KR101163922B1 - Anti-fingerprinting resin composition comprising photo-curable fluorine modified urethane (meth)acrylate resin and anti-fingerprinting coating composition - Google Patents
Anti-fingerprinting resin composition comprising photo-curable fluorine modified urethane (meth)acrylate resin and anti-fingerprinting coating composition Download PDFInfo
- Publication number
- KR101163922B1 KR101163922B1 KR1020100140032A KR20100140032A KR101163922B1 KR 101163922 B1 KR101163922 B1 KR 101163922B1 KR 1020100140032 A KR1020100140032 A KR 1020100140032A KR 20100140032 A KR20100140032 A KR 20100140032A KR 101163922 B1 KR101163922 B1 KR 101163922B1
- Authority
- KR
- South Korea
- Prior art keywords
- meth
- acrylate
- modified urethane
- fluorine
- weight
- Prior art date
Links
Classifications
-
- 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
- C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention relates to an anti-fingerprint composition and an anti-fingerprint composition comprising a photocurable fluorine-modified urethane (meth) acrylate resin, wherein a fluoroalkyl compound containing a specific hydroxyl group is copolymerized with an isocyanate to form a monomer. At least one functional group contains urethane (meth) acrylate oligomers, photopolymerizable monomers, and photopolymerization initiators having at least one functional group, so that curing reaction by ultraviolet rays is possible, and the spectroscopic properties can be improved by fluorine compounds. It relates to an anti-fingerprint composition and an anti-fingerprint composition comprising a pyrogenic fluorine-modified urethane (meth) acrylate resin.
Description
The present invention relates to an anti-fingerprint composition and an anti-fingerprint composition comprising a photocurable fluorine-modified urethane (meth) acrylate resin, and more specifically, to a film surface such as polyethylene terephthalate (PET). The anti-fingerprint composition comprising a photocurable fluorine-modified urethane (meth) acrylate resin which can be cured by ultraviolet rays by forming a coating film and which is not only high in hardness but also excellent in anti-fingerprint and scratch resistance. It relates to an anti-fingerprint composition.
Recently, many fingerprint marks are generated by components such as oil and moisture on the surface of an optical display device such as a touch screen panel (TSP), a mobile phone, a window film (safety film, and a security film), and the surface of a finger. Since the fingerprint marks are degraded due to such fingerprint marks, fingerprint marks are not left, or even fingerprint marks are easily and cleanly wiped, and there is an increasing demand for anti-fingerprint coatings having excellent scratch resistance.
As a method of improving antifouling properties such as anti-fingerprint properties, a method of improving antifouling properties by applying a silicone oil or a fluorine polymer has been proposed. It does not last, because the drying by heat after applying the antifouling agent takes a long time and has a lot of energy consumption problems.
Therefore, using a fluorine-based compound having a very low surface energy of about 5 to 6 dyne / cm, water repellency, oil repellency, and antifouling properties are imparted to improve fingerprint resistance. There is a need for anti-fingerprint compositions and anti-fingerprint compositions that can shorten working time and save energy.
The present invention has been created by the above needs, and the first object of the present invention is to provide a water-repellent, oil-repellent and antifouling properties by using a fluorine-based compound having a low surface energy to improve the fingerprinting and fingerprint composition and fingerprints It is to provide a composition.
In addition, the second object is an anti-fingerprint composition comprising a photocurable fluorine-modified urethane (meth) acrylate resin capable of photocuring by copolymerizing a fluorine-based compound and a urethane (meth) acrylate oligomer, which can shorten working time and save energy. And anti-fingerprint compositions.
The object of the present invention as described above is a fluorine-modified urethane (meth) acrylate prepolymer which is a copolymer of at least one diisocyanate compound, at least one hydroxyl group-containing fluoroalkyl compound and hydroxyl group-containing (meth) acrylate; And a (meth) acrylate monomer; and can be achieved by providing an anti-fingerprint composition comprising a photocurable fluorine-modified urethane (meth) acrylate resin.
The diisocyanate compound may be at least one of 4,4′-dicyclohexyl methane diisocyanate, 1,6-hexamethylene diisocyanate and isophorone diisocyanate.
