WO2010056056A2 - Deposition-free mirror-like color coating material - Google Patents

Abstract

Provided is a deposition-free mirror-like color coating material which can achieve mirror-like colors on a variety of materials, which can be implemented through a simple process, and which can produce color images comparable to the mirror-like color images which can be obtained by a deposition method. The deposition-free mirror-like color coating material of the present invention has a special coating layer structure, thereby remarkably improving the quality of mirror-like colors, and thus can be valuably applied to electronics, home appliances, and inner/outer parts of vehicles.

Description

Deposition-free mirror color coating

The present invention relates to a non-deposited mirror color coating that embodies a color (hereinafter referred to as mirror color) that exhibits a mirror-like feel.

With the development of ICT and industry, there are many demands of consumers for the design of mobile, electronic home appliances and exterior materials in automobiles. In addition to the functional design, the aesthetic and sensual design has also emerged as the importance of sensational design beyond the functions such as visual feeling through the color and sensational touch through the touch. The industry is leading the development of sensory designs to meet customer needs.

In recent years, mobile and home appliances have been using a lot of silver in the design trend to provide a mirror color.

2 is a cross-sectional view of a mirror color coating prepared through a conventional painting process. As shown in the drawing, a one-component silver lacquer resin is directly coated on a substrate, and after drying, a urethane resin or an ultraviolet curable resin is coated. Due to the limitation of the coating process, such a conventional mirror color coating material has a low brightness of the mirror color, which is significantly inferior to the mirror color feeling obtained through the deposition or plating method, and thus the technical competitiveness is remarkably inferior.

Therefore, a method of implementing a mirror color using deposition or plating instead of a coating process has been used in recent years. 3 is a cross-sectional view of a mirror collar structure produced by a conventional deposition process. As shown, after the primer treatment on the top of the substrate to move to the deposition apparatus to deposit a silver layer and then moved again to the primer treatment to form a top coat layer.

However, such deposition or plating has high brightness, but the production process is very complicated due to the complicated process, and the defect rate is very high due to the movement between processes, which is unproductive, difficult to apply to various materials, and required by each industrial part. It does not satisfy the problem.

The present invention is to solve the above problems, it is possible to implement a mirror color on a variety of materials, and the process is not only simple, but also compared to the mirror color image that can be obtained by evaporation method is not inferior to the mirror color coating material It aims to provide.

It is also an object of the present invention to provide a non-deposited mirror color coating that can significantly improve the quality of a mirror collar by having a special layer structure, which can be applied to electronic home appliances and automobile interior / exterior materials.

As a means for achieving the above object,

The present invention is an undercoat coating layer formed on the substrate; A mirror color coating layer formed on the bottom coating layer; It provides a non-deposited mirror color coating comprising a; and a top coat layer formed on the mirror color coating layer.

In addition, the bottom coating layer provides a non-evaporated mirror color coating, characterized in that formed of an ultraviolet curable resin composition, or a urethane two-component resin composition, or a heat-dried one-component lacquer resin composition.

In addition, the mirror color coating layer provides a non-deposited mirror color coating, characterized in that formed of a lacca resin composition to which aluminum paste or silver paste is added.

In addition, the UV-curable resin composition is a POMG added PTMG polyurethane acrylate resin is added, preferably provides a non-deposited mirror color coating, characterized in that added to within the range of 3 to 20 parts by weight relative to the total 100 weight of the composition. do.

In addition, a urethane two-component resin composition, or a heat-dried one-component lacquer resin composition is a non-deposited mirror, characterized in that a PTMG resin added with PO is added, preferably added in the range of 3 to 20 parts by weight based on 100 parts by weight of the total composition Provide a color coating.

In addition, the substrate provides a non-deposited mirror color coating, characterized in that the synthetic resin plate or a metal plate.

In addition, the brightness of the vapor-deposited mirror color coating is provided with a vapor-deposited mirror color coating is characterized in that at least 70% of the brightness of the mirror color structure formed after the silver deposition layer formed on the top of the substrate and the top coat layer formed. do.

In addition, the brightness of the non-deposited mirror color coating provides a non-deposited mirror color coating, characterized in that 300% or more of the brightness of the non-deposited mirror color coating in the case of omitting the undercoat coating layer.

According to the present invention having the above-described structural features, a mirror color must be implemented through complex processes such as plating and deposition, and a mirror layer having a specific structure can be implemented to implement a similar mirror color in a general coating process such as spray coating. The resin composition and the painting process for implementing the mirror color according to the present invention have applicability to various materials, excellent appearance, and physical and chemical properties, and also provide a cost effective product reduction by a very efficient painting process.

1 is a schematic cross-sectional view of a vapor deposition mirror color coating according to an embodiment of the present invention;

2 is a cross-sectional view of a mirror color coating prepared by a conventionally used painting process,

3 is a cross-sectional view of a mirror collar structure produced by a conventional deposition process.

** Description of the main symbols in the drawings **

1: description

2: undercoat coating layer

3: mirror color coating layer

4: top coat layer

Hereinafter, the present invention will be described in more detail with reference to the drawings and examples. The following description is intended to assist in the understanding of the present invention by describing specific or optimal examples, so that there may be definite or limited expressions, but it is not intended to limit the scope of rights defined by the claims. On the other hand, the non-deposition in the present invention means that the mirror color coating layer is not formed by the vapor deposition method, and does not exclude the vapor deposition method in the formation of other additional coating films or other structures.

