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

Abstract

To provide a fluorine-containing acrylic composition capable of imparting excellent liquid-repelling property, antifouling property and abrasion resistance without increasing a volatile organic compound which does not have a group reactive with an acrylic group (non reactive) as the whole curable composition when added to a curable composition and to provide a fluorine-containing active energy ray-curable composition comprising the composition and an article having a cured product layer of the composition on a substrate surface.SOLUTION: There is provided a fluorine-containing acrylic composition which comprises (A) a fluorine-containing acrylic compound having a specific structure which has a perfluoropolyether group, an acrylic group or an α-substituted acrylic group and has no urethane bond in the molecule and (B) an acrylic compound having a viscosity at 25°C of 100 mPa s or less and containing one or two (meth)acrylic groups in one molecule as the essential components, wherein the mass ratio between the component (A) and the component (B) is 0.01<(A) / (B)<10 and a volatile organic compound which does not have a group reactive with an acrylic group is not blended.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a fluorine-containing acrylic composition which can impart excellent liquid repellency, stain resistance and abrasion resistance by being added to an active energy ray-curable composition such as ultraviolet ray or electron beam, and a fluorine-containing active energy ray-curable composition containing the fluorine-containing acrylic composition, and an article having a cured product layer of the composition on the surface of a substrate. [Background technology]

[0002] Conventionally, hard coat treatment has been widely used as a means for protecting the surface of resin molded products, etc. This is a method of forming a hard cured resin layer (hard coat layer) on the surface of a molded product to make it less susceptible to scratches. As a material for forming the hard coat layer, a composition that can be cured by active energy rays, such as a thermosetting resin or an ultraviolet or electron beam curable resin, is often used.

[0003] With the expansion of the application fields of resin molded products and the trend towards higher added value, there is an increasing demand for higher functionality in cured resin layers (hard coat layers), one of which is the need to impart antifouling properties to hard coat layers. This is done by imparting properties such as water repellency and oil repellency to the surface of the hard coat layer, making it difficult to get dirty, or making it easy to remove any dirt that may get on it.

[0004] As a method for imparting antifouling properties to a hard coat layer, a method of applying and / or fixing a fluorine-containing antifouling agent to the surface of a hard coat layer once formed is widely used, but a method of simultaneously forming a hard coat layer and imparting antifouling properties by adding a fluorine-containing curable component to a curable resin composition before curing and applying and curing the composition has also been considered. For example, JP-A-6-211945 (Patent Document 1) shows the production of a hard coat layer imparted with antifouling properties by adding a fluoroalkyl acrylate to an acrylic curable resin composition and curing the composition.

[0005] The present inventors have also been developing various fluorine compounds that can impart antifouling properties to such curable resin compositions, and have proposed, for example, photocurable fluorine compounds as shown in JP-A-2010-53114 (Patent Document 2), JP-A-2010-138112 (Patent Document 3), JP-A-2010-285501 (Patent Document 4), etc.

[0006] These compounds can provide a high level of antifouling properties to curable resin compositions by having a fluoropolyether structure and multiple acrylic groups in one molecule, but since they are highly viscous liquids that are difficult to handle by themselves, they need to be diluted with highly volatile organic solvents to make them easier to handle and to improve their mixability with resin compositions. This poses the problem that they cannot be directly incorporated into solvent-free hard coat agents or paints.

[0007] On the other hand, in hard coat processing, coating liquids diluted with organic solvents are widely used to improve the coatability and film performance. However, in recent years, there has been a growing trend to curb the use of volatile organic compounds (VOCs) such as volatile organic solvents due to concerns about their impact on the environment and human body, and there is a strong demand for high-solid and solvent-free hard coat coating liquids. Accordingly, there is a demand for additive compositions that do not contain volatile organic compounds without reactive groups such as volatile organic solvents, which are added to the hard coat coating liquid to impart liquid repellency and antifouling properties.

[0008] Furthermore, hard coat compositions containing volatile organic compounds having no reactive groups, such as conventional volatile organic solvents, undergo particularly large dimensional changes between the time of application and the time of curing, making them particularly unsuitable for applications requiring high dimensional accuracy for the cured product, such as curable compositions for nanoimprints and curable compositions for 3D printers.

[0009] The present inventors have been developing various fluorine-containing acrylic compositions that do not contain volatile organic compounds that have no reactive groups, such as volatile organic solvents, and that can impart liquid repellency and stain resistance to curable resin compositions. For example, JP 2017-190429 A (Patent Document 5) proposes a fluorine-containing acrylic composition that can impart liquid repellency and stain resistance to curable resin compositions when added to a curable composition, by suppressing the content of volatile organic compounds that have no reactive groups, without increasing the amount of volatile organic compounds that do not have groups that react with acrylic groups (non-reactive) in the curable composition as a whole.

[0010] However, in recent years, there has been an increasing trend in the use of hard coats containing fluorine-containing compositions for articles that are likely to be touched by human fingers, such as touch panels. However, when conventional fluorine-containing compositions are used for such applications, the hard coat surface is worn away by abrasion caused by human fingers, resulting in a decrease in antifouling properties, and therefore the composition does not have abrasion resistance that is satisfactory for practical use. [Prior art documents] [Patent documents]

[0011] [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 [Patent Document 5] JP 2017-190429 A Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fluorine-containing acrylic composition which can impart excellent liquid repellency, stain resistance and abrasion resistance when added to an active energy ray-curable composition such as ultraviolet ray or electron beam, and a fluorine-containing active energy ray-curable composition containing the fluorine-containing acrylic composition, and an article having a cured product layer of this composition on the surface of a substrate. [Means for solving the problem]

[0013] As a result of further investigations to achieve the above object, the present inventors have found that (A) A fluorine-containing acrylic compound represented by the following general formula (1): Y-Rf 1 -Z 1 -Q 1 -[Z 2 -X] a (1) [In the formula, Rf 1 Z is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 and composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom. 1 Q is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms independently selected from oxygen atoms, nitrogen atoms and silicon atoms, and may contain a cyclic structure in the middle, but does not contain a urethane bond in the structure. 1 are each independently a (a+1)-valent linking group containing at least (a+1) silicon atoms, which may form a cyclic structure and may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a fluorine atom, provided that the structure does not contain a urethane bond. 2 are independently expressed by the following formula: -C O H 2O -(OC4H8) i (OC3H6) j (OC2H4) k (OCH2) l - (In the formula, each repeating unit may be linear or branched, each repeating unit may be bonded randomly, and i, j, k, and l are each independently Z 2is an integer of 0 to 10, and i+j+k+l=1 to 10, within the range of a molecular weight of 58 to 748. o is an integer of 2 to 10. X is a divalent alkylene ether group represented by the formula (I). X is independently a hydrogen atom, or a monovalent organic group containing an acrylic group or an α-substituted acrylic group which may contain at least one atom selected from oxygen atoms and nitrogen atoms, and contains at least one monovalent organic group containing the acrylic group or α-substituted acrylic group on average per molecule, with the proviso that the structure does not contain a urethane bond. a is independently an integer of 1 to 10. Y is a fluorine atom or -Z 1 -Q 1 -[Z 2 -X] a Z in formula (1) is a monovalent group represented by the formula: 1 and a Zs enclosed in [ ] 2 are all Q 1 bonded to the silicon atom in the structure, and (B) An acrylic compound having a viscosity of 100 mPa·s or less at 25°C and containing one or two (meth)acrylic groups per molecule. The inventors have found that a fluorine-containing acrylic composition containing the above essential components, wherein the mass ratio of component (A) to component (B) is within the range of 0.01<(A) / (B)<10, and which is free of volatile organic compounds having no groups reactive with acrylic groups, can be added to an active energy ray-curable composition without increasing the content of volatile organic compounds having no groups reactive with acrylic groups, and can provide a fluorine-containing active energy ray-curable composition that has good compatibility with the active energy ray-curable composition, has liquid repellency and antifouling properties, reduces the content of volatile organic compounds, and exhibits high abrasion resistance, thereby completing the present invention.

