WO2022259893A1

WO2022259893A1 - Curable resin composition, hard coat film, and production method for hard coat film

Info

Publication number: WO2022259893A1
Application number: PCT/JP2022/021816
Authority: WO
Inventors: 考浩加藤; 哲北村; 壮一郎渡邉; 慶介吉政; 彩子松本; 顕夫田村
Original assignee: 富士フイルム株式会社
Priority date: 2021-06-07
Filing date: 2022-05-27
Publication date: 2022-12-15
Also published as: JPWO2022259893A1; KR20240001251A

Abstract

Provided are: a curable resin composition comprising a polymer (S) having at least one structural unit that is selected from the group consisting of structural units (a) which include a fluorine atom and structural units (b) which include a cationically polymerizable group and a structural unit (z) that is represented by general formula (Z-1) which is set forth in the specification; a hard coat film formed using the curable resin composition; and a production method for the hard coat film. Thus, provided are a curable resin composition which makes it possible to form cured layer having excellent abrasion resistance, a hard coat film formed using the curable resin composition, and a production method for the hard coat film.

Description

Curable resin composition, hard coat film and method for producing hard coat film

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. For example, in 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), In order to prevent scratches on the substrate, it is preferable to provide an optical film (hard coat film) having a hard coat layer on the substrate, and a curable resin composition is used to form the hard coat layer. there is

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.

Japanese Patent Application Laid-Open No. 2015-175923

However, as a result of investigation by the present inventors, it has been found that a cured layer formed by curing a conventional curable resin composition does not have sufficient scratch resistance.
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.

The inventors diligently studied and found that the above problems could be solved by the following means.

<1>
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

In the general formula (Z-1),
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. One or more —CH ₂ — contained in the aliphatic group may be independently replaced with —CO—, —O— or —NR ^Z4 —. 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).

In general formulas (Ea-1) and (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.
<2>
With respect to all the structural units contained in the polymer (S), 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, and 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 %.
<3>
The curable resin composition according to <2>, wherein Wz satisfies 30 mol%≦Wz≦95 mol%.
<4>
Any one of <1> to <3>, wherein the polymer (S) further has a structural unit (c) which is a structural unit different from the structural unit (b) and has hydroxyl group bonding properties. The curable resin composition according to .
<5>
With respect to all the structural units contained in the polymer (S), 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, and the above constitution Where Wc is the content of the unit (c) based on the substance amount, and 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.
<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.
<9>
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 <1> The curable resin composition according to any one of <8>.
<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.
<12>
The curable resin composition according to any one of <1> to <11>, wherein the structural unit (a) has a group represented by the following general formula (f-1).

In general formula (f-1), q1 represents an integer of 0 to 12, q2 represents an integer of ₁ to 8, and Rq1 represents a hydrogen atom or a fluorine atom. * represents a binding position.
<13>
The curable resin composition according to any one of <1> to <12>, wherein the structural unit (a) has a group represented by the following general formula (B1).

In general formula (B1),
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.
<14>
The curable resin composition according to any one of <1> to <13>, wherein the structural unit (a) has a perfluoropolyether group.
<15>
Curing according to any one of <1> to <14>, wherein the cationic polymerizable group of the structural unit (b) is a group represented by any one of the following general formulas (C1) to (C3): elastic resin composition.

In general formulas (C1) to (C3), * represents a bonding position. In general formula (C3), R 2 _C represents a hydrogen atom or a substituent.
<16>
The curable resin composition according to any one of <1> to <15>, wherein the polymer (S) has a weight average molecular weight of 5,000 to 200,000.
<17>
A hard coat film comprising a substrate and a hard coat layer formed from the curable resin composition according to any one of <1> to <16>.
<18>
A method for producing a hard coat film comprising a substrate and a hard coat layer, wherein the curable resin composition according to any one of <1> to <16> is applied onto the substrate to form a coating film. and subjecting the coating film to a curing treatment to form the hard coat layer.
<19>
The method for producing a hard coat film according to <18>, wherein the curing treatment is a curing treatment using light and heat.

According to the present invention, 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.

