KR102279540B1 - Fluorine-containing copolymer having hydrophilic group, and surface modifying agent containing said copolymer - Google Patents

Abstract

The present invention is a novel fluorinated copolymer, that is, represented by the formulas A and C, that can respond to the demand for suitable hydrophilicity and smoothness in the fields of surface treatment agents for resins, films, fibers, glass, metals, etc., surface modifiers A fluorinated copolymer comprising a (meth)acrylate compound as a monomer unit, wherein the fluorinated copolymer contains a residue of a chain transfer agent for radical polymerization represented by formula (I). provide a synthesis. Rf represents a specific fluorine-containing group.

Description

Fluorine-containing copolymer having a hydrophilic group and a surface modifier comprising the copolymer {FLUORINE-CONTAINING COPOLYMER HAVING HYDROPHILIC GROUP, AND SURFACE MODIFYING AGENT CONTAINING SAID COPOLYMER}

The present invention relates to a fluorinated copolymer or reactive fluorine-containing copolymer that can be used as a surface modifier that is used in the fields of glass, resin, film, optical material, paint, etc., to modify the surface to be more hydrophilic and also has excellent surface smoothness. The present invention relates to a copolymer, and a surface modifier, an active energy ray-curable coating solution, and a cured film containing the fluorinated copolymer or reactive fluorine-containing copolymer.

In this specification, the fluorine-containing copolymer and the reactive fluorine-containing copolymer are sometimes simply referred to as "fluorinated copolymer".

Various additives are added to coating solutions used in the fields of resins, optical materials, and paints for the purpose of imparting various properties to the coating film. As an additive for obtaining a smooth surface state, a leveling agent, which is a surfactant such as hydrocarbon-based, fluorine-based, or silicone-based, is used. Among them, fluorine-based or silicon-based leveling agents have high surface smoothing performance, and are widely and generally used.

Fluorine-based or silicone-based surfactants have a high surface tension lowering ability, and the surface of the coating film containing them exhibits water repellency. When a water-soluble or water-based paint or the like is to be applied on the surface of these coating films, cissing is caused, and there is a problem that post-processing is difficult due to poor coating. On the other hand, although the leveling agent of a hydrocarbon type hardly produces such a coating defect, the surface smoothness performance is low.

Then, as shown in patent document 1, for example, by adding an ionic surfactant to a hard-coat coating liquid, the method of making the surface hydrophilic and improving coating defect is proposed. However, in this method, basic performance, such as hardness which a resin composition originally has, may be impaired. In addition, the solvent of the hard-coat coating liquid which added the ionic surfactant is methanol, and surfactant may not fully melt|dissolve in the organic solvent of the ketone type and ester type generally used for UV curing hard coating.

In such a situation, a surface modifier having leveling properties that facilitates post-processing by making the surface hydrophilic without impairing the basic performance such as coating film hardness inherent in the resin composition, and obtaining a smooth surface state is desired. have.

Japanese Patent Laid-Open 2001-272503

The present invention aims to provide a fluorinated copolymer and a surface modifier that can be used as a surface modifier that can be used as a surface modifier having excellent surface smoothness while at the same time modifying the surface of glass, resin, film, optical material, paint, etc. to a more hydrophilic tendency. do. Another object of the present invention is to provide an active energy ray-curable coating liquid and a cured film containing them.

That is, the present invention provides the fluorine-containing copolymer, reactive fluorine-containing copolymer, surface modifier, active energy ray-curable coating solution and cured film according to the following items 1 to 11.

paragraph 1

A fluorinated copolymer comprising at least the (meth)acrylate compound represented by the formulas A and C as a monomer unit, wherein the fluorinated copolymer contains a residue of a chain transfer agent of the radical polymerization reaction represented by the formula (I) A fluorinated copolymer, characterized in that:

[Wherein, Rf is a group represented by the following formula (1) or (2).

R ¹ is a divalent group having 2 to 50 carbon atoms. R ² is H or a methyl group.]

[R ⁵ is H or a methyl group. EO is an ethylene oxide group, n is the number of repeating units and is an integer from 2 to 20. R ⁶ is H or a methyl group.]

[R ⁷ is a divalent or trivalent hydrocarbon group having 2 to 10 carbon atoms. Z represents COOH or OH, and x is an integer of 1 or 2.].

paragraph 2

Further formula B:

[R ³ is an optionally substituted divalent group. R ⁴ is H or a methyl group.]

The fluorinated copolymer according to item 1, comprising a (meth)acrylate compound monomer unit represented by

paragraph 3

The fluorinated copolymer according to item 1 or 2, wherein the chain transfer agent is represented by the following formula (D):

[R ⁸ is a divalent or trivalent hydrocarbon group having 2 to 10 carbon atoms. Z represents COOH or OH, and x is an integer of 1 or 2.].

paragraph 4

The fluorine-containing copolymer according to any one of Items 1 to 3, wherein the fluorine content in the copolymer is 1% to 15% by mass.

paragraph 5

The fluorinated copolymer according to any one of items 2 to 4, wherein the mass ratio of the (meth)acrylate compound represented by the formulas B and C is 0.2≤B/C≤2.

paragraph 6

A fluorinated copolymer obtained by reacting a (meth)acrylate compound having an isocyanate group represented by the following formula (E) with the hydroxyl group in the fluorinated copolymer according to any one of Items 1 to 5.

[In the formula, R ⁹ is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may have an ether bond as desired). R ¹⁰ represents H or a methyl group. y is an integer of 1 or 2.]

