TWI725219B - Composition - Google Patents

Abstract

The object of the present invention is to provide a coating composition having good abrasion resistance.

The composition of the present invention contains: 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 compound (B) having a hydroxy group and an oxyalkylene unit, at least a part of hydrogen atoms of the oxyalkylene unit being substituted with fluorine atoms, the compound (B) having a number average molecular weight of less than 10,000.

Description

Composition

The present invention relates to a composition.

The film formed from the composition containing the fluorooxyalkylene compound has very low surface free energy, so it has water and oil repellency, chemical resistance, and release properties. Utilizing this property, Patent Document 1 discloses that (A) a hydrolyzable group-containing silane and/or a partial hydrolyzed condensate thereof modified by a polymer containing fluorooxyalkylene, and having the (A) (B) A fluorine-containing coating agent of a polymer containing a fluorooxyalkylene group that is below the average molecular weight of the component. The (B) fluorooxyalkylene group-containing polymer of Patent Document 1 mainly describes that it contains a non-functional fluorooxyalkylene group.

In addition, in Patent Document 2, it is disclosed that (A) a hydrolyzable group-containing silane and/or its partial hydrolysis condensate modified by a fluorooxyalkylene-containing polymer is compared with the component (A) (B) A fluorooxyalkylene-containing polymer with a large weight average molecular weight, and a fluorine-based surface treatment agent for vapor deposition with a mixing mass ratio of (A) component and (B) component of 6:4 to 9:1. The (B) fluorooxyalkylene group-containing polymer of Patent Document 2 is also described in Patent Document 1 as having no functional group.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2015-199915

[Patent Document 2] JP 2013-136833 A

Patent Document 1 mainly describes polymers containing non-functional oxyfluoroalkylene groups, which have excellent wear resistance. In Patent Document 2, it is also described that a fluorine-based surface treatment agent is vapor-deposited on a substrate by a vacuum vapor deposition method. It becomes a film with excellent durability. However, there is still room for improvement in the improvement of wear resistance.

The present invention is an invention in view of the above-mentioned problems, and its object is to provide a composition that can form a film having good abrasion resistance.

The composition of the present invention contains: (a1) a monovalent group having a perfluoropolyether structure and (a2) a compound (A) in which at least one of a hydrolyzable group and a hydroxyl group is bonded to a silicon atom; and a compound (A) having a hydroxyl group and The oxyalkylene unit, and at least a part of the hydrogen atom of the oxyalkylene unit is substituted by fluorine atoms, and the number average molecular weight is less than 10,000 of the compound (B).

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

In formula (1a), Rf ¹ is an alkyl group with 1 to 20 carbon atoms or a fluorine atom after more than one hydrogen atom is replaced by a fluorine atom, and Rf ^{2 is} each independently that one or more hydrogen atoms are replaced by a fluorine atom Is an alkyl group having 1 to 20 carbons or a fluorine atom, R ^{1 is} each independently a hydrogen atom or an alkyl group having 1 to 4 carbons, R ^{2 is} each independently an alkyl group having 1 to 20 carbons, and D is each independently For -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, R is a hydrogen atom, An alkyl group having 1 to 4 carbons or a fluorinated alkyl group having 1 to 4 carbons, E is each independently a hydrolyzable group or a hydroxyl group, and a1, b1, c1, d1, and e1 are each independently an integer from 0 to 600 , The total value of a1, b1, c1, d1, and e1 is 9 or more, n is an integer of 1 to 3, and each repeating unit enclosed in parentheses with a1, b1, c1, d1, and e1, as long as at least Some of them are arranged in the order of forming the perfluoropolyether structure, that is, they can be arranged in any order.

In formula (2a), Rf ³ is an alkyl group with 1 to 20 carbon atoms or a fluorine atom after one or more hydrogen atoms are replaced by fluorine atoms, and Rf ^{4 is} each independently that one or more hydrogen atoms are replaced by fluorine atoms. The substituted alkyl group having 1 to 20 carbons or a fluorine atom, R ^{3 is} each independently a hydrogen atom or an alkyl group having 1 to 4 carbons, R ^{4 is} each independently an alkyl group having 1 to 20 carbons, and M is each independently Independently -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, R is hydrogen Atom, an alkyl group having 1 to 4 carbons or a fluorinated alkyl group having 1 to 4 carbons, G is each independently a hydrolyzable group or a hydroxyl group, and Y is each independently a hydrogen atom or an alkyl group having 1 to 4 carbons, Z is a hydrogen atom or a halogen atom, a2, b2, c2, d2, and e2 are each independently an integer from 0 to 600, the total value of a2, b2, c2, d2, and e2 is 9 or more, and f2 is 1 to 20 G2 is an integer from 0 to 2 and p is an integer from 1 to 3, each repeating unit enclosed in parentheses with a2, b2, c2, d2, and e2, as long as it is formed by at least one part The order of the perfluoropolyether structure can be arranged in any order.

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

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

In the above 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 -OC(=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, each repeating unit enclosed in parentheses with a3 to c3 attached, As long as at least a part is arranged in the order in which the oxyalkylene unit is formed, each can be arranged in any order, and at least a part of the hydrogen atoms of the oxyalkylene unit are replaced by fluorine atoms.

The number of hydroxyl groups contained in the aforementioned compound (B) is preferably 1 to 2. In addition, in the aforementioned compound (B), the ratio of the number of fluorine atoms to the total number of hydrogen atoms other than hydrogen atoms in the hydroxyl 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, the compound (A) having a perfluoropolyether structure as a characteristic is used, and has a hydroxyl group and an oxyalkylene unit, and at least a part of the hydrogen atoms of the oxyalkylene unit is replaced by a fluorine atom. The substituted compound (B) can provide a water-repellent film with excellent abrasion resistance.

