CN113439095A - Fluorine-containing curable composition and article - Google Patents
Fluorine-containing curable composition and article Download PDFInfo
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- CN113439095A CN113439095A CN202080014883.5A CN202080014883A CN113439095A CN 113439095 A CN113439095 A CN 113439095A CN 202080014883 A CN202080014883 A CN 202080014883A CN 113439095 A CN113439095 A CN 113439095A
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- fluorine
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 170
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 239000011737 fluorine Substances 0.000 title claims abstract description 165
- 239000000203 mixture Substances 0.000 title claims abstract description 112
- -1 fluorinated acrylic compound Chemical class 0.000 claims abstract description 199
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 85
- 150000001875 compounds Chemical class 0.000 claims abstract description 80
- 239000011248 coating agent Substances 0.000 claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims description 46
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 29
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- 125000004430 oxygen atom Chemical group O* 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 claims description 15
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 15
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- 125000000217 alkyl group Chemical group 0.000 claims description 4
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- 229920001601 polyetherimide Polymers 0.000 description 1
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- 239000011241 protective layer Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
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- 150000003606 tin compounds Chemical class 0.000 description 1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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- 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
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- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/18—Esters containing halogen
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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Abstract
A fluorine-containing curable composition containing the following component (A), component (B) and component (C) in predetermined mixing ratios can form a cured coating film having excellent stain resistance and water repellency and a low coefficient of dynamic friction: the component (A) is a linear polymer having a fluoropolyether in the main chain and is composed of a compound having 1 or 2 (meth) acryloyl groups at one or both ends of the molecular chain, the average number of the (meth) acryloyl groups contained in 1 molecule is 2 or less, and the fluorine content is 48 mass% or more and less than 62 mass%, the component (B) is composed of a compound having 2 or more (meth) acryloyl groups at each molecular chain end in 1 molecule of the linear polymer having a fluoropolyether in the main chain, the average number of the (meth) acryloyl groups in 1 molecule is 4 to 10 (meth) acryloyl groups, and the fluorine content is 25 mass% or more and less than 45 mass%, and the component (C) is composed of a non-fluorinated acrylic compound having no fluoropolyether structure and 2 or more (meth) acryloyl groups in 1 molecule on average.
Description
Technical Field
The present invention relates to a fluorine-containing curable composition having excellent antifouling properties and sliding properties, and an article having a cured coating film of the composition on the 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 the molded article is hard to be scratched. As a material constituting the hard coat layer, a curable composition using an active energy ray such as a thermosetting resin, an ultraviolet or electron beam curable resin, or the like is used in a large amount.
On the other hand, with the expansion of the field of use of resin molded products and the trend toward higher added value, 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 property to the hard coat layer. This is to impart water repellency, oil repellency, and the like to the surface of the hard coat layer, thereby making it less likely to be contaminated or enabling easy removal 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 curable resin composition before curing and applying and curing the curable resin composition has also been studied. For example, japanese patent laying-open No. 6-211945 (patent document 1) discloses the production of a hard coat layer having antifouling properties imparted thereto by adding a fluoroalkyl acrylate to an acrylic curable resin composition and curing the mixture.
In recent years, the use of active energy ray-curable compositions containing such fluorine-containing acrylic compounds and having excellent antifouling properties has been greatly expanded, and new functions have been required.
With such a wide range of applications, in hard coatings, particularly, in antifouling treatment of surfaces of large-sized displays and surface treatment of displays and housings of portable information devices such as smart phones and tablet personal computers, higher performance is required for antifouling performance represented by water repellency and abrasion resistance represented by slidability. One means of meeting these requirements is to align the components with a high degree of fluorine modification on the surface. However, if the fluorine content is increased by using a fluorine-containing acrylic compound having a single structure, the solubility in other components of the nonfluorinated hard coating agent is lowered, and coating defects are caused by uneven portions such as defects on the coating surface.
As a prior art related to the present invention, the following documents are listed together with the above documents.
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 thereof is to provide a fluorine-containing curable composition having stable solubility, high antifouling property after curing, and high sliding property, and an article having a cured coating film of the composition on the surface.
Means for solving the problems
The present inventors have variously developed a fluorine compound capable of imparting antifouling properties to such a curable resin composition, and for example, proposed photocurable fluorine compounds shown in japanese patent laid-open nos. 2010-53114 (patent document 2), 2010-138112 (patent document 3) and 2010-285501 (patent document 4). In order to improve the antifouling property and the sliding property, a method of increasing the content of the fluorine component in the compound is considered. However, when the solubility in the non-fluorinated component is improved by the fluorine-containing acrylic compound having a single structure as described above, the concentration of the fluorine component on the coating surface is difficult to occur, and as a result, it is sometimes difficult to develop the antifouling performance.
Therefore, the present inventors have further studied and found that: a curable fluorine-containing composition containing the following component (A), component (B) and component (C) in predetermined mixing ratios can form a cured coating film having excellent stain resistance and water repellency and a low coefficient of dynamic friction, and the present invention has been completed,
the component (A) is a linear polymer having a fluoropolyether in the main chain, and is composed of a compound having 1 or 2 (meth) acryloyl groups at the end, the average value of the number of (meth) acryloyl groups contained in 1 molecule being 2 or less, and the fluorine content being 48 mass% or more and less than 62 mass%;
the component (B) is composed of a compound having 2 or more (meth) acryloyl groups at each end of 1 molecule of a linear polymer having a fluoropolyether in the main chain, having 4 to 10 (meth) acryloyl groups on average in 1 molecule, and having a fluorine content of 25 mass% or more and less than 45 mass%;
the component (C) is composed of a non-fluorinated acrylic compound having no fluoropolyether structure and having an average of 2 or more (meth) acryloyl groups in 1 molecule.
Accordingly, the present invention provides the following fluorine-containing curable composition and an article having a cured coating film of the composition on the surface.
[1] A fluorine-containing curable composition comprising a component (A), a component (B) and a component (C) as essential components, wherein the total amount of the component (A) and the component (B) is 0.05 to 50 parts by mass per 100 parts by mass of the component (C), the amount of the component (A) to be blended per 100 parts by mass of the component (B) is 1 to 100 parts by mass, the component (A) is composed of a compound having 1 or 2 (meth) acryloyl groups at one or both ends of a molecular chain, which is a linear polymer having a fluoropolyether in the main chain, the average number of (meth) acryloyl groups contained in 1 molecule is 2 or less, and the fluorine content is 48% or more and less than 62% by mass, and the component (B) is composed of a compound having 2 or more (meth) acryloyl groups at each molecular chain end in 1 molecule of a linear polymer having a fluoropolyether in the main chain, A compound having 4 to 10 (meth) acryloyl groups on average in 1 molecule and a fluorine content of 25 mass% or more and less than 45 mass%, and the component (C) is composed of a non-fluorinated acrylic compound having no fluoropolyether structure and having 2 or more (meth) acryloyl groups on average in 1 molecule.
[2] [1] the fluorine-containing curable composition further contains a photopolymerization initiator (D).
[3] [1] the fluorine-containing curable composition according to [1] or [2], wherein the component (A) is a fluorine-containing acrylic compound represented by any one of the following general formulae (1) or (2).
Rf1-O-Rf2-CF2-Z1-X1 (1)
X2-Z1-CF2O-Rf2-CF2-Z1-X1 (2)
(wherein Rf1Is a fluorine atom or a C1-8 fluorine-containing alkyl group which may contain an oxygen atom, Rf2The following 2 kinds of repeating units
-CF2O-
-CF2CF2O-
Randomly arranged perfluoropolyether groups having a molecular weight of 600 to 20000 and a valence of 2. Z1And a linking group selected from among a 2-valent hydrocarbon group having 1 to 20 carbon atoms, which may contain at least 1 heteroatom selected from an oxygen atom, a nitrogen atom and a silicon atom, -C (═ O) -and-C (═ O) O-, wherein the 2-valent hydrocarbon group may contain a cyclic structure in the middle, and a part of hydrogen atoms bonded to the carbon atoms may be substituted with fluorine atoms. X1Independently is a 1-valent organic group having a (meth) acryloyl group which may contain an oxygen atom and/or a nitrogen atom, X2Is hydroxy or X1。)
[4] The fluorine-containing curable composition according to any one of [1] to [3], wherein the component (B) is a fluorine-containing acrylic compound represented by the following general formula (3).
[ solution 1]
(wherein Rf2Is the following 2 kinds of repeat unitsYuan
-CF2O-
-CF2CF2O-
Randomly arranged perfluoropolyether groups having a molecular weight of 600 to 20000 and a valence of 2. Q1Independently a (a +1) -valent linking group containing at least (a +1) silicon atoms, may form a cyclic structure. a is an integer of 2 to 5. Z2Each independently is a C1-100 (C2) -valent hydrocarbon group which may contain an oxygen atom and/or a nitrogen atom and may contain a cyclic structure in the middle. R1Independently a hydrogen atom or a C1-C8 hydrocarbon group. R2Independently a hydrogen atom, or an organic group having a valence of 1 of a (meth) acryloyl group which may contain an oxygen atom and/or a nitrogen atom, however, R2The organic group has 2 or more at each end of 1 molecule and has 4 to 10 valences of 1 in the molecule on average. Z3Independently, the linking group is a 2-valent hydrocarbon group having 1 to 20 carbon atoms, which may contain at least 1 hetero atom selected from an oxygen atom, a nitrogen atom and a silicon atom, and may contain a cyclic structure in the middle, and a part of hydrogen atoms bonded to carbon atoms may be substituted with fluorine atoms. )
[5][3]Or [4]]The fluorine-containing curable composition, wherein, in the component (A), Z in the general formula (1) or (2)1Any one of the following structures is provided.
-C(＝O)-
-C(＝O)O-
-C(＝O)OCH2-
-C(＝O)OCH2CH2-
-CH2-
-CH2O-
-CH2OCH2-
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OC(＝O)NH-
-CH2OC(＝O)NHCH2CH2-
[6][3]～[5]The fluorine-containing curable composition according to any one of the above, wherein, in the component (A), X in the general formula (1) or (2)1Is represented by any one of the following.
-OC(＝O)CH＝CH2
-OC(＝O)C(CH3)＝CH2
-C[OC(＝O)CH＝CH2]2
-C[OC(＝O)C(CH3)＝CH2]2
-CH[CH2OC(＝O)CH＝CH2][CH2OC(＝O)C(CH3)＝CH2]
-C(CH3)[CH2OC(＝O)CH＝CH2]2
-CH2[CH2OC(＝O)C(CH3)＝CH2]2
-C[CH2OC(＝O)CH＝CH2]
-C(CH2CH3)[CH2OC(＝O)CH＝CH2]2
-C(CH2CH3)[CH2OC(＝O)C(CH3)＝CH2]2。
[7] The fluorine-containing curable composition according to any one of [3] to [6], wherein the fluorine-containing acrylic compound represented by the general formula (1) or (2) in the component (A) is represented by any one of the following.
