DE19814266A1 - Back-lined acrylic glass sanitary articles, e.g. bath tubs, shower trays, sinks and wash basins - Google Patents

Abstract

Acrylic glass sanitary articles are reinforced on the back with a glass fiber and asbestos-free cold-cured acrylic resin system which contains hollow microparticles filled with inert gas, possibly with other inert fillers and additives. Back-lined sanitary articles comprise an acrylic glass molded part reinforced at the back with glass fiber and asbestos-free polymer material 1.5-10 mm thick (RPM), which is firmly bonded to the acrylic without additional coupling agents. The RPM is obtained by hardening a cold-curing polymerizable, reactive (meth)acrylate system which has been sprayed on the back of the molding. This system comprises (A) a combination of (a) 30-100 wt% (meth)acrylate consisting of (a1) 0-100 wt% methyl (meth)acrylate, (a2) 0-100 wt% 2-4C (meth)acrylate, (a3) 0-50 wt% 5C or higher (meth)acrylate and (a4) 0-50 wt% polyfunctional (meth)acrylate with (b) 0-50 wt% comonomers comprising (b1) 0-30 wt% vinyl-aromatics and (b2) 0-30 wt% vinyl esters; (B) 0.05-5 parts by weight (pts. wt. per 1 pt. wt. A) of a (pre)polymer which is soluble or expandable in (A); (C) a redox system (accelerator and peroxide catalyst or initiator) in an amount sufficient for cold-curing, which is kept partly or completely separate until polymerization; (D) conventional additives; (E) 0-75 wt% fillers with a particle size of not more than 100 microns which are inert under depolymerisation conditions; and (F) 0.1-50 wt% hollow micro-particles filled with inert gas. An Independent claim is also included for a process for the production of back-lined sanitary articles by spraying a reactive resin system on the back of an acrylic glass molding and curing it in contact with the molding, using a resin system which hardens to form a polymer with a Tg of more than 70 deg C and contains up to 2.33 pts. wt. fillers which are inert under conditions required for depolymerisation of the acrylic glass (per 1 pt. wt. resin system).

Description

The invention relates to back-lined sanitary articles according to the preamble of claim 1 and a method for Manufacture of such sanitary ware.

In particular, the invention relates to bathing or bathing Shower trays or sinks, which is a preferably have deep-drawn acrylic molded part, which at his Back with fiberglass and asbestos-free, 1.5 to 10 mm thick polymer material is reinforced, which without additional adhesion promoter firmly to the acrylic molded part connected, this reinforcement by polymerization a (meth) acrylate system is available.

The following publications are cited for the more detailed state of the art:
D1 = Patent Abstracts of Japan, unexamined applications, Section M, Volume 17, No. 694, December 17, 1993, The Patent Office Japanese Government, page 45 M 1531; & JP-A-05 237 854;
D2 = DE 36 44 111 A1;
D3 = FR 2,640,909;
D4 = EP-A-0 693 503;
D5 = EP-A-0 285 046;
D6 = EP-A-0 345 581;
Reinforced acrylic molded parts as tubs or basins in the sanitary area are known in principle. The Japanese laid-open specification JP-A 05-237854 of Mitsubishi Rayon (= D1) describes a manufacturing process in which a filled resin mixture is poured into a gap between the mold and the deep-drawn acrylic molded part and then cured integrally while in contact with the molded part. For example, a mixture of 90 parts by weight of a prepolymer of a methacrylic ester and 10 parts by weight of a methacrylate monomer with 60% by weight of aluminum hydroxide is used as the filled resin mixture. This mixture, together with initiator and crosslinker, is poured into an 8 mm thick gap between the preformed acrylic glass part and the mold. The mixture in the gap is then allowed to cure for 4 hours, the surface of the gap between the mold and the molded part being covered with a polyester film.

As fillers for the resin mixture to be poured in addition to aluminum hydroxide also calcium carbonate, Glass fibers or carbon fibers are proposed.

Although according to the Japanese mentioned Offenlegungsschrift D1 proposed casting method laminated composite bodies, in particular bath or Shower trays or drain basins are available that regarding the adhesion of the reinforcement layer to the deep-drawn acrylic molded part of the base as well in terms of the strength of the entire composite body have quite satisfactory properties are both the molded part and the process for its Manufacture special in at least two ways disadvantageous.

On the one hand is for the production of the back-lined molded part a second molding tool is always required, with which the Pour the reinforcement mass with required volume must be taken into account.

On the other hand, there is only a relatively thick back lining of the deep-drawn molded part (in the above example 8 mm) possible, since it is easy to get larger with a casting process Differences in thickness can occur, which if too small Backing thicknesses as they are due to Material consumption and weight savings definitely would be desirable, is no longer tolerable.

From D2 (= DE 36 44 111 A1) is a method for Manufacture of a plastic reinforced bathtub known in which a tub that is made in the deep-drawing process Acrylic glass was made with one on the outside sprayed glass fiber reinforced polyester resin layer is reinforced. Both the fiber reinforcement and the Backing with polyester material is one of the options simple and essentially complete Countering the recyclability of used molded parts, yes this downright impossible.

FR 2 640 909 (= D3) relates to a sandwich component for the sanitary area made of thermoplastic resin (e.g. PMMA) and one on the component shape of the thermoplastic Resin part preformed fiberglass mat. Get connected these parts in a mold by injecting a syrupy polyester formulation between the preformed Acrylic and fiber parts. The possibility of using a Acrylic resin is also mentioned. As is the case with the D2 the use of glass fibers, be it in the form of a mat or from chopping a roving, as prohibitive for one Reconditioning of used molded parts too regard. It is also the case with the D3 proposed procedure in no case to a Spray process, but rather an injection (Spray) process, which is just as time-consuming and is disadvantageous like the casting process of the D1. It will several work steps, several people, several forms as well as post-processing steps needed to become a Product to come.

Reinforced sanitary ware that has a deep drawn Have acrylic molded part, on its back with a layer of a fibrous polymer material is reinforced, which is stuck without additional adhesion promoters is connected to the acrylic molded part, are also from the EP-A-0 693 503 (= D4) is known.

These back-lined sanitary articles are identified in that the reinforcement layer is 1 to 5 mm thick and by curing one on the back of the Acrylic molded part sprayed on, polymerizable, cold-curing, reactive (meth) acrylate system available is. The (meth) acrylate system contains as essential Components in addition to the polymerizable components Redox system, fine fillers and for reinforcement 10-50 Weight percent glass fiber chaff.

An advantage of the well-known back-lined sanitary article should now consist of its reprocessing through Depolymerization - an appropriate, appropriate one Assuming that the fine fillers are selected - no problem should be possible. This is true with regard to the D4 unrestricted to removable fine fillers, which in large amounts of fiberglass chaff needed for reinforcement are, however, not without problems during depolymerization, which unfortunately was due to extensive results from practice is confirmed. In theory, one can assume that the chaff from used parts is on the Surface of the metal bath required for depolymerization collect and skim off with a slider or squeegee can be, however, it has been shown that the chaff remain in the metal bath to a not insignificant extent and cannot be easily separated. In addition comes that the fiberglass chaff basically with respect to the To assess occupational safety similar to asbestos fibers are. A health hazard for the operating personnel due to the depolymerization partly in the form of dust accruing fiberglass chaff is not straightforward to exclude. A waiver of such fiber fillers would therefore be very desirable a priori.

Besides that, the reinforcement layers tend to stand out the (meth) acrylate systems on which the technology is based at least partially to hardening disorders, for example Air inclusions etc. The essentials for reinforcement Fiberglass chaff are sticking out, which means that some Centimeter-long fibers do not lie flat after spraying on rest on the back of the molded part, special that it at Formation of the tangle within the reinforcement material to a more or less pronounced protrusion of the fibers comes from the molding level. Thus, a roll to the Compensation of the hardening disturbances and pressing of the Fiber reinforcements are essential. This manual post-processing - i.e. post-processing by hand - is expensive and expensive the product.

Although one could get the impression that the D4 disclosed manufacturing variants even without Fiberglass reinforcement documents the D4 through all examples the need for Fiberglass reinforcements. In addition, component G) according to D4 as an essential part of Called reinforcement layer. An essential one However, the component cannot simply be omitted, without questioning the success of technical teaching. This is a clear indication that the technical Teaching the D4 no fiberglass free Reinforcing layers included and thus to the person skilled in the art no corresponding solution disclosed or made accessible will. So there is still the unsolved problem of fully recyclable, lined sanitary ware, which are free of fiberglass chaff and polyester resin and The result of this is, of course, an increased one Need for such articles.

The D5 and the D6 disclose in relation to the subject matter of the present application only technological Background.

Given what is mentioned herein and in detail discussed prior art, it was a task of Invention, fiberglass-free and asbestos-free reinforced To provide sanitary ware.

Furthermore, the creation is completely recyclable Sanitary articles based on molded acrylic glass parts The object of the invention has been.

Another object of the invention is to provide fully recyclable back lined Acrylic molded parts, which in particular are made using the depolymerization technique known for acrylic glass by means of metal baths, completely and, if possible, without Endangering the operating personnel are recyclable.

