WO2010090116A1 - Composition de résine durcissable par un rayonnement d'énergie actinique pour revêtement dur et son utilisation - Google Patents

Composition de résine durcissable par un rayonnement d'énergie actinique pour revêtement dur et son utilisation Download PDF

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Publication number
WO2010090116A1
WO2010090116A1 PCT/JP2010/051077 JP2010051077W WO2010090116A1 WO 2010090116 A1 WO2010090116 A1 WO 2010090116A1 JP 2010051077 W JP2010051077 W JP 2010051077W WO 2010090116 A1 WO2010090116 A1 WO 2010090116A1
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hard coat
resin composition
meth
energy ray
active energy
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Japanese (ja)
Inventor
一司 浅見
浩和 狩野
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4845—Polyethers containing oxyethylene units and other oxyalkylene units containing oxypropylene or higher oxyalkylene end groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/10—Epoxy resins modified by unsaturated compounds
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a resin composition for an active energy ray-curable hard coat that is excellent in scratch resistance, hardness, flexibility, fingerprint visibility and fingerprint wiping property on a plastic surface and can be overcoated. More specifically, the present invention relates to a resin composition for an active energy ray-curable hard coat, which is suitable for application to a plastic surface such as polyester, acrylic, triacetyl cellulose, polycarbonate, etc., is transparent, has excellent scratch resistance, and hardness.
  • the present invention relates to an active energy ray-curable resin composition suitable for a hard coat of a switch panel manufactured by a film used in a touch panel display or in-mold molding because of its excellent visibility and fingerprint wiping property.
  • the fingerprint visibility is the difficulty of seeing the fingerprint imprint
  • the fingerprint wiping is the ease of wiping off the attached fingerprint imprint.
  • the present invention provides a hard coat film capable of obtaining a molded product having the above characteristics without generating cracks in the curved surface portion of the molded product surface portion.
  • the present invention is particularly excellent in moldability, it is also suitable for a hard coat of a film used for in-mold molding.
  • plastics are used in large quantities in various industries including the automobile industry, home appliance industry, and electrical and electronics industry.
  • the reason why a large amount of plastic is used in this way is that, in addition to its processability and transparency, it is lightweight, inexpensive and has excellent optical properties.
  • plastic has a drawback that it is softer than glass or the like and the surface is easily damaged.
  • a hard coating agent a thermosetting hard coat agent such as silicone, acrylic or melamine is used.
  • silicone hard coat agents are especially used because of their high hardness and excellent quality, but they are long and expensive, and hard coats that are provided for continuously processed films It is not suitable.
  • Patent Document 1 photosensitive acrylic hard coating agents have been developed and used.
  • Such a photosensitive hard coating agent is immediately cured by irradiation with active energy rays such as ultraviolet rays to form a hard film, so that the processing speed is high, and the hardness, scratch resistance, etc. are excellent. Due to its performance and low total cost, it is now the mainstream of hard coating agents. In particular, it is used for continuous processing of films such as polyester.
  • polyester films examples include polyester films, acrylic films, polycarbonate films, vinyl chloride films, triacetyl cellulose films, and polyethersulfone films.
  • Polyester films have various excellent properties. Most widely used. This polyester film is, for example, a glass shatterproof film, an automobile light-shielding film, a whiteboard surface film, a system kitchen surface antifouling film, or a CRT flat TV, touch panel display, liquid crystal display (LCD) in terms of electronic materials. It is widely used as a functional film for plasma displays (PDP), organic EL displays, etc., and for body parts and switch panels of home appliances, casings of mobile phones and personal computers, and automobile interior parts.
  • PDP plasma displays
  • organic EL displays etc.
  • polycarbonate or acrylic sheets or substrates with a hard coat are used as liquid crystal related materials around optical disks and backlights.
  • a base material coated with a hard coating agent has been required to have other functions as well as performance as a hard coat called scratch resistance.
  • a display such as a CRT, LCD, PDP, or touch panel provided with a film has a problem that the display screen is difficult to see due to reflection and the eyes are likely to get tired. Processing is required (Patent Document 2).
  • Patent Document 3 a hard coat having an antistatic function using a surfactant or a conductive metal oxide has been developed.
  • the hard coat may be required to have properties such as elongation and flexibility contrary to the properties such as scratch resistance and hardness as the hard coat.
