Coincidence composition

Abstract

To provide a polymerizable composition that can give a film having high soil resistance and high mechanical strength.SOLUTION: A polymerizable composition contains (A) a compound represented by the formula (1) [where R1 is -(CH2)x-(O)z-(CH2)y-, x is an integer of 1-2, y is an integer of 1-2, z is 0 or 1, where the total of x, y and z is 3 or 4, and R2 is a C1-4 alkyl group], (B) a compound having a fluoropolyether group and having one or more carbon-carbon double bonds, and (C) a compound having an alkylene oxide group and a methacryloyl group and having two or more polymerizable groups.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a polymerizable composition.

Background Art

[0002] A film having a fine concavo-convex structure with a surface of a visible light wavelength or less is known to be used as an antireflection film. On the surface of such a concavo-convex structure, since the refractive index continuously changes from the air layer with respect to incident light, the reflected light can be dramatically reduced. Patent Documents 1 to 3 disclose films having such a fine concavo-convex structure on the surface.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] The film as described above has excellent antireflection properties due to the concavo-convex structure on its surface. On the other hand, in the film as described above, when dirt such as fingerprints (sebum) adheres to the surface, the dirt easily spreads along the concavo-convex structure, and it is difficult to wipe off the dirt because the dirt enters the concave portions. Furthermore, when wiping off the dirt adhering to the surface, there is also a problem that the concavo-convex structure collapses and the antireflection property is impaired. Since the difference from the reflectance of the normal portion becomes large at the portion where such dirt adheres or the portion where the concavo-convex structure collapses, the portion can be easily visually recognized even by the naked eye.

[0005] Accordingly, an object of the present disclosure is to provide a polymerizable composition capable of providing a film excellent in antifouling properties (e.g., fingerprint wiping property) and mechanical strength (e.g., scratch resistance). [Means for Solving the Problems]

[0006] The present disclosure includes the following aspects. [1] (A) The following formula (1): [Chemical formula] [In the formula: R 1 is -(CH2) x -(O) z -(CH2) y -, x is an integer from 1 to 2, y is an integer from 1 to 2, z is 0 or 1, provided that the sum of x, y, and z is 3 or 4, R 2 is a C 1-4 alkyl group.] a compound represented by (B) a compound having a fluoropolyether group and having one or more carbon-carbon double bonds, and (C) a compound having an alkylene oxide group and a (meth)acryloyl group and having two or more polymerizable groups, a polymerizable composition containing. [2] R 1 is -(CH2) x -O-(CH2) y -, x is 1 or 2, y is 1 or 2, provided that the sum of x and y is 3 or 4, the polymerizable composition according to the above [1]. [3] The compound of component (B) is any of the general formulas (A1), (A2), and (A3): [Chemical formula] [In the formula, Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, R 1 is a fluoro(poly)ether group, R 2 is represented by the following formula: -(Q) h -(CFZ) i -(CH2) j - (wherein Q represents an oxygen atom, a phenylene, a carbazolylene, -NR a -(wherein R a represents a hydrogen atom or an organic group) or a divalent polar group, Z represents a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, h, i and j are each independently an integer of 0 or more and 50 or less, and the sum of h, i and j is at least 1, and the order of presence of each repeating unit enclosed in parentheses is arbitrary in the formula.) and is a group represented by R 3 represents a divalent organic group, R 4 in each occurrence, each independently represents R 4a or R 4b : provided that at least one R 4 is R 4a ; R 4a in each occurrence, each independently represents a divalent organic group having a curable site, R 4b in each occurrence, each independently represents a divalent organic group having no curable site, n1 is an integer of 1 or more and 50 or less, R 5 represents -O-, -S-, -NH- or a single bond, R 6 is Rf-R 1 -R 2 (wherein Rf, R 1 , and R 2 are as defined above), a monovalent organic group or a hydrogen atom, R 7represents a (n2 + n3)-valent organic group which may have a ring structure, a heteroatom and / or a functional group, R 8 represents a divalent organic group, X 1 represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine, n2 is an integer of 1 or more and 3 or less, n3 is an integer of 1 or more and 3 or less.] The polymerizable composition according to the above [1] or [2], which is a compound represented by. [4] The compound of component (B) is represented by the general formula (1) or (2):

Chemical formula

[10] The compound of component (E) is selected from the group consisting of pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycerin diacrylate, glycerin dimethacrylate, glycerin triacrylate, glycerin trimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, N,N'-methylenebisacrylamide, N,N'-ethylenebisacrylamide, N,N'-(1,2-dihydroxyethylene)bisacrylamide, N,N',N''-triacryloyldiethylenetriamine, 1,3,5-triacryloylhexahydro-1,3,5-triazine and 1,3,5-trimethacryloylhexahydro-1,3,5-triazine, and is the polymerizable composition described in the above [9].

[11] A support, A polymer layer having, on its surface, an uneven structure in which a plurality of convex portions are provided at a pitch equal to or less than the wavelength of visible light, and a laminate comprising: The polymer layer is a cured product of the polymerizable composition according to any one of the above [1] to

[10] .

[12] An antireflection film comprising the laminate described in the above

[11] . [Advantages of the Invention]

[0007] According to the present disclosure, there is provided a polymerizable composition capable of providing a film having excellent antifouling properties and scratch resistance. [Brief Description of the Drawings]

[0008]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

MODE FOR CARRYING OUT THE INVENTION

[0009] (Polymerizable Composition) The polymerizable composition of the present disclosure comprises the following components (A) to (C): (A) The following formula (1):

CHEM.

[0010] (Component (A)) The compound of the above component (A) is the following formula (1):

CHEM.

[0011] In one embodiment, R 1 is -(CH2) m -O-(CH2) n -.

[0012] In another embodiment, R 1 is -(CH2) m -(CH2) n -.

[0013] In one embodiment, the sum of x, y and z is 3.

[0014] In another embodiment, the sum of x, y and z is 4.

[0015] The combination (x,y) of x and y is preferably (1,1), (2,1), or (1,2), more preferably (1,1).

[0016] R 2 In, the C 1-4 alkyl group may be linear or branched. In a preferred embodiment, the above C 1-4 alkyl group is linear.

[0017] R 2is preferably a methyl group or an ethyl group, more preferably a methyl group.

[0018] In a preferred embodiment, R 1 is -CH2-O-CH2-, and R 2 is a methyl group.

[0019] The content of component (A) relative to the total mass of the polymerizable composition is preferably 1.0% by mass to 50% by mass, more preferably 5.0% by mass to 40% by mass, and even more preferably 9.0% by mass to 30% by mass. By setting the content of component (A) within the above range, in addition to antifouling properties, high scratch resistance can be obtained. Here, the "total mass of the polymerizable composition" refers to the total mass of the non-volatile components excluding the solvent, and typically, it is the total mass of components (A) to (C) and other components (D) to (F) described below.

[0020] (Component (B)) The above component (B) is a compound having a fluoro(poly)ether group and one or more carbon-carbon double bonds (hereinafter also referred to as "compound (B)").

[0021] The above compound (B) can be a so-called active energy ray curable monomer. Compound (B) imparts functions such as fingerprint removability, water repellency, oil repellency, chemical repellency, and antifouling properties to the polymer layer.

[0022] The above fluoro(poly)ether group is preferably represented by the following formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [wherein, R Fa is, in each occurrence, independently a hydrogen atom, a fluorine atom or a chlorine atom, a, b, c, d, e, and f are each independently an integer from 0 to 200, the sum of a, b, c, d, e, and f is 1 or more, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f attached is arbitrary in the formula. is a group represented by.

[0023] In a preferred embodiment, the above fluoro(poly)ether group is a perfluoro(poly)ether group. That is, R Fa is a fluorine atom.

[0024] a, b, c, d, e, and f are preferably each independently an integer from 0 to 100.

[0025] The sum of a, b, c, d, e, and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. The sum of a, b, c, d, e, and f is preferably 200 or less, more preferably 100 or less, still more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0026] These repeating units may be linear or branched. For example, in the above repeating unit, -(OC6F 12 )- may be -(OCF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. -(OC5F 10)- may be, for example, -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. -(OC3F6)-(i.e., in the above formula, R Fa is a fluorine atom) may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. -(OC2F4)- may be any of -(OCF2CF2)- and -(OCF(CF3))-.

[0027] In one embodiment, the repeating unit is linear. By making the repeating unit linear, the surface slipperiness, friction durability, etc. of the cured product can be improved.

[0028] In one embodiment, the repeating unit is branched. By making the repeating unit branched, the coefficient of kinetic friction of the cured product can be increased.

[0029] In one embodiment, the fluoro(poly)ether group is independently a group represented by any of the following formulas (f1) to (f5). -(OC3F6) d - (f1) [wherein d is an integer from 1 to 200.]; -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [wherein, c and d are each independently an integer of 0 or more and 30 or less, e and f are each independently an integer of 1 or more and 200 or less, the sum of c, d, e and f is 2 or more, the order of existence of each repeating unit enclosed in parentheses with subscripts c, d, e or f is arbitrary in the formula.]; -(R 6 -R 7 ) g - (f3) [wherein, R 6 is OCF2 or OC2F4, R 7 is a group selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups, g is an integer of 2 to 100.]; -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f4) [wherein, e is an integer of 1 or more and 200 or less, a, b, c, d and f are each independently an integer of 0 or more and 200 or less, and the order of existence of each repeating unit enclosed in parentheses with subscripts a, b, c, d, e or f is arbitrary in the formula.] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) [wherein, f is an integer of 1 or more and 200 or less, and a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, and the order of presence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.]

[0030] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, still more preferably 15 to 50, for example 25 to 35. The above formula (f1) is preferably -(OCF2CF2CF2) d - or -(OCF(CF3)CF2) d -represented group, and more preferably -(OCF2CF2CF2) d -represented group.

[0031] In the above formula (f2), e and f are each independently preferably an integer of 5 or more and 200 or less, more preferably 10 to 200. Also, the sum of c, d, e, and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one aspect, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f -represented group. In another aspect, the formula (f2) may be -(OC2F4) e -(OCF2) f -represented group.

[0032] In the above formula (f3), R 6 is preferably OC2F4. In the above (f3), R 7is preferably a group selected from OC2F4, OC3F6 and OC4F8, or a combination of two or three groups independently selected from these groups, more preferably a group selected from OC3F6 and OC4F8. The combination of two or three groups independently selected from OC2F4, OC3F6 and OC4F8 is not particularly limited, and examples thereof include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4-, and -OC4F8OC2F4OC2F4-. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 may be either linear or branched, preferably linear. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g - or -(OC2F4-OC4F8) g -.

[0033] In the above formula (f4), e is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.

[0034] In the above formula (f5), f is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.

[0035] In one embodiment, the fluoro(poly)ether group is a group represented by the above formula (f1).

[0036] In one embodiment, the fluoro(poly)ether group is a group represented by the above formula (f2).

[0037] In one embodiment, the fluoro(poly)ether group is a group represented by the above formula (f3).

[0038] In one embodiment, the fluoro(poly)ether group is a group represented by the above formula (f4).

[0039] In one embodiment, the fluoro(poly)ether group is a group represented by the above formula (f5).

[0040] In the fluoro(poly)ether group, the ratio of e to f (hereinafter referred to as "e / f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, still more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. By setting the e / f ratio to 10 or less, the slipperiness, friction durability, and chemical resistance (for example, durability against artificial sweat) of the cured product obtained from this compound are further improved. The smaller the e / f ratio, the more improved the slipperiness and friction durability of the cured product. On the other hand, by setting the e / f ratio to 0.1 or more, the stability of the compound can be further enhanced. The larger the e / f ratio, the more improved the stability of the compound.

[0041] In one embodiment, the e / f ratio is preferably 0.2 to 0.95, more preferably 0.2 to 0.9.

[0042] In one embodiment, from the viewpoint of heat resistance, the e / f ratio is preferably 1.0 or more, more preferably 1.0 to 2.0.

[0043] In one aspect, the above compound (B) can be a compound obtained by reacting (a1) a compound having an isocyanate group (-NCO group) and (b1) a compound having an active hydrogen.

[0044] [(a1) A compound having an isocyanate group (-NCO group)] Examples of the compound (a1) having an isocyanate group include polyisocyanates. In the present specification, the polyisocyanate means a compound having two or more isocyanate groups in the molecule. The compound (a1) may be a polyisocyanate obtained by trimerizing a diisocyanate. The polyisocyanate obtained by trimerizing such a diisocyanate may be a triisocyanate. The polyisocyanate that is a trimer of a diisocyanate may exist as a polymer in which these are polymerized.

[0045] The diisocyanate is not particularly limited, but diisocyanates in which the isocyanate group is bonded to an aliphatic group such as trimethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate; and diisocyanates in which the isocyanate group is bonded to an aromatic group such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate.

[0046] In a preferred embodiment, the compound (a1) can be an isocyanurate-type polyisocyanate. The isocyanurate-type polyisocyanate may exist as a polymer obtained by polymerizing these. That is, the isocyanurate-type polyisocyanate may be a monocyclic compound having only one isocyanurate ring, or a polycyclic compound obtained by polymerizing this monocyclic compound, or a mixture thereof. Such isocyanurate-type polyisocyanates are commercially available, for example, as Sumidur® N3300 (manufactured by Sumitomo Bayer Urethane Co., Ltd.).

