BE732556A - - Google Patents

Description

  

   <Desc / Clms Page number 1>
 



   PATENT OF INVENTION Coating compositions and their preparation

 <Desc / Clms Page number 2>

 
 EMI2.1
 This invention concerns doa ODN? TL% Itioiu de rffltemmt and Game methodo to prepare case ition..L81DV8utioQ GOQCV "more particularly C9Ç08id.ona ootwpzanant several pbaa .. aquawaa, including one or more cartir: .." :. l one ¯ tkiu from revetsnant.

   At certain 69 of, 14tavmtion this r * worte 4 of the aqueous globules viiibiemont distinct from tPtk1au of rev8t8HIDt cu..I181 "". in an aqueous medium. an intrinsic limitation of the aonvontiomwileo coating do-.ment employing organic solvents. * and that elie * are 8U80.pt:Lble. only to provide :! ' r "" t: eMDt8 hRm4J., and that they require -> separate steps to produce two or more colors. different. go, where often an unpleasant odor to obtain results .1Btai.an they must be applied to a well prepared, non-porous and relatively smooth surface. Otherwise it is difficult to obtain a uniform appearance revote. The coating applied must have limited * dpaia * eur * so as not to give rise to left-handedness, wrinkling, or cracking.

   If you want to achieve a screened or large finish, a separate operation is required after coating has been applied.
 EMI2.2
 



  In order to overcome some of the prior limitations of conventional disclosure materials, aqueous emulsions and latexes have been employed. Like water soluble vehicles, these have distinct advantages, but they do not. do not give easily variable and adjustable textures, and they do not remove the limitation on monochrome rework.



   Another means of overcoming the difficulties and limitations associated with the use of conventional coating compositions or aqueous and latex emulsions is that described in U.S. Patent No. No. 2,591,904, issued to the applicant on 8 J.VRIL 1952.



  According to the compositions of this patent, it is possible to obtain textured and multicolored coatings by applying a single layer. The said patent coating compositions employ an aqueous dispersant medium containing a coating stabilizer, wherein the dispersed particles of an enamel or other organic solvent based coating composition are substantially immiscible.

   The separation of the oryanic solvent-based dispersed coating composition from the aqueous dispersant medium is accomplished by employing, in the dispersed droplets, organic solvents which are not miscible with the water.
 EMI2.3
 aqueous phase and coating materials which are substantially

 <Desc / Clms Page number 3>

 
 EMI3.1
 inaetwMea dm * law, m diop aant aqueous .. la4dm.c If sl = ¯¯ t.iwaa ........ -r N Wl88At aocept '.., U a.toe..1'ô' 4 'avqf.i -;'; l: 8OOU8 to omlvaate <Mr9Miquea provides some tnaonv '.. 1ent8..P.



  1, # * 801..t8 # pavent peevoquor certaina deqçe * "" 14- y. oemuoi 4 VobWn 4 * tOxi1% é and odors ddsa9riablas., De p1W In 8O! .ftDU # po1que. oonwnables are often * dared to be expensive.



  At the point of the CM 1 0% AtSm8 4 <MMt 1 0 posuito gp 1'on can aloY. on * #knt '1..M. "'8 i'om% ion do q (18hp08it: l.ona de rawitswat tNpo" .JnU88 of this. Disadvantage *.



  8on cet'- inrsi4o. there is provided an aqueous mixture of rn8teIMnt t plus aqueous base, the smokes * tails being iw # 4ttqu # mnt Ln801ubl .. one in the other or immiscible one. 1 aut & o, and U86 or glu8i.ra desditas pimaes 8qU8US88 containing a 9% ôriau da 1ov0t-nt, provided that <'tlo <Mq <M leu bases * qu * é6 @ a are goum for one. diepera6 gels. danced a mid nweoem. mi agsnt 1n8Ctlubiliaant is contained ow 80Uae dan. lolit a111eu cm obtains the results and 1, this new and unexpected effects of 1% priunt. invention thanks to compotitiooe de r.v8tesaent co <E! f <MMtpt plus an aqueous photo, including ugàe or plu * 1 * ux. * oonsieneunt as omt4ràAux coating.

   In bian cases, one of the aqueous phesen * does not consist of independent globules * <iu <mx which remain d.ne1bl ... nt adPar6o and distinct * from each other, that is to say that the dispersion is stable. In other cases, one uses "iaper.1onr passagiras, in 14i8 '" the globules or the droplets. dispersed can land one to the other, but break down by subsequent agitation. In both types of dispersion, the colors used in each phase remain substantially within the range.
 EMI3.2
 this phone.
 EMI3.3
 



  By the terms aqueous ophose "and" aqueous medium "are meant water-based composition but not excluding the presence, in minor quantities, of other solvents. For example, the aocpo.t1 may contain a euorganic solvent miscible with water. water C018D8 carbonating agents, or organic solvents immiscible with water
 EMI3.4
 as constituents of emulsified foil-forming vehicles.



  The properties * and the effects of the present compositions are
 EMI3.5
 noticeably different from those of emuleiones, colloidal dispersions, etc., in that the particle sizes are larger. The size and shape of the dispersed blood cells will depend on
 EMI3.6
 of the effect you want to produce.

 <Desc / Clms Page number 4>

 
 EMI4.1
 



  The unique effects of this invention depend on the coexistence of at least two aqueous phases, which is ensured in the present compositions by certain methods of lubrication.



  By "insolubil:.:; Ation" we denote the process of treating aqueous compositions in such a way that, when mixed, both the initial constituents and the re-eluting components of this mixture have only one solubility or uno m4scLability limited one in the other, form a c-composition of two or more
 EMI4.2
 aqueous and distinct phases, in which the materials coJ.o-
 EMI4.3
 rants which they may contain are kept significantly z6parate and listl1 \ "aa in their respective phases, that is to say read globules or 1 a droplets on the one hand and the dispersing medium on the other.

   We therefore consider log cases in which all the constituents
 EMI4.4
 results, whether dispersed or dispersants, are liquid
 EMI4.5
 or reletiveme:, t fluids or semi-fluids, and can be said to be immiscible or Jl ': 3o) .ubles one in the other, as well as the cases
 EMI4.6
 wherein one or more of the resulting components is a soft or consistent gel.
 EMI4.7
 



  Insolubilination can be accomplished using one or more of a number of means which can be used singly or in combination.
 EMI4.8
 the ones with the others. In some cases, we can use
 EMI4.9
 suitable products which tend to swell without completely dissolving
 EMI4.10
 tement in aqueous media, well we can modify the benefits available, for example, by polymerization or crosslinking,
 EMI4.11
 to make them either insoluble or not sufficiently insoluble. Some of them can be notably soluble when cheeked, but possess the limited solubility required at normal temperatures.

   In other * these, the required solubility characteristics can be obtained by nug + ntution of temp4r.ate. or by elective formulation of the solvarcts, for example "lIp'V 8 :() 1804ifiMt. aqueous media with or9114U. miscible aolvatites z 1'eGu.



  Herein a0wp08it: iona. we get 1'in8011lbi11. "!. $", ô rcquiae principal8ID8Dt% mr ut1U.8It.tion cS'8gcJDU appropriate inrolubilizers that we "use .. daM taD8 0-3 pla3 *! n * <t cie . phssrs .quft..8 Pti? exempltl, some r's1 forumt dec aolutiono 8q1I8U848 which are practically unmieeib1 .. 8Y8fJ 1 'ft 801at: ic'tDa aqwe aa c18' 1IU: t'6e resins. an important aspect of Iliriveration ..t: that of- lae-if we obtain the i.n801ubilt..t: we at the "1I! t of oyftèmm irtirolubilisemta which contionnant a 8g8ft iDGc1abil1MRt and a 0011.0161 hrdJ: OPb1] s, In a certain mother , the wcyeft of iD Oi1i8.tioft the plan

 <Desc / Clms Page number 5>

 
 EMI5.1
 appropriate depends on whether the dispersion is transient or stable.
 EMI5.2
 



  Considering the transient dispersions first, it is neither necessary nor desirable in this type of composition that the loose dispersed glonules remain permanently and completely independent of each other. T, pic7.iement these are not gels,
 EMI5.3
 but droplets of a fluid coating composition. We
 EMI5.4
 In this case, insolubilisatton is obtained by using, in the separated aqueous phases, laminated polymers which are practically incompatible with each other. For this reason, the leaf agent> gene must be found substantially in solution in its own aqueous medium, instead of closing a dispersed fAūt3cgcne product in a latex or enamel.

   Each polymer will be used as an autp agent, giving aqueous immiscible threshold-forming compositions of the required fluid type.



  The film-forming polywres which are useful for this type of composition include the hydrophilic colloids rea ('l.llairr-: 3 and the substantially soluble and dilutable polymers in Ileitu which form films resistant to temperature. <to by drying or cooking. ce3
 EMI5.5
 the latter usually contain enough hydrophilic groups
 EMI5.6
 to be at least partly solubilized by water, the solubilloution often being promoted by means of organic solvents miz.ible3 to a .. They include water-dilutable oils, rb-ainea .1yê8, resins acrylics, epoxy resins, polymers of styrene and maleic anhydriae, and the like.



  Obtaining sufficient non-miscibility depends on the incompatibility of the foil-forming vehicles, on the concentration of the foil-forming agent in each vehicle and on the weight ratio of ten agent fG \\ ll109ne the other, and on the tumpératurc . since the immiscibility c: .it with the concentration, the preferred concentration of fuming agents is the strongest which allows the desired fluidity pEopEiet & s. With hydrophilic COllOldOEt3, it can sometimes be less than about 1, but with other aqueous vehicles it is generally less than -, -, m 20 z In the published literature relating to], it is hydroe 001101d8s. ., ta '.; 2nd *, we dnnn .ou'V !!!; t r.lUle: J.gn8Mnt8 5 \ a ":' the vehicles with which their solutions are not miscible.

   It is unexpected, however, that these aqueous 14S vh1aues could be colored diffftotllll88ftt on each other *, and then be mixed without any colors, to produce unique multicolored compositions. DeLle

 <Desc / Clms Page number 6>

   ..., ..........
 EMI6.1
 Table I below show some of the hydrophilic colloids and other feuillocene products whose aqueous solutions tend to be immiscible with each other.



