TW201806992A - Fluorine-containing acryl composition and method for producing the same, fluorine-containing active energy ray-curable composition and article - Google Patents

Abstract

To provide a fluorine-containing acryl composition that can impart liquid-repellent and antifouling properties without increasing a volatile organic compound free of a group that reacts with an acrylic group, its production method, a fluorine-containing active energy ray-curable composition, and an article having a cured product layer thereof on the base material surface. A fluorine-containing acryl composition contains (A) a fluorine-containing acryl compound of the following formula: X-Rf1-Z1-Q1-[ZOR](Rf1 is a divalent perfluoropolyether group, Q1 is an Si-containing (a+1) valent linking group, Z1 is a divalent linking group, Z2 is a divalent hydrocarbon group, R1 is H, or an ([alpha]-substituted) acrylic group-containing monovalent organic group, X is a fluorine atom or a -Z1-Q1-[Z2OR1]group. a is 1-10) and (B) an acryl compound having a viscosity at 25 DEG C of 100 mPa.s or less and containing a (meth) acrylic group, with a mass ratio between them being 0.03 < (A)/(B) < 10, where the fluorine-containing acryl composition does not contain a volatile organic compound free of a group that reacts with an acrylic group.

Description

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

The present invention relates to a fluorine-containing acrylic composition capable of imparting 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. A fluorine-containing active energy ray-curable composition of the composition, and an article having a cured material layer of the composition on the surface of a substrate.

Conventionally, as a means for protecting the surface of a resin molded body or the like, a hard coating treatment has been widely used. This is because the hardened resin layer (hard coat layer) is formed on the surface of the molded body, which is difficult to scratch. As a material constituting the hard coat layer, a curable composition using active energy rays such as a thermosetting resin, an ultraviolet ray, or an electron beam-curable resin is widely used.

In addition, with the expansion of the field of use of resin molded products or the flow of high added value, the demand for higher functionalization of hardened resin layers (hard coatings) has been increased. Contamination resistance. This is because the surface of the hard coating layer has properties such as water repellency and oil repellency, which makes it difficult to contaminate, or it can be easily removed even if it is contaminated.

As a method for imparting antifouling properties to hard coatings, A method for coating and / or fixing a fluorine-containing antifouling agent on the surface of a hard coat layer once formed, but for a hardened resin composition in which a fluorine-containing hardening component is added before hardening, and the coating is hardened, Methods for simultaneously forming a hard coat layer and imparting antifouling properties have also been studied. For example, Japanese Patent Application Laid-Open No. 6-211945 (Patent Document 1) shows that a hard coat layer imparting antifouling properties is produced by adding a fluoroalkyl acrylate and curing it by adding 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 impact on the environment or the human body, the action of suppressing the use of volatile organic compounds (VOC), such as volatile organic solvents, has been increased, and coating solutions for hard coatings have also strongly demanded high solidification or no solvent. Into. Along with this, with regard to the additive composition added to impart liquid repellency and antifouling properties to the aforementioned hard coating coating liquid, volatile organic compounds that do not contain reactive groups such as non-volatile organic solvents are also being pursued The composer.

[Previous Technical Literature] [Patent Literature]

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

[Patent Document 2] Japanese Patent Laid-Open No. 2010-53114

[Patent Document 3] Japanese Patent Laid-Open No. 2010-138112

[Patent Document 4] Japanese Patent Laid-Open No. 2010-285501

The present invention has been made in view of the above problems, and by suppressing the content of volatile organic compounds having no reactive groups, it is possible to provide a hardening composition that does not increase the total amount of the hardening composition and that does not have an acrylic group. Reactive (non-reactive) volatile organic compounds (especially non-reactive volatile organic compounds that do not contain a (meth) acrylfluorenyl group in the molecule), and can impart liquid repellency and antifouling properties A fluorine-containing acrylic composition, a method for producing the fluorine-containing acrylic composition, a fluorine-containing active energy ray-curable composition having the composition, and an article having a hardened layer of the composition on the surface of a substrate are intended for the purpose. .

The present inventors have carried out various developments as fluorine compounds that can impart antifouling properties to such a curable resin composition. For example, Japanese Patent Application Laid-Open No. 2010-53114 (Patent Document 2) and Japanese Patent Application Laid-Open have been proposed. Photocurable fluorinated compounds as shown in 2010-138112 (Patent Document 3), Japanese Patent Laid-Open No. 2010-285501 (Patent Document 4), and the like.

With the structure of a fluoropolyether structure and a plurality of propylene fluorene groups in one molecule, although it is possible to impart a high antifouling property to the curable resin composition, on the other hand, it is a highly viscous liquid that is difficult to handle with monomers. In order to facilitate the operation and improve the miscibility 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 mixed with a solventless hard coat agent or coating.

Therefore, as a result of further research by the inventors, A fluorine-containing acrylic composition is present, which contains (A) a fluorine-containing acrylic compound represented by the formula (1) described later, and (B) has a viscosity of 100 mPa at 25 ° C. The acrylic compound containing s or less and containing one or two (meth) acrylfluorenyl groups in one molecule is characterized in that the mass ratio of the component (A) to the component (B) is 0.03 <(A) / (B) In the range of <10, volatile organic compounds that do not have a group that reacts with acryl fluorenyl group (especially non-reactive volatile organic compounds that do not contain (meth) acryl fluorenyl group in the molecule) are not blended. By adding this fluorinated 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, a method for producing the same, and the like.

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

(A) A 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 having a molecular weight of 800 to 20,000, which is composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Q ¹ independently includes at least (a + 1) (a + 1) th divalent linking group of silicon atom, may be a cyclic structure, selected may contain an oxygen atom, a nitrogen atom and a fluorine atom in at least one of; the Z ¹ independently of 1 to 20 carbon atoms may also contain A divalent linking group selected from at least one of an oxygen atom, a nitrogen atom, and a silicon atom, may include a ring structure on the way, may branch, and a part of hydrogen atoms may be replaced by fluorine atoms; Z ^{2 is} independently a carbon number of 1 to 200 may also include at least one type of divalent hydrocarbon group selected from an oxygen atom, a nitrogen atom, and a silicon atom, and may include a cyclic structure in the way; R ^{1 is} independently a hydrogen atom, or contains: At least one type of propylene fluorenyl group or α-substituted propylene fluorenyl group is a monovalent organic group of nitrogen atom. However, R ¹ has at least one propylene fluorenyl group or α-substituted propylene fluorenyl group in one molecule. 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. Acrylic compounds below s and containing one or two (meth) acrylfluorenyl groups 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 the volatile organic compound is not blended with a group that does not have a group that reacts with acrylfluorenyl group.

[2] The fluorinated acrylic composition according to [1], in which a part or all of the component (B) includes an acrylic compound represented by the following general formula (2), and CH ₂ = CR ⁶ COOR ⁵ (2)

(In the formula, R ⁵ is an alkyl group, an aryl group, or an aralkyl group having 1 to 20 carbon atoms, which may be branched or cyclic, and may include an aliphatic unsaturated bond, a urethane bond, an ether bond, Isocyanate group, hydroxyl group; R ⁶ is a hydrogen atom or a methyl group, a fluorine atom, and a fluoroalkyl group having 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 containing a hydrogen atom is replaced by a halogen atom selected from F, Cl, and Br.

[4] The fluorinated acrylic composition according to [3], wherein a part or all of the component (B) includes a fluorinated acrylic compound represented by the following general formula (3), and 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 having 1 to 8 carbon atoms, and the hydrogen atom in the hydrocarbon group may be replaced by F, Cl, Br; Z ³ is independently carbon Divalent hydrocarbon groups of 1 to 8 can be branched, and can include oxygen atoms and hydroxyl groups on the way; Rf ² is a fluoroalkyl group of 2 to 20 fluorine atoms, can include hydrogen atoms and oxygen atoms, and can be branched).

