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
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • 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
  • C08F290/08—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 side groups
  • C08F290/14—Polymers provided for in subclass C08G
  • C08F290/148—Polysiloxanes
• • 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
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
  • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
• • G—PHYSICS
  • G11—INFORMATION STORAGE
  • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
  • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
  • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
  • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
  • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
  • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
  • G11B2007/25303—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins

Definitions

• the present invention relates to a composition and articles such as a cured product and an optical recording medium using the composition.
• the present invention relates to a composition that provides a cured film having sufficient performance even in a thin film.
• the present invention relates to an optical article, particularly an optical recording medium such as a read-only optical disc, an optical recording disc, a magneto-optical recording disc, or a transparent article for an optical display such as a touch panel or a liquid crystal television.
• Plastic products such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile butadiene styrene copolymer (ABS), methyl methacrylate-styrene copolymer (MS resin), acrylonitrile styrene copolymer (AS resin), etc.
• Resin materials such as styrene resin, vinyl chloride resin, and cellulose acetate such as triacetyl cellulose are particularly excellent in lightness, ease of processing, impact resistance, etc. Used for various applications such as outer panels, window materials, roofing materials, packaging materials, various housing materials, optical disk substrates, plastic lenses, liquid crystal displays, plasma displays, base materials for display devices such as projection TVs, etc.
• Such a surface-cured film is usually obtained by dissolving or suspending the resin composition in a solvent and applying it to the surface of the product in the form of a paint, followed by curing.
• a coating film is obtained by coating and a cured film is further obtained, leveling properties are required for the resin composition. If the leveling property is inferior, the surface roughness or coating failure portion called so-called repellency is generated in the coating film or the cured film, which can be a serious obstacle in the production of the cured film. As a cause of repelling, bubbles are generated in the coating solution and the coating film and the bubbles are difficult to disappear.
• bubbles are easily generated in water-based paints, and measures are taken to solve the problem of repelling.
• a saturated hydrocarbon is contained in a water-based paint containing a surfactant in order to eliminate bubbles caused by the surfactant (Patent Document 1).
• Patent Document 1 since it is common to use a non-polar solvent for non-aqueous paints, it has been conventionally considered that bubbles are hardly generated.
• hardened surface films used for large-screen flat panel TV displays such as optical disks, touch panel displays, liquid crystal televisions, and plasma TVs are required to have not only surface hardness and durability but also high levels of contamination resistance.
• contaminants such as fingerprint stains have become a problem, affecting not only the appearance but also the performance, and have come to be regarded as important. It was.
• Patent Document 2 a specific copolymer containing a specific perfluoroalkyl group and an epoxy group, or a (meth) acrylic acid reaction product thereof, has excellent contaminant wiping properties and durability.
• the present invention provides a non-aqueous resin composition that is low in foaming properties and excellent in defoaming properties even when foaming may occur, and as a result, hardly causes defects in the formed coating film.
• the purpose is to do. Furthermore, it aims at providing the resin composition which provides the cured film which provides the outstanding hardness, scratch resistance, transparency, stain resistance, and its durability.
• the present invention is a cured product of such a composition, and an article having the cured product on its surface, particularly an article for optical applications such as an optical recording medium and a touch panel display, and has high hardness and wear resistance on the surface. It is another object of the present invention to provide an article that has excellent contamination resistance and contamination resistance durability.
• the present inventors have selected from a polymer having a hydroxyl group and a fluoroalkyl group and a weight average molecular weight of 1000 or more, and a (meth) acryloyl group and a vinyl group.
• the foaming of the resin composition by containing a hydrocarbon monomer containing one or more of the above, a specific amount of saturated hydrocarbon, and a solvent having an SP (Solubility Parameter) value of 10.0 or less It was found that the property can be reduced.
• a fluorine group-containing oligomer having a tension lowering ability of 2 mN / m or more and a solvent having an SP value of 10.0 or less containing a fluorine group-containing oligomer having a tension lowering ability of 2 mN / m or more and a solvent having an SP value of 10.0 or less.
• the polymer has a polysiloxane structure, and the silicon at the end of the polysiloxane structure or a saturated hydrocarbon group bonded to the silicon is bonded to the main chain of the polymer through an oxygen atom or a sulfur atom.
• the present inventors have found that the resin composition exhibits a particularly excellent water / oil repellency and exhibits a particularly excellent resin composition, thereby completing the present invention.
• the present invention is as follows.
• a resin composition comprising 0.01 to 25% by weight of a saturated hydrocarbon and a solvent having an SP value of 10.0 or less.
• the resin composition according to claim 1. [14] The resin composition according to any one of [3] to [13], which contains a saturated hydrocarbon having 5 to 18 carbon atoms. [15] The resin composition according to any one of [1] to [14], which contains a radical polymerizable photoinitiator.
• the resin composition of the present invention has a wide range of uses such as protection of the surface of optical recording media, optical displays such as touch panels and flat displays, mobile phone housings, automobile transparent parts protection, and protection of transparent parts such as agricultural greenhouses. It can be suitably applied to.
• room temperature refers to the temperature at the place where the experiment is conducted, for example, it means a temperature of 15 to 30 ° C., more preferably 20 to 25 ° C.
• the “normal oxygen concentration” means 18 to 22%, more preferably 19 to 21%.
• (meth) acrylate means “acrylate and / or methacrylate”, and the same applies to “(meth) acryloyl” and “(meth) acryl”.
• the resin composition which is one embodiment of the present invention (hereinafter sometimes abbreviated as “resin composition (A) according to the present invention”) has a hydroxyl group and a fluoroalkyl group, and has a weight average molecular weight of 1000 or more.
• a polymer, a hydrocarbon monomer containing one or more selected from a (meth) acryloyl group and a vinyl group, 0.01% to 25% by weight of a saturated hydrocarbon, and an SP value of 10 0.0 or less of a solvent is contained as an essential component.
• a resin composition which is another embodiment of the present invention (hereinafter sometimes abbreviated as “resin composition (B) according to the present invention”) has a hydroxyl group and a fluoroalkyl group, and has a weight average molecular weight of 1000.
• the polymer that is an essential component of the resin composition of the present invention has a hydroxyl group and a fluoroalkyl group, and has a weight average molecular weight of 1000 or more.
• the weight average molecular weight is not particularly limited as long as it is 1000 or more, but it is preferably 1000 to 30000, more preferably 1000 to 20000.
• the weight average molecular weight is measured using GPC (“HLC-8120GPC” manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent and polystyrene as a standard sample.
• the polymer having a polysiloxane structure is preferable from the viewpoint of imparting leveling property, slipping property, and peelability to the cured film.
• the silicon at the terminal of the polysiloxane structure or a saturated hydrocarbon group bonded to the silicon is bonded to the main chain of the polymer via an oxygen atom or a sulfur atom.
