# US 8,541,162 B2 · High resolution, solvent resistant, thin elastomeric printing plates

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- Number: US 8,541,162 B2
- Document ID: US8541162B2
- Status: Granted
- Kind: B2
- Application number: 12/873,584
- Filed: 2010-09-01
- Published: 2012-03-01
- Granted: 2013-09-24
- Earliest claimed: 2010-09-01
- Assignees: E. I. Du Pont de Nemours and Company
- Applicants: Gary Delmar Jaycox; Graciela Beatriz Blanchet; Nancy G. Tassi
- Inventors: Gary Delmar Jaycox; Graciela Beatriz Blanchet; Nancy G. Tassi
- Web page: https://patentgrep.com/patent/US8541162B2

## CPC

- G03F 7/0015: {Production of aperture devices, microporous systems or stamps}
- G03F 7/0046: {with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence)}
- G03F 7/027: Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds (G03F7/075 takes precedence)
- G03F 7/033: the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
- G03F 7/11: having cover layers or intermediate layers, e.g. subbing layers {(G03F7/091 - G03F7/093, B41N3/03 take precedence)}
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)

## Abstract

The present invention relates to a printing element comprising at least one polymer layer on a substrate which has photoimagable constituents and a chemically functionalized polymer to make the polymer layer either more hydrophobic or hydrophilic. In one embodiment of the present invention, the printing element comprises two adjacent polymer layers on a substrate in which the photoimaged layer comprises a polymer chemically modified with hydrophobic fluoroalkyl side groups to provide differential wetting with hydrophilic inks.

## Claims

### Claim 1

A process for making a printing element comprising:
a) providing a hydrophilic substrate
b) depositing a hydrophobic polymer layer on the substrate, the polymer layer comprising:
i) an eastomeric polymer containing hydrophobic fluoroalkyl side groups;
ii) a photoinitiator; and
iii) monomers selected from the group consisting of:
and mixtures thereof;
c) imaging a pattern on the polymer layer forming a crosslinked polymer pattern and a non-crosslinked polymer pattern; and
d) developing the imaged polymer layer wherein the non-crosslinked polymer pattern is dissolved, thereby creating a relief-based image on the printing element.

### Claim 2 (depends on 1)

The process of claim 1 wherein the elastomeric polymer is a block copolymer of styrene-butadiene-styrene or styrene-isoprene-styrene containing hydrophobic fluoroalkyl side groups.

### Claim 3 (depends on 1, 2)

The process of claim 1 or 2 wherein the single polymer layer has an elastic modulus in the range of 10 to 100 MPa.

### Claim 4 (depends on 1, 2)

The process of claim 1 or 2 wherein the single polymer layer has an elastic modulus in the range of 20 to 40 MPa.

### Claim 5

A process for making a printing element comprising:
a) providing a substrate;
b) depositing a first polymer layer on the substrate wherein the first polymer layer is hdrophhobic and comprises
i) an elastomeric polymer containing hydrophobic fluoroalkyl groups;
ii) an initiator;
iii) monomers selected from the group consisting of:
and mixtures thereof;
c) crosslinking the first polymer layer;
d) depositing a second polymer layer on the first polymer layer wherein the second polymer layer is hydrophilic and comprises;
i) an elastomeric polymer containing hydrophilic hydroxyl groups;
ii) a photoinitiator; and
iii) monomers selected from non-fluorinated acrylate or methacrylate;
e) imaging a pattern on the second polymer layer forming a crosslinked polymer pattern and a non-crosslinked polymer pattern; and
f) developing the imaged second polymer layer wherein the non-crosslinked polymer pattern is dissolved, thereby forming a relief-based image on the printing element.

### Claim 6 (depends on 5)

The process of claim 5 wherein the elastomeric polymer in the first polymer layer is a block copolymer of styrene-butadiene-styrene or styrene-isoprene-styrene containing hydrophobic fluoroalkyl side groups and the elastomeric polymer in the second polymer layer is a block copolymer of styrene-butadiene-styrene or styrene-isoprene-styrene containing hydrophilic hydroxyl side groups.

### Claim 7 (depends on 5)

The process of claim 5 wherein the first polymer layer and the second polymer layer have an elastic modulus in the range of 10 to 100 MPa.

### Claim 8 (depends on 5)

The process claim 5 wherein the first polymer layer and the second polymer layer have an elastic modulus in the range of 20 to 40 MPa.

