KR100845403B1 - Manufacturing method for organic-inorganic hybrid coating solution for ambient thermal polymerization - Google Patents

Abstract

An organic/inorganic hybrid coating agent is provided to improve transparency upon hybridization, to impart improved wear resistance, chemical resistance and interfacial adhesion to a coating layer, and to prevent generation of scratches on a surface coated with the coating agent. An organic/inorganic hybrid coating agent comprises: an acrylic polymer resin; 1-30 wt% of an alcohol solvent for the acrylic polymer based on the weight of the acrylic polymer resin, the alcohol solvent being selected from methanol, ethanol, butanol, isobutanol, propanol, isopropanol and a mixture thereof; 5-35 wt% of at least one sol-gel ceramic precursor selected from the group consisting of tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrakis(2-hydroxyethyl) orthosilicate, lithium orthosilicate, cesium aluminum orthosilicate, tetrabutyl orthosilicate, aluminum sec-butoxide, aluminum tributoxide, aluminum ethoxide, diethyl aluminum ethoxide, aluminum isopropoxide, aluminum tert-butoxide, aluminum nitrate anhydride, aluminum nitrate nonahydrate, aluminum nitrate enneahydrate, aluminum phenoxide, zirconium acetylacetonate, zirconium bis(diethylcitrato) dipropoxide, zirconium tert-butoxide, zirconium ethoxide, zirconium isopropoxide, zirconium trifluoroacetyl acetonate, zirconium tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionate), zirconium diisopropoxide bis(2,2,6,6-tetramethyl-3,5-heptanedionate), zirconium chloride, titanium bis(ethyl acetoacetato) diisopropoxide, titanium butoxide, titanium tert-butoxide, titanium chloride, titanium diisopropoxide bis(acetylacetonate), titanium diisopropoxide bis(2,2,6,6-tetramethyl-3,5-heptanedionate), titanium ethoxide, titanium 2-ethyl-1,3-hexanediolate, titanium 2-ethylhexyloxide, titanium isopropoxide, titanium methoxide, titanium nitrate, titanium oxide acetylacetonate, titanium propoxide, titanium (triethanolaminato) isopropoxide; distilled water for hydrolyzing the sol-gel inorganic ceramic precursor, added in an amount of 4-10 molar times of the sol-gel inorganic ceramic precursor; 0.5-5 wt% of a cationic, anionic or non-ionic surfactant based on the total weight of the above components, or at least one binder selected from silane-, silazane- and siloxane-based binders and added in an amount of 0.5-20 wt% based on the total weight of the above components; and 0.1-5 wt% of ceramic nanoparticles based on the total weight of the coating agent.

Description

Organic / inorganic hybrid coatings, manufacturing method and thermosetting method {Manufacturing method for organic-inorganic hybrid coating solution for ambient thermal polymerization}

1 is a schematic diagram of the chemical structure of an organic / inorganic hybrid coating agent according to the present invention.

Figure 2 is a graph showing the hardness of the coating layer using an organic / inorganic hybrid coating prepared according to the present invention.

Figure 3 is a photograph showing the indentation traces of the diamond indenter of the conventional UV polymerization coating layer (A; Vickers hardness 131 MPa) and the coating layer of the present invention at 50 times the ratio, respectively.

4 is a graph showing the Vickers hardness and peeling characteristics of the coating layer using the coating agent of the present invention.

5 is a graph showing the Vickers hardness according to the polymerization temperature and polymerization time of the coating agent of the present invention.

6 is a photo (C) artificially formed wrinkles on the coating layer immediately after the coating when the organic / inorganic hybrid coating agent of the present invention is spray-coated on a plastic substrate, and the photo (D) showing the leveling state of the coating layer after 5 minutes , After curing it at 75 ° C. for 1 hour, photographs (E) showing surface gloss were magnified 1.5 times, respectively.

Figure 7 is a photograph enlarged twice the appearance after the x-cut test of the coating layer using the organic / inorganic hybrid coating of the present invention.

8 is a view showing the results of measuring the surface roughness of the organic / inorganic hybrid coating agent coating layer of the present invention.

Figure 9 is an enlarged photograph 1500 times by observing the cross section of the coating layer of the organic / inorganic hybrid coating of the present invention by a scanning electron microscope.

The present invention relates to an organic / inorganic hybrid coating agent capable of thermal polymerization in air, a method of manufacturing the same, and a heat curing method, and more particularly, to provide a coating material that can be cured simply by thermal polymerization in air, thereby providing excellent wear resistance coating properties. The present invention relates to an organic / inorganic hybrid coating agent capable of thermal polymerization in air, a method for preparing the same, and a thermosetting method.

Currently, acrylic polymer coatings for surface protection are widely applied in various fields such as mobile phone cases, digital cameras, notebook cases, automobile exteriors, automotive parts, LCD protective parts, and printing fields.

Particularly, in case of mobile phone case, the top coat is applied after paint coating. Most of them use UV polymerization technology, but the existing acrylic polymer coating alone cannot significantly improve the wear resistance. A lot of scratches occur, and there is a limit in the interfacial bonding strength of the coating layer, which shows a limit in durability as a coating for hard coating.

In addition, due to the recent strengthening of environmental regulations at home and abroad, UV coating and polymerization methods have been considerably restricted in the coating coating field due to restrictions on the use of UV and restrictions on the use of harmful solvents such as xylene, toluene and benzene in UV coating solutions. The trend is changing to hydrophilic coatings in this field. In addition, surface wear resistance, chemical resistance, interfacial bonding strength and the like has emerged as a problem is demanding quality that can withstand more harsh environments.

Accordingly, various coating equipment manufacturers including domestic mobile phone case manufacturers are increasing the demand for coating technology and coating solution to replace UV polymerization while preparing for UV related environmental regulations of polymer coating, and at the same time, high price due to UV polymerization of polymer material The company is looking for ways to reduce the cost by replacing the device and the high maintenance cost. Along with such cost reduction measures, efforts to further improve quality in terms of wear resistance and interfacial bonding strength of the coating layer are urgently required.

