WO2022259893A1 - Composition de résine durcissable, film de revêtement dur et procédé de production de film de revêtement dur - Google Patents

Composition de résine durcissable, film de revêtement dur et procédé de production de film de revêtement dur Download PDF

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Publication number
WO2022259893A1
WO2022259893A1 PCT/JP2022/021816 JP2022021816W WO2022259893A1 WO 2022259893 A1 WO2022259893 A1 WO 2022259893A1 JP 2022021816 W JP2022021816 W JP 2022021816W WO 2022259893 A1 WO2022259893 A1 WO 2022259893A1
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Prior art keywords
group
structural unit
resin composition
curable resin
mol
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PCT/JP2022/021816
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English (en)
Japanese (ja)
Inventor
考浩 加藤
哲 北村
壮一郎 渡邉
慶介 吉政
彩子 松本
顕夫 田村
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富士フイルム株式会社
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Priority to JP2023527618A priority Critical patent/JPWO2022259893A1/ja
Priority to KR1020237041281A priority patent/KR20240001251A/ko
Publication of WO2022259893A1 publication Critical patent/WO2022259893A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings

Definitions

  • the present invention relates to a curable resin composition, a hard coat film, and a method for producing a hard coat film.
  • the curable resin composition can be used, for example, as a composition for forming a hard coat layer, and the hard coat layer can be formed by coating it on a substrate and curing it.
  • image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD), micro LEDs (Light Emitting Diodes), and micro OLEDs (Organic Light Emitting Diodes)
  • LCD liquid crystal display devices
  • PDP plasma display panels
  • ELD electroluminescence displays
  • micro LEDs Light Emitting Diodes
  • micro OLEDs Organic Light Emitting Diodes
  • Patent Document 1 describes a curable resin composition containing a polymer having a structural unit having a plurality of acryloyl groups and a structural unit containing a carboxy group, and a solvent.
  • An object of the present invention is to provide a curable resin composition capable of forming a cured layer having excellent scratch resistance, a hard coat film formed using the curable resin composition, and a method for producing the hard coat film. to provide.
  • At least one structural unit selected from the group consisting of a structural unit (a) containing a fluorine atom and a structural unit (b) containing a cationically polymerizable group, and a structural unit (z ) and a curable resin composition containing a polymer (S) having
  • D 1 represents a hydrogen atom, a methyl group, -CH 2 OR Z1 or -CH 2 COOR Z2 .
  • R Z1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R Z2 represents a hydrogen atom or a methyl group.
  • a 1 represents -O- or -NR Z3 -.
  • R Z3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • w represents an integer of 2 to 5;
  • L Z1 represents a w+1-valent linking group having at least one selected from the group consisting of an aliphatic group and an aromatic group.
  • R Z4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When multiple R Z4 are present, the multiple R Z4 may be the same or different.
  • L Z2 represents a divalent linking group having at least one selected from the group consisting of an alkylene group, an arylene group, —CO—, —O— and —NR Z5 —, or a single bond.
  • R Z5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When multiple R Z5 are present, the multiple R Z5 may be the same or different.
  • E 1 represents a group represented by the following general formula (Ea-1) or (Ea-2).
  • R E1 and R E2 each independently represent a hydrogen atom or a methyl group.
  • R E3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. * represents a binding position.
  • the content of the structural unit (a) based on the amount of substance is represented by Wa
  • the content of the structural unit (b) based on the amount of material is represented by Wb
  • the above constitution When Wz is the content of the unit (z) based on the amount of substance, Wa, Wb and Wz satisfy 0 mol% ⁇ Wa ⁇ 90 mol%, 0 mol% ⁇ Wb ⁇ 90 mol%, and 0 mol% ⁇ Wz ⁇ 100 mol% and the curable resin composition according to ⁇ 1>, wherein both Wa and Wb are not 0 mol %.
  • the content of the structural unit (a) based on the amount of substance is represented by Wa
  • the content of the structural unit (b) based on the amount of material is represented by Wb
  • Wc is the content of the unit (c) based on the substance amount
  • Wz is the content of the structural unit (z) based on the substance amount
  • Wa, Wb, Wc and Wz are each 0 mol% ⁇ Wa ⁇ 90 mol %, 0 mol% ⁇ Wb ⁇ 90 mol%, 0 mol% ⁇ Wc ⁇ 90 mol%, 0 mol% ⁇ Wz ⁇ 100 mol%, and both Wa and Wb are not 0 mol%, curing according to ⁇ 4> elastic resin composition.
  • ⁇ 6> The curable resin composition according to ⁇ 4> or ⁇ 5>, wherein the structural unit (c) has at least one selected from the group consisting of a boronic acid group, an isocyanate group, an aldehyde group, and an alkoxysilyl group.
  • the structural unit (c) has at least one selected from the group consisting of a boronic acid group, an isocyanate group, an aldehyde group, and an alkoxysilyl group.
  • ⁇ 7> The curable resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the polymer (S) has the structural unit (a), the structural unit (b), and the structural unit (z). thing.
  • ⁇ 8> The curable resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein L Z1 in general formula (Z-1) represents a w+1-valent aliphatic group.
  • L Z2 in the general formula (Z-1) represents a divalent linking group having at least one selected from the group consisting of an alkylene group, —CO—, and —O—, or a single bond
  • ⁇ 10> The curable resin composition according to any one of ⁇ 1> to ⁇ 9>, wherein the total number of carbon atoms contained in L Z1 and L Z2 in the general formula (Z-1) is 1 to 6. .
  • ⁇ 11> The curable resin composition according to any one of ⁇ 1> to ⁇ 10>, wherein the number of fluorine atoms contained in the structural unit (a) is 3 or more and 17 or less.
  • n represents an integer of 1 or more.
  • a plurality of n may be the same or different.
  • R b1 represents a hydrogen atom or a substituent.
  • R b2 represents a hydrogen atom or a substituent.
  • a plurality of R b2 may be the same or different.
  • L b1 represents an n+1-valent linking group.
  • a plurality of L b1 may be the same or different.
  • Z b1 represents a group containing a fluorine atom. Plural Z's may be the same or different.
  • * represents a binding position.
  • a curable resin composition capable of forming a cured layer having excellent scratch resistance, a hard coat film formed using the curable resin composition, and a method for producing the hard coat film. can provide.
  • the curable resin composition of the present invention contains a polymer (S).
  • the polymer (S) has at least one structural unit selected from the group consisting of a structural unit (a) containing a fluorine atom and a structural unit (b) containing a cationically polymerizable group, and is represented by general formula (Z-1). and a structural unit (z).
  • a structural unit (a) containing a fluorine atom is also referred to as a “structural unit (a)”.
  • a structural unit (b) containing a cationically polymerizable group is also referred to as a “structural unit (b)”.
  • a structural unit (z) represented by general formula (Z-1) is also referred to as a “structural unit (z)”.
  • D 1 represents a hydrogen atom, a methyl group, -CH 2 OR Z1 or -CH 2 COOR Z2 .
  • R Z1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R Z2 represents a hydrogen atom or a methyl group.
  • a 1 represents -O- or -NR Z3 -.
  • R Z3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • w represents an integer of 2 to 5;
  • L Z1 represents a w+1-valent linking group having at least one selected from the group consisting of an aliphatic group and an aromatic group.
  • R Z4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When multiple R Z4 are present, the multiple R Z4 may be the same or different.
  • L Z2 represents a divalent linking group having at least one selected from the group consisting of an alkylene group, an arylene group, —CO—, —O— and —NR Z5 —, or a single bond.
  • R Z5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When multiple R Z5 are present, the multiple R Z5 may be the same or different.
  • E 1 represents a group represented by the following general formula (Ea-1) or (Ea-2).
  • R E1 and R E2 each independently represent a hydrogen atom or a methyl group.
  • R E3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. * represents a binding position.
  • the polymer (S) has a structural unit (z) and at least one of a structural unit (a) and a structural unit (b). That is, the polymer (S) may be a polymer having the structural unit (a) and the structural unit (z), or may be a polymer having the structural unit (b) and the structural unit (z). Alternatively, it may be a polymer having a structural unit (a), a structural unit (b) and a structural unit (z).
  • the structural unit (a), the structural unit (b) and the structural unit (z) are preferably different structural units. That is, the structural unit (a) preferably does not contain a cationically polymerizable group.
  • Structural unit (a) is preferably not a structural unit represented by general formula (Z-1).
  • Structural unit (b) preferably does not contain a fluorine atom.
  • Structural unit (b) is preferably not a structural unit represented by general formula (Z-1).
  • Structural unit (z) preferably does not contain a fluorine atom.
