WO2015053397A1 - Composition de revêtement à photopolymérisation cationique, procédé de formation d'un film de revêtement et article revêtu de ce film - Google Patents

Composition de revêtement à photopolymérisation cationique, procédé de formation d'un film de revêtement et article revêtu de ce film Download PDF

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WO2015053397A1
WO2015053397A1 PCT/JP2014/077231 JP2014077231W WO2015053397A1 WO 2015053397 A1 WO2015053397 A1 WO 2015053397A1 JP 2014077231 W JP2014077231 W JP 2014077231W WO 2015053397 A1 WO2015053397 A1 WO 2015053397A1
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formula
group
hydrolyzable silane
coating composition
compound represented
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Japanese (ja)
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加藤　敦也
綾 境口
彰典 永井
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関西ペイント株式会社
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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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/08—Saturated oxiranes
    • C08G65/10—Saturated oxiranes characterised by the catalysts used
    • C08G65/105—Onium compounds
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • 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
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation

Definitions

  • the present invention relates to a photocation curable coating composition, a coating film forming method, and a coated article thereof.
  • Silsesquioxane is a general term for a series of network-like polysiloxanes having a basic structural unit of T units and a ladder-type, cage-type, and three-dimensional network type (random type) structure. Since this silsesquioxane is soluble in a general organic solvent, unlike silica, which is a complete inorganic substance represented by the general formula SiO 2 , it is easy to handle, processability such as film formation and the like. It has the feature of excellent moldability.
  • photocuring is a technology that modifies the surface of the substrate by irradiating and curing the viscous liquid applied to the substrate (metal, plastic, woodworking product, etc.) with light (for example, ultraviolet rays).
  • Photocuring is a technique that utilizes a chemical reaction initiated by light, and is classified into a radical polymerization system and a cationic polymerization system based on the difference in the initiation reaction mechanism.
  • radical polymerization systems cationic polymerization systems are less susceptible to cure inhibition by oxygen, cure shrinkage is small, and curing of areas where light irradiation does not reach because of the long life of active species and curing by heating gradually progress.
  • application to various fields has been studied.
  • Patent Documents 1 and 2 relate to a photocationic curable resin composition containing a silsesquioxane compound having an oxetanyl group and a cationic polymerization initiator.
  • This composition was excellent in surface hardness and compatibility, but was cured by being irradiated with ultraviolet rays 5 times, and when it was irradiated once with ultraviolet rays, its curability and scratch resistance were insufficient.
  • Patent Document 3 relates to a composition comprising an ultraviolet curable epoxy functional organopolysiloxane having an increased ability to solubilize an onium salt photoinitiator and an onium salt initiator.
  • This composition was excellent in compatibility with the onium salt initiator, but the scratch resistance was insufficient.
  • Patent Documents 4 and 5 relate to a cationic polymerization initiator having a cationic polymerization initiating ability.
  • this cationic polymerization initiator does not contain toxic elements such as arsenic and antimony, and has good compatibility with other cationic polymerizable compounds and excellent curability. However, this was a case where the curl resistance was insufficient.
  • JP-A-11-116682 Japanese Patent Laid-Open No. 11-199673 JP-A-1-297421 Japanese Patent Publication No. 2005-116038 JP 2012-22227 A
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photocationic curable coating composition having excellent transparency and curling resistance and scratch resistance of the resulting cured coating film, and It is providing the coating-film formation method.
  • a photocationic curable coating composition comprising a silsesquioxane compound (a) containing at least one photocationically polymerizable group and an iodonium salt photoacid generator (b),
  • the photocationically polymerizable group-containing silsesquioxane compound (a) is It is obtained by hydrolytic condensation of a hydrolyzable silane compound represented by formula (I) and / or a hydrolyzable silane compound represented by formula (II).
  • a photocationically curable coating composition Based on the total amount with the hydrolyzable silane compound represented by 55 to 100 mol% of a hydrolyzable silane compound represented by the formula (I), A photocationically curable coating composition, wherein the hydrolyzable silane compound represented by the formula (II) is 0 to 45 mol%.
  • R 1 represents a divalent alkylene group having 1 to 6 carbon atoms.
  • X is a halogen element or an alkoxy group having 1 to 6 carbon atoms, and the three Xs may be the same or different.
  • R 2 SiX 3 (II) [Formula (II) is a compound other than formula (I), and R 2 represents an optionally substituted monovalent organic group having 1 to 18 carbon atoms.
  • X is a halogen element or an alkoxy group having 1 to 6 carbon atoms, and the three Xs may be the same or different.
  • Item 2. The photocationic curable coating composition according to Item 1, wherein the photoacid generator (b) is an iodonium salt photoacid generator represented by the following formula (III).
  • R 3 represents an organic group bonded to I (iodine atom), and two R 3 s may be the same as or different from each other.
  • [Y] ⁇ is a phosphate anion represented by the formula (IV) or a boron compound anion represented by the formula (V), and Rf in the formula (IV) is fluorine in which all or part of the hydrogen atoms are fluorine.
  • An alkyl group which may be substituted with an atom is represented.
  • b is an integer of 0 to 5.
  • the b Rf's may be the same or different.
  • Item 3. Item 3.
  • Item 4. The photocationically curable coating composition according to any one of Items 1 to 3, further comprising a sensitizer (d).
  • Item 5 The photocationically curable coating composition according to any one of Items 1 to 4, wherein the epoxy equivalent of the photocationically polymerizable group-containing silsesquioxane compound (a) is 10 to 500 g / equivalent.
  • Item 6 When the cured coating film having a film thickness of 5 ⁇ m is formed on the acrylic resin plate having a thickness of 3 mm, the Martens hardness measured by a super micro hardness tester at a temperature of 23 ° C. and a load of 20 mN is 0.5. Item 6.
  • Item 7 A photocationically curable coating composition according to any one of Items 1 to 6 is applied on an object to be coated so that the dry film thickness is 1 to 10 ⁇ m, and setting and / or preheating is performed.
  • a coating film forming method characterized by irradiating with light after applying.
  • the present invention relates to an article having a film formed by the method for forming a coating film according to Item 7.
  • the photocationic curable coating composition of the present invention When the photocationic curable coating composition of the present invention is used, a cured coating film having excellent transparency can be obtained. Furthermore, according to the photocationic curable coating composition of the present invention, it is possible to obtain a cured coating film that can be cured at a low dose and that is excellent in curling resistance and scratch resistance of the resulting cured coating film.
  • the photocationic curable coating composition of the present invention contains a silsesquioxane compound (a) and an iodonium salt photoacid generator (b). This will be described in detail below.
  • silsesquioxane compound means only a silsesquioxane compound having a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed. Instead, it may also include a ladder structure in which Si—OH groups remain, an incomplete cage structure, and a random condensate silsesquioxane compound.
  • the ratio of the silsesquioxane compound having a structure in which all Si—OH groups are hydrolyzed and condensed is 80 mass% in the silsesquioxane compound as the component (a). % Or more, preferably 90% by mass or more, and more preferably 100% by mass from the viewpoint of liquid stability and scratch resistance.
  • the silsesquioxane compound (a) contains at least one cationic polymerizable group.
