WO2008075806A1 - Photo-curable coating composition comprising hyperbranched structure prepolymer, method for preparing the same and product prepared by the same - Google Patents

Photo-curable coating composition comprising hyperbranched structure prepolymer, method for preparing the same and product prepared by the same Download PDF

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Publication number
WO2008075806A1
WO2008075806A1 PCT/KR2006/005578 KR2006005578W WO2008075806A1 WO 2008075806 A1 WO2008075806 A1 WO 2008075806A1 KR 2006005578 W KR2006005578 W KR 2006005578W WO 2008075806 A1 WO2008075806 A1 WO 2008075806A1
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weight
acrylate
parts
meth
coating composition
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PCT/KR2006/005578
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French (fr)
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Hak Soo Han
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Hak Soo Han
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Priority to PCT/KR2006/005578 priority Critical patent/WO2008075806A1/en
Publication of WO2008075806A1 publication Critical patent/WO2008075806A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/005—Dendritic macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the present invention relates to a photo-curable coating composition. More specifically, the present invention relates to a photo-curable coating composition, which further improves physical properties of a film through the reaction of a hy- perbranched urethane acrylate prepolymer having high adhesiveness with acrylate having excellent physical properties, and has enhanced workability due to no need for a solvent, a method for preparing the same and a product prepared by the same method.
  • the surface of plastic molded products which are made of, for example, polycarbonate, polystyrene, styrene-acrylonitrile, polyester, acrylonitrile-butadiene-styrene, or the like, has disadvantages of inferior physicochemical properties such as low abrasion, scratch and solvent resistance, as compared to glass or metal products.
  • various methods for example a method of applying a silicone or melamine resin to the plastic surface of interest, and a method of forming a protective film having a metallic texture through aluminum vacuum deposition.
  • the silicone resin is a thermosetting material and therefore requires long-term heat exposure for formation of a coating film.
  • a method of forming a coating film which includes coating a substrate with a solution of polyurethane in an organic solvent and evaporating the solvent.
  • a urethane coating poses many limitations in use due to poor adhesiveness and strength, and the risk of air pollution resulting from evaporation of volatile organic compounds (VOCs).
  • VOCs volatile organic compounds
  • Korean Patent Application Publication No. 93-13027 Al discloses a
  • UV-curable coating composition for a vinyl chloride flooring material.
  • the composition disclosed therein exhibits an excessively high viscosity of 300 to 5,000 cPs at 25 0 C because it further incorporates a non-reactive oligomer which is a thermoplastic acrylic resin.
  • this prior art has various problems, such as poor workability due to inapplicability of spray coating, poor mechanical properties such as low heat, abrasion and scratch resistance and low flexibility which are not suitable for a coating material of a vast variety of plastic molded products, and yellowing of urethanes due to generation of a quinone-imide structure upon exposure of aromatic urethane to UV irradiation, when aromatic diisocyanate is used.
  • Korean Patent No. 139881 discloses a photo-curable resin composition
  • a photo-curable resin composition comprising an aliphatic multifunctional isocyanate containing an isocyanurate ring of hex- amethylene diisocyanate, a prepolymer in the form of a reaction product of hydroxy alkyl (meth)acrylate with caprolactone-modified hydroxy ethyl acrylate, a reactive diluent, a photoinitiator and other additives.
  • the above-mentioned photo- curable resin composition exhibits a high viscosity, so a spray coating method cannot be applied.
  • the present invention has been made in view of the above problems, and it is an object of the present invention to provide a photo-curable coating composition which is spray-coatable due to a low viscosity despite a solvent-free type, and can be applied to various substrates including general-purpose plastic, due to excellent adhesive strength with an adherend, high abrasion, chemical and scratch resistance, and low risk of yellowing.
  • a photo-curable coating composition comprising:
  • a hyperbranched ure thane acrylate prepolymer having repeating units of formula (I) radially bound in the molecular structure, through a urethane linkage between a hydroxyl group of polycaprolactone triol and an isocyanate group at one end of isophorone diisocyanate and a urethane linkage between an isocyanate group at the other end of isophorone diisocyanate and a hydroxyl group of polycaprolactone triol, hydroxyethyl (meth)acrylate or hydroxypropyl (meth)acrylate:
  • R is hydrogen or methyl
  • R is ethylene or propylene
  • each X is a residue other than hydrogen of a hydroxyl group in polycaprolactone triol, hydroxyethyl (meth)acrylate or hydroxypropyl (meth) aery late, and at least one of three X is a residue other than hydrogen of a hydroxyl group in polycaprolactone triol;
  • n is an integer of 1 to 5;
  • MMA methylmethacrylate
  • TMPTA trimethylol propane triacrylate
  • a method for preparing a photo-curable coating composition comprising: [22] (a) reacting polycaprolactone triol having a weight- average molecular weight of
  • IPDI isophorone diisocyanate
  • FIG. 1 is a graph showing an IR spectrum for a hyperbranched urethane acrylate prepolymer used in the present invention.
  • FIG. 2 is a graph showing the results of gravimetric analysis according to Example
  • a photo-curable coating composition in accordance with the present invention is characterized by excellent heat resistance, abrasion resistance, scratch resistance and adhesion with an adherend, and superior working efficiency resulting from no risk of yellowing, spray-coatability due to a low viscosity and consequently no use of an organic solvent.
  • the term "hyperbranched prepolymer” refers to a polymer having repeating units of a dendritic structure extending from a core thereof.
  • the prepolymer having a hyperbranched structure the prepolymer is already in a crosslinked form prior to photo-curing, whereby a crosslinking density is increased to thereby improve mechanical properties of the final coating film.
  • Heat resistance of the photo-curable coating composition is attributable to the nature of polyol and diisocyanate used in the present invention. That is, poly- caprolactone triol used in the urethane acrylate prepolymer according to the present invention exhibits substantially no temperature-dependent changes in physical properties, unlike polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol or polycarbonate diol which is used in the preparation of conventional urethane acrylate prepolymers. Further, there is no occurrence of thermal stress or thermal shock due to no heat generation or absorption during the curing process.
  • Isophorone diisocyanate used in the present invention exhibits excellent heat resistance and yellowing resistance, so it is possible to improve heat resistance and yellowing resistance of the final coating composition. Specifically, it is possible to prevent yellowing without addition of a UV absorber or antioxidant because use of isophorone diisocyanate causes no risk of formation of the quinone imide structure due to UV irradiation, unlike use of an aromatic diisocyanate compound. Further, cycloaliphatic di- isocyanate such as isophorone diisocyanate is advantageously superior in toughness and impact resistance.
  • the abrasion resistance and scratch resistance of a photo-curable coating composition in accordance with the present invention derives from properties of acrylate and a hyperbranched prepolymer used in the coating composition. That is, an increase in functional groups of acrylate to be used leads to increased hardness and improved mechanical properties of the coating film.
  • the present invention employs tri- functional trimethylol propane triacrylate, penta- or hexa- functional dipentaerythritol penta/hexa acrylate or a mixture thereof, so a crosslinking degree of the final coating film increases to thereby enhance the hardness of the coating film.
  • methylmethacrylate having excellent flexibility and elasticity is used together to offset such shortcomings.
  • a mixture of trimethylol propane triacrylate and dipentaerythritol penta/hexa acrylate is used to thereby provide combination of optimum hardness and flexibility.
  • abrasion resistance and scratch resistance can be improved since a crosslinking density increases due to the crosslinked structure of the hyperbranched prepolymer, as described above.
