KR102141297B1 - M/T Coating method for varied kinds of substrates and coated glass body obtained thereby - Google Patents

Abstract

Disclosed are a multilayer film coating method for varied kinds of substrates and a coated glass body obtained thereby. The coated glass body includes: a glass substrate; a hard base coating layer formed on the glass substrate; a transmittance and reflectance control layer comprising alumina (Al_2O_3) and zirconia formed on the hard base coating layer; a protective layer comprising silicon monoxide (SiO) formed over the transmittance and reflectance control layer; and a friction reducing and fingerprint-resistant layer including fluorine and silane formed on the protective layer.

Description

{M/T Coating method for varied kinds of substrates and coated glass body obtained thereby}

The present invention relates to a method for coating a multi-layered multilayer film and a glass coating obtained thereby. More specifically, the present invention includes plastic coatings, glass coatings and metal coatings that can be used as cases of various small electronic devices, such as, for example, feature phones, smartphones and tablet personal computers (PCs), notebook PCs, automobiles, and the like. It relates to a multi-substrate coating method capable of dramatically improving the product quality and production yield by significantly shortening the process in mass production, and a high quality plastic multilayer film coating, glass multilayer film coating, and metal multilayer film coating thus obtained. .

As the touch screen is used in earnest in the field of mobile phone technology such as a smart phone, an advanced mobile phone case design is required as the expression of the mobile phone is concentrated toward the mobile phone case. Accordingly, a method of realizing an aesthetic sense such as a color that cannot be realized only by coating with a coating has been used by forming a multi-layer coating made of a plurality of layers exerting their functions on a plastic mobile phone case. However, in order to form a plurality of layers on a plastic mobile phone case, a number of processes have to be performed, but as the number of processes increases, the problem of increasing production costs due to an increase in defective products, i.e., a decrease in production yield, is also serious. As described above, if a method of manufacturing a plastic mobile phone case by coating widely adopted in the technical field is used, it is difficult to mass-produce a high-quality mobile phone case in a timely manner to cope with market demands in a timely manner.

In order to solve this problem, the Republic of Korea Patent Publication No. 10-1406845 (published on June 16, 2014) "Plastic substrate coating method and the plastic coating obtained thereby" is a step of forming a flexible underlayer on the plastic substrate; Forming a light transmittance and reflectance control layer including a silicon oxide layer and a titanium oxide layer on the flexible undercoat layer; Forming a protective layer comprising aluminum oxide or silicon carbide on the light transmittance and reflectance control layer; And forming a friction reducing layer comprising at least one member selected from the group consisting of carbon fluoride resin, silicon fluoride resin, polysiloxane resin, and polysilazane resin on the protective layer, and controlling the light transmittance and reflectance control layer. The step of forming, the step of forming the protective layer, and the step of forming the friction reducing layer disclose a method for coating a plastic substrate by a continuous deposition process under a pressure lower than atmospheric pressure in the same chamber.

The Republic of Korea Patent Publication No. 10-1406845 can only be coated on a plastic substrate, there is a problem that it cannot be used as a general purpose coating method on a glass substrate or a metal substrate, and there is a limitation that it cannot be commercialized when manufactured according to the presented embodiment. .

Accordingly, one object of the present invention is to solve the above-described conventional problems, multi-layered multi-layer film coating capable of producing both plastic coatings, glass coatings and metal coatings that can be used as a case of a mobile phone such as a smartphone. Is to provide a way.

Another object of the present invention is to provide a plastic coating, a glass coating and a metal coating obtained by a multi-layer multilayer film coating method.

Another object of the present invention is to provide a plastic coating, glass coating and metal coating with improved light reflectance, hardness, fingerprint and stain resistance.

In order to achieve the problem to be solved, the coating method of a multi-substrate according to the present invention comprises the steps of forming a hard undercoat layer on one of a plastic substrate, a glass substrate, and a metal substrate, and alumina ( Al2O3) and forming a transmittance and reflectance control layer comprising zirconia, forming a protective layer using silicon monoxide (SiO) on the transmittance and reflectance control layer, and friction comprising fluorine and silane on the protective layer And forming a reduction and anti-fingerprint layer.

In order to achieve the problem to be solved, the coating method of a multi-substrate according to the present invention comprises the steps of forming a hard undercoating layer on a plastic glass metal substrate and protecting it using silicon monoxide (SiO) on the hard undercoating layer Forming a layer, forming a transmittance and reflectance control layer comprising alumina (Al2O3) and zirconia on the protective layer, and forming a friction reducing and fingerprint layer comprising fluorine and silane on the transmittance and reflectance control layer It may include the steps.

The hard undercoat layer may include propylene glycol monomethyl ether as a reactive diluent.

The hard undercoat layer may further include ethyl acetate, a photoinitiator, and an oligomer as a composition.

To achieve another problem to be solved, the glass coating according to the present invention is a glass substrate, a hard undercoat layer formed on the glass substrate, alumina (Al2O3) as a transmittance and reflectance control layer formed on the hard undercoat layer ) And a transmittance and reflectance control layer comprising zirconia, a protective layer formed using silicon monoxide (SiO) as a protective layer formed on the transmittance and reflectance control layer, and a fluorine and silane as a friction reduction and anti-fingerprint layer formed on the protective layer. It may include.

