TWI712623B - Fluorine-containing acrylic composition and its manufacturing method, fluorine-containing active energy ray curable composition and article - Google Patents

Abstract

The subject of the present invention is to provide a fluorine-containing acrylic composition that can impart liquid repellency and antifouling properties without increasing volatile organic compounds that do not have a group reactive with acryloyl groups, its preparation method, and curing of the fluorine-containing active energy rays Sexual composition, and articles with this hardened layer on the surface of the substrate.

As a solution of the present invention, a fluorine-containing acrylic composition is provided, which contains (A) and (B),

(A) Fluorinated acrylic compound of the following formula, X-Rf ¹ -Z ¹ -Q ¹ -[Z ² OR ¹ ] _a

(Rf ¹ is a divalent perfluoropolyether group, Q ¹ is a (a+1) valent linking group containing Si, Z ¹ is a divalent linking group, Z ² is a divalent hydrocarbon group, R ¹ is H, or contains ( α substituted) a monovalent organic group of acryloyl group, X is a fluorine atom or a group of -Z ¹ -Q ¹ -[Z ² OR ¹ ] _a ; a is 1~10)

(B) The viscosity at 25°C is 100mPa. s or less, and containing (meth)acrylic acid compound

The mass ratio of these is 0.03<(A)/(B)<10, and volatile organic compounds that do not have groups that react with acryl groups are not blended.

Description

Fluorine-containing acrylic composition and its manufacturing method, fluorine-containing active energy ray curable composition and article

The present invention relates to a fluorine-containing acrylic composition that can impart liquid repellency and antifouling properties by adding an active energy ray curable composition such as ultraviolet rays or electron beams, and a method for producing the fluorine-containing acrylic composition. The fluorine-containing active energy ray curable composition of the composition, and an article having a hardened layer of the composition on the surface of the substrate.

In the past, as a means for protecting the surface of a resin molded body, etc., a hard coat treatment has been widely used. This is to form a hard hardened resin layer (hard coat layer) on the surface of the molded body, making it difficult to scratch the person. As the material constituting the hard coat layer, a large amount of curable composition using active energy rays such as thermosetting resin or ultraviolet or electron beam curable resin is used.

In addition, with the expansion of the application field of resin molded products or the flow of high added value, the demand for high performance of the hardened resin layer (hard coat) has been increased. As one of these, the demand for hard coat Grant of antifouling properties. This is because the surface of the hard coat layer imparts water repellency, oil repellency, etc., which can be difficult to contaminate or can be easily removed even if contaminated.

As a method of imparting antifouling properties to hard coats, although widely used It is used for the method of coating and/or fixing the fluorine-containing antifouling agent on the surface of the hard coat layer once formed, but for the hardened resin composition before hardening by adding the hardenable fluorine component, by coating and hardening, The method of simultaneously forming a hard coat layer and imparting antifouling properties has also been studied. For example, in Japanese Patent Application Laid-Open No. 6-211945 (Patent Document 1), it is shown that a hard coat layer with antifouling properties is produced by adding a fluoroalkyl acrylate to an acrylic curable resin composition.

In addition, in order to improve the coatability or film performance of the hard coating process, the operation of the coating liquid diluted with an organic solvent has been widely performed. However, in recent years, from the suspense of the impact on the environment or the human body, the action to suppress the use of volatile organic solvents (VOC) has been improved, and the coating liquid for hard coating is also strongly required to be highly solid or solvent-free化. Along with this, for the additive composition added to impart liquid repellency and antifouling properties to the aforementioned hard-coated coating liquid, there is also a pursuit of volatile organic compounds that do not contain reactive groups such as volatile organic solvents. The constituents.

[Prior technical literature] 〔Patent Literature〕

[Patent Document 1] Japanese Patent Application Publication No. 6-211945

[Patent Document 2] JP 2010-53114 A

[Patent Document 3] JP 2010-138112 A

[Patent Document 4] JP 2010-285501 A

The present invention has been completed in view of the foregoing. By suppressing the content of non-reactive groups of volatile organic compounds, it provides a curable composition that does not increase the curable composition that does not have an acrylic acid group. Reactive (non-reactive) volatile organic compounds (especially non-reactive volatile organic compounds that do not contain (meth)acrylic acid groups in the molecule), and can impart liquid repellency and antifouling properties The fluorine-containing acrylic composition, the manufacturing method of the fluorine-containing acrylic composition, the fluorine-containing active energy ray curable composition having the composition, and the article having the hardened layer of the composition on the surface of the substrate are intended .

The inventors of the present invention have made various developments as fluorine compounds that can impart antifouling properties to such curable resin compositions. For example, Japanese Patent Application Publication No. 2010-53114 (Patent Document 2) and Japanese Patent Application Publication No. 2010-53114 have been proposed. Photocurable fluorine compounds shown in 2010-138112 (Patent Document 3) and JP 2010-285501 A (Patent Document 4).

These structures have a fluoropolyether structure and a plurality of acryl groups in one molecule, although high antifouling properties can be imparted to the curable resin composition, but on the other hand, because the monomer is a highly viscous liquid that is difficult to handle In order to facilitate handling and improve the compatibility with the resin composition, it is necessary to operate as a solution diluted with a highly volatile organic solvent. Therefore, there is a problem that it cannot be directly blended with solvent-free hard coat agents or paints.

Therefore, as a result of further research, the inventors found There is a fluorine-containing acrylic composition, which contains (A) the fluorine-containing acrylic compound represented by the formula (1) described later, and (B) the viscosity at 25° C. is 100 mPa. s or less, an acrylic compound containing one or two (meth)acrylic groups in a molecule, characterized in that the mass ratio of (A) component to (B) component is 0.03<(A)/(B) Within the range of <10, no volatile organic compounds (especially non-reactive volatile organic compounds that do not contain (meth)acrylic acid groups) that do not have groups reactive with acryloyl groups are incorporated in the molecule, by By adding the fluorine-containing acrylic composition to the active energy ray curable composition, a fluorine-containing active energy ray curable composition having liquid repellency and antifouling properties while suppressing the content of volatile organic compounds can be obtained. To complete the present invention.

Accordingly, the present invention provides the following fluorine-containing acrylic composition and its manufacturing method.

[1] A fluorine-containing acrylic composition containing the following (A) and (B) as essential components,

(A) The fluorine-containing acrylic compound represented by the following general formula (1), X-Rf ¹ -Z ¹ -Q ¹ -[Z ² OR ¹ ] _a (1)

(In the formula, Rf ¹ is a divalent perfluoropolyether group with a molecular weight of 800 to 20,000 formed by a perfluoroalkylene group with 1 to 6 carbon atoms and an oxygen atom, and Q ¹ independently contains at least (a+1) The (a+1) valence linking group of one silicon atom can be a cyclic structure and can contain at least one selected from oxygen atom, nitrogen atom and fluorine atom; Z ^{1 is} independently of carbon number 1-20 and can also be included A divalent linking group selected from at least one of oxygen atoms, nitrogen atoms and silicon atoms, which may contain a cyclic structure in the way, may become branched, and some of the hydrogen atoms may be substituted by fluorine atoms; Z ^{2 is} independently a carbon number of 1~ 200 may also include at least one divalent hydrocarbon group selected from oxygen atoms, nitrogen atoms and silicon atoms, and may include a cyclic structure in the way; R ^{1 is} independently a hydrogen atom, or contains: may also include oxygen atoms and At least one of the nitrogen atoms is a monovalent organic group of an acryloyl group or an α-substituted acryloyl group. However, R ¹ is an average of at least one containing the aforementioned acryloyl group or an α-substituted acryloyl group in one molecule. A valent organic group; X is a fluorine atom or -Z ¹ -Q ¹ -[Z ² OR ¹ ] _a monovalent group represented by a; a is an integer from 1 to 10)

(B) The viscosity at 25°C is 100mPa. s or less, and contains 1 or 2 (meth)acrylic acid compounds in one molecule

The mass ratio of the component (A) to the component (B) is in the range of 0.03<(A)/(B)<10, and moreover, it is not blended with a volatile organic compound that does not have a group reactive with an acryloyl group.

[2] The fluorine-containing acrylic composition according to [1], wherein, as part or all of component (B), it contains an acrylic compound represented by the following general formula (2), CH ₂ =CR ⁶ COOR ⁵ (2)

(In the formula, R ⁵ is an alkyl, aryl or aralkyl group with 1 to 20 carbon atoms, which may be branched or cyclic, and may contain aliphatic unsaturated bonds, urethane bonds, ether bonds, Isocyanate group, hydroxyl group; R ⁶ is a hydrogen atom or a methyl group, a fluorine atom, a fluoroalkyl group with 1 to 6 carbon atoms).

[3] The fluorine-containing acrylic composition according to [1] or [2], wherein the component (B) is an acrylic compound in which a part of hydrogen atoms is substituted with a halogen atom selected from F, Cl, and Br.

[4] The fluorine-containing acrylic composition according to [3], wherein, as part or all of component (B), it contains a fluorine-containing acrylic compound represented by the following general formula (3), CH ₂ =CR ² COOZ ³ Rf ² (3)

(However, in the formula, R ² is independently a hydrogen atom, F, Cl, Br or a monovalent hydrocarbon group with 1 to 8 carbons. The hydrogen atom in the hydrocarbon group can be replaced by F, Cl, Br; Z ³ is independently a carbon A divalent hydrocarbon group of 1 to 8 can be branched, and it can contain an oxygen atom and a hydroxyl group in the middle; Rf ² is a fluoroalkyl group with 2 to 20 fluorine atoms, which can contain a hydrogen atom and an oxygen atom, and can be branched).

[5] The fluorine-containing acrylic composition according to any one of [1] to [4], wherein, in the fluorine-containing acrylic compound represented by the general formula (1) of component (A), Rf ¹ is the following 3 types of structures Any one of the bivalent perfluoropolyether groups represented by the formula, -CF ₂ O-(CF ₂ O) _p (CF ₂ CF ₂ O) _q -CF _2-

(However, the arrangement of repeating units included in () is random, p is an integer from 1 to 200, q is an integer from 1 to 170, p+q is from 6 to 201; s is an integer from 0 to 6, t, u is an integer from 1 to 100, t+u is an integer from 2 to 120; v is an integer from 1 to 120).

