FI105792B - Method and device for manufacturing contact lenses - Google Patents

Abstract

A measured-out quantity of a material which can be crosslinked by exposure to a suitable form of energy, in particular UV light (3), is introduced into a two-part mould (1), the cavity (15) of which defines the shape of a moulded part (CL) to be produced. The two mould halves (11, 12) are kept at a small distance from each other, so that there is formed between them a thin annular gap (16), which is in connection with the mould cavity (15) and through which excess material can escape. The crosslinkage is initiated by exposure to the chosen form of energy, exposure being spatially limited to the cavity (15) by suitable masking (21), so that material outside the mould cavity is not crosslinked. In this way, moulded parts which do not require secondary finishing are obtained, and the mould is reusable. The process is suitable in particular, but not exclusively, for the production of contact lenses. <IMAGE>

Description

105792

Method and apparatus for making contact lenses

The invention relates to independent claims 1 to 3, respectively. 42 methods and apparatus for making contact lenses according to the preambles *.

5 '·

Contact lenses, which are economically advantageous to manufacture in large quantities, are preferably manufactured in so-called by mold or full mold methods. In these methods, the lenses are made between the two molds in their final shape so that no further processing of the lens surfaces or machining of the edges is required afterwards. Mold-10 methods are described, for example, in PCT patent application WO 87/04390 or EP patent application 0 367 513.

In these known methods, the cavity of the mold determines the geometry of the contact lens to be manufactured. The edge of the contact lens is also usually formed on the basis of a mold consisting of two mold halves. The geometry of the edges is determined by the contours of the mold halves in the area in which they contact each other.

When making a contact lens, a certain amount of fluid starting material is first placed in the female mold half. The mold is then closed with a male mold-20 drop half

Usually, the batch material is overdosed somewhat so that the excess amount · when the mold is closed, penetrates into the overflow space extending out of the mold cavity.

Subsequent polymerization or crosslinking of the starting material is accomplished by irradiation with UV-25 light or heat or other non-thermal method. This hardens both the starting material in the mold and the excess material in the overflow space. The curing of the excess material may be slightly slower, as it may be initially inhibited by oxygen in the air. In order for the contact lens to be properly separated from the excess material, a good seal or displacement of the excess material must be obtained in the contact zone 30 of the mold halves. This is the only way to get flawless contact lenses.

2 105792

Today, plastics, such as polypropylene, are primarily used as the material for the molds.

Molds are made by injection molding and are used only once (disposable molds). This is due to e.g. due to the fact that the excess material contaminates the molds to some extent, the molds are damaged when the contact lenses are removed or they are deformed in some places irreversibly.

Injection molds also have dimensional variations due to variations in the manufacturing process (temperature, pressure, material properties). In addition, the mold may still shrink after injection molding. These dimensional changes in the mold can lead to variations in the parameters (vertical refractive power, diameter, basic curve, average thickness, etc.) of the contact lenses to be improved, which in turn can lead to a deterioration in the quality of the lenses and a consequent decrease in yield. When the sealing between the mold halves is insufficient, the excess material does not separate precisely, which causes the so-called flap formation at the edge of the contact lens. When severely, such a cosmetic defect at the edge of the lens can cause irritation when the lens is used, and such lenses must be distinguished during inspection.

Also, due to the quality requirements for the edges of the contact lenses in particular, these molds are used only once, because a certain deformation of the molds in the contact area cannot be ruled out with certainty.

U.S. Pat. No. 4,113,224 describes another mold method, e.g. for the manufacture of contact lenses. This method uses a mold whose cavity is not completely closed, but is connected through a thin annular space to an annular tank channel (overflow gutter) surrounding the cavity. Through the annular space, material can flow from the container back into the mold cavity during the crosslinking step to compensate for the relatively high shrinkage of the lens material normally used.

The crosslinking of the material in the tank channel can then be prevented by using an inhibitory gas atmosphere or by masking the energy radiation used for the crosslinking. In order to ensure the backflow of material into the mold cavity, the material in the mold cavity is at least initially exposed only to radiation from a central region smaller than the diameter of the mold cavity, or exposed to a higher radiation intensity in the central region than the surrounding edge region. However, after the crosslinking has started in the central region and has progressed to a certain degree, the edge region with its associated ring spaces as well as the material 5 in the tank channel is also exposed to full radiation and crosslinked. In this case, the above-mentioned burr and fin surfaces are inevitably created, in which case the contact lenses or other molded parts manufactured by this known method also require further mechanical treatment.

In addition, EP-A-0 484 015 describes a mold method for raising the lenses of contact lenses. The lens material is fed into the mold cavity, whereby part of the material is introduced into the container in contact with the cavity. The lens material is polymerized by UV light, which can cause the lens to shrink, which is replaced by a file filing from the container. After the photopolymerization, the mold and the Lins material therein are further heated at a temperature of 80 ° C to 90 ° C. The lens blank obtained after opening the mold 15 is then ground to its final shape, in which case special edge machining is required. Economic production without post-processing is therefore not possible with this method.

It is an object of the present invention to further develop and improve the methods and apparatus described so that the effects and problems described above in connection with the manufacture of contact lenses by way of example can be avoided. In particular, conditions must be provided for the re-use of the necessary molds or mold halves and for the formation of burrs and fins on the manufactured contact lenses to be avoided, so that the rejection rate of the contact lenses is very low and no mechanical or other further processing of the contact lenses is required.

This object underlying the invention can be solved by the measures defined in the characterizing parts of independent method claim 1 and independent device claim 42. The dependent claims disclose particularly suitable and preferred embodiments of the method of the invention and the device of the invention.

4 105792 "Crosslinking" as used herein and hereinafter, in short, refers to all reactions in which a material, by polymerizing a suitable monomer, oligomer, and / or prepolymer, and / or a mixture thereof, is brought to a state in which it retains the shape assigned to it by the mold cavity. Suitable materials and polymerization / crosslinking reactions are known to those skilled in the art, and typical examples are described, e.g., in the aforementioned U.S. Patent 4,113,224 and references cited therein.

Thus, according to the general basic idea of the invention, the polymerization or crosslinking of the starting material is limited only to the area of the contact lens to be manufactured. Any additional material present may not be polymerized or crosslinked. In the method according to the invention, the sub-areas of the contact lenses are not formed by a mechanical restriction of the material by the edges of the molds, but by a regional restriction of the energy exposure (usually UV or other radiation) causing the polymerization or crosslinking, by mask masking and / or energy beam path control. . In both preferred embodiments, both of these measures can avoid contact between the mold halves so that they are not deformed and can thus be reused. In addition, the problem of volume shrinkage in crosslinking can now also be managed very simply without the need for further mechanical processing of the molded parts, as in the case of U.S. Pat. No. 4,113,20224: Other features and advantages of the method and apparatus of the invention will become apparent from the following. a detailed description of the working examples, taken with reference to the accompanying drawings, in which:

Figure 1 is a sectional view of a first embodiment of a device according to the invention designed for the method according to the invention with the mold closed;

Figure 2 is an enlarged detail of the symbol II in Figure 1; 30

Figures 3-5 show details analogous to Figure 2 of other embodiments of the device of the invention; 5 105792

Figures 6A-C show another embodiment of a device according to the invention;

Figures 7A-C show another embodiment of a device according to the invention; Figures 8A-C show a modification of the embodiment of Figures 7A-C;

Figures 9A-C show another embodiment of a device according to the invention; and

Figures 10-11 each show a modification of the method according to the invention, in each of which a mold half is used as a package.

The device shown in Figure 1 is designed for the manufacture of contact lenses from a flowable starting material which can be polymerized or crosslinked by UV radiation. It comprises a mold 1 and an energy source 2a shown here in a closed state, here a UV light source, and means 2b for directing energy from an energy source to the mold 1 in the form of a substantially parallel beam 3. Of course, the energy source 2a and the means 2b can also consist of a single unit.

The general structure of the device shown is similar to that of the devices described in the above-mentioned publications related to the prior art, so that in the following description only the essential points and the differences of the invention with respect to the prior art can be limited. Details of the general structure, dimensioning, materials, stability issues, etc., as well as possible materials and methodological aspects of the molded parts are comprehensively discussed in EP-A-0 367 25 513 and in particular in US-A-4 113 224, and thus these publications are incorporated by reference into this client

The mold 1 comprises two mold parts or mold halves 11 and 12, each of which has a curved mold surface 13 and 14, which together define a mold cavity 15, which in turn defines the shape of the contact lens CL to be manufactured. In the drawing, the mold surface 13 of the upper mold half 11 is convex and defines the rear or bottom surface of the contact lens and the associated edge area; this mold half is commonly referred to as 6,105,792 father mold half. On the opposite side, the mold surface 14 of the second mold half, correspondingly referred to as the mother mold surface, is formed concave, and defines the front surface of the contact lens to be manufactured, as well as the associated edge area.

5

In contrast to, for example, the molds known from WO 87/04390 or EP-A-0 367 513, for example, the mold cavity 15 is not completely and tightly closed, but in the embodiment shown in the region of the circumferential edge defining the edge of the contact lens to be manufactured, it is open along its entire length. and communicates therewith with a relatively narrow annular space 16, as is the case with the mold described in U.S. Patent 4,113,224. The annular space 16 is bounded by a flat mold wall 17 and 18, respectively, to the mother mold half Ilja and the mother mold half 12. To prevent complete closure of the mold, the mother mold 12 is provided with spacers consisting of e.g. several spacer pins 19a, 19b in common with the collar or flange 20. keeping the mold halves at such a distance from each other that said ring space 16 is obtained. The spacers may also be adjustable or spring-loaded, as symbolically shown in Fig. 1 in connection with the right spacer pin by a thread. In this way, the mold halves can be moved towards each other during crosslinking by adjusting the spacers (symbolically shown by the turning direction arrow 19c) or against a spring force to compensate for the shrinkage. The mold can, of course, be closed in the usual way by leaving it open, for example here: 'only the closing unit shown by the arrow symbol 1a. The distance adjustment of the mold halves for shrinkage compensation can also be performed, for example, by means of this external closing unit.

25

In another embodiment, not shown here, instead of the through-ring space 16 and the spacers 19a, 19b, several segment-shaped spaces can be used, whereby the spaces between the individual segment spaces take on the function of spacers. It is clear that other types of construction are also possible.

30

Both mold halves 11 and 12 are a material of the selected energy form, here as mentioned, UV light, as permeable as possible, e.g. polypropylene or other polyolefin commonly used for such purposes. Since the irradiation with UV light takes place here only unilaterally, from above, in fact only the upper one, i.e. here the father mold 11 needs to be UV-permeable. In the case of irradiation through the mother mold from below, the situation is of course similar. According to a particularly suitable and preferred embodiment of the invention, at least half of the mold is irradiated with UV light. This material has both particularly good UV permeability and is also very hard and durable, so molds made from this material can be reused very well. However, this requires, as will be described in more detail below, that the mold be closed either without the use of earth or not — completely so that the mold halves are not damaged by contact. As an alternative to quartz, UV-permeable special glasses or sapphires are also possible. Because molds or mold halves are not disposable, there is no need to compromise on manufacturing costs in an effort to provide molds of very high quality and reproducibility. Since the mold halves do not contact each other in the area of the lens to be manufactured, i.e. in the cavity or in the actual mold surfaces, damage caused by the contact cannot occur. For this reason, molds are also very durable. This also has a beneficial effect on the reproducibility of the contact lenses or molded articles produced.

20 In unilateral energy exposure, the mold half on the side away from the energy source can in principle be made of any material that is: compatible with the crosslinkable and crosslinked material or component thereof. However, when using metals, one must always be prepared for reflections that may be due to the type of energy radiation, which could potentially cause harmful effects such as overexposure, edge distortion, etc. Absorbent materials do not have these disadvantages.

Hitherto, the device, and in particular the mold 1, corresponds to that described in the aforementioned U.S. Patent 4,113,224. The most significant and important difference from the present invention is that the exposure of the material from which the molded article is made to the crosslinking energy form is limited to the mold cavity, i.e. only the crosslinkable material in the mold cavity is exposed to a suitable energy form, UV 8 105792 radiation, and only the material in the cavity crosslinks. In particular, it should be noted that the ring space surrounding the mold cavity and any material used in the associated container is not energized and does not network. By mold cavity is meant the void space of a closed mold defined by the perfect shape of the molded body to be molded, in particular the contact lens. The annular space 16 opening into the mold cavity is thus not part of the mold cavity 15.

In order to realize the inventive idea in practice, according to the embodiment shown in Figures 1 and 2, the mold wall 17 of the device is provided with 10 used energy forms, i.e. UV light, impermeable (or at least poorly permeable to the mold permeability) mask 21 extending immediately into the mold cavity. and, except that, prevent irradiated energy from entering any other part of the mold, hollow spaces or surfaces which may come into contact or are in contact at this stage with any fluid and non-crosslinked material which may be in contact. In the method according to the invention, the sub-areas of the lens edge are not formed by limiting the material by means of a mold wall, but by limiting the regional alignment of the radiation or other form of energy which causes polymerization or crosslinking. This is described in more detail below in connection with Figures 2-5.

When using UV light, the mask may preferably be a thin layer of chromium, which can be - produced by methods known from e.g. light or UV lithography. Other metals or metal oxides are also suitable as masking materials. The mask can also be coated with a protective layer which, when the material of the mold or mold half 25 is quartz, is e.g. silica. The mask does not necessarily have to be fixed, but it can also be designed, for example, to be detachable or replaceable. It is also not necessary, although it is recommended that the mask be arranged as shown in Figures 2-5. It can in principle be placed anywhere in the mold as long as it can fulfill its function, namely to cover all mold areas containing non-crosslinked material except the mold cavity. In principle, even the entire mask or mask can be omitted from the mold if it is otherwise possible to limit the energy exposure locally in the mold cavity 9 105792, taking into account the optical effect of the mold. In the case of UV radiation, this can be achieved, for example, by a regionally limited light source, by a suitable lens arrangement, possibly in combination with external masks, dimmers or the like, and taking into account the optical effect of the mold.

