JP6479774B2 - Fluorine-containing copolymer having hydrophilic group and surface modifier containing the copolymer - Google Patents

Description

  The present invention is used in the field of glass, resin, film, optical material, paint and the like, and it is possible to use it as a surface modifier which improves the surface to be more hydrophilic and also has excellent surface smoothness. The present invention relates to a polymer or a reactive fluorine-containing copolymer, and a surface modifier containing the fluorine-containing copolymer or a reactive fluorine-containing copolymer, an active energy ray-curable coating solution, and a cured film.

  In the present specification, the fluorine-containing copolymer and the reactive fluorine-containing copolymer may be combined and simply described as a “fluorine-containing copolymer”.

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

  The fluorine-based or silicone-based surfactant has high ability to reduce the surface tension, and the coating film surface containing these exhibits water repellency. When it is attempted to apply a water-soluble or water-based paint or the like on the surface of these coating films, there is a problem that it causes repelling and is difficult to be post-processed because of poor coating. On the other hand, hydrocarbon leveling agents are unlikely to cause such coating defects, but their surface smoothness performance is low.

  Therefore, for example, as disclosed in Patent Document 1, a method has been proposed in which the surface is made hydrophilic by adding an ionic surfactant to the hard coat coating liquid to improve the coating defect. However, in this method, basic performance such as hardness originally possessed by the resin composition may be impaired. In addition, the solvent of the hard coat coating solution to which the ionic surfactant is added is methanol, and the surfactant is not sufficiently dissolved in the ketone-based or ester-based organic solvent generally used in the UV curing hard coat. There is a case.

  Under such circumstances, the post-processing can be facilitated by making the surface hydrophilic, without inhibiting the basic performance such as the coating film hardness originally possessed by the resin composition, and a smooth surface state can be obtained. A surface modifier having leveling properties is desired.

Japanese Patent Application Publication No. 2001-272503

  The present invention is a fluorine-containing copolymer that can be used as a surface modifier that improves the surface of glass, resin, film, optical material, paint, etc. to be more hydrophilic and also has excellent surface smoothness. The purpose is to provide an agent. Another object of the present invention is to provide an active energy ray-curable coating solution and a cured film containing these.

  That is, the present invention provides a fluorocopolymer, a reactive fluorocopolymer, a surface modifier, an active energy ray-curable coating solution, and a cured film of the following items 1 to 11.

［式中、Ｒｆは下記式（１）または（２）で示される基である。

Ｒ^１は炭素原子数が２〜５０の二価の基である。Ｒ²はＨまたはメチル基である。］

[Ｒ^５はＨまたはメチル基である。ＥＯはエチレンオキシド基あり、ｎは繰り返し単位数であり２から２０の整数である。Ｒ^６はＨまたはメチル基である。]

[Ｒ^７は炭素原子数が２〜１０の二価または三価の炭化水素基である。Ｚは、ＣＯＯＨまたはＯＨを表し、ｘは１または２の整数である。]。Item 1
A fluorine-containing copolymer containing at least a (meth) acrylate compound represented by the general formulas A and C as a monomer unit, wherein the fluorine-containing copolymer has a radical polymerization reaction represented by the general formula (I) Fluorinated copolymers characterized in that they contain residues of chain transfer agents:

[Wherein, R f 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 methyl. ]

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

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

[Ｒ^３は、置換されていてもよい二価の基である。Ｒ^４は、Ｈまたはメチル基である。]
で表される（メタ）アクリレート化合物モノマー単位を含む、項１に記載の含フッ素共重合体。Item 2
Furthermore, the following general formula B:

[R ³ is a divalent group which may be substituted. R ⁴ is H or methyl. ]
Item 2. The fluorine-containing copolymer according to item 1, comprising a (meth) acrylate compound monomer unit represented by

[Ｒ^８は炭素原子数が２〜１０の二価または三価の炭化水素基である。Ｚは、ＣＯＯＨまたはＯＨを表し、ｘは１または２の整数である。]。Item 3
The fluorine-containing copolymer according to item 1 or 2, wherein the chain transfer agent is represented by the following general 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. ].

Item 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.

Item 5
The fluorine-containing copolymer according to any one of Items 2 to 4, wherein the mass ratio of the (meth) acrylate compound represented by the general formulas B and C is a ratio of 0.2 ≦ B / C ≦ 2.

［式中、Ｒ^９は、炭素原子数が２〜１０の二価または三価の飽和脂肪族炭化水素基（該飽和脂肪族炭化水素基は所望によりエーテル結合を有していてもよい。）である。Ｒ^１０はＨまたはメチル基を示す。ｙは、１または２の整数である。］ Item 6
The fluorine-containing copolymer which makes the (meth) acrylate compound which has an isocyanate group represented by the following general formula E react with respect to the hydroxyl group in the fluorine-containing copolymer in any one of Claims 1-5.

