WO1995028437A1

WO1995028437A1 - One-piece reactive melt moulding and process for producing it

Info

Publication number: WO1995028437A1
Application number: PCT/EP1995/001272
Authority: WO
Inventors: Rudolf Hinterwaldner; Harald Braun
Original assignee: Novamelt Research Gmbh
Priority date: 1994-04-15
Filing date: 1995-04-07
Publication date: 1995-10-26
Also published as: DE4413113A1

Abstract

The object of the invention is a one-piece, long-shelf-life, chemically reactive moulding for forming a coating, adhesive or sealing compound, consisting of (a) one or more reactive, meltable and/or thermoplastic backbone binder(s), (b) one or more meltable reactive compound(s) for curing or cross-linking and (c) other prior art additives, in which (a) and (b) have different melting and/or softening ranges and, after melting and mixing, cure or cross-link to form a duromer, and a process for producing this moulding.

Description

Description One-piece, reactive melt-molded body and process for its production

The invention relates to a one-piece melt mass molded body made of reactive, chemically setting backbone: binders or polymers, which hardens or crosslinks after heating and simultaneous mixing.

Physically setting hotmelt compositions, in particular hotmelt adhesives which can be reversibly liquefied by means of heat and solidify or set again on cooling, have been known for a long time and represent the state of the art. They are used in different manufacturing processes Assemblies and used in the handicraft and DIY sector. Such enamels include in the adhesive monographs by Ralf Jordan "Schmelzklebstoffe" Vol. a - 4c, Hinterwaldnererlag, Munich 1985/87 or G. habenicht "Kleben", Springer-Verlag, Berlin-Heidelberg, 2nd edition (1990), p. 139 ff.

Enamel compositions are also 100% solid systems and do not require any drying processes to set or solidify, as they are solvent-free and / or water-free. They are constructed on the basis of thermoplastic backbone polymers which have a thermally reversible nature and are thermosensitive.

The short setting times, which are given by rapid cooling, allow the use of melt masses in many industrial and artisanal manufacturing and assembly systems "coating, dipping, spraying and gluing" in order to be able to coat and / or connect products or elements. Among other things, Glue packaging, book spines, assembly parts, furniture parts and the like and / or protect elements, goods and the like by covering them against environmental influences.

The melt masses, in particular the hot melt adhesives, are processed - in industrial applications from granules or

Block goods in melting devices developed specifically for this purpose

and

- In the assembly, manual and do-it-yourself sector by means of heated melt guns, which can melt melt cartridges, threads or strands.

Moisture-curing hotmelt compositions, in particular hotmelt adhesives, are also known in the prior art. These include built on the basis of polyurethanes as a backbone binder. The chemical setting reaction is started after the mass has cooled and solidified by the ambient humidity, e.g. Air, initiated. The rate of chemical curing or crosslinking in order to cure or crosslink a layer is a function of time, moisture and / or diffusion, which generally takes from several days to a week. Lying e.g. If the moisture content in the environment is below or above critical threshold values, either chemical setting is completely prevented or there are no sufficient cross-linking bridges for the expected strength in a structural matrix. Furthermore, the part geometry in principle requires access to moisture in order to be able to carry out the chemical reaction at all.

Irrespective of this, the moisture-curing enamels require moisture-proof packaging containers, to which additional moisture-absorbing substances have to be added in order to protect them against premature setting or hardening during storage and transport.

In both types of melt mass, the backbone polymers or binders are already present with relatively higher molecular weights. This is especially true for those only physically setting enamel systems. Because organic

Polymers are generally poor heat conductors and in some cases have relatively high melting points and / or softening ranges, high amounts of thermal energy are required in order to convert them quickly from the solid to the liquid state. ^* Therefore, they must preferably be softened or liquefied at temperatures of 150 to 250 ° C. in order to be able to wet surfaces.

Due to their low thermal conductivity, thermoplastics in particular are also thermosensitive and tend to tend relatively quickly, among other things. for degradation and cracking, which is described in the professional world with the term "heat history".

As a result of such thermooxidative degradation, the backbone polymers or binders lose functional properties and strengths, and toxic degradation products and gases can additionally be formed.