Modes for carrying out the present invention will be described in detail below, but the present invention is not limited to these.
In this specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”.
As used herein, the term "(meth)acrylate" means "at least one of acrylate and methacrylate." The same applies to "(meth)acrylic acid", "(meth)acryloyl" and the like.
In the present specification, for each component, one type of substance applicable to each component may be used alone, or two or more types may be used in combination. Here, when two or more substances are used in combination for each component, the content of the component refers to the total content of the substances used in combination unless otherwise specified.
Moreover, the bonding direction of the divalent group described in this specification is not particularly limited.

[Curable resin composition]
The curable resin composition of the present invention contains a polymer (S).

<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)”.

In general formulas (Ea-1) and (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).

In the polymer (S), 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.

When 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.

With respect to all structural units contained in the polymer (S), let Wa be the content of the structural unit (a) based on the material amount, Wb be the content of the structural unit (b) based on the material amount, and 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 %.

From the viewpoint of improving scratch resistance, 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%.

From the viewpoint of improving scratch resistance, Wz preferably satisfies 30 mol% ≤ Wz ≤ 95 mol%.

Although the main chain structure of the polymer (S) is not particularly limited, it is preferably a (meth)acryl polymer or a (meth)acrylamide polymer.

[Structural Unit (a) Containing Fluorine Atom]
The structural unit (a) containing a fluorine atom will be explained.

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. Although 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. In addition, 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. Examples of 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.
Here, 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. Note that fa represents an integer from 0 to 12.
Examples of -CH ₂ - constituting a fluorine atom-containing alkyl group substituted with -O- for one or more -(CF ₂ ) _fb OC(CF ₃ ) ₃ and -CF ₂ CF ₂ O(CF ₂ CF ₂ O) _fc CF ₂ CF ₂ CF ₃ , —CF(CF ₃ )OCF ₂ CF(CF ₃ )OCF ₂ CF ₂ CF ₃ and the like. Note that fb represents an integer of 1-10, and fc represents an integer of 1-10.
Examples of fluorine atom-containing alkenyl groups include -C(CF ₃ )=C(CF(CF ₃ ) ₂ ) ₂ and the like.
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.

In general formula (f-1), q1 represents an integer of 0 to 12, q2 represents an integer of ₁ to 8, and 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).

In 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.).

In general formula (1), X ¹ and X ² each independently represent an oxygen atom or a sulfur atom, preferably an oxygen atom.

In general formula (1), R ¹ and R ² each independently represent a hydrogen atom or a substituent. When R ¹ and R ² represent a substituent, the type of substituent is not particularly limited, and any known substituent may be used. Examples of 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, mercapto group, halogen atom, cyano group, sulfo group, carboxy group, nitro group and silyl group. Moreover, when these substituents can further have one or more substituents, they may have the above-described substituents as further substituents.
When 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. Although 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.

m represents 0 or 1, preferably 0;
n represents 0 or 1, preferably 1;

In general formula (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.

When the structural unit (a) contains a fluorine-containing group and an acid-cleavable group, 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.
As 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 α-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).

In general formulas (AC1), (SA1) and (DS1), 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.
In general formulas (AC2), (SA2), (SA3) and (DS2), 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.
In general formulas (AC1), (AC2), (SA1), (SA2), (SA3), (DS1) and (DS2), * represents a binding position.

In general formulas (AC1), (SA1) and (DS1), 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.
In general formulas (AC2), (SA2), (SA3) and (DS2), 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.
Preferably, k represents 0 or 1.

When the polymer (S) is a polymer synthesized by radical polymerization of a monomer having a (meth)acryloyl group such as a (meth)acrylic polymer or a (meth)acrylamide polymer, 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).

In the general formula above, 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).

In general formulas (A-1) to (A-4), A represents -O- or -NH-, preferably -O-.

In general formulas (A-1) to (A-4), L ₁ represents a single bond or a divalent linking group. When 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. Examples of the substituent when R represents a substituent include an alkyl group and an aryl group.
As 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 α-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.

In general formulas (A-1) to (A-5), _Q1 represents a fluorine atom-containing group. The groups containing fluorine atoms are the same as those described above.

In general formulas (A-1) to (A-5), 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.

Since the scratch resistance of the cured layer obtained by curing the curable resin composition of the present invention can be further improved, the structural unit (a) has a group represented by the following general formula (B1). is preferred.

In general formula (B1),
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.

In general formula (B1) above, 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.
Examples of 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. In addition, the said substituent may be further substituted by the substituent.
Among them, as the substituent represented by one embodiment of R ^b1 , 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.