1 is a cross-sectional view of a vapor deposition mirror color coating according to an embodiment of the present invention. As shown, the bottom coating layer 2 formed on the substrate 1, the mirror color coating layer 3 formed on the bottom coating layer 3, and the top coating layer 4 formed on the mirror color coating layer 3; Characterized in that made. All of the coating layers can be formed by a painting process and can be manufactured in a very simple process. That is, after coating the undercoat coating layer 2 on the substrate 1 first, the mirror color coating layer 3 may be coated on top of the substrate 1, and then the top coat coating layer 4 may be applied to realize the mirror color.

The mirror color of the present invention is very excellent in design and brightness as compared to the conventional coating of the UV-curable resin composition for the top coat after the silver lacquer coating without a coat coat layer, it is possible to implement a design and brightness similar to deposition.

Hereinafter, each configuration will be described in detail.

(1) mention

The base material 1 is not particularly limited. It may be a synthetic resin plate or a metal plate, and for example, various materials such as PC, PMMA, ABS, PC / ABS, PC / GF, magnesium, aluminum, SUS, and PLA may be selected and applied.

In the present invention, it is characterized in that the undercoat coating layer 2 which is a special layer on the base 1 is formed. Through this, it was found that significantly improved luminance can be obtained compared to forming the mirror color coating layer immediately after forming the mirror color coating layer or simply performing a primer treatment.

This is thought to be because the coating layer prevents the surface of the substrate from being microscopically adversely affecting the mirror color coating layer formed thereon, resulting in a decrease in luminance.

(2) undercoat coating layer

The undercoat coating layer 2 may be coated through a coating process using a general coating composition. Preferably, it is preferably formed by coating with an ultraviolet curable resin composition, a urethane two-component resin composition, or a heat-dried one-component lacquer resin composition. The resin compositions enumerated above may be used in any of the resin compositions known or applicable in the art and are not limited.

In particular, more preferably, the UV curable resin composition, the urethane two-component resin composition, or the heat-dried one-component lacquer resin composition is a polytetramethylene glycol (PTMG) resin to which PO (Propylene Oxide) is added, or a PTMG to which PO is added. The addition of the polyurethane acrylate resin was excellent as shown in the examples below.

Preferably, PTUV polyurethane acrylate resin to which PO was added was added to the ultraviolet curable resin composition, and it was confirmed that it was excellent to add PTMG resin to which PO was added to the urethane two-component resin composition or the heat-dried one-component lacquer resin composition.

The content of PTMG resin added with PO or PTMG polyurethane acrylate resin added with PO is not limited, but UV curable resin or urethane 2-component resin composition or heat-dried one-component lacquer resin composition ranges from 3 to 20 parts by weight based on a total of 100 weight It is good to be added into.

Poly TetraMethylene Glycol (PTMG) resin to which PO (Propylene Oxide) is added is formed by reacting PO with PTMG, and the ratio of PO and PTMG is not limited but may be in a range of 20:80 to 50:50 by weight. PTMG is not limited, but it is preferable to use one having a molecular weight of 1000 to 4000.

PTMG may have a high crystallinity and may have a problem of poor elongation when added as it is. Therefore, in the present invention, elongation can be increased by adding PO, thereby improving workability and further improving at least one of adhesion, acid resistance, and wear resistance.

PO-added PTMG polyurethane acrylate resin is formed by reacting an isocyanate having an acryl group with a PO-added PTMG resin, or by reacting a PO-added PTMG, diisocyanate, and hydroxyalkyl acrylate. (Acrylate in the present invention is a broad meaning including methacrylate).

As a specific example, the urethane (meth) acrylate synthesized with PTMG to which PO having a molecular weight of 1000 to 4000 is added is PTMG to which PO having a molecular weight of 1000 to 4000 is added; Diisocyanate; And hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), hydroxybutyl acrylate (HBA) hydroxyethyl methacrylate (2-HEMA), and mixtures thereof. Synthesized is preferred.

The diisocyanate is hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 1,4-tetramethylene diisocyanate, 1,10-decamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate Isocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 1,5-naphthalene diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-chloro-1,3- Phenylene diisocyanate, 2,4-dimethyl-1,3-phenylene diisocyanate, 4,4- diisocyanate diphenyl ether, 4,4- diisocyanate dibenzyl, methylene-bis (4-phenyl isocyanate)- It is preferably selected from the group consisting of 1,3-phenylene diisocyanate and mixtures thereof.

Advantages of adding PO added PTMG resin or PO added PTMG polyurethane acrylate resin are as follows.

In general, when applying a mirror color after applying the UV curable resin composition and the urethane resin composition to the substrate, due to the high crosslinking density of the surface of the coating film through the UV curing reaction and the urethane curing reaction, the coating film formation during the spray coating of the silver lacquer coating Uneasy. That is, in general, due to the deterioration of the wetting, the coating film may be unstablely formed or the lack of the interlayer adhesion due to the addition of the wetting enhancer may be caused to cause problems of reliability. On the other hand, a method of lowering the crosslinking density by adjusting the crosslinking density of the ultraviolet curing reaction and the urethane curing reaction may be considered, but in this case, the coating film applied to the substrate by a solvent used for workability, etc., in spray coating of the silver lacquer paint may be considered. This can affect the swelling or melting of the coating layer.

However, it has been found that the above problems can be solved considerably as a result of adding a PTMG resin to which PO is added or a PTMG polyurethane acrylate resin to which PO is added to an ultraviolet curable resin composition or a urethane resin composition.

Hereinafter, the preferable example of each resin composition is demonstrated concretely.

