• the present invention has an activity to provide a transparent film that is cured by irradiation with active energy rays, has good abrasion resistance, and is excellent in antifouling property against greasy stains, particularly in removing fingerprints attached to the surface.
• the present invention relates to an energy ray-curable coating composition. Further, the present invention has a coating made of a cured product of the coating composition on the surface of a glass or plastic substrate, and has excellent abrasion resistance and antifouling property against oily stains over a long period of time. Related to molded products that exhibit fingerprint removability.
• Mirror-finished metal plates and inorganic glass show windows, show cases, automotive apertures, anti-reflective coatings, optical filters, optical lenses, liquid crystal displays, CRT displays, projection televisions, plasma displays, EL displays,
• fingerprints, sebum, sweat, cosmetics, and other oily stains often adhere to the environment in which they are placed. It is not easy to remove such greasy stains once they are adhered.
• the adhered stains are conspicuous and pose a problem.
• Japanese Patent Application Laid-Open No. 2002-248703 discloses that a silicone compound or a fluorine-containing compound is lubricated to impart abrasion resistance and lubricity to a cured product layer of a coated molded product. Coating compositions added as agents are used.
• the silicone-based compounds and fluorine-containing compounds exemplified in the above publication have a low affinity for the matrix resin, so that when coated, the bleed-out bleeds from the surface of the matrix resin, and the transparency of the coated portion is high. It is easy to damage Had a problem. Also, if a silicone compound is added as a lubricity imparting agent, sufficient antifouling properties cannot be exhibited.
• Japanese Patent Application Laid-Open No. 11-231 595 discloses a hard coating agent for optical recording media containing a fluorine-containing surfactant.
• the hard coat layer containing the fluorine-based surfactant has insufficient abrasion resistance, and is required to have a cross-linked fluorine-based surfactant and a non-cross-linked fluorine-based surfactant in order to impart antifouling property. It requires two types of fluorine-based surfactants, namely surfactants.
• Japanese Patent Application Laid-Open No. 2000-191668 discloses an antifouling method containing a fluorine-containing compound having an alkoxysilane structure at a terminal via a carbamate bond, and fine particles of an inorganic compound or an organic compound. Compositions are described. However, since the antifouling composition obtains adhesiveness by bonding an alkoxysilane contained in the composition to a layer made of an inorganic compound such as silicon dioxide, the inorganic compound layer does not exist on the substrate surface. In this case, there was a problem that the antifouling property could not be exhibited for a long time even if the antifouling property could be obtained temporarily.
• this antifouling composition is intended only for antifouling properties, does not have mechanical strength, and its surface is relatively easily scratched. For this reason, when it is necessary to impart mechanical strength such as abrasion resistance to the surface of the base material, it is necessary to provide a hard coat layer on the surface of the base material.
• the present invention solves the above-mentioned problems in the prior art, and has excellent abrasion resistance and oiliness on various kinds of substrates to be treated, particularly, glass, metal or plastic substrates. It is an object of the present invention to provide a coating composition which has excellent antifouling property against stains and can form a transparent film which exhibits excellent fingerprint removability over a long period. Another object of the present invention is to provide a molded product made of glass or plastic having a coating made of a cured product of the coating composition on its outer surface. Invention disclosure>
• the present invention relates to a water- and oil-repellency-imparting agent (B) in an amount of 0.01 to 10 parts by mass, based on 100 parts by mass of the active energy ray-curable polymerizable monomer (A).
• a coating composition containing 0.1 to 10 parts by mass of a reactive energy ray polymerization initiator (C), wherein the polymerizable monomer (A) is a polymerizable monomer contained in the coating composition.
• R 3 is an alkylene group having 6 to 20 carbon atoms
• X and y are integers of 5 to 100
• u is an integer of 3 to 5
• t is 1 to 20. It is an integer.
• the first coating composition of the present invention was applied to the surface of a base material because the water / oil repellency imparting agent (BT) had an appropriate compatibility with other components of the composition.
• the water / oil repellency-imparting agent (B-T) segregates on the surface of the coating film without impairing the transparency of the coating film before curing.
• the active energy ray-curable functional group in the water / oil repellency-imparting agent (BT) is cured by irradiation with an active energy ray, the active energy ray-curable functional group is bonded to and fixed to the resin matrix in the composition.
• the surface of the coating made of the cured product of the composition is excellent in water / oil repellency, and exhibits excellent fingerprint removability over a long period of time.
• the part (b-1) exhibiting the water / oil repellency is selected from the group consisting of the parts represented by the following formulas (5) to (9). It is preferred to have at least one.
• k is an integer of 1 to 16 and P q, r and s are integers of 00.
• the site (b) exhibiting the water / oil repellency is represented by the following formula (10) or the following formula (). It is preferable to have a portion to be formed.
• R f is a polyfluoroalkyl group having 1 to 16 carbon atoms (including those having an oxygen atom), n is an integer of 1 to 50, and m and L are 0 to 3 And 6 ⁇ m + L> 0.)
• R f is a polyfluoroalkyl group having 1 to 16 carbon atoms (including those having an oxygen atom), e is an integer of 1 to 50, and g and h are 0 to 3 And 6 ⁇ g + h> 0.)
• the coating composition of the present invention further contains 0.1 to 500 parts by mass of colloidal silica (D) based on 100 parts by mass of the polymerizable monomer (A).
• the colloidal silica (D) is a mercapto group-containing silane compound (S 1) or (meth) acryloyl group in which an organic group having a mercapto group, a hydrolyzable group or a hydroxyl group, and a silicon atom are bonded to a silicon atom.
• S 1 mercapto group-containing silane compound
• S 2 acryloyl group in which an organic group having the formula (1) and a hydrolyzable group or a hydroxyl group are bonded to a silicon atom.
• the mercapto group-containing silane compound (S 1) is preferably a compound represented by the following formula (12).
• R 1 is a divalent hydrocarbon group
• R 2 is a hydroxyl group or a hydrolyzable group
• R 5 is a monovalent hydrocarbon group
• f is an integer of 1 to 3.
• the (meth) acryloyloxy group-containing silane compound (S 2) is preferably a compound represented by the following formula (13).
• R 6 is a hydrogen atom or a methyl group
• R 7 is a divalent hydrocarbon group
• R 2 is a hydroxyl group or a hydrolyzable group
• R 5 is a monovalent hydrocarbon group
• f is an integer of 1 to 3. Represents.
• the present invention also relates to a coating composition for forming a film by curing, wherein the contact angle of the cured film surface with oleic acid is initially 60 ° or more and 55 ° C or more after the moisture resistance test, the haze value of the cured film is 3% or less, and the Taber abrasion test specified in IS09352 (Abrasion wheel: CS-10F, single wheel load) (A)
• the active energy ray-curable coating composition is characterized in that the change in the haze value of the film after curing before and after (500 g, 500 rotations) is 10% or less. .