  • the structural unit (z) preferably does not contain a cationic polymerizable group.
  • the polymer (S) has a structural unit (b) containing a cationically polymerizable group in addition to the structural unit (z) containing two or more radically polymerizable groups such as (meth)acryloyl groups, cationic curing and radical curing It is considered that high scratch resistance can be obtained due to the formation of a double network of Further, in addition to the structural unit (z) containing two or more radically polymerizable groups such as (meth)acryloyl groups, when the structural unit (a) containing a fluorine atom is present, the effect of the low surface energy of the fluorine atom maximizes It is thought that the crosslink density is increased by increasing the amount of surface radically polymerizable sites that are unevenly distributed on the surface, thereby improving the scratch resistance.
  • Wb be the content of the structural unit (b) based on the material amount
  • the structural unit (z) When the content of the substance amount standard is Wz, Wa, Wb and Wz respectively satisfy 0 mol% ⁇ Wa ⁇ 90 mol%, 0 mol% ⁇ Wb ⁇ 90 mol%, 0 mol% ⁇ Wz ⁇ 100 mol%, and Wa and It is preferable that both Wb and Wb are not 0 mol %.
  • the polymer (S) preferably has a structural unit (a), a structural unit (b) and a structural unit (z). It is more preferable to satisfy 0 mol% ⁇ Wa ⁇ 90 mol%, 0 mol% ⁇ Wb ⁇ 90 mol%, and 0 mol% ⁇ Wz ⁇ 100 mol%.
  • Wz preferably satisfies 30 mol% ⁇ Wz ⁇ 95 mol%.
  • the main chain structure of the polymer (S) is not particularly limited, it is preferably a (meth)acryl polymer or a (meth)acrylamide polymer.
  • the number of fluorine atoms contained in the structural unit (a) is preferably 3 or more and 17 or less.
  • Group containing a fluorine atom Structural unit (a) preferably contains a fluorine atom-containing group.
  • a group containing a fluorine atom (also referred to as a “fluorine-containing group”) is a group containing at least one fluorine atom, and examples thereof include a fluorine atom and an organic group having at least one fluorine atom.
  • the number of carbon atoms in the organic group is not particularly limited, it preferably has 1 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, even more preferably 4 to 10 carbon atoms, and 4 carbon atoms. ⁇ 8 is particularly preferred.
  • the organic group may have a linear structure, a branched structure, or a cyclic structure.
  • Examples of the organic group include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an alkoxy group, an aryl group, an aryloxy group, and a group formed by combining at least two of these groups. and preferably an alkyl group.
  • the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, alkoxy group, aryl group, and aryloxy group may further have a substituent other than the fluorine atom.
  • the fluorine-containing group is preferably an aliphatic hydrocarbon group having a fluorine atom.
  • the aliphatic hydrocarbon group may have an oxygen atom.
  • fluorine-containing groups include fluorine-containing alkyl groups, fluorine-containing alkyl groups in which one or more of -CH 2 - constituting the fluorine-containing alkyl group are substituted with -O-, and fluorine-containing alkenyl groups.
  • the fluorine atom-containing alkyl group includes an alkyl group in which some of the hydrogen atoms of —CH 2 — constituting the alkyl group are substituted with fluorine atoms, and a part of the carbon atoms constituting the alkyl group are fluorine atoms. (e.g., —CF 3 ), but is preferably a perfluoroalkyl group in which all hydrogen atoms of —CH 2 — constituting the alkyl group are substituted with fluorine atoms, and — (CF 2 ) fa CF 3 is more preferred.
  • fa represents an integer from 0 to 12.
  • fb represents an integer of 1-10
  • fc represents an integer of 1-10.
  • the number of carbon atoms in the aliphatic hydrocarbon group having a fluorine atom is not particularly limited, and is preferably 1-30, more preferably 3-20, and even more preferably 3-10.
  • the number of fluorine atoms contained in the aliphatic hydrocarbon group having fluorine atoms is not particularly limited, and is preferably 1-30, more preferably 5-25, and even more preferably 7-20.
  • the fluorine-containing group is preferably a fluoroalkyl group or a fluoropolyether group.
  • a fluoropolyether group is a divalent group in which a plurality of fluorocarbon groups are linked by ether bonds.
  • the fluoropolyether group is preferably a divalent group in which multiple fluoroalkylene groups are linked via ether linkages, and a divalent group in which multiple perfluoroalkylene groups are linked via ether linkages (perfluoropolyether group).
  • the fluorine-containing group is preferably a fluoroalkyl group having 1 to 20 carbon atoms, more preferably a fluoroalkyl group having 2 to 15 carbon atoms, and further preferably a fluoroalkyl group having 4 to 10 carbon atoms.
  • a fluoroalkyl group having 4 to 8 carbon atoms is particularly preferred.
  • the number of fluorine atoms contained in one fluorine-containing group is preferably 3 or more and 17 or less, more preferably 5 or more and 15 or less, and further preferably 9 or more and 13 or less. preferable.
  • the fluorine-containing group is preferably a group represented by general formula (f-1) below. That is, the structural unit (a) preferably has a group represented by general formula (f-1) below.
  • q1 represents an integer of 0 to 12
  • q2 represents an integer of 1 to 8
  • Rq1 represents a hydrogen atom or a fluorine atom.
  • * represents a binding position.
  • q1 preferably represents an integer of 1 to 7, more preferably an integer of 1 to 5, even more preferably 1 or 2.
  • q2 preferably represents an integer of 2 to 8, more preferably an integer of 4 to 8, even more preferably an integer of 4 to 6.
  • Rq 1 preferably represents a fluorine atom.
  • the structural unit (a) may contain a group represented by the following general formula (1).
  • X 1 and X 2 each independently represent an oxygen atom or a sulfur atom.
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent, and at least one of R 1 and R 2 represents a substituent.
  • R 1 and R 2 may combine to form a ring.
  • At least one of R 1 and R 2 may be combined with a portion other than the group represented by general formula (1) of the structural unit (a) to form a ring.
  • m and n each independently represent 0 or 1; However, n represents 1 when R 1 or R 2 represents a hydrogen atom. *1 and *2 represent binding positions.
  • the group represented by general formula (1) may be an acid-cleavable group.
  • An acid-cleavable group is a group that is cleaved by the action of an acid, typically a group that is cleaved by the action of an acid to produce a polar group (eg, a hydroxy group, a carboxyl group, a ketone group, etc.).
  • X 1 and X 2 each independently represent an oxygen atom or a sulfur atom, preferably an oxygen atom.
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent.
  • the type of substituent is not particularly limited, and any known substituent may be used.
  • substituents include alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, cycloalkynyl groups, aryl groups, heterocyclic groups, amino groups, alkoxy groups, aryloxy groups, heterocyclicoxy groups, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heterocyclicthio group, Phosphate amide group, hydroxy group, hydroxy group,
  • substituents can further have one or more substituents, they may have the above-described substituents as further substituents.
  • R 1 and R 2 represent a substituent
  • the substituent is preferably an organic group, and the organic group may have a linear structure, a branched structure, or a cyclic structure.
  • the above organic group is more preferably an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, an alkoxy group, or a group formed by combining at least two of these.
  • a cycloalkyl group, an aryl group or an alkoxy group is more preferred.
  • the number of carbon atoms in the organic group is not particularly limited, it is preferably 1-20, more preferably 1-10.
  • the organic group may further have a substituent. However, at least one of R 1 and R 2 represents a substituent. That is, it is not the case that both R 1 and R 2 represent hydrogen atoms.
  • R 1 and R 2 may combine to form a ring, and the ring is preferably an aliphatic hydrocarbon ring having 3 to 20 carbon atoms, more preferably an aliphatic hydrocarbon ring having 4 to 12 carbon atoms. It is more preferable to have The aliphatic hydrocarbon ring may have a substituent.
  • the above aliphatic hydrocarbon ring has —O—, —CO—, —COO—, —OCO—, —S—, —SO 2 —, —NR—, or these between the carbon-carbon bonds of the ring members. You may have the linking group which combines two or more.
  • R above represents a hydrogen atom or a substituent.
  • n 0 or 1, preferably 1;
  • *1 and *2 represent binding positions.
  • *1 and *2 include a partial structure other than the group represented by the general formula (1) of the structural unit (a) (one atom such as a hydrogen atom, a fluorine-containing group, the main chain of the polymer (S), etc. Atomic groups consisting of multiple atoms of ) bond.
