Classifications

• • 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
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
  • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
  • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/22—Esters containing halogen
  • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/062—Polyethers
• • 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
  • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
  • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
  • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
• • 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
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
• • 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
  • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
• • 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
  • 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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • 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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
  • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
  • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
  • C09D5/1637—Macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular
• • 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
  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
  • C08G2650/04—End-capping
• • 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
  • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
• • 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
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
• • 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
  • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers

Definitions

• the present invention is a fluorine-containing acrylic compound capable of imparting excellent liquid repellency, stain resistance, and abrasion resistance by adding it to an active energy ray-curable composition such as ultraviolet rays and electron beams, and the fluorine-containing acrylic compound.
• the present invention relates to a fluorine-containing active energy ray-curable composition having an acrylic compound, and an article having a cured product layer of this composition on the surface of a substrate.
• a hard coat treatment is widely and generally used as a means for protecting the surface of a resin molded product or the like.
• a hard cured resin layer (hard coat layer) is formed on the surface of the molded product to prevent it from being scratched.
• a curable composition using active energy rays such as a thermosetting resin or an ultraviolet or electron beam curable resin is often used.
• hard coat layer With the expansion of the fields of use of resin molded products and the trend toward higher added value, there is an increasing demand for higher functionality of the cured resin layer (hard coat layer), and one of them is the antifouling property of the hard coat layer. Is required to be granted. By imparting properties such as water repellency and oil repellency to the surface of the hard coat layer, it is difficult to get dirty, or even if it gets dirty, it can be easily removed.
• Patent Document 1 discloses the production of a hard coat layer imparted with antifouling property by adding and curing a fluoroalkyl acrylate to an acrylic curable resin composition. ing.
• the present inventors are proceeding with various developments as a fluorine-containing compound capable of imparting antifouling property to such a curable resin composition.
• Patent Document 2 Japanese Patent Application Laid-Open No. 2013-237824
• Patent Document 3 Proposes a method of imparting antifouling property by blending a fluorinated alcohol compound with a thermosetting resin.
• Patent Document 4 JP-A-2010-138112
• Patent Document 5 JP-A-2010-285501
• the present invention has been made in view of the above circumstances, and excellent liquid repellency, stain resistance, and abrasion resistance can be imparted by adding it to an active energy ray-curable composition such as ultraviolet rays or electron beams.
• An object of the present invention is to provide a fluorine-containing acrylic compound, a fluorine-containing active energy ray-curable composition having the fluorine-containing acrylic compound, and an article having a cured product layer of the composition on the surface of a substrate.
• Rf 1 is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom.
• Z 1 is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain one or more independently selected from an oxygen atom, a nitrogen atom and a silicon atom, and contains a cyclic structure in the middle. However, the structure does not contain urethane bonds.
• Q 1 is an (a + 1) -valent linking group that independently contains at least (a + 1) silicon atoms, may have a cyclic structure, and contains at least one selected from an oxygen atom, a nitrogen atom, and a fluorine atom. However, it does not contain a urethane bond in the structure.
• Z 2 is independently expressed by the following formula- CO H 2O- (OC 4 H 8 ) i (OC 3 H 6 ) j (OC 2 H 4 ) k (OCH 2 ) l- (In the formula, each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to each other, and i, j, k, and l have a molecular weight of Z 2 of 58.
• O is an integer of 2 to 10.
• It is a divalent alkylene ether group represented by.
• X is a monovalent organic group containing an acrylic group or an ⁇ -substituted acrylic group which may independently contain at least one selected from a hydrogen atom or an oxygen atom and a nitrogen atom, and is averaged in one molecule. It contains at least one monovalent organic group containing the acrylic group or ⁇ -substituted acrylic group, but does not contain a urethane bond in the structure.
• a is independently an integer from 1 to 10.
• Y is a fluorine atom or a monovalent group represented by -Z 1- Q 1- [Z 2- X] a .
• Rf 1 is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom.
• Z 1 is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain one or more independently selected from an oxygen atom, a nitrogen atom and a silicon atom, and contains a cyclic structure in the middle.
• Q 1 is an (a + 1) -valent linking group that independently contains at least (a + 1) silicon atoms, may have a cyclic structure, and contains at least one selected from an oxygen atom, a nitrogen atom, and a fluorine atom. However, it does not contain a urethane bond in the structure.
• Z 2 is independently expressed by the following formula- CO H 2O- (OC 4 H 8 ) i (OC 3 H 6 ) j (OC 2 H 4 ) k (OCH 2 ) l- (In the formula, each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to each other, and i, j, k, and l have a molecular weight of Z 2 of 58. In the range of ⁇ 330, they are independently integers of 0 to 10. O is an integer of 2 to 10.) It is a divalent alkylene ether group represented by.
