WO2019230598A1

WO2019230598A1 - Composition and article

Info

Publication number: WO2019230598A1
Application number: PCT/JP2019/020720
Authority: WO
Inventors: 信行音澤
Original assignee: Ａｇｃ株式会社
Priority date: 2018-05-30
Filing date: 2019-05-24
Publication date: 2019-12-05
Also published as: JP2021130725A

Abstract

The present invention provides: a composition which is capable of forming a coating film that has both durability and water sliding properties; and an article having a coating film which is formed using this composition and has both durability and water sliding properties. A composition that contains: a copolymer A which has a unit based on a monomer having a polyorganosiloxane group and a unit based on a monomer having a blocked isocyanate group; and a copolymer B which has a unit based on a fluoroolefin, and which is configured such that at least one of the units that constitute the copolymer B has a hydroxyl group. With respect to this composition, the content of the polyorganosiloxane group in the copolymer A is 20-45% by mass.

Description

Compositions and articles

The present invention relates to a composition and an article, and more particularly to a composition capable of forming a film having both durability and water slidability and an article having a film formed using the composition.

Conventionally, in various technical fields, it has been demanded that water droplets adhering to the surface of a substrate are easily slid, that is, imparting water slidability. As a method for imparting water slidability, generally, a water slidable film is formed on the surface of a substrate, and technical development relating to a composition for forming such a film has been made.

Conventionally, a polymer having a polyorganosiloxane group has been used in the composition for obtaining the above-mentioned water-slidable film. Moreover, in such a composition, it is calculated | required that the film obtained has durability, such as a weather resistance. Therefore, for example, Patent Document 1 discloses that a graft copolymer obtained by graft-polymerizing a monomer having a polyorganosiloxane group together with other monomers at a predetermined ratio to a fluororesin having a radical polymerizable unsaturated bond portion. A polymer is disclosed. However, although the coating obtained in Patent Document 1 has durability, it has insufficient lubricity.

Japanese Patent No. 3830664

The present invention has been made from the above viewpoint, and is a composition capable of forming a film having both durability and water slidability, and a film having both durability and water slidability formed using the composition. It aims at providing the article | item which has.

The gist of the present invention is as follows.
[1] A copolymer A having a unit based on a monomer having a polyorganosiloxane group and a unit based on a monomer having a blocked isocyanate group, and a copolymer B having a unit based on a fluoroolefin , At least one of the units constituting the copolymer B is a composition containing a copolymer B having a hydroxyl group,
A composition characterized in that the content of the polyorganosiloxane group in the copolymer A is 20 to 45% by mass.
[2] The composition according to [1], wherein the content of the blocked isocyanate group in the copolymer A is 0.20 to 2.00 mmol / g.
[3] The composition according to [1] or [2], wherein the monomer having a polyorganosiloxane group is (meth) acrylate or (meth) acrylamide having a polyorganosiloxane group.
[4] The composition according to any one of [1] to [3], wherein the monomer having a blocked isocyanate group is (meth) acrylate or (meth) acrylamide having a blocked isocyanate group.
[5] The composition according to any one of [1] to [4], wherein the copolymer A has a number average molecular weight of 5,000 to 100,000.
[6] Copolymer B has a unit based on a fluoroolefin having no hydroxyl group and a unit based on a monomer having no fluorine atom and having a hydroxyl group, according to any one of [1] to [5] The composition as described.
[7] The composition according to any one of [1] to [6], wherein the mass ratio of the copolymer A and the copolymer B is in the range of 1/99 to 40/60.
[8] The copolymer A has a hydrocarbon group having 3 to 16 carbon atoms which has neither a polyorganosiloxane group nor a blocked isocyanate group and may have an etheric oxygen atom between carbon atoms. The composition according to any one of [1] to [7], further comprising a unit based on a monomer.
[9] The composition according to any one of [1] to [8], further comprising a liquid medium.
[10] An article comprising a base material and a film formed on the surface of the base material using the composition according to any one of [1] to [9].
[11] A copolymer having a unit based on a monomer having a polyorganosiloxane group and a unit based on a monomer having a blocked isocyanate group, wherein the polyorganosiloxane group is contained in the copolymer A copolymer having an amount of 20 to 45% by mass.
[12] The copolymer according to [11], wherein the content of the blocked isocyanate group in the copolymer is 0.20 to 2.00 mmol / g.
[13] The copolymer according to [11] or [12], wherein the monomer having a polyorganosiloxane group is (meth) acrylate or (meth) acrylamide having a polyorganosiloxane group.
[14] The copolymer according to any one of [11] to [13], wherein the monomer having a blocked isocyanate group is (meth) acrylate or (meth) acrylamide having a blocked isocyanate group.
[15] The copolymer according to any one of [11] to [14], which has a number average molecular weight of 5,000 to 100,000.

According to the present invention, it is possible to provide a composition capable of forming a film having both durability and water slidability, and an article having a film having both durability and water slidability formed using the composition.
The article is preferably a facility, apparatus, instrument, component or the like that has water slidability and chemical resistance, in particular, alkali resistance is desired or required. By providing water slidability to the surface of the article, it is possible to obtain mud drop-off property (a property in which aqueous mud is easy to fall off) and ice / frost adhesion prevention property (a property in which ice and frost are difficult to adhere).

In this specification, the meanings of the following terms are as follows.
“Unit based on monomer” is a general term for an atomic group directly formed by polymerizing one monomer molecule and an atomic group obtained by chemically converting a part of the atomic group. . A unit based on a monomer is also referred to as a monomer unit.

The compound or group represented by the formula is also expressed as a compound or group with the number of the formula, for example, the compound represented by the formula (1) is also expressed as the compound (1).
“˜” representing a numerical range is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
“(Meth) acrylate” is a general term for methacrylate and acrylate. “(Meth) acrylic acid” is a general term for methacrylic acid and acrylic acid. The same applies to “(meth) acrylamide”.
The “polyorganosiloxane group” is a monovalent organic group represented by —SiR ₂ — [OSiR ₂ ] _n —R (R is a monovalent organic group, n is an integer of 2 or more).

[Composition]
The composition of the present invention comprises a copolymer A having a unit based on a monomer having a polyorganosiloxane group and a unit based on a monomer having a blocked isocyanate group, and a hydroxyl group having a unit based on a fluoroolefin. Containing copolymer B. In the composition of the present invention, the content of the polyorganosiloxane group in the copolymer A is 20 to 45% by mass.

As the monomer having a polyorganosiloxane group, (meth) acrylate or (meth) acrylamide is preferable, and (meth) acrylate is more preferable. As the monomer having a blocked isocyanate group, (meth) acrylate or (meth) acrylamide is preferable, and (meth) acrylate is more preferable.

