KR20190042033A - Composition - Google Patents

Abstract

It is an object of the present invention to provide a coating composition having good abrasion resistance. (A1) a monovalent group having a perfluoropolyether structure, (a2) a compound (A) in which at least one of a hydrolyzable group and a hydroxy group is bonded to a silicon atom, and a compound in which a hydroxy group and an oxyalkylene (B) in which at least a part of the hydrogen atoms of oxyalkylene units are substituted with fluorine atoms and the number average molecular weight is less than 10,000.

Description

Composition

The present invention relates to compositions.

Coatings formed from a composition containing a fluoroxyalkylene group-containing compound have water repellency and oil repellency, chemical resistance, releasability and the like because the surface free energy thereof is very small. Using this property, Patent Document 1 discloses a hydrolyzable group-containing silane and / or its partial hydrolysis-condensation product modified with (A) a fluoroxyalkylene group-containing polymer, and a hydrolyzable condensation product of the hydrolyzable group-containing silane and / (B) a fluorooxyalkylene group-containing polymer having an average molecular weight of at least 100 parts by weight. The effect of the fluorooxyalkylene group-containing polymer (B) of Patent Document 1 is to contain a fluorooxyalkylene group having no viscosity.

Further, Patent Document 2 discloses a method for producing a hydrolyzable silane containing a hydrolyzable group-containing silane and / or a partially hydrolyzed condensate thereof modified with (A) a fluoroxyalkylene group-containing polymer, ) Fluorooxyalkylene group-containing polymer, wherein a mixing mass ratio of the component (A) to the component (B) is from 6: 4 to 9: 1. As in Patent Document 1, the fluorooxyalkylene group-containing polymer (B) of Patent Document 2 is also described as being unaffected.

Japanese Unexamined Patent Application Publication No. 2015-199915 Japanese Unexamined Patent Application Publication No. 2013-136833

Patent Document 1 discloses that a polymer containing no fluorine oxyalkylene group has excellent abrasion resistance, and Patent Document 2 discloses that a fluorine-based surface treatment agent is deposited on a substrate by a vacuum deposition method to form a coating having excellent durability . However, there is still room for improvement in the improvement of wear resistance.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a composition capable of forming a film having good abrasion resistance.

(A1) a monovalent group having a perfluoropolyether structure, (a2) a compound (A) in which at least one of a hydrolyzable group and a hydroxy group is bonded to a silicon atom, and a compound in which a hydroxy group and an oxyalkylene (B) wherein at least a part of the hydrogen atoms of oxyalkylene units are substituted with fluorine atoms and the number average molecular weight is less than 10,000.

The compound (A) is preferably a compound represented by the following formula (1a) or (2a).

[Chemical Formula 1]

In formula (1a)

Rf ¹ is an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom or a fluorine atom,

Rf ² each independently represents an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom or a fluorine atom,

R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

R ² is independently an alkyl group having 1 to 20 carbon atoms,

D is independently selected from the group consisting of -O-, -C (= O) -O-, -OC (= O) -, -NR-, -NRC , R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms,

E is, independently of each other, a hydrolyzable group or a hydroxyl group,

a1, b1, c1, d1 and e1 are independently integers of 0 or more and 600 or less, the total value of a1, b1, c1, d1 and e1 is 9 or more,

n is an integer of 1 or more and 3 or less,

Each of the repeating units in parentheses attached with a1, b1, c1, d1 and e1 may be arranged in any order as long as they are arranged in the order of forming a perfluoropolyether structure at least in part.

(2)

In formula (2a)

Rf ³ is an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom or a fluorine atom,

Rf ⁴ are, each independently, an alkyl group or a fluorine atom of 1 to 20 carbon atoms substituted with at least one hydrogen atom with a fluorine atom,

R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

R ⁴ each independently represents an alkyl group having 1 to 20 carbon atoms,

M is independently selected from the group consisting of -O-, -C (= O) -O-, -OC (= O) -, -NR-, -NRC , R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms,

G is, independently of each other, a hydrolyzable group or a hydroxyl group,

Y is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

Z is a hydrogen atom or a halogen atom,

a2, b2, c2, d2 and e2 are independently an integer of 0 or more and 600 or less, and a total value of a2, b2, c2, d2 and e2 is 9 or more,

f2 is an integer of 1 or more and 20 or less,

g2 is an integer of 0 or more and 2 or less,

p is an integer of 1 or more and 3 or less,

Each of the repeating units in parentheses attached with a2, b2, c2, d2 and e2 may be arranged in any order as long as they are arranged in the order of forming a perfluoropolyether structure at least in part.

The compound (A) is a compound having a total of a1, b1, c1, d1 and e1 in the formula (1a) is 13 or more or a total value of a2, b2, c2, d2 and e2 in the formula Is preferably 13 or more.

The compound (B) is preferably a compound represented by the following formula (1b).

(3)

X is independently a hydrogen atom or a fluorine atom, Rf ⁵ is each independently a hydrogen atom, a fluorine atom, or -CF ₃ , J is -O-, -C (= O) -, A3 is not less than 1 but not more than 5, b3 is not less than 20 but not more than 200, c3 is not less than 5 but not more than 200, each repeating unit enclosed in parentheses a3 to c3 , And they may be arranged in any order as long as they are arranged in the order of forming an oxyalkylene unit at least in part. At least a part of the hydrogen atoms of the oxyalkylene unit are substituted with fluorine atoms.

The number of hydroxyl groups contained in the compound (B) is preferably 1 to 2. The compound (B) is also preferably such that the ratio of the number of fluorine atoms to the total of the number of hydrogen atoms other than hydrogen atoms in the hydroxyl group and the number of fluorine atoms is 40% or more.

The mass ratio of the compound (A) to the compound (B) is preferably 1 or more.

According to the composition of the present invention, a compound (A) having a perfluoropolyether structure and a compound in which at least a part of the hydrogen atoms of the oxyalkylene unit is substituted with a fluorine atom, with a hydroxy group and an oxyalkylene unit (B) is used, a water-repellent film having excellent abrasion resistance can be realized.

The composition of the present invention comprises a compound (A) having a perfluoropolyether structure and a compound (B) having a hydroxy group and an oxyalkylene unit. By the perfluoropolyether structure of the compound (A) and the oxyalkylene unit in which at least a part of the hydrogen atoms of the compound (B) are substituted with fluorine atoms, the coating film can exhibit good water repellency. Further, since the compound (B) has a hydroxyl group, wear resistance of the coating can be ensured.

