The present invention relates to a process for preparing phosphoric acid esters, in particular a process for preparing monomeric bridged bisaryl diphosphates, wherein a water-binding agent is added to the reaction solution.

The present invention relates to a process for preparing phosphoric acid esters, in particular a process for preparing monomeric bridged bisaryl diphosphates, wherein a water-binding agent is added to the reaction solution.
Bisaryl diphosphates, such as bisphenol A bis(diphenyl)phosphate and resorcinol bis(diphenyl)phosphate are known to be effective flame retardants for polymer resins. For example, a variety of polyphenylene oxide/high-impact polystyrene (xe2x80x9cPPO/HIPSxe2x80x9d) and polycarbonatc acrylonitrile-butadiene-styrene (xe2x80x9cPC/ABSxe2x80x9d) blends can be improved with bisaryl diphosphate flame retardants.
When using bisaryl diphosphates to impart flame retardancy to plastics it is desired to use compounds having a high percentage of the monomer. This is because monomeric bisaryl diphosphates import beneficial physical properties to the polymer, which properties are not provided by their dimeric or polymeric counterparts. For example, resins to which monormeric bisaryl diphosphates have been added exhibit improved impact strength, melt flow index, tensile properties and flexural properties when compared to resins combined with dimeric or polymeric aryl phosphates.
Because of their commercial utility, various processes for the manufacture of monomeric bisaryl diphosphates have been developed. For example, it is known that bisphenol-A bis(diphenyl)phosphate can be obtained by catalytically reacting a phosphorus oxyhalide with bisphenol A (BPA) and then reacting the intermediate with phenol.
WO 99/55771 describes a process for continuously preparing monomeric bisaryl diphosphates, wherein no additional auxiliary agents are used in addition to the catalyst.
WO 98/47631 discloses a process for preparing aryl diphosphate esters, which comprises a third stage of filtering off he catalyst which is unsoluble in the reaction medium.
WO 98/35970 describes a semicontinuous process for preparing bisaryl diphosphates using magnesium chloride as a catalyst. The reaction product is not worked up here either.
EP 0 485 807 B1 describes a process for preparing aryl diphosphate esters in eight process steps, a workup or extraction of the catalyst being carried out in aqueous alkaline solution.
JP-A 10/017 583 discloses a batchwise synthesis for preparing phosphate ester oligomers, the reaction being controlled via the liberation rate of HCl gas. Excess phenol is removed by distillation. whereas the catalyst, for example magnesium chloride, is removed by washing.
Finally, JP-A 10/007 689 discloses a process for removing the metal chloride catalyst by means of an acidic aqueous solution (pHxe2x89xa63) and at a temperature of at least 65xc2x0 C.
A disadvantage of these processes is that water is introduced into the reaction system by the raw materials used, such as bisphenol A, resorcinol and phenol. The POCl3 present is partially hydrolysed by water. This eventually leads to nonvolatile hydrolysis products which remain in the final product and damage the polymer during processing of the phosphates.
It is an object of the present invention to provide a process which produces oligophosphates comprising a significantly reduced proportion of hydrolysis products. It has now been found, surprisingly, that the addition of a water-binding agent to the reaction solution produces oligophosphates which comprise only small proportions of hydrolysis products.
The present invention therefore provides a process for the continuous, semicontinuous or batchwise preparation of phosphoric acid esters, characterized in that
(1) a phosphorus oxyhalide is reacted with a polyol in the presence of a waterbinding agent to produce a monomeric halophosphate intermediate, and
(2) the monomeric halophospate intermediate is reacted with an alcohol to produce the desired phosphoric acid ester.
In some preferred embodiments, the polyol in Step 1 is a dihydric alcohol, preferably bisphenol A or resorcinol, and that alcohol in Step 2 is a monohydric alcohol, preferably phenol. Conversely, in some preferred embodiments the phosphorus oxyhalide can also be reacted firstly with a monohydric alcohol to produce a monohalomonophosphoric acid diester intermediate. In some embodiments, the reaction of Step 1 and/or the reaction of Step 2 are carried out continuously. Particularly preferably, at least one step is carried out continuously or semicontinuously.
It is an object of the present invention to provide a method for continuously producing phosphoric acid esters using water-binding agents.
Another preferred object of the present invention is to provide a method for producing phosphoric acid esters in a (continuous reaction, wherein the monomeric halophosphate intermediate content of a reaction between phosphorus oxyhalide and a polyol is at least about 60%, preferably at least about 70% and particularly preferably at least about 80%.
The term continuous as used herein means that the reactants are fed into the apparatus at a constant flow rate and the reaction mixture is removed in an equally continuous manner. All reaction parameters are kept constant over time.
The term semicontinuous as used herein means that one reactant is introduced into the apparatus whereas another reactant is added slowly and continuously.
The term batchwise or discontinuously as used herein means that the reactants are introduced together into the apparatus, where they remain for a defined reaction time under set reaction conditions.
In a further preferred embodiment, Step 2 can be followed by a workup step 3 in which the product from Step 2 is worked up continuously, semicontinuously or batchwise in a phase separator at temperatures of 50 to 120xc2x0 C.
The workup of Step 3 comprises both an acidic wash and an alkaline wash, which can likewise be operated in contiguous, semicontinuous or batchwise mode, preferably in continuous mode.
Any aqueous acid can be used foil the acidic wash, for example HCl, H2SO4, H3PO4, CH3COOH. Particular preference is given to aqueous HCl, in particular in a concentration range from 0.5 to 10%. Any conventional basic salt can be used for the alkaline wash, for example NaOH, Na2CO3, NaHCO3, sodium acetate and corresponding potassium salts. Particular preference is given to Na salts, in particular NaOH in a concentration range from 0.5 to 10%.
The process of the invention is particularly suitable for continuously preparing bisphenol A diphosphate (BDP) or resorcinol diphosphate (RDP), in which case the polyol used is resorcinol.
A further object of the invention is to provide a process for preparing monomeric phosphoric acid ester products which can be used as flame retardants, for example in plastics.
For the purposes of promoting al understanding of the principles of the invention, reference will now be made to preferred embodiments and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended, such alterations and further modifications in the illustrated methods, and such further applications of the principles of the invention as illustrated therein, being contemplated as would normally occur to one skilled in the art to which the invention relates.
Preferably, the present invention relates generally to a continuous process for producing phosphoric acid esters, wherein at least one step is performed continuously, where a product can be produced which has a high monomeric halophosphate intermediate content relative to dimeric halophosphate intermediate content, along with high productivity, when the reaction is carried out in a continuous reactor system, such as a continuous stirred tank reactor (CSTR), using a dehydrating agent. The intermediate can be used, in certain embodiments, to form a desired monomeric phosphoric acid ester, including BPA bis(diphenyl)phosphate.
The preferred reactor design (i e., a continuous reactor) allows the production of product ratios otherwise unattainable in commercial quantities at high productivity.
The degree of oligomerization or polymerization can further be controlled to some extent by the degree of reaction completion in individual stages of a multiple stage continuous reactor series.
In one aspect of the invention, phosphoric acid esters are continuously produced by a two step process. In the first step, a content of at least about 60% monomeric halophosphate intermediate, preferably a bis(dichlorophosphate), is formed by continuously reacting a phosphorus oxyhalide with an alcohol, preferably a diol or other polyol. After preferably removing the excess phosphorus oxyhalide, the monomeric halophosphate intermediate is reacted with another alcohol, preferably a monohydric alcohol such as a phenol, to produce a desired phosphoric acid ester. The phosphorus oxyhalide, which has been removed for example by distillation, can be returned to the process, i.e. re-used for preparing the halophosphate intermediate.
The products of the Step 1 reaction are predominantly monomeric, and, as the monomeric product is used as a reactant in Step 2, the product of the Step 2 reaction will likewise be predominantly monomeric. However, it is recognized that, should one desire an oligomeric or polymeric component after forming the monomeric product from Step 1, the monomeric product from Step 1 may be reacted with a polyol in Step 2 and the resultant product may be further processed as desired.
In yet another aspect of the invention, the desired phosphoric acid esters are produced by continuously reacting phosphorous oxyhalide with a monohydric alcohol to produce a content of at least about 60% monohalomonophosphoric acid diester intermediate. The intermediate is then reacted with a polyol, preferably a dihydric alcohol, to produce the desired phosphoric acid ester.
Further describing one embodiment of the processes of the present invention, Step 1 of a process for preparing phosphoric acid esters preferably includes continuously reacting an appropriate alcohol with phosphorus oxyhalide in the presence of a Lewis acid catalyst. The phosphorus oxyhalide used in the present invention is generally of the formula POXn where X is a halide, including chloride or bromide, and n is preferably 3. Phosphorus oxychloride, POCl3, is the most preferred phosphorus oxyhalide.
Step 1 produces a monomeric halophosphate intermediate when a polyhydric alcohol, such as a dihydric alcohol, is used. In that embodiment, the Step 1 reaction proceeds, diagrammatically, as follows:
