Disclosure of Invention
In view of the technical problems set forth above, the present invention aims to provide a polyurea type reflective insulation coating for buildings and a preparation method thereof, so as to solve the disadvantages of the prior art. When the polyurea reflective thermal insulation coating for buildings prepared by the method is used for building external walls, the polyurea reflective thermal insulation coating for buildings can play a good thermal insulation role, and meanwhile, a coating film formed by the polyurea reflective thermal insulation coating for buildings has good stain resistance, long service life and good physical properties.
The present inventors have made intensive studies and completed the present invention.
According to an aspect of the present invention, there is provided a preparation method of a polyurea type reflective insulation coating for construction, the preparation method comprising the steps of:
a) mixing and reacting polyether amine, isophorone diisocyanate and a solvent, wherein the mole number of the isophorone diisocyanate is larger than that of the polyether amine;
b) adding a hydrophilic chain extender and a catalyst into the product obtained in the step a) and heating for reaction;
c) adding triethylamine into the product obtained in the step b) and reacting;
d) adding a polyamine aqueous solution into the product obtained in the step c) and reacting;
e) removing the solvent from the product obtained in step d) to obtain an aqueous polyurea emulsion;
f) mixing and dispersing the water-based polyurea emulsion obtained in the step e) with a defoaming agent, a hydrophobic agent, hollow glass beads, titanium dioxide and water to obtain the polyurea reflective heat-insulating coating for the building.
According to certain preferred embodiments of the present invention, the polyetheramine is selected from one or more of polyetheramines having an amine functionality of 2 or 3 and a number average molecular weight of 230 to 5000.
According to certain preferred embodiments of the present invention, the solvent is selected from one or more of ethyl acetate, acetone, methyl ethyl ketone and ethylene glycol dimethyl ether.
According to certain preferred embodiments of the present invention, the hydrophilic chain extender is selected from one or more of 2, 2-dimethylolpropionic acid and 2, 2-dimethylolbutyric acid.
According to certain preferred embodiments of the present invention, the catalyst is selected from one or more of dibutyltin dilaurate and stannous octoate.
According to certain preferred embodiments of the present invention, the polyamine is selected from one or more of ethylenediamine, 1, 3-propylenediamine, isophoronediamine, diaminodicyclohexylmethane, diethylenetriamine and piperazine.
According to certain preferred embodiments of the present invention, the defoamer is a polyether siloxane copolymer.
According to certain preferred embodiments of the present invention, the hydrophobic agent is an amino-functional polysiloxane hydrophobic agent or a water-soluble nonionic hydrophobic agent.
According to certain preferred embodiments of the present invention, the hollow glass microspheres have a diameter of 2 to 125 μm andthe true density is 0.39-0.43g/cm3。
According to certain preferred embodiments of the present invention, the water is deionized water.
According to certain preferred embodiments of the present invention, in step a), the molar ratio of the isophorone diisocyanate to the polyether amine is 2:1 to 6: 1.
According to certain preferred embodiments of the present invention, in step a), the ratio of the weight of the solvent to the sum of the weights of the polyetheramine and the isophorone diisocyanate is from 0.1:1 to 0.5: 1.
According to certain preferred embodiments of the present invention, the molar ratio of the hydrophilic chain extender employed in step b) to the isophorone diisocyanate employed in step a) is from 0.05:1 to 0.60: 1.
According to certain preferred embodiments of the present invention, the molar ratio of triethylamine employed in step c) to said hydrophilic chain extender employed in step b) is from 0.8:1 to 1.0: 1.
According to certain preferred embodiments of the present invention, the ratio between the number of moles of said polyamine employed in step d) and the number of moles of isocyanate groups in said isophorone diisocyanate employed in step a) is from 0.05:1 to 0.5: 1.
According to certain preferred embodiments of the present invention, the aqueous solution of the polyamine has a concentration of 5X 10-3-2×10-2Mol/l.