Section 7

When the number of moles of the (meth)acrylate compound having a hydroxyl group among the monomer units constituting the fluorinated copolymer is p and the number of moles of the (meth)acrylate compound represented by the formula (E) is q, the molar ratio is 0.01≤q/ The fluorinated copolymer according to item 6, characterized in that the ratio is p≤0.8.

paragraph 8

In any one of Items 1 to 7, the contact angle of water on the surface of the cured film obtained by curing the active energy ray-curable coating solution containing the fluorinated copolymer is lower than the contact angle when the fluorinated copolymer is not added. The fluorinated copolymers described.

paragraph 9

A surface modifier comprising the fluorinated copolymer according to any one of Items 1 to 8.

paragraph 10

An active energy ray-curable coating solution comprising the fluorinated copolymer according to any one of claims 1 to 8, a polyfunctional (meth)acrylic compound, and a photoinitiator.

paragraph 11

A cured film obtained by curing the active energy ray-curable coating liquid according to claim 10.

The fluorinated copolymer of the present invention can reduce the contact angle of water on the surfaces of resins, films, fibers, glass, metals, and the like, and can impart smoothness. Therefore, the fluorine-containing copolymer of the present invention is useful as a surface modifier for imparting surface smoothness by making their surface hydrophilic.

In this specification, (meth)acrylate means an acrylate and/or a methacrylate.

Fluorinated copolymer

The fluorinated copolymer of the present invention can be obtained by radical polymerization of formulas A and C and, if necessary, other (meth)acrylate compounds (monomer units). Since the chain transfer agent represented by the formula (D) is used in the radical polymerization reaction, the fluorinated copolymer of the present invention has a COOH group or an OH group at the terminal of the main chain.

As (meth)acrylate compounds other than the (meth)acrylate compound represented by the formulas A and C, the (meth)acrylate compound represented by the formula B, the (meth)acrylate compound represented by the formula F, or a compound thereof It is preferable to use two or more types of The use of the (meth)acrylate compound represented by the formula (B) is preferable from the viewpoint of improving hydrophilicity and introducing a functional group such as a (meth)acryloyl group by reacting with the formula (E). Use of the (meth)acrylate compound represented by the general formula (F) is preferable from the viewpoint of improving hydrophilicity and compatibility with the resin composition. The use of the (meth)acrylate compound represented by the formula (E) is preferable from the viewpoint of introducing a group capable of reacting with the UV-curing resin.

A copolymer obtained by polymerizing a monomer containing at least a (meth)acrylate compound represented by formulas A and C, etc. is referred to herein as a "fluorinated copolymer", and (meth)acryl represented by A, C, etc. Since the copolymer obtained by further reacting the copolymer obtained by polymerizing the monomer containing the rate compound and the (meth)acrylate compound represented by the formula (E) contains a reactive carbon-carbon double bond derived from acrylate, especially " reactive fluorine-containing copolymer”.

The content of fluorine in the copolymer is preferably 1% to 15% by mass, more preferably 2 to 14%, still more preferably 3 to 13%, still more preferably 4 to 12%. Practically, it is possible to use in a content of 1 to 10% in a narrower range and 2 to 8% in a narrower range.

The fluorine content of the fluorine-containing copolymer is expressed by ((atomic weight of fluorine × number of fluorine atoms in the entire copolymer) × 100/mass of the entire copolymer). When there is too much fluorine content, since hydrophilicity is not expressed by water and oil repellency being expressed by the effect of fluorine, it is unsuitable.

In the fluorinated copolymer of the present invention, the (meth)acrylate compound represented by the formula (A) (sometimes referred to as “compound A”) is represented by the following formula.

In the above formula, Rf is a group represented by the following formula (1) or (2).

R ¹ is a divalent group having 2 to 50 carbon atoms, preferably 2 to 10 carbon atoms. R ² is H or a methyl group.

Examples of the divalent group having 2 to 50 carbon atoms represented by R ^{1 include the following groups.}

-(CH ₂ ) _n1 - (n1=2∼50)

-XY-(CH ₂ ) _n2 - (n2=2-43)

-X-(CH ₂ ) _n3 - (n3=1-44)

-CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n4 - (n4=1~24)

-XCO(OCH ₂ CH ₂ ) _n5 - (n5=1-21)

(In the formula, X represents phenylene, biphenylene or naphthylene which may have 1 to 3 substituents selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom. Y represents -O-CO-, -CO-O-, -CONH- or -NHCO-.)

X is preferably 1,2-phenylene, 1,3-phenylene or 1,4-phenylene, particularly preferably 1,4-phenylene. Y is preferably -CO-O-.

As a particularly preferable ^{divalent group having 2 to 50 carbon atoms represented by R 1} , a divalent group having the following structures is specifically exemplified.

-(CH ₂ ) _n6 - (n6=2∼10)

-C ₆ H ₄ OCO(CH ₂ ) _n7 - (n7=2∼10)

-C ₆ H ₄ (CH ₂ ) _n8 - (n8=1∼10)

-CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n9 - (n9=1∼10)

-C ₆ H ₄ CO(OCH ₂ CH ₂ ) _n10 - (n10=1∼10)

R ² is H or a methyl group, preferably a methyl group.

The (meth)acrylate compound represented by the formula (A) can be prepared by a known method.

Content of compound A is 2-30 mass % of all (meth)acrylate compounds, Preferably it is 4-18 mass %.

In the fluorinated copolymer of the present invention, the (meth)acrylate compound represented by the formula (C) (sometimes referred to as “compound C”) is represented by the following formula.

