Radiatioin-curable mixture containing low-functionalised, partially saponified polyvinyl acetate
The invention relates to a radiation-curable mixture for generating relief structures, comprising a) at least one functionalized, part-hydrolyzed polyvinyl acetate comprising (i) vinyl alcohol units, (ii) vinyl acetate units, and (iii) vinyl acrylate units, where the vinyl acrylate units, which can be substituted, have the general structure where R is hydrogen or a linear or branched aliphatic or heteroaliphatic radical having 1 to 12 carbon atoms, or a cycloaliphatic, heterocyclic or aromatic radical having 3 to 12 carbon atoms, as component A, b) at least one initiator as component B, c) at least one ethylenically unsaturated compound different from component A, as component C, d) one or more adjuvants as component D, wherein the amount of vinyl acrylate units (iii) in the functionalized, part-hydrolyzed polyvinyl acetate a), based on all the units (i), (ii), and (iii), is 0.1 to <3 mol %, and component D comprises an additive capable of hydrogen bonding, in an amount of 0.001 to 30 wt %, based on the sum of components A to D.
1. A radiation-curable mixture for generating relief structures, comprising
a) an ethylenically unsaturated compound as component A, said compound being a functionalized, part-hydrolyzed polyvinyl acetate comprising (i) vinyl alcohol units, (ii) vinyl acetate units, and (iii) vinyl acrylate units, where the vinyl acrylate units, which can be substituted, have the general structure
wherein the amount of vinyl acrylate units (iii) in the functionalized, part-hydrolyzed polyvinyl acetate a), based on all the units (i), (ii), and (iii), is 0.1 to <3 mol %, where R is hydrogen or a linear or branched aliphatic or heteroaliphatic radical, or a cycloaliphatic, heterocyclic or aromatic radical having up to 12 carbon atoms;
b) an initiator or initiator system as component B,
c) an ethylenically unsaturated compound different from component A, as component C,
d) an additive capable of hydrogen bonding, as component D,
said additive being present in an amount of 1 to 30 wt %, based on the sum of all components in the radiation-curable mixture;
wherein the additive capable of hydrogen bonding is selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, polyethyleneimine, polyurethanes, polyethylene glycol, and polyvinyl alcohol/polyethylene glycol graft copolymer.
2. The radiation-curable mixture as claimed in claim 1 , wherein the amount of vinyl alcohol units (i) in component A, based on all the units (i), (ii), and (iii), is 65 to 99 mol %.
3. The radiation-curable mixture as claimed in claim 1 , wherein the amount of vinyl acetate units (ii) in component A, based on all the units (i), (ii), and (iii), is 5 to 35 mol %.
4. The radiation-curable mixture as claimed in claim 1 , wherein component A is present in an amount of 5 to 75 wt %, based on the sum of components A to D.
5. The radiation-curable mixture as claimed in claim 1 , wherein component B is present in an amount of 0.1 to 20 wt %, based on the sum of components A to D.
6. The radiation-curable mixture as claimed in claim 1 , wherein the ethylenically unsaturated compound of component C comprises at least one vinyl ether group and/or acrylate group and/or methacrylate group.
7. The radiation-curable mixture as claimed in claim 1 , wherein component C is present in an amount of 0.5 to 50 wt %, based on the sum of components A to D.
8. The radiation-curable mixture as claimed in claim 1 , wherein the additives are selected from the group consisting of plasticizers, solvents, further binders, colorants, stabilizers, chain transfer agents, UV absorbers, dispersing assistants, non-radically crosslinking crosslinkers, viscosity modifiers, and hydrogen bond-accepting additives.
9. The radiation-curable mixture as claimed in claim 1 , wherein component D is present in an amount of 1 to 25 wt %, based on the sum of components A to D.
10. A radiation-curable multilayer element at least comprising a relief-forming layer of the radiation-curable mixture as claimed in claim 1 on a carrier.
11. The radiation-curable multilayer element as claimed in claim 10 , comprising, on or under the relief-forming layer, at least one further layer selected from the group consisting of a protective layer, a release layer, a mask layer, a barrier layer, a layer for generating a surface structure, and a tie layer or any desired combinations thereof.