[0014] Accordingly, the present invention provides the following fluorine-containing acrylic composition, fluorine-containing active energy ray-curable composition, and article. [1] (A) One or more fluorine-containing acrylic compounds selected from the group consisting of fluorine-containing acrylic compounds represented by the following formula: [ka] [ka] [ka] [In the formula, Rf 2 -CF 2 O-(CF 2 O) p (CF 2 CF 2 O) q -CF 2 -, p is an integer from 1 to 199, q is an integer from 1 to 170, p+q is an integer from 6 to 200, and the arrangement of the repeating units enclosed in ( ) is random. v is an integer from 4 to 120. 2 are independently a hydrogen atom or a methyl group, R 3 are independently a hydrogen atom, a methyl group, or a phenyl group. 4 is expressed as follows: -C O H 2O -(OC 3 H 6 ) j’ (OC 2 H 4 ) k’ (OCH 2 ) l’ - (wherein each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to another repeating unit, j', k', and l' each independently represent an integer of 0 to 4, j'+k'+l'=1 to 10, and o represents an integer of 2 to 10), and m represents an integer of 2 to 5.] , and (B) An acrylic compound having a viscosity of 100 mPa·s or less at 25°C and containing one or two (meth)acrylic groups per molecule. as an essential component, wherein the mass ratio of component (A) to component (B) is within the range of 0.01<(A) / (B)<10, and wherein no volatile organic compound having no group reactive with an acrylic group is blended. [ 2 ] As a part or whole of the (B) component, CH2=CR 5 C(=O)OR 4 (6) (In the formula, R 4 R is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group.5 is a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms. [1 ] The fluorine-containing acrylic composition described above. [ 3 ] As a part or whole of the (B) component, CH2=CR 7 C(=O)OR 6 -O(O=)CR 7 C=CH2(7) (In the formula, R 6 R is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group. 7 each independently represents a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms. [1] Or [2] The fluorine-containing acrylic composition according to claim 1. [ 4 ] The acrylic compound of component (B) does not contain an alkyl group substituted with a fluorine atom. [1] - [ 3 13. The fluorine-containing acrylic composition according to any one of claims 1 to 12. [ 5 ] [1] to [ 4 0.005 to 40 parts by mass of the fluorine-containing acrylic composition according to any one of claims 1 to 4. [ 6 ] The active energy ray-curable composition (E) is (Ea) acrylic compound: 100 parts by mass, (Eb) Photopolymerization initiator: 0.1 to 15 parts by mass It contains [ 5 ] The fluorine-containing active energy ray-curable composition according to claim 1 . [ 7 ] It gives a cured product with a water contact angle of 90° or more at 25°C and a relative humidity of 40%. 5 ] or [ 6 ] The fluorine-containing active energy ray-curable composition according to claim 1 . [ 8 ] [ 5 ]~[ 7 13. An article having, on its surface, a layer of the cured product of the fluorine-containing active energy ray-curable composition according to any one of claims 1 to 21. Effect of the Invention

[0015] According to the fluorine-containing acrylic composition of the present invention, it is possible to provide a fluorine-containing active energy ray-curable composition that can be added to an active energy ray-curable composition without increasing the content of a volatile organic compound that does not have a group reactive with an acrylic group (particularly, a non-reactive volatile organic compound that does not contain a (meth)acrylic group in the molecule) to impart liquid repellency and antifouling properties. In addition, since the fluorine-containing acrylic compound contained in the fluorine-containing acrylic composition of the present invention does not contain a urethane bond in the molecule, the antifouling properties are unlikely to decrease even due to wear. Therefore, the fluorine-containing acrylic composition is useful as an antifouling additive for imparting liquid repellency, antifouling properties, and abrasion resistance to ultraviolet-curable or heat-curable hard coating agents, paints, resins, antireflective coating compositions, and the like. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The fluorine-containing acrylic composition of the present invention comprises (A) A fluorine-containing acrylic compound represented by the following general formula (1): Y-Rf 1 -Z 1 -Q 1 -[Z 2 -X] a (1) [In the formula, Rf 1 Z is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 and composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom. 1Q is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms independently selected from oxygen atoms, nitrogen atoms and silicon atoms, and may contain a cyclic structure in the middle, but does not contain a urethane bond in the structure. 1 are each independently a (a+1)-valent linking group containing at least (a+1) silicon atoms, which may form a cyclic structure and may contain at least one atom selected from an oxygen atom, a nitrogen atom, and a fluorine atom, provided that the structure does not contain a urethane bond. 2 are independently expressed by the following formula: -C O H 2O -(OC4H8) i (OC3H6) j (OC2H4) k (OCH2) l - (In the formula, each repeating unit may be linear or branched, each repeating unit may be bonded randomly, and i, j, k, and l are each independently Z 2 is an integer of 0 to 10, and i+j+k+l=1 to 10, within the range of a molecular weight of 58 to 748. o is an integer of 2 to 10. X is a divalent alkylene ether group represented by the formula (I). X is independently a hydrogen atom, or a monovalent organic group containing an acrylic group or an α-substituted acrylic group which may contain at least one atom selected from oxygen atoms and nitrogen atoms, and contains at least one monovalent organic group containing the acrylic group or α-substituted acrylic group on average per molecule, with the proviso that the structure does not contain a urethane bond. a is independently an integer of 1 to 10. Y is a fluorine atom or -Z 1 -Q 1 -[Z 2 -X] a Z in formula (1) is a monovalent group represented by the formula: 1 and a Zs enclosed in [ ] 2 are all Q 1 bonded to the silicon atom in the structure, and (B) An acrylic compound having a viscosity of 100 mPa·s or less at 25°C and containing one or two (meth)acrylic groups per molecule. as essential components, the mass ratio of component (A) to component (B) is within the range of 0.01<(A) / (B)<10, and further, no volatile organic compound having no group reactive with an acrylic group is blended.

[0017] The fluorine-containing acrylic composition of the present invention is capable of imparting excellent liquid repellency, stain resistance and abrasion resistance when added to an active energy ray-curable composition, since the fluorine-containing acrylic compound of component (A) has perfluoropolyether groups as water- and oil-repellent groups, and an acrylic group or an α-substituted acrylic group, and does not contain a urethane bond in the molecule.

[0018] The fluorine-containing acrylic compound of component (A), which is the first essential component in the fluorine-containing acrylic composition of the present invention, is represented by the following general formula (1). In the present invention, the term "acrylic compound" is a general term for compounds having an acrylic group or an α-substituted acrylic group, and includes compounds in which two or more acrylic groups or α-substituted acrylic groups have been introduced into the side chains or ends of various polymers by any method. In the present invention, the term "(meth)acrylate" refers to either or both of acrylate and methacrylate. Y-Rf 1 -Z 1 -Q 1 -[Z 2 -X] a (1)

[0019] In the above formula (1), Rf 1 is a divalent perfluoropolyether group having a molecular weight of 400 to 20,000 and composed of a perfluoroalkylene group having 1 to 6 carbon atoms and an oxygen atom, and Rf 1 The alkylene group preferably has a perfluorooxyalkylene structure having 1 to 6 carbon atoms, particularly preferably the following perfluorooxyalkylene structure having 1 to 3 carbon atoms, as a main repeating unit. -CF2O- -CF2CF2O- -CF(CF3)CF2O- -CF2CF2CF2O- These structures may be a homopolymer of any one of these structures, or a random or block polymer consisting of a plurality of structures.

[0020] Rf having such a structure 1 Examples of the above include the following structures: [ka] (In the formula, b is an integer of 1 to 3, independently for each unit. c, d, e, f, g, and h are each an integer of 0 to 200, and c+d+e+f+g+h=3 to 200. Each of these units may be linear or branched, and each repeating unit shown in parentheses with c, d, e, f, g, and h may be randomly bonded.)

[0021] In the above formula, b is an integer of 1 to 3, independently for each unit. Further, c, d, e, f, g, and h are each an integer of 0 to 200, preferably c is an integer of 5 to 100, d is an integer of 5 to 100, e is an integer of 0 to 100, f is an integer of 0 to 100, g is an integer of 0 to 100, and h is an integer of 0 to 100, and c+d+e+f+g+h=3 to 200, preferably 10 to 105, more preferably c+d is an integer of 10 to 105, particularly 15 to 60, and e=f=g=h=0. If c+d+e+f+g+h is smaller than the upper limit, adhesion and curability are good, and if it is larger than the lower limit, the characteristics of the fluoropolyether group can be fully exhibited, which is preferable. In the above formula, each unit may be linear or branched, and each repeat unit shown in parentheses with c, d, e, f, g, and h may be randomly bonded.

[0022] Rf having such a structure 1 Suitable examples of the above include the following structures: -CF2O-(CF2O) p (CF2CF2O) q -CF2- (In the formula, the arrangement of the repeating units enclosed in ( ) is random, p is an integer of 1 to 199, preferably 1 to 99, q is an integer of 1 to 170, preferably 1 to 99, and p+q is an integer of 6 to 200, preferably 10 to 100.) [ka] (In the formula, the arrangement of the repeating units enclosed in ( ) is random, s is an integer of 0 to 6, t is an integer of 1 to 100, u is an integer of 1 to 100, t+u is an integer of 2 to 120, preferably an integer of 4 to 100, and s+t+u is an integer of 3 to 126, preferably an integer of 4 to 100. v is an integer of 4 to 120, preferably an integer of 4 to 80.)

[0023] Rf 1 The molecular weight of the corresponding structural portion may be within the range of 400 to 20,000, preferably 800 to 10,000, and the molecular weight distribution (or polymerization degree distribution) is not particularly limited. In the present invention, the molecular weight (or polymerization degree or number of repeating units) can be determined as the polystyrene-equivalent number average molecular weight (or number average polymerization degree) by gel permeation chromatography (GPC) analysis using a fluorine-based solvent as the developing solvent, but preferably, 1 H-NMR analysis and 19 It is the number average molecular weight (or number average degree of polymerization) calculated from the characteristic peak intensity ratio between the terminal structure and the main chain structure of the fluorine-containing acrylic compound based on F-NMR analysis (hereinafter the same).