  • specific embodiments of the structural unit (a) include the following embodiments. 1) A mode in which a fluorine-containing group is bonded to *2 in general formula (1) directly or via a linking group. 2) A fluorine-containing group is bonded to at least one of R 1 and R 2 in general formula (1). 3) A mode in which a fluorine-containing group is bonded directly or via a linking group to *1 in the general formula (1)
  • the linking group in 1) and 3) above may be -O-, -CO-, -COO-, -OCO-, -S-, -SO 2 -, -NR-, or a combination of two or more thereof. groups, with —O— or —S— being preferred.
  • R above represents a hydrogen atom or a substituent. Examples of the substituent when R represents a substituent include an alkyl group and an aryl group.
  • alkyl group for example, a linear alkyl group having 1 to 18 carbon atoms, a branched or cyclic alkyl group having 3 to 18 carbon atoms is preferable, a linear alkyl group having 1 to 4 carbon atoms is more preferable, methyl groups or ethyl groups are more preferred.
  • the aryl group includes, for example, an aryl group having 6 to 12 carbon atoms, such as a phenyl group, an ⁇ -methylphenyl group, and a naphthyl group, with a phenyl group being preferred.
  • Structural unit (a) may have an acetal structure, a thioacetal structure or a dithioacetal structure.
  • the acetal structure is preferably a structure represented by the following general formula (AC1) or (AC2).
  • the thioacetal structure is preferably a structure represented by the following general formula (SA1), (SA2) or (SA3).
  • the dithioacetal structure is preferably a structure represented by the following general formula (DS1) or (DS2).
  • R 1 and R 2 each independently represent a hydrogen atom or a substituent, and at least one of R 1 and R 2 represents a substituent. R 1 and R 2 may combine to form a ring. At least one of R 1 and R 2 may combine with a portion other than the structure represented by general formula (AC1), (SA1) or (DS1) of structural unit (a) to form a ring.
  • R 3 represents a substituent and k represents an integer of 0-3. When k represents 2 or 3, multiple R 3 may be the same or different.
  • * represents a binding position.
  • R 1 and R 2 each have the same meaning as in general formula (1), and specific examples and preferred ranges are also the same.
  • R 3 represents a substituent
  • specific examples and preferred ranges are R 1 and R 2 in general formula (1) It is the same as the one mentioned as a substituent in the case of representing.
  • k represents 0 or 1.
  • the structural unit (a) has the following general formula (A- It may be a structural unit represented by any one of 1) to (A-5).
  • Ra 1 represents a hydrogen atom or a methyl group.
  • A represents -O- or -NH-.
  • L1 represents a single bond or a divalent linking group.
  • Q1 represents a group containing a fluorine atom.
  • L2 represents a single bond or a divalent linking group.
  • X 1 , X 2 , m, n, R 1 and R 2 each have the same meaning as in formula (1).
  • R 3 and k each have the same meaning as in general formula (AC2).
  • A represents -O- or -NH-, preferably -O-.
  • L 1 represents a single bond or a divalent linking group.
  • L 1 represents a divalent linking group, -O-, -CO-, -COO-, -S-, -SO 2 -, -NR-, an organic linking group having 1 to 20 carbon atoms (e.g., substituted an alkylene group optionally having a group, a cycloalkylene group optionally having a substituent, an arylene group optionally having a substituent, etc.), or a linking group formed by combining two or more of these.
  • R above represents a hydrogen atom or a substituent.
  • R represents a substituent
  • examples of the substituent when R represents a substituent include an alkyl group and an aryl group.
  • the alkyl group for example, a linear alkyl group having 1 to 18 carbon atoms, a branched or cyclic alkyl group having 3 to 18 carbon atoms is preferable, a linear alkyl group having 1 to 4 carbon atoms is more preferable, methyl groups or ethyl groups are more preferred.
  • the aryl group includes, for example, an aryl group having 6 to 12 carbon atoms, such as a phenyl group, an ⁇ -methylphenyl group, and a naphthyl group, with a phenyl group being preferred.
  • L 1 is preferably a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —CO—, —COO—, —S—, or a linking group consisting of a combination of two or more of these. More preferably, it is a bond, an alkylene group having 1 to 6 carbon atoms, —O—, —CO—, —COO—, —S—, or a linking group formed by combining two or more of these.
  • Q1 represents a fluorine atom-containing group.
  • the groups containing fluorine atoms are the same as those described above.
  • L2 represents a single bond or a divalent linking group. Specific examples and preferred ranges when L 2 represents a divalent linking group are the same as in the case where L 1 represents a divalent linking group.
  • X 1 , X 2 , m, n, R 1 and R 2 in general formulas (A-1) to (A-5) above each have the same meaning as in general formula (1), and specific examples and preferred The range is also the same.
  • R 3 and k each have the same meaning as in formula (AC2), and specific examples and preferred ranges are also the same.
  • the structural unit (a) has a group represented by the following general formula (B1). is preferred.
  • n represents an integer of 1 or more.
  • a plurality of n may be the same or different.
  • R b1 represents a hydrogen atom or a substituent.
  • R b2 represents a hydrogen atom or a substituent.
  • a plurality of R b2 may be the same or different.
  • L b1 represents an n+1-valent linking group.
  • a plurality of L b1 may be the same or different.
  • Z b1 represents a group containing a fluorine atom. Plural Z's may be the same or different. * represents a binding position.
  • R b1 represents a hydrogen atom or a substituent, preferably a substituent.
  • the type of substituent represented by one embodiment of R b1 is not particularly limited, and examples thereof include known substituents.
  • substituents include monovalent aliphatic hydrocarbon groups which may have an oxygen atom, and monovalent aromatic hydrocarbon groups which may have an oxygen atom. Specific examples include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, acyloxy groups, and combinations thereof.
  • the said substituent may be further substituted by the substituent.
  • an aliphatic hydrocarbon group having 1 to 18 carbon atoms is preferable, an alkyl group having 1 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 8 carbon atoms is preferable.
  • a linear alkyl group or a branched alkyl group having 3 to 8 carbon atoms is more preferable, and a methyl group is particularly preferable.
  • R b2 represents a hydrogen atom or a substituent.
  • a plurality of R b2 may be the same or different.
  • the type of substituent represented by one aspect of R b2 is not particularly limited, and examples include known substituents, and examples include the groups exemplified as the substituent represented by one aspect of R b1 in the general formula (B1). Among them, an alkyl group having 1 to 12 carbon atoms is preferable, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group having 3 to 8 carbon atoms is more preferable, and a methyl group is further preferable. preferable.
  • R b2 preferably represents a hydrogen atom.
  • L b1 represents an n+1-valent linking group.
  • the n+1-valent linking group is an optionally substituted n+1-valent hydrocarbon group having 1 to 24 carbon atoms, wherein some of the carbon atoms constituting the hydrocarbon group are substituted with heteroatoms.
  • the number of carbon atoms contained in the n+1-valent linking group is not particularly limited, and is preferably 1-24, more preferably 1-10.
  • the n+1-valent linking group is preferably a divalent to tetravalent linking group, more preferably a divalent to trivalent linking group, and still more preferably a divalent linking group.
  • the divalent linking group for example, a divalent hydrocarbon group optionally having a substituent, a divalent heterocyclic group, -O-, -S-, -N(Q)-, -CO -, or groups in which these are combined.
  • Q represents a hydrogen atom or a substituent.
  • the divalent hydrocarbon group includes, for example, an alkylene group having 1 to 10 carbon atoms (preferably 1 to 5), an alkenylene group having 1 to 10 carbon atoms, and an alkynylene group having 1 to 10 carbon atoms.
  • divalent aliphatic hydrocarbon groups divalent aromatic hydrocarbon groups such as arylene groups
  • divalent heterocyclic groups include divalent aromatic heterocyclic groups, and specific examples thereof include pyridylene group (pyridine-diyl group), pyridazine-diyl group, imidazole-diyl group, thienylene (thiophene -diyl group), quinolylene group (quinoline-diyl group), and the like.
  • the group consisting of the above-mentioned divalent hydrocarbon group, divalent heterocyclic group, -O-, -S-, -N(Q)-, and -CO- Groups in which two or more selected from are combined include, for example, —O-divalent hydrocarbon group —, —(O-divalent hydrocarbon group) p —O— (p is 1 or more represents an integer), and -divalent hydrocarbon group -O-CO-.
  • divalent linking groups linear alkylene groups having 1 to 10 carbon atoms, branched alkylene groups having 3 to 10 carbon atoms, cyclic alkylene groups having 3 to 10 carbon atoms, and 6 carbon atoms.
  • a divalent linking group is preferably a combination of 12 arylene groups and at least two groups selected from the group consisting of -O-.
  • L b1 is particularly preferably an alkylene group.
