Copper plated coating film and method for producing the same

Abstract

The application discloses a copper-plated coating film and a preparation method thereof, and relates to the field of film-coated materials. The copper-plated coating film comprises a base film layer, a primer layer, a copper layer and a top coating layer arranged in sequence, the primer layer and the top coating layer are prepared from polyurethane modified acrylate paint, and the preparation raw materials of the polyurethane modified acrylate paint comprise 30-40 parts by weight of 3-functionality modified polyurethane acrylate, 8.5-10.5 parts by weight of hydroxyethyl acrylate, 5.5-7.0 parts by weight of alkoxylated trimethylolpropane triacrylate, 1-2 parts by weight of an amine-based additive, 6-8 parts by weight of a photoinitiator and 1-1.5 parts by weight of a leveling agent. In the copper-plated coating film, the adhesion between the copper layer and the base film layer is good, the evaporation uniformity of the copper layer is good, and the copper layer is not prone to corrosion in a humid environment.

Description

Technical Field

[0001] This application relates to the field of coating materials, and in particular to a copper-plated coating film and its preparation method. Background Technology

[0002] Copper-plated films are widely used in many fields, such as electronics, packaging, and decoration. However, traditional copper-plated films still have some areas for improvement in practical applications:

[0003] 1. In the bonding process between the copper layer and the base film, corona treatment of the base film is usually required to enhance the adhesion between the copper layer and the base film. However, static charge is easily left after corona treatment. This static charge can easily attract dust or moisture from the environment, which can lead to pinholes and pits in the copper layer, which is not conducive to improving the uniformity of copper deposition.

[0004] 2. The copper layer of the copper-plated film is directly exposed to the air, and the copper layer is prone to oxidation and corrosion in humid environments, which affects its normal use. Summary of the Invention

[0005] In order to improve the adhesion between the copper layer and the base film layer in related technologies, improve the uniformity of copper layer deposition, and improve the problem of easy corrosion of copper layer, this application provides a copper-plated coating film and its preparation method.

[0006] Firstly, the copper-plated coating film provided in this application adopts the following technical solution:

[0007] A copper-plated coating film includes a base film layer, a primer layer, a copper layer, and a topcoat layer arranged sequentially. Both the primer layer and the topcoat layer are made of polyurethane-modified acrylate coating. The raw materials for preparing the polyurethane-modified acrylate coating include 30-40 parts by weight of trifunctional modified polyurethane acrylate, 8.5-10.5 parts by weight of hydroxyethyl acrylate, 5.5-7.0 parts by weight of alkoxylated trimethylolpropane triacrylate, 1-2 parts by weight of amine additives, 6-8 parts by weight of photoinitiator, and 1-1.5 parts by weight of leveling agent.

[0008] In this application, a base coating is added between the copper layer and the base film layer, and a top coating is added to the outer surface of the copper layer. The base coating is used to improve the adhesion between the copper layer and the base film layer, which can eliminate the step of corona treatment of the base film layer. This helps to prevent the copper layer from having pinholes due to the residual static charge after corona treatment, which can easily attract dust or moisture from the environment. The top coating is used to isolate the copper layer from the air, improve the problem of easy oxidation and corrosion of the copper layer in humid air, and extend the life of the copper plating coating film.

[0009] Furthermore, both the base coating and the top coating in this application are prepared using a polyurethane-modified acrylate coating made from trifunctional modified polyurethane acrylate, hydroxyethyl acrylate, alkoxylated trimethylolpropane triacrylate, amine additives, photoinitiators, and leveling agents in a specific ratio. The coating obtained by this polyurethane-modified acrylate coating has high adhesion to the base film and copper layer, and good density and uniformity. It will not affect the copper plating uniformity of the subsequent copper plating process, and can obtain a copper layer with good vapor deposition uniformity. At the same time, the coating obtained by this polyurethane-modified acrylate coating can also effectively block humid air and has good weather resistance. It can effectively protect the copper layer for a long time, prevent copper layer corrosion, and effectively extend the service life of the copper plating coating film.

[0010] In some specific embodiments, the amine auxiliaries are at least one of triethylamine, methyldiethanolamine, ethyl p-dimethylaminobenzoate, and N-phenylglycine, and the photoinitiator is at least one of photoinitiator TPO, photoinitiator 819, and photoinitiator 184.