• the polymer in the resin composition of the present invention can be produced by polymerizing a polymerizable monomer described below. A preferred method for producing the polymer is described below. In the following, the amount (part by weight) of each component in 100 parts by weight of the monomer mixture as the raw material for producing the polymer of the present invention may be referred to as “use amount”.
• a (meth) acrylate having a hydroxyl group will be described as a polymerizable monomer for producing a polymer.
• Some typical specific examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl acrylate, pentaerythritol triacrylate, etc., but are not limited to these, and the hydroxyl group is reacted by reaction. It may be a monomer having a functional group to be generated. If the amount of (meth) acrylate having a hydroxyl group is small, the hardness of the cured film obtained from the resin composition is inferior, and neither is preferable.
• examples of such a reaction include a reaction between an epoxy group and a carbonyl group, a ring-opening reaction or an addition reaction of an oxysilane skeleton, and the like.
• (meth) acrylate having an epoxy group examples include (meth) acrylate having a glycidyl group such as glycidyl acrylate and glycidyl methacrylate; 3,4-epoxycyclohexyl acrylate, 3,4-epoxy Examples include, but are not limited to, (meth) acrylates in which an epoxy group is directly bonded to an alicyclic structure such as cyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate. is not.
• glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate are easily available and easily modified with (meth) acrylic acid.
• 3,4-epoxycyclohexylmethyl methacrylate and the like are particularly preferable.
• Such (meth) acrylates having an epoxy group may be used alone or in combination of two or more.
• (meth) acrylates having a carbonyl group include acrylic acid, methacrylic acid, succinic acid-modified pentaerythritol triacrylate, and the like, but are not limited thereto.
• the hydroxyl group content in the polymer in the resin composition of the present invention is not particularly limited, but in the case of the resin composition (A) or the resin composition (B) according to the present invention, the lower limit is 0.2 weight. % Or more, more preferably 0.4% by weight or more, further preferably 0.5% by weight or more, particularly preferably 0.7% by weight or more, 1.0% Most preferably, it is at least% by weight.
• the upper limit value is preferably 5.0% by weight or less, more preferably 4.0% by weight, further preferably 3.5% by weight or less, and 3.0% by weight. Is most preferred.
• the amount of the monomer having a hydroxyl group is adjusted so as to fall within this range. Further, in the monomer mixture for producing the polymer, the amount of the monomer having a hydroxyl group based on the whole monomer is preferably 5 to 50% by weight, and more preferably 10 to 30% by weight.
• a monomer having a fluoroalkyl group will be described as a monomer used for polymer production.
• a monomer is preferably a (meth) acrylate containing a fluoroalkyl group.
• the (meth) acrylate containing a fluoroalkyl group is not particularly limited, but a (meth) acrylate containing a fluoroalkyl group other than a (meth) acrylate having a linear perfluoroalkyl group having 8 or more carbon atoms is available. preferable.
• Preferred (meth) acrylates having a fluoroalkyl group include (meth) acrylates having a linear fluoroalkyl group having 4 to 7 carbon atoms, such as perfluorohexylethyl (meth) acrylate, perfluorohexyl glycidyl.
• a (meth) acrylic acid adduct of ether, a (meth) acrylic acid adduct of perfluoroheptyl glycidyl ether and the like are preferable.
• (meth) acrylate having 6 or more carbon atoms and having a fluoroalkyl group having a difluoromethyl group at its end can be mentioned.
• 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexa Decafluorononyl (meth) acrylate and the like are preferable.
• (meth) acrylates having a straight-chain, saturated fluoroalkyl group having 6 carbon atoms for example, (meth) acrylic acid adducts of perfluorohexylethyl (meth) acrylate and perfluorohexyl glycidyl ether are particularly preferred.
• These (meth) acrylates having a fluoroalkyl group may be used alone or in combination of two or more.
• Examples of the (meth) acrylate having a linear perfluoroalkyl group having 8 or more carbon atoms include perfluorooctylethyl (meth) acrylate, perfluorodecylethyl (meth) acrylate, and 2- (perfluoro-7-methyl). 1 type, or 2 or more types, such as the (meth) acrylic acid adduct of octyl) ethyl (meth) acrylate, heptadecafluorononenyl (meth) acrylate, perfluorooctyl glycidyl ether, etc. are mentioned.
• the fluorine atom content in the polymer in the resin composition of the present invention is not particularly limited, but in the case of the resin composition (A) or the resin composition (B) according to the present invention, the lower limit is 1.0. It is preferably at least wt%, more preferably at least 4.0 wt%, even more preferably at least 4.5 wt%, particularly preferably at least 5.0 wt%. Most preferably, it is 0% by weight or more.
• the upper limit is preferably 34.0% by weight or less, more preferably 30.0% by weight or less, and further preferably 25.0% by weight.
• the fluorine atom content is less than this lower limit, effects such as improvement of oil resistance due to the oil repellency of the fluoroalkyl group are not sufficiently exhibited, and if this upper limit is exceeded, the polymer and other components May be reduced, or the hardness of the cured film may be reduced to reduce the surface scratch resistance and pencil hardness.
• the amount of the monomer having a fluoroalkyl group is adjusted so as to fall within this range.
• the amount of the (meth) acrylate having a perfluoroalkyl group based on the whole monomer is preferably 80.0% by weight or less, and 60.0% by weight or less. Is more preferable.
• the polymer in the present invention preferably has a polysiloxane structure as described above.
• the polysiloxane structure preferably has a repeating structural unit represented by the following general formula (1).
• each of R 1 and R 2 independently represents an optionally substituted alkyl group or an optionally substituted phenyl group, preferably substituted with a hydroxyl group or an alkoxy group.
• An alkyl group which may be substituted (more preferably, the alkoxy group and the alkyl group have 1 to 3 carbon atoms), more preferably an alkyl group having 1 to 3 carbon atoms having no substituent, most preferably Is a methyl group.
• the polymer having a polysiloxane structure is an epoxy group of a radical polymer of a monomer mixture containing (meth) acrylate or dimercaptan having a polysiloxane structure in addition to a hydroxyl group or an epoxy group and a fluoroalkyl group.
• the monomer used for the production of the polymer having such a polysiloxane structure is preferably (meth) acrylate or dimercaptan having a polysiloxane structure in which two or more repeating structural units represented by the formula (1) are connected.
• Examples of such monomers include polydimethylsiloxane having a methacryloyl group at one end (“Sylaplane FM-0725” manufactured by JNC (former Chisso)), and polydimethylsiloxane having a methacryloyl group at both ends (for example, Shin-Etsu Chemical).
• polydimethylsiloxane having epoxy groups at both ends polydimethylsiloxane having epoxy groups at both ends and side chains, polydimethylsiloxane derivatives having acryloyl groups at side chains (for example, Evonik Degussa) "Tego-Rad” manufactured by Japan), polydimethylsiloxane having acryloyl groups at both ends (for example, “DMS-U22” manufactured by Gelest), polydimethylsiloxane having mercapto groups at both ends (for example, "X manufactured by Shin-Etsu Chemical Co., Ltd.") -22-167B "), main Or in a side chain having a polydimethylsiloxane, and a copolymer having an acryloyl group and / or epoxy group in the side chain and / or terminal.
