WO2018034202A1

WO2018034202A1 - Composition

Info

Publication number: WO2018034202A1
Application number: PCT/JP2017/028728
Authority: WO
Inventors: 彩香櫻井; 知典宮本; みちる上原
Original assignee: 住友化学株式会社
Priority date: 2016-08-19
Filing date: 2017-08-08
Publication date: 2018-02-22
Also published as: TW201816009A; KR102338219B1; KR20190042033A; JP6996898B2; TWI725219B; JP2018031000A; CN109563338A; CN109563338B

Abstract

The purpose of the present invention is to provide a coating composition having good wear resistance. The present invention is a composition characterized by comprising: a compound (A) in which (a1) a monovalent group having a perfluoropolyether structure and (a2) at least either one of a hydrolyzable group and a hydroxy group are bonded to a silicon atom; and a compound (B) having a number-average molecular weight of less than 10,000 and having a hydroxy group and an oxyalkylene unit, at least some of hydrogen atoms in the oxyalkylene unit being substituted with a fluorine atom.

Description

Composition

The present invention relates to a composition.

A film formed from a composition containing a fluorooxyalkylene group-containing compound has water and oil repellency, chemical resistance, releasability and the like because its surface free energy is very small. Utilizing the property, Patent Document 1 discloses (A) a hydrolyzable group-containing silane modified with a fluorooxyalkylene group-containing polymer and / or a partial hydrolysis-condensation product thereof, and an average of the component (A). A fluorine-containing coating agent comprising (B) a fluorooxyalkylene group-containing polymer having an average molecular weight equal to or lower than the molecular weight is disclosed. Patent Document 1 describes that the (B) fluorooxyalkylene group-containing polymer contains a non-functional fluorooxyalkylene group.

In Patent Document 2, (A) a hydrolyzable group-containing silane modified with a fluorooxyalkylene group-containing polymer and / or a partially hydrolyzed condensate thereof, and a weight average molecular weight larger than that of the component (A) (B And a fluorooxyalkylene group-containing polymer, and a fluorine-based surface treatment agent for vapor deposition having a mixing mass ratio of the component (A) to the component (B) of 6: 4 to 9: 1 is disclosed. Similarly to Patent Document 1, (B) the fluorooxyalkylene group-containing polymer of Patent Document 2 is described as being non-functional.

Japanese Patent Laid-Open No. 2015-199915 JP 2013-136833 A

Patent Document 1 describes that a polymer containing a non-functional fluorooxyalkylene group is excellent in wear resistance, and Patent Document 2 is excellent in durability when a fluorine-based surface treatment agent is deposited on a substrate by a vacuum deposition method. It is described that it becomes a film. However, there is still room for improvement in improving wear resistance.

This invention is made | formed in view of the said subject, and it aims at providing the composition which can form the membrane | film | coat which has favorable abrasion resistance.

The present invention relates to a compound (A) in which (a1) a monovalent group having a perfluoropolyether structure and (a2) at least one of a hydrolyzable group and a hydroxy group are bonded to a silicon atom. And a composition containing a compound (B) having a hydroxy group and an oxyalkylene unit, wherein at least a part of hydrogen atoms of the oxyalkylene unit is substituted with a fluorine atom, and having a number average molecular weight of less than 10,000.

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

In formula (1a),
Rf ¹ is a C 1-20 alkyl group in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom,
Each Rf ² is independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom;
Each R ¹ is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
Each R ² is independently an alkyl group having 1 to 20 carbon atoms;
D is each independently —O—, —C (═O) —O—, —O—C (═O) —, —NR—, —NRC (═O) —, or —C (═O ) NR—, wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms,
E is each independently a hydrolyzable group or a hydroxy group,
a1, b1, c1, d1 and e1 are each independently an integer of 0 to 600, and the total value of a1, b1, c1, d1 and e1 is 9 or more,
n is an integer of 1 to 3,
As long as the repeating units a1, b1, c1, d1, and e1 are enclosed in parentheses are arranged in the order of forming a perfluoropolyether structure at least partially, they may be arranged in any order.

In formula (2a),
Rf ³ is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom,
Rf ⁴ each independently represents an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom;
Each R ³ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
Each R ⁴ is independently an alkyl group having 1 to 20 carbon atoms;
M is independently —O—, —C (═O) —O—, —O—C (═O) —, —NR—, —NRC (═O) —, or —C (═O ) NR—, wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms,
G is each independently a hydrolyzable group or a hydroxy group,
Y is each 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 or more and 600 or less, and the total value of a2, b2, c2, d2 and e2 is 9 or more,
f2 is an integer from 1 to 20,
g2 is an integer of 0 or more and 2 or less,
p is an integer of 1 to 3,
As long as the repeating units a2, b2, c2, d2, and e2 are enclosed in parentheses are arranged in the order of forming a perfluoropolyether structure at least partially, they may be arranged in any order.

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

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

In the above formula (1b), each X is independently a hydrogen atom or a fluorine atom, Rf ⁵ is each independently a hydrogen atom, a fluorine atom, or —CF ₃ , and J is —O—, —C ( ═O) —O— or —O—C (═O) —O—, a3 is from 1 to 5, b3 is from 20 to 200, c3 is from 5 to 200, and a3 to c3 are attached. Each of the repeating units enclosed in parentheses may be arranged in any order as long as at least a part of the repeating units are arranged in the order of forming the oxyalkylene unit, and at least a part of the hydrogen atoms of the oxyalkylene unit is fluorine. It is replaced by an atom.