  • the use of films is increasing in the field of molding such as casings for mobile phones and personal computers, automotive interior materials such as meter covers, display panels and switch buttons for AV equipment and home appliances, etc. It is coming.
  • plastic products are molded by injection molding using a mold.
  • a method of processing the surface of this product a method of attaching a film to the inner surface of the mold and attaching it to the surface of the molded product at the same time is proposed. It is called in-mold molding or film insert injection molding. That is, the film function can be imparted simultaneously with molding by sandwiching the film between the molds and simultaneously performing injection molding.
  • cosmetics and functionality such as decoration on the molded product and increased hardness can be imparted by printing a pattern or a pattern on the film to be mounted or using a hard coat film.
  • a hard coat is applied to the base film, and the hard coat is applied to the film having the release layer and in-mold lamination (IML) in which the hard coat film is integrally formed.
  • IML in-mold lamination
  • IMD in-mold decoration
  • the hard coat used for injection molding is on the top surface of the molded plastic product, not only the surface hardness, but also the cosmetic properties such as gloss and the performance such as elongation and flexibility that can withstand the molding process. Is also necessary. Therefore, when forming a hard coat layer on a substrate film, a method of integrally forming a hard coat film that has been cured (cross-linked), or first forming only a film of a hard coat film, and curing (cross-linking after molding) ).
  • a method for improving the fingerprint wiping property as the fingerprint resistance for example, there is a method of improving the water repellency and oil repellency of the surface by using a fluorine-based material, silicone oil or the like mixed in the coating composition.
  • fluorine and silicone are low refractive index components, when they are used as a coating on the surface, there is a disadvantage that the difference in refractive index from the fingerprint becomes large, and even a small amount of fingerprint is noticeable.
  • the wiping is insufficient, in addition to a large difference in refractive index, there are water repellent and oil repellent functions, so that the contact angle with the fingerprint becomes high and the fingerprint becomes more visible.
  • IMD performs further printing on the hard coat layer, if a fluorine-based material, silicone oil or the like is mixed in the coating composition, printing ink will be repelled and printing cannot be performed. is there.
  • the present invention improves the above-mentioned drawbacks, has good hardness, high transparency, good elongation and flexibility, and is an active energy ray-curable hard disk excellent in fingerprint visibility resistance and fingerprint wiping properties. It aims at providing the resin composition for a coat.
  • a composition containing a (meth) acrylate compound (B) having a refractive index of 1.45 to 1.55, and a contact angle of the cured film of the composition with oleic acid is Active energy ray-curable hard coat resin composition having a temperature of 25 degrees or less;
  • Hard coat resin composition A polyfunctional (meth) acrylate compound (A) having three or more (meth) acryloyl groups in the molecule is obtained by reacting a polyfunctional (meth) acrylate compound having active hydrogen with polyisocyanate.
  • the active energy ray-curable hard coat resin composition according to any one of (1) to (5), which is a compound; (7) A urethane having a (meth) acrylate compound (B) having a polytetramethylene glycol skeleton having a polytetramethylene glycol skeleton having a number average molecular weight of 600 or more and having two or more (meth) acryloyl groups in the molecule.
  • the active energy ray-curable hard coat resin composition according to any one of (1) to (6), which is a (meth) acrylate compound; (8) The addition amount of the (meth) acrylate compound (B) having a polytetramethylene glycol skeleton having a polytetramethylene glycol skeleton portion having a number average molecular weight of 600 or more is based on 100% by weight of the solid content of the resin composition.
  • an active energy ray-curable hard coat resin composition having excellent hardness, transparency, scratch resistance, flexibility, fingerprint visibility, fingerprint wiping property, etc., which can be used for in-mold molding. And a cured product thereof.
  • the present invention relates to a polyfunctional (meth) acrylate compound (A) having 3 or more (meth) acryloyl groups in the molecule and a polytetramethylene glycol skeleton having a number average molecular weight of 600 or more in the polytetramethylene glycol skeleton portion.
  • the present invention relates to a resin composition for an active energy ray-curable hard coat that is less than or equal to a degree.
  • the present invention will be described in detail.
