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WO2013011693A1 - Composition de résine polymérisable sous l'effet de la lumière et élément de tuyauterie et panneau fonctionnel l'utilisant - Google Patents

Composition de résine polymérisable sous l'effet de la lumière et élément de tuyauterie et panneau fonctionnel l'utilisant Download PDF

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Publication number
WO2013011693A1
WO2013011693A1 PCT/JP2012/004602 JP2012004602W WO2013011693A1 WO 2013011693 A1 WO2013011693 A1 WO 2013011693A1 JP 2012004602 W JP2012004602 W JP 2012004602W WO 2013011693 A1 WO2013011693 A1 WO 2013011693A1
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Prior art keywords
meth
acrylate
resin composition
photocurable resin
oligomer
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Ceased
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PCT/JP2012/004602
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English (en)
Japanese (ja)
Inventor
健延 石原
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Bridgestone Corp
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Bridgestone Corp
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Application filed by Bridgestone Corp filed Critical Bridgestone Corp
Priority to JP2013524613A priority Critical patent/JP5805192B2/ja
Priority to CN201280035679.7A priority patent/CN103717632B/zh
Publication of WO2013011693A1 publication Critical patent/WO2013011693A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • 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
    • 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
    • C08G18/61—Polysiloxanes
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • 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
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03C—DOMESTIC PLUMBING INSTALLATIONS FOR FRESH WATER OR WASTE WATER; SINKS
    • E03C1/00—Domestic plumbing installations for fresh water or waste water; Sinks
    • E03C1/12—Plumbing installations for waste water; Basins or fountains connected thereto; Sinks
    • E03C1/18—Sinks, whether or not connected to the waste-pipe

Definitions

  • the present invention relates to a photocurable resin composition, a water-surrounding member using the same, and a functional panel, and in particular, to improve slipperiness (slidability capable of easily removing water droplets on the surface).
  • the present invention relates to a possible photocurable resin composition, and a water-surrounding member and a functional panel using the same.
  • Functional panels as building materials are members that are arranged as the wall surface, floor surface, or ceiling wall surface of a building. Depending on the location, various functions such as soundproofing and humidity control are provided. Has been. Such functional panels are required to have various characteristics such as water repellency and slipperiness that can withstand more severe use environments, particularly when used as a water component in a bathroom, washroom or kitchen in a house. It is done.
  • Patent Document 1 discloses a water-circulating member having a cured coating material containing a low surface free energy compound on its surface. Further, as the low surface free energy compound, a silicone resin compound and a fluororesin compound are used. It is disclosed.
  • Patent Document 2 discloses a resin molded body in which a low surface free energy layer is formed on the surface of the base resin, and the surface of the molded body is a surface having a low surface free energy compared to the surface of the base resin. Further, it is disclosed that the contact angle between the surface of the resin molded body and water is 90 degrees or more and 170 degrees or less, and the falling angle between the surface of the resin molded body and water is 1 degree or more and 80 degrees or less.
  • the low surface free energy surface produced using the low surface free energy compound repels water and forms spherical water droplets on the surface, the water droplets often adhere strongly to the surface and do not fall. It can be seen. Attempts have been made to roughen the surface and make the contact angle of the surface as large as possible in order to drop the attached water droplets from the surface, but the roughening of the surface requires man-hours. However, there is a problem in that the cost is high and dirt is easily attached.
  • an object of the present invention is to provide a photocurable resin composition that can solve the above-described problems and can improve slipperiness.
  • Another object of the present invention is to provide a water-surrounding member and a functional panel which have an application layer formed by curing such a photo-curable resin composition and have good slipperiness.
  • Water droplets on the surface can be easily removed by using a dimethylsilicone (meth) acrylate oligomer obtained by reacting a (meth) acrylate monomer having a functional group capable of reacting with (D) and a fluorine-containing compound. It has been found that a water-slidable surface that can be formed can be formed, and the present invention has been completed.
  • “(meth) acrylate” refers to acrylate or methacrylate.
  • the inventors of the present invention have set an equivalent ratio (—NCO / —OH) of (b) isocyanate group (—NCO) in isocyanate to (a) hydroxyl group (—OH) in silicone polyol to be greater than 100/100 and 300 /
  • an equivalent ratio (—NCO / —OH) of (b) isocyanate group (—NCO) in isocyanate to (a) hydroxyl group (—OH) in silicone polyol By setting it to 100 or less, a prepolymer having an isocyanate group at the terminal can be prepared, and then, for example, a monomer having a hydroxyl group and a (meth) acryloyl group is reacted with the isocyanate group at the terminal of the prepolymer.
  • a highly water-repellent dimethyl silicone (meth) acrylate oligomer having a (meth) acryloyl group at the terminal can be produced, and the present invention has been completed.
  • the photocurable resin composition of the present invention is (A) (a) A silicone polyol represented by the following general formula (1), (b) an isocyanate, and (c) a (meth) acrylate monomer having a functional group capable of reacting with isocyanate at the terminal are reacted. (B) photopolymerizable oligomer and / or (C) photopolymerizable monomer, (D) fluorine, copolymerizable with (A) dimethylsilicone (meth) acrylate oligomer. It contains a containing compound and (E) a photopolymerization initiator.
  • n represents an integer arbitrarily selected so that the number average molecular weight of the (A) dimethyl silicone (meth) acrylate oligomer is 700 to 40,000, and R is the total carbon This represents an alkylene group having 1 to 30 carbon atoms or a functional group having 1 to 30 carbon atoms having an ether bond.
  • the solubility parameter (SP value) of the (C) photopolymerizable monomer is 20.0 (J / cm 3 ) 1/2 or less.
  • the (C) photopolymerizable monomer may be used alone or in combination of two or more.
  • SP value at the time of using 2 or more types of photopolymerizable monomers is the SP value that each monomer has in the SP value that each monomer has, and the blending ratio (mass ratio) (when the total amount of monomers is 1). It means a value obtained by multiplying the ratio of each monomer) and adding them.
  • the (C) photopolymerizable monomer is a compound represented by the following general formula (A).
  • (CH 2 CR 1 COO) n R 2 ⁇ formula (A)
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an n-valent hydrocarbon group having 5 to 20 carbon atoms
  • n is in the range of 1 to 4. Represents an integer.
  • the (B) photopolymerizable oligomer is a (meth) acrylate oligomer having a 1,2-polybutylene oxide unit.
  • the (b) isocyanate is a polyisocyanate compound having a cyclic skeleton in the molecular structure.
