Curable composition and film containing the cured layer thereof

Abstract

To provide a curable composition capable of forming a cured layer that offers smooth finger touch and superior wear resistance.SOLUTION: A curable composition includes the following components: (1) a perfluoropolyether group-containing methacrylate monomer with a number average molecular weight of 3000 or more and 7500 or less, (2) a fluorine group-containing methacrylate monomer with a number average molecular weight of 500 or more and less than 3000, (3) a monofunctional methacrylate monomer free of fluorine groups, (4) a polyfunctional methacrylate monomer (excluding the methacrylate monomers of (1)-(2)), (5) a photoinitiator and (6) an organic solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a novel curable composition. [Background technology]

[0002] For example, touch panels that allow operation by touching the screen with a touch sensor function (touch input function) are becoming widespread in the display sections of smartphones, tablet devices, PC monitors, ticket machines, information displays, in-car control panels, digital cameras, multifunction printers (monitor section), portable game devices, bank ATMs, digital audio players, etc. These displays have increased resolution and can display clearer images, but scratches and dirt on the screen surface can make it difficult to see clear images. Therefore, protective films are placed on the screen surface to maintain clear images over the long term.

[0003] Protective films are required to have transparency, abrasion resistance, stain resistance, water and oil repellency, and fingerprint-wiping properties for the purposes mentioned above. In addition, protective films that also possess other functions such as anti-reflective and antibacterial properties have been developed.

[0004] For example, a resin composition for forming a low refractive index layer is known, which is used to form the low refractive index layer of an anti-reflective film having a low refractive index layer, and is characterized by containing a polyfunctional monomer which is at least one polyfunctional acrylate monomer or methacrylate monomer having 3 to 8 functional groups, and a difunctional monomer which is a bifunctional acrylate monomer or methacrylate monomer represented by a specific general formula (Patent Document 1).

[0005] As a film for touch panels, for example, a hard coat film has been proposed which has a hard coat layer on a substrate, wherein the hard coat layer contains a cured product of an ionizing radiation-curable composition which contains an antifouling agent having an ionizing radiation-curable functional group and a binder resin component having an ionizing radiation-curable functional group, the hard coat layer is substantially free of particles, and the hard coat layer satisfies specific conditions (Patent Document 2).

[0006] Furthermore, for example, there is a known film having frictional properties such that when the relative dynamic friction coefficient μ is measured by changing the moving speed v (mm / s) of a contactor, the slope a of the straight line obtained by linear fitting with log(v), which is the common logarithm of the moving speed, on the horizontal axis and μ on the vertical axis is 0.01 or more, and the intercept b is 0.6 or less (Patent Document 3).

[0007] However, while these films can be used as protective films because they possess certain characteristics, there is room for further improvement before they can be used for touch panels (touchscreens). Specifically, there is a problem with finger glide.

[0008] Recently, with the increasing sophistication and miniaturization of devices, there has been a need to operate touch panels more precisely, requiring fine finger movements on the touch panel. In this case, if there is any snagging or resistance between the touch panel surface and the finger surface, it becomes difficult to move the finger smoothly, hindering quick operation and potentially leading to errors. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Japanese Patent Publication No. 2014-63061 [Patent Document 2] Japanese Patent Publication No. 2018-202697 [Patent Document 3] International release WO2019 / 82664 [Overview of the project] [Problems to be Solved by the Invention]

[0010] In contrast, the applicant of the present application has developed a curable composition capable of forming a cured layer having excellent finger slipperiness in order to provide a protective film or a hard coat in which the above points are improved, and has already filed a patent application.

[0011] Since the cured layer formed from this curable composition has excellent finger slipperiness, it can be suitably used as a protective film for a touch panel or the like. In this case, if higher abrasion resistance can be imparted to the cured layer, further expansion of applications is expected.

[0012] Therefore, the main object of the present invention is to provide a curable composition capable of forming a cured layer having excellent finger slipperiness and abrasion resistance. [Means for Solving the Problems]

[0013] As a result of intensive studies in view of the problems of the prior art, the present inventor has found that the above object can be achieved by adopting a composition having a specific composition, and has completed the present invention.

[0014] That is, the present invention relates to a curable composition described below and a film containing a cured layer thereof. 1. The following components: (1) A perfluoropolyether group-containing (meth) acrylate monomer having a number average molecular weight of 3000 or more and 7500 or less, (2) A fluorine group-containing (meth) acrylate monomer having a number average molecular weight of 500 or more and less than 3000, (3) A monofunctional (meth) acrylate monomer not containing a fluorine group, (4) A polyfunctional (meth) acrylate monomer (however, excluding the (meth) acrylate monomers of (1) to (2) above), (5) A photoinitiator and (6) An organic solvent A curable composition characterized by containing the above. 2. The curable composition according to item 1, wherein the solid content of the perfluoropolyether group-containing (meth)acrylate monomer is 10 to 30% by weight. 3. The curable composition according to item 1, wherein the fluorine group-containing (meth)acrylate monomer is contained in an amount of 150 parts by weight or more per 100 parts by weight of the perfluoropolyether group-containing (meth)acrylate monomer. 4. The curable composition according to item 1, wherein the organic solvent comprises at least one of a ketone solvent, an ester solvent, an alcohol solvent, and an amide solvent. 5. The curable composition according to item 1, further comprising a (meth)acryloyl group-containing polydimethylsiloxane. 6. A film in which a cured layer of the curable composition described in any one of items 1 to 5 above is disposed as the outermost layer. 7. The film according to item 6, wherein the thickness of the cured layer is 0.01 to 0.1 μm. 8. An optical product comprising the film described in item 6 above laminated on a substrate. 9. The optical product according to item 8, wherein the substrate is a display screen that serves as a touch sensor in a touch panel display. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a curable composition that can form a hardened layer that has excellent finger glide properties as well as excellent abrasion resistance.

[0016] In particular, the curable composition of the present invention uses a monofunctional (meth)acrylate monomer that does not contain a fluorine group, along with a perfluoropolyether group-containing (meth)acrylate monomer (component 1) and a fluorine group-containing (meth)acrylate monomer with a relatively small molecular weight (component 2). As a result, it is possible to exhibit high abrasion resistance while maintaining good finger glide. In addition to good finger glide, it is also possible to maintain relatively high liquid repellency. Although the mechanism of action is not clear, it is presumed that the use of the aforementioned monofunctional (meth)acrylate monomer improves adhesion (affinity) with adjacent layers or substrates.