Among the methods developed and used according to these requirements, the conventional radical polymerization process is required to polymerize in a vacuum or nitrogen atmosphere, so it is not suitable for mass production, and sputtering and anodizing are not suitable for mass production but are not suitable for mass production. There are disadvantages.

An object of the present invention for solving the above problems is composed of inorganic ceramics as the main component to the organic acrylic polymer, by adding a surfactant or a binder to transparently hybridize the organic and inorganic components and to add the ceramic nanoparticles coating layer Significantly improves the wear resistance, chemical resistance and interfacial bonding strength of the coating, and enables hard film formation by thermal polymerization in air after coating. To replace it at its source.

The coating agent of the present invention for achieving the above object is connected to the acrylic polymer resin, the sol-gel inorganic ceramic precursor added to the weight of the acrylic polymer resin, the organic acrylic polymer resin and the inorganic ceramic added to each other Surfactant or a binder, and ceramic nanoparticles added at 0.1 to 5% by weight based on the total weight.

In addition, the method for producing the paint is 1 to 30% by weight based on the acrylic polymer resin and at least one selected from the group consisting of epoxy, urethane, silicone, polyester, polyether, polyethylene and melamine. Preparing a polymer solution for stirring at least one alcohol solvent selected from% methanol, ethanol, butanol, isobutanol, propanol, and isopropanol; A ceramic hydrolysis step of adding an inorganic ceramic to 5-35 wt% based on the weight of the acrylic polymer resin, and adding and stirring distilled water corresponding to 4-10 times the number of moles to the inorganic ceramic; 0.5-5% by weight of cationic, anionic, or nonionic surfactant or silane, silazane, or siloxane based on the total weight of the polymer solution and the ceramic hydrolysis solution. Preparing a hybrid solution by adding one or both binders added in an amount of 0.5 to 20% by weight based on the total weight of the hydrolysis solution; It is to form a coating agent comprising adding 0.1 to 5% by weight of the ceramic nanoparticles, such as silica, alumina, zirconia and the like to the hybrid solution to the total weight of the hybrid solution.

In the above-described configuration, in the polymer solution preparation step, the acrylic monomer is further stirred by 5-30% by weight based on the acrylic polymer resin, and in the hydrolysis step, ethanol is further added to the inorganic ceramic in a 2-10-fold molar number.

In addition, 0.1 to 5% by weight of a polymerization initiator is added to the coating agent, and 0.1 to 2% by weight of a coating additive, that is, a leveling agent, is further added and stirred.

On the other hand, the thermosetting method of the paint according to the present invention by adding 0.5 to 5% by weight of the polymerization initiator and 0.1 to 2% by weight of the leveling agent to the coating agent configured as described above to inert air or nitrogen, argon, etc. It is spray-coated on metal, plastic and ceramic base materials in a gas atmosphere and thermally polymerized at 60-90 ° C for 30 minutes to 4 hours.

In the above-described configuration, the acrylic polymer resin is one or more resins selected from epoxy, urethane, silicone, polyester, polyether, polyethylene, melamine, and the like. Epoxy Resin, Epoxy Methadiacrylate, Poly (bisphenol A-co-epichlorohydrin) based on Epoxy Resin, Bisphenol A Diglycidyl ether of bisphenol A-based epoxy resins, epoxyacrylate oligomers, phenol-urethane resins, urethane resins, polyurethane resins (polyurethane resin), diurethane dimethacrylate, allyl aliphatic urethane di acrylate, urethane acrylate, aliphatic urethane methacrylate, aliphatic urethane diacrylate, polyurethane diol, polydimethyl siloxane, silicone Acrylate (silicone acrylate), silicone diacrylate (silocone diacrylate), silicone hexaacrylate (silocone hexaacrylate), polyester resins, polyester styrene resin, polyester acrylate (polyester acrylate), poly Polyester triacrylate, polyester tetraacrylate, polyester hexaacrylate, polyester urethane acrylate, polyether acrylate, poly Ether tetraacrylate Polyether tetraacrylate, polyether urethane acrylate, polyethylene resin, polyethylene glycol acrylate, polyethylene glycol diacrylate, polyethylene glycol methyl Polyethylene glycol methyl ether acrylate, polyethylene-co-methacrylate, polyethylene-co-ethyl acrylate, polyethylene-co-ethyl acrylate ( polyethylene-co-methyl acrylate, melamine resin, trichloromelamine, polymelamine-co-formaldehyde, hexakismethoxymethyl melamine, butyl ray Butylated melamine, isobutylated melamine melamine), isobutylated urea melamine, and trinaphthylmethyl melamine.

And, as the acrylic monomer, methyl acrylate (methyl acrylate), ethyl acrylate (ethyl acrylate), butyl acrylate (butyl acrylate), isobutyl acrylate (isobutyl acrylate), hydroxyethyl acrylate (hydroxyehtyl acrylate), methyl Methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, allyl methacrylate, ethylene glycol dimethacryl Ethylene glycol dimethacrylate, hydroxyethyl methacrylate, glycidyl methacrylate, hexandiol diacrylate, hexanediol dimethacrylate, Trimethylopropane trimethacrylate, ethylene-3-ethoxy acryl Ethyl-3-ethoxy acrylate, triethylene glycol dimethacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate hydroxybutyl acrylate), ethoxyethyl acrylate, ethoxyethyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, lauryl acrylate acrylate, lauryl methacrylate, ethylene diacrylate, ethyl-3-amino-3-ethoxy acrylate, tert-butyl acrylate (tert) -butyl acrylate), trimethylsilyl methacrylate, tripropylene glycol diacryla te), hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, phenyl methacrylate, tetraethylene glycol diacrylate, polyethylene Polyehtylene glycol phenyl ether acrylate, 2-hydroxy-3-phenoxypropyl acrylate, ethylene glycol dicyclopentenyl ether acrylate acrylate), ethylene glycol dicyclopentenyl ether methacrylate, sodium acrylate, sodium methacrylate, tridecyl methacrylate, hexyl acryl Hexyl acrylate, hexyl methacrylate l methacrylate, isodecyl acrylate, isodedecyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, benzyl 2-ethyl acrylate 2-ethyl acrylate), ethyl 2-N-propyl acrylate, benzyl 2-N-propyl acrylate, zinc acrylate, butanediol diacrylate, butanediol At least one selected from butanediol dimethacrylate, vinyl acrylate and vinyl methacrylate.

