CN111615526A - Fluorine-containing active energy ray-curable composition and article - Google Patents
Fluorine-containing active energy ray-curable composition and article Download PDFInfo
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- CN111615526A CN111615526A CN201880086993.5A CN201880086993A CN111615526A CN 111615526 A CN111615526 A CN 111615526A CN 201880086993 A CN201880086993 A CN 201880086993A CN 111615526 A CN111615526 A CN 111615526A
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- fluorine
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- active energy
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- 239000011737 fluorine Substances 0.000 title claims abstract description 165
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
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- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
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- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
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- 230000003405 preventing effect Effects 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
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- 238000007788 roughening Methods 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
Abstract
The fluorine-containing active energy ray-curable composition is characterized by containing a fluorine-containing compound (A) having a cyclic polysiloxane structure bonded to both ends of a 2-valent perfluoropolyether group via a 2-valent linking group, and having a hydroxyl group bonded to the cyclic polysiloxane structure via the 2-valent linking group and a (meth) acryloyl group bonded to the cyclic polysiloxane structure via the 2-valent linking group at either or both ends of the cyclic polysiloxane structure.
Description
Technical Field
The present invention relates to a fluorine-containing active energy ray-curable composition which is cured by ultraviolet rays, electron beams, or the like to impart excellent antifouling properties to a surface, and an article having a cured product layer of the composition on a substrate surface.
Background
Conventionally, hard coat treatment has been widely used as a means for protecting the surface of a resin molded article or the like. In this method, a hard cured resin layer (hard coat layer) is formed on the surface of the molded article, and this layer is hard to be damaged. As a material constituting the hard coat layer, a curable composition using an active energy ray such as a thermosetting resin, an ultraviolet ray or electron beam curable resin is often used.
On the other hand, with the expansion of the field of use of resin molded articles and the trend toward higher added values, there is an increasing demand for higher functionality of the cured resin layer (hard coat layer), and as one of them, it is required to impart antifouling properties to the hard coat layer. Among them, the surface of the hard coat layer is imparted with properties such as water repellency and oil repellency, so that it is hard to be contaminated or can be easily removed even if contaminated.
As a method for imparting antifouling property 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 formed temporarily has been widely used, and a method of simultaneously forming a hard coat layer and imparting antifouling property by adding a fluorine-containing curable component to a cured resin composition before curing and applying and curing the same has also been studied. For example, japanese patent application laid-open No. 6-211945 (patent document 1) discloses the production of a hard coat layer to which antifouling properties are imparted by adding a fluoroalkyl acrylate to an acrylic curable resin composition and curing the mixture.
The present inventors have variously developed a fluorine compound capable of imparting stain resistance to such a curable resin composition, and for example, proposed a photocurable fluorine compound as shown in japanese patent laid-open nos. 2010-53114 (patent document 2), 2010-138112 (patent document 3) and 2010-285501 (patent document 4).
On the other hand, in applications where a person has an opportunity to touch with a free hand, for example, in car-mounted touch panel displays of smart phones, tablet PCs, digital signboards, navigation systems, consoles, and the like, and displays for home large TVs and PCs, in particular, in a characteristic collectively called antifouling property, it is increasingly strongly required that adhesion of fingerprints is not conspicuous; the fingerprint erasure is excellent; further, the hard coat layer has excellent wear durability. Therefore, for these characteristics, an active energy ray-curable composition capable of providing more excellent characteristics than ever before is often required.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open 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 publication No. 2010-285501
Disclosure of Invention
Problems to be solved by the invention
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 active energy ray-curable composition which forms a cured coating film capable of imparting stain resistance, particularly excellent water-and oil-repellency, fingerprint-adhesion resistance, fingerprint-erasure resistance, and abrasion durability, and an article having a cured layer of the composition on a surface of a substrate.
Means for solving the problems
The present inventors have made extensive studies to achieve the above object, and as a result, have found that: among the various properties collectively referred to as stain resistance, the fluorine-containing active energy ray-curable composition containing a fluorine compound having the following structure, the fluorine-containing active energy ray-curable composition is excellent in resistance to the development of fingerprints, excellent in fingerprint erasure properties, and further excellent in abrasion durability as a hard coat layer: the present inventors have completed the present invention by bonding a cyclic polysiloxane structure to both ends of a perfluoropolyether group via a 2-valent linking group, bonding a hydroxyl group to the cyclic polysiloxane structure via a 2-valent linking group, and bonding a (meth) acryloyl group to the cyclic polysiloxane structure via a 2-valent linking group.
Accordingly, the present invention provides the following fluorine-containing active energy ray-curable composition and an article having a cured product layer of the composition on a surface of a substrate.
1. A fluorine-containing active energy ray-curable composition which is characterized by containing a fluorine-containing compound (A) having a cyclic polysiloxane structure bonded to both ends of a 2-valent perfluoropolyether group via a 2-valent linking group, and having a hydroxyl group bonded to the cyclic polysiloxane structure via a 2-valent linking group and a (meth) acryloyl group bonded to the cyclic polysiloxane structure via a 2-valent linking group, in either or both of the cyclic polysiloxane structures at both ends.
The fluorine-containing active energy ray-curable composition according to claim 1, wherein the molar ratio of the (meth) acryloyl group in the fluorine-containing compound (A) to the hydroxyl group contained in the fluorine-containing compound (A) [ (meth) acryloyl group (mol)/hydroxyl group (mol) ] is 0.1 or more and 25 or less on average.
The fluorine-containing active energy ray-curable composition according to claim 1 or 2, further comprising a fluorine-containing compound (B) having a cyclic polysiloxane structure bonded to both ends of the 2-valent perfluoropolyether group via the 2-valent linking group, and having the following structure at both ends: has a (meth) acryloyl group bonded to the cyclic polysiloxane structure via a 2-valent linking group and has no hydroxyl group.
4.3 the fluorine-containing active energy ray-curable composition, wherein the molar ratio of the total of (meth) acryloyl groups contained in the fluorine-containing compound (A) and (meth) acryloyl groups contained in the fluorine-containing compound (B) to hydroxyl groups contained in the fluorine-containing compound (A) [ (total (mol) of meth) acryloyl groups)/hydroxyl groups (mol) ] is 0.1 or more and 25 or less, on an average value contained in the entire composition.
5.1 to 4 the fluorine-containing active energy ray-curable composition, wherein the fluorine-containing compound (A) is represented by the following general formula (1)
X1-Z-Rf-Z-X1(1)
[ wherein Rf is selected from the following formulae (2) to (5)
[ solution 1]
(wherein Y is independently F or CF)3R is an integer of 2-6, m and n are each 0 &200, however, m + n is 2 to 200, and s is an integer of 0 to 6. The repeating units may be randomly combined. )
[ solution 2]
-CjF2j(OCF2CF2CF2)kOCjF2j- (3)
(wherein j is independently an integer of 1 to 3, and k is an integer of 1 to 200.)
[ solution 3]
(wherein Y, j is the same as above, p and q are each an integer of 0 to 200, however, p + q is 2 to 200. the repeating units may be randomly combined.)
[ solution 4]
-(CF2CF2O-CF2CF2CF2CF2O)tCF2- (5)
(wherein t is an integer of 1 to 100.)
Among the groups represented by (A), a 2-valent perfluoropolyether group having a molecular weight of 500 to 30000, X1Independently of each other, represented by the following formula (6)
[ solution 5]
[ wherein Q1The carbon atom number of the 2-valent linking group containing a bond selected from an ether bond, an ester bond, an amide bond and a urethane bond, and the cyclic structure or the branched structure may be contained in the linking group, and may be the same or different. R1Is composed of the following formula (7)
[ solution 6]
(in the formula, R2Independently is a hydrogen atom or a methyl group, R3C1-18 ether bond and/or ester bondA linking group having a valence of 2 or 3, and c is 1 or 2. )
The (meth) acryloyl group-containing group is represented by a and b each being an integer of 0 to 6, however, a + b is 2 to 11. The repeating units may be randomly combined. ]
Group represented by, X present in the molecule1Wherein a and b in total are each 2 or more. Z is represented by the following formula
[ solution 7]
[ solution 8]
[ solution 9]
[ solution 10]
[ solution 11]
-CH2-O-CH2-
[ solution 12]
-CH2-CH2-
[ solution 13]
[ solution 14]
[ solution 15]
[ solution 16]
Any one of them represents a 2-valent organic group. ]
And (4) showing.
The fluorine-containing active energy ray-curable composition according to any one of claims 1 to 5, further comprising an acrylic compound (C) other than the fluorine-containing compounds (A) and (B).
