Copper plating coating film and preparation method thereof

Abstract

The invention discloses a copper-plated coating film and a preparation method thereof, and relates to the field of coating materials. The copper-plated coating film comprises a base film layer, a bottom coating layer, a copper layer and a surface coating layer which are arranged in sequence, and the bottom coating layer and the surface coating layer are both prepared from polyurethane modified acrylate paint. The polyurethane modified acrylate coating is prepared from the following raw materials in parts by weight: 30 to 40 parts of 3-functionality modified polyurethane acrylate, 8.5 to 10.5 parts of hydroxyethyl acrylate, 5.5 to 7.0 parts of alkoxylated trimethylolpropane triacrylate, 1 to 2 parts of an amine auxiliary agent, 6 to 8 parts of a photoinitiator and 1 to 1.5 parts of a flatting agent. According to the copper-plated coating film, the adhesion firmness 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 being corroded in a humid environment.

Description

Technical Field

[0001] The present application relates to the field of coating materials, and particularly to a copper-coated film and a preparation method thereof. Background Art

[0002] Copper-coated films are widely used in many fields, such as electronics, packaging, decoration, etc. However, there are still some areas for improvement in the actual application of traditional copper-coated films: 1. In the bonding treatment between the copper layer and the base film layer, the base film layer usually needs to be corona-treated to enhance the adhesion strength between the copper layer and the base film layer. However, static charges are easily left after corona treatment, and these static charges are easily adsorbed with dust or moisture in the environment, which may lead to pinholes and pits on the copper layer, and is not conducive to improving the evaporation uniformity of the copper layer; 2. The copper layer of the copper-coated film is directly exposed to the air, and the copper layer is easily oxidized and corroded in a humid environment, affecting its normal use. Summary of the Invention

[0003] In order to improve the adhesion strength between the copper layer and the base film layer in the related art, while improving the evaporation uniformity of the copper layer and solving the problem that the copper layer is easily corroded, the present application provides a copper-coated film and a preparation method thereof.

[0004] In a first aspect, the copper-coated film provided by the present application adopts the following technical solution: A copper-coated film includes a base film layer, a bottom coating layer, a copper layer, and a top coating layer arranged in sequence. Both the bottom coating layer and the top coating layer are made of a polyurethane-modified acrylate coating. Among them, 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 auxiliary agent, 6-8 parts by weight of photoinitiator, and 1-1.5 parts by weight of leveling agent.

[0005] In the present application, a bottom coating layer is added between the copper layer and the base film layer, and a top coating layer is added on the outer surface of the copper layer. Among them, the bottom coating layer is used to improve the adhesion strength between the copper layer and the base film layer, and can omit the step of corona-treating the base film layer, which is beneficial to preventing the problem that static charges left after corona treatment of the base film layer are easily adsorbed with dust or moisture in the environment and cause pinholes and pits on the copper layer; the top coating layer is used to isolate the air, improve the problem that the copper layer is easily oxidized and corroded in humid air, and plays a role in extending the service life of the copper-coated film.

[0006] In addition, in this application, both the bottom coating and the top coating are prepared using a polyurethane-modified acrylate coating made from 3-functional modified polyurethane acrylate, hydroxyethyl acrylate, alkoxylated trimethylolpropane triacrylate, amine additives, photoinitiators, and leveling agents in specific proportions. The coating made from this polyurethane-modified acrylate coating has high adhesion to the base film layer and the copper layer, good density and uniformity, and will not affect the copper plating uniformity of the subsequent copper plating process. A copper layer with good evaporation plating uniformity can be obtained. At the same time, the coating made from this polyurethane-modified acrylate coating can also effectively block moist air and has good weather resistance, can effectively protect the copper layer for a long time, prevent the erosion of the copper layer, and can effectively extend the service life of the copper plating coating film.

[0007] In some specific embodiments, the amine additive is 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.

[0008] In some preferred specific embodiments, the amine additive is N-phenylglycine, and the photoinitiator is photoinitiator 184.