5

The individual steps in the manufacture of a contact lens are as follows: - Dispensing of a flowable, non-crosslinked starting material into the female mold half 12 of the opened mold 1. Generally, the dispensing is performed as an overdose, i.e. the dispensed space is greater than the volume of the mold cavity 15 or contact lens CL.

- Closing mold 1. When the mold is closed, the excess material penetrates the annular space 16 between the mold halves 11 and 12. The annular space 16 is chosen so wide or high (Ay) that contact of the mold halves 11 and 12 15 in the area of the mask 21 is avoided with certainty. The control and positioning of the mold halves (distance setting) takes place by means of outer control and response elements, symbolically shown here only by spacers 19a and 19b, which are in principle also known from the devices of U.S. Pat. No. 4,113,224. Typical room heights Ay are in the range of less than about 100 μτη when making contact lenses. Experiments have shown that when using energy radiation in at least one-20 directions, it is possible to achieve a clean edge shape at a space height of about 1 mm. On the other hand, of course, it is also possible: to reduce the width or height of the ring space to virtually zero if only the mold is closed without the use of force, i.e. the mating halves are against each other without external loading. In this case, only a few 25 micrometers thick film of non-crosslinked material remains between the mold halves in the area of the annular space, which, however, due to the covering of UV radiation, cannot lead to the formation of fin surfaces either. Due to the forceless closing of the mold, it was also not damaged, at least by choosing the right material.

30 - Polymerization or crosslinking of a material in a mold cavity 15. Irradiation with UV light (or usually by exposure to a suitable form of energy) results in polymerisation or crosslinking in an area corresponding to the contact lens (or molded article in general).

- Opening the mold and removing the crosslinked lens. After polymerization or crosslinking of the starting material in the mold cavity 15, the mold halves 11 and 12 are separated from each other using a device not shown, and the mold 1 is opened in this way. In this case, the lens CL appears freely and can be removed manually or similarly with a device not shown. In this case, if desired, it is possible to ensure, by means of suitable measures known per se, that the contact lens thus produced is preferably adhered to one of the two mold-side sizes. Suitable measures are described, for example, in U.S. Patent 4,113,224.

Figure 2 shows in more detail and enlarged the structure of the mold 1 in the transition area between the mold cavity 15 and the annular channel 16. Here, by way of example, the cavity 15 has a structure corresponding to the so-called soft contact lens CL typical 15 edge geometry. The cavity, and thus the edge of the lens, is formed here by two mutually perpendicular wall surfaces 22 and 23 formed on the male and female mold halves 11 and 12, respectively. The width and height of these wall surfaces and the contact area of the contact lens defined by them are denoted by X and Y: Yes. In practice, of course, the edge of the lens can also be somewhat rounded.

As can be clearly seen, the cylindrical wall surface 23 of the female mold half 12 does not fully extend to the flat wall surface 22 of the male mold half 11 or to the seamlessly associated wall surface 17, but is less than 25 Ay in height so that the already formed wall halves 11 and 12 tire space 16.

In this embodiment, the mask 21 placed on the wall surface 17 of the parent mold half 11 extends horizontally all the way to the extension 30 23a of the wall surface 23 of the mother mold half 12. When the crosslinking UV light enters as a parallel beam 3 perpendicular to the wall surfaces 22 and 17 or parallel to the cylindrical wall surface 23, the space f 11 105792 perpendicularly below the mask 21 is covered, and only the material inside the cavity 15, i.e. the imaginary wall extension 23a the material inside is networked to create a clean and burr-free lens edge that does not require any mechanical finishing. Thus, when parallel energy radiation is used, the shape of the mask 16 shifts, with the exception of the most often insignificant or— 5 bumping and scattering phenomena, two-dimensionally parallel (here) down to the edge area of the contact lens. Thus, if the mold halves 11 and 12 are separated from each other by a ring space 16 of height Ay, an outer edge is formed in this intermediate region by the effect of local masking of energy radiation.

In principle, it is also possible, in principle, to intentionally use the bending and / or scattering phenomenon to form the desired blurred contour or somewhat rounded edge of the molded part to be manufactured. A similar effect can also be achieved with masks whose permeability changes locally. The sharp edges of the molded article to be made can be rounded as desired by using incomplete crosslinking and dissolving the incompletely crosslinked area with a suitable solvent, which may also be the non-crosslinked material itself. In the case of HEMA (hydroxyethyl methacrylate), e.g. isopropanol is a suitable solvent.

After the molded body thus prepared has been removed from the mold, the non-crosslinked material which may have adhered to it can be simply rinsed off with a suitable solvent, which, depending on the material, may also be water.

In the embodiment of the device according to the invention shown in Figure 3, exposure to the network-causing energy takes place through the mother mold half 12, i.e. in drawing 25 from below. Accordingly, instead of the wall surface 17 of the father mold half 11, the mask 21 is placed on the wall surface 18 of the mother mold half 12. In other respects, the embodiment is in no way different from that of Figures 1 and 2.

In the embodiment of Figure 4, the energy irradiation takes place again from the side of the father mold half 11, and the mask 21 is again on the wall surface 17 of this mold half. However, the mother mold half 12 is not laterally extended, i.e. lacks the cylindrical wall surface indicated by reference numeral 23 in Figure 2. Instead, the ring space 16 12 105792 is formed wider or higher, respectively. Experiments have shown that in the manufacture of contact lenses, in the case of normal proportions, such a structure of the mold also leads to perfect results.

The embodiment of Fig. 5 corresponds to that of Fig. 4 with the difference that the energy exposure again takes place from below through the mother mold half 12, and the mask is placed on the wall surface 18 of this mold half.

It is clear that the exposure of the crosslinkable material in the mold cavity to the energy causing the crosslinking, instead of only one side, can also take place on both sides. One only has to make sure that the energy can only enter the cavity and is effectively kept away from other parts. This can be achieved, for example, by using two or more masks suitably tracked. The mask or masks do not usually have to be on the surfaces of the mold walls, but it is possible to place them inside the mold walls. Preferably, the mask or masks are placed on or just below the wall surface in contact with the non-crosslinked material, as this can prevent harmful bending and scattering phenomena.

According to an aspect of the invention, one of the two mold halves can also be used later as a contact lens package. For this purpose it is possible to use: both the father mold half 11 and the mother mold half 12, the whole mold only needs to be formed in a corresponding manner. This is shown in Figures 10 and 11, in each of which a mold half (in Figure 10 the father mold half 11, in Figure 11 the mother mold half 12) is used later as a package. This mold half is suitably formed into a disposable mold half, while correspondingly the other mold half may be formed into a multi-use mold half (e.g. made of quartz or sapphire). The mask 21 is in each case positioned in a multi-purpose mold half size. Exposure to the energy in the form of a UV beam 3 takes place in each case through 30 halves of the multi-purpose mold which are highly permeable to energy radiation (excluding the masked areas). In order for the lens formed by the shape of the cavity 15 to adhere to the disposable mold half after polymerization, this disposable mold half may be pretreated accordingly. After polymerization, the excess and non-polymerized material in the region of the mask 21 can then be removed from this mold half. The poly-merized lens attached to the disposable mold half can be hydrated in this mold half during further processing if hydration is necessary. The finished 5 lens is subsequently packaged in a disposable mold half, whereby the disposable mold half is sealed and sealed with a cover film.

One problem with previously known manufacturing methods is that air closures can form when the mold is closed. However, the consequence of air closures is that the 10 lenses are rejected in a subsequent inspection (quality control). Until now, the mold has correspondingly been closed slowly in order to allow the most complete escape of air from the mold cavity. However, such a relatively slow closure of the mold requires a correspondingly relatively long time.

According to a further aspect of the invention, it is thus advantageous to provide a method and a device according to the type definition which have a good efficiency, i.e. the mold can be utilized efficiently and at a relatively low cost, but always requiring that the molded parts produced (e.g. contact lenses) ) there are no air closures.

20

According to the method of the invention, this is achieved in such a way that the filling of the mold cavity takes place in a starting material which is at least partially still in a non-crosslinked state. This achieves the fact that when filling the mold, there can no longer be air in the mold from the very beginning, thus correspondingly avoiding air closures. As a result, the mold can be closed more quickly, and therefore can be utilized more efficiently and at the same time at a relatively very low cost. In other respects, in this way ^ · the exact dosage of the required amount of starting material is also obtained automatically, since the filling takes place in the starting material.

In one alternative of the method, the mold cavity may be contacted to fill it with the surrounding container in which the starting material is made and from which the mold cavity is filled. This is a technically particularly advantageous method alternative.

14 105792

In another method alternative, the mold is also sealed in the starting material to prevent the possibility that air could somehow enter the mold cavity during the sealing procedure.

In one alternative, a mold is used which comprises a container and a mold part which is displaceable in this container. This mold part can be moved away and towards the container wall opposite it to open and close the mold. During mold opening, the starting material flows between the container wall and the mold part, and during mold closing, the starting material flows away again. By moving the movable mold part away from the opposite tank wall, the space between the movable mold part and the tank cavity is filled with starting material without air entering the space.

The movable mold part is then guided towards the wall of the container by moving the starting material between the mold part and the container pin again, whereby the material in the mold body naturally remains therein. Also, when the mold part is moved towards the cavity wall, no air can enter the mold cavity, and thus air-seal-free molded parts can be produced in a simple and efficient manner.

For example, a mold having two mold halves may be used, with one mold half 20 located in the wall of the container and the other in the movable mold part. In this case, a mold with a parent mold half and a mother mold half can be used, wherein: the father mold half is placed in the tank wall and the mother mold half in the movable mold part for pumping in and out of the starting material can be advantageously used. In another preferred method alternative, pistons can be used to feed in and out of the starting material.

r * The crosslinked molded part can be removed from the mold in a particularly simple manner by rinsing the mold with the starting material. This can be done, for example, by removing the molded body from the mold when the mold is opened by the flow of starting material 30 and rinsing it out of the mold when closing the mold.

15 105792

In one method variant, the mold is opened and closed again during the first cycle. This is followed by at least the crosslinking required to remove the molded part from the mold by exposure to energy. During the second cycle, the mold is reopened, removing the molded body from the mold. The piston-like mold part 5 is then moved again towards the opposite container wall, i.e. the mold is closed again, whereby the crosslinked molded body is flushed out of the mold. This "two-cycle" variant of the method is characterized in that the molded part is made in the first cycle, after which it is rinsed out of the mold during the second cycle. During the "rinsing cycle", the mold can be cleaned at the same time.

10

The method alternative described above can be carried out either by first having a "manufacturing cycle" (first cycle) and then a separate "rinsing cycle" (second cycle, e.g. with rinsing liquid), or by rinsing together with a new molded article manufacturing cycle, i.e. with a new mold cavity. with the starting material, the molded article made in the previous section is rinsed out of the mold. The "two-cycle" option of the method then becomes the "one-cycle" option.

However, the crosslinked molded article can also be removed from the mold with a gripping device. This can take place in such a way that the molded body 20 lifted from the mold by the gripping device is placed in the movable mold part in a space outside the movable mold part and the container wall opposite it. The shaped body placed in the movable mold part can then be attached to it under reduced pressure and then removed therefrom under overpressure.

25 In one method variant, the mold is not completely closed after the starting material has been introduced into the mold cavity, but the ring space surrounding the mold cavity * and associated with the non-crosslinked starting material remains open. In this case, on the other hand, the shrinkage of the volume caused by the crosslinking can be compensated so that more starting material flows into the mold cavity through the annular space. On the other hand, it also prevents the mold halves from being tightly compressed during the manufacture of the molded part. In particular, due to the risk that the mold halves will be irreversibly deformed by mechanical stress, 16,105,792 mold halves have so far been used only once, as described above. According to this method variant, it is possible to use the mold halves several times.

It is also conceivable for the mold to be closed as the crosslinking shrinkage of the material progresses.

In any case, it is important that at least a rigidly flowing starting material is used prior to crosslinking so that the starting material used to compensate for shrinkage can flow through the annular space into the mold cavity.

The device of the invention solves the problems associated with possible air inclusions by placing the mold cavity in a starting material which is at least partially still in a non-crosslinked state. This ensures that when the mold is filled, there can no longer be air in the mold from the beginning, thus correspondingly avoiding air entrapment. As a result, the mold can be closed more quickly, and thus utilized more efficiently and at the same time at a relatively very low cost.

In one embodiment, the apparatus includes a container surrounding the mold cavity for making the starting material. This container can be connected to the mold cavity. When filling the mold cavity, the container is connected to the mold cavity and filled with the starting material.

In this case, several structurally particularly simple embodiments are possible, which will be described in more detail below.

25

In one embodiment, the device comprises means for closing the mold placed in the starting material, whereby also in this case the mold is always closed in the starting material, so that no air can remain in the mold cavity.

In a preferred embodiment, the mold comprises a container and a mold part which is displaceable in this container, which can be moved away and towards the wall of the container opposite it in order to open and close the mold. The container is provided with 17 105792 inlets, from which, during the opening of the mold, the starting material flows in between the wall of the container and the mold part. In addition, the container is provided with an outlet from which the starting material flows out again during the closing of the mold. This embodiment is structurally relatively simple and thus quite inexpensive, 5 and therefore very suitable for practical applications.

ί; ·, .ϊ.

r The mold then preferably has two mold halves, the other mold half; one is placed in the wall of the container and the other in the movable mold part. The mold has (especially when making contact lenses) a father mold half and a mother mold half. In this case, the father mold half is preferably placed in the tank wall and the mother mold half in the movable mold part. In this design, the molded parts (contact lenses) can later be removed in a particularly simple manner.

Pumps are preferably used to feed in and out of the starting material, by means of which the starting material is fed between the container wall and the mold part when the mold is opened from the inlet point and again discharged through the outlet point when the mold is closed. Such pumps operate reliably and thus do not incur any special costs.

In one embodiment, the piston-like movable mold part is provided with drive means. These can be located either in a device operating without pumps or in a device equipped with pumps for moving the piston-like movable mold part in the direction of the opposite tank wall and for pushing out the starting material between the mold halves again.