The compound (A) may be any compound that contains fluorine and can be a matrix of the coating by bonding the compounds (A) together with other monomers through a polymerization reaction (in particular, a polycondensation reaction). The compound (A) is preferably a compound containing at least one of a fluorine group and at least one of a hydrolyzable group and a hydroxyl group. Among them, in the present invention, as the compound (A), a perfluoropolyether structure (A2) a compound in which at least one of the hydrolyzable group and the hydroxyl group is bonded to a silicon atom is used.

The perfluoropolyether structure is a structure in which all the hydrogen atoms of the polyalkylene ether group or the polyalkylene glycol dialkyl ether residue are substituted with fluorine atoms, and a perfluoropolyalkylene ether group, May be referred to as a polyalkylene glycol dialkyl ether residue. The perfluoropolyether structure may also be referred to as a perfluorooxyalkylene group. The perfluoropolyether structure imparts water repellency to the obtained coating film. The number of carbon atoms contained in the longest straight-chain portion of the perfluoropolyether structure is, for example, preferably 5 or more, more preferably 10 or more, and still more preferably 20 or more. The upper limit of the number of carbon atoms is not particularly limited, and may be, for example, about 200.

In the compound (A), the monovalent group having the perfluoropolyether structure is bonded to the silicon atom. A suitable linking group may be present on the side where the perfluoropolyether structure bonds with the silicon atom, and the perfluoropolyether structure may be directly bonded to the silicon atom without the linking group. Examples of the linking group include a hydrocarbon group such as an alkylene group and an aromatic hydrocarbon group, a (poly) alkylene glycol group, a group in which at least a part of hydrogen atoms thereof are substituted with a fluorine atom, have. The number of carbon atoms in the linking group is, for example, 1 or more and 20 or less, preferably 2 or more and 10 or less.

A plurality of silicon atoms may be bonded to one connector, or a plurality of perfluoropolyether structures may be bonded to one connector. The number of the monovalent groups having a perfluoropolyether structure bonded to the silicon atom may be one or more, and may be 2 or 3, but is preferably 1 or 2, particularly preferably 1.

In the compound (A), at least one of a hydrolyzable group and a hydroxy group is bonded to the silicon atom, and the hydrolyzable group and the hydroxy group are bonded to each other through the hydrolysis and / or dehydration condensation reaction, Or an active hydrogen derived from the hydroxy group of the surface of the substrate (A) and the like. Examples of such a hydrolyzable group include an alkoxy group (particularly an alkoxy group having 1 to 4 carbon atoms), an acetoxy group, a halogen atom (in particular, a chlorine atom), and the like. Preferred hydrolyzable groups are an alkoxy group and a halogen atom, and particularly preferably a methoxy group, an ethoxy group and a chlorine atom.

The number of the hydrolysable groups to be bonded to the silicon atom may be one or more, and may be 2 or 3, but is preferably 2 or 3, particularly preferably 3. When two or more hydrolyzable groups are bonded to silicon atoms, different hydrolyzable groups may be bonded to silicon atoms, but it is preferable that the same hydrolyzable groups are bonded to silicon atoms. The total number of fluorine-containing groups bonded to silicon atoms and hydrolyzable groups is usually 4, but may be 2 or 3 (especially 3). 3 or less, for example, an alkyl group (particularly an alkyl group having 1 to 4 carbon atoms), a hydrogen atom, an isocyanate group, or the like may be bonded to the remaining bonded hands.

The monovalent group having a perfluoropolyether structure of the compound (A) may be in a linear form or may have a side chain.

The number average molecular weight of the compound (A) is not particularly limited, but is, for example, 6000 or more, preferably 7000 or more, and 15000 or less, preferably 12000 or less.

As the compound (A), for example, a compound of the following formula (1a) can be mentioned.

[Chemical Formula 4]

In formula (1a)

Rf ¹ is an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom or a fluorine atom,

Rf ² each independently represents an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom or a fluorine atom,

R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

R ² is independently an alkyl group having 1 to 20 carbon atoms,

D is independently selected from the group consisting of -O-, -C (= O) -O-, -OC (= O) -, -NR-, -NRC , R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms,

E is, independently of each other, a hydrolyzable group or a hydroxyl group,

a1, b1, c1, d1 and e1 each independently represents an integer of 0 or more and 600 or less, and the sum of a1, b1, c1, d1 and e1 is 9 or more, preferably 13 or more,

n is an integer of 1 or more and 3 or less,

Each of the repeating units in parentheses attached with a1, b1, c1, d1 and e1 may be arranged in any order as long as they are arranged in the order of forming a perfluoropolyether structure at least in part. Each of the repeating units may be contained in the molecule. In the present specification, the case where a plurality of repeating units are present in a molecule means that the repeating units are discontinuously present, for example, when two repeating units exist in the molecule and are sandwiched between two different repeating units .

Rf ¹ is preferably an alkyl group having 1 to 10 carbon atoms substituted by at least one fluorine atom, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, more preferably a perfluoroalkyl group having 1 to 5 carbon atoms Lt; / RTI >

Rf ² is preferably, independently of each other, a fluorine atom or a fluorine-containing alkyl group having 1 to 2 carbon atoms, more preferably a fluorine atom.

Each R ¹ is independently a hydrogen atom, or an alkyl group having 1 or 2 carbon atoms, and more preferably all hydrogen atoms.

R ² is preferably independently an alkyl group having 1 to 5 carbon atoms.

D is preferably each independently -C (= O) -O-, -O-, -O-C (= O) -, and more preferably all -O-.

E is preferably independently an alkoxy group having 1 to 4 carbon atoms or a halogen atom, and particularly preferably a methoxy group, an ethoxy group or a chlorine atom.

The repeating unit in which the b1 of the most fixed side (the side to be bonded with the silicon atom) is attached to the order of each repeating unit enclosed in parentheses by attaching a1, b1, c1, d1 and e1, More preferably, the repetition unit in which b1 and d1 on the most fixed side are attached and parenthesized is a repeating unit in which a1 and c1 of the most free side are attached and parenthesized It is located on the free end side of the bundled repeating unit. It is preferable that at least two repeating units in parentheses attached with e1 are present.

n is preferably 2 or more and 3 or less, and more preferably 3 or less.