  • Polycaprolactone triol which is polyol used in the present invention, contains large numbers of carbonyl groups in the molecular structure, thus providing high hy- drophilicity. Therefore, it is possible to improve adhesion with the adherend due to excellent adhesive strength and flexibility resulting from such high hydrophilicity. Further, the polycaprolactone triol contains both hydrophobic and hydrophilic units, so it is possible to easily blend the final coating composition with other polymer components.
  • the photo-curable coating composition according to the present invention comprises 80 to 800 parts by weight of methylmethacrylate, 80 to 150 parts by weight of trimethylol propane triacrylate, dipentaerythritol penta/hexa acrylate or a mixture thereof, and 10 to 30 parts by weight of the photoinitiator, based on 100 parts by weight of the hyperbranched urethane acrylate prepolymer. Only when the composition has the above-specified component ratio, it is possible to achieve optimal mechanical properties including adhesive strength, flexibility and abrasion resistance while having a spray-coatable viscosity.
  • Methylmethacrylate used in the present invention serves to impart flexibility and elasticity to the final coating film, while simultaneously diluting the final coating composition to control a viscosity, which allows for spray coating using a spray. If a content of methylmethacrylate is lower than 80 parts by weight, based on 100 parts by weight of the hyperbranched ure thane acrylate prepolymer, a viscosity is excessively high, which is not suitable for spray coating. On the other hand, if a content of methylmethacrylate is higher than 800 parts by weight, the hardness of the final coating film may be deteriorated. More preferably, the content of methylmethacrylate is in a range of 200 to 800 parts by weight.
  • 1,6-hexanediol diacrylate may be additionally used to control a viscosity of the composition.
  • a weight- average molecular weight of polycaprolactone triol used in the present invention may be preferably in a range of 300 to 900. If the weight-average molecular weight of the compound is lower than 300, excessively high hardness may result in brittleness of the coating film. On the other hand, if the weight-average molecular weight of the compound is higher than 900, a viscosity increases, and the coating film may be undesirably weakened because the hardness is too low when the final coating composition is cured.
  • the hyperbranched urethane acrylate prepolymer has a branched radial structure and is initially of a network structure. Accordingly, it is possible to further improve a crosslinking density of the final coating film upon UV curing of the composition, which may bring about further improvements in mechanical properties including abrasion resistance.
  • a weight- average molecular weight of the hyperbranched urethane acrylate prepolymer in accordance with the present invention may be preferably in a range of 1,000 to 4,000. If a weight-average molecular weight of the prepolymer is lower than 1,000, the hardness of the coating film may be excessively high. On the other hand, if a weight- average molecular weight of the prepolymer is higher than 4,000, a viscosity increases, and the coating film may be undesirably weakened because the hardness is too low when the final coating composition is cured.
  • the photo-curable coating composition according to the present invention may further comprise 10 to 150 parts by weight of any one selected from the group consisting of 1,6-hexanediol diacrylate, glycidyl (meth)acrylate, bisphenol A epoxy diacrylate, phosphate-terminated (meth)acrylate and a mixture thereof, based on 100 parts by weight of the hyperbranched urethane acrylate prepolymer.
  • 1,6-hexanediol diacrylate serves to reduce an amount of methyl- methacrylate to be used, while simultaneously eroding the basecoat during a coating process to thereby improve adhesive strength.
  • glycidyl (meth)acrylate or bisphenol A epoxy diacrylate may serve to improve the adhesive strength.
  • phosphate-terminated (meth)acrylate serves to improve adhesiveness with a metal surface via the action of phosphate groups.
  • a viscosity of the photo-curable coating composition at room temperature may be preferably in a range of 1.10 cP or less. If a viscosity of the composition is higher than 1.10 cP, this is not suitable for spray coating.
  • 2,2'-bis(hydroxymethyl)propionic acid prior to addition of hydroxy ethyl (me th) acrylate or hydroxypropyl (meth)acrylate. Due to having carboxyl groups, 2,2'-bis(hydroxymethyl)propionic acid further improves adhesiveness to the adherend, and serves as a chain extender to extend a chain length, thus increasing the mechanical strength of the film.
  • a method for preparing a photo-curable coating composition in accordance with the present invention comprises (a) reacting polycaprolactone triol having a weight- average molecular weight of 300 to 900 with isophorone diisocyanate to prepare a urethane oligomer; (b) reacting the urethane oligomer with hydroxyethyl (meth)acrylate or hydroxypropyl (meth) acrylate to prepare a hyperbranched urethane acrylate prepolymer; and (c) mixing the hyperbranched urethane acrylate prepolymer with 80 to 800 parts by weight of methylmethacrylate; 80 to 150 parts by weight of trimethylol propane triacrylate, dipentaerythritol penta/hexa acrylate or a mixture thereof; and 10 to 30 parts by weight of a photoinitiator, based on 100 parts by weight of the prepolymer.
  • An amount of isophorone diisocyanate used in Step (a) may be in a range of 2 to 3 mol, based on 1 mol of polycaprolactone triol, and an amount of hydroxyethyl (meth)acrylate or hydroxypropyl (meth) acrylate used in Step (b) may be in a range of 3 to 3.5 mol, based on 1 mol of polycaprolactone triol. If an amount of isophorone diisocyanate is lower than 2 mol, it is difficult to easily form a hyperbranched prepolymer.
  • isophorone diisocyanate may undesirably remain as side reaction impurities in the prepolymer as isocyanate groups of isophorone diisocyanate all react with hydroxyl groups of hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate which is added later, not with hydroxyl groups of polycaprolactone triol.
  • an amount of hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate is lower than 3 mol, unreacted isocyanate groups may remain due to insufficient end capping of isocyanate groups.
  • the reaction of Step (a) may be carried out at a temperature of about 8O 0 C to 100 0 C, for about 3 hours.
  • a catalyst such as dibutyl dilaurate may be used.
  • the reaction of Step (b) may be carried out at a temperature of about 5O 0 C to 7O 0 C for about 3 hours. Both reactions are carried out under nitrogen atmosphere.
  • a product which is prepared using the photo-curable coating composition in accordance with the present invention may be prepared by spray- applying the photo- curable coating composition to a substrate using a spray, followed by UV irradiation to cure the coating film.
  • a spray method There is no particular limit to the spray method.
  • spraying of the composition may be carried out by a spray gun equipped with an injection nozzle of 3 mm, using a 3/4 HP pump.
  • Hardness of the coating film formed by curing of the coating composition in accordance with the present invention may be preferably in a range of 5 to 9H. If hardness of the coating film is lower than 5H, the scratch resistance and abrasion resistance are not sufficient. On the other hand, if hardness of the coating film is higher than 9H, excessively high brittleness may cause disruption or cracking of the coating film.
  • photoinitiator there is no particular limit to the photoinitiator that can be used in the present invention, as long as it is conventionally used in the art.
  • An amount of the photoinitiator to be used may be in a range of 10 to 30 parts by weight, based on 100 parts by weight of the hyperbranched urethane acrylate prepolymer. If an amount of the photoinitiator is lower than 10 parts by weight, polymerization takes place at a slow rate. On the other hand, if an amount of the photoinitiator is higher than 30 parts by weight, this may result in deterioration of physical properties of the coating film.
  • the photo-curable coating composition in accordance with the present invention may further comprise conventional additives such as pigments, stabilizers, surfactants, fillers, e.g. metal microparticles, and UV-absorbers.