• the second coating composition of the present invention has excellent water and oil repellency on the surface of the cured film, and exhibits excellent water and oil repellency over a long period of time. Also, the cured film has excellent transparency and abrasion resistance.
• the coating composition preferably contains an active energy ray-curable polymerizable monomer (A).
• the coating composition having the above-mentioned properties of the cured film is preferably a coating composition containing (A), (B) and (C) described above.
• the present invention provides a molded article having a coating of 0.1 to 50 made of a cured product of the above-mentioned coating composition on a glass or plastic substrate surface.
• the first coating composition of the present invention (hereinafter, simply referred to as “first coating composition”) is added to 100 parts by mass of the active energy ray-curable polymerizable monomer (A).
• an active energy linear curing type coating containing 0.1 to 10 parts by mass of the water / oil repellency imparting agent (B) and 0.1 to 10 parts by mass of the active energy ray polymerization initiator (C). It is a composition for use.
• the active energy ray-curable polymerizable monomer (A) (hereinafter sometimes referred to as the polymerizable monomer (A)) is an active energy ray-curable polymerizable compound described below.
• an acryloyl group or a methacryloyl group is used as a polymerizable functional group.
• a polyfunctional polymerizable monomer (a-1) (hereinafter sometimes referred to as a monomer (a-1)) having two or more in a molecule, and a monofunctional polymerizable monomer described later It comprehensively represents other polymerizable monomers represented by (a-2). However, compounds corresponding to the water / oil repellency-imparting agent (B) described later are not included.
• an acryloyl group and a methyl acryloyl group are collectively referred to as a (meth) acryloyl group.
• the monomer (a-1) is described in JP-A-10-81 PT / JP2003 / 014385
• the monomer (a-1) has at least three polymerizable functional groups in the molecule from the viewpoint of exhibiting a high level of abrasion resistance. Those having a molecular weight of 120 or less are preferred. Examples of the monomer (a-1) satisfying such conditions include the following compounds.
• polyester which is a reaction product of pentaerythritol or polypentaerythritol and (meth) acrylic acid, and has three or more (meth) acryloyl groups, more preferably 4 to 20.
• Multifunctional compound Specifically, there are trimethicone propanetri (meth) acrylate, Penyu erythritol tri (meth) acrylate, Penyu erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Preferred are mentioned.
• acrylurethane a compound containing a (meth) acryloyl group having a urethane bond in the molecule
• the urethane bond acts as a pseudo-crosslinking point due to the action of the hydrogen bond, and the molecular weight per functional group
• the monomer (a_l) satisfying such conditions.
• Penyu erythritol is an acrylic urethane which is a reaction product of hydroxyl group-containing poly (meth) acrylate and polyisocyanate, and has at least three (meth) acryloyl groups. More preferably, a polyfunctional compound having 4 to 20 compounds.
• the first coating composition may contain, as the polymerizable monomer (A), a polymerizable monomer other than the monomer (a-1).
• a polymerizable monomer other than the monomer (a-1) a monofunctional polymerizable monomer having one (meth) acryloyl group in one molecule (hereinafter, referred to as a monomer) Body (a—2).) Or (meta)
• a monomer a monomer
• a—2 a monofunctional polymerizable monomer having one (meth) acryloyl group in one molecule
• a—2 a monofunctional polymerizable monomer having one (meth) acryloyl group in one molecule
• metal metal
• the content of the monomer (a-1) is 20 to: LOO mass%.
• the first coating composition is composed of a cured product.
• the abrasion resistance of the coating (hereinafter sometimes referred to as a cured coating) is excellent.
• the content of the monomer (a-1) is more preferably 50 to 100% by mass, and particularly preferably 70 to 100% by mass.
• the water- and oil-repellency-imparting agent (B) includes the water- and oil-repellency-imparting agent (BT) described below and another water- and oil-repellency-imparting agent described later. It is expressed as
• the coating composition of the present invention comprises the water- and oil-repellency-imparting agent (B) in an amount of from 0.01 to L0 parts by mass based on 100 parts by mass of the polymerizable monomer (A). And preferably 0.1 to 5.0 parts by mass. When the amount of the water and oil repellency imparting agent (B) is within this range, the cured film has excellent water and oil repellency and abrasion resistance.
• the cured film will have poor water / oil repellency.
• the water / oil repellency-imparting agent (B) is more than 10 parts by mass, the cured film is plasticized, abrasion resistance is reduced, and transparency is poor.
• the water- and oil-repellency-imparting agent (B-T) comprises a part (b-1) exhibiting water- and oil-repellency, an active energy ray-curable functional group (b-2), and the following formulas (1) to (4) A compound having at least one site (b-3) selected from the group consisting of the portions represented by in a molecule.
• R 3 is an alkylene group having 6 to 20 carbon atoms
• X and y are integers of 5 to 100
• u is an integer of 3 to 5
• t is:! Is an integer.
• the portion (b-11) (hereinafter sometimes referred to as the portion (b-1)) exhibiting water- and oil-repellency is generally a water repellent or Fluorine-containing compounds used as an oil repellent (for example, a homopolymer of a polymerizable monomer containing a polyfluoroalkyl group such as a (meth) acrylate ester containing a polyfluoroalkyl group, or a mixture thereof with another acrylic acid Ester, maleic anhydride, chloroprene, copolymers with polymerizable monomers such as benzene, methyl vinyl ketone, etc., fluorine-containing polyester compounds, fluorosilicon compounds, etc.)
• the site (b-1) is at least one selected from the group consisting of portions represented by the following formulas (5) to (9).
• the portion of the above formula (5) is a perfluoroalkyl group, and the number of carbons, k, is preferably from 1 to 16. When the carbon number is in this range, the crystallinity of the group is weak, and the transparency of the cured film is not impaired.
• Equation (9) represents the unit of difluoromethylene.
• p, q, r and s indicating the degree of polymerization, 100 or less is preferable.
• P, Q, r and s are more preferably integers from 1 to 80 4385
• the site (b-1) may have any one of the above formulas (5) to (9).
• a child may have two or more types.
• the site (b-1) preferably has a portion represented by the following formula (10).
• R f is a polyfluoroalkyl group having 1 to 16 carbon atoms (including those having an oxygen atom), n is an integer of 1 to 50, and m and L are Is an integer from 0 to 3 provided that the following relationship is satisfied.
• ⁇ C 3 F 6 means OCF 2 CF 2 CF 2 or ⁇ CF (CF 3 ) CF 2 .
• a polyfluoroalkyl (R f ) group refers to a group in which two or more hydrogen atoms of an alkyl group have been substituted with fluorine atoms.
• the R f group preferably has a straight-chain structure, but may have a branched structure. When the R f group has a branched structure, the branched portion exists at the terminal portion of the R f group, and the terminal portion has 1 carbon atom. It is preferably a short chain of up to 4.
