BE623262A - - Google Patents

Description

       

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   RESINS AND THEIR USE The present invention relates to ammonia soluble resins for use in wax emulsion compositions and to the process for preparing such resins. In another of its aspects, the invention relates to improved compositions of wax emulsions.



   Polishes based on waxes emulsions usually include the following components: a natural or synthetic wax, an ammonia soluble resin, an emulsifying agent and a diluent consisting of water and a basic component such as water. ammo-

 <Desc / Clms Page number 2>

 
 EMI2.1
 niaquo or the amines & vsaniquaa <: ne eottpiud o4.tGUX is dispersed in Water with the aid of the codifier and the basic component. The resin should be soluble in the basic composition of Pulse. of wax and comes out to improve the lustra removing the hardness due to Ilenotubtîque by acting OOL1ClO a binder and eh promoting the spreading of the waxy component.

   As is evident from the date of ammonia, a number of products and polymers have already been used, for example, the * 016phaned condensation products of md1quo acid and futnaric acid suf ia rosin # let) products of oondonsation of mal1qUQ anhydride at funaric aoid in back compounds poYdr1quQêj of µùtàM lacquer and casein .: toO: issOt10nt ouftaoeo tollos that the wooden floorings or the sold rovttomontg came linoleum, rubber, oarroU & 4th plastic material 11que et rcvatatucntë s1ml1a1rUé tu:

  o which one applies 1.9noaetiqÛO 'mdraoi Icà edgihoa used until now suffered UlqUdtb10 from the defect of Jtsuffie = io râsiutancb a ooM oo.rû to polishes containing'dl6mUls1on of! a1ê.



  The invention relates to an am1aquQ soluble resin. aËtelioro d <lèt: 1.hdG to be used in the do eteaue 9 as well as in the preparation process of rdgïho coats * your resin of the invention 6 is of color trks pAlot? 1 makes it possible to obtain a wavy donation based on emulsion do

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   Wax which have superior water resistance, excellent hardness and gloss. It acts as a superior spreading agent for the waxy component of the polish or emulsion. Other goals and advantages
 EMI3.1
 do the invention will become apparent on reading the following description.



   In accordance with the invention, an ammonia-soluble resin is obtained, which is superior for use in wax emulsion coapositions, by a process which comprises the following different stages: A) It is reacted together in order to produce a hydroxy derivative - ethereal:

  (1) a fusible condensation product, soluble in organic solvents, of a phenol and a
 EMI3.2
 aldehyde, containing units of ccndcnents which pot- 8'-don1o roupo. h, y4Z'03C, y .. 'hnoJ.1q'ule r611ot1tl', help groups xcaativa avaa los graupas hydroxy3.os (2) a substance reactive with phenolic hydroxyl groups, which is selected from the group consisting
 EMI3.3
 in the compounds with an oxirano ring, the haloh,} 'c1r: i: .cs of a.4ay, nai the carbonates of aloyy and their mixtures, and (B) the derivatives hydroxyéthúr63 are esterified by reaction with a selected substance in the group consisting of carboxylic acids, their anhydrides:

   
 EMI3.4
 their halogens and mixtures thereof, in order to obtain a thermoplastic ester derivative. the fusible and organic solvent soluble condensation products of a phenol and an aldehyde which are suitable for use as the starting material in the process of the invention are well known in the art and can be used. prepared by
 EMI3.5
 back well-known procedures.

   The condensate phcnol..r31.d4; o

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 must be soluble in organic solvents such as acetone and must not be carried up to the insolublo “C” stage or the “Reaito” stage. When the phenol is the actual phenol and the aliehyde is the aid. hyde fornic, a type of condensate that gives partial or freely satisfaction contains condensing units-which can be represented by the following formula:
 EMI4.1
 in which n represents a number ranging from avir-1 to 10, and even frequently more con @ ition that the resin is meltable and soluble in acetone or other organic solvents.

   Preferably, the phenol-aldehyde condensate is a "Novolak" which contains more than one mole of phenol per mole of aldehyde.



   Examples of phenols which can be used in the preparation of the phenel-aldehyde condensates for use in the invention include phenol itself and the substituted phenols (general formula);
 EMI4.2
 wherein R may be H, F, 01, Er, or an appropriate substituent selected from the following:

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 EMI5.1
 a) law of alooyics groups containing from 1 to 18 carbon atoms in any of their isomeric forms ot attached to the phenol ring in the ortho, meta, or 'para position;

      
 EMI5.2
 b) al.3.cyc.i groups, uas of 5 to 18 carbon atoms, such as cyclohaxylQ, cyclopontylo, methylcyclohoxyl butyloyolohoxylc, etc ***; o) aromatic or aralkyl groups of 6 to 18 carbon atoms, such as phenyl, alpha- .ndthylbenzyle, benzylo, cumyl, etc ...
 EMI5.3
 zij the alkyl-, aryl-, and aralooylcdtones and odionoe alicycliquee in which the hyd¯-Qlarbon4 group is as defined above e) the alkyl-, aryl- and ara.co3r.carborr.iç ues ut the carboxylic groups alicycliquos in which the hydrocarbon group is as defined above,

   and their mixtures
Suitable substituted phenols include
 EMI5.4
 the following 1 para-tort.-butyloh6nol, para-coo ..



  'uty.ph3nol lao para-torte-amylphu'nol, para ... sca .. ay.phdno., para-tort.-hcxylphenol, para-ioJcty1-phenol, para-phenylph.5nol, lo para -benzylplinol ,, and para-cyclohexylph6nol # para-lecylphenol, Ir para-doddcylphenol para-tdtradecylphdnol, para-octa-ddcylphdnol lu para-nonylphenol, para-ethylphenol para-bO-alpha-naphenol -naph4-Ylphnol, para-pentaddcylphdnol, binds para-cÓtYlp6nOl, para- cunylphCrnol, para-hydroxyacdtophdnonot para- hydroxybcnophnono, a phenol alkylated with linnènc, an alkylated phenol, as well as

 <Desc / Clms Page number 6>

 
 EMI6.1
 
 EMI6.2
 ortho and nota borrosponding drifts, oar.uao mrtabutylphdnol and 1 * dHUobutylph & iol and loura mdlan6one We will deduce.

   tac1ioon dc oo which preobdo that practiceciont all the phdnolo can be used in the invention, provided that they possess a phdnollquo reactive hydroxyl group and are able to react 4voc aldehydes conrao la 'foro.ald <3hydo giving a bonden have % 1013 pure refined phenols can be used, but this is not always necossary * For example, phs5nS can be alkylated and then reacted with an aldehyde in the form of a crude product which may contain a certain amount of polyalkyl phenol as well as good alkoyldo phenols. From p.6tÓronoo, we first prepare the pheno1-a.ldÓhydo resin and we have lco'1. ('Then the pht! Ne'liquo8 nuclei. We can iga7.anont' 'Ql /? Csdps P use.' R .1 (nn-IRoB ï cnns aidssucA 'use desIPu0no s mentioned above.