### Claim 9

A process for making a printing element comprising:
a) providing a substrate;
b) depositing a first polymer layer on the substrate wherein the first polymer layer is hydrophilic and comprises:
i) an elastomeric polymer containing hydrophilic hydroxyl side groups;
ii) an initiator;
iii) monomers selected from non-fluorinated acrylate or methacrylate;
c) crosslinking the first polymer layer;
d) depositing a second polymer layer on the first polymer layer wherein the second polymer layer is hydrophobic and comprises;
i) an elastomeric polymer containing hydrophobic fluoroalkyl side groups;
ii) a photoinitiator; and
iii) monomers selected from he group consisting of:
and mixtures thereof;
e) imaging a pattern on the second polymer layer forming a crosslinked polymer pattern and a non-crosslinked polymer pattern; and
f) developing the imaged second polymer layer wherein the non-crosslinked polymer pattern is dissolved, thereby forming a relief-based image on the printing element.

### Claim 10 (depends on 9)

The process of claim 9 wherein the elastomeric polymer in the first polymer layer is a block copolymer of styrene-butadiene-styrene or styrene-isoprene-styrene containing hydrophilic hydroxyl side groups and the elastomeric polymer in the second polymer layer is a block copolymer of styrene-butadiene-styrene or styrene-isoprene-styrene containing hydrophobic fluoroalkyl side groups.

### Claim 11 (depends on 9)

The process of claim 9 wherein the first polymer layer and the second polymer layer have an elastic modulus in the range of 10 to 100 MPa.

### Claim 12 (depends on 9)

The process claim 9 wherein the first polymer layer and the second polymer layer have an elastic modulus in the range of 20 to 40 MPa.

### Claim 13

A process for making a printing element comprising:
a) providing a substrate;
b) depositing a first polymer layer on the substrate wherein the first polymer layer is hydrophilic and comprises:
i) an elastomeric polymer;
ii) an initiator;
iii) monomers selected from non-fluorinated acrylate or methacrylate;
c) crosslinking the first polymer layer;
d) depositing a second polymer layer on the first polymer layer wherein the second polymer layer is hydrophobic and comprises;
i) an elastomeric polymer containing hydrophobic fluoroalkyl side groups;
ii) a photoinitiator; and
iii) monomers selected from the group consisting of:
and mixtures thereof;
e) imaging a pattern on the second polymer layer forming a crosslinked polymer pattern and a non-crosslinked polymer pattern; and
f) developing the imaged second polymer layer wherein the non-crosslinked polymer pattern is dissolved, thereby forming a relief-based image on the printing element.

### Claim 14 (depends on 13)

The process of claim 13 wherein the elastomeric polymer in the first polymer layer is a block copolymer of styrene-butadiene-styrene or styrene-isoprene-styrene and the elastomeric polymer in the second polymer layer is a block copolymer of styrene-butadiene-styrene or styrene-isoprene-styrene containing hydrophobic fluoroalkyl side groups.

### Claim 15 (depends on 13)

The process of claim 13 wherein the first polymer layer and the second polymer layer have an elastic modulus in the range of 10 to 100 MPa.

### Claim 16 (depends on 13)

The process claim 13 wherein the first polymer layer and the second polymer layer have an elastic modulus in the range of 20 to 40 MPa.

### Claim 17 (depends on 1, 5, 9, 13)

The process of any of claims 1, 5, 9 or 13 wherein the printing element is a flexographic printing plate.

### Claim 18 (depends on 1, 5, 9, 13)

The process of any of claims 1, 5, 9 or 13 wherein the printing element is a gravure printing plate.

### Claim 19 (depends on 1, 5, 9, 13)

The process of claims 1, 5, 9 or 13 wherein relief image comprises at least one relief feature having a step height (Δh)-to-feature size ratio of near unity.

### Claim 20 (depends on 1, 5, 9, 13)

The process of claims 1, 5, 9 or 13 wherein imaging is through a mask.

### Claim 21 (depends on 1, 5, 9, 13)

The process of claims 1, 5, 9 or 13 further comprising applying an ink to the relief-based image comprising raised relief features formed of the crosslinked polymer pattern to selectively wet the raised feature with the ink, and transferring the ink from the raised features to a substrate.

### Claim 22 (depends on 1, 5, 9, 13)

The process of claims 1, 5, 9 or 13 further comprising applying an ink to the relief-based image comprising recesses adjacent raised relief features formed of the crosslinked polymer pattern to selectively wet the recesses with the ink, and transferring the ink from the recesses to a substrate.