[6] The fluorinated acrylic composition according to any one of [1] to [5], wherein, in the component (A), Z ¹ in the general formula (1) is any structure represented by the following formula,- CH ₂ CH ₂ CH ₂ CH _2-

-CH ₂ OCH ₂ CH ₂ CH _2-

[7] The fluorine-containing acrylic composition according to any one of [1] to [6], wherein in component (A), Q ¹ in general formula (1) is a structure represented by the following formula,

(In the formula, a is an integer from 1 to 10 independently).

[8] The fluorinated acrylic composition according to any one of [1] to [7], wherein the component (A) is selected from fluorinated acrylic compounds represented by the following formulas,

(In the formula, Rf' is -CF ₂ O(CF ₂ O) _p (CF ₂ CF ₂ O) _q CF ₂ -, p is an integer from 1 to 200, q is an integer from 1 to 170, and p+q is 6. ~201; e1 is an integer from 1 to 30; R'is a hydrogen atom,

or

These can be mixed in one molecule; however, R'contains at least one monovalent organic group of the (meth)acryloyl group in one molecule on average, and v1 is an integer of 2 to 120).

[9] A method for producing a fluorine-containing acrylic composition, characterized by having a step of reacting (C) and (D) in the presence of (B) to produce (A), (B) at 25°C The viscosity is 100mPa. s or less, and an acrylic compound containing one or two (meth)acryloyl groups in one molecule; (C) a fluorine-containing polyfunctional alcohol compound represented by the following general formula (4); X ¹ -Rf ^1- Z ¹ -Q ¹ -[Z ² OH] _a (4)

(In the formula, X ¹ is a fluorine atom or _a group represented by -Z ¹ -Q ¹ -[Z ² OH] _a , Rf ¹ is composed of a perfluoroalkylene group with 1 to 6 carbon atoms and an oxygen atom with a molecular weight of 800 ~20,000 divalent perfluoropolyether group, Z ^{1 is} independently a divalent linking group with 1-20 carbon atoms, which may also contain at least one selected from oxygen atom, nitrogen atom and silicon atom, Q ¹ is independently at least The (a+1) valent linking group containing (a+1) silicon atoms can be a cyclic structure and can contain at least one selected from the group consisting of oxygen atoms, nitrogen atoms and fluorine atoms; Z ^{2 is} independently carbon number 1. ~200 can also contain at least one divalent hydrocarbon group selected from oxygen atoms, nitrogen atoms and silicon atoms, and can contain a cyclic structure on the way; a is an integer from 1 to 10); (D) has in 1 molecule A compound of one isocyanate group and at least one (meth)acryloyl group; (A) the fluorinated acrylic compound represented by the following general formula (1) X-Rf ¹ -Z ¹ -Q ¹ -[Z ² OR ¹ ] _a (1)

(In the formula, Rf ¹ , Z ¹ , Q ¹ , Z ² , and a are the same as above; R ¹ is independently a hydrogen atom, or contains: Propylene which may contain at least one selected from an oxygen atom and a nitrogen atom The monovalent organic group of an acyl group or an α-substituted acryloyl group, however, R ¹ is an average of at least one monovalent organic group containing the aforementioned acryloyl group or an α-substituted acryloyl group in one molecule, and X is a fluorine atom or -Z ¹ -Q ¹ -[Z ² OR ¹ ] _a represents the monovalent base)

The mass ratio of the above-mentioned (A) component and (B) component is within the range of 0.03<(A)/(B)<10. Moreover, it is obtained without blending of volatile organic compounds that do not have groups reactive with acryloyl groups Fluorinated acrylic composition.

[10] The method for producing a fluorine-containing acrylic composition according to [9], wherein part or all of component (B) contains an acrylic compound represented by the following general formula (2) and/or the following general formula ( 3) Fluorinated acrylic compound represented, CH ₂ =CR ⁶ COOR ⁵ (2)

(In the formula, R ⁵ is an alkyl, aryl or aralkyl group with 1 to 20 carbon atoms, which may be branched or cyclic, and may contain aliphatic unsaturated bonds, urethane bonds, ether bonds, Isocyanate group, hydroxyl group; R ⁶ is a hydrogen atom or a methyl group, a fluorine atom, a fluoroalkyl group with 1 to 6 carbon atoms)

CH ₂ =CR ² COOZ ³ Rf ² (3)

(However, in the formula, R ² is independently a hydrogen atom, F, Cl, Br or a monovalent hydrocarbon group with 1 to 8 carbons. The hydrogen atom in the hydrocarbon group can be replaced by F, Cl, Br; Z ³ is independently a carbon A divalent hydrocarbon group of 1 to 8 can be branched, and it can contain an oxygen atom and a hydroxyl group in the middle; Rf ² is a fluoroalkyl group with 2 to 20 fluorine atoms, which can contain a hydrogen atom, an oxygen atom, or it can be branched)

In the general formula (4) of component (C) and general formula (1) of component (A), Rf ¹ is any one of the divalent perfluoropolyether groups represented by the following three structural formulas, -CF ₂ O -(CF ₂ O) _p (CF ₂ CF ₂ O) _q -CF _2-

(However, the arrangement of repeating units included in () is random, p is an integer from 1 to 200, q is an integer from 1 to 170, p+q is from 6 to 201; s is an integer from 0 to 6, t, u is an integer from 1 to 100, t+u is an integer from 2 to 120; v is an integer from 1 to 120)

Z ¹ is any structure represented by the following formula, -CH ₂ CH ₂ CH ₂ CH _2-

-CH ₂ OCH ₂ CH ₂ CH _2-

Q ¹ is the structure represented by the following formula,

(In the formula, a is an integer from 1 to 10 independently).

[11] A fluorine-containing active energy ray curable composition characterized by containing 0.005 to 40 parts by mass of any of [1] to [8] relative to 100 parts by mass of the active energy ray curable composition (E) One item of fluorine-containing acrylic composition.

[12] The fluorine-containing active energy ray curable composition according to [11], wherein the active energy ray curable composition (E) contains (Ea) acrylic compound: 100 parts by mass, (Eb) photopolymerization initiator : 0.1-15 parts by mass.

[13] An article having a hardened layer of the fluorine-containing active energy ray hardenable composition such as [11] or [12] on the surface.

According to the fluorine-containing acrylic composition of the present invention, it is possible to provide a non-reactive volatile organic compound that does not have groups reactive with acryloyl groups (especially non-reactive volatile organic compounds that do not contain (meth)acryloyl groups in the molecule). The content of the organic compound) is added to the active energy ray curable composition, and can impart liquid repellency and antifouling properties to a fluorine-containing active energy ray curable composition.

The fluorine-containing acrylic composition of the present invention contains (A) the fluorine-containing acrylic compound represented by the formula (1) described later, and (B) the viscosity at 25° C. is 100 mPa. s or less, an acrylic compound containing one or two (meth)acrylic groups in a molecule, characterized in that the mass ratio of (A) component to (B) component is 0.03<(A)/(B) Within the range of <10, no volatile organic compound (especially non-reactive volatile organic compound that does not contain a (meth)acryloyl group) in the molecule is not blended with a group reactive with acryloyl group.

The fluorine-containing acrylic compound of component (A) which is the first essential component of the fluorine-containing acrylic composition of the present invention is represented by the following general formula (1). Furthermore, in the present invention, the so-called "acrylic compound" is a general term for compounds having acryloyl groups and α-substituted acryloyl groups, and also includes urethane acrylates having urethane bonds in the molecule, Or introduce 2 or more acryloyl and α-substituted acryloyl compounds into the side chains or ends of various polymers by any method. Also, in the present invention, the so-called "(甲 "Acrylate" means one or both of acrylate and methacrylate.

X-Rf ¹ -Z ¹ -Q ¹ -[Z ² OR ¹ ] _a (1)

In the above formula (1), Rf ¹ is a divalent perfluoropolyether group with a molecular weight of 800 to 20,000 composed of a perfluoroalkylene group having 1 to 4 carbon atoms, especially 1 to 4, and an oxygen atom. In particular, a linear perfluoropolyether group with a molecular weight of 1,000 to 10,000 is preferred. In the present invention, the molecular weight is a number average molecular weight calculated from the ratio of the terminal structure and the main chain structure based on ¹ H-NMR and ¹⁹ F-NMR.

As Rf ¹ , it is particularly preferable to be composed of any one or plural combination of the repeating unit group shown below.

-CF ₂ O-

-CF ₂ CF ₂ O-

-CF ₂ CF ₂ CF ₂ O-

-CF(CF ₃ )CF ₂ O-

Here, as a part that is not suitable for the main structure, the bonding part with Z ^{1 and} the initiator fragment or by-product structure when the main chain structure is constructed can be cited.

Among them, it is particularly suitable that Rf ¹ is any one of the following structures.

-CF ₂ O-(CF ₂ O) _p (CF ₂ CF ₂ O) _q -CF _2-

Thereto, P and q are diagrams () included in the structure of -CF ₂ O- and -CF ₂ CF ₂ O- total configuration of the individual, the individual structure -CF ₂ O- and -CF ₂ CF ₂ O- structure The arrangement is random. In this case, p is an integer from 1 to 200, q is an integer from 1 to 170, and p+q is an integer from 6 to 201.

Furthermore, taking s as an integer from 0 to 6, t and u are respectively an integer from 1 to 100, t+u is an integer from 2 to 120, and v is preferably an integer from 1 to 120.

When the value of p+q, t+u, or v is small, the characteristics sought as a fluorine compound are unlikely to appear. When these values are too large, the compatibility with other components deteriorates. The values of p, q and p+q, t, u and t+u or v in the composition can be single or distributed. In the case of distribution, the value sought by ¹⁹ F-NMR etc. The average molecular weight preferably satisfies the above range.

In the above formula (1), Z ¹ is independently a divalent linking group with 1 to 20 carbon atoms, which may also include at least one selected from an oxygen atom, a nitrogen atom, and a silicon atom, and may include a cyclic structure on the way, Become a branch, part of the hydrogen atoms can be replaced by fluorine atoms.

As a preferable ^one of Z ¹ , the following structures can be cited.

-CH ₂ CH _2-

-CH ₂ CH ₂ CH _2-

-CH ₂ CH ₂ CH ₂ CH _2-

-CH ₂ OCH ₂ CH _2-

-CH ₂ OCH ₂ CH ₂ CH _2-

Among them, as a particularly preferable structure of Z ¹ , the following can be cited.

