JPH07505425A - Method for producing pressure-sensitive adhesive materials in sheet form by radical polymerization of formulations containing acrylic acid and/or acrylic acid derivatives - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Sheet by radical polymerization of acrylic acid and/or acrylic acid derivative-containing formulations Description of how to produce pressure-sensitive adhesive materials The present invention uses a laser beam in the range of 1l80-400n to process acrylic acid and Pressure-sensitive The present invention relates to a method of manufacturing an adhesive.

Pressure-sensitive adhesives bond in an aggressive and durable manner in dry (solvent-free) form at room temperature. and can be applied to a large number of different surfaces by simply making contact (finger or hand pressure is sufficient). The name given to a special category of adhesives that stick to surfaces. water, solvent Alternatively, thermal activation is unnecessary. The use of such pressure-sensitive adhesives has become widespread. and these preferably require later removal and strength Bonding agents for which strict standards have not been established, e.g. adhesive tape and self-adhesive Adhesive films, self-adhesive labels, pressure sensitive adhesive labels, plasters, stamps, etc. used in the production of binders for

The base polymers for modern pressure-sensitive adhesives are mainly natural and synthetic rubbers, polyacrylates, etc. esters, polyesters, polychloroprenes, polyisobutynes, polyvinyl ethers, polyurethanes and silicones, which are often may be combined with additives such as resins, plasticizers, fillers and/or stabilizers. It is used as Pressure-sensitive adhesives are often Developed as a result of polyreaction and their further processing requires that they have a flowable consistency (flowab). It is necessary in advance to indicate the length of the data. deer After these are spread flat onto the desired substrate, they are often treated with a solvent or dispersion. The agent must be removed, and this is commonly done by applying heat. Because of this, expensive drying sections and suction plants are required. In addition, Recovering or removing solvents increases costs to prevent environmental pollution. Ru. Moreover, the flammability of most solvents poses an additional risk. to this In addition, most organic solvents are harmful to human organisms and, as a result, their Expensive safeguards must be taken for those employed in the business.

Only by eliminating solvents and dispersants can the above-mentioned drawbacks be eliminated. to this One related possibility proposed is that from suitable polymers and optional additives The resulting melt is prepared without solvent and then distributed in a flat state from this melt. distributed, pressure-sensitive heat melt adhesives sitive hot-meltadhes (1ves).

In contrast to classical hot melts, these exhibit pressure-sensitive adhesive properties at room temperature. This example It is described in European Patent Application No. 0 305 756. This person In the case of the law, there are significant energy expenditures and partly due to expensive mechanical equipment. Constraints that are conditional on certain conditions need to be judged as flaws. special cases and After carrying out the solution polymerization, the solvent is removed and the melt is A variant of dispensing the resulting pressure-sensitive adhesive in flat form may also be advantageous.

Producing polymers using bulk polymerization also eliminates the use of solvents and dispersants. This provides further possibilities for avoiding Pressing olefinic unsaturated materials Attempts to carry out radical polymerization in the extractor caused problems when controlling this polymerization. This results in a high polymer yield, which makes this technology Until now, it has prevented it from becoming a reality.

Through the influence of energy-rich light beams, it is possible to produce solvent-free and dispersant-free products. It is more preferable to carry out the polymerization in a monomer-containing formulation that exhibits good flow properties. Get results. In this connection, among others, radically proceeding olefinic systems There is a necessary force for polymerization of unsaturated compounds.

Particularly good results have been obtained using electron beams and ultraviolet light as light beams. It has been confirmed that the former is suitable for use in curing and cross-linking of surface coatings. I'm tired.

