CN109563338B

CN109563338B - Composition comprising a metal oxide and a metal oxide

Info

Publication number: CN109563338B
Application number: CN201780050159.6A
Authority: CN
Inventors: 樱井彩香; 宫本知典; 上原满
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2016-08-19
Filing date: 2017-08-08
Publication date: 2021-11-26
Anticipated expiration: 2037-08-08
Also published as: TWI725219B; JP6996898B2; KR102338219B1; WO2018034202A1; JP2018031000A; CN109563338A; TW201816009A; KR20190042033A

Abstract

The purpose of the present invention is to provide a coating composition having good abrasion resistance. The present invention is a composition characterized by comprising: a compound (A) in which (a1) a 1-valent group having a perfluoropolyether structure, and (a2) at least one of a hydrolyzable group and a hydroxyl group are bonded to a silicon atom; and a compound (B) having a hydroxyl group and an oxyalkylene unit, at least a part of hydrogen atoms of the oxyalkylene unit being substituted with fluorine atoms, and having a number average molecular weight of less than 10000.

Description

Composition comprising a metal oxide and a metal oxide

Technical Field

The present invention relates to compositions.

Background

A coating film formed from a composition containing a compound having a fluorooxyalkylene group has water-and-oil repellency, chemical resistance, mold release property, and the like because the surface free energy thereof is very small. By utilizing the properties thereof, patent document 1 discloses a fluorine-containing coating agent comprising (a) a hydrolyzable group-containing silane modified with a fluorooxyalkylene group-containing polymer and/or a partial hydrolysis-condensation product thereof, and (B) a fluorooxyalkylene group-containing polymer having an average molecular weight of the component (a) or less. Patent document 1 describes that the polymer (B) containing a fluoroalkylene group contains a nonfunctional fluoroalkylene group.

Patent document 2 discloses a fluorine-based surface treatment agent for vapor deposition, which contains (a) a hydrolyzable group-containing silane modified with a fluorooxyalkylene group-containing polymer and/or a partially hydrolyzed condensate thereof, and (B) a fluorooxyalkylene group-containing polymer having a larger weight average molecular weight than the component (a), and the mixing mass ratio of the component (a) to the component (B) is 6:4 to 9: 1. It is described that the polymer (B) containing a fluoroalkylene group in patent document 2 is also nonfunctional as in patent document 1.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2015-199915

Patent document 2: japanese patent laid-open publication No. 2013-136833

Disclosure of Invention

Problems to be solved by the invention

Patent document 1 describes that a polymer containing an nonfunctional oxyfluoroalkylene group is excellent in wear resistance, and patent document 2 describes that a coating film excellent in durability is formed when a fluorine-based surface treatment agent is vapor-deposited on a substrate by a vacuum vapor deposition method. However, there is room for improvement in the improvement of abrasion resistance.

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

Means for solving the problems

The present invention is a composition comprising: a compound (A) in which (a1) a 1-valent group having a perfluoropolyether structure, and (a2) at least one of a hydrolyzable group and a hydroxyl group are bonded to a silicon atom; and a compound (B) having a hydroxyl group and an oxyalkylene unit, at least a part of hydrogen atoms of the oxyalkylene unit being substituted with fluorine atoms, and having a number average molecular weight of less than 10000.

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

[ chemical formula 1]

In the formula (1a), the compound (A),

Rf¹is that more than 1 hydrogen atom is taken by fluorine atomA substituted alkyl group having 1 to 20 carbon atoms or a fluorine atom,

Rf²each independently an alkyl group having 1 to 20 carbon atoms in which 1 or more hydrogen atoms are replaced by fluorine atoms or a fluorine atom,

R¹each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

R²each independently an alkyl group having 1 to 20 carbon atoms,

d is independently-O-, -C (═ O) -O-, -O-C (═ O) -, -NR-, -NRC (═ O) -, or-C (═ O) NR-, R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms,

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

a1, b1, c1, d1 and e1 are each independently an integer of 0 to 600 inclusive, the total value of a1, b1, c1, d1 and e1 is 9 or more,

n is an integer of 1 to 3 inclusive,

the repeating units denoted by a1, b1, c1, d1, and e1 and enclosed in parentheses may be arranged in an order in which at least a part of the repeating units form a perfluoropolyether structure, and may be arranged in any order.

[ chemical formula 2]

In the formula (2a), the compound (A),

Rf³an alkyl group having 1 to 20 carbon atoms in which 1 or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom,

Rf⁴each independently an alkyl group having 1 to 20 carbon atoms in which 1 or more hydrogen atoms are replaced by fluorine atoms or a fluorine atom,

R³each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

R⁴each independently an alkyl group having 1 to 20 carbon atoms,

each M is independently-O-, -C (═ O) -O-, -O-C (═ O) -, -NR-, -NRC (═ O) -, or-C (═ O) NR-, R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms,

each G is independently 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 each independently an integer of 0 to 600 inclusive, the total value of a2, b2, c2, d2 and e2 is 9 or more,

f2 is an integer of 1 to 20 inclusive,

g2 is an integer of 0 to 2 inclusive,

p is an integer of 1 to 3 inclusive,

the repeating units denoted by a2, b2, c2, d2, and e2 and enclosed in parentheses may be arranged in an order in which at least a part of the repeating units form a perfluoropolyether structure, and may be arranged in any order.

The compound (a) is preferably a compound of the formula (1a) in which the total value of a1, b1, c1, d1 and e1 is 13 or more, or a compound of the formula (2a) in which the total value of a2, b2, c2, d2 and e2 is 13 or more.

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

[ chemical formula 3]

In the above formula (1b), X is each independently a hydrogen atom or a fluorine atom, Rf⁵Each independently being a hydrogen atom, a fluorine atom, or-CF₃J is-O-, -C (═ O) -O-, or-O-C (═ O) -O-, a3 is 1 or more and 5 or less, b3 is 20 or more and 200 or less, C3 is 5 or more and 200 or less, and each of the repeating units denoted by a3 to C3 and enclosed in parentheses may be arranged in any order as long as it is an order in which oxyalkylene units are formed from at least a part thereof, and at least a part of the oxyalkylene units may be arranged in any orderThe hydrogen atoms are replaced by fluorine atoms.