Another object of the invention is to be seen in to provide back-lined sanitary ware that the general ones with the highest possible material savings Requirements as they are with regard to the Stability can be placed on sanitary articles.

It was, among other things, the task of the invention Sanitary ware with sufficient durability of the Reinforcement layer also and especially without additional Provide adhesion promoter.

Also said to be the formation of cracks in the reinforcement layer be pushed back as much as possible.

Yet another task is to be deployed Impact-resistant coatings as possible for Acrylic molded parts can be seen.

In particular, the information is coated as thinly as possible and coated as highly impact-resistant as possible Acrylic molded parts one of the underlying principles of the invention Task.

In addition, the new sanitary ware should be as simple as possible be finished.

Furthermore, reworking by hand should be kept to a minimum be reduced.

It should be as safe a method as possible Manufacture of back-lined acrylic molded parts specified will.

Finally, the greatest possible and simple automation of the process for the production of back-lined acrylic glass moldings also plays a not insignificant role
These tasks as well as other tasks, which were not mentioned in detail in detail, but which can be readily deduced from the introductory discussion of the state of the art or can be deduced as a matter of course, by a back-lined sanitary article with all the features of claim 1.

Advantageous embodiments of the invention Sanitary ware are the subject of the independent Product claim related claims.

From a procedural point of view, the characteristics of the Claim 19 a solution of the invention with regard to the underlying procedural issues. Advantageous process variants are in the from independent process claim dependent Process claims placed under protection.

In particular, in that in the case of a back-lined sanitary article, having an acrylic molded part, which is reinforced on its rear side with glass fiber and asbestos-free, 1.5 to 10 mm thick polymer material, which is firmly connected to the acrylic molded part without additional adhesion promoters, the reinforcing material or reinforcing material by curing a polymerizable, cold-curing, reactive (meth) acrylate system sprayed onto the back of the acrylic molded part, which

• A)
  • a) (Meth) acrylate 30-100% by weight
    • a1) methyl (meth) acrylate 0-100% by weight
    • a2) C ₂ -C ₄ (meth) acrylate 0-100% by weight
    • a3) ≧ C ₅ (meth) acrylate 0-50% by weight
    • a4) polyvalent (meth) acrylates 0-50% by weight
    b) comonomers 0-50% by weight
    • b1) vinyl aromatics 0-30% by weight
    • b2) vinyl ester 0-30% by weight
• B) to 1 part by weight A) 0.05-5 parts by weight of one in A) soluble or swellable (pre) polymers
• C) one up to the polymerization of the to polymerizing components of the system entirely or partially separated redox system containing an accelerator and a peroxide catalyst or initiator in one Amount sufficient for cold curing of component A)
• D) common additives
• E) inert under the conditions of the depolymerization Fillers based on the sum A) -E) with a Fineness ≦ 100 µm 0-75% by weight
• F) hollow microparticles filled with inert gas, preferably made of plastic, based on the total A) -F) 0.1-50% by weight

contains,
it is possible to meet all of the requirements made by the standards institutes and industrial processors with regard to the physical properties of the sanitary article in an outstanding manner and to achieve a large number of other additional advantages.

These include, among others:

• - Complete recyclability on the way of the per se known depolymerization, among other things Avoidance of polyesters (freedom from polyester resin) coupled with avoidance in terms of health questionable dusts (no glass fiber chaff).
• - Elimination of the "rolling step" in production and further automation of the Manufacturing process by spray robots.
• - Mechanical properties according to DIN EN 198 (Deformability, impact strength, rigidity) adhered to in an excellent manner and about the the required dimensions are met.
• - High strength of the molded parts under stress and outstanding durability of the connection between Backing layer and molded acrylic glass part.
• - In contrast to JP-A 05-237854 it is the Method of the invention does not involve a Injection process in which the filled resin mixture in a gap between the deep-drawn acrylic molded part and a mold is filled, but rather a Injection process that does not require a molding tool will. A decisive advantage of the spraying process is the fact that with different Tub designs no appropriately shaped, expensive molding tools are needed.
• - In JP-A 05-237854 the curing time is the Mixture in the gap between the acrylic molded part and Mold specified with 4 hours. In contrast to hardens the spray system according to the invention at a Hardener dosage of 5% after 15-25 minutes. this means a substantial shortening of the Production time.
• - Due to the preferably solvent-free des (Meth) acrylate system is the risk of occurrence of Stress cracks minimized. Solvent-based systems tend especially in the temperature change test DIN EN 198 on stress cracks in the finished product Reinforcement layer.
• - Compared to EP-A-0 693 503 is not only for complete recyclability is a major advantage the fiberglass chaff or in general Glass fiber reinforcement freedom, it has in particular pointed out that in sanitary ware according to the EP-A-0 693 503 still has mechanical deficiencies occur, which the suitability of the article from the Question EP-A-0 693 503. So it works the use of certain fillers F) in the Reinforcement layer, just the mechanical and physical properties of an inventive Greatly improve sanitary ware.

A back-lined sanitary article of the invention has a Acrylic molded part and at least one reinforcing part Back lining layer on.

The acrylic molded part

Shape and type of acrylic molded part according to the invention is backed, are initially not subject to any special Restriction. Molded parts made of acrylic glass can be used be back-fed, which according to all the specialist for Shaping acrylic glass made known processes have been. These include processing via the viscous state, such as casting, pressing and application processes, preferably rotational molding, layer molding, compression molding, Injection molding, painting, dipping, coating, doctoring, Lamination and the like; processing via the elastoviscous state, such as kneading, rolling, calendering, Extrusion, injection molding, preferably sandwich Injection molding, RIM process; Processing via the elastoplastic state, such as drawing, stretch forming, Blowing, foaming, preferably cold forming such as Stretch forming, stretching, drawing forming, deep drawing, Vacuum forming, pultrusion, extrusion blow molding, injection blow molding, Injection blow molding, injection blow molding; Processing via the viscoelastic state, such as welding, sintering, Vortex sintering, flame spraying, hot jet spraying and the like; Processing beyond the solid state, such as cutting, Punching, forging, sawing, drilling, turning or milling. Deep drawing in all variations is preferred, Vacuum forming, vacuum forming without shape limitation, Vacuum negative process, drop form process, Vacuum stretch forming process, deep drawing suction process and the like. Deep drawing is particularly preferred for the invention available acrylic glass moldings.

Regarding the type of acrylic glass, there is also none Limitation. All common acrylic glasses are usable.

The acrylic molded parts, which are provided according to the invention with a backing layer, contain, with regard to the acrylic molded part, in addition to customary additives, predominantly structural units which obey the following formula I with regard to their chemical structure:

wherein
R ¹ C _1-6 -alkyl, preferably C _1-4 -alkyl,
R ² H, C _1-6 -alkyl, preferably H or C _1-4 -alkyl, very particularly preferably H or CH ₃ , and
n is a positive integer greater than 1
are.

C _1-4 -alkyl includes linear and branched alkyl radicals having one to four carbon atoms. Of particular interest are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-methyl-1-propyl, sec-butyl, 2-methyl-2-propyl.

C _1-6 -alkyl includes the _{radicals mentioned for C 1-4} -alkyl and additional radicals with 5 or 6 carbon atoms, such as preferably 1-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl-1-propyl, 3-methyl-1-butyl, 3-methyl-2-butyl, 2-methyl-2-butyl, 2-methyl-1-butyl, 1-hexyl.

For exemplary compounds which the aforementioned Have structural unit belong among others Polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, Polypropyl acrylate, polybutyl acrylate, polypropyl methacrylate, Polybutyl methacrylate and copolymers containing two or more of these types of polymer. The first four Compounds are preferred in the context of the invention. Quite Polymethyl methacrylate (PMMA) is particularly preferred.

In addition to the chemical mixtures (statistical copolymers or block copolymers), which by copolymerization of at least two substituted or unsubstituted Acrylic ester monomers are formed (e.g. Methyl methacrylate-n-butyl methacrylate copolymers) Acrylic molded parts are also made within the scope of the invention Use copolymers that are up to 50% by weight at least have another vinylically unsaturated monomer, which with at least one substituted or unsubstituted acrylic ester monomers copolymerizable is.

Examples include: Methyl methacrylate styrene Copolymers or methyl methacrylate-butyl acrylate-styrene Terpolymers.

The comonomers are optional Constituents or components that are preferably included in minor amount in the form of having them Copolymers are contained in acrylic glass. You will be in the Usually chosen so that they have no adverse effect the properties of that to be used according to the invention Have acrylic glass.

The mentioned comonomers or the mentioned comonomers can or can include can be used to improve the properties of the Modify copolymers in the desired manner, for example by increasing or improving the Flow properties when the copolymer is within its Processing into glass heated to the melting temperature or to reduce residual color in the copolymer or by using a polyfunctional monomer to in this way a certain amount of networking in introduce the copolymer.

Suitable monomers for this purpose include but are not limited to. Vinyl ester, vinyl chloride, vinylidene chloride, styrene, α-methylstyrene and the various halogen-substituted ones Styrenes, vinyl and isopropenyl ethers, dienes, such as for example 1,3-butadiene and divinylbenzene. the Color reduction of the copolymer can for example particularly preferred by using an electron-rich one Monomers, such as a vinyl ether, Vinyl acetate, styrene or α-methylstyrene can be achieved.