UV curable resin composition includes 20 to 50 parts by weight of polyurethane acrylate resin having 2 to 6 reactive acrylates in one molecule, and 0 to 40 parts by weight of polyester acrylate resin having 2 to 4 reactive acrylates in one molecule Part, 5 to 20 parts by weight of PTMG polyurethane acrylate resin added with PO. As diluent monomers, trimethylolpropane triacrylate (TMPTA), hexamethylene diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA) hydroxyethyl acrylate acrylate (HEA), hydroxypropyl acrylate (HPA), hydroxybutyl acrylate (HBA), isobonyl acrylate (IBOA), hydroxyethyl methacrylate (hydroxyethyl meta acrylate: 2-HEMA), etc., 10-30 weight, 2-hydroxy-1-4- [4- (2-hydroxy-2-methylpropionyl) by Ciba Specialty Chemicals as photopolymerization initiator -Benzyl] phenyl-2-2-methyl propane-1-one (Irgacure 127), 1-hydroxy cyclohexyl phenyl ketone (Irgacure 184), 2-benzyl-2- (dimethylamino) -1- [4- (4- Polyvinyl) 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 are used in an amount of 1.5 to 5 parts by weight. Examples of the solvent include methylisobutyl ketone, methylethyl ketone, dimethyl ketone, isopropyl alcohol, isobutyl alcohol and normal butyl alcohol ), Ethyl acetate, normal butyl acetate, ethyl cellusolve, ethyl cellusolve, butyl cellusolve, toluene, xylene, etc. Can be used.

In the case of the polyurethane acrylate resin and the polyester acrylate resin used above, the content and type may vary depending on the substrate.

Although not limited to the urethane two-component resin composition, polyols and isocyanate curing agents can be used. As the polyol, one or a combination of acrylic polyol, polyester polyol and modified acrylic polyol may be used.

Each of the polyols is classified by molecular weight and OH%. Generally, acrylic polyols used in mobile and home appliances have a molecular weight of 2,000 to 50,000, and OH% is 1 to 3% by 5 to 40 parts by weight, preferably 10 to 30 parts by weight of the molecular weight of 10,000 to 30,000 and OH% of 1 to 2%, 5 to 40 parts by weight of polyester polyol of the molecular weight of 5,000 to 30,000 and OH% of 1 to 3%, preferably molecular weight 5 to 15 parts by weight of 10,000 to 20,000 and 1 to 2% of OH%, and 5 to 40 parts by weight of modified acrylic polyol having a molecular weight of 5,000 to 80,000 and 0.5 to 5% of OH%, preferably having a molecular weight of 5 to 15 parts by weight of 10,000 to 20,000 and 1 to 2% of OH%, 5 to 20 parts by weight of PTMG synthetic resin with PO, and methyl isobutyl ketone (methylisobutyl) ketone, methylethyl ketone, dimethyl ketone, ethyl acetate, normal 40-60 parts by weight of butyl acetate, ethyl cellusolve, butyl cellusolve, toluene and xylene are used.

As the curing agent, isocyanates used for urethane reactions are preferably aliphatic or aromatic diisocyanates having two or more functional groups. For example, 1,6-hexamethylene diisocyanate, isophore Isophorene diisocyanate, 1,4-cyclohexyl diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylene diisocyanate diisocyanate) such as diisocyanate is used, and its type is changed according to workability, but in general, 1 ~ 6-hexamethylene diisocyanate (1,6-hexamethylene diisocyanate) is coated with 5 ~ 20 weight 35% by weight.

The heat-drying one-component lacquer resin composition includes 1/16 to 2000 in nitro cellulose (NC) RS TYPE, 1/8 to 1/2 in SS TYPE, and acrylic resin molecular weight 10,000 to 200,000. And there is a glass transition temperature (Tg) 20 ~ 100, as a vinyl resin (vinyl alcohol), vinyl acetate (vinyl acetate), vinyl chloride (vinyl chrolide) according to the ratio of VAGH, VMCA, cellulose Resin such as acetate butyrate resin (CAB) can be used.

Preferably, the nitro cellulose (NC) RS TYPE is 1/8 ~ 1000, 10 ~ 30 parts by weight, SS TYPE 1/8 ~ 1/2 is 5 ~ 30 parts by weight, acrylic resin molecular weight 10,000 0 to 30 parts by weight of 100 to 100 and a glass transition temperature (Tg) of 20 to 100, and the ratio of vinyl alcohol, vinyl acetate, and vinyl chromide as vinyl resin. According to VAGH, VMCA 10-30 parts by weight, cellulose acetate butyrate resin (CAB) 10-30 parts by weight. 3-10 weight part of PTMG synthetic resin to which PO was added can be used.

Solvents for effective spraying include methylisobutyl ketone, methylethyl ketone, dimethyl ketone, isopropyl alcohol, isobutyl alcohol and normal Butyl alcohol, ethyl acetate, normal butyl acetate, ethyl cellusolve, butyl cellusolve, toluene, xylene 30 to 70 parts by weight is used.

(3) mirror color coating layer

The mirror color coating layer 3 may provide a mirror color and may be used without limitation as long as it is a material capable of forming a coating film by a coating process such as a painting process. Preferably, a resin composition containing aluminum paste or silver paste is preferable, and an example of the resin composition is a lacca resin composition.

