Manufacturing methods for metal clad laminates

• US 8,764,960 B2
• Filed: 08/02/2007
• Issued: 07/01/2014
• Est. Priority Date: 08/07/2006
• Status: Active Grant

• Current Assignee: InkTec Company Limited
• Original Assignee: InkTec Company Limited
• Inventors: Chung, Kwang-Choon, Cho, Hyun-Nam, Uhm, Seong-Yong
• Primary Examiner(s): Hendricks, Keith
• Assistant Examiner(s): Sherrill, Stefanie
• Application Number:
  US12/376,892
• Publication Number:
  US 20100261031A1
• Time in Patent Office: 2,525 Days
• Field of Search: 205/136
• US Class Current: 205/184
• CPC Class Codes: C25D 5/48 After-treatment of electroplated surfaces
• CPC Class Codes: C25D 5/56 of plastics
• CPC Class Codes: H05K 2203/0723 Electroplating, e.g. finish plating
• CPC Class Codes: H05K 2203/1157 Using means for chemical reduction
• CPC Class Codes: H05K 2203/125 Inorganic compounds, e.g. silver salt
• CPC Class Codes: H05K 3/022 Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
• CPC Class Codes: H05K 3/105 by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
• CPC Class Codes: H05K 3/246 Reinforcing conductive paste, ink or powder patterns by other methods, e.g. by plating
• CPC Class Codes: Y10T 428/12396 Discontinuous surface component
• CPC Class Codes: Y10T 428/12896 Ag-base component

Abstract

The present invention relates to the manufacturing method of metal clad laminates by forming a conductive layer on a single side or both sides of a material film that is made of an insulating material using the silver complexes having a unique structure and electroplating metals outside of said conductive layer. The present invention can provide the manufacturing method of metal clad laminates, which has a fast operation speed for mass production, simple process steps to minimize defective ratio and cheap production cost.

Claims

1. A method of manufacturing a metal clad laminate comprising the steps of:

(i) forming a conductive layer on a material by coating a silver coating composition comprising silver complexes which are formed by a reaction between a silver compound of Formula 1, and an ammonium carbamate compound of Formula 2, an ammonium carbonate compound of Formula 3, or an ammonium bicarbonate compound of Formula 4; and

(ii) forming a metal-plated layer by electroplating metals on said conductive layer;

2. The method of claim 1, wherein said silver complexes have the structure of Formula 5:

Ag[A]_m 

 

[Formula 5]

A is the compound of Formula 2, Formula 3, or Formula 4 as shown in claim 1, and m ranges in 0.7 to 2.5.

3. The method of claim 1, wherein said silver compound is one or more compound selected from the group consisting of silver oxide, silver thiocyanate, silver cyanide, silver cyanate, silver carbonate, silver nitrate, silver nitrite, silver sulfate, silver phosphate, silver perchlorate, silver tetrafluoro borate, silver acetylacetonate, silver carboxylate, silver lactate, silver oxalate and their derivatives.

4. The method of claim 1, wherein R₁ to R₆ are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, ethylhexyl, heptyl, octyl, isooctyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, docodecyl, cyclopropyl, cyclopentyl, cyclohexyl, allyl, hydroxy, methoxy, hydroxyethyl, methoxyethyl, 2-hydroxy propyl, methoxypropyl, cyanoethyl, ethoxy, buthoxy, hexyloxy, methoxyethoxyethyl, methoxyethoxyethoxyethyl, hexamethyleneimine, morpholine, piperidine, piperazine, ethylenediamine, propylenediamine, hexamethylenediamine, triethylenediamine, pyrrol, imidazol, pyridine, carboxymethyl, trimethoxysilylpropyl, triethoxysilylpropyl, phenyl, methoxyphenyl, cyanophenyl, phenoxy, tolyl, benzyl, polyallylamine, polyethyleneimine and their derivatives, wherein at least one of R₁ to R₆ is independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, ethylhexyl, heptyl, octyl, isooctyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, docodecyl, cyclopropyl, cyclopentyl, cyclohexyl, allyl, hydroxy, methoxy, hydroxyethyl, methoxyethyl, 2-hydroxy propyl, methoxypropyl, cyanoethyl, ethoxy, buthoxy, hexyloxy, methoxyethoxyethyl, methoxyethoxyethoxyethyl, hexamethyleneimine, morpholine, piperidine, piperazine, ethylenediamine, propylenediamine, hexamethylenediamine, triethylenediamine, pyrrol, imidazol, pyridine, carboxymethyl, trimethoxysilylpropyl, triethoxysilylpropyl, phenyl, methoxyphenyl, cyanophenyl, phenoxy, tolyl, benzyl, polyallylamine, polyethyleneimine, and derivatives thereof.