Rf ¹ is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ² is a fluorine atom, R ¹ is a hydrogen atom, D is all -O-, E is a methoxy group, A1 is an integer of 1 to 3, c1 = d1 = 0, b1 and e1 are values set so that the compound of the formula (1a) can maintain a liquid at normal pressure, and n = 3 desirable. The total value of b1 and e1 can be 8 or more.

Examples of the compound represented by the formula (1a) include a compound represented by the following formula (1a-1).

[Chemical Formula 5]

In the formula (1a-1), R ¹⁰ is a perfluoroalkyl group having 1 to 5 carbon atoms, R ¹¹ is a perfluoroalkylene group having 1 to 5 carbon atoms, R ¹² is a perfluoroalkyl group having 1 to 3 carbon atoms a perfluoroalkyl group, R ¹³ is an alkylene group of 1 to 3 carbon atoms, R ¹⁴ is an alkyl group of 1 to 3 carbon atoms, an integer from both z2 and z3 is 1 to 3, z1 is the formula (1a -1) is a value which is set so as to maintain the liquid at normal pressure, and can be set to, for example, 3 or more.

The compound (A) may be a compound of the following formula (2a), preferably a compound of the following formula (2a) in addition to the compound of the formula (1a).

[Chemical Formula 6]

In the formula (2a)

Rf ³ is an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom or a fluorine atom,

Rf ⁴ are, each independently, an alkyl group or a fluorine atom of 1 to 20 carbon atoms substituted with at least one hydrogen atom with a fluorine atom,

R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

R ⁴ each independently represents an alkyl group having 1 to 20 carbon atoms,

M is independently selected from the group consisting of -O-, -C (= O) -O-, -OC (= O) -, -NR-, -NRC , R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms,

G is, independently of each other, a hydrolyzable group or a hydroxyl group,

Y is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

Z is a hydrogen atom or a halogen atom,

a2, b2, c2, d2 and e2 each independently represent an integer of 0 or more and 600 or less, and the sum of a2, b2, c2, d2 and e2 is 9 or more, preferably 13 or more,

f2 is an integer of 1 or more and 20 or less,

g2 is an integer of 0 or more and 2 or less,

p is an integer of 1 or more and 3 or less,

Each of the repeating units in parentheses attached with a2, b2, c2, d2 and e2 may be arranged in any order as long as they are arranged in the order of forming a perfluoropolyether structure at least in part. Each of the repeating units may be contained in the molecule.

Rf ³ is preferably an alkyl group having 1 to 10 carbon atoms substituted by at least one fluorine atom, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, more preferably a perfluoroalkyl group having 1 to 5 carbon atoms Lt; / RTI >

Rf ⁴ is preferably, independently of each other, a fluorine atom or a fluorine alkyl group having 1 to 2 carbon atoms, more preferably a fluorine atom.

R ³ is preferably a hydrogen atom, or an alkyl group having 1 or 2 carbon atoms, and more preferably all hydrogen atoms.

Each R ⁴ is independently an alkyl group having 1 to 5 carbon atoms.

M is preferably each independently -C (= O) -O-, -O-, -O-C (= O) -, and more preferably all -O-.

G is preferably independently an alkoxy group or a halogen atom, and particularly preferably a methoxy group, an ethoxy group or a chlorine atom.

Y is preferably, independently of each other, a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, more preferably a hydrogen atom.

Z is preferably a hydrogen atom.

Preferably, a2, c2 and d2 are respectively 1/2 or less of b2, more preferably 1/4 or less, more preferably c2 or d2 is 0, and particularly preferably c2 and d2 are 0.

e2 is preferably not less than 1/5 of the total value of a2, b2, c2 and d2, and is not more than the sum of a2, b2, c2 and d2.

b2 is preferably 20 or more and 600 or less, more preferably 20 or more, 200 or less, and still more preferably 50 or more and 200 or less. e2 is preferably 4 or more and 600 or less, more preferably 4 or more, 200 or less, and further preferably 10 or more and 200 or less. The total value of a2, b2, c2, d2 and e2 is preferably 20 or more and 600 or less, more preferably 20 or more, further preferably 200 or less, still more preferably 50 or more and 200 or less.

f2 is preferably 1 or more and 18 or less. More preferably not less than 1 and not more than 15.

g2 is preferably 0 or more and 1 or less.

p is preferably 2 or more and 3 or less, and more preferably 3 or less.

The repeating units in parentheses of b2 of the most fixed end side (the side to be bonded with the silicon atom) are preferably arranged in the order of repeating units enclosed in parentheses by attaching a2, b2, c2, d2 and e2, More preferably, the repetition unit in which b2 and d2 of the most fixed side are attached and parenthesized is a parenthesized structure in which a2 and c2 of the most free side are attached to the repeating unit in which the a2 of the free end side is attached and is located on the free end side of the repeating unit in parentheses It is located on the free end side of the bundled repeating unit. In addition, it is preferable that at least two repeating units in parentheses attached with e2 are present.

In formula (2a), it is particularly preferable that Rf ³ is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ⁴ is a fluorine atom, M is all -O-, G is a methoxy group, an ethoxy group, (More preferably 80 to 140), e2 is 30 to 60, c2 and d2 are 0, g2 is 0 or more and 1 or less, and Y1 and Z2 are both hydrogen atoms, a2 is 0, b2 is 30 to 150 (Particularly 0), p is 3, and f2 is 1 to 10.

Examples of the compound represented by the formula (2a) include compounds represented by the following formula (2a-1).

(7)

In the formula (2a-1), R ²⁰ is a perfluoroalkyl group having 2 to 6 carbon atoms, R ²¹ and R ²² are both a perfluoroalkylene group having 2 to 6 carbon atoms, and R ²³ is a perfluoroalkyl group having 2 to 6 carbon atoms To 6, and R < ²⁴ > is an alkyl group having 1 to 3 carbon atoms. The number of carbon atoms of R ²⁰ , R ²¹ , R ²² and R ²³ is independently preferably 2 to 4, more preferably 2 to 3. x 1 is 5 to 70, x 2 is 1 to 5, and x 3 is 1 to 10. x1 is preferably 10 to 60, more preferably 20 to 50, x2 is preferably 1 to 4, more preferably 1 to 3, x3 is preferably 1 to 8, and more preferably 1 to 6 .