  • the cation polymerizable group means a group that polymerizes in the presence of an initiator that gives a cation, and specifically includes, for example, an epoxy group (for example, an alicyclic epoxy group, a glycidyl group). Etc.), oxetane ring, vinyl ether group, methylol group, alkoxymethylol group, dioxolane group, trioxane group, styryl group and the like.
  • the silsesquioxane compound (a) is obtained by hydrolytic condensation of a hydrolyzable silane represented by the formula (I) and / or a hydrolyzable silane represented by the formula (II). It is a thing.
  • R 1 represents a divalent alkylene group having 1 to 6 carbon atoms.
  • X is a halogen element or an alkoxy group having 1 to 6 carbon atoms, and the three Xs may be the same or different.
  • R 2 SiX 3 (II) [Formula (II) is a compound other than formula (I), and R 2 represents an optionally substituted monovalent organic group having 1 to 18 carbon atoms.
  • X is a halogen element or an alkoxy group having 1 to 6 carbon atoms, and the three Xs may be the same or different. ].
  • R 1 in the formula (I) is bonded to a silicon atom constituting the silsesquioxane compound.
  • a three-membered ring containing oxygen is generically called an oxirane ring or an epoxy group.
  • the “alicyclic epoxy group” refers to those having an epoxy group in the ring of a cycloaliphatic group such as a cyclohexane ring and a cyclooctane ring, and the silsesquiquine component (a) of the present invention.
  • an alicyclic epoxy group-containing hydrolyzable silane having a structure represented by the formula (I) is used as an essential component.
  • the silsesquioxane compound as the component (a) is excellent in compatibility and reactivity with the iodonium salt photoacid generator, and therefore in the presence of the photoacid generator. And cured by light irradiation. Therefore, the cured coating film obtained by the photocationic curable coating composition of the present invention is excellent in transparency.
  • the alicyclic epoxy group is a part of the cationic photopolymerizable group of the silsesquioxane compound as the component (a) or From the viewpoint of scratch resistance of the cured coating film, the content is preferably 55 to 100 mol%, more preferably 75 to 100 mol%, and particularly preferably 90 to 100 mol%. .
  • R 1 in the formula (I) is not particularly limited as long as it is a divalent hydrocarbon group having 1 to 6 carbon atoms. Specific examples include methylene group, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4-butylene group, hexylene group and the like. Among these, a divalent hydrocarbon group having 2 to 4 carbon atoms is preferable from the viewpoint of scratch resistance of the resulting cured coating film.
  • the silsesquioxane compound as component (a) has an alicyclic epoxy group in a specific ratio, but other organic groups are not particularly limited.
  • organic groups examples include organic groups such as alkyl groups such as methyl group and ethyl group, 3-glycidyloxypropyl group, glycidyl group, oxetanyl group, vinyl group and phenyl group. Especially, it is preferable that a glycidyl group, an oxetanyl group, or a methyl group is included from a sclerosing
  • the weight average molecular weight of the silsesquioxane compound (a) is from 1,000 to 100,000, more preferably from 1,000 to 100,000, from the viewpoint of the viscosity and paintability of the photocationic curable coating composition. Within the range of 10,000 is preferred.
  • the weight average molecular weight of the silsesquioxane compound as component (a) is “HLC (registered trademark) -8120GPC” (trade name, manufactured by Tosoh Corporation) as a gel permeation chromatograph.
  • TSKgel registered trademark
  • G4000HXL TSKgel (registered trademark) G4000HXL
  • TSKgel registered trademark) G3000HXL
  • TSKgel registered trademark) G2500HXL
  • TSKgel registered trademark
  • G2000HXL trade names, all manufactured by Tosoh Corporation
  • a total of four lines can be used, and a differential refractometer can be used as a detector, and measurement can be performed under conditions of mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., and flow rate: 1 mL / min.
  • silsesquioxane compound as component (a) can be obtained by combining a production method used for production of general silsesquioxane and a conventionally known chemical reaction. For example, the following production It can be manufactured using a method.
  • Manufacturing method p examples include a production method using a hydrolyzable silane having a photocationically polymerizable group as a starting material.
  • a hydrolyzable silane represented by the above formula (I) as a starting material is subjected to hydrolysis condensation in the presence of a catalyst to produce a silsesquioxane compound as component (a). Is mentioned.
  • R 1 represents a divalent alkylene group having 1 to 6 carbon atoms.
  • examples of the divalent alkylene group having 1 to 6 carbon atoms include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, n-pentylene group, n-hexylene group and the like. Is mentioned.
  • the alkylene group is preferably an alkylene group having 1 to 3 carbon atoms.
  • X is a halogen element or an alkoxy group having 1 to 6 carbon atoms, and the three Xs may be the same or different.
  • examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like.
  • examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, and an n-pentyloxy group. And n-hexyloxy group.
  • Specific examples of X include chlorine, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group and the like.
  • hydrolyzable silane represented by the formula (I) examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrichlorosilane and the like.
  • the hydrolyzable silane of the formula (II) other than the hydrolyzable silane represented by the formula (I) may be used, and hydrolytic condensation is performed together with the hydrolyzable silane represented by the formula (I).
  • the silsesquioxane compound is not particularly limited as long as it can produce the compound.
  • R 2 in the formula (II) is preferably a monovalent organic group having 1 to 18 carbon atoms from the viewpoint of scratch resistance, and may be linear or branched, and 1 to 3 (preferably 1 May have a cyclic structure and may contain a urethane bond, an ester bond, an ether bond, or the like.
  • the organic group represented by R 2 includes a hydrocarbon group (an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms (such as a phenyl group), an alkenyl group having 2 to 18 carbon atoms), Examples thereof include hydrocarbon groups interrupted by the urethane bond, ester bond, ether bond and the like.
  • the number of these bonds is not limited.
  • the number of the above-mentioned bonds per organic group is 1 to 3, preferably 1 Is mentioned.
  • the number of carbon atoms in the organic group includes the number of carbons included in these bonds.
  • the carbon number of the methylcarbamoylethyl group (CH 3 —NH— (C ⁇ O) —O—C 2 H 4 —) is 4, and the propionyloxybutyl group (C 2 H 5 — (C ⁇ O)
  • the number of carbon atoms of —O—C 4 H 8 —) is 7, and the number of carbon atoms of the ethoxypropyl group (C 2 H 5 —O—C 3 H 6 —) is 5.
  • substituents such as an amino group, a glycidyl group, a (meth) acrylate group, and an oxetane ring, in the side chain and / or the terminal.
  • the number of substituents is not limited.
  • the number of the substituents per organic group is 1 to 3, preferably 1.
  • the carbon number of the substituent is not included in the carbon number of the “organic group”.
  • a glycidyl butyl group ((C 2 H 3 O) —C 4 H 8 —) corresponds to a butyl group, which is an organic group having 4 carbon atoms, substituted with one glycidyl group
  • the methyl-4-oxo-hex-5-en-1-yl group (CH 3 — (C ⁇ CH 2 ) — (C ⁇ O) —C 3 H 6 —) is propyl which is an organic group having 3 carbon atoms. This corresponds to a group in which one methacrylate group is substituted.