In the composition of the present invention, an isocyanate group is produced from the blocked isocyanate group of the copolymer A under predetermined conditions, and the hydroxyl group of the isocyanate group and the copolymer B is urethane-bonded to form a cured product. It is a curable composition. A film is formed by applying and curing the composition of the present invention on a substrate. The coating film thus obtained has excellent water slidability because the content of the polyorganosiloxane group in the copolymer A is in the above range. Further, the copolymer B is a component that contributes to the durability of the coating, and the copolymer A and the copolymer B are bonded by a urethane bond, so that the durability of the coating, for example, weather resistance and abrasion resistance are improved. improves.

The composition of the present invention preferably further contains a liquid medium, and may contain optional components described later. Hereinafter, each component contained in the composition will be described.

In the following description, a monomer having a polyorganosiloxane group, which is a monomer used for the copolymer A, is a monomer (a1), and a monomer having a blocked isocyanate group is a monomer ( It is also called a2). The fluoroolefin which is a monomer used for the copolymer B is also referred to as a fluoroolefin (b1). Furthermore, a unit based on the monomer (a1) is also referred to as a unit (a1). For other units, the symbols used for the monomers may be used for the units as they are.

<Copolymer A>
Copolymer A contains units (a1) and units (a2), and the content of polyorganosiloxane groups in copolymer A is 20 to 45% by mass.

When the content of the polyorganosiloxane group in the copolymer A is in the above range, the coating obtained using the composition can achieve both sliding properties and durability. The content of the polyorganosiloxane group is preferably 23% by mass or more, and more preferably 25% by mass or more. The content of the polyorganosiloxane group is preferably 42% by mass or less, and more preferably 40% by mass or less.

If the copolymer A contains a blocked isocyanate group, the film obtained using the composition can achieve both water slidability and durability. The content of the blocked isocyanate group is preferably 0.20 mmol / g or more from the viewpoint that a sufficient number of bonding points of urethane bonds with the copolymer B can be obtained and the durability of the resulting film is easily improved. 0.50 mmol / g or more is more preferable, 0.55 mmol / g or more is more preferable, and 0.60 mmol / g or more is particularly preferable. The content of the blocked isocyanate group is preferably 2.00 mmol / g or less, more preferably 1.75 mmol / g or less, from the viewpoint of maintaining the content of the polyorganosiloxane group in the above range. More preferred is mmol / g or less, and particularly preferred is 1.60 mmol / g or less.

In addition, it is preferable that the unit (a1) does not have a blocked isocyanate group. The unit (a2) preferably has no polyorganosiloxane group. That is, in the copolymer A, it is preferable that only the unit (a1) has the polyorganosiloxane group and only the unit (a2) has the blocked isocyanate group.

Copolymer A has units based on monomers other than monomer (a1) and monomer (a2) (hereinafter referred to as unit (a3)) in addition to unit (a1) and unit (a2). May be. The monomer which comprises each unit of the copolymer A in this invention is demonstrated below.

(Monomer (a1))
As the monomer (a1), a (meth) acrylate having a polyorganosiloxane group (hereinafter referred to as (meth) acrylate (a1-1)) and a (meth) acrylamide having a polyorganosiloxane group (hereinafter referred to as (meta) ) (Referred to as acrylamide (a1-2)), more preferably (meth) acrylate (a1-1).

(Meth) acrylate (a1-1) and (meth) acrylamide (a1-2) preferably do not have a blocked isocyanate group. Examples of such (meth) acrylate (a1-1) and (meth) acrylamide (a1-2) include (meth) acrylate (a11) and (meta) represented by formula (a11) and formula (a12), respectively. ) Acrylamide (a12) is preferred.

In formulas (a11) and (a12), R ¹ is a hydrogen atom or a methyl group, R ¹² is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, Q ¹ is a single bond or a divalent organic group, and n is 2 or more Is an integer. Examples of the substituent include a halogen atom and an alkoxy group having 1 to 10 carbon atoms.

R ¹ is preferably a methyl group from the viewpoint of copolymerization. R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently preferably an alkyl group having 1 to 8 carbon atoms or a fluoroalkyl group, more preferably a methyl group or a trifluoropropyl group, and particularly preferably a methyl group. preferable. In terms of easy synthesis, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are preferably the same. Depending on the required physical properties, different groups may be introduced into a part thereof.

In the present specification, unless otherwise specified, the alkyl group and the alkylene group may be linear, branched, cyclic, or a combination of these structures. The same applies to the alkyl group that the alkoxy group has. In addition, the carbon number when these groups have a branched structure means the carbon number of the skeleton including the branched portion. The carbon number in the case of having a cyclic structure means the carbon number of the skeleton including the cyclic portion.

N is preferably 10 or more, more preferably 20 or more, still more preferably 30 or more, and particularly preferably 50 or more, from the viewpoint of water slidability of the resulting coating. Further, from the viewpoint of compatibility with other resins, n is preferably 150 or less, and more preferably 100 or less.

Q ¹ represents an ether bond (—O—), an ester bond (—C (═O) O— or —OC (═O) —), an amide bond (—C (═O) NH—) between carbon atoms. A substituted or unsubstituted divalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a urethane bond (—NHC (═O) —O—) is preferable. Examples of the substituent include a halogen atom and an alkoxy group having 1 to 10 carbon atoms. Q ¹ is more preferably an alkylene group having 2 to 4 carbon atoms, and particularly preferably an alkylene group having 2 or 3 carbon atoms.

In (meth) acrylamide (a12), R ¹² is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and preferably a hydrogen atom.

As the (meth) acrylate (a11), a particularly preferable compound is represented by the following formula (a11-1). A particularly preferable compound as (meth) acrylamide (a12) is represented by the following formula (a12-1). In formula (a11-1) and formula (a12-1), R ¹ is a hydrogen atom or a methyl group, m is 2 or 3, and n1 is 50 to 100. In formula (a12-1), R ¹² represents a hydrogen atom.

In the copolymer A, the monomer (a1) may be used alone or in combination of two or more. When the monomer (a1) is (meth) acrylate (a1-1), one of them may be used, or two or more thereof may be used. The same applies to (meth) acrylamide (a1-2).

The content of the unit (a1) in the copolymer A is preferably 0.2 to 5 mol%, more preferably 1.0 to 3.5 mol based on all units in the copolymer A. %, More preferably 1.5 to 3.0 mol%. The content of the unit (a1) in the copolymer A is the same as the ratio of the monomer (a1) to the total monomers used for the polymerization. By setting the ratio of the monomer (a1) to the total monomer used in the polymerization within the above range, the content of the polyorganosiloxane group and the content of the blocked isocyanate group in the copolymer A are within the above range. Easy to adjust.

(Monomer (a2))
As the monomer (a2), (meth) acrylate having a blocked isocyanate group (hereinafter referred to as (meth) acrylate (a2-1)) and (meth) acrylamide having a blocked isocyanate group (hereinafter referred to as (meth) acrylate) ) Acrylamide (a2-2)) is preferred, and (meth) acrylate (a2-1) is more preferred.

