DD279251A1 - PROCESS FOR PRODUCING HAERTBARER LAYERS - Google Patents

Abstract

The invention relates to a process for the preparation of hair-hardenable layers, which are applicable due to their specific reactivity as protective layers, adhesives, resist materials or optical storage systems. It is the object of the invention to exploit the extremely low volume contraction of polymerizing spiroorthoester systems in the form of thermally or photochemically stress-free crosslinking layers. The object is achieved according to the invention in that a polymer layer is produced which contains spiroorthoester structural members and further additives and is crosslinked as a reactive layer by thermal or radiation-induced crosslinking.

Description

CH ₃ J

₃ CJ-

0 = c ⁿ ;. = ii, i: ii. ₅ , οιι., Χ (\ = ιι _{Γ /} οι),

, ₅ ,

CH ₃ O HCC - CH O-CH-R

H ₂ C-O ^N 0-CH ₂ Formal

3. The method according to claim 1, characterized in that are used as additives initiators, preferably arylium salts and / or photoactive radical formers, for example benzoin ethers, benzil ketal or benzopinacol.

4. The method according to claim 1, characterized in that as additives radically crosslinking monomers, preferably 2,2-bis [4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl] propane (bis-GMA), Trimethyiolproparitri (meth) acryiat or pentaerythritol tetra (meth) acrylate.

5. The method according to claim 1, characterized in that are used as additives radically and / or cationically polymerizable monomers, preferably oxiranes, dioxolanes, glycidyl (meth) acrylate or dioxolane (meth) acrylate.

Field of application of the invention

The invention relates to a method for He'stellung curable layers with Spiroorthoester structural members. Such layers are versatile in the use of additives due to their specific reactivity.

They can be used as protective layers for a wide variety of materials, as adhesives for joining lenses or other optical assemblies or as resist material.

Such reactive layers (active media) are therefore used primarily in electrical engineering / electronics and in the fine mechanical-optical industry. They can equally be part of substrate materials for optical storage systems (disk storage), which are increasingly used in data technology.

Characteristic of the known state of the art

There are no known methods for producing curable layers which are close to the invention.

Object of the invention

It is the object of the invention to exploit the advantageous properties of the spiroorthoesters, especially those of the poly-spiroorthoesters, without any appreciable volume contraction, and to use such poly-spiroorthoesters in the form of reactive layers, which crosslink thermally or by radiation crosslinking. It is a further object of the invention to maintain the positive properties of epoxy-spiroorthoester copolymers, as described in the patent DD 203623, in terms of excellent adhesion, but at the same time the good Fiirr.i.ildungseigenschaften the polymers with Spiroorihoester groups according to DD 233577 A1 for use as an active layer.

Explanation of the essence of the invention

It is an object of the invention to use poly-spiroorthoester so that the volume contraction-free polymerization of the spiroorthoester monomers and the good film-forming and adhesion behavior of the polymers are combined in a reactive layer (active medium). Furthermore, layers can be used in which the spiroorthoester properties are advantageously combined with those of other oxygen heterocycles and / or film-forming unsaturated monomers.

According to the invention the object is achieved in that curable layers are prepared containing spiroorthoester structural members and used after addition of additives in the form of initiators and / or monomers as reactive layers and crosslinked ring opening or thermal or radiation induced.

The introduction of the spiroorthoester structural members into the reactive layer takes place in the form of polymers, preferably of poly-spiroorthoesters of the formula 1, whose preparation is described in DD 233577 A1.

O = V, " II- II, CIL ₅ , CII ₀ X ¹ Cx = Rc, Cl),

C! L _o 0 (CII ₂ ) ₃ CII _{: 3} ,

CiL, η cn ₀ ocii ₀ cii (cn.,) ₀ ,

H CC - "M O-CII- :: Cll _o 0HuMiyl

II., ' : - '.) 'J-CiL, locniel i

However, the Spiroorthcsster structural members can also in the process of layering using the associated monomeric 2-substituted 8,8-dimethyl-9-methacryloyloxy-1,4,6-trioxa-spiro [4.4] nonane, their synthesis in DD 223715 A1 and DD-WP C 07 D / 302 737 4 is introduced into the reactive layer.

The curable layers contain as additives initiators that cause the crosslinking of the layers when exposed to heat or radiation.

