KR101795032B1 - Multilayered coating for dry plating, method of manufacturing thereof and plastic material comprising the same - Google Patents

Abstract

The present invention relates to a multilayer coating for dry plating, a method of producing the same, and a plastic material containing the same, which comprises a primer layer, a dry coating layer, and a top layer, wherein the primer layer is a one-pack type ultraviolet curing type paint, This two-part type urethane paint improves the adhesion to the dry plating layer and is excellent in appearance, productivity, moisture resistance, salt water repellency, heat resistance, heat resistance, heat cycle resistance, abrasion resistance and light resistance, The present invention relates to a dry coating multi-layer coating, a method for producing the same, and a plastic material containing the same.

Description

Technical Field [0001] The present invention relates to a multilayer coating for dry plating, a method of manufacturing the same, and a plastic material containing the same. [0002] MULTILAYERED COATING FOR DRY PLATING, METHOD OF MANUFACTURING THEREOF AND PLASTIC MATERIAL COMPRISING THE SAME [0003]

The present invention relates to a multilayer coating for dry plating, a method for producing the same, and a plastic material containing the same.

Generally, the surface treatment of interior and exterior parts of automobiles is mainly finished by painting. At this time, in order for the interior and exterior parts to exhibit a luxurious metal texture, a painting finish using a paint containing a metal pigment or an electroplating by a wet process is used. In the field of some home appliances such as mobile phones and televisions, dry plating may be applied instead of wet plating in order to display the metal texture.

However, in the case of coating finish using a paint containing a metal pigment, there is a limitation in showing a luxurious metal texture due to a lower brightness, a problem in that pollutants are discharged in the case of wet plating, There is a problem that the design selection is limited due to limitations of price increase and color implementation due to the substitution. In addition, the dry plating method used in the field of some home appliances instead of wet plating has a limitation in realizing performance as an external component such as light fastness and weathering.

Accordingly, the inventors of the present invention have recognized that there is a need to develop coating technology for dry-type coatings which can reduce the emission of pollutants by using a dry plating method instead of wet plating, enable various designs to be selected, and improve light resistance and weather resistance, It was.

In order to solve the above-mentioned conventional problems, the present invention provides a dry coating multi-layer coating comprising a lower layer, a dry coating layer and an upper coating layer with less emission of pollutants, various choices of design, improved light resistance, weather resistance, And a multilayer coating method using the same.

In order to attain the above object, the present invention provides a laminate comprising a primer layer, a dry-plated layer and a top layer, wherein the primer layer comprises 10 to 20% by weight of a urethane diacrylate oligomer, The leveling additive is from 0.2 to 1% by weight, the adhesion promoter is from 0.3 to 1% by weight, and the solvent is from 30 to 55% by weight, the amount of the oligomer is from 2 to 8% by weight, the content of the acrylate monomer is from 20 to 30% Wherein the upper layer comprises 60 to 70% by weight of an acrylic polyol containing a polyester-modified acrylic polyol based on the total weight of the composition, 1.5 to 4% by weight of an ultraviolet stabilizer, 0.2 to 1% by weight of a curing agent and 20 to 30% by weight of a solvent, wherein 2 to 10 parts by weight of a curing agent is contained in an amount of 5 to 15 parts by weight Dry consisting of urethane coating also provides an electroplating multi-layer coating.

The present invention also relates to a method of manufacturing a semiconductor device, comprising the steps of: a) pretreating a plastic material, b) coating a surface of the plastic material with a one-pack type ultraviolet curable paint to form a primer layer, c) sputtering a metal on the primer layer surface And d) coating a two-pack type urethane paint on the surface of the dry coating layer to form a top coat layer. The one-pack type ultraviolet-curable paint comprises 10 to 20% by weight of a urethane diacrylate oligomer, 2 to 8% by weight of a polyester modified urethane acrylate oligomer, 20 to 30% by weight of an acrylate monomer, 2 to 10% by weight of a photoinitiator, 0.2 to 1% by weight of a leveling additive, 0.3 to 1% And the solvent is contained in an amount of 30 to 55% by weight, and the two-pack type urethane paint comprises an acrylic polyol containing a polyester- Wherein the curing agent is contained in an amount of 5 to 15 parts by weight based on 100 parts by weight of the composition of the upper layer layer, A multilayer coating method for dry plating is provided.