  In the preparation of the phenol-a3.dYwrdQ 'condensate, an alda-
 EMI6.3
 
 EMI6.4
 any hydo or daidjhydoz mixture capable of
 EMI6.5
 do not react with a phenol and no containing rather do 8
 EMI6.6
 atones of carbon, by OXQ !: 1plo, provided that this or these
 EMI6.7
 aldehydes do not contain a functional group, or
 EMI6.8
 do not possess a structure, which in the reaction of the resolution or estrification, or the oxyalkylation of the resin. 'a.3.d shydo prdfccrc is the ior2c'é! zyda which can be in aqueous solution or knot one of its low p91ynero forpes, cocne parafornalduhydo or lao trioxano.

   Designed other examplesp ds.c4hyc: as, we will quote.! aeLtn3.dhydp, propionaldehyde, butyraldd- hyde, bonzaldehyde, lft furfural, 2 cthyhexac.7.,

 <Desc / Clms Page number 7>

 
 EMI7.1
 ethylbutyraldehyde, heptaldehyde, glyoxal, etc, **
The proportion of aldehyde to be condensed with the phenol may vary in order to prepare Novolaucs
 EMI7.2
 at varying weights, and the melting point of the final resin can be controlled by the molecular weight of the novolacs, preferably the proportion of aldehyde varies from 0.5 to 1.0% per sol of the phenol, when a mono- or a diphenol is used. When we
 EMI7.3
 used a triphenol, the linitg onpJ.dv'1ro p'J ::

  6r60 of the proportion of alduhydo can hearth about 0.85 mol per drop of phenol, to prevent the fomati n
 EMI7.4
 insoluble condensates ot infusiblos In the case where a Novolaquo is prepared observing the aldehyde-phenol ratios indicated ("'! ..- .r: SSU8 it is preferred to react the aldehyde and the phenol or the presence of an acid catalyst, coono attl'ic acid, oblorhydrïqtto acid or oxalic acid, but bagiquos catalysts can also be used.In some cases, oatalysoura may not titrate iiioce- sa.iros.

   Examples of alkaline oatalyaours include annoniaquo, aninca and quaternary arinnnire bases On. can also use anionic type wetting agents, such as a.cay.Fxyl. sodium sulfonates which can accelerate the reaction when using weak acids.
 EMI7.5
 When preparing "Rdsa.e", more than one mole of formalin can be used per mole of phenol. The particular phenols and aldehydes which may be used are described above and the alkaline catalysts mentioned above which may also be used.

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 EMI8.1
 



  Los Rdsolaa have oarbinol groups as well as phûnoliquos hydroxyl groups which can react
 EMI8.2
 with the reagents mentioned below.
 EMI8.3
 In accordance with the invention, it is possible to prepare
 EMI8.4
 improved polymers which preferably no
 EMI8.5
 will contain more free reactive phenol groups (per oxenple, less than about bzz of hydroxyla phenolic originally taken in the phenol-ald6hydo condensate).

   We can make it vagina
 EMI8.6
 resin- phenol-aldehyde with a suitable substance
 EMI8.7
 intended to etherify or break down the phenol-hydroxyl groups, provided that at least one phenol-aldehyde-hydroxyl group present in each unit of the phenol-aldehyde condensate either does not react with one or more substances which in turn will be easy. to react beforehand. polyoarboxyliquo compound.



  Preference is given to prooddor first to hydraxyal, oay.ation of phenolic hydroxyl groups, then ootirifïe *, then to the groups obtained with oarbo acid.
 EMI8.8
 xyliquo, an anhydride or an acid chloride La
 EMI8.9
 The preferred method of hydroxyalkylation is to react with compounds containing an oxiranoe. Examples of such compounds include the oxides of propylene, butylene, styrene, and cyclohoxeno, glycido and dpichlorhydrino. Many other aonoepoxides can be used, but usually the oxides of talcoylbno which do not contain more than 6 carbon atoms are usually used.

   COl '.: 1.'Jo other COL1pOOÓS utillS :: 1.bl .13, we can cite the related vinylglycidiquo uthor ot los 00pOSÓD prepared by rtoetion of 6pi.nilorhy (llïno on nonophenola alkylated and hülo, 56nÓa, horn 11 Ótho: r pcnta.ch2oroph6nyglycidi '

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 EMI9.1
 OOC1r.1U catalysts for the reaction of cyolo Ozirtui-li copous on the .Troups hydroxylos phcnollquos, one will quote Ion hydroxydoa alkaline or aloal1notoru :, aninua prirjairoo, aoco: ds, ixss or tqrtiairut or basic alkaline soils.

   Parai caux-oi, we will cite Ion hydroxydùa do eodiua, do POtaseiJI'1, de liJ '; i.iw1, do calcium ot do barYUL1, and we can also use the aminus oostao m6thyl- ,. diuethyl- ', didthyl "tri-.idthyl-9 tri6-u-hyl-, tripropyl-, la: .. tnyz .. boxizyl-m la clitl & thylh'droxyethyl .... diauthyl-2- hydro- x3ipxapyls.rainu, tc .... as well as sois .do strong basoa ot weak acids, conrao ltactat0 or bonzoute cte sodiua. The reaction can be tstcctu4o at eoaprisos temperatures between 50 and 25000, ot preferably there is no solvent, although one can use ao2-.w¯ts to decrease the viscosity.



  The hydroxylo ph 6noliç, ', H .: of the Novolacs could also be hydroxy alkylated by the reaction of halohyéir1- nos alooylbne on the hydroxyl ph6nQliue with the aid of
 EMI9.2
 3-equivalent proportions of alkali metal hydroxide
 EMI9.3
 causing the reaction. Cormo halohydrins of aJ.co; F''1. / Which are suitable, we quote the chi.or- to brormyc ''. In. :( 3 ethylene, chlor- or brochydrlne do propy2ér.o, 2 3-butylene chloro or bronhydrins and glycerol chloro or brorahydrints.



  Another method of hydroxyalkylation of novolacs consists in making them react with C.- nates of alkyl l1o, cor-nu ethylene carbonate, Io propylene carbonate, n using aata.7.;, A,: ura eotiio the potaosiuc eurbonato.

 <Desc / Clms Page number 10>

 
 EMI10.1
 



  Lee Novolaquos or binds Rdsoloe must react 80Ul: 1is to the reaction until practically all the reactive phenolic hydroxyl groups have reacted (with a residue preferably 1 inside 0.5% of hydroxyl ph no3, iquoa which have not not ejagi) t Co result is importunt for uf1pOoher oxidation ot
 EMI10.2
 an undesirable darkening of the product obtained * It
 EMI10.3
 At least 1 mole of ethylene oxide or other etherifying or weakening agent per 6 equivalents of phenolic hydrogen is required. However, los r6Bins prepared by reaction with a proportion of alkylene oxide of up to 3 aoloa per number of hydroxylo phûnoliquo can be used. At least one hydroxy ... alkyl group is needed per raolc: culu of condensate.



