DE1949258A1 - Color developing abrasive - Google Patents

Description

Colgate-Palmolive Company US 8i6 O92 - prio Η »4ο69

New York, N «Yo, V.StoAo 6505

26 Sep 1969

Color developing abrasive

The invention relates to detergents, in particular Abrasive agents which undergo a noticeable change in color when they come into contact with aqueous media.

It is well known in the detergent industry that the appearance of a product is often of crucial importance to its consumption by the consumer, and in many cases the saleability of a product is determined more by aesthetic considerations than efficacy considerations that certain colors trigger a certain "psychological marriage ¹ * reaction in the observer; it is an undisputed fact that white, blue and green hues and the resulting mixed colors in detergents are preferred by the consumer" regardless of the many explanations that have been given so far have tried to give, it is absolutely certain that the consumer associates the achievement or existence of a particularly hygienic effect with the colors mentioned · In contrast, certain other colors, eg yellow, brown and similar colors, in the vicinity of cleaning agents

Consumer dislike

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In response to these facts, iron became the relevant Industry extensive work on the development of cleaning agents such as detergents, abrasives and the like carried out, which respond to the consumer in the sense described above. Although this work too certain ?! Have led to successes, the products developed here still have some significant disadvantages

For example, an essential feature of the detergents of this type proposed so far is the product itself colored or partially colored. The main objection raised against these products is that they are not pure white when dry, in other words this, that the preference for green, blue and the like Color tones apparently relates more to the practical application of the means than to their original state, i.e. the Color should preferably be a direct result of the application of the product in water and not a property of the product itself

Be. "An optimal product müite when dry to be pure white and the color only when in use, such as _0, when added to aqueous media or otherwise touch old develop this.

The methods proposed so far to solve this problem however, have had limited success. 3o has the use of dyes in the leuco form, soft in Solutions of the cleaning agent on certain conditions, e.g. pH value, temperature etc., react with a color change,

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In all cases, all of them have not proven to be entirely satisfactory. So is the often inadequate stability of such dyes, especially in the presence of oxidizing substances in the Products, a major obstacle to their use. The insults to which the use of such substances is subject are so numerous in many cases that afterwards looked for other ways to solve the problem mentioned will ma.

Detergents which can be picked up or dispersed in Aqueous media to develop a conspicuous color have the further great advantage that they enable the consumer Reduce the concentration of the agent in aqueous media to estimate, i.e. the color development provides a measure of the dosage of the agent in practical use. Dartt over can be found on the basis of the color intensity or the disappearance of the Easily determine the color in the cleaning solution when the solution needs to be replaced.

It has now been found that there is a practical effect However, contact with aqueous media can cause a noticeable color-developing cleaning * - or abrasive agent, if «at the very best in its manufacture critical Conditions observed.

With the 'present invention, therefore, abrasives

suggested, which on contact nit aqueous

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Media experience a noticeable change in color, but the disadvantages described above are completely or at least largely eliminated. Furthermore, it is an object of the invention to propose abrasive agents of the type mentioned, which are particularly suitable for cleaning hard surfaces »Finally, the invention is also intended to provide a method for Manufacture of abrasives, which undergo a noticeable change in color in aqueous media.

The invention accordingly relates to virtually white scouring agents which, when they come into contact with aqueous media, undergo a noticeable change in color and are characterized by this are that they are essential ingredients 1) 45 to 95 parts of pebble abrasive, 2) 0.1 to 50 parts to the touch with aqueous media hypohalite releasing bleach,

3) 0.5 to 30 parts of water-soluble organic surfactant and

4) 0.001-0.1 part of a pigmented carrier, containing colorant that experiences parbextension on contact with aqueous media

"Color extension" is used in the present description a color formation or color development understood in the sense, that a color that can be seen with the naked eye develops <> Why this term was introduced can be seen from the following explanations?

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The colorants used in the products according to the invention can be selected from a relatively large group of substances, i.e. they can consist of one or more of the raw materials normally used for the production of abrasives, which are however brought into a suitable pigmented form for this purpose. The raw material chosen for the figment treatment can therefore be selected from. silica-like abrasives, aB «silicon dioxide, surfactants of all kinds, ie anion-active, cation-active, niohtionogenic or amphoteric surfactants, water-soluble inorganic builders, e.g. trisodium phosphate, pentasodium tripolyphosphate, tetrakailum pyrophosphate, tetrasodium pyrophosphate, tetrasodium pyrophosphate, tetrasodium pyrophosphate, alkali metal nitrilicates, - bicarbonates, and the like, of which like many, sB Natrlumbicarbonat, Katriummetasilikat and also act as buffers, bleaches, aB chlorinated trisodium phosphate (bleach N-Chlorimidtyp are not recommended because of the associated stability problems as a color carrier), bleach Help "agents, eg alkali halides such as sodium bromide _f antiseptics or germicides, as well as Pleokenentfernungsmltteln carboxylic acid ", in particular oxalic acid exist. For the composition of the colorant, ie the component understood under this designation in the present description, there are numerous possibilities for variation. The colorants suitable for the products according to the invention, however, are all characterized in that they are due to various factors such as avoidance of

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Parbexteneion In the dry state, particle size, concentration, etc. la Cteeaatprodukt not eind to recognize bloflen eye ia Soheueralttel bit.