The composition of the present invention contains a compound (A) having a perfluoropolyether structure, and a compound (B) having a hydroxyl group and an oxyalkylene unit. 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 replaced by fluorine atoms, the film can exhibit good water repellency. In addition, since the compound (B) has a hydroxyl group, the abrasion resistance of the film can be ensured.

The compound (A) only needs to contain fluorine and the compound (A) can be combined with each other or with other monomers through a polymerization reaction (especially a polycondensation reaction) to become a base material of the film. The compound (A) is preferably a compound containing a fluorine group, and at least one of a hydrolyzable group and a hydroxyl group. Among them, the compound (A) used in the present invention is (a1) having a monovalent perfluoropolyether structure (A2) A compound in which at least one of a hydrolyzable group and a hydroxyl group is bonded to a silicon atom.

The aforementioned perfluoropolyether structure refers to a structure in which all the hydrogen atoms of the polyalkylene ether group or the residue of the polyalkylene glycol dialkyl ether group are replaced by fluorine atoms, and can also be called a perfluoropolyalkylene ether group , Or the residue of perfluoropolyalkylene glycol dialkyl ether. The structure of perfluoropolyether can also be called perfluoroalkylene oxide. The perfluoropolyether structure imparts water repellency to the resulting film. The number of carbons contained in the longest linear part of the perfluoropolyether structure is preferably 5 or more, preferably 10 or more, and more preferably 20 or more. The upper limit of the aforementioned carbon number is not particularly limited, and may be about 200, for example.

In the compound (A), the above-mentioned monovalent group having a perfluoropolyether structure is bonded to a silicon atom. The perfluoropolyether structure is on the side that is bonded to the silicon atom, and there may also be an appropriate linking group. If there is no such linking group, the above-mentioned perfluoropolyether structure can also be directly bonded to the silicon atom. As the linking group, for example, hydrocarbon groups such as alkylene groups, aromatic hydrocarbon groups, (poly)alkylene glycol groups, and groups in which at least a part of these hydrogen atoms are substituted by fluorine atoms, and the like It is the base to connect appropriately. 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.

In addition, a plurality of silicon atoms may be bonded to a linking group, and a plurality of perfluoropolyether structures may be bonded to a linking group. The number of monovalent groups having the above-mentioned perfluoropolyether structure bonded to silicon atoms may be one or more, and may be 2 or 3. However, 1 or 2 is preferred, and 1 is particularly preferred.

In addition, in the compound (A), at least one of the hydrolyzable group and the hydroxyl group is bonded to a silicon atom, and the water-decomposable group and the hydroxyl group have a hydrolysis and/or dehydrogenation condensation reaction, respectively, so that the compound (A) can interact with each other , Or the combination of compound (A) with active hydrogen derived from hydroxyl groups on the surface of the substrate. Examples of such hydrolyzable groups include alkoxy groups (especially alkoxy groups having 1 to 4 carbon atoms), acetoxy groups, halogen atoms (especially chlorine atoms) and the like. Preferable hydrolyzable groups are alkoxy groups and halogen atoms, especially methoxy groups, ethoxy groups, and chlorine atoms.

The number of hydrolyzable groups bonded to silicon atoms is only 1. It can be more than one, and it can be 2 or 3, but 2 or 3 is preferred, and 3 is particularly preferred. When two or more hydrolyzable groups are bonded to the silicon atom, different hydrolyzable groups may be bonded to the silicon atom, but the same hydrolyzable group is preferably bonded to the silicon atom. The total number of fluorine-containing groups and hydrolyzable groups bonded to silicon atoms is usually 4, but it may be 2 or 3 (especially 3). In the case of 3 or less, the remaining bond may be bonded to an alkyl group (especially an alkyl group having 1 to 4 carbon atoms), a hydrogen atom, an isocyanate group, etc., for example.

The compound (A) is a monovalent group having a perfluoropolyether structure, and may be linear or side chain.

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

The compound (A) includes, for example, a compound of the following formula (1a).

In formula (1a), Rf ¹ is an alkyl group with 1 to 20 carbon atoms or a fluorine atom in which ^{one or more hydrogen atoms are replaced by fluorine atoms, and Rf 2 is} each independently that one or more hydrogen atoms are replaced by fluorine atoms. The substituted alkyl group having 1 to 20 carbons or a fluorine atom, R ^{1 is} each independently a hydrogen atom or an alkyl group having 1 to 4 carbons, R ^{2 is} each independently an alkyl group having 1 to 20 carbons, and each D Independently -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, R is hydrogen Atom, C1-C4 alkyl group or C1-C4 fluorine-containing alkyl group, E is each independently a hydrolyzable group or a hydroxyl group, a1, b1, c1, d1 and e1 are each independently 0 or more and 600 or less The total value of a1, b1, c1, d1 and e1 is 9 or more, preferably 13 or more, n is an integer of 1 or more and 3 or less, with a1, b1, c1, d1 and e1 attached and enclosed in parentheses As long as at least a part of the repeating units are arranged in the order of forming the perfluoropolyether structure, they can be arranged in any order. In addition, each repeating unit may be plural in the molecule. In this specification, the case where the repeating unit has a plural number in the molecule refers to the case where the repeating unit does not exist continuously. For example, there are two repeating units in the molecule, including two different ones. Repeat the situation where the unit is pinched.

Rf ^{1 is} preferably an alkyl group having 1 to 10 carbons substituted with one or more fluorine atoms, more preferably a perfluoroalkyl group having 1 to 10 carbons, and still more preferably a C1 to 5 alkyl group. Fluoroalkyl.

Rf ^{2 is} preferably each independently a fluorine atom or a fluorine-containing alkyl group having 1 to 2 carbons, and more preferably all of them are fluorine atoms.

R ^{1 is} preferably each independently a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and more preferably all of them are hydrogen atoms.

R ^{2 is} preferably each independently an alkyl group having 1 to 5 carbons.

D is preferably each independently -C(=O)-O-, -O-, -O-C(=O)-, more preferably all of them are -O-.