According to certain preferred embodiments of the present invention, in step f), 20 to 50 parts by weight of the aqueous polyurea emulsion is mixed and dispersed with 0.1 to 0.5 parts by weight of the antifoaming agent, 0.5 to 2.0 parts by weight of the water repellent, 30 to 70 parts by weight of the hollow glass microspheres, 5 to 15 parts by weight of the titanium dioxide, and 5 to 30 parts by weight of water to obtain the polyurea-type reflective insulation coating for construction.
According to certain preferred embodiments of the present invention, the preparation method of the polyurea type reflective insulation coating for construction includes the following steps:
a) slowly dropping polyether amine into a mixture of isophorone diisocyanate and a solvent at 0-10 ℃ and reacting at room temperature for 0.5-1.0 hour, wherein the mole number of the isophorone diisocyanate is larger than that of the polyether amine;
b) adding a hydrophilic chain extender and a catalyst to the product obtained in step a) and heating the resulting mixture to 50 to 90 ℃ for 2.0 to 4.0 hours;
c) adding triethylamine to the product obtained in step b) and reacting at 30 to 50 ℃ for 0.2 to 0.5 hour;
d) adding an aqueous solution of a polyamine to the product obtained in step c) and reacting for 0.5 to 1.0 hour;
e) removing the solvent from the product obtained in step d) to obtain an aqueous polyurea emulsion;
f) mixing the water-based polyurea emulsion obtained in the step e) with a defoaming agent, a hydrophobic agent, hollow glass beads, titanium dioxide and water, and dispersing for 0.5 to 1.0 hour at a rotating speed of 200 to 500 revolutions per minute to obtain the polyurea reflective heat-insulating coating for the building.
Compared with the existing synthesis method of the reflective thermal insulation coating for buildings, the preparation method of the polyurea type reflective thermal insulation coating for buildings according to the invention has the following advantages:
1) the polyurea reflective heat-insulating coating for the building, which is synthesized by the method, has higher elongation at break and strength;
2) the polyurea reflective heat-insulating coating for the building, which is synthesized by the method, has better glossiness and stain resistance;
3) the polyurea reflective heat-insulating coating for the building, which is synthesized by the method, has longer service life; and
4) the polyurea reflective heat insulation coating for buildings synthesized by the method has higher solid content.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. It will be appreciated that other embodiments are contemplated and may be made without departing from the scope or spirit of the present invention. The following detailed description is, therefore, not to be taken in a limiting sense.
Unless otherwise indicated, all numbers expressing feature sizes, quantities, and physical and chemical characteristics used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be suitably varied by those skilled in the art in seeking to obtain the desired properties utilizing the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
The invention provides a preparation method of polyurea type reflective heat-insulation coating for buildings, which comprises the following steps:
a) mixing and reacting polyether amine, isophorone diisocyanate and a solvent, wherein the mole number of the isophorone diisocyanate is larger than that of the polyether amine;
b) adding a hydrophilic chain extender and a catalyst into the product obtained in the step a) and heating for reaction;
c) adding triethylamine into the product obtained in the step b) and reacting;
d) adding a polyamine aqueous solution into the product obtained in the step c) and reacting;
e) removing the solvent from the product obtained in step d) to obtain an aqueous polyurea emulsion;
f) mixing and dispersing the water-based polyurea emulsion obtained in the step e) with a defoaming agent, a hydrophobic agent, hollow glass beads, titanium dioxide and water to obtain the polyurea reflective heat-insulating coating for the building.
According to the invention, in step a), the polyetheramine, the excess isophorone diisocyanate and the solvent are mixed and reacted. By "excess isophorone diisocyanate" according to the present invention is meant that the number of moles of isophorone diisocyanate is greater than the number of moles of polyetheramine. In the obtained polyether amine prepolymer, terminal amino active functional groups are reacted with isophorone diisocyanate. Wherein, at a lower temperature, the polyether amine is reacted with excessive polyisocyanate, under the condition, the chain extension of the obtained polyether amine prepolymer is less, and the viscosity of the obtained prepolymer is relatively low.
The polyetheramines according to the present invention have the meaning generally known in the art, i.e., polyetheramines are a class of polymers having a polyether structure in the main chain and amine groups as terminal reactive functional groups. According to certain embodiments of the present invention, the polyetheramine is selected from one or more of polyetheramines having an amine functionality of 2 or 3 and a number average molecular weight of 230 to 5000. Specific examples of polyetheramines that can be used in the present invention include Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, Jeffamine T-3000, and Jeffamine T-5000, which are manufactured by Huntsman Chemical Company.
