BE694797A - - Google Patents

Description

  

    <Desc / Clms Page number 1>
 



    Polymer lacquers with anchored chromogenic groups
The present invention relates to a process for manufacturing lacquers of polymers having an anchored chromogenic group.



   Common lacquer pigments have been prepared by forming water-insoluble metal salts, adding barium chloride, lead acetate or calcium chloride, etc., to acid dyes in which a group sulfo is bound

  <Desc / Clms Page number 2>

 directly to an aromatic nucleus of the chromogenic group, or by formation of water insoluble salts by adding a mixture of tannic acid and tartaric emetic, a mixture of arsenious acid and aluminum oxide , phosphotungstic acid, decides phosphomolybdic, phosphotungstc-molybdic acid or their salts,

     to basic dyes having an amino group.



   The pigment pigments thus obtained are characterized by excellent resistance to hot water and lime and by difficult solubility in alcohols and oils. Therefore, exudation does not occur easily, and they are widely used in various fields.



    However, the known lacquer pigments have the following disadvantage: the resistance to light is much lower than that of common pigments which do not have sulfo or amino groups in their structure.



   Further, it is well known that water-insoluble azo pigments, which have excellent light resistance, are characterized by poor resistance to solvents and chemicals and by unfavorable dispersibility in any medium. .



   In order to overcome these drawbacks, the

  <Desc / Clms Page number 3>

 
 EMI3.1
 dem1oreSS0 provides a process for preparing a color, more particularly a lacquer consti'u.ee from a polymer to which is bonded. chromogenic group. The said process consists in converting into a lacquer a polymer to which a chemogenic group is linked, and presentoo1t right! structures a radical capable of forming an epoljrmèro lacquer that 1-lozi will call hereafter "polymer il chromogenic midord for by addition of an agent of:

  lacquer formulation,
Such chromogen-anchored polymer lakes prepared by the process of the present invention have been found to have desirable characteristics and more advantageous properties than common pigments for lakes and other pigments.
 EMI3.2
 



  A 'chromoub-anchored polymer, having a radical capable of forming a lacquer, usable in the process according to the present invention, is prepared by any one of methods (A), (B), (C) and ( D)
 EMI3.3
 mentioned below. as chromoGene which can be used according to methods (A), (B), (0) or (D), mention may be made of anthraquicone compounds such as indanthronep flavanthrone, pyranthrone, acyl-amino-anthraquinone, a-triazinyl- alnino-onthraquinone, anthramide, anthra-

  <Desc / Clms Page number 4>

 
 EMI4.1
 quinone, carvazole, acridone, thioxznthone, benzanthrone, ibenzopyrenequinone, anzanthrone, pyrazo12TIthrone, pyrimidanthrone, thiazole.

   t1v.'phfJn0, imide.zole, derivatives of naphthalene-oar acids!. '' oxll.q '!.' !. t) s? oxa, zo? e, anthraquinone compounds of pyrasin, sldasin & acédianthrone, 1,4-naphthoquinone, enz0qu: u1one ± t alizarin, trioxyanthraquinone, polyo: 1: ":; '1 - !, n - :: hl'aqtd. none
 EMI4.2
 and the like; compounds such as
 EMI4.3
 copper, nickel, cobalt phthaloyenins and their derived derivatives and the like; quinacridone compounds such as quinacridonQ1.inear and
 EMI4.4
 analogues; indigo compounds such as
 EMI4.5
 indigoindole, thîoîndigop 1 ind: tgoindolethîonaphthalbne and the like; azole compounds such as azo coupling compounds and
 EMI4.6
 azo condensation compounds and their chelates or lakes; carbon black, aniline black;
 EMI4.7
 sulfur dyes;

   the compounds carbonà.1a, the
 EMI4.8
 quinone-imine compounds such as derivatives of
 EMI4.9
 diphenylmethane, tr.iphenylmé.lhx1o3, xanthme, phthalein, acridine, azine, oazine9 thiazine and the like; cyanine compounds, quinoline compounds, nitro compounds and naphthOtlp.inone compounds;

   
 EMI4.10
 fluorescent dyes and pigments such as
 EMI4.11
 compounds derived from diaminostilbenep distyrylbenzene, thiazole, oxazole, triasole, carbazole, imidazole,

  <Desc / Clms Page number 5>

   imidazolone, coumarin, pyridine, benzidine, oarbosty- ryl, pyrazoline, naphthalimide, aldazine, anilinoanthracene, oxacyanine, pyrimidanthrone, triphenylmethane, polycyolic quinone and derivatives of the above mentioned fluorescent compounds which may or may not have a chromophore group and / or one . aurochrome group in their molecule.



   It is also possible to use common dyes and pigments in which sulfuric and / or carboxylic groups have been introduced into the chromogenic moiety and chromogenic groups which can provide brilliant, black or fluorescent colorations, derived from their intermediates.



   The radical capable of forming a lacquer, which can be used in the process of the present invention, is a radical capable of forming salts which are insoluble in water or which are hardly soluble in water when a lac-forming agent is added to it,
The following table is a list of typical examples of radicals capable of forming a la-que:

   

  <Desc / Clms Page number 6>

 
 EMI6.1
 
 <tb>
 <tb> Name <SEP> of <SEP> radicals <SEP> Structure
 <tb> carboxyl <SEP> -COOH
 <tb> 'hydroxyl <SEP> phenolic <SEP> -OH
 <tb> imido <SEP> -CONHCOsulfo <SEP> -SO3H
 <tb> sulfate <SEP> -CSO3H
 <tb> amino <SEP> primary <SEP> -NH2
 <tb> amino Secondary <SEP> <SEP> (imino) <SEP> -NHamine <SEP> tertiary
 <tb> pyridinium
 <tb>
 
The following methods are used to prepare a chromogenic anchored lacquer polymer.



   (A) Method (A) comprises the following steps: diazotization of a chromogen having a radical. amino in its structure, obtained by introducing, directly or during synthesis, a primary amino radical into the chosen chromogenic group, stabilizing, if necessary ,. dinitrogen chromogen thus obtained by adding a heavy metal salt such as pomb chloride, stannic chloride and the like, alkyl-sulfuric, alkyl-aryl-sulphonic acids or their salts, saraosine. N-methyl-taurine, or their salts;

   mixture of the diazotized chromogen thus obtained with one or more species of addition polymerizable monomers, at least one of which has a radical capable of forming a

  <Desc / Clms Page number 7>

 
 EMI7.1
 lacquer the polymerization of said polymerinabL3S monomers by itlditlol-1 using diazotized chrOmOgbne. ;;> 4,, t-¯-.¯-.îgtoiirdepol: permeate;

   and the chemical reaction ...,. 1. 11.11 trolé'J etii. chromog, no with the addition polymfre obtained to form a polymer with
 EMI7.2
 oh :: anchored comogenic for lacquer, (B) Method (B) includes the following drapes: introduction directly or during
 EMI7.3
 synthesis of intermediates, of a polym4rif.H. '\ blfJ radical by addition such as
 EMI7.4
 

  <Desc / Clms Page number 8>

 
 EMI8.1
 
 EMI8.2
 in the chosen chromogeno: mix 01! 3h? '3B! Cgene polymeris7ole by addition thus obtained with 11.:, ") Or more species of polymerizable monomers.;.) 6 .: addition, at least one of which is a radical capable of forming
 EMI8.3
 a lacquer, and copolymerization of the two ::

   components
 EMI8.4
 using polyx initiators;,] a; .i, se,; 1.Dn well known jpouoe form -On Polymer, ohroBic -: - c anchored for lacquer.



  The polynlérisbl: 0 monomers by addition exhibiting a. rs, ¯.o capable of c: w: =: a lacquer usable in the methods CA) 64, (3) mentioned above, are chosen from the groups> J zlôivants (a) monomers poiyr3. = - a.? .vs; w addition which can .provide a radioeJ- aa.:;-:'b0:-J¯iqu the acids ovliqu0r usthacrylic, crotoniaue,.,. ii2.f3C, 't.!:. 1'., aeldiquor y.; âtl: "- :. i.d'r? r le'1 esters rs 3o.ßy.c, uo of acids 1:; ao <.n..q.1.0 l \ 1t '.. fusaric leiqu.e, itaconic soncamide ... mono amide Nalciqua, mono amide: 1Ximax-ique and the ha.oG?: tx.'sE,' s. $ ,: i.C''t acid anhydrides

  <Desc / Clms Page number 9>

 
 EMI9.1
 e-'i amide'3j, nitriiesp methyl and etbyl esters and (J é: ri.y, ± g 1alo1.06 monomers polymerizable by addii; i ;; # i mentioned c.desm.ts, 1:

  These can be easily converted to arboxylic radicals by simple treatment such as hydrolysis or the like. (B) Addition polymerizable monomers
 EMI9.2
 which can provide a radical follow-up!
 EMI9.3
 villyl-sulfone, sulfonated styrene, methyl-styrene sulfonated 11-z, fomethyl-aa3'ylLznude, N-sulfomethyl-methaor ,, jlaynide, monoemide N-sulfoEithyl'-. ltaoonic, diamide N, NI-QiG # lfomethyl-itaconiqu6t N-sulfoaro.inomethyl-p r :: ryls.micle, 11-sulfoamir..omethyl- itaQonen4, de, monoamide I-sulfoamino-mthyl-itaconiqe diamide N, N ' -disulfoeminomethyl-itaconic and the like; (c) addition polymerizable monomers which can provide an sv.l: furic ester radical; sulphate of, P-uyl and sulphate hydroxy- etl''la3rylique, sulphate hydro.MréthylméVancrylîqto
 EMI9.4
 and the like;

   (d) addition polymerizable monomers
 EMI9.5
 which can provide a phenolic hydroxy radical: vinyl-phenol, 11lyl-phenol and the like; (e) additive polymerizable monomers: l.çc,
 EMI9.6
 which can provide an imide radical; itaconic, maleic and the like imides;