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

Regarding the order of each repeating unit enclosed in parentheses with a1, b1, c1, and e1, it is preferable that the most fixed end side (the side to which the silicon atom is bonded) is enclosed with b1 and enclosed in parentheses Compared with the repetitive unit on the free end side with a1 attached and enclosed in parentheses, the repetitive unit is located on the free end side, and it is better that the most fixed end side with b1 and d1 attached in parentheses The bracketed repeating unit is located at the free end side compared to the bracketed repeating unit with a1 and c1 on the free end side. It is preferable that there are at least two repeating units enclosed in parentheses with e1.

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

In the above formula (1a), it is particularly preferred that Rf ¹ is a perfluoroalkyl group having 1 to 5 carbons, all Rf ² are fluorine atoms, ^{all R 1} are hydrogen atoms, all D is -O-, and E is methyl Oxy or ethoxy, a1 is an integer from 1 to 3, c1=d1=0, b1 and e1 are the values set in such a way that the compound of formula (1a) can maintain a liquid under normal pressure, n=3. The total value of b1 and e1 may be 8 or more.

As a compound represented by the said formula (1a), the compound of the following formula (1a-1) is mentioned, for example.

In the above formula (1a-1), R ¹⁰ is a perfluoroalkyl group having a carbon number of 1 to 5, R ¹¹ is a perfluoroalkylene group having a carbon number of 1 to 5, and R ¹² is a carbon number of 1 to 3. Perfluoroalkylene, R ¹³ is an alkylene having 1 to 3 carbons, R ¹⁴ is an alkyl having 1 to 3 carbons, z2 and z3 are both integers of 1 to 3, and z1 is The compound represented by the above formula (1a-1) can be set to a value such that it can maintain a liquid at normal pressure, and it may be 3 or more, for example.

In addition to the compound of the above formula (1a), the compound (A) can be exemplified by the compound of the following formula (2a), and the compound of the following formula (2a) is preferred.

In the above formula (2a), Rf ³ is an alkyl group with 1 to 20 carbon atoms or a fluorine atom in which ^{one or more hydrogen atoms are replaced by fluorine atoms, and Rf 4 is} each independently that one or more hydrogen atoms are replaced by fluorine. A C 1 to 20 alkyl group or a fluorine atom substituted by an atom, R ^{3 is} each independently a hydrogen atom or a C 1 to 4 alkyl group, R ^{4 is} each independently a C 1 to 20 alkyl group, M is independently -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, R Is a hydrogen atom, an alkyl group having 1 to 4 carbons or a fluorinated alkyl group having 1 to 4 carbons, G is each independently a hydrolyzable group or a hydroxyl group, and Y is each independently a hydrogen atom or an alkane having 1 to 4 carbons Group, Z is a hydrogen atom or a halogen atom, a2, b2, c2, d2, and e2 are each independently an integer from 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 of 1 to 20, g2 is an integer of 0 to 2 and p is an integer of 1 to 3, each repeated in parentheses with a2, b2, c2, d2, and e2 As long as at least part of the units are arranged in the order in which the perfluoropolyether structure is formed, each unit can be arranged in any order. In addition, each repeating unit may be plural in the molecule.

Rf ^{3 is} preferably an alkyl group having 1 to 10 carbons substituted by more than one fluorine atom, more preferably a perfluoroalkyl group having 1 to 10 carbons, and even more preferably a C1 to 5 alkyl group. Perfluoroalkyl.

Rf ^{4 is} preferably each independently a fluorine atom or a fluorine-containing alkyl group having 1 to 2 carbon atoms, and more preferably all of them are fluorine atoms.

R ^{3 is} preferably each independently a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, and more preferably all of them are hydrogen atoms.

R ^{4 is} preferably each independently an alkyl group having 1 to 5 carbons.

M is preferably each independently -C(=O)-O-, -O-, -O-C(=O)-, more preferably all of them are -O-.

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

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

Z is preferably a hydrogen atom.

Preferably, a2, c2, and d2 are each less than 1/2 of b2, more preferably less than 1/4, still more preferably c2 or d2 is 0, 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 less than the total value of a2, b2, c2, and d2.

b2 is 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 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 20 or more, preferably 600 or less, 20 or more, more preferably 200 or less, and more 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 3 is more preferable.

Regarding the order of the repeating units enclosed in parentheses with a2, b2, c2, d2, and e2, it is preferable that the most fixed end side (the side bonded to the silicon atom) is enclosed in parentheses with b2 The repetitive unit is located on the free end side compared to the repetitive unit with a2 attached to the free end side and enclosed in brackets. It is better that the most fixed end side is attached with b2 and d2 and bracketed The bracketed repeating unit is located at the free end side compared to the bracketed repeating unit with a2 and c2 attached to the free end side. In addition, each repeating unit enclosed in parentheses with e2 should preferably have at least two.

In formula (2a), it is particularly preferred that Rf ³ is a perfluoroalkyl group having 1 to 5 carbons, Rf ^{4 is} all fluorine atoms, all M is -O-, and G is methoxy, ethoxy or chlorine atom (Especially methoxy or ethoxy), any of Y and Z is a hydrogen atom, a2 is 0, b2 is 30 to 150 (more preferably 80 to 140), e2 is 30 to 60, c2 and d2 is 0, g2 is 0 or more and 1 or less (especially 0), p is 3, and f2 is 1-10.

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 a carbon number of 2 to 6, R ²¹ and R ²² are both perfluoroalkylene groups having a carbon number of 2 to 6, and R ²³ is a perfluoroalkylene group having 2 to 6 carbon atoms. A trivalent saturated hydrocarbon group having 2 to 6 ^{carbons, and R 24} is an alkyl group having 1 to 3 carbons. The carbon numbers of R ²⁰ , R ²¹ , R ²² and R ²³ are each independently preferably from 2 to 4, and more preferably from 2 to 3. x1 is 5 to 70, x2 is 1 to 5, and x3 is 1 to 10. x1 is preferably from 10 to 60, more preferably from 20 to 50, x2 is preferably from 1 to 4, more preferably from 1 to 3, and x3 is preferably from 1 to 8, and more preferably from 1 to 6.

