WO2022270442A1

WO2022270442A1 - Composition containing fluoropolyether group-containing compound

Info

Publication number: WO2022270442A1
Application number: PCT/JP2022/024402
Authority: WO
Inventors: 雅聡能勢; 健介茂原
Original assignee: ダイキン工業株式会社
Priority date: 2021-06-23
Filing date: 2022-06-17
Publication date: 2022-12-29
Also published as: JP2023003396A; JP7256428B2; KR20240023156A

Abstract

The present invention provides a composition containing a compound represented by the following formula (1) (where symbols are as described in the description).

Description

COMPOSITION CONTAINING FLUOROPOLYETHER GROUP-CONTAINING COMPOUND

The present disclosure relates to compositions containing fluoropolyether group-containing compounds.

It is known that a fluoropolyether group-containing compound can provide excellent water repellency, oil repellency, antifouling properties, etc. when used as an additive (Patent Document 1).

WO2021/024964

When a fluoropolyether group-containing compound is used as an additive in a resin composition, a film obtained from such a resin composition tends to have a high haze. Especially when the film thickness increases, this tendency becomes remarkable.

An object of the present disclosure is to provide a composition containing a fluoropolyether group-containing compound that can provide a low haze film.

The present disclosure includes the following aspects.
[1] Formula (1) below:

[In the formula:
RN is a trivalent organic group containing ^N ;
R ^F2 is -Rf ² _p -R ^F -O _q -;
Rf ² is a C _1-6 alkylene group optionally substituted by one or more fluorine atoms;
R ^F is a divalent fluoropolyether group;
p is 0 or 1;
q is 0 or 1;
X ^a is independently at each occurrence a single bond or a divalent organic group;
R ^A1 is independently at each occurrence an OR ^Ac group-containing group;
R ^Ac is a (meth)acryloyl group;
R ^B is independently at each occurrence R ^F1 -X ^a - or R ^A1 -X ^b -;
R ^F1 is Rf ¹ -R ^F -O _q -;
Rf ¹ is a C _1-16 alkyl group optionally substituted by one or more fluorine atoms;
X ^b is a divalent organic group containing at least two heteroatoms. ]
A composition comprising a compound represented by
[2] Furthermore, the following formula (2):

[In the formula:
RN is a trivalent organic group containing ^N ;
R ^F1 is Rf ¹ -R ^F -O _q -;
Rf ¹ is a C _1-16 alkyl group optionally substituted by one or more fluorine atoms;
R ^F is a divalent fluoropolyether group;
q is 0 or 1;
X ^a is a single bond or a divalent organic group;
R ^A1 is an OR ^Ac group-containing group;
R ^Ac is a (meth)acryloyl group;
X ^b is a divalent organic group containing at least two heteroatoms;
R ^B is R ^F1 -X ^a - or R ^A1 -X ^b -. ]
The composition according to [1] above, comprising a compound represented by
[3] Formula (1) is the following formula (1′):

[In the formula:
R ^F2 is -Rf ² _p -R ^F -O _q -;
Rf ² is a C _1-6 alkylene group optionally substituted by one or more fluorine atoms;
R ^F is a divalent fluoropolyether group;
p is 0 or 1;
q is 0 or 1;
X ^a is independently at each occurrence a single bond or a divalent organic group;
R ^A1 is independently at each occurrence an OR ^Ac group-containing group;
R ^Ac is a (meth)acryloyl group;
R ^B is independently at each occurrence R ^F1 -X ^a - or R ^A1 -X ^b -;
R ^F1 is Rf ¹ -R ^F -O _q -;
Rf ¹ is a C _1-16 alkyl group optionally substituted by one or more fluorine atoms;
X ^b is a divalent organic group containing at least two heteroatoms. ]
The composition according to [1] or [2] above.
[4] Formula (2) is the following formula (2′):

[In the formula:
R ^F1 is Rf ¹ -R ^F -O _q -;
Rf ¹ is a C _1-16 alkyl group optionally substituted by one or more fluorine atoms;
R ^F is a divalent fluoropolyether group;
q is 0 or 1;
X ^a is a single bond or a divalent organic group;
R ^A1 is an OR ^Ac group-containing group;
R ^Ac is a (meth)acryloyl group;
X ^b is a divalent organic group containing at least two heteroatoms;
R ^B is R ^F1 -X ^a - or R ^A1 -X ^b -. ]
The composition according to [2] or [3] above.
[5] R ^F is each independently represented by the formula:
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ R ^Fa ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f -
[wherein R ^Fa is independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom;
a, b, c, d, e and f are each independently an integer of 0 to 200, the sum of a, b, c, d, e and f is 1 or more; The order of existence of each repeating unit bracketed with c, d, e or f is arbitrary in the formula. ]
The composition according to any one of [1] to [4] above, which is a group represented by
[6] The composition according to [5] above, wherein R ^Fa is a fluorine atom.
[7] R ^F each independently represents the following formula (f1), (f2), (f3), (f4), (f5) or (f6):
-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)
[Wherein, d is an integer of 1 to 200, and e is 0 or 1. ],
-(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2)
[wherein c and d are each independently an integer of 0 to 30;
e and f are each independently an integer from 1 to 200;
the sum of c, d, e and f is an integer from 10 to 200;
The order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula. ],
-(R ⁶ -R ⁷ ) _g - (f3)
[wherein R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or two or three groups selected from these groups. is a combination of groups;
g is an integer from 2 to 100; ],
—(R ⁶ —R ⁷ ) _g —R ^r —(R ^7′ —R ^6′ ) _g′ − (f4)
[wherein R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or 2 independently selected from these groups or a combination of three groups,
R ^6' is OCF ₂ or OC ₂ F ₄ ;
R ^7′ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or independently selected from these groups a combination of two or three groups,
g is an integer from 2 to 100,
g' is an integer from 2 to 100,
^Rr is

(In the formula, * indicates the binding position.)
is. ];
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ F ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f - (f5)
[Wherein, e is an integer of 1 or more and 200 or less, a, b, c, d and f are each independently an integer of 0 or more and 200 or less, and a, b, c, d, e and f are at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula. ]
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ F ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f - (f6)
[Wherein, f is an integer of 1 or more and 200 or less, a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and a, b, c, d, e and f are at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula. ]
The composition according to any one of [1] to [4] above, which is a group represented by
[8] X ^a is the following formula:
-(CX ¹²¹ X ¹²² ) _x1 -(X ^a1 ) _y1 -(CX ¹²³ X ¹²⁴ ) _z1 -
[In the formula,
X ¹²¹ to X ¹²⁴ are each independently H, F, OH or —OSi(OR ¹²¹ ) ₃ (wherein three R ¹²¹ are each independently an alkyl group having 1 to 4 carbon atoms ) and
X ^a1 is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O- , or -NHC(=O)NH-, where the left side of each bond is attached to CX ¹²¹ X ¹²² .
x1 is an integer of 0-10, y1 is 0 or 1, and z1 is an integer of 1-10. ]
The composition according to any one of [1] to [7] above, which is a group represented by
[9] Any one of [1] to [8] above, wherein X ^a is a group represented by —(CH ₂ ) _m22 — (wherein m22 is an integer of 1 to 3) The composition according to .
[10] R ^A1 is -R ^A6 -R ^A4 -OR ^AC or -R ^A6 -R ^A5 -(OR ^AC ) ₂ ;
R ^A4 is a C _1-10 alkylene group,
R ^A5 is a trivalent hydrocarbon group having 1 to 10 carbon atoms,
R ^A6 is a single bond or -C _1-10 alkylene-O-;
^RAC is a (meth)acryloyl group,
The composition according to any one of [1] to [9] above.
[11] R ^A1 is -R ^A4 -OR ^AC or -R ^A5 -(OR ^AC ) ₂ ;
R ^A4 is a C _1-10 alkylene group,
R ^A5 is a trivalent hydrocarbon group having 1 to 10 carbon atoms,
^RAC is a (meth)acryloyl group,
The composition according to any one of [1] to [10] above.
[12] X ^b is -X ^c -X ^d -;
X ^c is a divalent organic group containing a heteroatom;
X ^d is -CO-NR ^d2 -, -OCO-NR ^d2 -, -NR ^d2 -CO-, or -NR ^d2 -COO-;
R ^d2 is a hydrogen atom or a C _1-6 alkyl group,
The composition according to any one of [1] to [11] above.
[13] X ^b is -X ^c -X ^d -;
X ^c is a divalent organic group containing a heteroatom;
X ^d is -CO-NR ^d2 -;
R ^d2 is a hydrogen atom or a C _1-6 alkyl group,
The composition according to any one of [1] to [12] above.
[14] R ^A1 is -R ^A5 -(OR ^AC ) ₂ ;
R ^A5 is a trivalent hydrocarbon group having 4 to 6 carbon atoms,
^RAC is a (meth)acryloyl group,
A composition according to any one of claims 1-13.
[15] X ^c is -[(R ^c1 ) _t1 -(X ^c1 ) _t2 ]-X ^c2 -;
R ^c1 at each occurrence is independently a single bond or a C _1-12 alkylene group;
X ^c1 is independently at _each occurrence O, NR ^x1 , S, SO or SO2;
each occurrence of R ^x1 is independently a hydrogen atom or a C _1-6 alkyl group;
X ^c2 is O or NR ^x2 ;
each occurrence of R ^x2 is independently a hydrogen atom or a C _1-6 alkyl group;
t1 is an integer from 1 to 6;
t2 is an integer from 1 to 6;
Here, in [(R ^c1 ) _t1 -(X ^c1 ) _t2 ], the order of existence of R ^c1 and X ^c1 is arbitrary in the formula,
The composition according to any one of [12] to [14] above.
[16] X ^c is —R ^c1′ —X ^c1 —R ^c1″ —X ^c2 —;
R ^c1′ is a C _1-6 alkylene group,
R ^c1″ is a C _1-12 alkylene group,
X ^c1 is O, NR ^x1 , S, SO or _SO2 ,
each occurrence of R ^x1 is independently a hydrogen atom or a C _1-6 alkyl group;
X ^c2 is O or NR ^x2 ;
each occurrence of R ^x2 is independently a hydrogen atom or a C _1-6 alkyl group;
The composition according to any one of [12] to [15] above.
[17] X ^c is —R ^c1′ —X ^c1 —R ^c1″ —X ^c2 —;
R ^c1′ is a C _2-4 alkylene group,
R ^c1″ is a C _2-12 alkylene group,
X ^c1 is S;
The composition according to any one of [12] to [16] above, wherein X ^c2 is O.
[18] The composition according to any one of [1] to [17] above, wherein R ^B is R ^A1 -X ^b -.
[19] The content of the compound represented by formula (1) is 10 to 90 mol% with respect to the total amount of the compound represented by formula (1) and the compound represented by formula (2). , the composition according to any one of [2] to [18] above.
[20] The composition according to any one of [1] to [19] above, which is an ink-repellent agent.
[21] The composition according to any one of [1] to [19] above, which is an additive for a resist resin composition.
[22] A curable composition comprising the composition according to any one of [1] to [19] above; and a matrix-forming composition.
[23] A substrate, and a layer formed on the surface of the substrate from the surface treatment agent according to any one of [1] to [19] above or the curable composition according to [22] above. Articles containing
[24] The article according to [23] above, wherein the article is an optical member.
[25] The composition according to any one of [1] to [19] above,
an alkali-soluble resin, and a polymerization initiator,
A resist resin composition comprising:
[26] The resist resin composition according to [25] above, which is for bank resist formation.

A composition containing the fluoropolyether group-containing compound of the present disclosure can provide a substrate with a surface treatment layer having water repellency, oil repellency, or antifouling properties and low haze.

As used herein, the term "organic group" means a monovalent group containing carbon. A monovalent organic group may be a hydrocarbon group or a derivative thereof unless otherwise specified. Derivatives of hydrocarbon groups have one or more of N, O, S, Si, amide, sulfonyl, sulfoxide, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain. means a group. Moreover, a "divalent organic group" means a divalent group containing carbon. Examples of such divalent organic groups include, but are not particularly limited to, divalent groups in which one hydrogen atom is further eliminated from an organic group.

As used herein, "hydrocarbon group" means a group containing carbon and hydrogen from which one hydrogen atom has been removed from a hydrocarbon. Such hydrocarbon groups include, but are not limited to, C _1-20 hydrocarbon groups optionally substituted by one or more substituents, such as aliphatic hydrocarbon groups, aromatic A hydrocarbon group etc. are mentioned. The above "aliphatic hydrocarbon group" may be linear, branched or cyclic, and may be saturated or unsaturated. Hydrocarbon groups may also contain one or more ring structures.

As used herein, the substituent of the "hydrocarbon group" is not particularly limited, but for example, a halogen atom, C _1-6 alkyl optionally substituted by one or more halogen atoms group, C _2-6 alkenyl group, C _2-6 alkynyl group, C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl groups, C _6-10 aryl groups and 5-10 membered heteroaryl groups.

A composition containing the fluoropolyether group-containing compound of the present disclosure will be described below.

