KR20240023156A - Composition containing a fluoropolyether group-containing compound - Google Patents

Abstract

The present invention has the following formula (1)

Provided is a composition comprising a compound represented by (wherein each symbol is as described in the specification).

Description

Composition containing a fluoropolyether group-containing compound

The present disclosure relates to a composition containing a fluoropolyether group-containing compound.

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).

International Publication No. 2021/024964

When a fluoropolyether group-containing compound is used as an additive in a resin composition, the film obtained from this resin composition tends to have an increased haze. In particular, as the film thickness increases, this tendency becomes more noticeable.

The purpose of the present disclosure is to provide a composition containing a fluoropolyether group-containing compound capable of providing a low-Haze film.

This disclosure includes the following aspects.

[1] Equation (1) below:

[Formula:

R ^N 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 which may be substituted with 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 a single bond or a divalent organic group in each occurrence;

R ^A1 , in each occurrence, is independently an OR ^Ac group-containing group;

R ^Ac is a (meth)acryloyl group;

R ^B is independently in 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 which may be substituted with 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] Additionally, the following equation (2):

[Formula:

R ^N 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 which may be substituted with 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 the compound represented by .

[3] Equation (1) is the following formula (1'):

[Formula:

R ^F2 is -Rf ² _p -R ^F -O _q -;

Rf ² is a C _1-6 alkylene group which may be substituted with 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 a single bond or a divalent organic group in each occurrence;

R ^A1 , in each occurrence, is independently an OR ^Ac group-containing group;

R ^Ac is a (meth)acryloyl group;

R ^B is independently in 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 which may be substituted with one or more fluorine atoms;

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

phosphorus, the composition according to [1] above or [2] above.

[4] Equation (2) is the following equation (2'):

[Formula:

R ^F1 is Rf ¹ -R ^F -O _q -;

Rf ¹ is a C _1-16 alkyl group which may be substituted with 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 -.]

phosphorus, the composition according to [2] or [3] above.

[5] R ^F is each independently expressed as:

[In the formula, R ^Fa is independently a hydrogen atom, a fluorine atom, or a chlorine atom in each occurrence,

a, b, c, d, e and f are each independently an integer from 0 to 200, the sum of a, b, c, d, e and f is 1 or more, a, b, c, d, The order of existence of each repeating unit enclosed in parentheses with 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 is each independently represented by the following formula (f1), (f2), (f3), (f4), (f5) or (f6):

[Wherein, d is an integer from 1 to 200, and e is 0 or 1.],

[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 enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula.],

[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 a combination of 2 or 3 groups selected from these groups;

g is an integer from 2 to 100.],

[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 a combination of 2 or 3 groups independently selected from these groups ego,

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 independently selected from these groups. It is a combination,

g is an integer from 2 to 100,

g ^' is an integer from 2 to 100,

R ^r is,

(In the formula, * represents the binding position.)

am.];

[In the formula, e is an integer from 1 to 200, a, b, c, d, and f are each independently integers from 0 to 200, and the sum of a, b, c, d, e, and f is It is 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 formula, f is an integer between 1 and 200, and a, b, c, d, and e are each independently integers between 0 and 200, and is the sum of a, b, c, d, e, and f. is 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 equation:

[During the ceremony,

^{X 121 to} _{_} ^_

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 bonded ^to CX ¹²¹

x1 is an integer from 0 to 10, y1 is 0 or 1, and z1 is an integer from 1 to 10.]

The composition according to any one of [1] to [7] above, which is a group represented by .

[9] The composition according to any one of [1] to [8], wherein X ^a is a group represented by -(CH ₂ ) _m22 - (wherein m22 is an integer of 1 to 3).

[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-,

R ^AC is (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,

R ^AC is (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 hetero atom,

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 hetero atom,

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,

R ^AC is (meth)acryloyl group,

The composition according to any one of claims 1 to 13.

[15] X ^c is -[(R ^c1 ) _t1 -(X ^c1 ) _t2 ]-X ^c2 -,

R ^c1 is, at each occurrence, independently a single bond or a C _1-12 alkylene group,

X ^c1 is, at each occurrence, independently O, NR ^x1 , S, SO or SO ₂ ,

R ^x1 is independently a hydrogen atom or a C _1-6 alkyl group in each occurrence,

X ^c2 is O or NR ^x2 ,

R ^x2 is independently a hydrogen atom or a C _1-6 alkyl group in each occurrence,

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 SO ₂ ,

R ^x1 is independently a hydrogen atom or a C _1-6 alkyl group in each occurrence,

X ^c2 is O or NR ^x2 ,

R ^x2 is independently a hydrogen atom or a C _1-6 alkyl group in each occurrence,

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,

X ^c2 is O

The composition according to any one of [12] to [16] above.

[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% based on the total amount of the compound represented by formula (1) and the compound represented by formula (2), [2] to [ 18] The composition according to any one of the 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 to a resist resin composition.

[22] The composition according to any one of [1] to [19] above; and

Composition forming a matrix

A curable composition containing.

[23] An article comprising a substrate and a layer formed on the surface of the substrate by the surface treatment agent according to any one of [1] to [19] above, or the curable composition according to [22] above.

[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,

Alkali soluble resin, and

polymerization initiator,

A resist resin composition containing.

[26] The resist resin composition according to [25] above, for forming a bank resist.

The composition containing the fluoropolyether group-containing compound of the present disclosure has water repellency, oil repellency, or stain resistance, and can provide a low haze surface treatment layer to the substrate.

As used herein, “organic group” means a monovalent group containing carbon. As a monovalent organic group, unless otherwise specified, it may be a hydrocarbon group or a derivative thereof. Derivative of a hydrocarbon group refers to a group containing one or more N, O, S, Si, amide, sulfonyl, sulfoxide, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain. do. Additionally, “divalent organic group” means a divalent group containing carbon. There are no particular limitations on such a divalent organic group, but examples include a divalent group in which one hydrogen atom is removed from the organic group.

As used in this specification, “hydrocarbon group” refers to a group containing carbon and hydrogen, and means a group in which one hydrogen atom is removed from a hydrocarbon. Such hydrocarbon groups are not particularly limited, but include C _1-20 hydrocarbon groups that may be substituted with one or more substituents, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The “aliphatic hydrocarbon group” may be linear, branched, or cyclic, and may be saturated or unsaturated. Additionally, the hydrocarbon group may contain one or more ring structures.

When used in this specification, the substituent for the “hydrocarbon group” is not particularly limited, but includes, for example, a halogen atom, a C _1-6 alkyl group which may be substituted with one or more halogen atoms, and C _{2- 6} alkenyl group, C _2-6 alkynyl group, C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, 5 to 10 membered heterocyclyl group, 5 to 10 membered unsaturated heterocyclyl group, C _6-10 aryl and one or more groups selected from 5- to 10-membered heteroaryl groups.

Hereinafter, a composition containing the fluoropolyether group-containing compound of the present disclosure will be described.

The present disclosure uses the following formula (1):

[Formula:

R ^N 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 which may be substituted with 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 a single bond or a divalent organic group in each occurrence;

R ^A1 , in each occurrence, is independently an OR ^Ac group-containing group;

R ^Ac is a (meth)acryloyl group;

R ^B is independently in 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 which may be substituted with one or more fluorine atoms,

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

A composition comprising a compound represented by is provided.

Said R ^N is a trivalent organic group containing N.

Said R ^N is preferably the following group:

It can be.

In a preferred embodiment, R ^N is:

It can be.

In this aspect, equation (1) becomes the following equation (1'):

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

It is displayed as .

Said R ^F2 is -Rf ² _p -R ^F -O _q -.

Said Rf ² is a C _1-6 alkylene group which may be substituted with one or more fluorine atoms.

The "C _1-6 alkylene group" in the C _1-6 alkylene group which may be substituted by one or more fluorine atoms may be straight chain or branched, and is preferably straight chain or branched C ₁ It is _{a -3} alkylene group, and more preferably a straight chain C _1-3 alkylene group.

The Rf ² is preferably a C _1-6 alkylene group substituted with one or more fluorine atoms, more preferably a C _1-6 perfluoroalkylene group, and still more preferably a C _1-6 alkylene group. ₃ It is a perfluoroalkylene group.

The C _1-6 perfluoroalkylene group may be straight-chain or branched, and is preferably a straight-chain or branched C _1-3 perfluoroalkylene group, and more preferably a straight-chain C _1-3 perfluoroalkylene group. Roalkyl group, specifically -CF ₂ -, -CF ₂ CF ₂ -, or -CF ₂ CF ₂ CF ₂ -.

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

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

The R ^F each independently represents a divalent fluoropolyether group.

R ^F is preferably expressed by the formula:

[Formula:

x1 is an integer from 1 to 6, independently for each (OC _x1 F _2x1 ),

x2 is an integer from 1 to 6, independently for each (OC _x2 F _2x2-2 ),

y1 is an integer from 0 to 300,

y2 is an integer from 0 to 300,

The sum of y1 and y2 is greater than or equal to 1,

The order of existence of each repeating unit enclosed in parentheses with y1 or t2 is arbitrary in the equation.]

It is a group represented by .