Furthermore, the physically setting enamel compositions have further disadvantages, which include the following are:

Low heat resistance, which is far below the melting points or ranges of the backbone polymers

- Creep under permanent loads

- often insufficient chemical resistance.

The same applies to the moisture-hardening enamels, as long as the isocyanate bridge members have not formed through hardening or crosslinking.

In order to be able to counter these negative properties, which still adhere to the above types of enamel, in more demanding applications, so-called two-component enamel, in particular hot melt adhesives, have recently been introduced to the market, as described, inter alia, in EP 0 270 831, 0 347,516 and 0,527,548. In this case, the individual components are liquefied in complex, expensive melting and processing devices and then made ready for processing in specifically developed metering and mixing devices, provided that it is not radiation-curable melting compounds. Due to the short pot life, the sensitive dosing and mixing devices have to be rinsed with a component at least once per shift so that the mixing chamber and the product-carrying valves do not become blocked by polymerized and / or through-polymerized components and cause long downtimes. Such very expensive melting, dosing and mixing devices can only be installed in sensitive high-tech areas, where a high level of maintenance is technically and economically justified for the use of expensive structural melting compounds. These costly melting, dosing and mixing devices for 2-component reaction melt compositions are not yet offered as a closed unit on the system market. They have to be created individually from individual units and functional parts.

With today's application technology, the use of high-quality 2-component hotmelt, in particular hotmelt adhesives, is very narrow.

Regardless of the above prior art for enamels, DE-PS 23 22 806 describes an adhesive and sealing compound consisting of a shaped body consisting of two strips lying side by side. This is a kneadable mass that is reactivated when the two strips are kneaded and then hardens. These one-piece moldings have a number of disadvantages, which include the following are:

- Surface stickiness, therefore the one-piece molded articles must be packed individually in packaging materials equipped with release agent;

- Temperature-dependent kneadability - Different mixing degrees, which influence the achievable end properties;

- long curing timeπ

- limited storage time

- high physiological concerns due to toxic ingredients in hand kneading due to absorption through the skin.

For these and other reasons, this mass could not assert itself on the market.

However, since there is a great need for two and multi-component hotmelt compositions, in particular hotmelt adhesives, in many areas of application if, among other things, Given simple and safe processing systems, the inventors have set themselves the task of providing technical and / or economic remedies for this. In particular for the assembly, manual and do-it-yourself sectors, in the vehicle and construction industry, in electrical engineering, fastening technology, assembly and repair technology, nevertheless, 2-component hotmelt, in particular hotmelt adhesives for the production of structural, aging and long-term - To be able to provide permanent connections economically is the task and the aim of the present invention.

The invention relates to a one-piece, storage-stable, meltable, chemically reacting molded body for forming a coating, adhesive and / or sealing compound, consisting of

a) one or more reactive, meltable and / or thermoplastic backbone binder (s)

b) one or more meltable, reactive compound (s) used for curing or crosslinking

and

c) optionally other known additives, - 6 - wherein a) and b) have different melting and / or softening ranges and harden or crosslink to a thermoset after melting and mixing.

It is particularly preferred according to the invention that the shaped body has a cylindrical, conical, cubic, cuboid, spherical, pearl, strip and / or platelet shape.

To increase the resistance to environmental influences and / or to render it inert during storage and transport, it is expedient for at least one of the reactive constituents, in particular in the case of highly reactive compounds, to be microencapsulated.

The homogeneous distribution of the reactive constituents in the shaped body according to the invention is improved in that at least one of the reactive constituents is embedded in the mass in the form of a sphere and / or beads.

A further preferred embodiment of the shaped body according to the invention is that at least one of the reactive components is embedded in the mass as a round profile or strip.

The molded body according to the invention can also be a two- or multi-layer laminate or sandwich composed of the reactive constituents a) and b).

In a further embodiment of the present invention, the molded body is coated with at least one of the reactive components.