The fluorine-containing active energy ray-curable composition according to claim 6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in 1 molecule and having no hydroxyl group in the molecule.
The fluorine-containing active energy ray-curable composition according to claim 6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups and 1 or more hydroxyl groups in 1 molecule.
The fluorine-containing active energy ray-curable composition according to 9.6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional urethane (meth) acrylate having a urethane bond in a molecule and having 6 or more (meth) acryloyl groups in 1 molecule.
10.1 to 9, further comprising (D) a photopolymerization initiator.
11. An article having a water-repellent surface with a water contact angle of 105 ° or more, and having a cured coating film of the fluorine-containing active energy ray-curable composition described in any one of 1 to 10 on the surface.
ADVANTAGEOUS EFFECTS OF INVENTION
By applying and curing the fluorine-containing active energy ray-curable composition of the present invention to the surface of the base material, water repellency, oil repellency, stain resistance, slidability, low visibility of attached fingerprints, fingerprint erasability, and abrasion resistance can be imparted.
Detailed Description
The fluorine-containing active energy ray-curable composition of the present invention contains a fluorine-containing compound (a) having the following structure: the cyclic polysiloxane structure having a valence of 3 or more (usually a valence of 3 to 12, preferably a valence of 3 to 8, more preferably a valence of 3 to 6) is bonded to both ends of the 2-valent perfluoropolyether group via 2-valent linking groups, and 1 or more hydroxyl groups bonded to the cyclic polysiloxane structure via 2-valent linking groups and (meth) acryloyl groups bonded to the cyclic polysiloxane structure via 2-valent linking groups are bonded to either or both of the cyclic polysiloxane structures at both ends. The fluorine-containing compound (a) has an effect of making fingerprints less noticeable by having the hydroxyl group, and has an effect of fixing a fluorine component exhibiting stain resistance to the surface by having the (meth) acryloyl group to obtain curability.
The ratio of the (meth) acryloyl group to the hydroxyl group contained in the fluorine-containing compound (a), particularly, the molar ratio of the (meth) acryloyl group to the hydroxyl group contained in the fluorine-containing compound (a) [ (meth) acryloyl group (mol)/hydroxyl group (mol) ] is preferably 0.1 or more and 25 or less, more preferably 0.15 or more and 19 or less, particularly preferably 0.2 or more and 10 or less, further preferably 0.2 or more and 5 or less, and most preferably 0.2 or more and 2.5 or less, based on the average value of the fluorine-containing compound (a) contained in the composition. If the molar ratio is larger than this, the effect of the hydroxyl group contained in the fluorine-containing compound (A) is small, and the difference in the characteristics after curing from the fluorine-containing compound containing no hydroxyl group becomes unclear. When the molar ratio is smaller than this, the content of molecules having no (meth) acryloyl group in the fluorine-containing compound (a) increases, and the solubility of the acrylic compound other than fluorine decreases, and the acrylic compound may become difficult to be applied as a uniform plane or may be cured poorly.
As the fluorine-containing compound (a), specifically, a compound having a structure represented by the following general formula (1) can be exemplified.
X1-Z-Rf-Z-X1(1)
In the formula (1), Rf has a particularly preferable main structure consisting of repeating unit groups shown below
-CF2O-
-CF2CF2O-
-CF2CF2CF2O-
-CF(CF3)CF2O-
-CF2CF2CF2CF2O-
Any one or a combination of a plurality of them. Among them, examples of the moiety not corresponding to the main structure include a binding moiety to Z, an initiator fragment in the case of constructing a main chain structure, and a by-product structure.
Among them, preferable is a 2-valent perfluoropolyether group having a molecular weight of 500 to 30000 selected from the group represented by the following formulae (2) to (5).
[ solution 17]
(wherein Y is independently F or CF)3R is an integer of 2 to 6, m and n are each an integer of 0 to 200, preferably an integer of 1 to 100, more preferably an integer of 4 to 50, however, m + n is an integer of 2 to 200, preferably an integer of 8 to 100, and s is an integer of 0 to 6. The repeating units may be randomly combined. )
[ solution 18]
-CjF2j(OCF2CF2CF2)kOCjF2j- (3)
(wherein j is independently an integer of 1 to 3, k is an integer of 1 to 200, preferably an integer of 2 to 100, more preferably an integer of 4 to 50.)
[ solution 19]
(wherein Y, j is the same as above, p and q are each an integer of 0 to 200, preferably an integer of 1 to 100, more preferably an integer of 4 to 50, however, p + q is 2 to 200, preferably 8 to 100. the repeating units may be randomly combined.)
[ solution 20]
-(CF2CF2O-CF2CF2CF2CF2O)tCF2- (5)
(wherein t is an integer of 1 to 100, preferably an integer of 2 to 60, more preferably an integer of 4 to 40.)
Among them, preferable are the structures represented by the formulae (2) and (4).
Further, Rf has a molecular weight of preferably 500 to 30000, particularly preferably 1500 to 10000. If the molecular weight is too small, the compatibility with the non-fluorinated component in the composition is excessively increased, and the component may not be aggregated on the surface (a) of the cured product (coating film) after coating, and if it is too large, the compatibility with the non-fluorinated component in the composition is excessively low, and turbidity, generation of precipitates, increase in haze of the cured product (coating film) after coating, chipping of the coating film, reduction in smoothness, and the like may occur at the time of compounding. The molecular weight can be determined as a value converted to polymethyl methacrylate in Gel Permeation Chromatography (GPC) analysis using various fluorine-containing solvents as elution solvents, for example, and is preferably determined as a number average molecular weight (the same applies below).
In the general formula (1), Z is a 2-valent organic group represented by any one of the following formulae.
[ solution 21]
[ solution 22]
[ solution 23]
[ solution 24]
[ solution 25]
-CH2-O-CH2-
[ solution 26]
-CH2-CH2-
[ solution 27]
[ solution 28]
[ solution 29]
[ solution 30]
Among them, Z is particularly preferred
[ solution 31]
-CH2-CH2-
[ solution 32]
-CH2-O-CH2-
[ solution 33]
[ chemical 34]
[ solution 35]
In the formula (1), the reaction mixture is,X1independently of each other, a group represented by the following formula (6).
[ solution 36]
[ wherein Q1The carbon atom number of the 2-valent linking group containing a bond selected from an ether bond, an ester bond, an amide bond and a urethane bond, and the cyclic structure or the branched structure may be contained in the linking group, and may be the same or different. R1Is composed of the following formula (7)
[ solution 37]
(in the formula, R2Independently is a hydrogen atom or a methyl group, R3Is a linking group with 2 or 3 valences containing ether bond and/or ester bond and having 1-18 carbon atoms, and c is 1 or 2. )
The (meth) acryloyl group-containing group is shown. a and b are each an integer of 0 to 6, preferably an integer of 1 to 6, more preferably an integer of 2 to 4, however, a + b is 2 to 11, preferably 2 to 7, more preferably 2 to 5. The repeating units may be randomly combined. Furthermore, in the formula (1), X is present in the molecule1Wherein a and b in total are each 2 or more.]
In the formula (6), Q1The carbon atom number 2-20 connecting group containing a bond selected from ether bond, ester bond, amido bond and urethane bond, preferably carbon atom number 3-20, especially carbon atom number 3-12 containing a bond selected from ether bond, ester bond, amido bond and urethane bond 2-valent hydrocarbon group, can contain a cyclic structure or a branched structure in the middle, and can be the same or different.
As Q1Among them, any of the following structures is preferable.
-CH2CH2CH2-
-CH2CH2CH2-O-CH2CH2-
-CH2CH2CH2-O-CH2CH2-O-CH2CH2-
-CH2CH2CH2-O-CH2CH2-O-CH2CH2-O-CH2CH2-
-[CH2CH(CH3)O]z-CH2CH(CH3)-
[ solution 38]
(wherein z is an integer of 0 to 10.)
In the formula (6), R1Is a (meth) acryloyl group-containing group represented by the following formula (7).
[ solution 39]
(in the formula, R2Independently is a hydrogen atom or a methyl group, R3Is a linking group with 2 or 3 valences containing ether bond and/or ester bond and having 1-18 carbon atoms, and c is 1 or 2. )
In the formula (7), R2Independently a hydrogen atom or a methyl group.
In addition, R3The carbon atom number of the 2-valent or 3-valent linking group which can contain ether bond and/or ester bond is 1-18, preferably carbon atom number of the 2-valent hydrocarbon group which can contain ether bond and/or ester bond, especially carbon atom number of 2-8, especially alkylene, for example, preferably represented by the following formula.
