# US 10,501,852 B2 · Formulation for the etching of polymer materials prior to coating of the materials

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- Number: US 10,501,852 B2
- Document ID: US10501852B2
- Status: Granted
- Kind: B2
- Application number: 16/226,606
- Filed: 2018-12-19
- Published: 2019-05-09
- Granted: 2019-12-10
- Earliest claimed: 2017-09-28
- Assignees: Avanzare InnovacióN TecnolóGica, S,L.
- Applicants: Avanzare InnovacióN TecnolóGica, S.L.
- Inventors: Julio Gomez Cordon; Luis Otaño Jimenez; Javier Perez Martinez
- Web page: https://patentgrep.com/patent/US10501852B2

## CPC

- C23C 18/24: using acid aqueous solutions
- C09K 13/10: containing a boron compound
- C23C 18/122: {Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes}
- C23C 18/1641: {Organic substrates, e.g. resin, plastic}
- C23C 18/1653: {Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating}
- C23C 18/2066: {Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers}
- C23C 18/2086: {with use of organic or inorganic compounds other than metals, first}
- C23C 18/28: Sensitising or activating
- C23C 18/30: Activating {or accelerating or sensitising with palladium or other noble metal}
- C25D 3/38: of copper
- C25D 5/56: of plastics
- C09K 2211/183: of the refractory metals, i.e. Ti, V, Cr, Zr, Nb, Mo, Hf, Ta or W
- C23C 18/32: Coating with nickel, cobalt or mixtures thereof with phosphorus or boron (C23C18/50 takes precedence)
- C23C 18/38: Coating with copper
- C23C 18/54: Contact plating, i.e. electroless electrochemical plating
- C23C 2222/10: Use of solutions containing trivalent chromium but free of hexavalent chromium
- 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 (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C25D: PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR

## Abstract

A new formulation of treatment baths for the etching of polymers prior to metallization or coating of the polymer using known technologies described in the state of the art, which are based on the use of salts and/or complexes of the Cr(III) cation, where the formulation includes a salt and/or Cr(III) complex in which the Cr(III) is coordinated to at least one or several mono, bi, tri, tetra, penta, hexadentate or bridging ligands that are coordinated to the chromium by the oxygen, sulfur or nitrogen atom or several of these atoms of the ligands, such that after the polymer piece has been etched with the Etching formulation described above, the metal coating is carried out by means of the application of chemical and electrolyte baths in the case of metallization, or by means of the application of paint or another organic coating.

## Claims

### Claim 1

A method of acid etching a thermoplastic, thermoset or elastomeric polymer material, the method comprising:
etching the thermoplastic, thermoset or elastomeric polymer material with an etching bath comprising an acid and Cr(III) coordination complexes, wherein the acid concentration in the etching bath is from 20 wt. % to 98 wt. %; and
applying a metallization coating or organic coating to the etched thermoplastic, thermoset or elastomeric polymer material.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the Cr (III) coordination complexes comprise one or more ligands selected from mono, bi, tri, tetra, penta, hexadentate or bridging ligands that are coordinated to the chromium by an oxygen, sulfur or nitrogen atom or a combination thereof.

### Claim 3 (depends on 2)

The method according to claim 2, wherein the ligands are selected from formate, acetate, propanoate, butanoate, benzoate, phenylacetate, phenylpropionate, cyanamate, alkylbenzoates, pyruvate, levulinate, citrate, isocitrate, aconitate, trimellitate, glycinate, valinate, leucinate, threoninate, lysinate, tryptophanate, histidinate, phenylalaninate, isoleucinate, argininate, methioninate, alaninate, prolinate, serinate, cysteinate, asparaginate, glutaminate, tyrosinate, aspartate, polyaspartate, glutamate, cysteinate, homocysteinate, ornithinate, nicotinate, oxalate, propanedioate, butanedioate, pentanedioate, hexanedioate, maleate, fumarate, phthalate, isophthalate, terephthalate, tartrate, itaconate, mesaconate, citraconate, glycolate, lactate, mandelate, salicylate, gluconate, ethylenediaminetetraacetate, nitrilotriacetate, iminodisuccinate, ethylenediaminedisuccinate, methylglycine diacetate, N,N,diacetate glutamate, cyclohexylenedinitrilotetraacetate, diethylenetriaminepentaacetate, aminoethyl ethylene glycol tetraacetate, triethylenetetramine hexaacetate, dihydroxyethylglycinate, iminodiacetate, oxamate, nitrilotripropionate, ethylenediamine dipropionate, thiodipropionate, dithiodipropionate, aminopropanoate, aminopentanoate, aminohexanoate, 2-aminobenzoate, 3-aminobenzoate, 4-aminobenzoate, 3-cyclohexylamino-propylamine, ethylenediamine, 1,3-diaminopropane, dimethylaminopropylamine, diethylaminopropylamine, bis(3-aminopropyl)-methylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, polyamines, 3-(2-aminoethyl)amino-propylamine, N,N′-bis(3-aminopropyl)ethylenediamine, neopentanediamine, cyclohexanediamine, hexane-1,6-diamine, imidazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethylimidazole, 2-ethyl-4-methyl-imidazole, N-(3-Aminopropyl)-imidazole, pyrazole, niacinamide, bipyridine, phenanthroline.

### Claim 4 (depends on 1)

The method according to claim 1, wherein the concentration of the Cr(III) complex is in the range of 2 mM and 2 M.

### Claim 5 (depends on 1)

The method according to claim 1, wherein the acid in the etching bath is selected from sulfuric acid, aminosulfuric (sulfamic) acid, phosphoric acid, diphosphoric acid, metaphosphoric acid, polyphosphoric acid, methanesulfonic acid, acid ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, alkylbenzenesulfonic acids, monoalkylphosphoric acids, dialkylphosphoric acids, isethionic acid, perchloric acid, chloric acid, nitric acid, trifluoromethanesulfonic acid, trifluoroacetic acid, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorosilicic acid, hydrofluoric acid, boric acid or mixtures thereof.

### Claim 6 (depends on 1)

The method according to claim 1, wherein the percentage by weight of acids is comprised between 65 and 98 wt. %.

### Claim 7 (depends on 1)

The method according to claim 1, wherein the etching temperature is comprised between 10° C. and 95° C.

### Claim 8 (depends on 1)

The method according to claim 1, wherein the etching time is comprised between 30 seconds and 1 hour.

### Claim 9 (depends on 1)

The method of claim 1, wherein the organic coating of polymer materials is by organic-based paint, varnish or coating.