# US 5,346,806 A · Acid-cleavable radiation-sensitive compounds, radiation-sensitive mixture containing these compounds, and radiation-sensitive recording material produced with this mixture

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- Number: US 5,346,806 A
- Document ID: US5346806A
- Status: Granted
- Kind: A
- Application number: 07/871,011
- Filed: 1992-04-20
- Granted: 1994-09-13
- Earliest claimed: 1991-04-20
- Assignees: Hoechst Aktiengesellschaft
- Inventors: Georg Pawlowski; Ralph Dammel; Horst Roeschert; Walter Spiess; Charlotte Eckes
- Web page: https://patentgrep.com/patent/US5346806A

## CPC

- C07C 309/65: of a saturated carbon skeleton
- C07C 309/66: Methanesulfonates
- C07C 309/73: to carbon atoms of non-condensed six-membered aromatic rings
- C07C 309/74: to carbon atoms of six-membered aromatic rings being part of condensed ring systems
- C07C 309/75: containing singly-bound oxygen atoms bound to the carbon skeleton
- C07C 309/77: containing carboxyl groups bound to the carbon skeleton
- G03F 7/039: Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023)
- C07C 2601/14: The ring being saturated
- C07C 2602/28: Hydrogenated naphthalenes
- C07C 2602/44: the bicyclo ring system containing eight carbon atoms
- C07C 2603/68: Dicyclopentadienes; Hydrogenated dicyclopentadienes
- Y10S 430/115: Cationic or anionic
- Y10S 430/12: Nitrogen compound containing
- Y10S 430/126: Halogen compound containing
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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)
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

Ligomeric sulfonic acid derivatives having repeating units of the formula I ##STR1## in which R.sup.1 is an alkyl, haloalkyl or aryl radical, R.sup.2 is a hydrogen atom, an alkyl, alkenyl or aryl radical or the group (R.sup.1 --SO.sub.2 --O--).sub.n X--, R.sup.3 is a cycloalkylenedialkyl, cycloalkenylenedialkyl, arylenedialkyl, heteroarylenedialkyl group, alkylene, alkenylene, alkynylene, cycloalkylene or arylene group, X is an alkylene, cycloalkylene or arylene group Y is O, S, CO, CO--O, SO.sub.2, SO.sub.2 --O, NR.sup.4, CO--NH, O--CO--NR.sup.5, NH--CO--NR.sup.5 or NR.sup.5 --CO--O, Z is O, CO--NR.sup.6, O--CO--NR.sup.6 or NH--CO--NR.sup.6, R.sup.4 is an acyl radical, R.sup.5 is a hydrogen atom or an alkyl-, cycloalkyl, alkenyl, alkynyl or aryl radical, R.sup.6 is an alkyl, cycloalkyl, alkenyl, alkynyl or aryl radical, k is 0, 1, 2, 3 or 4, m is an integer greater than 1 and n is 1, 2 or 3, generate sulfonic acids under irradiation and are cleavable by the latter. In combination with alkali-soluble binders, they give positive-working mixtures which are used especially in recording materials for UV radiation and high-energy radiation. The recording materials are distinguished by a high resolution in conjunction with high image contrast and excellent storage stability.

## Claims

### Claim 1

A positive-working radiation-sensitive mixture which comprises:
a) a polymeric binder which is insoluble in water and soluble or at least swellable in aqueous alkaline solutions, and
b) an oligomer having repeating units of the formula ##STR4## in which R.sup.1 is an alkyl, halalkyl or aryl radical,
R.sup.2 is a hydrogen atom, an alkyl, alkenyl or aryl radical or the group R.sup.1 --SO.sub.2 --O).sub.n X--,
R.sup.3 is a cycloalkylenedialkyl, cycloalkenylenedialkyl, arylenedialkyl, heteroarylenedialkyl, alkylene, alkenylene, alkynylene, cycloalkylene or arylene group,
X is an alkylene, cycloalkylene or arylene group if n is 1, or a (n+1)-valent radical of an alkene, cycloalkene, or arene if n is 2 or 3.
Y is O, S, CO, CO--O, SO.sub.2, NR.sup.4, CO--NH, O--CO--NR.sup.5, NH--CO--NR.sup.5 --CO--O,
Z is O, CO--NR.sup.6, O--CO--NR.sup.5 or NH--CO--NR.sup.6,
R.sup.4 is an acyl radical,
R.sup.5 is a hydrogen atom or an alkyl-, cycloalkyl, alkenyl, alkynyl or aryl radical,
R.sup.6 is an alkyl, cycloalkyl, alkenyl, alkynyl or aryl radical,
k is 0, 1, 2, 4 or 4,
m is an integer greater than 1 and
n is 1, 2 or 3,
where R.sup.3 and Y in recurring groupings (R.sup.3 --Y--) can have identical or different definitions.