R ⁵ is H or a methyl group. EO is an ethylene oxide group, n is the number of repeating units and is 2 to 20. R ⁶ is H or a methyl group.

(EO) _n represents an ethylene oxide group in which the number of repeating units is 2 to 20, and the number of repeating units in the ethylene oxide group is preferably 4 to 15.

The compound represented by the general formula (C) may be produced by a known method or may be obtained as a commercial item. As a commercial product of the compound represented by the formula (C), Nichiyu Co., Ltd. Blemmer AE-90, Nichiyu Co., Ltd. Blemmer AE-200, Nichiyu Co., Ltd. Blemmer AE-400, Nichiyu Co., Ltd. ) manufactured by Blemmer AME-90, Nichiyu Co., Ltd. Blemmer AME-200, Nichiyu Co., Ltd. Blemmer AME-400, Nichiyu Co., Ltd. Blemmer PE-350, etc. are mentioned.

If R ⁵ in the (meth) acrylate compound represented by the formula C is an H, a R ⁵ in the (meth) acrylate compound represented by the general formula C can be used in combination with methyl. When used in combination, the compound in which ^{R 5} is methyl can be used in an amount equal to or less than that of the compound in which ^{R 5 is H.}

^{When the compound in which R 5} in the (meth)acrylate compound represented by the formula (C) is H is used as the (meth)acrylate compound represented by the formula (C), the (meth)acrylate represented by the formula (E) compounds may be used.

The usage-amount of compound C is 2-8 mass parts with respect to the usage-amount of 1 mass part of compound A.

In the fluorinated copolymer of the present invention, as a copolymerization component, (meth)acrylate compounds represented by formulas B and F other than formulas A and C and mixtures of two or more thereof can be used.

The (meth)acrylate compound (sometimes referred to as "compound B") represented by the formula (B) is represented by the following formula.

R ³ is an optionally substituted divalent group. R ⁴ is H or a methyl group.

In the general formula (B), examples of the divalent group having 2 to 50 carbon atoms represented by ^{R 3} include the divalent groups exemplified by ^{R 3 above.} As for carbon number of this divalent group, 2-30 are preferable.

The compound represented by the general formula (B) may be produced by a known method or may be obtained as a commercial item. As a commercial product of the compound represented by the formula (B), 2-hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., Light Ester HO-250), 2-hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.) , light ester HOA), 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., 4-HBA), and the like.

In the fluorinated copolymer of the present invention, when compound B is used, the mass ratio of the (meth)acrylate compound represented by the formulas B and C is 0.2≤B/C≤2, particularly preferably 0.4≤ B/C≤1.

The (meth)acrylate compound (sometimes referred to as "compound F") represented by the formula F is represented by the following formula.

In the formula, R ¹¹ is H or a group having 1 to 20 carbon atoms. R ¹² is H or a methyl group.

As a specific example of a preferable compound in Formula F,

Methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, lauryl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, acrylic acid, methacrylic acid, benzyl methacrylate, etc. , Preferably methacrylic acid, tetrahydrofurfuryl methacrylate, etc., More preferably, methacrylic acid is mentioned.

As for the usage-amount of compound F, the quantity of 1-4 mass parts is used with respect to 1 mass part of compound A.

In the fluorinated copolymer of the present invention, a thiol compound represented by the formula (D) (sometimes referred to as "compound D") is used as a chain transfer agent in the copolymerization reaction, and the thiol compound is represented by the following formula.

In the formula, R ⁸ is a divalent or trivalent hydrocarbon group having 2 to 10 carbon atoms. Z represents COOH or OH, and x is an integer of 1 or 2.

The thiol compound represented by the formula (D) is not particularly limited as long as chain transfer occurs. When R ⁸ is divalent, R ⁸ is preferably an alkanediyl group, wherein x is 1. When R ⁸ is trivalent, R ⁸ is preferably an alkanetriyl group, where x is 2.

Preferred ^{examples of R 8} include aliphatic hydrocarbon groups having the following structures.

-(CH ₂ ) _n11 - (n11=2∼6).

Specifically as the compound represented by the formula (D), for example, thioglycolic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, 3-mercapto-2-methylpropionic acid, 4-mercaptobutanoic acid, 3-mercap Tobutanoic acid, 5-mercaptopentanoic acid, 4-mercaptopentanoic acid, 3-mercaptopentanoic acid, thiomalic acid, 2-mercaptoethanol, 3-mercapto-1-propanol, 3-mercapto-2-propanol, 3 -Mercapto-1,2-propanediol, 4-mercapto-1-butanol, 3-mercapto-2-butanol, 6-mercapto-1-hexanol, 3-mercapto-1- Hexanol, mercaptomethylbutanol, 3-mercapto-2-methylpentanol, and 3-mercapto-3-methylbutanol are mentioned.

The compound represented by the formula (D) may be produced by a known method or may be obtained as a commercial item. Particularly preferred compounds include mercaptopropionic acid, 3-mercapto-1,2-propanediol, and particularly mercaptopropionic acid.

By using the compound of D, a COOH or OH group can be introduced into the main chain terminal of the copolymer of the present invention. When the quantity of the compound of D makes the total amount of the said (meth)acrylate compound 100 mass parts, it is 0.5-4.5 mass parts, Preferably it is 0.5-4.0 mass parts.

In the present invention, a reactive fluorinated copolymer can be obtained by reacting a (meth)acrylate compound having an isocyanate group at the terminal of the formula (E) with respect to the hydroxyl group in the fluorinated copolymer.

