text:
|Publication number
|Publication type
|Application number
|Publication date
|Mar 23, 1993
|Filing date
|Apr 15, 1991
|Priority date
|Jun 19, 1989
|Fee status
|Publication number
|Karl Moschner
|Original Assignee
|Lever Brothers Company, Division Of Conopco, Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (27), Non-Patent Citations (2), Referenced by (18), Classifications (14), Legal Events (4)
|External Links: USPTO, USPTO Assignment, Espacenet
This is a continuation application of Ser. No. 07/368,437, filed June 19, 1989 now abandon.
This invention pertains to the field of bleaching articles and compositions for use in washing laundry articles.
Bleaching products for use in laundering of fabrics conventionally have been sold in the form of powders and liquids. Consumers have thus been required to measure appropriate dosages from containers holding these products each time they wish to bleach a load of laundry. This measuring process has several drawbacks which are perceived by consumers as rendering liquid or powder bleach inconvenient: the liquid or powder products are easy to spill and not simple to measure accurately. Moreover, consumers usually use about the same amount of bleach for each wash; thus, remeasuring the amount they desire repeats a step performed many times before. Bleach compositions have the additional problem that bleach activity is lost over time; this is especially so for chlorine bleaches in an aqueous liquid.
Liquid bleach compositions in several forms are known, e.g. liquids, powders or pastes (U.S. Pat. No. 4,105,573). It has sometimes been deemed desirable to thicken liquid bleaches. Bleach composition thickeners have included clay, alone or combined with certain polymers (U.S. Pat. Nos. 4,116,849 and 4,116,851) as well as with mixtures of detergents (U.S. Pat. No. 4,337,163); cellulose derivatives and colloidal silica (U.S. Pat. No. 4,011,172).
Delivery of bleach to a washer is made somewhat simpler by use of a pouch. Dry particulate bleach has thus been added in water-soluble film packets (U.S. Pat. No. 3,644,260) as well as in porous pouches (U.S. Pat. No. 4,286,016). Indeed, U.S. Pat. Nos. 4,638,907 and 4,659,390 disclose adding several cleaning actives at once, between two layers of polymeric material laminated together, in a product which segregates each active from the others.
Less common than pouch-delivery of bleach has been delivery of dry chlorine bleach particles by water-soluble sheets (U.S. Pat. No. 4,532,063; 4,557,852 and 4,654,395).
There has been little use of non-water soluble sheet delivery systems for bleach. Applicant believes such systems may afford significant benefits over the art.
Yet certain disadvantages arise with single sheet-type laundry articles. Thus, some substrates are weakened and torn apart by washing, leaving unpleasant pieces to be removed from laundry by the consumer. Many substrate materials for carrying the bleach composition are not bleach-stable and thus disintegrate during storage or become unattractive to use. The requirements of mechanical and bleach stability restricts the substrate materials which may be used.
Even if the substrate is bleach stable, the composite bleaching article should retain its pleasant feel and texture during storage. Some articles lose their pleasant feel and become brittle due, it is believed, to adsorption of ambient moisture. The need to impart a lasting hand and resilience to the bleaching articles also affects the substrates, as well as the chemical compositions, which may be used.
There are further difficulties in processing single sheet-type laundry articles. For example, the bleach composition applied to the sheet should preferably be a viscous material which does not tend to run off the substrate. Additionally, aqueous chlorine bleach compositions have insoluble bleach particles which may not be easily suspended. Syneresis in the bleach composition to be applied to the substrate thus may cause uneven bleach doses from sheet to sheet.
Accordingly, it is an object of the present invention to provide a bleaching article in the form of a bleach-carrying substrate which is flexible when handled, and has a pleasant supple feel rather than a wet, greasy or tacky feel.
It is also an object of the present invention to provide an effective bleaching article for use in an automatic washing machine for laundry fabrics.
Another object of the invention is to provide a bleaching article that is simple to manufacture and convenient to store.
It is a further object of the present invention to provide a bleaching article which does not suffer from loss of bleaching activity and does not suffer physical damage in storage or in use. Physical damage includes shredding of the substrate in the wash as well as substantial flaking off of bleaching composition from the substrate surface.
It is yet another object of the invention to provide an aqueous bleach composition which does not suffer from phase separation and may be applied to a flexible substrate.
In one embodiment of this invention, an aqueous liquid bleach composition comprises 20-90% of chlorine bleach compound, 2-50% of a dispersant and water, the composition forming an aqueous slurry having a pH of 5 to 8. The viscosity is from 100 to 100,000 centipoises at 25� C., preferably from 500 to 6,000 centipoise. The slurry may be further thickened by an alkali, metal salt.
The aqueous slurry may further comprise 2-35% of a cobinder material which contributes to binding undissolved particles of bleach to a flexible substrate. The slurry may further optionally include 0.1-10% surfactants and 0.1-10% fluorescent whitening agent.
A bleaching article is provided comprising:
( i) a flexible substrate; and
(ii) a dried bleaching composition carried on said substrate, said composition comprising:
a. 20-90 wt. % of a chlorine bleach, and
b. 2-50 wt. % of a dispersant material,
the dried composition being derived from an aqueous bleach slurry having pH of 5 to 8. The dried bleaching composition is substantially free of free water but may have up to 20% water of hydration.
It is important that the components of the slurry and bleaching article are bleach stable. Suitable dispersants, cobinders, substrate materials, etc. are identified as bleach stable by having ignition temperature (defined below) of at least 150� C., chlorine scavenging half life (defined below) of over 24 hours and chlorine capacity ratio (defined below) of less than 10% of their weight.
Once the liquid bleach composition has been dried to the substrate, the level of water of hydration adsorbed by the bleaching article depends on ambient humidity conditions and the composition of the dried bleaching composition. Certain suitable components of this composition (e.g. the dispersant or cobinder) are hygroscopic and may absorb waters of hydration from ambient humidity. A preferred embodiment has dispersant and cobinder components which have relatively little hygroscopicity.
A method of bleaching laundry and/or fabrics is further an aspect of the present invention: in this method, the bleaching article described above is placed in the washing machine with laundry and run through the full wash cycle. The bleach slurry material dried on and into the substrate dissolves or disassociates from the substrate to release active chlorine into the wash water.
FIG. 1 diagramatically illustrates the rise in the half life of chlorine in samples in the presence of a polyanionic dispersant.
FIG. 2 illustrates the apparatus used in the ignition tests in Example 4 below.
An aqueous bleach slurry composition may include 20-90% chlorine bleach, or 30-70%, or 35-65%. (Unless otherwise noted, all percentage amounts in this specification indicate % by weight.) The amount of bleach in the slurry may be chosen to deliver a certain amount of bleach to the wash.
The chlorine bleach compounds suitable for the thickened aqueous slurry should have low water solubility and good bleach performance on a weight basis. Suitable types of bleach compounds include chlorinated isocyanurates and halo hydantoins. Suitable chlorinated isocyanurates include sodium dichloroisocyanurate and its dihydrate ("NaDCC"), potassium dichloroisocyanurate, trichloroisocyanurate and the like. One commercially available sodium dichloroisocyanurate dihydrate which may be used in the slurry is CDB Clearon, ex Olin Corp., sold as a powder with particle size of from about 1 to about 200 microns. Among the halo hydantoins suitable for the slurry are dialkyl hydantoins, alkylaryl hydantoins or diaryl hydantoins. More particularly, these include 1,3-dichloro-5,5-dimethyl hydantoin ("DCDMH"), N-monochloro-5,5-dimethylhydantoin, methylene-bis 1,3-dichloro-5-methyl-5-n-isobutylhydantoin, 1,3-dichloro-5-methyl-5-n-amylhydantoin, bromochloro-5,5-dimethyl hydantoin ("BCDMH") and the like.
Other useful bleach compounds are trichloromelamine, N-chloromelamine, monochloramine, dichloramine, paratoluene sulfondichloroamide, N,N-dichlorooxodicarbonamide, N-chloroacetyl urea, and N,N-dichlorobiuret, chlorinated dicyandiamide, dichloroglycoluril, N,N-dichlorobenzoylene urea, and N,N-dichloro-P-toluene sulfonamide and mixtures, etc.
The aqueous slurry has pH of about 5-8. As demonstrated in Example 1 below, at preferred pH 5.5 to 7.5, bleach half life is nearly doubled over the half life at pH 5.0. And at most preferred pH 6.0 to 7.0, bleach half life is triple that at pH 5.0.
The thickened bleach composition may comprise several components in addition to bleach and water. But because the bleach slurry is more harsh than commercial caustic chlorine solutions (owing to the higher available chlorine concentration), and the neutral pH increases reactivity of free chlorine, hypochlorous acid and its salts, many compounds are not stable in such an environment. If components chosen are not bleach-stable, they may impair production of the bleach slurry, or render it unattractive or non-functional.
Three tests were developed to identify components which are compatible with the strongly oxidizing slurry: the ignition test, the chlorine scavenging test and the the chlorine capacity test, described in Examples 4 and 5 below. Satisfactory results for each of the tests are indicated in these Examples. However, it should be noted that a satisfactory result in one test does not indicate a component has bleach stability; rather, one must consider the results of all three tests.
Aside from such cosmetic and operational considerations, the bleach slurry and article require care in manufacture to avoid the risk of exothermic reactions. Ammonium compounds must not be used under any circumstances in the bleach slurry since they can give rise to chloramines. Of particular concern is the accidental use of the common ammonium salts of polymeric acids. Trichloramine is one of the most significant hazards faced when working with chlorine bleach. The chlorinated isocyanurates will generate chloramines in the presence of ammonia or ammonium salts or on their own in high concentrations at 10<pH<5. Other nitrogen compounds should also be avoided. Experience has shown that violent decomposition may occur without warning.
The bleach slurry further includes 2-50% by weight of a dispersant material. The dispersant acts to reduce solubility of the bleach, thereby salting out chlorine bleach. The result of this salting out is to increase the level of insoluble chlorine bleach in the slurry, thus increasing the viscosity of the slurry. Several dispersant materials also contribute to binding the dried slurry to the substrate in bleaching articles described below.
Suitable dispersants are those which have satisfactory ignition temperature, chlorine scavenging half life and chlorine capacity as defined in Examples 4 and 5. These dispersants include: oligomeric or polymeric polyanionic materials. These materials may be straight chain or branched. Suitable polymeric materials include homo- and copolymers of acrylates, methacrylates, maleates, vinyl acetate, styrene and sulfonated styrene. Copolymeric materials may have regular or block structures. Further suitable polymeric materials include sulfonated polystyrene-co-maleate and polyvinyl sulfonate. Preferred dispersants include polyacrylates and copolymers of acrylic and maleic acid.