The particle size of the medium for the invention Products with very precise and strict requirements meet ι Deviations from this make it impossible to produce a product of the desired pure white color Ib dry state su obtained,

. which on contact with old aqueous media a clear Parb development or parbextension seigt. 3o from the part size of the conveyor ia range from 50 to 600 microns be formed, with a range ion 200 to 400 microns is particularly advantageous, or - specified differently - it Buses about 95 * of the fttrbeaittelteilohsti a sieve bit one aaeohen size "on 0.044 Ba (U3 standard sieve 325) pass · How important it is to adhere to these limits of particle size arises from the fact that any major deviation therefrom leads to unusable products

^ specified wax 1 aal value significantly exceeding particle size a product alt Tarbextension, fl.h. old clearly recognizable colorsun *** see B. Bit blsuea, blaa-grönea or seineliohea Get the color tone · So the desired wave appearance is achieved not reached, but already found the dry state sine due to the dense accumulation of large particles Parbextension instead. On the other hand, the application performs very fine particles, i.e. in a «r UrUBe substantially below the

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specified child limit of lying particles, due to the large surface of such particles is also inevitable a color extension when dry. In any case it can the required degree of comminution of the particles with conventional grinding devices, taking into account the nature of the particles, i.e. their hardness, size, fragility and the like, easily obtained.

Prevent any possibility of Farbexteneion in dry state wrmeiden su, snzB the proportion of the colorant, that is, "are held in the abrasives also throughout bestioaten critical limits of the pigmented carrier, ie, it must be in the range of from about O to about 0.1 and ₉ OOI preferably • between 0.005 and 0.055 parts by weight, based on the weight of the total product.

According to a preferred method, aan provides the colorant by mixing the intended pigment beforehand with the particles serving as pigment carriers. As pigments know in the dyes for the products according to the invention Two substances from a relatively large class of substances are used, but they also have very specific requirements It is of course important that the pigment is "not extended" in the sense of the above explanation, ie, in the overall smell is not visible. Generally stick such pigments have been found to be suitable which are in water

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are easily dispersible »On the other hand, there are pigments which are not are dispersible in water, when added to aqueous Media out and are therefore for the products according to the invention not suitable; they form when introduced into aqueous media but not only insoluble color debris or deposits, which are objectionable from an aesthetic point of view « but also have a pronounced tendency for color extension in dry abrasives »Sine more

W The requirement for the choice of pigment relates to the composition of the pigment {pigments with a reflection in the wave range of the visible spectrum "from 450 to 535 millimicrons, which corresponds to the heflexion range iron blue to green wet as well as in dry condition to a large extent be resistant, 'especially in view of the fact that the follow-up in the manufacture of the scouring agent a very intimate contact of pigment and

^ May require bleach.

Of course, one of the above-mentioned requirements for the pigment also that it must not impair the desired effect of the finished abrasive in any way «within the The pigment can be selected from a relatively large class of substances, including the limits set out above other animal pigments, mineral pigments and synthetic pigments are used »Particularly beneficial

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Results are with Phthalocyanine Green and Phthalocyanine Blue obtained ο Of course, Piguentauchungen from two or more pigments are used, which is mainly from Aspects of manufacture is starred.

For best results it is recommended that when preparing the premix of pigment and carrier, a weight ratio of carrier to pigment in the range of about 1 to about 150 tons and preferably 10 to 100 tons. Again, compliance with these specifications is required to allow for parbextension in to keep the dry state as low as possible and accordingly a color change of sufficient contrast to ensure that the abrasive agent does not come into contact with aqueous media ο Within the specified limits, the Value to get the best results, of course, something move as it depends on various factors such as the nature and properties of the pigment and carrier depended

Without wishing to be bound by any particular theory, one can assume that the mixing of pigment and carrier leads to adsorption or mere adhesion of the pigment to the carrier surface, i.e. molecular diffusion, which is characteristic of an absorption process if Only takes place to a very small extent at all.

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In every pall and regardless of the ones actually taking place The process is, however, proven to be able to diaper the water Pigments adhere to the carrier with the required strength, so that they can be handled other manufacturing processes do not cause any difficulties.

The water-insoluble inorganic pebble-like abrasives for the products according to the invention can also be selected from a relatively large class of materials, ie all abrasives normally used for the production of cleaning agents for hard surfaces can be used. But again certain criteria must be considered in turn, vm products slt optimum effect to obtain. An essential requirement is that the pebble-like abrasive must have the desired, practically pure white color * The specification "white", "white color", "practically pure white * can, although they represent subjective values, even in significant objective values it is necessary that this component of the abrasive has a high reflection value of at least $ 80-85 at 550 m / u. Filter photometer model 610, a Sardner Parblifferenzmeter model AC-I or a 3pektropho to meter like a "Genesis 1 Electric Recording Specfcrophotoaster"

