JP2017008128A - Active energy ray curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray curable resin composition capable of enhancing antifouling durability such as oil-based ink wiping property or the like without generating appearance defect due to white turbidness in a resin coated film obtained after curing.SOLUTION: An active energy ray curable resin composition contains an active energy ray curable resin, a photoradical polymerization initiator, an organic solvent, a perfluoropolyether compound having a polymerizable unsaturated group with a specific structure and a fluorine-containing 2 block copolymer having a polymerizable unsaturated group with a specific structure.SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable resin composition. More specifically, the present invention relates to an active energy ray-curable resin composition capable of forming a resin coating film excellent in antifouling durability (particularly magic ink wiping property).

  For imparting antifouling properties such as magic ink resistance or fingerprint resistance to resin coatings, perfluorocarbons having a polymerizable unsaturated group as a surface modifier are added to the active energy ray-curable resin composition. A method of adding a polyether (hereinafter abbreviated as “PFPE”) compound is widely used (for example, Patent Documents 1 and 2).

  However, since the PFPE compound has low solubility in the active energy ray-curable resin or its organic solvent solution, it is difficult to form a uniform solution, and the cured resin coating film becomes cloudy (increased haze, visible light transmittance). There was a problem.

  As a means for solving such a problem, a method using a PFPE compound having a polymerizable unsaturated group having a PFPE chain having a weight average molecular weight of about 2000 or less in the molecule, or binding a non-fluorine molecule fragment to the end of the PFPE molecule And a method for reducing the fluorine content contained in the PFPE compound having a polymerizable unsaturated group is known. As another solution, a method using a fluorine-containing dendrimer, a fluorine-containing block, or a graft polymer as a dispersion material of a PFPE compound having a polymerizable unsaturated group is known (for example, Patent Documents 3 to 6). ).

  Patent Document 7 discloses a method using a fluorine-containing random copolymer as a dispersant or compatibilizer for a PFPE compound having a polymerizable unsaturated group. Patent Document 8 discloses a method using a fluorine-containing block copolymer as the dispersant or compatibilizer. However, none of the fluorine-containing random copolymer or the fluorine-containing block copolymer disclosed in Patent Documents 7 and 8 has sufficient ability to dissolve (uniformly disperse) the PFPE compound.

  Patent Documents 9 and 10 disclose a method using a fluorine-containing random copolymer obtained by copolymerizing a bifunctional PFPE compound as a dispersant or compatibilizing agent for a PFPE compound having a polymerizable unsaturated group. Yes. Here, the PFPE chain-containing fluorine-containing random copolymer has a good ability to disperse the PFPE compound. However, the addition of the copolymer tends to lower the antifouling durability, particularly the magic ink wiping property.

  As described above, the PFPE compound having a polymerizable unsaturated group as a modifier can be well dispersed in the active energy ray-curable resin or the organic solvent solution thereof, and excellent in the cured resin coating film. A method for exhibiting antifouling durability has not yet been found.

JP 2012-72232 A International Publication No. 2003-002628 International Publication No. 2012-074071 International Publication No. 2014-069634 JP 2015-28613 A JP 2015-28614 A JP 2010-196044 A JP 2010-235784 A JP 2010-285613 A JP 2014-70113 A

  The object of the present invention is made in view of the above circumstances, and in the resin coating obtained after curing, active energy ray curing that can improve antifouling durability such as wiping performance of magic ink without causing poor appearance due to white turbidity. It is in providing a conductive resin composition.

  As a result of extensive research, the present inventor has found that a fluorine-containing diblock copolymer having a polymerizable unsaturated group having a specific structure is suitable as a dispersant for a PFPE compound having a polymerizable unsaturated group. The headline and the present invention have been completed.

（式（１）中、Ｘは２〜５の整数であり、Ｒ^１は水素原子またはメチル基である。Ｌは分子量３０〜６００のＸ＋１価の有機基であり、その内部に複数のウレタン結合、エステル結合、アミド結合またはエーテル結合等を含んでいてもよい。ｐおよびｑはそれぞれ独立に１〜５０の整数である。）

（式（２）中、Ｘは２〜５の整数であり、Ｒ^１は水素原子またはメチル基である。Ｌは分子量３０〜６００のＸ＋１価の有機基であり、その内部に複数のウレタン結合、エステル結合、アミド結合またはエーテル結合等を含んでいてもよい。Ｒｆ^２は炭素数１〜３のパーフルオロアルキル基である。ｒは１〜５０の整数である。）

（式（３）中、Ｒ^１は水素原子またはメチル基であり、ｌは１〜５の整数であり、Ｒｆ^１は１価の炭素数１〜１６のフルオロ炭化水素基である。）

（式（４）中、Ｒ^１は水素原子またはメチル基であり、Ｒｆ^２は炭素数１〜３のパーフルオロアルキル基であり、Ｒｆ^３は−ＣＦ_２ＣＦ（ＣＦ_３）−基または−ＣＦ_２ＣＦ_２ＣＦ_２−基であり、Ｒｆ^４は−ＣＦ_２ＣＦ_２−基または−ＣＦ（ＣＦ_３）−基である。ｍは１〜３０の整数である。） That is, the active energy ray-curable resin composition according to the present invention includes an active energy ray-curable resin, a photo radical polymerization initiator, an organic solvent, a perfluoropolyether compound having a polymerizable unsaturated group, and polymerization. Containing a fluorine-containing diblock copolymer having a polymerizable unsaturated group,
The perfluoropolyether compound having a polymerizable unsaturated group is a perfluoropolyether compound having a polymerizable unsaturated group represented by the following general formula (1) or (2):
The fluorine-containing diblock copolymer having a polymerizable unsaturated group includes a non-fluorine (meth) acrylate polymer block containing a non-fluorine (meth) acrylate ester having a hydroxyl group as a constituent monomer, and the following general formula: Fluorinated alkyl (meth) acrylic acid ester represented by (3) and perfluorinated polyether chain-containing (meth) acrylic acid ester represented by the following general formula (4) Fluorine-containing 2 having a polymerizable unsaturated group produced by reacting a (meth) acrylic acid ester having an isocyanate group with a fluorine-containing diblock copolymer having a hydroxyl group and an acid ester polymer block It is a block copolymer.

(In Formula (1), X is an integer of 2 to 5, R ¹ is a hydrogen atom or a methyl group. L is an X + 1 valent organic group having a molecular weight of 30 to 600, and a plurality of urethane bonds are contained therein. An ester bond, an amide bond, an ether bond, etc. p and q are each independently an integer of 1 to 50.)

(In Formula (2), X is an integer of 2 to 5, R ¹ is a hydrogen atom or a methyl group. L is an X + 1 valent organic group having a molecular weight of 30 to 600, and a plurality of urethane bonds are contained therein. And an ester bond, an amide bond, an ether bond, etc. Rf ² is a C 1 to C 3 perfluoroalkyl group, and r is an integer of 1 to 50.)

(In Formula (3), R ¹ is a hydrogen atom or a methyl group, l is an integer of 1 to 5, and Rf ¹ is a monovalent C 1-16 fluorohydrocarbon group.)

(In the formula (4), ^{R 1} is a hydrogen atom or a methyl group, Rf ² is a perfluoroalkyl group having 1 to 3 carbon atoms, Rf ³ is _-CF 2 CF (CF ₃₎ - group or -CF ₂ CF ₂ CF ₂ — group, Rf ⁴ is —CF ₂ CF ₂ — group or —CF (CF ₃ ) — group, and m is an integer of 1-30.

（式（５）中、Ｒ^１は水素原子またはメチル基であり、ａ＝ｂ＝０またはａは１〜３の整数であり、ｂは１〜２の整数であり、ｎは１〜６の整数である。ａ≠０かつｂ≠０の場合、−Ｃ_ｎＦ_２ｎ＋１は−（ＣＦ_２ＣＨ_２）_ｂ−基のＣＨ_２に結合しており、−（ＣＦ_２ＣＦ_２）_ａ−基は−（ＣＦ_２ＣＨ_２）_ｂ−のＣＦ_２基に結合している。） Moreover, it is preferable that the fluorinated alkyl (meth) acrylate ester represented by the general formula (3) is a fluorinated alkyl (meth) acrylate ester represented by the following general formula (5).

In (formula (5), ^{R 1} is a hydrogen atom or a methyl group, a = b = 0 or a is an integer of 1 to 3, b is an integer of 1 to 2, n is 1 to 6 for .a ≠ 0 and b ≠ 0 is an _integer, -C _{n F 2n + 1} is _{- (CF 2 CH 2) b} - is bonded to CH _{2 groups, - (CF 2 CF 2)} a - group It is bonded to the CF ₂ group of — (CF ₂ CH ₂ ) _b —.)

（式（６）中、Ｒ^１は水素原子またはメチル基であり、ｓは１〜６の整数である。） Moreover, it is preferable that the fluorinated alkyl (meth) acrylic acid ester represented by the general formula (3) is a fluorinated alkyl (meth) acrylic acid ester represented by the following general formula (6).

(In the formula (6), ^{R 1} is a hydrogen atom or a methyl group, s is an integer from 1 to 6.)

（式（７）中、Ｒ^１は水素原子またはメチル基であり、ｍは１〜３０の整数である。Ｒｆ^２は炭素数１〜３のパーフルオロアルキル基である。） The perfluoropolyether chain-containing (meth) acrylic acid ester represented by the general formula (4) is a perfluoropolyether chain-containing (meth) acrylic acid ester represented by the following general formula (7). It is preferable.

(In the formula (7), ^{R 1} is a hydrogen atom or a methyl group, m is .Rf ² is an integer of 1 to 30 is a perfluoroalkyl group having 1 to 3 carbon atoms.)

（式（８）中、Ｒ^１は水素原子またはメチル基であり、ｍは１〜３０の整数である。Ｒｆ^２は炭素数１〜３のパーフルオロアルキル基である。） The perfluoropolyether chain-containing (meth) acrylic acid ester represented by the general formula (4) is a perfluoropolyether chain-containing (meth) acrylic acid ester represented by the following general formula (8). It is preferable.