5. The method of metal clad laminates of claim 1, wherein said ammonium carbamate compound of Formula 2 is one or more compound selected from the group consisting of ethylammonium ethylcarbamate, isopropylammonium isopropylcarbamate, n-butylammonium n-butylcarbamate, isobutylammonium isobutylcarbamate, t-butylammonium t-butylcarbamate, 2-ethylhexylammonium 2-ethylhexylcarbamate, octadecylammonium octadecylcarbamate, 2-methoxyethylammonium 2-methoxyethylcarbamate, 2-cyanoethylammonium 2-cyanoethylcarbamate, dibutylammonium dibutylcarbamate, dioctadecylammonium dioctadecylcarbamate, methyldecylammonium methyldecylcarbamate, hexamethyleneimineammonium hexamethyleneiminecarbamate, morpholinium morpholinecarbamate, pyridinium ethylhexylcarbamate, triethylenediaminium isopropylbicarbamate, benzylammonium benzylcarbamate, triethoxysilylpropylammonium triethoxysilylpropylcarbamate and their derivatives;

said ammonium carbonate compound of Formula 3 is one or more compound selected from the group consisting of ethylammonium ethylcarbonate, isopropylammonium isopropylcarbonate, n-butylammonium n-butylcarbonate, isobutylammonium isobutylcarbonate, t-butylammonium t-butylcarbonate, 2-ethylhexylammonium 2-ethylhexylcarbonate, 2-methoxyethylammonium 2-methoxyethylcarbonate, 2-cyanoethylammonium 2-cyanoethylcarbonate, octadecylammonium octadecylcarbonate, dibutylammonium dibutylcarbonate, dioctadecylammonium dioctadecylcarbonate, methyldecylammonium methyldecylcarbonate, hexamethyleneimineammonium hexamethyleneiminecarbonate, morpholineammonium morpholinecarbonate, benzylammonium benzylcarbonate, triethoxysilylpropylammonium triethoxysilylpropylcarbonate, triethylenediaminium isopropylcarbonate and their derivatives; and

said ammonium bicarbonate compound of Formula 4 is one or more compound selected from the group consisting of isopropylammonium bicarbonate, t-butylammonium bicarbonate, 2-ethylhexylammonium bicarbonate, 2-methoxyethylammonium bicarbonate, 2-cyanoethylammonium bicarbonate, dioctadecylammonium bicarbonate, pyridinium bicarbonate, triethylenediaminium bicarbonate and their derivatives.

6. The method of claim 1, wherein the silver coating composition further comprises an additive selected from solvents, stabilizers, leveling agents or film assistants.

7. The method of claim 6, wherein said solvents are one or more compounds selected from the group consisting of water, alcohol, glycol, acetate, ether, ketone, aliphatic hydrocarbon, aromatic hydrocarbon and halogen substituted hydrocarbon solvent.

8. The method of claim 6, wherein said solvents are one or more compounds selected from the group consisting of water, methanol, ethanol, isopropanol, butanol, ethyleneglycol, glycerine, ethyl acetate, butyl acetate, carbitol acetate, diethyl ether, tetrahydrofuran, dioxane, methyl ethyl ketone, acetone, hexane, heptane, benzene, toluene, chloroform, methylene chloride, carbontetrachloride and mixed solvents of the above.