  • polyfunctional (meth) acrylate compound (A) having 3 or more, preferably 3 to 12 (meth) acryloyl groups in the molecule contained in the active energy ray-curable hard coat resin composition of the present invention For example, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, epichlorohydrin (ECH) modified glycerol tri (meth) acrylate, ethylene oxide (EO) modified glycerol tri (meth) acrylate, propylene oxide (PO) modified glycerol triacrylate, pentaerythritol tri (meth) acrylate, EO modified tri (meth) acrylate phosphate, caprolactone modified trimethylolpropane tri (meth) acrylate, EO modified trimethyl Propane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, ditrimethylo
  • Examples of the polyfunctional (meth) acrylate having active hydrogen include pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol tetra (meth).
  • Pentaerythritols such as acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, methylols such as trimethylolpropane di (meth) acrylate, epoxy acrylates such as bisphenol A diepoxy acrylate, etc. Can be mentioned. Of these, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are preferable.
  • These polyfunctional (meth) acrylates having active hydrogen may be used alone or in admixture of two or
  • polyisocyanate polyisocyanates composed of chain saturated hydrocarbons, cyclic saturated hydrocarbons (alicyclic), and aromatic hydrocarbons can be used.
  • polyisocyanates include chain saturated hydrocarbon polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and methylenebis (4-cyclohexyl).
  • Isocyanate hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, etc., cyclic saturated hydrocarbon (alicyclic) polyisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene Diisocyanate, 3,3′-dimethyl-4,4′-diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate Aromatic polyisocyanates such as 1,5-naphthalene diisocyanate. Of these, isophorone diisocyanate and hexamethylene diisocyanate are preferable. These polyisocyanates may be used alone or in combination of two or more.
  • the polyfunctional urethane (meth) acrylate is obtained by reacting the polyfunctional (meth) acrylate having active hydrogen with a polyisocyanate.
  • polyisocyanate is usually in the range of 0.1 to 50 equivalent, preferably in the range of 0.1 to 10 equivalent as the isocyanate group equivalent. is there.
  • the reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C.
  • the end point of the reaction is the time when the polyisocyanate calculated by the method of reacting residual isocyanate with excess n-butylamine and back titrating with 1N hydrochloric acid is 0.5% by weight or less.
  • a catalyst may be added for the purpose of shortening the reaction time.
  • the catalyst either a basic catalyst or an acidic catalyst is used.
  • Examples of the basic catalyst include amines such as triethylamine, diethylamine, dibutylamine, and ammonia, phosphines such as tributylphosphine and triphenylphosphine, pyridine, and pyrrole.
  • amines such as triethylamine, diethylamine, dibutylamine, and ammonia
  • phosphines such as tributylphosphine and triphenylphosphine
  • pyridine pyrrole.
  • the acidic catalyst examples include metal salts such as copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, trititanium tetrabutoxide, zirconium tetrabutoxide, Lewis acids such as aluminum chloride, 2-ethylhexanetin, Examples thereof include tin compounds such as octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate.
  • the amount added can usually be about 0.1 to 1 part by weight per 100 parts by weight of the polyisocyanate.
  • a polymerization inhibitor for example, methoquinone, hydroquinone, methylhydroquinone, phenothiazine, etc.
  • the amount used is 0.01 weight with respect to the reaction mixture. % To about 1% by weight, preferably about 0.05% to 0.5% by weight.
  • the reaction temperature is 60 to 150 ° C, preferably 80 to 120 ° C.
  • the content of the polyfunctional (meth) acrylate compound (A) having three or more (meth) acryloyl groups in the molecule in the resin composition for an active energy ray-curable hard coat of the present invention is the solid content of the resin composition.
  • the content is 100% by weight, it is usually 20.0% to 99.9% by weight, preferably 45.0% to 90.0% by weight.
  • the (meth) acrylate compound (B) having a polytetramethylene glycol skeleton in which the number average molecular weight of the polytetramethylene glycol skeleton portion contained in the resin composition for an active energy ray-curable hard coat of the present invention is 600 or more
  • examples thereof include polyester (meth) acrylate of polytetramethylene glycol, epoxy (meth) acrylate of polytetramethylene glycol, urethane (meth) acrylate of polytetramethylene glycol, and the like.
  • urethane (meth) acrylate of polytetramethylene glycol is preferable.
  • the number average molecular weight of the polytetramethylene glycol skeleton is preferably about 600 to 10,000.
  • polyester (meth) acrylate of the polytetramethylene glycol and the epoxy (meth) acrylate of the polytetramethylene glycol include compounds shown in the following synthesis examples.