[Wherein, 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)] It is. R ¹⁰ represents H or a methyl group. y is an integer of 1 or 2. ]

Item 7
When the number of moles of the (meth) acrylate compound having a hydroxyl group among the monomer units constituting the fluorine-containing copolymer is p, and the number of moles of the (meth) acrylate compound represented by the general formula E is q, the molar ratio 7. The fluorine-containing copolymer according to item 6, wherein the ratio of 0.01 ≦ q / p ≦ 0.8.

Item 8
The contact angle of water on the surface of the cured film obtained by curing the active energy ray-curable coating solution containing the fluorine-containing copolymer is lower than the contact angle when no fluorine-containing copolymer is added. Item 8. The fluorine-containing copolymer according to any one of Items 1 to 7, characterized in that

Item 9
Item 9. A surface modifier comprising the fluorine-containing copolymer according to any one of items 1 to 8.

Item 10
Item 9. An active energy ray-curable coating solution comprising the fluorine-containing copolymer according to any one of items 1 to 8, a polyfunctional (meth) acrylic compound and a photopolymerization initiator.

Item 11
Item 11. A cured film obtained by curing the active energy ray-curable coating solution according to item 10.

  The fluorine-containing copolymer of the present invention can reduce the contact angle of water on the surface of a resin, film, fiber, glass, metal or the like, and at the same time, can impart smoothness. Therefore, the fluorine-containing copolymer of the present invention tends to render these surfaces hydrophilic and is useful as a surface modifier to impart surface smoothness.

  In the present specification, (meth) acrylate means acrylate and / or methacrylate.

Fluorocopolymer The fluorocopolymer of the present invention can be obtained by radical polymerization of the general formulas A and C and, if necessary, other (meth) acrylate compounds (monomer units). In order to use a chain transfer agent represented by the general formula D in the radical polymerization reaction, the fluorocopolymer of the present invention has a COOH group or an OH group at the end of the main chain.

  Examples of (meth) acrylate compounds other than (meth) acrylate compounds represented by the general formulas A and C include (meth) acrylate compounds represented by the general formula B, (meth) acrylate compounds represented by the general formula F, Or it is preferable to use 2 or more types of those compounds. The use of the (meth) acrylate compound represented by the general formula B is preferable in that it improves the hydrophilicity and can react with the general formula E to introduce a functional group such as a (meth) acryloyl group. The use of the (meth) acrylate compound represented by the general formula F is preferable in terms of the improvement of the hydrophilicity and the improvement of the compatibility with the resin composition. Use of the (meth) acrylate compound represented by the general formula E is preferred in that it can introduce a group capable of reacting with the UV curable resin.

  In the present specification, a copolymer obtained by polymerizing a monomer containing a (meth) acrylate compound represented by at least the general formulas A and C or the like is referred to as “fluorinated copolymer”. Obtained by further reacting a copolymer obtained by polymerizing a monomer containing the (meth) acrylate compound to be reacted with a (meth) acrylate compound represented by the general formula E has a reactivity derived from acrylate In particular, it may be described as a "reactive fluorine-containing copolymer" because it contains a carbon-carbon double bond of

  The fluorine content 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 narrower range of 1 to 10%, and a narrower range of 2 to 8%.

  The fluorine content of the fluorine-containing copolymer is represented by ((fluorine atomic weight × number of fluorine atoms in all copolymers) × 100 / mass of all copolymers). If the fluorine content is too high, it is unsuitable because the hydrophilicity is not expressed by the expression of water and oil repellency by the effect of fluorine.

上記式中、Ｒｆは下記式（１）または（２）で示される基である。

The (meth) acrylate compound (sometimes referred to as “compound A”) represented by General Formula A in the fluorine-containing copolymer of the present invention 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, preferably 2 to 10 carbon atoms. R ² is H or methyl.
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)
_{-X-Y- (CH 2) n2} - (n2 = 2~43)
_{-X- (CH 2) n3 - (} n3 = 1~44)
-CH ₂ CH ₂ (OCH ₂ CH ₂ ) _{n 4-} (n 4 = 1 to 24)
-XCO (OCH ₂ CH ₂ ) _n 5-(n 5 = 1 to 21)
(Wherein X is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenylene, biphenylene or napthylene optionally having 1 to 3 substituents selected from the group consisting of halogen atoms 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-.

Specific examples of the divalent group having 2 to 50 carbon atoms represented by R ¹ include a divalent group having the following structure.
_{- (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 methyl, preferably methyl.