The number of hydroxyl groups contained in the compound (B) is preferably 1 to 2. In the compound (B), it is also preferable that the ratio of the number of fluorine atoms to the total of the number of hydrogen atoms and the number of fluorine atoms excluding the hydrogen atoms in the hydroxyl group is 40% or more.

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

ADVANTAGEOUS EFFECTS OF INVENTION

The composition of the present invention uses a compound (a) characterized by a perfluoropolyether structure and a compound (B) having a hydroxyl group and an oxyalkylene unit in which at least a part of hydrogen atoms of the oxyalkylene unit is substituted with a fluorine atom, and thus can realize a hydrophobic film having excellent abrasion resistance.

Detailed Description

The composition of the present invention comprises a compound (A) having a perfluoropolyether structure and a compound (B) having a hydroxyl group and an oxyalkylene unit. The coating film can exhibit good hydrophobicity due to the perfluoropolyether structure of the compound (a) and oxyalkylene units in which at least a part of hydrogen atoms of the compound (B) is substituted with fluorine atoms. Further, by providing a hydroxyl group to the compound (B), the wear resistance of the coating film can be ensured.

The compound (a) may be any compound as long as it contains not only fluorine but also a base material capable of forming a coating film by bonding the compounds (a) to each other or to other monomers through a polymerization reaction (particularly, a polycondensation reaction). Preferably, the compound (a) is a compound containing a fluorine-containing group and at least one of a hydrolyzable group and a hydroxyl group, and in the present invention, a compound in which (a1) a 1-valent group having a perfluoropolyether structure and (a2) at least one of a hydrolyzable group and a hydroxyl group are bonded to a silicon atom is used.

The perfluoropolyether structure is a structure in which all hydrogen atoms of the polyalkylene ether group or polyalkylene glycol dialkyl ether residue are substituted with fluorine atoms, and may be referred to as a perfluoropolyether ether group or a perfluoropolyether glycol dialkyl ether residue. In addition, the perfluoropolyether structure can also be referred to as a perfluoroalkoxyalkylene. The perfluoropolyether structure imparts hydrophobicity to the obtained coating film. The number of carbon atoms included in the longest linear 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 1-valent group having a perfluoropolyether structure is bonded to a silicon atom. On the side of the perfluoropolyether structure bonded to the silicon atom, an appropriate linking group may be present, or the linking group may not be present, but the perfluoropolyether structure is directly bonded to the silicon atom. Examples of the linking group include a hydrocarbon group such as an alkylene group or an aromatic hydrocarbon group, a (poly) alkylene glycol group, a group obtained by substituting at least a part of hydrogen atoms thereof with a fluorine atom, and a group obtained by appropriately linking these groups. The number of carbon atoms of the linking group is, for example, 1 or more and 20 or less, preferably 2 or more and 10 or less.

It is to be noted that a plurality of silicon atoms may be bonded to one linking group, and a plurality of perfluoropolyether structures may be bonded to one linking group. The number of the 1-valent groups having a perfluoropolyether structure bonded to a silicon atom may be 1 or more, and may be 2 or 3, but is preferably 1 or 2, and particularly preferably 1.

In the compound (a), at least one of a hydrolyzable group and a hydroxyl group is bonded to a silicon atom, and the hydrolyzable group and the hydroxyl group each have a function of bonding the compounds (a) to each other or bonding the compound (a) to an active hydrogen such as a hydroxyl group from the surface of the substrate through hydrolysis and/or dehydration condensation reaction. 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 (particularly, a chlorine atom), and the like. The hydrolyzable group is preferably an alkoxy group and a halogen atom, and particularly preferably a methoxy group, an ethoxy group, or a chlorine atom.

The number of hydrolyzable groups bonded to the silicon atom may be 1 or more, and may be 2 or 3, but is preferably 2 or 3, and is particularly preferably 3. When 2 or more hydrolyzable groups are bonded to a silicon atom, different hydrolyzable groups may be bonded to the silicon atom, but it is preferable that the same hydrolyzable group is bonded to the silicon atom. The total number of fluorine-containing groups and hydrolyzable groups bonded to the silicon atom is usually 4, but may be 2 or 3 (particularly 3). When the number is 3 or less, 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 chemical bond.

The 1-valent group having a perfluoropolyether structure in the compound (a) may be linear or have a side chain.

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

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

[ chemical formula 4]

In the formula (1a), the compound (A),

Rf¹an alkyl group having 1 to 20 carbon atoms in which 1 or more hydrogen atoms are substituted with fluorine atoms or a fluorine atom,

R²each independently an alkyl group having 1 to 20 carbon atoms,

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

a1, b1, c1, d1 and e1 are each independently an integer of 0 to 600 inclusive, the total value of a1, b1, c1, d1 and e1 is 9 or more, preferably 13 or more,

n is an integer of 1 to 3 inclusive,

the repeating units denoted by a1, b1, c1, d1, and e1 and enclosed in parentheses may be arranged in an order in which at least a part of the repeating units form a perfluoropolyether structure, and may be arranged in any order. In addition, a plurality of the repeating units may be present in the molecule. In the present specification, the case where a plurality of repeating units are present in a molecule includes the case where the repeating units are not present continuously, for example, the case where 2 repeating units are present in a molecule and each repeating unit is sandwiched between 2 different repeating units.

Rf¹Preferably an alkyl group having 1 to 10 carbon atoms substituted with 1 or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and still more preferably a perfluoroalkyl group having 1 to 5 carbon atoms.

Rf²Each of the fluorine atoms is preferably a fluorine atom or a fluorine-containing alkyl group having 1 to 2 carbon atoms, and more preferably all fluorine atoms.

