KR20080108755A - Uv curable coating composition having excellent adhesiveness and contamination resistance - Google Patents

Abstract

A UV curable coating composition is provided to ensure excellent contamination resistance and to be applied to the various materials by allowing a fluoro acrylate polymer to contain a repeating unit induced from fluoro alkyl(meth)acrylate. A UV curable coating composition comprises a fluoro acrylate polymer having a DOPA functional group. The fluoro acrylate polymer having a DOPA functional group is comprised of the following steps of: (a) a step for manufacturing the acrylate having a DOPA functional group; (b) a step for polymerizing an acrylate having a DOPA functional group, hydroxyalkylacrylate, butylacrylate and fluoroacrylate to manufacture a polyol; (c) a step for reacting a isocyanate-based compound and hydroxyalkylacrylate to manufacture an acrylate having an isocyanate functional group; and (d) a step for polymerizing a polyol containing a DOPA functional group and fluorine, manufactured from the (b) step and an acrylate having an isocyanate functional group manufactured from the (c) step.

Description

UV curable coating liquid composition excellent in adhesion and stain resistance {UV CURABLE COATING COMPOSITION HAVING EXCELLENT ADHESIVENESS AND CONTAMINATION RESISTANCE}

The present invention relates to a UV-curable coating liquid composition excellent in adhesion and fouling resistance, and more particularly excellent in adhesion, can be applied to various substrates such as plastics, metals, and the like by reducing the adhesion of the surface of the coating film The present invention relates to an ultraviolet curable coating liquid composition that is excellent in crosslinkability.

Various displays such as CRTs for monitors, CRTs such as CPTs for TVs, TFT-LCD polarizers, PDP filters, RPTS filters, mobile phone liquid crystals, watches, photographs, picture frames, etc. are closely related to our lives. When the display is exposed to light such as natural light, eye fatigue or headache may be caused by reflected light, and an image produced inside the display may not be clearly formed in the eye, resulting in a decrease in contrast.

In order to solve this problem, there have been studies to develop a low reflection coating layer that reduces the reflectance by inducing extinction interference. Japanese Patent Application Laid-Open Nos. 9-208898 and 8-122501 describe a low reflection layer having a refractive index of 1.28 to 1.38 prepared using a silicic acid compound and magnesium fluoride (MgF ₂ ) metal oxide. Application No. 96118471 describes a coating liquid prepared by using a compound having a fluorine-based silane and a fluorine-based alkyl group and having a low reflection function and a stain-resistant function due to a decrease in surface energy.

In general, in order to have a resistance to a pollutant, the surface energy is low and fingerprints, etc. are not easily buried, and the charges on the surface are flowed without being offset or staying, so that dust does not adhere to the electrostatic attraction.

Therefore, there have been reported methods of improving the stain resistance to prevent the adhesion of dust and the like by not charging the surface. For example, Japanese Patent Application Laid-Open No. 94-65529 discloses Indium doped Tin Oxide ITO, Antimony-doped Tin Oxide (ATO), Antimony-doped Zinc Oxide (Antimony) Japanese Patent Laid-Open Publication Nos. 93-295353 and 94-32997 disclose a method of using a conductive metal oxide filler such as doped Zinc Oxide (AZO), and a method of using an antistatic agent made of a polymer, and Japanese Patent Laid-Open No. 93 -339336 describes a method of using a low molecular weight surfactant.

However, methods of preventing adhesion of dust and the like by using a conductive metal oxide or a conductive polymer cannot control a low refractive index and thus can not exhibit a low reflection function, and the used surfactant is released to the surface of the coating film with time, so that the effect is long. There is a problem that cannot be sustained.

Korean Patent Laid-Open Publication Nos. 2004-0083916 and 2004-0085484 describe a coating liquid composition containing a fluorine-based acrylate monomer. However, since the composition is added in a monomer state, polymerization is not performed well because of low reactivity. There was a problem of low. U. S. Patent No. 6,207, 777 describes a coating liquid composition having one component of a polymer composed of repeating units of fluorine-based acrylate, but has a problem of low adhesiveness.

In addition, Macromolucules (2006, 39, 1740-1748), US Patent Publication Nos. 2003-0087338, 2005-0148050, and 2005-0224175 use bioadhesive protein components such as DOPA to improve adhesion. Although a coating liquid composition is described, the patent has a problem of low pollution resistance.

Accordingly, an object of the present invention is to provide an ultraviolet curable coating liquid composition which is excellent in adhesiveness and can be variously applied to plastics, metals, stones, and glass.

Another object of the present invention is to provide an ultraviolet curable coating liquid composition excellent in fouling resistance.

Still another object of the present invention is to provide an ultraviolet curable coating liquid composition which is excellent in crosslinking property and is excellent in wear resistance and does not leak out even after long-term use.

