CN116964118A - Curable composition for hard coating - Google Patents

Curable composition for hard coating Download PDF

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Publication number
CN116964118A
CN116964118A CN202280020520.1A CN202280020520A CN116964118A CN 116964118 A CN116964118 A CN 116964118A CN 202280020520 A CN202280020520 A CN 202280020520A CN 116964118 A CN116964118 A CN 116964118A
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group
poly
hard coat
curable composition
film
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胁田健吾
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
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    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
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    • C08F20/24—Esters containing halogen containing perhaloalkyl radicals
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    • 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
    • C08F22/00—Homopolymers and 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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/10—Esters
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08G65/02—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
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    • 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
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains 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
    • C09D135/00—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 a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D135/02—Homopolymers or copolymers of esters
    • 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

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  • Paints Or Removers (AREA)

Abstract

The present invention provides a homogeneous curable composition free from suspended matters and precipitates, which can form a hard coat layer having both durability and sliding properties at a high level of properties and having high liquid repellency in addition to the actual use. The present invention provides a curable composition comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer having two or more (meth) acryloyl groups in one molecule; (b) 0.05 to 2 parts by mass of a perfluoropolyether having an active energy ray polymerizable group via a poly (oxyalkylene) group only at one end of a molecular chain containing the poly (oxyperfluoroalkylene) group and having a weight average molecular weight of 1500 to 3500; and (c) 1 to 20 parts by mass of a polymerization initiator generating radicals by active energy rays.

Description

Curable composition for hard coating
Technical Field
The present invention relates to a curable composition useful as a material for forming a hard coat layer applied to the surfaces of various display elements, and relates to a homogeneous curable composition which can form a hard coat layer excellent in slidability, scratch resistance, abrasion resistance and water repellency and free from suspended matters and precipitates.
Background
In recent years, touch panels have been introduced into various devices such as portable information terminal devices such as mobile phones and tablet computers, notebook personal computers, home electric appliances, and interior and exterior articles of automobiles, and the surfaces of the touch panels of display elements such as liquid crystal displays and organic EL displays have been operated by finger or pen contact. When finger manipulation is assumed, the surface of the touch panel is required to have water repellency and oil repellency for facilitating removal of attached fingerprints, and further, abrasion resistance is required to maintain water repellency and oil repellency even by repeated rubbing with fingers. Further, in the case of operating the surface of the touch panel with a finger or a pen, the surface is required to have slidability from the viewpoint of the touch feeling of the finger or the pen. Further, the surface of the touch panel is required to have scratch resistance in order to prevent damage. In order to impart these characteristics to the surface of the touch panel, a surface coating such as a hard coating is provided.
Since the fluorine-containing compound exhibits high slidability and water and oil repellency, for example, a method of adding a small amount of a fluorine-based surface modifier to a coating liquid for forming a hard coat layer to prepare a composition is used as a material for forming a hard coat layer. The fluorine-based surface modifier is known to segregate on the surface of the hard coat layer due to the low surface energy of fluorine atoms.
In general, in order to impart scratch resistance and abrasion resistance to a hard coat layer, a method of improving the surface hardness of the hard coat layer by forming a high-density crosslinked structure to thereby provide resistance to external force is employed. As a material for forming such a hard coat layer, a multifunctional acrylate material which is three-dimensionally crosslinked by radicals generated by irradiation with active energy rays is currently used at most. The fluorine-based surface modifier added to the coating liquid for forming the hard coat layer is also a material having an active energy ray polymerizable group for imparting scratch resistance and abrasion resistance to the hard coat layer (patent document 1).
On the other hand, as described in patent document 2, since durability characteristics such as scratch resistance and abrasion resistance are required for the hard coat layer, for example, in the case of using a fluorine-based surface modifier having a crosslinkable group, immobilization of a molecular chain containing a fluorine atom occurs, and the sliding property of the hard coat layer is lowered. That is, it is difficult to achieve a high level of characteristics while the durability characteristics such as scratch resistance and abrasion resistance are in a trade-off relationship with the sliding properties.
In order to improve the trade-off relationship, there is a method of introducing a crosslinkable group only at one end of a molecular chain containing a fluorine atom in order to improve the mobility of the molecular chain containing a fluorine atom. However, the hard coating layer is excellent in sliding properties as compared with the method of introducing crosslinkable groups at both ends of the fluorine atom-containing molecular chain, but generally tends to be poor in durability, and the fluorine atom-containing molecular chain tends to aggregate, and when a coating liquid for forming the hard coating layer is prepared, the coating liquid tends to be cloudy. When the fluorine-based surface modifier is aggregated in the coating liquid for forming the hard coat layer, the molecular chains containing fluorine atoms do not segregate sufficiently on the surface of the hard coat layer when the hard coat layer is formed using the coating liquid, and the original characteristics of slidability, water repellency, and scratch resistance cannot be exhibited.
In order to improve the solubility of the fluorine-based surface modifier, a method of reducing the content of fluorine atoms in the fluorine-based surface modifier, for example, a method of shortening the molecular chain containing fluorine atoms may be considered, but as a result, it is considered that the slidability and water repellency of the hard coating layer are reduced, and it is difficult to satisfy the high characteristic level of slidability and water repellency.
As a method for improving the solubility of a fluorine-based surface modifier, patent document 3 reports the use of a fluorine-containing polyether which becomes a agglomerate when a hard coat agent composition is obtained and becomes a factor of clouding of the composition, and a fluorine-containing block copolymer excellent in compatibility with the composition.
Prior art literature
Patent literature
Patent document 1: international publication No. 2016/163479
Patent document 2: japanese patent No. 6497449
Patent document 3: japanese patent laid-open No. 2005-179613
Disclosure of Invention
Problems to be solved by the invention
Patent document 3 describes that the fluorinated block copolymer described in the document has poor water repellency and lubricity compared to the fluorinated polyether, and therefore, the fluorinated block copolymer has a lower fluorine concentration than the fluorinated polyether, and it is easily conceivable that compatibility with the composition, slidability, and water repellency are difficult to be simultaneously achieved.
In the present invention, there is a problem in that a homogeneous curable composition free from suspended matters and precipitates is provided which enables the formation of a hard coat layer having both of durability characteristics and sliding properties in a trade-off relationship at a high characteristic level. In addition, the hard coat layer is required to have high liquid repellency in addition to the actual use.
Solution for solving the problem
A first aspect of the present invention is a curable composition comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer having two or more (meth) acryloyl groups in one molecule; (b) 0.05 to 2 parts by mass of a perfluoropolyether having an active energy ray polymerizable group via a poly (oxyalkylene) group only at one end of a molecular chain containing the poly (oxyperfluoroalkylene) group and having a weight average molecular weight of 1500 to 3500; and (c) 1 to 20 parts by mass of a polymerization initiator generating radicals by active energy rays.
Another aspect of the present invention is a curable composition comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer having two or more (meth) acryloyl groups in one molecule; (b) 0.05 to 2 parts by mass of a perfluoropolyether which is a reaction product of a starting perfluoropolyether having a hydroxyl group bonded to a poly (oxyalkylene) group only at one end of a molecular chain containing the poly (oxyperfluoroalkylene) group and having a number average molecular weight of 1500 to 3000, and a compound having a functional group reactive with the hydroxyl group and an active energy ray polymerizable group; and (c) 1 to 20 parts by mass of a polymerization initiator generating radicals by active energy rays.