The compound (B) has a hydroxy group and an oxyalkylene unit, at least a part of the hydrogen atoms of the oxyalkylene units are substituted with fluorine atoms, and the number average molecular weight is less than 10,000. Compared with the case where a compound having a similar structure having no hydroxy group is used in place of the compound (B) because the hydroxy group of the compound (B) interacts with the base such as glass or the compound (A) , It can be considered that the wear resistance of the coating improves.

It is important that the number average molecular weight of the compound (B) is less than 10,000 from the viewpoint of sufficiently securing the component derived from the compound (B) in the coating film obtained by the vacuum vapor deposition, and the lower limit is preferably about 1000 . The number average molecular weight of the compound (B) is preferably 8,000 or less, more preferably 6,000 or less.

There is at least one hydroxyl group in the compound (B), preferably 5 or less, and more preferably 2 or less. In the compound (B), the ratio of the number of fluorine atoms to the total of the number of hydrogen atoms other than hydrogen atoms in the hydroxy group and the number of fluorine atoms is preferably 40% or more. Thus, the water repellency can be exerted. The ratio of the number of fluorine atoms is more preferably 50% or more, still more preferably 55% or more, and the upper limit is not particularly limited and may be 100% or about 80%.

As the compound (B), for example, a compound represented by the following formula (1b) can be given.

[Chemical Formula 8]

In formula (1b), each X independently represents a hydrogen atom or a fluorine atom, Rf ⁵ each independently represents a hydrogen atom, a fluorine atom, or -CF ₃ , J represents -O-, -C (= O) -O A3 is not less than 1 but not more than 5, b3 is not less than 20 but not more than 200, c3 is not less than 5 but not more than 200, each repeating unit in parentheses attached with a3 to c3, May be arranged in any order as long as they are arranged in the order of forming an oxyalkylene unit at least in part. At least a part of hydrogen atoms of the oxyalkylene unit are substituted with a fluorine atom. Further, plural repeating units in parentheses attached with a3 to c3 may be contained in the molecule.

Rf ⁵ are each independently a hydrogen atom or a fluorine atom is preferred and, X is preferably a hydrogen atom, J is that the -O- is preferable, and, a3 is and is not less than 1 but not more than preferably 3, more preferably 1 or 2, (Most preferably 2). b3 is preferably 30 or more and 100 or less, and c3 is preferably 10 or more and 80 or less. b3 and c3 are preferably such that the number average molecular weight of the compound represented by the formula (1b) is 2000 to 4500, more preferably 2500 to 4500. And most preferably, Rf ⁵ are each independently a hydrogen atom or a fluorine atom, and X is a hydrogen atom, J is -O-, and a3 is 1 or 2, b3, c3 are, represented by the formula (1b) Is preferably a value determined so that the number average molecular weight of the losing compound is 2000 to 4500 (more preferably 2500 to 4500).

As the compound (B), for example, a polyalkylene glycol which may be substituted with a hydrogen atom of one OH group of a polyalkylene glycol having an OH group at both terminals, wherein at least a part of the hydrogen atoms of the alkylene group is substituted with a fluorine atom And polyalkylene glycols having a carboxyl group. As the compound (B), polyalkylene glycols in which at least a part of the hydrogen atoms of the alkylene group are substituted with fluorine atoms are preferable. Such polyalkylene glycols are, for example, compounds represented by the following formulas (1b-1) 2).

[Chemical Formula 9]

In the formula ^{(1b-1), R 30} , R 31, R 32, R 34 and R ³⁵ are, each independently are an alkylene group having a carbon number of 2~6, R ³³ is an alkylene group having a carbon number of 1~5, R ^{30 To} R < ^{35 &} gt ;, at least one of the hydrogen atoms in the at least one alkylene group is substituted with a fluorine atom. y1 is 2 to 10, y2 is 1 to 4, y3 to y5 are values determined so that the number average molecular weight of the compound represented by the formula (1b-1) is 2000 to 2400, y6 is 1 to 4, y7 is 2 ~ 10.

R ³⁰ , R ³¹ , R ³² , R ³⁴ and R ³⁵ are each independently an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 to 3 carbon atoms. R ³³ is preferably an alkylene group having 1 to 3 carbon atoms, more preferably an alkylene group having 1 to 2 carbon atoms. y1 is preferably from 3 to 9, more preferably from 4 to 8, y2 is preferably from 1 to 3, more preferably from 1 to 2, y6 is preferably from 1 to 3, more preferably from 1 And y7 is preferably from 3 to 9, more preferably from 4 to 8.

[Chemical formula 10]

In formula (1b-2), R ⁴⁰ and R ⁴³ are each independently an alkylene group having 1 to 3 carbon atoms, R ⁴¹ is an alkylene group having 1 to 5 carbon atoms in which at least one of the hydrogen atoms is substituted with a fluorine atom, R ⁴² is an alkylene group having 1 to 3 carbon atoms in which at least one of the hydrogen atoms is substituted with a fluorine atom, w 1 and w 4 are each independently 1 to 3, w 2 and w 3 are each a group represented by the formula (1b-2) Is a value determined so that the number average molecular weight is 3800 to 4200.

R ⁴⁰ and R ⁴³ are each independently an alkylene group having 1 to 2 carbon atoms, and R ⁴¹ is preferably an alkylene group having 1 to 3 carbon atoms in which at least one of the hydrogen atoms is substituted with a fluorine atom, and R ⁴² Is preferably an alkylene group having 1 to 2 carbon atoms in which at least one of the hydrogen atoms is substituted with a fluorine atom, w1 and w4 are each independently preferably 1 to 2, and more preferably satisfy these requirements simultaneously.

The mass ratio of the compound (A) to the compound (B) in the composition is preferably 1 or more. By doing so, the balance between water repellency and abrasion resistance of the obtained film can be improved. The mass ratio of the compound (A) to the compound (B) in the composition is more preferably 2.0 or more, still more preferably 3.5 or more, and still more preferably 5 or more (particularly 7 or more). The upper limit of the mass ratio is preferably 13 or less, and more preferably 11 or less, in consideration of the balance between water repellency and abrasion resistance of the obtained film.