The molecular weight of the polymeric polyanionic dispersants should be from about 1,000 to about 100,000, with weights of about 5,000 to about 50,000 being preferred.
Suitable oligomeric materials include homo- or co-oligomers of the monomeric materials identified above, and should have molecular weights of about 200 and 1,500. A suitable commercially available product is Belclene (ex Ciba Geigy), an oligomer of maleic acid available in molecular weights of 400-600 and 600-800.
Several inorganic salts may be used as auxiliary dispersants in the slurry. The greater solubility of these salts further reduces the solubility of the bleach. These salts include alkali or alkaline metal salts of mono-phosphates, sulfates, phosphonates and sulfonates. Potassium salts have the surprising ability to impart significantly greater viscosity, especially in combination with polymeric dispersants. Common dispersant materials such as polyphosphates are unsuitable because they have low solubility with respect to chlorine bleach. For example, when sodium dichloroisocyanurate is added to a solution of sodium diphosphate, the latter crystallizes out of solution. Sodium chloride is also unsuitable since chloride accelerates loss of chlorine bleach activity.
The preferred dispersant materials are the polymeric polyanionic compounds. These have been found to impart lowered solubility to the bleach in the slurry. The resulting higher viscosity is due, it is believed, to the greater amount of insoluble bleach and, in part, the polymeric dispersant molecules (see Example 3 below). But the polymeric dispersants also impart phase stability to the slurry: these dispersants help disperse the bleach particles in the slurry and prevent unattractive settling out, as demonstrated in Example 2.
Depending on the amount of dispersant added, the slurry viscosity may range from 100 to 10,000 centipoises, at 25� C. as measured with a Haake Rotovisco viscometer model RV-3 and either an MK-50 or MK-500 measuring head and an MV1 and SV1 cup and spindle. It is preferred that slurries have viscosity less than 6,000 centipoises for easy pouring; viscosities of less than 3,000 are more preferred, with viscosity from 500-1,500 imparting desirable pouring speed with attractive rich consistency to the slurry. The viscosity of the bleach slurry is examined in Examples 6.
Examples 1, 2 and 3 which follow illustrate the effect of neutral pH and dispersant level on bleach activity and physical stability of the bleach slurry.
The bleaching strength of an aqueous solution containing a chlorine bleach is expressed in terms of available chlorine. This strength, or oxidizing power, of the solution is measured by the ability of the solution to liberate iodine from an acidified iodide solution in a standard iodometric titration. This oxidizing power normally diminishes the longer dry chlorine bleaches are exposed to water, and can even be lost when most of the chlorine bleach is present as suspended particles.
Buffered aqueous solutions of 5% sodium polyacrylate (molecular weight 10,000) at pH values of 4.2, 4.9, 5.3, 6.0, 6.8, 7.0, 7.2, 7.4, 7.5, 7.7, 7.8 and 8.3 are made. Sodium dichloroisocyanurate dihydrate is added to give a concentration of 2000 ppm av. Cl2 in each solution. By performing iodometric titration of acidified aliquots periodically, the half life of chlorine in each solution is determined. At pH 4.3 and 8.2, half life is only about 50 hours. As FIG. 1 shows, in the presence of a polyanionic dispersant, the half life rises significantly between pH 5-8, is quadrupled at pH of 5.5-7.5 and quintupled at pH of 6.0-7.0. These are significant increases in half life: at preferred pH of 5.5 to 7.5, half life is nearly double that of pH 5.0, while at most preferred pH 6.0 to 7.0, half life is tripled.
The role of the dispersant as a stabilizer of the slurry is seen in the following test, where six 200 g slurries are mixed with 107 grams of bleach and different amounts of water (42-67 grams) and polyacrylate dispersant (51-26 grams of LMW-100N ex Rohm & Haas Corp., neat polymer molecular weight 10,000). The slurries are mixed well with a glass stirring rod and then transferred to 250 ml graduated cylinders with ground glass stoppers. Twenty four hours after mixing slurries 1 through 6, the settling of bleach particles in each is read by measuring the total slurry volume (Vt) and the volume of clear supernatant at the top of the slurry (Vs). The percentage of the total slurry which forms clear supernatant indicates the volume of slurry from which bleach has settled.
______________________________________ % by Vt Vs weight (in (in Vs/VtSlurry Components of slurry mls) mls) (%)______________________________________1 107 g bleach 53.5 115 6 4.7 42 g water 36.3 51 g polyacrylate 10.22 107 53.5 127 8 6.1 47 37.3 46 9.23 107 53.3 132 11 8.6 52 36.3 41 8.24 107 53.5 128 13 9.8 57 39.3 36 7.25 107 53.5 132 15 11.4 62 40.3 31 6.26 107 53.5 132 17 12.9 67 41.3 26 5.2______________________________________
As the amount of dispersant falls from 10.2 to 5.2 weight %, there is a corresponding increase in the amount of phase separation from 4.5 to 12.9 supernatant volume %. This shows that polyacrylate dispersant increases phase stability of the chlorine bleach slurries.
Bleach sheet articles are prepared in a fume hood by painting the day old slurry onto swatches of International Paper 9335064 polyester nonwoven. The articles are evaluated after drying over night at ambient 27% relative humidity.
______________________________________Dispersantin original slurry(wt %) Sheet Evaluation______________________________________10.2 excellent, flexible, very low dusting9.2 good, flexible, low dusting8.2 fair, dusty, limited web penetration7.2 fair, similar to 8.2% formulation6.2 unacceptable, too dusty5.2 unacceptable, too dusty______________________________________
Thus, the greater the amount of dispersant, the more retentive is the dried slurry to the substrate.
Three slurry compositions are made with the following ingredients:
______________________________________A B C______________________________________30 g NaDCC bleach 30 g NaDCC bleach 30 g NaDCC bleach10 g polyacrylate 10 g polyacrylate 10 g polyacrylate50 ml water 50 ml of 1M 50 ml of 1M Na phosphate K phosphatepH 7 pH 7 pH 7______________________________________
The compositions A-C are made by adding water to a vessel, followed by phosphate salt if any, then polyacrylate and finally bleach.
Each of the three bleach slurries is tested for the amount of chlorine present in the aqueous phase only. This is done by standard iodometric titration. The following levels of available chlorine are found:
______________________________________A B C______________________________________5.5% av Cl2 4.1% av Cl2 1.5% av Cl2(10% bleach) (7% bleach) (3% bleach)______________________________________
Usually, NaDCC is soluble in water up to about 35%. Thus, the dispersant polyacrylate alone reduces the amount of available chlorine in the aqueous phase of the slurry down to only about 10%. Phosphate salts, especially potassium phosphate, reduce the level even more, and can even be seen to increase the viscosity significantly.
While the polyacrylate acts as a binder for the bleach particles when dried, the slurry may further include an adhering substance, and further reducing the level of dusting by dried slurry from substrates. The adhering substance is believed to play a role in binding the undissolved bleach particles to the substrate. Suitable adhering substances, or "cobinders" have satisfactory ignition temperature, chlorine scavenging half life and chlorine capacity and include latexes.
(As will be discussed below, some substrates are composed of fibers held together by a resinous substance. The resinous substance, usually called a "binder", is present on the substrate fibers when received from the manufacturer. In this application, the term "co-binder" is used as a synonym for adhering substance, and is not to be understood, except for the circumstances explained below, as a binder material on a substrate.)
It is desirable to incorporate one or more cobinder materials into the bleach slurry for several reasons. The cobinder improves retention of the dried slurry to the substrate during storage. Also, cobinders such as film forming latexes have significantly lower hygroscopicity than many of the suitable. dispersant materials (e.g., polyacrylate). Thus, a slurry, and bleach sheet articles coated therewith, having a blend of dispersant and co-binder, absorb less ambient humidity. In addition, latexes with low glass transition temperature (Tg) are more flexible and less brittle than polyacrylates and thus contribute to a better "hand" for the bleach sheets.
The bleach slurry may include 2-35%, preferably 5-30% and most preferably 8-25% co-binder.
The bleach slurry may be formulated without surfactant: added directly to the wash the slurry bleaches well. Moreover, the slurry readily penetrates substrate materials despite the hydrophobic character of polyester and polyolefin substrates. Nevertheless, certain surfactants improve wetting of the slurry on the substrate and thereby assist application of the slurry to a substrate and foster wetting of the sheet in the wash cycle.
Surfactants are selected based on their performance and the bleach compatibility criteria used for dispersants (see Examples 4 and 5). Suitable surfactants among the anionics include C8 -C22 soaps; aryl sulfonates, available as Dowfax surfactants ex Dow Chemicals; long chain (C8 -C22) alkyl sulfates and sulfonates, and C6 -C18 alkyl benzene sulfonates. These alkyl groups may be straight or branched. Two commercially available branched alkylated anionics suitable for the bleaching article are sodium heptadecyl sulfate (Niaproof 7 ex Niacet Corp., Niagara Falls, N.Y.) and sodium 2-ethyl-hexyl sulfate (Niaproof 08 ex Niacet Corp.). Suitable nonionic surfactants include amine oxides.
While soaps, Dowfax and alkylbenzene sulfonates may improve substrate and bleach article wetting, they may also lead to deleterious foaming under certain processing conditions. Thus, levels of these materials should be minimized to 0.1-10%, or preferably 0.5-5% surfactant, or most preferably 1-3%. Surfactant amounts may be greater than 10%, i.e. up to 15 or 20%, but such levels will not significantly improve results.
Fluorescent whitening agents may optionally be included in the slurry. These are generally known to provide brightening benefits in the wash. However, most fluorescent whitening agents lose their activity in the presence of chlorine bleach, making it difficult to deliver fluorescers from a bleach system. A few special fluorescer materials, from the family of sulfonated stilbenes are more resistant to oxidative degradation. These include Tinopal CBS-X and Tinopal RBS-200 (ex Ciba Geigy and described in U.S. Pat. No. 4,460,485, hereby incorporated by reference) and Phorwhite BHC-766 (ex Bayer-Mobay). Any sulfonated stilbene fluorescer may be incorporated in the bleaching composition, however, the three identified fluorescers are preferred.