The fluorine-modified urethane (meth) acrylate prepolymer may have a weight average molecular weight of 500 to 2000 and an average urethane bond of 6 to 22 per molecule.
In addition, the fluoroalkyl compound may be characterized by having a weight average molecular weight of 1000 to 20000.
In addition, the fluoroalkyl compound is 2-nonafluoro butyl ethanol, 2-trideca fluoro hexyl ethanol, 2-heta deca fluoro octyl ethanol, 2-henaicosa fluorodecyl ethanol, 2,3-difluoro At least one of benzyl alcohol, 2-fluoro benzyl alcohol, 1- (tenta fluorophenyl) -ethanol and 2- (trifluoro methyl) -benzyl alcohol.
Meanwhile, an object of the present invention is to provide a fluorine-modified urethane (meth) acrylate prepolymer which is a copolymer of at least one diisocyanate compound, at least one hydroxyl group-containing fluoroalkyl compound and hydroxyl group-containing (meth) acrylate; (Meth) acrylate monomers; Photoinitiators; Inorganic fillers; And a diluent solvent; and may be achieved by providing an anti-fingerprint composition comprising a photocurable fluorine-modified urethane (meth) acrylate resin.
Moreover, photoinitiator is 1-hydroxycyclohexyl phenyl ketone, 2, 2- dimethoxy- 2-phenyl- acetophenone, benzaldehyde, anthraquinone, 3-methyl acetophenone, 4-chlorobenzo phenone, 4,4'- Dimethoxybenzophenone, benzoinpropylether, benzoinethylether, 1- (4-isopropyl-phenol) -2-hydroxy-2-methylpropan-1-one, thioxanthone, benzophenone and 2,4, It may be characterized in that any one of 6-trimethylbenzoyl-diphenylphosphine.
In addition, the inorganic filler may be characterized in that at least any one of silica, titania, alumina, zirconia, tin, zinc, antimony and indium.
In the anti-fingerprint composition comprising a photocurable fluorine-modified urethane (meth) acrylate resin, 10 to 40 parts by weight of the fluorine-modified urethane (meth) acrylate prepolymer and 10 to 30 parts by weight of the (meth) acrylate monomer. , Photo-initiator may be included in 2.5 to 7.5 parts by weight, inorganic filler 5 to 30 parts by weight, diluent solvent 30 to 60 parts by weight.
According to an embodiment of the present invention, the anti-fingerprint composition prepared using the curable fluorine-modified urethane (meth) acrylate resin of the present invention is a coating film for windows such as safety films, security films, and car tinting films. ) Is very suitable for use.
In addition, by using a window film, a touch screen panel, a mobile phone, a cosmetic case, etc., it is excellent in antifouling properties such as fingerprint resistance, scratch resistance, as well as workability improvement and energy saving by photocuring.
Hereinafter, preferred embodiments of the present invention will be described in detail. In addition, in the following description of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.
< Inner Gate Resin Composition>
The anti-fingerprint composition (hereinafter referred to as 'fingerprint-resin composition') containing the photocurable fluorine-modified resin of the present invention is a fluorine-modified urethane (meth) which is a copolymer of a diisocyanate compound, a hydroxyl-containing fluoroalkyl compound, and a hydroxyl-containing (meth) acrylate. ) Acrylate prepolymer and (meth) acrylate monomers.
The photocurable fluorine-modified resin in the inventors-fingerprint composition includes a urethane (meth) acrylate prepolymer and a (meth) acrylate monomer, wherein the urethane (meth) acrylate prepolymer used is a weight average molecular weight of 500 to 2000 The average urethane bonds per molecule are used. This is because when the weight average molecular weight is less than 500, the anti-fingerprint effect is lowered due to deterioration of adhesion and curing failure, and when the weight-average molecular weight is higher than 2000, the anti-fingerprint is deteriorated due to the lowering of the leveling.