In order to achieve another problem to be solved, the glass coating according to the present invention, a glass substrate, a hard undercoat layer formed on the glass substrate, a silicon monoxide (SiO) as a protective layer formed on the hard undercoat layer A protective layer formed by using, a transmittance and reflectance control layer comprising alumina (Al2O3) and zirconia as a transmittance and reflectance control layer formed on the protective layer, and a fluorine and silane as a friction reduction and anti-fingerprint layer formed on the transmittance and reflectance control layer. It may include a friction reduction and fingerprint-resistant layer comprising a.

The hard undercoat layer may include propylene glycol monomethyl ether as a reactive diluent.

The glass coating may be a mobile phone case, a tablet PC case, a notebook PC case, a car, or a glass coating that is a PDA (personal digital assistant) case.

To achieve another problem to be solved, the metal coating body according to the present invention is a metal substrate, a hard undercoat layer formed on the metal substrate, a silicon monoxide (SiO) as a protective layer formed on the hard undercoat layer A protective layer formed by using, a transmittance and reflectance control layer comprising alumina (Al2O3) and zirconia as a transmittance and reflectance control layer formed on the protective layer, and a fluorine and silane as a friction reduction and anti-fingerprint layer formed on the transmittance and reflectance control layer. It may include a friction reduction and fingerprint-resistant layer comprising a.

The hard undercoat layer may include propylene glycol monomethyl ether as a reactive diluent.

The metal coating may be a mobile phone case, a tablet PC case, a notebook PC case, a car, or a metal coating body that is a PDA (personal digital assistant) case.

To achieve another problem to be solved, the plastic coating according to the present invention, a plastic substrate, a hard undercoat layer formed on the plastic substrate, a silicon monoxide (SiO) as a protective layer formed on the hard undercoat layer A protective layer formed by using, a transmittance and reflectance control layer comprising alumina (Al2O3) and zirconia as a transmittance and reflectance control layer formed on the protective layer, and a fluorine and silane as a friction reduction and anti-fingerprint layer formed on the transmittance and reflectance control layer. It may include a friction reduction and fingerprint-resistant layer comprising a.

The hard undercoat layer may include propylene glycol monomethyl ether as a reactive diluent.

The plastic coating may be a mobile phone case, a tablet PC case, a notebook PC case, a car, or a plastic coating body that is a PDA (personal digital assistant) case.

According to the multi-layer film coating method of the present invention, instead of the conventional flexible undercoat layer, a hard undercoat layer is formed, and a transmittance and reflectance control layer including alumina and zirconia is formed to form a coating material on a glass substrate and a metal substrate as well as a plastic substrate. Can form. Therefore, according to the multi-layer film coating method of the present invention, it is possible to mass-produce economically high-quality plastic, glass, or metal cell phone cases in one process, and to respond to market demands in a timely manner.

In addition, the plastic coating body, the glass coating body and the metal coating body obtained by the multi-layer film coating method of the present invention have BB cream compared to the plastic coating body obtained by the conventional coating method by forming a friction reducing and inner order layer of fluorine and silane. The stain resistance for lipstick, jeans and complex ultraviolet rays is excellent.

1 is a flow chart for explaining a process for forming a coating made of a plurality of layers on a mobile phone case according to an embodiment of the present invention.
2 is a view showing a glass coating prepared according to an embodiment of the present invention.
3 is a view showing a metal coating prepared according to an embodiment of the present invention.

Hereinafter, a method for coating a multi-layered multilayer film according to specific embodiments of the present invention and a glass coating, a metal coating, and a plastic coating obtained thereby will be described in detail.

1 is a flow chart for explaining a process of forming a multi-layer coating made of a plurality of layers on a mobile phone case according to an embodiment of the present invention.

Referring to FIG. 1, a hard undercoating layer is formed on a mobile phone case (S1). To this end, the hard base layer composition is cured by spraying the hard base layer composition on the mobile phone case and irradiating with actinic rays, for example, ultraviolet rays to form a hard base layer. The hard undercoat layer may have a viscosity of 1000 cps to 2000 cps. If the viscosity is less than 1000 cps, it is difficult to form a base layer on the glass substrate and does not meet the property evaluation for use as a mobile phone case. Here, the mobile phone case may be a plastic mobile phone case, a glass mobile phone case or a metal mobile phone case. The plastic mobile phone case is, for example, polycarbonate, polyethylene terephthalate, polyester such as polybutylene terephthalate, acrylonitrile-butadiene-styrene (ABS) copolymer, polystyrene, vinyl-based resins such as polyvinyl chloride, And polyacetal. The glass cell phone case may be made of glass, and the metal cell phone case may be made of metal such as aluminum or titanium.

The hard base layer composition may include propylene glycol monomethyl ether, isopropyl alcohol, ethyl acetate, photoinitiator, reactive monomer, and oligomer. From the viewpoint of the present invention, normal temperature means a temperature range of 15°C to 25°C.