Further, the present invention provides a plastic material coated with the dry coating multi-layer coating.

According to the present invention, there is provided a one-pack type ultraviolet ray curing type coating material comprising a primer layer, a dry coating layer and a top layer, wherein the primer layer is an ultraviolet curing type coating material, This provides an excellent multilayer coating for dry plating.

The upper layer of the present invention is a two-pack type urethane paint having excellent adhesion with a dry plating layer and excellent in moisture resistance, salt water repellency, heat resistance, heat cycle resistance, abrasion resistance and light resistance, Thereby providing a dry coating multi-layer coating.

Hereinafter, the present invention will be described in detail.

The present invention includes a primer layer, a dry-plated layer and a top layer, wherein the primer layer comprises 10 to 20% by weight of a urethane diacrylate oligomer, a polyester modified urethane acrylate oligomer ( 2 to 8% by weight of a polyester modified urethane acrylate oligomer, 20 to 30% by weight of an acrylate monomer, 2 to 10% by weight of a photoinitiator, 0.2 to 1% by weight of a leveling additive, Wherein the upper layer is composed of an acrylic polyol containing a polyester modified acryl polyol in a total amount by weight of the composition, ) Of 60 to 70% by weight, an ultraviolet stabilizer of 1.5 to 4% by weight, an additive of 0.2 to 1% by weight and a solvent of 20 to 30% by weight, Layer coating comprising a two-component urethane paint containing 5 to 15 parts by weight of a curing agent based on 100 parts by weight of the top coat layer composition.

In order to form the multilayered coating of the present invention, a primer layer is first formed with a one-pack type ultraviolet curing type paint including urethane diacrylate oligomer, polyester modified urethane acrylate oligomer, acrylate monomer, photoinitiator, leveling additive, adhesion promoter and solvent . The undercoat layer is easy to adhere to various materials, especially plastic material and multi-layer coating, through the adhesion of the material, and it plays a role that the dry coating layer applied after forming the undercoat layer can be uniformly deposited.

The urethane diacrylate oligomer serves to improve the adhesion with the material to be bonded with the multilayer coating and to improve the impact resistance. At this time, the urethane diacrylate oligomer is preferably contained in an amount of 10 to 20% by weight based on the total weight of the one-pack type ultraviolet-curable paint constituting the primer layer. When the content is less than 10% by weight, If the content is more than 20% by weight, the adhesion and appearance of the deposited film become poor, and the hardness and curability of the coating film become poor.

The polyester-modified urethane acrylate oligomer serves to improve the adhesion with the material to be bonded with the multilayer coating and improve the impact resistance. At this time, the polyester-modified urethane acrylate oligomer is preferably contained in an amount of 2 to 8% by weight based on the total weight of the one-pack ultraviolet-curing type coating material constituting the primer layer. When the content is less than 2% by weight, If the content exceeds 8% by weight, the adhesion and appearance of the deposited film become poor, and the hardness and curability of the coating film become poor.

The acrylate monomer serves to harden the undercoating layer and to improve adhesion to the substrate. At this time, the acrylate monomer is preferably contained in an amount of 20 to 30% by weight based on the total weight of the one-pack ultraviolet-curing type coating material constituting the undercoat layer. When the content is less than 20% by weight, If the content is more than 30% by weight, there is a problem that deposition adhesion and water resistance become poor.

The acrylate monomer preferably includes, but is not limited to, pentaerythritol triacrylate monomer and tripropylene glycol diacrylate monomer.

The photoinitiator is preferably a hydroxycyclohexyl phenyl ketone for ultraviolet curing of the one-pack type ultraviolet-curing type paint and is contained in an amount of 2 to 10% by weight based on the total weight of the one-pack type ultraviolet-curing type paint . If the content is less than 2% by weight, the curability is deteriorated. If the content is more than 10% by weight, the adhesiveness is poor.

The leveling additive serves to improve smoothness and spraying workability in the undercoating layer and is preferably a polyether modified polysiloxane. The leveling additive is preferably used in an amount of 0.2 to 1% by weight based on the total weight of the one-pack type ultraviolet- . If the content is less than 0.2% by weight, the leveling becomes poor, and if the content exceeds 1% by weight, the deposition adhesion becomes poor.