R¹Each independently is preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and more preferably all hydrogen atoms.

R²Each independently preferably an alkyl group having 1 to 5 carbon atoms.

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

E is independently preferably 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 order of the repeating units denoted by a1, b1, c1, d1, and e1 and bracketed by the numerals is preferably such that the repeating unit denoted by b1 and bracketed by the most fixed end side (the side bonded to the silicon atom) is located closer to the free end side than the repeating unit denoted by a1 and bracketed by the most free end side, and more preferably such that the repeating unit denoted by b1 and d1 and bracketed by the most fixed end side is located closer to the free end side than the repeating unit denoted by a1 and c1 and bracketed by the most free end side. Each repeat unit designated e1 and enclosed in parentheses is preferably present in at least 2.

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

In the above formula (1a), Rf is particularly preferred¹Is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf²All being fluorine atoms, R¹All are hydrogen atoms, all D are — O-, E is methoxy or ethoxy, a1 is an integer of 1 to 3, c1 ═ D1 ═ 0, b1 and E1 are values set so that the compound of formula (1a) can maintain a liquid state at normal pressure, and n ═ 3. The total value of b1 and e1 can be 8 or more.

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

[ chemical formula 5]

In the above formula (1a-1), R¹⁰Is a perfluoroalkyl group having 1 to 5 carbon atoms, R¹¹Is C1-5 perfluoroalkylene, R¹²Is C1-3 perfluoroalkylene, R¹³Is alkylene having 1 to 3 carbon atoms, R¹⁴Is an alkyl group having 1 to 3 carbon atoms, z2 and z3 are each an integer of 1 to 3, and z1 is a value set so that the compound represented by the above formula (1a-1) can maintain a liquid under normal pressure, and may be set to 3 or more, for example.

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

[ chemical formula 6]

In the above-mentioned formula (2a),

R⁴each independently an alkyl group having 1 to 20 carbon atoms,

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

z is a hydrogen atom or a halogen atom,

a2, b2, c2, d2 and e2 are each independently an integer of 0 to 600 inclusive, the total value of a2, b2, c2, d2 and e2 is 9 or more, preferably 13 or more,

f2 is an integer of 1 to 20 inclusive,

g2 is an integer of 0 to 2 inclusive,

p is an integer of 1 to 3 inclusive,

the repeating units denoted by a2, b2, c2, d2, and e2 and enclosed in parentheses may be arranged in an order in which at least a part of the repeating units form a perfluoropolyether structure, and may be arranged in any order. In addition, a plurality of the repeating units may be present in the molecule.

Rf³Preferably an alkyl group having 1 to 10 carbon atoms substituted with 1 or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, and still more preferably a perfluoroalkyl group having 1 to 5 carbon atoms.

Rf⁴Each of the fluorine atoms is preferably a fluorine atom or a fluorine-containing alkyl group having 1 to 2 carbon atoms, and more preferably all fluorine atoms.

R³Each of which is preferably independently a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and more preferably all of which are hydrogen atoms.

R⁴Each independently preferably an alkyl group having 1 to 5 carbon atoms.

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

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

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

Z is preferably a hydrogen atom.

A2, c2 and d2 are each preferably 1/2 or less of b2, more preferably 1/4 or less, still more preferably c2 or d2 is 0, and particularly preferably c2 and d2 are 0.

e2 is preferably 1/5 or more of the total value of a2, b2, c2 and d2 and is preferably equal to or less than the total value of a2, b2, c2 and d 2.

b2 is preferably 20 or more and 600 or less, more preferably 20 or more and 200 or less, and further preferably 50 or more and 200 or less. e2 is preferably 4 or more and 600 or less, more preferably 4 or more and 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 and 200 or less, and further preferably 50 or more and 200 or less.

f2 is preferably 1 to 18 inclusive. More preferably 1 or more and 15 or less.

g2 is preferably 0 or more and 1 or less.

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

The order of the repeating units denoted by a2, b2, c2, d2, and e2 and bracketed by the numerals is preferably such that the repeating unit denoted by b2 and bracketed by the most fixed end side (the side bonded to the silicon atom) is located closer to the free end side than the repeating unit denoted by a2 and bracketed by the most free end side, and more preferably such that the repeating unit denoted by b2 and d2 and bracketed by the most fixed end side is located closer to the free end side than the repeating unit denoted by a2 and c2 and bracketed by the most free end side. In addition, each repeating unit labeled e2 and enclosed in parentheses is preferably present in at least 2.

In the formula (2a), Rf is particularly preferred³Is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf⁴All are fluorine atoms, all M are-O-, G is a methoxy group, an ethoxy group, or a chlorine atom (particularly a methoxy group or an ethoxy group), Y and Z are each a hydrogen atom, a2 is 0, b2 is 30 to 150 (more preferably 80 to 140), e2 is 30 to 60, c2 and d2 are 0, G2 is 0 or more and 1 or less (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 (2 a-1).

[ chemical formula 7]

In the above formula (2a-1), R²⁰Is a perfluoroalkyl group with 2-6 carbon atoms, R²¹And R²²All of which are C2-6 perfluoroalkylene, R²³Is a 3-valent saturated hydrocarbon group with 2-6 carbon atoms, R²⁴Is an alkyl group having 1 to 3 carbon atoms. R²⁰、R²¹、R²²And R²³The number of carbon atoms of (A) is preferably 2 to 4, more preferably 2 to 3, independently of each other. x1 is 5-70, x2 is 1-5, and x3 is 1-10. The x1 is preferably 10-60, more preferably 20-50, the x2 is preferably 1-4, more preferably 1-3, and the x3 is preferably 1-8, more preferably 1-6.

The compound (B) has a hydroxyl group and an oxyalkylene unit, at least a part of hydrogen atoms of the oxyalkylene unit is substituted with fluorine atoms, and the number average molecular weight is less than 10000. Since the hydroxyl group of the compound (B) interacts with a substrate such as glass or the compound (a) and is less likely to be peeled off, it is considered that the abrasion resistance of the coating film is improved as compared with the case where a compound having a similar structure and not having a hydroxyl group is used in place of the compound (B).