The total mass ratio of the compound (A) and the compound (B) in the composition is preferably 10 mass% or more, more preferably 12 mass% or more, and further preferably 14 mass% or more to be. The upper limit is not particularly limited, but is preferably 30 mass% or less, 27 mass% or less, and 25 mass% or less, for example.

The composition of the present invention preferably contains a fluorine-based solvent (C) together with the above-mentioned compounds (A) and (B). As the fluorine-based solvent (C), for example, a fluorinated ether solvent, a fluorinated amine solvent, a fluorinated hydrocarbon solvent (particularly a fluorinated aromatic solvent) can be used. As the fluorinated ether solvent, hydrofluoroethers such as fluoroalkyl (perfluoroalkyl group having 2 to 6 carbon atoms in particular) -alkyl (especially methyl or ethyl group) ether are preferable, and for example, ethylnonafluorobutyl ether or Ethyl nonafluoroisobutyl ether. Examples of ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether include Novec (registered trademark) 7200 (3M, molecular weight: about 264, boiling point: 76 ° C). As the fluorinated amine-based solvent, an amine in which at least one hydrogen atom of ammonia is substituted by a fluoroalkyl group is preferable, and a tertiary amine in which all hydrogen atoms of ammonia are substituted by a fluoroalkyl group (in particular, perfluoroalkyl group) Specific examples thereof include tris (heptafluoropropyl) amine and Fluorinert (registered trademark) FC-3283 (molecular weight: about 471, boiling point: 128 ° C). As the fluorinated hydrocarbon solvent, 1,3-bis (trifluoromethylbenzene) (boiling point: about 116 ° C) may be mentioned.

Examples of the fluorine-based solvent (C) include hydrofluorocarbons such as hydrochlorofluorocarbons such as Asahi Clean (registered trademark) AK225 (manufactured by Asahi Glass Co., Ltd.) and Asahikawa (registered trademark) AC2000 .

The molecular weight of the fluorine-containing solvent (C) is preferably 900 or less, more preferably 800 or less, and the lower limit is not particularly limited, but is, for example, about 300.

The content of the fluorine-based solvent (C) in the composition of the present invention is, for example, not less than 20% by mass, more preferably not less than 50% by mass, and more preferably not less than 70% by mass relative to the total mass of the composition , Preferably 90 mass% or less, more preferably 88 mass% or less, and further preferably 86 mass% or less.

The composition of the present invention may further contain a silanol condensation catalyst. Examples of the silanol condensation catalyst include metal complexes such as inorganic acids such as hydrochloric acid and nitric acid, organic acids such as acetic acid, titanium complexes (for example, Matsumoto Fine Chemical, Organotics TC-750 and the like) and tin complexes, metal alkoxides and the like . The amount of the silanol condensation catalyst is, for example, 0.00001 to 0.1 mass%, preferably 0.00002 to 0.01 mass%, more preferably 0.0005 to 0.001 mass%, based on the total mass of the composition.

The composition of the present invention may contain additives such as an antioxidant, a rust inhibitor, an ultraviolet absorber, a light stabilizer, a antifungal agent, an antimicrobial agent, an antifouling agent, a deodorant, a pigment, a flame retardant, , And the like.

When the composition of the present invention contains various additives, the content of various additives is, for example, from 0.01 to 70% by mass, preferably from 0.05 to 50% by mass, more preferably from 0.05 to 50% by mass, relative to the polymer component of the composition of the present invention Preferably 0.1 to 30 mass%, and more preferably 0.5 to 5 mass%.

The composition of the present invention is suitably used for forming a film on a substrate by vacuum vapor deposition. As conditions for the vacuum deposition, known conditions can be employed. The degree of vacuum is, for example, about 10 ^-2 Pa or less. As the heating method in the vapor deposition process, any of a resistance heating method and an electron beam heating method may be used, and the heating temperature is, for example, 100 to 400 占 폚. The film forming time is, for example, about 1 to 60 seconds.

After the vacuum deposition, moisture in the air is taken in the air and allowed to stand at room temperature or warmed (for example, at 50 to 150 캜 for 5 to 30 minutes) The hydrolyzable group is hydrolyzed, siloxane bonds are formed, and a cured film can be obtained. The film thickness of the obtained film may be, for example, 2 to 10 nm.

The material of the base material for depositing the composition of the present invention is not particularly limited and may be any of an organic material and an inorganic material. The shape of the base material may be planar or curved, and a three-dimensional structure It may be. Examples of the organic material include thermoplastic resins such as acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose resin, polyolefin resin and polyvinyl alcohol; A thermosetting resin such as a phenol resin, a urea resin, a melamine resin, an epoxy resin, an unsaturated polyester, a silicone resin, and a urethane resin. Examples of the inorganic material include metals such as iron, silicon, copper, zinc and aluminum, alloys containing such metals, ceramics and glass. Among them, it is particularly preferable to deposit the composition of the present invention on a substrate of an inorganic material such as glass, metal, ceramic or the like to form a film.

After the film is formed on the substrate, the film may be left as it is, or may be subjected to a predetermined post-treatment, and the post-treatment may further improve the wear resistance of the film. Examples of the post-treatment include heating, holding in a humidified atmosphere, ultrasonic cleaning, and surface cleaning with a solvent. Such post-treatment may be performed alone or in combination with two or more Or may be performed in combination. Among them, it is particularly preferable to heat-hold or ultrasonically clean. The heating may be carried out at a temperature of, for example, 100 to 200 캜 for 10 to 60 minutes. The ultrasonic cleaning may be performed by, for example, water, As a cleaning liquid for about 1 to 5 minutes. From the viewpoint of further improving the abrasion resistance, ultrasonic cleaning is preferable. Since the composition of the present invention includes the compound (B) having a hydroxy group, the compound (B) and the substrate (for example, glass) can be obtained by post treatment as compared with the case where the composition contains a compound having no conventional hydroxy group. Or the interaction with the compound (A) is expected to change to a state having higher durability.

The substrate may be subjected to the adhesion (easy adhesion) treatment in advance. Examples of the adhesion treatment include a hydrophilic treatment such as a corona treatment, a plasma treatment, and an ultraviolet ray treatment. In addition, a primer treatment with a resin, a silane coupling agent, tetraalkoxysilane or the like may be used. Further, the silicon dioxide layer may be formed by vapor deposition.