The use of ultraviolet light (UV light) in the production of pressure-sensitive adhesive tapes based on acrylates has already been This is disclosed in German Patent Application No. 15 94 193. that ultraviolet A high-pressure mercury lamp is used as the radiation source. The radiation time required for a layer of 50 g/m2 amounts to 15 minutes. using this In some cases, the radiation field required is long and the speed of moving the web to be processed is This method is more competitive than the normal method because it requires a forced The layer thickness of the pressure-sensitive adhesive to be produced is still G), depending on the choice of method. deciding on a choice. 100 μm or more and several millimeters thick (layer thickness force (so-called 0) It represents a "thick" layer. These advantages are that - the substrates to be bonded together are flat; their good compatibility and increased peel resistance. This is a major point. Generally, once from a pressure sensitive adhesive mass containing a solvent or dispersant It is impossible to produce such a layer with a coating operation of , does the vaporizing liquid become trapped within that layer as blisters or bubbles? It is et al. the production of several thin layers one after the other on each previous layer However, if you do this, you can avoid this effect. For thick layers produced in this way, their shear strength and amount of lamination There are many regrettable points regarding strength. In addition to this, the profitability of this method is also satisfied. It's not something you can do. Lamination of individually produced thin layers to produce one thick layer The method also exhibits the same drawbacks. Already shown in U.S. Pat. No. 4,181,752 As previously described, a new possibility is UV-initiated bulk polymerization. There is an active UV polymerization of solvent-free formulations based on rylates and containing monomers A method for producing a pressure sensitive adhesive by The initiation of the polymerization is initiated by illumination using a black light UV lamp in the range of 300 to 400 nm. It is carried out by shooting means. The part of the energy below 300 nm that this ray has is Must not exceed 10% of the amount of energy emitted between 300 and 400 nm. No. 7 milliwatts per square centimeter is specified as the maximum power density. It is. Although pressure-sensitive adhesives have been obtained that exhibit the given physical properties, it is clear that The UV irradiation time required for this method is several minutes long. This is inconsistent with making it a reality technically. Implementation of U.S. Patent No. 4.181.752 As will be seen in Example 26 (where the reaction in a layer 1.9 cm thick) (produced by exposure to light for 30 minutes), as a general rule: It is possible to cause polymerization using this method even with thick layers.

The long irradiation times again preclude practical application.

The subject matter of U.S. Pat. No. 4,968,558 is that U.S. A further method of performing V-polymerization to produce pressure sensitive adhesives.

The UV light in this case is in the range 280-350 nm [sent from the UV-BJ clamp]. The total radiant power density between 200 and 400 nm is does not exceed the value of 4.0 milliwatts per day. By performing sequential polymerization, mutual It is made by placing several layers on top of each other, and in this connection the thickness of one layer is 6 It may be from 25 to 1125 μm.

The length and production speed of this manufacturing plant are approximately 18 m and 18 m, respectively, from Example 1. and approximately 1.50 m·min−1. These numbers, as well as 10 The technical expense is low due to the fact that 0 rUV-BJ clamps need to be used. Although significant, the production rates achieved make commercial use questionable. It can be concluded that the speed is fast enough.

German Patent Application No. 39 35 097 also has a thick μm) A method for producing pressure-sensitive adhesive layers is claimed, in which radiation-polymerized Carboxyl group-containing polymers (po lymerisate) is polymerized, and then UV rays are cited as a trigger. Using this type of irradiation Laboratory tests have shown that this is the case; however, the suitability of this method is With regard to usability, all available information regarding economic and technical realization is available. (I couldn't get it.

Therefore, the object of the present invention is to provide a method containing acrylic acid and/or acrylic acid derivatives photopolymerizable, solvent-free, flowable formulations in the range of 1l80-400n. Flat rations (flat rations) are prepared by radical polymerization using ultraviolet radiation at To provide a method for producing pressure sensitive adhesives for distribution. The polymerization time required here is sufficient for a pressure sensitive adhesive layer up to 5000 am thick. Even when manufacturing, it is within the range that makes it economically meaningful to shift to production scale. .

According to the invention, the energy required for polymerization is supplied by monochromatic laser radiation. The above objectives are achieved by: This method uses only one wavelength. In the formulation in which the polymerization is to occur, a conventional UV lamp is used. It is possible to radiate energy to a degree that would be unattainable with other systems. On the other hand, Since this polymerization rate is particularly dependent on the magnitude of its initiation energy, Laser polymerization is a pressure-sensitive adhesive that overcomes the drawbacks of conventional technologies in terms of technical realization. It can be said that it is a method of manufacturing a drug.

Laser induced polymerization is sometimes known as such. For example, US patent No. 3,405,045 uses radicals generated by the action of a laser to It is disclosed that monomers are reacted within the same system.

However, this patent specification does not support the use of bulk polymerization in the production of pressure sensitive adhesives. It is impossible to infer any hints regarding. Publication La5ers Chem, 10 (1990) (7) pp. 349-366 by C., Carre et al. In rLasers and PhotopolymersJ, there is a laser induced A general explanation of expolymerization is given. Accordingly, acrylic acid derivatives were also tested. In particular, the use of polyfunctional monomers in the curing of surface coatings has been types are used. Bulk polymerization for producing pressure sensitive adhesives is not mentioned.