In order to achieve the above object,

The present invention provides an ultraviolet curable coating liquid composition having excellent adhesion and stain resistance, comprising a fluorine acrylate polymer having a DOPA functional group.

The present invention also provides a) a fluorine-based acrylate polymer having a DOPA functional group; b) polyfunctional acrylate monomers; c) reactive acrylate oligomers; d) UV curable initiators; And e) provides an ultraviolet curable coating liquid composition comprising a solvent, excellent in adhesion and stain resistance.

Hereinafter, the present invention will be described in detail.

UV curable coating liquid composition excellent in adhesion and fouling resistance according to the present invention comprises a fluorine-based acrylate polymer having a DOPA functional group.

DOPA according to the present invention includes all of the isomers such as L-DOPA, D-DOPA, DL-DOPA, and the like is preferably L-DOPA (3,4-dihydroxyphenyl-L-alanine) represented by the following formula (1). DOPA is a monomolecular compound that is a component of mussel adhesive proteins (MAP). The mussel adhesive protein is a protein having a very strong adhesion, it is known that the cause of adhesion is the DOPA.

The fluorine-based acrylate polymer having a DOPA functional group, which is a component of the UV-curable composition excellent in adhesion and fouling resistance according to the present invention, includes: i) an acrylate repeating unit having a DOPA functional group, ii) a fluoroalkyl acrylate repeating unit, iii) Butyl acrylate repeating units and iii) acrylate repeating units comprising urethane linkages.

The fluorine acrylate polymer having a DOPA functional group according to the present invention includes (i) a fluorine acrylate (fluoroalkyl acrylate) repeating unit, ii) a butyl acrylate repeating unit, iii) a hydroxy acrylate repeating unit, and iii) a DOPA functional group. Polyol (1) having an acrylate repeating unit having a, may be prepared by the urethane reaction of the acrylate (2) including an isocyanate group.

To prepare a fluorine-based acrylate polymer having a DOPA functional group as a component of the ultraviolet curable composition according to the present invention, first, a) preparing a acrylate having a DOPA functional group is performed. The amine group (-NH ₂ ) or the carboxyl group (-COOH), which is a DOPA functional group, reacts with the functional group of another compound to form a urethane bond, a peptide bond, an ester bond, and the like, and may be an acrylate having a DOPA functional group.

The acrylate having a DOPA functional group according to the present invention, for example, as shown in Scheme 1, comprising a step of preparing a acrylate having a DOPA functional group by ester-reacting hydroxy alkyl acrylate and DOPA Can be prepared.

The hydroxy alkyl acrylate of the present invention includes an acrylate compound, methacrylate, for example, an acrylate compound having a hydroxy alkyl group having 1 to 20 carbon atoms, specifically 1 to 5 carbon atoms, more specifically hydroxy Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxy-poly (alkyleneoxy) alkyl (meth) acrylate, pentaerythritol hydroxy tri (meth ) Acrylate, dipentaerythritol hydroxy penta (meth) acrylate, ditrimethylolpropane hydroxy tri (meth) acrylate, or mixtures thereof.

In this step, as the reaction solvent, a solvent commonly used in the reaction of an organic compound may be used without limitation, without limitation, dichloromethane, N, N-dimethylformamide, chloroform ( chloroform), water or mixtures thereof.

This step can be carried out in a conventional manner by mixing the reactants in the presence of a solvent, first blocking in order to reduce the nucleophilicity of the amine group (-NH ₂ ) of DOPA, as illustrated in Scheme 1 below. After the protection, an ester reaction may be performed, and then a process of deblocking hydrogen of the blocked amine group may be sequentially performed. This method has the advantage of increasing the reaction yield.

At this time, the amine group can be blocked using a known method including a conventional method without limitation, for example, it can be blocked using di-tert-butyldicarbonate.

Blocked amine groups can also be deblocked using known methods including, but not limited to, conventional methods, for example solutions containing 4M hydrochloric acid in 1,4-dioxane (4M HCl in 1,4-dioxane ) Can be deblocked.

The reaction conditions are determined in consideration of the reaction rate, the stability of the reactants, the boiling point of the reaction solvent, and the like. For example, the reaction temperature is room temperature, and the reaction pressure is normal pressure. The reaction time is not particularly limited, but if it is too short, the reaction yield is low, and if it is too long, it is economically disadvantageous without any particular advantage.

In addition, the acrylate having a DOPA functional group according to the present invention, for example, as shown in Scheme 2 below, one side of the isocyanate group (-NCO) of the diisocyanate (diisocyanate) amine of the DOPA (amine) (urea) (urea) ), And the other side may be an acrylate prepared by ester bonding an acrylate. More specifically, first, L-DOPA, thionyl chloride and methanol (methanol) are mixed and the reaction is carried out to obtain a product (1) in which the carboxyl group of L-DOPA is substituted with a methyl ester group. Next, hydroxy ethyl methacrylate (HEMA) and isophorone diisocyanate (IPDI) are reacted to obtain HEMA-IPDI, the product (2). Next, product (1) and product (2) are reacted to obtain an acrylate having a DOPA functional group according to the present invention.

