[go: up one dir, main page]

WO2025079585A1 - Composition durcissable, produit durci, agent de revêtement dur, revêtement dur, article, et stratifié - Google Patents

Composition durcissable, produit durci, agent de revêtement dur, revêtement dur, article, et stratifié Download PDF

Info

Publication number
WO2025079585A1
WO2025079585A1 PCT/JP2024/036006 JP2024036006W WO2025079585A1 WO 2025079585 A1 WO2025079585 A1 WO 2025079585A1 JP 2024036006 W JP2024036006 W JP 2024036006W WO 2025079585 A1 WO2025079585 A1 WO 2025079585A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
carbon atoms
curable composition
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/036006
Other languages
English (en)
Japanese (ja)
Inventor
賢明 岩瀬
成美 尾関
崇寛 木村
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toagosei Co Ltd
Original Assignee
Toagosei Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toagosei Co Ltd filed Critical Toagosei Co Ltd
Publication of WO2025079585A1 publication Critical patent/WO2025079585A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C08F299/08—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 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
    • 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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/04—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
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings

Definitions

  • Displays of various devices that display images are provided with a transparent coating layer that is excellent in abrasion resistance and hardness as a surface protective layer.
  • the coating layer has antifouling properties.
  • leveling agents which are substances with low surface free energy, to make the surface smooth and resistant to dirt.
  • fluorine-based resins and silicone resins have been used as such leveling agents.
  • Patent Document 1 discloses a hard coat composition in which a nonionic fluorine-containing compound is added as a leveling agent to a polyorganosilsesquioxane having polymerizable epoxy groups.
  • a hard coat obtained by curing the composition since there is no covalent bond between the silsesquioxane, which is the main component, and the leveling agent, the performance deteriorates due to bleeding out of the leveling agent, etc.
  • Patent Document 3 discloses a hard coat composition in which a leveling agent having a polymerizable functional group and silicone or perfluoropolyether is added to a polysilsesquioxane derivative, but the crosslinking density of the leveling agent is low, and there is a risk of the hardness of the coating surface decreasing.
  • R 1 's each independently represent at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group
  • at least one of R 1 's is a monovalent organic group having a polymerizable group
  • the alkyl group, aralkyl group, aryl group, and monovalent organic group having a polymerizable group in R 1 may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group
  • R 2 's each independently represent a hydrocarbon group having 1 to 20 carbon atoms substituted with a fluorine atom
  • R 3 , R 4 , and R R 3 , R 4 and R 5 each independently represent
  • R 6 , R 7 and R 8 each independently represent at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group
  • at least one of R 6 , R 7 and R 8 is a monovalent organic group having a polymerizable group
  • the alkyl group, aralkyl group, aryl group, and monovalent organic group having a polymerizable group in R 6 , R 7 and R 8 may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group
  • q represents a positive number
  • p, r and s each independently represent 0 or a positive number.
  • ⁇ 6> A cured product obtained by curing the curable composition according to any one of ⁇ 1> to ⁇ 5>.
  • ⁇ 7> A hard coat agent comprising the curable composition according to any one of ⁇ 1> to ⁇ 5>.
  • ⁇ 8> A hard coat obtained by curing the hard coat agent according to ⁇ 7>.
  • ⁇ 9> An article having the hard coat according to ⁇ 8>.
  • ⁇ 10> A laminate comprising the hard coat according to ⁇ 9> and a substrate.
  • the cured product according to ⁇ 6>, wherein the cured product produced on a steel plate has a pencil hardness of 5H or more and a dynamic friction coefficient of 0.35 or less.
  • the mass ratio of the structural unit (a) is preferably 10 mass% or less, more preferably 5 mass% or less, and even more preferably 0 mass% relative to the total mass of the polysiloxane represented by formula (1) from the viewpoints of viscosity and hardness when cured.
  • a mass ratio of 0 mass% means that the corresponding structural unit is not included, and the same applies below.
  • R 1 each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms (also referred to as the number of carbon atoms), an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group, at least one of R 1 is a monovalent organic group having a polymerizable group, and the alkyl group, aralkyl group, aryl group, and monovalent organic group having a polymerizable group in R 1 may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group.