  • Examples of the substituents that the divalent hydrocarbon group and the divalent heterocyclic group may have and the substituents represented by Q include a halogen atom, an alkyl group, an alkoxy group, an aryl group, and an aryl Examples include oxy, cyano, carboxy, alkoxycarbonyl, and hydroxy groups.
  • Halogen atoms include, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom or a chlorine atom.
  • alkyl group for example, a linear alkyl group having 1 to 18 carbon atoms, a branched or cyclic alkyl group having 3 to 18 carbon atoms is preferable, a linear alkyl group having 1 to 4 carbon atoms is more preferable, methyl groups or ethyl groups are more preferred.
  • alkoxy group for example, an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 1 to 4 carbon atoms is more preferable, and a methoxy group or an ethoxy group is even more preferable.
  • the aryl group includes, for example, an aryl group having 6 to 12 carbon atoms, such as a phenyl group, an ⁇ -methylphenyl group, and a naphthyl group, with a phenyl group being preferred.
  • the aryloxy group may be an aromatic heterocyclic oxy group such as phenoxy group, naphthoxy group, imidazoyloxy group, benzimidazolyloxy group, pyridin-4-yloxy group, pyrimidinyloxy group, quinazolinyl oxy, purinyloxy, and thiophen-3-yloxy groups.
  • Alkoxycarbonyl groups include, for example, methoxycarbonyl and ethoxycarbonyl groups.
  • Z b1 represents a group containing a fluorine atom.
  • a plurality of Z b1 may be the same or different.
  • the groups containing fluorine atoms are the same as those described above.
  • the structural unit (a) is preferably a structural unit represented by the following general formula (10).
  • r represents an integer of 1 or more.
  • R B1 represents a hydrogen atom or a substituent.
  • Y 1 represents -O- or -NR Z -.
  • R Z represents a hydrogen atom or a substituent.
  • L B1 represents an r+1-valent linking group.
  • B1 represents a group represented by the general formula (B1). However, when * in the above general formula (B1) represents the bonding position with L B1 and r is an integer of 2 or more, the plurality of B1 may be the same or different.
  • R B1 represents a hydrogen atom or a substituent.
  • the type of the substituent represented by one aspect of R B1 is not particularly limited, and examples include known substituents, and examples include the groups exemplified as the substituent represented by one aspect of R b1 in the general formula (B1). Among them, an alkyl group having 1 to 12 carbon atoms is preferable, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group having 3 to 8 carbon atoms is more preferable, and a methyl group is further preferable. preferable.
  • R B1 preferably represents a hydrogen atom or a methyl group.
  • Y 1 represents —O— or —NR Z —.
  • R Z represents a hydrogen atom or a substituent.
  • the type of the substituent represented by one aspect of R Z is not particularly limited, and includes known substituents. mentioned. Among them, an alkyl group having 1 to 12 carbon atoms is preferable, a linear alkyl group having 1 to 8 carbon atoms or a branched alkyl group having 3 to 8 carbon atoms is more preferable, and a methyl group is further preferable.
  • Y 1 preferably represents -O- or -NH-, more preferably -O-.
  • L B1 represents an r+1-valent linking group.
  • the r+1-valent linking group is an optionally substituted r+1-valent hydrocarbon group having 1 to 24 carbon atoms, in which part of the carbon atoms constituting the hydrocarbon group is substituted with a hetero atom.
  • the number of carbon atoms contained in the r+1-valent linking group is not particularly limited, and is preferably 1-24, more preferably 1-10.
  • a divalent to trivalent linking group is preferable, and a divalent linking group is more preferable.
  • the divalent linking group include the same as those exemplified as the divalent linking group represented by one embodiment of L b1 in the general formula (B1).
  • r represents an integer of 1 or more.
  • an integer of 1 to 3 is preferable, an integer of 1 to 2 is more preferable, and 1 is even more preferable.
  • Structural unit (a) may have a perfluoropolyether group.
  • a perfluoropolyether group refers to a perfluoroalkyl group having an ether bond, and may be a monovalent group or a divalent or higher group.
  • Perfluoropolyether groups may be linear, branched or cyclic. The number of carbon atoms contained in the perfluoropolyether group is preferably 1-200, more preferably 2-150, even more preferably 3-100.
  • perfluoropolyether groups examples include -(CF 2 O) pf -(CF 2 CF 2 O) qf -, -[CF(CF 3 )CF 2 O] pf -[CF(CF 3 )] qf - , -(CF 2 CF 2 CF 2 O) pf -, -(CF 2 CF 2 O) pf - and the like.
  • the above pf and qf each independently represent an integer of 0-20. However, pf+qf is an integer of 1 or more.
  • the sum of pf and qf is preferably 1-100, more preferably 1-75, even more preferably 3-50.
  • s and t below each independently represent an integer of 0 to 10; n represents an integer of 0 to 10, preferably an integer of 1 to 10, more preferably an integer of 1 to 4.
  • the structural unit (a ) is preferably more than 0 mol% and 90 mol% or less, more preferably 1 mol% or more and 50 mol% or less, based on the total structural units contained in the polymer (S), It is more preferably 2 mol% or more and 40 mol% or less, particularly preferably 3 mol% or more and 30 mol% or less, even more preferably 4 mol% or more and 20 mol% or less, and 5 mol% or more and 15 mol% or more. It is most preferably mol % or less.
  • the structural unit (b) containing a cationically polymerizable group will be described.
  • the cationically polymerizable group of the structural unit (b) is not particularly limited, and may be any known cationically polymerizable group.
  • Examples of cationic polymerizable groups include alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spiroorthoester groups, and vinyloxy groups.
  • the cationic polymerizable group is preferably an alicyclic ether group or a vinyloxy group, more preferably an epoxy group, an epoxycyclohexyl group, an oxetanyl group or a vinyloxy group, more preferably an epoxy group, an epoxycyclohexyl group or an oxetanyl group, and an epoxy group or Epoxycyclohexyl groups are most preferred.
  • each group described above may have a substituent.
  • the cationically polymerizable group is preferably a group represented by any one of the following formulas (C1) to (C3).
  • R C represents a hydrogen atom or a substituent.
  • R 1 C in formula (C3) represents a substituent
  • the substituent is not particularly limited, but is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms.
  • alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-hexyl group and the like.
  • R C preferably represents a hydrogen atom, a methyl group or an ethyl group, more preferably a methyl group or an ethyl group.
  • the structural unit (b) has the following general formula (CA- A structural unit represented by any one of 1) to (CA-3) is preferred.
  • Ra 1 represents a hydrogen atom or a methyl group.
  • A represents -O- or -NH-.
  • L3 represents a single bond or a divalent linking group.
  • R 1 C has the same meaning as in formula (C3) above.
  • A represents -O- or -NH-, preferably -O-.
  • L 3 represents a single bond or a divalent linking group.
  • L 3 represents a divalent linking group, -O-, -CO-, -COO-, -S-, -SO 2 -, -NR-, an organic linking group having 1 to 20 carbon atoms (e.g., substituted an alkylene group optionally having a group, a cycloalkylene group optionally having a substituent, an arylene group optionally having a substituent, etc.), or a linking group formed by combining two or more of these.
  • R above represents a hydrogen atom or a substituent.
  • L 3 is preferably a single bond, or an alkylene group having 1 to 10 carbon atoms, —O—, —CO—, —COO—, —S—, or a linking group formed by combining two or more of these. More preferably, it is a bond, an alkylene group having 1 to 6 carbon atoms, —O—, —CO—, —COO—, —S—, or a linking group formed by combining two or more of these.
  • R 1 C has the same meaning as in formula (C3) above, and specific examples and preferred ranges are also the same.
  • the structural unit (b) in the polymer (S) ) is preferably more than 0 mol% and 90 mol% or less, more preferably 5 mol% or more and 80 mol% or less, based on the total structural units contained in the polymer (S), It is more preferably 10 mol % or more and 70 mol % or less, particularly preferably 20 mol % or more and 60 mol % or less, and most preferably 30 mol % or more and 50 mol % or less.
  • D 1 represents a hydrogen atom, a methyl group, -CH 2 OR Z1 or -CH 2 COOR Z2 .
  • R Z1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R Z2 represents a hydrogen atom or a methyl group.
  • a 1 represents -O- or -NR Z3 -.
  • R Z3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • w represents an integer of 2 to 5;
  • L Z1 represents a w+1-valent linking group having at least one selected from the group consisting of an aliphatic group and an aromatic group.
  • R Z4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When multiple R Z4 are present, the multiple R Z4 may be the same or different.
  • L Z2 represents a divalent linking group having at least one selected from the group consisting of an alkylene group, an arylene group, —CO—, —O— and —NR Z5 —, or a single bond.