Rf1ORf2CF2CH2OC(＝O)CH＝CH2
Rf1ORf2CF2CH2OC(＝O)C(CH3)＝CH2
HOCH2CF2ORf2CF2CH2OC(＝O)CH＝CH2
HOCH2CF2ORf2CF2CH2OC(＝O)C(CH3)＝CH2
Rf1ORf2CF2C(＝O)OCH2CH2OC(＝O)CH＝CH2
Rf1ORf2CF2C(＝O)OCH2CH2OC(＝O)C(CH3)＝CH2
HOCH2CF2ORf2CF2C(＝O)OCH2CH2OC(＝O)CH＝CH2
HOCH2CF2ORf2CF2C(＝O)OCH2CH2OC(＝O)C(CH3)＝CH2
Rf1ORf2CF2C(＝O)OCH[CH2OC(＝O)CH＝CH2][CH2OC(＝O)C(CH3)＝CH2]
Rf1ORf2CF2CH2OC(＝O)NHCH2CH2OC(＝O)CH＝CH2
Rf1ORf2CF2CH2OC(＝O)NHCH2CH2OC(＝O)C(CH3)＝CH2
HOCH2CF2ORf2CF2CH2OC(＝O)NHCH2CH2OC(＝O)CH＝CH2
HOCH2CF2ORf2CF2CH2OC(＝O)NHCH2CH2OC(＝O)C(CH3)＝CH2
HOCH2CF2ORf2CF2CH2OC(＝O)NHC(CH3)[CH2OC(＝O)CH＝CH2]2
CH2＝C(CH3)C(＝O)OCH2CF2ORf2CF2CH2OC(＝O)C(CH3)＝CH2
CH2＝CHC(＝O)OCH2CF2ORf2CF2CH2OC(＝O)C(CH3)＝CH2
CH2＝CHC(＝O)OCH2CF2ORf2CF2CH2OC(＝O)CH＝CH2
CH2＝CHC(＝O)OCH2CH2NHC(＝O)OCH2CF2ORf2CF2CH2OCH2OC(＝O)CH＝CH2
CH2＝C(CH3)C(＝O)OCH2CH2NHC(＝O)OCH2CF2ORf2CF2CH2OCH2OC(＝O)C(CH3)＝CH2
CH2＝CHC(＝O)OCH2CH2NHC(＝O)OCH2CF2ORf2CF2CH2OC(＝O)NHCH2CH2OC(＝O)CH＝CH2
(wherein Rf1、Rf2As described above. )
[8][4]～[7]The fluorine-containing curable composition according to any one of the above, wherein, in the component (B), Z in the general formula (3)3Represented by any one of the following formulae.
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OCH2CH2-
-CH2OCH2CH2CH2-
[9][4]～[8]The fluorine-containing curable composition according to any one of the above, wherein Q in the general formula (3) is Q in the component (B)1Represented by the following formula.
[ solution 2]
(wherein a1 represents 2 or 3.)
[10] The fluorine-containing curable composition according to any one of [4] to [9], wherein the fluorine-containing acrylic compound represented by the general formula (3) in the component (B) is a fluorine-containing acrylic compound represented by the following general formula (4) or (5).
[ solution 3]
[ solution 4]
(in the formula, Z3、Q1A is as described above, Rf' is-CF2O(CF2O)m(CF2CF2O)nCF2- (CF) wherein m is an integer of 1 to 200, n is an integer of 1 to 170, and m + n is an integer of 6 to 2012O) -and- (CF)2CF2The arrangement of O) -is random, R3Is a hydrogen atom or a methyl group, d1 and e1 are integers of 0 to 10, and the fluorine content in the compound represented by the formula (4) or (5) is 25 mass% or more and less than 45 mass%. )
[11] [1] the fluorine-containing curable composition according to any one of [1] to [10], wherein the non-fluorinated acrylic compound of the component (C) is a polyfunctional acrylic compound having 2 or more (meth) acryloyl groups in 1 molecule and no urethane bond, or a polyfunctional urethane acrylate having 3 or more (meth) acryloyl groups in 1 molecule obtained by reacting the polyfunctional acrylic compound with an aliphatic polyisocyanate and an acrylic compound having a hydroxyl group, or a mixture of 2 or more acrylic compounds including the polyfunctional acrylic compound and the urethane acrylate.
[12] An article having a cured coating film of the fluorine-containing curable composition according to any one of [1] to [11] on the surface thereof.
ADVANTAGEOUS EFFECTS OF INVENTION
The fluorine-containing curable composition of the present invention has stable solubility, and can form a cured coating film having high antifouling property, dirt-removing property, and sliding property.
Detailed Description
The fluorine-containing curable composition of the present invention comprises a component (A), a component (B) and a component (C), wherein the component (A) is a linear polymer having a fluoropolyether in a main chain and is composed of a compound having 1 or 2 (meth) acryloyl groups at one or both ends of a molecular chain, the average number of (meth) acryloyl groups contained in 1 molecule is 2 or less, and a fluorine content is 48 mass% or more and less than 62 mass%, the component (B) is composed of a compound having 2 or more (meth) acryloyl groups at each molecular chain end (i.e., both molecular chain ends) in 1 molecule of the linear polymer having a fluoropolyether in a main chain, an average number of 4 to 10 (meth) acryloyl groups in 1 molecule, and a fluorine content of 25 mass% or more and less than 45 mass%, and the component (C) is composed of a non-fluorinated acrylic compound having no fluoropolyether structure and having 2 or more (meth) acryloyl groups in 1 molecule on average The fluorine-containing curable composition comprises the components (A), (B) and (C) as essential components.
In the present invention, "acrylic compound" is a general term for compounds having an acryloyl group and a methacryloyl group, and "(meth) acryloyl group" represents one or both of an acryloyl group and a methacryloyl group, "(meth) acrylic acid" represents one or both of acrylic acid and methacrylic acid, and "(meth) acrylate" represents one or both of an acrylate and a methacrylate. Further, "acrylates" are a generic name of compounds having acrylates and methacrylates.
In the present invention, it is not necessary that each of the components (a), (B), and (C) is a single compound, and for example, when the mass in the blending is taken into consideration, the total amount of the blended mixture of a plurality of compounds in accordance with the respective conditions of the components (a), (B), and (C) can be regarded as each component amount.
[ component (A) ]
The component (a) which is the first essential component in the photocurable composition of the present invention is a linear polymer having a fluoropolyether in the main chain, and is composed of a compound having 1 or 2 (meth) acryloyl groups at one or both ends of the molecular chain, and having an average value of the number of (meth) acryloyl groups contained in 1 molecule of 2 or less (1 to 2) (that is, having 1 (meth) acryloyl group at each end of the molecular chain, or having 1 or 2 (meth) acryloyl groups at one end of the molecular chain, respectively) and having a fluorine content of 48 mass% or more and less than 62 mass%.
The fluorine content of the compound of the component (a) is 48 mass% or more and less than 62 mass%, preferably 55 mass% or more and 61.5 mass% or less, and more preferably 57 mass% or more and 61 mass% or less. If the fluorine content is less than 48% by mass, the improvement of the antifouling property is insufficient as compared with the case where the component (A) is not used, and if it is 62% by mass or more, the solubility to the component (C) is insufficient, and it is difficult to obtain a smooth coated surface of the cured coating film. In the present invention, the fluorine content is based on the ratio of fluorine atoms in the molecule to fluorine atoms in the molecule19F-NMR and1the mass% value of the number average molecular weight calculated from the molecular formula of the compound obtained by H-NMR (the same applies below).
Examples of such a compound include a fluorine-containing acrylic compound represented by the following general formula (1) or (2).
Rf1-O-Rf2-CF2-Z1-X1 (1)
X2-Z1-CF2O-Rf2-CF2-Z1-X1 (2)
In the above formula (1), Rf1Is a fluorine atom or a 1-valent fluoroalkyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, which may contain an oxygen atom, and specifically, in addition to the fluorine atom, there are exemplified trifluoromethyl, pentafluoroethyl, perfluoroisopropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, and
CF3OCF2CF2-
CF3OCF2CF2CF2-
CF3CF2OCF2CF2-
(CF3)2CFOCF2CF2-
CF3OCF2CF2CF2CF2-
CF3CF2OCF2CF2CF2-
CF3CF2CF2OCF2CF2-
(CF3)2CFCF2OCF2CF2-
CF3CF2CF2CF2OCF2CF2-
CF3CF2CF2OCF2CF2CF2-
of these, CF is particularly preferred3-、CF3CF2-。
In the above formulae (1) and (2), Rf2Is the following 2 kinds of repeating units
-CF2O-
-CF2CF2O-
The randomly arranged 2-valent perfluoropolyether groups having a molecular weight of 600 to 20000, preferably 1200 to 10000 can be represented, for example, as follows.
-(CF2O)m(CF2CF2O)n-
m is an integer of 1 to 200, preferably 6 to 50, n is an integer of 1 to 170, preferably 6 to 50, m + n is an integer of 6 to 201, preferably 12 to 100, and if the values of m, n and m + n are too small, the effect of imparting stain resistance to the cured composition becomes small, and if too large, the compatibility with the non-fluorinated component becomes poor, which causes clouding of the coating liquid and coating failure. The values of m and n may have a distribution, in which case they are preferably represented by19The values of m + n obtained by F-NMR and the like are expressed in terms of number average and satisfy the above ranges.
In the above formulae (1) and (2), Z1Independently selected from the group consisting of,A 2-valent hydrocarbon group having 1 to 20 carbon atoms, which is at least one heteroatom of a nitrogen atom and a silicon atom, wherein the 2-valent hydrocarbon group may have a cyclic structure in the middle, and a part of hydrogen atoms bonded to carbon atoms may be substituted with fluorine atoms. As such Z1Preferred structures include the following groups.
-C(＝O)-
-C(＝O)O-
-C(＝O)OCH2-
-C(＝O)OCH2CH2-
-CH2-
-CH2O-
-CH2OCH2-
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OC(＝O)NH-
-CH2OC(＝O)NHCH2CH2-
Of these, particularly preferred is
-CH2-
-CH2OC(＝O)NH-
-CH2OC(＝O)NHCH2CH2。
In the above formulae (1) and (2), X1Independently are 1-valent organic groups, preferably having 1 or 2 (meth) acryloyl groups, which may contain oxygen atoms and/or nitrogen atoms, but having 1 or 2 of the above-mentioned 1-valent organic groups in 1 molecule. In the above formula (2), X2Is hydroxy or X1。
As X1Specific examples of the preferred structure of (b) include the following structures.
-OC(＝O)CH＝CH2
-OC(＝O)C(CH3)＝CH2
-C[OC(＝O)CH＝CH2]2
-C[OC(＝O)C(CH3)＝CH2]2
-CH[CH2OC(＝O)CH＝CH2][CH2OC(＝O)C(CH3)＝CH2]
-C(CH3)[CH2OC(＝O)CH＝CH2]2
-CH2[CH2OC(＝O)C(CH3)＝CH2]2
-C[CH2OC(＝O)CH＝CH2]
-C(CH2CH3)[CH2OC(＝O)CH＝CH2]2
-C(CH2CH3)[CH2OC(＝O)C(CH3)＝CH2]2
Particularly preferably
-OC(＝O)CH＝CH2
-OC(＝O)C(CH3)＝CH2。
As X2Specific examples of the preferred structure of (b) include the following structures.