Compound (B) has a hydroxyl group and an oxyalkylene unit, and at least a part of the hydrogen atoms of the oxyalkylene unit is substituted by fluorine atoms, and the number average molecular weight is less than 10,000. The hydroxyl group of the compound (B) interacts with the substrate such as glass or the compound (A), so it is difficult to peel off. Compared with the case where the compound (B) is replaced by a compound with a similar structure without a hydroxyl group, it is believed that the film is resistant to Those with increased abrasion.

In addition, from the viewpoint of sufficiently ensuring that the film obtained by vacuum deposition contains components derived from the compound (B), it is important that the number average molecular weight of the compound (B) is less than 10,000, and the lower limit is, for example, about 1,000 Better. 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) should just have at least one, preferably 5 or less, and more preferably 2 or less. In addition, the ratio of the number of fluorine atoms in the compound (B) to the total number of hydrogen atoms other than the number of hydrogen atoms in the hydroxyl group and the number of fluorine atoms is preferably 40% or more, and good water repellency can be exhibited by setting this. The ratio of the number of fluorine atoms is preferably 50% or more, more preferably 55% or more. The upper limit is not particularly limited, and it may be 100%, for example, it may be about 80%.

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

In 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 -OC(=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, each repeating unit enclosed in parentheses with a3 to c3 attached, as long as at least A part is arranged in the order of forming the oxyalkylene unit, that is, each is arranged in any order, and at least a part of the hydrogen atoms of the oxyalkylene unit are replaced by fluorine atoms. In addition, each repeating unit enclosed in parentheses with a3 to c3 may be plural in the molecule.

Rf ⁵ each independently is 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, and 1 or 2 is more preferred (most preferred Is 2). b3 is preferably not less than 30 and not more than 100, and c3 is preferably not less than 10 and not more than 80. b3 and c3 are preferably set so that the number average molecular weight of the compound represented by the above formula (1b) becomes 2000 to 4500, more preferably 2500 to 4500. Most preferably, Rf ^{5 is} each 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 the number of compounds represented by the above formula (1b) The average molecular weight is a value set so that it becomes 2000 to 4500 (more preferably, 2500 to 4500).

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

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 carbons, R ³³ is an alkylene group having 1 to 5 carbons, and R ^{Among all the alkylene groups from 30} to R ³⁵ , in at least one alkylene group, at least one hydrogen atom is substituted with a fluorine atom. y1 is 2 to 10, y2 is 1 to 4, y3 to y5 are values set so that the number average molecular weight of the compound represented by formula (1b-1) becomes 2000 to 2400, y6 is 1 to 4, y7 It is 2 to 10.

R ³⁰ , R ³¹ , R ³² , R ³⁴ and R ³⁵ are each independently an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 to 3 carbon atoms. Furthermore, R ³³ is preferably an alkylene having 1 to 3 carbons, and more preferably an alkylene having 1 to 2 carbons. 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 3-9, more preferably 4-8.

In the formula (1b-2), R ⁴⁰ and R ⁴³ are each independently an alkylene group having 1 to 3 carbon atoms, and R ⁴¹ is an alkylene group having 1 to 5 carbon atoms in which at least one hydrogen atom is substituted by a fluorine atom , R ⁴² is an alkylene group of 1 to 3 carbon atoms in which at least one hydrogen atom is substituted by a fluorine atom, w1 and w4 are each independently 1 to 3, w2 and w3 are represented by formula (1b-2) The number average molecular weight of the compound is set to a value from 3800 to 4200.

R ⁴⁰ and R ⁴³ are each independently preferably an alkylene having 1 to 2 carbons, R ⁴¹ is preferably an alkylene having 1 to 3 carbons in which at least one of the hydrogen atoms is replaced by a fluorine atom, and R ⁴² is A C1-C2 alkylene group in which at least one hydrogen atom is replaced by a fluorine atom is preferable, and w1 and w4 are each independently preferably 1 to 2, and it is more preferable to satisfy these requirements at the same time.

The mass ratio of the compound (A) with respect to the compound (B) in the composition is preferably 1 or more. With this setting, the balance between water repellency and abrasion resistance of the resulting film can be improved. The mass ratio of the compound (A) relative to the compound (B) in the composition is preferably 2.0 or more, more preferably 3.5 or more, and more preferably 5 or more (especially 7 or more). In addition, in consideration of the balance between the water repellency and abrasion resistance of the obtained film, the upper limit of the mass ratio is preferably 13 or less, and more preferably 11 or less.

Relative to the total mass of the composition, 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 the above. The upper limit is not particularly limited. For example, it may be 30% by mass or less, or 27% by mass or less, and preferably 25% by mass or less.

The composition of the present invention preferably contains the above-mentioned compounds (A) and (B) and a fluorine-based solvent (C). As the fluorine-based solvent (C), for example, fluorinated ether-based solvents, fluorinated amine-based solvents, fluorinated hydrocarbon-based solvents (especially fluorinated aromatic solvents), etc. can be used, and those having a boiling point of 100°C or higher are particularly preferred. The fluorinated ether solvent is preferably hydrofluoroether such as fluoroalkyl (especially perfluoroalkyl having 2 to 6 carbons)-alkyl (especially methyl or ethyl) ether, for example: ethyl Base nonafluorobutyl ether or ethyl nonafluoroisobutyl ether. Examples of ethyl nonafluorobutyl ether or ethyl nonafluoroisobutyl ether include Novec (registered trademark) 7200 (manufactured by 3M Corporation, molecular weight approximately 264, boiling point 76°C). The fluorinated amine-based solvent is preferably an amine in which at least one of the hydrogen atoms of ammonia is replaced by a fluoroalkyl group, and a tertiary grade in which all hydrogen atoms of ammonia are replaced by a fluoroalkyl group (especially a perfluoroalkyl group) Amine is preferred. Specifically, ginseng (heptafluoropropyl) amine, Fluorinert (registered trademark) FC-3283 (molecular weight about 471, boiling point 128°C) is equivalent to this. Examples of the fluorinated hydrocarbon solvent include 1,3-bis(trifluoromethylbenzene) (boiling point: about 116°C).