  • R Z5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When multiple R Z5 are present, the multiple R Z5 may be the same or different.
  • E 1 represents a group represented by the following general formula (Ea-1) or (Ea-2).
  • R E1 and R E2 each independently represent a hydrogen atom or a methyl group.
  • R E3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. * represents a binding position.
  • D 1 represents a hydrogen atom, a methyl group, -CH 2 OR Z1 or -CH 2 COOR Z2 .
  • R Z1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
  • D 1 preferably represents a hydrogen atom or a methyl group.
  • a 1 represents -O- or -NR Z3 -.
  • R Z3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
  • a 1 preferably represents -O- or -NH-, more preferably -O-.
  • w preferably represents an integer of 2 to 4, more preferably 2 or 3, and even more preferably 2.
  • R Z4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
  • L Z1 represents a w+1-valent linking group having at least one selected from the group consisting of an aliphatic group and an aromatic group.
  • the aromatic group is preferably an aromatic hydrocarbon group, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • L Z1 preferably represents a w+1-valent aliphatic group, more preferably a w+1-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a w+1-valent aliphatic hydrocarbon group having 1 to 5 carbon atoms.
  • the w+1 valent aliphatic hydrocarbon group is preferably linear or branched.
  • the w+1 valent aliphatic hydrocarbon group is preferably a group obtained by removing arbitrary w ⁇ 1 hydrogen atoms from an alkylene group.
  • L Z2 represents a divalent linking group having at least one selected from the group consisting of an alkylene group, an arylene group, —CO—, —O— and —NR Z5 —, or a single bond.
  • R Z5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
  • the alkylene group may be linear or branched, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and an alkylene group having 1 to 3 carbon atoms. more preferably a group.
  • the aryl group is preferably an aryl group having 6 to 10 carbon atoms.
  • L Z2 preferably represents an alkylene group, a divalent linking group having at least one selected from the group consisting of —CO—, —O—, and —NR Z5 —, or a single bond, and an alkylene group, —CO It more preferably represents a divalent linking group having at least one selected from the group consisting of - and -O-, or a single bond, and more preferably represents an alkylene group or a single bond.
  • the group consisting of L Z1 and L Z2 (-L Z1 -(L Z2 ) w -) is at least one selected from the group consisting of carbon atoms, hydrogen atoms and oxygen atoms for the reason that the scratch resistance is improved. is preferably composed of atoms, and more preferably composed of carbon atoms and hydrogen atoms.
  • the total number of carbon atoms contained in L Z1 and L Z2 is preferably 1 to 6, more preferably 1 to 5, still more preferably 1 to 4, and preferably 1 to 3.
  • the total number of oxygen atoms contained in L Z1 and L Z2 is preferably 0-4, more preferably 0-2.
  • R E3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
  • E 1 preferably represents a group represented by general formula (Ea-1).
  • E1 of the structural unit (z) is preferably a radically polymerizable group.
  • the content of the structural unit (z) in the polymer (S) is the constitution contained in the polymer (S). It is preferably more than 0 mol% and less than 100 mol%, more preferably 20 mol% or more and 97 mol% or less, and still more preferably 30 mol% or more and 95 mol% or less, relative to the entire unit. , is particularly preferably 40 mol % or more and 80 mol % or less, and most preferably 50 mol % or more and 70 mol % or less.
  • the polymer (S) may have any other structural unit in addition to the above structural units (a) to (c).
  • the polymer (S) may further have a structural unit (c) which is a structural unit different from the structural unit (b) and has hydroxyl group bonding properties.
  • a structural unit (c) having a hydroxyl group bonding property is also referred to as a “structural unit (c)”. “Having a hydroxyl group bonding property” means being able to bond to a hydroxyl group.
  • the structural unit (c) preferably contains a hydroxyl-bonding group, more preferably a group capable of chemically bonding with a hydroxyl group.
  • Structural unit (c) preferably has at least one selected from the group consisting of a boronic acid group, a boronate ester group, an isocyanate group, an aldehyde group, and an alkoxysilyl group. and an isocyanate group, and more preferably at least one selected from the group consisting of a boronic acid group and a boronate ester group.
  • the alkoxysilyl group is preferably an alkoxysilyl group having 1 to 20 carbon atoms, more preferably an alkoxysilyl group having 1 to 10 carbon atoms, still more preferably an alkoxysilyl group having 1 to 7 carbon atoms, and an alkoxysilyl group having 1 to 4 carbon atoms. Alkoxysilyl groups are particularly preferred.
  • the structural unit (c) preferably contains a group represented by the following general formula (BR-1) or (BR-2).
  • R 31 and R 32 each independently represent a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms).
  • the above alkyl group may have a substituent.
  • substituents include monovalent non - metallic atomic groups excluding hydrogen atoms. It is the same as a thing.
  • * represents a binding position.
  • E 21 and E 22 each independently represent —O— or —NR K1 —.
  • R K1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When multiple R K1 are present, the multiple R K1 may be the same or different.
  • L 31 represents an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms) or an arylene group (preferably an arylene group having 6 to 10 carbon atoms).
  • the alkylene group and the arylene group may have substituents. Examples of substituents include monovalent non - metallic atomic groups excluding hydrogen atoms. It is the same as a thing. * represents a binding position.
  • the structural unit (c) is preferably represented by the following general formula (3).
  • R4 represents a hydrogen atom, a fluorine atom, a chlorine atom or an alkyl group having 1 to 20 carbon atoms.
  • U 1 and U 2 each independently represent -O-, -S-, -COO-, -OCO-, -CONH-, -NHCOO- or -NH-.
  • R5 and R6 each independently represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heteroaryl group. R5 and R6 may be combined.
  • L4 represents a single bond or a divalent linking group.
  • R 4 in general formula (3) represents a hydrogen atom, a fluorine atom, a chlorine atom or an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group represented by R 4 may be linear or branched, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 7 carbon atoms, and more preferably 1 to 4 carbon atoms. is more preferably an alkyl group, and particularly preferably a methyl group.
  • R 4 preferably represents a hydrogen atom or a methyl group.
  • U 1 and U 2 in general formula (3) each independently represent -O-, -S-, -COO-, -OCO-, -CONH-, -NHCOO- or -NH-, and -O- or -NH- is preferred, and -O- is more preferred.
  • R 5 and R 6 in general formula (3) each independently represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heteroaryl group. R5 and R6 may be combined.
  • the aliphatic hydrocarbon group represented by R5 and R6 may have a substituent.
  • Aliphatic hydrocarbon groups represented by R 5 and R 6 include alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups and alkynyl groups which may have a substituent.
  • the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 7 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. .
  • alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl groups.
  • hexadecyl group, octadecyl group, eicosyl group isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-methylhexyl group, etc. or a branched alkyl group.
  • the cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 5 to 15 carbon atoms.
  • Specific examples of cycloalkyl groups include cyclopentyl, cyclohexyl, 1-adamantyl, and 2-norbornyl groups.
  • the alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms, still more preferably an alkenyl group having 2 to 7 carbon atoms, and particularly preferably an alkenyl group having 2 to 4 carbon atoms.
  • alkenyl groups include linear or branched alkenyl groups such as vinyl, 1-propenyl, 1-butenyl and 1-methyl-1-propenyl groups.
  • the cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms, more preferably a cycloalkenyl group having 5 to 15 carbon atoms.
  • Specific examples of the cycloalkenyl group include a 1-cyclopentenyl group and a 1-cyclohexenyl group.
  • the alkynyl group is preferably an alkynyl group having 2 to 20 carbon atoms, more preferably an alkynyl group having 2 to 10 carbon atoms, still more preferably an alkynyl group having 2 to 7 carbon atoms, and particularly preferably an alkynyl group having 2 to 4 carbon atoms.
  • Specific examples of alkynyl groups include ethynyl, 1-propynyl, 1-butynyl, and 1-octynyl groups.
  • the aryl group represented by R5 and R6 may have a substituent.
  • the aryl group represented by R 5 and R 6 is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, and even more preferably an aryl group having 6 to 12 carbon atoms.
  • the aryl group represented by R 5 and R 6 may be, for example, one in which 1 to 4 benzene rings form a condensed ring, or a benzene ring and an unsaturated five-membered ring form a condensed ring. .
  • aryl group represented by R 5 and R 6 include phenyl group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenabutenyl group, fluorenyl group and pyrenyl group.
  • the heteroaryl group represented by R5 and R6 may have a substituent.
  • the heteroaryl group represented by R 5 and R 6 is, for example, a heteroaromatic ring containing at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, and a hetero Examples include those with aryl groups.