The ethyl acetate is a polymer binder that serves to impart rigidity to the base layer composition. Preferably, the content is about 15 to about 25 parts by weight based on 100 parts by weight of the total composition. .

The oligomer may be a number average molecular weight of 200 to 5,000, preferably 300 to 3,000, more preferably 500 to 2,000, selected from polyurethane (meth)acrylate, polyester (meth)acrylate or mixtures thereof. One or more photo-curable (meth)acrylate-based oligomers may be used together in consideration of ease of production and application workability of the hard composition.

The oligomer is preferably used in an amount of 20 to 30 parts by weight based on 100 parts by weight of the total composition. At this time, if the amount of the oligomer is more than 30 parts by weight, the crosslinking density of the undercoat after curing is too high, the coating film is brittle, cracks are generated by heat or impact, and when it is less than 20 parts by weight, the rigidity is weakened, which makes it suitable for glass substrates. A coating body having a cannot be formed. In the present invention, it is preferable to use propylene glycol monomethyl ether and a reactive monomer as a reactive diluent for adjusting the viscosity of the oligomer. When the content of propylene glycol monomethyl ether and reactive monomer is low, the viscosity of the rigid composition is too high, and when the content of propylene glycol monomethyl ether and reactive monomer is high, the viscosity of the rigid composition is too small and the UV curability and curing properties are deteriorated. there is a problem.

Propylene glycol monomethyl ether as the reactive diluent is preferably used in an amount of 15 to 20 parts by weight based on 100 parts by weight of the total composition. When the content of the propylene glycol monomethyl ether is more than 20 parts by weight, the viscosity of the composition is lowered, which makes it impossible to form a coating film on the glass substrate, slows the curing rate and lowers the mechanical/chemical properties, and if it is less than 15 parts by weight, the viscosity of the composition Not only does the spray application workability become high, but the workability and leveling decreases, and the compatibility of the constituents deteriorates due to insufficient dilution ability.

The reactive monomer as the reactive diluent is preferably used in an amount of 15 to 25 parts by weight based on 100 parts by weight of the total composition. If the content of the reactive monomer is more than 25 parts by weight, the viscosity of the composition is lowered, which makes it impossible to form a desirable coating film, and also lowers the rigidity of the obtained undercoat, and if it is less than 15 parts by weight, the viscosity of the composition becomes high, and the spray coating workability becomes worse. In addition, workability and leveling are lowered, and the compatibility of the constituent components is deteriorated due to insufficient dilution ability.

Preferably, the hard undercoat composition may include 1 to 5 parts by weight of the photoinitiator. When the content of the photoinitiator exceeds 5 parts by weight, the molecular weight of the resin constituting the undercoat film becomes small and the brittleness of the coating film increases, and if it is less than 1 part by weight, a desired undercoat film property may not be obtained or uncured. The photoinitiator forms a radical by, for example, ultraviolet light, which serves to polymerize and crosslink the oligomer, propylene glycol monomethyl ether, and reactive monomer. A specific example of a photoinitiator that can be used in the present invention is 2-hydroxy-1-4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl commercially available from Ciba Specialty Chemicals. -2-2-methyl propan-1-one (Irgacure 127), 1-hydroxy cyclohexyl phenyl ketone (Irgacure 184), 2-benzyl-2-(dimethylamino)-1-[4-(4-mol Porinyl)phenyl]-1-butanone (Irgacure 369), bis(2,4,6-trimethyl benzoyl)phenyl phosphine oxide (Irgacure 819), 2,4,6-trimethyl benzoyl diphenyl phosphine ( TPO), 2-hydroxy-2-methyl-1-phenyl-1-propane (Darocur 1173), benzophenone (BP), and the like.

The hard base layer composition may further include an organic solvent as necessary. Specific examples of the organic solvent usable in the present invention may include isopropyl alcohol. The content of the organic solvent in the photocurable coating composition may be preferably 5 to 15 parts by weight. At this time, when the content of the organic solvent exceeds 15 parts by weight, the amount of the volatile organic compound is increased, and if it is less than 5 parts by weight, the compatibility of the components of the composition is deteriorated due to insufficient diluent power, and the spray coating property is reduced.

In addition, the hard base layer composition may additionally include a leveling agent, a wetting agent, a pigment, a dispersing agent, etc. in a conventional content as other additives.

The hard undercoating layer composition may be prepared by using a conventional method for preparing an ultraviolet curable coating. Specifically, it can be prepared by mixing in ethyl acetate, oligomer, propylene glycol monomethyl ether and reactive monomer and subject to homogenization treatment. If necessary, organic solvents and other additives may be further added and mixed and homogenized.

In the present invention, the hard undercoat layer formed by crosslinking and curing the hard undercoat composition by ultraviolet irradiation has a plastic layer, a glass substrate and a primer layer that serves to adhere well to the undercoat layer and transmittance formed by vacuum deposition. And a function of the undercoat layer that allows the reflectance control layer (inorganic multilayer coating layer) to adhere well, to be integrated into one layer.