[0047] Specific polyisocyanates are not particularly limited, but examples include compounds having the following structures.

[0048]

Chemical formula

[0049] These polyisocyanates may exist as polymers. For example, in the case of an isocyanurate-type polyisocyanate of hexamethylene diisocyanate, it may exist as a polymer having the following structure.

[0050]

Chemical formula

[0051] [Compound (b1) having active hydrogen] Compound (b1) includes the following two components: (b1-1) A compound having an active hydrogen and a perfluoropolyether group, and (b1-2) A monomer containing an active hydrogen and a carbon-carbon double bond, and preferably contains these. More preferably, compound (b1) further contains (b1-3) other compounds having active hydrogen.

[0052] As used herein, "active hydrogen" means a hydrogen atom that can be donated as a proton to an isocyanate group. Groups containing active hydrogen include, for example, -OH group, -C(=O)H group, -SH group, -SO3H group, -SO2H group, -SOH group, -NH2 group, -NH- group, or -SiH group, etc. For example, when the active hydrogen contained in compound (b1) is an -OH group, a urethane bond is formed when compound (a1) and compound (b1) react.

[0053] It is preferable that the number of moles of active hydrogen in compound (b1) is equal to the number of moles of isocyanate groups in compound (a1). For example, when the functional group having active hydrogen in compound (b1) is one, it is preferable that the number of moles of compound (b1) is equal to the number of moles of isocyanate groups in compound (a1).

[0054] [Compound (b1-1) having an active hydrogen and a perfluoropolyether group] Compound (b1-1) is a compound containing an active hydrogen and a perfluoropolyether group. For example, in addition to the perfluoropolyether group, it can be a compound having one group containing an active hydrogen at one molecular end, such as a hydroxyl group, or having a hydroxyl group at each of the two ends. Since the perfluoropolyether group has been described above, duplicate descriptions are omitted.

[0055] Compound (b1-1) is not particularly limited, but has a number average molecular weight of 500 to 12,000, preferably 1,000 to 10,000, more preferably 1,500 to 8,000. In the present invention, "average molecular weight" refers to the number average molecular weight, and the "average molecular weight" 19 is a value measured by 19F-NMR.

[0056] Preferably, compound (b1-1) is either of the following general formulas (b1-1-i) and (b1-1-ii): Rf 1 -PFPE-R 1 -CH2OH (b1-1-i) HOCH2-R1 -PFPE-R 1 -CH2OH (b1-1-ii) It may be at least one compound represented by the formula. Here, PFPE is as described above.

[0057] In the above formulas (b1-1-i) and (b1-1-ii), Rf 1 represents an alkyl group having 1 to 16 carbon atoms (for example, linear or branched) which may be substituted by one or more fluorine atoms, preferably a linear or branched alkyl group having 1 to 3 carbon atoms which may be substituted by one or more fluorine atoms. Preferably, Rf 1 is linear. Also preferably, the alkyl group which may be substituted by the above one or more fluorine atoms is a fluoroalkyl group or a perfluoroalkyl group in which the terminal carbon atom is CF2H- and all other carbon atoms are completely substituted by fluorine, more preferably a perfluoroalkyl group, specifically -CF3, -CF2CF3, or -CF2CF2CF3.

[0058] In the above formulas (b1-1-i) and (b1-1-ii), R 1 each independently represents the following formula: -(Y) f -(CF2) g -(CH2) h - It is a group represented by the following formula. In this formula, Y is a divalent polar group. Examples of this divalent polar group include, but are not particularly limited to, -COO-, -OCO-, -CONH-, -OCH2CH(OH)CH2-, -CH2CH(OH)CH2O-, -COS-, -SCO-, -O-, etc., and preferably -COO-, -CONH-, -CH2CH(OH)CH2O-, -O-. In this formula, f, g, and h are each independently an integer from 0 to 50, preferably from 0 to 20, for example, an integer from 1 to 20, and the sum of f, g, and h is at least 1, preferably from 1 to 10. It is more preferable that f, g, and h are integers from 0 to 2, and even more preferable that f = 0 or 1, g = 2, and h = 0 or 1. Also, the order of existence of each repeating unit enclosed in parentheses with subscripts f, g, and h is arbitrary in the formula.

[0059] In a preferred embodiment, the compound (b1-1) is a compound represented by the above formula (b1-1-i). Rf 1 -PFPE-R 1 -CH2OH (b1-1-i)

[0060] [(b1-2) A monomer containing an active hydrogen and a carbon-carbon double bond] The monomer (b1-2) having an active hydrogen and a carbon-carbon double bond is preferably a (meth)acrylate or vinyl monomer having an active hydrogen, particularly a hydroxyl group. Specific examples of the monomer (b1-2) include HO(CH2CH2) i OCO(R 18 )C=CH2 (In the formula, R 18 is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine, i = 1 to 10), for example, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; CH3CH(OH)CH2OCO(R 18 )C=CH2 (In the formula, R 18is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine), for example, 2-hydroxypropyl (meth)acrylate; CH3CH2CH(OH)CH2OCO(R 18 )C=CH2 (In the formula, R 18 is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine), for example, 2-hydroxybutyl (meth)acrylate; C6H5OCH2CH(OH)CH2OCO(R 18 )C=CH2 (In the formula, R 18 is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine), for example, 2-hydroxy-3-phenoxypropyl (meth)acrylate; HOCH2C(CH2OCO(R 18 )C=CH2)3 (In the formula, R 18 is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine), for example, pentaerythritol triacrylate; C(CH2OCO(R 18 )C=CH2)3CH2OCH2C(CH2OCO(R 18 )C=CH2)2CH2OH (In the formula, R 18 is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine), for example, dipentaerythritol polyacrylate; HOCH2CH2OCOC6H4COOCH2CH2OCO(R 18 )C=CH2 (In the formula, R 18 is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine), for example, 2-acryloyloxyethyl-2-hydroxyethyl phthalate; H(OCH2CH2) n11 OCO(R 18 )C=CH2 (wherein, n11 is 1 to 30, R 18 is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine), for example, poly(ethylene glycol) acrylate; H(OCH(CH3)CH2) n11 OCO(R 18 )C=CH2 (wherein, n11 is 1 to 30, R 18 is a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine), for example, poly(propylene glycol) acrylate HO(CH2) k CH=CH2 (k = 1 to 20); (CH3)3SiCH(OH)CH=CH2; and styrylphenol, may be mentioned.

[0061] [(b1-3) Compound having other active hydrogen] The compound (b1-3) having other active hydrogen preferably has no perfluoropolyether group and carbon-carbon double bond and has at least one active hydrogen. The compound (b1-3) may be a compound having one active hydrogen-containing group, for example, a hydroxyl group, at one molecular terminal, or a compound having one active hydrogen-containing group, for example, a hydroxyl group, at each of the two terminals. Preferred examples of the compound (b1-3) are a monohydric alcohol composed of a linear or branched hydrocarbon having 1 to 16 carbon atoms, a secondary amine composed of a linear or branched hydrocarbon having 1 to 16 carbon atoms, a secondary amine having an aromatic group, Rf alcohol; Q(CF2) l (CH=CH) m (CHI) n (CH2) o OH (Q is a hydrogen atom, a fluorine atom, a (CF3)2CF- group, l is an integer of 1 to 10, m and n are each independently 0 or 1, o is an integer of 1 to 10), a polyalkylene glycol monoester; for example, R3 (OCH2CH2) p OH, R 3 (OCH2CH2CH2) q OH(R 3 is a linear or branched hydrocarbon having 1 to 16 carbon atoms, or an acetyl group or an alkylphenoxy group, and p and q are each independently an integer from 1 to 20), aromatic alcohol, a silane compound having an active hydrogen, can be mentioned.

[0062] Specific examples of the silane compound having an active hydrogen include (CH3)3Si(CH2) s1 OH (s1 is an integer from 1 to 20) and compounds having the structures shown below can be mentioned.

[0063]

Chemical formula

[0064] The silane compound having an active hydrogen of the compound (b1-3) is not particularly limited, but may have a number average molecular weight of 100 to 20,000, preferably 500 to 15,000, more preferably 800 to 12,000.

[0065] In the above formulas (b1-3-i) and (b1-3-ii), R 11 , R 18 , R 13 , R 14 and R 15 are each independently an alkyl group or an aryl group.

[0066] The above alkyl group is not particularly limited, but examples include an alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group may be linear or branched, but is preferably linear. Preferred specific examples include an n-butyl group for R 11 , and a methyl group for R 18 ~R 15 .

[0067] The aryl group is not particularly limited, and examples thereof include aryl groups having 6 to 20 carbon atoms. The aryl group may contain two or more rings. A preferred aryl group is a phenyl group.

[0068] The alkyl group and the aryl group may, if desired, contain a heteroatom, such as a nitrogen atom, an oxygen atom, or a sulfur atom, in its molecular chain or ring.

[0069] Furthermore, the alkyl group and the aryl group may, if desired, be halogen; a C 1-6 alkyl group, a C 2-6 alkenyl group, a C 2-6 alkynyl group, a C 3-10 cycloalkyl group, a C 3-10 unsaturated cycloalkyl group, a 5- to 10-membered heterocyclyl group, a 5- to 10-membered unsaturated heterocyclyl group, a C 6-10 aryl group, or a 5- to 10-membered heteroaryl group, which may be substituted with one or more substituents selected therefrom.

[0070] In the above formulas (b1-3-i) and (b1-3-ii), R 16 represents a divalent organic group. Preferably, R 16 is -(CH2) r -(wherein r is an integer of 1 to 20, preferably an integer of 1 to 10).

[0071] In the above formulas (b1-3-i) and (b1-3-ii), l1 and n1 are each independently 0 or 1; m1 is an integer of 1 to 500, preferably an integer of 1 to 200, more preferably an integer of 5 to 150; o1 is an integer of 0 to 20, for example, an integer of 1 to 20; and p1 is 0 or 1.

[0072] Specific compounds represented by the above formula (b1-3-i) include, for example, the following compounds.

[0073] [Chemical formula]

[0074] Also, the compound (b1-3) may be a silane compound having an amino group as an active hydrogen-containing group. Examples of such compounds include, but are not limited to, the following. Here, m is from 1 to 500.

[0075] [Chemical formula]

[0076] The compounds (b1-1), (b1-2) and (b1-3) may be in the ranges of 0.1 to 2 moles, 5 to 8.85 moles and 0.05 to 2 moles, respectively, based on 9 moles of the isocyanate groups in (A).

[0077] In one aspect, component (A) preferably contains a structure in which -NHC(=O)- derived from the isocyanate group of compound (a1) is bonded to the portion from which the active hydrogen of compound (b1) has been eliminated. Component (A) has an R x1 -C(=O)NH- structure, and more preferably contains an R x2 -C(=O)NH- structure. Here, C(=O) represents a carbonyl group. For example, R x1 is Rf 1 -PFPE-R 1 -CH2O-, or HOCH2-R 1 -PFPE-R 1 -CH2O-, and R x2 is a structure represented by the following formula; CH2=C(R 18 )COO(CH2CH2) i O-, CH2=C(R 18 )COOCH2CH(CH3)O-, CH2=C(R 18 )COOCH2CH(CH2CH3)O-, CH2=C(R 18)COOCH2CH(CH2OC6H5)O-, (CH2=C(R 18 )COOCH2)3CCH2O-, C(CH2COO(R 18 )C=CH2)3CH2OCH2C(CH2OCO(R 18 )C=CH2)2CH2O-, CH2=C(R 18 )COOCH2CH2OCOC6H4COOCH2CH2O-, CH2=C(R 18 )COO(CH2CH2O) n11 -, CH2=C(R 18 )COO(CH2CH(CH3)O) n11 -, CH2=CH(CH2) k O-, CH2=CHCH(Si(CH3)3)O-, or Ar-Ph-O- any of which. Here, Ph is a benzene ring in which part of the hydrogen atoms may be substituted, and Ar is a structure having at least a styryl group. R 1 , R 18 , Rf 1 、 n11, i, k, and PFPE are as described above.

[0078] Specific structures of the component (A) of this embodiment include, but are not limited to, for example, those shown below.

[0079]

Chemical formula

[0080] Here, R x11 , R x12 and R x13 are, independently of each other, R x1 , R x2 or R x3 , and at least one of R x11 , R x12 and R x13 is R x1and R x11 、R x12 and R x13 at least one of which is R x2 。R y1 、R y2 and R y3 are, independently of one another, an alkylene group having 1 to 10 carbon atoms, preferably -(CH2) n5 -(wherein n5 is an integer of 1 to 10, preferably an integer of 3 to 6, typically 6) or has the structure shown below. Here, * indicates a bond. R x1 and R x2 are as described above. R x3 is a structure in which the active hydrogen of the compound (b1-3) has been eliminated.