(Meth) acrylate (a2-1) and (meth) acrylamide (a2-2) preferably have no polyorganosiloxane group. Examples of such (meth) acrylate (a2-1) and (meth) acrylamide (a2-2) include (meth) acrylate (a21) and (meta) represented by formula (a21) and formula (a22), respectively. ) Acrylamide (a22) is preferred.

In the formulas (a21) and (a22), R ⁷ is a hydrogen atom or a methyl group, R ¹³ is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms, and R ⁸ is a hydrogen atom or a carbon number 1 1 to 3 saturated hydrocarbon groups, and Q ² is a single bond or a divalent organic group. R ⁹ is a residue of a blocking agent that reacts with an isocyanate group to form a blocked isocyanate group.

R ⁷ is preferably a methyl group from the viewpoint of copolymerization. R ⁸ is preferably a hydrogen atom from the viewpoint of reactivity. Q ² can be specifically the same as Q ¹ in formula (a11) and formula (a12), and is preferably an ethylene group or a propylene group. R ¹³ is preferably a hydrogen atom.

Examples of the blocking agent include alcohol, phenol, caprolactam, oxime, active methylene compound, amino compound having an active hydrogen atom, and the like. Specifically, ε-caprolactam, 2-butanone oxime, 1,2,4-triazole, pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, diisopropylamine, diethyl malonate and the like are preferable, and 2-butanone oxime Pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, and ε-caprolactam are more preferable.

Specific examples of (meth) acrylate (a21) include 2-butanone oxime adduct of 2-isocyanatoethyl (meth) acrylate, pyrazole adduct of 2-isocyanatoethyl (meth) acrylate, 2-isocyanatoethyl (meth) 3,5-dimethylpyrazole adduct of acrylate, 3-methylpyrazole adduct of 2-isocyanatoethyl (meth) acrylate, ε-caprolactam adduct of 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate 2-butanone oxime adduct, 3-isocyanatopropyl (meth) acrylate pyrazole adduct, 3-isocyanatopropyl (meth) acrylate 3,5-dimethylpyrazole adduct, 3-isocyanatopropyl 3-methylpyrazole adduct of (meth) acrylate, ε-caprolactam adduct of 3-isocyanatepropyl (meth) acrylate, 2-butanone oxime adduct of 4-isocyanatobutyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate Pyrazole adduct, 4-isocyanatobutyl (meth) acrylate 3,5-dimethylpyrazole adduct, 4-isocyanatobutyl (meth) acrylate 3-methylpyrazole adduct, 4-isocyanatobutyl (meth) acrylate ε- Examples include caprolactam adducts.

Of the above, (meth) acrylate (a21) is preferably a 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth) acrylate, a 2-butanone oxime adduct of 2-isocyanatoethyl (meth) acrylate, or the like. .

In the copolymer A, the monomer (a2) may be used alone or in combination of two or more. When the monomer (a2) is (meth) acrylate (a2-1), one of them may be used, or two or more thereof may be used. The same applies to (meth) acrylamide (a2-2).

The content of the unit (a2) in the copolymer A is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, still more preferably 20 with respect to the total units in the copolymer A. ~ 40 mol%. The content of the unit (a2) in the copolymer A is the same as the ratio of the monomer (a2) to the total monomers used for polymerization. By setting the ratio of the monomer (a2) to the total monomer used in the polymerization within the above range, the content of the polyorganosiloxane group and the content of the blocked isocyanate group in the copolymer A are within the above range. Easy to adjust.

(Monomer (a3))
The monomer (a3) is a monomer having neither a polyorganosiloxane group nor a blocked isocyanate group. The monomer (a3) is used to adjust the physical properties of the copolymer A, such as hardness and flexibility, the copolymer B contained in the composition, the compatibility with the liquid medium as an optional component, and film-forming properties. Used in

As the monomer (a3), there are (meth) acrylate (hereinafter referred to as (meth) acrylate (a3-1)), polyorganosiloxane group and blocked isocyanate, which have neither a polyorganosiloxane group nor a blocked isocyanate group. Preferred are (meth) acrylamide (hereinafter referred to as (meth) acrylamide (a3-2)), styrene, vinylidene chloride, N-methylpyrrolidone, etc. that do not have any of the groups, and (meth) acrylates (a3-1) and (meth) ) Acrylamide (a3-2) is more preferred, and (meth) acrylate (a3-1) is most preferred.

As the monomer (a3), a monomer (a3) having no reactive group is preferable, having a substituted or unsubstituted hydrocarbon group which may have an etheric oxygen atom between carbon atoms, The monomer (a3) having no reactive group is more preferred. The hydrocarbon group has 1 to 30 carbon atoms, and examples of the substituent include a halogen atom and an alkoxy group having 1 to 16 carbon atoms.

As the monomer (a3), a monomer (a3) having a hydrocarbon group having 3 to 16 carbon atoms which may have an etheric oxygen atom between carbon atoms is preferable from the viewpoint of compatibility. As such a monomer (a3), (meth) acrylate (a31) represented by the formula (a31) and (meth) acrylamide (a32) represented by the formula (a32) are preferable.
CH ₂ = CR ¹⁰ -COOR ¹¹ (a31)
CH ₂ = CR ¹⁰ -CONR ¹⁴ R ¹¹ (a32)

In formulas (a31) and (a32), R ¹⁰ is a hydrogen atom or a methyl group, R ¹⁴ is a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms, and R ¹¹ is an etheric group between carbon atoms. A hydrocarbon group having 3 to 16 carbon atoms which may have an oxygen atom.

R ¹⁰ is preferably a methyl group from the viewpoint of copolymerization. R ¹⁴ is preferably a hydrogen atom. R ¹¹ is an alkyl group having 3 to 16 carbon atoms which may have an etheric oxygen atom between carbon atoms, an aryl group having 6 to 16 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, or the like. Among these, as R ¹¹ , a linear alkyl group having 4 to 12 carbon atoms, a cyclohexyl group, a tetrahydrofurfuryl group, and a benzyl group are preferable, and a benzyl group is particularly preferable.

In copolymer A, the monomer (a3) may be used alone or in combination of two or more. When the monomer (a3) is (meth) acrylate (a3-1), one of them may be used, or two or more thereof may be used. The same applies to (meth) acrylamide (a3-2).

The content of the unit (a3) in the copolymer A is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, still more preferably 30 with respect to the total units in the copolymer A. ˜60 mol%. The content of the unit (a3) in the copolymer A is the same as the ratio of the monomer (a3) to the total monomers used for the polymerization. By setting the ratio of the monomer (a3) to the total monomer used in the polymerization within the above range, the content of the polyorganosiloxane group and the content of the blocked isocyanate group in the copolymer A are within the above range. While maintaining, it is easy to adjust the physical properties such as the hardness and flexibility of the copolymer A, the compatibility with the copolymer B contained in the composition and the liquid medium as an optional component.