[0024] In the above formula (1), Z 1 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain one or more atoms selected from oxygen atoms, nitrogen atoms and silicon atoms, and which may contain a cyclic structure in the middle, provided that the structure does not contain a urethane bond. 1 Particularly preferred structures of the formula are as follows: In the following structures, the bond on the left side is Rf 1 And the bond on the right is Q 1 It is preferred to combine with -CH2CH2- -CH2CH2CH2- -CH2CH2CH2CH2- -CH2OCH2CH2- -CH2OCH2CH2CH2- [ka]

[0025] Z 1 As the above, the following is more preferable. -CH2CH2CH2CH2- -CH2OCH2CH2CH2- [ka]

[0026] In the above formula (1), each a is independently an integer of 1 to 10, and preferably an integer of 2 to 8.

[0027] In the above formula (1), Q 1 are independently (a+1)-valent linking groups containing at least (a+1) silicon atoms, which may form a cyclic structure and may contain at least one atom selected from oxygen atoms, nitrogen atoms and fluorine atoms, provided that the structure does not contain a urethane bond. 1 Preferred examples of the linking group include a siloxane structure having (a+1) Si atoms, an unsubstituted or halogen-substituted silalkylene structure, a silarylene structure, or a combination of two or more of these linking groups having a valence of (a+1).Specific examples of particularly preferred structures include the following structures.

[0028] In the following formulae, a is the same as a in the above formula (1) and is independently an integer of 1 to 10, preferably an integer of 2 to 8. a' is an integer of 2 to 10, preferably an integer of 2 to 7. r is an integer of 1 to 5, preferably an integer of 3 to 5. The arrangement of each unit is random, and the bonds (silicon atoms) of each of the (a+1) and (a'+1) units are each a Z2 and Z 1 It bonds to any of the groups listed below. [ka]

[0029] Here, T is an (a+1)-valent linking group, and examples thereof include the following. [ka]

[0030] Among these, Q in the above formula (1) 1 teeth, [ka] (In the formula, a' is as defined above.) A linking group having a valence of (a'+1) represented by the following formula is preferred.

[0031] In the above formula (1), Z 2 are independently expressed by the following formula: -C O H 2O -(OC4H8) i (OC3H6) j (OC2H4) k (OCH2) l - (In the formula, each repeating unit may be linear or branched, each repeating unit may be bonded randomly, and i, j, k, and l are each independently Z 2 is a divalent alkylene ether group represented by the formula: wherein i is an integer of 0 to 10 (i.e., the sum of i, j, k, and l is 1 to 10), and preferably i is an integer of 0 to 5, j is an integer of 0 to 5, k is an integer of 0 to 5, and l is an integer of 0 to 5, where i+j+k+l=1 to 10. o is an integer of 2 to 10, and preferably an integer of 2 to 8. In the above structure, the bond on the left side is Q 1 It is preferable that the bond on the right side is bonded to X.

[0032] Z 2 As a preferred structure, the following can be mentioned: -CH2CH2OCH2- -CH2CH2OCH2CH2- -CH2CH2OCH2CH2CH2- -CH2CH2CH2OCH2- -CH2CH2CH2(OC2H4) k1 (OC3H6) j1 (OC4H8) i1 -

[0033] Here, k1 is an integer from 0 to 10, j1 is an integer from 0 to 10, i1 is an integer from 0 to 10, and Z 2 The molecular weight of the repeating unit is 86 to 330. The arrangement of the repeating units is random regardless of the type. Each repeating unit may be a mixture of structural isomers rather than a single unit. 2 If the molecular weight is less than 58, it will be difficult to mix with the acrylic compound of component (B), and if it exceeds 748, the ability of the fluorine-containing acrylic compound to impart stain resistance will be insufficient.

[0034] Z 2 Particularly preferred structures include the following, and among them, those in which k1 is 1 to 4 and j1 is 1 to 4 are preferred. -CH2CH2CH2(OC2H4) k1 - -CH2CH2CH2(OC3H6) j1 -

[0035] In the above formula (1), X is independently a hydrogen atom, or a monovalent organic group containing an acrylic group or an α-substituted acrylic group which may contain at least one atom selected from oxygen and nitrogen atoms, and each molecule contains on average at least one monovalent organic group containing an acrylic group or an α-substituted acrylic group, with the proviso that the structure does not contain a urethane bond.

[0036] X is preferably a structure represented by the following formula: [ka] (In the formula, R 1 each independently represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; Z 3 represents a single bond, or a divalent or trivalent hydrocarbon group having 1 to 18 carbon atoms which may contain an ether bond and / or an ester bond, and n is 1 or 2.

[0037] Here, R 1 are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group, and a hydrogen atom and a methyl group are preferred. In addition, n here is 1 or 2, and is preferably 1.

[0038] Also, here, Z 3 is a single bond, or a divalent or trivalent hydrocarbon group having 1 to 18 carbon atoms which may contain an ether bond and / or an ester bond. Preferably, it is a single bond or the following structure: -CH2- -CH2CH2- -CH2CH2CH2- [ka]

[0039] X is preferably a group represented by the following formula: -Z'-OC(=O)-CR 8 =CH2 (In the formula, R 8 is a hydrogen atom or a methyl group, and Z' is a single bond, a methylene group, an ethylene group, or a propylene group.

[0040] The fluorine-containing acrylic compound represented by the above formula (1) is preferably one represented by the following general formula (2) or (3). [ka] (In the formula, Rf 1 , Z 1 , Z 2 , Q1 , R 1 , a is as above.)

[0041] The fluorine-containing acrylic compound represented by the above formula (1) is more preferably one represented by the following general formula (4) or (5). [ka] [In the formula, Rf 1 , Z 1 , Q 1 , a is as described above. Z 4 is expressed by the following formula: -C O H 2O -(OC3H6) j’ (OC2H4) k’ (OCH2) l’ - (wherein each repeating unit may be linear or branched, each repeating unit may be randomly bonded to another repeating unit, j', k', and l' each independently represent an integer of 0 to 4, j'+k'+l'=1 to 10, and o represents an integer of 2 to 10.)

[0042] More specific examples of the fluorine-containing acrylic compound represented by the above formula (1) include those shown below. [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, Rf 2 is -CF2O-(CF2O) p (CF2CF2O) q -CF2-, the sequence of the repeating units enclosed in ( ) is random, and R 2 are independently a hydrogen atom or a methyl group, R 3 are independently a hydrogen atom, a methyl group, or a phenyl group; m is an integer of 2 to 5; p, q, p+q, Z 4 , v is as above.)

[0043] Among these, the following are particularly preferred. [ka] [ka] [ka] (In the formula, Rf 2 , m, R 2 , R 3 , Z 4 , v is as above.)

[0044] The synthesis method of the fluorine-containing acrylic compound represented by the general formula (1) is not particularly limited. For example, as an embodiment of the fluorine-containing acrylic compound represented by the general formula (2) or (3), first, a compound represented by the following general formula (8) or (9) F-Rf 1 -Z 1 -Q 1 -[H] a (8) [H] a -Q 1 -Z 1 -Rf 1 -Z 1 -Q 1 -[H] a (9) (In the formula, Rf 1 , Z 1 , Q 1, a is as described above, and all of the a hydrogen atoms (H) enclosed in [ ] in formulas (8) and (9) are Q 1 It is bonded to the silicon atom in the structure.) and a fluoropolyether compound having a polyfunctional Si-H group represented by the following general formula (10): [ka] (In the formula, R 1 , i, j, k, and l are as described above. w is an integer from 0 to 8.) The compound can be obtained by subjecting a compound containing a terminal aliphatic unsaturated group (for example, an alkyl group having an aliphatic unsaturated double bond at its terminal, such as an alkenyl group, or a terminal alkenyl group) having (adjacent) an alkylene ether group represented by the following formula:

[0045] Examples of the fluoropolyether compounds having polyfunctional Si-H groups represented by the above formulas (8) and (9) include those shown below. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] (In the formula, Rf 2 , v is the same as above.)

[0046] Furthermore, examples of compounds containing a terminal aliphatic unsaturated group having (adjacent to) the alkylene ether group represented by the above formula (10) (for example, an alkyl group containing an aliphatic unsaturated double bond at its terminal, such as an alkenyl group, i.e., an alkyl group whose terminal is blocked with an external olefin (vinyl group) represented by CH=CH-, or the external olefin (vinyl group)) and an acrylic group or an α-substituted acrylic group include the following. CH2=CHCH2(OC2H4) k2 (OC3H6) j2 (OC4H8) i2 -OC(=O)-CH=CH2 CH2=CHCH2(OC2H4) k2 (OC3H6) j2 (OC4H8) i2 -OC(=O)-C(CH3)=CH2 CH2=CH(OC2H4) k2 (OC3H6) j2 (OC4H8) i2 -OC(=O)-CH=CH2 CH2=CH(OC2H4) k2 (OC3H6) j2 (OC4H8) i2 -OC(=O)-C(CH3)=CH2 (In the formula, k2 is an integer of 0 to 10, j2 is an integer of 0 to 10, i2 is an integer of 0 to 10, i2+j2+k2=1 to 16, and CH2=CH-C w H 2w -(OC4H8) i (OC3H6) j (OC2H4) k (OCH2) l The molecular weight of the portion corresponding to - is 57 to 747. The arrangement of the repeating units is random regardless of the type. In addition, each repeating unit may be a mixture of structural isomers rather than a single unit.