  • conventional additives such as pigments, stabilizers, surfactants, fillers, e.g. metal microparticles, and UV-absorbers.
  • bifunctional silicone acrylate may be added to improve the surface levelness of the coating film.
  • FIG. 1 is a graph showing an IR spectrum for the hyperbranched radial urethane acrylate prepolymer. Referring to FIG. 1, there is no peak at around 2270 cm , thus representing that all isocyanates took part in the reaction.
  • a photo-curable coating composition was prepared in the same manner as in
  • Example 1 except that 10 g of a hyperbranched radial urethane acrylate prepolymer obtained in Section 1-1 of Example l, 50 g of methylmethacrylate and 10 g of dipen- taerythritol penta/hexa acrylate were reacted.
  • a photo-curable coating composition was prepared in the same manner as in
  • Example 3 except that 10 g of a hyperbranched radial urethane acrylate prepolymer obtained in Example 3, 50 g of methylmethacrylate, 5 g of trimethylol propane triacrylate and 5 g of dipentaerythritol penta/hexa acrylate were reacted.
  • Test Example 1 Viscometry of coating compositions
  • the viscosity of coating compositions prepared in Examples 1 to 8 and Comparative Example 1 was measured using an Ostwald viscometer at 2O 0 C. The results obtained are given in Table 1 below.
  • Test Example 2 Heat resistance test [78] A coating composition prepared in Example 1 was applied to an ABS plate by a spray gun equipped with an injection nozzle of 3 mm using a 3/4 HP pump, and the coating film was photo-cured for about 10 sec by a mercury UV lamp (1400 mJ/cm , and irradiation distance of 15 cm). The thermogravimetric analysis was carried out. The results obtained are shown in FIG. 2. Referring to FIG. 2, it can be seen that the coating composition in accordance with the present invention has excellent thermal stability, because a temperature showing a rapid decrease of weight is 300 0 C or higher.
  • Test Example 3 Abrasion resistance test
  • Each of coating compositions prepared in Examples 1 to 8 was applied to a polycarbonate plate by a spray gun equipped with an injection nozzle of 3 mm using a 3/4 HP pump, and a coating composition of Comparative Example 1 was applied by doctor blade coating.
  • the coating films were photo-cured for about 10 sec by a mercury UV lamp (1400 mJ/cm , and irradiation distance of 15 cm). Wearability was then measured using RCA Abrasion Tester (Norman Tool Inc., USA). An abrasion of 50 cycles (33 strokes/min) with a 275 g load was used for each specimen.
  • the abrader was set in a standard cycle abrading mode and 11/16 inch wide paper (Tokyo Hi Max 11/16 inch x 33 cm). A specimen was regarded as passing the test when an underlying base of the coating surface was not exposed, whereas a specimen was regarded as failing to pass the test when an underlying base of the coating surface was exposed. The results obtained are given in Table 2 below.
  • Test Example 4 Hardness test (scratch resistance test) [83] Each of coating compositions prepared in Examples 1 to 8 was applied to a polycarbonate plate by a spray gun equipped with an injection nozzle of 3 mm using a 3/4 HP pump, and a coating composition of Comparative Example 1 was applied by doctor blade coating. The coating films were photo-cured for about 10 sec by a mercury UV lamp (1400 mJ/cm , and irradiation distance of 15 cm). A hardness test for the coating film was then carried out.
  • a pencil Mitsubishi Pencil Co., Ltd., Japan
  • a pencil was sharpened to expose a length of about 3 mm of a pencil lead and abraded vertically with circular motion on a sandpaper which was horizontally placed, such that a tip of the pencil lead was flat with a sharp angle.
  • the pencil was contacted at an angle of about 45 degrees on the coating surface.
  • a hardness tester ASTM D5178, Sunhayato Co., Ltd., Japan
  • the test was conducted in quintuplicate with changes of positions of specimens. Hardness of the pencil showing the occurrence of scratches in one or more out of 5 trials was taken as the hardness of the coating surface of interest. The results obtained are given in Table 3 below.
  • Test Example 5 Chemical resistance test
  • Each of coating compositions prepared in Examples 1 to 8 was applied to a polycarbonate plate by a spray gun equipped with an injection nozzle of 3 mm using a 3/4 HP pump, and a coating composition of Comparative Example 1 was applied by doctor blade coating.
  • the coating films were photo-cured for about 10 sec by a mercury UV lamp (1400 mJ/cm , and irradiation distance of 15 cm).
  • a printability tester KR-RCA-001, Korea QMS Corp., Korea
  • the tester was subjected to forward and backward moving while adding methanol (99.8%) to an extent that the coating surface is not dried completely. 250 cycles with 40 strokes/min were carried out to confirm a peeling state of the coating surface.
  • Each test included 10 coated plates. Plates showing exfoliation of the coating film were counted. The results obtained are given in Table 4 below.
  • Test Example 6 Yellowing test [89] Each of coating compositions prepared in Examples 1 to 8 was applied to a polycarbonate plate by a spray gun equipped with an injection nozzle of 3 mm using a 3/4 HP pump, and a coating composition of Comparative Example 1 was applied by doctor blade coating. The coating films were UV-irradiated for 10 min using a UV lamp and placed in a constant temperature and humidity chamber at 100 0 C and RH 80% for 24 hours. Yellowing of specimens before and after the test was examined with naked eyes. Each test included 10 coated plates. Plates showing yellowing of the coating film were counted. The results obtained are given in Table 5 below.
  • Test Example 7 Adhesive strength to polycarbonate (PC) (cross-cut test)
  • PC polycarbonate
  • FIG. 1 Adhesive strength to polycarbonate (PC) (cross-cut test)
  • FIG. 1 Each of coating compositions prepared in Examples 1 to 8 was applied to a polycarbonate plate by a spray gun equipped with an injection nozzle of 3 mm using a 3/4 HP pump, and a coating composition of Comparative Example 1 was applied by doctor blade coating.
  • the coating films were photo-cured for about 10 sec by a mercury UV lamp (1400 mJ/cm , and irradiation distance of 15 cm).
  • cross-cut squares of 1 mm x 1 mm were made on a surface of the coated specimen, using a cutting knife, and an OPP adhesive tape was applied thereto and strongly and vertically detached to thereby confirm a peeling state of the coating surface with naked eyes.
  • the average was applied to the evaluation according to the following standard:
  • Test Example 8 Adhesive strength to metal adherend (cross-cut test) [100] Each of coating compositions prepared in Examples 1 to 8 was applied to an aluminum sheet by a spray gun equipped with an injection nozzle of 3 mm using a 3/4 HP pump, and a coating composition of Comparative Example 1 was applied by doctor blade coating. The coating films were photo-cured for about 10 sec by a mercury UV lamp (1400 mJ/cm , and irradiation distance of 15 cm). Thereafter, cross-cut squares of 1 mm x 1 mm were made on a surface of the coated specimen, using a cutting knife, and an OPP adhesive tape was applied thereto and strongly and vertically detached to thereby confirm a peeling state of the coating surface with naked eyes. The average was applied to the evaluation according to the following standard:
  • the present invention provides a photo- curable coating composition which is free from environmental regulations due to no use of an organic solvent, and has superior working efficiency due to a low viscosity and consequent spray-coatability and high heat, abrasion, scratch, chemical and yellowing resistance. Therefore, the composition of the present invention can be widely used as a transparent coating material for a variety of substrates such as mobile phones.