• the Rf group preferably has 1 to 8 carbon atoms.
• the carbon number of the Rf group is in the above range, the crystallinity of the Rf group is relatively weak, and the cured film has excellent transparency.
• the R f group may contain another halogen atom other than a fluorine atom.
• a chlorine atom is preferable.
• An etheric oxygen atom, an ester bond, a sulfonamide group, or a thioetheric sulfur atom may be inserted between the carbon-carbon bonds in the R f group.
• the number of fluorine atoms in the R f group is [(the number of fluorine atoms in the R f group) / (the number of hydrogen atoms contained in the corresponding alkyl group having the same carbon number as the R f group)] X 100 (% )), It is preferably at least 60%, particularly preferably at least 80%.
• R f group is preferably a group in which all of the hydrogen atoms of the alkyl group have been substituted with fluorine atoms (that is, a perfluoroalkyl group) or a group having a perfluoroalkyl group at a terminal portion.
• R f group examples include the following groups.
• R f group is a group having an etheric oxygen atom, an ester bond, a sulfonamide group, or a thioetheric sulfur atom inserted between the -carbon bonds include the following groups.
• the R f group CF 3 one, C 2 F 5 one, C a F 7 one is preferable.
• the R f group is any of these groups, it is easy to obtain a raw material when synthesizing the site of the formula (10), and 2003/014385
• the site (b-1) preferably contains a portion represented by the following formula (11).
• R f is a polyfluoroalkyl group having 1 to 16 carbon atoms (including those having an oxygen atom), e is an integer of 1 to 50, and g and h are Is an integer from 0 to 3 provided that the following relationship is satisfied.
• R f in equation (11) is the same as described for R f in equation (10).
• the first coating composition comprises a plurality of water- and oil-repellency-imparting agents (B-T) having different portions (b-1) in combination as water- and oil-repellency-imparting agents (B-T). May be.
• the active energy ray-curable functional group (b-2) (hereinafter sometimes referred to as a functional group (b-2)) in the water- and oil-repellency-imparting agent (BT) refers to a radical reactivity.
• Any functional group may be used, and specific examples thereof include (meth) acryloyl, aryl, vinyl, vinyl ether, halogen, and mercapto groups.
• a (meth) acryloyl group is particularly preferred because of the stability of the chemical bond formed by radical reactivity. ⁇
• the water- and oil-repellency-imparting agent (BT) has the functional group (b-2), so that when the first coating composition is cured by irradiation with active energy rays, the functional group (b-2) ) Also causes a curing reaction, and is covalently bonded to the polymerizable monomer (A) constituting the resin component of the first coating composition.
• the ice repellency-imparting agent (B-T) bonds to the cured product of the first coating composition, that is, the cured film via a covalent bond, so that the water- and oil-repellency imparting agent (B-T) B—T) is fixed on the surface of the coating.
• the water- and oil-repellency-imparting agent (B-T) is not volatilized from the surface of the film, which is preferable.
• the water- and oil-repellency imparting agent (BT) is bonded to the film, the surface of the film after curing exhibits excellent water and oil repellency over a long period of time and excellent fingerprint removability for a long time.
• the water- and oil-repellency-imparting agent (BT) may have any one of the functional groups exemplified above as the functional group (b-2), or two or more of the functional groups in the same molecule. It may have a functional group. Further, the first coating composition has a water repellent property. T / JP2003 / 014385
• BT oiliness imparting agent
• a plurality of water / oil repellency imparting agents (BT) having different functional groups (b-2) may be used in combination.
• a part (b-3) having at least one selected from the group consisting of the parts represented by formulas (1) to (4) of the water / oil repellency imparting agent (BT) (hereinafter referred to as a part ( b) has the function of exhibiting compatibility with the polymerizable monomer (A).
• R 3 is an alkylene group having 6 to 20 carbon atoms
• X and y are integers of 5 to 100
• u is an integer of 35
• t is an integer of 1 to 20. It is.
• the portion (b-1) of the water- and oil-repellency-imparting agent (B-T) exhibiting the water- and oil-repellency has a low affinity for the resin matrix formed from the polymerizable monomer (A), so that it is coated.
• the water- and oil-repellency-imparting agent (BT) having a portion (b-3) having excellent compatibility with the polymerizable monomer (A) is a portion having a low affinity for the polymerizable monomer (A). Even when (b-1) is selected, it has an appropriate compatibility with the polymerizable monomer (A).
• the water- and oil-repellency-imparting agent (B-T) has an appropriate compatibility with the polymerizable monomer (A).
• the water / oil repellency imparting agent (BT) segregates on the surface of the coating film without impairing the transparency of the coating film before curing. Therefore, the transparency of the cured film is not impaired.
• the portion of the above formula (1) is a linear or branched alkylene group having 6 to 20 carbon atoms.
• the water- and oil-repellency imparting agent (B-T) has an appropriate compatibility with the polymerizable monomer (A), and the crystallinity of the group is relatively weak. It has excellent transparency of the cured film and excellent water and oil repellency of the surface of the film, and exhibits excellent fingerprint removability over a long period of time. If the number of carbon atoms is 5 or less, the compatibility with the polymerizable monomer (A) is low, so that the transparency of the coating film before curing is impaired. This impairs the transparency of the cured film. Means to be On the other hand, when the number of carbon atoms is more than 20, the crystallinity of the group becomes strong, so that the transparency of the cured film is also impaired.
• the portion of the above formula (2) represents a unit of ethylene oxide.
• X representing the degree of polymerization is from 5 to 100, preferably from 5 to 80.
• the water / oil repellency-imparting agent (BT) has appropriate compatibility with the polymerizable monomer (A), so that the transparency of the film after curing and the film It has excellent water and oil repellency on the surface and exhibits excellent fingerprint removal properties over a long period of time.
• X is 4 or less, the compatibility of the water / oil repellency imparting agent (BT) becomes low, and the transparency of the cured film is impaired.
• the above expression (3) represents a propylene oxide unit.
• Y representing the degree of polymerization is 5 to 100, preferably 5 to 80.
• the water / oil repellency-imparting agent (BT) has an appropriate compatibility with the polymerizable monomer (A), so that the transparency of the coating after curing and the coating property of the coating are high. It has excellent water and oil repellency on the film surface, and exhibits excellent fingerprint removal properties over a long period of time. If y is 4 or less, the compatibility of the water / oil repellency-imparting agent (BT) becomes low, and the transparency of the cured film is impaired.
• the part of the above formula (4) represents a unit obtained from the open lactone.
• the number of carbon atoms of the group is preferably 3 to 5 in terms of availability.
• t indicating the degree of polymerization is preferably 20 or less. When t is within the above range, the crystallinity of the group is not too strong, and the cured film has excellent transparency.