The number of hydroxy groups contained in the compound (B) is preferably 1 to 2. 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.

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

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

The composition of the present invention contains a compound (A) having a perfluoropolyether structure and a compound (B) having a hydroxy group and an oxyalkylene unit. The film can exhibit good water repellency 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. Moreover, the abrasion resistance of a film | membrane can be ensured because a compound (B) has a hydroxyl group.

The compound (A) may be any compound containing fluorine and capable of forming a film matrix by bonding with the compound (A) or other monomers through a polymerization reaction (particularly polycondensation reaction). The compound (A) is preferably a compound containing a fluorine-containing group and at least one of a hydrolyzable group and a hydroxy group, and in the present invention, as the compound (A), (a1) a perfluoropolyether structure is preferable. And (a2) a compound in which at least one of a hydrolyzable group and a hydroxy group is bonded to a silicon atom.

The perfluoropolyether structure is a structure in which all hydrogen atoms of a polyalkylene ether group or a polyalkylene glycol dialkyl ether residue are replaced with fluorine atoms, a perfluoro polyalkylene ether group, or a perfluoro polyalkylene glycol dialkyl. It can also be called an ether residue. The perfluoropolyether structure can also be said to be a perfluorooxyalkylene group. The perfluoropolyether structure imparts water repellency to the resulting 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 carbon number is not particularly limited, and may be about 200, for example.

In the compound (A), the monovalent group having the perfluoropolyether structure is bonded to a silicon atom. An appropriate linking group may be present on the side where the perfluoropolyether structure is bonded to 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 hydrocarbon groups such as alkylene groups and aromatic hydrocarbon groups, (poly) alkylene glycol groups, groups in which at least some of these hydrogen atoms are substituted with fluorine atoms, and these are suitable. And a group linked to. The carbon number of the linking group is, for example, 1 or more and 20 or less, preferably 2 or more and 10 or less.

Note 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 monovalent groups having the perfluoropolyether structure bonded to the silicon atom may be one or more, may be 2 or 3, but is preferably 1 or 2. It is particularly preferred.

In the compound (A), at least one of a hydrolyzable group and a hydroxy group is bonded to a silicon atom, and the hydrolyzable group and the hydroxy group are respectively subjected to hydrolysis and / or dehydration condensation reaction. It has the effect | action which couple | bonds compound (A) with each other or the active hydrogen derived from the compound (A), the hydroxyl group of the base-material surface, etc. 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. Preferred hydrolyzable groups are an alkoxy group and a halogen atom, and a methoxy group, an ethoxy group, and a chlorine atom are particularly preferable.

The number of hydrolyzable groups bonded to the silicon atom may be one or more, and may be 2 or 3, but 2 or 3 is preferable, and 3 is particularly preferable. When two or more hydrolyzable groups are bonded to a silicon atom, different hydrolyzable groups may be bonded to the silicon atom, but the same hydrolyzable group is bonded to the silicon atom. preferable. The total number of fluorine-containing groups and hydrolyzable groups bonded to silicon atoms is usually 4, but may be 2 or 3 (particularly 3). In the case of 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 can be bonded to the remaining bonds.

The monovalent group having a perfluoropolyether structure of the compound (A) may be linear or 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.

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

In formula (1a),
Rf ¹ is a C 1-20 alkyl group in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom,
Each Rf ² is independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom;
Each R ¹ is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
Each R ² is independently an alkyl group having 1 to 20 carbon atoms;
D is each independently —O—, —C (═O) —O—, —O—C (═O) —, —NR—, —NRC (═O) —, or —C (═O ) NR—, wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms,
E is each independently a hydrolyzable group or a hydroxy group,
a1, b1, c1, d1 and e1 are each independently an integer of 0 to 600, and 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,
As long as the repeating units a1, b1, c1, d1, and e1 are enclosed in parentheses are arranged in the order of forming a perfluoropolyether structure at least partially, they may be arranged in any order. Moreover, there may be a plurality of each repeating unit in the molecule. In this specification, the case where there are a plurality of repeating units in a molecule means that when there are discontinuous repeating units, for example, there are two repeating units in the molecule and each is sandwiched between two different repeating units. This includes cases where

Rf ¹ is preferably an alkyl group having 1 to 10 carbon atoms substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, still more preferably 1 to 1 carbon atoms. 5 perfluoroalkyl groups.
Rf ² is preferably each independently a fluorine atom or a fluorine-containing alkyl group having 1 to 2 carbon atoms, more preferably all fluorine atoms.
Each R ¹ is preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, 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) —, 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 each repeating unit with parentheses a1, b1, c1, d1 and e1 is preferably parenthesized with b1 on the most fixed end side (side bonded to the silicon atom). The repeating unit is located on the free end side with respect to the repeating unit enclosed in parentheses with a1 on the most free end side, and more preferably enclosed on parentheses with b1 and d1 on the most fixed end side The repeating unit is located closer to the free end than the repeating unit enclosed in parentheses with a1 and c1 on the most free end side. It is preferable that there are at least two repeating units attached with e1 and enclosed in parentheses.
n is preferably 2 or more and 3 or less, more preferably 3.