   TABLE I
Table of Vehicles Nen Miscibles Aroln 304 (Resin soluble in many hydrophilic colloids, Ashland Chemical Co.) such as polyvinyl alcohol, polyethylene oxide,
 EMI6.2
 some proteins9, and many derivatives of cellulosa such as alkyl-ethers, carboxy
 EMI6.3
 alkyl-ether, and water-soluble cellulose ester; also products such as glycol bori-borate, vinylpyrrolidone-vinyl acetate copolymer, and water-soluble salts of styrene-maleic anhydride copolymer.
 EMI6.4
 



  Soluble cellulose acetate Arolon 304, Arolon 1G1 (6in water (17% acetyl) not * water soluble, Aahiand Chemical Co.) and Latok-1 (re-
 EMI6.5
 sine aolubla in water, T.y. ael.t.rn tso.). eortaineK protein solutions Many colloids; hyarophicolloldales comna3 le Technical les OflSv2 alcohol pc'.1, = fli.Protein Colloid NO 69 from Swift that, ',, polyothy14ne oxide, & <: 0. and a lot of CC <\ t1D8 cellulose derives from * alk "yl-.th.r., hydJ: oxyIil-6II, and irboxyalkyl-6f. \ c ... uethyl cellulose Arnion 304, Arolon 1C01, T * cM1- .1 Prolaiei Colloid 1``69, Latok-1.



  Goum 1C8T'ey8 IolyYJ.ny1p, n'Ol1 \ 2n80 Polyacrylic acid see I18i: hyl 8 # ylat: 8 4e 8Od1118.



  81; ranol 'JZ-6d (polyvinyl alcohol-0a.s, aaia u 1 *% hyi vi) * yl x3tas / que, du? Have of 1188D \ R8. Ce.) An1 \ i48 ukldtq - 4o Qa8ftl
 EMI6.6
 anium ta Film C'Ct.).

 <Desc / Clms Page number 7>

 



   In the case of stable dispersions, the insolubilization must not only prevent dissolution of the dispersed phase in the dispersing medium, but must also prevent appreciable coalescence of the globules or droplets dispersed with each other. The dispersed globules of the coating material are therefore thickened to some extent, but preferably not more than
 EMI7.1
 n6ceeunirg to avoid coalescence and ensure sufficient retention of coloring matters in said globules.



   It is well known that aqueous compositions containing water soluble polymers can be gelled or precipitated to a greater or lesser degree by variations in the type and amount of inolubilizing agents used. We thus make a first aqueous composition practically insoluble in a
 EMI7.2
 second aqueous coLtq3onition.



  It has, however, been found that, if the solubilization is carried out in an obvious manner, by adding insolubilizing agents to the aqueous composition, it must precipitate sub8tPtDt; '11. or not gel strongly to achieve the required insolubility. To prevent substantial loss of color by dispersion in a second aqueous medium, one must render
 EMI7.3
 the agent f8Ui U.09 is gelatinous enough rigid so that it is little flowable and that it becomes a poor film-forming composition.

   To be used blue, such consistent and non-fluid goelqs must. be di. "r8 dem? uno scor9e film-forming composition which serves to hold them in place in the sound coating, To avoid excessive roughness, this * gel particles must also be relatively small,
 EMI7.4
 Mt cons! stanee of the dispersed globules, necessary to ensure an auffisante ineulubilization, nevertheless depends, in a aurorenante way, on the introduction of insolubilizing a'l9nts in the difffrliluton phase.

   Aqueous .. it has been observed that by oetiiisant agents incoAubili8aDu on the 11th, it was even possible to obtain global bzz cL "t..r (ja size q 3 well soivated and which have \ 1r. e -11te, which retien.e.1 f urtant amff13mawsnt leare tna, ibzea: olsxset4s:., which does not 8 zuni "SIII! t not l ': r) tab18lt.8nt the ones to the naked .. in the c; rcsitinn coating liquid, which forces off the deposit of the coherent art yarns! ': of nature een8ibl8D8ftt:

   li8a8, in Itabsonce of a fumogenic agent d8D8 the mililm di8p8l'sant. araao in the present tense, u dth0c2e., it is peMibK 6 <'show! r the C! On8i.t: anc:., the size and shape of the

 <Desc / Clms Page number 8>

 
 EMI8.1
 ,, 19)) ul ... dinp f & 68 dan * une waure ML <Mt plu * grau "qut J. # ..,. L 'ieaS.ukril3, iati, on 46pom 4o 1 & -Iomtion de gels risioge, 81. we do not want * qpe âaa V1 (roll of small tUI4. it may be sufficient to use 8g8Dta 1ub11i8aDt8 in the medium dia. per * have only. wou tos nv8t. 81ltiaolct .., aepen4ant. it is g6n6x4lamnt better than beamoup of Bleoauxu typing * 6 * are at ± fi <t <maMnt big po "puuvc4r easily 41 * tin + E * one another.

   In order to achieve this, the 1ti.OD 0quOUe @ which must fight the phao di..pez: 8M must if, l88Dt au. xelativownt viscous before being -jOQc (ie at a3.iieu dispersant equmx. 8len that in a certain -ur. this thickened C acter can 8t) ;. obtained by conventional means of tonaulat1oD of rosé vdhiculws. It is often preferred to use% Ilub11ieanta agents in this phase 48perS '.. tit in less amounts than in the dispersant phase ** A preferred metl' & od # typi that of 3naolubüisation ooapot'ï: .e, d 'first, the addition of an insolubilizing agent to a complete coating composition, the concentration of the insolubilizing agent being sufficient for ta.form8J:' the coating material: in a viscous and homogeneous mass. .

   Second, this coating combination is dispersed or partially insolubilized in an aqueous medium containing a binding agent at a concentration sufficient to prevent dissolution of the coating composition dispersed. Poi, r this ratuesn the activity of the agents * insolu-
 EMI8.2
 bilisants in the dispersant medium will generally aerate somewhat greater than that of insolubilizing agents. in the dispersed phase *.



  A particularly important aspect of the present invention is that it provides a means for forming novel coating compositions, not acclaimed with water soluble polymers,
 EMI8.3
 but also with a variety of film forming agents, aqusnat such as dispersions and coating materials. inorganic which does not
 EMI8.4
 do not resist insolubilizing agents. in the same way as the water soluble polymers.
 EMI8.5
 



  It is known that the aqueous coating vehicles can be precipitated from their 801ules or be flocculated from their dispersions.
 EMI8.6
 persions in various ways. For example, solutions of alkali silicates are gelled or precipitated by lowering their pH or
 EMI8.7
 by adding to them 1Dultivalent cationa such as Al or Ca. A latex can be gelled by aging, by heating, or by addition.
 EMI8.8
 tion of agents for deactivating stabilizing surfactants. The

 <Desc / Clms Page number 9>

 
 EMI9.1
 In801ubil1.6 product obtained in this way, however, either does not have the suitable consistency or is no longer in the range of condition required to spread a continuous and cohesive film from the aqueous composition.

   The condition of this product, as 0Xq1 @, may be that of a rigid gal, a sticky precipitate # or a goemwux flocculate.



  According to the invention, aqueous stirring compositions which cannot be satisfactorily insolubilized as they are, can be treated with the foregoing methods by incorporating therein an aqueous co-agent which is the preferred type of fluid gel. with the appropriate thirty maolubilixants. It has been observed that the products suitable for this purpose are those which are ordinarily called hydrophilic colloids *, and in particular, the
 EMI9.2
 organic colloid * mRaromo2écuîoire. In this aspest of the invention, the aqueous composition which
 EMI9.3
 The dispersed globule contains a primary laminate and a hydrophilic colloid, the latter often being present in relatively minor proportions.

   Insolubilizing agents are chosen which are active with respect to the hydrophilic colloid, but which
 EMI9.4
 are relatively inactive with respect to the primary lubricant agent. It has been found that by mixing it intimately with the hydrophilic colloid,
 EMI9.5
 the primary fumogen agent could be sufficiently insolubilized without substantially altering its film-forming characteristics.



  It appears possible that the hydrophilic colloid, when properly insolubilized, forms a matrix in which the primary foil-forming agent becomes trapped without substantially changing its initial state of solution or dispersion.
 EMI9.6
 



  This insolubilization method greatly expands the field of aqueous coating materials which are subject to treatment.
 EMI9.7
 according to this invention, For example, the primary agent fe1 ;; illoqene can be chosen from: (1) Water-dilutable dispersions, such as natural and synthetic polymer latexes or emulsions of drying oils, alkyd resins , bituminous materials: for example,
 EMI9.8
 acrid dispersions of homopolymers or copolymers of polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, polystyrene, polybutadiene, polyethylene, natural rubber, poly methyl methacrylate, or others estersacrylic polymers;

   (2) Water-dilutable solutions of film-forming polymers,

 <Desc / Clms Page number 10>

 
 EMI10.1
 not888nt those who lwuwe: t 0tr * tu..fomA., pu '1 & heat, by flooding, and /, or by afflte chuUq ,, in lumlubic thread in water by e mple, leo J:'. iM8 aàwàeo soluble in u, loo J: '. 1Dor. acxyliquas, ¯16111i.a6 .. oils, etc., sometimes used in conjunction with copula solvents. water mine ibles i
 EMI10.2
 (3) Water-soluble coema 1 ... 11icat .. alc.lino products f.u111o6n) (4) The aqueous diaparaiona "of organic poly" and the aqueous dispersiou8 of the COIIIII8 mineral products ( rittaa c6xanm.quee or unsintered cereal minerals,: .os flakes or metal powders which can t01 "MZO of films) coberent by firing, om6zoat1on, sintering, treatment with flan, etc;

  and (5) Other products which churn films or which give
 EMI10.3
 properties which are beneficial to other products which cause fungus, such as clay, sand, mica, pearls or glass fibers, powders, metallic fibers, cellulose or asbestos fibers, etc.
 EMI10.4
 It is possible to use fouillogbnea products such as those which have just been listed both in the dispersed phase and in the dispersing phase of the present compositions. As we have stated
 EMI10.5
 above, when used as a leaf-forming agent in the dispersed-independent globules, they are made insoluble in the dispersing medium or immiscible with the latter using
 EMI10.6
 Insolubilizing systems comprising (a) a hydrophilic colloid (b) an insolubilizing agent for said hydrophilic colloid.



   The products which are ordinarily called hydrophilic colloids are well known and widely used in many industries.
 EMI10.7
 chemicals for many different i iges. By way of example, some of the hydrophilic colloids which can be used in the insolubilizing systems of this invention are: (1) Cellulose derivatives, such as methyl cellulose and other compounds.
 EMI10.8
 Very alcohols: cellulose 1-ethers, cellulose carboxyalkyl ethers or their salts, such as carboxymethyl cellulose, and cellulose hydroxyalkyl ethers, such as hydroxyethyl cellulose.



  (2) Proteins such as casein, zein, or other plant or animal derivatives, (3) Carbohydrates such as starch, pectins, etc.

 <Desc / Clms Page number 11>

 
 EMI11.1
 (4) From MQaz8: U.e co ...} -. ' '9ant .; 11. 9081e 1: v.7 :, "f 'J ..- 9'" .801, the quar. ily, sne, the 110., .. 11. d '1²'1u.ii of, te. i5) 0. po \ J8k- 8yatbtt1qu ... ecMM 1'a% sgol polyv: l.nyl19 \ lo, 1 'de po1.Ytth11 .., polyawcyli4ue acid OS its salts,. los OE * O1p% eO 3 'arhyde' àe ¯l'1que with COIÇOii1 '. viny-,,, 11 0-- 'there ttyrèca or their le, etc.