[0009] In this application, the amine additive is preferably N-phenylglycine, and the photoinitiator is preferably photoinitiator 184. The combination of the two is beneficial to further promoting the stable curing of the bottom coating. On the one hand, it can improve the uniformity of the bottom coating, thereby further improving the thickness uniformity of the copper layer. On the other hand, it is beneficial to reduce the internal stress of the bottom coating, and can improve the adhesion strength between the bottom coating and the base film layer and the adhesion between the bottom coating and the copper layer.

[0010] In some specific embodiments, the alkoxylated trimethylolpropane triacrylate is at least one of ethoxylated trimethylolpropane triacrylate and propoxylated trimethylolpropane triacrylate.

[0011] In some preferred specific embodiments, the leveling agent is an organosilicon polyether acrylate leveling agent.

[0012] Compared with using polyether-modified polydimethylsiloxane as the leveling agent, using an organosilicon polyether acrylate leveling agent is beneficial to further improving the thickness uniformity of the copper layer.

[0013] Second, a preparation method for a copper plating coating film provided by this application adopts the following technical solution: A preparation method for a copper plating coating film includes the following steps: S1. Bottom coating: Coating a polyurethane-modified acrylate coating on one surface of the base film layer, and forming a bottom coating after curing; S2. Copper plating: Evaporate copper on the side of the bottom coating away from the base film layer to obtain a copper layer; S3. Top coating: Coating a polyurethane-modified acrylate coating on the side of the copper layer away from the bottom coating, and forming a top coating after curing to obtain a copper-plated coating film.

[0014] In some specific embodiments, the method for preparing the copper-plated coating film further includes a pre-preparation step of the polyurethane-modified acrylate coating. Among them, the preparation of the polyurethane-modified acrylate coating includes the following steps: Under light-shielded conditions, add hydroxyethyl acrylate and alkoxylated trimethylolpropane triacrylate into a container. After stirring evenly, add a photoinitiator and dissolve until it is transparent and free of particulate matter, and filter to obtain a semi-finished product; Under light-shielded conditions, add 3-functional modified polyurethane acrylate into another container, add a leveling agent, and stir and disperse to obtain a resin mixture. Under light-shielded conditions, add the semi-finished product and amine additives into the resin mixture, and stir and mix evenly to obtain a polyurethane-modified acrylate coating.

[0015] In this application, using the above method to prepare the polyurethane-modified acrylate coating is beneficial to promoting the uniform dispersion of each component and is beneficial to obtaining uniform bottom and top coatings.

[0016] In some specific embodiments, in steps S1 and S3, the curing energy required for the polyurethane-modified acrylate coating is 60-70 mj / cm 2 .

[0017] In this application, the curing energy required for the polyurethane-modified acrylate coating is preferably 60-70 mj / cm 2 , wherein, if the curing energy is too low, rapid curing cannot be achieved, and if the curing energy is too high, it is easy to cause adverse effects on the base film layer, such as causing shrinkage and yellowing of the base film layer.

[0018] In some specific embodiments, in step S2, during copper plating, the purity of the copper particles is above 99.99%, and before evaporating copper, titanium particles are incorporated into the copper particles, and the mass of the titanium particles is 0.45-0.55% of the mass of the copper particles.

[0019] In this application, before copper plating, incorporating titanium particles with a specific ratio into the copper particles, on the one hand, the titanium particles can preferentially react with the residual oxygen in the vacuum chamber to reduce the oxygen content of the copper layer, and on the other hand, the titanium particles can also promote the uniform nucleation of copper vapor, which is beneficial to improving the evaporation uniformity of the copper layer.