  • hydrolyzable silane represented by the formula (II) examples include alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane; phenyltrimethoxysilane, phenyltrimethoxysilane, and the like.
  • Phenyltrialkoxysilane such as ethoxysilane; (Meth) acryloyl such as 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltrialkoxysilane Oxy group-containing alkyltrialkoxysilane; 3-glycidyloxypropyltrimethoxysilane, glycidyl group-containing alkyltrialkoxysilane such as 3-glycidyloxypropyltriethoxysilane Examples include vinyl group-containing trialkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; oxetane ring-containing alkyltrialkoxysilanes such as 3-[(3-ethyloxetane-3-yl) methoxy] propyltrimeth
  • methyltrialkoxysilane, glycidyl group-containing alkyltrialkoxysilane, and oxetane ring-containing alkyltrialkoxysilane are preferable from the viewpoint of curability and scratch resistance.
  • silsesquioxane compound (a) those obtained by hydrolytic condensation of a hydrolyzable silane containing the hydrolyzable silane represented by the formula (I) are preferable.
  • the hydrolyzable silane used as the raw material of the silsesquioxane compound (a) may further contain a hydrolyzable silane represented by the formula (II).
  • the containing silsesquioxane compound (a) is: With respect to the total molar mass of the hydrolyzable silane represented by the formula (I) and the formula (II), Hydrolyzable silane 55-100 mol% represented by the formula (I), Hydrolyzable silane represented by the formula (II) 0 to 45 mol%, In particular, from the viewpoint of scratch resistance, the following range is preferable.
  • the hydrolyzable silane represented by the formula (I) is particularly in the range of 80 to 100 mol%, more particularly 90 to 100 mol%, and the hydrolyzable silane represented by the formula (II) is 0 to 20 mol%, more particularly in the range of 0 to 10 mol / g.
  • the amount of the hydrolyzable silane represented by the formula (II) being 0 mol% means that the silane is not used at all.
  • a catalyst can be used when producing the silsesquioxane compound as component (a).
  • a basic catalyst is preferably used.
  • the basic catalyst include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethyl
  • ammonium hydroxide salts such as ammonium hydroxide and ammonium fluoride salts such as tetrabutylammonium fluoride.
  • the amount of the catalyst used is not particularly limited, but if it is too much, there are problems such as high costs and difficulty in removal, and if it is too small, the reaction may be slow. Therefore, it is preferably in the range of 0.0001 to 1.0 mol, more preferably 0.0005 to 0.1 mol, per mol of hydrolyzable silane.
  • hydrolyzing and condensing hydrolyzable silane water is usually used.
  • the quantity ratio of hydrolyzable silane and water is not particularly limited.
  • the amount of water used is from 0.1 to 100 mol, more preferably from 0.5 to 3 mol, based on 1 mol of hydrolyzable silane in terms of the yield and purity of the silsesquioxane compound having the desired structure. It is preferable to be within the ratio.
  • the water to be used may be substituted with the water, and water may be added separately.
  • an organic solvent may be used. It is preferable to use an organic solvent from the viewpoint of preventing gelation and adjusting the viscosity during production.
  • organic solvent polar organic solvents and nonpolar organic solvents can be used alone or as a mixture.
  • polar organic solvent lower alcohols such as methanol, ethanol and 2-propanol, ketones such as acetone and methyl isobutyl ketone, and ethers such as tetrahydrofuran are used. Particularly, acetone and tetrahydrofuran have a low boiling point and the system is uniform. And the reactivity is improved.
  • nonpolar organic solvent a hydrocarbon solvent is preferable, and an organic solvent having a boiling point higher than that of water such as toluene and xylene is preferable.
  • an organic solvent azeotropic with water such as toluene efficiently removes water from the system. This is preferable because it is possible.
  • mixing a polar organic solvent and a nonpolar organic solvent provides the above-described advantages, so that it is preferably used as a mixed solvent.
  • the reaction temperature during the hydrolytic condensation is usually 0 to 200 ° C., preferably 10 to 190 ° C., more preferably 10 to 120 ° C. Although this reaction can be carried out regardless of pressure, a pressure range of 0.02 to 0.2 MPa is preferable, and a pressure range of 0.08 to 0.15 MPa is particularly preferable.
  • the reaction is usually completed in about 1 to 15 hours.
  • the condensation reaction proceeds with hydrolysis, and most of the hydrolyzable group of the hydrolyzable silane [specifically, for example, X in the formula (I), preferably 100% is hydroxyl. It is possible to condense liquid stability and scratch resistance by hydrolysis to a group (OH group) and further condensing most of the OH group, preferably 80% or more, more preferably 90% or more, and particularly preferably 100%. To preferred.
  • the alcohol, solvent, and catalyst generated by the reaction may be removed from the mixed solution after hydrolysis condensation by a known method.
  • the obtained product may be further purified by removing the catalyst by various purification methods such as washing, column separation, and adsorption with a solid adsorbent according to the purpose. From the viewpoint of efficiency, it is preferable to remove the catalyst by washing with water.
  • the product obtained by this production method includes a silsesquioxane compound having a structure in which all Si—OH groups (hydroxysilyl groups) are hydrolyzed and condensed.
  • a silsesquioxane compound having a ladder structure in which Si—OH groups remain, an incomplete cage structure, and / or a random condensate may be included, and is a component (A) obtained by this production method.
  • the silsesquioxane compound may contain these ladder structures, incomplete cage structures, and / or random condensates.
  • the silsesquioxane compound as the component (a) obtained by the above production method has a ratio of the silsesquioxane compound having a structure in which all Si—OH groups are hydrolyzed and condensed, preferably 80% by mass or more, More preferably, it is 90% by mass or more from the viewpoint of liquid stability and scratch resistance.
  • the photocationic curable coating composition of the present invention contains an iodonium salt photoacid generator (b).
  • the iodonium salt-based photoacid generator (b) is a compound that generates a cation (acid) by light and can serve as an initiator for cationic polymerization.
  • the photoacid generator (b) is preferably an iodonium salt photoacid generator represented by the following formula (III). *
  • R 3 represents an organic group bonded to I (iodine atom), and two R 3 s may be the same or different from each other.
  • [Y] ⁇ is a phosphate anion represented by the formula (IV) or a boron compound anion represented by the formula (V), and Rf in the formula (IV) is fluorine in which all or part of the hydrogen atoms are fluorine.
  • An alkyl group which may be substituted with an atom is represented.
  • b is an integer of 0 to 5. The b Rf's may be the same or different.
  • R 3 is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms.
  • the aryl group having 6 to 30 carbon atoms includes monocyclic aryl groups such as phenyl groups and condensed naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, anthraquinone, etc. And a polycyclic aryl group.
  • heterocyclic group having 4 to 30 carbon atoms examples include cyclic groups containing 1 to 3 heteroatoms such as oxygen, nitrogen and sulfur, which may be the same or different.
  • monocyclic heterocyclic groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl , Carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thiantenyl, phenoxazinyl, phenoxathinyl, chromanyl, isochromanyl, dibenzothienyl,
  • alkyl group having 1 to 30 carbon atoms examples include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexadecyl, okdadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, etc.