[0017] Furthermore, the curable composition of the present invention, by using a perfluoropolyether group-containing (meth)acrylate monomer (first component) having a relatively large molecular weight and a fluorine group-containing (meth)acrylate monomer (second component) having a relatively small molecular weight in combination, allows the first component, which alone is soluble only in fluorine-based solvents, to be effectively dissolved in general-purpose solvents such as methyl ethyl ketone (MEK), resulting in the formation of a cured layer with good finger glide. In particular, since this cured layer is composed of fluorine-based materials, its excellent water repellency and oil repellency (ink repellency) are also considered to contribute to the improvement of finger glide. That is, even if there is sweat or sebum on the fingertips, the cured layer can repel them, resulting in good finger glide on the surface of the cured layer.

[0018] Furthermore, since the curable composition of the present invention is provided in the form of a solution dissolved in a general-purpose solvent as described above, it can form a thin coating film, and in particular, it can provide a cured layer consisting of a thin film of 0.1 μm or less. As a result, even if there is an underlying layer with optical functions such as a refractive index control layer or an anti-reflective layer, it is possible to provide a cured layer or film having a top surface with desired finger-slip properties without interfering with those functions. In other words, the cured layer of the present invention can be suitably used as a film to protect the surface of an optical functional layer.

[0019] The curable composition of the present invention, having these characteristics, can be suitably used, for example, as a protective layer or protective film in optical products. In particular, it is ideal as a material for protecting the screen (outermost surface) of a touch panel that can be operated with fingers. [Modes for carrying out the invention]

[0020] 1.Curable composition The curable composition of the present invention (the present composition) comprises the following components: (1) Perfluoropolyether group-containing (meth)acrylate monomer (component 1) having a number average molecular weight of 3000 or more and 7500 or less, (2) Fluorine group-containing (meth)acrylate monomer (second component) with a number average molecular weight of 500 or more and less than 3000, (3) Monofunctional (meth)acrylate monomers that do not contain a fluorine group (third component), (4) Polyfunctional (meth)acrylate monomers (excluding the (meth)acrylate monomers of (1) and (2) above) (Fourth component), (5) Photoinitiator (component 5) and (6) Organic solvent (component 6) It is characterized by including.

[0021] In this invention, unless otherwise specified, acryloyl groups or methacryloyl groups are collectively referred to as "(meth)acryloyl groups." Acryloyloxy groups or methacryloyloxy groups are collectively referred to as "(meth)acryloyloxy groups." Furthermore, acrylates or methacrylates are collectively referred to as "(meth)acrylates," and acrylic acid or methacrylic acid are collectively referred to as "(meth)acrylic acid."

[0022] A. Components of the present invention composition Component 1 The perfluoropolyether group-containing (meth)acrylate monomer as the first component has a physical property that the number average molecular weight is 3000 or more and 7500 or less (preferably 4000 or more and 7000 or less). By using such a monomer with a relatively large molecular weight, high finger slipperiness can be obtained.

[0023] In the present invention, for example, a compound represented by the general formula A-PFPE-B (where PFPE represents a perfluoropolyether group, and one or both of A and B are (meth)acryloyl group-containing organic functional groups, and when A or B is not a (meth)acryloyl group-containing organic functional group, it is an alkyl group having 10 or less carbon atoms and in which part or all of the hydrogen atoms may be substituted with fluorine atoms.) can be used as the first component.

[0024] The perfluoropolyether group (PFPE) has a structure in which - (C x F 2x O) m - (x, m are non-zero integers.) is used as a basic unit (unit), and a plurality of these are linked. When m is 2 or more, each (C x F 2x O) may be the same as each other or different from each other. That is, PFPE may have a structure consisting of a repetition of a single type of unit alone, or may have a structure consisting of a combination of two or more different types of units. Also, (C x F 2x O) may have a carbon chain that is either linear or branched.

[0025] Examples of - (C x F 2x O) - that serves as a unit include, but are not limited to, CF2O, CF2CF2O, CF2CF2CF2O, CF2CF2CF2CF2CF2O, CF(CF3)CF2O, CF(CF3)CF(CF3)CF2O, CF2CF(CF3)CF2CF2O, etc. In particular, in the present invention, as PFPE, - (CF2CF2O) m - (CF2O) n-(where m and n are integers other than 0) etc. can be suitably adopted. In this case, m and n can be in the range of approximately 10 ≤ m ≤ 40 and 10 ≤ n ≤ 40, but are not limited to the above range of m and n as long as they are within the above molecular weight range.

[0026] The (meth)acryloyl group-containing organic functional groups A and B are not limited, and any organic functional group having a (meth)acryloyl group or a (meth)acryloyloxy group at its terminus is acceptable.

[0027] For example, as organic functional groups A and B containing a (meth)acryloyl group that does not have a urethane bond, -R 2 -R 1 (R 1 is a (meth)acryloyl group or a (meth)acryloyloxy group, R 2 This is an alkylene group having 10 or fewer carbon atoms, in which some or all of the hydrogen atoms may be substituted with fluorine atoms. Organic functional groups represented by ) can be suitably adopted. Therefore, for example, A or B may be -CF2-R 1 -CH2-R 1 -CF2CH2-R 1 ,-CF2CF2-R 1 ,-CF2CH2CH2-R 1 ,-CH2CF2-R 1 ,-CH2CH2-R 1 Examples include the following.

[0028] For example, as organic functional groups A and B containing a (meth)acryloyl group having a urethane bond, (i)-R 2 -OCONH-R 1 (R 1 is a (meth)acryloyl group or a (meth)acryloyloxy group, R 2 This is an alkylene group having 10 or fewer carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine atoms. (ii)-R 2 -OCONH-R 3 -(R 1 ) n (R1 is a (meth)acryloyl group or a (meth)acryloyloxy group, R 2 R is an alkylene group having 10 or fewer carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine atoms, 3 (where n is an integer, either 1 or 2, and may have a branched chain, and n is an integer, either 1 or 2.) The organic functional groups shown can be suitably adopted.

[0029] Therefore, a specific example of A or B is -CH2-OCONH-R 1 -CF2-OCONH-R 1 -CF2CH2-OCONH-R 1 -CF2CF2-OCONH-R 1 CF2CH2CH2-OCONH-R 1 -CH2CF2-OCONH-R 1 -CH2CH2-OCONH-R 1 -CF2CH2-OCONH-CH2CH2-R 1 -CF2CH2-OCONH-C(CH3)-(R 1 ) Second place can be mentioned.

[0030] Furthermore, if A or B is not an organic functional group containing a (meth)acryloyl group, it is preferable that A or B is an alkyl group having 10 or fewer carbon atoms, in which some or all of the hydrogen atoms may be substituted with fluorine atoms. Examples of organic groups include CF3-, CF3CF2-, CF3CH2-, CH3-, and CH3CF2-.

[0031] As for the first component itself, known or commercially available compounds can be used, or compounds synthesized by known manufacturing methods can be used.

