I 1111111111111111 11111 1111111111 11111 11111 111111111111111 IIIIII IIII IIII IIII
`US007300563B2
`
`c12) United States Patent
`Diaddario, Jr.
`
`(IO) Patent No.:
`(45) Date of Patent:
`
`US 7,300,563 B2
`Nov. 27, 2007
`
`(54) USE OF N-ALLLYL SUBSTITUTED AMINES
`AND THEIR SALTS AS BRIGHTENING
`AGENTS IN NICKEL PLATING BATHS
`
`(75)
`
`Inventor: Leonard L. Diaddario, Jr.,
`Independence, OH (US)
`
`(73) Assignee: Pavco, Inc., Charlotte, NC (US)
`
`( *) Notice:
`
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 253 days.
`
`(21) Appl. No.: 10/774,558
`
`(22) Filed:
`
`Feb. 9, 2004
`
`(65)
`
`Prior Publication Data
`
`US 2004/0154928 Al
`
`Aug. 12, 2004
`
`Related U.S. Application Data
`
`(60) Provisional application No. 60/445,612, filed on Feb.
`7, 2003.
`
`(51)
`
`Int. Cl.
`C25D 3/56
`(2006.01)
`C25D 3112
`(2006.01)
`C23C 16100
`(2006.01)
`(52) U.S. Cl. ...................... 205/259; 205/271; 106/1.27
`(58) Field of Classification Search ................ 205/259,
`205/271; 106/1.27
`See application file for complete search history.
`
`(56)
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`3,772,168 A
`3,862,019 A
`4,054,495 A
`4,077,855 A
`4,212,709 A
`4,435,254 A
`5,438,140 A
`5,445,727 A
`5,606,067 A
`5,611,906 A
`5,840,096 A
`
`11/1973 Dillenberg .................. 204/435
`1/1975 Rosenberg et al.
`........... 204/49
`10/ 1977 Law et al.
`. . . . . . . . . . . . . . . . . . . . 204/ 49
`3/ 1978 Popescu . . . . . . . . . . . . . . . . . . . . . . 204/ 49
`7/1980 Patsch et al.
`................. 204/49
`3/1984 Lemke ........................ 204/49
`8/1995 Oftring et al. .............. 546/147
`8/1995 Schwendemann et al ... 205/271
`2/1997 Burkhart et al. ............ 546/347
`3/1997 Burkhart et al. ............ 205/271
`11/1998 Tajima et al. ................ 65/30.1
`
`FOREIGN PATENT DOCUMENTS
`
`GB
`GB
`GB
`
`1001957
`1091197
`1550168
`
`8/1965
`11/1967
`8/1979
`
`OTHER PUBLICATIONS
`
`Lowenheim, Electroplating, c. 1978 (no month), pp. 205-220.*
`
`* cited by examiner
`
`Primary Examiner-Edna Wong
`(74) Attorney, Agent, or Firm-Fay Sharpe LLP
`
`(57)
`
`ABSTRACT
`
`An aqueous acidic plating bath for the electrodeposition of
`a nickel or nickel alloy deposit. The bath includes nickel ions
`and an additive having the general formula:
`
`[H2C~CHCH2N•R1 R2R3Jnxn-
`wherein R 1 , R2 and R3 are selected from the functional
`groups consisting of hydrogen, methyl, ethyl, propyl, ally!,
`propyn, propanediol and combinations thereof; and xn- is an
`n-valent inorganic or organic anion.
`
`2,876,177 A
`3,133,006 A *
`
`3/1959 Giindel ........................ 204/49
`5/1964 Ostrow et al. .............. 205/271
`
`20 Claims, No Drawings
`
`Mylan Exhibit 1144
`Mylan v. Regeneron, IPR2021-00881
`Page 1
`
`

`

`US 7,300,563 B2
`
`1
`USE OF N-ALLLYL SUBSTITUTED AMINES
`AND THEIR SALTS AS BRIGHTENING
`AGENTS IN NICKEL PLATING BATHS
`
`This application claims priority under 35 U.S.C. §119(e) 5
`to provisional application 60/445,612, filed on Feb. 7, 2003.