  • the functional group capable of reacting with an isocyanate group in the (c) (meth) acrylate monomer is a hydroxyl group.
  • the content of the (A) dimethyl silicone (meth) acrylate oligomer is (B) the photopolymerizable oligomer and / or (C) the photopolymerizable monomer. On the other hand, it is 0.05 mass% to 10 mass%.
  • the (D) fluorine-containing compound has a photopolymerizable functional group.
  • the ratio of the solid content of the (A) dimethyl silicone (meth) acrylate oligomer to the solid content of the (D) fluorine-containing compound (A / D) is 0.2-10.
  • the ratio of the solid content of the (A) dimethyl silicone (meth) acrylate oligomer to the solid content of the (D) fluorine-containing compound (A / D) is 0.4-3.
  • the water-surrounding member of the present invention is characterized by comprising a coating layer formed by curing the photocurable resin composition of the present invention and a base material layer.
  • the functional panel of the present invention is characterized by comprising a coating layer formed by curing the photocurable resin composition of the present invention and a base material layer.
  • (A) (a) a silicone polyol represented by the general formula (1), (b) an isocyanate, and (c) a (meth) acrylate monomer having a functional group capable of reacting with isocyanate at the terminal.
  • a dimethyl silicone (meth) acrylate oligomer obtained by reacting with (B) a photopolymerizable oligomer and / or (C) a photopolymerizable monomer, (D) a fluorine-containing compound, and (E) a photopolymerization initiator.
  • a photocurable resin composition capable of improving the slipperiness.
  • curing this photocurable resin composition is provided, and the water surrounding member and functional panel with favorable slipperiness
  • the photocurable resin composition of the present invention comprises (A) a dimethyl silicone (meth) acrylate oligomer, (B) a photopolymerizable oligomer and / or (C) a photopolymerizable monomer, (D) a fluorine-containing compound, ( E) a photopolymerization initiator, and (F) other components as required.
  • the synergistic effect of (D) fluorine-containing compound having low surface energy and high water repellency and (A) dimethylsilicone (meth) acrylate oligomer having high slipperiness for example, the synergistic effect of (D) fluorine-containing compound having low surface energy and high water repellency and (A) dimethylsilicone (meth) acrylate oligomer having high slipperiness.
  • the slipperiness of the water-surrounding member and the functional panel having a coating layer derived from the photocurable resin composition can be improved.
  • the photocurable resin composition of the present invention as a result of segregation of (A) dimethyl silicone (meth) acrylate oligomer and (D) fluorine-containing compound on the surface, for example, derived from the photocurable resin composition
  • the performance such as the slipperiness of the water-surrounding member and the functional panel including the coating layer can be improved.
  • the (A) dimethyl silicone (meth) acrylate oligomer used in the photocurable resin composition of the present invention comprises (a) a silicone polyol component, (b) an isocyanate component, and (c) a (meth) acrylate monomer component. Obtained by reaction.
  • the (A) dimethyl silicone (meth) acrylate oligomer is prepared by, for example, reacting (a) a silicone polyol with (b) an isocyanate to synthesize a silicone polyol prepolymer having an isocyanate group at a part or all of the terminals.
  • (c) (meth) acrylate monomer is added to the isocyanate group in the silicone polyol prepolymer.
  • isocyanates to obtain dimethylsilicone (meth) acrylate oligomers, it is possible to synthesize prepolymers with any number of repetitions, thereby allowing molecular weight or physical properties of the resulting oligomers (flexibility, strength, adhesion) In addition to being able to adjust the properties, etc., there is an advantage that compatibility design with the base resin is easy because any number of highly polar urethane bonds can be included in the molecule.
  • the number average molecular weight of the (A) dimethyl silicone (meth) acrylate oligomer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 700 to 40,000.
  • the number average molecular weight can be obtained from a retention time of a sample by preparing a calibration curve from a polystyrene standard by GPC. Tetrahydrofuran or chloroform can be used as the moving bed solvent for GPC.
  • a refractometer (RI), a UV detector, etc. can be used for a detector.
  • the number average molecular weight obtained by using such a method is less than 1000, the relative amount of dimethylsiloxane sites in the (A) dimethylsilicone (meth) acrylate oligomer will decrease, so that a sufficient effect can be exhibited. Therefore, it is necessary to increase the amount of addition.
  • the number average molecular weight exceeds 40,000, the compatibility between (A) dimethyl silicone (meth) acrylate oligomer and polymerizable (B) photopolymerizable oligomer and / or (C) photopolymerizable monomer is significantly reduced. As a result, the film surface becomes soft and the surface is easily damaged.
  • Dimethyl silicone (meth) acrylate oligomer is (a) silicone polyol represented by general formula (1), (b) isocyanate, (c) (meth) acrylate having a functional group capable of reacting with isocyanate at the terminal.
  • (d) other polyol components may be included.
  • (a) a silicone polyol, (d) another polyol, and (b) an isocyanate are copolymerized to synthesize a silicone polyol prepolymer having an isocyanate group at part or all of the terminals.
  • a (meth) acrylate monomer having a functional group capable of reacting with isocyanate at the terminal is added to the isocyanate group in the silicone polyol prepolymer.
  • a (meth) acrylate monomer having a functional group capable of reacting with isocyanate at the terminal is added to the isocyanate group in the silicone polyol prepolymer.
  • (B) Photopolymerizable oligomer and / or (C) Photopolymerizability It is preferably 0.05% by mass to 10% by mass and more preferably 0.1% by mass to 5.0% by mass with respect to the total with the monomers (whole resin).
  • the content of the (A) dimethyl silicone (meth) acrylate oligomer is the amount of the active ingredient (solid content) of the (A) dimethyl silicone (meth) acrylate oligomer.
  • the lubricity of the article coated with the photocurable composition of the present invention may not be sufficiently improved, and if it is more than 10% by mass, The compatibility with (B) the photopolymerizable oligomer and / or (C) the photopolymerizable monomer may deteriorate, and a uniform cured product may not be obtained.
  • the content of the (A) dimethyl silicone (meth) acrylate oligomer is within the more preferable range, surface segregation of the (A) dimethyl silicone (meth) acrylate oligomer becomes remarkable, and the photocurable resin of the present invention.
  • the lubricity of the article coated with the composition can be expressed. Moreover, since the addition effect is almost saturated at 5.0%, it is advantageous from the viewpoint of cost to make the content of the (A) dimethyl silicone (meth) acrylate oligomer within the more preferable range.
