The invention relates to the use of compounds of the general formula (I)

This invention relates to a new medical use for a group of heterocyclic compounds and pharmaceutical compositions containing them. In particular it relates to certain tetrahydrocarbazolone derivatives which may be used to promote gastric emptying and as anti-emetic agents.
A particularly important application for anti-emetic agents is in the prevention and treatment of nausea and vomiting associated with cancer chemotherapy. Emesis is a well-known and frequent side-effect of cancer chemotherapeutic agents, such as cisplatin. It causes serious problems in cancer chemotherapy, and in some patients emesis is so severe that therapy must be discontinued. Anti-emetic agents are therefore often administered in order to alleviate this side-effect of the cancer chemotherapeutic agent. The anti-emetic agents employed are usually benzamide derivatives, such as metoclopramide, which have dopamine antagonist activity.
Metoclopramide is also a gastric motility stimulant, i.e. it promotes gastric emptying. The promotion of gastric emptying is important in the treatment of gastro-intestinal disorders related to gastric stasis; and in radiological examinations.
In view of their dopamine antagonist activity benzamide derivatives such as metoclopramide themselves exhibit serious and undesirable side-effects, such as extra-pyramidal effects, i.e. tardive dyskinesia, acute distonia, akathisia and tremor. There is thus a need for a safe and effective anti-emetic agent and gastric motility stimulant.
In our British patent application No. 2153821A and our European patent application No. 86300423 we disclose 3-imidazolylmethyltetrahydrocarbazolones which may be represented by the general formula (I)
wherein
R1 represents a hydrogen atom or a C1-10 alkyl, C3-7 cycloalkyl, C3-7cycloalkyl-(C1-4)alkyl, C3-6 alkenyl, C3-10 alkynyl, phenyl or phenyl-C1-3alkyl group, and one of the groups represented by R2, R3 and R4 is a hydrogen atom or a C1-6 alkyl, C3-7 cycloalkyl, C2-6 alkenyl or phenyl-C1-3alkyl group and each of the other two groups, which may be the same or different, represents a hydrogen atom or a C1-6 alkyl group; and physiologically acceptable salts and solvates, e.g. hydrates, thereof.
Suitable physiologically acceptable salts of the carbazolones of general formula (I) include acid addition salts formed with organic or inorganic acids for example, hydrochlorides, hydrobromides, sulphates, phosphates, citrates, fumarates and maleates. The solvates may, for example, be hydrates.
The aforementioned specifications also disclose physiologically acceptable equivalents of the compounds of formula (I), i.e. physiologically acceptable compounds which are converted in vivo into the parent compound of formula (I).
The compounds of formula (I) are described in the aforementioned specifications as potent and selective antagonists of 5-hydroxytryptamine (5-HT) at xe2x80x98neuronalxe2x80x99 5-HT receptors of the type located on terminals of primary afferent nerves, and which are also believed to be present in the central nervous system. The compounds are described as being of use in the treatment of a human or animal subject suffering from a condition caused by a disturbance of neuronal 5HT function, for example in the treatment of a human subject suffering from migraine pain or a psychotic disorder such as schizophrenia. It is also stated that the compounds may be useful in the treatment of conditions such as anxiety, obesity and mania.
We have now surprisingly found that compounds of formula (I) promote gastric emptying and also that they are anti-emetic.
Accordingly, the invention provides a method of treatment for the relief of nausea and vomiting, and/or the promotion of gastric emptying e.g. for the relief of gastro-intestinal disorders associated with gastric stasis, which comprises administering to a human or animal subject an effective amount of a compound of formula (I), or a physiologically acceptable salt or solvate thereof.
Tests in animals have shown that compounds of formula (I) enhance gastric emptying. The compounds are therefore of use in the treatment and/or prevention of conditions which may be relieved by the promotion of gastric emptying e.g. gastric stasis which may occur, for example, post-operatively, and symptoms of gastro-intestinal dysfunction such as occur with dyspepsia, peptic ulcer, reflux oesophagitis and flatulence. The compounds may also be used to promote gastric emptying in diagnostic radiological procedures, such as radiological examinations.
Tests in animals have also shown that compounds of formula (I) inhibit emesis. The compounds are therefore also of use as anti-emetic agents, i.e. in the prevention and treatment of nausea and vomiting. The compounds are especially valuable for the prevention of emesis induced by cancer chemotherapeutic agents such as cisplatin. Particular mention may also be made of the treatment of radiation-induced emesis. Thus, the compounds of formula (I) may be used in the prevention of emesis induced by radiation therapy, e.g. irradiation of the thorax or abdomen, such as in the treatment of cancer; or in the treatment of radiation sickness.
The compounds of formula (I) do not possess dopamine antagonist activity and thus will not produce the undesirable side effects found with known anti-emetic agents such as metoclopramide.
It will be appreciated that the compounds of formula (I) may be used prophylactically and references in this specification to treatment include prophylactic treatment as well as the alleviation of acute symptoms.
A preferred class of compounds for use according to the invention is that represented by the formula (Ia):
(wherein R1a represents a hydrogen atom or a methyl, ethyl, propyl, prop-2-yl, prop-2-enyl or cyclopentyl group; R3a represents a hydrogen atom; and either R2a represents a-methyl, ethyl, propyl or prop-2-yl group and R4a represents a hydrogen atom or R2a represents a hydrogen atom and R4a represents a methyl or ethyl group) and physiologically acceptable salts and solvates (e.g. hydrates) thereof.
Preferred compounds for use according to the present invention are:
1,2,3,9-tetrahydro-3-[(2-methyl-1H-imidazol-1-yl)methyl]-9-(prop-2-enyl)-4H-carbazol-4-one;
9-cyclopentyl-1,2,3,9-tetrahydro-3-[(2-methyl-1H-imidazol-1-yl)methyl]-4H-carbazol-4-one; and
1,2,3,9-tetrahydro-3-[(2-methyl-1H-imidazol-1-yl)methyl]-9-(prop-2-yl)-4H-carbazol-4-one and their physiologically acceptable salts and solvates.
A particularly preferred compound is 1,2,3,9-tetrahydro-9-methyl-3-[(2-methyl-1H-imidazol-1-yl)methyl]-4H-carbazol-4-one, and the physiologically acceptable salts and solvates (e.g. hydrates) thereof. A preferred form of this compound is the hydrochloride dihydrate.
The compounds of formula (Ia) are well absorbed from the gastro-intestinal tract. They do not prolong sleeping time in the pentobarbitone anaesthetised mouse indicating that there is no undesirable interaction with drug metabolising enzymes. Indeed they exhibit no effects on normal behaviour, are non-toxic and exhibit no undesirable effects in mice at doses up to 1 mg/kg intravenously.
Accordingly, the invention also provides a pharmaceutical composition which comprises at least one compound selected from 3-imidazolylmethyltetrahydrocarbazolone derivatives of the general formula (I), their physiologically acceptable salts and solvates, e.g. hydrates, for use in human or veterinary medicine, for the relief of nausea and vomiting and/or the promotion of gastric emptying e.g. for the relief of gastro-intestinal disorders associated with gastric stasis.
In a yet further aspect, the invention provides the use of a compound of formula (I) or a physiologically acceptable salt or solvate thereof, for the manufacture of a medicament for the relief of nausea and vomiting, and/or the promotion of gastric emptying e.g. for the relief of gastro-intestinal disorders associated with gastric stasis.
Pharmaceutical compositions for use in accordance with the present invention may be formulated in conventional manner using one or more physiologically acceptable carriers or excipients.
Thus the compounds of formula (I) and their physiologically acceptable salts and solvates may be formulated for oral, buccal, parenteral or rectal administration or in a form suitable for administration by inhalation or insufflation (either through the mouth or the nose).
For oral administration, the pharmaceutical compositions may take the form of, for example, tablets or capsules prepared by conventional means with pharmaceutically acceptable excipients such as binding agents (e.g. pregelatinised maize starch, polyvinylpyrrolidone or hydroxypropyl methylcellulose); fillers (e.g. lactose, microcrystalline cellulose or calcium hydrogen phosphate); lubricants (e.g. magnesium stearate, talc or silica); disintegrants (e.g. potato starch or sodium starch glycollate); or wetting agents (e.g. sodium lauryl sulphate). The tablets may be coated by methods well known in the art. Liquid preparations for oral administration may take the form of, for example, solutions, syrups or suspensions, or they may be presented as a dry product for constitution with water or other suitable vehicle before use. Such liquid preparations may be prepared by conventional means with pharmaceutically acceptable additives such as suspending agents (e.g. sorbitol syrup, cellulose derivatives or hydrogenated edible fats); emulsifying agents (e.g. lecithin or acacia); non-aqueous vehicles (e.g. almond oil, oily esters, ethyl alcohol or fractionated vegetable oils); and preservatives (e.g. methyl or propyl-p-hydroxybenzoates or sorbic acid). The preparations may also contain buffer salts, flavouring, colouring and sweetening agents as appropriate.
Preparations for oral administration may be suitably formulated to give controlled release of the active compound.
For buccal administration the compositions may take the form of tablets or lozenges formulated in conventional manner.