In the copolymer A, the number average molecular weight is preferably 5,000 or more and 100,000 or less, more preferably 10,000 or more and 20,000 or less, from the viewpoint of durability of the obtained film and compatibility in the composition. In addition, the number average molecular weight of the copolymer A and the copolymer B in this specification is a polystyrene conversion molecular weight obtained by measuring by gel permeation chromatography using a calibration curve prepared using a standard polystyrene sample. is there.

The glass transition temperature (Tg) of the copolymer A is preferably −20 to 100 ° C., more preferably 0 to 60 ° C. When the Tg is not less than the lower limit of the above range, the water slidability is excellent, and when the Tg is not more than the upper limit of the above range, the coating is excellent in flexibility and cracks and the like can be prevented.

Copolymer A can be obtained by performing a polymerization reaction of a monomer in a polymerization solvent using a known method. That is, in the reaction vessel, monomer (a1) and monomer (a2) and optionally monomer (a3), preferably (meth) acrylate (a1-1) and (meth) acrylate (a2 -1) and, optionally, (meth) acrylate (a3-1) are added in such a proportion that the content of polyorganosiloxane groups and the content of blocked isocyanate groups in the copolymer A thus obtained are predetermined values. . Furthermore, a polymerization solvent is added, and a copolymer A is obtained through a step of adding a polymerization initiator, a chain transfer agent, and the like as necessary to cause a copolymerization reaction.

The polymerization solvent can be used without any particular limitation; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; alcohols such as methanol and 2-propyl alcohol; esters such as ethyl acetate and butyl acetate; diisopropyl ether, tetrahydrofuran Ethers such as dioxane, ethylene glycol, propylene glycol, or glycol ethers such as ethyl ether or methyl ether of dipropylene glycol and derivatives thereof; aliphatic hydrocarbons; aromatic hydrocarbons; perchloroethylene, trichloro- Halogenated hydrocarbons such as 1,1,1-ethane, trichlorotrifluoroethane, dichloropentafluoropropane; dimethylformamide; N-methyl-2-pyrrolidone; butyroacetone; Sulfoxide (DMSO) and the like are preferably used.

In the polymerization reaction for obtaining copolymer A, the total concentration of monomers in all of the raw materials (including the polymerization solvent) is preferably 5 to 60% by mass, and more preferably 10 to 40% by mass.

In the polymerization reaction for obtaining the copolymer A, it is preferable to use a polymerization initiator. The concentration of the polymerization initiator in the solvent is preferably 0.1 to 1.5 parts by mass with respect to 100 parts by mass of the total amount of monomers.

As the radical polymerization initiator to be used, conventionally known initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobiscyclohexane carbonate nitrile, 2,2′-azobis Azo initiators such as (2,4-dimethylvaleronitrile) and 2,2′-azobis (2-methylbutyronitrile); ketone peroxides such as cyclohexanone peroxide, hydrous such as tert-butyl hydroperoxide Peroxides, diacyl peroxides such as benzoyl peroxide, dialkyl peroxides such as di-tert-butyl peroxide, peroxyketals such as 2,2-di- (tert-butylperoxy) butane, tert -Al, such as butyl peroxypivalate (PBPV) Helper esters, peroxide initiators percarbonates such as diisopropyl peroxydicarbonate; and the like.

Further, when it is necessary to adjust the number average molecular weight of the copolymer A, a conventionally known chain transfer agent may be added as necessary. By using a chain transfer agent, there is an effect of increasing the total concentration of monomers in the solvent. Examples of chain transfer agents include alkyl mercaptans such as tert-dodecyl mercaptan, n-dodecyl mercaptan, stearyl mercaptan; aminoethanethiol, mercaptoethanol, 3-mercaptopropionic acid, 2-mercaptopropionic acid, thiomalic acid, thioglycolic acid, 3 , 3'-dithio-dipropionic acid, 2-ethylhexyl thioglycolate, n-butyl thioglycolate, methoxybutyl thioglycolate, ethyl thioglycolate, 2,4-diphenyl-4-methyl-1-pentene, four Carbon chloride and the like are preferred. The amount of chain transfer agent used is preferably 0 to 2 parts by mass with respect to 100 parts by mass of the total amount of monomers.

The reaction temperature in the polymerization reaction is preferably in the range from room temperature to the boiling point of the reaction mixture. From the viewpoint of efficiently using the polymerization initiator, it is preferably at least the half-life temperature of the polymerization initiator, more preferably from 30 to 90 ° C.

The composition of the present invention preferably contains the copolymer A so that the mass ratio of the copolymer A and the copolymer B is in the range of 1/99 to 40/60. When the mass ratio of the copolymer A and the copolymer B is 1/99 or more, the water slidability of the resulting coating is sufficiently obtained. When the mass ratio of the copolymer A and the copolymer B is 40/60 or less, the resulting coating has sufficient durability. The mass ratio of the copolymer A and the copolymer B is more preferably 2/98 or more, and further preferably 3/97 or more. The mass ratio of the copolymer A and the copolymer B is more preferably 30/70 or less, further preferably 20/80 or less, and particularly preferably 10/90 or less.

<Copolymer B>
Copolymer B is a copolymer having units based on fluoroolefin, and at least one of the units constituting the copolymer has a hydroxyl group. Copolymer B has a unit (b1), and can provide durability to the film obtained using the composition. Since at least one of the monomers constituting the unit of the copolymer B has a hydroxyl group, the copolymer B and the copolymer A are urethane-bonded at the time of curing, and a film having both water slidability and durability is obtained. It is done.

The copolymer B preferably has a unit based on a monomer having no fluorine atom, in addition to the unit (b1). In the copolymer B, the unit (b1) may have a hydroxyl group, but preferably does not have a hydroxyl group. In that case, the copolymer B preferably has units based on the unit (b1) and a monomer having no fluorine atom and having a hydroxyl group (hereinafter also referred to as monomer (b2)). Copolymer B may further have a unit based on a monomer having neither a fluorine atom nor a hydroxyl group (hereinafter also referred to as “monomer (b3)”).

The proportion of the unit (b1) in the copolymer B is preferably from 30 to 70 mol%, more preferably from the viewpoint of imparting durability to the coating film obtained, based on the total units in the copolymer B. It is 40 to 60 mol%, more preferably 45 to 55 mol%.

Further, the hydroxyl value in the copolymer B is preferably 10 mgKOH / g or more from the viewpoint that a sufficient number of urethane bond points with the copolymer A can be obtained and the durability of the resulting film is easily improved. / G or more is more preferable. The hydroxyl value in the copolymer B is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less, from the viewpoint of compatibility with the copolymer A contained in the composition and the liquid medium which is an optional component. Each monomer constituting the above unit of the copolymer B will be described below.