Fluorine-based solvents (C) can be used in addition to the above: Hydrochlorofluorocarbons such as ASAHIKLIN (registered trademark) AK 225 (manufactured by Asahi Glass Co., Ltd.) and hydrogen such as ASAHIKLIN (registered trademark) AC 2000 (manufactured by Asahi Glass Co., Ltd.) Fluorocarbon and so on.

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 may be, for example, about 300.

In the composition of the present invention, the content of the fluorine-based solvent (C) relative to the total mass of the composition is, for example, 20% by mass or more, more preferably 50% by mass or more, and still more preferably 70% by mass or more, It is preferably 90% by mass or less, more preferably 88% by mass or less, and still more preferably 86% by mass or less.

The composition of the present invention may further contain a silanol condensation catalyst. Silanol condensation catalysts include inorganic acids such as hydrochloric acid and nitric acid, organic acids such as acetic acid, titanium complexes (for example, Orgatix TC-750 manufactured by Matsumoto Seika Co., Ltd.), or metal complexes such as tin complexes. Compounds or metal alkoxides, etc. The amount of the silanol condensation catalyst relative to the total mass of the composition is, for example, 0.00001 to 0.1% by mass, preferably 0.00002 to 0.01% by mass, and more preferably 0.0005 to 0.001% by mass.

The composition of the present invention may also contain antioxidants, rust inhibitors, ultraviolet absorbers, light stabilizers, anti-fungal agents, antibacterial agents, anti-biological adhesion agents, deodorants, Various additives such as pigments, flame retardants, and antistatic agents.

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

The composition of the present invention is suitable for forming a film on a substrate by vacuum evaporation. Known conditions can be adopted for the conditions of vacuum vapor deposition. The degree of vacuum is, for example, about 10 ^-2 Pa or less. In addition, the heating method at the time of the vapor deposition process may use either a resistance heating method or an electron beam heating method, 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 evaporation, leave it in the air at room temperature or under heating (for example, 50 to 150°C for 5 to 30 minutes), and inhale the moisture in the air, then the hydrolyzable groups in compound (A) bound to silicon atoms It will be hydrolyzed to form a siloxane bond, and a hardened film can be obtained. The film thickness of the obtained film may be, for example, 2 to 10 nm.

The material of the substrate on which the composition of the present invention is to be vapor-deposited is not particularly limited. It can be any of organic or inorganic materials. The shape of the substrate can be either flat or curved, or a combination of multiple The three-dimensional structure of the surface. The aforementioned organic materials include: acrylic resin, polycarbonate resin, polyester resin, styrene resin, acrylic-styrene copolymer resin, cellulose resin, polyolefin resin, polyvinyl alcohol and other thermoplastic resins; phenol resin, urea Thermosetting resins such as resins, melamine resins, epoxy resins, unsaturated polyesters, silicone resins, urethane resins, etc. Examples of the aforementioned inorganic materials include metals such as iron, silicon, copper, zinc, and aluminum, alloys containing these metals, ceramics, and glass. Among them, it is particularly preferable to vapor-deposit the composition of the present invention on a substrate of inorganic materials such as glass, metal, and ceramics to form a film.

After the substrate is formed into a film, a predetermined post-treatment can be performed in the manner of vapor deposition, and the wear resistance of the film can be further improved by the post-treatment. Examples of post-treatments include heating and holding, standing in a humidified environment, ultrasonic cleaning, wiping the surface with a solvent, and the like. These post-treatments may be carried out alone or in combination of two or more kinds. Among them, heating retention and ultrasonic cleaning are particularly preferred. Heating retention, for example, only needs to be maintained at 100 to 200°C for 10 to 60 minutes, and ultrasonic cleaning, such as washing with water, fluorine-based solvents, or alcohol, etc. Liquid, about 1 to 5 minutes. From the viewpoint of improving abrasion resistance, ultrasonic cleaning is better. Since the composition of the present invention contains the compound (B) having a hydroxyl group, compared with the case where the composition contains a compound that does not contain a hydroxyl group in the past, it can be expected that the compound (B) will interact with the substrate (such as glass) by post-treatment. ) Or the interaction of the compound (A) changes into a state with higher durability.

The substrate may be subjected to easy bonding treatment in advance. Examples of easy bonding treatments include hydrophilization treatments such as corona treatment, plasma treatment, and ultraviolet treatment. In addition, primer treatment with resin, silane coupling agent, tetraalkoxysilane, etc. can also be used. In addition, it is also possible to form a silicon dioxide layer film by vapor deposition.

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

Si(X ² ) ₄ ‧‧‧(p1) (However, in the formula (p1), the plural X ² each independently represent a halogen atom, an alkoxy group, or an isocyanate group).

In the above formula (p1), ^{each of X 2 is} preferably a chlorine atom, an alkoxy group having 1 to 4 carbons, or an isocyanate group, and it is further preferred that the four X ^2s are the same.

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

The component (E) contained in the composition for forming a primer layer 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 above formula (p1) can be obtained by a general hydrolysis-condensation method using an acid or alkali catalyst. However, the degree of condensation (degree of polymerization) of the partial hydrolysis condensate must be such that the product can be dissolved in a solvent. The component (E) may be a compound represented by the above formula (p1), or a partial hydrolysis condensate of the compound represented by the above formula (p1), or a combination of the compound represented by the above formula (p1) and its partial hydrolysis condensate. The mixture, for example, may also be a partial hydrolysis condensate of the compound containing the unreacted compound represented by the above formula (p1). In addition, the compound represented by the above formula (p1) or its partial hydrolysis condensate has commercial products, and such commercial products may be used in the present invention.