  • the alkyl group having 1 to 10 carbon atoms may be linear or branched.
  • Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. From the viewpoints of heat resistance and hardness of the cured product, a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
  • the polymerizable group in the monovalent organic group having a polymerizable group examples include an ethylenically unsaturated group, an alkynyl group, and a cyclic ether group.
  • the polymerizable group in R1 is preferably at least one selected from the group consisting of an acryloyl group, a methacryloyl group, an epoxy group, an oxetanyl group, a vinyl group, and an allyl group, more preferably at least one selected from the group consisting of an acryloyl group, a methacryloyl group, and an oxetanyl group, and particularly preferably at least one selected from the group consisting of an acryloyl group and a methacryloyl group.
  • the number of fluorine atoms contained in the fluorine atom R2 is preferably 3 to 50, more preferably 5 to 40, even more preferably 7 to 30, and particularly preferably 9 to 21.
  • the number of carbon atoms contained in R2 there is no particular limitation on the number of carbon atoms contained in R2 , as long as R2 has 1 or more.
  • R2 is preferably a fluoroalkyl group having 2 to 30 carbon atoms, more preferably a fluoroalkyl group having 4 to 20 carbon atoms, even more preferably a fluoroalkyl group having 5 to 16 carbon atoms, and particularly preferably a fluoroalkyl group having 6 to 12 carbon atoms.
  • R2 is preferably a group in which an alkylene group and a fluoroalkyl group are bonded together.
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably has 2 to 4 carbon atoms, and is particularly preferably an ethylene group.
  • the alkyl group having 1 to 10 carbon atoms, the aralkyl group having 7 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, and the monovalent organic group having a polymerizable group in R3 are the same as the preferred aspects of the alkyl group having 1 to 10 carbon atoms, the aralkyl group having 7 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, and the monovalent organic group having a polymerizable group in R1.
  • the structural unit (d) has at least a structure represented by the following formula (S).
  • the molar ratio of the structural unit (d) to all structural units (y/(v+w+x+y+z)) is preferably 0.10 to 0.80, more preferably 0.15 to 0.75, even more preferably 0.20 to 0.60, and particularly preferably 0.25 to 0.50, from the viewpoints of durability, water repellency, antifouling properties, hardness, and surface smoothness.
  • the total molar ratio ((x+y)/(v+w+x+y+z)) of the structural units (c) and (d) to all structural units is preferably 0.10 to 0.80, more preferably 0.15 to 0.70, and particularly preferably 0.20 to 0.50, from the viewpoints of durability, water repellency, antifouling properties, hardness, and surface smoothness.
  • the total molar ratio ((w+x+y)/(v+w+x+y+z)) of the structural units (b), (c) and (d) to the total structural units is preferably 0.3 to 1, more preferably 0.5 to 1, even more preferably 0.7 to 1, and particularly preferably 0.9 to 1, from the viewpoints of durability, water repellency, antifouling properties, hardness and surface smoothness.
  • the structural unit (e) is an M unit having one O 1/2 (0.5 oxygen atoms) per silicon atom, and one R 6 and two R 5 bonded to the silicon atom.
  • the M unit means a unit having one O 1/2 per silicon atom.
  • R 4 and R 5 each independently represent at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group
  • the alkyl group, aralkyl group, aryl group, and monovalent organic group having a polymerizable group in R 4 and R 5 may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group.
  • the mass ratio of the structural unit (e) is preferably 50 mass% or less, more preferably 30 mass% or less, and even more preferably 10 mass% or less, relative to the total mass of the polysiloxane represented by formula (1), from the viewpoints of cure shrinkage rate, hardness, storage stability, and curability with active energy rays such as UV.
  • the structural unit (f) is an alkoxy group, which is a hydrolyzable group contained in the silicon compound described below, or an alkoxy group formed by the substitution of an alcohol contained in the reaction solvent for a hydrolyzable group in the silicon compound, and may be one that remains in the molecule without being hydrolyzed or polycondensed, or may be a hydroxyl group that remains in the molecule after hydrolysis without being polycondensed.
  • the proportion of the structural unit (f) in the polysiloxane represented by formula (1) is not particularly limited.
  • the molar ratio of the structural unit (f) to all structural units is preferably 0.15 or less, more preferably 0.1 or less, even more preferably 0.05 or less, and may be 0, from the viewpoint of viscosity and hardness when cured. It may also be 0.01 or more.
