Inkjet method for producing a spectacle lens

Abstract

An inkjet method for producing a spectacle lens and fluids that can be used in an inkjet method for producing a spectacle lens are disclosed. The inkjet method includes the following steps: a) providing a substrate to be printed on, b) applying to the substrate to be printed on from step a) at least two volume elements applied adjacently and/or adjoining one another, c) transferring the at least two volume elements applied adjacently and/or adjoining one another from step b) into at least one volume composite, d) transferring the at least one volume composite from step c) into at least one homogeneous volume composite, e) transferring the at least one homogeneous volume composite from step d) into at least one final volume composite.

Claims

1. An inkjet method of producing a spectacle lens, comprising at least: a) providing at least one fluid; b) providing a substrate to be printed on or providing a support material to be printed on and subsequently removed; c) applying at least one volume element of the at least one fluid from step a) to the substrate or support material from step b); d) activating a reaction within the at least one volume element from step c); e) applying at least one further volume element of the at least one fluid from step a) adjacent to and/or adjoining the at least one volume element from step c) to form at least two adjacently and/or mutually adjoiningly applied volume elements; f) coalescing, bonding, wetting, and/or contacting the at least two adjacently and/or mutually adjoiningly applied volume elements from step e) to form a homogeneous volume composite in which the reaction is not yet fully concluded; g) repeating steps e) and f); and h) concluding the reaction, wherein the coalescing, bonding, wetting, and/or contacting from step f) is effected with transmission of a reactivity between the adjacently and/or mutually adjoiningly applied volume elements and with transformation of the homogeneous volume composite to a final volume composite, wherein the at least one fluid from step a) contains: at least one hybrid system, at least one system containing at least one photolatent catalyst, at least one hybrid system containing at least one photolatent catalyst, or at least one thiol-ene system, and wherein repeating steps e) and f) includes effecting the transmission of the reactivity between adjacently applied and/or between mutually adjoining homogeneous volume elements of the homogeneous volume composite in which the reaction is not yet fully concluded in a repeated step f) before the reaction is concluded in an adjacently applied and/or mutually adjoining homogeneous volume element from which the reactivity has been transmitted to the homogenous volume composite.

2. The inkjet method as claimed in claim 1, wherein the reactivity is transmitted without reactivation.

3. An inkjet method of producing a spectacle lens, comprising at least: a) providing at least one fluid; b) providing a substrate to be printed on or providing a support material to be printed on and subsequently removed; c) applying at least two adjacent and/or mutually adjoining volume elements of the at least one fluid from step a) to the substrate or support material from step b); d) coalescing, bonding, wetting, and/or contacting the at least two adjacently and/or mutually adjoiningly applied volume elements from step c); e) activating a reactivity of the at least one fluid to initiate a reaction; f) applying at least one further volume element of the at least one fluid from step a); g) coalescing, bonding, wetting, and/or contacting the at least two adjacently and/or mutually adjoiningly applied volume elements from step d) with the at least one further volume element from step f) to form a homogeneous volume composite in which the reaction is not yet fully concluded; h) repeating steps f) and g) or repeating steps e), f) and g); and i) concluding the reaction, wherein the coalescing, bonding, wetting, and/or contacting from steps d) and g) is effected with transmission of the reactivity between the adjacently and/or mutually adjoiningly applied volume elements and with transformation of the homogeneous volume composite to a final volume composite, wherein the at least one fluid from step a) contains: at least one hybrid system, at least one system containing at least one photolatent catalyst, at least one hybrid system containing at least one photolatent catalyst, or at least one thiol-ene system, and wherein repeating steps e) and f) or steps e), f) and g) includes effecting the transmission of the reactivity between adjacently applied and/or between mutually adjoining homogeneous volume elements of the homogeneous volume composite in which the reaction is not yet fully concluded in a repeated step f) before the reaction is concluded in an adjacently applied and/or mutually adjoining homogeneous volume element from which the reactivity has been transmitted to the homogenous volume composite.

4. The inkjet method as claimed in claim 1, wherein the at least one hybrid system is selected from the group consisting of: at least one thiol-ene-(meth)acrylate hybrid system, at least one epoxythiol-(meth)acrylate hybrid system, and at least one epoxy-(meth)acrylate hybrid system.

5. The inkjet method as claimed in claim 1, wherein the at least one system containing the at least one photolatent catalyst is selected from the group consisting of: at least one epoxy-polyol system containing at least one photolatent acid, and at least one epoxythiol system containing at least one photolatent base.

6. The inkjet method as claimed in claim 1, wherein the at least one hybrid system containing the at least one photolatent catalyst is selected from the group consisting of: at least one epoxythiol-thiol/ene hybrid system containing at least one photolatent base, and at least one epoxythiol-(meth)acrylate hybrid system containing at least one photolatent base.

7. The inkjet method as claimed in claim 1, wherein the at least one fluid comprises the at least one thiol-ene system.

8. An inkjet method of producing a spectacle lens, comprising at least: a) providing at least one fluid; b) providing a substrate to be printed on or providing a support material to be printed on and subsequently removed; c) applying at least one volume element of the at least one fluid from step a) to the substrate or support material from step b); d) activating a reaction within the at least one volume element from step c); e) applying at least one further volume element of the at least one fluid from step a) adjacent to and/or adjoining the at least one volume element from step c) to form at least two adjacently and/or mutually adjoiningly applied volume elements; f) coalescing, bonding, wetting, and/or contacting the at least two adjacently and/or mutually adjoiningly applied volume elements from step e) to form a homogeneous volume composite in which the reaction is not yet fully concluded; g) repeating steps e) and f); and h) concluding the reaction, wherein the coalescing, bonding, wetting, and/or contacting from step f) is effected with transmission of a reactivity between the adjacently and/or mutually adjoiningly applied volume elements and with transformation of the homogeneous volume composite to a final volume composite, wherein the at least one fluid from step a) contains at least one photolatent catalyst, and wherein repeating steps e) and f) includes effecting the transmission of the reactivity between adjacently applied and/or between mutually adjoining homogeneous volume elements of the homogeneous volume composite in which the reaction is not yet fully concluded in a repeated step f) before the reaction is concluded in an adjacently applied and/or mutually adjoining homogeneous volume element from which the reactivity has been transmitted to the homogenous volume composite.

9. An inkjet method of producing a spectacle lens, comprising at least: a) providing at least one fluid; b) providing a substrate to be printed on or providing a support material to be printed on and subsequently removed; c) applying at least two adjacent and/or mutually adjoining volume elements of the at least one fluid from step a) to the substrate or support material from step b); d) coalescing, bonding, wetting, and/or contacting the at least two adjacently and/or mutually adjoiningly applied volume elements from step c); e) activating a reactivity of the at least one fluid to initiate a reaction; f) applying at least one further volume element of the at least one fluid from step a); g) coalescing, bonding, wetting, and/or contacting the at least two adjacently and/or mutually adjoiningly applied volume elements from step d) with the at least one further volume element from step f) to form a homogeneous volume composite in which the reaction is not yet fully concluded; h) repeating steps f) and g) or repeating steps e), f) and g); and i) concluding the reaction, wherein the coalescing, bonding, wetting, and/or contacting from steps d) and g) is effected with transmission of the reactivity between the adjacently and/or mutually adjoiningly applied volume elements and with transformation of the homogeneous volume composite to a final volume composite, wherein the at least one fluid from step a) contains at least one photolatent catalyst, and wherein repeating steps e) and f) or steps e), f) and g) includes effecting the transmission of the reactivity between adjacently applied and/or between mutually adjoining homogeneous volume elements of the homogeneous volume composite in which the reaction is not yet fully concluded in a repeated step f) before the reaction is concluded in an adjacently applied and/or mutually adjoining homogeneous volume element from which the reactivity has been transmitted to the homogenous volume composite.

10. The inkjet method as claimed in claim 8, wherein the at least one photolatent catalyst is at least one photolatent acid or at least one photolatent base.

11. The inkjet method as claimed in claim 10, wherein the at least one fluid comprises: the at least one photolatent acid in a total proportion from a range from 0.001% by weight to 2% by weight, based on a total weight of the at least one fluid, or the at least one photolatent base in a total proportion from a range from 0.001% by weight to 5.0% by weight, based on the total weight of the at least one fluid.

12. The inkjet method as claimed in claim 1, wherein the substrate is a finished spectacle lens or a thin lens.

13. The inkjet method as claimed in claim 1, wherein the activation is effected by means of actinic radiation and/or by means of thermal energy.

14. The inkjet method as claimed in claim 1, wherein the reactivity is transmitted: in an x and/or y direction and/or in a z direction, or independently of the x and/or y direction and independently of the z direction.

15. The inkjet method as claimed in claim 1, wherein the coalescing, bonding, wetting, and/or contacting the at least two adjacently and/or mutually adjoiningly applied volume elements is effected: laterally between volume elements adjacently applied and/or mutually adjoining in an x and/or y direction, in a z direction between volume elements adjacently applied and/or mutually adjoining, or independently of the x and/or y direction and independently of the z direction.

16. An inkjet method of producing a spectacle lens, comprising at least: a) providing a substrate to be printed on or providing a support material to be printed on and subsequently removed; b) providing at least one fluid; c) applying at least two adjacent and/or mutually adjoining volume elements containing the at least one fluid from step b) to the substrate or support material from step a); d) coalescing, bonding, wetting, and/or contacting the at least two adjacently applied and/or mutually adjoining volume elements from step c) with transformation of the at least two adjacently applied and/or mutually adjoining volume elements to a volume composite; e) activating a reaction of the fluid within the volume composite from step d) and commencement of the reaction with transformation of the volume composite into a homogeneous volume composite in which the reaction is not yet fully concluded; f) applying at least one further volume element containing the at least one fluid from step b) adjacent to and/or adjoining the homogeneous volume composite from step e); g) coalescing, bonding, wetting, and/or contacting the at least one further adjacently applied and/or mutually adjoining volume element from step f) with the homogeneous volume composite from step e) to extend the homogeneous volume composite; h) repeating steps f) and g); and i) concluding the reaction, wherein the coalescing, bonding, wetting, and/or contacting from steps d) and g) is effected with transmission of a reactivity between the adjacently and/or mutually adjoiningly applied volume elements and with transformation of the homogeneous volume composite to a final volume composite, wherein the fluid from step a) contains: at least one hybrid system, at least one system containing at least one photolatent catalyst, at least one hybrid system containing at least one photolatent catalyst, or at least one thiol-ene system, and wherein repeating steps e) and f) includes effecting the transmission of the reactivity between adjacently applied and/or between mutually adjoining homogeneous volume elements of the homogeneous volume composite in which the reaction is not yet fully concluded in a repeated step f) before the reaction is concluded in an adjacently applied and/or mutually adjoining homogeneous volume element from which the reactivity has been transmitted to the homogenous volume composite.