• the polysiloxane structure in the polymer of the present invention has a terminal silicon or a saturated hydrocarbon group bonded to the silicon bonded to the main chain of the polymer through an oxygen atom or a sulfur atom. It is preferable.
• the monomer having a polysiloxane structure for producing such a polymer include methacrylates such as dimethylpolysiloxypropyl methacrylate and ⁇ -butyl- ⁇ - (3-methacryloxypropyl) polydimethylsiloxane. There is no limitation to these.
• dimercaptan examples include ⁇ , ⁇ -dimercaptopolydimethylsiloxane, ⁇ , ⁇ -dimercaptopolydiethylsiloxane, ⁇ , ⁇ -dimercaptopolymethylethylsiloxane, ⁇ , ⁇ -dimercaptopolydihydroxymethyl.
• Examples include siloxane, ⁇ , ⁇ -dimercaptopolydimethoxymethylsiloxane.
• ⁇ , ⁇ -dimercaptopolydimethylsiloxane is preferred, and the mercapto group may be directly linked to the polysiloxane group or may be linked to the polysiloxane group via an alkylene group. More preferably, polysiloxane ( ⁇ , ⁇ -dimercaptopropylpolydimethylsiloxane) in which a mercapto group is linked to a polysiloxane group via a propylene group.
• polysiloxane ⁇ , ⁇ -dimercaptopropylpolydimethylsiloxane
• the (meth) acrylate or dimercaptan having a polysiloxane structure preferably has a number average molecular weight of about 1000 to 10,000 in order to achieve a good balance between stain resistance and hardness.
• the number average molecular weight is measured using GPC (“HLC-8120GPC” manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent and polystyrene as a standard sample.
• One (meth) acrylate or dimercaptan having a polysiloxane structure may be used alone, or two or more may be used in combination.
• the amount of (meth) acrylate or dimercaptan having a polysiloxane structure is 0.01 to 30% by weight, preferably 0.1 to 25%, based on the total amount of monomers in the monomer mixture for producing the polymer. % By weight, more preferably 1 to 20% by weight. If the amount of (meth) acrylate or dimercaptan having a polysiloxane structure is less than 0.01% by weight, the stain resistance is insufficient, and if it exceeds 30% by weight, the phase of the polymer obtained and other components is obtained.
• the amount of (meth) acrylate or dimercaptan having a polysiloxane structure is preferably 0.1% by weight or more, more preferably 1% by weight or more.
• the amount of (meth) acrylate or dimercaptan having a polysiloxane structure is preferably 25% by weight or less, more preferably 20% by weight or less.
• the monomer mixture prepared when producing the polymer in the present invention may contain other (meth) acrylates.
• Other (meth) acrylates are not particularly limited, but preferably have low reactivity with epoxy groups and do not reduce the stability of the polymer produced, or have a rigid skeleton and do not lower the hardness, stain resistance What can be improved further is required.
• Some specific examples of such other (meth) acrylates include styrene, lower alkyl groups having 1 to 4 carbon atoms, alkenyl group-substituted derivatives, and alkyl (meth) having 1 to 20 carbon atoms.
• examples thereof include radical polymerizable monomers such as acrylate, alkyl (meth) acrylamide, cycloalkyl (meth) acrylate having a (poly) cycloalkyl side chain having 5 to 20 carbon atoms, and (meth) acrylamides.
• Other (meth) acrylates may be used alone or in combination of two or more.
• the amount of other (meth) acrylate used is 50% by weight or less. When the amount of other (meth) acrylates used exceeds 50% by weight, the hardness of the polymer is lowered, and the scratch resistance and pencil hardness of the surface are lowered.
• the amount of other (meth) acrylates used is preferably 45% by weight or less, more preferably 40% by weight or less.
• a solvent may be added to the monomer mixture.
• solvents include ketone solvents such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA), and isobutanol; ethylene glycol dimethyl ether, propylene glycol
• ether solvents such as monomethyl ether
• ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate and 2-ethoxyethyl acetate
• aromatic hydrocarbon solvents such as toluene; and water.
• a radical polymerization initiator is preferably used for radical polymerization of the monomer mixture containing the above-described components.
• known initiators generally used for radical polymerization can be used.
• Organic peroxides such as benzoyl peroxide and di-t-butyl peroxide, 2,2′-azobisbutyro Preferred examples include azo compounds such as nitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile).
• One of these radical polymerization initiators may be used alone, or two or more thereof may be mixed and used.
• the mixing / dissolution method of the monomer component and the solvent when performing radical polymerization using a solvent and a radical polymerization initiator as necessary further on the monomer mixture containing the above-mentioned components. It is preferable to start the polymerization by adding a radical polymerization initiator within a certain time, preferably within 3 hours after mixing the monomer component and the solvent.
• the total concentration of the monomer components in the reaction solution subjected to radical polymerization is preferably 10% by weight or more and 60% by weight or less, and the radical polymerization initiator is preferably 0.1% by weight with respect to the total of the monomer components.
• the polymerization temperature is 20 to 150 ° C.
• the polymerization time is 1 to 72 hours, more preferably the polymerization temperature is usually 50 to 100 ° C., and the polymerization time is 3 to 36. It's time.
• the polymer in the present invention is a carboxylic acid having a (meth) acryloyl group in at least a part of the epoxy group of the radical polymer obtained as described above, preferably 1 to 5 (meth) per molecule. What added the carboxylic acid which has an acryloyl group is preferable. This is because the (meth) acryloyl group becomes a cross-linking point and the polymer has a cross-linked structure, thereby improving the wiping property of the contaminant and its durability.
• Examples of the carboxylic acid having a (meth) acryloyl group used herein include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, pentaerythritol tris.
• Adducts of (meth) acrylates and acid anhydrides such as succinic anhydride, phthalic anhydride and hexahydrophthalic anhydride, dipentaerythritol penta (meth) acrylate and acids such as succinic anhydride, phthalic anhydride and hexahydrophthalic anhydride
• An adduct of an anhydride can be used. One of these may be used alone, or two or more thereof may be mixed and used.
• the epoxy group of the radical polymer reacts with the carboxyl group of the carboxylic acid having a (meth) acryloyl group.
• the radical polymer and the carboxylic acid having a (meth) acryloyl group are the ratio of the epoxy group of the radical polymer to the carboxyl group of the carboxylic acid having a (meth) acryloyl group (hereinafter simply referred to as “epoxy group / carboxyl group”). In some cases) is preferably used at a ratio of 1 or more.
• the epoxy group / carboxyl group is preferably 10 or less, more preferably 5 or less, and still more preferably 2 or less.