As the primer layer, a layer formed by using a composition for forming a primer layer containing a compound represented by the following formula (p1) and / or a partial hydrolysis-condensation product thereof is preferable.

Si (X ² ) ₄ (p 1)

(Provided that plural X < ² > in the formula (p1) each independently represent a halogen atom, an alkoxy group or an isocyanate group).

In the formula (p1), each of X ² is independently preferably a chlorine atom, an alkoxy group having 1 to 4 carbon atoms, or an isocyanate group, and further, four X ² are preferably the same.

A compound represented by this formula (p1), _{specifically, Si (NCO) 4, Si} (OCH 3) 4, Si (OC 2 H 5) 4 is used the like are preferred. As the component (E), one type may be used alone, or two or more types may be used in combination.

The component (E) contained in the composition for forming a primer layer may be a partial hydrolyzed condensate of the compound represented by the above formula (p1). The partial hydrolysis condensation product of the compound represented by the formula (p1) can be obtained by applying a general hydrolysis and condensation method using an acid or base catalyst. The degree of condensation (degree of multiplication) of the partially hydrolyzed condensate needs to be such a degree that the product dissolves in the solvent. The component (E) may be a compound represented by the formula (p1) may be a partial hydrolyzed condensate of a compound represented by the formula (p1), and may be a mixture of a compound represented by the formula (p1) and a partially hydrolyzed condensate thereof, for example, The compound represented by the formula (p1) or its partial hydrolyzed condensate may be a commercially available product, and it is possible to use such a commercially available product in the present invention .

The composition for forming a primer layer may further contain (F) a component (E), a compound represented by the following formula (p2) (sometimes referred to as a compound (p2)) and / Or a partial hydrolysis and condensation product of the component (E) and the component (F) (provided that the component (E) and / or the compound (p2) may be contained) do.

(X ³ ) ₃ Si- (CH ₂ ) _p -Si (X ³ ) ₃ ( _{p 2} )

(In this formula, (p2) of the plurality which X ³ represents a hydrolyzable group or a hydroxyl group, each independently, p is an integer of 1-8.)

The compound represented by the formula (p2) is a compound having a hydrolyzable silyl group or silanol group at both terminals with a divalent organic group interposed therebetween.

In the formula (p2), examples of the hydrolyzable group represented by X < ³ > include the same groups or atoms as those described above for X < ² >. From the viewpoint of the balance between the stability of the compound represented by the formula (p2) and the ease of hydrolysis, as the X ³ , an alkoxy group and an isocyanate group are preferable, and an alkoxy group is particularly preferable. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group. These are suitably selected and used depending on the purpose of manufacture, use, and the like. A plurality of X < ³ > s in the formula (p2) may be different from each other in the same contribution, and the same group is preferred from the viewpoint of availability.

Specific examples of the compound represented by the formula (p2) include (CH ₃ O) ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₃ , (OCN) ₃ SiCH ₂ CH ₂ Si (NCO) ₃ , Cl ₃ SiCH ₂ CH _{2 SiCl 3, (C 2 H} 5 O) 3 SiCH 2 CH 2 Si (OC 2 H 5) 3, (CH 3 O) 3 SiCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 Si (OCH 3) 3 , etc. . As the component (F), one kind may be used alone, or two or more kinds may be used in combination.

The component contained in the composition for forming a primer layer may be a partial hydrolyzed condensate of a compound represented by the formula (p2). The partial hydrolysis-condensation product of the compound represented by the formula (p2) can be obtained in the same manner as described in the production of the partial hydrolysis-condensation product of the compound represented by the formula (p1). The degree of condensation (degree of increase in mass) of the partially hydrolyzed condensate must be such that the product dissolves in the solvent. The component (F) may be a compound represented by the formula (p2) or a partial hydrolysis-condensation product of the compound represented by the formula (p2), or a compound represented by the formula (p2) For example, a partial hydrolysis condensation product of the compound containing the compound represented by the formula (p2) which is not reacted. The compounds represented by the above formula (p2) and partial hydrolyzed condensates thereof are commercially available products, and such commercially available products can be used in the present invention.

In addition, various polysilazanes can be used for the primer layer so as to obtain an oxide film containing silicon as a main component similar to the above formula (p1).

The composition for forming a primer layer generally includes an organic solvent in consideration of economical efficiency, workability, ease of control of the thickness of the obtained primer layer, and the like, in addition to the solid content to be a layer constituting component. The organic solvent is not particularly limited as long as it dissolves the solid content contained in the composition for forming a primer layer. Examples of the organic solvent include the same compounds as those used in the composition of the present invention. The organic solvent is not limited to one kind but may be used by mixing two or more kinds of solvents having different polarities and evaporation rates. When the composition for forming a primer layer contains a partial hydrolyzed condensate or a partially hydrolyzed cocondensation, a solvent used for preparing them may be included.

Further, in the composition for forming a primer layer, even if it does not contain a partial hydrolysis condensation product or a partial hydrolysis co-condensation product, in order to promote the hydrolysis co-condensation reaction, It is also preferable to add a catalyst such as an acid catalyst. Even when a partial hydrolyzed condensate or a partially hydrolyzed cocondensed product is contained, it is preferable to add a catalyst when the catalyst used in the production does not remain in the composition. The composition for forming the primer layer may contain water for the hydrolysis-condensation reaction or the hydrolysis cocondensation reaction.

As a method of forming the primer layer by using the composition for forming the primer layer, it is possible to use a known method in the surface treating agent of the organosilane compound system. For example, a composition for forming a primer layer may be applied to the surface of a substrate by a method such as brushing, flow coating, spin coating, immersion coating, squeegee coating, spray coating, After drying and curing, a primer layer can be formed. The conditions of the curing are suitably controlled by the type, concentration, and the like of the composition to be used. The curing of the composition for forming a primer layer may be performed simultaneously with the curing of the water repellent film forming composition.

The thickness of the primer layer is not particularly limited as long as it can impart moisture resistance to the transparent film formed thereon and can provide adhesion with the base material and can cover alkali from the base material .