• X is a monovalent organic group containing an acrylic group or an ⁇ -substituted acrylic group which may independently contain at least one selected from a hydrogen atom or an oxygen atom and a nitrogen atom, and is averaged in one molecule. It contains at least one monovalent organic group containing the acrylic group or ⁇ -substituted acrylic group, but does not contain a urethane bond in the structure.
• a is independently an integer from 1 to 10.
• Y is a fluorine atom or a monovalent group represented by -Z 1- Q 1- [Z 2- X] a .
• Z 1 in formula (1) and a Z 2 enclosed in [] are all bonded to silicon atoms in the Q 1 structure.
• Rf 1 has the following formula.
• b is an integer of 1 to 3 independently for each unit.
• Each of these units. May be linear or branched, and each repeating unit shown in parentheses with c, d, e, f, g, h may be randomly combined.
• the fluorine-containing acrylic compound according to [1] which is a divalent perfluoropolyether group represented by.
• Rf 1 is represented by the following structural formula -CF 2 O- (CF 2 O) p (CF 2 CF 2 O) q -CF 2 - (However, the array of repeating units enclosed in () is random, p is an integer of 1 to 199, q is an integer of 1 to 170, p + q is 6 to 200, and s is an integer of 0 to 6.
• t and u are integers of 1 to 100, t + u is an integer of 2 to 120, s + t + u is an integer of 3 to 126, and v is an integer of 4 to 120.)
• Z 1 has the following formula-CH 2 CH 2 CH 2 CH 2- -CH 2 OCH 2 CH 2 CH 2-
• Q 1 is the following formula.
• a' is an integer from 2 to 10.
• X is the following formula.
• R 1 is independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group
• Z 3 contains a single bond or an ether bond and / or an ester bond having 1 to 18 carbon atoms.
• the fluorine-containing acrylic compound represented by the general formula (1) is the fluorine-containing acrylic compound represented by the following general formula (2) or (3), which is described in any one of [1] to [6].
• Acrylic compound. In the formula, Rf 1 , Z 1 , Z 2 , Q 1 , and a are as described above.
• R 1 is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
• the fluorine-containing acrylic compound represented by the general formula (1) is the fluorine-containing acrylic compound represented by the following general formula (4) or (5), according to any one of [1] to [7].
• Acrylic compound. [In the formula, Rf 1 , Z 1 , Q 1 , and a are as described above.
• Z 4 is of the formula -C O H 2O - (OC 3 H 6) j '(OC 2 H 4) k' (OCH 2) l '- (In the formula, each repeating unit may be linear or branched, and each repeating unit may be randomly connected, and j', k', and l'are independently 0 to 0 to each. It is an integer of 4, but the sum of j', k', and l'is not 0. o is an integer of 2 to 10.) It is a divalent alkylene ether group represented by. ] [9]
• the fluorine-containing acrylic compound according to any one of [1] to [8], which is selected from the fluorine-containing acrylic compounds represented by the following formulas.
• Rf 2 is -CF 2 O- (CF 2 O) p (CF 2 CF 2 O) q -CF 2-
• p is an integer of 1 to 199
• q is an integer of 1 to 170
• v is an integer from 4 to 120.
• R 2 is independently a hydrogen atom or a methyl group
• R 3 is independently a hydrogen atom, a methyl group or a phenyl group.
• Z 4 is of the formula -C O H 2O - (OC 3 H 6) j '(OC 2 H 4) k' (OCH 2) l '- (In the formula, each repeating unit may be linear or branched, and each repeating unit may be randomly connected, and j', k', and l'are independently 0 to 0 to each. It is an integer of 4, but the sum of j', k', and l'is not 0. o is an integer of 2 to 10.) It is a divalent alkylene ether group represented by, and m is an integer of 2 to 5.
• the fluorine-containing active energy ray-curable composition is characterized by containing 0.005 to 40 parts by mass of the fluorine-containing acrylic compound according to any one of [1] to [9] with respect to 100 parts by mass of the active energy ray-curable composition. Sex composition.
• An article having a cured product layer of the fluorine-containing active energy ray-curable composition according to [10] or [11] which has a water contact angle of 90 ° or more at 25 ° C. and a relative humidity of 40%.
• the fluorine-containing acrylic compound of the present invention does not contain a urethane bond in the molecule, the antifouling property is unlikely to decrease due to wear. Therefore, the fluorine-containing acrylic compound is used to provide liquid repellency, stain resistance, and abrasion resistance to UV-curable and thermosetting hard coating agents, paints, resins, antireflection coating compositions, and the like. It is useful as a stain additive and the like.
• the fluorine-containing acrylic compound of the present invention is represented by the following general formula (1), and may be a mixture.
• Y-Rf 1- Z 1- Q 1- [Z 2- X] a (1)
• Rf 1 is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom.