17. The inkjet method as claimed in claim 16, wherein the reactivity is transmitted without reactivation.

18. The inkjet method as claimed in claim 16, wherein the reaction in the volume composite has not yet commenced.

19. The inkjet method as claimed in claim 16, wherein the reaction commences as a result of activation by means of actinic radiation or by means of thermal energy.

20. The inkjet method as claimed in claim 16, wherein the at least two adjacently applied and/or mutually adjoining volume elements are transformed to the volume composite: a) laterally between volume elements adjacently applied and/or mutually adjoining in an x and/or y direction and the volume composite formed in the x and/or y direction is extended by volume elements applied in a z direction, or b) in the z direction between volume elements adjacently applied and/or mutually adjoining and the volume composite formed in the z direction is extended by volume elements applied in the x and/or y direction, or c) independently of the x and/or y direction and independently of the z direction.

21. The inkjet method as claimed in claim 16, wherein extending a volume composite V present in an x and/or y direction or a homogeneous volume composite Vh present in the x and/or y direction comprises: a) integration of volume elements applied in a z direction into the volume composite V present in the x and/or y direction or into the homogeneous volume composite Vh present in the x and/or y direction, or b) lateral transformation in the x and/or y direction of volume elements applied in the z direction to the volume composite V already present in the x and/or y direction or to the homogeneous volume composite Vh already present in the x and/or y direction to a further volume composite V1 or to a further homogeneous volume composite Vh1 and subsequent integration of the further volume composite V1 or the further homogeneous volume composite Vh1 into the volume composite V already present in the x and/or y direction or into the homogeneous volume composite Vh already present in the x and/or y direction, respectively, or c) integration of the volume elements applied in the z direction into the volume composite V present in the x and/or y direction or into the volume composite Vh present in the x and/or y direction and simultaneous transformation of the volume elements applied in the z direction to the further volume composite V1 or to the further homogeneous volume composite Vh1, respectively, or wherein the extending the volume composite V present in the z direction or of the homogeneous volume composite Vh present in the z direction comprises: d) integration of volume elements applied in the x and/or y direction into the volume composite V present in the z direction or into the homogeneous volume composite Vh present in the z direction, or e) transformation in the z direction of volume elements applied in the x and/or y direction to the volume composite V already present in the z direction or to the homogeneous volume composite Vh already present in the z direction to the further volume composite V1 or to the further homogeneous volume composite Vh1 and subsequent integration of the further volume composite V1 or the further homogeneous volume composite Vh1 into the volume composite V already present in the z direction or into the homogeneous volume composite Vh already present in the z direction, respectively, or f) integration of volume elements applied in the x and/or y direction into the volume composite V already present in the z direction or the volume composite Vh already present in the z direction and simultaneous conversion of the volume elements applied in the x and/or y direction to the volume composite V1 or to the homogeneous volume composite Vh1.

22. The inkjet method as claimed in claim 16, wherein the volume composite results from the coalescing, bonding, wetting, and/or contacting of at least two mutually adjoining and/or adjacently applied volume composites or from the coalescing, bonding, wetting, and/or contacting of at least one volume element and at least one adjoining and/or adjacently applied volume composite.

23. The inkjet method as claimed in claim 16, wherein the homogeneous volume composite is formed when the reaction: a) within a respective volume element and between adjacently applied and/or mutually adjoining volume elements, or b) within a respective volume composite and the reaction between the respective volume composite and at least one volume element, and the reaction within the at least one volume element, or c) within adjacently applied and/or mutually adjoining volume composites and between the adjacently applied and/or mutually adjoining volume composites, has not fully concluded.

24. The inkjet method as claimed in claim 16, wherein the final volume composite is formed when the reaction: a) within a volume element is at first not fully concluded, the reaction between adjacently applied and/or mutually adjoining volume elements is not fully concluded and the reactivity is transmitted between the adjacently applied and/or mutually adjoining volume elements, or b) within the homogeneous volume composite is at first not fully concluded, the reaction between adjacently applied and/or mutually adjoining homogeneous volume composites is at first not fully concluded and the reactivity is transmitted between the adjacently applied and/or mutually adjoining homogeneous volume composites, or c) within the homogeneous volume composite is at first not fully concluded, the reaction between the homogeneous volume composite and at least one adjacently applied and/or adjoining volume composite is at first not fully concluded, the reactivity is transmitted between the homogeneous volume composite and the at least one adjacently applied and/or adjoining volume composite, or d) within the volume element is at first not fully concluded, the reaction between the volume element and an adjacently applied and/or adjoining volume composite is at first not fully concluded, and the reactivity is transmitted from the volume element to the adjacently applied and/or adjoining volume composite, or e) within the homogeneous volume composite is at first not fully concluded, the reaction between the homogeneous volume composite and at least one adjacently applied and/or adjoining volume element is at first not fully concluded, and the reactivity is transmitted from the homogeneous volume composite to the at least one adjacently applied and/or adjoining volume element, or f) within the homogeneous volume composite and within at least one adjacently applied and/or adjoining volume element is at first not fully concluded, the reaction between the homogeneous volume composite and the at least one adjacently applied and/or adjoining volume element is at first not fully concluded, and the reactivity is transmitted between the homogeneous volume composite and the at least one adjacently applied and/or adjoining volume element, and the reaction is concluded after transmission of the reactivity.

25. The method as claimed in claim 16, wherein the reactivity is transmitted: a) in an x and/or y direction and/or in a z direction, or b) independently of the x and/or y direction and independently of the z direction.

26. The method as claimed in claim 16, wherein the substrate, after formation of the final volume, remains bonded to the final volume composite or is separated from the final volume composite.

27. The method as claimed in claim 16, wherein the at least one fluid contains the hybrid system.

28. The method as claimed in claim 27, wherein the hybrid system is selected from the group consisting of a thiol-ene-(meth)acrylate hybrid system, an epoxythiol-(meth)acrylate hybrid system, an epoxy-(meth)acrylate hybrid system, an epoxythiol-thiol/ene hybrid system containing at least one photolatent base, and an epoxythiol-(meth)acrylate hybrid system containing at least one photolatent base.

29. The method as claimed in claim 16, wherein the at least one fluid contains the thiol-ene system.

Description

DESCRIPTION OF EXEMPLARY EMBODIMENTS

(1) I Fluid to be Used in Accordance with the Disclosure Based on Hybrid Systems

(2) A hybrid system in the context of the present disclosure is understood to mean a composition in which at least two chemical subsystems with different curing reactions are used. These subsystems may either react as independent systems independently with polymerization or else may react partly with one another, in that, for example, individual components may occur as co-reactants in both curing reactions. The curing reactions involved may proceed identically or very similarly or differ, for example, in the curing mechanism, curing rate or degree of crosslinking.

(3) I.1 Fluid to be Used in Accordance with the Disclosure Based on Thiol-Ene-(Meth)Acrylate Hybrid Systems

(4) Thiol-ene-(meth)acrylate hybrid systems are a combination of at least one thiol-ene system and at least one (meth)acrylate system. The at least one (meth)acrylate system is typically UV- or radiation-curable. The at least one thiol-ene system comprises at least one thiol monomer and at least one ene monomer. The at least one thiol monomer and the at least one ene monomer are present here typically in a stoichiometric ratio or with a slight excess of ene monomer, typically in a stoichiometric ratio of at least one thiol monomer to at least one ene monomer from a range from 1:1.001 to 1:1.10, further typically from a range from 1:1.01 to 1:1.05. A slight excess of ene monomer avoids any residual content of thiol groups in the cured fluid. The at least one thiol monomer used is typically an at least difunctional thiol monomer. The at least one thiol monomer used is typically at least one difunctional mercapto ester and/or at least one difunctional mercapto thioether. The ene monomer used is typically a monofunctional ene monomer or an at least difunctional ene monomer. The at least one ene monomer used is typically at least one monofunctional or difunctional vinyl compound, more typically at least one monofunctional or difunctional vinyl ether and/or at least one monofunctional or difunctional allyl compound.

(5) The at least one (meth)acrylate system comprises at least one (meth)acrylate monomer and/or at least one thio(meth)acrylate monomer. The at least one (meth)acrylate monomer present in the at least one (meth)acrylate system may be at least one monofunctional (meth)acrylate monomer, at least one difunctional (meth)acrylate monomer, at least one trifunctional (meth)acrylate monomer, at least one tetrafunctional (meth)acrylate monomer, at least one pentafunctional (meth)acrylate monomer and/or at least one hexafunctional (meth)acrylate monomer. Typically, the at least one (meth)acrylate system comprises at least one difunctional (meth)acrylate monomer, at least one trifunctional (meth)acrylate monomer, at least one tetrafunctional (meth)acrylate monomer, at least one pentafunctional (meth)acrylate monomer and/or at least one hexafunctional (meth)acrylate monomer. If the at least one (meth)acrylate monomer comprises at least two functional groups, this facilitates the formation of a crosslinked polymer network. The at least one thio(meth)acrylate monomer present in the at least one (meth)acrylate system may be at least one monofunctional thio(meth)acrylate monomer, at least one difunctional thio(meth)acrylate monomer, at least one trifunctional thio(meth)acrylate monomer, at least one tetrafunctional thio(meth)acrylate monomer, at least one pentafunctional thio(meth)acrylate monomer and/or at least one hexafunctional thio(meth)acrylate monomer. Typically, the at least one (meth)acrylate system comprises at least one difunctional thio(meth)acrylate monomer, at least one trifunctional thio(meth)acrylate monomer, at least one tetrafunctional thio(meth)acrylate monomer, at least one pentafunctional thio(meth)acrylate monomer and/or at least one hexafunctional thio(meth)acrylate monomer. If the at least one thio(meth)acrylate monomer comprises at least two functional groups, this also facilitates the formation of a densely crosslinked polymer network.

(6) If the thiol-ene-(meth)acrylate hybrid system comprises at least two different thiol monomers, these may be present in any desired weight ratio to one another. If the thiol-ene-(meth)acrylate hybrid system comprises at least two different ene monomers, these may be present in any desired weight ratio to one another. If the thiol-ene-(meth)acrylate hybrid system comprises at least two different (meth)acrylate monomers, these may be present in any desired weight ratio to one another.

(7) Thiol monomers used in the thiol-ene-(meth)acrylate hybrid system may, for example, be glycol di (3-mercaptopropionate), trimethylolpropane tri (3-mercaptopropionate), pentaerythritol tetra(3-mercaptopropionate), glycol dimercaptoacetate, trimethylolpropane trimercaptoacetate, pentaerythritol tetramercaptoacetate, dimercaptodiethyl sulfide, bis(2-mercaptoethyl) ether, 4-mercaptomethyl-3,6-dithiaoctane-1,8-dithiol or mixtures thereof.