[0032] For commercially available products, for example, the product name "Fomblin MD40" (manufactured by Solvay Specialty Polymers Co., Ltd.) can be used.

[0033] When producing the first component, methods such as attaching (meth)acryloyl groups to both or one end of a perfluoropolyether group can be employed. More specifically, the first component can be suitably prepared by reacting an isocyanate group-containing (meth)acrylate compound with a compound (starting compound) having a perfluoropolyether group as the main chain and an OH group as one or both terminal groups.

[0034] The aforementioned starting compounds can be known or commercially available. Examples of commercially available products include hydroxyl group-containing perfluoropolyether compounds such as "ZMF-402" and "FLUOROLINK D-6000" (both manufactured by Solvay Specialty Polymers Co., Ltd.), "DOL-3000" and "DOL-4000" (both manufactured by Sinochem Japan Co., Ltd.). "ZMF-402" is represented by the following general formula (1). "FLUOROLINK D-6000" is represented by the following general formula (2).

[0035] [ka]

[0036] [ka]

[0037] In the above starting compounds, the terminal end that does not have an OH group may be an alkyl group having 10 or fewer carbon atoms, in which case some or all of the hydrogen atoms may be substituted with fluorine atoms. Examples include CF3-, CH3-, CF3CH2-, CF3CF2-, CH3CH2-, etc.

[0038] The above-mentioned isocyanate group-containing (meth)acrylate compound may be any compound having a (meth)acryloyl group or a (meth)acryloyloxy group and an isocyanate group, and known or commercially available compounds can be used. Suitable commercially available products include, for example, the products named "Karenz AOI," "Karenz BEI," and "Karenz MOI" (all manufactured by Showa Denko K.K.).

[0039] The manufacturing conditions are not particularly limited, but can be carried out by a method including, for example, a step of reacting a starting compound and an isocyanate group-containing (meth)acrylate compound in a solvent at a temperature of 20 to 70°C (reaction step) and a step of recovering the first component (target product) from the reaction product (recovery step).

[0040] In the reaction process, the charging ratio of the starting compound to the isocyanate group-containing (meth)acrylate compound is not particularly limited, but can be appropriately set within a range of approximately 1:1.1 to 1:3.5 in molar ratio.

[0041] Furthermore, a liquid-phase reaction using a solvent can be carried out in the reaction step. In this case, it is preferable to use a fluorine-based solvent. As a fluorine-based solvent, for example, hydrofluoroether-based solvents can be suitably used. Known or commercially available solvents can also be used. For example, 1,3-bis(trifluoromethyl)benzene can be used. As commercially available products, for example, products named "Novec HFE-7200" and "Novec HFE-7300" (both manufactured by 3M) can be suitably used.

[0042] The reaction process may be carried out in the presence of a catalyst as needed. As a catalyst, for example, an alkaline catalyst can be suitably used, and among these, at least one organic alkaline catalyst of triethylamine, tributylamine, pyridine, and 1,4-diazabicyclo[2.2.2]octane is particularly preferred.

[0043] In the recovery process, the method is not particularly limited as long as the target first component can be recovered (isolated). For example, an alcohol (methanol, ethanol, etc.) can be added to the reaction product, the mixture can be separated, and then the supernatant (the upper layer of the reaction product) can be removed. In other words, since the first component generally settles in the reaction product, it can be purified and separated by removing the supernatant. By repeating the series of steps of adding alcohol and removing the supernatant multiple times, the first component can be obtained in a higher yield. In this case, if necessary, the first component can also be recovered as a solid by performing measures such as reducing pressure and drying.

[0044] The method for measuring the number-average molecular weight in this invention is not particularly limited and can be performed by measurement using gel permeation chromatography on a polystyrene basis, or by measurement by structural analysis using nuclear magnetic resonance spectroscopy, etc.

[0045] The solid content of the first component in the composition of the present invention is not limited, but is usually about 10 to 30% by weight, and is particularly preferably 15 to 25% by weight. This makes it possible to more reliably form a coating film with excellent finger-slip properties.

[0046] Component 2 The second component, a fluorine-containing (meth)acrylate monomer, has the property of having a number-average molecular weight of 500 or more and less than 3000 (preferably 1000 or more and 2000 or less).

[0047] By using the second component in combination with the first component, a solution-type composition that dissolves in so-called general-purpose solvents such as methyl ethyl ketone can be provided. The first component alone can only be dissolved in fluorine-based solvents and is difficult to dissolve in general-purpose solvents, making it impossible to form a coating film with excellent finger-slip properties. On the other hand, fluorine-based solvents are a concern due to their environmental impact, and problems such as restrictions on the emission of volatile substances generated during coating processes arise. Therefore, in order to solve these problems, the present invention provides a composition that can form a coating film with excellent finger-slip properties only when the first component is combined with the second component and dissolved in a general-purpose solvent.

[0048] The fluorine-containing (meth)acrylate monomer is not particularly limited as long as it is within the above-mentioned range of number-average molecular weight, but perfluoropolyether-containing (meth)acrylate monomers can be suitably used. More specifically, compounds can be used in which a perfluoropolyether group is present as the main chain, and a (meth)acryloyl group or (meth)acryloyloxy group is bonded to both or one of the terminal groups, with or without an alkylene group having 10 or fewer carbon atoms, in which some or all of the hydrogen atoms may be substituted with fluorine atoms.

[0049] Such compounds can be those that are publicly known or commercially available, or compounds synthesized by known manufacturing methods.

[0050] Commercially available products include, for example, "FLUOROLINK AD-1700," "FLUOROLINK MD-700," and "FLUOROLINK 5101X" (all manufactured by Solvay Specialty Polymers Co., Ltd.), as well as "AC-1000," "AC-2000," and "CAE-1000" (all manufactured by Sinochem Japan Co., Ltd.). The above-mentioned "FLUOROLINK AD-1700" is represented by the following general formula (3) (where m and n are integers other than 0, and X is an organic functional group containing a (meth)acryloyl group).

[0051] [ka]

[0052] When preparing the second component, a method can be employed in which (meth)acryloyl groups are bonded to both or one end of a perfluoropolyether group. More specifically, for example, the second component can be suitably prepared by reacting an isocyanate group-containing (meth)acrylate compound with a compound (starting compound) having a perfluoropolyether group as the main chain and an OH group as one or both terminal groups.

[0053] The aforementioned starting compounds can be known or commercially available. Commercially available products include, for example, hydroxyl group-containing perfluoropolyether compounds such as "ZMF-23", "FLUOROLINK E10H", and "Fomblin D2" (all manufactured by Solvay Specialty Polymers Co., Ltd.), and "DOL-1000" and "DOL-2000" (both manufactured by Sinochem Japan Co., Ltd.). "ZMF-23" is represented by the following general formula (4). "Fomblin D2" is represented by the following general formula (5).