• Z 1 is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may contain one or more independently selected from an oxygen atom, a nitrogen atom and a silicon atom, and contains a cyclic structure in the middle. However, the structure does not contain urethane bonds.
• Q 1 is an (a + 1) -valent linking group that independently contains at least (a + 1) silicon atoms, may have a cyclic structure, and contains at least one selected from an oxygen atom, a nitrogen atom, and a fluorine atom. However, it does not contain a urethane bond in the structure.
• Z 2 is independently expressed by the following formula- CO H 2O- (OC 4 H 8 ) i (OC 3 H 6 ) j (OC 2 H 4 ) k (OCH 2 ) l- (In the formula, each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to each other, and i, j, k, and l have a molecular weight of Z 2 of 58.
• O is an integer of 2 to 10.
• It is a divalent alkylene ether group represented by.
• X is a monovalent organic group containing an acrylic group or an ⁇ -substituted acrylic group which may independently contain at least one selected from a hydrogen atom or an oxygen atom and a nitrogen atom, and is averaged in one molecule. It contains at least one monovalent organic group containing the acrylic group or ⁇ -substituted acrylic group, but does not contain a urethane bond in the structure.
• a is independently an integer from 1 to 10.
• Y is a fluorine atom or a monovalent group represented by -Z 1- Q 1- [Z 2- X] a .
• Z 1 in formula (1) and a Z 2 enclosed in [] are all bonded to silicon atoms in the Q 1 structure. ]
• the fluorine-containing acrylic compound containing a urethane bond in the molecule has excellent compatibility with a non-fluorine-based organic solvent, the present inventors wear it when added to an active energy ray-curable composition due to actual use. It was found that the antifouling property of the surface of the cured film was significantly reduced. Therefore, the fluorine-containing acrylic compound of the present invention has a perfluoropolyether group as a water- and oil-repellent group and an acrylic group or an ⁇ -substituted acrylic group, and does not contain a urethane bond in the molecule. It is characterized in that excellent liquid repellency, antifouling property, and abrasion resistance can be imparted by adding the compound to the active energy ray-curable composition.
• Rf 1 is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Rf 1 is a carbon.
• Those having the following perfluorooxyalkylene structure having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms as the main repeating unit are preferable.
• These structures may be any one homopolymer, or a random or block polymer composed of a plurality of structures.
• b is an integer of 1 to 3 independently for each unit.
• Each of these units. May be linear or branched, and each repeating unit shown in parentheses with c, d, e, f, g, h may be randomly combined.
• b is an integer of 1 to 3 independently for each unit.
• c, d, e, f, g, and h are integers of 0 to 200, respectively, preferably c is an integer of 5 to 100, d is an integer of 5 to 100, e is an integer of 0 to 100, and f is an integer of 0 to 100.
• An integer of 0 to 100, g is an integer of 0 to 100, h is an integer of 0 to 100, c + d + e + f + g + h 3 to 200, preferably 10 to 105, and more preferably c + d is 10 to 105, particularly 15 to.
• each unit may be linear or branched. Further, each repeating unit shown in parentheses with c, d, e, f, g, and h may be randomly combined.
• Rf 1 having such a structure include the following structures. -CF 2 O- (CF 2 O) p (CF 2 CF 2 O) q -CF 2- (In the formula, the array of repeating units enclosed in () is random, p is 1 to 199, preferably an integer of 1 to 99, q is 1 to 170, preferably an integer of 1 to 99, and p + q is 6. It is an integer of ⁇ 200, preferably 10-100.) (In the formula, the sequence of repeating units enclosed in () is random, s is an integer of 0 to 6, t is an integer of 1 to 100, u is an integer of 1 to 100, and t + u is 2 to 120, preferably. Is an integer of 4 to 100, s + t + u is an integer of 3 to 126, preferably 4 to 100. V is an integer of 4 to 120, preferably 4 to 80.)
• the molecular weight of Rf 1 may be such that the number average molecular weight of the corresponding structural portion is contained in the range of 400 to 20,000, preferably 800 to 10,000, respectively, and the molecular weight distribution thereof is particularly limited. is not.
• the molecular weight is a number average molecular weight calculated from the ratio of the terminal structure to the main chain structure based on 1 1 H-NMR and 19 F-NMR (hereinafter, the same applies).
• Z 1 is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may independently contain one or more selected from an oxygen atom, a nitrogen atom and a silicon atom. Yes, it may contain an annular structure in the middle, but does not contain a urethane bond in the structure.