In addition, from the viewpoint of sufficiently securing the component derived from the compound (B) in the coating film obtained by vacuum deposition, it is important that the number average molecular weight of the compound (B) is less than 10000, and the lower limit is preferably about 1000, for example. The number average molecular weight of the compound (B) is preferably 8000 or less, more preferably 6000 or less.

The hydroxyl group in the compound (B) may be present at least 1, preferably 5 or less, and more preferably 2 or less. In the compound (B), the proportion of the number of fluorine atoms to the total of the number of hydrogen atoms and the number of fluorine atoms excluding the hydrogen atoms in the hydroxyl group is preferably 40% or more, whereby good water repellency can be exhibited. The ratio of the number of fluorine atoms is more preferably 50% or more, and still more preferably 55% or more, and the upper limit is not particularly limited, and may be 100%, for example, may be about 80%.

Examples of the compound (B) include compounds represented by the following formula (1B).

[ chemical formula 8]

In the formula (1b), X is each independently a hydrogen atom or a fluorine atom, Rf⁵Each independently being a hydrogen atom, a fluorine atom, or-CF₃J is — O-, -C (═ O) -O-, or-O-C (═ O) -O-, a3 is 1 or more and 5 or less, b3 is 20 or more and 200 or less, and C3 is 5 or more and 200 or less, and each of the repeating units denoted by a3 to C3 and enclosed in parentheses may be arranged in any order as long as it is an order in which oxyalkylene units are formed from at least a part thereof, and at least a part of hydrogen atoms in the oxyalkylene units are substituted with fluorine atoms. Further, a plurality of the repeating units each having a3 to c3 enclosed in parentheses may be present in the molecule.

Rf⁵Each independently is preferably a hydrogen atom or a fluorine atom, X is preferably a hydrogen atom, J is preferably-O-, and a3 is preferably 1 or more and 3 or less, more preferably 1 or 2 (most preferably 2). b3 is preferably 30 to 100 inclusive, and c3 is preferably 10 to 80 inclusive. b3 and c3 are preferably determined so that the number average molecular weight of the compound represented by the formula (1b) is 2000 to 4500, more preferably 2500 to 4500. Most desirably, Rf is preferred⁵Each independently being a hydrogen atomOr a fluorine atom, X is a hydrogen atom, J is-O-, a3 is 1 or 2, and b3 and c3 are values determined so that the number average molecular weight of the compound represented by the above formula (1b) is 2000 to 4500 (more preferably 2500 to 4500).

Examples of the compound (B) include polyalkylene glycols in which one OH group of the polyalkylene glycol having OH groups at both ends is substituted with a hydrogen atom and at least a part of the hydrogen atoms of the alkylene group is substituted with a fluorine atom. As the compound (B), a polyalkylene glycol in which at least a part of hydrogen atoms of the alkylene group is substituted with fluorine atoms is particularly preferable, and such a polyalkylene glycol can be represented by, for example, the following formulae (1B-1) and (1B-2).

[ chemical formula 9]

In the formula (1b-1), R³⁰、R³¹、R³²、R³⁴And R³⁵Each independently an alkylene group having 2 to 6 carbon atoms, R³³Is alkylene having 1 to 5 carbon atoms, R³⁰～R³⁵In at least 1 alkylene group, at least 1 of hydrogen atoms in the total alkylene group(s) in (b) is substituted by 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 formula (1b-1) is 2000 to 2400, y6 is 1 to 4, and y7 is 2 to 10.

R³⁰、R³¹、R³²、R³⁴And R³⁵Each independently is preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms. In addition, R³³Preferably an alkylene group having 1 to 3 carbon atoms, and more preferably an alkylene group having 1 to 2 carbon atoms. y1 is preferably 3 to 9, more preferably 4 to 8, y2 is preferably 1 to 3, more preferably 1 to 2, y6 is preferably 1 to 3, more preferably 1 to 2, y7 is preferably 3 to 9, more preferably 4 to 8.

[ chemical formula 10]

In the formula (1b-2), R⁴⁰And R⁴³Each independently an alkylene group having 1 to 3 carbon atoms, R⁴¹Is an alkylene group having 1 to 5 carbon atoms in which at least 1 of the hydrogen atoms is substituted with a fluorine atom, R⁴²Is an alkylene group having 1 to 3 carbon atoms in which at least 1 of the hydrogen atoms is substituted with a fluorine atom, w1 and w4 are each independently 1 to 3, and w2 and w3 are values determined so that the number average molecular weight of the compound represented by the formula (1b-2) is 3800 to 4200.

R⁴⁰And R⁴³Each independently preferably an alkylene group having 1 to 2 carbon atoms, R⁴¹Preferably an alkylene group having 1 to 3 carbon atoms in which at least 1 of the hydrogen atoms is substituted with a fluorine atom, R⁴²Preferably, the alkylene group having 1 to 2 carbon atoms in which at least 1 of the hydrogen atoms is substituted by a fluorine atom, and w1 and w4 are each independently preferably 1 to 2, and more preferably satisfy both of these requirements.

The mass ratio of the compound (a) to the compound (B) in the composition is preferably 1 or more. This improves the balance between the water repellency and the abrasion resistance of the obtained coating film. 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). In view of the balance between the water repellency and the abrasion resistance of the obtained coating film, the upper limit of the mass ratio is preferably 13 or less, and more preferably 11 or less.