[0047] Among these, the following are particularly preferred: CH2=CHCH2-(OC2H4) k3 -OC(=O)-C(CH3)=CH2 CH2=CHCH2-(OC3H6) j3 -OC(=O)-C(CH3)=CH2 (In the formula, k3 is an integer of 1 to 4, and j3 is an integer of 1 to 4.)

[0048] Conventionally, when an acrylic group or an α-substituted acrylic group is introduced into a fluorine-containing compound by a hydrosilylation addition reaction, allyl methacrylate has been mainly used, but since the allyl group (terminal aliphatic unsaturated group) in allyl methacrylate has low reactivity in the hydrosilylation addition reaction, the hydrosilylation addition reaction proceeds not only at the target allyl group (terminal aliphatic unsaturated group) as a reaction site, but also at the methacrylic group as a side reaction, which is unsuitable. In the present invention, the reactivity of the terminal aliphatic unsaturated group is sufficiently guaranteed by using a compound containing an (adjacent) terminal aliphatic unsaturated group having an alkylene ether group, and an acrylic group or an α-substituted acrylic group, and therefore the progress of the hydrosilylation addition of the acrylic group or the α-substituted acrylic group as a side reaction is effectively suppressed.

[0049] The fluoropolyether compound having a polyfunctional Si-H group represented by the above formula (8) or (9) and the compound containing a terminal aliphatic unsaturated group represented by formula (10) and an acrylic group or an α-substituted acrylic group are mixed and stirred, and reacted in the presence of a platinum group metal-based addition reaction catalyst at a reaction temperature of 50 to 150°C, preferably 60 to 120°C, for 1 minute to 72 hours, and particularly 5 minutes to 12 hours. If the reaction temperature is too low, the reaction may stop before proceeding sufficiently, and if the reaction temperature is too high, the reaction may become uncontrollable due to the temperature rise caused by the reaction heat of hydrosilylation, and bumping or decomposition of the raw materials may occur.

[0050] In this case, the ratio of the fluoropolyether compound having a polyfunctional Si-H group represented by formula (8) or (9) and the compound containing a terminal aliphatic unsaturated group represented by formula (10) and an acrylic group or an α-substituted acrylic group is preferably 0.8 to 5 times the moles of the unsaturated group of the compound containing a terminal aliphatic unsaturated group represented by formula (10) and an acrylic group or an α-substituted acrylic group, particularly 1 to 2 times the moles of the unsaturated group of the compound containing a terminal aliphatic unsaturated group represented by formula (10) and an acrylic group or an α-substituted acrylic group, relative to the total moles of H enclosed in [ ] of the fluoropolyether compound having a polyfunctional Si-H group represented by formula (8) or (9). If the compound containing a terminal aliphatic unsaturated group represented by formula (10) and an acrylic group or an α-substituted acrylic group is too small, there is a possibility that a large amount of Si-H groups remain in the fluoropolyether compound having a polyfunctional Si-H group represented by formula (8) or (9), and the desired effect cannot be obtained. If the amount is too large, the homogeneity of the reaction solution decreases, making the reaction rate unstable. In addition, when removing the compound containing a terminal aliphatic unsaturated group represented by formula (10) and an acrylic group or an α-substituted acrylic group after the reaction, the conditions for heating, decompression, extraction, etc. must be made stricter in proportion to the increase in the amount of excess unreacted components.

[0051] The addition reaction catalyst may be, for example, a compound containing a platinum group metal such as platinum, rhodium, or palladium. Among them, a compound containing platinum is preferable, and examples of the compound that may be used include hexachloroplatinic acid (IV) hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex, complexes of chloroplatinic acid with olefins, aldehydes, vinylsiloxanes, acetylene alcohols, and the like, and platinum supported on activated carbon. The amount of the addition reaction catalyst is preferably such that the metal content is 0.1 to 5,000 ppm by mass, more preferably 0.1 to 1,000 ppm by mass, relative to the fluoropolyether compound having a polyfunctional Si-H group represented by formula (8) or (9).

[0052] The above-mentioned addition reaction can be carried out without the presence of a solvent, but may be diluted with a solvent if necessary. In this case, the dilution solvent may be a widely used organic solvent such as toluene, xylene, isooctane, etc. As such an organic solvent, it is preferable that the boiling point is equal to or higher than the target reaction temperature, does not inhibit the reaction, and the fluorine-containing acrylic compound represented by formula (2) or (3) produced after the reaction is soluble at the above-mentioned reaction temperature. For example, partially fluorine-modified solvents such as fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether are preferable, and m-xylene hexafluoride is particularly preferable. When a solvent is used, the amount of the solvent used is preferably 5 to 2,000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the fluoropolyether compound having a polyfunctional Si-H group represented by formula (8) or (9). If the amount is less than this, the effect of dilution by the solvent is weak, and if the amount is more, the degree of dilution becomes too high, which may lead to a decrease in the reaction rate.

[0053] After completion of the reaction, the unreacted terminal aliphatic unsaturated group represented by formula (10), and the compound containing an acrylic group or an α-substituted acrylic group, and the dilution solvent can be removed by a known method such as vacuum distillation, extraction, adsorption, etc., to obtain the fluorine-containing acrylic compound represented by formula (2) or (3).

[0054] The fluorine-containing acrylic compound represented by the general formula (1) obtained by the above reaction is used after purification and isolation procedures such as concentration, column purification, distillation, extraction, etc.

[0055] The fluorine-containing acrylic compound thus obtained does not contain a volatile organic compound (volatile organic solvent). The fluorine-containing acrylic compound (A) may be used alone or in combination of two or more kinds.

[0056] The second essential component in the fluorine-containing acrylic composition of the present invention is (B) an acrylic compound having a viscosity of 100 mPa s or less at 25° C. and containing one or two (meth)acrylic groups per molecule. The acrylic compound of component (B) may contain oxygen atoms and nitrogen atoms other than the acrylic structure, and specifically may contain an ether bond, a urethane bond, an isocyanate group or a hydroxyl group.

[0057] Considering the solubility of component (A), component (B) has a viscosity at 25°C of 100 mPa·s or less, and preferably 0.4 to 20 mPa·s. If the viscosity at 25°C exceeds 100 mPa·s, it becomes difficult to mix with component (A) and handling properties become poor. In the present invention, the viscosity can be measured with a rotational viscometer (for example, BL type, GH type, BS type, cone-plate type, rheometer, etc.) (the same applies hereinafter).

[0058] A preferred example of such a compound having one (meth)acryl group in the molecule of the component (B) is specifically one represented by the following general formula (6). CH2=CR 5 C(=O)OR 4 (6) (In the formula, R 4 R is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group. 5 is a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms.

[0059] In the above formula (6), R 4 R is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group or a hydroxyl group, and is preferably an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms, which may be branched or cyclic and may contain an aliphatic unsaturated (double) bond, a urethane bond, an ether bond, an isocyanate group or a hydroxyl group. 4Specific examples of such alkyl groups include methyl group, ethyl group, propyl group, butyl group, isobutyl group, hexyl group, cyclohexyl group, octyl group, 2-ethyl-hexyl group, isodecyl group, tridecyl group, isostearyl group, phenyl group, benzyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, furfuryl group, tetrahydrofuryl group, tetrahydropyranyl group, 2-(2-ethoxyethoxy)ethyl group, -CH2CH2-OH, -CH2CH(CH3)-OH, -CH2CH2CH2-OH, -CH2CH2CH2CH2-OH, -CH2CH2CH2CH2CH2-OH, -CH2CH2CH2CH2CH2-OH, 4-hydroxycyclohexyl group, -CH2CH2-NCO, and the like. Also, R 5 represents a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group, a trifluoropropyl group or a nonafluorobutyl group, and is particularly preferably a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group.

[0060] More specifically, such compounds include 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, tridecyl (meth)acrylate, isostearyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl ... Examples of the acrylates include hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxycyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenoxyethyl (meth)acrylate, and neopentyl glycol-(meth)acrylic acid-benzoic acid ester.

[0061] In addition, compounds not corresponding to formula (6), for example, acrylate compounds having a repeating unit structure of ethylene oxide, propylene oxide, tetramethylene oxide, lactone, or the like, and having various alkoxy terminals, such as (meth)acrylic compounds commercially available under the names of methoxypolyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, nonylphenol EO adduct acrylate, and the like, can also be used so long as they have a viscosity of 100 mPa s or less at 25°C.