[0011] In some preferred embodiments, the amine auxiliary is N-phenylglycine, and the photoinitiator is photoinitiator 184.

[0012] In this application, N-phenylglycine is preferred as the amine additive, and photoinitiator 184 is preferred as the photoinitiator. The combination of the two is beneficial to further promote the stable curing of the base coating. On the one hand, it can improve the uniformity of the base coating, thereby further improving the thickness uniformity of the copper layer. On the other hand, it can help reduce the internal stress of the base coating, thereby improving the adhesion between the base coating and the base film layer, as well as the adhesion between the base coating and the copper layer.

[0013] In some specific embodiments, the alkoxylated trimethylolpropane triacrylate is at least one of ethoxylated trimethylolpropane triacrylate and propoxylated trimethylolpropane triacrylate.

[0014] In some preferred embodiments, the leveling agent is an organosilicone polyether acrylate leveling agent.

[0015] Compared with using polyether-modified polydimethylsiloxane as a leveling agent, using organosilicon polyether acrylate leveling agent is beneficial to further improve the thickness uniformity of the copper layer.

[0016] Secondly, the method for preparing a copper-plated coating film provided in this application adopts the following technical solution:

[0017] A method for preparing a copper-plated coating film includes the following steps:

[0018] S1, Primer: A polyurethane-modified acrylate coating is applied to one surface of the base film layer and cured to form a primer layer;

[0019] S2, copper plating: evaporating copper on the side of the primer layer away from the base film layer to obtain a copper layer;

[0020] S3, top coating: coating polyurethane modified acrylate paint on the side of the copper layer away from the primer layer, and forming a top coating layer after curing to obtain a copper plated coating film.

[0021] In some specific embodiments, the method for preparing the copper plated coating film further comprises a pre-preparation step of the polyurethane modified acrylate paint, wherein the preparation of the polyurethane modified acrylate paint comprises the following steps:

[0022] Under light-proof conditions, hydroxyethyl acrylate and alkoxylated trimethylolpropane triacrylate are added into a container, and after stirring to be uniform, a photoinitiator is added to be dissolved to be transparent and free of particles, and then filtered to obtain a semi-finished product;

[0023] Under light-proof conditions, 3-functional modified polyurethane acrylate is added into another container, and a leveling agent is added and stirred to be dispersed to obtain a resin mixture,

[0024] Under light-proof conditions, the semi-finished product and an amine-based auxiliary agent are added into the resin mixture, and stirred to be mixed uniformly to obtain the polyurethane modified acrylate paint.

[0025] In the present application, the polyurethane modified acrylate paint is prepared by the above method, which is beneficial to uniformly disperse each component and obtain uniform primer and top coating layers.

[0026] In some specific embodiments, in steps S1 and S3, the curing energy required by the polyurethane modified acrylate paint is 60-70 mj / cm 2 .

[0027] In the present application, the curing energy required by the polyurethane modified acrylate paint is preferably 60-70 mj / cm 2 , wherein too low curing energy cannot achieve rapid curing, and too high curing energy is easy to cause adverse effects on the base film layer, such as shrinkage and yellowing of the base film layer.

[0028] In some specific embodiments, in step S2, when copper plating, the purity of copper particles is above 99.99%, and before evaporating copper, titanium particles are added into the copper particles, and the mass of the titanium particles is 0.45-0.55% of the mass of the copper particles.

[0029] In the present application, before copper plating, specific ratio of titanium particles is added into the copper particles, on the one hand, the titanium particles can preferentially react with residual oxygen in the vacuum cavity to reduce the oxygen content of the copper layer, and on the other hand, the titanium particles can also promote uniform nucleation of copper vapor, which is beneficial to improve the evaporation uniformity of the copper layer.