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

The composition of the present invention preferably contains not only the above-mentioned compounds (a) and (B), but also a fluorine-based solvent (C). As the fluorine-based solvent (C), for example, a fluoroether-based solvent, a fluoroamine-based solvent, a hydrofluorocarbon-based solvent (particularly, a fluorinated aromatic solvent) and the like can be used, and the boiling point is particularly preferably 100 ℃ or higher. The fluoroether solvent is preferably a hydrofluoroether such as a fluoroalkyl (particularly, a perfluoroalkyl group having 2 to 6 carbon atoms) -alkyl (particularly, methyl or ethyl) ether, and examples thereof include ethylnonafluorobutyl ether and ethylnonafluoroisobutyl ether. Examples of the ethylnonafluorobutyl ether and ethylnonafluoroisobutyl ether include Novec (registered trademark) 7200 (available from 3M company, molecular weight: about 264, boiling point: 76 ℃). The fluoroamine-based solvent is preferably an amine in which at least 1 of the hydrogen atoms of ammonia is substituted with a fluoroalkyl group, more preferably a tertiary amine in which all the hydrogen atoms of ammonia are substituted with a fluoroalkyl group (particularly, a perfluoroalkyl group), and specifically, tris (heptafluoropropyl) amine is mentioned, and Fluorinert (registered trademark) FC-3283 (molecular weight: 471, boiling point: 128 ℃ C.) belongs to this compound. As the fluorocarbon solvent, 1, 3-bis (trifluoromethylbenzene) (boiling point: about 116 ℃ C.) may be mentioned.

As the fluorine-containing solvent (C), in addition to the above, hydrochlorofluorocarbons such as ASAHIKLIN (registered trademark) AK225 (manufactured by Asahi glass company), hydrofluorocarbons such as ASAHIKLIN (registered trademark) AC2000 (manufactured by Asahi glass company) and the like can be used.

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, and is, for example, about 300.

The content of the fluorine-containing solvent (C) in the composition of the present invention is, for example, 20 mass% or more, more preferably 50 mass% or more, further preferably 70 mass% or more, preferably 90 mass% or less, more preferably 88 mass% or less, and further preferably 86 mass% or less, based on the total mass of the composition.

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

The composition of the present invention may contain various additives such as an antioxidant, a rust inhibitor, an ultraviolet absorber, a light stabilizer, a fungicide, an antibacterial agent, an antifouling agent, a deodorant, a pigment, a flame retardant, and an antistatic agent, in a range not to impair the effects of the present invention.

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

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

After vacuum deposition, the film can be left to stand at room temperature or heated (for example, held at 50 to 150 ℃ for 5 to 30 minutes) in the air to absorb moisture in the air, whereby the hydrolyzable group bonded to the silicon atom of the compound (a) is hydrolyzed to form a siloxane bond, thereby obtaining a cured coating film. The film thickness of the obtained coating film may be, for example, 2 to 10 nm.

The material of the substrate on which the composition of the present invention is deposited is not particularly limited, and may be any of an organic material and an inorganic material, and the shape of the substrate may be any of a plane and a curved surface, or may be a three-dimensional structure in which a plurality of surfaces are combined. Examples of the organic material include thermoplastic resins such as acrylic resins, polycarbonate resins, polyester resins, styrene resins, acrylic-styrene copolymer resins, cellulose resins, polyolefin resins, and polyvinyl alcohols; thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins, and urethane resins. Examples of the inorganic material include metals such as iron, silicon, copper, zinc, and aluminum, alloys containing these metals, ceramics, and glasses. Among them, it is particularly preferable to form a coating film by vapor deposition of the composition of the present invention on a substrate made of an inorganic material such as glass, metal, or ceramic.

After the film is formed on the substrate, the state after vapor deposition may be maintained, or a predetermined post-treatment may be performed, and the wear resistance of the film may be further improved by performing the post-treatment. The post-treatment may be carried out by heating, holding under a humidified atmosphere, ultrasonic cleaning, wiping the surface with a solvent, or the like, and these post-treatments may be carried out alone or in combination of 2 or more. Among them, it is particularly preferable to perform heat retention and ultrasonic washing, and the heat retention may be performed at 100 to 200 ℃ for 10 to 60 minutes, for example, and the ultrasonic washing may be performed for about 1 to 5 minutes using water, a fluorine-based solvent, an alcohol, or the like as a washing liquid, for example. From the viewpoint of further improving the abrasion resistance, ultrasonic washing is preferable. Since the composition of the present invention contains the compound (B) having a hydroxyl group, the interaction between the compound (B) and the substrate (e.g., glass) or the compound (a) can be expected to be in a state having higher durability by performing the post-treatment as compared with the case where the composition contains a conventional compound having no hydroxyl group.

The substrate may be subjected to an easy adhesion treatment in advance. Examples of the easy adhesion treatment include hydrophilization treatments such as corona treatment, plasma treatment, and ultraviolet treatment. In addition, an undercoating treatment based on a resin, a silane coupling agent, tetraalkoxysilane, or the like can be utilized. Alternatively, a silicon dioxide layer may be formed by vapor deposition.

The undercoat layer is preferably a layer formed using an undercoat layer-forming composition containing a component (E) formed from a compound represented by the following formula (p1) and/or a partial hydrolysis-condensation product thereof.

Si(X²)₄···(p1)

(wherein, in the formula (p1), a plurality of X's are present²Each independently represents a halogen atom, an alkoxy group or an isocyanate group. )

In the above formula (p1), X²Each independently preferably a chlorine atom, an alkoxy group having 1 to 4 carbon atoms or an isocyanate group,further, 4X's are preferable²The same is true.

As the compound represented by the formula (p1), specifically, Si (NCO) can be preferably used₄、Si(OCH₃)₄、Si(OC₂H₅)₄And the like. (E) The components can be used alone in 1 kind, or more than 2 kinds.