HO-
CH2＝C(CH3)C(＝O)O-
CH2＝CHC(＝O)O-
More specifically, the component (a) includes compounds represented by the following structural group.
Rf1ORf2CF2CH2OC(＝O)CH＝CH2
Rf1ORf2CF2CH2OC(＝O)C(CH3)＝CH2
HOCH2CF2ORf2CF2CH2OC(＝O)CH＝CH2
HOCH2CF2ORf2CF2CH2OC(＝O)C(CH3)＝CH2
Rf1ORf2CF2C(＝O)OCH2CH2OC(＝O)CH＝CH2
Rf1ORf2CF2C(＝O)OCH2CH2OC(＝O)C(CH3)＝CH2
HOCH2CF2ORf2CF2C(＝O)OCH2CH2OC(＝O)CH＝CH2
HOCH2CF2ORf2CF2C(＝O)OCH2CH2OC(＝O)C(CH3)＝CH2
Rf1ORf2CF2C(＝O)OCH[CH2OC(＝O)CH＝CH2][CH2OC(＝O)C(CH3)＝CH2]
Rf1ORf2CF2CH2OC(＝O)NHCH2CH2OC(＝O)CH＝CH2
Rf1ORf2CF2CH2OC(＝O)NHCH2CH2OC(＝O)C(CH3)＝CH2
HOCH2CF2ORf2CF2CH2OC(＝O)NHCH2CH2OC(＝O)CH＝CH2
HOCH2CF2ORf2CF2CH2OC(＝O)NHCH2CH2OC(＝O)C(CH3)＝CH2
HOCH2CF2ORf2CF2CH2OC(＝O)NHC(CH3)[CH2OC(＝O)CH＝CH2]2
CH2＝C(CH3)C(＝O)OCH2CF2ORf2CF2CH2OC(＝O)C(CH3)＝CH2
CH2＝CHC(＝O)OCH2CF2ORf2CF2CH2OC(＝O)C(CH3)＝CH2
CH2＝CHC(＝O)OCH2CF2ORf2CF2CH2OC(＝O)CH＝CH2
CH2＝CHC(＝O)OCH2CH2NHC(＝O)OCH2CF2ORf2CF2CH2OCH2OC(＝O)CH＝CH2
CH2＝C(CH3)C(＝O)OCH2CH2NHC(＝O)OCH2CF2ORf2CF2CH2OCH2OC(＝O)C(CH3)＝CH2
CH2＝CHC(＝O)OCH2CH2NHC(＝O)OCH2CF2ORf2CF2CH2OC(＝O)NHCH2CH2OC(＝O)CH＝CH2
(wherein Rf1、Rf2As described above, the average fluorine content of the compound corresponding to the component (a) is particularly preferably 55 mass% or more and less than 62 mass%. )
The component (A) is represented by the following general formula (1) or (2)
Rf1-O-Rf2-CF2-Z1-X1 (1)
X2-Z1-CF2O-Rf2-CF2-Z1-X1 (2)
(wherein Rf1、Rf2、Z1、X1、X2And the following steps: the same applies to the above. )
Preferred synthesis methods of the fluorine-containing acrylic compound include, for example, the following methods, for example, the methods represented by the following general formulae (6) and (7)
Rf1-O-Rf2-CF2-CH2-OH (6)
HO-CH2-CF2O-Rf2-CF2-CH2-OH (7)
(wherein Rf1、Rf2As described above. )
One of the fluorinated alcohol compounds represented by the following general formula (8)
CH2＝CR3C(＝O)X (8)
(in the formula, R3As described above, X is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or the like. ) A method of reacting the (meth) acryloyl halide represented by the formula (9)
CH2＝CR3C(＝O)OCH2CH2-N＝C＝O (9)
(in the formula, R3As described above. )
The (meth) acryloyl group-containing isocyanate compound of the present invention can be obtained by a method of reacting the (meth) acryloyl group-containing isocyanate compound of the present invention with a fluorine-containing acrylic compound of the formula (1) or (2).
Among them, as the (meth) acryloyl halide represented by formula (8), the following compounds can be mentioned.
CH2＝CHC(＝O)X
CH2＝C(CH3)C(＝O)X
(wherein X is the same as above.)
Acryloyl chloride and methacryloyl chloride are particularly preferred.
Examples of the (meth) acryloyl group-containing isocyanate compound represented by formula (9) include the following compounds.
CH2＝CHC(＝O)OCH2CH2-N＝C＝O
CH2＝C(CH3)C(＝O)OCH2CH2-N＝C＝O
These (meth) acryloyl halides or (meth) acryloyl group-containing isocyanate compounds are charged in an equimolar amount or more relative to the total amount of hydroxyl groups of the fluorine-containing alcohol compound, and the reaction is carried out to allow all hydroxyl groups to react, and in the compound of formula (7), 1 mole or more of (meth) acryloyl groups can be introduced on average relative to 1 mole of the fluorine-containing alcohol compound, and the hydroxyl groups are made excessive, so that unreacted (meth) acryloyl halides or (meth) acryloyl group-containing isocyanate compounds do not remain. Specifically, when the amount of the fluorine-containing alcohol compound in the reaction system is x moles and the total amount of the hydroxyl groups of the fluorine-containing alcohol compound is y moles, the amount of the (meth) acryloyl halide or the (meth) acryloyl group-containing isocyanate compound is preferably x moles or more and 2y moles or less, and particularly preferably 0.6y moles or more and 1.4y moles or less. If the amount is too small, the fluorine-containing alcohol compound in which the (meth) acryloyl group is not completely introduced may remain, and the solubility of the product may be lowered. If the amount is too large, it becomes difficult to remove the remaining unreacted (meth) acryloyl halide or (meth) acryloyl group-containing isocyanate compound.
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 (THF), 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 (also known as m-bistrifluoromethylene and benzylidene trifluoro, and fluorine-modified ether solvents such as methyl perfluorobutyl ether. The solvent can be removed by a known method such as distillation under reduced pressure after the reaction, and can be used as a diluted solution as it is according to the intended use.
The amount of the solvent used is not particularly limited, but is preferably 10 times or less the total mass of all the reaction components. If the amount of the solvent used is too large, there is a possibility 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 generally 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 all 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 acid remains without being trapped, and if the amount is too large, it becomes difficult to remove the remaining acid-accepting agent.
The dropping of the (meth) acryloyl halide is carried out for 20 to 60 minutes while maintaining the temperature of the reaction mixture at 0 to 35 ℃. Then, the stirring was continued for further 30 minutes to 10 hours. After the completion of the reaction, unreacted (meth) acrylic acid halide, a salt produced by the reaction, a reaction solvent, and the like are removed by a method such as distillation, adsorption, filtration, washing, and the like, whereby a fluorine-containing acrylic compound represented by the above formula (1) or (2) can be obtained.
When the reaction is stopped, an alcohol compound such as methanol or ethanol is added to the system, and the unreacted (meth) acrylic acid halide may be esterified. The acrylic esters formed can be removed by the same method as that for removing unreacted (meth) acrylic acid halide, and can also be used in the remaining state.
In the case of the reaction of the fluorinated alcohol compound and the (meth) acryloyl group-containing isocyanate compound, the reaction is carried out by stirring the fluorinated alcohol compound and the (meth) acryloyl group-containing isocyanate compound together with a solvent as necessary.
In this reaction, in order to increase the reaction rate, a suitable catalyst may be added. Examples of the catalyst include alkyl tin ester compounds such as 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 isopropoxyoctylsubethanoltitanium, zirconium tetraacetylacetonate, zirconium tributoxybis monoacetoacetonate, bis (ethylacetoacetate) zirconium monobutoxybis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate), zirconium tetraacetylacetonate and zirconium chelate compounds. These catalysts are not limited to 1 kind thereof, and can be used as a mixture of 2 kinds or more thereof. The reaction rate can be increased by adding 0.01 to 2 mass%, preferably 0.05 to 1 mass% of these catalysts to the total mass of the reactants.
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 and reaction solvent are removed by a method such as distillation, adsorption, filtration, washing, etc., whereby a fluorine-containing acrylic compound represented by the above formula (1) or (2) can be obtained.
When the reaction is stopped, an alcohol compound such as methanol or ethanol is added to the system, and a urethane bond can be formed with an unreacted isocyanate compound. The urethane acrylate produced can be removed by the same method as that for the unreacted isocyanate compound, and can be used after remaining.
[ component (B) ]
The component (B) as the second essential component in the photocurable composition of the present invention is composed of a compound having 2 or more, preferably 2 to 4 (meth) acryloyl groups at each molecular chain end (i.e., at both molecular chain ends) of 1 molecule of a linear polymer having a fluoropolyether in the main chain, an average of 4 to 10, preferably 4 to 8 (meth) acryloyl groups in 1 molecule, and a fluorine content of 25 mass% or more and less than 45 mass%.
Among them, the fluorine content of the compound of the component (B) is 25 mass% or more and less than 45 mass%, preferably 28 mass% or more and 43 mass% or less, and more preferably 33 mass% or more and 42 mass% or less. If the fluorine content is less than 25% by mass, the solubility in the component (A) is lowered, and if it is 45% by mass or more, the solubility in the component (C) is lowered, and therefore it is difficult to smoothly apply the composition as a whole.
Specifically, a fluorine-containing acrylic compound represented by the following general formula (3) can be shown as such a compound.
[ solution 5]
In the above formula (3), Rf2Rf of the above formulae (1) and (2)2The same is true.
In the above formula (3), R1The hydrocarbon group having a valence of 1 is independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, and specific examples of the hydrocarbon group having a valence of 1 include an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, or an octyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group, an allyl group, or a propenyl group, an aryl group such as a phenyl group, a tolyl group, or a xylyl group, and an aralkyl group such as a benzyl group or a phenylethyl group. As R1Hydrogen atom and methyl group are preferable.
In the above formula (3), R2Independently a hydrogen atom, or a 1-valent organic group having a (meth) acryloyl group that may contain an oxygen atom and/or a nitrogen atom. As the 1-valent organic group, a group having at least 1, preferably 1 or 2 (meth) acryloyl groups at the terminal is preferable. The structure may have an amide bond, an ether bond, an ester bond, or the like.
Examples of such a structure include the following structures.
CH2＝CHC(＝O)-
CH2＝C(CH3)C(＝O)-
CH2＝CHC(＝O)OCH2CH2-NHC(＝O)-
CH2＝C(CH3)C(＝O)OCH2CH2-NHC(＝O)-
CH2＝C(CH3)C(＝O)OCH2CH2OCH2CH2-NHC(＝O)-(CH2＝CHC(＝O)OCH2CH2)2C(CH3)-NHC(＝O)-
Among these, the following structure is particularly preferable.
CH2＝CHC(＝O)OCH2CH2-NHC(＝O)-
CH2＝C(CH3)C(＝O)OCH2CH2-NHC(＝O)-
In the formula (3), a is independently an integer of 2 to 5, preferably an integer of 2 to 4, and more preferably 2 or 3. If a is less than 2, the solubility in the component (C) may be low, and if a is more than 5, the solubility in the component (A) may be low.
