JP2018070832A - Composition, coating liquid, and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition which is capable of forming a film excellent in water repellency and water slipping property and is soluble in an incombustible solvent, and to provide a coating liquid and an article using the composition.SOLUTION: The composition contains: a copolymer (I) which contains: a unit (a) having a side group containing a perfluoroalkyl group and a unit (b) having a side group containing a hydrophilic group; copolymer (I) in which the molar ratio of the unit (a) to the unit (b) is 40/60-97/3; and a compound (II) containing a polyether polyol structure. The content of the compound (II) is 0.5-40 pts.mass based on 100 pts.mass of the copolymer (I).SELECTED DRAWING: None

Description

  The present invention relates to compositions, coating liquids and articles.

  Conventionally, water repellency is imparted to the surfaces of various equipment and instruments. As a method for imparting water repellency, generally, a method for decreasing the surface energy of the surface to be imparted with water repellency and increasing the water contact angle is applied. As a method for reducing the surface energy of the surface, for example, a method of forming a film on the surface using a water repellent such as a fluorine-containing compound or a silicone compound is known. In many cases, the water repellent is dissolved in a solvent that dissolves the water repellent.

  In recent years, in addition to water repellency, it is sometimes desired to impart lubricity. However, simply lowering the surface energy and increasing the water contact angle does not provide sufficient sliding properties, and conversely, sliding properties may decrease. For example, the water contact angle after the surface treatment is 110 ° or more and the water repellency is extremely high, but there are coating agents in which water droplets are adsorbed on the surface in that state and have no sliding property.

The following has been proposed as a composition capable of forming a film having excellent water slidability.
A composition containing a hydroxyl group-containing vinyl polymer, a functional group-containing siloxane polymer having an amino group, a carboxyl group or a glycidyloxy group at one end, a hydroxyl group-containing siloxane polymer having a hydroxyl group-containing organic group at both ends, and a specific crosslinking agent component (Patent Document 1).

JP 2000-26796 A

  Recently, from the viewpoint of safety, it has been desired that the solvent for dissolving the coating agent is nonflammable. However, since the composition described in Patent Document 1 does not dissolve in a nonflammable solvent, it is difficult to make the solvent nonflammable.

  An object of the present invention is to provide a composition that can form a film excellent in water repellency and water slidability and can be dissolved in a nonflammable solvent, and a coating liquid and article using the composition.

The present invention provides a composition, a coating liquid, and an article having the following configurations [1] to [11].
[1] comprising a unit (a) having a side group containing a perfluoroalkyl group and a unit (b) having a side group containing a hydrophilic group, wherein the molar ratio of the unit (a) to the unit (b) is Copolymer (I) which is 40/60 to 97/3,
A compound (II) containing a polyether polyol structure,
Content of said compound (II) is 0.5-40 mass parts with respect to 100 mass parts of said copolymers (I), The composition characterized by the above-mentioned.
[2] The composition of [1], wherein the unit (a) is a unit derived from a monomer represented by the following formula (1).
^{CX 1 X 2 = C (X} 3) -Q 1 -R f ··· (1)
However, X ¹ and X ² each independently represent a hydrogen atom or a fluorine atom, X ³ represents a hydrogen atom, a fluorine atom or a methyl group, Q ¹ represents a single bond or a divalent linking group, and R ^f represents A perfluoroalkyl group or —CHR ^f1 R ^f2 is shown. R ^f1 and R ^f2 each independently represent a perfluoroalkyl group.
[3] The composition of [1] or [2], wherein the unit (b) is a unit derived from a monomer represented by the following formula (2).
^{CX 4 X 5 = C (X} 6) -Q 2 -Z ··· (2)
X ⁴ and X ⁵ each independently represents a hydrogen atom or a fluorine atom, X ⁶ represents a hydrogen atom, a fluorine atom or a methyl group, Q ² represents a single bond or a divalent linking group, and Z represents a hydrophilic group. Indicates a group.
[4] The composition according to any one of [1] to [3], wherein the compound (II) is represented by the following formula (II-1).
_{^{R 2 - [O- (R 1}} -O) n -H] m ··· (II-1)
However, n represents an integer of 1 or more, m represents an integer of 1 to 4, R ¹ represents an alkylene group or a fluoroalkylene group, R ² represents a hydrogen atom when m is 1, and m represents In the case of 2 or more, m-valent chain saturated hydrocarbons in which some or all of the hydrogen atoms may be substituted with fluorine atoms and may have etheric oxygen atoms between carbon-carbon atoms. When n is 2 or more, n (R ² —O) may be the same or different.
[5] Q ¹ in the formula (1) is a single bond or a divalent linking group having no cyclic structure, R ^f is a C 1-8 perfluoroalkyl group, or —CHR ^f1 R ^f2 The composition according to [2], wherein R ^f1 and R ^f2 are each a perfluoroalkyl group having 1 to 4 carbon atoms.
[6] Q ² in the formula (2) is a single bond or a divalent linking group having no cyclic structure, and Z is —OH, —COOH, —Si (OH) ₃ , and —SO ₃ H. The composition according to [3], which is at least one selected from the group consisting of:
[7] The composition according to any one of [1] to [6], further comprising an isocyanate group-containing silane coupling agent.
[8] The composition according to any one of [1] to [7], which is a lubricant.
[9] A coating liquid comprising the composition according to any one of [1] to [8] and a solvent.
[10] The coating liquid according to [9], wherein the solvent is a nonflammable solvent.
[11] An article having a film formed from the composition of any one of [1] to [8] on the surface of a substrate.

According to the composition of the present invention, a film excellent in water repellency and water slidability can be formed. Moreover, the composition of this invention is soluble in a nonflammable solvent.
According to the coating liquid of the present invention, a film excellent in water repellency and water slidability can be formed. Moreover, even if the solvent is a nonflammable solvent, the composition of the present invention is well dissolved in the solvent.
The article of the present invention has a film excellent in water repellency and water slidability.

In this specification, the monomer represented by the formula (1) is also referred to as “monomer (1)”. The same applies to monomers represented by other formulas.
The meanings of the following terms in this specification are as follows.
“Non-flammable” means that the flash point is not measured by any of the tag sealing method defined in JIS K2265-1: 2007 and the Cleveland open method defined in JIS K2265-4: 2007 (the flash point is Does not exist).
The “unit” of the polymer indicates a structural unit derived from the monomer formed by polymerization of the monomer. The unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by treating a polymer obtained by the polymerization reaction.
“Side group” refers to a group bonded to the main chain of the polymer.
The “etheric oxygen atom” is an oxygen atom (—C—O—C—) that exists between carbon-carbon atoms.
The “perfluoroalkyl group” is a group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms. The “perfluoroalkylene group” is a group in which all hydrogen atoms of the alkylene group are substituted with fluorine atoms.
“(Meth) acrylate” is a general term for acrylate and methacrylate.