Phorwhite BHC-766 is the most effective of these whiteners, because it loses less activity than Tinopal CBS-X, and reacts less with the chlorine of the thickened bleach slurry than RBS-200. Phorwhite BHC-766 has additional benefits in being readily dispersible in the bleach slurry and retaining stability under processing and storage conditions. -The stability of Phorwhite BHC-766 is attributed to low reactivity and low solubility in the aqueous phase of the slurry. (See Example 7 below.)
The thickened bleach composition may contain from 0.01-10% fluorescing agent, or 0.5-5% or 1-3%.
A preferred embodiment of the bleach slurry comprises 40-60% chlorine bleach, 4-18% dispersants and binders, 0-10% fluorescer and 25-60% water.
The components of the aqueous bleach slurry may be mixed in any order using conventional equipment for making aqueous dispersions.
As indicated above, all the components of the slurry may be added to the water base as liquid solution or suspension or as a solid. When one or more of the oomponents are in liquid form (as when LMW-100N ex Rohm & Haas Corp., a 40% solution of polyacrylate is used), it is useful to add such liquid components to the water base before adding any solid ones. This is because some of the solid components may significantly increase viscosity of the aqueous composition. Thus, for example, if powder chlorine bleach is added to water, the slurry formed gradually becomes more and more viscous. Mixing in liquid components prior to making the aqueous composition becomes viscous assures thorough dispersion of all components throughout the slurry. Accordingly, a preferred method of stabilizing an aqueous bleach composition against phase separation comprises: adding 2-50% by weight of a dispersant material to an aqueous base, neutralizing this mixture to a pH of 5 to 8, and adding 20-90% by weight of a dry chlorine bleach to the neutralized mixture to form the bleach slurry.
In mixing the liquid components into the water base, conventional mixing machinery and techniques may be used; the mixing should run as long as needed to impart substantial homogeneity to the aqueous composition.
The addition of solid components may also be performed using conventional mixing machinery techniques. However, it is preferred to employ a high shear mixer, such as a Cowles mixer, if solid bleach is added to the aqueous base. The high shear imparted by this mixer is believed to mix the components better than non-high shear mixers.
When solid components are added to the water or aqueous base, it is preferred to add them gradually with constant mixing to avoid clumping. It is even more preferred to add solid components in constant weight amounts to the base followed by a set amount of time to mix the newly added solid adequately into the base.
Other components beside bleach may be added as solid, for example, the fluorescing agent. When adding solid components used in low amounts, it may be desirable to add them to the aqueous base prior to the bleach. Such an order of addition may mix the fluorescing agent more evenly through the entire slurry.
Alternatively, all the solid components may be combined and mixed when dry then added to the aqueous base.
Substrates employed herein are water-insoluble and are solid or substantially solid materials. They can be dense or open in structure, preferably the latter. Examples of suitable materials which can be used as a substrate include foam, sponge, paper, woven or nonwoven cloth. The absorbent capacity, thickness and fiber density of the substrate are not limitations on the substrate material which can be used herein, so long as the materials exhibit sufficient wet-strength to maintain structural integrity through the complete washing cycles in which they are used. Substrate materials, like non-bleach components of the bleach slurry, should have satisfactory ignition temperature, chlorine scavenging half life and chlorine capacity (see Examples 4 and 5).
The substrate may have any one of a number of physical forms such as sheets, blocks, rings, balls, rods or tubes. It is understood that the bleaching article described herein as a sheet may be any of these alternate forms. Such forms are preferably amenable to unit usage by the consumer, i.e. they should be capable of addition to the washing liquor in unit amounts, such as individual sheets, blocks or balls and unit lengths of rods or tubes.
The nonwoven fabric substrates usable in the invention herein can generally be defined as thermally bonded or adhesively bonded fibrous or filamentous products, having a web or carded fibre structure (where the fibre strength is suitable to allow carding) or comprising fibrous mats, in which the fibres or filaments are distributed haphazardly or in random array (i.e. an array of fibres in a carded web wherein partial orientation of the fibers is frequently present as well as a completely haphazard distributional orientation) or substantially aligned. The fibres or filaments can be natural (e.g. wool, silk, wood pulp, jute, hemp, cotton, linen, sisal or ramie), synthetic (e.g. rayon, cellulose, polyvinyl derivatives, polyolefins, polyamides or polyesters) or mixtures of any of the above. Examples of materials suitable to carry the thickened bleach composition include International Paper Co. code 9335064, a point-bonded polyester fiber material; Scott 6724, a polypropylene fiber material; Scott 6815, a polyester fiber material; and Reemay 2200, a polyester fiber material.
A preferred example of a thermally bonded nonwoven fabric substrate is the point-bonded polyester nonwoven fabric with weight of 1.25 ounce per square yard available from the International Paper Company, code 9335064.
However, it is noted that certain adhesive bonded substrates are not suitable for the bleaching article. The reason for adhesively bonding some substrates is that their fibers are not amenable to thermal bonding and must be adhesively bonded. When incorporated in the article, these substrates tend to become brittle and crumble in storage or to collapse and disintegrate in the wash, with the unpleasant result of releasing the thousands of fibers through the laundry. It is believed the undesirable brittleness and substrate disintegration are due to incompatibility of the adhesive binder on the substrate with bleach.
It is of course preferred that any adhesive bonded substrate employed for the bleaching article be bleach-stable. However, manufacturers of synthetic fiber substrate rarely disclose which adhesive material they use on the substrates. Thus, to identify substrates with bleach-stable adhesive binders, the chemical compatibility tests described below in Examples 4 and 5 may have to be run. Alternatively, one may subject the substrate material to mechanical and chemical compatability tests described below.
(In some cases, the resinous binder holding substrate fibers together may also help bind bleach particles to the substrate. Only in these cases does the adhesive substrate binder act as a "co-binder" or adhering substance for the bleach slurry. Generally, the bleach slurry applied to the substrate should include cobinder to assure sufficient binding of particles to the substrate. Resinous binders which are believed to help bind bleach articles in this manner include urethane binders.)
While these fibers have usually appeared in adhesively bonded substrates only, they are now appearing in substrates having blends of 2, 3 or more fiber types. A fiber blend may mix rayon with a fiber usually thermally bonded, e.g. polyester. Such substrates are also fully suitable for the bleach article and include 7332, a polyester, rayon, and nylon mixed fiber material; 7320, a polyester rayon mixed fiber material, Stearns & Foster F-4334, a 50/50 rayon/polyester blend that is acrylic resin bonded. Depending on the proportions of the fibers, the entire substrate may be entirely thermally bonded with no adhesive binder used at all.
A further class of substrate material that can be used in the present invention comprises an absorbent foam like material in the form of a sheet. The term absorbent foam-like material is intended to encompass three dimensional absorptive materials such as "gas blown foams", natural sponges and composite fibrous based structures such as are disclosed in U.S. Pat. Nos. 3,311,115 and 3,430,630 specifically incorporated herein by reference. A specific material of this type is a hydrophilic polyurethane foam in which the internal cellular walls of the foam have been broken by reticulation. Foams of this type are described in detail in U.S. Pat. No. 3,794,029 which is hereby incorporated by reference.
The substrate should be mechanically and chemically compatible with the bleach slurry and its processing and use conditions. Substrate materials that are mechanically compatible with conditions of use, i.e. which pass through the dryer cycle substantially without damage are preferred, are those which do not undergo minor changes in appearance during the wash cycle, viz., pilling, pulling, tearing, etc. Mechanical compatibility of the substrate is tested by subjecting a sheet substrate to actual wash and dry conditions. A normal sized sheet about 9" by 11" sheet is added to a washing machine. The machine has a 17 gallon capacity and is loaded with 6 pounds of white cotton ballast plus the sheet and a recommended amount of laundry detergent (e.g., 97 grams of Surf). The wash cycle is run on hot in 17 gallons of Edgewater, NJ municipal water at 130� F. for 15 minutes with a 5 minute rinse. The ballast with the sheet is then added to a clothes dryer and dried at normal or high heat settings. A polyester fiber substrate (Reemay 2200 ) survived these steps intact while showing some pilling, while a 50/50 rayon/polyester resin bond substrate (Stearns F-4355) disintegrated into a mass of shredded fibers. Other traits which desirable substrate materials should have include suitable softness and air porosity.
The chemical, or bleach, stability of different substrate materials should be determined by subjecting candidate substrate materials to the tests described in Examples 4 and 5 to treatment with concentrated chlorine bleach in a fume hood. A 3" by 3" swatch of the substrate is soaked for one hour at room temperature in one liter of an approximately 1000 ppm av. Cl2 hypochorite solution in 0.1 M phosphate buffer at about neutral pH. The bleach solution may be about one-fiftieth dilution of Clorox brand bleach. Phosphoric acid or aqueous sodium hydroxide may be used to adjust pH of the solution. The swatch is then removed from the bleach solution, squeezed dry and rinsed under cold running tap water, and air dried.
A control swatch is soaked in one liter of water for an hour at room temperature, then squeezed dry, rinsed and air dried. The standard tensile strength of each swatch is then measured. The tensile strength of the test and control swatch may be determined by the test method set forth by the American Society of Testing and Materials ("ASTM") in designation D168-64(75) "Breaking and Elongation of Textile Fabrics", hereby incorporated by reference. Substrates having tensile strength after the chlorine solution treatment of at least about 6.5 lbs. in the machine direction (MD) are deemed acceptable to bear the thickened bleach composition in the bleaching article of the invention.
In most cases, it is apparent which substrate materials lack bleach stability: swatches of such material undergo significant loss of tensile strength and may be pulled apart with little effort while the control has all or most of the integrity of a dry standard swatch of the same material.
Methods of making nonwoven cloths are not a part of this invention and being well known in the art, are not described in detail herein. Generally, such cloths are made by air or water laying processes in which the fibres or filaments are first cut to desired lengths from long strands, passed into a water or air stream, and then deposited onto a screen through which the fibre-laden air or water is passed. The deposited fibres or filaments are then adhesively bonded together, dried, cured and otherwise treated as desired to form the nonwoven cloth. Nonwoven cloths made of polyesters, polyamides, vinyl resins, and other thermoplastic fibres can be spunbonded, i.e. the fibres are spun out onto a flat surface and bonded (melted) together by heat or by chemical reactions.
The bleaching article may be made by any process which applies the slurry to the substrate such that the slurry is substantially evenly distributed over the substrate for impregnation thereof. The slurry-substrate complex is subjected to drying so the resulting article feels dry to the consumer and has no more than 30% free water. For good storage stability, the article should have no more than 15% free water.
