Organic resin laminate, methods of making and using the same, and articles comprising the same

• US 9,441,133 B2
• Filed: 08/26/2011
• Issued: 09/13/2016
• Est. Priority Date: 08/26/2011
• Status: Active Grant

• Current Assignee: SABIC Global Technologies BV (Government of Saudi Arabia), Shin-Etsu Chemical Company Limited
• Original Assignee: Exatec, LLC (Government of Saudi Arabia), Shin-Etsu Chemical Company Limited
• Inventors: Gilliam, Mary, Higuchi, Koichi
• Primary Examiner(s): Shah, Samir
• Assistant Examiner(s): Yang, Zheren J
• Application Number:
  US13/259,855
• Publication Number:
  US 20140170400A1
• Time in Patent Office: 1,845 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: B05D 1/62 Plasma-deposition of organic layers plasma deposition in general C23C14/00, C23C16/00
• CPC Class Codes: B32B 33/00 Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
• CPC Class Codes: C08J 2369/00 Characterised by the use of polycarbonates; Derivatives of polycarbonates
• CPC Class Codes: C08J 2433/04 esters
• CPC Class Codes: C08J 2433/14 of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C08J 2439/04 Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
• CPC Class Codes: C08J 2443/04 Homopolymers or copolymers of monomers containing silicon
• CPC Class Codes: C08J 7/042 with two or more layers, where at least one layer of a composition contains a polymer binder
• CPC Class Codes: C08J 7/0423 with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
• CPC Class Codes: C08J 7/043 Improving the adhesiveness of the coatings per se, e.g. forming primers adhesives in the form of films or foils characterised by the primer layers between the polymer carriers and the adhesives C09J7/50
• CPC Class Codes: C08J 7/046 Forming abrasion-resistant coatings; Forming surface-hardening coatings
• CPC Class Codes: C09D 133/062 Copolymers with monomers not covered by C09D133/06
• CPC Class Codes: C09D 133/14 of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• CPC Class Codes: C09D 143/04 Homopolymers or copolymers of monomers containing silicon
• CPC Class Codes: Y10T 428/24942 including components having same physical characteristic in differing degree
• CPC Class Codes: Y10T 428/24983 Hardness
• CPC Class Codes: Y10T 428/265 1 mil or less
• CPC Class Codes: Y10T 428/31507 Of polycarbonate
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

An organic resin laminate comprising an organic resin substrate and a multilayer coating system thereon has weather resistance and mar resistance. The multilayer coating system includes an outermost layer (I) which is a hard film resulting from plasma polymerization of an organosilicon compound and an intermediate layer (II) which is a cured film of a composite coating composition (2) comprising inorganic oxide nanoparticle and vinyl copolymer.

Claims

1. An organic resin laminate having weather resistance and mar resistance, comprising an organic resin substrate and a multilayer coating system on a surface of the substrate,

the multilayer coating system including an outermost layer (I) which is a hard film resulting from plasma polymerization of an organosilicon compound and an intermediate layer (II) which is a cured film formed from a composite coating composition (2), the intermediate layer (II) having one surface disposed contiguous to the outermost layer and another surface disposed contiguous to the organic resin substrate,

wherein the composite coating composition (2) comprises

(2-A) an inorganic oxide nanoparticle;

(2-B) a vinyl copolymer; and

(2-C) a solvent;

wherein the inorganic oxide nanoparticle comprises at least one of silica, zinc oxide, titanium oxide, and cerium oxide;

wherein the vinyl copolymer has an organic UV-absorptive group and a reactive group; and

wherein the reactive group is selected from among alkoxysilyl, hydroxyl, epoxy, carboxylic acid and amino groups;

wherein the outermost layer (I) includes an inner sub-layer and an outer sub-layer, wherein the inner sub-layer has a refractive index in the range of 1.449 to 1.463 and the outer sub-layer has a refractive index in the range of 1.430 to 1.434;

wherein the inner sub-layer has a nano-indentation hardness in the range of 1.616 to 1.676 GPa and the outer sub-layer has a nano indentation hardness in the range of 2.265 to 2.667GPa; and

wherein the inner sub-layer is contiguous with the intermediate layer (II).

2. The laminate of claim 1, wherein the outermost layer (I) is a hard film obtained from plasma polymerization and oxidation of an organosilicon compound and comprising silicon, oxygen, carbon, and hydrogen.

3. The laminate of claim 1, wherein the substrate is a single layer and wherein the multilayer coating system is in physical contact with the surface of the substrate.

4. The laminate of claim 1, wherein the substrate is a multilayer substrate comprising a coextruded or laminated base resin and cap-layer, wherein the multilayer coating system is in physical contact with the surface of the substrate.

5. The laminate of claim 4, wherein the cap-layer comprises a material selected from the group consisting of a urethane resin, an acrylic resin, and combinations comprising at least one of the foregoing.

6. The laminate of claim 1, wherein the outermost layer (I) has a total thickness in the range of 2.5 to 5.0 μ

m.

7. The laminate of claim 1, wherein the outermost layer (I) has a total thickness in the range of 2.7 to 3.5 μ

m.