HOxe2x80x94Rxe2x80x94OH+2POX3xe2x86x92X2OPxe2x80x94Oxe2x80x94Rxe2x80x94Oxe2x80x94POX2 (l)+2HX
Any unreacted POX3 is removed by distillation under reduced pressure, leaving the Step 1 intermediate product I. In the above diagram, R is the carbon chain portion (i.e. the aromatic, aliphatic, alicyclic portion or a combination thereof) of the alcohol, X is a halide as previously mentioned and compound I is the monomeric halophosphate intermediate product of Step 1.
Examples of appropriate alcohols include polyols, such as polyphenols, and including dihydric alcohols such as biphenols, bisphenol A, tetrabromobisphenol A, bisphenol S, bisphenol F, ethylene glycol, 1,4-butanediol, 1,2-hexanediol, resorcinol, catechol, hydroquinone and triflydric alcohols such as glycerol as well as other polyols. The aromatic and alicylic portions of the alcohols may be alkyl- or halo-substituted. The aliphatic portion of the alcohol may also be halo-substituted. The alkyl substituent comprises saturated or unsaturated aliphatic hydrocarbon groups which may be either straight-chain or branched and have a carbon chain length of from 1 to 18. For example, the alkyl group includes methyl, ethyl and structural isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, iexadecyl, heptadecyl and octadecyl. The halo substituent is preferably chlorine and/or bromine. It is further preferred that there is no more than one substituent ortho to each hydroxyl group on an aromatic alcohol. The catalyst may be any Lewis acid (capable of promoting the reaction. Examples include, but are not limited to, AlCl3, ZnCl2, CaCl2, MgO or MgCl2, preferably MgO or MgCl2.
The catalyst is used in an amount sufficient to allow the reaction to proceed smoothly and does not have to be removed from the final product. If it is desired to remove the catalyst as completely as possible from the product, the addition of Step 3 is recommended. The amount of catalyst used in Step 1 is typically in the range of about 100 ppm to about 5000 ppm (relative to the other reagents added to the first reactor), preferably 100 ppm to about 1000 ppm and most preferably about 300 ppm to about 700 ppm.
The reaction temperature in Step 1 will depend on the specific polyol reacted, but generally can be controlled over a wide range, from about 50xc2x0 C. to about 250xc2x0 C., and the process may be operated at atmospheric pressure, at a reduced pressure, or at an elevated pressure. However, a temperature of about 50xc2x0 C. to about 200xc2x0 C. is preferred, a temperature of about 80xc2x0 C. to about 140xc2x0 C. is particularly preferred, and a temperature of about 85xc2x0 C. to about 100xc2x0 C. in the first stage and second stage and about 100xc2x0 C. to about 120xc2x0 C. in subsequent stages is most preferred.
In the first step, the process may be operated with a sufficient excess of POX3 to yield a workable reaction mass ac the reaction temperature, or an unreactive solvent may be used. The phosphorus oxyhalide/polyol mole ratio is typically about 2.5:1 to about 10:1, preferably about 3:1 to about 6:1 and most preferably about 4:1 to about 5:1. The residence time in each reactor may vary from 0.25 hours to about 6 hours.
After the reaction is complete, excess POX3 is distilled off. This can be done both in the reactor and in suitable apparatuses, such as falling film or thin film evaporators. The distillation is carried out at a temperature of 80 to 200xc2x0 C. and at a pressure of 10 to 100 mbar.
As mentioned above, the degree of oligomerization or polymerization can further be controlled to some extent by the degree of reaction completion in individual stages of a multiple stage continuous reactor series. The degree of reaction completion in Stage 1 of Step 1 is typically about 10 to about 100%, and about 20% to about 100% in subsequent stages. However, it is preferred that the degree of reaction completion in Stage 1 be about 30% to about 80% and in subsequent stages about 50% to about 100%. It is most preferred that the degree of reaction completion in Stage 1 be about 30% to about 50%, in Stage 2 about 70% to about 100% and in subsequent stages about 85% to about 100%.
The reaction of Step 1 is carried out by continuous or semicontinuous or batchwise reaction of the above-described reagents. As used herein, the term xe2x80x9ccontinuously reactingxe2x80x9d means that at least one stem, such as Step 1 or 2 or, if desired, Step 3, can be carried out at least partly continuously (i.e. the step can be divided into various stages and at least one stage is carried out continuously) or the entire step can be carried out continuously. The number of stages may range from about 1 to about 5, preferably from about 1 to about 3 and most preferably from about 2 to about 3.
However, it is also possible to carry out Step 1 in continuous or semicontinuous mode and Step 2 in batchwise mode. Alternatively, it is also possible to carry out only Step 2 in continuous or semicontinuous mode and Step 1 in batchwise mode.
It is likewise possible to use any combination of continuous, semicontinuous or batchwise operation of the individual steps, including batchwise operation of all Steps 1, 2 and, if desired, 3.
The term xe2x80x9ccontinuous reactorxe2x80x9d as used herein refers to a vessel where raw materials or a feed stream containing unreacted or partially reacted material is added continuously or essentially continuously while material is being removed from the vessel to maintain an essentially constant reactor volume, and where conditions in the vessel are such that a finite degree of reaction occurs.
As indicated above, the selection of reactor design to accomplish the continuous portion of the reaction in either Step 1 or Step 2 plays an important role in determining the degree of oligomerization or polymerization and the quality of the product. Examples of commercially available reactors that might be used to practice the invention, and that one skilled in the art is familiar with, include falling film or thin film reactors, continuously stirred tank reactors (CSTRs), tube reactors and packed column reactors. Although a wide variety of reactors may be used to practice the invention, CSTRs are preferred.
A series of continuous reactors may employ the same type, or a different type, of reactor. It is further preferred that a CSTR be used in Stage 1 of a step and then either another CSTR may be used or a batch reactor may be used. It is most preferred to use a series of CSTRs or, alternatively, a series of CSTRs, the final stage being carried out in a batch reactor.
It is noted that, along with the monomeric product produced in the Step 1 reaction diagrammed above, dimeric, other oligomeric or polymeric products may be formed. For example, referring to the diagram of the Step 1 reaction above, compound I may react with Step 1 reactants (i.e., with the dihydric alcohol and POX3) to form the following dimeric component:
X2OPxe2x80x94Oxe2x80x94Rxe2x80x94Oxe2x80x94POXxe2x80x94Oxe2x80x94Rxe2x80x94Oxe2x80x94POX2
The above dimeric component may also be produced by reaction of the following reactants and intermediates from the reaction of Step 1:
HOxe2x80x94Rxe2x80x94Oxe2x80x94POX2+HOxe2x80x94Rxe2x80x94OHxe2x86x92HOxe2x80x94Rxe2x80x94Oxe2x80x94POXxe2x80x94Oxe2x80x94Rxe2x80x94OH+HXxe2x80x83xe2x80x83(1)
H2OPxe2x80x94Oxe2x80x94Rxe2x80x94Oxe2x80x94POX2+HOxe2x80x94Rxe2x80x94OHxe2x86x92HOxe2x80x94Rxe2x80x94Oxe2x80x94POXxe2x80x94Oxe2x80x94Rxe2x80x94Oxe2x80x94POX2+HXxe2x80x83xe2x80x83(2)
HOxe2x80x94Rxe2x80x94Oxe2x80x94POX2+HOxe2x80x94Rxe2x80x94Oxe2x80x94POX2xe2x86x92HOxe2x80x94Rxe2x80x94Oxe2x80x94POXxe2x80x94Oxe2x80x94Rxe2x80x94Oxe2x80x94POX2+HXxe2x80x83xe2x80x8393)
It is obvious that the product formed from (1)-(3) above must be further reacted with POX3 to form the dimeric component.
A suitable method for determining the relative amounts of monomer, dimer and further homologues of Step 1 is liquid chromatography (GPC) using an RI detector.
The reaction of Step 1 preferably forms a content of at least about 60% monomeric halophosphate intermediate. It is further preferred that the reaction of Step 1 forms a content of at least about 70%, particularly preferably at least about 80%, monomeric halophosphate intermediate.
Referring now to Step 2 of the process, the product of Step 1 is reacted with an alcohol, such as a monohydric alcohol including phenol, in a similar way using a Lewis acid catalyst. In one embodiment, Step 2 may be depicted diagrammatically as follows:
X2OPxe2x80x94Oxe2x80x94Rxe2x80x94Oxe2x80x94POX2+4Rxe2x80x2OHxe2x86x92(Rxe2x80x2O)2OPxe2x80x94Oxe2x80x94Rxe2x80x94Oxe2x80x94PO(ORxe2x80x2)2+4HX
X and R are as defined above for Step 1 and X2OPxe2x80x94Oxe2x80x94Rxe2x80x94Oxe2x80x94POX2 is a monomeric halophosphate intermediate. Rxe2x80x2OH is the monohydric alcohol, Rxe2x80x2 being the carbon chain portion (i.e., the aromatic, aliphatic, alicyclic, portion or a combination thereof) of the alcohol, and (Rxe2x80x2O)2OPxe2x80x94Oxe2x80x94Rxe2x80x94Oxe2x80x94PO(ORxe2x80x2)2 is the desired phosphoric acid ester product. When Rxe2x80x2OH includes an aromatic or alicyclic ring, the aromatic or alicyclic ring may be alkyl- or halo-substituted as discussed above for the dihydric alcohol in Step 1. The aliphatic portion of the alcohol may also be halo-substituted as discussed above. It is further preferred that there is no more than one substituent ortho to each hydroxyl group on an aromatic alcohol. Examples of the alcohol that may be reacted in Step 2 include, but are not limited to, phenol, xylenols, tribromophenol, methanol, t-butanol, cyclohexanol and phenol/formaldehyde condensates. It is preferred to carry out Step 2 by reacting the halophosphate intermediate product of Step 1 with phenol using magnesium chloride as a catalyst.
As in the first step, the phenol (or other alcohol) and the product of Step 1 can be continuously fed to a CSTR in Step 2. Alternatively, the phenol (or other alcohol) can be added as a single charge to the product of Step 1, and the resulting mixture can be fed continuously to the reactor.
The discharge from the first continuous reactor may be fed to a second continuous reactor where the material is held at 125-250xc2x0 C. for a residence time of about 0.25-6 hours. The total phenol charge may be added to the first reactor or split such that part of the total phenol charge is added to the first reactor and the remainder added to the second reactor.