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Determination of the reflection values In the above-mentioned apparatus, powdery samples of the sole agent are used; the determination itself is of course carried out according to the instructions for the respective apparatus. In practice, it often turns out to be necessary to "support the usual bleaching of the pebble-like abrasive, for example by using larger amounts of bleach, for example zinc hydrosulphite, in order to give the abrasive the genuine degree of whiteness. The particle size of the abrasive should range from about O _t OO1 whether lie ran to about 0.4; usually there are at least about 85 Gew.J * and preferably 97 wt _o? C of the abrasive · effective abrasives are obtained pass through a bit of a Hasehenwelte of 0.074 mn Especially if © used to abrasive parts he η, of which at least 8 wt. * £ about 0.037 mn or more in diameter. The abrasive is used in amounts of at least about 45% by weight, and preferably from about 45 to about 95% by weight, based on the chemical abrasive; A proportion in this area has proven to be very advantageous for achieving the flanged degree of cleaning when foiling tarnished metal surfaces and when removing greasy dirt or deposits of soft substances such as aluminum from Ponellan surfaces.Generally, a pebble-like soleplate with a high content is preferred of alpha-quartz and is absolutely acid-free, since acids, even in traces, have a harmful influence on every color,

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which is added to the abrasives. It is also of great importance that the moisture content of the oil-like abrasive is below about G, 1 #, this material must be practically water-free and it is obvious that the presence of relatively large amounts of moisture in the dry state of the product is necessary to avoid any possibility of early Parfcextension außzuschlieösB "pebble-like abrasive && r desired purity ^ ferbe etc", which look particularly good for are the erfitidungsgeiEflSen products, wn as Hendelsprodukte various companies erhältlichf as examples, that from a @ r Penn Glass Sand Corp. under the name "Super Whita Treated 160" traded Siliciumdiosqrd and to η of gl calibrate firssa under the Beasielinm ^ g •• Extra Bright DP 90 ^M geliandelte product be called "Other suitable siliceous abrasives sini next SiIiciuffidioxyd feldspar _f Btmateiii ₅ Vulkaneaclie, Matofaeene ^ öe, bentonite, OslumcarliOiimt, Talksi and dergleieiisn «owle mixtures of these substances. Particularly gate l-pgöbaisaa Bit SiliciusSioxjd and feldspar, obtained because flien® Suljstanseii both in terms of the they go through ice cream ^ ö <? ui; t © - _s superior to etsrse

Wie- already ges-ig ^ "v-ardio _t kmm © in feil ße ^ S ^ lilöilaittCi 2 © lg

"Ds? * feie I * iga-ziittrügen": ßrwen-

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The portion of the abrasive must of course be the same as the one above Carrier comply with given specifications in terms of proportion, particle size, etc.

The scouring agents according to the invention also contain as essential component of a bleach} These bleaches can generally be defined as substances, which is called Contact with aqueous media hypochlorite and / or Release hypobromite bromine. Such substances are known to the person skilled in the art and are sufficient in the relevant literature described. It is of course important to have the bleach is used in anhydrous form, but the presence of crystal or hydration water is permitted. Suitable bleaching agents are, for example, the dry particulate heterocyclic H-bromine and N-chloroimides such as trichlorocyanuric acid, tribromocyanuric acid, dibromocyanuric acid and trichlorocyanuric acid and its salts with water-solubilizing cations such as potassium and natriusu The bleaching agents can be used as mixtures of two or more bleaching agents; a particularly effective bleach of this type is, for example, the product available from Monsanto Chemical Company under the trade designation "AC 1, -66", where "ACIi" stands for "available chlorine" and "66" indicates the parts available chlorine per pound (454 g) «This Product consists of a mixture of potassium dichloroisocyanurafc (4 parts) and trichloroisocyanuric acid (I part)

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It is also possible to use other N-bromide and ir-chloroimides such as, for example, N-brominated and If-chlorinated sucoiniaid, malonimide, phthalimide and naphthalibide. Further suitable compounds are the hydantoins such as 1,3-dibromo- and 1,1-dichloro -5,5-dimethylhydantoin, W-Mbnochlor-C, C-diaethylhydantoin, Me thy len-bisCH-broe-CfC-diaiet hy! Hydantoin), 1,3-dibromo- and 1,3-dichloro-5-isobuty! hydantoin, 1,3-Dlbrom- and i ^ -Mehlor-Jj-methyl-S-ethylhydantoin, 1,3-Bibrom- and!, B-dichloro-StS-diisobutylhydantoin, 1,3-Dibrora- and 1,3- Dicblor-5-n-ethyl-5-n-anylhydantoin and the like ο Other suitable hyp ο halo genite-releasing compounds are, for example, TribroEiiaalaiain and üriohlomelanizt. Dry, particulate water-soluble anhydrous inorganic salts such as lithium hypochlorite and hypobromite are also suitable. qUmzu i ^ tiisäigen solid complex or hydrates werdöii? si & istä belong for example to fFatriuia ^ p-

- ^ roa & Bdartrilqrdrat, Hatriumbenzol-sulfo-chloraain-, öaleiu && ypobro »it tetrahydrate _t Calclunhypochlor t ~ tetrahydrate and the like. Brosiated and chlorinated trinatrium phosphate, which are obtained by dissolving a solution of sntaproch. * Rifl'Ti Watriuahypohalogenit with trinatrium phosphate (and water, if necessary), are also effective bleaching agents. which are both hypochlorite and hypobromite

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dismissed; these include, for example, the K-brominated N ¹ -chlorinated heterocyclic imides such as the IHBroia-N ^f -chloroyanurstturen and their salts, 8.B. ü-MonoljroiE-HjK-älchlorcyanuräure, H-MonobroR-N-monochlorcyanuräure, Ifatrims-N-BonobroM-R-eonochlorcyanurat and Baliue-N-monobroBJ-lf-aonochloioyanurat, as well as the N-brooierte H-ohlorierten. K-Broe-lf-ohlor-StS-diaethylhydantoin and N-bromo-lf-chloro-5-ethyl-5- * ethyl-hydantoin.