(In the formula (8), ^{R 1} is a hydrogen atom or a methyl group, m is .Rf ² is an integer of 1 to 30 is a perfluoroalkyl group having 1 to 3 carbon atoms.)

  Moreover, it is preferable that the weight average molecular weights of the said fluorine-containing diblock copolymer which has a polymerizable unsaturated group are 5000-50000.

  Moreover, it is preferable that the perfluoropolyether compound which has the said polymerizable unsaturated group is 0.005-1.0 weight part with respect to 100 weight part of said active energy ray curable resins.

  Moreover, it is preferable that the fluorine-containing diblock copolymer which has the said polymerizable unsaturated group is 0.001-0.2 weight part with respect to 100 weight part of said active energy ray curable resins.

（式（９）中、Ｒ^２およびＲ^３はそれぞれ独立に水素原子または炭素数１から３のアルキル基であり、Ｒ^２およびＲ^３どちらか一方にひとつのカルボキシル基を含んでいてもよい。Ｒ^４は炭素数１〜１８の直鎖状アルキル基である。） The fluorine-containing diblock copolymer having a hydroxyl group is produced by living radical polymerization in the presence of a trithiocarbonate represented by the following general formula (9). It is preferable that

(In Formula (9), R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and one of R ² and R ³ may contain one carboxyl group. R ⁴ is a linear alkyl group having 1 to 18 carbon atoms.)

  According to the present invention, the organic solvent solution of the active energy ray-curable resin has a PFPE compound having a polymerizable unsaturated group having a specific structure and a polymerizable unsaturated group having a specific structure as a dispersant. By adding a fluorine-containing diblock copolymer, a cured resin having a good appearance without white turbidity and excellent antifouling durability (especially wiping property for magic ink) on the surface of an inorganic base material or resin base material A coating film can be formed.

  Hereinafter, the present invention will be described in detail according to embodiments.

  The active energy ray-curable resin composition according to the present embodiment contains components [A] to [E] described below. In addition, you may contain various additives as needed.

Component [A]: Active energy ray curable resin In the active energy ray curable resin composition according to the present embodiment, the active energy ray curable resin is not particularly limited, but for example, an acrylic polyfunctional oligomer and an acrylic polyfunctional oligomer. Either one or both of the functional monomers (a mixture thereof) can be used.

  Examples of the acrylic polyfunctional oligomer include urethane acrylate, epoxy acrylate, and polyester acrylate.

  Examples of bifunctional acrylic monomers include 1,4-butane diacrylate, 1,6-hexane diacrylate, 1,9-nonane diacrylate, neopentyl diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethylene oxide modified Examples thereof include bisphenol A diacrylate, propylene oxide-modified bisphenol A diacrylate, and epichlorohydrin-modified bisphenol A diacrylate.

  Examples of tri- or more functional acrylic monomers include trimethylol pullane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, and propylene oxide modified glycerin triacrylate. Etc.

  Moreover, the active energy ray-curable resin according to the present embodiment may include a monofunctional monomer in addition to the acrylic polyfunctional oligomer and the acrylic polyfunctional monomer. Examples of the monofunctional monomer include aliphatic acrylates, alicyclic acrylates, ether acrylates, cyclic ether acrylates, hydroxyl group-containing acrylates, aromatic acrylates, and carboxyl group-containing acrylates.

Component [B]: Photoradical polymerization initiator In the active energy ray-curable resin composition according to the present embodiment, the photoradical polymerization initiator is not particularly limited. For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin compounds such as isopropyl ether, benzoin isobutyl ether, 2-phenyl-2- (p-toluenesulfonyloxy) acetophenone and methyl phenylglyoxylate, 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone and 2, Benzyl ketal compounds such as 2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-4 ′-(2-hydroxye Α) such as toxi) -2-methylpropiophenone and 2-hydroxy-1- [4- (4- (2-hydroxy-2-methyl-propionyl) -benzyl) phenyl] -2-methylpropan-1-one -Hydroxyacetophenone compounds, 2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone, 2-dimethylamino-2-[(4-methylphenyl) methyl] -4'-morpholinobutyrophenone and 2-methyl-4 ' Α-aminoacetophenone compounds such as-(methylthio) -2-morpholinopropiophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Acylphosphine oxide compounds, bis (η5-2,4 Titanocene compounds such as pentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, and 1,2-octanedione-1- [4- (phenylthio ) Phenyl-2- (O-benzoyloxime)] and ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) O-acyl oxime compounds and the like can be used.

  Further, for the purpose of improving the action of the photo radical polymerization initiator, for example, a photosensitizer such as thioxanthones, Mihilaz ketones and coumarins may be added.

  In the active energy ray-curable resin composition according to the present embodiment, the content of the photo radical polymerization initiator (component [B]) is 100 parts by weight of the active energy ray-curable resin (component [A]). Preferably it is 0.1-10 weight part, More preferably, it is 0.5-5 weight part.

Component [C]: Organic solvent In the active energy ray-curable resin composition according to the present embodiment, the organic solvent is not particularly limited. For example, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, methyl isobutyl ketone, cyclohexane Pentanone, cyclohexanone, acetylacetone, ethyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, 1,2-xylene, 1,3-xylene, 1,4-xylene, etc. Can be used. A fluorine-containing solvent such as 1,3-bis (trifluoromethyl) benzene can be used. Moreover, you may use 2 or more types of solvent chosen from the above by arbitrary mixing ratios.

  In the active energy ray-curable resin composition according to this embodiment, the content of the organic solvent (component [C]) is preferably 25 with respect to 100 parts by weight of the active energy ray-curable resin (component [A]). It is -900 weight part, More preferably, it is 50-400 weight part.

Component [D]: Perfluoropolyether compound having a polymerizable unsaturated group In the active energy ray-curable resin composition according to this embodiment, the perfluoropolyether compound having a polymerizable unsaturated group has the following general formula ( It is a perfluoropolyether compound having a polymerizable unsaturated group represented by 1) or (2).

上記一般式（１）において、Ｘは２〜５の整数であり、Ｒ^１は水素原子またはメチル基である。Ｌは分子量３０〜６００のＸ＋１価の有機基であり、その内部に複数のウレタン結合、エステル結合、アミド結合またはエーテル結合等を含んでいてもよい。ｐおよびｑはそれぞれ独立に１〜５０の整数であり、好ましくは５〜３０の整数である。なお、上記一般式（１）のパーフルオロポリエーテル鎖は、パーフルオロオキシメチレン基（ＣＦ_２Ｏ）およびパーフルオロオキシエチレン基（ＣＦ_２ＣＦ_２Ｏ）からなるランダム共重合体構造を有している。

In the general formula (1), X is an integer of 2 to 5, and R ¹ is a hydrogen atom or a methyl group. L is an X + 1 valent organic group having a molecular weight of 30 to 600, and may contain a plurality of urethane bonds, ester bonds, amide bonds, ether bonds, or the like. p and q are each independently an integer of 1 to 50, preferably an integer of 5 to 30. The perfluoropolyether chain of the general formula (1) has a random copolymer structure composed of a perfluorooxymethylene group (CF ₂ O) and a perfluorooxyethylene group (CF ₂ CF ₂ O). Yes.

上記一般式（２）において、Ｘ、Ｒ^１およびＬは、上記一般式（１）の定義と同義である。Ｒｆ^２は炭素数１〜３のパーフルオロアルキル基である。ｒは１〜５０の整数であり、好ましくは５〜３０の整数である。

In the general formula (2), X, ^{R 1} and L are the same as those defined in the general formula (1). Rf ² is a perfluoroalkyl group having 1 to 3 carbon atoms. r is an integer of 1-50, preferably an integer of 5-30.

In the general formulas (1) and (2), (CH ₂ ═CHCO ₂ ) x-L— is not particularly limited, and examples thereof include structures represented by the following formulas (I) to (XII). .

However, in the above formula (I) ~ (XII), * _represents a binding site for _{(CH 2 = CHCO 2) x} -L- subsequent oxygen atom, A represents an acryloyl group or a methacryloyl group.

  As the PFPE compound having such a polymerizable unsaturated group, a commercially available product or a synthesized product can be used. Examples of commercially available products include Fluorolink (registered trademark) AD1700 (manufactured by Solvay Solexis: tetrafunctional urethane acrylate compound). Moreover, as a synthetic product, the PFPE compound which has the polymerizable unsaturated group manufactured by the following methods is mentioned, for example.

The PFPE compound having a polymerizable unsaturated group having the chemical structure of the above formula (V) is, for example, a PFPE compound having a hydroxyl group at the terminal (represented by the following formula (V-1) or (V-2)). , And producing an isocyanate compound 1,1- (bisacryloyloxymethyl) ethyl isocyanate (represented by the following formula (V-3)) having a polymerizable unsaturated group by reacting in the presence of a urethanization catalyst. Can do.

  The said reaction can be performed at 0-100 degreeC in a fluorine-containing solvent. As the fluorine-containing solvent, for example, 1,3-bis (trifluoromethyl) benzene or the like can be used.

  As the urethanization catalyst, an organic tin compound, an organic titanium compound, an organic zirconium compound, or an organic amine compound can be used. Moreover, you may use together an amine compound and an organotin compound.

  Examples of the organic tin compound include dibutyltin dilaurate, bis (2-ethylhexanoate) tin, and dibutyltinbis (2,4-pentanedionate).

  Examples of the organic titanium compound include titanium diisopropoxy bis (ethyl acetoacetate).

  Examples of the organic zirconium compound include zirconium dibutoxybis (ethyl acetoacetate) and zirconium tetra (acetylacetonate).

  Examples of the organic amine compound include N-methylmorpholine, N-ethylmorpholine, triethylenediamine, bis (dimethylaminoethyl) ether, 1,4-diazabicyclo (2,2,2) octane, pentamethyldiethylenetriamine, N, N- Dimethylcyclohexylamine, N-methyldicyclohexylamine, N, N, N, N-tetramethylpropylenediamine, N, N, N, N-tetramethylhexamethylenediamine, N-methylmorpholine, N-ethylmorpholine, N, N -Dimethylethanolamine, N, N-diethylethanolamine, 1,8-diazabicyclo [5,4,0] undecene-7, and the like.