The present disclosure provides the following formula (1):

[In the formula:
RN is a trivalent organic group containing ^N ;
R ^F2 is -Rf ² _p -R ^F -O _q -;
Rf ² is a C _1-6 alkylene group optionally substituted by one or more fluorine atoms;
R ^F is a divalent fluoropolyether group;
p is 0 or 1;
q is 0 or 1;
X ^a is independently at each occurrence a single bond or a divalent organic group;
R ^A1 is independently at each occurrence an OR ^Ac group-containing group;
R ^Ac is a (meth)acryloyl group;
R ^B is independently at each occurrence R ^F1 -X ^a - or R ^A1 -X ^b -;
R ^F1 is Rf ¹ -R ^F -O _q -;
Rf ¹ is a C _1-16 alkyl group optionally substituted by one or more fluorine atoms,
X ^b is a divalent organic group containing at least two heteroatoms. ]
A composition is provided comprising a compound represented by

RN is a trivalent organic group containing ^N.

The above R ^N is preferably the following group:

can be

In a preferred embodiment, R ^N is:

can be

In such embodiments, formula (1) is represented by formula (1′) below:

[In the formula, each symbol has the same meaning as the above formula (1). ]
is represented by

R ^F2 is -Rf ² _p -R ^F -O _q -.

Rf ² above is a C _1-6 alkylene group optionally substituted with one or more fluorine atoms.

The "C _1-6 alkylene group" in the C _1-6 alkylene group optionally substituted by one or more fluorine atoms may be linear or branched, preferably is a linear or branched C _1-3 alkylene group, more preferably a linear C _1-3 alkylene group.

Rf ² above is preferably a C _1-6 alkylene group substituted with one or more fluorine atoms, more preferably a C _1-6 perfluoroalkylene group, still more preferably C _{1- 3} is a perfluoroalkylene group.

The C _1-6 perfluoroalkylene group may be linear or branched, preferably a linear or branched C _1-3 perfluoroalkylene group, more preferably is a linear C _1-3 perfluoroalkyl group, specifically -CF ₂ -, -CF ₂ CF ₂ -, or -CF ₂ CF ₂ CF ₂ -.

The above p is 0 or 1. In one aspect, p is zero. In another aspect, p is 1.

The above q is 0 or 1. In one aspect, q is zero. In another aspect q is 1.

Each R ^F above is independently a divalent fluoropolyether group.

R ^F preferably has the formula:
-(OC _x1 F _2x1 ) _y1 -(OC _x2 F _x2-2 ) _y2 -
[In the formula:
x1 is independently for each (OC _x1 F _2x1 ) an integer from 1 to 6;
x2 is independently for each (OC _x2 F _2x2-2 ) an integer from 1 to 6;
y1 is an integer from 0 to 300,
y2 is an integer from 0 to 300,
the sum of y1 and y2 is 1 or more;
The order of existence of each repeating unit bracketed with y1 or t2 is arbitrary in the formula. ]
is a group represented by

OC _x1 F _2x1 may be linear or branched. OC _x2 F _2x2-2 may contain an unsaturated bond and may contain a ring structure.

The ring structure may be the following three-, four-, five-, or six-membered ring.

[In the formula, * indicates a binding position. ]

The ring structure is preferably a four-, five- or six-membered ring, more preferably a four- or six-membered ring.

The repeating unit having a ring structure can preferably be the following units.

[In the formula, * indicates a binding position. ]

R ^F preferably has the formula:
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ R ^Fa ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f -
[In the formula:
R ^Fa is independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom;
a, b, c, d, e and f are each independently integers from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order of existence of each repeating unit bracketed with a, b, c, d, e or f is arbitrary in the formula. ]
is a group represented by

^RFa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom.

a, b, c, d, e and f may preferably each independently be an integer from 0 to 100.

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

These repeating units may be linear or branched. For example, the repeating units are -(OC ₆ F ₁₂ )-, -(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ CF ₂ CF ₂ ) -, - (OCF ₂ CF (CF ₃ ) CF ₂ CF ₂ CF ₂ ) -, - (OCF ₂ CF ₂ CF (CF ₃ ) CF ₂ CF ₂ ) -, - (OCF ₂ CF ₂ CF ₂ CF (CF ₃ )CF ₂ )-, -(OCF ₂ CF ₂ CF ₂ CF ₂ CF(CF ₃ ))-, and the like. - ₍ _OC5F10 )- is - ₍ _{OCF2CF2CF2CF2CF2} )-, - ₍ _OCF ₍ _CF3 ) _CF2CF2CF2 )-, - ₍ _OCF2CF ₍ _CF3 ) CF ₂ CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ )CF ₂ )-, -(OCF ₂ CF ₂ CF ₂ CF(CF ₃ ))- and the like. -( _OC4F8 )- is - ₍ _{OCF2CF2CF2CF2} )-, - ₍ OCF ₍ _CF3 ) _CF2CF2 )-, - ₍ _OCF2CF ₍ _CF3 ) _CF2 )- , -( _OCF2CF2CF ( _CF3 ))-, -(OC( _CF3 ) _2CF2 )-, -( _OCF2C _(CF3)2 ₎ _- , -(OCF ₍ _CF3 )CF( CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- and -(OCF ₂ CF(C ₂ F ₅ ))-. -(OC ₃ F ₆ )- (that is, in the above formula, R 3 ^Fa is a fluorine atom) is represented by -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- and -( OCF ₂ CF(CF ₃ ))—. -(OC ₂ F ₄ )- may be either -(OCF ₂ CF ₂ )- or -(OCF(CF ₃ ))-.

In one embodiment, the repeating unit is linear. By making the repeating unit linear, it is possible to improve the surface lubricity, friction durability, and the like of the surface treatment layer.

In one embodiment, the repeating unit is branched. By branching the repeating unit, the dynamic friction coefficient of the surface treatment layer can be increased.

In one embodiment, each R 1 ^F is independently a group represented by any one of the following formulas (f1) to (f6).
-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)
[In the formula, d is an integer of 1 to 200, and e is 0 or 1, preferably 1. ];
-(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2)
[Wherein, c and d are each independently an integer of 0 or more and 30 or less, e and f are each independently an integer of 1 or more and 200 or less,
the sum of c, d, e and f is greater than or equal to 2;
The order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula. ];
-(R ⁶ -R ⁷ ) _g - (f3)
[wherein R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or 2 independently selected from these groups or a combination of three groups,
g is an integer from 2 to 100; ];
—(R ⁶ —R ⁷ ) _g —R ^r —(R ^7′ —R ^6′ ) _g′ − (f4)
[wherein R ⁶ is OCF ₂ or OC ₂ F ₄ ;
R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or 2 independently selected from these groups or a combination of three groups,
R ^6' is OCF ₂ or OC ₂ F ₄ ;
R ^7′ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ or independently selected from these groups a combination of two or three groups,
g is an integer from 2 to 100,
g' is an integer from 2 to 100,
^Rr is

(In the formula, * indicates the binding position.)
is. ];
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ F ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f - (f5)
[Wherein, e is an integer of 1 or more and 200 or less, a, b, c, d and f are each independently an integer of 0 or more and 200 or less, and a, b, c, d, e and f are at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula. ]
- (OC ₆ F ₁₂ ) _a - (OC ₅ F ₁₀ ) _b - (OC ₄ F ₈ ) _c - (OC ₃ F ₆ ) _d - (OC ₂ F ₄ ) _e - (OCF ₂ ) _f - (f6)
[Wherein, f is an integer of 1 or more and 200 or less, a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and a, b, c, d, e and f are at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula. ]

In the above formula (f1), d is preferably an integer of 5-200, more preferably 10-100, still more preferably 15-50, for example 25-35. In one aspect, e is zero. In another aspect, e is 1. The -(OC ₃ F ₆ ) _d - is preferably a group represented by -(OCF ₂ CF ₂ CF ₂ ) _d - or -(OCF(CF ₃ )CF ₂ ) _d -, more preferably , -(OCF ₂ CF ₂ CF ₂ ) _d -.

In the above formula (f2), e and f are each independently an integer of preferably 5 or more and 200 or less, more preferably 10-200. Also, the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one aspect, the above formula (f2) is preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ ) _c -(OCF ₂ CF ₂ CF ₂ ) _d -(OCF ₂ CF ₂ ) _e -(OCF ₂ ) It is a group represented by _f- . In another embodiment, formula (f2) may be a group represented by -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -.

In formula (f3) above, R ⁶ is preferably OC ₂ F ₄ . In (f3) above, R ⁷ is preferably a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , or 2 independently selected from these groups, or A combination of three groups, more preferably a group selected from OC ₃ F ₆ and OC ₄ F ₈ . The combination of two or three groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited, but for example -OC ₂ F ₄ OC ₃ F ₆ -, -OC _2F4OC4F8- _, _-OC3F6OC2F4- _, _-OC3F6OC3F6- _, _-OC3F6OC4F8- _, _-OC4F8OC4F _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _8- _, _-OC4F8OC3F6- _, _-OC4F8OC2F4- _, _{-OC2F4OC2F4OC3F6-} _, _{-OC2F4OC2F4OC} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _4F8- _, _{-OC2F4OC3F6OC2F4-} _, _{-OC2F4OC3F6OC3F6-} _, _{-OC2F4OC4F8OC2F4-} _, _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{-OC3F6OC2F4OC2F4-} _, _{-OC3F6OC2F4OC3F6-} _, _{-OC3F6OC3F6OC2F4-} _, _and _-OC4F _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} ₈ OC ₂ F ₄ OC ₂ F ₄ - and the like. In the above formula (f3), g is an integer of preferably 3 or more, more preferably 5 or more. Said g is preferably an integer of 50 or less. In formula (f3) above, OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ may be linear or branched, preferably linear. is a chain. In this aspect, the above formula (f3) is preferably -(OC ₂ F ₄ -OC ₃ F ₆ ) _g - or -(OC ₂ F ₄ -OC ₄ F ₈ ) _g -.

In formula (f4) above, R ⁶ , R ⁷ and g have the same meanings as in formula (f3) above, and have the same aspects. R ^6′ , R ^7′ and g′ have the same meanings as R ⁶ , R ⁷ and g in formula (f3) above, respectively, and have the same aspects. R ^r is preferably

[In the formula, * indicates a binding position. ]
and more preferably

[In the formula, * indicates a binding position. ]
is.

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

In the above formula (f6), f is preferably an integer of 1 or more and 100 or less, more preferably 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.

In one aspect, R ^F is a group represented by the formula (f1).

In one aspect, R ^F is a group represented by the formula (f2).

In one aspect, R ^F is a group represented by the formula (f3).

In one aspect, R ^F is a group represented by the formula (f4).

In one aspect, R ^F is a group represented by the formula (f5).

In one aspect, R ^F is a group represented by the formula (f6).

In the above RF, the ratio of e to ^f (hereinafter referred to as “e/f ratio”) is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2. Yes, more preferably 0.2 to 1.5, still more preferably 0.2 to 0.85. By setting the e/f ratio to 10 or less, the slipperiness, friction durability and chemical resistance (for example, durability against artificial perspiration) of the surface treatment layer obtained from this compound are further improved. The smaller the e/f ratio, the more improved the sliding property and friction durability of the surface treatment layer. On the other hand, by setting the e/f ratio to 0.1 or more, the stability of the compound can be further enhanced. The higher the e/f ratio, the more stable the compound.

In one aspect, the e/f ratio is preferably 0.2 to 0.95, more preferably 0.2 to 0.9.

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

In the fluoropolyether group-containing compound, the number average molecular weight of R ^F1 is not particularly limited, but is for example 500 to 30,000, preferably 1,500 to 30,000, more preferably 2,000 to 10,000. In this specification, the number average molecular weights of R ^F1 and R ^F2 are values measured by ¹⁹ F-NMR.

In another embodiment, R ^F1 has a number average molecular weight of 500 to 30,000, preferably 1,000 to 20,000, more preferably 2,000 to 15,000, even more preferably 2,000 to 10,000. 000, for example 3,000 to 6,000.

In another aspect, R ^F1 may have a number average molecular weight of 4,000 to 30,000, preferably 5,000 to 10,000, more preferably 6,000 to 10,000.

Each occurrence of X ^a above is independently a single bond or a divalent organic group.

X ^a above is a single bond or a divalent linking group linking R ^F2 and R ^N in the groups at both ends, ie, the formula (1). X ^a is preferably a single bond, an alkylene group, or a divalent group containing at least one bond selected from the group consisting of an ether bond and an ester bond, and is a single bond or an alkylene group having 1 to 10 carbon atoms. , or a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one bond selected from the group consisting of an ether bond and an ester bond is more preferable.

X ^a is represented by the following formula:
-(CX ¹²¹ X ¹²² ) _x1 -(X ^a1 ) _y1 -(CX ¹²³ X ¹²⁴ ) _z1 -
(Wherein, X ¹²¹ to X ¹²⁴ are each independently H, F, OH, or —OSi(OR ¹²¹ ) ₃ (Wherein, three R ¹²¹ each independently have 1 to is an alkyl group of 4.),
X ^a1 above is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O -, or -NHC(=O)NH- (the left side of each bond is attached to CX ¹²¹ X ¹²² ),
x1 is an integer of 0-10, y1 is 0 or 1, and z1 is an integer of 1-10. )
A group represented by is more preferable.

The above X ^a1 is preferably -O- or -C(=O)O-.