  A large nonbro of acids, haloeÓnuroe d ttc3.d .... anhydridoQ of ac1dùB, etc ..., or luurü JlanvB, can be used to react with hydroxyalcoylphûnyl- ethurs dos Xcvolaquca or dos Rsolcs prepared confer to the invention. For example, the hydroxyalkylnovolacs are ostÓril1Qr by 0.5 to 490% of a dicayrboxy2lquu alphaMbOta-1naturÓ acid anhydride per hydroxyl equivalent, by the cr.rboxyl acids that can be used, or their chlorides ot theira anhydrides, mention will be made of phthaliquo, nadiquo and hoxahydrophthali- acids. that, tetrahydrophthaliquo, totrachlorophthaliquo, n'thyl- nadiquv and chlorondiquo.

   Cos cOwposJa oarboxyliquoa pont los conposde carboxy11qvs teacher created for the uploi
 EMI10.4
 in the invention, because their use in the compounds
 EMI10.5
 sitions of the invention restrain the fuaion point of the acid soluble in water reagent at about 6000, The previous range of fuaion points ost Co 60

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 EMI11.1
 at 140 0. The carboxylic compounds less p.Ót6: t-éa for use in the compositions of the invention are the acids, acid chlorides and anhydrides such as
 EMI11.2
 a3.3.que, chloronalcic, 6trlDaléiuo, itaconiquoi citraconiquo, nesaconiquc, Buociniquo ot trir.1011itiqua acids.

   The bromides and diacid iodides corresponding to the chlorides not mentioned above are also suitable, but are more expensive to use *
 EMI11.3
 L: ostrification of dr3.v3 hydroxy-6,;. Idrd ,; oat do rrdfdrenco cffactu6a at uno tonpdraturo a np.riso between about 100 ot 150 C, but we taste navura.Ilc :: ent observe tv! 1pé: Ólt'.n'ùs more o * lo \ N5es or lower * When Poly acids are used: rb3Xyliquoa. The progress of the formulation reaction can be observed very much by the amount of esterification water produced. Small amounts of toluene or xylene can be used as distillation agents.
 EMI11.4
 azdotropic to facilitate water distribution.

   When using acid chlorides, solvents are preferably used during the reaction. The acid chloride can be dissolved in a suitable solvent,
 EMI11.5
 CO1ù lo benzene and the chloride of ethylene, and added to the derivative hydroxy-dthdr6 equally dissolved in the aorta solvent or in a similar solvent. The reaction can be carried out at a temperature up to the boiling point of the solvent. The reaction can easily be eliminated, for example by vaporization, at the end of the reaction.

   The progress of the reaction carried out from the acid chloride can be observed by

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   measure the quantity of hydrochloric gas given off during the course of esterification. In addition, in
 EMI12.1
 the reactions carried out from acid chlorides, it is advantageous to use acceptors of halogenated hydraoidos, such as aninus and strong bases,
 EMI12.2
 Preferred acceptors are tertiary amines, C010, pyridin or tri6ethylminot. The acid chloride group remaining on the bibasic acid chlorides is hydrolyzed to acid.
 EMI12.3
 



  7.a solution of the resin soluble in 7.'aeironiaquf is easily prepared; intended for incorporation into a wax uuulsion composition. In a sample of preparation, one introduces from a container 1'0raÓ, in order to avoid the port of rjutieros vol: vï.vr 100 will leave the rdaïnu oolublo dcuis l 'ar \ fl0n: LI. \ CiuoJ vt 500 parts of water. While stirring the mixture, add onooro 25 parts of a solution
 EMI12.4
 of aononiun hydroxide at 2a and the titration is continued until complete dissolution of the resin. It was possible to cause gentle heating to accelerate the solubilization.

   In the preparation of the solution of
 EMI12.5
 resin, the o. :: u: 1oniaquc can be replaced wholly or in part by other alkaline natièroa, by oxam-
 EMI12.6
 full back of volatile organic auinos. Suitable volatile organic orabo aniius include aliphatic amines and hydroxylated aliphatic alders having melting points below about.
 EMI12.7
 200 0 at atmospheric pressure ot, pa oxoraplo, Dorpholino, 1 vthoxypxapyl, nr.üno! 2AlCino-2-u6thyl-1-propanol, Óthanolan1nc, 1: \ diúthylJthrul01lino,

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 EMI13.1
 ltdthylono diacina, and triethylacin, the resin solutions contain are generated! from about 5 to 25% of solid catalysts, preferably from about 15 to 20%.



  Many waxes, both natural and synthetic, and even polymeric backings are suitable for use in wax polishes based on ciro drau7.sion. Examples of generally preferred waxes are Carnauba wax and niorooristallinc waxes. Conno oxonplos do oatieros poly-. mbros cirousos, we can cite polytlelènoo waxes. Such a polyethylene wax is prepared by sounotting the ethylene either alone, or in prosenco of a coruaotif, at due toupdraturos conprisos untr approximately 150 ut 30009
 EMI13.2
 at pressures ranging from about 35 to several hundred
 EMI13.3
 of kg / in Lc polyrar4 obtained is a polyethylene dfdthylène
 EMI13.4
 solid, hard, waxy, consisting of an alipha- substance.

   saturated tick which is characterized by groups
 EMI13.5
 .CH2- repeats, having a noldculairo myon weight between about 1,000 and 3,000. The polymbrz. oet
 EMI13.6
 under one liquid phase with the action of a gas containing
 EMI13.7
 oxygen to cause an autocoir reaction
 EMI13.8
 approximately 5 kg of oxygen per 100 kg of wax is obtained
 EMI13.9
 an oxidized polyethylene wax containing at least 3% oxygen (based on the weight of the wax
 EMI13.10
 oxidized).
 EMI13.11
 



  The wax enuisions are prepared. used in the preparation of wax eductic compositions by dipping the waxy compound into the water with the aid of an ulcerative agent. Known enuCsifying agents which smolder, we can mention 14s organic anincs, fatty acids
 EMI13.12
 t

 <Desc / Clms Page number 14>

 
 EMI14.1
 superiors and their olangùs. ua organic amines that can be used are dnundr6os oi-doesus ot la triÓtha.nolc.w1na. Ooouo higher fatty acids, we oitora lot of saturated aliphatic acids ot insuturéo, containing 12 h 18 atones of oarbono, 0 \ in pxt3ou- bind the acids ol6quo $ linoluiquo, .inm.Gn3quo,
 EMI14.2
 lauriquo, palnitiquo ot stearic. wax solutions
 EMI14.3
 generally contain from about 5 to 25% of the solids, preferably from about 15 to 20% of the acid.
 EMI14.4
 solid.