  • urethane (meth) acrylates of polytetramethylene glycol include polytetramethylene glycol having a polytetramethylene glycol skeleton number-average molecular weight of 600 or more, hexamethylene diisocyanate, alicyclic polyisocyanate, and tolylene diisocyanate.
  • Organic polyisocyanates such as xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, Examples thereof include reactants with hydroxyl group-containing ethylenically unsaturated compounds such as ⁇ -caprolactone-modified 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate.
  • Polytetramethylene glycol, organic polyisocyanates, and hydroxyl group-containing ethylenically unsaturated compounds may be used alone or in admixture of two or more.
  • Other polyols may be used together with polytetramethylene glycol.
  • examples of other polyols include polyether polyols other than polytetramethylene glycol, ethylene glycol, 1,4-butanediol, neopentyl glycol, polycaprolactone polyol, polyester polyol, and polycarbonate diol.
  • Preferred compounds as the urethane (meth) acrylate of polytetramethylene glycol include, for example, a reaction product (acryloyl group: 2) of polytetramethylene glycol having a molecular weight of 1000 to 2000, isophorone diisocyanate, and 2-hydroxyethyl acrylate. Can be mentioned.
  • the urethane (meth) acrylate of polytetramethylene glycol is preferably 1.1 to 2.0 equivalents, preferably 70 to 90 ° C., of isocyanate groups of organic polyisocyanates per one equivalent of hydroxyl groups of polytetramethylene glycol.
  • the reaction can then be carried out by reacting 1.0 to 1.5 equivalents of the hydroxyl group-containing ethylenically unsaturated compound per equivalent of the reactant.
  • the urethane (meth) acrylate of the polytetramethylene glycol is preferably a compound in which an acryloyl group is bonded to two or more terminal portions of the molecule.
  • the content of the (meth) acrylate compound (B) having a polytetramethylene glycol skeleton in which the number average molecular weight of the polytetramethylene glycol skeleton portion in the resin composition for an active energy ray-curable hard coat of the present invention is 600 or more is:
  • the solid content of the resin composition is 100 wt%, it is usually 0.1 wt% to 10 wt%, preferably 1 wt% to 5 wt%.
  • the amount of the (meth) acrylate compound (B) is small, the fingerprint wiping property is deteriorated, and when the amount is too large, the hard coat property tends to be lowered.
  • the active energy ray-curable hard coat resin composition of the present invention may contain a photopolymerization initiator (C).
  • the photopolymerization initiator (C) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1, 1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopro Acetophenones such as pan-1-one, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, anthraquinones such as 2-amylanthraquinone
  • Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) and Irgacure 907 (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-produced by Ciba Specialty Chemicals, Inc., which are easily available from the market ON), and lucillin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) manufactured by BASF.
  • lucillin TPO 2,4,6-trimethylbenzoyldiphenylphosphine oxide
  • the content of the photopolymerization initiator (C) in the resin composition for an active energy ray-curable hard coat of the present invention is about 0 to 10% by weight when the solid content of the resin composition is 100% by weight. Preferably, it is about 1 to 7% by weight.
  • the photopolymerization initiator (C) can be used in combination with a curing accelerator.
  • the curing accelerator include triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid isoamyl ester, EPA and other amines, and 2-mercaptobenzoic acid.
  • Examples include hydrogen donors such as thiazole.
  • the content of the curing accelerator in the active energy ray-curable hard coat resin composition of the present invention is about 0 to 5% by weight when the solid content of the resin composition is 100% by weight.
  • the resin composition for an active energy ray-curable hard coat of the present invention may contain colloidal silica (D) having a primary particle size of 1 nm to 200 nm.
  • the colloidal silica (D) may be used as a colloidal solution dispersed in a solvent, or may be used as finely divided silica containing no dispersion solvent.
  • the dispersion solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, diacetone alcohol, polyhydric alcohols such as ethylene glycol or derivatives thereof, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylacetamide, and the like.
  • Ketones esters such as ethyl acetate and n-butyl acetate, nonpolar solvents such as toluene and xylene, acrylates such as 2-hydroxyethyl acrylate, other general organic solvents, water and the like can be used.
  • the amount used is usually 100% to 900% by weight with respect to 100% by weight of colloidal silica.
  • the colloidal silica can be produced by methods known in the literature, or commercially available products can be used.