• the epoxy group / carboxyl group is at least the lower limit value, it is possible to prevent a decrease in stability due to the carboxylic acid having a (meth) acryloyl group remaining unreacted. It is preferable because a decrease in stability can be prevented. Further, it is preferable that 50 to 99% of the epoxy groups of the radical polymer react with the carboxyl group of the carboxylic acid having a (meth) acryloyl group, and more preferably 70 to 98%. This addition reaction is preferably carried out at 50 to 110 ° C. for 3 to 50 hours, more preferably at 80 to 110 ° C. for 3 to 30 hours.
• one or more known catalysts such as triethylamine, tributylamine, triethylenediamine, N, N-dimethylbenzylamine, benzyltrimethylammonium chloride, and triphenylphosphine are used.
• the amount used is preferably 0.01% by weight or more, more preferably 0.05% by weight or more based on the reaction mixture (that is, the total of the radical polymer and the (meth) acryloyl group-containing carboxylic acid). Is preferred.
• the reaction in order to prevent radical polymerization of the carboxylic acid having a (meth) acryloyl group by the (meth) acryloyl group, for example, hydroquinone, hydroquinone monomethyl ether, catechol, pt-butylcatechol, phenothiazine, etc. It is preferable to use one or more polymerization inhibitors.
• the amount of the polymerization inhibitor used is preferably 0.01% by weight or more, more preferably 0.05% by weight or more based on the reaction mixture. Moreover, it is preferable that it is 1 weight% or less, and it is more preferable that it is 5 weight% or less.
• the polymer in this invention should just have the structure demonstrated above, and is not limited to what was obtained by the said manufacturing method. .
• the content of the polymer in the composition of the present invention varies depending on the use of the composition, the type of polymer used, and the composition of other components, but is preferably 0.5% by weight or more, more preferably 1 % By weight or more, preferably 20% by weight or less, more preferably 15% by weight or less.
• the content of the polymer is 0.5% by weight or more, the stain resistance is better, and when it is 20% by weight or less, the hardness is high and the coating property is excellent.
• hydrocarbon monomer that is an essential component of the resin composition of the present invention contains one or more selected from a (meth) acryloyl group and a vinyl group, and preferably contains a (meth) acryloyl group. This component gives good hardness to the cured film obtained from the resin composition.
• the “hydrocarbon monomer” as used herein may contain a bond containing atoms other than carbon and hydrogen.
• hydrocarbon monomer containing a vinyl group examples include styrene, p-chlorostyrene, p-methoxystyrene, divinylbenzene, N-vinylpyrrolidone, N-vinylcaprolactam, acrylonitrile, ethylene glycol divinyl ether, pentaerythritol divinyl ether, 1,6-hexanediol divinyl ether, trimethylolpropane divinyl ether, ethylene oxide modified hydroquinone divinyl ether, ethylene oxide modified bisphenol A divinyl ether, pentaerythritol trivinyl ether, dipentaerythritol hexavinyl ether, ditrimethylolpropane polyvinyl ether, etc. .
• hydrocarbon monomer containing a (meth) acryloyl group examples include those having one or more (meth) acryloyl groups in one molecule.
• Examples of the polyhydric alcohol in (i) and (ii) include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol, polypropylene glycol, and pentaerythritol. Dipentaerythritol and the like.
• Examples of the polybasic acid include phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid, and alkenyl succinic acid.
• (Iii) An epoxy acrylate in which an epoxy group of an epoxy resin is esterified with (meth) acrylic acid to form a (meth) acryloyl group as a functional group.
• the epoxy resin in (iii) include bisphenol A-epichlorohydrin type, phenol novolac-epichlorohydrin type, and alicyclic resin.
• (Iv) A polyurethane acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate with a polyvalent isocyanate compound.
• Examples of the polyvalent isocyanate compound in the above (iv) include those in which the center part of the molecule has a structure such as polyester, polyether, polyurethane, etc., and contains isocyanate groups at both ends.
• Others include polyether (meth) acrylate, melamine (meth) acrylate, alkyd (meth) acrylate, isocyanurate (meth) acrylate, silicon (meth) acrylate, and the like.
• Examples of these more specific compounds include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, hydroxypiparic acid ester neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,3- Bis (3 ′′ -acryloxyethoxy-2′-hydroxypropyl) 5,5-dimethylhydantoin, hydroxypiparic acid ester neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Intererythritol tri (meth) acrylate, dipentaerythritol
• polyfunctional (meth) acrylates having three or more (meth) acryloyl groups are more preferable. It is because the hardness of the cured film obtained from the resin composition can be further improved by using such a hydrocarbon monomer.
• pentaerythritol tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylol Propane tetra (meth) acrylate, polyester (meth) acrylates, polyfunctional urethane (meth) acrylates, polyepoxy (meth) acrylates, triethoxy (meth) acrylate having an isocyanurate ring (for example, ARONIX M315 manufactured by Toagosei Co., Ltd.) , M313, etc.), but is not limited thereto.
• isocyanurate ring for example, ARONIX M315 manufactured by Toagosei Co., Ltd.
• polyfunctional acrylates are preferable because of their good performance such as hardness, tris (acryloxyethyl) isocyanurate), bis (acryloxyethyl) isocyanurate), pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate and pentaerythritol tetra (meth) acrylate are preferred.
• the various hydrocarbon monomers mentioned above may be used alone or in combination of two or more. Further, the total content of these suitable contents in the composition is not particularly defined unless departing from the gist of the present invention, but when used as a composition requiring particularly high hardness.
• saturated hydrocarbon which is an essential component of the resin composition (A) according to the present invention
• known hydrocarbons can be widely used, but those having 5 to 18 carbon atoms are preferable. Those having less than 5 carbon atoms are gaseous at room temperature, and those having 18 or more carbon atoms are solid at room temperature and are difficult to handle.
• Preferable examples include hexane, heptane, octane, cyclohexane, cycloheptane and the like.
• the resin composition (B) based on this invention also contains a saturated hydrocarbon.
• the saturated hydrocarbon well-known ones can be widely used as in the case of the resin composition (A) according to the present invention, but those having 5 to 18 carbon atoms are preferable.
• the content of the saturated hydrocarbon in the resin composition (A) according to the present invention is 0.01 to 25% by weight, preferably 0.5% by weight or more, more preferably 1% by weight or more.
• the content of the saturated hydrocarbon in the resin composition (B) according to the present invention varies depending on the use of the composition, the type of polymer used, and the composition of other components, but is preferably 0.01% by weight. More preferably, it is 0.5% by weight or more, further preferably 1% by weight or more, preferably 25% by weight or less, more preferably 23% by weight or less, and particularly preferably 20% by weight or less.
• the content of the polymer is less than this lower limit, the defoaming property is not imparted, and if it is more than this upper limit, the polymer may be precipitated.
• the polymer and the saturated hydrocarbon which are essential components are preferably 5: 1 to 1:20 by weight ratio. When this ratio is within this range, the foaming property of the resin composition is easily suppressed by the interaction of both components, and the antifoaming property is easily improved.