The reaction of the reactive constituents of the molded article according to the invention is initiated by melting and mixing, which then chemically set, harden or crosslink by polymerization, polyaddition and / or polycondensation. The backbone binders for producing the molded articles according to the invention are thermoplastic and / or meltable polymers. Backbone binders are particularly preferred

addition-setting polymers, such as epoxy, polyurethane, isocyanate, polyamide resins and / or reactive derivatives thereof,

- polymerizing polymers that have at least one reactive

Group of the general formula

RI CH ₂ = C - X in the

RIX = - C -, - C - 0 -, - CH -, - CH ₂ -, - 0 -, - N -

0 0

R = H, - a C. - C. alkyl radical, halogen or - CN mean, have and / or

- Polycondensing polymers such as urea, melamine, phenol, cresol, novolak, resorcinol resins and / or their copolymers.

Particularly preferred backing binders have a dual functionality. That they contain reactive groups that bind via polyaddition, polymerization and / or polycondensation. Examples include polymers that contain both reactive epoxy and unsaturated groups or double bonds.

To improve the processing rheology and / or the final properties, the integral compositions can contain fillers, pigments and / or binders. If they also contain foam and blowing agents, end products with low density are created.

In a special embodiment, the moldings according to the invention are equipped with reversible and / or irreversible temperature measurement colors. The method for producing a one-piece molded body according to the present invention is characterized in that a hollow body is produced from a higher-melting or softening reactive component and the resulting cavity is filled with a melting or softening reactive component.

A further process for producing a one-piece molded body is characterized in that a hollow profile is drawn from the components a) or b) and the cooled and solidified continuous tube is then filled with the components a) or b).

One-piece moldings according to the present invention can be produced by mixing in or coating the higher-melting, still solid, small-sized constituents into the low-melting, liquid reactive constituents.

The one-piece, meltable and reactive moldings according to the present invention consist of at least 2 reactive components which are capable of polymerization, polycondensation and / or polyaddition with one another in the liquid state. At room temperature, however, the reaction components are solid and have a non-tacky surface. Only when heated above their own melting points do they begin to flow and change to a liquid state. Since the individual reaction components have different and / or diverging melting points, this physical property is an essential key to solving the problem according to the invention. If the gradual gradations of the melting points are used to produce the moldings according to the invention, only at least one of the reaction components has to be in the liquid and the other in the solid state. In order to achieve this goal in the production of the moldings according to the invention, the temperature intervals of the melting points of at least 2 of the reaction components must be = 10 ° C., preferably = 20 ° C. and in particular = 30 ° C. With a very sharp melting point of two reaction partners, a temperature interval of 10 ° C. can also be sufficient, as has surprisingly been found. Through the use according to the invention of the temperature interval of their melting points given by at least 2 reaction components, the production of the shaped bodies is considerably simplified, because

a) only one reaction component for processing, casting, extruding, incorporating and / or mixing has to be liquid and thus the mutual reaction affinity remains small

and

b) a chemically inert, solid physical state is quickly achieved by cooling.

An (initial) polymerization (interfacial polymerization) to be observed at the interfaces of the reaction components is desired according to the invention and contributes to the stability of the shaped body, because at least partial adhesion points form between components A and B (backbone binder and hardener or vice versa).

Using the melting point intervals from at least 2 reaction components, the moldings according to the invention can be produced economically using different process technologies.

According to the invention, i.a. four technologies in particular:

a) According to the principle of the casting technique, a hollow profile is produced in a mold from the higher melting reaction component. This form consists of a cooling medium tube and a jacket tube and the liquid reaction component is introduced on the front side between the two tubes. After cooling and off forming the hollow profile, the cooling medium tube provided with the release agent is removed and the hollow core of the casting is poured out with the low-melting reaction component. After cooling and solidification, the molded body is removed from the mold.

Since the plastics are poor heat conductors, the demolding can be carried out by simply heating the metal mold surfaces instead of using a release agent. Hollow profiles that are then filled can be produced in an analogous manner.

b) In contrast, when using the mixing technology, the procedure is the reverse. Here, the low-melting reaction component is liquefied by means of heat and placed in a mixing room. The high-melting particles are introduced into the liquid reaction component in the form of solid particles, mixed homogeneously and then converted into moldings by casting, molding and the like, with simultaneous cooling.