[0030] In summary, the present application at least includes the following beneficial technical effects:

[0031] 1. In the present application, a primer layer is added between the copper layer and the base film layer, and a topcoat layer is added to the outer surface of the copper layer, wherein the primer layer and the topcoat layer are prepared by using a polyurethane modified acrylic coating prepared by a specific ratio of 3-functional modified polyurethane acrylate, hydroxyethyl acrylate, alkoxylated trimethylolpropane triacrylate, amine adjuvant, photoinitiator and leveling agent, and the primer layer is used to improve the adhesion between the copper layer and the base film layer, which can omit the step of corona treatment of the base film layer, and is conducive to preventing the problem that the copper layer appears pinhole and pitting after the base film layer is easily adsorbed by the dust or moisture in the environment after the corona treatment. At the same time, the primer layer has good compactness and uniformity, and will not affect the copper plating uniformity of the subsequent copper plating process, so that a copper layer with good evaporation uniformity can be obtained. The topcoat layer also has good compactness and uniformity and weather resistance, can isolate air, improve the problem that the copper layer is easily oxidized and corroded in humid air, can effectively protect the copper layer, prevent the copper layer from being eroded, and can effectively prolong the service life of the copper plating coating film.

[0032] (2) In the present application, the amine adjuvant is preferably N-phenyl glycine, and the photoinitiator is preferably photoinitiator 184, and the combination of the two is conducive to further promoting the stable curing of the primer layer. On the one hand, it can improve the uniformity of the primer layer, thereby further improving the thickness uniformity of the copper layer, and on the other hand, it is conducive to reducing the internal stress of the primer layer, and can improve the adhesion between the primer layer and the base film layer and the adhesion between the primer layer and the copper layer. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 is a structural schematic diagram of a copper plating coating film according to the present application.

[0034] BRIEF DESCRIPTION OF DRAWINGS

[0035] 1. Base film layer; 2. Primer layer; 3. Copper layer; 4. Topcoat layer. DETAILED DESCRIPTION

[0036] The present application will be further described below in combination with specific experiments.

[0037] Preparation Example

[0038] Preparation Example 1

[0039] A polyurethane modified acrylic coating includes the following raw materials: 3-functional modified polyurethane acrylate: 30 kg; In this embodiment, the 3-functional modified polyurethane acrylate specifically uses a 3-functional modified polyurethane acrylate with a model number of L-8413 from Bluekote;

[0040] Hydroxyethyl acrylate: 10.5 kg;

[0041] alkoxylated trimethylolpropane triacrylate: 7.0 kg; in this embodiment, the alkoxylated trimethylolpropane triacrylate specifically uses ethoxylated trimethylolpropane triacrylate;

[0042] amine auxiliary agent: 1 kg; in this embodiment, the amine auxiliary agent specifically uses triethylamine;

[0043] photoinitiator: 8 kg; in this embodiment, the photoinitiator specifically uses photoinitiator 184;

[0044] leveling agent: 1 kg; in this embodiment, the leveling agent specifically uses TEGO 2100 silicone polyether acrylate leveling agent of Degussa.

[0045] The preparation method of the above-mentioned polyurethane modified acrylate coating includes the following steps:

[0046] Under the light-proof condition, the hydroxyethyl acrylate and the alkoxylated trimethylolpropane triacrylate are added into a container, and after being stirred uniformly, the photoinitiator is dissolved to be transparent and free of particles, and then the semi-finished product is obtained by filtration;

[0047] Under the light-proof condition, the 3-functional modified polyurethane acrylate is added into another container, and the leveling agent is added and stirred and dispersed to obtain a resin mixture,

[0048] Under the light-proof condition, the semi-finished product and the amine auxiliary agent are added into the resin mixture, and after being stirred and mixed uniformly, the polyurethane modified acrylate coating is obtained.

[0049] The minimum curing energy of the polyurethane modified acrylate coating is 55 mj / cm 2 .

[0050]

Preparation Example 2

[0051] A polyurethane modified acrylate coating, which is different from

Preparation Example 1

[0052] In this preparation example, the polyurethane modified acrylate coating includes the following raw materials:

[0053] 3-functional modified polyurethane acrylate: 40 kg; in this embodiment, the 3-functional modified polyurethane acrylate specifically uses the 3-functional modified polyurethane acrylate with the model number of L-8414 of Bluekote;

[0054] hydroxyethyl acrylate: 8.5 kg;

[0055] alkoxylated trimethylolpropane triacrylate: 5.5 kg; in this embodiment, the alkoxylated trimethylolpropane triacrylate specifically uses propoxylated trimethylolpropane triacrylate;

[0056] Amine assistant: 2 kg; in this embodiment, the amine assistant specifically uses methyldiethanolamine;

[0057] Photoinitiator: 6 kg; in this embodiment, the photoinitiator specifically uses photoinitiator 184;

[0058] Leveling agent: 1.5 kg; in this embodiment, the leveling agent specifically uses TEGO 2100 silicone polyether acrylate leveling agent.