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2CH2CH2CH2CH2CH2-
-CH2CH2OCH2CH2-
-CH2CH2OCH2CH2OCH2CH2-
-CH2CH2OCH2CH2OCH2CH2-
c is 1 or 2, preferably 1.
Further, in the fluorine-containing compound (a) according to the present invention, the hydroxyl group bonded to the cyclic polysiloxane structure having a valence of 3 or more (usually, a valence of 3 to 12, preferably, a valence of 3 to 8, more preferably, a valence of 3 to 6) bonded to both ends of the perfluoropolyether group having a valence of 2 via the linking group having a valence of 2 and the (meth) acryloyl group bonded to the cyclic polysiloxane structure having a valence of 2 via the linking group having 1 or more, preferably 1 to 6, more preferably 2 to 4, independently of each other, in either or both of the cyclic polysiloxane structures having both ends, and in the above formula (1), the total amount of a corresponding to the total amount of the (meth) acryloyl groups in the molecule (i.e., the total amount of the (meth) acryloyl groups in the cyclic polysiloxane structures having both ends) is 1 or more, preferably 1 to 12, more preferably 2 to 8, further preferably 4 to 6, and the total amount of b corresponding to the total amount of the hydroxyl groups in the molecule (i.e., the total number of hydroxyl groups in the cyclopolysiloxane structure at both ends) is 1 or more, preferably 1 to 12, more preferably 2 to 8, and still more preferably 4 to 6.
In each of the cyclopolysiloxane structures represented by the above formula (6), the value of a + b is usually 2 to 11, preferably 2 to 7, more preferably 2 to 5, each independently, and in the above formula (1), the sum of the values of (a + b) corresponding to the sum of the number of (meth) acryloyl groups and the number of hydroxyl groups in the molecule (that is, 2X in the molecule1The total of the number of (meth) acryloyl groups and the number of hydroxyl groups in the group) is usually 4 to 22, preferably 6 to 14, and more preferably 6 to 10.
In addition, in the production of the fluorine-containing compound (a), a compound having a structure represented by the following general formula (8) may be by-produced, and these compounds may be removed by various means such as distillation, extraction, and separation chromatography, or a product containing them may be used as it is.
X1-[Z-Rf-Z-X2]v-Z-Rf-Z-X1(8)
In the general formula (8), X1Z, Rf is the same as general formula (1), v is an integer of 1 to 4, X2Independently of each other, a group represented by the following formula (9).
[ solution 40]
(in the formula, Q1、R1As described above, d and e are each an integer of 0 to 3, preferably 1 to 3, and d + e is an integer of 1 to 10, preferably 1 to 6. The repeating units may be randomly combined. )
As a preferred structure of the fluorine-containing compound (a), specifically, the following structure can be exemplified.
[ solution 41]
[ solution 42]
[ in the formula, Rf' may be the same as Rf, and is preferably-CF2O(CF2O)p’(CF2CF2O)q’CF2Examples of the- (p ', q's) include the same groups as those of the above-mentioned p and q. R4Is a hydrogen atom or a (meth) acryloyl group-containing group, and R is contained in the molecule4The number of hydrogen atoms of (A) is defined as nHN represents the number of (meth) acryloyl group-containing groupsAWhen n is greater than nH、nAEach is an integer of 1 to 5, and n is an integer of n for each moleculeH+nA=6。]
Wherein R is4The group is a hydrogen atom or a (meth) acryloyl group-containing group, and the (meth) acryloyl group-containing group is preferably a group shown below.
CH2=CHCO-
CH2=C(CH3)CO-
CH2=CHCOOCH2CH2-NH-CO-
CH2=CCH3COOCH2CH2-NH-CO-
CH2=CCH3COOCH2CH2OCH2CH2-NH-CO-
[CH2=CCH3COOCH2]2CH(CH3)-NH-CO-
R is a group contained in the molecule of the fluorine-containing compound (A)14The number of hydrogen atoms of (A) is defined as nHN represents the number of (meth) acryloyl group-containing groupsAWhen n is greater than nH、nAEach is an integer of 1 to 5, and n is an integer of n for each moleculeH+nA=6。
The fluorine-containing compound (a) according to the present invention is preferably produced by any of the following methods, for example, although the effects thereof are not changed by any of the production methods. That is, the fluorine-containing compound (a) can be obtained by reacting a part of the hydroxyl groups of a compound (fluorine-containing alcohol compound) having a plurality of OH groups (hydroxyl groups) at both ends of a fluoropolyether group with a (meth) acryloyl group-introducing agent such as a (meth) acryloyl halide or a (meth) acryloyl group-containing isocyanate compound, and partially introducing (meth) acryloyl groups into the hydroxyl groups.
Among them, as a compound (fluorine-containing alcohol compound) having a plurality of OH groups at both ends of the fluoropolyether group, which becomes a precursor of the fluorine-containing compound (a), specifically, the following compounds can be mentioned.
[ solution 43]
[ solution 44]
(wherein Rf' is the same as described above.)
Examples of the (meth) acryloyl group-introducing reagent include (meth) acryloyl halides such as acryloyl chloride and methacryloyl chloride, and (meth) acryloyl group-containing isocyanate compounds (acrylic acid derivatives having an isocyanate group) shown below.
CH2=CHCOOCH2CH2-N=C=O
CH2=CCH3COOCH2CH2-N=C=O
CH2=CCH3COOCH2CH2OCH2CH2-N=C=O
[CH2=CCH3COOCH2]2CH(CH3)-N=C=O
In these (meth) acryloyl halides or (meth) acryloyl group-containing isocyanate compounds, a method of charging and reacting the compounds without an excess amount of the compounds with respect to the total amount of hydroxyl groups of the fluorine-containing alcohol compounds is preferred. Specifically, when the total amount of hydroxyl groups of the fluorine-containing alcohol compound in the reaction system is x moles, and the amount of halogen atoms or isocyanate groups of the (meth) acryloyl halide or (meth) acryloyl group-containing isocyanate compound is y moles, the reaction system may be fed preferably at a ratio of 0.1. ltoreq. y/(x-y). ltoreq.25, more preferably at a ratio of 0.15. ltoreq. y/(x-y). ltoreq.19, particularly preferably at a ratio of 0.2. ltoreq. y/(x-y). ltoreq.10, further preferably at a ratio of 0.2. ltoreq. y/(x-y). ltoreq.5, and most preferably at a ratio of 0.2. ltoreq. y/(x-y). ltoreq.2.5, and the reaction system may be entirely or in a desired amount. In addition, a method of feeding at the above ratio of y/(x-y) >25 and stopping without completing the reaction can also be used, and in this case, the reaction must be stopped reliably by removing the reaction catalyst or the like.
These reactions can be carried out by diluting with an appropriate solvent as required. Such a solvent can be used without any particular limitation as long as it does not react with the hydroxyl group of the fluorinated alcohol compound, the halogen atom of the (meth) acryloyl halide, or the isocyanate group of the (meth) acryloyl group-containing isocyanate compound, and specific examples thereof include hydrocarbon solvents such as toluene, xylene, and isooctane, ether solvents such as tetrahydrofuran, diisopropyl ether, and dibutyl ether, ketone solvents such as acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, and cyclohexanone, fluorine-modified aromatic hydrocarbon solvents such as hexafluoro-m-xylene and benzylidene trifluoro, and fluorine-modified ether solvents such as methyl perfluorobutyl ether. The solvent may be removed by a known method such as distillation under reduced pressure after the reaction, or may be used as a diluted solution depending on the intended use. The amount of the solvent used is not particularly limited, but is preferably 10 times or less the total mass of the reaction components. If the amount of the solvent used is too large, there is a risk that the reaction rate is greatly reduced.
In the reaction, a polymerization inhibitor may be added as necessary. The polymerization inhibitor is not particularly limited, and a polymerization inhibitor used as a polymerization inhibitor for acrylic compounds can be usually used. Specific examples thereof include hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, and dibutylhydroxytoluene. The amount of the polymerization inhibitor to be used is not particularly limited, and may be determined depending on the reaction conditions, purification conditions after the reaction, and final use conditions, and is usually 0.01 to 5000ppm, and particularly preferably 0.1 to 500ppm, based on the total mass of the reaction components.
When the (meth) acryloyl halide is reacted with the fluorine-containing alcohol compound, it is particularly preferable to react acryloyl chloride or methacryloyl chloride to form an ester. The ester formation reaction is carried out by dropping (meth) acryloyl halide while mixing and stirring the reaction intermediate (fluorinated alcohol compound) and the acid acceptor. As the acid acceptor, triethylamine, pyridine, urea and the like can be used. The amount of the acid-receiving agent to be used is preferably about 0.9 to 3 times the molar number of (meth) acryloyl halide fed. If the amount is too small, a large amount of the acid that is not trapped remains, and if the amount is too large, removal of the remaining acid-receiving agent becomes difficult.