The solid particles of the higher-melting reaction components can have the form of microspheres, microcapsules, beads, granules, platelets, and the like.

c) extrusion technology

Both components are extruded in a coextrusion line as endless strands, with no mixing of the two components.

d) microsphere technology

The Nukem microsphere technology from Nukem GmbH in D-63755 Alzenau is particularly suitable for producing homogeneous, one-piece microspheres with diameters of 50 to 4000 μm from reaction components A and B. Here, microspheres with homogeneous diameters are prefabricated from the higher-melting component and then coated in the melt of the low-melting component. The coated microspheres - 11 - are then immediately cooled, for example in a cold protective gas stream (N "or the like.). This production can take place in a continuous process technology.

The dimensioning of the void volumes in the molded articles according to the invention are determined by the mixing ratios of the respective reactants. Depending on the reaction components, mixing ratios between 99: 1 and 10:90 are possible. Mixing ratios between 10: 1 to 1: 2 are particularly preferred, as a result of which sufficient mixing of the reaction components is ensured during application.

Using the above and other process technologies, the one-piece, meltable and reactive moldings according to the invention can be economically produced from two-component or multi-component hotmelt compositions, in particular hotmelt adhesives. They can have cylindrical, conical, cubic, cuboid, pearl, plate, and / or stripe form. The cylindrical, pearl and / or strip shapes are particularly preferred because they can be processed on known melt guns. The lengths and cross sections of the moldings according to the invention can be variable.

1 to 5 show examples of the reactive moldings according to the invention made of hotmelt compositions, in particular hotmelt adhesives, but are not limited to these.

Fig.l: 1-piece, reactive, round shaped body, consisting of at least 2 reactants, with a variable diameter as an endless strand, cylinder, stick or disc.

2: 1-piece molded body, consisting of at least 2 reaction substances, with a square or rectangular base as an endless strand, in an elongated form or as platelet granules; the second component has a square or rectangular base. Fig .3: 1-piece molded body consisting of at least 2 reactants, endless or cut to length as a triangular, 1/4 to 1/2 circular or round base.

4: 1-piece molded body consisting of 2 reaction substances, of which one of components A or B is embedded in a microencapsulated manner.

Fig. 5: One-piece beads or microspheres, of which the higher melting component is coated with the lower melting component.

All the reactive backbone polymers or binders and the compounds used for curing or crosslinking are suitable for producing the shaped bodies according to the invention, prior to the curing or crosslinking reaction

- Thermoplastic and / or meltable properties and

- At temperatures = + 30 ° C, in particular = + 40 ° C have semi-solid to solid physical states.

Suitable backbone polymers or binders include the following, which are listed below according to their curing or crosslinking principle.

Polyaddition: epoxy resins, for example bisphenol A diglycidyl ether, phenol novolak glycidyl ether, N, N diglycidylaniline, cycloaliphatic, heterocyclic and aliphatic epoxy resins; Polysulfides, polyurethane resins, silicone resins, polyamides, polyimides, polyols, polyesters and polyisocyanates Polycondensation: aldehyde condensation resins, such as urea, melamine, phenol and novolak resins

Polymerization: acrylic and / or methacrylic resins, unsaturated polyester resins and epoxies.

The compounds used for curing or crosslinking are monomeric and / or polymeric reactants, reaction initiators and / or reaction accelerators, depending on the particular types of reaction. Typical examples of this are:

Polyaddition: For the conversion of epoxy, hydroxyl and / or isocyanate group-containing backbone binders are suitable, inter alia. Compounds which carry active H atoms, such as polyamides, polyimides, polyamines, azines, carbamides, carboxylic acids, mercaptans, hydrogen silicates, isocyanates.

Polycondensation: acidic hardener components, e.g. Phosphoric acid, p-toluenesulfonic acid, phthalic acids, maleic acids; alkaline hardener components, such as amine and ammonium salts, compounds containing aldehyde groups.

Polymerization: reaction initiators, such as organic peroxides, per compounds, organometallic compounds, Lewis and / or protonic acids and / or bases, for example BF ₃ complexes, imidazoles, tertiary amines, photosensitizers.

The individual reactive components of the moldings according to the invention can contain further additives. These additives include plasticizers, flexibilizing substances, waxes, fillers, adhesion promoters, pigments and dyes in order to give them characteristic features and / or specific properties, if necessary. The nature of these additives is primarily determined by their compatibility with the backbone polymers or binders and the compounds used for curing or crosslinking.