25

In one embodiment, the device is provided with flow generating means. This flow detaches the molded body when the mold is opened from the mold and flushes it out of the mold when the mold is closed. These means may be formed as nozzles or similarly functioning means. It is important that they provide a flow or vortex flow of starting material between the mold-30 halves so that the molded body (contact lens) is released from the mold halves by flow or vortexing.

18 105792

In one embodiment of the device, in the first stage ("manufacturing cycle"), the starting material flows first between the container wall and the movable mold part via the inlet and then again through the outlet. The amount of energy required to cure the molded body from the energy source is then applied to effect crosslinking. Then, in a second section, the starting material flows again between the tank wall and the movable mold part through the inlet, and it removes the molded part from the mold and rinses it out via the outlet.

This "two-cycle" device is characterized in that the shaping of the molded part takes place in the first cycle, after which it is rinsed out of the mold in the second cycle (rinsing cycle, cleaning cycle), whereby the mold is also cleaned at the same time.

The device may be configured to use first a "fabrication cycle" and then a separate "rinse cycle" (second cycle) as described, but it may also be configured to co-rinse with a new molded article fabrication cycle, i.e. a new while filling the starting material into the mold cavity, the molded body made in the previous section is rinsed out of the mold at the same time. A "dual-cycle" device thus becomes a "single-cycle" device. However, in a "single-cycle" apparatus, the starting material must be used for rinsing, while in a "two-cycle" device it is also possible to use a specific cleaning fluid.

• ’

To remove the molded part, a gripping device can be used to remove the crosslinked molded parts from the mold. Preferably, for this purpose, the wall 25 of the container has a recess in a different wall than the wall provided with the mold, which extends substantially in the direction of movement of the movable mold part. The gripping device is placed in this * recess. The movable mold part has a recess in the outer wall which is not located opposite the container wall provided with the mold, into which the gripping device places the removed molded part. This is a structurally special purpose-simple and simple design of the device.

i 19 105792

The device can still be further formed in such a way that the movable mold part has a channel leading to its recess, which can be connected to a source of overpressure or underpressure. The channel is when the gripping device places the mold part of the removed molded part at the cause? connected to a vacuum source. To remove the lens, it is then connected to 5 overpressure sources. Thus, the lens can be manufactured during one cycle and removed during the second cycle, placed in the mold part, and then removed from the mold part. This is possible both in a device formed as a "two-cycle" device and in a device formed as a single-cycle device.

ilpilSSS * 1 '_ 10 In one embodiment of the device, the mold is provided with spacers which hold I ..s.

1! 'mold halves in a closed mold at a small distance from each other so as to form a ring space surrounding and associated with the mold.

! j- * V:. · In this way, on the one hand, the space occurring in connection with the crosslinking can be compensated for, since new starting material can flow into the mold cavity through the ring space. On the other hand, it is also prevented that the mold halves are pressed tightly against each other during the production of the molded part. In particular, due to the risk that the mold halves would be irreversibly deformed by mechanical stress, the mold halves have hitherto been used only once, as described above 20. Using this embodiment of the device, it is possible to use the mold halves several times. • that the device is provided with flexible means or adjustment means which allow the interlocking shrinkage of the mold halves corresponding to each other.

The method and the devices described make it possible to produce specially shaped bodies, in particular optical lenses, and specifically contact lenses.

The embodiment of the device according to the invention shown in Figures 6A-C is intended for the production of contact lenses from a flowable starting material which can be polymerized or crosslinked, e.g. by means of UV radiation. In Figure 6A, the mold 1 is seen in a closed state. The mold 1 is placed in a container 10 filled with a non-crosslinked flowable starting material M. The device further comprises an energy source consisting of a UV light source 2a and means 2b for directing the energy generated by the UV light source in a parallel beam 3 to the mold 1. These means 2a may also include in particular 2a a dimmer traced between the UV light source 2a and the container 10. The UV light source 2a and the means 2b can, of course, also consist of a single unit.

The mold 1 comprises two mold halves 11 and 12, each of which has a curved mold surface 13 or 14, which together define a mold cavity 15, which in turn determines the shape of the contact lens CL to be manufactured. The tip 13 of the mold-10 of the upper mold half 11 is concave and defines a front surface and an associated edge area. This mold half is usually called the mother half. The mold surface 14 of the lower mold half 12 is convex and defines the rear or bottom surface of the contact lens CL and the associated edge area. This mold half 12 is commonly referred to as the father half.

The space between the mold halves 11 and 12 and thus also the mold cavity 15 is placed in the non-crosslinked starting material M throughout the manufacturing process. According to the inventive idea, at least the mold cavity is always placed in the completely non-crosslinked starting material during filling. It can be seen from Fig. 6B that even in the open state, the upper mold half 11 does not completely protrude from the starting material-strip M, and the space between the mold halves 11 and 12 always remains below the liquid surface of the starting material M in the container 10. Thus, the space between the mold halves, and in particular also the mold cavity, is in constant contact with the starting material M in the container 10. In this way, no air can enter between the mold halves 11 and 12 at any stage.

25

Once the mold cavity is filled with the mold closed (Fig. 6A), UV irradiation is performed, and crosslinking of the molded body is thus obtained.

After crosslinking, the mold is opened and the molded article 30 in the form of a contact lens CL is removed from the mold, i.e., detached and removed from the mold. Fig. 6C shows a gripping device 4 for this purpose, which, after lifting the upper mold half, removes the contact lens CL from the parent mold half 12 (Fig. 6B) and removes 21 105792 from the mold (Fig. 6C). However, the removal and removal of the contact lens or molded part from the mold can also take place in other ways, as will be described in connection with other embodiments. After removing the contact lens or molded part, the mold can be closed again and a new contact lens can be made.

5

Since the entire manufacturing process according to Figures 6A-C takes place below the liquid surface of the starting material M in the container 10, no air can enter between the mold halves 11 and 12 and in particular the mold cavity 15. Because the mold is opened and closed below the liquid surface, the mold can also be closed relatively quickly, which has not been possible with prior art methods and devices. In this way, contact lenses without any air closures can be produced efficiently and at low cost.

In addition, in the embodiment shown in Figures 6A-C, the irradiation of the material 15 with UV radiation is also limited to the mold cavity 15, for which reason only the material in the mold cavity 15 crosslinks. In particular, no energy is applied to the starting material in the annular space 16 surrounding the mold cavity 15 and elsewhere in the container 10 and it does not crosslink. By mold cavity is meant herein the empty space of the closed mold which defines the complete shape of the molded article to be manufactured, in particular the contact lens CL. The annular space 16 opening into the mold cavity thus does not belong to the mold cavity 15.

In the practical implementation, according to Figures 6A-C, a spent energy, i.e. here UV light, impermeable (or at least poorly permeable to the mold permeability) mask 21 is placed in the mold wall 17 in the area of the annular space 16, extending immediately to the mold cavity and blocking irradiated energy «Access to all other parts of the mold, hollow spaces or surfaces which may come into contact or are in contact at this stage with fluid and non-crosslinked, possibly excess material. The sub-areas of the lens edge are not formed by limiting the material by the mold wall, but by limiting the spatial alignment of radiation or other forms of energy that cause polymerization or crosslinking. The side edges of the upper mold half are also provided with a mask 21 to prevent the starting material surrounding the mold in the container 10 from crosslinking.

Figures 7A-C show another embodiment of a device according to the invention. In this embodiment, the second mold half, here the parent mold half, is formed by the wall of the container 10a, here the bottom 100a of the container. The parent mold half is thus formed directly on the bottom 100a of the container. In addition, the container 10a is provided with a piston-like movable mold part 11a, which can be moved away from the container wall opposite it, here the container bottom 100a, and again back to the container bottom sealingly along the side walls of the container. In this way, the mold can be opened and closed. The container bottom surface 17a of the mold part 11a is correspondingly formed as a mother mold half. The container base 100a and the mold surface 17a define the mold cavity 15a of the mold in the closed state (Figure 7a). It is clear that the mold part does not necessarily have to be piston-shaped, a membrane to which the drip half of the mold-15 is attached could just as well be used. Other volume change arrangements are also possible.

An inlet 101a is traced into the container 10a, here to the container bottom 100a, through which the starting material can flow into the space between the mold part 11a and the container wall 100a. To this end, the space between the mold part 11a and the tank wall 100a is permanently connected to the tank R. By means of pumps P1 and P2 in the inlet 101a and the outlet 102a, the starting material can be led into and out of the space between the mold part 11a and the tank base 100a. the space between the tank bottom 100a is always filled with the starting material M, so that no air can enter the space. Pumps P1 and P2 are shown with integrated non-return valves, but pumps without integrated non-return valves can also be used, in which case they are connected between the pump and the tank, or, depending on the type of pump, such non-return valve can be omitted altogether.

When the mold is closed (Fig. 7a), it is exposed to energy, here again to UV radiation. Here, too, the energy exposure of the mold takes place from above. This provides networking. The crosslinked molded body CL is then removed and removed from the mold. To this end, first, 101a of the feedstock 105a is fed from the feed 101a to the space M between the container wall 100a and the mold part 11a, and the piston-shaped mold part 11a is moved upwards (Fig. 7b). The molded part, here the contact lens CL, can now be removed and removed from the mold. This can take place, for example, with a special gripping device, as already described in connection with Figure 6. However, the contact lens CL 5 can also be rinsed out of the mold, as will be explained in more detail below.

The piston-moving mold part 11a is then moved down again, and the material between the mold part 11a and the container bottom 100a is discharged through the outlet 102a 10 (Fig. 7c). Material removal can be performed with a pump P2 tracked for removal.

In principle, it is conceivable here that the driving force of the piston-moving displacement mold part 11a is only between the mold part 11a and the tank bottom 100a and the liquid starting material 15 is fed in it, whereby the pumps P1 and P2 produce the necessary operating energy. It is also conceivable that the pumps are not used at all, and the piston-moving mold part 11a is driven mechanically, and that during the upward movement the starting material is sucked in and during the downward movement the starting material is pushed out again. It is clear that a combination of pumps and mechanical drive can also be used.

: A mask 21a is placed in the mold part 11a. It extends, as in the upper mold part 11 of Figures 6A-C, over the annular space 16a to the mold cavity 15a and possibly along the side wall of the piston-shaped mold part 11a. When the mold is then irradiated with UV radiation 3, networking takes place in the area of the mold cavity 15a and only there and thus the formation of the molded body. In other areas, in particular in the ring space 16a and in the tank 10a, the other starting material does not crosslink. The materials, fabrication, and placement of such masks are subject in principle to the same considerations as those already made in connection with the description of Figures 6A-C.

Figures 8A-C show an embodiment of the device, which in principle corresponds to the embodiment of Figures 7A-C. However, the difference is that in the example of the embodiment of Figures 8A-C 105792, the outlet 102a does not have a pump P2, but the outlet 102a is formed as a deformable tongue or a plate or flap. The following description of Figures 8A-C focuses mainly on removing the molded body, here the contact lens CL, from the mold. The filling of the mold cavity 15a takes place analogously to the directing example of Figs. 7A-C by means of the pump P1. When the mold is closed (Fig. 8A), the contact lens CL is made by crosslinking so that the mold is irradiated with UV radiation 3.

As the piston-shaped mold part 11a is moved upwards (Fig. 8b), a flowable starting material flows into the container 10a 10 between the container base 100a and the piston-like movable mold part 11a. The inlet 101a may be formed as a nozzle or a flow generating means operating in a similar manner. When passing the flowable starting material through the inlet, the obtained flow is detached from the mold of the crosslinked contact lens CL and, under the effect of the corresponding arrangement of the nozzle, flushes it in the direction of its discharge. It is here formed as a shape-changing language or disk.

The pressure generated when the piston-shaped mold part 11a is moved downward (Fig. 8C) turns the tongue downwards and opens the outlet 102a, whereby the liquid starting material of the contact lens CL can be flushed out through the outlet 102a. The contact lens can be trapped in a sieve S which passes through the flowing starting material. For example, the starting material can be recycled and reused, possibly after purification. During the rinsing of the contact lens, the mold cavity 15a is filled with a new starting material, so that the new contact lens CL can be immediately crosslinked by irradiation with UV light 3.

It has been described above that for removal and rinsing, a flowable starting material is fed to the container 10a, the mold cavity 15a is refilled in the same section, and the mold is again irradiated in a closed state with UV radiation 3 to crosslink and manufacture the next contact lens CL. The device thus functions as a seemingly "single-cycle" device. Namely, in each section (upward and downward movement of the piston-like mold part 11a) a contact lens is manufactured and rinsed out of the mold.

30

However, it is also conceivable that the contact lens is manufactured in a first stage ("manufacturing cycle"), i.e., the piston-like mold portion 11a is moved upward, flowing starting material flows between the mold portion 11a and the container base 100a, and the mold portion 11a is then radiated downward again. then in a closed 4 · state with UV radiation 3, whereby crosslinking takes place and a contact lens CL is formed.The contact lens can now be rinsed from the mold in a special second section ("rinsing-5 section") without making a new contact lens in this second section, while in a "single-section" In a "two-cycle" device, both a flowing starting material and, in particular, a special cleaning fluid can be used for rinsing, which is advantageous in that the mold can be cleaned particularly well during the rinsing cycle before the next 10 stages flow in again. material and the following contact lens CL is prepared.

Thus, in the embodiment of Figures 8A-C, it is possible to apply a "single-cycle" procedure (a contact lens is made in each cycle) and a "two-cycle" procedure (in the first cycle a contact lens is made, in the second cycle it is rinsed out and the mold is cleaned without a new contact lens).

15

Figures 9A-C show another embodiment of the device according to the invention. This embodiment corresponds in principle to the embodiments described in connection with Figures 7A-C and 8A-C, but differs significantly from them in that it has a slightly different structure of the piston-displaceable mold part 11b. The container 10b is also significantly different in structure in that its side wall 103b is provided with a recess 104b extending in the direction of movement of the piston-like mold part 11b. A gripping device 4b is placed in this recess 104b. The wall 113b of the mold part 11b has a recess 114b just where the recess 104b in the side wall 103b of the container 11b is located. The mold part 11b 25 further has a channel 115b which can be connected to a vacuum or overpressure source P3. The gripping device 4b can also be connected to this vacuum or overpressure source P3.