The laser to be used according to the invention is one in the wavelength range of 180 to 400 nm. emits a beam of light. In this context, the energy released is continuous Occurs in a pulsed form. As an example of a continuous laser, e.g. ion ion - argon ion laser (approximately 350 nm) and helium ion laser (approximately 350 nm) It is necessary to mention the domium ion laser (325 nm).

However, pulsed lasers are preferred because they This is because the range produces a higher impulse capacity. For example, mainly fluorine or So-called excimer lasers operated with inert gas-halogen mixtures - (Excimer 1asers) belongs to it. As typical of these , ArF (193nm), KrF (248nm), XeC1 (308nm), and XeF (351 nm) lasers. In this specification, pal S-type Nd:YAG lasers can also be used, by doubling their frequency. This is because the emission can then be shifted to the UV range (266 and 365 nm). Ru.

Gas lasers in the range 1180-400n, referred to herein as explicit An extensive table on the rHandbook of La5er 5cienc e and Technology J, Volume 2, pp. 1497-500, CRC Pr Included in essSBoca Reton 1985. the brackets shown above The numbers inside represent typical emission wavelengths. Pulses for these laser types The duration is in the range of less than 50 billionths of a second (50 nanoseconds) and can last several hundred seconds. The pulse repetition frequency can be set over a range of settings. The total number of pulses generated The number can be programmed. The intermediate power output of these lasers is 100 It is possible to approach the value of Watsuto. Approximately 20 megawatts when generating pulses power density of 1 square centimeter can be achieved. More than 1 gigawatt per cm (10' watts/cm2). achievement The pulse energy of several hundred mjoules that can be much higher than the radiant energy that UV lamps have. In connection with this , the energy values given for UV lamps always refer to the entire spectral range. We are not referring to a single wavelength.

The formulations that can be polymerized according to the invention contain olefinically unsaturated monomers. These monomers are preferably of the acrylate family, i.e. acrylic acid and are derived from all monomers obtained from derivatives of The conductor can be modified by substitution in the 1st and/or 2nd positions and/or the carboxy group. means a derivative that can be derived from acrylic acid. Glass below -20℃ All derivatives resulting in homopolymers or copolymers exhibiting a transition temperature are Suitable for the production of pressure sensitive adhesives. Esters of acrylic acid and methacrylic acid Preferred are butyl acrylate, n-octyl, isooctyl, 2-ethylhexyl sil, nonyl or isononyl, as well as decyl and dodenyl methacrylates Can be mentioned.

As is generally known, pressure-sensitive adhesives are made by crosslinking polymers. - Improves the adhesion of the coating material. There are two main possibilities. Number 1 Specifically, it is possible to incorporate olefinically unsaturated carboxylic acids through copolymerization. , through this carboxyl group, polyisocyanates, metal salt esters, gold Genus chelates, metal alcoholades, epoxies, aziridines, triazines or Producing crosslinking by reacting with melamine formaldehyde resin Can be done. In addition to acrylic acid and methacrylic acid, examples of suitable acids include B-acryloylhydroxypropionic acid, vinyl acetic acid, aconitic acid, Lichloroacrylic acid, dimethylacrylic acid, crotonic acid, fumaric acid and itaco Mention may be made of phosphoric acid. Acrylic acid, methacrylic acid and B-acryloyl hydride Roxypropionic acid was found to give particularly good results. the other bridge The method involves incorporating polyunsaturated monomers into this formulation through polymerization. This results in the formation of a network structure. A member of the acrylate family is used here as well. this squirrel Although the list is not claimed to be complete, examples may include the following compounds: . Ethylene glycol di(meth)acrylate, Butanedio di(meth)acrylate hexanediol di(meth)acrylate, decamethyl di(meth)acrylate Rangeol, diethylene glycol di(meth)acrylate, di(meth)acrylate Triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate , propylene glycol di(meth)acrylate, dipropylene di(meth)acrylate Ren glycol, neopentyl glycol di(meth)acrylate, tri(meth) Trimethylolpropane acrylate, pentaerythritol tri(meth)acrylate glycerylpropoxy tri(meth)acrylate, tri(meth)acrylic acid Trimethylolpropane ethoxy and/or tetra(meth)acrylate pen Taerythritol. The following are particularly suitable: 1,6-hexacrylic acid diol, tetraethylene glycol diacrylate and trimethacrylic acid Trimethylolpropane. In certain cases, this pressure sensitive adhesive material has special properties vinyl acetate, vinyl propionate, etc. N-vinylpyrrolidone, vinylimidazole, vinylidene chloride, 4-butyl Mono- or di-esters of styrene and maleic and/or fumaric acids. It is advantageous to include further radically polymerizable monomers such as esters. It is advantageous.