  Laa: o1loUv bl'dl: opb1a pr68entlmt a% grand air.'utâ: and # da nowhroMC moye scat conDU8 à0ne In technique for inI801u -... bi11 ... trovoca des r't ';, nc: ü dars many textoa is aan <the literature of mohreux suppliers of hydrophilic collolds.



  It will be understood that the most effective means of inaolubilising a hydrophalic colloid domt depends first of all on its chemical type. Far exaeaple, Table IX below contains a list of some ... of the categories of the categories of e01101d &. Organic, with amtains of * the most effective insolubilizing agents for each cot'90r i.



  TABLE II 11Q'f'.vdrqt1iti Agent in, solubilizing Polymer8 uontanant groups- Salts giving recurrent polymenta carboxyl cations, coma valents and a pH of not higher .. the carboxymetbyl celluloce, the approximately 7, hill C4C12 'MgS04. copolymers of styrene and acid
 EMI11.2
 maleic, usually .olubili-
 EMI11.3
 born in the form of alkaline nela.
 EMI11.4
 Polymers containing chelated titanium batera groups, couan
 EMI11.5
 recurring hydroxyl elements, such as titanium lactite. me carboxymethyl cellulose
 EMI11.6
 sodium, polyvinyl alcohol.
 EMI11.7
 



  Galactomannoglyc8ne and their salts giving riveted borate ions, known as guar, gum and a pH of at least about 7, traga801 starch and its derivatives: often together with dES zels
 EMI11.8
 polyvinyl alcohol and copoly- giving phosphate ions, for example
 EMI11.9
 mothers of vinyl alcohol, for example, Net2B407, NH 4 2 B 4 O 7, ÉÉÉ / 'Na5p3010' (NHJ 2HPO4 2 4 and vinyl alcohol. J.u
 EMI11.10
 Cellulose ethers soluble in Soluble chlorinated phenol salts
 EMI11.11
 water, such as methyl cellulose in water, such as pentachioro-
 EMI11.12
 or ethyl cellulose. sodium phenol,

 <Desc / Clms Page number 12>

 
 EMI12.1
 ...............
 EMI12.2
 



  'bl9IAU I (continued) Collolde h] idropbJ.1¯q Insolubilizing agent Many mac polymers: cr.tU t6- Tannic acid and its solucular salts such as poly-blue alocoî in water. vinyl, pc, 1Y't1! len-5 oxide, casein, Q; idcn, iaz cellulose derivatives forgotten in water, such as ether and
 EMI12.3
 carboxylic ethers.
 EMI12.4
 



  It was found in particular that the reduced siliceous U \., J, e hydrophilic clays (silicates colloiciaax of mc: .c; nfsiwr ... alÙ1f'.inium) and colloidal silica were very useful .. to insolubilize many types of col1oSdee hyarophilea or, 3miiqç * e When a hydrophilic clay is combined with an organic hydrophilic colloid, agents which tend to dissolubilize the clay ((Ca or Mg ions) often make it possible to insolubilize all of the CO8POaiion.



  For men. From the art of hydroilic colloids, it will be obvious that a very large number of inaolubilant agents, including organic solvents miscible in 1a..u.e are virtual! as useful in the present syst4ma inaolnbiliaanta,, t that the agents of interest will be faailameat sundr6 * by the chemical nature of the hydrophilic colloid. In practice, onpmhent, it has been discovered that, apart from the hyajfophilea $ Adr. \ I1C 0 '= Il 1J hydrophilic clays, the agents * in801ubi118ant8 which are most generally found are organic salts, Mta11àquK, a or x.rirbux soluble in water. Since the pH is often porous in the inaolubiliton, it can of course be added to aid the addition of in4UrG. dlcidea or bars. but one set it to 80 ..? i8dt p) .1 f8c11¯4t1t 'Using ..the ewid4) o or bb81.q \ 1ea ..



  The agt8 Úl8l) l \ 1bil M: lt8 pr: 8tiCfIMUJ mat those which are active at concentrations * of avirsa c, 1% 4k qpai pou cent, but preferably at pR.8 plov ct'8Drirou 1. or 2 Si ..1ÎI88 agmeir who whose,! to me d 1 ent-tzm iré, 1 - o, 2S% c1oinm :: a'è: i1: l àrea pra: it, because Ils r.sqwat 6th; 10'118 4 <MMH <tagw taa ei4 6 a. it,;. d: p aipitation que d '..,. u de jolitimtioa, au poel àwopcwtio co- - ad & 1 <", o8na1u àeutta vax sent p81'foic <tti for 1! liai of the agent trs801tt1l1U.¯ i0! aie << CC! - the mute 188 lN .1 ... Z i liz Oi-t> JfrlO'AIt, 1. & 110SM hydrophilic lai .111 little j.llIdaf.8 .8'9'Ù ...... ..- 1 i 19ft1rN! 1Id1f1Q.



  Lor8qG 'il ne axlfls JIII8 l' 89MIt totkillr4ë yralâ, 1.1 8ft

 <Desc / Clms Page number 13>

 often desirable to limit the proportion of hydrophilic colloid
 EMI13.1
 the to the quantity the p} 11 ± low possible in order to minimize the sensitivity to water. In this case, the preferred hydrophilic colloids are the organic macrarular polymers which are characterized by the predominance of linear colloids rather)! as spherical colloids, and in particular those of high raoiecular weight.



  As a general rule, the proportion of hydrophilic colloid need not be more than 5% of the main sheet-forming product, and can sometimes be on the order of 1% or less.



   As indicated above, stable dispersions and
 EMI13.2
 transient dispersions require somewhat different methods of inlubiljD3tion. In some cases, the quality of stable dispersions can be improved by a combination of cos methods
 EMI13.3
 (see e.g. Example III below), using in the dispersant phase not only an insolubilizing agent for the hydrophilic colloid, which tends to modify its viscosity, but also a water-soluble sheet resin which is not not miscible with hydrophilic colloid solution.

   By this combination of methods, can we obtain stable dispersions? with globules that which has a viscosity lower than, would be increased required with certain types of insolubilizing systems. This widens the field of products which can be insolubilized such that the globules have a desirable consistency for xxxxxx
 EMI13.4
 in a composition of .cevétement,
The basic coating materials employed in the present invention can be prepared with a mixing equipment.
 EMI13.5
 conventional. The d: 1..persiou8 are then formed by agitating these compositions by agitating them with the appropriate second aqueous p1ase.



  This is usually done by stirring an example 9-j-P component using a rotary rotor type mixer, while adding the other one proqresstv8m9nt. In general, a dispersant medium is added to the revatemont composition which forms in the discontinuous phase / <:! 'ec Created combination methods may be more suitableao For the preparation: the * multiple aispernions, co ... glue * which contain materials. -3, ux of xev8tt of !!: = x or plaei <Mirw color * scattered * in a sevi mili # it is! 'In6r..88Ut pctf maple of diaper r 86pu6lD8nt -: .- hÓque Material 3 vétseast dst-. 0 the dispersing medium, and 40 COLt't'1: - raftn1ee the d1ff'rMat: M diepor.81on8.

   In all 188 cases it is 4alorimt poceible in the tile

 <Desc / Clms Page number 14>

 multiple dispersions by adding each material successively, or even simultaneously, to the same portion of dispersing medium.



   An alternative, but often less convenient, method of preparing these dispersions involves simultaneous insolubilization and dispersion. According to this method, the appropriate treatments are carried out on a single aqueous composition, in which the dispersed globules are formed in the composition, and the remaining product becomes the dispersing medium. Two or more of these dispersions are then mixed to force the desired multiple dispersion.



   The size of the dispersed globules depends in part on the degree of agitation and the agitation time. The consistency of the disposed phase is of course determined primarily by compositional factors, such as the viscosity of the coating material and the type of insclubilizing system. When these factors are suitably chosen, the size of the pheasant dispersed globules can easily be adjusted by varying the type of agitation.



   The viscosity and other properties of these dispersians are influenced by the volume ratio of the dispersant phase to the dispersant phase. The chosen ratio will depend on the products used and the desired application. Very high ratios increase stabilization problems, and tend to give high viscosities, while very low ratios lead to discontinuous or scattering effects of the dispersed globules.



  In most applications, a desirable ratio of dispersed phase to dispersant phase will be between 0.5 1 and 4: 1.

 <Desc / Clms Page number 15>

 
 EMI15.1
 The effect of temperature depends on the specific composition, since an increase in temperature, for example. can raise as well as lower viscosity. At constant temperature and with constant stirring, the size of the globules tends to increase with an increase in the viscosity of the dispersed phase, with a decrease in the viscosity of the dispersing medium, and with a lower ratio of the phase independent globules to the dispersing medium phase.



   In order to promote the stability of the dispersion and the uniior-
 EMI15.2
 Similar to the words fa, it is generally better if all the phases have roughly equal densities. In some cases a minor difference may be preferred, such as in coating compositions designed to produce a clear protective layer.
 EMI15.3
 



  The present compositions can be used to obtain monochromatic or miiltichronc.-3 coatings in a single application. Many of their unique characteristics are independent of the multicolored effects which they make possible. For example, they can give heterogeneous coatings in
 EMI15.4
 which law parts disti.-icteg different from each other by a constituent other than the coloring matter, for example by the binders or by the inert fillers. These coatings can
 EMI15.5
 have interesting 7 ';, ur: -ri6t's physics.- which cannot be obtained with hotnogenic compositions, or with heterogeneous compositions and small portions, such as those obtained by mixing emulsions or different latexes.
 EMI15.6
 



  In p1 "li.r, the present compositions can be used to obtr.tc, in a single application, a film thickness of 0.127 mm 0. More, without encountering the problems of warping in. By the inventive rovotomonto in solution. or in dispersion. lei making varicose veins the size and consistency of globules or heads, or may obtain attractive textures or films 1J4D81bl¯nt l 9ses, then crude analogous textures produce .. & V '- (: 4 & t I \ :, normally more than one ..esrtioa. lu fa1p ..}. t V) M'i <M * la d4! gr ".....: h & vc1BQnt of the cover, we can pEOd :, lt of ft²8i; 8MDt8 having Jec degrees vad fthles of porosity, c5epW.è: es film of microscopic porosity up to films-. i! tsaresa on 801) RI: .t ont '1itIJiblê t. the naked eye.