  • a cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • alkenyl group having 2 to 30 carbon atoms examples include linear or branched such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl Can be mentioned.
  • alkynyl group having 2 to 30 carbon atoms examples include linear or branched ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl and the like. Things.
  • the aryl group having 6 to 30 carbon atoms, the heterocyclic group having 4 to 30 carbon atoms, the alkyl group having 1 to 30 carbon atoms, the alkenyl group having 2 to 30 carbon atoms, or the alkynyl group having 2 to 30 carbon atoms is at least 1
  • the substituent may include a linear alkyl group having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, okdadecyl; isopropyl, isobutyl, sec-butyl, tert-butyl A branched alkyl group having 1 to 18 carbon atoms; a cycloalkyl group having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; a hydroxy group; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, straight-
  • arylthio groups having 6 to 20 carbon atoms; methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, dodecylthio, etc.
  • a heterocyclic group having 4 to 20 carbon atoms such as nyl; an aryloxy group having 6 to 10 carbon atoms such as phenoxy and naphthyloxy; methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, octylsulfur Linear or branched alkylsulfinyl groups having 1 to 18 carbon atoms such as ynyl; arylsul
  • iodonium cation examples include diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, bis (4-ethoxyphenyl) iodonium, (4-octyloxy Phenyl) phenyliodonium, bis (4-decyloxy) phenyliodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, 4-isobutylphenyl (p-tolyl) iodonium, etc. Iodonium ion.
  • Rf represents an alkyl group in which all or part of the hydrogen atoms may be substituted with fluorine atoms.
  • the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and cyclopropyl, cyclobutyl and cyclopentyl.
  • a cycloalkyl group such as cyclohexyl, etc., and a preferable carbon number is 1 to 4.
  • all or part of the hydrogen atoms may be substituted with fluorine atoms, and the substitution ratio is 80% or more, more preferably 90% or more, particularly 100% from the viewpoint of polymerization curability and scratch resistance. It is preferable that
  • Rf is a linear or branched alkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%.
  • Specific examples include CF 3 , CF 3 CF 2 , (CF 3 ) 2 CF , CF 3 CF 2 CF 2, CF 3 CF 2 CF 2 CF 2, (CF 3) 2 CFCF 2, CF 3 CF 2 (CF 3) CF, include (CF 3) 3 C.
  • particularly preferred Rf is a linear or branched unsubstituted alkyl group having 1 to 4 carbon atoms, and specific examples include CH 3 , CH 3 CH 2 , (CH 3 ) 2. CH, CH 3 CH 2 CH 2 , CH 3 CH 2 CH 2 CH 2, (CH 3) 2 CHCH 2, CH 3 CH 2 (CH 3) CH, include (CH 3) 3 C.
  • [Y] ⁇ is preferably a phosphate anion represented by formula (IV).
  • the number b of Rf is an integer of 0 to 5, more preferably 1 to 4, more preferably 2 or 3, from the viewpoint of scratch resistance.
  • the b Rf's may be the same or different.
  • preferred phosphate anions include fluorinated phosphate anions ([PF 6 ] ⁇ ), [(CF 3 CF 2 ) 3 PF 3 ] ⁇ , [(CF 3 CF 2 CF 2 ) 3 PF 3 ] ⁇ , [((CF 3 ) 2 CF) 3 PF 3 ] ⁇ , [((CF 3 ) 2 CF) 2 PF 4 ] ⁇ , [((CF 3 ) 2 CFCF 2 ) 3 PF 3 ] ⁇ and Fluorinated alkyl phosphate anions such as [((CF 3 ) 2 CFCF 2 ) 2 PF 4 ] — and the like can be mentioned.
  • the anionic species is particularly preferably a fluorinated alkyl phosphate anion.
  • particularly preferred phosphate anions include ([PF 6 ] ⁇ ) and [(CH 3 CH 2 ) 3 PF 3 ] ⁇ , [(CH 3 CH 2 CH 2 ) 3 PF 3 ] ⁇ , [((CH 3 ) 2 CH) 3 PF 3 ] ⁇ , [((CH 3 ) 2 CH) 2 PF 4 ] ⁇ , [((CH 3 ) 2 CHCH 2 ) 3 PF 3] - and [((CH 3) 2 CHCH 2) 2 PF 4] - , and the like fluorinated alkyl phosphate anion, such as.
  • iodonium salt photoacid generator (b) a commercially available product can be used.
  • Irgacure (registered trademark) 250 trade name, fluorinated iodonium phosphate salt manufactured by BASF
  • IK-1 examples include San Apro, trade name, fluorinated alkyl phosphate iodonium salt
  • PI-2074 Rhone Plan, trade name, fluorinated phenyl borate iodonium salt
  • the photoacid generator may be dissolved in advance in a solvent that does not inhibit cationic polymerization. .
  • Solvents include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate and diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and 2-heptanone; ethylene glycol, ethylene glycol Multivalents such as monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether Alcohols and derivatives thereof; cyclic amines such as dioxane Ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl ace
  • the blending ratio of the photoacid generator (b) is preferably in the range of 0.1 to 15 parts by mass, more preferably 0.5 to 8 parts by mass with respect to 100 parts by mass of the total weight of the component (a).
  • photocationic curable coating composition of the present invention may further contain other photocationically polymerizable group-containing compound (c).
  • the other photocationically polymerizable group-containing compound (c) is a compound other than the component (a), which is ionically polymerized using a cation as a chain carrier (growth seed).
  • a compound having one or more photocationically polymerizable groups particularly an epoxy group-containing compound and / or an oxetane compound in which the photocationically polymerizable group is an epoxy group and / or an oxetane ring.
  • the epoxy group include an oxiranyl group, a glycidyl group, and an alicyclic epoxy group (such as an epoxycycloalkyl group).
  • the compound examples include a glycidyl group-containing compound having one or more glycidyl groups, and an oxetane ring.
  • An oxetane compound having one or more, an epoxy group-containing oxetane compound having at least one oxetane ring and an epoxy group hereinafter referred to as an epoxy group-containing oxetane compound
  • an alicyclic epoxy having at least one alicyclic epoxy group It is preferably at least one selected from the group-containing compound group.
  • the glycidyl group-containing compound is a compound having at least one glycidyl group in the molecule, and examples of the compound having one glycidyl group include phenyl glycidyl ether and butyl glycidyl ether, and a compound having two or more epoxy groups.
  • Contains ethylene glycol diglycidyl ether, hexanediol diglycidyl ether, tetraethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, novolac type epoxy compound, glycidyl group An acrylic resin etc. are mentioned.
  • the glycidyl group-containing acrylic resin is, for example, a glycidyl group-containing polymerizable unsaturated monomer (hereinafter sometimes abbreviated as “glycidyl monomer”) and, if necessary, other polymerizable monomers copolymerizable with these monomers. It is obtained by copolymerizing a saturated monomer (hereinafter, sometimes abbreviated as “other monomer”).
  • any polymerizable unsaturated monomer containing a glycidyl group can be used without particular limitation.
  • Typical examples thereof include glycidyl acrylate, glycidyl methacrylate, methyl glycidyl acrylate, methyl glycidyl methacrylate, and allyl glycidyl.