`
`FIELD OF THE INVENTION
`
`The present invention relates to aqueous acid nickel
`electroplating solutions and a method for electroplating
`nickel coatings. Specifically, the invention relates to an
`acidic nickel electroplating solution including an additive
`that produces an extremely ductile, leveled and highly
`brilliant deposit.
`
`BACKGROUND OF THE INVENTION
`
`2
`Other patents disclose the use of single or multi ring
`nitrogen containing heterocyclic amines as Class II bright(cid:173)
`eners for bright nickel electroplating systems. U.S. Pat. Nos.
`2,876,177 and 3,862,019 discuss the use of pyridine sulfo(cid:173)
`betaines. U.S. Pat. No. 4,212,709 expands on the pyridine(cid:173)
`based brighteners to include mononuclear and polynuclear
`aromatic heterocyclic nitrogen bases. U.S. Pat. Nos. 5,438,
`140 and 5,45,727 describe the use of alkyl derivatives of
`nitrogen containing heterocycles as brighteners for nickel
`10 electroplating systems. U.S. Pat. Nos. 5,606,067 and 5,611,
`906 disclose the preparation of these compounds.
`The above mentioned brightener systems, however, may
`exhibit one or more of the following limitations: poor
`ductility; limited low-current density coverage; poor level-
`15 ing at low-current densities; burning at high current densi(cid:173)
`ties; or decreased receptivity to subsequent chromium
`deposits. It is therefore desirable to develop an brightener
`system for an acidic nickel plating bath that will produce an
`extremely ductile, leveled and highly bright deposit over a
`20 wide range of current densities.
`
`Nickel is one of the most important electrodeposited
`metals due to its excellent decorative and corrosion-resis(cid:173)
`tance properties. Most nickel electrolyte systems are based
`on the Watts plating bath, which generally contains nickel
`sulfate, nickel chloride, and boric acid. Electroplating baths
`have been developed to produce ductile, low-stress, high
`leveling, semi-bright and bright nickel deposits. A multilay(cid:173)
`ered nickel deposit, containing a sulfur-free semi-bright
`nickel layer with a sulfur-containing bright nickel layer,
`significantly improves corrosion protection.
`A variety of organic compounds are used as brighteners in 30
`nickel baths to provide a bright, level, and ductile nickel
`deposit. Nickel brighteners are generally divided into two
`classes. Class I, or primary, nickel brighteners include
`compounds such as aromatic or unsaturated aliphatic sul(cid:173)
`fonic acids, sulfonamides, sulfonimides, and sulfimides. 35
`Class I brighteners are used in relatively high concentrations
`and produce a hazy or cloudy deposit on the metal substrate.
`Class I brighteners decompose during the electroplating
`process, and sulfur is incorporated into the deposit, which
`reduces the internal tensile stress of the deposit.
`Class II, or secondary, nickel brighteners are used in
`combination with Class I brighteners to produce a fully
`bright and leveled nickel deposit. Class II brighteners are
`generally unsaturated organic compounds. A variety of
`organic compounds containing unsaturated functional 45
`groups such as aldehydic, olefinic, acetylinic, nitrite, and
`pyridine groups have been used as Class II brighteners.
`Typically, Class II brighteners are derived from acetylinic or
`ethylenic alcohols, ethoxylated acetylenic alcohols, cou(cid:173)
`marins and pyridine based compounds. Mixtures of such 50
`unsaturated compounds with mixtures of Class I brighteners
`are combined to obtain maximum brightness or ductility for
`a given rate of leveling. Class II brighteners, however, cause
`brittleness and increase internal stress in a deposit, and,
`therefore, cannot be used alone.
