Moisture-stable holographic media

Patent metadata

Field	Value
Publication number	US-10329244-B2
Application number	US-201515536841-A
Country	US
Kind code	B2
Filing date	Dec 11, 2015
Priority date	Dec 19, 2014
Publication date	Jun 25, 2019
Grant date	Jun 25, 2019

Abstract

The invention relates to novel compounds which are especially suitable for use as writing monomers in holographic media. The invention further provides a photopolymer and a holographic medium comprising the inventive compounds, and an optical display, a security document and a holographic optical element comprising an inventive holographic medium.

First claim

The invention claimed is:

1. A photopolymer comprising matrix polymers, writing monomers and photoinitiators, wherein the writing monomers comprise compound of formula (I)

in which
R 1 is an aliphatic hydrocarbyl radical having 1-8 carbon atoms;
R 2 is hydrogen or methyl;
Ar is an aromatic radical of the formula (II)

in which
R 3 are independently radicals selected from the group of substituted or unsubstituted phenyl, substituted or unsubstituted phenylthiyl, branched or unbranched alkyl, branched or unbranched alkylthiyl, halogen, where at least one of the R 3 radicals is a radical selected from the group of substituted or unsubstituted phenyl, substituted or unsubstituted phenylthiyl;
n=1 to 5;

or Ar is an aromatic radical of the formula (III)

in which
R 3 are independently radicals selected from the group of substituted or unsubstituted phenyl, substituted or unsubstituted phenylthiyl, branched or unbranched alkyl, branched or unbranched alkylthiyl, halogen, where at least one of the R 3 radicals is a radical selected from the group of substituted or unsubstituted phenyl, substituted or unsubstituted phenylthiyl;
o=1 to 3;
p=1 to 4,

wherein the compound of the formula (I) has only one radiation-curing group, and wherein a reflection hologram comprising the photopolymer has a refractive index modulation of Δn>0.025 and value of ΔT min (1) of <2 nm and a value ΔT min (2) of <5 nm, wherein ΔT min (1) is determined by first obtaining T min (1), the resonance frequency (in nm) in the transmission spectrum at the lowest transmission from a sample stored at 100° C. in an oven for two days and cooled within 2 minutes, subsequently obtaining T min (2) from a sample stored at about 20° C. and 40%-50% relative humidity for 7 days, and taking the difference in the peak wavelengths of the two measurements T min (1) and T min (2), and wherein ΔT min (2) is determined by first obtaining T min (3) the resonance frequency (in nm) in the transmission spectrum at the lowest transmission from a sample stored at 60° C./95% relative air humidity for two days and cooled within 2 minutes, subsequently obtaining T min (4) from a sample stored at about 20° C. and 40%-50% relative humidity for 7 days, and taking the difference in the peak wavelengths of the two measurements T min (3) and T min (4).

2. The photopolymer according to claim 1 , wherein at least one of the R 3 radicals is selected from the group of phenyl, phenylthiyl, phenylthiylphenylthiyl, alkylphenyl, alkylphenylthiyl, biphenyl.

3. The photopolymer according to claim 1 , wherein Ar is a radical of the formula (II).

4. The photopolymer according to claim 1 , wherein o=1.

5. The photopolymer according to claim 1 , wherein R 1 is a radical selected from the group of —CH 2 —CH 2 —, —CH 2 —CH 2 —CH 2 —, —CH 2 —CHCH 3 —, —CH 2 —CH 2 —CH 2 —CH 2 —.

6. The photopolymer according to claim 1 , wherein the matrix polymers are crosslinked matrix polymers, preferably three-dimensionally crosslinked matrix polymers and most preferably are three-dimensionally crosslinked polyurethanes.

7. The photopolymer according to claim 1 , wherein it comprises monomeric fluorourethanes.

8. A holographic medium comprising a photopolymer according to claim 1 which is coated as a film.

9. The holographic medium according to claim 8 , wherein the film has a film thickness of 0.3 μm to 500 μm, more preferably with a film thickness of 0.5 μm to 200 μm and yet more preferably with a film thickness of 1 μm to 100 μm.

10. An optical display comprising a holographic medium according to claim 8 .

11. A security document comprising a holographic medium according to claim 8 .

12. A holographic optical element comprising a holographic medium according to claim 8 .

13. A photopolymer comprising matrix polymers, writing monomers, monomeric fluorourethanes, and photoinitiators, wherein the writing monomers comprise compound of formula (I)

in which
R 1 is an aliphatic hydrocarbyl radical having 1-8 carbon atoms;
R 2 is hydrogen or methyl;
Ar is an aromatic radical of the formula (II)

in which
R 3 are independently radicals selected from the group of substituted or unsubstituted phenyl, substituted or unsubstituted phenylthiyl, branched or unbranched alkyl, branched or unbranched alkylthiyl, halogen, where at least one of the R 3 radicals is a radical selected from the group of substituted or unsubstituted phenyl, substituted or unsubstituted phenylthiyl;
n=1 to 5;

or Ar is an aromatic radical of the formula (III)

in which
R 3 are independently radicals selected from the group of substituted or unsubstituted phenyl, substituted or unsubstituted phenylthiyl, branched or unbranched alkyl, branched or unbranched alkylthiyl, halogen, where at least one of the R 3 radicals is a radical selected from the group of substituted or unsubstituted phenyl, substituted or unsubstituted phenylthiyl;
o=1 to 3;
p=1 to 4,

wherein the compound of the formula (I) has only one radiation-curing group and wherein a hologram comprising the photopolymer has a refractive index modulation of Δn>0.025 and value of ΔT min (1) of <2 nm and a value ΔT min (2) of <5 nm, wherein ΔT min (1) is determined by first obtaining T min (1), the resonance frequency (in nm) in the transmission spectrum at the lowest transmission from a sample stored at 100° C. in an oven for two days and cooled within 2 minutes, subsequently obtaining T min (2) from a sample stored at about 20° C. and 40%-50% relative humidity for 7 days, and taking the difference in the peak wavelengths of the two measurements T min (1) and T min (2), and wherein ΔT min (2) is determined by first obtaining T min (3) the resonance frequency (in nm) in the transmission spectrum at the lowest transmission from a sample stored at 60° C./95% relative air humidity for two days and cooled within 2 minutes, subsequently obtaining T min (4) from a sample stored at about 20° C. and 40%-50% relative humidity for 7 days, and taking the difference in the peak wavelengths of the two measurements T min (3) and T min (4).

Assignees

• Covestro Deutschland Ag

Inventors

• Fäcke Thomas
• Bruder Friedrich-Karl
• Rölle Thomas
• Hönel Dennis

Classifications

• G03H2260/31

  Ageing or resistance of the material (G03H2250/39 takes precedence) · CPC title

• G03H2260/12

  Photopolymer · CPC title

• G03H2001/0264

  Organic recording material · CPC title

• G03H1/0011

  for security or authentication (holograms on information-bearing cards B42D25/328; testing papers with holograms G07D7/0032) · CPC title

• G03F7/035

  the binders being polyurethanes · CPC title