The adhesion-promoting agent is preferably Epoxysilane for enhancing humidity resistance and cold-heat cycleability in the undercoat layer, and is preferably contained in an amount of 0.3 to 1% by weight based on the total weight of the one-pack type ultraviolet-curing type paint . If the content is less than 0.3 wt%, the adhesiveness is deteriorated. If the content is more than 1 wt%, the water resistance is poor.

The solvent is used to maintain the thickness of the coating film and improve the workability of coating, and acetate can be used. If the content is less than 30% by weight, the workability is deteriorated and the appearance becomes poor. When the content is more than 55% by weight, the There is a problem that a coating film is not formed.

In forming the multilayered coating of the present invention, the components for the undercoating layer are mixed to prepare a one-pack type ultraviolet-curing type coating composition, which is applied to the surface of the plastic substrate to form a primer layer, followed by drying, A dry plating layer is formed on the surface. The method for forming the dry plating layer is not particularly limited and may be formed by a conventional dry plating process using a vacuum evaporator. There is no particular limitation on the kind of metal contained in the dry plating layer. As shown in FIG. Preferably, the dry plating layer can be formed by using chromium (Cr), aluminum (Al), or titanium (Ti) by a sputtering method.

When the dry plating layer is formed, a top coat layer is formed on the surface thereof with a two-component urethane paint including an acrylic polyol containing a polyester-modified acrylic polyol, a UV stabilizer, an additive, a solvent and a curing agent. The upper layer protects the dry plating layer through adhesion with the dry plating layer and has excellent moisture resistance, cold cycle resistance, light resistance, weather resistance, and the like so that the multilayer coating can exhibit excellent physical properties.

The acrylic polyol containing the polyester-modified acrylic polyol improves the physical properties of the coating film such as smoothness, gloss, moisture resistance, adhesion of metal deposition and adhesion of the material of the coating film and is preferably 60 to 70 By weight. If the content of the acrylic polyol is less than 60% by weight, the adhesion of the material tends to deteriorate, the drying property tends to be poor, and the moisture resistance tends to be lowered, thereby deteriorating the physical properties of the metal vapor deposition film. There is a fear of deteriorating the sex. If the content of the acrylic polyol exceeds 70% by weight, adhesion with the metal vapor-deposited film may deteriorate, spray workability is lowered, the smoothness of the coating film is lowered, the hardening density of the coating film is lowered, The impact resistance may be lowered.

Preferably, the acrylic polyol containing the polyester-modified acrylic polyol has a solid content of 45 to 55% by weight, an OH value of 70 to 90 mgKOH / g, a weight average molecular weight of 7,500 to 8,500, a glass transition temperature (Tg And a glass transition temperature (Tg) of from 25 to 35 DEG C, and a glass transition temperature (Tg) of from 25 to 35 DEG C, It is preferable that the acrylic polyol is included.

At this time, it is preferable that the polyester-modified acrylic polyol is contained in an amount of 25 to 40% by weight based on the total weight of the acrylic polyol including the polyester-modified acrylic polyol. If the content of the polyester-modified acrylic polyol is less than 25% by weight, adhesion with the metal vapor deposition film becomes poor. If the content exceeds 40% by weight, hardness of the coating film due to the delay of curing may occur. The polyester-modified acrylic polyol preferably has a solid content of 65 to 75% by weight, an OH value of 120 to 140 mgKOH / g, a weight average molecular weight of 15,000 to 17,000, and a glass transition temperature (Tg) of 0 to 10 ° C Do.

(OH value) of from 85 to 95 mg KOH / g, a weight average molecular weight of from 2,500 to 3,500, a glass transition temperature (Tg), and a glass transition temperature (Tg) based on the total weight of the acrylic polyol containing the polyester- More preferably 5 to 15% by weight of an acrylic polyol having a melting point of 20 to 26 캜. By including the above-mentioned acrylic polyol, an excellent effect of moisture resistance and impact resistance is exhibited.