The discharge from the second reactor is fed to a buffer tank. The buffer tank is used to feed a continuous or batch vacuum stripper adapted to remove excess alcohol from Step 2, such as phenol. The alcohol, for example phenol, excess which has been removed can be returned to the process, i.e. reused for carrying out Step 2. A catalyst is used as in the reaction of Step 1.
The reaction of Step 2 is typically performed at a temperature sufficient to convert the halophosphate intermediate to the desired phosphoric acid ester product. Although this temperature may vary depending on the reagents used and the desired product, the temperature of the material in the reactor advantageously ranges from 50xc2x0 C. to about 250xc2x0 C., but preferably from about 125xc2x0 C. to about 250xc2x0 C. The volume of the reactor is preferably adjusted so that the residence time ranges from about 0.25 to 6 hours.
The alcohol/monomeric halophosphate intermediate mole ratio is typically about 4:1 to about 5:1, but preferably abort 4.04:1 to about 4.40:1, and most preferably about 4.04:1 to about 4.12:1. As in the first step, an excess of the alcohol may be used to improve the ease of processing, or an unreactive solvent may be employed. Any excess of alcohol is removed subsequent to Step 2 under reduced pressure, which can likewise be done continuously or batchwise.
In a preferred embodiment of the first aspect of the invention, BPA is continuously added to magnesium chloride and phosphorus oxychloride in a dissolution vessel at a temperature of about 50xc2x0 C. The relative feed rates are such that the phosphorous oxychloride/BPA mole ratio is about 5:1. The reaction mixture is then fed to a first CSTR at a temperature of about 90xc2x0 C. The volume of the reactor is maintained to give a residence time of about 1 hour.
The contents of the first reactor are continuously removed and transferred to further CSTRs arranged in series, successively increasing the temperature to about 100xc2x0 C. and finally 120xc2x0 C. The feed and discharge rates from the reactor are such that the residence time is about 1 hour in each case.
The discharge from the last reactor is fed to a buffer tank, which is maintained at about 90xc2x0 C. while being filled. The filled buffer tank is used to feed a continuous distillation to remove the excess POCl3 from the product of Step 1.
The product of Step 1 is then reacted with phenol using magnesium chloride as a catalyst.
As briefly mentioned above, the inventive continuous process may be operated such that part of the first step or second step is performed in a continuous reactor with the rest of the reaction being completed in a batchwise reactor or reactors. Similarly, an entire step may be performed in a continuous reactor or series of continuous reactors, while the other step is carried out in batch reactors. The steps may be carried out so as to maximize production of monomeric halophosphate intermediate product and, consequently, monomeric phosphoric acid ester product.
The monomer content of the reaction product of Step 2 depends on the presence of a high percentage of monomeric halophosphate intermediate which acts as a reactant in Step 2. Thus, if a large amount of monomeric halophosphate intermediate is produced in Step 1 relative to the (dimeric component, the monomer content of the reaction of Step 2 will also be relatively large. That is, relatively large amounts of the monomeric phosphoric acid ester product of Step 2 will be formed compared to dimeric, oligomeric or polymeric phosphoric acid ester product.
Parameters that can affect the properties and quality of the products of Step 1 and Step 2 include catalyst selection and amount of catalyst used, and phosphorus oxyhalide/alcohol ratio. Each of these parameters has an optimum range to give a flame retardant material exhibiting the desired properties. In addition, the moisture content of each starting material has an effect on the final product quality. For example, if the moisture content of the reactants is kept low, a larger amount of monomeric product can be obtained.
When Step 1 or Step 2 are performed in a series of reactors, at least one of which is a continuous reactor, the raw materials, such as solvent, catalyst, phosphorus oxyhalide, alcohol (i.e. phenol or polyol, such as a diol) may be added to just the first reactor in the series or to downstream reactors in addition to the first. This can be done to improve the ease of processing, to control product quality and/or to obtain the desired product or mixture of products.
Water removal agents used may be both physical and chemical agents, such as zeolites, PCl5, P4O10, silica gel, water-binding salts, magnesium alkyls and other organometallic compounds or other substances known to the person skilled in the art to have a water-binding effect. These agents are used in a sufficent amount to remove the water introduced by the starling materials. The required amount depends on the type of water-binding agent used. A typical amount to be used is from 0.1 to 5% (based on the sum of the starting materials). These water-binding agents can be added in Step 1 and/or Step 2 of the reaction. It is furthermore possible to generate the water-binding agent in situ in one of the reagents, for example by converting PCl3 to from PCl5 by chlorination.
In an alternative embodiment, a process for preparing phosphoric acid esters is provided which is characterized in that
(1) a phosphorus oxyhalide is reacted continuously, semicontinuously or batchwise with a monohydric alcohol in the presence of a dehydrating agent to produce a monohalomonophosphoric acid diester intermediate, and
(2) said monohalomonophosphoric acid diester intermediate is reacted continuously, semicontinuously or batchwise with a polyol to produce the desired phosphoric acid ester.
This process is followed, if desired, by an additional workup step in which the product from Step 2 is worked up continuously, semicontinuously or batchwise in a phase separator at temperatures of 50 to 120xc2x0 C., preferably 70 to 90xc2x0 C.
In this second aspect of the invention, the products from this step are then reacted with the chosen alcohol selected from the alcohols described above, preferably a polyol, such as a diol, to give the desired phosphoric acid ester. This route also utilizes Lewis acid catalysts, water-binding agents and continuous addition of reactants as described for the other embodiments. Step 2 product composition and properties are similar to those obtained in the previously described route. The inventive continuous process may be operated in a similar fashion as described above. For example, in certain embodiments the reaction of the intermediate with the polyol may also be performed in a continuous reactor. Alternatively, the first reaction may be performed in a batch reactor and the second reaction may be performed continuously.
Referring more specifically to the above alternative embodiment, the Step 1 reaction of the monohydric alcohol with the phosphorus oxyhalide may be diagrammed as follows:
POX3+2Rxe2x80x2OHxe2x86x92(Rxe2x80x2O)2POX(II)+2HX
Rxe2x80x2OH and X are as previously defined and compound II is the monohalomonophosphoric acid diester intermediate.
The specific catalyst and the quantify used are the same as in the previous embodiments discussed. The same applies to the type and quantity of the water-binding agents.
The reaction temperature in Step 1 of the alternative embodiment can likewise be controlled over a wide range, from about 50xc2x0 C. to about 250xc2x0 C., and the process may similarly be operated under various pressures. However, a temperature of 50xc2x0 C. to about 200xc2x0 C. is preferred, and a temperature of about 90xc2x0 C. to about 140xc2x0 C. is particularly preferred. Moreover, residence times are typically about 0.25 hours to about 6 hours.
The alcohol/phosphorus oxyhalide mole ratio is advantageously from about 1.5:1 to about 3:1, and particularly preferably from about 1.75:1 to about 2.25:1.
Reaction of phosphorus oxyhalide with a monohydric alcohol may yield the following undesired compounds:
Compound III is a dihalomonophosphoric acid monoester intermediate and Compound IV is a phosphoric acid triester. Compound IV is undesired as this compound can no longer react with a polyol in Step 2 to produce a desired phosphoric acid ester product. Compound III is undesired because it has the potential of reacting with the reactants and intermediates formed in the reaction of Step 2, and can thus lead to formation of dimeric, oligomeric or polymeric products in Step 2. As one skilled in the art is aware of the specific undesired reactions that may proceed and products that may be produced, it is not necessary to describe them here.
The reaction between phosphorus oxyhalide and the monohydric alcohol will typically produce a content of at least about 60% monohalomonophosphoric acid diester.
It is further preferred that at least about 70%, particularly preferably at least about 80%, of the monohalomonophosphate diester is produced.
Step 2 of the alternative embodiment may be diagrammed as follows:
2(Rxe2x80x2O)2POX+HOxe2x80x94Rxe2x80x94OHxe2x86x92(Rxe2x80x2O)2OPxe2x80x94Oxe2x80x94Rxe2x80x94PO(ORxe2x80x2)2+2HX
Rxe2x80x2 and X are as defined above. The reaction of Step 2 produces the desired monomeric phosphoric acid ester product, (Rxe2x80x2O)2OPxe2x80x94Oxe2x80x94Rxe2x80x94Oxe2x80x94PO(ORxe2x80x2)2.
The specific catalyst and the quantity used is the same as in the embodiments discussed previously. The same applies to the type and quantity of the water-binding agents.
The reaction temperature in Step 2 of the alternative embodiment can also be controlled over a wide range, from about 50xc2x0 C. to about 250xc2x0 C., and the process may similarly be operated under various pressures. However, a temperature of about 125xc2x0 C. to about 250xc2x0 C. is preferred. Moreover, residence times are typically about 0.25 hours to about 6 hours.
The polyol/monohalomonophosphoric diester intermediate mole ratio is advantageously from about 0.3:1 to about 0.8:1, and particularly preferably from about 0.4:1 to about 0.6:1. The preferred degrees of reaction completion in Step 1 are similar to those described above.
The phosphoric acid esters prepared by the methods of the present invention can be utilized as flame retardants in resin compositions. The resin may be a polymer and may include polyphenylene oxide, high-impact polystyrene, polycarbonate, polyurethane, polyvinyl chloride, acrylonitrile-butadiene-styrene, polybutylene terephthalate and mixtures thereof. A wide variety of other polymer resins may also be used.

