CN113957421B - PET surface roughening liquid and preparation method thereof - Google Patents
PET surface roughening liquid and preparation method thereof Download PDFInfo
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- CN113957421B CN113957421B CN202111225262.4A CN202111225262A CN113957421B CN 113957421 B CN113957421 B CN 113957421B CN 202111225262 A CN202111225262 A CN 202111225262A CN 113957421 B CN113957421 B CN 113957421B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
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Abstract
The invention provides PET surface roughening liquid, which is prepared from the following components: 30-35 g/L of potassium permanganate, 20-25 g/L of sodium hydroxide, 2-4 g/L of 4-methylimidazole, 5-6 g/L of tetramethyl fluorourea hexafluorophosphate, 3-4 g/L of auxiliary agent and the balance of water. The invention also provides a preparation method of the PET surface roughening liquid. The PET surface roughening liquid provided by the invention has a good roughening effect.
Description
Technical Field
The invention relates to a roughening liquid, in particular to a PET surface roughening liquid and a preparation method thereof.
Background
The plastic electroplating generally adopts the following technological method: the method comprises the steps of degreasing, roughening, sensitization, activation and electroless nickel (or copper) deposition, wherein the roughening is an important link, the bonding force, the brightness and the integrity of a plating layer are directly influenced by the roughening, the surface of a plated part can be hydrophilic and form proper roughness through roughening, or the surface can form micropores, and the adsorption of colloidal palladium and the good adhesive force of the plating layer are ensured.
At present, most of roughening solutions for plastics contain chromic anhydride, and the roughening solution with the chromic anhydride formula can obtain good roughening effects on the surfaces of ABS and PC, but needs high-temperature heating in the use process, brings great harm to the environment and operators, and has poor roughening effects when being applied to the surfaces of PET.
The Chinese name of PET is polyethylene glycol terephthalate, which is prepared by exchanging dimethyl terephthalate with ethylene glycol or synthesizing dihydroxyethyl terephthalate by esterifying terephthalic acid with ethylene glycol, and then carrying out polycondensation reaction. The PET has smoother surface and stronger hydrophobicity, the roughening liquid containing the chromic anhydride has weak effect of improving the roughness of the PET surface, and the formed pits are also less, so that the roughening effect is poor.
Chinese patent application CN201610507429.9 discloses "a roughening solution for special engineering plastics", each liter of the roughening solution for special engineering plastics is composed of the following components: 150-250g/L of NaPS, 15-80g/L of benzene, 30-60g/L of tetrahydrofuran and 40-100ml/L of sulfuric acid. The roughening solution disclosed by the invention does not contain chromic acid in components, so that the pollution to the environment is small, but the roughening effect is poor when the roughening solution is applied to the PET surface.
Disclosure of Invention
The invention aims to solve the technical problem of providing PET surface roughening liquid which has a good roughening effect.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a PET surface roughening liquid is prepared from the following components: 30-35 g/L of potassium permanganate, 20-25 g/L of sodium hydroxide, 2-4 g/L of 4-methylimidazole, 5-6 g/L of tetramethyl fluorourea hexafluorophosphate, 3-4 g/L of auxiliary agent and the balance of water.
Further, the invention is made of the following components: 32g/L of potassium permanganate, 21g/L of sodium hydroxide, 3g/L of 4-methylimidazole, 5.5g/L of tetramethyl fluorourea hexafluorophosphate, 3.5g/L of auxiliary agent and the balance of water.
Further, the auxiliary agent is N, N-dimethylformamide.
Further, the water of the invention is deionized water.
The invention provides a preparation method of the PET surface roughening liquid.
In order to solve the technical problems, the technical scheme is as follows:
the preparation method of the PET surface roughening liquid comprises the following steps:
s1, adding potassium permanganate into water with the weight being 20 times that of the potassium permanganate, and stirring for 10-20 minutes to obtain a solution A;
s2, adding sodium hydroxide into water of which the weight is 20 times that of the sodium hydroxide, and stirring for 10-20 minutes to obtain an ethyl solution
S3, adding the 4-methylimidazole, the tetramethyl fluorourea hexafluorophosphate and the auxiliary agent into the rest water, and stirring until the mixture is uniformly mixed to obtain a propyl solution;
s4, mixing the first solution obtained in the step S1, the second solution obtained in the step S2 and the third solution obtained in the step S3, and stirring for 20-30 minutes to obtain the PET surface roughening liquid.