[0081] [Chemical formula]

[0082] In one embodiment, the above compound (B) is any of the general formulas (A1), (A2), and (A3): [Chemical formula] [wherein, Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, R 1 is a fluoro(poly)ether group, R 2 is the following formula: -(Q) h -(CFZ) i -(CH2) j -[[]]END]] (wherein, Q represents an oxygen atom, a phenylene, a carbazolylene, -NR a -(wherein, R a represents a hydrogen atom or an organic group) or a divalent polar group, Z represents a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, h, i and j are each independently an integer of 0 or more and 50 or less, and the sum of h, i and j is at least 1, and the order of presence of each repeating unit enclosed in parentheses is arbitrary in the formula.) is a group represented by R 3 represents a divalent organic group, R 4 in each occurrence, is independently, R 4a or R 4b represents: provided that at least one R 4 is R 4a and R 4a in each occurrence, independently represents a divalent organic group having a curable site, R 4b in each occurrence, independently represents a divalent organic group having no curable site, n1 is an integer of 1 or more and 50 or less, R 5 represents -O-, -S-, -NH- or a single bond, R 6 is Rf-R 1 -R 2 (wherein, Rf, R 1 , and R 2 are as defined above), represents a monovalent organic group or a hydrogen atom, R 7 represents a (n2 + n3)-valent organic group which may have a ring structure, a hetero atom and / or a functional group, R 8 represents a divalent organic group, X 1 represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine, n2 is an integer of 1 or more and 3 or less, n3 is an integer of 1 or more and 3 or less.] It may be a compound represented by.

[0083] In the above formula, unless otherwise specified, the "alkyl group" includes, for example, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 6, more preferably 1 to 3, still more preferably 1) (e.g., methyl group, ethyl group, propyl group, isopropyl group). The "alkyl group" may be linear or branched, but is preferably linear.

[0084] In the above formula, unless otherwise specified, the "hydrocarbon group" means a group containing carbon and hydrogen. The "hydrocarbon group" is not particularly limited, and examples thereof include hydrocarbon groups having 1 to 20 carbon atoms which may be substituted by one or more substituents, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The above "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. Further, the hydrocarbon group may contain one or more ring structures. Note that such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at its terminal or in the molecular chain.

[0085] In the above formula, unless otherwise specified, the substituents of the "hydrocarbon group" are not particularly limited, and examples thereof include halogen; C 1-6 alkyl group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5- to 10-membered heterocyclyl group, 5- to 10-membered unsaturated heterocyclyl group, C 6-10 aryl group, 5- to 10-membered heteroaryl group, etc.

[0086] In the above formula, unless otherwise specified, the "organic group" or "monovalent organic group" means a group containing carbon. The "organic group" or "monovalent organic group" is not particularly limited, and examples thereof include the above hydrocarbon groups. Further, the "divalent organic group" means a divalent group derived by removing one more hydrogen atom from the "monovalent organic group".

[0087] In the above formulas (A1) and (A3), Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms.

[0088] The alkyl group having 1 to 16 carbon atoms which may be substituted by one or more of the above fluorine atoms is a linear or branched alkyl group having 1 to 16 carbon atoms which may be substituted by one or more of the above fluorine atoms, preferably a linear or branched alkyl group having 1 to 3 carbon atoms which may be substituted by one or more of the above fluorine atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms which may be substituted by one or more of the above fluorine atoms. Preferably, the alkyl group which may be substituted by one or more of the above fluorine atoms is a fluoroalkyl group in which the terminal carbon atom is CF2H- and all other carbon atoms are completely substituted by fluorine, or a perfluoroalkyl group, more preferably a perfluoroalkyl group, specifically -CF3, -CF2CF3, or -CF2CF2CF3.

[0089] In the above formula, R 1 is the above-mentioned fluoro(poly)ether group.

[0090] In the above formulas (A1) and (A2), R 2 is a group represented by the formula: -(Q) h -(CFZ) i -(CH2) j -. Here, h, i, and j are each independently an integer of 0 or more and 50 or less, the sum of h, i, and j is at least 1, and the order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula.

[0091] In the above formula, Q represents an oxygen atom, phenylene, carbazolylene, -NR a -(wherein R a represents a hydrogen atom or an organic group) or a divalent polar group, preferably an oxygen atom or a divalent polar group, more preferably an oxygen atom.

[0092] The "divalent polar group" in the above Q is not particularly limited, but -C(O)-, -C(=NR b )-, and -C(O)NR b -(in these formulas, R b(which represents a hydrogen atom or a lower alkyl group). The "lower alkyl group" is, for example, an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, and these may be substituted with one or more fluorine atoms.

[0093] In the above formula, Z represents a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom.

[0094] The above "lower fluoroalkyl group" is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, and still more preferably a trifluoromethyl group.

[0095] R 2 is preferably a group represented by the formula: -(O) h -(CF2) i -(CH2) j (wherein h, i and j have the same meanings as defined above, and the order of existence of each repeating unit enclosed in parentheses is arbitrary in the formula).

[0096] The above formula: -(O) h -(CF2) i -(CH2) j - Examples of the group represented by - include, for example, -(O) h’ -(CF2) i’ -(CH2) j’ -O-[(CH2) j” -O-] j’’’ (wherein h' is 0 or 1, i', j' and j'' are each independently an integer of 1 to 10, and j''' is 0 or 1).

[0097] In the above formulas (A1) and (A2), R 3 represents a divalent organic group.

[0098] R 3 The group is preferably -C(R 3a )(R 3b) - is as follows. Here, R 3a and R 3b each independently represents a hydrogen atom or an alkyl group, and preferably, one of R 3a and R 3b is an alkyl group.

[0099] In the above formulas (A1) and (A2), R 4 in each occurrence independently represents R 4a or R 4b . However, at least one R 4 is R 4a .

[0100] The above R 4a in each occurrence independently represents a divalent organic group having a curable site.

[0101] The above "curable site" is not particularly limited, but preferably a group containing a carbon-carbon double bond, a carbon-carbon triple bond, a cyclic ether group, a hydroxyl group, a thiol group, an amino group, an azide group, a nitrogen-containing heterocyclic group, an isocyanate group, a halogen atom, a phosphate-containing group, or a silane coupling group, or a group containing a precursor group thereof.

[0102] Examples of the above curable site include an epoxy group, a glycidyl group, an alicyclic epoxy group, a vinyl group, an allyl group, an optionally substituted acryloyl group, a cinnamoyl group, a 2,4-hexadienoyl group, a vinyl ether (vinyloxy) group, a hydroxyl group, an oxetanyl group, an isocyanate group, a catechol group, a thiol group, an amino group, an alkylamino group, a dialkylamino group, an azide group, a phosphate-containing group, a carboxyl group, an imidazolyl group, a triazolyl group, a benzotriazolyl group, a tetrazolyl group, a halogen atom, or a silane coupling group, or a precursor group thereof.

[0103] The above alicyclic epoxy group preferably has the following formula:

Chemical formula

[0104] The above alicyclic epoxy group is more preferably [Chemical formula] is

[0105] The above optionally substituted acryloyl group is CH2=CX 1 -C(O)- is a group represented by

[0106] The above X 1 represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, for example, a methyl group.

[0107] The above optionally substituted acryloyl group is preferably an acryloyl group or a methacryloyl group. Hereinafter, the acryloyl group and the methacryloyl group are collectively referred to as "(meth)acryloyl group".

[0108] The above phosphoric acid-containing group is not particularly limited as long as it contains a phosphoric acid group. For example, C 1-6 alkylene-OP(O)(OH)(OR) (wherein R is a hydrogen atom or C 1-3 alkyl.) can be

[0109] In one aspect, the above curable site can be an epoxy group, a glycidyl group, an alicyclic epoxy group, a vinyl group, an allyl group, a (meth)acryloyl group, a cinnamoyl group, a 2,4-hexadienoyl group, or a vinyl ether (vinyloxy) group.

[0110] In a preferred aspect, the above curable site is an epoxy group, a glycidyl group or CH2=CX 1’ -C(O)- (wherein X 1’represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine, and is preferably an epoxy group, a glycidyl group, or a (meth)acryloyl group.

[0111] In one embodiment, the curable site may be an allyl group, a cinnamic acid group, a sorbic acid group, an acryloyl group, and a methacryloyl group.

[0112] The preferred curable site varies depending on the material to be coated. For example, when the material is an amorphous synthetic resin (e.g., an acrylic resin), the "curable site" is preferably an allyl group, a cinnamic acid group, a sorbic acid group, or CH2=CX 1 -C(O)-(wherein X 1 represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine) (e.g., a (meth)acryloyl group), and more preferably, an acryloyl group and a methacryloyl group.

[0113] R 4a is preferably the following formula:

Chemical formula

[0114] In the above formula, R 31 represents, in each occurrence, independently of each other, a hydrogen atom or an alkyl group. The R 31 is preferably a hydrogen atom.

[0115] In the above formula, R 32 represents, in each occurrence, independently of each other, a hydrogen atom or an alkyl group. The R 32 is preferably a methyl group or a hydrogen atom, and more preferably a hydrogen atom

[0116] In the above formula, R 33 represents, in each occurrence, independently of each other, a curable site.

[0117] In one embodiment, R 33 may be an epoxy group, a glycidyl group, an alicyclic epoxy group, a vinyl group, an allyl group, an optionally substituted acryloyl group, a cinnamoyl group, a 2,4-hexadienoyl group, a vinyl ether (vinyloxy) group, a hydroxyl group, an oxetanyl group, an isocyanate group, a catechol group, a thiol group, an amino group, an alkylamino group, a dialkylamino group, an azide group, a phosphate-containing group, a carboxyl group, an imidazolyl group, a triazolyl group, a benzotriazolyl group, a tetrazolyl group, a halogen atom, or a silane coupling group, or a precursor group thereof.

[0118] In a preferred embodiment, R 33 may be an epoxy group, a glycidyl group, an alicyclic epoxy group, a vinyl group, an allyl group, a (meth)acryloyl group, a cinnamoyl group, a 2,4-hexadienoyl group, or a vinyl ether (vinyloxy) group.

[0119] In a more preferred embodiment, R 33 may be an epoxy group, a glycidyl group, an alicyclic epoxy group, or a (meth)acryloyl group, preferably an epoxy group, a glycidyl group, or a (meth)acryloyl group, particularly a (meth)acryloyl group.

[0120] In the above formula, Y 1 represents -O-, -N(R c )-, phenylene or carbazolylene. Here, R c represents an organic group, preferably an alkyl group.

[0121] Y 1 is preferably -O-, phenylene, or carbazolylene, more preferably -O- or phenylene, and even more preferably -O-.

[0122] In the above formula, Y 2 represents a linker having 1 to 16 (more preferably 2 to 12, even more preferably 2 to 10) main chain atoms. The Y 2Examples include, but are not particularly limited to, -(CH2-CH2-O) p1 -(where p1 represents an integer from 1 to 10, for example, an integer from 2 to 10), -(CHR d ) p2 -O-(where p2 is an integer from 1 to 40, and R d represents hydrogen or a methyl group), -(CH2-CH2-O) p3 -CO-NH-CH2-CH2-O-(where p3 represents an integer from 1 to 10, for example, an integer from 2 to 10), -CH2-CH2-O-CH2-CH2-, -(CH2) p4 -(where p4 represents an integer from 1 to 6), -(CH2) p5 -O-CONH-(CH2) p6 -(where p5 represents an integer from 1 to 8, preferably 2 or 4, and p6 represents an integer from 1 to 6, preferably 3), or -O- (provided that Y 1 is not -O-). Preferred Y 2 Examples include, but are not particularly limited to, -(CH2-CH2-O) p1 -(where p1 represents an integer from 1 to 10, for example, an integer from 2 to 10) or -(CHR d ) p2 -O-(where p2 is an integer from 1 to 40, and R d represents hydrogen or a methyl group), specifically, -(CH2-CH2-O)2- or -CH2-CH2-O-. These groups are bonded at the left end to the molecular main chain side (Y 1 side) and at the right end to the curable site side (R 33 side).

[0123] R 4a is more preferably a group represented by the following formula:

Chemical formula

[0124] 1 ​represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, for example, a methyl group. In the above formula, q1 is an integer of 1 to 10, preferably an integer of 1 to 5, for example, 1 or 2. q2 is an integer of 1 to 10, preferably an integer of 1 to 5, for example, 2.

[0125] The above R 4b is, in each occurrence, independently, a divalent organic group having no curable site.

[0126] R 4b is preferably -(CHR 4c -CR 4d R 4e ) s0 -. Here, R 4c and R 4d each independently represent a hydrogen atom or an alkyl group, s0 is an integer of 0 to 50, and the R 4e group is -Q’-R 4f . Here, Q’ has the same meaning as the above Q, and R 4f is an organic group having no curable site and is a group in which the group R 4g described later is bonded to Q’ via a linker or directly.