activating the C=C double bonds contained within the formulation using UV light; At least one photoinitiator must be present, since it is difficult if possible at all. may be recommended. These compounds absorb UV radiation energy and at the same time It has the function of generating radicals, and therefore has the function of starting this polymerization reaction. doing. In the practice of this invention, the photoinitiator is at the emission wavelength of the laser used. The choice of photoinitiator is required to have absorption capacity for It depends on the laser type. In the wavelength range of 180 to 400 nm, e.g. , a large number of photoinitiators belong to the following groups: benzophenones, benzene derivatives, benzoin derivatives, dialkoxyacetophenones, hydroxyalkyl derivatives, benzoin derivatives, dialkoxyacetophenones, Killphenones, α-acyl oxime esters, α-halogen ketones, thio xanthones, fluorenone derivatives, anthraquinone derivatives, iron/arene complexes, Dibenzosuberone and Mikler's Ketone.

This reaction between the photoinitiator and UV light can be achieved by using suitable additives (polymerization accelerators). and can be facilitated by For example, amines and 2-ethylhquinolcarboxylic acid of salts withstood the test. The formulation contains one or more further auxiliaries. may be compatible with the rest of its ingredients and sensitive to the effects of UV light. It is assumed that it does not have enough influence to be known. In this connection, J thickeners, Possible plastics, tackifiers, stabilizers, fillers, matting agents, pigments and/or dyes It will be done. Thickeners are used to improve the handling requirements of their flowable formulations. These are particularly important as they are absolutely essential. This fluid thing The viscosity of the mer mixture is often reduced by additional remedies, namely the layer pre-quate (del Without using 1 quarts, it is possible to place this on the substrate in a thick (and stable) manner. The reason for this is that it is impossible to distribute it in sheet form. same Prepolymerides of the same monomer mixture, ori sesamers or polymers with different chemical compositions (which themselves are free radicals) (which may contain reactive groups and/or fillers) By this, the viscosity can be increased. As an example here, higher Urethane acrylates with high crosslinking density, acrylates containing carboxyl groups, etc. Microspheres made from rylate oligomers, silicon dioxide, and appropriate materials can be mentioned.

The monomer portion in this formulation is from 15 to 95% by weight, preferably from 30 to 80% by weight. Must be in percent by weight.

For example, doctoring, roller coating, roll coating Apply this flowable formulation over the entire surface or in a pattern using a gun or nozzle in the desired layer thickness. The method according to the invention is carried out, preferably continuously, by spreading on a substrate in the form of implement. In this context, the layer thickness is between 5 and 500011 m, preferably between 30 and 30 m. 3000+m. A surface from which the resulting pressure-sensitive adhesive layer can be removed All products having a flat shape with surfaces are suitable as substrates. Preferably When choosing the material of the substrate in the form of a web, e.g. polyethylene, polypropylene polymers such as polyester, polyester and polyamide, or paper (where the surface is e.g. If the adhesive is kept away by silicone treatment, etc.) I can do it. Additionally, the substrate may include metal or textile fabric. Special Polytetrafluoroethylene and polyvinyl chloride may also be used if not otherwise treated. Appropriate.