The coating film obtained from the composition of the present invention is excellent in static water repellency and dynamic water repellency. The static water repellency can be evaluated, for example, by an initial contact angle that is interpreted by the? / 2 method by a liquid droplet method, and the dynamic water repellency can be evaluated by contact angle hysteresis or sliding angle measured by the sliding method . For example, the initial contact angle measured by an aqueous solution of 3 mu L can be, for example, 110 DEG or more, preferably 113 DEG or more, more preferably 115 DEG or more, and the upper limit is not particularly limited, For example, about 125 degrees. The contact angle hysteresis measured by an aqueous solution of 6.0 mu L can be, for example, 12 DEG or less, preferably 10 DEG or less, more preferably 9 DEG or less, and the lower limit is not particularly limited, For example, it is about 3 °. The sliding angle measured by an irregular amount of 6 mu L is, for example, 30 DEG or less, preferably 25 DEG or less, more preferably 23 DEG or less, and the lower limit is not particularly limited, but may be 5 DEG Respectively.

[Example]

Hereinafter, the present invention will be described more specifically by way of examples. The present invention is not limited to the following embodiments, and it is of course possible to carry out the present invention by appropriately modifying it within a range that is suitable for the purpose of the latter, and they are all included in the technical scope of the present invention.

The coatings obtained in Examples and Comparative Examples of the present invention were measured by the following methods.

(1) Measurement of film thickness

For the measurement, an X-ray reflectance meter (Smart Lab) manufactured by Rigaku Corporation was used. A wavelength (?) Of CuK? Ray = 0.15418 nm or a wavelength? (?) Of CuK? 1 ray = 0.15406 nm by an X-ray generator of 45 kW as an X-ray source and a Cu target and a monochrometer are not used. As a setting condition, the sampling width was set to 0.01 deg., And the scanning range was set to 0.0 to 2.5 deg. Then, the measurement was performed under the above setting conditions, and a reflectance measurement value was obtained. The obtained measurement values were analyzed using the company's analysis software (Global Fit).

(2) Measurement of initial contact angle

The contact angle of water on the surface of the coating film was measured with a contact angle measuring apparatus (DM700 manufactured by Kyowa Interface Science Co., Ltd.) and a liquid amount of 3 mu L by a droplet method (analysis method:? / 2 method).

(3) Measurement of contact angle hysteresis and sliding angle

(DM700), and the sliding method (analytical method: contact method, volume: 6.0μL, gradient method: continuous gradient, slip detection: after slip, moving determination: forward angle, determination distance of slip: 0.125mm) , The dynamic water repellency characteristics (contact angle hysteresis, sliding angle) of the coating surface were measured.

(4) Evaluation of abrasion resistance

A wear test was conducted by using a scratch device equipped with an erecting HB pencil manufactured by Mitsubishi Mfg. Co., Ltd., and moving the sample at 40 r / min under a load of 500 g while the eraser was in contact with the sample. The contact angle was measured every 1000 times of abrasion, and the number of times from the initial contact angle until it became -15 degrees or less was measured.

Example 1

(Number average molecular weight: about 8000) represented by the following formula (a) was synthesized by the method described in Synthesis Examples 1 and 2 of JP-A-2014-15609.

(11)

In the above formula (a), n is 43 and m is an integer of 1 to 6.

As the compound (A), the compound (b1) (number average molecular weight: about 2240) represented by the following formula (b1) was used as the compound (a) and the compound (B) represented by the above formula (a).

[Chemical Formula 12]

In the formula (b1), r and s are integers in the range of the average molecular weight. In the formula (b1), the ratio of the number of fluorine atoms to the total of the number of hydrogen atoms other than hydrogen atoms in the hydroxy group and the number of fluorine atoms is 40% or more.

A composition in which the ratio of the compound (A): the compound (B): the fluorine-based solvent (C) = 89: 11: 400 was prepared using Novec 7200 (registered trademark) as the fluorine-based solvent (C). After 1 mL of the solution was dropped onto a Ta boat heated to evaporate the solvent, a sample for vapor deposition was prepared. Alkali glass EAGLE-XG (manufactured by Nippon Paper Industries Co., Ltd.) was prepared by vacuum evaporation (resistive heating method, pressure 8 × 10 ^-3 Pa, applied current 20 A, (Registered trademark, made by Corning Incorporated), and used as a film performance evaluation sample.

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. The initial contact angle in Example 1 was 115.8 deg., The sliding angle was 27.7 deg., And the contact angle hysteresis was 10.6 deg.

Example 2

After the film formation, the same operation as in Example 1 was carried out except that the heat treatment was further carried out at 150 占 폚 for 30 minutes to obtain a sample for evaluating the film performance.

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. In Example 2, the initial contact angle was 115.8 deg., The sliding angle was 17.3 deg., And the contact angle hysteresis was 7.1 deg.

Example 3

After the film formation, the same operation as in Example 1 was carried out except that the ultrasonic cleaning treatment was further performed in water for 3 minutes to obtain a sample for evaluating the film performance.

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. In Example 3, the initial contact angle was 117.9 °, the sliding angle was 22.3 °, and the contact angle hysteresis was 8.3 °.

Example 4

The procedure of Example 2 was repeated except that Fluorolink (registered trademark) D4000 (number average molecular weight: about 4000) represented by the following formula (b2) was used instead of the compound (b1) Fluorolink (registered trademark) D4000 has a hydroxy group at the end and an oxyalkylene unit, and a part of the hydrogen atoms of the oxyalkylene unit is substituted with a fluorine atom. In Fluorolink D4000, the ratio of the number of fluorine atoms to the total of the number of hydrogen atoms other than hydrogen atoms in the hydroxy group and the number of fluorine atoms is 40% or more.

[Chemical Formula 13]

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. The initial contact angle in Example 4 was 111.1 °, the sliding angle was 7.3 °, and the contact angle hysteresis was 4.8 °.

Example 5

The procedure of Example 2 was repeated except that the composition ratio of the compound (A): the compound (B): the fluorinated solvent (C) was changed to 80: 20: 400, Respectively.

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. In Example 5, the initial contact angle was 114.9 °, the sliding angle was 26.3 °, and the contact angle hysteresis was 14.5 °.

Example 6

The procedure of Example 4 was repeated except that the mass ratio of the compound (A): the compound (B): the fluorinated solvent (C) = 80: 20: 400 was changed to give a film performance evaluation sample Respectively.