Particularly preferred among the comonomer mentioned Compounds are aromatic vinyl monomers, such as for example styrene or α-methylstyrene.

Physical mixtures, so-called blends, are also for the acrylic molded parts preferred.

It is, inter alia, also take into account that the term "Acrylic glass" is basically a collective term for represents organic synthetic glasses made of polymethacrylates, these by bulk or bead polymerization (Suspension polymerization) and subsequent extrusion or injection molding in the form of sheets, pipes, rods, Blocks are made.

In the context of the invention, however, by definitions the modifications described hereinabove under the The term "acrylic glass" should be understood.

However, they are also particularly preferred for the invention Artificial glasses made from polymethacrylic acid methyl esters.

The back lining layer (s)

In the sanitary ware according to the invention, for. B. tubs and Basin, it succeeds in that the reinforcement material a relatively small thickness in the range of 1.5 to 10 mm, preferably 1.5- <8 mm, can have a high weight and to realize material savings, with which if compliance the required strength values a reduction in Unit costs. This is reinforced Additional savings effect due to the nature of the Reinforcement layer, especially with regard to the Fillers F), and the type of application of the Reinforcement layer forming materials. A additional savings result from the fast Curing time.

Through the use in the backing layer or layers of hollow plastic microparticles that are inert with Gas are filled, does not succeed in easily predictably, a surprising improvement from important properties of reinforced sanitary ware according to the invention.

Thus, the hollow spheres that can be used according to the invention have a relatively low density compared to others Finest fillers, which increases the density of the injectable material is reduced. This causes at similar layer thickness results in a material saving of approx. 1/3.

In addition, the mechanical ones improve Properties of the cured material are significant. Not only surprising is the fact that at all Properties such as impact resistance or Adhesive tensile strength of the composite of acrylic molded part and Backfeeding to be improved is much more surprising nor the quality of improvement. So are improvements to register the adhesive tensile strength of 100% and more, compared to reinforcement layers without hollow microspheres.

Finally, the settling behavior of the fillers becomes apparent dramatically in cold-curing (meth) acrylate resins improved. With conventional resins you already have to a few weeks or even days of storage time Fighting segregation problems are those (Meth) acrylate resins with fillers of category F) also after several months still absolutely homogeneous and show no sediment whatsoever, which means that it can be processed by the Significantly easier for the user.

In a very special embodiment, a sanitary article according to the invention is characterized in that the reinforcement material consists of a first and a second layer, the first layer being cured by curing a polymerizable, cold-curing, reactive, first (meth) acrylate system sprayed onto the back of the acrylic molded part is available which

• A)
  • a) (Meth) acrylate 30-100% by weight
    • a1) methyl (meth) acrylate 0-100% by weight
    • a2) C ₂ -C ₄ (meth) acrylate 0-100% by weight
    • a3) ≧ C ₅ (meth) acrylate 10-50% by weight
    • a4) polyvalent (meth) acrylates 0-50% by weight
    b) comonomers 0-50% by weight
    • b1) vinyl aromatics 0-30% by weight
    • b2) vinyl ester 0-30% by weight
• B) to 1 part by weight A) 0.05-5 parts by weight of one in A) soluble or swellable (pre) polymers
• C) one up to the polymerization of the to polymerizing components of the system entirely or partially separated redox system containing an accelerator and a peroxide catalyst or initiator in one Amount sufficient for cold curing of component A)
• D) common additives
• E) inert under the conditions of the depolymerization Finest fillers based on the sum A) -E) with a fineness ≦ 100 µm 0-75% by weight
• F) hollow microparticles sensed with inert gas, preferably made of plastic, based on the total A) -F) 0.1-50% by weight

contains,
and the second layer is obtainable by curing a polymerizable, cold-curing, reactive, second (meth) acrylate system which is sprayed onto the first layer and which is different from the first (meth) acrylate system, the second (meth) acrylate system being System except for component a3), ie except for the content of ≧ C ₅

(Meth) acrylate, which is 0 to <10 wt .-%, and up to the component F), based on the sum A) -F) in a Amount of 0-50% by weight is present, same general The definition applies as to the first (meth) acrylate system.

Although with a single layer reinforcement due to the special fillers already meet all the requirements of the DIN EN 198 can be met, has the two-layer Reinforcement within the scope of the invention has the advantage that certain mechanical properties (especially the Impact strength) of the finished sanitary article can be improved.

The back lining or reinforcement layer as well as which in an expedient modification of the invention that Acrylic molded part reinforcing at least two Backing layers are made by curing an or by curing two or more polymerizable, cold-curing, reactive (meth) acrylate systems available, each consisting of components A) to D) put together, which together represent the binding agent, as well as the fillers E) and F).

In a first variant, this means that a (Meth) acrylate system the only one on the back Reinforcement layer of a sanitary article made of molded Acrylic forms.

This also means that in a second variant a first (meth) acrylate system a first back layer on the acrylic molded part, while a second (Meth) acrylate system a second back layer on the Acrylic molded part and the first back layer trains.

Although in the latter case both, i.e. both the first as well as the second (meth) acrylate system from the components A) to F) are the individual components in terms of type and / or quantity so out of the specified Definitions chosen that first and second (Meth) acrylate system are clearly different from one another.

The binder

The binder of a (meth) acrylate system settles in turn together from polymerizable monomers A), optionally in this soluble or swellable (pre) polymer B), a redox system C) and optionally other customary ones Additives D).

The component A)

Component A) is an essential part of the Binder and thus the reinforcement layer.

First variant: only one reinforcement layer

A single monomer can be used as monomer A), e.g. B. methyl methacrylate, but usually a mixture is used. The composition of component A) is:

(Meth) acrylate 30-100% by weight Methyl (meth) acrylate 0-100% by weight C ₂ -C ₄ (meth) acrylate 0-100% by weight ≧ C ₅ (meth) acrylate 0-50% by weight polyvalent (meth) acrylates 0-50% by weight Comonomers 0-50% by weight Vinyl aromatics 0-30% by weight Vinyl ester 0-30% by weight

Styrene is preferably to a maximum of 20% by weight in A) limited, as a higher salary leads to disruptions in the Cold curing leads to and with strong odor nuisance is to count.

A component in brackets stands for it optional usability, d. H. (Meth) acrylate stands for Acrylate and / or methacrylate.

The monomer component A) contains at least 30% by weight (meth) acrylate, monovalent (meth) acrylates having a C ₁ -C ₄ ester group being preferred. Longer-chain esters, ie those with a C ₅ or longer-chain ester radical, are limited to 50% by weight in component A).

The long-chain (meth) acrylates make the system more impact-resistant in the specified amount. In this way, these esters make the backing of the acrylic molded parts more flexible, but also softer, as a result of which the usage properties would be restricted for quantities above 50% by weight. Component A) preferably also contains polyvalent (meth) acrylates. Preferably, ≧ C ₅ (meth) acrylates in the first case in the (meth) acrylate system are contained in component A) in an amount of 10-30% by weight, particularly expediently in an amount of 15-25% by weight.

In addition to the (meth) acrylates, component A) can also contain other comonomers, the proportion of which increases 50 wt .-% is limited. Among these comonomers can Vinyl aromatics and / or vinyl esters each up to 30 wt .-% be contained in component A). Higher It is difficult to find proportions of vinyl aromatics polymerize and can lead to segregation of the System. Higher proportions of vinyl ester can still insufficient at low temperatures through hardening and tend to a greater shrinkage behavior.

Component A) is preferably composed of 80-100% by weight and particularly preferably 90-100% by weight of (meth) acrylates, since these monomers can be used to achieve favorable processing and use properties for backing. The proportion of C ₂ -C ₄ esters in (meth) acrylates is preferably limited to 50% by weight in component A), these esters are preferably a maximum of 30% by weight and particularly advantageously a maximum of 20% by weight .-% contained in component A). This allows particularly flexible backing layers to be built up.

Suitable monofunctional (meth) acrylates are in particular Methyl methacrylate, butyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, ethyltriglycol methacrylate, Hydroxypropyl methacrylate.

Particularly suitable comonomers are vinyl toluene, Styrene, vinyl ester.

Polyfunctional (meth) acrylates are particularly advantageous contained in component A), the content of which usually in the range from 1 to 50% by weight and usually at 1 up to 10% by weight in A). The polyfunctional (Meth) acrylates are used to link polymers between linear molecules. This allows properties like Flexibility, scratch resistance, glass transition temperature, Melting point or hardening processes are influenced.