(8) Ene monomers used in the thiol-ene-(meth)acrylate hybrid system may, for example, be vinyl compounds such as butane-1,4-diol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, cyclohexane-1,4-dimethanol divinyl ether, 1,2,4-trivinylcyclohexane, divinylbenzene or mixtures thereof.

(9) Ene monomers used in the thiol-ene-(meth)acrylate hybrid system may, for example, be allyl compounds such as triallyl-s-triazinetrione, diallyl ether, allyl methacrylate, diallyl sulfide, diallyl disulfide, triallylamine, diallyltrifluoroacetamide or mixtures thereof.

(10) (Meth)acrylate monomers used in the thiol-ene-(meth)acrylate hybrid system may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, butane-1,3-diol di(meth)acrylate, butane-1,4-diol di(meth)acrylate, hexane-1,6-diol di(meth)acrylate, nonane-1,9-diol di(meth)acrylate, 3-methylpentane-1,5-diol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol-[9EO] di(meth)acrylate, polyethylene glycol-200 di(meth)acrylate, polyethylene glycol-400 di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane-[3EO] triacrylate, trimethylolpropane-[3PO] tri(meth)acrylate, pentaerythritol-[5EO] tetra(meth)acrylate, tris-[2-((meth)acryloyloxy)ethyl] isocyanurate, bis(ethylthio(meth)acrylate) sulfide, 2-(perfluorobutyl)ethyl (meth)acrylate or mixtures thereof. Thio(meth)acrylates used in the thiol-ene-(meth)acrylate hybrid system may, for example, be (meth)acryloylthioethane, glycidyl thio(meth)acrylate, 1,2-bis[(meth)acryloylthio]ethane, 1,3-bis[(meth)acryloylthio]propane, 1,2-bis[2-(meth)acryloyl-thioethylthio]-3-[(meth)acryloylthio]propane, 1,4-bis[(meth)acryloylthio]butane, bis[(2-(meth)acryloylthioethyl] ether, 1,4-bis(acryloylthiomethyl)benzene, 1,4-bis[(meth)acryloyl-thiomethyl]benzene, 1,4-bis[2-(meth)acryloylthioethylthiomethyl]benzene, bis[(2-(meth)acryloylthioethyl)] sulfide, bis(4-acryloylthiophenyl) sulfide, bis(4-methacryloyl-thiophenyl) sulfide or mixtures thereof.

(11) The thiol-ene-(meth)acrylate hybrid system comprises the at least one thiol-ene system in a proportion from a range from typically 10% by weight to 70% by weight, further typically 11% by weight to 60% by weight, further typically 12% by weight to 53% by weight, especially typically 13% by weight to 46% by weight and most typically 14% by weight to 33% by weight, based in each case on the total weight of the thiol-ene-(meth)acrylate hybrid system. If the proportion of the thiol-ene system is <10% by weight or >70% by weight, based in each case on the total weight of the thiol-ene-(meth)acrylate hybrid system, there will be insufficient reaction of the thiol-ene system with the (meth)acrylate system, and no formation of a sufficiently stable thiol-ene-(meth)acrylate hybrid system.

(12) The curing of the thiol-ene-(meth)acrylate hybrid system is typically effected by UV-induced polyaddition. The thiol-ene-(meth)acrylate hybrid system, by contrast with commercially available print fluids based on UV-curing (meth)acrylate monomers, can be polymerized under air without unwanted inhibition effects by (atmospheric) oxygen at the interface of a volume element and/or of a volume composite and/or of a homogeneous volume composite with air in each case. This is extremely advantageous since there is no need to provide an inert gas atmosphere. By contrast, the use of UV-curing (meth)acrylate monomers in print fluids under inert conditions has the disadvantage that the reaction thereof proceeds very quickly. During the printing process, a print fluid comprising UV-curing (meth)acrylate monomers may show unwanted incomplete curing at the interface with air as a result of oxygen inhibition of the free-radical reaction, as a result of which a subsequently applied volume element is incapable of binding fully and, in the worst case, includes an incompletely cured layer in the volume of an object to be produced. It is possible to avoid oxygen inhibition of the free-radical reaction by laborious purging with inert gas, but this distinctly increases the reaction rate and hence makes it difficult to control the process. An increase in the reaction rate may in turn lead to faster curing of the individually applied volume elements, which in turn promotes the formation of interfaces in the volume of an object. In each case, the UV curing results in an altered surface layer and also in unwanted gradients and/or inhomogeneities in the volume of an object, since the curing reaction proceeds from the surface, from the top and/or from the bottom. Both the crosslinking density and the refractive index vary locally, both of which are unwanted. In addition, objects that have been formed from a print fluid comprising (meth)acrylate monomers frequently have a very low softening point of T.sub.g<60° C. and a refractive index of about n.sub.e=1.49 to 1.56. Refractive indices of at least 1.56 can be achieved, for example, when aromatic (meth)acrylate monomers are used, but in that case only in association with a low Abbe number, or using at least one sulfur-containing (meth)acrylate, thio(meth)acrylate and/or mercapto thioether.

(13) A fluid to be used in accordance with the disclosure based on a thiol-ene-(meth)acrylate hybrid system enables the production of spectacle lenses having a refractive index n.sub.e of 1.49 to 1.65.

(14) Thiol-ene polymers can have a positive influence on the mechanical properties of (meth)acrylate polymers in a thiol-ene-(meth)acrylate hybrid system, in that the brittle network of the (meth)acrylate polymers becomes more flexible by virtue of the thiol-ene polymers.

(15) Printing inks comprising UV-curing (meth)acrylate monomers, on account of the low viscosity thereof of below 50 mPas (25° C.), usually have good printability by means of inkjet methods.

(16) The fluid to be used in accordance with the disclosure based on a thiol-ene-(meth)acrylate hybrid system typically has a viscosity at the printing temperature of less than 50 mPas, further typically from a range from 5 mPas to 20 mPas, more typically from a range from 7 mPas to 12 mPas and most typically from a range from 8 mPas to 9 mPas. A viscosity from aforementioned ranges is a compromise between very good processability of the thiol-ene-(meth)acrylate hybrid system by means of different printheads or multinozzle arrays and the immobilization of a volume element. The lower the viscosity of the fluid based on a thiol-ene-(meth)acrylate hybrid system is to be within the aforementioned ranges, the greater the preference with which the thiol-ene system comprises at least one low-viscosity vinyl ether.

(17) In thiol-ene-(meth)acrylate hybrid systems, in the course of UV curing, the polyaddition of the thiol-ene component proceeds predominantly in parallel with the polymerization of the (meth)acrylate system. The properties of the resultant copolymer are a combination of poly(meth)acrylate and thiol-ene polymer.

(18) The thiol-ene-(meth)acrylate hybrid system is typically cured by UV polymerization at wavelengths below 420 nm, typically with LED sources. Examples of suitable UV initiators include hydroxyphenyl ketones, α-keto esters, phenylphosphine oxides and/or thioxanthones.

(19) In addition to UV polymerization, thermal post-curing may be advisable if the level of polymerization after the UV irradiation is insufficient. Examples of suitable thermal coinitiators include dialkyl peroxides (e.g., di-tert-amyl peroxides), peroxycarbonates (e.g., tert-butylperoxy-2-ethylhexyl carbonate), hydroperoxides (e.g., cumene hydroperoxide), peroxy esters (e.g., tert-butyl peroxybenzoate). The SADT (self-accelerating decomposition temperature) of the thermal coinitiators should be >60° C. or well above the printing temperature.

(20) The increase in processing time of the thiol-ene-(meth)acrylate hybrid system can be achieved by addition of sterically hindered phenols, for example 2,6-di-tert-butyl-4-methylphenol (BHT), in amounts of 0.1% by weight to 5% by weight, based on the total weight of the thiol-ene-(meth)acrylate hybrid system.

(21) Addition of UV absorbers of the hydroxyphenyl benzotriazole type results in an absorption edge in the thiol-ene-(meth)acrylate hybrid system within a range from 350 nm to 400 nm, depending on the chemical structure of the UV absorber and the concentration thereof in the respective thiol-ene-(meth)acrylate hybrid system.

(22) The advantage of a thiol-ene-(meth)acrylate hybrid system over a (meth)acrylate system is that it is possible here to transmit the reactivity via different polymerization mechanisms partly or fully between volume elements. It is likewise possible to control the mechanical and thermal properties of the polymer formed to a greater degree than in a (meth)acrylate system.

(23) I.2. Fluid to be Used in Accordance with the Disclosure Based on Epoxythiol-(Meth)Acrylate Hybrid Systems

(24) Epoxythiol-(meth)acrylate hybrid systems are a combination of at least one epoxythiol system and at least one (meth)acrylate system. The at least one (meth)acrylate system is typically UV-polymerizable. The at least one epoxythiol system comprises at least one epoxy monomer and at least one thiol monomer. The at least one epoxy monomer used is typically an at least difunctional epoxy monomer. The at least one thiol monomer used is typically an at least difunctional thiol monomer. The at least one epoxy monomer used is typically at least one diglycidyl ether. The at least one thiol monomer used is typically at least one difunctional mercapto ester and/or at least one difunctional mercapto thioether.

(25) The at least one (meth)acrylate system comprises at least one (meth)acrylate monomer and/or at least one thio(meth)acrylate monomer. The at least one (meth)acrylate monomer present in the at least one (meth)acrylate system may be at least one monofunctional (meth)acrylate monomer, at least one difunctional (meth)acrylate monomer, at least one trifunctional (meth)acrylate monomer, at least one tetrafunctional (meth)acrylate monomer, at least one pentafunctional (meth)acrylate monomer and/or at least one hexafunctional (meth)acrylate monomer. Typically, the at least one (meth)acrylate system comprises at least one difunctional (meth)acrylate monomer, at least one trifunctional (meth)acrylate monomer, at least one tetrafunctional (meth)acrylate monomer, at least one pentafunctional (meth)acrylate monomer and/or at least one hexafunctional (meth)acrylate monomer. If the at least one (meth)acrylate monomer comprises at least two functional groups in each case, this facilitates the formation of a densely crosslinked polymer network. The at least one thio(meth)acrylate monomer present in the at least one (meth)acrylate system may be at least one monofunctional thio(meth)acrylate monomer, at least one difunctional thio(meth)acrylate monomer, at least one trifunctional thio(meth)acrylate monomer, at least one tetrafunctional thio(meth)acrylate monomer, at least one pentafunctional thio(meth)acrylate monomer and/or at least one hexafunctional thio(meth)acrylate monomer. Typically, the at least one (meth)acrylate system comprises at least one difunctional thio(meth)acrylate monomer, at least one trifunctional thio(meth)acrylate monomer, at least one tetrafunctional thio(meth)acrylate monomer, at least one pentafunctional thio(meth)acrylate monomer and/or at least one hexafunctional thio(meth)acrylate monomer. If the at least one thio(meth)acrylate monomer comprises at least two functional groups, this also facilitates the formation of a densely crosslinked polymer network.