〔Composition〕
The composition of the present invention (hereinafter also referred to as “the present composition”) contains a copolymer (I) and a compound (II).
The composition may further comprise a crosslinking agent. Thereby, film | membrane hardness improves.
The composition may further contain other components other than those described above as required, as long as the stability, water repellency, water slidability, appearance, etc. of the composition are not impaired.
This composition does not contain the solvent mentioned later.

(Copolymer (I))
The copolymer (I) includes a unit (a) having a side group containing a perfluoroalkyl group and a unit (b) having a side group containing a hydrophilic group.
Copolymer (I) may further contain units (c) other than unit (a) and unit (b).

<Unit (a)>
The unit (a) is used to increase the solubility of the composition in a nonflammable solvent (particularly a fluorine-containing nonflammable solvent) and the water repellency of a film formed from the composition.
The perfluoroalkyl group may be linear or branched, and is preferably linear in that the water repellency is enhanced by densely arranging the perfluoroalkyl groups on the film surface.

The side groups containing a perfluoroalkyl group, include, for example, ^-Q 1 -R ^f. However, ^{Q 1} represents a single bond or a divalent linking group, ^{R f} represents perfluoroalkyl group or a ^-CHR f1 ^{R f2.} R ^f1 and R ^f2 each independently represent a perfluoroalkyl group. When Q ¹ is a single bond, R ^f is directly bonded to the main chain.

1-8 are preferable and, as for carbon number of the perfluoroalkyl group of ^Rf , 6-7 are especially preferable. As the carbon number of the perfluoroalkyl group is larger, the solubility of the copolymer (I) in the fluorine-containing nonflammable solvent is increased, and the storage stability of the coating liquid is increased.
1-4 are respectively preferable and, as for carbon number of ^Rf1 and ^Rf2 , respectively, 1-3 are especially preferable.
-CHR ^f1 R number of carbon atoms of ^f2 is preferably 3-9, more preferably 3-8, 3-7 is particularly preferred.

Examples of the divalent linking group for Q ¹ include —C (O) OQ ¹¹ —, — (R ^f3 —O) _y —, a substituted or unsubstituted alkylene group, and the like. However, Q ¹¹ represents a single bond or a divalent linking group. R ^f3 represents a perfluoroalkylene group, and y is an integer of 1 to 3.

As the divalent linking group for Q ¹¹ , for example, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, an oxyalkylene group (however, the oxygen atom side is bonded to R ^f ), -W ^1- Q ¹² -W ^2- and the like can be mentioned. However, W ¹ and W ² each independently represent a substituted or unsubstituted alkylene group, and Q ¹² represents —O—, —S—, —C (O) —, —C (O) O—, —C. _{^{(O) S -, - N}} (R 3) -, - SO 2 -, - PO 2 -, - N (R 3) -C (O) O -, - N (R 3) -C (O) - , —N (R ³ ) —SO ₂ —, or —N (R ³ ) —PO ₂ —, wherein R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

1-4 are preferable and, as for carbon number of the alkylene group in Q < ¹ >, Q < ¹¹ >, 1-2 are especially preferable. The alkylene group may be linear or branched, and is preferably linear in terms of increasing the film density and ensuring the film strength and durability.
Examples of the substituent of the substituted alkylene group include a halogen atom (F, Cl, Br, I), a cyano group, an alkoxy group (methoxy group, ethoxy group, butoxy group, octyloxy group, methoxyethoxy group, etc.), alkylthio group, and the like. Groups (such as methylthio and ethylthio groups), acyl groups (such as acetyl and propionyl groups), sulfonyl groups (such as methanesulfonyl groups), acyloxy groups (such as acetoxy groups), sulfonyloxy groups (such as methanesulfonyloxy groups), phosphonyl Group (diethylphosphonyl group etc.), amide group (acetylamino group etc.), carbamoyl group (N, N-dimethylcarbamoyl group etc.), alkenyl group (vinyl group, 1-propenyl group etc.), alkoxyacyloxy group (acetyloxy) Group), alkoxycarbonyl group (methoxycarbonyl group, etho Aryloxycarbonyl group), a polymerizable group (vinyl group, an acryloyl group, methacryloyl group, a silyl group, and cinnamic acid residue, etc.) and the like.

The number of carbon atoms of the alkenylene group in Q ¹¹ is 2 to 5, and particularly preferably 2-3. The alkenylene group may be linear or branched, and is preferably linear in terms of increasing the film density and ensuring the film strength and durability.
Examples of the substituent that the substituted alkenylene group has include the same substituents as those in the substituted alkylene group.

The alkylene group for W ¹ and W ² in —W ¹ -Q ¹² -W ² — is the same as described above.

1-5 are preferable and, as for carbon number of ^Rf3 , 1-3 are especially preferable. R ^f3 may be linear or branched. Specific examples of R ^f3 _{is, - (CF 2) 2 -} , - CF 2 CF (CF 3) -, - (CF 2) 3 -, - CF 2 CF (CF 3) -CF 2 (CF 3) - Etc.
y is preferably 1 or 2.

Q ¹ is preferably a single bond or a divalent linking group having no cyclic structure from the viewpoint of film stability and film strength securing. That it is preferred ^-Q 1 -R ^f is a radical having no cyclic structure.
As the divalent linking group having no cyclic structure, for example, in —C (O) OQ ¹¹ —, Q ¹¹ is a single bond, an alkylene group, an alkenylene group, an oxyalkylene group, or W ¹ and W ² are each independently represents an alkylene group in which ^-W 1 ^-Q 12 ^{-W 2} - a is _{^{group, - (R f3 -O) y}} -, such as an alkylene group. The alkylene group of Q ¹¹ , W ¹ and W ² and the alkenylene group of Q ¹¹ may each be unsubstituted, or may have a substituent that does not have a cyclic structure as a substituent.

Q ¹ is preferably a single bond, —C (O) O—Q ¹¹ —, or — (R ^f3 —O) _y —, wherein Q ¹¹ is an unsubstituted alkylene group, and Q ¹¹ is Particularly preferred is —C (O) OQ ¹¹ —, which is an unsubstituted linear alkylene group.