  • the (a) silicone polyol used as one of the starting materials for the (A) dimethyl silicone (meth) acrylate oligomer is represented by the following general formula (1).
  • n is such that the number average molecular weight of the (A) dimethyl silicone (meth) acrylate oligomer is 700 to 40000 (the number average molecular weight of the silicone polyol is 500 to 40000).
  • it represents an arbitrarily selected integer there is no particular limitation, and it can be appropriately selected according to the purpose.
  • R is not particularly limited as long as it is an alkylene group having 1 to 30 carbon atoms in total or a functional group having 1 to 30 carbon atoms having an ether bond. It can be appropriately selected depending on the case.
  • the alkylene group having 1 to 30 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene and octylene. And an alkylene group having 1 to 30 carbon atoms and having no ether bond.
  • the functional group having 1 to 30 carbon atoms having an ether bond is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the reason why the total number of carbon atoms in R is 30 or less is from the viewpoint of dimethyl silicone concentration, heat resistance, and the like.
  • R is preferably a propylene group or —C 3 H 6 —O—C 2 H 4 — from the viewpoint of easy availability in the market.
  • n is such that the number average molecular weight of the (A) dimethyl silicone (meth) acrylate oligomer is 700 to 40000 (the number average molecular weight of the silicone polyol is 500 to 40000). And so on) represents an arbitrarily selected integer, p represents an integer in the range of 0-9, and q represents an integer in the range of 3-9.
  • the commercial product of the (a) silicone polyol is not particularly limited and may be appropriately selected depending on the purpose.
  • p and q represent the integer within said range.
  • the compatibility with the base resin can be changed.
  • the silicone concentration in the structure is relatively lowered, so that a sufficient function cannot be exhibited.
  • p and q are within the above ranges, there is no influence on the purpose of improving the slipperiness (slidability capable of easily removing water droplets on the surface), which is the object of the present invention, and the function is fully expressed. can do.
  • the (a) silicone polyol can be produced, for example, by addition reaction of a terminal Si—H group-containing dimethylpolysiloxane and a compound having a hydroxyl group and an alkenyl group at each end with a platinum catalyst.
  • the number average molecular weight (Mn) of the (a) silicone polyol is not particularly limited as long as it is 500 to 20000, and can be appropriately selected according to the purpose.
  • the number average molecular weight can be obtained from a retention time of a sample by preparing a calibration curve from a polystyrene standard by GPC. Tetrahydrofuran or chloroform can be used as the moving bed solvent for GPC.
  • a refractometer (RI), a UV detector, etc. can be used for a detector.
  • the number average molecular weight is less than 500, the relative amount of dimethylsiloxane sites in the structure decreases, so in order to exert a sufficient effect, it is necessary to increase the amount of addition, and if it exceeds 20000, (A) Compatibility with dimethyl silicone (meth) acrylate oligomer and polymerizable (B) photopolymerizable oligomer and / or (C) photopolymerizable monomer is significantly reduced and separated, and the crosslinking density is reduced. By doing so, the film surface becomes soft and the surface is easily damaged.
  • the (b) isocyanate used as one of the starting materials for the (A) dimethylsilicone (meth) acrylate oligomer is not particularly limited and may be appropriately selected depending on the intended purpose. Polyisocyanate compounds having
  • the (A) dimethyl silicone (meth) acrylate oligomer itself derived from the isocyanate also has a cyclic skeleton in the molecular structure.
  • the cyclic skeleton present in the molecular structure of the (A) dimethylsilicone (meth) acrylate oligomer may become steric hindrance, and the (A) dimethylsilicone (meth) acrylate oligomer may sink into the photocurable resin composition.
  • (A) dimethyl silicone (meth) acrylate oligomer segregates on the surface.
  • the polyisocyanate compound (b) having a cyclic skeleton in the molecular structure is particularly limited as long as it has a cyclic skeleton (cyclic structure portion) in the molecular structure and a plurality of isocyanate groups (NCO groups). And can be appropriately selected according to the purpose.
  • NDI naphthalene diisocyanate
  • TDI tolylene diisocyanate
  • XDI xylene diisocyanate
  • IPDI isophorone diisocyanate
  • MDI diphenylmethane diisocyanate
  • PPDI paraphenylene diisocyanate
  • TODI tolidine diisocyanate
  • DADI dicyclohexylmethane diisocyanate
  • H12MDI 1,3-bis (isocyanatomethyl) cyclohexa
  • TMXDI tetramethyl xylene diisocyanate
  • NDI naphthalene diisocyanate
  • TDI tolylene diisocyanate
  • XDI xylene diisocyanate
  • IPDI isophorone diisocyanate
  • the amount of the (a) silicone polyol and (b) isocyanate used can be appropriately changed.
  • the equivalent ratio of the isocyanate group (—NCO) in the isocyanate to the hydroxyl group in the (a) silicone polyol (—NCO) / -OH) is preferably in the range of more than 100/100 and not more than 300/100.
  • a urethane prepolymer having (b) isocyanate and (a) a hydroxyl group in the silicone polyol is reacted to have an isocyanate group at a part or all of the terminals.
  • the equivalent ratio (—NCO / —OH) of the isocyanate group (—NCO) in (b) isocyanate and the hydroxyl group in (a) silicone polyol may be made larger than 1.
  • the equivalent ratio (-NCO / -OH) of the isocyanate group (-NCO) in the isocyanate (b) to the hydroxyl group in the silicone polyol (a) greater than 1, a prepolymer having isocyanate groups at both ends is obtained.
  • This isocyanate group can be used to react with a functional group (for example, an isocyanate group) in the (c) (meth) acrylate monomer.
  • a catalyst for urethanization reaction is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the urethanization reaction catalyst is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the (c) (meth) acrylate monomer used as one of the starting materials for the (A) dimethyl silicone (meth) acrylate oligomer is not particularly limited as long as it contains a functional group capable of reacting with isocyanate at the end, It can be appropriately selected according to the purpose.
  • the functional group capable of reacting with the isocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydroxyl group (—OH), a carboxyl group (—COOH), a primary amino group, and a secondary amino group. Group, and the like. Among these, a hydroxyl group is preferable in terms of good reactivity with the isocyanate, a wide variety of commercially available products, and easy availability.
  • the (meth) acrylate monomer having a hydroxyl group (—OH) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Examples include acrylate, trimethylolpropane di (meth) acrylate, and pentaerythritol tri (meth) acrylate.