[0054] [ka]

[0055] [ka]

[0056] In the above starting compounds, the terminal end that does not have an OH group may be an alkyl group having 10 or fewer carbon atoms, in which case some or all of the hydrogen atoms may be substituted with fluorine atoms. Examples include CF3-, CH3-, CF3CH2-, CF3CF2-, CH3CH2-, etc.

[0057] The above-mentioned isocyanate group-containing (meth)acrylate compound may be any compound having a (meth)acryloyl group or a (meth)acryloyloxy group and an isocyanate group, and known or commercially available compounds can be used. Suitable commercially available products include, for example, the products named "Karenz AOI," "Karenz BEI," and "Karenz MOI" (all manufactured by Showa Denko K.K.).

[0058] The manufacturing conditions are not particularly limited, but can be carried out by a method including, for example, a step of reacting a starting compound and an isocyanate group-containing (meth)acrylate compound in a solvent at a temperature of 20 to 70°C (reaction step) and a step of recovering a second component (target product) from the reaction product (recovery step).

[0059] In the reaction process, the charging ratio of the starting compound to the isocyanate group-containing (meth)acrylate compound is not particularly limited, but can be appropriately set within a range of approximately 1:1.1 to 1:3.5 in molar ratio.

[0060] Furthermore, a liquid-phase reaction using a solvent can be carried out in the reaction step. In this case, it is preferable to use a fluorine-based solvent. As a fluorine-based solvent, for example, hydrofluoroether-based solvents can be suitably used. Known or commercially available solvents can also be used. For example, 1,3-bis(trifluoromethyl)benzene can be used. As commercially available products, for example, products named "Novec HFE-7200" and "Novec HFE-7300" (both manufactured by 3M) can be suitably used.

[0061] The reaction process may be carried out in the presence of a catalyst as needed. As a catalyst, for example, an alkaline catalyst can be suitably used, and among these, at least one organic alkaline catalyst of triethylamine, tributylamine, pyridine, and 1,4-diazabicyclo[2.2.2]octane is particularly preferred.

[0062] In the recovery process, the method is not particularly limited as long as the target second component can be recovered (isolated). For example, an alcohol (methanol, ethanol, etc.) can be added to the reaction product, the mixture can be separated, and then the supernatant (the upper layer of the reaction product) can be removed. In other words, since the second component generally settles in the reaction product, it can be purified and separated by removing the supernatant. By repeating the series of steps of adding alcohol and removing the supernatant multiple times, the second component can be obtained in a higher yield. In this case, if necessary, the second component can also be recovered as a solid by performing measures such as reducing pressure and drying.

[0063] The method for measuring the number-average molecular weight in this invention is not particularly limited and can be performed by measurement using gel permeation chromatography on a polystyrene basis, or by measurement by structural analysis using nuclear magnetic resonance spectroscopy, etc.

[0064] The solid content of the second component in the composition of the present invention is not particularly limited, but is usually about 10 to 50% by weight, and is particularly preferably 15 to 45% by weight. This further improves the solubility of the first component in general-purpose solvents, and consequently makes it possible to more reliably obtain a coating film with excellent finger-slip properties.

[0065] Furthermore, the ratio of the first component to the second component is not limited and can be set appropriately depending on the type of the first component, etc. However, it is particularly desirable to set the weight ratio of the first component to the second component to approximately 1:1.4 to 1:2, and within that range, it is even more desirable to set it to 1:1.5 to 1:1.8. By setting the ratio within this range, the first component becomes more easily uniformly soluble in general-purpose organic solvents such as MEK, resulting in better finger glide and a more reliable acquisition of a highly transparent coating film.

[0066] Third component The third component is a monofunctional (meth)acrylate monomer that does not contain a fluorine group. This can be used alone or in combination of two or more.

[0067] Examples of third components that do not contain hydroxyl groups include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, lauryl (meth)acrylate, and acroylmorpholine.

[0068] Examples of third components containing hydroxyl groups include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, and glycerol mono(meth)acrylate.

[0069] The solid content of the third component in the composition of the present invention is not particularly limited, but in order to more reliably exert the functions of the third component as described above, it is usually set to about 5 to 20% by weight, and particularly preferably to 5 to 15% by weight.

[0070] Furthermore, in the composition of the present invention, by setting the solid content of the third component to within the range of 30 to 120 parts by weight relative to 100 parts by weight of the solid content of the fourth component, even better wear resistance can be obtained.

[0071] Component 4 The fourth component is a polyfunctional (meth)acrylate monomer (excluding the first and second components). The fourth component is particularly useful in securely fixing the first and second components to the substrate or underlying layer, thereby contributing to the development of coating film performance and durability. The polyfunctional (meth)acrylate monomer can be two-functional or more, but three-functional to six-functional monomers are particularly preferred.

[0072] A polyfunctional (meth)acrylate monomer is a (meth)acrylate monomer that has two or more functional groups containing carbon-carbon unsaturated bonds.

[0073] Examples of difunctional (meth)acrylate monomers include alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate; polyalkylene glycol di(meth)acrylates such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polybutylene glycol di(meth)acrylate; neopentyl glycol di(meth)acrylate; tricyclodecanedimethanol di(meth)acrylate; polycarbonate diol di(meth)acrylate; polyester diol di(meth)acrylate; ethoxylated bisphenol A di(meth)acrylate; propoxylated bisphenol A di(meth)acrylate; and polyurethane di(meth)acrylate.

[0074] Examples of trifunctional (meth)acrylate monomers include trimethylolpropane tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, ε-caprolactone-modified tris((meth)acrooxyethyl) isocyanurate, and pentaerythritol tri(meth)acrylate.

[0075] Examples of tetrafunctional (meth)acrylate monomers include ditrimethylolpropanetetra(meth)acrylate and pentaerythritoltetra(meth)acrylate.

[0076] Examples of pentafunctional (meth)acrylate monomers include dipentaerythritol penta(meth)acrylate.

[0077] Examples of hexa-functional (meth)acrylate monomers include dipentaerythritol hexa(meth)acrylate.

[0078] The solid content of the fourth component in the composition of the present invention is not particularly limited, but in order to more reliably exert the functions of the third component as described above, it is usually set to about 10 to 50% by weight, and particularly preferably to 15 to 30% by weight.

[0079] Component 5 The fifth component is a photoinitiator (photopolymerization initiator). This ensures that the composition of the present invention can reliably initiate curing by ultraviolet irradiation or the like.

[0080] As photoinitiators, for example, dimethyl-2,2′-azobis(2-methylpropionate), 4,4-bis(diethylamino)benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2 Examples include benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, diethylthioxanthone, isopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, methylbenzoyl formate, 2-benzyl-2-dimethylamino-4-morpholinobylophenone, and 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one. Commercially available products can also be used as such photopolymerization initiators. These can be used individually or in combination of two or more.