In the above formula (1a), particularly Rf ¹ is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ² is all fluorine atoms, R ¹ is all hydrogen atoms, and D is all —O—. , E is a methoxy group or an ethoxy group, a1 is an integer of 1 to 3, c1 = d1 = 0, and b1 and e1 are set so that the compound of formula (1a) can maintain a liquid at normal pressure It is preferable that n = 3. The total value of b1 and e1 can be 8 or more.

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

In the above 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, and R ¹² is 1 carbon atom. A perfluoroalkylene group having 3 to 3, R ¹³ is an alkylene group having 1 to 3 carbon atoms, R ¹⁴ is an alkyl group having 1 to 3 carbon atoms, and z2 and z3 are both 1 to 3 It is an integer, and z1 is a value set so that the compound represented by the formula (1a-1) can maintain a liquid at normal pressure, and can be, for example, 3 or more.

As the compound (A), in addition to the compound of the above formula (1a), a compound of the following formula (2a) can be exemplified, and a compound of the following formula (2a) is preferable.

In the above formula (2a),
Rf ³ is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom,
Rf ⁴ each independently represents an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom;
Each R ³ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
Each R ⁴ is independently an alkyl group having 1 to 20 carbon atoms;
M is independently —O—, —C (═O) —O—, —O—C (═O) —, —NR—, —NRC (═O) —, or —C (═O ) NR—, wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms,
G is each independently a hydrolyzable group or a hydroxy group,
Y is each 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, and the total value of a2, b2, c2, d2 and e2 is 9 or more, preferably 13 or more,
f2 is an integer from 1 to 20,
g2 is an integer of 0 or more and 2 or less,
p is an integer of 1 to 3,
As long as the repeating units a2, b2, c2, d2, and e2 are enclosed in parentheses are arranged in the order of forming a perfluoropolyether structure at least partially, they may be arranged in any order. Moreover, there may be a plurality of each repeating unit in the molecule.

Rf ³ is preferably an alkyl group having 1 to 10 carbon atoms substituted by one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbon atoms, still more preferably 1 to 1 carbon atom. 5 perfluoroalkyl groups.
Rf ⁴ is preferably each independently a fluorine atom or a fluorine-containing alkyl group having 1 to 2 carbon atoms, more preferably all fluorine atoms.
R ³ is preferably each independently a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, more preferably all hydrogen atoms.
R ⁴ is preferably each 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 —O—.
G is independently preferably an alkoxy group or a halogen atom, particularly preferably a methoxy group, an ethoxy group or a chlorine atom.
Y is preferably independently a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, more preferably all hydrogen atoms.
Z is preferably a hydrogen atom.
Preferably, a2, c2 and d2 are each ½ or less of b2, more preferably ¼ 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 not more than the total value of a2, b2, c2 and d2.
b2 is preferably 20 or more and 600 or less, more preferably 20 or more and 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 and 200 or less, and still more 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 or more and 18 or less. More preferably, it is 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, and more preferably 3.
The order of each repeating unit in parentheses with a2, b2, c2, d2 and e2 is preferably parenthesized with b2 on the most fixed end side (side bonded to the silicon atom). The repeating unit is located on the free end side more than the repeating unit enclosed in parentheses with a2 on the most free end side, and more preferably enclosed on parentheses with b2 and d2 on the most fixed end side The repeating unit is located closer to the free end than the repeating unit enclosed in parentheses with a2 and c2 on the most free end side. Moreover, it is preferable that there are at least two repeating units each attached with e2 and enclosed in parentheses.

In the formula (2a), particularly Rf ³ is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf ⁴ is all fluorine atom, M is all —O—, G is methoxy group, ethoxy group, or chlorine atom (particularly methoxy group) Or ethoxy group), Y and Z are all hydrogen atoms, a2 is 0, b2 is 30 to 150 (more preferably 80 to 140), e2 is 30 to 60, c2 and d2 are 0, and g2 is 0 or more and 1 or less. (Especially 0), p is preferably 3, and f2 is preferably 1 to 10.

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

In the above formula (2a-1), R ²⁰ is a perfluoroalkyl group having 2 to 6 carbon atoms, R ²¹ and R ²² are both perfluoroalkylene groups having 2 to 6 carbon atoms, and R ²³ Is a trivalent saturated hydrocarbon group having 2 to 6 carbon atoms, and R ²⁴ is an alkyl group having 1 to 3 carbon atoms. R ²⁰ , R ²¹ , R ²² and R ²³ each independently preferably has 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms. x1 is 5 to 70, x2 is 1 to 5, and x3 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, and x3 is preferably 1 to 8, and more preferably 1 to 6.

Compound (B) has a hydroxy group and an oxyalkylene unit, and at least a part of the hydrogen atoms of the oxyalkylene unit is substituted with a fluorine atom, and the number average molecular weight is less than 10,000. Since the hydroxy group of compound (B) forms an interaction with a base material such as glass or compound (A) and is difficult to peel off, a compound having a similar structure having no hydroxy group is used instead of compound (B). It is considered that the wear resistance of the film is improved as compared with the case of using.