  In addition to the above, an organic acid salt of 1,8-diazabicyclo [5,4,0] -7-undecene can also be used as the urethanization catalyst. As an organic acid salt of 1,8-diazabicyclo [5,4,0] -7-undecene, for example, 1,8-diazabicyclo [5,4,0] -7-undecene formate, 2-ethylhexanoate , Phenol salts, octylates, p-toluenesulfonates and orthophthalates.

  Moreover, the PFPE compound which has a polymerizable unsaturated group which has the chemical structure of said formula (VI) can be manufactured according to patent document 1, for example. Moreover, the PFPE compound which has a polymerizable unsaturated group which has a chemical structure of the said formula (XII) can be manufactured according to patent document 2, for example.

  In the active energy ray-curable resin composition according to this embodiment, the content of the perfluoropolyether compound having a polymerizable unsaturated group (component [D]) is the active energy ray-curable resin (component [A]). Preferably it is 0.005-1.0 weight part with respect to 100 weight part, More preferably, it is 0.01-0.5 weight part.

Component [E]: Fluorine-containing diblock copolymer having a polymerizable unsaturated group In the active energy ray-curable resin composition according to this embodiment, the fluorine-containing diblock copolymer having a polymerizable unsaturated group is: A non-fluorine (meth) acrylate polymer block containing a non-fluorine (meth) acrylate having a hydroxyl group as a constituent monomer, a fluorinated alkyl (meth) acrylate represented by the following general formula (3), and Fluorine-containing 2 block having a hydroxyl group comprising a fluorine-containing (meth) acrylate polymer block having a perfluoropolyether chain-containing (meth) acrylate represented by the following general formula (4) as a constituent monomer It is produced by reacting a copolymer with a (meth) acrylic acid ester having an isocyanate group. That.

上記一般式（３）において、Ｒ^１は水素原子またはメチル基であり、ｌは１〜５の整数であり、Ｒｆ^１は１価の炭素数１〜１６のフルオロ炭化水素基である。

In the above general formula (3), R ¹ is a hydrogen atom or a methyl group, 1 is an integer of 1 to 5, and Rf ¹ is a monovalent C 1-16 fluorohydrocarbon group.

上記一般式（４）において、Ｒ^１は水素原子またはメチル基である。Ｒｆ^２は炭素数１〜３のパーフルオロアルキル基であり、例えばトリフルオロメチル基、パーフルオロエチル基、パーフルオロ‐ｎ‐プロピル基およびパーフルオルイソプロピル基等が挙げられる。Ｒｆ^３は−ＣＦ_２ＣＦ（ＣＦ_３）−基または−ＣＦ_２ＣＦ_２ＣＦ_２−基であり、Ｒｆ^４は−ＣＦ_２ＣＦ_２−基または−ＣＦ（ＣＦ_３）−基である。また、ｍは１〜３０の整数である。

In the general formula (4), R ¹ is a hydrogen atom or a methyl group. Rf ² is a perfluoroalkyl group having 1 to 3 carbon atoms, and examples thereof include a trifluoromethyl group, a perfluoroethyl group, a perfluoro-n-propyl group, and a perfluoroisopropyl group. Rf ³ is a —CF ₂ CF (CF ₃ ) — group or a —CF ₂ CF ₂ CF ₂ — group, and Rf ⁴ is a —CF ₂ CF ₂ — group or a —CF (CF ₃ ) — group. Moreover, m is an integer of 1-30.

  In the present specification, the phrase “(meth) acrylic acid ester” is used as a concept including both an acrylic acid ester and a methacrylic acid ester. Further, the phrase “non-fluorine” attached to a compound or a solvent is used to clarify that it is not “fluorine-containing”, that is, does not contain a fluorine atom in the molecule.

  The fluorine-containing diblock copolymer having a polymerizable unsaturated group having a PFPE chain in the polymer chain side chain according to the present embodiment is, for example, a polymerizable unsaturated group having a PFPE chain having a weight average molecular weight of 2000 or more in the molecule. A PFPE compound having an organic solvent can be dispersed in an organic solvent solution of an active energy ray curable resin to form a uniform solution, and antifouling properties such as wiping of magic ink can be obtained without impairing the appearance of the resin coating film obtained after curing. Durability can be improved effectively.

  In the active energy ray-curable resin composition according to the present embodiment, the content of the fluorine-containing diblock copolymer (component [E]) having a polymerizable unsaturated group is the active energy ray-curable resin (component [A] ]) Preferably it is 0.001-0.2 weight part with respect to 100 weight part, More preferably, it is 0.002-0.1 weight part. When there is too little content of the fluorine-containing diblock copolymer (component [E]) which has a polymerizable unsaturated group, it is enough with respect to the perfluoro polyether compound (component [D]) which has the said polymerizable unsaturated group. There is a tendency that a dispersion effect cannot be obtained, and when it is too much, the magic ink wiping property of the cured resin coating film tends to be lowered.

  Next, the production process and form of the fluorine-containing diblock copolymer (component [E]) having a polymerizable unsaturated group will be described.

(Fluorine-containing diblock copolymer having a hydroxyl group)
The fluorine-containing diblock copolymer having a hydroxyl group is represented by the non-fluorine (meth) acrylic acid ester polymer block containing a non-fluorine (meth) acrylic acid ester having a hydroxyl group as a constituent monomer, and the general formula (3). Fluorinated alkyl (meth) acrylic acid ester and perfluoropolyether chain-containing (meth) acrylic acid ester represented by the general formula (4) as a constituent monomer It consists of blocks.

  In this embodiment, the composition ratio (weight ratio) of each block in the fluorine-containing diblock copolymer having a hydroxyl group is 10 to 90% by weight of the non-fluorine (meth) acrylic acid ester polymer block. The fluorine-containing (meth) acrylic acid ester polymer block is preferably 90 to 10% by weight.

  Moreover, in this embodiment, it is preferable that the weight average molecular weights of the fluorine-containing diblock copolymer which has a hydroxyl group are 5,000-100,000, More preferably, it is 5,000 to 50,000.

((Non-fluorine (meth) acrylic acid ester polymer block))
The non-fluorine (meth) acrylate polymer block contains a non-fluorine (meth) acrylate ester having a hydroxyl group as a constituent monomer. Such a non-fluorine (meth) acrylic acid ester polymer block can be formed, for example, by polymerizing a non-fluorine (meth) acrylic acid ester having a hydroxyl group.

  Although the non-fluorine (meth) acrylic acid ester having a hydroxyl group is not particularly limited, for example, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid-2-hydroxy Propyl, (meth) acrylic acid-4-hydroxybutyl, (meth) acrylic acid-2-hydroxybutyl, polyethylene glycol mono (meth) acrylic acid ester, propylene glycol mono (meth) acrylic acid ester, 1,4-cyclohexanedi Examples include methanol mono (meth) acrylic acid ester and 1,3-dihydroxyadamantane mono (meth) acrylic acid ester.

  Moreover, the non-fluorine (meth) acrylic acid ester polymer block may contain a non-fluorine (meth) acrylic acid ester copolymerizable with a non-fluorine (meth) acrylic acid ester having a hydroxyl group as a constituent monomer. Examples of such non-fluorine (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid. n-butyl, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth) acrylic acid n-octyl, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, ( Benzyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, (meth Dicyclopentanyl acrylate and (meth) dicyclopentenyl acrylic acid.

  In this embodiment, it is preferable that the structural ratio (weight ratio) of the (meth) acrylic acid ester having a hydroxyl group in the non-fluorine (meth) acrylic acid ester polymer block is 5 to 100% by weight.

((Fluorine-containing (meth) acrylic ester polymer block))
The fluorine-containing (meth) acrylic acid ester polymer block includes a fluorinated alkyl (meth) acrylic acid ester represented by the general formula (3) and a perfluoropolyether chain represented by the general formula (4). Containing (meth) acrylic acid ester as a constituent monomer. Such a fluorine-containing (meth) acrylic acid ester polymer block includes, for example, a fluorinated alkyl (meth) acrylic acid ester represented by the general formula (3) and a par It can be formed by random copolymerization with a fluoropolyether chain-containing (meth) acrylic acid ester.

  In this embodiment, the fluorinated alkyl (meth) acrylate represented by the general formula (3) is a fluorinated alkyl (meth) acrylate represented by the following general formula (5) or (6). Preferably, it is a fluorinated alkyl (meth) acrylic acid ester represented by the following general formula (6).

上記一般式（５）において、Ｒ^１は水素原子またはメチル基であり、ａ＝ｂ＝０またはａは１〜３の整数であり、ｂは１〜２の整数であり、ｎは１〜６の整数である。ａ≠０かつｂ≠０の場合、−Ｃ_ｎＦ_２ｎ＋１は−（ＣＦ_２ＣＨ_２）_ｂ−基のＣＨ_２に結合しており、−（ＣＦ_２ＣＦ_２）_ａ−基は−（ＣＦ_２ＣＨ_２）_ｂ−のＣＦ_２基に結合している。

In the general formula (5), ^{R 1} is a hydrogen atom or a methyl group, a = b = 0 or a is an integer of 1 to 3, b is an integer of 1 to 2, n is 1 to 6 Is an integer. When a ≠ 0 and b ≠ 0, —C _n F _{2n + 1} is bonded to CH ₂ of the — (CF ₂ CH ₂ ) _b — group, and — (CF ₂ CF ₂ ) _a — group is — (CF ₂ Bonded to the CF ₂ group of CH ₂ ) _b —.

上記一般式（６）において、Ｒ^１は水素原子またはメチル基であり、ｓは１〜６の整数である。好ましくは、ｓは４〜６の整数である。

In the general formula (6), ^{R 1} is a hydrogen atom or a methyl group, s is an integer from 1 to 6. Preferably, s is an integer of 4-6.