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

The ring structure may be the following 3-membered ring, 4-membered ring, 5-membered ring, or 6-membered ring.

[In the formula, * represents the binding position.]

The ring structure may be preferably a 4-membered ring, a 5-membered ring, or a 6-membered ring, and more preferably a 4-membered ring or a 6-membered ring.

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

[In the formula, * represents the binding position.]

R ^F is preferably expressed by the formula:

[Formula:

R ^Fa is independently a hydrogen atom, a fluorine atom, or a chlorine atom in each occurrence,

a, b, c, d, e and f are each independently an integer 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 enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.]

It is a group represented by .

R ^Fa is preferably a hydrogen atom or a fluorine atom, and more preferably a fluorine atom.

a, b, c, d, e and f may each independently be an integer of 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, further 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 unit is -(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 ))-, etc. may be used. -(OCF ₅ F ₁₀ )- is, -(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ CF ₂ )-, -(OCF ₂ CF(CF ₃ ) CF ₂ CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ )CF ₂ )-, -(OCF ₂ CF ₂ CF ₂ CF(CF ₃ ))-, etc. may be used. -(OCF ₄ F ₈ )- is -(OCF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ )-, -(OCF ₂ CF(CF ₃ )CF ₂ )- , -(OCF ₂ CF ₂ CF(CF ₃ ))-, -(OC(CF ₃ ) ₂ CF ₂ )-, -(OCF ₂ C(CF ₃ ) ₂ )-, -(OCF(CF ₃ )CF( CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )-, and -(OCF ₂ CF(C ₂ F ₅ ))- may be used. -(OC ₃ F ₆ )- (i.e., where R ^Fa is a fluorine atom) is -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- and -(OCF Any of ₂ CF(CF ₃ ))- may be used. -(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 units linear, the surface slipperiness and friction durability of the surface treatment layer can be improved.

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

In one embodiment, R ^F is each independently a group represented by any of the following formulas (f1) to (f6).

[Wherein, d is an integer from 1 to 200, and e is 0 or 1, preferably 1.];

[In the formula, c and d are each independently an integer from 0 to 30, and e and f are each independently an integer from 1 to 200,

The sum of c, d, e and f is 2 or more,

The order of existence of each repeating unit enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula.];

[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 a combination of 2 or 3 groups independently selected from these groups ego,

g is an integer from 2 to 100.];

[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 a combination of 2 or 3 groups independently selected from these groups ego,

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 independently selected from these groups. It is a combination,

g is an integer from 2 to 100,

g ^' is an integer from 2 to 100,

R ^r is,

(In the formula, * represents the binding position.)

am.];

[In the formula, e is an integer from 1 to 200, a, b, c, d, and f are each independently integers from 0 to 200, and the sum of a, b, c, d, e, and f is It is 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 formula, f is an integer between 1 and 200, and a, b, c, d, and e are each independently integers between 0 and 200, and is the sum of a, b, c, d, e, and f. is 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 an integer of preferably 5 to 200, more preferably 10 to 100, further preferably 15 to 50, for example 25 to 35. In one aspect, e is 0. In another aspect, e is 1. The -(OC ₃ F ₆ ) _d - is preferably -(OCF ₂ CF ₂ CF ₂ ) _d - Or it is a group represented by -(OCF(CF ₃ )CF ₂ ) _d -, and more preferably, it is a group represented by -(OCF ₂ CF ₂ CF ₂ ) _d -.

In the above formula (f2), e and f are each independently an integer of preferably 5 to 200, more preferably 10 to 200. Additionally, 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 embodiment, the 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 aspect, equation (f2) also has a contribution expressed as -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -.

In the above formula (f3), 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 a combination of 2 or 3 groups independently selected from these groups. , and more preferably, it is a group selected from OC ₃ F ₆ and OC ₄ F ₈ . The combination of 2 or 3 groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited, but examples include -OC ₂ F ₄ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₄ F ₈ -, -OC ₃ F ₆ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₃ F ₆ -, -OC ₃ F ₆ OC ₄ F ₈ -, -OC ₄ F ₈ OC ₄ F ₈ -, -OC ₄ F ₈ OC ₃ F ₆ -, -OC ₄ F ₈ OC ₂ F ₄ -, -OC ₂ F ₄ OC ₂ F ₄ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₂ F ₄ OC ₄ F ₈ -, -OC ₂ F ₄ OC ₃ F ₆ OC ₂ F ₄ -, -OC ₂ F ₄ OC ₃ F ₆ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₄ F ₈ OC ₂ F ₄ -, - OC ₃ F ₆ OC ₂ F ₄ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₃ F ₆ -, -OC ₃ F ₆ OC ₃ F ₆ OC ₂ F ₄ - and -OC ₄ F ₈ OC ₂ F ₄ OC ₂ F ₄ - etc. can be mentioned. In the above formula (f3), g is an integer of preferably 3 or more, more preferably 5 or more. The g is preferably an integer of 50 or less. In the above formula (f3), OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ may be either straight chain or branched, and are preferably straight chain. In this aspect, the formula (f3) is preferably -(OC ₂ F ₄ -OC ₃ F ₆ ) _g - or -(OC ₂ F ₄ -OC ₄ F ₈ ) _g -.

In the formula (f4), R ⁶ , R ⁷ and g have the same meaning as those described in the formula (f3) and have the same aspects. R ^6' , R ^7' and g ^' each have the same meaning as R ⁶ , R ⁷ and g described in the above formula (f3) and have similar aspects. R ^r is preferably,

[In the formula, * represents the binding position.]

And, more preferably,

[In the formula, * represents the binding position.]

am.

In the above formula (f5), e is preferably an integer of 1 to 100, more preferably 5 to 100. 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 to 100, more preferably 5 to 100. 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 embodiment, R ^F is a group represented by the formula (f1).

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

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

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

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

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

In the above R ^F , 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, and still more preferably is 0.2 to 1.5, and more preferably 0.2 to 0.85. By setting the e/f ratio to 10 or less, the slipperiness, friction durability, and chemical resistance (for example, durability against artificial sweat) of the surface treatment layer obtained from this compound are further improved. The smaller the e/f ratio, the more improved the slipperiness 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 improved. The larger the e/f ratio, the more improved the stability of the compound.

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

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

In the above 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, and more preferably 2,000 to 10,000. In this specification, the number average molecular weight of R ^F1 and R ^F2 is the value measured by ¹⁹ F-NMR.

In another embodiment, the number average molecular weight of R ^F1 may be 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, for example 3,000 to 6,000. .

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

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

The above X ^a is a group at both ends, a single bond or a divalent linking group that connects R ^F2 and R ^N in formula (1). ^As and a divalent hydrocarbon group having 1 to 10 carbon atoms containing at least one bond selected from the group consisting of an ester bond.

For X ^a , the following equation:

(In ^{the formula} , ^{X 121} _to .)ego,

The X ^a1 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 bonded to ^{CX 121}

x1 is an integer from 0 to 10, y1 is 0 or 1, and z1 is an integer from 1 to 10.)

A group represented by is more preferable.

As the above X ^a1 , -O- or -C(=O)O- is preferable.

As X ^a above, the following formula:

(In the formula, m11 is an integer from 1 to 3, m12 is an integer from 1 to 3, and m13 is an integer from 1 to 3.)

A group represented by

(In the formula, m14 is an integer from 1 to 3, m15 is an integer from 1 to 3, and m16 is an integer from 1 to 3.)

A group represented by

(In the formula, m17 is an integer from 1 to 3, and m18 is an integer from 1 to 3.)

A group represented by

(In the formula, m19 is an integer from 1 to 3, m20 is an integer from 1 to 3, and m21 is an integer from 1 to 3.)

A group represented by, or

(In the formula, m22 is an integer from 1 to 3.)

The group represented by is particularly preferable.

As X ^a above, there is no particular limitation, 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 from 0 to 4), -(CF ₂ ) _n5 -(CH ₂ ) _m5 -(n5 and m5 are each independently, 0 to 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. can be mentioned.

Each occurrence of R ^A1 is independently an OR ^Ac group-containing group.

Said R ^Ac is a (meth)acryloyl group. Here, in this specification, “(meth)acryloyl group” includes acryloyl group and methacryloyl group.

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

In one aspect, R ^AC is an acryloyl group.

In another aspect, 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 replacing R ^A1 with -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 aspect, R ^A1 is -R ^A5 -(OR ^AC ) ₂ or -R ^A6 -R ^A5 -(OR ^AC ) ₂ . By replacing R ^A1 with -R ^A5 -(OR ^AC ) ₂ or -R ^A6 -R ^A5 -(OR ^AC ) ₂ , the solubility of the compound of the present disclosure in solvents can be further improved, and further, the solubility of the compound of the present disclosure can be improved. The durability of the resulting surface treatment layer can be increased.

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

Said 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 a preferred embodiment, R ^A5 is the following group.

(In the formula, * is connected to OR ^AC , and ** is connected to X ^b .)

The 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 is -C _1-10 alkylene-O-.

The -C _1-10 alkylene-O- is preferably -C _1-6 alkylene-O-, more preferably -C _2-6 alkylene-O-, and even more preferably -C _{2- 4} It may be alkylene-O-.