• the water- and oil-repellency-imparting agent (BT) may have any one of the above formulas (1) to (4) as the moiety (b-3), or It may have two or more types. Further, the first coating composition comprises a plurality of water- and oil-repellency-imparting agents (B-T) having different portions (b-3) as the water- and oil-repellency-imparting agents (B-T). Is also good.
• the bonding form of each part in the water / oil repellency-imparting agent (BT) is not particularly limited.
• the bonding form of each part in the water and oil repellency imparting agent (BT) Specifically, the following examples are preferably mentioned.
• Linear type A type in which the site (b-1), site (b-3) and functional group (b-2) are connected linearly. Hereinafter, it is referred to as a linear type.
• a compound having the site (b-1) and having a hydroxyl group-modified terminal is preferably used as the raw material compound forming the site (b-1).
• a compound having the site (b-1) and having a hydroxyl group-modified terminal is preferably used.
• the above-mentioned formula (10) or the above-mentioned formula (11) in which the terminal is modified by a hydroxyl group, polyhexafluoropropylene oxide whose terminal is modified by a hydroxyl group, and the like are preferable.
• a site (b-3) can be constructed adjacent to the site (b-1).
• a polymer such as polyethylene render glycol, polypropylene glycol, or the like can be linked to the site (b_l) by a urethane bond using bifunctional isocyanate or the like.
• the acidity of the terminal hydroxyl group is too high, and the polymerization of monomers such as ethylene oxide, propylene oxide, and lactone proceeds smoothly. May not.
• ethylene carbonate is added while decarboxylation in the presence of a catalyst, and one unit of ethylene oxide is inserted to reduce the acidity of the terminal hydroxyl group. Then, ethylene oxide, propylene oxide, and lactide are added.
• the site (b-3) can also be constructed by polymerizing monomers such as tons.
• the terminal of the site (b-3) is a hydroxyl group. Therefore, as a method for introducing a functional group (b-2) (for example, a (meth) acryloyl group), a method of introducing a (meth) acrylic acid, (meth) acrylic acid chloride, or the like through an ester bond is used. 2-hydroxymethyl acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Preferable examples include a method of introducing a (meth) acrylate or the like through a bifunctional isocyanate via a urethane bond.
• a functional group (b-2) for example, a (meth) acryloyl group
• Preferable examples include a method of introducing a (meth) acrylate or
• a polymer such as polyethylene glycol or polypropylene glycol having one terminal already modified with a (meth) acryloyl group is used to form a bifunctional isocyanate or the like between the terminal hydroxyl group at the site (b-1).
• a polymer such as polyethylene glycol or polypropylene glycol having one terminal already modified with a (meth) acryloyl group is used to form a bifunctional isocyanate or the like between the terminal hydroxyl group at the site (b-1).
• the method of linking the position (b-3) and the functional group (b-2) in this order is also preferable.
• Copolymer type A radical polymerizable macromer having a site (b-1) and a radical polymerizable macromer having a site (b-3) may be prepared, and these macromers may be copolymerized. .
• a functional group (b-2) may be further introduced into the obtained copolymer.
• the macromer having a site (b_l) include, for example, those wherein the terminal of the above formula (10) or the above formula (11) is modified with a (meth) acryloyl group, or
• a preferred example is a fluorinated alkyl ester of acrylic acid.
• Examples of the macromer having the moiety (b-3) include, for example, a polymer in which one end of a polymer such as polyethylene glycol or polypropylene glycol is modified with a (meth) acryloyl group, or a polymer of (meth) acrylic acid.
• Preferable examples include those in which one terminal of a ring-opened polymer of alkyl ester or lactone is modified with a (meth) acryloyl group.
• the functional group (b-2) there is a method in which the above two types of macromers are copolymerized and then introduced into the terminal.
• the hydroxyl group at the end of the two macromers to which the (meth) acryloyl group is not added is converted to an ester bond using (meth) acrylic acid, (meth) acrylic acid chloride, or the like.
• the method of introduction and the method of introduction by urethane binding using a small amount of 2-ethyl methacrylate are preferred.
• the functional group (b-12) is preferably bonded adjacent to the site (b-3).
• the site (b-1) is compared with the case where the functional group (b-2) is bonded adjacent to the site (b-1). This is because the surface migration of) is high, and the cured coating surface has excellent water and oil repellency.
• the water and oil repellency-imparting agent (B) is other than the above-mentioned water- and oil repellency-imparting agent (B—T) May contain a known water / oil repellency imparting agent.
• water- and oil-repellency imparting agents include fluorine-based water- and oil-repellency using fluorine resins such as tetrafluoroethylene and vinylidene fluoride, and fluorine compounds having a perfluoroalkyl group.
• a silicone-based water / oil repellency-imparting agent using an organopolysiloxane having an alkyl group such as a methyl group, an ethyl group or a propyl group or a fluoroalkyl group having a siloxane bond in a main chain and a side chain A wax-based water / oil repellency-imparting agent using beeswax or paraffin, a salt of zirconium and a fatty acid, a metal salt-based water / oil repellency-imparting agent using a salt of aluminum and a fatty acid, and the like.
• the known water- and oil-repellency-imparting agent in the present specification does not include the compound corresponding to the above-mentioned water- and oil-repellency-imparting agent (BT).
• BT water- and oil-repellency-imparting agent
• the content of B) is 30 parts by mass or less based on 100 parts by mass of the total mass.
• the first coating composition further comprises, in addition to the above constitution, 0.1 to 10 parts by mass of the active energy ray polymerization initiator (C) based on 100 parts by mass of the polymerizable monomer (A). Contains parts by mass.
• the amount of the active energy ray polymerization initiator (C) is within the above range, the curability is sufficient, and at the time of curing, all the active energy ray polymerization initiators (
• the active energy ray polymerization initiator (C) as used herein widely includes known photopolymerization initiators.
• photopolymerization initiators include arylketone photopolymerization initiators (e.g., acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethyl ketals, benzones). Dibenzobenzenes, ⁇ -acryloxy esters, etc.), sulfur-containing photopolymerization initiators (eg, sulfides, thioxanthones, etc.), acyl phosphoxides (eg, acyl diaryl phosphoxide), and others.
• photopolymerization initiator Two or more photopolymerization initiators may be used in combination. Further, the photopolymerization initiator may be used in combination with a photosensitizer such as an amine. Specific photopolymerization initiators include, for example, the following compounds, but are not limited thereto.
• Acetofphenone 2—Hydroxy-1-2-Methyl-1-phenylpropane-one-one, 1_ (4-isopropylphenyl) -1-2-Hydroxy-2-—Methylpropane-1-1-one, 1-1- (4-dodecyl) Phenyl) — 2-Methyl-butane 1-one, 1 — ⁇ 4- (2-hydroxyethoxy) phenyl ⁇ -2 —Hydroxy-2-methyl-propane 1-one, 1-hydroxy Xyl phenyl ketone, 2-methyl-1- ⁇ 4- (methylthio) phenyl ⁇ —2-morpholinopropane—one.