«

The fabrication of the contact lens CL by irradiating the mold with UV radiation 3a again takes place in the same manner as described above in connection with Figs. 7A-C and Figs. 8A-C. Thus, the description of Figures 30A-C focuses primarily on the method of removing the contact lens CL. The mold is again irradiated closed with UV radiation and the contact lens CL is made by crosslinking (Fig. 9A). The starting material 26 105792 is then pumped by the pump P1 between the mold part lib and the tank bottom 100b, and the mold part 11b is moved upwards (Fig. 9B). At this point, the gripping device 4b pivots from the recess 104b onto the contact lens CL. The gripping plate 40b of the gripping device 4b has a bore through which it is now connected to the vacuum source P3 so that the contact lens can be detached and sucked 5 against the gripping plate 40b. After the contact lens CL is absorbed into the gripping plate 40b, the gripping device 4b is turned back into the recess 104b, and the mold part 11b is moved downward again. In this case, the liquid starting material between the mold part 11b and the container base 100b is sucked out by the pump P2 (Fig. 9C).

The gripping device in the recess 104b then slides along the outer wall 113b of the mold part 11b or is held in the recess 104b until the gripping plate 40b is opposite the recess 114b of the outer wall of the mold part 11b. At this time, an overpressure is applied to the gripping plate 40b through the bore, so that the contact lens CL detaches from the gripping plate 40b and moves into the recess 114b. Namely, a vacuum is applied to the channel 115b leading to the recess 114b at the same time as the contact lens CL detaches from the gripping plate 40b, whereby the contact lens CL moves from the gripping plate to the recess 114b in a simple manner (Fig. 9A).

When the mold part 11b is moved upwards, the recess 114b of the mold part 11b is above the container 10b 20 (Fig. 9B). When an overpressure is now introduced through the channel 115b, the contact lens CL detaches from the recess 114b and can be subjected to further processing. In this connection, it should be noted in particular that the side wall 103b may extend even further upwards and may have a further extension S3 'into which the contact lens CL can be moved or rinsed. In this case, an even better movement fit of the mold part 11b and protection of its sealing surfaces 25, which slide along the container wall, is achieved.

In order to generate overpressure and underpressure, a pump P3 is used in Figures 9A-C, the overpressure connection HP or the underpressure connection NP of which is always connected to the channel 115b or the bore of the gripping plate 40b, depending on the position of the piston-moving mold part 11b. This pump P3 can suck from the tank R in which the starting material is produced the starting material with which the required pressure is generated. Figures 9A-C show two separate tanks at inlet 101b 27 105792 and outlet 102b into which pumps P1 and P2 and P3, respectively, extend, but it is clear that only a single tank can be used here.

In this connection, it should also be noted that the embodiment of Figures 9A-C can also function as both a "single-cycle" device and a "two-cycle" device. However, in a "single-cycle" device, it must be ensured that only the starting material always flows into the tank 10b. In the "two-cycle" device, on the other hand, a cleaning liquid can be supplied in the second cycle, in which the contact lens CL is then removed.

Furthermore, it is clear that the device described in connection with the images may have several per cavity instead of only one cavity, so that several contact lenses can be manufactured during one period. This option is especially effective.

Furthermore, in an embodiment where a piston-shaped mold part is used, the flow can be intentionally adjusted by first applying a mechanical force to the piston-shaped mold part and releasing the starting material somewhat in a slow manner into the container or slightly out of the container during feeding. This also applies to the option of using both pumps and piston mechanically. By these measures, a vacuum can be intentionally created in the tank at the inlet 20 and an overpressure at the outlet, or the pressure of the tank can generally be adjusted.

‘In addition, an option is also conceivable in which the number of cycles after which a new contact lens is always manufactured can be changed. For example, a detector may be used to indicate whether the contact lens has also actually been flushed out of the mold, and only when the detector has detected such a flushed contact lens will the mold be completely closed and a new contact lens made. If the detector has not detected a rinsed contact lens, continue rinsing the mold until the contact lens has rinsed out of the mold.

As the starting material for the contact lenses, which can be crosslinked by irradiation with UV light, for example, HEMA (hydroxyethyl methacrylate) or poly-HEMA, which is frequently used for this purpose, can be used, in particular in admixture with a suitable crosslinker 28 105792, such as ethylene glycol dimethacrylate. In connection with other molded parts, other crosslinkable materials are always used according to the intended use, in which case other forms of energy can be used to perform crosslinking depending on the type of crosslinkable material, e.g. electron beam, gamma radiation, thermal energy, etc. Contact lenses are usually UV-crosslinkable starting materials. ordinary but not mandatory.

According to an aspect of the invention, specific prepolymers, in particular those based on polyvinyl alcohol, which contain cyclic acetal groups and crosslinking groups, can also be used as starting material.

Contact lenses based on polyvinyl alcohol are already known. Thus, for example, EP 216 074 describes contact lenses containing polyvinyl alcohol having (meth) acryloyl groups bonded via urethane groups. EP 189 375 describes contact lenses made of polyvinyl alcohol crosslinked with polyepoxides.

In addition, a few specific acetals containing crosslinking groups are also known. In this connection, reference is made, for example, to EP 201 693, 215 245 and 211 20 432. EP 201 693 describes, inter alia, acetals of straight-chain aldehydes having 2 to 11 carbon atoms and an amino group at the end, which amino group is substituted with an unsaturated organic radical. This organic radical has a functionality that attracts the electrons of the nitrogen atom, and the olefinically unsaturated functionality is polymerizable. EP 201 693 also relates to the reaction products of the acetals characterized above with 1,2-diol, 1,3-diol, polyvinyl alcohol or cellulose. However, such products have not been concretely described.

When acetals according to EP 201 693 are mentioned at all in connection with e.g. polyvinyl-30 alcohol - such as e.g. in Example 17 of the patent application, then the acetal to be polymerized via its olefinic groups is first copolymerized with e.g. vinyl acetate. The copolymer thus obtained is then allowed to react

- I

29 105792 with polyvinyl alcohol, and a 37% solids emulsion with a pH of 5.43 and a viscosity of 11640 cps is obtained.

In contrast, the present invention relates to prepolymers having a 1,3-diol-5 backbone, wherein a certain percentage of the 1,3-diol units can be modified to 1,3-dioxane having a polymerizable but non-polymerized residue at the 2-position. In particular, a polymerizable residue is an aminoalkyl residue having a polymerizable group attached to a nitrogen atom. This invention also relates to homopolymers and copolymers of said prepolymers, to a process for the preparation of new prepolymers and homopolymers and copolymers obtained therefrom, to molded articles made from these homopolymers and copolymers, and to a process for the production of contact lenses using said homopolymers.

The chip polymer according to the invention is preferably a derivative of a polyvinyl alcohol having a molecular weight of at least about 2000, containing from about 0.5 to about 80%, based on the number of hydroxyl groups of the polyvinyl alcohol, of units of formula I | | Wherein R is lower alkyl up to 8 carbon atoms, R 1 is hydrogen or lower alkyl and R 2 is olefinically unsaturated, electron withdrawing, copolymerizable residue, preferably having carbon atoms up to 8 carbon atoms Up to 25.

R2 is, for example, an olefinically unsaturated acyl residue of the formula R3-CO-, wherein R3 is an olefinically unsaturated copolymerizable residue having 2-24 30 30 105792

carbon atoms, preferably 2 to 8 carbon atoms, particularly preferably 2 to 4 carbon atoms. In another embodiment, R 2 is a residue of formula II

-C0-NH- (R4-NH-CO-O) q-R5-O-C0-R3 (II) 5 wherein q is zero or one, and R4 and R5 are independently lower alkylene of 2-8 carbon atoms, 6- Arylene of 12 carbon atoms, a saturated divalent cycloaliphatic group of 6 to 10 carbon atoms, arylene alkylene or alkylene arylene of 7 to 14 carbon atoms, or arylene alkylene arylene of 13 to 16 carbon atoms, and wherein R 3 is as defined above.

The prepolymer according to the invention is thus in particular a derivative of polyvinyl alcohol having a molecular weight of at least about 2000, containing about 0.5 to about 80%, based on the number of hydroxyl groups of the polyvinyl alcohol, of units of formula III \ ch ^ CH2 \ ch ^ CH2 \ 20 ° \ ch / (m) I / R '

R-NC

: [C0-NH- (R4-NH-CO-O) q-R5-01rCO-R3 wherein R is lower alkylene, R1 is hydrogen or lower alkyl, p is zero or one, q is zero or one, R3 is an olefinically saturated copolymerizable residue having 2 to 8 carbon atoms, and R 4 and R 5 are independently lower alkyl of 2 to 8 carbon atoms, arylene of 6 to 12 carbon atoms, a saturated divalent cycloaliphatic group of 6 to 10 carbon atoms, arylene alkylene of 7 to 14 carbon atoms, alkylene or alkylene or arylenealkylene arylene of 13 to 16 carbon atoms.

31 105792

In lower alkylene, R preferably has up to 8 carbon atoms and may be straight-chain or branched. Suitable examples are octylene, hexylene, Pentylene, butylene, propylene, ethylene, methylene, 2-propylene, 2-butylene or 3-pentylene. Preferably in lower alkylene R has up to 6 carbon atoms 5 and particularly preferably up to 4. Particularly preferably it is methylene and butylene.

R 1 is preferably hydrogen or lower alkyl up to seven, in particular up to four, carbon atoms, in particular hydrogen.

10

In lower alkylene, R4 or R5 preferably has 2 to 6 carbon atoms and is particularly straight-chain. Suitable examples are propylene, butylene, hexylene, dimethylethylene and particularly preferably ethylene.

Arylene R4 or R5 is preferably phenylene which is unsubstituted or! substituted by lower alkyl or lower alkoxy, in particular 1,3-phenylene or 1,4-phenylene or methyl-1,4-phenylene.

A saturated divalent cycloaliphatic group R4 or R5 is preferably cyclohexylene or cyclohexylene lower alkylene, e.g. cyclohexylene methylene, which is unsubstituted or substituted by one or more methyl groups, for example trimethylcyclohexylene methylene, e.g. a divalent isophorone residue.

The arylene unit of alkylene arylene or arylene alkylene R4 or R5 is preferably phenylene, unsubstituted or substituted by lower alkyl or lower alkoxy, its alkylene unit being preferably lower alkylene, such as methylene or ethylene, especially methylene. The radicals R4 and R5 are then preferably phenylene methylene or methylenephenylene.

Arylenealkylene arylene R4 or R5 is preferably phenylene-lower alkylene-phenylene having up to 4 carbon atoms in the alkylene unit, e.g. phenylene-ethylenephenylene.

32 105792 The radicals R4 and R5 are, independently of one another, preferably lower alkylene of 2 to 6 carbon atoms, phenylene, unsubstituted or substituted by lower alkyl, cyclohexylene or cyclohexylene-lower alkylene-aliphenylene-aliphenylene-aliphenylene-aliphatic-alkylene -phenylene.

The term "lower" in the context of this invention means, in connection with residues and compounds, unless otherwise specified, radicals or compounds having up to 7 carbon atoms, preferably up to 4.

10

Lower alkyl has in particular up to 7 carbon atoms, preferably up to 4, and is e.g. methyl, ethyl, propyl, butyl or tert-butyl.

The lower alkoxy has in particular up to 7 carbon atoms, preferably up to 15 to 4, and is e.g. methoxy, ethoxy, propoxy, butoxy or tert-butoxy.

The olefinically unsaturated copolymerizable residue R3 of 2 to 24 carbon atoms is preferably alkenyl of 2 to 24 carbon atoms, especially alkenyl of 2 to 8 carbon atoms, and particularly preferably alkenyl of 2 to 4 carbon atoms, e.g. ethenyl, 2-propenyl, 3-propenyl, 2-butynyl. hexenyl, octenyl or dodecenyl. Preferred are ethenyl and 2-propynyl, where the group -CO-R3 represents an acrylic acid or methacrylic acid: acyl residue

The divalent group -R4-NH-CO-O- occurs when q is one and is absent when q is zero. Prepolymers where q is zero are preferred.

The divalent group -CO-NH- (R4-NH-CO-O) q-R5-O- occurs when p is one and is absent when p is zero. Prepolymers where p is zero are preferred.

In a prepolymer where p is one, the subscript q is preferably zero. Particularly preferred are prepolymers in which p is one, the subscript q is zero and R 5 is lower alkylene.

33 105792

Thus, a preferred prepolymer according to the invention is in particular a derivative of a polyvinyl alcohol having a molecular weight of at least about 2000, containing from about 0.5 to about 80%, based on the number of hydroxyl groups of the polyvinyl alcohol, of units of formula III wherein R is lower alkylene up to 6 up to carbon atom, p is zero and R3 is alkenyl of 2 to 8 carbon atoms.

Thus, another preferred prepolymer of the invention is ----- especially polyvinyl alcohol having a molecular weight of at least about 2000. .. a derivative containing from about 0.5 to about 80%, hydroxyl-10 of polyvinyl alcohol. based on the number of groups, units of formula III in which R is lower alkylene up to 6 carbon atoms, p is one, q is zero, R 5 is lower by 2-6 carbon atoms! o alkylene and R 3 is alkenyl of 2 to 8 carbon atoms.

Thus, another preferred prepolymer of the invention is, in particular, a derivative of a polyvinyl alcohol having a molecular weight of at least about 2000, containing from about 0.5% to about 80%, based on the number of hydroxyl groups in the polyvinyl alcohol, wherein R is lower alkylene up to 6 up to 1 carbon atom, p is one, q is one, R 4 is lower alkylene of 2 to 6 carbon atoms, phenylene, unsubstituted or substituted by lower alkyl, cyclohexylene or cyclohexylene-lower alkylene, unsubstituted or substituted by lower alkylene, lower alkylene, phenylene-lower -phenylene or phenylene-lower alkylene-phenylene, R 5 is lower alkylene of 2 to 6 carbon atoms and R 3 is alkenyl of 2 to 8 carbon atoms.