Process for preparing phosphoric acid esters


A non-destructive monitoring method for internal pressure intensity of a pipeline. The method establishes an equation relationship by the fact that the variation of the internal diameter of the pipeline is the same as that measured by FBG sensors, and can effectively obtain the value of the internal pressure intensity of the pipeline by measuring the strain values of the FBG sensors installed on the pipeline so as to monitor the internal pressure intensity of the pipeline. The present invention has the advantages of simple principle, convenient installation, no damage to pipeline structure, long-distance real-time on-line monitoring and the like, and can measure the pressure intensity of various pipelines with different diameters by changing the calibration distance of sensors and the dimension of sensor clamps. This can complete non-destructive, real-time and accurate monitoring on the internal pressure intensity of the pipeline.

With the rapid development of industrial economy, the demand for resources such as petroleum and natural gas which are vital to human development continuously increases. With the advantages of low cost, energy saving, high safety, stable supply and the like, the pipeline can be used for long-distance transportation of petroleum and natural gas and thus its usage is also on the increase. In order for the media in the pipeline to be transported normally, it is essential to apply appropriate pressure intensity in the pipeline. However, on one hand, pressure intensity that is too high makes the pipeline unable to withstand excessive pressure and thus damaged, shortening the service life of the pipeline; on the other hand, pressure intensity that is too low makes the pipeline unable to transport the media normally, increasing the economic cost. Therefore, real-time monitoring on the internal pressure intensity at key joints of the pipeline can ensure the safe and effective operation of the pipeline and enhance the overall economic benefit.
At present, the main methods of measuring the internal pressure intensity of the pipeline are a method of measurement by installing a pressure gage and a method of measurement by installing a pressure transmitter. For the above two methods, it is necessary to form an opening in the pipeline to connect the pressure gage or the pressure transmitter to the pipeline structure through a valve so as to measure the internal pressure intensity of the pipeline. The two methods both cause damage to the pipeline structure and have potential safety hazards for the long-term operation of the pipeline in the future, and the pressure measurement device is not easy to replace once damaged. In addition, manual reading is required for the value of the internal pressure intensity of the pipeline measured by the method of measurement by installing a pressure gage, which not only consumes manpower but also cannot monitor the change of the internal pressure intensity of the pipeline in real time. The pressure transmitter is an electrical sensor. Although it can solve the problem of manual monitoring of pressure intensity data, it is extremely flammable for petroleum and natural gas pipelines, petroleum and natural gas. The installation and use of electrical sensors on such pipelines still pose a risk of flammability and explosion to the pipelines.
In recent years, with the successful application of the optical fiber sensing technology in safety monitoring of the fields such as military, aviation and infrastructure, the optical fiber sensing technology is also introduced into pipeline monitoring. The fiber bragg grating (FBG) sensor has the advantages of anti-electromagnetic interference, no direct use of power, high sensitivity, easy realization of long-distance signal collection and the like, and can achieve accurate and real-time monitoring on the internal pressure intensity of the pipeline.

Non-destructive monitoring method for internal pressure intensity of pipeline


An electronic meter incorporates a TCP/IP protocol suite and an HTTP server to provide two-way access to the meter data. Alternatively, the TCP/IP protocol suite may be incorporated into a gateway serving multiple meters connected through a power line or wireless two-way network. The gateway may incorporate an HTTP server for accessing data from multiple meters and for transmission of data to individual meters. Other aspects of the disclosed system include the use of a common gateway interface for remote access to meter data and to set meter parameters using HTML forms in HTTP browsers; remote reading and setting of multiple meter parameters using a TCP/IP protocol suite; a TCP/IP protocol suite implemented in designated nodes in a CEBus LAN with remote access through TCP/IP to routers and brouters and to individual meters on the LAN; and an SLIP-PPP enabled gateway for remote TCP/IP access through a serial interface to a single or multiple meter parameters.

The present invention relates to automatic meter reading (AMR) systems for use in automatically reading electrical energy and other utility meters (e.g., water and gas meters). The invention is more particularly intended for, although not limited to, use in an electronic meter. Further background information on electronic meters can be found in U.S. Pat. No. 5,548,527, Aug. 20, 1996, titled "Programmable Electrical Energy Meter Utilizing a Non-Volatile Memory" (assigned to ABB Power T&D Company Inc.) Further background on automatic meter reading systems can be found in U.S. Pat. No. 5,553,094, Sep. 3, 1996, titled "Radio Communication Network for Remote Data Generating Stations."

This patent is subject to a terminal disclaimer.

Remote access to electronic meters using a TCP/IP protocol suite


A mobile electronic device may include a memory device and a memory controller including an error correction code (ECC) encoder to encode data, a constrained channel encoder configured to encode an output of the ECC encoder based on one or more constraints, a reinforcement learning pulse programming (RLPP) component configured to identify a programming algorithm for programming the data to the memory device, an expectation maximization (EM) signal processing component configured to receive a noisy multi-wordline voltage vector from the memory device and classify each bit of the vector with a log likelihood ration (LLR) value, a constrained channel decoder configured to receive a constrained vector from the EM signal processing component and produce an unconstrained vector, and an ECC decoder configured to decode the unconstrained vector. A machine learning interference cancellation component may operate based on or independent of input from the EM signal processing component.

The following relates generally to data storage, and more specifically to data storage for a mobile device.
Memory devices are commonly used electronic components for storing data. NAND flash memory devices allow several bits of data to be stored in each memory cell, providing improvements in manufacturing costs and performance. A memory cell in which multiple bits of data are stored may be referred to as a multi-level memory cell. A multi-level memory cell partitions a threshold voltage range of a memory cell into several voltage states, and data values written to the memory cell are extracted using the memory cell voltage levels.
However, storing multiple bits per memory cell may decrease the dynamic voltage range of each voltage state, making the memory cells more susceptible to noise. Compensating for this noise may require increased computational power, which may hinder performance in a mobile device. Therefore. There is a need in the art for reliable, low power multi-cell memory systems for use in mobile electronic devices.


A storage module having at least one exterior panel of a motorized vehicle, at least one door, and at least one inner panel. The door is at least partially formed by at least one of the exterior panels. At least one of the exterior panels and at least one of the interior panels define at least one area to form the storage module.

Most vehicles have areas designed for storage, whether it is a trunk in a sedan or a truck bed in a pick-up truck. Additionally, storage areas can be added onto a motorized vehicle in order to give the user additional space to store objects or materials. For example, storage boxes can be mounted to the truck bed in order to give the user a defined storage area to store smaller objects such as tools. The storage boxes are typically mounted to the truck bed adjacent to a cab of the vehicle. These storage areas can also be mounted on top of the side walls of the truck bed. Thus, the storage areas are mounted to a box section that forms the top of the side walls. Typically, the box section has a greater width than the remaining portions of the side walls, which allow for the storage areas to be mounted to the side walls.
However, when these additional storage areas are mounted to the truck bed or the side wails of the truck bed, it can be difficult for the user to reach the objects in these storage areas. For example, when the storage boxes are mounted in the truck bed, the user has to get into the truck bed in order to access the storage areas. Likewise, when the storage areas are located on top of the side walls of the truck bed, the storage areas can be too high for some users due to the height of the vehicle in combination with the storage boxes being mounted on top of the side walls of the truck bed. In both scenarios, it is difficult for the user to get the objects out of the storage boxes, and often times the user must get into the truck bed to access the storage boxes.
Further, both scenarios require additional components to be added to the body of the vehicle. These additional manufacturing steps increase the cost of including storage areas on the vehicles. Further, securely fastening the storage area to the truck bed can be complex.
Therefore, it is desirable to develop a storage module that is integrated into the frame of a vehicle so that the storage compartment is integrated into the vehicle rather than having additional space added onto the vehicle for storage.


A multilayer ceramic matrix composite structure is disclosed. The ceramic matrix composite structure may include a three-dimensional weave fabric forming a core layer. The ceramic matrix composite structure may also include a two-dimensional weave fabric attached to an outer top surface of the three-dimensional weave fabric such that the two-dimensional weave fabric forms a top layer, and a two-dimensional weave fabric attached to an outer bottom surface of the three-dimensional weave fabric generally opposite to the outer top surface such that the two-dimensional weave fabric forms a bottom layer. The structure may include increased interlaminar shear strength.

Parts made from ceramic matrix composite (CMC) materials permit higher operating temperatures than do metal alloy materials due to the inherent nature of ceramic materials. High temperature environments such as state of the art turbine engines require such materials. This high temperature capability translates into reduced cooling requirements, resulting in higher power, greater efficiency, and reduced emissions from the machine. Conventional CMC components formed from two-dimensional fiber arrangements have sufficient in-plane, bending strength, but often lack sufficient in-plane shear stress strength to carry stress loads from backside pressure loads.

Multilayered ceramic matrix composite structure having increased structural strength


Device for locking the articulated joint in the longitudinal direction between the plate of a dust mop and the handle, which permits deactivation and subsequent reactivation of the locking of the articulated joint between the handle and the plate in a longitudinal direction, carried out by the user with his feet instead of his hands.

As is well-know the plates for dust mops are connected to their relative handle with the usual attachments that allow the handle to be articulated with respect to the plane of the plate both in the transversal as well as in the longitudinal direction.
Sometimes, for some cleaning operations, it is necessary to make it solid and prevent any swinging between the plate and the handle in the longitudinal direction of the plane of the handle, by locking the relative articulated joint.
On the market the devices that carry this out are extremely complex and therefore costly.
For the deactivation and subsequent activation operation, for said devices on the market you have to use your hands, something that is extremely inconvenient for the user.
The purpose of this patent is to make a simple, and therefore cheap, device which permits deactivation and subsequent reactivation of the locking of the articulated joint between the handle and the plate in a longitudinal direction, carried out by the user with his feet instead of his hands.
The base element, with an open female type connection on the bridge-shaped pivot with an elliptical section and joined to the plate, which creates the articulated joint in the transversal direction with respect to plane of the plate, has above the hinge zone, in order to carry out the articulated joint in the longitudinal direction of the plate, an extension configured as a female with central hollow.
The handle-holder element fitted with threading for the flange (not drawn), in addition to the lower hinge zone for coupling with the base element for creating the articulated movement in the longitudinal direction of the plate, has a fork configuration for the entire zone above up to where the chamber for inserting the handle ends.
The arms of the fork, for the section relative to the extension above the hinge zone, have some raised areas on the internal walls functioning as a guide for a sled element to be inserted inside.
On the four lower walls of the arms there are two arrays of conchoidal imprints joined to the planes of the above-mentioned walls, and which are used by the sled element for coupling the raised areas with which it is equipped, for remaining in a stopped position during the execution of two different operating actions (locking and unlocking).
The sled element, whose section is configured in a complementary way to the transversal section of the stroke of the fork along which it has to travel going up and going down, has a male appendage on its lower surface whose size corresponds to the female hollow on the upper extension of the base element into which it has to go to lock the articulated joint.
Said sled element has two sturdy cantilever extensions in the centre of the sides, in the form of arms, to be maneuvered with the foot of the operator who uses the dust mop for cleaning, fitted with device of which the sled element is a part.
What has been described is clarified in the enclosed drawings.