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

By containing at ^least two heteroatoms in

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

The above X ^c is a divalent organic group containing a hetero atom.

In a preferred embodiment, X ^c is of the following formula

[During the ceremony,

R ^c1 is, at each occurrence, independently a single bond or a C _1-12 alkylene group,

X ^c1 is, at each occurrence, independently O, NR ^x1 , S, SO or SO ₂ ,

R ^x1 is independently a hydrogen atom or a C _1-6 alkyl group in each occurrence,

X ^c2 is O or NR ^x2 ,

R ^x2 is independently a hydrogen atom or a C _1-6 alkyl group in each occurrence,

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]

It is a group represented by .

By having the above-described group as X ^c , the compound of the present disclosure can further improve the friction durability of the surface treatment layer obtained from this compound.

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

For R ^c1 , the C _1-12 alkylene group is preferably a C _1-10 alkylene group, more preferably a C _2-10 alkylene group, for example, a C _2-9 alkylene group.

The above X ^c1 is independently -S-, -SO- or -SO ₂ - in each occurrence, and is more preferably -S-.

The above X ^c2 is preferably O.

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

The t2 is an integer of 1 to 6, preferably an integer of 1 to 3, more preferably an integer of 1 to 2, and even 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 SO ₂ ,

R ^x1 is independently a hydrogen atom or a C _1-6 alkyl group in each occurrence,

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 SO ₂ ,

X ^c2 is O.

In a more 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.

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

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

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

Said R ^B is independently in each occurrence, R ^F1 -X ^a - or R ^A1 -X ^b -. Here, when R ^B is R ^F1 -X ^a -, there are multiple R ^F1 -X ^a - in the formula, but they may be the same or different. Similarly, when R ^B is R ^A1 -X ^b -, there are multiple R ^A1 -X ^b - in the formula, but they 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 treatment 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 improved.

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 2,500. 6,000, more preferably 2,500 to 5,000. In this specification, the number average molecular weight of the fluorine-containing isocyanur compound is the value measured by ¹⁹ F-NMR. By setting the number average molecular weight of the fluorine-containing isocyanur compound within the above range, the solubility of the fluorine-containing isocyanur compound in the solvent is improved. Additionally, the initial contact angle and friction durability of the surface treatment layer obtained from the compound can be improved.

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

[Formula:

R ^N 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 which may be substituted with 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 -.]

Includes compounds represented by .

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

In a preferred embodiment, R ^N is:

It can be. In this aspect, equation (2) becomes the following equation (2'):

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

It is displayed as .

Said R ^F1 is Rf ¹ -R ^F -O _q -.

In the above formula, Rf ¹ is a C _1-16 alkyl group which may be substituted with one or more fluorine atoms.

The "C _1-16 alkyl group" in the C _1-16 alkyl group which may be substituted by one or more fluorine atoms may be straight chain or branched, and is preferably straight chain or branched C _1-6 It is an 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.

The Rf ¹ is preferably a C _1-16 alkyl group substituted with one or more fluorine atoms, more preferably a CF ₂ HC _1-15 perfluoroalkylene group, and even more preferably a C ₁ It is a _-16 perfluoroalkyl group.

The C _1-16 perfluoroalkyl group may be straight-chain or branched, and is preferably a straight-chain or branched C _1-6 perfluoroalkyl group, especially a C _1-3 perfluoroalkyl group, and more preferably It is a straight-chain 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 .

In one embodiment, in the composition of the present disclosure, the compound represented by formula (1) is 100 mol% relative to the total of the compound represented by formula (1) and the compound represented by formula (2). 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, the compound represented by formula (1) is preferably 1 mol% or more relative to the total of the compound represented by formula (1) and the compound represented by formula (2). It is 99 mol% or less. The lower limit of the content of the compound represented by formula (1) relative 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, it may be 50 mol%, even more preferably 60 mol%, for example, 70 mol%, 80 mol%, or 90 mol%. The upper limit of the content of the compound represented by formula (1) relative 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%, 80 mol%. It may be mol%, or 70 mol%. The compound represented by formula (2) relative 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%. It is 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.

Equation (1a):

[Formula:

R ^F2 is -Rf ² _p -R ^F -O _q -;

Rf ² is a C _1-6 alkylene group which may be substituted with 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 which may be substituted with one or more fluorine atoms.]

To the compound represented by the following formula (1b)

[Formula:

X ^c1 is, at each occurrence, independently O, NR ^x1 , S, SO or SO ₂ ,

R ^x1 is independently a hydrogen atom or a C _1-6 alkyl group in each occurrence,

R ^b2 is a C _1-10 alkylene group.]

By reacting the compound represented by, the following formula (1c):

[Formula:

R ^F1 , Rf ¹ , R ^F , q, X ^a , X ^c1 , and R ^b2 have the same meaning as above,

R ^Bb is R ^F1 -X ^a - or -(CH ₂ ) ₃ -X ^c1 -R ^b2 -OH.]

Obtain the compound represented by

In addition, the compound represented by the formula (1c) obtained above has the following formula (1d)

By reacting the compound represented by , the compound represented by formula (1) of the present disclosure can be obtained.

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 monomers. A composition comprising the compound of the present disclosure and a polymerizable coating monomer is also one of the present inventions (sometimes referred to as composition (a) in this specification). Since composition (a) has the above structure, a coating film is obtained that has a large static contact angle with water or n-hexadecane, is transparent, has excellent release properties, is difficult for fingerprints to adhere to, and can be completely wiped off even if fingerprints are adhered. Lose.

As the polymerizable coating monomer, a monomer having a carbon-carbon double bond is preferable.

Examples of the polymerizable coating 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”). ), monofunctional and/or polyfunctional urethane (meth)acrylate, monofunctional and/or polyfunctional epoxy (meth)acrylate. The composition forming the matrix is not particularly limited, but is generally a composition that acts as a hard coating agent or anti-reflection agent, for example, a hard coating agent containing a polyfunctional (meth)acrylate or a fluorine-containing (meth)acrylate. and an anti-reflective agent containing the anti-reflection agent. The hard coating agent is, for example, available as Beam Set 502H, 504H, 505A-6, 550B, 575CB, 577, 1402 (brand name) from Arakawa Kagaku Kogyo Co., Ltd., and as EBECRYL40 (brand name) from Daicel Scitech Co., Ltd. , is commercially available from Yokohama Rubber Co., Ltd. as the HR300 series (brand name). This anti-reflective agent is commercially available from Daikin Kogyo Co., Ltd., for example, as Optul AR-110 (brand name).

Composition (a) also contains antioxidants, thickeners, leveling agents, antifoaming agents, antistatic agents, antifogging agents, ultraviolet absorbers, pigments, dyes, inorganic fine particles such as silica, fillers such as aluminum paste, talc, glass frit, and metal powder, It may contain polymerization inhibitors such as butylated hydroxytoluene (BHT) and phenothiazine (PTZ).

Composition (a) may further contain a catalyst for urethanization, for example, 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 tetraacetylacetonato.

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 catalyst include diazabicycloundecene.

Composition (a) preferably also contains a solvent. Examples of the solvent include a fluorine-containing organic solvent or a fluorine-free organic solvent.

Examples of the fluorine-containing organic solvent include perfluorohexane, perfluorooctane, perfluorodimethylcyclohexane, perfluorodecalin, perfluoroalkylethanol, perfluorobenzene, perfluorotoluene, and perfluorocarbon. Roalkylamine (Fluorinaut (brand name), etc.), perfluoroalkyl ether, perfluorobutyltetrahydrofuran, polyfluoro aliphatic hydrocarbon (Asahiclin AC6000 (brand name)), hydrochlorofluorocarbon (Asahiclin AK -225 (brand name), etc.), hydrofluoroether (Novec (brand name), HFE-7100 (brand name), HFE-7300 (brand name), etc.), 1,1,2,2,3,3,4-heptafluor Rocyclopentane, fluorine-containing alcohol, perfluoroalkyl bromide, perfluoroalkyl iodide, perfluoropolyether (Krytox (brand name), Demnum (brand name), Fomblin (brand name), etc.), 1,3 - Bistrifluoromethylbenzene, 2-(perfluoroalkyl)ethyl methacrylate, 2-(perfluoroalkyl)ethyl acrylate, perfluoroalkylethylene, Freon 134a, and hexafluoropropene oligomer. there is.

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, and propylene glycol mono. Ethyl ether acetate, 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, dimethyl sulfoxide, 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 said solvent may be used individually by 1 type, or may be used in combination of 2 or more types.

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

For example, an antifouling layer can be formed by applying composition (a) to a substrate. Additionally, it is also possible to form an antifouling layer by polymerizing after application. Examples of the base material include resins (particularly non-fluorine resins).

The compounds of the present disclosure can be used together with alkali-soluble resins, curable resins, or curable monomers. A composition comprising the above-mentioned compound and a curable resin or curable monomer is also one of the present inventions (sometimes referred to as composition (b) in this specification). Since the composition (b) has the above-described structure, it is difficult for fingerprints to adhere, and even if fingerprints adhere, a coating film that can be completely wiped off is obtained.