Further, in the step S3, the auxiliary agent is N, N-dimethylformamide.
Further, in the steps S1, S2, and S3 of the present invention, the water is deionized water.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention mainly comprises potassium permanganate, sodium hydroxide, 4-methylimidazole, tetramethyl fluorourea hexafluorophosphate, an auxiliary agent N, N-dimethylformamide and the like, wherein the auxiliary agent N, N-dimethylformamide has a swelling effect on the surface energy of PET; the potassium permanganate plays a role in oxidizing and corroding the PET surface energy in an alkaline environment, so that the roughness of the PET surface is improved; the 4-methylimidazole can strengthen the oxidation corrosion performance of potassium permanganate, so that the roughness of the PET surface and the binding force between PET and a coating are further improved, the consumption of potassium permanganate and sodium hydroxide can be reduced, and the pollution to the environment is reduced.
2) The tetramethyl fluorourea hexafluorophosphate used in the invention can effectively promote the hydrolysis process of ester bonds in PET surface molecules, hydrolyze the ester bonds to obtain hydroxyl groups, generate pits on the PET surface, further increase roughness, and simultaneously effectively improve the hydrophilicity of the PET surface, thereby further improving the binding force between PET and a coating, and in addition, the tetramethyl fluorourea hexafluorophosphate can effectively reduce the grain size of the coating, thereby improving the compactness of the coating.
Detailed Description
The present invention will be described in detail with reference to specific examples, wherein the exemplary embodiments of the present invention and the descriptions thereof are provided for the purpose of illustrating the present invention, but are not to be construed as limiting the present invention.
Example 1
PET surface roughening liquid is prepared from the following components: 32g/L potassium permanganate, 21g/L sodium hydroxide, 3 g/L4-methylimidazole, 5.5g/L tetramethyl fluorourea hexafluorophosphate, 3.5g/L N, N-dimethylformamide and the balance deionized water.
The preparation method of the PET surface roughening liquid comprises the following steps:
s1, adding potassium permanganate into deionized water with the weight being 20 times that of the potassium permanganate, and stirring for 15 minutes to obtain a solution A;
s2, adding sodium hydroxide into deionized water with the weight being 20 times of that of the sodium hydroxide, and stirring for 15 minutes to obtain an ethyl solution
S3, adding 4-methylimidazole, tetramethyl fluorourea hexafluorophosphate and N, N-dimethylformamide into the rest deionized water, and stirring until the mixture is uniformly mixed to obtain a propyl solution;
s4, mixing the first solution obtained in the step S1, the second solution obtained in the step S2 and the third solution obtained in the step S3, and stirring for 25 minutes to obtain the PET surface roughening liquid.
Example 2
PET surface roughening liquid is prepared from the following components: 33g/L of potassium permanganate, 22g/L of sodium hydroxide, 4g/L of 4-methylimidazole, 5g/L of tetramethyl fluorourea hexafluorophosphate, 3.3g/L of N, N-dimethylformamide and the balance of deionized water.
The preparation method of the PET surface roughening liquid comprises the following steps:
s1, adding potassium permanganate into deionized water with the weight being 20 times that of the potassium permanganate, and stirring for 18 minutes to obtain a solution A;
s2, adding sodium hydroxide into deionized water of which the weight is 20 times that of the sodium hydroxide, and stirring for 12 minutes to obtain an ethyl solution
S3, adding 4-methylimidazole, tetramethyl fluorourea hexafluorophosphate and N, N-dimethylformamide into the rest deionized water, and stirring until the mixture is uniformly mixed to obtain a propyl solution;
s4, mixing the first solution obtained in the step S1, the second solution obtained in the step S2 and the third solution obtained in the step S3, and stirring for 30 minutes to obtain the PET surface roughening liquid.
Example 3
PET surface roughening liquid is prepared from the following components: 30g/L of potassium permanganate, 25g/L of sodium hydroxide, 2g/L of 4-methylimidazole, 6g/L of tetramethyl fluorourea hexafluorophosphate, 3g/L of N, N-dimethylformamide and the balance of deionized water.