On usable multifunctional (meth) acrylates include among others:

(i) Difunctional (meth) acrylates

Compounds of the general formula:

wherein R is hydrogen or methyl and n is a positive integer between 3 and 20, such as. B. Di (meth) acrylate of propanediol, butanediol, hexanediol, octanediol, nonanediol, decanediol and eicosanediol, compounds of the general formula:

where R is hydrogen or methyl and n is positive integer between 1 and 14, e.g. B. di (meth) acrylate of ethylene glycol, diethylene glycol, Triethylene glycol, tetraethylene glycol, Dodecaethylene glycols, tetradecaethylene glycols, Propylene glycols, dipropylene glycols, and Tetradecapropylene glycol; and glycerol di (meth) acrylate, 2,2'-bis [p- (γ-methacryloxy-β-hydroxypropoxy) - phenylpropane] or bis-GMA, biphenol-A-dimethacrylate, Neopentyl glycol di (meth) acrylate, 2,2'-di (4- methacryloxypolyethoxyphenyl) propane with 2 to 10 Ethoxy groups per molecule and 1,2-bis (3-methacryloxy-2- hydroxypropoxy) butane.

(ii) Tri- or multifunctional (meth) acrylates

Trimethylolpropane tri (meth) acrylate and Pentaerythritol tetra (meth) acrylate.

Preferred common polyfunctional (meth) acrylates include among other triethylene glycol dimethacrylate (TEDNA), Trimethylolpropane trimethacrylate (TRIM), 1,4-butanediol dimethacrylate (1,4-BDMA), Ethylene glycol dimethacrylate (EDMA).

Second variant: at least two reinforcement layers

a) first (meth) acrylate system, d. H. Methacrylate system of first reinforcement layer, i.e. the one Reinforcement layer, which is applied directly to the Acrylic molded part is sprayed and hardened on it.

The composition of component A) is in this case:

(Meth) acrylate 30-100% by weight Methyl (meth) acrylate 0-100% by weight C ₂ -C ₄ (meth) acrylate 0-100% by weight ≧ C ₅ (meth) acrylate 10-50% by weight polyvalent (meth) acrylates 0-50% by weight Comonomers 0-50% by weight Vinyl aromatics 0-30% by weight Vinyl ester 0-30% by weight

Longer-chain (meth) acrylates, ie those with a C ₅ or longer-chain ester radical, are an essential component of the (meth) acrylates of the first (meth) acrylate system, since they contain at least 10% by weight of the (meth) acrylates and thus also the Make up component A) of the first (meth) acrylate system.

b) second (meth) acrylate system, d. H. (Meth) acrylate system the second reinforcement layer, i. e. that layer which on an already on the acrylic molded part First reinforcement layer sprayed on the back is sprayed and on the first reinforcement layer is cured.

With regard to the nature of the monomers (component A)), the same general definition applies to the second (meth) acrylate system as applies to component A) of the first (meth) acrylate system, with ≧ C ₅ -Methacrylates make a major difference.

The composition of component A) is:

(Meth) acrylate 30-100% by weight Methyl (meth) acrylate 0-100% by weight C ₂ -C ₄ (meth) acrylate 0-100% by weight ≧ C ₅ (meth) acrylate 0- <10% by weight polyvalent (meth) acrylates 0-50% by weight Comonomers 0-50% by weight Vinyl aromatics 0-30% by weight Vinyl ester 0-30% by weight

Longer-chain esters, ie those with a C ₅ or longer-chain ester radical, are limited to <10% by weight in component A). These esters make the backing of the acrylic molded parts more flexible, but also softer, which limits their performance properties. As a result, the setting of the second layer (low proportion of ≧ C ₅ esters) is harder and thus more rigid compared to the first layer.

The component B)

The following description applies to both a single layer reinforcement as well for the first as well the second (meth) acrylate system of a multilayer Reinforcement, with the presence of several Reinforcement layers the respective component B) in each of the systems independently of each other of the following Definition obeys.

Component B) is essential.

To adjust the viscosity of the binder and the overall rheology of the system as well as the better Through curing, component A) becomes a polymer or Prepolymer B) added. This (pre) polymer should be in A) be soluble or swellable. Part A) is 0.05 up to 5 parts of the prepolymer B) are used. Are suitable in particular poly (meth) acrylates, these as solid Polymer can be dissolved in A) or wherein a so-called syrup can be used, d. H. partially polymerized masses of corresponding monomers. Farther are suitable polyvinyl chloride, polyvinyl acetate, Polystyrene, epoxy resins, epoxy (meth) acrylates, unsaturated Polyesters, polyurethanes or mixtures thereof. These Polymers cause in the binder z. B. special Flexibility properties, shrinkage regulation, act as Stabilizer, skin builder or flow improver.

The backing layers preferably contain 10-30% by weight, particularly advantageously 15-20% by weight, of one high molecular weight polymer B), e.g. B. poly (meth) acrylate, based on the sum A) + B).

In a preferred embodiment, the weight ratio is of components B) and A) of the binder in the range of 0.1: 1 to 2: 1. This creates an optimal match achieved.

Weight ratios B): A) im are particularly useful Range from 0.2: 1 to 1: 1.

Component B) ((pre) polymer) can be a Suspension polymer, emulsion polymer and / or Be grinding granulate from recycling processes. The middle one Particle diameter of the prepolymers is then usually at <0.8 mm.

The prepolymer B) is very advantageously one PMMA lacquer bead obtainable by suspension polymerisation.

In particular, this also allows single-layer reinforcements with sufficient impact strength.

The mean particle diameter of the lacquer bead is about 0.1-0.8 mm. 0.2-0.8 mm are preferred, especially 0.4-0.8 mm.

The following description of component B) des Binder and thus a reinforcing layer applies especially for the embodiment with at least two reinforcing layers.

(Pre) polymer B) is preferably a Copolymer, with hardness and flexibility of the Reinforcement layers by the type and amount of comonomer in the (pre) polymer B). To be used Comonomers that contribute to the structure of the respective (pre) polymer B) involved include, inter alia. Acrylates and methacrylates, which are different from methyl methacrylate (MMA), Vinyl ester, vinyl chloride, vinylidene chloride, styrene, α-methylstyrene and the various halogen-substituted ones Styrenes, vinyl and isopropenyl ethers, dienes, such as for example 1,3-butadiene and divinylbenzene.

Preferred comonomers for methyl acrylate include, Ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, Ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, 2-ethylhexyl methacrylate, propyl acrylate, propyl methacrylate, Methacrylic acid, ethyl triglycol methacrylate, Hydroxypropyl methacrylate.

The comonomer content of the prepolymers B) is for the first Reinforcement layer favorably at 30-80%, for that second reinforcement layer advantageously at 0- <30%, each based on the total weight of the building one Prepolymers B involved monomers or monomer units.

The component C)

Component C) is an essential component of the Binder and thus of each reinforcement layer.

The following description applies to both a single layer reinforcement as well for the first as well the second (meth) acrylate system of a multilayer Reinforcement, with component C) in each of the systems independently obey the definition.

That to be used according to the invention in the (meth) acrylate system Binder (A) to D)) is suitable for each Work hardening, d. H. contains a for polymerization Redox system consisting of an accelerator and a peroxide Catalyst or initiator, these components in sufficient amount for cold curing of component A) be admitted.

It is understood that either the redox system or at least parts of it by the desired time Polymerization of the polymerizable substances of the Binders are to be kept separate.

The accelerator is usually used in an amount of 0.01 to 5% by weight in A) to D) are used, especially advantageously from 0.5 to 1.5% by weight.

Amines and are particularly suitable as accelerators Mercaptans, preferred are dimethyl-p-toluidine, Diisopropoxy-p-toluidine, diethylol-p-toluidine, Dimethylaniline and glycol dimercaptoacetate. Further serve as accelerators organic metal salts that usually in the range from 0.001 to 2% by weight in A) to D) can be used. Suitable are e.g. B. cobalt naphthenate, Copper naphthenate, cobalt oleate, copper oleate.

Particularly suitable peroxide catalysts are Dibenzoyl peroxide and dilauroyl peroxide. The peroxides will be usually 0.1 to 10% by weight and in particular 0.5 up to 5% by weight in the binder. Appropriate is as peroxide catalyst for the spray resin system aqueous 40% suspension of phlegmatized Dibenzoyl peroxide (e.g. Cadox 40 E from Akzo) used.

Component C) can already contain the Accelerator, e.g. B. Dimethylparatoluidin, be included, without any polymerization at ambient temperature takes place. By adding the remaining components of the Component C) the reaction is started, the Component C) is usually dimensioned so that the (Meth) acrylate system has a pot life in the range of 10 minutes up to 30 min.

The (meth) acrylate system according to the invention therefore only contains the complete component immediately before use C), until use, the component C) is not or only partly included.

Solvent-free are very particularly preferred Hardener components used.

The component D)

The following description applies to both a single layer reinforcement as well for the first as well the second (meth) acrylate system of a multilayer Reinforcement, with component D) in each of the systems independently obey the definition.

Component D) is an optional one Component.

The binders (A) to D)) can also be customary Contain additives D), as they are in reactive (meth) acrylate Systems are mostly used. These additives serve z. B. the lifting of oxygen inhibition, are for this in particular paraffins at 0.05 to 5% by weight in the binder (A) to D)) and / or phosphites to 0.01 to 1% by weight in A) to D) as well as a polymer skin formation (paraffin-free) suitable. For the latter you can order a non-inhibited Achieve surface without paraffin, e.g. B. extreme high molecular weight polymers as an additive, especially for Use of methyl methacrylate alone. Methyl methacrylate evaporates during the curing process the surface and leaves a tack-free surface by polymer skin formation.