In the formula, R ⁹ is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may optionally have an ether bond). R ¹⁰ represents H or a methyl group, preferably H. y is an integer of 1 or 2.

Examples of the divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms, preferably 2 to 4, represented by R ^{9 include the following groups, and the corresponding (meth)acrylate compound of formula (E)} also shown.

R ⁹ :

-(CH ₂ ) _n12 - (n12=2∼10)

-C ₆ H ₁₂ -(OCH ₂ CH ₂ ) _n13 - (n13=1∼2)

-C(CH ₃ )[(CH ₂ ) _n14 ] ₂ (n14=1-4)

When p is the number of moles of an acrylate compound having a hydroxyl group among monomer units constituting the fluorinated copolymer, and q is the number of moles of the (meth)acrylate compound represented by the formula (E), the molar ratio is 0.01≤q/p≤0.8 is the ratio of Especially preferably, it is a ratio of 0.05<q/p<=0.5.

Preparation of fluorinated copolymer

As a polymerization method of (meth)acrylate for obtaining a fluorinated copolymer, a known polymerization method can be used, but it is preferable to radically copolymerize the raw material monomer, polymerization initiator and chain transfer agent in a state in which they are dissolved in a polymerization solvent. Specifically, (meth)acrylates A, B, C and F are mixed in a desired ratio, D is added as an appropriate amount of a polymerization initiator and a chain transfer agent, and in the presence of an organic solvent, 1 to 24 at a temperature of about room temperature to 100° C. react for about an hour. Thereby, the reaction proceeds quantitatively. The mixing order of (meth)acrylates A, B, C and F is not particularly limited.

As a polymerization initiator, the following photoinitiator is mentioned, For example, azobisisobutyronitrile, benzoyl peroxide, etc. can be used preferably.

Although the organic solvent will not be specifically limited if the said reaction advances, For example, an aprotic solvent is mentioned. As the aprotic solvent, dimethoxyethane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, toluene, and propylene glycol monomethyl ether acetate are preferable. is exemplified This organic solvent may be used individually by 1 type, and may mix and use 2 or more types.

In the fluorinated copolymer, the repeating unit does not need to be positioned as shown by the formula, and the hydroxyl group-containing copolymer may be a random polymer or block copolymer of (meth)acrylates A, B, C, and F.

In the reaction of the fluorinated copolymer and the isocyanate group-containing (meth)acrylate E, (meth)acrylate E is mixed in a predetermined ratio with the obtained hydroxyl group-containing copolymer solution, and the mixture is -20°C to 100°C. , Preferably it can achieve by stirring at 20 degreeC - 90 degreeC for 1 to 48 hours. Thereby, the hydroxyl group derived from the (meth)acrylate B or C component in the hydroxyl group-containing copolymer and the isocyanate group of the (meth)acrylate E react to form a urethane bond, resulting in the reactivity of the present invention A fluorine oligomer is obtained. At this time, the mixed (meth)acrylate E reacts quantitatively.

On the occasion of the said reaction, you may use an alkaline catalyst. Although the alkaline catalyst will not be specifically limited as long as the said reaction advances, As a preferable alkaline catalyst, For example, organic types, such as triethylamine, tributylamine, pyridine, 1, 4- diazabicyclo[2.2.2]octane, of alkaline catalysts. The alkaline catalyst is particularly preferably 1,4-diazabicyclo[2.2.2]octane. This alkaline catalyst may be used individually by 1 type, and may mix and use 2 or more types.

The weight average molecular weight of the fluorine-containing copolymer or the fluorine-containing reactive copolymer of the present invention is usually 2000 to 50000, preferably 3000 to 20000.

What is necessary is just to measure a weight average molecular weight by conventionally well-known methods, such as a gel filtration chromatography, a viscosity method, and a light scattering method.

The fluorinated copolymer and reactive fluorinated copolymer of the present invention can be used as a solution, but are usually mixed with additives such as a resin component, a solvent component, a polymerization initiator component, and a filler component to be used as a resin composition.

When used as a solution, examples of the solvent include toluene, xylene, diethyl ether, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetone, acetonitrile, diethylene glycol monoethyl ether, diethylene glycol. Although organic solvents, such as diethyl ether, ethanol, isopropanol, tetrahydrofuran, 1, 4- dioxane, are mentioned, Preferably it is methyl isobutyl ketone. A solvent may be used individually by 1 type, and may mix and use 2 or more types. When using as a solution, as for a density|concentration, 0.01 mass % - 5 mass % are preferable.

By applying a solution containing the fluorinated copolymer and/or reactive fluorinated copolymer of the present invention to the surface of a substrate such as a resin, film, fiber, glass, or metal by coating, coating, spraying, etc. , can modify the properties of the substrate surface.

The surface of the cured film obtained by curing the active energy ray-curable coating solution to which the fluorinated copolymer of the present invention and/or the photopolymerization initiator has been added has a lower water contact angle compared to the case where it is not added. Forming an overcoat layer on the hard coating surface where the contact angle of water exceeds 60° may cause clumping and staining. The fluorinated copolymer of the present invention is used for the purpose of suppressing clumping and unevenness of the overcoat layer by, for example, setting the contact angle of water on the hard coating surface to 60° or less. As shown in the Examples, when dipentaerythritol hexaacrylate or urethane acrylate oligomer is used for the resin monomer or oligomer of the active energy ray-curable coating solution, the contact angle of water on the surface of the coating film is in the range of 45° to 60°. , a suitable hydrophilic surface. If the contact angle of water is within this range, it is preferable because agglomeration does not easily occur when a water-soluble paint or the like is applied.

