Curable high refractive index ink compositions and articles prepared from the ink compositions

Patent metadata

Field	Value
Publication number	US-11667803-B2
Application number	US-201816631201-A
Country	US
Kind code	B2
Filing date	Jul 23, 2018
Priority date	Jul 26, 2017
Publication date	Jun 6, 2023
Grant date	Jun 6, 2023

Abstract

Curable ink compositions include a curable aromatic monomer composition, and surface treated metal oxide nanoparticles. The surface treated metal oxide nanoparticles are surface treated with a mixture of at least two silane-functional surface treatment agents, at least one aromatic-containing silane-functional surface treatment agent and at least one silane-functional surface treatment agent comprising a co-polymerizable group. The curable ink composition is inkjet printable, having a viscosity of 30 centipoise or less at a temperature of from room temperature to 60° C., and is free from solvents. The curable ink composition, when printed and cured, has a refractive index of 1.55 or greater, and is optically clear.

First claim

What is claimed is:

1. A curable ink composition comprising:
a curable aromatic monomer composition, wherein the curable monomer composition comprises:
at least one aromatic (meth)acrylate compound of Formula III:

wherein R2 is H or CH 3 ;
X is linked to the aromatic group at either the ortho, para, or meta position and is O, S, or a single bond;
Q is a single bond, O, S, SiR 2 where R is an alkyl group, a carbonyl group (C═O), an amino group NR where R is hydrogen or an alkyl, or an SO 2 group;
n is an integer ranging from 0 to 10; and
L is an alkylene group having 1 to 5 carbon atoms;
at least one multifunctional aromatic (meth)acrylate monomer of general Formula IV:
H 2 C═CR2-(CO)—O—W—O—(CO)—R2C═CH 2   Formula IV

where R2 is hydrogen or methyl,
(CO) is a carbonyl group C═O, and
W is a divalent group comprising a heteroaromatic group, a fused aromatic group, or a group containing both heteroalkylene and aromatic groups; and
at least on initiator; and

surface treated metal oxide nanoparticles, wherein the surface treated metal oxide nanoparticles comprise metal oxide nanoparticles that have been surface treated with a mixture of at least two silane-functional surface treatment agents;
wherein the curable ink composition is inkjet printable, having a viscosity of 30 centipoise or less at a temperature of from room temperature to 60° C., and is free from solvents, and wherein the curable ink composition when printed and cured has a refractive index of 1.55 or greater, and is optically clear.

2. The curable ink composition of claim 1 , wherein the metal oxide nanoparticles comprise titania nanoparticles.

3. The curable ink composition of claim 1 , wherein the at least two silane-functional surface treatment agents comprise at least one aromatic-containing silane-functional surface treatment agent with the general Formula I:
(R a ) 3-d (R b O) d —Si-A-Y  I

wherein each R a independently comprises an alkyl group with 1-5 carbon atoms;
each R b independently comprises an alkyl group with 1-3 carbon atoms;
d is an integer of 1-3;
A is a divalent linking group containing 1-5 carbon atoms; and
Y is an aromatic-containing group;
and at least one silane-functional surface treatment agent comprising a co-polymerizable group with the general Formula II:
(R a ) 3 d(R b O) d —Si—B—Z  II

wherein each R a independently comprises an alkyl group with 1-5 carbon atoms;
each R b independently comprises an alkyl group with 1-3 carbon atoms;
d is an integer of 1-3;
B is a divalent linking group containing at least 3 carbon atoms; and
Z is an ethylenically unsaturated functional group.

4. The curable ink composition of claim 3 , wherein the silane-functional surface treatment agent of general Formula I comprises:
(R a ) 3-d (R b O) d —Si-A-Y  I

wherein each R a independently comprises an alkyl group with 1-5 carbon atoms;
each R b independently comprises an alkyl group with 1-3 carbon atoms;
d is an integer of 1-3;
A is a divalent hydrocarbon linking group of —(CH 2 )— a where a is an integer of 1-5; a divalent aromatic-containing linking group; or a hydrocarbon linking group substituted with one or more heteroatoms; and
Y is an aromatic-containing group of Ar; —O—Ar; —O—(CO)—Ar; or —(CO)—Ar
wherein each Ar is an aryl group; and (CO) is a carbonyl group C═O.