Specifically, the lacca resin composition containing aluminum paste is 0-40 parts by weight of 1/16 to 2000 in Nitro cellulose (NC) RS TYPE, and 0 to 40 in 1/8 to 1/2 in SS TYPE. Parts by weight, acrylic resin molecular weight 10,000-200,000 and glass transition temperature (Tg) 20-98 0-40 parts by weight, vinyl alcohol, vinyl acetate, vinyl chromide as vinyl resin Depending on the ratio of (vinyl chrolide), VAGH, VMCH 0-40 parts by weight, cellulose acetate butyrate resin (CAB) 0-40 parts by weight, AL paste to give a sense of mirror, uncoated AL paste 2 ~ 8 parts by weight, and methyl isobutyl ketone, methyl ethyl ketone, dimethyl ketone, isopropyl alcohol, isobutyl alcohol, normal as solvent Butyl alcohol, at 30 to 60 parts by weight of ethyl acetate, normal butyl acetate, ethyl cellusolve, butyl cellusolve, toluene and xylene Can be used.

(4) top coat layer

The top coat layer 4 may protect the mirror color coat layer and adjust color, gloss, and the like. The material may be selected from materials known or applicable in the art, and examples thereof include conventional UV curable resins.

The top coat layer may have a multilayer structure. As an example, various functional layers may be added to implement a specific texture or color. As an example, a top coat layer can be formed by using a textured urethane two-component paint. In the case of commercially available textured paints, surface textures are indicated by the use of matting agents and waxes through the dry solvent. However, in order to apply such a textured paint, it is necessary to protect the mirror color coating layer. This is because the orientation of the silver that implements the mirror color is vulnerable to a solvent, such as a solvent, a coating of a mirror color coating layer and a protective coating film of the acrylic resin composition, and a textured urethane two-component coating.

The non-deposited mirror color coating according to the embodiment of the present invention may be prepared through the following coating process.

First, in the case of the base material, in order to remove the release agent and contaminants, the process is washed with isopropyl alcohol (IPA), and then the coating layer is coated on the base material so that the film thickness is 6 to 15 μm, and then 1 to 3 minutes at 60 ° C. After drying, the amount of light is UV cured at 900mj, or the urethane two-component composition or the one-component lacquer composition is coated so that the coating film thickness is 6-15 µm and dried at 80 ° C for 30 minutes.

After that, the middle aluminum paste lacquer composition is coated on the upper surface of the undercoat layer with a coating thickness of 1 to 5 μm and dried at 60 to 80 ° C. for 3 to 10 minutes to form a mirror color coating layer. By coating with UV and curing under UV light, a mirror color coating can be obtained simply by a coating process. It is possible to use only the painting process, so it is well suited for a series of continuous automation processes and thus has excellent productivity.

This coating process is much more efficient than the deposition and plating processes currently in use. For example, in the deposition process, a primer for deposition is coated on a PC material that is reliable for deposition, and topcoat UV and urethane are coated to protect the deposition film after deposition. However, the physical properties of the deposited film and the top UV and urethane resin are not sufficient, so the primer coating and the top UV and urethane resin coating are performed after the deposition, which requires a lot of processes, and sputtering, CVD (Chemical Vapor Deposition) and PVD ( physical vapor deposition, etc., which is an independent process due to the lack of current automated line equipment. Therefore, the implementation of the mirror color through deposition is not very efficient because the continuous process is not performed.

The non-deposited mirror color coating according to the present invention is minimized in the loss of brightness as compared to forming the mirror color layer as a deposition layer can be used industrially without difficulty. As can be seen in the experiments described later, the non-deposited mirror color coating according to the present invention is primed on top of the substrate, the silver deposition layer is formed and the top coat layer is formed 70% or more of the brightness of the mirror color structure, most of which is 80% It can be seen that the above is provided.

In addition, the brightness of the non-deposited mirror color coating according to the present invention, as shown in the experiments described below, provide 300% or more of the brightness of the non-deposited mirror color coating in the case of omitting the undercoat coating has been seen very technically advanced Can be.

Preparation of Resin Compositions

Preparation Example 1

15 parts by weight of polyurethane acrylate (EB-1290, SK UCB) with 6 reactive acrylates in one molecule, 8 parts by weight of polyurethane acrylate (EB-9270, SK UCB) with 2 reactive acrylates in one molecule 7 parts by weight of PTMG polyurethane acrylate resin to which PO was added. 10 parts by weight of trimethylolpropane triacrylate (TMPTA), a reactive monomer, 7 parts by weight of tripropylene glycol diacrylate (TPGDA), Irgacure 184 (Ciba Specialty Chemical) as a photoinitiator used for UV curing. G) 3 parts by weight, 10 parts by weight of methyl ethyl ketone, 10 parts by weight of ethyl acetate, 10 parts by weight of normal butyl acetate, and ethyl cellulose to enable the spray process. An ultraviolet curable resin composition having 10 parts by weight of an ethyl cellulose, 5 parts by weight of toluene, and 5 parts by weight of xylene is prepared by a conventional manufacturing method.

Preparation Example 2

10 parts by weight of polyurethane acrylate (EB-1290, SK UCB) with 6 reactive acrylates in one molecule, 10 parts by weight of polycarbonate urethane acrylate (Oligomer-1, SSCP) with 2 reactive acrylates in one molecule 10 parts by weight of PTMG polyurethane acrylate resin to which PO was added. 10 parts by weight of trimethylolpropane triacrylate (TMPTA), a reactive monomer, 7 parts by weight of tripropylene glycol diacrylate (TPGDA), Irgacure 184 (Ciba Specialty Chemical) as a photoinitiator used for UV curing. G) 3 parts by weight, 10 parts by weight of methyl ethyl ketone, 10 parts by weight of ethyl acetate, 10 parts by weight of normal butyl acetate, and ethyl cellulose to enable the spray process. An ultraviolet curable resin composition having 10 parts by weight of an ethyl cellulose, 5 parts by weight of toluene, and 5 parts by weight of xylene is prepared by a conventional manufacturing method.