Abstract

Provided is a photo-curable coating composition which can be widely used as a coating material for a variety of substrates. The coating composition comprises 80 to 800 parts by weight of methylmethacrylate, 80 to 150 parts by weight of trimethylol propane triacrylate or a dipentaerythritol penta/hexa acrylate mixture, and 10 to 30 parts by weight of a photoinitiator, based on 100 parts by weight of the hyperbranched urethane acrylate prepolymer. The coating composition of the present invention is free from environmental regulations due to no use of an organic solvent and has superior working efficiency due to a low viscosity resulting in spray-coatability and high heat, abrasion, scratch, chemical and yellowing resistance. Therefore, the composition of the present invention can be widely used as a coating material for a variety of substrates.

Description

Description
PHOTO-CURABLE COATING COMPOSITION COMPRISING HYPERBRANCHED STRUCTURE PREPOLYMER, METHOD FOR PREPARING THE SAME AND PRODUCT PREPARED BY
THE SAME Technical Field
[1] The present invention relates to a photo-curable coating composition. More specifically, the present invention relates to a photo-curable coating composition, which further improves physical properties of a film through the reaction of a hy- perbranched urethane acrylate prepolymer having high adhesiveness with acrylate having excellent physical properties, and has enhanced workability due to no need for a solvent, a method for preparing the same and a product prepared by the same method. Background Art
[2] The surface of plastic molded products, which are made of, for example, polycarbonate, polystyrene, styrene-acrylonitrile, polyester, acrylonitrile-butadiene-styrene, or the like, has disadvantages of inferior physicochemical properties such as low abrasion, scratch and solvent resistance, as compared to glass or metal products. For the purpose of remedying these problems and drawbacks, there have been attempted various methods, for example a method of applying a silicone or melamine resin to the plastic surface of interest, and a method of forming a protective film having a metallic texture through aluminum vacuum deposition. However, the silicone resin is a thermosetting material and therefore requires long-term heat exposure for formation of a coating film. Unfortunately, such long-term heating results in deterioration of productivity, and a high-process temperature may have adverse effects on physical properties of plastic substrates. Further, the aluminum vacuum deposition still suffers from problems associated with poor adhesion between the coating material and aluminum, which is likely to result in the risk of easy separability of the vapor- deposited film upon practical use of the product.
[3] In order to solve these problems, a method of forming a coating film has been proposed which includes coating a substrate with a solution of polyurethane in an organic solvent and evaporating the solvent. However, such a urethane coating poses many limitations in use due to poor adhesiveness and strength, and the risk of air pollution resulting from evaporation of volatile organic compounds (VOCs). As a great deal of attention has been directed to environmental concerns throughout the world, many countries have significantly strengthened regulations on emission and disposal of VOCs including organic solvents. For instance, US instituted or enacted various laws and regulations, for example California Rule 66 (1966) for prevention of photochemical smog, Clean Air Act (CAA, 1977) legislated by The Environmental Protection Agency (EPA), and Reasonably Available Control Technology (RACT) as a guide line for control of VOC emissions from coating operations. The Clean Air Act Amendments (CAA) of 1990 established a new approach for national emission standards of Hazardous Air Pollutants (HAPs), which regulates emission and disposal concentration of hazardous organic compounds depending upon kinds and classes of compounds. In order to cope with this trend, regulations and restrictions have been gradually strengthened for uses and applications of coating solutions that are required to use such organic solvents.
[4] Meanwhile, Korean Patent Application Publication No. 93-13027 Al discloses a
UV-curable coating composition for a vinyl chloride flooring material. However, the composition disclosed therein exhibits an excessively high viscosity of 300 to 5,000 cPs at 250C because it further incorporates a non-reactive oligomer which is a thermoplastic acrylic resin. As a result, this prior art has various problems, such as poor workability due to inapplicability of spray coating, poor mechanical properties such as low heat, abrasion and scratch resistance and low flexibility which are not suitable for a coating material of a vast variety of plastic molded products, and yellowing of urethanes due to generation of a quinone-imide structure upon exposure of aromatic urethane to UV irradiation, when aromatic diisocyanate is used.
[5] Korean Patent No. 139881 discloses a photo-curable resin composition comprising an aliphatic multifunctional isocyanate containing an isocyanurate ring of hex- amethylene diisocyanate, a prepolymer in the form of a reaction product of hydroxy alkyl (meth)acrylate with caprolactone-modified hydroxy ethyl acrylate, a reactive diluent, a photoinitiator and other additives. However, the above-mentioned photo- curable resin composition exhibits a high viscosity, so a spray coating method cannot be applied. Consequently, such a composition requires use of an organic solvent which, in turn, results in the problems of air pollution as mentioned above, and deterioration of process efficiency. Further, this prior art suffers from disadvantages associated with easy separability of a coating film from an adherend (or a target substrate to be coated) due to poor adhesive strength to the adherend, and other problems associated with insufficient mechanical properties, e.g. low heat, abrasion and scratch resistance and poor flexibility. Disclosure of Invention Technical Problem [6] Therefore, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a photo-curable coating composition which is spray-coatable due to a low viscosity despite a solvent-free type, and can be applied to various substrates including general-purpose plastic, due to excellent adhesive strength with an adherend, high abrasion, chemical and scratch resistance, and low risk of yellowing.
[7] It is another object of the present invention to provide a method for preparing the aforesaid photo-curable coating composition.
[8] It is yet another object of the present invention to provide a product which is prepared using the aforesaid photo-curable coating composition. Technical Solution
[9] In accordance with an aspect of the present invention, the above and other objects can be accomplished by the provision of a photo-curable coating composition, comprising:
[10] a hyperbranched ure thane acrylate prepolymer having repeating units of formula (I) radially bound in the molecular structure, through a urethane linkage between a hydroxyl group of polycaprolactone triol and an isocyanate group at one end of isophorone diisocyanate and a urethane linkage between an isocyanate group at the other end of isophorone diisocyanate and a hydroxyl group of polycaprolactone triol, hydroxyethyl (meth)acrylate or hydroxypropyl (meth)acrylate:
[H]
Figure imgf000005_0001
[12] (I)
[13] wherein:
[14] R is hydrogen or methyl;
[15] R is ethylene or propylene;
[16] each X is a residue other than hydrogen of a hydroxyl group in polycaprolactone triol, hydroxyethyl (meth)acrylate or hydroxypropyl (meth) aery late, and at least one of three X is a residue other than hydrogen of a hydroxyl group in polycaprolactone triol; and
[17] n is an integer of 1 to 5;
[18] methylmethacrylate (MMA);
[19] trimethylol propane triacrylate (TMPTA), dipentaerythritol penta/hexa aery late
(DPHA), or a mixture thereof; and [20] a photoinitiator.
[21] In accordance with another aspect of the present invention, there is provided a method for preparing a photo-curable coating composition, comprising: [22] (a) reacting polycaprolactone triol having a weight- average molecular weight of
300 to 900 with isophorone diisocyanate (IPDI) to prepare a urethane oligomer; [23] (b) reacting the urethane oligomer with hydroxyethyl (meth)acrylate or hy- droxypropyl (meth)acrylate to prepare a hyperbranched urethane acrylate prepolymer; and
[24] (c) mixing the hyperbranched urethane acrylate prepolymer with 80 to 800 parts by weight of methylmethacrylate; 80 to 150 parts by weight of trimethylol propane triacrylate, dipentaerythritol penta/hexa acrylate or a mixture thereof; and 10 to 30 parts by weight of a photoinitiator, based on 100 parts by weight of the prepolymer. Brief Description of the Drawings
[25] FIG. 1 is a graph showing an IR spectrum for a hyperbranched urethane acrylate prepolymer used in the present invention; and
[26] FIG. 2 is a graph showing the results of gravimetric analysis according to Example
1 of the present invention. Best Mode for Carrying Out the Invention
[27] Hereinafter, the present invention will be described in more detail.