(26) If the epoxythiol-(meth)acrylate hybrid system comprises at least two different epoxy monomers, these may be present in any desired weight ratio to one another.

(27) If the epoxythiol-(meth)acrylate hybrid system comprises at least two different thiol monomers, these may be present in any desired weight ratio to one another. If the epoxythiol-(meth)acrylate hybrid system comprises at least two different (meth)acrylate monomers, these may be present in any desired weight ratio to one another. In the epoxythiol system, the ratio of the at least one epoxy monomer to the at least one thiol monomer is typically stoichiometric.

(28) In the epoxythiol-(meth)acrylate hybrid system, the proportion of the epoxythiol system is typically within a range from 15% by weight to 85% by weight, further typically within a range from 20% by weight to 80% by weight, more typically within a range from 25% by weight to 60% by weight and most typically within a range from 30% by weight to 50% by weight, based in each case on the total weight of the epoxythiol-(meth)acrylate hybrid system.

(29) In the epoxythiol-(meth)acrylate hybrid system, the proportion of the (meth)acrylate system is typically within a range from 5% by weight to 65% by weight, further typically within a range from 10% by weight to 60% by weight, more typically within a range from 15% by weight to 50% by weight and most typically within a range from 20% by weight to 40% by weight, based in each case on the total weight of the epoxythiol-(meth)acrylate hybrid system.

(30) The at least one epoxy monomer used in the epoxythiol-(meth)acrylate hybrid system may, for example, be ethyl glycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C8-C10 glycidyl ether (CAS No. 68609-96-1), C12-C14 glycidyl ether (CAS No. 68609-97-2), cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, nonylphenyl glycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether, bisphenol A (2,3-dihydroxypropyl) glycidyl ether, diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, butane-1,4-diol diglycidyl ether, cyclohexane-1,4-dimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol(400) diglycidyl ether, hexane-1,6-diol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol A propoxylate diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, resorcinol diglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, triphenylolmethane triglycidyl ether, tris(2,3-epoxypropyl) isocyanurate, tris(4-hydroxyphenyl)methane triglycidyl ether, 1,1,1-tris(4-hydroxyphenyl)ethane triglycidyl ether, glycerol triglycidyl ether, glycerol propoxylate triglycidyl ether, N,N-diglycidyl-4-glycidyloxyaniline, pentaerythritol tetraglycidyl ether, dipentaerythritol tetraglycidyl ether, tetraglycidylbenzylethane, sorbitol tetraglycidyl ether, tetraglycidyldiaminophenylmethane, tetraglycidylbisaminomethylcyclohexane.

(31) In the epoxythiol-(meth)acrylate hybrid system, the at least one thiol monomer used may be at least one of the thiol monomers listed in “I.1 Fluid to be used in accordance with the disclosure based on thiol-ene-(meth)acrylate hybrid systems,” “I.1 Thiol-ene-(meth)acrylate hybrid system” hereinafter.

(32) In the epoxythiol-(meth)acrylate hybrid system, the at least one (meth)acrylate monomer or the at least one thio(meth)acrylate monomer used may be at least one of the (meth)acrylate monomers or thio(meth)acrylate monomers listed in section “I.1 Thiol-ene-(meth)acrylate hybrid system.”

(33) The advantage of an epoxythiol-(meth)acrylate hybrid system over a (meth)acrylate system is that it is possible here to transmit the reactivity via different polymerization mechanisms partly or fully between volume elements. It is likewise possible to control the mechanical and thermal properties of the polymer formed to a greater degree than in a (meth)acrylate system.

(34) I.3 Fluid to be Used in Accordance with the Disclosure Based on Epoxy-(Meth)Acrylate Hybrid Systems

(35) Epoxy-(meth)acrylate hybrid systems are a combination of at least one epoxy system and at least one (meth)acrylate system. The at least one (meth)acrylate system is typically UV-polymerizable. The at least one epoxy system comprises at least one epoxy monomer. The at least one epoxy monomer used is typically an at least difunctional epoxy monomer. The at least one epoxy system typically further comprises an at least difunctional polyol or an at least difunctional amine, more typically an at least difunctional polyol.

(36) The at least one (meth)acrylate system comprises at least one (meth)acrylate monomer and/or one thio(meth)acrylate monomer. The at least one (meth)acrylate monomer present in the at least one (meth)acrylate system may be at least one monofunctional (meth)acrylate monomer, at least one difunctional (meth)acrylate monomer, at least one trifunctional (meth)acrylate monomer, at least one tetrafunctional (meth)acrylate monomer, at least one pentafunctional (meth)acrylate monomer and/or at least one hexafunctional (meth)acrylate monomer. Typically, the at least one (meth)acrylate system comprises at least one difunctional (meth)acrylate monomer, at least one trifunctional (meth)acrylate monomer, at least one tetrafunctional (meth)acrylate monomer, at least one pentafunctional (meth)acrylate monomer and/or at least one hexafunctional (meth)acrylate monomer. If the at least one (meth)acrylate monomer comprises at least two functional groups, this facilitates the formation of a densely crosslinked polymer network. The at least one thio(meth)acrylate monomer present in the at least one (meth)acrylate system may be at least one monofunctional thio(meth)acrylate monomer, at least one difunctional thio(meth)acrylate monomer, at least one trifunctional thio(meth)acrylate monomer, at least one tetrafunctional thio(meth)acrylate monomer, at least one pentafunctional thio(meth)acrylate monomer and/or at least one hexafunctional thio(meth)acrylate monomer. Typically, the at least one (meth)acrylate system comprises at least one difunctional thio(meth)acrylate monomer, at least one trifunctional thio(meth)acrylate monomer, at least one tetrafunctional thio(meth)acrylate monomer, at least one pentafunctional thio(meth)acrylate monomer and/or at least one hexafunctional thio(meth)acrylate monomer. If the at least one thio(meth)acrylate monomer comprises at least two functional groups, this also facilitates the formation of a densely crosslinked polymer network.

(37) If the epoxy-(meth)acrylate hybrid system comprises at least two different epoxy monomers, these may be present in any desired weight ratio to one another. If the epoxy-(meth)acrylate hybrid system comprises at least two different (meth)acrylate monomers, these may be present in any desired weight ratio to one another.

(38) If the epoxy system, as well as at least one epoxy monomer, comprises at least one polyol, the molar ratio of the at least one epoxy monomer to the at least one polyol is typically within a range from 1.2:1 to 10:1.

(39) If the epoxy system, as well as at least one epoxy monomer, comprises at least one polyol, the proportion of the at least one epoxy monomer is typically within a range from 65% by weight to 99% by weight, further typically within a range from 70% by weight to 98% by weight, more typically within a range from 75% by weight to 94% by weight and most typically within a range from 80% by weight to 92% by weight, based in each case on the total weight of the epoxy system. The proportion of the at least one polyol is typically within a range from 1% by weight to 35% by weight, further typically within a range from 2% by weight to 30% by weight, more typically within a range from 6% by weight to 25% by weight and most typically within a range from 8% by weight to 20% by weight, based in each case on the total weight of the epoxy system.

(40) In the epoxy-(meth)acrylate hybrid system, the proportion of the epoxy system is typically within a range from 15% by weight to 85% by weight, further typically within a range from 20% by weight to 80% by weight, more typically within a range from 30% by weight to 50% by weight and most typically within a range from 40% by weight to 60% by weight, based in each case on the total weight of the epoxy-(meth)acrylate hybrid system.

(41) In the epoxy-(meth)acrylate hybrid system, the proportion of the (meth)acrylate system is typically within a range from 15% by weight to 85% by weight, further typically within a range from 20% by weight to 80% by weight, more typically within a range from 30% by weight to 50% by weight and most typically within a range from 40% by weight to 60% by weight, based in each case on the total weight of the epoxy-(meth)acrylate hybrid system.

(42) The at least one epoxy monomer present in the epoxy-(meth)acrylate system may, for example, be at least one of the epoxy monomers listed in section “I.2. Fluid to be used in accordance with the disclosure based on epoxythiol-(meth)acrylate hybrid systems,” “I.2 Epoxythiol-(meth)acrylate hybrid system” hereinafter.

(43) The at least one (meth)acrylate monomer present in the epoxy-(meth)acrylate system may, for example, be at least one of the (meth)acrylate monomers and/or thio(meth)acrylate monomers listed in section “I.1 Thiol-ene-(meth)acrylate hybrid system.”

(44) The at least one polyol present in the epoxy-(meth)acrylate system may be at least one di-, tri-, tetra-, penta- or hexafunctional polyol or an oligomeric polyol. Aliphatic polyols used may, for example, be ethylene glycol, cyclohexanedimethanol, triethylene glycol, 1,2-propylene glycol, 1,4-butylglycol, pentane-1,5-diol, propane-1,2,3-triol, hexane-1,2,6-triol, pentaerythritol, 2,2-bis(4-hydroxycyclohexyl)propane. An oligomeric polyol may come, for example, from the group of the polyester polyols or polyether polyols.

(45) The advantage of an epoxy-(meth)acrylate hybrid system over a (meth)acrylate system is that it is possible here to transmit the reactivity via different polymerization mechanisms partly or fully between volume elements. It is likewise possible to control the mechanical and thermal properties of the polymer formed to a greater degree than in a (meth)acrylate system.

(46) II Fluid to be Used in Accordance with the Disclosure Based on Systems Comprising at Least One Photolatent Catalyst

(47) The controlled activation of the respective reaction within at least one volume element, within at least one volume composite, within at least one homogeneous volume composite, between adjacently applied and/or mutually adjoining volume elements and/or between adjacently applied and/or mutually adjoining volume composites and/or between adjacently applied and/or mutually adjoining homogeneous volume composites is typically achieved by means of at least one photolatent catalyst. The principle of action of a photolatent catalyst is based on the controlled release of the active catalyst by exposure of an inactive or distinctly less active precursor of the catalyst in the UV and/or VIS region. The controlled release of the at least one active catalyst offers the advantage that a reaction catalyzable by this at least one active catalyst commences only at the desired juncture. This in turn has the effect that the processing time of a material comprising the inactive or distinctly less active precursor of the at least one catalyst is distinctly increased. The differences in catalyst strength of a photolatent base, for example, may be up to 4 orders of magnitude. Typically, the processing time of a material comprising the inactive or distinctly less active precursor of the at least one catalyst is ≥10 minutes, more typically ≥1 hour, and most typically more than 1 day. In addition, a material comprising the inactive or distinctly less active precursor of the at least one catalyst may comprise at least one photosensitizer in addition to the catalyst precursor. A fluid comprising at least one photolatent catalyst may also exhibit dark curing or shadow curing in regions that have not been directly exposed.

(48) At least one photolatent catalyst used may be at least one photolatent base (PLB) and/or at least one photolatent acid. The at least one photolatent catalyst used is typically at least one photolatent base.