-CH ₂ CH ₂ CH ₂ CH _2-

-CH ₂ OCH ₂ CH ₂ CH _2-

In the above formula (1), Q ¹ is an (a+1) valent linking group independently containing at least (a+1) silicon atoms, which can be a cyclic structure, and can contain oxygen atoms, nitrogen atoms and fluorine atoms At least one of them. As such a preferred Q ¹ , siloxane structures having (a+1) Si atoms, unsubstituted or halogen-substituted silylene structures, silylene structures, or the like (A+1)-valent linking group composed of two or more combinations.

As a particularly preferable structure, specifically, the following structure is shown.

However, a is the same as a in the above formula (1), and is independently an integer from 1 to 10, preferably an integer from 1 to 8, and more preferably an integer from 1 to 4. In addition, b is an integer of 1 to 5, preferably an integer of 3 to 5. The arrangement of each unit is random, (a+1) the bonding part of each unit, etc. is connected to the end of one Z ¹ (CH ₂ etc.) and the end of a Z ² included in [] (CH ₂ Etc.) Bonding.

Here, T is a (a+1)-valent linking group, for example, the following are illustrated.

Among them, the best Q ¹ is below.

In the above formula (1), Z ² is independently a divalent hydrocarbon group having 1 to 200 carbon atoms and may also include at least one selected from the group consisting of oxygen atoms, nitrogen atoms, and silicon atoms, preferably 2 to 80. Contains ring structure.

Z ² as the preferred configuration, exemplified by the following.

-CH _2-

-CH ₂ CH _2-

-CH ₂ CH ₂ CH _2-

-CH ₂ CH ₂ CH ₂ CH _2-

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2-

-CH ₂ CH ₂ CH ₂ OCH ₂ CH _2-

-CH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH _2-

-CH ₂ CH ₂ CH ₂ [OC ₂ H ₄ ] _d [OC ₃ H ₆ ] _e [OC ₄ H ₈ ] _f-

Here, d is an integer from 0 to 99, e is an integer from 0 to 66, and f is an integer from 0 to 50. The total number of carbons is less than 200. The arrangement of repeating units is random regardless of type. Moreover, each repeating unit is not a monomer but can be a structure Make a mixture of isomers.

As a particularly preferable structure of Z ² , the following may be mentioned. Among them, those with d of 1-30 and e of 1-30 are suitable.

-CH ₂ CH ₂ CH ₂ [OC ₂ H ₄ ] _d-

-CH ₂ CH ₂ CH ₂ [OC ₃ H ₆ ] _e-

In the above formula (1), R ¹ is independently a hydrogen atom, or a monovalent organic group containing at least one acryloyl group selected from an oxygen atom and a nitrogen atom or an α-substituted acryloyl group, but , R ¹ is an average of at least one monovalent organic group containing the aforementioned acryloyl group or α-substituted acryloyl group in one molecule. As the monovalent organic group, it is preferred to have at least one at the end, preferably 1 to 5 acryloyl groups or α-substituted acryloyl groups. Examples of the substituent include methyl, ethyl, and From halogen atoms in F, CF ₃ , Cl and Br, etc. In addition, it may have an amide bond, an ether bond, an ester bond, etc. in the middle of the structure, and in particular, the R ¹ O- group may include a urethane bond (-NH(C=O)O-). Examples of the structure of such R ¹ include the following.

CH ₂ =CHCO-

CH ₂ =C(CH ₃ )CO-

CH ₂ =C(C ₂ H ₅ )CO-

CH ₂ =CFCO-

CH ₂ =CClCO-

CH ₂ =CBrCO-

CH ₂ =C(CF ₃ )CO-

CH ₂ =CHCOOCH ₂ CH ₂ -NHCO-

CH ₂ =C(CH ₃ )COOCH ₂ CH ₂ -NHCO-

CH ₂ =C(CH ₃ )COOCH ₂ CH ₂ OCH ₂ CH ₂ -NHCO-

(CH ₂ =CHCOOCH ₂ CH ₂ ) ₂ C(CH ₃ )-NHCO-

Among them, the following are particularly suitable.

CH ₂ =CHCOOCH ₂ CH ₂ -NHCO-

CH ₂ =C(CH ₃ )COOCH ₂ CH ₂ -NHCO-

In the fluorine-containing acrylic compound represented by formula (1), although part of R ¹ may be hydrogen atoms, not all of them are hydrogen atoms, and it contains on average more than one acryloyl group and/or α-substituted acryloyl group in one molecule Base.

In the above formula (1), X is a fluorine atom or _a monovalent group represented by -Z ¹ -Q ¹ -[Z ² OR ¹ ] _a . Here, Z ¹ , Q ¹ , Z ² , R ¹ , and a are the same as described above.

As the fluorine-containing acrylic compound represented by the above formula (1), when X is -Z ¹ -Q ¹ -[Z ² OR ¹ ] _a , more specifically, the following structure can be represented.

(In the formula, Rf' is -CF ₂ O(CF ₂ O) _p (CF ₂ CF ₂ O) _q CF ₂ -, p, q, p+q are the same as above, for example, q/p=0.9, p+ q≒45. e1 is an integer from 1 to 30, such as 2, 4, 9. R'is a hydrogen atom,

or

These can be mixed in one molecule. However, R'contains at least one monovalent organic group of the (meth)acryloyl group in one molecule on average).

As the fluorine-containing acrylic compound represented by the above formula (1), a preferable structure when X is a fluorine atom, specifically the following structure can be represented.

(In the formula, v1 is an integer from 2 to 120, preferably an integer from 4 to 60, and e1 and R'are as described above).

These (A) components may be singular or may be a mixture of plural compounds as defined above. In the case of a mixture, the total content of the compounds corresponding to (A) may be calculated as the content of the (A) component.

The second essential component of the fluorine-containing acrylic composition of the present invention is (B) an acrylic compound containing one or two (meth)acryloyl groups in one molecule. The (B) component has a viscosity of 100 mPa at 25°C in terms of its solubility with (A) component and its compatibility with (C) component described later. s or less, preferably 0.4-20mPa. s. The hydrogen atom of the acrylic compound of component (B) may be partially substituted by chlorine atom (Cl), fluorine atom (F), or bromine atom (Br), and may contain oxygen and nitrogen atoms other than the acrylic structure, and may also contain ether Bond, urethane bond, isocyanate group, hydroxyl group.

As a preferable example of a compound having one (meth)acryloyl group in the molecule among such components (B), specifically, the following are shown General formula (2) said.

CH ₂ =CR ⁶ COOR ⁵ (2)

(In the formula, R ⁵ is an alkyl, aryl or aralkyl group with 1 to 20 carbon atoms, preferably 1 to 10, which may be branched or cyclic, and may contain aliphatic unsaturated (double) bonds, Ethyl urethane bond, ether bond, isocyanate group, hydroxyl group. Specific examples of R ⁵ include methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, phenyl, and dicyclopentane group, a dicyclopentenyl group, furfuryl group, tetrahydrofuranyl, _{tetrahydropyranyl, -CH 2 CH 2 -OH, -CH} 2 CH (CH 3) -OH, -CH 2 CH 2 -NCO like .R ⁶ It is a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms, and a hydrogen atom, a methyl group, a fluorine atom, and a trifluoromethyl group are particularly preferred).

As such compounds, more specifically, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, Isobutyl (meth)acrylate, hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethyl-hexyl (meth)acrylate, isodecyl (meth)acrylate Ester, tridecyl (meth)acrylate, isostearyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, tetrahydrofuran (meth)acrylate Acrylate, isobornyl (meth)acrylate, phenoxyethyl acrylate, neopentyl glycol-acrylic acid-benzoate, etc.

In addition, as an acrylate compound having a repeating unit structure of ethylene oxide, propylene oxide, tetramethylene oxide, lactone, etc., and various alkoxy groups, for example, methoxy polyethylene glycol (methyl )Acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxy polypropylene Glycol (meth)acrylate, nonylphenol EO adduct acrylate, etc. The commercially available (meth)acrylic compounds have a viscosity of 100mPa at 25°C. s or less can also be used.

In addition, as a compound having two acryloyl groups in one molecule, specific examples include 1,3-butanediol di(meth)acrylate and 1,4-butanediol di(meth)acrylic acid Ester, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, three Ethylene glycol di(meth)acrylate, nonanediol di(meth)acrylate, etc.

Furthermore, as a part or the whole of (B) component, it is suitable that a part of hydrogen atom is substituted by F, Cl, and Br, and it is especially desirable to be an acrylic compound represented by the following general formula (3).

CH ₂ =CR ² COOZ ³ Rf ² (3)

In the above formula (3), R ² is independently a hydrogen atom, F, Cl, Br, or a monovalent hydrocarbon group with 1 to 8 carbon atoms, and the hydrogen atom in the hydrocarbon group may be substituted by F, Cl, or Br.

Examples of monovalent hydrocarbon groups having 1 to 8 carbon atoms, especially carbon numbers 1 to 6, include alkyl groups such as methyl and ethyl groups, and fluoroalkyl groups such as trifluoromethyl groups. As R ² , a hydrogen atom and a methyl group are preferable.

In the above formula (3), Z ³ is independently a carbon number of 1 to 8, especially a divalent hydrocarbon group of carbon number of 1 to 4, which may be branched and may contain an oxygen atom and a hydroxyl group in the middle.

As particularly preferable Z ³ , the following can be cited.

-CH _2-

-CH ₂ CH _2-

-CH ₂ -CH(OH)-CH _2-

-CH ₂ -CH ₂ -O-CH ₂ CH _2-

In the above formula (3), Rf ² is a fluoroalkyl group having 2 to 20 fluorine atoms, especially 1 to 10, which may contain hydrogen atoms and oxygen atoms, and may be branched.

As Rf ² , specifically, it means the following.

-CF ₃

-C ₂ F ₅

-C ₃ F ₇

-C ₄ F ₉

-C ₆ F ₁₃

-CF ₂ H

-C ₂ F ₄ H

-CF ₂ CF ₂ H

-CF ₂ CF ₂ CF ₂ CF ₂ H

-CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ H

-CF ₂ CF ₂ CF(CF ₃ ) ₂

-CF(CF ₃ ) ₂

-CH(CF ₃ ) ₂

-CF ₂ CHFCF ₃

-CF ₂ CF ₂ OCF ₃

As the acrylic compound of the component (B) satisfying the above conditions, the following can be specifically exemplified.