In addition, the number average molecular weight of the compound (B) is important to be less than 10,000 from the viewpoint of sufficiently securing the component derived from the compound (B) in the film obtained by vacuum deposition, and the lower limit is about 1000, for example. It is preferable. The number average molecular weight of the compound (B) is preferably 8000 or less, more preferably 6000 or less.

There may be at least one hydroxy group in the compound (B), preferably 5 or less, more preferably 2 or less. In the compound (B), the ratio of the number of fluorine atoms to the total number of hydrogen atoms other than hydrogen atoms in the hydroxy group and the number of fluorine atoms is preferably 40% or more. Can exhibit excellent water repellency. 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%, for example, about 80%. .

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

In the formula (1b), X is each independently a hydrogen atom or a fluorine atom, Rf ⁵ is each independently a hydrogen atom, a fluorine atom, or —CF ₃ , and J 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 a3 to c3 are attached. Each of the repeating units enclosed in parentheses may be arranged in any order as long as they are arranged in the order of forming at least a part of the oxyalkylene unit, and at least a part of the hydrogen atoms of the oxyalkylene unit are fluorine atoms. Has been replaced. Further, there may be a plurality of repeating units in parentheses attached with a3 to c3 and enclosed in parentheses.

Rf ⁵ is independently preferably a hydrogen atom or a fluorine atom, X is preferably a hydrogen atom, J is preferably —O—, a3 is preferably 1 or more and 3 or less, more preferably 1 or 2 Preferred (most preferably 2). b3 is preferably 30 or more and 100 or less, and c3 is preferably 10 or more and 80 or less. It is also preferable that b3 and c3 are 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 preferably, Rf ⁵ is independently a hydrogen atom or a fluorine atom, X is a hydrogen atom, J is —O—, a3 is 1 or 2, and b3 and c3 are represented by the above formula ( The number average molecular weight of the compound represented by 1b) is preferably a value determined so as to be 2000 to 4500 (more preferably 2500 to 4500).

Compound (B) is, for example, a polyalkylene glycol in which one OH group of a polyalkylene glycol having both OH groups at its ends may be substituted, and at least a part of the hydrogen atoms of the alkylene group And polyalkylene glycol in which is substituted with a fluorine atom. The compound (B) is particularly preferably a polyalkylene glycol in which at least part of the hydrogen atoms of the alkylene group is substituted with fluorine atoms. Examples of such polyalkylene glycols include the following formulas (1b-1) and (1b- 2).

In formula (1b-1), R ³⁰ , R ³¹ , R ³² , R ³⁴ and R ³⁵ are each independently an alkylene group having 2 to 6 carbon atoms, and R ³³ is an alkylene group having 1 to 5 carbon atoms. And at least one of the alkylene groups of R ³⁰ to R ³⁵ has at least one hydrogen atom 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, and y6 is 1 to 4 , Y7 is 2-10.

R ³⁰ , R ³¹ , R ³² , R ³⁴ and R ³⁵ are preferably 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 3 to 9, more preferably 4 to 8, y2 is preferably 1 to 3, more preferably 1 to 2, and y6 is preferably 1 to 3, more preferably 1 to 2. Y7 is preferably from 3 to 9, more preferably from 4 to 8.

In formula (1b-2), R ⁴⁰ and R ⁴³ are each independently an alkylene group having 1 to 3 carbon atoms, and R ⁴¹ is a carbon atom having 1 to 3 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. Wherein R ⁴² is an alkylene group having 1 to 3 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, w1 and w4 are each independently 1 to 3, and w2 And w3 are values determined such that the number average molecular weight of the compound represented by the formula (1b-2) is 3800 to 4200.

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

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

The total mass ratio of the compound (A) and the compound (B) in the composition is preferably 10% by mass or more, more preferably 12% by mass or more, and still more preferably 14% by mass with respect to the total mass of the composition. % Or more. Although an upper limit is not specifically limited, For example, it is 30 mass% or less, 27 mass% or less may be sufficient, and it is also preferable that it is 25 mass% or less.

The composition of the present invention preferably contains a fluorine-based solvent (C) together with the above-described compounds (A) and (B). As the fluorine-based solvent (C), for example, a fluorinated ether-based solvent, a fluorinated amine-based solvent, a fluorinated hydrocarbon-based solvent (particularly a fluorinated aromatic solvent) or the like can be used. It is preferable. The fluorinated ether solvent is preferably a hydrofluoroether such as fluoroalkyl (especially a perfluoroalkyl group having 2 to 6 carbon atoms) -alkyl (particularly a methyl group or ethyl group) ether, such as ethyl nonafluorobutyl ether or ethyl nona. Fluoroisobutyl ether is mentioned. Examples of ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether include Novec (registered trademark) 7200 (manufactured by 3M, molecular weight of about 264, boiling point: 76 ° C.). As the fluorinated amine solvent, an amine in which at least one hydrogen atom of ammonia is substituted with a fluoroalkyl group is preferred, and a third in which all hydrogen atoms of ammonia are substituted with fluoroalkyl groups (particularly perfluoroalkyl groups). Secondary amines are preferred, and specific examples include tris (heptafluoropropyl) amine, and Florinate (registered trademark) FC-3283 (molecular weight of about 471, boiling point 128 ° C.) corresponds to this. Examples of the fluorinated hydrocarbon solvent include 1,3-bis (trifluoromethylbenzene) (boiling point: about 116 ° C.).