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

  The content of the compound A is 2 to 30% by mass, preferably 4 to 18% by mass, of the total (meth) acrylate compound.

The (meth) acrylate compound (sometimes referred to as “compound C”) represented by General Formula C in the fluorine-containing copolymer of the present invention is represented by the following formula.

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

(EO) _n represents an ethylene oxide group having a repeating unit number of 2 to 20, and the repeating unit number of the ethylene oxide group is preferably 4 to 15.

  The compounds represented by the general formula C can be produced by known methods or can be obtained as commercial products. Commercially available products of the compound represented by the general formula C include Brenmer AE-90 manufactured by NOF Corporation, Blenmer AE-200 manufactured by NOF Corporation, Blenmer AE-400 manufactured by NOF Corporation, Oil Co., Ltd. Brenmer AME-90, NOF Corporation Co. Brenmer AME- 200, NOF Corporation Co., Ltd. Blenmar AME-400, NOF Corporation Co., Ltd. Blenmer PE-350, etc. may be mentioned. .

When R ⁵ in the (meth) acrylate compound represented by the general formula C is H, a compound in which R ⁵ in the (meth) acrylate compound represented by the general formula C is methyl can be used in combination. When used in combination, a compound in which R ⁵ is methyl can be used in an amount equal to or less than that of a compound in which R ⁵ is H.
When a compound where R ⁵ in the (meth) acrylate compound represented by the general formula C is H is used as a (meth) acrylate compound represented by the general formula C, (meth) represented by the general formula E Acrylate compounds can be used.

  The amount of compound C used is 2 to 8 parts by mass relative to the amount used of 1 part by mass of compound A.

  In the fluorine-containing copolymer of the present invention, (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 as copolymerization components.

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

R ³ is a divalent group which may be substituted. R ⁴ is H or methyl.

Examples of the divalent group having 2 to 50 carbon atoms represented by R ³ in General Formula B include the divalent groups exemplified for R ³ above. The number of carbon atoms of this divalent group is preferably 2 to 30.

  The compounds represented by the general formula B can be prepared by known methods or can be obtained as commercial products. As commercially available products of the compound represented by the general 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 (Osaka Organic Chemical Industry Ltd. make, 4-HBA) etc. are mentioned.

  When the compound B is used in the fluorine-containing copolymer of the present invention, the mass ratio of the (meth) acrylate compound represented by the general formulas B and C is a ratio of 0.2 ≦ B / C ≦ 2, particularly Preferably, 0.4 ≦ B / C ≦ 1.

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

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

Specific examples of preferred compounds in the general formula F are
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.
The amount of compound F used is 1 to 4 parts by mass with respect to 1 part by mass of compound A.

The fluorine-containing copolymer of the present invention uses a thiol compound (sometimes referred to as "compound D") represented by the general formula D as a chain transfer agent in the copolymerization reaction, and the thiol compound is Be done.

In the above 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 general formula D is not particularly limited as long as it causes chain transfer. When R ⁸ is divalent, R ⁸ is preferably an alkanediyl group, where x is 1. When R ⁸ is trivalent, R ⁸ is preferably an alkanetriyl group, where x is 2.

Specific examples of R ⁸ include aliphatic hydrocarbon groups having the following structures.
_{- (CH 2) n11 - (} n11 = 2~6).

  Specific examples of the compound represented by Formula D include, for example, thioglycolic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, 3-mercapto-2-methylpropionic acid, 4-mercaptobutanoic acid, and 3-mercapto Butanoic 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-methyl pen Tanol, 3-mercapto-3-methyl butane Like the Nord.

The compounds represented by the general formula D can also be produced by known methods or can be obtained as commercial products. Particularly preferred compounds include mercaptopropionic acid, 3-mercapto-1,2-propanediol, in particular mercaptopropionic acid.
By using the compound D, a COOH or an OH group can be introduced at the main chain terminal of the copolymer of the present invention. The amount of the compound D is 0.5 to 4.5 parts by mass, preferably 0.5 to 4.0 parts by mass, based on 100 parts by mass of the total amount of the (meth) acrylate compounds.

In the present invention, a reactive fluorine-containing copolymer can be obtained by reacting a (meth) acrylate compound having an isocyanate group at an end represented by the general formula E with a hydroxyl group in the fluorine-containing 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). is there. 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 carbon atoms, represented by R ⁹ include the following groups, and The meta) acrylate compound is shown collectively.
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 the number of moles of an acrylate compound having a hydroxyl group among monomer units constituting the fluorine-containing copolymer is p, and the number of moles of a (meth) acrylate compound represented by General Formula E is q, the molar ratio is 0. It is a ratio of 01 ≦ q / p ≦ 0.8. Particularly preferably, the ratio is 0.05 ≦ q / p ≦ 0.5.