  <Desc / Clms Page number 10>

 
 EMI10.1
 (f) addition polymerizable monomers which can provide a primary amine group:
 EMI10.2
 1 'anino- s ty J-é no, l' ally'l>;} 1! 5l ') ,,!; N-Vil1YY> phtaJ-imide and} i-vinyl-oxyamide which can be easily converted to give the said radical t: .nk and the like;

   (g) Sidditioa pa-c polymerizable monomers which can provide an amino radical. qYda. e 1! allyl-methy'l-amine, wrr-aâ, .y # i.-oznixz.o. ethylaorylate, ïV-â'tr-e.m.uo-.éthy..a.ox'ß3..a8,? e Nmârhy, -a.m: 1 no - âxyâth, ory3 .. e, the Iv - â thrlzn3.:oé thy? .. methaorylate and the like; (h) addition polymerizable monomers which can provide an omino tortiaira radical; l,! Jd.imethyl-vinrl - :. 3.n1ine 1T, 11-dimethylanino-ethylacrylate, n, 1i-diethylë: .1Ii ': L \ Jo-éthyll2.crYlo.te, i', Nd .tnâ thyla, rn.r.0-ë h.mâ '; he.Cxyis, ac, hr, N4-diâ-z; hy! smino-ethyl methacrylate and ane.J.ogues; (i) ro: yrâ.rj â ... e monomers by addition which can provide a 2yr.i.di1.iUJ1 la Iv = v3n; '! ¯yrid.ne, 2-vinyl-5-metbyl-
 EMI10.3
 pyridine and the like.
 EMI10.4
 



  In the implementation of methods (A) and (3j, the polymerization can be carried out by any of the known methods of po3 ,,, merisatlon by
 EMI10.5
 addition, such as: polymerization in solution, in

  <Desc / Clms Page number 11>

 
 EMI11.1
 suspension, emulsion or musse. Moreover, the
 EMI11.2
 Well-known polymerization 5 .-, i oiazxnrs may be 3. "-" rw: w'je in the case of the method (.fI.). The 1.Il''sie: ēr¯- "¯. <] i and (D) can be carried out at the same time. '' 3jJâ The polymer, -lation, can also be 8% re e ± fec4x-ied by mixing the polymeric monomer by addition having a radical capable of forming iaoeo lacquer, with the polymerizable monomer by e.e ..

    ? azë
 EMI11.3
 running
 EMI11.4
 Examples of common po1yuld- monomers
 EMI11.5
 risable by addition, mentioned above and which can be used in the process of the present invention, are as follows
 EMI11.6
 (1) The compounds' mthy.ol3t Insatures and their derivatives -Gels as unsaturated acids and v.na.1ogu.eo
 EMI11.7
 amide, for example
 EMI11.8
 compose l '! - méilqlo1és1 alkoxym6thyl: tq: l..wa, sulfomcthylolés et aminomethylolÓo .e ao., x, do, methacrya..mide, 1; a crotonwaide, monoemide itacon1quGF d5.a..micle i taconic, the mono amide a.7.is.- ,, le. muéic diamide, oa: oa.n3.de y "a.ari zxe, fumaric diamidej, vinyl-I la, 6-d.anz:i.nom vr-s xi ass and analon, iies5 compounds presenting iLn glyoidyliquo radical such as:

   àcr3, late rlycidylee Kiëthacyyla.te <3rd
 EMI11.9
 

  <Desc / Clms Page number 12>

 
 EMI12.1
 glycidyl, glycidyl crotonate, mono- on di- (glyoidyl) - 'i taconate, mono- or di- (glycidyl) 119lés> tet Mono- or di- (glyoidyl) -f'umar8> te a7.ly.-lrcinrrh .r; kox and ürïcrae.? compounds having a radical e3 "C 3, '¯":' '7 a ,:' SdJ'C? J.'i3Î '"' r; = a propyl such as: aoyylate of .rr :: i.3.a :. ".lTdran ^ rn. propyl. 1 mé'ihv, cryla te àe # -chlor? - li; - <.i; JG-1.> x;> .- n-ç> ropylo, t {-cbJ.oro- f) -. crotonate, hy (lro: xy-n-p: "I) py: 3." mono- ite-oonate, or di- r G # LLO ^. "fJ F-'Cï" -hy.7 .- '"! -. ,,; t? yle'" '3:' F .. ' ia; f of mono- or di- (-ch.loro- r.> - byd! 'CX.) i-1-1rropyl: 0 ..'; larate of mono- or di (g -coro- µ -bydroiq -n-1> Jnpyl e), # -chlorl-p -hrdroxy-n-po; yl-ally? -4iier and the like; compounds having an aldehydiqvc group such as;

   acrolein, methacrolein, cwo'Vons, lix. '., rE and the like; compounds having a chloride group (11 acid such as; acrylic chloride ;, li1Ó ':: Xtvl "chloride, j-: i' .ue and the like; compounds having an alt'l1, y ', ::' #. of acid such as: itaconic anhydride? maleic anhydride and the like compounds having an isooyanate group such as; isooyanate of 'Y.Ld :,, i.Qg i30Cja ..:;?, te of propenyl and GgZ2G .. () G y ^ We can introduce !;: 1 :: 3 - ":: \ ';::. #' â.4a ', î.t ,.' from polymer to O?" GTJ.G, PGi7. '' ' anc;: 'é a fortomently reactive radical using the L'1onomè ::' fJO 1fl7.1i: ':: "o: l above together with the lcZl.4f: .1-'x'C; ? o} ¯ym0l'.s: ". bl '1 by addition exhibiting a redlc, 5l capable of forming a lacquer.
 EMI12.2
 



  In addition, one can also introduce 'a radical capable of forming a lacquer in the polymer to

  <Desc / Clms Page number 13>

 
 EMI13.1
 anchored, in f'j.8e; l1t react the said radical !.
 EMI13.2
 reactive with it compound having a capable radical
 EMI13.3
 of fo2: x "-r 1st lacquer, used in the, method (D)
 EMI13.4
 mentioned below,
 EMI13.5
 (2) The amides ixee: hzi ± z and J-eu% + o analogues po. #.

   I $ acrylaL - 1-de, lue cJ-otonaanids, ie mono amide i taconic $ diamide mono maleic acid, cUam3. <e l és w.i>, fujnariqu-e monoemide, fumari qne diamide, la, vinyï- "urea, 4,6-diami.no-2-einyl-c-triaz'ne and the like
 EMI13.6
 compounds having hydroxy radicals such as;
 EMI13.7
 ethylene glycol monoaoxylate, ethylene glycol monouidchaoi7lnbe, 1: ethylneglysol nonoorotonate, propylene glycol monoacrylate, nonomei, *. inc2? yl, propylene glycol -Lo monoacxyllycolate, polyethylene glycol monoacxylate; polyethylene glycol. polypropylene glycol monoacrylate, polypropylene glycol monomethaorylate, and the like.
 EMI13.8
 



  A weakly reactive radical (passive reaction) can be introduced into the polymer lacquer
 EMI13.9
 anchored chromogen formed using the monomers
 EMI13.10
 mentioned above together with the monomer
 EMI13.11
 addition polymerisabio, exhibiting 'us. capable radical
 EMI13.12
 to form a lacquer, by reaction of the said weak radical-
 EMI13.13
 ment reactive with an ooaposed having a radical capable of forming U.l:! 6 lacquer, used in method (D)
 EMI13.14
 mentioned below.

  <Desc / Clms Page number 14>

 
 EMI14.1
 



  (3) Addition polymerizable monomers such as: alkyl acrylates, alkyl acrylates, alkyl c3ÙjYlates, alkyl orotonates, mono- or di-alkyl i.tacol1a: '3! $ , waleates, ':!',:.> Q # .- # ", o1à-dialkyl, mono- or di-alkyl fL1TJ1arates (the alkyl radicals mentioned above are x> adi.;: a; ir; dM fo? m'nle CnH2n + 1 in which n is equal to ' <to S), vinyl ao e.i a.c #, vinyl propionate, stearate; vinyISi, styrene, vinyl-toluene, chl, n "" ux- :; of wine. v5, n.y] Lidene chloride, ac / 2-on.i.ii7lflLeo, me% hacrylonitrile, methyl-vinyl-ketone, vinyl-pyrrolidone, butadiene, isoprene, olJoi opnane and the like.
 EMI14.2
 



  The ability to grind and disperse, the degree of lacquer formation and the compatibility with solvents and auxiliary agents of the lacquer.
 EMI14.3
 A0i polymer / chromogen anchor, can easily be removed
 EMI14.4
 controlled by the choice of the monomers mentioned above
 EMI14.5
 sonjointement with the sand monomer by addition having an oapab -'..- radical; do form a lacquer.



  The following examples are intended to 2 .. illustrate methods A and B enioréG8 above .. r! Étho.c \! 3 JAl - :. 1.



  4 parts of a paste of copper trianiiK.û-phthalocyanine hydrochloride (by weight zee) 3 cc are mixed in such a manner as to mix 20 parts of a 35% aqueous solution of ehlo Î> irdric acid, and we have

  <Desc / Clms Page number 15>

 
 EMI15.1
 smel1é 10 melflTIg0;> # b ± m1 vznit to 130 parts by sedition
 EMI15.2
 è'0 Qt d2 ¯ß ', 4'., Four .'7? "ß .. '' 'LiG a reaction of" ".