  • the (meth) acrylate monomer having a carboxyl group (—COOH) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the (meth) acrylate monomer having an amino group is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a (meth) acrylic acid ester whose side chain is a 1-aminoethyl group And (meth) acrylic acid ester which is a 1-aminopropyl group.
  • the (meth) acrylate monomer may contain both a functional group capable of reacting with isocyanate and a photopolymerizable (meth) acryloyl group in the structure. Any number of the (meth) acryloyl groups can be used, but the larger the number (polyfunctional), the more the (A) dimethyl silicone (meth) acrylate oligomer becomes polyfunctional.
  • (meth) acrylate monomers have higher reactivity with (B) photopolymerizable oligomers or (C) photopolymerizable monomers, but the higher the number of functional groups, the more reactive the steric hindrance. The rate may decrease.
  • the (meth) acrylate monomer preferably has a functional group number of 2 to 10, and a larger number is more preferable (closer to 10) between them.
  • the (meth) acrylate monomer is more preferable as the number of functional groups is increased because the crosslinks become denser and can stably segregate on the surface and increase the surface hardness.
  • Said (c) (meth) acrylate monomer may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the (c) (meth) acrylate monomer used can be appropriately changed.
  • a reaction product (urethane prepolymer) comprising a polyisocyanate compound in which a silicone polyol and (b) isocyanate have a cyclic skeleton in the molecular structure.
  • the equivalent (functional group / -NCO) of the functional group capable of reacting with the isocyanate in the (c) (meth) acrylate monomer may be used more than 1 equivalent to the isocyanate group (-NCO) in the polymer).
  • the (B) photopolymerizable oligomer and / or (C) photopolymerizable monomer used in the photocurable resin composition of the present invention is a radical polymerizable reactive group such as a (meth) acryloyl group [CH 2 ⁇ CHCO— Or CH 2 ⁇ C (CH 3 ) CO—] and the like.
  • a radical polymerizable reactive group such as a (meth) acryloyl group [CH 2 ⁇ CHCO— Or CH 2 ⁇ C (CH 3 ) CO—] and the like.
  • the above (A) dimethyl silicone (meth) acrylate oligomer is excluded from the (B) photopolymerizable oligomer.
  • the blending amount of (B) the photopolymerizable oligomer and (C) the photopolymerizable monomer is 100: 0 to 0: 100, preferably 80:20 to 20:80, more preferably 30: by mass ratio. It is in the range of 70 to 70:30.
  • the (B) photopolymerizable oligomer is not particularly limited and may be appropriately selected depending on the intended purpose. However, an acryloyloxy group [CH 2 ⁇ CHCOO—] or a methacryloyloxy group [CH 2 ⁇ C (CH 3 ) A (meth) acrylate oligomer having one or more COO—] is preferred, and a (meth) acrylate oligomer having a 1,2-polybutylene oxide unit is particularly preferred.
  • the (meth) acrylate oligomer having the 1,2-polybutylene oxide unit has low polarity, it has good compatibility with (A) dimethyl silicone (meth) acrylate oligomer, and (A) dimethyl silicone (meth) acrylate is widely used. It is possible to add oligomers. Therefore, even when the amount of (A) dimethyl silicone (meth) acrylate oligomer added is large, it is possible to suppress white turbidity, layer separation, etc., uniform properties after curing, and good appearance of the coating film.
  • the used water-surrounding member and the functional panel can also form good physical properties and appearance.
  • the low polarity of the (meth) acrylate oligomer (A) can be specifically represented by a value of n-heptane tolerance, and such value is preferably 0.5 g / 10 g or more, more preferably Is 0.7 g / 10 g or more.
  • the n-heptane tolerance means the value of the amount (g) of n-heptane that can be added until 10 g of the resin is kept at 25 ° C. while adding n-heptane dropwise and becoming cloudy. It becomes an index of solubility in a solvent, and the larger the value, the lower the polarity.
  • (meth) acrylate oligomer there is no restriction
  • a urethane type (meth) acrylate oligomer an epoxy-type (meth) acrylate oligomer, an ether type (meth) acrylate oligomer , Ester (meth) acrylate oligomers, polycarbonate (meth) acrylate oligomers, silicone (meth) acrylate oligomers, and the like.
  • (meth) acrylate oligomers include polyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, bisphenol A type epoxy resin, phenol novolac type epoxy resin, adducts of polyhydric alcohol and ⁇ -caprolactone, (meth) It can be synthesized by reaction with acrylic acid or by urethanizing a polyisocyanate compound and a (meth) acrylate compound having a hydroxyl group.
  • the photopolymerizable oligomer (B) may be a monofunctional oligomer, a bifunctional oligomer, or a polyfunctional oligomer, and is multifunctional from the viewpoint of realizing an appropriate crosslinking density of the resulting photocurable resin composition.
  • An oligomer is preferable.
  • urethane (meth) acrylate oligomers excellent in chemical resistance are preferable from the viewpoint of imparting suitable characteristics as a water-surrounding member and a functional panel.
  • the urethane-based (meth) acrylate oligomer may be, for example, a urethane prepolymer synthesized from (i) a polyol and (ii) polyisocyanate, and (iii) a compound having a functional group capable of reacting with isocyanate in the urethane prepolymer, For example, it can be produced by adding a (meth) acrylate having a hydroxyl group.
  • the polyol used for the synthesis of the urethane prepolymer is not particularly limited as long as it is a compound having a plurality of hydroxyl groups (—OH), and can be appropriately selected according to the purpose.
  • polyether polyol, polyester polyol examples thereof include polytetramethylene glycol, polybutadiene polyol, alkylene oxide-modified polybutadiene polyol, and polyisoprene polyol. These may be used individually by 1 type and may use 2 or more types together.
  • the polyether polyol can be obtained by addition polymerization.
  • an alkylene oxide such as ethylene oxide or propylene oxide is added to a polyhydric alcohol such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, or sorbitol.
  • a polyether polyol by ring-opening polymerization.
  • the polyether polyol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran (THF).
  • the polyester polyol can be obtained by addition polymerization, for example, a polyhydric alcohol such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, propylene glycol, trimethylolethane, trimethylolpropane, and the like.
  • a polyvalent carboxylic acid such as adipic acid, glutaric acid, succinic acid, sebacic acid, pimelic acid, and suberic acid
  • a polyester polyol can also be obtained by ring-opening polymerization.
  • the polyester polyol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a lactone polyester polyol obtained by ring-opening polymerization of ⁇ -caprolactone.
  • the (meth) acrylate oligomer having the 1,2-polybutylene oxide unit can be produced.