• Fluorine group-containing oligomer having surface tension reducing ability of 2 mN / m or more> A well-known thing can be widely employ
• the surface tension reducing ability of the fluorine group-containing oligomer is not particularly limited as long as it is 2 mN / m or more, but the upper limit is preferably 15 mN / m or less, more preferably 12 mN / m or less, particularly preferably 10 mN / m or less. It is. Moreover, as a lower limit, Preferably it is 2 mN / m or more, More preferably, it is 3.5 mN / m or more, Most preferably, it is 5 mN / m or more. If it is below this upper limit value, it is preferable since compatibility is good, and if it is above this lower limit value, it is preferable because antifoaming property is good.
• the surface tension reducing ability is a value calculated using a surface tension meter (“DropMaster series” manufactured by Kyowa Interface Chemical Co., Ltd.). Further, the surface tension reducing ability is a numerical value determined by the molecular structure of the additive. If the structure has a fluorine atom or Si atom, the surface tension reducing ability tends to increase. Determined by the tendency to decrease
• the fluorine group-containing oligomer is not particularly limited as long as the surface tension reducing ability is 2 mN / m or more, but the lower limit of the weight average molecular weight is preferably 5000 or more, more preferably 6000 or more, particularly preferably. 7000 or more.
• the upper limit Preferably it is 40000 or less, More preferably, it is 20000 or less, Most preferably, it is 15000 or less. If it is below this upper limit, since compatibility with other components is good, it is preferable. If it is more than this lower limit, since antifoaming property is favorable, it is preferable.
• the weight average molecular weight is measured using GPC (“HLC-8120GPC” manufactured by Tosoh Corporation), using tetrahydrofuran as a solvent and polystyrene as a standard sample.
• the fluorine group-containing oligomer preferably has no acryloyl group since it has good antifoaming properties.
• the fluorine group-containing oligomer is preferably nonionic since it has excellent antifoaming properties. Specifically, for example, Neogent's Footent 710FM, DIC's MegaFuck F-555, Daikin's NS-9013 and the like can be mentioned. You may mix and use the said oligomer.
• the preferred content of the fluorine group-containing oligomer in the resin composition (B) according to the present invention is not particularly defined unless it deviates from the gist of the present invention, but the entire resin composition (B) according to the present invention is not limited.
• the amount is preferably 0.005 to 10% by weight, and more preferably 0.01 to 5% by weight. When the content is less than 0.005% by weight, foaming of the resin composition may not be suppressed. When the content is more than 10% by weight, defects such as streaks and repellency may occur when the resin composition is applied. .
• the resin composition (A) according to the present invention also preferably contains a fluorine group-containing oligomer, and preferably contains a nonionic fluorine group-containing oligomer. This is to further improve the foaming prevention of the resin composition.
• the nonionic fluorine group-containing oligomer preferably has a polymerization average molecular weight of 5,000 to 20,000, more preferably 5,000 to 10,000.
• Footage 710FM Mega-Face F-555
• NS-9013 preferred are Footage 710FM, Mega-Face F-555, and NS-9013.
• the polymerization average molecular weight is measured using GPC (“HLC-8120GPC” manufactured by Tosoh Corporation), using tetrahydrofuran as a solvent and polystyrene as a standard sample.
• the content of the nonionic fluorine group-containing oligomer in the resin composition (A) according to the present invention is not particularly limited, but is 0.005 to 10% by weight of the entire resin composition (A) according to the present invention. Is preferably 0.01 to 5% by weight, more preferably 0.1 to 2% by weight. When the content is less than 0.005% by weight, foaming of the resin composition may not be suppressed. When the content is more than 10% by weight, defects such as streaks and repellency may occur when the resin composition is applied. .
• the solvent that is an essential component of the resin composition of the present invention has an SP value of 10.0 or less, preferably 9.5 or less, more preferably 9.3 or less, and particularly preferably 9.0 or less. . If it is below this upper limit, since antifoaming property is favorable, it is preferable. Moreover, as a lower limit, Preferably it is 7.5 or more, More preferably, it is 7.8 or more, More preferably, it is 8.0 or more, Especially preferably, it is 8.2 or more, Most preferably, it is 8.5 or more. If it is more than this lower limit, since compatibility is favorable, it is preferable.
• the SP value represents a solubility parameter, and the value is calculated by the method proposed by Fedors et al. Specifically, please refer to “POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147 to 154)”.
• the SP value is a physical property value determined by the content of the hydrophobic group or hydrophilic group of the molecule. When a mixed solvent is used, it can be appropriately prepared by mixing a solvent having a small SP value and a large solvent. It is.
• ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK); ethanol, methanol, isopropyl alcohol (IPA), alcohol solvents such as isobutanol; ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 2-ethoxyethyl acetate; Preferred examples include aromatic hydrocarbon solvents such as toluene.
• ketone solvents such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK) are more preferable from the viewpoint of low foaming and high compatibility with the polymer of the present invention. These solvents may be used alone or in a combination of two or more.
• the solid content concentration thereof is 10% by weight or more, particularly 20% by weight or more, and 90% by weight, by including these organic solvents. In the following, it is particularly preferable that the amount is adjusted to 70% by weight or less.
• the resin composition of the present invention preferably further contains a radical polymerizable initiator in addition to the essential components. This is for efficiently curing the resin composition.
• the resin composition is cured by irradiating with active energy rays, but can be omitted when the irradiation energy is very strong as in electron beam (EB) and the addition of a radical polymerizable initiator is not required. .
• EB electron beam
• radical polymerizable photoinitiator known ones can be widely used.
• alkylphenone type compounds ⁇ -hydroxyacetophenone type, ⁇ -aminoacetophenone type, benzyl ketal type, etc.
• acylphosphine oxide type compounds examples thereof include oxime ester compounds, oxyphenyl acetates, benzoin ethers, phenyl formates, and ketone / amine compounds.
• benzoin methyl ether benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2, 4,6-trimethylbenzoindiphenylphosphine oxide, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Butan-1-one, methylbenzoylformate, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone and the like are preferable.
• These radical polymerizable photoinitiators may be used alone or in combination of two or
• the content of the radically polymerizable photoinitiator in the resin composition of the present invention can be appropriately determined depending on the type of the radically polymerizable photoinitiator used, but the polymer in the composition and other colloidal silica described later are mainly used. It has a (meth) acryloyl group bonded to the inorganic oxide fine particle as a component through an —O—Si—R— bond (R represents a linear or branched alkylene group having 2 to 10 carbon atoms).
• compositions such as organic-inorganic composites, radical polymerizable organic (meth) acrylate compounds and / or radical polymerizable organic (meth) acrylamide compounds, polymers having radical polymerizable groups other than the polymer of the present invention It is preferably 10% by weight or less, more preferably 8% by weight or less, and preferably 0.5% by weight or more based on the total of the sex components. If the content of the radical polymerizable photoinitiator is less than this range, the curing is insufficient, and if it is large, the hardness may be lowered or the stain resistance may be lowered.