Production of Fluorine-Containing Copolymer As a polymerization method of (meth) acrylate for obtaining a fluorine-containing copolymer, a known polymerization method can be used, but a raw material monomer, a polymerization initiator and a chain transfer agent It is preferable to carry out radical copolymerization in a dissolved state. Specifically, (meth) acrylates A, B, C and F are mixed in a desired ratio, D is added as an appropriate amount of polymerization initiator and chain transfer agent, and at a temperature of about room temperature to about 100 ° C. in the presence of an organic solvent. React for about 1 to 24 hours. The reaction then proceeds quantitatively. The order of mixing of (meth) acrylates A, B, C and F is not particularly limited.

Examples of the polymerization initiator include the following photopolymerization initiators. For example, azobisisobutyronitrile, benzoyl peroxide and the like can be preferably used.
The organic solvent is not particularly limited as long as the above reaction proceeds, and examples thereof include aprotic solvents. Preferred examples of the aprotic solvent include dimethoxyethane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, tetrahydrofuran, N, N-dimethylformamide, toluene and propylene glycol monomethyl ether acetate. The organic solvents may be used singly or in combination of two or more.

  In the fluorine-containing copolymer, the repeating unit may not be located as shown in the chemical formula, and the hydroxyl group-containing copolymer is a random polymer or block copolymer of (meth) acrylates A, B, C, and F. It may be.

  The reaction of the fluorocopolymer and the isocyanate group-containing (meth) acrylate E is carried out by mixing (meth) acrylate E in a predetermined ratio with the obtained hydroxyl group-containing copolymer solution, and C., preferably 20.degree. C. to 90.degree. C., by stirring for 1 to 48 hours. Thereby, the hydroxyl group derived from the (meth) acrylate B or C component in the hydroxyl group-containing copolymer reacts with the isocyanate group of (meth) acrylate E to form a urethane bond, and the reactive fluorine-containing oligomer of the present invention Is obtained. At this time, the mixed (meth) acrylate E reacts quantitatively.

  In the reaction, an alkaline catalyst may be used. The alkaline catalyst is not particularly limited as long as the above reaction proceeds, but preferred alkaline catalysts include organic alkaline catalysts such as triethylamine, tributylamine, pyridine, 1,4-diazabicyclo [2.2.2] octane, etc. Can be mentioned. The alkaline catalyst is particularly preferably 1,4-diazabicyclo [2.2.2] octane. The alkaline catalysts may be used singly or in combination of two or more.

  The weight average molecular weight of the fluorine-containing copolymer or fluorine-containing reactive copolymer of the present invention is usually from 2,000 to 50,000, preferably from 3,000 to 20,000.

  The weight average molecular weight may be measured by gel filtration chromatography, viscosity method, light scattering method, etc. by a conventionally known method.

  The fluorine-containing copolymer and reactive fluorine-containing copolymer of the present invention can be used as a solution, but usually, they are mixed with additives such as a resin component, a solvent component, a polymerization initiator component, and a filler component. And 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 diethyl ether, ethanol, isopropanol, tetrahydrofuran, 1,4 -An organic solvent such as dioxane is mentioned, preferably methyl isobutyl ketone. The solvents may be used singly or in combination of two or more. When used as a solution, the concentration is preferably 0.01% by mass to 5% by mass.

  By applying the solution containing the fluorocopolymer and / or reactive fluorocopolymer of the present invention to the surface of equipment such as resin, film, fiber, glass, metal, etc. by adhesion, coating, spray or the like And the properties of the substrate surface can be modified.

  The surface of the cured film obtained by curing the active energy ray-curable coating solution to which the fluorine-containing copolymer and / or the photopolymerization initiator of the present invention is added has a low water contact angle as compared with the case where it is not added Become. If an overcoat layer is formed on the hard coat surface where the water contact angle exceeds 60 °, repelling and unevenness may be caused. The fluorine-containing copolymer of the present invention is used, for example, for the purpose of suppressing the repelling and unevenness of the overcoat layer by reducing the contact angle of water on the surface of the hard coat to 60 ° or less. As shown in the examples, when dipentaerythritol hexaacrylate or urethane acrylate oligomer is used as the resin monomer or oligomer of the active energy ray-curable coating solution, the contact angle of water on the surface of the coating is 45 ° to 60 °. It becomes a range and becomes a moderate hydrophilic surface. When the contact angle of water is within this range, repelling is unlikely to occur when the water-soluble paint or the like is overcoated, which is preferable.