The unit (a) is preferably a unit having one side group containing a perfluoroalkyl group from the viewpoint of enhancing the water repellency of the film. Examples of such a unit include a unit derived from the monomer (1).
^{CX 1 X 2 = C (X} 3) -Q 1 -R f ··· (1)
However, X ¹ and X ² each independently represent a hydrogen atom or a fluorine atom, X ³ represents a hydrogen atom, a fluorine atom or a methyl group, and Q ¹ and R ^f are the same as defined above.

As preferable specific examples of the monomer (1), CH ₂ ═C (CH ₃ ) —C (O) O— (CH ₂ ) ₂ —C ₆ F ₁₃ , CH ₂ ═CH—C (O) O— ( _{CH 2) 2 -C 6 F 13} , CH 2 = C (CH 3) -C (O) O- (CH 2) 3 -C 6 F 13, CH 2 = CH-C (O) O- (CH 2 _{) 3 -C 6 F 13, CH} 2 = C (CH 3) -C (O) O-CH 2 -C 2 F 5, CH 2 = C (CH 3) -C (O) O-CH 2 -CF _{3, CH 2 = C (CH} 3) -C (O) O-CF 3, CH 2 = C (CH 3) -C (O) O-CH 2 -CF (CF 3) 2, CH 2 = C ( _{CH 3) -C (O) O} -CF (CF 3) 2, CH 2 = C (CH 3) -C (O) O-CH 2 -CH (CF 3) 2, CH 2 = C (CH 3) -C _{(O) O-CH (CF} 3) 2, CF 2 = CF-CF 2 CF 2 CF 3, CF 2 = CF-CF 2 CF (CF 3) -O-CF 2 CF 2 CF 3, CF 2 = CF _{-CF 2 CF (CF 3) -O} -CF 2 CF (CF 3) -O-CF 2 CF 2 CF 3 and the like. Among _{them, CH 2 = C (CH 3} ) -C (O) O- (CH 2) 2 -C 6 F 13, CH 2 = CH-C (O) O- (CH 2) 2 -C 6 F _{13, CH 2 = C (CH} 3) -C (O) O- (CH 2) 3 -C 6 F 13, CH 2 = CH-C (O) O- (CH 2) 3 -C 6 F 13, _{CH 2 = C (CH 3)} -C (O) O-CH 2 -C 2 F 5, CH 2 = C (CH 3) -C (O) O-CH 2 -CF 3, CH 2 = C (CH _{3) -C (O) O-} CH 2 -CF (CF 3) 2, CH 2 = C (CH 3) -C (O) O-CH 2 -CH (CF 3) 2 is preferred.

<Unit (b)>
Unit (b) is used to increase the water slidability of the film formed from the present composition.
Examples of the hydrophilic group in the unit (b) include —OH, —COOH, —Si (OH) ₃ , —SO ₃ H, and the like.

The side groups containing a hydrophilic group, include, for example, ^-Q 2 -Z. However, Q ² represents a single bond or a divalent linking group, Z is shown a hydrophilic group. If Q ² is a single bond, Z is directly attached to the main chain.
The hydrophilic group of Z is the same as the hydrophilic group in the unit (b).
Examples of the divalent linking group for Q ² include —C (O) O—Q ¹¹ —, — (O—R ^f3 ) _y —, a substituted or unsubstituted alkylene group, and the like. Q ¹¹ , R ^f3 and y are as defined above. Examples of the alkylene group are the same as those described above. However, the divalent linking group in Q ^{2 and} the divalent linking group in Q ¹ may be the same or different.

Q ² is preferably a single bond or a divalent linking group having no cyclic structure, as in Q ¹ . That it is preferred -Q 2 ^-Z is a radical having no cyclic structure. Examples of the divalent linking group having no cyclic structure include the same groups as described above.

Q ² is a single bond, —C (O) O—Q ¹¹ —, — (O—R ^f3 ) _y —, or an unsubstituted alkylene group, among the above, Q ¹¹ is an unsubstituted alkylene group. ^preferably, -C ^{Q 11} is an unsubstituted straight-chain alkylene group (O) ^{O-Q 11} - is particularly preferred.

The unit (b) is preferably a unit having one side group containing a hydrophilic group in terms of imparting water slidability while maintaining the water repellency of the film. Examples of such a unit include a unit derived from the monomer (2).
^{CX 4 X 5 = C (X} 6) -Q 2 -Z ··· (2)
However, X ⁴ and X ⁵ each independently represent a hydrogen atom or a fluorine atom, X ⁶ represents a hydrogen atom, a fluorine atom or a methyl group, and Q ² and Z are the same as defined above.

As preferable specific examples of the monomer (2), CH ₂ ═C (CH ₃ ) —C (O) O— (CH ₂ ) ₂ —OH, CH ₂ ═C (CH ₃ ) —C (O) O— _{(CH 2) 4 -OH, CH} 2 = C (CH 3) -C (O) O-CH 2 -COOH, CH 2 = C (CH 3) -C (O) O-CH 2 -Si (OH) ₃ , CF ₂ ═CF—O— (CF ₂ ) ₃ —COOH, CF ₂ ═CF—O—CF ₂ CF (CF ₃ ) —O— (CF ₂ ) ₂ —COOH, CF ₂ ═CF—O— ( _{CF 2) 3 -O- (CF 2} ) 2 -COOH, CH 2 = CH-COOH, CH 2 = CH-OH, CH 2 = CH-CH 2 -OH, CH 2 = C (CH 3) -CH 2 -OH etc. are mentioned. Among _{them, CH 2 = C (CH 3} ) -C (O) O- (CH 2) 2 -OH, CH 2 = C (CH 3) -C (O) O- (CH 2) 4 -OH, _{CH 2 = C (CH 3)} -C (O) O-CH 2 -COOH, are CH 2 = C (CH 3) -C (O) O-CH 2 -Si (OH) 3 preferred.

<Unit (c)>
Examples of the unit (c) include units derived from monomers other than the monomer (1) and the monomer (2). Other monomers are not particularly limited as long as they are copolymerizable with monomer (1) and monomer (2), and examples thereof include the following.
alkyl (meth) acrylates such as n-propyl (meth) acrylate and n-butyl (meth) acrylate; cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate; CH ₂ = CH-OR ⁹ (where R ⁹ is And a vinyl ether compound such as tetrafluoroethylene and vinylidene fluoride; and the like. Olefin etc.
Specific examples of CH ₂ ═CH—OR ⁹ include CH ₂ ═CH—O— (CH ₂ ) ₂ —O—C ₂ H ₅ , CH ₂ ═CH—O— (CH ₂ ) ₂ —O—C _4. H ₉ and the like.