As the above X ^a , the following formula:
-(CF ₂ ) _m11 -(CH ₂ ) _m12 -O-(CH ₂ ) _m13 -
(Wherein, m11 is an integer of 1 to 3, m12 is an integer of 1 to 3, and m13 is an integer of 1 to 3.)
A group represented by
-(CF ₂ ) _m14 -(CH ₂ ) _m15 -O-CH ₂ CH(OH)-(CH ₂ ) _m16 -
(Wherein, m14 is an integer of 1 to 3, m15 is an integer of 1 to 3, and m16 is an integer of 1 to 3.)
A group represented by
-(CF ₂ ) _m17 -(CH ₂ ) _m18 -
(Wherein, m17 is an integer of 1 to 3, and m18 is an integer of 1 to 3.)
A group represented by
-(CF ₂ ) _m19 -(CH ₂ ) _m20 -O-CH ₂ CH(OSi(OCH ₃ ) ₃ )-(CH ₂ ) _m21 -
(Wherein, m19 is an integer of 1 to 3, m20 is an integer of 1 to 3, and m21 is an integer of 1 to 3.)
or a group represented by
-( _CH2 ) _m22-
(Wherein, m22 is an integer of 1 to 3.)
A group represented by is particularly preferred.

The above X ^a is not particularly limited, but specifically,
—CH ₂ —, —C ₂ H ₄ —, —C ₃ H ₆ —, —C ₄ H ₈ —, —C ₄ H ₈ —O—CH ₂ —, —CO—O—CH ₂ —CH(OH) —CH ₂ —, —(CF ₂ ) _n5 — (n5 is an integer of 0 to 4), —(CF ₂ ) _n5 —(CH ₂ ) _m5 — (n5 and m5 are each independently 0 4), —CF ₂ CF ₂ CH ₂ OCH ₂ CH(OH)CH ₂ —, —CF ₂ CF ₂ CH ₂ OCH ₂ CH(OSi(OCH ₃ ) ₃ )CH ₂ —
etc.

R ^A1 above is independently at each occurrence an OR ^Ac group-containing group.

R ^Ac is a (meth)acryloyl group. Here, in the present specification, "(meth)acryloyl group" includes acryloyl group and methacryloyl group.

By containing a (meth)acryloyl group, the compound of the present disclosure can improve the solubility in solvents and further improve the friction durability of the surface treatment layer obtained from such a compound.

In one aspect, the ^RAC is an acryloyl group.

In another aspect, the R ^AC is a methacryloyl group.

In a preferred embodiment, R ^A1 is -R ^A6 -R ^A4 -OR ^AC or -R ^A6 -R ^A5 -(OR ^AC ) ₂ .

In one embodiment, R ^A1 is -R ^A4 -OR ^AC or -R ^A5 -(OR ^AC ) ₂ .

In one embodiment, R ^A1 is -R ^A4 -OR ^AC or -R ^A6 -R ^A4 -OR ^AC . By setting R ^A1 to -R ^A4 -OR ^AC or -R ^A6 -R ^A4 -OR ^AC , the initial contact angle of the surface treatment layer obtained from the compound of the present disclosure can be increased.

In another embodiment, R ^A1 is -R ^A5 -(OR ^AC ) ₂ or -R ^A6 -R ^A5 -(OR ^AC ) ₂ . By setting R ^A1 to -R ^A5 -(OR ^AC ) ₂ or -R ^A6 -R ^A5 -(OR ^AC ) ₂ , the solubility of the compounds of the present disclosure in solvents can be further improved, and the present disclosure The durability of the surface treatment layer obtained from the compound of (1) can be further enhanced.

R ^A4 above is a C _1-10 alkylene group, preferably a C _2-6 alkylene group, more preferably a C _2-4 alkylene group.

R ^A5 is a trivalent hydrocarbon group having 1 to 10 carbon atoms, preferably a trivalent hydrocarbon group having 4 to 6 carbon atoms.

In preferred embodiments, R ^A5 is the following group.

(Where * binds to OR ^AC and ** binds to ^Xb .)

R ^A6 is a single bond or -C _1-10 alkylene-O-,

In one embodiment, R ^A6 is a single bond.

In another aspect, R ^A6 above is -C _1-10 alkylene-O-.

The above -C _1-10 alkylene-O- is preferably -C _1-6 alkylene-O-, more preferably -C _2-6 alkylene-O-, still more preferably -C _2-4 alkylene-O- could be.

X ^b above is a divalent organic group containing at least two heteroatoms.

By containing at least two heteroatoms in ^Xb , the compound of the present disclosure can further improve the solubility in solvents, and further improve the friction durability of the surface treatment layer obtained from such a compound. .

In a preferred embodiment, X ^b is -X ^c -X ^d -.

X ^c above is a divalent organic group containing a heteroatom.

In a preferred embodiment, X ^c is represented by the following formula -[(R ^c1 ) _t1 -(X ^c1 ) _t2 ]-X ^c2 -
[In the formula,
R ^c1 at each occurrence is independently a single bond or a C _1-12 alkylene group;
X ^c1 is independently at _each occurrence O, NR ^x1 , S, SO or SO2;
each occurrence of R ^x1 is independently a hydrogen atom or a C _1-6 alkyl group;
X ^c2 is O or NR ^x2 ;
each occurrence of R ^x2 is independently a hydrogen atom or a C _1-6 alkyl group;
t1 is an integer from 1 to 6;
t2 is an integer from 1 to 6;
Here, in [(R ^c1 ) _t1 -(X ^c1 ) _t2 ], the order of existence of R ^c1 and X ^c1 is arbitrary in the formula]
is a group represented by

By having the above group as ^Xc , the compound of the present disclosure can further improve the friction durability of the surface-treated layer obtained from such a compound.

In one aspect, R ^c1 is independently at each occurrence a C _1-12 alkylene group.

In R ^c1 above, the C _1-12 alkylene group is preferably a C _1-10 alkylene group, more preferably a C _2-10 alkylene group, such as a C _2-9 alkylene group.

Each occurrence of X ^c1 above is independently preferably -S-, -SO- or -SO ₂ -, more preferably -S-.

^Xc2 above is preferably O.

The above t1 is an integer of 1 to 6, preferably an integer of 2 to 4, more preferably 2 to 3, still more preferably 2.

The above t2 is an integer of 1 to 6, preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and still more preferably 1.

In a preferred embodiment, t1 is 2 and t2 is 1.

In a preferred embodiment,
X ^c is —R ^c1′ —X ^c1 —R ^c1″ —X ^c2 —;
R ^c1′ is a C _1-6 alkylene group,
R ^c1″ is a C _1-12 alkylene group,
X ^c1 is O, NR ^x1 , S, SO or _SO2 ,
each occurrence of R ^x1 is independently a hydrogen atom or a C _1-6 alkyl group;
X ^c2 is O or NR ^x2 ;
Each occurrence of R ^x2 is independently a hydrogen atom or a C _1-6 alkyl group.

In a more preferred embodiment,
X ^c is —R ^c1′ —X ^c1 —R ^c1″ —X ^c2 —;
R ^c1′ is a C _1-6 alkylene group,
R ^c1″ is a C _1-12 alkylene group,
X ^c1 is S, SO or _SO2 ,
X ^c2 is O;

In a further preferred embodiment,
X ^c is —R ^c1′ —X ^c1 —R ^c1″ —X ^c2 —;
R ^c1′ is a C _2-4 alkylene group,
R ^c1″ is a C _2-12 alkylene group,
X ^c1 is S;
X ^c2 is O;

X ^d above is -CO-NR ^d2 -, -OCO-NR ^d2 -, -NR ^d2 -CO-, or -NR ^d2 -COO-.

R ^d2 above is a hydrogen atom or a C _1-6 alkyl group,

In a preferred embodiment, X ^d above is -CO-NR ^d2 -.

Each occurrence of R ^B above is independently R ^F1 -X ^a - or R ^A1 -X ^b -. Here, when R ^B is R ^F1 -X ^a -, a plurality of R ^F1 -X ^a - are present in the formula, and these may be the same or different. Similarly, when R ^B is R ^A1 -X ^b -, there are multiple instances of R ^A1 -X ^b - in the formula, which may be the same or different.

In one aspect, R ^B is R ^F1 -X ^a -. By setting R ^B to R ^F1 —X ^a —, the initial contact angle of the surface-treated layer obtained from the compound of the present disclosure can be increased.

In a preferred embodiment, R ^B is R ^A1 -X ^b -. By setting R ^B to R ^A1 -X ^b -, the solubility of the compound of the present disclosure in a solvent can be further improved, and the durability of the surface treatment layer obtained from the compound of the present disclosure can be further increased. .

The number average molecular weight of the fluorine-containing isocyanuric compounds represented by the above formulas (1) and (2) is not particularly limited, but is for example 1,000 to 30,000, preferably 2,000 to 20,000. , more preferably 2,500 to 6,000, still more preferably 2,500 to 5,000. In this specification, the number average molecular weight of the fluorine-containing isocyanurate compound is a value measured by ¹⁹ F-NMR. By setting the number average molecular weight of the fluorine-containing isocyanurate compound within the above range, the solubility of the fluorine-containing isocyanurate compound in solvents is improved. Moreover, the initial contact angle and friction durability of the surface treatment layer obtained from the compound can be improved.

In one aspect, the composition of the present disclosure has the following formula (2):

[In the formula:
RN is a trivalent organic group containing ^N ;
R ^F1 is Rf ¹ -R ^F -O _q -;
Rf ¹ is a C _1-16 alkyl group optionally substituted by one or more fluorine atoms;
R ^F is a divalent fluoropolyether group;
q is 0 or 1;
X ^a is a single bond or a divalent organic group;
R ^A1 is an OR ^Ac group-containing group;
R ^Ac is a (meth)acryloyl group;
X ^b is a divalent organic group containing at least two heteroatoms;
R ^B is R ^F1 -X ^a - or R ^A1 -X ^b -. ]
Including the compound represented by.

R ^N , X ^a , X ^b , R ^A1 , and R ^B have the same meanings as in formula (1) above.

In a preferred embodiment, R ^N is:

can be In such embodiments, formula (2) is represented by formula (2′) below:

[In the formula, each symbol has the same meaning as the above formula (2). ]
is represented by

R ^F1 is Rf ¹ —R ^F —O _q —.

In the above formula, Rf ¹ is a C _1-16 alkyl group optionally substituted by one or more fluorine atoms.

The "C _1-16 alkyl group" in the C _1-16 alkyl group optionally substituted by one or more fluorine atoms may be linear or branched, preferably is a straight or branched C _1-6 alkyl group, especially a C _1-3 alkyl group, more preferably a straight chain C _1-6 alkyl group, especially a C _1-3 alkyl group.

Rf ¹ above is preferably a C _1-16 alkyl group substituted with one or more fluorine atoms, more preferably a CF ₂ H—C _1-15 perfluoroalkylene group, still more preferably It is a C _1-16 perfluoroalkyl group.

Said C _1-16 perfluoroalkyl groups may be linear or branched, preferably linear or branched C _1-6 perfluoroalkyl groups, especially C _1-3 perfluoroalkyl groups. an alkyl group, more preferably a linear C _1-6 perfluoroalkyl group, especially a C _1-3 perfluoroalkyl group, specifically -CF ₃ , -CF ₂ CF ₃ or -CF ₂ CF ₂ CF ₃ is.

In one aspect, in the composition of the present disclosure, the compound represented by formula (1) is 100 in mol %. That is, the composition of the present disclosure contains the compound represented by formula (1) and does not contain the compound represented by formula (2).

In another aspect, in the composition of the present disclosure, relative to the sum of the compound represented by formula (1) and the compound represented by formula (2), the compound represented by formula (1) is preferably is 1 mol % or more and 99 mol % or less. The lower limit of the content of the compound represented by formula (1) with respect to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 10 mol%, more preferably 20 mol %, more preferably 50 mol %, even more preferably 60 mol %, such as 70 mol %, 80 mol %, or 90 mol %. The upper limit of the content of the compound represented by formula (1) with respect to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 95 mol%, for example 90 mol%, It can be 80 mol % or 70 mol %. The compound represented by formula (2) with respect to the total of the compound represented by formula (1) and the compound represented by formula (2) is preferably 10 mol% or more and 99 mol% or less, more preferably 20 mol % or more and 95 mol % or less, for example, 50 mol % or more and 95 mol % or less.

The compound represented by the above formula (1) can be synthesized, for example, as follows.

Formula (1a) below:

[In the formula:
R ^F2 is -Rf ² _p -R ^F -O _q -;
Rf ² is a C _1-6 alkylene group optionally substituted by one or more fluorine atoms;
R ^F is a divalent fluoropolyether group;
p is 0 or 1;
q is 0 or 1;
X ^a is a single bond or a divalent organic group;
R ^Ba is R ^F1 —X ^a — or an allyl group;
R ^F1 is Rf ¹ -R ^F -O _q -;
Rf ¹ is a C _1-16 alkyl group optionally substituted by one or more fluorine atoms. ]
to the compound represented by the following formula (1b)
HX ^c1 -R ^b2 -OH (1b)
[In the formula:
X ^c1 is independently at _each occurrence O, NR ^x1 , S, SO or SO2;
each occurrence of R ^x1 is independently a hydrogen atom or a C _1-6 alkyl group;
R ^b2 is a C _1-10 alkylene group. ]
By reacting a compound represented by the following formula (1c):

[In the formula:
R ^F1 , Rf ¹ , R ^F , q, X ^a , X ^c1 and R ^b2 have the same meanings as above;
R ^Bb is R ^F1 —X ^a — or —(CH ₂ ) ₃ —X ^c1 —R ^b2 —OH. ]
A compound represented by is obtained.

Furthermore, to the compound represented by the formula (1c) obtained above, the following formula (1d)
OCN-R ^A1 (1d)
can be reacted to provide compounds of formula (1) of the present disclosure.