(49) The at least one photolatent acid used is typically at least one diaryliodonium salt (Ar.sub.2I.sup.+) or at least one triarylsulfonium salt (Ar.sub.3S.sup.+).

(50) The fluid to be used in accordance with the disclosure comprises the at least one photolatent acid in a total proportion typically from a range from 0.001% by weight to 2% by weight, more typically from a range from 0.1% by weight to 1.0% by weight and especially typically from a range from 0.2% by weight to 0.5% by weight, based in each case on the total weight of the fluid to be used in accordance with the disclosure. Aforementioned ranges are applicable both to the use of a single type of photolatent acid and to mixtures of different photolatent acids.

(51) The at least one photolatent base used is typically at least one of the photolatent base compounds according to WO 03/033500 A1 or according to WO 2008/119688 A1. Further typically, the at least one photolatent base used is at least one of the photolatent base compounds according to WO 03/033500 A1, claim 1, or according to WO 2008/119688 A1, claim 1. More typically, the at least one photolatent base used is at least one photolatent base according to WO 03/033500 A1, claim 1, or according to WO 03/033500 A1, example 1, 5-benzyl-1,5-diazabicyclo[4.3.0]nonane.

(52) The fluid to be used in accordance with the disclosure comprises the at least one photolatent base in a total proportion typically from a range from 0.001% by weight to 5.0% by weight, more typically from a range from 0.1% by weight to 2.0% by weight and especially typically from a range from 0.2% by weight to 1% by weight, based in each case on the total weight of the fluid to be used in accordance with the disclosure. Fluids comprising at least one photolatent base have particularly favorable polymer formation, since the respective curing mechanisms are effective both in the case of shadow curing and in the case of exposure, and hence the same polymer structure is formed. Aforementioned ranges are applicable both to the use of a single type of photolatent base and to mixtures of different photolatent bases.

(53) II.1 Fluid to be Used in Accordance with the Disclosure Based on an Epoxy-Polyol System Comprising at Least One Photolatent Acid

(54) Photolatent acids are used, for example, in formulations comprising at least one epoxy monomer. Typical representatives of a photolatent acid are, for example, diaryliodonium salts (Ar.sub.2I.sup.+) or the thermally very stable triarylsulfonium salts (Ar.sub.3S.sup.+). Formulations comprising photolatent acids generally do not show any oxygen inhibition and generally have dark curing or shadow curing in regions that have not been exposed. One example of a formulation comprising at least one epoxy monomer is the formulation that follows, which can be cationically cured after exposure with release of the triarylsulfonium salt:

(55) ##STR00001##

(56) The reaction rate of the uncatalyzed reaction between the polyol and the epoxy monomer is so slow that no significant dark reaction or shadow reaction proceeds. The curing reaction may be influenced, for example, by the concentration of the triarylsulfonium salt, by the choice of exposure wavelength, the intensity of the radiation source and the exposure time, and also the temperature.

(57) The epoxy-polyol system comprises the at least one photolatent acid in a total proportion typically from a range from 0.001% by weight to 2% by weight, more typically from a range from 0.1% by weight to 1.0% by weight and especially typically from a range from 0.2% by weight to 0.5% by weight, based in each case on the total weight of the epoxy-polyol system. Aforementioned ranges are applicable both to the use of a single type of photolatent acid and to mixtures of different photolatent acids.

(58) II.2 Fluid to be Used in Accordance with the Disclosure Based on an Epoxythiol System Comprising at Least One Photolatent Base

(59) ##STR00002##

(60) The epoxythiol system comprises at least one epoxy monomer and at least one thiol monomer and/or a thiol oligomer. Typically, the epoxythiol system comprises an at least difunctional epoxy monomer as at least one epoxy monomer. Typically, the epoxythiol system comprises an at least difunctional thiol monomer as at least one thiol monomer.

(61) The epoxythiol system may comprise, for example, at least one of the epoxy monomers listed in section “I.2 Epoxythiol-(meth)acrylate hybrid system.”

(62) The epoxythiol system may comprise, for example, at least one of the thiol monomers listed in section “I.1 Thiol-ene-(meth)acrylate hybrid system.”

(63) The at least one epoxy monomer and the at least one thiol monomer are typically present stoichiometrically in the epoxythiol system relative to one another.

(64) The at least one photolatent base used is typically at least one of the photolatent base compounds according to WO 03/033500 A1, claim 1, or according to WO 2008/119688 A1, claim 1. More typically, the at least one photolatent base used is at least one photolatent base according to WO 03/033500 A1, claim 1, or according to WO 03/033500 A1, example 1, 5-benzyl-1,5-diazabicyclo[4.3.0]nonane.

(65) The epoxythiol system comprises the at least one photolatent base in a total proportion typically from a range from 0.001% by weight to 5.0% by weight, further typically from a range from 0.1% by weight to 2.0% by weight and especially typically from a range from 0.2% by weight to 1% by weight, based in each case on the total weight of the epoxythiol system. Aforementioned ranges are applicable both to the use of a single type of photolatent base and to mixtures of different photolatent bases.

(66) The epoxy-thiol system is typically mixed directly prior to printing. As soon as the epoxy-thiol system is exposed, the polymerization reaction is accelerated very significantly. However, the reaction rates are much lower compared to the (meth)acrylate systems, and so it is readily possible for adjacent volume elements to form a homogeneous volume composite. In particular, the simultaneous production of the base in the volume results in more homogeneous crosslinking. As a result of insensitivity toward oxygen, there is also no marked surface layer. By virtue of the specific form of the photolatent base, curing is additionally possible even without exposure or under inhomogeneous radiation distribution, i.e., shadow curing is also possible; the same polymer is formed throughout.

(67) The use of at least one thiol monomer results in a high refractive index, with both adjustability of the refractive index and variability of the dispersion (n.sub.e (23° C.)=1.52 to 1.65). In addition, the reactivity may be influenced by the concentration of the photolatent base, by the choice of exposure wavelength, the intensity of the radiation source and the exposure time, and also the temperature.

(68) III Fluid to be Used in Accordance with the Disclosure Based on Hybrid Systems Comprising at Least One Photolatent Catalyst

(69) III.1 Fluid to be Used in Accordance with the Disclosure Based on Epoxythiol-Thiol/Ene Hybrid Systems Comprising at Least One Photolatent Base

(70) The epoxythiol-thiol/ene hybrid system comprises a combination of at least one epoxythiol system and at least one thiol/ene system. Production of the epoxythiol system requires at least one epoxy monomer and at least one thiol monomer. The at least one epoxy monomer here typically comprises an at least difunctional epoxy monomer. Further typically, the at least one thiol monomer usable in the epoxythiol system comprises an at least difunctional thiol monomer. Production of the thiol/ene system requires at least one thiol monomer and at least one ene monomer. Typically, the at least one thiol monomer usable for production of the thiol/ene system comprises an at least difunctional thiol monomer. Further typically, the at least one ene monomer usable for production of the thiol/ene system comprises an at least difunctional ene monomer. The at least one thiol monomer usable in the epoxythiol system may be the same as or different than the at least one thiol monomer usable in the thiol/ene system. Typically, the at least one thiol monomer usable in the epoxythiol system is the same as the at least one thiol monomer usable in the thiol/ene system.

(71) For production of the epoxythiol-thiol/ene hybrid system, the at least one epoxy monomer used may, for example, be at least one of the epoxy monomers mentioned in section “1.2 Epoxythiol-(meth)acrylate hybrid system.”

(72) For production of the epoxythiol-thiol/ene hybrid system, the at least one thiol monomer used may, for example, be at least one of the thiol monomers mentioned in section “I.1 Thiol-ene-(meth)acrylate hybrid system.”

(73) The ene monomer used for production of the epoxythiol-thiol/ene hybrid system is typically at least one at least monofunctional vinyl compound and/or at least one at least monofunctional allyl compound. For example, the at least one ene monomer used may be at least one of the vinyl compounds and/or allyl compounds mentioned in section “I.1 Thiol-ene-(meth)acrylate hybrid system.”

(74) In the epoxythiol-thiol/ene hybrid system, the epoxythiol system and the thiol/ene hybrid system are typically each in a stoichiometric ratio.

(75) In the epoxythiol-thiol/ene hybrid system, the proportion of the epoxythiol system is typically within a range from 15% by weight to 55% by weight, further typically within a range from 20% by weight to 50% by weight, more typically within a range from 35% by weight to 45% by weight and most typically within a range from 30% by weight to 40% by weight, based in each case on the total weight of the epoxythiol-thiol/ene hybrid system.

(76) In the epoxythiol-thiol/ene hybrid system, the proportion of the thiol/ene system is typically within a range from 2% by weight to 25% by weight, further typically within a range from 3% by weight to 22% by weight, more typically within a range from 5% by weight to 20% by weight and most typically within a range from 8% by weight to 15% by weight, based in each case on the total weight of the epoxythiol-thiol/ene hybrid system.

(77) If the epoxythiol-thiol/ene hybrid system is produced using at least two different epoxy monomers, these may be present in any desired weight ratio to one another. If the epoxythiol-thiol/ene hybrid system is produced using at least two different thiol monomers, these may be present in any desired weight ratio to one another. If the epoxythiol-thiol/ene hybrid system is produced using at least two different ene monomers, these may be present in any desired weight ratio to one another.

(78) The epoxythiol-thiol/ene hybrid system is produced using at least one photolatent base. The photolatent base used is typically at least one of the photolatent base compounds according to WO 03/033500 A1, claim 1, or according to WO 2008/119688 A1, claim 1. More typically, the at least one photolatent base used is at least one photolatent base according to WO 03/033500 A1, claim 1, or according to WO 03/033500 A1, example 1, 5-benzyl-1,5-diazabicyclo[4.3.0]nonane.

(79) The epoxythiol-thiol/ene hybrid system is produced using the at least one photolatent base in a total proportion typically from a range from 0.01% by weight to 5.0% by weight, more typically from a range from 0.1% by weight to 3.0% by weight and most typically from a range from 0.5% by weight to 2.0% by weight, based in each case on the total weight of the epoxythiol-thiol/ene hybrid system. Aforementioned ranges for the total proportion are applicable both to the use of just a single type of photolatent base and to use of at least two different photolatent bases.

(80) The epoxythiol-thiol/ene hybrid system is also typically produced using at least one photoinitiator in a total proportion typically from a range from 0.01% by weight to 2.0% by weight, more typically from a range from 0.1% by weight to 1.5% by weight and especially typically from a range from 0.2% by weight to 1.0% by weight, based in each case on the total weight of the epoxythiol-thiol/ene hybrid system. Aforementioned ranges for the total proportion are applicable both to the use of just a single type of photoinitiator and to use of at least two different photoinitiators. The at least one photoinitiator may, for example, be 2-hydroxy-2-methyl-1-phenylpropan-2-one (Omnicure 1173, IGM Resins B.V.).