Here, the fluorine-modified urethane (meth) acrylate prepolymer is a copolymer of at least one or more diisocyanate compounds, at least one or more hydroxyl-containing fluoroalkyl compounds, and hydroxyl-containing (meth) acrylates, and such fluorine-modified urethane (meth) acrylates By using a prepolymer, a fingerprint resin composition capable of improving fingerprint resistance and scratch resistance can be produced. There are various methods of introducing a double bond to both ends of a fluorine-modified urethane prepolymer substituted with a diisocyanate. Among them, 2 moles of hydroxyl group-containing (meth) acrylate is used per 1 mole of the fluorine-modified urethane prepolymer. It is preferable to use the prepolymer method to make it react. The hydroxyl group-containing (meth) acrylate used at this time has 2 to 6 carbons in the alkyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( Methacrylate or pentaerythritol tri (meth) acrylate may be selected or a mixture thereof may be used.
On the other hand, as the diisocyanate compound to be used in the present invention, the aliphatic, cycloaliphatic and aromatic diisocyanate compounds may be used. -Hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, 2,2-bis-4'-propane isocyanate, 6-isopropyl-1,3-phenyldiisocyanate, bis (2-isocyanate ethyl) -puma Rate, 1,6-hexane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'- dimethylphenylene diisocyanate, 3,3'- dimethyl-4,4'- diphenylmethane diisocyanate, p- Phenylene diisocyanate, m-phenylene diisocyanate, 1, 5- naphthalene diisocyanate, 1, 4- xylene diisocyanate, 1, 3- xylene diisocyanate , 4,4'-dicyclohexyl methane diisocyanate can be selected or a mixture thereof can be used, in particular, 4,4'- dicyclohexyl methane diisocyanate and isomers thereof, 1,6- Preference is given to selecting one of hexamethylene diisocyanate, isophorone diisocyanate or using a mixture thereof.
In addition, the fluoroalkyl compound containing the hydroxyl group to be used in the present invention is 2-nonafluoro butyl ethanol, 2-trideca fluoro hexyl ethanol, 2-heta deca fluoro octyl ethanol, 2-hen- icosa fluoro Decyl ethanol, 2,3-difluoro benzyl alcohol, 2-fluoro benzyl alcohol, 1- (tenta fluoro phenyl) -ethanol, 2- (trifluoro methyl) -benzyl alcohol or their Preference is given to using mixtures. On the other hand, it is preferable to use the fluoroalkyl compound whose weight average molecular weights are 1000-20000. This is because when the weight average molecular weight of the fluoroalkyl compound is less than 1000, the anti-fingerprint effect is lowered due to deterioration of adhesion and curing failure.
The photocurable resin comprising a fluorine-modified urethane (meth) acrylate prepolymer and a (meth) acrylate monomer synthesized by copolymerizing a hydroxyl group-containing fluorine alkyl compound and a hydroxyl group-containing (meth) acrylate with a diisocyanate compound. When used in, antifouling properties such as scratch resistance and anti-fingerprint are improved, and photocuring is possible, thereby reducing the work time and saving energy.
On the other hand, the (meth) acrylate monomer diluted in the fluorine-modified urethane (meth) acrylate prepolymer can use the monofunctional monomer which has one (meth) acrylate group, and the polyfunctional monomer which has two or more (meth) acrylate groups. have.
As the monofunctional monomer, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, t-octyl (meth) acrylate, N, N-dimethyl (meth) acrylate, N-vinyl caprolactam, N-vinylpyrrolidone, isobutoxy (meth) acrylamide, diacetone (meth) acrylamide, carbonyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclo Fentanyl (meth) acrylate, dicyclopentadiene (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, meth Toxyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth ) Acrylate, benzyl (meth) acrylate, epoxydiethylene glycol (meth) acrylate, butoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, styryl (meth) acrylate, octadecyl (Meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, isodecyl (meth) acrylate, nonyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isoamyl ( Meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, propyl (meth) acrylate, ethyl (meth) acrylate , Methyl (meth) acrylate can be selected or a mixture thereof can be used.
As the polyfunctional monomer, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane EO-modified triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate Ethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth ) Acrylate, tricyclodecane dimethanol di (meth) acrylate can be selected or a mixture thereof can be used.
In the anti-fingerprint composition of the present invention, it is preferable to use a monomer having three or more (meth) acrylate groups in one molecule in order to improve the hardenability and improve the hardness of the coating film as a dilution monomer. For example, it is preferable to use pentaerythritol triacrylate, pentaerythritol EO modified triacrylate, trimethylolpropane EO modified triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like.