[0062] Furthermore, among the components (B), preferred examples of compounds having two (meth)acryl groups in the molecule include those represented by the following general formula (7). CH2=CR 7 C(=O)OR 6 -O(O=)CR 7 C=CH2(7) (In the formula, R 6 R is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group. 7 each independently represents a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms.

[0063] In the above formula (7), R 6 R is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group or a hydroxyl group, and is preferably an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an arylene group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, or an aralkylene group having 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms, which may be branched or cyclic and may contain an aliphatic unsaturated (double) bond, a urethane bond, an ether bond, an isocyanate group or a hydroxyl group. 6Specific examples of such groups include a methylene group, an ethylene group, a propylene group (trimethylene group, methylethylene group), a butylene group (tetramethylene group, methylpropylene group), a hexylene group (hexamethylene group), a cyclohexylene group, an octamethylene group, a nonamethylene group, a decamethylene group, -CH2CH2-O-CH2CH2-, -C3H6-O-C3H6-, a phenylene group, a dicyclopentanylene group, a dicyclopentenylene group, a furfurylene group, a tetrahydrofulrylene group, and a tetrahydropyranylene group. Also, R 7 each independently represents a hydrogen atom, a methyl group, a fluorine atom, a trifluoromethyl group, a trifluoropropyl group, a nonafluorobutyl group or other fluoroalkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group.

[0064] More specifically, such compounds include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and the like.

[0065] The acrylic compound of component (B) may contain an alkyl group substituted with a fluorine atom. However, acrylic compounds containing an alkyl group substituted with a fluorine atom are more likely to cause environmental load than acrylic compounds that do not contain fluorine atoms. From the viewpoint of VOC emission regulations, it is desirable for the acrylic compound of component (B) to have a low content of acrylic compounds containing an alkyl group substituted with a fluorine atom, and it is particularly desirable for the acrylic compound of component (B) to not contain an acrylic compound containing an alkyl group substituted with a fluorine atom.

[0066] Component (B) may be a single compound or a mixture of multiple compounds that meet the above definition, and in the case of a mixture, the total content of the compounds that fall under component (B) may be calculated as the content of component (B). Compounds that fall under component (B) can be synthesized by known methods as necessary, but various compounds are commercially available from reagent manufacturers, etc., and these can also be used as they are.

[0067] The fluorine-containing acrylic composition of the first embodiment of the present invention contains the above-mentioned components (A) and (B) as essential components, and the mass ratio of component (A) to component (B) is within the range of 0.01<(A) / (B)<10, preferably 0.015≦(A) / (B)≦8, and more preferably 0.02≦(A) / (B)≦5. In another embodiment of the present invention, the fluorine-containing acrylic composition is mixed with the active energy ray curable composition (E) described later to form a fluorine-containing active energy ray curable composition, which is then applied and cured to provide a liquid-repellent and stain-resistant cured layer on a substrate. The liquid-repellent and stain-resistant properties are expressed by the presence of the component (A) dispersed in the component of the active energy ray curable composition (E) on the surface of the cured layer. Therefore, when the mass ratio (A) / (B) is 0.01 or less, the content of the component (A) in the fluorine-containing acrylic composition becomes too small, making it difficult to finally express the liquid-repellent and stain-resistant properties. On the other hand, when the mass ratio (A) / (B) is 10 or more, the workability decreases due to the high viscosity of the component (A), and the compatibility and mixability with the component (E) decrease.

[0068] When (A) / (B) is within the above range, the viscosity of the fluorinated acrylic composition at 25° C. is preferably 0.1 to 10,000 mPa s, more preferably 0.5 to 5,000 mPa s, and even more preferably 1 to 1,000 mPa s. When the composition has such a viscosity, a curable composition having good handleability can be obtained.

[0069] The fluorine-containing acrylic composition of the present invention is one that does not contain a volatile organic compound having no group reactive with an acrylic group (particularly, a non-reactive volatile organic compound (or volatile organic solvent) having no (meth)acrylic group in the molecule) (i.e., a solvent-free fluorine-containing acrylic composition).

[0070] The fluorine-containing acrylic composition of the present invention can be added to the active energy ray-curable composition (E) described below to form a fluorine-containing active energy ray-curable composition. The amount of the fluorine-containing acrylic composition added is 0.005 to 40 parts by mass, preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the active energy ray-curable composition (E) described below. If the amount of the compound is less than this, the compound cannot be sufficiently arranged on the surface when a cured product is formed, and the expected liquid repellency and antifouling properties cannot be exhibited, whereas if the amount is greater than this, the effect of the fluorine-containing acrylic compound on the strength and hardness of the cured product layer becomes too large, resulting in the loss of the original cured product properties of the active energy ray-curable composition.

[0071] The active energy ray-curable composition (E) is not particularly limited as long as it gives a cured product upon irradiation with active energy rays such as ultraviolet rays and electron beams. In particular, it is preferable that the active energy ray-curable composition (E) contains an acrylic compound (Ea) and a photopolymerization initiator (Eb).

[0072] The acrylic compound (Ea) may be either monofunctional or polyfunctional. For example, the above-mentioned monofunctional and bifunctional acrylic compounds as the component (B) may be used, but it is particularly preferable that the component (Ea) contains a non-fluorinated acrylic compound having two or more acrylic groups in one molecule.

[0073] Such a non-fluorinated acrylic compound may be any compound having two or more acrylic groups or α-substituted acrylic groups in one molecule, and examples thereof include 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, isocyanuric acid ethylene oxide modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, hydrogen phthalate-(2,2,2-tri-(meth)acryloyloxymethyl) phthalate, and the like. Preferred examples of the (meth)acrylic compound include di- to hexafunctional (meth)acrylic compounds such as ethyl acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and sorbitol hexa(meth)acrylate; epoxy acrylates obtained by adding acrylic acid to these (meth)acrylic compounds with ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, or alkyl groups; and copolymers in which a (meth)acryloyl group has been introduced into the side chain of an acrylic acid ester copolymer.

[0074] Also usable are urethane acrylates, those obtained by reacting a polyisocyanate with a (meth)acrylate having a hydroxyl group, those obtained by reacting a polyester of a polyisocyanate and a terminal diol with a (meth)acrylate having a hydroxyl group, and those obtained by reacting a polyisocyanate obtained by reacting an excess of a diisocyanate with a polyol with a (meth)acrylate having a hydroxyl group. Among these, preferred examples include urethane acrylates obtained by reacting a (meth)acrylate having a hydroxyl group selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol triacrylate with a polyisocyanate selected from hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylene bis(4-cyclohexyl isocyanate), 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, and diphenylmethane diisocyanate.

[0075] Alternatively, the compound may be a mixture of at least two types of acrylic compounds, including a polyfunctional acrylic compound having two or more acrylic groups or α-substituted acrylic groups in one molecule and no urethane bond, or a polyfunctional urethane acrylate having three or more acrylic groups or α-substituted acrylic groups in one molecule obtained by reacting this polyfunctional acrylic compound with an aliphatic polyisocyanate and an acrylic compound having a hydroxyl group.

[0076] In this case, examples of polyfunctional acrylic compounds having two or more acrylic groups or α-substituted acrylic groups in one molecule and no urethane bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, 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 compounds obtained by modifying these with ethylene oxide or propylene oxide.

[0077] In addition, examples of polyfunctional urethane acrylates having three or more acrylic groups or α-substituted acrylic groups in one molecule obtained by reacting an aliphatic polyisocyanate with an acrylic compound having a hydroxyl group include hexamethylene diisocyanate, norbornane diisocyanate, isophorone diisocyanate, and trimers thereof, and difunctional or higher polyisocyanates obtained by reacting these difunctional or trifunctional isocyanates with aliphatic diols, aliphatic polyols, and polyacrylates having a hydroxyl group in the side chain, and trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, etc. Examples of the copolymer include those obtained by reacting bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and their ethylene oxide or propylene oxide modified products, and those obtained by reacting aliphatic polyols and polyacrylates having hydroxyl groups on the side chains with 2-isocyanatoethyl (meth)acrylate, 1,1-(bisacryloyloxymethyl)ethyl isocyanate, or other acrylic compounds having an isocyanate group.

[0078] Furthermore, the component (Ea) may not only be a liquid component, but may also include fine particle-like high molecular weight substances or fine inorganic filler particles whose surfaces have been modified with acrylic groups.

[0079] The above-mentioned component (Ea) can be used alone, but a combination of two or more corresponding compounds can also be used to improve the coatability and properties of the cured coating.

[0080] Furthermore, by including a photopolymerization initiator as the component (Eb), it is possible to provide a curable composition that has improved curability when ultraviolet light is used as the active energy ray.

[0081] The photopolymerization initiator of the component (Eb) is not particularly limited as long as it can cure an acrylic compound by irradiation with ultraviolet light. Preferred examples of the photopolymerization initiator include acetophenone, benzophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanon-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one. -(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2-(o-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, and the like. One type may be used alone, or two or more types may be used in combination.

