High speed aqueous solvent developable photopolymer compositions

• US 5,235,015 A
• Filed: 02/21/1991
• Issued: 08/10/1993
• Est. Priority Date: 02/21/1991
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Company
• Inventors: Ali, M. Zaki, Ali, Mahfuza B., Moren, Dean M.
• Primary Examiner(s): BRAMMER, JACK
• Application Number:
  US07/658,983
• Time in Patent Office: 901 Days
• Field of Search: 430/281, 430/286, 430/287, 522/14, 522/15, 522/34, 522/121, 522/149, 526/288, 526/292.2, 526/304, 526/306
• US Class Current: 526/304
• CPC Class Codes: C08F 20/00 Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
• CPC Class Codes: C08F 8/30 Introducing nitrogen atoms or nitrogen-containing groups
• CPC Class Codes: G03F 7/0388 with ethylenic or acetylenic bands in the side chains of the photopolymer
• CPC Class Codes: Y10T 428/31692 Next to addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31696 Including polyene monomers [e.g., butadiene, etc.]

Abstract

Novel photosensitive compositions based on azlactone derived polymers are described. The polymers have a hydrocarbyl backbone and pendant peptide groups with free-radically polymerizable functionality attached thereto, said polymer further comprising at least one oxyacid group or salt thereof, and optionally quaternary ammonium salt groups. A high speed durable printing plate having a mild pH aqueous developability is disclosed which incorporates these polymers in combination with a photoinitiator. The polymers are also useful as proofing films in graphic arts applications.

Claims

1. An energy sensitive polymer having the formula:

##STR11## wherein R¹ independently is hydrogen or methyl;

R² is given by ##STR12## wherein n is 0 or 1;

R⁵, R⁶, R⁷, and R⁸ are independently an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms, an aryl or aralkyl group having 6 to 12 carbon atoms or at least one of the pairs R⁵ and R⁶, and R⁷ and R⁸, taken together with the carbon to which it is joined forms a 5- or 6-membered carbocyclic ring, or any of R⁵, R⁶, R⁷, and R⁸ may be H when n is 1;

W is --NH--, -NR²⁰, --S-- or --O--;

wherein R²⁰ is alkyl of 1 to 12 carbon atoms; and

Z represents ##STR13## wherein R⁵, R⁶, R⁷, R⁸, and n are as previously described;

R³ is a polymerizable, ethylenically unsaturated group selected from

(a) ##STR14## in which R⁹ is an alkylene group having 1 to 12 carbon atoms, an arylene group having 6 to 10 carbon atoms, an oxyalkylene group or a poly(oxyalkylene) in which said alkylene group has 2 to 4 carbon atoms, the number of oxygen atoms is a positive integer less than or equal to four;

R¹⁰ is hydrogen, cyano, a carboxyl group, or a --C(═

O)NH₂ group; and

R¹¹ is hydrogen, an alkyl group having 1 to 12 carbon atoms, or a phenyl group or naphthyl group;

or

(b) -R⁹ -W-T in which R⁹ is as defined as in (a), W is as previously defined, and T is an ethylenically unsaturated group selected from the group consisting of acryloyl, methacryloyl, cinnamoyl, maleoyl, fumaroyl, itaconoyl, and crotonoyl, and is preferably acryloyl or methacryloyl;

a, b, c, and d are independently integers, wherein a and b are at least 1, and the sum of a+b+c+d is sufficient to provide a polymer having a number average molecular weight in the range of 2,000 to 1,000,000;

G is given by -R⁹ -N⁺ R¹² R¹³ R¹⁴ X^-, wherein R⁹ is as previously defined, and R¹² -R¹⁴ are independently an alkyl group having 1 to 16 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms, an aryl or aralkyl group having 6 to 12 carbon atoms or any two or all three of R¹² -R¹⁴ taken together with the nitrogen to which they are joined can form a 5- to 8-membered heterocyclic ring, and X^- represents any non-interfering anion including anions located elsewhere on the polymeric backbone or side chains;

R represents an aryl group having from 6 to 30 carbon atoms, cyano, --CO₂ H, carboalkoxy group having from 2 to 40 carbon atoms, or a mono- or dialkylcarbamoyl group having from 2 to 40 carbon atoms;

R⁴ represents hydrogen, a solubilizing cation, or -E-A wherein E represents an organic divalent connecting group having up to a total of about 18 C, N, S, and nonperoxidic O atoms, and A is an acid selected from carboxylic acids, sulfonic acids, phosphonic acids, and salts thereof.

2. The polymer according to claim 1 wherein R¹ is H, and R⁵ and R⁶ are methyl, and n is 0.

3. The polymer according to claim 1 which has a homopolymeric backbone.

4. The polymer according to claim 1 which has a copolymeric backbone.

5. The polymer according to claim 1 wherein the A group of R⁴ is an alkali metal or a tetra-substituted ammonium salt of a carboxyl, sulfo, or phospho group.

6. The polymer according to claim 1 wherein the A group of R⁴ is PO₃ H₂, SO₃ H, or CO₂ H.

7. The polymer according to claim 1 wherein R is --COOH.

8. The polymer according to claim 1 which is derived from an alkenylazlactone monomer.

9. The polymer according to claim 1 which is derived from an alkenylazlactone monomer and at least one additional free-radically polymerizable comonomer.

10. The polymer according to claim 9 wherein said comonomer is a diacid.

11. The polymer according to claim 9 wherein said alkenylazlactone is present in the range of 10 to 100 weight percent and said at least one comonomer is present in the range of more than 0 to 90 weight percent.

12. The polymer according to claim 1 having a number average molecular weight in the range of 2,000 to 1,000,000.