CH ₂ =CHCOOCH ₂ CH ₂ C ₄ F ₉

CH ₂ =CHCOOCH ₂ CH ₂ C ₆ F ₁₃

CH ₂ =C(CH ₃ )COOCH ₂ CH ₂ C ₄ F ₉

CH ₂ =C(CH ₃ )COOCH ₂ CH ₂ C ₆ F ₁₃

The component (B) may be a single component or a mixture of plural compounds as defined above. In the case of a mixture, the total content of the compound corresponding to (B) may be calculated as the content of the component (B). Although the compound corresponding to the component (B) can be synthesized by a known method if necessary, it is commercially available from various reagent manufacturers, etc., and can be used directly.

The fluorine-containing acrylic composition of the first embodiment of the present invention has the aforementioned (A) and (B) components as essential components, and the mass ratio of (A) component and (B) component is 0.03<(A)/(B) )<10, preferably 0.05≦(A)/(B)≦8, more preferably within the range of 0.1≦(A)/(B)≦5, and even if it is not blended, it does not have any reaction with acryl group Volatile organic compounds (especially non-reactive volatile organic compounds that do not contain (meth)acrylic acid groups) in the molecule.

As another embodiment of the present invention, the fluorine-containing acrylic composition and the active energy ray-curable composition (E) described later are mixed to form the fluorine-containing active energy ray-curable composition, and the case is applied and cured Next, although it is possible to provide a liquid-repellent and antifouling hardened layer on the substrate, the liquid-repellent and antifouling properties are achieved by being dispersed in the components of the active energy ray curable composition (E) ( A) The components are present on the surface of the hardened layer. Therefore, when the above-mentioned mass ratio (A)/(B) is 0.03 or less, the content of the (A) component in the fluorinated acrylic composition is excessively reduced, making it difficult to express the final liquid repellency and antifouling properties. In addition, when the mass ratio (A)/(B) is 10 or more, Due to the high viscosity of (A) component, the workability is reduced, and the compatibility or mixing with (E) component is reduced.

In the fluorine-containing acrylic composition of the first embodiment of the present invention, the production method is not particularly limited, and the components (A) and (B) produced by various methods can be mixed. However, the acrylic compound of component (A) improves its liquid repellency and antifouling properties, and increases its viscosity. It tends to be difficult to remove volatiles and become high-viscosity compounds. When volatiles are removed, it is effective in reducing pressure, Conditions such as heating cause polymerization of the acryl group in the structure of component (A), and there is a high risk of thickening or gelation. Therefore, it is more preferable to prepare a raw material from which volatile components (volatile organic compounds that do not have a reactive group with the acryl group) have been removed in the synthesis step before the introduction of the acryl group, and use this to synthesize in the presence of component (B) (A) It is desired to obtain the target fluorine-containing acrylic composition for the component.

As the method for producing the fluorine-containing acrylic compound represented by the formula (1) of the component (A), for example, first, a polyfunctional Si-H group represented by the following general formula (5) is produced by a conventionally known method Fluoropolyether compound, X'-Rf ¹ -Z ¹ -Q ¹ -[H] _a (5)

(In the formula, Rf ¹ , Z ¹ , Q ¹ , and a are the same as above, and the a H series included in [] are all bonded to the silicon atom in the Q ¹ structure. X'is a fluorine atom or -Z ^1- Q ¹ -[H] _a ), and the following general formula (6) with an unsaturated group-containing alcohol at the end (a compound having an alkenyl group and an alcoholic hydroxyl group in the molecule) for hydrosilation reaction, CH ₂ =CR ⁴ -Z ³ -OH (6)

(In the formula, the -CH ₂ -CHR ⁴ -Z ³ -structure formed by hydrogenation of R ⁴ and Z ³ is sufficient if it satisfies the requirements of Z ² in formula (1), and R ⁴ and Z ³ can be Bonded into a ring structure)

A fluorine-containing polyfunctional alcohol compound represented by the following general formula (4) as an intermediate is obtained.

X ¹ -Rf ¹ -Z ¹ -Q ¹ -[Z ² OH] _a (4)

(In the formula, X ¹ is a fluorine atom or _a group represented by -Z ¹ -Q ¹ -[Z ² OH] _a , and Rf ¹ , Z ¹ , Q ¹ , Z ² and a are as described above).

Here, as the fluoropolyether compound having the polyfunctional Si-H group represented by the above formula (5), the following can be exemplified.

(In the formula, Rf' is the same as above).

(In the formula, v1 is the same as above).

In addition, as the terminal unsaturated group-containing alcohol represented by the above formula (6), the following can be exemplified.

CH ₂ =CH-CH ₂ -OH

CH ₂ =CH-CH ₂ -OCH ₂ CH ₂ -OH

CH ₂ =CH-CH ₂ -OCH ₂ CH ₂ CH ₂ -OH

CH ₂ =CH-CH ₂ -OCH ₂ CH(CH ₃ )-OH

CH ₂ =CH-CH ₂ -OCH ₂ CH ₂ CH ₂ CH ₂ -OH

CH ₂ =CH-CH ₂ -(OCH ₂ CH ₂ ) _d1 -OH

CH ₂ =CH-CH ₂ -(OC ₃ H ₆ ) _e1-1 -OCH ₂ CH(CH ₃ )-OH

(In the formula, d1 is an integer from 1 to 30, and e1 is the same as above).

This hydrosilation (addition) reaction is expected to mix a fluoropolyether compound having a polyfunctional Si-H group represented by formula (5), an alcohol with an unsaturated group at the end represented by formula (6), and a platinum group metal In the presence of the addition reaction catalyst, the reaction is carried out at a reaction temperature of 50-150°C, preferably 60-120°C, for 1 minute to 48 hours, especially 10 minutes to 12 hours. When the reaction temperature is too low, the reaction may not proceed sufficiently to stop the reaction. When it is too high, the reaction cannot be controlled due to the temperature rise caused by the reaction heat of hydrosilation, which may cause bumping or decomposition of raw materials.

In this case, it is expected that the reaction ratio of a fluoropolyether compound having a multifunctional Si-H group represented by the formula (5) and an alcohol having an unsaturated group at the end represented by the formula (6) is relative to that of the alcohol having a formula (5) The total number of moles of H included in the [] of the multifunctional Si-H-based fluoropolyether compound, using 0.5 to 5.0 times the moles of the terminal unsaturated group of the alcohol with an unsaturated group represented by the formula (6) , Especially using 0.9~2.0 times mole for reaction. When there are fewer alcohols with unsaturated groups at the end represented by formula (6) than this, it may become difficult to obtain a fluorine-containing polyfunctional alcohol compound with high solubility. When more than this, the uniformity of the reaction solution is reduced , The reaction rate becomes unstable, and when the unsaturation-containing alcohol at the end represented by the formula (6) is removed after the reaction, only the remaining unreacted alcohol must be heated, depressurized, Conditions for extraction, etc.

As the addition reaction catalyst, for example, compounds containing platinum group metals such as platinum, rhodium or palladium can be used. Among them, compounds containing platinum are preferred, and hexachloroplatinum (IV) acid hexahydrate, platinum carbonyl vinyl methyl complexes, platinum-divinyl tetramethyl disiloxane complexes, platinum -Cyclovinylmethylsiloxane complex, platinum-octylaldehyde/octanol complex, or platinum supported on activated carbon.

The blending amount of the addition reaction catalyst is preferably 0.1 to 5,000 mass ppm relative to the fluoropolyether compound having a multifunctional Si-H group represented by formula (5), and the amount of metal contained in the addition reaction catalyst More preferably, the amount is 1 to 1,000 ppm by mass.

The above-mentioned addition reaction can be carried out even in the absence of a solvent, but it can be diluted with a solvent if necessary. At this time, although toluene, xylene, isooctane and other commonly used organic solvents can be used as the dilution solvent, it is preferable that the boiling point is higher than the intended reaction temperature and does not hinder the reaction. The resulting fluorine-containing polyfunctional after the reaction The alcohol compound is soluble at the above reaction temperature. As such a solvent, for example, fluorine-modified aromatic hydrocarbon solvents such as meta-xylene hexafluoride and Benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether are expected to be partially processed The fluorine-modified solvent is particularly preferably metaxylene hexafluoride.

When a solvent is used, the amount used is relative to 100 parts by mass of the fluoropolyether compound having a multifunctional Si-H group represented by formula (5), preferably 5 to 2,000 parts by mass, more preferably 50 to 500 parts by mass . If it is less than this, the dilution effect of the solvent becomes thinner, if it is more, the dilution becomes too high, which may result in a decrease in the reaction rate.

After the completion of the reaction, the unreacted alcohol or diluent solvent with unsaturated group at the end represented by formula (6) is removed by vacuum distillation, and it is preferably removed by well-known methods such as extraction and adsorption. Although these methods can be implemented individually or in combination with multiple methods, especially in the final stage of removal, by using vacuum distillation or molecular distillation, for example, by using an internal temperature of 85°C or higher and a reduced pressure of 0.133kPa or less. The condition is to perform distillation until the distillation of the fraction is stopped, and it is desirable that the content of the volatile organic compound corresponding to a boiling point of 260° C. or less under normal pressure is 1% by mass or less.

As the fluorine-containing polyfunctional alcohol compound represented by formula (4) obtained in this way, the following can be exemplified.

(In the formula, Rf', e1, and v1 are the same as above).

Secondly, the fluorine-containing acrylic compound (A) can be obtained by introducing an acrylic group into the fluorine-containing polyfunctional alcohol compound obtained above.

In another embodiment of the present invention, the fluorine-containing polyfunctional alcohol compound represented by the above formula (4) obtained as described above is used as the component (C), and in the presence of the component (B) described above, it has The compound (D) of one isocyanate group and at least one (meth)acryloyl group is reacted to synthesize component (A) to obtain the first embodiment of the present invention, which is a method of fluorine-containing acrylic composition.

As the compound (D) having one isocyanate group and at least one (meth)acryloyl group in one molecule, the following can be cited.

CH ₂ =CHCOOCH ₂ CH ₂ -N=C=O

CH ₂ =CCH ₃ COOCH ₂ CH ₂ -N=C=O

CH ₂ =CCH ₃ COOCH ₂ CH ₂ OCH ₂ CH ₂ -N=C=O

[CH ₂ =CCH ₃ COOCH ₂ ] ₂ CH(CH ₃ )-N=C=O

Among them, particularly preferred are the following two types.