The dropping of the (meth) acryloyl halide is carried out by maintaining the temperature of the reaction mixture at 0 to 35 ℃ for 20 to 60 minutes. Then, the stirring was continued for further 30 minutes to 10 hours. After the completion of the reaction, unreacted (meth) acryloyl halide, a salt produced by the reaction, a reaction solvent, and the like are removed by a method such as distillation, adsorption, filtration, and washing, whereby the fluorine-containing compound (a) according to the present invention can be obtained.
When the reaction is stopped, an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted (meth) acryloyl halide. The (meth) acrylic acid esters formed can be removed by the same method as that for removing the unreacted (meth) acrylic acid halide, but they can also be used in the remaining state.
When the (meth) acryloyl group-containing isocyanate compound is reacted with the fluorine-containing alcohol compound, the fluorine-containing alcohol compound and the (meth) acryloyl group-containing isocyanate compound are stirred together with a solvent as necessary to carry out the reaction.
In this reaction, in order to increase the reaction rate, a suitable catalyst may be added. Examples of the catalyst include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctoate and stannous dioctoate, titanates or titanium chelate compounds such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra (2-ethylhexyloxy) titanium, dipropoxybis (acetylacetonato) titanium and isopropoxyoctyleneglycol titanium, zirconium tetraacetylacetonate, tributoxybis-monoacetoacetonate, bis (ethylacetoacetate) zirconium monobutoxybis (ethylacetoacetate), dibutoxybis-ethylacetoacetate-zirconium, tetraacetylacetonate and zirconium chelate compounds. These are not limited to 1, and can be used as 2 or more, and particularly preferably used as a titanium compound and a zirconium compound having low environmental impact.
The reaction rate can be increased by adding 0.01 to 5 mass%, preferably 0.05 to 3 mass%, of these catalysts to the total mass of the fluorinated alcohol compound and the (meth) acryloyl group-containing isocyanate compound.
The reaction is carried out at a temperature of 0 to 120 ℃, preferably 10 to 70 ℃, for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may be too slow, and if the reaction temperature is too high, polymerization of the (meth) acryloyl group may occur as a side reaction.
After the reaction is completed, unreacted isocyanate compound, reaction solvent and the like are removed by a method such as distillation, adsorption, filtration and washing, and the fluorine-containing compound (a) according to the present invention can be obtained.
When the reaction is stopped, an alcohol compound such as methanol or ethanol may be added to the system to form a urethane bond with an unreacted isocyanate compound. The urethane (meth) acrylates formed can be removed by the same method as the unreacted isocyanate compound, and can be used in a remaining state.
In the fluorine-containing active energy ray-curable composition of the present invention, a compound having a plurality of alcohols at both ends of the fluoropolyether group, which is not reacted with the precursor, may remain and may be contained due to factors such as the incorporation ratio of a (meth) acryloyl group by-produced in the production of the fluorine-containing compound (a). Further, there is a possibility that a compound in which all of the (meth) acryloyl groups are introduced into the hydroxyl groups may be generated, and it is considered that the compound corresponds to the fluorine-containing compound (B) described later.
As another constitution method of the fluorine-containing active energy ray-curable composition of the present invention, there can be shown a fluorine-containing active energy ray-curable composition comprising a fluorine-containing compound (a) and a fluorine-containing compound (B), the fluorine-containing compound (B) having the following structure: the cyclic polysiloxane structure is bonded to both ends of the perfluoropolyether group via a 2-valent linking group, and the (meth) acryloyl group is bonded to the cyclic polysiloxane structure via a 2-valent linking group, and does not contain a hydroxyl group.
Specifically, the fluorine-containing compound (B) can be exemplified by a compound having a structure represented by the following general formula (10).
X3-Z-Rf-Z-X3(10)
[ wherein Rf and Z are the same as defined above. X3Independently of each other, represented by the following formula (11)
[ solution 45]
(in the formula, Q1、R1As described above. f is an integer of 2 to 11, preferably an integer of 2 to 7, and more preferably an integer of 2 to 5. The repeating units may be randomly combined. )
The group shown. ]
In addition, in the production of the fluorine-containing compound (B), a compound having a structure represented by the following general formula (12) may be by-produced, and these compounds may be removed by various means such as distillation, extraction, and separation chromatography, or a product containing them may be used as it is.
X3-[Z-Rf-Z-X4]w-Z-Rf-Z-X3(12)
In the general formula (12), Rf, Z and X3Same as the general formula (10), w is an integer of 0 to 5, X4Independently of each other, a group represented by the following formula (13).
[ solution 46]
(in the formula, Q1、R1Similarly, g is an integer of 1 or more, preferably an integer of 1 to 7, and more preferably an integer of 2 to 3. The repeating units may be randomly combined. )
That is, the fluorine-containing compound (B) can represent X in the compound represented by the general formula (1)1A compound wherein b is 0.
As a preferred structure of the fluorine-containing compound (B), the following structure can be specifically exemplified.
[ solution 47]
[ solution 48]
(in the formula, wherein,rf' is the same as above, R5Is a (meth) acryloyl group-containing group. )
Wherein, as R5The (meth) acryloyl group-containing group of (2) can be exemplified by the group represented by R4The (meth) acryloyl group-containing groups exemplified in (1) above are the same groups.
Such a fluorinated compound (B) can be obtained by feeding the fluorinated compound (a) in the above-exemplified synthesis method of the fluorinated compound (a) at a ratio such that x moles of the halogen atoms or the amount of isocyanate groups of the (meth) acryloyl group-introducing reagent with respect to the total amount of hydroxyl groups of the fluorinated alcohol compound are x < y, and allowing all of the hydroxyl groups to react.
In the embodiment of the present invention in which the fluorine-containing compound (a) and the fluorine-containing compound (B) are used in combination, the same effect as that obtained by changing the ratio of the (meth) acryloyl group to the hydroxyl group with the fluorine-containing compound (a) monomer can be obtained by adjusting the content ratio of the fluorine-containing compound (a) and the fluorine-containing compound (B). In this case, the molar ratio of the total of the (meth) acryloyl group contained in the fluorine-containing compound (A) and the (meth) acryloyl group contained in the fluorine-containing compound (B) to the hydroxyl group contained in the fluorine-containing compound (A) [ (total (mol) of meth) acryloyl groups)/hydroxyl group (mol) } is the average value of the total of the fluorine-containing compound (A) and the fluorine-containing compound (B) contained in the composition]Preferably 0.2 to 19, more preferably 0.3 to 10, and still more preferably 0.4 to 5. That is, the total mole number of (meth) acryloyl groups contained in the fluorine-containing compound (A) contained in the system is defined as NaAThe total number of moles of hydroxyl groups is defined as NaHN represents the total mole number of (meth) acryloyl groups contained in the fluorine-containing compound (B)bAWhen it is used, it is desirably 0.2. ltoreq. NaA+NbA)/NaH≤19。
If the amount is larger than this, the difference in the characteristics of the single compound with the fluorine-containing compound (B) becomes unclear, and if the amount is smaller than this, the solubility of the acrylic compound with non-fluorine decreases, and uniform application at a concentration necessary for the characteristics to be exhibited becomes difficult.
The fluorine-containing active energy ray-curable composition can be used as a single fluorine-containing compound (a) or as a mixture of only the fluorine-containing compound (a) and the fluorine-containing compound (B), and any of them can be used as long as it can be mixed with the fluorine-containing compound (a) and the fluorine-containing compound (B) and cured. Specific examples of such a compound include an acrylic compound (C) which is not equivalent to the fluorine-containing compounds (a) and (B), preferably contains no fluorine atom in the molecule (non-fluorinated), and contains or does not contain a urethane bond in the molecule. Examples of the acrylic compound (C) include 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide isocyanurate-modified di (meth) acrylate, EO isocyanurate-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-tris- (meth) acryloyloxymethyl) ethyl phthalate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol (meth) acrylate, trimethylolpropane tetra (meth) acrylate, pentaerythritol penta (meth) acrylate, and mixtures thereof, Acrylic compounds such as 2 to 6-functional (meth) acrylic compounds such as dipentaerythritol hexa (meth) acrylate and sorbitol hexa (meth) acrylate, ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, alkyl-modified products of these (meth) acrylic compounds, epoxy (meth) acrylates obtained by adding an epoxy resin to (meth) acrylic acid, and copolymers having a (meth) acryloyl group introduced into a side chain of an acrylate copolymer.