The layer of the formulation thus produced is then exposed to the monochromatic radiation of the laser. The substrate and laser beam can also be moved in relation to each other. It is Noh. Thus, for example, in a direction perpendicular to the direction in which its carrier web moves By rotating and moving the laser beam, the entire surface is can be started. Locally fixed laser beam and below with a carrier web moving along it, and its radiation with radiant energy Special process steps are required to achieve the point densities typical of lasers. these The step includes installing an optical device within the laser beam, which This allows the laser beam to be directed in a small direction (both in one direction and preferably in the direction of its movement). Spread perpendicularly to the direction. To spread this laser beam in this way Of course, the illumination within surfaces exposed to radiation ) is accompanied by a decline. However, the special properties exhibited by lasers The fact that one primary ray has high energy means that polymerization does not occur even when spread at a high angle. range 1 to 320 m joules, which is the luminance value required to start the This means that it is possible to reach 100 ml/cm”. It should be observed that morphism occurs. Of course, even if this temperature is outside room temperature, Good, but you don't get any special benefits in this case. During the polymerization process, polymerization occurs However, this has a negative effect. It does not bring about a process of growth. IR radiation normally present in UV lamps In many cases, there is no need to use cooling. however , special attention should be paid to the oxygen content of the atmosphere. As is generally known, this oxygen molecule is 10,000 to 1,000,000 lower than the actual polymerization reaction rate, depending on the polymer. This is because it reacts with radicals at twice the speed. In addition, oxygen is less than 200 nm absorbs UV rays. Therefore, whether the goal is to shorten the reaction time or If it is necessary to carry out irradiation at wavelengths below 200 nm, non-containing substances such as nitrogen may be used. It is always recommended to exclude oxygen by choosing an active atmosphere or using a vacuum. can be done. Effective protection in this matter is also a UV-transparent sheet for the irradiation. This can be achieved by covering the desired substrate.

In a preferred realization of the method according to the invention, the substrate is designed in the form of a web, This means that the possible web speed is the pressure sensitive adhesive material produced per unit of time. This means that the amount of This web speed is determined by a number of parameters. the composition of this formulation, the layer thickness of this formulation as well as the maximum influence It depends on the irradiation time etc. Effective irradiation time of less than 1 second when using a pulsating laser On the other hand, to polymerize thick layers it is possible to use longer An irradiation time is required, which in the method according to the invention ranges from 10-9 to 1 03 seconds, and the preferred range is 10-2 to 3x102 seconds. Most continuous operation The irradiation time of interest is less than 1 second as far as productivity is concerned. This is because the web speed is thereby in the meter range. Quite the same or by simultaneously using several lasers exhibiting different emission wavelengths. It is also possible to increase the speed. Divide the -next beam into two partial beams. so that they can be directed at fixed intervals onto the formulation layer. It is also possible to achieve spatially displaced double irradiation by .

Particularly when this method is carried out intermittently, long irradiation times of 1 second or more may not be used. I can do it.

After spreading this formulation in a layer on a substrate that is transparent to UV light, Irradiation from the side is also possible, and here we use glass fiber optics to do so. You can bring the laser to the appropriate position.

This irradiation may be done before, during, or after the irradiation of the upper side. is possible. A particular advantage of the above variant of this method is that for thicknesses up to 5000 μm The advantage is that even very thick pressure-sensitive adhesive layers can be produced.

When selecting parameters for this method, the following (some) Basic rules should be observed.

The shorter the laser emission wavelength, the faster the polymerization rate.

The larger the number of pulses of the laser, the higher the conversion rate (turnove). r) becomes higher.

The higher the pulse repetition frequency, i.e. the longer the time interval between pulses. The more it is, the lower the conversion rate will be.

The lower the pulse repetition frequency, the higher the molecular weight of the final product.

In the polymerization according to the present invention, commercially available monomers are prepared prior to carrying out the polymerization. It is not necessary to remove the polymerization inhibitor that is usually added.

The conversion rate using this method is at least 90%. This polymerization reaction is completed After that, the resulting sheet of pressure-sensitive adhesive material is removed if the substrate is rotated. If it is an endless conveyor belt, it can be removed again from this conveyor belt. After transferring this to another substrate that can be It is supplied in the form of pieces for the required processing. The underside of this substrate is also connected. If you want to keep the adhesive out, put these strips inside themselves. It can be rolled up. If this is not possible, keep the adhesive at bay. It is necessary to use one layer of thick cover. Also, handling pieces of this pressure sensitive adhesive material Similar considerations will be made regarding During this polymerization, the substrate is also If the substrate constitutes a substrate during further processing, the transfer step described above can be eliminated. can be done.

The invention may be used in the pressure sensitive adhesive industry or for sealing, mounting or other applications. For example, fixing structural parts of the car body and trim strips to the car body. may be used in some other industries to do this, but here we will However, there is no need to drill holes in the vehicle body when performing this fixing.

A detailed explanation of the invention is provided using the following examples. All of these examples smell Excimer laser type LPX 210 (LA Using MBDA-Physic): Emission wavelength: 351 nm Maximum average output 28W Maximum pulse energy 320mJ Pulse duration: 3Qns Maximum pulse repetition frequency: 100 Hz.