The prepolymers of the invention are derivatives of a polyvinyl alcohol having a molecular weight of at least about 2,000, containing from about 0.5% to about 80%, based on the number of hydroxyl groups in the polyvinyl alcohol, of formula III.

units, especially about 1-50%, more preferably 1-25, preferably about 2-15%, and particularly preferably about 3-10%. The prepolymers according to the invention for the preparation of contact lenses contain in particular about 0.5 to about 25%, based on the number of hydroxyl groups of the polyvinyl alcohol, of units of the formula III, in particular about 1-15% and particularly preferably about 2-12%.

34 105792

The molecular weight of the polyvinyl alcohols which can be derivatized according to the invention is preferably at least 10,000. The upper molecular weight of the polyvinyl alcohols is limited to 1,000,000. Preferably, the molecular weight of the polyvinyl alcohols is up to 300,000, in particular up to about 100,000 and particularly preferably up to about 50,000. 5

Suitable polyvinyl alcohols according to the invention usually have a predominantly poly (2-hydroxy) ethylene structure. However, the polyvinyl alcohols derivatized according to the invention may also have hydroxy groups in the form of 1,2-glycols, such as 1,2-dihydroxyethylene copolymer units, which can be obtained, for example, by alkaline hydrolysis of vinyl acetate-vinylene carbonate copolymers.

In addition, the polyvinyl alcohols derivatized according to the invention may also contain a small amount, e.g. up to 20%, preferably up to 5%, of copolymer units consisting of ethylene, propylene, acrylamide, methacrylamide, di-methacrylamide, hydroxyethylmethacrylate, hydroxyethylmethacrylate, , ethyl acrylate, vinylpyrrolidone, hydroxyethyl acrylate, allyl alcohol, styrene or other similar commonly used comonomers.

Commercial polyvinyl alcohols can be used, for example Vinol® 107, Air Products (MM = 22000-31000, 98-98.8% hydrolyzed); Polysciences 4397 (MM = • 25,000, 98.5% hydrolyzed); BF 14, Chan Chun; Elvanol® 90-50, DuPont; UF-120,

Unity; Moviol® 4-88, 10-98 and 20-98, Hoechst. Other manufacturers include Nippon Gohsei (Gohsenol®), Monsanto (Gelvatol®), Wacker (Polyviol®) or 25 Japanese manufacturers Kuraray, Denki and Shin-Etsu.

«

As mentioned above, copolymers of hydrolyzed vinyl acetate can also be used, which are available, for example, as hydrolyzed ethylene-vinyl acetate (EVA), or as vinyl chloride-vinyl acetate, N-vinylpyrrolidone-vinyl acetate-tin and maleic anhydride.

35 105792

Polyvinyl alcohol is usually prepared by hydrolyzing the corresponding homopolymer polyvinyl acetate. In a preferred embodiment, the polyvinyl alcohol derived according to the invention contains less than 50% polyvinyl acetate units, in particular less than 20% polyvinyl acetate units.

5 _.......

Compounds containing units of formula III may be prepared in a manner known per se. For example, a polyvinyl alcohol having a molecular weight of at least about 2,000 and containing 10 units of formula IV -CH (OH) -CH 2 - (IV) may be reacted with about 0.5 to 80%, based on the number of hydroxyl groups of the compound of formula IV. (V) compound 15 R 'R *

I I

0 \ cn / ° (V) I / "* 20 \ 1CO-NH- (R4-NH-CO-O) q-R5-01p-CO-R3? Wherein R 'and R" are independently hydrogen, lower alkyl or lower alkanoyl, such as acetyl or propionyl, and other variables as defined for formula III, especially in an acidic medium.

25

Alternatively, a polyvinyl alcohol having a molecular weight of at least about I 'may be used. 2000, which contains units of formula IV, reacts with a compound of formula VI 36 105792

RT ’RT

I I

o o _ \ CH ^ (VI) I / «'R-

\B

Wherein the variables are the same as those defined for the compound of formula V, especially under acidic conditions, and then reacting the cyclic acetal thus obtained with a compound of formula VII OCN- (R 4 -NH-CO-O), -R 5 -O-CO-R 3 (VII ) 15 where the variables are the same as defined for the compound of formula V.

Alternatively, a reaction product of a compound of formula IV and a compound of formula VI, such as the product obtained as described above, may be reacted with a compound of formula VIII X-CO-R 3 (VIII) wherein R 3 is e.g. alkenyl of 2-8 carbon atoms and X is a reactive group, e.g. 25 etherified or esterified hydroxy, e.g. halogen, especially chlorine.

Compounds of formula V in which p is zero are known from EP 201 693. It also describes compounds of formula VI. The compounds of formula VII are known per se and can be prepared in a known manner. An example of a compound of formula VII where 30 q is zero is isocyanate ethyl methacrylate. An example of a compound of formula VII wherein q is one is the reaction product of isophorone diisocyanate with 0.5 equivalents of hydroxyethyl methacrylate. The compounds of formula VIII are known per se, a typical representative of which is methacryloyl chloride. Compounds of formula V wherein p and / or q is 1 may be prepared from the above compounds in a manner known per se, e.g. by reacting a compound of formula VI with isocyanate ethyl methacrylate or by reacting a compound of formula VI with isophorone diisocyanate first terminated at 0.5 equivalent of hydroxyethyl methacrylate.

The prepolymers of formulas I and III are surprisingly excellently stable. This is unexpected for a person skilled in the art, because e.g. highly functional acrylates usually have to be stabilized. If such compounds are not stabilized, rapid polymerization usually occurs. However, the prepolymers of the invention do not exhibit spontaneous crosslinking due to homopolymerization. The prepolymers of the formulas I and III can furthermore be purified in a manner known per se, for example by mixing with acetone, dialysis or ultrafiltration, with ultrafiltration being particularly preferred. By such a purification procedure, the prepolymers of formulas I and III can be obtained in very pure form, e.g. as a concentrated aqueous solution, with no or at least substantially no reaction products, such as salts, or starting materials, such as, for example, compounds of formula V, or other non-polymeric ingredients.

The preferred purification procedure for the prepolymers according to the invention, ultrafiltration, can be carried out in a manner known per se. In this case, it is possible to carry out the ultrafiltration repeatedly, for example two to ten times. Alternatively, ultrafiltration can also be performed continuously until the desired degree of purity is achieved. The desired degree of purity can in principle be chosen to be any high. A suitable measure of the degree of purity is, for example, the salinity of the solution, which is easy to determine in a known manner.

The prepolymers of formulas I and muk according to the invention can also be crosslinked in a very efficient manner and expediently, in particular by photocrosslinking.

In light crosslinking, a photoinitiator is suitably used which can initiate radical crosslinking. Such photoinitiators are well known to those skilled in the art, and examples of suitable photoinitiators include, in particular, benzoin methyl ether, 1-hydroxycyclohexylphenyl ketone, Daracure 1173 or Irgacure type. The crosslinking can then be effected by actinic radiation, such as UV light, or by ionizing radiation, such as gamma radiation or X-ray radiation.

The photopolymerization is suitably carried out in a solvent. Suitable solvents are, in principle, all solvents which dissolve polyvinyl alcohol and, if appropriate, further vinyl comonomers, e.g. water, alcohols, such as lower alkanols, e.g. ethanol or methanol, and in addition carbonic amides, such as dimethylformamide, or dimethyl sulfoxide, as well as suitable solvents. a mixture of water and an alcohol such as a water / ethanol or water / methanol mixture.

The photocrosslinking is preferably carried out directly on an aqueous solution of the prepolymers according to the invention, obtained as a result of the recommended purification step - ultrafiltration - after the addition of any additional vinyl comonomer.

Photocrosslinking can occur, for example, in about 15-40% aqueous solution.

The process for preparing the polymers according to the invention can be characterized, for example, in that the prepolymer containing units of formula I or III is photocrosslinked in particularly pure form, i.e. after single or multi-stage ultrafiltration, preferably in solution, especially in aqueous solution, in the presence or absence of other vinyl comonomer.

The vinyl comonomer which may further be used according to the invention may be hydrophilic, hydrophobic or a mixture of hydrophobic and hydrophilic vinyl monomer. Suitable vinyl monomers are in particular those commonly used in the manufacture of contact lenses. By hydrophilic vinyl monomer is meant a monomer which, as a homopolymer, is typically a polymer that is water soluble or can absorb at least 10% by weight of water. By analogy, a hydrophobic vinyl monomer is one that, as a homopolymer 30, is typically a polymer that is insoluble in water and can absorb less than 10 weight percent water.

39 105792

In general, about 0.01 to 80 units of a typical vinyl comonomer react per unit of formula I or ΙΠ.

i. ί v, ,, If a vinyl comonomer is used, the crosslinked | 5 polymers preferably about 1-15%, particularly preferably about 3-8% by weight of the hydroxyl groups of the polyvinyl alcohol of formula I or III. . ·. . by reacting with about 0.1 to 80 units · vinyl monomer.

The proportion of vinyl comonomers, if used, is preferably 0.5 to 80

ί \ V-V

| Units per unit of formula I, in particular 1 to 30 units of vinyl comonomer per unit of formula I and particularly preferably 5 to 20 units per unit of formula I.

In addition, it is preferred to use a hydrophobic vinyl comonomer or a mixture of a hydrophobic vinyl comonomer with a hydrophilic vinyl comonomer, wherein the mixture contains at least 50% by weight of the hydrophobic vinyl comonomer. In this way, it is possible to improve the mechanical properties of the polymer without substantially reducing the water content. In principle, however, it can be stated that both conventional hydrophobic vinyl comonomers and conventional hydrophilic vinyl comonomers are suitable for the copolymerization of polyvinyl alcohol containing groups of the formula I.

Suitable hydrophobic vinyl comonomers include, but are not limited to, C 1 -C 18 alkyl acrylates and methacrylates. C 1 -C 6 alkyl acrylamides and methacrylamides, acrylonitrile, methacrylonitrile, C 1-6 alkyl, vinyl-C -C 1-6 haloalkenes, styrene, C 1 -C 6 alkylstyrenes, vinylalkyl ethers having 1 to 6 carbon atoms in the alkyl moiety, C 1-6 perfluoroalkyl acrylates and methacrylates or the like Partially Forged acrylates and methacrylates, C 3 -C 2 Alkyl ethyl thiocarbonylaminoethyl acrylates and methacrylates, acryloxy and methacryloxyalkylsiloxanes, N-vinylcarbazole, maleic acid, fumaric acid, * itaconic acid, mesaconic acid and the like C 1-4 alkyl esters Preferred are C 1-4 alkyl esters of vinyl-unsaturated carboxylic acids having 3 to 5 carbon atoms, for example, and vinyl esters of carboxylic acids up to 5 carbon atoms.

Examples of suitable hydrophobic vinylic comonomers include methyl-5-acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, sykloheksyyliak methacrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, pro-methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidene chloride , acrylonitrile, 1-butene, butadiene, methacrylonitrile, vinyylitoluoli, vinyl ethyl, perfluoro-10 heksyylietyylitiokarbonyyliaminoetyylimetakrylaatti, isobomyylimetakrylaatti, trifluoro ethyl methacrylate, hexafluoro-isopropyl methacrylate, heksafluoributyylimetakry-methacrylate, tris-trimethylsilyloxy-silyylipropyylimetakrylaatii, 3-metakryloksipropyyIi-pentametyylidisiloksaani and bis (metakryloksipropyyli) tetramethyldisiloxane.

15 Suitable hydrophilic vinylic comonomers include, but are not limited to, substituted by hydroxy alempialkyyliakrylaatit acrylates and methacrylates, acrylamide, methacrylamide, alempialkyyliakryyliamidit and methacrylamides, ethoxylated acrylates acrylate and methacrylates, hydroxy-substituted alempialkyyliakryyliamidit and methacrylamides, hydroxy-substituted alempialkyylivinyylieetterit, natriumeteeni 20-sulfonate, sodium styrene sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, N-vinylpyrrole, N-vinylsuccinimide, N-vinylpyrrolidone, 2- or 4-: vinylpyridine, acrylic acid, methacrylic acid, amino "also includes" (including mono-lower alkylamino or di-lower alkylamino-lower alkyl acrylate and methacrylate, allyl alcohol and the like. Preferred are, for example, hydroxy-substituted Q-Q-alkyl (meth) acrylates, five- to seven-membered N-vinyl lactams, N, N-di-C1-C4-alkyl (meth) - *; acrylamides and vinyl - unsaturated carboxylic acids having a total of 3 to 5 carbon atoms.

Examples of suitable hydrophilic vinyl comonomers are hydroxyethyl methacrylate, hydroxyethyl acrylate, acrylamide, methacrylamide, • · · 41 105792 dimethacrylamide, allyl alcohol, vinylpyridine, vinylpyridine, vinylpyrrolidone, glycerin, glycerin corresponding.

Preferred hydrophobic vinyl comonomers are methyl methacrylate and vinyl acetate.

Preferred hydrophilic vinyl comonomers are 2-hydroxyethyl methacrylate, N-vinylpyrrolidone and acrylamide.

The polymers according to the invention can be converted into shaped bodies in a manner known per se, in particular into contact lenses, and, for example, by prepolyming the prepolymers according to the invention in a suitable contact lens mold. The invention thus relates to molded articles which consist essentially of a polymer according to the invention. Other examples of molded articles of the invention include, in addition to contact lenses, biomedical or specific ophthalmic molded articles, e.g., intraocular lenses, blindfolds, surgical molded articles such as heart valves, artificial veins, or the like, membranes, membranes or membranes, e.g., diffusions, e.g. or photoresist materials, e.g., membranes or molded articles used as etching resistors or screen printing resistors.

: A specific embodiment of the invention relates to contact lenses which contain a polymer according to the invention or which consist essentially or entirely of a polymer according to the invention. Such contact lenses have a number of unusual and very advantageous properties. These properties include, for example, their excellent tolerability in human handsome, based on a balanced relationship between water content, oxygen permeability and mechanical properties. The lenses according to the invention are also very shape-stable. Not even after autoclaving at about 120 ° C, for example, no changes in form-30 can be observed.