Defoamers can also be added, Wetting agents, thixotropic agents, inhibitors, Matting agents, bluing agents, UV stabilizers, Polymerization chain regulator.

Of these, thixotropic agents are particularly preferred. These serve to improve the storage stability and the Settling behavior of particles in the resin components.

In a preferred embodiment, the back is lined Sanitary articles of the invention therefore characterized that at least one of the for the back lining resin systems used based on the fillers E) to to 0.5 part of thixotropic agent to 1 part of the particles E) contains.

Usual thixotropic agents are z. B. silica, e.g. B. Aerosil® 200, Aerosil® 300.

The fillers

The fillers of a (meth) acrylate system of the invention are made up of types E) and F). The variety E) is optional, while the fillers F) are essential at least for one of the reinforcements according to the invention are.

The component E)

The following description applies to both a single layer reinforcement as well for the first as well the second (meth) acrylate system of a multilayer Reinforcement, the component E) in each of the systems independently obey the definition.

As optional ingredients included the only one as well as the first and the second (meth) acrylate system die Component E), namely one or more of the Conditions for the depolymerization of the (meth) acrylates inert filler (s) with a fineness ≦ 100 µm and based on the sum A) to E) in one amount at 0-75% by weight. It goes without saying that the first (Meth) acrylate system can have fillers other than the second, that the type and amount of fillers in the specified frames are independent of each other.

Here are in relation to the invention under Fillers under the conditions of depolymerization the (meth) acrylates are inert, such substances understood the depolymerization of acrylate polymers do not have a material adverse effect or even impossible do.

Acrylate polymers, especially PMMA, are among the few Plastics that are excellent for direct chemical Are suitable for recycling. This means that these polymers turn out to be at certain temperatures and pressures again completely into the corresponding monomer building blocks Allow to disassemble (depolymerization), if appropriate Way heat is supplied. For example, the Depolymerization of polymethyl methacrylate (PMMA) and Recovery of the resulting monomer Methyl methacrylate (MMA) by thermal treatment of Acrylic glass waste at temperatures <200 ° C, condensation the resulting monomer vapors and working up the crude Monomers in the literature and in the patents various continuous and discontinuous Procedures described. In the industrial on The most common method used is the polymer material placed in a cauldron partially filled with lead, the is heated from the outside. At temperatures of over 400 ° C depolymerizes the polymer material and the resulting Monomer vapors enter one via a pipeline Condenser where they become a raw, liquid monomer be condensed. Appropriate Depolymerization processes are, for example, from DE-OS 21 32 716 known.

The fillers E), as they are now within the scope of the invention are used, may not be substances or in the course the depolymerization result in decomposition products that have a Work-up of the crude, liquid monomer that is in the Depolymerization is to be recycled, make impossible or make it unnecessarily difficult. Therefore, those are preferred Fillers that act on the surface of the metal as Collect slag and, for example, during operation of the reactor with a rake, slide valve or the like can be removed. Using inventive Fillers E) is therefore a back-lined Sanitary ware that is completely recyclable.

Mineral fillers are usually used as fillers used. To the in a single or in the first and / or second (meth) acrylate system which can advantageously be used In the context of the invention, fillers include mica, Aluminum hydroxide, calcitic fillers such as chalk and marble, quartzitic fillers such as wollastonite, Cristobalite and similar, amorphous silicates, fly ash, Silicon carbide and / or barite.

Of these, mica and aluminum trihydrate are used for the invention (Aluminum hydroxide), quartzitic and calcitic Fillers are particularly suitable. That is extremely advantageous Use of mica in both the first and second (Meth) acrylate system or also in the (meth) acrylate system a single layer reinforcement.

The fillers E) are either alone or in Combination of several used. The amount is like already stated between 0 and 75 wt .-% based on the Sum of components A) to E) of the binder + Fillers.

If the proportion of fillers E) is higher than 75% by weight, then this can affect the mixing and processing properties of the Negatively affect the backing material, in particular it can be a mixture with such high Fillers only poorly sprayed or pumped will. In addition, it cannot be used with higher filler contents more ensure that there is enough binder to use Is available to obtain a stable coating.

On the other hand, according to the invention, there is a relatively high proportion of fillers E) are preferred. In particular, is made For reasons of cost, the aim is as high a quantity as possible. Fillers E) are preferred in an amount of 40-65% by weight, particularly preferably in an amount of 50-60% by weight, based in each case on the sum of the Components A) -E) included.

Smooth fillers are preferred for the invention. These include surfaces that are as smooth as possible Understanding particles. The particle size of the fillers according to the invention is ≦ 100 μm. It deals are therefore about the finest fillers. The particle size of the Fillers E) is determined by sieve analysis and is in of the specified size required to process the Filler E) + binder A) -D) system too guarantee. Especially when processing The size of the filler particles is sprayed through the The nozzle system used is limited. The size of the However, filler particles E) is a person skilled in the art To adapt the requirements of the processing system.

In addition, small filler particles with smoother The surface is better enveloped by binding agent, less too Tend aggregation and no air pockets in the Form reinforcement layer.

This is why a back-lined sanitary article is characterized the invention in a special modification in that the Fillers E) of the first (meth) acrylate system, which for first back layer hardens, a delicacy 30 mm. Such fine fillers allow a particularly clean and easy curing of the first Layer as well as easy application of the second Layer.

The component F) First variant: single-layer reinforcement

The following description concerns the case first a single layer reinforcement.

The filler component F) is for a single layer Reinforcement essential to the invention. These are the Microparticles F) an essential component of a single layer reinforcement.

For the reinforcement layer according to the invention is a whole Range of microparticles can be used. Basically acts they are hollow particles that are regular or irregular may be, but preferably spherical or are spherical and have inert gas in their cavity.

Concerning the hollow microspheres that can be used as component F) basically count hollow microspheres from different Materials such as B. glass, metals, metal oxides, Polymers and organic compounds.

Hollow microspheres are preferred for the invention Plastic used.

Are particularly preferred in the present invention as component F) for the reinforcement layer Hollow microspheres used, which consist of polymers, such as B. polystyrene, polyvinyl chloride, Polyvinylidene chloride, polyvinyl acetate, polyacrylate, Polyacrylonitrile, polybutadiene, polyethylene terephthalate; Furthermore, hollow microspheres are also preferred Copolymers or terpolymers based on such monomers based, which form the copolymers mentioned.

Examples of such polymers and copolymers which the Hollow spheres themselves include vinylidene chloride Acrylonitrile copolymer, polyvinylidene chloride, Acrylonitrile vinylidene chloride copolymer, Acrylonitrile methacrylonitrile copolymer, acrylonitrile divinylbenzene-vinylidene chloride copolymer and the like

In the context of the invention, as component F) preferably also use mixtures of hollow microspheres.

The hollow microspheres that can be used according to the invention or Microparticles can be used to adapt the Processing properties or to vary the Reinforcement properties be coated with coatings.

Modifications of the simple ones are also particularly suitable Hollow microspheres. For example, such hollow microspheres of particular interest, which consist of polymers, which are covered (coated) with mineral substances are to provide better stability against the influence of the surrounding medium (methacrylate resin).

The coating of the hollow microspheres can be made from fine-grained minerals such as B. calcium carbonate, Quartz, mica, aluminum hydroxide, cristobalite and such as exist.

Hollow microspheres are particularly preferred, in particular those made of plastic coated with calcium carbonate are.

The hollow microspheres which act particularly favorably as component F) within the scope of the invention can, in addition to other methods, in principle be produced in the following ways:

• - Coating of a core (sacrificial core) with the relevant material, then the core is through different methods removed (e.g. dissolve in a solvent, evaporation or volatilization), so that only the shell remains. With this method are mainly hollow ceramic balls Materials and metal oxides.
• - Production in a nozzle reactor (Nozzle-Reactor System):
  The gas in the hollow microspheres and the liquefied material for the shell of the spheres are sprayed through specially designed nozzle systems (concentric openings).
  The liquefied material cools down in a type of spray tower and solidifies to form a _{hollow microsphere filled with the respective gas (e.g. H 2} O, CO ₂ , SO ₂ , air, N ₂ , etc.). This method is mainly used to produce hollow microspheres from polymeric materials.
• - Phase separation of emulsions by liquid extraction:
  Here, the spherical, liquid-filled particles (micelles) present in an emulsion are separated from the surrounding liquid and then dried. This method is used primarily to produce hollow microspheres from metal oxides, but also from polymers.

An overview of the production of hollow microspheres can be found for example in Mat. Res. Soc. Symp. Proc. Vol. 372, 1995 Materials Research Society with David L. Wilcox, Sr. and Morris Berg, pp. 3-13, and those cited therein Literature.

To particularly suitable types of gas-filled Hollow microspheres made of plastic include, among other things ®Dualite types, e.g. B. ®Dualite M 6017AE, (Pierce & Stevens Corp.); ®Expancel types, e.g. B. ®Expancel 642 WU, ®Ropaque- Types, e.g. B. ®Ropaque OP 62 (Rohm and Haas Co.), Matsumoto Microsphere, e.g. B. Microsphere F-30E (Matsumoto Yushi Seiyaku Co. Ltd.) and the like.