The preparation method of the PET surface roughening liquid comprises the following steps:
s1, adding potassium permanganate into deionized water with the weight being 20 times that of the potassium permanganate, and stirring for 10 minutes to obtain a solution A;
s2, adding sodium hydroxide into deionized water of which the weight is 20 times that of the sodium hydroxide, and stirring for 20 minutes to obtain an ethyl solution
S3, adding 4-methylimidazole, tetramethyl fluorourea hexafluorophosphate and N, N-dimethylformamide into the rest deionized water, and stirring until the mixture is uniformly mixed to obtain a propyl solution;
s4, mixing the first solution obtained in the step S1, the second solution obtained in the step S2 and the third solution obtained in the step S3, and stirring for 20 minutes to obtain the PET surface roughening liquid.
Example 4
PET surface roughening liquid is prepared from the following components: 35g/L potassium permanganate, 20g/L sodium hydroxide, 2.5 g/L4-methylimidazole, 5.7g/L tetramethyl fluorourea hexafluorophosphate, 4g/L N, N-dimethylformamide and the balance deionized water.
The preparation method of the PET surface roughening liquid comprises the following steps:
s1, adding potassium permanganate into deionized water with the weight being 20 times that of the potassium permanganate, and stirring for 20 minutes to obtain a solution A;
s2, adding sodium hydroxide into deionized water of which the weight is 20 times that of the sodium hydroxide, and stirring for 10 minutes to obtain an ethyl solution
S3, adding 4-methylimidazole, tetramethyl fluorourea hexafluorophosphate and N, N-dimethylformamide into the rest deionized water, and stirring until the mixture is uniformly mixed to obtain a propyl solution;
s4, mixing the first solution obtained in the step S1, the second solution obtained in the step S2 and the third solution obtained in the step S3, and stirring for 28 minutes to obtain the PET surface roughening liquid.
Reference example 1:
the difference from example 1 is that: the component lacks 4-methylimidazole.
Reference example 2:
the difference from example 1 is that: the component lacks tetramethyl fluorourea hexafluorophosphate.
Comparative example: example 1 of chinese patent application No. CN 201610507429.9.
Test example 1: roughness test
PET copper plating process: cutting the PET plate into test pieces with the length of 4cm multiplied by 4cm for horizontal copper deposition, wherein the steps are as follows: placing the test piece in a sodium hydroxide solution with the mass concentration of 20% for degreasing for 5 minutes at 50 ℃, taking out and washing with water; placing the test piece in surface roughening liquid (the surface roughening liquid prepared in examples 1-4, reference examples 1-2 and comparative examples) for roughening for 10 minutes at 50 ℃, taking out and washing with water; putting the test piece into a sensitization solution (15 g/L stannous chloride and 20ml/L hydrochloric acid) to be sensitized for 3 minutes at 50 ℃, transferring the test piece into an activation solution (0.25 g/L palladium chloride and 20ml/L hydrochloric acid) to be activated for 5 minutes at 40 ℃, taking out and washing with water; the test piece was placed in an electroless copper plating solution (copper sulfate 10g/L, sodium hypophosphite 25g/L, EDTA 33g/L, potassium sodium tartrate 20g/L, pH 11) and plated at 50℃for 30 minutes.
The test pieces corresponding to examples 1 to 4, reference examples 1 to 2 and comparative examples were respectively tested for surface roughness after roughening using an atomic force microscope, and the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the surface roughness of the PET surface roughening solutions prepared in examples 1 to 4 of the present invention is higher than that of the PET surface roughening solution prepared in comparative example, which shows that the PET surface roughening solution prepared in the present invention has a good effect of improving the PET surface roughness. The partial components of reference examples 1 and 2 are different from those of example 1, and the surface roughness of the reference examples 1 and 2 is reduced compared with that of example 1, which shows that the 4-methylimidazole and the tetramethyl fluorourea hexafluorophosphate used in the invention can effectively improve the roughness of PET surface.
Test example 2: plating binding force test
The test pieces corresponding to examples 1 to 4, reference examples 1 to 2, and comparative examples were respectively tested for plating adhesion after electroless copper plating with reference to ASTM D3330 standard peel test method, and the test results are shown in table 2:
TABLE 2
| Plating binding force (N/cm) | |
| Example 1 | 15.9 |
| Example 2 | 15.5 |
| Example 3 | 15.8 |
| Example 4 | 15.6 |
| Reference example 1 | 13.4 |
| Reference example 2 | 14.1 |
| Comparative example | 11.7 |
As can be seen from Table 2, the binding force of the coating in the examples 1-4 of the invention is higher than that in the comparative example, which shows that the PET surface roughening solution prepared by the invention has better effect of improving the binding force between PET and the coating. The components of reference examples 1 and 2 are different from those of example 1, and the binding force of the plating layers of reference examples 1 and 2 is reduced compared with that of example 1, which shows that the 4-methylimidazole and the tetramethyl fluorourea hexafluorophosphate used in the invention can effectively improve the binding force between PET and the plating layers.