Subsequently, a transmittance and reflectance control layer including alumina (Al2O3) and zirconia (Zro2) is formed as a transmittance and reflectance control layer on the hard undercoat layer (S2). To this end, a plastic base material such as a plastic mobile phone case with a hard base layer formed, a glass base material such as a glass mobile phone case, or a metal base material such as a metal mobile phone case is placed in the deposition chamber of the vacuum deposition equipment, and then alumina is applied on the hard base layer. The (AI2O3) layer is formed by vacuum deposition. The transmittance and reflectance control layer functions to control transmittance and reduce reflectivity using zirconia (Zro2). As the transmittance and reflectance control layer, the alumina (AI2O3) layer plays a role of color correction of the reflected light. Conventionally, it was possible to form a flexible base layer on a plastic substrate to deposit a titanium oxide layer as a metal material, but by forming a rigid undercoat layer on a plastic base material, a glass base material and a metal base material, titanium metal as a metal material was coated with a multi-layer film. Since it is unreasonable to the sieve, it is proved that the mixture of alumina and zirconia forms a transmittance and reflectance control layer to meet the property evaluation.

Subsequently, a protective layer is formed on the transmittance and reflectance control layer using silicon monoxide (SiO) as a protective layer (S3). To this end, when formation of the transmittance and reflectance control layer is completed, a protective layer containing silicon is vacuum-deposited on the transmittance and reflectance control layer in the same deposition chamber. Since all of this silicon is a high hardness material used for Mohs hardness of 9 or more, the wear resistance of a plastic glass metal substrate can be greatly improved. Therefore, the plastic substrate manufactured according to the present invention has excellent scratch resistance. Silicon has a structure that is dense enough to be used as a gas barrier layer material to protect the cell phone battery cover from moisture and other aggressive materials. Particularly, in the present invention, since silicon is coated by vacuum deposition, it is possible to obtain an incomparable strong abrasion resistance, scratch resistance and durability compared to a method of protecting the surface of the transmittance and reflectance control layer which is a coating using a conventional coating method. Can.

Meanwhile, in the embodiment illustrated in FIG. 1, a protective layer is formed on the light transmittance and reflectance control layer, but according to another embodiment of the present invention, on the contrary, a protective layer may be formed under the transmittance and reflectance control layer. have. That is, in this case, after forming a protective layer on the hard undercoat layer, a transmittance and reflectance control layer is formed. In particular, in the present invention, since the transmittance and reflectance control layers and the protective layer are continuously vacuum-deposited in the same vacuum chamber, it is particularly easy to change the deposition order of the two layers.

Subsequently, a friction reduction and anti-fingerprint layer is formed on the protective layer (S4). To this end, when the formation of the protective layer is completed, the friction reduction and fingerprint layer are vacuum-deposited on the protective layer continuously in the same deposition chamber. The friction reducing and anti-fingerprint layer may be formed of fluorine and silane. Fluorine and silane can be obtained from the product name OR-112. The friction-reducing and anti-fingerprint layer formed of fluorine and silane can improve the wear resistance by replacing the middle layer and top layer used to protect the surfaces of the light transmittance and reflectance control layers in the conventional method. The above-mentioned friction reduction and anti-fingerprint layer materials are fluorine and silane, and thus have low surface tension, thus preventing contamination of the substrate surface and easily being removed even when contaminated. In particular, the present invention has the effect of conforming to characteristic evaluations such as BB cream, lipstick, jeans, and complex ultraviolet rays by using fluorine and silane.

Therefore, the above-described protective layer, and the plastic coating, glass coating and metal coating obtained according to the present invention having the friction reduction and fingerprint are deformed or discolored due to wear or moisture penetration of the cell phone battery cover or the plastic substrate. In addition to this phenomenon, it plays a role in preventing fingerprints from being stained on the exterior of a cell phone battery cover or plastic glass metal substrate, and contaminated by dust, etc. In particular, it is prevented from contaminating the surface by BB cream, lipstick, jeans, and complex ultraviolet rays. .

In the embodiment illustrated in FIG. 1, a friction reduction and fingerprint resistant layer is formed on the protective layer, but according to another embodiment described above, on the contrary, a friction reduction and fingerprint resistant layer is formed on the transmittance and reflectance control layer. In particular, in the present invention, it is particularly easy to change the deposition order of the two layers because the transmittance and reflectance control layers, the protective layer, and the friction reduction and fingerprint resistant layers are continuously vacuum-deposited in the same vacuum chamber.

The process in which the light transmittance and reflectance control layer, the protective layer, and the friction reduction and inner order layer are continuously vacuum deposited in the same vacuum chamber is an electron beam (e-beam) vacuum deposition or sputtering vacuum deposition among vacuum deposition methods. Vacuum deposition can be performed at a vacuum level of, for example, 10-5 torr, under process conditions well known to the average person skilled in the art. In particular, when using a method of evaporating and depositing a target material by e-beam irradiation, an organic material and an inorganic material are alternately used easily and easily, while the transmittance and reflectance control layers, the protective layer, the friction reducing layer, and the fingerprint layer are the same vacuum. It can be deposited continuously in the chamber.