The curable resin may be either a photo-curable resin or a thermo-curable resin, and is not particularly limited as long as it is a resin that has heat resistance and strength. However, a photo-curable resin is preferable and an ultraviolet curable resin is more preferable.

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

The curable resin or the monomer constituting the curable resin specifically includes, for example, alkyl vinyl ethers such as cyclohexylmethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, and 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-vinylpy Rolidone, dimethylaminoethyl methacrylate, silicone-based acrylate, maleic anhydride, vinylene carbonate, linear branched polyacrylate, cyclic branched 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 preferable.

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)acrylate, (f) (meth)acrylate monomer, etc.

Specific examples of the curable monomer include the following.

(a) As urethane (meth)acrylate, poly(meth) represented by tris(2-hydroxyethyl)isocyanurate diacrylate and tris(2-hydroxyethyl)isocyanurate triacrylate. [Acryloyloxyalkyl] isocyanurate.

(b) Epoxy (meth)acrylate is obtained by adding a (meth)acryloyl group to an epoxy group, and generally uses bisphenol A, bisphenol F, phenol novolac, and alicyclic compounds 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, and 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, alkenyl succinic acid, etc. .

(d) Examples of polyether (meth)acrylate include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polyethylene glycol-polypropylene glycol di(meth)acrylate.

(e) Silicone (meth)acrylate is obtained by modifying one end or both ends of dimethylpolysiloxane with a molecular weight of 1,000 to 10,000 into a (meth)acryloyl group. Examples of the silicone (meth)acrylate include the following compounds.

(f) Examples of (meth)acrylate monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and 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, n-octyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate , 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (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 , 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate.

Among the curable resins and curable monomers, the following are available and preferred from the market.

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

Examples of the curable monomer 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, and two-end (meth)acrylic type 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, Silaplane FM-0711 of single-ended (meth)acrylic type. , Silaplane FM-0721, Silaplane FM-0725, Silaplane TM-0701, and Silaplane TM-0701T (manufactured by JCN).

As multifunctional acrylates, 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 (produced by Shin Nakamura High School), etc. can be mentioned.

Examples of polyfunctional methacrylates include TMPT (manufactured by Shinnakamura Kogyo).

Examples of (meth)acrylates containing an alkoxysilane group include 3-(meth)acryloyloxypropyltrichlorosilane, 3-(meth)acryloyloxypropyltrimethoxysilane, and 3-(meth)acryloyloxypropyl. Triethoxysilane, 3-(meth)acryloyloxypropyltriisopropoxysilane (also known as (triisopropoxysilyl)propyl methacrylate (abbreviated name: TISMA) and triisopropoxysilyl)propyl acrylate), 3-(meth)acryloxyisobutyltriethoxysilane, 3-(meth)acryloxyisobutyltriethoxysilane, 3-(meth)acryloxyisobutyltriisopropoxy 3-(meth)acryloxyisobutyltrime Toxisilane, etc. are mentioned.

Composition (b) also preferably contains a crosslinking catalyst. Examples of the crosslinking catalyst include radical polymerization initiators and acid generators.

The radical polymerization initiator is a compound that generates radicals by heat or light, and includes a radical thermal polymerization initiator and a radical photopolymerization initiator. In the present invention, the 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, and diisopropyl peroxide. Peroxycarbonates such as oxydicarbonate and bis(4-t-butylcyclohexyl)peroxydicarbonate, and alkyl peresters such as t-butyl peroxyoctoate and t-butyl peroxybenzoate. peroxide compounds such as these, and radical-generating azo compounds such as azobisisobutyronitrile.

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 such as thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis Benzophenones such as (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, 2-benzyl-2-dimethylamino-1-(4-mor Acetophenones such as polynophenyl)-butan-1-one, quinones such as anthraquinone and 1,4-naphthoquinone, ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. Aminobenzoic acids such as (n-butoxy)ethyl, isoamyl 4-dimethylaminobenzoate, and 2-ethylhexyl 4-dimethylaminobenzoate, halogen compounds such as phenacyl chloride and trihalomethylphenylsulfone, and acylphosphineoxy. Peroxides such as Drew and di-t-butyl peroxide can be mentioned.

The following are exemplified as commercial products of the radical photopolymerization initiator.

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),

IRGACURE 261, IRGACURE 369, IRGACURE 500,

DAROCUR 1173: 2-Hydroxy-2-methyl-1-phenyl-propan-1-one,

DAROCUR TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide,

DAROCUR 1116, DAROCUR 2959, DAROCUR 1664, DAROCUR 4043,

IRGACURE 754 Oxyphenylacetic acid: mixture of 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester, oxyphenylacetic acid, 2-(2-hydroxyethoxy)ethyl ester,

IRGACURE 500: mixture of IRGACURE 184 and benzophenone (1:1);

IRGACURE 1300: mixture of IRGACURE 369 and IRGACURE 651 (3:7);

IRGACURE 1800: mixture of CGI 403 and IRGACURE 184 (1:3);

IRGACURE 1870: mixture of CGI 403 and IRGACURE 184 (7:3);

DAROCUR 4265: A mixture of DAROCUR TPO and DAROCUR 1173 (1:1).

Additionally, IRGACURE is made by BASF, and DAROCUR is made by Merck Japan.

In addition, when using a radical photopolymerization initiator as the crosslinking catalyst, diethylthioxanthone, isopropylthioxanthone, etc. may be used together as a sensitizer, and as a polymerization accelerator, DAROCUR EDB (ethyl-4-dimethylamino Benzoate), DAROCUR EHA (2-ethylhexyl-4-dimethylaminobenzoate), etc. may be used together.

The compounding amount of the sensitizer when using the sensitizer is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin or the curable monomer. More preferably, it is 0.1 to 2 parts by mass.

In addition, when using the polymerization accelerator, the compounding amount of the polymerization accelerator is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin or the 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 a thermal acid generator and a photoacid generator. In the present invention, a photoacid generator is preferred.

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

The photoacid generator is composed of a chromophore that absorbs light and an acid precursor that becomes an acid after decomposition. When the photoacid generator with this structure is irradiated with light of a specific wavelength, the photoacid generator is excited and acid is generated from the acid precursor portion. do.

Examples of the photoacid generator include diazonium salt, phosphonium salt, sulfonium salt, iodonium salt, CF ₃ SO ₃ , p-CH ₃ PhSO ₃ , p-NO ₂ PhSO ₃ (where Ph is a phenyl group), etc. salts, organic halogen compounds, orthoquinone-diazide sulfonyl chloride, or sulfonic acid esters. Other photoacid generators include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound, 2-trihalomethyl-5-aryl-1,3,4-oxadiazole compound, 2 -Trihalomethyl-5-hydroxyphenyl-1,3,4-oxadiazole compounds and the like can also be mentioned. Additionally, the organic halogen compound is a compound that forms hydrohalogen acid (for example, hydrogen chloride).

The following are exemplified as commercial products of the photoacid generator.

WPAG-145 [bis(cyclohexylsulfonyl)diazomethane], WPAG-170[bis(t-butylsulfonyl)diazomethane], and WPAG-199[bis(p-toluenesulfonyl) manufactured by Wako Pure Chemical Industries, Ltd. )Diazomethane], WPAG-281[triphenylsulfoniumtrifluoromethanesulfonate], WPAG-336[diphenyl-4-methylphenylsulfoniumtrifluoromethanesulfonate], WPAG-367[diphenyl-2 , 4,6-trimethylphenylsulfonium p-toluenesulfonate], IRGACURE PAG 103 [(5-propylsulfonyloximino-5H-thiophen-2-ylidene)-(2-methylphenyl) manufactured by Chiba Specialty Chemicals. ) Acetonitrile], IRGACURE PAG 108 [(5-octysulfonyloxymino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile)], IRGACURE PAG 121 [5-p-toluenesulfony Oximino-5H-thiophen-2-ylidene-(2-methylphenyl)acetonitrile], IRGACURE PAG 203, CGI 725, TFE-triazine [2-[2-(furan-2-yl)] manufactured by Sanwa Chemical Co., Ltd. Ethenyl]-4,6-bis(trichloromethyl)-s-triazine], TME-triazine[2-[2-(5-methylfuran-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 compounding 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 the curable monomer. Within this range, a sufficient cured body can be obtained. The compounding 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.

Additionally, when using the acid generator as the crosslinking catalyst, diffusion of the acid generated from the acid generator may be controlled by adding an acid scavenger if necessary.

The acid scavenger is not particularly limited, but basic compounds such as amines (particularly organic amines), basic ammonium salts, and basic sulfonium salts are preferred. Among these acid capture agents, organic amines are more preferable because they have excellent image performance.

The acid scavenger specifically includes 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,4-diazabicyclo[4.3.0]-5-nonene. Zabicyclo[2.2.2]octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazole, hydroxypyridine, pyridine, 4,4'-diaminodi Phenyl ether, pyridinium p-toluenesulfonate, 2,4,6-trimethylpyridinium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, tetrabutylammonium lactate, triethylamine, tributylamine, etc. I can hear it. Among these, 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, imidazole, hydroxypyridine, pyridine, 4,4'-diaminodiphenyl ether, triethylamine, Organic amines such as tributylamine are preferred.