  Examples of the fluorinated alkyl (meth) acrylate represented by the general formula (5) include 3,3,4,4,4-pentafluorobutyl (meth) acrylate, 3,3,4,4,5. , 5,6,6,6-nonafluorohexyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl (meth) Acrylate, 3,3,4,4,5,5,7,7,8,8,8-undecafluorooctyl (meth) acrylate, 3,3,4,4,5,5,7,7,8 , 8,9,9,10,10,10-pentadecafluorodecyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,9,9,10,10, 10-pentadecafluorodecyl (meth) acrylate, 3,3,4,4,5,5,7,7 9,9,10,10,10-tridecafluorodecyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11 , 12, 12, 12-Nonadecafluorododecyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,9,9,11,11,12,12,12- Heptadecafluorododecyl (meth) acrylate, 3,3,4,4,5,5,7,7,9,9,10,10,11,11,12,12,12-heptadecafluorododecyl (meth) Acrylate and 3,3,4,4,5,5,6,6,7,7,9,9,11,11,12,12,13,13,14,14,14-heneicosafluorotetradecyl (Meth) acrylate etc. are mentioned. Among them, 3,3,4,4,5,5,6,6,6-nonafluorohexyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8, 8,8-tridecafluorooctyl (meth) acrylate and 3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12 -Nonadecafluorododecyl (meth) acrylate is preferred.

  Examples of the fluorinated alkyl (meth) acrylate represented by the general formula (6) include 2,2-difluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoro-n-propyl (meth) ) Acrylate, 2,2,3,3,4,4,5,5-octafluoro-n-pentyl (meth) acrylate and 2,2,3,3,4,4,5,5,6,6 Examples include 7,7-dodecafluoro-n-heptyl (meth) acrylate. Among them, 2,2,3,3,4,4,5,5-octafluoro-n-pentyl (meth) acrylate and 2,2,3,3,4,4,5,5,6,6,7 , 7-dodecafluoro-n-heptyl (meth) acrylate is preferred.

  In this embodiment, the perfluoropolyether chain-containing (meth) acrylic acid ester represented by the general formula (4) has a perfluoropolyether chain content represented by the following general formula (7) or (8) ( It is preferably a (meth) acrylic acid ester.

上記一般式（７）において、Ｒ^１は水素原子またはメチル基であり、ｍは１〜３０の整数である。Ｒｆ^２は炭素数１〜３のパーフルオロアルキル基である。

In the general formula (7), ^{R 1} is a hydrogen atom or a methyl group, m is an integer of 1 to 30. Rf ² is a perfluoroalkyl group having 1 to 3 carbon atoms.

上記一般式（７）において、Ｒ^１は水素原子またはメチル基であり、ｍは１〜３０の整数である。Ｒｆ^２は炭素数１〜３のパーフルオロアルキル基である。

In the general formula (7), ^{R 1} is a hydrogen atom or a methyl group, m is an integer of 1 to 30. Rf ² is a perfluoroalkyl group having 1 to 3 carbon atoms.

  As the perfluoropolyether chain-containing (meth) acrylic acid ester represented by the general formula (4), more specifically, perfluoropolyethers represented by the following general formulas (4-1) to (4-12) Examples include chain-containing (meth) acrylic acid esters.

  In the general formulas (4-1) to (4-12), m is an integer of 1 to 30. In actual use, perfluoropolyether chain-containing (meth) acrylic acid ester in which m has a single value may be used, or a mixture thereof may be used.

  In this embodiment, the constituent ratio (weight ratio) of the fluorinated alkyl (meth) acrylate ester and perfluoropolyether chain-containing (meth) acrylate ester in the fluorine-containing (meth) acrylate polymer block is as follows: It is preferable that it is 1 / 99-90 / 10 (all units are weight%).

((Method for producing fluorine-containing diblock copolymer having a hydroxyl group))
The fluorine-containing diblock copolymer having a hydroxyl group can be produced, for example, by controlled living radical polymerization. Representative methods of controlled living radical polymerization include, for example, reversible addition-fragmentation chain transfer polymerization (RAFT polymerization), atom transfer radical polymerization (ATRP), and nitroxide-mediated radical polymerization (NMP).

  Since ATRP uses a transition metal catalyst such as a copper catalyst, a step of removing the transition metal catalyst may be required after the polymerization step. NMP requires a relatively high polymerization temperature. On the other hand, RAFT polymerization is applicable to a wide range of non-fluorine (meth) acrylic acid esters and fluorine-containing (meth) acrylic acid esters. It is. In RAFT polymerization, a dithiobenzoate compound, a trithiocarbonate compound, a dithiocarbamate compound, a xanthate compound, or the like can be used, but a trithiocarbonate compound is suitable as a RAFT agent from the viewpoint of polymerization control.

  The process for producing a fluorine-containing diblock copolymer having a hydroxyl group includes, for example, a first process and a second process. In the first step, a fluorinated alkyl (meth) acrylate represented by the general formula (3) and a perfluoropolyether represented by the general formula (4) in the presence of a trithiocarbonate and a radical polymerization initiator. This is a step of randomly copolymerizing a chain-containing (meth) acrylic acid ester. The second step is a step of polymerizing a non-fluorine (meth) acrylic acid ester having a hydroxyl group in the presence of the fluorine-containing (meth) acrylic acid ester polymer obtained in the first step.

  In the first step, the trithiocarbonate is not particularly limited, but from the viewpoint of the polymerization rate and the polymerization yield, those represented by the following general formula (9) can be suitably used in the present embodiment.

上記一般式（９）中、Ｒ^２およびＲ^３はそれぞれ独立に水素原子または炭素数１から３のアルキル基であり、Ｒ^２およびＲ^３どちらか一方にひとつのカルボキシル基を含んでいてもよい。好ましいＲ^２およびＲ^３として、例えば水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基および２−カルボキシエチル基等が挙げられる。Ｒ^４は炭素数１〜１８の直鎖状アルキル基である。トリチオ炭酸エステルの耐加水分解性を考慮すると、Ｒ^４は炭素数６〜１８の直鎖状アルキル基が好ましい。

In the general formula (9), R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and one of R ² and R ³ may contain one carboxyl group. . Preferred examples of R ² and R ³ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a 2-carboxyethyl group. R ⁴ is a linear alkyl group having 1 to 18 carbon atoms. Considering the hydrolysis resistance of the trithiocarbonate, R ⁴ is preferably a linear alkyl group having 6 to 18 carbon atoms.

  Examples of the trithiocarbonate include 2-cyano-2-propyldodecyltrithiocarbonate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid, and cyanomethyldodecyltrithiocarbonate.

  The amount of trithiocarbonate used is preferably 1 to 20% by weight based on the total weight of the fluorinated alkyl (meth) acrylate and the perfluoropolyether group-containing (meth) acrylate.

  The copolymerization of the fluorinated alkyl (meth) acrylic acid ester and the perfluoropolyether chain-containing (meth) acrylic acid ester can be carried out in the absence of a solvent (bulk) or in a suitable organic solvent. As the polymerization solvent, for example, a fluorine-containing solvent such as 1,3-bis (trifluoromethyl) benzene can be used. Moreover, as a cosolvent of a fluorine-containing solvent, the mixed solvent which added the non-fluorine solvent can also be used. Examples of the non-fluorine solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, toluene and xylene.

  It is preferable that the usage-amount of a solvent is 0-100 weight part with respect to 100 weight part of fluorine-containing (meth) acrylic acid ester. If it exceeds 100 parts by weight, the polymerization rate becomes slow, which is not practical.

  The copolymerization of the fluorinated alkyl (meth) acrylate ester and the perfluoropolyether chain-containing (meth) acrylate ester is preferably performed at 0 to 150 ° C., more preferably at 40 to 100 ° C. preferable. If it is less than 0 degreeC, sufficient polymerization rate may not be achieved but it may lead to the fall of a polymerization yield. On the other hand, when the temperature exceeds 150 ° C., an inactive fluorine-containing (meth) acrylic acid ester copolymer that does not contain a trithiocarbonate ester fragment at the polymer end tends to be easily formed.

  The radical polymerization initiator used in the first step is not particularly limited as long as the polymerization reaction can proceed smoothly without any particular problem. For example, an azo radical polymerization initiator can be preferably used. Examples of such azo radical polymerization initiators include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1'-azobis (cyclohexane). Carbonitrile) and 4,4-azobis (4-cyanovaleric acid).

  The radical polymerization initiator is preferably used in an amount of 5 to 35 mol%, more preferably 10 to 30 mol%, based on the trithiocarbonate. If it is less than 5 mol%, the polymerization yield may be reduced. On the other hand, if it exceeds 35 mol%, an inert fluorine-containing (meth) acrylic acid ester polymer that does not contain a trithiocarbonate ester fragment at the polymer end tends to be easily formed.

  The second step is a step of polymerizing the non-fluorine (meth) acrylic acid ester having a hydroxyl group in the presence of the polymer of the fluorine-containing (meth) acrylic acid ester obtained in the first step. In the second step, the above-mentioned non-fluorine (meth) acrylic acid ester having a hydroxyl group can be used as a monomer. In addition to the non-fluorine (meth) acrylic acid ester having a hydroxyl group, a non-fluorine (meth) acrylic acid ester copolymerizable with a non-fluorine (meth) acrylic acid ester having a hydroxyl group may be used in combination. As the copolymerizable non-fluorine (meth) acrylic acid ester, those described above can be used.

  The second step can be performed by adding a (meth) acrylic acid ester having a hydroxyl group, a radical polymerization initiator and a polymerization solvent to the polymer solution obtained in the first step. In addition, the (meth) acrylic acid ester having a new hydroxyl group is newly isolated and purified by reprecipitation operation such as adding the fluorine-containing (meth) acrylic acid ester polymer obtained in the first step to a poor solvent, It can also be carried out by adding a radical polymerization initiator and a polymerization solvent.