CH ₂ =CHCOOCH ₂ CH ₂ -N=C=O

CH ₂ =CCH ₃ COOCH ₂ CH ₂ -N=C=O

Although the component (D) can be reacted by placing equal mol or more with respect to the total amount of the hydroxyl groups of the component (C) as an isocyanate group, and reacting all the hydroxyl groups to urethane, it is relative to (C) The component 1 mol is averaged, and if 1 mol or more of acryloyl group is introduced, the remaining amount of unreacted (D) component can be reduced by making the hydroxyl group equal to the isocyanate group or making the hydroxyl group slightly excessive. Specifically, it is expected to be equivalent to (C) in the reaction system In the case where the total amount of the compound is divided into x mol, and the total amount of hydroxyl groups of the component (C) is defined as y mol, the blending amount of the component (D) is x mol or more and 1.05 mol or less. Preferably, it is 0.5 y mol or more and 1.0 y mol or less. When the component (D) is too small, the possibility that the component (C) into which the acryl group has not been introduced will remain at all is increased, and the curability of the final composition or the solubility of the product may be reduced. When there are too many components (D), the remaining amount of the component (D) increases, which may affect the antifouling performance of the final composition.

The mixing ratio of each component (B), (C), (D) during the reaction, the blending amount of (D) component is 1.0y or less, and if (D) component does not remain after the reaction, the mass ratio It is better to satisfy the following.

0.03<[(C)+(D)]/(B)<5

In addition, if the blending amount of component (D) is greater than 1.0y, and component (D) remains after the reaction, the remaining component (D) is recognized as part of component (B). That is, the (B) component contained other than the remaining (D) component is designated as (B1), and the mass of the (D) component equivalent to 1.0 y is designated as (d1), from the blended total (D) When the value of the component mass minus (d1) is set as (d2), it is better to satisfy the following requirements.

0.03<[(C)+(d1)]/[(B1)+(d2)]<5

In addition, a polymerization inhibitor can be added if necessary during the reaction. Although it is not particularly limited as a polymerization inhibitor, it can usually be used as a polymerization inhibitor for acrylic compounds. Specifically, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene, etc. can be mentioned.

The blending amount is expected to be 1 of the total mass of components (B), (C), and (D) ~3,000ppm, more preferably 1~500ppm.

In this reaction, an appropriate catalyst can be added in order to increase the reaction speed. As the catalyst, for example, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin dioctanoate (Dioctate) tin, dioctyl tin diacetate, dioctyl tin dilaurate, and dioctyl tin are exemplified. Dioctanoate (Dioctoate) tin, stannous dioctoate and other alkyl tin ester compounds, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetrakis (2-ethylhexyloxy), dipropoxy Bis(acetylacetonyl) titanium, titanium isopropoxy octanediol, etc. titanate or titanium chelating agent compound, zirconium tetraacetone, zirconium tributoxymonoacetone, zirconium monobutoxyacetone Zirconium acetone bis (ethyl acetyl acetate), zirconium dibutoxy bis (ethyl acetyl acetate), zirconium tetraacetone acetone, zirconium chelating agent compounds, etc. These are not limited to one type, and although they can be used as a mixture of two or more types, it is particularly preferable to use titanium compounds and zirconium compounds that have a low environmental impact.

With respect to the total mass of the reactants (the total mass of the components (C) and (D)), the reaction rate can be increased by adding these catalysts to 0.01-2% by mass, preferably 0.05-1% by mass.

Reaction If necessary, each component of (B), (C), (D) and the above-mentioned polymerization inhibitor or catalyst are stirred and mixed, and if necessary, heating is carried out to make the reaction proceed.

The reaction is carried out at a temperature of 0 to 120°C, preferably 10 to 70°C, for 1 minute to 500 hours, preferably 10 minutes to 48 hours. When the reaction temperature is too low, the reaction rate may become excessively slow, and when the reaction temperature is too high, there is a possibility of polymerization of the acryl group as a side reaction.

After the reaction, if necessary, it can be treated by adsorption or over The coloring component or insoluble component is removed by methods such as filtration and washing to obtain the fluorine-containing acrylic composition of the present invention.

The fluorine-containing acrylic composition obtained in this way becomes one that is not blended with volatile organic compounds.

The fluorine-containing acrylic composition of the present invention can be added to the active energy ray curable composition (E) described later to become a fluorine-containing active energy ray curable composition.

The active energy ray curable composition (E) used in one embodiment of the present invention is not particularly limited if it is administered to the cured product by irradiation of active energy rays such as ultraviolet rays, electron beams, etc., but especially It is preferable to contain an acrylic compound (Ea) and a photopolymerization initiator (Eb).

As the acrylic compound (Ea), both monofunctional and polyfunctional can be used. For example, although the above-mentioned component (B), namely, monofunctional and bifunctional acrylic compounds can also be used, as the component (Ea), it is especially a non-fluorinated acrylic compound containing two or more acryl groups in one molecule Better.

As such a non-fluorinated acrylic compound, if it has two or more acryl groups or α-substituted acryl groups in one molecule, for example, the compound includes 1,6-hexanediol di(meth)acrylic acid Ester, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, isocyanurate ethylene oxide modified di(meth)acrylate, isocyanurate EO modified three ( Meth) acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, ginseng (meth)acryloxyethyl phosphate , Hydrogen phthalate-(2,2,2-tris-(meth)acrylic acid) Oxymethyl) ethyl ester, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate and other 2~6 functional (meth)acrylic compounds, these (meth)acrylic compounds are used in ethylene oxide, propylene oxide, Epichlorohydrin, fatty acids, alkyl modified products, epoxy resins are added with acrylic acid, and (meth)acrylic acid copolymers are introduced into the side chains of the obtained epoxy acrylates and acrylate copolymers Wait.

In addition, urethane acrylates, those obtained by reacting (meth)acrylates having hydroxyl groups in polyisocyanates, and (meth) having hydroxyl groups in polyesters of polyisocyanates and terminal diols can also be used. Those obtained by reacting acrylates, or those obtained by reacting excess diisocyanates with polyols, and those obtained by reacting (meth)acrylates having hydroxyl groups in polyisocyanates. Among them, it is preferably a (methyl) group selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol triacrylate. Acrylate, and use selected from hexamethylene diisocyanate, isophorone diisocyanate, phenylmethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, 1,3-bis(isocyanate Methyl)cyclohexane, methylene bis(4-cyclohexyl isocyanate), 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanate Urethane acrylates in which the polyisocyanate in cyclohexane and diphenylmethane diisocyanate reacts.

In particular, polyfunctional acrylics having two or more acryloyl groups or α-substituted acryloyl groups in one molecule and no urethane bond can be cited. Acrylic acid compound, or a polyfunctional amine containing three or more acryloyl groups or α-substituted acryloyl groups in one molecule, obtained by reacting an aliphatic polyisocyanate with an acrylic compound having a hydroxyl group, containing the multifunctional acrylic compound A mixture of at least two types of acrylic compounds among the ethyl formate acrylates.

Here, as a multifunctional acrylic compound having two or more acryloyl groups or α-substituted acryloyl groups in one molecule, and no urethane bond, trimethylolpropane tri(meth)acrylic acid can be cited Ester, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate Acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, and these compounds modified with ethylene oxide or propylene oxide.

As a polyfunctional ethyl urethane acrylate having three or more acryl groups or α-substituted acryl groups in one molecule obtained by reacting aliphatic polyisocyanates with an acrylic compound having a hydroxyl group, it can be expressed in hexadecane Methyl diisocyanate, norbornane diisocyanate, isophorone diisocyanate and these 3 quantified products, and these difunctional and trifunctional isocyanates make aliphatic diols, aliphatic polyols and side The polyisocyanate obtained by reacting polyacrylates with hydroxyl groups in the chain is a polyisocyanate with two or more functionalities, which is trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, bis(2-( (Meth)acryloyloxyethyl)hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylic acid Ester and this Reactors such as ethylene oxide and propylene oxide reformers, or make aliphatic polyols and polyacrylates with hydroxyl groups on the side chains and 2-isocyanatoethyl (meth)acrylate or 1,1 -(Bisacryloxymethyl) ethyl isocyanate and other acrylic compounds having isocyanate groups to react.

Furthermore, as the component (Ea), not only a liquid component, but also the surface of a fine particle-shaped high molecular weight body or the surface of an inorganic filler fine particle is modified with an acryl group.

The above-mentioned (Ea) component can be used singly, but it can also be used by blending a plurality of compounds corresponding to the properties of the coating film after coating or curing.

Furthermore, by containing a photopolymerization initiator as the component (Eb), it can be a curable composition that improves the curability when using ultraviolet rays as the active energy rays.

The photopolymerization initiator of the component (Eb) is not particularly limited if it is capable of curing the acrylic compound by ultraviolet irradiation, but preferably, acetophenone, benzophenone, 2,2- Dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[ 4-(2-Hydroxyethoxy)phenyl)-2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1-(4-methylthiophenyl)-2- Morpholinyl propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl) butanone-1, 2-(dimethylamino)-2- [(4-Methylphenyl)methyl]-1-[4-(4-morphoyl)phenyl]-1-butanone, 2,4,6-trimethylbenzyl-diphenyl Benzyl-phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2 -(o-benzyl oxime)], ethyl ketone-1-[9-ethyl-6-(2-methylbenzyl oxime) Yl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanyl)benzyl Yl]phenyl}-2-methylpropan-1-one, etc., may be used alone or in combination of two or more kinds.

Although the content of the component (Eb) can be appropriately determined according to the curing conditions and the physical properties of the cured product of the curable composition (E) by the intended active energy ray, it is desirable, for example, to be relative to the total 100 parts by mass of the component (Ea) 0.1 to 15 parts by mass, especially 1 to 10 parts by mass. When the amount of addition is smaller than this, the hardenability may decrease, and when it is larger than this, the effect on the physical properties after hardening may increase.

In addition to the active energy ray curable composition (E), thiol compounds, maleimide compounds, etc., active energy ray reactive compounds other than acryl, organic solvents, and polymerization inhibitors can also be blended , Antistatic agents, defoamers, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and polymer or inorganic fillers. These do not particularly limit the structure, and well-known ones can be used within the scope not to impair the purpose of the present invention.