[5] The fluorine-containing acrylic composition according to any one of [1] to [4], wherein the fluorine-containing acrylic compound represented by the general formula (1) of the component (A), Rf ¹ is a structure of the following three types Any of the divalent 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 6 to 201, and 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 fluorine-containing acrylic composition according to any one of [1] to [5], wherein in the component (A), Z ¹ in the general formula (1) has any one 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 the component (A), Q ¹ in the general formula (1) is a structure represented by the following formula,

(Where a is an integer of 1 to 10).

[8] The fluorine-containing acrylic composition according to any one of [1] to [7], wherein the component (A) is selected from a fluorine-containing acrylic compound represented by the following formula,

(Where, 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 may be mixed in one molecule; however, R 'is a monovalent organic group containing at least one of the above (meth) acrylfluorenyl groups in one molecule, 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) with (D) in the presence of (B) to form (A), (B) at 25 ° C The viscosity is 100mPa. s or less and an acrylic compound containing one or two (meth) acrylfluorenyl 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 molecular weight of 800 by a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom. Divalent perfluoropolyether group of ~ 20,000, Z ^{1 is} independently a divalent linking group which may contain at least one kind selected from oxygen atom, nitrogen atom and silicon atom, and Q ¹ is independently at least The (a + 1) -valent linking group containing (a + 1) silicon atoms can form a cyclic structure and can include at least one selected from the group consisting of an oxygen atom, a nitrogen atom, and a fluorine atom; Z ^{2 is} independently a carbon number of 1 ~ 200 may also contain a divalent hydrocarbon group of at least one selected from the group consisting of an oxygen atom, a nitrogen atom, and a silicon atom, and may include a cyclic structure in the way; a is an integer of 1 to 10); (D) has 1 molecule A compound of one isocyanate group and at least one (meth) acryl group; (A) a 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 , 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 kind of propylene selected from an oxygen atom and a nitrogen atom. A fluorenyl group or an α-substituted propylene fluorenyl monovalent organic group. However, R ¹ is at least one monovalent organic group containing the aforementioned propylene fluorenyl or α-substituted propylene fluorenyl group in one molecule, and X is a fluorine atom or -Z ¹ -Q ^1- [Z ² OR ¹ ] _a 1-valent base)

The mass ratio of the above (A) component to (B) component is in a range of 0.03 <(A) / (B) <10, and a volatile organic compound that is not blended with a group that does not react with acrylhydrazone is obtained. Fluorine-containing acrylic composition.

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

(In the formula, R ⁵ is an alkyl group, an aryl group, or an aralkyl group having 1 to 20 carbon atoms, which may be branched or cyclic, and may include an aliphatic unsaturated bond, a urethane bond, an ether bond, Isocyanate group, hydroxyl group; R ⁶ is a hydrogen atom or a methyl group, a fluorine atom, and a fluoroalkyl group having 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 having 1 to 8 carbon atoms, and the hydrogen atom in the hydrocarbon group may be replaced by F, Cl, Br; Z ³ is independently carbon Divalent hydrocarbon groups of 1 to 8 can be branched, and can include oxygen atoms and hydroxyl groups on the way; Rf ² is a fluoroalkyl group of 2 to 20 fluorine atoms, which can include hydrogen atoms, oxygen atoms, or branches)

In the general formula (1) of the component (C) and the general formula (1) of the component (A), Rf ¹ is any of the divalent perfluoropolyether groups represented by the following three types of 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 6 to 201, and 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 a structure represented by the following formula,

(Where a is an integer of 1 to 10).

[11] A fluorine-containing active energy ray-curable composition containing 100 parts by mass of the active energy ray-curable composition (E) and containing 0.005 to 40 parts by mass as in any of [1] to [8] 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) an acrylic compound: 100 parts by mass, (Eb) a photopolymerization initiator : 0.1 to 15 parts by mass.

[13] An article comprising a hardened material layer having a fluorine-containing active energy ray hardening 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 volatile organic compound which does not have a group which does not react with acrylfluorene group (especially non-reactive volatilization which does not contain (meth) acrylfluorene group in the molecule). (Active organic compound) is added to the active energy ray-curable composition, and the fluorine-containing active energy ray-curable composition can impart liquid repellency and antifouling properties.

The fluorine-containing acrylic composition of the present invention comprises (A) a fluorine-containing acrylic compound represented by formula (1) described later, and (B) has a viscosity of 100 mPa at 25 ° C. The acrylic compound containing s or less and containing one or two (meth) acrylfluorenyl groups in one molecule is characterized in that the mass ratio of the component (A) to the component (B) is 0.03 <(A) / (B) In the range of <10, a volatile organic compound (in particular, a non-reactive volatile organic compound that does not contain a (meth) acrylic acid fluorenyl group) is not blended with a group that does not react with an acrylic acid fluorenyl group.

The fluorine-containing acrylic compound of the 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). In the present invention, the so-called "acrylic compound" is a generic term for compounds having an acryl group and an α-substituted acryl group, and also includes urethane acrylates having an urethane bond in the molecule, Alternatively, a compound having two or more acrylfluorenyl groups and α-substituted acrylfluorenyl groups may be introduced into the side chains or terminals of various polymers by any method. In the present invention, "(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 having a molecular weight of 800 to 20,000 composed of a perfluoroalkylene group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms, and an oxygen atom. Especially 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 a ratio of a terminal structure to a main chain structure based on ¹ H-NMR and ¹⁹ F-NMR.

Rf ^{1 is} particularly preferably constituted by any one or a combination of plural repeating unit groups mainly shown below.

-CF ₂ O-

-CF ₂ CF ₂ O-

-CF ₂ CF ₂ CF ₂ O-

-CF (CF ₃ ) CF ₂ O-

Here, examples of the portion that is not suitable for the main structure include a bonding portion with Z ^1, an initiator fragment or a by-product structure during the construction of the main chain structure.

Among them, Rf ¹ is particularly suitable for 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 preferably an integer from 6 to 201.

In addition, s is an integer from 0 to 6, t and u are integers from 1 to 100, t + u is an integer from 2 to 120, and v is an integer from 1 to 120.

When the values of p + q, t + u, or v are small, the characteristics sought for fluorine compounds are difficult to appear. When the values are too large, the compatibility with other components is deteriorated. The values of p, q and p + q, t, u, and t + u or v in the composition may be single or may have a distribution. In the case of a distribution, the value sought by ¹⁹ F-NMR or the like The average molecular weight preferably satisfies the above range.

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

As a preferable ^one of Z1, the following structures are mentioned.

-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 the structure of Z ¹ which is particularly good, the following may be mentioned.

-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, and may be a cyclic structure, and may be selected from an oxygen atom, a nitrogen atom, and a fluorine atom. At least one of them. As such a preferred Q ¹ , a siloxane structure having (a + 1) Si atoms, a non-substituted or halogen-substituted silyl structure, a silyl structure, or the like can be listed respectively. (A + 1) -valent linking group composed of two or more combinations.

As a particularly preferable structure, the following structures are shown.

However, a is the same as a in the above formula (1), and is independently an integer of 1 to 10, preferably an integer of 1 to 8, and more preferably an integer of 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, and the bonding part of each unit (a + 1) and 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 an (a + 1) -valent linking group, and the following examples are exemplified.

Among them, Q ¹ is the best.