As the isocyanate compound, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI) or a mixture thereof can be preferably used.

In order to produce a fluorine-based acrylate polymer having a DOPA functional group as a component of the ultraviolet curable composition according to the present invention, as shown in the following Scheme 3, b) an acrylate having a manufactured DOPA functional group, hydroxy alkyl acrylic The rate, butyl acrylate and fluorine-based acrylate are polymerized to prepare a polyol including a DOPA functional group and fluorine.

In this step, the hydroxy alkyl acrylate may be a compound of the same kind as the acrylate usable in step a).

In this step, the fluorine-based acrylate may be a (meth) acrylate having a fluoroalkyl group, and preferably 1H, 1H-perfluoro-n-octylacrylate (1H, 1H-perfluoro- n-octylacrylate) can be used.

As the reaction solvent, toluene, n-butyl acetate or a mixture thereof can be used without limitation.

This step can be carried out by adding a polymerization initiator, if necessary, can be used a conventional polymerization initiator used for polymer synthesis, preferably using an initiator represented by the trade name V-65 (manufactured by Wako Pure Chemical Co., Ltd.) Can be.

Since hydroxy alkyl acrylate and butyl acrylate have a problem that a polymerization reaction occurs between each homogeneous compound when one compound is excessively excessive, gelation phenomenon occurs. It can be selected, for example 1: 1 by weight ratio.

The fluorine-based acrylate is preferably 0.1 to 1 parts by weight based on 100 parts by weight of hydroxy alkyl acrylate and butyl acrylate. If the amount is too high, mixing with other acrylates is not smooth and phase separation occurs, resulting in subsequent polyols. There is a problem that the reactivity of the manufacturing step is significantly lowered or not synthesized.

The amount of acrylate having a DOPA functional group is preferably 1 to 10 parts by weight based on 100 parts by weight of the total amount of hydroxy alkyl acrylate and butyl acrylate. There is a problem of poor polymerization reactivity.

The amount of the reaction solvent may be selected in an appropriate range in consideration of the concentration of the reactant, the occurrence of gelation during the reaction, and the like.

The amount of the polymerization initiator to be used is not particularly limited, and may be appropriately adjusted and used as necessary based on the amount usually used.

This step may be carried out by a conventional method of mixing the reactants in the presence of a solvent and adding an initiator. The reaction conditions are determined in consideration of the reaction rate, stability of the reactants, boiling point of the reaction solvent, and the like. For example, it is 80-150 degreeC, and reaction pressure is normal pressure, for example. The reaction time is not particularly limited, but if it is too short, sufficient polymerization will not be achieved. If it is too long, the reaction will end at an appropriate degree of polymerization because it is gelled. As a real number from 0 to 1, where a + b + c + d = 1.

C) Next, as illustrated in Scheme 4 below, an isocyanate compound and hydroxy alkyl acrylate are reacted to prepare an acrylate having an isocyanate functional group.

In this step, as the isocyanate compound, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI) or a mixture thereof may be preferably used.

As the hydroxy alkyl acrylate, a compound of the same kind as the acrylate usable in steps a) and b) may be used.

As the reaction solvent, n-hexane or the like can be used.

As illustrated in Scheme 4 below, this step preferably reacts only one isocyanate functional group in the isocyanate compound with a hydroxyl group (—OH) to form a urethane bond. Therefore, this step is carried out while slowly adding dropwise hydroxy alkyl acrylate (at a very low concentration of hydroxy alkyl acrylate) to a mixed solution of isocyanate compound mixed with a solvent, or isocyanate compound mixed at a constant ratio. Preference is given to slowly adding the solvent dropwise to the mixture of hydroxy alkyl acrylates.

The reaction mixture ratio of the isocyanate compound and the hydroxy alkyl acrylate is preferably 1: 1 in an equivalent ratio.

The reaction conditions are determined in consideration of the reaction rate, the stability of the reactants, the boiling point of the reaction solvent, the reaction temperature is, for example, room temperature, and the reaction pressure is, for example, atmospheric pressure. The reaction time is not particularly limited, but if it is too short, the reaction yield is low, and if it is too long, it is economically disadvantageous without any particular advantage, for example, 20 hours.

Next, as illustrated in Scheme 5, step d) of reacting the DOPA functional group prepared in step b) and the polyol containing fluorine and the acrylate having the isocyanate functional group prepared in step c) is performed (Scheme Scheme). 5, a, b, c, d, and e are mole fractions of each repeating unit, which is a real number of 0 to 1, and a + b + c + d + e = 1.

This step can be carried out in a conventional manner by reacting the reactants in the presence of a solvent with mixing and stirring.