[0082] The content of the (Eb) component can be appropriately determined depending on the curing conditions and the desired physical properties of the cured product of the active energy ray-curable composition (E), but for example, it is desirable that the content be 0.1 to 15 parts by mass, particularly 1 to 10 parts by mass, per 100 parts by mass of the (Ea) component in total. If the amount added is less than this, the curability may decrease, and if the amount added is more than this, the effect on the physical properties after curing may be large.

[0083] The active energy ray-curable composition (E) may also contain other active energy ray-reactive compounds other than acrylic groups, such as thiol compounds and maleimide compounds, organic solvents, polymerization inhibitors, antistatic agents, antifoaming agents, viscosity modifiers, light resistance stabilizers, heat resistance stabilizers, antioxidants, surfactants, colorants, and polymer or inorganic fillers, etc. The structures of these are not particularly limited, and known ones can be used within the scope of the present invention.

[0084] As the active energy ray curable composition (E), an existing composition that is commercially available from various companies as a paint, ink, hard coat agent, etc., as an active energy ray curable composition in which the components (Ea) and (Eb) and various additives have already been blended, may be used as a part or the whole of the component (E). Even when using a commercially available hard coat agent in this way, organic solvents, polymerization inhibitors, antistatic agents, antifoaming agents, viscosity modifiers, light resistance stabilizers, heat resistance stabilizers, antioxidants, surfactants, colorants, fillers, etc. may be added and blended depending on the purpose within a range that does not impair the effects of the present invention.

[0085] The fluorine-containing active energy ray-curable composition of the present invention obtained as described above can suppress the inclusion of volatile organic compounds that are not incorporated into the structure of the cured product, and since it contains a fluorine-containing acrylic compound having a perfluoropolyether group as the water- and oil-repellent group, and an acrylic group or an α-substituted acrylic group as the active energy ray-curable group, it can give a cured product that is excellent in water repellency, oil repellency, slipperiness, antifouling properties, fingerprint wiping properties, low refractive index properties, solvent resistance, chemical resistance, etc., and since this fluorine-containing acrylic compound does not contain a urethane bond in the molecule, a cured product that is also excellent in abrasion resistance can be obtained.

[0086] Further, the present invention provides an article (an article having a cured product layer (also called a cured coating or cured resin layer) on its surface) obtained by applying the above-mentioned fluorine-containing active energy ray curable composition of the present invention to the surface of a substrate and curing it. As described above, by using the fluorine-containing active energy ray curable composition of the present invention, it is possible to form a cured coating (cured resin layer) having excellent surface properties on the surface of the substrate. In particular, it is useful for imparting water repellency, oil repellency, and antifouling properties to the surface of an acrylic hard coat. This makes it difficult for stains due to fingerprints, sebum, sweat, and other human oils, cosmetics, etc. to adhere, and also provides the substrate (article) with a hard coat surface that is easy to wipe off. Therefore, the fluorine-containing active energy ray curable composition of the present invention can provide a coating film or protective film for the surface of a substrate (article) that may be stained by human oils, cosmetics, etc. by contact with the human body.

[0087] The cured coating (cured resin layer) formed using the fluorine-containing active energy ray-curable composition of the present invention can be directly applied to the surface of an article to which properties are to be imparted and cured, or the fluorine-containing active energy ray-curable composition of the present invention can be applied to various substrate films (e.g., films of polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, vinyl chloride resin, polystyrene, acrylic resin, polycarbonate, polyphenylene sulfide, polyether ether ketone, polyether sulfone, aramid, polyimide, etc.) to prepare a cured coating, and the film can be attached to the surface of the desired article, thereby imparting properties to various articles.

[0088] Here, the method for coating the fluorine-containing active energy ray curable composition of the present invention is not particularly limited, and for example, known coating methods such as roll coating, gravure coating, flow coating, dip coating, spray coating, spin coating, bar coating, and screen printing can be used. After coating, the coating film is irradiated with active energy rays to cure it. Here, any active energy rays such as electron beams and ultraviolet rays can be used, but ultraviolet rays are particularly preferred. Mercury lamps, metal halide lamps, and LED lamps are suitable as sources of ultraviolet rays. The amount of ultraviolet irradiation should be 10 to 10,000 mJ / cm because too little will leave uncured components and too much may deteriorate the coating film and substrate. 2 , especially 20 to 4,000 mJ / cm 2 In order to prevent the inhibition of curing by oxygen, the irradiation atmosphere during ultraviolet irradiation may be replaced with an inert gas not containing oxygen molecules, such as nitrogen, carbon dioxide, or argon, or the coating surface may be covered with a protective layer having releasability and ultraviolet light transmission and then irradiated with ultraviolet light, or, if the substrate has ultraviolet light transmission, the coating surface may be covered with a protective layer having releasability and then ultraviolet light may be irradiated from the opposite side of the substrate to the coated surface. In order to effectively level the coating film or polymerize the acrylic group in the coating film, the coating film and substrate may be heated by any method, such as a hot air drying oven, before and during ultraviolet light irradiation.

[0089] In addition, the thickness of the cured coating film (cured resin layer) formed using the fluorine-containing active energy ray-curable composition of the present invention is not particularly limited. However, if the obtained film thickness is too thin, sufficient surface hardness cannot be obtained, and if it is too thick, the mechanical strength of the hard coat film decreases and it becomes prone to cracks. Therefore, the thickness is usually preferably 5 nm to 100 μm, and particularly preferably 1 μm to 20 μm.

[0090] In addition, it is desirable that the cured coating (cured resin layer) formed using the fluorine-containing active energy ray-curable composition of the present invention has a water contact angle of 90° or more, preferably 95° or more, at 25°C and a relative humidity of 40%. In the present invention, the water contact angle is a value measured using a contact angle meter Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) under the condition of a droplet: 2 μl. In order to achieve the above water contact angle, it is preferable that the fluorine-containing active energy ray-curable composition is mixed uniformly.

[0091] Examples of such articles include the housings of various devices carried by hand, such as tablet computers, mobile phones, and smartphones, mobile (communication) information terminals, notebook PCs, digital media players, watch-type and glasses-type wearable computers, digital cameras, digital video cameras, and electronic book readers; surfaces of display and operation devices, such as various flat panel displays, such as liquid crystal displays, plasma displays, organic EL displays, rear projection displays, fluorescent display tubes (VFDs), field emission projection displays, CRTs, and toner-based displays, and TV screens; exteriors of automobiles; glossy surfaces of pianos and furniture; architectural stone surfaces, such as marble; decorative building materials for water-related areas, such as toilets, baths, and washrooms; protective glass for displaying art works, show windows, showcases, covers for photo frames, watches, automobile window glass, window glass for trains and aircraft, transparent glass or transparent plastic (acrylic resin, polycarbonate, etc.) parts, such as automobile headlights and taillights; and various mirror parts, and are useful as coating films and surface protective films.

[0092] In particular, it is useful as a surface protective film for various devices having display input devices such as touch panel displays that allow operations to be performed on the screen with a person's fingers or palm, for example, tablet computers, notebook PCs, watch-type wearable computers, activity monitors, mobile (communication) information terminals such as mobile phones and smartphones, digital media players, e-book readers, digital photo frames, game consoles and game console controllers, digital cameras, digital video cameras, navigation devices for automobiles, etc., automatic cash withdrawal / deposit machines, automated cash dispensers, vending machines, digital signage (electronic billboards), security system terminals, POS terminals, various controllers such as remote controllers, and display input devices such as panel switches for in-vehicle devices.

[0093] Furthermore, the cured coating formed from the fluorine-containing active energy ray-curable composition of the present invention is useful as a surface protective coating for optical recording media such as magneto-optical disks and optical disks; eyeglass lenses, camera lenses, projector lens prisms, lens sheets, pellicle films, polarizing plates, optical filters, lenticular lenses, Fresnel lenses, anti-reflection films, optical fibers, optical couplers and other optical components and optical devices, or as a surface protective coating for various protective parts of these devices.

[0094] Furthermore, the cured coating film formed by the fluorine-containing active energy ray-curable composition of the present invention has a smaller dimensional change between the time of application and the time of curing compared to a cured coating film formed by a conventional hard coat composition containing a volatile organic compound, and is therefore useful in applications requiring high dimensional accuracy for the cured product, such as a surface protective film for a curable composition for nanoimprints or a curable composition for 3D printers. EXAMPLES

[0095] The present invention will be specifically described below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples.