• the first coating composition may contain, if necessary, an ultraviolet absorber, a light stabilizer, an antioxidant, a thermal polymerization inhibitor, a leveling agent, a defoaming agent, a thickener, a sedimentation inhibitor, One or more functions selected from the group consisting of pigments (organic coloring pigments, inorganic pigments), coloring dyes, infrared absorbers, fluorescent enhancers, dispersants, conductive fine particles, antistatic agents, antifogging agents, and coupling agents Sexual ingredients may be included.
• an ultraviolet absorber e.g., a light stabilizer, an antioxidant, a thermal polymerization inhibitor, a leveling agent, a defoaming agent, a thickener, a sedimentation inhibitor
• UV absorbers benzotriazole UV absorbers and benzophenone UV absorbers commonly used as UV absorbers for synthetic resins 03 014385
• a salicylic acid-based ultraviolet absorber and a phenyltriazine-based ultraviolet absorber include compounds described in paragraph No. 0788 of JP-A-11-26819.
• the first coating composition and composition contain a polyfunctional polymerizable monomer (a-1), 2- (2-hydroxy-5- (2-acryloyloxyxethyl) phenic acid is used.
• a hindered amine light stabilizer which is generally used as a light stabilizer for a synthetic resin is preferable.
• compounds described in paragraph No. 0800 of JP-A No. 11-266196 are exemplified.
• those having a polymerizable functional group in the molecule such as N-methyl-4-methacryloyloxy 2,2,6,6-tetramethylpiperidine, are particularly preferred.
• antioxidants examples include hindered phenol-based antioxidants such as 2,6-di-tert-butyl-p-cresol, and phosphorus-based antioxidants such as triphenylphosphite.
• thermal polymerization inhibitor examples include hydroquinone monomethyl ether.
• leveling agent examples include a silicone resin-based reppelling agent and an ataryl resin-based reppelling agent.
• antifoaming agent examples include silicone resin antifoaming agents such as polydimethylsiloxane.
• thickener examples include polymethyl methacrylate-based polymers, hydrogenated castor oil-based compounds, and fatty acid amide-based compounds.
• Examples of the organic coloring pigment include a condensed polycyclic organic pigment and a phthalocyanine organic pigment.
• examples of the inorganic pigment include titanium dioxide, cobalt oxide, molybdenum red, and titanium black.
• Examples of the coloring dye include an organic solvent-soluble azo metal complex dye and an organic solvent-soluble phthalocyanine dye.
• infrared absorbers examples include polymethine, phthalocyanine, metal complex, aminium, dimonium, anthraquinone, dithiol metal complex, naphthoquinone, indolephenol, azo, and triarylmethane compounds. And the like. JP2003 / 014385
• Examples of the conductive fine particles include metal powders such as zinc, aluminum, and nickel, iron phosphide, and antimony-pump tin oxide.
• antistatic agent examples include a nonionic antistatic agent, a cationic antistatic agent, and an anionic antistatic agent.
• force coupling agents examples include silane coupling agents, titanate coupling agents, and the like.
• colloidal silica (D) may be added to the first coating composition for the purpose of further improving the abrasion resistance of the cured film.
• Colloidal silica (D) is ultra-fine particles of a silicic acid anhydride dispersed in a colloidal state in a dispersion medium, and the dispersion medium is not particularly limited, but water, lower alcohols, cellosolves and the like are preferable.
• Specific dispersion media include water, methanol, ethanol, isopropyl alcohol, n-butanol, ethylene glycol, methyl sorb, ethyl sorb, butyl sorb, propylene glycol monomethyl ether acetate, dimethyl Acetoamide, toluene, xylene, methyl acetate, ethyl acetate, pentyl acetate, acetone, etc.
• the average particle size of colloidal silica (D) is not particularly limited, but high transparency of the cured skin is exhibited. To achieve this, the thickness is preferably 1 to 100 nm, particularly preferably 1 to 200 nm, and particularly preferably 1 to 50 nm.
• Colloidal silica (D) can also be used by modifying the particle surface with a hydrolyzate of a hydrolyzable silane compound in order to improve the dispersion stability.
• the surface is modified with the hydrolyzate means a state in which the hydrolyzate of the silane compound is physically or chemically bonded to some or all of the silanol groups on the surface of the colloidal silica particles. This means that the surface properties have been modified.
• silicide particles in which the condensation reaction of the hydrolyzate has progressed are also included. This surface modification can be easily carried out by hydrolyzing a part or all of the hydrolyzable groups of the silane compound in the presence of the silica particles, or by causing a hydrolysis and condensation reaction.
• hydrolyzable silane compound an organic group having a functional group such as a (meth) acryloyl group, an amino group, an epoxy group or a mercapto group and a hydrolyzable group such as an alkoxy group or a hydroxyl group are bonded to a silicon atom.
• a functional group such as a (meth) acryloyl group, an amino group, an epoxy group or a mercapto group and a hydrolyzable group such as an alkoxy group or a hydroxyl group
• Preferred silane compounds are preferred.
• the term “hydrolysable group” refers to a group that can be hydrolyzed at a bond to a silicon atom. For example, 3— (meth) acryloyloxy 2003/014385
• hydrolyzable silane compound examples include a mercapto group-containing silane compound (S 1) in which an organic group having a mercapto group and a hydrolyzable group or a hydroxyl group are bonded to a silicon atom. It is preferable from the viewpoint of high reactivity with A).
• the mercapto group-containing silane compound (S 1) is preferably a compound represented by the following formula (12).
• R 1 represents a divalent hydrocarbon group
• R 2 represents a hydroxyl group or a hydrolyzable group
• R 5 represents a monovalent hydrocarbon group
• f represents an integer of 1 to 3.
• R 1 in the formula (12) is preferably an alkylene group having 2 to 6 carbon atoms, particularly preferably an alkylene group having 3 carbon atoms.
• R 5 is preferably an alkyl group having 4 or less carbon atoms, and particularly preferably a methyl group and an ethyl group.
• R 2 is preferably a hydrolyzable group, more preferably a halogen group or an alkoxy group having 4 or less carbon atoms, and particularly preferably an alkoxy group having 4 or less carbon atoms.
• the halogen chlorine or bromine is preferable.
• As the alkoxy group a methoxy group and an ethoxy group are preferable because of good hydrolyzability.
• f is preferably 2 or 3.
• OMe represents a methoxy group
• ⁇ Et represents an ethoxy group
• O Pr represents an n-propoxy group.
• hydrolyzable silane compound an organic group having a (meth) acryloyl group and a hydrolyzable group or a hydroxyl group are bonded to a silicon atom.
• the (meth) acryloyl group-containing silane compound (S 2) is preferred from the viewpoint of high reactivity with the polymerizable monomer (A) and stability of the bond.
• As the (meth) acryloyl group-containing silane compound (S 2) a compound represented by the following formula (13) is preferable.