   Tr.1t '1 "coatings are also suitable for I 8PP11aatiGn a 1 .. surfacea of 16' tbgf - **, ati paper, leather, eaea0 .. a * straw, eo des matrer, .- austiquss turkeys da5a

 <Desc / Clms Page number 16>

 
 EMI16.1
 pldolill laws (aU leu ae; rg .....: DP8 1 <L of rcv $ t aant <G8N, go can obtain 1 '1I \ .1ftt of prizes a1Uon. with dea particul ** fil un 41 .. ..tJ: da que1qu .. OD. atulematà que 110ft n1, p8'.at distinguish ViD 1.Gll8nt aaaa 9 * 4i * Mnt appl'kiable.

   A Qdnéral, a good opac1.1, .4 e *% favoriede ON 'a weak $ p <i <Wall of film towards the small% é * tall @ a 48 yalo, and a good opening power is f.1 ': f .. = - inch 11s CU ...; {en.u.r6s by (r8! .4.8 ti & 111es of pRti.c \ t1 ... an i'1MMI4t of size * * and often 1 nter. 8Mte, and 18. '"F'aantea n * Uw4oeoe pe1'1l8ttet A large flexible .. d, adaptation dez tt6. 4ouisa for uses
 EMI16.2
 specific.
 EMI16.3
 



  If we must obtain .ua =. "It ..- nt aulric: olore, in the healthy one of the aqueous phases must be diftrCDt8 from another phase by the color or by its aspect. Psr <! M <ftpl << des 91.01 : 2u1e. Colored * peovent liter 4i8p81.a6. In a clear aqueous, or the aqueous dispersing medium can <tt <Qolor6 difieromant of the dispersed globules. On the other hand, globules having dal or more tsiates or a different color * can be diupersed in a a clear aqueous medium, or in a medium which is colored differently from the dispersed globules. If 04 is to obtain a multicolour effect essentially by means of 9 different colored objects from each other, a dispersion of the stable type is required, in which the globules dispersed thus being separate and distinct, without unifying sensibly at each other.



  A wide variety of colors can be obtained
 EMI16.4
 with variations in size, tonne or alignment of the elements
 EMI16.5
 scattered things. When very small particles are used, one obtains sonically monotonous * effects even when pits of one color are present.
 EMI16.6
 mixed colors, however, have a characteristic appearance which is
 EMI16.7
 surprisingly different from obi; c,:! when mixing conventional color coatings r the colored elements are pigments <3f <microscopic size quC9.
 EMI16.8
 



  When it is worth obtaining a clearly visible multicolored effect,
 EMI16.9
 we must provide a nodel of colors or distinct shades in the
 EMI16.10
 which a large number of element. or groupings of the model
 EMI16.11
 prlvrt be di8tirué8 with the naked eye or with a little magnifying glass
 EMI16.12
 magnifying. For this reason, at least some of the cells may be relatively large, for example having a size of

 <Desc / Clms Page number 17>

 
 EMI17.1
 greater than 25 microns. When vout'mbkm4r * rqu4a contrasts, the prdmentge compositions can provide blood cells whose uno 411HD8ion at Mina may be of the order of 1 to 10 B or greater.

   When Ipe dispersions are paaaagaraa and when one droplets easily land one. to others at the time of application of the film or before setting, the predominant factor is the size. 4 9 ("ltte> .ott8o 8 will balance it and at rest dat) 'the compouit4on liquid or in the film ds re'l8t..nt, and not during the agitation or movement of application.



   In an application, when we want to obtain a relative film
 EMI17.2
 Vamant thin with good opacity, we prepare a multicolored clothing by mixing a dispersion, containing colored globules that can be distinguished with the eye. an aqueous paint conventionr & it cosmetics a latex of another color. In this case however, many of the colored blood cells are often partly hidden by the latex paint. Instead of the latter, it is often preferable to use one of the present compounds.
 EMI17.3
 tions in which the3 diper.ée8 particles are relatively small, for example a few microns in diameter.

   This
 EMI17.4
 provides sufficient substrate coverage for normal film cutters, but with poorer scatter cell stimulation than that encountered with the latex coating.



   The dispersed globules or droplets can take a variety of shapes ranging from spheres to elongated beads, depending largely on the consistency of the dispersed phase and the type of agitation employed to form the dispersion. In many
 EMI17.5
 case the shape is irregular, but somewhat rounded by the interfacial forces. In the coating applied, the shape of the globules may vary with the method of application.
The coating composition of this invention, which they
 EMI17.6
 contain imnochrome or multichrome coating materials, can be applied in a single coating operation, for example by spraying, roller, brush,
 EMI17.7
 tempered, etc., to produce MayV..3 coatings having a unique texture, character and appearance.

   The type of pattern formed depends in part on the method of application, as those which produce appreciable shear tend to align or twist the particles to some extent. especially with transient dispersions, application to pineesu may produce

 <Desc / Clms Page number 18>

 
 EMI18.1
 of * efteta dc, xeyura or of vo4.M of no <thr * ux tfflai whose cartel we recall the: .Ua of the boiv or the uwkrbru of, $ pftW.tu1t4 utw: e1 ..



  During the t IIp., U.Qat1oA daa EOW & 1: .. coq aitionst the revdtenuunto dàicéa lot will form supported by simple 8êch ..., air or pax e1mpl8 Cu; .. 2OD at t.t: UJ88 low. Beyond ear, ilo does not become .recti.f8 until after (A. Un at.t¯nt tbln1quQ which & OU will do the piitlOtp8l t'9mt 'eu111og' "and which pa4XKù will destroy the co3lcxds hyckopbi 1 0 which aor % Je linking t8lp) r-.1n. Pes Mtexple, certain rev6teNent * organiqaa oomw those of poJ.ytft;

   t "aflt1Ozo6thyl6ne, no effective devionnuat C08UD8 binder @ that after -.gglC80ration with heat of the polymer garticulta. flan9 a pu more # wrs dea pb% s * 3 aqueuaec contitnnnent some frit c6XOEà ± that or non-trittied ceramic minerals, the '- "04.0SJQ.it1one pP.4 will give:' ceramic enamels or t: utU1."., IIIQnoc: hr # 1. or multiooloreo, usable on ceramic articles, on glass or on metal surfaces. In this application the hydrophilic colloid is easily calcined during the agglomeration process.



   The compositions of the present invention are also suitable
 EMI18.2
 to form diaper globules ind6x'Reente in which the main scavenging agent is not an organic compound but a product such as cellulose asbestos fibers, sawdust, etc.

   If the globules which contain these products are colored, for example, the dispersions are useful in producing multi-colored paper films, asbestos cloths, or cardboard.
 EMI18.3
 fiber tone. Alternatively, globules which contain a hydrophilic colloid as the sole foil-forming agent can be used to introduce a multicolored pattern by adding dispersions of colored globules to the dough slurry as in Example 1 below, or by applying them to the dough slurry. wet paper during the manufacturing process.



   Although in many cases the present dispersions of independent aqueous globules are designed to be applied in a fluid state, they also provide a unique method of preparing independent dry granules, by simple methods of dispersing and drying. using dispersions or conventional aqueous solutions. The? Dry granules are useful in a wide variety of processes requiring heat and / or pressure for the production of coatings or molded articles, such as plastic moldings, in manufacturing operations.

 <Desc / Clms Page number 19>

 
 EMI19.1
 w ....... #, ¯ ,,.



  Q8lOW% 0g * 1: 111- "pou will produce dis; 8v81: -f \ t .. 40 sole-4- th place * ,, tma Ùv * & a ** operations da ravtfament ùij,% îaànÙsJfi 'don pouftes atMtât andm le . putvirinat-ion at aee, there jpulu4rigneion an ohalu.'eew. 10 dptt 61ec: tt "'t1ql1e, and the coating <aent feu, lit flui4i.8t.



  The '88Dt granule formation prooffl @ * ce is parti- cml1' & '88At v <tl <tblt ce 1DO: Nn .ùo: .., to prepare iOl.1dr2' MifttivMMt fiosa. com cmlleo gon% the majority of pactiçu7.eu has a * <miM <8 mins as 3t? o.ç.a; or m8IM of less than 5 microns this * and UY8nt errruàa3.tabW, For example, the use of fine powders pomat the application of thin films in the continuous state, which d * -4mbe the ant6ri tacbDolog1e. of dry powder was difficult or tmpo..1ble. Unapplication of the powders will not affect the sdherono <since the cohesive strength of the thick coatings reduced their adhesive character.



  The conventional methods of separating dry products from conditioning require either dissolution of the conditioning binder in volatile organic solvents, which results in violations, or heavy mechanical operations to mix the binder with the other constituents. of the coating in the aec state, which generally requires high temperatures. After for-
 EMI19.2
 mulation i1 ssç, the grrtaulation to the desired fineness is difficult, because the lieni-r tbemopla:

  They are typically hard and gummy, and the resin in the coating can also degrade or even burn under the effect of the heat released in the grinding process, requiring complex cooling systems.
 EMI19.3
 According to the method of the present invention, the ubdi7Saio to the desired size is easily done with a minimum of energy expenditure using relatively fluid compositions, which,
 EMI19.4
 lorn of the diaperniun, can be broken up by simple agitation. The transformation into dry granules is then completed by a conventional drying operation.



   In a non-aspect, the present invention further provides a means for reconstituting the dry granules, by addition of an aqueous medium, to produce a liquid coating composition. The production and reconstitution of the bag granules.
 EMI19.5
 are illustrated in Example VII below. These granules or globules can be used in the form of single or mixed colors.
 EMI19.6
 The following examples illustrate embodiments

 <Desc / Clms Page number 20>

 specific to the invention. Examples 1, II and III illustrate these stable dispersions in which the hydrophilic colloid is the only fumogenic agent of the dispersed phase.



   Example IV illustrates an unstable dispersion which contains two immiscible phases, one of which contains pi-alcohol. vinyl. the other phase containing an anianl protein like
 EMI20.1
 agent feui3.1o <3don.



  Examples V, VI, VII, VIII and IX illustrate stable dispersions of which the primary leaf-forming agent of the idle phase is not a hydrophilic collot. Examples VI and
 EMI20.2
 1X illustrate the use of a film forming agent in the dispersed phase and in the dispersant phase.



   The examples specifically illustrate the preparation of dispersions which can be applied in a single coat to obtain multi-colored films. However, it became evident that the
 EMI20.3
 Examples 1, II, III, V, ffl and VII also illustrate the production of monochrome dispersions, which can be applied either as such to obtain monotonic coatings, or mixed.
 EMI20.4
 later to obtain multi-colored coating caapositlons.
 EMI20.5
 



  2Xeu \ $ .. 1.



  Coating composition: multi-component with mono6thyl cellulose composition, A¯¯- d1sP8% .1Q blue monoethyl cellulose
 EMI20.6
 
<tb>
<tb> Parts <SEP> in <SEP> weight
<tb> Solution <SEP> to <SEP> 4% <SEP> of <SEP> monoethyl <SEP> cellulose <SEP> in <SEP> wing
<tb> water, <SEP> dispersion <SEP> of <SEP> pigment <SEP> blue <SEP> cobalt,
<tb>
 
 EMI20.7
 45% solids in the-a8u. 1.8
 EMI20.8
 The di 8pt1r: -aJ.on & t pigment was mixed with the solution of monoethyl callule. at approximately 4 ° C. By reheating the ¯18ag8 to 32.C Gth "US stirring, there is * st 90 = 6 a constant freezing, with some aacsudiHtiou liquid.