The compounds of formula (I) may be formulated for parenteral administration by injection e.g. by bolus injection or continuous infusion. Formulations for injection may be presented in unit dosage form e.g. in ampoules or in multi-dose containers, with an added preservative. The compositions may take such forms as suspensions, solutions or emulsions in oily or aqueous vehicles, and may contain formulatory agents such as suspending, stabilising and/or dispersing agents. Alternatively, the active ingredient may be in powder form for constitution with a suitable vehicle, e.g. sterile pyrogen-free water, before use.
The compounds of formula (I) may also be formulated in rectal compositions such as suppositories or retention enemas, e.g. containing conventional suppository bases such as cocoa butter or other glycerides.
In addition to the formulations described previously, the compounds may also be formulated as a depot preparation. Such long acting formulations may be administered by implantation (for example subcutaneously or intramuscularly) or by intramuscular injection. Thus, for example, the compounds of formula (I) may be formulated with suitable polymeric or hydrophobic materials (for example as an emulsion in an acceptable oil) or ion exchange resins, or as sparingly soluble derivatives, for example, as a sparingly soluble salt.
For administration by inhalation the compounds for use according to the present invention are conveniently delivered in the form of an aerosol spray presentation from pressurised packs or a nebuliser, with the use of a suitable propellant, e.g. dichlorodifluoromethane, trichlorofluoromethane, dichlorotetrafluoroethane, carbon dioxide or other suitable gas. In the case of a pressurised aerosol the dosage unit may be determined by providing a valve to deliver a metered amount. Capsules and cartridges of e.g. gelatin for use in an inhaler or insufflator may be formulated containing a powder mix of a compound of formula (I) and a suitable powder base such as lactose or starch.
The compositions may, if desired, be presented in a pack or dispenser device which may contain one or more unit dosage forms containing the active ingredient. The pack may for example comprise metal or plastic foil, such as a blister pack. The pack or dispenser device may be accompanied by instructions for administration.
A proposed dose of the compounds of the invention for administration in man (of approximately 70 kg body weight) is 0.05 to 20 mg, preferably 0.1 to 10 mg of the active ingredient per unit dose which could be administered, for example, 1 to 4 times per day. The dose will depend on the route of administration and the body weight of the patient. It will be appreciated that it may be necessary to make routine variations to the dosage depending on the age and weight of the patient as well as the severity of the condition to be treated.
For oral administration a unit dose will preferably contain from 0.5 to 8 mg of the active ingredient. A unit dose for parenteral administration will preferably contain 0.1 to 8 mg of the active ingredient.
Aerosol formulations are preferably arranged so that each metered dose or xe2x80x98puffxe2x80x99 delivered from a pressurised aerosol contains 0.2 mg to 4 mg of a compound of the invention, and each dose administered via capsules and cartridges in an insufflator or an inhaler contains 0.2 to 20 mg of a compound of the invention. The overall daily dose by inhalation will be within the range 0.4 to 80 mg. Administration may be several times daily, for example from 2 to 8 times, giving for example 1, 2 or 3 doses each time.
The compounds of formula (I) may be administered in combination with other therapeutic agents, for example to aid absorption of the therapeutic agent where this is hindered by the patient""s condition, such as by gastric stasis associated with migraine. Thus, for example, the compounds may be administered in combination with antimigraine agents such as ergotamine, or antisecretory agents such as ranitidine. They may also be administered in combination with anticancer (e.g. cytostatic) drugs, for example to prevent nausea and vomiting associated with these agents. Cytostatic agents with which compounds of formula (I) may be administered include cyclophosphamide; alkylating agents; and platinum complexes such as cisplatin. Thus, a compound of formula (I) may be presented together with another therapeutic agent as a combined preparation for simultaneous, separate or sequential use, for the relief of nausea and vomiting, or gastrointestinal disorders associated with gastric stasis. Such a combined preparation may be, for example, a twin-pack. A preferred combination comprises a compound of formula (I) with a cytostatic agent, especially cisplatin.
In general, the presently available dosage forms of the known therapeutic agents will be suitable for use in such combined preparations. Thus, cisplatin may be provided in vials containing 10, 25 or 50 mg of the active ingredient.
The compounds of general formula (I) may be prepared by the process described in British patent application No. 2153821A.
Example 22 of British patent application 2153821 describes the preparation of a compound of formula (Ia) which is 3R-1,2,3,9-Tetrahydro-9-methyl-3-[(2-methyl-1H-imidazol-1-yl)methyl]-4H-carbazol-4-one maleate.
A solution of the product from Example 7 (1,2,3,9-Tetrahydro-9-methyl-3-[(2-methyl-1H-imidazol-1-yl)methyl]4H-carbazol-4-one) (0.5 g) was dissolved in hot methanol (30 ml) and treated with a hot solution of (xe2x88x92)di-p-toluoyl-L-tartaric acid monohydrate (0.7 g) in methanol (10 ml) and the resulting solution allowed to crystallise overnight to give the desired salt (0.8 g). This salt was dissolved in hot dimethylformamide (DMF, 20 ml), diluted with hot water (10 ml) and allowed to crystallise for 3 days. The product was filtered off, and dried in vacuo to give ca 95% enantiomerically pure (as shown by n.m.r.)(xe2x88x92)-di-p-toluoyl-L-tartaric salt (0.26 g) m.p. 170xc2x0-172xc2x0. A sample of the salt (0.2 g) was partitioned between 8% sodium bicarbonate (25 ml) and chloroform (2xc3x9725 ml). The combined extracts were dried and evaporated in vacuo to give pure free base (0.12 g). The base was dissolved in methanol (5 ml) acidified with maleic acid (0.045 g) and the salt precipitated by adding excess dry ether (80 ml) to give the title compound (0.08 g) m.p. 142-145xc2x0.
T.I.c. Silica, dichloromethane/ethanol/0.88 ammonia (100:8:1) Rf 0.3 detection u.v. and iodoplatinic acid, identical to the product from Example 7 (1,2,3,9-Tetrahydro-9-methyl-3-[(2-methyl-1H-imidazol-1-yl)methyl]-4H-carbazol-4-one). The enantiomer ratio, determined by ""H n.m.r. was 95:5. A sample of the maleate salt showed no significant optical rotation in methanol. The free base, regenerated from the maleate salt, gave [xcex1]24D+16xc2x0 (c-0.34, MeOH). Analogous processes are also described in European patent application No. 86300423.
The efficacy of compounds of formula (I) in the promotion of gastric emptying and their anti-emetic activity have been demonstrated in standard animal models as described below.
(A) Gastric Emptying
Test compound: 1,2,3,9-tetrahydro-9-methyl-3-[(2-methyl-1H-imidazol-1-yl)methyl]-4H-carbazol-4-one hydrochloride dihydrate. The effect of the test compound on gastric emptying was determined in guinea-pigs by following the progress of polystyrene-coated barium sulphate spheres (1 mm diameter) through the gut. The experimental method was based on that described by B. Costall et. al., Eur. J. Pharmacol 91, 197-205, 1983 and B. Cox et. al., Br. J. Pharmacol. 70, 104, 1980.
The spheres (approximatley 30 in number) were administered orally in 0.2 ml carboxymethylcellulose with 0.05 ml glycerine. At the same time, the test compound was administered intraperitoneally at doses of 0.001, 0.01 and 0.1 mg/kg. The control animals received saline, administered intraperitoneally, in place of the test compound. Passage of the spheres through the gut was monitored at 30-60 minute intervals over a period of 2 hours by X-ray location. The number of spheres leaving the stomach was recorded and expressed as a percentage of the total.
The results are given in Table 1 below
(B) Anti-Emesis
Test compound: 1,2,3,9-tetrahydro-9-methyl-3-[(2-methyl-1H-imidazol-1-yl)methyl]-4H-carbazol-4-one hydrochloride dihydrate.
The effect of the test compound on emesis was demonstrated in ferrets according to the general method described by Florezyk, Schurig and Bradner (Cancer Treatment Report, 1982 66(1) 187-9) and summarised below. Both the test compound and cisplatin were prepared and administered in normal saline. The dose of test compound was calculated as the free base.
a) Controlxe2x80x94without Test Compound
Emesis was induced in groups of 6 male ferrets weighing between 1.5-2 kg, by intravenous administration of cisplatin at a dose of 10 mg/kg. The onset of emesis occurred between 38 and 75 minutes after injection and over a period of 2 hours the number of vomits/retches (episodes) was in the range 30-62 (average 42xc2x15 vomits/retches per 2 h). Behavioural changes characteristic of emesis were also noted.
b) With Test Compound
The test compound was administered to groups of 6 male ferrets (1.5-2 kg) by intravenous administration at doses of 0.01, 0.1 and 1 mg/kg, immediately prior to administration of cisplatin as described above. The animals were observed for 3 hours.
The results obtained are given in Table 2 below.
The effect of the test compound on emesis was also demonstrated following intraperitoneal administration, using a similar procedure to that described above.
Thus cisplatin was administered intraperitoneally to a group of 4 male ferrets at a dose of 9 mg/kg, and the time to onset of emesis and the number of emetic episodes were recorded. In a second group of four male ferrets the test compound was administered at a dose of 1 mg/kg i.p. 30 minutes before and 1 hour after intraperitoneal administration of cisplatin. The results are given in Table 3:
The following example illustrates the preparation of a compound of formula (I). Temperatures are in xc2x0C. Where indicated, solutions were dried over Na2SO4 and solids were dried in vacuo over P2O5 at 50xc2x0 overnight. Chromatography was carried out using the technique described by W. C. Still et al (J. Org. Chem., 1978, 43, 2923-2925), on kieselgel 9385.