< Anti-fingerprint Composition>
The anti-fingerprint composition (hereinafter referred to as 'fingerprint coating composition') comprising the photocurable fluorine-modified urethane (meth) acrylate resin of the present invention is at least one diisocyanate compound, at least one hydroxyl group-containing fluoroalkyl compound and hydroxyl group At least one or more of a photoinitiator, an inorganic filler, and a dilution solvent for curing with ultraviolet light to a photocurable resin comprising a fluorine-modified urethane (meth) acrylate prepolymer and a (meth) acrylate monomer, which are copolymers of a containing (meth) acrylate. Include your choice. Meanwhile, since the diisocyanate compound, the hydroxyl group-containing fluoroalkyl compound, and the hydroxyl group-containing (meth) acrylate have already been described in detail in the above description of the anti-fingerprint composition, hereinafter, their content ratios and photoinitiators in the anti-fingerprint compositions, Inorganic fillers and diluent solvents are described in detail.
The fluorine-modified urethane (meth) acrylate prepolymer included in the anti-fingerprint composition of the present invention preferably contains 10 to 40 parts by weight based on the total weight of the anti-fingerprint composition. When the fluorine-modified urethane (meth) acrylate prepolymer is contained in less than 10 parts by weight, the fluorine content is low and the fingerprint resistance is low. When the fluorine-modified urethane (meth) acrylate prepolymer is contained in an amount of more than 40 parts by weight, the coating film is too flexible, so that the scratch resistance is not good, and the curability is remarkably high. This is because problems occur that fall.
In addition, it is preferable that the (meth) acrylate monomer included in the to-fingerprint composition of the present invention contain 10 to 30 parts by weight based on the total weight of the to-fingerprint composition. This is because when the (meth) acrylate monomer is included in less than 10 parts by weight, the viscosity of the composition is too high and the hardness of the coating film is lowered. .
On the other hand, the anti-fingerprint coating composition of the present invention is to increase the curing speed by curing with ultraviolet rays, may comprise a photoinitiator for ultraviolet curing. Photoinitiators include 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenyl-acetophenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxy Benzophenone, benzoin propylether, benzoin ethyl ether, 1- (4-isopropyl-phenol) -2-hydroxy-2-methylpropan-1-one, thioxanthone, benzophenone, 2,4,6- Trimethylbenzoyl-diphenylphosphine may be used in any one or a mixture thereof.
In addition, commercially supplied photoinitiators such as Irgacure184, Irgacure651, Irgacure500, Irgacure819, Irgacure907, Irgacure1800 (Shibagai Corporation) and Darocure1116, Darocure1173 (Merck Corporation), Lucirine LR8728 (BASF), Micure HP-8, TPO, CP-4 , BK-6, BP (Miwon Corporation) etc. can be used.
Such a photoinitiator is preferably included in the 2.5 to 7.5 parts by weight based on the total weight of the to-fingerprint composition, when the photoinitiator is contained less than 2.5 parts by weight, the curability by the ultraviolet light is lowered, when included in excess of 7.5 parts by weight of photocuring is too This is because a lot of the adhesion is reduced.
Inventive to fingerprint coating composition may include an inorganic filler which is a filler of inorganic particles in order to improve the scratch resistance of the surface. By using an inorganic filler, scratch resistance can be improved by increasing the coating film hardness on the surface of the coating layer. It is preferable that these inorganic particles are about 10-60 nanometers in average particle diameters.
Inorganic fillers that may be used in the present inventors' fingerprint compositions include silica, titania, alumina, zirconia, tin, zinc, antimony, indium, and the like, and may be used by mixing at least one of them. Among these, it is preferable to use silica, titania, alumina, zirconia. Furthermore, these inorganic particles are preferably modified by a functional group capable of photocuring the particle surface, that is, an acrylate group.
Such an inorganic filler is preferably included in an amount of 5 to 30 parts by weight based on the total weight of the to-fingerprint composition. When the inorganic filler is included in an amount of less than 5 parts by weight, it is difficult to improve scratch resistance, and when it is included in an amount exceeding 30 parts by weight, the curability is included. This is because a problem occurs that the coating film strength of the coating layer is lowered.