As an inorganic ceramic, tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrakis (2-hydroxyethyl) orthosilicate ), Lithium orthosilicate, cesium aluminum orthosilicate, tetrabutyl orthosilicate, aluminum sec-butoxide, aluminum sec-butoxide, aluminum tributoxide, aluminum Ethoxide (aluminum ethoxide), diethyl aluminum ethoxide, aluminum isopropoxide, aluminum tert-butoxide, aluminum nitrate anhydride anhydride), aluminum nitrate nonahai Aluminum nitrate nonahydrate, aluminum nitrate eneahydrate, aluminum phenoxide, zirconium acetylacetonate, zirconium bis (diethyl citrato) dipropoxide bis (diethyl citrato) dipropoxide, zirconium tert-butoxide, zirconium ethoxide, zirconium isopropoxide, zirconium trifluoroacetyl acetonate ), Zirconium tetrakis (2,2,6,6-tetramethyl-3,5-heptanedionate), zirconium tetrakis (2,2,6,6-tetramethyl-3,5-heptanedionate), zirconium diiso Zirconium diisopropoxide bis (2,2,6,6-tetramethyl-3,5-heptanedionate), zirconium chloride chloride), tee Titanium bis (ethyl acetoacetato) diisopropoxide, titanium butoxide, titanium tert-butoxide, titanium chloride , Titanium diisopropoxide bis (acetylacetonate), titanium diisopropoxide bis (2,2,6,6-tetramethyl-3,5-heptanedionate) ( titanium diisopropoxide bis (2,2,6,6-tetramethyl-3,5-heptanedionate), titanium ethoxide, titanium 2-ethyl-1,3-hexanediolate (titanium 2-ethyl-1, 3-hexanediolate, titanium 2-ethylhexyloxide, titanium isopropoxide, titanium methoxide, titanium nitrate, titanium oxide acetylacetonate titanium oxide acetylacetonate) Propoxide (titanium propoxide), titanium (triethanol amino Nei Sat) is selected one or more of the isopropoxide (titanium (triethanolaminato) isopropoxide).

As the surfactant, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether ether, polyoxyothylene stearyl ether, polyoxyethylene oleic ether, polyoxyethylene branched decyl ether, polyoxyethylene tridecyl ether tridecyl ether, polyoxyethylene lauryl amine, polyoxyethylene stearyl amine, polyoxyethylene oleic amine, polyoxyethylene tallow amine Of these, at least one of them is selected and used.

As a binder, disilane, dichlorodimethylsilane, dimethyldichlorosilane, 1,1,1-trimethyl-2,2,2-triphenyldisilane (1,1,1-trimethyl-2 , 2,2-triphenyldisilane, diethoxydimethylsilane, hexamethylcyclotrisilane, hydroxycyclohexasilane, ethyldisilane, dibityldichlorosilane, Acetoxytrimethylsilane, 2,4,6,8-tetraoxa-5-carbanonasilane (2,4,6,8-tetraoxa-5-carbanonasilane), octaphenyloxacyclopentasilane, 2 , 2-dichloro-1-trimethylsiloxytrisilane (2,2-dichloro-1-trimethylsiloxytrisilane), 2-bromo-1-chloro-1,1-dimethyl-2-phenyl-3-propyltrisilane (2 -bromo-1-chloro-1,1-dimethyl-2-phenyl-3-propyltrisilane, acetyltrimethylsilane, dichloroethyl Silane (dichloroethylsilane), allyloxy-trimethylsilane (allyloxytrimethylsilane), silane (allyltriethoxysilane), γ- aminopropyl methyl dimethoxy silane (γ -aminopropylmethyldimethoxysilane), silane (3-aminopropyltriethoxysilane) to 3-aminopropyl allyl tree, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropyl-trimethoxysilane (N-aminoethyl-3-aminopropyl -trimethoxysilane, N-aminoethyl-3-aminopropyl-dimethoxymethylsilane, phenyltrimethoxysilane, phenyltriethoxysilane, methacryl Oxysilane (methacryloxysilane), 3-methacryloxytrimethoxysilane, 3-methacryloxytriethoxysilane, 3-methacryloxysilane Peel trimethylsilane (3-methacryloxypropyltrimethylsilane), γ - methacryloxypropyl triethylsilane (γ -methacryloxypropyltriethylsilane), γ - methacryloxypropyl trimethoxy silane (γ -methacryloxypropyltrimethoxysilane), published 3-ethoxy-methacryloxy propyltriethoxysilane (3-methacryloxypropyltriethoxysilane), 3-chloropropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3-mercaptopropyltrimethoxysilane (3 -mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, methylsilane, ethylsilane, ethylbutyl, butylsilane, trimethylsilane, triethylsilane, Tributylsilane, tripropylsilane, butyltrichlorosilane, triisopropylsil ane), dimethylphenylsilane, trimethoxysilane, tetramethoxysilane, triethoxysilane, methyltrimethoxysilane, methyldietoxysilane , Methyltriethoxysilane, methyltriethoxysilane, methoxytrimethylsilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethoxytrimethylsilane, ethoxytrimetylsilane, dimethylisopropylsilane ), Trimethoxypropylsilane (trimethoxypropylsilane), triethoxypropylsilane (triethoxypropylsilane), triethoxy-3-ureidopropylsilane (triethoxy-3-ureidopropylsilane), trimethoxy-3-methacryloxypropylsilane ( trimethoxy-3-methacryloxypropylsilane), 3-diethylaminopropyltrimethoxysilane, isobutyltrimethoxysilane (i sobutyltrimethoxysilane), 3-glycidyloxypropyltrimethylsilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane (3-glycidyloxypropyltriethoxysilane ), γ - glycidyl oxy propyl trimethoxy silane (γ -glycidoxypropyltrimethoxysilane), vinyl triethoxysilane (vinyltriethoxysilane), silane (3-isocyanatopropyltriethoxysilane 3-isocyanato propyltriethoxysilane), tri-sila agent (trisilazane) , 1-aminodisilazane (1-aminodisilazane), hexamethyldisilazane, hexamethyldisilazane, aminosilazane (aminosilazane), disiloxane, hexasiloxane, 1,1,1-trimethyldisiloxane (1,1,1-trimethyldisiloxane), cyclotrisiloxane, hexamethylcyclotrisiloxane, 2-methoxycyclotrisiloxane, hexachlorodisil Acid (hexachlorodisiloxane), D is phenyl siloxane is used at least one selected from the diol (diphenylsiloxanediol).