Conventional means for manufacturing the bleaching article include coating the substrate with slurry via slot die extrusion, reverse role coating, and dip and squeeze techniques. Any series of steps which allows the substrate sufficient residence time in the slurry (or exposure time to the slurry) to substantially saturate the substrate is preferred.
Conventional means further include removing moisture from the slurry-substrate complex, for example, by drying processes such as air flotation, convection drying, infrared drying and microwave drying.
It will be recalled that the chlorine bleach slurry is a harsh corrosive substance. Thus, industrial machinery used to manufacture the bleaching article will preferably be shielded appropriately to protect parts susceptible to corrosion by the chlorine bleach. For example, rollers used in dip and squeeze techniques resemble rollers used in paper-making. Rather than having rubber or bare metal surfaces however, it is preferred the roller surfaces exposed to the slurry have a thermoplastic or Teflon� coat. Similarly, if a doctor blade is used to scrape excess slurry from the substrate, the blade may preferably be a bleach-stable plastic, or metal rather than a corrodable metal.
In one method of making the bleaching article, the bleach slurry is applied to nonwoven cloth by a method generally known as padding. The slurry is placed into a pan or trough, which may be heated if desired to provide desired fluidity. A roll of absorbent substrate is then set up on an apparatus so that it can unroll freely. As the substrate unrolls, it travels downwardly and, submersed, passes through the pan or trough containing the bleach slurry at a slow enough speed to allow sufficient impregnation. The absorbent substrate then travels, at the same speed, onwardly and between a doctor blade and roller or through a pair of rollers which squeeze off excess slurry. The coated substrate is then dried by passage through a convective air-impingement oven to dry the slurry-substrate complex to a free-water level of about 8% plus or minus 7%. After this drying step, the slurry-coated substrate can be folded, cut or perforated at uniform lengths, and the final bleaching article then packaged and/or used.
The preferred execution in this case is application of the slurry using a slot-die applicator in which the bleach slurry is pumped through a slotted orifice onto the moving web which may be backed by a roller or other support. This process allows direct application to the substrate providing good penetration and has the advantage that the orientation of the applicator has little impact on the coating application. In addition, the coating level may be readily regulated to an extent by adjusting the pumping rate to the speed of the moving web. Maintaining the slurry in a closed system until application avoids over thickening resulting from evaporation of the fluid which may occur when using an open pan. This method of application is known primarily for the application of hot melt adhesives.
The amount of bleach delivered to the washing machine depends on the size of the substrate carrying the dried slurry, the amount of slurry coated on the substrate and the concentration of chlorine bleach in the slurry.
The size and shape of the substrate sheet is a matter of choice and is determined principally by factors associated with the convenience of its use. Thus, the sheet should not be so small as to become trapped in the crevices of the machine or the clothes being washed or so large as to be awkward to package and dispense from the container in which it is sold. For the purposes of the present invention, sheets may range in surface area from 5 to 250 square inches. The preferred size range is from about 80 to about 120 square inches.
The concentration of chlorine bleach in the slurry and the amount of slurry on the substrate are also matters of choice which may be determined mainly by convenience. Since many consumers habitually use a liquid chlorine bleach, it is deemed desirable that each bleaching article deliver an amount of bleach comparable to some standard amount of liquid bleach. One standard volume of liquid bleach consumers use is one cup (English volume measurement); frequently, the amount of liquid bleach added to a wash is a fraction or multiple of a single cup of bleach. The bleaching article may be formulated so that one cup (or fraction or multiple thereof) will be delivered by each article. Thus, a unit dose of the bleaching article may contain the amount of bleach in 0.05-2.0 cups of commercial sodium hypochlorite solution, or preferably 0.1-2.0 cups and most preferably 0.25-0.5 cups. Since each cup of commercial sodium hypochlorite solution delivers about 180 ppm to the wash, these volumes of bleach correspond respectively to 9 to 360 ppm, preferably 18 to 180 ppm and most preferably 45 to 90 ppm of bleach delivered to the wash.
A highly preferred article herein comprises the chlorine bleach compound in water-releasable combination with a sheet which should be flexible so as to make it compatible with the movement of the fabrics in the washing machine and to facilitate its handling during manufacture and use of the product. Preferably, the sheet is water permeable, i.e. water can pass from one surface of the sheet to the opposite surface and, for film type substrates, perforation of the sheet is desirable. The most preferred form of the substrate is a sheet of woven or nonwoven fabric or a thin sheet of open cellular plastic material. Woven fabric sheets can take the form of a plain weave natural or synthetic fibre of low fibre count/unit length, such as is used for surgical dressings, or of the type known as cheese cloth. Loading limitations on sheet type substrates limit the amount of bleach that can be applied to the sheet namely to a range represented by a slurry:sheet weight ratio of about 0.5:1 to about 40:1, preferably 1:1 to 20:1 and most preferably 2:1-5:1. (See Example 8 below.)
The following examples will more fully illustrate the embodiments of the invention. As will be readily apparent to persons of ordinary skill in the art to which the present invention pertains, various modifications of such invention as hereinbefore set forth and as further defined in the appended claims may be made without departing from the spirit and scope thereof.
This example discusses the ignition temperature of bleach slurry and bleaching article components. Because many materials undergo exothermic reaction at elevated temperatures with oxidants such as bleach, this test is performed to identify components likely to cause such runaway reactions.
In the test, a sample of equal parts by weight of a dry bleach and a slurry or article component is formed. (Neat samples of bleach are tested without any other component.) The sample is then heated at about 3�-5� C. per minute, and its temperature rise is recorded.
The ignition temperature (Ti) is arbitrarily defined as that temperature at which the sample heating rate is significantly greater than the applied heating rate, ie over 10� C. per minute.
The following guidelines were used in evaluating the safety of compositions.
______________________________________Ti(�C.) Interpretation______________________________________<100 Unsafe. Do not use.>100 May be used with extreme caution on an experimental scale. Monitor samples closely for any signs of reactions. dispose of unnecessary materials. Additional testing and evaluation necessary.>120 Use with caution. May be scaled up if sufficient experience is developed and additional stability compatability tests have been conducted.>150 Unreactive. May be used with appropriate caution.______________________________________
It should be noted that the Ti may vary for one component depending on the bleach with which it is tested. Reactivity of one component with one bleach may provide an indication of reactivity with another; however, the Ti of a dispersant with NaDCC may be within the unreactive range, but in the range of caution or extreme caution with another bleach.
The apparatus used in these tests is shown in FIG. 2.
The ignition test protocol is set forth more particularly as follows. A 1.5-10.0g sample (Note 1) of the test material is placed in a thick-walled 25�200 mm test tube. A thermocouple probe in a protective PYREX glass sleeve is inserted into the sample which is then lowered into a steel pipe in a sand heating bath constructed from a heating mantle as shown in the FIG. 2. A safety shield is placed around the sand bath which is then heated at a rate of 3�-5� C./min (Note 2) by applying an appropriate fixed voltage while the sample temperature was recorded. The test is halted when the sample temperature exceeds 200� C.
Note 1: The sample size may be varied depending on the intensity of the thermal transitions and the potential hazards. The sensitivity of the thermocouple, however, typically requires a minimum sample of 1 g while samples greater than 5 g may present an unacceptable hazard.
Note 2: The heating rate of 3�-5� C./min is specified to complete tests in 20-30 mins. and to minimize dissipation of exotherms by the apparatus.
There follow ignition temperatures for several components of the bleach slurry or the bleaching article.
______________________________________ Sample Ti a Wt. (g) (�C.)______________________________________Sample DescriptionNeat NaDCC 2.5 >200Int. Paper polyester nonwoven #9335064 5.0 >200LMW-100N 3.0 >200Phorwhite BHC-766, Bayer-Mobay 5.0 190Ignition Temperatures for 1:1 NaDCC AdmixturesSample DescriptionPolymersHPC, hydroxypropylcellulose 5.0 86Polyvinyl alcohol 2.0 86PVP K-60 5.0 90Acrysol ASE-60 5.0 164Rhoplex HA-8 5.0 166NS-78-6312 5.0 141NS-78-6210 5.0 182NS-78-6146 5.0 180NS-78-6295 5.0 >200SMA-1440A, poly(styrene-co-maleicanhydride) derivatives:Fully hydrolyzed 5.0 154n-Octyl monoester 5.0 106EMA-1103, poly(ethylene-co-maleicanhydride) derivatives:Monomethyl ester, 10% esterified 2.0 170n-Butyl ester, 10% esterified 5.0 164Sodium isethionate ester, 10% esterified 3.0 >200SolventsAcetonitrile 20.0 .sup. 1401Isopropanol 20.0 >200Methanol 20.0 .sup. 1003Ethanol 20.0 >200Acetone 20.0 >200Miscellaneous MaterialsCyanuric acid 5.0 >200Urea 5.0 .sup. 453Silwet 5.0 112Melamine -- .sup. 1403Ammelide -- .sup. 1343Ignition Temperatures for 1:1 DCDMH AdmixturesSample DescriptionNeat DCDMH -- >200PolymersHPC -- .sup. 523LMW-100N 5.0 200Tamol 850 -- 180Tamol 960 -- 174Monofax 1214 -- 100SMA-1440A n-octyl ester -- 100EMA-1103 derivatives:Hydrolyzed to the diacid 2.0 136Methyl ester, 10% esterified 2.0 130n-Butyl ester, 10% esterified 2.0 132Sodium isethionate ester, 10% esterified 2.0 154Miscellaneous MaterialsPolyester substrate, Int. Paper 9335064 -- 194Silwet 2.0 120Ignition Temperatures for 1:1 BCDMH AdmixturesSample DescriptionNeat BCDMH -- 190PolymersLMW-100N 10 .sup. 1501EMA-1103, fully hydrolyzed -- .sup. 1803HPC -- .sup. 703Silwet -- .sup. 1403Lauryl alchol sulfate -- .sup. 1003Talc 10 .sup. 1622______________________________________Polymers And Their SuppliersTrade Name Description Supplier______________________________________Acrsol LMW-100N Rohm & Haas SodiumpolyacrylateAcrysol ASE60 Acrylic copolymer emul- Rohm & Haas sionEMA 1103 Poly(ethylene-co-maleic Rohm & Haas anhydride)NS-78-6146 Poly(acrylate-co-styrene) National Starch emulsionNS-78-6210 Acrylic copolymer emul- National Starch sionNS-78-6295 Acrylic resin National StarchNS-78-6312 Vinyl-acrylic copolymer National Starch emulsionRhoplex HA-8 Acrylic latex resin Rohm & HaasSokalan CP-5 Sodium poly(acrylate-co- BASF maleate)Sokalan CP-7 Sodium poly(acrylate-co- BASF maleate)SMA 1440A Poly(maleic anhydride-co- ARCO styrene)Tamol 850 Polymethacrylate Rohm & HaasTamol 960 Polymethacrylate Rohm & HaasVersa TL-3 Sodium poly(maleate-co- National Starch styrenesulfonate)Versa TL-70 Sodium polystyrenesul- National Starch fonate______________________________________ a 3 = severe, 2 = strong, 1 = moderate, none = mild
The reactivity of material with chlorine bleach is an important consideration in selection of potential bleach slurry and bleaching article components. The ignition tests in Example 4 provide an evaluation of compatibility of dry mixtures. Two additional tests,"Chlorine Scavenging" and "Chlorine Capacity", were developed to gauge the reactivity of chlorine bleach with bleach slurry or article additives under conditions which mimic the aqueous bleach slurry. These tests are primarily of use to evaluate polymeric dispersants and binders but may also be used to evaluate a variety of additives, such as surfactants.
