# US 9,138,733 B2 · Stable tin free catalysts for electroless metallization

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- Number: US 9,138,733 B2
- Document ID: US9138733B2
- Status: Granted
- Kind: B2
- Application number: 13/589,019
- Filed: 2012-08-17
- Published: 2013-08-22
- Granted: 2015-09-22
- Earliest claimed: 2011-08-17
- Assignees: Rohm and Haas Electronic Materials LLC
- Applicants: Feng Liu; Maria Anna Rzeznik
- Inventors: Feng Liu; Maria Anna Rzeznik
- Web page: https://patentgrep.com/patent/US9138733B2

## CPC

- C23C 18/1834: {Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers}
- B01J 23/44: Palladium
- B01J 31/061: {Chiral polymers}
- B01J 31/28: of the platinum group metals, iron group metals or copper
- B01J 35/23: in a colloidal state
- B01J 35/393: {Metal or metal oxide crystallite size}
- B01J 35/45: Nanoparticles
- B01J 37/0201: {Impregnation}
- B01J 37/0209: {involving a reaction between the support and a fluid}
- B01J 37/0213: {Preparation of the impregnating solution}
- B01J 37/16: Reducing
- C23C 18/1831: {Use of metal, e.g. activation, sensitisation with noble metals}
- C23C 18/1879: {Use of metal, e.g. activation, sensitisation with noble metals}
- C23C 18/1882: {Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers}
- C23C 18/206: {Use of metal other than noble metals and tin, e.g. activation, sensitisation with metals (sensitising with tin C23C18/285, sensitising with noble metals C23C18/30)}
- 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 18/30: Activating {or accelerating or sensitising with palladium or other noble metal}
- C23C 18/34: using reducing agents
- C23C 18/40: using reducing agents
- C23C 18/50: with alloys based on iron, cobalt or nickel
- H05K 3/422: {characterised by electroless plating method; pretreatment therefor}
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- B01J 2531/0272: derived from carbohydrates, including e.g. tartrates or DIOP
- B01J 2531/824: Palladium
- 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: 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)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- H05K: PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS

## Abstract

Catalysts which include nanoparticles of palladium metal and cellulose derivatives are used in electroless metal plating. The palladium catalysts are free of tin.

## Claims

### Claim 1

An aqueous catalyst solution consisting of one or more antioxidants, nanoparticles of palladium metal and one or more compounds chosen from polymers having a formula:
wherein R1, R2, R3, R4, R5, R6 and R7 are the same or different and chosen from —H, —CH2COOX, —C(O)—CH3, —C(O)—(CH2)z—CH3 and
wherein n is an integer of at least 2, z is an integer of at least 1 and X is —H or a counter cation, and a reaction product of a polymer having a formula:
wherein R9, R10, R11, R12, R13, R14, and R15 are the same or different and are chosen from —H, —CH3, —CH2CH3, —CH2OH, —[CH2CHR8]x—OH, —CH2CH(OH)CH3 and —(CH2CHR8O)y—H, with the proviso that at least one of R9, R10, R11, R12, R13, R14, and R15 is —CH2OH, —[CH2CHR8]x—OH, —CH2CH(OH)CH3 or —(CH2CHR8O)y—H, wherein R8 is —H or —CH3, x and y are integers of at least 1 and n and z are as described above, and a quaternary compound having a formula:
wherein m is an integer from 1 to 16, Y is halogen, Z− is a counter anion, R16, R17 and R18 are the same or different and are —H, —CH3 or —(CH2)p—CH3, and R19 is —H or —CH3 and p is an integer of 1 to 9, and one or more cross-linking agents, the catalyst is free of tin.

### Claim 2 (depends on 1)

The aqueous catalyst of claim 1, wherein at least one of R2, R3, R5, R6 and R7 is —CH2COOX or —C(O)—CH3.

### Claim 3 (depends on 1)

The aqueous catalyst of claim 1, wherein the nanoparticles are 1 nm to 1000 nm.

### Claim 4 (depends on 1)

The aqueous catalyst of claim 1, wherein the cross-linking agent is chosen from one or more of haloepoxy compounds and di-epoxy compounds.