An embodiment of the present invention having the above characteristics will be described in more detail with reference to the accompanying drawings.

1 is a schematic view showing the chemical structure of a high wear-resistant organic / inorganic hybrid coating agent according to the present invention, the paint according to the present invention is an organic acrylic polymer resin (1), an inorganic ceramic (2), the organic acrylic polymer resin ( It consists of surfactant (1) and binder (3) which connect 1) and inorganic ceramic (2) with each other, and ceramic nanoparticle (4).

The organic / inorganic hybrid coating agent of the present invention configured as described above is a compound of an sol gel silicate which is an acrylic polymer resin and an inorganic ceramic, and since the acrylic polymer resin shows hydrophobicity and the sol gel silicate shows hydrophilicity, In order to bond with each other, a binder having both a hydrocarbon polymer group and a hydroxyl group is added, or chemically bonded in a hybrid form using a surfactant having both a hydrophobic group and a hydrophilic group.

In addition, in the case of adding the ceramic nanoparticles, the addition content is limited to less than 5% by weight, the addition of more than the opacity of the solution occurs not only reduces the glossiness of the coating layer but also affects the surface roughness. The size of the ceramic nanoparticles also has a very large effect. Particles of 50 nm or less must be added, and if the particle size is larger than this, sedimentation occurs in the solution, and after coating, the surface of the coating layer becomes uneven and rough.

In the above-described configuration, the acrylic polymer resin has a very high viscosity of 2,000 to 15,000 cPs at room temperature, so it is not easily dissolved in alcohol at room temperature, and thus requires very strong agitation. The stirring medium should be at least 3/4 of the diameter of the container for sufficient stirring. This is possible.

In addition, in order to dissolve the acrylic polymer resin, an acrylic monomer may be added together with the alcohol solvent, and in this case, the degree of polymerization may be further improved during the thermal polymerization process. However, when the content of the acrylic monomer is added more than 30% by weight of the total, the coating layer dissolves or penetrates the paint layer or reacts with the surface of the acrylic base material to lower the interface bonding force.

As the content of ceramic components including sol-gel silicates in the coating increases, the Vickers hardness of the coating layer increases, but when too much is added, the hardness value increases, while the contraction and elastic modulus of the coating layer increase, resulting in interfacial peeling or coating surface cracking. Because of this, it is necessary to adjust the proper content.

Figure 2 is spray coating on the plastic substrate of the organic-inorganic hybrid coating prepared according to the addition amount of the ceramic including tetraethyl silicate and alumina ceramic nanoparticles sol-gel silicate in the present invention, and cured at 75 ℃ for 1 hour, then Vickers It shows the hardness of the coating layer measured by applying a load of 50g with a hardness tester.

As shown in FIG. 2, when the ceramic component is not added as in the conventional UV coating, the Vickers hardness value is about 130 MPa, and when the ceramic component is added about 5% by weight, the hardness value is increased to about 161 MPa. It can be seen. Although the surface hardness increases with the ceramic content, the surface hardness is greatly improved to 250 MPa or more when the ceramic component is added more than 20% by weight. After the bonding test, a large part of the lattice is peeled off. In addition, because of the high hardness, the elastic force is lowered, so that a large crack occurs on the surface in the bending state is not preferable for the durability of the coating layer.

3 shows the indentation traces of the diamond indenter after the Vickers hardness measurement described above at 50 times magnification.

A is a diamond indenter station shown after measuring the Vickers hardness of the coating layer coated only with the polymer paint by the conventional UV polymerization method without adding the ceramic component. The Vickers hardness was about 131 MPa, and as shown in the photograph, the edge of the indentation trail that is typical of the polymer is pushed out. On the other hand, the addition of 10 wt% tetraethylsilicate to the polymer content in the organic / inorganic hybrid coating of the present invention resulted in a Vickers hardness of about 194 MPa, with very sharp indenter edges, typical of high hardness materials. It is showing. In addition, the smaller size of the indentation traces supports higher hardness.

Figure 4 shows the Vickers hardness and interfacial peeling properties according to the content of tetraethyl silicate for the polymer.

In general, the content of water for hydrolysis of the alkoxide depends on the number of alkoxy groups of the starting material alkoxide and the molar drainage thereto. Tetraethyl silicate has four ethoxy groups, and in order to completely hydrolyze it, at least four times more moles of distilled water are required than the number of moles of tetraethyl silicate. When distilled water is added, the ethoxy group of tetraethyl silicate is substituted with a hydroxyl group after hydrolysis, and the hydroxyl group can be combined with a polymer or a binder.

However, tetraethylsilicate itself exhibits hydrophobic properties, and when hydrolyzed, the ethoxy group is changed to a hydrophilic group by changing to a hydroxyl group, so that the opacity is maintained without mixing with the acrylic polymer. In order to improve this, a hydrophobic polymer and a hydrophilic tetraethyl silicate may serve as a crosslinking agent or a binder. In this process, when too much distilled water is added, the opacity is maintained and the opacity is maintained even after coating.