• Particularly preferable structures of Z 1 include the following. In the following structure, it is preferable that the left-hand bond is bonded to Rf 1 and the right-side bond is bonded to Q 1 . -CH 2 CH 2- -CH 2 CH 2 CH 2 - -CH 2 CH 2 CH 2 CH 2 - -CH 2 OCH 2 CH 2- -CH 2 OCH 2 CH 2 CH 2- -CH 2 OCH 2 CH 2 CH 2-
• a is independently an integer of 1 to 10, preferably an integer of 2 to 8.
• Q 1 is an (a + 1) -valent linking group that independently contains at least (a + 1) silicon atoms and may have a cyclic structure, and is composed of oxygen atoms, nitrogen atoms and fluorine atoms. It may contain at least one selected, provided that no urethane bond is contained in the structure.
• Such Q 1 is preferably composed of a siloxane structure having (a + 1) Si atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more thereof (a + 1).
• the linking group of Specifically, the following structure is shown as a particularly preferable structure.
• a is the same as a in the above equation (1), and is independently an integer of 1 to 10, preferably an integer of 2 to 8.
• a' is an integer of 2 to 10, preferably an integer of 2 to 7.
• r is an integer of 1 to 5, preferably an integer of 3 to 5.
• the arrangement of each unit is random, and the bonds (silicon atoms) of each of the (a + 1) and (a'+ 1) units are a Z 2 enclosed by [] in the above formula (1). And Z 1 binds to any of the groups.
• T is a linking group having a (a + 1) valence, and the following are exemplified.
• Q 1 in the above equation (1) is (In the formula, a'is as described above.)
• a linking group having a (a'+ 1) valence represented by is preferable.
• each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to each other, and i, j, k, and l have a molecular weight of Z 2 of 58.
• ⁇ 330 preferably 72 to 300, they are independently integers of 0 to 10 (that is, the sum of i, j, k, and l is 1 or more), and i is preferably 0 to 5.
• J is an integer of 0 to 5
• k is an integer of 0 to 5
• l is an integer of 0 to 5.
• o is an integer of 2 to 10, preferably an integer of 2 to 8.
• It is a divalent alkylene ether group represented by. In the above structure, it is preferable that the left-hand bond is Q 1 and the right bond is X.
• k1 is an integer of 0 to 10
• j1 is an integer of 0 to 10
• i1 is an integer of 0 to 10
• the molecular weight of Z 2 may be 86 to 330.
• the array of repeating units is random regardless of type. Further, each repeating unit may be a mixture of structural isomers as well as a simple substance. If the molecular weight of Z 2 is less than 58, it becomes difficult for the fluorine-containing acrylic compound to be mixed with a general non-fluorine-based organic solvent, and if it exceeds 330, the antifouling ability of the fluorine-containing acrylic compound becomes insufficient.
• particularly preferable structures include the following, and among them, those having k1 of 1 to 4 and j1 of 1 to 4 are preferable. -CH 2 CH 2 CH 2 (OC 2 H 4 ) k1- -CH 2 CH 2 CH 2 (OC 3 H 6 ) j1-
• X is a monovalent organic group containing an acrylic group or an ⁇ -substituted acrylic group which may independently contain at least one selected from a hydrogen atom or an oxygen atom and a nitrogen atom. Moreover, one molecule contains a monovalent organic group containing at least one acrylic group or ⁇ -substituted acrylic group on average, but does not contain a urethane bond in the structure.
• R 1 is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group
• Z 3 is a single bond or an ether bond and / or an ester bond having 1 to 18 carbon atoms. It is a divalent or trivalent hydrocarbon group that may be contained, and n is 1 or 2.
• R 1 is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and a hydrogen atom and a methyl group are preferable.
• n is 1 or 2, preferably 1.
• Z 3 is a divalent or trivalent hydrocarbon group which may contain a single bond or an ether bond and / or an ester bond having 1 to 18 carbon atoms.
• a single bond or the following structure is preferable.
• X a group represented by the following formula is preferable.
• -Z'-OC ( O)
• -CR 4 CH 2 (In the formula, R 4 is a hydrogen atom or a methyl group, and Z'is a single bond, a methylene group, an ethylene group, or a propylene group.)
• fluorine-containing acrylic compound represented by the above formula (1) those represented by the following general formula (2) or (3) are preferable.
• Rf 1 , Z 1 , Z 2 , Q 1 , R 1 , and a are as described above.
• each repeating unit may be linear or branched, and each repeating unit may be randomly connected, and j', k', and l'are independently 0 to 0 to each. It is an integer of 4, but the sum of j', k', and l'is not 0. o is an integer of 2 to 10.) It is a divalent alkylene ether group represented by. ]
• Rf 2 is ⁇ CF 2 O ⁇ (CF 2 O) p (CF 2 CF 2 O) q ⁇ CF 2 ⁇ , and the sequence of repeating units enclosed in () is random. It is an integer of 2 to 5, R 2 is an independent hydrogen atom or methyl group, and R 3 is an independent hydrogen atom, methyl group or phenyl group. P, q, p + q, Z 4 and v are described above. It's a street.)