[28] A photo-curable coating composition in accordance with the present invention is characterized by excellent heat resistance, abrasion resistance, scratch resistance and adhesion with an adherend, and superior working efficiency resulting from no risk of yellowing, spray-coatability due to a low viscosity and consequently no use of an organic solvent.
[29] As used herein, the term "hyperbranched prepolymer" refers to a polymer having repeating units of a dendritic structure extending from a core thereof. As the present invention employs the prepolymer having a hyperbranched structure, the prepolymer is already in a crosslinked form prior to photo-curing, whereby a crosslinking density is increased to thereby improve mechanical properties of the final coating film.
[30] Heat resistance of the photo-curable coating composition is attributable to the nature of polyol and diisocyanate used in the present invention. That is, poly- caprolactone triol used in the urethane acrylate prepolymer according to the present invention exhibits substantially no temperature-dependent changes in physical properties, unlike polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol or polycarbonate diol which is used in the preparation of conventional urethane acrylate prepolymers. Further, there is no occurrence of thermal stress or thermal shock due to no heat generation or absorption during the curing process. Isophorone diisocyanate used in the present invention exhibits excellent heat resistance and yellowing resistance, so it is possible to improve heat resistance and yellowing resistance of the final coating composition. Specifically, it is possible to prevent yellowing without addition of a UV absorber or antioxidant because use of isophorone diisocyanate causes no risk of formation of the quinone imide structure due to UV irradiation, unlike use of an aromatic diisocyanate compound. Further, cycloaliphatic di- isocyanate such as isophorone diisocyanate is advantageously superior in toughness and impact resistance.
[31] Further, the abrasion resistance and scratch resistance of a photo-curable coating composition in accordance with the present invention derives from properties of acrylate and a hyperbranched prepolymer used in the coating composition. That is, an increase in functional groups of acrylate to be used leads to increased hardness and improved mechanical properties of the coating film. The present invention employs tri- functional trimethylol propane triacrylate, penta- or hexa- functional dipentaerythritol penta/hexa acrylate or a mixture thereof, so a crosslinking degree of the final coating film increases to thereby enhance the hardness of the coating film. However, when the hardness is excessively high, brittleness of the film increases, and a viscosity of the composition prior to curing thereof is excessively high, so it is not suitable as a solvent-free sprayable coating material. Therefore, methylmethacrylate having excellent flexibility and elasticity is used together to offset such shortcomings. In the most preferred embodiment of the present invention, a mixture of trimethylol propane triacrylate and dipentaerythritol penta/hexa acrylate is used to thereby provide combination of optimum hardness and flexibility. Meanwhile, abrasion resistance and scratch resistance can be improved since a crosslinking density increases due to the crosslinked structure of the hyperbranched prepolymer, as described above.
[32] Polycaprolactone triol, which is polyol used in the present invention, contains large numbers of carbonyl groups in the molecular structure, thus providing high hy- drophilicity. Therefore, it is possible to improve adhesion with the adherend due to excellent adhesive strength and flexibility resulting from such high hydrophilicity. Further, the polycaprolactone triol contains both hydrophobic and hydrophilic units, so it is possible to easily blend the final coating composition with other polymer components.
[33] The photo-curable coating composition according to the present invention comprises 80 to 800 parts by weight of methylmethacrylate, 80 to 150 parts by weight of trimethylol propane triacrylate, dipentaerythritol penta/hexa acrylate or a mixture thereof, and 10 to 30 parts by weight of the photoinitiator, based on 100 parts by weight of the hyperbranched urethane acrylate prepolymer. Only when the composition has the above-specified component ratio, it is possible to achieve optimal mechanical properties including adhesive strength, flexibility and abrasion resistance while having a spray-coatable viscosity.
[34] Methylmethacrylate used in the present invention, as previously described above, serves to impart flexibility and elasticity to the final coating film, while simultaneously diluting the final coating composition to control a viscosity, which allows for spray coating using a spray. If a content of methylmethacrylate is lower than 80 parts by weight, based on 100 parts by weight of the hyperbranched ure thane acrylate prepolymer, a viscosity is excessively high, which is not suitable for spray coating. On the other hand, if a content of methylmethacrylate is higher than 800 parts by weight, the hardness of the final coating film may be deteriorated. More preferably, the content of methylmethacrylate is in a range of 200 to 800 parts by weight. Occasionally, there is a need to reduce an amount of methylmethacrylate to be used because it gives off unpleasant odor under working conditions. If a content of methylmethacrylate is lower than 200 parts by weight, 1,6-hexanediol diacrylate may be additionally used to control a viscosity of the composition.
[35] Further, if a content of trimethylol propane triacrylate, dipentaerythritol penta/hexa acrylate or a mixture thereof is lower than 80 parts by weight, this may result in decreased hardness of the final coating film. On the other hand, a content of the compound exceeding 150 parts by weight may lead to deterioration in flexibility of the final coating film.
[36] A weight- average molecular weight of polycaprolactone triol used in the present invention may be preferably in a range of 300 to 900. If the weight-average molecular weight of the compound is lower than 300, excessively high hardness may result in brittleness of the coating film. On the other hand, if the weight-average molecular weight of the compound is higher than 900, a viscosity increases, and the coating film may be undesirably weakened because the hardness is too low when the final coating composition is cured.
[37] When polycaprolactone triol is used according to the present invention, the hyperbranched urethane acrylate prepolymer has a branched radial structure and is initially of a network structure. Accordingly, it is possible to further improve a crosslinking density of the final coating film upon UV curing of the composition, which may bring about further improvements in mechanical properties including abrasion resistance.
[38] A weight- average molecular weight of the hyperbranched urethane acrylate prepolymer in accordance with the present invention may be preferably in a range of 1,000 to 4,000. If a weight-average molecular weight of the prepolymer is lower than 1,000, the hardness of the coating film may be excessively high. On the other hand, if a weight- average molecular weight of the prepolymer is higher than 4,000, a viscosity increases, and the coating film may be undesirably weakened because the hardness is too low when the final coating composition is cured.
[39] The photo-curable coating composition according to the present invention may further comprise 10 to 150 parts by weight of any one selected from the group consisting of 1,6-hexanediol diacrylate, glycidyl (meth)acrylate, bisphenol A epoxy diacrylate, phosphate-terminated (meth)acrylate and a mixture thereof, based on 100 parts by weight of the hyperbranched urethane acrylate prepolymer. 1,6-hexanediol diacrylate, as previously described above, serves to reduce an amount of methyl- methacrylate to be used, while simultaneously eroding the basecoat during a coating process to thereby improve adhesive strength. Due to having epoxy groups, glycidyl (meth)acrylate or bisphenol A epoxy diacrylate may serve to improve the adhesive strength. Further, phosphate-terminated (meth)acrylate serves to improve adhesiveness with a metal surface via the action of phosphate groups.
[40] A viscosity of the photo-curable coating composition at room temperature may be preferably in a range of 1.10 cP or less. If a viscosity of the composition is higher than 1.10 cP, this is not suitable for spray coating.