The hypohalite-releasing compound is in a Total product-related amount of 0.1 to 50 wt. ^ C and preferably about 0.1 to 25 wt. C. used

Water-soluble organic surfactants which are stable in the presence of the hypohalite-releasing bleaching agent used can be used as surfactants in products according to the invention. These surfactants can be anion-active, cation-active, ajq> hoter or non-ionogenic in nature, whereby it is of course assumed that they are compatible with the total product in the specified proportions. If the surfactant is liquid under normal conditions, as is generally the case for non-ionic surfactants, it can be converted into a solid part of the composition if it is adsorbed in a known manner on organic clay or similar agents , the etifiar for an aueraie-nöefi iltebilitSt as «Eat TmmM m

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are, fee matches the color, i.e. the tens id must be from the above reasons such as appearance of the finished abrasive, Avoidance of color axtension when dry, strong Color change on contact with water and the like are practically pure white in color.

The anion-active surfactants which can be used in the products according to the invention are surface-active compounds with an organic hydrophobic group and an anionic soluble group. Typical examples of the anionic group that follow are the sulfonate, sulfate, carboxylate, phosphonate and phosphate groups. Anion-active surfactants that can be used for the purposes of the invention are, for example, the soaps such as the water-soluble salts of higher fatty acids and harsaätts * © n _s which can be derived from animal or vegetable fats, oils and waxes, & .B * the sodium soaps -from tallow- , coconut- and fellUlfeitsäuren or mixtures thereof as well as the _P e d sulfate η un5 sulfonijerten Tensiie synthetic, particularly those having 8-26 KbfeleEistoffatomen and vorsugsweise 12-22 Ib & LMIS to ff atoms in! felektil "

s ^ ntte ti his aniona & T LVE fessiie are beispieie the einkernig® "fcMimm AU ^ lerylsiElibxiate * ζ" Έ "higher iosiaie iiit 10-t6 WsihlmwAmff & TQM & n in § @ r barren ^^ rzweigten alky! group _f s ₆ B _c ÖIE ifetrium

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salts of decyl, undecyl, dodecyl (lauryl), trideoyl, Tetradecyl, pentadeoyl and hexadeoylbenzenesulfonates, higher Alkyltoluene-, -xylene- and -phenolsulfone te as well as alkylnaphthalenesulfonate, e.g. asmoniumdiamylnaphthaliiisulfonat and Natriuod inonylnaphthallnsulfora t < >

Further suitable anionic surfactants are the olefin sulfonates, soft long-chain alkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxy alkane sulfonates. These olefin sulfonates can be prepared in a known manner by reacting SO with long-chain olefins having 8-25 and preferably 12-21 carbon atoms of the general formula RCH = CHE ¹ , in which H is an alkyl group and R is an alkyl group or a hydrogen atom, to a mixture of sultones and alkene sulfonic acids and subsequent treatment of the mixture to convert the sultones into sulfonates. Further suitable sulfated or sulfonated surfactants are the paraffin sulfonates such as the reaction products of ^ -olefins with bisulfites, for example sodium bisulfite, for example the primary paraffin sulfonates with about 10-20 and preferably about 19-20 carbon atoms, the sulfates of higher alcohols and the salts of -sulfofetta acid esters With, for example, 10-20 carbon atoms such as methylol -sulfo myr is tat or -oc-sulfotalg fatty acid ester.

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009846/1732

Furthermore, sulfates of higher alcohols such as nafcrium Iaarylaulfat and fiatriuabalgalkoholauLfat, turkish red oil or other sulfated oils, sulfates of fatty acid mono- or -dlglyoeriden, z, B, stearic acid monoglyceride monosulfate, alkyl poly (ethenoxy) ether sulfates such as the sulfates of the Eondensationaprodukte of ethylene oxide and lauryl alcohol, which generally contain 1-5 ethenoxy groups in the molecule, and lauryl other higher alkyl glyceryl ether sulfonates as well as aromatic ones £ oLy (ethenoxy) ether sulphates such as the sulphates of the condensation products of ethylene oxide and ITonylphenol, which in general 1-20 and preferably 2-12 oxyethylene groups in the molecule contain.

the reusable anion-active teneids also include the Acylsareoainate, ss.B, sodium lauroylsarcoainate, the acylestar, See the oil acid sturgeon, the isäthionate and the aoyl-N-nethyltauriöe, e.g. potassium-N-metbyllauroyl- or oleyltauride »

Particularly preferred water-soluble anionic surfactants are the ammonium salts and substituted ammonium salts such as the Mono-, bi- and triethano-amine salts, alkali salts such as these Hatriun and Eallua aces and alkaline earth salts such as the Caloium and magnesium salts of the higher alkyl benzene sulfonates and Olafinaulfonate, the higher alkyl sulfates and the? Ettaäureaionoglycerideulfafeeo Which salt is chosen in detail,

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depends on the composition of the finished product and the sä using proportions from "

The non-ionogenic surfactants, which can also be used in the products according to the invention, are surface-active compounds of an organic hydrophobic group and a hydrophilic group formed by the reaction product a solubilizing group such as a carboxylate, hydroxyl, Amido or amino group, bit ethylene oxide or polyethylene glycol is formed.