  • the polysiloxane represented by formula (1) can be produced by a known method.
  • the method for producing polysiloxane is disclosed in detail in WO 2013/031798, JP 2000-044689, etc.
  • the hydrolysis step it is preferable to carry out not only hydrolysis of the organosilicon compound but also hydrolysis and polycondensation reaction of the organosilicon compound and, if necessary, other silicon compounds.
  • the organosilicon compound and, if necessary, other silicon compounds may be subjected to hydrolysis and polycondensation reactions to obtain an intermediate product, polysiloxane, and then the obtained intermediate product may be further subjected to hydrolysis and polycondensation reactions with the organosilicon compound and the like.
  • examples of the compound in which m is 3 and k is 1 include the M monomer, trimethylmethoxysilane, trimethylethoxysilane, tri(perfluoromethyl)methoxysilane, tri(perfluoroethyl)methoxysilane, trimethylchlorosilane, dimethylphenylmethoxysilane, methoxydimethylvinylsilane, ethoxydimethylvinylsilane, chlorodimethylvinylsilane, dimethylvinylsilanol, (3-acryloyloxypropyl)dimethylmethoxysilane, (3-methacryloyloxypropyl)dimethylmethoxysilane, p-styryldimethylmethoxysilane, and ethynyldimethylmethoxysilane.
  • R 11 and R 14 each independently represent an alkoxy group, an aryloxy group, an alkyl group, a cycloalkyl group, or an aryl group, and two R 11 and R 14 present in one molecule may be the same group or different groups.
  • the reactive silicone compound those in which the R 12 and R 13 present in a plurality in one molecule are methyl groups or ethyl groups can be produced from inexpensive raw materials, and the cured product obtained using the curable resin obtained using the polysiloxane represented by formula (1) of the present disclosure is particularly preferred from the viewpoints of durability, water repellency, antifouling properties, hardness, and surface smoothness, and those in which all are methyl groups are particularly preferred because these effects are remarkable.
  • the reactive silicone compound may be a mixture of compounds in which j in formula (3) and formula (4) has a single value or multiple values, and the average value J is, from the same viewpoint as above, a number of 1 or more, preferably 2 or more, more preferably 3 to 50, further preferably 4 to 30, and particularly preferably 6 to 20.
  • the average value J can be calculated, for example, from the average molecular weight of the reactive silicone.
  • the organic solvent used in the hydrolysis step may be an alcohol alone or may be a mixed solvent with at least one auxiliary solvent.
  • the auxiliary solvent may be either a polar solvent or a non-polar solvent, or a combination of both.
  • organic solvents other than alcohol include xylene, toluene, methyl ethyl ketone, methyl isobutyl ketone, and propylene glycol monomethyl ether.
  • the hydrolysis and polycondensation reaction of silicon compound may be carried out without catalyst or with catalyst.
  • catalyst preferred are inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid; organic acids such as formic acid, acetic acid, oxalic acid and paratoluenesulfonic acid; base catalysts such as ammonia, tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and more preferred are acid catalysts.
  • the proportion of the structural unit (g) in the polysiloxane represented by formula (2) is not particularly limited.
  • the molar ratio of the structural unit (g) to all structural units (p/(p+q+r+s)) is preferably 0.6 or less, more preferably 0.5 or less, even more preferably 0.3 or less, and even more preferably 0.1 or less, from the viewpoint of viscosity.
  • the Mw of the polysiloxane represented by formula (2) is not particularly limited and may be, for example, 300 to 30,000, 500 to 15,000, 700 to 10,000, or 1,000 to 5,000.
  • the viscosity of the polysiloxane represented by formula (2) at 25° C. is not particularly limited, and it may be a solid.
  • the polysiloxane represented by formula (2) is preferably a liquid from the viewpoint of handling, and in this case, the viscosity is not particularly limited, but is preferably 10 mPa ⁇ s to 100,000 mPa ⁇ s, more preferably 100 mPa ⁇ s to 80,000 mPa ⁇ s, further preferably 300 mPa ⁇ s to 60,000 mPa ⁇ s, and particularly preferably 500 mPa ⁇ s to 50,000 mPa ⁇ s.
  • the viscosity at 25° C. means a value measured using an E-type viscometer (a cone-plate type viscometer, for example, a TVE22H viscometer manufactured by Toki Sangyo Co., Ltd.).
  • the method for producing the polysiloxane represented by formula (2) is not particularly limited and can be produced by a known method, which is disclosed in detail in WO 2013/031798 and the like as a method for producing polysiloxane.
  • the method for producing the polysiloxane represented by formula (1) described above can also be referenced.