`A variety of amine compounds have been reported as
`brightening or leveling agents. Several patents describe the
`use of acyclic amines as Class II brighteners that require the
`use of other Class I and Class II brighteners. U.S. Pat. No.
`4,077,855 is directed to the use of olefinic or acetylenic 60
`sulfobetaines and carboxybetaines. U.S. Pat. Nos. 4,054,495
`and 4,435,254 disclose the use of acetylenic amines in
`combination with acetylenic compounds as an effective
`brightener and leveling system. U.S. Pat. No. 5,840,986
`describes the synthesis ofN-alkyl-substituted aminoalkynes, 65
`which could potentially be used as a brightener in nickel
`baths.
`
`SUMMARY OF THE INVENTION
`
`25
`
`Accordingly, it is a primary advantage of this invention to
`provide a new and improved brightener system for acidic
`nickel or nickel-alloy plating baths. It is a further object of
`this invention to provide a new and improved brightener
`system for acidic nickel or nickel-alloy plating baths that
`provides an extremely ductile, leveled and highly bright
`nickel deposit over a wide range of current densities without
`the need for alkyl sulfonates and pyridine-based brightening
`and leveling agents. Additional objectives and advantages of
`the invention will be set forth in part in the description that
`follows and in part will be apparent from description or
`learned by the practice of the invention. The advantages of
`the invention may be realized and attained by means of the
`instrumentalities and combinations particularly pointed out
`in the appended claims.
`To achieve the foregoing objects, and in accordance with
`40 the purpose of the invention, as embodied and broadly
`described herein, the present invention provides, in a first
`aspect, a brightener for use in the electrodeposition of a
`nickel or nickel-alloy on a substrate, in which the brightener
`comprises an additive having the general formula:
`
`wherein R 1 , R2 and R3 are selected from the functional
`groups consisting of hydrogen, methyl, ethyl, propyl, ally!,
`propyn, propanediol and combinations thereof; and xn- is an
`n-valent inorganic or organic anion.
`The present invention provides, in a second aspect, a
`process for the electrodeposition of a nickel or nickel-alloy
`55 coating on a metal substrate comprising immersing the metal
`substrate in a bath comprising nickel ions and an additive
`formula H2 C=CHCH2NR1 R2 or
`having
`the general
`[H2 C=CHCH2N+R1R2 R3Jnxn- wherein R 1 , R2 and R3 are
`selected from the functional groups consisting of hydrogen,
`methyl, ethyl, propyl, ally!, propyn, propanediol and com(cid:173)
`binations thereof; and xn- is an n-valent inorganic or
`organic anion.
`In another aspect, the present invention provides an
`aqueous acidic plating bath for the electrodeposition of a
`nickel or nickel alloy deposit on a substrate comprising
`nickel ions; and an additive having the general formula
`C=CHCH2NR1R2 or [H2C=CHCH2N+R1R2 R3Jnxn-
`H
`
`2
`
`Mylan Exhibit 1144
`Mylan v. Regeneron, IPR2021-00881
`Page 2
`
`

`

`3
`wherein R 1 , R2 and R3 are selected from the functional
`groups consisting of hydrogen, methyl, ethyl, propyl, ally!,
`propyn, propanediol and combinations thereof; and xn- is an
`n-valent inorganic or organic anion.
`In a further aspect, the invention provides an aqueous
`acidic plating bath for the electrodeposition of a nickel or
`nickel alloy deposit on a substrate comprising nickel ions; at
`least one Class I brightener; and an additive having the
`general formula H2C=CHCH2NR1 R2 or [H2C=CHCH2N+
`R 1 R 2R3 ]nxn- wherein Ri, R2 and R3 are selected from the
`functional groups consisting of hydrogen, methyl, ethyl,
`propyl, ally!, propyn, propanediol and combinations thereof;
`and xn- is an n-valent inorganic or organic anion.