Both tests are conducted at pH 7.0, nearly optimum for NaDCC slurries. Sodium hypochlorite is used as the bleach instead of NaDCC for convenience and because it is the actual active bleaching agent generated by hydrolysis of the dissolved NaDCC.
The chlorine scavenging test measures the rate of bleach activity loss of sodium hypochlorite in a large excess of the additive. This is, in a sense, a pseudo first order rate study. The activity loss is monitored over a period of 3-4 half lives, until it is <50 ppm av Cl2.
Separate solutions are prepared of about 200 ml of a 11.1 wt % (or 5.6 wt %) of the material to be tested and sodium hypochlorite at 5000 ppm av Cl2 in 0.2 M pH 7.0 phosphate buffer. A 20 ml portion of the chlorine solution is added to a 180 g portion of the test solution giving a mixture 10 wt % (or 5 wt %) in the test material and 500 ppm av Cl2 as hypochlorite. The start time is taken at the point when half of the stock chlorine solution has been added. A separate blank solution is also prepared by adding 20 ml of the stock chlorine solution to 180 g of phosphate buffer. Aliquots (10-20 g) of the blank solution and the mixture are taken at appropriate intervals and analyzed for changes in pH and remaining activity by iodometric titration. The half lives for chlorine scavenging are determined from a plot of the percent remaining activity verses time.
A blank solution shows almost no activity loss while those containing polymeric dispersants and binders have varying rates of reaction as shown in the accompanying figure. Materials are judged on the basis of their relative reactivities as measured by their half lives (t1/2) listed in the table below. Unless otherwise noted, the components are tested at a 10 wt % concentration.
______________________________________Polymer Chlorine Scavenging Half LivesComponent t1/2______________________________________LMW-100N 5.5LMW-100N (5 wt %) 24.0LMW-10N 10.0LMW-20N 0.3LMW-45N 15.0LMW-400N 5.5Acrysol A-1 1.5Acrysol A-3 <0.2Acrysol A-5 <0.2Sokalan CP-5 0.2Sokalan CP-7 0.3Sulfonated polystyrene 0.7Versa TL-3 0.03Versa TL-70 0.4Narlex D-52 1.5NS 78-6146 (5 wt %) 0.5NS 78-6210 (5 wt %) 1.1NS 78-6312 (5 wt %) 1.5Rhoplex HA-8 (5 wt %) 1.5______________________________________
Polyacrylates as a group are seen to have the slowest rates of reaction. Such slower rates of reaction are preferred. Many potential dispersants and binders react very quickly In some cases rates of reaction are inconsistent with expectations based on the compounds structure. The curves of the activity loss versus time suggest that there is an initial fast reaction followed by a much slower one. It was thought that the initial rate is possibly due to the presence of highly reactive impurities or additives such as surfactants used in the preparation of the materials especially with latexes. A chlorine capacity test was devised to determine, in effect, the amount of hypochlorite required to neutralize these reactive materials.
The chlorine capacity test is conducted under similar conditions as the scavenging test. Basically, a 5 wt % solution of the polymer in 0.2 M pH 7.0 phosphate buffer is treated with portions concentrated sodium hypochlorite solution until the reaction half life exceeds an acceptable value of 24 hrs., comparable to that of LMW-100N.
More particularly, 200 g of a 5 wt % solution of the material to be tested in 0.2 M pH 7.0 phosphate buffer is prepared and treated with sufficient commercial sodium hypochlorite solution (about 4 ml at 5 % av Cl2) to give a concentration of about 1000 ppm av Cl2. The test solution is evaluated after 24 hrs for any change in pH and remaining activity by iodometric titration of a 5 g aliquot. The test is repeated by adding fresh portions of sodium hypochlorite after daily analysis until the remaining activity was >500 ppm av Cl2 or until six portions of hypochlorite have been added. The amount of sodium hypochlorite which results in a residual activity ≧500 ppm av Cl2 is defined as the chlorine capacity Materials which exhibit chlorine capacities >5000 ppm av Cl2 or a chlorine capacity of greater than 10% are considered unacceptable.
The results for several materials are listed below.
______________________________________Chlorine Capacities Chlorine CapacityComponent ppm av. Cl2 Ratio (%)a______________________________________NS 78-6146 2600 5.2NS 78-6210 2750 5.5NS 78-6295 3100 6.2NS 78-6312 >5000 >10Versa TL-3 1800 3.6Versa TL-70 2200 4.4Narlex D-52 2200 4.4Rhoplex HA8 3100 6.2______________________________________ a Ratio = (wt % av Cl2)/(wt % polymer)
Materials with chlorine capacities <10% of their weight are considered acceptable for testing and evaluation unless other tests, such as ignition studies prove negative. Caution must be exercised since the "neutralized" component may pose a latent hazard. Initial formulation studies should be conducted on as small a scale as is practical with frequent monitoring. The polymers are generally pretreated with an amount of hypochlorite defined by their chlorine capacities before use in bleach sheet slurry formulations.
WARNING: Normal precautions used in working with chlorine bleaches should be employed when conducting these tests. Under no circumstances should amines, ammonium salts, or most other nitrogen compounds be used since they potentially give rise to extremely hazardous chloramines.
The viscosity of several bleach dispersions was measured on a Haake Rotovisco viscometer model RV-3 with either an MK-50 or an MK-500 measuring head and an MV1 and SV1 cup and spindle. The temperature was regulated using a Lauda RMS-6 refrigerating circulator with a claimed control accuracy of + or -0.01� C. The viscometer was calibrated against standard oils and then the bleach slurries were measured. The reported single value viscosities were determined by shearing the slurries at a constant shear rate of 80 per sec for 20-30 minutes after which a steady shear stress was observed.
Powdered sodium dichloroisocyanurate ("NaDCC") was added as supplied by Olin Corp. to water and polyacrylate as indicated:
______________________________________ PolyacrylateBleach LMW-100N Water Viscosity(Wt %) (Wt %) (Wt %) (cP at 25� C.)______________________________________68.0 4.0 28.0 310365.0 4.0 31.0 131060.0 5.0 35.0 68359.5 12.0 28.5 621054.0 10.0 36.0 118754.0 5.0 41.0 14446.0 13.0 41.0 58345.0 5.0 50.0 10040.0 13.0 47.0 241______________________________________
Three fluorescent whitening agents are evaluated for incorporation into the bleach slurry and sheet: Ciba-Geigy Tinopal RBS-200 and CBS-X and Bayer-Mobay Phorwhite BHC-766. CBS-X loses a significant amount of activity when formulated with the bleach slurry. RBS-200 also loses some of its fluorescent activity during short term processing. In comparison, BHC loses no activity even under prolonged use, delivers excellent brightening benfits, and is easy to incorporate into the standard formulation with no changes. BHC is therefore used as the fluorescer of choice.
The evaluation of three commercial bleach-stable fluorescers is by standard F-Dye tests (described in U.S. Pat. No. 4,460,485 hereby incorporated by reference). Individually preweighed mixtures of the fluorescer with 1.217 g of powdered NaDCC in sample vials are provided for use in these Kleenette studies. The pertinent results for the cummulative five wash fluorescence effects are summarized in the tables below. The first table gives the results for both high and low fluorescer concentrations using dye-free liquid "all". The high and low concentrations are equivalent to 1 g and 0.1 g per normal wash dose (sheet), respectively.
______________________________________Fluorescer Dose Monitor Cloth Type(Supplier) g/3 gals. Cotton Nylon Dacron______________________________________Phorwhite BHC-766 0.1765 42.1 28.9 5.7(Bayer-Mobay) 0.0177 22.6 15.7 4.2Tinopal RBS-200 0.277 36.4 31.3 25.7a(57% active) 0.0277 23.2 18.2 6.1(Ciba Geigy)Tinopal CBS-X 0.1765 34.7 17.5 4.3(Ciba Geigy) 0.0177 6.8 4.1 3.8______________________________________ a Yellowed.
A chlorine bleach slurry and a bleaching article are made with the following formulation:
______________________________________Component Slurry Wet Sheet Dry Sheet______________________________________Bleach 51.2% 43.0% 55.4%Dispersants & 11.2 9.4 12.1BindersFluorescer 1.6 1.3 1.7Water 36.0 30.2 10.0Substrate -- 16.1 20.8______________________________________
The bleaching article has a wet loading ratio of about 5.2:1 and a dry loading ratio of about 3.8:1.