Resin composition containing fluorinated copolymer

The curable resin composition contained in this invention is prepared as a coating liquid for apply|coating to a base material. In the curable resin composition (coating liquid), a fluorine-containing copolymer and/or a reactive fluorine-containing copolymer as a component exhibiting antifouling properties and leveling properties, an energy ray-curable resin monomer or resin oligomer mainly functioning as a resin film, and other polymerization initiators , solvents, etc. are blended. However, in the case of using a solvent-free coating liquid, a solvent is not mix|blended, and in the case of radiation hardening, a polymerization initiator is not required. In addition, you may add another component to a coating liquid as needed.

The content of the fluorinated copolymer and/or the reactive fluorinated copolymer in the total amount of the curable resin composition of the present invention (when a solvent component is used, the amount of the solvent component is excluded) is usually 0.001 to 10% by mass. degree, Preferably it is about 0.01-5 mass %, More preferably, it is 0.1 mass % - 2 mass %.

Energy ray-curable resin monomer or resin oligomer component

The curable resin composition of the present invention is, in addition to the fluorinated copolymer and/or reactive fluorine-containing copolymer, an energy ray-curable resin monomer and/or resin oligomer (hereinafter referred to as a resin monomer and a resin oligomer that reacts with it to form a cured resin film). may be included).

Such resin monomers and resin oligomers are not particularly limited as long as they react with the fluorinated copolymer and/or the reactive fluorine-containing copolymer to form a cured film, and an energy ray-curable resin usually used for a hard coating film or an anti-reflection coating film Monomers and/or resin oligomers may optionally be used.

As the said resin monomer and resin oligomer, reactive compounds, such as acryl type, such as various acrylates and acryl urethane, urethane type, and an epoxy type, are mentioned, for example, An acrylic resin is used preferably. In particular, since the curable resin composition of the present invention is used in the form of a film after being cured, it is preferable to use a resin monomer and/or a resin oligomer having a reactive functional group having a bifunctional or higher function.

Examples of the resin monomer and resin oligomer having a reactive functional group having more than two functional groups include tricyclodecanedimethylol diacrylate, bisphenol F EO modified diacrylate, bisphenol A EO modified diacrylate, isocyanuric acid. EO modified diacrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylpropane PO modified triacrylate, glycerin PO Addition triacrylate, trimethylolpropane EO modified triacrylate, trimethylolpropane EO modified trimethacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid EO modified triacrylate, ε-caprolactone-modified tris(acryloxyethyl)isocyanurate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipenta Although erythritol hexaacrylate and various urethane acrylate oligomers (Nippon Synthetic Chemical Industry Co., Ltd. Shico series, Negami Industrial Co., Ltd. artresin series, etc.) etc. are mentioned, It is not specifically limited to these. Although the said resin monomer and resin oligomer can be used also by 1 type, you may mix|blend and use 2 or more types by arbitrary ratios.

A radiation, an electron beam, an ultraviolet-ray, a visible light, etc. are mentioned as an energy beam which hardens a resin monomer and a resin oligomer. In curing by radiation or electron beams, since the energy of electromagnetic waves is high, polymerization is possible only with a polymerizable double bond. When using ultraviolet and visible light as an energy source, it is preferable to mix|blend the polymerization initiator component mentioned later.

Content of the said resin monomer and resin oligomer in curable resin composition whole amount of this invention (when using a solvent component, the quantity of a solvent component is excluded) is about 55-99.9 mass % normally, Preferably 60- It is about 99.5 mass %, More preferably, it is about 70-99 mass %.

In addition, the ratio of the resin monomer and resin oligomer to the fluorinated copolymer and/or the reactive fluorinated copolymer is based on 100 parts by mass of the resin monomer and the resin oligomer, the fluorinated copolymer and/or the reactive fluorinated copolymer. is usually about 0.001 to 10 parts by mass, preferably about 0.01 to 5 parts by mass, and more preferably about 0.1 to 2 parts by mass.

polymerization initiator component

The curable resin composition of the present invention may contain, if necessary, a polymerization initiator component in addition to the above fluorinated copolymer and/or reactive fluorinated copolymer, resin monomer and/or resin oligomer.

A conventionally well-known thing can be used for a polymerization initiator component, For example, a photoinitiator can be used.

As a photoinitiator, a wide variety of things are known, and what is necessary is just to select and use it suitably. For example, 1-hydroxycyclohexyl-phenylketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1 -one, benzophenone, 1-[4-(2-hydroxyethoxy-phenyl)-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methyl Thio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, bis(2,6-dimethoxy Benzoyl)-2,4,4-trimethylbenzylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-hydroxy-1-{4-[4-(2-) Hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O -benzoyloxime)], ethanone, [9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), 2,2-bis(2 -Chlorophenyl)-4,4,5,5-tetraphenyl-1,2-biimidazole, 2,2-diethoxyacetophenone, benzophenone, methyl O-benzoylbenzoate, 4,4-bis(di Methylamino) benzophenone, dibenzyl ketone, fluorenone, 2-hydroxy-2-methylpropiophenone, thioxanthone, benzyldimethyl ketanol, benzyl methoxyethyl acetal, benzoin, anthraquinone, anthrone , dibenzosuberone, 4,4-bis(dimethylamino)chalcone, P-dimethylaminocinnamylideneindanone, 2-(P-dimethylaminophenylvinylene)-isonaphthothiazole, 3, 3-carbonyl-bis(7-diethylaminocoumarin), 3-phenyl-5-benzoylthio-tetrazole, etc. are mentioned.