### Claim 2 (depends on 1)

A radiation-sensitive mixture as claimed in claim 1, wherein R.sup.1 is an alkyl, highly fluorinated alkyl or perfluoro-alkyl radical, each having 1 to 6 carbon atoms or an aryl radical having 6 to 12 carbon atoms, wherein the aryl radical is optionally substituted with one or more of halogen atoms, nitro groups, cyano groups, or alkyl or alkoxy groups having 1 to 3 carbon atoms.

### Claim 3 (depends on 1)

A radiation-sensitive mixture as claimed in claim 1, wherein R.sup.2 is a hydrogen atom.

### Claim 4 (depends on 1)

A radiation-sensitive mixture as claimed in claim 1, wherein R.sup.2 is the group (R.sup.1 --SO.sub.2 --O--).sub.n X--.

### Claim 5 (depends on 1)

A radiation-sensitive mixture as claimed in claim 1, wherein X is an alkylene or cycloalkylene group having 2 to 10 carbon atoms or an arylene group having 6 to 12 carbon atoms.

### Claim 6 (depends on 1)

A radiation-sensitive mixture as claimed in claim 1, wherein R.sup.4 is an aroyl radical.

### Claim 7 (depends on 1)

A radiation-sensitive mixture as claimed in claim 1, wherein m is greater than 3.

### Claim 8 (depends on 1)

A radiation-sensitive mixture as claimed in claim 1, wherein m is between 4 and 40.

### Claim 9 (depends on 1)

A radiation-sensitive mixture as claimed in claim 1, wherein said oligomer (b) is sensitive to light of a wavelength from 190 to 350 nm.

### Claim 10 (depends on 1)

A radiation-sensitive mixture as claimed in claim 1, which contains (b) in a concentration from 2 to 60% by weight, based on the total weight of solids present in the mixture.

### Claim 11 (depends on 1)

A radiation-sensitive mixture as claimed in claim 1, wherein (a) has an extinction of less than 0.5 .mu.m.sup.-1 in the wavelength region of the sensitivity of (b).

### Claim 12 (depends on 11)

A radiation-sensitive mixture as claimed in claim 11, wherein (a) comprises a polymer having phenolic hydroxy groups.

### Claim 13 (depends on 1)

A radiation-sensitive mixture as claimed in claim 1, which contains (a) in a concentration from 40 to 98% by weight, based on the total weight of solids in the mixture.

### Claim 14 (depends on 1)

A radiation-sensitive mixture as claimed in claim 1, wherein said (a) comprises at most 30% by weight of a novolak condensation resin.

### Claim 15 (depends on 1)

A radiation-sensitive recording material comprising a support and a radiation-sensitive layer, wherein the layer is comprised of a radiation-sensitive mixture as claimed in claim 1.

### Claim 16 (depends on 15)

A method of producing a recording material as claimed in claim 15 which comprises applying said radiation-sensitive layer to said support.

### Claim 17 (depends on 16)

A method as claimed in claim 16, comprising dissolving said mixture in a solvent to form a solution, applying the resultant solution to said support, and removing said solvent.

### Claim 18 (depends on 16)

A method as claimed in claim 16, which comprises first applying said radiation-sensitive layer to a temporary support, and then applying said support to said radiation-sensitive layer, and then optionally removing said temporary support.

### Claim 19 (depends on 1)

A radiation-sensitive mixture as claimed in claim 1, wherein the polymeric binder comprises a homopolymer or copolymer of p-hydroxystyrene or of an alkyl derivative thereof.

### Claim 20 (depends on 1)

A coating solution comprising a solvent and a mixture as claimed in claim 1.