   We give below an operative part of the preparation.
 EMI14.5
 tion of an axorapl3 of watering do ciru in baao do cjro do
 EMI14.6
 Oarnauba.
 EMI14.7
 



  CIRSE EMULSION A On n4l.n, ge 9.8 parts of airo do Chmaubn. refined with 4.1 parts of a resinous condensation product ter, pèno..phdno3., We heat the riJlangc I: .1l.Jua stirring until tuiipdraturu do 17700 do so as to obtain a mdlango uniforno, then we cools bzz 100 0, after which 2.2 parts of celango ru oleic aoido are added. We heat the c61Mgù to i 00 C ot it is raa3.ntiont the nôco teuporaturo with stirring until it is uniforudnont fluid; Mora is added 1.5 parts of unrpholino. Continue reading 1Do until the conposition is uniformly fluid. Z: n6lango resino-oiro-enulsifier obtained cot then added with rapid stirring to 81 parts of water b, uil- lt \ 3 and the rofroidio denulsion at anhicaito temperature.



  We prepare an oxonplo of ú! .. u1aion do ciry Uo polyethylene by operating the uanier-j mÛ.uU1to:

 <Desc / Clms Page number 15>

 
 EMI15.1
 MULSION OF WAX B
 EMI15.2
 Melt at a temperature not exceeding 132 ° C>.
 EMI15.3
 
 EMI15.4
 bzz 9 parts of "AC Polycthylono G29", prepared * by the firm Alied Chemical and Dye Corporation, On. 1jcuto then 0 with stirring 2 1 parts of acid oluinuo with molten wax and the mixture is warmed to 10 C a day / i still stirring until fluidity uniforuo; we added / 2, 4 artivs do norpholino. The alango is warmed to 12100 and stirring continues until uniformity of the co) c3ition.



  The obtained u61c.ngo is added to 81 6 parts of water c'4zuZ- fairy at uno toapuraturo just below the boiling point, then it is cooled rapidly, rt the pulse to tonpraturo axbianto with stirring.



  It is within the scope of the intention to be poror in the colipositis d'dnulsion do ciro, 'nutw.,. components, by due uaulaions or latex duo polynèros, OOt: 1'.1 ';: the resins of polystyrene, of chibruro of polyvinyl and p01yo.Ol'yli'lw) G. C.) / 3 enulsio1: ', s may contain from 5 to 25% Ú) content: 1 solids, preferably from about 10 to 25% of t: ati: r4s solids.

   C:.: .... to suitable components of this type, we cite3:; a, los dnulsions do rdsinos do polystyrôno z, high nclculairoa, of about 5,000 do uoldoulairu ov do pr6f3ronao oellos which possess due higher aolculairca weights. at 10,000âo. those of these oonpositiono '..1. \ i are dos daulsio-is aqueous drilled in the preparation due to rdsinus do polybtyrbnu and oO \ lro.r.1f.1 \ .mt nl).' '; J6Qs "latex"
 EMI15.5
 are, in general, preferred.

 <Desc / Clms Page number 16>

 
 EMI16.1
 



  A typical polyocre lulo ion is prepared by operating 40 as follows 8; POLYMER C UHSIQi7 A polystyrene prepared by UB8 * Chcnical Corporation under Nénagac is introduced into an apparatus for uelango feru6 34, p parts of U-2003 Ubatol. in the container 11.5 parts
 EMI16.2
 of water and we continue the nelango until homogeneous,
 EMI16.3
 then a further solution of 1 part of dibutyl phthalate ot 0.9 part of triabutoxyethyl phosphate and 5.6 parts of () is added to the mixture. Stirring is continued 20 rlinuteae The polishes are emitted under the The invuntion are usually prepared by ± 3B by ra!, rnßa dos diff3rints component cenno the solution do roaino solublo to the atlt10n buo, the <: bu1aion do derive from and the other dvtuellolient solutions of 0sireoa in the particular formulation.

   The wax emulsion cracks contain approximately 5 to 25 parts of the total solids per 100 parts by weight of dispersion. The content of solid nctlergs comprises a general of about 1 to 15 portion fio rdsino solublo to a: noniaquu ot do 1 to 15 parts of
 EMI16.4
 wax for 100 partios. we weight, do the dispersion. Cos encaustiquas its characterized by a very
 EMI16.5
 clairo L-t due qualifia wJliorüûa do brilliant, do hardness ot do resistpioo to water.



  The following oxoplvs illuutrùnt the invention, however, liuiter. Luis plum oxonplos illustrate the preparation of phenolaldehyde resins intended for use in the compositions of the invention.

 <Desc / Clms Page number 17>

 



    EXAMPLE j.
 EMI17.1
 In a 40 liter rcaotour doubled to see, 7.050 parts of phenol, 35 parts of oxalic acid and 14 parts of a wetting agent are introduced.
 EMI17.2
 nnioniquo. The phenol is heated to 90-100 Gf and then about 4040 parts of a 37% fornol solution is added over 1 hour. We wear the rdsino
 EMI17.3
 reflux until it is free of torsdl1yde, then the water and the phenol which has not reerged by distillation are removed, which are teraino. 200 C under ', c = 6500 parts of a phdnol-nldéhydo unoi6sin of weight 1: 11' \ 1 (: 0 ", 1" mean iro about 520.



   EXAMPLE 2.



   In a 40 liter double orro-liter reactor, 6850 parts of phenol and 6.6 parts of sulfuric acid are placed, the solution is heated to 100 C and then 2912 parts of styrene are added slowly, When the addition of styrene has been completed. , we cool the phenol
 EMI17.4
 Styrofoam. & 100 0 ot 4540 parts alum solution are added to the reactor. 37 do fornaldehyde solution, are added to the reaction at reflux until it is free from hydrochloride, then distilled. water falling to 200 C knots empty.

   10900 parts of a phenol-containing polymer containing 0 4 mol of styrene are obtained per phosphorus of phenol. In the same way, phenoraldehyde resins containing 0.5 are prepared; 0.625; 0.75 and 1 styrene layer
 EMI17.5
 by nola do phonol.

 <Desc / Clms Page number 18>

 



  EXDMPLE 3.
 EMI18.1
 



  Another ph6ro resin is prepared. .l.ddhyda of the nanibro d60ritu in oxonplo 2, mia on roopl9tmt lo styrene per 3304 parts of vinyltoluënoé the resin obtained contains 0.5% of vinyltolubno per molo of phenol, EXAMPLE 4
This oxomple illustrates the process in which the phenol-aldehyde resin is alkylated after preparation.
 EMI18.2
 do the resin. The resin prepared in Example 1 is introduced into a 3.3 r6aciour, 5200 parts of the resin and is heated to 12c1-3a C! R then f, 2 parts of aulturiquo are added. We introduce oncoro'dnns lo o3.cu; o 4090 parts of l1l: .onèno ot on porto 4 la tOL1p6rt'.turo do 160 C.

   After 2 hours a vacuum is applied to the reaction and 365 parts of lino are distilled off. *
 EMI18.3
 nèno who did not react which nontro q1fto 0.55 aolo do li. .., no n reacted by noio do phenol, the d8h3tdroxylo index of the final resin is 170 The following oxonploes illustrate the prJp'f \ tion of a phno resin, a7.d4hydo hydroxyalooyl, of which LiJo is used in 1 ' invention.