When using a polymerization initiator component, although use individually by 1 type is also possible, you may mix|blend and use 2 or more types arbitrarily. The addition amount of the polymerization initiator component is usually about 0.1 to 50 parts by mass based on 100 parts by mass of the polymerizable resin component (the total amount of the fluorinated copolymer and/or the reactive fluorinated copolymer, the resin monomer and/or the resin oligomer). , Preferably it is about 0.5-30 mass parts, More preferably, it is about 1-10 mass parts.

solvent component

Although curable resin composition of this invention does not need to contain a solvent component, it may contain the solvent component as needed. As the solvent component, a conventionally known solvent component may be used, for example, alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, toluene , aromatic hydrocarbons such as xylene, ethers such as diethyl ether, alkylene glycol monoethers such as diethylene glycol monoethyl ether, alkylene glycol diethers such as diethylene glycol diethyl ether, tetrahydrofuran, 1,4-dioxane is mentioned. Although these solvent components can be used also by 1 type, you may mix|blend and use 2 or more types by arbitrary ratios.

When a solvent component is used, the amount of the solvent component used in the curable resin composition of the present invention is the amount of the polymerizable resin component (the total amount of the fluorinated copolymer and/or reactive fluorinated copolymer, the resin monomer and/or the resin oligomer) With respect to 100 mass parts, it is about 25-5000 mass parts normally, Preferably it is about 40-2000 mass parts, More preferably, what is necessary is just about 60-1000 mass parts.

other ingredients

Curable resin composition of this invention may mix|blend microparticles|fine-particles, a filler, etc. as needed in order to provide a shape to the cured film surface, or to provide another desired function.

Method for producing a cured film

In this invention, after making curable resin composition of this invention into a coating liquid and apply|coating this coating liquid to a base material, it can be set as a cured film by performing light irradiation etc.

As a procedure for obtaining the cured film of the present invention, a fluorine-containing copolymer and/or a reactive fluorine-containing copolymer, a resin monomer and/or a resin oligomer, and, if necessary, a polymerization initiator component, a solvent component, fine particles, a filler, and the like are suitable It is mixed and dissolved at a compounding ratio, and the curable resin composition of this invention is prepared as a coating liquid. Then, the coating solution is applied to a constant film thickness on the substrate, the solvent component is removed by hot air drying, vacuum drying, etc., and then a cured film is obtained by irradiating energy rays such as radiation, electron beams, ultraviolet rays, and visible rays. can

The coating method of the coating liquid is not particularly limited, but for example, it is applied by wet coating, and as the method, for example, a gravure method, a bar coating method, a wire bar method, a spin coating method, a doctor blade method, a dip coating method, A slit coating method etc. are mentioned.

Although it will not specifically limit as a base material which produces a cured film if support of a cured film is possible, For example, when using as a hard coat for optical uses, the sheet|seat which has transparency is preferable. Glass, plastic, etc. are mentioned as a material of a transparent sheet|seat, Especially a plastic sheet is preferable. As plastic, thermoplastic resin, thermosetting resin, etc. can be used, For example, polyolefin resin, such as polyethylene and polypropylene, polyester resin, such as polyethylene terephthalate, cellulose resin, such as triacetyl cellulose and butyl cellulose, polystyrene resin, poly Urethane resin, polyvinyl alcohol, polyvinyl chloride, acrylic resin, polycarbonate resin, polyacrylonitrile, cycloolefin polymer, polyethersulfone, etc. are mentioned. These sheets may be subjected to a transfer treatment such as a binder treatment, corona treatment, plasma treatment, or flame treatment as needed.

The thickness of the cured film of this invention is not specifically limited, What is necessary is just to select suitably according to a use. Usually, it can be set as about 100 nm - 30 micrometers.

Example

The contents of the present invention will be described with reference to the following examples, but the contents of the present invention should not be construed as being limited by the examples.

The fluorine-containing (meth)acrylate (A-1) used in the synthesis example was synthesized by a known synthesis method (for example, the synthesis method described in JP 2010-47680 ).

Synthesis Example 1

In a three-necked flask (50 mL) equipped with a cooling tube, 1.00 g of fluorinated acrylate (A-1), methoxy polyethylene glycol monoacrylate (C-1: AME-400 manufactured by Nichiyu Corporation) 4.00 g, 4- 4.00 g of hydroxybutyl acrylate (B-1), 18.00 g of methyl isobutyl ketone, 0.065 g of 2,2'-azobisisobutyronitrile, and 0.2 g of mercaptopropionic acid were added. Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was replaced with nitrogen. After nitrogen substitution, the reaction solution was heated to 80°C while stirring to initiate the reaction. After that, stirring was continued at 80 degreeC for 14 hours. The completion of the reaction was confirmed by disappearance of a peak characteristic of each acrylate ^{in 1 H-NMR.} The desired fluorinated oligomer was obtained quantitatively (33% by mass methyl isobutyl ketone solution). The obtained fluorinated copolymer was prepared by adding methyl isobutyl ketone so that the solid content concentration was 30% by mass.

The weight average molecular weight (Mw) of the obtained fluorinated polymer was measured under the following conditions using the following apparatus. The fluorinated polymer obtained in Synthesis Example 1 had a weight average molecular weight of 6700.