  The polymerization solvent used in the second step is appropriately selected in consideration of the solubility of the fluorine-containing (meth) acrylic acid ester polymer obtained in the first step and the non-fluorine (meth) acrylic acid ester having a hydroxyl group. . As the polymerization solvent, for example, a fluorine-containing solvent such as 1,3-bis (trifluoromethyl) benzene is used. A mixed solvent obtained by adding a non-fluorine solvent as an auxiliary solvent to a fluorine-containing solvent can also be used. Examples of the non-fluorine solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, isobutyl acetate, toluene and xylene.

  The amount of the solvent used is 50 to 200 parts by weight based on the total weight of the fluorine-containing (meth) acrylic acid ester polymer obtained in the first step and the monomer newly added in the second step. preferable. If it is less than 50 parts by weight, the viscosity of the reaction solution increases with the progress of polymerization, and stirring and mixing may become difficult. On the other hand, if it exceeds 200 parts by weight, the polymerization rate becomes slow, which is not practical.

  Polymerization of the monomer containing a non-fluorine (meth) acrylic acid ester having a hydroxyl group is preferably performed at 0 to 150 ° C, more preferably at 40 to 100 ° C. If it is less than 0 degreeC, sufficient polymerization rate may not be achieved but it may lead to the fall of a polymerization yield. On the other hand, when it exceeds 150 ° C., a polymer of non-fluorine (meth) acrylic acid ester having an inactive hydroxyl group that does not contain a trithiocarbonate ester fragment at the polymer end tends to be easily formed.

Examples of the radical polymerization initiator used in the second step include the same radical polymerization initiators used in the first step.
The radical polymerization initiator is preferably used in an amount of 5 to 35 mol% with respect to the trithiocarbonate ester fragment contained in the fluorine-containing (meth) acrylic acid ester polymer obtained in the first step, more preferably 10 to 30 mol%. If the radical polymerization initiator is less than 5 mol%, the polymerization yield may be reduced. On the other hand, if the radical polymerization initiator is more than 35 mol%, a non-fluorine (meth) acrylate polymer having an inactive hydroxyl group that does not contain a trithiocarbonate ester fragment at the polymer end tends to be easily formed. It is in.

(Method for producing fluorine-containing diblock copolymer having a polymerizable unsaturated group)
The fluorine-containing diblock copolymer having a polymerizable unsaturated group is produced by reacting the fluorine-containing diblock copolymer having a hydroxyl group with a (meth) acrylic acid ester having an isocyanate group.

  Here, the molar equivalent ratio (-NCO / -OH) between the isocyanate group of the (meth) acrylic acid ester having an isocyanate group and the hydroxyl group contained in the fluorine-containing diblock copolymer having a hydroxyl group is 0.2 to It is preferably 1.2, more preferably 0.5 to 1.2.

  The (meth) acrylic acid ester having an isocyanate group is not particularly limited. For example, 2- (meth) acryloyloxyethyl isocyanate, 3- (meth) acryloyloxypropyl isocyanate and 1,1- (bis (meth) acryloyloxymethyl) ) Ethyl isocyanate and the like.

  Moreover, it is preferable to perform reaction of the fluorine-containing diblock copolymer which has a hydroxyl group, and the (meth) acrylic acid ester which has an isocyanate group in presence of a urethanization catalyst.

  As the urethanization catalyst, the organic tin compound, the organic titanium compound, the organic zirconium compound, the organic amine compound, or the organic acid salt of 1,8-diazabicyclo [5,4,0] -7-undecene exemplified above is used. be able to. Further, an organic amine compound and an organic tin compound may be used in combination.

  The urethanization catalyst is preferably used in an amount of 0.000001 to 0.01 mole equivalent relative to the hydroxyl group to be isocyanated. The hydroxyl group to be isocyanate is a hydroxyl group of a fluorine-containing diblock copolymer having a hydroxyl group.

  The reaction between the fluorine-containing diblock copolymer having a hydroxyl group and the (meth) acrylic acid ester having an isocyanate group is performed in a non-fluorine solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate and toluene, or For example, in a fluorine-containing solvent such as 1,3-bistrifluoromethylbenzene. Moreover, it can also carry out in the mixed solvent of a non-fluorine solvent and a fluorine-containing solvent.

  Production of a fluorinated diblock copolymer having a polymerizable unsaturated group is obtained by adding a urethane-containing diblock copolymer having a hydroxyl group isolated from a polymerization solution to a urethanization catalyst and an isocyanate group (meth) acrylic acid ester. Or an organic solvent may be added, or a urethanization catalyst, a (meth) acrylic acid ester having an isocyanate group, an organic solvent, etc. may be appropriately added to the polymerization solution containing the copolymer as necessary. Can also be done.

  The reaction between the fluorine-containing diblock copolymer having a hydroxyl group and the (meth) acrylic acid ester having an isocyanate group is preferably performed in the presence of a polymerization inhibitor in order to suppress polymerization of the unsaturated group. . As the polymerization inhibitor, for example, 4-methoxyphenol and 2,6-di-t-butyl-4-methylphenol can be used. The polymerization inhibitor is preferably used in the range of 1 to 5,000 ppm with respect to the fluorine-containing diblock copolymer having a hydroxyl group.

  Moreover, reaction with the fluorine-containing diblock copolymer which has a hydroxyl group, and the (meth) acrylic acid ester which has an isocyanate group can be performed at 0-100 degreeC. In particular, in order to suppress gelation due to polymerization of the fluorine-containing diblock copolymers having a polymerizable unsaturated group to be generated, it is more preferable to carry out at 0 to 60 ° C.

Other components The active energy ray-curable resin composition according to the present embodiment contains various additives in addition to the essential components (A) to (E) as long as they do not depart from the object of the present invention. Also good. Such additives can be appropriately selected according to need, and examples thereof include photosensitizers, polymerization inhibitors, antioxidants, plasticizers, pigments, inorganic fillers such as silica fine particles, and the like.

Preparation of active energy ray-curable resin composition The active energy ray-curable resin composition according to this embodiment can be prepared by weighing each of the above components and mixing them by a known method. Examples of such a mixing method include shaking agitation, agitation mixing with a rotary blade, and mixing with a homogenizer.

Formation of Cured Resin Coating Film The active energy ray-curable resin composition according to this embodiment is applied to the surface of an inorganic substrate or an organic substrate, and after removing volatile components, the active energy rays such as ultraviolet rays or electron beams are used. By curing, a cured resin coating film can be formed on an inorganic substrate or an organic substrate.

Examples of the inorganic base material include glass, ceramic, and stone.
Examples of the organic substrate include polyethylene terephthalate, polymethyl methacrylate, polycarbonate, triacetyl cellulose, polyethylene, polypropylene, polyurethane, and acrylonitrile styrene butadiene resin.

  Application | coating to the base material of the active energy ray curable resin composition which concerns on this embodiment is performed by wet coating, such as a bar coat, a spin coat, a dip coat, and a spray coat, for example.

  The removal of the volatile components may be natural drying at room temperature and atmospheric pressure, but warm air drying or vacuum drying at 100 ° C. or lower is preferable.

  Curing can be performed by active energy rays such as electron beam, ultraviolet ray, and radiation.

  The active energy ray-curable resin composition according to this embodiment can form a cured resin coating film having excellent antifouling durability such as magic ink wiping property and having a good appearance.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment, All the aspects included in the concept of this invention and a claim are included, and various within the scope of this invention. Can be modified.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples.

(1) Raw material The abbreviation of the used raw material is shown below.
FAAC10 (2H): 3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-nonadecafluorododecyl acrylate [ (Made by Unimatec)
FAAC6: 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate (manufactured by Unimatec)
FAMAC6: 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate (manufactured by Unimatec)
FAAC4: 3,3,4,4,5,5,6,6,6-nonafluorohexyl acrylate (manufactured by Unimatec)
FAAC6H: 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate [manufactured by Daikin]
_{· PO6AC: CH 2 = CH-} CO 2 -CH 2 -CF (CF 3) - [OCF 2 CF (CF 3)] 4 -OCF 2 CF 2 CF 3 Experiment synthetic]
_{· PO20AC: CH 2 = CH-} CO 2 -CH 2 -CF (CF 3) - [OCF 2 CF (CF 3)] 18 -OCF 2 CF 2 CF 3 ( where subscript numerical 18 is the average value. ) [Experimental synthetic product]
LPOD17AC: CH ₂ = CH—CO ₂ CH ₂ —CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) ₁₅ —OCF ₂ CF ₂ CF ₃ (however, subscript value 15 is an average value) [Experimental synthesis Product)
CPDTC: 2-cyano-2-propyldodecyl trithiocarbonate (manufactured by Aldrich)
AIBN: 2,2′-azobis (isobutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
MTF: 1,3-bistrifluoromethylbenzene (manufactured by Wako Pure Chemical Industries, Ltd.)
・ MEK: Methyl ethyl ketone [Wako Pure Chemical Industries, Ltd.]
・ MMA: Methyl methacrylate [Wako Pure Chemical Industries, Ltd.]
HEA: 2-hydroxyethyl acrylate [manufactured by Wako Pure Chemical Industries, Ltd.]
AOI: 2-acryloyloxyethyl isocyanate (manufactured by Wako Pure Chemical Industries, Ltd.)
DBTDL: Dibutyltin dilaurate (Wako Pure Chemical Industries, Ltd.)
BHT: 2,6-di-t-butyl-4-methylphenol (Wako Pure Chemical Industries, Ltd.)
MQ: 4-methoxyphenol [manufactured by Wako Pure Chemical Industries, Ltd.]
HCPK: 1-hydroxycyclohexyl phenyl ketone (manufactured by Aldrich)
Karenz (registered trademark) BEI: 1,1- (bisacryloyloxymethyl) ethyl isocyanate (manufactured by Showa Denko KK)
Fluorolink (registered trademark) D4000: HOCH ₂ CF ₂ O (CF ₂ O) ₁₄ (CF ₂ CF ₂ O) ₁₄ CF ₂ CH ₂ OH (however, the subscript value 14 is an average value) (Solve Solexis)
LPOD17: HOCH ₂ CF ₂ CF ₂ (OCF ₂ CF ₂ CF ₂ ) ₁₅ -OCF ₂ CF ₂ CF ₃ (however, subscript value 15 is an average value) [experimental synthesized product]

(2) Measurement method and evaluation method The measurement method and evaluation method are shown below.
〔composition〕
The composition of the fluorine-containing diblock copolymer having a hydroxyl group was calculated by ¹ H-NMR.
Apparatus: JEOL: JNM-LA300 (manufactured by JEOL Ltd.)
Solvent: chloroform-d or acetone-d6
Chemical shift: TMS standard

[Molecular weight]
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the fluorine-containing diblock copolymer having a hydroxyl group were calculated in terms of polystyrene using GPC.
Column: Four Shodex (registered trademark) KF-807 (manufactured by Showa Denko KK) Measurement temperature: 40 ° C
Sample injection volume: 100 μl
Outflow rate: 1 ml / min
Eluent: Tetrahydrofuran

(Polymerization rate)
The final polymerization rate of the fluorine-containing diblock copolymer having a hydroxyl group was calculated by the following formula.
Polymerization rate = Solid content concentration of polymerization solution (actual value) / Solid content concentration assuming 100% polymerization rate (calculated value)

[Observation of resin composition solution]
About the resin composition solution immediately after preparation, the dispersion state was observed visually. Moreover, about the resin composition solution stood overnight after preparation, the presence or absence of precipitation of insoluble matter (perfluoropolyether compound having a polymerizable unsaturated group) was visually observed. The resin composition solution is preferably a homogeneous solution that does not precipitate even after being left overnight.