Preparation Example 3

10 parts by weight of polyurethane acrylate (EB-1290, SK UCB) with 6 reactive acrylates in one molecule, 20 parts by weight of polyurethane acrylate (EB-9270, SK UCB) with 2 reactive acrylates in one molecule Part, 10 parts by weight of PTMG polyurethane acrylate resin added with PO, 5 parts by weight of trimethylolpropane triacrylate (TMPTA) as a reactive monomer, and 3 parts of tripropylene glycol diacrylate (TPGDA) 7 Parts by weight, 3 parts by weight of Irgacure 184 (Ciba Specialty Chemicals) as a photoinitiator used for UV curing, 5 parts by weight of methyl ethyl ketone, 10 parts by weight of ethyl acetate, to enable the spray process 10 parts by weight of normal butyl acetate, 10 parts by weight of ethyl cellusolve, 5 parts by weight of toluene, and Alkylene (xylene) is prepared by a conventional method for producing the 5 parts by weight of ultraviolet curable resin composition.

Preparation Example 4

15 parts by weight of polyurethane acrylate (EB-1290, SK UCB) with 6 reactive acrylates in one molecule, 15 parts by weight of polycarbonate urethane acrylate (Oligomer-1, SSCP) with 2 reactive acrylates in one molecule Part, 5 parts by weight of trimethylolpropane triacrylate (TMPTA), which is a reactive monomer, 10 parts by weight of PTMG polyurethane acrylate resin added with PO, 7 parts by weight of tripropylene glycol diacrylate (TPGDA) 3 parts by weight of Irgacure 184 (Ciba Specialty Chemicals) as a photoinitiator used for ultraviolet curing, 5 parts by weight of methyl ethyl ketone, 10 parts by weight of ethyl acetate to enable the spray process , 10 parts by weight of normal butyl acetate, 10 parts by weight of ethyl cellusolve, toluene 5 The ultraviolet curable resin composition which is a weight part and 5 weight part of xylene is manufactured by a conventional manufacturing method.

Preparation Example 5

18 parts by weight of polyurethane acrylate (EB-1290, SK UCB) with 6 reactive acrylates in one molecule, 7 parts by weight of polyurethane acrylate (EB-9270, SK UCB) with 2 reactive acrylates in one molecule part. , 5 parts by weight of PTMG polyurethane acrylate resin added PO. 10 parts by weight of trimethylolpropane triacrylate (TMPTA), a reactive monomer, 7 parts by weight of tripropylene glycol diacrylate (TPGDA), Irgacure 184 (Ciba Specialty Chemical) as a photoinitiator used for UV curing. G) 3 parts by weight, 10 parts by weight of methyl ethyl ketone, 10 parts by weight of ethyl acetate, 10 parts by weight of normal butyl acetate, and ethyl cellulose to enable the spray process. An ultraviolet curable resin composition having 10 parts by weight of an ethyl cellulose, 5 parts by weight of toluene, and 5 parts by weight of xylene is prepared by a conventional manufacturing method.

Preparation Example 6

A molecular weight of 10,000 OH% polymerized using a hydroxy acrylic monomer is 20 parts by weight of an acrylic polyol (AP-1.SSCP) having 2%, and a polyester polyol (PE-1.SSCP) having a molecular weight of 15,000 OH% of 1.5%. 10 parts by weight, 10 parts by weight of modified acrylic polyol (SAP-1.SSCP) having a molecular weight of 45,000 OH% of 1.5%, and 5 parts by weight of PTMG synthetic resin (KDS-1.SSCP) added with PO methylisobutyl ketone 10 parts by weight of ketone, 5 parts by weight of methyl ethyl ketone, 10 parts by weight of dimethyl ketone, 10 parts by weight of ethyl acetate, 10 parts by weight of normal butyl acetate, 5 parts by weight of toluene and 5 parts by weight of xylene are prepared by a conventional production method.

Preparation Example 7

12 parts by weight of BR-73 (molecular weight 85000, Tg 100) for acrylic resin, 13 parts by weight of VMCH for vinyl resin, 5 parts by weight of PTMG synthetic resin (KDS-1.SSCP) with PO and methyl isobutyl as solvent 20 parts by weight of methylisobutyl ketone, 20 parts by weight of methylethyl ketone, 10 parts by weight of normal butyl alcohol ethyl acetate, 10 parts by weight of ethyl cellusolve, 5 parts of toluene To 5 parts by weight of xylene (xylene) is mixed to prepare a conventional method.

<Production of Medium Silver Lacquer Composition>

The present invention relates to an intermediate silver lacquer resin composition (Production Example 8) and a general silver lacquer resin composition (Comparative Example 1) and vapor deposition (Comparative Example 2) which are currently used for implementing a mirror color.

Preparation Example 8

Nitro cellulose (NC) RS TYPE 10 parts by weight RS-1 / 2, Nitro cellulose (NC) SS TYPE SS-1 / 4 10 parts by weight, acrylic resin BR- 73 (Molecular Weight 85000, Tg 100) 5 parts by weight, 10 parts by weight of VMCH as vinyl resin, 10 parts by weight of cellulose acetate butyrate resin (CAB), AL not coated with AL paste to give mirror color 5 parts by weight of paste, and 10 parts by weight of methylisobutyl ketone as solvent, 10 parts by weight of methylethyl ketone, 10 parts by weight of normal butyl alcohol ethyl acetate, ethyl cellusolve 10 parts by weight, 5 parts by weight of toluene, and 5 parts by weight of xylene are mixed to prepare a conventional method.