  • sulfonium salt examples include bis[4-(diphenylsulfonio)phenyl]sulfide.bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide.bishexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide.bistetrafluoroborate, bis[4-(diphenylsulfonio)phenyl]sulfide.tetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium.hexafluorophosphate, diphenyl-4-(phenylthio)phenylsulfonium.hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium.tetrafluoroborate, diphen
  • peroxides include hydrogen peroxide; inorganic peroxides such as sodium persulfate, ammonium persulfate, and potassium persulfate; 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-dibutyl t-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,
  • a redox reaction by combining a peroxide with a redox polymerization initiation system using a reducing agent such as ascorbic acid, sodium ascorbate, sodium erythorbate, tartaric acid, citric acid, a metal salt of formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite, or ferric chloride.
  • a reducing agent such as ascorbic acid, sodium ascorbate, sodium erythorbate, tartaric acid, citric acid, a metal salt of formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite, or ferric chloride.
  • the other components are not particularly limited, and examples thereof include solvents, polymerizable compounds other than the polysiloxane represented by formula (1) and the polysiloxane represented by formula (2), resins, silicones, monomers, fillers, surfactants, antistatic agents (e.g., conductive polymers), leveling agents, photosensitizers, ultraviolet absorbers, antioxidants, heat resistance improvers, stabilizers, lubricants, pigments, dyes, plasticizers, suspending agents, adhesion imparting agents, nanoparticles, nanofibers, nanosheets, etc.
  • Polysiloxanes other than the polysiloxane represented by formula (1) and the polysiloxane represented by formula (2) include polysiloxanes having polymerizable groups only in units other than the T unit.
  • Examples of monofunctional (meth)acrylates include Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; Monofunctional (meth)acrylates having an alicyclic group, such as cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecane methylol (meth)acrylate; Monofunctional (meth)acrylates having an aromatic group, such as benzyl (meth)acrylate and phenyl (meth)acrylate; (meth)acrylates of alkylene oxide adducts of phenol derivatives, such as (meth)acrylates of phenol ethylene oxide adducts, (meth)acrylates of phenol propylene oxide adducts, (meth)
  • a urethane (meth)acrylate can also be used.
  • the urethane (meth)acrylate include a compound obtained by addition reaction of an organic polyisocyanate with a hydroxyl group-containing (meth)acrylate, and a compound obtained by addition reaction of an organic polyisocyanate with a polyol and a hydroxyl group-containing (meth)acrylate.
  • the monofunctional (meth)acrylates, polyfunctional (meth)acrylates, etc. may be used alone or in combination of two or more kinds, or different kinds may be used in combination.
  • hydroxyl group-containing (meth)acrylate examples include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and hydroxyl group-containing polyfunctional (meth)acrylates such as pentaerythritol tri(meth)acrylate, di(meth)acrylate of an adduct of 3 moles of alkylene oxide with isocyanuric acid, and dipentaerythritol penta(meth)acrylate. These may be used alone or in combination of two or more kinds, or different kinds may be used in combination.
  • hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate
  • hydroxyl group-containing polyfunctional (meth)acrylates such as pentaerythritol tri(me
  • a compound having one ethylenically unsaturated group in one molecule other than the (meth)acrylate compound may be added to the curable composition.
  • the ethylenically unsaturated group is preferably a (meth)acryloyl group, a maleimide group, a (meth)acrylamide group, or a vinyl group.
  • Specific examples of the compound having an ethylenically unsaturated group include (meth)acrylic acid, a Michael addition type dimer of acrylic acid, N-(2-hydroxyethyl)citraconimide, N,N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone, and N-vinylcaprolactam. These may be used alone or in combination of two or more.
  • the cured product of the present disclosure is obtained by curing the curable composition of the present disclosure.
  • the cured product of the present disclosure can be obtained by irradiating the curable composition of the present disclosure with active energy rays or by heating the curable composition of the present disclosure.
  • the method of applying the curable composition is not particularly limited.
  • the application method include ordinary application methods such as casting, spin coating, bar coating, dip coating, spray coating, roll coating, flow coating, and gravure coating.