In the above formula (1), Z ² is independently a divalent hydrocarbon group having 1 to 200 carbon atoms and may include at least one selected from an oxygen atom, a nitrogen atom, and a silicon atom, preferably 2 to 80. Contains a 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, and the total number of carbon atoms may be 200 or less. The arrangement of duplicate units is random regardless of the type. Also, each repeating unit is not a monomer Make a mixture of isomers.

As Z ² , particularly preferable structures include the following. Among them, those in which d is 1 to 30 and e is 1 to 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 kind of acrylfluorenyl group or an α-substituted acrylfluorenyl group selected from an oxygen atom and a nitrogen atom, but R ^{1 is} , on average, at least one monovalent organic group containing the acrylfluorenyl group or α-substituted acrylfluorenyl group in one molecule. As the monovalent organic group, a group having at least one at the terminal, preferably having 1 to 5 acrylfluorenyl groups or α-substituted acrylfluorenyl groups is preferred. Examples of the substituent include methyl, ethyl, and From halogen atoms in F, CF ₃ , Cl and Br, etc. In addition, it may have a amide bond, an ether bond, an ester bond, and the like in the middle of the structure. In particular, the R ¹ O- group may include a urethane bond (-NH (C = O) O-). Examples of the structure of 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 a hydrogen atom, but not all of them are hydrogen atoms, it is based on one molecule containing at least one of the aforementioned propylene fluorenyl group and / or α-substituted propylene fluorene Base.

In the formula (1), X is _a monovalent group represented by _a fluorine atom or -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.

(Where 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, for example, 2, 4, and 9. R 'is a hydrogen atom,

or

These may be mixed in one molecule. However, R 'is an average monovalent organic group containing at least one of the (meth) acrylfluorenyl groups in one molecule).

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

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

These (A) components may be single or may be a mixture of a plurality of compounds to which the above definition is applied. In the case of a mixture, the total content of the compounds equivalent 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 an acrylic compound containing one or two (meth) acrylfluorenyl groups in one molecule of (B). The component (B) has a viscosity at 25 ° C of 100 mPa from the viewpoint of solubility with the component (A) and miscibility with the component (C) described later. s or less, preferably 0.4 to 20 mPa. s. (B) The acrylic compound-based hydrogen atom of the component may be partially substituted by a chlorine atom (Cl), a fluorine atom (F), or a bromine atom (Br), and may include an oxygen atom, a nitrogen atom other than the acrylic structure, and may also include an ether. Bond, urethane bond, isocyanate group, hydroxyl group.

As a preferable example of the compound (B) which has one (meth) acrylfluorenyl group in a molecule | numerator, specifically, it shows the following Expressed by the general formula (2).

CH ₂ = CR ⁶ COOR ⁵ (2)

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

Specific examples of such compounds include meth (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) acrylic acid Ester, tridecyl (meth) acrylate, isostearyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, tetrahydrofuryl (meth) Acrylate, isobornyl (meth) acrylate, phenoxyethyl acrylate, neopentyl glycol-acrylic acid-benzoate and the like.

In addition, as an acrylate compound having a repeating unit structure such as ethylene oxide, propylene oxide, tetramethylene oxide, and lactone, and having various alkoxy terminals, for example, methoxy polyethylene glycol (methyl ) Acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene Commercially available (meth) acrylic compounds with the names of glycol (meth) acrylate, nonylphenol EO adduct acrylate, etc., if the viscosity at 25 ° C is 100 mPa. It can also be used below s.

Moreover, as a compound which has two acryl fluorenyl groups in one molecule, 1,3-butanediol di (meth) acrylate and 1,4-butanediol di (meth) acrylic acid are mentioned specifically, 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, and the like.

Furthermore, as a part or the whole of (B) component, it is suitable for a part of hydrogen atom to be substituted by F, Cl, and Br, and it is especially preferable that it is 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 having 1 to 8 carbon atoms, and a hydrogen atom in the hydrocarbon group may be substituted by F, Cl, Br.

Examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms and 1 to 6 carbon atoms include alkyl groups such as methyl and ethyl, and fluoroalkyl groups such as trifluoromethyl. R ^{2 is} preferably a hydrogen atom or a methyl group.

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

Examples of Z ³ which are particularly preferred include the following.

-CH _2-

-CH ₂ CH _2-

-CH ₂ -CH (OH) -CH _2-

-CH ₂ -CH ₂ -O-CH ₂ CH _2-

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

Specifically, Rf ² represents 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 which satisfies the above condition (B) component, 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 or a mixture of a plurality of compounds to which the above definition is applied. In the case of a mixture, the total content of the compounds corresponding to (B) may be calculated as the content of the component (B). Although a compound corresponding to the component (B) can be synthesized by a known method if necessary, it is commercially available from various manufacturers such as test drug manufacturers, and it can also be used directly.

The fluorine-containing acrylic composition according to the first embodiment of the present invention uses the above-mentioned components (A) and (B) as essential components, and the mass ratio of the components (A) and (B) is 0.03 <(A) / (B ) <10, preferably in the range of 0.05 ≦ (A) / (B) ≦ 8, more preferably 0.1 ≦ (A) / (B) ≦ 5, and, unblended, does not have Volatile organic compounds (especially non-reactive volatile organic compounds that do not contain a (meth) acrylfluorenyl group in the molecule).

As another embodiment of the present invention, this fluorine-containing acrylic composition is mixed with an active energy ray-curable composition (E) to be described later, and it is determined as a fluorine-containing active energy ray-curable composition, and this is applied and cured. Next, although a liquid-repellent and antifouling hardened material layer can be provided on the substrate, the liquid-repellent and antifouling properties are dispersed among the components of the active energy ray-curable composition (E) ( A) A component exists on the surface of a hardened | cured material layer and expresses it. 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, and the final performance of liquid repellency and antifouling becomes difficult. When the mass ratio (A) / (B) is 10 or more, Due to the high viscosity of the component (A), workability is reduced, and compatibility or miscibility with the component (E) is reduced.

The manufacturing method of the fluorine-containing acrylic composition in the first embodiment of the present invention is not particularly limited, and it may be mixed with the component (A) and component (B) obtained by various methods. However, the more the acrylic compound of the component (A) improves the properties of imparting liquid repellency and antifouling properties, and the more it increases the viscosity, there is a tendency that it is difficult to remove volatiles and become a high viscosity compound. Conditions such as heating cause the polymerization of the acrylamide group in the structure of the component (A), and there is a high risk of thickening or gelation. Therefore, it is more preferable to prepare a raw material from which a volatile component (a volatile organic compound which does not have a group which reacts with acrylfluorene group) has been removed, and to synthesize it in the presence of the component (B) using a synthesis step before the acrylfluorene group is introduced. (A) As a component, it is desirable to obtain the fluorine-containing acrylic composition as a target.

As a method for producing the fluorine-containing acrylic compound represented by the formula (1) as the component (A), for example, first, a polyfunctional Si-H group represented by the following general formula (5) manufactured 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 all the a H systems included in [] are bonded to the silicon atom in the structure of Q ^1. X ′ is a fluorine atom or -Z ^1- Q ^1- [H] _a ), and hydrosilylation reaction with an alcohol having an unsaturated group at the end represented by the following general formula (6) (a compound having an alkenyl group and an alcoholic hydroxyl group in the molecule), CH ₂ = CR ⁴ -Z ³ -OH (6)

(In the formula, R ⁴ and Z ³ are -CH ₂ -CHR ⁴ -Z ³ -structures formed after hydrosilylation if the requirements of Z ² in formula (1) are satisfied. R ⁴ and Z ³ may be (The bond becomes a ring structure)

A fluorine-containing polyfunctional alcohol compound represented by the following general formula (4) of the 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 a fluoropolyether compound which has a polyfunctional Si-H group represented by the said Formula (5), the following can be illustrated.