Comparative Production Example 1

Currently commercially available silver lacquer resin composition, 15 parts by weight of BR-73 (molecular weight 85000, Tg 100) as acrylic resin, 15 parts by weight of VMCH as vinyl resin, 5 parts by weight of uncoated AL paste, and methyl iso 20 parts by weight of methyl isobutyl ketone, 10 parts by weight of methyl ethyl ketone, 10 parts by weight of normal butyl alcohol ethyl acetate, 10 parts by weight of ethyl cellusolve, toluene 10 By weight, 5 parts by weight of xylene are mixed to prepare by a conventional production method.

Comparative Production Example 2

Tin deposition was carried out in the form of eva in the sputtering method to the current commercial deposition method. In the case of the material, it was applied to the PC substrate which is widely used in mobile.

<Example 1>

The resin composition manufactured by the manufacture example 1 is subjected to a painting process to the PC base material with the structure similar to FIG. At this time, in the case of undercoat UV, a coating film was formed with a thickness of 8 μm, and dried for 1 minute at 60 ° C., followed by ultraviolet curing (900mj). Thereafter, the resin composition prepared in Preparation Example 8 was diluted 1: 1.5 with a diluent (700 diluent, SSCP) and spray-coated to have a coating thickness of 3 μm, and then dried at 60 to 80 ° C. for 5 minutes.

In the case of top UV, spray coating is performed using a conventional UV curable resin (UV # HST 210 (G), SSCP) to have a thickness of 20 μm, followed by drying for 60 minutes for 1 minute, followed by UV curing (900mj).

Example 2

The resin composition prepared in Preparation Example 2 is subjected to a coating process on the PMMA substrate with the same structure as in FIG. 1. At this time, in the case of undercoat UV, a coating film was formed with a thickness of 8 μm, and then dried at 60 ° C. for 1 minute and then UV cured (900mj). Thereafter, the resin composition prepared in Preparation Example 8 was diluted 1: 1.5 with a diluent (700 diluent, SSCP) and spray-coated to have a coating thickness of 3 μm, and then dried at 60 to 80 ° C. for 5 minutes.

In the case of top UV, spray coating is performed using a conventional UV curable resin (UV # HST 210 (G), SSCP) to have a thickness of 20 μm, followed by drying at 60 ° C. for 1 minute, and then performing UV curing (900mj).

Example 3

The resin composition prepared in Preparation Example 3 is subjected to a painting process on the PC / GF substrate with the structure as shown in FIG. 1. At this time, in the case of undercoat UV, a coating film was formed with a thickness of 8 μm, and then dried at 60 ° C. for 1 minute and then UV cured (900mj). Thereafter, the resin composition prepared in Preparation Example 8 was diluted 1: 1.5 with a diluent (700 diluent, SSCP) and spray-coated so that the coating thickness was 3 μm, followed by drying for 5 minutes at 60 to 80 ° C.

In the case of top UV, spray coating is performed using a conventional UV curable resin (UV # HST 210 (G), SSCP) to have a thickness of 20 μm, followed by drying at 60 ° C. for 1 minute, and then performing UV curing (900mj).

Example 4

The resin composition manufactured by the manufacture example 4 is apply | coated to AL base material in the structure similar to FIG. At this time, in the case of undercoat UV, a coating film was formed with a thickness of 8 μm, and then dried at 60 ° C. for 1 minute and then UV cured (900mj). Thereafter, the resin composition prepared in Preparation Example 8 was diluted 1: 1.5 with a diluent (700 diluent, SSCP) and spray-coated so that the coating thickness was 3 μm, followed by drying for 5 minutes at 60 to 80 ° C.

In the case of top UV, spray coating is performed using a conventional UV curable resin (UV # HST 210 (G), SSCP) to have a thickness of 20 μm, followed by drying at 60 ° C. for 1 minute, and then performing UV curing (900mj).

Example 5

The resin composition prepared in Preparation Example 4 is subjected to a coating process on the MG substrate with the same structure as in FIG. 1. At this time, in the case of undercoat UV, a coating film was formed with a thickness of 8 μm, and then dried at 60 ° C. for 1 minute and then UV cured (900mj). Thereafter, the resin composition prepared in Preparation Example 8 was diluted 1: 1.5 with a diluent (700 diluent, SSCP) and spray-coated so that the coating thickness was 3 μm, followed by drying for 5 minutes at 60 to 80 ° C.

In the case of top UV, spray coating is performed using a conventional UV curable resin (UV # HST 210 (G), SSCP) to have a thickness of 20 μm, followed by drying at 60 ° C. for 1 minute, and then performing UV curing (900mj).

Example 6

The resin composition prepared in Preparation Example 5 is subjected to a coating process with a structure as shown in Figure 1 on a PC substrate containing PLA. At this time, in the case of undercoat UV, a coating film is formed with a thickness of 8 μm, and then dried at 60 ° C. for 1 minute, followed by ultraviolet curing (900mj). Thereafter, the resin composition prepared in Preparation Example 8 was diluted 1: 1.5 with a diluent (700 diluent, SSCP) and spray-coated so that the coating thickness was 3 μm, followed by drying for 5 minutes at 60 to 80 ° C.