This step is a step of forming a urethane bond (urethane bonding) of the unreacted isocyanate period of the polyol prepared in step b) and the acrylate prepared in step c). Therefore, the mixing is performed in consideration of the hydroxyl equivalent number of the polyol and the equivalent number of unreacted isocyanate groups. If the equivalent number of hydroxyl groups of the polyol is too high, there is a risk that the branching point is increased during polymerization and gelation occurs. At this time, the hydroxyl group: isocyanate group is preferably 1: 1 or less in an equivalent ratio, more preferably 1: 1, and even more preferably 4: 3.

In the fluorine-based acrylate polymer having a DOPA functional group prepared in this step, all or part of the hydroxyl group (except the hydroxyl group of DOPA) of the polyol may be urethane reacted according to the present equivalence ratio and the reaction conditions. The compound represented by 2 may be sufficient, and the compound represented by General formula (3) may be sufficient.

The reaction solvent of this step may be used without limitation methyl ethyl ketone (MEK, methyl ethyl ketone), cyclohexanone (cylohexanone) or a mixture thereof.

Dibutyl tin dilaurate (DBTDL) may also be added as a catalyst for the urethane bond reaction.

In Formula 2, a, b, c, d, and e are mole fractions of each repeating unit, which is a real number of 0 to 1, and a + b + c + d + e = 1.

In Formula 3, a, c, d, and e are mole fractions of each repeating unit, which is a real number of 0 to 1, and a + c + d + e = 1.

The fluorine acrylate polymer having a DOPA functional group according to the present invention prepared by the above method has a molecular weight of, for example, a maximum of 15,000, and is in a pre-polymer state in which the oligomer and the polymer are in an intermediate state. Therefore, the UV curable coating liquid composition according to the present invention has excellent functional crosslinkability due to less functional groups participating in the reaction during UV curing, easy to control the crosslinking rate, and is used together with the polyfunctional acrylate monomer and the reactive acrylate oligomer to cure for a long time. It does not leak out even when used, there is an advantage that can form a coating film excellent in wear resistance.

In the fluorine-based acrylate polymer having a DOPA functional group according to the present invention prepared by the above method, a branch connected to a carbon-carbon main chain has an ester bond, a urethane bond, and the like. In this case, physical properties such as durability and strength are superior to those in which only carbon-carbon chains are connected, and synthetic conditions are better. Since the fluorine-based acrylate polymer of the present invention is a prepolymer which is an intermediate state between the oligomer and the polymer, it may also be referred to as an ester acrylate prepolymer, an acrylate prepolymer, or a urethane acrylate prepolymer.

UV-curable coating liquid composition excellent in adhesion and fouling resistance according to the present invention comprises a) a fluorine-based acrylate polymer having a DOPA functional group; b) polyfunctional acrylate monomers; c) reactive acrylate oligomers; d) UV curable initiators; And e) a solvent.

a) The fluorine-based acrylate polymer having a DOPA functional group is preferably contained in an amount of 0.1 to 1% by weight based on the whole UV curable coating liquid composition. If it is less than the above range, there is a slight problem of improvement of physical properties such as adhesion and fouling resistance, and if it exceeds the above range, if the improvement of fouling resistance is insignificant or lowered, the cross-linking density of the hard coating resin is reduced. There is a problem that the hardness is lowered and the hardness is lowered.

b) Multifunctional acrylate monomers include dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hydroxy pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, Propoxylated glycerol triacrylate, trimethylpropane ethoxy triacrylate or mixtures thereof can be used.

b) The polyfunctional acrylate monomer is preferably included in the amount of 5 to 15% by weight based on the total UV curable coating liquid composition, and if the content is less than the above range, since the DPHA and PETIA have three or more functional groups, the crosslinking density of the resin (cross linking density) and hardness. Therefore, as the content is increased, the wear resistance is better, but the film is brittle, the haze is severe, and the transparency is lowered.

c) Reactive acrylate oligomers are compounds represented by trade names EB600 (bisphenol-A epoxy diacrylate, SK UCB), EB9260 (SK UCB) or EB 294 / 25HD (SK UCB, SK cytec) or mixtures thereof. Can be used. EB 600 improves wear resistance, solvent resistance and gloss, while EB 294 / 25HD and EB 9260 improve the flexibility of the coating.

c) The reactive acrylate oligomer is preferably included in 5 to 15% by weight based on the entire hard coating liquid composition.

d) As the UV curable initiator, UV curable initiators commonly known and known UV curable initiators can be used without limitation, and preferably 1-hydroxy cyclohexylphenyl ketone, benzyl dimethyl ketal, hydroxydimethylacetophenone, benzo Phosphorus, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether or mixtures thereof can be used. For example, the trade names Daracur 1173 ^** , Irgacure 184 ^**,, Irgacure 907 ^** may be the initiator represented by the formula (at least Ciba Inc.).