The solvent used in the technical solution according to the present invention is not particularly limited as long as it can dissolve or disperse the respective components and can be removed by distillation under reduced pressure at the end of the preparation process. According to certain embodiments of the present invention, the solvent is selected from one or more of ethyl acetate, acetone, methyl ethyl ketone, and ethylene glycol dimethyl ether.
Step b) according to the present embodiment is a step of carrying out a chain extension reaction to increase the chain length of the polyetheramine prepolymer obtained in step a). According to certain embodiments of the present invention, the hydrophilic chain extender is selected from one or more of 2, 2-dimethylolpropionic acid and 2, 2-dimethylolbutyric acid.
The catalyst employed in step b) is a catalyst which promotes the reaction between the polyetheramine prepolymer obtained in step a) and the hydrophilic chain extender. Preferably, the catalyst is selected from one or more of dibutyltin dilaurate and stannous octoate.
In step c), triethylamine is added to the product obtained in step b) and a neutralization reaction is carried out.
In step d), adding an aqueous solution of polyamine to the product obtained in step c) and carrying out chain extension emulsification reaction. According to certain embodiments of the present invention, the polyamine is selected from one or more of ethylenediamine, 1, 3-propylenediamine, isophoronediamine, diaminodicyclohexylmethane, diethylenetriamine and piperazine.
In step e), the solvent is removed from the product obtained in step d) to obtain an aqueous polyurea emulsion. The method for removing the solvent is not particularly limited, and for example, a distillation method generally employed in the art, particularly a distillation method under reduced pressure can be used.
In the step f), mixing and dispersing the water-based polyurea emulsion obtained in the step e) with a defoaming agent, a hydrophobic agent, hollow glass beads, titanium dioxide and water to obtain the polyurea reflective heat-insulating coating for the building. The specific type of the defoaming agent is not particularly limited, and defoaming agents generally used in the field of reflective insulation coatings for buildings may be used. The defoamer can be a polyether siloxane copolymer. Specific examples of defoamers include TEGO Foamex 810, TEGO Foamex 825, and TEGO Airex 902w, supplied by Digao Germany. The specific type of the hydrophobizing agent is not particularly limited, and hydrophobizing agents generally used in the field of reflective insulation coatings for buildings can be used. The hydrophobing agent may be an amino-functional polysiloxane hydrophobing agent or a water-soluble nonionic hydrophobing agent. Specific examples of such hydrophobing agents include TEGO phobe 1401, supplied by Digao, Germany, and hydrophobing agent AD3105, supplied by Auda. The specific type of the hollow glass beads is not particularly limited, and hollow glass beads generally used in the field of reflective insulation coatings for buildings may be used. Preferably, the hollow glass microspheres have a diameter of 2 to 125 μm, preferably 10 to 100 μm, and a true density of 0.39 to 0.43g/cm3。
According to the technical scheme of the invention, preferably, the water adopted in the preparation method of the polyurea type reflective insulation coating for buildings is deionized water.
According to certain embodiments of the present invention, in step a), the molar ratio of the isophorone diisocyanate to the polyether amine is 2:1 to 6:1, preferably 2:1 to 5:1 and more preferably 2:1 to 4: 1.
According to certain embodiments of the present invention, in step a), the ratio of the weight of the solvent to the sum of the weights of the polyetheramine and the isophorone diisocyanate is from 0.1:1 to 0.5:1, preferably from 0.1:1 to 0.4:1 and more preferably from 0.1:1 to 0.2: 1.
According to certain embodiments of the present invention, the molar ratio of the hydrophilic chain extender employed in step b) to the isophorone diisocyanate employed in step a) is from 0.05:1 to 0.60:1, preferably from 0.10:1 to 0.60:1 and more preferably from 0.3:1 to 0.5: 1.
According to certain embodiments of the present invention, the molar ratio of triethylamine employed in step c) to the hydrophilic chain extender employed in step b) is from 0.8:1 to 1.0:1, preferably from 0.9:1 to 1.0:1 and more preferably from 0.95:1 to 1.0: 1.