Device: ACQUITY UPLC H-Class (Waters)

Detector: ACQUITY UPLC ELS Detection (Waters)

Column: TSKgel α-5000 (φ7.8mm×30cm) (Tosoh)

Guide column: TSK guard α (φ6.0mm×4cm) (Tosoh)

Solvent: tetrahydrofuran (Kanto Chemical)

Column temperature: 40°C

Sample concentration: 0.05 to 0.1 wt%

Injection volume: 0.01ml

Molecular Weight Correction: Monodisperse Polyethylene Glycol (Tosoh)

Synthesis Examples 2 to 6, and 10 to 12, 14, 17 to 18

In the same procedure as in Synthesis Example 1, a fluorinated copolymer was synthesized by changing the ratios of monomers A, B, C, F and compound D. The monomer ratio and the monomer species are as shown in Table 1. In Table 1, numbers in parentheses indicate mass ratios (except for the column of monomer E). The number in parentheses of the monomer E indicates the equivalent ratio of the monomer E to the hydroxyl group in the fluorinated copolymer.

Synthesis Example 7

In the fluorinated copolymer obtained in Synthesis Example 1, 0.2 equivalent of 2-(isocyanate ethyl)acrylate (E-1) and 0.01 equivalent of the hydroxyl group-containing acrylate compound (B-1); 4-diazabicyclo[2.2.2]octane was added, and stirring of the reaction solution was continued at 50 degreeC for 20 hours. The completion of the reaction was confirmed by disappearance of -N=C=O absorption (2275-2250 cm ^{-1 ) using FT-IR.} The desired reactive fluorine-containing oligomer was obtained quantitatively (30 mass % methyl isobutyl ketone solution).

Synthesis Example 8

A reactive fluorinated copolymer was synthesized in the same manner as in Synthesis Example 7 except that the ratio of the monomers B and C was changed.

Synthesis Example 9

A reactive fluorinated copolymer was synthesized in the same manner as in Synthesis Example 7 except that the ratio of the monomer E was changed.

Synthesis Example 13

A reactive fluorinated copolymer was synthesized in the same manner as in Synthesis Example 7 except that the ratio of the monomers B and C was changed.

Synthesis Example 15

A reactive fluorinated copolymer was synthesized in the same manner as in Synthesis Example 1 except that the ratio of the monomers B and C was changed. The fluorinated polymer obtained in Synthesis Example 15 had a weight average molecular weight of 12000.

Synthesis Example 16

A reactive fluorinated copolymer was synthesized in the same manner as in Synthesis Example 7 except that the copolymer obtained in Synthesis Example 15 was used. The fluorinated polymer obtained in Synthesis Example 16 had a weight average molecular weight of 12000.

Synthesis Example 19

A reactive fluorinated copolymer was synthesized in the same manner as in Synthesis Example 7 except that the ratio of the monomers B and C was changed and the compound D was changed. The fluorinated polymer obtained in Synthesis Example 19 had a weight average molecular weight of 19000.

(A-1): C ₉ F ₁₇ OC ₆ H ₄ CO ₂ CH ₂ CH ₂ OC(=O)C(CH ₃ )=CH ₂

(A-2): C ₆ F ₁₃ CH ₂ CH ₂ OC(=O)CH=CH ₂

(B-1): 4-hydroxybutyl acrylate

(C-1): methoxy polyethylene glycol monoacrylate

(Blemmer AME-400 manufactured by Nichiyu Corporation, n≒9)

(C-2): poly (ethylene oxide) acrylate

(Blemmer AE-400 manufactured by Nichiyu Corporation, n≒10)

(C-3): poly (ethylene oxide) acrylate

(Blemmer AE-200 manufactured by Nichiyu Corporation, n≒4.5)

(C-4): methoxy polyethylene glycol monomethacrylate

(Blemmer PME-400 manufactured by Nichiyu Corporation, n≒9)

(F-1): methacrylic acid

(F-2): tetrahydrofurfuryl acrylate

(D-1): mercaptopropionic acid

(D-2): 3-mercapto-1,2-propanediol

(D-3): 1-dodecanethiol

(E-1): 2-(ethyl isocyanate) acrylate (Showa Denko Co., Ltd. make, Karenz AOI)

50 parts by mass of dipentaerythritol hexaacrylate (manufactured by Toa Synthesis Co., Ltd., trade name: M-402) as a curable resin monomer or 50 parts by mass of urethane acrylate resin (trade name: UV7640B, manufactured by Nippon Synthetic Chemical Co., Ltd.) 1- as a photoinitiator 2.0 parts by mass of hydroxycyclohexyl-phenyl-ketone (Ciba Specialty Chemicals, trade name: Irgacure 184), 1.5 parts by mass of the compounds of Synthesis Examples 1 to 19 (30 mass % solution), as a solvent 46.5 mass parts of methyl isobutyl ketone (MIBK) were mixed, and the curable coating liquid was created. This is No. 8, spread on a polyester film (Toyo Spinning Agent, trade name: Cosmoshine A4100) with a bar coater, put into a dryer set at 100 ° C. for 3 minutes, volatilize the solvent, and then UV irradiation to obtain a cured film. Table 2 shows the evaluation results.

Assessment Methods

(1) compatibility

The compatibility of the curable coating solution was visually observed.

Evaluation criteria: Transparent = ○

Cloudy, sediment oil = ×

(2) contact angle

The contact angle of water with respect to the surface of the cured film immediately after production was measured with a contact angle measuring device (DropMaster600 made by Kyowa Interface Chemicals).

Evaluation standard:

Contact angle value of 55° or less = ◎

The value of the contact angle is greater than 55° and less than or equal to 60° = ○

The value of the contact angle is greater than 60° and less than or equal to 65° = △

Value of contact angle is 65° or more = ×

(3) pencil hardness

According to JIS K 5600-5-4, the lead of the pencil was placed at an angle of about 45° to the test plate and moved forward by about 10 mm or more at a uniform speed while pushing it against the test plate with a load of 750 g. The hardness symbol of the hardest pencil without scratches, dents or cracks in the coating film was taken as the coating film hardness.