In addition, the composition for forming a primer layer contains the above-mentioned (E) component, and is composed of a compound represented by the following formula (p2) (also referred to as a compound (p2)) and/or a partial hydrolysis condensate thereof The composition of the component (F), or it may be a partial hydrolysis condensate containing the component (E) and the component (F) (However, it may also contain the component (E) and/or the compound (p2) )) of the composition.

(X ³ ) ₃ Si-(CH ₂ ) _p -Si(X ³ ) ₃ ‧‧‧(p2) (However, in the formula (p2), the plural X ³ each independently represent a hydrolyzable group or a hydroxyl group, and p is An integer from 1 to 8.)

The compound represented by the formula (p2) is a compound having a hydrolyzable silyl group or a silanol group at both ends via a divalent organic group.

Examples of the hydrolyzable group represented by ^{X 3} in the formula (p2) include the same groups or atoms as the ^{above-mentioned X 2.} 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 and an isocyanate group, and particularly preferably an alkoxy group. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group. These can be appropriately selected and used in accordance with the manufacturing purpose, use, etc. ^{The multiple X 3} in the formula (p2) may be the same base or different bases. From the viewpoint of easy availability, the same base is preferred.

Specifically, the compound represented by the formula (p2) can be exemplified: (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 CH 2 Si(OCH ₃ ) _3, etc. (F) A component may be used individually by 1 type, and may use 2 or more types together.

The component contained in the composition for forming a primer layer may be a partial hydrolysis condensate of the compound represented by formula (p2). The partial hydrolysis condensate of the compound represented by formula (p2) can be obtained using the same method as described in the production of the partial hydrolysis condensate of the compound represented by formula (p1). The degree of condensation (degree of polymerization) of the partial hydrolysis condensate must be such that the product can be dissolved in the solvent. The component (F) can be a compound represented by formula (p2) or a partial hydrolysis condensate of a compound represented by formula (p2), a mixture of a compound represented by formula (p2) and its partial hydrolysis condensate, for example It may also be a partial hydrolysis condensate of the compound containing unreacted compound represented by formula (p2). In addition, the compound represented by the above formula (p2) or its partial hydrolysis condensate is commercially available, and it is possible to use such a commercially available product in the present invention.

In addition, in the primer layer, various polysilazanes that can obtain an oxide film mainly composed of silicon as in the above formula (p1) can be used.

The composition for forming a primer layer generally contains an organic solvent in consideration of economy, workability, and ease of controlling the thickness of the primer layer obtained, in addition to the solid content of the constituent components of the layer. The organic solvent is not particularly limited as long as it can dissolve the solid content contained in the composition for forming the primer layer. 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 type, and two or more types of solvents having different polarities and evaporation rates may be mixed and used. When the composition for forming a primer layer contains a partially hydrolyzed condensate or a partially hydrolyzed co-condensate, it may contain a solvent used for the production of these.

In addition, even if the composition for forming a primer layer does not contain partial hydrolysis condensates or partial hydrolysis co-condensates, in order to promote the hydrolysis co-condensation reaction, the same acid contact as generally used in the partial hydrolysis condensation reaction is formulated. A catalyst such as a medium is preferred. Even if it contains a partially hydrolyzed condensate or a partially hydrolyzed co-condensate, when the catalyst used in the manufacture of these does not remain in the composition, it is better to mix the catalyst. The composition for forming a primer layer may contain water for the hydrolytic condensation reaction or the hydrolytic co-condensation reaction of the above-mentioned contained components.

As a method of forming a primer layer using the composition for forming a primer layer, a conventional method in organosilane compound-based surface treatment agents can be used. For example, brush coating, flow coating, spin coating, dip coating, knife coating, spray coating, hand coating, etc., the primer layer forming composition is coated on the surface of the substrate, in the atmosphere or in a nitrogen environment, as needed After drying, it is hardened to form a primer layer. The curing conditions are appropriately controlled depending on the type and concentration of the composition used. In addition, the curing of the composition for forming a primer layer may be performed simultaneously with the curing of the composition for forming a water-repellent film.

The thickness of the primer layer can not only impart moisture resistance to the transparent film formed thereon, but also impart adhesion to the substrate, as long as it can block alkali from the substrate. Special restrictions.

The film obtained from the composition of the present invention has excellent static water-repellent properties and dynamic water-repellent properties. The static water repellency characteristics can be evaluated, for example, by the initial contact angle analyzed by the θ/2 method in the drop method, and the dynamic water repellency characteristics are the contact angle hysteresis (Hysteresis) or slip angle measured by the sliding method. It can be evaluated. For example, the initial contact angle measured at a water drop volume of 3 μL may be 110° or more, preferably 113° or more, and more preferably 115° or more. The upper limit is not particularly limited, and may be about 125°, for example. In addition, the contact angle hysteresis measured at a water drop volume of 6.0 μL may be, for example, 12° or less, preferably 10° or less, and more preferably 9° or less. The lower limit is not particularly limited, and may be, for example, about 3°. Furthermore, the slip angle measured at a water drop volume 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, and may be about 5°, for example.

[Example]

Hereinafter, the present invention will be explained more specifically with reference to Examples. The present invention is not limited to the following embodiments, but can of course be appropriately modified and implemented within the scope suitable for the aforementioned and later gist, and any of these are included in the technical scope of the present invention.

The films obtained in the Examples and Comparative Examples of the present invention were measured by the following method.