   EXAMPLE 5.
 EMI18.4
 



  5200 parts of the tós1no proparoo in Example 1 are introduced into a doubla do vorro reactor and increase the pressure and heat to about 150 C.
 EMI18.5
 injooto in the reactor by pupnge 86 g of tri.:1Óthyl ..



   iriino, followed by 8680 parts of propylene oxide, at a flow rate such that the tecpuraturo so f1O.inticnno at 150-170 * 0 and the pressure below 5.6 kg / on '. After one hour, the pressure oat tonbso at 3.5 BÎQn2I is dôtond

 <Desc / Clms Page number 19>

 
 EMI19.1
 
 EMI19.2
 The excess of propylated oxide is removed by ôiamlation, distillation which is vacuum-drained. the. rdsijic hY3rcx;, sroprl3e has a content of hydroxyl groups p, r.oZlrtos ir¯'riure 3 0 t # and an hydroxyl number
 EMI19.3
 do 346.
 EMI19.4
 



  0-, i proceeds e.-Ba.Qnt to 1'hydrocypropyl:;. We assay phenolic substitutes doz a: eales 2 3 and 4 operating by Io operating code described in ltoxoriplo 5 It takes a reaction time of 3 to 4 hours in the oven lower, the rate of hydroxyls phdno3.iqucs to uno val3u: nCr.euro, 021, é, We obtain leo réeu2tats
 EMI19.5
 following TABLHAU ,!
 EMI19.6
 1 li "- Substituent; i Nolos do Subati- Tor.our eu {Includes! R killing by t10113s hycroxylos: d'1'I; / -. I do phenol phcfnoliquco 1 t: 1> (.>: Ylq de pl: enal 4 en Pole- $ erc zyldl,., ". w..a.wrrw.r!! | '6 aSyx' & iQ 0.4 0.10 j! 270 j 6 f re, c 0.4 0.10 270 7 l, ti.n; oluê, Q 0.5 0.15 46:

   Lir.1CY ', o 1 0.55 0.12 164 9 Styrene 0.625 0f10 2.6 j 10 st: T & ao 0.50 0.09 261 ± 1' il Styrene, 75 0.13 i 233 ff Ji 12 r Styrene 1 jojo 0.15, '"T 1211:
 EMI19.7
 The exonr-100 resins 1 and 2 are also reacted with 6 'ethylene oxide by the operating process described in Example 5, but using Cat- lysour l'i', from Gi6thylauino. Lao results of these oscais are reported in Table II below:

 <Desc / Clms Page number 20>

 
 EMI20.1
 TAFâ: le'1?:
 EMI20.2
 jjt Mole of subati- Content on Index Exfnpl killing by drown Content on J '"è.iO' <J '" & 1 Substitute of phenol; c Croxyla phenol 5 in weight 13 116ant 0.05 374 14 Styrene Oe4 0010 289 H j Styrene I 0.4 l Cf, 10. l 289
 EMI20.3
 The following examples illustrate the preparation
 EMI20.4
 ammonia soluble resins of the invention.



  EXEI '2'. ' 0; 1 Introduced into a 20 liter reactor
 EMI20.5
 double glass 4860 parts of the prepared resin
 EMI20.6
 in Example 5 and the mixture is heated to a temperature of 120 to 13,000. 4380 parts of phthalic anhydride are added to the reactor. At the end of about 1 hour, the obtained! -Daine, which possesses an indigo dia- cide of 210th, was poured into a plaitrol.



  By operating in a loving way to that. described in Example 15, the hydroxyalkylated phenolics of oxides 6 to 14 are reacted with the carboxylic compounds in addition to phthalic anhydride, tJtra! 1hydro} 1'hthalic anhydride, ttrach7 anhydride. oroph'aliqua, aucciniruo anhydride, ma anhydride, 7.biqua, and nadioue anhydride. The properties of the results obtained are indicated in Table III below with the results of the example
 EMI20.7
 15.

 <Desc / Clms Page number 21>

 
 EMI21.1
 



  TAU11Z.Ati He!
 EMI21.2
 3Y.c.ple R.ssi "\ 3 lcoy- Ratio of O: cyde of a1- Compound car- 1-ciec Point da Goulet: - * 1: # sub;:; titu6nt. Coy10r. Bo; ylïqu dtauwà. . iuz.;. 0 ;. Gardndr ¯L¯ ir: ¯¯ hEdt'l. ±!? - ± # 1 !! ī b) "¯¯J2.l¯- 15 :: eaaat Oxyde do prcpyl anhydride pht11i 'lUC 210 6S-76 <1 16 Of oxydv arethylene anhydride phthaliquo 41f 63-72 4 17 If oxyce do bu, ylènc arliyt-irièd phthaliquc? 00 66-86 if 18 "prop: oxide," lk :. t, jtrahydru .. phthalic anhydride 19t 72-76 2 19 styrene 0.4 / 1 prcpylèn3 oxide pht anhydride (l! r, 3 175 61.-eo <1 20 styr "" 1e 0.5 / 1 oxyda df0th: l (> 11 phthalic anhydride3 180 51-64 7 21 styc-n 0.5 / 1 oxide do? rOp71 annhydride r.ccinicue 13 55-65 4 22 vin / 3 t7..3ne 0.5 / 1 oxide prop- 1 ùn-, r.lyc:

   i? e pl ta 1 i que 160 71 - $, t ,, 1 23 1L-noibr., j 0.55 / 1 o :: yde of prcny 1 phthalic anhydride 132 7ë-ë / 5 24. ctyi'3 0 , 5/1 oxida of -1 cro p. . 1 - 'r., A:' 11'è ::: - iè ':! nadic 212 65-75 1 25 st; -xv ^ e 0.5 / 1 o'C: rf:.: de prc.-7.ca2 rnhyuride pht: Üiq1.'a $ 9 66-E2 - =. 1 26 ct ; yf? .rfâ 0.625 / 1 oxide d.- prc.py?t,ca,r.5'dl-¯'ie phtaliqm 176 71-C4 1 27 ztyi'î.J.2 0.75 / 1 oxyda de . propyl phthalic anhydride xi 69-é'4 1
 EMI21.3
 ('<} ro.:-1t' melting determined by heating a crushed sample of the resin in a Cé'-wi.t tube: 1ire1 in an oil bath, quickly; / -: dt "e: lo'i :: '.. n'! r5 C psr ni: 1ut :;); observation of the vx3ria2 which the, 1Ch; u'H ilIon becomes liquid, (2) Color at the Gar.! scale. w :: n ", d't, 2rs; ir .. * i3 by C: '1F: l :: - aioo1 (' e color 3 = a sample with the values d .;

   colors t = ar La .r i ': ur: .. 5 per 1 - :. 3 3 G-rdor Laboratoriec, "= th2S.ï. 1.:3't"'fl:Ü""ld.