[41] Upon preparation of the hyperbranched urethane acrylate prepolymer, mechanical properties and adhesiveness may be further improved by adding
2,2'-bis(hydroxymethyl)propionic acid prior to addition of hydroxy ethyl (me th) acrylate or hydroxypropyl (meth)acrylate. Due to having carboxyl groups, 2,2'-bis(hydroxymethyl)propionic acid further improves adhesiveness to the adherend, and serves as a chain extender to extend a chain length, thus increasing the mechanical strength of the film.
[42] A method for preparing a photo-curable coating composition in accordance with the present invention comprises (a) reacting polycaprolactone triol having a weight- average molecular weight of 300 to 900 with isophorone diisocyanate to prepare a urethane oligomer; (b) reacting the urethane oligomer with hydroxyethyl (meth)acrylate or hydroxypropyl (meth) acrylate to prepare a hyperbranched urethane acrylate prepolymer; and (c) mixing the hyperbranched urethane acrylate prepolymer with 80 to 800 parts by weight of methylmethacrylate; 80 to 150 parts by weight of trimethylol propane triacrylate, dipentaerythritol penta/hexa acrylate or a mixture thereof; and 10 to 30 parts by weight of a photoinitiator, based on 100 parts by weight of the prepolymer.
[43] An amount of isophorone diisocyanate used in Step (a) may be in a range of 2 to 3 mol, based on 1 mol of polycaprolactone triol, and an amount of hydroxyethyl (meth)acrylate or hydroxypropyl (meth) acrylate used in Step (b) may be in a range of 3 to 3.5 mol, based on 1 mol of polycaprolactone triol. If an amount of isophorone diisocyanate is lower than 2 mol, it is difficult to easily form a hyperbranched prepolymer. On the other hand, if an amount of isophorone diisocyanate is higher than 3 mol, isophorone diisocyanate may undesirably remain as side reaction impurities in the prepolymer as isocyanate groups of isophorone diisocyanate all react with hydroxyl groups of hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate which is added later, not with hydroxyl groups of polycaprolactone triol. On the other hand, if an amount of hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate is lower than 3 mol, unreacted isocyanate groups may remain due to insufficient end capping of isocyanate groups. On the other hand, if an amount of the compound is higher than 3.5 mol, this may result in a side reaction where an excessive amount of the compound will react with two isocyanate groups present at both ends of the unreacted isophorone diisocyanate, or otherwise may cause formation of unreacted residual material in the hyperbranched prepolymer.
[44] The reaction of Step (a) may be carried out at a temperature of about 8O0C to 1000C, for about 3 hours. For reaction activity, a catalyst such as dibutyl dilaurate may be used. The reaction of Step (b) may be carried out at a temperature of about 5O0C to 7O0C for about 3 hours. Both reactions are carried out under nitrogen atmosphere.
[45] A product which is prepared using the photo-curable coating composition in accordance with the present invention may be prepared by spray- applying the photo- curable coating composition to a substrate using a spray, followed by UV irradiation to cure the coating film. There is no particular limit to the spray method. For example, spraying of the composition may be carried out by a spray gun equipped with an injection nozzle of 3 mm, using a 3/4 HP pump.
[46] Hardness of the coating film formed by curing of the coating composition in accordance with the present invention may be preferably in a range of 5 to 9H. If hardness of the coating film is lower than 5H, the scratch resistance and abrasion resistance are not sufficient. On the other hand, if hardness of the coating film is higher than 9H, excessively high brittleness may cause disruption or cracking of the coating film.
[47] There is no particular limit to the photoinitiator that can be used in the present invention, as long as it is conventionally used in the art. For example, mention may be made of hydroxy cyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyl, acetophenone, benzophenone, and phenyl-2-hydroxy-2-propyl ketone. An amount of the photoinitiator to be used may be in a range of 10 to 30 parts by weight, based on 100 parts by weight of the hyperbranched urethane acrylate prepolymer. If an amount of the photoinitiator is lower than 10 parts by weight, polymerization takes place at a slow rate. On the other hand, if an amount of the photoinitiator is higher than 30 parts by weight, this may result in deterioration of physical properties of the coating film.
[48] The photo-curable coating composition in accordance with the present invention may further comprise conventional additives such as pigments, stabilizers, surfactants, fillers, e.g. metal microparticles, and UV-absorbers. For example, bifunctional silicone acrylate may be added to improve the surface levelness of the coating film. Mode for the Invention
[49] EXAMPLES [50] Now, the present invention will be described in more detail with reference to the following Examples. These examples are provided only for illustrating the present invention and should not be construed as limiting the scope and spirit of the present invention.
[51] Example 1
[52] 1 - 1. Preparation of hyperbranched radial urethane acrylate prepolymer
[53] 0.01 mol of polycaprolactone triol having a weight- average molecular weight of
900 (manufactured by Aldrich) and 0.025 mol of isophorone diisocyanate (manufactured by Aldrich) were added to a flask and mixed in an oil bath at 8O0C for 1 hour. Then, the resulting solution was cooled to 6O0C, and 0.03 mol of hydroxyethyl methacrylate was added thereto, followed by reaction for 1 hour. 1 or 2 drops of dibutyltin dilaurate as a catalyst were added to the solution and the mixture was reacted for another 1 hour to afford a hyperbranched radial urethane acrylate prepolymer having a weight- average molecular weight of 3,000.
[54] FT-IR: 3000 cm"1 (N-H stretching), 1720 cm"1 (C=O stretching), and 1530 cm"1
(C-NH stretching in urethane)
[55] FIG. 1 is a graph showing an IR spectrum for the hyperbranched radial urethane acrylate prepolymer. Referring to FIG. 1, there is no peak at around 2270 cm , thus representing that all isocyanates took part in the reaction.
[56] 1-2. Preparation of photo-curable coating composition
[57] 10 g of the hyperbranched radial urethane acrylate prepolymer obtained in Section
1-1 was introduced in an Erlenmeyer flask to which 30 g of methylmethacrylate (manufactured by Aldrich) and 10 g of trimethylol propane triacrylate (manufactured by Aldrich) were then added, followed by mixing at 6O0C for 60 min. Finally, 1 -hydroxy cyclohexyl phenyl ketone was added as 3% by weight of the total weight to prepare a photo-curable coating composition.
[58] Example 2
[59] A photo-curable coating composition was prepared in the same manner as in
Example 1, except that 10 g of a hyperbranched radial urethane acrylate prepolymer obtained in Section 1-1 of Example l, 50 g of methylmethacrylate and 10 g of dipen- taerythritol penta/hexa acrylate were reacted.
[60] Example 3
[61] In order to improve mechanical properties and adhesiveness prior to introduction of hydroxyethyl methacrylate in Section 1-1 of Example 1, 0.2 g of 2,2'-bis(hydroxymethyl)propionic acid was added, followed by reaction for 1 hour, and 0.03 mol of hydroxy ethyl methacrylate was then added, followed by reaction for another 1 hour. 10 g of the resulting hyperbranched radial urethane acrylate prepolymer and 30 g of methylmethacrylate were mixed, and then 10 g of trimethylol propane triacrylate was added thereto, followed by mixing at 6O0C for 60 min. Finally, 1 -hydroxy cyclohexyl phenyl ketone was added as 3% by weight of the total weight to prepare a photo-curable coating composition.