The bleaching article delivers 4.4 grams of active chlorine (g av Cl 2) to the wash.
|Cited Patent
|Filing date
|Publication date
|Jul 29, 1969
|May 25, 1971
|Cassella Farbwerke Mainkur Ag
|Stable alkali chlorite mixtures
|Feb 9, 1970
|Jan 11, 1972
|Colgate Palmolive Co
|Bleaching packets
|May 3, 1972
|Jun 11, 1974
|Procter & Gamble
|Laundering aid
|Jan 29, 1974
|Mar 23, 1976
|The Procter & Gamble Company
|Bleaching article
|Sep 9, 1974
|Oct 12, 1976
|The Procter & Gamble Company
|Scouring compositions
|Nov 12, 1973
|Jan 25, 1977
|The Procter & Gamble Company
|Scouring compositions
|Mar 27, 1975
|Mar 8, 1977
|The Procter & Gamble Company
|Bleaching articles
|Mar 27, 1975
|Apr 12, 1977
|The Procter & Gamble Company
|Bleaching articles
|Sep 4, 1975
|Sep 27, 1977
|The Procter & Gamble Company
|Abrasive scouring compositions
|Oct 1, 1976
|Aug 8, 1978
|The Procter & Gamble Company
|Dishwasher detergent composition
|Jun 20, 1977
|Sep 26, 1978
|The Procter & Gamble Company
|Thickened bleach compositions for treating hard-to-remove soils
|Nov 10, 1975
|Dec 19, 1978
|The Procter & Gamble Company
|Bleaching process
|Feb 6, 1978
|Apr 24, 1979
|The Clorox Company
|Built liquid bleaching compositions
|May 25, 1978
|Sep 4, 1979
|Colgate-Palmolive Company
|Liquid bleach-softener compositions
|Nov 21, 1977
|Dec 9, 1980
|Lever Brothers Company
|Additives for clothes dryers
|May 25, 1978
|Jun 16, 1981
|Colgate-Palmolive Company
|Article for dispensing liquid bleach softener composition
|Apr 12, 1979
|Aug 25, 1981
|The Drackett Company
|Pouch bleach
|Nov 21, 1980
|Jun 29, 1982
|Lever Brothers Company
|Liquid, thickened chlorine bleaching composition
|Jul 13, 1981
|Jul 5, 1983
|The Procter & Gamble Company
|Controlled release laundry bleach product
|Aug 23, 1983
|Jul 16, 1985
|The Procter & Gamble Company
|Tissue paper
|Aug 15, 1983
|Jul 30, 1985
|S. C. Johnson & Son, Inc.
|Dissolvable bleach sheet
|Apr 9, 1984
|Dec 10, 1985
|S. C. Johnson & Son, Inc.
|Polymer sheet for delivering laundry care additive and laundry care product formed from same
|Nov 28, 1984
|Jan 27, 1987
|The Procter & Gamble Company
|Laminated laundry product
|Jun 25, 1985
|Mar 24, 1987
|The Procter & Gamble Company
|Oxidation resistant tissue for dry laundry actives and bleach compatible products
|Apr 30, 1984
|Feb 16, 1988
|The Dow Chemical Company
|Systems for delayed release of bleaching agents
|Feb 19, 1987
|Apr 26, 1988
|The Procter & Gamble Company
|Soil release polymer coated substrate containing a laundry detergent for improved cleaning performance
|May 9, 1988
|Jan 10, 1989
|S. C. Johnson & Son, Inc.
|Polymer sheet for delivering laundry care additive and laundry care product formed from same
|Attachment 1 Industrial Uses of ACL Chlorinating Compositions.
|Attachment 1--Industrial Uses of ACL Chlorinating Compositions.
|Citing Patent
|Filing date
|Publication date
|Aug 23, 1993
|Nov 8, 1994
|Rodriguez Ricardo M
|Bleaching and finishing composition and method
|May 26, 1995
|Aug 27, 1996
|Reckitt & Colman Inc.
|Thickened alkali metal hypochlorite composition
|Jan 23, 1997
|Oct 6, 1998
|Ecolab Inc.
|Dispensing a viscous use solution by diluting a less viscous concentrate
|Feb 5, 1997
|Oct 26, 1999
|Ecolab, Inc.
|Thickened noncorrosive cleaner
|Feb 6, 1998
|Oct 10, 2000
|Precision Fabrics Group, Inc.
|Laundry detergent compositions containing silica for laundry detergent sheets
|Nov 13, 1997
|Apr 3, 2001
|The Clorox Company
|Sequesterants as hypochlorite bleach enhancers
|May 10, 1996
|Oct 2, 2001
|The Clorox Company
|Sequesterants as hypochlorite bleach enhancers
|Nov 30, 1999
|Oct 30, 2001
|Amway Corporation
|Method of inhibiting soil redeposition
|Jul 27, 1999
|Nov 19, 2002
|Milliken & Company
|Method of retaining antimicrobial properties on a halamine-treated textile substrate while simultaneously reducing deleterious odor and skin irritation effects
|Oct 23, 2000
|Jun 10, 2003
|Milliken & Company
|Method of retaining antimicrobial properties on a halamine-treated textile substrate while simultaneously reducing deleterious odor and skin irritation effects
|Nov 7, 2001
|Mar 8, 2005
|Newlund Laboratories, Inc.
|Method of making a laundry detergent article containing detergent formulations
|Oct 25, 2000
|Aug 22, 2006
|Kao Corporation
|Method for producing sheetlike detergent
|Dec 15, 2005
|Oct 14, 2014
|Kimberly-Clark Worldwide, Inc.
|Wiper for use with disinfectants
|Dec 15, 2005
|Jun 21, 2007
|Clark James W
|Wiper for use with disinfectants
|Oct 9, 2007
|Apr 10, 2008
|Mario Elmen Tremblay
|Calcium hypochlorite for use in a laundry washing process
|Sep 19, 1997
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|Bleaching compositions
|Aug 28, 1998
|Apr 1, 1999
|The Procter & Gamble Company
|Bleaching compositions
|Nov 25, 2014
|Jun 11, 2015
|Little Island Patents Limited
|Cleaning additives in the form of a sheet
|U.S. Classification
|252/186.25, 252/187.1, 510/513, 8/101, 252/186.34, 510/295
|International Classification
|Cooperative Classification
|European Classification
|Apr 8, 1996
|Fee payment
Year of fee payment: 4
|Oct 17, 2000
|Maintenance fee reminder mailed
|Mar 25, 2001
|Lapse for failure to pay maintenance fees
|May 29, 2001
|Expired due to failure to pay maintenance fee
Effective date: 20010323


text:
|"Listen, you're not alone anymore. We have a new family now. We stick together, you hear me?"
|~ —Fang to Vanille
Oerba Yun Fang is a playable character in Final Fantasy XIII who appears as a non-playable character in Final Fantasy XIII-2 and as a temporary party member in Lightning Returns: Final Fantasy XIII. Her full name stands for "Fang of the Yun clan, from the village of Oerba".
Fang and Vanille share a similar Australian accent in the game's English version.
Appearance and Personality
|"You want to keep breathing? Shut up and come quiet."
|~ —Fang while apprehending Snow.
Fang is a tall woman, standing at 5'9". Despite her chronological age, she has the physical appearance of a twenty-one-year-old. Fang has bronze skin and wavy dark brown hair with a braid behind her left ear. Fang's eyes are green and there is a beauty mark underneath her right eye. Fang wears purple claw-shaped earrings. She has scars on her right arm and shoulder, and wears blue clothing resembling the traditional Indian sari adorned with tribal accessories.
In addition to the sari, Fang wears a short black top, black sleeves over her forearm, tan leather open-toed sandals, and two fur pelts hanging from a cord beneath a belt that holds her spear. Fang has the brand of a l'Cie on her right shoulder and a large tattoo on the other. Unlike the other l'Cie in the game whose brands are black and change as the story progresses, Fang's l'Cie brand is white and does not progress.
Character designer Tetsuya Nomura has stated that when compared to the other characters personality-wise, Fang is stronger than Lightning and more stubborn than Snow. In Final Fantasy XIII Episode Zero -Promise-, Lightning comments on Fang having a "wild fearlessness to her". This is supported by Fang never wanting to back down from a fight no matter who or what the opponent. She believes strongly in Lady Luck, and has a caring and compassionate side, especially when it comes to Vanille and would do anything to prevent Vanille from becoming a Cie'th.

subset: commoncrawl


text:
body procedure, Non-Surgical, PDO Threads
PDO Body Thread Lift – Remove the Sag for Summer
When we get to that certain age we can start to sag and lose firmness, even ex-swimmers can have sagginess after muscle loss under the arm. How great that we now have a procedure to lift the skin and leave it firm and tight again, all this without doing any surgery!
body procedure, cellulite treatment, fat burn injection, injection, Non-Surgical
Lipoless why YES – non surgical procedure to reduce unwanted fat
Lipolysis non surgical procedure for fat dissolve
In aesthetic word there are a lot of innovative approaches to shape the body without surgery. Sometimes diet and exercise are time-tested methods for improving how you look and feel, but they are not always able to combat persistent fat deposits.
One of them called lipolysis injection which can help to reduce unwanted fat and dissolve cellulite.
Nowadays there are many types of this injection some of them including combination of vitamins and acids. A Lipolysis injection contains a solution of lipotropic nutrients that are made up of one or more of the following fat burning compounds: choline, inositol, methionine, amino acids, vitamin b12 and other vitamins and minerals. Each of these properties are important because they each have a key role in utilising fat, distributing energy, and removing toxins from the body.
Botox, Face lift, injection, Men's treatments, News, Non-Surgical, Wrinkle
TOP 7 Non-Surgical Face and Body Treatments for Men
Most popular aesthetic procedures for Men
Recently reported in The HarleyStreet Journal in the survey was discovered that a quarter of men are having non invasive treatments to reward themselves.
Here are the TOP 7 men's treatments that are growing in demand and popularity
1. Botox, also known as botulinum toxin, is a non-invasive injectable treatment used to rejuvenate the face. Botox works by relaxing the underlying muscles that cause the skin to crease and develop lines or wrinkles. Botox is considered to be one of the safest and most widely researched cosmetic products available today.
injection, Non-Surgical, Nose, Reshaping
Non Surgical Nose Reshaping
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After a season of uncertainty, the sun shone brightly on Sunday, September 7 as Danielle and Joe (diagnosed with Stage IV Metastatic Melanoma on his brain)prepared to fulfill their dream of starting a new life together. All the festivities took place inside the idyllic La Banque de Fleuve, a beautifully renovated historic building in Havre de Grace, Maryland where the Susquehanna River meets the Chesapeake Bay. Originally constructed as the First National Bank in 1904, this one-of-a-kind venue set the perfect tone for this long awaited day.
The theme was casual country chic with the bridesmaids in strapless ivory lace dresses and cowgirl boots (flower girls, too) and all the men wore tan suits minus the jacket and accessorized with pink ties. Danielle looked confident and calm in a sweeping strapless ball gown accompanied by a simple updo.
Every element of the ceremony was given a personalized touch—from Danielle and Joe reading their own vows—to Joe's daughter reading something she wrote for the couple. In addition to Joe's daughter, Danielle's two daughters and son were prominently featured in the wedding party. To further signify the joining of their two families, all four kids participated in a sand ceremony with their parents.