  • Examples of the colloidal silica include organosilica sol MEK-ST manufactured by Nissan Chemical Industries.
  • a silica surface treated with a silane coupling agent or the like to have a reactive group may be used.
  • the primary particle diameter means the smallest particle diameter of the particles when the aggregation is broken, and can be measured as the average particle diameter of the BET method.
  • colloidal silica (D) those having a primary particle diameter of 1 nm to 200 nm, preferably 1 nm to 100 nm, more preferably 1 nm to 50 nm can be used.
  • 1 nm to 100 nm transparency is secured, and in the case of 1 nm to 50 nm, sufficiently good results are obtained with transparency and haze.
  • the active energy ray-curable hard coat resin composition of the present invention contains colloidal silica (D) having a primary particle size of 1 nm to 200 nm, the content is 100% by weight based on the solid content of the resin composition.
  • the solid content excluding the dispersion medium is 0 to 70% by weight, preferably 5 to 50% by weight.
  • the active energy ray-curable hard coat resin composition of the present invention may contain a diluent (E).
  • E a diluent
  • ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -heptalactone, ⁇ - Lactones such as acetyl- ⁇ -butyrolactone and ⁇ -caprolactone, dioxane, 1,2-dimethoxymethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether, Ethers such as triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, ethylene carbonate Carbonates such as carbonate, propylene carbonate, ketones such as methyl ethyl
  • the active energy ray-curable hard coat resin composition of the present invention may contain a (meth) acrylic compound (F) having 1 to 2 (meth) acryloyl groups in the molecule.
  • the acrylic compound (F) is a compound other than the component (B), for example, diglycol di- (meth) acrylate, tripropylene glycol di (meth) acrylate, and ⁇ -caprolactone adduct of hydroxypivalate neopentyl glycol.
  • (Meth) acrylate for example, KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.
  • di (meth) acrylate of bisphenol A EO adduct 1,4-butanediol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di ( Acrylate), alicyclic (meth) acrylates (tricyclodecane (meth) acrylate, dicyclopentadieneoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantane (meth) Acrylate, etc.), phenylglycidyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth
  • the content of the (meth) acrylic compound (F) having 1 to 2 (meth) acryloyl groups in the molecule in the resin composition for an active energy ray-curable hard coat of the present invention depends on the solid content of the resin composition. Is 100 wt%, 0 wt% to 20.0 wt%, preferably 1.0 wt% to 10.0 wt%.
  • the active energy ray-curable hard coat resin composition of the present invention of the present invention includes a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor, if necessary. It is also possible to add inorganic fine particles other than the cross-linking agent and colloidal silica (D), fillers, and the like to impart the intended functionality.
  • leveling agent it is preferable to use an acrylic or high boiling point solvent system that does not interfere with fingerprint resistance.
  • ultraviolet absorbers examples include benzotriazole compounds, benzophenone compounds, and triazine compounds.
  • light stabilizers include hindered amine compounds and benzoate compounds.
  • antioxidants include phenol compounds. Is mentioned.
  • Examples of the polymerization inhibitor include methoquinone, methylhydroquinone, hydroquinone and the like, and examples of the crosslinking agent include the polyisocyanates and melamine compounds.
  • inorganic fine particles include zinc antimonate, gallium-doped zinc oxide, aluminum-doped zinc oxide, tin oxide, antimony-doped tin oxide, phosphorus-doped tin oxide, and indium-doped tin oxide, and other conductive metal oxides such as titanium oxide and zirconium oxide. Examples thereof include metal oxides for adjusting the refractive index.
  • fillers examples include silica, acrylic beads, urethane beads, and the like having an average particle size of micron order, and can be used for the purpose of forming irregularities on the coating film surface.
  • the active energy ray-curable hard coat resin composition of the present invention comprises the component (A), the component (B), and optionally the component (C), the component (D), the component (E), and the component (F). And other ingredients in any order.
  • the active energy ray-curable hard coat resin composition of the present invention has a refractive index of 1.45 to 1.55 at 25 ° C. when the solid content is 100% (excluding the refractive index of the diluent). It is the resin composition which is the range. If the refractive index is out of this range, the difference in refractive index from the attached fingerprint imprint will be too large and the fingerprint imprint will tend to be very visible.
  • the active energy ray-curable hard coat resin composition of the present invention thus obtained is stable over time.