5. The curable ink composition of claim 4 , wherein the silane-functional surface treatment agent of general Formula I comprises:
(R a ) 3-d (R b O) d —Si-A-Y  I

each R b independently comprises an alkyl group with 1-2 carbon atoms;
d is 3;
A is a divalent hydrocarbon linking group of —(CH 2 )— a where a is an integer of 1-5; and
Y is phenyl; substituted phenyl; biphenyl, substituted biphenyl; —O-Ph;
—O—(CO)-Ph; or —(CO)-Ph wherein each Ph is a phenyl or substituted phenyl group;
and (CO) is a carbonyl group C═O.

6. The curable ink composition of claim 3 , wherein the at least one silane-functional surface treatment agent comprising a co-polymerizable group with the general Formula II:
(R a ) 3 d(R b O) d —Si—B—Z  II

wherein each R a independently comprises an alkyl group with 1-5 carbon atoms;
each R b independently comprises an alkyl group with 1-3 carbon atoms;
d is an integer of 1-3;
B is a divalent hydrocarbon linking group of —(CH 2 )— b where b is an integer of 3-10; and
Z is an ethylenically unsaturated functional group comprising —O—(CO)—C(R2)=CH 2 , where (CO) is a carbonyl group C═O, and R2 is a hydrogen atom or a methyl group.

7. The curable ink composition of claim 3 , wherein the molar ratio of aromatic-containing silane-functional surface treatment agent to silane-functional surface treatment agent comprising a co-polymerizable group is in the range of 30:70 to 5:95.

8. The curable ink composition of claim 1 , wherein the curable ink composition comprises at least 2% by weight of surface treated metal oxide nanoparticles.

9. A method of preparing an article comprising:
providing a substrate with a first major surface and a second major surface;
providing a curable ink composition wherein the curable ink composition comprises:
a curable aromatic monomer composition, wherein the curable monomer composition comprises:
at least one aromatic (meth)acrylate compound of Formula III:

wherein R2 is H or CH 3 ;
X is linked to the aromatic group at either the ortho, para, or meta position and is O, S, or a single bond;
Q is a single bond, O, S, SiR 2 where R is an alkyl group, a carbonyl group (C═O), an amino group NR where R is hydrogen or an alkyl, or an SO 2 group;
n is an integer ranging from 0 to 10; and
L is an alkylene group having 1 to 5 carbon atoms;
at least one multifunctional aromatic (meth)acrylate monomer of general Formula IV:
H 2 C═CR2-(CO)—O—W—O—(CO)—R2C═CH 2   Formula IV

where R2 is hydrogen or methyl,
(CO) is a carbonyl group C═O, and
W is a divalent group comprising a heteroaromatic group, a fused aromatic group, or a group containing both heteroalkylene and aromatic groups; and
at least on initiator; and

surface treated metal oxide nanoparticles, wherein the surface treated metal oxide nanoparticles comprise metal oxide nanoparticles that have been surface treated with a mixture of at least two silane-functional surface treatment agents;
wherein the curable ink composition is inkjet printable, having a viscosity of 30 centipoise or less at a temperature of from room temperature to 60° C., and is free from solvents, and wherein the curable ink composition when printed and cured has a refractive index of 1.55 or greater, and is optically clear;

disposing the curable ink composition on at least a portion of the second major surface of the substrate to form a curable layer;
curing the curable layer to form a cured layer; and
depositing an inorganic barrier layer on the cured layer.

Assignees

• 3M Innovative Properties Company

Inventors

• Schwartz Evan L
• Hartmann-Thompson Claire
• Mackey Sonja S
• Mahoney Wayne S
• Chakraborty Saswata
• Volp Kelly A

Classifications

• C08K2201/011

  Nanostructured additives · CPC title

• C08K2003/2241

  Titanium dioxide · CPC title

• B82Y40/00

  Manufacture or treatment of nanostructures · CPC title

• C09D11/326 Primary

  characterised by the pigment dispersant · CPC title

• C08K3/22

  of metals · CPC title