Tetraethyl silicate content is also one of the most important factors. As the content increases, the hardness increases, but due to the large shrinkage characteristic of the sol-gel process, tensile stress is applied at the interface, resulting in peeling of the coating layer.

As shown in FIG. 4, the peeling of the tetraethyl silicate is less than 10 wt% with respect to the polymer, but the peeling is not relatively low, and the hardness is relatively low, and when it is added in the range of 10 to 15 wt%, it exhibits suitable hardness and interfacial bonding properties. In addition, when more than 20% by weight, most of the coating layer is peeled.

Figure 5 shows the Vickers hardness according to the polymerization temperature and polymerization time after coating the plastic base material with a paint added with 5% by weight inorganic sol gel silicate in the organic / inorganic hybrid coating of the present invention.

In general, the thermal polymerization degree of the polymer coating is greatly affected by the polymerization temperature and time. The higher the polymerization temperature, the longer the polymerization time, the higher the degree of polymerization, but in order to increase the coating yield, it is important to improve the properties of the coating layer while reducing the polymerization time as much as possible. In the case of UV polymerization, the polymerization takes place within a few seconds by the UV polymerization initiator, but in the case of thermal polymerization, sufficient polymerization does not occur within 30 minutes, and radicals are formed by decomposition of the polymerization initiator, and monomers or polymer resins are bonded to the chains. It takes enough time to form.

As shown in FIG. 5, as the polymerization temperature increases, the Vickers hardness increases, which means that the degree of polymerization increases. Overall, the polymerization time is further improved when the polymerization time is longer than 1 hour to 2 hours, it can be seen that the degree of polymerization is stable at 90 ℃ or more when coated with the organic / inorganic hybrid solution of the present invention and polymerized. However, when the polymerization was carried out for about 2 hours at a temperature of 90 ℃ or more, the shrinkage of the coating layer is relatively high, and the coating layer is peeled off in the x-cut test. In the organic / inorganic hybrid coating solution of the present invention, when 5 wt% of inorganic sol-gel silicate was added, the polymerization performance was excellent when the polymerization was performed at 85 ° C. for 2 hours.

Hereinafter, the present invention will be described in more detail with reference to Examples 1 to 3. However, the following examples are merely to illustrate the invention, the present invention is not limited by the following examples.

< Example  1 ~ 3> acrylic polymer Tetraethylsilicate  / Inorganic containing alumina ceramic nanoparticles hybrid Coating Paint  Produce

For Examples 1 to 3, a polyester tetraacrylate resin was weighed in a three-necked glass flask, and methyl methacrylate was added to the resin and stirred at 20 to 50% by weight. Ethanol was added to 5 to 10% by weight of the polymer content and stirring was continued until the resin was completely dissolved. When the polymer resin was sufficiently dissolved, 10 to 20 wt% of ethyl methacrylate or isobutyl acrylate was added to the resin and stirred to prepare a polymer starting solution.

Tetraethyl-silicate alkoxide was added to the prepared polymer starting solution as an inorganic component in an amount of 5 to 20% by weight based on the polymer content, and ethanol corresponding to 5 times the molar number of tetraethyl silicate was added as a solvent. Added. For hydrolysis, hydrolysis was carried out while slowly adding distilled water corresponding to 10 times the number of moles to tetraethyl silicate.

As described above, the solution mixed with the organic polymer and the inorganic tetraethyl silicate was not mixed with each other, and in order to hybridize it, polyoxyethylene nonyl phenyl ether was added in an amount of 1 to 5% by weight based on the total weight. . Tetramethylethylsilane was added in an amount of 5 to 10% by weight based on the total weight as a binder to bond well with the base material when the solution was coated, and the stirring was continued until the solution became clear.

When the solution became clear, 0.8 wt% of AIBN (α, α'-azobisisobutyronitrile) was added as a polymerization initiator and stirred until completely dissolved. As a coating additive, 0.1-2.0 weight% of polyether modified polydimethylsiloxane and polysiloxane were added and stirred. Finally, by adding 3% by weight of the ceramic alumina nanoparticles of 20nm size to complete the double reinforced organic / inorganic hybrid coatings.

The completed solution was spray-coated onto a polycarbonate plastic substrate, and the polymerization temperature was polymerized at 70 to 85 ° C. and the polymerization time was 1 to 2 hours, respectively. The polymerized specimen was cut to a size of 20 mm x 20 mm in length, and a diamond indenter was applied to the surface of the coating layer with a micro-Vickers hardness tester for 10 seconds under a load of 50 g, and then the horizontal and vertical diagonal lengths of the indenter were measured. By applying the Vickers hardness value for each specimen was obtained, the results are also shown in Table 1.

Tetraethyl Silicate Content 75 ℃ 1 hour 75 ℃ 2 hours 80 ℃ 1 hour 80 ℃ 2 hours 85 ℃ 1 hour 85 ℃ 2 hours Example 1  5 wt% 152 165 158 174 167 180 Example 2  10 wt% 176 182 179 188 186 194 Example 3  20 wt% 236 246 240 255 252 268 Comparative Example 1  Conventional UV Polymerization    131

Table 1 shows the Vickers hardness (unit: MPa) by tetraethyl silicate content for the polymer, the hardness value of the coating layer was increased with increasing tetraethyl silicate content, containing tetraethyl silicate and alumina nanoparticles When applied, the hardness value was much higher than that of the conventional UV coating layer. Also, the higher the polymerization temperature, the longer the polymerization time, the higher the hardness value. However, when the tetraethyl silicate content is added 20% by weight, when the polymerization at a temperature of 80 ℃ or more, most of the phenomenon was peeled off in the x-cut test, in this case it was confirmed that 75 ℃ is the most suitable polymerization temperature.