As the fluorine-based solvent (C), in addition to the above, hydrochlorofluorocarbons such as Asahiklin (registered trademark) AK225 (manufactured by Asahi Glass Co., Ltd.), hydrofluorocarbons such as Asahiclin (registered trademark) AC2000 (manufactured by Asahi Glass Co., Ltd.), etc. Can be used.

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

Content of the fluorine-type solvent (C) in the composition of this invention is 20 mass% or more with respect to the total mass of a composition, More preferably, it is 50 mass% or more, More preferably, it is 70 mass%. It is above, Preferably it is 90 mass% or less, More preferably, it is 88 mass% or less, More preferably, it is 86 mass% or less.

The composition of the present invention may further contain a silanol condensation catalyst. Examples of the silanol condensation catalyst include inorganic acids such as hydrochloric acid and nitric acid, organic acids such as acetic acid, metal complexes such as titanium complexes (for example, ORGATICS TC-750 manufactured by Matsumoto Fine Chemical) and tin complexes, and metal alkoxides. The amount of the silanol condensation catalyst is, for example, 0.00001 to 0.1% by mass, preferably 0.00002 to 0.01% by mass, and more preferably 0.0005 to 0. 0% by mass with respect to the total mass of the composition. 001 mass%.

The composition of the present invention is an antioxidant, a rust inhibitor, an ultraviolet absorber, a light stabilizer, a fungicide, an antibacterial agent, an anti-bioadhesive agent, a deodorant, and a pigment as long as the effects of the present invention are not impaired. In addition, various additives such as a flame retardant and an antistatic agent may be contained.

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 0.8%, based on the polymer component of the composition of the present invention. 05 to 50% by mass, more preferably 0.1 to 30% by mass, still more preferably 0.5 to 5% by mass.

The composition of the present invention is suitably used for forming a film on a substrate by vacuum deposition. Known conditions can be adopted as the conditions for vacuum deposition. The degree of vacuum is, for example, about 10 ⁻² Pa or less. As a heating method during the vapor deposition process, either a resistance heating method or an electron beam heating method may be used, and the heating temperature is, for example, 100 to 400 ° C. The film formation time is, for example, about 1 to 60 seconds.

After vacuum deposition, it is allowed to stand at room temperature in the air or heated (for example, at 50 to 150 ° C. for 5 to 30 minutes) to take in moisture in the air, and the silicon atom of compound (A) The hydrolyzable group bonded to is hydrolyzed to form a siloxane bond, and a cured film can be obtained. The film thickness of the resulting film can be 2 to 10 nm, for example.

The material of the base material on which the composition of the present invention is vapor-deposited is not particularly limited, and may be either an organic material or an inorganic material. The shape of the base material may be either a flat surface or a curved surface. A three-dimensional structure in which 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; phenol resin, urea resin, melamine resin, epoxy Examples thereof include thermosetting resins such as 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 glass. Among these, it is particularly preferable to form a film by vapor-depositing the composition of the present invention on a substrate of an inorganic material such as glass, metal, or ceramic.

After the film is formed on the substrate, it may be deposited or may be subjected to a predetermined post-treatment, and the post-treatment can further improve the wear resistance of the film. Post-treatment includes heating and holding, standing in a humidified atmosphere, ultrasonic cleaning, wiping the surface with a solvent, and the like. The above may be combined. Of these, heating and holding are particularly preferable, and ultrasonic cleaning is preferable. The heating and holding may be held, for example, at 100 to 200 ° C. for 10 to 60 minutes. Etc. may be used for about 1 to 5 minutes. From the viewpoint of further improving the wear 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 group are subjected to post-treatment as compared with the case where the composition includes a conventional compound having no hydroxy group. It is expected that the interaction with the material (eg glass) or compound (A) will change to a more durable state.

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

The primer layer is preferably a layer formed using a primer layer forming composition containing a component (E) composed of a compound represented by the following formula (p1) and / or a partial hydrolysis condensate thereof.

Si (X ² ) ₄ (p1)
(However, in the formula (p1), a plurality of X ² each independently represents a halogen atom, an alkoxy group or an isocyanate group.)

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

Specifically, Si (NCO) ₄ , Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) _{4 and the} like are preferably used as such a compound represented by the formula (p1). (E) A component may be used individually by 1 type and may use 2 or more types together.

The component (E) contained in the primer layer forming composition may be a partial hydrolysis 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-condensation method using an acid or a base catalyst. However, the degree of condensation (degree of multimerization) of the partially hydrolyzed condensate needs to be such that the product is dissolved in the solvent. The component (E) may be a compound represented by the above formula (p1) or a partial hydrolysis condensate of a compound represented by the above formula (p1). A mixture of the compound represented by the partial hydrolysis-condensation product thereof, for example, a partial hydrolysis-condensation product of the compound containing the unreacted compound represented by the formula (p1) may be used. In addition, there exists a commercial item as a compound represented by the said formula (p1), and its partial hydrolysis-condensation product, It is possible to use such a commercial item for this invention.