The inventors of the present invention may include an organic solvent as a dilution solvent for controlling workability. Organic solvents used as diluents include toluene, xylene, methyl ethyl ketone, acetone, methyl isobutyl ketone, acetone, cyclohexanone, hexaine, heptane, octane, mineral spirit, diethyl ether, isopropyl ether, Tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , Methanol, ethanol, propanol, butanol, and the like, and these solvents may be used by mixing at least one or more thereof.
Such a dilution solvent is preferably included in 30 to 60 parts by weight based on the total weight of the toluene paint composition, which is less than 30 parts by weight of the diluent solvent, the viscosity of the composition is high, the smoothness is lowered, if it exceeds 60 parts by weight This is because insufficient coating of solvent evaporates during coating.
Hereinafter, the manufacture example of a urethane (meth) acrylate prepolymer, and the Example of the anti-fingerprint composition containing a photocurable fluorine-modified urethane (meth) acrylate resin are described. However, the following examples are only preferred examples of the present invention, and the present invention is not limited to the following examples.
[ Manufacturing example ]
In a 5 liter round bottom flask with a stirrer, 350.625 g (0.15 mol) of fluoro olefin copolymer having a weight average molecular weight of 2337.5, 577.2 g (2.6 mol) of isophorone diisocyanate (IPDI), 688.8 g (2.05 mol) of polyethoxyacrylate ), 1513.4 g (2.3 mol) of pentaerythritol triacrylate and 0.1 g of dibutyltindilaurylate were added thereto. After the reaction temperature is maintained at 70-80 ° C., the reaction is allowed to react until the NCO concentration of the reactant reaches the theoretical NCO concentration. The reaction temperature is then lowered to 50 ° C. and 0.25 g of hydroquinone and 0.25 g of phenoxy as a polymerization inhibitor. Orin was added, and 361.9 g (0.55 mol) of pentaerythritol triacrylate was added to advance the reaction. After the addition, the reaction temperature was maintained at 70-80 ℃ for 8-9 hours and the reaction was completed by infrared spectroscopy (FT-IR) until the -NCO peak disappeared completely.The reaction was completed at 25 ℃ and the viscosity of 15,343cps. A fluorine-modified urethane (meth) acrylate prepolymer having a weight average molecular weight of 1425 was obtained.
[ Example 1 ]
10 parts by weight of the fluorine-modified urethane (meth) acrylate prepolymer obtained by the production example, 25 parts by weight of pentaerythritol ethoxytriacrylate, 5 parts by weight of photoinitiator, 10 parts by weight of inorganic filler, 20 parts by weight of methyl isobutyl ketone, 30 parts by weight of methyl ethyl ketone was mixed to prepare an anti-fingerprint composition containing a photocurable fluorine-modified urethane (meth) acrylate resin.
[ Example 2 ]
20 parts by weight of a fluorine-modified urethane (meth) acrylate prepolymer obtained by the production example, 15 parts by weight of pentaerythritol ethoxytriacrylate, 5 parts by weight of a photoinitiator, 10 parts by weight of an inorganic filler, 20 parts by weight of methyl isobutyl ketone, 30 parts by weight of methyl ethyl ketone was mixed to prepare an anti-fingerprint composition containing a photocurable fluorine-modified urethane (meth) acrylate resin.
[ Example 3 ]
30 parts by weight of the fluorine-modified urethane (meth) acrylate prepolymer obtained by the preparation example, 5 parts by weight of pentaerythritol ethoxytriacrylate, 5 parts by weight of photoinitiator, 10 parts by weight of inorganic filler, 20 parts by weight of methyl isobutyl ketone, 30 parts by weight of methyl ethyl ketone was mixed to prepare an anti-fingerprint composition containing a photocurable fluorine-modified urethane (meth) acrylate resin.
[ Example 4 ]
30 parts by weight of the fluorine-modified urethane (meth) acrylate prepolymer obtained by the production example, 10 parts by weight of pentaerythritol ethoxytriacrylate, 5 parts by weight of photoinitiator, 5 parts by weight of inorganic filler, 20 parts by weight of methyl isobutyl ketone, 30 parts by weight of methyl ethyl ketone was mixed to prepare an anti-fingerprint composition containing a photocurable fluorine-modified urethane (meth) acrylate resin.