< Experimental Example  1> organic / inorganic hybrid Coating paints  Painting characteristics

6 is an organic / inorganic hybrid coating agent prepared according to Example 2, when the spray coating on a plastic substrate, the photo (C) artificially formed wrinkles on the coating layer immediately after coating, and the leveling state of the coating layer after 5 minutes The photo (D) and the photo (E) showing the surface gloss after curing for 1 hour at 75 ° C. are each magnified 1.5 times.

Polyether-modified polydimethylsiloxane, which is one of the leveling agents added in the present invention, exhibits excellent surface leveling, that is, coating layer flattening in a short time by maintaining a proper and uniform surface tension while well blending hydrophobic organic polymer and hydrophilic sol-gel tetraethyl silicate. Could confirm.

< Experimental Example  2> organic / inorganic hybrid  Interfacial Bonding Force Characteristics of Coating Layer

FIG. 7 is an organic / inorganic hybrid coating solution prepared according to Example 2, and cross-shaped lattice is artificially formed on a specimen cured for 1 hour at 75 ° C. after spray coating on a plastic substrate, and a transparent adhesive tape is attached thereto. The x-cut test was performed to remove and show a double enlarged picture of the adhesion of the coating layer without the dropping grating.

As can be seen in Examples 1 to 3, since the sol-gel silicate itself has a large shrinkage during drying, the lattice is dropped in the x-cut test when the addition amount is out of the critical range. However, in the present invention, when the content of tetraethyl silicate is less than 10%, it was confirmed that the tetramethylethylsilane binder added during the polymerization at 85 ° C. or less bonds the plastic base material and the coating layer well.

< Experimental Example  3> organic / inorganic hybrid  Of coating layer Surface roughness  characteristic

Figure 8 shows the result of spray coating on the plastic substrate with the organic / inorganic hybrid coating solution of the present invention and cured at 75 ℃ for 1 hour, and then measured the surface roughness with a laser surface roughness.

As shown in FIG. 8, it can be seen that the surface is very smooth, which is derived from excellent surface leveling characteristics, as shown in Experimental Example 1 above. The Ra value, which is evaluated as an index of surface roughness, is about 25 nm, which supports the glossiness and reflectivity of the coating layer.

< Experimental Example  4> organic / inorganic hybrid  Thickness of coating layer

9 is sprayed on a plastic substrate with an organic / inorganic hybrid coating solution of the present invention and cured at 75 ° C. for 1 hour, and then the cross section of the coating layer is observed by scanning electron microscopy and shows a magnified 1500 times.

When sprayed about 8 times in each direction by the spray coating method, the thickness of the coating layer was about 18 μm, and when the spray amount was adjusted, it was confirmed that the thickness thereof was sufficiently low.

The coating agent is used as an exterior coating agent, a fiber adhesive, a binder for the console box fiber coating, in the case of the exterior coating agent, the wear resistance and interfacial bonding strength is significantly improved, and the fiber adhesive and the binder for the console box fiber coating significantly improve the interfacial bonding strength. .

As described above, the organic / inorganic hybrid coating material of the present invention can significantly increase wear resistance and chemical resistance corrosion resistance by reinforcing ceramic components compared to conventional UV polymerization methods, and only inorganic sol gel silicate is added as compared to conventional hybrid methods. In addition, the addition of additional ceramic nanoparticles can double the abrasion resistance, and can further improve the performance of protecting the surface of plastics, metals, and ceramic products compared to conventional coating solutions, resulting in further durability of the product. have.

In addition, the present invention does not use any UV, and also because it is an environmentally friendly coating that uses only water and alcohol as a solvent without harmful solvents such as thinner, it is possible to prepare for environmental regulations as well as meet the trend of the future coating field. .

In addition, the interfacial bonding force with the base material is greatly improved by the added binder, thereby significantly improving the problem of peeling off the coating layer.

In addition, the organic / inorganic hybrid coating agent of the present invention contains a low surface tension alcohol, there is no need to use a solvent such as thinner when spraying paint coating, and the coating environment is also excellent due to the excellent leveling properties after coating due to acrylic leveling additives It can be greatly improved.

Claims (16)