[0127] The linker is preferably (a)-(CH2-CH2-O) s1 -(s1 represents an integer of 1 to 10, for example, an integer of 2 to 10.) (b)-(CHR 4h ) s2 -O-(s2 represents the number of repetitions which is an integer of 1 to 40. R 4h represents a hydrogen or methyl group.) (c)-(CH2-CH2-O) s1 -CO-NH-CH2-CH2-O-(s1 has the same meaning as above.) (d)-CH2-CH2-O-CH2-CH2- (e)-(CH2) s3 -(s3 represents an integer of 1 to 6.), or (f)-(CH2) s4 -O-CONH-(CH2) s5 -(s4 represents an integer from 1 to 8, preferably 2 or 4. s5 represents an integer from 1 to 6, preferably 3), or (g)-O- (provided that Q’ is not -O-) is as follows.

[0128] R 4g is preferably one of the following groups. (i) Alkyl group Examples: Methyl, ethyl

[0129] (ii) A chain group containing an alkyl group substituted with fluorine Examples:

Chemical formula

[0130] (iii) A group containing one or more cyclic moieties selected from the group consisting of monocyclic carbocyclic rings, bicyclic carbocyclic rings, tricyclic carbocyclic rings, and tetracyclic carbocyclic rings Examples:

Chemical formula

[0131] (iv) A group containing a hydrocarbon group substituted with one or more (preferably 1 or 2) carboxy groups Examples:

Chemical formula

[0132] (v) A group containing one or more (preferably 1) amino group (vi) Hydrogen (vii) A group containing an imidazolium salt Examples:

Chemical formula

[0133] R 4g is more preferably a hydrogen atom, or an alkyl group which may be fluorinated and may be bonded via an ethylene chain, more preferably a hydrogen atom, a methoxyethyl group, an isobutyl group, or R 3i -CF2-(CF2) s6 -(CH2) s7 -O-(CH2)2-(R x is a fluorine atom or a hydrogen atom, s6 is an integer of 0 to 6, and s7 is an integer of 1 to 6), and more preferably a 3-(perfluoroethyl)propoxyethyl group [structural formula: CF3-(CF2)-(CH2)3-O-(CH2)2-].

[0134] In the above R 4 Among them, the constituent unit R 4a and the constituent unit R 4b may each form a block or may be randomly bonded.

[0135] In the above formulas (A1) and (A2), n1 is an integer of 1 or more and 100 or less, preferably an integer of 1 or more and 50 or less, and more preferably an integer of 2 or more and 30 or less.

[0136] In the above formulas (A1) and (A2), R 5 represents -O-, -S-, -NH- or a single bond, preferably -O-.

[0137] In the above formulas (A1) and (A2), R 6 is Rf-R 1 -R 2 (wherein Rf, R 1 , and R 2 have the same meanings as defined above), represents a monovalent organic group or a hydrogen atom.

[0138] R 6 is preferably an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably methyl.

[0139] In the above formula (A3), R7 represents a (n2 + n3)-valent organic group which may have a ring structure, a heteroatom and / or a functional group.

[0140] In the above formula (A3), n2 is an integer of 1 or more and 3 or less.

[0141] In the above formula (A3), n3 is an integer of 1 or more and 3 or less.

[0142] Preferably, n2 + n3 is 3. For example, n2 is 1 and n3 is 2, or n2 is 2 and n3 is 1.

[0143] The above R 7 Examples of the "(n2 + n3)-valent organic group which may have a ring structure, a heteroatom and / or a functional group" in R include groups derived by further removing (n2 + n3 - 1) hydrogen atoms from a monovalent organic group.

[0144] R 7 Preferably, R is represented by the following formula:

Chemical formula

[0145] More preferably, R 7 is represented by the following formula:

Chemical formula

[0146] In the above formula (A3), R 8 represents a divalent organic group. The R 8 is preferably -O-(CH2) r -(where r is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 3 or less), -NH-(CH2) r -(where r has the same meaning as above), and more preferably -O-(CH2) r -(where r is an integer of 1 or more and 3 or less).

[0147] In the above formula (A3), X 1 represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine.

[0148] X 1 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and still more preferably a hydrogen atom or methyl.

[0149] The compounds represented by the above formulas (A1) to (A3) are not particularly limited, but may have a number average molecular weight of about 5×10 2 to 1×10 5 . Among such a range, having a number average molecular weight of about 2,000 to 10,000 is preferable from the viewpoint of frictional durability. The number average molecular weight can be determined by 19 F-NMR.

[0150] In one aspect, the above compound (B) is the following formula (B1) or (B2): [Chemical formula] [Wherein: R F1 is, in each occurrence, independently of one another, Rf 1 -R F -O q -; R F2 is -Rf 2 p -R F -O q -; Rf 1 is, in each occurrence, independently of one another, a C 1-16 alkyl group which may be substituted by one or more fluorine atoms; Rf 2 is a C 1-6 alkylene group which may be substituted by one or more fluorine atoms; R Fis, in each occurrence, independently of one another, a divalent fluoropolyether group; p is 0 or 1; q is, in each occurrence, independently of one another, 0 or 1; X A is, independently of one another, a single bond or an organic group having a valence of 2 to 10; R D is, in each occurrence, independently of one another, a group containing a carbon-carbon double bond; α is an integer from 1 to 9; β is an integer from 1 to 9; γ is, independently of one another, an integer from 1 to 9.] It may be a compound represented by the formula.

[0151] In the above formula (B1), R F1 is, in each occurrence, independently of one another, Rf 1 -R F -O q -.

[0152] In the above formula (B2), R F2 is -Rf 2 p -R F -O q -.

[0153] In the above formula, Rf 1 is, in each occurrence, independently of one another, a C 1-16 alkyl group which may be substituted by one or more fluorine atoms.

[0154] In the above C 1-16 alkyl group which may be substituted by one or more fluorine atoms, the "C 1-16 alkyl group" may be linear or branched, preferably a linear or branched C 1-6 alkyl group, particularly a C 1-3 alkyl group, more preferably a linear C 1-6 alkyl group, particularly a C 1-3 alkyl group.

[0155] The above Rf 1 is preferably a C 1-16 alkyl group substituted by one or more fluorine atoms, more preferably a CF2H-C 1-15 perfluoroalkylene group, and even more preferably a C 1-16 perfluoroalkyl group.

[0156] The above C 1-16 perfluoroalkyl group may be linear or branched, preferably a linear or branched C 1-6 perfluoroalkyl group, particularly a C 1-3 perfluoroalkyl group, more preferably a linear C 1-6 perfluoroalkyl group, particularly a C 1-3 perfluoroalkyl group, specifically -CF3, -CF2CF3, or -CF2CF2CF3.

[0157] In the above formula, Rf 2 may be a C 1-6 alkylene group substituted by one or more fluorine atoms.

[0158] The "C 1-6 alkylene group" in the above alkylene group substituted by one or more fluorine atoms may be linear or branched, preferably a linear or branched C 1-6 alkylene group, more preferably a linear C 1-3 alkylene group. 1-3 is an alkylene group.

[0159] The above Rf 2 is preferably a C 1-6 alkylene group substituted by one or more fluorine atoms, more preferably a C 1-6 perfluoroalkylene group, and even more preferably a C 1-3 perfluoroalkylene group.

[0160] The above C 1-6The perfluoroalkylene group may be linear or branched, preferably a linear or branched C 1-3 perfluoroalkylene group, more preferably a linear C 1-3 perfluoroalkylene group, specifically -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0161] In the above formula, p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0162] In the above formula, q is independently 0 or 1 at each occurrence. In one embodiment, q is 0. In another embodiment, q is 1.

[0163] In the above R F1 and R F2 wherein R F is, at each occurrence, independently a divalent fluoropolyether group.

[0164] R F can be the above-mentioned fluoro(poly)ether group.

[0165] In the above formula, X A each independently represents a single bond or a divalent to decavalent organic group. The X A is understood as a linker connecting R D and R F1 or a group having R F2 . Therefore, the X A can be any organic group as long as the compounds represented by formulas (B1) and (B2) can exist stably.

[0166] α in the above formula is an integer from 1 to 9, β is an integer from 1 to 9, and γ is an integer from 1 to 9. These α, β, and γ are determined according to the valence of X A . In formula (B1), the sum of α and β is the value of the valence of X A . For example, X AWhen it is a decavalent organic group, the sum of α and β is 10. For example, α can be 9 and β can be 1, α can be 5 and β can be 5, or α can be 1 and β can be 9. Also, X A When it is a divalent organic group, α and β are 1. In formula (B2), γ is a value obtained by subtracting 1 from the valence value of X A .

[0167] The above X A is preferably an organic group with a valence of 2 to 7, more preferably 2 to 4, and even more preferably 2. α, β, and γ can be integers from 1 to 6, integers from 1 to 3, or 1, etc., depending on X A .

[0168] Examples of the above X A are not particularly limited. For example, the following formula: -(R 31 ) p’ -(X a ) q’ -R 32 - [In the formula: R 31 represents a single bond, -(CH2) s’ -, or an o-, m-, or p-phenylene group, preferably -(CH2) s’ -, R 32 represents a single bond, -(CH2) t’ -, or an o-, m-, or p-phenylene group, preferably -(CH2) t’ -, s’ is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and even more preferably 1 or 2, t’ is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3, X a represents -(X b ) r’ -, X b is, in each occurrence, independently, -O-, -S-, an o-, m-, or p-phenylene group, a substituted or unsubstituted C 3-10Cycloalkylene, a substituted or unsubstituted o-, m- or p-phenylene group, -C(O)O-, -CONR 34 -, -O-CONR 34 -, -NR 34 -, -Si(R 33 )2-, -(Si(R 33 )2O) m’ -Si(R 33 )2-, and -(CH2) n’ - represents a group selected from the group consisting of, The above substituents have the same meaning as the substituents of the above hydrocarbon groups, R 33 In each occurrence, each is independently a phenyl group, C 1-6 alkyl group or C 1-6 alkoxy group, preferably C 1-6 alkyl group, more preferably a methyl group, R 34 In each occurrence, each is independently a hydrogen atom, a phenyl group or C 1-6 alkyl group (preferably a methyl group), m' is, in each occurrence, independently an integer from 1 to 100, preferably an integer from 1 to 20, n' is, in each occurrence, independently an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, r' is an integer from 1 to 10, preferably an integer from 1 to 5, more preferably an integer from 1 to 3, p' is 0 or 1, q' is 0 or 1, Here, at least one of p' and q' is 1, and the order of existence of each repeating unit enclosed in parentheses with p' or q' is arbitrary.] Examples thereof include a divalent group represented by

[0169] R D In each occurrence, each is independently a group containing a carbon-carbon double bond.

[0170] The above R DThe group containing a carbon-carbon double bond in the formula is -Y-A (wherein Y represents a single bond, an oxygen atom or a divalent organic group, and A is -CR 11 =CH2, and R 11 each independently represents a hydrogen atom or a C 1-3 alkyl group (preferably a methyl group).).

[0171] The above Y represents a single bond, an oxygen atom or a divalent organic group. Y is preferably a single bond, an oxygen atom, -CR 24 2- or -CO-, more preferably -CO-.

[0172] The above R 24 each independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group. In a preferred embodiment, R 24 is a hydrogen atom.

[0173] In a preferred embodiment, R D is the following formula (D1), (D2) or (D3):

Chemical formula

[0174] In the above formula, R a1 is, in each occurrence, independently of each other, -Z 1 -Y-A.

[0175] The above Z 1 is, in each occurrence, independently of each other, an oxygen atom or a divalent organic group. Incidentally, the structure described as Z 1 below is bonded to the right side (SiR 21 p1 R 22 q1 R 23 r1 ).

[0176] In a preferred embodiment, Z 1 is a divalent organic group.

[0177] The above Z 1 is preferably a C 1-6 alkylene group, -(CH2) z1 -O-(CH2) z2 -(wherein, z1 is an integer from 0 to 6, for example, an integer from 1 to 6, and z2 is an integer from 0 to 6, for example, an integer from 1 to 6), -(CH2) z3 -phenylene-(CH2) z4 -(wherein, z3 is an integer from 0 to 6, for example, an integer from 1 to 6, and z4 is an integer from 0 to 6, for example, an integer from 1 to 6) or -(CH2) z5 -C 3-10 cycloalkylene-(CH2) z6 -(wherein, z5 is an integer from 0 to 6, for example, an integer from 1 to 6, and z6 is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6The alkylene group may be linear or branched, but is preferably linear. These groups are, for example, a fluorine atom, C 1-6 alkyl group, C 2-6 alkenyl group, and C 2-6 alkynyl group, and may be substituted with one or more substituents selected therefrom, but is preferably unsubstituted.

[0178] In a preferred embodiment, Z 1 is a C 1-6 alkylene group or -(CH2) z3 -phenylene-(CH2) z4 -, preferably -phenylene-(CH2) z4 -. When Z 1 is such a group, the light resistance, particularly the ultraviolet resistance, can be higher.

[0179] In another preferred embodiment, the above Z 1 is a C 1-3 alkylene group. In one embodiment, Z 1 can be -CH2CH2CH2-. In another embodiment, Z 1 can be -CH2CH2-.

[0180] In the above formula, R b1 is, in each occurrence, independently a hydrogen atom, a hydroxyl group or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0181] In the above R b1 the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, still more preferably a methyl group.