(4) surface smoothness

The cured film surface after UV irradiation was visually observed.

Evaluation criteria: No streaks, lumps, etc. ○

There are stripes, lumps, etc. ×

As can be seen from Table 2, the cured films of Examples 1 to 16 all showed good surface smoothness, did not show a decrease in film strength, and it was found that the contact angle of water was 60° or less and showed a moderate hydrophilic tendency. could From Comparative Example 2, when the fluorine-containing (meth)acrylate component A was a straight-chain tridecafluorooctyl group, although it was excellent in surface smoothness, the contact angle value was high, and a water-repellent surface was obtained. From Comparative Example 3, when the fluorine-containing (meth)acrylate component A was not contained, the surface was not smooth and did not become hydrophilic. Further, in Comparative Example 4 in which 1-dodecanethiol was used as the chain transfer agent, the decrease in the contact angle of water was small, and a sufficient hydrophilic tendency was not shown.

The fluorinated copolymer according to the present invention is useful as a surface modifier for making the surface used in the fields of glass, fiber, metal, resin, film, optical material, paint, etc., hydrophilic, for example, and is suitable for the surface of a substrate It is useful as a compound capable of imparting hydrophilicity and smoothness. Since the curable composition containing the fluorinated copolymer of the present invention is excellent in transparency, it can also be used in fields requiring transparency, such as optical applications.

Claims (12)

A fluorine-containing copolymer comprising at least the (meth)acrylate compound represented by the formulas A and C as a monomer unit, wherein the fluorine content in the fluorine-containing copolymer is 1% to 15% by mass, and the fluorine-containing copolymer is a fluorinated copolymer comprising a residue of a chain transfer agent in a radical polymerization reaction represented by the formula (I):

[Wherein, Rf is a group represented by the following formula (1) or (2).

R ¹ is a divalent group having 2 to 50 carbon atoms. R ² is H or a methyl group.]

[R ⁵ is H or a methyl group. EO is an ethylene oxide group, n is the number of repeating units and is an integer from 2 to 20. R ⁶ is H or a methyl group.]

[R ⁷ is a divalent or trivalent hydrocarbon group having 2 to 10 carbon atoms. Z represents COOH or OH, and x is an integer of 1 or 2.]. The method of claim 1,
Further formula B:

[R ³ is a divalent group having 2 to 50 carbon atoms which may be substituted,
-(CH ₂ ) _n1 - (n1=2∼50)
-XY-(CH ₂ ) _n2 - (n2=2-33)
-X-(CH ₂ ) _n3 - (n3=1-34)
-CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n4 - (n4=20∼24)
-XCO(OCH ₂ CH ₂ ) _n5 - (n5=1∼16)
(In the formula, X represents phenylene, biphenylene or naphthylene which may have 1 to 3 substituents selected from the group consisting of an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom. Y represents -O-CO-, -CO-O-, -CONH- or -NHCO-). R ⁴ is H or a methyl group.]
A fluorinated copolymer comprising a (meth)acrylate compound monomer unit represented by. 3. The method according to claim 1 or 2,
A fluorinated copolymer in which the chain transfer agent is represented by the following formula (D):

[R ⁸ is a divalent or trivalent hydrocarbon group having 2 to 10 carbon atoms. Z represents COOH or OH, and x is an integer of 1 or 2.]. 3. The method according to claim 1 or 2,
A fluorine-containing copolymer, wherein the fluorine content in the copolymer is 2% to 14% by mass. 3. The method of claim 2,
A fluorinated copolymer in which the mass ratio of the (meth)acrylate compound represented by the formulas B and C is 0.2≤B/C≤2. A fluorinated copolymer obtained by reacting a (meth)acrylate compound having an isocyanate group represented by the following formula (E) with the hydroxyl group in the fluorinated copolymer according to claim 1, wherein ^{R 5 is H.}

[In the formula, R ⁹ is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may have an ether bond as desired). R ¹⁰ represents H or a methyl group. y is an integer of 1 or 2.]. A fluorinated copolymer obtained by reacting a (meth)acrylate compound having an isocyanate group represented by the following formula (E) with the hydroxyl group in the fluorinated copolymer according to claim 2 .

[In the formula, R ⁹ is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may have an ether bond as desired). R ¹⁰ represents H or a methyl group. y is an integer of 1 or 2.]. 8. The method according to claim 6 or 7,
When the number of moles of the (meth)acrylate compound having a hydroxyl group among the monomer units constituting the fluorinated copolymer is p and the number of moles of the (meth)acrylate compound represented by the formula (E) is q, the molar ratio is 0.01≤q/ A fluorinated copolymer, characterized in that the ratio of p≤0.8. 8. The method of any one of claims 1, 2, 6, and 7, wherein
A fluorinated copolymer, characterized in that the contact angle of water on the surface of the cured film obtained by curing the active energy ray-curable coating solution containing the fluorinated copolymer is lower than that in the case where the fluorinated copolymer is not added. A surface modifier comprising the fluorinated copolymer according to any one of claims 1, 2, 6, and 7. An active energy ray-curable coating liquid comprising the fluorinated copolymer according to any one of claims 1, 2, 6, and 7, a polyfunctional (meth)acrylic compound, and a photopolymerization initiator. A cured film obtained by curing the active energy ray-curable coating liquid according to claim 11 .