• R 6 is a hydrogen atom or a methyl group
• R 7 is a divalent hydrocarbon group
• R 2 is a hydroxyl group or a hydrolyzable group
• R 5 is a monovalent hydrocarbon group
• f is an integer of 1 to 3. Represents a number.
• R 1 in the formula (13) is preferably an alkylene group having 2 to 6 carbon atoms, particularly preferably an alkylene group having 3 carbon atoms.
• R 5 is preferably an alkyl group having 4 or less carbon atoms, and particularly preferably a methyl group and an ethyl group.
• R 2 is preferably a hydrolyzable group, more preferably a halogen group or an alkoxy group having 4 or less carbon atoms, and particularly preferably an alkoxy group having 4 or less carbon atoms.
• the halogen chlorine or bromine is preferable.
• As the alkoxy group a methoxy group and an ethoxy group are preferable because of good hydrolyzability.
• f is preferably 2 or 3.
• the blending amount (solid content) is preferably at least 0.1 part by mass and at most 500 parts by mass with respect to 100 parts by mass of the polymerizable monomer (A). It is more preferably from 1 part by mass to 300 parts by mass, and particularly preferably from 10 parts by mass to 200 parts by mass. Within this range, the film after curing has sufficient abrasion resistance, hardly generates haze, and hardly causes cracks and the like due to external force.
• an organic solvent may be added to the first coating composition for the purpose of improving the coatability of the coating composition and the adhesion to the substrate surface.
• the organic solvent there is a problem in the solubility of the polymerizable monomer (A), the water / oil repellency imparting agent (B), the active energy ray polymerization initiator (C), the colloidal silica (D), and other additives. There is no particular limitation as long as it satisfies the above performance. Also, two or more organic solvents can be used in combination.
• the amount of the organic solvent to be used is preferably 100 times or less, more preferably 50 times or less, based on the weight of the polymerizable monomer (A).
• organic solvent examples include lower alcohols such as ethyl alcohol, butyl alcohol and isopropyl alcohol, ketones such as methyl isopropyl ketone, methyl ethyl ketone and acetone, dioxane, diethylene glycol dimethyl ether, tetrahydrofuran, and methyl t-butyl ether.
• organic solvents such as ethers, methylcellosolve, ethylsesolve, butylcellesolve, and cellosolves such as propylene glycol monomethyl ether acetate are preferred.
• esters such as n-butyl acetate, isoamyl acetate, diethylene glycol monoacetate, polyfluoro hexane, polyfluoromethylcyclohexane, and polyfluoro-1,3-dimethylcyclohexane, etc.
• esters such as n-butyl acetate, isoamyl acetate, diethylene glycol monoacetate, polyfluoro hexane, polyfluoromethylcyclohexane, and polyfluoro-1,3-dimethylcyclohexane, etc.
• Perfluoroaliphatic hydrocarbons polyfluorinated aromatic hydrocarbons such as bis (trifluoromethyl) benzene, octogenated hydrocarbons such as polyfluorinated aliphatic hydrocarbons, and toluene , Xylene, hexane and other hydrocarbons can also be used.
• These organic solvents may be used as a mixture of two or
• an organic solvent is included in the first coating composition, it is preferable to select an appropriate organic solvent according to the type of the substrate on which the coating is formed.
• the substrate is made of an aromatic polycarbonate resin having low solvent resistance, it is preferable to use a solvent having low solubility in the aromatic polycarbonate resin, and it is preferable to use a lower alcohol, a cellosolve, an ester, or the like. Ethers and mixtures thereof are suitable.
• the first coating composition is applied to a glass or plastic substrate by dipping, spin coating, flow coating, spraying, bar coating, gravure coating, mouth-coating, blade
• the composition is applied by a coating method, an air-knife coating method, or the like.
• the composition is dried and then cured by irradiation with active energy rays.
• the active energy ray is preferably an ultraviolet ray, an electron beam, an X-ray, radiation, a high-frequency ray, or the like, and particularly preferably an ultraviolet ray having a wavelength of 180 to 500 nm is economically preferable.
• Active energy radiation sources include xenon lamps, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, carbon arc lamps, evening stainless lamps, and other ultraviolet irradiation devices, electron beam irradiation devices, X-ray irradiation devices, and high-frequency generators. Etc. can be used.
• the irradiation time of the active energy ray can be appropriately changed depending on the type of the polymerizable monomer (A), the type of the active energy ray linear polymerization initiator (C), the thickness of the coating, the active energy ray source and the like.
• the goal is usually achieved by irradiating for 0.1 to 60 seconds. Further, for the purpose of completing the curing reaction, heat treatment can be performed after irradiation with active energy rays.
• a coating having a thickness of 0.1 to 5 is preferred, and a coating having a thickness of 0.2 to 20 x m is particularly preferred. It is preferable that the thickness of the coating be in the above range, since the abrasion resistance becomes sufficient and the hardening of the deep part of the coating becomes sufficient.
• the most preferred coating thickness is from 0.3 to: L 0 m.
• the cured film has good transparency, and has excellent abrasion resistance and water / oil repellency on its surface, and exhibits excellent fingerprint removability over a long period of time. Therefore, the film is excellent in antifouling property against oily stains such as fingerprints, sebum, sweat, cosmetics, etc., and it is difficult for such oily stains to adhere, and even if attached, it is easily wiped off. be able to. JP2003 / 014385
• the cured film of the first coating composition exhibits excellent fingerprint removability for the following reasons.
• the surface of the cured film has excellent water and oil repellency, even if a “fingerprint” adheres to the surface of the film, the surface of the film repels the water and sebum components contained in the “fingerprint”, and the “fingerprint” It is considered that "does not adhere to the surface of the coating, and that spherical moisture and sebum components are on the surface of the coating. Therefore, the sebum component and the like can be easily wiped off. This is considered to be excellent in fingerprint removal.
• the second coating composition of the present invention (hereinafter, referred to as “second coating composition”) is an active energy ray-curable coating composition that forms a film by curing. It has characteristics.
• the initial contact angle of the cured film surface with oleic acid is 60 ° or more and 55 ° or more after the moisture resistance test
• Haze value of cured film is 3% or less
• the second coating composition has the above properties, so that the cured coating surface has excellent water and oil repellency, and the excellent water and water repellency. Oiliness develops over a long period of time.
• the contact angle of a droplet specifically, a droplet of water and oleic acid placed on the surface of a cured film is used as an index of water / oil repellency.
• the second coating composition has the following contact angle of the cured film surface as measured by the procedure described in Examples described later.
• Water 85 degrees or higher, preferably 90 degrees or higher, more preferably 95 degrees or higher (initial), 80 degrees or higher (after moisture resistance test)
• Oleic acid 60 degrees, preferably 65 degrees or more, more preferably 70 degrees or more (initial), 55 degrees or more (after moisture resistance test)
• the second coating composition has the above properties, so that the cured film has excellent transparency.