The (b) perfluoropolyether has the active energy ray polymerizable group via the poly (oxyalkylene) group only at one end of a molecular chain containing the poly (oxyperfluoroalkylene) group, and has a weight average molecular weight of 1500 to 3500.
The perfluoropolyether (b) has the active energy ray-polymerizable group via a urethane bond bonded to the poly (oxyalkylene) group.
The poly (oxyalkylene) group is a poly (oxyethylene) group.
The poly (oxyperfluoroalkylene) group has a repeating unit- (CF) 2 O) -and/or repeating units- (CF) 2 CF 2 O) -, in the case of having both repeating units, the poly (oxyperfluoroalkylene) group is a group in which these repeating units are bonded by block bonding, random bonding, or both block bonding and random bonding.
The molecular chain comprising the poly (oxidized perfluoroalkylene) group has a structure represented by the following formula [1 ].
(above formula [1]]In which m is a repeating unit- (CF) 2 CF 2 Number of O) -and n is the repeating unit- (CF) 2 O) -amount, satisfying 5.ltoreq.m+n.ltoreq.30, m and n each independently represent an integer of 0 or more, q is the amount of oxyethylene groups, and represents an integer of 2 to 20. )
In the formula [1], m and n each independently represent an integer of 1 or more.
The perfluoropolyether (b) is a compound represented by the following formula [2 ].
(in the above formula [2], m, n and q have the same meanings as defined in the above formula [1], A represents a terminal group having the above active energy ray-polymerizable group.)
The terminal group A is a group represented by the following formula [ A1] or formula [ A2 ].
(above formula [ A1]]And [ A2]]Wherein R is 1 And R is 2 Each independently represents a hydrogen atom or a methyl group, and the formula [2]]The urethane bonds of the compounds shown are bonding bonds. )
The curable composition of the present invention further comprises (d) a solvent.
Another embodiment of the present invention is a cured film obtained from the curable composition of the present invention.
Another embodiment of the present invention is a hard coat film comprising a hard coat layer on at least one surface of a film base material, wherein the hard coat layer is composed of the cured film.
And a lower layer having a hard coat layer between the surface of the film base material and the hard coat layer, wherein the film base material is a resin film.
The hard coat layer has a film thickness of 1 μm to 20 μm.
Another aspect of the present invention is a method for producing a hard coat film, comprising: a step of forming a coating film by applying the curable composition of the present invention to a film substrate; and a step of forming a hard coat layer by irradiating the coating film with an active energy ray to cure the coating film.
Another aspect of the present invention is a method for producing a hard coat film, comprising: a step of forming a coating film by applying the curable composition of the present invention to a film substrate; a step of removing the solvent from the coating film by heating; and a step of forming a hard coat layer by irradiating the coating film with an active energy ray to cure the coating film.
A method for producing a hard coat film, further comprising: and forming a lower layer of a hard coat layer on the surface of the film base material, wherein the film base material is a resin film, and the coating film is formed on the lower layer of the hard coat layer.
Another embodiment of the present invention is a perfluoropolyether compound having an active energy ray polymerizable group via a poly (oxyalkylene) group only at one end of a molecular chain containing a poly (oxyperfluoroalkylene) group and having a weight average molecular weight of 1500 to 3500.
Another embodiment of the present invention is a perfluoropolyether compound which is a reaction product of a starting perfluoropolyether having a hydroxyl group bonded to a poly (oxyalkylene) group only at one end of a molecular chain containing the poly (oxyperfluoroalkylene) group and having a number average molecular weight of 1500 to 3000, and a compound having a functional group reactive with the hydroxyl group and an active energy ray polymerizable group.
The perfluoropolyether compound has the active energy ray polymerizable group via the poly (oxyalkylene) group only at one end of a molecular chain containing the poly (oxyperfluoroalkylene) group, and has a weight average molecular weight of 1500 to 3500.
The molecular chain comprising the poly (oxidized perfluoroalkylene) group has a structure represented by the following formula [1 ].
(above formula [1]]In which m is a repeating unit- (CF) 2 CF 2 Number of O) -and n is the repeating unit- (CF) 2 O) -number, satisfying 5.ltoreq.m+n.ltoreq.30, m and n each independently represent an integer of 0 or more, and in the case of having repeating units of both sides, these repeating units are bonded by block bonding, random bonding, or block bonding and random bonding, q is the number of oxyethylene groups, and represents an integer of 2 to 20. )
In the formula [1], m and n each independently represent an integer of 1 or more.
The perfluoropolyether compound is a compound represented by the following formula [2 ].
(in the above formula [2], m, n and q have the same meanings as defined in the above formula [1], A represents a terminal group represented by the following formula [ A1] or formula [ A2] having the above active energy ray-polymerizable group.)
(above formula [ A1]]And [ A2]]Wherein R is 1 And R is 2 Each independently represents a hydrogen atom or a methyl group, and the formula [2] ]The urethane bonds of the compounds shown are bonding bonds. )
Effects of the invention
According to the present invention, there can be provided a curable composition having excellent uniformity, which is useful for forming a cured film and a hard coat layer having excellent abrasion resistance/wear resistance and excellent sliding properties even in a film having a thickness of 1 μm to 20 μm. Further, according to the present invention, a cured film obtained from the curable composition or a hard coating film having a hard coating layer composed of the cured film can be provided, and a hard coating film excellent in both durability characteristics such as scratch resistance and abrasion resistance and sliding properties in a trade-off relationship can be provided. The present invention can provide a curable composition useful for forming a cured film and a hard coating layer which have both the above characteristics and also have high water repellency, and a hard coating film having a hard coating layer excellent in these characteristics.
Detailed Description
Curable composition
The components of the curable composition of the present invention will be described below.
[ (a) active energy ray-curable multifunctional monomer having two or more (meth) acryloyl groups in one molecule ]
(a) The active energy ray-curable polyfunctional monomer having two or more (meth) acryloyl groups in one molecule of the component (hereinafter, also simply referred to as "(a) polyfunctional monomer") means a monomer that undergoes polymerization reaction and curing by irradiation of active energy rays such as ultraviolet rays.
In the curable composition of the present invention, the preferable (a) polyfunctional monomer is a monomer selected from the group consisting of polyfunctional (meth) acrylate compounds, and further, examples thereof include: the monomer selected from the group consisting of multifunctional urethane (meth) acrylate compounds, and the monomer selected from the group consisting of lactone-modified multifunctional (meth) acrylate compounds, which will be described later. In the present invention, as the (a) polyfunctional monomer, one selected from the group consisting of the above polyfunctional (meth) acrylate compounds may be used alone, or two or more kinds may be used in combination. In the present invention, (meth) acrylate compounds include both acrylate compounds and methacrylate compounds, and for example, (meth) acrylic acid includes acrylic acid and methacrylic acid.
The (a) polyfunctional monomer may be an oxyalkylene-modified polyfunctional monomer, and examples of the oxyalkylene modification include: oxymethylene modification, oxyethylene modification and oxypropylene modification. Examples of the oxyalkylene-modified polyfunctional monomer include those modified with an oxyalkylene group among the polyfunctional (meth) acrylate compounds and polyfunctional urethane (meth) acrylate compounds described above. The oxyalkylene-modified polyfunctional monomer may be used singly or in combination of two or more.