All percentage data are to be understood as % by weight.

Example basic exam Acrylic acid 1) 2-ethylhegysyl acid is 86% and acrylic acid is 12%. and photoinitiator 1rgacure (trademark) 184 (to 1-hydroxy-cyclo xyl-phenylketone) to a layer thickness of 100 μm. Polytetrafluoroethylene (PTFE) with a flat bottom to ensure ) in a plate at room temperature. The cross-sectional area of the available laser beam is l, 4x3 Choose the size of the dish so that cm completely covers the formulation layer. The following article This formulation layer is exposed to radiation under conditions.

Such pulse energy: 200mJ Such pulse repetition frequency: 10 Hz Pulse number: 200 Le’,,%-Noyon 48mJ-cm-” Duration 20 seconds.

The layer obtained from this formulation then acquires pressure-sensitive adhesive properties and further Remove it from the pan for testing purposes.

a) Yield determination, drying the sample at a temperature of 180 °C for 1 hour and After cooling to room temperature, the gravity I measurement is performed again. In this first approximation, this weight The loss represents the role played by uncovered monomers. The case As a result, this amount of loss is 1.8% by weight, which is due to the amount of polymer lost from the monomer used. This corresponds to a conversion rate to reamer of 98.2%.

b) Molecular weight determination This is carried out using Nigel permeation chromatography. with this The equipment used was Polymer 5tandad 5service, imported from Germany. The process was carried out using cross-linked polystyrene as column packing. cormorant. Tetrahydrofuran with t-butylhydroxytoluene added as internal standard The measurement is carried out in solution. The median molecular weight M resulting from this evaluation is 822,000 It's Dalton.

C) Measurement of peel strength (adhesion) and AFER of the resulting pressure-sensitive adhesive fragments As a result of testing according to A standard 4001, the peel strength of this 7 is 12.6N/1 ．． It was measured to have a value of 4 cm.

Example 2 thicker layer The formulation according to Example 1 was placed in the PTFE pan with a layer thickness of 11000a. and then exposed to radiation with the following settings: such pulse energy 15 0mJ Such pulse repetition frequency: 5 Hz Pulse number: 400 Rumifuin-a-an 36rrd + Cm-2 duration 80 seconds.

This flowable formulation layer is then transformed to yield a tacky pressure-sensitive adhesive layer. The usability of this was confirmed through sensory testing.

Example 3 Polymerization accelerator It additionally contains a polymerization accelerator in the form of Sn(I)-2-ethylhexanoate. Example 2 was repeated using a formulation with (20% of the amount of photoinitiator), but now The required irradiation time was 40 seconds (Nockles number 200). pressure sensitive adhesive again A drug layer was obtained, which could not be distinguished from Example 2 even by sensory testing. There wasn't.

Formulation with a thickness of 5000 μm in an aluminum mold pan using the test method of Example 1. Prepare the material layer. The following parameter settings: Pulse energy 300 mJ Such pulse repetition frequency: 10 Hz Pulse number: 800 Duration: 80 seconds After irradiation at , a fully polymerized pressure-sensitive adhesive layer was obtained.

Example 5 crosslinking agent Example 1 to contain 0.5% crosslinking agent in the form of acetylacetone A1. Change the test method. 1000 μm was selected as the layer thickness, and the irradiation conditions were corresponds to that of the second embodiment.

The resulting pressure-sensitive adhesive layer exhibits high tackiness and 5. 9N/1゜4cm It has a peel strength of .

Example 6-13 Composition of monomers The layer thickness of this formulation is 11000i1. This composition along with its measured pull is Table 1 shows the peeling strength.

In all cases, pressure sensitive with a peel strength that does not necessarily reach the expected value An adhesive polymer is obtained. The composition of these monomers and their irradiation conditions must be optimized. The reason should be found in what is not being done.

Example 14 Thickening of the formulation Test methods for this formulation: 42% 2-ethylhexyl acrylate 6% acrylic acid 1% Irgacure(TM) 184 (see Example 1) 1% ZLI 3 331 (see Table 1) 50% Ebecryl(TM) 230 (oligomer urethane acrylate (UCB).

After mixing, this formulation has a viscosity of 1.5 Pa-s (Type B viscometer). and without causing deliquescence (this can be applied as a sheet distribution onto a substrate). I was able to expand it.

Irradiation of a layer with a thickness of 1000 μm is carried out under the following conditions.