  • the thickness to which the curable composition of the present disclosure is applied is not particularly limited, and examples thereof include wood, metal, inorganic materials, plastics, paper, fibers, and fabrics.
  • metals include copper, silver, iron, aluminum, silicon, silicon steel, stainless steel, etc.
  • inorganic materials include metal oxides such as aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, zinc oxide, indium tin oxide, and gallium oxide, metal nitrides such as aluminum nitride, gallium nitride, and silicon nitride, ceramics such as silicon carbide and boron nitride, mortar, concrete, and glass, etc.
  • metal oxides such as aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, zinc oxide, indium tin oxide, and gallium oxide
  • metal nitrides such as aluminum nitride, gallium nitride, and silicon nitride
  • ceramics such as silicon carbide and boron nitride, mortar, concrete, and glass, etc.
  • plastics include acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate, polyvinyl chloride resins, polycarbonate resins, epoxy resins, polyamide resins such as nylon and aramid, fluororesins such as polyimide resins, polyamideimide resins, and tetrafluoroethylene resins, polyolefin resins such as cross-linked polyethylene resins, vinylidene chloride resins, acrylonitrile-butadiene-styrene (ABS) resins, polystyrene resins, polyacrylonitrile resins, cycloolefin polymers (COP), cycloolefin copolymers (COC), acetate resins, polyarylates, cellophane, norbornene resins, acetylcellulose resins such as triacetylcellulose (TAC), polychloroprene, polyphenylene sulfide, polysulfone, poly(vin
  • the fibers include natural fibers, regenerated fibers, semi-synthetic fibers, metal fibers, glass fibers, carbon fibers, ceramic fibers, and known chemical fibers.
  • the fabric may be a woven fabric or a nonwoven fabric, and can be produced, for example, using the above-mentioned fibers. These materials may be used alone, or two or more of them may be used in combination, mixture, or composite.
  • the shape of the substrate is not particularly limited, and examples thereof include plate, sheet, film, rod, sphere, fiber, powder, lens, and other regular or irregular shapes.
  • the curing temperature is preferably 80° C. to 200° C., more preferably 100° C. to 180° C., and even more preferably 110° C. to 150° C.
  • the curing temperature may be constant or may be increased. A combination of increasing and decreasing the temperature may also be used.
  • the curing time is appropriately selected depending on the type of thermal polymerization initiator, the content ratio of other components, etc., and is preferably 10 to 360 minutes, more preferably 30 to 300 minutes, and even more preferably 60 to 240 minutes.
  • the cured product of the present disclosure has excellent hardness, and can be applied to hard coats, optical members, and the like.
  • a hard coat having excellent hardness can be obtained by curing a hard coat agent containing the curable composition of the present disclosure.
  • the hard coat agent of the present disclosure may be provided on a substrate, and for example, a substrate having a hard coat can be obtained by curing a hard coat agent applied on a substrate.
  • the hard coat agent of the present disclosure may contain various components as necessary.
  • the cured product or hard coat of the present disclosure has excellent weather resistance.
  • aqueous solution was prepared by mixing 35% hydrochloric acid (1.0 g, 9.6 mmol as hydrogen chloride) and pure water (150.7 g) separately.
  • the aqueous solution prepared in the mixture was added dropwise from the dropping funnel over about 1 hour while stirring the reaction solution, and then the mixture was left to stand overnight at room temperature.
  • the amount of water added was 2.8 times the molar amount of the total amount of hydrolyzable groups in the raw material organosilicon compound.
  • the reaction solution was heated to 60° C. while the solvent and the like in the reaction solution were distilled off under reduced pressure, obtaining 170 g of a colorless, transparent liquid polysiloxane 9.
  • 1 H-NMR analysis confirmed that each structural unit was quantitatively introduced according to the raw material charging ratio.
  • the synthesized polysiloxane 9 had a viscosity of 6,270 mPa ⁇ s at 25° C. and a weight average molecular weight (Mw) of 2,010.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polysiloxane were determined by separation using a gel permeation chromatograph (HLC-8320GPC manufactured by Tosoh Corporation, hereinafter abbreviated as "GPC") in a tetrahydrofuran solvent at 40°C using a GPC column "TSK gel SuperMultiporeHZ-M” (manufactured by Tosoh Corporation), and the molecular weight in terms of standard polystyrene was calculated from the retention time.
  • GPC gel permeation chromatograph
  • UV irradiation conditions Lamp: High pressure mercury lamp Lamp height: 10cm Conveyor speed: 5.75 m/min Accumulated light amount per pass: 360 mJ/cm 2 (UV-A) Atmosphere: Air Number of passes: 10