• the fluorine-containing acrylic compound represented by the general formula (1) is not particularly limited in its synthesis method, but for example, in the embodiment of the fluorine-containing acrylic compound represented by the general formula (2) or (3).
• the following general formula (6) or (7) F-Rf 1- Z 1- Q 1- [H] a (6) [H] a- Q 1- Z 1- Rf 1- Z 1- Q 1- [H] a (7)
• Rf 1 , Z 1 , Q 1 , and a are as described above, and all a hydrogen atoms (H) enclosed in [] in the formulas (6) and (7) are Q 1 respectively.
• R 1 , i, j, k, l are as described above.
• W is an integer of 0 to 8.
• Adjacent) terminal aliphatic unsaturated group having an alkylene ether group represented by for example, an alkyl group containing an aliphatic unsaturated double bond such as an alkenyl group at the end, or a terminal alkenyl group
• an acrylic group Alternatively, it can be obtained by subjecting a compound containing an ⁇ -substituted acrylic group to a hydrosilylation addition reaction.
• examples of the fluoropolyether compound having a polyfunctional Si—H group represented by the above formulas (6) and (7) include those shown below. (In the formula, Rf 2 and v are the same as above.)
• the reactivity of the terminal aliphatic unsaturated group is sufficiently ensured by using a compound containing a (adjacent) terminal aliphatic unsaturated group having an alkylene ether group and an acrylic group or an ⁇ -substituted acrylic group. Therefore, the progress of hydrosilyl addition of the acrylic group or ⁇ -substituted acrylic group in the side reaction is effectively suppressed.
• a fluoropolyether compound having a polyfunctional Si—H group represented by the above formulas (6) and (7), a terminal aliphatic unsaturated group represented by the formula (8), and an acrylic group or an ⁇ -substituted acrylic group is mixed and stirred, and in the presence of a platinum group metal-based addition reaction catalyst, the reaction temperature is 50 to 150 ° C., preferably 60 to 120 ° C. for 1 minute to 72 hours, particularly 5 minutes to 12 hours. It is desirable to carry out the reaction.
• reaction temperature is too low, the reaction may stop without sufficiently proceeding, and if it is too high, the reaction may become uncontrollable due to the temperature rise due to the heat of reaction of hydrosilylation, resulting in sudden boiling or decomposition of the raw material. ..
• the charging ratio of the compound containing an acrylic group is the total number of moles of H enclosed in [] of the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (6) or (7).
• the terminal aliphatic unsaturated group represented by the formula (8), and the unsaturated group of the compound containing an acrylic group or an ⁇ -substituted acrylic group are used in an amount of 0.8 to 5 times mol, particularly 1 to 2 times mol. It is desirable to react.
• the amount of the compound containing the terminal aliphatic unsaturated group represented by the formula (8) and the acrylic group or the ⁇ -substituted acrylic group is too small, the polyfunctional Si-represented by the formulas (6) and (7) In a fluoropolyether compound having an H group, a large amount of Si—H groups may remain and the desired effect may not be obtained. If the amount is more than this, the uniformity of the reaction solution is lowered and the reaction rate becomes unstable, and after the reaction, the terminal aliphatic unsaturated group represented by the formula (8) and the acrylic group or the ⁇ -substituted acrylic group are contained. When removing a compound, it is necessary to make the conditions such as heating, depressurization, and extraction stricter as the excess unreacted components increase.
• a compound containing a platinum group metal such as platinum, rhodium or palladium
• a platinum group metal such as platinum, rhodium or palladium
• compounds containing platinum are preferable, and hexachloroplatinic (IV) acid hexahydrate, platinum carbonylvinyl methyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex,
• a complex of chloroplatinic acid and an olefin, aldehyde, vinyl siloxane, acetylene alcohol, or the like, or platinum supported on activated carbon can be used.
• the blending amount of the addition reaction catalyst is such that the amount of metal contained is 0.1 to 5,000 mass ppm with respect to the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (6) or (7). It is preferably 0.1 to 1,000 mass ppm.
• the above addition reaction can be carried out in the absence of a solvent, but may be diluted with a solvent if necessary.
• a widely used organic solvent such as toluene, xylene, and isooctane can be used.
• a fluorine-containing acrylic compound represented by the formula (2) or (3) which has a boiling point above the target reaction temperature and does not inhibit the reaction and is produced after the reaction, is used at the above reaction temperature. Soluble is preferred.
• a partially fluorine-modified solvent such as a fluorine-modified aromatic hydrocarbon solvent such as m-xylene hexafluorolide and benzotrifloride and a fluorine-modified ether solvent such as methyl perfluorobutyl ether is desirable, and particularly m-xylene. Hexafluorolides are preferred.