Abstract: wherein

Abstract: R1 represents a hydrogen atom or a C1-10 alkyl, C3-7 cycloalkyl, C3-7 cycloalkyl-(C1-4)alkyl, C3-6 alkenyl, C3-10 alkynyl, phenyl or phenyl-C1-3 alkyl group; and one of the groups represented by R2, R3 and R4 is a hydrogen atom or a C1-6 alkyl, C3-7cycloalkyl, C2-6 alkenyl or phenyl-C1-3 alkyl group and each of the other two groups, which may be the same or different, represents a hydrogen atom or a C1-6 alkyl group;

Abstract: and physiologically acceptable salts and solvates thereof, for the relief of nausea and vomiting and/or the promotion of gastric emptying and for the manufacture of a medicament for this purpose.


A protection structure for outer shell of a hub comprises: a hub and an outer shell mounted at one end of the hub, the outer shell is provided at one end close to the hub with an enlarged flange, on an outer peripheral surface of the outer shell are annularly and spaced-apart formed a plurality of splines and at least one positioning rib, at least at one side of each splines is disposed with a protecting member whose material is different from that of the outer shell. By such arrangements, the protecting member can be assembled with a sprocket to prevent the sprocket from touching the splines. Thus, damages of the outer shell of the hub are prevented.

1. Field of the Invention
The present invention relates to a hub for bicycle, and more particularly to a protection structure for outer shell of a hub.
2. Description of the Prior Art
The conventional bicycle hubs for connecting the spokes and wheel are provided at one end with an outer shell thereof. A sprocket can be mounted onto the end of the hub. Most of the outer shells sold on the market are made of aluminum alloy in order to reduce the weight of the outer shell. However, aluminum alloy is a kind of soft metal while the sprocket is made of hard metal steel for the sake of structural rigidity.
To make it easy and quick for the splines made of aluminum alloy to be engaged with the receiving hole of the sprocket made of steel, it requires a tolerance when assembling the outer shell with the sprocket. However, the tolerance will cause a few impacts of hitting to the sprocket and the outer shell of the hub when the sprocket drives the hub to rotate. As what is mentioned, the sprocket is made of hard metal while the outer shell of the hub is made of soft metal. After the sprocket drove and collided with the outer shell for a long time, the splines on the outer peripheral surface of the outer shell would be damaged and worn down easily, reducing the engagement tightness of the splines.
A solution to the above problem is to replace the outer shell of the hub. However, replacing the outer shell will cause other problems. For example, the high price of the raw material such as aluminum is increasing rapidly, resulting in a problem of high cost. Therefore, the first impact of replacing the damaged aluminum outer shell is the increased cost.
On the other hand, there are two methods to assemble the sprocket and the outer shell of the hub. The first method is to screw the outer shell to the hub, as mentioned above, so that the outer shell can be replaced separately. The second method is that the outer shell is integrally formed on the hub, leading to a result that the outer shell must be replaced together with the hub. Thus, the second method costs more expanses on the raw material than the first method indirectly.
Therefore, the present invention has arisen to mitigate and/or obviate the afore-described disadvantages.

Protection structure for outer shell of a hub


The present invention provides wall and floor coverings based on a carrier coated with one or more layers. The carrier includes a fiberglass containing mat consolidated with a binder, a non-woven made of organic synthetic fibers bonded with the fiberglass containing mat by needling. Part of the organic fibers penetrate through the fiberglass mat, and one or more layers coated on a glass fiber side of said carrier, opposite the non-woven synthetic mat.

1. Field of the Invention
This invention relates to wall and floor coverings based on a laminate carrier including a fiberglass mat and an organic synthetic non-woven, and to a method of preparing the same.
2. Description of the Related Art
Carriers composed of bonded fabrics are useful in roofing felts and insulation. They are particularly useful in wall and floor coverings of constructions such as residential and commercial structures.
A floor and wall covering is described in Patent Document WO 98/17455, wherein the covering is manufactured without the use of a carrier. A plastic material in the form of spherically shaped particles are placed on a substrate, such as a conveyor. A band conveyor made of steel is provided on which the spheres are sintered together.
Various other laminates employed as floor and wall coverings and their method of manufacturing are known in the art. For example, European Patent Document EP 0 132 325 B1 discloses a method for fixing a surface covering on a bottom covering. A glass mat is used as a carrier and it is coated with a PVC material.
Patent Document WO 97/19219 A1 discloses a floor covering based on a carrier coated on both sides. European Patent Document EP 0 899 372 A2 simply describes a coated textile glass mat.
Some of the disadvantages associated with the carrier laminates described above is the mechanical, dimensional and noise attenuation of these composites when they are used as wall or floor coverings.
To meet the requirements of the flooring and insulation industries, it is an object of the invention to provide a wall or flooring carrier laminate based on two or more layers including a fiberglass mat and an organic synthetic fibers non-woven, bound by needling.
It is another object of the present invention to provide a wall or floor covering having improved noise attenuation properties, and in particular reduced noise propagation, generated from walking a floor having such a covering.
It is a further object of the present invention to provide wall or floor coverings which are high adaptable to thermal changes and provides crack bridging which may occur. Nevertheless, these coverings provide sufficient elasticity.
It is yet another object of the present invention to provide a wall or floor covering based on a carrier having improved thermal and dimensional stability, wherein the carrier is easily reproduced and provides an increased comfort level (i.e., they are soft).
Other objects and aspects of the invention will become apparent upon review of the specification and claims appended thereto.
In accordance with a first aspect of the invention, wall and floor coverings based on a carrier coated with one or more layers is provided. The carrier includes a fiberglass containing mat consolidated with a binder, a non-woven made of organic synthetic fibers bounded with the fiberglass containing mat by needling. Part of the organic fibers penetrate through the fiberglass containing mat, and one or more layers coated on a glass fiber side of said carrier, opposite the non-woven synthetic mat.
In accordance with a second aspect of the invention, a method for manufacturing wall and floor coverings based on a carrier coated with one or more layers is provided. The process includes providing an organic synthetic fiber or chemical fiber non-woven, and a fiberglass containing mat pre-consolidated with a binder. The mat and the non-woven are bounded by needling such that a portion of the organic synthetic fibers penetrate through said fiberglass containing mat and optionally a part of the fibers emerges from the side of synthetic fiber non-woven and lies adjacent thereto. One or more layers are coated on the glass fiber side of the bounded carrier opposite the non-woven organic mat.
The invention will now be described with reference to the exemplary embodiments thereof. In an exemplary embodiment of the invention, wall and floor coverings based on a carrier coated with one or more layers. The carrier includes a fiberglass containing mat and an organic synthetic fibers non-woven bound by needling in a manner where part of the synthetic fibers may extend through the entire fiberglass mat, and preferably a part of the organic fiber lie adjacent to the side opposed to the non-woven organic non-woven. The laminate (e.g., composite) includes one or more layers coated on the same glass fiber side, opposite the non-woven.
The synthetic fibers can be staple fiber, but preferably filamentous fibers. These filamentous fibers are also known to those skilled in the art as xe2x80x9cendlessxe2x80x9d fibers. The fibers are preferably organic synthetic fibers, such as polyester, polypropylene, polyamide or any other suitable chemical or synthetic fibers. Bico fibers can also be utilized.
The synthetic fibers non-woven can be pre-consolidated before bonding with the fiberglass mat by hydrodynamically, mechanically or thermal means. In addition, thermal fixation may be performed. Pre-consolidation can be also performed by a combination of these techniques.
The fiberglass mat is produced according to either the a so-called wet, or dry method, wherein fibers of E, C class, mixture thereof and ECR glass are pre-consolidated through the employment of preferably a water insoluble binder. Suitable binders include acrylate copolymerized with vinyl acetate, styrene, etc. Other suitable binders include acrylic, urea-formaldehyde or melamine formaldehyde, melamine and urea resins. The diameter of the glass fibers is about 8 to 16 xcexcm, and preferably about 10 to 13 xcexcm. The length of the fibers is about 8 to 32 xcexcm. The weight of the glass mat produced is about 30 to 100 g/m2, and preferably about 40 to 70 g/m2. It will readily be recognized by the skilled artisan that up to 40 percent of the glass fibers can be substituted by other fibers. In particular, cellulose based fibers, polyacrylonitrile, polyester, polyamide, etc.
The organic synthetic non-woven of staple fiber can be made on a carding machine, which is well known in the art. Preferably, the filamentous non-wovens are made by the spunbond method described in DE OS 24 60 755 and herein incorporated by reference in its entirety. Several spinning beams or the like are utilized to manufacture the so-called curtains which are laid down on a moving conveyor in a randomly distributed arrangement.
The formed synthetic fiber mat is thermally fixed prior to bonding with the fiberglass mat by either calendering or through the utilization of a hot-air oven. Optionally, the mat is passed through an infrared path where the mat is exposed to radiation. In this manner, the thermal shrinking of the non-woven upon formation into a carrier laminate is removed, thereby avoiding a wave formation due to differential shrinkage phenomenon as a result of a subsequent thermal treatment (i.e., coating of the carrier laminate).
The synthetic fibers may be shrunk separately, and therefore before a non-woven is produced using these shrunken fibers. Preferably, the organic fibers are shrunk when they are present in the form of a non-woven or in the form of corresponding layers. The shrinking may take place before a mechanical or hydro-dynamical pre-consolidation. Optionally, the non-woven is shrunk after a corresponding pre-consolidation. The shrinking is preferably performed by heating in an oven at temperatures of about 140 to 220xc2x0 C.
Upon obtaining the mats, the organic synthetic fibers non-woven is laid on the pre-consolidated fiberglass containing mat where they are mechanically needled together. Needling can be performed such that the needles penetrate the organic fiber non-woven and press part of the organic fibers through the fiberglass mat in a manner where part of the organic fibers emerge from the fiberglass mat, and optionally are adjacent thereto.
Preferably, the mats are bounded to each other by water beam needling (i.e., hydrodynamically). The needling takes place from the side of the non-woven synthetic, and with an increased water beam pressure. Preferably, the water beam pressure is in the range of about 100 to 400 bar, and even more preferably about 200 to 400 bar. Thus, a part of the fibers or filaments are pushed through the glass mats, while reducing the damage to glass and synthetic fibers. This process is further described in detail in co-pending application Ser. No. 09/619,528, filed Jul. 19, 2000, now U.S. Pat. No. 6,412,154, and hereby incorporated by reference in its entirety.
The two layer system needled together can subsequently be provided with a binder, in order to achieve a final consolidation. In this exemplary embodiment very small amounts of binder are employed. It is preferred that the binder is in a range of about 0 to 25 weight percent, and even more preferably 0 to 10 weight percent. The binder can be selected from the group including pure acrylates, copolymers of styrene, butadiene, acrylates and mixtures of duroplastic binders such as urea and melamine resins.
Thereafter, the formed carrier laminate is manufactured with one or more polymeric coatings applied to the fiberglass mat, away from the synthetic non-woven. Polyvinyl-chloride can be employed as a preferred coating. However, other polymers such as acrylates in the form of a paste, polyolefins contained in different kinds of mixtures and reproductive raw materials like natural resins can be employed. Coating compositions are further described in European Patent Document EP 0 132 325 B1 and Patent Document WO 97/19 219 which are hereby incorporated by reference in their entirety.
The coating may be placed through several techniques, such as the so-called xe2x80x9cspread coatingxe2x80x9d (barber""s knife) or the xe2x80x9ccalenderxe2x80x9d technique. In both techniques, a viscous polyvinyl-chloride (PVC) is pressed into the glass substrate. The coating temperature is dependent on the required viscosity for PVC. Typically a temperature of about 185xc2x0 C. is sufficient in most applications.
The temperature required and the choice of coating materials also depends on the type of synthetic fibers. For example, polypropylene non-wovens require a temperature lower than 185xc2x0 C., while polyester non-wovens can be heated to this temperature.
In accordance with the exemplified embodiment, several coating layers of different physical characteristics, and in particular hardness, can be placed on the carrier laminate. The coatings can in turn be layers, having a pattern or a colored designs. In addition, the outer layer can include embossing on the outer surface, to prevent slipping or other accidents that may occur. Naturally, the bond between the coatings and carrier is particularly improved where the synthetic fibers penetrate through the fiberglass mat and are adjacent to the underside of the fiberglass mat which is coated on a side away from the non-woven. The fibers provide an especially improved bond of the covering on the laminated material.
It will readily be recognized by those skilled in the art that modifications can be performed on the laminate to vary the physical and/or mechanical properties (e.g., hardness) of the wall and floor coverings. For example, the thickness of the floor and wall coverings can be varied by varying the thickness of the individual layers (i.e., the organic fibers non-woven and the fiberglass mat). Further, it is possible to vary the thickness of the final product depending on the application in which it is to be used, by varying the number of coatings and their layers.
In another exemplary embodiment, the wall and floor coverings are manufactured as described-above, no final consolidation with a binder is performed. This process is further described in co-pending application Ser. No. 09/619,535, and is incorporated herein by reference in its entirety.
Thus, in accordance with the invention, wall and floor coverings having improved properties may be manufactured in an quick and facile manner, which is economically advantageous. For instance, the impact noise attenuation (e.g. reduced noise propagation from walking a floor) having such a covering and the bridging of cracks are excellent. The materials may adapt well to changes of the bottom floor or the wall. For example, thermal expansion of floors and crack formation due to stresses are compensated for, so that fissures do not extend to the surface of the covering.
The non-woven layer of synthetic organic fibers provides noise attenuation and improved elasticity. On the one hand, noise propagation from the room in which the noise is generated is reduced, and on the other hand, noise generated in the other rooms are muted in the rooms equipped with floor and wall covering prepared in accordance with the invention. Accordingly, improved insulation within an apartment or apartment building can be provided.
Furthermore, the layered laminate carrier manufactured in accordance with the invention, reduces the amount of glass fragments and dust produced, thus avoiding injury to the operator and reducing harm to the environment.
The formed laminate""s thickness can be adjusted through the hydrodynamic needling method, or optionally through a secondary operation such as compression performed by a calender, a fabric-belt or laminate calender.
Furthermore, the product manufactured by the process outlined above provides dimensional stability and eliminates neck-down during coating or saturation PVC or other coating materials.

Method of making wall and floor coverings


Adhesives comprising:

1. Field of the Invention
The present invention relates to adhesives comprising an aqueous polymer dispersion obtainable by free-radical copolymerization in the presence of at least one protective colloid based on a prepolymer, to processes for their preparation and to their use.
2. Description of the Background
Packaging materials made from paper, board or card, such as folding boxes, are produced, and paper labels attached to nonabsorbent substrates, especially to hollow structures made from glass, plastic or metal, such as bottles or glasses, using adhesives which are referred to in general as packaging adhesives. Systems which are widespread as packaging adhesives are those comprising a polymer dispersion or a blend of a polymer dispersion with other active adhesive constituents.
Kleb- und Dichtstoffe, Vol. 40, 6/96, p. 22 f. describes, in general terms, dispersion adhesives in the paper and packaging industry. Accordingly, monomers considered for preparing the disperse phase which forms the adhesive substance are, for example, vinyl acetate, ethylene, vinyl propionate, acrylates, and dibutyl maleate. In addition to the chemical structure of the polymer dispersion and, in particular, the particle size distribution, the nature and amount of the emulsifiers and protective colloids have a decisive influence on the adhesive properties. Since the components used to stabilize the polymer dispersion are also incorporated into the adhesive film, they influence the properties of this film, for example its water resistance. A further important property of the resulting films, especially when the adhesive is used in the application of transparent labels such as printed polymer films, for example, is its transparency. Below a temperaturexe2x80x94the white point or minimum film-forming temperaturexe2x80x94which is characteristic for every polymer dispersion white layers are obtained instead of transparent films, with film labels losing their transparency especially at the unprinted areas and the visual color saturation of the printed image on the label suffering an overall loss in depth and brilliance.
The adhesives systems employed for the wet labeling of bottles are predominantly those based on an acrylate dispersion which is used either alone or as a blend with natural substances of high viscosity, such as starch or casein. A disadvantage of the known packaging adhesives based on acrylate dispersions is that these dispersions generally form films which exhibit marked clouding.
An essential requirement for an adhesive system to be used for the labeling of hollow articles is the formation of a film with high adhesion and low cohesion. For optimum deployment on the customary machines for the wet labeling of bottles it is necessary for the adhesive used to have a high viscosity at low shear rates, for example a viscosity in a range from about 2000 to 10,000 mPaxc2x7s at 25 sxe2x88x921.
Particular requirements are imposed, furthermore, on adhesives to be used for the production or labeling of packaging which comes into contact with foods. Important properties then, in addition to those mentioned above, are the toxicological acceptability of the adhesive and the exclusion of factors which impair taste and odor. In addition to the toxicological aspects regarding the foods to be packaged, further particular requirements are imposed on the ingredients of the dispersions to be used in packaging adhesives in respect of any possible irritation to, and/or harm to the health of, the personnel entrusted with processing. For instance, some dispersions employed for the preparation of adhesives include butenol as polymerization regulator, which is not entirely acceptable from a toxicological standpoint.
It is an object of the present invention to provide new adhesives suitable for the production and labeling of packaging. As well as good performance properties, such as high tack, low cohesion and high viscosity at low shear rates, these adhesives should in particular form a clear, transparent film in order to avoid the abovementioned disadvantages in connection with wet labeling using transparent films.
Furthermore, the dispersions employed.should as far as possible include no components regarded as toxicologically unacceptable.
We have found that this object is achieved, surprisingly, if an aqueous polymer dispersion obtainable by free-radical copolymerization in the presence of a particular protective colloid, based on a prepolymer, is employed in adhesives.
The invention thus provides an adhesive comprising:
a) from 5.0 to 95.0% by weight of an adhesive dispersion having a viscosity in the range from 2000 to 10,000 mPaxc2x7s, which comprises
a1) an aqueous polymer dispersion which is obtainable by free-radical polymerization of a mixture M which comprises at least one ethylenically unsaturated monomer A to give a polymer P in the presence of at least one protective colloid based on a water-soluble prepolymer which comprises at least one water-soluble monomer B, and further additives if desired,
a2) if desired, a base selected from the group consisting of alkali metal hydroxides, ammonia and volatile organic amines,
a3) if desired, a completely water-miscible organic solvent,
and, if desired, further additives;
b) from 0 to 90.0% by weight of a polysaccharide and/or a protein and/or a protein degradation product;
c) from 0 to 95.0% by weight of at least one filler;
d) from 0 to 10.0% by weight of at least one emulsifier;
e) from 0 to 30.0% by weight of further additives;
f) water to 100% by weight.
a1):
The monomer mixture M used to prepared the polymers P contains from 50 to 100% by weight, preferably 60.to 99.9% by weight, of at least one free-radically polymerizable, ethylenically unsaturated monomer A (principal monomer) and from 0 to 50% by weight, if desired from 0.1 to 40% by weight, of at least one comonomer C and also, depending on the polymerization process, if desired, at least one water-soluble monomer B in the amounts described below.
Suitable monomers A are esters of xcex1,xcex2-monoethylenically. unsaturated C3-C6 mono- and dicarboxylic acids with alkanols having preferably 1 to 12 carbons, particularly preferably 1 to 8 carbons and, in particular, 1 to 4 carbons, for example esters of acrylic and/or methacrylic acid with methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and 2-ethylhexanol, esters of vinyl alcohol with C1-C20 monocarboxylic acids, for example vinyl formate, acetate, propionate, n-butyrate, laurate and stearate, and vinyl esters of highly branched, saturated monocarboxylic acids having C9, C10 and C11 side chains (Versatic acids), vinylaromatic compounds, such as styrene, xcex1-methylstyrene, p-methylstyrene, xcex1-n-butylstyrene, p-n-butylstyrene, p-n-decylstyrene, o-chlorostyrene or vinyltoluene, and mixtures thereof.
Suitable comonomers C are, for example, vinyl halides and vinylidene halides, for example vinyl chloride and vinylidene chloride, xcex1,xcex2-ethylenically unsaturated nitriles, for example acrylonitrile and methacrylonitrile, C2-C6 monoolefins, for example ethylene and propylene, and nonaromatic hydrocarbons having 2 to 8 carbons and at, least 2 conjugated olefinic double bonds, for example butadiene, isoprene and chloroprene, and also mixtures thereof.
Further suitable comonomers C are crosslinking monomers, which in addition to their ethylenically unsaturated double bond have an epoxy, hydroxyl, N-methylol or carbonyl function or two nonconjugated, ethylenically unsaturated double bonds. The monomer mixture M can contain from 0 to 40% by weight, preferably from 0 to 20% by weight and, with particular preference, from 0.2 to 15% by weight of these crosslinking monomers. The crosslinking reaction preferably takes place not until during the drying of the polymers, and can be accelerated by heat treatment and, if desired, by adding catalysts, for example proton donors, such as maleic acid, diammonium hydrogenphosphate or ammonium nitrate.
Examples of crosslinking monomers C are the esters of xcex1,xcex2-unsaturated carboxylic acids with diols, for example hydroxyalkyl acrylates and hydroxyalkyl methacrylates, N-hydroxyalkylated amides of xcex1,xcex2-unsaturated carboxylic acids, for example N-hydroxyalkylated acrylamides and methacrylamides, such as N-methylolacrylamide and N-methylolmethacrylamide, and also monomers having at least two vinyls, at least two vinylidenes or at least two alkenyls. Examples of these include alkylene glycol diacrylates and alkylene glycol dimethacrylates, for example ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate or methylbisacrylamide.
Other crosslinking-monomers C are acrylamidoglycolic acid and methacrylamidoglycolic acid and their ethers, esters or ether esters with alcohols, such as alkanols, having up to 12 carbons, examples being acrylamidomethoxyacetic acid, methyl acrylamidohydroxyacetate, methyl acrylamidomethoxyacetate, ethacrylamidomethoxyacetic acid, methyl ethacrylamidohydroxyacetate, methyl ethacrylamidomethoxyacetate, and the corresponding butyl and butoxy derivatives, butyl acrylamidobutoxyacetate and butyl ethacrylamidobutoxyacetate.
Further crosslinking monomers C are olefinically unsaturated ketones or aldehydes. Suitable copolymerizable olefinically nsaturated ketones or aldehydes are monomers having at least one aldo or keto group and a polymerizable double bond. Of particular interest are acrolein, methacrolein, diacetoneacrylamide, formylstyrene, vinyl alkyl ketones having preferably 4 to 7 carbons, such as in particular vinyl methyl ketone, vinyl ethyl ketone and vinyl isbbutyl ketone, and/or (meth)acryloyloxyalkylpropanals of the formula (I)
where R1 is hydrogen or methyl, R2 is hydrogen or C1-C3-alkyl, R3 is C1-C3-alkyl and R4 is C1-C4-alkyl. Such (meth)acryloyloxyalkylpropanals can be prepared by the method described in DE-A-27 22 097 by esterifying xcex2-hydroxyalkylpropanals of the formula (II)
where R2, R3 and R4 are as defined above with acrylic or methacrylic acid in the presence of diluents and small amounts of sulfonic acids and mineral acids. Other suitable keto-carrying monomers are diacetone acrylate, diacetone methacrylate, acetonyl acrylate, 2-hydroxypropyl acrylate acetylacetate and 1,4-butanediol acrylate acetylacetate. The amount of the aldo- or keto-containing copolymerized comonomers is generally from about 0.5 to 10% by weight, preferably from 1 to 5% by weight, based on the monomer amount of the copolymer.
The monomer A is preferably selected from the three following classes in the preferred proportions given above:
Class I
Esters of acrylic and/or methacrylic acid with C1-C12-alkanols and/or styrene;
Class II
Styrene and/or conjugated dienes, preferably 1,3-butadiene;
Class III
Vinyl esters and/or aliphatic hydrocarbons having 1 or 2 double bonds and 2 to 8 carbons and/or esters of acrylic and/or of methacrylic acid.
Particular preference is given to mixtures M with monomers of Class I. In a particularly preferred embodiment the mixture M then comprises, as ethylenically unsaturated monomers A, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, or mixtures thereof. The latter include, in particular, mixtures comprising from 50 to 90% by weight of methyl acrylate, from 10 to 40% by weight of n-butyl acrylate and also, if desired, styrene and/or vinyl acetate.
The free-radical homo- or copolymerization of the mixture M takes place in the presence of a prepolymer which is employed as protective colloid. This prepolymer is preferably prepared, as described below, in situ at the beginning of the polymerization of the mixture M. If desired, however, it is also possible to employ a separately prepared prepolymer.
The prepolymer preferably contains, in copolymerized form, from 0.2 to 5.0% by weight, more preferably from 0.3 to 1.5% by weight and, in particular, from 0.5 to 1.1% by weight of at least one water-soluble monomer B which contains acid groups, the amounts of the monomer B being based on the overall amount of the monomers of mixture M and of the prepolymer. The prepolymer also generally contains from about 3.5 to 6.5% by weight, preferably from 4.0 to 6.0% by weight, of additional monomers selected from the aforementioned monomers A and/or C of the mixture M, likewise based on the overall amount of the monomers of mixture M and of the prepolymer that are to be polymerized, in copolymerized form. The K value of the prepolymer, determined by the method of H. Fikentscher, Cellulose Chemie 13 (1932), p. 58 ff., is not more than 80, preferably not more than 60 and, in particular, not more than 40.
Examples of suitable monomers B are acrylamide and methacrylamide and their N-alkylated derivatives, xcex1,xcex2-monoethylenically nsaturated C3-C6 mono- and dicarboxylic acids, and the anhydrides and monoesters thereof.
Preferred monomers B are monomers containing acid groups, especially acrylic, methacrylic, maleic, fumaric, itaconic and rotonic acid, maleic anhydride, monoesters of maleic and/or fumaric acid with C1-C10-alkanols, vinylsulfonic acids, and their water-soluble salts and/or mixtures thereof. Particularly preferred monomers B are acrylic acid, methacrylic acid or a mixture thereof.
According to one specific embodiment the polymer P is a terpolymer of acrylic acid, methyl acrylate and n-butyl acrylate.
In a preferred embodiment the solubility of the overall amount of the monomers A, B and C in 100 g of water at 25xc2x0 is chosen such that at least 50% by weight of the monomers have a solubility which is within a range from 1.5 g to 10 g. Preferably at least 50% by weight, in particular at least 70% by weight, of the monomers have a solubility in the range from 4.0 to 10.0 g. according to another preferred embodiment the solubility of the overall amount of the monomers A, B and C in 100 g of water at 25xc2x0 is chosen so that not more than 50% by weight, preferably from 20 to 30% by weight, of the monomers have a solubility of not more than 0.2 g.
The glass transition temperature of the polymer P is preferably xe2x89xa615xc2x0 C., especially xe2x89xa610xc2x0 C. It is preferably in a range from +5xc2x0 C. to xe2x88x925xc2x0 C. The glass transition temperature of the polymer can be determined by the method of differential thermalanalysis (DTA) or differential scanning calorimetry (DSC, as described in ASTM 3418/82).
The protective colloids employed in accordance with the invention can be employed either as individual dispersants or else in a mixture with other surface-active substances as additives. These can either be added to the novel adhesives, in component a1), or, if desired, added in the formulation of the adhesives, as component d).
Further suitable surface-active additives in a1) and/or d) are the emulsifiers and protective colloids which are commonly employed as dispersants in connection with emulsion polymerization, and as are described, for example, in Houben-weyl, Methoden der organischen Chemie, Volume XIV/1, Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 411-420. Suitable additional protective colloids are, for example, polyvinyl alcohols and partially hydrolyzed polyvinyl acetates, polyacrylates, polyvinylpyrrolidone, cellulose and cellulose derivatives, for example methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, starch and starch derivatives, for example cyanoalkyl ether starch, hydroxyalkyl ether starch, carboxymethylstarch, etc. Suitable emulsifiers include anionic, cationic and nonionic emulsifiers.
As surface-active substances it is preferred to employ emulsifiers, whose relative molecular weights, unlike those of the protective colloids, are usually below 3500 daltons.
Nonionic emulsifiers which can be used are araliphatic or aliphatic nonionic emulsifiers, for example ethoxylated mono-, di- and trialkylphenols (EO units: 3 to 50, alkyl: C4-C10), ethoxylates of long-chain alcohols (EO units: 3 to 50, alkyl: C8-C36) and polyethylene oxide/polypropylene oxide block copolymers. Preference is given to ethoxylates of long-chain alkanols (alkyl: C10-C22, mean degree of ethoxylation from 10 to 50) and, of these, particular preference is given to those having a linear C12-C8-alkyl radical and a mean degree of ethoxylation of from 10 to 50, and also ethoxylated monoalkylphenols.
Examples of suitable anionic emulsifiers are alkali metal salts and ammonium, salts of alkyl sulfates (alkyl: C8-C22), of sulfuric monoesters of ethoxylated alkanols (EO units: 2 to 50, alkyl: C12-C18) and of ethoxylated alkylphenols (EO units: 3 to 50, alkyl: C4-C9), of alkylsulfonic acids (alkyl: C12-C18) and of alkylarylsulfonic acids (alkyl: C9-C18). Other suitable emulsifiers are given in Houben-Weyl, loc. cit. pp. 192-208. Likewise suitable as anionic emulsifiers are bis(phenylsulfonic acid) ethers and/or the alkali metal or ammonium salts thereof which carry a C4-C24-alkyl on one or both aromatic rings. These compounds are generally known, for example from U.S. Pat. No. 4,269,749, and are obtainable commercially, for example as Dowfax(copyright) 2A1 (Dow Chemical Company).
Suitable cationic emulsifiers are preferably quaternary ammonium halides, for example trimethylcetylammonium chloride, methyltrioctylammonium chloride, benzyltriethylammonium chloride or quaternary compounds of Nxe2x80x94C6-C20-alkylpyridines, -morpholines or -imidazoles, for example N-laurylpyridinium chloride.
According to one appropriate embodiment the emulsifier employed is an xcex1-sulfo-xcfx89-(dodecyloxy)poly(oxyethyl)ammonium salt, for example C12H25(EO)30 SO2NH4, obtainable as Disponil(copyright) grades from Henkel KGaA.
If one of the abovementioned emulsifiers is used it should be selected in accordance with its compatibility with the prepolymer. The amount of emulsifier is generally from about 0.01 to 10% by weight, based on the amount of polymerized monomers.
The polymerization of the mixture M to form a polymer P, and/or the preparation of the prepolymer, can preferably be carried out in the presence of a starch degradation product as protective colloid. Examples of suitable starch degradation products are those having a weight-average molecular weight of 2500 to 25,000. The starch degradation ;products are obtainable from starch by hydrolysis in the aqueous phase or by thermal degradation (roast dextrins). Starch degradation products obtainable by hydrolysis in the aqueous phase, in contrast to the roast dextrins, are usually referred to as sugared starches and are obtainable commercially (for example the C*PUR products 01906, 01908, 01910, 01912, 01915, 01921, 01924, 01932 or 01934 from Cerestar Deutschland GmbH, Krefeld).
The preparation of sugared starches is generally known and is described, inter alia, in Gxc3xcnther Tegge, Stxc3xa4rke und Stxc3xa4rkederivate, Behr""s Verlag, Hamburg 1984, p. 173 and p. 220 ff., and also in EP-A 441 197. The sugared starches to be used in accordance with the invention are preferably those whose weight-average molecular weight Mw is in the range from 4000 to 16,000, particularly preferably in the range from 6500 to 13,000.
Component a1) may additionally comprise at least one seed latex which can be prepared in situ or separately beforehand. The seed latex preferably employed is a previously prepared, fine polystyrene dispersion having a solids content in the range from about 30 to about 35% by weight.
The free-radical copolymerization of the mixture M preferably takes place in the presence of a polymerization regulator as additive a1). In this context, in preparing the novel adhesive dispersions a), the use of butenol, which is regarded as not entirely acceptable from a toxicological standpoint, as polymerization regulatoris avoided. The monomer mixture M is preferably polymerized in the presence of mercaptans as polymerization regulators. In this case t-dodecyl mercaptan is preferably employed as polymerization regulator. The amount will then be in general from about 0.01 to 5% by weight, based on the overall amount of the mixture M.
Further customary additives can also be added to the adhesive dispersions a), in the initial charge, in one of the feed streams or after the polymerization has been concluded. Thus it is possible, if desired, to adjust the pH of the dispersion using acids or bases, for example alkali metal hydroxides, carbonates, phosphates or acetates, ammonia, HCl, etc. The prepolymer based on the monomers B containing acid groups is preferably employed in at least partially neutralized form, so that some of component a2) described below is added actually during the preparation of the prepolymer. Other suitable additives are reducing agents and bleaches, for example the alkali metal salts of hydroxymethanesulfinic acid (for example Rongalit(copyright) C from BASF AG).
The polymers P are generally prepared as aqueous dispersions having overall solids contents of from 20 to 70% by weight, preferably from 30 to 60% by weight. Alternatively, the polymers can be obtained as powders, for example by spray drying, and can be redispersed.
To formulate the novel adhesive dispersions a), the pH of the aqueous polymer dispersions obtained by free-radical emulsion polymerization in the presence of one of the abovementioned prepolymers can be adjusted by adding a base, for example an alkali metal hydroxide, such as sodium hydroxide or potassium hydroxide, ammonia, a volatile organic amine, preferably mono-, di- or triethanolamine or a mono-, di- or trialkylamine such as ethylamine, dimethylamine, trimethylamine or triethylamine, and cyclic amines, such as pyrrolidine, piperidine, piperazine or morpholine, or mixtures thereof. For neutralization it is preferred to employ sodium hydroxide or ammonia. The pH of the resulting adhesive dispersions a) is from about 6 to 8, preferably about 7.
The adhesive dispersions a) may if desired include a water-miscible solvent. The proportion of organic solvents in the case of the novel adhesives is preferably low and is not more than about 10% by weight based on the overall weight of component a). Examples of suitable water-miscible organic solvents are C1-C4 alcohols, such as methanol, ethanol, n-propanol, isopropanol and n-butanol, or ketones, such as methyl ethyl ketone or acetone. Isopropanol is preferably used.
If desired the adhesive dispersion a) can have further water added to it in addition to the amounts of water present in components a) to a3).
The viscosity of the adhesive dispersion a) is preferably from about 3000 to 7000 mPaxc2x7s.
According to one possible process variant the abovementioned adhesive dispersions a) are not formulated separately; instead, the above-described components a1) to a3) are formulated in one step with components b), c) and d) to form the novel adhesive.
In the novel process it is possible as component b) to employ generally customary polysaccharides. Examples of these include cellulose, cellulose degradation products, starches, for example natural starches from the group consisting of cornstarch, potato starch, wheat starch, rice starch, tapioca starch, sago starch, sorghum starch, cassava starch, pea starch and mixtures of the natural starches stated. If starches with a defined amylopectin content are desired, then these can be obtained, for example, by starch fractionation of customary natural starches or from those plants which produce virtually pure amylopectin starch. Suitable starches and starch derivatives are described in Gxc3xcnther Tegge, Stxc3xa4rke und Stxc3xa4rkederivate, Hamburg, Behr""s-Verlag 1984. In addition to the natural starches, hydrolytically or enzymatically degraded starches are also suitable, for example dextrins, such as white or yellow dextrins and maltodextrins, or oxidized starches, for example dialdehyde starch. Chemically modified starches, for example starches esterified with organic or inorganic acids, in particular phosphated and acetylated starches, and starches etherified with organic halogen compounds, epoxides or sulfates, are also suitable. Starches and processes for their degradation and their chemical modification are described in Ullmanns Encyclopedia of Industrial Chemistry, 5th edition, Volume A25, p. 2 f., which is hereby incorporated by reference.
Further suitable components b) are proteins and/or protein degradation products. Suitable starting proteins are obtained, for example, from animal or vegetable sources. They include, for example, animal proteins, such as gelatin, casein or fish proteins, which are obtained, for example, from hair, horns, hooves, claws, nails, bones or milk by customary techniques. The vegetable proteins include, for example, proteins from rice, wheat, potatoes or oilseeds, which are likewise obtained in a customary manner. To prepare protein degradation products, these starting proteins can be cleaved open with the aid of acids, alkalis or enzymes to give oligopeptides and polypeptides having a lower molecular weight than the starting proteins. To prepare the novel adhesives it is preferred to employ casein. This can be obtained, for example, as casein ST 50 F from Txc3xcrmerleim.
The novel adhesives may additionally comprise at least one filler c). Examples of suitable fillers are chalk, calcite, dolomite, quartz flour, titanium dioxide, aluminum silicate, talc, mica, kieselguhr, gypsum, magnesite, slate flour, barium sulfate, hard polymers or mixtures thereof.
Component c) can be present in the novel adhesives preferably in an amount of from about 40 to 80% by weight.
The novel adhesives can additionally comprise at least one emulsifier which, as mentioned above, can be added to component a) during the actual polymerization of the mixture M. Suitable emulsifiers d) are those mentioned above.
Examples of additives e) which are suitable in addition are preservatives, dyes, pigments, pigment dispersants, plasticizers, thickeners, phenol-formaldehyde resins, melamine resins, (thio)urea, borax, isocyanates, epoxides, natural latex, other polymer dispersions, for example dispersions based on esters of vinyl alcohol with monocarboxylic acids, such as vinyl formate, vinyl acetate, vinyl propionate, etc., and also polyvinyl alcohol.
If desired, an additional amount of water may also be added to the novel adhesives.
The invention additionally provides a process for preparing the above-described adhesives, which comprises
i) reacting, in a reactor, at least one water-soluble monomer B which preferably contains acid groups, with or without any further monomers selected from the aforementioned monomers A and/or C, in the presence or absence of components a2) and/or a3) and/or of further additives, to give a prepolymer,
ii) reacting the mixture M in the presence of the prepolymer, and in the presence or absence of components a2) and/or a3) and/or of further additives, to give a polymer P,
iii) and, if desired, adding at least one further component selected from a2), a3), b), c), d), e), f) and mixtures thereof.
Stage i)
The prepolymer which in the course of polymerization of the mixture M serves as protective colloid is preferably prepared in situ, prior to the polymerization of the mixture M, by the technique of free-radical aqueous emulsion polymerization, generally at from about 30 to 120xc2x0 C. and preferably from about 40 to 95xc2x0 C. The polymerization medium can consist either only of water or of mixtures of water with water-miscible liquids such as methanol, for example. Preferably, just water is used. The emulsion polymerization can be carried out either as a batch process or in the form of a feed process, including stage and gradient procedures. Preference is given to the latter feed techniques, in which first the prepolymer is reacted and then the mixture M without isolating the prepolymer in between. A preferred procedure is initially to charge to the reactor a portion of the polymerization medium, which may include a portion of the polymerization batch, to heat this initial charge to the polymerization temperature, to carry out an initial polymerization if desired, with the formation of a seed latex, and then to supply to the polymerization zone the remainder of the batch, usually by way of two or more spatially separate feed streams of which one or more may contain the monomers in pure form or in emulsified form, these feed streams being added continuously, in stages or with the superimposition of a concentration gradient and while maintaining the polymerization.
In accordance with one appropriate embodiment of the novel process the reaction in step i) takes place in the presence of a seed latex. These seed latices can be prepared in situ by introducing an initial charge of appropriate monomers and subjecting them to partial polymerization. It is preferred to employ a prefabricated seed latex, for example the fine polystyrene dispersions indicated earlier as being suitable, which can be added to one of the feed streams or, preferably, to the initial charge.
According to another suitable embodiment of the novel process the reaction in step i) for preparing the prepolymer takes place in the presence of an additional protective colloid. In this case it is preferred to employ the protective colloids based on starch degradation products that were mentioned above as being suitable, and which are preferably added to the initial charge.
The water-soluble monomers B containing acid groups which are employed to prepare the prepolymer are preferably used in partially neutralized form or are partially neutralized in the course of polymerization. According to another preferred embodiment of the novel process, therefore, a portion of the above-described component a1) is included in stage i) in the initial charge or is added to one of the feeds, said component a1) preferably being ammonia. Then the weight ratio of monomer B to ammonia is in general from about 3.5:1 to 7:1, preferably from about 4:1 to 6.5:1, this weight ratio not including the amount of component a2) which is additionally required for adjusting the pH. According to another preferred embodiment, the polymerization regulator described above as component a1) is included in the polymerization batch in step i). In this case, the polymerization regulator can either be included in the initial charge or added to one of the feed streams.
To prepare the prepolymers which are employed in accordance with the invention as protective colloid it is possible to add a portion of the abovementioned monomers A and/or C to the polymerization batch in step i); in that case, these monomers are copolymerized with the water-soluble monomer B which contains acid groups. In step i) it is preferred to react not more than 25% by weight, preferably not more than 10% by weight and, in particular, not more than 6% by weight of the total amount of monomers A and/or B and/or C which are to be polymerized.
Polymerization initiators which can be employed to polymerize the prepolymer and/or the mixture M in steps i) and/or ii) are all compounds which dissociate into free radicals under the polymerization conditions, examples being peroxides, hydroperoxides, hydrogen peroxide, persulfates, azo compounds and the redox catalysts. Preference is given to the use of water-soluble initiators. In some cases it is advantageous to use mixtures of different polymerization initiators, for example mixtures of hydrogen peroxide and sodium or potassium peroxodisulfate. Mixtures of hydrogen peroxide and sodium peroxodisulfate can be used in any desired proportions. Organic peroxides which are likewise suitable as initiators are described in EP-A-0 536 597. The polymerization initiators indicated are employed in customary amounts, for example from 0.01 to 5% by weight, preferably from 0.1 to 2.0% by weight, based on the monomers to be polymerized.
Further suitable initiators are redox catalysts. As oxidizing component, the redox catalysts include at least one of the abovementioned per compounds, and as reducing component they include, for example, ascorbic acid, glucose, sorbose, ammonium or alkali metal hydrogensulfite, sulfite, thiosulfate, hyposulfite, pyrosulfite or sulfide, metal salts such as iron(II) ions or silver ions, or sodium hydroxymethylsulfoxylate.
In general the amount of free-radical initiator systems employed, based on the overall amount of the monomers A and/or B and/or C which are to be polymerized, is from 0.1 to 2% by weight. Particular preference is given to the usexe2x80x94alone or as a constituent of combined systemsxe2x80x94of ammonium and/or alkali metal peroxodisulfates as initiators. Particular preference is given to the use of sodium peroxodisulfate.
The free-radical initiator system can either be included entirely in the initial charge to the polymerization vessel or else can be added continuously or in stages, at the rate at which it is consumed in the course of the free-radical aqueous emulsion polymerization in stages i) and/or ii). In each specific case this will depend, as is known, both on the chemical nature of the initiator system and on the polymerization temperature. The initiator system is preferably supplied to the polymerization zone at the rate at which it is consumed.
The free-radical aqueous emulsion polymerization takes place in stages i) and/or ii) in general at atmospheric pressure, although it may also take place at superatmospheric or subatmospheric pressure.
Step ii)
The homo- and/or copolymerization of the mixture M for preparing the aqueous polymer dispersions P by the process of free-radical aqueous emulsion polymerization in the presence of the above-described prepolymers as protective colloids takes place in a customary manner. The polymerization conditions essentially correspond to those for the preparation of the prepolymer. If desired, however, it is also possible to establish polymerization conditions which deviate from those used before. Such conditions include, for example, the choice of a different polymerization temperature, the addition of water-miscible liquids to the polymerization medium, or the use of other of the abovementioned additives. The reaction in step ii) preferably takes place at a pH in the range from about 4 to 6, preferably from about 4.9 to 5.7. The addition of the monomers and/or of further additives can again be made by way of two or more spatially separate feed streams, in pure or emulsified form, continuously, in stages or with the superimposition of a concentration gradient, while maintaining the polymerization.
The reactions in steps i) and ii) can be carried out either separately, in other words in two or more stages, or else in a single stage in a gradient procedure. According to one preferred embodiment the reactions of stages i) and ii) take place as a two-stage process. In this case, in general, at least 60% by weight, preferably at least 70% by weight and in particular, at least 90% by weight of the total amount of the monomers B is supplied to the reaction zone in the course of 35% of the total polymerization time for preparing the prepolymer and the polymer P.
Step iii)
The formulations of the novel adhesives, especially the mixing of component a) with the other components, can be carried out using the customary apparatus and by the customary methods. The former include, for example, customary stirring devices, which are known to the skilled worker.
The novel adhesive dispersions and the adhesives formulated from them are notable for high viscosity at low shear rates. Alone or in blends with natural substances of high viscosity, preferably with casein, they form films of high tack and low cohesion. Furthermore, in the case of the novel adhesives the use of toxicologically unacceptable components, especially the polymerization regulator butenol, has been avoided. They are therefore suitable for use in the foods sector and do not in general have any health-damaging and/or irritant effect on the processing staff. The novel adhesives advantageously form transparent films which are thus also suitable for the application of film labels.
The invention therefore also provides for the use of the novel adhesives for producing packaging made fom paper, board or card, and for labeling nonabsorbent substrates. The latter include, preferably, substrates of glass, metal and plastics which are employed in particular for the packaging of foodstuffs.