  • Specific examples of heteroaromatic rings containing one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom include pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxazole, and isoxazole.
  • R 5 and R 6 may have include monovalent nonmetallic atomic groups excluding hydrogen atoms. is the same as those exemplified as the substituent when represents the substituent.
  • R5 and R6 preferably represent a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group. It is further preferred that both R 5 and R 6 represent a hydrogen atom or both represent an alkyl group, and that R 5 and R 6 are bonded (i.e., R 5 and R 6 represent an alkylene linking group). preferable.
  • L4 in general formula ( 3 ) represents a single bond or a divalent linking group.
  • the divalent linking group represented by L 4 is -O-, -S-, -COO-, -OCO-, -CONR 13 -, -NR 13 COO-, -CR 13 N-, substituted or unsubstituted 2 It preferably represents a divalent linking group selected from the group consisting of a valent aliphatic group, a substituted or unsubstituted divalent aromatic group, and a combination thereof.
  • R 13 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • L 4 contains a substituted or unsubstituted divalent aliphatic group
  • the number of carbon atoms in the aliphatic group is preferably 1-20, more preferably 1-15, even more preferably 1-10.
  • the number of aromatic rings is preferably 1-3, more preferably 1-2, even more preferably 1.
  • L 4 is -O-, -COO-, -OCO-, -CONR 13 -, -NR 13 COO-, a substituted or unsubstituted divalent aliphatic group, a substituted or unsubstituted divalent aromatic group , And preferably a divalent linking group selected from the group consisting of combinations thereof, -O-, -COO-, -OCO-, substituted or unsubstituted divalent aliphatic group, substituted or unsubstituted A substituted divalent aromatic group, and more preferably a divalent linking group selected from the group consisting of combinations thereof, -O-, -COO-, -OCO-, substituted or unsubstituted alkylene It is more preferably a divalent linking group selected from the group consisting of a group, a substituted or unsubstituted arylene group, and a combination thereof.
  • the repeating unit represented by general formula (3) is obtained by polymerizing a compound represented by general formula (3m) below.
  • R 4 , U 1 , U 2 , R 5 , R 6 and L 4 are R 4 , U 1 , U 2 , R 5 , R 6 and L in general formula (3), respectively. 4 , and the description, specific examples, and preferred ranges for each are also the same.
  • Wb be the content of the structural unit (b) based on the material amount
  • Wc is the content based on the amount of substance
  • Wz is the content of the structural unit (z) based on the amount of material
  • the content of the structural unit (c) in the polymer (S) is more than 0 mol% 90% with respect to the total structural units contained in the polymer (S). It is preferably mol % or less, more preferably 5 mol % or more and 85 mol % or less, and even more preferably 10 mol % or more and 80 mol % or less.
  • the weight average molecular weight (Mw) of the polymer (S) is preferably 5,000 to 200,000, more preferably 8,000 to 150,000, even more preferably 10,000 to 100,000.
  • the molecular weight dispersity (Mw/Mn) of the polymer (S) is, for example, 1.00 to 4.00, preferably 1.10 to 3.70, more preferably 1.20 to 3.00. , more preferably 1.20 to 2.50.
  • Mw represents the weight average molecular weight
  • Mn represents the number average molecular weight.
  • the weight average molecular weight and molecular weight dispersity of the polymer (S) are the values measured by GPC (converted to polystyrene). Specifically, the weight average molecular weight is obtained by preparing HLC-8220 (manufactured by Tosoh Corporation) as an apparatus, using tetrahydrofuran as an eluent, using TSKgel (registered trademark) G3000HXL + TSKgel (registered trademark) G2000HXL as a column, at a temperature of 23 ° C. , at a flow rate of 1 mL/min, using a differential refractive index (RI) detector.
  • RI differential refractive index
  • polymer (S) Specific examples of the polymer (S) are shown below, but are not limited to these.
  • Polymer (S) can be produced by a known method.
  • a monomer containing a group containing a fluorine atom as described above, a monomer containing a cationically polymerizable group as described above, a monomer containing a radically polymerizable group as described above, and any other monomer are mixed, and in an organic solvent, a radical It can be produced by polymerization using a polymerization initiator.
  • the radical polymerization it is preferable to protect the radically polymerizable group of the structural unit (z) by a known method in order to prevent the radically polymerizable group from reacting.
  • the content of the polymer (S) in the curable resin composition of the present invention is not particularly limited, and can be appropriately adjusted depending on the application of the curable resin composition.
  • the polymer (S) can be used as a main component or as an additive.
  • the main component is the component with the highest content among the solids contained in the curable resin composition.
  • the additive is a component that is not the main component among the solids contained in the curable resin composition.
  • the content of the polymer (S) is It is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, relative to the total solid content in the resin composition).
  • the upper limit of the polymer (S) content is not particularly limited, but is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 97% by mass or less.
  • the total solid content means all components other than the solvent.
  • the content of the polymer (S) is With respect to the total solid content in the resin composition), for example, it can be 0.001 to 10% by mass, it can be 0.01 to 7% by mass, and it is 0.1 to 5% by mass It can also be 0.1 to 3% by mass.
  • curable resin composition of the present invention only one type of polymer (S) may be used, or two or more types having different structures may be used in combination.
  • curable resin composition preferably hard coat layer-forming composition
  • curable resin composition preferably hard coat layer-forming composition
  • the curable resin composition of the present invention can contain a polyorganosilsesquioxane (a1) having a cationically polymerizable group (also referred to as "polyorganosilsesquioxane (a1)").
  • the cationic polymerizable group in the polyorganosilsesquioxane (a1) is not particularly limited, and may be any known cationic polymerizable group.
  • Examples of cationic polymerizable groups include alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spiroorthoester groups, and vinyloxy groups.
  • the cationic polymerizable group is preferably an alicyclic ether group or a vinyloxy group, more preferably an epoxy group, an epoxycyclohexyl group, an oxetanyl group or a vinyloxy group, more preferably an epoxy group, an epoxycyclohexyl group or an oxetanyl group, and an epoxy group or Epoxycyclohexyl groups are most preferred.
  • each group described above may have a substituent.
  • the cationically polymerizable group is preferably a group represented by any one of the following formulas (ca1) to (ca3).
  • the polyorganosilsesquioxane (a1) preferably has structural units represented by any of the following general formulas (csa-1) to (csa-3).
  • L5 represents a single bond or a divalent linking group.
  • Rca has the same meaning as in formula (ca3).
  • SiO 1.5 represents a structural portion (silsesquioxane unit) composed of siloxane bonds (Si—O—Si) in polysilsesquioxane.
  • Polysilsesquioxane is a network-type polymer or polyhedral cluster having siloxane structural units derived from a hydrolyzable trifunctional silane compound, and can form a random structure, ladder structure, cage structure, etc. by siloxane bonds.
  • SiO 1.5 described in this specification is the same as above.
  • L5 represents a single bond or a divalent linking group.
  • L 5 represents a divalent linking group, -O-, -CO-, -COO-, -S-, -SO 2 -, -NR-, an organic linking group having 1 to 20 carbon atoms (e.g., substituted an alkylene group optionally having a group, a cycloalkylene group optionally having a substituent, an arylene group optionally having a substituent, etc.), or a linking group formed by combining two or more of these.
  • R above represents a hydrogen atom or a substituent.
  • L 5 is preferably a single bond, an alkylene group having 1 to 10 carbon atoms, —O—, —CO—, —COO—, —S—, or a linking group formed by combining two or more of these. More preferably, it is a bond, an alkylene group having 1 to 6 carbon atoms, —O—, —CO—, —COO—, —S—, or a linking group formed by combining two or more of these.
  • Rca has the same meaning as in formula (ca3), and specific examples and preferred ranges are also the same.
  • the content of the structural unit represented by any of the above general formulas (csa-1) to (csa-3) in the polyorganosilsesquioxane (a1) is included in the polyorganosilsesquioxane (a1). It is preferably 50 mol% or more and 100 mol% or less, more preferably 70 mol% or more and 100 mol% or less, and 90 mol% or more and 100 mol% or less with respect to the entire structural unit. More preferred.
  • the polyorganosilsesquioxane (a1) may have any other structural unit in addition to the structural units represented by any of the general formulas (csa-1) to (csa-3). good.
  • the polyorganosilsesquioxane (a1) has a standard polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC), preferably 500 to 6000, more preferably 1000 to 4500, still more preferably 1500-3000.
  • Mn polystyrene-equivalent number average molecular weight measured by gel permeation chromatography
  • the polyorganosilsesquioxane (a1) has a standard polystyrene-equivalent molecular weight dispersity (Mw/Mn) measured by GPC, for example, 1.0 to 4.0, preferably 1.1 to 3.7, and more It is preferably 1.2 to 3.0, more preferably 1.3 to 2.5.