In general formula (B1) above, R ^b2 represents a hydrogen atom or a substituent. However, 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.

In general formula (B1) above, L ^b1 represents an n+1-valent linking group. However, a plurality of L ^b1 may be the same or different.
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. is preferably a hydrocarbon group which may contain a carbon atom, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom or a nitrogen atom.

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.
As 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. valent aliphatic hydrocarbon groups; divalent aromatic hydrocarbon groups such as arylene groups;
Examples of 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.
Further, as a group in which these are combined, 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-.
Among these 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.
As 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.
As the 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 α-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.

In general formula (B1) above, Z ^b1 represents a group containing a fluorine atom. However, 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).

In the above 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.

In general formula (10) above, 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.

In general formula (10) above, Y ¹ represents —O— or —NR ^Z —. However, R ^Z represents a hydrogen atom or a substituent.
Here, 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. preferable.
Y ¹ preferably represents -O- or -NH-, more preferably -O-.

In general formula (10) above, 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. is preferably a hydrocarbon group which may contain a carbon atom, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may contain an oxygen atom or a nitrogen 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.

As the r+1-valent linking group, a divalent to trivalent linking group is preferable, and a divalent linking group is more preferable.
Examples of 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).

In the above general formula (10), r represents an integer of 1 or more. Among them, from the viewpoint of synthesis suitability, 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.

Examples of perfluoropolyether groups 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.

Specific examples of the structural unit (a) are shown below, but are not limited to these. 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.

From the viewpoint of further improving the scratch resistance of the cured layer obtained by curing the curable resin composition of the present invention, when the polymer (S) contains the structural unit (a), 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.

[Structural Unit (b) Containing Cationic Polymerizable Group]
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. In addition, 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).

In formulas (C1) to (C3), * represents a bonding position. In formula (C3), R _C represents a hydrogen atom or a substituent.

When 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. Examples of 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.

When the polymer (S) is a polymer synthesized by radical polymerization of a monomer having a (meth)acryloyl group such as a (meth)acrylic polymer or a (meth)acrylamide polymer, the structural unit (b) has the following general formula (CA- A structural unit represented by any one of 1) to (CA-3) is preferred.

In general formulas (CA-1) to (CA-3), 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. In general formula (CA-3), R 1 _C has the same meaning as in formula (C3) above.

In general formulas (CA-1) to (CA-3), A represents -O- or -NH-, preferably -O-.

In general formulas (CA-1) to (CA-3), L ₃ represents a single bond or a divalent linking group.
When 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.

In general formula (CA-3), R 1 _C has the same meaning as in formula (C3) above, and specific examples and preferred ranges are also the same.

Specific examples of the structural unit (b) containing a cationic polymerizable group are shown below, but are not limited to these.

From the viewpoint of further improving the scratch resistance of the cured layer obtained by curing the curable resin composition of the present invention, when the polymer (S) contains the structural unit (b), 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.

[Structural Unit (z) Represented by General Formula (Z-1)]
The structural unit (z) represented by general formula (Z-1) will be described.

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. More preferably, it represents a w+1-valent aliphatic hydrocarbon group having 1 to 3 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. Especially preferred. The total number of oxygen atoms contained in L ^Z1 and L ^Z2 is preferably 0-4, more preferably 0-2.

In general formula (Ea-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.

Specific examples of the structural unit (z) are shown below, but are not limited to these.

From the viewpoint of further improving the scratch resistance of the cured layer obtained by curing the curable resin composition of the present invention, 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).

[Structural Unit (c) Having Hydroxyl Group Bonding Property]
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).

In general formula (BR-1) above, 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. Examples of substituents include ^monovalent non ^- metallic atomic groups excluding hydrogen atoms. It is the same as a thing. * represents a binding position.
In general formula (BR-2) above, 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).

In 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. .
Specific examples of 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. .
Specific examples of 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. .
Specific examples of the 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. , oxadiazole, thiazole, thiadiazole, indole, carbazole, benzofuran, dibenzofuran, thianaphthene, dibenzothiophene, indazole benzimidazole, anthranil, benzisoxazole, benzoxazole, benzothiazole, purine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, quinoline, acridine, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthyridine, phenanthroline, pteridine and the like.

Examples of substituents that 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.
When 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.
When L ⁴ contains a substituted or unsubstituted divalent aromatic group, 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.