(1) Measurement of film thickness

An X-ray reflectance measuring device (Smart Lab) manufactured by Rigaku Corporation was used for the measurement system. The 45kW X-ray generator of the X-ray source uses the Cu Kα line wavelength λ=0.15418nm or the Cu Kα1 line wavelength λ=0.15406nm, and does not use the monochromator. The setting conditions are that the sample width is 0.01°, and the scanning range is set to 0.0 to 2.5°. Then, the measured value of reflectance can be obtained by measuring under the above-mentioned setting conditions. The obtained measurement value was analyzed using the analysis software (Global Fit) of the same company.

(2) Measurement of initial contact angle

Using a contact angle measuring device (DM700 manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle on the surface of the film was measured by the drop method (analysis method: θ/2 method) liquid volume: 3 μL.

(3) Measurement of contact angle hysteresis and slip angle

Using the DM 700 manufactured by Concord Interface Science Co., Ltd., by the sliding method (analysis method: contact method, water drop volume: 6.0μL, tilt method: continuous tilt, sliding detection: after sliding, movement judgment: forward angle, sliding judgment distance: 0.125 mm), to measure the dynamic water repellency characteristics of the film surface (contact angle hysteresis, slip angle).

(4) Evaluation of wear resistance

Use a gripping device with an HB pencil with an eraser manufactured by Mitsubishi Pencil Company. When the eraser is in contact with the sample, add a load of 500g, and move the sample at a speed of 40r/min for abrasion test. Measure the contact angle per 1,000 times of abrasion, and measure the number of times from the initial contact angle to -15 degrees or less.

Example 1

According to the method described in Synthesis Examples 1 and 2 of JP 2014-15609 A, the compound represented by the following formula (a) (number average molecular weight approximately 8000) was synthesized.

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

The compound (A) uses the compound (a) represented by the above formula (a), and the compound (B) uses the compound (b1) represented by the following formula (b1) (number average molecular weight approximately 2240).

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

Using Novec 7200 (registered trademark) as a fluorine-based solvent (C), a composition having a mass ratio of compound (A): compound (B): fluorine-based solvent (C)=89:11:400 was prepared. After dropping this 1 mL on the Ta boat for vapor deposition, the solvent was evaporated to prepare a sample for vapor deposition. VPC-410A manufactured by ULVAC Kiko Co., Ltd. was used, and the aforementioned samples were removed by vacuum evaporation method (resistance heating method, pressure 8×10 ^-3 Pa, applied current 20A, and evaporation treatment time of 15 seconds). A thin film was formed on the alkali glass EAGLE-XG (registered trademark, manufactured by Corning Incorporated), and it was used as a sample for evaluating the performance of the film.

Table 1 shows the evaluation results of the abrasion resistance of the obtained film. In addition, in Example 1, the initial contact angle is 115.8°, the slip angle is 27.7°, and the contact angle hysteresis is 10.6°.

Example 2

After forming the film, except for further heat treatment at 150° C. for 30 minutes, the rest was performed in the same manner as in Example 1 to prepare a sample for evaluating the film performance.

Table 1 shows the results of evaluation of the abrasion resistance of the obtained film. In addition, in Example 2, the initial contact angle is 115.8°, the slip angle is 17.3°, and the contact angle hysteresis is 7.1°.

Example 3

After the film was formed, except that the ultrasonic cleaning treatment was further performed in water for 3 minutes, the rest was performed in the same manner as in Example 1 to prepare a sample for evaluating the film performance.

Table 1 shows the evaluation results of the abrasion resistance of the obtained film. In addition, 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

Except that Fluorolink (registered trademark) D4000 (number average molecular weight about 4000) represented by the following formula (b2) was used instead of compound (b1), the rest was performed in the same manner as in Example 2 to prepare a sample for evaluating film performance . Fluorolink (registered trademark) D4000 has a hydroxyl group and an oxyalkylene unit at the end, and part of the hydrogen atoms of the oxyalkylene unit is substituted by fluorine atoms. In addition, in Fluorolink D4000, the ratio of the number of fluorine atoms to the total number of hydrogen atoms excluding hydrogen atoms in the hydroxyl group and the number of fluorine atoms is 40% or more.

Table 1 shows the evaluation results of the abrasion resistance of the obtained film. In addition, 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

Except that the mass ratio of the composition was changed to the ratio of compound (A): compound (B): fluorine-based solvent (C)=80:20:400, the rest was performed in the same manner as in Example 2, and it was used for evaluating film performance. Sample.

Table 1 shows the evaluation results of the abrasion resistance of the obtained film. Furthermore, in Example 5, the initial contact angle is 114.9°, the slip angle is 26.3°, and the contact angle hysteresis is 14.5°.

Example 6

Except that the mass ratio of the composition was changed to the ratio of compound (A): compound (B): fluorine-based solvent (C)=80:20:400, the rest was performed in the same manner as in Example 4, and it was used to evaluate film performance. Sample.

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

Example 7

Except that the mass ratio of the composition was changed to the ratio of compound (A): compound (B): fluorine-based solvent (C)=67:33:400, the rest was performed in the same manner as in Example 4, and it was used to evaluate film performance. Sample.

Table 1 shows the evaluation results of the abrasion resistance of the obtained film. In addition, 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

Except that Fomblin (registered trademark) M03 (number average molecular weight about 4000) represented by the following formula (c) was used instead of compound (b1), the rest was the same as in Example 1 to prepare a sample for evaluating film performance . Fomblin (registered trademark) M03 has an oxyalkylene unit, and although all the hydrogen atoms of the oxyalkylene unit are replaced by fluorine atoms, there is no hydroxyl group in the molecule.

Table 1 shows the evaluation results of the abrasion resistance of the obtained film. In addition, in Comparative Example 1, the initial contact angle was 115.7° and the slip angle was greater than 50°, but even if the substrate was tilted to 50°, the water droplets did not slip off.

Comparative example 2

Except that Fomblin (registered trademark) M03 was used in place of compound (b1), the same procedures as in Example 2 were carried out to prepare samples for evaluating film performance.