In addition, as active energy ray curable composition (E), as active energy ray curable composition blended with components (Ea) and (Eb) and various additives, coatings, inks, and hardeners can be used from various companies Classification of paints, etc. Existing commercially available compositions are used as part or all of component (E). Even when using commercially available hard coat agents, organic solvents, polymerization inhibitors, antistatic agents, defoamers, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, and interfacial activity can be added to suit the purpose. Agents, colorants, and fillers are blended.

An embodiment of the present invention is a fluorine-containing active energy ray curable composition characterized by containing 100 parts by mass of the above-mentioned active energy ray curable composition (E), which is the first embodiment of the present invention. The fluoroacrylic acid composition is 0.005 to 40 parts by mass, preferably 0.01 to 20 parts by mass. The blending amount of the fluorinated acrylic composition is not particularly limited if it is in the above range, but it is desirable that the blending amount of the (A) component in the fluorinated acrylic composition is 0.005 in the fluorinated active energy ray curable composition. ~10% by mass. When the amount of component (A) is less than this, when the hardened product is formed, component (A) cannot be fully arranged on the surface, and the expected liquid repellency and antifouling properties cannot be displayed. When it is larger than this, the hardened layer If the influence of the component (A) on the strength or hardness of the active energy ray becomes too large, the original hardened properties of the active energy ray curable composition (E) will be lost.

If the fluorine-containing active energy ray curable composition of the present invention obtained as described above can suppress the content of volatile organic compounds that are not incorporated into the structure of the cured product, it can form antifouling properties on the surface of any substrate. A curable composition with extremely low generation of volatile organic compounds in the cured resin layer with excellent liquid repellency.

Furthermore, in the present invention, there is provided an article in which the above-mentioned fluorine-containing active energy ray curable composition of the present invention is applied to the surface of a substrate to be cured. As described above, if the fluorine-containing active energy ray curable composition of the present invention is used, a cured film (cured resin layer) having excellent surface characteristics can be formed on the surface of the substrate. In particular, it is useful because it imparts water repellency, oil repellency, and antifouling properties to the acrylic hard-coated surface. With this, it is difficult to adhere to the pollution caused by fingerprints, sebum, sweat and other human grease, cosmetics, etc., and wipe off The hard-coated surface with excellent performance is attached to the substrate (article). Therefore, the curable fluorine-containing active energy ray composition of the present invention can provide a coating film or a protective film for the surface of a substrate (article) that may be contaminated by human body contact with human fat, cosmetics, etc.

The cured film (cured resin layer) formed by using the fluorine-containing active energy ray curable composition of the present invention can be cured by directly coating on the surface of a property-provided article, or coated on various substrates The cured film of the fluorine-containing active energy ray curable composition of the present invention is attached to the surface of the target article to impart characteristics to various articles.

Here, the coating method of the curable fluorine-containing active energy ray composition of the present invention is not particularly limited, but for example, roll coating, gravure coating, flow coating, dip coating, spray coating, spin coating, bar coating can be used. Well-known coating methods such as coating and screen printing. After coating, the coating film is irradiated with active energy rays to harden it. Here, as the active energy ray, any of electron beams and ultraviolet rays can be used, but ultraviolet rays are particularly preferred. As the ultraviolet source, mercury lamps, metal halide lamps, and LED lamps are suitable. As the ultraviolet irradiation amount, because too small, the remaining uncured component, is too large, the possibility of deterioration of the coating and the substrate, it is desirably 10 ~ 10,000mJ / cm ^2, especially in the range of 20 ~ 4,000mJ / cm ² of . In addition, in order to prevent the hardening caused by oxygen, the irradiation environment can be replaced with inert gases that do not contain oxygen molecules such as nitrogen, carbon dioxide, argon, etc., or the surface of the coating film can be releasable with ultraviolet rays. A transparent protective layer is coated. When ultraviolet rays are irradiated from it, or the substrate has ultraviolet transmittance, the surface of the coating film can be covered with a mold-releasing protective layer, and from the opposite to the coated surface of the substrate The side is irradiated with ultraviolet rays. In addition, in order to effectively level the coating film or polymerize the acryl group in the coating film, the coating film and the substrate can be heated by any method such as a hot air drying oven before and during ultraviolet irradiation.

In addition, although the thickness of the cured film (cured resin layer) formed using the fluorine-containing active energy ray curable composition of the present invention is not particularly limited, if the resulting film thickness is too thin, sufficient If the surface hardness is too thick, the mechanical strength of the hard coating film will be reduced. From the point of view that it is easy to fall into cracks, it is usually 5nm~100μm, especially 1μm~20μm.

As such items, such as tablet computers, mobile phones. Mobile (communication) information terminals, notebook computers, digital media players, phenotypes such as smart phones. Glasses-type wearable computers, digital cameras, digital cameras, e-book readers, etc., the frames of various machines that are held by humans to walk; liquid crystal displays, plasma displays, organic EL displays, rear projection displays, fluorescent display tubes ( VFD), field emission projection display, CRT, toner display (toner display) and other flat panel displays and TV screens, etc. to indicate the surface of the operating machine, the exterior of the car, the glossy surface of the piano or furniture, the building of marble, etc. Decorative building materials around water used in stone surfaces, toilets, bathrooms, washrooms, etc., protective glass for art display, showcases, display cabinets, covers for photo frames, watches, car window glass, window glass for trains, aircraft, etc., and automobiles It is useful for coating films and surface protection films for transparent glass or transparent plastic (acrylic, polycarbonate, etc.) components such as headlights and taillights, and various mirror components.

Especially with a touch panel display and other human fingers or hands Various machines of display and input devices that perform operations on the screen, such as tablet computers, notebook computers, wearable computers, activity meters, and mobile phones. Mobile (communication) information terminals such as smartphones, digital media players, e-book readers, digital photo frames, game consoles and game console controllers, digital cameras, digital cameras, navigation devices for automobiles, etc., automatic cash deposits It is useful for the surface protection film of various controllers such as pick-up devices, cash dispensers, vending machines, digital signage (electronic signage), security system terminals, POS terminals, remote controls, and display input devices such as panel switches for in-vehicle devices.

Furthermore, the cured film formed by the fluorine-containing active energy ray curable composition of the present invention is used as an optical recording medium for magneto-optical discs, optical discs, etc.; eyeglass lenses, camera lenses, projector lenses, lens sheets, protective films , Polarizing plate, optical filter, biconvex lens, Fresnel lens, anti-reflection film, optical fiber and optical coupler as optical parts. The surface protective film of the optical device or the surface protective film of various protective parts of such equipment is also useful.

[Example]

Although synthesis examples, examples, and comparative examples are shown below to specifically describe the present invention, the present invention is not limited to the following examples.

[Synthesis example 1] Synthesis of fluoroalcohol compound (C-1)

A 2,000 mL three-necked flask equipped with a reflux device and a stirring device in a dry nitrogen environment is put into the following formula CH ₂ =CH-CH ₂ -O-CH ₂ -Rf'-CH ₂ -O-CH ₂ -CH=CH ₂

Rf': -CF ₂ O(CF ₂ O) _p1 (CF ₂ CF ₂ O) _q1 CF _2-

(q1/p1=0.9, p1+q1≒45)

The indicated perfluoropolyether 500g (0.125 mol), 700g of m-xylene hexafluoride, and 361g (1.50 mol) of tetramethylcyclotetrasiloxane are heated to 90°C while stirring. Put here 0.442g of toluene solution of platinum/1,3-divinyl-tetramethyldisiloxane complex (containing 1.1×10 ^-6 mol as Pt monomer), and maintain the internal temperature at 90°C Continue stirring directly for 4 hours. After confirming the disappearance of the allyl group of the raw material by ¹ H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Then, activated carbon treatment was performed to obtain 498 g of a colorless and transparent liquid compound (I) represented by the following formula.

Rf': -CF ₂ O(CF ₂ O) _p1 (CF ₂ CF ₂ O) _q1 CF _2-

(q1/p1=0.9, p1+q1≒45)

In a dry air environment, with respect to 200.0 g of the compound (I) obtained above (Si-H group amount 0.133 mol), 28.20 g (0.276 mol) of 2-allyloxyethanol and m-xylene hexafluoride were mixed 200.0 g, and 0.0884 g of toluene solution of chloroplatinic acid/vinylsiloxane complex compound (containing 2.2×10 ^-7 mol as Pt monomer), and stirred at 100° C. for 4 hours. After confirming the disappearance of Si-H groups by ¹ H-NMR and IR, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure and treated with activated carbon to obtain a light yellow transparent liquid containing fluorine expressed by the following formula 216.1 g of alcohol compound (C-1).

Rf': -CF ₂ O(CF ₂ O) _p1 (CF ₂ CF ₂ O) _q1 CF _2-

(q1/p1=0.9, p1+q1≒45)

[Synthesis example 2] Synthesis of fluoroalcohol compound (C-2)

In a dry nitrogen environment, put the following formula CH ₂ =CH-CH ₂ -O-CH ₂ -Rf'-CH ₂ -O-CH ₂ -CH=CH into a 3,000 mL three-necked flask equipped with a reflux device and a stirring device ₂

Rf': -CF ₂ O(CF ₂ O) _p2 (CF ₂ CF ₂ O) _q2 CF _2-

(q2/p2=1.2, p2+q2≒18.5)

The indicated perfluoropolyether 500g (0.272 mol), 1,000 g of m-xylene hexafluoride, and 660 g (2.72 mol) of tetramethylcyclotetrasiloxane are heated to 90°C while stirring. Put 0.884 g of toluene solution of platinum/1,3-divinyl-tetramethyldisiloxane complex here (containing 2.2×10 ^-6 mol as Pt monomer), and maintain the internal temperature at 90°C Continue stirring directly for 4 hours. After confirming the disappearance of the allyl group of the raw material by ¹ H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Then, activated carbon treatment was performed to obtain 581 g of a colorless and transparent liquid compound (II) represented by the following formula.

Rf': -CF ₂ O(CF ₂ O) _p2 (CF ₂ CF ₂ O) _q2 CF _2-

(q2/p2=1.2, p2+q2≒18.5)

In a dry air environment, with respect to 200.0 g of the compound (II) obtained above (the amount of Si-H group is 0.518 mol), 105.8 g (1.04 mol) of 2-allyloxyethanol and m-xylene hexafluoride are mixed 400.0 g, and 1.77 g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 4.4×10 ^-7 mol as Pt monomer), and stirred at 100°C for 4 hours. After confirming the disappearance of Si-H groups by ¹ H-NMR and IR, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure and treated with activated carbon to obtain a light yellow transparent liquid containing fluorine expressed by the following formula Alcohol compound (C-2) 240.4g.