According to certain embodiments of the present invention, the ratio between the number of moles of said polyamine employed in step d) and the number of moles of isocyanate groups in said isophorone diisocyanate employed in step a) is from 0.05:1 to 0.5:1, preferably from 0.1:1 to 0.5:1 and more preferably from 0.1:1 to 0.3: 1.
According to certain embodiments of the invention, the aqueous solution of the polyamine has a concentration of 5 x 10-3-2×10-2Mol/l. Preferably, the weight of the deionized water in the aqueous solution of the polyamine is 1 to 3 times the weight of all the reactants added in steps a) -d) of the preparation method of the polyurea-type reflective insulation coating for construction according to the present invention.
According to some embodiments of the present invention, in step f), 20 to 50 parts by weight, 30 to 45 parts by weight of the aqueous polyurea emulsion is mixed and dispersed with 0.1 to 0.5 parts by weight, preferably 0.1 to 0.3 parts by weight of the antifoaming agent, 0.5 to 2.0 parts by weight, preferably 0.5 to 1.5 parts by weight of the hydrophobizing agent, 30 to 70 parts by weight, preferably 40 to 70 parts by weight of the hollow glass microspheres, 5 to 15 parts by weight, preferably 2 to 12 parts by weight of titanium dioxide, and 5 to 30 parts by weight, preferably 10 to 30 parts by weight of deionized water to obtain the polyurea-based reflective insulation coating for buildings.
More specifically, the preparation method of the polyurea type reflective insulation coating for buildings according to the present invention comprises the following steps:
a) slowly dropping polyether amine into a mixture of isophorone diisocyanate and a solvent at 0-10 ℃ and reacting at room temperature for 0.5-1.0 hour, wherein the mole number of the isophorone diisocyanate is larger than that of the polyether amine;
b) adding a hydrophilic chain extender and a catalyst to the product obtained in step a) and heating the resulting mixture to 50 to 90 ℃ for 2.0 to 4.0 hours;
c) adding triethylamine to the product obtained in step b) and reacting at 30 to 50 ℃ for 0.2 to 0.5 hour;
d) adding an aqueous solution of a polyamine to the product obtained in step c) and reacting for 0.5 to 1.0 hour;
e) removing the solvent from the product obtained in step d) to obtain an aqueous polyurea emulsion;
f) mixing the water-based polyurea emulsion obtained in the step e) with a defoaming agent, a hydrophobic agent, hollow glass beads, titanium dioxide and water, and dispersing for 0.5 to 1.0 hour at a rotating speed of 200 to 500 revolutions per minute to obtain the polyurea reflective heat-insulating coating for the building.
The present invention will be described in more detail with reference to examples. It should be noted that the description and examples are intended to facilitate the understanding of the invention, and are not intended to limit the invention. The scope of the invention is to be determined by the claims appended hereto.
Examples
In the present invention, unless otherwise indicated, all reagents used were commercially available products and were used without further purification treatment. Further, "%" mentioned is "% by weight", and "parts" mentioned is "parts by weight".
Test method
In the following examples, properties of each polyurea-type reflective insulation coating for construction obtained in each of examples 1 to 5 were measured and the measurement results are shown in Table 1. Specific measurement methods for relevant performances are described in GB/T25261-2010 reflective thermal insulation coating for buildings, GB/T9755-2001 synthetic resin emulsion exterior wall coating and GB 24408-2009.
Example 1
In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux unit, 27.8 g of isophorone diisocyanate and 60 g of acetone were charged, and nitrogen was introduced. 100 g of a polyetheramine Jeffamine D-2000 having a functionality of 2 and a molecular weight of 2000 were slowly added dropwise at 5 ℃ in a water bath under cooling, and after completion of the dropwise addition, the mixture was stirred at 25 ℃ for 0.5 hour. 5.9 g of 2, 2-dimethylolbutyric acid and 0.05 g of dibutyltin dilaurate were added to the above mother liquor, and the mixture was heated to 70 ℃ to react for 2.5 hours. The reaction was then cooled to 40 ℃ and 4.2 g triethylamine was added and reacted at 40 ℃ for 15 min. An aqueous solution of 2.0 grams piperazine and 180 grams deionized water was added to the mixture for emulsification and chain extension for 10 minutes. Thereafter, the mixture was dispersed in a disperser at 1000 rpm for 1.0 hour, and acetone was distilled off under reduced pressure to obtain an aqueous polyurea emulsion.