The component (E) contained in the composition for forming an undercoat layer may be a partial hydrolysis condensate of the compound represented by the formula (p 1). The partial hydrolysis-condensation product of the compound represented by the formula (p1) can be obtained by applying a conventional hydrolysis-condensation method using an acid or base catalyst. However, the degree of condensation (degree of polymerization) of the partial hydrolysis condensate needs to be such that the product is soluble in the solvent. The component (E) may be a compound represented by the above formula (p1), a partially hydrolyzed condensate of a compound represented by the above formula (p1), a mixture of a compound represented by the above formula (p1) and a partially hydrolyzed condensate thereof, or a partially hydrolyzed condensate of the compound including an unreacted compound represented by the above formula (p 1). The compound represented by the above formula (p1) and a partial hydrolysis condensate thereof are commercially available, and such commercially available products can be used in the present invention.

The composition for forming an undercoat layer may be a composition containing the component (E) and a component (F) formed from a compound represented by the following formula (p2) (which may be referred to as a compound (p2)) and/or a partial hydrolysis condensate thereof, or a composition containing a partial hydrolysis condensate of the component (E) and the component (F) (which may contain the component (E) and/or the compound (p 2)).

(X³)₃Si-(CH₂)_p-Si(X³)₃···(p2)

(wherein, in the formula (p2), a plurality of X's are present³Each independently represents a hydrolyzable group or a hydroxyl group, and p is an integer of 1 to 8. )

The compound represented by the formula (p2) is a compound having hydrolyzable silyl groups or silanol groups at both ends with a 2-valent organic group interposed therebetween.

Formula (A), (B) andp2), as X³Examples of the hydrolyzable group represented by the formula (I) include the groups represented by the formula (I) and (II)²The same group or atom. From the viewpoint of the balance between the stability of the compound represented by the above formula (p2) and the ease of hydrolysis, X is³Alkoxy groups and isocyanate groups are preferred, and alkoxy groups are particularly preferred. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group. They can be suitably selected and used according to the purpose, use, and the like of production. In the formula (p2), there are plural X' s³The groups may be the same or different, and are preferably the same from the viewpoint of availability.

Specific examples of the compound represented by the formula (p2) include (CH)₃O)₃SiCH₂CH₂Si(OCH₃)₃、(OCN)₃SiCH₂CH₂Si(NCO)₃、Cl₃SiCH₂CH₂SiCl₃、(C₂H₅O)₃SiCH₂CH₂Si(OC₂H₅)₃、(CH₃O)₃SiCH₂CH₂CH₂CH₂CH₂CH₂Si(OCH₃)₃And the like. (F) The components can be used alone in 1 kind, or more than 2 kinds.

The component contained in the composition for forming an undercoat layer may be a partial hydrolysis condensate of the compound represented by formula (p 2). The partial hydrolysis condensate of the compound represented by the formula (p2) can be obtained by the same method as that described for the production of the partial hydrolysis condensate of the compound represented by the formula (p 1). The degree of condensation (degree of polymerization) of the partial hydrolytic condensate needs to be such that the product is soluble in the solvent. The component (F) may be a compound represented by the formula (p2), a partially hydrolyzed condensate of a compound represented by the formula (p2), a mixture of a compound represented by the formula (p2) and a partially hydrolyzed condensate thereof, for example, a partially hydrolyzed condensate of a compound containing an unreacted compound represented by the formula (p 2). The compound represented by the above formula (p2) and a partial hydrolysis condensate thereof are commercially available, and such commercially available products can be used in the present invention.

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

The composition for forming an undercoat layer usually contains an organic solvent in addition to a solid component as a layer-constituting component, in consideration of economy, workability, ease of controlling the thickness of the obtained undercoat layer, and the like. The organic solvent is not particularly limited as long as it dissolves solid components contained in the composition for forming an undercoat layer. Examples of the organic solvent include the same compounds as those usable in the composition of the present invention. The organic solvent is not limited to 1 type, and 2 or more types of solvents having different polarities, evaporation rates, and the like may be mixed and used. When the composition for forming an undercoat layer contains a partial hydrolysis condensate or a partial hydrolysis cocondensate, a solvent used for producing the same may be contained.

In addition, in the composition for forming an undercoat layer, even when a partial hydrolysis condensate or a partial hydrolysis cocondensate is not contained, it is preferable to add a catalyst such as an acid catalyst as is generally used in a partial hydrolysis condensation reaction in advance in order to promote the hydrolysis cocondensation reaction. Even when the composition contains a partially hydrolyzed condensate or a partially hydrolyzed co-condensate, it is preferable to add a catalyst when the catalyst used for producing the partially hydrolyzed condensate or the partially hydrolyzed co-condensate does not remain in the composition. The composition for forming an undercoat layer may contain water for subjecting the above-mentioned components to a hydrolysis condensation reaction or a hydrolysis co-condensation reaction.

As a method for forming an undercoat layer using the composition for forming an undercoat layer, known methods in surface treatment agents of organosilane compound series can be used. For example, the undercoat layer can be formed by applying the composition for forming an undercoat layer to the surface of a substrate by a method such as brush coating, flow coating, spin coating, dip coating, blade coating, spray coating, or hand coating, drying the composition in the air or in a nitrogen atmosphere as needed, and then curing the composition. The curing conditions may be appropriately controlled depending on the kind, concentration, and the like of the composition to be used. The curing of the composition for forming an undercoat layer may be performed simultaneously with the curing of the composition for forming a hydrophobic film.

The thickness of the undercoat layer is not particularly limited, and may be any thickness as long as it can impart moisture resistance to the transparent film formed thereon, can impart adhesion to the substrate, and can isolate the substrate from alkali and the like.

The coating film obtained from the composition of the present invention is excellent in static hydrophobic properties and dynamic hydrophobic properties. The static hydrophobic property can be evaluated by, for example, an initial contact angle analyzed by a θ/2 method using a droplet method, and the dynamic hydrophobic property can be evaluated by a contact angle hysteresis (contact angle hysteresis) or a slip angle measured using a slip method. For example, the initial contact angle measured with a droplet amount of 3 μ L may be, for example, 110 ° or more, preferably 113 ° or more, and more preferably 115 ° or more, and the upper limit is not particularly limited, and may be, for example, about 125 °. The contact angle hysteresis measured with a droplet volume of 6.0. mu.L can be, for example, 12 ℃ or less, preferably 10 ℃ or less, more preferably 9 ℃ or less, and the lower limit is not particularly limited, and can be, for example, about 3 ℃. The slip angle measured by the amount of water droplets of 6 μ L is, for example, 30 ° or less, preferably 25 ° or less, and more preferably 23 ° or less, and the lower limit is not particularly limited, and is, for example, about 5 °.