The composition of the present disclosure can be used for various purposes.

The compounds of the present disclosure can be used together with polymerizable coating agent monomers. A composition characterized by comprising a compound of the present disclosure and a polymerizable coating agent monomer is also one aspect of the present invention (sometimes referred to herein as composition (a)). Since the composition (a) has the above structure, the composition (a) has a large static contact angle with respect to water or n-hexadecane, is transparent, has excellent releasability, is resistant to fingerprints, and can be completely wiped off even if fingerprints are attached. A coating film is obtained which can be

A monomer having a carbon-carbon double bond is preferable as the polymerizable coating agent monomer.

Examples of the polymerizable coating agent monomer include, but are not particularly limited to, monofunctional and/or polyfunctional acrylates and methacrylates (hereinafter, acrylates and methacrylates are collectively referred to as "(meth)acrylates"), It means a composition containing compounds that are monofunctional and/or polyfunctional urethane (meth)acrylates, monofunctional and/or polyfunctional epoxy (meth)acrylates. The composition forming the matrix is not particularly limited, but is generally a hard coating agent or an antireflection agent, such as a hard coating agent containing a polyfunctional (meth)acrylate. Alternatively, an antireflection agent containing a fluorine-containing (meth)acrylate may be used. The hard coating agent is, for example, Beamset 502H, 504H, 505A-6, 550B, 575CB, 577, 1402 (trade name) from Arakawa Chemical Industries, Ltd., Daicel Cytec Co., Ltd. as EBECRYL40 (trade name), HR300. (trade name) from Yokohama Rubber Co., Ltd. The antireflection agent is commercially available from Daikin Industries, Ltd. as OPTOOL AR-110 (trade name), for example.

Composition (a) further contains an antioxidant, a thickener, a leveling agent, an antifoaming agent, an antistatic agent, an antifogging agent, an ultraviolet absorber, pigments, dyes, inorganic fine particles such as silica, aluminum paste, and talc. , glass frit, fillers such as metal powder, and polymerization inhibitors such as butylated hydroxytoluene (BHT) and phenothiazine (PTZ).

The composition (a) may further contain a urethanization catalyst, such as a tin-based catalyst, a titanium-based catalyst, a zirconia-based catalyst, a bismuth-based catalyst, or an organic amine-based catalyst.

Examples of the tin-based catalyst include di-n-butyltin (IV) dilaurate.
Examples of the titanium-based catalyst include titanium diisopropoxybis(ethylacetoacetate), titanium tetra-n-butoxide, titanium tetra-2-ethylhexoxide, and titanium tetraacetylacetonate.
Examples of the zirconia-based catalyst include zirconium tetraacetylacetonate, zirconium tetra-n-butoxide, and zirconium dibutoxybis(ethylacetoacetate).
Examples of the bismuth-based catalyst include bismuth tris(2-ethylhexanoate).
Examples of the organic amine-based catalyst include diazabicycloundecene.

The composition (a) preferably further contains a solvent. Examples of the solvent include fluorine-containing organic solvents and fluorine-free organic solvents.

Examples of the fluorine-containing organic solvent include perfluorohexane, perfluorooctane, perfluorodimethylcyclohexane, perfluorodecalin, perfluoroalkylethanol, perfluorobenzene, perfluorotoluene, perfluoroalkylamine (Fluorinert (trade name) etc.), perfluoroalkyl ether, perfluorobutyltetrahydrofuran, polyfluoroaliphatic hydrocarbon (Asahiklin AC6000 (trade name)), hydrochlorofluorocarbon (Asahiklin AK-225 (trade name), etc.), hydrofluoroether (Novec (trade name), HFE-7100 (trade name), HFE-7300 (trade name), etc.), 1,1,2,2,3,3,4-heptafluorocyclopentane, fluorine-containing alcohol, perfluoroalkyl bromide , perfluoroalkyl iodide, perfluoropolyether (Krytox (trade name), Demnum (trade name), Fomblin (trade name), etc.), 1,3-bistrifluoromethylbenzene, methacrylic acid 2-(perfluoro alkyl)ethyls, 2-(perfluoroalkyl)ethyl acrylates, perfluoroalkylethylenes, freon 134a, and hexafluoropropene oligomers.

Examples of the fluorine-free organic solvent include acetone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol. monobutyl ether acetate, dipropylene glycol dimethyl ether pentane, hexane, heptane, octane, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, carbon disulfide, benzene, toluene, xylene, nitrobenzene, diethyl ether, dimethoxyethane, diglyme, triglyme, ethyl acetate , butyl acetate, dimethylformamide, dimethylsulfoxide, 2-butanone, acetonitrile, benzonitrile, butanol, 1-propanol, 2-propanol, ethanol, methanol, and diacetone alcohol.

Among them, the solvent is preferably methyl isobutyl ketone, propylene glycol monomethyl ether, hexadecane, butyl acetate, acetone, 2-butanone, cyclohexanone, ethyl acetate, diacetone alcohol or 2-propanol.

The above solvents may be used singly or in combination of two or more.

The above solvent is preferably used in the composition (a) in a range of 30 to 95% by mass. More preferably, it is 50 to 90% by mass.

For example, an antifouling layer can be formed by applying the composition (a) to a substrate. It is also possible to form an antifouling layer by polymerizing after coating. Examples of the base material include resins (especially non-fluororesins).

The compounds of the present disclosure can be used with alkali-soluble resins, curable resins or curable monomers. A composition characterized by containing the above compound and a curable resin or a curable monomer is also one aspect of the present invention (herein sometimes referred to as composition (b)). Since the composition (b) has the above structure, it is possible to obtain a coating film which is resistant to fingerprints and which can be completely wiped off even if fingerprints are attached.

The curable resin may be either a photocurable resin or a thermosetting resin, and is not particularly limited as long as it has heat resistance and strength, but is preferably a photocurable resin, and an ultraviolet curable resin. more preferred.

Examples of the curable resin include acrylic polymers, polycarbonate polymers, polyester polymers, polyamide polymers, polyimide polymers, polyethersulfone polymers, cyclic polyolefin polymers, fluorine-containing polyolefin polymers (such as PTFE), Fluorine-containing cyclic amorphous polymers (Cytop (registered trademark), Teflon (registered trademark) AF, etc.) and the like.

Specific examples of the curable resin or monomers constituting the curable resin include alkyl vinyl ethers such as cyclohexylmethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, glycidyl vinyl ether, vinyl acetate, vinyl pivalate, various (meth) Acrylates: phenoxyethyl acrylate, benzyl acrylate, stearyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, allyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate , trimethylol, propane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, ethoxyethyl acrylate, methoxyethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyoxyethylene glycol Diacrylate, tripropylene glycol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl vinyl ether, N,N-diethylaminoethyl acrylate, N,N-dimethylaminoethyl acrylate, N-vinylpyrrolidone, dimethyl Aminoethyl methacrylate Silicon-based acrylate, maleic anhydride, vinylene carbonate, chain side chain polyacrylate, cyclic side chain polyacrylate polynorbornene, polynorbornadiene, polycarbonate, polysulfonic acid amide, fluorine-containing cyclic amorphous polymer (Cytop ( registered trademark), Teflon (registered trademark) AF, etc.).

The curable monomer may be either a photocurable monomer or a thermosetting monomer, but an ultraviolet curable monomer is preferred.

Examples of the curable monomer include (a) urethane (meth)acrylate, (b) epoxy (meth)acrylate, (c) polyester (meth)acrylate, (d) polyether (meth)acrylate, (e) silicone (meth)acrylates, (f) (meth)acrylate monomers, and the like.

Specific examples of the curable monomer include the following.
(a) Urethane (meth)acrylates include poly[(meth)acryloyloxyalkyl]isocyanurates typified by tris(2-hydroxyethyl)isocyanurate diacrylate and tris(2-hydroxyethyl)isocyanurate triacrylate. mentioned.
(b) Epoxy (meth)acrylate is obtained by adding a (meth)acryloyl group to an epoxy group, and bisphenol A, bisphenol F, phenol novolak, and alicyclic compounds are generally used as starting materials.
(c) Polyhydric alcohols constituting the polyester portion of polyester (meth)acrylate include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol, Polypropylene glycol, pentaerythritol, dipentaerythritol, etc., and polybasic acids include phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid, alkenylsuccinic acid, and the like.
(d) Polyether (meth)acrylates include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol-polypropylene glycol di(meth)acrylate and the like.
(e) Silicon (meth)acrylate is a dimethylpolysiloxane with a molecular weight of 1,000 to 10,000 modified with (meth)acryloyl groups at one or both ends. exemplified.

(f) (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate , sec-butyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, 3-methylbutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethyl-n-hexyl (meth)acrylate ) acrylate, n-octyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy Propyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, neopentyl glycol mono (meth)acrylate , 3-chloro-2-hydroxypropyl (meth)acrylate, (1,1-dimethyl-3-oxobutyl) (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1, Examples include 6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate.

Among the above-mentioned curable resins and curable monomers, the following are commercially available and preferable.

Examples of the curable resin include silicone resins PAK-01 and PAK-02 (manufactured by Toyo Gosei Chemical Co., Ltd.), nanoimprint resin NIF series (manufactured by Asahi Glass Co., Ltd.), nanoimprint resin OCNL series (manufactured by Tokyo Ohka Kogyo Co., Ltd.), NIAC2310 (Daicel Kagaku Kogyo Co., Ltd.), epoxy acrylate resins EH-1001, ES-4004, EX-C101, EX-C106, EX-C300, EX-C501, EX-0202, EX-0205, EX-5000, etc. (Kyoeisha Chemical Co., Ltd. (manufactured by Sumitomo Bayern Urethane), hexamethylene diisocyanate-based polyisocyanates, Sumidule N-75, Sumidule N3200, Sumidule HT, Sumidule N3300, and Sumidule N3500 (manufactured by Sumitomo Bayern Urethane).

Examples of the curable monomers include silicone acrylate resins, polyfunctional acrylates, polyfunctional methacrylates, and alkoxysilane group-containing (meth)acrylates.

Silicone acrylate resins include Silaplane FM-0611, Silaplane FM-0621, Silaplane FM-0625, double-ended (meth)acrylic Silaplane FM-7711, Silaplane FM-7721 and Silaplane FM -7725, etc., Silaplane FM-0411, Silaplane FM-0421, Silaplane FM-0428, Silaplane FM-DA11, Silaplane FM-DA21, Silaplane-DA25, single-ended (meth)acrylic Silaplane FM-0711, Silaplane FM-0721, Silaplane FM-0725, Silaplane TM-0701 and Silaplane TM-0701T (manufactured by JCN) and the like.

Polyfunctional acrylates include A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A -TMPT, A-TMMT (manufactured by Shin-Nakamura Kogyo Co., Ltd.) and the like.

Examples of polyfunctional methacrylates include TMPT (manufactured by Shin-Nakamura Kogyo Co., Ltd.).

Alkoxysilane group-containing (meth)acrylates include 3-(meth)acryloyloxypropyltrichlorosilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-( meth)acryloyloxypropyltriisopropoxysilane (also known as (triisopropoxysilyl)propyl methacrylate (abbreviation: TISMA) and triisopropoxysilyl)propyl acrylate), 3-(meth)acryloxyisobutyltrichlorosilane, 3-(meth) acryloxyisobutyltriethoxysilane, 3-(meth)acryloxyisobutyltriisopropoxy, 3-(meth)acryloxyisobutyltrimethoxysilane, and the like.

The composition (b) also preferably contains a cross-linking catalyst. Examples of the cross-linking catalyst include radical polymerization initiators and acid generators.

The radical polymerization initiator is a compound that generates radicals by heat or light, and includes radical thermal polymerization initiators and radical photopolymerization initiators. In the present invention, the above radical photopolymerization initiator is preferred.

Examples of the radical thermal polymerization initiator include diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diisopropyl peroxydicarbonate, Peroxycarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyoctoate, peroxide compounds such as alkyl peresters such as t-butyl peroxybenzoate, and azobis iso Radical-generating azo compounds such as butyronitrile and the like are included.

Examples of the radical photopolymerization initiator include -diketones such as benzyl and diacetyl, acyloins such as benzoin, acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, thioxanthone, 2,4- Thioxanthones such as diethylthioxanthone and thioxanthone-4-sulfonic acid, benzophenones such as benzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, acetophenone, 2-(4- Toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl[4-(methylthio)phenyl]-2-morpholino-1 -propanone, acetophenones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, anthraquinone, quinones such as 1,4-naphthoquinone, 2-dimethylaminobenzoic acid aminobenzoic acids such as ethyl, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, phenacyl chloride, Examples thereof include halogen compounds such as trihalomethylphenylsulfone, acylphosphine oxides, and peroxides such as di-t-butyl peroxide.