In general formula (3m), 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.

Specific examples of the compound represented by general formula (3m) capable of forming the repeating unit represented by general formula (3) are described below, but are not limited thereto.

With respect to all structural units contained in the polymer (S), let Wa be the content of the structural unit (a) based on the material amount, Wb be the content of the structural unit (b) based on the material amount, and the structural unit (c) Wc is the content based on the amount of substance, and Wz is the content of the structural unit (z) based on the amount of material, where Wa, Wb, Wc and Wz are respectively 0 mol% ≤ Wa ≤ 90 mol% and 0 mol% ≤ It is preferable that Wb≦90 mol%, 0 mol%<Wc<90 mol%, 0 mol%<Wz<100 mol%, and that both Wa and Wb are not 0 mol%.

When the polymer (S) contains the structural unit (c), 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 and Mn represents the number average molecular weight.

Unless otherwise specified, 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.

Specific examples of the polymer (S) are shown below, but are not limited to these.

<Method for producing polymer (S)>
Polymer (S) can be produced by a known method.
For example, 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. In 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.
In the curable resin composition of the present invention, 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.
When the curable resin composition of the present invention is used as a composition for forming a hard coat layer and the polymer (S) is used as a main component, 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.
In addition, the total solid content means all components other than the solvent.
When the curable resin composition of the present invention is used as a composition for forming a hard coat layer and the polymer (S) is used as an additive, 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.

In the 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.

Other components that the curable resin composition (preferably hard coat layer-forming composition) of the present invention may contain are described below.

(Polyorganosilsesquioxane (a1) having a cationic polymerizable group)
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. In addition, 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).

In formulas (ca1) to (ca3), * represents a bonding position. In formula (ca3), _Rca represents a hydrogen atom or a substituent.

Specific examples and preferred ranges of the substituent when R 2 _ca in formula (ca) represents a substituent are the same as the substituent when R 2 _C in formula (C3) above represents a substituent.

The polyorganosilsesquioxane (a1) preferably has structural units represented by any of the following general formulas (csa-1) to (csa-3).

In general formulas (csa-1) to (csa- ₃ ), L5 represents a single bond or a divalent linking group. In general formula (csa-3), _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.
Hereinafter, "SiO _1.5 " described in this specification is the same as above.

In general formulas (csa-1) to (csa- ₃ ), L5 represents a single bond or a divalent linking group. When 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.

In general formula (csa-3), _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.

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 and 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.

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.
In addition, the total solid content means all components other than the solvent.

(Radical polymerization initiator)
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. Further, 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.

(Cationic polymerization initiator)
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. More specifically, for example, at least one cation selected from aromatic sulfonium, aromatic iodonium, aromatic diazonium and pyridinium, and BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ and at least one anion selected from B(C ₆ F ₅ ) ₄ ⁻ , and cationic polymerization initiators such as onium salts and aluminum complexes.
A cationic polymerization initiator can be synthesized by a known method and is also available as a commercial product. Commercially available products include, for example, CI-1370, CI-2064, CI-2397, CI-2624, CI-2639, CI-2734, CI-2758, CI-2823, CI-2855 and CI-5102 manufactured by Nippon Soda Co., Ltd. etc., PHOTOINITIATOR 2047 manufactured by Rhodia, etc., UVI-6974, UVI-6990 manufactured by Union Carbite, CPI-10P, CPI-100P, CPI-101P, CPI-110P, TA-100 manufactured by Sun-Apro, etc., Sanshin Chemical Industry Co., Ltd. San-Aid SI-B2A, San-Aid SI-B3A and the like manufactured by San-Aid Co., Ltd. can be mentioned.

Specific commercial products of the iodonium salt-based photocationic polymerization initiator 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.

Only one type of cationic polymerization initiator may be used, or two or more types having different structures may be used in combination.
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.

(solvent)
The curable resin composition of the present invention may contain a solvent.
As the solvent, an organic solvent is preferable, and one or two or more organic solvents can be mixed in an arbitrary ratio and used. Specific examples of 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. , xylene and the like; glycol ethers such as propylene glycol monomethyl ether; acetic esters such as methyl acetate, ethyl acetate and butyl acetate; diacetone alcohol and the like.
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.

[Hard coat film]
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.

(Film thickness of hard coat layer)
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 μm, more preferably 1 to 25 μm, and more preferably 2 to 20 μm. 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.

