Process for the production of images using sequentially liquid polymerizing compositions and photocuring

• US 4,604,344 A
• Filed: 01/23/1985
• Issued: 08/05/1986
• Est. Priority Date: 02/03/1984
• Status: Expired due to Fees

• Current Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Original Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Inventors: Irving, Edward, Smith, Terence J.
• Primary Examiner(s): Kittle, John E.
• Assistant Examiner(s): Hamilton, Cynthia
• Application Number:
  US06/694,178
• Time in Patent Office: 559 Days
• Field of Search: 430/325, 430/327, 430/18, 430/281, 430/280, 430/270, 430/286, 430/271
• US Class Current: 430/325
• CPC Class Codes: G03F 7/168 Finishing the coated layer, e.g. drying, baking, soaking
• CPC Class Codes: H05K 3/0079 characterised by the method of application or removal of the mask H05K3/0091 takes precedence

Abstract

A polymerizing agent is applied to a substrate followed by a layer of a liquid composition containing both a polymerizable residue and a photocurable residue. The polymerizable residue is polymerized by the polymerizing agent first applied so that the layer solidifies but remains photocurable. Subsequently this solidified layer is exposed to actinic radiation in a predetermined pattern and those parts of the layer that are not photocured are removed by treatment with a suitable solvent.

Typical polymerizable residues include cyanoacrylates, the polymerizing agents for which may be water, ammonium hydroxide solution, an alkali metal hydroxide solution, or an amine. Typical photocurable residues include acrylates and methacrylates.

The process is suitable for the manufacture of printing plates and printed circuits.

Claims

1. A process for the production of an image which comprises

(a) applying to a substrate a polymerizing agent,

(b) applying to the polymerizing agent on the substrate a layer of a liquid composition containing a residue that is polymerizable on contact with the polymerizing agent, and a photocurable residue, such that the layer solidifies but remains photocurable,

(c) exposing the solidified layer to actinic radiation in a predetermined pattern such that exposed parts of the layer are photocured, and

(d) removing those parts of the layer which have not become substantially photocured by treatment with a solvent therefor.

2. A process according to claim 1, in which the liquid composition comprises a substance having polymerizable and photocurable groups on the same molecule.

3. A process according to claim 1, in which the liquid composition comprises a mixture of one or more materials that are polymerizable on contact with the polymerizing agent, together with one or more photocurable materials.

4. A process according to claim 1, in which the polymerizable residue comprises a single species or two or more similar species which polymerize under the catalytic influence of the polymerizing agent.

5. A process according to claim 1, in which the polymerizable residue comprises two or more co-reacting species that are stable until reaction between them is catalyzed or accelerated by the polymerizing agent.

6. A process according to claim 4, in which the polymerizable residue and its polymerizing agent are selected from the group consisting of

(i) a cyanoacrylate with water, aqueous ammonium hydroxide solution, an aqueous alkali metal hydroxide solution or an amine,

(ii) an isocyanate-terminated prepolymer with water, aqueous ammonium hydroxide solution, an aqueous alkali metal hydroxide solution, or an amine,

(iii) an epoxy resin with a boron trifluoride or boron trichloride complex, a boron difluoride chelate, dicyandiamide, an imidazole, an amine, or an acid anhydride, and

(iv) a phenolic resin with an acid or an aqueous acidic solution.

7. A process according to claim 5 in which the polymerizable residue and its polymerizing agent are selected from the group consisting:

(i) a mixture of a polyol and an isocyanate with aqueous ammonium hydroxide solution, an aqueous alkali metal hydroxide solution, or an amine,

(ii) a polyene-polythiol mixture with aqueous ammonium hydroxide solution, an aqueous alkali metal hydroxide solution, or an amine,

(iii) an epoxy resin-amine mixture with an acid, aqueous acid solution, an acid salt solution or a metal perchlorate, trifluoromethanesulfonate, trihalocarboxylate, or nitrate,

(iv) an epoxy resin-thiol mixture with an aqueous ammonium hydroxide solution or an amine, and

(v) a mixture of an acrylate or methacrylate and a peroxide initiator with an amine, a Schiff'"'"'s base, or a transition metal or its salt.

8. A process according to claim 6, in which the polymerizable residue is

(i) a cyanoacrylate of formula ##STR10## in which R¹ has, at most, 18 carbon atoms and is an alkyl, alkenyl, aralkyl, haloalkyl, cycloalkyl, aryl or alkoxyalkyl group,

(ii) an isocyanate-terminated prepolymer formed by reaction of a polyol, polyamine, or polycarboxylic acid with an aliphatic, cycloaliphatic or aromatic diisocyanate,

(iii) an epoxy resin containing at least two groups of formula ##STR11## directly attached to an atom or atoms of oxygen, nitrogen or sulfur, where either R² and R⁴ each represent a hydrogen atom, in which case R³ denotes a hydrogen atom or a methyl group, or R² and R⁴ together represent --CH₂ CH₂ --, in which case R³ denotes a hydrogen atom,

(iv) an epoxy resin in which some or all of the epoxide groups are in non-terminal positions, or

(v) a phenolic resin that is a resole made from a phenol and an aldehyde.