The amount of filler F) in the or a reinforcement layer according to the invention is generally critical. If the proportion of hollow microspheres F) is below of 0.1 wt .-% based on the sum of all components of the (Meth) acrylate system, the inventive Effects will not be pronounced enough, in particular the physical properties are insufficient improved. A use of the microparticles, which is preferable are made of plastic, based on the sum A) -F) over 50% by weight is generally not advisable as there is no im Effect related to the additional cost in terms of improving physical Properties of the reinforcement layer seems achievable.

In a special embodiment of the invention Sanitary article this has the filler F) im (Meth) acrylate system or in the first and / or second (Meth) acrylate system in an amount ranging from 1 to 25 wt .-%, based on the weight of the sum of Components A) -F).

Furthermore, it is particularly advantageous if the Sanitary articles the filler F) in the (meth) acrylate system or in the first and / or second (meth) acrylate system in an amount in the range of 2 to 15 wt .-%, based on the Weight of the sum of the components A) -F).

Another preferred embodiment provides that the Sanitary articles according to the invention are thereby indicates that the filler F) is in the (meth) acrylate system or in the first and / or second (meth) acrylate system in an amount in the range of 3 to 10 wt .-%, based on the Weight of the sum of the components A) -F), is included.

Second variant: two- or multi-layer reinforcement

With regard to the nature of the filler F) applies basically the same as with the single-layer variant was executed. It is important that two or two according to the invention multilayer back linings in at least one Layer have the hollow microspheres F). Accordingly but can also do this in each individual layer Hollow microspheres be included. The particles are preferred F) in the first backing layer, i.e. the one Layer, which is the first layer on the Acrylic molded part is applied.

Within the specified limits, the person skilled in the art can Ingredients with simple experiments according to type and quantity select that it is one that complies with DIN EN 198 single layer back lining is preserved or in case a two-layer back lining a first Backing layer, which the sanitary article the required impact strength, and that he has a second backing layer is given, which the Gives sanitary ware the necessary rigidity.

The total reinforcement is usually 1.5 to 10 mm thick. Two layers together are i. d. R. also about 1.5 to 10 mm thick. It is an advantage here to be the first Layer thinner and the second layer thicker than the first Form layer. The second layer is advantageous about 2 to 3 times as thick as the first. That is advantageous total reinforcement in any case 1.5 to <8 mm thick.

The first layer expediently has a thickness in the range of 0.5-2.5 mm and the second layer has a thickness im Range of 3- <5.5 mm.

It was particularly astonishing that it was with a one or two-layer back lining according to the invention managed to get sufficiently reinforced sanitary ware without Generate fiberglass reinforcement.

Usually the fiberglass chaff form in the finished A backing layer according to the prior art Tangled up.

This matting effect was previously considered to be inevitable considered to be mechanically sufficiently strong To get reinforcements. It is all the more surprising Assess invention.

The present invention also includes a method for Production of a glass fiber and asbestos-free, back-lined sanitary ware with a reactive Resin system on the back of a molded part made of acrylic glass is sprayed on, the resin system in contact with the Acrylic molded part hardens and becomes with the Acrylic molded part connects, the process thereby is characterized in that a predominantly based on (meth) acrylates based resin system is used, which becomes a polymer hardens with a glass transition temperature Tg <70 ° C and based on 1 part by weight of the resin system up to 2.33 parts by weight of such fillers, which are under the Conditions for the depolymerization of the acrylic molded part are inert, the resin system being those specified herein Has composition.

Preferably, the method is carried out so that two different from one another, predominantly based on (meth) acrylates based resin systems are used one after the other, the each to a polymer with a Cure glass transition temperature Tg <70 ° C and cover to 1 part by weight of the resin system up to 2.33 parts by weight such fillers may have the under Conditions for the depolymerization of the acrylic molded part are inert, initially on the acrylic molded part first resin system is sprayed on, which the required impact strength imparted, and after that Curing on which a second resin system is sprayed, that gives the necessary rigidity.

From EP-A-0 693 503 it is known to have a (Meth) acrylate based resin system in the spray process to raise. In analogy to this, in a preferred variant of the invention two layers applied one after the other, additionally when choosing of the possible fillers for their harmlessness in the Depolymerization of the polymers is respected by a careful coordination of material selection (both molded part as well as backing are based on (meth) acrylates, Fillers are inert) and application method of the Backing layers are one hundred percent recyclable Product becomes accessible, which at the same time as a result of the Spray method is particularly material-saving and simple can be produced.

In addition, and above all, be in all, be it in one or in both or more layers of glass fibers avoided.

The method of the invention is preferably characterized in that a polymerizable, cold-curing, reactive (meth) acrylate system is used as the first resin system

• A)
  • a) (Meth) acrylate 30-100% by weight
    • a1) methyl (meth) acrylate 0-100% by weight
    • a2) C ₂ -C ₄ (meth) acrylate 0-100% by weight
    • a3) ≧ C ₅ (meth) acrylate 10-50% by weight
    • a4) polyvalent (meth) acrylates 0-50% by weight
    b) comonomers 0-50% by weight
    • b1) vinyl aromatics 0-30% by weight
    • b2) vinyl ester 0-30% by weight
• B) to 1 part A) 0.05-5 parts of one soluble in A) or swellable (pre) polymers
• C) one to the polymerization of the polymerizable components of the system entirely or partially separated redox system containing an accelerator and a peroxide catalyst or initiator in one Amount sufficient for cold curing of component A)
• D) common additives
• E) fillers, based on the Sum A) -E) 0-75% by weight, the fillers having a particle size ≦ 100 µm exhibit
• F) hollow microparticles filled with inert gas, preferably made of plastic, based on the total A) -F) 0.1-50% by weight

contains.

Furthermore, it is preferred that a polymerizable, cold-curing, reactive (meth) acrylate system is used as the second resin system, which

• A)
  • a) (Meth) acrylate 30-100% by weight
    • a1) methyl (meth) acrylate 0-100% by weight
    • a2) C ₂ -C ₄ (meth) acrylate 0-100% by weight
    • a3) ≧ C ₅ (meth) acrylate 0- <10% by weight
    • a4) polyvalent (meth) acrylates 0-50% by weight
    b) comonomers 0-50% by weight
    • b1) vinyl aromatics 0-30% by weight
    • b2) vinyl ester 0-30% by weight
• B) to 1 part A) 0.05-5 parts of one soluble in A) or swellable (pre) polymers
• C) one up to the polymerization of the polymerizable Components of the system completely or partially separated Redox system to be maintained containing an accelerator and a peroxide catalyst or initiator in an amount sufficient to work harden the component A)
• D) common additives
• E) fillers, based on the sum A) -E) 0-75% by weight,
  the fillers having a particle size of <100 µm
• F) hollow microparticles filled with inert gas, preferably made of plastic, based on the total A) -F) 0.1-50% by weight

contains.

To the settling behavior of the fillers E) with longer To improve storage times before use and thus the To increase storage stability, it is preferred that the Fillers E) before using the reactive resin system a homogenization unit with the addition of a Thixotropic agent in an amount of 0.01-0.5 parts based on 1 part E) in the first and / or second system from binders A) -D) are incorporated.

By using a suitable homogenizing unit in the manufacture of the resin system, the The size and shape of the filler particles are positive influenced.

Leave the back-lined sanitary articles according to the invention one after the other by spraying or squirting one Resin systems A) to F) or the respective resin systems A) to F) on the back of the acrylic molded part.

Here, two are preferred during each spraying Material streams mixed with one another, a first of the Material flows the polymerizable components of the Resin mixture and a second stream of material up to Polymerization of the polymerizable components of the Resin system to be kept separately components of the Has component C) of the resin system.

High-pressure airless paints are preferred for spraying Spray systems (e.g. applicator IP 8000 from ESSKA, Hamburg), surface jet spray systems from Glascraft or two-component dosing and mixing system with Working pressure 40 to 60 bar (e.g. "twin injection" from the company Reinhardt Technik, Kierspe) is used. Under use such systems can be especially in Fan beam coating under simultaneous significantly reduce the emission values. This can be done advantageously with spray guns that have a individual regulation of the loss-free laminate application enable.

Mixing and atomizing processes are particularly suitable Subject of EP 38 481.

The method of the invention is particularly notable in that it is carried out at ambient temperature can be, d. H. usually between 0 and 35 ° C, but also, if desired, at more extreme temperatures such as -10 up to + 45 ° C.

In the following the invention is based on Embodiments and comparative examples in more detail explained.

Comparative example 1 (CE1) Single-layer reinforcement without hollow microspheres, approx. 3 mm thickness

40.00 parts by weight of a binder consisting of
18.00% polymethyl methacrylate
75.00% methyl methacrylate
5.00% triethylene glycol dimethacrylate
0.50% paraffins (melting point <56 ° C)
0.50% dimethyl paratoluidine
0.50% diisopropoxyparatoluidine
0.50% additives, stabilizers
be with
60.00 parts by weight mica (<100 µm) and
0.10 parts by weight of thixotropic agent (Byk 410)
stirred for 4 hours.