  In the copolymer (I), the molar ratio of the unit (a) to the unit (b) (unit (a) / unit (b) is 40/60 to 97/3, and 70/30 to 97/3. 90/10 to 97/3 is more preferable, and 93/7 to 97/3 is particularly preferable, if the unit (a) / unit (b) is equal to or more than the lower limit of the above range, a perfluoroalkyl group is sufficient. Therefore, the solubility of the composition in a non-flammable solvent and the water repellency of the film formed from the composition are excellent, and the copolymer (I) is difficult to dissolve in water. If the unit (a) / unit (b) is not more than the upper limit of the above range, the water-sliding property of the film formed from the composition is excellent.

  The total content of the unit (a) and the unit (b) in the copolymer (I) is 70 mol% with respect to the total mass (100 mol%) of all the units constituting the copolymer (I). The above is preferable, and 85 mol% or more is particularly preferable. The upper limit of this content is not specifically limited, 100 mol% may be sufficient.

  The content of the unit (c) in the copolymer (I) varies depending on the type, but is 30 mol% or less with respect to the total mass (100 mol%) of all the units constituting the copolymer (I). Is preferable, and 15 mol% or less is particularly preferable.

In the present invention, the molar ratio of each unit in the copolymer can be measured by a known measurement method such as a nuclear magnetic resonance (NMR) method.
A value that is considered that all of the polymerization raw materials (monomers) used in the polymerization constitute a copolymer may be the molar ratio of each unit in the copolymer. For example, when unit (a) is a unit derived from monomer (1), the molar ratio of unit (a) (percentage of the number of moles of unit (a) contained therein relative to the total number of moles of all units) is The ratio is determined substantially as the ratio of the number of moles of the monomer (1) to the total number of moles of the polymerization raw material used for the polymerization. The molar ratio of other units in the copolymer is also determined in the same manner.

The arrangement of the unit (a) and the unit (b) in the copolymer (I) is not particularly limited. The arrangement of the unit (c) when the unit (c) is optionally included is the same.
The copolymer (I) may be any of a random copolymer, a block copolymer, a graft copolymer, and the like, but is preferably a random copolymer.

The molecular weight of the copolymer (I) is not particularly limited, but the number average molecular weight (Mn) is preferably 1 × 10 ³ to 1 × 10 ^{7 and} particularly preferably 1 × 10 ⁴ to 1 × 10 ⁶ . When Mn is not less than the lower limit of the above range, the film forming property is excellent. When Mn is not more than the upper limit of the above range, the solubility in a solvent is excellent.
Mn of the copolymer (I) is a standard polymethyl methacrylate equivalent value measured by gel permeation chromatography (GPC).

  The production method of the copolymer (I) is not particularly limited, and various known methods can be adopted. For example, it can be obtained by copolymerizing the monomer (1), the monomer (2), and other monomers as required. The polymerization method is not particularly limited, and examples thereof include a solution polymerization method and an emulsion polymerization method. When the polymerization raw material is gaseous, it may be continuously supplied under pressure using a pressure vessel. The polymerization can be carried out by appropriately adopting known addition polymerization conditions for unsaturated compounds. For example, a normal initiator such as an organic peroxide, an azo compound, or a persulfate can be used as a polymerization initiation source. In addition, a chain transfer agent can be used in the polymerization reaction for adjusting the molecular weight.

(Compound (II))
Compound (II) contains a polyether polyol structure.
By combining the copolymer (I) having the unit (b) and the compound (II), excellent water lubricity can be expressed in the film formed from the composition.
Compound (II) may or may not contain a fluorine atom. It is preferable not to contain a fluorine atom in that the specific gravity smaller than that of the perfluoroalkyl group contained in the copolymer (I) tends to improve the water slidability by moving to the film surface.

The hydroxyl value of compound (II) is preferably 20 to 150 mgKOH / g, more preferably 40 to 100 mgKOH / g, and particularly preferably 50 to 80 mgKOH / g. If the hydroxyl value is not less than the lower limit of the above range, the water-sliding property of the film formed from the composition is more excellent. If the hydroxyl value is not more than the upper limit of the above range, the water repellency is more excellent.
The hydroxyl value is measured by titration with potassium hydroxide.

The number average molecular weight (Mn) of the compound (II) is preferably 400 to 30,000, more preferably 1,000 to 10,000, and particularly preferably 1,500 to 5,000. If the number average molecular weight is equal to or more than the lower limit of the above range, it is difficult to volatilize during film formation and the like, and the water slidability is easily developed. If the number average molecular weight is not more than the upper limit of the above range, the solubility in a fluorine-containing nonflammable solvent is more excellent.
The number average molecular weight of the compound (II) is a standard polymethyl methacrylate conversion value measured by gel permeation chromatography (GPC).

As the compound (II), the compound (II-1) represented by the following formula (II-1) is preferable in that the effect of imparting water slidability is more excellent.
_{^{R 2 - [O- (R 1}} -O) n -H] m ··· (II-1)
However, n represents an integer of 1 or more, m represents an integer of 1 to 4, R ¹ represents an alkylene group or a fluoroalkylene group, R ² represents a hydrogen atom when m is 1, and m represents In the case of 2 or more, m-valent chain saturated hydrocarbons in which some or all of the hydrogen atoms may be substituted with fluorine atoms and may have etheric oxygen atoms between carbon-carbon atoms. In the case where n is 2 or more, n (R ¹ -O) may be the same or different.

n is preferably a value such that the number average molecular weight of the compound (II-1) falls within the above preferred range.
m is preferably an integer of 1 to 3, and particularly preferably an integer of 2 to 3.

R number of carbon atoms of the alkylene group for ¹ to 5 preferably 1 to 3 is particularly preferable. The alkylene group may be linear or branched. Specific examples of the alkylene group include — (CH ₂ ) ₂ —, —CH ₂ CH (CH ₃ ) —, —CH ₂ CH (CH ₃ ) CH (CH ₃ ) —, and the like.
1-5 are preferable and, as for carbon number of a fluoroalkylene group, 1-3 are especially preferable. The fluoroalkylene group may be linear or branched. Specific examples of the fluoroalkylene group include —CF ₂ —, — (CF ₂ ) ₂ —, —CF ₂ CF (CF ₃ ) —, —CF ₂ CF (CF ₃ ) CF (CF ₃ ) —, and the like. .
R ¹ is preferably an alkylene group, and preferably has a branched chain alkylene group in that the specific gravity is smaller than that of the perfluoroalkyl group contained in the copolymer (I) and the surface tends to improve lubricity. Are more preferable, and —CH ₂ CH (CH ₃ ) — is particularly preferable.