d) UV curing initiator is preferably contained in 1 to 5% by weight based on the entire hard coating liquid composition resin, if the content is less than the above range there is a door hardening does not occur, if it exceeds the above range surface curing (Surface curing / through curing) is a serious problem, so choose appropriately.

e) solvents include benzene, toluene, methyl ethyl ketone, methyl isobutyl ketone, acetone, ethanol, tetrahydrofurfuryl alcohol, propyl alcohol, propylene carbonate, N-methyl pyrrolidinone, N-vinyl pyrrolidinone, N- Acetyl pyrrolidinone, N-hydroxy methyl pyrrolidinone, N-butyl pyrrolidinone, N-ethyl pyrrolidinone, N- (N-octyl) pyrrolidinone, N- (N-dodecyl) pyrrolidineone , 2-methoxyethyl ether, xylene, cyclohexane, 3-methyl cyclohexanone, ethyl acetate, butyl acetate, tetrahydrofuran, methanol, amyl propionate, methyl propionate, propylene glycol methyl ether, di Ethylene glycol monobutyl ether, dimethyl sulfoxide, dimethyl formamide, ethylene glycol, hexafluoroantimonate, monoalkyl ether of ethylene glycol, dialkyl ether of ethylene glycol, cellosolves thereof Cellosolves or mixtures thereof can be used.

The type and content of the solvent may be appropriately selected in consideration of physical properties such as coating film smoothness, substrate erosion by the solvent, adhesiveness, haze, and pinhole phenomenon, and an erosive solvent and a non-erosive solvent are appropriately selected. Silver is preferably contained in 65 to 80% by weight based on the entire coating liquid composition.

Since the conventional coating liquid composition is adhered by solvent erosion and interlocking adhesion, there is a disadvantage that it can be applied only to a substrate eroded in a solvent such as plastic. However, the UV-curable coating liquid composition according to the present invention is a component of the fluorine-based acrylate polymer, one of the mussel adhesive proteins (MAP) which is a very strong protein, DOPA (3, 4) as a cause of adhesion -dihydroxyphenyl-L-alanine), which has a functional group derived from a single molecule, is excellent in adhesiveness and adhered by interlocking, so it is irrelevant to whether the substrate is eroded by the solvent and the degree of curing according to the depth. It is adhered to the polymer substrate, and can be applied not only to a polymer substrate, but also to various substrates such as metal substrates such as ships and oil pipes, and building materials such as stones and glass.

In addition, since the UV curable coating liquid composition according to the present invention includes a repeating unit derived from fluoro-acrylate (fluoroalkyl (meth) acrylate), one component of the fluorine-based acrylate polymer, the adhesive force on the surface of the coating film is reduced to prevent contamination. There is an excellent advantage.

In addition, since the UV-curable coating liquid composition according to the present invention is added as a fluorine-based acrylate polymer as one component thereof as a pre-polymer state, which is an intermediate state between the oligomer and the polymer, the functional group participating in the reaction during UV curing is less and thus crosslinking is possible. It is excellent, it is easy to control the crosslinking rate, it is used together with the multifunctional acrylate monomer and the reactive acrylate oligomer and cured so that it does not leak out even after long time use and it is possible to form a coating film having excellent wear resistance. have.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Example 1 DOPA Preparation of fluorine-containing methacrylate polymer having a functional group

a) DOPA Preparation of methacrylate having a functional group

Preparation of Reactant 2

As shown in Scheme 1, 1.97 g (10 mmol) of 3,4-dihydroxyphenyl alanine was dissolved in 20 mL of chloroform, and the solution was dissolved in sodium bicarbonate. ) 15mL of 0.84g aqueous solution and 2g of sodium chloride were added thereto, and then 2.18g (10 mmol) of di-tert-butyldicarbonate was added thereto, followed by stirring for 12 hours. Next, the reaction was extracted into an organic layer under basic conditions, dried over anhydrous sodium sulfate, and then condensed under reduced pressure to obtain 4.35 g of a compound of reactant 2 (yield: 48.8%).

Preparation of Reactant 3

As shown in Scheme 1, 3.06 g (10.30 mmol) of the compound of Reaction 2 prepared above was dissolved in 45 mL of dimethyl formamide (DMF), and 3.19 g (15.45) of dicyclohexylcarbodiimide was dissolved in the solution. mmol) and 4-dimethylaminopyridine, 126 mg (1.03 mmol) were added thereto, followed by stirring, and then 1.88 mL (15.45 mmol) of 2-hydroxyethyl methacrylate was added thereto. After stirring at 12 ° C. for 12 hours, the solvents were all removed under reduced pressure and purified by silica gel chromatography to prepare Reactant 3 Compound.