`The present invention also provides, in a further aspect, an
`aqueous acidic plating bath for the electrodeposition of a
`nickel or nickel alloy deposit on a substrate comprising
`nickel ions; at least one Class II brightener; and an additive
`formula H2 C=CHCH2NR1R2 or
`having
`the general
`[H2C=CHCH2N+R1R2 R3Jnxn- wherein Ri, R2 and R3 are
`selected from the functional groups consisting or hydrogen,
`methyl, ethyl, propyl, ally!, propyn, propanediol and com(cid:173)
`binations thereof; and xn- is an n-valent inorganic or
`organic anion.
`In another aspect, the present invention provides an
`aqueous acidic plating bath for the electrodeposition of a
`nickel or nickel alloy deposit on a substrate comprising
`nickel ions; at least one Class I brightener; at least one Class
`II brightener; and an additive having the general formula
`C=CHCH2NR1R2 or [H2C=CHCH2N+R1R2R3Jnxn(cid:173)
`H
`wherein R 1 , R2 and R3 are selected from the functional
`groups consisting of hydrogen, methyl, ethyl, propyl, ally!,
`propyn, propanediol and combinations thereof; and xn- is an
`n-valent inorganic or organic anion.
`In yet another aspect, the present invention provides an
`aqueous acidic plating bath for the electrodeposition of a 35
`nickel or nickel alloy deposit on a substrate comprising
`nickel ions; alloying metal ions; at least one Class I bright(cid:173)
`ener; at least one Class II brightener; and an additive having
`the
`general
`formula
`H2C=CHCH2NR1 R2
`or
`[H2C=CHCH2N+R1 R 2 R3 ]nxn- wherein Ru R2 and R3 are 40
`selected from the functional groups consisting of hydrogen,
`methyl, ethyl, propyl, ally!, propyn, propanediol and com(cid:173)
`binations thereof; and xn- is an n-valent inorganic or
`organic anion.
`The present invention provides an extremely ductile,
`leveled and highly bright nickel deposit over a wide range of
`current densities without the need for alkyl sulfonates and
`pyridine-based brightening and leveling agents.
`
`2
`
`DETAILED DESCRIPTION OF THE
`INVENTION
`
`In accordance with the present invention, N-allyl substi(cid:173)
`tuted amines and their salts are employed as the main
`brightener and leveling additives in a nickel plating bath.
`The additives of the present invention are characterized by
`the following general formula:
`
`wherein R 1 , R2 and R3 are selected from the functional
`groups consisting of hydrogen, methyl, ethyl, propyl, ally!,
`propyn, propanediol and combinations thereof; and xn- is an
`n-valent inorganic or organic anion. Suitable n-valent anions
`include, but are not limited to chloride, bromide, fluoride,
`sulfate, acetate, and tetrafluoroborate. The N-allyl substi-
`
`US 7,300,563 B2
`
`4
`tuted amine or their salts are preferably present in a nickel
`plating bath at a concentration of from about 5 mg/I to about
`160 mg/I; more preferably at a concentration of from about
`5 mg/I to about 100 mg/I; and most preferably from about 6
`5 mg/I to about 80 mg/I.
`The use of N-allyl substituted amines or their salts has
`been found to produce a nickel deposit that is extremely
`ductile, exhibits excellent leveling, and is highly brilliant,
`i.e., bright, over a wide range of current densities. Further,
`10 the use ofN-allyl substituted amines or their salts in acidic
`nickel baths produces such deposits without the need for
`alkyl sulfonates and pyridine based brighteners and leveling
`agents.
`The N-allyl substituted amines and their salts act as Class
`15 II brighteners. Thus, N-allyl substituted amines are prefer(cid:173)
`ably used in combination with at least one Class I brightener.
`Additionally, the baths of the present invention may
`include one or more secondary, or Class II, brighteners.
`Non-limiting examples of Class II brighteners suitable for
`20 use with the present invention include ally! alcohols, prop(cid:173)
`argyl alcohols, butenediols or butynediols.