The m-valent chain saturated hydrocarbon group for R ² may have a branched structure or may not have a branched structure. 1-3 are preferable and, as for carbon number of a saturated hydrocarbon group, 1-2 are especially preferable.
When m is 1, R ² is an alkylene group or a fluoroalkylene group, and examples thereof are the same as those for R ¹ .
When m is 2 or more, R ² is not particularly limited. For example, R ² is a group represented by the following formula (where R ⁴ is an alkyl group, preferably a methyl group or an ethyl group), Examples include a group in which part or all of the hydrogen atoms are substituted with fluorine atoms.

  Specific examples of the compound (II) include the compound (II-11) represented by the following formula (II-11), the compound (II-12) represented by the following formula (II-12), and the following formula (II- And the compound (II-13) represented by 13).

Where g and h each represent 0 or 1, R ¹¹ represents H when g is 0, CH ₂ when g is 1, and R ¹² represents H or h when h is 0. In the case of 1, CH ₂ is indicated, j, l and m each represent an integer of 1 or more, provided that j + m + 1 = 2 or more, r represents an integer of 2 or more, and p and q each represents an integer of 1 or more. Show.
j + l + m is preferably a value such that the number average molecular weight of the compound (II-11) falls within the above preferred range. r is preferably a value such that the number average molecular weight of the compound (II-12) falls within the above preferred range. p + q is preferably a value such that the number average molecular weight of the compound (II-13) falls within the above-mentioned preferable range.
In [(CF ₂ CF ₂ O) _p (CF ₂ O) _q ] in formula (II-13), the bonding order of p (CF ₂ CF ₂ O) and q (CF ₂ O) is limited. Not. For example, these groups may be arranged randomly, alternately, or in blocks.

  A commercial item can be used as compound (II). You may use what was manufactured by the well-known manufacturing method. Examples of commercially available products include Exenol (registered trademark) 2020, Exenol 3030, Exenol 4020, manufactured by Asahi Glass Co., and Fluorolink (registered trademark) D-10H manufactured by Solvay. The production method of compound (II) is described, for example, in JP-A-54-30110, JP-B-54-44720, JP-A-56-38322, JP-A-56-43322, and the like. The method is mentioned.

(Crosslinking agent)
Examples of the crosslinking agent include bifunctional or higher functional isocyanate compounds such as hexamethylene diisocyanate and trimethylhexamethylene disonate, and isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane. These crosslinking agents may be used alone or in combination of two or more.

(Other ingredients)
Other components include, for example, pH adjusters, surfactants, rust inhibitors, and the concentration control of the polymer in the solution when the composition is diluted with a solvent. And dyes, dye stabilizers, flame retardants, antifoaming agents, antistatic agents and the like for distinguishing from untreated parts. These additives may be used alone or in combination of two or more.

(Content ratio of each component)
In this composition, content of compound (II) is 0.5-40 mass parts with respect to 100 mass parts of copolymer (I), 5-30 mass parts is preferable, 5-15 mass parts Is particularly preferred. If the content of the compound (II) is at least the lower limit of the above range, the water lubricity of the film formed from the present composition is excellent. If the content of compound (II) is not more than the upper limit of the above range, the water repellency of the film formed from the present composition will be excellent. In addition, since the film is difficult to dissolve in water, it is difficult for the film to have traces of water droplets.

  70 mass% or more is preferable with respect to the total mass (100 mass%) of this composition, and, as for the total mass of copolymer (I) and compound (II), 85 mass% or more is especially preferable. The upper limit of the total mass is not particularly limited, and may be 100% by mass. When the total mass is not less than the lower limit, the water repellency and water slidability of the film formed from the composition are more excellent.

  When this composition contains a crosslinking agent, 2-7.5 mass parts is preferable with respect to 100 mass parts of copolymer (I), and 3-6 mass parts is especially preferable. If content of a crosslinking agent is more than the lower limit of the said range, the hardness of the film | membrane formed from this composition and adhesiveness with a base material (glass, a metal substrate etc.) will increase. If the content of the crosslinking agent is not more than the upper limit of the above range, the hydrophilic group in the unit (b) and the hydroxyl group in the compound (II) remain sufficiently, and the film formed from the present composition has sufficient lubricity. Expressed in

  5 mass% or less is preferable with respect to the total mass (100 mass%) of this composition, and, as for content of the other component in this composition, 3 mass% or less is especially preferable. The lower limit is not particularly limited, and may be 0% by mass.

(Function and effect)
In the present composition, the copolymer (I) containing the unit (a) and the unit (b), wherein the unit (a) / unit (b) is 70/30 to 99/1, and a polyether Compound (II) containing a polyol structure, and the content of compound (II) is 0.5 to 40 parts by mass with respect to 100 parts by mass of copolymer (I), so that it has excellent water repellency and water slidability Film can be formed. Moreover, this composition is soluble in a nonflammable solvent.
Since the composition can be dissolved in a nonflammable solvent, the composition can be dissolved in a solvent containing a nonflammable solvent to form a nonflammable coating liquid as a whole.

The reason why the water repellency of the film is excellent is that the copolymer (I) contains the unit (a) at a certain ratio or more, so that sufficient perfluoroalkyl groups are distributed throughout the film and the hydrophobicity is increased. It is conceivable that the surface energy is lowered.
When water droplets are present on the surface of a hydrophobic membrane such as a membrane containing perfluoroalkyl groups, the water droplets will conform to the surface of the hydrophobic membrane, so that the water droplets will aggregate more and have a positive charge, and the hydrophobic surface will have a negative charge. It is known to be tinged (Hirachi Murase, coloring material, 73, P60-66, 2000). This phenomenon is considered to be the reason why there is a film having high water repellency but no slidability. As in the present invention, when a very small amount of hydrophilic group is present on the film surface, the structure of the aggregated water is relaxed due to the influence of the hydrophilic group, and at the same time, electrostatic binding is also relaxed, so that the lubricity is excellent. Conceivable.

  Because of the above effects, the present composition is useful as a lubricant or the like. By using this composition as a lubricant, water repellency and water slidability can be imparted to the surface of any substrate.

[Coating solution]
The coating liquid of the present invention (hereinafter also referred to as “the present coating liquid”) includes the present composition and a solvent. The present coating liquid is a liquid form composition containing the present composition in a solvent.

  The concentration of the present composition in the present coating liquid is preferably from 0.1 to 20% by weight, particularly preferably from 1 to 10% by weight. When the concentration of the present composition is within the above range, the thickness of the film formed using the present coating liquid tends to be within a suitable range in which various performances such as water repellency and water slidability are sufficiently exhibited.