  After having cut the gel into 1D gjcoe., .. t43, the following was added: Water 16.4
Total 100
 EMI20.9
 By stirring ¯C! An1qn6 1DOd6S1N, we then cMe4 the gel and loft dimm * 6 in the external phase.

 <Desc / Clms Page number 21>

 
 EMI21.1
 Compo.> I - <; io! \ '! L :: - Disperica. monoethyl cr2 lulose white
 EMI21.2
 
<tb>
<tb> Solution <SEP> to <SEP> 4% <SEP> of <SEP> monoetyl <SEP> cellulose <SEP> in <SEP> 81.4
<tb>
 
 EMI21.3
 water, titanium dioxide cip'rsion,: '96 solids in water 2.4
 EMI21.4
 
<tb>
<tb> @au <SEP> 16.2
<tb>
 
 EMI21.5
 1 ¯, Lal 100
 EMI21.6
 We have prepaid this c m: .x> .: ôi t1.on of the more mn: 2nd than composition A.



  Composition C - Blue and white mUlti2010re coating with M2npétbyk cellulose
Equal parts of Compositions A and B were mixed and stirred vigorously (3-step mixer, 900 rpm) for
 EMI21.7
 approximately 1/4 hour, until the 3 dispersed cross-hairs approach the desired average particle size and are visible to the naked eye. To 83 parts of this mixture was then added
 EMI21.8
 t4, with vigorous stirring, 17 parts of a 35% solution of sodium penta-chlorophenol in water.



   The resulting dispersion was relatively stable at a temperature (approximately 4 ° C) at which the monodthyl cellulose is soluble in water.



   Composition C was sprayed onto cardboard with a common lacquer gun. The blue and white particles were easily distinguished with the naked eye after the coating film had cured in place.
 EMI21.9
 



  In this example, the pentachlorophenol promoted the insolubilization of the dispersed particles inQ4P.8nte. at teMp <5ratures all :)) 1 ar.: e ..



  C, 1tt Q \ 1 'el' ¯e can serve as "'8.tl' au de rwte..ent in itself, a dispersion equivalent to the compoflEtl1n C could be mixed with an aqueous slurry of paste de cellulouo, which by 1.'8i ttlftl8nt :: ormai gave a paper with a multi-3 ers label 1: t8D) nt visible.



  ., ¯ EBX2-Éo # o-.lÀ t; Q8iX) f'it.iOI1 -da n; .., ftdlMn1: i.j ro'so at .a8. dt! DI: O'tn, St! 1) ChJiOD IL J; lut: i "n da DZ'Oté.tT.: J.ûiH

 <Desc / Clms Page number 22>

 
 EMI22.1
 
<tb>
<tb> Parts <SEP> in <SEP> weight <SEP>
<tb> Soy <SEP> <SEP> protein <SEP> 14.0
<tb> Ammonia <SEP> aqueous <SEP> to <SEP> 10% <SEP> 3.93
<tb>
 
 EMI22.2
 Sodium salt 0.07% pentachlorophenol
 EMI22.3
 
<tb>
<tb> Water <SEP> 53.5
<tb> <SEP> solution of <SEP> formaldehyde <SEP> to <SEP> 2.5% <SEP> 28.5
<tb> Total <SEP> 100
<tb>
 
After wetting the protein in cold water, ammonia was added, and the temperature was brought to 60 ° C. with stirring.
 EMI22.4
 mechanical tation rcrdrt = a. After maintaining at 600C for about 15 minutes, we added to the mixture pentachlomphenol we form eolutiou at 5%.

   The formaldebyde solution was then added progessively, stirring carefully between the additions.



  Son, 8iti9 B - Bae de .prot6ī .. 4yellow
 EMI22.5
 
<tb>
<tb> Party; <SEP> in <SEP> weight
<tb> Composition <SEP> A
<tb> Dispersion <SEP> to <SEP> 33% <SEP> of <SEP> pigment <SEP> yellow <SEP> cadmium <SEP> clans <SEP> 90
<tb>
 
 EMI22.6
 water, containing 0.3% tri-sodium dodecahydrate pt18phate6. 5 33% titanium dioxide disgersion in water, containing 0.3w ae trisodium phosphate dodecahydrate, 5 Total 100 Sion C - Di.DQrs1n of yellow iprotiin CC! Ftpc, .it. () N B 64.5 Solution 1% ualcium chloride 32.3 5% carbthylce11ulou solution. sodium (high quality visrvxity) 3:

  t
 EMI22.7
 
<tb>
<tb> Total <SEP> 100
<tb>
 
 EMI22.8
 We prepared this' -JO..1..tlon by adding the <oàgw * 1> Kon B. the 4nlotion 8qUeu.8. 1 de eh \ C> X "\ I1'8 de calai = at while stirring tjM'A obtain the size royen 4, m fflticul 'YOIoÙ.U8. We have 011CJr added the aasbauitit.icaüuï.sa sodium, still stirring 8Ufri .IMIft for the wiarav, at i:; .. eu disperse.



  Ucn-¯ 9 Di8D8Z'8ion i '\ fti) ,. Motéinw Un * pz- '' '' 'votto 0C8R1908iu'Gh dé la môm aanièra que la GCMP08t.u'ÓJn C, tilittant à la plao- 6o La Ilion 1 wro baaa blue equivalent of pMtAiHw omtmmt a floemt kriss1801t at the pMtAiHw omtmmt a floemt kriss1801t from P4 "t * t jame adt3r.

 <Desc / Clms Page number 23>

 
 EMI23.1
 Composition E - RsVGt: = -., E: ït mLticolor of yellow and blue pr teilne
 EMI23.2
 
<tb>
<tb> Speaks <SEP> in <SEP> weight
<tb> Composition <SEP> C <SEP> 54.0
<tb> Composition <SEP> D <SEP> 36.5
<tb> Water <SEP> 9.5
<tb> Total <SEP> 100
<tb>
 compositions C and D were mixed, they were diluted to 1 .au,
 EMI23.3
 and stirred to obtain a uniform dispersion.



  We sprayed 4. -e.a 4taposition E on cardboard with a common lacquer gun. The yellow and blue particles are easily seen with the naked eye after the coating film has cured in place.
 EMI23.4
 



  In this example, a hydrophilic leaf-like hydrophilic groteia was used. The insolubilizing agents were formaldehyde in the dried phase and calcium chloride in the dispersant phase. Carboyrnethylcellu! C3e was used as a thickening agent.
 EMI23.5
 Example III Composition of multicolored cellulose rav6 # e <a * nt-employing r.ze soluble resin tooth water in ocnoee non-miscible ir¯scluil3sant and clear binder¯¯¯¯¯¯¯¯¯¯¯¯¯ ¯¯¯¯ composition A - 2a8Q ... blanr; h. cs. med% .1 cellulose
 EMI23.6
 
<tb>
<tb> Parts <SEP> in <SEP> poies
<tb> Aqueous <SEP> solution <SEP> to <SEP> 2% <SEP> of <SEP> methyl <SEP> cellulose
<tb> (15,000 <SEP> sps) <SEP> 99
<tb>
 
 EMI23.7
 Titanium dioxide (tt-900, at Pont) 1
 EMI23.8
 
<tb>
<tb> Total <SEP> 100
<tb>
 
 EMI23.9
 Ct3mD08iti.OD B .. .i2D¯Mc:

  he of methvl c911ulosé!
 EMI23.10
 COIIIOeJ. 1: 10Q A 57.2 This ecaesit3an was added. to a dispersing medium c: ont4lftant 18 solution of 1 * wheat resin in 1 water (Arolo; "1304, A8bl8ICS Cbe8ical C'e '..) 27, 81c: raftif 1Iq"' - .. 1ft.11-wanaee. b-4 0,: 5 solution <tq'M! C. 8G1tle tannic 1.35
 EMI23.11
 we have 8g1d the ot4inne 4th gagea x) odér6 * until * *, nbto.ait the size -zyeh * e 4th particles vclulue.

   Then we puco64 at 1 '.-. 1: 1- d'mM t, j.gp8rdon 2% clay
 EMI23.12
 de oatro.lloaits MfafiMM! "eim the water 1 .. 14 2
 EMI23.13
 
<tb>
<tb> Total <SEP> 100
<tb>
<tb>
 

 <Desc / Clms Page number 24>

 
 EMI24.1
 We continued the Alte.tj.QI \ for a blessed instant vour ubtsaaLx a di.pe.104 usi.fosmm. ' ummieic) n C ¯ .w $ oggrq $ gn 59-fl µg] jvl C911UIC) ms we prepared eatte.; .. J.t1OD from mom 88D1k8 than Composition B, in UtÂl ± R0ÀXi & 1.a p1aoe de Action A, a red mud equivalent to -.1 o * 1luloa * containing a red pigment of osydo in place of 4o 4 of titanium.



  90! "} JOaition D - a ') dnt, j. D r63nt 1 ns the esu of methyl celluiwjJ1uab. Art." J8.



  We mixed bed agitd 4as po + * i equal to 488 c0ap081t..a.Qn8 B * t C until a 4 \ 8periJ1OA un1fom8 was obtained. composition D was sprayed onto cardboard using a common lacquer gun. With the naked eye, we could easily distinguish the red and white particles * after the film had revived.
 EMI24.2
 hardened in place.
 EMI24.3
 



  This example is analogous to axample x, in that a cellulose ether called leuillogenic hydrophilic colloldo is employed in the diapers6o phase. In the present illustration, sodium pentachlorophenol was not required to be harmless as a result of the use of a water soluble and non-miacible xeinin (Arolon 304). 8 employing in the dispersion medium a film-forming agent which was not miscible with the stirring agent of the dispersed phase, the dispersion was obtained with par-
 EMI24.4
 dispersed ticles of greater fluidity than would otherwise have been obtained.

 <Desc / Clms Page number 25>

 Example IV
 EMI25.1
 a-tone of multicolored clothing eqploying 801uiqpg my Comooaition Z. - g2lui:

  iLom D91.14'.I1-cool covviiou
 EMI25.2
 Partial enz Batch solution of polyvinyl alcohol 94 Cana water (8li, ml 51-05) Black dispersion of tun6e in alcohol! Ooprapy11que, S01 ± de aolidea (Alcoblak 339. Colombiion CarLon) Total 100 Composition B - solution b, jnre ...! . '' 3.fi "ls Part. In Egids Solution of animal protein raffin6o; Flaxd 00110 ... (1 NI '69, Swift & Co.) 73
 EMI25.3
 
<tb>
<tb> Water <SEP> 24.5
<tb> Titanium <SEP> <SEP> Dioxide
<tb> Total <SEP> 100
<tb>
 
 EMI25.4
 Composition C - Coating1: multicolored black and white alcohol P2! Yvinvliae and proteinē¯¯¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯¯¯¯
67 parts of composition A were mixed with 33 parts of competition B, and stirred with moderate agitation until the particle size was near equilibrium.