(Fluoroolefin (b1))
The fluoroolefin (b1) is a compound in which part or all of the hydrogen atoms bonded to the carbon atoms of the olefin hydrocarbon are substituted with fluorine atoms. The fluoroolefin (b1) may have a halogen atom other than a fluorine atom such as chlorine. The number of fluorine atoms contained in the fluoroolefin (b1) is preferably 2 or more, more preferably 2 to 6, and still more preferably 3 to 4. When the number of fluorine atoms is 2 or more, durability such as weather resistance of a film obtained using the composition of the present invention is sufficient.

Examples of the fluoroolefin (b1) include tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, and the like. Tetrafluoroethylene and chlorotrifluoroethylene are particularly preferred. In the copolymer B, the fluoroolefin (b1) may be used alone or in combination of two or more.

The amount of the fluoroolefin (b1) used when polymerizing the copolymer B is preferably 30 to 70 mol%, more preferably 40 to 60 mol%, and still more preferably 45 to the total amount of monomers used. ~ 55 mol%. By setting the amount of the fluoroolefin (b1) within this range, the composition of the copolymer B falls within the above range.

When the amount of the fluoroolefin (b1) used for the polymerization is not less than the lower limit, durability such as weather resistance is sufficient, and when it is not more than the upper limit, the solubility in a liquid medium or a diluent is good.

(Monomer (b2))
The monomer (b2) is a monomer having a hydroxyl group and no fluorine atom, and having a double bond copolymerizable with the fluoroolefin (b1).

Specifically, the monomer (b2) is preferably a monomer having a structure of the formula (b21).
CH ₂ = CR ²¹ (CH ₂ ) _n2 -Q ³ -R ²² -OH (b21)

In formula (b21), R ²¹ represents a hydrogen atom or a methyl group, n2 represents 0 or 1, Q ³ represents an oxygen atom, a group represented by —C (═O) O—, or —OC (═ O) —, and R ²² is an alkylene group having 2 to 20 carbon atoms which may have a branched structure or a ring structure.

In the monomer (b21), R ²² is more preferably a linear alkylene group. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. In the monomer (b2), Q ³ is preferably an oxygen atom.

Examples of the monomer (b2) include hydroxyalkyl vinyl ethers, hydroxyalkyl carboxylic acid vinyl esters, hydroxyalkyl allyl ethers, hydroxyalkyl carboxylic acid allyl esters, and (meth) acrylic acid hydroxyalkyl esters. .

Specific examples of the monomer (b2) include hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, hydroxymethyl vinyl ether and 4-hydroxybutyl vinyl ether; hydroxyalkyl allyl ethers such as hydroxyethyl allyl ether; (Meth) acrylic acid hydroxyalkyl esters such as acrylate) are preferred.

Hydroxyalkyl vinyl ethers are more preferable because of excellent copolymerizability and good durability such as weather resistance of the resulting film. In particular, 4-hydroxybutyl vinyl ether is preferable. In the copolymer B, the monomer (b2) may be used alone or in combination of two or more.

The content of the unit (b2) in the copolymer B is preferably 5 to 40 mol%, more preferably 8 to 35 mol%, based on all units in the copolymer B. By setting it as the said range, it is easy to adjust the ratio of the unit (b1) in the copolymer B, and a hydroxyl value to said range.

When the content of the monomer (b2) is not less than the lower limit, a coating film obtained by introducing a sufficient amount of hydroxyl groups into the copolymer B with an isocyanate group produced from the copolymer A and urethane bonding Sufficient durability can be imparted. Further, when the content of the monomer (b2) is not more than the upper limit value, when the composition of the present invention is used as a solution, the viscosity can be kept sufficiently low even if the solid content is high.

(Monomer (b3))
The monomer (b3) is a monomer other than the fluoroolefin (b1) and the monomer (b2), which has neither a fluorine atom nor a hydroxyl group. The monomer (b3) is an object of adjusting the physical properties such as hardness and flexibility, the copolymer A contained in the composition, the compatibility with the liquid medium as an optional component, and the glass transition temperature in the copolymer B. Used in The monomer (b3) is a monomer having a double bond copolymerizable with the fluoroolefin (b1) and the monomer (b2).

Specifically, the monomer (b3) is preferably a monomer having the structure of the formula (b31).

CH ₂ = CR ²³ (CH ₂ ) _n3 -Q ⁴ -R ²⁴ -H (b31)

In the formula (b31), R ²³ is a hydrogen atom or a methyl group, n3 is 0 or 1, Q ⁴ is an oxygen atom, a group represented by —C (═O) O—, or —OC (= O) —, and R ²⁴ is an alkylene group having 2 to 20 carbon atoms which may have a branched structure or a ring structure.

As the monomer (b3), alkyl vinyl ethers, alkyl carboxylic acid vinyl esters, alkyl allyl ethers, alkyl carboxylic acid allyl esters or (meth) acrylic acid esters are preferable.

Specific examples of the monomer (b3) are preferably ethyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether and the like. In the copolymer B, the monomer (b3) may be used alone or in combination of two or more.

In particular, when the monomer (b3) contains cyclohexyl vinyl ether, the copolymer B has high rigidity, is soluble in a solvent, is easy to apply, particularly when applied to film formation, and provides a hard film. More preferred. Moreover, when the monomer (b3) contains ethyl vinyl ether, it is more preferable in terms of toughness of the film.

The content of the unit (b3) in the copolymer B is preferably 0 to 45 mol%, more preferably 3 to 35 mol%, still more preferably 5 to 30 mol%, based on all units. . By making it into this range, while maintaining the proportion of the unit (b1) in the copolymer B and the hydroxyl value within the above range, the hardness and flexibility of the copolymer B, the copolymer A contained in the composition In addition, it is easy to adjust physical properties such as compatibility with a liquid medium which is an optional component and film toughness.

The content of the units (b2) and the units (b3) in the copolymer B is preferably 30 to 70 mol%, more preferably 40 to 60 mol% with respect to the total units in the copolymer B. The mol% is more preferably 45 to 55 mol%. By setting it as the said range, the composition of the copolymer B becomes said range.

The number average molecular weight of the copolymer B is preferably from 3,000 to 20,000, more preferably from 4,000 to 15,000, from the viewpoint of durability of the resulting film and compatibility in the composition. Moreover, when the number average molecular weight of the copolymer B is 9000 or less, when the composition of the present invention is used as a solution, the viscosity can be kept sufficiently low even if the solid content is high.

Copolymer B can be obtained by performing a polymerization reaction of a monomer in a polymerization solvent using a known method. That is, in the reaction vessel, the fluoroolefin (b1) and the monomer (b2), and optionally the monomer (b3), preferably the ratio of the unit (b1) and the hydroxyl value in the copolymer B obtained. Input at a rate that gives a predetermined value. Furthermore, a polymerization solvent is added, and a copolymer B is obtained through a process of adding a polymerization initiator, a chain transfer agent, and the like as necessary to cause a copolymerization reaction.

The type, amount, polymerization conditions, and the like of the polymerization solvent, polymerization initiator, chain transfer agent, etc. used for the polymerization of the copolymer B can be the same as those for the copolymer A.