Further, in the present invention, as the preferable (a) polyfunctional monomer, polyfunctional monomers having at least two (meth) acryloyl groups in one molecule, preferably polyfunctional monomers having at least three (meth) acryloyl groups in one molecule, more preferably polyfunctional monomers having at least four (meth) acryloyl groups in one molecule, are exemplified.
Examples of the polyfunctional (meth) acrylate compound (among them, a compound having no urethane bond) include: trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ethoxyAlkylated dipentaerythritol hexa (meth) acrylate, ethoxylated glycerol tri (meth) acrylate, ethoxylated bisphenol a di (meth) acrylate, 1, 3-propanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 2-methyl-1, 8-octanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tricyclo [5.2.1.0 2，6 ]Decanedimethanol di (meth) acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxy propane, 2-hydroxy-1, 3-di (meth) acryloyloxy propane, 9-bis [4- (2- (meth) acryloyloxy) ethoxy) phenyl]Fluorene, bis [4- (meth) acryloylthiophenyl ]]Thioether, bis [2- (meth) acryloylthioethyl]Thioether, 1, 3-adamantanediol di (meth) acrylate, 1, 3-adamantanedimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate. Among them, preferable polyfunctional (meth) acrylate compounds include: pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
Examples of the oxyalkylene-modified polyfunctional (meth) acrylate compound include (meth) acrylate compounds of a polyol modified with an oxyalkylene group. Examples of the polyol include: glycerol, diglycerol, triglycerol, tetraglycerol, pentaglycerol, hexaglycerol, decaglycerol, polyglycerol, trimethylolpropane, di (trimethylol) propane, pentaerythritol and dipentaerythritol.
The above-mentioned polyfunctional urethane (meth) acrylate compound is a compound having a plurality of acryl groups or methacryl groups in one molecule and having one or more urethane bonds [ -NHC (=O) O- ], and may further have urea bonds [ -NHC (=O) NH- ]. Examples of the polyfunctional urethane (meth) acrylate compound include: the compound obtained by the reaction of the polyfunctional isocyanate and the (meth) acrylate having a hydroxyl group, and the compound obtained by the reaction of the polyfunctional isocyanate and the (meth) acrylate having a hydroxyl group and the polyol, but the polyfunctional urethane (meth) acrylate compound usable in the present invention is not limited to these examples.
Examples of the polyfunctional isocyanate include: toluene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate. Examples of the (meth) acrylate having a hydroxyl group include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tripentaerythritol hepta (meth) acrylate. Examples of the polyol include: diols such as ethylene glycol, propylene glycol, neopentyl glycol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, dipropylene glycol, etc.; polyester polyols which are reaction products of these diols with aliphatic dicarboxylic acids or dicarboxylic anhydrides such as succinic acid, maleic acid, adipic acid, etc.; polyether polyols; and (3) polycarbonate diol.
(a) The polyfunctional monomer may be a lactone-modified polyfunctional (meth) acrylate compound, and epsilon-caprolactone is preferable as the modified lactone. Examples of the lactone-modified polyfunctional (meth) acrylate compound include: epsilon-caprolactone-modified pentaerythritol tri (meth) acrylate, epsilon-caprolactone-modified pentaerythritol tetra (meth) acrylate, epsilon-caprolactone-modified dipentaerythritol penta (meth) acrylate, and epsilon-caprolactone-modified dipentaerythritol hexa (meth) acrylate.
[ (b) an active energy ray-polymerizable group via a poly (oxyalkylene) group only at one end of a molecular chain comprising the poly (oxyperfluoroalkylene) group, and a perfluoropolyether having a weight-average molecular weight of 1500 to 3500 ]
Hereinafter, the perfluoropolyether having an active energy ray polymerizable group only at one end of a molecular chain containing a poly (oxyperfluoroalkylene) group and having a weight average molecular weight of 1500 to 3500 is also referred to simply as "(b) perfluoropolyether"). (b) The perfluoropolyether is obtained, for example, by reacting a starting perfluoropolyether having a hydroxyl group bonded to a poly (oxyalkylene) group only at one end of a molecular chain containing the poly (oxyperfluoroalkylene) group with a compound having a functional group reactive with the hydroxyl group and the active energy ray polymerizable group, and having a number average molecular weight of 1500 to 3000. Examples of the functional group that reacts with the hydroxyl group include: hydroxyl, carboxyl, and isocyanate groups. In the curable composition of the present invention, (b) the perfluoropolyether preferably has the active energy ray polymerizable group only at one end of a molecular chain containing the poly (oxyperfluoroalkylene) group via a urethane bond bonded to the poly (oxyalkylene) group.
(b) The perfluoropolyether has a poly (oxyalkylene) group, and therefore has excellent compatibility with (a) the polyfunctional monomer, and can function as a surface modifier in a hard coat layer formed from the curable composition of the present invention by only (b) the perfluoropolyether. As the above-mentioned poly (oxyalkylene) group, a poly (oxyethylene) group is preferable.
(b) The perfluoropolyether is not limited to having one active energy ray polymerizable group only at one end of a molecular chain including a poly (oxidized perfluoroalkylene) group via a poly (oxyalkylene) group, and may have two or more active energy ray polymerizable groups. Examples of the active energy ray-polymerizable group include a (meth) acryloyl group and a vinyl group, and examples of the terminal group having the active energy ray-polymerizable group include a group represented by the formula [ A1] or the formula [ A2 ]. Of these terminal groups, those having two active energy ray-polymerizable groups and represented by the formula [ A2] are preferable.
The poly (oxyperfluoroalkylene) group is preferably present in the cured film from the viewpoint of obtaining a cured film having excellent scratch resistance 2 O]- (oxidized perfluoromethylene) and- [ CF 2 CF 2 O]Both of the (perfluoroethylene oxide) groups are repeating units. In this case, the bonding of these oxidized perfluoroalkylenes may be any of block bonding and random bonding.
(b) The fluorine atom content of the perfluoropolyether is preferably 35% by mass or more and 60% by mass or less, more preferably 40% by mass or more and 55% by mass or less. When the fluorine atom content is 35 mass% or more, a hard coat layer excellent in water repellency and sliding properties can be obtained, and when 60 mass% or less, the hard coat layer is sufficiently compatible with the (a) polyfunctional monomer, and a hard coat layer with little cloudiness can be obtained.
(b) The perfluoropolyether has a weight average molecular weight of 1500 to 3500, preferably 1600 to 3500, more preferably 1700 to 3000. When the weight average molecular weight of the perfluoropolyether (b) is in the above range, the perfluoropolyether (b) is liable to remain on the surface of the hard coat layer obtained from the curable composition of the present invention, and the shear stress on the surface of the layer becomes sufficiently small, so that a hard coat layer excellent in sliding properties can be obtained. In addition, when the weight average molecular weight of the perfluoropolyether (b) is in the above range, a hard coat layer excellent in durability such as scratch resistance can be obtained by appropriately adjusting the hardness of the layer surface. That is, when the weight average molecular weight of the perfluoropolyether (b) is in the above range, both slidability and durability can be achieved.