42 105792

It can further be mentioned that the contact lenses according to the invention can be manufactured in a very simple and efficient manner compared to the prior art. This is due to several factors. First, the starting materials are inexpensive to obtain or manufacture. Secondly, it is preferred that the prepolymers be surprisingly stable so that they can be purified very well. Thus, a material can be used for crosslinking which practically no longer requires any post-purification, such as, for example, the expensive extraction of non-polymerized components. In addition, the polymerization takes place in aqueous solution, eliminating the need for a subsequent hydration step. Finally, the light polymerization takes place in a short time, so that the manufacturing process of the contact lenses 10 according to the invention can also be made very economical in this respect.

All of the above advantages naturally apply not only to contact lenses but also to other molded articles according to the invention. The sum of the various advantageous features achievable in the manufacture of the molded articles according to the invention makes the molded articles according to the invention particularly suitable for bulk articles, such as contact lenses, which are used only for a short time and then replaced with new lenses.

In the following examples, amounts are by weight unless otherwise indicated and temperatures are given in degrees Celsius. The examples are not intended to limit the invention in any way, e.g. only to the scope of the examples.

»F

Example 1a): 105.14 parts of aminoacetaldehyde dimethyl acetal and 101.2 parts of triethylamine in 200 parts of dichloromethane are added dropwise in an ice bath to 104.5 parts of meta-25 cryloyl chloride dissolved in 105 parts of dichloromethane at a maximum of 15 ° C over 4 hours. After completion of the reaction, the dichloromethane phase is washed with 200 parts of water, then with 200 parts of 1N HG solution, then twice with 200 parts of water. After drying over anhydrous magnesium sulfate, the dichloromethane phase is evaporated and stabilized with 0.1%, based on the reaction product, of 2,6-di-tert-butyl-p-cresol. After distillation at 90 ° C / 10 x 3 mbar, 112 g of methacrylamidoacetaldehyde dimethyl acetal are obtained in the form of a colorless liquid, boiling point 92 ° C / 10 x 3 mbar (yield 65%).

i 43 105792

Example 1b): 52.6 g of aminoacetaldehyde dimethyl acetal are dissolved in 150 ml of deionized water and cooled in an ice bath to 5 ° C. Then 50 ml of methacrylic acid chloride and 50 ml of 30% sodium hydroxide solution are added simultaneously over 40 minutes so that the pH remains at 10 and the temperature does not rise above 20 ° C. At the end of the addition, the residual content of aminoacetaldehyde dimethyl acetal is 0.18% by gas chromatography. By adding a further 2.2 ml of methacrylic acid chloride and 2.0 ml of 30% sodium hydroxide solution, the amine reacted completely. The solution is then neutralized with 1N hydrochloric acid (pH = 7). The aqueous phase is extracted with 50 ml of petroleum ether and washed with water. The petroleum ether phase contains 3.4 g of by-product. The aqueous phase is purified to give 402.8 g of methacrylamidoacetaldehyde dimethyl acetal. According to the gas chromatogram, the product is 98.2%.

Example 2: 10 parts of a polyvinyl alcohol having a molecular weight of 22,000 and a degree of saponification of 97.5-99.5% are dissolved in 90 parts of water, 2.5 parts of methacrylamidoacetaldehyde dimethyl acetal are added and acidified with 10 parts of concentrated hydrochloric acid. The solution is stabilized with 0.02 parts of 2,6-di-tert-butyl-p-cresol. After stirring for 20 hours at room temperature, the pH of the solution is adjusted to 7 using 10% sodium hydroxide solution, and then ultrafiltered seven times with a 3 kD membrane (1: 3 ratio). After concentration, an 18.8% aqueous solution of methacrylamidoacetaldehyde-1,3-acetal of polyvinyl alcohol with a viscosity of 2240 cP at 25 ° C is obtained.

Example 3: 10 parts of the methacrylamidoacetaldehydo-1,3-acetal solution of polyvinyl alcohol obtained according to Example 2 are photochemically crosslinked by mixing 0.034 parts of Darocure 1173 (CIBA-GEIGY). This mixture is exposed as a 100 micron thick layer between two glass plates in a Staub 5000 W exposure apparatus with 200 pulses. A solid transparent film is obtained which •.

the solids content is 31%.

Example 4: 110 g of polyvinyl alcohol (Moviol 4-88, Hoechst) are dissolved in 440 g of deionized water at 90 ° C and cooled to 22 ° C. 100.15 g of a 20.6% aqueous solution of methacrylamidoacetaldehyde dimethyl acetal, 38.5 g of concentrated hydrochloric acid (37% p.a., Merck) and 44.7 g of deionized water are added. The mixture is stirred at room temperature for 22 hours, after which the pH is adjusted to 7 with 5% NaOH solution. The solution is diluted to 3 liters with deionized water, filtered and ultrafiltered on a Filtron 1-KD-Omega membrane. After three to five passes of the sample volume, the solution is concentrated. 660 g of a 17.9% solution of methacrylamidoacetaldehyde-1,3-acetal of polyvinyl alcohol with a viscosity of 210 cp are obtained. The intrinsic viscosity of the polymer is 0.319. The nitrogen content is 0.96%. According to NMR, 11 mol% of the OH group is acetalized and 5 mol% of the OH groups are acetylated. Concentration of the aqueous polymer solution under reduced pressure and air-10 stream gives a 30.8% solution with a viscosity of 3699 cp.

Example 5: 133.3 g of a 15% polyvinyl alcohol solution (Moviol 4-88, Hoechst) are mixed with 66.6 g of deionized water, 3.3 g of monomeric 4-methacrylamidobutyraldehyde diethyl acetal and 20.0 g of with conc. hydrochloric acid (37% 15 p.a., Merck) and stirred at room temperature for 8 hours. The pH of the solution is then adjusted with 5% sodium hydroxide solution 7. After ultrafiltration through a Filtron 3 KD-Omega membrane to reduce the sodium chloride content of the polymer solution from 2.07% to 0.04%, methacrylamidobutyraldehyde-1,3 of polyvinyl alcohol is obtained. -acetal 20% polymer solution with a viscosity of 400 cp. The intrinsic viscosity of the polymer is 0.332. The nitrogen content is 0.41%. According to NMR, 7.5 mol% of the OH groups have acetal groups and 7.3 mol% of the OH groups have acetate groups.

Example 6: To 200 g of a 10% solution of polyvinyl alcohol (Moviol 4-88, Hoechst) is mixed 2.4 g (14.8 mmol) of aminobutyraldehyde diethyl acetal (Fluka) and 20 g of conc. hydrochloric acid (37% p.a., Merck). The solution is stirred for 48 hours at room temperature and then neutralized with 10% sodium hydroxide solution. The solution is diluted to 400 ml. 200 ml of this solution are worked up as in Example 7. To the remaining 200 ml of this solution is mixed 0.85 g (8.1 mmol) of methacrylic acid chloride 30 (Fluka) and the pH is maintained at 10 with 2N sodium hydroxide solution. After 30 minutes at room temperature, the pH is adjusted to 7.0 and the solution is purified on a Filtron 3-KD-Omega membrane analogously to Example 5. After concentration, 45,105,792, a 27.6% polymer solution of polyvinyl alcohol methacrylamidobutyridehydo-1,3-acetal with a viscosity of 2920 cp is obtained. The intrinsic viscosity of the polymer is 0.435. The nitrogen content is 0.59%.

Example 7: 1.3 g (8.5 mmol) of 2-isocyanate ethyl ethyl methacrylate are mixed with 200 ml of the polymer solution of Example 6 and the pH is maintained at 10 with 2N sodium hydroxide solution. After 15 minutes at room temperature, the solution is neutralized with 2N hydrochloric acid and ultrafiltered analogously to Example 6. After concentration, a 27.1% polymer solution of 4- (2-methacryloylethylureido) butyraldehyde-1,3-acetal of polyvinyl alcohol with a viscosity of 2320 cp is obtained. The intrinsic viscosity of the polymer is 0.390, the nitrogen content is 1.9%.

Example 8: A 30.8% polymer solution according to Example 4 with a viscosity of about 3600 cp is mixed with 0.7% Darocur 1173 (based on polymer content). The solution is filled into a contact lens mold made of transparent polypropylene, and the mold is sealed. The solution is exposed for 6 seconds at a distance of 18 cm with a 200 watt Oriel UV lamp. The mold is opened so that the finished contact lens can be removed. The contact lens is transparent and has a water content of 61%. The modulus is 0.9 mPa, elongation at break 50%. The contact lens is subjected to a 40-minute autoclave treatment at 121 ° C.

20 No deformation of any kind can be observed in the contact lens thus treated.

Example 9: 10.00 g of the 27.1% polymer solution according to Example 7 are mixed with 0.0268 g of Darocur 1173 (based on 0.7% polymer content) and 0.922 g of methyl methacrylate. After the addition of 2.3 g of methanol, a clear solution is obtained. This solution is illuminated in analogy to Example 8 for 14 seconds with a 200 watt Oriel lamp. A transparent contact lens with a water content of 70.4% is obtained.

Example 10: To 12.82 g of a 24.16% solution of the prepolymer of Example 4 are mixed 1.04 g of acrylamide and 0.03 g of Darocur 1173. The clear solution is then exposed 30 analogously to Example 8 with a 200 watt Oriel lamp for 14 seconds. A contact lens with a water content of 64.4% is obtained.

Claims (62)