Further, urethane (meth) acrylates, products obtained by reacting polyisocyanates with (meth) acrylates having hydroxyl groups, products obtained by reacting polyesters of polyisocyanates and terminal diols with (meth) acrylates having hydroxyl groups, and products obtained by reacting polyisocyanates obtained by reacting polyols with excess diisocyanates with (meth) acrylates having hydroxyl groups can also be used. Among these, preferred are urethane (meth) acrylates obtained by reacting a hydroxyl group-containing (meth) acrylate selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate and pentaerythritol tri (meth) acrylate with a polyisocyanate selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, lysine diisocyanate, norbornane diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, methylenebis (4-cyclohexyl isocyanate), 2-methyl-1, 3-diisocyanatocyclohexane, 2-methyl-1, 5-diisocyanatocyclohexane and diphenylmethane diisocyanate.
Among them, a non-fluorinated multifunctional (meth) acrylate having 3 or more (meth) acryloyl groups in 1 molecule and having no hydroxyl group in the molecule, with or without a urethane bond; a non-fluorinated polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups and 1 or more hydroxyl groups in 1 molecule, and optionally containing a urethane bond; and a non-fluorinated polyfunctional urethane (meth) acrylate having a urethane bond in a molecule and having 6 or more (meth) acryloyl groups in 1 molecule, or a combination of 2 or more.
(C) The components can be used alone in 1 kind, or more than 2 kinds can be used together. In addition, in order to adjust the physical properties of the composition, fluorinated and non-fluorinated 1-functional (meth) acrylates may be added.
Further, the fluorine-containing active energy ray-curable composition of the present invention contains a photopolymerization initiator as the component (D), and thus can be a curable composition which can be easily cured by ultraviolet rays even in the presence of active energy rays. (D) The photopolymerization initiator as the component (B) is not particularly limited as long as it can cure the acrylic compound by ultraviolet irradiation, and examples thereof include acetophenone, benzophenone, 2-dimethoxy-1, 2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, and the like, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2- (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-benzoyl oxime) ], ethanone-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -1- (O-acetyloxime), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one, and the like, and these can be used alone in 1 kind, or 2 or more kinds can be used in combination.
The fluorine-containing active energy ray-curable composition according to one embodiment of the present invention contains the component (a), and is essentially characterized by imparting water-and oil-repellency, stain-proofing property, fingerprint resistance, abrasion durability and other properties to the surface after curing, and the amount of each component to be blended may be appropriately determined depending on the desired water-and oil-repellency, solubility of the composition, coating conditions, curing conditions, hardness of the obtained article, and the like, and may be set to any desired value
(A) Has the components of,
(A) Component (B) and component (B),
(A) Component (C) and component (C),
(A) Component (D) and component (D),
(A) Component (B), component (C),
(A) Component (C) and component (D),
(A) Component (B), component (C), and component (D),
And these are used in combination with other additives described later, if necessary, and a composition containing the components (a) and (B), and the components (C) and (D) is preferable.
In this case, the amount of component (B) to be added is preferably such that the molar ratio of the total of (meth) acryloyl groups contained in component (a) and component (B) to the hydroxyl groups contained in component (a) [ (total (mol) of meth) acryloyl groups)/hydroxyl groups (mol) ] becomes 0.2 to 19, as described above.
The amount of component (C) to be blended is not particularly limited, but is preferably 0.1 to 10000 parts by mass, more preferably 1 to 1000 parts by mass, and particularly preferably 5 to 800 parts by mass, in view of the ratio to the total of components (a) and (B). If the amount of the component (C) is too small, the coating properties and cured product properties expected by blending the component (C) may not be obtained, and if it is too large, the antifouling properties expected for the component (A) may not be obtained.
Further, the amount of component (D) to be blended is preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total amount of components (a), (B) and (C). If the amount of the component (D) is too small, curing failure may occur, and desired properties of the cured product may not be obtained, and if it is too large, defects may occur in the surface of the cured product, cloudiness may occur in the cured product, or coloring may be enhanced.
Further, various products have been sold by various companies in the case of an acrylic composition and a hard coating agent in which the component (D) is blended with the component (C). The fluorine-containing active energy ray-curable composition of the present invention may be a commercially available product to which the component (a) or the components (a) and (B) are added. Examples of commercially available hard coating agents include "ビームセット" of Ishikawa chemical industry, "ユービック" of Bridgman chemical industry, "UV コート" of オリジン electric industry, "カシュー UV" of カシュー, "デソライト" of JSR, "セイカビーム" of Dari refining industry, "Violet" of Japan synthetic chemistry, "canker" フジハード, "Mitsubishi rayon" ダイヤビーム, "Wucang paint" ウルトラバイン, "and" ユニディック "of DIC. When these commercially available compositions are used, the component (C) and the component (D) may be added as required.
[ other additives ]
The fluorine-containing active energy ray-curable composition of the present invention may further contain an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light-resistant stabilizer, a heat-resistant stabilizer, an antioxidant, a surfactant, a colorant, a filler, and the like, depending on the purpose. In addition, even when a commercially available hard coating agent is used as described above, an organic solvent, a polymerization inhibitor, an antistatic agent, an antifoaming agent, a viscosity modifier, a light stabilizer, a heat stabilizer, an antioxidant, a surfactant, a colorant, a filler, and the like can be blended depending on the purpose.
In addition, various inorganic fine particles such as reactive or non-reactive hollow or solid silica fine particles may be blended for improving various properties such as film strength, scratch resistance, transparency, and the like, and for improving properties such as adjustment of refractive index.
Examples of the organic solvent include alcohols such as 1-propanol, 2-propanol, isopropanol, n-butanol, isobutanol, t-butanol, and diacetone alcohol; ketones such as methyl propyl ketone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), and cyclohexanone; ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Propylene Glycol Monomethyl Ether (PGME), and propylene glycol monomethyl ether acetate; esters such as ethyl acetate, propyl acetate, butyl acetate and cyclohexyl acetate, fluorine-modified aromatic hydrocarbon solvents such as hexafluorom-xylene and benzylic trifluoro, and fluorine-modified ether solvents such as methyl perfluorobutyl ether. The organic solvent can be used alone in 1, also can be mixed with more than 2.
The amount of the organic solvent used is not particularly limited, but is preferably 50 to 10000 parts by mass, particularly preferably 80 to 1000 parts by mass, per 100 parts by mass of the total of the components (A) to (C).
In addition, as the polymerization inhibitor, antistatic agent, defoaming agent, viscosity modifier, light stabilizer, heat stabilizer, antioxidant, surfactant, colorant and filler, known ones can be used without particular limitation within the range not to impair the object of the present invention.
The method for curing the fluorine-containing active energy ray-curable composition of the present invention is not particularly limited, and a composition containing the component (a) alone, the component (a) and the component (B), the component (a) and the component (C), or the component (a), the component (B) and the component (C) may be diluted with a solvent and applied as appropriate, and the resultant may be cured by an active energy ray such as an electron beam, and in the case of further containing a photopolymerization initiator of the component (D), the composition may be cured by ultraviolet rays. In the case of curing by ultraviolet rays, ultraviolet irradiation can be performed in air, but in order to prevent curing inhibition by oxygen, it is preferable to control the oxygen concentration to 5000ppm or less, and it is particularly preferable to cure the resin in an inert gas atmosphere such as nitrogen, carbon dioxide, or argon.
When the resin composition is used as a coating layer of a substrate such as a film, a coating material for various articles, or the like, the component (C) and other additives can be freely blended depending on desired properties.
In addition, as a general use form of the fluorine-containing active energy ray-curable composition of the present invention, any substrate can be coated with the fluorine-containing active energy ray-curable composition layer of the present invention as long as it is closely adhered or bonded after curing, in particular, the resin substrate can be exemplified by resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetylcellulose, triacetylcellulose, acetylcellulosebutyrate, cellulose acetate propionate, cycloolefin polymer, cycloolefin copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, fluororesin, nylon, acrylic resin, and the like. They are in any form such as films, plates and molded members, and can be used on the surface thereof.
In addition, in the case of coating the film substrate, a pressure-sensitive adhesive may be coated on the surface opposite to the surface on which the fluorine-containing active energy ray-curable composition layer is coated and formed, and a release film for protecting the pressure-sensitive adhesive may be further provided.
The film base may be a base including only the resin film listed above, but a primer layer may be provided on the resin film to improve adhesion to the fluorine-containing active energy ray-curable composition of the present invention. Examples of the primer layer include primer layers made of polyester resin, polyurethane resin, acrylic resin, and the like.
