Photopolymerisation process with two exposures of a single layer

• US 4,440,850 A
• Filed: 07/12/1982
• Issued: 04/03/1984
• Est. Priority Date: 07/23/1981
• Status: Expired due to Fees

• Current Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Original Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Inventors: Losert, Ewald, Paul, John G., Stark, Bernard P.
• Primary Examiner(s): Brammer, Jack P.
• Application Number:
  US06/397,373
• Time in Patent Office: 631 Days
• Field of Search: 430/270, 430/281, 430/325, 430/394, 204/159.14, 204/159.22
• US Class Current: 430/325
• CPC Class Codes: C07D 207/452 with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
• CPC Class Codes: C07D 209/78 with oxygen and nitrogen atoms in positions 1 and 3
• CPC Class Codes: C07D 493/08 Bridged systems
• CPC Class Codes: G03F 7/027 Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence

Abstract

A layer of a liquid composition containing a compound (A) having in the same molecule at least one (meth)acryloyl group and at least one bicyclo[2.2.1]hept-2-ene-6-yl unit is exposed to actinic radiation so that the layer solidifies due to photopolymerisation of (A) through the (meth)acryloyl group(s), remaining, however, photocrosslinkable. When desired, the solidified layer is exposed, as through a negative, to a substantially greater amount of actinic radiation, the parts so further exposed becoming more highly photocrosslinked through the bicyclo[2.2.1]hept-2-ene-6-yl unit(s) and hence insoluble. An image is produced which can be developed by means of suitable solvents. Examples of (A) include 3-(methacryloyloxy)-2-hydroxypropyl bicyclo[2.2.1]hept-2-ene-6-carboxylate and 2-(acryloyloxy)ethyl methyl-5-carboxybicyclo[2.2.1]hept-2-ene-6-carboxylate.

Claims

1. A process for production of an image which comprises

(1) exposing to actinic radiation a layer, supported on a carrier, of a liquid composition containing a compound (A) having in the same molecule both at least one group of formula ##STR47## and at least one group of formula ##STR48## such that the layer solidifies and becomes essentially nontacky due to photopolymerisation of (A) through the group or groups of formula I but remains substantially photocrosslinkable, and subsequently P1 (2) exposing as through an image-bearing transparency consisting of substantially opaque and substantially transparent areas at least part of the layer so solidified to a substantially greater amount of actinic radiation such that the further exposed part or parts of the photopolymerised layer undergo photocrosslinking through the group or groups of formula II, and

(3) developing the image by dissolving in a solvent parts of the layer which have not become substantially photocrosslinked, where

R denotes a hydrogen atom or a methyl group,

a is zero or an integer of from 1 to 4,

R₁ denotes a methyl group, or, if a is 1, may alternatively denote an allyl group,

R² denotes a hydrogen atom, a carboxyl group, a carbonyloxyalkyl group (which may be interrupted in the chain by an ether oxygen atom), a carbonyloxyalkene group joined through an oxygen atom to a group of formula I, the alkyl or alkylene group having up to 8 carbon atoms, or together with one of the indicated free valencies, R² denotes a cyclic imide group of structure ##STR49## and X denotes a methylene bridge, a methylene bridge substituted by one or two of the aforesaid methyl groups R¹, a methylene bridge substituted by the allyl group R¹, or an oxygen atom.

2. The process of claim 1 in which (A) is of formula ##STR50## where b and c are each independently an integer of at least 1,

R³ denotes the residue of a compound containing at least (b+c) glycidyl groups directly attached to an atom or atoms of oxygen, nitrogen, or sulfur, after removal of (b+c) such glycidyl groups, and

R⁴ denotes the residue, after removal of (b+c) alcoholic hydroxyl or phenolic hydroxyl groups respectively, of an alcohol having at least (b+c) alcoholic hydroxyl groups or of a phenol having at least (b+c) phenolic hydroxyl groups.

3. The process of claim 1 in which (A) is of formula ##STR51## where R⁵ denotes an alkylene group of 2 to 6 carbon atoms.

4. The process of claim 1 in which (A) is of formula ##STR52## where b and c are each independently an integer of at least 1 and

R⁶ denotes the residue of a compound containing at least (b+c) primary amino groups, after removal of (b+c) such amino groups.

5. The process of claim 1 in which (A) is of formula ##STR53## where R⁵ denotes an alkylene group of 2 to 6 carbon atoms,

R⁷ denotes a carbon-carbon bond or a divalent group of 1 to 10 carbon atoms,

g denotes zero or 1, and

h denotes zero, 1, or 2.

6. The process of claim 1 in which (A) is of formula ##STR54## where R⁵ denotes an alkylene group of 2 to 6 carbon atoms,

h denotes zero, 1, or 2, and

R⁸ represents the residue, after removal of the two isocyanate groups, of an organic di-isocyanate.

7. The process of claim 1 in which (A) is of formula ##STR55##

8. The process of claim 1 in which (A) is of formula ##STR56## where b and c are each independently an integer of at least 1 and

R⁹ denotes the residue of a compound containing at least (2b+c) alcoholic hydroxyl groups, after removal of (2b+c) alcoholic hydroxyl groups.

9. The process of claim 1 in which (A) is of formula ##STR57## where R⁵ denotes an alkylene group of 2 to 6 carbon atoms and

R¹¹ denotes an alkyl group of 1 to 8 carbon atoms, or an alkyl group of 1 to 8 carbon atoms interrupted in the chain by an ether oxygen atom.

10. The process of claim 1 in which (A) is of formula ##STR58## where R¹² denotes as alkylene group of 1 to 6 carbon atoms.

11. The process of claim 1 in which (A) is 3-(methacryloyloxy)-2-hydroxypropyl bicyclo[2.2.1]hept-2-ene-6-carboxylate, 2-(acryloyloxy)ethyl methyl-5-carboxybicyclo[2.2.1]hept-2-ene-6-carboxylate, 2-(acryloyloxy)ethyl 5-carboxy-7-oxabicyclo[2.2.1]hept-2-ene-6-carboxylate, 2-(methacryloyloxy)ethyl methyl-5-carboxybicyclo[2.2.1]hept-2-ene-6-carboxylate, 3-(methacryloyloxy)-2-hydroxypropyl methyl-5-carbomethoxybicyclo[2.2.1]hept-2-ene-6-carboxylate, 2-(methacryloyloxy)ethyl 5-carboxy-7-oxabicyclo[2.2.1]hept-2-ene-6-carboxylate, or N-2-(methacryloyloxy)ethyl methylbicyclo[2.2.1]hept-2-ene-5,6-dicarboximide.

12. The process of claim 1 in which the said liquid composition contains as (A) a compound of formula ##STR59## where R⁵ denotes an alkylene group of 2 to 6 carbon atoms and further contains a compound (B) which has in the molecule both at least one group of formula I and at least one free sulfonic, phosphonic, or carboxylic acid group but has no group of formula II, and the solvent employed for development of the image is an aqueous solution of a base.

13. The process of claim 1 in which the said liquid composition also contains a compound (B) which has in the molecule both at least one group of formula I and at least one primary, secondary, or tertiary amino group but has no group of formula II, and the solvent employed for development of the image is an aqueous solution of an acid.