    '; z' ta? '' -, ':' 7.11. ), 8- "1.J!; ,,, e aqueous 12.!.) ,, iJ ... 19 de -:; ê", ::. 1 '' - l ',' (n, n. . "?,: '. $. C', rest the 'J161a: r.ge l.):.:'! 3: L - i '; t1.te ;, .J: p 1: .sJ decomposition f1 , c :!. '. sY: ta.eide
 EMI15.3
 i -''- euK by de 1: e; ciù> zi.fl-1c = uigu, e;:. n iatii. , Ecuif le p '?.! I': sr. ', I: d, ica, "ceu> c at- starch r.t iodide <l .; B> o "le, s.: Jfl, um, o", s:;:;, ', 0.5. - 'tUle aqueous solution of blet% da,; iitiiLc.yj; #z;,;, np to follow diazo. ;; éi La, diasotee solution ± .i-> ,,, <1, iIn.ni; .c f.a'u filtered and or added to it 14 by'Gi0f3 &, '# m.J 1 1; acrylic. on 1, -,; aélù-y? 'ÓSLÙ 1; ü.nt 1 ?. tempôra, urio ambiiA-1te for 20 minutes then qtt1oY! At 65%, l20 addition polymerization occurred with good foaming.

   After extra hours d? Oezlh #>. IX, we, 1 ?. oesspi '* foam formation After po.yTs & r.'. sation :. we add # ;. i., i; at.;#. m'Jlanse 200 parts of, 'e,;., taken oi; ; 1os filtered. We o ': npi'% ;; iie 503, Ll% to-? 1i aqueous to, e pO1QrtùliI, c "bound 1 ;. 13Ul Ol: Pàfiici, µôL. ± = ¯p:. = Ôi # = ': 1: -> tant 1ù # # 45 ./: aJ, c ": '. Pable da' '.'ors.oy ie J, r que> by c'.ddiio. d Utlx10 fiqu.ú'1ce solution of "oude 1.iJltÓ0 b, the r" ù.ii ;;: thus o'bte? M.c 'oix n, j5, ix.ti ;; <; µThe pH d ;; n> isl-anje µ) & p? s fi3.t?. '., - 1; fl.on, nn ù <j #zsii> ±, ii ± .. 10 la .Jon, con.1afiôn ì.? i> 11, t, '> zn; 3.1; éa, ;; - ùv.m.1 of. pol. '.' ro ..l.i6 li. : =. = J cl;>: = ùnoàone.

  <Desc / Clms Page number 16>

 
 EMI16.1
 



  Y ', t.1.9d'f J..Al :: We select h (.. 1 :: r; o! Z; ne Uj:',: ..; '9Q.:'tio of C. . '' z., Câ '!' !; yT :. 'rJ.': blue '7 "n':" or; "" 'w "',. +" 10 "" "" '' '' : '' J'J '' with 20 parts of a SO:!.:!. L, 't;: iO?: 1 e, q1) ¯1..1.Be -a. ::; 5 1- a. 5. <.. hydrofluoric crt 0,; 5 part of: 1i t -.... j .. "J. ,, ''.: 1Xi.i) .J. is scout at tjl U: '4 so1.ut: tone. o.:; ::. 'on 0 - ::' i <s: 'J';:), (, '3, .ii.fl, a5.>.%. a,' i, 1.t> n according to the method described in (A), 1.



  Once there. ,:>: 7¯ '': w '..' '.% ;:' v. : ii: 4..l: v; we di () r- ,: t0 el1- meJ..e.1 ".. ge sD..9.f3''i: <to '; i parts decides 14.Jv1:'. c- -yJ..i..qt1 .. (.t 1 part of acid: 1. ti? 110l1ic and we 3: t-. ':'; '1 ::;:. ", 1.C \, 30.,% W': i3â.v;, F3% 3.- .l'on; âi..J.ZP'c3.t ': proceed <yeei: =; 1 <1 in a,> 1 (;: - method (A) -1 to obtain an aqueous solution of the polY8e :: fJ binds to a chromo {; ol1e having a capo..o.!. 0 radical to form a lacquer.

   After filtration, we sjjust to '10 the Gonoentra-
 EMI16.2
 * ion of the solution.
 EMI16.3
 y ". ..:.", - UC 0 - ,. ii ..: ¯ On ..i: f: - "P.tl, P, -. ') v: vg.ft: 3 4 é #. a.:.?5,es of triaminccuivra phthalocyanin hydrochloride. 8J'ec 20 parts, 1 .i'.mc solution C'.c .: .'- '!. t3l: Z- ()) L: 55 5 '0. e.ç, -' .. {'0: 1'ÚÙorhydr: tq'tl and' 1 -L1.X1lÈJX18 le ât '., .... ¯:.', F; f resulting Ùi 1 G ; .. '' ^ '%., se # .P.: ... by 6 /' i ..ion '?, "water ot t1 GJ \ C0G r \ ....... ¯'i" e; -.? .lcr.?.: .. 1. ::. 't1, #. til ", n of ... ::, c ..' 'u'.ei.PC.7.v, : ... by 5. '' '. ditiop. of: 1: l'C ': i. 18 '¯¯ Vt; .t' from sodiusi to. mix ± fú [0 and filter Is ll1 (: ¯t) .. ng.3 d: .. :( rtê On:?: 5p.; 1: rc 11! l ::. éJ;> Yl- :. "\ -: A 1:; Ç011.

   Ka <iranAe

  <Desc / Clms Page number 17>

 
 EMI17.1
 1.ié.chaciJjla% e <Di-ethyl-amino-ethyl: 12 parts :: t (:::: f.Ll,; methyl r0 g 8 parts Q2! 20 parts Total 40 in.r-t1ez
 EMI17.2
 We charge this mixture .... '1g0 of monomers in the.' .: ESdril, k, of polymerization, and we add to it the mull9-nr; '$ diasoted above. The O.ßI2? Il'k .fi: .i'sif ?? '. according to the process described in method (A) -1e Once the; 30! ,, 'f: 3lî ". 3S: LCSh finish, the pH of the mixture is adjusted by adding 3. '1..1.1, \ 3 dilute aqueous sodium hydroxide solution and, on:,: 1.4 ta ^ ,, .. 7 "t le a, i. =, Aa.:3 li to L.'. Ii. 'CYI1C), ".' '?' 1E3, We separate by: ii ..

   A1? wr: .Cil the polymer 6 '\;
 EMI17.3
 it is dissolved in a hydrochloric acid solution
 EMI17.4
 diluted for ùht & '1.: tr a solution e, qu0l1..S0 du. ¯.3ilÏ;: 2t'- ,: ': li to the chromogen ç> 1? 4sentaàll; mi radios. 1 capable of forging
 EMI17.5
 a lacquer;
 EMI17.6
 After filtration is adjusted to 0! .2t C011.0 in tration of the filtrate. rîhoâe (A - ° On 1: a.à? .s-nje intimerrsnt 6 parts of ohlox'hydrate de tria.mir, e,.; n.1.ivre ph'ba1, ocY! 2.uillS aux; 42.3 parts of a 35% aqueous solution of acid

  <Desc / Clms Page number 18>

 
 EMI18.1
 ahl.ox.ytx3.q, a, and we adjust the mixture xz? 1.-a.n- to 180 parts by rs.r3? L.on e v and de glaceo We perform 1.a. reaction of a ::. ::.: Z, C- dation P? ',; c'> addition of 1.8 parts dp r.dtri "El,! J. È 4> 1.iir according to 1 proceeds described in .'1.s .s, ß:

   T: ¯ ': would have'? FlCO (±) - '1, After: d p.' ;: ':: i7. 'rrç .ia.sott jn.!: sandstone ìl't;:> é; t;: L? n m ..- (. ",,,, -, -. --.-" V,' " v.,. stabilizes J, a sel cle diasonius of blue '\ * $:.: LGJ.ü :: .. 3 "' :: 1: l:!. 1rrt :: pMalocyaninp}, if. '> J: 'iJ, c: d: t "1'.): 1 1). ';) 27: la1' '' ,,:!. 0.3 of Qh2.-0:: '- J.re de sine. separate pel from c1.iazon '::' i :; "': .par ::' :(. 1 tre.t: to; nv we dissolve it in -1: ± fiz;.; nn: e :; .'i of water pou.): obtain
 EMI18.2
 225 parties.
 EMI18.3
 We prepare a mixture of it, as follows:
 EMI18.4
 acrylic acid. 16 parts
 EMI18.5
 
 <tb>
 <tb> acrylamide <SEP>: <SEP> 3 <SEP> parties
 <tb>
 
 EMI18.6
 water. 32Lt} .ec Total pC parts
 EMI18.7
 This batch of monomers.;: -: "1; introduced into a polymer reactor .- '. Sr.'"; Lvia et c? 1 adds the solution of the salt of. aon., stabiliaae.

   We Q [ite the mixture to. ambient temperature pend1x, '; 30 m. The polymerization was then carried out at 60% for 2 hours then 1165 (1 for 4 hours.



  After that, 'cfcl' is obtained: 1 0% aqueous solution of the polymer bound to the el: fr.; ',: does not exhibit a radical cae. "Of forpier 1.t \' l0 lac, by dissolution in a solution aqueous sodium hydroxide dilu6o according to the procedure described in method (A) -l.

  <Desc / Clms Page number 19>

 
 EMI19.1
 Method LA) -2 Part of 2,4,6tis- (ino-anthraquinonylamino) a-triazin0 is suspended in 30 pa1;:; ::. from an aqueous solution to. 35% shiorhydri * acid.

   Then 0.34 part of sodium nitrite dcma 17 part of water is dissolved, and it is added to the su, spel1siou 0.90Q the diazotization is carried out at (-2 Ci pend = .b J0 minutes and decomposed. excess nitrous acid by addition of sulfamic acid.
 EMI19.2
 We prepare a; n <µlence of the zulv way; nts
 EMI19.3
 Monomethyll itaconate 1 part
 EMI19.4
 
 <tb>
 <tb> acid <SEP> acrylic <SEP>; <SEP> 5 <SEP> parties
 <tb> water <SEP>: <SEP> 20 <SEP> parties
 <tb> Total <SEP> 26 <SEP> parties
 <tb>
 
 EMI19.5
 This monomer mixture is charged to a polymerization reactor, the mixture is added to it.
 EMI19.6
 diazotized above and performs the Hclon polymerization by the method described in claus lam3thodg (A) -1. x.if 't3ta.'. 'i.'! 'X'a.'i T2, we r.11C3'i the GOncç.21 "trt {;:!. one of the 10% solution.
 EMI19.7
 



  Method (A) - 6,100 parts of an aqueous mixture containing 1 part of the llillzonj salt, 1 ml of the pigment. vs'. represented by the formula below?