The fluorine-containing active energy ray-curable composition of the present invention can be applied and cured to a layer of a curable composition which is not compatible with the present invention, and which is cured or uncured. For example, the fluorine-containing active energy ray-curable composition of the present invention can be applied to a cured product layer having higher hardness, durability, antistatic properties, and deformation preventing properties such as curling.
In order to improve the adhesion to the fluorine-containing active energy ray-curable composition of the present invention, the surface of the resin film may be subjected to a surface roughening treatment by sandblasting, solvent treatment, or the like, a corona discharge treatment, a chromic acid treatment, a flame treatment, a hot air treatment, ozone, an ultraviolet irradiation treatment, an oxidation treatment, or the like.
The method for applying the fluorine-containing active energy ray-curable composition of the present invention to the substrate or the article is not particularly limited, and for example, a known application method such as roll coating, gravure coating, flow coating, curtain coating, dip coating, spray coating, spin coating, bar coating, screen printing, or the like can be used.
After the coating, the coating film is cured by irradiation with active energy rays. Among them, as the active energy ray, any active energy ray such as an electron beam and ultraviolet ray can be used, and ultraviolet ray is particularly preferable. As the ultraviolet source, a mercury lamp, a metal halide lamp, and an LED lamp are preferable. The ultraviolet irradiation amount is preferably 10 to 10000mJ/cm because if it is too small, uncured components remain, and if it is too large, the coating film and the substrate may be deteriorated2Particularly preferably in the range of 100 to 4000mJ/cm2The range of (1).
In order to prevent the inhibition of curing by oxygen, the irradiation atmosphere may be replaced with an inert gas containing no oxygen molecule, such as nitrogen, carbon dioxide, or argon, or the surface of the coating film may be covered with a protective layer having ultraviolet permeability and having releasability and irradiated with ultraviolet rays, or the surface of the coating film may be covered with a protective layer having releasability and irradiated with ultraviolet rays from the opposite side of the coated surface of the substrate in the case where the substrate has ultraviolet permeability. In addition, in order to efficiently perform leveling of the coating film or polymerization of the (meth) acryloyl group in the coating film, the coating film and the substrate may be heated by any method such as an infrared ray or a hot air drying oven before and during ultraviolet irradiation.
The thickness of the cured product layer of the thus obtained fluorine-containing active energy ray-curable composition is not particularly limited, but is preferably 0.01 to 5,000 μm, and particularly preferably 0.05 to 200 μm.
The cured product layer of the fluorine-containing active energy ray-curable composition of the present invention obtained in this way is preferably a water-and oil-repellent surface in which a 2 μ L droplet of ion-exchanged water has a static water contact angle of 100 ° or more, particularly 105 ° or more, as measured from the angle formed by the liquid surface and the solid surface after 1 second from the contact with the liquid, and a static oleic acid contact angle of 60 ° or more, particularly 65 ° or more, as measured from the angle formed by the liquid surface and the solid surface after 1 second from the contact with the liquid. In order to obtain the contact angle, the cured product layer of the fluorine-containing active energy ray-curable composition of the present invention is preferably formed in an amount of 10nm or more on average relative to the total surface area of the cured product layer. Further, the more the surface of the cured product layer is free from unreacted (meth) acryloyl groups, the more preferable is the one obtained by curing the (meth) acryloyl groups in an inert gas atmosphere such as nitrogen or carbon dioxide.
As described above, the fluorine-containing active energy ray-curable composition of the present invention can be cured by an active energy ray such as ultraviolet ray, and can form a cured resin layer excellent in water-and oil-repellency, stain-proofing property, slidability, and abrasion resistance on the surface of an article.
Further, the present invention provides an article having a cured coating film obtained by applying and curing the above-described fluorine-containing active energy ray-curable composition of the present invention on a surface thereof. As described above, if the fluorine-containing active energy ray-curable composition of the present invention is used, it becomes possible to form a cured film (cured resin layer) having excellent surface characteristics on the surface of a substrate (article). In particular, it is useful for imparting water repellency, oil repellency, and stain resistance to the surface of an acrylic hard coat layer. This makes it difficult for fingerprints, sebum, human fats such as sweat, dirt generated from cosmetics, mechanical oil, and the like to adhere to the hard coat layer, and can impart a hard coat layer surface having excellent wiping properties to the substrate. Therefore, the fluorine-containing active energy ray-curable composition of the present invention can provide an antifouling coating film or a protective film on the surface of a substrate (article) which may be contaminated with human body fat, cosmetics, or the like by human contact, or a process material film or the like used in a machine which may be contaminated with human body fat, machine oil, or the like by an operator.
The cured coating (cured resin layer) formed using the fluorine-containing active energy ray-curable composition of the present invention can be used as a case of various devices such as a tablet computer, a portable (communication) information terminal such as a notebook PC, a mobile phone, and a smartphone, a digital media player, and an electronic book reader, and a watch-type and glasses-type wearable computer; display operation equipment surfaces of various flat panel displays such as liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear projection displays, fluorescent display tubes (VFDs), field emission projection displays, CRTs, toner-based displays, and screens of TVs, various optical films used in the interior of these, exterior of automobiles, gloss surfaces of pianos and furniture, surfaces of building stones such as marble, toilets, bathtubs, decorative building materials for water use places such as restrooms, protective glass for art exhibition, showcases, front covers for picture frames, watches, window glass for automobiles, window glass for trains and aircrafts, transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members such as automobile headlamps and tail lamps, and coating films and surface protective films for various mirror members.
Among them, various devices having a display input device which can be used as a touch panel display or the like for performing an operation on a screen with a human finger or palm, for example, surface protective films of a tablet computer, a notebook PC, a smart phone, a mobile phone, another portable (communication) information terminal, a smart watch, a digital media player, an electronic book reader, a digital photo frame, a game machine, a digital camera, a digital video camera, a GPS display recording device, a navigation device for automobiles or the like, a control panel for automobiles or the like, an automatic cash dispensing and storing device, a cash automatic payment machine, an automatic vending machine, a digital signboard (electronic signboard), a security system terminal, various controllers such as a POS terminal and a remote controller, a display input device such as a panel switch for an in-vehicle device, and the like.
Furthermore, the cured coating film formed by using the fluorine-containing active energy ray-curable composition of the present invention can also be used as an optical recording medium such as a magneto-optical disk and an optical disk; a surface protective film for optical components such as spectacle lenses, prisms, lens sheets, surface films, polarizing plates, optical filters, lenticular lenses, fresnel lenses, antireflection films, various camera lenses, various protective filters for lenses, optical fibers, and optical couplers, and optical devices.
The fluorine-containing active energy ray-curable composition of the present invention as described above has excellent properties such as water repellency, oil repellency, slidability, stain resistance, resistance to fingerprint development, fingerprint peelability, abrasion resistance, low refractive index characteristics, solvent resistance, and chemical resistance, and is essentially characterized by being prepared by disposing the perfluoropolyether structure of the fluorine-containing compound (a) of the present invention on the surface of a target article.
When the fluorine-containing active energy ray-curable composition of the present invention is used, an appropriate method of use can be selected based on known techniques suitable for various applications, depending on the combination of compounds, the composition ratio, and which properties are regarded as important. Such known techniques include not only techniques for fluorine-containing compositions but also methods used in conventional active energy ray-curable compositions, and can be included in the scope of research.
For example, when the fluorine-containing active energy ray-curable composition of the present invention is prepared by compounding, in addition to the fluorine-containing compound (a) of the present invention, when various compounds in the above-described present curable composition are combined, in the case where low refractive index characteristics are regarded as important and low reflection characteristics thereof are utilized, reactive hollow silica, hollow silica having no reactive group, a polyfunctional acrylic compound are used; further, when the film strength and scratch resistance are improved, a polyfunctional acrylic compound is blended in an appropriate amount; or a combination of a multifunctional acrylic compound having 6 or more functions and an acrylic compound having 3 or less functions in order to balance the hardness and bendability, and the like, can be easily inferred from the knowledge that a known acrylic curable composition is compounded.
In addition, in the case of obtaining an article by applying the fluorine-containing active energy ray-curable composition of the present invention, for example, in the case of applying a film base material, adjustment is made to an appropriate coating film thickness in order to prevent interference fringes; the thickness of the film base is adjusted so as to easily suppress curling, or the elastic modulus of the base film is adjusted so as to suppress deformation of the coating film of the fluorine-containing active energy ray-curable composition after curing, cracks of the coating film, and the like, and the thickness can be easily realized by a combination of conventional techniques by selecting the thickness based on a combination of conventional conditions suitable for each characteristic.