[0020] In summary, this application at least includes the following beneficial technical effects: 1. In this application, a bottom coating is added between the copper layer and the base film layer, and a top coating is added on the outer surface of the copper layer. Among them, both the bottom coating and the top coating are prepared with a polyurethane-modified acrylate coating made from 3-functional modified polyurethane acrylate, hydroxyethyl acrylate, alkoxylated trimethylolpropane triacrylate, amine additives, photoinitiator, and leveling agent in a specific ratio. The bottom coating is used to improve the adhesion fastness between the copper layer and the base film layer, which can omit the step of corona treatment on the base film layer, and is beneficial to preventing the problem that the residual static charge on the base film layer after corona treatment is likely to adsorb dust or moisture in the environment, resulting in pinholes and pockmarks on the copper layer. At the same time, the bottom coating has good density and uniformity, does not affect the copper plating uniformity of the subsequent copper plating process, and can obtain a copper layer with good evaporation plating uniformity. The top coating also has good density and uniformity as well as 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 for a long time, prevent the erosion of the copper layer, and can effectively extend the service life of the copper plating coating film.

[0021] (2) In this application, the amine additive is preferably N-phenylglycine, and the photoinitiator is preferably photoinitiator 184. The cooperation of the two is beneficial to further promoting the stable curing of the bottom coating. On the one hand, it can improve the uniformity of the bottom coating, thereby further enhancing the thickness uniformity of the copper layer. On the other hand, it is beneficial to reduce the internal stress of the bottom coating, and can improve the adhesion fastness between the bottom coating and the base film layer as well as the adhesion between the bottom coating and the copper layer. Description of the Drawings

[0022] Figure 1 It is a schematic structural diagram of a copper plating coating film of this application.

[0023] Description of the Reference Numerals: 1. Base film layer; 2. Bottom coating; 3. Copper layer; 4. Top coating. Detailed Embodiments

[0024] The following further illustrates this application in combination with specific experiments.

[0025] Preparation Example

Preparation Example 1

[0026] The preparation method of the above polyurethane-modified acrylate coating includes the following steps: Under light-shielded conditions, add hydroxyethyl acrylate and alkoxylated trimethylolpropane triacrylate to a container. After stirring evenly, add the photoinitiator and dissolve until transparent without particulate matter, and filter to obtain a semi-finished product; Under light-shielded conditions, add 3-functional modified polyurethane acrylate to another container, add the leveling agent, and stir and disperse to obtain a resin mixture. Under light-shielded conditions, add the semi-finished product and amine additives to the resin mixture, and stir and mix evenly to obtain a polyurethane-modified acrylate coating.

[0027] The minimum curing energy of this polyurethane-modified acrylate coating is 55 mj / cm 2 .

[0028]

Preparation Example 2

Preparation Example 1

[0029] In this preparation example, the polyurethane-modified acrylate coating includes the following raw materials: 3-functional modified polyurethane acrylate: 40 kg; In this example, the 3-functional modified polyurethane acrylate is specifically the 3-functional modified polyurethane acrylate of the brand Blue Coral with the model L-8414; Hydroxyethyl acrylate: 8.5 kg; Alkoxylated trimethylolpropane triacrylate: 5.5 kg; In this example, the alkoxylated trimethylolpropane triacrylate is specifically propoxylated trimethylolpropane triacrylate; Amine additive: 2 kg; In this example, the amine additive is specifically methyldiethanolamine; Photoinitiator: 6 kg; In this example, the photoinitiator is specifically Photoinitiator 184; Leveling agent: 1.5 kg; In this example, the leveling agent is specifically Degussa leveling agent TEGO 2100 silicone polyether acrylate leveling agent.

[0030] The minimum curing energy of this polyurethane-modified acrylate coating is 60 mj / cm 2 .

[0031]

Preparation Example 3

[0032] The minimum curing energy of this polyurethane-modified acrylate coating is 60 mj / cm 2 .

[0033]

Preparation Example 4

[0034] The minimum curing energy of this polyurethane-modified acrylate coating is 60 mj / cm 2 ..

[0035]

Preparation Example 5

[0036] The minimum curing energy of this polyurethane-modified acrylate coating is 60 mj / cm 2 .