Commercially available products of the radical photopolymerization initiator are exemplified below.
IRGACURE 651: 2,2-dimethoxy-1,2-diphenylethan-1-one,
IRGACURE 184: 1-hydroxy-cyclohexyl-phenyl-ketone,
IRGACURE 2959: 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one,
IRGACURE 127: 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one,
IRGACURE 907: 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one,
IRGACURE 369: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,
IRGACURE 379: 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone,
IRGACURE 819: bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide,
IRGACURE 784: bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium,
IRGACURE OXE 01: 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)],
IRGACURE OXE 02: ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime),
IRGACURE261, IRGACURE369, IRGACURE500,
DAROCUR 1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one,
DAROCUR TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide,
DAROCUR1116, DAROCUR2959, DAROCUR1664, DAROCUR4043,
IRGACURE 754 oxyphenylacetic acid: a mixture of 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester and oxyphenylacetic acid, 2-(2-hydroxyethoxy)ethyl ester,
IRGACURE 500: a mixture of IRGACURE 184 and benzophenone (1
: 1),
IRGACURE 1300: a mixture of IRGACURE 369 and IRGACURE 651 (3:7);
IRGACURE 1800: a mixture of CGI403 and IRGACURE 184 (1:3),
IRGACURE 1870: a mixture of CGI403 and IRGACURE 184 (7:3);
DAROCUR 4265: a mixture of DAROCUR TPO and DAROCUR 1173 (1:1).
IRGACURE is manufactured by BASF, and DAROCUR is manufactured by Merck Japan.

When a radical photopolymerization initiator is used as the crosslinking catalyst, diethylthioxanthone, isopropylthioxanthone, or the like can be used in combination as a sensitizer, and DAROCUR EDB (ethyl-4-dimethylaminobenzoate) can be used as a polymerization accelerator. ), DAROCUR EHA (2-ethylhexyl-4-dimethylaminobenzoate), etc. may be used in combination.

When the sensitizer is used, the blending amount of the sensitizer is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin or curable monomer. More preferably, it is 0.1 to 2 parts by mass.

Further, when the polymerization accelerator is used, the amount of the polymerization accelerator to be blended is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin or curable monomer. More preferably, it is 0.1 to 2 parts by mass.

The acid generator is a material that generates acid by applying heat or light, and includes thermal acid generators and photoacid generators. In the present invention, photoacid generators are preferred.

Examples of the thermal acid generator include benzoin tosylate, nitrobenzyl tosylate (particularly 4-nitrobenzyl tosylate), other alkyl esters of organic sulfonic acids, and the like.

The photoacid generator is composed of a chromophore that absorbs light and an acid precursor that becomes an acid after decomposition. The acid generator is excited to generate acid from the acid precursor portion.

Examples of the photoacid generator include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, CF ₃ SO ₃ , p-CH ₃ PhSO ₃ , p-NO ₂ PhSO ₃ (where Ph is a phenyl group) and the like. Salts, organic halogen compounds, orthoquinone-diazide sulfonyl chlorides, sulfonate esters, and the like can be mentioned. In addition, as photoacid generators, 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds, 2-trihalomethyl-5-aryl-1,3,4-oxadiazole compounds, 2-trihalo Also included are methyl-5-hydroxyphenyl-1,3,4-oxadiazole compounds. The organic halogen compound is a compound that forms a hydrohalic acid (for example, hydrogen chloride).

Commercially available products of the photoacid generator are exemplified below.
Wako Pure Chemical Industries, Ltd. WPAG-145 [bis (cyclohexylsulfonyl) diazomethane], WPAG-170 [bis (t-butylsulfonyl) diazomethane], WPAG-199 [bis (p-toluenesulfonyl) diazomethane], WPAG-281 [triphenylsulfonium trifluoromethanesulfonate], WPAG-336 [diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate], WPAG-367 [diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate], Ciba Specialty Chemicals IRGACURE PAG103 [(5-propylsulfonyloximino-5H-thiophen-2-ylidene) -(2-methylphenyl) acetonitrile], IRGACURE PAG108 [(5-octylsulfonyloximino-5H-thiophene-2- ylidene)-(2-methylphenyl)acetonitrile)], IRGACURE PAG121 [5-p-toluenesulfonyloximino-5H-thiophen-2-ylidene-(2-methylphenyl)acetonitrile], IRGACURE PAG203, CGI725, Sanwa Chemical TFE-triazine [2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine], TME-triazine [2-[2-(5-methyl furan-2-yl)ethenyl]-4,6-bis(tri-chloromethyl)-s-triazine]MP-triazine[2-(methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine] , dimethoxy[2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(tri-chloromethyl)-s-triazine].

The blending amount of the crosslinking catalyst is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the curable resin or curable monomer. Within such a range, a sufficient cured product can be obtained. The blending amount of the crosslinking catalyst is more preferably 0.3 to 5 parts by mass, and still more preferably 0.5 to 2 parts by mass.

Further, when the acid generator is used as the crosslinking catalyst, an acid scavenger may be added as necessary to control the diffusion of the acid generated from the acid generator.

Although the acid scavenger is not particularly limited, basic compounds such as amines (particularly organic amines), basic ammonium salts, and basic sulfonium salts are preferred. Among these acid scavengers, organic amines are more preferable from the viewpoint of excellent image performance.

Specific examples of the acid scavenger include 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,4- diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4'-diaminodiphenyl ether, pyridinium p-toluenesulfonate , 2,4,6-trimethylpyridinium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, and tetrabutylammonium lactate, triethylamine, tributylamine, and the like. Among these, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,4-diazabicyclo[2.2.2] Organic amines such as octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4'-diaminodiphenyl ether, triethylamine and tributylamine are preferred.

The amount of the acid scavenger compounded is preferably 20 parts by mass or less, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the acid generator. 5 parts by mass.

The composition (b) may contain a solvent. Examples of the solvent include water-soluble organic solvents, organic solvents (especially oil-soluble organic solvents), water, and the like.

Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, methyl amyl ketone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (PGMEA), dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene Glycol dimethyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol diacetate, tripropylene glycol, 3-methoxybutyl acetate (MBA), 1,3-butylene glycol diacetate, cyclohexanol acetate, dimethylformamide, dimethyl sulfoxide, methyl cellosolve , cellosolve acetate, butyl cellosolve, butyl carbitol, carbitol acetate, ethyl lactate, isopropyl alcohol, methanol, ethanol and the like.

Examples of the organic solvent include chloroform, HFC141b, HCHC225, hydrofluoroether, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl isobutyl ketone, and acetic acid. butyl, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichlorethylene, perchlorethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane and the like. These solvents may be used alone or in combination of two or more.

From the viewpoint of the solubility and safety of the components contained in the resist composition, PGMEA and MBA are particularly preferable as the solvent.

The solvent is preferably used in the composition (b) in a range of 10 to 95% by mass. More preferably, it is 20 to 90% by mass.

For example, a resist film can be formed by applying the composition (b) to a substrate. Examples of materials for the base material include synthetic resins.

Examples of the synthetic resin include cellulose resins such as triacetyl cellulose (TAC), polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer (EVA), cyclic polyolefins, modified Polyolefin, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly-(4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylic-styrene copolymer (AS resin), butadiene-styrene copolymer, ethylene-vinyl alcohol copolymer (EVOH), polyester such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexane terephthalate (PCT), polyether, polyether ketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluorine Various thermoplastic elastomers such as styrene-based, polyolefin-based, polyvinyl chloride-based, polyurethane-based, fluororubber-based, and chlorinated polyethylene-based resins, epoxy resins, phenolic resins, urea resins, melamine resins, unsaturated polyesters, silicone resins , polyurethane, etc., or copolymers, blends, polymer alloys, etc. mainly composed of these, and the like, and these may be used alone or in combination of two or more (for example, as a laminate of two or more layers). can.

The above resist film can be used for nanoimprinting. For example, a step of pressing a mold having a fine pattern formed on its surface against the resist film to transfer the fine pattern, a step of curing the resist film on which the transfer pattern is formed, and obtaining a cured resist having the transfer pattern; And, a pattern-transferred cured resist can be obtained by a manufacturing method including the step of releasing the cured resist from the mold.

The compounds of the present disclosure can be used with solvents. A composition characterized by containing the above compound and a solvent is also one aspect of the present invention (sometimes referred to herein as composition (c)).

In the composition (c), the concentration of the compound is preferably 0.001 to 5.0% by mass, more preferably 0.005 to 1.0% by mass, and further 0.01 to 0.5% by mass. preferable.

A fluorine-based solvent is preferable as the solvent. Examples of the fluorine-based inert solvent include perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, and dichloropentafluoropropane (HCFC-225).

Composition (c) also preferably contains a fluorine-containing oil. As the fluorine-containing oil,
Formula: R ¹¹¹ -(R ¹¹² O) _m -R ¹¹³
(R ¹¹¹ and R ¹¹³ are independently F, an alkyl group having 1 to 16 carbon atoms, a fluorinated alkyl group having 1 to 16 carbon atoms, —R ¹¹⁴ —X ¹¹¹ (R ¹¹⁴ is a single bond or X ¹¹¹ is -NH ₂ , -OH, -COOH, -CH=CH ₂ , -OCH ₂ CH=CH ₂ , halogen, phosphoric acid, phosphoric acid ester, carboxylic acid ester, thiol, thioether, alkyl Ether (which may be substituted with fluorine), aryl, aryl ether, amide), R ¹¹² is a fluorinated alkylene group having 1 to 4 carbon atoms, and m is an integer of 2 or more) are more preferred.

R ¹¹¹ and R ¹¹³ are independently F, an alkyl group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, or —R ¹¹⁴ —X ¹¹¹ (R ¹¹⁴ and X ¹¹¹ are as described above) is preferably F, a fully fluorinated alkyl group having 1 to 3 carbon atoms or —R ¹¹⁴ —X ¹¹¹ (R ¹¹⁴ is a single bond or an alkylene group having 1 to 3 carbon atoms, X ¹¹¹ is —OH or —OCH ₂ CH= CH ₂ ) is more preferred.

m is preferably an integer of 300 or less, more preferably an integer of 100 or less.

R ¹¹² is preferably a fully fluorinated alkylene group having 1 to 4 carbon atoms. —R ¹¹² O— is, for example,
Formula: -(CX ¹¹² ₂ CF ₂ CF ₂ O) _n111 (CF(CF ₃ )CF ₂ O) _n112 (CF ₂ CF ₂ O) _n113 (CF ₂ O) _n114 (C ₄ F ₈ O) _n115 -
(n111, n112, n113, n114 and n115 are independently integers of 0 or 1 or more, ^X112 is H, F or Cl, the order of existence of each repeating unit is arbitrary),
Formula: -(OC ₂ F ₄ -R ¹¹⁸ ) _f -
(R ¹¹⁸ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , and f is an integer of 2 to 100).

Each of n111 to n115 is preferably an integer of 0 to 200. The sum of n111 to n115 is preferably 1 or more, more preferably 5 to 300, even more preferably 10 to 200, and particularly preferably 10 to 100.

R ¹¹⁸ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ or a combination of two or three groups independently selected from these groups. The combination of two or three groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited, but for example -OC ₂ F ₄ OC ₃ F ₆ -, -OC _2F4OC4F8- _, _-OC3F6OC2F4- _, _-OC3F6OC3F6- _, _-OC3F6OC4F8- _, _-OC4F8OC4F _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _8- _, _-OC4F8OC3F6- _, _-OC4F8OC2F4- _, _{-OC2F4OC2F4OC3F6-} _, _{-OC2F4OC2F4OC} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _4F8- _, _{-OC2F4OC3F6OC2F4-} _, _{-OC2F4OC3F6OC3F6-} _, _{-OC2F4OC4F8OC2F4-} _, _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{-OC3F6OC2F4OC2F4-} _, _{-OC3F6OC2F4OC3F6-} _, _{-OC3F6OC3F6OC2F4-} _, _and _-OC4F _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} _{_} ₈ OC ₂ F ₄ OC ₂ F ₄ - and the like. f is an integer of 2-100, preferably an integer of 2-50. In the above formula, OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ may be linear or branched, preferably linear. In this aspect, the formula -(OC ₂ F ₄ -R ¹¹⁸ ) _f - is preferably the formula -(OC ₂ F ₄ -OC ₃ F ₆ ) _f - or the formula -(OC ₂ F ₄ -OC ₄ F ₈ ) _f −.

The fluoropolyether preferably has a weight average molecular weight of 500 to 100,000, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 6,000 or less. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

Commercially available fluoropolyethers include Demnum (manufactured by Daikin Industries, Ltd.), Fomblin (manufactured by Solvay Specialty Polymers Japan), Barrierta (manufactured by NOK Klüber), Krytox (manufactured by DuPont), and the like. mentioned.

The fluorine-containing oil is, for example, 50% by mass or less, preferably 30% by mass or less, relative to the compounds represented by formulas (1) and (2) of the present disclosure (the total when two or more are used). obtain. In one aspect, the fluorine-containing oil is, for example, 0.1% by mass or more, preferably may be included in an amount of 1% by weight or more, for example 5% by weight or more.

The composition (c) can be used to form a release layer on the substrate. The release layer can be formed by a method of immersing the substrate in the composition (c), a method of exposing the substrate to the vapor of the composition (c) for vapor deposition, or printing the composition (c) on the substrate. and a method of applying the composition (c) to the base material using an inkjet method. After the immersion, vapor deposition, printing, and application, drying may be performed. A mold having an uneven pattern formed thereon can be used as the substrate, and the mold having a release layer formed thereon can be used for nanoimprinting.

Examples of the base material include resins such as polymer resins such as silicone.

The present disclosure also provides an antifouling agent characterized by containing the above compound or the above composition.

The above antifouling agent can be used by applying it to a resin (especially non-fluororesin).