As initiators, it is preferred to use arylonium salts, for example diaryliodonium or triarylsulfonium salts, alone or in the presence of rough-flow images, for example benzopinacol, benzoin ethers or benzil ketal. Advantageously, the curable layers 1-5Ma .-% of said initiators.

The free-radically crosslinking monomers used are preferably trimethylolpropane tri (meth) acrylate or pentaerythritol'ira (meth) acrylate, alone or in combination with 2,2-bis [4- (2-hydroxy-3-methacryloyloxypropoxy) phenylpropane (Bis-GMA) , The use advantageously takes place as a solution in monomeric (2-substituted) 8,8-dimothyl-9-methacryloyloxy-1,4,6-trioxaspiro [4.4] nonanes. These solutions are applied to suitable supports and fixed by short-term free-radical crosslinking copolymerization in the form of a reactive layer with spiroorthoester structural members. Preferred free-radically and / or cationically polymerizable monomers are preferably oxiranes, dioxolanes, dioxo (meth) acrylate or glycidyl (meth) acrylate or in combination. The use is advantageously in the form that polymers of formula 1 are dissolved in these monomers and these solutions are used for film formation.

To form curable layers in the form of films, for example, solutions of the components involved in acetone, dichloromethane, toluene and the like may be used. be used. The curing is carried out in such a way that the layers are irradiated with light of the wavelength 250-420nm. The layers are then crosslinked at the sites of light hit, and insoluble.

The irradiation teas are 3-5 minutes when the polymers of formula 1 are used alone. They shorten dramatically (seconds) when oxiranes, such as diandiglycidyl ethers, are included in the layer or when the layer contains bis-GMA and / or trimethylolpropane tri (meth) acrylate or pentaerythritol tetra (meth) acrylate.

If necessary for the application, the unexposed areas of the curable layers can be peeled off. In the case of the use according to the invention, the crosslinking can also be effected thermally, preferably in a temperature range of 80-120 ° C. The process for producing curable layers will be explained below with 3 examples.

embodiments example 1

1.0 g of polymer of the formula (R = CH ₂ OPhenyl) are dissolved in 9.0 g of AZ solvent together with 2% by weight of di-iodoiodonium tolueno-fluoroborate and 5% by weight of benzil dimethyl ketal. With this solution, a film is produced on a chrome-evaporated glass plate. The film is irradiated through a mask for 5 minutes with the unfiltered light of a high pressure mercury lamp HBO 2OC. At the irradiated sites, the reactive layer is crosslinked and on the film, the image of the mask is visible. The uncrosslinked areas of the film can be dissolved away with acetone, toluene or similar solvents.

At game 2

1.5ρ polymer of the formula 1 | R = CH ₂ OCH ₂ CH (CHj) ₂ ), 1.0 g of diandiglycidyl ether and 2.5 g of 2-isobutoxymethyl-8,8-dimethyl-9-methacryloyloxy-1,4,6-trioxaspiro [4.4) nonane are homogeneously dissolved in heat. Before use, 3% by weight ditolyl iodonium hexafluoroantimonate is added. The mixture is brought as a thin layer between quartz / quartz, glass / metal or metal / metal and cured by irradiating with the unfiltered light of HBO 200 for 5 minutes or by heating to 100 ° C for non-transparent parts. The parts to be joined are then firmly connected.

Example 3

1.0 g of 2-methyl-8,8-dimethyl-9-methacn / ioyloxy-1,4,6-trioxaspiro [4.4] nonane are made into a homogeneous solution with a mixture of 10 g of pentaerythritol tetraacrylate / triglycol bisacrylate (in a ratio of 1: 1) prepared and treated with 0.1 g Ditolyliodonium hexafluoroantimonate and 1.0 g of benzil dimethyl ketone. The viscous solution is stirred until complete dissolution of the initiators and is then ready for use. The irradiation time for fixing a layer produced therefrom is 10 s. The complete crosslinking of the spiroorthoester structural members takes place by additional irradiation or heat treatment at 80.degree.

Claims (2)

claims: 1. A process for the preparation of curable layers, characterized in that they contain spiroorthoester structural members and are used after addition of additives in the form of initiators and / or monomers as reactive layers and thermally or radiation-induced ring-opening crosslinking. 2. The method according to claim 1, characterized in that are used as Spiroorthoester structural members Polyspiroorthoester, preferably polymers of formula 1