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

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

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, and 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, etc.

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, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichlorethylene, perchlorethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane etc. can be mentioned. These solvents may be used individually, or two or more types may be mixed and used.

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

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

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

Examples of the synthetic resin include cellulose resins such as triacetylcellulose (TAC), polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer (EVA), cyclic polyolefins, modified polyolefins, Polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polyamidoimide, polycarbonate, poly-(4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylic -Styrene copolymer (AS resin), butadiene-styrene copolymer, ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polyputylene terephthalate (PBT), polycyclohexane terephthalate (PCT), etc. of polyester, polyether, polyether ketone (PEK), polyether ether ketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluorine-based resins, various thermoplastic elastomers such as styrene-based, polyolefin-based, polyvinyl chloride-based, polyurethane-based, fluororubber-based, chlorinated polyethylene-based, epoxy resin, phenol Resins, urea resins, melamine resins, unsaturated polyesters, silicone resins, polyurethanes, etc., or copolymers mainly made of these, blends, polymer alloys, etc. may be used, and one or two or more of these may be used in combination (e.g. For example, it can be used as a laminate of two or more layers.

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

The compounds of the present disclosure can be used together with solvents. A composition comprising the above-mentioned compound and a solvent is also one of the present inventions (sometimes referred to as composition (c) in this specification).

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

As the solvent, a fluorine-based solvent is preferable. 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 with 1 to 16 carbon atoms, a fluorinated alkyl group with 1 to 16 carbon atoms, -R ¹¹⁴ -X ¹¹¹ (R ¹¹⁴ is a single bond or an alkylene group with 1 to 16 carbon atoms, 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 (substituted with fluorine) (optional), 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.

R ¹¹¹ and R ¹¹³ are independently preferably 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), and 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, and X ¹¹¹ is -OH or -OCH ₂ CH=CH ₂ ).

As m, an integer of 300 or less is preferable, and an integer of 100 or less is more preferable.

As R ¹¹² , a fully fluorinated alkylene group having 1 to 4 carbon atoms is preferable. As -R ¹¹² O-, for example

_{Equation : - (} ^C _{_ _ _ _ _ _ _ _ _ _ _}

(n111, n112, n113, n114 and n115 are independently 0 or an integer of 1 or more, X ¹¹² is H, F or Cl, the order of existence of each repeating unit is arbitrary),

Equation: -(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)

etc. can be mentioned.

It is preferable that n111 to n115 are each integers of 0 to 200. The total of n111 to n115 is preferably 1 or more, more preferably 5 to 300, further preferably 10 to 200, and especially 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 2 or 3 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 includes, for example, -OC ₂ F ₄ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₄ F ₈ -, -OC ₃ F ₆ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₃ F ₆ -, -OC ₃ F ₆ OC ₄ F ₈ -, -OC ₄ F ₈ OC ₄ F ₈ -, -OC ₄ F ₈ OC ₃ F ₆ -, -OC ₄ F ₈ OC ₂ F ₄ -, -OC ₂ F ₄ OC ₂ F ₄ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₂ F ₄ OC ₄ F ₈ -, -OC ₂ F ₄ OC ₃ F ₆ OC ₂ F ₄ -, -OC ₂ F ₄ OC ₃ F ₆ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₄ F ₈ OC ₂ F ₄ -, - OC ₃ F ₆ OC ₂ F ₄ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₃ F ₆ -, -OC ₃ F ₆ OC ₃ F ₆ OC ₂ F ₄ - and -OC ₄ F ₈ OC ₂ F ₄ OC ₂ F ₄ - and the like. The f is an integer of 2 to 100, preferably an integer of 2 to 50. In the above formula, OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ may be either straight chain or branched, and are preferably straight chain. 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, further preferably 10,000 or less, and especially preferably 6,000 or less. The weight average molecular weight can be measured by gel permeation chromatography (GPC).

Examples of the commercially available fluoropolyethers include Demnum (manufactured by Daikin Industries, Ltd.), Fomblin (manufactured by Solvay Specialty Polymers Japan), Varierta (manufactured by NOK Kluber Corporation), and Crytox (manufactured by DuPont Corporation). there is.

The fluorine-containing oil may contain, 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 (sum of two or more types). there is. In one embodiment, the fluorine-containing oil is, for example, 0.1 mass% or more, preferably 0.1% by mass or more, relative to the compounds represented by formulas (1) and (2) of the present disclosure (sum of two or more types). It may contain 1% by mass or more, for example, 5% by mass or more.

Composition (c) can be used to form a release layer on a substrate. The release layer can be formed using a method of immersing the substrate in the composition (c), a method of exposing the substrate to vapor of the composition (c) and depositing it, a method of printing the composition (c) on the substrate, or using an inkjet. and a method of applying the composition (c) to the substrate. It may be dried after the immersion, the deposition, the printing, and the application. As the substrate, a mold in which a concavo-convex pattern is formed can be used, and the mold in which a release layer is formed can be used for nanoimprinting.

Examples of the substrate include resins, such as polymer resins such as silicone.

The present disclosure also provides an antifouling agent comprising the above compound or the above composition.

The antifouling agent can be used by applying it to a resin (particularly, a non-fluorine resin).

The antifouling agent can be used in a variety of products (particularly, optical materials) that require surface antifouling properties and swelling properties. Examples of articles include front protection plates, anti-reflection plates, polarizers, and anti-glare plates for displays such as PDP and LCD; cover windows for foldable displays, rollable displays, and bending displays; Devices such as mobile phones and mobile information terminals; touch panel sheet; Optical discs such as DVD discs, CD-Rs, and MOs; spectacle lenses; optical fiber; housing; Examples include interior items of automobiles (specifically, seat sheets and their sides inside the automobile, ceiling, walls and floor within the automobile, dashboard and its lower portion, panels around the driver's seat, switches, levers, etc., and the interior of the trunk). .

Optical materials such as optical discs are perfluorocarbons contained in a composition containing a carbon-carbon double bond, or in a polymer composed of a composition containing a carbon-carbon double bond, or in a polymer of a composition containing a carbon-carbon double bond and a monomer containing a carbon-carbon double bond. It is preferable that the surface is coated with a film formed by adding low polyether (PFPE) content to 0.01% by weight to 10% by weight. At 0.01% by weight to 10% by weight, the characteristic physical properties (antifouling, etc.) of PFPE addition appear, surface hardness is high, and transmittance is high.

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

With the release agent, a release layer can be formed on the substrate. The release layer may be formed by a method of immersing the substrate in the release agent, a method of depositing the substrate by exposing it to vapor of the release agent, a method of printing the composition on the substrate, or applying the composition to the substrate using an inkjet. How to do it, etc. It may be dried after the immersion, the vapor deposition, the printing, and the application. As the substrate, a mold in which a concavo-convex pattern is formed can be used, and the mold in which a release layer is formed can be used for nanoimprinting.

Examples of the substrate include metals, metal oxides, polymer resins such as quartz and silicon, 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 ㎛, preferably 0.1 to 30 ㎛, more preferably 0.5 to 20 ㎛, to ensure optical performance, surface slipperiness, friction durability and antifouling properties. It is desirable in that respect.

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

The compound of the present disclosure can be used together with an alkali-soluble resin or a polymerization initiator. A composition comprising the above-mentioned compound and a curable resin or curable monomer is also one of the present inventions (sometimes referred to as composition (d) in this specification). 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 to a resist composition, and the present disclosure provides a resist resin composition containing the composition of the present disclosure, an alkali-soluble resin, and a polymerization initiator.

The 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 preferable.

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

The photocurable functional group is preferably an ethylenic double bond. Examples of the ethylenic double bond include double bonds having addition polymerization, such as (meth)acryloyl group, allyl group, vinyl group, vinyloxy group, and vinyloxyalkyl group. These may be used individually or in combination of two or more types. Additionally, some or all of the hydrogen atoms of the ethylenic double bond may be substituted with an alkyl group such as a methyl group.

Examples of the alkali-soluble resin having an ethylenic double bond include a resin having a side chain having an acidic group and a side chain having an ethylenic double bond, and a resin in which an acidic group and an ethylenic double bond are introduced into an epoxy resin. These may be used individually or in combination of two or more types. As such an alkali-soluble resin, those described in specification WO2014/084279 can be used.

Resins having a side chain having an acidic group and a side chain having an ethylenic double bond include those made by reacting a copolymer of acrylic acid, 2-hydroxymethacrylate, and other monomers with 2-acyloyloxytylisocyanate, etc. . In addition, the unsaturated group-containing urethane resin as component (A) of Japanese Patent Publication No. 2001-33960, the polyurethane compound as component (E) of Japanese Patent Publication No. 2003-268067, and the (A) component of Japanese Patent Publication No. 2010-280812. and urethane-based resins such as phosphorus-reactive 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, and a diisocyanate compound such as trimethylhexamethylene diisocyanate, with glycidyl as an optional component. Resins obtained by reacting polybasic acid anhydrides such as methacrylate and phthalic anhydride can be mentioned.