A micro mirror device includes a first hinge supported by a substrate, a mirror plate tiltable around the first hinge and having a first set of arms facing the substrate, and a second set of arms on the substrate. The first set of arms and the second set of arms can be interdigitated when the mirror plate is tilted. The micro mirror device includes a first lateral guard on the substrate (or the mirror plate). The first lateral guard can limit movement of the mirror plate to a position in a first direction substantially parallel to an upper surface of the substrate to prevent the first set of arms from contacting the second set of arms when the arms are in the interdigitated position.

The present invention relates to improved micro mirrors and their method of fabrication.
A spatial light modulator (SLM) can be built with an array of tiltable mirror plates. Each mirror plate can be tilted by electrostatic forces to an "on" position and an "off" position. The electrostatic forces can be generated by electric potential differences between a planar electrode on the mirror plate and one or more opposing electrodes underneath the planar electrode on the mirror plate. In the "on" position, a reflective surface of the micro mirror plate can reflect incident light to form an image pixel in a display image. In the "off" position, the micro mirror plate directs incident light away from the display image. Despite the advances in the designs and fabrication of micro mirrors, relatively high voltages are usually required to produce enough electrostatic forces to produce appropriate tilt movements in the mirror plate. High voltages require high voltage drive electronic circuits that add complexity and cost to the devices. In addition, planar and stepped electrode mirror devices generate small electrostatic forces and suffer from adhesion problems when they operate in mechanical contact mode.

Micro mirrors having a mirror plate with interdigitated arms


The loop segment switching system includes a plurality of signal sources, each producing an output signal; and, a plurality of signal sinks, each signal sink normally accepting an output signal from an associated signal source and for increasing the power of the output signal to a desired level. A node switching system of the loop segment switching system includes a plurality of switch nodes and control means. Each switch node, in its basic form, includes a first relay, a second relay, and a third relay. Associated signal sources and amplifiers are normally connected to each other via the third relay. The switch nodes are normally connected in one continuous interconnecting loop from the first relay of a node to the second relay of an adjacent node. The control means is connected to the switch nodes for activating the plurality of switch nodes in order to reconnect signal sources and signal sinks from the normal connection in the event of a failure of a signal source or a signal sink. The reconnections are implemented by disconnecting a segment of the interconnecting loop and using that segment as a connection between the desired signal source and signal sink.

1. Field of the Invention
The present invention relates to switching systems and more particularly to switching systems that require switching between multiple signal sources and multiple signal sinks. It is particularly useful for modular, multiple radio systems. It utilizes a loop segment switching scheme that obviates the requirement of matrix switching.
2. Description of the Related Art
Modern modular radio systems typically utilize a "pool" of exciters to generate low power signals with a selected frequency and modulation, and a "pool" of power amplifiers which increase the low level signal from an exciter to the desired radiated power level. The system generally maps one exciter to one power amplifier. Connecting more than one exciter to a single power amplifier raises issues with linearity versus generation of spurious intermodulation distortion (IMD) products, and peak envelope power (PEP) derating of the amplifier with multiple signals (whereby the vector voltage limited power amplifier must have the input signals reduced such that the peak vector voltage input of multiple signals times the amplifier gain does not exceed the peak voltage output capacity of the amplifier to prevent severe IMD product generation).
In designing modern modular radio systems the designer is faced with an architectural challenge based on the fact that the system configuration uses modular exciters and banded amplifiers. There is a choice as to whether the exciter is hardwired to the amplifier or whether to provide a switch matrix to allow connection of any exciter output to any amplifier input. The reason for wanting to switch them is for fault tolerance, and being able to reroute around failed modules.
One of the key features of the new modular radio systems (typified by the US Department of Defense Joint Tactical Radio System (JTRS) is that the exciter module is capable of operating at output frequencies of 2-2000 MHz with selectable software-generated bandwidths and modulations. That is to say that the exciter is common across all frequencies, modes and waveforms. Modes and frequencies may be changed in multiples of microseconds to milliseconds without physical action; all features are switchable/selectable via software command busses.
On the other hand, the high power RF and antenna subsystem is generally still banded due to component and physics limitations. Typically, a military radio system is divided by frequency bands and their unique band attributes as follows:
HF (2-30 MHz) has 1000 watts transmitter output or more due to link power budget and atmospheric noise considerations, with physically large (35-50 feet tall) antennas commensurate with the wavelength; narrowband linear 3 KHz waveforms.
VHF Combat Net Radio (30-88 MHz) has 50 watt transmitters with 8-10 foot tall antennas, operates in line-of-sight (LOS) modes to manpack or handheld radios from larger base stations on platforms or movable command posts; non-linear narrowband waveforms on 25 KHz channelization.
UHF (225400 MHz) has 100 watt transmitters with 2-3 foot tall antennas, operates in LOS modes among platforms and movable command posts; linear and non-linear narrowband waveforms on 25 KHz channelization except special waveforms up to several megahertz bandwidth.
UHF SATCOM (240-318 MHz) has 200 watt transmitters with steerable directional antennas; linear and non-linear narrowband waveforms of 5 or 25 KHz; four 200 watt transmitters combined into one antenna via −6 db combining network, net of 50 watts per channel radiated power.
High UHF (>400 MHz) uses 100 watt transmitters (with exception of JTIDS, with dedicated higher power transmitters and antennas) with 1-2 foot tall antennas; linear and non-linear waveforms up to ten's of megahertz wide.
The point of the description of the transmitters used is that each band has a unique power output and power amplifier requirement. With modern technology and these differing requirements, the amplifiers generally used to satisfy the total frequency coverage needs include:
HF: Due to the high power needs, the HF amplifiers are segmented as separate devices operating only 2-30 MHz. High power devices with sufficiently large junctions typically have unsatisfactory characteristics for VHF/UHF operation.
VHF/UHF: The state-of-the-art allows construction of 30450 MHz 100 watt amplifiers, both linear and non-linear, using LDMOS silicon devices. Two or more amplifers are coherently hybrid-combined for higher power outputs (i.e., for satellite communications). Current LDMOS silicon devices cannot be broadbanded to obtain 30-2000 MHz in a single amplifier.
>450 MHz UHF: The state-of-the-art is shaky in this frequency range. Silicon devices are usable up to 2000 MHz, but due to the rapidly decreasing gain (up to a usable limit of about 2000 MHz), must be tuned and cannot be broadbanded except over a small band (typically 5-10% of tuned frequency). GaN and GaAs devices are not yet available with sufficient power density, and SiC devices are just being introduced into the market. Hence this band is typically covered with banded amplifiers.
Thus, in summary multiple banded amplifiers are required to meet the operational requirements of present military radio systems. However, one common exciter module can generate low level signals for all bands.
A particular example of the problem facing large multiple radio systems involves those found on military ships that may have upwards of twenty-five to fifty radios. These are traditionally connected to an RF crosspoint matrix switch to allow the system to reroute around failures and maintain critical communications circuits in the face of those failures. Newer systems being proposed under the Joint Tactical Radio System (JTRS) program may have closer to one-hundred channel radio systems, using common modular components, requiring a 100×100 RF matrix switch to achieve the traditional reconfigurability. Such a large size RF matrix switch will be heavy, expensive, and itself a reliability risk relative to the systems it is to reroute.
In attempting to determine whether to hardwire an exciter to an amplifier, or provide a switch matrix to allow connecting any exciter output to any amplifier input some of the factors to be considered are:
What is the mean time between failure (MTBF) and availability of the system with hardwired versus switched exciter/amplifier pairs?
What is the cost of an exciter crosspoint switch matrix?
Is the baseband switch at the digital input of the exciter sufficient switching, given that all exciters can operate at any mode and frequency?
This becomes a complex system trade. The motivation for wanting to switch any exciter to any amplifier/antenna must be understood, given that any exciter can generate any waveform at any frequency. The primary motivation is that the failure of an exciter would leave an unused amplifier/antenna channel. This could be resolved by matrix-switching a replacement or spare exciter into that amplifier, or simply having sufficient exciter and amplifier spares in each band to provide the required reliability/availability without switching (e.g., hardwired).
Assuming for discussion that switching is justified, then large systems (64 to 80 exciters) which require connecting any exciter to any amplifier would require a commensurate crosspoint matrix, which is a large and expensive hardware item, albeit one available as COTS.
Although the discussion above has been directed toward modular, multiple radio systems similar switching problems are equally applicable in many areas where switching is required between multiple sources and multiple sinks such in optical switching, data communications, energy related systems, etc. As will be disclosed below, the principles of the present invention apply equally to a variety of fields.


A clip has a retainer for securing the clip and a wire harness to a bolt protruding from a vehicle surface. The retainer includes a beam having an aperture with an inner wall. The aperture receives the bolt. A flange projects into the aperture from the wall. An opening in the wall opposite the flange communicates with a passage in the beam. A sliding component of the retainer has a flanged end for insertion into the passage and through the beam into the aperture. The flange and the flanged end of the component are received between selected threads of the bolt to clamp the bolt in the aperture. Projections extending from opposite edges of the sliding component are received in cavities along side walls of the beam passage in positions corresponding to the size of the bolt. The projections and cavities cooperate to secure the sliding component in the beam.