Examples

The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples, and may be carried out by appropriately changing the examples within a range that can meet the gist described above and below, and all of them are included in the technical scope of the present invention.

The coating films obtained in the 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 measuring apparatus (SmartLab) manufactured by Rigaku Corporation was used. As the X-ray source, an X-ray generator of 45kW, a CuK α ray wavelength λ of 0.15418nm or a CuK α 1 ray wavelength λ of 0.15406nm from a Cu target, and a monochromator were used. As setting conditions, the sampling width is set to 0.01 DEG, and the scanning range is set to 0.0-2.5 deg. Then, the reflectance is measured under the above-mentioned set conditions to obtain a measured reflectance value. The obtained measurement values were analyzed using the company analytical software (GlobalFit).

(2) Determination of initial contact Angle

The contact angle of water on the surface of the coating film was measured by a liquid drop method (analysis method: θ/2 method) using a contact angle measuring apparatus (DM 700, manufactured by Kyowa Kagaku Co., Ltd.) in a liquid amount of 3 μ L.

(3) Determination of contact Angle hysteresis and slip Angle

The dynamic hydrophobic properties (contact angle hysteresis, slip angle) of the surface of the coating were measured by the slip method (analytical method: contact method, amount of water droplets: 6.0. mu.L, tilt method: continuous tilt, slip detection: slip after, movement determination: advancing angle, slip determination distance: 0.125mm) using DM700, manufactured by Kyowa interface science Co., Ltd.

(4) Evaluation of abrasion resistance

The abrasion test was performed by applying a 500g load to a scratch device equipped with an HB pencil with an eraser manufactured by Mitsubishi Pencil corporation, in a state where the eraser was in contact with the sample, and moving the sample at 40 r/min. The contact angle was measured every 1000 wear cycles, and the number of wear cycles was measured until the initial contact angle became-15 degrees or less.

Example 1

A compound represented by the following formula (a) (number average molecular weight about 8000) was synthesized by the method described in synthesis examples 1 and 2 of jp 2014-15609 a.

[ chemical formula 11]

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

The compound (a) represented by the above formula (a) was used as the compound (a), and the compound (B1) (number average molecular weight about 2240) represented by the following formula (B1) was used as the compound (B).

[ 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 and the number of fluorine atoms excluding the hydrogen atoms in the hydroxyl group is 40% or more.

As the fluorine-based solvent (C), Novec7200 (registered trademark) was used to prepare a mixture of the compound (a): compound (B): a composition wherein the fluorine-containing solvent (C) is contained in a ratio of 89:11: 400. This was dropped into 1mL of a Ta boat for vapor deposition, and then the solvent was evaporated to prepare a sample for vapor deposition. VPC-410A manufactured by ULVAC KIKO, Inc. was used, and vacuum deposition (resistance heating method, pressure 8X 10) was performed^-3Pa, applied current 20A, vapor deposition treatment time 15 seconds), and the above-described sample was formed into a film on alkali-free glass EAGLE-XG (registered trademark, manufactured by Corning corporation), thereby preparing a sample for film performance evaluation.

The results of evaluating the wear resistance of the obtained coating are shown in table 1. In example 1, the initial contact angle was 115.8 °, the slip angle was 27.7 °, and the contact angle hysteresis was 10.6 °.

Example 2

The same operation as in example 1 was carried out except that the film was formed and then heat treatment was carried out at 150 ℃ for 30 minutes. Samples for evaluation of film properties were prepared.

The results of evaluating the wear resistance of the obtained coating are shown in table 1. In example 2, the initial contact angle was 115.8 °, the slip angle was 17.3 °, and the contact angle hysteresis was 7.1 °.

Example 3

A sample for evaluation of film performance was prepared in the same manner as in example 1, except that ultrasonic washing treatment was further performed in water for 3 minutes after the film formation.

The results of evaluating the wear resistance of the obtained coating are shown in table 1. In example 3, the initial contact angle was 117.9 °, the slip angle was 22.3 °, and the contact angle hysteresis was 8.3 °.

Example 4

A sample for evaluation of film performance was prepared in the same manner as in example 2, except that Fluorolink (registered trademark) D4000 (number average molecular weight about 4000) represented by the following formula (b2) was used instead of compound (b 1). Fluorolink (registered trademark) D4000 has not only a hydroxyl group at the terminal but also an oxyalkylene unit in which a part of the hydrogen atom is substituted with a fluorine atom. In FluorolinkD4000, the ratio of the number of fluorine atoms to the total of the number of hydrogen atoms and the number of fluorine atoms excluding the hydrogen atoms in the hydroxyl group is 40% or more.

[ chemical formula 13]

The results of evaluating the wear resistance of the obtained coating are shown in table 1. In example 4, the initial contact angle was 111.1 °, the slip angle was 7.3 °, and the contact angle hysteresis was 4.8 °.

Example 5

Changing the mass ratio of the composition to compound (A): compound (B): a sample for film performance evaluation was prepared in the same manner as in example 2, except that the fluorine-based solvent (C) was used in a ratio of 80:20: 400.

The results of evaluating the wear resistance of the obtained coating are shown in table 1. In example 5, the initial contact angle was 114.9 °, the slip angle was 26.3 °, and the contact angle hysteresis was 14.5 °.

Example 6

Changing the mass ratio of the composition to compound (A): compound (B): a sample for film performance evaluation was prepared in the same manner as in example 4, except that the fluorine-based solvent (C) was used in a ratio of 80:20: 400.