The ultraviolet stabilizer serves to improve the weatherability and the like of the upper layer, and preferably includes hydroxyphenyl-benzotriazole and benzotriazine. The ultraviolet light stabilizer is preferably contained in an amount of 1.5 to 4% by weight based on the total weight of the composition. When the content is less than 1.5% by weight, adhesion after the accelerated weathering test becomes poor, And when the content exceeds 4% by weight, yellowing occurs.

The additive is added for leveling the upper layer, and it is preferably a polyether modified polysiloxane and a silicon type defoamer. The content of the additive is preferably 0.2 to 1% by weight based on the total weight of the composition. When the content is less than 0.2% by weight, the leveling becomes poor. When the content exceeds 1% by weight, ) Is generated.

The solvent serves to improve the spraying workability, and may include xylene, acetate, and the like. The content of the solvent is preferably 20 to 30% by weight based on the total weight of the top layer composition. When the content is less than 20% by weight, the air spray properties are deteriorated and the appearance becomes poor. When the content is less than 30% , It is possible to cause the problem of overheating.

In the two-pack type urethane paint composition, it is preferable that the curing agent is included in an amount of 5 to 15 parts by weight based on 100 parts by weight of the composition comprising the polyester-modified acrylic polyol-containing acrylic polyol, ultraviolet light stabilizer, additives and solvent. If the content of the curing agent is less than 5 parts by weight, moisture resistance and abrasion resistance may deteriorate. If the content exceeds 15 parts by weight, the curability may become poor and cracks may occur.

Further, the curing agent is preferably a curing agent containing a polyisocyanate group, more preferably hexamethylene diisocyanate. The curing agent containing the polyisocyanate group is preferably such that the equivalent ratio of the hydroxyl group to the polyisocyanate group in the acrylic polyol is from 1: 0.8 to 1: 1.2. When the amount of the curing agent containing a polyisocyanate group is less than the above range, the curing is not sufficiently carried out. If the amount exceeds the above range, the curing is excessively performed and the desired physical properties are not exhibited.

It is preferable that the adhesion promoter is further included in an amount of 0.3 to 3% by weight based on the total weight of the two-pack type urethane paint. If the content is less than 0.3% by weight, the adhesiveness is not improved. If the content is more than 3% by weight, the water repellency is deteriorated. The adhesion-promoting agent preferably includes an epoxy silane (Epoxysilane) and a vinyl silane.

The present invention relates to a method for forming a dry coating layer on a surface of a substrate, comprising the steps of: a) pretreating a plastic material, b) coating a surface of the plastic material with a one-pack type ultraviolet curable paint to form a primer layer, c) And d) coating a two-pack type urethane paint on the surface of the dry plating layer to form a top layer, wherein the one-pack type ultraviolet curing type paint comprises 10 to 20% by weight of a urethane diacrylate oligomer, 2 to 8% by weight of acrylate oligomer, 20 to 30% by weight of acrylate monomer, 2 to 10% by weight of photoinitiator, 0.2 to 1% by weight of leveling additive, 0.3 to 1% by weight of adhesion promoter, 55% by weight, and the two-pack type urethane paint comprises 60 to 70% by weight of an acrylic polyol containing a polyester-modified acrylic polyol, A dry coating multilayer coating comprising 1.5 to 4% by weight of a stabilizer, 0.2 to 1% by weight of an additive and 20 to 30% by weight of a solvent, wherein the curing agent is contained in an amount of 5 to 15 parts by weight based on 100 parts by weight of the composition ≪ / RTI >

At this time, the plastic material is preferably acrylonitrile butadiene styrene (ABS), but is not limited thereto.

Further, the present invention provides a plastic material coated with the dry coating multi-layer coating.

The present invention will be described more specifically with reference to the following examples. However, these embodiments are merely illustrative and do not limit the technical scope of the present invention.

<Examples>

< Example  1>

One. Bottom layer  And Dry plated layer  formation

15 wt% of an aliphatic urethane diacrylate oligomer, 5 wt% of a polyester modified urethane acrylate oligomer, 21.5 wt% of pentaerythritol triacrylate monomer, 2.5 wt% of hydroxycyclohexyl phenyl ketone, 0.5 wt% of a polyether modified polysiloxane, 0.5% by weight of silane and 55% by weight of a solvent were mixed to prepare a one-pack type ultraviolet curing type paint. The one-pack type ultraviolet curing type paint was applied on the surface of acrylonitrile butadiene styrene (ABS) as a plastic substrate to a thickness of 20 μm, pre-heated for about 10 minutes, and irradiated with ultraviolet rays to form a primer layer.