[0096] [Synthesis Example 1] Synthesis of fluorine-containing acrylic compound (A-1) In a dry nitrogen atmosphere, add the following mixture to a 2,000 mL three-neck flask equipped with a reflux device and a stirrer: CH2=CH-CH2-O-CH2-Rf'-CH2-O-CH2-CH=CH2 Rf': -CF2O(CF2O) p1 (CF2CF2O) q1 CF2- (q1 / p1=0.9, p1+q1≒45, 19 Number average molecular weight calculated from F-NMR: ≒ 4,300) 500 g (0.12 mol) of perfluoropolyether represented by the formula (I) above, 700 g of m-xylene hexafluoride, and 361 g (1.50 mol) of tetramethylcyclotetrasiloxane were added and heated to 90° C. with stirring. 0.442 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (1.1×10 as Pt alone) was added to the flask. -6 mol) was added, and stirring was continued for 4 hours while maintaining the internal temperature at 90°C or higher. 1 After confirming the disappearance of the allyl group of the raw material by H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. After that, activated carbon treatment was performed, and 498 g of a colorless, transparent liquid compound (a) represented by the following formula was obtained. [ka] Rf': -CF2O(CF2O) p1 (CF2CF2O) q1 CF2- (q1 / p1=0.9, p1+q1≒45, 19 Number average molecular weight calculated from F-NMR: ≒ 4,800)

[0097] Under a dry air atmosphere, 10.0 g of the compound (a) obtained above (Si-H group amount 1.3 × 10 -2 mol) of allyloxyethyl methacrylate, 3.2 g (1.88 × 10 -2 mol), 10.0 g of m-xylene hexafluoride, and 1.0 × 10 toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 g (0.3×10 as Pt alone) -7The mixture was stirred at 80° C. for 4 hours. 1 After confirming the disappearance of the Si-H group by H-NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, and the residue was treated with activated carbon to obtain 10.4 g of a colorless and transparent fluorine-containing acrylic compound (A-1) represented by the following formula. [ka] Rf': -CF2O(CF2O) p1 (CF2CF2O) q1 CF2- (q1 / p1=0.9, p1+q1≒45)

[0098] [Synthesis Example 2] Synthesis of fluorine-containing acrylic compound (A-2) In a dry nitrogen atmosphere, add the following mixture to a 1,000 mL three-neck flask equipped with a reflux device and a stirrer: CH2=CH-CH2-O-CH2-Rf”-CH2-O-CH2-CH=CH2 Rf”:-CF2O(CF2O) p2 (CF2CF2O) q2 CF2- (q2 / p2=1.3, p2+q2≒16, 19 Number average molecular weight calculated from F-NMR: ≒ 1,800) 188 g (0.10 mol) of perfluoropolyether represented by the formula (I) above, 188 g of m-xylene hexafluoride, and 361 g (1.50 mol) of tetramethylcyclotetrasiloxane were added and heated to 90° C. with stirring. 0.442 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (1.1×10 as Pt alone) was added to the flask. -6 mol) was added, and stirring was continued for 4 hours while maintaining the internal temperature at 90°C or higher. 1 After confirming the disappearance of the allyl group of the raw material by H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. After that, activated carbon treatment was performed, and 192 g of a colorless, transparent liquid compound (b) represented by the following formula was obtained. [ka] Rf”:-CF2O(CF2O) p2 (CF2CF2O) q2 CF2- (q2 / p2=1.3, p2+q2≒16, 19 Number average molecular weight calculated from F-NMR: ≒ 2,300)

[0099] Under a dry air atmosphere, 10.0 g of the compound (b) obtained above (Si-H group amount 2.6 × 10 -2 mol) of allyloxyethyl methacrylate, 5.1 g (2.60 × 10 -2 mol), 10.0 g of m-xylene hexafluoride, and 2.0 × 10 toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 g (Pt alone is 0.6×10 -7 The mixture was stirred at 80° C. for 4 hours. 1 After confirming the disappearance of the Si-H group by H-NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, and the residue was treated with activated carbon to obtain 11.6 g of a colorless and transparent fluorine-containing acrylic compound (A-2) represented by the following formula. [ka] Rf”:-CF2O(CF2O) p2 (CF2CF2O) q2 CF2- (q2 / p2=1.3, p2+q2≒16)

[0100] [Synthesis Example 3] Synthesis of fluorine-containing acrylic compound (A-3) In a dry nitrogen atmosphere, add the following mixture to a 2,000 mL three-neck flask equipped with a reflux device and a stirrer: CH2=CH-CH2-O-CH2-Rf'-CH2-O-CH2-CH=CH2 Rf': -CF2O(CF2O) p1 (CF2CF2O) q1 CF2- (q1 / p1=0.9, p1+q1≒45, 19 Number average molecular weight calculated from F-NMR: ≒ 4,300) 500 g (0.12 mol) of perfluoropolyether represented by the formula (I) above, 700 g of m-xylene hexafluoride, and 451 g (1.50 mol) of pentamethylcyclopentasiloxane were added and heated to 90° C. with stirring. 0.442 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (1.1×10 as Pt alone) was added to the flask. -6 mol) was added, and stirring was continued for 4 hours while maintaining the internal temperature at 90°C or higher. 1 After confirming the disappearance of the allyl group of the raw material by H-NMR, the solvent and excess pentamethylcyclopentasiloxane were distilled off under reduced pressure. After that, activated carbon treatment was performed, and 511 g of a colorless, transparent liquid compound (c) represented by the following formula was obtained. [ka] Rf': -CF2O(CF2O) p1 (CF2CF2O) q1 CF2- (q1 / p1=0.9, p1+q1≒45, 19 Number average molecular weight calculated from F-NMR: ≒ 4,900)

[0101] Under a dry air atmosphere, 10.0 g of the compound (c) obtained above (Si-H group amount 1.6 × 10 -2 4.2 g (2.44 × 10 moles) of allyloxyethyl methacrylate -2 mol), 10.0 g of m-xylene hexafluoride, and 1.0 × 10 toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 g (0.3×10 as Pt alone) -7 The mixture was stirred at 80° C. for 4 hours. 1 After confirming the disappearance of the Si-H group by H-NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, and the residue was treated with activated carbon to obtain 10.1 g of a colorless and transparent fluorine-containing acrylic compound (A-3) represented by the following formula. [ka] Rf': -CF2O(CF2O) p1 (CF2CF2O)q1 CF2- (q1 / p1=0.9, p1+q1≒45)

[0102] [Synthesis Example 4] Synthesis of fluorine-containing acrylic compound (A-4) In a dry nitrogen atmosphere, add the following mixture to a 1,000 mL three-neck flask equipped with a reflux device and a stirrer: CH2=CH-CH2-O-CH2-Rf”-CH2-O-CH2-CH=CH2 Rf”:-CF2O(CF2O) p2 (CF2CF2O) q2 CF2- (q2 / p2=1.3, p2+q2≒16, 19 Number average molecular weight calculated from F-NMR: ≒ 1,800) 188 g (0.10 mol) of perfluoropolyether represented by the formula (I) above, 188 g of m-xylene hexafluoride, and 451 g (1.50 mol) of pentamethylcyclopentasiloxane were added and heated to 90° C. with stirring. 0.442 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (1.1×10 as Pt alone) was added to the flask. -6 mol) was added, and stirring was continued for 4 hours while maintaining the internal temperature at 90°C or higher. 1 After confirming the disappearance of the allyl group of the raw material by H-NMR, the solvent and excess pentamethylcyclopentasiloxane were distilled off under reduced pressure. After that, activated carbon treatment was performed, and 199 g of a colorless, transparent liquid compound (d) represented by the following formula was obtained. [ka] Rf”:-CF2O(CF2O) p2 (CF2CF2O) q2 CF2- (q2 / p2=1.3, p2+q2≒16, 19 Number average molecular weight calculated from F-NMR: ≒ 2,400)

[0103] Under a dry air atmosphere, 10.0 g of the compound (d) obtained above (Si-H group amount 3.3 × 10 -2mol) of allyloxyethyl methacrylate, 8.7 g (5.11 × 10 -2 mol), 10.0 g of m-xylene hexafluoride, and 2.0 × 10 toluene solution of chloroplatinic acid / vinylsiloxane complex. -2 g (Pt alone is 0.6×10 -7 The mixture was stirred at 80° C. for 4 hours. 1 After confirming the disappearance of the Si-H group by H-NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, and the residue was treated with activated carbon to obtain 11.6 g of a colorless and transparent fluorine-containing acrylic compound (A-4) represented by the following formula. [ka] Rf”:-CF2O(CF2O) p2 (CF2CF2O) q2 CF2- (q2 / p2=1.3, p2+q2≒16)

[0104] [Synthesis Example 5] Synthesis of fluorine-containing acrylic compound (A-5) In a 100 mL four-neck flask equipped with a reflux device and a stirrer, add the following [ka] Compound (e) represented by the formula: 10.0 g (Si-H group amount 8.65 × 10 -3 mol), allyloxyethyl methacrylate 2.2 g (1.30 × 10 -2 10.0 g of m-xylene hexafluoride was added and heated to 90°C under a nitrogen atmosphere with stirring. -2 g (Pt alone is 0.6×10 -7 mol) was added and stirred at 80° C. for 4 hours. 1 After confirming the disappearance of the Si-H group by H-NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, and the residue was treated with activated carbon to obtain 8.9 g of a semi-transparent white highly viscous liquid fluorine-containing acrylic compound (A-5) represented by the following formula. [ka]

[0105] [Synthesis Example 6] Synthesis of fluorine-containing acrylic compound (A-6) In a 100 mL four-neck flask equipped with a reflux device and a stirrer, add the following [ka] Compound (f) represented by the formula: 10.0 g (Si-H group amount 8.88 × 10 -3 mol), allyloxyethyl methacrylate 2.3 g (1.33 × 10 -2 10.0 g of m-xylene hexafluoride was added and heated to 90°C under a nitrogen atmosphere with stirring. -2 g (Pt alone is 0.6×10 -7 mol) was added and stirred at 80° C. for 4 hours. 1 After confirming the disappearance of the Si-H group by H-NMR and IR, the solvent and excess allyloxyethyl methacrylate were distilled off under reduced pressure, and the residue was treated with activated carbon to obtain 8.9 g of a semi-transparent white highly viscous liquid fluorine-containing acrylic compound (A-6) represented by the following formula. [ka]

[0106] The fluorine-containing acrylic compounds (A-1) to (A-6) obtained in the above Synthesis Examples 1 to 6 do not contain any volatile organic compounds.