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

Resins in which acidic groups and ethylenic double bonds are introduced into epoxy resins include bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, phenol novolak-type epoxy resins, cresol novolac-type epoxy resins, trisphenol methane-type epoxy resins, and naphthalene skeleton. An epoxy resin having an epoxy resin having a biphenyl skeleton, a fluorenyl-substituted bisphenol A type epoxy resin, and a resin in which an acidic group and an ethylenic double bond are introduced into the epoxy resin described in Japanese Patent Application Laid-Open No. 2006-84985 are preferred. .

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

The mass average molecular weight (Mw) of the alkali-soluble resin is preferably 1.0×10 ³ to 20×10 ³ , and particularly preferably 2×10 ³ to 15×10 ³ . Additionally, the number average molecular weight (Mn) is preferably 500 to 13×10 ³ , and particularly preferably 1.0×10 ³ to 10×10 ³ . If the mass average molecular weight (Mw) and number average molecular weight (Mn) are more than the lower limit of the above range, curing during exposure is sufficient, and if the mass average molecular weight (Mw) and number average molecular weight (Mn) are less than the upper limit of the above range, developability is good. The number average molecular weight (Mn) and mass average molecular weight (Mw) are those measured by gel permeation chromatography using polystyrene as a standard material.

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

Examples of the polymerization initiator include α-diketones such as methylphenylglyoxylate and 9,10-phenanthrenequinone; acylophosphones such as benzoin; Acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; Thioxanthone such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, and 2,4-diethylthioxanthone; Benzophenones such as benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-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)-butan-1-one Acetophenones such as; Quinones such as anthraquinone, 2-ethylanthraquinone, camphorquinone, and 1,4-naphthoquinone; Aminobenzoic acids such as 2-dimethylaminobenzoic acid ethyl and 4-dimethylaminobenzoic acid (n-butoxy)ethyl; Halogen compounds such as phenacyl chloride and trihalomethylphenylsulfone; Acylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; Peroxides such as di-t-butyl peroxide; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime), ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole- Oxime esters such as 3-yl]-1-(O-acetyloxime), triethanolamine, methyldiethanolamine, triisopropanolamine, n-butylamine, N-methyldiethanolamine, diethylaminoethyl methacrylate and aliphatic amines. The photopolymerization initiator may be used individually by 1 type or may be used in combination of 2 or more types.

Composition (d) may also include a crosslinking 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 also has a crosslinking agent (hereinafter referred to as , also called “non-acidic cross-linking agent”). The composition containing the cross-linking agent becomes a sufficiently cured cured film by cross-linking with the cross-linking agent when the alkali-soluble resin polymerizes through exposure to light.

The mass average molecular weight (Mw) of the polyfunctional low molecular weight compound is preferably 300 to 1000, and more preferably 500 to 800. Moreover, the number average molecular weight (Mn) is preferably 300 to 1000, and particularly preferably 500 to 800. If the mass average molecular weight (Mw) and number average molecular weight (Mn) are within the above ranges, alkali solubility and developability are good.

Examples of the polyfunctional low molecular weight compound include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, and polyisocyanate compounds and (meth)acryloyl-containing hydroxy compounds. Examples include compounds in which an acidic group is introduced by leaving two or more unsaturated bonds (ethylenic double bonds) in an ethylenic compound having a urethane skeleton obtained by reacting the compound.

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

Examples of the aliphatic polyhydroxy compound in the ester of the aliphatic polyhydroxy compound introducing an acidic group and an unsaturated carboxylic acid include compounds having three or more hydroxy groups, such as trimethylolpropane, trimethylolethane, pentaerythritol, Dipentaerythritol, tripentaerythritol, tetrapentaerythritol, etc. can be mentioned. Examples of unsaturated carboxylic acids include (meth)acrylic acid, itaconic acid, irotonic acid, and maleic acid.

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

Specific examples of the aromatic carboxylic acid anhydride used to introduce an acidic group into the ester include phthalic anhydride, and specific examples of the non-aromatic carboxylic acid anhydride include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. , alkylated hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride, and among these, succinic anhydride is preferable.

In the polyfunctional low molecular weight compound, as a compound obtained by reacting an aromatic carboxylic acid anhydride with an aliphatic polyhydroxy compound and an ester of an unsaturated carboxylic acid, for example, three hydroxy groups of pentaerythritol are substituted with acryloyloxy groups. , and the remaining hydroxy group is, for example, 2,2,2-triacryloyloxymethylethylphthalic acid, which has a structure in which phthalic acid and ester are bonded.

As the polyfunctional low molecular weight compound, a compound having a dipentaerythritol skeleton is preferable. As a compound having a dipentaerythritol skeleton, for example, five hydroxy groups of dipentaerythritol are replaced with (meth)acryloyloxy groups, and the remaining one hydroxy group is ester bonded with succinic acid, for example, thereby introducing an acidic group. compounds are preferred.

The acid value of the polyfunctional low molecular weight compound is preferably 10 to 100 mgKOH/g, and more preferably 20 to 95 mgKOH/g. If the acid value of the polyfunctional low molecular weight compound is more than the above lower limit, better solubility in a developer solution can be obtained in the negative photosensitive composition, and if it is less than the above upper limit, manufacturing and handling properties are good, and sufficient polymerizability can be secured. Therefore, the curability, such as surface smoothness, of the resulting coating film also improves.

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 di(meth)acrylate. Trimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol heptaacrylate, tripentaerythritol octaacrylate, tetrapenta Erythritol heptaacrylate, tetrapentaerythritol octaacrylate, tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, ethoxylated isocyanuric acid tri(meth)acrylate, tris-(2-acrylic acid) Urethane skeleton in which HDI (hexamethylene diisocyanate) is bonded to 1oxyethyl)isocyanurate, ε-caprolactone-modified tris-(2-acryloyloxyethyl)isocyanurate, and dipentaerythritolpentaacrylate. Monomers (ten functionals) and urethane acrylates having , etc. can be mentioned. Non-acidic crosslinking agents may be used individually or in combination of two or more types.

The content ratio of the crosslinking agent in the total solid content in the composition (d) is preferably 5 to 80% by mass, and particularly preferably 10 to 60% by mass.

The content ratio of the polyfunctional low molecular weight compound in the total solid content in the composition (d) is preferably 5 to 80% by mass, and more preferably 7 to 60% by mass. When the content ratio 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 ratio of the non-acidic cross-linking agent in the total solid content in the composition is preferably 0.1 to 50% by mass, and more preferably 1.0 to 40% by mass. Additionally, the ratio of the polyfunctional low molecular weight compound to the total of 100 parts by mass of the polyfunctional low molecular weight compound and the non-acidic crosslinking agent is preferably 10 to 90 parts by mass, and more preferably 15 to 70 parts by mass. By setting the polyfunctional low molecular weight compound and the non-acidic crosslinking agent in the above ratio, it becomes easy to adjust the acid value and the number of photocurable functional groups of the entire crosslinking agent.

In addition, as a crosslinking agent, a mixture of a polyfunctional low molecular weight compound and a non-acidic crosslinking agent is commercially available, such as dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid of dipentaerythritol pentaacrylate. An ester mixture, etc. may be used.

Composition (d) may also include 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, Ethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide And at least one solvent selected from the group consisting of 2-propanol is more preferable.

When the solvent contains water, the water content is preferably 10 mass% or less of the total solvent. Within the above range, unevenness of the patterned substrate consisting of a partition formed from the cured film obtained from the composition (d) can be reduced. Moreover, it is more preferable that the water content is 1 to 10 mass%. If it is within the above range, the dispersion stability of the composition is good.

The solvent content in the composition (d) is preferably 10 to 99% by mass, more preferably 20 to 95% by mass, and particularly preferably 50 to 90% by mass, based on the total amount of the composition. Moreover, with respect to a total of 100 mass% of alkali-soluble resin and crosslinking agent, 0.1 to 3000 mass% is preferable, and 0.5 to 2000 mass% is more preferable.

Composition (d) may also, if necessary, contain a thiol compound, a phosphoric acid compound, a polymerization inhibitor, a thermal crosslinking agent, a polymer dispersant, a dispersing aid, a silane coupling agent, fine particles, a curing accelerator, a thickener, a plasticizer, an antifoaming agent, a leveling agent and a cratering agent. It may contain one or more other additives selected from the group consisting of inhibitors.

Composition (d) can be used to form a cured film or barrier rib used in optical devices, such as organic EL devices, 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 has few development residues. In particular, the bank resist obtained from composition (d) has good ink repellency on the upper surface, good development adhesion to the substrate, and has little development residue, making it suitable for optical elements, especially those produced by the inkjet method. When used in organic EL devices, quantum dot displays, TFT arrays, or thin film solar cells, ink is uniformly applied to the openings to form dots with high precision.

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

As an apparatus for performing X-ray photoelectron spectroscopy to measure the atomic composition of the cured film and the ratio of constituent atoms, XPS, PHI5000VersaProbeII manufactured by ULVAC PHI, Inc. can be used. The measurement conditions for XPS analysis include 25W of monochromated AlKα rays as the X-ray source, a photoelectron detection area of 1400 ㎛ ), it is possible to set the pass energy to 23.5 eV, etc., and to use Ar ions as sputter ions. The composition of the surface of the cured film can be determined by observing the peak areas of C1s, O1s, and F1s and calculating the atomic ratios of carbon, oxygen, and fluorine using the above-described device and measurement conditions.