Resin Composition Containing Fluorocopolymer The curable resin composition included in the present invention is prepared as a coating liquid for coating on a substrate. The curable resin composition (coating liquid) contains a fluorine-containing copolymer and / or a reactive fluorine-containing copolymer as a component exhibiting antifouling property and leveling property, and an energy ray-curable property mainly functioning as a resin film A resin monomer or resin oligomer, as well as a polymerization initiator, a solvent and the like are blended. However, in the case of a solventless coating solution, no solvent is mixed, and in the case of radiation curing, no polymerization initiator is required. Moreover, you may add another component to a coating liquid as needed.

  The content of the fluorine-containing copolymer and / or the reactive fluorine-containing copolymer in the total amount of the curable resin composition of the present invention (excluding the amount of the solvent component when a solvent component is used) is usually It is about 0.001 to 10% by mass, preferably about 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass.

Energy ray curable resin monomer or resin oligomer component The curable resin composition of the present invention is added to the fluorine-containing copolymer and / or the reactive fluorine-containing copolymer and reacts with this to form a resin cured film It contains a radiation curable resin monomer and / or a resin oligomer (hereinafter sometimes referred to as a resin monomer or a resin oligomer).

Such resin monomers and resin oligomers are not particularly limited as long as they react with the fluorine-containing copolymer and / or the reactive fluorine-containing copolymer to form a cured film, and usually a hard coat film or a reflection The energy ray-curable resin monomer and / or resin oligomer used for the protective coating film can optionally be used.
As the said resin monomer and resin oligomer, reactive compounds, such as acrylics, such as various acrylates and acrylic urethanes, urethane type, an epoxy type, are mentioned, for example, Preferably acrylic resin is used. In particular, since the curable resin composition of the present invention is cured and used in the form of a film, it is preferable to use a resin monomer and / or a resin oligomer having a reactive functional group having two or more functional groups.

  Examples of resin monomers and resin oligomers having a reactive functional group having two or more functional groups include tricyclodecane dimethylol 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, trimethylolpropane PO modified triacrylate, glycerol PO addition triacrylate, trimethylolpropane EO modified triacrylate, trimethylolpropane EO modified trimethacrylate , Isocyanuric acid EO modified diacrylate, isocyanuric acid EO modified triacrylate, ε-cap Lolactone modified tris (acoxyethyl) isocyanurate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, various urethane acrylate oligomers (Nippon Synthetic Chemical Industry Co., Ltd. Shizuka series, manufactured by Negami Kogyo Co., Ltd. Art resin series etc.), etc. may be mentioned, but it is not particularly limited thereto. Although the said resin monomer and resin oligomer can be used even by 1 type, you may mix | blend and use 2 or more types by arbitrary ratios.

  Examples of energy rays for curing the resin monomer and the resin oligomer include radiation, electron beam, ultraviolet light, visible light and the like. Since the energy of electromagnetic waves is high in curing by radiation and electron beam, polymerization is possible only with the polymerizable double bond. In the case of using ultraviolet light or visible light as the energy source, it is preferable to blend a polymerization initiator component described later.

  The content of the resin monomer and the resin oligomer in the total amount of the curable resin composition of the present invention (excluding the amount of the solvent component when the solvent component is used) is usually about 55 to 99.9% by mass, preferably Is about 60 to 99.5% by mass, more preferably about 70 to 99% by mass.

  In addition, the ratio of the resin monomer and the resin oligomer to the fluorine-containing copolymer and / or the reactive fluorine-containing copolymer is 100 parts by mass of the resin monomer and the resin oligomer. The amount of the reactive fluorine-containing 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 In the curable resin composition of the present invention, in addition to the above-mentioned fluorine-containing copolymer and / or reactive fluorine-containing copolymer, resin monomer and / or resin oligomer, as necessary, polymerization initiation It may contain an agent component.

  As the polymerization initiator component, conventionally known ones can be used, and for example, a photopolymerization initiator can be used.

  A wide variety of photopolymerization initiators are known and may be appropriately selected and used. For example, 1-hydroxycyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzophenone, 1- [1 4- (2-hydroxyethoxy-phenyl) -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-benzyl phosphine oxide, bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-hydroxy-1- {4- [4- (2-hydroxy) 2-Methyl-propionyl) -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 (dimethylamino) benzophenone, dibenzyl ketone, fluorenone, 2-hydroxy -2-Methylpropiophenone, thioxanthone, benzyldimethylketanol, benzyl methoxyethyl acetal, ben In, anthraquinone, anthrone, dibenzosuberone, 4,4-bis (dimethylamino) chalcone, P-dimethylaminocinnamylidene indanone, 2- (P-dimethylaminophenylvinylene) -isonaphthothiazole, 3, 3- Examples thereof include carbonyl-bis (7-diethylaminocoumarin), 3-phenyl-5-benzoylthio-tetrazole and the like.