  • examples thereof include ether and vinyl glycidyl ether. Of these, glycidyl acrylate and glycidyl methacrylate are preferably used.
  • the other monomer copolymerizable with the glycidyl monomer is a monomer that is appropriately used as required according to the intended performance of the resulting glycidyl group-containing acrylic resin, such as methyl acrylate, methyl methacrylate, ethyl Acrylate, ethyl methacrylate, n-, i- or t-butyl acrylate, n-, i- or t-butyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl C1-C24 alkyl or cycloalkyl ester of acrylic acid or methacrylic acid such as methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, etc.
  • acrylic acid or methacrylic acid such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate Hydroxyalkyl esters; ⁇ , ⁇ -ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid; acrylamide, methacrylamide, N-methyl acrylamide, N-ethyl methacrylamide, diacetone acrylamide N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide, etc.
  • acrylic acid or methacrylic acid such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-
  • Rilamide or derivatives thereof aromatic vinyl monomers such as styrene, vinyltoluene, ⁇ -methylstyrene; vinyl propionate, vinyl acetate, acrylonitrile, methacrylonitrile, vinyl pivalate, and veova monomer (made by Shell Chemical Co., vinyl of branched fatty acids) Ester), Silaplane (registered trademark) FM0711, FM0721, FM0721 (all of which are manufactured by Chisso Corp., polydimethylsiloxane macromonomer having a methacryloyl group at the end). . Of these monomers, styrene and methyl methacrylate are particularly preferred.
  • the glycidyl group-containing acrylic resin is a solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization of the monomer component consisting of the above glycidyl monomer and other monomers as required, for example, in the presence or absence of a radical polymerization initiator. It can obtain by superposing
  • the glycidyl group-containing acrylic resin preferably has a weight average molecular weight in the range of 1,000 to 100,000, particularly 2,000 to 50,000.
  • the blending ratio of each monomer component in the polymerization of the glycidyl group-containing acrylic resin is preferably within the following range with respect to 100 parts by mass of the total amount of monomer components.
  • Glycidyl monomer 10 to 100 parts by mass, preferably 20 to 80 parts by mass, Other monomers: 0 to 90 parts by mass, preferably 20 to 80 parts by mass.
  • the concentration of glycidyl groups is preferably in the range of 0.1 to 7.0 equivalent / kg, particularly 0.2 to 5.0 equivalent / kg.
  • the oxetane compound is a compound having at least one oxetane ring in the molecule, and is preferably a compound having 1 to 3 oxetane rings.
  • Compounds having one oxetane ring include 3-ethyl-3-methoxymethyloxetane, 3-ethyl-3-ethoxymethyloxetane, 3-ethyl-3-butoxymethyloxetane, 3-ethyl-3-hexyloxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-allyloxymethyloxetane, 3-ethyl-3- (2'-hydroxyethyl) oxymethyloxetane, 3- Ethyl-3- (2′-hydroxy-3′-phenoxypropyl) oxymethyloxetane, 3-ethyl-3- (2′-hydroxy-3′-butoxypropyl) oxymethyloxetane, 3-ethyl-3- [2 '-(2 "-ethoxyethyl) oxymethyl] oxet
  • the compound having two or more oxetane rings is a compound having at least two oxetane rings capable of photocationic polymerization (hereinafter referred to as a polyoxetane compound).
  • a polyoxetane compound for example, di [1-ethyl (3-oxetanyl)] methyl ether; xylylene bisoxetane; reaction product of 3-lower alkyl-3-hydroxyoxetane and polyisocyanate compound; 3-lower alkyl-3-hydroxyoxetane and alcohol A reaction product of 3-lower alkyl-3-hydroxyoxetane with a polycarboxylic acid, and the like.
  • the 3-lower alkyl-3-hydroxyoxetane include 3-methyl-3-hydroxymethyloxetane and 3-ethyl-3-hydroxymethyloxetane.
  • the epoxy group-containing oxetane compound is a compound having one or more oxetane rings and epoxy groups in the molecule (hereinafter referred to as an epoxy group-containing oxetane compound), preferably including a compound having a molecular weight of less than 1,000, Specific examples include compounds represented by the following formula (VI).
  • R 4 represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched fluoroalkyl group having 1 to 6 carbon atoms, or an allyl group
  • R 5 represents an epoxy group
  • a typical example of the epoxy-containing oxetane compound is a compound in the above formula (VI) in which R 4 is an ethyl group and R 5 is a glycidyl group or a 3,4-epoxycyclohexylmethyl group.
  • the alicyclic epoxy group-containing compound is a compound having at least one such alicyclic epoxy group in the molecule and is a compound other than the compound (a), and preferably has 2 to 3 alicyclic epoxy groups. And a compound having a weight average molecular weight of less than 2,000 and more preferably 100 to 1,500.
  • the alicyclic epoxy group-containing compound preferably has an epoxy equivalent of 50 to 500 g / equivalent, particularly 100 to 300 g / equivalent, from the viewpoint of reaction rate.
  • the epoxy equivalent is the number of grams of resin containing 1 gram equivalent of an epoxy group measured by a method according to JIS K7236.
  • alicyclic epoxy group-containing compound examples include dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, epoxycyclohexenecarboxylic acid ethylene glycol diester, bis (3,4-epoxycyclohexylmethyl) adipate Bis (4,5-epoxy-2-methylcyclohexylmethyl) adipate, ethylene glycol-bis (3,4-epoxycyclohexanecarboxylate), 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 1,2,5,6-diepoxy-4,7-methanoperhydroindene, 2- (3, 4- Epoxycyclohexyl) -3 ', 4'-epoxy-1,3-dioxane-5-
  • Celoxide (registered trademark) 2000 Celoxide (registered trademark) 2021P
  • Celoxide (registered trademark) 2081 Celoxide (registered trademark) 3000 (all , Trade name, manufactured by Daicel Chemical Industries, Ltd.).
  • photocationically polymerizable group-containing compound (c) in addition to the above compound group, for example, butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, butanediol monovinyl ether, butanediol divinyl ether, cyclohexanedimethanol Divinyl ether, cyclohexanedimethanol monovinyl ether, diethylene glycol divinyl ether, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol divinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol divinyl ether, tetraethylene glycol monovinyl ether Tert-butyl vinyl ether, tert-acyl vinyl ether, ethylhexyl vinyl ether, dode
  • the content of the other photocationically polymerizable compound (c) is preferably 50 parts by mass or less and 30 parts by mass or less with respect to 100 parts by mass of the component (a) from the viewpoint of curling resistance.
  • the photocationic curable coating composition of the present invention may be solventless or may further contain an organic solvent. *
  • organic solvent examples include alcohol solvents such as methanol, ethanol, butanol, methyl isobutyl carbinol, 2-ethyl hexanol and benzyl alcohol; ketone solvents such as acetone and methyl isobutyl ketone; ethyl acetate, butyl acetate, methyl benzoate, Ester solvents such as methyl propionate; ether solvents such as cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, isopropyl glycol; diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3 -Glycol ether aromatic hydrocarbon solvents such as methoxybutyl acetate, aliphatic hydrocarbons Agents. These can be used in appropriate combination depending on the purpose such as adjustment of viscosity and adjustment
  • organic solvents it is preferable to use an organic solvent having a boiling point of 100 ° C. or less from the viewpoint of finish and curability.