1. Field of the Invention
The invention relates in general to clips for securing wire harnesses to vehicle surfaces, and more specifically to a clip with a stud bolt retainer that can accommodate different-sized stud bolts and can be removed from the stud bolt without damage to the retainer and clip.
2. Discussion of Related Art
One type of a conventional wire harness clip is shown in U.S. Pat. No. 5,390,882. The clip comprises an open, contoured or curved shell to which a wire harness can be taped. The shell is integral with a flat section forming a stud retainer. The retainer includes an aperture through the flat section and upward-angled, flexible, radial grippers extending into the aperture from its inner circumferential wall. A threaded weld stud protrudes from a vehicle body panel or other frame surface and is forced through the aperture, securing the clip and thereby the wire harness to the vehicle. The grippers are flexed or bent by the threads until they are engaged between selected threads and friction fit against the threads. The traditional shape of the threads and the angle and design of the radial grippers hinder removal of the retainer from the stud. The insertion force of the stud into the beam aperture is relatively high, since the flat section has to be forced onto the weld stud through and against the grippers. During disassembly, or the reverse of insertion, the grippers cannot flex as readily and may often be damaged, reducing the ability of the retainer to clamp against the stud properly or even preventing reuse of the clip. In addition, it is more than likely that a different clip having specifically-sized aperture and projections has to be provided for each stud size.
U.S. Pat. No. 5,760,338 discloses a wire harness clip that can be released from a stud or bolt and reused. Resilient members with teeth for engaging the threads of the stud have free ends extending away from each other. The free ends can be gripped and forced apart to separate the teeth from the threads, allowing removal of the clip from the stud. However, the clip cannot be adjusted for different-sized studs while maintaining optimal engagement of the teeth and threads. The resilient members are not locked into position around the stud and it appears that they can be inadvertently released from the stud if accidentally bumped or jostled.
Prior art attempts to provide a clip that accommodates different types of threads include U.S. Pat. No. 5,423,647. A claw arrangement in a retainer is designed to absorb variations in the bolt pitch and still provide a strong holding power. But the retainer does not adapt to variations in stud or bolt size and it seems that each claw must somehow be manually retracted from the threads before attempting to remove the retainer from the bolt.

Adjustable and reusable stud bolt retainer


A gas delivery arrangement for respirators and anesthesia apparatus includes a radial flow compressor (10) with bent-backwards blades. The compressor impeller (11) is arranged in a stationary housing (14). The gas inlet (12) is located in the area of the axis of rotation of the compressor impeller (11) and the blades (13) extend from the gas inlet (12) in the area of the axis of rotation to the circular outer edge of the compressor impeller (11) and end there nearly tangentially. The free gas flow path between the outer edge of the compressor impeller (11) and the inner wall of the housing (14) passes over into the gas outlet (15) of the gas delivery arrangement in the direction of gas flow. The compressor impeller is driven by an electric motor and has a radius of up to 40 mm and a mass moment of inertia of up to about 4.times.10.sup.-6 kg.times.m.sup.2. The arrangement is an extremely compact gas delivery arrangement, which requires few components and no valves, can be used in a versatile manner and is able to change pressures in a highly dynamic manner, is provided by the subject of the present invention. The pneumatic resistance of the gas delivery arrangement according to the present invention is less than 4 mbar at a gas flow rate of 60 L per minute.

Such radial flow compressors have been known, in principle, and special designs of such radial flow compressors have also been proposed for respirators.
WO 87/01599 shows a radial flow compressor, which is driven by pressurized oxygen in order to pump an oxygen-air mixture to the patient. Electrically driven respirators or anesthesia apparatus without pressurized gas supply for intermittent respiration use mostly either reciprocating pumps or continuously operating compressors with valve control. Large-volume reciprocating pumps are unable to follow the spontaneous breathing of patients rapidly enough, and small pistons operated at high frequency generate undesired pulsations in the breathing gas. Continuously operated compressors require an external pneumatic circuit with valves and are therefore technically complicated; in addition, the increase in the temperature of the breathing gas is undesirable. In addition, there are devices which operate as double-flow side-channel compressors based on a special principle of action and permit intermittent forms of exhalation without additional valves based on the manufacture of highly complicated individual parts, and they comprise many components. However, as a consequence of the greatly sloped pressure-flow characteristics of this type of compressor, the necessary properties can be obtained only by means of an expensive control of the characteristics and by the use of a microprocessor.

Gas delivery means for respirators and anesthesia apparatus


An optical alignment composition, an alignment layer formed using the same with an excellent thermal stability, and an LCD having the alignment layer are provided. The optical alignment composition includes a multifunctional cinnamate compound and a cinnamate group containing polymer in a weight ratio of 1:9 to 2:8. Thus, an optical alignment composition and an alignment layer each having excellent thermal stability and alignment property can be obtained while adopting a non-destructive optical alignment method. Accordingly, an LCD with improved performance can be obtained.

1. Field of the Invention
The present invention relates to a liquid crystal display device (LCD), and more particularly, to an optical alignment composition, an alignment layer formed using the optical alignment composition, and an LCD having the alignment layer.
2. Description of the Related Art
In general, a liquid crystal has an intermediate property of a liquid and a solid, having the fluidity of a liquid and having the optical property of a solid, and can be changed in its optical anisotropy by an electrical field or heat. A liquid crystal display device (LCD) utilizes such properties. FIG. 1 is a sectional view of a general LCD.
Referring to FIG. 1, transparent electrodes 3 and 3' made of indium tin oxide (ITO) are formed on a pair of transparent substrates 2 and 2' made of glass. Insulating layers 4 and 4' and alignment layers 5 and 5' for aligning liquid crystals are sequentially formed on the transparent electrodes 3 and 3'. A spacer 6 for maintaining a constant cell gap is interposed between the alignment layers 5 and 5'. A liquid crystal material is injected into the cell gap to form a liquid crystal layer 7. Polarizing plates 1 and 1' for polarizing entering and transmitting lights are provided at the exterior of the substrates 2 and 2'.
One of the determining factors in the performance of an LCD is an appropriate alignment of liquid crystals. Alignment layers are generally used for the purpose of aligning liquid crystals appropriately. Among them, conventionally, the alignment layer formed by rubbing a polymer layer has been widely used. However, according to the rubbing treatment, dust or static electricity may be generated due to mechanical contact between a rubbing cloth and the alignment layer.
Thus, to solve the problem caused by the rubbing treatment, a non-destructive optical alignment technology has been developed. According to this technology, polarized light is irradiated into a photopolymeric alignment layer, causing anisotropic photopolymerization. As a result, liquid crystal molecules are uniformly aligned.
As the material of a photopolymeric alignment layer, a polycinnamate such as PVCN (polyvinyl cinnamate) or PVMC (polyvinyl methoxycinnamate) has been used. However, such polymers have poor thermal stability, although they have an excellent optical alignment property. In other words, the thermal stability of an alignment layer depends upon that of the polymer, which depends upon a glass transition temperature and cross linking density. Since the polycinnamate generally has a glass transition temperature of 100.degree. C. or below and is difficult to subject to a photo-reaction of 50% or more in a solid state, increasing the cross linking density is limited, which weakens the thermal stability of the alignment layer.

Optical alignment composition, alignment layer formed using the same and LCD having the alignment layer


An application document known to include malware (such as a document exploit) is opened and executed by its corresponding software application. Behaviors of this document (such as registry, file system, network and process) are monitored and recorded using internal software drivers and hook modules. A behavior report is generated and a baseline pattern is created including a number of regular expressions. A suspicious document of the same type as the monitored document is opened and executed by the same corresponding software application. Behaviors are monitored in the same way and a behavior report is generated. This behavior report is compared to the baseline pattern and a determination is made as to whether a document exploit is present. Known benign documents may also be opened, monitored and their behavior recorded, resulting in creation of a known benign pattern for the corresponding software application.

Attacks upon computer systems are increasingly becoming more sophisticated and targeted. One particular type of threat, known as an advanced persistent threat (APT), refers to targeted attacks that aggressively pursue and compromise chosen targets, and is commonly associated with a government or other group that has the resources to maintain such an attack. Often, such a long-term pattern of attacks is aimed at other governments, companies, and political activists. Individuals (such as individual hackers) are usually not referred to as being an advanced persistent threat because they rarely have the resources to launch a sophisticated attack or be persistent.
An advanced persistent threat is characterized by: targeting a specific organization or individual; gaining a foothold; accessing the target network; deploying additional tools; and covering tracks in order to maintain future access. One common method of attack, and usually the first vector of an advanced persistent threat, is to exploit a vulnerability in an application program, typically through one of its documents, in order to cause harm. The vulnerability may be some type of flaw, error or poor coding technique in the application program that allows the attacker to exploit the program for a malicious purpose.
This so-called "document exploit" can affect many types of software applications and their corresponding documents. For example, standard computer document types such as Flash files, PDF files, Word documents, Excel documents, PowerPoint documents, RTF files, etc., can be exploited because of flaws in their corresponding application programs. For example, one family of malware modifies PDF files in order to exploit vulnerabilities in Adobe Acrobat and Adobe Reader by executing JavaScript code when the file is opened. The embedded JavaScript may contain malicious instructions to download and install other malware. A computer may become infected when the user visits a compromised Web site or opens the malicious PDF file. This family may exploit over a dozen known vulnerabilities.
Even lesser-known software applications can be the subject of a document exploit, such as the Korean proprietary word processing application Hangul and its HWP file types. Even file types that users would not normally create and that would seem above suspicion are at risk. For example, the help files (extension ".HLP") in the Microsoft operating system are being used in targeted attacks because malware authors can use these files to call an operating system API for a malicious purpose.
A database of common vulnerabilities and exposures (the CVE database) keeps track of publicly known vulnerabilities using unique, common identifiers. For example, two of the most common vulnerabilities exploited by malware in Microsoft Word are CVE-2010-3333 and CVE-2012-0158. Not surprisingly, the methods used to exploit a Microsoft Word document (for example) will differ based upon the particular vulnerability chosen by a malicious program. Often, the payload delivered by the malware falls into particular categories such as launching another malicious process, crashing the computer, downloading another malicious file from the Web, or dropping a file from the original malware.
In addition to the vulnerabilities shown in the CVE database, many of the attacking methods used by a document exploit are well-known such as the stack-based buffer overflow attack, the heap spray attack, use of shell code, or invoking an unsafe method. Accordingly, and unfortunately, most if not all of the prior art detection techniques are based upon the known CVE database or based upon the known attacking methods. For example, static techniques based upon virus signatures only work for known document exploits; these techniques will not work for unknown exploits for which no signature yet exists. Emulation-based techniques have associated overhead, rarely open certain types of files, and often cannot monitor the real behavior of a document because of the emulation.
Other techniques such as private memory usage monitoring, NOP sled detection, string detection and null page allocation often are not helpful because they all attempt to detect the exploit known as "Heap Spray." If no heap spray technique is used in the document, these techniques will not be helpful. And, protection techniques such as ASLR and DEP are not able to stop well-constructed exploits. For example, exploit techniques such as "Return Oriented Programming" and "Information Leak" are ways to bypass both of these protection techniques. Finally, the above detection techniques can be unsuccessful or at best, inefficient, in the case of a zero-day attack.
Accordingly, a new method to detect document exploits that is more efficient, that does not adversely impact system performance, and that is effective in the case of the zero-day attack is desirable.