   Shortly after stirring - * - stirring, composition C was spread on cardboard using an ordinary brush.



  As the film was allowed to set, the portions *, of the white composition tended to rise to the surface, giving a black and white pattern with a striped effect, in the direction of the brush strokes, which was clearly visible. with the naked eye.



   Likewise, Composition C was sprayed onto cardboard using a common lacquer gun shortly after stirring was ceased.
 EMI25.5
 We obtained a multicolored f.'Ln, similar to that obtained with a brush, but with a more disordered pattern. The appearance of the pattern could be varied considerably by varying
 EMI25.6
 factors such as wet film peace of mind and application temperature.



   The effects obtained in this example are associated with the relative instability of the dispersion, which allows a certain degree of coalescence of the particles, allowing the formation of a visible size pattern.

 <Desc / Clms Page number 26>

 
 EMI26.1
 



  Dl \ na this -.ple, polyvinyl alcohol and wet44jis <Ma: w <nt 1: 0118 of dO binder * 4th revotemint. tt .ua! -: doe. inaoln4lÀ * wantM pou lois p: oduiu cS8 "* 'other &" 4o ire, NBMdJL.! <L .it: .tan f8 MYMWMt MUÀSRIM 5b lat 9qJyj.Í'1U.



  This "p18 and 1 '& oglO euivwnt tllU8 \: rent in f0J: 848tàoG de cx4moeit * iona de ravotemmt 4ana 18equetl .. lu ws: tj.ou1u' tÙ, # Q8" copiqueo de d1apcaiC; Q8 de latex and da t # nt3 . &? n W40: l: ant '- "tI hundred OWL = er4es, in W18 motràoe iD801gJ, iU.'e d'i, n ccl1.lè & 8} 1yckopb.fL, in colored particles da aill. visible.

   In this way, it is possible to employ inventive monohcotMw diîperuioua for ± -or r% multicolored coating compositions. r11tQ!) - mine bltue a ft.att aG / vlàm.
 EMI26.2
 gangtea in 4oxylic, 46% of ttolidaw (Mwpl âC-33) 50 DiBpers'ion of pigment cobalt blue 43% of 5 solids in water Disporeizn of arqil,% at * montmorillonite me: gné; 3emlo z1 5% in l 'water 3 G, 9
 EMI26.3
 
<tb>
<tb> After <SEP> have. <SEP> mixed <SEP> these <SEP> component, <SEP> on <SEP> a <SEP> employee
<tb>
 
 EMI26.4
 Mixture vigorously to incorporate into them: 1.5% solution of ethylene oxide polymer (polyox YISR-301) in blue water. 3 Total 100 Composition B - Dispersion .8e latex aorviimie
50 parts of Composition A were added to 50 parts of a 1% dispersion of magnesian montmorillonite clay in water.
 EMI26.5
 



  To effect the dispervion, this mixture was stirred with a 3-blade paddle at 200 rpm for approximately 1/4 hour. Composition G -¯Dig2graion 1aune de latex, l1çrvli111e
This composition was prepared in an analogous manner to Composition B, using a yellow dispersion base equivalent to Composition A. A dispersion of cadmium yellow pigment in the yellow dispersion base was used.



  Composition D - Multicolored coating of blue and yellow acrylic latex
Equal parts of Compositions B and C were mixed and stirred until a uniform dispersion was obtained.



   Composition D was sprayed onto cardboard and a textile material, using a common lacquer gun. We

 <Desc / Clms Page number 27>

 
 EMI27.1
 . uww .r..¯ W 4à @%> qUàst .18 .. \ les xti4alas).). W8 "jauq. 'fi 1 naked eye atpsue that KwvêtwMat's film has 4 \ # <" 1 aus p1I \ ae' ". 'Donna oet 1 .. the Latwac a # yl: h'". L8 was the rdsine "u11 pd.ll8uCI 'and the pot of cayde 416t: hylb8 6a ± 1 & 001101- 11 .. X,' aq1ls QOut -11: Jt; agent: I.n801u}, \ U..fUIt.



  . l QiaQQIj, da a: v, 'O. 1Jt + A ".FV} .. m UJJ.a. # nA -vent .uil109.- pigmented by the hau; oontinues. we obtained from' cat example a <rwv6teMcnt m \! tico1Q; p: e with f.404 PDR1c: ul .. 41 "" J: s. of a color ball, The cpoaf.t3aas of this type are pa.rtiou1U :: aD8nt: useful <for the app1S aamion au pinasau, and when one, reutt obtimtr multicolored effects in at fUZ8 <M3mtivwMnt minoan. gamoltba 8 - Base Q21x * from ..tex acrv1guo
 EMI27.2
 
<tb>
<tb> Parts <SEP> in <SEP> 221 <SEP>
<tb> Latex <SEP> acrylic <SEP> 46.5% <SEP> of <SEP> solid * <SEP> (Polyco <SEP> 2719) <SEP> 29.6
<tb>
 
 EMI27.3
 88t ..... loool at 10 at: cmtt1l da carbon, not 0.9 mitt to water (ùei.-P1) Solution it x. 5% gua 'in water (high visoeott6, St8:

  ln, Bail T - 8-1) 2 ?. 5
 EMI27.4
 
<tb>
<tb> On <SEP> a <SEP> combined <SEP> the <SEP> latex <SEP> with <SEP> the <SEP> agent of <SEP> coalescence,
<tb> then <SEP> on <SEP> the <SEP> adds <SEP> in <SEP> shaking <SEP> to <SEP> the <SEP> solution
<tb> of <SEP> guar, <SEP> on <SEP> a <SEP> stirred <SEP> this <SEP> mixture <SEP> gradually
<tb> in <SEP> one <SEP> combination <SEP> dea <SEP> two <SEP> dispersions <SEP> of
<tb> pigment <SEP> and <SEP> extender <SEP> shown <SEP> below.
<tb>



  Oxylde <SEP> de <SEP> iron <SEP> black <SEP> 5.26
<tb> Polyvinyl alcohol <SEP>, <SEP> low <SEP> viscosity <SEP> (Elvanol <SEP> EP <SEP> 55-70) <SEP> 0.027
<tb> Agent <SEP> dispersant <SEP> of <SEP> pigment <SEP> anionic <SEP> polymer
<tb> (Tamol <SEP> 731) <SEP> 0.013
<tb> Water <SEP> 3.89
<tb> Kaolin <SEP> 7.82
<tb> Talc <SEP> 7.82
<tb> <SEP> magnesium <SEP> silicate <SEP> hydrated <SEP> (Ben-A-Gel <SEP> L'il) <SEP> 0.34
<tb> Agent <SEP> disperse <SEP> of <SEP> pigment <SEP> anionic <SEP> polymer
<tb> (Tamol <SEP> 731) <SEP> 0.24
<tb>
 
 EMI27.5
 Tr.i.polypI1Ospb, c.e .e sodium 0.05
 EMI27.6
 
<tb>
<tb> Water <SEP> 16.54
<tb> Total <SEP> 100
<tb>
 

 <Desc / Clms Page number 28>

 
 EMI28.1
 Composition B - Painted 1st white latex acrvliaue
 EMI28.2
 
<tb>
<tb> Parts <SEP> in <SEP> weight
<tb> <SEP> titanium dioxide <SEP> <SEP> 31.3
<tb> Kaolin <SEP> 18,

   <SEP> 8 <SEP>
<tb> Agent <SEP> dispersant <SEP> of <SEP> pigment <SEP> anionic <SEP> polymer
<tb> (Tamol <SEP> 731) <SEP> 0.3
<tb> Latex <SEP> acrylic, <SEP> 46.5% <SEP> of <SEP> aolides <SEP> (Polyco <SEP> 2719) <SEP> 41.3
<tb> Ester-alcohol <SEP> at <SEP> 12 <SEP> atoms <SEP> da <SEP> carbon <SEP> not <SEP> miscible
<tb> to <SEP> water <SEP> (Texanol) <SEP> 1.3
<tb> Water <SEP> 7.0
<tb> Total <SEP> 100
<tb>
 
 EMI28.3
 Composition C - Rev81: e: nent multicolour che latex
 EMI28.4
 
<tb>
<tb> ecr.vliaue <SEP> black <SEP> and <SEP> white¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯¯ <SEP> Parts <SEP> in <SEP> weight
<tb> Composition <SEP> A <SEP> solo
<tb> on <SEP> a <SEP> addition: 6 <SEP> this <SEP> composition <SEP> to <SEP> the <SEP> solution <SEP> following
<tb>
 
 EMI28.5
 Carboxym4tJbyl cellulose, liaute vi.co.i4 (Cel10.i18 cl P-75-XH) 0.04 B3 ammonium borate O.

   C4 Water 16.42 hours after mechanical stirring sufficient to obtain the average size of V, ticuluvoulu4 ,, we added the point;.,. 1;) lanc: hu do latox wt on 1.'a Mixed with the ciatinue phenomenon.



  Ctraposition B 3.S
 EMI28.6
 
<tb>
<tb> Total <SEP> 100
<tb>
 
 EMI28.7
 Oexpoitàon C was sprayed and brushed on cardboard, which * 01.% 4 of the multieui notices were clearly visible after the rwvttaoxnt film was 46ce.



  In this X \ 1I8Pl., The latex has # yliqu. said 18 resin feuillogéne prJ.1M1n. The g "r eU: 18 001101- hytiropbile, which was 1n801ub11" by 1 b2J: m: a'C8 à'aoc3.t ,. The ui: 1118!,:, .- 1cn of polyvinyl alcohol ca8M <tgent of 4iep8t1oA Aa pà4e> * nt emigible for borate a "uwrn mw boràw. Rftentiot ,. to. Piquomt in the clispeaesisr phase.



   Example VII
 EMI28.8
 Using dimto 8.4 a "-1188'1 la piafé; *> m '.......; fiu rÂOle3 later

 <Desc / Clms Page number 29>

 
 EMI29.1
 .. -o .. - - ..4 ...