Suitable non-ionic surfactants are, for example, the condensation products of alkylphenols or ethylene oxide, for example the reaction product of leooctylphenol with about 6-30 ethylene oxide units, the condensation products of alkylthiopnenols with 10-15 ethylene oxide units, the condensation products of the monoethyl alcohol esters of x hexahydric alcohols and inner Xther same as sorbitolmemcoleat 3orbitamaonolaumt _f and Mannttaneonopaleitat and the Kondensatlonsprodukte of polypropylene glycol having Xthylenoxyd.

Sectional surfactants can also be used. BJlesee a surface-active compound with an organ:! e? hen bfdrophobic group and an economic group

009848/1732

Group. Typical cationic * solubilizing groups are and ^ uaternary groups.

e synthetic katiomlrfeive surfactants are for example the ΙΉsstine as those of the general formula Rg ^ g word »H is a © Allcylgruppe with about 12 r-22 carbon atoms, S ₀ B _0? <~ 2-Jlmiß0iithyl8tearylamin and N ~ 2-Arainoäthylmyri8tylamin _f imine with AstiaftLnaungen such as those of the general formula R ¹ CQIfHC ^ H JfEU _? where E ^{1 is} an alkyl group with about 9-20 Ebalen, »eBo- ii-g-Aiainoäthylete & ryiamiä and K-Amino-

qimternttre AnmioniumverTjinoungeii "in which an" fgis 3tist © ffat © B B ± m alkyl group with 12-18 carbon groups "si & xwl Alkjlgruppmi with 1-3 K & hleB. @ t off atoms mim! wnä Si © Äl ^ 3 ^ rupp © n rait 1 ™ 3 EoSilsi ^ toffatosisa still. inert substituents such as phenyl groups and in which an anion such as a halogen, acetate or kethosulfate ion or the like is present

Ben zyl-diethyl-etesrjl-ammoniunchlorid ₉ Έτΐηβthyl ~ _f stearylamnaiiliimohloriä trimethyl-cetyl-ajuBBonluKbromid _f Dimethyiathyl tlilsuryl-aiaaoniumshlο ri d, Simsthyl'-p ^ opyl-myristyl ^ asmoni.um chloride eorde (Hq corresponding Methoeulfate and acetate «*

R'.r the erfinflungößfSB & een products suitable amphoteric Tc-nside einü neiss ^ ielsweise R-alkyl-.beta.-asjinopropionsäureni

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rr ~ alkyl-fl-iminod iproplonic acids and N-alkyl-H, Η-dime fchylglycine _t in which the alkyl group is, for example, from cocob fatty alcohols, lauryl alcohol, myristyl alcohol, a lauryl / lfyrietyl alcohol mixture, hydrogenated tallow alcohols, cefcyial alcohol, sfcearyl alcohol or mixtures of alcohols of this type fatty acids having, for example, 10-20 carbon atoms, with diethylene triamine and Mbnobalogenearbons & acids having 2-6 carbon atoms the products obtained, for example, _e i-coco-5-hydroxyethyl-5-carboxymethyl-iHiidazolin, betaines, which instead of the carboxyl group of a Sulfonsäüregruppe contain betaines in which the long-chain substituent without an intermediate nitrogen atom is bound to the carboxyl group, for example internal salts of 2-trimethylamino-fatty acids such as 2-triaethylaminolauric acid, and compounds of the types mentioned above in which the nitrogen atom has been replaced by a phosphorus atom.

The surfactants are used in the products according to the invention in terms of about 0.5 to 30 weight per weight, based on the total product ilen and preferably 1 to 7 weight points are used.

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009846/1732

In addition, various other components can be incorporated into the product according to the invention. Other preferred additives are the water-soluble builders, which include inorganic and organic, natural and neutral water-soluble salts. These builders are based on the total product, in amounts of O ¹ to 95 wt. #, And used preferably from about 3 to about 30 wt »# · Suitable Builders include, for example, trinatrium phosphate, tetra triophosphate, acid sodium pyrophosphate, sodium tripolyphosphate, basic sodium phosphate, dibasic fratrius phosphate, tlairium hexametaphoaphate ratio, hatriunium carbonate from 1 to 2> 3 _{% sodium carbonate with a SiO 2} > _{2% sodium carbonate ratio} , ^ atriiaasulfat »borax UNFI like · em suitable organic build include salts of organic acids, especially the" esserluslichen salts of Aainopolycarbonsäuren »• irks3jps Salsa Bi ^ i the Allcalisalse as the Vatrlua-, potassium xjä l'ithluäasaläe that Ammnlvaa.- and substituted aaaonium