Test example 3: plating grain size test
The crystal structure characterization of the plating layers of the test pieces corresponding to examples 1 to 4, reference example 2 and comparative example after electroless copper plating were respectively tested using an X-ray diffractometer, and the grain sizes were calculated by Scherrer formula, and the test results are shown in table 3:
TABLE 3 Table 3
| Grain size (nm) | |
| Example 1 | 13.6 |
| Example 2 | 13.9 |
| Example 3 | 14.2 |
| Example 4 | 13.8 |
| Reference example 2 | 15.7 |
| Comparative example | 17.5 |
As can be seen from Table 3, the grain sizes of examples 1 to 4 of the present invention are all lower than those of the comparative examples, indicating that the PET surface roughening liquid prepared by the present invention has a good effect of reducing the grain size of the coating formed by PET. The partial composition of reference example 2 is different from that of example 1, and the grain size of reference example 2 is not increased much as compared with example 1, indicating that the tetramethyl fluorourea hexafluorophosphate used in the present invention can effectively reduce the grain size of the plating layer.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (7)
1. The PET surface roughening liquid is characterized in that: is prepared from the following components: 30-35 g/L of potassium permanganate, 20-25 g/L of sodium hydroxide, 2-4 g/L of 4-methylimidazole, 5-6 g/L of tetramethyl fluorourea hexafluorophosphate, 3-4 g/L of auxiliary agent and the balance of water.
2. The PET surface roughening liquid according to claim 1, wherein: is prepared from the following components: 32g/L of potassium permanganate, 21g/L of sodium hydroxide, 3g/L of 4-methylimidazole, 5.5g/L of tetramethyl fluorourea hexafluorophosphate, 3.5g/L of auxiliary agent and the balance of water.
3. The PET surface roughening liquid according to claim 1, wherein: the auxiliary agent is N, N-dimethylformamide.
4. The PET surface roughening liquid according to claim 1, wherein: the water is deionized water.
5. The method for preparing the PET surface roughening liquid according to any one of claims 1 to 4, which is characterized in that: the method comprises the following steps:
s1, adding potassium permanganate into water with the weight being 20 times that of the potassium permanganate, and stirring for 10-20 minutes to obtain a solution A;
s2, adding sodium hydroxide into water of which the weight is 20 times that of the sodium hydroxide, and stirring for 10-20 minutes to obtain an ethyl solution
S3, adding the 4-methylimidazole, the tetramethyl fluorourea hexafluorophosphate and the auxiliary agent into the rest water, and stirring until the mixture is uniformly mixed to obtain a propyl solution;
s4, mixing the first solution obtained in the step S1, the second solution obtained in the step S2 and the third solution obtained in the step S3, and stirring for 20-30 minutes to obtain the PET surface roughening liquid.
6. The method for preparing the PET surface roughening liquid according to claim 5, which is characterized in that: in the step S3, the auxiliary agent is N, N-dimethylformamide.
7. The method for preparing the PET surface roughening liquid according to claim 5, which is characterized in that: in the steps S1, S2 and S3, the water is deionized water.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0139090A1 (en) * | 1983-08-05 | 1985-05-02 | Schering Aktiengesellschaft | Process for the pre-treatment of polyimides |
| JP2000265028A (en) * | 1999-03-15 | 2000-09-26 | Ibiden Co Ltd | Resin composition for forming roughened surface and printed wiring board |
| CN101928937A (en) * | 2009-06-22 | 2010-12-29 | 比亚迪股份有限公司 | Colloid palladium activation solution, preparation method thereof and non-metal surface activation method |
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- 2021-10-21 CN CN202111225262.4A patent/CN113957421B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0139090A1 (en) * | 1983-08-05 | 1985-05-02 | Schering Aktiengesellschaft | Process for the pre-treatment of polyimides |
| JP2000265028A (en) * | 1999-03-15 | 2000-09-26 | Ibiden Co Ltd | Resin composition for forming roughened surface and printed wiring board |
| CN101928937A (en) * | 2009-06-22 | 2010-12-29 | 比亚迪股份有限公司 | Colloid palladium activation solution, preparation method thereof and non-metal surface activation method |
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