A method of manufacturing contact lenses by suitable energy exposure from a crosslinkable material in a mold (1) permeable to at least partially crosslinking energy 5 having a mold cavity (15) defining the shape of a contact lens (CL) to be manufactured, the material being introduced into the mold cavity at least partially crosslinking by exposing it to the crosslinking energy to a sufficient extent to remove the contact lens from the mold, the exposure of the material to the crosslinking energy (3) being limited to the region of the mold cavity (15), characterized in that the crosslinking energy (3) is limited to the entire mold cavity (15) the energy providing the crosslinking by at least partially impermeable masking of the mold (1) and / or by controlling the path of the energy beams, wherein this regional energy limitation determines the contact lens 15, including the contact lens; the final shape of the ireuna and the post-processing of the contact lens (CL) thus obtained are not required. 2. For the purposes of paragraph 1, the energy is determined by means of an energy-saving method, in particular UV-radiation, gamma-ray, electron-stripping and thermal treatment. 15 3. Förfarandc cnligt krav 2, kännetecknat därav, att strälningsenergin används i shape av ett väscntligcn parallellt strälknippe (3). Method according to Claim 1, characterized in that radiant energy, in particular UV radiation, gamma radiation, electron radiation or thermal radiation, is used as the network-providing energy. Method according to Claim 2, characterized in that the radiant energy is used in the form of a substantially parallel beam (3). 4. For the purposes of this Regulation, the Community shall be responsible for the formulation (1) of the formulation of the energy in the form of energy from the first 20 years of the formulation, and of the local formulation of the energy source. this is not the case with any other genomic energy market. Method according to one of the preceding claims, characterized in that a mold (1) is used which is highly permeable to the energy providing crosslinking on at least one side, and in that the regional exposure of the energy exposure is limited to a part of the mold which is poorly formed of crosslinking energy. permeable or completely impermeable. 30 5. Förfarandc cnligt nägot av föregäende krav, kännetecknat därav, att en forma (1) 25 används, vilcn ätminstone i en riktning är väl genomsläpplig för Energy For a first-time commercial use, and for the local production of energy in the form of an ordinance mask (21) which does not form part or all of the genomics in the energy of the field. 30 6. For the purposes of paragraph 5, the first step is shown in the figure (21) in the form of a separation, respectively, of a separate form, specifically and in particular (17,18), of which the material has been removed. 105792 58 Method according to one of the preceding claims, characterized in that. using a mold (1) which is highly permeable to the energy of crosslinking in at least one direction, and that the regional limitation of energy exposure is effected by a mask (21) of poorly permeable or impermeable crosslinking energy placed outside the mold cavity (15). « Method according to Claim 5, characterized in that the mask (21) is arranged in the region of the separating planes or separating surfaces of the separate mold parts, in particular in the regions (17, 18) in contact with their crosslinkable material. 7. The first of the steps of paragraphs 1 to 6, having the form (1) after which the material of the form (15) has been fully enclosed, the form of the material of the head (15) being of the same type (16) above. öppen, vilken företrädesvis omsluter fonnkaviteten, och innehäller icke tvärbundet material, 5 och att Energin som ästadkommer tvärbindningen hälles ätskild frän det i denna spalt (16) befintliga materialet. Method according to one of Claims 1 to 6, characterized in that the mold (1) is not completely closed after the material has been introduced into the mold cavity (15), but in such a way that at least one contact with the mold cavity (15) remains open. preferably a gap (16) containing non-crosslinked material surrounding it, and that the energy providing crosslinking is kept out of contact with the material in this gap (16). 15 8. For the purposes of paragraph 7, the terms of reference (1) are set out below in terms of the amount of material used in the material and proportion of the amount of the item 10. A method according to claim 7, characterized in that the mold (1) is closed further according to the crosslinking shrinkage as the crosslinking of the material progresses. 9. For the purposes of paragraph 7, the following is an example of the use of the same material as in the case of energy, the energy of which is the same as in the case of (in addition to 15) 15). Method according to Claim 7, characterized in that at least a rigidly flowing starting material is used before the crosslinking and a container not exposed to the crosslinking energy, from which the material for shrinkage compensation f can flow through the gap (16) into the mold cavity (15). 10. For the purposes of paragraphs 1 to 9, the contact with the contact lens (CL) is replaced by the contact lenses (CL) and the form of the contact material (CL) has been used to replace the material of the genome. Method according to one of the preceding claims 1 to 9, characterized in that after the contact lens (CL) has been removed from the mold, the non-crosslinked or only partially crosslinked material adhering thereto is removed by rinsing with a suitable solvent. • « 11. A method according to any one of claims 1 to 10, which comprises the form (1) of the form of a kraft, the form of the form (11,12) being connected to a portion 25 of the present invention. Method according to one of the preceding claims 1 to 10, characterized in that the mold (1) is closed without the application of force, so that the mold halves (11, 12) rest on one another without external loading. • 48 105792 12. The first of these forms is set out in paragraphs 1 to 11, which are shown in the form of a form (15) in which the minimum value is determined by the use of solid materials. 30 Method according to one of the preceding claims 1 to 11, characterized in that the filling of the mold cavity (15) takes place in a starting material (M) which is at least partially still non-crosslinked. 13. A method according to claim 12, which comprises a formulation (15) of the same type of material (R) as a whole, in which 59 105792 are used in the form of materials, in which case (15) fylles med vätska. Method according to Claim 12, characterized in that, in order to fill the mold cavity (15), it is brought into contact with a container (R) surrounding it, in which the starting material is produced and from which it is allowed to flow into the mold cavity (15). 14. For example, 12 or 13, according to the form (1), 5 or more materials. Method according to Claim 12 or 13, characterized in that the mold (1) 10 is closed in the starting material. 15. A method according to any one of claims 12 to 14, further comprising a form of a ring, having a handle (10a, 10b) and having a form of a handle (11a, 11b) having a shape and a handle (11a, 11b). a maximum of 10 times the same value (100a, 100b), and in the case of a colorless material (100a, 100b) and a form of the same (11a, 11b), and the color of the formulation bortledes. 15. A further form according to claim 15, having a form (1) with a form (1a), 11a, 11b and a second form (11a, 11b). ). Method according to one of Claims 12 to 14, characterized in that a mold is used which comprises a container (10a, 10b) and a mold part (11a, 11b) movable in this container, which can be moved from the opposite side to open and close the mold. away from the container wall (100a, 100b) and towards this container wall, wherein during the opening of the mold the starting material is fed between the container wall (100a, 100b) and the mold part (11a, 11b), and during the closing of the mold the starting material is removed again. Method according to Claim 15, characterized in that a mold (1) with two mold halves is used, the second mold half being: placed in the container wall (100a, 100b) and the other mold half in the movable mold part (11a, 11b). 17. A method according to claim 16, comprising a form of fader-20 in the form of a form and a form of a form, including a form of the form of a fuse (100a, 100b), and a form of the form of a form; formdelen (IIa, Ilb). A method according to claim 16, characterized in that a mold comprising a father mold half and a mother mold half is used, wherein *. the parent mold half is located in the container wall (100a, 100b) and the mother mold half in the movable mold part (11a, 11b). 18. The first step is shown in Figures 15 to 17, the first step being as shown in Figures 25 and 25, and in the case of a double material (P1, P2). Method according to one of Claims 15 to 17, characterized in that pumps (PI, P2) are used for the inlet and outlet of the starting material. 49 105792 19. For example, the first of the steps of 15 to 17, the first step is to read more than one or more of the materials used in the form (Ha, 11b). 30 20. For example, the form is shown in Figures 12 to 19, which is defined as the form of the group (CL) used to form the genome of the formulation with the above material. 105792 60 Method according to one of Claims 15 to 17, characterized in that a movable mold part (11a, 11b) is used for feeding in and out of the starting material. R-N \ r2: wherein R is lower alkylene up to 8 carbon atoms, R1 is hydrogen or lower alkyl and R2 is olefinically saturated, electron-withdrawing, copolymerizable residue, preferably having up to 25 carbon atoms. 25 Method according to one of Claims 12 to 19, characterized in that the crosslinked molded body (CL) is removed from the mold by rinsing the mold with the starting material. 21. For example, the form is shown in Figures 15 to 19 and is preferably set to form, (CL) in the form of a group (CL) in the form of a genomic material having a formulation, and a spool or form having a formulation. 5 Method according to one of Claims 15 to 19 and 20, characterized in that the molded body (CL) is removed when the starting material is opened from the mold; : flow and rinse out of the mold when closing the mold. 10 22. For the purposes of Article 20, the first or more of the cycles are set out in the form of an energy-sensitive form (CL) and the formulation of the genome of energy (3), and In the form of an end of the form, the colors of the form are separated from the form and the form (11a) by means of the form of the form of the form (100a). A method according to claim 20, characterized in that in the first section the mold is opened and closed again, and then at least; the crosslinking required to remove the molded body (CL) from the mold by exposing it to energy (3), and that in the second section the mold is reopened, the molded body 15 is removed from the mold and then the mold part (11a) is moved to close the mold: again to the opposite container wall (100a). the piece is washed out of the mold. 23. The first of these forms is set out in paragraphs 12 to 19, with the result that the form of the infection control form (4). 15 Method according to one of Claims 12 to 19, characterized in that the crosslinked shaped body 20 is removed from the mold by means of a gripping device (4). Method according to one of Claims 15 to 19 and 23, characterized in that the molded body (CL) removed from the mold by the gripping device (4, 4b) is placed in the movable mold part (11b) of the movable mold part (11b) and the opposite wall. 100b) outside the space between. 24. For example, the face is shown in Figures 15 to 19 and is shown in Figure 23, which is shown in the form of an influenza formulation (4,4b) in the form of a plurality of forms (CL) in the form of a formulation (11b). (Uh) och den mit emot ligand behällarväggen (100b). 20 25. Förfarande cnligt krav 24, kännetecknat därav, att den pä den förskjutbara; formdelen avlagda formkroppen fasthälles vid denna genom undertryck (NP) och löses sedan frän denna genom övertryck (HP). 25 26. Förfarande cnligt nägot av kraven 12 - 25, kännetecknat därav, att formen efter införandet av matcrialct i formkaviteten inte stänges fullständigt, sää en ringpalt. · (16) förblir öppen, vilcn omsluter formkaviteten och stör i för innchällcr ickc tvärbundet material. 30 27. For the purposes of Article 26, the terms of reference are set out below in the case of the provision of material resources in proportion to the number of transactions. 61 105792 25 Patentkrav. · 1. A patent for the production of contact lenses in the form of energy-saving materials in the form of energy (1) in the form of a source of energy in the form of energy-saving materials in the form (15), in the form of 30 contact lenses (CL) in the form of contact lenses, colors and materials of the same type as those specified in this Regulation, and in the case of energy-related genomes from energy sources in the form of contact materials in accordance with 57 105792 in the case of materials (3) in which the power supply unit is located locally to the formwork (15), the energy of the power supply (3) in the case of power units (15) in the form of a power supply (15) 1) the energy of the energy source for the energy of the energy supply, and / or In this case, the energy of the genome is determined by the localization of the energy in contact with the contact lenses, including the contact lenses, and in the case of contact lenses (CL). 10 25. CH / <m> I / R1 n-nC \ [C0-NH- (n4-NH-C0-O) q-R5-01p-C0-R3 • wherein R is lower alkylene, R1 is hydrogen or lower alkyl , p is zero or one, q is zero or one, R 3 is an olefinically unsaturated copolymerizable residue having 2 to 8 carbon atoms, and R 4 and R 5 are independently lower alkylene of 2 to 8 carbon atoms, arylene of 6 to 12 carbon atoms, 6- A saturated divalent cycloaliphatic group of 10 carbon atoms, arylene alkylene or alkylene arylene of 7 to 14 carbon atoms, or arylene alkylene arylene of 13 to 16 carbon atoms. A method according to claim 24, characterized in that the molded part placed in the movable mold part is attached to it under reduced pressure (NP) and then removed therefrom under overpressure (HP). 30 Method according to one of Claims 12 to 25, characterized in that the mold is not completely closed after the material has been introduced into the mold cavity, but in such a way that a ring space surrounding the mold cavity and connected to it, containing non-crosslinked material, remains open. (16). A method according to claim 26, characterized in that the mold is closed for a further 5 crosslinking shrinkages, respectively, as the crosslinking of the material progresses. 28. A further method according to claim 27, which comprises the use of additional materials for use in the form of crystallization compensation (16) in the form of a ring (15). 5 29. Förfarande enligt nägot av föregäende krav, kännetecknat därav, att utegängs materialet är en prepolymer, vilken är ett derivat av en polyvinylalkohol med en molekylvikt av ätminstone ca 2000, vilken innehäller ca 0,5 - ca 80%, räknat pä antalet hydroxylgrper in the case of polyvinyl alcohols, the enhancer is in the form of formula I, 10 R 2 is R 2 in R 1 or R 2 is an oligintant in the form of an electrolyte sampolymer serrate account 25 cholatomers. 20 A method according to claim 27, characterized in that at least a rigidly flowing starting material is used before crosslinking, and that the starting material can flow through the gap (16) into the mold cavity (15) in order to compensate for the shrinkage. 10 Process according to one of the preceding claims, characterized in that the starting material is a prepolymer which is a derivative of a polyvinyl alcohol having a molecular weight of at least about 2000, containing from about 0.5 to about 80%, based on the number of hydroxyl groups of the polyvinyl alcohol, 15 II Vch / 0 ® I / R ' 30. A compound according to claim 29, which comprises the use of a pre-polymer, wherein R2 or an olefin is alkylated with the form R3-CO-, or R3 or an olefin is a shampoo polymer with a mixture of 2 to 24 cholomaters, and 8 cholatomers, brisket spheres with 2-4 cholatomers. 25 Process according to Claim 29, characterized in that the starting material is; a prepolymer wherein R 2 is an olefinically unsaturated alkyl residue of the formula R 3 -CO-, wherein R 3 is an olefinically unsaturated copolymerizable residue having 2 to 24 carbon atoms, preferably 2 to 8 carbon atoms, particularly preferably 2 to 4 carbon atoms. 51 105792 31. A preferred compound according to claim 30 is selected from the group consisting of pre- * polymer, wherein R3 is alkenyl of 2-8 cholatomers. Process according to Claim 30, characterized in that the starting material is a prepolymer in which R 3 is alkenyl of 2 to 8 carbon atoms. 32. A compound according to claim 29, which comprises the use of a pre-30 polymer, wherein R2 is a residue of formula II -CO-NH- (R4-NH-CO-O), -R5-0-C0-R3 (II) 105792 62 are selected from the group consisting of 2 to 8 cholatomers, arylenes of 6 to 12 cholatomers, optionally bivalent cycloaliphatic groups having 6 to 10 cholatomers, arylenalkylenes and alkylene aryls of 7 -14 cholatomers, or arylenalkylenarylenes with 13 to 16 cholatomers, and with R3 and olefins having the same polymeric moiety with 2 to 24 cholaters, spherical discharges with 2 to 8 cholatomers, spherical discharges with 2 to 4 cholatomers. Process according to Claim 29, characterized in that the starting material is a prepolymer in which R 2 is a residue of the formula Π i i -,! -C0-NH- (R4-NH-CO-O) rR5-O-CO-R3 (II) t · .