[0081] The solid content of the fifth component in the composition of the present invention can be appropriately set depending on, for example, the type of polymerization initiator used, but from the viewpoint of the role of the fifth component, it is usually set to about 3 to 15% by weight, and particularly preferably to 5 to 10% by weight.

[0082] Component 6 The composition of the present invention contains an organic solvent as a sixth component. The type of organic solvent can be appropriately determined depending on the type of the first component, etc. In particular, in the present invention, it is preferable to use an organic solvent that contains at least one of the commonly used organic solvents that can uniformly dissolve the first component and the second component, such as a ketone solvent, an ester solvent, an alcohol solvent, and an amide solvent. It is desirable that the organic solvent does not contain a fluorine solvent.

[0083] Examples of ketone-based solvents include acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone.

[0084] Examples of ester solvents include ethyl acetate, butyl acetate, methoxybutyl acetate, and methoxypropyl acetate.

[0085] Examples of alcohol-based solvents include methanol, ethanol, 1-propanol, isopropyl alcohol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether (1-methoxy-2-propanol).

[0086] Examples of amide solvents include dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and diethylformamide.

[0087] The amount of organic solvent used is not limited, and can be appropriately adjusted according to the type of components used, the desired viscosity, etc., so that the solid content of the composition of the present invention is within the range of approximately 0.1 to 90% by weight (preferably approximately 0.1 to 50% by weight). For example, when using the composition of the present invention as a paste, the solid content should be set higher.

[0088] Other ingredients In addition to the first to sixth components, other components may be appropriately blended into the composition of the present invention as needed, within a range that does not impede the effects of the present invention. Examples include crosslinking agents, reactive diluents (e.g., monofunctional monomers), inorganic fine particles (oxide fine particles such as silica, alumina, titania, and zirconia), antifouling agents (slip agents), surface modifiers, ultraviolet absorbers, light stabilizers, dispersants (surfactants), wetting agents, thickeners, antioxidants, polymerization inhibitors, silane coupling agents, and colorants.

[0089] In particular, in the present invention, by including (meth)acryloyl group-containing polydimethylsiloxane (component 7), the coefficient of dynamic friction of the formed hardened layer can be further reduced, resulting in higher finger glide and higher wear resistance.

[0090] Examples of the (meth)acryloyl group-containing polydimethylsiloxane for component 7 include compounds having dimethylpolysiloxane as the basic skeleton and having at least (meth)acryloyl groups introduced to its side chains and / or terminals. Such compounds are not particularly limited, and known or commercially available compounds can be used. Therefore, commercially available (meth)acryloyl group-containing modified polydimethylsiloxanes can be suitably used, for example.

[0091] The solid content of the seventh component in the composition of the present invention is not particularly limited, but in order to more reliably exert the functions of the seventh component as described above, it is usually set to about 5 to 40% by weight, and particularly preferably to 5 to 30% by weight.

[0092] Furthermore, by setting the seventh component to 250 parts by weight or less, preferably 50 to 250 parts by weight, and more preferably 50 to 130 parts by weight, relative to 100 parts by weight of the solid content of the first component, even better finger glide can be obtained.

[0093] B. Properties of the composition of the present invention The composition of the present invention is usually in liquid form. The viscosity (at 20°C) in this case can be appropriately set according to the desired thickness of the hardened layer (hard coat), and can be, for example, about 1 to 500 mPa·s, but is not limited to this.

[0094] The composition of the present invention may be in the form of a solution or a dispersion, as long as it does not hinder the effects of the present invention, but it is particularly desirable that it be in the form of a solution in which at least the first and second components are dissolved in an organic solvent, which is the sixth component. By forming it in the form of a solution, it is possible to form a coating film (cured film) that exhibits higher finger glide.

[0095] C. Preparation of the present invention composition The composition of the present invention can be prepared by uniformly mixing the above-mentioned components. The mixing order is not particularly limited, and any order can be adopted.

[0096] Mixing can be carried out using known or commercially available equipment such as mixers or kneaders. The mixing atmosphere is usually at room temperature and atmospheric pressure, but is not limited to this.

[0097] D. Use of the present invention composition A desired cured layer can be formed by curing the coating film of the composition of the present invention. In other words, a cured layer (cured film) with excellent finger-slip properties, abrasion resistance, water repellency, etc., can be more reliably obtained from the composition of the present invention.

[0098] The cured layer may be transparent, translucent, or opaque. In particular, when used as a protective film for display device screens, etc., it is desirable for the cured layer to be transparent or translucent. In this case, the transparency is not limited, but usually a haze value of around 0.1 to 5% is sufficient, although it is especially desirable for it to be 1% or less.

[0099] Furthermore, the thickness of the hardened layer can be appropriately set according to the desired hardness, moldability, etc., but is usually about 0.1 μm or less, preferably 0.01 to 0.1 μm, and particularly preferably 0.01 to 0.05 μm. In particular, when an optical functional layer such as a refractive index control layer is provided as a layer below the hardened layer, setting the thickness as described above allows the optical properties of the optical functional layer to be effectively exhibited without interfering with them. In other words, the hardened layer of the present invention can be suitably used as a hardened layer to protect the surface of an optical functional layer.

[0100] The method for forming the cured layer is not particularly limited and can be suitably carried out by, for example, a method including a) forming a coating film of the composition of the present invention on a substrate film and b) curing the coating film.

[0101] The base film that forms the underlayment (bottom layer) of the cured layer is not particularly limited, and examples include acrylic resins (such as polymethyl methacrylate), olefin resins (such as polyethylene and polypropylene), polyester resins (such as polyethylene terephthalate and polybutylene terephthalate), polyamide resins (such as nylon), polycarbonate resins, polyurethane resins, vinyl resins (such as vinyl chloride resins and vinyl acetate resins), fluororesins, and silicone resins. In particular, transparent films such as polyethylene terephthalate can be suitably used because they offer excellent transparency.

[0102] The thickness of the base film can be appropriately changed depending on the application, location of use, etc., and can be, for example, about 0.05 to 1 mm, but is not limited to this.

[0103] The coating film of the composition of the present invention can be formed by any known coating method, such as the doctor blade method, bar coating method, dipping method, air spray method, roller brush method, or roller coater method.

[0104] The amount of coating film formed can be set to, for example, an amount that results in the desired thickness of the cured layer, and can usually be appropriately set within a range of approximately 0.1 μm or less (preferably within the range of 0.01 to 0.05 μm).

[0105] Furthermore, the resulting coating film may undergo a drying process as needed before hardening. The drying method may include natural drying or, for example, heating at a temperature of approximately 60-120°C.