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

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

Examples of the alcohol containing a terminal unsaturated group represented by the formula (6) include the following.

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).

In this hydrosilylation (addition) reaction system, it is desirable to mix a fluoropolyether compound having a polyfunctional Si-H group represented by the formula (5) and an alcohol containing an unsaturated group at the terminal represented by the formula (6). In the presence of the addition reaction catalyst, the reaction is performed at a reaction temperature of 50 to 150 ° C., preferably 60 to 120 ° C. for 1 minute to 48 hours, especially 10 minutes to 12 hours. When the reaction temperature is too low, the reaction may be stopped directly if the reaction is not sufficiently carried out. When the reaction temperature is too high, the temperature may increase due to the reaction heat of the hydrosilylation, which may make it impossible to control the reaction, and may cause bumping or decomposition of raw materials.

In this case, it is desirable that the reaction ratio of the fluoropolyether compound having a polyfunctional Si-H group represented by the formula (5) to an alcohol having an unsaturated group at the terminal represented by the formula (6) is expressed relative to the formula (5) The poly molybdenum of polyfunctional Si-H-based fluorinated polyether compounds [] includes 0.5 to 5.0 times the total mole number of H of the Molar formula (6). , Especially using 0.9 ~ 2.0 times mole. When the alcohol containing unsaturated groups at the terminal represented by formula (6) is smaller than this, it may be difficult to obtain a fluorine-containing polyfunctional alcohol compound having high solubility. When there are more than this, the uniformity of the reaction solution may be reduced. When the reaction rate becomes unstable, and when the alcohol containing an unsaturated group at the terminal represented by the formula (6) is removed after the reaction, it is necessary to strictly heat, decompress, and increase only the remaining unreacted alcohol. Conditions for extraction, etc.

As the addition reaction catalyst, for example, a compound of a platinum group metal including platinum, rhodium, or palladium can be used. Among them, compounds containing platinum are preferred, and hexachloroplatinum (IV) acid hexahydrate, platinum carbonyl vinyl methyl complex, platinum-divinyltetramethyldisilaxane complex, and platinum can be used. -A cyclovinylmethylsiloxane complex, a platinum-octylaldehyde / octanol complex, or platinum carried on activated carbon.

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

Although the above-mentioned addition reaction can be performed even in the absence of a solvent, it can be diluted with a solvent if necessary. At this time, although a widely used organic solvent such as toluene, xylene, and isooctane can be used as the diluent solvent, it is preferable that the boiling point is higher than the intended reaction temperature and does not hinder the reaction. The fluorine-containing polyfunctionality generated after the reaction The alcohol compound is soluble at the above reaction temperature. As such a solvent, for example, a part of a fluorine-modified aromatic hydrocarbon-based solvent such as m-xylene hexafluoride, benztrifluoride (Benzotrifluoride), or a fluorine-modified ether-based solvent such as methyl perfluorobutyl ether is desired. Fluoro-modified solvents, especially m-xylene hexafluoride, are preferred.

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

After completion of the reaction, it is preferable to distill off the unreacted alcohol containing an unsaturated group at the terminal represented by formula (6) or dilute the solvent under reduced pressure, and to remove it by a known method such as extraction or adsorption. Although these methods can be implemented alone or in combination, especially in the final stage of removal, by using reduced pressure distillation or molecular distillation, for example, by internal temperature of 85 ° C or higher and 0.133kPa or lower, etc. The conditions are such that distillation is performed until the distillation is stopped, and it is desirable that the content of the volatile organic compound at normal pressure and equivalent to a boiling point of 260 ° C. or lower be 1% by mass or less.

Examples of the fluorine-containing polyfunctional alcohol compound represented by the formula (4) obtained in this manner include the following.

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

Next, a fluorine-containing acrylic compound (A) can be obtained by introducing a propylene fluorenyl group into the fluorine-containing polyfunctional alcohol compound obtained as described 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), one molecule A method in which an isocyanate group is reacted with at least one (meth) acrylfluorene compound (D) to synthesize the component (A), thereby obtaining a fluorine-containing acrylic composition according to the first embodiment of the present invention.

Examples of the compound (D) having one isocyanate group and at least one (meth) acrylfluorenyl group in one molecule include the following.

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

The component (D) can be reacted by adding more than equal moles as isocyanate groups to the total amount of hydroxyl groups of the component (C), and the entire hydroxyl groups can be reacted to form urethane. The components are averaged at 1 mole, and it is only necessary to introduce an acrylic fluorenyl group of 1 mole or more. The remaining amount of the unreacted (D) component can be reduced by making the hydroxyl groups equal to the isocyanate groups or making the hydroxyl groups excessive. Specifically, it is desirable to make it equivalent to (C) in the reaction system. When the total compound amount is set to x moles, and when the total amount of the hydroxyl groups of the component (C) is set to y moles, the blending amount of the (D) component is not less than x moles and less than 1.05y moles. It is preferably 0.5y moles or more and 1.0y moles or less. (D) When there are too few components, there exists a possibility that the (C) component which does not introduce | transmit a propenyl group at all may remain, and there exists a possibility that the hardenability of the final composition or the solubility of a product may fall. When there are too many (D) components, the residual amount of (D) component may increase, and there exists a possibility that the antifouling performance of the final composition may be affected.

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

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

In addition, if the blending amount of the (D) component is larger than 1.0 y, and if the (D) component remains after the reaction, the remaining (D) component is considered to be a part of the (B) component. That is, the component (B) contained in the remaining (D) component is defined as (B1), and the mass of the component (D) equivalent to 1.0y is defined as (d1). When the value of the component minus (d1) is determined as (d2), it is preferable to satisfy the following.

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

If necessary, a polymerization inhibitor may be added during the reaction. Although it is not particularly limited as a polymerization inhibitor, it can be generally used as a polymerization inhibitor user of an acrylic compound. Specific examples include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, and dibutylhydroxytoluene.

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

In this reaction, an appropriate catalyst can be added in order to increase the reaction speed. Examples of the catalyst include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin diacetate, dioctyltin dilaurate, and dioctyl. Dioctoate tin, stannous dioctanoate and other alkyl tin ester compounds, titanium tetraisopropoxide, titanium tetra-n-butoxy, titanium (2-ethylhexyloxy), dipropoxy Titanate or titanium chelator compounds of bis (acetamylacetone) titanium, titanium isopropoxyoctanediol, zirconium tetraacetamidine acetone, zirconium tributoxymonoacetamidine, zirconium monobutoxyethyl Samarium acetone bis (ethylacetoacetate), zirconium dibutoxy bis (ethylacetoacetate), zirconium tetraacetamidine acetone, zirconium chelator compounds, and the like. These are not limited to one type, and although they can be used as a mixture of two or more types, titanium compounds and zirconium compounds having low environmental impact are particularly preferred.

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

In the reaction, if necessary, the components (B), (C), and (D) are stirred and mixed together with the above-mentioned polymerization inhibitor or catalyst, and if necessary, heated to allow the reaction to 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 may be a possibility that polymerization of the propylene fluorenyl group may occur as a side reaction.

After the reaction, if necessary, The coloring component or the insoluble component is removed by a method such as filtration and washing to obtain the fluorine-containing acrylic composition of the present invention.

The fluorinated acrylic composition obtained in this manner becomes a person not blended with a volatile organic compound.

The fluorine-containing acrylic composition of the present invention can be added to an active energy ray-curable composition (E) to be described later to form 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 as long as it is given to the cured product by irradiation of active energy rays such as ultraviolet rays and electron beams, but it is particularly The acrylic compound (Ea) and the photopolymerization initiator (Eb) are preferably contained.

As the acrylic compound (Ea), either monofunctional or polyfunctional can be used. For example, although the above-mentioned (B) component may be used as a monofunctional and bifunctional acrylic compound, as the (Ea) component, particularly, a non-fluorinated acrylic compound having two or more acrylfluorenyl groups contained in one molecule Better.

Such a non-fluorinated acrylic compound may be one having two or more propylene fluorenyl groups or α-substituted propylene fluorenyl groups in one molecule, and examples thereof include 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, ginsyl (meth) acryloxyethyl phosphate , Hydrogen phthalate- (2,2,2-tri- (meth) acrylic acid Oxymethyl) ethyl ester, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2 to 6-functional (meth) acrylic compounds such as dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, etc., and these (meth) acrylic compounds are used in ethylene oxide, propylene oxide, Copolymer of epichlorohydrin, fatty acid, alkyl modified product, epoxy resin with acrylic acid, and (meth) acrylfluorene group introduced into the side chain of the obtained epoxy acrylates and acrylate copolymer Wait.

In addition, urethane acrylates may be used, and a (meth) acrylate obtained by reacting a (meth) acrylate having a hydroxyl group in a polyisocyanate may be used, and a (methyl) having a hydroxyl group in a polyester of the polyisocyanate and a terminal diol may be used. A polyisocyanate obtained by reacting an acrylate with a polyisocyanate obtained by reacting an excess of a diisocyanate with a polyol. A product obtained by reacting a (meth) acrylate having a hydroxyl group. Among them, a (meth) group having a hydroxyl group selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-propenyloxypropylmethacrylate, and pentaerythritol triacrylate is preferred. Acrylate, and selected from hexamethylene diisocyanate, isophorone diisocyanate, methylenephenyl diisocyanate, lysine diisocyanate, norbornane diisocyanate, 1,3-bis (isocyanate (Methyl) cyclohexane, methylene bis (4-cyclohexyl isocyanate), 2-methyl-1,3-diisocyanocyclohexane, 2-methyl-1,5-diisocyanate Urethane acrylates that react with the polyisocyanates in cyclohexane and diphenylmethane diisocyanate.

In particular, polyfunctional propyl groups having two or more propylene fluorenyl groups or α-substituted propylene fluorenyl groups and having no urethane bond can be listed in one molecule. An enoic acid compound, or a polyfunctional amine having 3 or more acryl fluorenyl groups or α-substituted acryl fluorenyl groups in one molecule, obtained by reacting a polyfunctional acrylic compound with an aliphatic polyisocyanate and an acrylic compound having a hydroxyl group. A mixture of at least two types of acrylic compounds among urethane acrylates.

Here, as a polyfunctional acrylic compound having two or more propylene fluorenyl groups or α-substituted propylene fluorenyl groups in one molecule and not having a urethane bond, trimethylolpropane tri (meth) acrylic acid can be mentioned. Ester, pentaerythritol tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (methyl) Acrylates, dipentaerythritol hexa (meth) acrylates, sorbitol hexa (meth) acrylates, and compounds modified with ethylene oxide or propylene oxide.

Polyfunctional urethane acrylates having three or more acrylfluorene groups or α-substituted acrylfluorene groups in one molecule obtained by reacting an aliphatic polyisocyanate with an acrylic compound having a hydroxyl group can be expressed in Liuya Methyl diisocyanate, norbornane diisocyanate, isophorone diisocyanate, and these 3 quantified products, and these bifunctional and trifunctional isocyanates make aliphatic diols, aliphatic polyols, and the like Polyisocyanates of more than two functions obtained by reacting polyacrylates having a hydroxyl group on the chain, such as trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, and bis (2- ( (Meth) acryloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylic acid Ester and this Those who react with ethylene oxide and propylene oxide modifiers, or make aliphatic polyols and polyacrylates with hydroxyl groups on the side chain and 2-isocyanatoethyl (meth) acrylate or 1,1 -A reaction of an acrylic compound having an isocyanate group such as (bispropenyloxymethyl) ethyl isocyanate.

Furthermore, as the (Ea) component, not only the liquid component, but also the surface of the high-molecular-weight body in the form of fine particles or the surface of the inorganic filler fine particles may be modified with an acryl group.

Although the (Ea) component as described above can be used alone, it can also be used in combination with a plurality of compounds equivalent to improve the coatability or the characteristics of the film after curing.

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

The photopolymerization initiator of the (Eb) component is not particularly limited as long as it can harden an acrylic compound by irradiation with ultraviolet rays, but preferred examples include acetophenone, benzophenone, and 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- Morpholinylpropane-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 -Phosphine oxide, bis (2,4,6-trimethylbenzyl) -phenylphosphine oxide, 1,2-octanedione-1- [4- (phenylthio) -2 -(o-benzylideneoxime)], ethyl ketone-1- [9-ethyl-6- (2-methylbenzidine ) -9H-carbazol-3-yl] -1- (O-ethenyloxime), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanyl) benzyl The group] phenyl} -2-methylpropane-1-one and the like may be used alone or in combination of two or more.

The content of the (Eb) component can be appropriately determined depending on the hardening conditions and the physical properties of the hardened material of the active energy ray-curable composition (E) which is the purpose, but it is desired to be, for example, 100 parts by mass based on the total of the (Ea) component The amount is 0.1 to 15 parts by mass, especially 1 to 10 parts by mass. When the addition amount is less than this, the hardenability may be reduced, and when it is more, the effect on the physical properties after hardening may increase.

In addition to the active energy ray-curable composition (E), active energy ray-reactive compounds other than acryl fluorenyl groups, organic solvents, and polymerization inhibitors, such as thiol compounds or maleimide compounds, may be blended. , Antistatic agent, defoaming agent, viscosity adjuster, light stabilizer, heat stabilizer, antioxidant, surfactant, colorant, and fillers for polymers or inorganic materials. These structures are not particularly limited, and a known one can be used as long as the object of the present invention is not impaired.

In addition, as the active energy ray-curable composition (E), as the active energy ray-curable composition in which (Ea), (Eb) components and various additives have been blended, coatings, inks, and hardeners from various companies can be used Classifications of paints and the like Existing compositions that are commercially available are used as part or all of the component (E). In this case, even if a commercially available hard coating agent is used, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity adjusting agent, a light-resistant stabilizer, a heat-resistant stabilizer, an antioxidant, and an interfacial activity can be added depending on the purpose. Agents, colorants, and fillers.

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

With the fluorinated active energy ray-curable composition of the present invention obtained as described above, the content of volatile organic compounds in a structure that does not incorporate a cured product can be suppressed, and antifouling properties can be formed on the surface of any substrate. A hardening composition having very little occurrence of volatile organic compounds in a hardened resin layer having 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 and hardened. As described above, by using the fluorine-containing active energy ray-curable composition of the present invention, a cured film (cured resin layer) having excellent surface characteristics can be formed on the surface of a substrate. In particular, it is useful because it imparts water repellency, oil repellency, and stain resistance to the surface of the acrylic hard coat. With this, it is difficult to attach the pollution caused by fingerprints, sebum, sweat, human fat, cosmetics, etc., and wipe A hard-coated surface having excellent properties is attached to a substrate (article). Therefore, the fluorine-containing active energy ray-curable composition of the present invention can provide a coating film or a protective film on the surface of a substrate (article) that is likely to be contaminated by human fat, cosmetics, and the like.

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

Here, although the coating method of the fluorine-containing active energy ray-curable composition of the present invention is not particularly limited, for example, roll coating, gravure coating, flow coating, dip coating, spray coating, spin coating, and rod can be used. Coating, screen printing, and other well-known coating methods. After coating, the coating film was irradiated with active energy rays to harden it. Here, as the active energy ray, any of an electron beam and ultraviolet rays can be used, but ultraviolet rays are particularly preferred. As an ultraviolet source, it is suitable for a mercury lamp, a metal halide lamp, and an LED lamp. As the amount of ultraviolet radiation is too small, uncured components remain, and if too much, the coating film and substrate may deteriorate, so it is desirable to be in the range of 10 to 10,000 mJ / cm ² , especially 20 to 4,000 mJ / cm ² . . In addition, in order to prevent the hardening caused by oxygen, the irradiation environment may be replaced with an inert gas containing no oxygen molecules such as nitrogen, carbon dioxide, argon, etc., or the surface of the coating film may be provided with ultraviolet rays having mold release properties. When a transparent protective layer is coated, and when the substrate is irradiated with ultraviolet rays, or the substrate has ultraviolet permeability, the surface of the coating film may be covered with a mold-removable protective layer, and may be opposite to the coating 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 fluorene group in the coating film, the coating film and the substrate may be heated by an arbitrary method such as a hot air drying furnace before and during ultraviolet irradiation.

In addition, although the thickness of the hardened film (hardened resin layer) formed by using the fluorine-containing active energy ray-curable composition of the present invention is not particularly limited, the obtained film is not sufficiently obtained when the thickness is too thin. When the surface hardness is too thick, the mechanical strength of the hard coating film is lowered. From the point of easily falling into cracks, it is usually 5 nm to 100 μm, particularly preferably 1 μm to 20 μm.

As such items, for example, as a tablet computer, a mobile phone. Mobile (communication) information terminals such as smart phones, notebook computers, digital media players, and models. Glasses-type wearable computers, digital cameras, digital video cameras, e-book readers, and other human-made walking frames; liquid crystal displays, plasma displays, organic EL displays, rear-projection displays, fluorescent display tubes ( VFD), field emission projection displays, CRTs, toner displays, and other flat panel displays, TV screens, etc. indicate the surface of the operating machine, the exterior of a car, the glossy surface of a piano or furniture, the construction of marble, etc. Decorative materials such as stone surfaces, toilets, bathrooms, washrooms, etc., protective glass for art exhibitions, display windows, display cabinets, covers for photo frames, watches, glass for car windows, window glass for trains, aircraft, etc., automobiles Coating films and surface protection films for transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members such as headlights and taillights, and various mirror members are useful.

Especially with a finger or hand using a touch panel display, etc. Various devices that display input devices for performing operations on the screen, such as tablet computers, notebook computers, watch-type wearable computers, activity meters, and mobile phones. Mobile (communication) information terminals such as smartphones, digital media playback devices, e-book readers, digital photo frames, game consoles and game console controllers, digital cameras, digital video cameras, navigation devices for automobiles, automatic cash deposit Various surface protection films such as take-out devices, automatic cash dispensers, vending machines, digital signage (electronic signage), security system terminals, POS terminals, remote controllers, and display input devices such as panel switches for in-vehicle devices are useful.

Furthermore, the hardened film formed by the fluorine-containing active energy ray-curable composition of the present invention is used as an optical recording medium such as a magneto-optical disc, an optical disc, an eyeglass lens, a camera lens, a projector lens, a lens sheet, and a protective film. , Polarizers, optical filters, lenticular lenses, Fresnel lenses, anti-reflection films, optical fibers and optical couplers as optical components. Surface protective films for optical devices or surface protective films for various protective parts of such machines are also useful.

[Example]

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

[Synthesis Example 1] Synthesis of fluorine-containing alcohol compound (C-1)

A 2,000 mL three-necked flask equipped with a reflux device and a stirring device in a dry nitrogen environment, and 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)

500 g (0.125 mol) of perfluoropolyether shown, 700 g of m-xylene with hexafluoride, and 361 g (1.50 mol) of tetramethylcyclotetrasiloxane, were heated to 90 ° C while stirring. Here, 0.442 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisilaxane complex (containing 1.1 × 10 ^-6 mol as Pt monomer) was charged, and the internal temperature was maintained at 90 ° C. The above was continuously stirred for 4 hours. After the disappearance of the allyl group of the raw material was confirmed by ¹ H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Thereafter, 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, 28.20 g (0.276 mol) of 2-allyloxyethanol and m-xylene hexafluoride were mixed with 200.0 g (Si-H group amount: 0.133 mol) of the compound (I) obtained above. 200.0 g and 0.0884 g of a toluene solution of a chloroplatinic acid / vinylsiloxane complex (containing 2.2 × 10 ⁻⁷ mol as Pt monomer) were stirred at 100 ° C. for 4 hours. After confirming the disappearance of the Si-H group by ¹ H-NMR and IR, the solvent and excess 2-allyloxy ethanol were distilled off under reduced pressure, and activated carbon treatment was performed to obtain a pale yellow transparent liquid containing fluorine represented by the following formula: 216.1 g of the 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 fluorine-containing alcohol compound (C-2)

Under a dry nitrogen environment, a 3,000 mL three-necked flask equipped with a reflux device and a stirring device was charged with 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) _p2 (CF ₂ CF ₂ O) _q2 CF _2-

(q2 / p2 = 1.2, p2 + q2 ≒ 18.5)

500 g (0.272 mol) of perfluoropolyether shown, 1,000 g of m-xylene with hexafluoride, and 660 g (2.72 mol) of tetramethylcyclotetrasiloxane, were heated to 90 ° C while stirring. Here, 0.884 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisilaxane complex (containing 2.2 × 10 ^-6 mol as Pt monomer) was charged, and the internal temperature was maintained at 90 ° C. The above was continuously stirred for 4 hours. After the disappearance of the allyl group of the raw material was confirmed by ¹ H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Thereafter, 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, 105.8 g (1.04 mol) of 2-allyloxyethanol and m-xylene hexafluoride were mixed with 200.0 g (Si-H group amount: 0.518 mol) of the compound (II) obtained above. 400.0 g of a toluene solution of chloroplatinic acid / vinylsiloxane complex (containing 4.4 × 10 ^-7 mole as Pt monomer) was stirred at 100 ° C. for 4 hours. After confirming the disappearance of the Si-H group by ¹ H-NMR and IR, the solvent and excess 2-allyloxy ethanol were distilled off under reduced pressure, and activated carbon treatment was performed to obtain a pale yellow transparent liquid containing fluorine represented by the following formula: The alcohol compound (C-2) was 240.4 g.

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 fluorinated acrylic composition (F-1)

In a dry air environment, (B-1) 2- (perfluorohexyl) ethyl acrylate was mixed with 50.0 g (hydroxyl amount of 0.058 moles) of the fluorine-containing alcohol compound (C-1) obtained in Synthesis Example 1 [ Viscosity 4mPa. s / 25 ° C] 57.9 g, (D) 7.87 g (0.055 moles) of propylene ethoxyethyl isocyanate, and heated to 50 ° C. with stirring for 1 hour. To this was added 0.05 g of dioctyltin (di) laurate, and the mixture was stirred at 50 ° C. for 8 hours. From the results of ¹ H-NMR, it was confirmed that the methylene peak of 4.2 ppm of unreacted propylene ethoxyethyl isocyanate and the methylene peak of 4.1 ppm after the formation of the urethane bond were all changed. The disappearance of the peak of the isocyanate group at 2,260 cm ^{-1 was} confirmed from the IR spectrum. After the heating was completed, activated carbon treatment was performed on the obtained reaction solution to obtain 100.3 g of a pale yellow liquid. Thereby, the reactants of (C-1) and (D), that is, the fluorine-containing acrylic compound (A-1) and 2- (perfluorohexyl) ethyl acrylate (B-1) shown below are obtained as ( The fluorine-containing acrylic composition (F-1) is mixed at 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 fluorinated acrylic composition (F-2)

In a dry air environment, (B-2) 2- (perfluorohexyl) ethyl methacrylic acid was mixed with 50.0 g (hydroxyl amount of 0.058 moles) of the fluorine-containing alcohol compound (C-1) obtained in Synthesis Example 1. Ester [viscosity 5mPa. s / 25 ° C] 57.9g, (B-3) isobutyl acrylate [viscosity 1mPa. s / 25 ° C] 115.8 g, (D) 7.87 g (0.055 moles) of propylene ethoxyethyl isocyanate, heated to 50 ° C. and stirred for 1 hour. To this was added 0.05 g of tin (di) laurate, and the mixture was stirred at 50 ° C for 8 hours. From the results of ¹ H-NMR, it was confirmed that the methylene peak of 4.2 ppm of unreacted propylene ethoxyethyl isocyanate and the methylene peak of 4.1 ppm after the formation of the urethane bond were all changed. The disappearance of the peak of the isocyanate group at 2,260 cm ^{-1 was} confirmed from the IR spectrum. After the heating was completed, activated carbon treatment was performed on the obtained reaction solution to obtain 170.1 g of a pale yellow liquid. Thereby, the reactants of (C-1) and (D), that is, the fluorine-containing acrylic compound (A-1) and 2- (perfluorohexyl) ethyl methacrylate (B-2) shown below are obtained. ) And isobutyl acrylate (B-3), a fluorine-containing acrylic composition (F-2) with a mass ratio of (A-1) / [(B-2) + (B-3)] = 0.33 .

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

In a dry air environment, 50.0 g of m-xylene hexafluoride and (D) acryloxyethyl were mixed with 50.0 g (hydroxyl amount of 0.058 moles) of the fluorine-containing alcohol compound (C-1) obtained in Synthesis Example 1. 7.87 g (0.055 mole) of isocyanate, heated to 50 ° C. and stirred for 1 hour. To this was added 0.05 g of tin (di) laurate, and the mixture was stirred at 50 ° C for 8 hours. From the results of ¹ H-NMR, it was confirmed that the methylene peak of 4.2 ppm of unreacted propylene ethoxyethyl isocyanate and the methylene peak of 4.1 ppm after the formation of the urethane bond were all changed. From the IR spectrum, the disappearance of the peak of the isocyanate group at 2,260 cm ^{-1 was} confirmed, and the heating was terminated. Activated carbon treatment was performed on the obtained reaction solution to obtain 98.2 g of a pale yellow liquid. The obtained pale yellow liquid was distilled off under reduced pressure for 3 hours on a rotary evaporator at 60 ° C. and 133.32 Pa, and the single ion (A-1) was used as 55.2 g of a pale yellow ointment-like component. It was confirmed that the obtained (A-1) heat-dried mass at 105 ° C. for 3 hours was reduced to 0.01% by mass or less.

10 g of the obtained (A-1) was placed in a glass container with a lid, and (B-4) 2- (perfluorobutyl) ethyl acrylate [viscosity 3 mPa. s / 25 ° C] 10g, (B-5) tetrahydrofuryl acrylate [viscosity 3mPa. s / 25 ° C] 30g, shake with a vibrator until it dissolves uniformly, and obtain a fluorine-containing 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, 254.8 g of (B-3) isobutyl acrylate and (D) propylene were mixed with 50.0 g (with a hydroxyl amount of 0.102 mol) of the fluorine-containing alcohol compound (C-2) obtained in Synthesis Example 2. 13.7 g (0.097 mol) of methoxyethyl isocyanate was heated to 50 ° C. and stirred for 1 hour. To this was added 0.10 g of dioctyltin (di) laurate, and the mixture was stirred at 50 ° C. for 8 hours. From the results of ¹ H-NMR, it was confirmed that the methylene peak of 4.2 ppm of unreacted propylene ethoxyethyl isocyanate and the methylene peak of 4.1 ppm after the formation of the urethane bond were all changed. The disappearance of the peak of the isocyanate group at 2,260 cm ^{-1 was} confirmed from the IR spectrum. After the heating was completed, activated carbon treatment was performed on the obtained reaction solution to obtain 318.7 g of a pale yellow liquid. Thereby, the reactant of (C-2) and (D), that is, the fluorinated acrylic compound (A-2) and (B-3) isobutyl acrylate shown below as (A-2) / (B-3) A fluorine-containing acrylic composition (F-4) mixed at 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)

However, the fluorinated acrylic composition obtained in the above Examples 1 to 4 does not contain a volatile organic compound.

[Comparative Example 1]

In Example 3, although it was replaced with (B-5) tetrahydrofuryl acrylate, trimethylolpropane triacrylate [viscosity 110 mPa. s / 25 ° C] An attempt was made to prepare the composition, but it was separated without being dissolved.

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

Using the following acrylic compound (Ea) and photopolymerization initiator (Eb), an active energy ray-curable composition (E) was prepared.

(Ea-1) Dipentaerythritol penta / hexaacrylate

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

(Ea-2) pentaerythritol triacrylate

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

(Ea-3) Pentaerythritol ethoxytetraacrylate

[EBECRYL 40 by Daicel ornex Co., Ltd.]

(Ea-4) tetrahydrofuryl acrylate (Eb-1) 1-hydroxycyclohexylphenyl ketone

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

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

[IRGACURE 127 made 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 hardening composition (E4):

(Ea-3) 100 parts by mass

(Eb-2) 3 parts by mass

Comparative composition modulation

The comparative compositions (G-1) and (G-2) were prepared at 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 fluorinated active energy ray hardening composition

The fluorine-containing acrylic compositions (F-1) to (F-4) obtained in the above examples, the fluorine-containing acrylic compounds (A-1), and 2- (perfluoro Hexyl) ethyl acrylate (B-1) or the above-mentioned comparative compositions (G-1), (G-2), and the above-mentioned active energy ray-curable compositions (E1) to (E4), to prepare a fluorine-containing activity Energy ray hardening composition. The appearance of the obtained composition was measured and shown in Table 1.

Coating and production of hardened film

Each of the fluorine-containing active energy ray-curable compositions of Examples and Comparative Examples was spin-coated on a carbonate substrate. After coating, leveling at room temperature for 10 minutes, using a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Electric Works), the coating surface was irradiated with ultraviolet rays with a cumulative irradiation amount of 1,600 mJ / cm ² in a nitrogen environment. The composition was cured to obtain a cured film having a thickness of 9 μm. 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 obtained cured film was visually measured, and the measurement of the water contact angle and the evaluation of the oil resistance signature were performed by the methods described 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.), 2 μL of the droplet was dropped on the cured film, and the contact angle after 1 second was measured. The average value of N = 5 was used as the measured value.

[Evaluation of Oil-Resistant Signature]

Draw a straight line on the surface of the cured film with an oil-based signature pen (Large-size universal ink manufactured by Terase Chemical Industry Co., Ltd.), and mark ○ for those who reject ink, and × for those who do not.

