EP0758413A1

EP0758413A1 - Binding compound for the production of non-woven material

Info

Publication number: EP0758413A1
Application number: EP95919367A
Authority: EP
Inventors: Stan Thyssen
Original assignee: Teodur NV
Current assignee: Teodur NV
Priority date: 1994-05-03
Filing date: 1995-04-29
Publication date: 1997-02-19
Anticipated expiration: 2015-04-29
Also published as: CZ290886B6; DE59505660D1; WO1995030034A1; ZA953558B; US5852102A; CZ319496A3; ES2133770T5; JPH09512575A; EP0758413B1; AU2523495A; EP0758413B2; ATE178957T1; ES2133770T3

Abstract

PCT No. PCT/EP95/01643 Sec. 371 Date Jan. 28, 1997 Sec. 102(e) Date Jan. 28, 1997 PCT Filed Apr. 29, 1995 PCT Pub. No. WO95/30034 PCT Pub. Date Nov. 9, 1995A mixture for producing moulded articles from fibre mats containing a) 20 to 45 wt. % of a powdered binder mixture, b) 80 to 55 w. % of organic and/or inorganic fibres, characterised in that the powdered binder mixture contains a1) 30 to 90 wt. % of phenol resin and a2) 70 to 10 wt. % of powder coating waste and moulded articles produced therefrom.

Description

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Binder composition for the production of fibrous materials

The invention relates to a special binder mixture for the production of nonwoven fabrics, and to processes for their production. The prepregs made from the nonwovens and binders are also described.

Molded parts based on nonwovens are widely used in industry. These are nonwovens made of various types of fiber that can be mixed with binders. Pre-products can then be produced from these nonwovens, the so-called prepregs, which are then shaped, hardened and, if necessary, assembled with the appropriate processing tools. It is also possible to produce the corresponding nonwoven fiber nonwoven directly from the fibers and the binder powder. These molded parts or planware are used in a wide range. In the automotive industry, these products are used, for example, as molded parts, e.g. used as insulation for bonnets, wheel arches or trunk insulation. Another area of application is the use as planware, e.g. as insulation in washing machines, tumble dryers or loudspeakers, in sound-absorbing walls. They can be provided with additional coatings, e.g. by flocking, laminating or laminating. These molded parts or sheet parts thus equipped with an optically stable and decorative surface coating can then e.g. can be used as door side cladding, as a parcel shelf or as ceiling cladding in the automotive industry.

The methods for producing nonwoven fabrics or for mixing these nonwovens with binder powder are known. The fiber material is homogenized, for example in a fiber mixing chamber, and placed on a conveyor belt as a loose fiber layer. The binder mixture is then applied to the fiber material, for example using metering rollers or vibrating troughs. The fiber / binder mixture is then swirled in a closed system by means of an air stream and mixed homogeneously. The homogeneous mixture of fiber and binder powder is laid down to form a continuous fleece. The components of this mixture can either be glued to one another by gentle heating and then cooling, the prepregs being formed, or sheet or roll goods which are already completely hardened are produced. The prepregs have not yet been fully cured, but are stable in storage. After processing into the final shape, these prepregs are thermally crosslinked under the influence of heat at up to 210 ^* C, whereby three-dimensional thermosetting molded parts are obtained.

The requirements placed on these moldings with regard to surface structure and color are variable, but there must be sufficient mechanical stability at elevated temperatures or long-term stress. However, a binder must be used for their production which connects the nonwovens used so well that a stable molded part is obtained after the final shaping and curing. The binders currently used are relatively expensive. Phenolic resins are also hazardous to health. Industry is keen to cut costs. In the case of the molded parts described above, such as the insulating materials for bonnets, wheel arches or insulation materials, alternatives to the expensive, technically pure resins are sought.

The object of the present invention is to provide a binder mixture for the production of nonwoven molded parts, in which a considerable part of the pure resins usually used can be replaced by other components, which nevertheless leads to stable, reactive binder mixtures which lead to the production of Fiber non-woven prepregs or hardened non-woven fabrics are suitable. Another task is to reduce the proportion of harmful substances. These binder mixtures have to meet the usual requirements for the production of nonwoven molded parts, and in doing so result in hardened, stable molded parts which can be adapted to the various purposes.