In the above formula (3), Q1Independently a (a +1) -valent linking group containing at least (a +1) silicon atoms, may form a cyclic structure. As such Q1Preferable structures of (b) include (a +1) -valent linking groups each having a siloxane structure having at least (a +1) silicon atoms, an unsubstituted or halogen-substituted silylene structure, a silylarylene structure, or a combination of 2 or more thereof. In this case, (a +1) bonding ends preferably have (a +1) silicon atoms, respectively. Specifically, the following configuration is shown as a particularly preferable configuration.
However, in the following structure, a is the same as a in the above formula (3). In addition, b is an integer of 1 to 5, preferably an integer of 1 to 3. The arrangement of the units is random, the binding end of (a +1) units, etc. and Z3Used of' He]A number of CH2Any of the groups in (1) is bound.
[ solution 6]
Wherein T' is a (a +1) -valent linking group, and examples thereof include the following linking groups.
[ solution 7]
Among these, the following linking groups are particularly preferable.
[ solution 8]
(wherein a1 represents 2 or 3.)
In the above formula (3), Z2Each independently is a C1-100, preferably C1-40, 2-valent hydrocarbon group that may contain an oxygen atom and/or a nitrogen atom, and may contain a cyclic structure in the middle.
As Z2Preferable examples of the structure of (c) include the following structures.
-CH2[OC2H4]d[OC3H6]e[OC4H8]fOCcH2c-
(wherein d is an integer of 0 to 29, preferably 0 to 10, e is an integer of 0 to 29, preferably 0 to 10, f is an integer of 0 to 14, preferably 0 to 7, and c is an integer of 2 to 4. the total of the above structures may be such that the number of carbon atoms is 3 to 100, preferably 3 to 30. the arrangement of the repeating units is random regardless of the kind
As Z2Particularly preferred structures include the following 2 structures, and among them, a structure in which d is an integer of 0 to 10 and e is an integer of 0 to 10 is preferred.
-CH2[OC2H4]dOC2H4-
-CH2[OC3H6]eOCH2CH(CH3)-
In addition, as Z2The following structures can also be cited.
[ solution 9]
In the above formula (3), Z3Independently, the linking group is a 2-valent hydrocarbon group having 1 to 20 carbon atoms, which may contain at least 1 hetero atom selected from an oxygen atom, a nitrogen atom and a silicon atom, and may contain a cyclic structure in the middle, and a part of hydrogen atoms bonded to carbon atoms may be substituted with fluorine atoms. As such Z3Preferred structures include the following groups.
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OCH2CH2-
-CH2OCH2CH2CH2-
[ solution 10]
Of these, particularly preferred is
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OCH2CH2-
-CH2OCH2CH2CH2-。
As a more preferable structure of the fluorine-containing acrylic compound represented by the above formula (3), compounds represented by the following general formulae (4) and (5) can be exemplified.
[ solution 11]
[ solution 12]
(in the formula, Z3、Q1A is as described above, Rf' is-CF2O(CF2O)m(CF2CF2O)nCF2- (CF) wherein m, n and m + n are the same as defined above2O) -and- (CF)2CF2The arrangement of O) -is random, R3Is a hydrogen atom or a methyl group, d1 and e1 are integers of 0 to 10, and the fluorine content in the compound represented by the formula (4) or (5) is 25 mass% or more and less than 45 mass%. )
As the component (B), specifically, the following compounds can be exemplified.
[ solution 13]
[ solution 14]
[ solution 15]
[ solution 16]
[ solution 17]
(wherein Rf' is the same as above, for example, n/m is 0.9, m + n is approximately equal to 45. e2 is an integer of 1 to 10, for example, 4.)
The fluorine-containing acrylic compound represented by the formula (3) of the component (B) can be synthesized, for example, by the methods disclosed in jp 2010-285501 a and jp 2015-199910 a.
For example, the fluorine-containing acrylic compound represented by the above formula (3) is first prepared by reacting a compound represented by the following general formula (10)
[ solution 18]
(wherein Rf2、Z3、Q1And a is the same as above, using]A total of H and Q1Silicon atoms in the structure are bonded. )
A fluoropolyether compound having a polyfunctional Si-H group represented by the following general formula (11)
CH2＝CR1-Z2-OH (11)
(in the formula, R1、Z2As described above. )
The alcohol having an unsaturated group at the end (compound having an alkenyl group and a hydroxyl group at the molecular end) shown above is subjected to a hydrosilylation reaction, whereby a fluorine-containing alcohol compound as an intermediate can be obtained.
Among them, examples of the fluoropolyether compound having a polyfunctional Si — H group represented by the above formula (10) include the following compounds.
[ solution 19]
(wherein Rf' is the same as described above.)
Examples of the alcohol having a terminal unsaturated group represented by the formula (11) include the alcohols shown below.
CH2＝CH-CH2-OCH2CH2-OH
CH2＝CH-CH2-OCH2CH(CH3)-OH
CH2＝CH-CH2-(OC3H6)2-OCH2CH(CH3)-OH
CH2＝CH-CH2-(OC3H6)4-OCH2CH(CH3)-OH
CH2＝CH-CH2-(OC3H6)9-OCH2CH(CH3)-OH
[ solution 20]
In the hydrosilylation (addition) reaction, it is preferable that the fluoropolyether compound having a polyfunctional Si — H group represented by formula (10) and the alcohol having a terminal unsaturated group represented by formula (11) are mixed and reacted in the presence of a platinum group metal-based addition reaction catalyst at a reaction temperature of 50 to 150 ℃, preferably 60 to 120 ℃, for 1 minute to 48 hours, particularly 10 minutes to 12 hours. If the reaction temperature is too low, the reaction may not proceed sufficiently, and the reaction may be stopped, and if it is too high, the reaction may not be controlled due to the temperature rise caused by the reaction heat of hydrosilylation, and bumping, decomposition of the raw material, and the like may occur.
In this case, the ratio of the reaction of the fluoropolyether compound having a polyfunctional Si — H group represented by the formula (10) and the alcohol having a terminal unsaturated group represented by the formula (11) is preferably 0.5 to 5 times by mole, particularly 0.9 to 2 times by mole, of the terminal unsaturated group of the alcohol having a terminal unsaturated group represented by the formula (11) relative to the total number of moles of H [ ] included in the fluoropolyether compound having a polyfunctional Si-H group represented by the formula (10). If the amount of the alcohol having a terminal unsaturated group represented by the formula (11) is too small compared to the above amount, it may be difficult to obtain a fluorine-containing alcohol compound having high solubility, and if the amount is too large, the uniformity of the reaction solution is lowered and the reaction rate becomes unstable, and if the amount is increased after the reaction to remove the alcohol having a terminal unsaturated group represented by the formula (11), the amount of the unreacted alcohol remaining must be increased by a degree corresponding to the strict control of the conditions of heating, pressure reduction, extraction and the like.
As the addition reaction catalyst, for example, a compound containing platinum group metal such as platinum, rhodium, or palladium can be used. Among them, platinum-containing compounds are preferable, and hexachloroplatinic (IV) acid hexahydrate, platinum carbonyl vinyl methyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octanal/octanol complex, or platinum supported on activated carbon can be used.
The amount of the addition reaction catalyst to be added is preferably 0.1 to 5000ppm by mass, more preferably 0.2 to 1000 ppm by mass, relative to the amount of the metal contained in the multifunctional Si-H group-containing fluoropolyether compound represented by the formula (10).
The addition reaction can be carried out even in the absence of a solvent, and if necessary, the reaction mixture can be diluted with a solvent. In this case, the diluting solvent may be any of generally widely used organic solvents such as toluene, xylene and isooctane, and is preferably a solvent having a boiling point of not lower than the target reaction temperature and not inhibiting the reaction, and the fluorine-containing alcohol compound formed after the reaction is soluble at the reaction temperature. Examples of such a solvent include partially fluorine-modified solvents such as fluorine-modified aromatic hydrocarbon solvents such as hexafluorometaxylene and benzylidene trifluoro, and fluorine-modified ether solvents such as methyl perfluorobutyl ether, and hexafluorometaxylene is particularly preferable.
When a solvent is used, the amount of the solvent used is preferably 5 to 2000 parts by mass, and 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 (10). If the amount is less than this, the effect of dilution by the solvent is weak, and if it is more than this, the dilution degree is excessively increased, which may cause a decrease in the reaction rate.
After the completion of the reaction, the unreacted alcohol having a terminal unsaturated group represented by the formula (11) and the diluting solvent are preferably removed by a known method such as reduced pressure distillation, extraction, adsorption, etc., and the reaction mixture containing them can be used directly in the next reaction.
Examples of the fluorine-containing alcohol compound thus obtained include the following compounds.
[ solution 21]
[ solution 22]
[ solution 23]
(wherein Rf' and e are the same as defined above.)
Next, a (meth) acryloyl group is introduced into the fluorine-containing alcohol compound obtained above, whereby a fluorine-containing acrylic compound can be obtained. The method for introducing a (meth) acryloyl group into a fluorochemical alcohol compound includes a method of reacting with a (meth) acryloyl halide represented by the following formula (12) to form an ester, and a method of reacting with an isocyanate compound having a (meth) acryloyl group represented by the following formula (13), and by these methods, the fluorochemical acrylic compound targeted by the present invention can be obtained.
CH2＝CR3C(＝O)X (12)
CH2＝CR3C(＝O)OCH2CH2-N＝C＝O (13)
(in the formula, R3And X is the same as above. )
Among them, as the (meth) acryloyl halide represented by formula (12), the following compounds can be mentioned.
CH2＝CHC(＝O)X
CH2＝C(CH3)C(＝O)X
(wherein X is the same as above.)
Acryloyl chloride and methacryloyl chloride are particularly preferred.
Examples of the (meth) acryloyl group-containing isocyanate compound represented by formula (13) include the following compounds.
CH2＝CHC(＝O)OCH2CH2-N＝C＝O
CH2＝C(CH3)C(＝O)OCH2CH2-N＝C＝O
These (meth) acryloyl halides or (meth) acryloyl group-containing isocyanate compounds may be charged in an amount equal to or greater than the total amount of hydroxyl groups of the fluorine-containing alcohol compound, and reacted to react all of the hydroxyl groups, and on average 1 mole or more of (meth) acryloyl groups may be introduced to 1 mole of the fluorine-containing alcohol compound, and the hydroxyl groups may be made excessive, thereby preventing unreacted (meth) acryloyl halides or (meth) acryloyl group-containing isocyanate compounds from remaining. Specifically, when the amount of the fluorine-containing alcohol compound in the reaction system is x moles and the total amount of hydroxyl groups of the fluorine-containing alcohol compound is y moles, the (meth) acryloyl halide or the (meth) acryloyl group-containing isocyanate compound is preferably x moles or more and 2y moles or less, and particularly preferably 0.6y moles or more and 1.4y moles or less. If the amount is too small, the possibility that the fluorochemical alcohol compound into which no (meth) acryloyl group has been introduced remains increases, and the solubility of the product may decrease. If the amount is too large, it becomes difficult to remove the remaining unreacted (meth) acryloyl halide or (meth) acryloyl group-containing isocyanate compound.