[62] Example 4
[63] A photo-curable coating composition was prepared in the same manner as in
Example 3, except that 10 g of a hyperbranched radial urethane acrylate prepolymer obtained in Example 3, 50 g of methylmethacrylate, 5 g of trimethylol propane triacrylate and 5 g of dipentaerythritol penta/hexa acrylate were reacted.
[64] Example 5
[65] In order to improve adhesiveness, 10 g of the hyperbranched radial urethane acrylate prepolymer obtained in Section 1-1 of Example 1, 8 g of dipentaerythritol penta/hexa acrylate, 35 g of methylmethacrylate and 5 g (20%) of bisphenol A epoxy diacrylate/l,6-hexanediol diacrylate were added and mixed at 6O0C for 60 min. Finally, 1 -hydroxy cyclohexyl phenyl ketone was added as 3% by weight of the total weight to prepare a photo-curable coating composition.
[66] Example 6
[67] In order to improve adhesiveness, 10 g of the hyperbranched radial urethane acrylate prepolymer obtained in Section 1-1 of Example l, 10 g of dipentaerythritol penta/hexa acrylate, 50 g of methylmethacrylate, and 10 g of glycidyl methacrylate were added and mixed at 6O0C for 60 min. Finally, 5 g of methylphenylglyoxalate/ hydroxy phenylpropan-1-one as a photoinitiator was added to prepare a photo-curable coating composition.
[68] Example 7
[69] In order to improve adhesiveness and reduce malodor caused by methylmethacrylate, 10 g of the hyperbranched radial urethane acrylate prepolymer obtained in Section 1-1 of Example l, 10 g of dipentaerythritol penta/hexa acrylate, 8 g of methylmethacrylate, 15 g of trimethylol propane triacrylate, 15 g of 1,6-hexanediol diacrylate, 1O g of glycidyl methacrylate and 0.1 of bifunctional silicone acrylate to improve the surface levelness were added and mixed at 6O0C for 60 min. Finally, 1 -hydroxy cyclohexyl phenyl ketone was added as 3% by weight of the total weight to prepare a photo-curable coating composition.
[70] Example 8
[71] In order to improve adhesiveness with metal, 10 g of the hyperbranched radial urethane acrylate prepolymer obtained in Section 1-1 of Example 1, 10 g of dipentaerythritol penta/hexa acrylate, 25 g of methylmethacrylate, 15 g of trimethylol propane triacrylate and 20 g of phosphate-terminated methacrylate were added and mixed at 6O0C for 60 min. Finally, 1 -hydroxy cyclohexyl phenyl ketone was added as 3% by weight of the total weight to prepare a photo-curable coating composition. [72] Comparative Example 1 [73] 40 parts of urethane acrylate produced by reacting 1 mol of 2,4-toluene diisocyanate with 0.3 mol of polyester polyol (a condensation product of adipic acid and neopentyl glycol), 0.2 mol of polytetrahydrofuran (weight- average molecular weight: 650) and 1 mol of 2-hydroxyethyl acrylate; 10 parts of a non-reactive oligomer produced by reacting 620 parts of methylmethacrylate, 7 parts of methyl acrylate, 50 parts of butyl acrylate and 100 parts of polypropylene glycol monoacrylate in the presence of methyl isobutyl ketone using benzyl peroxide as a catalyst; 10 parts of 1,6-hexanediol diacrylate, 10 parts of 2-ethyl hexyl acrylate, 25 parts of N-vinyl-2-pyrrolidone, 2.5 parts of benzophenone, 2 parts of 1 -hydroxy cyclohexyl phenyl ketone, and 0.5 parts of silicone polyacrylate (Ebecryl 360, available from UCB) were stirred at 4O0C to prepare a photo-curable coating composition.
[74] Test Example 1 : Viscometry of coating compositions [75] The viscosity of coating compositions prepared in Examples 1 to 8 and Comparative Example 1 was measured using an Ostwald viscometer at 2O0C. The results obtained are given in Table 1 below.
[76] Table 1
Figure imgf000013_0001
[77] Test Example 2: Heat resistance test [78] A coating composition prepared in Example 1 was applied to an ABS plate by a spray gun equipped with an injection nozzle of 3 mm using a 3/4 HP pump, and the coating film was photo-cured for about 10 sec by a mercury UV lamp (1400 mJ/cm , and irradiation distance of 15 cm). The thermogravimetric analysis was carried out. The results obtained are shown in FIG. 2. Referring to FIG. 2, it can be seen that the coating composition in accordance with the present invention has excellent thermal stability, because a temperature showing a rapid decrease of weight is 3000C or higher.
[79] Test Example 3: Abrasion resistance test [80] Each of coating compositions prepared in Examples 1 to 8 was applied to a polycarbonate plate by a spray gun equipped with an injection nozzle of 3 mm using a 3/4 HP pump, and a coating composition of Comparative Example 1 was applied by doctor blade coating. The coating films were photo-cured for about 10 sec by a mercury UV lamp (1400 mJ/cm , and irradiation distance of 15 cm). Wearability was then measured using RCA Abrasion Tester (Norman Tool Inc., USA). An abrasion of 50 cycles (33 strokes/min) with a 275 g load was used for each specimen. The abrader was set in a standard cycle abrading mode and 11/16 inch wide paper (Tokyo Hi Max 11/16 inch x 33 cm). A specimen was regarded as passing the test when an underlying base of the coating surface was not exposed, whereas a specimen was regarded as failing to pass the test when an underlying base of the coating surface was exposed. The results obtained are given in Table 2 below.
[81] Table 2
Figure imgf000014_0001
[82] Test Example 4: Hardness test (scratch resistance test) [83] Each of coating compositions prepared in Examples 1 to 8 was applied to a polycarbonate plate by a spray gun equipped with an injection nozzle of 3 mm using a 3/4 HP pump, and a coating composition of Comparative Example 1 was applied by doctor blade coating. The coating films were photo-cured for about 10 sec by a mercury UV lamp (1400 mJ/cm , and irradiation distance of 15 cm). A hardness test for the coating film was then carried out. For this purpose, a pencil (Mitsubishi Pencil Co., Ltd., Japan) was sharpened to expose a length of about 3 mm of a pencil lead and abraded vertically with circular motion on a sandpaper which was horizontally placed, such that a tip of the pencil lead was flat with a sharp angle. The pencil was contacted at an angle of about 45 degrees on the coating surface. Then, a hardness tester (ASTM D5178, Sunhayato Co., Ltd., Japan) was set parallel to the coating surface and then allowed to move forward about 10 mm. The test was conducted in quintuplicate with changes of positions of specimens. Hardness of the pencil showing the occurrence of scratches in one or more out of 5 trials was taken as the hardness of the coating surface of interest. The results obtained are given in Table 3 below.
[84] Table 3
Figure imgf000014_0002
Figure imgf000015_0001
[85] Test Example 5: Chemical resistance test [86] Each of coating compositions prepared in Examples 1 to 8 was applied to a polycarbonate plate by a spray gun equipped with an injection nozzle of 3 mm using a 3/4 HP pump, and a coating composition of Comparative Example 1 was applied by doctor blade coating. The coating films were photo-cured for about 10 sec by a mercury UV lamp (1400 mJ/cm , and irradiation distance of 15 cm). A printability tester (KR-RCA-001, Korea QMS Corp., Korea) was equipped with a pencil rubber eraser which was then contacted with a 500 g load on the coating surface. The tester was subjected to forward and backward moving while adding methanol (99.8%) to an extent that the coating surface is not dried completely. 250 cycles with 40 strokes/min were carried out to confirm a peeling state of the coating surface. Each test included 10 coated plates. Plates showing exfoliation of the coating film were counted. The results obtained are given in Table 4 below.