It has been shown that this object can be achieved by using powder coating waste as or in binders for the production of molded parts from nonwoven fabrics. Surprisingly, it has been found that the resins usually used can be replaced, at least to a considerable extent, by powder coating waste.

An object of the invention is a mixture for the production of molded parts from nonwoven fabrics containing

a) 20 to 45% by weight of a powdery binder mixture,

b) 80 to 55% by weight of organic and / or inorganic fibers, which is characterized in that the powdered binder mixture

a.) 30 to 90 wt .-% phenolic resin and

a ₂ ) contains 70 to 10 wt .-% powder coating waste.

Another object of the present invention is the use of powder coating waste for the production of moldings which contain fiber fleece.

Another object is the use of this varnish waste for binding nonwoven fabrics.

Powder coatings are increasingly used in the coatings industry. These have the advantage that a solvent-free application process is possible. This can significantly reduce emissions to the environment. However, the application methods for powder coatings have the disadvantage that a significant proportion of the powder is not based on the layering object arrives. These powders are collected in the painting booth as a so-called overspray. Powder size distribution and purity are sensitive. Therefore, this over-spray must be disposed of as waste. In the last stage of paint powder production, the crushed paint powder extrudates are ground. Fine dust accumulates during this grinding process, which has a disruptive effect on the painting process. Therefore, this dust is largely removed. This dust is difficult to reprocess and must be disposed of as special waste.

The fibers that can be used for the various nonwovens are woven, matted or mixed fibers. The fibers consist of the known materials, e.g. natural, organic and inorganic fibers. Examples include glass fibers, rock wool fibers, polyester fibers, acrylic resin fibers, polyolefin fibers, wool fibers, cotton fibers, linseed fibers or the like. Textile fibers, especially cotton fibers, e.g. Fiber waste from the textile industry used. These fibers or the non-woven fabrics made from them are known in industry. The processes with which they can be produced are also known. This can be done, for example, by weaving or matting. The resulting nonwovens should be essentially dry; they can, if necessary, be impregnated with additives.

The phenolic resins which can be used in the mixtures according to the invention are the customary reactive phenolic resins which have long been known in the industry. These are, for example, reactive, non-crosslinked, powdered phenolic resins containing OH groups. Such resins are already used for the production of molded parts from nonwoven fabrics. For example, phenol resins based on phenol and formaldehyde, as are known, for example, as resols or novolaks, can be used. As possible crosslinking agents, these resins can contain condensation products of formaldehyde.

These resins have been widely described in the literature, for example in RN Shreve, "The Chemical Process Industries", Chapt. Plastics, 1945 and commercially available. Further phenolic resins are also described in DE-A-3833 656, EP-A-0369539 and EP-A-0376432. Phenolic resins of the novolak type are particularly preferred. The reactivity of the phenolic resins is also determined by the type and amount of the crosslinking agent used. In general, a crosslinking reaction between 120 ^* 0 and 222 ^* C occurs.

The resins are generally in powder form. Suitable grain sizes are, for example, between 0.1 and 500 μm, preferably between 2 and 150 μm, particularly preferably between 10 and 60 /.

The grain sizes of the powder coating waste used are, for example, in the same range as that of the resins and are preferably between 1 to 300 μm, particularly preferably between 10 and 60 μm. If powder coating waste is used whose grain sizes are too small for the desired application, it is possible to obtain larger grain sizes by caking the particles.

The powder coating wastes which can be used according to the invention are those of the customary known powder coating materials. The binders of the powder coatings can be based, for example, on epoxy resins, polyester resins, polyurethane resins or acrylate resins. This powder coating waste occurs, for example, as overspray from painting booths or as batches in the manufacture of the powder coating. It is also possible for filter dust to be collected and used, and for residues from the grinding of the powders.

The powder coating waste which can be used in the mixture according to the invention has not yet been crosslinked. They contain reactive groups such as carboxyl groups, epoxy groups, hydroxyl groups, amino groups, amide groups or isocyanate derivatives. These can react with each other when heated. The crosslinking temperature depends on its basic structure. They are usually between 120 and 220 ^* 0. Powder coatings with crosslinking temperatures above 180 ^* 0 are preferably added only in small amounts in order to achieve the most complete possible crosslinking of the binder used, even at curing temperatures of the moldings of about 160 ^* 0. In addition, at high crosslinking temperatures, especially when using nonwoven made of synthetic There is a risk that the fibers are broken down, which leads to a lowering of the stability of the molded part. It is preferred that the coating powder / crosslinking temperatures are below 160 ^* 0.