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 THF, 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 can be removed by a known method such as distillation under reduced pressure after the reaction, and can be used as a diluted solution as it is according to the intended use.
The amount of the solvent used is not particularly limited, but is preferably 10 times or less the total mass of all 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 generally 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 all 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 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 for 20 to 60 minutes while maintaining the temperature of the reaction mixture at 0 to 35 ℃. Then, the stirring was continued for further 30 minutes to 10 hours. After the completion of the reaction, unreacted (meth) acrylic acid halide, a salt produced by the reaction, a reaction solvent, and the like are removed by a method such as distillation, adsorption, filtration, washing, and the like, whereby a fluorine-containing acrylic compound represented by the above formula (3) can be obtained.
When the reaction is stopped, an alcohol compound such as methanol or ethanol is added to the system, and the unreacted (meth) acrylic acid halide may be esterified. The (meth) acrylic esters formed can be removed by the same method as that for removing unreacted (meth) acrylic acid halide, and can also be used in the remaining state.
In the case of the reaction of the fluorinated alcohol compound and the (meth) acryloyl group-containing isocyanate compound, the reaction is carried out by stirring the fluorinated alcohol compound and the (meth) acryloyl group-containing isocyanate compound together with a solvent as necessary.
In this reaction, in order to increase the reaction rate, a suitable catalyst may be added. Examples of the catalyst include alkyl tin ester compounds such as 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 isopropoxyoctylsubethanoltitanium, zirconium tetraacetylacetonate, zirconium tributoxybis monoacetoacetonate, bis (ethylacetoacetate) zirconium monobutoxybis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate), zirconium tetraacetylacetonate and zirconium chelate compounds. These catalysts are not limited to 1 type, and can be used as 2 or more types of mixtures, and particularly preferably used are titanium compounds and tin compounds having low environmental impact. The reaction rate can be increased by adding 0.01 to 2 mass%, preferably 0.05 to 1 mass% of these catalysts to the total mass of the reactants.
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 and reaction solvent are removed by a method such as distillation, adsorption, filtration, washing, etc., whereby the fluorine-containing acrylic compound represented by the above formula (3) can be obtained.
When the reaction is stopped, an alcohol compound such as methanol or ethanol is added to the system, and a urethane bond can be formed with an unreacted isocyanate compound. The urethane acrylate produced can be removed by the same method as that for the unreacted isocyanate compound, and can be used after remaining.
[ component (C) ]
The component (C) as the third essential component in the fluorine-containing curable composition of the present invention is a non-fluorinated acrylic compound having no fluoropolyether structure and having an average of 2 or more (meth) acryloyl groups in 1 molecule. The component (C) also includes urethane acrylates having a urethane bond in the molecule, and compounds having 2 or more (meth) acryloyl groups introduced into the side chains or the terminals of various polymers by any method.
Examples of the non-fluorinated acrylic compound (C) include compounds having 2 or more (meth) acryloyl groups in 1 molecule, and examples thereof 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 ester, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, di (trimethylolpropane) tetra (meth) acrylate, propylene glycol mono (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol mono (meth) acrylate, and ethylene glycol mono (meth) acrylate, 2-6 functional (meth) acrylic compounds such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and sorbitol hexa (meth) acrylate, epoxy acrylates obtained by adding (meth) acrylic acid to an epoxy resin, and copolymers in which a (meth) acryloyl group is introduced in a side chain of a (meth) acrylate copolymer, and the like, wherein the (meth) acrylic compounds are modified with ethylene oxide, propylene oxide, epichlorohydrin, a fatty acid, an alkyl group, and the like.
Further, urethane acrylates, products obtained by reacting a (meth) acrylate having a hydroxyl group with a polyisocyanate and a polyester of a terminal diol, and products obtained by reacting a (meth) acrylate having a hydroxyl group with a polyisocyanate obtained by reacting an excess of a diisocyanate with a polyol can also be used. Among these, preferred are urethane 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.
Component (C) can be used alone or in combination with a plurality of the above compounds in order to improve coatability and the characteristics of the cured film.
It is particularly preferable to use a mixture of at least 2 kinds of acrylic compounds including a polyfunctional acrylic compound having 2 or more (meth) acryloyl groups in 1 molecule and having no urethane bond, or a polyfunctional urethane acrylate having 3 or more (meth) acryloyl groups in 1 molecule obtained by reacting an aliphatic polyisocyanate and an acrylic compound having a hydroxyl group with the polyfunctional acrylic compound.
Among them, examples of the polyfunctional acrylic compound having 2 or more (meth) acryloyl groups in 1 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.
Examples of the polyfunctional urethane acrylate having 3 or more (meth) acryloyl groups in 1 molecule obtained by reacting an aliphatic polyisocyanate and an acrylic compound having a hydroxyl group include hexamethylene diisocyanate, norbornane diisocyanate, isophorone diisocyanate, and a trimer thereof, and 2 or more functional polyisocyanates obtained by reacting these 2 or 3 functional isocyanates with an aliphatic diol, an aliphatic polyol, and a polyacrylate having a hydroxyl group in a side chain, trimethylolpropane di (meth) acrylate, glycerol di (meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and mixtures thereof, Dipentaerythritol penta (meth) acrylate and modified products thereof with ethylene oxide and propylene oxide, and products obtained by reacting an aliphatic polyol and a polyacrylate having a hydroxyl group in a side chain with an acrylic compound having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate and 1, 1- (bisacryloxymethyl) ethyl isocyanate.
The component (C) may include not only a liquid component but also a modified product of the surface of a fine particulate high molecular weight material or the surface of an inorganic filler fine particle with a (meth) acryloyl group.
In the fluorine-containing curable composition of the present invention, the total amount of the component (a) and the component (B) is preferably 0.05 to 50 parts by mass, particularly preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the component (C), and the amount of the component (a) to 100 parts by mass of the component (B) is preferably 1 to 100 parts by mass, particularly preferably 3 to 50 parts by mass. If the total amount of the components (A) and (B) is too large relative to the component (C), the performance as a hard coat film is lowered, and if it is too small, sufficient antifouling performance cannot be exhibited. If the amount of the component (a) is too large relative to the component (B), the solubility to the component (C) may be excessively deteriorated, resulting in coating failure, and if it is too small, no difference is observed from the component (B) used alone.
The fluorine-containing curable composition of the present invention can also be cured by heat, electron beam or the like of a product blended with only 3 components of the above-mentioned components (a), (B) and (C) as essential components, and can also contain components other than the 3 components as necessary depending on workability.
In particular, by containing a photopolymerization initiator as the component (D), a curable composition having improved curability when ultraviolet rays are used as the active energy rays can be produced.
[ component (D) ]
The photopolymerization initiator of the component (D) is not particularly limited as long as it is a photopolymerization initiator capable of curing an acrylic compound by ultraviolet irradiation, and preferable examples thereof include acetophenone, benzophenone, 2-dimethoxy-1, 2-diphenylethane-1-one, 1-hydroxycyclohexyl-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-benzoyloxime) ], 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, 1 species may be used alone, or 2 or more species may be used in combination.
The content of the component (D) can be suitably determined depending on the curing conditions and the aimed physical properties of the composition, and is, for example, preferably 0.1 to 15 parts by mass, and particularly preferably 1 to 10 parts by mass, based on 100 parts by mass of the component (C). If the amount of addition is less than this, curability may be reduced, and if it is more than this, the influence on physical properties after curing may be increased.
These components (A), (B), (C) and (D) can be used as a single compound or a mixture of compounds having the same structure as defined for each compound. In the case of a mixture of a plurality of compounds, the total mass of each compound group can be regarded as the respective mass in consideration of the amount of compounding.
The fluorine-containing curable composition of the present invention may further contain, as a reactive diluent, a 1-functional acrylic compound, a thiol compound, a maleimide compound, etc., (meth) acryloyl group-other active energy ray-reactive compound, 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 polymer or inorganic filler, etc., depending on the purpose.
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, and cyclohexanone; ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate; esters such as propyl acetate, butyl acetate, and cyclohexyl acetate, and aromatics such as toluene, xylene, triethylbenzene, and alkylbenzenes. The above solvents may be used alone in 1 kind, or 2 or more kinds may be mixed and used.
The amount of the solvent used is not particularly limited, but is preferably 20 to 10000 parts by mass, particularly preferably 100 to 1000 parts by mass, per 100 parts by mass of the total of the components (A) to (C).
The polymerization inhibitor, antistatic agent, defoaming agent, viscosity modifier, light stabilizer, heat stabilizer, antioxidant, surfactant, colorant and filler are not particularly limited, and known components can be used within a range not impairing the object of the present invention.
The component (a) and (B) in the present invention may contain by-products produced during production of the components (a) and (B), residual unreacted components, and the like, within a range not impairing the object and the effect of the present invention. As such a component, for example, a case where the fluorinated alcohol compound represented by the above-mentioned formulae (6) and (7) remains as an unreacted component, and the like can be considered.
Further, various hard coating agents containing the component (C) and various additives are commercially available from various companies. The fluorine-containing curable composition of the present invention may be a product obtained by adding the component (a) and the component (B) to such a commercially available hard coating agent. Examples of commercially available hard coating agents include "BEAMSET" from Ishikawa chemical industry, "Ubic" from bridge chemical industry, "UV coat" from Origin Electric, "Cashew UV" from Cashew, "Desolite" from JSR, "SEIKABEHAM" from Dari refining industry, "Violet" from Japanese Synthesis chemical, "FUJIHARD" from Bing chemical industry, "Diabam" from Mitsubishi rayon, and "ULTRAVIN" from Wucang paint.
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 added and blended according to the purpose.
For the above components (C) and (D) and other additives which can be optionally compounded, for example, in methods of TECHNINET Kabushiki Kaisha (edited materials by Photocurability data letters, Inc.) (2000, TECHNINET Kabushiki Kaisha), photopolymer Seisakusho (edited handbook of photopolymer (1989, Industrial research Association), Integrated technology center (edited technology UV EB curing technology) (1982, Integrated technology center), RadTech research institute (UV EB curing Material, 1992, CMC), technical information Association (edited sources of curing failure, obstruction and countermeasure thereof in UV curing) (2003, technical information Association), technical information Association (edited design of compounding UV curing resin, evaluation of characteristics and New application) (2017, technical information Association), CMC publication (published products) (market reality and expectation of UV EB curing Material products) (2007, published CMC), scientific & technical optimization of UV curing technology (2008), Science & technology), etc., and they can be used in any combination.
The method of mixing the fluorine-containing curable composition of the present invention may be carried out by any method according to the application, and is not particularly limited, but it is preferable to sufficiently mix the component (a) and the component (B) before mixing them with other components, and for example, a method of mixing the component (a) and the component (B) at a desired ratio, mixing a product diluted with a solvent as necessary with the component (C) and other components, or mixing the component (a) diluted with a solvent and the component (B) diluted with a solvent and mixing with the component (C) and other components is preferable.