The content of the copolymer B in the composition of the present invention is preferably such that the mass ratio of the copolymer A and the copolymer B is in the range of 1/99 to 40/60. A preferable range of the content is as shown for the copolymer A. In addition, the copolymer A and the copolymer B may each be used individually by 1 type, and may be used in combination of 2 or more type.

Further, the content ratio of the copolymer A and the copolymer B in the composition of the present invention is such that the hydroxyl group of the copolymer B is 0.5 to 2 with respect to 1 mol of the blocked isocyanate group of the copolymer A. The ratio of mol is preferable, and the ratio of 0.3 to 3 mol is more preferable.

(Liquid medium)
For example, the composition of the present invention is applied to the surface of a substrate and cured to be used as a film. In that case, it is usually preferable to contain a liquid medium. The liquid medium is preferably an organic solvent. The organic solvent is preferably an organic solvent that can dissolve both the copolymer A and the copolymer B.

The organic solvent is preferably at least one organic solvent selected from the group consisting of aromatic hydrocarbon solvents, ketone solvents, ether ester solvents, ester solvents, and weak solvents.

The ether ester solvent is a compound having both an ether bond and an ester bond in the molecule. The weak solvent is a solvent classified as a third type organic solvent in the Japanese Industrial Safety and Health Act.

As the aromatic hydrocarbon solvent, toluene, xylene, ethylbenzene, aromatic petroleum naphtha, tetralin, Solvesso # 100 (Exxon Chemical Co., Ltd. registered trademark), Solvesso # 150 (Exxon Chemical Co., Ltd. registered trademark) is preferable, and xylene More preferred are toluene, ethylbenzene.

As the ketone solvent, acetone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, diisobutyl ketone, cyclohexanone and isophorone are preferable.

As the ether ester solvent, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, and methoxybutyl acetate are preferable.

Weak solvent is a group consisting of gasoline, coal tar naphtha (including solvent naphtha), petroleum ether, petroleum naphtha, petroleum benzine, turpentine oil, mineral spirit (including mineral thinner, petroleum spirit, white spirit and mineral turpentine). It is the solvent which consists of 1 or more types chosen from these.

As the weak solvent, a mineral spirit (including mineral thinner, petroleum spirit, white spirit, and mineral turpentine) is preferable because its flash point is room temperature or higher.

As the ester solvent, methyl acetate, ethyl acetate, n-propyl acetate, isobutyl acetate, and t-butyl acetate are preferable.

Of these, the organic solvent is more preferably an aromatic hydrocarbon solvent, and the aromatic hydrocarbon solvent is preferably xylene, toluene, or ethylbenzene. More preferably, the solvent contains 10 to 100% by mass of ethylbenzene and 0 to 90% by mass of xylene, and the content of ethylbenzene is more preferably 10 to 80% by mass.

Further, from the viewpoint of reducing the environmental load, as an organic solvent, a solvent corresponding to PRTR (Pollutant Release and Transfer Register) method and HAPs (Hazardous Air Polrants) regulation, that is, an organic solvent not containing an aromatic or a weak solvent Can also be used.

Specifically, ketone solvents, ether ester solvents, weak solvents such as paraffinic solvents and naphthenic solvents that do not comply with the PRTR method and HAPs regulations can be used.

The liquid medium may consist of only one type of solvent or a mixed solvent of two or more types. The polymerization solvent used for the polymerization of the copolymer A and the copolymer B may be used as it is as a liquid medium of the composition. Moreover, it is good also as a liquid medium of a composition combining the organic solvent etc. which were added separately from the polymerization solvent.

When the composition of the present invention contains a liquid medium, the content of the liquid medium is preferably 100 to 9900 parts by mass as the amount of the liquid medium with respect to 100 parts by mass in total of the copolymer A and the copolymer B, and 200 More preferred is 900 parts by mass. In other words, the total content of the copolymer A and the copolymer B in the composition is preferably 1 to 50% by mass, and more preferably 10 to 33% by mass.

In the composition of the present invention, the copolymer A and the copolymer B are preferably prepared in the above-mentioned mass ratio, and if necessary, a liquid medium and optional components shown below are appropriately added and mixed. can get.

The composition of the present invention may further comprise a curing catalyst, a colorant, a matting agent, an ultraviolet absorber, a light stabilizer, a leveling agent, a surfactant, an anti-sagging agent, or the like, as long as the effects of the present invention are not impaired. A silane coupling agent for improving the adhesion of the coating may be included. Furthermore, you may mix | blend other resin well-known as resin for coating materials, such as a cellulose acetate butyrate, a nitrocellulose, an acrylic resin, a polyester resin, an epoxy resin.

[Goods]
The article of the present invention has a base material and a film formed on the surface of the base material using the composition of the present invention (hereinafter also referred to as “the present composition”). As described above, the coating film comprises a cured product of the present composition. Here, the cured product of the present composition is derived from the present composition formed after applying the present composition. In addition, a film may be formed in part or all according to the surface shape of a base material.

The coating film made of the cured product of the present composition has excellent water slidability because the ratio of the polyorganosiloxane group to the total amount of the copolymer A is in the above range, and the copolymer A and the copolymer B are urethanes. Since they are bonded by bonding, the coating has excellent durability, for example, weather resistance and wear resistance.

The water slidability on the coating surface of the article of the present invention can be evaluated using, for example, a water falling angle and a water falling speed measured by the following method as indices.

(Water drop angle (5 μL), (10 μL), (20 μL))
Under an environment of 25 ° C. and 40% RH, when 5 μL of distilled water is dropped onto the surface of the coating and tilted at a tilt rate of 1 degree / second, the angle when moved 1 mm is defined as the water drop angle (5 μL) To do. For example, DMo-501SA manufactured by Kyowa Interface Science Co., Ltd. is used to measure the water falling angle (5 μL). Similarly, a water falling angle (10 μL) and a water falling angle (20 μL) obtained by changing the dropping amount of distilled water to 10 μL and 20 μL are used for evaluation.

(Water falling speed (20 μL, 30 degrees))
In a 25 ° C., 40% RH environment, 20 μL of distilled water is dropped onto the surface of the coating, and the rate at which the water drops fall when tilted to 30 degrees is defined as the water falling speed (20 μL, 30 degrees). The water falling speed (20 μL, 30 degrees) is measured, for example, by taking a picture of a water drop falling with a high speed camera and using DMo-501SA manufactured by Kyowa Interface Science Co., Ltd.

The water falling angle (5 μL) on the coating surface of the article of the present invention is preferably 35 degrees or less, more preferably 25 degrees or less, and particularly preferably 20 degrees or less. The water falling angle (10 μL) is preferably 20 degrees or less, more preferably 15 degrees or less, and particularly preferably 10 degrees or less. The water falling angle (20 μL) is preferably 15 degrees or less, and more preferably 10 degrees or less. The water falling speed (20 μL, 30 degrees) on the coating surface of the article of the present invention is preferably 20 mm / min or more, more preferably 25 mm / min or more, and particularly preferably 50 mm / min or more.