In the curable composition of the present invention, the content of the perfluoropolyether (b) is 0.05 to 2 parts by mass relative to 100 parts by mass of the polyfunctional monomer (a). Since the content of the perfluoropolyether (b) is 0.05 parts by mass or more and the perfluoropolyether (b) is sufficiently present on the surface of the hard coat layer obtained from the curable composition of the present invention, a hard coat layer excellent in sliding properties can be obtained. In addition, the content of the perfluoropolyether (b) is 2 parts by mass or less, whereby the perfluoropolyether (b) is sufficiently compatible with the polyfunctional monomer (a) to give a hard coat layer having little cloudiness.
(b) The perfluoropolyether may be used singly or in combination of two or more.
[ (c) polymerization initiator ]
The polymerization initiator (c) used in the curable composition of the present invention is preferably a polymerization initiator that generates radicals by irradiation with active energy rays such as electron beams, ultraviolet rays, and X rays, in particular, ultraviolet rays.
Examples of the polymerization initiator (c) include: benzoin, alkylbenzene, thioxanthone, azo, azide, diazonium, o-quinone diazide, acylphosphine oxide, oxime ester, organic peroxide, benzophenone, biscoumarin, bisimidazole, titanocene, thiol, halogenated hydrocarbon, trichloromethyl triazine, iodonium salt, sulfonium salt, and other onium salts. These polymerization initiators may be used singly or in combination of two or more. In the present invention, an alkylbenzene type is preferably used as the (c) polymerization initiator from the viewpoints of transparency, surface curability and film curability. By using the alkylbenzene, a cured film having further improved scratch resistance can be obtained.
Examples of the alkylbenzene ketones include: alpha-hydroxyalkylphenones such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one, 2-hydroxy-1- (4- (2-hydroxy-2-methylpropanoyl) benzyl) phenyl) -2-methylpropan-1-one, and the like; α -aminoalkyl phenones such as 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one; 2, 2-dimethoxy-1, 2-diphenylethan-1-one; methyl phenylglyoxylate.
In the curable composition of the present invention, the content of the (c) polymerization initiator is 1 to 20 parts by mass, preferably 2 to 10 parts by mass, relative to 100 parts by mass of the (a) polyfunctional monomer.
[ (d) solvent ]
The curable composition of the present invention may contain (d) a solvent as an optional component, that is, may be in the form of a varnish. The solvent (d) may be appropriately selected in consideration of the solubility/dispersibility of the above-mentioned components (a) to (c), workability at the time of application of a curable composition related to formation of a cured film (hard coat layer) to be described later, drying property before and after curing, and the like.
Examples of the solvent (d) include: aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetrahydronaphthalene; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits, and cyclohexane; halides such as methyl chloride, methyl bromide, methyl iodide, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, and o-dichlorobenzene; esters or ester ethers such as ethyl acetate, propyl acetate, butyl methoxyacetate, methyl cellosolve acetate, ethyl cellosolve acetate, and Propylene Glycol Monomethyl Ether Acetate (PGMEA); ethers such as diethyl ether, tetrahydrofuran (THF), 1, 4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene Glycol Monoethyl Ether (PGME), propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, and propylene glycol mono-n-butyl ether; ketones such as acetone, methyl Ethyl Ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, and cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol, and ethylene glycol; amides such as N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP); and sulfoxides such as dimethyl sulfoxide (DMSO), and a solvent obtained by mixing two or more of these solvents.
In the curable composition of the present invention, the content of the solvent (d) is not particularly limited, and is, for example, a concentration of 1 to 70 mass%, preferably 5 to 50 mass% of the solid content of the curable composition of the present invention. The solid content concentration (also referred to as nonvolatile content concentration) herein means the content of the solid component (the portion from which the solvent component is removed from the entire components) of the curable composition of the present invention relative to the total mass (total mass) of the components (a) to (d) and other additives.
[ other additives ]
In the curable composition of the present invention, as long as the effect of the present invention is not impaired, a usual additive may be appropriately blended, for example, one of a polymerization inhibitor, a photosensitizer, a leveling agent, a surfactant, an adhesion-imparting agent, a plasticizer, an ultraviolet absorber, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, a dye, or the like, alone or in combination of two or more of them may be appropriately blended as required.
< cured film >)
The curable composition of the present invention can be applied (coated) onto a substrate to form a coating film, and the coating film is irradiated with an active energy ray to polymerize (cure) the coating film to form a cured film, which is also the object of the present invention. As the hard coat layer in the hard coat film described later, a hard coat layer composed of the cured film described above may be used.
Examples of the base material include: various resins (polyesters such AS polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET), and polyethylene naphthalate (PEN), polyurethanes, thermoplastic Polyurethanes (TPU), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, cellulose Triacetate (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene resin), metals, wood, paper, glass, and slate (slate). The shape of these substrates may be plate-like, film-like or three-dimensional molded bodies. In addition, for example, a primer layer, an ultraviolet absorbing layer, an infrared absorbing layer, a near infrared absorbing layer, an electromagnetic wave absorbing layer, a color correction layer, a refractive index adjusting layer, a weather resistant layer, an antireflection layer, an antistatic layer, an anti-discoloration layer, a gas barrier layer, a water vapor barrier layer, a light scattering layer, an electrode layer, and the like may be formed as an underlayer of a hard coat layer on the surface of the substrate, or a plurality of underlayer of the hard coat layer may be laminated. The layer formed on the surface of the substrate is not particularly limited as long as the effect of the present invention is not impaired.
The coating method on the substrate may be appropriately selected from a cast coating method (cast coat method), a spin coating method, a doctor blade method, a dip coating method, a roll coating method, a spray coating method, a bar coating method, a die coating method, an inkjet method, a printing method (a relief printing method, a gravure printing method, a lithographic printing method, a screen printing method, etc.), among which a relief printing method is preferably used from the viewpoint of availability of a roll-to-roll method, and a gravure coating method is particularly preferably used from the viewpoint of film coatability. The curable composition of the present invention is preferably applied by filtration using a filter having a pore diameter of about 0.2 μm or the like. In the case of coating, a solvent may be further added to the curable composition as needed. The solvent in this case includes various solvents listed in the above [ (d) solvent ].
After the curable composition of the present invention is applied to a substrate to form a coating film, the coating film is pre-dried by a heating unit such as a heating plate or an oven as necessary to remove the solvent (solvent removal step). The conditions for the heat drying at this time are preferably, for example, 40 to 120℃for about 30 seconds to 10 minutes. After drying, the coating film is cured by irradiation with active energy rays such as ultraviolet rays. Examples of the active energy ray include: ultraviolet rays, electron beams, and X-rays, ultraviolet rays being particularly preferred. As a light source for ultraviolet irradiation, for example, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, and a UV-LED can be used. Further, the polymerization may be completed by post-baking, specifically, heating by a heating unit such as a heating plate or an oven.
The thickness of the cured film formed after drying and curing is usually 0.1 μm to 20. Mu.m, preferably 0.5 μm to 10. Mu.m.
< hard coating film >)
The curable composition of the present invention can be used to produce a hard coat film having a hard coat layer on at least one surface (surface) of a film substrate. The hard coat film is also an object of the present invention, and is preferably used for protecting the surfaces of various display elements such as touch panels and liquid crystal displays, for example.