[ Example 5 ]
15 parts by weight of the fluorine-modified urethane (meth) acrylate prepolymer obtained by the production example, 10 parts by weight of pentaerythritol ethoxytriacrylate, 5 parts by weight of photoinitiator, 20 parts by weight of inorganic filler, 20 parts by weight of methyl isobutyl ketone, 30 parts by weight of methyl ethyl ketone was mixed to prepare an anti-fingerprint composition containing a photocurable fluorine-modified urethane (meth) acrylate resin.
The liquid composition obtained in Examples 1 to 5 was coated on the film in the following manner and the physical properties thereof were measured.
Experimental Method
① Film coating
The prepared composition was barcoated to a dry film thickness of 2 to 3 microns with a bar coater # 7 on a PET film (thickness 100 microns), and heated in an oven at 60 ° C. to 80 ° C. for 30 seconds to 60 seconds to obtain a solvent. After removal, the anti-fingerprint film was prepared after curing with an energy of 250 mJ / cm 2 in an ultraviolet irradiator equipped with a high pressure mercury lamp.
② Adhesion
A total of 100 cured anti-fingerprint film specimens were made to have a length of 1 mm in width and length, and 3M scotch tape was attached and then peeled off to evaluate the adhesiveness by the number of remaining pieces.
③ anti-fingerprint
Finger prints were placed on the cured anti-fingerprint film specimens and then wiped with a soft cloth for 10 round trips. Haze of the sample before evaluation test and after evaluation test was measured, and (triangle | delta) haze value was calculated | required. According to the measured haze value, the fingerprint was evaluated by the following criteria.
5 points: △ Haze less than 0.5
4 points: △ Haze is 0.5 or more and less than 1.0
3 points: △ Haze is 1.0 or more, less than 3.0
2 points: △ Haze is 3.0 or more and less than 5.0
1 point: △ Haze 5.0 or more
④ pencil hardness
The degree to which scratches occur when the pencil is drawn at a 45-degree angle by type of pencil (B, HB, F, H, 2H, 3H) on a cured coating film using a pencil hardness tester at 500 g load on the cured anti-fingerprint film specimen. It was evaluated visually.
⑤ scratch resistance
Scratch marks left on the coating film were observed after reciprocating the cured anti-fingerprint film specimens 20 times in the same direction and at right angles with the fingernail. The observation result was evaluated by the following method.
○: No trace
△: marks are slightly visible
X: Marks appear clearly.
[ Result example ]
The adhesion, fingerprint, pencil hardness, and scratch resistance of the anti-fingerprint composition including the photocurable fluorine-modified urethane (meth) acrylate resin prepared in Examples (1 to 5) were measured by the above experimental method. The results are shown in Table 1 below.
As shown in the experimental results of Table 1, it can be seen that a significant difference in the adhesion and fingerprint properties according to the content of the fluorine-modified urethane (meth) acrylate prepolymer. In the pencil hardness measurement, the crosslinking density was different after curing depending on the content of the fluorine-modified urethane (meth) acrylate prepolymer and the content of the dilution monomer. Could. In the scratch resistance measurement, it can be seen that the scratch resistance is improved when the content of the inorganic filler is large.
Although the technical spirit of the present invention has been described above with reference to the accompanying drawings, it is intended to exemplarily describe the best embodiment of the present invention, but not to limit the present invention. In addition, it is obvious that any person skilled in the art may make various modifications and imitations without departing from the scope of the technical idea of the present invention.
Claims (9)
An anti-fingerprint composition comprising a photocurable fluorine-modified urethane (meth) acrylate resin, comprising a (meth) acrylate monomer.
The diisocyanate compound,
It is at least any one of 4,4'- dicyclohexyl methane diisocyanate, 1, 6- hexamethylene diisocyanate, and isophorone diisocyanate, It is the fingerprint resin containing the photocurable fluorine-modified urethane (meth) acrylate resin characterized by the above-mentioned. Composition.
The fluorine-modified urethane (meth) acrylate prepolymer,
Weight average molecular weight is 500 to 2000,
An anti-fingerprint composition comprising a photocurable fluorine-modified urethane (meth) acrylate resin, wherein the average urethane bond is 6 to 22 per molecule.