'ii.al. £ s like ill β Methylassaoiiioai-, Diethenolajamonium- and Tri ~ EthanolaniQonnalze as well as the eel salts like the Mono-, DiuaS friäthanolaBinsalae, Msihjlaain-, Octylanin-, Diethylenlü-lajoln- and Xfchylendiaainaalze. The acid part of the salts Can also be derived from acids such as Hltrilodieseigsäure, H- (2-HydroxyäShyl) nitrilodLeaalgaäurs, Nitrilotriacetic acid, ÄShyi & ni! Laminka fcraeesigsäurθ, fi- (2-iIydroxyäthyl) äthylenediamine triacetic acid, S-HydroxsföthjrlleinodieBesigBäure, 1,2-Diaalnoc] rclohexanedi acetic acid, Biäthjlenetrlaninpentaacetic acid and the like

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derive o The builders are preferably used in such amounts added so that a pH of 8.5 to 13 and preferably 9.5 to 11.5 is achieved in water.

As already stated above, the surfactants mentioned can and builders are also partially used as a carrier for the pigment, in which case they then serve as a colorant component for this purpose they must of course correspond to the specifications given above for the colorant

In a particularly advantageous Execute ungs of the invention uses BR n addition to the above hypochlorite * and / or HypobroBitbleiohmitteln still a BleichhilfsBlttelo door this purpose are particularly water-soluble inorganic halides such as sodium bromide. The function of the Natrlumbromids in supporting Bleiohwirkung the hypohalogenitabgebenden bleach mark perhaps the beds as ^M Aual8eer ^rt effectively referred werönn, D * H * dae lead chhilfsmittel the delivery triggers hypochlorite "· and / or HypGbrcEiitionen from * Products containing both a bleaching agent and a Bleichhilfsnittel included "in general as offering" double

Products of this type develop Blelohgetjeh ^ inSigireiten «βσ that they are special

Be © Kfsti ^ itimliromta is

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009846/1732

BATH ORIGINAL

1349258

dag Pl @ B © »t | -ei © therefore not only promotes de », öeteeiicliewe ^ i? oee soaiern © shares a ier ^ rr-ögenie © means

i € © Pigments in ims HftiElgiiiigssittel das ** Die bein liateirigsii of an abrasive ^ r; elehes pi fetriwibromiS si © Mi'bsmittel entMlt «in g

almost sisggabliclslisii © rfolgendie -Par ^ bveifLnooi ^ ung seigt ale g ii © Ent ^ iellung or ÄuslSguag © trier Bl © ioli

^ eyäes ls!? ii? isa _f sisiä fesiepielweise entiseptisohe substances _e ßsE'Ei.sM © 5 FarfUEe isaä. äergleioben "These substances" rerdexa s? .ur Mssgea s set, i "o" at see the ti © iien ^ on 0 _f 05 Ms 3 Ge \? "So as preferred rcopfums eiEfl solefes liC 'a fioiatene ^ ttgBH ^ asmch Ptrlwi .3 ßijai such Esit eg v; ei3CK ;; ■:.: SIl ^ Esiaeii iintsr ö®s Besfiefeiiiiß / ieii "Cit5? Ea« ll " vmä

eic wc SQigyii: ^: ies

G sharp egg - 25

0098 4 6/1732

ORIGINAL BATHROOM

serve for the pigment; Of course, you also have to do this comply with the specifications given above for the colorant in terms of particle size, concentration, etc.

For the production of the inventive cutting agents it is - if you want to achieve optimal results - recommended, to observe the sequence described below «In In certain cases, for example when adding perfumes, it is even essential to adhere to the described sequence. Bas mixing can be done in any suitable apparatus using Stirring device, e.g. a belt agitator mixer * In practice there are initially about 40 to 6O36 of the pebble-like Abrasive in the agitator saw and then continues the perfume in the order given (if used), the colorant, surfactant, builder, bleach and finally the Reut abrasives too. Ss is recommended after adding each component before adding · * the Näshetsji one to mix for a certain period of time in order to be homogeneous and even distribution of this component in the Miashurg too ensure, in particular, one must bsi the Parftoazugaba Take extra care to keep the perfume over * the whole Evenly distribute the surface of the mixture *. Blows best achieved by adding the perfume to the mixture sprays · If the perfume is not distributed carefully enough, it agglomerates easily and then leads to reactions between

- 26 -

0 0 9 8 4 6/1732 bad original

Perfume and bleach, being highly toxic gases like For example, 3 ticke t of chloride, chlorine, and bromine gases and develop the like «

Are after all components mixed together .are, the mixture may Tn brings in a magnetic separator for removing existing metal impurities some cases it has been found dad metallic impurities with the components introduced which have been previously subjected to crushing "is Thereafter, the Msehußg in a suitable milling transferred, for example, a Schleudersehlagmtthle, "set m £ p ?? @ Jä the mixture" to the final Teilck After grinding, the daa iJslienanaittel let ready for packaging, which in the usual manner

You Brfimtmag is in the following examples in more detail ¹ S _{9 is} not limited to the same ο not otherwise noted, all Mengan in Tsilsn or percent refer to the weight *