The powder coatings used are known binder systems. These are customary resins, for example those based on epoxy, polyester, polyurethane or acrylate.

The epoxy powder coatings contain epoxy resins as the main binder component. These often crosslink via hardeners containing hydroxyl groups, especially those containing amide or amine groups.

Furthermore, polyester powder coatings are known in which the main binder constituent is polyester containing carboxyl groups. Crosslinkers present in parts are, for example, crosslinkers containing epoxy groups or crosslinkers containing amino or amide groups. It is common for the crosslinking agents to be more functional than the main binder component. If epoxy / polyester is used as powder, so-called hybrid systems, the proportions of polyesters or epoxy resins are approximately the same.

Polyurethane powder coatings are based on hydroxyl-containing polyesters, which are reversibly blocked polyisocyanates, e.g. are protected with known capping agents such as caprolactam or ketoxime, can be crosslinked or are present as urethdione.

Powder coatings of the acrylate type are generally mixtures of two or more acrylate resins, each containing functional groups such as epoxy groups, carboxyl groups, hydroxyl groups or isocyanate groups. The mutually reactive groups are distributed among different molecules.

These binder powders are described, for example, in ST Harris, "The Technology of Powder Coatings", 1976 or in DA Bäte, "The Science of Powder Coatings" Vol I, 1990. Colorless or pigmented powder coatings can be used, the customary known inorganic or organic color pigments being possible as pigments. It is also possible for effect pigments, for example metallic pigments, to be incorporated into the powders. A

Color separation is not necessary. The grain fineness of the powder is not essential, it should only be ensured that an average sample of the various powder residues is generally used for the preparation of the binder mixture. This leads to better mixing behavior and to a more constant production of the binder mixture.

Any individual powder coating can be used. In order to achieve a composition of the binder mixture a) which is as constant as possible, it is preferred that a mixture of epoxy powders and polyester powder is present as a ₂ ). Up to 60% by weight of a ₂ ), preferably up to 30%, can optionally be replaced by polyurethane powder and / or polyacrylate powder. It is possible to directly produce a mixture a ₂ ) within the desired weight ratios and thus to store it. Another possible method of operation is that the various powder coating components are stored separately according to the chemical types described above and are only mixed with the phenolic resins later before further processing. Within these chemical types, the resulting materials are mixed homogeneously, ie a sample mixed in the grain size distribution composition and pigmentation is formed. The amounts required in each case are then mixed together from the mixtures of the powder coating binders obtained in this way during the preparation of the binder powders a). If necessary, it is possible to introduce further additional crosslinkers into the binder mixture.

The powder coating waste which can be used according to the invention is in the form of ground powders. It may be necessary to grind portions of the binding agent which are in the coarser form beforehand to a suitable particle size. This can be of the order of magnitude specified for the phenolic resins. If necessary, customary additives or additives can be added together with the powders. These can be, for example, catalysts, accelerators or flame retardants. Tin compounds such as dibutyltin dilaurate are preferred as catalysts,

Carboxylic acid salts such as lithium benzoate, quaternary ammonium compounds such as tetrabutylam onium bromide, cetyltrimethylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride or tetramethylammonium chloride or tertiary amines such as triisopropylamine or methyl idazole. Suitable accelerators and crosslinkers are, for example, basic compounds containing epoxy groups, such as triglycidyl isocyanurates, glycolurils, dicyandiamide or beta-hydroxylamides. These additives can be added individually as powdery substances. They can also be introduced as a masterbatch mixed with binder components or they are added as a mixture with the binder powder a.).

Flame retardant substances can also be introduced. These are the usual known substances that are contained in fire protection coatings. Examples of such compounds are borates such as sodium borate; Phosphates such as ammonium phosphate or sodium phosphate; Aluminum hydroxides or oxides; further suitable compounds are, for example, heavy metal-containing compounds such as tin oxide compounds or perbroated or perchlorinated compounds such as tetrabromophenol. However, heavy metal-free and halogen-free flame retardant substances should preferably be used. These flame retardant substances are available as a powder. They can be introduced via a separate master batch or they are metered in via the binder powders a.) Or a ₂ ) in each case as a homogeneous mixture with the powder component.