Document exploit detection using baseline comparison


An ink container opener having a first member having an opening formed therein; and, a second member received within the opening of the first member. The second member further has an opening for receiving an ink container for separating a top portion from a bottom portion of the ink container.

An ink container typically includes a container body and a container cap. The cap is usually ultrasonically welded, glued or heat staked to the body after the container has been filled with ink during initial manufacturing. Once the ink has been depleted from the container, the container can be reused by refilling it with ink. Refilling ink containers with ink is a two step process. First, access must be provided such as by breaking open and removing the cap from the cartridge. Second, the reservoir must be refilled. To assist in refilling the ink container, and as an alternative to removing the cap, the user usually drills holes through the cap to provide access into the interior of the container so that ink can be added. At times the ink container cap may be fabricated of a rigid plastic material that is difficult to penetrate using a hand-held drill bit which is typically supplied with ink refill kits. Thus, drilling holes into the cap can be difficult for the user, especially for a color ink container where three holes are required.
Accordingly, there is a need for a way to easily remove the cap from an ink supply container to enable the addition of more ink, thereby extending the useful life of the container. Thus, there is a need for an ink container opener that allows the consumer or user to remove the container cap without drilling holes into the cap.
One drawback of prior ink container openers is the lack of a firm grip for the container during a somewhat delicate procedure of separating the top and bottom portions of the container. Furthermore, another drawback of some of the openers is they can be used to only open one type of ink container. While these openers have been effective apparatus for opening containers, there is a need for an improved ink container opener having enhanced gripping and stability features. Furthermore, it is desirable to provide a cap removal tool which can be used with more than one type of ink container.

Ink container opener with multiple inserts for different container types


The present invention is directed to a method for treating a material to impart wrinkle reduction and temporary crease resistance thereto, and improve feel. The method involves: applying to said material a solution of a treatment composition in an amount effective to impart temporary crease and stain resistance, said fabric treatment composition comprising a hydroxy urea or hydroxy amide compound; and allowing said treatment composition to dry at ambient temperature,