The method for curing the fluorine-containing curable composition of the present invention is not particularly limited, and a product obtained by diluting and applying a composition containing the components (a), (B), and (C) with a solvent as appropriate can be cured by using an active energy ray such as heat or an electron beam, and in the case where a photopolymerization initiator of the component (D) is further contained, the curing can be performed by using ultraviolet rays. In the case of curing with ultraviolet rays, ultraviolet irradiation can be performed in air, and in order to prevent curing inhibition by oxygen, it is preferable to suppress 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.
In addition, as a general use form of the fluorine-containing curable composition of the present invention, as long as the layer of the fluorine-containing curable composition of the present invention is adhered or bonded after curing, any substrate can be coated, and specific examples thereof include resin substrates such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetylcellulose, triacetylcellulose, acetylcellulose butyrate, cellulose acetate propionate, cycloolefin polymer, cycloolefin copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyether ether ketone, polyether sulfone, polyether imide, polyimide, fluororesin, nylon, acrylic resin, and the like. These may be in any form such as a film, a plate, a molded member, etc., and can be used on the surface thereof.
In the case of applying the pressure-sensitive adhesive to the film base, a pressure-sensitive adhesive may be applied to the surface opposite to the surface on which the fluorine-containing curable composition layer is applied and formed, and a release film for protecting the pressure-sensitive adhesive may be further provided.
The film base may be a base composed of only the resin film listed above, and a primer layer may be provided on the resin film in order to improve adhesion to the photocurable composition of the present invention. Examples of the primer layer include primer layers made of polyester resins, polyurethane resins, acrylic resins, and the like.
The fluorine-containing 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 curable composition of the present invention can be superimposed on a cured product layer having higher hardness, durability, antistatic properties, curling resistance, and other properties against deformation.
In order to improve the adhesion to the fluorine-containing curable composition of the present invention, the surface of the resin base material may be subjected to a surface roughening treatment by a sand blast method, a solvent treatment method, or the like, a corona discharge treatment, a chromic acid treatment, a flame treatment, a hot air treatment, an ozone/ultraviolet irradiation treatment, an oxidation treatment, or the like.
The method for applying the fluorine-containing curable composition of the present invention to the above-mentioned substrate or 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 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 then ultraviolet rays may be irradiated therefrom. 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 fluorine-containing curable composition obtained in this way is not particularly limited, but is preferably 0.01 to 5000. mu.m, and particularly preferably 0.05 to 200. mu.m.
The cured product layer of the fluorine-containing curable composition of the present invention thus obtained is preferably a water-and oil-repellent surface having a static water contact angle of 114 ° or more, particularly 115 ° or more, as measured from the angle formed by the liquid surface and the solid surface after 1 second from the contact of a droplet of 2 μ L of ion-exchanged water with the droplet, and a static oleic acid contact angle of 73 ° or more, particularly 74 ° or more, as measured from the angle formed by the liquid surface and the solid surface after 1 second from the contact of a droplet of 4 μ L of oleic acid with the droplet. The cured product layer of the fluorine-containing curable composition of the present invention is preferably a water-and oil-repellent surface having a low dynamic friction coefficient, which can be a cured coating film, of 0.10 or less, particularly 0.09 or less. Further, in order to obtain the contact angle and/or the dynamic friction coefficient, it is preferable that the cured product layer of the fluorine-containing curable composition of the present invention is 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 unreacted (meth) acryloyl group does not remain on the surface of the cured product layer, the more preferable is a cured product layer cured in an inert gas atmosphere such as nitrogen or carbon dioxide.
As described above, the fluorine-containing curable composition of the present invention can be cured by an active energy ray such as ultraviolet rays, and can form a cured resin layer having excellent water-and oil-repellency, stain-proofing property, sliding property, and abrasion resistance on the surface of an article.
Further, the present invention provides an article having a cured film obtained by applying and curing the above-described fluorine-containing curable composition of the present invention to a surface thereof. As described above, when the fluorine-containing curable composition of the present invention is used, a cured coating film (cured resin layer) having excellent surface characteristics can be formed 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 possible to provide a hard coat surface to a substrate, which is less likely to adhere to fingerprints, sebum, human fat such as sweat, dirt generated from cosmetics, mechanical oil, and the like, and which has excellent scratch resistance. Therefore, the fluorine-containing 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, 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 of an operator.
The cured film (cured resin layer) formed using the fluorine-containing curable composition of the present invention can be used as a surface of display operation equipment such as a portable (communication) information terminal such as a tablet personal computer, a notebook PC, a mobile phone, a smartphone and the like, a housing of various devices such as a digital media player, an electronic book reader and the like, a watch-type or spectacle-type wearable computer, a head-mounted display, a liquid crystal display, a plasma display, an organic EL (electroluminescence) display, a rear projection display, a fluorescent display tube (VFD), a field emission projection display, a CRT, a toner-based display, a Quantum Dot (QD) display and the like, and a screen of a TV and various optical films used in the surface and the interior thereof, an exterior of an automobile, a piano, a glossy surface of furniture, a surface of a building stone such as marble and the like, a decorative material around water in a toilet, a bathroom, a restroom and the like, Protective glass for art display, showcases, covers for photo frames, watches, exterior cases for cosmetic containers, exterior cases for decorative containers, window glass for automobiles, window glass for trains and aircrafts, transparent glass or transparent plastic (acrylic, polycarbonate, etc.) members for automobile headlamps and tail lamps, cover members for automobile sensors such as millimeter-wave lasers, coating films for various mirror members, and surface protective films.
Among these, various devices that can be used as display input devices for performing operations on a screen with a human finger or palm, such as a tablet PC, 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, a control panel for automobiles, an automatic cash dispensing and depositing device, a cash dispenser, an automatic vending machine, a digital signage (electronic signboard), a security system terminal, various controllers such as a POS terminal and a remote controller, and a display input device such as a panel switch for an in-vehicle device, are particularly surface protective films.
Further, the cured coating film formed by using the fluorine-containing 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; surface protective films for optical components and optical devices 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 are used.
The essential feature of the fluorine-containing curable composition of the present invention is that the fluoropolyether structure of the compounds of the components (a) and (B) according to the present invention is disposed on the surface of the target article, thereby imparting excellent properties such as water repellency, oil repellency, slidability, stain resistance, resistance to visible light of a fingerprint, fingerprint erasability, abrasion resistance, low refractive index characteristics, solvent resistance, and chemical resistance.
When the fluorine-containing curable composition of the present invention is used, an appropriate method of use can be selected based on a known technique suitable for each application, depending on the combination of the compounds, the composition ratio, and what properties are regarded as important. Such known techniques include not only a fluorine-containing composition but also a method used in a conventional active energy ray-curable composition, and can be included in the scope of research.
For example, when the above-mentioned various compounds are combined in the present fluorine-containing curable composition in addition to the components (A) and (B) according to the present invention, 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 are used, or particularly, in the case where 3 or more kinds of non-fluorine-based polyfunctional acrylic compounds are used as the component (C), and in the case where film strength and scratch resistance are improved, 2 or more kinds of non-fluorine-based polyfunctional acrylic compounds are blended as the component (C) in an appropriate amount, or a combination of 6 or more kinds of non-fluorine-based polyfunctional acrylic compounds and 3 or less kinds of non-fluorine-based acrylic compounds is used as the component (C) in order to obtain a balance between hardness and flexibility, the knowledge of compounding a known acrylic curable composition can be easily analogized.
In the case of obtaining an article by applying the fluorine-containing curable composition of the present invention, for example, in the case of applying the composition to a film base material, in order to prevent interference fringes, selection is performed by performing a screening operation based on a combination of existing conditions in accordance with each characteristic, by adjusting the thickness of the film base material so as to easily suppress curling, or by adjusting the elastic modulus of the base material film so as to suppress deformation, cracking, and the like of a coating film of the fluorine-containing curable composition after curing, and can be easily realized by combining the present invention with the existing techniques.
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)
A300L four-necked flask equipped with a reflux unit and a stirrer was charged with a solution having an average structure represented by the following formula (I)
HOCH2CF2O(CF2CF2O)20.1(CF2O)21.6CF2CH2OH (I)
A compound of (wherein, -CF)2CF2O-and-CF2The arrangement of the repeating units of O-is random) 100g (OH groups 0.0508mol) of the following formula (II)
CH2＝CHC(＝O)OCH2CH2-N＝C＝O (II)
7.17g of the compound represented by (1) and 200g of hexafluoro-m-xylene were heated to 40 ℃ under stirring in a dry air atmosphere. Then, 0.01g of dioctyltin dilaurate was added, and after stirring while heating was continued for 6 hours, the heating was stopped. By passing through the reaction solution19F-NMR confirmed that it was derived from-OCF2CH2CF of OH2All of the peaks (-81.1ppm, -83.15ppm) were changed to be derived from-OCF2CH2-OC (-O) - (-78.4ppm, -80.4 ppm). 2g of activated carbon was added to the obtained reaction solution, and after stirring at room temperature for 3 hours, the mixture was filtered through a filter plate. The obtained filtrate was distilled off under reduced pressure at 50 ℃ to obtain 97.8g of a compound having an average structure of the following (A-1) and having a target fluorine content of 57.5 mass%.
CH2＝CHC(＝O)OCH2CH2NHC(＝O)OCH2CF2O(CF2CF2O)20.1(CF2O)21.6CF2CH2OC(＝O)NHCH2CH2OC(＝O)CH＝CH2 (A-1)
Synthesis example 2 Synthesis of fluorine-containing acrylic Compound (A-2)
In Synthesis example 1, the following formula (III) was used as an average structure in place of the above formula (I)
HOCH2CF2O(CF2CF2O)31.1(CF2O)30.5CF2CH2OH(III)
A compound of (wherein, -CF)2CF2O-and-CF2The procedure of synthetic example 1 was carried out in the same manner except that the repeating units of O-were randomly arranged) was changed to 100g (OH groups: 0.0345mol) and the amount of the compound of the formula (II) was changed to 4.86g, whereby 96.2g of the compound (A-2) having a fluorine content of 59.2 mass% was obtained as an average structure.
CH2＝CHC(＝O)OCH2CH2NHC(＝O)OCH2CF2O(CF2CF2O)31.1(CF2O)30.5CF2CH2OC(＝O)NHCH2CH2OC(＝O)CH＝CH2 (A-2)
Synthesis example 3 Synthesis of fluorine-containing acrylic Compound (A-3)
In a 300L four-necked flask equipped with a reflux apparatus and a stirring apparatus, 100g (0.0508 mol of OH group) of the compound of the formula (I), 7.20g of triethylamine, and 150g of hexafluoro-m-xylene were added dropwise over 30 minutes while stirring at room temperature under a dry air atmosphere, a mixture of 6.38g (0.0704mol) of acryloyl chloride and 50g of hexafluoro-m-xylene. Stirring was continued for 6 hours and then stopped, and filtration using filter paper was performed. The obtained filtrate was poured into 1000g of hexane, and the generated precipitate was recovered, dissolved in 100g of hexafluoro-m-xylene, and then the solvent was distilled off under reduced pressure at 50 ℃ to obtain a filtrate19F-NMR confirmed that 90.5g of the target compound (A-3) having an average structure shown below and a fluorine content of 60.0 mass% was obtained.