(solvent)
The solvent is not particularly limited as long as it can dissolve the copolymer (I) and the compound (II), and can be appropriately selected from various known solvents.
The solvent is preferably a nonflammable solvent. When the solvent is a nonflammable solvent, the present coating liquid can be made nonflammable or flame retardant to enhance safety.
The content of the nonflammable solvent is preferably an amount that makes the entire coating liquid nonflammable.

Examples of the incombustible solvent include a fluorine-containing incombustible material that can dissolve the copolymer (I) and the compound (II) and has a fluorine atom content (hereinafter also referred to as “F content”) of 45 mass% or more. A solvent is mentioned. As for F content rate of a fluorine-containing nonflammable solvent, 47 mass% or more is preferable. The upper limit of F content rate is not specifically limited, For example, it may be 50 mass%.
F content rate is calculated | required by the following Formula.
F content = number of fluorine atoms in molecule × 19 / molecular weight × 100

Specific examples of the fluorine-containing incombustible solvent include the following.
Hydrochlorofluorocarbon (HCFC) such as CF ₃ CF ₂ CHCl ₂ (F content 46.8% by mass), CClF ₂ CF ₂ CHClF (F content 46.8% by mass); CF ₃ (CF ₂ ) ₅ CH ₂ Hydrofluorocarbon (HFC) such as CH ₃ (F content 71.0% by mass); Hydrofluoroether (HFE) such as CF ₃ CH ₂ OCF ₂ CF ₂ H (F content 47.5% by mass); These solvents may be used alone or in combination of two or more.

As for content of the said fluorine-containing nonflammable solvent, 50 mass% or more is preferable with respect to the total mass (100 mass%) of a solvent. An upper limit is not specifically limited, 100 mass% may be sufficient.
Content of the said fluorine-containing nonflammable solvent may be 50-70 mass% with respect to the total mass (100 mass%) of this coating liquid, for example.

In addition to the fluorine-containing incombustible solvent, the solvent may further contain other solvents other than the fluorine-containing incombustible solvent as long as the entire coating liquid is not combustible. By using another solvent in combination, the solubility of the present composition in the solvent can be increased.
Other solvents may be used as long as they are miscible with the fluorine-containing nonflammable solvent and can dissolve the copolymer (I) and the compound (II). Specific examples of other solvents include m-xylene hexafluoride (hereinafter also referred to as “m-XHF”), p-xylene hexafluoride (hereinafter also referred to as “p-XHF”), 1, 1 Combustible fluorine-containing solvent having an F content of less than 55% by mass, such as 2, 2, and tetrafluoropropanol, and a fluorine-containing solvent that is incombustible but cannot dissolve compound (2), such as (C ₄ F ₉ ) ₃ N Is mentioned.
The content of the other solvent is preferably 50% by mass or less with respect to the total mass (100% by mass) of the solvent. The lower limit is not particularly limited, and may be 0% by mass.

The solvent preferably contains a fluorine-containing incombustible solvent, can make the entire coating liquid incombustible, and can dissolve the copolymer (I) and the compound (II).
Examples of the solvent containing a fluorine-containing incombustible solvent include a single solvent of a fluorine-containing incombustible solvent or a mixed solvent of two or more thereof, and the above-mentioned fluorine-containing incombustible solvent and another solvent are mixed in a range that does not become combustible. A mixed solvent etc. are mentioned. As the other solvent, a flammable fluorine-containing solvent is preferable.

Although the specific example of a preferable solvent is given to the following, it is not necessarily limited to this.
CF ₃ CH ₂ OCF ₂ CF ₂ H,
CF ₃ CF ₂ CHCl ₂ ,
CClF ₂ CF ₂ CHClF,
CF ₃ CH ₂ OCF ₂ CF ₂ H: m-XHF = 1: 1 (mass ratio) mixed solvent,
CF ₃ CH ₂ OCF ₂ CF ₂ H: p-XHF = 1: 1 (mass ratio) mixed solvent or the like.

0.1-20 mass% is preferable, as for the solid content concentration in this coating liquid, 1-15 mass% is more preferable, 1-10 mass% is further more preferable, and 2-5 mass% is especially preferable. The solid concentration of the present coating solution is equal to the concentration of the present composition. When the solid content concentration is within the above range, the thickness of the film formed using the present coating liquid tends to be within a suitable range in which various performances such as water repellency and water slidability are sufficiently exhibited.
The solid content concentration of the coating liquid can be calculated from the mass after the coating liquid is vacuum-dried at 80 ° C. for 3 hours and the mass of the coating liquid before heating. You may calculate from the quantity of this composition and solvent mix | blended at the time of manufacture of this coating liquid.

  The coating liquid preferably contains 80 to 99.9% by mass of the solvent, more preferably 85 to 99% by mass, further preferably 90 to 99% by mass, and particularly preferably 95 to 98% by mass. preferable.

  The manufacturing method of this coating liquid is not specifically limited. For example, the present composition is prepared in advance, a method of mixing the present composition and a solvent, a polymerization raw material such as monomer (1) or monomer (2) is added to the solvent, and this solvent is used as a polymerization medium. A solution of the copolymer (I) by solution polymerization, and adding the compound (II) and, if necessary, an additional solvent to the solution; emulsion polymerization of the polymerization raw material in an aqueous medium, An emulsion of the compound (I) is obtained, and the copolymer (I) is separated from the emulsion and dissolved in a solvent to obtain a solution of the copolymer (I). Depending on the case, a method of adding an additional solvent may be used.

(Function and effect)
Since the present coating liquid contains the present composition and a solvent, a film excellent in water repellency and water slidability can be formed when the present coating liquid is applied onto a substrate and dried. Further, since the present composition can be dissolved in a non-flammable solvent, the present composition is well dissolved in the solvent even if the entire coating liquid contains an amount of non-flammable solvent that is non-flammable. Therefore, it is excellent in storage stability. Moreover, when this coating liquid is apply | coated on a base material, the film | membrane excellent in film thickness uniformity can be formed.

[Articles]
The article of the present invention has a film formed from the composition on the surface of the substrate.

The thickness of the film is preferably 150 to 1,000 nm, particularly preferably 200 to 400 nm. If the thickness of the film is not less than the lower limit of the above range, sufficient water repellency and water slidability are likely to be exhibited. When the thickness of the film is not more than the upper limit of the above range, the film strength is excellent.
The thickness of the membrane is It is determined by measurement with an ellipsometer represented by A. Woollam.

(Base material)
The substrate in the present invention is not particularly limited as long as it is a substrate for which water repellency or water slidability is required. Examples of the base material include metals, resins, glass, sapphire, ceramics, stones, wood, fibers, and composite materials of two or more of these.