  <Desc / Clms Page number 20>

 
 EMI20.1
 3 parts of acrylic acid and 1 part of acrylonitrile are charged to a polymerization reactor and the polymerization is carried out according to the procedure described in method (A) -1.



     After polymerization, an aqueous solution of the polymer bound to a chromogen having a radical capable of forming a lacquer is obtained, in the same manner as described in method (A) -1. After filtration, the concentration of the solution is adjusted to 10%.



  Method (A) -7
100 parts of an aqueous mixture containing 1 part of the diazonium salt of the azo pigment represented by the azo pigment are charged to a polymerization reactor.
 EMI20.2
   3 parts of hydrochloric acid and 1 part of methyl acrylate and the spraying is carried out according to the process described in method (A) -1 -

  <Desc / Clms Page number 21>

 
 EMI21.1
 After plYIT1isation we obtain the solution
 EMI21.2
 sçi.tl,;? 4i p; # iiynnôi? <9 lie ar. chromone, showing LL'1 l. "àdô>! E: 1 '' se -...-. wheat ± = =; 1" iomtìl. ' a 1-ù, ql10, àe le, tsëM tlS2Rli.à3i? that 4-- :: -. ;; 1; <1>: ixii l.n. Hierod (A) "1
 EMI21.3
 Apvss:? J..ltra. '!: ic'a., <> # - .T, j ':. 2'be a.

   N 0 $$ the cost .- ".-? Aion of the 6C.lV. '" Ji. ± <i) - <, féj] .jgiµ = 3¯¯ (¯à j-µ We load in tm rdac'beur di> .'r.l .-. 'aii.s. <o t: j.u.tz 100 parts crun aélL <; - aqueous ngc contens'L. t,; R .:.> :; i ';: li; do salt of. éLLzon: Lun1 de pimen '': asoTaue: tepl'96fS (: 1'0 "#iA" "the. formula And. '. ivan'ce:
 EMI21.4
 
 EMI21.5
 and 4. parts (p:, (Q.0.:;- acryT5. ::: 1 () :, we perform 1.i ,, '1., "; i :. ¯ rise: 1 ;; Lon. ; l <J, prQ <;; 1 3-r- iff, d. é f.3K. <; 4% c; rii # in! Iî8thoQ'- '(1:.) =' 1 After 90: lnJ5rif, -i; ior.tp we obtain llT10 aqueous sol1.:t tion of the ... polymer binds Q, 'un chlom'JGfÀ2 gl :: é' rit:?. 2 'an x-adical capable of torsion 1me lacquer, the same m i.:L'):8 as 6id'ws.'fJ da:' \, f, 3 le, method (l !.) "", 'After f'iL tl:; \ "Í; i # l ,. we adjust the crxr'. 'c: r ..- :, r of le, solution h 10% 0

  <Desc / Clms Page number 22>

 
 EMI22.1
 l4éthod e (-4 - ¯ We load (.l # -! s a.). 'Ó. ,,:; ";

  '0U,; - 5. ,, w. - ¯.: X,. :::: .¯..¯ 4 °:,;? Parties d9tu3. aqueous mixture of: u ::,. :: ¯. ¯ .l) Í '¯ç: = i:' i.l: diazoni'um salt of piZ'1l0n'i :; :? n.: w .- -.... ¯,; the formula below!
 EMI22.2
 
 EMI22.3
 6 parts acry2.îc.%., - o e.i; part ',' ''! c Mé'Miaexylate do môtliy3, e, e1 = on po? ymérf, se according to 1 & joedé â writes 1; sà, ii method (A) '1 1> jgi ô zJ p o? j + n; é;.> i. / Dt =.?: '. ->: ..; # .. = x +1; .. 0 5, <-;,% an aqueous solution ".- <';? polymera linked to '' '' ': ..--.' 3EMgèno presenting a radic - '! l ii;>? al;?. ef; e foran'y ## - .. i, aque as described in ? - <: rft'ëlMde '/ - "!., .i8âs-A) l & On ch? .zngo in a' r <'... siet'!: - r '' '' '.-alymerisation 100 part ;; 0. 'a selection has </:. o <. i. , -c tt.:!l'i; 0.7 parts of salt <iia, zi; ni.'ihi; d'1t g> ieii-t f.uor'3'jQent presenting the form s # ail.i "# ..... i". ;

   

  <Desc / Clms Page number 23>

 
 EMI23.1
 
 EMI23.2
 g) ±: J!) tt 0m of acid -'ß.7 ..? s' .. 1 and pe-rtie decides; l1; li. ",: O nj..ll). (7 a,. j é.3. $ 1 0..j: à;: a. '! Çs' solon le prooétll1 (: t7: 3. ::: 1.t J.aD ..: 1 la w'û;: 1. (to - 1
 EMI23.3
 ALyi t 4v. '. 'tY.L :: iZ..W .iû I V; one obi; 3.e> a '; 1 ::: 'c' aqueous solution (hi. Fe..5'.lrï'3 1: 1.6 li un oho: t'mO {) m.0 iis¯ ".,? S '^-being a capable radical ce- for; Her une lac Lle le. same manner as d.è; rit; dDJU ', the method (A) -' 1 TtY, ¯ac7 â't-'i ,, 3 We load?; ::: ? i :: izn r% 4; <toiioe Ae p0¯. n; ::.; tn .. "..



  % 5, we have 100 parts of a 7'.i .'...: '.. ¯'3r. ", E' ::; '. (FJ0UZ. ÈJO :: - <4; GI1S '!' T't 'j, 7
 EMI23.4
 part of salt doe <: 1.5,?. Ior ;; liam du 9i [: n1cnt fluorescent ';,' 'N3 -.'-.': "" Health by the formula vī'-2r '
 EMI23.5
 
 EMI23.6
 6 parts a.5aid .. ':' acrylic G: 1 part: ï ', C'; '; i .3é v: # 6.i, methyl and 1.' on!,; Fi '('; t1) , '::' 11, ù. polymerization of ap # + 1. process dëori-ë dca'3 11: "method (A) - 't9

  <Desc / Clms Page number 24>

 
 EMI24.1
 After polyrisa'on in 9b'tiQK "a solu-.% Ion aquause Ql1% ol, j <i? #re linked to. c: 1 ;; r> oitbne - ':( Be11 "ro'l:' il; 1.
 EMI24.2
 radical oapable of:; '02: 1: nel' ";; n #. i-.l.y: 1s. ---: n1il0 described in method (A) -1 <eth.9JLe (11.) -. tg On C1.1aj} L; f: dan # :. a :: 4act: ll ..: f:

   -% -s; 'a :: G: ....,. tion 'i00 parts fi. '>; n mé12: tlG': J f;! qV.Ci11 (; 0i1 ',; ">: i: -dj L part of' hri- (diasoniuNehlc: rure); the l" "O" ,,, ,,, y- '.01, "dwarf, O 2 part of salt c1 ;; - :; diazo;:' .: 1 ..: J1: 1", - piled: J.1, l,) yesoent represented over there. i ... tu w 3LL: w 'y 4.,, i q ..E ..'; V .. l S 1
 EMI24.3
 
 EMI24.4
 and 7 par'oies decides. .v. '.:.: i.5 ,. we :,/'' <-ÓCtt.'I.0 the. .po1y ... adrisation t1 G. prs the process <iéàci =; 1, 'J in the. ': 1'31; hode (A) -1 After polY',:> ':'; '; 1, S1J.; J¯! N ", r,' :, gets u. ::. <1G aqueous solution of p02, ymèl'G .Li0 1 :. u. '.

   C:.:, 'É: .Iç ") ¯.f'i preson-' 4c.1t: a yadioal capable of fo:" ';'; ': -: .. "t! NE" lf.;, Ç), 1; .e de, 19. same way as described in 1 '),: "1;'; - t;": ', (;. I;: p., A 9
 EMI24.5
 Aprbs ï: .è .. '::'., G: Ë # :. . '',! ùj 'tt3' ;; the 1'4r: 3v: s'c ^. ': l..ü? 'to 0 the 10% solution.

  <Desc / Clms Page number 25>

 
 EMI25.1
 Flethod (A) -1,
100 parts of an aqueous mixture containing 1 part of the diazonium salt of the azo pigment represented by the following formula are charged to a polymerization reactor:
 EMI25.2
 
 EMI25.3
 3 parts of acrylic acid and 1 part of methyl asxylate and the polymerization process is carried out
 EMI25.4
 described in method (A) -1.



  After polymerization, an aqueous solution of the polymer bound to the chromogen is obtained, exhibiting a radical capable of forming a lacquer according to the process described in method (A) -1.



   After filtration, the concentration of the solution is adjusted to 10%.
 EMI25.5
 



  Method (A) -14
100 parts of an aqueous mixture containing one part of the stabilized diazonium salt of the azo dye represented by the following formula are charged to a polymerization reactor.

  <Desc / Clms Page number 26>

 
 EMI26.1
 
 EMI26.2
 and 7 parts of acid cxr2iue the polymerization is carried out according to the procedure described by éio-1iz the method
 EMI26.3
 (A) -1.
 EMI26.4
 



  After polymerization, an aqueous solution of the polymer bound to chrcaogen is obtained, having a radical capable of forcing r? * - 3 lac, according to the procedure described in Aan> the method (.1) -, 1, lh!) "!: ' 'z filt'Óa.Jc: tolt, on J1j11ste ["' - 10 1G la 'Xl?' G: Y '.' G ç3 :. ' of the solution. l :: 1r? tb. 0 e ¯Otl. ::.! 14 parts of (; 1 '- &' 1l: 1.no) -: '1.t "' lilide i .-: jGtY's3r. '.'! ^ ...: are dissolved in 126 parts of acetone. 'SiCbï (.31?, Ée After complete dissolution, we add;) l1.t ,, ;; to solution 4 <7 parts of pyridine, dropwise in 1 minute at a 1> empéialflare of 500.