Rf': -CF ₂ O(CF ₂ O) _p2 (CF ₂ CF ₂ O) _q2 CF _2-

(q2/p2=1.2, p2+q2≒18.5)

[Example 1] Preparation of fluorine-containing acrylic composition (F-1)

In a dry air environment, with respect to 50.0 g of the fluoroalcohol compound (C-1) obtained in Synthesis Example 1 (amount of hydroxyl group 0.058 mol), (B-1) 2-(perfluorohexyl) ethyl acrylate [ Viscosity 4mPa. s/25°C] 57.9 g, (D) 7.87 g (0.055 mol) of propylene oxyethyl isocyanate, heated to 50°C and stirred for 1 hour. 0.05 g of dioctyltin (di)laurate was added thereto, and the mixture was stirred at 50°C for 8 hours. From the results of ¹ H-NMR, it was confirmed that the 4.2 ppm methylene peak of unreacted propylene oxyethyl isocyanate and the 4.1 ppm methylene peak after the formation of the urethane bond all changed. Again, It was confirmed from the IR spectrum that the peak of the isocyanate group at 2,260 cm ^-1 disappeared. After the heating, the resultant reaction liquid was treated with activated carbon to obtain 100.3 g of light yellow liquid. Thereby, the reactants of (C-1) and (D), namely the fluorinated acrylic compound (A-1) shown below and 2-(perfluorohexyl)ethyl acrylate (B-1), are obtained ( A fluorinated acrylic composition (F-1) mixed with a mass ratio of A-1)/(B-1)=1.

Rf': -CF ₂ O(CF ₂ O) _p1 (CF ₂ CF ₂ O) _q1 CF _2-

(q1/p1=0.9, p1+q1≒45)

[Example 2] Preparation of fluorine-containing acrylic composition (F-2)

In a dry air environment, with respect to 50.0 g of the fluorine-containing alcohol compound (C-1) obtained in Synthesis Example 1 (amount of hydroxyl group 0.058 mol), mix (B-2) 2-(perfluorohexyl) ethyl methacrylic acid Ester [viscosity 5mPa. s/25℃] 57.9g, (B-3) isobutyl acrylate [viscosity 1mPa. s/25°C] 115.8 g, (D) 7.87 g (0.055 mol) of acryloxyethyl isocyanate, heated to 50°C and stirred for 1 hour. 0.05 g of tin (two) laurate was added thereto, and the mixture was stirred at 50°C for 8 hours. From the results of ¹ H-NMR, it was confirmed that the 4.2 ppm methylene peak of unreacted propylene oxyethyl isocyanate and the 4.1 ppm methylene peak after the formation of the urethane bond all changed. Again, It was confirmed from the IR spectrum that the peak of the isocyanate group at 2,260 cm ^-1 disappeared. After heating, the resultant reaction liquid was treated with activated carbon to obtain 170.1 g of light yellow liquid. Thereby, the reactants of (C-1) and (D), namely the fluorinated acrylic compound (A-1) and 2-(perfluorohexyl)ethyl methacrylate (B-2) shown below, are obtained. ) And isobutyl acrylate (B-3), a fluorinated acrylic composition (F-2) with a mass ratio of (A-1)/[(B-2)+(B-3)]=0.33 .

[Example 3] Preparation of fluorine-containing acrylic composition (F-3)

In a dry air environment, with respect to 50.0 g of the fluoroalcohol compound (C-1) obtained in Synthesis Example 1 (amount of hydroxyl group 0.058 mol), 50.0 g of m-xylene hexafluoride and (D) propylene oxyethyl are mixed 7.87 g (0.055 mol) of methyl isocyanate was heated to 50°C and stirred for 1 hour. 0.05 g of tin (two) laurate was added thereto, and the mixture was stirred at 50°C for 8 hours. From the results of ¹ H-NMR, it was confirmed that the 4.2 ppm methylene peak of unreacted propylene oxyethyl isocyanate and the 4.1 ppm methylene peak after the formation of the urethane bond all changed. Again, It was confirmed from the IR spectrum that the peak of the isocyanate group at 2,260 cm ^-1 disappeared, and the heating was terminated. The resultant reaction liquid was treated with activated carbon to obtain 98.2 g of a pale yellow liquid. The obtained light yellow liquid was distilled off under reduced pressure with a rotary evaporator at 60° C. and 133.32 Pa for 3 hours, and (A-1) was isolated as a light yellow ointment component of 55.2 g. It was confirmed that the mass of (A-1) obtained after heating and drying at 105°C for 3 hours was reduced to 0.01% by mass or less.

Put 10g of (A-1) obtained above into a glass bottle container with a lid, and add (B-4) 2-(perfluorobutyl) ethyl acrylate [viscosity 3mPa. s/25℃] 10g, (B-5) tetrahydrofuryl acrylate [viscosity 3mPa. s/25℃] 30g, vibrate with a vibrator until uniformly dissolved, and obtain a fluorinated acrylic composition (F) with a mass ratio of (A-1)/[(B-4)+(B-5)]=0.25 -3).

[Example 4] Preparation of fluorine-containing acrylic composition (F-4)

In a dry air environment, with respect to 50.0 g of the fluoroalcohol compound (C-2) obtained in Synthesis Example 2 (amount of hydroxyl group: 0.102 mol), 254.8 g of (B-3) isobutyl acrylate and (D) propylene were mixed 13.7 g (0.097 mol) of oxyethyl isocyanate was heated to 50°C and stirred for 1 hour. 0.10 g of dioctyltin (di)laurate was added thereto, and the mixture was stirred at 50°C for 8 hours. From the results of ¹ H-NMR, it was confirmed that the 4.2 ppm methylene peak of unreacted propylene oxyethyl isocyanate and the 4.1 ppm methylene peak after the formation of the urethane bond all changed. Again, It was confirmed from the IR spectrum that the peak of the isocyanate group at 2,260 cm ^-1 disappeared. After the heating, the resultant reaction liquid was treated with activated carbon to obtain 318.7 g of light yellow liquid. Thereby, the reactants of (C-2) and (D), namely the fluorine-containing acrylic compound (A-2) and (B-3) isobutyl acrylate shown below, are obtained with (A-2)/ (B-3) = A fluorine-containing acrylic composition (F-4) mixed with a mass ratio of 0.25.

Rf': -CF ₂ O(CF ₂ O) _p2 (CF ₂ CF ₂ O) _q2 CF _2-

(q2/p2=1.2, p2+q2≒18.5)

Furthermore, the fluorine-containing acrylic composition obtained in the foregoing Examples 1 to 4 does not contain volatile organic compounds.

[Comparative Example 1]

In Example 3, although (B-5) tetrahydrofuryl acrylate was replaced, trimethylolpropane triacrylate, a trifunctional acrylic compound, was used [viscosity 110mPa. s/25°C] Tried preparation of the composition, but separated without dissolving.

[Examples 5-10, Comparative Examples 2-5]

The following acrylic compound (Ea) and photopolymerization initiator (Eb) were used to prepare an active energy ray curable composition (E).

(Ea-1) Dipentaerythritol penta/hexaacrylate

[A-9550 manufactured by Shinnakamura Chemical Co., Ltd.]

(Ea-2) pentaerythritol triacrylate

[A-TMM-3 manufactured by Shinnakamura Chemical Co., Ltd.]

(Ea-3) pentaerythritol ethoxy tetraacrylate

[EBECRYL 40 manufactured by Daicel Ornex Co., Ltd.]

(Ea-4) Tetrahydrofuryl acrylate (Eb-1)1-Hydroxycyclohexyl phenyl ketone

[IRGACURE 184 manufactured by BASF Japan Co., Ltd.]

(Eb-2)2-Hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanyl)benzyl]phenyl}-2-methylpropan-1-one

[IRGACURE 127 manufactured by BASF Japan Co., Ltd.]

Active energy ray hardening composition (E1):

(Ea-1) 70 parts by mass

(Ea-4) 30 parts by mass

(Eb-1) 3 parts by mass

Active energy ray hardening composition (E2):

(Ea-1) 70 parts by mass

(Ea-2) 30 parts by mass

(Eb-1) 3 parts by mass

Active energy ray hardening composition (E3):

(Ea-1) 30 parts by mass

(Ea-2) 70 parts by mass

(Eb-1) 3 parts by mass

Active energy ray curable composition (E4):

(Ea-3) 100 parts by mass

(Eb-2) 3 parts by mass

Preparation of comparative composition

In addition, the comparative compositions (G-1) and (G-2) were prepared with the following ratios.

(G-1): (B-1) 50 parts by mass, (B-2) 100 parts by mass

(G-2): (B-1) 50 parts by mass, (B-2) 150 parts by mass

Preparation of fluorine-containing active energy ray curable composition

Mix the fluorinated acrylic composition (F-1)~(F-4) obtained in the above example, the above fluorinated acrylic compound (A-1), 2-(perfluoroacrylic acid compound) at the blending ratio shown in Table 1 below. Hexyl) ethyl acrylate (B-1) or the above-mentioned comparative composition (G-1), (G-2), and the above-mentioned active energy ray curable composition (E1) to (E4) to prepare fluorine-containing activity Energy ray curable composition. The appearance of the obtained composition was measured and shown in Table 1.

Coating and curing film production

Each fluorine-containing active energy ray curable composition of the Examples and Comparative Examples was applied on the carbonate substrate by spin coating. After coating, after leveling at room temperature for 10 minutes, use a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Electric Works) to irradiate the coated surface with a cumulative amount of 1,600mJ/cm ² of ultraviolet radiation in a nitrogen environment , The composition is cured to obtain a cured film with a thickness of 9μm. For Example 10, instead of flattening at room temperature for 10 minutes, heating was performed at 100°C for 1 minute.

Evaluation of hardened film

The appearance (transparency) of the cured film obtained above was visually measured, and at the same time, the measurement of the water contact angle and the evaluation of the oil resistance signature were performed by the method shown below. The results are shown in Table 1.

〔Measurement of water contact angle〕

Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), a 2 μL drop was dropped on the cured film, and the contact angle after 1 second was measured. Take the average value of N=5 as the measured value.