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne : une composition durcissable contenant, par rapport à la teneur totale en solides de la composition durcissable, de 0,1 % en masse à moins de 10 % en masse d'un polysiloxane représenté par la formule (1) ; un produit durci obtenu par durcissement de ladite composition durcissable ; un agent de revêtement dur dans lequel la composition durcissable est utilisée ; un revêtement dur ; un article ; et un stratifié. Au moins un R1 est un groupe organique monovalent ayant un groupe polymérisable, chaque R2 représente indépendamment un groupe hydrocarboné en C1-20 substitué par un atome de fluor, w représente un nombre positif, v, x, y et z représentent chacun indépendamment 0 ou un nombre positif, x et/ou y représente un nombre positif, une structure représentée par la formule (S) est incluse lorsque x est 0, et n représente un nombre égal ou supérieur à 3.
PCT/JP2024/036006 2023-10-13 2024-10-08 Composition durcissable, produit durci, agent de revêtement dur, revêtement dur, article, et stratifié Pending WO2025079585A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023177806 2023-10-13
JP2023-177806 2023-10-13

Publications (1)

Publication Number Publication Date
WO2025079585A1 true WO2025079585A1 (fr) 2025-04-17

Family

ID=95395812

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/036006 Pending WO2025079585A1 (fr) 2023-10-13 2024-10-08 Composition durcissable, produit durci, agent de revêtement dur, revêtement dur, article, et stratifié

Country Status (2)

Country Link
TW (1) TW202536024A (fr)
WO (1) WO2025079585A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005040245A1 (fr) * 2003-10-24 2005-05-06 Nippon Kayaku Kabushiki Kaisha Composition de resine photosensible et film comprenant un revetement durci forme a partir de ladite composition
JP2007293325A (ja) * 2006-03-31 2007-11-08 Fujifilm Corp 反射防止フィルム、偏光板、及び画像表示装置
JP2012251035A (ja) * 2011-06-01 2012-12-20 Yokohama Rubber Co Ltd:The 硬化性樹脂組成物
WO2014069478A1 (fr) * 2012-10-31 2014-05-08 旭硝子株式会社 Composition de résine photosensible négative, film durci en résine, paroi de séparation et élément optique
JP2018130716A (ja) * 2017-01-20 2018-08-23 株式会社トクヤマ 表面修飾可能な積層体の製法
JP2020134941A (ja) * 2019-02-15 2020-08-31 ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ 反射防止コーティング
WO2020175338A1 (fr) * 2019-02-27 2020-09-03 富士フイルム株式会社 Polyorganosilsesquioxane et composition de formation de couche de revêtement dur
WO2020175337A1 (fr) * 2019-02-27 2020-09-03 富士フイルム株式会社 Corps stratifié, article ayant un corps stratifié, et dispositif d'affichage d'image
WO2022102732A1 (fr) * 2020-11-16 2022-05-19 株式会社豊田自動織機 Agent de revêtement, élément résineux et procédé de production associé