For visual control of the sensitive parameters during melting and processing by the user, the reaction components of the molded bodies according to the invention can be colored or pigmented in different shades. In addition to the known dyes and / or pigments, according to the present invention, thermophilic dyes and / or pigments are particularly suitable for coloring, which also includes the temperature measurement varnishes, temperature measurement inks, temperature indicators and liquid crystals. They are summarized below under the term "temperature measuring colors".

The temperature measurement colors change their characteristic hue reversibly or irreversibly at specific temperature values. In the present invention, the reversible and / or the temperature measurement colors having several color change points are particularly preferred because, among other things, in the application of the moldings according to the invention

a) heating and attaining the prescribed processing temperature and b) the quality of the mix obtained, which is obtained after melting and pressing out from a heated device,

becomes visually controllable and also offers and communicates a high level of quality assurance to non-specialists.

The selection criteria that are placed on the temperature measurement colors for use in the reaction co-piπten of the moldings according to the invention include depending on:

- Compatibility with the ingredients of the individual reaction components

- The softening temperatures and / or melting points of the individual reaction components - The change in color when the processing temperature is reached and - The desired mixed color from the individual reaction components.

The temperature measuring inks integrated in the hardened or crosslinked melt masses, in particular hot melt adhesives, can then also take over essential control functions if they

a) reversible colors and / or in a temperature interval

b) multiple color change points with color change with increasing temperatures

possess, as was surprisingly found. This enables the temperature loads on coatings and adhesive films to be monitored and controlled. This can be of current interest, for example, if

a) in the case of coatings or films, a predetermined limit in temperature resistance is exceeded and / or b) in the case of adhesive bonding, in particular in the case of structural adhesive compounds, the adhesive layer is damaged or destroyed because the temperature is too high and / or too long, and the adhesive joint opens.

This fact provides an additional security check when monitoring aging and long-term behavior.

Basically, according to the present invention, there is the possibility that only one reaction component is colored with temperature measuring ink and the others with inert dyes or pigments.

Chemically, the temperature measurement colors are usually based on copper, cobalt, nickel, chromium, vanadium, molybdenum or uranium salts. Examples include: - Ni (NH ₄ ) P0 ₄ . 6 H ₂ 0 (^ 120 ° C light green -> gray)

- (H ₄ ) ₃ P0 ₄ . 12 Mo 0 ₃ (^ 140 - 160 ° C yellow- ^ black)

- Cu (CNS) ₂ . 2 pyridine (■>, 135 ° C green ■> yellow and

/ 220 ° C yellow • ■ black)

Co (NH_) _R (C- 0.) „(- ^ 215 ° C yellow -» violet ^J ° ^ά 250-270 ° C violet -> brown 320-350 ° C brown •> black)

- Co (N0) ₂ • 2 hexamethylenetetramine. 10 h _? 0 (reversible at 75 ° C from pink to purple)

In the case of liquid crystals, the so-called cholesterol phases are of current interest.

The moldings according to the invention can be used in many areas of technology, the commercial economy, handicrafts and home improvement. Due to the one-tier application form and the secure processing in known or modified melting devices, e.g. Hot-melt or hot-melt adhesive guns, the molded articles according to the invention offer the skilled worker and the non-specialist a high level of safety in processing and application, with a pronounced economy. At the same time, the moldings according to the invention make an essential contribution to occupational hygiene and environmental protection because

- When loading the application devices, the moldings are solid and

- Less waste is produced during processing and this can be disposed of as industrial waste after hardening or crosslinking.

A large number of materials and / or substrates can be coated or coated, connected to and with one another, fastened and / or sealed with the shaped bodies according to the invention from the reactive melt compositions. - 17 - The materials and / or substrates can include metals such as steel and aluminum; inorganic materials such as stones, concrete, glass and ceramics; Elastomers; Plastics such as thermoplastics and thermosets; Wood and wood materials; Foils, plastic laminates; textile materials, paper, cardboard and the like.