[0059] The minimum curing energy of the polyurethane modified acrylate coating is 60 mj / cm 2 .

[0060] Preparation Example 3

[0061] A polyurethane modified acrylate coating, which is different from Preparation Example 1 in that the amine assistant is different, and in this preparation example, the amine assistant specifically uses methyldiethanolamine.

[0062] The minimum curing energy of the polyurethane modified acrylate coating is 60 mj / cm 2 .

[0063] Preparation Example 4

[0064] A polyurethane modified acrylate coating, which is different from Preparation Example 1 in that the amine assistant is different, and in this preparation example, the amine assistant specifically uses N-phenylglycine.

[0065] The minimum curing energy of the polyurethane modified acrylate coating is 60 mj / cm 2 .

[0066] Preparation Example 5

[0067] A polyurethane modified acrylate coating, which is different from Preparation Example 4 in that the photoinitiator is different, and in this preparation example, the photoinitiator specifically uses photoinitiator 819.

[0068] The minimum curing energy of the polyurethane modified acrylate coating is 60 mj / cm 2 .

[0069] Preparation Example 6

[0070] A polyurethane modified acrylate coating, which is different from Preparation Example 4 in that the photoinitiator is different, and in this preparation example, the photoinitiator specifically uses photoinitiator TPO.

[0071] The minimum curing energy of the polyurethane modified acrylate coating is 60 mj / cm 2 .

[0072] Comparative Preparation Example

[0073]

Comparative Preparation Example 1

[0074] A polyurethane-modified acrylate coating, which is different from

Preparation Example 1

[0075] The hydroxyethyl acrylate is replaced with an equal amount of ethyl acrylate.

[0076] The minimum curing energy of the polyurethane-modified acrylate coating is 60 mj / cm 2 .

[0077]

Comparative Preparation Example 2

[0078] A polyurethane-modified acrylate coating, which is different from

Preparation Example 1

[0079] The ethoxylated trimethylolpropane triacrylate is replaced with an equal amount of trimethylolpropane triacrylate.

[0080] The minimum curing energy of the polyurethane-modified acrylate coating is 60 mj / cm 2 .

[0081]

Comparative Preparation Example 3

[0082] A polyurethane-modified acrylate coating, which is different from

Preparation Example 1

[0083] 3-functional modified polyurethane acrylate: 20 kg; in this example, the 3-functional modified polyurethane acrylate specifically uses a 3-functional modified polyurethane acrylate with a brand of L-8413 from Bluekote;

[0084] Hydroxyethyl acrylate: 15 kg;

[0085] Alkoxylated trimethylolpropane triacrylate: 10 kg; in this example, the alkoxylated trimethylolpropane triacrylate specifically uses ethoxylated trimethylolpropane triacrylate;

[0086] Amine-based auxiliary agent: 1 kg; in this example, the amine-based auxiliary agent specifically uses triethylamine;

[0087] Photoinitiator: 8 kg; in this example, the photoinitiator specifically uses photoinitiator 184;

[0088] Leveling agent: 1 kg; in this example, the leveling agent specifically uses a TEGO 2100 silicone polyether acrylate leveling agent from Degussa.

[0089] The minimum curing energy of the polyurethane-modified acrylate coating is 60 mj / cm 2 .

[0090] Embodiment

[0091] Example 1

[0092] A copper-plated coating film, with reference to Figure 1 , comprising a base film layer 1, a primer layer 2, a copper layer 3 and a top coating layer 4 arranged in sequence, the thickness of the base film layer 1 is 18 μm, the thickness of the primer layer 2 is 2 μm, the thickness of the copper layer 3 is 250 A, and the thickness of the top coating layer 4 is 2 μm, the primer layer 2 and the top coating layer 4 are both made of polyurethane modified acrylate paint. Among them, the base film layer 1 of the embodiment specifically adopts PET film.