A dry plating layer containing chromium (Cr) was formed on the surface of the undercoating layer to a thickness of 0.1 to 0.2 탆 by a sputtering method which is one of the dry plating methods.

2. Top layer  formation

30% by weight of acrylic polyol A (solid content 50% by weight, OH Value = 80 mgKOH / g, weight average molecular weight about 8,000, Tg = 15 캜 acrylic polyol), acrylic polyol B (65% by weight of solid content, OH Value = 120 mgKOH / 25 weight%), acrylic polyol D (solid content 70% by weight, OH Value = 130 mgKOH / g, weight average molecular weight 16,000, Tg = 5 占 폚, polyester modified acrylic polyol) %, A hydroxyphenylbenzotriazole 1.8 weight%, a benzotriazine 0.7 weight, a polyether modified polysiloxane and silicone type antifoaming agent 1 weight%, and a solvent 24.5 weight%. The two-component urethane coating composition was coated on the surface of the dry plating layer to a thickness of 20 탆 and dried at a temperature of 70 캜 for 60 minutes to form an upper layer.

< Example  2>

One. Bottom layer  And Dry plated layer  formation

15 wt% of aliphatic urethane diacrylate oligomer, 5 wt% of polyester modified urethane acrylate oligomer, 11.5 wt% of pentaerythritol triacrylate monomer, 10 wt% of tripropylene glycol diacylate monomer, 2.5 wt% of hydroxycyclohexyl phenyl ketone , 0.5% by weight of a polyether-modified polysiloxane, 0.5% by weight of an epoxy silane and 55% by weight of a solvent were mixed to prepare a one-pack type ultraviolet ray curing type paint. The one-pack type ultraviolet curing type paint was applied on the surface of acrylonitrile butadiene styrene (ABS) as a plastic substrate to a thickness of 20 μm, pre-heated for about 10 minutes, and irradiated with ultraviolet rays to form a primer layer.

A dry plating layer containing chromium (Cr) was formed on the surface of the undercoating layer to a thickness of 0.1 to 0.2 탆 by a sputtering method which is one of the dry plating methods.

2. Top layer  formation

Acrylic polyol E 30% by weight, acrylic polyol B 15% by weight, acryl polyol D 20% by weight, acrylic polyol E (solid content 55% by weight, OH Value = 90 mgKOH / g, weight average molecular weight about 3,000, Tg = 8 weight% of hydroxyphenyl benzotriazole, 0.7 weight% of benzotriazine, 0.5 weight% of epoxy silane and vinyl silane, 1 weight% of polyether modified polysiloxane and silicone defoamer and 23 weight% of solvent To prepare a two-pack type urethane paint composition. The two-component urethane coating composition was coated on the surface of the dry plating layer to a thickness of 20 탆 and dried at a temperature of 70 캜 for 60 minutes to form an upper layer.

< Comparative Example >

One. Bottom layer  And Dry plated layer  formation

20 wt% of an aliphatic urethane diacrylate oligomer, 21.5 wt% of a pentaerythritol triacrylate monomer, 2.5 wt% of hydroxycyclohexyl phenyl ketone, 0.5 wt% of a polyether-modified polysiloxane, 0.5 wt% of an epoxy silane, and 55 wt% Thereby preparing a one-pack type ultraviolet ray curing type paint. The one-pack type ultraviolet curing type paint was applied on the surface of acrylonitrile butadiene styrene (ABS) as a plastic substrate to a thickness of 20 μm, pre-heated for about 10 minutes, and irradiated with ultraviolet rays to form a primer layer.

A dry plating layer containing chromium (Cr) was formed on the surface of the undercoating layer to a thickness of 0.1 to 0.2 탆 by a sputtering method which is one of the dry plating methods.