(Product manufacturing method)
The article of the present invention can be produced, for example, by a method in which the coating liquid is applied to the surface of a substrate and dried to form a film.
As a coating method of this coating liquid, a known wet coating method can be used. For example, a dip coating method, a spin coating method, a wipe coating method, a spray coating method, a squeegee coating method, a die coating method, an inkjet method, a flow coating method, a roll Examples thereof include a coating method, a casting method, a Langmuir / Blodgett method, and a gravure coating method.
As a drying method, a method of heating at a temperature equal to or higher than the boiling point of the solvent is preferable. However, when heat drying is difficult due to the material of the substrate, etc., heating should be avoided to dry. What is necessary is just to select a heating condition according to a composition, application area, etc. of this coating liquid.

(Function and effect)
Since the film | membrane which the article | item of this invention has on the surface of a base material is a film | membrane formed from this composition, it is excellent in water repellency and water slidability.

(Use of goods)
The article of the present invention is preferably a facility, apparatus, instrument, component or the like in which at least one of water repellency and water slidability, preferably both of them are desired or required.
Specific examples of articles include automobile window glass, automobiles, motorcycles, bicycle paint surfaces, kitchen equipment, kitchenware, exhaust equipment attached to kitchen equipment, fins and filters for air conditioners such as air conditioners, bathing equipment, etc. , Toiletries, medical facilities, medical equipment, mirrors, eyeglasses, inkjet printer parts, toilets, and the like.
Equipment, equipment, appliances, parts, etc. that are subjected to water washing such as refrigerators, freezers, fins and filters of air conditioning equipment are required to have a function to make water droplets difficult to adhere in order to improve drainage after water washing. . It can also be used as an anti-icing film for fins and filters of freezers and air conditioning equipment. Since a film excellent in both water repellency and water slidability does not easily adhere to water droplets, facilities, devices, instruments, parts, etc. that are subjected to water washing are suitable as the article of the present invention.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited by the following description. “%” Indicates “mass%” unless otherwise specified.
Among Examples 1 to 29 to be described later, Examples 1 to 5, 7 to 9, 16, 18, 22, and 25 are comparative examples, and other examples are examples.
The evaluation methods and materials used in each example are shown below.

〔Evaluation method〕
(Number average molecular weight (Mn))
The number average molecular weight of a polymer is a polymethyl methacrylate (PMMA) conversion molecular weight by a gel permeation chromatography (GPC) method.

(Water contact angle)
In an environment of 25 ° C. and 40% RH, about 2 μL of ion-exchanged water is dropped on the surface of the film-coated glass substrate, and the contact angle (water contact angle) is measured with a contact angle meter (DM-500 manufactured by Kyowa Interface Science Co., Ltd.). ) Was measured. The larger this value, the higher the water repellency.

(Water falling angle)
In an environment of 25 ° C. and 40% RH, 20 μL of ion-exchanged water is dropped on the surface of the glass substrate with the film, and the glass substrate with the film is formed using a contact angle meter (DM-500 manufactured by Kyowa Interface Science Co., Ltd.). It was tilted at a rate of 1.6 ° / second from 0 ° to 90 ° with respect to the horizontal plane. Under the present circumstances, the inclination angle with respect to the horizontal surface of the glass substrate with a film when a water droplet began to roll was made into the water fall angle. The smaller this value, the higher the lubricity. Those in which water droplets did not slide even when tilted by 90 ° were described as “no falls”.

(Trace of water drops)
After the measurement of the water contact angle, water droplets on the membrane surface were blown off with a blower, and it was visually confirmed whether or not traces of water droplets were generated on the membrane.

(Solubility in solvent)
In an environment of 25 ° C., the composition and the same solvent used for the coating liquid are mixed so that the composition concentration becomes 0.1%, and the obtained liquid is visually observed to determine the composition. The case where the total amount was dissolved was “◯” (passed), and the case other than that was “×” (failed).

(Flammable)
The flash point was measured by the following procedure, and the presence or absence of the flash point was determined. In both (a) and (b), the case where there was no flash point was set to “No”, and the other cases were set to “Yes”. In both (a) and (b), if there is no flash point, it is nonflammable.
<Flash point measurement procedure>
(A) Flash point measurement was performed by a tag sealing method defined in JIS K2265-1: 2007.
(B) When the flash point could not be measured at a temperature of 80 ° C. or less in the above (a), the flash point was measured by the Cleveland open method defined in JIS K2265-4: 2007.

〔material〕
(Monomer)
The monomers used for the production of the copolymer are shown below.
Monomer _{1: CH 2 = C (CH} 3) -C (O) O- (CH 2) 2 -C 6 F 13.
Monomer _{2: CH 2 = C (CH} 3) -C (O) O- (CH 2) 2 -OH.
Monomer _{3: CH 2 = C (CH} 3) -C (O) O- (CH 2) 3 -CH 3.
Monomer _{4: CH 2 = C (CH} 3) -C (O) O-R c ( however, ^{R c} represents a cyclohexyl group.).
Monomer _{5: CH 2 = C (CH} 3) -C (O) O-CH 2 -COOH.
Monomer _{6: CH 2 = C (CH} 3) -C (O) O-CH 2 -CF 3.
Monomer _{7: CH 2 = CH-C} (O) O- (CH 2) 2 -C 6 F 13.

(Compound)
Compound A: A polyether polyol represented by the formula (II-11), wherein g is 1, h is 0, R ¹¹ is CH ₂ , and R ¹² is H.
Compound B: A polyether polyol represented by the formula (II-11), wherein g is 1, h is 0, R ¹¹ is CH ₂ and R ¹² is H.
Compound C: A polyether polyol represented by the formula (II-11), wherein g and h are 1, and R ¹¹ and R ¹² are CH ₂ .
Compound D: A polyether polyol represented by the formula (II-11), wherein g is 1, h is 0, R ¹¹ is CH ₂ , and R ¹² is H.
Compound E: Fluorolink D-10H (manufactured by Solvay). A compound represented by the formula (II-13).
Compound F: A modified silicone compound having an alkoxysilyl group at the end, which is a polyether polyol represented by the formula (II-11), wherein g and h are 1, R ¹¹ and R ¹² are CH ₂ as a precursor.
Compound G: Compound represented by the following formula (G).
Compounds A to D and compound F precursors were prepared according to the method described in JP-A No. 54-30110. Compound F was produced by converting the OH group of the precursor to an alkoxysilyl group in accordance with the method described in JP2011-116947A.
Table 1 shows the number average molecular weights and hydroxyl values of the compounds A to G.

(Additive)
Additive 1: Hexamethylene diisocyanate (HDI), manufactured by Tokyo Chemical Industry Co., Ltd.
Additive 2: 3-isocyanatopropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.