  • the active energy ray-curable hard coat resin composition of the present invention is applied onto a base film so that the thickness of the resin composition after drying is usually 0.1 ⁇ m to 50 ⁇ m, preferably 1 ⁇ m to 20 ⁇ m.
  • a film obtained by irradiating an active energy ray after drying to form a cured film is also included in the present invention.
  • the base film is not particularly limited, and examples thereof include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triacetylcellulose, polyethersulfone, and cycloolefin-based polymer.
  • the film to be used may be a film provided with a handle, an easy-adhesion layer, a base layer, a surface treatment such as a corona treatment, or a mold release treatment.
  • Examples of the application method of the active energy ray-curable hard coat resin composition include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, and micro reverse. Examples include gravure coater coating, die coater coating, dip coating, spin coat coating, and spray coating.
  • Examples of the active energy ray for curing the active energy ray-curable hard coat resin composition of the present invention include ultraviolet rays and electron beams.
  • an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp or the like is used as a light source, and the amount of light, the arrangement of the light source, etc. are adjusted as necessary.
  • a high-pressure mercury lamp it is preferable to cure at a conveyance speed of 5 to 60 m / min for one lamp having an energy of 80 to 120 W / cm 2 .
  • the photopolymerization initiator (D) may not be used.
  • the contact angle of the cured film obtained by curing the active energy ray-curable hard coat resin composition of the present invention with oleic acid is preferably 25 degrees or less, more preferably 23 degrees or less. If it is 30 degrees or more, even if the refractive index falls within the range of 1.45 to 1.55, the attached fingerprint imprint becomes easy to see. Since oleic acid is a substance close to the component of the fingerprint imprint, it is expected that the fingerprint imprint will be difficult to see if the contact angle with oleic acid is lowered.
  • a substrate having a cured film of the resin composition for an active energy ray-curable hard coat of the present invention is also included in the present invention.
  • the display member and touch panel member which have this cured film are also contained in this invention.
  • the present invention includes a hard coat film for a touch panel having the cured film, a hard coat film for a display, and a hard coat film used for in-mold molding, and molded products such as a touch panel and a display having the cured film are also included in the present invention. included.
  • Synthesis example 1 1395.1 parts of polytetramethylene glycol (PTG-2000SN manufactured by Hodogaya Chemical Co., Ltd .; molecular weight 1993) and 311.2 parts of isophorone diisocyanate were placed in a drying container, and the temperature was gradually raised to 80 ° C. while stirring. It was made to react with. When the ratio of isocyanate is in the range of 6.7 to 7.2%, 167.4 parts of 2-hydroxyethyl acrylate and 0.5 part of methoquinone are added, and the temperature is gradually raised again to 80 ° C. for 5 hours.
  • the reaction was allowed to proceed with stirring, and then 0.15 part of dibutyltin laurate was added, and the reaction was further continued until the isocyanate ratio became 0.1% or less and the reaction was almost quantitatively completed.
  • the synthesized urethane acrylate of polytetramethylene glycol had two acryloyl groups.
  • Synthesis example 2 In a drying container, 595.0 parts of polytetramethylene glycol (PTG-850SN manufactured by Hodogaya Chemical Industry; molecular weight 850) and 311.2 parts of isophorone diisocyanate were placed and gradually heated to 80 ° C. while stirring. It was made to react with. When the isocyanate ratio falls within the range of 6.7 to 7.2%, 167.4 parts of 2-hydroxyethyl acrylate and 0.5 part of methoquinone are added, and the temperature is gradually raised to 80 ° C.
  • the reaction was continued with stirring for a period of time, and then 0.15 part of dibutyltin laurate was added, and the reaction was further continued until the isocyanate ratio became 0.1% or less and the reaction was almost quantitatively completed.
  • the synthesized urethane acrylate of polytetramethylene glycol had two acryloyl groups.
  • Synthesis example 3 In a drying container, 2030.0 parts of polytetramethylene glycol (PTG-2900 manufactured by Hodogaya Chemical Co., Ltd .; molecular weight 2900) and 311.2 parts of isophorone diisocyanate were placed, and gradually heated to 80 ° C. while stirring. It was made to react with. When the ratio of isocyanate is in the range of 6.7 to 7.2%, 167.4 parts of 2-hydroxyethyl acrylate and 0.5 part of methoquinone are added, and the temperature is gradually raised again to 80 ° C. for 5 hours.