-27 -

BATH ORIGINAL

009346/1732

18/0/58

Ks became a -'ietoeuermmittel δβι * the following
producedι

Fti »atrtnahlentts Siy (cli-» itfliehe particle size! Barfux

ojß to »Phthaloojfiminlilau tfatriu & hroBie (Seals)

Ifikron) Uli _f Wt £ 0.250 fi

O _t 7i8 fi- £ 6,085

too ₁ 000 «: ■

Dr »PrcßJkt had a prt & tiseii pure white appearance? Λ ^ Λ
ei »a» Rf flf-rJonawert ran about Q8 $ _f ssmeeeeß i. ?? eiacm irfv 5 aafrter Modiell AG-1, with more precise TletsslZer tJ>

ii ScheueiscitticXß IfOFifiteii K-ilKFici Γί »you niij *. '! p-iErt:? :: ei ims re * 4it €? ies- £ c> £ ^: ^ * tr & rden« Ηβίάϊ des Aiaflöfssn in ^ H.eeri ^' i - Fföier evf-

8> iftrai «λ *» l'j nf.ii vt-.r. vj

f «S

o himself sis O &
all ar-t ^? »* \ So fstt _f
lllfthGi? how

f \ ii 0 ft / t "/ 1 ^e i% ^

Vx

BATH ORIGINAL

(Manufacturer Great Lakes Chemical Co.) mixed. This Colorant had an average particle size of 10-150 microns.

The product was made into one in the following mixing sequence Agitator mixer manufactured with weighing device, the mixer being continuous during the entire mixing process operated at a speed of 37.5 rpm »

1) The belt agitator was switched on earlier.

2) Some of the total abrasive to be used (about 4O-6Q56) was added to the mixer

3) The perfume was sprayed in order to avoid the formation of agglomerates by evenly distributing the perfume over the entire surface of the mixture; after adding the perfume, mixing continued for about 3 minutes «

4} Bas of blue-pigmented sodium bromide was added and evenly distributed over the entire surface of the mixture; after that it was welter for about 1 minute

mixed.

5) Until the entire amount of Ten aid was added and mixed thoroughly.

6) The entire amount of trisodium phosphate was added and thoroughly mixed.

7) The entire amount of trichloroisocyanuric acid was added.

- 29 -

009846/1732

19A9258

θ) The remainder of the total amount of abrasive was added

S) The mixture was transferred to a magnetic separator.

10) The mixture was transferred to a centrifugal sole mill

The product had a particle size of Example 2

Example 1 was repeated, except that the colorant was a premix of phthalocyanine green (2.5 parts) and sodium bromide (97 t 5 parts) used From the product to aqueous media, there was a noticeable color change to luminous OrUn. Also pointed that Product has an excellent whitening effect when treating hard surfaces of various types.

Example 3

In this example the trichloroisocyanuric acid used in Example 1 was replaced by chlorinated trisodium phosphate replaced. The product, which was prepared in the same way as in Example 1, had the following composition!

- 30 -

009846/1732

Finely ground β silica 85.798 #

Perfume 0.250 *

Phthaloeyanine blue premix

and sodium bromide 0.512 5 *

! fetriumelkylbenzenesulfomt 3.940 #

Sodium carbonate 2,000 #

chlorinated trisodium phosphate 7,5OQ j »

100,000 i>

* Example 4

Example 3 was repeated jedooh the gleiohe Vornieohung from phthalocyanine green g and Natriunbroald was as a coloring agent used in Example 2 · tia were similar Srgebniese as in vorhergehest & n examples with respect to an eye-catching larbuaiol ^ ae in "Löaen in aqueous media, get Bleloheffekt etc. .

Example 5 to 18 P Example 1 was repeated bit the following modifications »

- 31>

003046/1732

at Bleach ? tirbmittel carrier pigment Phthalocyanine blue Weight game green behaves Phthalooyaniη-
blue nis Phthalo oyanine-
blue Carrier: Phthalocyanine pigment Silicon dioxide Phthalocyanine blue 50i1 5 Trichloro blue Nat riuMbroiai d / Fhthalr ayaDin- Phthalocyanine cyanuric acid Nmtriuabroeid Phthalocyanine 3ilioixi »dioxide blue 25 «1 6th Tribromyo- blue (aew.Tsrh.1t1) oyanure acid Silicon dioxide Phthalocyanine Sodium Eiacat 50t 1 7th Dichloriso grtin Sodium sulfate cyanuric acid Natriuabroside Phthalo cyanine Feldepat 25: 1 8th Dibroalso- green oyanuric acid Trinatriua Phthalocyanine NatriUBbromide 75Π 9 Sodium dichloro phoapbat green isooyanurate Sodium Phthalocyanine dine thylhyiftnto in 50i1 10 KaliUBdibrott- bio carbonate green ieocyanurate Sodium dodecyl Phthalocyanine 25i1 11th Caloium hypo- benioleulfonate grttn chlorite Silicon dioxide phthalocyanine
jrriln 5Oi 1 12th Lithium hypo-
broait Ratriuabromide 25i1 13th Potassium dichloro ieoojanurat (4 parts) and Trichloriso cyanuric acid (Part 1) 50i1 U KiBl iuaeonobroM- aonochlor- oyanurate 75i1 15th H-Broneucoin-
iaid 75i1 16 H-chlorauocin-
i »id 50t 1 17th iso cyanuric acid 25t 1 18th lf-Monobroe-H- «Onochlor-5« 5-