(81) The activation is typically effected within a range from 200 nm to 450 nm, further typically from 280 nm to 420 nm, and most typically within a range from 365 nm to 405 nm. Further typically, the activation is effected with a radiation dose typically from a range from 0.1 Fein′ to 20 Fein′, further typically from a range from 0.2 Fein′ to 5 Fein′, more typically from a range from 0.5 Rem′ to 2 Rem′. In the inkjet method, the activation may follow after application of at least two adjacently applied and/or mutually adjoining volume elements, after application of at least one layer of volume elements, after formation of at least one volume composite and/or after formation of at least one homogeneous volume composite. Final activation is typically effected for transformation of a homogeneous volume composite to a final volume composite. The final activation can be effected in a different wavelength range and/or with a different radiation dose. For final activation, a thermal treatment is optionally additionally possible. Optionally, a final volume composite may finally be subjected to thermal treatment.

(82) The advantage of an epoxythiol-thiol/ene hybrid system over a (meth)acrylate system is that it is possible here to transmit the reactivity via different polymerization mechanisms to partly or fully between volume elements. It is likewise possible to control the mechanical and thermal properties of the polymer formed to a greater degree than in a (meth)acrylate system.

(83) III.2 Fluid to be Used in Accordance with the Disclosure Based on Epoxythiol-(Meth)Acrylate Hybrid Systems Comprising at Least One Photolatent Base

(84) Epoxythiol-(meth)acrylate hybrid systems are a combination of at least one epoxythiol system and at least one (meth)acrylate system, as already described in section “1.2 Epoxythiol-(meth)acrylate hybrid system.” In the epoxythiol system, the at least one epoxy monomer is typically used stoichiometrically relative to the at least one thiol monomer. If different epoxy monomers and/or different thiol monomers are used in the epoxythiol system, the different epoxy monomers and/or the different thiol monomers may each be used in any desired weight ratio relative to one another.

(85) In the epoxythiol-(meth)acrylate hybrid system, the proportion of the epoxythiol system is typically within a range from 20% by weight to 80% by weight, further typically within a range from 22% by weight to 70% by weight, more typically within a range from 25% by weight to 60% by weight and most typically within a range from 30% by weight to 50% by weight, based in each case on the total weight of the epoxythiol-(meth)acrylate hybrid system.

(86) In the epoxythiol-(meth)acrylate hybrid system, the proportion of the (meth)acrylate system is typically within a range from 10% by weight to 60% by weight, further typically within a range from 13% by weight to 55% by weight, more typically within a range from 15% by weight to 50% by weight and most typically within a range from 20% by weight to 40% by weight, based in each case on the total weight of the epoxythiol-(meth)acrylate hybrid system.

(87) The proportion of the at least one photolatent base in the epoxythiol-(meth)acrylate hybrid system is typically within a range from 0.001% by weight to 5.0% by weight, further typically from a range from 0.1% by weight to 2.0% by weight and especially typically from a range from 0.2% by weight to 1% by weight, based in each case on the total weight of the epoxythiol-(meth)acrylate hybrid system. Aforementioned ranges are applicable both to the use of a single type of photolatent base and to mixtures of different photolatent bases.

(88) In relation to the monomers to be used with preference in the epoxythiol-(meth)acrylate hybrid system, reference is made to the details in section “1.2 Epoxythiol-(meth)acrylate hybrid system.” In relation to the photolatent base to be used with preference in the epoxythiol-(meth)acrylate hybrid system, reference is made to the details in section “II Material to be used in accordance with the disclosure based on systems comprising at least one photolatent catalyst.”

(89) The advantage of an epoxythiol-(meth)acrylate hybrid system over a (meth)acrylate system is that it is possible here to transmit the reactivity via different polymerization mechanisms partly or fully between volume elements. It is likewise possible to control the mechanical and thermal properties of the polymer formed to a greater degree than in a (meth)acrylate system.

(90) IV Fluid to be Used in Accordance with the Disclosure Based on a Thiol-Ene System

(91) ##STR00003##

(92) The thiol-ene system utilizes the thiol-ene reaction as curing mechanism. This reaction initiated by a free-radical initiator does not experience any oxygen inhibition. By virtue of a relatively high proportion of sulfur-containing monomers, in turn, a high refractive index is enabled, with adjustability of refractive index and dispersion (n.sub.e (23° C.) 1.50-1.65). In addition, the curing reaction may be influenced by the concentration of the free-radical initiator, by the choice of exposure wavelength, the intensity of the radiation source and the exposure time, and also the temperature.

(93) The fluids to be used above in the sections “I Fluid to be used in accordance with the disclosure based on hybrid systems,” “II Material to be used in accordance with the disclosure based on systems comprising at least one photolatent catalyst,” “III Fluid to be used in accordance with the disclosure based on hybrid systems comprising at least one photolatent catalyst” and “IV Fluid to be used in accordance with the disclosure based on a thiol-ene system” may optionally comprise at least one additive which serves, for example, to improve the adhesion of the fluid on a substrate to be printed, to improve the printability of the fluid, to improve the flow characteristics of the fluid, to improve the wettability of the substrate, to increase the processing time, to optimize droplet formation and/or to avoid foam. Alternatively or additionally, the fluid to be used may optionally comprise at least one additive selected from UV absorbers, light stabilizers, stabilizers, biocides and dyes.

(94) The fluid to be used in accordance with the disclosure may be applied to a wide variety of different substrates. After application to a substrate and subsequent curing of the fluid to be used in accordance with the disclosure, the spectacle lens obtained from the fluid to be used in accordance with the disclosure may remain bonded to the substrate and may form the finished spectacle lens together with the substrate. Alternatively, the fluid to be used in accordance with the disclosure, after application to a substrate and subsequent curing, may be separated from the substrate and may form the finished spectacle lens without the substrate. The substrate in the latter case serves as support material to be removed again and/or as mold.

(95) If the substrate together with at least one cured volume element and/or with at least one final volume composite forms the finished spectacle lens, the substrate may comprise at least one polymeric material and/or at least One mineral glass. The polymeric material or the mineral glass here may each take the form of a lens blank, i.e., of a preformed piece of material for production of a lens in any state prior to completion of surface processing according to DIN EN ISO 13606:2013-10, paragraph 8.4.1, of a semifinished spectacle lens, i.e., of a lens blank having just one optically ready-processed face according to DIN EN ISO 13666:2013-10, paragraph 8.4.2, or of a finished spectacle lens, i.e., of a spectacle lens having two ready-processed optical faces before or after edge processing according to DIN EN ISO 13666:2013-10, paragraph 8.4.6. The semifinished lens blanks nay take the form of single-vision semifinished lens blanks, multifocal semifinished lens blanks or progressive-power semifinished lens blanks according to DIN EN ISO 13666:2013-10, paragraphs 8.4.3, 8.4.4 and 8.4.5. The finished lenses may be single-vision lenses, multifocal lenses, bifocal lenses, trifocal lenses, progressive-power lenses degressive-power lenses pursuant to DIN EN ISO 13666:2013-10 paragraphs 8.3.1, 8.3.2, 8.3.3, 8.3.4, 8.3.5 and 8.1.6. The lens blanks, semifinished lens blanks or finished lenses usable as substrate may be based, for example, on the base materials specified in table 1 below.

(96) TABLE-US-00001 TABLE 1 Examples of base materials for lens blanks, semifinished lens blanks or finished lenses Average refractive Abbe index number Trade name Base material n.sub.D* v.sub.D CR-39, CR-330, CR-607, Poly(allyldiglycol 1.500 56 CR-630, RAV 700, RAV carbonate), (PADC) 7NG, RAV 7AT, RAV 710, RAV 713, RAV 720 RAVolution Polyurea/Polyurethane 1.500 54 Trivex Polyurea/Polyurethane 1.530 45 Panlite, Lexan, Polycarbonate (PC) 1.586 29 Makrolon MR-6 Polythiourethane 1.598 MR-8 Polythiourethane 1.598 41 MR-7 Polythiourethane 1.664 32 MR-10 Polythiourethane 1.666 32 MR-174 Polyepisulfide 1.738 32 MGC 1.76 Polyepisulfide 1.76 30 Mineral 1.5 1.525 58 Mineral 1.6 1.604 44 Mineral 1.7 1.701 39.2 Mineral 1.8 1.802 34.4 Mineral 1.9 1.885 30 *Based on the sodium D line

(97) When a lens blank is used as substrate, it is possible to provide either just one or both of the faces with at least one volume element. If just one of the two faces is provided with at least one volume element, the opposite face is typically transformed to an optically ready-processed faced by mechanical processing, for example machining and/or grinding and/or turning and/or polishing.

(98) When a semifinished spectacle lens is used as substrate, either the optically ready-processed face or the opposite face may be provided with at least one volume element. If the optically ready-processed face is provided with at least one volume element, the opposite face is typically transformed to an optically ready-processed faced by mechanical processing, for example machining and/or grinding and/or turning and/or polishing.

(99) When a finished spectacle lens is used as substrate, it is possible to provide either just one or both of the ready-processed optical faces with at least one volume element. Typically, just one of the ready-processed optical faces is provided with at least one volume element.

(100) Particular preference is given to using a finished spectacle lens as substrate.

(101) Very particular preference is given to using at least one thin lens as substrate. The surface topography of the thin lens may, for example, be spherical, aspherical, toric, atoric, planar or progressive. A thin lens having a planar surface topography may be reshaped by means of a convex- or concave-shaped mold shell that has the negative shape and negative surface topography of the thin lens to be produced. A thin lens having a planar surface topography is understood to mean a thin lens without macroscopic visible bending or curvature. Preference is given to applying at least one volume element or at least one final volume composite to the reverse face of the thin lens. The reverse face of the thin lens is that face which, after completion of the spectacle lens, faces the eye in a spectacle frame; the front face of the thin lenses is that face which, after completion of the spectacle lens, faces away from the eye in a spectacle frame.

(102) The at least one thin lens may be based on various glass corn positions, for example borosilicate glass, aluminoborosilicate glass or alkali-free borosilicate glass. The at least one thin lens is typically based on a borosilicate glass or an aluminoborosilicate glass.

(103) The at least one thin lens typically has an average thickness from a range from 10 μm to 1000 μm, further from a range from 20 μm 800 μm, further typically from a range from 30 μm to 500 μm, more typically from a range 40 μm to 300 μm and most typically from a range from 50 μm to 3000 μm. The at least one thin lens more typically has an average thickness from a range from 100 μm to 250 μm. The average thickness of the at least one thin lens is understood to mean the arithmetic average Below an average thickness of 10 μm, the at least one thin lens is too mechanically unstable to be utilizable as substrate in an inkjet method without breaking of the at least one thin lens. Above ail average thickness of 1000 μm, the at least one thin lens can lead to spectacle lenses that would have too great an edge thickness or too great a middle thickness. The average thickness of the at least one thin lens is typically determined with a chromatic-confocal sensor, for example the ConfocalDT IFS2405 sensor from Micro-Epsilon Messtechnik GmbH & Co. KG, or interferometry sensor, for example the CHRocodile 2 IT sensor from Precitec GmbH & Co. KG. The average thickness of the at least one thin lens is typically determined on the basis of the at least one thin lens before the application of at least one volume element.