In the case of top UV, spray coating is performed using a conventional UV curable resin (UV # HST 210 (G), SSCP) to have a thickness of 20 μm, followed by drying at 60 ° C. for 1 minute, and then performing UV curing (900mj).

Example 7

* The resin composition manufactured by Production Example 6 is subjected to a painting process on a PC substrate with a structure similar to that of FIG. 1. At this time, the coating film thickness of a urethane 2K resin composition is made into 8 micrometers, and a coating film is formed and it dried for 60 degreeC for 3 minutes. Thereafter, the resin composition prepared in Preparation Example 8 was diluted 1: 1.5 with a diluent (700 diluent, SSCP) and spray-coated so that the coating thickness was 3 μm, followed by drying for 5 minutes at 60 to 80 ° C.

In the case of top UV, spray coating is performed using a conventional UV curable resin (UV # HST 210 (G), SSCP) to have a thickness of 20 μm, followed by drying at 60 ° C. for 1 minute, and then performing UV curing (900mj).

Example 8

The resin composition manufactured by the manufacture example 7 is subjected to the coating process to the PC base material with the structure similar to FIG. For easy spray painting, the coating film was formed with a diluent (700 diluent, SSCP) and diluted 1: 1.5 with a film thickness of the diluted 1K lacquer resin composition to 8 μm and dried at 60 ° C. for 3 minutes. Thereafter, the resin composition prepared in Preparation Example 8 was diluted 1: 1.5 with a diluent (700 diluent, SSCP) and spray-coated so that the coating thickness was 3 μm, followed by drying for 5 minutes at 60 to 80 ° C.

In the case of top UV, spray coating is performed using a conventional UV curable resin (UV # HST 210 (G), SSCP) to have a thickness of 20 μm, followed by drying at 60 ° C. for 1 minute, and then performing UV curing (900mj).

Example 9

In Comparative Preparation Example 1, a coating process was performed on the PC substrate with the structure as shown in FIG. The resin composition prepared in Comparative Example 1 was diluted 1: 1.5 with a diluent (700 diluent, SSCP) and spray-coated so that the coating thickness was 3 μm, followed by drying for 5 minutes at 60 to 80 ° C. Then, the resin composition prepared in Preparation Example 8 was diluted 1: 1.5 with a diluent (700 diluent, SSCP) for easy spray coating, and a coating film was formed with a thickness of 8 μm and dried at 60 to 80 ° C. for 5 minutes. .

In the case of top UV, spray coating is performed using a conventional UV curable resin (UV # HST 210 (G), SSCP) to have a thickness of 20 μm, followed by drying at 60 ° C. for 1 minute, and then performing UV curing (900mj).

Example 10

In the case of the undercoat coating, the coating is sprayed with a conventional UV curable resin (UV # HST 210 (G), SSCP) to have a thickness of 20 μm, dried at 60 ° C. for 1 minute, and then subjected to UV curing (900mj). And the resin composition prepared in Preparation Example 8 was diluted 1: 1.5 with a diluent (700 diluent, SSCP) for effective spray coating to form a coating film with a coating film thickness of 8㎛ and dried for 60 ~ 80 ℃ 5 minutes.

In the case of top UV, spray coating is performed using a conventional UV curable resin (UV # HST 210 (G), SSCP) to have a thickness of 20 μm, followed by drying at 60 ° C. for 1 minute, and then performing UV curing (900mj).

Comparative Example 1

The resin composition prepared in Comparative Production Example 1 is subjected to a painting process on the PC substrate with the structure as shown in FIG. 2. The resin composition prepared in Comparative Preparation Example 1 was diluted 1: 1.5 with a diluent (700 diluent, SSCP), spray-coated so that the coating thickness was 3 μm, and then dried at 60 to 80 ° C. for 5 minutes.

In the case of top UV, spray coating is performed using a conventional UV curable resin (UV # HST 210 (G), SSCP) to have a thickness of 20 μm, followed by drying at 60 ° C. for 1 minute, and then performing UV curing (900mj).

Comparative Example 2

A vapor deposition step is carried out according to Comparative Production Example 2. At this time, the physical properties of the deposition film on the PC material, etc. are incomplete, so that the deposition process is performed with the structure as shown in FIG. 3. First, a coating film is formed to have a coating thickness of 8 μm by spray coating with a coating primer for coating (UV # WIN 100. SSCP), dried at 60 ° C. for 5 minutes, and subjected to ultraviolet curing ultraviolet curing (900mj), and the coated PC specimen is vacuum chamber. Put it in the vacuum deposition by EVA type. At this time, the surface to be deposited is performed on the surface coated with a primer for deposition. After spraying the coating film to minimize the contamination of the deposited film (Enpra Primer. SSCP) to a film thickness of 5㎛ and goes through a drying process at 60 ℃ 10 minutes.

After that, the coating is spray-coated with a conventional UV curable resin (UV # HST 210 (G), SSCP) to have a thickness of 20 μm for the protection of the deposition on the substrate and dried at 60 ° C. for 1 minute, followed by UV curing (900mj). Is carried out.

<Test Example: Measurement of appearance and physical properties>

Test Example 1 : Luminance

Examples 1 to 11 to check the appearance.

It is about the brightening of the mirror, and it should be transparent and transparent like a mirror.

Usually visual observation is performed. (Judgment 0-> 5, bad-> very good)

Test Example 2 : Gloss.

Examples 1 to 11 to check the appearance.