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. The initial contact angle in Example 6 was 117.1 °, the sliding angle was 26.7 °, and the contact angle hysteresis was 16.3 °.

Example 7

The procedure of Example 4 was repeated except that the composition ratio of the compound (A): the compound (B): the fluorine-containing solvent (C) was changed to 67: 33: 400, Respectively.

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. In Example 7, the initial contact angle was 115.6 deg., The sliding angle was 22.7 deg., And the contact angle hysteresis was 9.5 deg.

Comparative Example 1

The procedure of Example 1 was repeated except that Fomblin (registered trademark) M03 (number average molecular weight: about 4000) represented by the following formula (c) was used instead of the compound (b1) . Fomblin (R) M03 had an oxyalkylene unit, and all of the hydrogen atoms in the oxyalkylene units were substituted with fluorine atoms, but did not have a hydroxyl group in the molecule.

[Chemical Formula 14]

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. In addition, the initial contact angle in Comparative Example 1 was 115.7 deg., The sliding angle was larger than 50 deg., And even when the substrate was tilted to 50 deg.

Comparative Example 2

A procedure was performed in the same manner as in Example 2 except that Fomblin (R) M03 was used instead of the compound (b1) to prepare a sample for evaluating the film performance.

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. The initial contact angle in Comparative Example 2 was 116.5 deg., The sliding angle was 13.7 deg., And the contact angle hysteresis was 4.2 deg.

Comparative Example 3

A procedure was performed in the same manner as in Example 3 except that Fomblin (R) M03 was used instead of the compound (b1) to obtain a sample for evaluating the film performance.

The evaluation results of the abrasion resistance of the obtained film are shown in Table 1. In Comparative Example 3, the initial contact angle was 118.3 deg., The sliding angle was 13.3 deg., And the contact angle hysteresis was 6.5 deg.

From Table 1, it can be seen that Examples 1 to 7 using the compound (B) having a hydroxy group have improved abrasion resistance as compared with Comparative Examples 1 to 3. Further, in the coating film obtained by using the composition of the present invention, the post-treatment after the coating film formation can further improve the abrasion resistance. In particular, in Examples 1 to 3 in which the conditions other than the post- The abrasion resistance was the best in Example 3 in which cleaning was performed.

[Industrial Availability]

The composition of the present invention can be applied to a display device such as a touch panel display, an optical device, a semiconductor device, a building material, a nano imprint technology, a solar cell, a metal product such as a window glass of an automobile or a building, It is possible to form a film suitable for automobile parts and the like, which is industrially useful. It is also preferably used in kitchens, bathrooms, wash basins, mirrors, articles of each member around the toilet, goggles, glasses, and the like.

Claims (7)

(a1) a monovalent group having a perfluoropolyether structure, (a2) a compound (A) wherein at least one of a hydrolyzable group and a hydroxy group is bonded to a silicon atom, and
(B) having a hydroxy group and an oxyalkylene unit, at least a part of the hydrogen atoms of oxyalkylene units being substituted by fluorine atoms, and having a number average molecular weight of less than 10,000. The method according to claim 1,
The compound (A) is represented by the following formula (1a) or (2a).
[Chemical Formula 1]

In formula (1a)
Rf ¹ is an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom or a fluorine atom,
Rf ² each independently represents an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom or a fluorine atom,
R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ² is independently an alkyl group having 1 to 20 carbon atoms,
D is independently selected from the group consisting of -O-, -C (= O) -O-, -OC (= O) -, -NR-, -NRC , R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms,
E is, independently of each other, a hydrolyzable group or a hydroxyl group,
a1, b1, c1, d1 and e1 are independently integers of 0 or more and 600 or less, the total value of a1, b1, c1, d1 and e1 is 9 or more,
n is an integer of 1 or more and 3 or less,
Each of the repeating units in parentheses attached with a1, b1, c1, d1 and e1 may be arranged in any order as long as they are arranged in the order of forming a perfluoropolyether structure at least in part.
(2)

In formula (2a)
Rf ³ is an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom or a fluorine atom,
Rf ⁴ are, each independently, an alkyl group or a fluorine atom of 1 to 20 carbon atoms substituted with at least one hydrogen atom with a fluorine atom,
R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ⁴ each independently represents an alkyl group having 1 to 20 carbon atoms,
M is independently selected from the group consisting of -O-, -C (= O) -O-, -OC (= O) -, -NR-, -NRC , R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms,
G is, independently of each other, a hydrolyzable group or a hydroxyl group,
Y is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
Z is a hydrogen atom or a halogen atom,
a2, b2, c2, d2 and e2 are independently integers of 0 to 600, the sum of a2, b2, c2, d2 and e2 is 9 or more,
f2 is an integer of 1 or more and 20 or less,
g2 is an integer of 0 or more and 2 or less,
p is an integer of 1 or more and 3 or less,
Each of the repeating units in parentheses attached with a2, b2, c2, d2 and e2 may be arranged in any order as long as they are arranged in the order of forming a perfluoropolyether structure at least in part. 3. The method of claim 2,
The compound (A) is a compound having a total of a1, b1, c1, d1 and e1 in the formula (1a) is 13 or more or a total value of a2, b2, c2, d2 and e2 in the formula Is at least 13. 4. The method according to any one of claims 1 to 3,
The compound (B) is a compound represented by the following formula (1b).
(3)

X is independently a hydrogen atom or a fluorine atom, Rf ⁵ is each independently a hydrogen atom, a fluorine atom, or -CF ₃ , J is -O-, -C (= O) -, A3 is not less than 1 but not more than 5, b3 is not less than 20 but not more than 200, c3 is not less than 5 but not more than 200, each repeating unit enclosed in parentheses a3 to c3 , And they may be arranged in any order as long as they are arranged in the order of forming an oxyalkylene unit at least in part. At least a part of the hydrogen atoms of the oxyalkylene unit are substituted with fluorine atoms. 5. The method according to any one of claims 1 to 4,
Wherein the compound (B) contains 1 to 2 hydroxyl groups. 6. The method according to any one of claims 1 to 5,
Wherein the ratio of the number of fluorine atoms to the total of the number of hydrogen atoms other than hydrogen atoms in the hydroxy group and the number of fluorine atoms is 40% or more. 7. The method according to any one of claims 1 to 6,
Wherein the mass ratio of the compound (A) to the compound (B) is 1 or more.