Aqueous developable high performance curable polymers

An ink jet printhead which comprises (i) an upper substrate with a set of parallel grooves for subsequent use as ink channels and a recess for subsequent use as a manifold, the grooves being open at one end for serving as droplet emitting nozzles, (ii) a lower substrate in which one surface thereof has an array of heating elements and addressing electrodes formed thereon, and (iii) a layer deposited on the surface of the lower substrate and over the heating elements and addressing electrodes and patterned to form recesses therethrough to expose the heating elements and terminal ends of the addressing electrodes, the upper and lower substrates being aligned, mated, and bonded together to form the printhead with the grooves in the upper substrate being aligned with the heating elements in the lower substrate to form droplet emitting nozzles, said layer comprising a crosslinked or chain extended polymer-containing composition formed by crosslinking or chain extending a precursor polymer having terminal end groups and monomer repeat units, at least some of said monomer repeat units having water solubility- or water dispersability-imparting substituents and at least some monomer repeat units having photosensitivity-imparting substituents which enable crosslinking or chain extension of the precursor polymer upon exposure to actinic radiation, said precursor polymer having monomer repeat units of the formula

• wherein x is an integer of 0 or 1;
• P is a functional group which imparts photosensitivity to polymers of formula III and formula IV;
• W is a functional group which imparts water solubility or dispersability to polymers of formula III and formula IV;
• e, f, g, h, i, j, k, and m are each integers of 0, 1, 2, 3, or 4, provided that the sum of i+e is no greater than 4, the sum of j+f is no greater than 4, the sum of k+g is no greater than 4, and the sum of m+h is no greater than 4, provided that at least one of e, f, g, and h is equal to at least 1 in at least some of the monomer repeat units of polymers of formula III and formula IV, and provided that at least one of i, j, k, and m is equal to at least 1 in at least some of the monomer repeat units of polymers of formula III and formula IV;
• A is
• or mixtures thereof, B is
• wherein v is an integer of from 1 to about 20,
• wherein z is an integer of from 2 to about 20,
• wherein u is an integer of from 1 to about 20,
• wherein w is an integer of from 1 to about 20,
• or mixtures thereof, and n is an integer representing the number of repeating monomer units, said crosslinking or chain extension occurring through photosensitivity-imparting substituents “P” contained on at least some of the monomer repeat units of the precursor polymer which form crosslinks or chain extensions in the precursor polymer upon exposure to actinic radiation, said precursor polymer also containing at least some monomer repeat units with water-solubility- or water-dispersability-imparting substituents “W”.

A crosslinked or chain extended polymer formed by crosslinking or chain extending a precursor polymer having terminal end groups and monomer repeat units, at least some of said monomer repeat units having photosensitivity-imparting water solubility- or water dispersability-imparting substituents which enable crosslinking or chain extension of the precursor polymer upon exposure to actinic radiation, said precurso polymer having monomer repeat units (1) of the formula

• wherein x is an integer of 0 or 1;
• PW is a functional group which imparts both photosensitivity and water solubility or dispersability to polymers of formula I:
• a, b, c, and d are each integers of 0, 1, 2, 3, or 4, provided that at least one of a, b, c, and d is equal to or greater than 1 in at least some of the monomer repeat units of polymers of formula I;
• wherein (a) A is
• or mixtures thereof, and B is
• wherein v is an integer of from 1 to about 20,
• wherein z is an integer of from 2 to about 20,
• wherein u is an integer of from 1 to about 20,
• wherein w is an integer of from 1 to about 20,
• or mixtures thereof;
• of (b) A is
• or mixtures thereof, and B is
• wherein u is an integer of from 1 to about 20,
• or mixtures thereof;
• and n is an integer representing the number of repeating monomer units;
• or (2) of the formula
• wherein x is an integer of 0 or 1;
• PW is a functional group which imparts both photosensitivity and water solubility or dispersability to polymers of formula II;
• a, b, c, and d are each integers of 0, 1, 2, 3, or 4, provided that at least one of a, b, c, and d is equal to or greater than 1 in at least some of the monomer repeat units of polymers of formula II;
• wherein A is
• or mixtures thereof, B is
• wherein v is an integer of from 1 to about 20,
• wherein z is an integer of from 2 to about 20,
• wherein u is an integer of from 1 to about 20,
• wherein w is an integer of from 1 to about 20,
• or mixtures thereof;
• and n is an integer representing the number of repeating monomer units;
• said crosslinking or chain extension occurring through “PW” photosensitivity-imparting substituents contained on at least some of the monomer repeat units of the precursor polymer which form crosslinks or chain extensions in the precursor polymer upon exposure to actinic radiation.