[0106] Next, the coating film is cured. The method for curing the coating film is not particularly limited, but a curing method using radiation (active energy rays) can be preferably employed. Any radiation can be used as long as it has an energy level sufficient to cleave the photopolymerization initiator. Examples of radiation include electromagnetic radiation and particle radiation, and it is particularly preferable to use ultraviolet light, infrared light, visible light, far-infrared light, etc.

[0107] In this invention, ultraviolet light can be suitably used, particularly because curing can be carried out relatively easily. Furthermore, when irradiating with ultraviolet light, the light source is not limited, and examples include high-pressure mercury lamps, iron-doped metal halide lamps, gallium lamps, low-pressure mercury lamps, ultra-high-pressure mercury lamps, ultraviolet lasers, LEDs, etc. Therefore, curing can be carried out using known or commercially available equipment equipped with these.

[0108] When irradiating with ultraviolet light, for example, the wavelength range should be around 100-400 nm, with an illuminance of 80-1000 mW / cm². 2 Approximate cumulative light intensity: 100-5000 mJ / cm² 2Ultraviolet irradiation with a certain energy level can be used, but is not limited to that. Ultraviolet irradiation can be carried out using a known or commercially available UV irradiation device.

[0109] The temperature conditions for UV irradiation are not particularly limited, but are usually within the range of 100°C or below. Therefore, it can be suitably carried out even at room temperature (around 10-40°C).

[0110] 2. Film The present invention also includes films (films of the present invention) that have a cured layer of the composition of the present invention on their outermost surface. Therefore, examples of films of the present invention include not only films composed of a single layer of the cured layer of the composition of the present invention, but also laminated films formed by laminating a base film or other layers. However, even in the case of laminated films, at least the cured layer is arranged on the outermost surface.

[0111] The base film is not limited, and for example, the resin film described above can be suitably used. Furthermore, to obtain a film composed of a single layer of the cured layer of the composition of the present invention (assuming the cured layer is peeled off during use), a release film can also be used as the base film.

[0112] Other layers laminated with the cured layer of the composition of the present invention may include, for example, a printed layer, an optically functional layer (refractive index control layer, anti-reflective layer, field of view control layer, etc.), an adhesive layer, an antistatic layer, etc., as long as they do not interfere with the effects of the present invention. These can be formed according to known methods.

[0113] In particular, the present invention provides a film comprising an optically functional layer and a cured layer of the present invention laminated on its surface as the outermost layer. That is, a film in which the cured layer is formed to protect the surface of the optically functional layer, such as an anti-reflective layer, is desirable. The cured layer of the present invention can exhibit desired finger-slip properties, etc., with a relatively thin thickness, so it can effectively bring out the optical functions of the optically functional layer.

[0114] As an example of a more specific embodiment, a film comprising a) a base film, b) a refractive index control layer (lower layer) formed on the base film, and c) a cured layer (upper layer) of the composition of the present invention laminated in direct contact with the refractive index control layer can be suitably employed.

[0115] In this case, the base film and cured layer can be formed according to the method described above.

[0116] Furthermore, the refractive index control layer is not particularly limited as long as it can provide an anti-reflective function. Known refractive index control layers (anti-reflective layers) can be used, and for example, a cured layer of a curable composition containing a polyfunctional (meth)acrylate monomer, oxide-containing fine particles, polymerization initiator, and organic solvent can be suitably used. The cured layer of such a curable composition is shown below as an example of an embodiment.

[0117] As the polyfunctional (meth)acrylate monomer mentioned above, the same compounds as those exemplified in the fourth component above can be used. Its content can be appropriately set within a range of about 1 to 10% by weight in the curable composition.

[0118] As oxide-containing fine particles, known or commercially available fine particles added to optical materials can be used. For example, fine particles of inorganic oxides such as silica and zirconia, as well as fine particles composed of composite materials of these and resins, can be used. These fine particles may be solid or hollow. The shape of the fine particles is usually preferably spherical, but is not limited to this. The average particle size of the fine particles can be, for example, about 0.005 to 0.1 μm. The content of oxide-containing fine particles is not particularly limited, but can be appropriately set within a range of about 1 to 10% by weight in the curable composition.

[0119] The polymerization initiator can be the same as the compound exemplified in the fifth component described above. Its content can be appropriately set within a range of approximately 0.1 to 10% by weight in the curable composition.

[0120] Furthermore, the same type of organic solvent as the one exemplified in the sixth component can be used. In this case, the amount of organic solvent used is not limited and can be appropriately set according to the type of components used, the desired viscosity, etc., such that the solid content is within the range of approximately 5 to 90% by weight.

[0121] A curable composition containing these elements is used to form a refractive index control layer, which is a cured layer. The method for forming it can be carried out in the same manner as the method for forming the cured layer of the composition of the present invention.

[0122] The thickness of the refractive index control layer (lower layer) is not particularly limited, but is usually around 0.05 to 1 μm, and is particularly preferably 0.1 to 0.5 μm.

[0123] 3.Optical products The present invention encompasses optical products in which the film of the present invention is laminated on a substrate. In particular, in the present invention, the screen surface of a display can be used as the substrate in order to protect the screen surface of the display. Among these, it is desirable that the substrate is a display screen that serves as a touch sensor in a touch panel display.

[0124] Such touch panel displays (devices) can be any device that requires the film to have at least transparency and finger glide. Examples include smartphones, tablet terminals, PC monitors, ticket machines, information displays, in-vehicle control panels, digital cameras, multifunction printers (monitor section), portable game devices, bank ATMs, and digital audio players. Products in which the film of the present invention is laminated on the surface of the display screen of these devices are also included in the optical products of the present invention.

[0125] The method for laminating the film of the present invention onto a substrate may be the same as the method for laminating known or commercially available protective films. For example, a method in which a removable adhesive is interposed between the substrate and the film and the film is attached to the substrate is possible, but is not limited thereto.

[0126] As described above, the film of the present invention may be a single layer of cured material or a laminate including a combination of an optically functional layer and a cured layer. In the former case, the structure is substrate / cured layer. In the latter case, the structure is substrate / (optically functional layer / cured layer), substrate / (substrate film / optically functional layer / cured layer), etc. [Examples]

[0127] Examples and comparative examples are shown below to give a more detailed explanation of the features of the present invention. However, the scope of the present invention is not limited to the examples.