9. A process according to claim 7, in which the polymerizable residue is

(i) a mixture of an alkylene glycol, a polyoxyalkylene glycol, an alkane triol, a hydroxy group-containing reaction product of an epoxy resin with a carboxylic acid, carboxylic anhydride, phenol, primary or secondary amine, or thiol, pentaerythritol or a hydroxy group-containing polymer, with an aliphatic, cycloaliphatic or aromatic isocyanate,

(ii) a mixture of a polyene having a molecular weight of 50 to 20,000 and containing two or more ethylenic or ethynylic bonds capable of participating in a free-radical polymerization reaction, or an epoxy resin having at least two groups of formula II or having some or all of the epoxide groups in non-terminal positions, with a polythiol having a molecular weight within the range 50 to 20,000 which is an ester of thioglycolic, alphamercaptopropionic or beta mercaptopropionic acid with a glycol, triol, tetraol, pentaol or hexol,

(iii) a mixture of an epoxy resin having at least two groups of formula II or having some or all of the epoxide groups in non-terminal positions with an aliphatic, alicyclic, unsaturated heterocyclic, aromatic or araliphatic primary, secondary or tertiary amine, or

(iv) a mixture of an acrylate or methacrylate monomer which is acrylic or methacrylic acid, or an alkyl acrylate, alkylenediol diacrylate, 1,1,1-trimethylolpropane triacrylate, polypropylene glycol diacrylate, allyl acrylate, an acrylate ester of an epoxide or a phenolic resole, or a corresponding methacrylate, with hydrogen peroxide, tert.butyl hydroperoxide, cumene hydroperoxide, or 2,4-dimethyl-2,4-hexane dihydroperoxide.

10. A process according to claim 1, in which the polymerizable residue, and its polymerizing agent, are selected from the group consisting of:

(i) an alkyl cyanoacrylate in which the alkyl group has 1 to 8 carbon atoms, with water,

(ii) a mixture of a dual-functional hydroxyl group-containing reaction product of an epoxide resin with acrylic or methacrylic acid and a diisocyanate, with an aromatic primary amine,

(iii) an epoxide resin containing at least two epoxide groups with a boron difluoride chelate,

(iv) a mixture of an epoxide resin having at least two epoxide groups and an aromatic primary diamine, with a metal nitrate accelerator,

11. (v) a dual functional reaction product of acrylic or methacrylic acid and a phenolic resole made from phenol and formaldehyde, with an acid,

(vi) a mixture of a peroxide initiator and an acrylate or methacrylate of an alkylenediol or trimethylolpropane, a hydroxyalkyl acrylate or methacrylate or a reaction product of acrylic or methacrylic acid and a polyglycidyl ether of a monohydric alcohol or phenol, with a transition metal salt accelerator, and

(vii) a mixture of a peroxide initiator and a dual-functional reaction product of acrylic or methacrylic acid and a phenolic resole made from phenol and formaldehyde, with a transition metal salt accelerator.

12. A process according to claim 1, in which the photocurable residue present is one in which cure is effected by direct activation of photosensitive groups through irradiation.

13. A process according to claim 11, in which the material having photosensitive groups is one having at least two azido, coumarin, stilbene, maleimido, pyridinone, chalcone, propenone, pentadienone, or anthracene groups or acrylic ester groups which are substituted in their 3-position by a group having ethylenic unsaturation or aromaticity in conjugation with the ethylenic double bond of the acrylic group.

14. A process according to claim 1, in which the photocurable residue present is one in which irradiation activates a suitable initiator molecule which then activates a photopolymerizable group.

15. A process according to claim 13, in which the photocurable residue is an epoxide resin, phenolic resin, urea-formaldehyde resin, cyclic ether, cyclic ester, cyclic sulfide, cyclic amine, or organosilicon cyclic in combination with a radiation-sensitive aromatic `onium or iodosyl salt, or a full or partial ester of acrylic or methacrylic acid with an aliphatic monohydric alcohol, glycol, or higher functional polyol or with a compound containing one or more glycidyl groups, or an ester formed by reaction of a polyepoxide with an adduct of a hydroxyalkyl acrylate or methacrylate with a saturated or unsaturated polycarboxylic acid anhydride.

16. A process according to claim 2 in which the substance having polymerizable and photocurable groups on the same molecule is an epoxide or a phenolic resole containing a photocurable group, or, together with an isocyanate, a hydroxy compound containing a photocurable group.

17. A process according to claim 1 in which the photocurable residue is selected from the group consisting of:

(i) an epoxide resin obtained by advancement with a bisphenol of a diglycidyl ether of a bisphenol containing a pentadienone group,

(ii) a cycloaliphatic epoxide resin in combination with a radiation-sensitive aromatic onium salt,

(iii) methylol groups in a dual-functional reaction product of acrylic or methacrylic acid and a phenol-formaldehyde resole, in combination with a radiation-sensitive aromatic onium salt,

(iv) acrylate or methacrylate groups in a dual-functional reaction product of acrylic or methacrylic acid and a phenolformaldehyde resole,

(v) an acrylate or methacrylate of an alkylene diol or 1,1,1-trimethylolpropane, and

(vi) a reaction product of acrylic or methacrylic acid and a polyglycidyl ether of a polyhydric alcohol or phenol.

18. A process according to claim 1 in which the polymerization stage and the photocuring stage are effected through different chemical processes.

19. A process according to claim 1, in which the polymerizing agent is applied by spraying, dipping, brushing or spin-coating, using a solution or suspension in water or an organic solvent where the agent is not a liquid.

20. A process according to claim 1, in which the modified layer is exposed to actinic radiation of wavelength 200-600 nm.

21. A substrate bearing an image produced by a process according to claim 1.