A crosslinked or chain extended polymer formed by crosslinking or chain extending a precursor polymer having terminal end groups and monomer repeat units, at least some of said monomer repeat units having water solubility- or water dispersability-imparting substituents and at least some monomer repeat units having photosensitivity-imparting substituents which enable crosslinking or chain extension of the precursor polymer upon exposure to actinic radiation, said precursor polymer having monomer repeat units (1) of the formula

• wherein x is an integer of 0 or 1;
• P is a functional group which imparts photosensitivity to polymers of formula III;
• W is a functional group which imparts water solubility or dispersability to polymers of formula III;
• e, f, g, h, i, j, k, and m are each integers of 0, 1, 2, 3, or 4, provided that the sum of i+e is no greater than 4, the sum of j+f is no greater than 4, the sum of k+g is no greater than 4, and the sum of m+h is no greater than 4, provided that at least one of e, f, g, and h is equal to at least 1 in at least some of the monomer repeat units of polymers of formula III, and provided that at least one of i, j, k, and m is equal to at least 1 in at least some of the monomer repeat units of polymers of formula III;
• wherein (a) A is
• or mixtures thereof, and B is
• wherein v is an integer of from 1 to about 20,
• wherein z is an integer of from 2 to about 20,
• wherein u is an integer of from 1 to about 20,
• wherein w is an integer of from 1 to about 20,
• or mixtures thereof;
• or (b) A is
• or mixtures thereof, and B is
• wherein u is an integer of from 1 to about 20,
• or mixtures thereof, and n is an integer representing the number of repeating monomer units;
• or (2) of the formula
• wherein x is an integer of 0 or 1;
• P is a functional group which imparts photosensitivity to polymers of formula IV;
• W is a functional group which imparts water solubility or dispersability to polymers of formula IV;
• e, f, g, h, i, j, k, and m are each integers of 0, 1, 2, 3, or 4, provided that the sum of i+e is no greater than 4, the sum of j+f is no greater than 4, the sum of k+g is no greater than 4, and the sum of m+h is no greater than 4, provided that at least one of e, f, g, and h is equal to at least 1 in at least some of the monomer repeat units of polymers of formula IV, and provided that at least one of i, j, k, and m is equal to at least 1 in at least some of the monomer repeat units of polymers of formula IV;
• wherein A is
• or mixtures thereof, B is
• wherein v is an integer of from 1 to about 20,
• wherein z is an integer of from 2 to about 20,
• wherein u is an integer of from 1 to about 20,
• whereinn w is an integer of from 1 to about 20,
• or mixtures thereof, and n is an integer representing the number of repeating monomer units, said crosslinking or chain extension occurring through photosensitivity-imparting substituents “P” contained on at least some of the monomer repeat units of the precursor polymer which form crosslinks or chain extensions in the precursor polymer upon exposure to actinic radiation, said precursor polymer also containing at least some monomer repeat units with water-solubility- or water-dispersability-imparting substituents “W”.

A crosslinked or chain extended polymer formed by crosslinking or chain extending a precursor polymer having terminal end groups and monomer repeat units, at least some of said monomer repeat units having photosensitivity-imparting water solubility- or water dispersability-imparting substituents which enable crosslinking or chain extension of the precursor polymer upon exposure to actinic radiation, said precursor polymer having monomer repeat units (a) of the formula

• wherein x is an integer of 0 or 1;
• PW is a functional group which imparts both photosensitivity and water solubility or dispersability to polymers of formula I and is selected from (i) unsaturated ammonium groups of the formula
• wherein X is
• R1 and R2 each, independently of the other, are hydrogen atoms, alkyl groups, substituted alkyl groups, aryl groups, substituted aryl groups, arylalkyl groups, or substituted arylalkyl groups, wherein R1 and R2 can be joined to form a ring, R3 is an alkylene group, a substituted alkylene group, an arylene group, a substituted arylene group, an arylalkylene group, or a substituted arylalkylene group, R4, R5, and R6 each, independently of the others, are hydrogen atoms, alkyl groups, substituted alkyl groups, aryl groups, substituted aryl groups, arylalkyl groups, or substituted arylalkyl groups, wherein two or more of R4, R5, and R6 can be joined together to form a ring, and R7 and R8 each, independently of the other, are hydrogen atoms, alkyl groups, substituted alkyl groups, aryl groups, substituted aryl groups, arylalkyl groups, or substituted arylalkyl groups, x is an integer of from 1 to about 6, y is an integer of from 1 to about 50, and R and R′ each, independently of the other, are hydrogen atoms or alkyl groups;
• (ii) unsaturated phosphonium groups;
• (iii) unsaturated ether groups;
• or (iv) mixtures thereof;
• a, b, c, and d are each integers of 0, 1, 2, 3, or 4, provided that at least one of a, b, c, and d is equal to or greater than 1 in at least some of the monomer repeat units of polymers of formula I;
• and either (1) A is
• or mixtures thereof, and B is
• wherein v is an integer of from 1 to about 20,
• wherein z is an integer of from 2 to about 20,
• wherein u is an integer of from 1 to about 20,
• wherein w is an integer of from 1 to about 20,
• or mixtures thereof;
• or (2) A is
• —C(CH3)2—
• and B is
• wherein z is an integer of from 2 to about 20,
• wherein u is an integer of from 1 to about 20,
• wherein w is an integer of from 1 to about 20,
• or mixtures thereof;
• or (b) of the formula
• wherein x is an integer of 0 or 1;
• PW is a functional group which imparts both photosensitivity and water solubility or dispersability to polymers of formula II;
• a, b, c, and d are each integers of 0, 1, 2, 3, or 4, provided that at least one of a, b, c, and d is equal to or greater than 1 in at least some of the monomer repeat units of polymers of formula II;
• A is
• or mixtures thereof, B is
• wherein v is an integer of from 1 to about 20,
• wherein z is an integer of from 2 to about 20,
• wherein u is an integer of from 1 to about 20,
• wherein w is an integer of from 1 to about 20,
• or mixtures thereof, and n is an integer representing the number of repeating monomer units;
• said crosslinking or chain extension occurring through “PW” photosensitivity-imparting substituents contained on at least some of the monomer repeat units of the precursor polymer which form crosslinks or chain extensions in the precursor polymer upon exposure to actinic radiation.