Protective colloid stabilized emulsion polymerization of ethylenically unsaturated monomers, and adhesive product thereof

Abstract: Adhesives comprising:

Abstract: a) from 5.0 to 95.0% by weight of an adhesive dispersion having a viscosity in the range from 2000 to 10,000 mpPaxc2x7s, which comprises (a1) an aqueous polymer dispersion which is obtainable by free-radical polymerization of a mixture M which comprises at least one ethylenically unsaturated monomer A to give a polymer P in the presence of at least one protective colloid-based on a water-soluble prepolymer which comprises at least one water-soluble monomer B, and further additives if desired, (a2) if desired, a base selected from the group consisting of alkali metal.hydroxides, ammonia and volatile organic amines, (a3) if desired, a completely water-miscible organic solvent, and, further additives; (b) from 0 to 90.0% by weight of a polysaccharide and/or a protein and/or a protein degradation product; (c) from 0 to 95.0% by weight of at least one filler; (d) from 0 to 10.0% by weight of at least one emulsifier; (e) from 0 to 30.0% by weight of further additives; (f) water to 100% by weight;

Abstract: processes for their preparation, and their use.


An awning, especially an articulated arm awning, comprises an awning cloth that can be wound up in the form of a cloth roll and a front bar that is disposed at the free outer end of the awning cloth, connected to the same, said front bar incorporating at least one swivel joint having an approximately horizontal or forwarded tilted swivel axis.

1. Field of the Invention
The present invention is directed to an awning, especially an articulated arm awning, comprising an awning cloth that can be wound up into a cloth roll and a front bar that is disposed at the free outer end of the awning cloth, connected to the same.
2. Background of the Invention
Awnings of this type in their extended position have the problem, particularly during heavy rains, that the rainwater does not run off in a defined and continuous manner, but the awning cloth bulges and accumulations of water accordingly form in the region in front of the front bar, which, due to the relatively great lever arm, subject the awning structure to significant stress. Furthermore, the water carries with it dirt particles, which then also do not run off with the water but can remain as unsightly stains after the accumulated water has dried off.
Based on this, the invention has as its object to improve an awning of the above type in such a way that an even water runoff can be attained while preventing water accumulations, and new design options are opened up at the same time.
This object is met according to the invention in such a way that the front bar incorporates at least one swivel joint with an approximately horizontal axis. Approximately horizontal, in this context, also means the usual forward tilt of awnings of this type of, e.g., 30xc2x0. A swivel axis of this type permits the front bar to be folded centrically up or down, for example, and, hence, impress onto an awning cloth that is fastened to the front bar a corresponding fold, so that rainwater will either, like with a gable roof, run off to the side in case of an upward fold, or, in case of a downward fold, run off in a defined manner within the region of the horizontal swivel axis. The swivel joint is preferably executed as a hinge, to attain sufficient stability.
A coupling means is advantageously provided such that when the awning is extended, the same is folded around its horizontal swivel axis, either up, similar to a gable roof, or down, and when the awning or front bar is retracted, the front bar is moved into a straight position. A separate activity is therefore not required to create the folded position of the front bar.
It is also possible, of course, within the frame of the invention, to dispense with an automatic folding and provide a locking means in the region of the horizontal swivel joint, in order to create a folded position only after releasing such a locking means.
In an alternate embodiment, the coupling means may be formed by a cable pull mechanism, which engages at the articulated arm sections and accomplishes the folding of the front bar. To the extent in which a cable pull mechanism is mentioned here, the term xe2x80x9ccablexe2x80x9d shall be understood in the broadest sense as a flexible force transmission medium, i.e., belts, straps, chains, or the like may, of course, be considered as well.
In a further embodiment, provision is made for the coupling means to be formed by articulated arm sections that are swivel-mounted at least in sections around an approximately horizontal swivel axis, so that this swivel movement is transferable to the given front bar sections, and a folding of the front bar is attained in this manner.
If the given outer articulated arm section is connected via a universal joint to the front bar, this universal joint may be selectively blocked or released, e.g., by means of a pin, to cause the front bar to fold by blocking, or prevent its folding by releasing.
The swivel joint that is formed between the outer and inner articulated arm section preferably has a swivel axis that is tilted against the vertical plane and advantageously disposed offset from the center longitudinal axis of the inner and outer articulated arm section, preferably on an offset curvature. The inventive design achieves not only a problem-free water runoff but it furthermore opens up completely novel design options, for instance by permitting the awnings to take a shape similar to a gable roof. If, for example, like on the window front of a department store, multiple awnings of this type are disposed side by side, it is possible, for example, to work only with awnings that are folded up like a gable roof, or to place alternating awnings, one folded up and one folded down, side by side in order to create a type of jagged peaks structure.
The invention will be explained in more detail below based on preferred embodiments in conjunction with the drawing.

Awning, especially articulated arm awning


In a procedure for cleaning floors by hand with the help of flat cleaning mops, mops provided with a certain quantity of cleaning solution are used. In this case, at least one mop is removed from a storage container (1), and saturated with solution before or during removal; the solution is applied onto the surface of the mop; the mops are stored as is after use in a holding container (2) up to their disposal for purposes of regeneration. A device for fitting and preparing a larger number of flat cleaning mops consists of a storage container, which has a removal opening (5) for removing mops, and is provided inside with a feeding device (11) for prior saturating the removed mops with cleaning solution.

The invention relates to a procedure for cleaning floors by hand with the help of flat cleaning mops, wherein mops provided with a certain quantity of cleaning solution are used.
This procedure is carried out on large surfaces by means of a device for supplying and preparing flat cleaning mops with a storage container, which stores a larger number of mops.
The use of flat cleaning mops, so called flat mops, in cleaning technology is very widespread. Flat mops are used in particular on floors that need to be cleaned by hand, e.g., in laboratories, hospitals, production facilities with high demands on purity and cleanliness, e.g., in computer technology, chip manufacture, medical technology, and the like.
Flat mops have the advantage of covering a large floor surface area, wherein the operator can easily check the result. One special advantage lies in the fact that the used flat mop need only be replaced by a fresh one at the latest when the cleaning solution applied to the fresh flat mop has been used up. The precondition for achieving a high standard of cleaning is that the operator does not have to rinse, wring and again saturate the flat mop, as is usually the case.
As a result, this invention proceeds from the knowledge that the mop replacement principle is to replace on-site mop cleaning, i.e., the used mop, whose cleaning solution has been used up, is replaced by a fresh mop saturated with fresh cleaning solution. The cleaning solution is to be applied to a fresh mop in the dosage needed for the desired cleaning result.
To ensure a suitable dosage, it is already known from EP 90850020 B1 to pack a cleaning mop in a sealed cover, which also encompasses a sealed container with cleaning solution, so that the liquid is separate from the mop, and the container can be opened without tearing open the cover, so that the liquid flows out inside the cover, and saturates the mop. After use, the mop is taken to the washing plant, where it is washed and packed in a new cover for reuse in the manner described.
Also known from U.S. Pat. No. 4,174,977 is to have a conventional cleaning cart with rinsing bucket, mop press and waste container incorporate a metering device, which makes it possible to saturate the mop rinsed and dry-pressed for reuse with a selectable quantity of fresh cleaning solution. Metering device operation is valve-controlled, wherein a settable quantity of cleaning solution is diverted from a storage container and applied by means of a swiveling dispensing tube onto the mop bundled in a bucket, which consists of a bundle of mop element skeins. This type of metering device is unsuitable for flat mops, since it cannot be used to achieve a uniform distribution of cleaning solution. In addition, bundled mops are less suitable for the reliable performance of cleaning jobs where high demands are placed on the cleaning result.
By contrast, the object of this invention is to create a procedure and device of the kind mentioned at the outset for cleaning floor surfaces that not only satisfy the highest demands on cleaning quality; in particular, the goal is to support an environment-friendly, cost-effective cleaning procedure with a suitable device that does not require renewed on-site preparation of the cleaning mop.
This object is achieved in the procedure according to the invention in that at least one mop is removed from a storage container, that the mops are saturated with solution before or during removal, that the solution is applied onto the surface of the mop, and that the mops are kept as is after use in a holding container until disposed of for purposes of their regeneration.
This procedure can be advantageously supported by means of a suitable device for fitting and preparing flat cleaning mops with a storage container, which stores a larger number of mops, has a removal opening for removing mops, and is provided inside with a feeding device for prior saturating the removed mops with cleaning solution.
In addition to at least one storage container, this device advantageously encompasses at least one holding container, which accommodates the dirty mops following their use.
The procedure and device according to the invention provide, as it were, a novel way for mastering cleaning jobs involving large surfaces, e.g., of the kind handled in particular by large companies in the cleaning industry, and for which the solution proposed by the invention is therefore of special interest. Because the device according to the invention makes it possible to automatically control how much cleaning solution is metered per mop, requirements for an elevated cleaning quality can be harmonized in an ideal fashion with those for an economical utilization of resources. A suitable metering of cleaning solution makes it possible to adjust the quantity of cleaning solution applied per unit area of the floor surface to be cleaned in a highly reliable and accurate manner; at the same time, this sets the consumption of fresh water and cleansing agent. In comparison to the conventional, individual metering based on cleaning power, an economical use of cleaning agent can therefore also be generally achieved. The fact that the used mops are not washed on-site, but instead collected and washed in a large number at a washing plant, eliminates additional problems involving the disposal of dirty water. This means that fresh water is not used at the cleaning site, and nor must dirty water be removed. Therefore, an economic cost calculation can advantageously be based either on the cleaned surface or number of used mops. This makes it possible to calculate very precisely the financial burden placed on the customer for the xe2x80x9ccleaningxe2x80x9d service while still ensuring cleaning quality.
The cleaning system proposed by the invention, which is based on the use of flat mops and their exchange, is particularly suitable for use in franchise systems, which are suitably organized to perform cleaning services on-site and maintain a system for supplying fresh flat mops and disposing of dirty flat mops. This activity centers around the device according to the invention, which the franchise sets up in the number required at the customer, and there fits it with fresh flat mops, whose metering device must be serviced accordingly, and which can have a holding container for keeping the used mops, whose contents must be disposed of.
The mops are advantageously fanned out and stacked one on top of the other in a storage container of the device according to the invention. In this case, either only the mop removed from the stack, e.g., the top mop, is saturated with solution, wherein the remaining stack remains essentially dry, or several mops are moistened simultaneously, if used simultaneously or in rapid succession.
The mops are advantageously saturated with cleaning solution by spraying the mops with the solution until saturated. As an alternative, the mops can be saturated through immersion in a corresponding bath with cleaning solution.
For saturation purposes, the mops are removed from the stack of fresh flat mops in the storage container, preferably from the top, by first saturating the uppermost or lowermost mop of the stack with cleaning solution and then removing it. Another possibility is to remove the respective top mop of the stack and only then saturating it with solution in the direction taken off behind the stack. In this variant, the stack remains completely dry. Saturation can either take place by spraying immediately before removal, or drawing the mop through a bath filled with solution. To ensure a uniform saturation of the mop, it makes sense for the removal of the mop from the storage container to be automatically controlled.
The device according to the invention can be configured to have a metering device that routes an adjustable quantity of solution to the feeding device from a tank with fresh cleaning solution, which is advantageously designed as a spraying device.
Within the framework of the device according to the invention, the storage container has a magazine with a preferably horizontal cross section, which corresponds roughly to the dimensions of a fanned out mop, and whose height is dimensioned according to the stacking height of the number of fresh mops stacked one on top of the other therein. In this way, up to 50 or even up to 100 fresh mops can be stored in a dry state without any problem. Based on a cleaned floor surface per mop of 20 m2, for example, this yields a savings of approx. $2.00 per liter of used cleaning solution in favor of the cleaning system according to the invention, calculated according to the statistical data valid in the U.S. In terms of the U.S. national economy, this denotes an overall savings of approx. 800 million dollars per year. These savings can essentially be attributed to the ability to precisely, and hence economically, meter the cleaning solution per mop, the surface coverage per mop depending on the cleaning job, and the rational maintenance, fitting and disposal of the device components according to the invention used in the process.
In another proposal according to the invention, the storage container has a removal opening in the front, under which is located the stack with fresh mops, and above which the feeding device is accommodated. In this case, it makes sense for an intermediate floor in the storage container to be adjustable in height based on the stack height, which diminishes as the mops stacked in the magazine are removed. The height of the intermediate floor can here be incrementally adjusted, wherein the height is adjusted by about the thickness of one mop in each increment.
In addition, actuation of the metering device can be linked with each height adjustment, so that the respectively removed mop or the uppermost mop of the stack is saturated with solution. As already stated above, this can either take place while the uppermost mop is still on the stack, or only after the uppermost mop has been taken off the stack.
Instead of a height-adjustable intermediate floor, the stack can rest on a fixed decking, wherein the removal opening adjusts to the stack height.
As concerns the structure of the storage container, the invention provides that the feeding device consists of spray nozzles distributed over the container cross section, which are connected to the metering device by a system of lines.
In one advantageous configuration of the metering device, the latter is situated with the tank for the cleaning solution and a compressed air bottle to convey the solution by means of compressed air to the feeding device in a separate casing.
Storage and holding containers are advantageously set up one next to the other on the casing for the metering device. The casing can be mounted on wheels, so that the operator can bring it along. This minimizes the time required to change out the mop.
For purposes of maintaining the device according to the invention, it makes sense that its storage and holding container each have a lid section that can be swing open to the side on hinges. Unlatching and tilting the lid makes it easy to both refill the storage container with fresh mops, and remove the dirty mops from the holding container.
In an advantageous form of execution of the invention, the magazine with stack of fresh flat mops is located inside the storage container, specifically above the intermediate floor, wherein the stack is bounded on the sides by vertical guide rods.
The height of the intermediate floor is advantageously adjusted by a spring force, exerted by the removal of the stack weight or through the use of an upper stop. Tension and/or compression springs that act on the intermediate floor are here used.
The storage container preferably has a drip floor below the stack for cleaning solution released to the sides of the stack, which can be returned for reuse. It makes sense to use a drain to connect the drip floor with a collecting basin provided in the lower part of the storage container.
In another advantageous configuration of the invention, the removal opening of the storage container is sealed form outside by means of a flap, which, when opened, actuates the metering device, whose subsequent actuation is disabled until the saturated mop has been removed. This ensures that the same mop cannot be moistened over and over again simply by opening the flap. The flap can also be provided with a lock, so that it additionally serves as a safety element when the device is not in use.
In order to reliably prevent already used mops given an empty magazine from again being taken from the holding container, the invention also provides that the holding container have a feed inlet on its lid section that is bridged to the inside by a deflection compartment, which prevents a hand from reaching in. The deflection compartment also enables a better utilization of space for the holding container.
The invention shall now be described based on respective examples of the first and second embodiments of the invention.

Procedure and device for cleaning floors with flat cleaning mops