The hard coat layer in the hard coat film of the present invention can be formed by a method comprising: a step of forming a coating film by applying the curable composition of the present invention to a film substrate; a step of removing the solvent by heating as needed; and a step of curing the coating film by irradiating the coating film with active energy rays such as ultraviolet rays. The method for producing a hard coat film comprising these steps and having a hard coat layer on at least one surface of a film base material is also an object of the present invention.
As the film base material, various transparent resin films which can be used for optical applications among the base materials listed in the above-mentioned < cured film > can be used. Preferable resin films include, for example: films of polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyurethanes, thermoplastic Polyurethanes (TPU), polycarbonates, polymethacrylates, polystyrene, polyolefin, polyamide, polyimide, and cellulose Triacetate (TAC).
The film base material may be formed by stacking a plurality of layers. For example, a primer layer, an ultraviolet absorbing layer, an infrared absorbing layer, a near infrared absorbing layer, an electromagnetic wave absorbing layer, a color correction layer, a refractive index adjusting layer, a weather resistant layer, an antireflection layer, an antistatic layer, an anti-discoloration layer, a gas barrier layer, a water vapor barrier layer, a light scattering layer, an electrode layer, and other layers different from the resin film may be laminated on the surface of the resin film as an underlayer of the hard coat layer, or a plurality of layers of the underlayer of the hard coat layer may be laminated. The layer to be laminated on the surface of the resin film is not particularly limited as long as the effect of the present invention is not impaired.
The method for applying the curable composition of the present invention to the film substrate (coating film forming step) and the method for irradiating the coating film with active energy rays (curing step) can be the methods listed in the above < cured film >. In the case where the curable composition of the present invention contains a solvent (in the form of a varnish), a step of drying the coating film to remove the solvent may be included as necessary after the coating film forming step. In this case, a method of drying the coating film (solvent removal step) listed in the above-mentioned < cured film > can be used.
The layer thickness (film thickness) of the hard coat layer thus obtained is, for example, 1 μm to 20 μm, preferably 1 μm to 10 μm.
< perfluoropolyether Compound >
The perfluoropolyether compound, which is the reaction product of a starting perfluoropolyether having a hydroxyl group bonded to a poly (oxyalkylene) group only at one end of a molecular chain containing the poly (oxyperfluoroalkylene) group and having a number average molecular weight of 1500 to 3000, and a compound having a functional group reactive with the hydroxyl group and an active energy ray polymerizable group, is also the object of the present invention.
Examples
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the examples. In the examples, the apparatus and conditions for preparing the sample and analyzing the physical properties are as follows.
(1) Coating with bar coater
The device comprises: PM-9050MC manufactured by SMT.
Rod: OSG SYSTEM PRODUCTS A-Bar OSP-30, manufactured by Kyowa Kagaku Co., ltd.) has a maximum wet film thickness of 30 μm (film thickness 6 μm after drying) or OSP-15, and a maximum wet film thickness of 15 μm (film thickness 3 μm after drying).
Coating speed: 4 m/min.
(2) Film thickness measurement
The device comprises: f20 film thickness measuring system manufactured by Filmetrics Inc.
(3) Baking oven
The device comprises: a double-layer clean oven (upper and lower formula) PO-250-45-D manufactured by Sanji instruments (Co., ltd.).
(4) UV curing
The device comprises: CV-110QC-G manufactured by Heraeus Co.
A lamp: electrodeless lamp H-bulb manufactured by Heraeus Co.
(5) Scratch resistance test and abrasion resistance test
The device comprises: TRIBOGEAR TYPE, a reciprocating abrasion tester manufactured by New east science Co., ltd.): 30S.
Scanning speed: 3200 mm/min.
Scanning distance: 50mm.
(6) Contact angle measurement
The device comprises: dropMaster DM-501, available from Kyowa interface science, inc.
Measuring temperature: 23 ℃.
(7) Dynamic coefficient of friction measurement
The device comprises: load-variable friction abrasion test system TRIBOGEAR (registered trademark) TYPE, manufactured by New DONG scientific Co., ltd.): HHS2000.
And (3) probe: 0.6mmR sapphire needle.
Load: 200g.
Scanning speed: 2 mm/s.
Scanning distance: 10mm.
(8) Total light transmittance, haze measurement
The device comprises: haze meter NDH5000 manufactured by japan electrochromic industry co.
(9) Weight average molecular weight determination
Gel Permeation Chromatography (GPC).
The device comprises: HLC-8420GPC manufactured by Tosoh Co., ltd.
Chromatographic column: TSKgelG2000HXL, TSKgelG3000HXL manufactured by Tosoh corporation.
Measuring temperature: 40 ℃.
Eluent: tetrahydrofuran.
And (3) detection: RI.
(10) Combustion ion chromatography
Automatic sample combustion device system: AQF-2100H was manufactured by Nitto Seiko analytical technique (Mitsubishi chemical analytical technique, original Co.).
Ion chromatograph: thermoFisher Scientific Dionex Interon, inc.
Sample: 2mg.
Absorption liquid: 2.7mM sodium carbonate+0.3 mM sodium bicarbonate aqueous solution.
Eluent: 2.7mM sodium carbonate+0.3 mM sodium bicarbonate aqueous solution.
Chromatographic column: thermoFisher Scientific AG-12A/AS-12A.
Flow rate: 1.5 mL/min.
A detector: conductivity (using suppressors).
Standard sample: fluoride ion standard solution (F-1000) Fuji film and Wako pure chemical industries, ltd.
When the solvent in the sample does not contain a fluorine atom-containing solvent, the fluorine concentration is measured while the solvent is contained, and the fluorine concentration in the solute is calculated from the solid content concentration.
Further, the shorthand notation indicates the following meanings.
Multifunctional acrylate PA1: dipentaerythritol pentaacrylate/hexaacrylate mixture [ ARONIX (registered trademark) M-403, manufactured by Toyama Synthesis Co., ltd ].
Multifunctional acrylate PA2: an oxyethylene modified multifunctional acrylate [ New front (registered trademark) MF-001 manufactured by first industry Co., ltd.).
Multifunctional acrylate PA3: multifunctional urethane acrylate [ ART RESIN (registered trademark) UN-3320HS, manufactured by Kogyo Co., ltd.).
Multifunctional acrylate PA4: pentaerythritol triacrylate/pentaerythritol tetraacrylate [ PET30 manufactured by Japanese chemical Co., ltd ].
PFPE1: the perfluoropolyether having one hydroxyl group at only one end via a poly (oxyethylene) group, having the following structure [ Fomblin (registered trademark) 4102X, manufactured by Solvay Specialty Polymers Co., ltd., based on 19 F-NMR 1 Number average molecular weight 1900 calculated from the analysis result of H-NMR]。
(in the above formula, m is a repeating unit- (CF) 2 CF 2 Number of O) -and n is the repeating unit- (CF) 2 O) -amount, satisfying 5.ltoreq.m+n.ltoreq.30, m and n each independently represent an integer of 0 or more, q is the amount of oxyethylene groups, and represents an integer of 2 to 20. )
PFPE2: not via poly (oxyalkylene) groups only at one endAnd a perfluoropolyether having one hydroxyl group and having the following structure [ Solvay Specialty Polymers Co., ltd. 7324X, based on 19 F-NMR 1 Number average molecular weights 1750 to 1950 calculated as a result of analysis by H-NMR]。
(in the above formula, m is a repeating unit- (CF) 2 CF 2 Number of O) -and n is the repeating unit- (CF) 2 O) -amount, satisfying 5.ltoreq.m+n.ltoreq.30, m and n each independently represent an integer of 0 or more. )
PFPE3: a perfluoropolyether having one hydroxyl group at only one end thereof without a poly (oxyalkylene) group, FO2 made by the company Apollo Scientific, having the following structure, having a molecular weight of 978.15.