(solvent)
Solvent 1: 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (CF ₃ CH ₂ OCF ₂ CF ₂ H) (Asahi Kulin (registered trademark) AE-3000, manufactured by Asahi Glass Co., Ltd.) ).
Solvent 2: dichloropentafluoropropane (CF ₃ CF ₂ CHCl ₂ / CClF ₂ CF ₂ CHClF) (Asahi Clin AK-225, manufactured by Asahi Glass Co., Ltd.).
The solvent _{3: CF 3 CH 2 OCF 2} CF 2 H: m-XHF = 1: mixed solvent of 1 (mass ratio).
Solvent 4: Mixed solvent of CF ₃ CH ₂ OCF ₂ CF ₂ H: p-XHF = 1: 1 (mass ratio).
All of the solvents 1 to 4 were nonflammable.

[Examples 1 to 29]
As the monomer corresponding to each of the units (a) to (c), the monomers listed in Table 2 have a molar ratio of unit (a) / unit (b) / unit (c) shown in Table 2. Into the polymerization tank, 4 times m-XHF in terms of mass with respect to the total mass of all monomers as a solvent, 0.01 times V-601 (trade name, manufactured by Wako Pure Chemical Industries) as an initiator. And polymerized at 70 ° C. for 18 hours to obtain a copolymer solution. Then, the solvent was removed by vacuum drying at 80 ° C. for 3 hours to obtain a solid copolymer.
The obtained copolymer, the compounds shown in Table 2, and the additives 1 and 2 were mixed at a mass ratio of copolymer / compound / additive 1 / additive 2 shown in Table 2 to obtain a composition. . About the obtained composition, the solubility to a solvent was evaluated. The results are shown in Table 2.
The obtained composition and the solvent shown in Table 2 were mixed so that the composition concentration was 3% to obtain a coating solution. The obtained coating liquid was evaluated for nonflammability. The results are shown in Table 2.
The obtained coating solution is applied onto a glass substrate by spin coating (1,000 rotations per minute, 30 seconds), dried in an oven adjusted to 100 ° C. for 10 minutes to form a film, and with a film A glass substrate (article) was obtained. The film was evaluated for water repellency, water trace, and water slidability. The results are shown in Table 2.

From the above results, a copolymer containing unit (a) and unit (b), wherein unit (a) / unit (b) is 40/60 to 97/3, and a compound containing a polyether polyol structure In combination, by setting the content of the compound to 0.5 to 40 parts by mass with respect to 100 parts by mass of the copolymer, a film excellent in water repellency and water slidability can be formed, and a nonflammable solvent can be formed. It turns out that it becomes soluble.
From the results of Examples 12 to 15, it can be seen that the compound having a polyether polyol structure has a higher number average molecular weight or a higher hydroxyl value, so that it is more likely to exhibit lubricity.
From the results of Examples 12 to 15 and 17, it can be seen that the compound containing the polyether polyol structure does not contain a fluorine atom, and the water slidability is more easily developed than the case where the compound contains a fluorine atom.

  The composition, coating solution and article of the present invention can be used for various applications where water repellency, water slidability, etc. are required or required. Specific examples include painted windows on automobile windows, automobiles, motorcycles, bicycles, kitchen equipment (for example, refrigerators and freezers), kitchenware, exhaust equipment attached to kitchen equipment, fins for air conditioners such as air conditioners, Examples include filters, bathing facilities, wash facilities, medical facilities, medical equipment, mirrors, glasses, inkjet printer parts, toilets, and the like.

Claims (11)

A unit (a) having a side group containing a perfluoroalkyl group and a unit (b) having a side group containing a hydrophilic group are included, and the molar ratio of the unit (a) to the unit (b) is 40/60. A copolymer (I) of ~ 97/3;
A compound (II) containing a polyether polyol structure,
Content of the said compound (II) is 0.5-40 mass parts with respect to 100 mass parts of the said copolymer (I), The composition characterized by the above-mentioned. The composition according to claim 1, wherein the unit (a) is a unit derived from a monomer represented by the following formula (1).
^{CX 1 X 2 = C (X} 3) -Q 1 -R f ··· (1)
However, X ¹ and X ² each independently represent a hydrogen atom or a fluorine atom, X ³ represents a hydrogen atom, a fluorine atom or a methyl group, Q ¹ represents a single bond or a divalent linking group, and R ^f represents A perfluoroalkyl group or —CHR ^f1 R ^f2 is shown. R ^f1 and R ^f2 each independently represent a perfluoroalkyl group. The composition according to claim 1 or 2, wherein the unit (b) is a unit derived from a monomer represented by the following formula (2).
^{CX 4 X 5 = C (X} 6) -Q 2 -Z ··· (2)
X ⁴ and X ⁵ each independently represents a hydrogen atom or a fluorine atom, X ⁶ represents a hydrogen atom, a fluorine atom or a methyl group, Q ² represents a single bond or a divalent linking group, and Z represents a hydrophilic group. Indicates a group. The composition according to any one of claims 1 to 3, wherein the compound (II) is represented by the following formula (II-1).
_{^{R 2 - [O- (R 1}} -O) n -H] m ··· (II-1)
However, n represents an integer of 1 or more, m represents an integer of 1 to 4, R ¹ represents an alkylene group or a fluoroalkylene group, R ² represents a hydrogen atom when m is 1, and m represents In the case of 2 or more, m-valent chain saturated hydrocarbons in which some or all of the hydrogen atoms may be substituted with fluorine atoms and may have etheric oxygen atoms between carbon-carbon atoms. In the case where n is 2 or more, n (R ¹ -O) may be the same or different. Q ¹ in the formula (1) is a single bond or a divalent linking group having no cyclic structure, R ^f is a C 1-8 perfluoroalkyl group, or —CHR ^f1 R ^f2 and R The composition according to claim 2, wherein ^f1 and ^Rf2 are each a perfluoroalkyl group having 1 to 4 carbon atoms. Q ² in the formula (2) is a single bond or a divalent linking group having no cyclic structure, and Z is a group consisting of —OH, —COOH, —Si (OH) ₃ , and —SO ₃ H. The composition of Claim 3 which is at least 1 sort (s) chosen from.   The composition according to any one of claims 1 to 6, further comprising an isocyanate group-containing silane coupling agent.   The composition according to any one of claims 1 to 7, which is a water slide agent.   A coating liquid comprising the composition according to any one of claims 1 to 8 and a solvent.   The coating liquid according to claim 9, wherein the solvent is a nonflammable solvent.   An article having a film formed from the composition according to any one of claims 1 to 8 on a surface of a substrate.