[0037]

Preparation Example 6

[0038] The minimum curing energy of this polyurethane-modified acrylate coating is 60 mj / cm 2 .

[0039] Comparative Preparation Example

Comparative Preparation Example 1

[0040] The minimum curing energy of this polyurethane-modified acrylate coating is 60 mj / cm 2 .

[0041]

Comparative Preparation Example 2

[0042] The minimum curing energy of this polyurethane-modified acrylate coating is 60 mj / cm2 .

[0043]

Comparative Preparation Example 3

Preparation Example 1

[0044] The minimum curing energy of this polyurethane-modified acrylate coating is 60 mj / cm 2 . Example

[0045]

Example 1

[0046] In addition, in this example, the preparation method of the copper-plated coating film includes the following steps: S1. Primer coating: Coating the polyurethane-modified acrylate coating prepared in

Preparation Example 1

[0047] [Example 2] A copper-plated coating film, which is different from [Example 1] in that: the polyurethane-modified acrylate coatings in steps S1 and S3 are the polyurethane-modified acrylate coatings prepared in [Preparation Example 2].

[0048] [Example 3] A copper-plated coating film, which is different from [Example 1] in that: the polyurethane-modified acrylate coatings in steps S1 and S3 are the polyurethane-modified acrylate coatings prepared in [Preparation Example 3].

[0049] [Example 4] A copper-plated coating film, which is different from [Example 1] in that: the polyurethane-modified acrylate coatings in steps S1 and S3 are the polyurethane-modified acrylate coatings prepared in [Preparation Example 4].

[0050] [Example 5] A copper-plated coating film, which is different from [Example 1] in that: the polyurethane-modified acrylate coatings in steps S1 and S3 are the polyurethane-modified acrylate coatings prepared in [Preparation Example 5].

[0051] [Example 6] A copper-plated coating film, which is different from [Example 1] in that: the polyurethane-modified acrylate coatings in steps S1 and S3 are the polyurethane-modified acrylate coatings prepared in [Preparation Example 6].

[0052] Comparative Example [Comparative Example 1] A copper-plated coating film, which is different from [Example 1] in that: the polyurethane-modified acrylate coatings in steps S1 and S3 are the polyurethane-modified acrylate coatings prepared in [Comparative Preparation Example 1].

[0053] [Comparative Example 2] A copper-plated coating film, which is different from [Example 1] in that: the polyurethane-modified acrylate coatings in steps S1 and S3 are the polyurethane-modified acrylate coatings prepared in [Comparative Preparation Example 2].

[0054] [Comparative Example 3] A copper-plated coating film, which is different from [Example 1] in that: The polyurethane-modified acrylate coatings in steps S1 and S3 are the polyurethane-modified acrylate coatings prepared in [Comparative Preparation Example 3].

[0055] Performance Detection Test (1) Corrosion resistance: The copper-coated film prepared in each example and comparative example was subjected to a corrosion resistance test. The test method was as follows: The copper-coated film was placed in an environment with a temperature of 40 °C and a humidity of 90% and left standing for 1000 h, and then observed whether there was a blackening phenomenon after the corrosion resistance test of the copper-coated film.

[0056] (2) Copper layer evaporation uniformity: Referring to ASTM B568, the thickness uniformity of the copper layer obtained in step S2 was detected, and the coefficient of variation was recorded in Table 1 below. The smaller the coefficient of variation, the better the copper layer evaporation uniformity.

[0057] (3) Adhesion of copper layer: Referring to BB / T 0030, the adhesion between the copper layer obtained in step S2 and the bottom coating was detected, and the results were recorded in Table 1 below.

