DD287796A5 - SPECTRAL SENSITIZED PHOTOPOLYMERIZABLE MATERIAL - Google Patents

Abstract

The invention relates to a spectrally sensitized photopolymerizable material. The invention relates to near-UV and short-wavelength visible light (310 nm 420 nm) sensitized photopolymerizable materials with increased photosensitivity for information recording, the production of printing plates and printed circuits. The object of the invention is to provide a novel initiator system for a spectrally sensitized photopolymerizable material having high sensitivity and improved storage stability. According to the invention, the object is achieved in that the material contains a light absorbing 1,4-dihydropyridine of general structure I together with a coinitiator of general formula II R 1 (R 2) p (R 3) q On Z. {1,4-dihydropyridine; iodonium salt; sulfonium; photopolymerization; Photoinitiator; Printing plate; printed circuit; Information recording}

Description

R ¹ (R ² ) p (R ³ ) _q On®Z ^e Ι ' ι

wherein R ¹ , R ² , R ³ = alkyl, aralkyl, aryl

On® = I®, Cl®, Br®, S®, Se®, Te®

Ζ ^θ = anion, which does not react with On® at 2O ⁰ C and light exclusion, z. B. Cl®, Br ^e , BF ₄ ⁹ , HSO ₄ ⁰ ,

ASF ₆ ⁰ , SbF ₆ ⁰ (p = 0,1,2; q = 1,2).

2. spectrally sensitized photopolymerizable material according to claim 1, characterized in that the two-component system I, II contains the components in a ratio l: ll between 0.1 and 10.

3. spectrally sensitized photopolymerizable material according to claim 1, characterized in that for a short time preferably to 50-80 ⁰ C is heated to increase the sensitivity of cationically polymerizable monomers.

4. spectrally sensitized photopolymerized material according to claim 1, characterized in that the total mass of the monomer to the total mass of the initiators I, II may be in a ratio of 5: 1 to 60: 1.

Field of application of the invention

The photoinitiator system described can be used in negative-working materials for information recording and production of printing plates, printed circuits, light-curing adhesives and for surface coating.

Characteristic of the known state of the art

Numerous photopolymerizable materials have been described. They generally consist of a binder, base, monomers, oligomers, initiators and additives such as plasticizers, stabilizers, dyes. Under the action of light, reactive species are generated by the initiator system, which in turn initiate the polymerization. The formation of this species can be done by different mechanisms:

1. By photodissociation Lei direct excitation or sensitization

2. By photoredox reactions linked to H abstraction

α h'V. ., + HB ^

A > A · - > .AH

- B.

3. By photoredox reaction associated with e ~ transfer

A A · -> At + CT or AT + Ct

The main representatives of the I. group are benzoin and benzoin derivatives (DE-OS 1769168,2232365; GB-PS1429053) as well as peroxides (SG Cohen, BE Osterberg, PB Sparrow, LR Blont, J. Polym., Sci 3 [1949] 264 )

2nd group:

Benzophenone and derivatives (DE-OS 1949010) Mixtures of benzophenone and Michler's ketone (DE 2216154) Anthraquinone, xanthone (OE-OS 17S5 089, US-PS 30 47127, JP-PS 77 55 631, GB-PS 8 61438, US-PS 3046127.29 51758)

3rd Group: Dye-Redox Systems (UV-PS 3092096)

Arendiazonium salts with donors (UV-PS 3615452, T.Yamase, T.lkawa, H. Koado, E.lnone, Sci. And Eng. 17 (1973) 23268) Furthermore, it is known that in the decomposition of Oh®, such as RN ₂ * (GB-PS 1321263, US-PS3708 296.4171974), acids

arise, which are able to trigger the cationic polymerization of suitable compounds.

By combining the On® with the initiators mentioned above to bivalent initiators can often be a significant Sensitivity increase (DD-PS 158281). The use of 1,4-dihydropyridines in the manner described above as an initiator for polymer building reactions is in the Patent literature unknown. In contrast, there are applications for printing plate production, but based on other principles, such as degradation of Polymers and deactivation of redox compounds (DE-OS 2242106, DE-OS 2758210, DE-OS 2710417, DE-OS 2718130,

DE-OS 2808010, JP 58223147).

Consequently, they are positive materials. Object of the invention

The object of the invention is to provide a photopolymerizable material of high sensitivity in the spectral range of 310nm to 420nm with a good thermal stability and storability, which can find wide application for information recording and for the production of printing plates and pressed circuits.

Explanation of the essence of the invention

By introducing a novel component in the photoirror system to initiate radical and / or cationic polymerization (bivalent initiator) in polymerizable materials of conventional composition (binder, initiator, monomers, additives), the range of such composites is to be expanded and in individual quality-determining properties ( Sensitivity, storage stability, system compatibility, universal applicability, availability of chemicals) can be modified and improved. According to the invention, the object is achieved by the use of 1,4-dihydropyridines, formula I:

R * 3 & ix

R '

• ΛΛ

R ¹ = H, alkyl, aralkyl, R ^1l -CO (R "= alkyl, aralkyl)

R ² , R ² = alkyl

R ³ , ft ^y = COO alkyl, CO alkyl, COOH, COMR "R" (R ³¹ , R "= alkyl, aralkyl), CN R ⁴ = H, alkyl, aralkyl, C _e He. _n Y _n (Y = Cl, Br, I, F, NO, alkyl, alkoxy), furanyl