[0107] The following fluorine-containing acrylic compositions (F-1) to (F-6) were prepared using the fluorine-containing acrylic compounds (A-1) to (A-6) obtained in the above Synthesis Examples 1 to 6 and the following acrylic compounds (B-1) to (B-3). (B-1) Isobutyl acrylate (B-2) Tetrahydrofurfuryl acrylate (B-3) 1,6-Hexanediol diacrylate

[0108] Fluorine-containing acrylic composition (F-1): (A-1) 20 parts by mass (B-1) 80 parts by mass

[0109] Fluorine-containing acrylic composition (F-2): (A-2) 20 parts by mass (B-3) 80 parts by mass

[0110] Fluorine-containing acrylic composition (F-3): (A-3) 20 parts by mass (B-1) 80 parts by mass

[0111] Fluorine-containing acrylic composition (F-4): (A-4) 20 parts by mass (B-3) 80 parts by mass

[0112] Fluorine-containing acrylic composition (F-5): (A-5) 20 parts by mass (B-2) 80 parts by mass

[0113] Fluorine-containing acrylic composition (F-6): (A-6) 20 parts by mass (B-2) 80 parts by mass

[0114] [Examples 1 to 6, Comparative Examples 1 and 2] Preparation of fluorine-containing active energy ray-curable composition Using the prepared fluorine-containing acrylic compositions (F-1) to (F-6), or the fluorine-containing acrylic compounds (A-1) and (A-2), fluorine-containing active energy ray-curable compositions were prepared in the ratios shown in Table 1 below.

[0115] [Table 1]

[0116] A-9550: Dipentaerythritol penta / hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) A-TMM-3: Pentaerythritol triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) IBA: Isobutyl acrylate THF-A: Tetrahydrofurfuryl acrylate HDDA: 1,6-Hexanediol diacrylate O-1173: 2-hydroxy-2-methylpropiophenone (Omnirad-1173, manufactured by BASF Japan Ltd.)

[0117] Coating and curing Each of the fluorine-containing active energy ray-curable compositions of the Examples and Comparative Examples was applied to a polycarbonate substrate by spin coating. After application, the substrate was leveled at room temperature (25°C) for 10 minutes, and then exposed to a total irradiation dose of 1,600 mJ / cm in a nitrogen atmosphere using a conveyor-type metal halide UV irradiation device (manufactured by Panasonic Electric Works Co., Ltd.). 2 The coated surface was irradiated with ultraviolet light to cure the composition, yielding a cured film having a thickness of about 9 μm.

[0118] The appearance (transparency) of the cured film obtained above was visually observed, and the water contact angle was measured to evaluate the stain resistance, the resistance to marker ink, and the water contact angle after the abrasion test to evaluate the abrasion resistance, all by the methods described below. The results are shown in Table 2.

[0119] Antifouling evaluation [Water contact angle measurement] The contact angle of the cured film produced above with water was measured using a contact angle meter Drop Master (Kyowa Interface Science Co., Ltd.) (droplet: 2 μl, temperature: 25° C., humidity (RH): 40%).

[0120] [Evaluation of resistance to marker ink (marker repellency)] A straight line was drawn on each of the cured films prepared above with a magic marker (large magic marker ink, manufactured by Teranishi Chemical Industry Co., Ltd.). Those that repelled ink were marked with an ◯, and those that did not repel ink were marked with an X.

[0121] Wear resistance evaluation [Measurement of water contact angle after abrasion test] The cured film surface was subjected to an abrasion test using a rubbing tester (manufactured by Shinto Scientific Co., Ltd.), and the water contact angle after the test was measured. The average value of N=8 measured values ​​was calculated. The test conditions are shown below. Eraser: RUBBER STICK (Minoan) Travel distance (one way): 40mm Traveling speed: 3,200mm / min Load: 500g / 6mm 2 φ Wear resistance: 1,000 times

[0122] [Table 2]

[0123] Examples 1 to 6, which used fluorine-containing acrylic compositions (F-1) to (F-6) prepared by blending fluorine-containing acrylic compounds (A-1) to (A-6) not containing a urethane bond in the molecular structure and acrylic compound (B) containing 1 to 2 (meth)acrylic groups in one molecule in a specific ratio as agents for imparting water / oil repellency and antifouling properties, showed excellent antifouling properties and were confirmed to have high abrasion resistance. On the other hand, Comparative Examples 1 and 2, in which fluorine-containing acrylic compounds (A-1) or (A-2) not containing a urethane bond in the molecular structure were added directly without being mixed with acrylic compound (B) containing 1 to 2 (meth)acrylic groups in one molecule, showed a cloudy appearance of the cured film and showed low antifouling properties.

Claims

1. (A) One or more fluorine-containing acrylic compounds selected from the group consisting of fluorine-containing acrylic compounds represented by the following formula: 【Chemistry 1】 【Chemistry 2】 【Chemistry 3】 [In the formula, Rf 2 is --CF 2 O--(CF 2 O) p (CF 2 CF 2 O) q --CF 2 --, p is an integer from 1 to 199, q is an integer from 1 to 170, p+q is 6 to 200, and the arrangement of the repeating units enclosed in parentheses is random. v is an integer from 4 to 120. R 2 is independently a hydrogen atom or a methyl group, and R 3 is independently a hydrogen atom, a methyl group, or a phenyl group. Z 4 is a group represented by the following formula: -C O H 2O - (OC 3 H 6 ) j' (OC 2 H 4 ) k' (OCH 2 ) l' - (wherein each repeating unit may be linear or branched, and each repeating unit may be randomly bonded to another repeating unit, j', k', and l' are each independently an integer of 0 to 4, j'+k'+l'=1 to 10, and o is an integer of 2 to 10), and m is an integer of 2 to 5. (B) an acrylic compound having a viscosity of 100 mPa·s or less at 25° C. and containing one or two (meth)acrylic groups per molecule; as essential components, the mass ratio of component (A) to component (B) being within the range of 0.01<(A) / (B)<10, and further comprising no volatile organic compound having no group reactive with an acrylic group.

2. As a part or the whole of the component (B), CH 2 =CR 5 C(=O)OR 4 (6) (In the formula, R 4 R is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group. 5 is a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms. The fluorine-containing acrylic composition according to claim 1, which contains an acrylic compound represented by the formula:

3. As a part or the whole of the (B) component, the following general formula (7) CH 2 =CR 7 C(=O)O-R 6 -O(O=)CR 7 C=CH 2 (7) (In the formula, R 6 R is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a urethane bond, an ether bond, an isocyanate group, or a hydroxyl group. 7 are each independently a hydrogen atom, a methyl group, a fluorine atom, or a fluoroalkyl group having 1 to 6 carbon atoms. The fluorine-containing acrylic composition according to claim 1 or 2, which contains an acrylic compound represented by the formula:

4. The fluorine-containing acrylic composition according to any one of claims 1 to 3, wherein the acrylic compound of the component (B) does not contain an alkyl group substituted with a fluorine atom.

5. A fluorine-containing active energy ray-curable composition comprising 0.005 to 40 parts by mass of the fluorine-containing acrylic composition according to any one of claims 1 to 4 relative to 100 parts by mass of the active energy ray-curable composition (E).

6. The active energy ray-curable composition (E) is (Ea) Acrylic compound: 100 parts by mass, (Eb) Photopolymerization initiator: 0.1 to 15 parts by mass 6. The fluorine-containing active energy ray-curable composition according to claim 5, which comprises

7. 7. The fluorine-containing active energy ray-curable composition according to claim 5 or 6, which gives a cured product having a water contact angle of 90° or more at 25° C. and a relative humidity of 40%.

8. An article having a layer of the cured product of the fluorine-containing active energy ray-curable composition according to any one of claims 5 to 7 on a surface thereof.

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