[0182] The above k1 is, in each occurrence, independently an integer of 1 to 3, and l1 is, in each occurrence, independently an integer of 0 to 2. Incidentally, the sum of k1 and l1 is 3.

[0183] In a preferred embodiment, in formula (D2), k1 is 2 or 3, preferably 3.

[0184] R d1 is, in each occurrence, independently of one another, -Z 2 -CR 31 p2 R 32 q2 R 33 r2 .

[0185] Z 2 is, in each occurrence, independently of one another, a single bond, an oxygen atom or a divalent organic group. It should be noted that the structure described below for Z 2 is bonded on the right side to (CR 31 p2 R 32 q2 R 33 r2 ).

[0186] In a preferred embodiment, Z 2 is a divalent organic group.

[0187] Said Z 2 is preferably a C 1-6 alkylene group, -(CH2) z5 -O-(CH2) z6 -(wherein, z5 is an integer from 0 to 6, for example, an integer from 1 to 6, and z6 is an integer from 0 to 6, for example, an integer from 1 to 6), -(CH2) z7 -phenylene-(CH2) z8 -(wherein, z7 is an integer from 0 to 6, for example, an integer from 1 to 6, and z8 is an integer from 0 to 6, for example, an integer from 1 to 6) or -(CH2) z9 -C 3-10 cycloalkylene-(CH2) z10 -(wherein, z9 is an integer from 0 to 6, for example, an integer from 1 to 6, and z10 is an integer from 0 to 6, for example, an integer from 1 to 6). Such a C 1-6 alkylene group may be linear or branched, but is preferably linear. These groups are, for example, a fluorine atom, a C 1-6 alkyl group, a C2-6 An alkenyl group, and C 2-6 It may be substituted with one or more substituents selected from an alkynyl group, but is preferably unsubstituted.

[0188] In a preferred embodiment, Z 2 is a C 1-6 alkylene group or -(CH2) z7 -phenylene-(CH2) z8 -, preferably -phenylene-(CH2) z8 -. When Z 2 is such a group, the light resistance, particularly the ultraviolet resistance, can be higher.

[0189] In another preferred embodiment, the above Z 2 is a C 1-3 alkylene group. In one embodiment, Z 2 can be -CH2CH2CH2-. In another embodiment, Z 2 can be -CH2CH2-.

[0190] R 31 is, in each occurrence, independently of one another, -Z 2’ -CR 32’ q2’ R 33’ r2’ is.

[0191] Z 2’ is, in each occurrence, independently of one another, a single bond, an oxygen atom or a divalent organic group. Incidentally, the structure described as Z 2’ below is bonded to the right side at (CR 32’ q2’ R 33’ r2’ ).

[0192] The above Z 2’ is preferably a C 1-6 alkylene group, -(CH2) z5’ -O-(CH2) z6’ -(wherein, z5’ is an integer from 0 to 6, for example, an integer from 1 to 6, and z6’ is an integer from 0 to 6, for example, an integer from 1 to 6), -(CH2)z7’ -phenylene-(CH2) z8’ -(wherein, z7’ is an integer from 0 to 6, for example, an integer from 1 to 6, and z8’ is an integer from 0 to 6, for example, an integer from 1 to 6) or -(CH2) z9’ -C 3-10 cycloalkylene-(CH2) z10’ -(wherein, z9’ is an integer from 0 to 6, for example, an integer from 1 to 6, and z10’ is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 alkylene group may be linear or branched, but is preferably linear. These groups are, for example, a fluorine atom, C 1-6 alkyl group, C 2-6 alkenyl group, and C 2-6 alkynyl group, and may be substituted by one or more substituents selected therefrom, but is preferably unsubstituted.

[0193] In a preferred embodiment, Z 2’ is C 1-6 alkylene group or -(CH2) z7’ -phenylene-(CH2) z8’ -, preferably -phenylene-(CH2) z8’ -. When Z 2’ is such a group, the light resistance, especially the ultraviolet resistance, can be higher.

[0194] In another preferred embodiment, the above Z 2’ is C 1-3 alkylene group. In one embodiment, Z 2’ can be -CH2CH2CH2-. In another embodiment, Z 2’ can be -CH2CH2-.

[0195] The above R 32’ is, in each occurrence, independently, -Z 3 -Y-A.

[0196] The above Z 3 is, in each occurrence, independently, a single bond, an oxygen atom or a divalent organic group. Incidentally, hereinafter Z 3The structure described as such has its right side coupled to Y.

[0197] In one embodiment, Z 3 is an oxygen atom.

[0198] In one embodiment, Z 3 is a divalent organic group.

[0199] The above Z 3 is preferably a C 1-6 alkylene group, -(CH2) z5” -O-(CH2) z6” -(wherein, z5” is an integer from 0 to 6, for example, an integer from 1 to 6, and z6” is an integer from 0 to 6, for example, an integer from 1 to 6), -(CH2) z7” -phenylene-(CH2) z8” -(wherein, z7” is an integer from 0 to 6, for example, an integer from 1 to 6, and z8” is an integer from 0 to 6, for example, an integer from 1 to 6) or -(CH2) z9” -C 3-10 cycloalkylene-(CH2) z10” -(wherein, z9” is an integer from 0 to 6, for example, an integer from 1 to 6, and z10” is an integer from 0 to 6, for example, an integer from 1 to 6). Such C 1-6 alkylene group may be linear or branched, but is preferably linear. These groups may be substituted by one or more substituents selected from, for example, a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group, but is preferably unsubstituted.

[0200] In a preferred embodiment, Z 3 is a C 1-6 alkylene group or -(CH2) z7” -phenylene-(CH2) z8” -, preferably -phenylene-(CH2) z8” -. When Z 3 is such a group, the light resistance, particularly the ultraviolet resistance, can be higher.

[0201] In another preferred embodiment, the above Z 3 is a C 1-3 alkylene group. In one embodiment, Z 3 can be -CH2CH2CH2-. In another embodiment, Z 3 can be -CH2CH2-.

[0202] The above R 33’ is, in each occurrence, independently of one another, a hydrogen atom, a hydroxyl group or a monovalent organic group. Such monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0203] In the above R 33’ , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, still more preferably a methyl group.

[0204] In another embodiment, R 33’ is such that the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.

[0205] The above q2’ is, in each occurrence, independently of one another, an integer from 0 to 3, and the above r2’ is, in each occurrence, independently of one another, an integer from 0 to 3. Incidentally, the sum of q2’ and r2’ is 3 in the (CR 32’ q2’ R 33’ r2’ ) unit.

[0206] q2’ is, independently for each (CR 32’ q2’ R 33’ r2’ ) unit, preferably an integer from 1 to 3, more preferably 2 to 3, still more preferably 3.

[0207] R 32 is, in each occurrence, independently of one another, -Z 3 -Y-A. Such -Z 3 -Y-A is the above R32’ has the same meaning as the description in

[0208] The above R 33 is, in each occurrence, independently, a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such a monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0209] The above R 33 in, the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, still more preferably a methyl group.

[0210] In another embodiment, R 33 is, the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.

[0211] The above p2 is, in each occurrence, independently, an integer from 0 to 3, q2 is, in each occurrence, independently, an integer from 0 to 3, and r2 is, in each occurrence, independently, an integer from 0 to 3. Note that the sum of p2, q2, and r2 is 3 in the (CR 31 p2 R 32 q2 R 33 r2 ) unit.

[0212] In one embodiment, p2 is 0.

[0213] In one embodiment, p2 is, for each (CR 31 p2 R 32 q2 R 33 r2 ) unit, independently, an integer from 1 to 3, an integer from 2 to 3, or 3. In a preferred embodiment, p2' is 3.

[0214] In one embodiment, q2 is, for each (CR 31 p2 R32 q2 R 33 r2 ) is an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably 3, independently for each unit.

[0215] In one embodiment, p2 is 0, and q2 is (CR 31 p2 R 32 q2 R 33 r2 ) is an integer of 1 to 3, preferably an integer of 2 to 3, and even more preferably 3, independently for each unit.

[0216] The above R e1 is, independently for each occurrence, -Z 3 -Y-A. Such -Z 3 -Y-A is as defined in the above R 32’ .

[0217] The above R f1 is, independently for each occurrence, a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such monovalent organic group is a monovalent organic group excluding the above hydrolyzable group.

[0218] In the above R f1 , the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group, and even more preferably a methyl group.

[0219] In another embodiment, R f1 is, the monovalent organic group is preferably a C 1-20 alkyl group, more preferably a C 1-6 alkyl group.

[0220] The above k2 is, independently for each occurrence, an integer of 0 to 3, l2 is, independently for each occurrence, an integer of 0 to 3, and m2 is, independently for each occurrence, an integer of 0 to 3. Incidentally, the sum of k2, l2, and m2 is (CR d1k2 R e1 l2 R f1 m2 ) In the unit, it is 3.

[0221] In a preferred embodiment, in formula (D3), k2 is 0, l2 is 2 or 3, preferably 3, and n2 is 2 or 3, preferably 3.

[0222] In one embodiment, R D is a group represented by formula (D1).

[0223] In one embodiment, R D is a group represented by formula (D2).

[0224] In one embodiment, R D is a group represented by formula (D3).

[0225] As the above compound (B), for example, the following are commercially available. Optool (registered trademark) DAC-HP (Daikin Industries, Ltd.) Fluorinert (registered trademark) MD700 (Solvay) Fluorinert (registered trademark) AD1700 (Solvay) Fomblin (registered trademark) MT70 (Solvay) SHIN-ETSU SUBELYNK KY-1203 (Shin-Etsu Chemical Co., Ltd.) SHIN-ETSU SUBELYNK KY-1211 (Shin-Etsu Chemical Co., Ltd.) SHIN-ETSU SUBELYNK KY-1207 (Shin-Etsu Chemical Co., Ltd.)

[0226] As the above component (B), the above compound (B) may be used alone or as a mixture of two or more.

[0227] The content of component (B) relative to the total mass of the above-mentioned polymerizable composition is preferably 0.1% by mass to 10% by mass, more preferably 0.2% by mass to 8% by mass, and still more preferably 0.5% by mass to 5% by mass. By setting the content of component (B) to 0.1% by mass or more, the blending amount of component (B) on the surface of the polymer layer becomes sufficient, and excellent water and oil repellency, surface slipperiness, etc. can be obtained. By improving the surface slipperiness, the scratch resistance is also improved. Further, by setting the content of component (B) to 10% by mass or less, the compatibility with other components in the above-mentioned polymerizable composition can be maintained at a high level. By increasing the compatibility, the separation of each component can be suppressed. As a result, the concentration of component (B) on the surface of the polymer layer (the surface opposite to the support) can be made uniform, and excellent antifouling properties and scratch resistance can be obtained. Further, by setting the content of component (B) to 10% by mass or less, it is possible to suppress the distribution of component (B) also on the support side of the polymer layer. As a result, a decrease in the adhesion between the polymer layer and the substrate can be suppressed, and further, bleed-out in a high-temperature / high-humidity environment can be suppressed, and high reliability (optical properties) can be obtained.

[0228] (Component (C)) The compound of the above-mentioned component (C) is a compound having an alkylene oxide group and a (meth)acryloyl group and having two or more polymerizable groups (hereinafter also referred to as "compound (C)").

[0229] The above-mentioned compound (C) can be a so-called active energy ray-curable monomer. Since compound (C) has an alkylene oxide group, it can impart appropriate flexibility to the cured product, and since it has two or more polymerizable groups, it can impart appropriate hardness to the cured product. As a result, a polymer layer excellent in scratch resistance can be formed.

[0230] The above-mentioned alkylene oxide group is -C s H 2sIt is a group represented by O-. In the formula, s is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, still more preferably 2 or 3, and even more preferably 2. When a plurality of alkylene oxide groups are included in one compound, the alkylene oxide groups may be the same or different.

[0231] The above (meth)acryloyl group includes an acryloyl group and a methacryloyl group, and is a group represented by CH2=CHR-CO-. In the formula, R is a hydrogen atom or a methyl group.

[0232] In a preferred embodiment, the above compound (C) may have an alkylene oxide equivalent of less than 100 and a (meth)acrylic equivalent of less than 200.

[0233] The above alkylene oxide equivalent is the mass of the compound per mole of the alkylene oxide group, and is obtained by dividing the molecular weight of the compound by the number of alkylene oxide groups in the compound molecule.

[0234] The above acrylic equivalent is the mass of the compound per mole of the (meth)acryloyl group, and is obtained by dividing the molecular weight of the compound by the number of (meth)acryloyl groups in the compound molecule.

[0235] In the above embodiment, the alkylene oxide equivalent of the above compound (C) is less than 100, and may preferably be 60 to 98, more preferably 70 to 97, and still more preferably 75 to 96. By having the alkylene oxide equivalent of compound (C) within the above range, appropriate flexibility can be imparted to the cured product.

[0236] In the above embodiment, the (meth)acrylic equivalent of the above compound (C) is less than 200, and may preferably be 100 to 195, more preferably 125 to 190, and still more preferably 128 to 186. By having the (meth)acrylic equivalent of compound (C) within the above range, appropriate hardness can be imparted to the cured product.

[0237] In a preferred embodiment, compound (C) has two or more identical polymerizable groups.