[0093] In addition, in the embodiment, the preparation method of the copper-plated coating film comprises the following steps:

[0094] S1, primer: coating the polyurethane modified acrylate paint prepared in

Preparation Example 1

[0095] S2, copper plating: evaporating copper on the side of the primer layer 2 away from the base film layer 1 to obtain the copper layer 3; when evaporating copper, the purity of copper particles is more than 99.99%, and before evaporating copper, titanium particles are added into the copper particles, and the mass of the titanium particles is 0.5% of the mass of the copper particles;

[0096] S3, top coating: coating the polyurethane modified acrylate paint prepared in

Preparation Example 1

[0097] Example 2

[0098] A copper-plated coating film, which is different from

Example 1

Preparation Example 2

[0099] Example 3

[0100] A copper-plated coating film, which is different from

Example 1

Preparation Example 3

[0101] Example 4

[0102] A copper-plated coating film, which is different from

Example 1

Preparation Example 4

[0103] Example 5

[0104] A copper plated coating film, which is different from Example 1 in that the polyurethane-modified acrylate coating material in S1 and S3 steps is the polyurethane-modified acrylate coating material prepared in Preparation Example 5.

[0105] Example 6

[0106] A copper plated coating film, which is different from Example 1 in that the polyurethane-modified acrylate coating material in S1 and S3 steps is the polyurethane-modified acrylate coating material prepared in Preparation Example 6.

[0107] Comparative Example

[0108] Comparative Example 1

[0109] A copper plated coating film, which is different from Example 1 in that:

[0110] The polyurethane-modified acrylate coating material in S1 and S3 steps is the polyurethane-modified acrylate coating material prepared in Comparative Preparation Example 1.

[0111] Comparative Example 2

[0112] A copper plated coating film, which is different from Example 1 in that:

[0113] The polyurethane-modified acrylate coating material in S1 and S3 steps is the polyurethane-modified acrylate coating material prepared in Comparative Preparation Example 2.

[0114] Comparative Example 3

[0115] A copper plated coating film, which is different from Example 1 in that:

[0116] The polyurethane-modified acrylate coating material in S1 and S3 steps is the polyurethane-modified acrylate coating material prepared in Comparative Preparation Example 3.

[0117] Performance test test

[0118] (1) Corrosion resistance: The copper plated coating films prepared in each example and comparative example were subjected to a corrosion resistance test, and the test method was as follows: the copper plated coating film was placed in an environment with a temperature of 40°C and a humidity of 90% for 1000h, and whether the copper plated coating film had a blackening phenomenon after the corrosion resistance test was observed.

[0119] (2) Copper layer evaporation uniformity: The thickness uniformity of the copper layer obtained in S2 step was detected with reference to ASTM B568, and the coefficient of variation was recorded in Table 1 below. The smaller the coefficient of variation, the better the copper layer evaporation uniformity.

[0120] (3) Copper layer adhesion: Refer to BB / T 0030 to test the adhesion between the copper layer obtained in step S2 and the base layer, and record the results in Table 1 below.

[0121] Table 1 Performance Test Data

[0122]

[0123] Based on the descriptions in Comparative Examples 1-3 and Example 1, as well as the test data in Table 1, it can be seen that: compared with Example 1, the copper-plated coating films in Comparative Examples 1-3 are prone to corrosion and blackening of the copper layer 3 in humid environments. This is because the topcoat 4 formed by the polyurethane-modified acrylic coating used in Comparative Examples 1-3 has poor density and uniformity, resulting in poor air barrier performance and thus a decrease in the corrosion resistance of the copper-plated coating film in humid environments. Secondly, compared with Example 1, the coefficient of variation of the copper layer 3 in the copper-plated coating film of Comparative Example 3 is significantly increased. This is because the uniformity of the base coat 2 formed by the polyurethane-modified acrylic coating is poor, leading to a decrease in the vapor deposition uniformity of the copper layer 3. In addition, compared with Example 1, the adhesion between the copper layer 3 and the base coat 2 in the copper-plated coating films of Comparative Examples 1-3 is reduced, indicating that hydroxyethyl acrylate, alkoxylated trimethylolpropane triacrylate, and the ratio of each component are all key factors in improving the adhesion between the copper layer 3 and the base coat 2.