And sequentially adding 30 parts by weight of the obtained water-based polyurea emulsion, 0.5 part by weight of German Digao Foamex 810 defoaming agent, 1.5 parts by weight of German Digao Phobe 1401 hydrophobic agent, 40 parts by weight of H40 hollow glass microspheres of New Material Ltd of Maanshan mineral institute, 5 parts by weight of titanium dioxide and 23 parts by weight of deionized water into a dispersion machine, and dispersing for 0.5 hour at the rotating speed of 200 revolutions per minute to obtain the polyurea type reflective heat-insulating coating for the building.
Example 2
In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux unit, 27.8 g of isophorone diisocyanate and 100 g of ethyl acetate were charged, and nitrogen gas was introduced. 100 g of a polyetheramine Jeffamine T-3000 having a functionality of 3 and a molecular weight of 3000 were slowly added dropwise at 0 ℃ in a water bath under cooling, and after completion of the dropwise addition, the mixture was stirred at 25 ℃ for 0.5 hour. 7.4 g of 2, 2-dimethylolbutyric acid and 0.03 g of stannous octoate were added to the above mother liquor and heated to 75 ℃ for reaction for 2.5 hours. The reaction was then cooled to 40 ℃ and 4.5 g triethylamine was added and reacted at 40 ℃ for 15 min. An aqueous solution of 1.1 grams of ethylenediamine and 150 grams of deionized water was added to the above mixture for emulsification and chain extension for 10 minutes. Thereafter, the mixture was dispersed in a disperser at 1000 rpm for 1.0 hour, and ethyl acetate was distilled off under reduced pressure to obtain an aqueous polyurea emulsion.
And sequentially adding 50 parts by weight of the obtained water-based polyurea emulsion, 0.5 part by weight of TEGO Foamex 825 defoaming agent, 0.5 part by weight of Australian AD3105 hydrophobing agent, 30 parts by weight of H40 hollow glass microspheres of New Material Co., Ltd, 8 parts by weight of titanium dioxide and 11 parts by weight of deionized water into a dispersion machine, and dispersing for 0.5 hour at the rotating speed of 200 r/min to obtain the polyurea type reflective heat-insulating coating for the building.
Example 3
33.3 g of isophorone diisocyanate and 50 g of methyl ethyl ketone were placed in a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a reflux unit, and nitrogen was introduced thereinto. 100 g of a polyetheramine Jeffamine D-2000 having a functionality of 2 and a molecular weight of 2000 were slowly added dropwise at 5 ℃ in a water bath under cooling, and after completion of the dropwise addition, the mixture was stirred at 25 ℃ for 0.5 hour. 2.7 g of 2, 2-dimethylolpropionic acid and 0.05 g of stannous octoate were added to the mother liquor and heated to 75 ℃ for reaction for 2.5 hours. The reaction was then cooled to 40 ℃ and 2.0 g of triethylamine was added and reacted at 40 ℃ for 15 min. An aqueous solution of 4.7 grams piperazine and 200 grams deionized water was added to the mixture for emulsification and chain extension for 10 minutes. Thereafter, the mixture was dispersed in a dispersion machine at 1000 rpm for 1.0 hour, and methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous polyurea emulsion.
And sequentially adding 30 parts by weight of the obtained aqueous polyurea emulsion, 0.2 part by weight of TEGO Airex 902w defoaming agent, 0.3 part by weight of German Digao TEGO phobe 1401 hydrophobic agent, 44 parts by weight of H40 hollow glass microspheres of New Material Co., Ltd, 8 parts by weight of titanium dioxide and 16.5 parts by weight of deionized water into a dispersion machine, and dispersing for 0.5 hour at the rotating speed of 200 r/min to obtain the polyurea type reflective insulation coating for the building.