Preparation of Reactant 4

As shown in Scheme 1 below, 41 g (2.44 mmol) of the reactant 3 prepared above was prepared with 6 mL (4.0 M HCl in 1,4-dioxane) (24.4) in 6 mL (24.4 mmol) of 1,4-dioxane. mmol)) and stirred at room temperature for 1 hour. Next, the solvents were all removed under reduced pressure, and after basifying, the compound of reactant 4 obtained was used in the next step.

Scheme 1

a) DOPA Preparation of Polyols Containing Functional Groups and Fluorine

Toluene and n-butyl acetate were each mixed at a ratio of 1: 1 by 9.8% by weight, and added to the reactor in advance, followed by nitrogen injection and heat to the contents. 50 parts by weight of hydroxy propyl methacrylate, butyl acrylate, and 1H, 1H-perfluoro-n-octyl acrylate, and the methacrylate having the DOPA functional group prepared above when the solvent of the content is 80 ° C. 95.96% by weight of the monomer mixture mixed at a ratio of: 50: 0.1: 1 and 1.39% by weight of the thermal initiator V-65 (manufactured by Wako Pure Chemical Co., Ltd.) were added to 13.06% by weight of n-butyl acetate, and then slowly added for about 2 hours. It was. Thereafter, the mixture was stirred for about 1 hour and then reacted to prepare a polyol.

c) Preparation of a methacrylate having an isocyanate functionality

IPDI-HEMA (1: 1) adduct was prepared using methods well known in the art as shown in Scheme 6 below. 97.81 g (440 mmol) of IPDI (isophorone diisocyanate) is added to n-hexane (880 mL), and 68.72 g (528 mmol) of hydroxyethyl methacrylate (HEMA) is slowly added at room temperature over 20 hours. The solvent is then removed by distillation under reduced pressure to afford the desired compound.

d) DOPA Preparation of fluorine-containing methacrylate polymer having a functional group

The prepared polyol (19.93 g, -OH value 398.6) and the prepared isocyanate reactant (13.22 g) were mixed in an equivalent ratio of 4: 3. This was added to cyclohexanone (32.00 g) with DBTDL (1 mol per 100 mol of isocyanate reactant) and stirred at 80 ° C. for 3 hours to perform a urethane reaction to prepare a fluorine-based methacrylate polymer having a DOPA functional group.

Example 2 DOPA Preparation of fluorine-containing methacrylate polymer having a functional group

In step b) of Example 1, 50:50 of methacrylate having hydroxy ethyl methacrylate, butyl-arclate, 1H, 1H-perfluoro-n-octylacrylate, and the DOPA functional group prepared above is added. A fluorine-based methacrylate polymer having a DOPA functional group was prepared in the same manner as in Example 1, except that the monomer mixture was used in a ratio of 0.1: 5.

Example 3 DOPA Preparation of fluorine-containing methacrylate polymer having a functional group

In step b) of Example 1, the methacrylate having hydroxy propyl methacrylate, butyl acrylate, 1H, 1H-perfluoro-n-octylacrylate, and the DOPA functional group prepared above is 50:50: A fluorine-based methacrylate polymer having a DOPA functional group was prepared in the same manner as in Example 1, except that the monomer mixture was used at a ratio of 0.1: 5.

Example 4 DOPA Preparation of fluorine-containing methacrylate polymer having a functional group

In step b) of Example 1, the methacrylate having hydroxy propyl methacrylate, butyl acrylate, 1H, 1H-perfluoro-n-octylacrylate, and the DOPA functional group prepared above is 50:50: A fluorine-based methacrylate polymer having a DOPA functional group was prepared in the same manner as in Example 1, except that the monomer mixture was used at a ratio of 0.1: 10.

[Examples 5 to 10, Comparative Example 1] Preparation of UV Curable Coating Liquid Composition

The materials of Table 1 were added in order to the reactor, mixed until the coating solution became uniform, and then filtered with a filter of 0.45 μm in size to prepare a coating solution composition (but the unit in Table 1 is parts by weight).

division Example Comparative Example 1 5 6 7 8 9 10 Dipentaerythritol hexaacrylate 9 9 9 9 9 9 9 Pentaerythritol tetraacrylate 1.6 1.6 1.6 1.6 1.6 1.6 1.6 EB 600 ^{* 16 16 16 16 16 16 16 EB  294/25 HD * 0.48 0.48 0.48 0.48 0.48 0.48 0.48 EB  9260 * 6 6 6 6 6 6 6 Example  1 of DOPA And fluorine-containing Methacrylate  Polymer 0.1 One 2 - - - - Example  2 of DOPA And fluorine-containing Methacrylate  Polymer - - - 0.1 - - - Example  3 of DOPA And fluorine-containing Methacrylate  Polymer - - - - 0.1 - - Example  4 of DOPA And fluorine-containing Methacrylate  Polymer - - - - - 0.1 - Daracur  1173 ** 0.65 0.65 0.65 0.65 0.65 0.65 0.65 Irgacure  184 ** 0.65 0.65 0.65 0.65 0.65 0.65 0.65 Irgacure  907 ** 0.65 0.65 0.65 0.65 0.65 0.65 0.65 ethyl Cellulsolve 25 25 25 25 25 25 25 ethanol 8.33 8.33 8.33 8.33 8.33 8.33 8.33 Ethyl acetate 5 5 5 5 5 5 5 n- Butanol 16.75 16.75 16.75 16.75 16.75 16.75 16.75 Tego  270 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Tego  410 0.07 0.07 0.07 0.07 0.07 0.07 0.07 [Note] *: SK - UCB four multi acrylate  **: Ciba four UV initiator}