   After 3 hours of stirring, a'vie by filtration of the resulting mixture is obtained (-metha.srylaEiide) .-. A3.ilide 2-hydrcxynaphthol-
 EMI26.5
 than.
 EMI26.6
 The slÜvan mixture is prepared: t;

  <Desc / Clms Page number 27>

 
 EMI27.1
 (3'-methaorylamido) aa-ilide sodium salt 2-liydro-Vnarh-L ol: only 0 * 3 parts
 EMI27.2
 
 <tb>
 <tb> acid <SEP> acrylic <SEP>: <SEP> 9 <SEP> parties
 <tb> -persulfate <SEP> of <SEP> potassium <SEP> 0.2 <SEP> "
 <tb> water <SEP>: <SEP> 87.8 <SEP> "
 <tb> Total <SEP>: <SEP> 100 <SEP> parties
 <tb>
 
The polymerization is carried out under the following conditions:
 EMI27.3
 Q.ondi t.i9J1 r. .
 EMI27.4
 



  Teoperation; 70 0 Men-Da; '! Terapéra time: t1) .re: t 1Q Time! 2 hours.
 EMI27.5
 
 <tb>
 <tb> After <SEP> polymerization.) <SEP> on <SEP> rule <SEP> to <SEP> 8 <SEP> on <SEP> pH
 <tb>
 
 EMI27.6
 of the solution obtained from. Polynnner 116 at the coupling czent :, by addition of a dilute aqueous solution of sodium hydroxide and this solution is copulated with 3-a-aino-4-siethoxy-bensamide dj.asot8t After coupling, the polymer bound to the chromogen is> Elare; 1.'té by adjusting the pH of the solution to 2 by adding a dilute hydrochloric acid aqueous solution and filtering.

   The resulting filtrate cake is then added and the pH of the
 EMI27.7
 Mél8i: '... e to 9.5 by adding a dilute Eisaline solution, to obtain the polymer bound to the chromogen having a radical capable of forming a lacquer. After filtration, the concentration of the solution obtained is adjusted to 5%.

  <Desc / Clms Page number 28>

 
 EMI28.1
 



  MethodE) L BI - 9 The (4'-amino) -anilide 2 - hydroxyaaphthoic-e is condensed with i taconlq-aa anhydride to obtain (4'-itaconic monoamide) - anilide 2naph4; o! queo We prepare the mixture m :, '.. \ 1;:' ''; 'lt
 EMI28.2
 (4. '-i% acon-monoanià.àe) sodium salt - "snilide --hrz? ^ o. <3, ph.to., O'tea g 2 parts
 EMI28.3
 
 <tb>
 <tb> above
 <tb>
 
 EMI28.4
 o.ium salt 3.i.cot 5 part monoethyl- 1'C3'i.iG: "" rs2w.Ci. 3 parts w: C3't? ... ^. '; 4 G 'of potassium ce', y part '3' ,. 8g, 4 parts Total 100 parts
 EMI28.5
 We do # -a. polymerization, according to the described process <; er = the metho & o (B) -1.



  1;, pi '?> Z polyserization,;> n copulates the mixture aes lalphs, -?' A: '.:': ios! Thraç.uiB.oe iILx.uQ'ùôn À> ui, x on yela.K 'g) j. @ 1c- j? 5J, yix% e bound to OEarotoc, zene containing one part of sodium chloride and / "± 1; parts of acetone.



  , hi; xùi- fi-li; taflsion, the p *, 1 # +. era aLns ''. obtained is washed with 30 parts of acetyl and dried ± at 1% free. The product is added with water and dissolved additionally and a dilute aqueous solution of sodium to 9.5.



  An aqueous solution of the polymer bound to the chromogen containing a radioal capable of forxr'.u. '\ .. 1J: 16 is obtained. After ± Lltte ,? ' on, 1 = c0cntration of the solution is adjusted to 5%.

  <Desc / Clms Page number 29>

 
 EMI29.1
 kliJ ... j.ill.:2 Gelov the process described in, method (B) ',. '..} 1), cbtien-G Je. .s, rn.dean7.de 2-hydro'- .ab: 'a3e. , starting from (: 5 '-amino) -ardlide 2-hydroxy-' ..r,;? htf! 'Lt {t1.G and acrylic chloride.



  The mixture is prepared su.1veJ ', i;
 EMI29.2
 (3 -ac-yl as'ide) "anilido 2-hydtoJqliai '); o7'ouo obtained above-s' 1 part ùiie, cr, -J, ite of NpN-diëthyl'-amino' '' ethyl 6 pa: i-: 3 methyl acrylate 710 parts azo-bisiaobutyrol1itrilo 0, $ Po,? t: lG ethylene monoethyl'-ether; yco ?. 0 6 D grti. é s¯
 EMI29.3
 
 <tb>
 <tb> Total <SEP> 100 <SEP> parties
 <tb>
 
 EMI29.4
 01a effeotu.0 the polymerization 7 (,; J (1 for 3 hours ot at 80-0 pCl1dQ.i'.J. 4 hours'3S After OIL gradually add a solution 8 thatUû $ è. 2% sodium hydroxide to the polymer6 o: LdGSS1U '; 1 with violent agitation.

   We cop1..lle ensu1te 10 sëlcnse resaltant? .Teo o-n.i'bro-p-chloraRiline? After coupling ;, we release 3.> .: polymer bound to Cll "omogene by addition of 2000 parts of dôuàae
 EMI29.5
 dilute aqueous sodium hydroxide solution, After filtration, the filter cake is dissolved in a dilute aqueous solution of acetic acid, and one obtains?
 EMI29.6
 solution of the polymer bound to the chromogen, exhibiting a
 EMI29.7
 radical capable of forming a lacquer. After filtration,

  <Desc / Clms Page number 30>

 
 EMI30.1
 we adjust 10.0% the conoentra / CioH. of the. solution n b µj @ thoàe E -4 Le (4-NMMide 4.'iiE j, o'iâ: a.2¯ '.. e ... w; vl.:, J ..

   G.i 2hydroxy-naph'bcique obtained according to 1 pt> <#i? d to iiôcr: 1: 1; da # ns -Method (B) -2 Si 4 copul.5 with 'le 2' -'- '.': '-. cM. "!' ':' c- 4iphénfil-ether; d ..?, a, zo4; 6 to get "¯.3 pi; y:; ei ;; f '1'} '^ i3' ..,: m: yisable by sdaitioa.



  We prepared the mil-eng>;> 1, =; Jes, # oux polysdrisable pigment P-O - C a-ddition
 EMI30.2
 L0 o% exiu, (::! .- u.em ;; 1, .1, S 1, 7 paycie 4iv..v acrylic parts b: r, .G.CAldhp siethyl 5 2 parts ::: c- 'i-.ar-., i .. 1 0, 5 part 1 1 p iÎ-d, ilàôUly] .- fù miù µflDide 1 9 5, 25 parts .5? i! c ",. 10C parts
 EMI30.3
 We do it. a..n .¯3e ::. o according to the procedure described in i, s>, method (B] .- ,, 5 '.



  After polji1n.;: D sat: t: xt '!, V' r1 R.'f7 "3.x," '"LL' 'the Dolyciëre linked ÛX' .. oh.l'omo [; è1l.'3 en 'lE: ..', 3ia: .4 le r'1, jlaD, S'J poly- ': n6ris ± t "Z 4t3r1.' etSllS 2000 left '' 3 days ,, .i'¯d¯C2J; '. I aqueous 0hJ.orhyd! acid!' if: pJ.e. After :: i '; U': r.: I: io: 1.:> The cake of ± 1,1i = x.a, ti <> n es.l; water was added, and the pH was adjusted to.



  9.5 by addition of 1.IDe GC.,} Xl (;,; ', "' :: 1 f.Ù (; 2.": '. Nc aquff.1.r: o diluted? We get Tune aqueous solution of a polymer bound to a chroffiot! èl1e "having a radical capable of forming 1.1m) lac. After filtration, the concentration of the solution obtained is increased to 5 '.

  <Desc / Clms Page number 31>

 
 EMI31.1
 11éthcde fa) = ï 'On P''pa.: C0 le i: ..': r,, next! additionally polynerizable s0ïQG dye 1.yI3J1J 1a '?' cY '' '- :; i., F:, .s.kt1 S w.'a si 3 2 parts
 EMI31.2
 
 EMI31.3
 aory18: e of sod5.um t 5 la. ':: L,' G "i acr.methy18 le 2 pt13S pelûUlfate de potaDsiu..112 0.12 part water v 9 0, P-.r3 b '± 9.s "a., F3F .:

   "" "'-" ""' "::: L =" = '- 7: - ..; w Total "j00 Jlllti0S
 EMI31.4
 We perform a 901fi6ristion according to the # 7V41 "'UN described in the Pi.'idi.w4ü: i (J3) 1 0 ÁP1't' ;; O i'olym6: d :::::> tion, we adjust lo oh of the melaYJ {';' 3 ç> e?, im16z.Laô to 9 C OR then release the polymbro linked to, uu chromoG0n0? prescmtan1i lm padical capable of nr ',' 11 "a lacquer by addition of 5 parts of ohlort. 1.re of sodium and 500 parts ono. r; filtration, washing the product i.E 4Q parts L.'y-033C? ç, on. l9 dissolves in water and adjusts the i if, µ;

   After a nOV} Y. ;: 10 gadfly gas, the concentration of the solution is adjusted to 10).
 EMI31.5
 obtained.,

  <Desc / Clms Page number 32>

 
 EMI32.1
 X4-thode ijil - 6 We prepare a mixture (the for ':.' 3t '}: ra?:;) Asoic pigment polymôz.isab3> e by addition? of the following structural formula:

   2 parts
 EMI32.2
 
 EMI32.3
 
 <tb>
 <tb>: \ cide <SEP> methacrylic <SEP> 3 <SEP> parties
 <tb> acid <SEP> itaconic <SEP> 2 <SEP> parties
 <tb>
 
 EMI32.4
 Potassium yersulfate Ù, 15 part 68.1.t ..J1.?, 1.85 f \ l: tie,! 1.
 EMI32.5
 
 <tb>
 <tb> .Total <SEP> 100 <SEP> parties
 <tb>
 
 EMI32.6
 The polrm.é,: i ": at: to1J. Is carried out according to the method described in the method (B- J ,, Ç> '; (- H3 polyîtifµrisi2! .Tio1'l" the pH of the mixture is adjusted; * i ;, iùµ # - #, se to 10 by addition of a solution i3.Q, v.ense of soda d, i1ué .. mznite os relaru.3 the Cru'omog'me anorated polymer by addition of one part of chloride 1'1.0 é.9â?;. ïâià and 500 parts of, esetone.