<Base material>
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.

(polymer)
The substrate is preferably a plastic substrate and preferably comprises a polymer.
As the polymer, a polymer excellent in optical transparency, mechanical strength, thermal stability and the like is preferable.

Examples of polymers 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). 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.

In particular, 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. For example, 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.
As the amide-based polymer, aromatic polyamide (aramid-based polymer) is preferable.
The substrate preferably contains at least one polymer selected from imide-based polymers and aramid-based polymers.

(Thickness of base material)
The substrate is preferably film-like.
The thickness of the substrate is more preferably 100 μm or less, still more preferably 80 μm or less, and most preferably 50 μm or less. From the viewpoint of ease of handling of the substrate, the thickness of the substrate is preferably 3 μm or more, more preferably 5 μm or more, and most preferably 15 μm or more.

(Scratch resistance)
The hard coat film of the present invention has excellent scratch resistance.
As 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.
Evaluation environment conditions: 25°C, relative humidity 60%
Rubbing material: steel wool (manufactured by Japan Steel Wool Co., Ltd., grade No. #0000)
Wrap around the rubbing tip (1 cm x 1 cm) of the tester in contact with the sample and fix the band Moving distance (one way): 13 cm
Rubbing speed: 13 cm/sec Load: 100 g/cm ²
Tip contact area: 1 cm x 1 cm
Number of times of rubbing: 50 times reciprocating, 100 times reciprocating, 300 times reciprocating After the test, the surface of the hard coat film opposite to the rubbed surface (surface of the hard coat layer) (surface of base material) is painted with oil-based black ink, It is visually observed with reflected light, and the number of times of rubbing when a scratch occurs in the portion in contact with the steel wool is counted and evaluated.

<Scratch resistant layer>
The hard coat film of the present invention may further have a scratch resistant layer. When the hard coat film of the present invention has a scratch resistant layer, it preferably has a substrate, a hard coat layer, and a scratch resistant layer in this order.
Although 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).

(Radical 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. In addition, 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.

Only one type of compound (c1) may be used, or two or more types having different structures may be used in combination.

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. Preferably, 90% by mass or more is more preferable.

(Radical polymerization initiator)
The scratch-resistant layer-forming composition preferably contains a radical polymerization initiator.
One 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.

(solvent)
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.

(Other additives)
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.

(Film thickness of scratch resistant layer)
From the viewpoint of resistance to repeated bending, the thickness of the scratch-resistant layer is preferably less than 3.0 μm, more preferably 0.1 to 2.0 μm, and more preferably 0.1 to 1.0 μm. More preferred.

<Method for producing hard coat film>
A method for producing the hard coat film of the present invention will be described.
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. Preferably, 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 (preferably ionizing radiation) 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. For example, if 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.

In the case of thermal curing, 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.

The present invention will be described in more detail below with reference to examples, but the scope of the present invention should not be construed as being limited by these examples.

<Synthesis of Monomer m1>
A 2 L reactor equipped with a stirrer and a dropping funnel was charged with 100 g of glycerin monomethacrylate and 544 g of N,N-dimethylacetamide. It was added dropwise with a dropping funnel over a period of time. After raising the temperature to room temperature, the mixture was stirred at 25° C. for 4 hours to react. The resulting reaction solution was washed successively with an aqueous sodium hydrogencarbonate solution and saturated brine, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain 191 g of a monomer m1 represented by the following formula m1 (yield: 90 %).

<Synthesis of monomer m2>
A monomer m2 represented by the following formula m2 was synthesized according to the following scheme.

<Synthesis of b>
200 g of 2-acetylbutyrolactone (compound represented by formula a in the above scheme), 320 g of hydrogen bromide aqueous solution (48%) and 300 mL of toluene were weighed into a 2000 mL eggplant flask and stirred at 60° C. for 1 hour. The reaction solution was cooled to room temperature, transferred to a separating funnel, and 100 mL of hexane was added. The resulting organic layer was washed with 100 mL of saturated sodium bicarbonate solution containing 10 g of sodium thiosulfate and 100 mL of saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give compound b as a brown liquid ( , the compound represented by the formula b) was obtained in an amount of 260.0 g.