[Observation of resin coating after curing]
The transparency of the cured resin coating film was visually observed. Specifically, the presence or absence of cloudiness (white turbidity) was confirmed on the surface of the cured resin coating film. In this example, the one without cloudiness was considered good.

[Contact angle]
The contact angles for water and n-hexadecane were measured by DropMaster DM500 (manufactured by Kyowa Interface Science Co., Ltd.). In addition, it means that it is excellent in water repellency or oil repellency, so that a contact angle is large.

[Magic ink repellency]
A line was drawn on the surface of the resin coating film with a black oil-based pen Himackey 1 mm (registered trademark, manufactured by Zebra Corporation), and the state of the magic ink on the surface of the resin coating film was visually observed. In the evaluation, a resin coating film that repels magic ink was marked with ◯, and a resin coating film that did not repel magic ink was marked with x.

[Magic ink wiping property]
The process of drawing a line with black oil-based Pen Hi Mackey 1 mm (registered trademark, manufactured by Zebra Corporation) on the surface of the resin coating film and the process of wiping with a waste cloth after leaving for 5 minutes is one cycle, and the magic ink on the surface of the resin coating film is used. The cycle was repeated until it could not be wiped off, and the number of times was evaluated. Note that the greater the number of repetitions of the cycle, the better the magic ink wiping property. In this example, 20 times or more was considered good.

(Reference Example 1)
[First Step: Copolymerization of FAAC10 (2H) and PO20AC]
Magnet Glass Stirrer, FAAC10 (2H) 0.70 g, PO20AC 1.05 g, CPDTC 56 mg, AIBN 5.3 mg and MTF in a 96 ml Hiper Glass (registered trademark) cylinder (HPG-96: manufactured by Pressure Glass Industrial Co., Ltd.) 0.5 g was charged. The cylinder was immersed in liquid nitrogen to freeze the contents, and then degassed with an oil rotary vacuum pump for 5 minutes. After closing the needle valve, the cylinder was immersed in an oil bath at 90 ° C. for 10 hours to conduct a polymerization reaction. In this way, a solution containing a copolymer of FAAC10 (2H) and PO20AC was obtained.

[Second Step: Copolymerization of MMA and HEA]
After the first step, MMA 1.20 g, HEA 0.30 g, AIBN 5.3 mg and MTF 3.0 g were added into the cylinder. The cylinder was immersed in liquid nitrogen to freeze the contents, and then degassed with an oil rotary vacuum pump for 5 minutes. After closing the needle valve, the cylinder was immersed in an oil bath at 85 ° C. for 16 hours to conduct a polymerization reaction, thereby obtaining a solution containing a fluorine-containing diblock copolymer having a hydroxyl group. From the solid content concentration of the contents, it was found that the final polymerization rate including the first step was 99%.
A part of the obtained polymerization solution was dropped into n-hexane, and a reprecipitation operation was performed. Then, the fluorine-containing diblock copolymer which has a hydroxyl group was obtained by making it dry at 60 degreeC under pressure reduction. Table 1 shows the composition, molecular weight, and polydispersity PDI (Mw / Mn) of the obtained copolymer.

[Third step: Reaction of fluorine-containing diblock copolymer having a hydroxyl group with AOI]
After completion of the second step, 0.36 g of AOI, 5 mg of DBTDL, 5 mg of BHT, 10 mg of MQ and 3.0 g of MTF were added into the cylinder. After degassing the inside of the cylinder with an oil rotary vacuum pump, reaction was performed at 30 ° C. for 4 hours to obtain a solution containing a fluorine-containing diblock copolymer having a polymerizable unsaturated group (active ingredient 35 wt%). . This was diluted 35 times (by weight) with MTF to obtain a fluorine-containing diblock copolymer solution FB1 having a polymerizable unsaturated group of 1.0% by weight of the active ingredient.

(Reference Example 2)
Reference Example 2 performs the first step, the second step and the third step in the same manner as Reference Example 1 except that each raw material shown in Table 1 is used, and contains a fluorine-containing 2 block having a polymerizable unsaturated group. A copolymer solution FB2 was obtained (active ingredient 35% by weight). This was diluted 35 times (by weight) with MTF to obtain a fluorine-containing diblock copolymer solution FB2 having a polymerizable unsaturated group of 1.0% by weight of the active ingredient.

(Reference Example 3)
Reference Example 3 performs the first step, the second step and the third step in the same manner as Reference Example 1 except that each raw material shown in Table 1 is used, and contains a fluorine-containing 2 block having a polymerizable unsaturated group. A copolymer solution FB3 was obtained (active ingredient 22% by weight). This was diluted 22 times (weight conversion) with MTF to obtain a fluorine-containing diblock copolymer solution FB3 having a polymerizable unsaturated group of 1.0% by weight of the active ingredient.

(Reference Example 4)
In Reference Example 4, except that each raw material shown in Table 1 was used, the first step, the second step and the third step were performed in the same manner as in Reference Example 1, and the fluorine-containing 2 block having a polymerizable unsaturated group A copolymer solution FB4 was obtained (active ingredient 35% by weight). This was diluted 35 times (by weight) with MTF to obtain a fluorine-containing diblock copolymer solution FB4 having a polymerizable unsaturated group of 1.0% by weight of the active ingredient.

(Reference Example 5)
[First step: random copolymerization of FAAC10 (2H), PO20AC, MMA and HEA]
Magnet Glass Stirrer, FAAC10 (2H) 0.70 g, PO20AC 1.05 g, CPDTC 56 mg, AIBN 5.3 mg, MMA in a 96 ml Hiper Glass (registered trademark) cylinder (HPG-96: manufactured by Pressure Glass Industrial Co., Ltd.) 1.20 g, HEA 0.30 g and MTF 3.5 g were charged. The cylinder was immersed in liquid nitrogen to freeze the contents, and then degassed with an oil rotary vacuum pump for 5 minutes. After closing the needle valve, the cylinder was immersed in an oil bath at 85 ° C. for 16 hours to conduct a polymerization reaction. In this way, a solution containing a random copolymer of FAAC10 (2H), PO20AC, MMA and HEA was obtained. The polymerization rate was 99%.
Further, in the same manner as in Reference Example 1, a fluorine-containing random copolymer having a hydroxyl group was obtained from a part of the polymerization solution. Table 1 shows the composition, molecular weight, and polydispersity PDI (Mw / Mn) of the obtained copolymer.

[Second step (corresponding to the third step of Reference Example 1): Reaction of fluorine-containing random copolymer having a hydroxyl group with AOI]
After the first step, AOI 0.36 g, DBTDL 5 mg, BHT 5 mg, MQ 10 mg and MTF 9.5 g were added into the cylinder. After degassing the inside of the cylinder with an oil rotary vacuum pump, reaction was performed at 30 ° C. for 4 hours to obtain a solution containing a fluorine-containing random copolymer having a polymerizable unsaturated group (active ingredient 22% by weight). This was diluted with MTF 22 times (weight conversion) to obtain a fluorine-containing random copolymer solution FR1 having a polymerizable unsaturated group of 1.0% by weight of the active ingredient.

(Reference Example 6)
[First step: copolymerization of MMA and HEA]
Magnet Glass Stirrer, MMA 2.8 g, HEA 0.7 g, CPDTC 42 mg, AIBN 4.0 mg and MEK 2.5 g in a 96 ml Hiper Glass (registered trademark) cylinder (HPG-96: manufactured by Pressure Glass Industrial Co., Ltd.) Was charged. The cylinder was immersed in liquid nitrogen to freeze the contents, and then degassed with an oil rotary vacuum pump for 5 minutes. After closing the needle valve, the cylinder was immersed in an oil bath at 85 ° C. for 16 hours to conduct a polymerization reaction.

[Second Step: Polymerization of FAAC10 (2H)]
After completion of the first step, 1.5 g of FAAC 10 (2H), 3.0 mg of V-65 and 2.0 g of MEK were added to the polymerization solution in the cylinder. The cylinder was immersed in liquid nitrogen to freeze the contents, and then degassed with an oil rotary vacuum pump for 5 minutes. After closing the needle valve, the cylinder was immersed in an oil bath at 60 ° C. for 16 hours to conduct a polymerization reaction, thereby obtaining a solution containing a fluorine-containing diblock copolymer having a hydroxyl group. From the solid content concentration of the contents, it was found that the final polymerization rate including the first step was 99%.
Further, in the same manner as in Reference Example 1, a fluorine-containing diblock copolymer having a hydroxyl group was obtained from a part of the polymerization solution. Table 1 shows the composition, molecular weight, and polydispersity PDI (Mw / Mn) of the obtained copolymer.