• a haze value is used as an index of transparency of a cured film.
• the haze value of the coating after curing of the second coating composition is defined by the haze value of a 1.2 im thick coating formed on a 3 mm thick polycarbonate substrate.
• the haze value of the cured film is 3% or less, preferably 1% or less, more preferably 0.5% or less.
• the second coating composition having the above-mentioned properties also has excellent abrasion resistance on the surface of the coating after curing.
• the change in haze value of the coating before and after the test is performed.
• the change in the haze value of the film after curing is 10% or less, preferably 8% or less, more preferably 6% or less.
• the second coating composition Since the second coating composition has the above characteristics, it has excellent surface lubricity on the cured film surface.
• a dynamic friction coefficient of the coating surface measured by a procedure shown in Examples described later is used as an index of the surface lubricity of the cured coating surface.
• the initial dynamic friction coefficient and the dynamic friction coefficient after the moisture resistance test of the cured film are all 0.1 or less.
• the second coating composition is an active energy ray-curable coating composition, and widely includes those having the above characteristics.
• the second coating composition is preferably an active energy ray-curable polymerizable monomer (A), that is, a polyfunctional polymerizable monomer (a-1) and / or a monofunctional polymerizable monomer. And (a-2) etc.
• the content ratio of (a-1) in the polymerizable monomer (A) may be arbitrary, but is preferably 20 to 100% in the total mass of the polymerizable monomer (A).
• the content is 100% by mass, more preferably 40 to 100% by mass, and particularly preferably 70 to 100% by mass.
• a particularly preferred embodiment of the second coating composition is the above-mentioned first coating composition.
• the first and second coating compositions of the present invention are applied to the surface of a glass or plastic substrate used as an optical member, and have excellent transparency, abrasion resistance and water / oil repellency. It forms a cured film that exhibits excellent fingerprint removability over a long period of time.
• the material of the plastic base material that forms the coating is a transparent bra Stick materials and plastic materials having poor abrasion resistance are preferred.
• aromatic polycarbonate resin polymethyl methacrylate resin, polymethacrylimide resin, polystyrene resin, polyvinyl chloride resin, unsaturated polyester resin
• examples include polyolefin resin, ABS resin, and MS (methyl methacrylate / styrene) resin.
• a 3 L droplet is formed at the tip of the needle in a dry state (20 ° C, relative humidity 65%), and this is sampled.
• the droplets were made in contact with the surface of the coating film.
• the contact angle is the angle between the solid surface and the tangent to the liquid surface at the point where the solid and liquid come into contact, and was defined as the angle that included the liquid. Distilled water and oleic acid were used for the liquid, respectively.
• the contact angle was measured for the initial sample and the sample after the moisture resistance test (stored for 60 hours at 60 in a humid environment of 95% relative humidity).
• the haze (%) at four places was measured over time, and the average value (initial haze) was calculated.
• the coefficient of kinetic friction of the film surface of the sample was measured.
• the coefficient of kinetic friction was determined as “the weight / load” by measuring the weight (g) of the sliding piece required to move the load horizontally under the following conditions.
• Test pad non-woven fabric made of cellulose (Bencott, manufactured by Asahi Kasei Corporation)
• Test environment 25 ° C, relative humidity 45%
• the surface of the coating of the sample was cut with a razor to make 11 cuts at 1 mm intervals in each of the vertical and horizontal directions, make 100 squares, and adhered a commercially available cellophane tape (manufactured by Nichipan). It is expressed as the number of crosscuts (pieces) that remained without peeling off the film when it was suddenly peeled forward.
• A-1 Acrylic urethane with a molecular weight of 230 and an average number of acryloyl groups per molecule of 15 obtained by reacting hydroxyl group-containing dipentyl erythritol polyacrylate with hexamethylene diisocyanate. .
• A-2 Dipentaerythritol hexaacrylate.
• A—3 Isopolnylate acrylate.
• D-1 Solvent-dispersed colloidal silica with an ethyl ester mouth (silica content: 30% by mass, average particle diameter: 11 nm) 2.5 parts by mass of 3-mercaptopropyltrimethoxysilane was added to 100 parts by mass, and Colloidal silica having a hydrolytic condensate of a mercapto group-containing silane compound on the surface, which is obtained by heating and stirring for 5 hours in a nitrogen stream at 12 ° C., and then aging for 12 hours at room temperature.
• D-2 100 parts by mass of propylene glycol monomethyl ether acetate dispersed colloidal silica (silica content: 30% by mass, average particle size: llnm.): 2.5 parts by mass of 3-methacryloyloxypropyltrimethoxysilane After stirring at 50 ° C. for 3 hours, the mixture was aged at room temperature for 12 hours. Colloidal silica having a methacryloyl group-containing silane compound hydrolyzed condensate on the surface.
• the number average molecular weight described below is a value measured by gel permeation chromatography using polystyrene as a standard substance.
• B - 2 A four neck flask of 3 0 0 m L equipped with a stirrer, 1 0 0 g of the C 3 F 7 (OCF 2 CF 2 CF 2) 2 0 ⁇ (CF 2) 2 CH 2 OH , 5O mg of dibutyltin dilaurate and 25O mg of 2,6-di-t-butyl-p-cresol were added, and the mixture was stirred at room temperature for 30 minutes, and then stirred at 3.6.
• B-3 In a 30 OmL four-necked flask equipped with a stirrer and condenser, 60 Omg of 2,2'-azobis (2-methylpropionitrile), 74 mg of n-dodecylmer Butane, 90 g of butyl acetate and 90 g of hexafluorometa-xylene were added, and the mixture was stirred at room temperature for 15 minutes. Then, 45 g of the water- and oil-repellency-imparting agent (B-2) was added.
• B-4 In a 30-OmL four-necked flask equipped with a stirrer and condenser, 600 mg of 2,2'-azobis (2-methylpropionitrile), 74 Omg of n_dodecylmercaptan After adding 180 g of butyl acetate and stirring at room temperature for 15 minutes, 35 g of the water- and oil-repellency-imparting agent (B-2), 2 Og of stearyl acrylate and 5 g of 2-Hydroxyshetyl acrylate was added, and after purging with nitrogen, the mixture was stirred at 70 ° C. for 18 hours to carry out polymerization to obtain a reaction product.
• B-2 water- and oil-repellency-imparting agent
• a butyl acetate solution (solid content: about 25% by mass) of the water- and oil-repellency-imparting agent (B-4) thus obtained was obtained.
• the number average molecular weight of (B-4) was 2,780,000.
• B-5 In a 30-OmL four-necked flask equipped with a stirrer and condenser, 600 mg of 2,2'-azobis (2-methylpropionitrile), 74 Omg of n-dodecylmercaptan And 180 g of butyl acetate were added thereto, and the mixture was stirred at room temperature for 15 minutes. Then, 45 g of the water- and oil-repellency imparting agent (B-2) and 15 g of unsaturated fatty acid hydroxyalkyl ester were added.