[0238] The above polymerizable group is a group that can participate in a polymerization reaction by an active radical generated from a polymerization initiator or the like. Examples of the polymerizable group include a group having a carbon-carbon double bond, such as a (meth)acryloyl group, a vinyl group, a vinyloxy group, an isopropenyl group, an oxiranyl group, an oxetanyl group, and the like. In a preferred embodiment, the polymerizable group can be a (meth)acryloyl group.

[0239] The above compound (C) has the above polymerizable group. The polymerizable group may be one kind or two or more kinds. Compound (C) preferably has at least two identical polymerizable groups in the molecule. In one embodiment, compound (C) has 2 to 10, preferably 2 to 6 identical polymerizable groups in the molecule.

[0240] The molecular weight of the above compound (C) is not particularly limited, but may preferably be 200 to 2,500, more preferably 250 to 1,500.

[0241] In a preferred embodiment, the above compound (C) can be a compound represented by the following formula. CH2=CHR 11 -CO-O(C s H 2s O) t -CO-CHR 11 =CH2 CR 12 x R 13 4-x O{-C a H 2a -CR 12 y R 13 3-y}2 [In the formula, R 11 each independently represents a hydrogen atom or a C 1-3 alkyl group, R 12 each independently represents -(Cs H 2s O) t -CO-CHR 11 =CH2, and R 13 is, independently of one another, a hydrogen atom or -C b H 2b -R 14 and R 14 is, independently of one another, a hydrogen atom or a hydroxyl group, s is, independently for each (C s H 2s O) unit, an integer from 1 to 6, t is, independently of one another, an integer from 1 to 10, a is an integer from 1 to 6, b is an integer from 1 to 6, x is an integer from 2 to 4, y is an integer from 1 to 3, The alkylene oxide equivalent is less than 100, (meth)acrylic equivalent is less than 200, It has two or more identical polymerizable groups.]

[0242] In a preferred embodiment, in the above formula: R 11 is, independently of one another, a hydrogen atom or a methyl group, R 12 is, independently of one another, -(C s H 2s O) t -CO-CHR 11 =CH2, and R 13 is, independently of one another, a hydrogen atom or -(C b H 2b )-R 14 and R 14 is, independently of one another, a hydrogen atom or a hydroxyl group, s is, independently for each (C s H 2s O) unit, an integer from 1 to 3, more preferably an integer from 1 to 2, t is, independently of each other, an integer from 1 to 6, a is an integer from 1 to 3, more preferably an integer from 1 to 2, b is an integer from 1 to 6, more preferably an integer from 1 to 2, x is an integer from 3 to 4, y is an integer from 2 to 3.

[0243] In a more preferred embodiment, the compound (C) has the following formula: CH2=CHR 11 -CO-O(C s H 2s O) t -CO-CHR 11 =CH2 [wherein: R 11 is a hydrogen atom or a methyl group, s is an integer from 1 to 4, t is an integer from 1 to 10. ] It may be a compound represented by

[0244] In the above embodiment, s is preferably an integer from 1 to 3, more preferably 2 or 3, still more preferably 2.

[0245] In the above embodiment, t is preferably an integer from 1 to 10, more preferably an integer from 2 to 8, still more preferably an integer from 3 to 6.

[0246] The compound (C) is not particularly limited, and examples thereof include triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, hexaethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaethylene glycol dimethacrylate, tetrapropylene glycol diacrylate, tetrapropylene glycol dimethacrylate, ethylene oxide 12 mol modified dipentaerythritol hexaacrylate, and the like.

[0247] In a more preferred embodiment, the above compound (C) has the following formula: CH2=CHR 11 -CO-O(CH2CH2O) t -CO-CHR 11 =CH2 [wherein: R 11 is a hydrogen atom or a methyl group, and t is an integer from 1 to 10, preferably an integer from 3 to 6.] It may be a compound represented by

[0248] As the above compound (C), preferably, triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, hexaethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and pentaethylene glycol dimethacrylate can be mentioned.

[0249] The above compound (C) can be obtained, for example, as Brenmer (registered trademark) ADE-200 (NOF Corporation), Brenmer (registered trademark) ADE-300 (NOF Corporation), Brenmer (registered trademark) ADE-400A (NOF Corporation), Brenmer (registered trademark) PDE-150 (NOF Corporation), Brenmer (registered trademark) PDE-200 (NOF Corporation), A-200 (Shin-Nakamura Chemical Co., Ltd.), Funcril (registered trademark) FA-220M (Hitachi Chemical Co., Ltd.), Light Acrylate (registered trademark) 3EG-A (Kyoeisha Chemical Co., Ltd.), Light Acrylate 4EG-A (Kyoeisha Chemical Co., Ltd.), Light Ester (registered trademark) 3EG (Kyoeisha Chemical Co., Ltd.), Light Ester (registered trademark) 4EG (Kyoeisha Chemical Co., Ltd.), KAYARAD DPEA-12 (Nippon Kayaku Co., Ltd.), Aronix (registered trademark) M-240 (Toagosei Co., Ltd.), etc.

[0250] As the above component (C), the above compound (C) may be used alone or as a mixture of two or more.

[0251] The content of component (C) with respect to the total mass of the above-described polymerizable composition is preferably 0.1% by mass to 97% by mass, more preferably 5.0% by mass to 95% by mass, still more preferably 10% by mass to 90% by mass, and still more preferably 15% by mass to 80% by mass. By setting the content of component (C) within the above range, the scratch resistance is improved.

[0252] (Component (D)) In one aspect, the polymerizable composition of the present disclosure may further contain (D) a polymerization initiator.

[0253] Examples of the above polymerization initiator include a photopolymerization initiator, a thermal polymerization initiator, etc. The polymerization initiator is preferably a photopolymerization initiator. A photopolymerization initiator is a compound that is active with respect to active energy rays and initiates a polymerization reaction to polymerize monomers.

[0254] The above photopolymerization initiator is not particularly limited, and examples thereof include radical polymerization initiators, anion polymerization initiators, cation polymerization initiators, etc. Examples of such photopolymerization initiators include acetophenones such as p-tert-butyltrichloroacetophenone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one; ketones such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone; benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzyl ketals such as benzyldimethyl ketal, hydroxycyclohexyl phenyl ketone; acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; alkylphenones such as 1-hydroxy-cyclohexyl-phenyl-ketone, etc.

[0255] Examples of the above photopolymerization initiator include the following commercially available products. 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide: IRGACURE® TPO (IGM Resins) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide: IRGACURE® 819 (IGM Resins) 1-Hydroxy-cyclohexyl-phenyl-ketone: IRGACURE® 184 (IGM Resins)

[0256] As the above component (D), the above polymerization initiator may be used alone or as a mixture of two or more kinds.

[0257] When the polymerizable composition of the present disclosure contains the component (D), the content of the component (D) relative to the total mass of the polymerizable composition is 0.1% by mass to 10% by mass, preferably 0.5% by mass to 5.0% by mass.

[0258] (Component (E)) In one aspect, the polymerizable composition of the present disclosure may further contain a compound (hereinafter also referred to as "compound (E)") that does not have an alkylene oxide group, has a (meth)acryloyl group, and has two or more carbon-carbon double bonds.

[0259] In a preferred aspect, the above component (E) is a compound having a molecular weight of 140 to 350, not having an alkylene oxide group, having a (meth)acryloyl group, having a (meth)acrylic equivalent of 137 or less, and having two or more carbon-carbon double bonds.

[0260] The above compound (E) can be a so-called active energy ray curable monomer. The compound (E) can improve the adhesion between the polymer layer and the support, and by having two or more carbon-carbon double bonds, can impart appropriate hardness to the cured product, and as a result, can form a polymer layer excellent in scratch resistance.

[0261] The above compound (E) does not have an alkylene oxide group. By not having an alkylene oxide group, an appropriate hardness can be imparted to the cured product.

[0262] The (meth)acryloyl group in the above compound (E) has the same meaning as the (meth)acryloyl group described for the above compound (C). The (meth)acryloyl group in the above compound (C) and the (meth)acryloyl group in the above compound (C) may be the same or different.

[0263] In the above compound (E), the (meth)acrylic equivalent is preferably 137 or less, more preferably 50 to 120, still more preferably 70 to 105, and even more preferably 76 to 101. By having the (meth)acrylic equivalent within the above range, an appropriate hardness can be imparted to the cured product.

[0264] The above compound (E) has two or more carbon-carbon double bonds, preferably 2 to 10, more preferably 2 to 6, and still more preferably 2 to 3. The carbon-carbon double bond may be included as the above polymerizable group. Such polymerizable groups may be one type or two or more types.

[0265] The molecular weight of the above compound (E) is preferably 140 to 350, more preferably 145 to 330, still more preferably 150 to 300, and even more preferably 153 to 299.

[0266] In a preferred embodiment, the above compound (E) may be a compound represented by the following formula. CH2=CHR 11 -CO-O(C n H 2n O) m -CO-CHR 11 =CH2 CR 12 x R 13 4-x O{-C a H 2a -CR12 y R 13 3-y}2 CH2=CHR 11 -CO-NH-(C c H 2c )-NH-CO-CHR 11 =CH2 R 15 -NH-(C d H 2d )-NR 15 -(C d H 2d )-NH-R 15 (Trivalent triazine ring)R 20 z R 21 3-z [In the formula, R 11 each independently represents a hydrogen atom or a C 1-3 alkyl group, R 12 each independently represents -(C n H 2n O) m -CO-CHR 11 =CH2, R 13 each independently represents a hydrogen atom or -C b H 2b -R 14 and R 14 each independently represents a hydrogen atom or a hydroxyl group, R 15 represents a hydrogen atom or -CO-CHR 11 =CH2, R 20 represents -CO-CHR 11 =CH2, R 21 represents a hydrogen atom, m each independently represents an integer from 1 to 6, n is, for each (C n H 2n O) unit, independently an integer from 1 to 6, a represents an integer from 1 to 6, b is an integer from 1 to 6, c is an integer from 1 to 6, d is, independently of each other, an integer from 1 to 6, x is an integer from 2 to 4, y is an integer from 1 to 3, z is an integer from 2 to 3, the molecular weight is 140 or more and 350 or less, it does not have an alkylene oxide group, (meth)acrylic equivalent is 137 or less, and has two or more carbon-carbon double bonds.]

[0267] In a preferred embodiment, in the above formula: R 11 is, independently of each other, a hydrogen atom or a methyl group, R 12 is, independently of each other, -(C n H 2n O) m -CO-CHR 11 =CH2, R 13 is, independently of each other, a hydrogen atom or -(C b H 2b )-R 14 and R 14 is, independently of each other, a hydrogen atom or a hydroxyl group, R 15 is a hydrogen atom or -CO-CHR 11 =CH2, R 20 is -CO-CHR 11 =CH2, R 21 is a hydrogen atom, m is, independently of each other, an integer from 1 to 6, n is, independently of each other for each (C n H 2n O) unit, an integer from 1 to 3, more preferably an integer from 1 to 2, a is an integer from 1 to 3, more preferably an integer from 1 to 2, b is an integer from 1 to 6, more preferably an integer from 1 to 2, c is an integer from 1 to 6, more preferably an integer from 1 to 3, d is an integer from 1 to 6, more preferably an integer from 1 to 3, x is an integer from 3 to 4, y is an integer from 2 to 3, z is an integer from 2 to 3.

[0268] The compound (E) is not particularly limited. For example, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycerin diacrylate, glycerin dimethacrylate, glycerin triacrylate, glycerin trimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, N,N'-methylenebisacrylamide, N,N'-ethylenebisacrylamide, N,N'-(1,2-dihydroxyethylene) bisacrylamide, N,N',N''-triacryloyldiethylenetriamine, 1,3,5-triacryloylhexahydro-1,3,5-triazine, 1,3,5-trimethacryloylhexahydro-1,3,5-triazine and the like can be mentioned.

[0269] The above compound (E) can be obtained as Brenmer GMR-M (NOF Corporation), Brenmer GMR-R (NOF Corporation), Brenmer GAM (NOF Corporation), Brenmer GAM-R (NOF Corporation), A-TMM-3 (Shin-Nakamura Chemical Co., Ltd.), A-TMM-3L (Shin-Nakamura Chemical Co., Ltd.), A-TMM-3LM-N (Shin-Nakamura Chemical Co., Ltd.), A-TMPT (Shin-Nakamura Chemical Co., Ltd.), TMPT (Shin-Nakamura Chemical Co., Ltd.), 701A (Shin-Nakamura Chemical Co., Ltd.), 701 (Shin-Nakamura Chemical Co., Ltd.), Light Acrylate PE-3A (Kyoeisha Chemical Co., Ltd.), Light Acrylate TMP-A (Kyoeisha Chemical Co., Ltd.), Light Ester TMP (Kyoeisha Chemical Co., Ltd.), Light Ester G-201P (Kyoeisha Chemical Co., Ltd.), Light Ester G-101P (Kyoeisha Chemical Co., Ltd.), FAM-301 (Fuji Film Co., Ltd.), Aronix M-309 (Toagosei Co., Ltd.), Aronix M-305 (Toagosei Co., Ltd.), Aronix M-306 (Toagosei Co., Ltd.), Aronix M-920 (Toagosei Co., Ltd.), Aronix M-930 (Toagosei Co., Ltd.), etc.