• the amount used is preferably 5 to 2,000 mass by mass with respect to 100 parts by mass of the fluoropolyether compound having a polyfunctional Si—H group represented by the formula (6) or (7). It is a part, more preferably 50 to 500 parts by mass. If it is less than this, the effect of dilution with a solvent is weak, and if it is more than this, the degree of dilution becomes too high and the reaction rate may decrease.
• the fluoroacrylic compound represented by the general formula (1) obtained by the above reaction is subjected to purification and isolation operations such as concentration, column purification, distillation, and extraction, and the reaction solution is used as it is in the general formula (1). It can also be used as a mixture containing a fluorine-containing acrylic compound represented by, or further diluted with an organic solvent or the like.
• the amount of the fluorine-containing acrylic compound according to the first embodiment of the present invention is 0.005 to 40 parts by mass, preferably 0, based on 100 parts by mass of the active energy ray-curable composition described later. It is a fluorine-containing active energy ray-curable composition characterized by containing 0.01 to 20 parts by mass. If the blending amount of the compound is smaller than this, the compound cannot be sufficiently arranged on the surface when the cured product is formed, and the expected liquid repellency and antifouling property cannot be exhibited. The influence of the fluorine-containing acrylic compound on the strength and hardness of the cured product layer becomes too large, and the cured product characteristics of the original active energy ray-curable composition are lost.
• the active energy ray-curable composition used in one embodiment of the present invention is not particularly limited as long as it gives a cured product by irradiation with active energy rays such as ultraviolet rays and electron beams, but is particularly non-fluorinated acrylic. It is preferable to contain the compound (a) and the photopolymerization initiator (b).
• the non-fluorine acrylic compound (a) can be used regardless of whether it is monofunctional or polyfunctional.
• Such an acrylic compound may have two or more acrylic groups or ⁇ -substituted acrylic groups in one molecule, and for example, 1,6-hexanediol di (meth) acrylate and neopentyl glycol di (meth).
• Preferable examples include those containing a copolymer or the like into which the above is introduced.
• urethane acrylates those obtained by reacting polyisocyanate with (meth) acrylate having a hydroxyl group, those obtained by reacting polyisocyanate with (meth) acrylate having a hydroxyl group with polyester of a terminal diol, and those obtained by reacting polyisocyanate with a (meth) acrylate having a hydroxyl group, and excess in polyol. It is also possible to use one obtained by reacting a (meth) acrylate having a hydroxyl group with a polyisocyanate obtained by reacting the diisocyanate of the above.
• (meth) acrylate having a hydroxyl group selected from 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol triacrylate, hexamethylene diisocyanate, isophorone diisocyanate, and tolylene diisocyanate.
• a polyfunctional acrylic compound having two or more acrylic groups or ⁇ -substituted acrylic groups in one molecule and not having a urethane bond or this polyfunctional acrylic compound, and an acrylic compound having an aliphatic polyisocyanate and a hydroxyl group. It may be a mixture of at least two kinds of acrylic compounds including those composed of polyfunctional urethane acrylates having 3 or more acrylic groups or ⁇ -substituted acrylic groups in one molecule obtained by reacting.
• trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) are examples of polyfunctional acrylic compounds having two or more acrylic groups or ⁇ -substituted acrylic groups in one molecule and not having a urethane bond.
• examples of the polyfunctional urethane acrylates having three or more acrylic groups or ⁇ -substituted acrylic groups in one molecule obtained by reacting an aliphatic polyisocyanate with an acrylic compound having a hydroxyl group include hexamethylene diisocyanate and norbornean.
• the component (a) may include not only a liquid component but also a fine particle high molecular weight body surface and an inorganic filler fine particle surface modified with an acrylic group.
• the component (a) as described above can be used alone, but it can also be used by blending a plurality of applicable compounds in order to improve the coatability and the characteristics of the film after curing.
• a curable composition having enhanced curability when ultraviolet rays are used as active energy rays can be obtained.
• the photopolymerization initiator of the component (b) is not particularly limited as long as it can cure the acrylic compound by irradiation with ultraviolet rays, but is preferably, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2-.
• the content of the component (b) can be appropriately determined according to the curing conditions and the physical properties of the cured product of the target active energy ray-curable composition. For example, with respect to a total of 100 parts by mass of the component (a).
• the amount is preferably 0.1 to 15 parts by mass, particularly 1 to 10 parts by mass. If the amount added is less than this, the curability may decrease, and if it is more than this, the effect on the physical properties after curing may increase.
• the active energy ray-curable composition includes active energy ray-reactive compounds other than acrylic groups such as thiol compounds and maleimide compounds, organic solvents, polymerization inhibitors, antistatic agents, defoaming agents, viscosity modifiers, etc.