Acrylic polymer resin, Alcohol solvent for acrylic polymer resin composed of at least one selected from 1 to 30% by weight of methanol, ethanol, butanol, isobutanol, propanol and isopropanol with respect to the acrylic polymer resin; Tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, and tetrakis (2-hydroxy) added at an amount of 5-35% by weight based on the weight of the acrylic polymer resin. Ethyl) tetrakis (2-hydroxyethyl) orthosilicate, lithium orthosilicate, cesium aluminum orthosilicate, tetrabutyl orthosilicate, aluminum sec-butoxide butoxide, aluminum tributoxide, aluminum ethoxide, diethyl aluminum ethoxide, aluminum isopropoxide, aluminum tert-butoxide butoxide), aluminum nitrate anhydride anhydride, aluminum nitrate nonahydrate, aluminum nitrate eneahydrate, aluminum phenoxide, zirconium acetylacetonate, zirconium acetylacetonate, zirconium bis (diethyl citrato) ) Zirconium bis (diethyl citrato) dipropoxide, zirconium tert-butoxide, zirconium ethoxide, zirconium isopropoxide, zirconium isopropoxide, zirconium trifluoro Zirconium trifluoroacetyl acetonate, zirconium tetrakis (2,2,6,6-tetramethyl-3,5-heptanedionate) (zirconium tetrakis (2,2,6,6-tetramethyl-3,5- heptanedionate)), zirconium diisopropoxide bis (2,2,6,6-tetramethyl-3,5-heptanedionate )), Zirconium chloride, titanium bis (ethyl acetoacetato) diisopropoxide, titanium butoxide, titanium tert-butoxide Titanium chloride, titanium diisopropoxide bis (acetylacetonate), titanium diisopropoxide bis (2,2,6,6-tetramethyl-3, 5-heptanedionate) (titanium diisopropoxide bis (2,2,6,6-tetramethyl-3,5-heptanedionate)), titanium ethoxide, titanium 2-ethyl-1,3-hexanediolate ( titanium 2-ethyl-1,3-hexanediolate), titanium 2-ethylhexyloxide, titanium isopropoxide, titanium methoxide, titanium nitrate Titanium oxide acetyla Sat carbonate (titanium oxide acetylacetonate), titanium propoxide (titanium propoxide), titanium (triethanol amino Nei Sat) isopropoxide (titanium (triethanolaminato) isopropoxide) the selected one or more of the inorganic sol-gel ceramic precursor, Distilled water for hydrolysis of sol-gel inorganic ceramic precursors corresponding to 4-10 times the number of moles of sol-gel inorganic ceramic precursors, 0.5-5% by weight of cationic, anionic or nonionic surfactant, or silane, silazane or siloxane based on the total weight of the polymer resin, alcohol solvent, sol-gel inorganic ceramic precursor and distilled water. Binder is added and 0.5 to 20% by weight, An organic / inorganic hybrid coating agent, characterized in that composed of ceramic nanoparticles added by 0.1 to 5% by weight based on the total weight of the components. According to claim 1, wherein the acrylic polymer resin, epoxy resin (epoxy resin), epoxy methadiacrylate (epoxy methadiacrylate), poly (bisphenol A-copolymer- epichlorohydrin) epoxy resin (poly (bisphenol A- co-epichlorohydrin based on epoxy resin, diglycidyl ether of bisphenol A-based epoxy resins, epoxyacrylate oligomers, phenol-urethane resins, urethane resins, polyurethane resins, diurethane dimethacrylates, allyl aliphatic urethane diacrylates, urethane acrylates Aliphatic urethane methacrylate, aliphatic urethane diacrylate, polyurethane diol urethane diol, polydimethyl siloxane, silicone acrylate, silicone diacrylate, silicone hexaacrylate, polyester styrene as polyester resin resins, polyester acrylates, polyester triacrylates, polyester tetraacrylates, polyester hexaacrylates, polyester urethane acrylates acrylate, polyether acrylate, polyether tetraacrylate, polyether urethane acrylate, polyethylene resin, polyethylene glycol acrylate ), Polyethylene glycol diacrylate, polyethylene glycol methyl ether acrylate, polyethylene-co-methacrylate, polyethylene-copolymer-ethyl acrylate co-ethyl acrylate), polyethylene-co-methyl acrylate, melamine resin, trichloromelamine, polymelamine-co-formaldehyde , Hexakismethoxymethyl melamine, butylated melamine, isobutylated melamine, isobutylated urea melamine, trinaphthylmethyl melamine melamine) organic / inorganic high, characterized in that at least one selected from the use Breed Coatings. The organic / inorganic hybrid coating agent according to claim 1, wherein the acrylic monomer is added in an amount of 5-30% by weight based on the acrylic polymer resin. The method of claim 3, wherein the acrylic monomer is methyl acrylate (methyl acrylate), ethyl acrylate (ethyl acrylate), butyl acrylate (butyl acrylate), isobutyl acrylate (isobutyl acrylate), hydroxyethyl acrylate ( hydroxyehtyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, allyl methacrylate, Ethylene glycol dimethacrylate, hydroxyethyl methacrylate, glycidyl methacrylate, hexandiol diacrylate, hexanediol dimethacrylate (hexandiol dimethacrylate), trimethylopropane trimethacrylate, ethylene-3- Ethoxy-3-ethoxy acrylate, triethylene glycol dimethacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acryl Hydroxybutyl acrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, lauryl acrylate lauryl acrylate, lauryl methacrylate, ethylene diacrylate, ethyl-3-amino-3-ethoxy acrylate, tertiary butyl acrylate (tert-butyl acrylate), trimethylsilyl methacrylate, tripropylene glycol diacrylate ne glycol diacrylate, hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, phenyl methacrylate, tetraethylene glycol diacrylate , Polyethylene glycol phenyl ether acrylate, 2-hydroxy-3-phenoxypropyl acrylate, ethylene glycol dicyclopentenyl ether acrylate dicyclopentenyl ether acrylate, ethylene glycol dicyclopentenyl ether methacrylate, sodium acrylate, sodium methacrylate, tridecyl methacrylate, Hexyl acrylate, hexyl meta Hexyl methacrylate, isodecyl acrylate, isodecyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, benzyl 2-ethyl acrylic Benzyl 2-ethyl acrylate, ethyl 2-N-propyl acrylate, benzyl 2-N-propyl acrylate, zinc acrylate, butanediol diacrylate ), Butanediol dimethacrylate (butanediol dimethacrylate), vinyl acrylate (vinyl acrylate), vinyl methacrylate (vinyl methacrylate), characterized in that at least one organic / inorganic hybrid coating agent. delete The method of claim 1, wherein the surfactant is polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene Cetyl ether, polyoxyothylene stearyl ether, polyoxyethylene oleic ether, polyoxyethylene branched decyl ether, polyoxyethylene Tridecyl ether, polyoxyethylene lauryl amine, polyoxyethylene stearyl amine, polyoxyethylene oleic amine, polyoxyethylene taloamine one or more selected