  • the butylene oxide-modified polyol is a polyether polyol obtained by addition polymerization of 1,2-butylene oxide (BO) to a polyhydric alcohol in the presence of an alkali catalyst. Further, it may be a polyether polyol obtained by addition polymerization of not only 1,2-butylene oxide (BO) but also other alkylene oxides such as propylene oxide (PO).
  • the ratio of 1,2-butylene oxide (BO) to other alkylene oxide is 20:80 to 100: 0, preferably 50:50 to 100: 0, in terms of molar ratio.
  • the number average molecular weight of these butylene oxide-modified polyols by GPC is usually 100 to 15000, preferably 500 to 5000.
  • the polyisocyanate is not particularly limited as long as it is a compound having a plurality of isocyanate groups (—NCO), and can be appropriately selected according to the purpose.
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • Crude MDI Crude diphenylmethane diisocyanate
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • HDI hexamethylene diisocyanate
  • HDI hexamethylene diisocyanate
  • the urethanization reaction catalyst is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the amount of the catalyst for urethanization reaction is not particularly limited and may be appropriately selected depending on the intended purpose, but is 0.001 to 2.0 parts by mass with respect to 100 parts by mass of (i) polyol. Part by mass is preferred.
  • the compound having a functional group capable of reacting with isocyanate (iii) to be added to the urethane prepolymer has at least one functional group (for example, hydroxyl group) capable of reacting with isocyanate, and exhibits a photopolymerizability ( A compound having one or more (meth) acryloyloxy groups [CH 2 ⁇ CHCOO— or CH 2 ⁇ C (CH 3 ) COO—]).
  • the compound having a functional group capable of reacting with (iii) isocyanate can be added to the isocyanate group in the urethane prepolymer.
  • the compound having a functional group capable of reacting with (iii) isocyanate is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the glass transition temperature exhibited by the coating layer obtained by curing the photocurable resin composition can be optimized, and an effect excellent in slipperiness can be obtained.
  • the photocurable composition which can be exhibited can be obtained.
  • the (C) photopolymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a (meth) acrylate monomer having one or more-] is preferable, and any of (i) a monofunctional monomer, (ii) a bifunctional monomer, and (iii) a polyfunctional monomer may be used.
  • the (C) photopolymerizable monomer may be used alone or in combination of two or more.
  • the SP value is the SP value possessed by each monomer and the SP value possessed by each monomer in each blending ratio (mass ratio) (each monomer when the total amount of monomers is 1). It is the value obtained by multiplying these by the ratio.
  • the monofunctional monomer (i) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, (meth) acryloylmorpholine, 2-hydroxyethyl (meth) ) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate , Butyl (
  • the (ii) bifunctional monomer is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a trimethylol propane tri (meth) acrylate an ethoxylated trimethylol propane tri (meth) acrylate, propoxy Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol monohydroxypenta (Meth) acrylate, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
  • solubility parameter (SP value) of the said photopolymerizable monomer there is no restriction
  • the lower limit of the SP value is not particularly limited, but is usually preferably 17.0 (J / cm 3 ) 0.5 or more.
  • Low SP value improves compatibility with (A) dimethylsilicone (meth) acrylate oligomer and (D) fluorine-containing compound, and (A) dimethylsilicone (meth) acrylate oligomer and (D) fluorine-containing over a wide range It is possible to add compounds. Therefore, even when the addition amount of (A) dimethyl silicone (meth) acrylate oligomer and (D) fluorine-containing compound is large, white turbidity, layer separation, etc. can be suppressed, and the appearance after curing is good. The functional panel can also form a good appearance.
  • the SP value can be estimated only from the chemical structure according to the Fedors method (see “Solubility Parameter Values”, Polymer Handbook, 4th edition (edited by J. Brandrup et al.)).
  • the SP value means a value calculated by the Fedors method, and the lower the value, the lower the polarity of the photopolymerizable monomer (C).
  • R 1 is a hydrogen atom or a methyl group
  • R 2 is an n-valent hydrocarbon group having 5 to 20 carbon atoms, does not contain a hetero atom, and may be a chain or a ring. There may be. Further, —CH 2 — in the group may be replaced with —CH ⁇ CH—.
  • n is an integer of 1 to 4.
  • R 2 is an alkyl group having 5 to 20 carbon atoms
  • R 2 is carbon. It becomes an alkylene group of several 5 to 20.
  • R 2 is an alkanetriyl group having 5 to 20 carbon atoms
  • R 2 is an alkane having 5 to 20 carbon atoms. Tetrayl group.
  • R 2 examples include —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH (CH 3 ) CH 3 , cyclohexyl group, cycloheptane group, cyclooctane group, cyclononane group, cyclodecane group, and the like.
  • alkanetriyl groups such as those represented by C (CH 2 —) 4 .
  • the carbon number of R 2 is less than 5, in the case of a chain hydrocarbon group, the SP value of the monomer tends to increase, and (A) a dimethyl silicone (meth) acrylate oligomer and (D) a fluorine-containing compound
  • the compatibility with the above is lowered, and in the case of a cyclic hydrocarbon group, it is difficult to obtain it.
  • the number of carbon atoms of R 2 exceeds 20, crosslinking density of the photocurable composition obtained tends to decrease. If the crosslink density is lowered more than necessary, a dye such as a hair color tends to be leached into the coating layer, and the panel may be dyed.
  • the monomer represented by the general formula (A) include, for example, isobornyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, isoamyl (meth) ) Acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, cyclohexanedimethanol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate
  • Tricyclodecane di (meth) acrylate is preferable, and 1,6-hexanediol di (meth) acrylate, isobornyl (meth) acrylate, and 1,9-nonanediol di (meth) acrylate are more preferable.
  • SP value solubility parameter
  • the resin obtained by curing the photocurable composition has high hydrophobicity, it is highly resistant to water and stains such as detergents and hair colors used around the water, is difficult to get dirty, and is slippery. Is more stable.
  • the number of functional groups of the photopolymerizable monomer is usually 1 to 6, and preferably 1 to 4.
  • the number of functional groups is 1, the crosslinking density tends to decrease.
  • the glass transition temperature becomes high and good film properties can be maintained.
  • the number of functional groups is 2 to 6, preferably 2 to 4, the crosslinking reaction of the photocurable composition tends to be appropriately maintained. It is presumed that the phenomenon in which the water-surrounding member and the functional panel are dyed can be more effectively suppressed. Therefore, in this case as well, a water-surrounding member and a functional panel in which a coating layer having suitable curability is formed while effectively retaining not only good antifouling properties but also chemical resistance and dyeing resistance are provided. Obtainable.