  When using a polymerization initiator component, although it is also possible to use one kind alone, two kinds or more may be arbitrarily blended and used. The addition amount of the polymerization initiator component is 100 parts by mass with respect to 100 parts by mass of the polymerizable resin component (the total amount of the fluorine-containing copolymer and / or the reactive fluorine-containing copolymer, the resin monomer and / or the resin oligomer) Usually, about 0.1 to 50 parts by mass, preferably about 0.5 to 30 parts by mass, and more preferably about 1 to 10 parts by mass.

Solvent Component The curable resin composition of the present invention does not need to contain a solvent component, but may contain a solvent component as required. As the solvent component, conventionally known solvent components may be used, and examples thereof include 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 and xylene And aromatic hydrocarbons, ethers such as diethyl ether, alkylene glycol monoethers such as diethylene glycol monoethyl ether, alkylene glycol diethers such as diethylene glycol diethyl ether, tetrahydrofuran, and 1,4-dioxane. These solvent components may be used alone or in combination of two or more in any proportion.

  When a solvent component is used, the amount of the solvent component in the curable resin composition of the present invention is the polymerizable resin component (the fluorine-containing copolymer and / or the reactive fluorine-containing copolymer, the resin monomer, and The amount is usually about 25 to about 5000 parts by mass, preferably about 40 to about 2000 parts by mass, and more preferably about 60 to about 1000 parts by mass, with respect to 100 parts by mass of (or total amount of resin oligomers).

Other Components In the curable resin composition of the present invention, fine particles, fillers and the like may be blended as needed in order to provide a shape on the surface of the cured film and to impart other desired functions.

Method of Producing Cured Film In the present invention, after the curable resin composition of the present invention is used as a coating liquid and the coating liquid is applied to a substrate, a cured film can be obtained by light irradiation or the like.

  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 The curable resin composition of the present invention is prepared as a coating solution by mixing and dissolving the components, fine particles, fillers and the like at an appropriate compounding ratio. Next, a coating solution is applied on the substrate to a constant film thickness, solvent components are removed by hot-air drying, vacuum drying, etc., and then energy rays such as radiation, electron beam, ultraviolet rays, visible light are irradiated. Thus, a cured film can be obtained.

  Although the coating method of the coating liquid is not particularly limited, for example, it is coated by wet coating, and as the method, for example, a gravure method, a bar coat method, a wire bar method, a spin coat method, a doctor blade method, a dip coat method, a slit coat method Etc.

  The substrate for producing the cured film is not particularly limited as long as the cured film can be supported, but for example, a sheet having transparency is desirable when used as a hard coat for optical applications. Examples of the material of the transparent sheet include glass, plastic and the like, and a plastic sheet is particularly preferable. As the plastic, thermoplastic resin, thermosetting resin and the like 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, polyurethane resin, Examples thereof include polyvinyl alcohol, polyvinyl chloride, acrylic resin, polycarbonate resin, polyacrylonitrile, cycloolefin polymer, polyether sulfone and the like. These sheets may be subjected to easy-adhesion treatments such as binder treatment, corona treatment, plasma treatment, and flame treatment, as necessary.

  The thickness of the cured film of the present invention is not particularly limited, and may be appropriately selected according to the application. Usually, it can be about 100 nm to 30 μm.

  The contents of the present invention will be explained by the following examples, but the contents of the present invention are not 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-A-2010-47680).

Synthesis example 1
In a three-necked flask (50 mL) equipped with a condenser, 1.00 g of fluorine-containing acrylate (A-1), 4.00 g of methoxypolyethylene glycol monoacrylate (C-1: AME-400 manufactured by NOF Corporation), There were added 4.00 g of 4-hydroxybutyl acrylate (B-1), 18.00 g of methyl isobutyl ketone, 0.065 g of 2,2'-azobisisobutyro nitrile, and 0.2 g of mercaptopropionic acid. Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring to initiate the reaction. Stirring was then continued at 80 ° C. for 14 hours. The end of the reaction was confirmed by the disappearance of the peak unique to each acrylate in ¹ H-NMR. The target fluorine-containing oligomer was obtained quantitatively (33% by mass methyl isobutyl ketone solution). The obtained fluorine-containing copolymer was prepared by adding methyl isobutyl ketone to a solid concentration of 30% by mass.

  The weight average molecular weight (Mw) of the obtained reduced fluoropolymer was measured using the following apparatus under the following conditions. The weight average molecular weight of the fluoropolymer obtained in Synthesis Example 1 was 6,700.