-. ^ In '. · 'Jrr' ": '' wherein q is zero or one, and R 4 and R 5 are independently lower alkylene of 2 to 8 carbon atoms, arylene of 6 to 12 carbon atoms, saturated divalent cycloaliphatic group of 6 to 10 carbon atoms, arylene alkylene of 7 to 14 carbon atoms or alkylenearylene, arylphenylalkyleneemyrene having 13 to 16 carbon atoms, and wherein R 3 is olefinically saturated copolymerizable or has 2 to 24 carbon atoms, preferably 2 to 8 carbon atoms. , particularly preferably 2 to 4 carbon atoms 33. A compound according to claim 29, which comprises a prepolymer which is derived from a polyvinyl alcohol having a molecular weight of about 2000, a weight of about 10 about 0.5 to about 80%, the hydroxyl group having a polyvinyl alcohol, an enhancer of formula III, ° \ oh / ° (m> I / n 'R tr SvN (CO-NH- (R ^ * NH-CO-O) IJ-ne * 0) ^ - CO * R3 20 from R is slurry, R1 is eller lägalkyl, p är noll eller ett, q är noll eller ett, R3 är en olefint omättad sampolymeriserbar rest med 2-8 kolatomer, och R4 och R5 är; oberoende av varandra lägalkylen med 2-8 kolatomer, arylen med 6-12 kol an atom having a bivalent cycloaliphatic group of 6 to 10 cholaters, arylenylalkyl or alkylenaryl of 7 to 14 cholatomers or arylenalkylenaryl of 13 to 16 of 25 cholatomers .. · 34.Furfarande enligt krav 33, kännetecknat därav, att utgängsmaterialet en engängsmaterialet en en. R 6 is alkalkyl with up to 6 cholaters, p is zero and R 3 is alkenyl with 2-8 cholaters. A process according to claim 29, characterized in that the prepolymer is a derivative of a polyvinyl alcohol having a molecular weight of at least about 2000, containing about 0.5 to about 80%, based on the number of hydroxyl groups of the polyvinyl alcohol, of units of formula III: \ ch / CH '\ II c> o Process according to Claim 33, characterized in that the starting material is a prepolymer in which R is lower alkylene up to 6 carbon atoms, p is zero and R 3 is alkenyl of 2 to 8 carbon atoms. 35. A compound according to claim 33, which comprises the use of a pre-polymer, such as R 6 is substituted with 6 chapters, R 5 is n, R 5 is alkyl with 2 to 6 chapters, and R 3 is alkenyl with 2 to 8 cholatomers. i; L. «·, b :: ·. ·: I 1 - r 5 36. For the purposes of Article 33, the provisions of this Regulation shall apply to pre-. - a polymer, such as R 6 is substituted by a 6-membered atom, a pair, a single member, R4 is a member of a 2-6-cholatomer, a phenyl, a substituent or a substituent of a membered alkyl, - .. Cyclohexylen or a cyclohexylene-alkylene , unsubstituted or substituted with alkyl, phenylene, alkylene, alkylene-phenylene-phenylphenylene-alkylalken-phenyl, R 5 is 10 alkyl with 2 to 6 cholatomers, and R 3 is alkenyl with 2 to 8 cholatomers. .5 vn-vr,. ;. v Process according to Claim 33, characterized in that the starting material is a prepolymer in which R is lower alkylene up to 6 carbon atoms, p is one, q is zero, R 5 is lower alkylene of 2 to 6 carbon atoms and R 3 is 2 to 8 carbon atoms. alkenyl of a carbon atom. Process according to Claim 33, characterized in that the starting material is a prepolymer in which R is lower alkylene up to 6 carbon atoms, p is one, q is one, R 4 is lower alkylene of 2 to 6 carbon atoms, phenylene, unsubstituted or lower alkyl-substituted, cyclohexylene or cyclohexylene-lower alkylene, unsubstituted or lower alkyl-substituted, phenylene-lower alkylene, lower alkylene-phenylene or phenylene-lower alkylene-phenylene, R 5 is lower alkylene of 2 to 6 carbon atoms and R 3 is lower alkylene of 2 to 6 carbon atoms. 37. For the purposes of Article 29, the provisions of this Regulation apply to pre-existing materials; A polymer which is derived from a polyvinyl alcohol having a molecular weight. ‘;; , 'ilr ·;' ii>; ·; ne ca 2000, vilken innehäller ca 1 - ca 15%, räknat pä antalet hydroxylgrupper i 15 polyvinylalkoholen, enheter med formuleln I. 37. A process according to claim 29, characterized in that the starting material is a prepolymer which is a derivative of a polyvinyl alcohol having a molecular weight of at least about 2000 *, containing about 1 to about 15%, based on the number of hydroxyl groups of the polyvinyl alcohol. 38. A method according to any one of claims 1 to 37, wherein the formulation (1) and the form (1) and (12,12) form a contact for contact lenses (CL). 20 39. A method according to claim 38 is shown as being moderately shaped (12) and having a contact lens (CL). c Method according to one of Claims 1 to 37, characterized in that the second mold half (11, 12) of the mold (1) is used for packaging a contact lens (CL). A method according to claim 38, characterized in that the mother mold half (12) is used as a package for a contact lens (CL). 30 40. A first or more form 38 or 39, provided in the form of a mold (11,12) is used in the form of a side mold, and in the form of a mold (12,11) and 25 is used in the form of a side mold, the colors are molded in contact with the contact. • „ A method according to claim 38 or 39, characterized in that the second mold half (11, 12) is formed as a multi-purpose mold half and the second mold 105 (11, 11) is formed as a disposable mold half, wherein the disposable mold half is used as a contact lens package. 41. A method according to claim 40, comprising a fader-shaped halve (11) for use in the form of a halogen-shaped halva, and a moderform-halva (12) in the form of a halogen-shaped halva (12); · I _ „2 105792 64 A method according to claim 40, characterized in that the father mold half (11) 5 is formed as a multi-purpose mold half and the mother mold half (12) as a disposable mold half, wherein the mother mold half (12) is used as a contact lens package. 42. Anordning for the contact lens, with the contact lens and the shape of the contact lens (1), with the contact lens and the shape of the contact lens (15) with a fast contact lens (CL) with the contact lens (CL) in the form of a contact lens, with the same material and shape genomics for energy utilization for energy 5 for the production of energy, in which case (2a) for energy for energy production, and for energy (2b) for energy consumption in the form of energy (2) for energy consumption in energy production integration in the form of energy (1) for energy in the form of energy in the form of energy (15), in the case of energy in the form of energy in the form of energy (1) yes or no other genomic energy for the energy supply, and / or other elements for the production of the energy, ormeasures (15) in which the contact lenses are exposed to energy, and in which the contact lenses (CL) are in contact with the contact wire (CL), and after 15 contact with the contact lenses (CL). Apparatus for making contact lenses, comprising a closable and openable mold (1) having a mold cavity (15) defining the shape of the contact lens (CL) to be manufactured, the mold 10 being adapted to receive crosslinkable material and formed of at least partially externally introduced material for crosslinking material a source (2a) of crosslinking energy and means (2b) for exposing the mold (1) to the crosslinking energy, and means for regionally limiting the exposure of the mold (1) to the crosslinking energy in the region of the mold cavity (15), characterized in that that the means for limiting the exposure of the mold to the energy are formed as an impermeable or poorly permeable mold masking of the crosslinking energy and / or elements for guiding the path of the beams so as to expose the entire mold cavity (15) including the contact lens and the contact lens (CL); The final shape of the contact lens edge, including u-20 channels, becomes determined and post-processing of the contact lens thus obtained is not required. 43. An arrangement according to claim 42, which comprises a mask (21) and a mask (21), which is provided with a shape (15) by means of a screen (16) which may contain any material, 20 respektive formhalvoma (17,18), vilka kan komma i kontakt med materialet, mot Energin som ästadkommer tvärbindningen. Device according to Claim 42, characterized in that the masking of the mold (1) is formed as a mask (21) which, with the exception of the mold cavity (15), covers all empty spaces (16) or mold surfaces (17, 18) of the mold capable of containing non-crosslinked material. which may come into contact with the material, from the energy that causes the crosslinking. 44. Anordning enligt krav 42 eller 43, kännetecknad därav, att formen (1) omfattar tvä formhalvor (11,12), vilka är ätskilda längs en separationsyta (17, 18), och att 25 Masken (21) is anordnad vid en av the shape of the shape (11,12) and / or the shape of the shape of the shape (17,18) after the shape (15). Device according to Claim 42 or 43, characterized in that the mold comprises two mold halves (11, 12) separated by a separating surface (17, 18) and in that the mask (21) is arranged on the second mold half (11, 12) and / or or on both mold halves in the area of the separating surface (17, 18) outside the mold cavity (15). 54 105792 45. An arrangement according to claim 44, which comprises (UV) a method for measuring UV (and 12) a form of (11,12) having a form (1, 12) with a form (1) of 30 UV-translucent material, specially quartz. 1 · I. 65 105792 Device according to Claim 44, characterized in that the source (2a) generates UV radiation and in that at least one of the mold halves (11, 12) of the mold (1) is a UV-permeable material, in particular quartz. 46. An arrangement according to claim 45, which is shown in Figure (21), is based on the fact that the UV material is a genomic material, specifically metal or metal oxide, special and chromium plated. Device according to Claim 45, characterized in that the mask (21) consists of a layer of UV-impermeable material, in particular a metal or metal oxide layer, in particular a chromium layer. 46 105792 47. Anordning enligt segot av kraven 42-46, kännetecknad därav, att formen (1) är försedd med distansmedel (19a, 19b), vilka häller formhalvoma (11,12) vid sluten form pä ett ring ring avständ (Äy) frän varandra, This image (16) shows a single color in the form (15) and a stem in the form of a color, the colors of the color (21) in the form of a color. 10 Device according to one of Claims 42 to 46, characterized in that the mold (1) is provided with spacers (19a, 19b) which hold the mold halves (11, 12) in a closed mold at a small distance (Ay) from each other so as to form at least preferably a slit (16) surrounding the mold cavity (15), the mask (21) being located in the region of this slit. 48. An arrangement according to claim 47, which comprises (1) is provided with an elastic means or an installation means (19b), which can be used to change the shape of the halves (11, 12) from the above. Device according to Claim 47, characterized in that the mold is provided with elastic means or adjustment means (19b) which allow the mold halves (11, 12) to approach one another as a result of crosslinking shrinkage. 49. The method is set out in recitals 42 to 46, which refer to the form of the form (15) in which the materials and materials (M) are used, which may be used as a result. Device according to one of Claims 42 to 46, characterized in that, when the mold cavity (15) 20 is filled, it is arranged in a starting material (M) which is at least partially still in the non-crosslinked state. 50. Anordning enligt krav 49, kännetecknad därav, att den omfattar en behällare (R) 20 för astadkommande avggingsmaterialet, vilken omger formkaviteten (15) ochär a dörbindelse med formavitten (15), och at vid fyllandet av formkaviteten R) formulation with a formulation (15) and a flap in the case. Device according to claim 49, characterized in that it comprises a container (R) for producing a starting material surrounding the mold cavity (15) and connectable to the mold cavity (15), and that when filling the mold cavity the container (R) is connected to the mold cavity (15) and the mold cavity is filled from it. 51. Anordning enligt nägot av kraven 49 eller 50, kännetecknad därav, att den 25 omfattar medel (la) för a stänga den i utgängsmaterialet anordnade formen (1). Device according to claims 49 or 50, characterized in that it comprises means (1a) for closing the mold (1) placed in the starting material. 30 52. The arrangement of the faces of paragraphs 49 to 51, which may be of the form (10a, 10b), and of the form of the form (11a, 11b), is shown in the form of a form of the form (11a, 11b). of which 30 times the same value (100a, 100b), and the same number of characters (100a, 100b), and which are used in addition to the end (101a, 101b), the genome being used as a tool in the form of 100 characters, , 105792 66 100b) and form (11a, lib), and at the end (102a, 102b9), and the genome is selected under the form of a form of a material other than the same. Device according to one of Claims 49 to 51, characterized in that the mold comprises a container (10a, 10b) and a mold part (11a, 11b) movable in this container, which can be moved from an opposite container wall (100a) to open and close the mold i 105 105792. 100b) away and towards this container wall, and that the container is provided with an inlet (101a, 101b) through which starting material flows between the container wall (100a, 100b) and the mold part (11a, 11b) during the opening of the mold, and that the container is provided with with an outlet (102a, 102b) through which the starting material flows out again during the closing of the mold. 53. An arrangement according to claim 52, further defined in the form (1), comprises a form, colors and a form according to the form (100a, 100b), and a form according to the form (11a, 11b). Device according to Claim 52, characterized in that the mold (1) has two mold halves, one mold half being arranged in the container wall (100a, 100b) and the other mold half in the movable mold part (11a, 11b). 54. An arrangement according to claim 53, which comprises a fader-10 form and an additional form, and an additional form according to the form (100a, 100b), and an additional form according to the form (11a). Device according to claim 53, characterized in that the mold comprises a master mold half and a mother mold half, and in that the father mold half is arranged in the container wall (100a, 100b) and the mother mold half in the movable mold part (11a, 11b). 55. The arrangement of the face of the headings 52 to 54, which are connected to the pump 15 (PI, P2), is further adapted to the form of the end of the genome (101a, 101b) using a material (100a, 100b) and the form (11a, 11b), and the formulation of the form of the genome utilized (102a, 102b). Device according to one of Claims 52 to 54, characterized in that it is provided with pumps (PI, P2) which, when the mold is opened, feed the starting material between the container wall (100a, 100b) and the mold part (11a, 11b) via an inlet (101a, 101b). , 20 and guide the mold again when it is closed via the outlet (102a, 102b). ! Device according to one of Claims 52 to 55, characterized in that it is provided with operating means for the movable mold part (11a, 11b). 56. Anordning enligt nägot av kraven 52 - 55, kännetecknad därav, att den är för-20 sedd med medel för att driva den förskjutbara formdelen (lla.Ilb). 57. Anordning enligt nägot av kraven 49 - 56, kännetecknad därav, att den är är för- sedd med medi för att ästadkomma en strömning, vilken vid öppnandet av formen löser formcroppen frän formen, och vid stängandet av formen spolar ut den ur ur 25 formen. · 58. Anordning enligt segot av kraven 49 - 56, kännetecknad därav, att den är försedd med en fluanordning (4), vilken tar ut den denärbundna formkroppen (CL) ur forma. 30 Device according to one of Claims 49 to 56, characterized in that it is provided with means for generating a flow which, when the mold is opened, detaches the molded part from the mold and rinses it when the mold is closed out of the mold. Device according to one of Claims 49 to 56, characterized in that it is provided with a gripping device (4) which removes the crosslinked molded body (CL) from the mold. 56 105792 59. Anordning enligt segot av kraven 52-56 och 58, kännetecknad därav, att be-hällaren (10b) head en behälarvägg (103b) s skiljer sig frän den formgivande ytan 67 105792 (100b) uppvisar en utbuktning eller nisch (104b), the light is shown at the same time in the form of the formulation (Hb), the color of the formulation (4b) and in the case of the formulation (104b), and in the case of the formulation (11b) in the case of the formulation (114b) in which the ligament does not have 5 forms of formulation (100b), and in the form of an adhesive form (4b) in the form of a blank (CL). Device according to one of Claims 52 to 56 and 58, characterized in that the wall (103b) of the container (10b) other than the forming surface (100b) has a bulge or recess (104b) which extends substantially in the direction of movement of the movable mold part (11b), the gripping device (4b) is placed in this bulge or recess (104b), and that the movable mold part (11b) has a recess (114b) in the outer wall (113b) not opposite the shaping container surface (100b) into which the gripping device (4b) removed molded part (CL). 60. Anordning enligt krav 59, kännetecknad därav, att den förskjutb formdelen enpuktar en account inbuktningen (114b) ledande kanal (115b), vilken kan anslutas account en 10 över- resp undertryckskälla (P3), varvid kanalen (115b) dä, när gripanordn (4b) is provided with the form of a blank (CL) and an insert (114b) having a form (Hb), which is provided with an undercut fork, and then with an overcut for the lens. Device according to Claim 59, characterized in that the movable mold part has a channel (115b) leading to the recess (114b), which can be connected to an overpressure or vacuum source (P3), the channel (115b) being present when the gripping device (4b) ) places the removed molded body (CL) in a recess (114b) in the mold part (11b) connected to the vacuum source, and then to detach the lens to the overpressure source. 61. Anordning enligt nägot av kraven 53 - 60, kännetecknad därav, att formen är försedd med distansmedel (19), vilka häller formhalvorna vid stängd form perlitet avständ frän varandra, sä att en ringpalt (16) bildas vilken omsluter formkaviteten (15) och stär i förbindelse med denna. Device according to one of Claims 53 to 60, characterized in that the mold is provided with spacers (19) which hold the mold halves in a closed mold at a small distance from each other so as to form an annular gap (16) surrounding and connected to the mold cavity (15). Device according to Claim 61, characterized in that the mold is provided with elastic means or adjustment means which allow the mold halves to approach one another as a result of crosslinking shrinkage. 62. The provisions of paragraph 61, which are based on the form of an elastic medium or an installation, are shown in the form of an alternative to the form of a transfer account. «« • · l - -