Such tasks for connecting, fastening, sealing, filling, covering and / or filling are available in many areas of research, industry, assembly, home and handicraft. This includes the construction industry with civil engineering and interior construction; wood and plastics processing industry; Vehicle, ship and aircraft construction, machine and apparatus construction, also many areas of home and handicraft, assembly, installation and repair.

According to the present invention, not only are new, innovative, reactivatable and meltable, one-piece molded articles made of hotmelt compositions, in particular hotmelt adhesives, provided for many areas of application and use which do not have the many disadvantages, but they also have a number of additional processes - and application-technical advantages that have long been unfulfilled in practice.

These advantages are dependent, inter alia, on the particular molding composition. the following:

- During processing reactive, meltable and hardenable or crosslinkable one-piece molded body with the known advantages of a two- or multi-component melt mass;

- Easy and uncritical use, since no mixing is required.

- no mixing errors - Easy and uniform reactivability

- Pre-programmed reactions, such as gelling and. Curing times

- Low-shrinkage and / or -free hardening and hardening

- Good storage stability of the molding compounds

- Reduction and / or elimination of physiological and toxicological concerns regarding occupational hygiene and / or environmental problems when using and processing hazardous substances.

The invention is explained in more detail by the following examples, but without being restricted thereto.

example 1

Using the casting technique, a one-piece molded body was produced from a 2-component hot melt adhesive based on polyamide. The 2-component hot melt adhesive (Curemelt 570/100 from Union Camp) had the following characteristics:

Component A (polyamide)

Ring & Ball softening point 135 ° C viscosity at 190 ° C 7000 mPa.s

Component B (epoxy resin)

Ring & Ball softening point 50 ° C viscosity at 130 ° C 500 mPa.s

Mixing ratios of components A: B ^{• * ■} 10: 1 volume parts

The mold for producing the molded body according to the invention by means of the casting technique consisted of a jacket tube and a medium tube which was closed at one end by means of a plate. The shape is made of stainless steel. The medium pipe was not firmly connected to the jacket pipe and was therefore easily removable. The inn ^e re surface of the jacket tube and the & ^■ .3ere surface of the medium pipe is provided with an epoxidized isoolefin as a release agent (eg, Permethyl 100 epoxides, Permethyl Corp., Pottstown, PA, USA) and assembled.

The cavities had the following volumes:

- between jacket and medium pipe: 200 ml

- Medium tube: 20 ml.

With component A, a hollow molded body was first produced in such a way that the polyamide resin was heated to 190 ° C. and the melt produced was introduced into the cavity between the jacket and carrier pipe via the end face. After filling this cavity without bubbles, the mold was placed in a cold water bath for cooling. The medium pipe was used for faster solidification of the Blown cold air. As soon as component A had cooled and solidified, the medium pipe was removed from the

Mold removed.

The cavity created in the casting - after removing the medium pipe - was then cast and filled with component B (epoxy resin) heated to 100 ° C. The mold was constantly cooled until the core of the molded body solidified. Finally, the mold was removed.

The resulting shaped body had a diameter of 11 mm and was cut to lengths of 90 mm.

The cut-to-length shaped bodies, also called sticks or cartridges in practice, were placed in a commercially available hot-melt adhesive handgun and then processed by melting and squeezing.

Steel and plastic adhesive bonds were produced with the melt produced from the molded body according to the invention, and the strength values determined were compared with analog bonds, in which the same hot melt adhesive was prepared and processed using an expensive two-component melting, mixing and metering system. The following values were determined:

Shaped body melting plant according to the invention (comparison)

Open time: 48 seconds 45 seconds

Gel time: 6-7 minutes 6 minutes

Tensile strenght:

Steel 3.9 MPa 4 MPa

ABS 4.7 MPa 4.6 MPa

Peel strength (N / 25 mm)

PVC 195 197

The melting temperature was 190 ° C in both cases. Example 2

Example 1 is repeated with the following modifications that components A and B form a polyurethane system and are colored with dyes. The moldings according to the invention have the following composition:

Component A

A mixture of copolyesters (Dynacoll ^ RP 360/130/250 = 40:20:60 parts by weight) with an average hydroxyl number of 27 and a melting range of 110-120 ° C.