  • Mw represents the weight average molecular weight
  • Mn represents the number average molecular weight.
  • the method for measuring the weight average molecular weight and molecular weight dispersity of the polyorganosilsesquioxane (a1) is the same as the method for measuring the weight average molecular weight and molecular weight dispersity of the polymer (S) described above.
  • polyorganosilsesquioxane (a1) Only one type of polyorganosilsesquioxane (a1) may be used, or two or more types having different structures may be used in combination.
  • the content of the polyorganosilsesquioxane (a1) in the curable resin composition of the present invention is not particularly limited, but may be 50% by mass or more with respect to the total solid content of the curable resin composition. , 70% by mass or more, and may be 80% by mass or more.
  • the upper limit of the content of the polyorganosilsesquioxane (a1) in the curable resin composition is not particularly limited, but it can be 99.999% by mass or less, and can be 99.99% by mass or less. , 99.9% by mass or less.
  • the total solid content means all components other than the solvent.
  • the curable resin composition of the present invention may contain a radical polymerization initiator.
  • One radical polymerization initiator may be used alone, or two or more different structures may be used in combination.
  • the radical polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.
  • the content of the radical polymerization initiator in the curable resin composition of the present invention is not particularly limited, but is preferably 0.1 to 500 parts by mass with respect to 100 parts by mass of polymer (S), 0.5 to 20 parts by mass is more preferable.
  • the curable resin composition of the present invention may contain a cationic polymerization initiator.
  • the cationic polymerization initiator may be a photocationic polymerization initiator or a thermal cationic polymerization initiator.
  • Examples of cationic polymerization initiators include, but are not limited to, sulfonium salts, ammonium salts, iodonium salts (eg, diaryliodonium salts), triarylsulfonium salts, diazonium salts, and iminium salts.
  • a cationic polymerization initiator can be synthesized by a known method and is also available as a commercial product.
  • iodonium salt-based photocationic polymerization initiator examples include, for example, B2380 manufactured by Tokyo Chemical Co., Ltd., BBI-102 manufactured by Midori Chemical Co., Ltd., WPI-113 manufactured by Fuji Film Wako Pure Chemical, and manufactured by Fuji Film Wako Pure Chemical. WPI-124, WPI-169 manufactured by Fuji Film Wako Pure Chemical, WPI-170 manufactured by Fuji Film Wako Pure Chemical, and DTBPI-PFBS manufactured by Toyo Gosei Chemical Co., Ltd. can be mentioned.
  • the content of the cationic polymerization initiator in the curable resin composition of the present invention is not particularly limited. Parts by mass are preferable, and 1 to 50 parts by mass are more preferable.
  • the curable resin composition of the present invention may contain a solvent.
  • a solvent an organic solvent is preferable, and one or two or more organic solvents can be mixed in an arbitrary ratio and used.
  • organic solvents include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone; cellosolves such as ethyl cellosolve; toluene.
  • the content of the solvent in the curable resin composition of the present invention can be appropriately adjusted within a range in which the coating suitability of the curable resin composition can be ensured. For example, it can be 50 to 500 parts by mass, preferably 80 to 200 parts by mass, per 100 parts by mass of the total solid content of the curable resin composition.
  • a curable resin composition is usually in the form of a liquid.
  • the solid content concentration of the curable resin composition is usually 10 to 90% by mass, preferably 20 to 80% by mass, and particularly preferably 40 to 75% by mass.
  • the curable resin composition of the present invention may contain components other than those described above. may contain.
  • the curable resin composition of the present invention can be prepared by mixing the various components described above simultaneously or sequentially in any order.
  • the preparation method is not particularly limited, and a known stirrer or the like can be used for preparation.
  • the hard coat film of the present invention is a hard coat film comprising a substrate (preferably a plastic substrate) and a hard coat layer formed from the curable resin composition of the present invention described above.
  • the thickness of the hard coat layer that can be formed from the curable resin composition of the present invention is not particularly limited, but is preferably 0.5 to 30 ⁇ m, more preferably 1 to 25 ⁇ m, and more preferably 2 to 20 ⁇ m. is more preferable.
  • the film thickness of the hard coat layer is calculated by observing the cross section of the laminate with an optical microscope.
  • a cross-section sample can be prepared by a microtome method using a cross-section cutting device ultramicrotome, a cross-section processing method using a focused ion beam (FIB) device, or the like.
  • the curable resin composition of the present invention can be applied onto a substrate and cured to form a hard coat layer.
  • the substrate used for the hard coat film preferably has a transmittance in the visible light region of 70% or more, more preferably 80% or more, and even more preferably 90% or more.
  • the substrate is preferably a plastic substrate and preferably comprises a polymer.
  • a polymer excellent in optical transparency, mechanical strength, thermal stability and the like is preferable.
  • polymers examples include polycarbonate-based polymers, polyester-based polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymer (AS resin).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • AS resin styrene-based polymers
  • Polyolefins such as polyethylene and polypropylene, norbornene resins, polyolefin polymers such as ethylene/propylene copolymers, (meth)acrylic polymers such as polymethyl methacrylate, vinyl chloride polymers, nylon, and amides such as aromatic polyamides.
  • -based polymer imide-based polymer, sulfone-based polymer, polyethersulfone-based polymer, polyetheretherketone-based polymer, polyphenylene sulfide-based polymer, vinylidene chloride-based polymer, vinyl alcohol-based polymer, vinyl butyral-based polymer, arylate-based polymer, polyoxy A methylene-based polymer, an epoxy-based polymer, a cellulose-based polymer represented by triacetyl cellulose, a copolymer of the above-mentioned polymers, and a polymer obtained by mixing the above-mentioned polymers are also included.
  • amide-based polymers such as aromatic polyamides and imide-based polymers have a large number of times of breaking and bending measured by an MIT tester according to JIS (Japanese Industrial Standards) P8115 (2001), and have relatively high hardness. It can be preferably used.
  • aromatic polyamides such as those described in Example 1 of Japanese Patent No. 5699454, JP-T-2015-508345, JP-T-2016-521216, and polyimides described in WO2017/014287 are preferably used as a base material. can be used.
  • aromatic polyamide (aramid-based polymer) is preferable.
  • the substrate preferably contains at least one polymer selected from imide-based polymers and aramid-based polymers.
  • the substrate is preferably film-like.
  • the thickness of the substrate is more preferably 100 ⁇ m or less, still more preferably 80 ⁇ m or less, and most preferably 50 ⁇ m or less. From the viewpoint of ease of handling of the substrate, the thickness of the substrate is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and most preferably 15 ⁇ m or more.
  • the hard coat film of the present invention has excellent scratch resistance.
  • an index of scratch resistance the surface of the hard coat layer of the hard coat film of the present invention was subjected to a rubbing test using a rubbing tester under the following conditions. It is more preferable that no scratch occurs when rubbed back and forth 100 times, and more preferably no scratch occurs when rubbed back and forth 300 times.
  • the hard coat film of the present invention may further have a scratch resistant layer.
  • a scratch resistant layer it preferably has a substrate, a hard coat layer, and a scratch resistant layer in this order.
  • the scratch-resistant layer is not particularly limited, it is preferably a layer obtained by curing a composition for forming a scratch-resistant layer containing the radically polymerizable compound (c1).
  • the radically polymerizable compound (c1) (also referred to as “compound (c1)”) will be described.
  • Compound (c1) is a compound having a radically polymerizable group.
  • the radically polymerizable group in the compound (c1) is not particularly limited, and generally known radically polymerizable groups can be used.
  • the radically polymerizable group includes a polymerizable unsaturated group, specifically a (meth)acryloyl group, a vinyl group, an allyl group, and the like, preferably a (meth)acryloyl group.
  • each group described above may have a substituent.
  • Compound (c1) is preferably a compound having two or more (meth)acryloyl groups in one molecule, more preferably a compound having three or more (meth)acryloyl groups in one molecule.
  • the molecular weight of compound (c1) is not particularly limited, and may be a monomer, an oligomer, or a polymer.
  • the content of the compound (c1) in the scratch-resistant layer-forming composition is preferably 80% by mass or more, more preferably 85% by mass or more, based on the total solid content in the scratch-resistant layer-forming composition.
  • 90% by mass or more is more preferable.
  • the scratch-resistant layer-forming composition preferably contains a radical polymerization initiator.
  • a radical polymerization initiator may be used alone, or two or more different structures may be used in combination. Further, the radical polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator.