[87] Table 4
Figure imgf000015_0002
[88] Test Example 6: Yellowing test [89] Each of coating compositions prepared in Examples 1 to 8 was applied to a polycarbonate plate by a spray gun equipped with an injection nozzle of 3 mm using a 3/4 HP pump, and a coating composition of Comparative Example 1 was applied by doctor blade coating. The coating films were UV-irradiated for 10 min using a UV lamp and placed in a constant temperature and humidity chamber at 1000C and RH 80% for 24 hours. Yellowing of specimens before and after the test was examined with naked eyes. Each test included 10 coated plates. Plates showing yellowing of the coating film were counted. The results obtained are given in Table 5 below.
[90] Table 5
Figure imgf000015_0003
Figure imgf000016_0001
[91] Test Example 7: Adhesive strength to polycarbonate (PC) (cross-cut test) [92] Each of coating compositions prepared in Examples 1 to 8 was applied to a polycarbonate plate by a spray gun equipped with an injection nozzle of 3 mm using a 3/4 HP pump, and a coating composition of Comparative Example 1 was applied by doctor blade coating. The coating films were photo-cured for about 10 sec by a mercury UV lamp (1400 mJ/cm , and irradiation distance of 15 cm). Thereafter, cross-cut squares of 1 mm x 1 mm were made on a surface of the coated specimen, using a cutting knife, and an OPP adhesive tape was applied thereto and strongly and vertically detached to thereby confirm a peeling state of the coating surface with naked eyes. The average was applied to the evaluation according to the following standard:
[93] O: No cross-cut squares peeled off. [94] Δ: Cross-cut squares remaining unpeeled were 2/3 or more. [95] X: Cross-cut squares remaining unpeeled were less than 2/3. [96] The results obtained are given in Table 6 below. [97] Table 6
Figure imgf000016_0002
[98] Referring to FIG. 6, it was confirmed that the coating composition in accordance with the present invention exhibits very excellent adhesive strength to a polycarbonate adherend.
[99] Test Example 8: Adhesive strength to metal adherend (cross-cut test) [100] Each of coating compositions prepared in Examples 1 to 8 was applied to an aluminum sheet by a spray gun equipped with an injection nozzle of 3 mm using a 3/4 HP pump, and a coating composition of Comparative Example 1 was applied by doctor blade coating. The coating films were photo-cured for about 10 sec by a mercury UV lamp (1400 mJ/cm , and irradiation distance of 15 cm). Thereafter, cross-cut squares of 1 mm x 1 mm were made on a surface of the coated specimen, using a cutting knife, and an OPP adhesive tape was applied thereto and strongly and vertically detached to thereby confirm a peeling state of the coating surface with naked eyes. The average was applied to the evaluation according to the following standard:
[101] ©: No cross-cut squares peeled off. [102] O: Cross-cut squares remaining unpeeled were 4/5 or more. [103] Δ: Cross-cut squares remaining unpeeled were 2/3 or more. [104] X: Cross-cut squares remaining unpeeled were less than 2/3. [105] The results obtained are given in Table 7 below. [106] Table 7
Figure imgf000017_0001
Industrial Applicability
[107] As apparent from the above description, the present invention provides a photo- curable coating composition which is free from environmental regulations due to no use of an organic solvent, and has superior working efficiency due to a low viscosity and consequent spray-coatability and high heat, abrasion, scratch, chemical and yellowing resistance. Therefore, the composition of the present invention can be widely used as a transparent coating material for a variety of substrates such as mobile phones.

Claims

Claims
[1] A photo-curable coating composition comprising: a hyperbranched urethane acrylate prepolymer having repeating units of formula (I) radially bound in the molecular structure, through a urethane linkage between a hydroxyl group of polycaprolactone triol with an isocyanate group at one end of isophorone diisocyanate and a urethane linkage between an isocyanate group at the other end of isophorone diisocyanate with a hydroxyl group of polycaprolactone triol, hydroxyethyl (meth)acrylate or hydroxypropyl (meth)acrylate:
Figure imgf000018_0001
(I) wherein:
R is hydrogen or methyl; R is ethylene or propylene; each X is a residue other than hydrogen of a hydroxyl group in polycaprolactone triol, hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate, and at least one of three X is a residue other than hydrogen of a hydroxyl group in polycaprolactone triol; and n is an integer of 1 to 5; methylmethacrylate ; trimethylol propane triacrylate, dipentaerythritol penta/hexa acrylate, or a mixture thereof; and a photoinitiator.
[2] The composition according to claim 1, wherein the composition comprises 80 to
800 parts by weight of methylmethacrylate, 80 to 150 parts by weight of trimethylol propane triacrylate, dipentaerythritol penta/hexa acrylate or a mixture thereof, and 10 to 30 parts by weight of the photoinitiator, based on 100 parts by weight of the hyperbranched urethane acrylate prepolymer.
[3] The composition according to claim 1, wherein the composition further comprises 10 to 150 parts by weight of any one selected from the group consisting of 1,6-hexanediol diacrylate, glycidyl (meth)acrylate, bisphenol A epoxy diacrylate, phosphate-terminated (me th) acrylate and a mixture thereof, based on 100 parts by weight of the hyperbranched urethane acrylate prepolymer.
[4] The composition according to claim 1, wherein the polycaprolactone triol has a weight- average molecular weight of 300 to 900.
[5] The composition according to claim 1, wherein the hyperbranched urethane acrylate prepolymer has a weight- average molecular weight of 1000 to 4000, and a viscosity of the photo-curable coating composition at room temperature is in the range of 1.02 to 1.10 cP.
[6] A method for preparing a photo-curable coating composition, comprising:
(a) reacting polycaprolactone triol having a weight-average molecular weight of 300 to 900 with isophorone diisocyanate to prepare a urethane oligomer;
(b) reacting the urethane oligomer with hydroxyethyl (meth)acrylate or hy- droxypropyl (meth)acrylate to prepare a hyperbranched urethane acrylate prepolymer; and
(c) mixing the hyperbranched urethane acrylate prepolymer with 80 to 800 parts by weight of methylmethacrylate; 80 to 150 parts by weight of trimethylol propane triacrylate, dipentaerythritol penta/hexa acrylate or a mixture thereof; and 10 to 30 parts by weight of a photoinitiator, based on 100 parts by weight of the prepolymer.
[7] The method according to claim 6, wherein the amount of isophorone diisocyanate used in Step (a) is in the range of 2 to 3 mol, based on 1 mol of polycaprolactone triol, and an amount of hydroxyethyl (meth) acrylate or hy- droxypropyl (meth)acrylate used in Step (b) is in the range of 3 to 3.5 mol, based on 1 mol of polycaprolactone triol.
[8] The method according to claim 6, further comprising adding
2,2'-bis(hydroxymethyl)propionic acid prior to Step (b).
[9] A product which is prepared by applying the coating composition of any one of claims 1 to 5 to a surface of the product and curing the resulting coating film with UV irradiation.
[10] The product according to claim 9, wherein hardness of the coating film is in the range of 6 to 9H.
PCT/KR2006/005578 2006-12-19 2006-12-19 Photo-curable coating composition comprising hyperbranched structure prepolymer, method for preparing the same and product prepared by the same WO2008075806A1 (en)

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