〔Evaluation of signature for oil resistance〕

On the surface of the hardened film, draw a straight line with an oil-based pen (manufactured by Sisei Chemical Industry Co., Ltd., universal ink large-scale), and mark those who reject ink as ○ and those who do not reject it as ×.

Claims (13)

A fluorine-containing acrylic composition characterized by containing the following (A) and (B) as essential components, (A) a fluorinated acrylic compound represented by the following general formula (1), X-Rf ¹ -Z ^1- Q ¹ -[Z ² OR ¹ ] _a (1)(In the formula, Rf ¹ is a divalent perfluoropolyether with a molecular weight of 800~20,000 composed of a perfluoroalkylene group with 1~6 carbon atoms and oxygen atoms Q ¹ is an (a+1) valence linking group independently containing at least (a+1) silicon atoms, which can be a cyclic structure and can contain at least one selected from oxygen atoms, nitrogen atoms, and fluorine atoms; Z ^{1 is} independently a divalent linking group with 1 to 20 carbon atoms and may include at least one selected from oxygen atom, nitrogen atom and silicon atom. It may include a cyclic structure in the way, may become branched, and part of hydrogen atoms may Substituted by a fluorine atom; Z ^{2 is} independently a divalent hydrocarbon group with 1 to 200 carbon atoms, which may also include at least one selected from an oxygen atom, a nitrogen atom, and a silicon atom, and may include a cyclic structure on the way; R ^{1 is} independently hydrogen Atoms, or containing: a monovalent organic group containing at least one acryloyl group or α-substituted acryloyl group selected from the group consisting of oxygen atoms and nitrogen atoms, however, R ¹ is an average of at least one containing in one molecule The monovalent organic group of the aforementioned acryloyl group or α-substituted acryloyl group; X is a fluorine atom or -Z ¹ -Q ¹ -[Z ² OR ¹ ] _a monovalent group represented by a; a is an integer from 1 to 10) ( B) The viscosity at 25°C is 100mPa. s or less, and containing 1 or 2 (meth)acrylic groups in a molecule, the mass ratio of the acrylic compound (A) to the (B) component is in the range of 0.03<(A)/(B)<10 In addition, it is not blended with volatile organic compounds that do not have groups that react with acryl groups. For example, the fluorine-containing acrylic composition of claim 1, which, as part or all of component (B), contains an acrylic compound represented by the following general formula (2), CH ₂ =CR ⁶ COOR ⁵ (2) (where , R ⁵ is an alkyl, aryl or aralkyl group with 1 to 20 carbon atoms, which may be branched or cyclic, and may contain aliphatic unsaturated bonds, urethane bonds, ether bonds, isocyanate groups, Hydroxyl group; R ⁶ is a hydrogen atom, a methyl group, a fluorine atom, a fluoroalkyl group with 1 to 6 carbon atoms). The fluorine-containing acrylic composition of claim 1 or 2, wherein, as the component (B), an acrylic compound in which a part of hydrogen atoms is substituted with a halogen atom selected from F, Cl, and Br. For example, the fluorine-containing acrylic composition of claim 3, wherein, as part or all of component (B), it contains a fluorine-containing acrylic compound represented by the following general formula (3), CH ₂ =CR ² COOZ ³ Rf ² (3 ) (However, in the formula, R ² is independently a hydrogen atom, F, Cl, Br or a monovalent hydrocarbon group with 1 to 8 carbons. The hydrogen atom in the hydrocarbon group can be replaced by F, Cl, Br; Z ³ is independently A bivalent hydrocarbon group with 1 to 8 carbon atoms can be branched and can contain oxygen atoms and hydroxyl groups on the way; Rf ² is a fluoroalkyl group with 2 to 20 fluorine atoms, which can contain hydrogen atoms and oxygen atoms, and can be branched). For the fluorinated acrylic composition of claim 1 or 2, wherein the fluorinated acrylic compound represented by the general formula (1) of the component (A), Rf ¹ is a divalent perfluoropolyether represented by the following 3 types of structural formulas Any one of the groups, -CF ₂ O-(CF ₂ O) _p (CF ₂ CF ₂ O) _q -CF _2-

(However, the arrangement of repeating units included in () is random, p is an integer from 1 to 200, q is an integer from 1 to 170, p+q is from 6 to 201; s is an integer from 0 to 6, t, u is an integer from 1 to 100, t+u is an integer from 2 to 120; v is an integer from 1 to 120). The fluorine-containing acrylic composition of claim 1 or 2, wherein, in the component (A), Z ¹ in the general formula (1) is any structure represented by the following formula, -CH ₂ CH ₂ CH ₂ CH _2- -CH ₂ OCH ₂ CH ₂ CH _2-

Such as the fluorine-containing acrylic composition of claim 1 or 2, wherein in component (A), Q ¹ in general formula (1) is a structure represented by the following formula,

(In the formula, a is an integer from 1 to 10 independently). The fluorinated acrylic composition of claim 1 or 2, wherein the component (A) is selected from the fluorinated acrylic compound represented by the following formula,

(In the formula, Rf' is -CF ₂ O(CF ₂ O) _p (CF ₂ CF ₂ O) _q CF ₂ -, p is an integer from 1 to 200, q is an integer from 1 to 170, and p+q is 6. ~201; e1 is an integer from 1 to 30; R'is a hydrogen atom,

or

These can be mixed in one molecule; however, R'contains at least one monovalent organic group of the above-mentioned (meth)acryloyl group in an average of one molecule, v1 is an integer of 2 to 120). A method for manufacturing a fluorinated acrylic composition characterized by the step of reacting (C) and (D) in the presence of (B) to form (A), and the viscosity of (B) at 25°C is 100mPa. s or less, and an acrylic compound containing one or two (meth)acryloyl groups in one molecule; (C) a fluorine-containing polyfunctional alcohol compound represented by the following general formula (4); X ¹ -Rf ^1- Z ¹ -Q ¹ -[Z ² OH] _a (4) (In the formula, X ¹ is a fluorine atom or _a group represented by -Z ¹ -Q ¹ -[Z ² OH] _a , and Rf ^{1 has a} carbon number of 1~ A bivalent perfluoropolyether group with a molecular weight of 800 to 20,000 formed by perfluoroalkylene radicals of 6 and oxygen atoms, Z ^{1 is} independently a carbon number of 1 to 20, and can also be selected from oxygen atoms, nitrogen atoms and silicon atoms At least one kind of divalent linking group, Q ¹ is an (a+1) valent linking group independently containing at least (a+1) silicon atoms, can be a cyclic structure, and can contain selected from oxygen atoms, nitrogen atoms and At least one of the fluorine atoms; Z ^{2 is} independently a divalent hydrocarbon group with 1 to 200 carbon atoms, which may also include at least one selected from an oxygen atom, a nitrogen atom, and a silicon atom, and may include a cyclic structure on the way; a is An integer from 1 to 10); (D) a compound having one isocyanate group and at least one (meth)acryloyl group in one molecule; (A) the fluorine-containing acrylic compound X-Rf represented by the following general formula (1) ¹ -Z ¹ -Q ¹ -[Z ² OR ¹ ] _a (1) (wherein Rf ¹ , Z ¹ , Q ¹ , Z ² , and a are the same as above; R ^{1 is} independently a hydrogen atom, or contains: It may also contain at least one acryloyl group selected from oxygen atoms and nitrogen atoms or a monovalent organic group of α-substituted acryloyl group. However, R ¹ has at least one acryloyl group in one molecule on average. Or α-substituted monovalent organic group of propylene group, X is a fluorine atom or -Z ¹ -Q ¹ -[Z ² OR ¹ ] _a monovalent group represented by _a ) The mass ratio of the above component (A) to component (B) In the range of 0.03<(A)/(B)<10, moreover, a fluorinated acrylic composition containing no volatile organic compound that does not have a group reactive with acryl group is obtained. The method for producing a fluorinated acrylic composition according to claim 9, wherein part or all of component (B) contains an acrylic compound represented by the following general formula (2) and/or the following general formula (3) The fluorine-containing acrylic compound, CH ₂ =CR ⁶ COOR ⁵ (2) (In the formula, R ⁵ is an alkyl, aryl or aralkyl group with 1 to 20 carbon atoms, which may be branched or cyclic, and may contain Aliphatic unsaturated bond, urethane bond, ether bond, isocyanate group, hydroxyl group; R ⁶ is a hydrogen atom or a methyl group, a fluorine atom, a fluoroalkyl group with 1 to 6 carbon atoms) CH ₂ =CR ² COOZ ³ Rf ² (3) (However, in the formula, R ² is independently a hydrogen atom, F, Cl, Br, or a monovalent hydrocarbon group with 1 to 8 carbons. The hydrogen atom in the hydrocarbon group can be substituted by F, Cl, Br; Z ³ is independently a divalent hydrocarbon group with 1 to 8 carbon atoms, which can be branched, and can contain oxygen atoms and hydroxyl groups on the way; Rf ² is a fluoroalkyl group with 2 to 20 fluorine atoms, which can contain hydrogen atoms, oxygen atoms, and It can be branched) In the general formula (4) of component (C) and general formula (1) of component (A), Rf ¹ is any one of the divalent perfluoropolyether groups represented by the following three structural formulas, -CF ₂ O-(CF ₂ O) _p (CF ₂ CF ₂ O) _q -CF _2-

(However, the arrangement of repeating units included in () is random, p is an integer from 1 to 200, q is an integer from 1 to 170, p+q is from 6 to 201; s is an integer from 0 to 6, t, u are each an integer of 1 to 100, t + u is an integer of from 2 to 120; V is the integer of 1 to 120) of any one of the Z ¹ represents a configuration of the following _{formula, -CH 2 CH 2 CH 2 CH} 2 - - CH ₂ OCH ₂ CH ₂ CH _2-

Q ¹ is the structure represented by the following formula,

(In the formula, a is an integer from 1 to 10 independently). A fluorine-containing active energy ray curable composition characterized by containing 0.005 to 40 parts by mass of the fluorine-containing composition of any one of claims 1 to 8 relative to 100 parts by mass of the active energy ray curable composition (E) Acrylic composition. For example, the fluorine-containing active energy ray curable composition of claim 11, wherein the active energy ray curable composition (E) contains (Ea) acrylic compound: 100 parts by mass, (Eb) photopolymerization initiator: 0.1~ 15 parts by mass. An article having a hardened layer of the fluorine-containing active energy ray hardening composition as claimed in claim 11 or 12 on the surface.