Pigments can also be introduced into the binder mixture a). In general, however, it is preferred not to introduce any additional pigments, but only to use the fibrous fillers of the nonwoven or the pigments contained in the powder coatings a ₂ ). The present invention further relates to molded parts which can be produced by molding and partially or completely curing the mixture of fibers and binder described above. If the mixtures of fibers and binder are only partially cured, the so-called prepregs are obtained, which can then be brought into their final shape by heating in a further processing step and can be fully cured. If the mixture is to be fully cured, it is molded into the appropriate shape in a manner known per se and cured at the crosslinking temperatures suitable for the particular binder mixture.

The prepreg or the finished molded part formed before curing generally contains 55 to 80% by weight of fibers and 20 to 45% by weight of the binder mixture.

In a preferred embodiment, the binder mixture consists of 45 to 70% by weight of phenolic resins and 30 to 55% by weight of powder coating binder. The additives and additives described above can be contained in an amount of up to 20% by weight, preferably up to 15% by weight, the sum of the individual components giving 100% by weight. Any powder coating waste can be used. Only one type of powder coating or a mixture of several can be used, but a mixture of polyester and epoxy resins is preferred. It is further preferred that the ratio of polyester powder to epoxy powder is 0.2: 1 to 7: 1, preferably 0.8: 1 to 3: 1. When selecting powder coating waste, care should be taken to ensure that it has a sufficient number of reactive groups.

To produce the moldings according to the invention, the binder mixtures are homogenized and, together with any additives, applied to the nonwoven fabric. This is done using known methods. The binder mixture is distributed evenly on the nonwoven fabric and then, if necessary, a heating step can be carried out. The result of this is that the binder particles soften on the surface and bond firmly to the nonwoven fabric. It arises So-called prepregs, which result in storage-stable, deformable web-shaped nonwovens. It is important to ensure that no complete crosslinking occurs yet, but that the binders are deformed even further in the heat and can flow and crosslink.

The binder mixture a), the prepregs and also the hardened moldings have a reduced proportion of free phenols or formaldehyde. This reduces the risks posed by these harmful substances. The molded parts according to the invention can then be produced from the prepregs obtained in this way. This takes place according to known methods such as, for example, shaping and / or laminating, making up the prepregs. After the prepregs have been brought into a suitable shape, they are cross-linked by applying pressure and heat. Crosslinking takes place at temperatures from 140 to 200 ^* C. The time can be between 10 and 500 seconds, preferably less than 120 seconds. It is selected depending on the phenolic resin a) used. The binder powder melts and flows, whereby the fibers are at least partially embedded and chemical crosslinking of the resins takes place. This creates a hardened thermoset material. Depending on the amount of material used and the pressure applied, the moldings may contain parts of voids. The density of the molded parts can be between 50 to 1000 kg / m ³ . It depends on the amount and type of fibers and binders. The moldings formed have ver¬ various advantages, such as good thermal insulation, dimensional stability up to 130 ^* C, good sound insulation, good flexural strength, are physiologically acceptable and have a moisture-regulating, can easily be processed weiter¬.

These molded parts can still be coated or they serve as carriers for other components. This can be done, for example, by applying a film to the surface of the molded part together with the crosslinking and molding of the molded parts. This is firmly bound to the surface by the chemical reaction. Furthermore, it is possible to laminate and laminate foils to achieve re coating of the surface. Processes for laminating molded parts are widely used in industry. They can be carried out according to the state of the art.

It is also possible to flock the surface of the molded parts. Short fibers are brought onto the surface essentially perpendicularly by means of adhesives, which then produce a dense and soft surface. Flocking methods are also known. The molded parts produced from the compositions according to the invention can optionally be painted. All known coating agents known in the industry can be used. After heating, smooth, shiny coatings are created.

The molded parts coated in this way have an appealing decorative effect. Depending on the selection of the method, smooth, soft, grained or also chemical-resistant coated surfaces can be obtained. By additionally using flame retardant additives, molded parts can also be obtained which are resistant to fire.