The fluoroalkyl compound,
The weight-average molecular weight is 1000 to 20000, the anti-fingerprint composition comprising a photocurable fluorine-modified urethane (meth) acrylate resin.
The fluoroalkyl compound,
2-nonafluoro butyl ethanol, 2-trideca fluoro hexyl ethanol, 2-hetadeca fluoro octyl ethanol, 2-henacosa fluoro decyl ethanol, 2,3-difluoro benzyl alcohol, 2-fluoro At least one of benzyl alcohol, 1- (tenta fluorophenyl) -ethanol, and 2- (trifluoromethyl) -benzyl alcohol; or a tallow resin comprising a photocurable fluorine-modified urethane (meth) acrylate resin. Composition.
(Meth) acrylate monomers;
Photoinitiators;
Inorganic fillers; And
Diluent solvent; Anti-fingerprint composition comprising a photocurable fluorine-modified urethane (meth) acrylate resin comprising a.
The photoinitiator,
1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenyl-acetophenone, benzaldehyde, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, Benzoinpropyl ether, benzoin ethyl ether, 1- (4-isopropyl-phenol) -2-hydroxy-2-methylpropan-1-one, thioxanthone, benzophenone and 2,4,6-trimethylbenzoyl- The anti-fingerprint composition comprising a photocurable fluorine-modified urethane (meth) acrylate resin, which is any one of diphenylphosphine.
The inorganic filler,
An anti-fingerprint composition comprising a photocurable fluorine-modified urethane (meth) acrylate resin, which is at least one of silica, titania, alumina, zirconia, tin, zinc, antimony and indium.
In the anti-fingerprint composition comprising the photocurable fluorine-modified urethane (meth) acrylate resin,
The fluorine-modified urethane (meth) acrylate prepolymer is 10 to 40 parts by weight,
The (meth) acrylate monomer is 10 to 30 parts by weight,
The photoinitiator 2.5 to 7.5 parts by weight,
5 to 30 parts by weight of the inorganic filler,
Anti-fingerprint composition comprising a photocurable fluorine-modified urethane (meth) acrylate resin, characterized in that it can be included in 30 to 60 parts by weight of the dilution solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100140032A KR101163922B1 (en) | 2010-12-31 | 2010-12-31 | Anti-fingerprinting resin composition comprising photo-curable fluorine modified urethane (meth)acrylate resin and anti-fingerprinting coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100140032A KR101163922B1 (en) | 2010-12-31 | 2010-12-31 | Anti-fingerprinting resin composition comprising photo-curable fluorine modified urethane (meth)acrylate resin and anti-fingerprinting coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR101163922B1 true KR101163922B1 (en) | 2012-07-11 |
Family
ID=46716461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020100140032A KR101163922B1 (en) | 2010-12-31 | 2010-12-31 | Anti-fingerprinting resin composition comprising photo-curable fluorine modified urethane (meth)acrylate resin and anti-fingerprinting coating composition |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101163922B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101752489B1 (en) * | 2015-07-24 | 2017-07-11 | 공주대학교 산학협력단 | Photo-curable silicone-fluorine modified urethane (metha)acrylate resin having excellent anti-fouling and anti-fingerprinting and resin composition for coating including the same |
| KR20210106716A (en) * | 2020-02-21 | 2021-08-31 | 조광페인트주식회사 | Photo-curable composition for pre-coated metal and method for manufacturing pre-coated metal using the same |
| CN115746602A (en) * | 2022-11-12 | 2023-03-07 | 烟台德邦科技股份有限公司 | High-reliability UV protective coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100403667B1 (en) | 1995-12-30 | 2004-04-03 | 고려화학 주식회사 | Photocurable coating composition using urethane acrylate oligomer |
| KR100432211B1 (en) | 1995-12-30 | 2004-08-31 | 고려화학 주식회사 | Method for producing photocurable fluoro-modified urethane acrylate oligomer having excellent heat resistance |
-
2010
- 2010-12-31 KR KR1020100140032A patent/KR101163922B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100403667B1 (en) | 1995-12-30 | 2004-04-03 | 고려화학 주식회사 | Photocurable coating composition using urethane acrylate oligomer |