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005040245A1 (fr) * 2003-10-24 2005-05-06 Nippon Kayaku Kabushiki Kaisha Composition de resine photosensible et film comprenant un revetement durci forme a partir de ladite composition
JP2007293325A (ja) * 2006-03-31 2007-11-08 Fujifilm Corp 反射防止フィルム、偏光板、及び画像表示装置
JP2012251035A (ja) * 2011-06-01 2012-12-20 Yokohama Rubber Co Ltd:The 硬化性樹脂組成物
WO2014069478A1 (fr) * 2012-10-31 2014-05-08 旭硝子株式会社 Composition de résine photosensible négative, film durci en résine, paroi de séparation et élément optique
JP2018130716A (ja) * 2017-01-20 2018-08-23 株式会社トクヤマ 表面修飾可能な積層体の製法
JP2020134941A (ja) * 2019-02-15 2020-08-31 ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ 反射防止コーティング
WO2020175338A1 (fr) * 2019-02-27 2020-09-03 富士フイルム株式会社 Polyorganosilsesquioxane et composition de formation de couche de revêtement dur
WO2020175337A1 (fr) * 2019-02-27 2020-09-03 富士フイルム株式会社 Corps stratifié, article ayant un corps stratifié, et dispositif d'affichage d'image
WO2022102732A1 (fr) * 2020-11-16 2022-05-19 株式会社豊田自動織機 Agent de revêtement, élément résineux et procédé de production associé

Also Published As

Publication number Publication date
TW202536024A (zh) 2025-09-16

Similar Documents

Publication Publication Date Title
JP5050473B2 (ja) フッ素系重合体および樹脂組成物
KR102510268B1 (ko) 함불소 아크릴 화합물 및 그 제조 방법, 경화성 조성물, 및 물품
JP4517590B2 (ja) 耐汚染性付与剤及びそれを用いた耐汚染性物品
JP5750436B2 (ja) 修飾金属酸化物ゾル
JP5051383B2 (ja) （メタ）アクリル変性シロキサン化合物及びそれを含有する硬化性組成物
JP5083444B2 (ja) フッ素系重合体および樹脂組成物
CN1418912A (zh) 含阳离子聚合化合物的组合物和由该组合物得到的涂层
TWI851733B (zh) 含氟硬化性組成物及物品
WO2023100991A1 (fr) Dérivé de silsesquioxane, composition durcissable, agent de revêtement dur, objet durci, revêtement dur, et substrat
JP2017170827A (ja) 積層体、タッチパネル、タッチパネル表示装置、及び積層体の製造方法
JP2016160342A (ja) 光または熱硬化性樹脂組成物、硬化物及び積層体
WO2025079585A1 (fr) Composition durcissable, produit durci, agent de revêtement dur, revêtement dur, article, et stratifié
JP2025070322A (ja) 反射防止フィルムおよび反射防止フィルムの製造方法
JP7616247B2 (ja) 無機物質層積層用アンダーコート剤組成物、その硬化物及びその製造方法
JP7276183B2 (ja) 活性エネルギー線硬化性組成物、コーティング剤、および被膜物品
WO2025225088A1 (fr) Composition de revêtement, film de revêtement et matériau de base
WO2023100992A1 (fr) Dérivé de silsesquioxane, composition durcissable, objet durci, et substrat
WO2024247756A1 (fr) Dérivé de silsesquioxane, composition durcissable, produit durci, agent de revêtement dur, revêtement dur, article et stratifié
WO2025121040A1 (fr) Composition pour revêtements durs, son procédé de production, revêtement dur et substrat
WO2023238835A1 (fr) Dérivé de silsesquioxane et son procédé de production, composition durcissable, agent de revêtement dur, produit durci, revêtement dur et matériau de base
WO2024122417A1 (fr) Procédé de production d'un stratifié avec une couche de revêtement dur et stratifié avec couche de revêtement dur
WO2024122416A1 (fr) Procédé de production d'un corps stratifié avec une couche de revêtement dur
KR102776228B1 (ko) 코팅용 수지 조성물 및 코팅필름
WO2023238836A1 (fr) Dérivé de silsesquioxane et son procédé de production, composition durcissable, agent de revêtement dur, produit durci, revêtement dur et matériau de base
WO2025153618A1 (fr) Revêtement dur de polysiloxane exempt de fluor

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24877180

Country of ref document: EP

Kind code of ref document: A1