 <Desc / Clms Page number 22>

 
 EMI22.1
 



  1!:; I1I (continued)
 EMI22.2
 'Example Rêsiao sico- Ratio of Ox / of al- Compound car- Index Point d3 Color R linked by substituent boxylic cicqe Gardner fusion ¯¯¯¯¯ ¯¯¯¯ # ¯¯¯¯ hydrocarbon ¯¯ ¯¯ ec (1) (2) 28 strèn3 0.5 / 1 propylene oxide maleic anhydride 1'lg 48-68 5 29 e'r & ne 1/1 propylene oxide phthalic anhydride 167 73-6 1

 <Desc / Clms Page number 23>

 
 EMI23.1
 The following examples illustrate the pzdp r, t..o: dos solutions a! .JDou; 1.Glco.lea dos resins eo ".ub.as with 2'oniaqua.



   EXAMPLE 30 Assea roughly 150 parts of the
 EMI23.2
 resin prepared in example 15 and then added with stirring to a solution of 40 parts
 EMI23.3
 28% aqueous aranoniaquo in 800 parts water, temperature aabianto <The. resin d :, caout to ^ p, ;; e: a, .nt and rapidly in aononia giving a transparent solution of color pays.
 EMI23.4
 the resins soluble in ananoniaquc prJares in Examples 16 to 29 are Jol1ont treated -le this!: thong.

   The properties of Ioluticn 0; .11:, '' '1 ".: 1. :: \ .- calo are reported in table IV cl-apraf cOfipart1cQont to glues of a soluble rdsino de1 is the aornoniaquo du conneroo treated in a ... way: The glue wax described above. As a result, diva the case of the conacroo plant, it is necessary to dissolve it in a hot solution of aoaoniauqe, then to filter a certain quantity of insoluble material * An examination of the results given in Table IV below against that the color of the solution
 EMI23.5
 The anaoniacal cation of the commercial resin is much darker than the glue of the resins of the invention.

 <Desc / Clms Page number 24>

 



  TABLE IV
 EMI24.1
 10 ± SOLUTIONS; IACAMS
 EMI24.2
 1 Resin Color Viscosity Appearance of the n "RT na ce exon- Gardner Gardncr solution le n z0 15 1 <A solution e2ixo
 EMI24.3
 
<tb> 31 <SEP> 16 <SEP> 2 <SEP> <A <SEP> e <SEP> n
<tb>
<tb>
<tb>
<tb> 32 <SEP> ¯ <SEP> 17 <SEP> ¯ <SEP> 2 <SEP> ¯ <SEP> <A <SEP> ¯ <SEP> @ <SEP> "
<tb>
<tb>
<tb>
<tb> 33 <SEP> 18 <SEP> <1 <SEP> <A
<tb>
<tb>
<tb>
<tb>
<tb> 34 <SEP> 19 <SEP> <1 <SEP> <1
<tb>
<tb>
<tb>
<tb>
<tb> 35 <SEP> 20 <SEP> 4 <SEP> <A <SEP> "<SEP>"
<tb>
 
 EMI24.4
 36 21 4 <A * le; f; 1 :::, or.1o \ 1t troubla, 37 22 <1 <A z 01 ': \ il' (38 23 1.2 / ... l ...

   He i
 EMI24.5
 
<tb> 39 <SEP> ¯ <SEP> 24 <SEP> ¯ <SEP> <1 <SEP> ¯ <SEP> <A <SEP> ¯ <SEP> @ <SEP> "<SEP> ¯
<tb>
 
 EMI24.6
 40 as <1 <A k n 41 26 - trouble, dov
 EMI24.7
 
<tb> phases
<tb>
<tb> 42 <SEP> 27 <SEP> "<SEP>" <SEP> "<SEP>"
<tb>
<tb> 43 <SEP> 28 <SEP> 5 <SEP> <A <SEP> "<SEP> ciniro
<tb>
 
 EMI24.8
 44 29 # # trcublo, s 5iaj-
 EMI24.9
 
<tb> ¯ <SEP> 44 <SEP> ¯ <SEP> <> <SEP> ¯ <SEP> - <SEP> ¯ <SEP> - <SEP> ¯ <SEP> trusted
<tb>
 
 EMI24.10
 45 resin> AS olairo, anbrc 45 d coraraerae ", -A dark '¯¯¯¯¯¯¯¯¯¯¯¯¯¯I¯.¯¯¯¯¯..¯¯¯¯¯¯¯ * ## ######.
 EMI24.11
 



  The prepariant ammoniacal solutions in Examples 30 to 45 are combined with proportions
 EMI24.12
 various oonposants described in the foregoing description under the name of "Wax emulsion A", wax tljbula10n BU had "Polymer emulsion C'r for the purpose of preparing self-waxing waxes.

 <Desc / Clms Page number 25>

 The formulations used are shown in Table V below. The polishes prepared in accordance with the invention in oxomplos 46 to 57 were applied to the backs of parquet floors or linoleum and a vinyl plastic composition.

   The observed performance characteristics are also reported in Table V in which they are compared with oncaustic glues prepared from the resin of Example 45, as well as with those of three commercially available glues.



   The comparison shows that the polishes prepared in accordance with the invention are as good or better than the trade polishes for gloss properties, spreading characteristics and water resistance * It was shown above, in the examples relating to Table IV, that the ammonia soluble resins of the invention were much superior in color to those of the commercial resins.

 <Desc / Clms Page number 26>

 
 EMI26.1
 Table V Example of Solution of Emulsion Solution Emulsion Emulsion Characteristic of Dtfflcac1t Resin of wax resin of puly- Brillant Etalt.:mcnt.

   Reîlstance 1! exampie n ne parts by weight # '' re ea1..l
 EMI26.2
 
<tb> parts <SEP> weight
<tb>
 
 EMI26.3
 .i6 30 20 - 5 25 fairly good to good bad fairly good to good asaeztcnàbcn fairly good 7 32 15 10 - 25 If If n "> bcnàbu2 fairly b0nno :: 48 32 20 10 25 If '" fairly good 48 32 20 - 5 25 bad good enough àb (n good enough good 49 33 15 10 25 bad bad bad àbrn as ::; Z bad good; 50 33 20 - 5 25 bada1 ::;

   bad
 EMI26.4
 
<tb> 51 <SEP> 34 <SEP> 2 <SEP> - <SEP> 5 <SEP> 25 <SEP> good <SEP> good <SEP> good
<tb> 52 <SEP> 34 <SEP> 20 <SEP> 10 <SEP> - <SEP> 25 <SEP> "<SEP>" <SEP> "
<tb>
 
 EMI26.5
 53 37 60, 40 - 100 If 11
 EMI26.6
 
<tb> 54 <SEP> 37 <SEP> 80 <SEP> - <SEP> 20 <SEP> 100
<tb> 55 <SEP> 38 <SEP> 10 <SEP> 25 <SEP> - <SEP> 65
<tb> 56 <SEP> 40 <SEP> 60 <SEP> 60 <SEP> - <SEP> 100
<tb> 57 <SEP> 40 <SEP> 80 <SEP> - <SEP> 20 <SEP> 100 <SEP> "<SEP>"
<tb> 58 <SEP> 45 <SEP> 60 <SEP> 40 <SEP> - <SEP> 100
<tb>
 

 <Desc / Clms Page number 27>

   TABLE V (continued)
 EMI27.1
 Example Solution Solution Emulsion Emulsir) n Emision 'ctér1sti (' read effectively # resin of wax resbe A wax B of poly-gloss Resistance spreading example no parts in pulua mother Gloss Spreading Water resistance 'I.} ...-- 59 45 80 - Li.