The above antifouling agents can be used in various ways for articles (especially optical materials) that require surface antifouling properties and swelling properties. Examples of articles include front protective plates, antireflection plates, polarizing plates, anti-glare plates for displays such as PDP and LCD; cover windows for foldable displays, rollable displays and bending displays; mobile phones, personal digital assistants, etc. Equipment; touch panel sheet; DVD disc, CD-R, optical disc such as MO; spectacle lens; optical fiber; , dashboard and its lower part, panels around the driver's seat, switches, levers, etc., inside the trunk).

Optical materials such as optical discs contain carbon-carbon double bond-containing compositions or carbon-carbon double bond-containing compositions and carbon-carbon double bond-containing compositions It is preferable that the surface is coated with a film formed by adding perfluoropolyether (PFPE) to the polymerized product of the contained monomer so that the content is 0.01% by weight to 10% by weight. At 0.01% by weight to 10% by weight, the characteristic physical properties of PFPE addition (antifouling, etc.) appear, the surface hardness is high, and the transmittance is high.

The present disclosure is also a release agent characterized by containing the compound or composition of the present disclosure.

A release layer can be formed on the substrate from the release agent. The release layer can be formed by a method of immersing the base material in the release agent, a method of exposing the base material to the vapor of the release agent for vapor deposition, a method of printing the composition on the base material, or an inkjet method. and a method of applying the composition to the base material using the above method. After the immersion, vapor deposition, printing, and application, drying may be performed. A mold having an uneven pattern formed thereon can be used as the substrate, and the mold having a release layer formed thereon can be used for nanoimprinting.

Examples of the base materials include metals, metal oxides, quartz, polymeric resins such as silicone, semiconductors, insulators, and composites thereof.

The thickness of the surface treatment layer is not particularly limited. In the case of optical members, the thickness of the surface treatment layer is in the range of 0.05 to 60 μm, preferably 0.1 to 30 μm, more preferably 0.5 to 20 μm. It is preferable in terms of durability and antifouling properties.

As described above, the compositions (a) to (c) of the present disclosure are used as so-called surface treatment agents.

The compounds of the present disclosure can be used together with alkali-soluble resins or polymerization initiators. A composition characterized by containing the above compound and a curable resin or a curable monomer is also one aspect of the present invention (herein sometimes referred to as composition (d)). Since the composition (d) has the above structure, it can be used as a resist resin composition, particularly a bank resist resin composition, typically a negative photosensitive resin composition.

Accordingly, the composition of the present disclosure can be used as an additive for resist compositions, and the present disclosure provides a resist resin composition comprising the composition of the present disclosure, an alkali-soluble resin, and a polymerization initiator. .

The above alkali-soluble resin is an alkali-soluble resin having a photocurable functional group. As the alkali-soluble resin, a photosensitive resin having an acidic group and an ethylenic double bond in one molecule is preferred.

Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group, and the like, and these may be used alone or in combination of two or more.

An ethylenic double bond is preferable as the photocurable functional group. Examples of ethylenic double bonds include double bonds having addition polymerizability such as (meth)acryloyl groups, allyl groups, vinyl groups, vinyloxy groups and vinyloxyalkyl groups. These may be used individually by 1 type, or may use 2 or more types together. In addition, some or all of the hydrogen atoms of the ethylenic double bond may be substituted with an alkyl group such as a methyl group.

The alkali-soluble resin having an ethylenic double bond includes a resin having a side chain having an acidic group and a side chain having an ethylenic double bond, and an epoxy resin into which an acidic group and an ethylenic double bond are introduced. resin and the like. These may be used individually by 1 type, or may use 2 or more types together. As such an alkali-soluble resin, those described in WO2014/084279 can be used.

As a resin having a side chain having an acidic group and a side chain having an ethylenic double bond, a copolymer of acrylic acid, 2-hydroxy methacrylate and other monomers is reacted with 2-acryloyloxytyl isocyanate or the like. things are mentioned. In addition, the unsaturated group-containing urethane resin that is the (A) component of JP-A-2001-33960, the polyurethane compound that is the (E) component of JP-A-2003-268067, and the reactivity that is the (A) component of JP-A-2010-280812 Examples include urethane-based resins such as polyurethane compounds.

Specifically, a compound having a double bond and a hydroxyl group obtained by reacting a bifunctional epoxy resin with acrylic acid, a diol compound having a carboxyl group such as dimethylolpropionic acid, a diisocyanate compound such as trimethylhexamethylene diisocyanate, and optional components. Examples include resins reacted with polybasic acid anhydrides such as glycidyl methacrylate and phthalic anhydride.

Examples of the bifunctional epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, trisphenolmethane type epoxy resin, epoxy resin having a naphthalene skeleton, and biphenyl skeleton. and fluorenyl-substituted bisphenol A type epoxy resins.

Examples of resins in which an acidic group and an ethylenic double bond are introduced into an epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, and trisphenolmethane type epoxy resin. , an epoxy resin having a naphthalene skeleton, an epoxy resin having a biphenyl skeleton, a fluorenyl-substituted bisphenol A-type epoxy resin, and an epoxy resin described in JP-A-2006-84985, each having an acidic group and an ethylenic double bond introduced therein. is preferred.

The number of ethylenic double bonds that the alkali-soluble resin has in one molecule is preferably 3 or more on average, and particularly preferably 6 or more on average. When the number of ethylenic double bonds is at least the lower limit of the above range, the difference in alkali solubility between the exposed and unexposed areas is likely to occur, making it possible to form a fine pattern with a smaller amount of exposure.

The mass average molecular weight (Mw) of the alkali-soluble resin is preferably 1.0×10 ³ to 20×10 ³ , particularly preferably 2×10 ³ to 15×10 ³ . Also, the number average molecular weight (Mn) is preferably 500 to 13×10 ³ , particularly preferably 1.0×10 ³ to 10×10 ³ . When the weight average molecular weight (Mw) and number average molecular weight (Mn) are at least the lower limits of the above ranges, curing during exposure is sufficient, and when they are at most the upper limits of the above ranges, the developability is good. The above number average molecular weight (Mn) and mass average molecular weight (Mw) are those measured by gel permeation chromatography using polystyrene as a standard substance.

The acid value of the alkali-soluble resin is preferably 10-300 mgKOH/g, particularly preferably 10-150 mgKOH/g.

Examples of the polymerization initiator include α-diketones such as methylphenylglyoxylate and 9,10-phenanthrenequinone; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone; benzophenone, 4,4′-bis(dimethylamino)benzophenone, 4 , benzophenones such as 4'-bis(diethylamino)benzophenone; acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p -methoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane- Acetophenones such as 1-one; Quinones such as anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone; Ethyl 2-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, etc. Aminobenzoic acids; Halogen compounds such as phenacyl chloride and trihalomethylphenyl sulfone; Acylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; Di-t-butyl peroxide and the like Peroxide; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime), ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-1-(O-acetyloxime) and other oxime esters, triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, diethylaminoethyl methacrylate and other aliphatic amines, etc. is mentioned. A photoinitiator may be used individually by 1 type, or may use 2 or more types together.

The composition (d) may further contain a cross-linking agent.

The above contains a polyfunctional low-molecular-weight compound having an acidic group and two or more photocurable functional groups in one molecule, and preferably further has two or more photocurable functional groups in one molecule. and contains a cross-linking agent having no acidic group (hereinafter also referred to as "non-acidic cross-linking agent"). A composition containing a cross-linking agent is cross-linked by the cross-linking agent when the alkali-soluble resin is polymerized by exposure to form a sufficiently cured cured film.

The mass average molecular weight (Mw) of the polyfunctional low molecular weight compound is preferably 300 or more and less than 1000, more preferably 500 or more and less than 800. Also, the number average molecular weight (Mn) is preferably 300 or more and less than 1000, and particularly preferably 500 or more and less than 800. When the mass average molecular weight (Mw) and number average molecular weight (Mn) are within the above ranges, good alkali solubility and developability are obtained.

Examples of the polyfunctional low-molecular-weight compounds include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, polyisocyanate compounds and (meth)acryloyl-containing hydroxy compounds. Examples include compounds in which acidic groups are introduced so as to leave two or more unsaturated bonds (ethylenic double bonds) in an ethylenic compound having a urethane skeleton that has been reacted with.

The polyfunctional low-molecular-weight compound is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an aromatic carboxylic acid anhydride or a non-aromatic carboxylic acid anhydride is attached to the unreacted hydroxy group of the aliphatic polyhydroxy compound. A polyfunctional low-molecular-weight compound having an acidic group by reacting a substance is preferable, and a polyfunctional low-molecular-weight compound having an acidic group by reacting a non-aromatic carboxylic acid anhydride is more preferable.

The aliphatic polyhydroxy compound in the ester of the unsaturated carboxylic acid and the aliphatic polyhydroxy compound into which an acidic group is introduced includes compounds having three or more hydroxy groups, such as trimethylolpropane, trimethylolethane, and pentaerythritol. , dipentaerythritol, tripentaerythritol, tetrapentaerythritol, and the like. Unsaturated carboxylic acids include (meth)acrylic acid, itaconic acid, irotonic acid, maleic acid and the like.

In the above ester of the aliphatic polyhydroxy compound and unsaturated carboxylic acid, the aliphatic polyhydroxy compound is preferably pentaerythritol and/or dipentaerythritol, particularly preferably dipentaerythritol. As the unsaturated carboxylic acid, (meth)acrylic acid is preferable, and acrylic acid is more preferable.

Specific examples of the aromatic carboxylic anhydride used to introduce an acidic group into the ester include phthalic anhydride, and specific examples of the non-aromatic carboxylic anhydride include tetrahydrophthalic anhydride, alkylation Examples include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride, of which succinic anhydride is preferred.

Among polyfunctional low-molecular-weight compounds, compounds obtained by reacting an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid with an aromatic carboxylic acid anhydride include, for example, three hydroxy groups of pentaerythritol substituted with acryloyloxy groups. and 2,2,2-triacryloyloxymethylethyl phthalic acid having a structure in which the remaining one hydroxyl group is ester-bonded to phthalic acid, for example.

A compound having a dipentaerythritol skeleton is preferable as the polyfunctional low-molecular-weight compound. As a compound having a dipentaerythritol skeleton, for example, five hydroxy groups of dipentaerythritol are substituted with (meth)acryloyloxy groups, and the remaining one hydroxy group is ester-bonded with, for example, succinic acid to form an acidic group. is preferably introduced.

The acid value of the polyfunctional low molecular weight compound is preferably 10-100 mgKOH/g, more preferably 20-95 mgKOH/g. When the acid value of the polyfunctional low-molecular-weight compound is at least the above lower limit, better solubility in a developing solution can be obtained in the negative photosensitive composition. Handleability is improved, sufficient polymerizability can be ensured, and curability such as surface smoothness of the resulting coating film is also improved.

Examples of the non-acidic crosslinking agent include diethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate. , dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapentaerythritol heptaacrylate, tetrapentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetra Pentaerythritol decaacrylate, ethoxylated isocyanuric acid tri(meth)acrylate, tris-(2-acryloyloxyethyl) isocyanurate, ε-caprolactone-modified tris-(2-acryloyloxyethyl) isocyanurate, dipentaerythritol pentaacrylate and HDI Examples include monomers (10-functional) having a urethane skeleton to which (hexamethylene diisocyanate) is bonded, urethane acrylates, and the like. The non-acidic cross-linking agents may be used alone or in combination of two or more.

The content of the cross-linking agent in the total solid content of the composition (d) is preferably 5-80% by mass, particularly preferably 10-60% by mass.

The content of the polyfunctional low-molecular weight compound in the total solid content of the composition (d) is preferably 5-80% by mass, more preferably 7-60% by mass. When the content of the polyfunctional low-molecular-weight compound is within the above range, the photocurability and developability of the negative photosensitive resin composition are good.

When the composition (d) contains a non-acidic cross-linking agent as a cross-linking agent, the content of the non-acidic cross-linking agent in the total solid content of the composition is preferably from 0.1 to 50% by mass, and from 1.0 to 40% by mass is more preferred. The ratio of the polyfunctional low molecular weight compound to 100 parts by weight in total of the polyfunctional low molecular weight compound and the non-acidic cross-linking agent is preferably 10 to 90 parts by weight, more preferably 15 to 70 parts by weight. By adjusting the ratio of the polyfunctional low-molecular-weight compound and the non-acidic cross-linking agent to the above ratio, it becomes easy to adjust the acid value and the number of photocurable functional groups of the cross-linking agent as a whole.

Moreover, as a cross-linking agent, those commercially available as a mixture of a polyfunctional low molecular weight compound and a non-acidic cross-linking agent, such as dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and a succinate ester mixture of dipentaerythritol pentaacrylate, etc. may be used.

The composition (d) may further contain a solvent.

Examples of the solvent include alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, alcohols, solvent naphthas, and water. Among them, at least one solvent selected from the group consisting of alkylene glycol alkyl ethers, alkylene glycol alkyl ether acetates, and alcohols is preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol. at least one selected from the group consisting of monoethyl ether acetate, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide and 2-propanol Seed solvents are more preferred.

When the solvent contains water, the content of water is preferably 10% by mass or less of the total solvent. Within the above range, it is possible to reduce the unevenness of the patterned substrate comprising partition walls formed from the cured film obtained from the composition (d). Also, the content of water is more preferably 1 to 10% by mass. Within the above range, the dispersion stability of the composition is good.