Component B

2,2'-Diisocyanato-Dipheπylmethan with a melting point of 45 - 47 ° C and an NCO content of 33.6%.

The mixing ratio of components A: B = 100: 8 parts by volume

Component A was colored at a temperature of 125 ° C. by adding 0.05% by weight of the temperature measuring color with the formula Cu (CNS) ₂ '2 pyridine. It has 2 temperature-dependent color change levels, namely

- from green - ^• yellow: approx. 135 ° C and

- from yellow - ^■ > black: approx. 220 ° C.

Component B was colored with 0.01% by weight of a normal blue azo dye.

With the colored component A melt with a temperature of 125 ° C. and a green color, a hollow body was produced in the mold by cooling the melt. The cavity was then cast with the blue-colored component B melt (55 ° C.) and converted into a solid state by cooling the moldings according to the invention. The sticks made from it were then melted in a hot melt glue gun and processed by pressing. In order to visual control the color changes

Application via

- Melting and processing temperatures

- Mix quality

- Theological processing properties and

- If necessary, thermo-oxidative damage

3 different temperatures of 125, 140 and 230 ° C were selected to enable this. The following were determined as comparative results:

At 125 ° C

The melt which was pressed out was highly viscous and of a slightly greenish blue color. A sign that the melting and processing temperature was too low, there was no homogeneous mixture. The test specimens bonded to them showed a high coefficient of variation of 25% in their strength values - tensile strength 20 N / mm - and on average 20% lower tensile strengths.

At 140 ° C

The pressed melt had an average viscosity of approx. 14,000 to 16,000 mPa.s and a uniform green color. The green hue was created from the yellow hue of the temperature measuring color and the blue azo dye. The test specimens glued to it provided tensile strength values of 20 to 22 N / mm ² .

At 230 ° C

The melt that was pressed out was colored black. A visual sign that the possible processing temperature was exceeded and that thermo-oxidative damage or degradation of the hot melt adhesive is to be expected. The assumption was confirmed in the strength tests. The values were on average 25% lower than at the application temperature of 140 ° C. It has thus been possible to prove that temperature measuring colors in the molded body according to the invention are a useful aid for quality and mixing control.

Example 3 a

Another shaped body according to the invention was produced by mixing solid particles into a melt. The solid particles were so-called microspheres.

For this purpose, a melt made of an epoxy resin, e.g. N, N, N ', N' -Tetraglycidyl- c ^* , CΛ-. ^, -bis- (4-aminophenyl) -p-diisopropylbenzene (FP 50 ° C), like Epikote © 1071 from Shell Chemical at approx. 80 ° C kept constant. The microspheres with a diameter of 50 μm, prefabricated from OL, θ (-bis- (4-aminophenyl) -p-diiso-propylbenzene (FP 164 ° C.), like Epikure * - '1061 from Shell Chemical, become the melt in equimolar proportions This mixture is used to produce sticks 90 mm long and 11 mm in diameter in a simple round hollow mold made of stainless steel.

Example 3 b

In repetition of Example 1, κf _* - _t rf -bis- (4-aminopheynl) -p-diisopropylbeπzol (Epikure * - '1061). a hollow body is made by casting from the melt (180 - 185 ° C) and demolded after cooling. The cavity was then filled with the epoxy resin "Epikote ^w 1071" from its melt (80 ° C) and brought to cool.

The sticks are then processed using a hot melt gun. Example 4

A molded article according to the invention was produced from a novolak epoxydimethacrylate (FP 60 ° C) and a microencapsulated Dibπzoylperoxid with a wall material made of a polymer wax (FP 110 ° C) by ^" mixing at 70 ° C and then pouring into a one-piece mold The molded body produced was melted in a hot melt handgun at 170 ° C. and the melted mass was applied to a cleaned steel surface via a slot die.The coating layer had reached a degree of crosslinking of 90% after 15 minutes.