• radical polymerizable photoinitiators 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- ⁇ -Aminoacetophenone initiators such as butan-1-one, Ciba Specialty Chemicals, oxime ester initiators such as Irgacure OXE-01, ⁇ -hydroxyketone initiators such as 1-hydroxycyclohexyl phenyl ketone and Michler's ketone
• oxime ester initiators such as Irgacure OXE-01
• ⁇ -hydroxyketone initiators such as 1-hydroxycyclohexyl phenyl ketone and Michler's ketone
• the resin composition of the present invention further includes radicals other than the polymer of the present invention in order to adjust coating film properties such as hardness when the composition is formed into a film, and liquid properties such as viscosity of the composition.
• the organic-inorganic composite having a (meth) acryloyl group and one or more selected from inorganic fine particles may be included.
• contents are not particularly defined as long as they do not depart from the gist of the present invention, but are preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight of the entire resin composition. . If the content is less than 0.1% by weight, it is difficult to obtain the effects intended by the addition of these additional components (for example, improving the hardness of the coating film, suppressing curling, etc.). The physical properties of the coating film may deteriorate.
• the polymer other than the polymer of the present invention preferably, a (meth) acrylate polymer other than the polymer of the present invention having a radical polymerizable group such as an acryloyl group or a methacryloyl group in the side chain, A copolymer of such a polymer and another radical polymerizable monomer such as styrene may be mentioned.
• glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate were polymerized as main components.
• a polymer obtained by adding (meth) acrylic acid to a polymer and having a (meth) acryloyl group in the side chain is preferred. Of course, nothing other than these is not excluded. These may be used alone or in combination of two or more.
• the weather resistance is remarkably improved, which may be preferable.
• Preferred examples of the ultraviolet absorber include benzotriazole, benzophenone, salicylic acid, cyanoacrylate, and triazine ultraviolet absorbers.
• this type of anti-staining agent such as antioxidants (eg, hindered phenols, sulfurs, phosphorous antioxidants), anti-blocking agents, slip agents, leveling agents, etc. You may mix
• the amount of these additives is preferably 0.01% by weight or more and 2% by weight or less with respect to the other solid contents.
• the inorganic oxide fine particles used in the organic-inorganic composite (C2) described above may be blended into the resin composition of the present invention untreated for the purpose of further improving hardness, blocking resistance and the like.
• a commercially available antifoaming agent such as a silicon compound may be supplementarily included.
• the resin composition of the present invention has excellent antifoaming properties. Therefore, when used as a coating paint, no repelling occurs in the coating film, and the cured film obtained from the coating film has excellent leveling properties.
• the excellent defoaming property means that the solid content (polymer and hydrocarbon monomer as essential components of the resin composition) is a solid content concentration of 50% by weight and the ratio of the polymer in the solid content.
• the antifoaming property is improved by the suppression, and the saturated hydrocarbon breaks down the molecular arrangement in the solution of the polymer having the hydrophilic and hydrophobic groups forming the foam. It is presumed that the effects of the present invention are exhibited.
• the hydrophobicity of the solvent by using a solvent having an SP value of a specific value or less, and adding an additive having a surface tension reducing ability of a certain value or more, the hydrophobicity of the solvent.
• the defoaming property is improved by suppressing the formation of bubbles by the polymer, and the polymer solution having hydrophilic and hydrophobic groups in which the fluorine group-containing oligomer forms bubbles. It is presumed that by destructing the molecular arrangement therein, it becomes a starting point for defoaming and exhibits the effects of the present invention.
• a cured film having excellent physical properties to be described later can be obtained.
• a cured film can be obtained by polymerizing polymerizable components in the composition by irradiating active energy rays after forming a coating film by solvent drying.
• Preferred examples of the coating method include spin coating, dip coating, flow coating, spray coating, bar coating, gravure coating, roll coating, blade coating, and air knife coating.
• the thickness of the film obtained by coating, drying, polymerization, and curing is not particularly defined, and may be, for example, 5 ⁇ m or more, or 2 ⁇ m or less.
• the thickness of the cured film is particularly preferably 0.01 ⁇ m or more and 50 ⁇ m or less, particularly preferably when the hardness is important, and is preferably 2 ⁇ m or more and 20 ⁇ m or less, and particularly preferably when the hardness is relatively not important, 0.04 ⁇ m. This is 2 ⁇ m or less.
• ultraviolet rays emitted from a light source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, or an electron beam extracted from a particle accelerator of 20 to 2000 kV is usually used.
• a light source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, or an electron beam extracted from a particle accelerator of 20 to 2000 kV is usually used.
• ⁇ -rays, ⁇ -rays, ⁇ -rays and other active energy rays can be used, and these active energy rays are irradiated onto the coating film and cured to form a cured film.
• a cured film formed by irradiation with such active energy rays is particularly preferable
• the cured resin of the present invention is formed by irradiating the above-mentioned resin composition of the present invention with active energy rays to polymerize the polymerizable component in the composition, and it is particularly preferable to satisfy the following suitable physical properties.
• the curing of the coating film containing the resin composition of the present invention is not limited to ultraviolet rays, and active energy rays such as electron beams, ⁇ rays, ⁇ rays, and ⁇ rays can be used.
• Preferred examples of the “polymerization upon irradiation” include photoradical polymerization and photocationic polymerization. In the following, ultraviolet irradiation is usually performed in an oxygen concentration atmosphere.
• a cured product obtained by curing the resin composition of the present invention has the following physical properties.
• high hardness means that the hardness is HB or higher under the conditions of the pencil hardness JIS K-5400 standard.
• the pencil hardness is determined as 6B, 5B,..., B, HB, F, H, 2H, 3H,.
• the resin composition of the present invention was applied on an 188 ⁇ m-thick easy-adhesion PET substrate, and the obtained coating film was applied with UV light having a wavelength of 254 nm of 500 mJ / cm 2 using a high-pressure mercury lamp with an output density of 120 W / cm.
• the pencil hardness of a cured film having a film thickness of 5 ⁇ m formed by irradiating with a light amount is preferably B or higher, particularly HB or higher.
• the resin composition of the present invention contains dipentaerythritol hexaacrylate
• this is applied onto an 188 ⁇ m-thick easy-adhesive PET substrate, and the resulting coating film is used with a high-pressure mercury lamp with an output density of 120 W / cm.
• the pencil hardness of a cured film having a thickness of 5 ⁇ m formed by irradiating ultraviolet rays having a wavelength of 254 nm so as to have an integrated light quantity of 500 mJ / cm 2 is preferably 3H or more.
• composition used for the evaluation of the pencil hardness uses only 1-hydroxycyclohexyl phenyl ketone as a radical polymerizable photoinitiator, and is 1 for 100 parts by weight of solid content other than 1-hydroxycyclohexyl phenyl ketone. -Containing 2.5 parts by weight of hydroxycyclohexyl phenyl ketone.
• the cured product of the present invention exhibits excellent water and oil repellency.