009846/1732

1949253

All of the above products showed a noticeable change in color when placed in aqueous media. In all cases, the products themselves were of an appealingly white color and showed no traces of non-Meissen hues or parallels of 1 Ma 1500 microns, while the k total product after the treatment in the centrifugal flour mill had in all cases a particle size in the range from 1 to 500 microns _o

The moisture content was in the products of all the examples _r based on the total product, adjusted to untei ^v 0 _y 4 # ο As frosted was further stated above, limited to the moisture content of the individual components, preferably to a very low value, d * h. practically anhydrous components are used to eliminate any possibility of color expansion when dry. The individual components are used in a practically dry state, doh. they must contain practically no free water, but they may include crystal water or water of hydration, doho water in its bound form. The specified moisture content relates to the content of free water. Most commercially available 3-silicas, doh. the components making up the predominant constituent of the products according to the invention have moisture contents below about 0.1 ^ ₀

- 33 - ■

009646/1732,

BAD ORfGIMAL

Results similar to the above examples were obtained obtained when instead of the surfactants used there, nonionic, cationic or amphoteric surfactants are used were »The non-ionic surfactants are particularly suitable for products that shouldn't foam as much. On the other hand, cationic surfactants are preferred if you have a Want to achieve bacteriostatic effect, since these surfactants often have a pronounced germicidal effect.

In some cases it may be desirable to use the pigment as such as a colorant, ie not to use a separate carrier component for this purpose. In general, however, the use of a carrier is preferred as this aids in the even distribution of the colorant throughout the product. In any case, the terms "colorant ¹¹ ," pigmented carrier "etc. apply to both embodiments, unless the context indicates otherwise.

009846/1732

Claims (1)

Colgate-Palmolive Company New York, H.Y., V. St ..A. Claims Practically white abrasives, which! Is in contact with aqueous media experience a noticeable change in parh, characterized in that they are essential components 1) 45 to 95 parts silica-like abrasive, 2) 0.1 to 50 parts in contact with old aqueous media Hypohalogenous bleach, 3) 0.5 to 30 parts of water-soluble organic surfactant and 4) 0.001 to 0.1 part of a pigmented carrier, old aqueous media when touched Parbextension experiencing dye contain· 2. Abrasive agent according to claim 1, characterized in that that the carrier in coloring agents made of sodium bromide, silicon " diocide, trinuminum phosphate, sodium carbonate, sodium dodecylbenzolaullbnat, a compound of hatriurabromide and silicon dioxide, sodium silicate, natrixima sulfate or Feldspar is made. . - 35 - 009848/1732 BAD ORiGINAL . - 35 - 3 "Abrasive agent according to claims t and 2, characterized in that it is used as an organic ensl.a Hatrlumdodeoylbenisolaulforat with. 4 «Scouring agent according to claims 1 hereby · 3t characterized as having a compound as a bleach from the class of N-chloroimides, N-broraimides and H-bromine-chloroimides. 5 * abrasive according to claim 4, characterized in that _t it as a bleaching agent trichloroisocyanuric, tribromoisocyanuric, Bichloriaocyanureäure, Dibromieocyanursäure and / or a Alkaliaalz containing the same. ο Scouring agent according to claim 5, characterized in that it contains a mixture of 4 parts potassium dichloro isocyanurate and 1 part trichloroisocyanuric acid as bleaching agent. 7 · Scouring agent according to claims 1 to 6, characterized characterized that the oe still contains 3 to 95 parts of aaser-soluble builder. . ' ^: . 8. Scouring agent according to claims 1 to 7, characterized indicated that there was still a small amount of perfume contains « - 36 - 009846/1732 9. Abrasive agent according to claim 8, characterized in that that there are all abrasives Siliciumdiojcyd, as bleaches Trichloroisocyanuric acid, as an organic surfactant sodium dodeoylbenzenesulfonate, as a coloring agent phthalocyanine " contains pigmented sodium bromide and trinatriuraphosphate as a builder. 10. Scouring agent according to claim 6, characterized in that that silicon dioxide is used as an abrasive, chlorinated trisodium phosphate as a bleaching agent, and organic as an organic Tens id sodium dodecylbenzenesulfonate, as a coloring agent phthalocyanine pigmented sodium bromide and as a builder contains sodium bicarbonate. 11. Process for bleaching hard surfaces, thereby characterized in that the surface to be bleached is treated with a scouring agent according to claims 1 to 10. 12. Process for the production of abrasives. According to Claim 1 to 11, characterized in that in a ribbon mixer to etna 40-6Q? s provided : Total amount of abrasive one from one pigmented Existing carrier in contact with aqueous media Farbztenslon experienced coloring agent gives, both mixed to a homogeneous mixture and then - 37 - 009846/1732 ORiGiNALSNSPECTED in the order given surfactant, builder, bleach and the. remaining amount of abrasive added, whereby after adding each component, nan ensures an even mowing and during the entire process Mixing sequence moves the mass continuously. 009846/1732