[0124] Based on the test data from Examples 1, 3-6 and Table 1, it can be seen that the copper layer 3 in the copper-plated coating film of Example 4 has a smaller coefficient of variation, and the adhesion between the copper layer 3 and the base coating 2 is the greatest. This is because N-phenylglycine is selected as the amine additive and photoinitiator 184 is selected as the photoinitiator. The combination of the two is conducive to further promoting the stable curing of the base coating. On the one hand, it can improve the uniformity of the base coating 2, thereby further improving the evaporation uniformity of the copper layer 3. On the other hand, it is conducive to reducing the internal stress of the base coating 2, which can improve the adhesion between the base coating 2 and the base film layer 1, as well as the adhesion between the base coating 2 and the copper layer 3.

[0125] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this specific embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A copper-plated coating film, characterized in that: The coating comprises a base film layer, a primer layer, a copper layer, and a topcoat layer arranged sequentially. Both the primer layer and the topcoat layer are made of polyurethane-modified acrylate coating. The raw materials for preparing the polyurethane-modified acrylate coating include 30-40 parts by weight of trifunctional modified polyurethane acrylate, 8.5-10.5 parts by weight of hydroxyethyl acrylate, 5.5-7.0 parts by weight of alkoxylated trimethylolpropane triacrylate, 1-2 parts by weight of amine additives, 6-8 parts by weight of photoinitiator, and 1-1.5 parts by weight of leveling agent.

2. The copper-plated coating film according to claim 1, characterized in that: The amine auxiliaries are at least one of triethylamine, methyldiethanolamine, ethyl p-dimethylaminobenzoate, and N-phenylglycine, and the photoinitiator is at least one of photoinitiator TPO, photoinitiator 819, and photoinitiator 184.

3. The copper-plated coating film according to claim 2, characterized in that: The amine auxiliary is N-phenylglycine, and the photoinitiator is photoinitiator 184.

4. The copper-plated coating film according to claim 1, characterized in that: The alkoxylated trimethylolpropane triacrylate is at least one of ethoxylated trimethylolpropane triacrylate and propoxylated trimethylolpropane triacrylate.

5. The copper-plated coating film according to claim 1, characterized in that: The leveling agent used is an organosilicone polyether acrylate leveling agent.

6. A copper-plated coating film according to any one of claims 1-5, characterized in that: The thickness of the base coating and the top coating is 1-3 μm, and the thickness of the copper layer is 300-400 angstroms.

7. A method for preparing a copper-plated coating film as described in any one of claims 1-6, characterized in that, Includes the following steps: S1, Primer: A polyurethane-modified acrylate coating is applied to one surface of the base film layer and cured to form a primer layer; S2. Copper plating: Copper is deposited on the side of the base coating layer that is away from the base film layer to obtain a copper layer; S3. Topcoat: Apply a polyurethane-modified acrylate coating to the side of the copper layer away from the base coating, and after curing, form a topcoat to obtain a copper-plated coating film.

8. The method for preparing a copper-plated coating film according to claim 7, characterized in that: It also includes a pre-preparation step for the polyurethane-modified acrylic coating, wherein the preparation of the polyurethane-modified acrylic coating includes the following steps: Hydroxyethyl acrylate and alkoxylated trimethylolpropane triacrylate were added to a container under light-protected conditions, stirred evenly, and then a photoinitiator was added to dissolve until the mixture was transparent and free of particulate matter. The mixture was then filtered to obtain a semi-finished product. Under light-protected conditions, trifunctional modified polyurethane acrylate was added to another container, a leveling agent was added, and the mixture was stirred and dispersed to obtain a resin mixture. Under light-protected conditions, the semi-finished product and amine additives are added to the resin mixture and stirred until homogeneous to obtain a polyurethane-modified acrylic coating.

9. The method for preparing a copper-plated coating film according to claim 7, characterized in that: In steps S1 and S3, the curing energy required for the polyurethane-modified acrylate coating is 60-70 mJ / cm. 2 .

10. The method for preparing a copper-plated coating film according to claim 7, characterized in that: In step S2, when evaporating copper, the purity of the copper particles is above 99.99%, and before evaporating copper, titanium particles are added to the copper particles, with the mass of the titanium particles being 0.45-0.55% of the mass of the copper particles.

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