The article of the present invention can be produced, for example, by a wet coating method in which the composition containing a liquid medium is applied to the surface of a substrate to obtain a coating film, and the resulting coating film is cured by heating or the like to form a coating film. Hereinafter, this composition is demonstrated as what contains a liquid medium.

As a method of applying the present composition to the substrate surface, a known wet coating method can be used, for example, dip coating method, spin coating method, wipe coating method, spray coating method, squeegee coating method, die coating method, ink jet method, Examples thereof include a flow coating method, a roll coating method, a casting method, a Langmuir / Blodgett method, and a gravure coating method.

In order to cure the coating film made of the present composition, it is necessary to dissociate the blocked isocyanate group of copolymer A to form an isocyanate group, to make a urethane reaction with the hydroxyl group of copolymer B, and to remove the liquid medium. It is. The dissociation of the blocked isocyanate group is usually performed by heating. The dissociation temperature depends on the type of the blocked isocyanate group, but in the case of the blocked isocyanate group exemplified above, the dissociation temperature can be dissociated in the range of about 100 to 150 ° C. The liquid medium is preferably removed by heating at a temperature equal to or higher than the boiling point of the liquid medium.

Therefore, the heating temperature of the coating film is set in consideration of the dissociation temperature of the blocked isocyanate group and the boiling point of the liquid medium. However, the temperature for removing the liquid medium can be adjusted to be lower than the removal temperature at atmospheric pressure by conditions such as reduced pressure, so if the boiling point of the liquid medium is higher than the dissociation temperature of the blocked isocyanate group, Alternatively, the liquid medium may be removed.

Usually, the urethane reaction and the removal of the liquid medium can proceed simultaneously. As a condition for curing the coating film made of the present composition, the temperature is preferably from 100 to 180 ° C, more preferably from 120 to 150 ° C. The curing time is preferably 5 minutes to 2 hours, more preferably 15 minutes to 1 hour.

The thickness of the coating film to be obtained is not particularly limited as long as durability and sliding properties are sufficiently obtained, and is preferably 0.01 to 100 μm. When the thickness of the coating is increased, the wear durability is lowered. When the coating is thin, it is difficult to obtain a uniform coating. The thickness of the coating can be measured, for example, by observing a cross-sectional image of the coating with a scanning electron microscope.

The base material is not particularly limited as long as it is a base material that is required to impart lubricity. Examples of the material of the base material include inorganic materials such as concrete, natural stone, and glass; metals such as iron, stainless steel, aluminum, copper, brass, and titanium; and organic materials such as plastic, rubber, adhesive, and wood. Further, the present invention can also be applied to a substrate made of a material such as fiber reinforced plastic (FRP), resin reinforced concrete, or fiber reinforced concrete, which is an organic-inorganic composite material.

In addition, depending on the material of the base material, considering the adhesive strength between the base material and the coating or the rust prevention function, an undercoat layer such as epoxy paint, acrylic urethane paint, silane coupling agent, intermediate coat layer, etc. It is preferable to select appropriately.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the embodiments and examples described below. Examples 1 to 8 are Examples, Example 9 is a Reference Example, and Examples 10 to 16 are Comparative Examples.

(Production of Copolymer A and Copolymer Acf)
Using the (meth) acrylate, polymerization initiator, chain transfer agent, and polymerization solvent shown below, the copolymer A for the composition of the example and the copolymer for the comparative example not in the category of the copolymer A Combined Acf was produced.

(Meth) acrylate (a1-1); KF-2012 (manufactured by Shin-Etsu Chemical Co., Ltd., in formula (a11-1, R ¹ is methyl group, m is 3, polyorganosiloxane group equivalent; 4600 g / mol) Compound),
(Meth) acrylate (a2-1); 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl methacrylate (hereinafter referred to as “MOIBP”)
(Meth) acrylate (a3); benzyl methacrylate (hereinafter referred to as “BzMA”)
Radical polymerization initiator; 2,2'-azobis (2-methylbutyronitrile)
Chain transfer agent; n-dodecyl mercaptan (hereinafter referred to as “DoSH”)
Polymerization solvent; Toluene

A glass reactor having an internal volume of 100 mL is charged with (meth) acrylate, a polymerization initiator, a chain transfer agent, and a polymerization solvent in the mass composition (g) shown in Table 1, and dissolved in the liquid by pressurizing and purging with nitrogen. Oxygen was removed. The temperature of the reactor was raised to 60 ° C., and the reaction was continued while maintaining the temperature. After 48 hours, the reaction was stopped by cooling the reactor with water. The polymerization solvent was removed from the resulting reaction solution to obtain copolymers A-1 to A-4 and copolymers Acf-1 to Acf-2.

For the obtained copolymers A-1 to A-4 and copolymers Acf-1 to Acf-2, the ratio (mass%) of polyorganosiloxane groups in the copolymer was calculated, and the number average molecular weight was measured. did. The results are also shown in Table 1. In Table 1, the polyorganosiloxane group is indicated as “POS group”. In Table 1, the blank indicates the preparation amount “0”.

(Production of copolymer B)
A stainless steel pressure resistant reactor with an internal volume of 2500 mL equipped with a stirrer, 587 g of xylene, 168 g of ethanol, 206 g of ethyl vinyl ether (EVE), 129 g of 4-hydroxybutyl vinyl ether (HBVE), 208 g of cyclohexyl vinyl ether (CHVE), potassium carbonate 11 g and 3.5 g of tert-butyl peroxypivalate (PBPV) were charged, and dissolved oxygen in the liquid was removed by pressurization / purging with nitrogen and deaeration.

Next, 660 g of chlorotrifluoroethylene (CTFE) was introduced, the temperature was gradually raised, and the reaction was continued while maintaining the temperature at 65 ° C. After 12 hours, the reactor was cooled with water to stop the reaction. After cooling this reaction liquid (copolymer B solution) to room temperature, unreacted monomers were purged and the reactor was opened.

Potassium carbonate was removed from the obtained reaction solution (copolymer B solution), and the solvent was xylene to obtain a xylene solution having a solid content concentration of copolymer B of 60% by mass. Moreover, the composition analyzed based on the ¹³ CNMR spectrum of the copolymer B was 50.0: 14.7: 25.5: 9.8 in the molar ratio of CTFE: CHVE: EVE: HBVE. The number average molecular weight of the copolymer B was 13,200.

[Examples 1 to 16]
0.5 g of each of copolymer A and copolymer Acf polymerized above was dissolved in 9.5 g of xylene using a mix rotor to obtain a solution of copolymer A or copolymer Acf. Table 2 shows a solution of copolymer A or copolymer Acf, a xylene solution having a solid content of 60% by mass of copolymer B obtained above, and further xylene for dilution as required. The blending amount was adjusted so as to obtain the composition, and the mixture was stirred for 3 hours with a mix rotor to prepare the compositions of Examples 1 to 16. In Example 9 and Example 10 of Table 2, the column of the copolymer not used was indicated as “0”.