Table 1 shows the evaluation results of the abrasion resistance of the obtained film. In addition, in Comparative Example 2, the initial contact angle is 116.5°, the slip angle is 13.7°, and the contact angle hysteresis is 4.2°.

Comparative example 3

Except that Fomblin (registered trademark) M03 was used in place of compound (b1), the same procedure as in Example 3 was carried out to prepare a sample for evaluating film performance.

Table 1 shows the evaluation results of the abrasion resistance of the obtained film. In addition, in Comparative Example 3, the initial contact angle is 118.3°, the slip angle is 13.3°, and the contact angle hysteresis is 6.5°.

It can be seen from Table 1 that, compared with Comparative Examples 1 to 3, Examples 1 to 7 using the compound (B) having a hydroxyl group have improved abrasion resistance. In addition, the film obtained using the composition of the present invention can be further improved in wear resistance by post-treatment after the film is formed, especially in Examples 1 to 3 where all the conditions except for the post-treatment conditions are the same. For comparison, Example 3, which was subjected to ultrasonic cleaning, had the best abrasion resistance.

[Industrial Utilization Possibility]

The composition of the present invention is used in display devices such as touch panel displays, optical elements, semiconductor elements, building materials, nanoimprint technology, solar cells, windows glass of automobiles or buildings, metal products such as conditioning appliances, food utensils, etc. Among the ceramic products, plastic automobile parts, etc., it can be suitable for film formation and is useful in industry. In addition, it is also suitable for use in kitchens, bathrooms, washstands, mirrors, toilets, and other materials, goggles, glasses, etc.

Claims (7)

A composition containing: (a1) a monovalent group having a perfluoropolyether structure and (a2) a compound (A) in which at least one of a hydrolyzable group and a hydroxyl group is bonded to a silicon atom, and a compound having a hydroxyl group and an oxygen extension Alkyl unit, and at least a part of the hydrogen atoms of the oxyalkylene unit are substituted by fluorine atoms, and the number average molecular weight is less than 10,000. The compound (B) at both ends are hydroxy groups. The composition described in item 1 of the scope of patent application, wherein the compound (A) is represented by the following formula (1a) or (2a):

In formula (1a), Rf ¹ is an alkyl group with 1 to 20 carbon atoms or a fluorine atom in which ^{one or more hydrogen atoms are replaced by fluorine atoms, and Rf 2 is} each independently that one or more hydrogen atoms are replaced by fluorine atoms The latter alkyl group having 1 to 20 carbons or a fluorine atom, R ^{1 is} each independently a hydrogen atom or an alkyl group having 1 to 4 carbons, R ^{2 is} each independently an alkyl group having 1 to 20 carbons, and D is each independently Independently -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, R is hydrogen Atom, C1-C4 alkyl group or C1-C4 fluorinated alkyl group, E is each independently a hydrolyzable group or a hydroxyl group, a1, b1, c1, d1, and e1 are each independently 0 or more and 600 or less The total value of a1, b1, c1, d1 and e1 is 9 or more, n is an integer of 1 or more and 3 or less, each repeating unit enclosed in parentheses with a1, b1, c1, d1, and e1, As long as at least some of them are arranged in the order of forming the perfluoropolyether structure, they can be arranged in any order.

In formula (2a), Rf ³ is an alkyl group with 1 to 20 carbon atoms or a fluorine atom in which ^{one or more hydrogen atoms are replaced by fluorine atoms, and Rf 4} is each independently one or more hydrogen atoms are replaced by fluorine atoms The substituted alkyl group having 1 to 20 carbons or a fluorine atom, R ^{3 is} each independently a hydrogen atom or an alkyl group having 1 to 4 carbons, and R ^{4 is} each independently an alkyl group having 1 to 20 carbons, M Each independently is -O-, -C(=O)-O-, -OC(=O)-, -NR-, -NRC(=O)-, or -C(=O)NR-, R is A hydrogen atom, an alkyl group having 1 to 4 carbons or a fluorinated alkyl group having 1 to 4 carbons, G is each independently a hydrolyzable group or a hydroxyl group, and Y is each independently a hydrogen atom or an alkyl group having 1 to 4 carbons , Z is a hydrogen atom or a halogen atom, a2, b2, c2, d2, and e2 are each independently an integer from 0 to 600, the total value of a2, b2, c2, d2, and e2 is 9 or more, and f2 is 1 to 20 For the following integers, g2 is an integer from 0 to 2 and p is an integer from 1 to 3, each repeating unit enclosed in parentheses with a2, b2, c2, d2, and e2, as long as at least part of it is The order of forming the perfluoropolyether structure can be arranged in any order. The composition described in item 2 of the scope of the patent application, wherein the compound (A) is a compound in which the sum of a1, b1, c1, d1, and e1 of the above formula (1a) is 13 or more, or the above formula (2a) ) A compound whose total value of a2, b2, c2, d2, and e2 is 13 or more. The composition described in any one of items 1 to 3 in the scope of the patent application, wherein the compound (B) is represented by the following formula (1b),

In the above formula (1b'), X is 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 -OC(=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, each repeating unit enclosed in parentheses with a3 to c3, as long as at least one The parts are arranged in the order in which the oxyalkylene unit is formed, that is, each is arranged in any order, and at least a part of the hydrogen atoms of the oxyalkylene unit are replaced by fluorine atoms. The composition described in any one of items 1 to 3 in the scope of the patent application, wherein the number of hydroxyl groups contained in the compound (B) is two. The composition according to any one of items 1 to 3 in the scope of patent application, wherein, in compound (B), the number of fluorine atoms is less than the total number of hydrogen atoms other than hydrogen atoms in the hydroxyl group and the number of fluorine atoms The ratio is more than 40%. The composition according to any one of items 1 to 3 in the scope of the patent application, wherein the mass ratio of the compound (A) to the compound (B) is 1 or more.