The coating liquid composition prepared in Examples 5 to 10 and Comparative Example 1 was coated on the optical base PET by a roll coating process, dried at 60 to 90 ° C. for 3 to 10 minutes to form a film, and then UV (300 to 2,000 mJ). ) Was irradiated and cured to prepare a fouling resistant coating film.

Then, using the coating films prepared in Examples 5 to 10 and Comparative Example 1 to evaluate the stain resistance, scratch resistance, and adhesion (adhesion) of the film in the following manner, and the results are shown in Table 2 Shown in

1. Pollution resistance

The surface of the coating film prepared in Examples 5 to 10 and Comparative Example 1 was wiped with Kimwipes after 10 seconds of dirtying the black oil pen. This operation was repeated to evaluate the stain resistance by the number of times until the trace of the pen remained. At this time, evaluation was made into (circle) if it could wipe out a pen 10 times or more, (triangle | delta) if it could wipe out a pen by 5-10 times, (triangle | delta), and if it could wipe off a pen by 1 to 5 times.

2. Scratch resistance

A load of 1 kg was placed on the wearer provided with steel batting # 0000, and the presence or absence of scratches was visually observed and evaluated.

3. Adhesiveness of membrane test )

A cross cut nichiban tape peel test was performed on the coating film (crosslinked cured film) formed in Examples 5 to 10 and Comparative Example 1. Specifically, 11 pieces of horizontal and vertical scales, each of which spans the substrate at 1 mm intervals, were made on the coating film, making 100 eyes of 1 mm ² , attaching a cellophane tape on it, and rapidly removing it three times at one location. Was measured. The measurement results are shown in Table 1 below.

○: cross-linking curing even if repeated three times

(Triangle | delta): When the number of peeling eyes is 1-50 by repeating 3 times

X: 3 times repetition when the number of peeling eyes is 51-100

division Pollution resistance Scratch resistance Adhesiveness of membrane Example 5 ○ Good △ Example 6 ○ Good O Example 7 △ Good O Example 8 ○ Good △ Example 9 ○ Good O Example 10 ○ Good O Comparative Example 1 X Good X

As shown in Table 2, the coating film of Examples 5 to 10 according to the present invention was excellent in stain resistance, scratch resistance, and adhesion of the film. In particular, it was confirmed that the adhesion and fouling resistance of the membrane is significantly superior to that of Comparative Example 1.

Since the UV curable coating liquid composition according to the present invention has a functional group derived from DOPA as one component of the fluorine-based acrylate polymer, the adhesiveness is excellent, and therefore, as well as polymers such as plastics, metal substrates such as ships and oil pipes, stones There is an advantage that can be applied to a variety of building exterior materials, such as glass.

In addition, since the UV curable coating liquid composition according to the present invention includes a repeating unit derived from fluoro-acrylate (fluoroalkyl (meth) acrylate), one component of the fluorine-based acrylate polymer, the adhesive force on the surface of the coating film is reduced to prevent contamination. There is an excellent advantage.

In addition, since the UV-curable coating liquid composition according to the present invention is added as a fluorine-based acrylate polymer as one component thereof as a pre-polymer state, which is an intermediate state between the oligomer and the polymer, the functional group participating in the reaction during UV curing is less and thus crosslinking is possible. It is excellent, it is easy to control the crosslinking rate, it is used together with the multifunctional acrylate monomer and the reactive acrylate oligomer and cured so that it does not leak out even after long time use and it is possible to form a coating film having excellent wear resistance. have.

The present invention described above is not limited to the above-described embodiment and the accompanying drawings, and various substitutions, modifications, and changes are possible within the scope of the technical spirit of the present invention. It is obvious to one with ordinary knowledge.