According to the multi-layer film coating method of the present invention, by using a hard base layer composition having a special chemical composition that can play the role of a conventional primer layer and a base layer together, multiple substrates are continuously deposited in one chamber without changing the setting. There is an effect that can carry out the process. In addition, the steps of forming the transmittance and reflectance control layer, the step of forming the protective layer, and the step of forming the friction reducing and fingerprint resisting layer are not carried out in separate places but may be carried out by a continuous deposition process in one and the same chamber. Can.

Therefore, the multi-layer film coating method of the present invention continuously forms a wet process of spray application and curing to form a hard undercoating layer, and a transmittance and reflectance control layer, a protective layer, and a friction reducing and anti-fingerprint layer continuously in one and the same chamber. It consists of a two-step process of the dry deposition process to form a high-quality multilayer film coating on a plastic cell phone case, a glass cell phone case, and a metal cell phone case. Therefore, according to the multi-layer film coating method of the simple process of the present invention, compared to the conventional coating method, the production cost can be slowed down and the productivity and yield can be greatly improved, and there is only one step of the ultraviolet irradiation process. Warping, cracking and yellowing can also be greatly reduced, and environmental problems caused by the use of large amounts of volatile organic compounds (VOC) can be minimized by minimizing the use of UV curable paints.

Therefore, according to the method for coating a multilayer film of the simple process of the present invention, it is possible to mass-produce economically high-quality multi-material mobile phone cases in a timely manner to meet market demands.

In addition, the plastic coating body, the glass coating body and the metal coating body such as the plastic cell phone case, the glass cell phone case and the metal cell phone case obtained by the multilayer film coating method of the present invention are more durable and resistant than the plastic coating body obtained by the conventional coating method. It has excellent properties such as wetness, abrasion resistance, scratch resistance, texture, stain resistance, weather resistance, anti-fingerprint and chemical resistance.

Therefore, the present invention not only protects the transmittance and reflectance control layer, which is a multi-layer coating layer, by using a specially designed primer layer and a rigid undercoating layer, but also protects the light transmittance and reflectance control layer using excellent performance vacuum-deposited silicon. At the same time, by applying friction reduction and anti-fingerprint layer made of fluorine and silane, it is possible to coat multiple substrates in one facility and coating method, thereby reducing additional facilities and processes. In addition, the plastic coating, glass coating and metal coating obtained according to the method of the present invention can exhibit light reflectance, hardness, anti-fingerprint effect and contamination resistance that cannot be realized in a plastic coating used as a conventional mobile phone case. .

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are intended to illustrate the invention and the scope of the invention is not limited thereby.

Preparation Example 1: Preparation of flexible undercoating composition used in Comparative Example

1.0 equivalent of dihydroxy-functional polymethacrylate polyol (Diol BD 1000 from Gold Schmidt, Germany) was placed in a four-necked round flask with a catalyst and a polymerization inhibitor, and then equipped with a condenser, stirrer, and thermometer to set the temperature to 40°C. The temperature was raised. Thereafter, 2 equivalents of isophorone diisocyanate trimer (manufactured by Olin, Inc., product name: LUXATE ITM 800) were placed in a dropping tube and dropped for 1 hour to react for 1 hour while maintaining 45°C. Thereafter, 1.1 equivalents of caprolactone acrylate was placed in a dropping tube and added dropwise for 30 minutes to maintain reaction at 65° C. until all the isocyanate groups disappeared, thereby preparing an ultraviolet curable polyurethane acrylate oligomer having a number average molecular weight of about 1,800.

800 g of polymethyl methacrylate (manufacturer: Mitsubishi Rayon Co., Ltd.) having a weight average molecular weight of about 300,000, 650 g of the ultraviolet curable polyurethane acrylate oligomer, 100 g of ethoxylated trimethylol propane triacrylate (trade name: TMPEOTA, Miwon Corporation), 1,6-hexanediol diacrylate (trade name: HDDA, Miwon Corporation) 250g, styrene monomer 1200g, photoinitiator (trade name: Irgacure 369, Ciba Specialty Chemicals) 30g, leveling agent (EBECRYL350, SK-UCB) stirred 10g Thus, a UV curable flexible undercoat layer having a viscosity of about 500 cps at 25°C was prepared.

Preparation Example 2: Preparation of hard undercoat composition used in Examples

600 g of propylene glycol monomethyl ether, 200 g of isopropyl alcohol, 710 g of ethyl acetate, 30 g of photoinitiator (trade name: Irgacure 369, Ciba Specialty Chemicals), 650 g of reactive monomer, 800 g of the ultraviolet curable polyurethane acrylate oligomer, leveling agent (EBECRYL350, SK -UCB) 10 g was stirred to prepare a UV curable hard undercoat layer having a viscosity of about 1500 cps at 25°C.

Example 1

A glass case for a smartphone having a thickness of 1.0 mm was mounted on a jig. Mounting the jig on the spindle spray line for manufacturing a mobile phone case, spraying the hard undercoating layer composition obtained in Preparation Example 2 onto the case, drying it at about 40°C to 50°C for about 2 to 3 minutes, and then irradiating it with ultraviolet light (Product name: Metal halide UV LAMP, manufacturer: Korea Ultraviolet Co., Ltd.) using a line speed of 13m/min to 14m/min, a wavelength range of about 250 to 450nm under curing conditions of 900 mJ/cm2 to 1000 mJ/cm2 Was irradiated with ultraviolet rays to form a hard undercoat layer having a thickness of 25±3㎛.