12. A method for producing the multilayer element having a relief structure from a radiation-curable multilayer element as claimed in claim 10 , comprising irradiating the relief-forming layer through an integral or appliable mask layer and removing the uncured regions of the relief-forming layer.
13. A method for producing the multilayer element having a relief structure from a radiation-curable multilayer element as claimed in claim 10 , comprising irradiating the relief-forming layer and engraving a relief into cured regions of the relief-forming layer.
14. A radiation-curable mixture for generating relief structures, comprising
a) a functionalized, part-hydrolyzed polyvinyl acetate as component A, comprising (i) vinyl alcohol units, (ii) vinyl acetate units, and (iii) vinyl acrylate units, where the vinyl acrylate units, which can be substituted, have the general structure
wherein the amount of vinyl acrylate units (iii) in the functionalized, part-hydrolyzed polyvinyl acetate a), based on all the units (i), (ii), and (iii), is 0.1 to <3 mol %;
where R is chosen from:
a hydrogen,
a linear aliphatic or heteroaliphatic radical having 1 to 12 carbon atoms,
a branched aliphatic having 3 to 12 carbon atoms,
a heteroaliphatic radical having 2 to 12 carbon atoms,
a cycloaliphatic, heterocyclic having 3 to 12 carbon atoms or
an aromatic radical having 4 to 12 carbon atoms,
b) an initiator or initiator system, as component B,
c) an ethylenically unsaturated compound, as component C,
d) an additive capable of hydrogen bonding, as component D, wherein said additive forms hydrogen bonds with the hydrolyzed polyvinyl acetate and wherein component D is present in an amount of 1 to 30 wt %, based on all components within the radiation-curable mixture, said component D being selected from the group consisting of alcohols, ketones, aldehydes, amines, amides, amino acids, carboxylic acids, thioethers, thiols, urethanes, esters, lactones, lactams, and combinations thereof.
15. The radiation-curable mixture as claimed in claim 1 , wherein component D is present in an amount of 5 to 20 wt %,based on the sum of components A to D.
16. The radiation-curable mixture as claimed in claim 1 , wherein component D is present in an amount of 10 to 20 wt %,based on the sum of components A to D.
17. The radiation-curable mixture as claimed in claim 1 , wherein
component A is present in an amount of 5 to 75 wt %, based on the sum of components A to D,
component B is present in an amount of 0.1 to 20 wt %, based on the sum of components A to D,
component C is present in an amount of 0.5 to 50 wt %, based on the sum of components A to D, and
component D is present in an amount of 1 to 25 wt %, based on the sum of components A to D.
18. The radiation-curable mixture as claimed in claim 14 , wherein
component A is present in an amount of 5 to 75 wt %, based on the sum of components A to D,
component B is present in an amount of 0.1 to 20 wt %, based on the sum of components A to D,
component C is present in an amount of 0.5 to 50 wt %, based on the sum of components A to D, and
component D is present in an amount of 1 to 25 wt %, based on the sum of components A to D.
19. The radiation-curable mixture as claimed in claim 1 , wherein
R is an aliphatic radical chosen from a linear or branched C1-C12 alkyl substituted by at least one halogen, hydroxyl, mercapto, ether, amine, carboxylic acid, ester, urethane, aldehyde, nitro, CF3, a cyano group or substituted with a C1-C4 alkyl; or wherein
R is a cycloaliphatic radical chosen from a cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, cyclopetatadiene, decalin, adamantane, or camphor radical; or wherein
R is a heterocyclic radical chosen from a 2-pyrrolidine, tetrahydrofuran, tetrahydrothiophene, pyran, thiopyran, pyrazole, imidazole, piperidine, or morpholine radical; or wherein
R is an aromatic or heteroaromatic radical chosen from a phenyl, benzyl, pyridine, naphthyl, pyrrole, furan, thiophene, pyridine, pyrazole, benzimidazole, indole, isoquinoline, purine, pyrimidine, oxazole, or thioazole radical.