  • organic solvents it is preferable to use at least one selected from dimethoxyethane.
  • composition of the present invention may further contain a sensitizer (d).
  • the sensitizer (d) usually absorbs at a wavelength longer than the maximum absorption wavelength indicated by the iodonium salt photoacid generator (b), and initiates polymerization by the iodonium salt photoacid generator (b). It is a compound that promotes.
  • the sensitizer (d) is preferably a compound that absorbs light having a wavelength longer than 350 nm.
  • the iodonium salt-based photoacid generator (b) usually exhibits maximum absorption at a wavelength near or shorter than 300 nm, generates a cationic species or a Lewis acid in response to light at a wavelength near the iodonium salt photoacid generator, Cationic polymerization of the oxan compound (a) is initiated, but if the sensitizer (d) as described above is added, it will be sensitive to light having a longer wavelength, particularly longer than 350 nm. .
  • Examples of the sensitizer (d) include anthracene sensitizers and thioxanthone sensitizers.
  • anthracene sensitizer examples include, for example, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentyloxyanthracene, 9,10-dihexyloxyanthracene, 9,10-bis (2-methoxyethoxy) anthracene, 9,10-bis (2-ethoxyethoxy) anthracene, 9,10-bis (2-butoxyethoxy) anthracene, 9,10-bis (3-butoxypropoxy) anthracene, 2-methyl- or 2-ethyl-9,10-dimethoxyanthracene, 2-methyl- or 2-ethyl-9,10-diethoxyanthracene, 2-methyl- or 2-ethyl-9,10-dipropoxyanthracene, 2-
  • thioxanthone sensitizer examples include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, chloropropoxythioxanthone, and the like.
  • a commercial item can be used as said sensitizer (d).
  • Examples of commercially available anthracene sensitizers include “Anthracure (registered trademark) UVS-1331”, “Anthracure (registered trademark) UVS-1221” (manufactured by Kawasaki Kasei Kogyo Co., Ltd.) and the like.
  • Examples of commercially available thioxanthone sensitizers include “KAYACURE (registered trademark) DETX-S” (manufactured by Nippon Kayaku Co., Ltd.), “Speedcure (registered trademark) ITX”, and “Speedcure (registered trademark) DETX”. "Speedcure (registered trademark) CPTX” (manufactured by LAMBSON).
  • an anthracene sensitizer is preferably used as the sensitizer (d).
  • the solid content of the sensitizer is selected from the above-mentioned sills from the viewpoint of the scratch resistance of the formed coating film and the storage stability of the coating composition. It is in the range of 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the solid content of the sesquioxane compound (a). Is preferred.
  • composition of the present invention may further contain an auxiliary sensitizer (e).
  • auxiliary sensitizer (e) is a compound that further promotes the action of the sensitizer.
  • the auxiliary sensitizer (e) is not particularly limited, and various types can be used.
  • a naphthalene-based auxiliary sensitizer can be preferably used.
  • Specific examples of the naphthalene-based auxiliary sensitizer include, for example, 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, 4-butoxy-1-naphthol, 4-hexyloxy-1-naphthol, 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, Examples thereof include 1,4-dibutoxynaphthalene.
  • the solid content of the auxiliary sensitizer (e) depends on the scratch resistance of the formed coating film and the storage of the coating composition. From the viewpoint of stability, 0.01 to 10 parts by mass, preferably 0.05 to 8 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the solid content of the silsesquioxane compound (a). It is preferable to be within the range of 5 parts by mass.
  • the composition of the present invention may further contain various additives, saturated resins and the like.
  • the additive include a thermal acid generator, an ultraviolet absorber, a light stabilizer, a polymerization inhibitor, an antioxidant, an antifoaming agent, a surface conditioner, a flow conditioner, a plasticizer, and a colorant.
  • the saturated resin include a saturated acrylic resin, a saturated polyester resin, a saturated urethane resin, these gel particles, and fine particle powder.
  • the non-volatile content of the photocationic curable coating composition of the present invention is not particularly limited, but is 20 to 100% by mass, and further 25 to 70% from the viewpoint of smoothness of the coating film and shortening of the drying time. Within the range of mass% is preferable.
  • the non volatile matter of the cation curable coating composition of this invention is the value which totaled the mass of all the components mix
  • the photocationic curable coating composition of the present invention has a coating film surface when a cured coating film having a thickness of 5 ⁇ m is formed on an acrylic resin plate having a thickness of 3 mm.
  • a coating film having a Martens hardness measured at 20 mN of 0.5 to 350 N / mm 2 can be formed.
  • the “acrylic resin plate having a thickness of 3 mm” means a plate made by Mitsubishi Rayon Co., Ltd. and Acrylite (registered trademark) L001 having a thickness of 3 mm.
  • the Martens hardness is 150 to 340 N / mm 2 and the elastic recovery rate of the coating film is 70% or more.
  • the elastic recovery rate is preferably 74% or more, more preferably 83% or more from the viewpoint of scratch resistance.
  • “Martens hardness (HM)” in the present invention is the hardness of the coating film obtained from the test load and the indentation surface area when indented from the surface of the coating film by the Vickers indenter, and is an index of the hardness of the object surface.
  • the “elastic recovery rate ( ⁇ IT)” in the present invention is a numerical representation of how much the recessed coating film returns, and is the ratio of elastic work (elastic deformation / total deformation).
  • the ratio of the elastic work amount can also be stopped by (W elast / W total ) ⁇ 100.
  • W elast is the work of elastic recovery [ Nmm ]
  • W total is the total indentation work [Nmm].
  • the numerical value of each work amount can be measured and determined together with the Martens hardness measurement.
  • a coating film having a large “elastic recovery rate” has elasticity and good scratch resistance.
  • a coating film having a Martens hardness of the coating film formed by the present coating composition, and more preferably an elastic recovery rate in the above range or more, has an appropriate balance between hardness and elasticity, and scratched the coating film. Sometimes, even if the scar is recovered, it is easy to return to the original coating state, and the scratch resistance is extremely excellent.
  • the cured coating is a cured and dried state as defined in JIS K 5600-1-1 (2004), that is, the center of the coating surface is strongly sandwiched between the thumb and index finger, and the coating surface is dented by a fingerprint. It is a coating film in which the movement of the coating film is not felt, the center of the coating surface is rapidly rubbed with a fingertip, and the coating surface is not rubbed.
  • the uncured coating film is a state where the coating film has not reached the above-mentioned cured and dried state, and includes a dry-to-touch state and a semi-cured and dried state as defined in JIS K 5600-1-1.
  • the photocationic curable coating composition is applied on the object to be coated so that the dry film thickness is 1 to 10 ⁇ m, and setting and / or After preheating, light irradiation is performed.
  • This step of setting and / or preheating is performed to reduce the volatile content of the coating film immediately after coating or to remove the volatile content, and can be performed by an air blow, an IR furnace or the like.
  • Setting can usually be performed by leaving the coated article to stand in a dust-free atmosphere at room temperature for 30 to 600 seconds.