Moreover, the composition for primer layer formation consists of the said (E) component, the compound (it may be called a compound (p2)) represented by the following formula (p2), and / or its partial hydrolysis-condensation product (F). Or a partial hydrolysis-condensation product of the component (E) and the component (F) (however, the component (E) and / or the compound (p2) may be included). There may be.

(X ³ ) ₃ Si— (CH ₂ ) _p —Si (X ³ ) ₃ ... (P2)
(However, in the formula (p2), a plurality of X ³ each 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 a hydrolyzable silyl group or silanol group at both ends 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 X ² described above. From the viewpoint of the balance between the stability of the compound represented by the above formula (p2) and the ease of hydrolysis, X ³ is preferably an alkoxy group or an isocyanate group, and particularly preferably an alkoxy group. As the alkoxy group, an alkoxy group having 1 to 4 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable. These are appropriately selected and used according to the purpose of manufacture, application and the like. A plurality of X ³ present in the formula (p2) may be the same group or different groups, and are preferably the same group from the viewpoint of easy availability.

As the compound represented by the formula (p2), specifically, (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. are mentioned. (F) A component may be used individually by 1 type and may use 2 or more types together.

The component contained in the primer layer forming composition may be a partially hydrolyzed condensate of the compound represented by the formula (p2). The partially hydrolyzed condensate of the compound represented by the formula (p2) can be obtained by the same method as described in the production of the partially hydrolyzed condensate of the compound represented by the formula (p1). The degree of condensation (degree of multimerization) of the partially hydrolyzed condensate must be such that the product is dissolved 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), which is represented by the formula (p2). It may be a mixture of a compound and a partial hydrolysis condensate thereof, for example, a partial hydrolysis condensate of the compound including an unreacted compound represented by the formula (p2). In addition, there exists a commercial item as a compound shown by the said Formula (p2), or its partial hydrolysis-condensation product, It is possible to use such a commercial item for this invention.

In the primer layer, various polysilazanes capable of obtaining the same silicon-based oxide film as in the above formula (p1) may be used.

The primer layer-forming composition usually contains an organic solvent in addition to the solid content as a layer constituent component in consideration of economy, workability, ease of controlling the thickness of the resulting primer layer, and the like. The organic solvent is not particularly limited as long as it dissolves the solid content contained in the primer layer forming composition. Examples of the organic solvent include the same compounds as the solvent used in the composition of the present invention. The organic solvent is not limited to one kind, and two or more kinds of solvents having different polarities and evaporation rates may be mixed and used. When the composition for primer layer formation contains the partial hydrolysis-condensation product and the partial hydrolysis-condensation product, you may include the solvent used in order to manufacture these.

Furthermore, in the composition for forming a primer layer, even if it does not contain a partial hydrolysis condensate or partial hydrolysis cocondensate, in order to promote the hydrolysis cocondensation reaction, It is also preferable to blend a catalyst such as an acid catalyst that is generally used. Even when a partially hydrolyzed condensate or a partially hydrolyzed cocondensate is included, when the catalyst used for the production thereof does not remain in the composition, it is preferable to add a catalyst. The composition for forming a primer layer may contain water for the above-described components to undergo a hydrolysis condensation reaction or a hydrolysis cocondensation reaction.

As a method for forming the primer layer using the primer layer forming composition, a known method for an organosilane compound-based surface treatment agent can be used. For example, the primer layer forming composition is applied to the surface of the substrate by a method such as brush coating, flow coating, spin coating, dip coating, squeegee coating, spray coating, or hand coating, and is necessary in the air or in a nitrogen atmosphere. The primer layer can be formed by curing after drying. Curing conditions are appropriately controlled depending on the type and concentration of the composition used. In addition, you may perform hardening of the composition for primer layer formation simultaneously with hardening of the composition for water-repellent film formation.

The thickness of the primer layer is not particularly limited as long as it is capable of imparting moisture resistance to the transparent film formed thereon, as well as being capable of imparting adhesion to the substrate, and capable of barriering alkali from the substrate. Not.

The 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 by the initial contact angle analyzed by the θ / 2 method, for example, by the droplet method, and the dynamic water repellency can be evaluated by the contact angle hysteresis or the slide angle measured by the slide method. . For example, the initial contact angle measured with a water droplet volume of 3 μL can be, for example, 110 ° or more, preferably 113 ° or more, more preferably 115 ° or more, and the upper limit is not particularly limited. Degree. The contact angle hysteresis measured with a water droplet amount of 6.0 μL can be, for example, 12 ° or less, preferably 10 ° or less, more preferably 9 ° or less, and the lower limit is not particularly limited. It is about 3 °. Further, the sliding angle measured with a water droplet amount of 6 μL is, for example, 30 ° or less, preferably 25 ° or less, more preferably 23 ° or less, and the lower limit is not particularly limited, but is, for example, about 5 °.

Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by the following examples, and can of course be implemented with appropriate modifications within a range that can be adapted to the above-described gist. Included in the range.

The films obtained in the examples and comparative examples of the present invention were measured by the following methods.

(1) Measurement of film thickness For measurement, a Rigaku X-ray reflectivity measuring device (SmartLab) was used. An X-ray generator of 45 kW is used as the X-ray source, a CuKα ray wavelength λ = 0.15418 nm or a CuKα1 ray wavelength λ = 0.15406 nm by a Cu target, and a monochromator is not used. As setting conditions, the sampling width was set to 0.01 ° and the scanning range was set to 0.0 to 2.5 °. And it measured on the said setting conditions, and obtained the reflectance measured value. The obtained measured values were analyzed using company analysis software (GlobalFit).