Claims (13)

A fluorine-containing acrylic composition characterized by containing the following (A) and (B) as essential components, (A) a fluorine-containing acrylic compound represented by the following general formula (1), X-Rf ¹ -Z ^1- Q ^1- [Z ² OR ¹ ] _a (1) (where, Rf ¹ is a divalent perfluoropolyether having a molecular weight of 800 to 20,000 and composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom. Group, Q ¹ is an (a + 1) valent linking group independently containing at least (a + 1) silicon atoms, which can be a cyclic structure, and may include at least one selected from the group consisting of an oxygen atom, a nitrogen atom, and a fluorine atom; Z ^{1 is} independently a divalent linking group having 1 to 20 carbon atoms and may include at least one selected from the group consisting of an oxygen atom, a nitrogen atom, and a silicon atom, and may include a cyclic structure on the way, may branch, and a part of hydrogen atoms may Substituted by a fluorine atom; Z ^{2 is} independently a divalent hydrocarbon group having 1 to 200 carbon atoms and may include at least one selected from an oxygen atom, a nitrogen atom, and a silicon atom, and may include a cyclic structure in the way; R ^{1 is} independently hydrogen Atom or containing: It may also contain at least one kind of acrylyl group selected from oxygen atom and nitrogen atom or a monovalent organic group substituted with α-substituted acrylyl group. However, R ¹ is at least one in one molecule. before Bing Xixi group α or substituent group of Bing Xixi monovalent organic group; X is a fluorine atom or a ^{-Z 1 -Q 1 - [Z 2} OR 1] a represents a monovalent radical of 1; a is an integer of 1 to 10) (B ) The viscosity at 25 ℃ is 100mPa. The mass ratio of the acrylic compound (A) component to the (B) component of the acrylic compound containing one or two (meth) acrylfluorenyl groups in one molecule is 0.03 <(A) / (B) <10 In addition, it is not a volatile organic compound which does not have a group which reacts with acrylyl group. For example, the fluorine-containing acrylic composition according to claim 1, wherein a part or all of the component (B) includes an acrylic compound represented by the following general formula (2), and CH ₂ = CR ⁶ COOR ⁵ (2) (wherein R ⁵ is an alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, which may be branched or cyclic, and may include aliphatic unsaturated bonds, urethane bonds, ether bonds, isocyanate groups, Hydroxyl group; R ⁶ is a hydrogen atom or a methyl group, a fluorine atom, and a fluoroalkyl group having 1 to 6 carbon atoms). The fluorine-containing acrylic composition according to claim 1 or 2, wherein the component (B) is an acrylic compound in which a part of hydrogen atoms is replaced by a halogen atom selected from F, Cl, and Br. For example, the fluorine-containing acrylic composition according to claim 3, wherein a part or all of the component (B) includes a fluorine-containing acrylic compound represented by the following general formula (3), and 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 having 1 to 8 carbon atoms, and the hydrogen atom in the hydrocarbon group may be replaced by F, Cl, Br; Z ³ is independently A bivalent hydrocarbon group having 1 to 8 carbon atoms can be branched and can include oxygen atoms and hydroxyl groups on the way; Rf ² is a fluoroalkyl group having 2 to 20 fluorine atoms and can include hydrogen atoms and oxygen atoms and can be branched). If the fluorine-containing acrylic composition according to any one of claims 1 to 4, wherein the fluorine-containing acrylic compound represented by the general formula (1) of the component (A), Rf ¹ is a bivalent value represented by the following three types of structural formulas: Any of the perfluoropolyether 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 6 to 201, and 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 according to any one of claims 1 to 5, wherein, in the component (A), Z ¹ in the general formula (1) is any one of the structures represented by the following formula, -CH ₂ CH ₂ CH ₂ CH ₂ --CH ₂ OCH ₂ CH ₂ CH _2- If the fluorine-containing acrylic composition according to any one of claims 1 to 6, wherein (A) component, Q ¹ in the general formula (1) is a structure represented by the following formula, (Where a is an integer of 1 to 10). The fluorine-containing acrylic composition according to any one of claims 1 to 7, wherein the component (A) is selected from a fluorine-containing acrylic compound represented by the following formula, (Where, 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 may be mixed in one molecule; however, R ′ is an average monovalent organic group containing at least one of the above (meth) acrylfluorenyl groups in one molecule, and v1 is an integer of 2 to 120). A method for producing a fluorine-containing acrylic composition, which is characterized by having a 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) acrylfluorenyl 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) (wherein X ¹ is a fluorine atom or _a group represented by -Z ¹ -Q ^1- [Z ² OH] _a , and Rf ^{1 is determined} by carbon number 1 ~ Divalent perfluoropolyether group having a molecular weight of 800 to 20,000 and composed of a perfluoroalkylene group of 6 and an oxygen atom. Z ^{1 is} independently a carbon number of 1 to 20 and may also be selected from the group consisting of an oxygen atom, a nitrogen atom, and a silicon atom. 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, which can be a cyclic structure, and may include a group selected from an oxygen atom, a nitrogen atom, and At least one kind of fluorine atom; Z ^{2 is} independently a divalent hydrocarbon group having 1 to 200 carbon atoms and may include at least one kind selected from oxygen atom, nitrogen atom, and silicon atom, and may include a cyclic structure in the way; a is (Integer number from 1 to 10); (D) a compound having one isocyanate group and at least one (meth) acryl group in one molecule; (A) a fluorine-containing acrylic compound X-Rf represented by the following general formula (1) ¹ -Z ¹ -Q ^1- [Z ² OR ¹ ] _a (1) (where Rf ¹ , Z ¹ , Q ¹ , Z ² , a Is the same as above; R ^{1 is} independently a hydrogen atom or contains: it may also contain at least one kind of propenyl group selected from an oxygen atom and a nitrogen atom or a monovalent organic group substituted with an α-substituted propenyl group; however, R ¹ It is an average of at least one monovalent organic group containing the aforementioned propylene fluorenyl group or α-substituted propylene fluorenyl group in one molecule, and X is a fluorine atom or -Z ¹ -Q ^1- [Z ² OR ¹ ] _a monovalent Group) The mass ratio of the component (A) to the component (B) is in the range of 0.03 <(A) / (B) <10. In addition, a volatile organic compound that is not blended and does not have a group that reacts with acrylfluorenyl group is obtained A fluorinated acrylic composition of a compound. The method for producing a fluorine-containing acrylic composition according to claim 9, wherein a part or all of the component (B) includes an acrylic compound represented by the following general formula (2) and / or the following general formula (3) Fluorine-containing acrylic compound, CH ₂ = CR ⁶ COOR ⁵ (2) (where R ⁵ is an alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, which may be branched or cyclic, and may include Aliphatic unsaturated bond, urethane bond, ether bond, isocyanate group, hydroxyl group; R ⁶ is a hydrogen atom or a methyl group, a fluorine atom, and a fluoroalkyl group having 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 having 1 to 8 carbon atoms. The hydrogen atom in the hydrocarbon group may be replaced by F, Cl, Br; Z ³ is independently a divalent hydrocarbon group having 1 to 8 carbon atoms, which can be branched, and can include oxygen atoms and hydroxyl groups on the way; Rf ² is a fluoroalkyl group having 2 to 20 fluorine atoms, and can include hydrogen atoms and oxygen atoms. (Can be branched) In the general formula (4) of the component (C) and the general formula (1) of the component (A), Rf ¹ is any of the divalent perfluoropolyether groups represented by the following three types of 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 6 to 201, and 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 a structure represented by the following formula, (Where a is an integer of 1 to 10). A fluorine-containing active energy ray-curable composition containing 100 parts by mass of the active energy ray-curable composition (E) and containing 0.005 to 40 parts by mass of the fluorine-containing compound according to any one of claims 1 to 8. Acrylic composition. For example, the fluorine-containing active energy ray-curable composition according to claim 11, wherein the active energy ray-curable composition (E) contains (Ea) an acrylic compound: 100 parts by mass, (Eb) a photopolymerization initiator: 0.1 to 15 parts by mass. An article comprising a cured product layer having a fluorine-containing active energy ray-curable composition as claimed in claim 11 or 12.