Examples
The present invention will be described in more detail below by way of synthetic examples, examples and comparative examples, but the present invention is not limited to the following examples.
Synthesis example 1 Synthesis of fluorine-containing acrylic Compound (A-1)
Under the dry air atmosphere, the reaction is carried out under the reaction condition of the following formula
[ solution 49]
Rf1:-CF2O(CF2O)p1(CF2CF2O)q1CF2-
(q1/p1=0.9、p1+q1≈45)
50.0g of methyl ethyl ketone and 1.34g (0.00950 moles) of acryloyloxyethyl isocyanate were mixed with 50.0g (0.056 mole in the amount of hydroxyl group) of the fluorinated alcohol compound (E-1) shown above, and the mixture was heated to 50 ℃ and stirred for 1 hour. To this was added 0.05g of dioctyltin dilaurate, and the mixture was stirred at 50 ℃ for 8 hours. By1As a result of H-NMR, it was confirmed that all of the methylene peaks at 4.2ppm of acryloyloxyethyl isocyanate unreacted were urine4.1ppm methylene peak after alkane bond formation, and 2260cm was confirmed by IR spectrum-1Disappearance of the peak of the isocyanate group (2). After the completion of the heating, the obtained reaction solution was treated with activated carbon, and the obtained pale yellow liquid was treated with an evaporator at 80 ℃/133Pa for 2 hours, whereby 47.2g of a fluorine-containing acrylic compound (a-1) as a pale yellow highly viscous substance having an acryloyl/hydroxyl group content of 0.20 represented by the following formula was obtained.
[ solution 50]
Rf1:-CF2O(CF2O)p1(CF2CF2O)q1CF2-
(q1/p1=0.9、p1+q1≈45)
Synthesis example 2 Synthesis of fluorine-containing acrylic Compound (A-2)
The same procedures were carried out except for using 2.64g (0.0187 mol) of acryloyloxyethyl isocyanate in synthesis example 1 to obtain 48.0g of a fluorine-containing acrylic compound (a-2) as a pale yellow highly viscous substance having an acryloyl group/hydroxyl group content of 0.5.
Synthesis example 3 Synthesis of fluorine-containing acrylic Compound (A-3)
The same procedures were carried out except for using 7.50g (0.0532 moles) of acryloyloxyethyl isocyanate in synthesis example 1 to obtain 52.8g of a fluorine-containing acrylic compound (a-3) as a pale yellow highly viscous substance having an acryloyl group/hydroxyl group content of 19.
Synthesis example 4 Synthesis of fluorine-containing acrylic Compound (A-4)
Under the dry air atmosphere, the reaction is carried out under the reaction condition of the following formula
[ solution 51]
Rf2:-CF2O(CF2O)p2(CF2CF2O)q2CF2-
(q2/p2=1.2、p2+q2≈18.5)
50.0g of methyl ethyl ketone and 4.61g (0.0327 mol) of acryloyloxyethyl isocyanate were mixed with 50.0g (0.098 mol in terms of hydroxyl group content) of the fluorinated alcohol compound (E-2) shown above, and the mixture was heated to 50 ℃ and stirred for 1 hour. To this was added 0.10g of dioctyltin dilaurate, and the mixture was stirred at 50 ℃ for 8 hours. By1As a result of H-NMR, it was confirmed that all of the methylene peaks at 4.2ppm of the unreacted acryloyloxyethyl isocyanate were 4.1ppm after urethane bond formation, and that 2260cm was confirmed by IR spectrum-1Disappearance of the peak of the isocyanate group (2). After the completion of the heating, the obtained reaction solution was treated with activated carbon, and the obtained pale yellow liquid was treated with an evaporator at 60 ℃/133Pa for 2 hours, whereby 50.8g of a fluorine-containing acrylic compound (a-4) as a pale yellow highly viscous substance having an acryloyl/hydroxyl group content of 0.5 represented by the following formula was obtained.
[ solution 52]
Rf2:-CF2O(CF2O)p2(CF2CF2O)q2CF2-
(q2/p2=1.2、p2+q2≈18.5)
Synthesis example 5 Synthesis of fluorine-containing acrylic Compound (B-1)
The same operation was carried out with the exception that the amount of acryloyloxyethyl isocyanate used in Synthesis example 1 was 8.59g (0.0609 mol)13The disappearance of 62ppm of the peak derived from the carbon atom adjacent to the hydroxyl group was confirmed by C-NMR spectrum, whereby 53.0g of the fluorine-containing acrylic compound (B-1) was obtained as a pale yellow highly viscous substance without remaining hydroxyl groups represented by the following formula.
[ Hua 53]
Rf1:-CF2O(CF2O)p1(CF2CF2O)q1CF2-
(q1/p1=0.9、p1+q1≈45)
[ Synthesis example 6] Synthesis of fluorine-containing acrylic Compound (B-2)
The same operation was carried out with the exception that the amount of acryloyloxyethyl isocyanate used in Synthesis example 4 was changed to 15.1g (0.107 mol)13The disappearance of 62ppm of the peak derived from the carbon atom adjacent to the hydroxyl group was confirmed by C-NMR spectrum, whereby 58.9g of a fluorine-containing acrylic compound (B-2) was obtained as a pale yellow highly viscous substance without remaining hydroxyl groups represented by the following formula.
[ solution 54]
Rf2:-CF2O(CF2O)p2(CF2CF2O)q2CF2-
(q2/p2=1.2、p2+q2≈18.5)
Examples 1 to 7 and comparative examples 1 to 5
Preparation of fluorine-containing active energy ray-curable composition
The compounds (A-1) to (A-4), (B-1) and (B-2) obtained in the above synthesis examples were mixed with the acrylic compounds (C-1) to (C-4) shown below, the photopolymerization initiators (D-1) and (D-2), and the organic solvents (S-1) to (S-4) shown below at the compounding ratios shown in tables 1 and 2 below to prepare fluorine-and non-fluorine-containing active energy ray-curable compositions. Further, the theoretical value of the total molar amount of acryloyl groups contained in component (A) and component (B) of each composition is represented by NAThe theoretical value of the molar amount of hydroxyl groups is NHN in each compositionA/NHThe values of (b) are shown in tables 1 and 2 below.
(C-1): pentaerythritol triacrylate (number of acryloyl groups: 3, number of hydroxyl groups: 1 in molecule)
(C-2): a mixture of dipentaerythritol pentaacrylate (number of acryloyl groups: 5 and number of hydroxyl groups: 1 in molecule)/dipentaerythritol hexaacrylate (number of acryloyl groups: 6 and number of hydroxyl groups: 0 in molecule)
(C-3): multifunctional urethane acrylate "U-6 LPA" (the number of acryl groups in the molecule: 6 or more) manufactured by Mitsumura chemical Co., Ltd.)
(C-4): multifunctional urethane acrylate "UN-3320 HS" (the number of acryloyl groups in the molecule: 6 or more) manufactured by Kokusha Kogyo Co., Ltd
(D-1): 1-hydroxy-cyclohexyl-phenyl-ketones
(D-2): 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] phenyl } -2-methyl-propan-1-one
(S-1): methyl ethyl ketone
(S-2): acetic acid ethyl ester
(S-3): propylene glycol monomethyl ether
(S-4): 2-propanol
Fabrication of coated and cured films
The active energy ray-curable compositions of examples and comparative examples were each coated on a polycarbonate substrate by spin coating. The coated surface was irradiated with a cumulative irradiation amount of 1600mJ/cm in a nitrogen atmosphere using a conveyor type metal halide UV irradiation apparatus (manufactured by Sonk electric Co., Ltd.)2The composition was cured by the ultraviolet ray of (2), to obtain a cured film having a thickness of about 5 μm and about 3 μm for example 5.
Evaluation of cured film
The cured films obtained above were subjected to measurement of water contact angle and oleic acid contact angle, and evaluation of abrasion resistance, fingerprint resistance and all-purpose pen resistance by the methods shown below. The results are shown in tables 3 and 4.
[ measurement of Water contact Angle ]
A2. mu.L drop was dropped on the cured film using a contact angle meter (DropMaster, manufactured by Kyowa Kagaku K.K.), and the contact angle after 1 second was measured. The average value of N-5 was used as the measurement value.
[ measurement of oleic acid contact Angle ]
A4. mu.L drop was dropped on the cured film using a contact angle meter (DropMaster, manufactured by Kyowa Kagaku K.K.), and the contact angle after 1 second was measured. The average value of N-5 was used as the measurement value.