<Synthesis of c>
256 g of compound b, 165.6 g of trimethyl formate, 9 g of p-toluenesulfonic acid monohydrate and 400 mL of methanol were weighed into a 2000 mL eggplant flask and stirred at room temperature for 1 hour. 15 mL of diisopropylethylamine was added, and the solvent was distilled off with an evaporator. Add 500 mL of hexane and 50 mL of ethyl acetate, transfer to a separating funnel, separate and wash twice with 500 mL of a saturated aqueous sodium hydrogen carbonate solution, dry the resulting organic layer over anhydrous magnesium sulfate, and concentrate to give compound c as a brown liquid. 248.0 g of (compound represented by formula c in the above scheme) was obtained.

<Synthesis of d>
50 g of compound c, 0.45 g of p-toluenesulfonic acid monohydrate, 172.5 g of 1H,1H,2H,2H-perfluorohexan-1-ol, and 100 mL of hexane were weighed into a 500 mL eggplant flask and heated to 77°C. was fitted with a Dean Stark and stirred for 6 hours.
Then, 1 mL of diisopropylethylamine was added, and the solvent was distilled off using an evaporator. Add 700 mL of hexane and 400 mL of acetonitrile, transfer to a separating funnel, separate the hexane layer and concentrate with an evaporator to obtain 73.0 g of compound d (compound represented by formula d in the above scheme) as a brown liquid. .

<Synthesis of monomer m2>
50 g of compound d, 50 mg of dibutylhydroxytoluene (BHT), 1.23 g of potassium iodide, 12 g of sodium methacrylate, and 50 mL of N,N-dimethylacetamide were weighed into a 300 mL eggplant flask and stirred at 80° C. for 5 hours. . After cooling to room temperature, 200 mL of water was added, and after stirring for 5 minutes, the mixture was transferred to a separating funnel, and 200 mL of hexane and 20 mL of ethyl acetate were added. After shaking the separating funnel, the aqueous layer was removed. A saturated sodium chloride aqueous solution was added to separate and wash. The resulting organic layer was dried over anhydrous sodium sulfate, concentrated, and subjected to column chromatography to obtain 41 g of monomer m2.

<Synthesis of polymer (S-1)>
2.0 g of monomer m2, 1.71 g of cyclomer M100 (manufactured by Daicel Co., Ltd.), 6.29 g of monomer m1, 18.57 g of methyl ethyl ketone (MEK), 2,2′-azobis(isobutyrate) dimethyl (polymerization 2.85 g of an initiator (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was measured and stirred at 70° C. for 6 hours.
After the reaction, reprecipitation was performed using 500 mL of hexane. 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. While maintaining the resulting solution at 25° C., 31.09 g (0.07 mol) of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and biphenyltetracarboxylic dianhydride were added. 8.83 g (0.03 mol) of product (BPDA) was added and stirred for a certain period of time to react. After that, 20.302 g (0.1 mol) of terephthaloyl chloride (TPC) was added to obtain a polyamic acid solution with a solid concentration of 13% by mass. Next, 25.6 g of pyridine and 33.1 g of acetic anhydride were added to the polyamic acid solution, stirred for 30 minutes, further stirred at 70° C. for 1 hour, and then cooled to room temperature. 20 L of methanol was added thereto, and the precipitated solid matter was filtered and pulverized. Then, it was dried under vacuum at 100° C. for 6 hours to obtain 111 g of polyimide powder.

(Preparation of 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 μm.

[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 μm 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

(Manufacturing of hard coat film)
The curable resin composition HC-1 was bar-coated on a polyimide substrate K-1 having a thickness of 30 μm using a wire bar #18 so that the film thickness after curing was 18 μm. 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). .
In Comparative Example 5, 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.

(Evaluation of scratch resistance)
Using a rubbing tester, the surface of the hard coat layer of the hard coat film of each of the manufactured examples and comparative examples was subjected to a rubbing test under the following conditions to obtain an index of scratch resistance.
Evaluation environment conditions: 25°C, relative humidity 60%
Rubbing material: steel wool (manufactured by Japan Steel Wool Co., Ltd., grade No. #0000)
Wrap around the rubbing tip (1 cm x 1 cm) of the tester in contact with the sample and fix the band Moving distance (one way): 13 cm
Rubbing speed: 13 cm/sec Load: 100 g/cm ²
Tip contact area: 1 cm x 1 cm
Number of times of rubbing: 10 times reciprocating, 50 times reciprocating, 100 times reciprocating, 300 times reciprocating After the test, oily black was applied to the surface of the hard coat film opposite to the rubbed surface (surface of hard coat layer) (surface of base material). The ink was applied, and the surface was visually observed with reflected light, and the number of rubbing times when the portion in contact with the steel wool was scratched was counted and evaluated.
A: No scratches when rubbed back and forth 300 times B: No scratches when rubbed back and forth 100 times, but scratches when rubbed 300 times back and forth C: Scratches when rubbed 50 times back and forth D: No scratches when rubbed 10 times back and forth, but scratches when rubbed 50 times back and forth E: Scratches when rubbed 10 times back and forth