[Third step: Reaction of fluorine-containing diblock copolymer having a hydroxyl group with AOI]
After the completion of the second step, 0.85 g of AOI, 10 mg of DBTDL, 15 mg of BHT, 20 mg of MQ and 6.0 g of MEK were added to the polymerization solution in the cylinder. After degassing the inside of the cylinder with an oil rotary vacuum pump, reaction was performed at 20 ° C. for 2 hours to obtain a solution containing a fluorine-containing diblock copolymer having a polymerizable unsaturated group (active ingredient 36% by weight) . This was diluted 36 times (by weight) with MEK to obtain a fluorine-containing diblock copolymer solution FB5 having a polymerizable unsaturated group of 1.0% by weight of the active ingredient.

(Reference Examples 7 and 8)
Reference Examples 7 and 8 were the same as Reference Example 1 except that the raw materials shown in Table 2 were used. The first step, the second step and the third step were performed, and the fluorine-containing compound having a polymerizable unsaturated group A diblock copolymer solution was obtained (active ingredient 23% by weight). These were diluted 23 times (by weight) with MEK to obtain fluorine-containing diblock copolymer solutions FB6 and 7 having a polymerizable unsaturated group of 1.0% by weight of the active ingredient.

(Reference Examples 9-12)
Reference Examples 9 to 12 use the raw materials shown in Table 2, and the first step, the second step, and the third step as in Reference Example 1, except that the polymerization time in the first step is 6 hours. To obtain a fluorine-containing diblock copolymer solution having a polymerizable unsaturated group (23% by weight of active ingredient). These were each diluted 23 times (by weight) with MEK to obtain fluorine-containing diblock copolymer solutions FB8 to 11 having a polymerizable unsaturated group of 1.0% by weight of the active ingredient.

(Reference Example 13)
In Reference Example 13, a polymerization reaction was carried out in the same manner as in Reference Example 5 except that each raw material shown in Table 2 was used to obtain a fluorinated random copolymer solution having a polymerizable unsaturated group (active ingredient). 23% by weight). This was diluted with MEK 23 times (weight conversion) to obtain a fluorine-containing random copolymer solution FR2 having a polymerizable unsaturated group of 1.0% by weight of the active ingredient.

(Reference Example 14)
[Preparation of perfluoropolyether compound FLD4000BEI having polymerizable unsaturated group]
Into a 50 ml Schlenk tube, put a magnetic stirrer, 2.0 g of Fluorolink (registered trademark) D4000, 0.24 g of Karenz (registered trademark) BEI, 9.0 mg of DBTDL, 3.0 mg of MQ and 5.0 g of MTF, and oil After degassing the interior with a rotary pump, the cock was closed. This was immersed in an oil bath at 60 ° C. for 5 hours. After cooling, a part of the product was extracted, and when the presence or absence of an isocyanate group was confirmed by an infrared absorption spectrometer, it was confirmed that the reaction was completed because 2260 cm ⁻¹ absorption due to the isocyanate group was not observed. did. Next, MTF was distilled off from the reaction mixture under reduced pressure to obtain a perfluoropolyether compound (FLD4000BEI) having a polymerizable unsaturated group shown below.

なお、上記式においてｙは１４、ｚは１４である。但し、ｙおよびｚは^１９Ｆ−ＮＭＲ分析より求めた値である。下記Ｉ（-ppm）は、所定の^１９Ｆ−ＮＭＲケミカルシフトのピーク積分値を示す。
ｙ＝２×{Ｉ（-54.8ppm）＋Ｉ（-56.4ppm）＋Ｉ（-58.1ppm）}／{Ｉ（-84.1ppm）＋Ｉ（-86.1ppm）＋Ｉ（-86.4ppm）＋Ｉ（-86.1ppm）}
ｚ＝{Ｉ（-91.8ppm）＋Ｉ（-93.4ppm）}／{Ｉ（-84.1ppm）＋Ｉ（-86.1ppm）＋Ｉ（-86.4ppm）＋Ｉ（-86.1ppm）}

In the above formula, y is 14 and z is 14. However, y and z are values obtained from ¹⁹ F-NMR analysis. The following I (-ppm) indicates a peak integrated value of a predetermined ¹⁹ F-NMR chemical shift.
y = 2 × {I (−54.8 ppm) + I (−56.4 ppm) + I (−58.1 ppm)} / {I (−84.1 ppm) + I (−86.1 ppm) + I (−86.4 ppm) + I (−86.1 ppm) }
z = {I (-91.8 ppm) + I (-93.4 ppm)} / {I (-84.1 ppm) + I (-86.1 ppm) + I (-86.4 ppm) + I (-86.1 ppm)}

(Reference Example 15)
[Preparation of perfluoropolyether compound LPOD17BEI having polymerizable unsaturated group]
Put a magnetic stir bar, 2.0 g LPOD17, 0.17 g Karenz (registered trademark) BEI, 9.0 mg DBTDL, 3.0 mg MQ and 5.0 g MTF in a Schlenk tube with a capacity of 50 ml. After degassing, the cock was closed. This was immersed in an oil bath at 60 ° C. for 5 hours. After cooling, a part of the product was extracted, and when the presence or absence of an isocyanate group was confirmed by an infrared absorption spectrometer, it was confirmed that the reaction was completed because 2260 cm ⁻¹ absorption due to the isocyanate group was not observed. did. Next, MTF was distilled off from the reaction mixture under reduced pressure to obtain a perfluoropolyether compound (LPOD17BEI) having a polymerizable unsaturated group shown below.

(Reference Example 16)
[Preparation of UV curable resin solution I]
Urethane acrylate UV curable resin Hitaloid (registered trademark) 7909-1 (solid content 80 wt%: manufactured by Hitachi Chemical Co., Ltd.) 125 parts by weight, MEK 123 parts by weight and HCPK 2 parts by weight are mixed, and UV curable resin solution I was obtained (resin solid content 40% by weight).

(Reference Example 17)
[Preparation of UV curable resin solution II]
Urethane acrylate UV curable resin beam set (registered trademark) 575CB (solid content 100% by weight, photopolymerization initiator blending grade: manufactured by Arakawa Chemical Co., Ltd.) 100 parts by weight and MEK 150 parts by weight are mixed and UV curable. Resin solution II was obtained (resin solid content 40 wt%).

Example 1
In 250 parts by weight of the ultraviolet curable resin solution I obtained in Reference Example 16, 0.05 part by weight of the perfluoropolyether compound FLD4000BEI having a polymerizable unsaturated group obtained in Reference Example 14 and obtained in Reference Example 1 The resulting fluorine-containing diblock copolymer solution having a polymerizable unsaturated group (active ingredient 1.0% by weight) FB1 (1.00 part by weight) was added. The obtained ultraviolet curable resin composition solution was shaken and stirred, and the transparency was visually observed. Thereafter, the solution was allowed to stand overnight, and the presence or absence of insoluble precipitates was visually confirmed on the bottom of the container. The results are shown in Table 3.
Further, the ultraviolet curable resin composition solution was shaken and stirred again, and then uniformly applied to a 76 mm × 26 mm × 1.0 mm glass slide, and left in an oven at 60 ° C. for 5 minutes to remove the solvent. Thereafter, ultraviolet rays (180 mJ / cm ² ) were irradiated with a high-pressure mercury lamp in a nitrogen atmosphere to form a resin coating film having a thickness of about 100 μm on the glass. About the obtained resin coating film, the transparency of the resin coating film surface, a static contact angle, a dynamic contact angle, and the repelling property and wiping property of magic ink were evaluated. The results are shown in Table 3.

(Example 2)
In Example 2, instead of the fluorine-containing diblock copolymer solution FB1 having a polymerizable unsaturated group, 1.00 part by weight of FB2 (active ingredient 1.0% by weight) obtained in Reference Example 2 was used. Except that, the procedure was the same as in Example 1. The results are shown in Table 3.

(Example 3)
In Example 3, instead of the fluorine-containing diblock copolymer solution FB1 having a polymerizable unsaturated group, 1.00 part by weight of FB3 (active ingredient 1.0% by weight) obtained in Reference Example 3 was used. Except that, the procedure was the same as in Example 1. The results are shown in Table 3.

Example 4
In Example 4, 0.05 part by weight of LPOD17BEI obtained in Reference Example 15 was used instead of the perfluoropolyether compound FLD4000BEI having a polymerizable unsaturated group, and a fluorine-containing diblock copolymer having a polymerizable unsaturated group. The same procedure as in Example 1 was conducted except that 1.00 part by weight of FB4 (1.0% by weight of active ingredient) obtained in Reference Example 4 was used instead of Solution FB1. The results are shown in Table 3.

(Comparative Example 1)
In Comparative Example 1, instead of the fluorinated diblock copolymer solution having a polymerizable unsaturated group (active ingredient 1.0% by weight) FB1, FB5 (active ingredient 1.0% by weight) obtained in Reference Example 6 was used. ) Performed in the same manner as in Example 1 except that 1.00 parts by weight was used. The results are shown in Table 3.

(Comparative Example 2)
Comparative Example 2 was carried out in the same manner as in Example 1 except that the fluorine-containing diblock copolymer solution having a polymerizable unsaturated group (active ingredient 1.0% by weight) FB1 was not added. The results are shown in Table 3.

(Comparative Example 3)
Comparative Example 3 was carried out in the same manner as in Example 4 except that the fluorine-containing diblock copolymer solution having a polymerizable unsaturated group (active ingredient 1.0% by weight) FB1 was not added. The results are shown in Table 3.

(Comparative Example 4)
In Comparative Example 4, the perfluoropolyether compound FLD4000BEI having a polymerizable unsaturated group and the fluorine-containing diblock copolymer solution having a polymerizable unsaturated group (active ingredient 1.0% by weight) FB1 were not added. Except for this, the same procedure as in Example 1 was performed. The results are shown in Table 3.