The mixture has a viscosity of 11,000-13,000 mPas on.

This mixture is applied to the molded acrylic glass part with a high-pressure airless spray system of the type Applicator IP 8000 together with Cadox 40 E in a volume ratio of 100: 2 to 100: 5, with a spray pressure of 180 bar. The application rate is 6-7 kg / m ² . Manual post-processing is not required. A backing layer approximately 3 mm thick is obtained.

With hardener dosage 100: 2 the hardening time is about 15-25 min.

With a hardener dosage of 100: 4, the hardening time is about 5-15 min.

Comparative example 2 (CE2)

Two-layer reinforcement with reinforcement layer 1a, however, both layers without hollow microspheres, common Thickness of the two layers together approx. 6 mm;

(i) Reinforcement layer 1a

40.00 parts by weight of a binder consisting of
30.00% polymethyl methacrylate
42.00% methyl methacrylate
25.70% 2-ethylhexyl acrylate
0.50% triethylene glycol dimethacrylate
0.80% diisopropylene paratoluidine
0.70% dimethyl paratoluidine
0.30% paraffins (melting point <56 ° C)
be with
60.00 parts by weight calcium carbonate (<100 microns) and
0.10 parts by weight of thixotropic agent (Byk 410)
stirred for 4 hours.

The mixture has a viscosity of 6000-10,000 mPas on.

This mixture is applied to the molded acrylic glass part with a high-pressure airless spray system of the type Applicator IP 8000 together with Cadox 40 E in a volume ratio of 100: 2 to 100: 5, with a spray pressure of 180 bar. Manual post-processing is not required. The application rate is 2-4 kg / m ² .

With hardener dosage 100: 2 the hardening time is 15-40 min.

With a hardener dosage of 100: 5, the hardening time is 5-20 min.

This is followed by a second spray application following mixture:

(ii) Reinforcement Layer 1

40.00 parts by weight of a binder consisting of
18.00% polymethyl methacrylate
75.00% methyl methacrylate
5.00% triethylene glycol dimethacrylate
0.50% paraffins (melting point <56 ° C)
0.50% dimethyl paratoluidine
0.50% diisopropylene paratoluidine
0.50% additives, stabilizers
be with
60.00 parts by weight mica (<100 µm)
0.10 parts by weight of thixotropic agent (Byk 410)
stirred for 4 hours.

The mixture has a viscosity of 11,000-13,000 mPas on.

The hardener dosage is 100: 2 to 100: 5.

The injection pressure is 180 bar.

The application rate is 6-10 kg / m ² .

The hardening time is 15-30 min with hardener dosage 100: 2.

With a hardener dosage of 100: 5, the hardening time is about 5-15 min.

Example 3 (B3)

Single-layer reinforcement with hollow microspheres, thickness of the backing layer approx. 3 mm; 40.00 parts by weight of a binder consisting of
18.00% polymethyl methacrylate
75.00% methyl methacrylate
5.00% triethylene glycol dimethacrylate
0.50% paraffins (melting point <56 ° C)
0.50% dimethyl paratoluidine
0.50% diisopropoxyparatoluidine
0.50% additives, stabilizers
be with
54.00 parts by weight mica (<100 µm)
6.00 parts by weight of gas-filled, calcium carbonate-coated hollow microspheres made of acrylonitrile copolymer with an average particle size of about 95 μm of the ®Dualite 6032 type from Pierce & Stevens Corporation and
0.10 parts by weight of thixotropic agent (Byk 410)
stirred for 4 hours.

The mixture has a viscosity of 11,000-13,000 mPas on.

This mixture is applied to the molded acrylic glass part with a high-pressure airless spray system of the type Applicator IP 8000 together with Cadox 40 E in a volume ratio of 100: 2 to 100: 5, with a spray pressure of 180 bar. The application rate is about 4-7 kg / m ² . Manual post-processing is not required. A backing layer approximately 3 mm thick is obtained.

With hardener dosage 100: 2 the hardening time is about 15-25 min.

With a hardener dosage of 100: 4, the hardening time is about 5-15 min.

Example 4 (B4)

Two-layer reinforcement with reinforcement layer 1a, first reinforcement layer 1a with hollow microspheres, second Reinforcement layer without hollow microspheres, thickness each Reinforcement layer about 1.5mm, thickness of the entire Reinforcement about 3 mm;

(i) Reinforcement layer 1a

40.00 parts by weight of a binder consisting of
30.00% polymethyl methacrylate
42.00% methyl methacrylate
25.70% 2-ethylhexyl acrylate
0.50% triethylene glycol dimethacrylate
0.80% diisopropylene paratoluidine
0.70% dimethyl paratoluidine
0.30% paraffins (melting point <56 ° C)
be with
54.00 parts by weight mica (<100 µm)
6.00 parts by weight of gas-filled, calcium carbonate-coated hollow microspheres made of acrylonitrile copolymer with an average particle size of about 95 μm of the ®Dualite 6032 type from Pierce & Stevens Corporation and
0.10 parts by weight of thixotropic agent (Byk 410)
stirred for 4 hours.

The mixture has a viscosity of 6000-10,000 mPas on.

This mixture is applied to the molded acrylic glass part with a high-pressure airless spray system of the type Applicator IP 8000 together with Cadox 40 E in a volume ratio of 100: 2 to 100: 5, with a spray pressure of 180 bar. Manual post-processing is not required. The application rate is about 2-3.5 kg / m ² .

With hardener dosage 100: 2 the hardening time is 15-40 min.

With a hardener dosage of 100: 5, the hardening time is 5-20 min.

This is followed by a second spray application following mixture:

(ii) Reinforcement Layer 1

40.00 parts by weight of a binder consisting of
18.00% polymethyl methacrylate
75.00% methyl methacrylate
5.00% triethylene glycol dimethacrylate
0.50% paraffins (melting point <56 ° C)
0.50% dimethyl paratoluidine
0.50% diisopropylene paratoluidine
0.50% additives, stabilizers
be with
60.00 parts by weight mica (<100 µm)
0.10 parts by weight of thixotropic agent (Byk 410)
stirred for 4 hours.

The mixture has a viscosity of 11,000-13,000 mPas on.

The hardener dosage is 100: 2 to 100: 5.

The injection pressure is 180 bar.

The application rate is 2-3.5 kg / m ² .

The hardening time is 15-30 min with hardener dosage 100: 2.

With a hardener dosage of 100: 5, the hardening time is about 5-15 min.

After hardening, the complete tubs are the Tests according to DIN EN 198 and the test specimens from the finished tubs are cut out for exams according to DIN ISO 4624, DIN ISO 178 and DIN ISO 179. The regulations from the in each year were used 1996 regulations.

When testing in the hot water alternation test according to DIN EN 198 is a tub alternating with water at 75 ° C and then from 12 ° C filled. DIN EN 198 calls for this to be harmless Existence of 100 such cycles. Existence includes that the condition of the tubs does not detach the reinforcement and no cracks in the acrylic glass.

The behavior in the event of shock loads according to the ball drop test according to DIN EN 198 is considered acceptable if none Damage to the surface and the underside of a Tub after falling from a height of a steel ball of 200 g from 1 m to the bottom of the tub.

These and the other results can be found in Table 1 can be removed.

Table 1

Claims (26)

1. Back-lined sanitary article, comprising an acrylic molded part, which is reinforced on its back with fiberglass and asbestos-free, 1.5 to 10 mm thick polymer material, which is firmly connected to the acrylic molded part without additional adhesion promoters, characterized in that the reinforcing polymer material by curing a polymerizable, cold-curing, reactive (meth) acrylate system sprayed onto the rear side of the molded acrylic glass part, which

• A)
  • a) (Meth) acrylate 30-100% by weight
    • a1) methyl (meth) acrylate 0-100% by weight
    • a2) C ₂ -C ₄ (meth) acrylate 0-100% by weight
    • a3) ≧ C ₅ (meth) acrylate 0-50% by weight
    • a4) polyvalent (meth) acrylate 0-50% by weight
  • b) comonomers 0-50% by weight
    • b1) vinyl aromatics 0-30% by weight
    • b2) vinyl ester 0-30% by weight
• B) to 1 part by weight of A) 0.05-5 parts by weight of a (pre) polymer which is soluble or swellable in A)
• C) a redox system to be kept completely or partially separate from the constituents of the system to be polymerized up to the point of polymerization, comprising an accelerator and a peroxide catalyst or initiator in an amount sufficient for cold curing of component A)
• D) common additives
• E) fillers inert under the conditions of the depolymerization based on the sum A) -E) with a fineness ≦ 100 µm 0-75% by weight
• F) hollow microparticles filled with inert gas, based on the sum A) -F) 0.1-50% by weight

contains. 2. Sanitary article according to claim 1, characterized in that the reinforcing material consists of a first and a second layer, the first layer being obtainable by curing a polymerizable, cold-curing, reactive, first (meth) acrylate system sprayed onto the back of the acrylic molded part , which