The results are shown in Table 1 below.

As shown in Table 1, the hard coat films of Examples 1 to 13 were excellent in scratch resistance.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is a Japanese patent application (Japanese patent application 2021-95314) filed on June 7, 2021, a Japanese patent application (Japanese patent application 2021-106802) filed on June 28, 2021, and a Japanese patent application filed on February 4, 2022 (Japanese Patent Application No. 2022-16722), the contents of which are incorporated herein by reference.

Claims

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

In the general formula (Z-1),
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. One or more —CH 2 — contained in the aliphatic group may be independently replaced with —CO—, —O— or —NR Z4 —. 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).

In general formulas (Ea-1) and (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.
With respect to all the structural units contained in the polymer (S), 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, and the 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% 2. The curable resin composition according to claim 1, wherein both Wa and Wb are not 0 mol %.
The curable resin composition according to claim 2, wherein the Wz satisfies 30mol%≤Wz≤95mol%.
4. The polymer (S) according to any one of claims 1 to 3, further comprising a structural unit (c) which is a structural unit different from the structural unit (b) and has hydroxyl bonding properties. curable resin composition.
With respect to all the structural units contained in the polymer (S), 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, and the constitution Where Wc is the content of the unit (c) based on the substance amount, and 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%. elastic resin composition.
The curable resin composition according to claim 4 or 5, wherein the structural unit (c) has at least one selected from the group consisting of boronic acid groups, isocyanate groups, aldehyde groups, and alkoxysilyl groups.
The curable resin composition according to any one of claims 1 to 6, wherein the polymer (S) has the structural unit (a), the structural unit (b) and the structural unit (z).
The curable resin composition according to any one of claims 1 to 7, wherein L Z1 in the general formula (Z-1) represents a w+1 valent aliphatic group.
Claim 1, wherein 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. 9. The curable resin composition according to any one of 8.
The curable resin composition according to any one of claims 1 to 9, wherein the total number of carbon atoms contained in L Z1 and L Z2 in general formula (Z-1) is 1 to 6.
The curable resin composition according to any one of claims 1 to 10, wherein the number of fluorine atoms contained in the structural unit (a) is 3 or more and 17 or less.
The curable resin composition according to any one of claims 1 to 11, wherein the structural unit (a) has a group represented by the following general formula (f-1).

In general formula (f-1), q1 represents an integer of 0 to 12, q2 represents an integer of 1 to 8, and Rq1 represents a hydrogen atom or a fluorine atom. * represents a binding position.
The curable resin composition according to any one of claims 1 to 12, wherein the structural unit (a) has a group represented by the following general formula (B1).

In general formula (B1),
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.
The curable resin composition according to any one of claims 1 to 13, wherein the structural unit (a) has a perfluoropolyether group.
The curable resin according to any one of claims 1 to 14, wherein the cationic polymerizable group of the structural unit (b) is a group represented by any one of the following general formulas (C1) to (C3). Composition.

In general formulas (C1) to (C3), * represents a bonding position. In general formula (C3), R 2 C represents a hydrogen atom or a substituent.
The curable resin composition according to any one of claims 1 to 15, wherein the polymer (S) has a weight average molecular weight of 5,000 to 200,000.
A hard coat film comprising a substrate and a hard coat layer formed from the curable resin composition according to any one of claims 1 to 16.
A method for producing a hard coat film comprising a substrate and a hard coat layer, wherein the curable resin composition according to any one of claims 1 to 16 is applied onto the substrate to form a coating film. and forming the hard coat layer by subjecting the coating film to a curing treatment.
The method for producing a hard coat film according to claim 18, wherein the curing treatment is a curing treatment using light and heat.