Example 5

Example 1 is repeated in such a way that one-piece beads in sizes of 50-100 μm are produced from components A (Curemelt 570) and B (Curemelt 100). These one-piece beads are produced in two process steps. Beads or microspheres are prefabricated from the higher-melting polyamide (Curemelt 570). These have diameters from 50 to 60 μm. These polyamide microspheres are continuously fed to the coating bath from the epoxy resin melt (Curemelt 100). The melt has a temperature of 75 ° C. The polyamide microspheres - in free fall - migrate through the melt, the coating with component B taking place in the required ratio of 10: 1. The coated microspheres are continuously removed from the bottom of the melting tank and immediately cooled in a cold protective gas stream (N ₂ ) with a temperature of -10 ° C. and collected in a container as one-piece beads with diameters of 60 to 80 μm.

Claims

- 25 - Claims

1. One-piece, storage-stable, fusible, chemically reactive molded body to form a coating adhesive and / or sealing compound, characterized in that it consists of

a) one or more reactive, meltable and / or thermoplastic backbone binder (s)

b) one or more meltable reactive compound (s) serving for curing or crosslinking and, if appropriate

c) other known additives,

where a) and b) have different melting and / or softening ranges and harden or crosslink after melting and mixing to form a duromer.

2. Shaped body according to claim 1, characterized in that it has a cylindrical, conical, cubic, cuboid, spherical, pearl, strand, strip and / or platelet shape.

3. Shaped body according to claim 1 and 2, characterized in that at least one of the reactive components is microencapsulated.

4. Shaped body according to one of claims 1 to 3, characterized ge indicates that at least one of the reactive constituents is embedded in the mass as balls and / or beads.

5. Shaped body according to one of claims 1 to 4, characterized in that at least one of the reactive components is embedded in the mass as a round profile or strip.

6. Shaped body according to one of claims 1 to 5, characterized ge indicates that 2- and multilayer laminates or sandwiches are formed from the reactive components a) and b).

7. Shaped body according to one of claims 1 to 6, characterized ge indicates that they are coated with at least one of the reactive components.

8. Shaped body according to one of claims 1 to 7, characterized in that addition-setting backbone binders have been used.

9. Shaped body according to claim 8, characterized in that the backbone binder is an epoxy, polyurethane, isocyanate and / or polyamide resin ^' and / or reactive derivative thereof.

10. Shaped body according to one of claims 1 to 7, characterized in that polymerizing backbone binders have been used.

11. Shaped body according to claim 10, characterized in that the backbone binder has at least one reactive group of the general formula:

CH, = C - X in the

X = - C -, - C - 0 -, - CH -, - CH „-, - 0 -, - N li H <

0 0

R = H, - is a C ₁ - C ₄ alkyl radical, halogen or - CN.

12. Shaped body according to one of claims 1 to 7, characterized in that polycondensing backbone binders have been used. - 27 -

13. Shaped body according to claim 12, characterized in that the polycondensing backbone binders are urea, melamine, phenol, cresol, novolak and / or resorcinol resins and / or their copolymers.

14. Shaped body according to one of claims 1 to 13, characterized in that the backbone binders have a dual functionality.

15. Shaped body according to one of claims 1 to 14, characterized in that the one-piece mass contains binders, fillers, pigments and / or foam and blowing agents.

16. Shaped body according to one of claims 1 to 15, characterized in that it is colored for temperature and / or Mischgut¬ control with reversible and / or irreversible temperature measurement colors.

17. A method for producing a one-piece molded body, which consists of

a) one or more reactive, meltable and / or thermoplastic backbone binder (s)

c) other known additives,

where a) and b) have different melting and / or softening ranges and, after melting and mixing, harden or crosslink to form a duromer, characterized in that a hollow body is produced from one of the higher-melting or softening, reactive constituents is and the resulting cavity is filled with a low-melting or softening reactive component.

18. A method for producing the one-piece molded body according to claim 17, characterized in that a hollow profile is drawn from the components a) or b) and then the cooled and solidified continuous tube is filled with the components a) or b).

19. Process for the production of the one-piece molded body, which consists of

a) one or more reactive, meltable and / or thermoplastic backbone binder (s)

b) one or more meltable reactive compounds (s) serving for curing or crosslinking and, if appropriate

c) other known additives,

where a) and b) have different melting and / or softening ranges and harden or cross-link after melting and mixing to form a Duromereπ, characterized in that the higher-melting, still solid, small-scale constituents into the low-melting, liquid reactive constituents mixed and / or coated with it.