  • the reaction was allowed to proceed with stirring, and then 0.15 part of dibutyltin laurate was added, and the reaction was further continued until the isocyanate ratio became 0.1% or less and the reaction was almost quantitatively completed.
  • the synthesized urethane acrylate of polytetramethylene glycol had two acryloyl groups.
  • Synthesis example 4 1395.1 parts of polytetramethylene glycol (PTG-2000SN manufactured by Hodogaya Chemical Industry; molecular weight 1993) and 235.2 parts of hexamethylene diisocyanate were placed in a drying container, and the temperature was gradually raised to 80 ° with stirring. The reaction was carried out at ° C. When the isocyanate ratio is in the range of 6.7 to 7.2%, add 184.7 parts of 2-hydroxypropyl acrylate and 0.5 part of methoquinone, and gradually raise the temperature to 80 ° C again for 5 hours.
  • the reaction was allowed to proceed with stirring, and then 0.15 part of dibutyltin laurate was added, and the reaction was further continued until the isocyanate ratio became 0.1% or less and the reaction was almost quantitatively completed.
  • the synthesized urethane acrylate of polytetramethylene glycol had two acryloyl groups.
  • Synthesis example 5 In a dry container, 1300.0 parts of polytetramethylene glycol diglycidyl ether (Epogosei manufactured by Yokkaichi Chemical Co., Ltd .; molecular weight 650), 146.9 parts of acrylic acid, 0.5 parts of TMAC (tetramethylammonium chloride), BHT ( 0.5 part of dibutylhydroxytoluene) was added, and the temperature was gradually raised to 98 ° C. and reacted at 98 ° C.
  • the synthesized polytetramethylene glycol epoxy acrylate had an epoxy equivalent of 15800, an acid value of 0.73, and two acryloyl groups.
  • Synthesis example 7 1395.1 parts of polypropylene glycol (Hodogaya Chemical Co., Ltd. PPG-2000SN; molecular weight 2000) and 235.2 parts of hexamethylene diisocyanate were placed in a drying container, and the temperature was gradually raised to 80 ° C. while stirring, And reacted.
  • the isocyanate ratio is in the range of 6.7 to 7.2%, add 184.7 parts of 2-hydroxypropyl acrylate and 0.5 part of methoquinone, and gradually raise the temperature to 80 ° C again for 5 hours.
  • the reaction was allowed to proceed with stirring, and then 0.15 part of dibutyltin laurate was added, and the reaction was further continued until the isocyanate ratio became 0.1% or less and the reaction was almost quantitatively completed.
  • the synthesized urethane acrylate of polytetramethylene glycol had two acryloyl groups.
  • Synthesis example 8 In a drying container, 1395.1 parts of polytetramethylene glycol (PTG-2000SN manufactured by Hodogaya Chemical Co., Ltd .; molecular weight 1993) and 235.2 parts of hexamethylene diisocyanate were placed and gradually heated to 80 ° C. while stirring. The reaction was carried out at ° C. When the ratio of isocyanate is in the range of 6.7 to 7.2%, 425.7 parts of pentaerythritol triacrylate and 0.5 part of methoquinone are added, and the temperature is gradually raised to 80 ° C. and stirred for 5 hours.
  • the synthesized urethane acrylate of polytetramethylene glycol had 6 acryloyl groups.
  • Synthesis Example 9 In a drying container, 2030.0 parts of polytetramethylene glycol (PTG-2900 manufactured by Hodogaya Chemical Co., Ltd .; molecular weight 2900) and 235.2 parts of hexamethylene diisocyanate were placed, and gradually heated to 80 ° C. while stirring. The reaction was carried out at ° C. When the ratio of isocyanate is in the range of 6.7 to 7.2%, 425.7 parts of pentaerythritol triacrylate and 0.5 part of methoquinone are added, and the temperature is gradually raised to 80 ° C. and stirred for 5 hours.
  • the synthesized urethane acrylate of polytetramethylene glycol had 6 acryloyl groups.
  • Synthesis Example 10 In a drying container, 1395.1 parts of polytetramethylene glycol (PTG-2000SN manufactured by Hodogaya Chemical Co., Ltd .; molecular weight 1993) and 235.2 parts of hexamethylene diisocyanate were placed and gradually heated to 80 ° C. while stirring. The reaction was carried out at ° C. When the ratio of isocyanate is in the range of 6.7 to 7.2%, add 744.1 parts of dipentaerythritol triacrylate and 0.5 parts of methoquinone, and gradually raise the temperature to 80 ° C again for 5 hours.