   100 con good good
 EMI27.2
 
<tb> 60 <SEP> 45 <SEP> 10 <SEP> 25 <SEP> 65
<tb> 61 <SEP> Commercial <SEP> Polish <SEP> A <SEP> fairly <SEP> good <SEP> to <SEP> good <SEP> fairly <SEP> good <SEP> to <SEP> good <SEP > fairly <SEP> good
<tb> "<SEP> fairly <SEP> good <SEP> good
<tb> 62 <SEP> Commercial <SEP> Polish <SEP> B <SEP> fairly <SEP> good <SEP> good
<tb> 63 <SEP> commercial <SEP> polish <SEP> C <SEP> good <SEP> good <SEP> good
<tb>
 

 <Desc / Clms Page number 28>

 
 EMI28.1
 FXP, MPLZ 64 This exception illustrates 110 Deployment of a halohydrino
 EMI28.2
 of alkyleno in the invention *
 EMI28.3
 In a 5 liter flask with 3 nozzles, 520g of unō lYovolaquu prérarÓo are introduced as described in Oxenpio 1 and 600g of ethyl alcohol. Or add to the radiant 880g of a sodium hydroxide solution. 3rd.

   The solution is heated to 80C ot one adds, one hour, 443g of hydrochloride do glycol.



  The mixture is brought to reflux until it rises.
 EMI28.4
 free from hydroxylo phdnoliquo. Alcohol is distilled
 EMI28.5
 and the r6mina is washed in very hot water until it is 1, so that olla is free from odiur chloride. Gold dries the residue pure heating at 15000 under video.



  We react the resin with it. enüydri; 1a alita- liqir and dissolved the amnioniaquo oom1C 'described in ezenplea 5 and 30 The following exonples illustrate 11ot, p.70. in the invention of dtalcoylèneu carbonates
 EMI28.6
 EXAMPLE 65
 EMI28.7
 We iadlango en3emble 212g of Novolac prc: nardo in 1 example 1, zig of carbonate d thyleno ot 1.5g of carboncto do potassiun and heated to 180C under a stream of nitrogen. It ddffftgo of the g'.z oax.- bonique. At the end of 6 hours, the. resides is o; CO: .11 ') to of phenolic hydroxyl and exhibits' ± .1 number of 11hydro--.
 EMI28.8
 xylo do 357.
 EMI28.9
 



  EXAMPLE 66 212g of ilovalaque 1) are mixed in a target, ':) ç'.! '0o as described in example 290g of carbonata do propyleno and 1 5g of potassium carbonate and heated to 170-180 0 under a nitrogen stream 1cmc1nnt

 <Desc / Clms Page number 29>

 
 EMI29.1
 12 hours. 2 *. 00 releases carbon dioxide. Rusino is hydroxyl phenolic oxenpto and has a hydroxyl number of 338.
 EMI29.2
 



  Los r60inea dos examples 65 and 66 are designed to react with phts anhydride, 7.iquo ot discussed in Itarmoniaque or described in exonplos 15 and 30,
EXAMPLE 67
 EMI29.3
 In a reaction apparatus equipped with a CGr.l. ('111- sour at reflux, 3 dolos dhloruro disc. Phthalylo are placed and heated to 12000. 163 parts of the resin described in the example are then added slowly. 5, dissolved in 200 parts of dioxauo.
 EMI29.4
 the ohlorhydriquo forou gas is swept away with a stream of azoto ot collected in the water phège.

   Heating is continued until 1% of HCl has been collected. The condenser is removed at reflux and the dioxano and acid chloride are distilled off and oxidized. under video, at a liquid temperature of 150 C under an absolute pressure of 1 mm Hg.
 EMI29.5
 



  Do we cool the oatmeal to 13,000? 10 µl 36 parts water are added and the 1: Hcl which emerges from the water trap is collected. When we have collected a
 EMI29.6
 mole dIH01, vacuum is applied to ulicinur excess dtot'1.u. The resin obtained is dissolved in 3. ' :year:

  tc, as described in Example 30, EXAMPLE 68
3 moles of adipic acid are placed in one. Reaction apparatus equipped with a reflux condenser and the mixture is heated to 120 C. Then 160 parts of the resin described in Example 5 are added, followed by 1.6 parts.
 EMI29.7
 of paratoluene stfoniqu dissolved in 200

 <Desc / Clms Page number 30>

 
 EMI30.1
 xylene parts # Heating is continued junrtl # 4 until it is released 1 nolo of water.

   We withdraw
 EMI30.2
 then the condenser h reflux and the
 EMI30.3
 xylene and the excess of adipirno acid under vacuum at 15000 under an absolute proportion of 1 na Hg, We cool the reolno 4 tonpdraturo aubinnte and we dissolve it in the aunoniaquo coatao ddorit dnna lt oxol1: plo 30à Dais la prdsoyito donando, we use oxprucaion -resino solublo to the} on1aquo "to define a resino which this solublo'à 3000 in uno aqueous solution of BCr.1on1utl hydroxide at an OÓtlcontro.t" one between 5 and 25? .


    

Claims (1)