`The nickel baths of the present invention may also include
`any other desirable additive, as are conventional in the use
`of nickel plating baths, including but not limited to wetting
`25 agents, anti-pitting agents, etc. A non-limiting example of a
`suitable wetting agent is sodium lauryl ethoxy sulfate or
`sodium lauryl ethoxy sulfonate.
`The base electrolyte solution for the aqueous acidic nickel
`plating baths of the present invention include conventional
`30 aqueous acidic nickel electrolyte solutions known to those
`skilled in the art. Such baths contain free nickel ions.
`Typically, nickel ions are provided by nickel sulfate and/or
`nickel chloride. A typical acidic nickel plating solution
`suitable for use in the present invention is the Watts nickel
`plating bath. The baths of the invention are preferably
`Watts-type plating baths having the following general for-
`mula: 225-375 g/1 nickel sulfate (NiSO4 .6H2 O); 60-120 g/1
`nickel chloride (NiCl 2 .6H2 O); and 35-50 g/1 boric acid
`(H3 BO3 ). The pH of the baths is within the range of about
`2 to about 5. Additionally, the baths according to the present
`invention include any conventional electrolyte solution,
`known to those skilled in the art, for plating nickel-alloys.
`Nickel-alloy plating solutions contain alloying metal ions.
`Any metal suitable for producing a nickel-alloy plate or
`45 coating on a substrate may be used. Preferably, the alloying
`metal ions are selected from the group consisting of iron,
`cobalt, tin, and zinc.
`The present invention also includes a process for produc(cid:173)
`ing a nickel or nickel-alloy deposit on a substrate. A sub-
`50 strate is immersed in a nickel or nickel-alloy electrolyte
`solution that contains nickel ions and/or alloying metal ions,
`and also contains an additive having the general formula
`C=CHCH2NR1R2 or [H2C=CHCH2N+R1R2 R3Jnxn(cid:173)
`H
`wherein R 1 , R2 and R3 are selected from the functional
`55 groups consisting of hydrogen, methyl, ethyl, propyl, ally!,
`propyn, propanediol and combinations thereof; and xn- is an
`n-valent inorganic or organic anion. A current, sufficient to
`apply the desired amount of nickel or nickel-alloy, is applied
`to an anode that has been placed in the bath. Typically, nickel
`60 anodes are used as the anodes for the electrodeposition of
`nickel. The substrate to which the nickel or nickel-alloy
`deposit is applied acts as the cathode.
`The nickel electroplating process may be carried out at
`temperatures of about 50° C. to about 70° C. with or without
`65 agitation. Preferably, the electroplating process is performed
`with agitation of the plating bath. Agitation may be provided
`by mechanical movement of the article being plated, air
`
`2
`
`Mylan Exhibit 1144
`Mylan v. Regeneron, IPR2021-00881
`Page 3
`
`

`

`US 7,300,563 B2
`
`5
`agitation of the solution/plating bath during electrodeposi(cid:173)
`tion, or both mechanical and air agitation.
`The aqueous nickel plating baths of the present invention
`may be used to apply a nickel coating on a substrate. The
`substrate is preferably a metal or metal alloy. Non-limiting
`examples of suitable metal or metal alloys include iron,
`steel, aluminum, copper, brass and alloys thereof.
`The following examples illustrate the inventive additives
`and plating baths of the invention.
`
`EXAMPLES
`
`Various brightening additives of the present invention
`were added to a Watts nickel plating bath having a compo(cid:173)
`sition set forth in the following table.
`
`6
`described in conjunction with specific embodiments thereof,
`it is evident that many alternatives, modifications, and
`variations will be apparent to those skilled in the art in light
`of the foregoing description. Accordingly, the foregoing
`5 description is intended to embrace all such alternatives,
`modifications, and variations which fall within the spirit and
`scope of the appended claims.