• B-7 In a 30 OmL four-necked flask equipped with a stirrer and condenser, 8 Omg of titanium tetraisobutoxide, 100 g of polyfluoropolyethylene oxide having hydroxyl groups at both ends (100 g) Solvay Solexis, product name Fomblin Z—do 1100, HOCH 2 (CF 2 CF 2 0) p (CF 2 ⁇ ) s CF 2 CF 2 CH 2 OH, average molecular weight 100 0) and 25 g of ⁇ -force prolacton were added, and heated at 150 ° C for 5 hours to form a white box with ⁇ -force prolactone ring-opened to both ends of polyfluoropolyethylene oxide. The compound was obtained. The number average molecular weight was 125, and the polymerization degree of cabrolactone at each end was about 1.1.
• the crude liquid was filtered under reduced pressure, and then the recovered liquid was dried with a vacuum drier (50, 667 Pa) for 12 hours.
• the crude liquid obtained here was dissolved in 100 ml of AK-225 and washed three times with 100 ml of saturated aqueous sodium hydrogen carbonate to recover the organic phase. Further, magnesium sulfate (1.0 g) was added to the collected organic phase, and the mixture was stirred for 12 hours. Thereafter, magnesium sulfate was removed by filtration under pressure, and AK-225 was distilled off at Evapore Yuichi to obtain 56.lg of a liquid polymer at room temperature.
• the obtained polymer was CH 3 O (CH 2 CH 2 O) p + ! COCF (CF 3) OCF 2 CF (CF 3 ) ⁇ CF 2 CF 2 CF 3 (p has the same meaning as described above) was confirmed to be a compound represented by the following step 2)
• 5 OO mL of Hastelloy R-11 (156Og) was added to the autoclave, and the mixture was stirred and kept at 25 ° C.
• a cooler kept at 20 " ⁇ , a packed bed of NaF pellets, and a cooler kept at 20 ° were installed in series. It was kept at 120 ° C.
• a liquid return line was installed to return the condensed liquid from the cooler to the autoclave.
• fluorine gas diluted to 10% with nitrogen gas (hereinafter referred to as 10% fluorine gas) was blown at a flow rate of 24.8 LZh for 1 hour.
• Step 3 The 30 O mL round-bottomed flask into which the stirrer chip was charged was sufficiently purged with nitrogen. Methanol (36 g), NaF (5.6 g) and AK-225 (50 g) were added, and the product obtained in step 2 (43.5 g) was added dropwise. While stirring at room temperature, the mixture was vigorously stirred. The NAS flask outlet was sealed with nitrogen.
• Step 4) The 30 O mL round-bottomed flask into which the silicon chip was charged was sufficiently purged with nitrogen. 2-propanol (3 0 g), AK - 2 2 5 (5 0. 0 g) and, in addition to N a BH 4 (4. 1) , the product from Step 3 (. 2 6 2 g) was diluted with AK-225 (30 g) and added dropwise. Then, the mixture was vigorously stirred at room temperature, and the outlet of the round bottom flask was sealed with nitrogen.
• AK-225 100 g was added, and while stirring, a 0.2 N aqueous hydrochloric acid solution (500 g) was added dropwise. After dropping, stirring was maintained for 6 hours. Thereafter, the organic phase was washed three times with distilled water (500 g), and the organic phase was recovered by two-layer separation. Further, magnesium sulfate (1.0 g) was added to the collected organic phase, and the mixture was stirred for 12 hours. Thereafter, magnesium sulfate was removed by filtration under pressure, and AK-225 was distilled off at an evaporator to obtain 24.8 g of a liquid polymer at room temperature.
• B—8 In a 30 O mL four-necked flask equipped with a stirrer and condenser, 8 O mg of titanium tetraisobutoxide, 100 g of compound M and 25 g of ⁇ -force Add prolacton and heat at 150 ° C for 5 hours.
• the molecular weight of ( ⁇ -8) was 125, and the degree of polymerization of caprolactone was about 2.2.
• B—10 In a 300 mL four-necked flask equipped with a stirrer, 100 g of Compound M and 6 O mg of 2,6-di-t-butyl_p—cresol were added. After stirring for 30 minutes, add 31.0 g of 2-methacryloyloxetyl isocyanate and stir at room temperature for another 24 hours. An imparting agent (B-10) was obtained. The number average molecular weight of (B-10) was 116.
• B-13 In a 30 OmL four-necked flask equipped with a stirrer and condenser, add 580 mg of potassium fluoride, 100 g of Compound M and 9.12 g of ethylene carbonate. The mixture was heated for 40 hours while decarboxylation was performed at 160. Thus, a colorless and transparent oily compound in which 1 unit of ethylene oxide was added to the end of compound M was obtained.
• B—14 Dimethyl silicone oil in which a part of the side chain is substituted with C 8 FJ 7 CH 2 CH 2 group (trade name “FLS525” manufactured by Asahi Glass Co., Ltd.). Water / oil repellency-imparting agent having no functional group (b-2) and site (b-3).
• the polymerizable monomer (A), the water / oil repellency imparting agent (B), the active energy ray polymerization initiator (C), the colloidal silica (D) and the organic solvent in the coating composition in Example 1 are shown in Table 1.
• Samples 2 to 9 and 11 to 19 were prepared in the same manner as in Example 1 except that the type and amount (in brute force, unit: g) described in 3 were changed. An evaluation was made.
• the mixture was stirred for 1 hour at room temperature and shielded from light to obtain a coating composition (Q10).
• the substrate surface is spin-coated with (Q 10) (200 rpm XI 0 seconds) and dried in a hot air circulating oven at 90 ° C for 1 minute. (Light amount: 1200 mJZ cm 2 , wavelength integrated energy of ultraviolet light in the wavelength range of 300 to 390 nm) to cure the film, and the polymerizable monomer (A — A cured product layer with a thickness of 1.2 mm formed by curing 1).
• Example 4 a cured layer of B was formed on the cured film containing A, C, and D. Table 4
• a glass or plastic molded article having a coating formed of a cured product of the coating composition of the present invention on its surface has an antifouling property, and particularly, an antifouling property against fingerprints, sebum, sweat, and cosmetics. It is excellent in soiling, and it is difficult for such greasy soil to adhere, and even if it does, it can be easily wiped off. Further, the molded article is excellent in abrasion resistance and transparency. For this reason, it is preferable as an optical member such as an antireflection film, an optical film, an optical lens, a liquid crystal display, an EL display, and an optical disk, in which adhesion of greasy dirt is a problem in appearance.
• an optical member such as an antireflection film, an optical film, an optical lens, a liquid crystal display, an EL display, and an optical disk, in which adhesion of greasy dirt is a problem in appearance.

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