A glossmeter (BYK Gardener glossmeter) is closely adhered to the cured and dried coating film, and the gloss at an angle of 60 degrees is measured.

Test Example 3 : Particles.

Examples 1 to 11 to check the appearance.

Determine the size of silver particles in the cured and dried coating coatings.

It is generally considered very good when there is no sense of particle like mirror surface. Visual judgment.

(Judgment 0-> 5, bad-> very good)

Test Example 4 : Evaluation by Initial Attachment ASTM D3359-87

In Examples 1 to 11 to check the adhesion of each material.

In the case of the adhesion test, check the UV curable resin coating film having a fine pattern and the different coating thickness and material.

Adhesive test method is to cross-cut the UV curable resin film with a fine pattern to 100 1mm X 1mm 100, and then perform the adhesion test 5 times with 3M tape. 5B: No falling off of the coating film at the cut edges, no peeling of the coating film in the lattice

4B: Deterioration of the edge is weakly observed and peeling occurs within 5% of the whole.

3B: Peeling and chipping of corners are observed and peeled off within 15%.

2B: Even within the lattice, peeling and chipping are observed and peeled off within 35%.

1B: A large ribbon peeling is observed and 35% to 65% peeling.

0B: Peeled at an area of 65% or more and poor adhesion.

Test Example 5 : Acid Resistance.

Example 1 to 11 to confirm the acid resistance.

The specimens coated in a standard solution of pH 4.6 are immersed for 72 hours and then subjected to appearance deformation and adhesion.

Test Example 6: Vibration abrasion resistance.

Examples 1 to 11 are put into the vibration abrasion resistance machine to check vibration abrasion resistance.

Vibration Wear Resistor: Rösler Tester (Test CAPA: 4 SET)

       Wear media: Material Ceramic. Loessler RKF 10K, Loessler RKK 15P

       Wear media ratio: Roesler RKF 10K, Roesler RKK 15P = 3: 1

      Additives: compound (Rösler FC120) and distilled water.

Table 1 The test results of the above Test Examples 1 to 6 are summarized in the following table (the determination criteria were determined as 0-> 5 (bad-> very good), OK, NG, as in the above sacrifice).

	Test Example 1	Test Example 2	Test Example 3	Test Example 4	Test Example 5	Test Example 6
Example 1	4	450	4	OK	OK	OK
Example 2	4	450	4	OK	OK	OK
Example 3	4	450	4	OK	OK	OK
Example 4	4	450	4	OK	OK	OK
Example 5	4	450	4	OK	OK	OK
Example 6	4	450	4	OK	OK	OK
Example 7	4	450	4	OK	OK	OK
Example 8	4	400	4	OK	OK	OK
Example 9	2	100	One	NG	NG	NG
Example 10	5	500	5	NG	NG	NG
Comparative Example 1	One	100	One	OK	OK	NG
Comparative Example 2	5	500	5	OK	NG	NG

Looking at the results of the above test results of applying the resin composition of the present invention has a very good physical properties, it can derive the results that can be applied to a variety of materials. Similar results were obtained for the material, brightness and glossiness, and the conclusion is that an efficient coating process, which is the object of the present invention, can have very good productivity. However, in the case of Example 9, when the resin of the material of the undercoat coating layer is the same as the resin of the mirror color coating layer material, an exception phenomenon occurs in which quality deterioration occurs due to coating film loss.

The vapor-deposited mirror color coating of the present invention can realize a similar mirror color by a general coating process such as spray coating, has applicability to various materials, excellent appearance, physical and chemical properties, and is a very efficient coating process of the product. It is very useful industrially because production cost can be reduced.

Claims (10)

1. A bottom coating layer formed on the substrate;

   A mirror color coating layer formed on the bottom coating layer; And

   And a top coat layer formed on the mirror color coating layer.
2. The non-deposited mirror color coating of claim 1, wherein the undercoat layer is formed of an ultraviolet curable resin composition, a urethane two-component resin composition, or a heat-dried one-component lacquer resin composition.
3. The non-deposited mirror color coating of claim 1, wherein the mirror color coating layer is formed of a lacquer resin composition to which an aluminum paste or silver paste is added.
4. The vapor-deposited mirror color coating of claim 2, wherein the UV-curable resin composition is added with PTMG polyurethane acrylate resin to which PO is added.
5. The non-deposited mirror color coating according to claim 2, wherein the urethane two-component resin composition or the heat-dried one-component lacquer resin composition is added with PTMG resin to which PO is added.
6. The non-deposited mirror color coating of claim 4, wherein the PO added PTMG polyurethane acrylate resin is added within a range of 3 to 20 parts by weight based on 100 parts by weight of the ultraviolet curable resin composition.
7. The non-deposited mirror color coating according to claim 5, wherein the PTMG resin to which PO is added is added within a range of 3 to 20 parts by weight based on 100 parts by weight of the total amount of the urethane two-component resin composition or the heat-dried one-component lacquer resin composition. .
8. The non-deposited mirror color coating of claim 1, wherein the substrate is a synthetic resin plate or a metal plate.
9. The method according to any one of claims 1 to 8, wherein the brightness of the vapor-deposited mirror color coating is at least 70% of the brightness of the mirror color structure in which the silver deposition layer is formed and the top coat layer is formed after being primed on top of the substrate. A no-deposit mirror mirror coating, characterized in that.
10. 9. The non-deposited mirror collar according to any one of claims 1 to 8, wherein the brightness of the non-deposited mirror color coating is 300% or more relative to the brightness of the non-deposited mirror color coating when the undercoat is omitted. Coatings.

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