`
`What is claimed is:
`1. An aqueous acidic plating bath for the electrodeposition
`of a nickel or nickel alloy deposit on a substrate comprising:
`a) nickel ions; and
`b) an additive having the general formula:
`
`10
`
`15
`
`Bath Component
`
`Concentration
`
`NiSO4.6H2O
`NiC12.6H2O
`H3 BO3
`1,2-benzisothizolin-3-one-1,1-dioxide,
`Na salt
`Propargyl alcohol ethoxylate
`2-butyne-1,4-diol
`butynediol ethoxylate
`1-diethylamino-2-propyne
`
`300 g/1
`90 g/1
`45 g/1
`5 g/1
`
`3 mg/1
`10 mg/1
`5 mg/1
`12.5 mg/1
`
`20
`
`25
`
`The pH of the bath was adjusted to 4.0 using sulfuric acid.
`Plating evaluations were conducted in a 267 ml heated
`Hull cell using N-allyl substituted amines or their salts as a
`brightener. Plating was conducted using a nickel anode and
`a brass cathode. Prior to plating, the brass Hull cell panels
`used as the cathode were anodically cleaned in an alkaline
`electrolyte. All plating was performed at 60° C. The bright- 35
`erring and leveling capabilities of nickel baths containing
`N-allyl substituted amines or their salts was evaluated based
`on plating tests under the above conditions. The results of
`the use of N-allyl substituted amines as brightening agents
`are given in the following table.
`
`40
`
`wherein R 1 , R2 and R3 are selected from the functional
`groups consisting of hydrogen, methyl, ethyl, propyl, ally!,
`propanediol and combinations thereof; and xn- is an n-va(cid:173)
`lent inorganic or organic anion and n=l or 2.
`2. The bath according to claim 1 wherein xn- is an
`n-valent anion selected from the group of chloride, bromide,
`fluoride, sulfate, acetate, and tetrafluoro borate.
`3. The aqueous acidic plating bath according to claim 1,
`wherein the additive comprises diallylamine.
`4. The aqueous acidic plating bath according to claim 1,
`wherein the additive comprises triallylamine.
`5. The aqueous acidic plating bath according to claim 1,
`30 wherein the additive comprises diallyldimethyl armnonium
`chloride.
`6. The aqueous acidic plating bath according to claim 1,
`wherein the additive is present in an amount of from about
`5 mg/I to about 160 mg/I.
`7. The aqueous acidic plating bath according to claim 1,
`wherein the additive is present in an amount of from about
`5 mg/I to about 100 mg/I.
`8. The aqueous acidic plating bath according to claim 1,
`wherein the additive is present in an amount of from about
`6 mg/I to about 80 mg/I.
`9. An aqueous acidic plating bath for the electrodeposition
`of a nickel or nickel alloy deposit on a substrate comprising:
`a) nickel ions;
`b) at least one Class I brightener; and
`c) an additive having the general formula:
`
`45
`
`[H2C~CHCH2N•R1 R2R3Jnxn-
`50 wherein R 1 , R2 and R3 are selected from the functional
`groups consisting of hydrogen, methyl, ethyl, propyl, ally!,
`propanediol and combinations thereof; and xn- is an n-va(cid:173)
`lent inorganic or organic anion and n=l or 2.