2. Top layer  formation

, 27% by weight of acrylic polyol A, 25% by weight of acrylic polyol B, 20% by weight of acrylic polyol C (solid content 60% by weight, OH Value = 100 mgKOH / g, weight average molecular weight about 2,500, Tg = 41 캜 acrylpolyol) A two-pack type urethane paint composition was prepared comprising 1.8% by weight of benzotriazole, 0.7% by weight of benzotriazine, 1% by weight of polyether modified polysiloxane and silicone defoamer, and 24.5% by weight of solvent. The two-component urethane coating composition was coated on the surface of the dry plating layer to a thickness of 20 탆 and dried at a temperature of 70 캜 for 60 minutes to form an upper layer.

Category (Unit:% by weight) Comparative Example Example 1 Example 2 Aliphatic urethane diacrylate oligomer 20 15 15 The polyester-modified urethane acrylate oligomer - 5 5 Pentaerythritol triacrylate monomer 21.5 21.5 11.5 Tripropylene glycol diacylate monomer - - 10 Hydroxycyclohexyl phenyl ketone 2.5 2.5 2.5 Polyether-modified polysiloxane 0.5 0.5 0.5 Epoxy silane 0.5 0.5 0.5 solvent 55 55 55 Sum 100 100 100

Category (Unit:% by weight) Comparative Example Example 1 Example 2 Acrylic polyol A 27 30 30 Acrylic polyol B 25 17 15 Acrylic polyol C 20 - - Acrylic polyol D - 25 20 Acrylic polyol E - - 8 Hydroxyphenylbenzotriazole 1.8 1.8 1.8 Benzotriazine 0.7 0.7 0.7 Epoxy silane and vinyl silane - - 0.5 Polyether modified polysiloxanes and silicon type antifoaming agents One One One solvent 24.5 24.5 23 Sum 100 100 100 Acrylic polyol A: solid content 50% by weight, OH Value = 80 mgKOH / g, weight average molecular weight about 8,000, Tg = 15 占 폚 Acrylic polyol
Acrylic polyol B: 65% by weight of solid content, OH Value = 120 mgKOH / g, weight average molecular weight of about 3,000, Tg = 30 占 폚 Acrylic polyol
Acrylic polyol C: solid content 60% by weight, OH Value = 100 mgKOH / g, weight average molecular weight about 2,500, Tg = 41 占 폚 Acrylic polyol
Acrylic polyol D: 70% by weight of solids, OH Value = 130 mgKOH / g, weight average molecular weight of about 16,000, Tg = 5 占 폚 Polyester modified acrylic polyol
Acrylic polyol E: 55% by weight of solid content, OH Value = 90 mgKOH / g, weight average molecular weight: about 3,000, Tg = 23 캜 Acrylic polyol

<Experimental Example>

One. Attachment

The surface of each of the prepared examples and comparative examples was squeezed with a knife at intervals of 2 mm each at a width of 2 mm and a length of 100 mm to prepare 100 lattices.

2. Pencil Hardness

A pencil (Mitsubishi Corp., Uni-pencil) was used to evaluate the occurrence of scratches on the surfaces of the prepared examples and comparative examples.

3. Non-stickiness

Five pieces of gauzes each having a size of 50 mm in length and width were stacked on the surfaces of the prepared examples and comparative examples and a columnar weight having a bottom surface of 40 mm in diameter and 500 g in mass was placed in the center of the gauze, After holding for 2 hours in the maintained thermostatic chamber, the gauze was pulled out from the drawing and the traces of the gauze attached to the figure were evaluated.

4. Alkali resistance

0.2 ml of 0.1 N sodium hydroxide was dropwise added to the surfaces of the prepared examples and comparative examples and allowed to stand at a temperature of 20 ± 2 ° C. and a humidity of 65 ± 5% for 24 hours, then washed with water and air blow ) And allowed to stand at room temperature for 1 hour, and then the appearance change of the coating film was evaluated.

5. Acid resistance

After the 0.1 N sulfuric acid solution was spotted at room temperature for 24 hours on the surfaces of the prepared examples and comparative examples, the appearance change of the coating film was evaluated.

6. Impact resistance

The weights of 500g and 12.7mm in diameter were dropped at a height of 20cm by using a fall drop tester of the ISO 6272 or JIS K 5600-5-3 for the prepared examples and comparative examples, .