CH2＝CHC(＝O)OCH2CF2O(CF2CF2O)20.1(CF2O)21.6CF2CH2OC(＝O)CH＝CH2 (A-3)
Synthesis example 4 Synthesis of fluorine-containing acrylic Compound (A-4)
In Synthesis example 1, the following formula (IV) was used as an average structure in place of the above formula (I)
CF3O(CF2CF2O)20.1(CF2O)19.2CF2CH2OH (IV)
A compound of (wherein, -CF)2CF2O-and-CF2The arrangement of the repeating units of O-was random) 100g (OH group 0.0264mol), the same procedure as in Synthesis example 1 was carried out except that the amount of the compound of the formula (II) was changed to 4.11g and 0.2g of tetrakis (2-ethylhexyl) orthotitanate was used in place of dioctyltin dilaurate, whereby 97.5g of the compound (A-4) having a fluorine content of 60.2 mass% was obtained as an average structure.
CF3O(CF2CF2O)20.1(CF2O)19.2CF2CH2OC(＝O)NHCH2CH2OC(＝O)CH＝CH2(A-4)
Synthesis example 5 Synthesis of fluorine-containing acrylic Compound (B-1)
A5000 mL three-necked flask equipped with a reflux apparatus and a stirring apparatus was charged with a nitrogen atmosphere
CH2＝CH-CH2-O-CH2-Rf’-CH2-O-CH2-CH＝CH2
Rf’：-CF2O(CF2CF2O)20.9(CF2O)21.2CF2-
1000g (0.245mol) of the perfluoropolyether, 1400g of hexafluoro-m-xylene, and 722g (3.00mol) of tetramethylcyclotetrasiloxane were heated to 90 ℃ with stirring. 0.884g (2.2X 10 in terms of Pt as simple substance) of a toluene solution of platinum/1, 3-divinyl-tetramethyldisiloxane complex was put therein-6mol) of the reaction solution, and stirring was continued for 4 hours while maintaining the internal temperature at 90 ℃ or higher. By passing1After confirming the disappearance of allyl groups in the starting material by H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Then, activated carbon treatment was carried out to obtain 993g of a colorless transparent liquid compound (V) represented by the following formula.
[ solution 24]
Rf’：-CF2O(CF2CF2O)20.9(CF2O)21.2CF2-
50.0g (Si-H amount 0.0657mol) of the compound (V) obtained above was mixed with 7.05g (0.0690mol) of 2-allyloxyethanol, 50.0g of hexafluorometaxylene, and 0.0442g of a toluene solution of chloroplatinic acid/vinylsiloxane complex (containing 1.1X 10 in terms of Pt as a simple substance) in a dry air atmosphere-7mol), stirred at 100 ℃ for 4 hours. By passing1After completion of the H-NMR and IR confirmation of disappearance of Si-H groups, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure and treated with activated carbon to obtain 54.9g of a pale yellow transparent liquid fluoroalcohol compound (VI) represented by the following formula.
[ solution 25]
Rf’：-CF2O(CF2CF2O)20.9(CF2O)21.2CF2-
50.0g (0.058 mol in terms of hydroxyl group content) of the resulting fluorine-containing alcohol compound (VI) was mixed with 50.0g of THF50.0g and 9.00g (0.0638mol) of acryloyloxyethyl isocyanate in a dry air atmosphere, and the mixture was heated to 50 ℃. To this was added 0.15g of tetra (2-ethylhexyl) orthotitanate, and the mixture was stirred at 50 ℃ for 24 hours. After completion of the heating, the residue was distilled off under reduced pressure at 80 ℃ under 0.266kPa to obtain 58.5g of a pale yellow paste. By1As a result of H-NMR and IR, it was confirmed that the fluorine-containing acrylic compound had a fluorine content of 41.0 mass% as shown below.
[ solution 26]
Rf’：-CF2O(CF2CF2O)20.9(CF2O)21.2CF2-
[ Synthesis example 6] Synthesis of fluorine-containing acrylic Compound (B-2)
A500 mL three-necked flask equipped with a reflux apparatus and a stirring apparatus was charged with a nitrogen atmosphere
CH2＝CH-CH2-O-CH2-Rf”-CH2-O-CH2-CH＝CH2
Rf”：-CF2O(CF2CF2O)9.8(CF2O)9.1CF2-
The perfluoropolyether (100 g, 0.0501mol), hexafluoro-m-xylene (100 g), and tetramethylcyclotetrasiloxane (121 g, 0.502mol) were heated to 90 ℃ with stirring. 0.442g (based on Pt as a simple substance, 1.1X 10) of a toluene solution of platinum/1, 3-divinyl-tetramethyldisiloxane complex was charged therein-6mol) of a component (B), stirring was continued for 4 hours while maintaining the internal temperature at 90 ℃ or higher. By passing1After confirming the disappearance of allyl groups in the starting material by H-NMR, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Then, activated carbon treatment was carried out to obtain 112g of a colorless and transparent liquid compound (VII) represented by the following formula.
[ solution 27]
Rf”：-CF2O(CF2CF2O)9.8(CF2O)9.1CF2-
50.0g (Si-H amount 0.121mol) of the compound (VII) obtained above was mixed with 15.1g (0.149mol) of 2-allyloxyethanol, 100.0g of hexafluorometaxylene, and 0.0884g (containing 2.2X 10 in terms of Pt simple substance) of a toluene solution of chloroplatinic acid/vinylsiloxane complex in a dry air atmosphere-7mol), stirred at 100 ℃ for 4 hours. By passing1H-NMR and IR confirmed that Si-H group disappearedThe solvent and excess 2-allyloxyethanol were distilled off under reduced pressure and treated with activated carbon to obtain 60.2g of a pale yellow transparent liquid fluoroalcohol compound (VIII) represented by the following formula.
[ solution 28]
Rf”：-CF2O(CF2CF2O)9.8(CF2O)9.1CF2-
50.0g (0.097 mol of hydroxyl group) of the resulting fluorine-containing alcohol compound (VIII) was mixed with 50.0g of THF50.0g and 17.7g (0.125mol) of acryloyloxyethyl isocyanate in a dry air atmosphere, and the mixture was heated to 50 ℃. To this was added 0.05g of dioctyltin dilaurate, and the mixture was stirred at 50 ℃ for 24 hours. After completion of the heating, the residue was distilled off under reduced pressure at 80 ℃ under 0.266kPa to obtain 63.5g of a pale yellow highly viscous liquid. By1As a result of H-NMR and IR, it was confirmed that the fluorine-containing acrylic compound had a fluorine content of 29.7% by mass as shown below.
[ solution 29]
Rf”：-CF2O(CF2CF2O)9.8(CF2O)9.1CF2-
Examples 1 to 11 and comparative examples 1 to 7
The following shows raw material components of the fluorine-containing curable composition of the present invention.
(A) Fluorine-containing acrylic compound
(A-1) the fluorine-containing acrylic compound obtained in Synthesis example 1
(A-2) the fluorine-containing acrylic compound obtained in Synthesis example 2
(A-3) the fluorine-containing acrylic compound obtained in Synthesis example 3
(A-4) fluorine-containing acrylic Compound obtained in Synthesis example 4
(B) Fluorine-containing acrylic compound
(B-1) fluorine-containing acrylic Compound obtained in Synthesis example 5
(B-2) fluorine-containing acrylic Compound obtained in Synthesis example 6
(C) Non-fluorinated acrylic compounds
(C-1) pentaerythritol Ethoxytetraacrylate
[ Daicel-Allnex Ltd. EBECRYL 40)
(C-2) pentaerythritol triacrylate
(C-3) polyfunctional acrylate comprising pentaerythritol triacrylate and hexamethylene diisocyanate (UA-306H, Co., Ltd.)
(D) Photopolymerization initiator
(D-1) 1-Hydroxycyclohexylphenylketone (trade name: IRGACURE 184, manufactured by BASF Japan)
(D-2) 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl ] phenyl } -2-methylpropan-1-one (trade name: IRGACURE 127, manufactured by BASF Japan K.K.)
[ preparation of fluorine-containing curable composition ]
The components (a) and (B) were all diluted to 20 mass% with methyl ethyl ketone, and the component (C) was diluted to 40 mass% with butyl acetate. Further, the diluting solvent (C-1) was replaced with 2-propanol from butyl acetate, and the product diluted to 40 mass% was blended as (C-4).
The compounding ratios of the components (a) to (D) other than the solvent component were mixed so as to be shown in table 1 below, to obtain a fluorine-containing curable composition.
[ Table 1]
The blending ratios of the components (A) to (D) (excluding solvent components) in examples and comparative examples
[ dissolved state of composition ]
The dissolved state (coating liquid appearance) of each composition was visually observed. The composition in which the precipitate was generated was not evaluated thereafter. The results are shown in table 2.
Coating and preparation of cured product
Each of the compositions of examples and comparative examples was coated on a polycarbonate substrate using a wire bar No.7 (wet film thickness: 16.0 μm). After the coating was dried at 100 ℃ for 1 minute, the cumulative dose of irradiation was 400mJ/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 irradiating the coated surface with ultraviolet rays to obtain a cured film having a thickness of 5 μm.
[ evaluation of Water-and oil-repellency ]
1) Water contact Angle measurement
A droplet of 2. mu.L of water was dropped on the cured film using a contact angle meter (DropMaster, manufactured by Kyowa Kagaku K.K.), and the water contact angle after 1 second was measured. The average value of N-5 was used as the measurement value. The results are shown in table 2.
2) Oleic acid contact Angle determination
A4. mu.L drop of oleic acid was dropped onto the cured film using a contact angle meter (DropMaster, manufactured by Kyowa Kagaku K.K.), and the contact angle of oleic acid after 1 second was measured. The average value of N-5 was used as the measurement value. The results are shown in table 2.
[ measurement of coefficient of kinetic Friction ]
The dynamic friction coefficient of the cured film against benchmark (manufactured by asahi chemicals) was measured under the following conditions using a surface property tester 14FW (manufactured by new eastern science corporation). The results are shown in table 2.
Contact area: 10mm by 35mm
Loading: 100g
[ evaluation of repellency of Universal Pen ]
The surface of the cured film was marked with a straight line by a universal pen (HI Mckee bold letters, manufactured by ZEBRA corporation), and the repellency was evaluated by visual observation. The results are shown in table 2.
[ evaluation of Erasing Property with Universal Pen ]
On the surface of the cured film, a straight line was drawn with a universal pen (HI mcke bold letters manufactured by ZEBRA corporation), and after 1 minute, the surface was lightly rubbed with toilet paper 3 times, and the absence of the trace by the universal pen was evaluated as "erased" and the trace residue was evaluated as "unerased". The results are shown in table 2.