   After f: Llt: t '!: 1.tion, 1.G púl.: R1 "1st to chromogenic anchored thus obtained is washed with 30 parts of acetone and dried in the open air. Then the product is added.

  <Desc / Clms Page number 33>

 
 EMI33.1
  <1 = tonr #, -1.1; ,) (", & '"' - ,, f:, o0f: t ';: 1.j pH of the solution at 9 v :; P') UJ :? ,, - ¯ ¯: .¯¯ ', il 1 r, \.,: T; :: t (' Íi aqueous du. Po1.ymè}; ti) & chromc- {;,: ', -'. 'j: - 1:.' (: "3o ûsß'i E? i3 s :. '#; ¯Y" ^,;', '', :: i'O 011 a) uDtü la C (. '1CCu . "which .¯¯ ...: Gol1}" t :() t obtained at 5; fll, É ii23C. 'â¯'. f.



  ..¯:; - p: / f ..j.e i ': 6. r; 1Ó1.aDg (from i {"} - '-: 5 sr.i" "Mi'j.'.



  1J:; w, ';: h: t ;:' .:; .- !. <S: c "1.tG PO: L: TIliE8J)] ,. 0 by i1: i: 1.-G ,: <'"da expanded formula 5J>: t ::': 'r" ¯4.';) g t; pP.:,"'ofond:;;,,""'5
 EMI33.2
 
 EMI33.3
 acido <r.y] -iq #; e p pa .b5, é.e aesyla'ce of Biëthyle. pi; ce..Bi. =. c persulfate of .GH) tL-f.G8i'tUll Éi = 1 3 part water 32., 85? a,: ': ". l3 &: Total 1; J, .p # ;> + li% àe
 EMI33.4
 % carries out a polymerization according to the method deerit daas la, ili (hhodú (11) -1, .bi, 5:; polymerization the pH of the.! j, lal1ge is adjusted to 10 by addition of \ "1 ... ' 1e sol1.1.t5.on ".f! LeUse of diluted sodium hydroxide, 1>" ...... ¯-O, one rele, rgue the anchored chromogenic polymer pc.a7 addition
 EMI33.5
 of one, part of sodium chloride and 500 parts of

  <Desc / Clms Page number 34>

 
 EMI34.1
 methanol.

   After fil.lrati> i?., The p *; ,, <tnéi% e à r "z, aiùo # çzz-, anchored thus obtained is washed with- '0 p;.:;. l; 1 * s'" e mô% 1 # <; <. and dried in free air "We add 1.3. '--LJ-t,: ¯: 3 ::, 1 ..:' ..;: mi; in water and we adjust the pile d3 iÎ..a. .; ¯ .. - ..i.> = 9.5 lice "obtain an aqueous solution <sort pr.it;. "e '' 010: .'''.- 'anchored for lacquer.

   Ap2'os filtra.1: ic .., o af a = "; + la - ..; ncest;:. 1 ';' ai; ion of g # Qîia.lS.51: to 5. '.; 1: {B) - 'We prepay vn # xél, anè de i <;: # = # ziiL: #. ± -iiii nte. ; pilent fluorescent olysis' -. 'isa.ble 1,) ai.' c.ddiA3, on, from forEm3.e "d- ± #;> to.; ppôe suiyunte 0 part
 EMI34.2
 
 EMI34.3
 , acrylic acid Il 4 w3: ic ::. c; rl [1: t; e of methyl i. ^ '¯ ..'. CW3 p0rsu1: t'ate de? (iffïw; i: .a. '!. il; g'1 part 0S.1., 1, '.: 3 parts Total 11800 parts
 EMI34.4
 We foe <;;: .. rl, X ' <'..', 'L'; :::.: T3D: ;; "Oil sel.'C! The procedure described C! W'3: ^, é; ïtc'f <: vi i13j- .. After polyinerization, the m61an5) oJ.yu6: çisé is poured into 500 parts of T30ï methanol ..: 'yelarguer the polymer to F.mi', ",; 'rflFJü3'it> anchor .

  <Desc / Clms Page number 35>

 
 EMI35.1
 



  &. after ié = '. 3; "; r *; tion; we add Ott9 the g: bea.1.1. of filtration 4. & iiis 1L' Ec; #M. and we 8, just the p3 of the resulting solution to . 9, 1, Ç'1) get it 1> = ie 3p iJ ': GYà Ctt3L3Fs of the eliromogenic polymers ù.11created for lacquer,, kprÍJc fil% ra: l' on, the a011Cel1: bra; cion of the solution is adjusted bzz) 1 * Method (B) -9
A mixture of the following formula is prepared: fluorescent pigment which can be polymerized by addition, of the following structural formula; : 0.5 part
 EMI35.2
 
 EMI35.3
 sodium aorylate; w parts methyl aoxylate part peysulfate d;

   po '; a.ssius 0Q 15 part
 EMI35.4
 
 <tb>
 <tb> water <SEP> 94.35 <SEP> parties
 <tb>
 
 EMI35.5
 o ziL 109 gone to s
 EMI35.6
 9.; A.i is carried out according to the method described 3w :. the Dé:; hodo (B) -1 0 After :. polyw $ rlaation, the, :: 61a:. '1gc: polym6: ds6 is poured into 500 parts of keton0 to release the anchored chromogenic polymer. After the filtration, the filter cake is checked with water and the pH of the resulting solution is adjusted to 9.5 to obtain an aqueous solution of the polymer at

  <Desc / Clms Page number 36>

 
 EMI36.1
 , CI ancn - :, é for lacquer.

   After: iâ.ûC i3'G. '' ..:. ",) Ù adjust the glue of the solution to. 5; J 15,] 9d e (B); :: jQ We prepare 'f.2.C mixture dq, ',) r, nu.1e ;;;: u, iVt: 1J: 1tf; addition polyNerisable azo pigment, of formula dô <next relopp4e: 2 1 - p c = ": 1. *
 EMI36.2
 
 EMI36.3
 fluorescent pigment, .nb'Lo o addition ;, de -t '? Y'3'Ai.te' w trrr't Cs'i; 3: '8iv> te: t.r "9 E part
 EMI36.4
 
 EMI36.5
 8.03. Of acrylic o '' J '^.%' 'C2.F3E4 czoi> 1 xi sobt? Tyranitrii, e Q,% 1 parts rna-.y.the. ethylene glycol: 9 2, to 2 parts Total loo parts

  <Desc / Clms Page number 37>

 Polymerization is carried out according to the
 EMI37.1
 x'ofi: c: dl e C.0c:; 'i t dar.el la. method (D) ...> '.

   After p01ymét .. s; tlon; or add 100 parts of aqueous sodium hydroxide solution to 1000 parts of acetone to the mixture to release the polymer has chotlQGèn0! ': 11'10l'é JC?; Y! L ,, ü0e}? 3.'3S filtration? the product thus obtained is washed with 30 parts. ao wox Bnsuitet '.e filter cake. is placed in water and the pH of the solution is adjusted to 10. After filtration !, the concentration of the solution is adjusted to 5%.
 EMI37.2
 



  (0) A process oonsie% a.-1t to, will introduce to the chromogen chosen directly or to the stage: ïrt.d: .. 3e a radical chosen from the reactive condensable radicals mentioned below:
 EMI37.3
 Radios structure Kethylol .., CH20H Al..1>: ylmethylol -aiI0à (aikoxymethyl) (R CnH2Yl + 1;

   J dl 1-6)
 EMI37.4
 
 <tb>
 <tb> Epoxy <SEP> -CH-CH2
 <tb> # O #
 <tb>
 
 EMI37.5
 C11lorbydrine -00-002
 EMI37.6
 
 <tb>
 <tb>
 <tb> OH <SEP> 01
 <tb> # CH2
 <tb> Ethyleneimido <SEP> CH
 <tb> -CON # 2
 <tb>
 
 EMI37.7
 N-sulfoethylenimido -CONIICH2C! {2S03H Ethylèneurde.-IlSCON4 il.2 Ethylenerea -} mCONH2
 EMI37.8
 
 <tb>
 <tb> CH2
 <tb>
 

  <Desc / Clms Page number 38>

 
 EMI38.1
 T.zl.'crh.nuxee -1 \ jEOOJ: EI,:; ::: r0SO .;

  , rL
 EMI38.2
 
 <tb>
 <tb> @
 <tb> chloride <SEP> diacid <SEP> -COOl
 <tb>
 
 EMI38.3
 
 EMI38.4
 o6tèl'lS -OEl = C = 0
 EMI38.5
 
 <tb>
 <tb> aldehyde <SEP> -CHO
 <tb>
 
 EMI38.6
 --7.sooyang.te ..neo
 EMI38.7
 or else the condensable radicals mentioned below which can react with the condensable reactive radicals above,
 EMI38.8
 
 <tb>
 <tb> Radicals <SEP> Structure
 <tb> hydroxyl <SEP> -OR
 <tb> mercapto <SEP> -SI .:
 <tb> amino <SEP> -N @ 2
 <tb> imino <SEP> -NH-
 <tb>
 
 EMI38.9
 cl3, rboxyl <a0 <Joii carboxajnide = -001ill2 "vw Obii s1.Ù: t'e..wide = SO ..., 1! FH ..- -S0hfiluréiclo ureyléne i" iàj.Ca4.rtillp -> M60i> ùicarbejnyloxy -MVIUÇ> D -

  <Desc / Clms Page number 39>

 
 EMI39.1
 1-, -;

   1s chromogen thus obtained having a radical;>; rn4, qii. '; -' 1.9 nvee one or more spaces di ';' ; 5. Ï: EC: 'F3
 EMI39.2
 'jiara's -' .. ¯t.û 7v;, '. 21 :(; - ";' t: <, 'E3' 3iZ ':: /; 3,9 species contains im l'l:?, (1 ,. ±'.: # .-:.: -. T ".: 4 ¯? Zjt9; '; or avee donkey or.