[0270] As the above component (E), the above compound (E) may be used alone or as a mixture of two or more.

[0271] When the polymerizable composition of the present disclosure contains component (E), the content of component (E) relative to the total mass of the polymerizable composition is preferably 1.0% by mass to 97% by mass, more preferably 5.0% by mass to 50% by mass, and still more preferably 8.0% by mass to 30% by mass. By setting the content of component (E) to 1.0% by mass or more, the adhesion of the polymer layer to the substrate is improved, and by setting it to 98% by mass or less, the scratch resistance is improved.

[0272] (Component (F)) In one aspect, the polymerizable composition of the present disclosure may contain a component (F) different from components (A) to (E). Such component (F) is used to impart appropriate transparency, viscosity, refractive index, flexibility, etc. to the polymerizable composition and / or its cured product.

[0273] The compound of the above component (F) preferably has one or more carbon-carbon double bonds and may contain fluorine. The compound of component (F) is not particularly limited, and examples thereof include polyethylene glycol diacrylate, ethoxylated glycerin triacrylate, dipentaerythritol hexaacrylate, acryloylmorpholine, propoxylated pentaerythritol triacrylate, tripropylene glycol diacrylate, and the like.

[0274] As the component (F), for example, the following are commercially available. Polyethylene glycol diacrylate: A-1000 (Shin-Nakamura Chemical Co., Ltd.) Ethoxylated glycerin triacrylate: A-GLY-9E (Shin-Nakamura Chemical Co., Ltd.) Dipentaerythritol hexaacrylate: A-DPH (Shin-Nakamura Chemical Co., Ltd.) Acryloylmorpholine: ACMO (KJ Chemicals Co., Ltd.) Propoxylated pentaerythritol triacrylate: ATM-4PL (Shin-Nakamura Chemical Co., Ltd.) Tripropylene glycol diacrylate: APG-200 (Shin-Nakamura Chemical Co., Ltd.)

[0275] As the above component (F), the above compound may be used alone or as a mixture of two or more.

[0276] The content of component (F) relative to the total mass of the above polymerizable composition may preferably be 55% by mass or less, more preferably 45% by mass or less, and still more preferably 35% by mass or less.

[0277] In one aspect, the polymerizable composition of the present disclosure contains, in addition to the above components (A) to (C), one or more compounds selected from the above components (D) to (F). For example, the polymerizable composition of the present disclosure may be a composition containing the following combinations of components. (i) Components (A) to (D) (ii) Components (A) to (E) (iii) Components (A) to (F) (iv) Components (A) to (D) and (F)

[0278] In a preferred aspect, the polymerizable composition of the present disclosure may be a composition containing the above components (A) to (D).

[0279] In a preferred aspect, the polymerizable composition of the present disclosure may be a composition containing the above components (A) to (E).

[0280] In a preferred aspect, the polymerizable composition of the present disclosure contains the above components (A) to (E), and based on the total mass of the polymerizable composition, the content of the above component (A) is 1.0% by mass to 50% by mass, the content of the above component (B) is 0.1% by mass to 10% by mass, the content of the above component (C) is 1.0% by mass to 97% by mass, the content of the above component (D) is 0.1% by mass to 10% by mass, the content of the above component (E) is 1.0% by mass to 97% by mass.

[0281] (Solvent) The polymerizable composition of the present disclosure may further contain a solvent. Examples of such solvents include alcohols (having 1 to 10 carbon atoms, such as methanol, ethanol, n- or i-propanol, n-, sec-, or t-butanol, benzyl alcohol, octanol, etc.), ketones (having 3 to 8 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, dibutyl ketone, cyclohexanone, etc.), esters or ether esters (having 4 to 10 carbon atoms, such as ethyl acetate, butyl acetate, ethyl lactate, etc.), γ-butyrolactone, ethylene glycol monomethyl acetate, propylene glycol monomethyl acetate, ethers (having 4 to 10 carbon atoms, such as EG monomethyl ether (methyl cellosolve), EG monoethyl ether (ethyl cellosolve), diethylene glycol monobutyl ether (butyl cellosolve), propylene glycol monomethyl ether, etc.), aromatic hydrocarbons (having 6 to 10 carbon atoms, such as benzene, toluene, xylene, etc.), amides (having 3 to 10 carbon atoms, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), halogenated hydrocarbons (having 1 to 2 carbon atoms, such as methylene dichloride, ethylene dichloride, etc.), petroleum solvents (such as petroleum ether, petroleum naphtha, etc.).

[0282] The above solvents may be used alone or as a mixture of two or more.

[0283] (Laminate) As shown in FIG. 1, the laminate of the present disclosure includes a support 2 and a polymer layer 3 having an uneven structure on its surface in which a plurality of convex portions are provided at a pitch equal to or less than the wavelength of visible light. Such a polymer layer is a layer obtained by curing the polymerizable composition of the present disclosure.

[0284] (Support) The above support 2 is not particularly limited as long as a polymer layer of the polymerizable composition of the present disclosure can be formed on its surface, but is preferably in the form of a film.

[0285] The thickness of the above-mentioned support 2 is not particularly limited. For example, 50 to 100 μm is preferable, and 60 to 80 μm is more preferable. By setting the thickness of the support within the above range, it becomes easier to ensure transparency and processability.

[0286] As the material constituting the above-mentioned support 2, various film-shaped plastics or glasses having transparency can be used. Examples of the material of the transparent plastic film include polyester resins, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth)acrylic resins, polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins, norbornene resins, and other resins. Specifically, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), triacetyl cellulose (TAC), polyethersulfone, polycarbonate (PC), polyarylate, polyetheretherketone, cycloolefin polymer (COP), cycloolefin copolymer (COC), PMMA / PC laminated film, etc. are preferable. Note that polyethylene terephthalate and polyethylene naphthalate are more preferable because they are excellent in mechanical strength, dimensional stability, heat resistance, chemical resistance, optical properties, etc., and the smoothness of the film surface and handleability. Polycarbonate is more preferable because it is excellent in transparency, impact resistance, heat resistance, dimensional stability, and flammability. Triacetyl cellulose is more preferable because it has little optical anisotropy.

[0287] In addition to the above materials, the above-mentioned support 2 may further appropriately contain additives such as plasticizers.

[0288] The surface of the above-mentioned support 2 may be subjected to an easy adhesion treatment (for example, primer treatment). For example, as the above-mentioned support, a triacetyl cellulose film or a polyethylene terephthalate film subjected to an easy adhesion treatment can be used. Further, the surface of the above-mentioned support may be subjected to a saponification treatment. For example, as the above-mentioned support, a triacetyl cellulose film subjected to a saponification treatment can be used. Furthermore, a super-birefringent polyester film with coloring by birefringence and suppressed iridescence can be used.

[0289] (Polymer layer) The above-mentioned polymer layer 3 is a layer formed by the effect of the polymerizable composition of the present disclosure described above.

[0290] The thickness of the above-mentioned polymer layer 3 can preferably be 1 μm to 20 μm, more preferably 5 μm to 15 μm.

[0291] The above-mentioned polymer layer 3 preferably has an uneven structure in which a plurality of convex portions are provided at a pitch equal to or less than the wavelength of visible light.

[0292] The shape of the above-mentioned uneven structure is not particularly limited, and either the shape of the concave portion or the convex portion may be any of a pillar shape, a conical shape, a bell shape, a triangular prism, a polygonal prism shape such as a quadrangular prism, a frustum shape of these, etc. Further, in the uneven structure, those with high shape regularity or random ones may be used. In a preferred embodiment, the uneven structure has regularly arranged convex portions having a shape such as a conical shape.

[0293] The shape of the above-mentioned convex portion is preferably substantially cylindrical, but is not limited thereto, and other shapes such as a triangular prism, a polygonal prism shape such as a quadrangular prism, and a frustum shape of these with a tapered top may also be used.

[0294] In a preferred embodiment, the above-mentioned uneven structure is preferably a so-called moss eye structure in which a plurality of substantially cylindrical shapes are arranged side by side.

[0295] The pitch between the convex portions present on the surface of the polymer layer 3 (the distance P between the vertices of adjacent convex portions 7) is preferably 20 nm to 400 nm, more preferably 50 nm to 350 nm, and even more preferably 100 nm to 300 nm. By setting the pitch within the above range, a higher anti-reflectance ability can be obtained.

[0296] The height of the convex portions present on the surface of the polymer layer 3 is preferably 50 nm to 500 nm, more preferably 50 nm to 400 nm, and even more preferably 100 nm to 300 nm. By setting the height within the above range, a higher anti-reflection ability can be obtained.

[0297] The aspect ratio of the convex portions present on the surface of the polymer layer 3 is preferably 0.13 to 25, more preferably 0.3 to 10, and even more preferably 1.0 to 5.0. By setting the aspect ratio within the above range, the reflectance becomes lower. Here, the aspect ratio refers to the ratio (H / P) of the pitch P between adjacent convex portions and the height H of the convex portion.

[0298] (Other layers) In one aspect, as shown in FIG. 2, another antifouling layer 4 may be provided on the surface of the polymer layer 3 (the surface opposite to the support). Such an antifouling layer 4 may be formed by a step of applying and drying a composition containing an antifouling agent after performing Step 1 described below, or may be formed by a step of applying and drying a composition containing an antifouling agent after performing Step 4 described below.

[0299] The laminate of the present disclosure is suitably used as an antireflection layer. Therefore, the laminate of the present disclosure can be suitably used in optical films (such as antireflection films for displays), optical elements, decorative films (interior decoration, exterior decoration), etc. These can be used in televisions, in-vehicle displays, various optical sensors, PCs (desktop PCs, notebook PCs, etc.), mobile terminals (smartphones, tablets, e-readers, etc.), digital signage, etc. Further, it can also be suitably used in bulletin boards, showrooms, stadiums, restaurants, show windows, showcases, art exhibitions, etc. where visibility through a low-reflection transparent material is required.

[0300] (Method for manufacturing a laminate) The method for manufacturing the above laminate of the present disclosure is (1) A step of applying the polymerizable composition of the present disclosure on the surface of a support to form a polymerizable composition layer; (2) A step of pressing the above polymerizable composition layer against a mold to form a concavo-convex structure on the surface of the polymerizable composition layer; (3) A step of curing the polymerizable composition layer having the concavo-convex structure on the surface to form a polymer layer, and (4) A step of peeling the above mold from the polymer layer is included.

[0301] (Step 1) In Step 1, as shown in FIG. 3, the polymerizable composition of the present disclosure is applied on the surface of a support to form a polymerizable composition layer 5. Examples of the application method of the polymerizable composition include methods of applying by a spray method, a gravure method, a slot die method, a bar coating method, etc. From the viewpoints of making the film thickness uniform and improving productivity, a method of applying by a gravure method or a slot die method is preferable.

[0302] When the above polymerizable composition contains a solvent (volatile component), a heat treatment (drying treatment) for removing the solvent may be performed after the application of the polymerizable composition. The heating temperature is not particularly limited, but it is preferably not less than the boiling point of the solvent.

[0303] (Step 2) In Step 2, as shown in FIG. 4, the polymerizable composition layer 5 is pressed against a mold 6 to form a concavo-convex structure on the surface of the polymerizable composition layer. At this time, the polymerizable composition layer is sandwiched between the mold and the support. As a result, the concavo-convex structure on the surface of the mold is transferred to the surface of the polymerizable composition layer (the surface opposite to the support side).

[0304] (Step 3) In Step 3, the polymerizable composition layer 5 having the concavo-convex structure on the surface is cured to form a polymer layer 3. As a result, a polymer layer having a concavo-convex structure on the surface is formed.

[0305] Examples of the method for curing the polymerizable composition layer include methods such as irradiation with active energy rays and heating. From the viewpoint of high productivity, it is preferable that the polymerizable composition layer is cured by irradiation with active energy rays, and among them, it is more preferable that the curing is performed by irradiation with ultraviolet rays. The irradiation with active energy rays may be performed from the support side of the polymerizable composition or from the mold side of the polymerizable composition. Further, the number of times of irradiation with active energy rays on the polymerizable composition may be only once or may be a plurality of times. This Step 3 may be performed at the same timing as Step 2.

[0306] The active energy rays are not particularly limited, and examples thereof include electromagnetic waves in a wavelength region of 350 nm or less, that is, ultraviolet light, electron beams, X-rays, γ-rays, and the like.

[0307] (Step 4) In Step 4, as shown in FIG. 5, the mold 6 is peeled off from the polymer layer 3. As a result, the laminate of the present disclosure is obtained.

[0308] (Alternative method) As an alternative method to Steps 1 and 2 above, after applying the polymerizable composition of the present disclosure to the surface of a mold to form a polymerizable composition layer, the support may be pressed against the polymerizable composition layer on the mold in a state where the polymerizable composition layer is sandwiched between the mold and the support to form a concavo-convex structure on the surface of the polymerizable composition layer.