  • the reaction was allowed to proceed with stirring, and then 0.15 part of dibutyltin laurate was added, and the reaction was further continued until the isocyanate ratio became 0.1% or less and the reaction was almost quantitatively completed.
  • the synthesized urethane acrylate of polytetramethylene glycol had 10 acryloyl groups.
  • Examples 1 to 14 and Comparative Examples 1 to 5 A resin composition containing the components shown in Table 1 is applied on a readily adhesive-treated PET (polyethylene terephthalate) film (100 ⁇ m) with a bar coater, dried at about 80 to 100 ° C., and then an ultraviolet irradiator.
  • a readily adhesive-treated PET (polyethylene terephthalate) film 100 ⁇ m
  • a bar coater dried at about 80 to 100 ° C., and then an ultraviolet irradiator.
  • High-pressure mercury lamp 80 W / cm
  • Lamp height 10 cm
  • Conveyor speed 5 m / min ⁇ 3 passes (Energy: about 200 mW / cm 2 , about 360 mJ / cm 2 ) to obtain a hard coat film having a thickness of about 4 ⁇ m.
  • the unit represents “part”.
  • the artificial fingerprint liquid described later was imprinted on a coated film having the above composition using a resin mold having a pitch of 50 to 100 ⁇ m, and the imprint was confirmed by haze measurement.
  • the contact angle of the coating film having the above composition was measured using an automatic contact angle meter (DM500 manufactured by Kyowa Interface Science Co., Ltd.). Specifically, oleic acid was dropped on a polyester film having a cured film to be measured.
  • DM500 manufactured by Kyowa Interface Science Co., Ltd.
  • the film having the cured film of the active energy ray-curable hard coat resin composition of the present invention had good hardness, fingerprint visibility and fingerprint wiping property.
  • the hardness was good, but the fingerprint resistance visibility and the fingerprint wiping property were poor.
  • Comparative Example 2 in which the skeleton of the component (B) is polypropylene glycol, the fingerprint resistance visibility and the fingerprint wiping property were inferior.
  • Comparative Example 3 Even if the skeleton part is polytetramethylene glycol, in Comparative Example 3 having no di (meth) acryloyl group, the fingerprint wiping property was inferior. Further, Comparative Example 4 having a refractive index of more than 1.55 has poor fingerprint visibility-2 (visual observation), and Comparative Example 5 having a contact angle of oleic acid of more than 30 degrees has fingerprint resistance and fingerprint wiping properties. It was extremely bad.
  • Examples 12 to 14 including the component (B) having a polyfunctional acryloyl group the hardness was further improved.
  • the hard coat film obtained by using the active energy ray-curable hard coat resin composition of the present invention has high hardness and good fingerprint visibility and fingerprint wiping properties.
  • the resin composition also has a good stretch ratio. Accordingly, the resin composition for an active energy ray-curable hard coat of the present invention is suitable for a hard coat of a film used for a touch panel display, and is also suitable as a material for a hard coat film used for forming such as having a folding process.

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Abstract

L'invention porte sur une composition de résine durcissable par un rayonnement d'énergie actinique pour des revêtements durs qui atteint une dureté satisfaisante, une transparence élevée, un allongement satisfaisant et une souplesse satisfaisante, une visibilité des empreintes réduites et une excellente aptitude à l'élimination des empreintes par essuyage. La composition de résine durcissable par un rayonnement d'énergie actinique pour des revêtements durs comprend (A) un composé (méth)acrylate polyfonctionnel ayant trois ou plus de trois groupes (méth)acryloyles par molécule et (B) un composé (méth)acrylate ayant un squelette de polytétraméthylèneglycol ayant une masse moléculaire moyenne en nombre supérieure ou égale à 600, la composition ayant un indice de réfraction de 1,45 à 1,55 et donnant un film durci qui a un angle de contact avec l'acide oléique inférieur ou égal à 25 degrés.
PCT/JP2010/051077 2009-02-04 2010-01-28 Composition de résine durcissable par un rayonnement d'énergie actinique pour revêtement dur et son utilisation Ceased WO2010090116A1 (fr)

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