  ¯i: I: .. ¯ ¯: i - n,,> c e; =. -. '-Ij-10z: (n.-s uoildensables L $ vt $ .1 espocs c.' .0i ± 1S '1ç, rnpo: rte un a' ± '....:> 4? Eapable do' C ' C3 :: sî. '' Li10 10. (1 '.. 1, :) :; and Ù. (: ÜÍ ",; 1.Cl128: i.' With lrymli 1.iS polymbros
 EMI39.3
 eondcnsables or h cocondeneey the said = 'a; s con6 "n" sables to form the said 3.3 1Tl.liE? Qhromosune ano2ú
 EMI39.4
 little'? lacquer,
 EMI39.5
 The polymer having a radical i; t3z3L .. u 4. <form a lacquer which out reacts with the condensable chr0nO ±; Ô11.0 and which can be used without the iJioc4àô de!, -. method (C) y is J.0 é; .. a r having a condensable radical o-ù é8a.lemen a radical capable of J: orii1Cr 'ia.-t'à0 lac, by s;: em1) l ;. phenol resin,; = ± si: ne 1f; '?,:' :; ',} modified ptl.1.' tm ao: 1 ..; 1 e or 'uns:

   : 3.1! 1in resin do n! L6inc modified by mei acid (fil a (; '>. Minct rdeine 110 .'¯ üa .'...- "ius?: S. il4 j modified by aC0 or 11C amine, protulnefO resin: .1: "Ualdehyde, aid polyesters ob% enux to pr. # tJ. :: ' <i'i> ùi acid poly, ::: t # bo: il.i.que and im alcohol polyhydx'n ;; yl6,; polyamide scide or basiqm got to party? 11Ui polycayboxylic acid and a -07tJ "." '.. 11.4.iZ9: r6e1xw 6po;: y basic 1-¯atq from p,: ïch. phcl ..n4m of di-shiorhydrin or of compound '' ..4, .8'ia "- and aminos copolytaërcs obtained
 EMI39.6
 from m0l1 ') !: r.J.'08 polymt: .risabl {> 8 by addition, a; lan. "; 2;" ¯z

  <Desc / Clms Page number 40>

 
 EMI40.1
 radical capable of forming a lacquer, which Pf, U ;; be 'F' ,,? .. 3 a 'in methoeG (! L) and U3)' iî '' 't, 3' C: '.' 3,:.: 0'L a ''. '.¯ .. monomer rJ..x: ûGir47k pa = J J6, <ii. "tie> #i qv :,!. ::. ¯ 3 ....., .." F:

   , 'mt, b?' lsé in the methods (&.) and (: 8) .pz- ":, 1." =. ii.l, <#x> .. ,, eopolymers in which we have :: '1'l,;:,' od1Ü ;; in 'Â :, C3' tUl padice-L reactive functiomial and esds; 1; o1> ¯.I.Y'Jlj, è:: "'.-- :: rlS which we have also introduced ua.: carl:! .. {, a]" l''1.pa :::: ,, ;, .;at
 EMI40.2
 foraier '' lacquered me.



  The monomer yes can provide a condensable rdsm syant a raft .. 'f', é.iJN.e '.' S of foxsar a lacquer and which can be used in the p;.: Uc6dé of method (C) denotes a condor menomer :. 't., 1-; J.6 which can be condensed with the chromogen, having the ..: ¯: i. condensa ... ole above given by 13. <'7. condensation reaction and can provide s: J.m: u.1.te ;; iG:, r: m't r: 1. radical capable of closing a 1; 'n ..; :: Z '' polyr.1è '.'-: "bound,:', 1}. I2 '(? IP2d'TXB for example the acids F3 é .s.," E,.' I? .À: i ) <'... T, ll.t'ï such that s Rcide .a;:. R-.iau acid ^ .. ¯.:, U, àicid r,': '';:; ' /; gl: u.taric;} .. 10 pimelic acid, f acid <1) ac.q, 'Ue,,: ..;: \). D <.;

   at. a'3: qu acid phl; alic acid .L0.Jili.;! 14 .. 's4l.t. \ io acid t, 3 ::. 8.91'j: t, lifne> o.c1de 1iÓtrachlo!' oph- t; al iq1.1.0) aoido .ā a,. "v '.. it'Lar acid: .. l.Lmny" ": .quQ c.de ch1Qr? onifl-4fl.que, aoid- <to úichlororn21éic, acid oi t 'aconiq \;'. 0g aoide mfJlc0.15.c,) - lev itaconiquet acid aeide tetà-aliyti1-opiitali.que, .iw:

   C3.rb.Lquo and 103 analogtM3 at their acid chlorides ($) methyl esters and ethyl Gstcr8; phthalic acid anhydrides of waléic acid, itaconic acid and 1130 7.sV zs' The

  <Desc / Clms Page number 41>

 halogen acids and their esters such as mono-, di- and trichloroacetic acids and their alkyl esters
 EMI41.1
 q, es9 l t a.! 11IIloniac and alkylamines having from 1 to 18 carbon atoms; mono-, di- or trihydrosyamines; polyalkylenepolys such as: ethylenedismine, propylenediamine, tetramethylbnediamino, hexamethylenediamine, ethylenetriwain, propylenetriamine, polyethyleneimine and the like; aromatic amoebae such as:

     aniline, toluidine, xylidine, anisidine,
 EMI41.2
 phnylenedßen3ne, p - era3nophdnyltmine, benzidine, dianisidine, tolidine and the like,
In addition, among the monomers which can be used in the process according to the invention and which can be condensed or co-condensed with the condensable monomers mentioned above, one can
 EMI41.3
 mention: foiv-ald6l, .ydep trioxane, para-formald6llydep hexamethylbnetetramine,: nbthy 3.olurbe mbthy3.o..mb.sm.ze, Dréep melamine, cumudine, biguanide, dicyancdiamide; polyepoxy compounds such as: épii2alohydr.n.e 'dihalohydrin, glycidol, diglyoidylphenylethar, z diglyo3.dyJ.oxyphenylisopropa.ne,' -bisglyoidylphenyln-propane, acid 4 <4'-diglycidyloxyphenyl-n-pentanoXque and the like;

   polyhydrozqjlés compounds such as ethylene glycol, diethyleneglyool, tri6thylbnegly, "polyethylene, glycol, propylene glycolt polypropylene glycol, tbtrambthylneg3.ycolt hexamethyleneglyool, 2,2-

  <Desc / Clms Page number 42>

 
 EMI42.1
 diethy.propsn.edio3. 1,5-butonediol, 1, t ,, n.ed.o e 2, -iutyléned.o., Glyoérine, pe; rrl; a ry'i; hr: i: '; o1.v S01it! -I; JJ and the like; the isoayana'oe te3.:- q, -4. toluylene-diisooyanate, .exauethyl.ner3.isoo; eaxa:; e and the analognesa These monomers can be chosen e, 30 veme = :; -st cadensed according to the desired use.



   The following examples illustrate method (C) mentioned above.



  Method (C) -1
A mixture of the following formula is prepared: condensable fluorescent pigment of the following structural formula 1 part
 EMI42.2
 
 EMI42.3
 tetramethylolmelamine .2; J parts
 EMI42.4
 
 <tb>
 <tb> methanol <SEP> 10 <SEP> parties
 <tb> water <SEP> 49 <SEP> parties
 <tb> Total <SEP> 100 <SEP> parties
 <tb>
   After mixing at 75 ° C. for 40 minutes, the mixture is cooled to 45 ° C. Then, 1.5 parts of sulfamic acid are added to the mixture which is stirred for 20 minutes. After having rushed

  <Desc / Clms Page number 43>

 
 EMI43.1
 a PEt crystal! ' addition of a drop of. mÓlan [1'G in 100 parts of water. cold, we adjust the pI! ruélenaa at "10 by addition of 20% aqueous sodium hydroxide.

   Then? the 1 = 1ei, snge is cooled to 150 e ": 10 parts of aé.tlrnnol are added thereto. 0n obtains by filtration an aqueous solution of the anorated chromogenic polymer for laquo.
 EMI43.2
 (D) A method of producing the
 EMI43.3
 chromoeene reactive polymer anchored using Y3f: monomer or. a reactive polymer instead of a monoacr? or d9-uii polymer ant a radical capable of faithEcr Pià; <lacquer as described in methods (A) and (n), react the reactive polymer. to ohromoGf: ne t: mc: ':' thus obtained with a compound having a radical capable of forming a lacquer and of introducing the dik:. a.d.cu.