`10. An aqueous acidic plating bath for the electrodeposi-
`55 tion of a nickel or nickel alloy deposit on a substrate
`comprising:
`a) nickel ions;
`b) at least one Class II brightener; and
`c) an additive having the general formula:
`
`Concentration
`(mg/1)
`
`Appearance
`(brightness)
`
`cloudy
`cloudy
`cloudy
`cloudy
`cloudy
`bright
`cloudy
`cloudy
`bright
`bright
`bright
`slightly cloudy
`
`Leveling
`
`poor
`poor
`poor
`poor
`poor
`excellent
`fair
`fair
`excellent
`good
`excellent
`fair
`
`bright
`
`good
`
`Brightener
`
`none
`N-allylaniline
`N-allylaniline
`N-allylaniline
`N-allylaniline
`N-allylpyridine
`1-allylimidizole
`1-allylimidizole
`diallylamine
`triallylamine
`triallylamine
`diallyldimethyl
`ammonium
`chloride
`diallyldimethyl
`ammonium
`chloride
`diallyldimethyl
`ammonium
`chloride
`
`20
`40
`80
`160
`6
`20
`40
`20
`20
`40
`20
`
`40
`
`80
`
`bright
`
`excellent
`
`60
`
`Thus, 1t 1s apparent that there has been provided in
`accordance with this invention, an aqueous acidic nickel 65
`plating bath that fully satisfies the objects, aims and advan(cid:173)
`tages set forth above. While the invention has been
`
`wherein R 1 , R2 and R3 are selected from the functional
`groups consisting or hydrogen, methyl, ethyl, propyl, ally!,
`propyn, propanediol and combinations thereof; and xn- is an
`n-valent inorganic or organic anion and n=l or 2.
`
`Mylan Exhibit 1144
`Mylan v. Regeneron, IPR2021-00881
`Page 4
`
`

`

`US 7,300,563 B2
`
`7
`11. An aqueous acidic plating bath for the electrodeposi(cid:173)
`tion of a nickel or nickel alloy deposit on a substrate
`comprising:
`a) nickel ions;
`b) at least one Class I brightener;
`c) at least one Class II brightener; and
`d) an additive having the general formula:
`
`8
`14. A process for the electrodeposition of a nickel or
`nickel-alloy coating on a substrate, the process comprising:
`immersing a metal substrate in a bath comprising nickel
`ions and an additive having the general formula:
`
`wherein R 1 , R2 and R3 are selected from the functional
`groups consisting or hydrogen, methyl, ethyl, propyl, ally!,
`propyn, propanediol and combinations thereof; and xn- is an
`n-valent inorganic or organic anion and n=l or 2.
`12. An aqueous acidic plating bath for the electrodeposi(cid:173)
`tion of a nickel or nickel alloy deposit on a substrate
`comprising:
`a) nickel ions;
`b) alloying metal ions;
`c) at least one Class I brightener;
`d) at least one Class II brightener; and
`e) an additive having the general formula:
`
`[H2C~CHCH2N•R1 R2R3Jnxn-
`wherein R 1 , R2 and R3 are selected from the functional
`groups consisting or hydrogen, methyl, ethyl, propyl, ally!,
`propyn, propanediol and combinations thereof; and xn- is an
`n-valent inorganic or organic anion and n=l or 2.
`13. The bath according to claim 12 wherein the alloying
`metal ions are selected from the group of iron, cobalt, tin,
`and zinc.
`
`10
`
`15
`
`wherein R 1 , R2 and R3 are selected from the functional
`groups consisting of hydrogen, methyl, ethyl, propyl, ally!,
`propanediol and combinations thereof; and xn- is an n-va(cid:173)
`lent inorganic or organic anion and n equals 1 or 2; and
`electrodepositing nickel onto the metal substrate.
`15. The process according to claim 14 wherein xn- is
`selected from the group consisting of chloride, bromide,
`fluoride, sulfate, acetate, and tetrafluoro borate.
`16. The process according to claim 14 wherein the bath
`further comprises alloying metal ions, and electrodepositing
`20 nickel onto the metal substrate comprises electrodepositing
`a nickel-alloy onto the metal substrate.
`17. The process according to claim 16, wherein the
`alloying metal ions are selected from the group consisting of
`iron, cobalt, tin, and zinc.
`18. The process according to claim 14, wherein the
`additive comprises diallylamine.
`19. The process according to claim 14, wherein the
`additive comprises triallylamine.
`20. The process according to claim 14, wherein the
`additive comprises diallyldimethyl ammonium chloride.
`
`25
`
`30
`
`* * * * *
`
`Mylan Exhibit 1144
`Mylan v. Regeneron, IPR2021-00881
`Page 5
`
`