Additionally, the composition of the cured film in the depth direction can be analyzed by XPS. As measurement conditions for XPS analysis, monochromated AlKα rays are used at 25 W as the X-ray source, the photoelectron detection area is 1400 ㎛ degrees, 90 degrees), the pass energy is set to 23.5 eV, etc., and Ar ions can be used as sputter ions. 1 to 100 nm is etched by sputtering with Ar ions, and the composition in the cured film at the depth after each etching can be obtained. Additionally, by adjusting the photoelectron detection angle of the XPS analysis described above, the detection depth can be appropriately adjusted. For example, by making it a shallow angle close to 20 degrees, the detection depth can be made to about 3 nm, while by making it a deep angle close to 90 degrees, the detection depth can be made about dozens of nm.

The fluorine atom concentration on the surface of the cured film obtained by the composition of the present disclosure may be preferably 40% or more, more preferably 45% or more, and still more preferably 50% or more. The upper limit of this 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 in this range, the cured film obtained from the composition of the present disclosure has excellent ink repellency.

The cured film obtained by composition (d) of the present disclosure has a high perfluoropolyether group (PFPE) concentration on the surface. Here, the perfluoropolyether group concentration on the surface of the cured film can be measured by XPS. For example, focusing on the O1s orbital, the CO bond of CF ₂ CF ₂ -O-CF ₂ CF ₂ in the perfluoropolyether group was detected at 535 eV, and the COC bond from the hard coat agent was detected at 533 eV, C=O. Binding is detected at 531ev each. Therefore, the perfluoropolyether group ratio can be determined as the ratio of the peak area with the peak top around 535 to 536 eV among the total amount of peak area observed at about 530 to 540 eV, which is considered to be the O1s orbital.

The perfluoropolyether group concentration on the surface of the cured film obtained by the composition of the present disclosure may be preferably 30% or more, more preferably 40% or more, and still more preferably 50% or more. 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 in this range, the cured film obtained from the composition of the present disclosure has excellent ink repellency.

Above, the composition of the present disclosure has been described in detail. In addition, the use of the composition of the present disclosure, the method of use, the method of manufacturing the article, etc. are not limited to those exemplified above.

Example

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

Synthesis Example 1: Preparation of PFPE-containing compound (A)

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, and according to the method described in WO2018/056413A1, the following perfluoropolyether (PFPE) ) containing compound (A) was synthesized.

PFPE-containing compounds (A):

Synthesis Examples 2 to 5: Preparation of PFPE-containing compounds (B), (C), (D), and (E)

Using the PFPE-containing compound (A) obtained above, the following perfluoropolyether (PFPE)-containing compounds (B), (C), (D), and (E) were prepared according to the method described in WO2021/024964A1. was synthesized, and for each compound, a 20 wt% solution in a mixed solvent of 1,1,2,2,3,3,4-heptafluorocyclopentane and 2-butanone was obtained.

PFPE-containing compounds (B):

PFPE-containing compounds (C):

PFPE-containing compounds (D):

PFPE-containing compounds (E):

Synthesis Example 6: Preparation of PFPE-containing compound (F)

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, and according to the method described in WO2018/056413A1, the following perfluoropolyether (PFPE) ) containing compound (F) was synthesized.

Compounds containing PFPE (F):

Synthesis Examples 7 to 9: Preparation of PFPE-containing compounds (G), (H), and (I)

Using the PFPE-containing compound (F) obtained above as a starting material, the following perfluoropolyether (PFPE)-containing compounds (G), (H), and (I) were prepared according to the method described in WO2021/024964A1. , a 20 wt% solution of 1,1,2,2,3,3,4-heptafluorocyclopentane and 2-butanone in a mixed solvent was obtained, respectively.

PFPE-containing compounds (G):

Compounds containing PFPE (H):

PFPE-containing compounds (I):

<Compatibility with PGMEA>

The PFPE-containing compound (B), or a mixture of the PFPE-containing compound (B) and the PFPE-containing compound (G) in the ratios shown in Table 1 were each added to PGMEA (propylene glycol monomethyl ether acetate) at a concentration of 4.0 wt%. After mixing as much as possible and shaking well, the appearance of the mixed liquid was evaluated according to the following standards. The results are shown in Table 1.

◎: Colorless and transparent solution

○: Becomes slightly translucent

(Manufacture of cured film)

Beam set 575CB (manufactured by Arakawa Chemical Industry Co., Ltd.) and methyl isobutyl ketone were mixed and the solid concentration was adjusted to 50 wt%, and then PFPE-containing compound (B) or PFPE-containing compound (B) and PFPE-containing compound (G) were mixed as shown in the table. The mixture mixed in the ratio (molar ratio) shown in 1 was added so that the solid content ratio was 1.0% by mass with respect to Beam Set 575CB, and stirred for 1 hour with a rotary mixer under light blocking to obtain a PFPE-containing hard coat material.

(evaluation)

<Evaluation of properties 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 obtained coating film was irradiated with a light containing UV light of 365 nm at an intensity of 600 mJ/cm2 in a nitrogen atmosphere, and each hard coat material was cured to obtain a cured film (surface treatment layer). The film thickness of the cured film was 5 to 6 μm. About the obtained cured film, initial characteristics were evaluated as follows.

(Measurement of Haze)

For each cured film, Haze was measured. Specifically, using a haze meter (Nippon Denshoku Kogyo Co., Ltd., 7000SP), three different points on the substrate were measured using a measurement method based on ASTM, and the average value was calculated and used. The measurement results are shown in Table 1.

<Evaluation of antifouling properties>

(Fingerprint adhesion)

A finger was pressed against the cured film, and the ease of attachment of the fingerprint was visually determined. Evaluation was made based on the following criteria. The results are shown in Table 1.

○: It was difficult for a fingerprint to be attached, but even if it was attached, the fingerprint was not noticeable.

×: A fingerprint is clearly attached.

(Fingerprint wipeability)

After the above fingerprint adhesion test, the attached fingerprint was wiped five times with a Kimwipe (product name: Jujo Kimberly Co., Ltd.), and the ease of wiping off the attached fingerprint was visually determined. Evaluation was made based on the following criteria. The results are shown in Table 1.

○: Fingerprints can be completely wiped off.

×: The wipe marks of the fingerprint 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 DropMaster700 (manufactured by Kyowa Kaimen Chemical Co., Ltd.). The results are shown in Table 1.

<Method for measuring static contact angle>

The static contact angle was determined by dropping 3 μL of the test liquid from a microsyringe on a horizontally placed substrate and taking a still image 1 second after the drop using a video microscope. Regarding the measured value of the static contact angle of the test liquid, five different points of the surface treatment layer of the substrate were measured, and the average value was calculated and used. For the cured films of the PFPE-containing hard coat materials of Examples 1 to 5, the initial values were measured. The results are shown in Table 1. Regarding the test liquids, measurements were performed on five types of water, n-hexadecane, PGMEA, 1,6-bis(acryloyloxy)hexane, and anisole, and the judgment criteria for each test liquid were as follows. did. The results are shown in Table 1.

Judgment criteria for static contact angle of water

◎: Contact angle 111 degrees or more

○: Contact angle 106 degrees or more, less than 111 degrees

△: Contact angle 100 degrees or more, less than 106 degrees

×: Contact angle less than 100 degrees

Judgment criteria for the static contact angle of n-hexadecane

◎: Contact angle 62 degrees or more

○: Contact angle 61 degrees or more, less than 62 degrees

△: Contact angle 59 degrees or more, less than 61 degrees

×: Contact angle less than 59 degrees

Judgment 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

Judgment criteria for the 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 angle less than 64 degrees

Judgment criteria for static contact angle of anisole

◎: 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 angle less than 64 degrees

In the same manner as above, PFPE-containing compound (C) or a mixture of PFPE-containing compound (C) and PFPE-containing compound (H) in the ratio shown in Table 2 was evaluated as Examples 6 to 10. The results are shown in Table 2.

In the same manner as above, PFPE-containing compound (D) or a mixture of PFPE-containing compound (D) and PFPE-containing compound (I) in the ratio shown in Table 3 was evaluated as Examples 11 to 15. The results are shown in Table 3.

In the same manner as above, PFPE-containing compound (E), or a mixture of PFPE-containing compound (E) and PFPE-containing compound (G), (H) or (I) in the ratio shown in Table 4 was prepared as Examples 16 to 25. , evaluation was performed. The results are shown in Table 4.

Comparative Examples 1 and 2

The PFPE-containing compound was changed to the fluorine-containing compound (J) shown below, and measurement was performed in the same manner as in Example 1 above, except that it was added to 4.0 mass% with respect to beam set 575CB (Comparative Example 1 ). In addition, the hard coat material containing only the mixed solution of beam set 575CB and methyl isobutyl ketone without any PFPE-containing compound was measured in the same manner as in Example 1 (Comparative Example 2). The results are shown in Table 5.