(Example 5)
In Example 5, the addition amount of the perfluoropolyether compound FLD4000BEI having a polymerizable unsaturated group was 0.10 parts by weight, and instead of the fluorine-containing diblock copolymer solution FB1 having a polymerizable unsaturated group, Reference Example The same procedure as in Example 1 was performed except that 1.00 part by weight of FB2 obtained in 2 (active ingredient 1.0% by weight) was used. The results are shown in Table 4.

(Example 6)
Example 6 is the same as Example 5 except that the amount of the fluorinated diblock copolymer solution having a polymerizable unsaturated group (active ingredient 1.0 wt%) FB2 was 2.00 parts by weight. The same was done. The results are shown in Table 4.

(Example 7)
Example 7 is the same as Example 5 except that the addition amount of the fluorine-containing diblock copolymer solution having a polymerizable unsaturated group (active ingredient 1.0% by weight) FB2 was 3.00 parts by weight. The same was done. The results are shown in Table 4.

(Comparative Example 5)
Comparative Example 5 was carried out in the same manner as in Example 5 except that the fluorine-containing diblock copolymer solution having a polymerizable unsaturated group (active ingredient 1.0 wt%) FB2 was not added. The results are shown in Table 4.

(Example 8)
In Example 8, 2.00 parts by weight of FB1 (active ingredient 1.0% by weight) obtained in Reference Example 1 was used in place of the fluorine-containing diblock copolymer solution FB2 having a polymerizable unsaturated group. Except that, the same procedure as in Example 5 was performed. The results are shown in Table 4.

(Comparative Example 6)
In Comparative Example 6, instead of the fluorine-containing diblock copolymer solution FB2 having a polymerizable unsaturated group, a fluorine-containing random copolymer solution having a polymerizable unsaturated group obtained in Reference Example 5 (active ingredient 1 0.0 wt%) FR1 was carried out in the same manner as in Example 5 except that 2.00 parts by weight of FR1 was used. The results are shown in Table 4.

Example 9
Example 9 is the same as Example 6 except that 250 parts by weight of the UV curable resin solution II obtained in Reference Example 17 was used instead of the UV curable resin solution I obtained in Reference Example 16. The same was done. The results are shown in Table 4.

(Comparative Example 7)
Comparative Example 7 was carried out in the same manner as Example 9 except that fluorinated diblock copolymer solution having a polymerizable unsaturated group (active ingredient 1.0 wt%) FB2 was not added. The results are shown in Table 4.

(Example 10)
In Example 10, the perfluoropolyether compound FLD4000BEI having a polymerizable unsaturated group was added in an amount of 0.10 parts by weight, and instead of the fluorine-containing diblock copolymer solution FB1 having a polymerizable unsaturated group, a reference example was used. Example 1 was performed except that 2.00 parts by weight of FB6 (1.0% by weight of active ingredient) obtained in 7 was used. The results are shown in Table 5.

(Examples 11 to 15 and Comparative Example 8)
In Examples 11 to 15 and Comparative Example 8, instead of the fluorine-containing diblock copolymer solution FB6 having a polymerizable unsaturated group, FB7 to 11 and FR2 (active ingredients 1. 0% by weight) was used in the same manner as Example 10. The results are shown in Table 5.

  According to the ultraviolet curable resin compositions of Examples 1 to 15 according to the present invention, it is confirmed that the cured resin coating film has a good appearance without cloudiness and exhibits excellent magic ink wiping properties. It was.

  On the other hand, in the ultraviolet curable resin composition of Comparative Example 1, since the fluorine-containing diblock copolymer having a polymerizable unsaturated group having a structure different from that specified in the present invention is used, the PFPE compound is dispersed. Insufficient ability to form, cloudiness occurs in the cured resin coating film, and further, compared with the ultraviolet curable resin composition of Examples 1-15 according to the present invention, the magic ink of the cured resin coating film It was confirmed that the wiping property was inferior.

  Further, in the ultraviolet curable resin compositions of Comparative Examples 2, 3, 5 and 7, since the fluorine-containing diblock copolymer having a specific polymerizable unsaturated group according to the present invention is not contained, a uniform resin It was confirmed that a composition solution was not obtained and cloudiness was generated in the cured resin coating film.

  Moreover, since the fluorine-containing random copolymer which has a polymerizable unsaturated group is used in the ultraviolet curable resin composition of the comparative example 6, the ultraviolet curable resin composition of Examples 1-15 which concerns on this invention It was confirmed that the magic ink wiping property of the resin coating film after curing was inferior in particular. Similarly, the ultraviolet curable resin composition of Comparative Example 8 was also fogged in the cured resin coating film, and its magic ink wiping property was also the ultraviolet curable resin composition of Examples 1 to 15 according to the present invention. It was confirmed that it was inferior to the product.

  Further, in the ultraviolet curable resin composition of Comparative Example 4, since no PFPE compound having a polymerizable unsaturated group was originally added, there was no problem of dispersibility, and the cured resin coating had no magic resistance. It was confirmed that antifouling properties such as ink properties were not imparted.

Claims (9)

Contains an active energy ray-curable resin, a radical photopolymerization initiator, an organic solvent, a perfluoropolyether compound having a polymerizable unsaturated group, and a fluorine-containing diblock copolymer having a polymerizable unsaturated group And
The perfluoropolyether compound having a polymerizable unsaturated group is a perfluoropolyether compound having a polymerizable unsaturated group represented by the following general formula (1) or (2):
The fluorine-containing diblock copolymer having a polymerizable unsaturated group is a non-fluorine (meth) acrylic acid ester polymer block containing a non-fluorine (meth) acrylic acid ester having a hydroxyl group as a constituent monomer; Fluorinated alkyl (meth) acrylic acid ester represented by (3) and perfluorinated polyether chain-containing (meth) acrylic acid ester represented by the following general formula (4) Fluorine-containing 2 having a polymerizable unsaturated group produced by reacting a (meth) acrylic acid ester having an isocyanate group with a fluorine-containing diblock copolymer having a hydroxyl group and an acid ester polymer block An active energy ray-curable resin composition, which is a block copolymer.

(In Formula (1), X is an integer of 2 to 5, R ¹ is a hydrogen atom or a methyl group. L is an X + 1 valent organic group having a molecular weight of 30 to 600, and a plurality of urethane bonds are contained therein. An ester bond, an amide bond, an ether bond, etc. p and q are each independently an integer of 1 to 50.)

(In Formula (2), X is an integer of 2 to 5, R ¹ is a hydrogen atom or a methyl group. L is an X + 1 valent organic group having a molecular weight of 30 to 600, and a plurality of urethane bonds are contained therein. And an ester bond, an amide bond, an ether bond, etc. Rf ² is a C 1 to C 3 perfluoroalkyl group, and r is an integer of 1 to 50.)

(In Formula (3), R ¹ is a hydrogen atom or a methyl group, l is an integer of 1 to 5, and Rf ¹ is a monovalent C 1-16 fluorohydrocarbon group.)

(In the formula (4), ^{R 1} is a hydrogen atom or a methyl group, Rf ² is a perfluoroalkyl group having 1 to 3 carbon atoms, Rf ³ is _-CF 2 CF (CF ₃₎ - group or -CF ₂ CF ₂ CF ₂ — group, Rf ⁴ is —CF ₂ CF ₂ — group or —CF (CF ₃ ) — group, and m is an integer of 1-30. The active energy according to claim 1, wherein the fluorinated alkyl (meth) acrylate represented by the general formula (3) is a fluorinated alkyl (meth) acrylate represented by the following general formula (5). A linear curable resin composition.

In (formula (5), ^{R 1} is a hydrogen atom or a methyl group, a = b = 0 or where a is an integer of 1-3, b is an integer of 1 to 2, n is 1 to 6 for .a ≠ 0 and b ≠ 0 is an _integer, -C _{n F 2n + 1} is _{- (CF 2 CH 2) b} - is bonded to CH _{2 groups, - (CF 2 CF 2)} a - group It is bonded to the CF ₂ group of — (CF ₂ CH ₂ ) _b —.) The active energy according to claim 1, wherein the fluorinated alkyl (meth) acrylate represented by the general formula (3) is a fluorinated alkyl (meth) acrylate represented by the following general formula (6). A linear curable resin composition.

(In the formula (6), ^{R 1} is a hydrogen atom or a methyl group, s is an integer from 1 to 6.) The perfluoropolyether chain-containing (meth) acrylic acid ester represented by the general formula (4) is a perfluoropolyether chain-containing (meth) acrylic acid ester represented by the following general formula (7): The active energy ray-curable resin composition according to any one of Items 1 to 3.

(In the formula (7), ^{R 1} is a hydrogen atom or a methyl group, m is .Rf ² is an integer of 1 to 30 is a perfluoroalkyl group having 1 to 3 carbon atoms.) The perfluoropolyether chain-containing (meth) acrylic acid ester represented by the general formula (4) is a perfluoropolyether chain-containing (meth) acrylic acid ester represented by the following general formula (8): The active energy ray-curable resin composition according to any one of Items 1 to 3.

(In the formula (8), ^{R 1} is a hydrogen atom or a methyl group, m is .Rf ² is an integer of 1 to 30 is a perfluoroalkyl group having 1 to 3 carbon atoms.)   The active energy ray-curable resin composition according to any one of claims 1 to 5, wherein the fluorine-containing diblock copolymer having a polymerizable unsaturated group has a weight average molecular weight of 5,000 to 50,000.   The perfluoropolyether compound having the polymerizable unsaturated group is 0.005 to 1.0 part by weight with respect to 100 parts by weight of the active energy ray curable resin. The active energy ray-curable resin composition described.   The fluorine-containing diblock copolymer having the polymerizable unsaturated group is 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the active energy ray curable resin. The active energy ray-curable resin composition according to one item. The fluorine-containing diblock copolymer having a hydroxyl group is a fluorine-containing diblock copolymer having a hydroxyl group produced by living radical polymerization in the presence of a trithiocarbonate represented by the following general formula (9). The active energy ray-curable resin composition according to any one of claims 1 to 8.

(In Formula (9), R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and one of R ² and R ³ may contain one carboxyl group. R ⁴ is a linear alkyl group having 1 to 18 carbon atoms.)