[0309] (Mold) The above mold has an uneven structure corresponding to the uneven structure of the polymer layer on its surface.

[0310] The shape of the above mold is not particularly limited, and examples include a flat plate shape, a roll shape, etc.

[0311] In one aspect, the shape of the mold is a roll shape with an uneven structure on its outer peripheral surface. By using such a mold, the above steps 1 to 4 can be carried out continuously and efficiently, and productivity can be improved.

[0312] The material of the above mold is not particularly limited, and examples include glass; metals such as stainless steel and nickel; polyolefin resins such as polypropylene, polymethylpentene, and cyclic olefin-based polymers (typically, norbornene-based resins, for example, "Zeonor (registered trademark)" manufactured by Zeon Corporation, "Arton (registered trademark)" manufactured by JSR Corporation); polycarbonate resins; resins such as polyethylene terephthalate, polyethylene naphthalate, and triacetyl cellulose.

[0313] The method for manufacturing the uneven structure of the above mold is not particularly limited, and examples include an anodization method, a photolithography method, a laser drawing method, an electron beam drawing method, a plasma etching method, a mechanical cutting method, etc.

[0314] It is preferable that the surface of the above mold is subjected to a release treatment. By subjecting the surface of the mold to a release treatment, the mold can be easily peeled off from the polymer layer. In addition, since the surface free energy of the mold becomes low, in the above step 2, when the support is pressed against the mold, the compound (B) can be uniformly oriented on the surface of the polymerizable composition layer in contact with the mold, and the antifouling property is improved.

[0315] Examples of the mold release agent used for the mold release treatment of the above mold include, for example, fluorine-based compounds, silicon-based compounds, phosphate ester-based compounds, etc. In particular, fluorine-based compounds are preferred, and examples include Optool (registered trademark) DSX (Daikin Industries, Ltd.).

[0316] Hereinafter, the article of the present disclosure will be described in Examples, but the present disclosure is not limited to the following Examples.

[0317] Synthesis Example 57 g of SUMIDUR N3300 (cyclic trimer of hexamethylene diisocyanate, manufactured by Sumitomo Bayer Urethane Co., Ltd., NCO group content 21.9%) was dissolved in 1000 g of Zeorola H (manufactured by Nippon Zeon Co., Ltd.), 0.1 g of dibutyltin dilaurate was added, and at room temperature, while stirring, 244 g of a solution of CF3CF2O-(CF2CF2CF2O) n -CF2CF2CH2OH (n = 11) dissolved in 300 g of Zeorola H was added dropwise, and the mixture was stirred overnight at room temperature. The solution was heated to 40 - 45 °C, 24.4 g of hydroxyethyl acrylate was added dropwise and stirred. The end point of the reaction was determined by IR when the absorption of NCO completely disappeared, and a composition A containing a fluoropolyether group-containing compound with a solid content of 20% by mass was obtained. Example As the components contained in the polymerizable composition of the present disclosure, the compounds shown in Table 1 below were prepared.

[0318]

Table 1

[0319] As a support, Fujitac TD-60 (60 μm thick, Fujifilm Corporation) (hereinafter also referred to as "TAC") was prepared.

[0320] As a mold, an intaglio plate made of Ni (Kyodo International Co., Ltd.) with conical recesses having a pitch of 250 nm and a depth of 350 nm being patterned was prepared. Such a mold was immersed in a solution in which Optool DSX (Daikin Industries, Ltd.) was diluted 200-fold with S-135 (Fluorotechnology Co., Ltd.) for 3 minutes. Next, the lifted mold was annealed at 100 °C for 1 hour. Then, the surface of the mold was rinsed with S-135 to remove unreacted Optool DSX.

[0321] ·Manufacture of laminate Predetermined components were uniformly dissolved in a light-shielding container in the formulation shown in Table 2 below to obtain a polymerizable composition. The obtained polymerizable composition was applied onto the surface of a support with a bar coater such that the thickness of the polymerizable composition became 7 μm. Next, with the polymerizable composition layer sandwiched between the mold and the support, the support was pressed against the mold, and ultraviolet rays (integrated irradiation dose: 1,200 mJ / cm 2 ) were irradiated from the support side using a UV lamp "LIGHT HANMAR6J6P3" manufactured by Heraeus to cure the polymerizable composition layer and form a polymer layer. The mold was peeled off from the polymer layer to obtain a film which is the laminate of the present disclosure.

[0322] ·Evaluation Regarding the obtained film, as shown below, the substrate adhesion, scratch resistance, fingerprint wiping property, and visual reflectance were measured. The results are shown in Table 2.

[0323] <Substrate adhesion> First, with respect to the surface of the film, using a cutter knife, vertical 11 cuts and horizontal 11 cuts were made in a grid pattern at 1 mm intervals to engrave 100 square meshes (1 mm square). Next, a polyester adhesive tape "No. 31B" manufactured by Nitto Denko Corporation was pressure-bonded to the mesh portion, and then the adhesive tape was peeled off from the surface of the mesh portion in a direction of 90° at a speed of 100 mm / s. Thereafter, the peeling state of the polymer layer on the substrate was visually observed. The criteria for determination are as follows. 〇: No peeling occurred at all meshes. ×: Peeling occurred at one or more meshes.

[0324] <Scratch resistance> Using a "rubbing tester" (manufactured by Imoto Seisakusho Co., Ltd.) as the testing machine, the film was fixed horizontally on the stage. Using the Tracie standard "Color Cloth (Navy)" (Toray Industries, Inc.) as the friction element, with a load of 1 kg / cm 2 , a stroke width of 30 mm, a speed of 80 rpm, and 30,000 reciprocations of rubbing, the surface of the film was rubbed. Then, the rubbing state of the film surface was visually observed. The judgment criteria were as follows. ○: There was no change compared to before rubbing. △: It appeared slightly whitened. ×: It appeared clearly whitened.

[0325] <Fingerprint wiping property> First, a black PET plate was attached to the surface of the film opposite to the polymer layer of the support via an optical adhesive layer. Then, fingerprints were attached to the surface of the polymer layer of the film (the surface opposite to the side where the black PET plate was attached), and after rubbing 10 times with "BEMCOT M-3II" (Asahi Kasei Corporation), it was visually observed whether the fingerprints could be wiped off. The judgment criteria were as follows. ○: The fingerprints were completely wiped off and no residue was visible. △: The fingerprints were not prominent, but when light from a fluorescent lamp was shone on it, a slight residue was visible. ×: The fingerprints could not be wiped off at all.

[0326] <Visual reflectance> First, a black PET plate was attached to the surface of the film opposite to the polymer layer of the support via an optical adhesive layer. Then, for the surface of the polymer layer of the film (the surface opposite to the side where the black PET plate was attached), the visual reflectance under a D65 light source was measured using a spectrophotometer "CM-26d" (Konica Minolta Inc.). The lower the visual reflectance, the better the anti-reflection property. Also, the visual reflectance was measured in the same way for the evaluation sites of the above-mentioned scratch resistance and fingerprint wiping property. It is preferable that there is no change in the visual reflectance after scratching and after wiping the fingerprints.

[0327]

Table 2

[0328] From the above results, it was confirmed that Examples 1 to 11 in which the polymer layer was formed using the polymerizable composition of the present invention had excellent substrate adhesion, scratch resistance, fingerprint wiping property, and visual reflectance.

Industrial Applicability

[0329] The laminate having the polymer layer obtained from the polymerizable composition of the present disclosure can be suitably used in optical films (such as anti-reflection films for displays), optical elements, decorative films (interior decoration, exterior decoration), and the like.

Explanation of Reference Numerals

[0330] 2…Support 3…Polymer layer 4…Antifouling layer 5…Polymerizable composition layer 6…Mold

Claims

1. (A)The following formula (1): 【Chemical 1】 [wherein: R １ is -(CH ２ ) ｘ -(O) ｚ -(CH ２ ) ｙ - and x is an integer from 1 to 2, y is an integer from 1 to 2, z is 0 or 1, provided that the sum of x, y and z is 3 or 4, R ２ is a C １－４ alkyl group.] a compound represented by, (B)a compound having a fluoropolyether group and having one or more carbon-carbon double bonds, and (C)a compound having an alkylene oxide group and a (meth)acryloyl group and having two or more polymerizable groups, comprising, with respect to 100% by mass in total of the polymerizable composition, (A) 1.0% by mass to 50% by mass, (B) 0.1% by mass to 10% by mass, and (C) 0.1% by mass to 97% by mass, a polymerizable composition.

2. R １ is -(CH ２ ) ｘ -O-(CH ２ ) ｙ - and x is 1 or 2, y is 1 or 2, provided that the sum of x and y is 3 or 4, the polymerizable composition according to Claim 1.

3. The compound of component (B) is any one of general formulas (A1), (A2) and (A3): 【Chemical 2】 [wherein, Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, R １ is a fluoro(poly)ether group, R ２ is represented by the following formula: -(Q) ｈ -(CFZ) ｉ -(CH ２ ) ｊ - (In the formula, Q represents an oxygen atom, a phenylene, a carbazolylene, -NR ａ - (wherein R ａ represents a hydrogen atom or an organic group) or a divalent polar group, Z represents a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, h, i and j are each independently an integer of 0 or more and 50 or less, and the sum of h, i and j is at least 1, and the order of presence of each repeating unit enclosed in parentheses is arbitrary in the formula.) is a group represented by, R ３ represents a divalent organic group, R ４ In each occurrence, independently of one another, R ４ａ or R ４ｂ is represented, provided that at least one R ４ is R ４ａ and R ４ａ represents, in each occurrence independently, a divalent organic group having a curable site, R ４ｂ represents, in each occurrence independently, a divalent organic group having no curable site, n1 is an integer from 1 to 50, R ５ represents -O-, -S-, -NH- or a single bond, R ６ is Rf−R １ −R ２ (wherein Rf, R １ , and R ２ are as defined above), represents a monovalent organic group or a hydrogen atom, R ７ represents an optionally substituted (n2 + n3)-valent organic group having a ring structure, a hetero atom and / or a functional group, R ８ represents a divalent organic group, X １ represents a hydrogen atom, a chlorine atom, a fluorine atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by fluorine, n2 is an integer from 1 to 3, n3 is an integer from 1 to 3.] the polymerizable composition according to Claim 1 or 2, which is a compound represented by.

4. The compound of component (B) is general formula (1) or (2): 【Chemical 3】 [wherein: R Ｆ１ is, in each occurrence independently, Rf １ -R Ｆ -O ｑ -; R Ｆ２ is -Rf ２ ｐ -R Ｆ -O ｑ - and; Rf １ is, in each occurrence, independently, a C １－１６ alkyl group which may be substituted by one or more fluorine atoms; Rf ２ is an alkylene group which may be substituted by one or more fluorine atoms; １－６ ​ R Ｆ is, in each occurrence, independently a divalent fluoropolyether group; p is 0 or 1; q is, in each occurrence, independently 0 or 1; X Ａ is, independently of one another, a single bond or a divalent to decavalent organic group; R Ｄ is, in each occurrence, independently a group containing a carbon-carbon double bond; α is an integer from 1 to 9; β is an integer from 1 to 9; γ is, independently, an integer from 1 to 9.] the polymerizable composition according to Claim 1 or 2, which is a compound represented by.

5. The compound of component (C) is the following formula: CH ２ =CHR １１ -CO-O(C ｓ H ２ｓ O) ｔ -CO-CHR １１ =CH ２ [wherein: R １１ is a hydrogen atom or a methyl group, s is an integer from 1 to 4, t is an integer from 1 to 10.] the polymerizable composition according to any one of Claims 1 to 4, which is a compound represented by.

6. The polymerizable composition according to Claim 5, wherein s is 2.

7. The compound of component (C) is a compound selected from the group consisting of triethylene glycol diacrylate, tetraethylene glycol diacrylate, pentaethylene glycol diacrylate, hexaethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and pentaethylene glycol dimethacrylate, the polymerizable composition according to any one of Claims 1 to 6.

8. Furthermore, a polymerizable composition according to any one of claims 1 to 7, comprising (D) a polymerization initiator.

9. Furthermore, a polymerizable composition according to any one of claims 1 to 8, comprising (E) a compound having no alkylene oxide group, having a (meth)acryloyl group, and having two or more carbon-carbon double bonds.

10. The compound of component (E) is selected from the group consisting of pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, glycerin diacrylate, glycerin dimethacrylate, glycerin triacrylate, glycerin trimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, N,N'-methylenebisacrylamide, N,N'-ethylenebisacrylamide, N,N'-(1,2-dihydroxyethylene)bisacrylamide, N,N',N''-triacryloyldiethylenetriamine, 1,3,5-triacryloylhexahydro-1,3,5-triazine, and 1,3,5-trimethacryloylhexahydro-1,3,5-triazine. A polymerizable composition according to claim 9.

11. A support, A polymer layer having, on its surface, a concavo-convex structure in which a plurality of convex portions are provided at a pitch equal to or less than the wavelength of visible light, A laminate comprising: The polymer layer is a cured product of a polymerizable composition according to any one of claims 1 to 10. A laminate.

12. An antireflection film comprising the laminate according to claim 11.

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