  • the photopolymerizable oligomer and the (C) photopolymerizable monomer may be used only as an oligomer or as a monomer, but it is preferable to use a combination of the oligomer and the monomer.
  • the photocurable composition of the present invention further comprises (D) a fluorine-containing compound.
  • (D) fluorine-containing compound By including the (D) fluorine-containing compound, the water repellency and water slidability of the photocurable composition can be improved.
  • fluorine-containing compound Any fluorine-containing compound can be used as the fluorine-containing compound.
  • photocuring containing (A) dimethyl silicone (meth) acrylate oligomer, (B) photopolymerizable oligomer and / or (C) photopolymerizable monomer, and (E) photopolymerization initiator.
  • the fluorine-containing compound (D) preferably has a photopolymerizable functional group (reactive group) in the structure in the sense that it is immobilized in the system by reacting with the functional composition.
  • (D) fluorine-containing compound there is no restriction
  • the commercial product of the (D) fluorine-containing compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include light acrylate FA-108 (manufactured by Kyoeisha Chemical Co., Ltd.), RS-75 (DIC stock).
  • the mass ratio (A / D) of the solid content of the (A) dimethyl silicone (meth) acrylate oligomer to the solid content of the (D) fluorine-containing compound is preferably in the range of 0.2 to 10.0. A range of 0.4 to 3.0 is more preferable.
  • the mass ratio (A / D) is an effective component ratio (solid content ratio) of (A) dimethylsilicone (meth) acrylate oligomer and (D) fluorine-containing compound in the photocurable composition.
  • both (D) fluorine-containing compound-derived high water repellency and (A) dimethylsilicone (meth) acrylate oligomer-derived water repellency can be expected, If it is 0.4 or more, the concentration of the surface fluorine-containing compound and (A) dimethylsilicone (meth) acrylate oligomer will be high, so the above-described effects can be expected more.
  • the content of the (D) fluorine-containing compound is 0.05 mass relative to a total of 100 mass parts of the (B) photopolymerizable oligomer and (C) photopolymerizable monomer.
  • the range is preferably from 5.0 parts by weight to 5.0 parts by weight, and more preferably from 0.1 parts by weight to 3.0 parts by weight.
  • the content of the fluorine-containing compound (D) is the amount (the amount of solid content) of the active ingredient of the fluorine-containing compound (D).
  • the (E) photopolymerization initiator used in the photocurable resin composition of the present invention is the above-described (A) dimethyl silicone (meth) acrylate oligomer and (B) photopolymerizable when irradiated with light such as ultraviolet rays. It has the effect
  • the (E) photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose.
  • 4-dimethylaminobenzoic acid 4-dimethylaminobenzoic acid ester, 2,2-dimethoxy- Benzophenone derivatives such as 2-phenylacetophenone, acetophenone diethyl ketal, alkoxyacetophenone, benzyldimethyl ketal, benzophenone and 3,3-dimethyl-4-methoxybenzophenone, 4,4-dimethoxybenzophenone, 4,4-diaminobenzophenone, benzoylbenzoic acid Alkyl, bis (4-dialkylaminophenyl) ketone, benzyl derivatives such as benzyl and benzylmethyl ketal, benzoin derivatives such as benzoin and benzoin isobutyl ether, benzoin isopropyl ether, 2-hydroxy-2-methylpropyl Piophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, xanthone, thioxan
  • (A) Dimethyl silicone (meth) acrylate A range of 0.1 to 10 parts by mass is preferable with respect to 100 parts by mass in total of the oligomer and (B) the photopolymerizable oligomer and / or (C) the photopolymerizable monomer (D) fluorine-containing compound. If the blending amount of the (E) photopolymerization initiator is 0.1 parts by mass or more, the polymerization reaction can be sufficiently started. On the other hand, if it exceeds 10 parts by mass, the effect of initiating the polymerization reaction is saturated. On the other hand, coloring becomes remarkable, and the cost of the raw material of the photocurable resin composition increases.
  • the photocurable resin composition of the present invention may further contain a photosensitizer as necessary in consideration of the required curing reactivity and stability.
  • the photosensitizer absorbs energy when irradiated with light, and the energy or electrons move to the polymerization initiator to initiate polymerization.
  • Examples of the photosensitizer include p-dimethylaminobenzoic acid isoamyl ester.
  • photosensitizers are blended in a total amount of 100 parts by mass of (A) a photopolymerizable silicone oligomer, (B) a photopolymerizable oligomer and / or (C) a photopolymerizable monomer, and (D) a fluorine-containing compound.
  • A a photopolymerizable silicone oligomer
  • B a photopolymerizable oligomer and / or
  • C a photopolymerizable monomer
  • D a fluorine-containing compound.
  • the range of 0.1 to 10 parts by mass is preferable.
  • the photocurable resin composition of the present invention may contain a polymerization inhibitor as necessary in consideration of the required curing reactivity and stability.
  • the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butyl-p-cresol, butylhydroxyanisole, Examples include 3-hydroxythiophenol, ⁇ -nitroso- ⁇ -naphthol, p-benzoquinone, 2,5-dihydroxy-p-quinone, and the like.
  • polymerization inhibitors are added in a total amount of 100 parts by mass of (A) dimethyl silicone (meth) acrylate oligomer and (B) photopolymerizable oligomer and / or (C) photopolymerizable monomer (D) fluorine-containing compound.
  • A dimethyl silicone (meth) acrylate oligomer
  • B photopolymerizable oligomer
  • C photopolymerizable monomer
  • fluorine-containing compound the range of 0.1 to 10 parts by mass is preferable.
  • the photocurable resin composition of the present invention may contain an organic solvent such as ether, ketone or ester as a diluent solvent.
  • organic solvent include propylene glycol monomethyl ether acetate (PMA), methyl ethyl ketone ( MEK), methyl isobutyl ketone (MIBK), acetone, butyl lactate and the like. These dilution solvents may be used individually by 1 type, and may use 2 or more types together.
  • the photocurable resin composition of the present invention can be applied as a coating liquid to a surface on a substrate using a diluting solvent as necessary.
  • the method for applying is not particularly limited, and a known method can be employed. For example, gravure coating, roll coating, reverse coating, knife coating, die coating, lip coating, doctor coating, extrusion coating, slide coating, Examples thereof include wire bar coating, curtain coating, extrusion coating, and spin coating.