(R ² and R ¹ or R ^r , R ^r may be cyclically linked) in conjunction with a coinitiator of the general formula II: R ¹ JR ² Ip (R ³ JqOn ⁰ Z ⁹ II

R ¹ , R ¹ , R ³ = alkyl, aralkyl, aryl, C _e He. _n Y _n (Y = Cl, Br, I, alkyl, alkoxy !, NO ₂ ), COR ₄ (R ₄ = alkyl, aralkyl, aryl) On® ^m I® Cl® Br® S® Se® Te® P® Z ^e - Anlon.'which does not react with On® at 20 ° C and light leakage, e.g. B. Cl ^e , Br ⁰ , Ι ^θ , HSO ₄ ⁹ , BF ₄ ^e , PF » ⁹ , ASF« ⁹ , SbF ,, ⁹ .

H ₂ PO ₄ ⁹ , NO ₃ ⁹ ) (p - 0,1,2; q = 0,1,2) dissolved; which generate polymerization-inducing species (radicals, cations) only under the action of light with high efficiency. The basic mechanism is a photoinitiated electron transfer, whereby the high efficiency is ensured by the ability of the 1,4-dihydropyridines to release a second electron in a thermal reaction step as a competition to the back electron transfer.

embodiments

The indicated amounts of solid substances are dissolved in the binder solution. This gassing solution is uniformly distributed with a roller or by means of a sling on oiner pad and dried. To exclude the inhibiting effect of oxygen, a protective layer of polyvinyl alcohol or polyvinylpyrrolidone can be applied. This can be cured immediately or after a reduction (~ one year) in contact with a 200 W Hg high pressure lamp (HBO 200, VEB Narva [exposure times 1 to 4 min.)]. Developed by moving in a solution adapted to the binder.

example 1 The following composition is applied to a 180 μm thick polyester film:

0.5 g diphenyliodonium tetrafluoroborate 0.02 g 2,6-dimethyl-3,5-diethoxycarbonyl-4-methyl-1,4-dihydropyridine 10 g pentaerythritol tetraacrylate 0.1 g hydroquinone monomethyl ether 30 ml 10% solution of polyvinylpyrrolidone in methanol. Development in methanol.

Example 2 On a roughened aluminum plate are applied:

0.5g dicumyliodonium chloride 0.02g 2,6-dimethyl-3,5-dimethoxycarbonyl-4-phenyl-1,4-dihydropyridine 5g pentaerythritol tetraacrylate 5g diandiglycidyl ether diacrylate 0.1g hydroquinone monomethyl ether 30ml 15% solution of a-methylstyrenemalkenoic acid copolymer mono-n-butyl ester in n-butanol / Acetone = 1V / 4V

Development is in a 5% aqueous silicate solution. Example 3 Coating is done with a solution of:

0.5gTriphenylsulfonium tetrafluoroborate 0.02g 2,6-dimethyl-3,5-diethoxycarbonyl-1,4-dihydropyridine 5g pentaerythritol tetraacrylate, triacrylate 5g diandiglycidyl ether diacrylate 0.1g hydroquinone monomethyl ether 15% mixture 10/1 = α-methylstyrenemalein anhydride copolymer mono-n-butyl ester / n-octyl ester in n-butanol / acetone = 1V / 4V

Example 4 On a roughened aluminum plate are applied:

0.5g dicumyliodonium chloride 0.02g 1,2,6-trimethyl-3,5-diethoxycarbonyl-4- (p-methoxy) phenyl-1,4-dihydropyridine 7.5g diandiglycidyl ether dimethacrylate 2.5g pentaerythritol triacrylate 0.1g hydroquinone monomethyl ether 30ml 15% igo solution of α-methylstyrene maleic acid copolymer mono-n-butanol / acetone = 1V / 4V

It is developed with a 5%) aqueous, basic silicate solution. Example 5 Applied to a roughened aluminum plate:

1.5 g of dicumyliodonium chloride 0.02 g of 2,6-dimethyl-3,5-diethoxycarbonyl-4- (p-chlorophenyl) -1,4-dihydropyridine 10 g of digiycid ether of a dianobedine novolak

Pouring is made from a 15% solution of a Dian based novolak (30ml). After 15 minutes of irradiation is developed in 0.5M aqueous NaOH and stained with rhodamine B.

Claims (1)

1. Spectral sensitizartKartes photopolymerizable material, consisting of pad, at least one layer-forming, or by suitable additives layer-forming made to be able to radically or cationically polymarisierbaren monomers, a 1,4-dihydropyridine, a coinitiator, a binder and optionally further additives, characterized by Combination of one or more 1,4-dihydropyridine compounds of the general formula I: in the R ¹ = H, alkyl, aralkyl, R ¹¹ -CO (R ¹¹ = alkyl, aralkyl) R ² / R ² = same or different H, alkyl R ³ , R ³ '= the same or different COO alkyl, CO alkyl. COOH, CONR ³¹ R ³² (R ³¹ , R ³² = H, alkyl, aralkyl), CN R ⁴ = H, alkyl, aralkyl, C ₆ H ₆ T ₁ Y _n (Y = Cl, Br, I, F, NO ₂ alkyl, alkoxy), furanyl (R ² , R ³ or R ² ', R ³ 'may be cyclically linked) with a coinitiator of general formula II: