Method for improving adhesion of water-based inks to halogen-containing resin articles

A method for improving the water wettability of a PVC article which comprises mixing a vinyl chloride resin with a latent mercaptan having the formula:

• wherein a is 1, m is 0, and n is 0 or 1;
• y=1 to 4;
• R1 is R′C(O)OH, wherein R′ is an alkylene radical having 2 or 3 carbon atoms, or R1 is an alkyl, pentaerythrityl, alkylene, cycloalkyl, cycloalkylene, aryl, alkaryl, aralkyl, aralkytene, hydroxyalkyl, dihydroxyalkyl, alkoxyalkyl, acyloxyalkyl, hydroxy(polyalkoxy)alkyl, acyloxy(hydroxyalkyl), acyloxy(alkoxyalkyl), acyloxy(polyalkoxy)alkyl, benzoyloxy(polyalkoxy)alkyl, alkylene bis-(acyloxyalkyl), hydroxyalkoxyalkyl, alkoxy(hydroxyalkyl), alkoxy(polyalkoxy)alkyl, alkoxycarbonylalkylenyl, hydroxyalkoxycarbonylalkyl, hydroxy(polyalkoxy)carbonylalkyl, alkoxy(polyalkoxy)carbonylalkyl, mercaptoalkoxycarbonylalkyl, mercaptoalkoxycarbonylalkylenyl, mercaptoalkyl, mercaptoalkylene, tetrahydropyranyloxy(polyalkoxy)carbonylalkyl, tetrahydropyranyloxyalkyl, hydroxyaryl, or mercaptoaryl radical having from 1 to 22 carbon atoms;
• R2, R3, R4, R5, R6, and R7 are independently hydrogen, a hydroxyl, mercapto, alkyl, alkylene, acyl, aryl, haloaryl, alkaryl, aralkyl, hydroxyalkyl, alkenyloxyalkoxy, alkoxy, aryloxy, alkaryloxy, mercaptoalkyl, hydroxyalkylmercaptoalkyl, mercaptoalkylene, hydroxyaryl, alkoxyaryl, alkoxyhydroxyaryl, arylcarbonyl, or mercaptoaryl radical having from 1 to 22 carbon atoms;
• X is a heteroatom selected from the group consisting of oxygen and sulfur, and one or both of the R3 and R5 alkylene radicals joins with R7 and X to form a heterocyclic moiety with X as the heteroatom;
• with a zinc ionomer as the sole metal-containing stabilizer and heating the mixture to the incipient resin decomposition temperature.

A heat-stable PVC resin composition comprising a blocked mercaptan having the structure:

• wherein a is 0 or 1, m is 0 or 1, and n is 0 or 1;
• y=1 to 4, when y=1, z is 1 to 4, when y is more than 1, z is 1;
• R1 is R′C(O)OH, wherein R′ is an alkylene radical having 2 or 3 carbon atoms, or R1 is an alkyl, alkylene, pentaerythrityl, cycloalkyl, cycloalkylene, aryl, alkaryl, aralkyl, aralkylene, hydroxyalkyl, dihydroxyalkyl, alkoxyalkyl, acyloxyalkyl, hydroxy-(polyalkoxy)alkyl, hydroxy(polyalkoxyoarbonylalkyl), acyloxy-(hydroxyalkyl), acyloxy(alkoxyalkyl), acyloxy(polyalkoxy)alkyl, acyloxy(polyalkoxycarbonylalkyl), alkoxycarbonylalkyl, oxy[bis(alkoxycarbonylalkyl)], oxy[bis(polyalkoxycarbonylalkyl)], benzoyloxy(polyalkoxy)alkyl, benzoyloxy(poryalkoxy)carbonylalkyl, alkylene bis-(acyloxyalkyl), thio-bis-[alkoxycarbonylalkyl], dithio-bis-[alkoxycarbonylalkyl], alkoxy(polyalkoxy)carbonylalkyl, hydroxyalicoxyalkyl, alkoxy(hydroxyalkyl), alkoxy(acyloxyalkyl), alkoxy(polyalkoxy)alkyl, mercaptoalkyl, mercaptoalkylene, tetrahydropyranyloxy(polyalkoxy)carbonylalkyl, tetrahydropyranyloxyalkyl, hydroxyaryl, or mercaptoaryl radical having from 1 to 22 carbon atoms;
• R2, R3, R4, R5, R6, and R7 are independently hydrogen, a hydroxyl, mercapto, alkyl, alkylene, acyl, aryl, haloaryl, alkaryl, aralkyl, hydroxyalkyl, chloroalkoxy, alkenyloxyalkoxy, alkoxy, aryloxy, alkaryloxy, mercaptoalkyl, hydroxyalkylmercaptoalkyl, mercaptoalkylenyl, hydroxyaryl, alkoxyaryl, alkoxyhydroxyaryl, arylcarbonyl, or mercaptoaryl radical having from 1 to 22 carbon atoms;
• X is phenyl, halophenyl, alkylphenyl, hydroxyphenyl, dihydroxyphenyl, alkoxyphenyl, phenylcyclohexyl, or a heteroatom selected from the group consisting of oxygen and sulfur, and one or both of the R3 and R5 alkylene radicals joins with R7 and X to form a heterocyclic moiety with X as the heteroatom;
• and a uracil having the formula:
• wherein R* and R**, are independently hydroqen, alkyl, hydroxyalkyl, or alkoxyalkyl, and R*** is hydrogen, alkyl, phenyl, or hydroxyphenyl, wherein each of the alkyl moieties have from 1 to 4 carbon atoms, and optionally,
• as the sole metal-containing stabilizer, an amount of a zinc ionomer effective to improve the wettability by water-based paints and inks of an article formed from the PVC resin composition.

A heat-stable PVC resin composition comprising a blocked mercaptan having the structure:

• wherein a is 0 or 1, m is 0 or 1, and n is 0 or 1;
• y=1 to 4, when y=1, z is 1 to 4, when y is more than 1, z is 1;
• R1 is R′C(O)OH, wherein R′ is an alkylene radical having 2 or 3 carbon atoms, or R1 is an alkyl, alkylene, pentaerythrilyl, cycloalkyl, cycloalkylene, aryl, alkaryl, aralkyl, aralkylene, hydroxyalkyl, dihydoxyalkyl, alkoxyalkyl, acyloxyalkyl, hydroxy(polyalkoxy)alkyl, hydroxy(polyalkoxy)acyl, acyloxy(hydroxyalkyl), acyloxy(alkoxyalkyl), acyloxy(polyalkoxy)alkyl, acyloxy(polyalkoxy)acyl, alkoxycarbonylalkyl, oxy[bis(alkoxycarbonylalkyl)], oxy[bis(polyalkoxycarbonylalkyl)], benzoyloxy(polyalkoxy)alkyl, benzoyloxy(polyalkoxy)carbonylalkyl, alkylene bis-(acyloxyalkyl), thio-bis-[alkoxycarbonylalkyl], dithio-bis-[alkoxycarbonylalkyl], alkoxy(polyalkoxy)carbonylalkyl, hydroxyalkoxyalkyl, alkoxy(hydroxyalkyl), alkoxy(acyloxyalkyl), alkoxy(polyalkoxy)alkyl, mercaptoalkyl, mercaptoalkylene, tetrahydropyranyloxy(polyalkoxy)carbcinylalkyl, tetrahydropyranyloxyalkyl, hydroxyaryl, or mercaptoaryl radical having from 1 tt 22 carbon atoms;
• R2, R3, R4, R5, R6, and R7 are independently hydrogen, a hydroxyl, mercapto, alkyl, alkylene, acyl, aryl, haloaryl, alkaryl, aralkyl, hydroxyalkyl, chloroalkoxy, alkenyloxyalkoxy, alkoxy, aryloxy, alkaryloxy, mercaptoalkyl, hydroxyalkylmercaptoalkyl, mercaptoalkylenyl, hydroxyaryl, alkoxyaryl, alkoxyhydroxyaryl, arylcarbonyl, or mercaptoaryl radical having from 1 to 22 carbon atoms;
• X is phenyl, halophenyl, alkylphenyl, hydroxyphenyl, dihydroxyphenyl, alkoxyphenyl, phenylcyclohexyl, or a heteroatom selected from the group consisting of oxygen and sulfur, and one or both of the R3 and R5 alkylenyl radicals joins with R7 and X to form a heterocyclic moiety with X as the heteroatom;
• and a pyrrolodiazine dione described by the formula:
• wherein R⋄, R2⋄, R3⋄, and R4⋄are independently hydrogen or C1-C4 alkyl;
• and optionally,
• as the sole metal-containing stabilizer, an amount of a zinc ionomer effective to improve the wettability by water-based paints and inks of an article formed from the PVC resin composition.