• A)
  • a) (Meth) acrylate 30-100% by weight
    • a1) methyl (meth) acrylate 0-100% by weight
    • a2) C ₂ -C ₄ (meth) acrylate 0-100% by weight
    • a3) ≧ C ₅ (meth) acrylate 10-50% by weight
    • a4) polyvalent (meth) acrylates 0-50% by weight
  • b) comonomers 0-50% by weight
    • b1) vinyl aromatics 0-30% by weight
    • b2) vinyl ester 0-30% by weight
• B) to 1 part by weight of A) 0.05-5 parts by weight of a (pre) polymer which is soluble or swellable in A)
• C) a redox system to be kept completely or partially separate from the constituents of the system to be polymerized up to the point of polymerization, comprising an accelerator and a peroxide catalyst or initiator in an amount sufficient for cold curing of component A)
• D) common additives
• E) fine fillers inert under the conditions of the depolymerization based on the sum A) -E) with a fineness ≦ 100 µm 0-75% by weight
• F) hollow microparticles felt with inert gas, based on the sum A) -F) 0.1-50% by weight

contains,
and the second layer is obtainable by curing a polymerizable, cold-curing, reactive, second (meth) acrylate system which is sprayed onto the first layer and which is different from the first (meth) acrylate system, the second (meth) acrylate system being System except for component a3), ie except for the content of ≧ C ₅ (meth) acrylate, which is 0 to <10 wt .-%, and except for component F), which is based on the sum A) -F ) is present in an amount of 0-50% by weight, the same general definition applies as for the first (meth) acrylate system. 3. Sanitary article according to claim 1 or 2, characterized, that the filler F) from gas-filled, expanded Hollow microspheres made of plastic. 4. Sanitary article according to claim 3, characterized, that the hollow microspheres coated with calcium carbonate are. 5. Sanitary ware according to one or more of the preceding claims, characterized, that the filler F) in the (meth) acrylate system or in first and / or second (meth) acrylate system in one Amount in the range of 1 to 25 percent by weight, based on on the weight of the sum of the components A) to F), is included. 6. Sanitary ware according to one or more of the preceding claims 1 to 4, characterized, that the filler F) in the (meth) acrylate system or in first and / or second (meth) acrylate system in one Amount in the range of 2 to 15 percent by weight, based on on the weight of the sum of the components A) to F), is included. 7. Sanitary ware according to one or more of the preceding claims 1 to 4, characterized, that the filler F) in the (meth) acrylate system or in first and / or second (meth) acrylate system in one Amount in the range of 3 to 10 percent by weight, based on on the weight of the sum of the components A) to F), is included. 8. Sanitary article according to claim 1 or 2, characterized, that the fillers E) mica, aluminum hydroxide, Calcium carbonate, chalk, marble, quartzite, wollastonite and / or cristobalite. 9. Sanitary article according to claim 1, characterized, that the filler E) in the (meth) acrylate system is mica is. 10. Sanitary article according to claim 2, characterized, that the filler E) in the first and second (Meth) acrylate system is mica. 11. Sanitary ware according to one or more of the preceding claims, characterized, that the fillers E) in the (meth) acrylate system or in first and / or second (meth) acrylate system in one Amount of 40-65% by weight, preferably 50-60% by weight, based on the sum A) -E). 12. Sanitary ware according to one or more of the preceding claims, characterized, that the (meth) acrylate or the (meth) acrylate systems the components B): A) in a weight ratio im Range from 0.1: 1 to 2: 1. 13. Sanitary article according to claim 12, characterized, that the weight ratio of B): A) is in the range of 0.2: 1 to 1: 1. 14. Sanitary article according to one of the preceding claims, characterized, that B) one obtainable by suspension polymerization PMMA lacquer bead, an emulsion polymer and / or Regrind from a recycling process with a medium Particle diameter is up to 0.8 mm. 15. Sanitary article according to claim 14 insofar as this on Claim 2 or a claim based on it Refers to characterized, that the prepolymer B) of the first reinforcing layer a comonomer content between 30 and 80% by weight, the of the second reinforcement layer between 0 and Has <30 wt .-%. 16. Sanitary article according to claim 15, characterized, that the comonomer methyl acrylate, ethyl acrylate, Butyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, 2-ethylhexyl methacrylate, propyl acrylate, Propyl methacrylate, methacrylic acid, Ethyl triglycol methacrylate and / or Is hydroxypropyl methacrylate. 17. Sanitary ware according to one or more of the preceding claims, characterized, that in the (meth) acrylate system or in the first and / or second (meth) acrylate system based on 1 part by weight of E) or F) contain up to 0.5 parts of thixotropic agent are. 18. Sanitary ware according to one or more of the preceding claims, characterized, that in the presence of two reinforcement layers the first layer a thickness of 0.5-2.5 mm and the second layer a thickness in the range of 2.5- <5.5 mm exhibit. 19. Process for the manufacture of a fiberglass and asbestos-free, back-lined sanitary ware where at least one reactive resin system on the back a molded part made of acrylic glass is sprayed on, wherein the resin system in contact with the acrylic molded part hardens and becomes with the acrylic molded part connects, characterized, that a resin system based on (meth) acrylates that is used to form a polymer with a Glass transition temperature Tg <70 ° C hardens and based on 1 part by weight of the respective resin system to to 2.33 parts by weight of such fillers under the conditions of the depolymerization of the Acrylic molded part are inert, the (meth) acrylate The system has the composition specified in claim 1 having. 20. The method according to claim 19, characterized, that two different from each other predominantly on (Meth) acrylate-based resin systems are used each become a polymer with a Cure glass transition temperature Tg <70 ° C and based on 1 part by weight of the respective resin system to can contain 2.33 parts by weight of such fillers, under the conditions of the depolymerization of the Acrylic molded part are inert, with the Acrylic molded part initially a first resin system is sprayed on, whichever is required Impact strength imparted, and after it has hardened then a second resin system is sprayed on, which the gives necessary rigidity. 21. The method according to claim 20, characterized in that a polymerizable, cold-curing, reactive (meth) acrylate system is used as the first resin system, which

• A)
  • a) (Meth) acrylate 30-100% by weight
    • a1) methyl (meth) acrylate 0-100% by weight
    • a2) C ₂ -C ₄ (meth) acrylate 0-100% by weight
    • a3) ≧ C ₅ (meth) acrylate 10-50% by weight
    • a4) polyvalent (meth) acrylates 0-50% by weight
  • b) comonomers 0-50% by weight
    • b1) vinyl aromatics 0-30% by weight
    • b2) vinyl ester 0-30% by weight
• B) to 1 part A) 0.05-5 parts of a (pre) polymer which is soluble or swellable in A)
• C) a redox system which is to be kept completely or partially separate from the polymerizable constituents of the system up to the point of polymerization and contains an accelerator and a peroxide catalyst or initiator in an amount sufficient for cold curing of component A)
• D) common additives
• E) fillers, based on the sum A) -E) 0-75% by weight, the fillers having a particle size ≦ 100 µm,
• F) hollow microparticles filled with inert gas, based on the sum A) -F) 0.1-50% by weight

contains. 22. The method according to claim 20 or 21, characterized in that a polymerizable, cold-curing, reactive (meth) acrylate system is used as the second resin system, which

• A)
  • a) (Meth) acrylate 30-100% by weight
    • a1) methyl (meth) acrylate 0-100% by weight
    • a2) C ₂ -C ₄ (meth) acrylate 0-100% by weight
    • a3) ≧ C ₅ (meth) acrylate 0- <10% by weight
    • a4) polyvalent (meth) acrylates 0-50% by weight
  • b) comonomers 0-50% by weight
    • b1) vinyl aromatics 0-30% by weight
    • b2) vinyl ester 0-30% by weight
• B) to 1 part A) 0.05-5 parts of a (pre) polymer which is soluble or swellable in A)
• C) a redox system which is to be kept completely or partially separate from the polymerizable constituents of the system up to the point of polymerization and contains an accelerator and a peroxide catalyst or initiator in an amount sufficient for cold curing of component A)
• D) common additives
• E) fillers, based on the sum A) -E) 0-75% by weight, the fillers having a particle size <100 μm
• F) hollow microparticles filled with inert gas, based on the sum A) -F) 0-50% by weight

contains. 23. The method according to claim 21 or 22, characterized, that the fillers E) before using the reactive Resin systems with a homogenization unit below Addition of a thixotropic agent in an amount of 0.01-0.5 parts based on 1 part E) in the first and / or a second system of respective binders A) -D) are incorporated. 24. The method according to any one of claims 21-23, characterized, that as fillers E) Aluminum hydroxide, calcium carbonates such as chalk or Marble, barite and / or quartzite such as wollastonite, Cristobalite, amorphous silicates, fly ash and / or Mica can be used. 25. The method according to claim 22 or 23, characterized, that mica is used as filler E). 26. The method according to one or more of claims 20 to 25, characterized, that the resin systems successively on the back of the Acrylic molded part are sprayed on, while of spraying two streams of material together are mixed and a first one of the material streams the polymerizable components of the resin mixture and a second stream of material leading up to the polymerization of the polymerizable components of the resin system components of component C) to be kept separate of the resin system.