Table 2 also shows the mass ratio of copolymer A or copolymer Acf and copolymer B in the composition. In the composition of the present invention, the mass ratio is preferably in the range of 1/99 to 40/60, that is, in the range of 0.01 to 0.677, and preferably in the range of 0.03 to 0.1. Is more preferable.

[Evaluation]
The compatibility of the obtained composition was evaluated. Moreover, a film was formed on a glass plate using the obtained composition, and the film formability was evaluated. Furthermore, the water slidability and abrasion resistance were evaluated about the obtained coating film. The results are also shown in Table 2.

(1) Compatibility The prepared composition was allowed to stand for 12 hours, and the compatibility was visually determined. A uniform transparent solution was evaluated as “◯” (excellent), white turbidity but no precipitate was evaluated as “Δ” (good), and a precipitate was observed as “x” (bad). The evaluations “◯” to “Δ” are suitable for practical use, and “○” is most suitable.

(Preparation of coating)
The prepared composition was applied to one surface of a 5 cm square glass plate having a thickness of 1.5 mm with a spin coater (500 rpm, 30 seconds) to form a coating film. The glass plate with a coating film was heat-treated in an oven at 150 ° C. for 30 minutes to cure the coating film to obtain a glass plate with a coating film. The thickness of the obtained coating film was 100 nm.
(2) Film formability The film surface obtained was visually observed to evaluate the film formability. “○” (excellent) when a transparent and smooth coating is formed, “△” (good) when the resulting coating is striped and white turbidity is applied, and it is applied to the coating (applied part and applied). The case where a non-appearing part occurs) was evaluated as “x” (bad). The evaluations “◯” to “Δ” are suitable for practical use, and “○” is most suitable.

(3-1) Water sliding (water falling angle)
The water falling angle (5 μL) was measured by the above method. In the same manner, 10 μL or 20 μL of distilled water was dropped, and the water falling angle (10 μL) and the water falling angle (20 μL) were measured. If the water falling angle (5 μL) is 35 degrees or less, the water falling angle (10 μL) is 20 degrees or less, and the water falling angle (20 μL) is 15 degrees or less, the sliding property is considered good.

(3-2) Sliding property (water falling speed (20 μL, 30 degrees))
The water falling speed (20 μL, 30 degrees) was measured by the above method. If the water falling speed (20 μL, 30 degrees) is 20 mm / min or more, the sliding property is considered good.

(4) Abrasion resistance A pro-wipe (manufactured by Daio Paper Co., Ltd.) was pressed against the surface of the coating and reciprocated 10 times, and then the presence or absence of scratches on the coating surface was visually evaluated. The case where no scratch was observed was evaluated as “◯” (excellent), the case where a slight scratch was observed was evaluated as “Δ” (good), and the case where many scratches were observed was evaluated as “x” (bad). The evaluations “◯” to “Δ” are suitable for practical use, and “○” is most suitable.
(5) Contact angle The contact angle of 2 μL of distilled water placed on the surface-treated surface of the substrate having the surface treatment layer was measured using DMo-501SA (manufactured by Kyowa Interface Science Co., Ltd.). Measurement was performed at five different locations on the surface-treated surface of the substrate, and the average value was calculated. The 2θ method was used to calculate the contact angle.

In the present invention, an article having a coating film having both durability and water slidability can be provided. The article of the present invention is attached to a window glass of an automobile, an automobile, a motorcycle, a bicycle painted surface head lamp cover, a sensor cover, an outdoor antenna receiver or its cover, a lamp cover of a traffic light, kitchen equipment, kitchen utensils, and kitchen equipment. It can be used for fins and filters for air conditioners such as exhaust devices, air conditioners, home appliances, bathing facilities, wash facilities, medical facilities, medical equipment, mirrors, glasses, inkjet printer parts, toilets, etc.

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. . The film formed using the composition of the present invention can also be used as an anti-icing film for fins and filters of freezers and air conditioning equipment. Since the surface treatment layer excellent in water slidability is difficult for water droplets to adhere to it, the article of the present invention can be used in facilities, apparatuses, instruments, parts and the like where water washing is performed.
It should be noted that the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2018-103782 filed on May 30, 2018 are incorporated herein as the disclosure of the specification of the present invention. It is.

Claims

A copolymer A having a unit based on a monomer having a polyorganosiloxane group and a unit based on a monomer having a blocked isocyanate group, and a copolymer B having a unit based on a fluoroolefin; At least one of the units constituting the polymer B is a composition containing a copolymer B having a hydroxyl group,
A composition characterized in that the content of the polyorganosiloxane group in the copolymer A is 20 to 45% by mass.
The composition according to claim 1, wherein the content of the blocked isocyanate group in the copolymer A is 0.20 to 2.00 mmol / g.
The composition according to claim 1 or 2, wherein the monomer having a polyorganosiloxane group is (meth) acrylate or (meth) acrylamide having a polyorganosiloxane group.
The composition according to any one of claims 1 to 3, wherein the monomer having a blocked isocyanate group is (meth) acrylate or (meth) acrylamide having a blocked isocyanate group.
The composition according to any one of claims 1 to 4, wherein the copolymer A has a number average molecular weight of 5,000 to 100,000.
The composition according to any one of claims 1 to 5, wherein the copolymer B has a unit based on a fluoroolefin having no hydroxyl group and a unit based on a monomer having no hydroxyl group and having no fluorine atom.
The composition according to any one of claims 1 to 6, wherein the mass ratio of the copolymer A and the copolymer B is in the range of 1/99 to 40/60.
The copolymer A is a single monomer having neither a polyorganosiloxane group nor a blocked isocyanate group and a hydrocarbon group having 3 to 16 carbon atoms which may have an etheric oxygen atom between carbon atoms. The composition according to any one of claims 1 to 7, further comprising units based on a body.
The composition according to any one of claims 1 to 8, further comprising a liquid medium.
An article having a base material and a film formed on the surface of the base material using the composition according to any one of claims 1 to 9.
A copolymer having a unit based on a monomer having a polyorganosiloxane group and a unit based on a monomer having a blocked isocyanate group, wherein the content of the polyorganosiloxane group in the copolymer is 20 -45% by weight of copolymer.
The copolymer according to claim 11, wherein the content of the blocked isocyanate group in the copolymer is 0.20 to 2.00 mmol / g.
The copolymer according to claim 11 or 12, wherein the monomer having a polyorganosiloxane group is (meth) acrylate or (meth) acrylamide having a polyorganosiloxane group.
The copolymer according to any one of claims 11 to 13, wherein the monomer having a blocked isocyanate group is (meth) acrylate or (meth) acrylamide having a blocked isocyanate group.
The copolymer according to any one of claims 11 to 14, which has a number average molecular weight of 5,000 to 100,000.