After sealing it with a kiss, it was time to celebrate. Guests headed upstairs for cocktails and a chance to get silly in the photo booth. Back downstairs the ceremony site was transformed for dinner and dancing with a mixture of natural wood accents in the table number holders and centerpieces, and festive mason jars.
Taking advantage of the beautiful weather and surroundings, the evening ended with a sparkler sendoff into a future Danielle and Joe will bravely face together.
Our Michigan chapter granted this wish and we'd like to thank all the phenomenal Maryland vendors that worked with them to make Danielle and Joe's day one they'll never forget:
Gimmie Style Salon


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SOUTHFIELD, Mich., Dec. 20, 2016 /PRNewswire/ -- Nyman Turkish PC, a national disability and litigation law firm, has asked the United States Supreme Court to hear the case of Angelo Binno, a blind Michigan man who sued the American Bar Association (ABA) over five years ago for disability discrimination.
"This case is about far more than just one student," said Jason Turkish, managing partner of Nyman Turkish, who took on Binno's appeal to the nation's highest court pro bono. "This case is fundamentally about whether we're going to treat people with disabilities equally in this country or not. Angelo isn't seeking damages. He's not asking to be graded on a curve. He's simply asking for a level playing field and a chance to be judged on his merits. The Law School Admission Test (LSAT), as currently configured, simply doesn't allow him that chance."
Despite graduating from Wayne State University, speaking three languages and previously holding a high-level security clearance with the Department of Homeland Security, Binno was unable to gain admission to law school because he is unable to complete the "logic games" portion of the LSAT.
The "logic games" section requires test-takers to perceive spatial relationships and draw diagrams and pictures. Binno, 34, was rejected by every law school he applied to after taking the LSAT because he couldn't draw diagrams and thus scored too low.
The ABA has long since recognized the discriminatory nature of the LSAT yet it threatens law schools it regulates with loss of accreditation should those schools make the simple accommodation of waiving this inherently discriminatory exam. Until the mid-1990s, the ABA allowed law schools to waive the LSAT requirement for those who are "physically incapable" of taking the test. That exception was repealed by the ABA, and now all law school applicants must take the LSAT, regardless of disability. Binno contends that asking him to draw diagrams and perceive spatial relationships illegally tests him on his inability to see rather than on his aptitude for the study of law.
Contact: TJ Bucholz, 517.657.3944
To view the original version on PR Newswire, visit:http://www.prnewswire.com/news-releases/blind-michigan-student-petitions-us-supreme-court-to-give-the-sightless-an-equal-chance-at-becoming-lawyers-300382076.html
SOURCE Nyman Turkish PC


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The Folk by the Oak team strive to bring together a truly memorable 'line-up of headliners' each year. For 2017 we are planning another day of exceptional wall to wall music across our 2 stages.
Be sure to follow us on social media using the links below, or sign up to our newsletter using the link on the home page to be the first to hear when announcements are made.


text: 3135 LOMA LANE, CHARLOTTE, NC 28205 < New Search Schedule Showing ScheduleShowing Request Info RequestInfo Save To Favorites Save ToFavorites Schedule Showing × Message First Name* Last Name* Email* Phone * Preferred Time and Date* 8:00 AM 8:30 AM 9:00 AM 9:30 AM 10:00 AM 10:30 AM 11:00 AM 11:30 AM 12:00 PM 12:30 PM 1:00 PM 1:30 PM 2:00 PM 2:30 PM 3:00 PM 3:30 PM 4:00 PM 4:30 PM 5:00 PM 5:30 PM 6:00 PM 6:30 PM 7:00 PM 7:30 PM 8:00 PM 8:30 PM Alternate Time and Date* 8:00 AM 8:30 AM 9:00 AM 9:30 AM 10:00 AM 10:30 AM 11:00 AM 11:30 AM 12:00 PM 12:30 PM 1:00 PM 1:30 PM 2:00 PM 2:30 PM 3:00 PM 3:30 PM 4:00 PM 4:30 PM 5:00 PM 5:30 PM 6:00 PM 6:30 PM 7:00 PM 7:30 PM 8:00 PM 8:30 PM Message *Your name, phone number, and email address are required so that we may contact you to schedule an appointment. By submitting this form with your telephone number you are consenting for Savvy Girl Homes and authorized representatives to contact you even if your name is on the Federal "Do-not-call List." Send Close More Info × Message First Name* Last Name* Email* Phone * Message *Required fields. Your personal information is strictly confidential and will not be shared with any outside organizations. By submitting this form with your telephone number you are consenting for Savvy Girl Homes and authorized representatives to contact you even if your name is on the Federal "Do-not-call List." Send Close Save To Favorites × Registered Users (please sign in) Message Email Sign In New Users Message First Name* Last Name* Email* Phone * *Required fields. A confirmation email will be sent to you with instructions for activating your account, so please be sure your email address is entered accurately. Sign up Close Email Listing × Close Pinterest Twitter Google+ Map Schools Walk Score Mortgage Calculator Virtual Tour 3135 Loma Lane, Charlotte, NC 28205 Map × Close 3135 Loma Lane, Charlotte, NC 28205 Schools × Close 3135 Loma Lane, Charlotte, NC 28205 Walk Score × Score Your Home: Close 3135 Loma Lane, Charlotte, NC 28205 Mortgage Calculator × $ per month Year Fixed. % Interest Rate. Principal + Interest: $ Monthly Tax: $ Monthly Insurance: $ Term yrs Interest Rate % Down Payment $ List Price: $ Based on a fully amortized fixed rate loan. Ask your agent for the tax rates in your area. Insurance estimate is based on an average cost, your final premium cost will be determined by the type of coverage you select. This program only provides an estimate. Close 3135 Loma Lane Charlotte, NC 28205 $1,875,000 (Active) Beds: 6 Baths: 6 | 1 Sq. Ft.: 6,939 Type: Single Family Home Listing # 3243872 Elegant, easy living minutes from Uptown. Situated on a private .76 acre lot adjacent to Charlotte Country Club, this 6 bed/6.5 bath home is completely updated for modern life -- open floorplan, dream kitchen & loads of lovely spots to enjoy family & friends. Backyard boasts pool & easy access to fab garage apt w/ spa-like bath & mini-kitchen. Great storage on every level. A full home generator kicks in if electricity goes out. 100 year slate roof was installed in 2001. A must see! Features Features Property Features Location Information County: Mecklenburg Subdivision: Midwood Interior Features Master on Main: yes Rooms: 2nd Living Quarters Floor Bathroom(s), Bed/Bonus, 2nd Kitchen, Main Floor Bathroom(s), Bedroom(s), Dining Rm, Family Room, Foyer, Great Rm, Kitchen, Laundry, Living Rm, Master BR, Mud, Office, Pantry, Sunroom, Upper Floor Bathroom(s), Bedroom(s), Family Room, Laundry, Office Interior: Attic Stairs Pulldown, Attic Walk-in, Built-Ins, Kitchen Island, Open Floorplan, Skylight(s), Vaulted Ceiling, Walk-In Closet(s), Wet Bar, Window Treatments, Walk-In Pantry 1/2 Baths: 1 Has Fireplace: yes Fireplace Description: FAMILYRM, Living Room Laundry: 1st Floor, 2nd Floor Water Heater: Gas Additional Equipment: Cable Prewire, Ceiling Fan(s), CO Detector, Cooktop Gas, Dishwasher, Disposal, Double Oven, Downdraft Cooktop, Generator, Ice Maker Connection, Refrigerator, Security System, Self Cleaning Oven, Warming Drawer Sq. Ft. Basement: 0 Exterior Features Style: Traditional Stories: 1.5 Story Is New Construction: No Exterior: Enclosed Patio, Fenced Yard, In-Ground Irrigation, Patio, Pool-In-Ground Siding: Brick Veneer Partial, Wood Foundation: Slab Water: City Water Parking Description: Carport - 1 Car, Detached Garage, Driveway, Garage - 2 Car, On-Street Parking, Other Has Garage: yes Driveway: Asphalt Has a Pool: yes Has Golf Course: No Lot Description: Cul-de-sac Lot, Green Area, Private, Trees Lot Size in Acres: 0.76 Has Waterfront: No School Elementary School: Unspecified Jr. High School: Unspecified High School: Unspecified Additional Information Property Type: SFR Property SubType: 1.5 Story Year Built: 1952 Status: Active Doors Windows: Insulated Windows, Screen Door(s) Listing Courtesy of: Dickens Mitchener & Associates Inc © 2017 Carolina Multiple Listing Services, Inc.. All rights reserved. The data relating to real estate on this web site derive in part from the Carolina Multiple Listing Services, Inc. IDX program. Brokers make an effort to deliver accurate information, but buyers should independently verify any information on which they will rely in a transaction. All properties are subject to prior sale, change or withdrawal. Neither Savvy Girl Homes, LLC nor any listing broker shall be responsible for any typographical errors, misinformation, or misprints, and they shall be held totally harmless from any damages arising from reliance upon this data. This data is provided exclusively for consumers' personal, non-commercial use and may not be used for any purpose other than to identify prospective properties they may be interested in purchasing. © 2017 Carolina Multiple Listing Services, Inc. CarolinaMLS data last updated at October 18, 2017 9:29 PM ET Real Estate IDX Powered by iHomefinder


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Sweeten the pot.
A sugar saucepan is a must-have for pastry and chocolate fanatics. You don't have to be a chef or a specialist to appreciate its careful design that was created with caramelizing sugar and heating sauces in mind. Copper conducts heat efficiently to melt sugar without clumping, while the built-in spout ensures an even, no-splatter pour (because there are few things scarier in the kitchen than scalding hot sugar). Now roll your sleeves up; that caramel you've been dreaming of awaits.
Sourced from: Mauviel
Our return policy.
Photography by Bobbi Lin and James Ransom.
Before first use and after use, carefully wash with hot soapy water then rinse and dry. Be careful not to clean with bleach, which could lead to irreparable damage. To restore the shiny copper surface, pick up a bottle of Copperbrill cleaner.
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This page has been speech-enabled for Macintosh owners using the Talker Netscape Plug-in. Hit Escape to discontinue speech.