The content of the solvent in the composition (d) is preferably 10-99% by mass, more preferably 20-95% by mass, and particularly preferably 50-90% by mass, relative to the total amount of the composition. Further, it is preferably 0.1 to 3000% by mass, more preferably 0.5 to 2000% by mass, based on the total 100% by mass of the alkali-soluble resin and the cross-linking agent.

The composition (d) may further optionally contain a thiol compound, a phosphoric acid compound, a polymerization inhibitor, a thermal cross-linking agent, a polymer dispersant, a dispersing aid, a silane coupling agent, fine particles, a curing accelerator, a thickener, At least one other additive selected from the group consisting of additives, plasticizers, antifoaming agents, leveling agents and anti-cratering agents may be contained.

The composition (d) can be used to form cured films and barrier ribs used in optical elements such as organic EL elements, quantum dot displays, TFT arrays or thin-film solar cells. By using the composition (d) of the present disclosure, it is possible to produce a resist, especially a bank resist, which has good ink repellency on the surface, good development adhesion to the substrate, and little development residue. . In particular, the bank resist obtained from the composition (d) has good ink repellency on the upper surface, good development adhesion to the substrate, and little development residue. When used in an organic EL device, a quantum dot display, a TFT array, or a thin film solar cell manufactured by the method, the ink is uniformly applied to the openings and dots can be formed with high accuracy.

The cured film obtained from the composition (d) of the present disclosure has a high fluorine concentration on the surface. Here, the fluorine concentration on the cured film surface can be measured by X-ray photoelectron spectroscopy (XPS).

XPS, PHI5000VersaProbe II manufactured by ULVAC-PHI, Inc. can be used as an apparatus for performing X-ray photoelectron spectroscopy for measuring the atomic composition and ratio of constituent atoms of the cured film. The measurement conditions for the XPS analysis are as follows: monochromatic AlKα rays of 25 W for the X-ray source, a photoelectron detection area of 1400 μm×300 μm, a photoelectron detection angle of 20 degrees to 90 degrees (eg, 20 degrees, 45 degrees, 90 degrees), It is possible to set the pass energy to 23.5 eV or the like and use Ar ions as the sputtering ions. The composition of the surface of the cured film can be obtained by observing the peak areas of C1s, O1s and F1s and calculating the atomic ratio of carbon, oxygen and fluorine using the above apparatus and measurement conditions.

In addition, XPS can analyze the composition in the depth direction of the cured film. The measurement conditions for the XPS analysis are as follows: monochromatic AlKα rays at 25 W are used as the X-ray source, the photoelectron detection area is 1400 μm×300 μm, and the photoelectron detection angle is in the range of 20 degrees to 90 degrees (eg, 20 degrees, 45 degrees, 90 degrees degree), pass energy of 23.5 eV, etc., and Ar ions can be used as sputtering ions. It is possible to etch 1 to 100 nm by sputtering with Ar ions and obtain the composition in the cured film at each depth after etching. Incidentally, the detection depth can be appropriately adjusted by adjusting the photoelectron detection angle of the XPS analysis. For example, a shallow angle close to 20 degrees allows the detection depth to be about 3 nm, while a deep angle close to 90 degrees allows the detection depth to be about 10 and several nm. can.

The fluorine atom concentration on the surface of the cured film obtained from the composition of the present disclosure is preferably 40% or higher, more preferably 45% or higher, and even more preferably 50% or higher. The upper limit of the fluorine atom concentration is not particularly limited, but may be, for example, 80% or less, 70% or less, or 60% or less. By having a fluorine atom concentration within this range, the cured film obtained from the composition of the present disclosure has excellent ink repellency.

The cured film obtained from the composition (d) of the present disclosure has a high perfluoropolyether group (PFPE) concentration on the surface. Here, the perfluoropolyether group concentration on the cured film surface can be measured by XPS. For example, focusing on the O1s orbital, the C—O bond of CF ₂ CF ₂ —O—CF ₂ CF ₂ in the perfluoropolyether group was detected at 535 eV, and the C—O—C bond derived from the hard coating agent was detected at 533 eV. , C=O bonds are detected at 531 ev, respectively. Therefore, the perfluoropolyether group ratio can be obtained as the ratio of the peak area having a peak top near 535 to 536 eV in the total amount of peak areas observed at approximately 530 to 540 eV, which is regarded as the O1s orbit.

The perfluoropolyether group concentration on the surface of the cured film obtained from the composition of the present disclosure is preferably 30% or higher, more preferably 40% or higher, and even more preferably 50% or higher. The upper limit of the perfluoropolyether group concentration is not particularly limited, but may be, for example, 80% or less, 70% or less, or 60% or less. By having a perfluoropolyether group concentration within such a range, the cured film obtained from the composition of the present disclosure has excellent ink repellency.

The composition of the present disclosure has been described in detail above. It should be noted that the application, usage method, article manufacturing method, and the like of the composition of the present disclosure are not limited to those exemplified above.

The present disclosure will be described below in Examples, but the present disclosure is not limited to the following Examples. In this example, the chemical formulas of the polymers shown below all represent average compositions.

Synthesis Example 1: Production of PFPE-containing compound (A) Using HOCH ₂ CF ₂ CF ₂ O—(CF ₂ CF ₂ CF ₂ O) ₂₅ —CF ₂ CF ₂ CH ₂ OH as a starting material, the method described in WO2018/056413A1 The following perfluoropolyether (PFPE)-containing compound (A) was synthesized according to.

PFPE-containing compound (A):

Synthesis Examples 2 to 5: Production of PFPE-containing compounds (B), (C), (D), and (E) Accordingly, the following perfluoropolyether (PFPE)-containing compounds (B), (C), (D), and (E) were synthesized, and for each compound, 1, 1, 2, 2, 3, 3 , 4-heptafluorocyclopentane and 2-butanone in a mixed solvent to obtain a 20 wt % solution.

PFPE-containing compound (B):

PFPE-containing compound (C):

PFPE-containing compound (D):

PFPE-containing compound (E):

Synthesis Example 6: Production of PFPE-containing compound (F) Using CF ₃ CF ₂ CF ₂ O—(CF ₂ CF ₂ CF ₂ O) ₂₅ —CF ₂ CF ₂ CH ₂ OH as a starting material, the method described in WO2018/056413A1 The following perfluoropolyether (PFPE)-containing compound (F) was synthesized according to.

PFPE-containing compound (F):

Synthesis Examples 7 to 9: Production of PFPE-containing compounds (G), (H), and (I) Using the PFPE-containing compound (F) obtained above as a starting material, according to the method described in WO2021/024964A1, Mixtures of 1,1,2,2,3,3,4-heptafluorocyclopentane and 2-butanone for the following perfluoropolyether (PFPE)-containing compounds (G), (H), and (I), respectively A 20 wt% solution in solvent was obtained.

PFPE-containing compound (G):

PFPE-containing compound (H):

PFPE-containing compound (I):

<Compatibility with PGMEA>
PFPE-containing compound (B), or a mixture obtained by mixing PFPE-containing compound (B) and PFPE-containing compound (G) in the proportions shown in Table 1, was added to PGMEA (propylene glycol monomethyl ether acetate) to a concentration of 4.0 wt%. After mixing well and shaking well, the appearance of the mixture was evaluated according to the following criteria. Table 1 shows the results.
◎: Colorless and transparent solution 〇: Slightly translucent

(Production of cured film)
Beamset 575CB (manufactured by Arakawa Chemical Industries, Ltd.) and methyl isobutyl ketone were mixed to make the solid content concentration 50 wt%, and then the PFPE-containing compound (B) or the PFPE-containing compound (B) and the PFPE-containing compound (G) were mixed. A mixture mixed at the ratio (molar ratio) shown in Table 1 was added to the beam set 575CB so that the solid content ratio was 1.0% by mass, and the mixture was stirred for 1 hour with a rotating mixer under light shielding to obtain a mixture containing PFPE. A hard coat material was obtained.

(evaluation)
<Characteristic evaluation of cured film>
Each of the hard coat materials obtained above was placed on a PET film (Cosmo Shine A4160, manufactured by Toyobo Co., Ltd.), and a uniform coating film was formed using a bar coater. The resulting coating film was irradiated with a light beam containing UV light of 365 nm at an intensity of 600 mJ/cm ² in a nitrogen atmosphere to cure each hard coat material to obtain a cured film (surface treatment layer). The film thickness of the cured film was 5 to 6 μm. The initial properties of the resulting cured film were evaluated as follows.

(Measurement of Haze)
Haze was measured for each cured film. Specifically, using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., 7000SP), three different points on the substrate were measured by a measurement method based on ASTM, and the average value was calculated and used. . Table 1 shows the measurement results.

<Evaluation of antifouling property>
(fingerprint adhesion)
A finger was pressed against the cured film, and the susceptibility to fingerprints was visually determined. Evaluation was based on the following criteria. Table 1 shows the results.
◯: Fingerprints are hard to adhere, or fingerprints are inconspicuous even if adhered.
x: Fingerprints are clearly attached.

(Fingerprint wiping ability)
After the above-mentioned fingerprint adhesion test, the adhered fingerprints were wiped off with a Kimwipe (trade name, manufactured by Jujo Kimberly Co., Ltd.) five times, and the easiness of wiping off the adhered fingerprints was visually determined. Evaluation was based on the following criteria. Table 1 shows the results.
O: Fingerprints can be completely wiped off.
x: Wiping traces of fingerprints spread and are difficult to remove.

(static contact angle)
The static contact angle was measured by the following method using a fully automatic contact angle meter DropMaster 700 (manufactured by Kyowa Interface Science Co., Ltd.). Table 1 shows the results.

<Method for measuring static contact angle>
The static contact angle was obtained by dropping 3 μL of the test liquid from a microsyringe onto a substrate placed horizontally, and taking a still image 1 second after dropping with a video microscope. The static contact angle of the test liquid was measured at five different points on the surface treatment layer of the base material, and the average value was calculated and used. Initial values were measured for the cured films of the PFPE-containing hard coat materials of Examples 1-5. Table 1 shows the results. As test liquids, five types of water, n-hexadecane, PGMEA, 1,6-bis(acryloyloxy)hexane, and anisole were measured, and the judgment criteria for each test liquid were as follows. Table 1 shows the results.

Judgment criteria for static contact angle of water ◎: Contact angle of 111 degrees or more ○: Contact angle of 106 degrees or more and less than 111 degrees △: Contact angle of 100 degrees or more and less than 106 degrees ×: Contact angle of less than 100 degrees

Criteria for static contact angle of n-hexadecane ◎: Contact angle of 62 degrees or more ○: Contact angle of 61 degrees or more and less than 62 degrees △: Contact angle of 59 degrees or more and less than 61 degrees ×: Contact angle of less than 59 degrees

Criteria for static contact angle of PGMEA ◎: Contact angle 62 degrees or more ○: Contact angle 60 degrees or more, less than 62 degrees △: Contact angle 58 degrees or more, less than 60 degrees ×: Contact angle less than 58 degrees

Criteria for static contact angle of 1,6-bis (acryloyloxy) hexane ◎: Contact angle 70 degrees or more ○: Contact angle 67 degrees or more, less than 70 degrees △: Contact angle 64 degrees or more, less than 67 degrees ×: Contact less than 64 degrees

Judgment criteria for static contact angle of anisole ◎: Contact angle of 70 degrees or more ○: Contact angle of 67 degrees or more and less than 70 degrees △: Contact angle of 64 degrees or more and less than 67 degrees ×: Contact angle of less than 64 degrees

In the same manner as above, PFPE-containing compound (C), or mixtures of PFPE-containing compound (C) and PFPE-containing compound (H) mixed at the ratio shown in Table 2 were evaluated as Examples 6-10. Table 2 shows the results.

In the same manner as above, PFPE-containing compound (D) or mixtures of PFPE-containing compound (D) and PFPE-containing compound (I) mixed at the ratio shown in Table 3 were evaluated as Examples 11 to 15. Table 3 shows the results.

In the same manner as described above, the PFPE-containing compound (E), or the PFPE-containing compound (E) and the PFPE-containing compound (G), (H) or (I) were mixed in the proportions shown in Table 4. 25 was evaluated. Table 4 shows the results.

Comparative Examples 1 and 2
Measurement was performed in the same manner as in Example 1 above, except that the PFPE-containing compound was changed to the fluorine-containing compound (J) shown below and added to the beam set 575CB so as to be 4.0% by mass. was performed (Comparative Example 1). A hard coat material consisting only of a mixed solution of Beamset 575CB and methyl isobutyl ketone to which no PFPE-containing compound was added was also measured in the same manner as in Example 1 above (Comparative Example 2). Table 5 shows the results.

Fluorine-containing compound (J):

As can be seen from the results in Tables 1-5 above, the treated substrates having cured films obtained from the hard coat materials of Examples 1-25 containing the PFPE-containing compounds of the present disclosure had a clear, clean appearance with low haze. , and the treated substrate exhibited excellent water repellency and oil repellency. On the other hand, the composition containing the fluorine-containing compound (J) and Comparative Examples 1 and 2, in which no PFPE-containing compound was added, had insufficient fingerprint adhesion and fingerprint wiping-off properties, and also had low water repellency and oil repellency.