  • the content of the radical polymerization initiator in the scratch-resistant layer-forming composition is not particularly limited. ⁇ 50 parts by mass is more preferable.
  • the scratch-resistant layer-forming composition may contain a solvent.
  • the solvent is the same as the solvent that the curable resin composition may contain.
  • the content of the solvent in the composition for forming a scratch resistant layer in the present invention can be appropriately adjusted within a range in which the applicability of the composition for forming a scratch resistant layer can be ensured. For example, it can be 50 to 500 parts by mass, preferably 80 to 200 parts by mass, per 100 parts by mass of the total solid content of the scratch-resistant layer-forming composition.
  • the scratch-resistant layer-forming composition usually takes the form of a liquid.
  • the concentration of the solid content of the scratch-resistant layer-forming composition is usually 10 to 90% by mass, preferably 15 to 80% by mass, and particularly preferably 20 to 70% by mass.
  • the scratch-resistant layer-forming composition may contain components other than those described above, such as inorganic particles, leveling agents, antifouling agents, antistatic agents, slip agents, and solvents.
  • the thickness of the scratch-resistant layer is preferably less than 3.0 ⁇ m, more preferably 0.1 to 2.0 ⁇ m, and more preferably 0.1 to 1.0 ⁇ m. More preferred.
  • the method for producing a hard coat film of the present invention is a method for producing a hard coat film including a substrate and a hard coat layer, and the curable resin composition of the present invention is applied onto the substrate to form a coating film.
  • the method for producing a hard coat film comprises forming a hard coat layer by subjecting the coating film to a curing treatment.
  • the base material is as described above.
  • the curing treatment is preferably a curing treatment using at least one of light and heat, and more preferably a curing treatment using light and heat because the curing reaction rate can be increased.
  • Curing treatment with light is treatment in which a polymerization reaction proceeds by irradiation with light (preferably ionizing radiation).
  • the curing treatment by heat is a treatment for promoting a polymerization reaction by heating.
  • the method of applying the curable resin composition is not particularly limited, and known methods can be used. Examples thereof include dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating and die coating.
  • the type of light is not particularly limited and includes X-rays, electron beams, ultraviolet rays, visible light, infrared rays and the like, but ultraviolet rays are preferably used.
  • the hard coat layer coating film is UV curable, it is preferable to semi-cure the curable compound by irradiating UV rays with an irradiation dose of 10 mJ/cm 2 to 2000 mJ/cm 2 from an UV lamp. It is more preferably 50 mJ/cm 2 to 1800 mJ/cm 2 and even more preferably 100 mJ/cm 2 to 1500 mJ/cm 2 .
  • a metal halide lamp, a high-pressure mercury lamp, or the like is preferably used as the type of ultraviolet lamp.
  • the temperature reached by heating the hard coat layer is not particularly limited, but is preferably 80° C. or higher and 200° C. or lower, more preferably 100° C. or higher and 180° C. or lower. It is preferably 120° C. or higher and 160° C. or lower, more preferably.
  • the oxygen concentration during curing is preferably 0 to 1.0% by volume, more preferably 0 to 0.1% by volume, and most preferably 0 to 0.05% by volume.
  • the hard coat film of the present invention has excellent surface properties and scratch resistance, and can be used, for example, as an optical film. Further, the hard coat film of the present invention can be used as a surface protective film for image display devices (surface protective film for image display devices).
  • a surface protective film for an image display device is a protective film placed on the surface of an image display device in order to protect the display surface (display surface) of the image display device.
  • the present invention also relates to an article provided with the hard coat film of the present invention and an image display apparatus provided with the hard coat film of the present invention as a surface protection film.
  • BHT dibutylhydroxytoluene
  • the resulting solid was dissolved in 15 g of MEK, 11 g of triethylamine and 0.01 g of p-methoxyphenol were added, and the mixture was stirred at 60° C. for 4 hours. After cooling the reaction solution to room temperature, it was reprecipitated using 500 mL of a 1:1 mixed solvent of methanol and water, and dissolved in 25 g of MEK to obtain 7.0 g of polymer (S-1) (yield 70%). .
  • Polymers (S-2) to (S-6) and (S2-1) to (S2-7) are synthesized according to the synthesis method of the polymer (S-1), respectively, the type and amount of the monomer, the polymerization initiator was synthesized by changing the amount of
  • the structural formula and weight average molecular weight (Mw) of each polymer used are shown below.
  • the content (content ratio) of each structural unit in the following structural formula is based on the amount of substance, and the unit is "mol %".
  • ⁇ Preparation of base material> (Manufacturing of polyimide powder) 832 g of N,N-dimethylacetamide (DMAc) was added to a 1 L reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a condenser under a nitrogen stream, and then the temperature of the reactor was reduced to 25. °C. 64.046 g (0.2 mol) of bistrifluoromethylbenzidine (TFDB) was added thereto and dissolved.
  • DMAc N,N-dimethylacetamide
  • TFDB bistrifluoromethylbenzidine
  • base material K-1 100 g of the above polyimide powder was dissolved in 670 g of N,N-dimethylacetamide (DMAc) to obtain a 13% by weight solution. The resulting solution was cast on a stainless plate and dried with hot air at 130° C. for 30 minutes. After that, the film was peeled off from the stainless steel plate and fixed to the frame with pins. The frame with the film fixed was placed in a vacuum oven and heated for 2 hours while gradually increasing the heating temperature from 100°C to 300°C, and then gradually. cooled to After the cooled film was separated from the frame, it was further heat-treated at 300° C. for 30 minutes as the final heat-treatment step to obtain a base material K-1 made of a polyimide film and having a thickness of 30 ⁇ m.
  • DMAc N,N-dimethylacetamide
  • Example 1 ⁇ Preparation of curable resin composition (composition for forming hard coat layer)> (Curable resin composition HC-1)
  • the following components were put into a mixing tank in the following amounts and stirred.
  • the resulting composition was filtered through a polypropylene filter having a pore size of 0.45 ⁇ m to obtain a curable resin composition HC-1.
  • Polymer (S-1) 94.75 parts by mass Irgacure 127 5.00 parts by mass RS-90 0.25 parts by mass MIBK (methyl isobutyl ketone) 100.00 parts by mass
  • Irgacure 127 (Irg.127): Photoradical polymerization initiator, manufactured by BASF RS-90: Slip agent, manufactured by DIC Corporation
  • the curable resin composition HC-1 was bar-coated on a polyimide substrate K-1 having a thickness of 30 ⁇ m using a wire bar #18 so that the film thickness after curing was 18 ⁇ m. A coat layer coating was applied. Next, after drying the hard coat layer coating film at 120° C. for 1 minute, it was irradiated with ultraviolet rays using an air-cooled mercury lamp under conditions of 25° C. and an oxygen concentration of 100 ppm (parts per million). Thus, the hard coat layer coating film was cured. Thus, a hard coat film having a hard coat layer (a layer obtained by curing the curable resin composition HC-1) on the substrate was obtained.
  • Examples 2 to 13, Comparative Examples 1 to 5 Hard coat films of Examples 2 to 13 and Comparative Examples 1 to 5 were produced in the same manner as in Example 1, except that the polymers listed in Table 1 below were used instead of the polymer (S-1). .
  • polymer (SX-1) and polymer (SX-4) were used at a mass ratio of polymer (SX-1):polymer (SX-4) of 1:1, and polymer (SX-1) and The total content of polymer (SX-4) was the same as the content of polymer (S-1) in Example 1.
  • the hard coat films of Examples 1 to 13 were excellent in scratch resistance.
  • a curable resin composition capable of forming a cured layer having excellent scratch resistance, a hard coat film formed using the curable resin composition, and a method for producing the hard coat film. can provide.

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Abstract

L'invention concerne : une composition de résine durcissable comprenant un polymère (S) ayant au moins une unité structurale qui est sélectionnée dans le groupe constitué par des unités structurales (a) qui comprennent un atome de fluor et des unités structurales (b) qui comprennent un groupe polymérisable par voie cationique et une unité structurale (z) qui est représentée par la formule générale (Z-1) qui est présentée dans la description ; un film de revêtement dur formé à l'aide de la composition de résine durcissable ; et un procédé de production du film de revêtement dur. Ainsi, l'invention concerne une composition de résine durcissable qui permet de former une couche durcie ayant une excellente résistance à l'abrasion, un film de revêtement dur formé à l'aide de la composition de résine durcissable, et un procédé de production du film de revêtement dur.
PCT/JP2022/021816 2021-06-07 2022-05-27 Composition de résine durcissable, film de revêtement dur et procédé de production de film de revêtement dur WO2022259893A1 (fr)

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