• the excellent water and oil repellency is that the resin composition of the present invention is applied onto an easily adhesive PET substrate having a thickness of 188 ⁇ m, and a high-pressure mercury lamp with an output density of 120 W / cm is used for the obtained coating film.
• the contact angle of water on the surface of a 5 ⁇ m-thick cured film formed by irradiating ultraviolet light having a wavelength of 254 nm with an integrated light quantity of 500 mJ / cm 2 is 100 ° or more, 120 ° or less, particularly 102 ° or more. 115 degrees or less, and the contact angle to hexadecane is 50 degrees or more and 90 degrees or less, particularly 52 degrees or more and 75 degrees or less.
• the method for measuring the contact angle will be described in detail in examples described later.
• the cured product of the present invention is excellent in stain resistance and further in durability of its properties. In particular, it exhibits excellent antifouling properties against oily soils.
• the excellent stain resistance is that when black magic is adhered to the surface of the cured product or cured film of the resin composition of the present invention and wiped off with a tissue paper at a load of 200 g, the wiping operation within 3 reciprocations, more preferably 2 It can be evaluated by its extremely high fingerprint resistance so that the fingerprint can be completely removed within a round trip.
• the superior durability of stain resistance can be evaluated by the fact that fingerprint removability does not deteriorate even if black magic is attached, wipes 3 times with tissue paper at a load of 200 g, and repeats the wiping operation 5 times. Is a greater feature of the cured product of the present invention. Even if a stain resistance imparting agent that can be wiped off with a small number of wipes is used, the conventional ones have insufficient hardness or are not fixed to the film surface. The surface was finely scratched after a dozen times, and fingerprints (or artificial fingerprint liquid) entered the gap, or the stain resistance imparting agent itself was lost from the surface, resulting in poor fingerprint removal durability. .
• the resin composition of the present invention has a high hardness after curing and is fixed to the film surface, the black magic wiping property does not deteriorate even if the operation is repeated 5 times or more, preferably 10 times or more. It has the feature of having extremely high wiping performance durability.
• a cured product obtained by irradiating the resin composition of the present invention with active energy rays to polymerize a polymerizable component in the composition is excellent in characteristics such as stain resistance and hardness. Therefore, an article having a cured film on the surface obtained by irradiating the resin composition of the present invention with active energy rays is excellent in properties such as stain resistance and hardness.
• This cured film may be formed by applying the resin composition of the present invention to the surface of the article main body and then irradiating and polymerizing the active energy rays, or by curing by irradiating and polymerizing the active energy rays. The film may be separately formed and then laminated on the article.
• the cured film of the present invention can be applied to various articles.
• an optical recording medium an optical display, a transparent film for agricultural greenhouses (because it is necessary to take in sunlight effectively, a contamination resistance function is necessary), Surface protection transparent film for solar cells (contamination-resistant function is necessary to prevent battery efficiency degradation), transparent film for retroreflective sign surface protection (to make the sign characters easier to see even in relatively dark lights such as headlamp lights and outside light) Therefore, it can be applied to optical lenses, optical prisms, prism sheets, automobile window materials, building window materials, spectacle lenses, and the like. In particular, it is preferably applied to an optical article that requires high transparency.
• the resin composition of the present invention is suitably used for forming a hard coat layer by coating, drying and curing on various substrates.
• the type of the substrate is not particularly limited, but a substrate made of a resin is preferable because of its high adhesiveness.
• the resin base material may be any of a plate shape, a sheet shape, and a film shape, and may be a molded product having an arbitrary shape.
• a base material may be a part of laminated body, and another layer may be interposed between a base material and a cured film.
• the resin substrate may be a thermoplastic resin or a cured resin cured by heat or active energy rays.
• thermoplastic resin examples include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polymethyl methacrylate (PMMA), and methyl methacrylate (MMA) -containing copolymers (methyl methacrylate-styrene copolymer resin (MS Resin)), polycarbonate (PC), triacetyl cellulose, acrylonitrile-butadiene-styrene copolymer (ABS resin), modified polyolefin resin, fluororesin (for example, vinylidene fluoride resin (PVDF), vinyl fluoride resin (PVF)) Etc.), hydrogenated polystyrene resins, cycloolefin resins (for example, Arton manufactured by JSR, ZEONEX manufactured by ZEON, ZEONOR, and APPEL manufactured by Mitsui Chemicals, Inc.).
• PET polyethylene terephthalate
• PMMA polymethyl methacrylate
• MMA methyl methacrylate
• the curable resin examples include an epoxy resin, a urethane resin, a cured product of a thermosetting or photocurable acrylic resin, a cured product such as a thermosetting or photocurable organic-inorganic hybrid resin, and the like.
• These base materials may be, for example, films formed by coating themselves, or may be molded products by various molding methods.
• the base material is preferably formed by any one of a coating method, a melt extrusion method, and a solvent cast method.
• a base material contains the functional group which can be hardened
• inorganic oxide fine particles and / or urethane acrylate in order to increase the hardness of the base material or reduce the curing shrinkage.
• transparent generally means that the transmittance of light having a target wavelength is 80% or more.
• the cured film of the present invention can also be suitably used as a stain-resistant hard coat layer for optical recording media.
• the resin composition of the present invention can be suitably used for optical display applications.
• it is preferable as an agent for imparting stain resistance to the display panel surface of flat display (liquid crystal display, plasma display, rear projection display, front projector screen, inorganic EL display, organic EL display, etc.).
• It can be preferably used as a hard coat layer on the surface of a mobile information terminal (PDA or the like), a display having a touch panel input function in a PC monitor or the like, or a flat TV (particularly a liquid crystal television) widely used at home.
• the resin composition of the present invention When the resin composition of the present invention is applied to a laminate used for such an optical recording medium or display, a transparent resin substrate is used, and the resin composition of the present invention is applied to at least one outermost surface of the laminate. It is preferable to form a cured film formed by polymerization by irradiation with active energy rays.
• a cured product obtained by polymerizing the resin composition of the present invention by irradiation with active energy rays is excellent in properties such as stain resistance and hardness.
• An article having on its surface a film formed by polymerizing the resin composition of the present invention by irradiating active energy rays is excellent in properties such as stain resistance and hardness.
• the composition After the composition is applied to the surface of the article, the composition may be polymerized by irradiation with active energy rays, or a film polymerized by irradiation with active energy rays may be laminated on the article.
• ⁇ Synthesis Example 2 Synthesis of polymer (A-02)> Add 50 g of perfluorohexylethyl methacrylate, 10 g of lauryl methacrylate, 10 g of ⁇ , ⁇ -dimercaptopropylpolydimethylsiloxane (number average molecular weight 1600), 30 g of glycidyl methacrylate, 0.9 g of dodecyl mercaptan, 200 g of 1-methoxy-2-propanol, The internal temperature was raised to about 60 ° C. under a nitrogen stream.