| KR100432211B1 (en) | 1995-12-30 | 2004-08-31 | 고려화학 주식회사 | Method for producing photocurable fluoro-modified urethane acrylate oligomer having excellent heat resistance |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101752489B1 (en) * | 2015-07-24 | 2017-07-11 | 공주대학교 산학협력단 | Photo-curable silicone-fluorine modified urethane (metha)acrylate resin having excellent anti-fouling and anti-fingerprinting and resin composition for coating including the same |
| KR20210106716A (en) * | 2020-02-21 | 2021-08-31 | 조광페인트주식회사 | Photo-curable composition for pre-coated metal and method for manufacturing pre-coated metal using the same |
| KR102365398B1 (en) * | 2020-02-21 | 2022-02-22 | 조광페인트주식회사 | Photo-curable composition for pre-coated metal and method for manufacturing pre-coated metal using the same |
| CN115746602A (en) * | 2022-11-12 | 2023-03-07 | 烟台德邦科技股份有限公司 | High-reliability UV protective coating and preparation method thereof |
| CN115746602B (en) * | 2022-11-12 | 2023-12-01 | 烟台德邦科技股份有限公司 | High-reliability UV protective coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100884079B1 (en) | Composition for hard coating | |
| JP5607162B2 (en) | Optical fiber with multilayer coating system | |
| JP5744064B2 (en) | Highly transparent plastic substrate coated with scratch resistance, in particular a jacket for electronic devices, its production method and its use | |
| KR20090057597A (en) | Hard-coating composition having good hardness, heat-resistance and flexibility | |
| KR101664735B1 (en) | Anti-fingerprint hardcoating composition and anti-fingerprint hardcoating film using the same | |
| CN105733434B (en) | Photocurable resin composition and cured film, band film base material and its manufacturing method | |
| TWI717649B (en) | Curable compositions containing thiol compounds | |
| JPWO2011013497A1 (en) | Photocurable hydrophilic coating, hydrophilic coating, and hydrophilic article | |
| KR101752489B1 (en) | Photo-curable silicone-fluorine modified urethane (metha)acrylate resin having excellent anti-fouling and anti-fingerprinting and resin composition for coating including the same | |
| KR20090090866A (en) | Prism sheet of high refractive index and elasticity, the composition for producing the same and the method for its production | |
| KR101134383B1 (en) | Coating agent for Poly?methyl methacrylate?pannel nano imprinting having superior anti-light reflection | |
| KR101163922B1 (en) | Anti-fingerprinting resin composition comprising photo-curable fluorine modified urethane (meth)acrylate resin and anti-fingerprinting coating composition | |
| JP2008208226A (en) | Radiation-curable resin composition | |
| KR101403769B1 (en) | Ultraviolet-curable color composition and steel sheet using the same | |
| JP2009237284A (en) | Liquid curable resin composition | |
| KR20150135243A (en) | Active-energy-ray-curable coating composition | |
| KR20150007076A (en) | Uv curable liquid phase adhesive composition with high refractive | |
| JP4699037B2 (en) | Energy ray curable composition | |
| KR102179180B1 (en) | Photo-curable coating composition for pre-coated metal and preparation method for pre-coated metal using the same | |
| JP2011026409A (en) | Fingerprint-resistant curable resin composition and method for forming fingerprint-resistant coating film using the same | |
| JP2012031312A (en) | Optical curable coating material composition | |
| WO2008120983A2 (en) | Ribbon matrix material for optical fiber with excellent bending resistance | |
| JP2009096825A (en) | Coating agent composition for vehicle and coating method of painting surface of vehicle body | |
| JP6288509B2 (en) | Antifouling coating agent and article | |
| WO2018207828A1 (en) | Curable composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20150702 Year of fee payment: 4 |
|
| FPAY | Annual fee payment |
Payment date: 20160704 Year of fee payment: 5 |
|
| FPAY | Annual fee payment |
Payment date: 20170704 Year of fee payment: 6 |
|
| FPAY | Annual fee payment |
Payment date: 20180703 Year of fee payment: 7 |
|
| FPAY | Annual fee payment |
Payment date: 20190703 Year of fee payment: 8 |