High energy ray-curable composition
View Patent ↗Disclosed is a high energy ray-curable composition which is excellent in storage stability before curing and enables to form a cured coating film which is excellent in hardness, property of preventing adhesion of fats and oils, property of wiping off fats and oils, abrasion resistance, transparency, water repellency, adhesion, smoothness and uniformity. Specifically disclosed is a high energy ray-curable composition containing the following components (A)-(D). (A) 100 parts by weight of a polyfunctional acrylate (B) 1-30 parts by weight of an organoalkoxysilane having an aliphatic unsaturated bond (C) 1-100 parts by weight of colloidal silica (D) 0.2-20 parts by weight of a fluorine compound having an aliphatic unsaturated bond.
1. A high energy ray-curable storage stable composition comprising the following components (A) to (D) and (G):
(A) 100 parts by weight of a polyfunctional acrylate, wherein said polyfunctional acrylate comprises a combination of two or more polyfunctional acrylates selected from pentafunctional or higher polyfunctional acrylates,
(B) 1 to 30 parts by weight of an organoalkoxysilane having an aliphatic unsaturated bond,
(C) 1 to 100 parts by weight of colloidal silica, and
(D) 0.2 to 20 parts by weight of a fluorine compound having an aliphatic unsaturated bond; wherein the fluorine compound is a reactive group-containing composition comprising a reaction product of (i) a triisocyanate formed by trimerizing a diisocyanate and (ii) at least two active hydrogen-containing compounds, and
the component (ii) comprises:
(ii-1) a perfluoropolyether having at least one active hydrogen, and
(ii-2) a monomer having an active hydrogen and a self-crosslinking functional group; and
(G) a photopolymerization initiator selected from the group consisting of organic peroxides, carbonyl compounds, organic sulfur compounds and azo compounds; wherein when said components (A) to (D) and (G) are combined, the composition exhibits storage stability, and when the composition is exposed to said high energy ray, a composition having oil, fat and scratch resistance is formed.
2. The high energy ray-curable composition according to claim 1 , wherein the fluorine compound has a perfluoropolyether structure.
3. The high energy ray-curable composition according to claim 1 , wherein the fluorine compound has a partial structure represented by the following general formula (a):
—(CX 0 2 CF 2 CF 2 O) n1 —[CF(CF 3 )CF 2 O] n2 —(CF 2 CF 2 O) n3 —(CF 2 O) n4 — (a)
wherein n1, n2, n3 and n4 are the same or different and each is an integer of 0 or 1 or more, and n1+n2+n3+n4 is an integer of 7 to 40; and respective X 0 are the same or different and each is H, F or Cl.
4. The high energy ray-curable composition according to claim 1 , wherein the self-crosslinking functional group of the monomer (ii-2) is at least one selected from the group consisting of:
X 1 is H, CH 3 or F; and X 2 is H or CH 3 .
5. The high energy ray-curable composition according to claim 1 , wherein the perfluoropolyether (ii-1) is a compound which has one hydroxyl group at one molecular end, or has one hydroxyl group at each of both ends.
6. The high energy ray-curable composition according to claim 1 , wherein the perfluoropolyether (ii-1) contains a compound represented by the general formula:
wherein X is F or a —CH 2 OH group; Y and Z are the same or different and each is F or —CF 3 ; a is an integer of 1 to 16, c is an integer of 0 to 5, b, d, e, f and g are the same or different and each is an integer of 0 to 200, and h is an integer of 0 to 16.
7. The high energy ray-curable composition according to claim 1 , wherein the fluorine compound is a reaction product obtained by reacting an isocyanato group (—NCO group) of the triisocyanate component (i) with the component (ii-1) and then reacting with the component (ii-2).
8. The high energy ray-curable composition according to claim 1 , wherein the fluorine compound is a reaction product obtained by reacting 1 mol of the triisocyanate component (i) with a sum total of the active hydrogen of the component (ii-1) and the component (ii-2) of from 2.5 to 3.5 mol in which a molar ratio of the active hydrogen of the component (ii-1) to the active hydrogen of the component (ii-2) is ½ or less.
9. The high energy ray-curable composition according to claim 1 , which further contains 10 to 1000 parts by weight of (E) a solvent.
10. The high energy ray-curable composition according to claim 1 , which further contains (F) water.
11. A coating agent comprising the high energy ray-curable composition according to claim 1 .
12. A substrate selected from the group consisting of plastic, glass, ceramics, metal, concrete, wood, fiber cloth, fiber, nonwoven fabric, leather, paper and stone, comprising the high energy ray-curable composition according to claim 1 on a surface thereof.
13. A high energy ray-curable composition according to claim 1 , where the photopolymerization initiator is selected from the group consisting of acetophenone, propiophenone, benzophenone, xanthol, fluoreine, benzaldehyde, anthraquinone, triphenylamine, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4-dimethoxybenzophenone, 4-chloro-4-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin methyl ether, benzoin butyl ether, bis(4-dimethylaminophenyl)ketone, benzyl methoxy ketal, 2-chlorothioxanthone, diethylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl [4-(methylthio)phenyl]2-morpholino-1-propanone, 2,2-dimethoxy-2-phenylacetophenone and diethoxyacetophenone.
14. The high energy ray-curable composition according to claim 1 , wherein the polyfunctional acrylate is a pentafunctional to decafunctional acrylate.