• active energy ray-reactive compounds other than acrylic groups such as thiol compounds and maleimide compounds, organic solvents, polymerization inhibitors, antistatic agents, defoaming agents, viscosity modifiers, etc.
• Light-resistant stabilizers, heat-resistant stabilizers, antioxidants, surfactants, colorants, and fillers of polymers and inorganic substances can also be blended.
• the structure of these is not particularly limited, and known ones can be used as long as the object of the present invention is not impaired.
• the active energy ray-curable composition containing the components (a) and (b) and various additives is classified by each company as a paint, an ink, a hard coat agent, etc.
• Existing commercially available compositions may be used as part or as a whole of the active energy ray-curable composition. Even when a commercially available hard coat agent is used in this way, an organic solvent, a polymerization inhibitor, an antistatic agent, a defoaming agent, a viscosity modifier, a light-resistant stabilizer, a heat-resistant stabilizer, and an oxidation are used depending on the purpose.
• Inhibitors, surfactants, colorants, fillers and the like can be added and blended.
• the fluorine-containing acrylic compound of the present invention has excellent compatibility with a non-fluorine-based organic solvent, it is not necessary to add a volatile fluorine compound as a phase solvent in the preparation of the fluorine-containing active energy ray-curable composition.
• the content of the volatile fluorine compound is 1 part by mass or less (0 to 1 part by mass), particularly 0.1 part by mass or less (0 to 0.) With respect to 100 parts by mass of the above-mentioned active energy ray-curable composition. Even if it is 1 part by mass), a uniform fluorine-containing active energy ray-curable composition can be prepared.
• the fluorine-containing active energy ray-curable composition of the present invention obtained as described above contains a perfluoropolyether group as a water- and oil-repellent group and an acrylic group or an ⁇ -substituted acrylic group as the active energy ray-curable group. Since it contains a fluoroacrylic compound, it provides excellent cured products such as water repellency, oil repellency, slipperiness, antifouling property, fingerprint wiping property, low refractive index property, solvent resistance, and chemical resistance. Since this fluorine-containing acrylic compound does not contain a urethane bond in the molecule, a cured product having excellent wear resistance can be obtained. Furthermore, it is also suitable as an intermediate of a formulation that imparts these functions.
• the above-mentioned fluorine-containing active energy ray-curable composition of the present invention is applied to the surface of a base material and cured, and the surface has a cured product layer (also referred to as a cured film or a cured resin layer). Goods).
• a cured product layer also referred to as a cured film or a cured resin layer.
• Goods As described above, by using the fluorine-containing active energy ray-curable composition of the present invention, it is possible to form a cured film (cured resin layer) having excellent surface characteristics on the surface of the base material. In particular, it is useful for imparting water repellency, oil repellency, and stain resistance to the surface of the acrylic hard coat.
• the fluorine-containing active energy ray-curable composition of the present invention provides a coating film or a protective film on the surface of a base material (article) that may be touched by the human body and contaminated by human fat, cosmetics, or the like. Can be done.
• the cured film (cured resin layer) formed by using the polystyrene-containing active energy ray-curable composition of the present invention is directly applied to the surface of an article to be imparted with properties and cured, or various base films (for example, various base films).
• an energy ray-curable composition to prepare a cured film and attaching the film to the surface of a target article, properties can be imparted to various articles.
• the coating method of the fluorine-containing active energy ray-curable composition of the present invention is not particularly limited, but for example, roll coat, gravure coat, flow coat, dip coat, spray coat, spin coat, bar coat. , A known coating method such as screen printing can be used.
• the coating film is irradiated with active energy rays to cure it.
• the active energy ray any beam such as an electron beam and ultraviolet rays can be used, but ultraviolet rays are particularly preferable.
• the ultraviolet source a mercury lamp, a metal halide lamp, and an LED lamp are suitable. If the amount of ultraviolet irradiation is too small, uncured components will remain, and if it is too large, the coating film and base material may deteriorate.
• the irradiation atmosphere is replaced with an inert gas that does not contain oxygen molecules such as nitrogen, carbon dioxide, and argon during ultraviolet irradiation, and the surface of the coating film is transmitted by ultraviolet rays that have releasability.
• an inert gas that does not contain oxygen molecules such as nitrogen, carbon dioxide, and argon during ultraviolet irradiation
• the surface of the coating film is transmitted by ultraviolet rays that have releasability.
• the coating film and the base material may be heated by an arbitrary method such as a hot air drying oven before and during the irradiation with ultraviolet rays.
• the thickness of the cured film (cured resin layer) formed by using the fluorine-containing active energy ray-curable composition of the present invention is not particularly limited, but when the obtained film thickness is too thin, the thickness is not particularly limited. Since sufficient surface hardness cannot be obtained and if it is too thick, the mechanical strength of the hard coat film is lowered and cracks are likely to occur, it is usually preferably 5 nm to 100 ⁇ m, particularly preferably 1 ⁇ m to 20 ⁇ m.
