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Chrome-free etch solutions for chemically resistant polymer materials

a technology of etch solution and polymer material, which is applied in the direction of liquid/solution decomposition chemical coating, coating, chemical apparatus and processes, etc., can solve the problems of toxic and environmentally unfriendly etch solution, etch solution of cr(vi) present undue hazards to workers in the plating arts as well as the environment, and no satisfactory commercial product which is free of cr(vi) is currently available on the market. , the probability of adhesion failure and blistering between the surfa

Inactive Publication Date: 2019-01-31
ROHM & HAAS ELECTRONICS MATERIALS LLC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

The methods described in this patent allow for effective etching of chemically resistant polymer materials, such as acrylonitrile butadiene styrene and acrylonitrile butadiene styrene-polycarbonate, to prepare them for electroless metallization. The etched surface provides good metal adhesion, resulting in strong peeling strength between the metal layers and reduces the likelihood of adhesion failure and blistering. The method is also safe for the environment as it is a chrome-free etch solution and does not contain hazardous acids.

Problems solved by technology

However, such etching solutions are toxic and environmentally unfriendly.
Etch solutions of Cr(VI) present undue hazards to workers in the plating arts as well as the environment.
Although great efforts have been made over the years by many chemical suppliers and the plating industry to replace currently used toxic etching solutions, no satisfactory commercial product which is free of Cr(VI) is currently available on the market.
The acid is highly corrosive and disposal is expensive.
In general, working with sulfuric acid is hazardous.
Sulfuric acid fumes are toxic and have target organ effects on skin, respiratory, reproductive systems and fetal tissue.
Oxidizing agents are consumed either by the etching process or due to the instability of the oxidants.
However, either in an acidic or alkaline medium, Mn(VII) is unstable and tends to reduce to its lower oxidation states, especially to Mn(IV), consequently forming a large quantity of the insoluble MnO2 and causing quality issues on the treated polymer surfaces.
Therefore, such etch solutions are inadequate to meet the demands of the metal plating industry for polymer preparation for electroless metallization, including electroless metallization of chemically resistant polymers, such as acrylonitrile butadiene styrene and acrylonitrile butadiene styrene-polycarbonate.

Method used

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  • Chrome-free etch solutions for chemically resistant polymer materials
  • Chrome-free etch solutions for chemically resistant polymer materials
  • Chrome-free etch solutions for chemically resistant polymer materials

Examples

Experimental program
Comparison scheme
Effect test

example 1 (

Invention)

Copper Adhesion to ABS and ABS-PC Etched with an Aqueous Alkaline Hydrogen Peroxide Composition of the Invention

[0046]1. ABS-PC coupons are etched for 6 minutes at about 70° C. in an aqueous alkaline composition composed of 14 g / L hydrogen peroxide, 18 g / L sodium hydroxide with the balance water and the pH is 12.8, then the etched coupons are rinsed with DI water at room temperature for 2 minutes;[0047]2. The etched coupons are treated in CIRCUPOSIT™ Conditioner 3325 aqueous alkaline solution or CIRCUPOSIT™ Conditioner 231 aqueous alkaline solution at 60° C. for 5 minutes, then rinsed with DI water for 2 minutes;[0048]3. The etched and conditioned coupons are submerged in an acidic pre-dip solution maintained at pH 2 with nitric acid for 1 minute before applying an ionic catalyst;[0049]4. Each etched and conditioned coupon is immersed into ionic aqueous alkaline catalyst solutions for 5 minutes at 40° C., wherein the catalyst includes palladium ions complexed with 2,5-dime...

example 3 (

Invention)

Aqueous Alkaline Hydrogen Peroxide Etch of ABS

[0071]A plurality of injection molded NOVODUR™ P2MC ABS polymer coupons available from Styrolution Group Corporation are cleaned in a 1.5% by volume solution of Dow product Cleaner PM-900 (available from The Dow Chemical Company, Midland, Mich.).

[0072]Each ABS polymer coupon is immersed in the cleaning solution for 5 minutes at 50° C. The cleaned coupons are then rinsed with DI water at room temperature for 2 minutes.

[0073]The cleaned coupons are then treated with a solvent swell which has the formulation described in Table 1.

TABLE 1COMPONENTAMOUNTPropylene carbonate130 g / L EO / PO Block Copolymer110 g / Lγ-butyrolactone60 g / LWaterTo one liter1PLURONIC ™ L-64 available from Sigma Aldrich.

[0074]Each cleaned ABS coupon is then immersed in the solvent swell for 2 minutes at about 40° C. The swelled ABS coupons are rinsed with DI water at room temperature for 2 minutes. The surface of each coupon is then analyzed for surface morphology...

example 4 (

Invention)

Electroless Copper Plating of ABS and ABS-PC Coupons Etched with an Aqueous Alkaline Solution of the Invention

[0076]A plurality of injection molded NOVODUR™ P2MC ABS polymer coupons and BAYBLEND™ T45PG ABS-PC polymer blend coupons (available from Bayer) are provided. The coupons are treated and electroless copper plated according to the following method:[0077]1. Each coupon is treated in a cleaning solution as disclosed in Example 3 for 5 minutes at about 50° C., then each coupon is rinsed with DI water for 2 minutes at room temperature;[0078]2. The cleaned coupons are then treated with a solvent swell as disclosed in Example 1, Table 2 for 2 minutes at about 40° C. to swell the ABS and ABS-PC, then each coupon is rinsed with DI water for 2 minutes at room temperature;[0079]3. The solvent swelled coupons are then etched for 6 minutes at about 70° C. in an aqueous alkaline composition composed of 13.5 g / L hydrogen peroxide, 17 g / L sodium hydroxide with the balance water and...

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Abstract

Chemically resistant polymers are etched using a chrome-free etch solution which is aqueous and alkaline. The chrome-free etch aqueous alkaline solution is environmentally friendly and can be used in the preparation of chemically resistant polymers for electroless metal plating including the plating of through-hole walls in the manufacture of printed circuit boards.

Description

FIELD OF THE INVENTION[0001]The present invention is directed to chrome-free etch solutions and methods for etching chemically resistant polymer materials. More specifically, the present invention is directed to chrome-free etch solutions and methods for etching chemically resistant polymer materials, wherein the chrome-free etch solutions are aqueous alkaline solutions and are environmentally friendly and the chemically resistant polymer materials include acrylonitrile butadiene styrene, acrylonitrile butadiene styrene-polycarbonate or combinations thereof.BACKGROUND OF THE INVENTION[0002]Prior to electroless metallization a substrate surface containing organic polymers is typically etched with an etch solution to achieve good adhesion between the substrate surface and electroless plated metals. Chemically resistant polymers such as, for example, acrylonitrile butadiene styrene and acrylonitrile butadiene styrene-polycarbonate are highly desirable for articles and products which ar...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C23C18/24
CPCC23C18/24C09K13/02C08J7/12C08J2355/02C08J2369/00C08J2455/02C08J2469/00C23C18/2086C23C18/22C23C18/32C23C18/38C23C18/48C23C18/50C09K13/00C23C18/1641C23C18/1872
Inventor MULZER, CATHERINE
Owner ROHM & HAAS ELECTRONICS MATERIALS LLC
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