The results of evaluating the wear resistance of the obtained coating are shown in table 1. In example 6, the initial contact angle was 117.1 °, the slip angle was 26.7 °, and the contact angle hysteresis was 16.3 °.

Example 7

Changing the mass ratio of the composition to compound (A): compound (B): a sample for film performance evaluation was prepared in the same manner as in example 4, except that the fluorine-based solvent (C) was used in a ratio of 67:33: 400.

The results of evaluating the wear resistance of the obtained coating are shown in table 1. In example 7, the initial contact angle was 115.6 °, the slip angle was 22.7 °, and the contact angle hysteresis was 9.5 °.

Comparative example 1

A sample for evaluation of film performance was prepared in the same manner as in example 1, except that Fomblin (registered trademark) M03 (number average molecular weight about 4000) represented by the following formula (c) was used instead of the compound (b 1). Fomblin (registered trademark) M03 has an oxyalkylene unit, all hydrogen atoms of which are substituted with fluorine atoms, but does not have a hydroxyl group in its molecule.

[ chemical formula 14]

The results of evaluating the wear resistance of the obtained coating are shown in table 1. In comparative example 1, the initial contact angle was 115.7 °, the slip angle was greater than 50 °, and the water droplet did not slip even when the substrate was tilted to 50 °.

Comparative example 2

A sample for evaluation of film performance was prepared in the same manner as in example 2, except that Fomblin (registered trademark) M03 was used instead of the compound (b 1).

The results of evaluating the wear resistance of the obtained coating are shown in table 1. In comparative example 2, the initial contact angle was 116.5 °, the slip angle was 13.7 °, and the contact angle hysteresis was 4.2 °.

Comparative example 3

A sample for evaluation of film performance was prepared in the same manner as in example 3, except that Fomblin (registered trademark) M03 was used instead of the compound (b 1).

The results of evaluating the wear resistance of the obtained coating are shown in table 1. In comparative example 3, the initial contact angle was 118.3 °, the slip angle was 13.3 °, and the contact angle hysteresis was 6.5 °.

[ Table 1]

The post-treatment conditions are that the water is used for ultrasonic washing for 3 minutes at 150 ℃ for 30 minutes

As is clear from table 1, examples 1 to 7 using the compound (B) having a hydroxyl group have improved abrasion resistance as compared with comparative examples 1 to 3. Further, the coating film obtained using the composition of the present invention can be further improved in abrasion resistance by performing post-treatment after the formation of the coating film, and particularly, as is clear from comparison with examples 1 to 3 in which conditions other than the post-treatment conditions are completely the same, the abrasion resistance is the best in example 3 in which ultrasonic cleaning is performed.

Industrial applicability

The composition of the present invention is industrially useful for forming a film suitable for display devices such as touch panel displays, optical devices, semiconductor devices, building materials, nanoimprint technology, solar cells, automobiles, window glass of buildings, metal products such as kitchen ware, ceramic products such as tableware, automobile parts made of plastics, and the like. Further, the present invention can be preferably used for articles such as kitchen, bathroom, washstand, mirror, members around the bathroom, goggles, glasses, and the like.

Claims

1. A composition characterized by comprising:

a compound (a) in which (a1) a 1-valent group having a perfluoropolyether structure, and at least one of (a2) a hydrolyzable group and a hydroxyl group are bonded to a silicon atom; and

a compound (B) having a hydroxyl group and an oxyalkylene unit, at least a part of hydrogen atoms of the oxyalkylene unit being substituted with fluorine atoms, a number average molecular weight of less than 10000, both terminals of the compound (B) being hydroxyl groups,

wherein the compound (A) is represented by the following formula (1a) or (2a),

[ chemical formula 1]

In the formula (1a), the compound (A),

R²each independently an alkyl group having 1 to 20 carbon atoms,

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

n is an integer of 1 to 3 inclusive,

the repeating units denoted by a1, b1, c1, d1 and e1 and enclosed by parentheses may be arranged in the order in which at least a part of the repeating units form a perfluoropolyether structure, and may be arranged in any order,

[ chemical formula 2]

In the formula (2a), the compound (A),

R⁴each independently an alkyl group having 1 to 20 carbon atoms,

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

z is a hydrogen atom or a halogen atom,

f2 is an integer of 1 to 20 inclusive,

g2 is an integer of 0 to 2 inclusive,

p is an integer of 1 to 3 inclusive,

the repeating units denoted by a2, b2, c2, d2 and e2 and enclosed by parentheses may be arranged in the order in which at least a part of the repeating units form a perfluoropolyether structure, and may be arranged in any order,

the compound (B) is represented by the following formula (1B'),

[ chemical formula 3]

In the above formula (1 b'), X is a hydrogen atom or a fluorine atom, Rf⁵Each independently being a hydrogen atom, a fluorine atom, or-CF₃J is-O-, -C (═ O) -O-, or-O — C (═ O) -O-, a3 is 1 or more and 5 or less, b3 is 20 or more and 200 or less, C3 is 5 or more and 200 or less, and each repeating unit denoted by a3 to C3 and enclosed in parentheses may be arranged in the order in which oxyalkylene units are formed from at least a part thereof, and each may be arranged in an arbitrary order, at least a part of hydrogen atoms in the oxyalkylene units being substituted with fluorine atoms,

in the compound (B), the proportion of the number of fluorine atoms to the total of the number of hydrogen atoms other than the hydrogen atoms in the hydroxyl group and the number of fluorine atoms is 40% or more and 80% or less.

2. The composition according to claim 1, wherein the compound (A) is a compound of the formula (1a) wherein the total value of a1, b1, c1, d1 and e1 is 13 or more, or a compound of the formula (2a) wherein the total value of a2, b2, c2, d2 and e2 is 13 or more.

3. The composition according to claim 1 or 2, wherein the number of hydroxyl groups contained in the compound (B) is 2.

4. The composition according to any one of claims 1 to 3, wherein the mass ratio of the compound (A) to the compound (B) is 1 or more.