PFPE4: a perfluoropolyether having one hydroxyl group at only one end thereof without passing through a poly (oxyalkylene) group (1H, 1H-perfluoro-3, 6, 9-trioxatridecan-1-ol) [ C10GOL, manufactured by the company Exfluor Research, molecular weight 548.1].
N1: 1, 1-bis (acryloyloxymethyl) ethyl isocyanate [ Karenz (registered trademark) BEI, manufactured by Showa electric Co., ltd ].
N2: 2-acryloyloxyethyl isocyanate [ Karenz (registered trademark) AOI manufactured by Showa electric Co., ltd ].
And N3: 2-methacryloyloxyethyl isocyanate [ Karenz (registered trademark) MOI manufactured by Showa electric Co., ltd ].
DOTDD: dioctyltin di neodecanoate [ NEOSTANN (registered trademark) U-830, manufactured by Nitto chemical Co., ltd.).
SMA7: perfluoropolyethers having a total of four active energy ray polymerizable groups at both ends of a molecular chain containing a poly (oxidized perfluoroalkylene) group [ Fluorolink (registered trademark) AD-1700, manufactured by Solvay Specialty Polymers company), a nonvolatile 70 mass% solution, weight average molecular weight measured in terms of polystyrene based on GPC: mw is 3973, dispersity: mw/Mn was 2.1 (Mn is a number average molecular weight), and the fluorine atom content in the perfluoropolyether compound calculated by combustion ion chromatography was 29 mass%.
MEK: methyl ethyl ketone.
PGME: propylene glycol monomethyl ether.
PGMEA: propylene glycol monomethyl ether acetate.
O2959: 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one [ OMNIRAD (registered trademark) 2959, manufactured by IGM Resins Co., ltd.).
PREPARATION EXAMPLE 1 preparation of perfluoropolyether Compound SMA1
Into the screw tube were charged PFPE 1.08 g (1.6 mmol), N1.39 g (1.6 mmol), DOTDD 0.035g (0.01 times the total mass of PFPE1 and N1) and PGMEA 3.5g. The mixture was stirred using a stirrer at room temperature (about 23 ℃) for 72 hours, to obtain a 50 mass% PGMEA solution of the target perfluoropolyether compound SMA 1. Weight average molecular weight of SMA1 obtained, measured in terms of polystyrene based on GPC: mw of 1908, dispersity: mw/Mn was 1.0. The fluorine atom content in SMA1 calculated by combustion ion chromatography was 47 mass%.
PREPARATION EXAMPLE 2 preparation of perfluoropolyether Compound SMA2
A screw tube was charged with 3.23g (1.7 mmol) of PFPE, 0.24g (1.7 mmol) of N2, 0.035g of DOTDD (0.01 times the total mass of PFPE1 and N2) and 3.5g of PGMEA. The mixture was stirred using a stirrer at room temperature (about 23 ℃) for 72 hours, to obtain a 50 mass% PGMEA solution of the target perfluoropolyether compound SMA 2. Weight average molecular weight of the obtained SMA2 as measured in terms of polystyrene based on GPC: mw was 1894, dispersity: mw/Mn was 1.1.
PREPARATION EXAMPLE 3 preparation of perfluoropolyether Compound SMA3
A screw tube was charged with 1.20 g (1.7 mmol) of PFPE, 0.26g (1.7 mmol) of N, 0.035g of DOTDD (0.01 times the total mass of PFPE1 and N3) and 3.5g of PGMEA. The mixture was stirred using a stirrer at room temperature (about 23 ℃) for 72 hours, to obtain a 50 mass% PGMEA solution of the target perfluoropolyether compound SMA 3. Weight average molecular weight of SMA3 obtained, measured in terms of polystyrene based on GPC: mw was 1868, dispersity: mw/Mn was 1.1.
PREPARATION EXAMPLE 4 preparation of perfluoropolyether Compound SMA4
Into the screw tube were charged 2.20g (1.2 mmol) of PFPE, 0.28g (1.2 mmol) of N, 0.025g (0.01 times the total mass of PFPE2 and N1) of DOTDD, and 0.6g of MEK. The mixture was stirred using a stirrer at room temperature (about 23 ℃) for 72 hours, to give an 80 mass% MEK solution of the target perfluoropolyether compound SMA 4. Weight average molecular weight of SMA4 obtained, measured in terms of polystyrene based on GPC: mw is 1710, dispersity: mw/Mn was 1.0. The fluorine atom content in SMA4 calculated by combustion ion chromatography was 63 mass%.
PREPARATION EXAMPLE 5 preparation of perfluoropolyether Compound SMA5
A screw tube was charged with 2.78g (2.9 mmol) of PFPE3, 0.68g (2.9 mmol) of N, 0.035g of DOTDD (0.01 times the total mass of PFPE3 and N1) and 3.5g of PGMEA. The mixture was stirred using a stirrer at room temperature (about 23 ℃) for 72 hours, to obtain a 50 mass% PGMEA solution of the target perfluoropolyether compound SMA 5. Weight average molecular weight of the obtained SMA5 as measured in terms of polystyrene based on GPC: mw of 1299, dispersity: mw/Mn was 1.0. The content of fluorine atoms in SMA5 calculated by combustion ion chromatography was 51 mass%, and a value equivalent to the content of fluorine atoms of 51 mass% calculated theoretically from the structure of SMA5 was shown.
PREPARATION EXAMPLE 6 preparation of perfluoropolyether Compound SMA6
Into the screw tube were charged 2.41g (4.4 mmol) of PFPE4, 1.05g (4.4 mmol) of N, 0.035g of DOTDD (0.01 times the total mass of PFPE4 and N1) and 3.5g of PGMEA. The mixture was stirred using a stirrer at room temperature (about 23 ℃) for 72 hours, to obtain a 50 mass% PGMEA solution of the target perfluoropolyether compound SMA 6. Weight average molecular weight of the obtained SMA6 as measured in terms of polystyrene based on GPC: mw was 1029, dispersity: mw/Mn was 1.0. The content of fluorine atoms in SMA6 calculated by combustion ion chromatography was 46 mass%, and a value equivalent to 47 mass% of the content of fluorine atoms calculated theoretically from the structure of SMA6 was shown.
Examples 1 to 8 and comparative examples 1 to 4
The components shown in table 1 were mixed to prepare curable compositions having the solid content concentrations shown in table 1. Herein, the solid component means a component other than a solvent. In table 1, [ parts ] means [ parts by mass ], [% ] means [ percent by mass ]. The polyfunctional acrylate and the surface modifier in table 1 each represent a solid component.