Device: ACQUITY UPLC H-Class (Waters)
Detector: ACQUITY UPLC ELS detection (Waters)
Column: TSKgel α-5000 (φ 7.8 mm × 30 cm) (Tosoh Corporation)
Guard column: TSK guard α (φ 6.0 mm × 4 cm) (Tosoh Corporation)
Solvent: Tetrahydrofuran (Kanto Chemical)
Column temperature: 40 ° C
Sample concentration: 0.05 to 0.1 wt%
Injection volume: 0.01 ml
Molecular weight calibration: Monodispersed polyethylene glycol (Tosoh)

Synthesis Examples 2 to 6 and 10 to 12, 14, 17 to 18
In the same manner as in Synthesis Example 1, a fluorine-containing copolymer was synthesized by changing the proportions of the monomers A, B, C, F and the compound D. The proportions of monomers and types of monomers are as shown in Table 1. The numbers in parentheses in Table 1 represent mass ratios (except for the column of monomer E). The numbers in parentheses of the monomer E represent the equivalent ratio of the monomer E to the hydroxyl group in the fluorine-containing copolymer.

Synthesis example 7
In the fluorine-containing copolymer obtained in Synthesis Example 1, 0.2 equivalent of 2- (isocyanatoethyl) acrylate (E-1) and 0.01 equivalent of a hydroxyl group-containing acrylate compound (B-1) The 1,4-diazabicyclo [2.2.2] octane was added and stirring of the reaction solution was continued at 50 ° C. for 20 hours. The end of the reaction was confirmed by FT-IR by the disappearance of -N = C = O absorption (2275-2250 cm- ¹ ). The desired reactive fluorine-containing oligomer was obtained quantitatively (30% by mass methyl isobutyl ketone solution).

Synthesis example 8
A reactive fluorine-containing 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 fluorine-containing copolymer was synthesized in the same manner as in Synthesis Example 7 except that the proportion of the monomer E was changed.

Synthesis example 13
A reactive fluorine-containing 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 fluorine-containing copolymer was synthesized in the same manner as in Synthesis Example 1 except that the ratio of monomers B and C was changed. The weight average molecular weight of the fluoropolymer obtained in Synthesis Example 15 was 12,000.
Synthesis example 16
A reactive fluorine-containing copolymer was synthesized in the same manner as in Synthesis Example 7 except that the copolymer obtained in Synthesis Example 15 was used. The weight average molecular weight of the fluoropolymer obtained in Synthesis Example 16 was 12,000.

Synthesis example 19
A reactive fluorine-containing 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 weight average molecular weight of the fluoropolymer obtained in Synthesis Example 19 was 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): methoxypolyethylene glycol monoacrylate (Branmer AME-400 manufactured by NOF Corporation, n 9 9)
(C-2): poly (ethylene oxide) acrylate (manufactured by NOF Corporation, Blenmer AE-400, n ≒ 10)
(C-3): poly (ethylene oxide) acrylate (Blender AE-200 manufactured by NOF Corporation, n 4.5 4.5)
(C-4): Methoxy polyethylene glycol monomethacrylate (Blender PME-400 manufactured by NOF 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- (isocyanate ethyl) acrylate (Karen AOI, manufactured by Showa Denko KK)

  50 parts by mass of dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., trade name: M-402) as a curable resin monomer, or 50 parts by mass of urethane acrylate resin (trade name: UV7640 B, manufactured by Japan Synthetic Chemical Co., Ltd.) Parts by weight of 1-hydroxycyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 184), 1.5 parts by weight of a compound of Synthesis Examples 1 to 19 (30% by weight solution Product) and 46.5 parts by mass of methyl isobutyl ketone (MIBK) as a solvent were mixed to prepare a curable coating liquid. This is spread with a No. 8 bar coater on a polyester film (made by Toyobo Co., Ltd., trade name: Cosmoshine A4100), charged in a dryer set at 100 ° C. for 3 minutes, the solvent is volatilized, and then UV irradiation is performed. The cured film was obtained. The evaluation results are shown in Table 2.

Evaluation Method (1) Compatibility The compatibility of the curable coating liquid was visually observed.
Evaluation criteria: Transparent = ○
White turbidity / Presence existence = ×

(2) Contact Angle The contact angle of water to the surface of the cured film immediately after preparation was measured using a contact angle measurement device (DropMaster 600, manufactured by Kyowa Interface Chemicals Co., Ltd.).
Evaluation criteria:
Contact angle less than 55 ° = 以下
The contact angle value is greater than 55 ° and less than 60 ° = ○
The contact angle value is greater than 60 ° and less than 65 ° = Δ
Contact angle value is more than 65 ° = ×

(3) Pencil hardness According to JIS K 5600-5-4, place the pencil lead at an angle of about 45 ° to the test coated plate surface, press it against the test coated plate surface with a load of 750 g, and move forward about uniformly at uniform speed. I moved more than 10 mm. The hardness symbol of the hardest pencil having no scratches, dents or tears on the coating was taken as the coating hardness.