Senator Charles Grassley, R-Iowa, a board member of the Office of Technology Assessment, has proposed S-974, "The Anti-electronic Racketeering Act." In his statements to the Senate, he declared that "Eliot Ness needs to meet the Internet," and thus he is proposing legislation intended to crack down on computer crime and other threats posed by computer-using drug cartels, money launderers and terrorists. (For those of you playing along at home, Eliot Ness was the "G-Man" most noted for enforcing the "Noble Experiment" known as Prohibition, which was, of course, ended on a national scale in 1933, after only thirteen years of sporadic enforcement, by passage of the 21st Amendment to the Constitution).
One of the provisions in Senator Grassley's bill is an amendment to 18 U.S.C. Section 1962 (part of the Racketeer Influenced and Corrupt Organization provisions), which, in addition to making illegal the use of any computer or computer network in the furtherance of a racketeering activity, as defined in Section 1962(1), would also make it illegal to "damage or threaten to damage electronically or digitally stored data."
Based on Senator Grassley's statements, one may assume this is intended to be used to fight computer crackers and virus authors; however it does not distinguish these groups from, say, someone who wants to delete a file from his or her own hard drive, or who accidentally leaves a compact disk on the dashboard of his or her car on a bright summer day. Of course, five disks left on the dashboard to melt produces five "predicate" violations leading to a RICO offense.
Continuing on, Grassley's bill proposes the addition of a new section, 18 U.S.C. Section 1030A, which would make it unlawful to use a computer or computer network to transfer unlicensed computer software, regardless of whether the transfer is performed for economic consideration. It would also make it illegal to operate a computer or computer network primarily to facilitate racketeering activity or primarily to engage in conduct prohibited by federal or state law.
These sections would address cases such as U.S. v. LaMacchia, 871 F. Supp 535 (D. Mass. 1994), which I have discussed here in a previous column. In LaMachia, the operator of a bulletin board system used to distribute pirated computer software was held not to be punishable under the wire fraud statute, 18 U.S.C. Section1343, because by running a free service, his actions did not amount to a criminal copyright violation needed to trigger the wire fraud statute. 871 F. Supp. at 542-543.
Again, unfortunately, this section does not account for two common means used to distribute software. Software that is distributed for free ("Freeware") is unlicensed, as is public domain software. Shareware is commercial software, but it is arguably unlicensed at the point it is transferred-- a license is generally given after payment of the shareware fee is made after a trial period. At the time of the software's actual transfer, it is unlicensed. And, of course, running a bulletin board system used solely to distribute public domain software under this provision becomes a federal offense.
Even more mundane tasks, such as two programmers exchanging pieces of computer code (unlicensed software) could result in the 'corrupt programmers' being treated as if they were drug dealers.
While these are likely unintentional side-effects of the legislation, the same section also seeks to make it unlawful to distribute computer software that encodes or encrypts electronic or digital communications to computer networks that the person distributing the software knows or reasonably should know, is accessible to foreign nationals and foreign governments, regardless of whether such software has been designated as nonexportable.
This section is not as bad as it sounds-- it allows an affirmative defense to prosecution if the software uses a "universal decoding device or program that was provided to the Department of Justice prior to distribution."
Under this section, no software capable of encrypting messages is exportable, even if the government has allowed its export in the past, unless the Department of Justice is given the "key." This is even more strict than the Administration's failed "Clipper Chip" plan, which at least would require that two separate agencies keep portions of any decryption key, and which was supposedly intended to be a voluntary scheme.
Once again though, this section does not contain reasonable limits on its reach-- any software which "encodes" an electronic communication is prohibited, which would not only cover strong encryption programs such as Pretty Good Privacy (PGP) but also garden variety compression programs such as Macintosh Binhex and DOS PKZIP software used to shrink files for quicker transmission and archiving would be covered.
(Though it is comforting to know that you could still, say, distribute a pig-Latin conversion program, so long as you give the Justice Department a "universal decoding device". Otherwise, for each person that download the software, you have committed a criminal act.)
It is worth noting that the proposed law does not actually make it illegal for racketeers to use strong encryption software, it just makes certain types of distribution illegal.
Another feature of Senator Grassley's bill is that, in some instances, it loosens the privacy protections provided by the Privacy Protection Act of 1980 (42 U.S.C. Section 2000aa) which were discussed in last month's column.
The Electronic Frontier Foundation notes that this is a direct attack on the holding in Steve Jackson Games v. United States Secret Service, 816 F. Supp. 432 (W.D. Tex. 1993), affŐd, 36 F.3d 457 (5th Cir. 1994), in which the Court found the U. S. Secret Service liable for seizing Steve Jackson Games' computers and bulletin board system, without bothering to address the concerns raised by the seizure of a publisher's computer, its work product, or the publisher's BBS (complete with users' e-mail).
These are only some of the highlights of this proposed legislation. This article does not even address the provisions outlawing anonymous electronic financial transactions, the attempted extension of U.S. jurisdiction to cover any acts which begin and end in a foreign country, yet involve communications which merely pass through U.S. based computers, etc.
The legislature is to be applauded for discovering the wonders of modern communication. If nothing else, the legislature's new discovery has been providing a number of topics for this column.
The Internet is growing exponentially. The major on-line services, such as CompuServe and America On-Line are growing by leaps and bounds. Digital cash is not the future-- in many ways, it is the present (e.g. direct deposit, credit and debit cards). Some of this growth raises legitimate concerns which need to be addressed.
However, if Congress is going to try passing laws affecting these and related topics, it would make some sense if the drafters of the legislation actually tried to understand some of the issues involved before setting pen to paper (or hands to keyboards) to draft bills such as Senator Grassley's. Quick coverage of the events of the day is welcome in the context of news reporting, but often produces bad law in the legislative context.


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Barbara is an exciting breath of fresh air when delivering what God has laid on her heart. She has been invited to speak to a variety of women's events for many different functions from Christmas Teas, to one day retreats. She speaks on a selection of topics such as "Stepping Out Of Your Comfort Zone", "Participating in the Great Commission", "Love Is", "Obedience to God's Calling" and anything else that follows the theme of your event. Her testimony has been an inspiration to many who want to pursue their dreams. She speaks often at an event that includes her husband and he will accompany her if special music is needed.
Please contact her at email@example.com to book her for your event.
Following a church service in Portage La Prairie – Pastor says he was really impressed with both of you this weekend and felt you were a real blessing to the churchs. Thanks for your support and encouragement.
August 12 – Service at Capitol Heights Baptist Church, Pierre SD –
It was our extreme blessing to have you guys with us and at the church. Everything you said was God honoring. Can any of us ask for more? We will certainly be in touch. We love you guys and so enjoyed the time together. Travel safe.
love and prayers,Pastor Bob and Debby Bogart.


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Zenith Constantine
In an original architecture combining beauty with functionality, replete with high-tech equipment, Zenith room Constantine, now nearing completion, is undoubtedly the flagship structure of the event "Constantine, the capital of 2015 Arab culture. " First of its kind in Algeria, this room with a capacity of 3,000 seats, conducted at the Zouaghi city, on the heights of Ain El Bey gives admire an imposing figure who seduces at first glance with its fully glazed facade and slope aluminum cover Launched in work there just one year, the Zenith Constantine reflects, as stated by the Minister of Housing, Planning and the city during a visit to Constantine, the power and Chinese know-how with the construction of a structure of 43,000 m2 in twelve months. A site where the dynamism is at its zenith ... At the entrance of the administrative block of the room, a sign indicates that there are 40 days to deliver the project. The China State Construction Engineering Corporation (CSCEC), responsible for the study and the project, "Do not mess with the time and expects to meet its obligations by delivering the hall on March 15," said at the outset APS, Sonia, the Chinese site manager. Like a giant anthill site "swarming" of the world. Crews are working to put the seats in the large auditorium and in the adjoining room of 150 seats, Italian technicians put the final touches to the sound system, while other teams are working to install directional signs and various other facilities of this mega-project, all on background AEDs Malouf music. Outside the construction site, workers are finalizing work on the esplanade, others are working to maintain green spaces while another team loop tarring the East parking lot of the building. "We have already made the necessary technical tests of air conditioning, air handling unit (AHU), public sound systems, projectors and the safety device and the tests are conclusive, "said the engineer of management of public facilities (DEP), responsible for monitoring the site, Mourad Boutamine. Spanning a total area of 60,000 m2, the building at a footprint of 13,800 m2 and a total catch of built floor of about 43,000 m2. Its structure is three-dimensional with large spans of up to 24 meters high while its metal cover totaled 14,500 m2. The walls of the building, some of which reach 29 m in height are completely covered in aluminum. Site, gigantic, required at the height of activity, mobilization of not less than 1,000 workers. "Since the launch of the work, at least 200 people occupying the site 7 days 7", says Boutamine. In parallel, nearly sixty engineers and architects of the Chinese company, the Lebanese Dar El Handassa design office, the Algerian BEREP design office (design office engineering realization of projects) responsible for climate engineering, and DEP managers oversee a watchful eye work. Zenith concert hall was also the subject since the launch of the project, from architects visits and expert engineers in the contract between the client Dar El Handassa. A fortnightly meeting also includes the client (DEP) CSCEC and teams of project monitoring to assess the progress of work, says one. A huge asset for the city In this whirlwind of numbers, standards and statistics came a great fluidity structure reflecting a sense of transparency and lightness thanks to the light that floods the scene and materials, including glass and steel. Mr. Boutamine argues that beyond its lightweight aesthetic, the Zenith meets the technical criteria for a modular auditorium. The hall of 3,000 seats is the central element of this building designed as a space flexible, able to change its configuration to accommodate different shows The seats in the stalls are retractable and removable 1,000 chairs were set there with a space reserved for the disabled. The scene covers 600 m2. In this room that offers security conditions that meet the highest standards, particular attention was paid to "visual and auditory comfort, thanks to the multiple combinations stage and bleachers, and blackout possibilities of one or more parts of the total space, "says Boutamine. "The layout of the amphitheater bleachers as slope and allow maximum visibility, while the absence of echo and reverb guarantees a perfect sound," he says again. From either side of the room, deploy two theaters of 300 and 150 seats, an exhibition area of 2,400 m2 and a permanent gallery, smaller than 1.400 m2. The artist space consisting of "star lodges," "groups lodges", a catering area, a modular rehearsal room, a media room and two recording studios. The building also includes a consumer space and sales counters for spectators and service spaces, administrative offices, rooms for technicians and car parks. Complementing current cultural structures of the city, the Zenith Constantine confirms and consolidate the status of the regional capital of the city of bridges, a city that has chosen to turn resolutely towards modernity.