(104) The at least one thin lens typically has a surface roughness Ra of <10 nm. Further typically, the surface roughness Ra of the at least one thin lens is within a range from 0.1 nm to 0.8 nm, more typically within a range of 0.3 nm to 0.7 nm and most typically in a range of 0.4 nm to 0.6 nm. The aforementioned values for the surface roughness Ra are each based on the front face and the reverse face of the at least one unformed planar thin lens. After forming, the aforementioned values are each applicable solely to that surface of the at least one thin lens which has not been brought into contact with the shaped body used for forming. Depending on the shaped body used for forming, the aforementioned values may also be applicable to the surface of the at least one thin lens that was in contact with the shaped body used for forming. The surface roughness of the at least one thin lens is typically determined by means of white-light interferometry, typically using the New View 7100 instrument (from Zygo Corporation). If the at least one thin lens has further unevennesses, the area analysis of the respective surface car: also be determined by phase-measuring ectometry, typically with the SpecGage instrument (from 3D-Shape GmbH).

(105) The at least one thin lens may comprise at least one colorant or no colorant. The at least one thin lens typically does not comprise any colorant.

(106) Further typically, the transmittance of the at least one thin lens without colorant in the wavelength range from 400 nm to 800 nm is ≥90%, more typically ≥92%. The transmittance of the at least one thin lens without colorant is typically determined by means of a UV/VIS spectrophotometer, typically with the LAMBDA 950 UV/Vis/NIR Spectrophotometer (from Perkin Elmer Inc.).

(107) The at least one thin lens typically has a refractive index from a range of n=1.490 to n=1.950, further typically from a range of n=1.501 to n=1.799, more typically from a range of n=1.510 to n=1.755 and most typically from a range from n=1.521 to n=1.747, where the refractive index at a temperature of 21° C. is reported for the wavelength of the sodium D line.

(108) Thin lenses are commercially available, for example, under the D 263® T eco, D 263® LA eco, D 263® M, AF 32® eco, SCHOTT AS 87 eco, B 270® i names, each from Schott AG, Corning Willow Glass or Corning Gorilla Glass, each from Corning Inc.

(109) The substrate may not have an optical correction effect. Alternatively, the substrate may be endowed with an optical correction effect and/or an aberration correction for the viewing eye. Optical correction effect is understood to mean spherical correction, astigmatic correction and correction of the axis position and optionally correction by a prism with a base setting. This optical correction effect is conventionally implemented for distance viewing or close viewing in single-vision lenses. In the case of multifocal spectacle lenses, bifocal spectacle lenses, trifocal spectacle lenses, varifocal spectacle lenses or degressive spectacle lenses, the optical correction effect for distance vision and/or for close vision may in each case include a spherical correction, an astigmatic correction, a correction of the axis position and optionally a correction by a prism with a base setting. Aberration correction for the viewing eye, regardless of whether the aberration correction is for near vision or distance vision, is typically calculated analogously to Werner Köppen “Konzeption and Entwicklung von Gleitsichtgläsern” [Design and Development of Varifocal Lenses], Deutsche Optiker Zeitschrift DOZ, October 1995, pages 42-45. For this purpose, the surface properties of at least one substrate surface, in an optimization process, are varied by iteration until a desired aberration distribution for the viewing eye has been attained within a defined tolerance, i.e., until the merit function has gone below a defined value.

(110) If the substrate to be coated has already been endowed with an optical correction effect and/or an aberration correction for the viewing eye, the at least one volume element to be applied may serve to alter the optical correction effect and/or the aberration correction for the viewing eye.

(111) If the substrate comprises both at least one polymeric material and at least one mineral glass, the mineral glass typically takes the form of a thin lens, and the polymeric material typically takes the form of a semifinished lens blank or of a finished lens or of at least one polymer film.

(112) If the substrate comprises at least one thin lens and at least one polymer film as polymeric material, the at least one polymer film is typically disposed between at least two thin lenses. The at least one polymer film is typically based on polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polymethylmethacrylate, polyvinyl chloride, polyvinyl acetate, polyvinyl butyrate and/or mixtures thereof. The at least one polymer film may be stabilized with cellulose triacetate, for example. The at least one polymer film may be colored or uncolored. If the substrate that comprises at least a polymer film and at least a thin lens is to be colored, the at least one polymer film is typically colored. The at least one polymer film typically has an average thickness from a range from 10 μm to 600 μm, further typically from a range from 50 μm to 400 μm and most typically from a range from 80 μm to 250 μm.

(113) If, in this exemplary embodiment, the substrate to be coated comprises at least one thin lens and at least one finished spectacle lens as polymeric material, at least one thin lens may be on the front face and/or on the reverse face of the finished spectacle lens. Typically, at least one thin lens is on the front face of the finished spectacle lens and at least one volume element is applied to the reverse face of the finished spectacle lens.

(114) If, in this exemplary embodiment, the substrate to be coated comprises at least one thin lens and at least one semifinished spectacle lens product as polymeric material, preference is given to first processing the optically unfinished face and then bonding the front face and/or the reverse face of the finished spectacle lens thus obtained to at least one thin lens. Alternatively, in the case of use of a semifinished lens blank as polymeric material, the at least one thin lens is bonded to the already finished optical surface, the optically unfinished surface is processed, and then this processed surface is optionally bonded to at least one further thin lens. Bonding to at least one further thin lens is typical here. Typically, the finished optical surface of the semifinished lens blank is the front face thereof, and the optically unfinished surface is the reverse face thereof. As an alternative to the transformation of the optically unfinished face to a second optically finished face and the bonding thereof to at least one thin lens, this second face, before or after transformation to a second optically finished face, may be provided with at least one volume element or at least one coating. This coating is typically selected from the group consisting of at least one hardcoat layer, at least one antireflection layer, at least one antifog layer, at least one electrically conductive or electrically semiconductive layer, and at least one cleancoat layer. Particular preference is given to at least one hardcoat layer, at least one antireflection layer and at least one cleancoat layer as coating, in which case the at least one hardcoat layer is the layer closest to the substrate and the at least one cleancoat layer is the layer furthest removed from the substrate. If the surface of the substrate provided with at least one volume element is to be provided with at least one coating, this at least one coating may be selected from the group consisting of at least one hardcoat layer, at least one antireflection layer, at least one antifog layer, at least one electrically conductive or electrically semiconductive layer, at least one photochromic layer, at least one coloring layer and at least one cleancoat layer.

(115) The at least one thin lens bonded to the front face of the finished spectacle lens may be identical or different, for example in respect of glass composition, average thickness and/or shape, to the at least one thin lens bonded to the reverse face of the finished spectacle lens. The same also applies in the case of use of at least one semifinished lens blank or at least one polymer film as polymeric material. In the case of use of a semifinished lens blank, the optically unfinished surface, prior to the bonding to at least one thin lens, is transformed to an optically finished surface.

(116) The bonding of the at least one thin lens to the optically finished surface, typically the front face, of the semifinished lens blank, or to one of the finished optical surfaces, typically the front face, of the finished lens is typically cohesive and form-fitting. The reverse face of the at least one thin lens and/or the optically finished front face of the semifinished lens blank or of the finished lens may be provided with at least one coating. This at least one coating may comprise at least one coloring layer, at least one photochromic layer and/or at least one polarizing layer.

(117) The optional, preferred bonding of the second, finished optical surface of the semifinished lens blank or of the finished lens to at least one further thin lens is typically likewise cohesive and form-fitting.

(118) The front face and/or the reverse face of the at least one thin lens can each be coated by means of a PVD method and/or a wet coating process such as dip- or spin-coating. The subsequent curing of the coating obtained by wet coating methods can be effected either thermally or by radiation curing. Typically, this coating is cured by radiation curing.

(119) The bonding of the respectively optically finished surface of the semifinished lens blank or of the at least one finished optical surface of the finished lens or of the at least one polymer film to the at least one thin lens in each case is typically effected by an adhesive means. The adhesive means may serve here, for example, as primer or compensation material for the different thermal expansion of the individual components. In addition, via the selection of the adhesive, matching of any difference in refractive index Δn.sub.e that exists between the individual components can be achieved. What is typically effected here is not just the matching of the refractive index n.sub.e but also the matching of the dispersion, such that the change in the refractive index of the individual components is the same across the visible spectrum. Usable adhesive means are described, for example, in DE 10 2012 210 185 A1, WO 2009/056196 A1 or WO 2015/121341 A1. Typically, the individual components are bonded to one another by means of an adhesive means based on an amine-catalyzed thiol hardening of epoxy resins analogously to WO 2015/121341 A1, especially analogously to claim 1 of WO 2015/121341 A1, at a temperature from a range from 20° C. to 80° C., typically from a range from 40° C. to 70° C. and more typically from a range from 45° C. to 65° C.

(120) There may be at least one layer between the surface of the at least one thin lens facing the ready-processed optical face of the semifinished spectacle lens or of the finished spectacle lens and the ready-processed optical face. This at least one layer typically has the same surface topography as the respective surface beneath to which this at least one layer has been applied. Slight differences in the surface topography of the two surfaces to be joined to one another can be filled, for example, by means of an adhesive means. For form-fitting bonding of the respective surfaces, it is preferable that the radii of curvature of the components to be respectively bonded to one another typically differ from one another by less than 1 mm, further typically within a range from 0.03 mm to ≤0.8 mm, more typically within a range from 0.04 mm to ≤0.7 mm and most typically within a range from 0.05 mm to ≤0.6 mm.

(121) The at least one thin lens and the semifinished lens blank or the finished lens, before being joined by means of an adhesive means, typically have the same diameter and the same radius of curvature. Typically, the at least one polymer film has a diameter sufficiently great that the at least one polymer film completely covers the front face of the eye-side thin lens and the reverse face of the object-side thin lens. Any excess polymer film is typically cut off. If the at least one polymer film already has the same radius of curvature as the thin lens to be bonded thereto, the at least one polymer film typically has the same diameter as the thin lens.

(122) If a final volume composite is to be separated again from the substrate, prior to the application of the at least one volume element to the substrate, this may be provided with at least one adhesive layer or at least one separating layer, for example with a layer of an organomodified silane or siloxane. The substrate may also be provided with the desired coating of the spectacle lens, which is then separated from the substrate along with the final volume composite.