  • the water-surrounding member includes an application layer formed by curing the photocurable composition of the present invention and a base material layer.
  • the water-surrounding member is a member that requires water drainage on the surface.
  • the water-surrounding member is not particularly limited and may be appropriately selected depending on the purpose. For example, the kitchen sink, kitchen wall material, wash basin, bathroom wall material, bathtub, bathroom ceiling material, bathroom use Floor materials, bathroom counters, toilets, water storage tanks, etc.
  • the functional panel of the present invention comprises a coating layer formed by curing the photocurable resin composition of the present invention and a base material layer, for example, the coating layer is formed on the base material layer.
  • a coating layer formed by curing the photocurable resin composition of the present invention and a base material layer, for example, the coating layer is formed on the base material layer.
  • the coating layer is formed on the base material layer.
  • the coating layer may be formed on both the front surface and the back surface of the base material layer, and if necessary, in addition to the base material layer and the coating layer, a multilayer in which an intermediate layer made of various materials is formed between these layers. It is good also as a structure. In this case, since the coating layer has excellent slipperiness as described above, it is desirable to form the coating layer as the outermost surface layer of the functional panel.
  • the intermediate layer is not particularly limited and may be appropriately selected depending on the purpose.
  • the undercoat layer for improving the adhesion between the base material layer and the coating layer, the design of the functional panel examples thereof include a decorative layer provided with a pattern or color for improvement.
  • the functional panel of the present invention thus obtained has excellent slipperiness due to the formation of the coating layer on the base material layer, and has abrasion resistance, chemical resistance, warm water resistance and dyeing resistance. It is also excellent in properties, and it is difficult to cause alteration or deterioration even by using a highly irritating cleaning agent containing acid or alkali while effectively suppressing the adhesion of various types of dirt typified by scale. Further, discoloration and dyeing hardly occur even when a dyeing agent such as a hair color is used. Therefore, the functional panel of the present invention is particularly suitable as a functional panel disposed in a bathroom or kitchen in a house.
  • An application layer can be formed on a base material layer by applying the photocurable resin composition of the present invention on a base material, and then making it photocure.
  • a method of photocuring a method of irradiating light such as ultraviolet rays is common.
  • the surface on the base material layer forming the coating layer may be only one surface or both surfaces of the front surface and the back surface, and may be appropriately selected as necessary.
  • the irradiation amount of light at the time of curing the photocurable resin composition of the present invention is not particularly limited and can be appropriately selected according to the purpose.
  • the irradiation intensity is usually 20 mW / cm 2 ⁇ 2000mW / cm 2, an irradiation amount 100mJ / cm 2 ⁇ 5000mJ / cm 2, thereby, the photocurable resin composition of the present invention is cured in the usual several seconds to several tens of seconds.
  • the productivity of the functional panel obtained can be improved.
  • the thickness of the coating layer is not particularly limited and may be appropriately selected depending on the purpose from the required design properties and chemical resistance, but it is usually in the range of 1 ⁇ m to 200 ⁇ m. It is assumed.
  • the ultraviolet curing reaction is a radical reaction, it is susceptible to inhibition by oxygen. Therefore, after apply
  • the material of the base material layer used in the functional panel of the present invention is not particularly limited and can be appropriately selected according to the purpose.
  • a material obtained by adding glass fiber or carbon fiber to an organic material so-called FRP (fiber reinforced plastic) is preferable.
  • FRP fiber reinforced plastic
  • the FRP is not particularly limited and can be appropriately selected depending on the purpose.
  • the FRP is a sheet-like sheet molding compound (SMC) containing an unsaturated polyester resin, a filler and glass fiber or carbon fiber, SMC,
  • the composite material include a bulk bulk molding compound (BMC) including short fibers.
  • the FRP generally contains a thermosetting resin, an organic peroxide (curing agent), a filler, a low shrinkage agent, an internal mold release agent, a reinforcing material, a crosslinking agent, a thickener, and the like. These are used by being put in a mold set at a predetermined temperature and pressurized, and formed into a shape corresponding to a place to be arranged as a building material.
  • the FRP containing unsaturated polyester as a thermosetting resin, a filler, and glass fiber or carbon fiber as a reinforcing material can further improve the strength and durability of the entire functional panel obtained. it can.
  • the unsaturated polyester includes unsaturated polybasic acids such as maleic anhydride and fumaric acid, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, trimethylpentanediol, neopentyl glycol, trimethylpropane mono It is produced from polyhydric alcohols such as allyl ether, hydrogenated bisphenol and bisphenol dioxypropyl ether.
  • unsaturated polybasic acids such as maleic anhydride and fumaric acid
  • the filler is not particularly limited and may be appropriately selected depending on the intended purpose.
  • Examples thereof include calcium carbonate and aluminum hydroxide.
  • calcium carbonate is preferable from the viewpoint of cost reduction
  • aluminum hydroxide is preferable from the viewpoint of improving the chemical resistance of FRP itself.
  • the coating layer is formed, the chemical resistance of the entire functional panel can be sufficiently improved even if FRP using calcium carbonate as a filler is used as a base material.
  • a functional panel having a base material layer made of low-cost FRP can be easily realized.
  • the glass fiber and carbon fiber as the reinforcing material are not particularly limited and may be appropriately selected depending on the intended purpose, but those having a fiber length of about 20 mm to 50 mm and a fiber diameter of about 5 ⁇ m to 25 ⁇ m are preferable. It is preferably used and contained in the FRP in an amount of 10 mass% to 70 mass%.
  • the FRP used as the base material layer is manufactured as an FRP having a predetermined thickness and size by mixing these components and using an FRP manufacturing apparatus or the like.
  • VESTANAT IPDI isophorone diisocyanate
  • urethane prepolymer solution 0.2 mol of pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) is added to the total amount of the obtained prepolymer solution, and further stirred for 4 hours to complete the reaction, and dimethylsilicone (meth) having a number average molecular weight of about 3000.
  • PE-3A pentaerythritol triacrylate
  • Production Example 9 In Production Example 1, instead of adding pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.), 2-hydroxyethyl acrylate (trade name: Light Ester HOA, manufactured by Kyoeisha Chemical Co., Ltd.) was added. In the same manner as in Production Example 1, a dimethyl silicone (meth) acrylate oligomer having a number average molecular weight of about 3000 was obtained.
  • PE-3A pentaerythritol triacrylate
  • 2-hydroxyethyl acrylate trade name: Light Ester HOA, manufactured by Kyoeisha Chemical Co., Ltd.