(2) Measurement of initial contact angle Using a contact angle measuring device (DM700 manufactured by Kyowa Interface Science Co., Ltd.), the liquid surface is 3 μL by the droplet method (analysis method: θ / 2 method), and the contact angle of water on the film surface Was measured.

(3) Measurement of contact angle hysteresis and sliding angle Using DM700 made by Kyowa Interface Science Co., Ltd., sliding method (analysis method: contact method, water droplet amount: 6.0 μL, tilting method: continuous tilt, sliding detection: movement after sliding) Determination: advance angle, sliding determination distance: 0.125 mm), the dynamic water repellency (contact angle hysteresis, sliding angle) of the coating surface was measured.

(4) Evaluation of wear resistance Using a scratch device equipped with an HB pencil with an eraser manufactured by Mitsubishi Pencil Co., Ltd., with the eraser in contact with the sample, applying a load of 500 g and moving the sample at 40 r / min, the wear test was performed. went. The contact angle was measured every 1000 wears, and the number of times until the initial contact angle became −15 degrees or less was measured.

Example 1
A compound (number average molecular weight of 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.

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

As the compound (A), the compound (a) represented by the above formula (a) and the compound (B1) (number average molecular weight of about 2240) represented by the following formula (b1) were used as the compound (B).

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

Novec7200 (registered trademark) was used as the fluorinated solvent (C), and a composition having a mass ratio of Compound (A): Compound (B): Fluorinated solvent (C) = 89: 11: 400 was prepared. After 1 mL of this was dropped onto a Ta boat for vapor deposition, the solvent was evaporated to prepare a sample used for vapor deposition. Using the VPC-410A manufactured by ULVAC-KIKO Co., Ltd., the above-mentioned sample was subjected to a non-alkali glass EAGLE-XG by a vacuum deposition method (resistance heating method, pressure 8 × 10 ⁻³ Pa, applied current 20 A, deposition time 15 seconds) A film was formed on (registered trademark, Corning) and used as a film performance evaluation sample.

Table 1 shows the evaluation results of the wear resistance of the obtained film. In Example 1, the initial contact angle was 115.8 °, the sliding angle was 27.7 °, and the contact angle hysteresis was 10.6 °.

Example 2
After the film formation, the same operation as in Example 1 was performed except that a heat treatment was further performed at 150 ° C. for 30 minutes to obtain a film performance evaluation sample.

Table 1 shows the evaluation results of the wear resistance of the obtained film. In Example 2, the initial contact angle was 115.8 °, the sliding angle was 17.3 °, and the contact angle hysteresis was 7.1 °.

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

Table 1 shows the evaluation results of the wear resistance of the obtained film. 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
In place of the compound (b1), the same operation as in Example 2 was performed except that Fluorolink® D4000 (number average molecular weight of about 4000) represented by the following formula (b2) was used. did. Fluorolink (registered trademark) D4000 had a hydroxy group at the terminal and an oxyalkylene unit, and a part of the hydrogen atoms of the oxyalkylene unit was substituted with a fluorine atom. In Fluorolink D4000, the ratio of the number of fluorine atoms to the total number of hydrogen atoms other than hydrogen atoms in the hydroxy group and the number of fluorine atoms is 40% or more.

Table 1 shows the evaluation results of the wear resistance of the obtained film. In Example 4, the initial contact angle was 111.1 °, the sliding angle was 7.3 °, and the contact angle hysteresis was 4.8 °.

Example 5
Membrane performance evaluation was carried out in the same manner as in Example 2 except that the composition mass ratio was changed to the ratio of compound (A): compound (B): fluorinated solvent (C) = 80: 20: 400. A sample was used.

Table 1 shows the evaluation results of the wear resistance of the obtained film. 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
Membrane performance evaluation was carried out in the same manner as in Example 4 except that the composition mass ratio was changed to the ratio of compound (A): compound (B): fluorinated solvent (C) = 80: 20: 400. A sample was used.

Table 1 shows the evaluation results of the wear resistance of the obtained film. In Example 6, the initial contact angle was 117.1 °, the sliding angle was 26.7 °, and the contact angle hysteresis was 16.3 °.

Example 7
Membrane performance evaluation was carried out in the same manner as in Example 4 except that the composition mass ratio was changed to the ratio of compound (A): compound (B): fluorinated solvent (C) = 67: 33: 400. A sample was used.

Table 1 shows the evaluation results of the wear resistance of the obtained film. In Example 7, the initial contact angle was 115.6 °, the sliding angle was 22.7 °, and the contact angle hysteresis was 9.5 °.

Comparative Example 1
For the evaluation of the membrane performance, the same operation as in Example 1 was performed except that Fomblin (registered trademark) M03 (number average molecular weight of about 4000) represented by the following formula (c) was used instead of the compound (b1). A sample was used. Fomblin (registered trademark) M03 had an oxyalkylene unit, and all of the hydrogen atoms of the oxyalkylene unit were substituted with fluorine atoms, but did not have a hydroxy group in the molecule.