8. The laminate of claim 1, wherein the laminate exhibits a pass rate of at least 97% in the adhesion test of ASTM D3359 Method B and ASTM D870 using de-ionized water at 65°

C. for 3 days and a delta haze value of less than 2% in the Taber abrasion test of ASTM D1044 using 1000 cycles.

9. The laminate of claim 1, wherein the vinyl copolymer (2-B) is a copolymer comprising (2-B-i) 5 wt % to 50 wt % of a vinyl monomer having an organic UV absorptive group, (2-B-ii) 2 wt % to 30 wt % of a vinyl monomer having a reactive group selected from among alkoxysilyl, hydroxyl, epoxy, carboxylic acid, amino groups, and combinations comprising at least one of the foregoing reactive groups, and (2-B-iii) 20 wt % to 93 wt % of another monomer capable of copolymerizing with the vinyl monomers.

10. The laminate of claim 9, wherein the reactive group is selected from among alkoxysilyl, hydroxyl, epoxy groups, and combinations comprising at least one of the foregoing reactive groups.

11. The laminate of claim 1, wherein the composite coating composition (2) further comprises (2-D) a silicone resin obtained from (co)hydrolytic condensation of a member selected from alkoxysilanes having the general formulae (1) to (3) and partial hydrolytic condensates thereof,

(R¹)_m(R²)_nSi(OR³)₄₋

m−

n 

 

(1)

wherein R¹ and R² are each independently hydrogen or a substituted or unsubstituted monovalent hydrocarbon group, R¹ and R² may bond together, R³ is C₁-C₃ alkyl, m and n are independently 0 or 1, and m+n is 0, 1 or 2,

(R⁴O)<sub>3−

p</sub>(R⁶)_pSi—

R⁸—

Si(R⁷)_q(OR⁵)<sub>3−

q</sub> 

 

(2)

wherein R⁴ and R⁵ are each independently C₁-C₃ alkyl, R⁶ and R⁷ are each independently hydrogen or a substituted or unsubstituted monovalent hydrocarbon group, R⁸ is oxygen, phenylene, or substituted or unsubstituted C₂-C₁₀ alkylene, p and q are independently 0 or 1,

X—

[(R¹⁵)Si(R¹⁶)_y(OR¹⁷)<sub>3−

y</sub>]_z 

 

(3)

wherein X is a 1,3,5-trimethylcyclotrisiloxane residue, 1,3,5,7-tetramethylcyclotetrasiloxane residue or isocyanurate residue, R¹⁵ is C₁-C₃ alkylene, R¹⁶ is hydrogen or a substituted or unsubstituted monovalent hydrocarbon group, R¹⁷ is C₁-C₃ alkyl, y is 0 or 1, and z is an integer of 3 to 4.

12. The laminate of claim 11, wherein the silicone resin (2-D) is obtained from alkoxysilanes of formulae (1), (2) and (3) which are combined such that a ratio of (1)/[(2)+(3)] is from 50/50 to 0/100 in Si-mol %.

13. The laminate of claim 11, wherein in formula (1), R¹ is a monovalent hydrocarbon group substituted with a methyl or UV absorptive group, m=1, n=0, and R³ is methyl, in formula (2), R⁸ is substituted or unsubstituted C₂-C₈ alkylene, p=q=0, R⁴ and R⁵ are methyl, and in formula (3), X is isocyanurate residue, y=0, R¹⁵ is propylene, R¹⁷ is methyl, and z=3.

14. The laminate of claim 1, wherein the silicone resin (2-D) is obtained from hydrolytic condensation of a member selected from alkoxysilanes having formulae (2) and (3) and partial hydrolytic condensates thereof.

15. The laminate of claim 1, wherein the silicone resin (2-D) is obtained from hydrolytic condensation of an alkoxysilane having formula (3) and partial hydrolytic condensate thereof.

16. The laminate of claim 1, wherein the composite coating composition (2) further comprises an organic UV absorber and/or organic UV stabilizer other than (2-B).

17. The laminate of claim 1, wherein the organic resin substrate is a molded polycarbonate resin.

18. A method of making an organic resin laminate, comprising:

forming a an organic resin substrate;

applying a composite coating composition (2) to a surface of the substrate, wherein the composite coating composition comprises

(2-A) an inorganic oxide nanoparticle ;

(2-B) a vinyl copolymer; and

(2-C) a solvent;

wherein the inorganic oxide nanoparticle comprises at least one of silica, zinc oxide, titanium oxide, and cerium oxide;

wherein the vinyl copolymer has an organic UV-absorptive group and a reactive group; and

wherein the reactive group is selected from among alkoxysilyl, hydroxyl, epoxy, carboxylic acid and amino groups;

forming an outermost layer (I) onto the composite coating composition by plasma polymerization of an organosilicon compound; and

curing the coating composition (2) to form an intermediate layer (II);

wherein the outermost layer (I) includes an inner sub-layer and an outer sub-layer, wherein the inner sub-layer is contiguous with the intermediate layer (II)

wherein the inner sub-layer has a refractive index in the range of 1.449 to 1.463 and the outer sub-layer has a refractive index in the range of 1.430 to 1.434; and

wherein the inner sub-layer has a nano-indentation hardness in the range of 1.616 to 1.676 GPa and the outer sub-layer has a nano indentation hardness in the range of 2.265 to 2.667 GPa.