A crosslinked or chain extended polymer formed by crosslinking or chain extending a precursor polymer having terminal end groups and monomer repeat units, at least some of said monomer repeat units having water solubility- or water dispersability-imparting substituents and at least some monomer repeat units having photosensitivity-imparting substituents which enable crosslinking or chain extension of the precursor polymer upon exposure to actinic radiation, said precursor polymer having monomer repeat units (a) of the formula

• wherein x is an integer of 0 or 1;
• P is a functional group which imparts photosensitivity to polymers of formula III and is selected from unsaturated ester groups, alkylcarboxymethylene groups, ether groups, epoxy groups, allyl ether groups, hydroxyalkyl groups, unsaturated ammonium groups, unsaturated phosphonium groups, or mixtures thereof;
• W is a functional group which imparts water solubility or dispersability to polymers of formula III and is selected from quaternary ammonium groups, quaternary phosphonium groups, sulfonium groups, or mixtures thereof;
• e, f, g, h, i, j, k, and m are each integers of 0, 1, 2, 3, or 4, provided that the sum of i+e is no greater than 4, the sum of j+f is no greater than 4, the sum of k+g is no greater than 4, and the sum of m+h is no greater than 4, provided that at least one of e, f, g, and h is equal to at least 1 in at least some of the monomer repeat units of polymers of formula III, and provided that at least one of i, j, k, and m is equal to at least 1 in at least some of the monomer repeat units of polymers of formula III;
• and either (1) A is
• or mixtures thereof, and B is
• wherein v is an integer of from 1 to about 20,
• wherein z is an integer of from 2 to about 20,
• wherein u is an integer of from 1 to about 20,
• wherein w is an integer of from 1 to about 20,
• or mixtures thereof;
• or (2) A is
• —C(CH3)2—
• and B is
• wherein z is an integer of from 2 to about 20,
• wherein u is an integer of from 1 to about 20,
• wherein w is an integer of from 1 to about 20,
• or mixtures thereof;
• or (b) of the formula
• wherein x is an integer of 0 or 1;
• P is a functional group which imparts photosensitivity to polymers of formula IV;
• W is a functional group which imparts water solubility or dispersability to polymers of formula IV;
• e, f, g, h, i, j, k, and m are each integers of 0, 1, 2, 3, or 4, provided that the sum of i+e is no greater than 4, the sum of j+f is no greater than 4, the sum of k+g is no greater than 4, and the sum of m+h is no greater than 4, provided that at least one of e, f, g, and h is equal to at least 1 in at least some of the monomer repeat units of polymers of formula IV, and provided that at least one of i, j, k, and m is equal to at least 1 in at least some of the monomer repeat units of polymers of formula IV;
• A is
• or mixtures thereof, B is
• wherein v is an integer of from 1 to about 20,
• wherein z is an integer of from 2 to about 20,
• wherein u is an integer of from 1 to about 20,
• wherein w is an integer of from 1 to about 20,
• or mixtures thereof, and n is an integer representing the number of repeating monomer units, said crosslinking or chain extension occurring through photosensitivity-imparting substituents “P” contained on at least some of the monomer repeat units of the precursor polymer which form crosslinks or chain extensions in the precursor polymer upon exposure to actinic radiation, said precursor polymer also containing at least some monomer repeat units with water-solubility- or water-dispersability-imparting substituents “W”.

A process which comprises reacting a polymer containing at least some monomer repeat units with haloalkyl substituents thereon and of the formula

• wherein x is an integer of 0 or 1, R is an alkyl group, a substituted alkyl group, an arylalkyl group, or a substituted arylalkyl group, X is a halogen atom, a, b, c, and d are each integers of 0, 1, 2, 3, or 4, provided that at least one of a, b, c, and d is equal to or greater than 1 in at least some of the monomer repeat units of the polymer, A is
• or mixtures thereof, B is
• wherein v is an integer of from 1 to about 20,
• wherein z is an integer of from 2 to about 20,
• wherein u is an integer of from 1 to about 20,
• wherein w is an integer of from 1 to about 20,
• or mixtures thereof, and n is an integer representing the number of repeating monomer units, with an unsaturated amine, unsaturated phosphine, or unsaturated alcohol, thereby forming a water-soluble or water-dispersable photopatternable polymer with unsaturated ammonium, unsaturated phosphonium, or unsaturated ether functional groups.