Method of decorating laminated glass

• US 7,955,470 B2
• Filed: 09/28/2009
• Issued: 06/07/2011
• Est. Priority Date: 02/28/2005
• Status: Active Grant

• Current Assignee: Ferro Corporation
• Original Assignee: Ferro Corporation
• Inventors: McGowan, David L., Kapp, David C., Stewart, Kimberly Ann, Sakoske, George E., Stotka, David M.
• Primary Examiner(s): Tucker; Philip C
• Assistant Examiner(s): Orlando; Michael N
• Application Number:
  US12/567,876
• Publication Number:
  US 20100071837A1
• Time in Patent Office: 617 Days
• Field of Search: 156/63, 156/99, 156/325, 428/203, 428/204
• US Class Current: 156/325
• CPC Class Codes: B32B 17/10036 comprising two outer glass sheets
• CPC Class Codes: B32B 17/10247 Laminated safety glass or glazing containing decorations or patterns for aesthetic reasons containing metal wires for aesthetic reasons B32B17/10422
• CPC Class Codes: B32B 17/10697 being cross-linked
• CPC Class Codes: B32B 17/10761 containing vinyl acetal
• CPC Class Codes: B32B 17/10779 containing polyester
• CPC Class Codes: B44F 1/066 comprising at least two transparent elements, e.g. sheets, layers layered products of glass and synthetic resin containing decorations or patterns B32B17/10247; window units comprising two or more parallel glass panes E06B3/66
• CPC Class Codes: Y10T 428/24868 Translucent outer layer
• CPC Class Codes: Y10T 428/24876 Intermediate layer contains particulate material [e.g., pigment, etc.]

Abstract

A method of decorating laminated glass is disclosed. A pigment package composition comprising a cross-linkable thermoset resin, a crosslinker capable of crosslinking the thermoset resin, and a pigment is applied to a glass substrate. The crosslinker and thermoset resin are cured at a relatively low temperature (ca. 400° F.). The use of an organic based pigment composition allows use of thinner glass sheets than with traditional ceramic enamel pigment compositions.

Claims

1. A method of forming a laminated decorated glass structure comprising:

a. applying to a first glass substrate an organic pigment package comprising, prior to curing,

i. a crosslinkable thermoset resin selected from the group consisting of polyesters, urethanes, vinyl polymers, acrylics, styrenes, polyolefins, polycarbonates, copolymers thereof, and blends thereof,

ii. a crosslinker capable of crosslinking the thermoset resin, selected from the group consisting of;

amines, amino resins, amido resins, isocyanates, ureas, and dialdehydes, and

iii. a pigment,

wherein prior to curing, the crosslinker and thermoset resin are present in an equivalence ratio of about 0.2 to about 1.2;

b. curing the crosslinker and the thermoset resin to form a cured layer on the first substrate;

c. stacking an acetal layer and a second glass substrate onto the cured layer such that the acetal and the cured layer lie between the first substrate and a second glass substrate; and

d. heating the first and second stacked glass substrates to flow the acetal layer and effect interpenetration of the acetal layer with the cured layer.

2. The method of claim 1, wherein, prior to curing, the crosslinker and thermoset resin are present in an equivalence ratio of about 0.4 to about 0.9.

3. The method of claim 1, wherein the crosslinker is a melamine-formaldehyde, and the thermoset resin is a polyester and wherein, prior to curing, the equivalence ratio of crosslinker to polyester is about 0.45 to about 0.7.

4. The method of claim 1, wherein the crosslinker is selected from the group consisting of melamines, acetoguanamines, benzoguanamines, ureas, and combinations thereof.

5. The method of claim 1, wherein the crosslinker is selected from the group consisting of:

diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, methylene bis-cyclohexylisocyanate, isophorone diisocyanate, methyl isocyanate, and polymethylene polyphenyl isocyanate.

6. The method of claim 1, wherein the crosslinker is selected from the group consisting of fully alkylated melamine-formaldehyde resins, partially alkylated melamine-formaldehyde resins, and high imino melamine-formaldehyde resins.

7. The method of claim 1, wherein the pigment package further comprises at least one of

a. a surfactant,

b. an adhesion promoter,

c. an acid catalyst,

d. a light stabilizer,

e. a solvent, and

f. a rheology modifier.

8. The method of claim 1, wherein the pigment is selected from the group consisting of azo dyes, cyanine dyes, pyridine dyes, dioxane dyes, stilbene dyes, coumarin dyes, rhodamine dyes, oxazine dyes, quinone dyes, anthraquinone dyes, and naphthalimide dyes, quinacridone, phthalocyanine blue, phthalocyanine green, disazo yellow, dibromoantoanthrone, dioxane violet, 1,4-bis(2-methylstyryl)benzene, and trans-4,4′

-diphenylstilbene.

9. The method of claim 1, wherein the pigment is selected from the group consisting of iron pigments, cobalt pigments, cadmium pigments, chromium pigments, copper mercury pigments, titanium pigments, zinc pigments, lead pigments, magnesium pigments, manganese pigments, and vanadium pigments.

10. The method of claim 1, wherein the pigment is selected from the group consisting of:

carbon black, titanium dioxide, Fe₂O₃, Fe₃O₄, V₂O₅, CoO—

Al₂O₃—

TiO₂—

Cr₂O₃, CoO—

Al₂O₃, CeO₂, ZrO₂, zinc oxide, magnesium ferrite, mercuric sulfide, cadmium sulfoselenide, molybdenum chromate, zircon, copper chrome black, iron nickel manganese chrome black, cobalt aluminate blue, zinc iron chrome brown, and iron cobalt chrome.

11. The method of claim 1, wherein the pigment package comprises:

a. about 60 to about 85 wt % of thermoset resin+crosslinker,

b. about 5 to about 15 wt % of pigment, and

c. further comprises a solvent, wherein said solvent is present in the pigment package to the extent of about 3 to about 15 wt % of a solvent.

12. The method of claim 1, wherein the pigment package composition comprises:

a. about 60 to about 65 wt % thermoset resin,

b. about 7 to about 13 wt % crosslinker,

c. about 5 to about 10 wt % pigment,

d. about 0.1 to about 1 wt % surfactant,

e. about 0.1 to about 3 wt % rheological modifier,

f. about 0.1 to about 1 wt % adhesion promoter,

g. about 0.1 to about 4 wt % light stabilizers/blockers,

h. about 5 to about 15 wt % solvent, and

i. about 0.1 to about 2 wt % catalyst.

13. The method of claim 1, wherein the thermoset resin is a polyester resin having a hydroxyl equivalent weight of about 200 to about 1500.

14. The method of claim 1, wherein the decorated glass structure is a flat piece of automotive glass.

15. The method of claim 1, wherein, prior to applying the organic pigment package to the first glass substrate, the first and second glass substrates are bent.

16. The method of claim 1, wherein during the step (a) of applying to the first glass substrate an organic pigment package, a technique selected from the group consisting of screen printing, roll coating, air-assisted spray, airless spray, inkjet, rotary screen print, thermal transfer ribbon, electrostatic disk, and electrostatic bell is utilized.

17. The method of claim 1, wherein the first and second glass substrates are bent prior to applying the pigment composition and wherein the pigment composition is applied to the first glass substrate by ink jet printing.