TABLE 1
A4-size PET film having a primer layer formed by subjecting both sides to an easy-to-adhere treatment by a bar coater [ Lumirror (registered trademark) U403 (known as U40, available from Toray Co., ltd.) had a thickness of 100. Mu.m ]These curable compositions were applied thereon to obtain a coating film. The film was dried in an oven at 60℃for 8 minutes, and the solvent was removed. The film obtained was irradiated with a radiation exposure of 300mJ/cm under a nitrogen atmosphere 2 By exposure to UV light, a hard coat film having a hard coat layer (cured film) with a film thickness of 3 μm or 6 μm was produced.
The uniformity of each curable composition, and the scratch resistance, water repellency, abrasion resistance, sliding property, and haze of the obtained hard coating film were evaluated. The procedure of evaluation is shown below. The results are shown in Table 2.
[ homogeneity of composition ]
The appearance of each of the prepared curable compositions was visually confirmed, and evaluated according to the following criteria.
A: clear solution (no suspended matter, precipitate and phase separation).
C: there are any of suspended matter, precipitate, and phase separation.
[ scratch resistance ]
The hard coat surface of the obtained hard coat film was repeatedly wiped 2500 times with a stroke (stroke) of 50mm by applying a load of 1kg to steel wool [ BONSTAR (registered trademark) #0000 (ultra fine) ] mounted on a reciprocating abrasion tester. Then, the degree of the scratch in the region other than the 5mm width range at both ends of the stroke of 50mm was visually checked, and the scratch was checked on the hard coat surface by a microscope (KEYENCE corporation), and evaluated according to the following criteria A, B and C. In addition, when the hard coat layer is practically used, at least B, preferably a, is required.
A: no flaw (flaw 0 pieces).
B: the flaws (1 to 4 flaws of 1 to 9mm in length) were generated.
C: generating flaws (more than 5 flaws with the length of 1mm to 9mm or more than 1 flaw with the length of more than 1 cm).
[ Water repellency ]
The contact angle θ was measured five times after 10 seconds by allowing 1 μl of water to adhere to the hard coat layer surface, and the average value was evaluated according to the following criteria. In addition, when the hard coat layer is practically used, at least B, preferably a, is required.
A：θ≥105°。
B：90°≤θ＜105°。
C：θ＜90°。
[ abrasion resistance ]
The hard coat surface was reciprocally wiped 2500 times with a cylindrical eraser [ RUBBER STICK, phi 6.0mm ] mounted on a reciprocal abrasion tester, applied with a load of 1 kg. The wiped portion was allowed to adhere with 1 μl of water, and the contact angle θ was measured at five places for 5 seconds, and the average value was evaluated as a contact angle value according to the following criteria. Note that a is desirable when it is assumed that the composition is actually used as a hard coat layer.
A：θ≥90°。
B：80°≤θ＜90°。
C：80°＜θ。
[ sliding Property ]
The coefficient of dynamic friction μ' at five points of the hard coat surface was measured, and the average value thereof was evaluated according to the following criteria. The smaller the coefficient of dynamic friction value is, the smaller the friction with the probe is, which is a criterion for slidability. The smaller the coefficient of dynamic friction value, the better the slidability upon contact, and therefore the smaller the coefficient of dynamic friction value, the more preferable.
A：μ′≤0.035。
B：0.035＜μ′≤0.050。
C：μ′＞0.050。
[ haze ]
As a reference value, haze at three places of the hard coat surface was measured, and an average value thereof was calculated. The haze of the PET film [ LumirrorU 403 (registered trademark) manufactured by Toray Co., ltd.) (sometimes referred to as U40) used herein was 1.6 as a base material, and the thickness was 100. Mu.m.
TABLE 2
As shown in table 1, the curable compositions of examples 1 to 8 include multifunctional acrylates PA1 to PA4 and the following: any one of the isocyanate compound groups N1 to N3 having the active energy ray-polymerizable group is reacted with a perfluoropolyether PFPE1 having a number average molecular weight 1900 having only one hydroxyl group bonded to a poly (oxyethylene) group at one end of a molecular chain containing a poly (oxyperfluoroalkylene) group, SMA1 having a weight average molecular weight 1908, SMA2 having a weight average molecular weight 1894, or SMA3 having a weight average molecular weight 1868. As shown in table 2, the curable compositions of examples 1 to 8 showed excellent homogeneity, and the hard coat film having the hard coat layer obtained from the curable composition showed excellent sliding properties, abrasion resistance, water repellency, and abrasion resistance.
On the other hand, as shown in table 1, the curable composition of comparative example 1 contains a multifunctional acrylate PA1 and the following substances: an SMA4 of weight average molecular weight 1710 obtained by reacting an isocyanate compound N1 having the active energy ray-polymerizable group with a perfluoropolyether compound PFPE2 having one hydroxyl group at only one end of a molecular chain containing a poly (oxidized perfluoroalkylene) group and having a number average molecular weight of 1750 to 1950 not via a poly (oxyalkylene) group, the curable composition of comparative example 2 comprising a multifunctional acrylate PA1 and: an isocyanate compound N1 having the active energy ray-polymerizable group is reacted with an SMA5 having a weight average molecular weight 1299, which is obtained by reacting a perfluoropolyether compound PFPE3 having a molecular weight 978.15 having one hydroxyl group only at one end of a molecular chain including a poly (oxidized perfluoroalkylene) group, not via a poly (oxyalkylene) group. As shown in table 2, the curable compositions of comparative examples 1 and 2 were poor in homogeneity, and the hard coating films including the hard coating layers obtained from the curable compositions were poor in slidability and abrasion resistance, because the cohesive forces of SMA4 and SMA5 were high and SMA4 and SMA5 could not be sufficiently segregated on the surfaces of the hard coating layers, as compared with the hard coating films including the hard coating layers obtained from the curable compositions of examples 1 to 8.
As shown in table 1, the curable composition of comparative example 3 includes a polyfunctional acrylate PA1 and the following substances: an isocyanate compound N1 having the active energy ray-polymerizable group is reacted with an SMA6 having a weight average molecular weight of 1029, which is obtained by reacting a perfluoropolyether compound PFPE4 having a molecular weight 548.1 having one hydroxyl group only at one end of a molecular chain including a poly (oxidized perfluoroalkylene) group, without passing through the poly (oxyalkylene) group. As shown in table 2, the curable composition of comparative example 3 had good homogeneity, but the hard coating film including the hard coating layer obtained from the curable composition had a short molecular chain including a poly (oxidized perfluoroalkylene) group of SMA6, and therefore, the hard coating film including the hard coating layer obtained from the curable compositions of examples 1 to 8 had poor sliding properties, abrasion resistance, and abrasion resistance.
Further, as shown in table 1, the curable composition of comparative example 4 contains a multifunctional acrylate PA1 and the following substances: a perfluoropolyether compound SMA7 having a weight average molecular weight 3973 having active energy ray polymerizable groups at both ends of a molecular chain containing a poly (oxidized perfluoroalkylene) group. As shown in table 2, although the curable composition of comparative example 4 had good homogeneity, SMA7 had active energy ray polymerizable groups at both ends of the molecular chain containing the poly (oxyperfluoroalkylene) group in the hard coating film having the hard coating layer obtained from the curable composition, and therefore the molecular mobility of the poly (oxyperfluoroalkylene) chain was reduced, and the sliding property and abrasion resistance were poor as compared with the hard coating film having the hard coating layer obtained from the curable compositions of examples 1 to 8.