• V65 2,2′-azobis (2,4-dimethylvaleronitrile)
• V65 2,2′-azobis (2,4-dimethylvaleronitrile)
• V65 2,2′-azobis (2,4-dimethylvaleronitrile)
• the solid concentration was about 34%.
• 0.1 g of p-methoxyphenol and 0.5 g of triphenylphosphine were added. After 5 minutes, 50.6 g of acrylic acid was dissolved in 19 g of 1-methoxy-2-propanol and added dropwise over 30 minutes. During this time, the liquid temperature was kept at 90 to 105 ° C. Thereafter, the liquid temperature was raised to 110 ° C., maintained at this temperature for 12 hours, and then returned to room temperature. The solid content was 35% (X-01).
• DPHA Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.) M-313: Isocyanuric acid EO-modified di- and triacrylate (“Aronix M-313” manufactured by Toagosei Co., Ltd.) irg184: hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by BASF) MegaFuck F-555: DIC's “MegaFuck F-555” Footage 710FM: Neos "Fuagegent 710FM" MIBK: methyl isobutyl ketone MEK: methyl ethyl ketone PGM: 1-methoxy-2-propanol PGMAc: 1-methoxypropyl-2-acetate
• the antifoaming properties of the resin compositions of Examples 1-1 to 1-9 and Comparative Examples 1 to 9 prepared as described above were evaluated.
• the evaluation method is as follows. 15 mL of the resin compositions of Examples 1-1 to 1-9 and Comparative Examples 1 to 9 were each placed in a 30 mL capacity bottomed cylindrical container with an inner diameter of 1.5 cm and shaken 20 times for 5 seconds (swing width) 10 to 20 cm), and then left to stand to measure the time required for the bubbles on the liquid surface to disappear. Visually measure the "defoaming ability" in three stages ( ⁇ : less than 3 minutes, ⁇ : 3 minutes to less than 20 minutes) , X: 20 minutes or more). Further, the transparency and uniformity of the liquid before shaking were observed, and the “appearance” was evaluated in two stages ( ⁇ : transparent, x: white turbidity and precipitation). The results are shown in Table 2.
• the resin compositions of Examples 1-1 to 1-9 exhibited excellent defoaming properties.
• the resin compositions of Comparative Examples 1 to 7 easily foamed and the foam did not disappear easily.
• the liquid became cloudy and difficult to observe, and the defoaming property could not be evaluated.
• Comparative Example 8 using a polymer having a hydroxyl group and having no fluoroalkyl group
• Comparative Example 9 using a polymer having no hydroxyl group and having a fluoroalkyl group
• the resin composition These bubbles are caused by hydroxyl groups and fluoroalkyl groups present in the polymer.
• the cured films prepared as described above were evaluated for the following items (1) to (6).
• (1) Transparency The haze value of the cured film was measured using a haze meter (“HAZE METER HM-65W” manufactured by Murakami Color Research Laboratory) according to JIS K-7105.
• the contact angle meter (“DropMaster DM500” manufactured by Kyowa Interface Science Co., Ltd.) is used. Then, 0.002 mL of pure water or hexadecane was dropped onto the cured film, and after 1 minute, the contact angle with water and the contact angle with hexadecane were measured using a contact angle meter (DropMaster 500, manufactured by Kyowa Interface Science Co., Ltd.). (Unit: degree).
• Adhesiveness Tested by a cross cut method described in JIS K5400.
• Table 3 shows the evaluation results of the cured film.
• the cured film obtained by curing the resin composition of the present invention was good in all of transparency, hardness, water / oil repellency, adhesion, stain resistance, and stain resistance durability.
• the resin composition of the present invention has low foaming properties and excellent leveling properties. Furthermore, it was shown that the resin composition of the present invention achieves a cured product having high hardness and excellent stain resistance and durability, water / oil repellency, and adhesion by curing.
• DPHA Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.) M-313: Isocyanuric acid EO-modified di- and triacrylate (“Aronix M-313” manufactured by Toagosei Co., Ltd.) irg184: hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by BASF) MegaFuck F-555: DIC's “MegaFuck F-555” Megafuck F-477: DIC's “Megafuck F-477” MegaFuck F-444: DIC's “MegaFuck F-444” Footage 710FM: Neos "Fuagegent 710FM" Footage 208G: Neos "Fargent 208G” Aftergent 215M: Neos "Furgent 215M” Footage 245F: Neos'"
• the measuring method of the physical-property value of the additive used by the Example and the comparative example is as follows.
• a literature value (IUPAC Gold Book-solubility parameter) was used for the SP value of the solvent.
• the surface tension reducing ability was measured by measuring the surface tension of a 1% PGMAc solution of a fluorine group-containing oligomer using a surface tension meter (“DropMaster series” manufactured by Kyowa Interface Chemical Co., Ltd.). It was calculated as “surface tension of 1% PGMAc solution”.
• the weight average molecular weight is measured using GPC (“HLC-8120GPC” manufactured by Tosoh Corporation) using tetrahydrofuran as a solvent and polystyrene as a standard sample. Table 5 shows the measurement results of the physical properties of the oligomer.
• the antifoaming properties of the resin compositions of Examples and Comparative Examples prepared as described above were evaluated.
• the evaluation method is as follows. Each of 15 mL of the resin compositions of Examples and Comparative Examples was put into a 30 mL bottomed cylindrical container having an inner diameter of 1.5 cm, shaken 20 times in 5 seconds (running width 10 to 20 cm), and allowed to stand. The time required for the bubbles on the liquid surface to disappear was measured visually. A product of 15 minutes or longer was used as a comparative example because the productivity was actually poor. Further, the transparency and uniformity of the liquid before shaking were observed, and the “appearance” was evaluated in two stages ( ⁇ : transparent, x: white turbidity and precipitation). The results are shown in Table 6.
• the resin compositions of the examples exhibited excellent antifoaming properties.
• the resin composition of the comparative example easily foamed and the foam did not disappear easily.
• the cured films prepared as described above were evaluated for the following items (1) to (6).
• (1) Transparency The haze value of the cured film was measured using a haze meter (“HAZE METER HM-65W” manufactured by Murakami Color Research Laboratory) according to JIS K-7105.
• the contact angle meter (“DropMaster DM500” manufactured by Kyowa Interface Science Co., Ltd.) is used. Then, 0.002 mL of pure water or hexadecane was dropped onto the cured film, and after 1 second, the contact angle with water and the contact angle with hexadecane were measured using a contact angle meter (DropMaster 500, manufactured by Kyowa Interface Science Co., Ltd.). (Unit: degree).
• Adhesiveness Tested by a cross cut method described in JIS K5400.
• Table 7 shows the evaluation results of the cured film.
• the cured film obtained by curing the resin composition of the present invention was good in all of transparency, hardness, water / oil repellency, adhesion, stain resistance, and stain resistance durability.
• the resin composition of the present invention has low foaming properties and excellent leveling properties. Furthermore, it was shown that the resin composition of the present invention achieves a cured product having high hardness and excellent stain resistance and durability, water / oil repellency, and adhesion by curing.

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