Subsequently, the jig is mounted in a vacuum evaporator, and a first pocket for receiving alumina (AI2O3) target material, a second pocket for receiving zirconia (ZrO2) target material, and a third for receiving silicon monoxide (SiO) target material, respectively A pocket, a fourth pocket containing fluorine and silane target materials, was mounted in the vacuum evaporator. Then, when the vacuum degree reaches 5.0x10-5 torr by evacuating the inner space of the vacuum evaporator, the e-beam is irradiated from the first pocket to adjust the transmittance and reflectance of the AI2O3 layer having a thickness of about 1500 Å over the hard undercoat layer. The layers were deposited. Then, the second pocket was irradiated with an e-beam to deposit a transmittance and reflectance control layer of a ZrO2 layer having a thickness of about 1000 Pa over the AI2O3 layer of 1500 Pa. The e-beam is again irradiated to the first pocket to deposit a transmittance and reflectance control layer of an AI2O3 layer having a thickness of about 1600 위에 over the 1000 Å ZrO2, and the e-beam is irradiated to the second pocket to be thick over the AI2O3 layer of 1600 Å. A transmittance and reflectance control layer formed of a multilayer film was formed by depositing a transmittance and reflectance control layer of about 1200 Å ZrO2 layer. Subsequently, an e-beam was irradiated to the third pocket to deposit a protective layer of a layer formed on the transmittance and reflectance control layer using SiO having a thickness of about 371 mm 3.

Subsequently, an e-beam is irradiated to the fourth pocket to continuously deposit a friction reduction and fingerprint layer of fluorine and silane having a thickness of about 150 위에 on the protective layer of the layer formed using the SiO to deposit a glass case coating for a smartphone. It was prepared.

2 is a photograph of a glass case coating prepared according to Example 1.

Example 2

Reflectivity and transmittance control, including an Al2O3 layer with a thickness of about 1550 mm2, a ZrO2 layer with a thickness of about 1010 mm2 on it, a Al2O3 layer with a thickness of about 1650 mm2, and a layer of about 1220 mm2 ZrO2 on it A glass case coating for a smartphone was prepared in the same manner as described in Example 1, except that the layer was deposited.

Example 3

Reflectivity and transmittance control, including an Al2O3 layer with a thickness of about 1600 mm2, a ZrO2 layer with a thickness of about 1060 mm2, a Al2O3 layer with a thickness of about 1700 mm2 on it, and a layer of about 1240 mm2 ZrO2 thereon A glass case coating for a smartphone was prepared in the same manner as described in Example 1, except that the layer was deposited.

Example 4

A metal case coating body for a smart phone was manufactured in the same manner as the method described in Example 1, except that a metal case for a smartphone having a thickness of 1.0 mm was mounted on a jig.

3 is a photograph of a metal case coating prepared in accordance with Example 4.

Example 5

A plastic case coating body for smarts was manufactured in the same manner as described in Example 1, except that a smartphone case having a thickness of 1.0 mm injection-molded with polycarbonate resin was mounted on a jig.

Comparative Example 1

A case for a smartphone having a thickness of 1.0 mm injection-molded with polycarbonate resin was mounted on a jig. The jig is mounted on a spindle spray line for manufacturing a mobile phone case, spray-coated the flexible base layer composition obtained in Preparation Example 1 onto the case, dried at about 40°C to 50°C for about 2 to 3 minutes, and then irradiated with ultraviolet ( Product name: Metal halide UV LAMP, manufacturer: Korea Ultraviolet Co., Ltd., using a line speed of 13m/min to 14m/min, and a UV wavelength of 900 mJ/cm2 to 1000 mJ/cm2 in curing conditions with a wavelength of about 250 to 450nm A flexible undercoat layer having a thickness of 25±3 μm was formed by irradiation with ultraviolet light.

Subsequently, the jig is mounted in a vacuum evaporator, and a first pocket for receiving alumina (AI2O3) target material, a second pocket for receiving titanium dioxide (TiO2) target material, and silicon monoxide (SiO) for receiving target material, respectively A third pocket and a fourth pocket containing a fluorine target material were mounted in the vacuum evaporator. Then, when the vacuum degree reaches 4.0x10-5 torr by evacuating the inner space of the vacuum evaporator, an e-beam is repeatedly irradiated to the first pocket and the second pocket to form an Al2O3 layer having a thickness of about 1500 Å over the flexible undercoat layer. , A light transmittance and reflectance control layer including a TiO2 layer having a thickness of about 1000 mm 2, an Al2O3 layer having a thickness of about 1,600 mm 2, and a TiO2 layer having a thickness of about 1,200 mm 2 thereon were deposited thereon.

Subsequently, an e-beam was irradiated to the third pocket to deposit a protective layer of a layer formed using SiO of about 100 mm 2 thickness on the light transmittance and reflectance control layer.

Subsequently, an e-beam was irradiated to the fourth pocket to continuously deposit a friction reducing layer of a fluorine layer having a thickness of about 100 mm 2 over the protective layer of the layer formed using SiO to prepare a plastic case coating for a smartphone.