Table 1 shows the evaluation results of the wear resistance of the obtained film. In Comparative Example 1, the initial contact angle was 115.7 °, the sliding angle was greater than 50 °, and no water droplets slipped even when the substrate was tilted to 50 °.

Comparative Example 2
A sample for evaluation of membrane performance was prepared in the same manner as in Example 2 except that Fomblin (registered trademark) M03 was used instead of the compound (b1).

Table 1 shows the evaluation results of the wear resistance of the obtained film. In Comparative Example 2, the initial contact angle was 116.5 °, the sliding angle was 13.7 °, and the contact angle hysteresis was 4.2 °.

Comparative Example 3
A sample for evaluation of membrane performance was prepared in the same manner as in Example 3 except that Fomblin (registered trademark) M03 was used instead of the compound (b1).

Table 1 shows the evaluation results of the wear resistance of the obtained film. In Comparative Example 3, the initial contact angle was 118.3 °, the sliding angle was 13.3 °, and the contact angle hysteresis was 6.5 °.

From Table 1, it can be seen that Examples 1 to 7 using the compound (B) having a hydroxy group have improved wear resistance as compared with Comparative Examples 1 to 3. In addition, in the film obtained using the composition of the present invention, the wear resistance can be further improved by performing a post-treatment after the film formation, and in particular, the conditions other than the post-treatment conditions were all the same. In comparison with Examples 1 to 3, Example 3 which was subjected to ultrasonic cleaning showed the best wear resistance.

The composition of the present invention includes a display device such as a touch panel display, an optical element, a semiconductor element, a building material, a nanoimprint technology, a solar cell, a metal product such as a window glass of an automobile or a building, a cooking appliance, a ceramic product such as tableware, a plastic Films can be suitably formed on manufactured automobile parts and the like, which is industrially useful. It is also preferably used for kitchens, bathrooms, washstands, mirrors, articles of each member around the toilet, goggles, glasses and the like.

Claims

(A1) a compound (A) in which a monovalent group having a perfluoropolyether structure and (a2) at least one of a hydrolyzable group and a hydroxy group are bonded to a silicon atom;
A composition comprising a compound (B) having a hydroxy group and an oxyalkylene unit, wherein at least a part of hydrogen atoms of the oxyalkylene unit is substituted with a fluorine atom, and having a number average molecular weight of less than 10,000. object.
The composition according to claim 1, wherein the compound (A) is represented by the following formula (1a) or (2a).

In formula (1a),
Rf 1 is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom,
Each Rf 2 is independently an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom;
Each R 1 is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
Each R 2 is independently an alkyl group having 1 to 20 carbon atoms;
D is each independently —O—, —C (═O) —O—, —O—C (═O) —, —NR—, —NRC (═O) —, or —C (═O ) NR—, wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms,
Each E is independently a hydrolyzable group or a hydroxy group;
a1, b1, c1, d1 and e1 are each independently an integer of 0 to 600, and the total value of a1, b1, c1, d1 and e1 is 9 or more,
n is an integer of 1 to 3,
As long as the repeating units a1, b1, c1, d1, and e1 are enclosed in parentheses are arranged in the order of forming a perfluoropolyether structure at least partially, they may be arranged in any order.

In formula (2a),
Rf 3 is an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom,
Rf 4 each independently represents an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, or a fluorine atom;
Each R 3 is independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
Each R 4 is independently an alkyl group having 1 to 20 carbon atoms;
M is independently —O—, —C (═O) —O—, —O—C (═O) —, —NR—, —NRC (═O) —, or —C (═O ) NR—, wherein R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms,
Each G is independently a hydrolyzable group or a hydroxy group;
Y is each 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 or more and 600 or less, and the total value of a2, b2, c2, d2 and e2 is 9 or more,
f2 is an integer from 1 to 20,
g2 is an integer of 0 or more and 2 or less,
p is an integer of 1 to 3,
As long as the repeating units a2, b2, c2, d2, and e2 are enclosed in parentheses are arranged in the order of forming a perfluoropolyether structure at least partially, they may be arranged in any order.
The compound (A) is a compound in which the total value of a1, b1, c1, d1 and e1 in the formula (1a) is 13 or more, or a2, b2, c2, d2 and e2 in the formula (2a) The composition according to claim 2, which is a compound having a total value of 13 or more.
The composition according to any one of claims 1 to 3, wherein the compound (B) is represented by the following formula (1b).

In the above formula (1b), X is independently a hydrogen atom or a fluorine atom, Rf 5 is independently a hydrogen atom, a fluorine atom, or —CF 3 , and J is —O—, —C ( ═O) —O— or —O—C (═O) —O—, a3 is from 1 to 5, b3 is from 20 to 200, c3 is from 5 to 200, and a3 to c3 are attached. Each of the repeating units enclosed in parentheses may be arranged in any order as long as at least a part of the repeating units are arranged in the order of forming the oxyalkylene unit, and at least a part of the hydrogen atoms of the oxyalkylene unit is fluorine. It is replaced by an atom.
The composition according to any one of claims 1 to 4, wherein the number of hydroxy groups contained in the compound (B) is 1 to 2.
The composition according to any one of claims 1 to 5, wherein the compound (B) has a 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 of 40% or more. .
The composition 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.