7. Moisture resistance

The prepared examples and comparative examples were allowed to stand in a constant temperature and humidity room at a temperature of 50 DEG C and a relative humidity of 98% for 168 hours, and then evaluated for adhesion damage.

8. Water Resistance

The samples thus prepared were immersed in tap water (TAP Water) at a temperature of 40 ± 2 ° C. for 240 hours, taken out, and then subjected to air blowing to remove moisture on the surface. The samples were allowed to stand at room temperature for 1 hour, Was evaluated, and an adhesion test was carried out.

9. Salt water silent

For the prepared examples and comparative examples, a salt spray tester having a sodium chloride (NaCl) concentration of 50 ± 5 g / L with a pH of 6.5 to 7.2 was added, sprayed for 240 hours, washed with water, After removing moisture from the surface by air blowing, the surface condition of the coating film was examined and the adhesion test was performed.

10. Heat resistance

The prepared examples and comparative examples were allowed to stand at a temperature of 80 ° C for 300 hours, and then evaluated for appearance and adhesion damage.

11. Heat-resistant cyclic property

For the above-mentioned Examples and Comparative Examples, the reaction was allowed to stand at a temperature of 80 ° C for 3 hours, at room temperature for 1 hour, at a temperature of -30 ° C for 3 hours, at a room temperature of 1 hour, at a temperature of 50 ° C for 3 hours, One cycle was repeated three cycles in total, and then the product was evaluated for deformation.

12. Weatherability

For the above-mentioned Examples and Comparative Examples, a weather-resistant tester (Light-Tube) comprising a combination of quartz (Quartz inner filter) and S type-borosilicate (outer filter) o-meter), irradiated with ultraviolet rays of 340 nm wavelength at 2500 KJ / m 2 energy, and the surface of the coated film was cleaned with a neutral detergent, and then the surface moisture was removed by air blowing. Thereafter, the surfaces of the examples and comparative examples were wiped with a polishing wax, and the surface state (visual observation), color difference (? E *) and gray scale of the coating film were examined and adhesion test, abrasion resistance test and cycle test were carried out .

13. Chemical resistance

After applying the gloss wax, detergent, artificial perspiration liquid and grease to the surface of the prepared examples and comparative examples after being embedded in the gauze, one cycle in the evaluation of the cold and heat cycleability was carried out to evaluate whether or not the adhesion of the outer appearance was damaged.

14. Abrasion resistance

The prepared examples and comparative examples were subjected to dry 10,000 times and wet 10,000 times using a reciprocating abrasion tester (load 1 kg, test speed 60 times / minute, friction stroke 100 mm, double sided canvas # 10 (KS K 1450) And the exposure of the material was evaluated.

15. Chipping resistance

Cm &lt; ² &gt; at a temperature of 20 [deg.] C and -40 [deg.] C, using a zeolite having a diameter of 2.5 to 5 mm and a weight of 500 g by a gravelometer (SAE J 400 standard product) The chipping test was carried out using the air pressure.

16. CASS

The solution mixed with 1 L of the test small amount and 0.26 ± 0.02 g of copper (II) chloride was sprayed on the surface of the prepared examples and comparative example at a temperature of 50 ° C for 72 hours to evaluate the denaturation.

17. Coordination Court

500 ml of distilled water and 2.5 g of copper nitrate, 7 ml of distilled water, 33 ml of a mixture of 2.5 g of ferric chloride, 500 ml of distilled water and 10 ml of a mixture of 50 g of ammonium chloride were mixed with 30 g of white clay to prepare a slurry, , And dried in the room for 1 hour. Thereafter, the sample was allowed to stand for 20 hours at a temperature of 38 DEG C and a relative humidity of 80 to 99%, and the process was performed for a total of 2 cycles and then evaluated.

18. Diarrhea

7.45 g of calcium chloride, 6 g of clay, 1.4 ml of cupric nitrate, 6.6 ml of ferric chloride and 2 ml of ammonium chloride were mixed to prepare a calcium chloride corrosion slurry. The above-mentioned calcium chloride corrosion slurry was applied to the surfaces (254 mm 2) of the prepared examples and the comparative examples, respectively, and allowed to stand for 48 hours at a temperature of 60 ° C to evaluate whether or not they were denatured.