  • Preheating (preheating) can be usually performed by heating the coated article in a drying furnace at a temperature of 40 to 90 ° C., preferably 50 to 70 ° C. for 1 to 30 minutes.
  • air blow can be usually performed by blowing air heated to a normal temperature or a temperature of 25 ° C. to 80 ° C. on the coated surface of the object to be coated.
  • the preheating time can usually be 30 seconds to 600 seconds.
  • the heating temperature condition at the time of performing the preheating is not particularly limited, but the component that volatilizes by heat, for example, the other photocationically polymerizable compound (c) contains a low boiling point compound ( In the case of containing less than 150 ° C.), the heating temperature is preferably less than 70 ° C., more preferably 40 ° C. to 70 ° C.
  • heat from a light source for example, heat generated by a lamp
  • the light irradiation may be performed in a state where the object to be coated is heated (a state having residual heat).
  • a primer layer, an electrodeposition coating layer, an intermediate coating layer, a top coating layer, etc. are formed in advance by applying a primer coating, a cationic electrodeposition coating, an intermediate coating, a top coating, etc. May be.
  • the dry film thickness is preferably in the range of 1 to 10 ⁇ m, more preferably 1 to 8 ⁇ m, in view of the appearance and curability of the coating film, scratch resistance, and curl resistance.
  • the curling property can be observed in terms of the degree of cure shrinkage of the coating composition.
  • the coating plate after the photocationic curable coating composition is formed on the surface of the plastic substrate is placed on a horizontal table with the coating surface facing up. Then, the distance (lifting distance) between the four corners of the test piece and the horizontal table can be measured and evaluated by the total length. The smaller the shrinkage during curing, the smaller the total length and the better the curl resistance.
  • the light irradiation source in the light irradiation step is not particularly limited, and is an ultrahigh pressure, high pressure, medium pressure, low pressure mercury lamp, chemical lamp, KrF excimer laser, ArF excimer laser, extreme ultraviolet (EUV: Extreme). Examples thereof include an Ultra Violet lamp, an X-ray, and an electron beam (e-beam), a carbon arc lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, an LED (light emitting diode) lamp, a tungsten lamp, and the sun.
  • the said irradiation source can be used individually or in combination of 2 or more types.
  • the light referred to in the present invention includes sunlight, laser light, radiated light (infrared rays, visible rays, ultraviolet rays, ⁇ rays, ⁇ rays, X rays) and the like, and is not particularly limited to visible rays.
  • the light has a function of activating a compound that generates a cation (acid) by light irradiation and advancing a cation polymerization reaction.
  • Irradiation amount varies depending radiation source, for example, when using a high pressure mercury lamp, 10 ⁇ 500mJ / cm 2 in the integrated irradiation dose, it is possible to further curing in the range of 50 ⁇ 120mJ / cm 2.
  • the light irradiation may be performed in an air atmosphere or an inert gas atmosphere.
  • a step of heating the coating film after light irradiation may be provided.
  • the distortion of the coating film generated by curing the coating film by light irradiation can be alleviated.
  • the heating may improve the hardness or adhesion of the coating film.
  • the heating temperature is preferably within the temperature range shown above.
  • the product form of the article in which the film is formed with the photocationic curable coating composition of the present invention is not particularly limited. However, since it has excellent transparency and scratch resistance, it can be particularly suitably used as a hard coat agent. .
  • Article to be coated (a) an acrylic resin plate: 100 ⁇ 150 mm having a thickness of 3mm was cut into an acrylic resin plate (Mitsubishi Rayon Co., Ltd. ACRYLITE (R) L001, a methacrylic resin plate [polymethyl methacrylate and methyl methacrylate An article to be coated (a) was obtained by degreasing a copolymer of n-butyl acrylate with a content of 88% or more] with isopropyl alcohol.
  • PET resin sheet A4 size, 100 ⁇ m thick polyethylene terephthalate resin sheet (trade name “Cosmo Shine (registered trademark) A4100” manufactured by Toyobo Co., Ltd.) was used as the article to be coated (b).
  • Coating film formation method (A) After coating each cationic curable coating composition on a coated material with a bar coater under a condition that the film thickness after curing is 5 ⁇ m, and preheating at 60 ° C. for 30 seconds to remove the solvent. Then, ultraviolet rays (peak top wavelength 365 nm) were irradiated with an ultraviolet irradiation device under the condition of an integrated irradiation amount of 100 mJ / cm 2 to obtain a cured coating film.
  • UV irradiation device belt conveyor type UV irradiation device
  • Lamp 240 W / cm 2 high-pressure mercury lamp (1 lamp number) (Heraeus Noblelight Fusion Ubuy Co., Ltd.)
  • Lamp output 60% Illuminance (measured with UV integrated light meter UIT (registered trademark) -250, photoreceiver UVD-C365 (manufactured by USHIO INC.)): 140 mW / cm 2 ⁇
  • Irradiation distance 10cm ⁇
  • UV-LED 96 lamps
  • Illuminance measured with UV integrated light meter UIT-250, receiver UVD-C365
  • Irradiation distance 1cm
  • Integrated irradiation dose measured with UV integrated light meter UIT-250, photoreceiver UVD-C365
  • conveyor speed Speed 2 m / min Total irradiation dose equivalent to 500 mJ / cm 2 .
  • Example (Example 1) Photocationic curable coating composition No. 1 A 50% nonvolatile solution of the product (A-1) obtained in Production Example 1, a photoacid generator (Note 1) of the following formula (B-1), and BYK-333 (Note 10) in a mass ratio of 100 5: 0.1, diluted with methyl ethyl ketone to a non-volatile content of 40%, stirred, and photocationic curable coating composition No. 1 was produced.
  • Table 2 shows the blending amount of each component by mass ratio.
  • a cured coating film obtained by curing the obtained photocationic curable coating composition by the coating film forming method (a) was allowed to stand for 1 hour in an atmosphere of 23 ° C. and 50% relative humidity within 30 minutes after curing.
  • the plate was used as a test plate.
  • the coating film had a Martens hardness (Note 11) of 245 N / mm 2 and an elastic recovery rate (Note 12) of 81%.
  • Table 2 also shows the Martens hardness and the elastic recovery rate of the coating film obtained by curing the obtained photocationic curable coating composition.
  • the notes in the table are as follows. (Note 1)
  • Photoacid generator No. B-1 An iodonium salt-based photocationic polymerizable initiator represented by the above formula (B-1), (Note 2)
  • Photoacid generator No. B-2 an iodonium salt-based photocationic polymerizable initiator represented by the above formula (B-2), (Note 3)
  • Photoacid generator No. B-3 An iodonium salt-based photocationically polymerizable initiator represented by the above formula (B-3), (Note 4)
  • Photoacid generator No. B-4 a sulfonium salt-based photocationically polymerizable initiator represented by the above formula (B-4), (Note 5)
  • Component C-1 Celoxide (registered trademark) 2012P (trade name, manufactured by Daicel Corporation, compound represented by the following formula C-1, epoxy equivalent of 118 to 145 g / equivalent.