Characteristic evaluation

The characteristics of the following items were evaluated for the case coating bodies for smartphones obtained in Examples 1 to 5 and Comparative Example 1. The evaluation method was as follows.

(1) Overall yield

According to the method described in each example and comparative example, 30 case coating bodies for smartphones were prepared, and yields were calculated according to the following formula from the number of good products.

Total yield = number of good products/30 × 100 (%).

When observed with the naked eye, when a crack occurred on the surface of the coating body, when the coating body was bent, or when foreign matter was formed on the coating body, all were regarded as defective products.

(2) Reflectance

The reflectance is soda-lime glass obtained by placing a soda-lime glass of a size similar to that of a case coating body for a smartphone into a vacuum evaporator and simultaneously depositing a multi-layer coating layer of a metal oxide or a mixture of a transmittance and reflectance control layer and a protective layer. The coating was measured using a spectrometer (product name: UV-5200, manufacturer: Mizubishi). The reference wavelength used for the measurement was 550 nm, and the transmittance of this light was measured and the reflectance was maintained at 25% using the following relationship.

Light reflectance (%) = 100- Light transmittance (%).

(3) pencil hardness

According to the methods and conditions specified in ASTM D3363-74, if the pencil is placed at a 45° angle on the surface of the coating and pushed under a load of 1 kg, the scratched pattern or fracture of the surface of the coating does not occur more than twice when measured 5 times. The hardness value was taken as the surface hardness value.

(4) Adhesion

The adhesion between the multi-layer film M/T coating layer and a glass substrate, a metal substrate or a polycarbonate substrate was evaluated according to the methods and conditions specified in ASTM D3359-87.

A cellophane tape with excellent adhesion is made by drawing 11 rows of each horizontally and vertically with a knife and making 100 squares of 2mm×2mm to reach the glass substrate, metal substrate, or polycarbonate substrate at 2 mm intervals on the surface of the coating body. And sharply remove it to close to an angle of 180°. This is repeated 3 times in the same position, and the criteria for determining adhesion are as follows:

Poor: Peeling occurs in one or more grids.

Excellent: Peeling does not occur on all grids.

However, the triangular shape of the edges of the grid was not considered in the judgment.

(5) Antifouling property and decontamination property

After using the blue oil-based magic to line the surface of the coating in a direction of 45 degrees, the ink was completely dried and then rubbed with a clean cloth to determine the condition of the naked eye. It evaluated by the following criteria.

Excellent: the ink is completely removed from the rubbed surface.

Poor: Ink is not completely removed from the rubbed surface.

(6) Water absorption rate

The water absorption was determined by placing the coating inside the thermo-hygrostat at 100% humidity and 25°C and measuring the weight change after 24 hours.

(7) Bending characteristics

It was evaluated based on the following criteria by visually observing whether the surface layer or the material is cracked when the both ends of the coating body are held and bent at 90 degrees or 180 degrees.

Excellent: Coated cotton remains intact

Normal: Cracks occur in the same direction as the bending direction.

Poor: Cracks occurred in all directions.

(8) BB cream

When buried in BB cream for 1 hour, it was evaluated based on whether the surface of the coating was contaminated.

Excellent: No contamination on the surface.

Poor: There is contamination on the surface.

(9) Lipstick

When the lipstick was smeared for 1 hour, it was evaluated based on whether the surface of the coating was contaminated.

Excellent: No contamination on the surface.

Poor: There is contamination on the surface.

(10) Jeans

When soaked in jeans dye for 1 hour, it was evaluated based on whether the surface of the coating was contaminated.

Excellent: No contamination on the surface.

Poor: There is contamination on the surface.

(11) Compound ultraviolet rays

When irradiated with composite ultraviolet rays for 1 hour, it was evaluated based on whether the surface of the coating was contaminated.

Excellent: No contamination on the surface.

Poor: There is contamination on the surface.

Table 1 summarizes the properties evaluation results for the smartphone case coating obtained in Examples 1 to 5 and Comparative Example 1.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Overall yield 94.5% 94.3% 94.0% 94.5% 94.5% 93.4% reflectivity 26% 28.5% 30%
25% 25% 21% Pencil hardness 5H or more 5H or more 5H or more 4H or more 4H or more 2H Adhesion with substrate Great Great Great Great Great Great Antifouling Great Great Great Great Great Great Contaminant desorption Great Great Great Great Great Great Water absorption 0.22% 0.2% 0.21% 0.22% 0.22% 0.22% Bending properties Great Great Great Great Great Great BB Cream Great Great Great Great Great Bad lipstick Great Great Great Great Great Bad Blue jeans Great Great Great Great Great Bad Compound ultraviolet rays Great Great Great Great Great Bad

Referring to Table 1, in the case of Examples 1 to 3 according to the present invention (glass substrate), as in Comparative Example 1, it can be seen that the overall yield is all higher than 90%, pencil hardness, adhesion to the substrate, It can be seen that a coating with excellent antifouling properties, contaminant desorption properties, moisture absorption rate, and bending properties can be obtained in good yield. In particular, by using zirconia, it can be confirmed that Examples 1 to 5 according to the present invention were higher in Comparative Example 1 in pencil hardness. In addition, by mixing the fluorine and silane to form a friction reduction and anti-fingerprint layer, it can be seen that Examples 1 to 5 according to the present invention are superior to BB cream, lipstick, jeans, and complex UV-resistant than Comparative Example 1 .