[ Table 2]
From the above results, it was found that the compositions of comparative examples 1 to 3 in which the component (B) was not blended and only the components (a) and (C) were blended had poor dissolution state of the composition and generated precipitates, while the compositions of examples 1 to 11 of the present invention in which the components (a), (B) and (C) were blended could produce transparent and uniform coating liquids, and the compositions of examples 1 to 11 of the present invention could form surfaces having high liquid repellency and slidability as compared with the compositions of comparative examples 4, 5 and 7 in which the component (a) was not blended and only the components (B) and (C) were blended.
Claims (12)
1. A fluorine-containing curable composition comprising a component (A), a component (B) and a component (C) as essential components, wherein the total amount of the components (A) and (B) is 0.05 to 50 parts by mass per 100 parts by mass of the component (C), and the amount of the component (A) is 1 to 100 parts by mass per 100 parts by mass of the component (B),
the component (A) is a linear polymer having a fluoropolyether in the main chain, and is composed of a compound having 1 or 2 (meth) acryloyl groups at one or both ends of the molecular chain, the average number of (meth) acryloyl groups contained in 1 molecule being 2 or less, and the fluorine content being 48 mass% or more and less than 62 mass%,
the component (B) is composed of a compound having 2 or more (meth) acryloyl groups at each molecular chain end in 1 molecule of a linear polymer having a fluoropolyether in the main chain, 4 to 10 (meth) acryloyl groups on average in 1 molecule, and a fluorine content of 25 mass% or more and less than 45 mass%,
the component (C) is composed of a non-fluorinated acrylic compound having no fluoropolyether structure and having an average of 2 or more (meth) acryloyl groups in 1 molecule.
2. The fluorine-containing curable composition according to claim 1, further comprising a photopolymerization initiator (D).
3. The fluorine-containing curable composition according to claim 1 or 2, wherein the component (A) is a fluorine-containing acrylic compound represented by any one of the following general formulae (1) and (2),
Rf1-O-Rf2-CF2-Z1-X1 (1)
X2-Z1-CF2O-Rf2-CF2-Z1-X1 (2)
in the formula, Rf1Is a fluorine atom or a C1-8 fluorine-containing alkyl group which may contain an oxygen atom, Rf2The following 2 kinds of repeating units
-CF2O-
-CF2CF2O-
Randomly arranged perfluoropolyether groups having a molecular weight of 600 to 20000 and a valence of 2, Z1Independently a linking group selected from a C1-20 (C2) hydrocarbon group which may contain at least 1 hetero atom selected from an oxygen atom, a nitrogen atom and a silicon atom, -C (═ O) -, and-C (═ O) O-, the C2 hydrocarbon group may contain a cyclic structure in the middle, a part of hydrogen atoms bonded to the carbon atoms may be substituted with fluorine atoms, and X is1Independently is a 1-valent organic group having a (meth) acryloyl group which may contain an oxygen atom and/or a nitrogen atom, X2Is hydroxy or X1。
4. The fluorine-containing curable composition according to any one of claims 1 to 3, wherein the component (B) is a fluorine-containing acrylic compound represented by the following general formula (3),
[ solution 1]
In the formula, Rf2The following 2 kinds of repeating units
-CF2O-
-CF2CF2O-
Randomly arranged 2-valent perfluoropolyether groups having a molecular weight of 600 to 20000, Q1Independently a (a +1) -valent linking group containing at least (a +1) silicon atoms, which may form a cyclic structure, a is an integer of 2 to 5, Z2Each independently is a C1-100 (C2) hydrocarbon group which may contain an oxygen atom and/or a nitrogen atom, may contain a cyclic structure in the middle, and R1Independently hydrogen atom or C1-C8 alkyl group, R2Independently a hydrogen atom, or an organic group having a valence of 1 of a (meth) acryloyl group which may contain an oxygen atom and/or a nitrogen atom, wherein R2Z is an organic group having 2 or more at each end in 1 molecule and having 4 to 10 of the above-mentioned valences 1 on average in 1 molecule3Independently, the linking group is a 2-valent hydrocarbon group having 1 to 20 carbon atoms, which may contain at least 1 hetero atom selected from an oxygen atom, a nitrogen atom and a silicon atom, and may contain a cyclic structure in the middle, and a part of hydrogen atoms bonded to carbon atoms may be substituted with fluorine atoms.
5. The fluorine-containing curable composition according to claim 3 or 4, wherein in the component (A), Z in the general formula (1) or (2)1In order to achieve any of the following configurations,
-C(＝O)-
-C(＝O)O-
-C(＝O)OCH2-
-C(＝O)OCH2CH2-
-CH2-
-CH2O-
-CH2OCH2-
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OC(＝O)NH-
-CH2OC(＝O)NHCH2CH2-。
6. the fluorine-containing curable composition according to any one of claims 3 to 5, wherein X in the general formula (1) or (2) in the component (A)1As indicated by any one of the following descriptions,
-OC(＝O)CH＝CH2
-OC(＝O)C(CH3)＝CH2
-C[OC(＝O)CH＝CH2]2
-C[OC(＝O)C(CH3)＝CH2]2
-CH[CH2OC(＝O)CH＝CH2][CH2OC(＝O)C(CH3)＝CH2]
-C(CH3)[CH2OC(＝O)CH＝CH2]2
-CH2[CH2OC(＝O)C(CH3)＝CH2]2
-C[CH2OC(＝O)CH＝CH2]
-C(CH2CH3)[CH2OC(＝O)CH＝CH2]2
-C(CH2CH3)[CH2OC(＝O)C(CH3)＝CH2]2。
7. the fluorine-containing curable composition according to any one of claims 3 to 6, wherein the fluorine-containing acrylic compound represented by the general formula (1) or (2) in the component (A) is represented by any one of the following,
Rf1ORf2CF2CH2OC(＝O)CH＝CH2
Rf1ORf2CF2CH2OC(＝O)C(CH3)＝CH2
HOCH2CF2ORf2CF2CH2OC(＝O)CH＝CH2
HOCH2CF2ORf2CF2CH2OC(＝O)C(CH3)＝CH2
Rf1ORf2CF2C(＝O)OCH2CH2OC(＝O)CH＝CH2
Rf1ORf2CF2C(＝O)OCH2CH2OC(＝O)C(CH3)＝CH2
HOCH2CF2ORf2CF2C(＝O)OCH2CH2OC(＝O)CH＝CH2
HOCH2CF2ORf2CF2C(＝O)OCH2CH2OC(＝O)C(CH3)＝CH2
Rf1ORf2CF2C(＝O)OCH[CH2OC(＝O)CH＝CH2][CH2OC(＝O)C(CH3)＝CH2]
Rf1ORf2CF2CH2OC(＝O)NHCH2CH2OC(＝O)CH＝CH2
Rf1ORf2CF2CH2OC(＝O)NHCH2CH2OC(＝O)C(CH3)＝CH2
HOCH2CF2ORf2CF2CH2OC(＝O)NHCH2CH2OC(＝O)CH＝CH2
HOCH2CF2ORf2CF2CH2OC(＝O)NHCH2CH2OC(＝O)C(CH3)＝CH2
HOCH2CF2ORf2CF2CH2OC(＝O)NHC(CH3)[CH2OC(＝O)CH＝CH2]2
CH2＝C(CH3)C(＝O)OCH2CF2ORf2CF2CH2OC(＝O)C(CH3)＝CH2
CH2＝CHC(＝O)OCH2CF2ORf2CF2CH2OC(＝O)C(CH3)＝CH2
CH2＝CHC(＝O)OCH2CF2ORf2CF2CH2OC(＝O)CH＝CH2
CH2＝CHC(＝O)OCH2CH2NHC(＝O)OCH2CF2ORf2CF2CH2OCH2OC(＝O)CH＝CH2
CH2＝C(CH3)C(＝O)OCH2CH2NHC(＝O)OCH2CF2ORf2CF2CH2OCH2OC(＝O)C(CH3)＝CH2
CH2＝CHC(＝O)OCH2CH2NHC(＝O)OCH2CF2ORf2CF2CH2OC(＝O)NHCH2CH2OC(＝O)CH＝CH2
in the formula, Rf1、Rf2As described above.
8. The fluorine-containing curable composition according to any one of claims 4 to 7, wherein in the component (B), Z in the general formula (3)3Represented by any one of the following formulae:
-CH2CH2-
-CH2CH2CH2-
-CH2CH2CH2CH2-
-CH2OCH2CH2-
-CH2OCH2CH2CH2-。
9. the fluorine-containing curable composition according to any one of claims 4 to 8, wherein Q in the general formula (3) is Q in the component (B)1Is represented by the following formula (I),
[ solution 2]
Wherein a1 is 2 or 3.
10. The fluorine-containing curable composition according to any one of claims 4 to 9, wherein the fluorine-containing acrylic compound represented by the general formula (3) in the component (B) is a fluorine-containing acrylic compound represented by the following general formula (4) or (5),
[ solution 3]
[ solution 4]
In the formula, Z3、Q1A is as described above, Rf' is-CF2O(CF2O)m(CF2CF2O)nCF2- (CF) wherein m is an integer of 1 to 200, n is an integer of 1 to 170, and m + n is an integer of 6 to 2012O) -and- (CF)2CF2The arrangement of O) -is random, R3Is a hydrogen atom or a methyl group, d1 and e1 are integers of 0 to 10, and the fluorine content in the compound represented by the formula (4) or (5) is 25 mass% or more and less than 45 mass%.
11. The fluorine-containing curable composition according to any one of claims 1 to 10, wherein the non-fluorinated acrylic compound of the component (C) is a polyfunctional acrylic compound having 2 or more (meth) acryloyl groups in 1 molecule and having no urethane bond, or a polyfunctional urethane acrylate having 3 or more (meth) acryloyl groups in 1 molecule obtained by reacting the polyfunctional acrylic compound with an aliphatic polyisocyanate and an acrylic compound having a hydroxyl group, or a mixture of 2 or more acrylic compounds including the polyfunctional acrylic compound and the urethane acrylate.
12. An article having a cured coating film of the fluorine-containing curable composition according to any one of claims 1 to 11 on the surface thereof.
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| JP2019026484 | 2019-02-18 | ||
| JP2019-026484 | 2019-02-18 | ||
| PCT/JP2020/002114 WO2020170698A1 (en) | 2019-02-18 | 2020-01-22 | Fluorine-containing curable composition and article |
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| JP (1) | JP7255666B2 (en) |
| KR (1) | KR20210127973A (en) |
| CN (1) | CN113439095A (en) |
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| CN114350260A (en) * | 2022-01-18 | 2022-04-15 | 美氟新材料科技(常州)有限公司 | Fluorine release coating with wear resistance and high stability and preparation method thereof |
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| JPWO2022203060A1 (en) | 2021-03-25 | 2022-09-29 | ||
| IL313421A (en) * | 2021-12-14 | 2024-08-01 | Shinetsu Chemical Co | Fluorine-containing active energy ray-curable composition, cured product, and article |
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| TW202041610A (en) | 2020-11-16 |
| WO2020170698A1 (en) | 2020-08-27 |
| KR20210127973A (en) | 2021-10-25 |
| JP7255666B2 (en) | 2023-04-11 |
| TWI844620B (en) | 2024-06-11 |
| JPWO2020170698A1 (en) | 2021-12-02 |
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