Item Comparative Example Example 1 Example 2 Attachment ○ ○ ○ Pencil hardness F F F Non-stickiness ○ ○ ○ Alkali resistance ○ ○ ○ Acid resistance ○ ○ ○ Impact resistance ○ ○ ○ Moisture resistance × ○ ○ Water resistance × △ ○ Salt water silent × ○ ○ Heat resistance × ○ ○ Heat-resistant cyclic property × ○ ○ Weatherability × △ ○ Chemical resistance ○ ○ ○ Abrasion resistance × ○ ○ Chipping resistance ○ ○ ○ CASS × ○ ○ Coordination Court ○ ○ ○ Diarrhea ○ ○ ○ ?: Excellent,?: Normal, X: Bad

According to the evaluation results of Table 3, it can be confirmed that Examples 1 and 2 are superior in moisture resistance, salt water repellency, heat resistance, heat cycle resistance, abrasion resistance, light resistance, water resistance and weather resistance.

Claims (10)

An undercoat layer, a dry-plated layer, and a topcoat layer,
Wherein the undercoat layer comprises 10 to 20% by weight of a urethane diacrylate oligomer, 2 to 8% by weight of a polyester modified urethane acrylate oligomer, 20 to 30% by weight of an acrylate monomer, 2 to 30% by weight of a photoinitiator, 1-part type ultraviolet curing type paint comprising 10 to 10% by weight of a leveling additive, 0.2 to 1% by weight of a leveling additive, 0.3 to 1% by weight of an adhesion promoting agent and 30 to 55% by weight of a solvent,
Wherein the top layer comprises 60 to 70% by weight of an acrylic polyol containing a polyester-modified acrylic polyol based on the total weight of the composition, 1.5 to 4% by weight of an ultraviolet stabilizer, 0.2 to 1% by weight of an additive, and 20 to 30% And a curing agent is contained in an amount of 5 to 15 parts by weight based on 100 parts by weight of the upper layer composition. The dry coating multilayer coating according to claim 1, wherein the acrylate monomer comprises pentaerythritol triacrylate monomer and tripropylene glycol diacrylate monomer. The dry coating multilayer coating according to claim 1, wherein the polyester-modified acrylic polyol is contained in an amount of 25 to 40% by weight based on the total weight of the acrylic polyol. The acrylic polyol according to claim 3, wherein the acrylic polyol having a solid content of 50 to 60 wt%, a hydroxyl value of 85 to 95 mg KOH / g, a weight average molecular weight of 2,500 to 3,500, and a glass transition temperature of 20 to 26 DEG C By weight to 15% by weight based on the total weight of the dry coating. The dry coating multilayer coating according to claim 1, wherein the dry plating layer comprises chromium, titanium or aluminum. The dry coating multilayer coating according to claim 1, wherein the adhesion promoter is further contained in an amount of 0.3 to 3% by weight based on the total weight of the two-pack type urethane paint. The dry coating multilayer coating according to claim 1, wherein the curing agent is a curing agent containing a polyisocyanate group. a) pre-treating the plastic material,
b) coating a surface of the plastic material with a one-pack type ultraviolet curable paint to form a primer layer,
c) forming a dry plating layer on the surface of the undercoat layer by sputtering metal; and
d) coating a two-component urethane paint on the surface of the dry plating layer to form a top coat layer,
The one-pack type ultraviolet ray curing type coating material comprises 10 to 20% by weight of a urethane diacrylate oligomer, 2 to 8% by weight of a polyester modified urethane acrylate oligomer, 20 to 30% by weight of an acrylate monomer, 2 to 10% 0.2 to 1% by weight of a leveling additive, 0.3 to 1% by weight of an adhesion promoter and 30 to 55% by weight of a solvent,
The two-pack type urethane paint comprises 60 to 70% by weight of an acrylic polyol containing a polyester-modified acrylic polyol, 1.5 to 4% by weight of an ultraviolet stabilizer, 0.2 to 1% by weight of an additive and 20 to 30% by weight of a solvent And 5 to 15 parts by weight of a curing agent based on 100 parts by weight of the top coat layer composition. The method according to claim 8, wherein the plastic material is acrylonitrile butadiene styrene. A plastic material coated with the dry coating multi-layer coating of claim 1.