S1: hard base layer formation step
S2: Transmittance and reflectance adjustment layer forming step
S3: protective layer forming step
S4: friction reduction and fingerprint layer formation step

Claims (8)

Forming a rigid underlayer on one of the plastic substrate, the glass substrate, and the metal substrate;
Forming a transmittance and reflectance control layer comprising alumina (Al2O3) and zirconia on the hard base layer;
Forming a protective layer on the transmittance and reflectance control layer using silicon monoxide (SiO); And
Forming a friction reducing and anti-fingerprint layer comprising fluorine and silane on the protective layer,
The hard base layer,
Contains propylene glycol monomethyl ether, isopropyl alcohol, ethyl acetate, photoinitiators, reactive monomers and oligomers,
The hard base layer,
15 to 20 parts by weight of the propylene glycol monomethyl ether, 15 to 25 parts by weight of the ethyl acetate, 1 to 5 parts by weight of the photoinitiator, 15 to 25 parts by weight of the reactive monomer, and the oligomer based on 100 parts by weight of the total composition Contains 20 to 30 parts by weight,
The hard base layer has a viscosity of 1000 cps to 2000 cps, characterized in that the multi-layer multilayer film coating method. Forming a hard undercoating layer on one of the plastic substrate, the glass substrate and the metal substrate;
Forming a protective layer using silicon monoxide (SiO) on the hard undercoat layer;
Forming a transmittance and reflectance control layer comprising alumina (Al2O3) and zirconia on the protective layer; And
And forming a friction reducing and anti-fingerprint layer comprising fluorine and silane on the transmittance and reflectance control layer,
The hard base layer,
Propylene glycol monomethyl ether, isopropyl alcohol, ethyl acetate, photoinitiators, reactive monomers and oligomers,
The hard base layer,
15 to 20 parts by weight of the propylene glycol monomethyl ether, 5 to 15 parts by weight of the isopropyl alcohol, 15 to 25 parts by weight of the ethyl acetate, 1 to 5 parts by weight of the photoinitiator, and the reactivity based on 100 parts by weight of the total composition The monomer contains 15 to 25 parts by weight and the oligomer contains 20 to 30 parts by weight,
The hard base layer has a viscosity of 1000 cps to 2000 cps, characterized in that the multi-layer multilayer film coating method. delete delete Glass substrates;
A hard undercoat layer formed on the glass substrate;
A transmittance and reflectance control layer including alumina (Al2O3) and zirconia as a transmittance and reflectance control layer formed on the hard undercoat layer;
A protective layer formed using silicon monoxide (SiO) as a protective layer formed on the transmittance and reflectance control layer; And
Friction reduction and anti-fingerprint layer formed on the protective layer, including fluorine and silane
The hard base layer,
Contains propylene glycol monomethyl ether, isopropyl alcohol, ethyl acetate, photoinitiators, reactive monomers and oligomers,
The hard base layer,
15 to 20 parts by weight of the propylene glycol monomethyl ether, 5 to 15 parts by weight of the isopropyl alcohol, 15 to 25 parts by weight of the ethyl acetate, 1 to 5 parts by weight of the photoinitiator, and the reactivity based on 100 parts by weight of the total composition The monomer contains 15 to 25 parts by weight and the oligomer contains 20 to 30 parts by weight,
The rigid base layer has a viscosity of 1000 cps to 2000 cps, characterized in that the friction reduction and the glass coating comprising a fingerprint layer. Glass substrates;
A hard undercoat layer formed on the glass substrate;
A protective layer formed using silicon monoxide (SiO) as a protective layer formed on the hard undercoat layer;
A transmittance and reflectance adjustment layer including alumina (Al2O3) and zirconia as a transmittance and reflectance adjustment layer formed on the protective layer; And
A friction reduction and anti-fingerprint layer formed on the transmittance and reflectance control layer, including a friction reduction and anti-fingerprint layer comprising fluorine and silane,
The hard base layer,
Contains propylene glycol monomethyl ether, isopropyl alcohol, ethyl acetate, photoinitiators, reactive monomers and oligomers,
The hard base layer,
15 to 20 parts by weight of the propylene glycol monomethyl ether, 5 to 15 parts by weight of the isopropyl alcohol, 15 to 25 parts by weight of the ethyl acetate, 1 to 5 parts by weight of the photoinitiator, and the reactivity based on 100 parts by weight of the total composition The monomer contains 15 to 25 parts by weight and the oligomer contains 20 to 30 parts by weight,
The rigid coating layer has a viscosity of 1000 cps to 2000 cps, characterized in that the glass coating. delete The method of claim 5 or 6,
The glass coating is a mobile phone case, tablet PC case, notebook PC case, automobile, or PDA (personal digital assistant) case is a glass coating.

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