  Composition A - Soy protein a.euse solution
 EMI29.2
 
<tb>
<tb> Parts <SEP> in <SEP> weight <SEP>
<tb>
 
 EMI29.3
 Sua protein (alpha irotein
 EMI29.4
 
<tb>
<tb> of <SEP> viscosity <SEP> medium) <SEP> 10
<tb> Solution <SEP> accuses <SEP> of ammonia <SEP> to <SEP> 10% <SEP> 3
<tb>
 
 EMI29.5
 5% aqueous solution of pentachlorophenol code 1
 EMI29.6
 
<tb>
<tb> Water <SEP> 86
<tb> Total <SEP> 100
<tb>
 
 EMI29.7
 Composition B - Solution of styrene-anhydride resin ma7. ° Sc--
 EMI29.8
 
<tb>
<tb> Parts <SEP> in <SEP> weight
<tb>
 
 EMI29.9
 Pclyt. ".. îe ue styrà.e" "lÜ1 .:

  Maleic rider (Vinylite SYIitl) (high quality, has Vi5cosity) 4, 9 Aqueous source of 10% ammonia 5, 9
 EMI29.10
 
<tb>
<tb> Water <SEP> 89.2
<tb> Total <SEP> 100
<tb>
 In compositions A and B, prepared the solutions of
 EMI29.11
 the way conventionnex, 1a.



  Conition C - Lai = ,. éu anulated acetate.do DOlvvinvle
 EMI29.12
 
<tb>
<tb> Party. <SEP> in <SEP> weight
<tb>
 
 EMI29.13
 Polyvinyl latex P lic4ita1: e (55% solids-
 EMI29.14
 
<tb>
<tb> Gelva <SEP> ts-66) <SEP> 21.7
<tb> Dispersion <SEP> to <SEP> 45% <SEP> clay <SEP> of <SEP> aluminum silicate <SEP>
<tb> hydrated <SEP> in <SEP> a <SEP> solution <SEP> to <SEP> 0.1% <SEP> of <SEP> phoephte
<tb> trisoddque <SEP> 6.5
<tb>
 
 EMI29.15
 Disperalon at 45% of blue cobalt pigment in a 0.4% solution of tri80ttic phosphate 615 Diçe ::; ion, 5% of titanium dioxide in a 0.5% solution of tfieo'tif la phosphate, 9 We have eoigneue 1'418Dl; 1f these iDlJdcUnni.a before adding, year I861aDgCII.:m1: after each addition:

   
 EMI29.16
 
<tb>
<tb> Composition <SEP> A <SEP> la, <SEP> 9 <SEP>
<tb>
 
 EMI29.17
 ea.po.it1n a 2187
 EMI29.18
 
<tb>
<tb> Water <SEP> 21.8
<tb> Total <SEP> 100
<tb>
 
 EMI29.19
 We then have ft2: 0 & lerri: 4M the cL. i1 obt.8Ia de 4mvià = 300., af1: i8tJ of used atluticm 8qU8C28 a O, 25% da cb1o!: '\ lft de cmlciumf w gi <tion <!) e << t, which has âo6 um d3srlae de pu't: 1cml- 'li ... nAttt1l88 .. une 1a 1' c3.t, t, we have aal8 .. !! b.rUlIiM c18 ob1onn "- caleim for Io 8JIfoI wolatioa at 1O'J15

 <Desc / Clms Page number 30>

 in the extrene or dispersing phase, and stirring continued for 15 minutes. The particles were then allowed to settle and after having separated the liquid phase, they were washed twice with fresh water, then dried at 38 ° C. with occasional stirring.

   This gave particles of variable length up to about 1.27 years, and especially of the order of 1 to 10 mm. The particle size is influenced by factors such as the viscosity of the dispersion base, the concentration
 EMI30.1
 initial calcium chloride serving as the d.i pc3rsant medium, the stirring load during dispersion and the extent of agitation during and after drying.
 EMI30.2
 çaup2s; Ltign L V Intex b lane granulated .of DOlvin7le acetate
The dispersion base was the same as in composition C. and the cobalt blue pigment dispersion was removed, and we
 EMI30.3
 used 10.9 parts of herbal dioxide pigment dispersion instead of 10.9 parts.

   The mixture was then poured into about 450 parts of a 0.35% aqueous solution of calcium chloride with moderate stirring. The concentration of calcium chloride was then brought to 10%, the dispersion was slowly stirred for 15 minutes, and the particles were washed and dried.
 EMI30.4
 voeoen den * composition C. In this .1t: iol1. 18s dry icicles had lengths comprised mainly between 0.2 and 3 mm.
 EMI30.5
 COaq.

   J8H: 1on - composition of regenerated coating of latex ise onoclrc
 EMI30.6
 
<tb>
<tb> Part- <SEP> in <SEP> weight
<tb>
 
 EMI30.7
 f.:t':1'l1OSliUon P 20 Solution 8IJG.e, 2% phosphate 4i8DtOnique 60
 EMI30.8
 
<tb>
<tb> Water
<tb> Total <SEP> 100
<tb>
 
 EMI30.9
 h1: ¯131'118 avrc wolction tte phosphate, low p8Riculc.s <èc <9s confluence K <Mt & 'II801U.¯ft: and poe ag1.t: a .11 .. ue% * n pftl ..} * rtlCNle8 # & 1 801 '\. qu. in poumik a1k ftalê7. le aknge!: \ 1 p: l.Daea1l .i..1 nm> xe das p * iaùure * 0I'dln1n # .. lt ... whereUoD CIOft8t: ibe - s- 1.1e de pe! m: 1. CQJ'iJ.oaI ', w: "1e p, ta 8ftr; tt .. ual .. v ... G) 8i1: 88: n.! T; 8 .L iça: ft8D8 <18 8iaHei 4418 aat lieno an wfl 4ib adHiwa 6 <'4iaio. ce C' "le ta fU & 81 fta1 a * orb from 6 to 7.

 <Desc / Clms Page number 31>

 
 EMI31.1
 



  -................



  Composition with 'Regenerated J.eue Dispersion of lër {; ax 1 acetate ::' Y'l, .il1vle .. ------.
 EMI31.2
 Partiaa in! 3p.:. Ds
 EMI31.3
 
<tb>
<tb> Composition <SEP> C <SEP> 19
<tb> Aqueous <SEP> solution <SEP> to <SEP> 2% <SEP> of <SEP> phosphate <SEP> motioaamtonioue <SEP> 55
<tb> Water <SEP> 27
<tb> rotai <SEP> 100
<tb>
 By mixing with the phosphate solution the particles
 EMI31.4
 The dryer swelled and softened, most of the MM by extensive mixing or mixing as in the case of composition E. The final pH of the dispersion medium was in this case of the order of 5 to
 EMI31.5
 6. L.o'bjf.IC: "f was here from ir, 6-orliiire of macro-particles' 1tili!; .. ';.) le in vtac"' 1s1) 8rsio1: NUltoJoc.

   After formation of the dispersion, the final size of the pa-tioulc was related to the degree of agitation, such as the au'tJ: fI-8 ltX'J: 1ples of this invention.



  Composition G - dittpersion; : J, c: 'he regenerated acetate latex of! X) lV7i11vlft. -.-, 'It was 1 ..... that COO1sition F, May.9 using 13 CCIIDp) 811: lon D instead -le l # orepo8ition C.



  Composition 13 - 81! On of: multicolored coating ré9'6Mr of latex dl, * em2 da DO: 't.: A.:. Wle -
 EMI31.6
 
<tb>
<tb> Parts <SEP> in <SEP> weight
<tb> Compostiton <SEP> to <SEP> 40
<tb> Composition <SEP> C <SEP> 40
<tb> Nau <SEP> Tatal <SEP> 20/100
<tb>
 
 EMI31.7
 Or. Aqitd6 the 1161ange of ingredients to make a 4S.8). * ZII: 1Qa uniMPMt, pays it was sprayed on enrton lk the eià% of a spray at 1Aw;, rant. La. Part1, eule3 46p0. '. "' E1 (> ü pet! .8 & ad * a18Dt: 8tra .eant & i8ir.gu" 1! S los ones deu sntrr.e l'8ei.: Z :: ftprts 4ria le xement film had 1 '\ u: i on plam. well where 4MW this color tone 0haql \ 8 was regenerated: a' ,, \\ r.1: 8G1.aogep1 4.a8 6MB) S maiogu4a! .. V \ 4itIU. that it can auV \ ,,., 1161 "t = p. the state rra ee ktwe r.'9"! '. A. at the same time.



  In oât 9 the 1.a (\ .., polyvinyl c6bt. Is Ac% 661! ... il1.og pri8! 8ifto. The soybean #oUii and the pcl'II1r. Of 8ty, * 1 & t M141 that are the ("J () l1ut & a hydrophy.u. And '1 de odai8 laughs agent i,:! Lubit8nt.

 <Desc / Clms Page number 32>

 Example VIII
 EMI32.1
 ÇOllDO, W9J1 4! .. r.tr "t M: icopM M se <anauim smaN, t19u é - HUana. 4. 8iUsata M. DOtJ .. .., 1. Inilit
 EMI32.2
 
<tb>
<tb> parts <SEP> in <SEP> Weight
<tb> Aqueous <SEP> solution <SEP> of <SEP> silicate <SEP> of <SEP> petasium.
<tb>
 
 EMI32.3
 



  40.75 'aaum4 (Ueil JIll 6) 50 Dieperu10n aqueous it 3% of M? 9i da mont-
 EMI32.4
 
<tb>
<tb> morillonite <SEP> magnesian <SEP> 50
<tb> Total <SEP> le).)
<tb>
 
 EMI32.5
 i Mélanae e carby: l =, 1;,. p12U s04 & è and. from -iy- (0xv4. c1 'vltP, l
 EMI32.6
 
<tb>
<tb> parts <SEP> in <SEP> Weight
<tb>
 
 EMI32.7
 2% car'thyl aquwcae solution
 EMI32.8
 
<tb>
<tb> cellulose <SEP> sodium <SEP> (quality <SEP> high <SEP> viscosity) <SEP> 22
<tb> Aqueous <SEP> solution <SEP> to <SEP> 1.5 <SEP>% <SEP> of <SEP> polymer <SEP> of oxide
<tb>
 
 EMI32.9
 ethylene (Polyox WSK-301) 78
 EMI32.10
 
<tb>
<tb> Total <SEP> 100
<tb>
 
 EMI32.11
 como81tion Dispersion with potassium silicate
 EMI32.12
 
<tb>
<tb> Parts <SEP> in <SEP> weight
<tb> Composition <SEP> A <SEP> 22.5
<tb> Solution <SEP> of <SEP> silicate <SEP> of <SEP> potassium <SEP> 35,

  5
<tb> The <SEP> mix <SEP> of <SEP> these <SEP> components <SEP> has <SEP> been <SEP> followed <SEP> by
<tb> addition <SEP> and <SEP> incorporation <SEP> of <SEP>: <SEP>
<tb> Dispersion <SEP> of <SEP> pigment <SEP> yellow <SEP> cadmium, <SEP> 33 <SEP>% <SEP> of
<tb> solids <SEP> in <SEP> water <SEP> 5.6
<tb>
 
 EMI32.13
 This mixture was stirred lI16c: "Ú.qually at 200 rpm
 EMI32.14
 
<tb>
<tb> during <SEP> addition <SEP> of <SEP>:

   <SEP>
<tb> Composition <SEP> B <SEP> 31.7
<tb> After <SEP> that <SEP> the <SEP> parts <SEP> insolubilized <SEP> have <SEP> been <SEP> well
<tb> dispersed, <SEP> on <SEP> a <SEP> continued <SEP> agitation <SEP> during <SEP> addition
<tb> from <SEP>:
<tb> Composition <SEP> A <SEP> 4.7
<tb> Total <SEP> 100
<tb>
 This had the effect of increasing the average particle size due to partial aggregation of the particles.
 EMI32.15
 Composition D - Blue potassium silicate dispersion This composition was prepared in the same manner as

 <Desc / Clms Page number 33>

 
 EMI33.1
 4 -se- ** te a -.- ove- -90 "Ccapo81tioa C, in C: Ut.8Cm an equivalent diapartion of pi91Ul1t bltu quoted instead of the yellow diaperttioa of ': 84N.ua. Uzmo4 && M 2 - % vé $ jwgn $ Dn11twolor ,, 1 tif ta.J8ia yellow and blue On;

  % mixed 62 parts of CCmpoBit.ion C to 38 parts of Composition D, and a uniform disappearance was achieved. Composition 3 was sprayed on cardboard and on slag cement using slag cement. a running lacquer gun. The yellow and blue particles were easily distinguished with the naked eye after the coating film had cured in place.