<Surface analysis>
The surface composition of the surface treatment layer of the above-treated substrate was determined using an X-ray photoelectron spectroscopic analyzer (XPS, PHI5000VersaProbeII manufactured by ULVAC-Phi, Inc.). The measurement conditions for the XPS analysis were as follows.
X-ray source: monochromatic AlKα rays (25 W)
Photoelectron detection area: 1400 μm×300 μm
Photoelectron detection angle: 45 degrees Pass energy: 23.5 eV

In the surface treatment layers of Examples 1, 5, 9, 14, 16, 19 and 22, and Comparative Examples 1 and 2, the peak areas of C1s, O1s and F1s were observed by the above XPS, and their peak area ratios were calculated. By doing so, the composition of carbon atoms, oxygen atoms, and fluorine atoms on the surface of the surface treatment layer was determined. Table 6 shows the results.

Also, the PFPE ratio on the surface of the surface treatment layer was determined as follows.
Focusing on the O1s orbital, the C—O bond of CF ₂ CF ₂ —O—CF ₂ CF ₂ in PFPE was detected at 535 eV, the C—O—C bond derived from the hard coating agent was detected at 533 eV, and the C═O bond was detected at 531ev, respectively. Therefore, the above XPS was measured, and the PFPE ratio was obtained as the ratio of the peak area having the peak top near 535 to 536 eV among the total amount of peak areas observed at approximately 530 to 540 eV, which is regarded as the O1s orbit. Table 6 shows the results.

As shown in Table 6, it was confirmed that the surface treatment agent substrate of the present disclosure exhibited a high fluorine concentration on the substrate surface, and that PFPE was highly segregated on the surface.

As described above, the surface of the surface treatment agent treated with the composition of the present disclosure has highly segregated PFPE on the surface and has a high surface fluorine concentration. useful as an agent.

<Evaluation of Eraser Friction Durability>
The cured films shown in Table 7 below were evaluated for friction durability by an eraser friction durability test. Specifically, the sample article on which the surface treatment layer is formed is horizontally arranged, and an eraser (manufactured by Minoan, hardness 81 (Durometer A type), planar dimension 0.6 cm diameter circle) is brought into contact with the surface of the surface treatment layer. , and a load of 1000 gf was applied thereon, and then the eraser was reciprocated at a speed of 48 mm/sec (friction speed of 40 rpm) while the load was applied. The static contact angle of water (degrees) was measured every 1000 reciprocations. The evaluation was stopped when the measured contact angle was less than 95 degrees. Table 7 below shows the number of reciprocations when the contact angle finally exceeded 95 degrees.

From the above results, it was confirmed that the composition of the present disclosure can form a transparent and clean film compared to conventional products, and that the surface treatment layer obtained from such a composition can exhibit a high level of friction durability. .

<Dependence on film thickness>
PFPE-containing compound (D), or a mixture obtained by mixing PFPE-containing compound (D) and PFPE-containing compound (I) at the ratio shown in Table 8, was used as Examples 26 to 30, and the film thickness was set to the thickness shown in Table 8. Except for this, the properties of the cured film were evaluated in the same manner as in Example 1.

When a normal resin composition is used, increasing the film thickness worsens haze and lowers the function, but as shown in Table 8, when the composition of the present disclosure is used, the film thickness It was confirmed that deterioration of haze is suppressed and high water and oil repellency is obtained even when the is large.

The composition of the present disclosure can be used as a surface treatment agent for various resin substrates. The composition of the present disclosure can also be used as an additive for resin compositions, particularly bank resists.

Claims

Formula (1) below:

[In the formula:
RN is a trivalent organic group containing N ;
R F2 is -Rf 2 p -R F -O q -;
Rf 2 is a C 1-6 alkylene group optionally substituted by one or more fluorine atoms;
R F is a divalent fluoropolyether group;
p is 0 or 1;
q is 0 or 1;
X a is independently at each occurrence a single bond or a divalent organic group;
R A1 is independently at each occurrence an OR Ac group-containing group;
R Ac is a (meth)acryloyl group;
R B is independently at each occurrence R F1 -X a - or R A1 -X b -;
R F1 is Rf 1 -R F -O q -;
Rf 1 is a C 1-16 alkyl group optionally substituted by one or more fluorine atoms;
X b is a divalent organic group containing at least two heteroatoms. ]
A composition comprising a compound represented by
Furthermore, the following formula (2):

[In the formula:
RN is a trivalent organic group containing N ;
R F1 is Rf 1 -R F -O q -;
Rf 1 is a C 1-16 alkyl group optionally substituted by one or more fluorine atoms;
R F is a divalent fluoropolyether group;
q is 0 or 1;
X a is a single bond or a divalent organic group;
R A1 is an OR Ac group-containing group;
R Ac is a (meth)acryloyl group;
X b is a divalent organic group containing at least two heteroatoms;
R B is R F1 -X a - or R A1 -X b -. ]
2. The composition of claim 1, comprising a compound represented by:
Formula (1) is the following formula (1′):

[In the formula:
R F2 is -Rf 2 p -R F -O q -;
Rf 2 is a C 1-6 alkylene group optionally substituted by one or more fluorine atoms;
R F is a divalent fluoropolyether group;
p is 0 or 1;
q is 0 or 1;
X a is independently at each occurrence a single bond or a divalent organic group;
R A1 is independently at each occurrence an OR Ac group-containing group;
R Ac is a (meth)acryloyl group;
R B is independently at each occurrence R F1 -X a - or R A1 -X b -;
R F1 is Rf 1 -R F -O q -;
Rf 1 is a C 1-16 alkyl group optionally substituted by one or more fluorine atoms;
X b is a divalent organic group containing at least two heteroatoms. ]
3. The composition of claim 1 or 2, wherein
Formula (2) is the following formula (2′):

[In the formula:
R F1 is Rf 1 -R F -O q -;
Rf 1 is a C 1-16 alkyl group optionally substituted by one or more fluorine atoms;
R F is a divalent fluoropolyether group;
q is 0 or 1;
X a is a single bond or a divalent organic group;
R A1 is an OR Ac group-containing group;
R Ac is a (meth)acryloyl group;
X b is a divalent organic group containing at least two heteroatoms;
R B is R F1 -X a - or R A1 -X b -. ]
4. The composition of claim 2 or 3, wherein
Each R F is independently of the formula:
- (OC 6 F 12 ) a - (OC 5 F 10 ) b - (OC 4 F 8 ) c - (OC 3 R Fa 6 ) d - (OC 2 F 4 ) e - (OCF 2 ) f -
[wherein R Fa is independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom;
a, b, c, d, e and f are each independently an integer of 0 to 200, the sum of a, b, c, d, e and f is 1 or more; The order of existence of each repeating unit bracketed with c, d, e or f is arbitrary in the formula. ]
The composition according to any one of claims 1 to 4, which is a group represented by
6. The composition of claim 5, wherein RFa is a fluorine atom.
R F each independently represents the following formula (f1), (f2), (f3), (f4), (f5) or (f6):
-(OC 3 F 6 ) d -(OC 2 F 4 ) e - (f1)
[Wherein, d is an integer of 1 to 200, and e is 0 or 1. ],
-(OC 4 F 8 ) c -(OC 3 F 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f - (f2)
[wherein c and d are each independently an integer of 0 to 30;
e and f are each independently an integer from 1 to 200;
the sum of c, d, e and f is an integer from 10 to 200;
The order of existence of each repeating unit bracketed with subscript c, d, e or f is arbitrary in the formula. ],
-(R 6 -R 7 ) g - (f3)
[wherein R 6 is OCF 2 or OC 2 F 4 ;
R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or two or three groups selected from these groups. is a combination of groups;
g is an integer from 2 to 100; ],
—(R 6 —R 7 ) g —R r —(R 7′ —R 6′ ) g′ − (f4)
[wherein R 6 is OCF 2 or OC 2 F 4 ;
R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or 2 independently selected from these groups or a combination of three groups,
R 6' is OCF 2 or OC 2 F 4 ;
R 7′ is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or independently selected from these groups a combination of two or three groups,
g is an integer from 2 to 100,
g' is an integer from 2 to 100,
Rr is

(In the formula, * indicates the binding position.)
is. ];
- (OC 6 F 12 ) a - (OC 5 F 10 ) b - (OC 4 F 8 ) c - (OC 3 F 6 ) d - (OC 2 F 4 ) e - (OCF 2 ) f - (f5)
[Wherein, e is an integer of 1 or more and 200 or less, a, b, c, d and f are each independently an integer of 0 or more and 200 or less, and a, b, c, d, e and f are at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula. ]
- (OC 6 F 12 ) a - (OC 5 F 10 ) b - (OC 4 F 8 ) c - (OC 3 F 6 ) d - (OC 2 F 4 ) e - (OCF 2 ) f - (f6)
[Wherein, f is an integer of 1 or more and 200 or less, a, b, c, d and e are each independently an integer of 0 or more and 200 or less, and a, b, c, d, e and f are at least 1, and the order of existence of each repeating unit enclosed in parentheses with a, b, c, d, e or f is arbitrary in the formula. ]
The composition according to any one of claims 1 to 4, which is a group represented by
X a has the following formula:
-(CX 121 X 122 ) x1 -(X a1 ) y1 -(CX 123 X 124 ) z1 -
[In the formula,
X 121 to X 124 are each independently H, F, OH or —OSi(OR 121 ) 3 (wherein three R 121 are each independently an alkyl group having 1 to 4 carbon atoms is.) and
X a1 is -C(=O)NH-, -NHC(=O)-, -O-, -C(=O)O-, -OC(=O)-, -OC(=O)O- , or -NHC(=O)NH-, where the left side of each bond is attached to CX 121 X 122 .
x1 is an integer of 0-10, y1 is 0 or 1, and z1 is an integer of 1-10. ]
The composition according to any one of claims 1 to 7, which is a group represented by
The composition according to any one of claims 1 to 8, wherein X a is a group represented by -(CH 2 ) m22 - (wherein m22 is an integer of 1 to 3).
R A1 is -R A6 -R A4 -OR AC or -R A6 -R A5 -(OR AC ) 2 ;
R A4 is a C 1-10 alkylene group,
R A5 is a trivalent hydrocarbon group having 1 to 10 carbon atoms,
R A6 is a single bond or -C 1-10 alkylene-O-;
RAC is a (meth)acryloyl group,
A composition according to any one of claims 1-9.
R A1 is -R A4 -OR AC or -R A5 -(OR AC ) 2 ;
R A4 is a C 1-10 alkylene group,
R A5 is a trivalent hydrocarbon group having 1 to 10 carbon atoms,
RAC is a (meth)acryloyl group,
A composition according to any one of claims 1-10.
X b is -X c -X d -,
X c is a divalent organic group containing a heteroatom;
X d is -CO-NR d2 -, -OCO-NR d2 -, -NR d2 -CO-, or -NR d2 -COO-;
R d2 is a hydrogen atom or a C 1-6 alkyl group,
A composition according to any one of claims 1-11.
X b is -X c -X d -,
X c is a divalent organic group containing a heteroatom;
X d is -CO-NR d2 -;
R d2 is a hydrogen atom or a C 1-6 alkyl group,
A composition according to any one of claims 1-12.
R A1 is -R A5 -(OR AC ) 2 ;
R A5 is a trivalent hydrocarbon group having 4 to 6 carbon atoms,
RAC is a (meth)acryloyl group,
A composition according to any one of claims 1-13.
X c is -[(R c1 ) t1 -(X c1 ) t2 ]-X c2 -;
R c1 at each occurrence is independently a single bond or a C 1-12 alkylene group;
X c1 is independently at each occurrence O, NR x1 , S, SO or SO2;
each occurrence of R x1 is independently a hydrogen atom or a C 1-6 alkyl group;
X c2 is O or NR x2 ;
each occurrence of R x2 is independently a hydrogen atom or a C 1-6 alkyl group;
t1 is an integer from 1 to 6;
t2 is an integer from 1 to 6;
Here, in [(R c1 ) t1 -(X c1 ) t2 ], the order of existence of R c1 and X c1 is arbitrary in the formula,
A composition according to any one of claims 12-14.
X c is —R c1′ —X c1 —R c1″ —X c2 —;
R c1′ is a C 1-6 alkylene group,
R c1″ is a C 1-12 alkylene group,
X c1 is O, NR x1 , S, SO or SO2 ,
each occurrence of R x1 is independently a hydrogen atom or a C 1-6 alkyl group;
X c2 is O or NR x2 ;
each occurrence of R x2 is independently a hydrogen atom or a C 1-6 alkyl group;
A composition according to any one of claims 12-15.
X c is —R c1′ —X c1 —R c1″ —X c2 —;
R c1′ is a C 2-4 alkylene group,
R c1″ is a C 2-12 alkylene group,
X c1 is S;
A composition according to any one of claims 12 to 16, wherein X c2 is O.
A composition according to any preceding claim, wherein R B is R A1 -X b -.
The content of the compound represented by formula (1) is 10 to 90 mol% with respect to the total amount of the compound represented by formula (1) and the compound represented by formula (2). 19. The composition according to any one of items 2-18.
The composition according to any one of claims 1 to 19, which is an ink-repellent agent.
The composition according to any one of claims 1 to 19, which is an additive for a resist resin composition.
A curable composition comprising a composition according to any one of claims 1 to 19; and a matrix-forming composition.
An article comprising a substrate and a layer formed from the composition according to any one of claims 1 to 19 or the curable composition according to claim 22 on the surface of the substrate.
The article according to claim 23, wherein the article is an optical member.
A composition according to any one of claims 1 to 19,
an alkali-soluble resin, and a polymerization initiator,
A resist resin composition comprising:
The resist resin composition according to claim 25, which is for bank resist formation.