[0128] Example 1 The curable composition (coating liquid A) of the present invention was prepared by uniformly mixing each component shown in the "upper layer" of Table 1. On the other hand, the curable composition for forming the lower layer (coating liquid B) was prepared by uniformly mixing each component shown in the "lower layer" of Table 1. The unit of the composition (numerical value) of each component in Table 1 is "weight %". A commercially available polyethylene terephthalate (PET) film (Toyobo Co., Ltd., "Cosmoshine A4100") was used as the base film, and a lower layer and an upper layer were formed on it in sequence. More specifically, coating liquid B was applied to the PET film using a No. 3 bar coater, and dried in an oven (ESPEC Corporation, dryer "SPH-102") at 90°C for 1 minute. Next, ultraviolet irradiation (illuminance 500 mW / cm²) is performed using an ultraviolet irradiation device (H06-L41 ultraviolet curing lamp and ECS-601 conveyor-type ultraviolet irradiation device manufactured by iGraphics Co., Ltd.). 2 , cumulative light intensity 500 mJ / cm 2 The lower layer was then cured. In this way, a lower layer (theoretical film thickness of 200 nm) was formed on the PET film. Subsequently, coating solution A was diluted 50 times with MEK and applied to the lower surface using a No. 4 bar coater, and then dried in the oven at 90°C for 1 minute. Next, ultraviolet irradiation (illuminance 500 mW / cm²) was performed using an ultraviolet irradiation device (H06-L41 ultraviolet curing lamp and ECS-601 conveyor-type ultraviolet irradiation device, manufactured by iGraphics Co., Ltd.). 2 , cumulative light intensity 500 mJ / cm 2 The following procedure was performed to cure each layer. In this way, a laminate was obtained in which a lower layer (theoretical film thickness 200 nm) and an upper layer (theoretical film thickness 17 nm) were formed sequentially on a PET film.

[0129] Examples 2-9 The laminate was prepared in the same manner as in Example 1, except that the composition of the coating liquid used to form the upper and lower layers was changed to that shown in Table 1.

[0130] Comparative Examples 1-2 The laminate was prepared in the same manner as in Example 1, except that the composition of the coating liquid used to form the upper and lower layers was changed to that shown in Table 1.

[0131] [Table 1]

[0132] The components shown in Table 1 were obtained using the following products or manufacturing methods. Furthermore, the "molecular weight" mentioned below refers to the "number-average molecular weight."

[0133] (A) Component 1 (A1) Long chain PFPE acrylate 1 In a 10 ml round-bottom flask containing a stirring bar, weighed out Fluorolink D-6000 (0.5 mmol, 3.00 g) from Solvay Specialty Polymers, Inc., Karenz BEI (1.2 mmol, 0.287 g) from Showa Denko Corporation, triethylamine (0.05 mmol, 0.05 g) from Fujifilm Wako Pure Chemical Industries, Ltd., and 3.0 g of Novec HFE-7200 from 3M. The reaction mixture was stirred at 60°C for 6 hours. Methanol from Fujifilm Wako Pure Chemical Industries, Ltd. was added to the reaction mixture after the reaction, and the mixture was separated into layers. Since the lower layer was the target product, the solvent in the upper layer was removed. The methanol washing step was repeated three times. The product was placed in a round-bottom flask, and the solvent was removed by drying under reduced pressure to synthesize the target product, perfluoropolyether-containing acrylate (yield 88%, 2.89 g). In this way, a long-chain PFPE acrylate 1 (molecular weight 6500) having acrylates at both ends of a perfluoropolyether with a molecular weight of 6000 was obtained. (A2) Long chain PFPE acrylate 2 In a 50 ml round-bottom flask containing a stirring bar, 12.0 g each of Solvay Specialty Polymers' "ZMF-402" (3.0 mmol, 12.00 g), Showa Denko's "Kalenz AOI" (3.6 mmol, 0.508 g), Fujifilm Wako Pure Chemical Industries' triethylamine (0.3 mmol, 0.030 g), and 3M's "Novec HFE-7200" were weighed. The reaction mixture was stirred at 60°C for 6 hours. Methanol from Fujifilm Wako Pure Chemical Industries was added to the reaction mixture after the reaction, and the mixture was separated into layers. Since the lower layer was the target product, the solvent in the upper layer was removed. The washing step with methanol was repeated three times. The product was placed in a round-bottom flask, and the solvent was removed by vacuum drying to synthesize the target product, a perfluoropolyether-containing acrylate (yield 90%, 11.2 g). In this way, we obtained long-chain PFPE acrylate 2 (molecular weight 4200) having an acrylate at one end of a perfluoropolyether with a molecular weight of 4000.

[0134] (B) Second component AD-1700: Fluorolink AD-1700 (manufactured by Solvay Specialty Polymers Co., Ltd.) is a perfluoropolyether with a molecular weight of approximately 1500 and acrylates at both ends (70% non-volatile content, molecular weight 1700).

[0135] (C) Third component (C1) ACMO: Acryloylmorpholine (manufactured by KJ Chemicals Co., Ltd.) (C2) Light ester L: Lauryl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) (C3) Light ester HO-250(N): 2-hydroxyethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)

[0136] (D) Fourth component M-306: Arronix M-306 (manufactured by Toagosei Co., Ltd.) is a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (pentaerythritol triacrylate content 65-70%).

[0137] (E) Fifth component Omnirad184: IBM RESINS BV: 1-Hydroxycyclohexyl-phenylketone

[0138] (F) Component 6 MEK: Methyl ethyl ketone (manufactured by Kanto Chemical Co., Ltd.)

[0139] (G) Seventh component BYK-UV3505: Manufactured by Bic Chemie Japan Co., Ltd., modified polydimethylsiloxane containing acrylate (40% non-volatile content).

[0140] Test Example 1 The following characteristics were investigated for the laminates obtained in each example and comparative example. The results are also shown in Table 1.

[0141] (1) Hayes Measurements were taken using a haze meter: NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. The criteria for judgment were "○" if the haze value was 1% or less, and "×" if it exceeded 1%.

[0142] (2) Water contact angle The contact angle with water was measured using the "Drop Master 700" manufactured by Kyowa Interface Science Co., Ltd. The measurement temperature was 20°C. The criteria for evaluation were as follows: a contact angle of 110° or more was marked "◎", 105° or more but less than 110° was marked "○", 100° or more but less than 105° was marked "△", and less than 100° was marked "×".

[0143] (3) Coefficient of kinetic friction Measurements were taken using the "Tribogear Type14FW" manufactured by Shinto Kagaku Co., Ltd., under the following conditions: terminal: weighing paper, load: 500g, measurement speed: 1000mm / min, scanning distance: 50mm. The judgment criteria were as follows: a dynamic friction coefficient of 0.05 or less was marked "◎", between 0.05 and 0.10 was marked "○", between 0.10 and less than 0.15 was marked "△", and 0.15 or more was marked "×".

[0144] (4) Finger glide A sensory test was conducted in which the coated surface of the laminate was traced with a finger approximately 10 cm long five times. Specifically, the tactile sensation was evaluated by lightly tracing the surface of the upper layer (the hardened layer of the present invention) with a finger five times, as if touching an actual tablet device or smartphone. The evaluation criteria were as follows: "◎" indicated that the finger glided smoothly without catching, "○" indicated that the finger caught once every five times (no problem in actual use), and "×" indicated that the finger always caught without gliding.