9. The method of claim 6, wherein said stabilizers are more than one selected from the group consisting of amine compounds, ammonium carbamate compounds of Formula 2, ammonium carbonate compounds of Formula 3, ammonium bicarbonate compounds of Formula 4, phosphorus compounds and sulfur compounds:

10. The method of claim 9, wherein phosphorus compounds are selected from compounds represented by Formula 6, Formula 7 or Formula 8:

R₃P 

 

[Formula 6]

(RO)₃P 

 

[Formula 7]

(RO)₃PO 

 

[Formula 8]

In the formula above, R is a substituted group selected from alkyl or aryl group of carbon number 1 to 20.

11. The method of claim 9, wherein sulfur compounds are selected from the group consisting of butan thiol, n-hexanethiol, diethyl sulfide, alkylmercaptoacetate, mercaptobenzothiazole and tetrahydrothiophene.

12. The manufacturing method of metal clad laminates of claim 6, wherein film assistants are more than one selected from the group consisting of organic acid, organic acid ammonium salt and organic acid metal salt.

13. The method of claim 1, wherein said material is selected from the group consisting of polyimide (PI), polyethyleneterephthalate (PET), polyethylenenaphthalate (PEN), polyethersulfone (PES), nylon, polytetrafluoroethylene (PTFE), polyetheretherketone (PEEK), polycarbonate (PC) or polyarylate (PA).

14. The method of claim 1, wherein the coating is performed by brushing, spray coating, dip coating, roll coating, spin coating, inkjet printing, offset printing, screen printing, pad printing, Gravure printing, Flexo printing, Imprinting or Riso printing.

15. The method of claim 1, wherein said silver coating composition further comprises binder resins to improve adhesive power between silver coating composition and the materials.

16. The method of claim 15, wherein said binder resins are more than one selected from the group consisting of acrylic resins, cellulose resins, polyester, vinyl resins, polyamide, polyurethane, polyether, urea resins, alkyd resins, silicone resins, fluoride resins, polyolefin, petroleum resins, rosin, epoxy resins, unsaturated polyester, diallylphthalate resins, phenol resins, oxetane resins, oxazine resins, bismaleimide resins, modified silicone resins, melamine resin, rubber, natural polymer, glass resins and glass frit.

17. The method of claim 1, further comprising an after-treatment process, which is selected from oxidation treatment, reduction treatment, heat treatment, infrared ray, ultraviolet, electronic ray or laser, after formation of a conductive layer by coating the silver coating composition.

18. The method of claim 17, wherein said after-treatment process is done in air, nitrogen, argon, carbon monoxide, hydrogen or their mixed gas condition.

19. The method of claim 1, wherein the thickness and the conductivity of a conductive layer are 0.005 to 5 μ

m and 10 mΩ

to 1 kΩ

/°

C., respectively.

20. The method of claim 1, wherein the thickness of a metal-plated layer is 1 to 50 μ

m.

21. The method of claim 1, wherein the material for a metal-plated layer is more than one selected from the group consisting of copper, aluminum, nickel, silver, gold, chrome or alloys of these.

22. The method of claim 1, wherein the conductive layer is a conductive pattern layer formed by printing the silver coating composition directly on the materials.

23. The method of claim 22, wherein said printing method is selected from the group consisting of inkjet printing, offset printing, screen printing, pad printing, Gravure printing, Flexo printing, Imprinting or Riso printing.

24. The method of claim 22, wherein the electroplating is performed by a plating cartridge comprising a cathode which contacts the conductive pattern layer and an anode placed inside of the plating cartridge.

25. The method of claim 24, wherein said plating cartridge comprises an insulating sponge which can support an electroplating solution and said sponge contacts the anode and the cathode.

26. The method of claim 25, wherein an oscillator is comprised inside of said plating cartridge for contacting the electroplating solution to the cathode of the conductive pattern.

27. Metal clad laminates prepared by the manufacturing method of claim 1.

28. Metal clad laminates prepared by the manufacturing method of claim 22.