[ abrasion resistance ]
The reciprocal abrasion test was performed under the following conditions, and the number of times the water contact angle was 100 ° or less was recorded every 2000 times.
Friction material: nonwoven (BEMCOT M-3II, manufactured by Xuhua chemical Co., Ltd.)
Loading: 1kg of
Contact area: 3cm2
Friction speed: 90mm/s
Friction distance: 20mm
[ evaluation of easy visibility of fingerprint ]
The ease of visibility when a fingerprint was attached was visually evaluated by the following criteria.
1: are difficult to be obviously
2: is slightly hard to be obvious
3: same as in comparative example 1
[ evaluation of easy Erasure of fingerprint ]
The ease of wiping when wiping a fingerprint tissue was evaluated visually with the following criteria.
O: can be easily erased
X: can not be erased
[ evaluation of repellency of Universal Pen ]
A straight line was drawn on the surface of the cured film with a universal pen (ハイマッキー T manufactured by ゼブラ K.), and the case of repelling ink was marked as "O" and the case of not repelling ink was marked as "X".
[ evaluation of Erasing Property with Universal Pen ]
Each sample used for evaluation of the universal pen repellency was erased with a facial tissue after 10 minutes, and the case of erasing without leaving any mark was marked as o, and the case of leaving any mark was marked as x.
[ Table 1]
[ Table 2]
[ Table 3]
Test items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 |
Water contact angle [ ° ]] | 110 | 112 | 113 | 113 | 112 | 111 | 111 |
Oleic acid contact Angle [ ° ]] | 73 | 73 | 72 | 72 | 73 | 72 | 71 |
Abrasion resistance] | 14,000 | 12,000 | 8,000 | 8,000 | 14,000 | 8,000 | 6,000 |
The fingerprints are easy to be obvious | 1 | 1 | 2 | 1 | 2 | 1 | 1 |
Easy fingerprint erasability | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
Universal pen repellency | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
Easy erasability of universal pen | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
[ Table 4]
Test items | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
Water contact angle [ ° ]] | 113 | 113 | 112 | 111 | 60 |
Oleic acid contact Angle [ ° ]] | 73 | 72 | 72 | 72 | 21 |
Abrasion resistance] | 6,000 | 6,000 | 8,000 | 4,000 | -* |
The fingerprints are easy to be obvious | 3 | 3 | 3 | 3 | 2 |
Easy fingerprint erasability | ○ | ○ | ○ | ○ | × |
Universal pen repellency | ○ | ○ | ○ | ○ | × |
Easy erasability of universal pen | ○ | ○ | ○ | ○ | × |
*: before the test, the water contact angle was 100 ℃ or less, and therefore no test was conducted
From the above results, it is understood that examples 1 to 7 using the fluorine-containing active energy ray-curable composition of the present invention obtained by blending the fluorine-containing acrylic compounds (A-1) to (A-4) are excellent in water repellency, oil repellency, abrasion resistance, resistance to conspicuous fingerprints, easy fingerprint erasure, universal pen repellency, and universal pen erasure. In comparative examples 1 to 4 using the fluorine-containing active energy ray-curable composition obtained by blending the fluorine-containing acrylic compound (a) and the fluorine-containing acrylic compounds (B-1) and (B-2), the abrasion resistance was inferior to those of the corresponding examples, and the fingerprint was clear. Further, in comparative example 5 using a non-fluorine active energy ray-curable composition containing neither the fluorine-containing acrylic compounds (A-1) to (A-4) nor the fluorine-containing acrylic compounds (B-1) and (B-2), the water repellency, oil repellency, abrasion resistance, easy erasure of fingerprints, universal pen repellency, and universal pen erasure were inferior to those of the above examples.
Claims (11)
1. A fluorine-containing active energy ray-curable composition which is characterized by containing a fluorine-containing compound (A) having a cyclic polysiloxane structure bonded to both ends of a 2-valent perfluoropolyether group via a 2-valent linking group, and having a hydroxyl group bonded to the cyclic polysiloxane structure via a 2-valent linking group and a (meth) acryloyl group bonded to the cyclic polysiloxane structure via a 2-valent linking group, in either or both of the cyclic polysiloxane structures at both ends.
2. The fluorine-containing active energy ray-curable composition according to claim 1, wherein a molar ratio of (meth) acryloyl groups to hydroxyl groups contained in the fluorine-containing compound (A) [ (meth) acryloyl groups (moles)/hydroxyl groups (moles) ] in the fluorine-containing compound (A) is 0.1 or more and 25 or less on average.
3. The fluorine-containing active energy ray-curable composition according to claim 1 or 2, further comprising a fluorine-containing compound (B) having a cyclic polysiloxane structure bonded to both ends of the 2-valent perfluoropolyether group via a 2-valent linking group, and having the following structure at both ends: has a (meth) acryloyl group bonded to the cyclic polysiloxane structure via a 2-valent linking group and has no hydroxyl group.
4. The fluorine-containing active energy ray-curable composition according to claim 3, wherein a molar ratio of the total of (meth) acryloyl groups contained in the fluorine-containing compound (A) and (meth) acryloyl groups contained in the fluorine-containing compound (B) to hydroxyl groups contained in the fluorine-containing compound (A) [ (total (mol) of meth) acryloyl groups)/hydroxyl groups (mol) ] is 0.1 or more and 25 or less, on an average value contained in the entire composition.
5. The fluorine-containing active energy ray-curable composition according to any one of claims 1 to 4, wherein the fluorine-containing compound (A) is represented by the following general formula (1):
X1-Z-Rf-Z-X1(1)
wherein Rf is a 2-valent perfluoropolyether group having a molecular weight of 500 to 30000 selected from the group represented by the following formulae (2) to (5), and X1Independently of each other, a group represented by the following formula (6),
[ solution 1]
In which Y are independent of each otherGround is F or CF3R is an integer of 2 to 6, m and n are each an integer of 0 to 200, m + n is 2 to 200, s is an integer of 0 to 6, and the repeating units may be randomly combined,
[ solution 2]
-CjF2j(OCF2CF2CF2)kOCjF2j- (3)
Wherein j is independently an integer of 1 to 3, k is an integer of 1 to 200,
[ solution 3]
Wherein Y, j is the same as above, p and q are each an integer of 0 to 200, p + q is 2 to 200, and the repeating units may be randomly combined,
[ solution 4]
-(CF2CF2O-CF2CF2CF2CF2O)tCF2- (5)
Wherein t is an integer of 1 to 100,
[ solution 5]
In the formula, Q1A linking group having 3 to 20 carbon atoms and having a valence of 2 and comprising a bond selected from the group consisting of an ether bond, an ester bond, an amide bond and a urethane bond, and having a cyclic structure or a branched structure in the middle, wherein R may be the same or different1A group containing a (meth) acryloyl group represented by the following formula (7), a and b are each an integer of 0 to 6, a + b is 2 to 11, and repeating units may be randomly combined,
[ solution 6]
In the formula, R2Independently is a hydrogen atom or a methyl group, R3A 2-or 3-valent linking group having 1 to 18 carbon atoms and containing an ether bond and/or an ester bond, c is 1 or 2,
x present in the molecule1Wherein a and b are each 2 or more in total, and Z is represented by the following formula
[ solution 7]
[ solution 8]
[ solution 9]
[ solution 10]
[ solution 11]
-CH2-O-CH2-
[ solution 12]
-CH2-CH2-
[ solution 13]
[ solution 14]
[ solution 15]
[ solution 16]
Any one of (a) and (b) represents a 2-valent organic group.
6. The fluorine-containing active energy ray-curable composition according to any one of claims 1 to 5, further comprising an acrylic compound (C) other than the fluorine-containing compounds (A) and (B).
7. The fluorine-containing active energy ray-curable composition according to claim 6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in 1 molecule and having no hydroxyl group in the molecule.
8. The fluorine-containing active energy ray-curable composition according to claim 6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups and 1 or more hydroxyl groups in 1 molecule.
9. The fluorine-containing active energy ray-curable composition according to claim 6, wherein the acrylic compound (C) is a non-fluorinated polyfunctional urethane (meth) acrylate having a urethane bond in a molecule and having 6 or more (meth) acryloyl groups in 1 molecule.
10. The fluorine-containing active energy ray-curable composition according to any one of claims 1 to 9, further comprising (D) a photopolymerization initiator.
11. An article having a water-repellent surface with a water contact angle of 105 ° or more, the article having a cured coating film of the fluorine-containing active energy ray-curable composition according to any one of claims 1 to 10 on the surface thereof.
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