  • Component C-2 Aron Oxetane (registered trademark) OXT-221 (trade name, manufactured by Toagosei Co., Ltd., compound represented by the following formula (C-2), boiling point 119 ° C./0.67 kPa ,
  • ⁇ Measurement procedure> (1-1) Load is applied until the load reaches 10 mN at a speed of 20 mN / 25 seconds. (1-2) Unloading until the load reaches 0.4mN at the same speed. The above procedure was repeated while changing the measurement position, and three data points were taken for each sample.
  • Example 19 On the object to be coated (b), the photocation curable coating composition No. 1 obtained in Example 1 was used. 1 was applied, and the coated sheet cured by the method of the coating film forming method (a) was left as it was for 1 hour in an atmosphere of 23 ° C. and 50% relative humidity within 30 minutes after curing as a test sample, It used for various evaluation. The evaluation results are shown in Table 3.
  • Example 19 test samples were prepared and subjected to various evaluations in the same manner as in Example 19 except that the objects to be coated, the coating film forming method, and the cured film thickness were those described in Table 3. The evaluation results are shown in Table 3. The notes in the table are as follows.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Molecular Biology (AREA)
  • Paints Or Removers (AREA)
  • Epoxy Resins (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention vise à créer une composition de revêtement à photopolymérisation cationique qui présente une transparence excellente et permet d'obtenir un film de revêtement durci présentant une excellente résistance à l'enroulement et aux rayures, ainsi qu'un procédé de formation d'un film de revêtement. A cet effet, la composition de revêtement à photopolymérisation cationique de l'invention contient un composé silsesquioxane (a) et un générateur photoacide à base d'un sel d'iodonium (b). Le composé silsesquioxane (a) contenant un groupe à photopolymérisation cationique est obtenu par hydrolyse-condensation d'un composé silane hydrolysable représenté par la formule (I) ou d'un mélange d'un composé silane hydrolysable représenté par la formule (I) et d'un composé silane hydrolysable représenté par la formule (II). En ce qui concerne le rapport du mélange d'un composé silane hydrolysable représenté par la formule (I) et d'un composé silane hydrolysable représenté par la formule (II), la proportion du composé silane hydrolysable représenté par la formule (I) est de 55-100 % en mole et la proportion du composé silane hydrolysable représenté par la formule (II) est de 0-45 % en mole rapportées à la quantité totale des composés silane hydrolysables représentés par la formule (I) et/ou la formule (II).
PCT/JP2014/077231 2013-10-11 2014-10-10 Composition de revêtement à photopolymérisation cationique, procédé de formation d'un film de revêtement et article revêtu de ce film WO2015053397A1 (fr)

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WO2018207647A1 (fr) * 2017-05-09 2018-11-15 株式会社ダイセル Composition pour former un film isolant, film isolant et dispositif semi-conducteur comprenant un film isolant
EP3470484A1 (fr) * 2017-10-16 2019-04-17 Samsung Electronics Co., Ltd. Composition, article, fenêtre pour dispositif électronique et dispositif électronique
WO2019188441A1 (fr) * 2018-03-30 2019-10-03 富士フイルム株式会社 Composition pour former une couche de revêtement dur, film de revêtement dur, article pourvu d'un film de revêtement dur, dispositif d'affichage d'image et procédé de fabrication d'un film de revêtement dur
WO2020059726A1 (fr) * 2018-09-18 2020-03-26 富士フイルム株式会社 Composition de revêtement dur, film de revêtement dur, article comportant un film de revêtement dur, dispositif d'affichage d'images et procédé de fabrication d'un film de revêtement dur
JPWO2020110966A1 (ja) * 2018-11-27 2021-09-30 富士フイルム株式会社 ハードコートフィルム、ハードコートフィルムを備えた物品、及び画像表示装置
CN114539915A (zh) * 2022-02-07 2022-05-27 厦门三德信科技股份有限公司 一种低收缩率、高硬度、可挠曲、防指纹硬化涂层及其制备方法
KR20220165184A (ko) 2021-06-07 2022-12-14 후지필름 가부시키가이샤 경화층 형성용 조성물, 적층체, 적층체의 제조 방법, 적층체를 구비한 물품, 화상 표시 장치 및 플렉시블 디스플레이
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JPWO2016204114A1 (ja) * 2015-06-17 2018-05-10 株式会社ダイセル 硬化性組成物、接着シート、硬化物、積層物、接着シートの製造方法、及び装置
WO2016204114A1 (fr) * 2015-06-17 2016-12-22 株式会社ダイセル Composition durcissable, feuille adhésive, produit durci, stratifié, procédé de production de feuille adhésive, et dispositif
US11773253B2 (en) * 2016-12-09 2023-10-03 Lg Chem, Ltd. Encapsulating composition
WO2018207647A1 (fr) * 2017-05-09 2018-11-15 株式会社ダイセル Composition pour former un film isolant, film isolant et dispositif semi-conducteur comprenant un film isolant
JP2018188563A (ja) * 2017-05-09 2018-11-29 株式会社ダイセル 絶縁膜形成用組成物、絶縁膜、及び絶縁膜を備えた半導体デバイス
EP3470484A1 (fr) * 2017-10-16 2019-04-17 Samsung Electronics Co., Ltd. Composition, article, fenêtre pour dispositif électronique et dispositif électronique
WO2019188441A1 (fr) * 2018-03-30 2019-10-03 富士フイルム株式会社 Composition pour former une couche de revêtement dur, film de revêtement dur, article pourvu d'un film de revêtement dur, dispositif d'affichage d'image et procédé de fabrication d'un film de revêtement dur
JPWO2019188441A1 (ja) * 2018-03-30 2021-02-12 富士フイルム株式会社 ハードコート層形成用組成物、ハードコートフィルム、ハードコートフィルムを有する物品、画像表示装置、及びハードコートフィルムの製造方法
CN112469790A (zh) * 2018-09-18 2021-03-09 富士胶片株式会社 硬涂组合物、硬涂膜、具有硬涂膜的物品、图像显示装置及硬涂膜的制造方法
CN112469790B (zh) * 2018-09-18 2022-02-11 富士胶片株式会社 硬涂组合物、硬涂膜、具有硬涂膜的物品、图像显示装置及硬涂膜的制造方法
WO2020059726A1 (fr) * 2018-09-18 2020-03-26 富士フイルム株式会社 Composition de revêtement dur, film de revêtement dur, article comportant un film de revêtement dur, dispositif d'affichage d'images et procédé de fabrication d'un film de revêtement dur
JPWO2020110966A1 (ja) * 2018-11-27 2021-09-30 富士フイルム株式会社 ハードコートフィルム、ハードコートフィルムを備えた物品、及び画像表示装置
JP7281481B2 (ja) 2018-11-27 2023-05-25 富士フイルム株式会社 ハードコートフィルム、ハードコートフィルムを備えた物品、及び画像表示装置
KR20220165184A (ko) 2021-06-07 2022-12-14 후지필름 가부시키가이샤 경화층 형성용 조성물, 적층체, 적층체의 제조 방법, 적층체를 구비한 물품, 화상 표시 장치 및 플렉시블 디스플레이
CN114539915A (zh) * 2022-02-07 2022-05-27 厦门三德信科技股份有限公司 一种低收缩率、高硬度、可挠曲、防指纹硬化涂层及其制备方法

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