The present invention relates to the use of a treatment composition comprising a hydroxy urea or hydroxy amide compound in the treatment of a material to reduce wrinkles, impart temporary crease resistance and improve fabric hand (feel), and increase moisture absorbance. More specifically, the method of the invention involves applying a solution of the hydroxy compound to a material, and allowing the material to dry at ambient temperature, without the application of an external heat source.
Clothing, fabric, and other materials, free of wrinkles are viewed in a more favorable light than the same materials that are wrinkled. Thus there have been many methods developed to reduce wrinkles on clothing and other materials, and to develop materials resistant to wrinkling. The use of thermosetting resins or reactants to impart crease resistance and dimensional stability to textile materials is well-known in the art. These materials, known as xe2x80x9caminoplast resinsxe2x80x9d, include the products of the reaction of formaldehyde with such compounds as urea, thiourea, ethylene urea, dihydroxyethylene urea, melamines or the like. A serious drawback to the use of such materials is that they contain free formaldehyde. This is present during the preparation and storage of the finishing agent and its use in treating textiles, on the treated fabric, and on the finished garments. Also, when the fabrics or garments made therefrom are stored under humid conditions, additional free formaldehyde is produced.
The presence of even less than one percent of free formaldehyde, based on the total weight of the product, is undesirable, not only because of its unpleasant odor, but because it is an allergen and an irritant, causing severe reactions in the operators who manufacture the agent and who treat and handle the treated fabrics and to persons who handle and wear garments fabricated from the treated fabrics.
Solutions containing lubricants such as silicone compounds are known to reduce interfiber friction, allowing fibers to slide past each other and thereby reducing wrinkling. Such compounds are described in the art such as in U.S. Pat. No. 5,968,404, and in WO 11/24857.
U.S. Pat. No. 5,879,749 describes compositions containing a poly-functional molecule having at least two functional groups selected from carboxyl, anhydride and amine which is crosslinked using a (hydroxyalkyl)urea crosslinking agent. U.S. Pat. No. 5,965,466 describes the use of hydroxyalkyl urea and/or xcex2-hydroxyalkylamide for imparting permanent press properties to a textile containing cellulose fibers. U.S. Pat. No. 4,076,917 describes xcex2-hydroxyalkylamides as curing agents for polymers containing one or more carboxy or anhydride functions. These references require a heating step following application of the composition to the fabric, in order to effect a cross-linking reaction.
Treating textiles with resin compositions that do not contain or evolve formaldehyde is also known, as in U.S. Pat. No. 3,260,565 which describes finishing agents formed by the reaction of alkyl or aryl ureas or thioureas with glyoxal. U.S. Pat. Nos. 4,332,586 and 4,300,898 describe alkylated glyoxal/cyclic urea condensates as crosslinking agents for textiles. U.S. Pat. No. 4,295,846 describes a finishing agent for textiles which is prepared by reacting urea or symmetrically disubstituted ureas in an aqueous solution with glyoxal. These agents, however, have the disadvantage of having marginal permanent press properties. Finishing agents formed by the reaction of ethylene urea with glyoxal are described in Japanese publication No. 5 3044-567, but they too do not have satisfactory properties.
Copending U.S. application Ser. No. 09/456,358 describes a textile antiwrinkling composition containing polyhydroxyalkyl urea crease resistance agents having at least two urea moities.
There is a need for a material treatment composition which can be applied to a material to reduce wrinkles and impart temporary permanent press properties, without the need to follow the application with the addition of an external heat source. Ideally the treatment composition should be one which does not emit formaldehyde. Surprisingly, it has been found that a hydroxy urea or hydroxy amide compound, when applied to a fabric by means such as a spray, will reduce wrinkles, without the need for the addition of an external heat source. This method provides consumers the ability to provide crease resistance properties easily and cost-effectively to clothing at home, and even the ability to reduce wrinkles on clothing being worn. Furthermore, there is a need for anti-wrinkling treatments that do not discolor the fabric. Additionally the treatment should not negatively impact stain removal unlike the silicones that are difficult to clean because they attract oily stains. Finally, there is a need for a material that does not leave the fabric with an oily type of finish. The method of the present invention fulfills these needs.
The present invention relates to a method of treating a material which comprises applying to the material an amount of a treatment composition which is effective to impart temporary crease resistance. The treatment composition comprises a hydroxy compound which is either a hydroxy urea or a hydroxy amide. The material treatment composition may be applied to clothing, fabric, and textiles; and without the need of an external heat source, reduce wrinkles and provide the material temporary crease resistance. In addition, there is no build-up of the composition on clothes or irons, and no residual flaking is noted, even on dark fabric. The treated material also has a tactile sensation of feeling soft, and increased moisture absorbance. Moreover, there is no discoloration of the fabric and the material does not hold on to oily stains unlike the silicones typically used.
This invention relates to a method for imparting wrinkle reduction, permanent press properties, and improved feel, and increased moisture absorbance to a material. As used herein, xe2x80x9ccrease resistancexe2x80x9d shall be synonymous with wrinkle resistance, durable press, dimensional stability, shrinkage resistance, and wrinkle recovery. The method involves applying a treatment composition of a hydroxy compound to a material, and allowing the material to dry at ambient temperature without application of an external heat source, to impart crease resistance properties to the material. The treatment composition is essentially free of formaldehyde and may be applied in the form of a solution or neat.
The material treated by the method of the present invention consists of a natural or synthetic material. The material may be a material such a leather, or a fibrous material. Fibrous materials may be natural, synthetic, or a mixture thereof. Such material includes, but is not limited to, fabrics, textiles, non-wovens, and finished products made from these materials. The material preferably is a cellulosic fabric or textile, and may be woven or non-woven, and includes 100 percent cellulosic fabrics, for example, cotton, rayon, and linen, as well as blends, for example, polyester/cotton or polyester/rayon . The fibrous material may also be a non-cellulosic natural or synthetic fiber, such as for example nylon, silk, and polyester. Both white and colored (printed, dyed, yarn-dyed, cross-dyed, etc.) materials can be effectively treated with the material treatment composition of the present invention. The materials may comprise new or used clothing including previously worn clothing and/or laundered clothing.
The hydroxy compound is either a hydroxy urea or a hydroxy amide. The hydroxy urea useful in the present invention is one containing one urea functionality and at least one hydroxyl functionality. The term urea, as used herein, refers to a Nxe2x80x94COxe2x80x94N moiety in which the other two bonds on each nitrogen atom form additional attachments, as for example those found in the illustrations and examples herein. The urea and hydroxyl functionalities may be separated from each other in the compound by one carbon atom. Preferably they are separated by at least two carbon atoms. The hydroxy amide useful in the invention is one containing at least one amide functionality and at least one hydroxyl functionality. Preferably the hydroxy compound should not be a formaldehyde emitter. The preferred compounds of the invention are either a hydroxyalkyl urea, or a xcex2-hydroxyalkyl amide, or a mixture thereof.
Preferred hydroxy urea compounds are derived from urea, and comprise only a single urea group, at least one hydroxyl group, at least two carbon atoms disposed between the urea group and each of the hydroxyl groups. The two carbons disposed between the hydroxyl and urea groups may be in linear, branched or substituted configuration. The hydroxy urea compound is represented by structure (I) as follows:
wherein R8 is H, methyl or ethyl, R9 is H, methyl or ethyl, and R10 is H, methyl or ethyl.
Preferred hyroxy urea compounds are N-2-hydroxyethyl urea, N,N-bis(2-hydroxyethyl)urea, tetrakis(2-hydroxyethyl)urea, tris(2-hydroxyethyl)urea, N,Nxe2x80x2-bis(2-hydroxyethyl)urea, N,Nxe2x80x2-bis(3-hydroxypropyl)urea, N,Nxe2x80x2-bis(4-hydroxybutyl)urea, N-methyl-D-glucourea, and 2-urea-2-ethyl-1,3-propanediol. Most preferably, the hydroxy urea compound is N,Nxe2x80x2-bis(2-hydroxyethyl)urea. Combinations of hydroxy urea compounds can also be used in the method of the invention.
The hydroxy urea compound is the reaction product of urea and an alkanolamine with the evolution of ammonia. Preferred alkanolamines include, but are not limited to, diethanolamine, monoethanolamine, 2-amino-2-methyl-1,3-propanediol, bis(hydroxymethyl)amino-methane, 2-methyl-3-amino-1-propanol and 2-methylaminoethanol. Processes for preparing the hydroxy urea compound is described in U.S. patent application Ser. No. 08/783,350 which is hereby incorporated herein by reference.
Preferred hydroxy amide compounds are xcex2-hydroxyalkyl amide compounds represented by structure (II) as follows:
In structure (II), A is a bond, hydrogen or a monovalent or polyvalent organic radical derived from a saturated or unsaturated alkyl radical wherein the alkyl radical contains from 1 to 60 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, eicosyl, triacontyl, tetracontyl, pentacontyl, hexylcontyl and the like; aryl, for example, mono-and dinuclear aryl such as phenyl, naphthyl and the like; tri-lower alkyleneamino such as trimethyleneamino, triethyleneamino and the like; or an unsaturated radical containing one or more ethylenic groups such as ethenyl, 1-methylethenyl, 3-butenyl-1,3-diyl, 2-propenyl-1,2-diyl, carboxy lower alkenyl, such as 3-carboxy-2-propenyl and the like, lower alkoxy carbonyl lower alkenyl such as 3-ethoxycarbonyl-2-propenyl and the like; R11 is hydrogen, lower alkyl of from 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, pentyl and the like or hydroxy lower alkyl of from 1 to 5 carbon atoms such as hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxy-2-methylpropyl, 5-hydroxypentyl, 4-hydroxypentyl, 3-hydroxypentyl, 2-hydroxypentyl and the isomers of pentyl; R12 and R13 are the same or different radicals selected from hydrogen, straight or branched chain lower alkyl of from 1 to 5 carbon atoms or one of the R12 and one of the R13 radicals may be joined to form, together with the carbon atoms, such as cyclopentyl, cyclohexyl and the like; n is an integer having a value of 1 or 2 and nxe2x80x2 is an integer having a value of 0 to 2 or when nxe2x80x2 is 0.
A preferred xcex2-hydroxyalkyl amide compound is represented by structure (III) as follows:
In structure (III), R11 is H, lower alkyl, or HO(R13)2C(R12)2Cxe2x80x94, n and nxe2x80x2 are each 1, xe2x80x94Axe2x80x94 is xe2x80x94(CH2)[m]xe2x80x94, m is 0-8, preferably 2-8, each R12 is H, and one of the R13 radicals in each case is H and the other is H or a C1-C5 alkyl; that is wherein R11, R13, and m have the meanings just given. The most preferred xcex2-hydroxyalkyl amide compound is represented by structure (IV) as follows:
In structure (IV), R13 is H or xe2x80x94CH3.
Specific examples of xcex2-hydroxyalkyl amide compounds are bis[N, N-di(beta-hydroxyethyl)] adipamide, bis[N,N-di(beta-hydroxypropyl)] succinamide, bis[N,N-di(beta-hydroxyethyl)] azelamide, bis[N-N-di(beta-hydroxypropyl)] adipamide, and bis[N-methyl-N-(beta-hydroxyethyl)] oxamide.
The xcex2-hydroxyalkyl amide compounds are either known compounds or may be prepared by treating an ester with an amine at a temperature in the range of from about ambient to about 200xc2x0 C. Suitable esters are prepared by esterifying the corresponding acid by standard esterifying procedures. Among the preferred acids used to prepare the xcex2-hydroxyalkyl amide crosslinking agents are oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, 1,4-cyclohexane and the like and alkyl derivatives thereof. Dimer and trimer acids may also be used. Suitable amines used to prepare the xcex2-hydroxyalkyl amide compounds are 2-aminoethanol; 2-methylaminoethanol; 2-ethylaminoethanol; 2-n-propylaminoethanol; 2,2xe2x80x2-iminodiethanol; 2-aminopropanol; 2,2xe2x80x2-iminodiisopropanol; 2-aminocyclohexanol; 2-aminocyclopentanol; 2-aminomethyl-2-methylethanol; 2-n-butylaminoethanol; 2-methylamino-1,2-dimethylethanol; 2-amino-2-methyl-1-propanol; 2-amino-2-methyl-1,3-propanediol; 2-amino-2-ethyl-1,3-propanediol and 2-amino-2-hydroxymethyl-1,3-propanediol. The xcex2-hydroxyalkyl amide compounds are prepared according to processes described in U.S. Pat. No. 4,076,917 which is hereby incorporated herein by reference.
The treatment composition of the present invention can be used either in the neat form, or as a solution. A solution can be in any solvent which forms a solution or suspension with the hydroxy compound. Examples of useful solvents include, but are not limited to, water, acetone and alcohols such as methanol, ethanol, propanols and butanols, and mixtures of such solvents. A preferred solvent is water. An aqueous solution containing the hydroxy compound preferably has a pH of from about 1 to about 12, more preferably from about 2 to about 10, and most preferably from 4 to 7. Most preferably, an aqueous solution containing the hydroxy compound has a pH of from about 3 to about 8. It is understood that any means of adjusting the pH of the aqueous solution may be employed in the method of the invention to achieve a desired pH. When used in a solution form, the solution may contain other materials including, but not limited to, surfactants, buffers, dyes, polymers, and fragrance.
Any method of applying the treatment composition to the material is acceptable. Some examples of application methods include, but are not limited to, spray or mist application, application in the laundering processxe2x80x94especially in the rinse cycle, application from a sheet of material containing the treatment compoundxe2x80x94for example in a dryer, and immersion in a solution containing the treatment composition.
A preferred method of applying the treatment composition to a material is by spray or mist application by means of a pump or aerosol, or other methods known in the art. One method, useful for individual use, is application from a spray or mist bottle. The treatment composition may be applied to clothing, which is being worn, as well as to clothing not being worn.
The material may be impregnated with an aqueous solution of the treatment composition. As used herein, xe2x80x9cimpregnatexe2x80x9d refers to the penetration of the solution into the fiber matrix of the material, and to the distribution of the solution in a preferably substantially uniform manner into and through the interstices in the material. The solution therefore preferably envelopes, surrounds, and/or impregnates individual fibers substantially through the thickness of the material as opposed to only forming a surface coating on the material.
The treatment composition may be applied to the textile in a textile manufacturing process as part of the durable press finishing operation. Where the textile is not treated in a textile manufacturing process, the treatment composition may be applied in a laundering process, most preferably to rinse water in the rinse cycle of the laundering process at home or at a laundromat.
The treatment composition may also be transferred to the material to be treated through contact with another material impregnated with the treatment composition. An example would be the addition to a dryer or tumbling device of a sheet containing the treatment composition of the invention, and the transfer of the treatment composition to laundry through contact in the dryer. Since heat is not required for the method of the present invention, this method of application is useful on no-heat or low-heat settings.
Additionally, the treatment composition may be applied by soaking the textile in a solution containing the treatment composition.
The material treated with the treatment composition of the present invention is dried at ambient temperature, without the need for an external heat source. Application of an external heat source could speed the drying process, but is not required for the method of the present invention.
The hydroxy compound is present in an amount sufficient to provide about 0.00001 to about 10 percent of hydroxy compound in the material based on the oven-dry weight of the material. Preferably, the hydroxy compound is present in an amount sufficient to provide from about 0.1 to about 5 weight percent, and more preferably from about 0.5 to about 2 weight percent of hydroxy compound in the material based on the oven-dry weight of the material.
A dilute solution of the material is typically sprayed on to the fabric. The spray solution may contain 0.001 to 20 weight percent of the hydroxy urea compound, preferably 0.1 to 10 percent and most preferably 0.5 to 5 percent.
The method of the present invention provides crease resistance properties to materials treated therewith. Moreover, the treated textiles have a tactile sensation of feeling soft and retain their smoothness even after laundering.

Method for reducing wrinkles and improving feel in fabrics

Abstract: wherein said hydroxy urea compound comprises one urea and at least one hydroxyl group and said hydroxy amide compound comprises at least one amide group and at least one hydroxyl group. The material treatment is useful in reducing wrinkles in clothing, improving the feel of fabrics, and increasing the moisture adsorbence and retention in natural and synthetic fabrics.

National Starch and Chemical Investment Holding Corporation