Claims (24)

1. A curable composition comprising:
(a) 100 parts by mass of an active energy ray-curable polyfunctional monomer having two or more (meth) acryloyl groups in one molecule;
(b) 0.05 to 2 parts by mass of a perfluoropolyether having an active energy ray polymerizable group via a poly (oxyalkylene) group only at one end of a molecular chain containing the poly (oxyperfluoroalkylene) group and having a weight average molecular weight of 1500 to 3500; and
(c) 1 to 20 parts by mass of a polymerization initiator generating radicals by active energy rays.
2. A curable composition comprising:
(a) 100 parts by mass of an active energy ray-curable polyfunctional monomer having two or more (meth) acryloyl groups in one molecule;
(b) 0.05 to 2 parts by mass of a perfluoropolyether which is a reaction product of a starting perfluoropolyether having a hydroxyl group bonded to a poly (oxyalkylene) group only at one end of a molecular chain containing the poly (oxyperfluoroalkylene) group and having a number average molecular weight of 1500 to 3000, and a compound having a functional group reactive with the hydroxyl group and an active energy ray polymerizable group; and
(c) 1 to 20 parts by mass of a polymerization initiator generating radicals by active energy rays.
3. The curable composition according to claim 2, wherein,
the (b) perfluoropolyether has the active energy ray polymerizable group via the poly (oxyalkylene) group only at one end of a molecular chain containing the poly (oxyperfluoroalkylene) group, and has a weight average molecular weight of 1500 to 3500.
4. The curable composition according to any one of claim 1 to 3, wherein,
the perfluoropolyether (b) has the active energy ray-polymerizable group via a urethane bond bonded to the poly (oxyalkylene) group.
5. The curable composition according to any one of claim 1 to 4, wherein,
the poly (oxyalkylene) group is a poly (oxyethylene) group.
6. The curable composition according to any one of claims 1 to 5, wherein,
the poly (oxyperfluoroalkylene) group has a repeating unit- (CF) 2 O) -and/or repeating units- (CF) 2 CF 2 O) -, in the case of having both repeating units, the poly (oxyperfluoroalkylene) group is a group in which these repeating units are bonded by block bonding, random bonding, or both block bonding and random bonding.
7. The curable composition according to claim 6, wherein,
The molecular chain comprising the poly (oxidized perfluoroalkylene) group has a structure represented by the following formula [1],
the said [1]]Wherein m isRepeating units- (CF) 2 CF 2 Number of O) -and n is the repeating unit- (CF) 2 O) -amount, satisfying 5.ltoreq.m+n.ltoreq.30, m and n each independently represent an integer of 0 or more, q is the amount of oxyethylene groups, and represents an integer of 2 to 20.
8. The curable composition according to claim 7, wherein,
in the formula [1], m and n each independently represent an integer of 1 or more.
9. The curable composition according to claim 7 or 8, wherein,
the perfluoropolyether (b) is a compound represented by the following formula (2),
in the formula [2], m, n and q have the same meanings as defined in the formula [1], and A represents a terminal group having the active energy ray-polymerizable group.
10. The curable composition according to claim 9, wherein,
the terminal group A is a group represented by the following formula [ A1] or formula [ A2],
the [ A1]]And [ A2]]Wherein R is 1 And R is 2 Each independently represents a hydrogen atom or a methyl group, and the formula [2]]The urethane bonds of the compounds shown are bonding bonds.
11. The curable composition according to any one of claim 1 to 10, wherein,
The curable composition further comprises (d) a solvent.
12. A cured film obtained from the curable composition according to any one of claims 1 to 11.
13. A hard coat film comprising a hard coat layer comprising the cured film according to claim 12 on at least one surface of a film substrate.
14. The hard coat film according to claim 13, wherein,
and a lower layer having a hard coat layer between the surface of the film base material and the hard coat layer, wherein the film base material is a resin film.
15. The hard coat film according to claim 13 or 14, wherein,
the hard coat layer has a film thickness of 1 μm to 20 μm.
16. A method for producing a hard coat film, comprising:
a step of forming a coating film by applying the curable composition according to any one of claims 1 to 11 to a film substrate; and
and a step of forming a hard coat layer by curing the coating film by irradiation with an active energy ray.
17. A method for producing a hard coat film, comprising:
a step of forming a coating film by applying the curable composition according to claim 11 to a film substrate;
a step of removing the solvent from the coating film by heating; and
and a step of forming a hard coat layer by curing the coating film by irradiation with an active energy ray.
18. The method for producing a hard coat film according to claim 16 or 17, wherein,
the method for producing a hard coat film further comprises: and forming a lower layer of a hard coat layer on the surface of the film base material, wherein the film base material is a resin film, and the coating film is formed on the lower layer of the hard coat layer.
19. A perfluoropolyether compound having the active energy ray polymerizable group via a poly (oxyalkylene) group only at one end of a molecular chain containing the poly (oxyperfluoroalkylene) group and having a weight average molecular weight of 1500 to 3500.
20. A perfluoropolyether compound which is a reaction product of a starting perfluoropolyether having a hydroxyl group bonded to a poly (oxyalkylene) group only at one end of a molecular chain containing the poly (oxyperfluoroalkylene) group and having a number average molecular weight of 1500 to 3000, and a compound having a functional group reactive with the hydroxyl group and an active energy ray polymerizable group.
21. The perfluoropolyether compound of claim 20, wherein,
the perfluoropolyether compound has the active energy ray polymerizable group via the poly (oxyalkylene) group only at one end of a molecular chain containing the poly (oxyperfluoroalkylene) group, and has a weight average molecular weight of 1500 to 3500.
22. A perfluoropolyether compound according to any one of claims 19 to 21, wherein,
the molecular chain comprising the poly (oxidized perfluoroalkylene) group has a structure represented by the following formula [1],
the said [1]]In which m is a repeating unit- (CF) 2 CF 2 Number of O) -and n is the repeating unit- (CF) 2 O) -number, satisfying 5.ltoreq.m+n.ltoreq.30, m and n each independently represent an integer of 0 or more, in the case of having both repeating units, these repeating units are bonded by a block, randomly bonded, or blockedBonding and random bonding, q is the number of oxyethylene groups, and represents an integer of 2 to 20.
23. The perfluoropolyether compound of claim 22, wherein,
in the formula [1], m and n each independently represent an integer of 1 or more.
24. A perfluoropolyether compound according to claim 22 or 23, wherein,
the perfluoropolyether compound is a compound represented by the following formula (2),
in the formula [2], m, n and q have the same meanings as defined in the formula [1], A represents a terminal group represented by the following formula [ A1] or formula [ A2] having the active energy ray-polymerizable group,
the [ A1]]And [ A2]]Wherein R is 1 And R is 2 Each independently represents a hydrogen atom or a methyl group, and the formula [2] ]The urethane bonds of the compounds shown are bonding bonds.
CN202280020520.1A 2021-03-11 2022-02-28 Curable composition for hard coating Pending CN116964118A (en)

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