The molded parts obtained in this way can be used in various industrial areas. In particular, they can be used in the automotive industry, e.g. as interior trim parts for automotive interiors or sound and heat protection parts. Furthermore, the binder mixtures can be used as resins in coatings for clutches. These resins can also be used for mold construction in the foundry industry. The resulting molded parts are extremely stable and can be shaped in a variety of ways. Through the addition of various additives or through the surface coating, it is possible to use them in different fields of application.

example 1

It becomes a mixture of 48 g of a commercially available powder Phenolic resin (novolak with hexamethylenetetramine) with an average grain size of 35 μm and a crosslinking temperature of 150 ^° C. and 3.4 g of a pigmented powder coating based on commercially available epoxy resin powder and 10.2 g of a pigmented powder coating based on polyester resins , the powder coating materials each having a pigment content of 13%, homogenized in a commercially available mixing unit.

(Polyester: epoxy = 3: 1, 20% powder coating)

The mixture can be stored for a long time without further loss of reactivity.

Example 2

A previously homogenized mixture of 15.8 g of an epoxy resin powder coating material and 14.2 g of a polyester powder coating material, both unpigmented, is added to 70 g of a phenolic resin analogously to Example 1.

(Polyester: epoxy = 0.9: 1, 30% powder coating).

20 g of a flame retardant based on ammonium phosphate, melamine borate and aluminum hydroxide are added to this mixture and homogenized on a conventional mixing unit. A slight warming up to 40 ^* C may occur due to the mixture energy. However, the various powder fractions should not be caked.

Example 3

21 g of an epoxy resin powder pigmented to 10% with barium sulfate are added to 60 g of a phenolic resin according to Example 1 and homogenized. 30.1 g of a non-pigmented polyester powder coating material and 0.4 g of tetrabutylammonium bromide are then mixed in, and the entire mixture is then thoroughly homogenized. (Polyester: epoxy = 1.6: 1, 45% powder coating)

The mixture has a long shelf life.

Filter dusts from the manufacture of the powder coatings are used as polyester powder or epoxy powder. These are homogenized and then an average sample of these fractions is used in the examples.

Prepregs are produced from the powders of Examples 1 to 3 using a nonwoven fabric produced in a known manner and containing over 80% cotton fibers. For this purpose, the nonwovens are mixed homogeneously with the binder powder by mechanical movement and passed through a heating channel (approx. 2 to 3 minutes, 80 ° C. to 10 ° C.). This results in prepregs in which resin and fiber are stable connected with each other.

The prepregs can be made differently according to size and resin / fiber content. The bulk density is between 25 and 75 kg / m ^3, depending on the application.

Molded parts are produced from these prepregs. The Pre¬ pregs are cut, placed in a press in the intended shape and cured therein 100 seconds to 110 seconds at temperatures of between 140 ^* C and 160 ^* C. After curing, thermosetting products are formed which retain their shape under heat. The density can be influenced via the amount of the prepreg or via the set pressure. The resulting crosslinked molded parts can be flocked in a known manner or they are laminated with foils.

The molded parts obtained in this way have an optically homogeneous surface, they are dimensionally stable and have only a low content of free phenol or formaldehyde.

Claims

Claims:

1. Mixture for the production of molded parts from non-woven fabrics containing

a) 20 to 45% by weight of a powdered binder mixture,

b) 80 to 55% by weight of organic and / or inorganic fibers,

characterized in that the powdered binder mixture

a.) 30 to 90 wt .-% phenolic resin and

a ₂ ) contains 70 to 10 wt .-% powder coating waste.

2. Mixture according to claim 1, characterized in that it contains further additives.

3. Mixture according to claim 1 or 2, characterized in that the powder coating waste is reactive coating powder based on epoxy, polyester, polyurethane and / or acrylate resins.

4. Mixture according to one of claims 1 to 3, characterized in that epoxy resin and polyester resin are used in a ratio of 1: 0.2 to 1: 7 as powder coating waste.

5. Mixture according to one of claims 1 to 4, characterized in that at least one flame retardant is added as an additive.

6. Molding obtained by molding and partially or completely curing a mixture according to one of claims 1 to 5.

7. Use of paint waste for the production of molded parts from fiber webs.

8. Use of paint waste to bind non-woven fabrics.