[0145] (5) Abrasion resistance Using the "Tribogear Type14FW" manufactured by Shinto Kagaku Co., Ltd., the coating surface of the laminate was subjected to friction testing under the following conditions: terminal width 3, load 130g, measurement speed 5000mm / min, scanning distance 50mm, and number of reciprocations 3000 to 8000. The water contact angle of the surface was measured in the same manner as in (2) above after 3000, 5000, and 8000 reciprocations. Based on these measurement results, the following criteria were used for evaluation. (a) If the contact angle after 8000 cycles is 100° or more: "◎" (b) If the contact angle after 5000 cycles is 100° or more, and the contact angle after 8000 cycles is less than 100°: "○" (c) If the contact angle after 3000 cycles is 100° or more, and the contact angle after 5000 cycles is less than 100°: "△" (d) If the contact angle after 3000 cycles is less than 100°: "×"

[0146] As is clear from the results in Table 1, a comparison of Examples 1 and 2 shows that a molecular weight of PFPE for the first component is preferably 3000 or higher.

[0147] Comparing Example 2 with Comparative Example 1, it can be seen that the abrasion resistance is improved in Example 2 by adding the third component.

[0148] The results from Examples 1, 3, and 4 show that the desired effect can be obtained with various monofunctional (meth)acrylate monomers as the third component. In particular, using hydrophilic components such as ACMO or light ester HO-250(N) yields higher wear resistance.

[0149] From a comparison of Examples 3 and 5 with Comparative Example 2, it can be seen that when the mixing ratio of the third and fourth components is 0.3 to 1.2 times that of the solid content of the fourth component, the abrasion resistance is good, while when it is 3.6 times or more, the abrasion resistance decreases.

[0150] A comparison of Examples 1, 6, 7, and 8 shows that adding the seventh component lowers the coefficient of dynamic friction and results in higher wear resistance. The mixing ratio should be 0.5 to 2.5 times the solid content of the first component, and a ratio of 0.5 to 1.3 times is particularly preferable from the viewpoint of water repellency.

[0151] In Example 9, only the upper layer is laminated to the base film without laminating the lower layer, but it can be seen that the desired effect is obtained.

Claims

1. The following ingredients: (1) Perfluoropolyether group-containing (meth)acrylate monomers having a number average molecular weight of 3000 or more and 7500 or less, (2) A fluorine group-containing (meth)acrylate monomer which has a number average molecular weight of 500 or more and less than 3000, (3) As monofunctional (meth)acrylate monomers that do not contain a fluorine group, at least one of the following: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, lauryl (meth)acrylate, acroylmorpholine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate and glycerol mono(meth)acrylate, (4) Polyfunctional (meth)acrylate monomers (excluding the (meth)acrylate monomers in (1) to (2) above): ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, polycarbonate diol di(meth)acrylate Relate, polyester diol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, polyurethane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated isocyanurate tri(meth)acrylate, ε-caprolactone modified tris((meth)acrooxyethyl) isocyanurate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate or dipentaerythritol hexa(meth)acrylate, (5) Photoinitiator and (6) Organic solvents including, and, (a) The solid content of the fluorine group-containing (meth)acrylate monomer in (2) above is 10 to 50% by weight, (b) The solid content of the monofunctional (meth)acrylate monomer without fluorine groups described in (3) is 30 to 120 parts by weight per 100 parts by weight of the polyfunctional (meth)acrylate monomer described in (4). A curable composition characterized by the following features.

2. The curable composition according to claim 1, wherein the solid content of the perfluoropolyether group-containing (meth)acrylate monomer in (1) is 10 to 30% by weight.

3. The curable composition according to claim 1, wherein the fluorine group-containing (meth)acrylate monomer is contained in an amount of 150 parts by weight or more per 100 parts by weight of the perfluoropolyether group-containing (meth)acrylate monomer of (1) above.

4. The curable composition according to claim 1, wherein the organic solvent comprises at least one of a ketone solvent, an ester solvent, an alcohol solvent, and an amide solvent.

5. The curable composition according to claim 1, further comprising (7) (meth)acryloyl group-containing polydimethylsiloxane in addition to the components (1) to (6) described above.

6. The curable composition according to claim 5, wherein the solid content of the (meth)acryloyl group-containing polydimethylsiloxane is 5 to 40% by weight.

7. The curable composition according to claim 1, wherein the perfluoropolyether group-containing (meth)acrylate monomer in (1) is a compound represented by the general formula A-PFPE-B (wherein PFPE represents a perfluoropolyether group, and one or both of A and B are (meth)acryloyl group-containing organic functional groups, and if A or B is not a (meth)acryloyl group-containing organic functional group, it is an alkyl group having 10 or fewer carbon atoms in which some or all of the hydrogen atoms may be substituted with fluorine atoms).

8. The (meth)acryloyl group-containing organic functional group is (1)-R ２ -R １ (R １ is a (meth)acryloyl group or a (meth)acryloyloxy group, R ２ This is an alkylene group having 10 or fewer carbon atoms, in which some or all of the hydrogen atoms may be substituted with fluorine atoms.) (2)-R ２ -OCONH-R １ (R １ is a (meth)acryloyl group or a (meth)acryloyloxy group, R ２ This is an alkylene group having 10 or fewer carbon atoms, in which some or all of the hydrogen atoms may be substituted with fluorine atoms.) Or, an organic functional group represented by, (3)-R ２ -OCONH-R ３ -(R １ ) ｎ (R １ is a (meth)acryloyl group or a (meth)acryloyloxy group, R ２ is an alkylene group having 10 or less carbon atoms and in which part or all of the hydrogen atoms may be substituted with fluorine atoms, R ３ is a hydrocarbon group having 1 to 10 carbon atoms which may have a branched chain, and n is an integer of 1 or 2.) An organic functional group represented by The curable composition according to claim 7.

9. The curable composition according to claim 1, wherein the solid content of the monofunctional (meth)acrylate monomer that does not contain a fluorine group is 5 to 20% by weight.

10. The curable composition according to claim 1, wherein the solid content of the polyfunctional (meth)acrylate monomer is 10 to 50% by weight.

11. A film in which a cured layer of the curable composition according to any one of claims 1 to 10 is disposed as the outermost layer.

12. The film according to claim 11, wherein the thickness of the cured layer is 0.01 to 0.1 μm.

13. An optical product comprising a film according to claim 11 laminated on a substrate.

14. The optical product according to claim 13, wherein the substrate is a display screen that serves as a touch sensor in a touch panel display.

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