Such pulse energy: 150mJ Such pulse repetition frequency: 5 Hz Pulse number: 400 Luminescence 36mJ-cm-2 Duration 80 seconds.

The pressure-sensitive adhesive layer thus obtained is fully polymerized and suitable for skivining. The skiving strength was 5.8N/1.4cm.

Example 15 Using the formulation test method of Example 14 and using a coating box, a thickness of 1 The specified A layer of 1000 gm is produced continuously, which can be passed under the radiation source at speed. release The width of the web to be exposed to the radiation in the direction perpendicular to the direction of movement is 30 cm. Then, an optical device is used to widen the laser beam.

The irradiation conditions are as follows: Such pulse energy: 300mJ Such pulse repetition frequency 50 hertz luminescence 7.6 mJ-cm- ”.

A pressure-sensitive adhesive layer was obtained at a web speed of 3.80 m min−1, which was can be further processed by dividing it into scrolls. This production rate is, of course, extremely dependent on the layer thickness; however, this test method cannot be used appropriately. by changing the rate, e.g. by adding polymerization accelerators. can be raised. Regarding this issue, processing should be carried out in an inert atmosphere. also shows an effect.

Although the invention has been described in terms of certain special embodiments, this does not mean that the invention It is not intended to be limited to these embodiments. Departing from the scope of the invention Submit a copy of the corrected sound and a translation of the corrected sound (a translation of the corrected sound may occur to the engineer). (Patent Law Article 184-8) October 3, 1994

Claims (19)

[Claims] 1. Flowable, photopolymerizable, and solvent-free acrylic acid and/or acrylic acid derivative-containing formulations in the violet range of 180-400 nm. By radical polymerization using external radiation, a pressure-sensitive adhesive in sheet form is produced. In this method, the energy required for this polymerization is supplied by monochromatic laser radiation. A method characterized by feeding by line. 2. The energy required to initiate the polymerization is provided by the monochromatic radiation of a laser. The method according to claim 1, characterized in that: 3. The method according to claim 1 or 2, characterized in that a pulsed laser is used. Law. 4. Claims characterized in that a photoinitiator capable of absorbing ultraviolet radiation is added to the formulation. The method described in Ranges 1 to 3. 5. Process according to claim 4, characterized in that a polymerization accelerator is added to the formulation. . 6. The polymerization accelerator is selected from the group of amines and salts of 2-ethylhexylcarboxylic acid. 6. The method according to claim 5, characterized in that the method is selected from: 7. Thickening that is compatible with the rest of its ingredients and does not worsen the effectiveness of UV rays agents, plasticizers, tackifiers, stabilizers, fillers, matting agents, pigments and dyes. The preceding claim is characterized in that one or more additives from the group of The method described in one or more of the items in the box. 8. The laser beam used is 0.1-320 mjoules/c on the formulation. according to one or more of the preceding claims, characterized in that it produces an illumination of m2. Method. 9. Sheet-like rations with a thickness of 5 to 5000 μm, preferably 30-3000 μm (2) exposing the formulation to said UV radiation as The method described above. 10. characterized in that the duration of its UV irradiation ranges from 10-9 to 103 seconds A method according to one or more of the preceding claims. 11. Claim characterized in that the duration is in the range of 10-2 to 3x102 seconds. The method according to claim 10. 12. Claims characterized in that oxygen is excluded when carrying out the UV irradiation. The method described in one or more of the items in the box. 13. Coupled by moving the laser beam and the compound in relation to each other. Process according to one or more of the preceding claims, characterized in that the polymerization is carried out continuously. 14. the compounding into a laser beam spread in at least one direction using an optical device; A method according to one or more of the preceding claims, characterized in that the method comprises exposing an object. 15. Several lasers can be used simultaneously or sequentially to carry out the polymerization. A method according to one or more of the preceding claims. 16. Claims characterized in that the lasers exhibit the same or different emission wavelengths The method described in Box 15. 17. The sheet or layered formulation is spread on a substrate that is transparent to UV light. and irradiation is also performed from below. The method described in item 1 or more. 18. Bring the laser beam to the proper position using glass fiber optics 18. The method according to claim 17, characterized in that: 19. Is the irradiation from the lower side performed before or while the irradiation is performed from the upper side? or later on, and this is done especially for thick pressure-sensitive adhesives in layers up to 5000 μm. 19. The method according to claim 18, characterized in that it is used in the case of layers.