(123) Irrespective of whether a resultant final volume composite is or is not removed again from a substrate after the application of one of the above-described fluids to the substrate, it is preferable that the resultant final volume composite, at least on the surface remote from the substrate, is not subjected to any mechanical treatment, for example machining and/or grinding and/or turning and/or polishing.

EXAMPLES

(124) I Production of a Fluid of the Disclosure

Example 1: Production of a Fluid Based on a Thiol-Ene-(Meth)Acrylate Hybrid System

(125) TABLE-US-00002 % by wt. Part A Pentaerythritol tetrakis(3-mercaptopropionate) PETMP 52.63 Part B 1,3,5-Triallyl-1,3,5-triazine-2,4,6- TTT 36.26 (1H,3H,5H)-trione Hexane-1,6-diol diacrylate HDDA 9.07 2,6-Di-tert-butyl-4-methylphenol BHT 0.45 2-Hydroxy-2-methyl-1-phenylpropan-1-one Omnicure 1.36 1173 Nonionic fluorosurfactant Zonyl 0.23 FSN

(126) The constituents of part B were premixed at room temperature. The resultant portions were blended by stirring in a mixing ratio of 50% by volume of part A to 50% by volume of part B, or 52.63% by weight of part A to 47.37% by weight of part B.

Example 2: Production of a Fluid Based on a Thiol-Ene-(Meth)Acrylate Hybrid System

(127) TABLE-US-00003 % by wt. Trimethylolpropane trimercaptopropionate TPMP 12.59 Butane-1,4-diol divinyl ether BDDVE 6.78 Dipropylene glycol diacrylate DPGDA 77.48 2,6-Di-tert-butyl-4-methylphenol BHT 0.97 2-(2H-Benzotriazol-2-yl)-4-(1,1,3,3- Tinuvin 0.24 tetramethylbutyl)phenol 329 2-Hydroxy-2-methyl-1-phenylpropan-1-one Omnicure 0.48 1173 2,4,6-Trimethylbenzoyldiphenylphosphine Omnirad 1.45 oxide TPO

(128) The main components of the fluid were mixed, and the additives were then added while stirring.

Example 3: Production of a Fluid Based on a Thiol-Ene-(Meth)Acrylate Hybrid System

(129) TABLE-US-00004 % by wt. Dimercaptodiethyl sulfide DMDS 8.48 Trivinylcyclohexane TVCH 5.98 Bis(2-methacryloylthioethyl) sulfide S-2EG 81.93 2,6-Di-tert-butyl-4-methylphenol BHT 0.96 2-(2H-Benzotriazol-2-yl)-4-(1,1,3,3- Tinuvin 0.24 tetramethylbutyl)phenol 329 2-Hydroxy-2-methyl-1-phenylpropan-1-one Omnicure 0.96 1173 2,4,6-Trimethylbenzoyldiphenylphosphine Omnirad 1.45 oxide TPO

(130) The main components of the fluid were mixed, and the additives were then added while stirring.

Example 4: Production of a Fluid Based on an Epoxythiol-(Meth)Acrylate Hybrid System

(131) TABLE-US-00005 % by wt. Part A Bisphenol F diglycidyl ether Rütapox 19.10 0158 Bisphenol A diglycidyl ether Rütapox 19.10 0162 3-Glycidyloxypropyltrimethoxysilane GPTS 1.15 Dipropylene glycol diacrylate DPGDA 30.56 2,6-Di-tert-butyl-4-methylphenol BHT 0.38 2-Hydroxy-2-methyl-1-phenylpropan-1-one Omnicure 1.14 1173 Part B Pentaerythritol tetrakis(3-mercapto- PETMP 28.53 propionate) 1,4-Diazabicyclo[2.2.2]octane DABCO 0.04

(132) The constituents of part A and part B were each mixed at room temperature by stirring. The resultant portions were blended by stirring in a mixing ratio of 71.43% by weight of part A to 28.57% by weight of part B.

Example 5. Production of an Epoxy(Meth)Acrylate Hybrid System

(133) TABLE-US-00006 % by wt. Part A 3,4-Epoxycyclohexylmethyl 3,4-epoxy- Celloxide 20.00 cyclohexanecarboxylate 2021P Bis((3,4-epoxycyclohexyl)methyl) adipate ERL 4299 20.00 2-Ethylhexane-1,3-diol EHD 8.00 3-Glycidyloxypropyltrimethoxysilane GPTS 0.40 Triarylsulfonium hexafluoroantimonate, Cyracure 1.60 about 50% in propylene carbonate 6976 Part B Tripropylene glycol diacrylate TPGDA 48.78 2,6-Di-tert-butyl-4-methylphenol BHT 0.24 2-Hydroxy-2-methyl-1-phenylpropan-1-one Omnicure 0.98 1173

(134) The constituents of part A and part B were each mixed at room temperature by stirring. The resultant portions were blended by stirring in a mixing ratio of 50.0% by weight of part A to 50.0% by weight of part B, although the proportion of part B (acrylate content) may be varied on account of the independence of the two reaction systems.

Example 6: Production of an Epoxythiol-Thiol/Ene Hybrid System Comprising a Photolatent Base

(135) TABLE-US-00007 % by wt. Part A Bisphenol F diglycidyl ether Rütapox 23.98 0158 Bisphenol A diglycidyl ether Rütapox 15.99 0162 3-Glycidyloxypropyltrimethoxysilane 1.20 1,3,5-Triallyl-1,3,5-triazine-2,4,6- TTT 11.99 (1H,3H,5H)-trione 2-Hydroxy-2-methyl-1-phenylpropan-1-one Omnicure 2.40 1173 Part B GST/XDI prepolymer (100 parts 4-mercapto- 42.73 methyl-3,6-dithiaoctane-1,8-dithiol (GST) + 16 parts xylylene 1,3-diisocyanate (XDI) 1-Benzyloctahydropyrrolo[1,2-a]pyrimidine CGI 90 1.71

(136) The constituents of part A and part B were each mixed at room temperature by stirring. The resultant portions were blended by stirring in a mixing ratio of 55.56% by weight of part A to 44.44% by weight of part B.

Example 7: Production of an Epoxythiol-Thiol/Ene Hybrid System Comprising a Photolatent Base

(137) TABLE-US-00008 % by wt. Part A Bisphenol F diglycidyl ether Rütapox 23.48 0158 Bisphenol A diglycidyl ether Rütapox 15.65 0162 3-Glycidyloxypropyltrimethoxysilane GPTS 1.17 1,3,5-Triallyl-1,3,5-triazine-2,4,6- TTT 13.70 (1H,3H,5H)-trione 2-Hydroxy-2-methyl-1-phenylpropan-1-one Omnicure 3.13 1173 Part B Pentaerythritol tetrakis(3-mercaptopropionate) PETMP 40.82 1-Benzyloctahydropyrrolo[1,2-a]pyrimidine CGI 90 2.04

(138) The constituents of part A and part B were each mixed at room temperature by stirring. The resultant portions were blended by stirring in a mixing ratio of 57.14% by weight of part A to 42.86% by weight of part B.

Example 8: Production of an Epoxythiol-(Meth)Acrylate Hybrid System Comprising a Photolatent Base

(139) TABLE-US-00009 % by wt. Part A Bisphenol F diglycidyl ether Rütapox 20.13 0158 Bisphenol A diglycidyl ether Rütapox 20.13 0162 3-Glycidyloxypropyltrimethoxysilane GPTS 1.21 Dipropylene glycol diacrylate DPGDA 24.15 2,6-Di-tert-butyl-4-methylphenol BHT 0.40 2-Hydroxy-2-methyl-1-phenylpropan-1-one Omnicure 2.01 1173 Part B Pentaerythritol tetrakis(3-mercaptopropionate) PETMP 30.45 1-Benzyloctahydropyrrolo[1,2-a]pyrimidine CGI 90 1.52

(140) The constituents of part A and part B were each mixed at room temperature by stirring. The resultant portions were blended by stirring in a mixing ratio of 68.03% by weight of part A to 31.97% by weight of part B.

(141) II Polymerization of the Fluids of the Disclosure

(142) For polymerization of the fluids of the disclosure, a thin film of each fluid was exposed using the parameters listed in table 2 under air.

(143) TABLE-US-00010 TABLE 2 Parameters for polymerization of the fluids of the disclosure. UV-LED, UV-LED, Exposure wavelength, power, time, Curing of the epoxy Example nm mW/cm.sup.2 s component 1 365 80 90 — 2 365 200 60 — 3 365 400 90 — 4 365 100 60 Thermal epoxy curing: 15 h at 25° C./1 h at 80° C. 5 365 100 60 Simultaneous cationic epoxy curing 6 365 200 60 Photoactivation of the amine-catalyzed epoxy curing 7 365 200 60 Photoactivation of the amine-catalyzed epoxy curing 8 365 100 60 Photoactivation of the amine-catalyzed epoxy curing

(144) III Characterization of the Fluids of the Disclosure

(145) IIIa Determination of the Stability of the Fluids of the Disclosure at Room Temperature

(146) In order to determine the stability of the fluids from examples 1, these were stored in closed containers under an air atmosphere in the dark at room temperature, and the flow characteristics were assessed at regular intervals.

(147) IIIb Determination of the Viscosity of the Fluids of the Disclosure

(148) The viscosity of the fluids was determined with the aid of the C-VOR rotary viscometer from Bohlin Instruments in a cone-plate arrangement (1° geometry) at a shear rate of 100 s.sup.1.

(149) IIIc Determination of the Refractive Indices of the Fluids of the Disclosure

(150) A determination of the refractive indices and of the dispersion was conducted with the aid of the Abbe 60/ED Abbe refractometer from Bellingham & Stanley and different spectral lamps (Na, Hg, Cd, He).

(151) TABLE-US-00011 TABLE 3 Properties of the fluids of the disclosure Viscosity, Refractive Refractive Storage stability 25° C. index n.sub.e.sup.21, index n.sub.e.sup.21, (25° C., darkness), Example mPas fluid polymer months 2 21 1.4632 1.5066 >6 3 12 1.5666 1.6274 >6 6 not not 1.628 not determined determined determined

(152) The foregoing description of the exemplary embodiments of the disclosure illustrates and describes the present invention. Additionally, the disclosure shows and describes only the exemplary embodiments but, as mentioned above, it is to be understood that the disclosure is capable of use in various other combinations, modifications, and environments and is capable of changes or modifications within the scope of the concept as expressed herein, commensurate with the above teachings and/or the skill or knowledge of the relevant art.

(153) The term “comprising” (and its grammatical variations) as used herein is used in the inclusive sense of “having” or “including” and not in the exclusive sense of “consisting only of.” The terms “a” and “the” as used herein are understood to encompass the plural as well as the singular.

(154) All publications, patents and patent applications cited in this specification are herein incorporated by reference, and for any and all purposes, as if each individual publication, patent or patent application were specifically and individually indicated to be incorporated by reference. In the case of inconsistencies, the present disclosure will prevail.