   This example employs a water soluble mineral binder,
 EMI33.2
 potassium silicate as the primary ogan agent, and polyethylene oxide as the primary hydrophilic colloid. In this case, the insolubilization was most easily effected by mixing the clay insolubilizing agent with the primary foil-forming agent, followed by gradual addition of the organic hydropnilic colloid. Another addition of insolubilizing agent completed the process.



   Carboxymethyl cellulose is a hydrophilic colloid which is less strongly influenced by the insolubilizing agent than oxy-
 EMI33.3
 of polyethylene. It therefore serves as a modifier of the acti -: .-. T4 & gelation of the primary insolubilizing system. This prevents gel syneresis which would otherwise occur, and maintains the gelatinous globules in a highly hydrated state which allows their mutual coalescence during film formation.



   Example IX
 EMI33.4
 Ceramic-based coating-multicolor composition
The starting ceramic materials used in this example were typical commercial tile glazes with the composition shown below:
 EMI33.5
 
<tb>
<tb> Composition <SEP> A <SEP> Composition <SEP> B
<tb> Parts <SEP> in <SEP> Weight
<tb> Frit <SEP> ceramic <SEP> 50.6 <SEP> 51.7
<tb> Clay <SEP> 4.4 <SEP> 4.4
<tb> Silicate <SEP> of <SEP> zirconium <SEP> 3.8 <SEP> 3.8
<tb> Ceramic <SEP> <SEP> yellow <SEP> dye <SEP> 3.8
<tb> Colorant <SEP> blue <SEP> of <SEP> ceramic- <SEP> 1.9
<tb> Water <SEP> 37.4 <SEP> 38.2
<tb> Total <SEP> 100 <SEP> Total <SEP> 100
<tb>
 

 <Desc / Clms Page number 34>

 
 EMI34.1
 çametion gaz deluli st "clu ua - ¯¯ ¯ ¯ ¯¯¯ ¯¯ ç.tt9I1 i81 .4 '+ bi" Faùlaw' 9xo # .. "1., I.
 EMI34.2
 
<tb>
<tb>



  Parts <SEP> in <SEP> Weight
<tb>
 
 EMI34.3
 CCttpOtition A 3910 seution 1! 1% acetic acid 4 * M water 513 Aqueous support at 1% quar (high quality virecai.t6) 55.7
 EMI34.4
 
<tb>
<tb> Total <SEP> 100
<tb>
 
 EMI34.5
 This CaDpO8i1: C ion was prepared by modifying the pu with an 80lution of acetic acid, followed by stirring in the gucr solution to obtain an alien-fluid haogenous gel.



  Comaoeition D - Medium 4i8D8run1; OOr $ UMt 1- il ue blue
 EMI34.6
 rartb! tt! tn- 1703-of composition B 62 5 Aqueous solution of 2% rarboocyméhy3 sodium cellulose Í2.5 Aqueous dispersion of 2% of argi7re 8a montmorillonite
 EMI34.7
 
<tb>
<tb> magnesian <SEP> 12.5
<tb> Water <SEP> 12.5
<tb> Total <SEP> 100
<tb>
 
The sodium carboxymethyl cellulose and clay were mixed thoroughly and then added with stirring to the ceramic enamel of Composition B.
 EMI34.8
 



  Composition E - Multicolored Disegraion of Qr. 3 yellow and blue ceramics
55 parts of Composition C were dispersed in 45 parts of Composition D, and the mixture was stirred with moderate agitation until the desired average particle size was obtained. After spraying Composition E onto a ceramic biscuit and calcining at approximately 10400 ° C., a bright and smooth multicolored ceramic enamel was obtained, in which the individual blue and yellow areas were easily distinguished with the naked eye.



   In this example, the hydrophilic colloid was guar, which is gelled by water soluble salts such as alkali borates, which are commonly found in ceramic enamels. They are, however, practically inactive in acidic media. In order to allow mixing of the ceramic coating and the guar, it was therefore necessary to adjust the pH with an acid to prevent excessive insolubilization prior to the addition of the dispersed phase to the dispersing medium.

   Insolubilizing agents
 EMI34.9
 include magnesian monranorillonite clay as well as

 <Desc / Clms Page number 35>

 
 EMI35.1
 sala 8OJ.1 .. c1an. 11 14 provided by 1,4p & it e # raNiq <la cpogq-. mathyl ealluloae 8OClic \ a8 followed 4G4ju ;; '' \ At: de 8icm thitto- t: z: op1que. tw irovotçmmt <t'4'aH o6rudque c04etit.it. the COX'p8 touilloQine: d.ra1J: 8, which was activated by fusion after oaciti <p of the guar. another uwen from oblantioa da c3iUOl8 de re 8temenfi ¯c6raniqu * un.1q-.a .... lco la pc <: ntw 1nvMtiOi't. consists of ¯eh.r, .of8 cU8pw86 globules. of C6ramsquebe compositions, 0 <X8M li * m # l1; .ftt Ilaxemple VII, for a latex coating composition.

   We can then apply on the & \ r.f4a.,. desired 1 ..... ieur8 of these focnMltione 061: am1qu .., whether in the state <or in aqueous dispersion, and melting them lice obtain the predicted c6ram1r., - u. vc -.1u. If the compositions c6J: ua1qu .. differ one d4t the other by their color or by their appearance, i1. ee forms a Multicolored revatsaent.

 

Claims (1)

EMI36.1 R B V E N D 1 C A T I O N S 1. view aqueous coating composition characterized in that it comprises more than one aqueous phase, the aqueous phases being substantially insoluble in each other. the other or immiscible with each other, and by the fact that one or more of said phases EMI36.2 Aqueous coating materials contain, provided that when the aqueous phases are in the form of one or more gels dispersed in an aqueous medium, an insolubilizing agent is contained at least in said medium. 2. An aqueous coating composition according to claim 1, characterized in that at least one desites aqueous phases is formed of independent particles dispersed in an aqueous dispersing medium. 3. An aqueous coating composition according to claim 2, characterized in that the independent aqueous particles are formed from aggregate of smaller particles. 4. An aqueous coating composition according to claim EMI36.3 2 or 3, characterized in that the independent p; trticulea aqu "u..111 form two or more distinct aqueous phase * dispersed in the aqueous dispersant medium. 5. An aqueous coating composition according to the preceding claims 1, 2, 3 or 4, characterized in that the aqueous Phass are made insoluble in one another by the presence of a hydrophilic colloid in one or more of * says. * watery stick insect * EMI36.4 6. An aqueous coating composition e <1 la rdvwndicut3tx 5, charac :: ': riM. by the fact that the stemmed phoaes are insoluble x6nùueoe 1'une in the autxa at the 8n of a ts9ttt in801ubi reading: for said hydrophilic colloid. 7. A coating composition mt lIq1IeuM 88lorJ the revenaicetion 6. characri.a6e by the fa1 que leva * .8lU.U8 phome aqu oes contains an agent feuU1 ... which also has an MC0n4 agent: feuil10gibM 4118ble. 1 J ¯u. 8. ta1 cpositian de Mveteee <m l11tl # les r wnlie * t4cne prevéaeMMW! 1, 2, 3 or 4, .i. '-1: 18 made that 188 by equeueee, yielded i, usol 1' .. daf} 8 aem by 18 ft, j1G8 of an annoyance, intJClub11i8ant 4 4 sct 9o p1 $ tQ .... c1e8d1- .. watery pbea. 9. A c ... 1.ian of ft11lIt, 1ttJU1I ... 81t.m 1a sà3asit 8. * & Zkéù3. @ E not the <& it cpI8 Ile4t "1a1Ml1 \ MJ.i88 & t 'bc * Ma <Desc / Clms Page number 37> hydrophilic colioid. le, An aqueous coating composition according to claims EMI37.1 p16 <iL <1,; ntoeo 1, 2, 3, 4, 5, 6, 7, 8 or, characterized in that at least one of the aqueous phases is colored. He. An aqueous coating composition according to the preceding claims 1, 2, 3,4, 5, 6,7, 8, 9 or 10, characterized in that at least two of the aqueous phases have a different color or tint. 12. A method of preparing an aqueous coating composition characterized by mixing, in the presence of one or more EMI37.2 i.solubilizing agents, from at least one aqueous coating material to an aqueous dispersing medium to form a mixture comprising more than one separate aqueous phase, provided that when the EMI37.3 The coating material forms a gel, an inse.Ljbilisant agent is contained at least in the dispersant medium. 13. A method according to claim 12, characterized by the EMI37.4 causes that two or more phsaea tons of independent aqueous particles are dispersed in the aquenx dispersant medium by successive addition of said phases to said medium disposing a EMI37.5 mixing step following each addition suce8sj, V'o. 14. A method according to claim 12, characterized by Jr that disperses two or more different aqueous phases in separate portions of the aqueous dispersant medium, and that EMI37.6 mixtures of dispersions instinctively. 15. A method according to rf: l ': 1a.tdi.cation 12, ca; act6r1à6; 1: C the fact that an insolubilizer is added to an initially boraogenic aqueous composition containing a coating material., And that the ecmpoo is allowed to form a dispersion. 16. Una m4Llio ,, Ic according to claim 15, whereby the process of claim 15 is repeated with a different aqueous reheating material to form a distinct dispersion than one then mixing with the pxaaièrs dispersion.