Fluorine-containing compounds (J):

As understood from the results in Tables 1 to 5, the treated substrate having a cured film obtained from the hard coat materials of Examples 1 to 25 containing the PFPE-containing compound of the present disclosure has a transparent and clean appearance with low Haze and does not adhere to fingerprints. In addition to excellent water resistance and fingerprint wiping properties, this treated substrate exhibited excellent water and oil repellency. On the other hand, the compositions containing the fluorine-containing compound (J) and Comparative Examples 1 and 2 without the addition of the PFPE-containing compound did not have sufficient fingerprint adhesion and fingerprint wiping properties, and also had low water and oil repellency.

<Surface analysis>

The surface composition of the surface treatment layer of the above-mentioned treated substrate was determined using an The measurement conditions for XPS analysis were as follows.

X-ray source: monochromatic AlKα ray (25W)

Photoelectronic detection area: 1400㎛×300㎛

Photoelectric detection angle: 45 degrees

Pass energy: 23.5eV

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 XPS, and their peak area ratios were By calculating, the composition of carbon atoms, oxygen atoms, and fluorine atoms on the surface of the surface treatment layer was determined. The results are shown in Table 6.

Additionally, the PFPE ratio on the surface of the surface treatment layer was determined as follows.

Focusing on the O1s orbital, the CO bond of CF ₂ CF ₂ -O-CF ₂ CF ₂ in PFPE is detected at 535 eV, the COC bond derived from the hard coat agent is detected at 533 eV, and the C=O bond is detected at 531 eV, respectively. Therefore, the XPS was measured, and the PFPE ratio was determined as the ratio of the peak area with the peak top around 535 to 536 eV out of the total area of the peak observed at about 530 to 540 eV, which is considered the O1s orbit. The results are shown in Table 6.

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

As described above, the surface of the surface treatment agent treated with the composition of the present disclosure is useful as a liquid-repellent additive, particularly as a liquid-repellent additive for bank resist, because PFPE is highly segregated on the surface and has a high surface fluorine concentration.

<Eraser friction durability evaluation>

The friction durability of the cured films shown in Table 7 below was evaluated by an eraser friction durability test. Specifically, the sample article on which the surface treatment layer was formed was placed horizontally, an eraser (manufactured by Minoan, hardness 81 (Durometer Atype), round surface diameter 0.6 cm) was brought into contact with the surface of the surface treatment layer, and 1000 gf was applied thereon. A load was applied, and then the eraser was reciprocated at a speed of 48 mm/sec (friction speed 40 rpm) with the load applied. The static contact angle (degrees) of water was measured every 1000 round trips. The evaluation was stopped when the measured contact angle value became less than 95 degrees. Finally, the number of reciprocations when the contact angle exceeds 95 degrees is shown in Table 7 below.

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

<Film thickness dependence>

PFPE-containing compound (D), or a mixture of PFPE-containing compound (D) and PFPE-containing compound (I) in 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. Otherwise, the properties of the cured film were evaluated in the same manner as in Example 1.

When a normal resin composition is used, when the film thickness is increased, Haze worsens and the function deteriorates. However, as shown in Table 8, when the composition of the present disclosure is used, even when the film thickness is large, the Haze is reduced. It was confirmed that deterioration was suppressed and that it had high water and oil repellency.

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

Claims (26)

Equation (1):

[Formula:
R ^N 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 which may be substituted with 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 a single bond or a divalent organic group in each occurrence;
R ^A1 , in each occurrence, is independently an OR ^Ac group-containing group;
R ^Ac is a (meth)acryloyl group;
R ^B is, at each occurrence, independently 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 which may be substituted with one or more fluorine atoms;
X ^b is a divalent organic group containing at least two heteroatoms.]
A composition comprising a compound represented by . According to paragraph 1,
Additionally, the following equation (2):

[Formula:
R ^N 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 which may be substituted with 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 -.]
A composition comprising a compound represented by . According to claim 1 or 2,
Equation (1) is the following equation (1'):

[Formula:
R ^F2 is -Rf ² _p -R ^F -O _q -;
Rf ² is a C _1-6 alkylene group which may be substituted with 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 a single bond or a divalent organic group in each occurrence;
R ^A1 , in each occurrence, is independently an OR ^Ac group-containing group;
R ^Ac is a (meth)acryloyl group;
R ^B is, at each occurrence, independently 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 which may be substituted with one or more fluorine atoms;
X ^b is a divalent organic group containing at least two heteroatoms.]
Phosphorus, composition. According to paragraph 2 or 3,
Equation (2) is the following equation (2'):

[Formula:
R ^F1 is Rf ¹ -R ^F -O _q -;
Rf ¹ is a C _1-16 alkyl group which may be substituted with 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 -.]
Phosphorus, composition. According to any one of claims 1 to 4,
R ^F are each independently expressed as:

[In the formula, R ^Fa is independently a hydrogen atom, a fluorine atom, or a chlorine atom in each occurrence,
a, b, c, d, e and f are each independently an integer from 0 to 200, the sum of a, b, c, d, e and f is 1 or more, a, b, c, d, The order of existence of each repeating unit enclosed in parentheses with e or f is arbitrary in the formula.]
The gin, composition indicated by . According to clause 5,
R ^Fa is a fluorine atom. According to any one of claims 1 to 4,
R ^F is each independently represented by the following formula (f1), (f2), (f3), (f4), (f5) or (f6):

[Wherein, d is an integer from 1 to 200, and e is 0 or 1.],

[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 enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula.],

[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 a combination of 2 or 3 groups selected from these groups;
g is an integer from 2 to 100.],

[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 a combination of 2 or 3 groups independently selected from these groups ego,
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 independently selected from these groups. It is a combination,
g is an integer from 2 to 100,
g ^' is an integer from 2 to 100,
R ^r is,

(In the formula, * represents the binding position.)
am.];

[In the formula, e is an integer from 1 to 200, a, b, c, d, and f are each independently integers from 0 to 200, and the sum of a, b, c, d, e, and f is It is 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 formula, f is an integer between 1 and 200, and a, b, c, d, and e are each independently integers between 0 and 200, and is the sum of a, b, c, d, e, and f. is 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 gin, composition indicated by . According to any one of claims 1 to 7,
X ^a is given by the following equation:

[During the ceremony,
^{X 121 to} _{_} ^_
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 bonded to CX ¹²¹
x1 is an integer from 0 to 10, y1 is 0 or 1, and z1 is an integer from 1 to 10.]
The gin, composition indicated by . According to any one of claims 1 to 8,
A composition where X ^a is a group represented by -(CH ₂ ) _m22 - (wherein m22 is an integer of 1 to 3). According to any one of claims 1 to 9,
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-,
R ^AC is (meth)acryloyl group,
Composition. According to any one of claims 1 to 10,
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,
R ^AC is (meth)acryloyl group,
Composition. According to any one of claims 1 to 11,
X ^b is -X ^c -X ^d -,
X ^c is a divalent organic group containing a hetero atom,
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,
Composition. According to any one of claims 1 to 12,
X ^b is -X ^c -X ^d -,
X ^c is a divalent organic group containing a hetero atom,
X ^d is -CO-NR ^d2 -,
R ^d2 is a hydrogen atom or a C _1-6 alkyl group,
Composition. According to any one of claims 1 to 13,
R ^A1 is -R ^A5 -(OR ^AC ) ₂ ,
R ^A5 is a trivalent hydrocarbon group having 4 to 6 carbon atoms,
R ^AC is (meth)acryloyl group,
Composition. According to any one of claims 12 to 14,
X ^c is -[(R ^c1 ) _t1 -(X ^c1 ) _t2 ]-X ^c2 -,
R ^c1 is, at each occurrence, independently a single bond or a C _1-12 alkylene group,
X ^c1 is, at each occurrence, independently O, NR ^x1 , S, SO or SO ₂ ,
R ^x1 is independently a hydrogen atom or a C _1-6 alkyl group in each occurrence,
X ^c2 is O or NR ^x2 ,
R ^x2 is independently a hydrogen atom or a C _1-6 alkyl group in each occurrence,
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,
Composition. According to any one of claims 12 to 15,
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 SO ₂ ,
R ^x1 is independently a hydrogen atom or a C _1-6 alkyl group in each occurrence,
X ^c2 is O or NR ^x2 ,
R ^x2 is independently a hydrogen atom or a C _1-6 alkyl group in each occurrence,
Composition. According to any one of claims 12 to 16,
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
Composition. According to any one of claims 1 to 17,
R ^B is R ^A1 -X ^b -, the composition. According to any one of claims 2 to 18,
A composition wherein the content of the compound represented by formula (1) is 10 to 90 mol% based on the total amount of the compound represented by formula (1) and the compound represented by formula (2). According to any one of claims 1 to 19,
Ink repellent agent, composition. According to any one of claims 1 to 19,
A composition that is an additive to a resist resin composition. The composition according to any one of claims 1 to 19; and
Composition forming a matrix
A curable composition containing. An article comprising a substrate and a layer formed on the surface of the substrate by the composition according to any one of claims 1 to 19, or the curable composition according to claim 22. According to clause 23,
An article, wherein the article is an optical member. The composition according to any one of claims 1 to 19,
Alkali soluble resin, and
polymerization initiator,
A resist resin composition containing. According to clause 25,
Resist resin composition for forming bank resist.