(4) Surface smoothness The surface of the cured film after UV irradiation was visually observed.
Evaluation criteria: No streaks, no hajiki, etc. ○
There are streaks, hajiki etc. ×

  As can be seen from Table 2, all of the cured films of Examples 1 to 16 exhibited good surface smoothness and did not show a decrease in film strength, and the water contact angle was 60 ° or less, which is appropriate. Was found to exhibit a positive tendency to hydrophilicity. From Comparative Example 2, when the fluorine-containing (meth) acrylate A component was a linear tridecafluorooctyl group, the contact angle value of the material having excellent surface smoothness was high, and the surface became a water repellent surface. From Comparative Example 3, when the fluorine-containing (meth) acrylate A component was not contained, no surface smoothness was exhibited and no hydrophilization was performed. 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 it did not show sufficient hydrophilic tendency.

  The fluorine-containing copolymer according to the present invention is useful, for example, as a surface modifier to render the surface used in the field of glass, fiber, metal, resin, film, optical material, paint etc. hydrophilic. It is useful as a compound that can impart appropriate hydrophilicity and smoothness to the surface. Since the curable composition containing the fluorine-containing copolymer of the present invention is also excellent in transparency, it can also be used in fields requiring transparency such as optical applications.

Claims (11)

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

[Wherein, R f 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 methyl. ]

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

[R ⁷ is a divalent or trivalent hydrocarbon group having from 2 to 10 carbon atoms. Z represents COOH or OH, and x is an integer of 1 or 2. ]. Furthermore, the following general formula B:

[R ³ is a divalent group having 2 to 50 carbon atoms which may be substituted,
_{- (CH 2) n1- (n1} = 2~50)
_{-X-Y- (CH 2) n2} - (n2 = 2~43)
_{-X- (CH 2) n3 - (} n3 = 1~44)
-CH ₂ CH ₂ (OCH ₂ CH ₂ ) _{n 4-} (n 4 = 20 to 24)
-XCO (OCH ₂ CH ₂ ) _n 5-( n 5 = 1 to 21)
(Wherein X is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenylene, biphenylene or napthylene optionally having 1 to 3 substituents selected from the group consisting of halogen atoms Y is selected from -O-CO-, -COO-, -CONH- or -NHCO- . R ⁴ is H or methyl. ]
The fluorine-containing copolymer of Claim 1 which contains the (meth) acrylate compound monomer unit represented by these. The fluorine-containing copolymer according to claim 1 or 2, wherein the chain transfer agent is represented by the following general 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. ]. The fluorine-containing copolymer according to any one of claims 1 to 3, wherein the fluorine content in the copolymer is 2 % to 14 % by mass.   The mass ratio of the (meth) acrylate compound represented by general formula B, C is a ratio of 0.2 <= B / C <= 2, The fluorine-containing copolymer of any one of Claims 2-4. The hydroxyl group in the fluorine-containing copolymer according to claim 1 wherein R ⁵ is H and / or the hydroxyl group in the fluorine-containing copolymer according to any one of claims 2 to 5 is represented by the following general formula E The fluorine-containing copolymer which makes the (meth) acrylate compound which has an isocyanate group represented react.

[Wherein, 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)] It is. R ¹⁰ represents H or a methyl group. y is an integer of 1 or 2. ].   When the number of moles of the (meth) acrylate compound having a hydroxyl group among the monomer units constituting the fluorine-containing copolymer is p, and the number of moles of the (meth) acrylate compound represented by the general formula E is q, the molar ratio The ratio of 0.01 ≦ q / p ≦ 0.8 is the fluorine-containing copolymer according to claim 6.   The contact angle of water on the surface of the cured film obtained by curing the active energy ray-curable coating solution containing the fluorine-containing copolymer is lower than the contact angle when no fluorine-containing copolymer is added. The fluorine-containing copolymer of any one of the Claims 1-7 characterized by the above-mentioned.   The surface modifier containing the fluorine-containing copolymer of any one of Claims 1-8.   An active energy ray-curable coating solution comprising the fluorine-containing copolymer according to any one of claims 1 to 8, a polyfunctional (meth) acrylic compound and a photopolymerization initiator.   A cured film obtained by curing the active energy ray-curable coating solution according to claim 10.