CLAIMS 1, -A wax emulsion composition comprising a waxy component, a resin soluble in ammonia, an emulsifying agent and a diluent consisting of water and an alkaline compound selected from ammonia, volatile organic amines and their mixtures, characterized in that the resin soluble in ammonia is prepared by a process which comprises the following steps: (A) reacting together to obtain a hydroxyether derivative (1) a fusible and soluble organic condensation product of a phenol and an aldehyde, containing condensate units which have reactive phenolic hydroxyl groups and (2) a substance reactive with phenolic hydroxyl groups, selected from compounds which contain an oxirane ring, alkyl non-halohydrins, alkylene carbonates and mixtures thereof, and (B) the hydroxyether derivative is esterified in reacting it with a substance selected from carboxylic acids, their anhydrides, their halides and mixtures thereof, in order to prepare a thermoplastic ester derivative containing practically no more free reactive phenolic hydroxyl groups. 2.- Wax emulsion composition comprising a wax component, a resin soluble in ammonia, an emulsifying agent and a diluent consisting of water and an alaalin compound selected from ammonia, volatile organic amines. and mixtures thereof, characterized in that the resin soluble in ammonia is prepared by a process which comprises the following steps: (A) reacting together in order to obtain a hydroxyether derivative (1) a product <Desc / Clms Page number 32> of fusible and solvent-soluble condensation organ-) that @ of a phenol and foraaldehyde, containing units'. condensates which carry phenolic hydroxyl groups (2) an alkylene oxide and (B) the derivative is esterified EMI32.1 hydroX1 ethereal by reacting it with a carboxylic acid anhydride to prepare a thernoplastic derivative containing virtually no free reactive phenolic hydroxyl groups. 3.- Composition of cir emulsion according to the re- EMI32.2 Vendication 2, characterized in that the alkylene oxide used for the production of the hydroxfetb4rt derivative is propyltne oatide. 4.- Composition of wax emulsion according to the re- EMI32.3 vendication 2, characterized in that aladllr, e phenol with styrene. 5.- Circulation emulsion composition according to the re- EMI32.4 vendioation 2, characterized in that the bound oxy of col1'e used for the production of 'h7drOX1'b'r' derivative has ethylene oxy. 6, - Wax emulsion composition according to the re- EMI32.5 Vendication 2, characterized in that the carboxylic acid anhydride used for the preparation of thermoplastic derivative is phthalic anhydride. EMI32.6 7.- Resin soluble in ammoniaq'- intended for use in a composition of wax emulolob and constituted by a thermoplaetiql ester derivative. Prepared by the process comprising the following steps: (A) is carried out EMI32.7 react together in order to obtain a hydroxyether derivative (1) a fusible and soluble organic condensation product of a phenol and an aldehyde, containing condensate units which bear phenolic hydroxyl groups reactants and (2) a substance reactive with <Desc / Clms Page number 33> phenolic hydroxyl groups, selected from compounds which contain an oxirane ring, alocy- lene halohydrines, alkylene carbonates and mixtures thereof, and (B) the hydroxyether derivative is esterified by reacting it with a substance chosen from carboxylic acids, their anhydrides, their halides and their mixtures, in order to prepare a thermoplastic ester derivative which no longer contains reactive phenolic hydroxyl groups free. 8.- Resin soluble in ammonia intended to be used in a wax emulsion composition and constituted by a thermoplastic ester derivative prepared by the process comprising the following stages: (A) reacting together in order to obtain a hydroxyether derivative (1) a fusible and solvent-soluble organic condensation product of a phenol and formaldehyde, containing condensate units which bear reactive phenolic hydroxyl groups and (2) an alkylene oxide, and (B) esterifying the hydroxyether derivative by reacting it with an oarboxylic acid anhydride, to prepare a thermoplastic ester derivative containing substantially no free reactive phenolic hydroxyl groups. 9.- Resin soluble in ammonia according to claim 8, characterized in that the alkylene oxide used for the preparation of the hydroxyether derivative is propylene oxide. 10.- Resin soluble in ammonia according to claim 8, characterized in that the phenol is alkylated with styrene * 11.- Resin soluble in ammonia according to claim 8, characterized in that the oxide of The alkylene used for the production of the hydroxyether derivative is propylene oxide. <Desc / Clms Page number 34> 12. An ammonia soluble resin according to claim 8, characterized in that the carboxylic acid anhydride used to produce the thermoplastic ester derivative is phthalic anhydride. 13. A process for preparing an improved wax emulsion composition consisting of a waxy component, an ammonia soluble renin, an emulsifying agent and a diluent / water and a compound. alkali chosen from ammonia, volatile organic amines and their mixtures, characterized in that an ammonia-soluble resin prepared by a process comprising the following stages is incorporated into the composition, t (A) is reacted together to obtain a hydroxyether derivative (1) a fusible, organic solvent soluble condensation product of a phenol and an aldehyde, contained condensate units which bear reactive phenolic hydroxyl groups and (2) a substance reactive with phenolic hydroxyl groups. , chosen * from the compounds which contain an oxirane ring, the halohydrinea of alkylene, Alkylene carbonates and their mixtures, and (B) the hydroxyether derivative is esterified by reacting it with a substance selected from carboxylic acids, their anhydrides, their halides and their mixtures, for the preparation of a thermoplastic ester derivative containing virtually no free reactive phenolic hydroxyl groups * 14.- A process for preparing a perfect composition of wax emulsion consisting of a waxy component, a resin soluble in ammonia, an emulsifying agent and a diluent comprising water and an al- compound. cuddle selected from ammonia, volatile organic amines and their mixtures, characterized in that one incorporates <Desc / Clms Page number 35> in the composition an ammonia-soluble resin prepared by a process comprising the following steps (A) is reacted together in order to obtain a hydroxyether derivative (1) a fusible and organic solvent soluble condensation product of a phenol and formaldehyde, containing condensate units which bear hy- EMI35.1 phenolic droxylea It Ut> an alkylene oxide and (B) the hydroxyether derivative is esterified by reacting it with EMI35.2 an arboorlic acid anhydride, in order to prepare a thermoplastic ester derivative which does not contain virtually any free reactive phenolic hydroxyl groups. 15. A process according to claim 14, characterized in that the alkylene oxide used for the production of the hydroxyether derivative is propylene oxide. 16. A process according to claim 14, characterized in that the phenol-alkylated with styrene. 17. A process according to claim 14, characterized in that the alkylene oxide used for the production EMI35.3 of derivatives iiydroxyétheré3 and ethylene oxide. 18. A process according to claim 14, characterized in that the carboxylic acid anhydride used for the preparation of thermoplastic derivatives is phthalic anhydride. 19.- Resin solution for use in a wax emulator, which solution comprises an alkaline component selected from ammonia, colatile organic amines and their mixtures, water, and a ammonia soluble resin prepared by the process comprising the following steps: (A) reacting together to obtain a hydroxyether derivative (1) a fusible and organic solvent soluble condensation product of a phenol and an aldehyde, containing condensate units which <Desc / Clms Page number 36> EMI36.1 carry said grouped htdQXJ1 "1; nOliqu'8 réaotifo and (2) an abe ce r, ct.e a-foc oo e 1! k. i hydroxyl groups ph'no11qu'8, chosen rm1 the compounds qfii 1p * ionnent a oxirane ring, acorlèria tmiohydrinea, alooylene8 carbonates and lura mixed, and (B) the hydroxyethyl derivative is esterified by reacting it with a) substance selected from among EMI36.2 coxylque8 CidBs; their; yrides. their halides and their 'lange8. in order to prepare a thermoplastic ester derivative containing practically no more free reactive phenolic hydroxyl groups, EMI36.3 20. Reaim solution for use in a sire mixture, which solution comprises an alkaline component selected from ammonia, volatile organic amines and mixtures thereof. water, and an ammonia soluble resin prepared by the process comprising the following steps: (A) reacting together to obtain a hydroxyether derivative (1) a fusible and organic solvent soluble condensation product of a phenol and formaldehyde, containing condensate units which bear phenolic hydroxyl groups and (2) an alkylene oxide and (B) esterifying the droxyether derivative by reacting it with a carboxylic acid anhydride, in EMI36.4 for the preparation of a derivative enter thermoplasflque containing practically no more free reactive phenolic hydroxyl groups.