from (polyoxyethylene tallow amine) Organic / inorganic hybrid coatings. The method of claim 1, wherein the binder is disilane, dichlorodimethylsilane, dimethyldichlorosilane, 1,1,1-trimethyl-2,2,2-triphenyldisilane (1,1 , 1-trimethyl-2,2,2-triphenyldisilane, diethoxydimethylsilane, hexamethylcyclotrisilane, hydroxycyclohexasilane, hydroxycyclohexasilane, ethyldisilane, dibutyl dichloro Silane (dibytyldichlorosilane), acetoxytrimethylsilane, 2,4,6,8-tetraoxa-5-carbanonasilane (2,4,6,8-tetraoxa-5-carbanonasilane), octaphenylroxacyclopenta Silane (octaphenyloxacyclopentasilane), 2,2-dichloro-1-trimethylsiloxytrisilane, 2-bromo-1-chloro-1,1-dimethyl-2-phenyl-3 Propyltrisilane (2-bromo-1-chloro-1,1-dimethyl-2-phenyl-3-propyltrisilane), acetyltrimethylsilane , Dichloroethyl silane (dichloroethylsilane), allyloxy-trimethylsilane (allyloxytrimethylsilane), allyl silane (allyltriethoxysilane), γ- aminopropyl methyl dimethoxy silane (γ -aminopropylmethyldimethoxysilane), a 3-aminopropyl triethoxysilane (3- aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropyl-trimethoxysilane (N-aminoethyl- 3-aminopropyl-trimethoxysilane, N-aminoethyl-3-aminopropyl-dimethoxymethylsilane, phenyltrimethoxysilane, phenyltriethoxysilane , Methacryloxysilane (methacryloxysilane), 3-methacryloxytrimethoxysilane, 3-methacryloxytriethoxysilane, 3-methacryloxytriethoxysilane Other methacrylic oxy trimethyl silane (3-methacryloxypropyltrimethylsilane), γ - methacryloxypropyl triethylsilane (γ -methacryloxypropyltriethylsilane), γ - methacryloxypropyl trimethoxy silane (γ -methacryloxypropyltrimethoxysilane), 3- methacryloxy-propyltriethoxysilane 3-methacryloxypropyltriethoxysilane, 3-chloropropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3-mercaptopropyltrimethoxy 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, methylsilane, ethylsilane, butylsilane, trimethylsilane, triethylsilane triethylsilane, tributylsilane, tripropylsilane, butyltrichlorosilane, triisopropyl Triisopropylsilane, dimethylphenylsilane, trimethoxysilane, tetramethoxysilane, triethoxysilane, methyltrimethoxysilane, methyldiethoxysilane metyldietoxysilane, methyltriethoxysilane, methoxytrimethylsilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethoxytrimethylylsilane, dimethylisopropylsilane (dimethylisopropylsilane), trimethoxypropylsilane, triethoxypropylsilane, triethoxy-3-ureidopropylsilane, trimethoxy-3-methacryloxypropyl Trimethoxy-3-methacryloxypropylsilane, 3-diethylaminopropyltrimethoxysilane, isobutyl Isobutyltrimethoxysilane, 3-glycidyloxypropyltrimethylsilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyltriethoxysilane (3-glycidyloxypropyltriethoxysilane), γ - glycidyl oxy propyl trimethoxy silane (γ -glycidoxypropyltrimethoxysilane), vinyl triethoxysilane (vinyltriethoxysilane), 3- isocyanatomethyl Ito propyl triethoxysilane (3-isocyanatopropyltriethoxysilane), tree sila Trisilazane, 1-aminodisilazane, hexamethyldisilazane, hexamethyldisilazane, aminosilazane, disiloxane, hexasiloxane, 1,1,1 -Trimethyldisiloxane (1,1,1-trimethyldisiloxane), cyclotrisiloxane, hexamethylcyclotrisiloxane, 2-methoxycyclotrisiloxane, hex An organic / inorganic hybrid coating agent, characterized in that at least one selected from hexachlorodisiloxane, diphenylsiloxanediol. The organic / inorganic hybrid coating according to claim 1, wherein ethanol is further added to the inorganic ceramic in an amount of 2 to 10 times the number of moles. The organic / inorganic hybrid coating agent according to claim 1, wherein 0.1 to 5% by weight of a polymerization initiator is added to the coating agent, and 0.1 to 2% by weight of a leveling agent is further added. The organic / inorganic hybrid coating agent according to claim 1, wherein the ceramic nanoparticles have a particle size of 10-50 nm and are selected from at least one selected from silica, alumina, zirconia, titanium dioxide, potassium oxide, and silicon carbide. . The method according to any one of claims 1, 2, 3, 4, 6, 7, 8, 9, 10, wherein the coating agent is an outer coating agent, a fiber adhesive, a console box fiber coating bond Organic / inorganic hybrid coatings, characterized in that used as a zero. Preparing a polymer solution for stirring the acrylic polymer resin and at least one alcohol solvent selected from 1 to 30% by weight of methanol, ethanol, butanol, isobutanol, propanol, and isopropanol with respect to the acrylic polymer resin; A ceramic hydrolysis step of adding an inorganic ceramic to 5-35 wt% based on the weight of the acrylic polymer resin, and adding and stirring distilled water corresponding to 4-10 times the number of moles to the inorganic ceramic; 0.5-5% by weight of cationic, anionic, or nonionic surfactant or silane, silazane, or siloxane based on the total weight of the polymer solution and the ceramic hydrolysis solution, and the polymer solution and ceramic solution Preparing a hybrid solution by adding one or both binders added in an amount of 0.5 to 20% by weight based on the total weight of the decomposition solution; The method of manufacturing an organic / inorganic hybrid coating agent capable of thermal polymerization in air, comprising adding 0.1 to 5 wt% of the ceramic nanoparticles to the hybrid solution based on the total weight of the hybrid solution. The method of claim 12, wherein in the preparing of the polymer solution, the acrylic monomer is added to the acrylic polymer resin by adding 5-30% by weight. The method of claim 12, wherein in the hydrolysis step, ethanol is added to the inorganic ceramic in a 2-10-fold molar number as a solvent to thermally polymerize the air / inorganic hybrid coating agent. 13. The thermal polymerization in air according to claim 12, wherein the polymerization initiator is added in an amount of 0.1 to 5% by weight and the leveling agent is added in an amount of 0.1 to 2% by weight based on the total weight of the hybrid solution prepared in the hybrid solution manufacturing step. This is a possible organic / inorganic hybrid coating method. The organic / inorganic hybrid coating agent prepared by the method of claim 12 is spray-coated to a metal, plastic, ceramic base material in at least one atmosphere selected from air, nitrogen and argon, and thermally polymerized at 60-90 ° C. for 30 minutes to 4 hours. Thermosetting method of organic / inorganic hybrid coating which can be thermally polymerized in air.

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