Claims (16)

An ultraviolet curable coating liquid composition comprising a fluorine-based acrylate polymer having a DOPA functional group, and having excellent adhesion and stain resistance. The method of claim 1, The fluorine-based acrylate polymer having a DOPA functional group comprises an acrylate repeating unit having a DOPA functional group, a fluoroalkyl acrylate repeating unit, a butyl acrylate repeating unit, and an acrylate repeating unit having a urethane bond. . The method of claim 1, The fluorine acrylate polymer which has a DOPA functional group, a) preparing an acrylate having a DOPA functional group; b) polymerizing an acrylate, hydroxy alkyl acrylate, butyl acrylate and fluorine acrylate having a DOPA functional group to prepare a polyol comprising a DOPA functional group and fluorine; c) reacting an isocyanate compound and hydroxy alkyl acrylate to prepare an acrylate having an isocyanate functional group; And d) polymerizing a polyol containing a DOPA functional group and a fluorine prepared in step b) and an acrylate having an isocyanate functional group prepared in step c); and a UV curable coating liquid composition prepared by the method comprising a. . The method of claim 3, Hydroxy alkyl acrylate is an ultraviolet curable photochromic coating liquid composition, which is an acrylate having a hydroxy alkyl group having 1 to 20 carbon atoms. The method of claim 3, Hydroxyalkyl acrylates include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxy-poly (alkyleneoxy) alkyl (meth) acrylate, penta UV curable type selected from the group consisting of erythritol hydroxy tri (meth) acrylate, dipentaerythritol hydroxy penta (meth) acrylate, ditrimethylolpropane hydroxy tri (meth) acrylate, and mixtures thereof Photochromic coating solution composition. The method of claim 3, Acrylate having a DOPA functional group of step a), A UV curable coating liquid composition prepared by esterifying hydroxy alkyl acrylate with DOPA. The method of claim 3, Acrylate monomer having a DOPA functional group of step a), An ultraviolet curable coating liquid composition, which is prepared by urea bonding an amine group of DOPA to one isocyanate group of the diisocyanate and ester bonding of an acrylate to the other. The method of claim 1, The fluorine-type acrylate polymer which has a DOPA functional group has a molecular weight of 15,000 or less, The ultraviolet curable coating liquid composition. The method of claim 1, The fluorine-based acrylate polymer having a DOPA functional group is a compound represented by the following formula (2) or formula (3), UV curable coating liquid composition. [Formula 2]

In Formula 2, a, b, c, d, and e are mole fractions of each repeating unit, which is a real number of 0 to 1, and a + b + c + d + e = 1. [Formula 3]

In Formula 3, a, c, d, and e are mole fractions of each repeating unit, which is a real number of 0 to 1, and a + c + d + e = 1. The method of claim 1, DOPA is UV-curable coating liquid composition is L-DOPA. The method of claim 1, a) a fluorine acrylate polymer having a DOPA functional group; b) polyfunctional acrylate monomers; c) reactive acrylate oligomers; d) UV curable initiators; And e) solvent; UV curable coating liquid composition comprising a, excellent adhesion and stain resistance. The method of claim 1, Regarding the entire ultraviolet curing coating liquid composition, a) 0.1 to 2% by weight of a fluorine acrylate polymer having a DOPA functional group; b) 5-15 wt% of the multifunctional acrylate monomer; c) 5 to 15% by weight reactive acrylate oligomer; d) 1 to 5% by weight of UV curing initiator; And e) 65 to 80% by weight solvent Containing, UV-curable coating liquid composition The method of claim 12, The polyfunctional acrylate monomers include dipentaerythritol hexaacrylate, dipentaerythritol hydroxy pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylate, An ultraviolet curable coating liquid composition selected from the group consisting of trimethylpropane ethoxy triacrylate and mixtures thereof. The method of claim 12, The reactive acrylate oligomer is selected from the group consisting of a compound represented by the brand name EB600, a compound represented by the brand name EB9260, a compound represented by the brand name EB 294 / 25HD, and a mixture thereof. The method of claim 12, Initiators for UV curing are 1-hydroxy cyclohexylphenyl ketone, benzyl dimethyl ketal, hydroxydimethylacetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether and their An ultraviolet curable coating liquid composition, selected from the group consisting of a mixture. The method of claim 12, Solvents are benzene, toluene, methyl ethyl ketone, methyl isobutyl ketone, acetone, ethanol, tetrahydrofurfuryl alcohol, propyl alcohol, propylene carbonate, N-methyl pyrrolidinone, N-vinyl pyrrolidinone, N-acetyl pyrroli Dinone, N-hydroxy methyl pyrrolidinone, N-butyl pyrrolidinone, N-ethyl pyrrolidinone, N- (N-octyl) pyrrolidinone, N- (N-dodecyl) pyrrolidinone, 2- Methoxyethyl ether, xylene, cyclohexane, 3-methyl cyclohexanone, ethyl acetate, butyl acetate, tetrahydrofuran, methanol, amyl propionate, methyl propionate, propylene glycol methyl ether, diethylene glycol mono Butyl ether, dimethyl sulfoxide, dimethyl formamide, ethylene glycol, hexafluoroantimonate, monoalkyl ethers of ethylene glycol, dialkyl ethers of ethylene glycol, derivatives thereof and mixtures thereof UV curable coating liquid composition, selected from the group consisting of a compound.