• the cured film (cured resin layer) formed by using the fluorine-containing active energy ray-curable composition of the present invention has a water contact angle of 90 ° or more, preferably 95 ° or more at 25 ° C. and a relative humidity of 40%. Is desirable.
• the water contact angle is a value measured under the condition of droplets: 2 ⁇ l using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.). Further, in order to obtain the water contact angle, it is preferable that the fluorine-containing active energy ray-curable composition is uniformly mixed.
• Examples of such articles include tablet computers, mobile (communication) information terminals such as mobile phones and smartphones, notebook PCs, digital media players, clock-type and eyeglass-type wearable computers, digital cameras, digital video cameras, and electronic books. Housing for various devices such as readers that can be carried by hand; various flat panels such as liquid crystal displays, plasma displays, organic EL displays, rear projection displays, vacuum fluorescent displays (VFD), field emission projection displays, CRTs, and toner-based displays.
• various flat panels such as liquid crystal displays, plasma displays, organic EL displays, rear projection displays, vacuum fluorescent displays (VFD), field emission projection displays, CRTs, and toner-based displays.
• Display operation equipment surfaces such as displays and TV screens, automobile exteriors, glossy surfaces of pianos and furniture, architectural stone surfaces such as marble, decorative building materials around water such as toilets, baths, and washrooms, protection for art exhibitions
• Transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members such as glass, show windows, showcases, photo frame covers, watches, automobile window glass, window glass for trains and aircraft, automobile headlights, tail lamps, etc. It is useful as a coating film and a surface protective film for various mirror members and the like.
• various devices such as touch panel displays that have display input devices that operate on the screen with human fingers or palms, such as tablet computers, notebook PCs, clock-type wearable computers, activity meters, mobile phones, smartphones, and other mobile phones ( Communication) Information terminals, digital media players, electronic book readers, digital photo frames, game machines and game machine controllers, digital cameras, digital video cameras, navigation devices for automobiles, automatic cash withdrawal deposit devices, automatic cash payment machines, It is useful as a surface protective film for various controllers such as vending machines, digital signage (electronic signage), security system terminals, POS terminals, remote controllers, and display input devices such as panel switches for in-vehicle devices.
• various controllers such as vending machines, digital signage (electronic signage), security system terminals, POS terminals, remote controllers, and display input devices such as panel switches for in-vehicle devices.
• the cured film formed by the fluorine-containing active energy ray-curable composition of the present invention is an optical recording medium such as a photomagnetic disk or an optical disk; a glasses lens, a camera lens, a projector lens prism, a lens sheet, a pellicle film, a polarizing plate. It is also useful as a surface protective film for optical components and optical devices such as optical filters, lenticular lenses, frennel lenses, antireflection films, optical fibers and optical couplers, or as a surface protective film for various protective components of these devices.
• E-40 4-functional acrylate (EBECRYL 40, manufactured by Daicel Cytec Co., Ltd.)
• IPA Solvent (isopropanol)
• I-184 1-Hydroxycyclohexylphenyl ketone (Irgacure 184, manufactured by Ciba Japan Co., Ltd.)
• Examples 1 to 6 prepared by using fluorine-containing acrylic compounds (compounds (A) to (F)) containing no urethane bond in the molecular structure as a water / oil repellency and antifouling property-imparting agent are excellent in prevention. It showed stain resistance and high wear resistance was confirmed.
• Comparative Example 1 produced by using a fluorine-containing acrylic compound containing a urethane bond in the molecular structure as a water / oil repellent and antifouling property imparting agent showed excellent antifouling property, but was subjected to an abrasion test. The water contact angle was greatly reduced, indicating low wear resistance.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Polyethers (AREA)
• Silicon Polymers (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=74060834

Family Applications (1)

Country Status (7)

Cited By (6)

Families Citing this family (2)

Citations (10)

Family Cites Families (3)

• 2020
  • 2020-06-22 US US17/621,348 patent/US12378339B2/en active Active
  • 2020-06-22 EP EP20833589.3A patent/EP3992215A4/en active Pending
  • 2020-06-22 JP JP2021526957A patent/JP7279788B2/ja active Active
  • 2020-06-22 WO PCT/JP2020/024285 patent/WO2020262272A1/ja not_active Ceased
  • 2020-06-22 CN CN202080044473.5A patent/CN114008108B/zh active Active
  • 2020-06-22 KR KR1020227002137A patent/KR102938888B1/ko active Active
  • 2020-06-24 TW TW109121427A patent/TWI864030B/zh active

Patent Citations (10)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events