Example 4
In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux unit, 22.2 g of isophorone diisocyanate and 50 g of acetone were charged, and nitrogen was introduced. 100 g of a polyetheramine Jeffamine T-5000 with a functionality of 3 and a molecular weight of 5000 are slowly dropped in under the cooling condition of a water bath at 5 ℃, and stirred for 0.5 hour at 25 ℃ after dropping. 3.4 g of 2, 2-dimethylolpropionic acid and 0.02 g of stannous octoate were added to the mother liquor and heated to 75 ℃ for reaction for 2.5 hours. The reaction was then cooled to 40 ℃ and 2.4 g triethylamine was added and reacted at 40 ℃ for 15 min. An aqueous solution of 4.8 grams of isophorone diamine and 220 grams of deionized water was added to the above mixture for emulsification and chain extension for 10 minutes. Thereafter, the mixture was dispersed in a disperser at 1000 rpm for 1.0 hour, and acetone was distilled off under reduced pressure to obtain an aqueous polyurea emulsion.
And sequentially adding 40 parts by weight of the obtained water-based polyurea emulsion, 0.7 part by weight of German Digao Foamex 810 defoaming agent, 0.3 part by weight of German Digao Phobe 1401 hydrophobic agent, 40 parts by weight of H40 hollow glass microspheres of New Material Ltd of Maanshan mineral institute, 5 parts by weight of titanium dioxide and 14 parts by weight of deionized water into a dispersion machine, and dispersing for 0.5 hour at the rotating speed of 200 revolutions per minute to obtain the polyurea type reflective heat-insulating coating for the building.
Example 5
In a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet and a reflux unit, 33.3 g of isophorone diisocyanate and 50 g of ethyl acetate were charged, and nitrogen gas was introduced. 50 g of a polyetheramine Jeffamine D-2000 having a functionality of 2 and a molecular weight of 2000 and 50 g of a polyetheramine T-3000 having a functionality of 3 and a molecular weight of 3000 were slowly added dropwise under cooling in a water bath at 5 ℃ and stirred at 25 ℃ for 0.5 hour after the addition. 5.4 g of 2, 2-dimethylolpropionic acid and 0.05 g of stannous octoate were added to the above mother liquor and heated to 75 ℃ for reaction for 2.5 hours. The reaction was then cooled to 40 ℃ and 3.9 g triethylamine was added and reacted at 40 ℃ for 15 min. An aqueous solution of 4.0 grams piperazine and 150 grams deionized water was added to the mixture for emulsification and chain extension for 10 minutes. Thereafter, the mixture was dispersed in a disperser at 1000 rpm for 1.0 hour, and ethyl acetate was distilled off under reduced pressure to obtain an aqueous polyurea emulsion.
And sequentially adding 40 parts by weight of the obtained water-based polyurea emulsion, 0.5 part by weight of German Digao Foamex 810 defoaming agent, 0.5 part by weight of German Digao Phobe 1401 hydrophobic agent, 40 parts by weight of H40 hollow glass microspheres of New Material Ltd of Maanshan mineral institute, 5 parts by weight of titanium dioxide and 14 parts by weight of deionized water into a dispersion machine, and dispersing for 0.5 hour at the rotating speed of 200 revolutions per minute to obtain the polyurea type reflective heat-insulating coating for the building.
Table 1 shows the results of the performance tests of the polyurea-type architectural insulating reflective coatings obtained in examples 1 to 5 according to the present invention. The technical requirement refers to the technical standard required to be met by the heat-insulating reflective coating for buildings according to the related test method.
TABLE 1
The above examples 1 to 5 confirm that the reflective insulation coating for construction prepared by the method according to the present invention can give reflective insulation coating films for construction having good stain resistance, long service life and good physical properties.
The embodiments of the present invention are described only for the preferred embodiments of the present invention, and not for the purpose of limiting the spirit and scope of the present invention, and various modifications and improvements made to the technical solutions of the present invention by those skilled in the art without departing from the design concept of the present invention shall fall within the protection scope of the present invention, and the technical contents of the present invention as claimed are all described in the claims.