[0058] Table 1 Performance Detection Data Table Combined with the content recorded in Comparative Examples 1-3 and Example 1 and the detection data in Table 1, it can be seen that: compared with Example 1, the copper layer 3 of the copper-coated film in Comparative Examples 1-3 is prone to corrosion and blackening in a humid environment. The reason is that the dense uniformity of the surface coating 4 formed by the polyurethane-modified acrylate coating used in Comparative Examples 1-3 is poor, and the air-blocking performance is poor, resulting in a decrease in the corrosion resistance of the copper-coated film in a humid environment. Secondly, compared with Example 1, the coefficient of variation of the copper layer 3 in the copper-coated film of Comparative Example 3 increases significantly. The reason is that the uniformity of the bottom coating 2 formed by the polyurethane-modified acrylate coating is poor, resulting in a decrease in the evaporation uniformity of the copper layer 3. In addition, compared with Example 1, the adhesion between the copper layer 3 and the bottom coating 2 in the copper-coated film of Comparative Examples 1-3 decreases, indicating that hydroxyethyl acrylate, alkoxylated trimethylolpropane triacrylate, and the ratio of each component are all key factors for improving the adhesion between the copper layer 3 and the bottom coating 2.

[0059] Combined with Example 1 and Examples 3-6 and the detection data in Table 1, it can be seen that: the copper layer 3 in the copper-coated film of Example 4 has a smaller coefficient of variation, and at the same time, the adhesion between the copper layer 3 and the bottom coating 2 is the largest. The reason is that the amine-based additive is selected as N-phenylglycine, and the photoinitiator is selected as photoinitiator 184. The combination of the two is beneficial to further promoting the stable curing of the bottom coating. On the one hand, it can improve the uniformity of the bottom coating 2, thereby further improving the evaporation uniformity of the copper layer 3. On the other hand, it is beneficial to reduce the internal stress of the bottom coating 2, and can improve the adhesion fastness between the bottom coating 2 and the base film layer 1 and the adhesion between the bottom coating 2 and the copper layer 3.

[0060] This specific implementation manner is only an interpretation of the present application and does not limit the present application. After reading this specification, those skilled in the art can make modifications that do not contribute creatively to this specific implementation manner as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A copper-plated coating film, characterized in that: The invention comprises a base film layer, a primer layer, a copper layer and a top coat layer which are arranged in sequence, wherein the primer layer and the top coat layer are both made of a polyurethane modified acrylate coating, wherein the raw materials for preparing the polyurethane modified acrylate coating comprise 30-40 parts by weight of a 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 an amine auxiliary agent, 6-8 parts by weight of a photoinitiator and 1-1.5 parts by weight of a leveling agent.

2. The copper-plated coating film according to claim 1, characterized in that: The amine auxiliary agent is 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 agent 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 is an organosilicon polyether acrylate leveling agent.

6. A copper-plated coating film according to any one of claims 1 to 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 Å.

7. A method for preparing a copper-plated coating film according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1, primer: coating one surface of the base film layer with a polyurethane modified acrylate coating, and forming a primer after curing; S2, copper plating: evaporating copper on the side of the primer layer away from the base film layer to obtain a copper layer; S3, top coating: applying a polyurethane modified acrylate coating on the side of the copper layer away from the base coating, and forming a top coating after curing to obtain a copper-plated coating film.

8. The method for preparing a copper-plated coating film according to claim 7, characterized in that: The method also includes a pre-preparation step of the polyurethane modified acrylate coating, wherein the preparation of the polyurethane modified acrylate coating includes the following steps: Add hydroxyethyl acrylate and alkoxylated trimethylolpropane triacrylate into a container under light-proof conditions, stir evenly, add a photoinitiator and dissolve until transparent and free of particles, and filter to obtain a semi-finished product; Add the trifunctional modified polyurethane acrylate to another container under light-proof conditions, add a leveling agent, stir and disperse, and obtain a resin mixture. The semi-finished product and the amine auxiliary agent are added into the resin mixture under light-proof conditions, and the mixture is stirred and mixed evenly to obtain a polyurethane-modified acrylate 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 copper is evaporated, the purity of the copper particles is above 99.99%, and before the copper is evaporated, titanium particles are added to the copper particles, and the mass of the titanium particles is 0.45-0.55% of the mass of the copper particles.

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