  • Production Example 10 In Production Example 1, instead of adding pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.), dipropylene glycol acrylate (trade name: DPGA, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added. In the same manner as in Production Example 1, a dimethyl silicone (meth) acrylate oligomer having a number average molecular weight of about 3000 was obtained.
  • PE-3A pentaerythritol triacrylate
  • DPGA dipropylene glycol acrylate
  • Production Example 11 In Production Example 1, instead of adding pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.), 2-acryloyloxyethyl succinate (trade name: A-SA, manufactured by Shin-Nakamura Chemical Co., Ltd.) was added. Except that, a dimethyl silicone (meth) acrylate oligomer having a number average molecular weight of about 3000 was obtained in the same manner as in Production Example 1.
  • PE-3A pentaerythritol triacrylate
  • A-SA manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Production Example 13 Polyethylene glycol having a number average molecular weight of 1000 (PEG # 1000, NOF Corporation) was not added, and instead of adding 0.3 mol of isophorone diisocyanate, 0.2 mol of isophorone diisocyanate was added. In the same manner as in Production Example 1, a dimethyl silicone (meth) acrylate oligomer having a number average molecular weight of about 2000 was obtained.
  • the slipping property was evaluated by measuring the falling angle of water.
  • DM-500 and DM-SA manufactured by Kyowa Interface Science Co., Ltd. were used for evaluation of slipperiness.
  • a 30 ⁇ L water droplet was dropped on the substrate, the stage was tilted at a speed of 7.5 degrees / second, and the angle at which the water droplet began to move was taken as the value of the falling angle.
  • the measurement was performed twice, and the average value was taken as the value of the sliding angle.
  • Dimethylsilicone (meth) acrylate oligomer obtained (manufactured by Miwon, “SIU2400”, number average molecular weight: about 7000, number of functional groups: 10) * 4 Dimethylsilicone (meth) acrylate oligomer obtained in Production Example 1 * 4-2 Dimethylsilicone (meth) acrylate oligomer obtained in Production Example 2 * 4-3 Dimethylsilicone (meth) obtained in Production Example 3
  • R is an alkyl group in order to eliminate terminal reactivity, and has no essential contribution to the present invention.
  • * 6 “FM-7711” manufactured by Chisso Corporation, methacryl-modified dimethyl silicone oil at both ends, number average molecular weight (Mn) 1000, specific gravity 0.98, refractive index 1.419, viscosity 20 mm 2 / s, the following general formula ( 4) a compound outside the scope of claims
  • Me represents a methyl group and n represents arbitrary integers.
  • Polyol was obtained by adding 12 mol of butylene oxide to 1 mol of propylene glycol (manufactured by Kanto Chemical Co., Ltd.) at a reaction temperature of 110 ° C. using potassium hydroxide as a catalyst. To the polyol, 2 mol of 2,4-tolylene diisocyanate was charged into a reaction vessel equipped with a nitrogen gas introduction tube, a stirrer and a cooling tube, and reacted at 70 ° C. for 2 hours.

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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
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Abstract

La présente invention concerne une composition de résine polymérisable sous l'effet de la lumière et présentant des caractéristiques améliorées, notamment en termes de glissance. Ladite composition de résine polymérisable sous l'effet de la lumière contient : (A) un oligomère de (méth)acrylate de silicone diméthylique résultant de la réaction (a) d'un silicone polyol représenté par la formule générale (1), (b) d'un isocyanate et (c) d'un monomère de (méth)acrylate comportant un groupe fonctionnel terminal capable de réagir avec l'isocyanate ; (B) un oligomère photopolymérisable et/ou (C) un monomère photopolymérisable pouvant faire l'objet d'une copolymérisation avec l'oligomère de (méth)acrylate de silicone diméthylique (A) susmentionné ; (D) un composé contenant du fluor ; et (E) un initiateur de photopolymérisation. Dans la formule générale (1), n représente un nombre entier choisi librement de façon à ce que la masse moléculaire moyenne en nombre de l'oligomère de (méth)acrylate de silicone diméthylique se situe entre 700 et 40 000, bornes incluses ; et R représente un groupe alkylène en C1 à C30 ou un groupe fonctionnel en C1 à C30 comportant une liaison éther.
PCT/JP2012/004602 2011-07-19 2012-07-19 Composition de résine polymérisable sous l'effet de la lumière et élément de tuyauterie et panneau fonctionnel l'utilisant Ceased WO2013011693A1 (fr)

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WO2014034030A1 (fr) * 2012-08-28 2014-03-06 株式会社ブリヂストン Élément ayant une couche durcie formé par durcissement d'une composition de résine durcissable sur au moins une surface de celui-ci
CN110606932A (zh) * 2019-10-28 2019-12-24 广东昊辉新材料有限公司 一种光固化聚氨酯丙烯酸酯水分散体及其制备方法
CN111057203A (zh) * 2019-12-31 2020-04-24 北京松井工程技术研究院有限公司 硅氟聚氨酯丙烯酸树脂及其制备方法与应用
US20210163668A1 (en) * 2018-04-12 2021-06-03 Basf Se Electroactive polymers
JP2023000961A (ja) * 2021-06-17 2023-01-04 アイカ工業株式会社 無溶剤光硬化型樹脂組成物

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CN105733434B (zh) * 2014-12-26 2019-09-24 中国涂料株式会社 光固化性树脂组合物、及固化膜、带膜基材及其制造方法
EP4186933A4 (fr) * 2020-07-21 2024-08-07 Nitto Shinko Corporation Composé durcissable, composition durcissable et procédé de production de composition durcissable

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WO2014034030A1 (fr) * 2012-08-28 2014-03-06 株式会社ブリヂストン Élément ayant une couche durcie formé par durcissement d'une composition de résine durcissable sur au moins une surface de celui-ci
US20210163668A1 (en) * 2018-04-12 2021-06-03 Basf Se Electroactive polymers
CN110606932A (zh) * 2019-10-28 2019-12-24 广东昊辉新材料有限公司 一种光固化聚氨酯丙烯酸酯水分散体及其制备方法
CN111057203A (zh) * 2019-12-31 2020-04-24 北京松井工程技术研究院有限公司 硅氟聚氨酯丙烯酸树脂及其制备方法与应用
JP2023000961A (ja) * 2021-06-17 2023-01-04 アイカ工業株式会社 無溶剤光硬化型樹脂組成物
JP7734516B2 (ja) 2021-06-17 2025-09-05 アイカ工業株式会社 無溶剤光硬化型樹脂組成物

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