   N capable of forming a lacquer therein to form a polymer with clJ.rOr: 10 $ mG o.rwI; 'Ó PCV- \ 1.rqim, Among the radicals: reagents of m0J: 10ID0: 1: ') f; reagents which can be used in the procedure lo.1ün method (D) of:. nv cn ar3 wn can rJ1 & ntlonner 1 - #; J radioaus of condensation described in the mc-chode (C) P.'3cn'sg know? Rëthylel ss.; 4; m ;, dporjt 1 c .. # 11orhYù'rino:; lar'tn; 3, .da, ws.at; ri: 9a imidop ethylenourea, GUlfoéhylèneur6e, acid halide, ch1oro ' criaziné, ceteary aldenydo, il3ocya..1'u ...; \; (., acid amide, h.rra.u: :: 2.nQ, hydro,: ß ', mercapto, # n.no, amino, oarboJla1 carboxwaîdep sulfam1dsv ure4-do,

  <Desc / Clms Page number 44>

 
 EMI44.1
 l.1.::Óylène and oarb # nylo;: ty and analogues, Said monomers having vi i a; 11, .l ße.o:.:

   are illustrated in methods (A) and (B) above a as reactive polymerizable monomers: by addHi (J'l which can be copolymerized with 1'5S monomeric polymerisablos by addition having 1,111 radical capable of leaving a lacquer,
Among the compounds having;

   a radical capable of forming a lacquer which can be used in the process according to the invention there may be mentioned the compounds having the said radical capable of forming a lacquer and also a radical capable of reacting with a radical
 EMI44.2
 9 reactant of said polymer with anarous ohromosena, for example polyacids and 1011rs anhydridesv ll:> ¯1.0 ::; enu.: Res of acids, haloacetic acids, mmo-niac,: tmines ethyleneimine and their derivatives, condensates 1 .; "i <J.rJev, ri- obtained a. from amines and d pi: .ayohydw? ., a;:; 1.of su1: fa.ro.ic, mlfa-nilic acid, sā.cr.s.q? s4 sodium bisulfite sulfuric acid ai; the:

   C, '), lI.O [, 1. "> These will illustrate the monomers which can be used in method (0). These compounds can be chosen at will according to
 EMI44.3
 1a, the desired acti vi t6 of ro.d.L ('f> .1 reagent of pol joei% e chromogenic reagents / 3110ra and the desired application of the polymer lacquer to chromogenic anchored.,
The following examples illustrate method (D) above sloped.

  <Desc / Clms Page number 45>

 



  Method (D) -1
Diazotize 4 parts of blue hydrochloride
 EMI45.1
 of 'bri, .. I1:.' linophta1.ocys-1'line cupric to obtain a solution of diazonium salt of said product according to the process described in method (A) -1.



   A mixture of the following formula is prepared: solution of diazonium salt of cupric phthalocyanine blue such as
 EMI45.2
 qu-opienue ci-aesms 1 iv per-lifes
 EMI45.3
 
 <tb>
 <tb> amide <SEP> acrylic <SEP>: <SEP> 5 <SEP> parties
 <tb> acrylate <SEP> of <SEP> methyl <SEP> 1 <SEP> part
 <tb> water <SEP> 4 <SEP> parties
 <tb> Total <SEP> 100 <SEP> parties
 <tb>
 Polymerization is carried out according to the
 EMI45.4
 proceeds described in the method (gas 1. After polymerization, the anchored chromogenic polyniber is released again by adding 500 parts of methanol, filtered, washed with acetone and air dried.



   4 parts of the anchored chromogenic polymer powder thus obtained are dissolved in 96 parts of 5% aqueous sodium hydroxide solution to obtain a 4% aqueous solution of the anchored chromogenic polymer. The
 EMI45.5
 aqueous solution is subjected to the hydrolysis reaction at 75 µl for 6 hours and at 8000 for 3 hours.

   After hydrolysis, the pH of the solution is adjusted to 2 to release the hydrolyzed anchored chromogenic polymer. Then, the product is filtered, it is added to

  <Desc / Clms Page number 46>

 water and the pH of the solution thus obtained is adjusted to 9.5 by adding a dilute aqueous sodium hydroxide solution. After filtration, the concentration of the 10% solution is checked.
 EMI46.1
 The method (pJ = 4 parts of triaElinophthalocyanino blue hydrochloride followed by nitrogen is obtained to obtain a solution of the diazonium salt of this product according to the process described in method (A) -1.



   A mixture is then prepared having the following formula: solution of diazonium salt of cupric phthalocyanine blue such as
 EMI46.2
 that given above 90 parts ethyl acrylate 6 parts polyethylenegisrcol alkyl ethor: 0.3 part
 EMI46.3
 
 <tb>
 <tb> water <SEP>:

    <SEP> 3.7 <SEP> parties
 <tb> Total <SEP> 100 <SEP> parties
 <tb>
 
Polymerization is carried out according to the process described in Method (A) -1. After polymerization
 EMI46.4
 sation, relar; a.e the anchor chrcmogen polymer by adding 200 parts of methanel, filtered, washed with methanol and dried in the open air ,,
5 parts of the chromogen-anchored polymer powder thus obtained are dissolved in 95 parts of benzene. Then add 80 parts of solution
 EMI46.5
 of potash 5 game in 1. itx.x? o. and we hydrolyze the

  <Desc / Clms Page number 47>

 resulting solution at 75 C for 12 hours.

   After hydrolysis, the lacquer anchored chromogenic polymer is released, filtered, washed with 50 parts of ethanol and dried in the open air.



  Method (D) -3
In a polymerization vessel, we
 EMI47.1
 charge 2 parts of the aorylamide-methyl aorylate copolymer bonded to cupric phthalocyanine blue obtained in the first part of the procedure of method (D) -1, 20 parts of melanin, 53 parts of formalin, 10 parts of methanol and 30 parts of 'water. The pH of the mixture is adjusted to 7.5 by addition of 5% aqueous sodium carbonate solution and the methylolation reaction is carried out at 80 ° C. for 60 minutes.



   The reaction mixture is cooled to 45 C,
 EMI47.2
 To this was added 5 part of 0 su.l: f a.mic acid and the mixture was stirred for 20 minutes. When a crystal has precipitated by adding a drop of the mixture of reagents in 1000 parts of cold water, the pH of the mixture is adjusted to 10 by adding aqueous sodium hydroxide to a 20% solution.

   When the mixture has cooled to 15 ° C., 10 parts of methanol are added and one obtains by
 EMI47.3
 filtration an aqueous solution of the chromogen anchored lacquer polymer.
 EMI47.4
 é.: t.hoAē. (D) -4 We prepare the ir (-hydz o.i.-apl2ttrylj; a ..

  <Desc / Clms Page number 48>

 
 EMI48.1
 (methaorylauido) aniline according to the method described in method (B) -1.



   We then prepare a mixture of the following formula!
 EMI48.2
 1- 2 ^ hydroxy-i ^ naphoy. -ueth.orrldo ^
 EMI48.3
 
 <tb>
 <tb> aniline <SEP> such <SEP> that obtained <SEP> above <SEP>: <SEP> 1 <SEP> part
 <tb> methacrylate <SEP> of <SEP> glycidyl <SEP>: <SEP> 3 <SEP> parties
 <tb> acrylate <SEP> of <SEP> methyl <SEP>: <SEP> 2 <SEP> parties
 <tb>
 
 EMI48.4
 lobisisobutyronitrile 0.15 parts ethylene glycol monoethylated glycol monoacetate; 93.85 parts
 EMI48.5
 
 <tb>
 <tb> Total <SEP> 100 <SEP> parties
 <tb>
 
Polymerization is carried out according to the process described in method (B) -3. After polymerization
 EMI48.6
 At the station, 10 parts of a 20% solution of 6ùhylbneglycol Lronoethyl6ther monoaoetate in diethylam-me at 50 ° C. are added dropwise in one hour.

   After stirring at 65 ° C for 2 hours, the reaction mixture is cooled to 15 ° C. Then 10 parts of 2% aqueous E'oude are gradually added with vigorous stirring, and then diazotized p-chloro-o-toluidine to effect copulation.



   After the coupling, the polymer is released
 EMI48.7
 to chromogbne anchor by addition of 2000 partios of aqueous sodium hydroxide solution. After filtration, we dissolve
 EMI48.8
 the g0: t0D.U of filtration in dilute aqueous hydrochloric acid. After filtration, the E! Is adjusted. concentrated

  <Desc / Clms Page number 49>

 tion of the 10% solution.



   The lacquer forming agents which can be used in the process of the invention are inorganic or organic compounds which can form a lacquer from the chromogenic lacquer anchor polymer obtained by one of the methods (A), (B), (0) or (D) above. Using this compound, an appropriate compound is selected depending on the type of radical capable of forming the lacquer which is contained in the anchored chromogenic polymer.



   For carboxyl, hydroxy, phenolic, imido and sulfimido radicals, a water soluble salt which can provide one of the ions of the metals listed in group 1-b and groups 2 to 8 of the periodic table can be used. sulfo- and alkylsulfuric ester radicals, a water soluble salt such as barium chloride, lead acetate, lead nitrate, strontium chloride and the like can be used which can provide strontium ion, lead ion or the barium ion.

   In addition, for the primary -amino radical, the secondary amino radical, the tertiary amine radical and the pyridinium radical, it is possible to use tannic acid, sodium phosphate, an arsenious acid-alumina mixture, glau @ onie, terraabla, phosphotungstic acid, phosphotungstic-molybdic acid, naphthalene acid condensate

  <Desc / Clms Page number 50>

 sulfonic and formaldehyde, thiophenol, rosin soap and the like,
A process for forming lacquer from the lacquer anchored chromogen polymer using the above pentated lacforming agents,

     consists in dissolving or finely disposing the lacquer anchored chromogen polymer in water or a solvent such as alcohol, the pH of which is suitable for forming a lacquer from said. radical capable of forming a lacquer, then adding an aqueous solution or an organic solvent agent (such as alcohol) of said lac-forming agent while stirring to carry out the lac-forming reaction. Then we release the lacquer or we have it. precipitated and filtered, washed, dried, and sprayed or incorporated directly into an aqueous paste to obtain the coloring agent.



   In the lacquer-forming of the lacquer-anchored chromogen polymer by means of a lac-forming agent, known dyes, inorganic pigments, organic pigments or their intermediates, charge blanks or their intermediates can be used. dispersing agents such as surfactants and lubricants and the like, auxiliary agents such as stabilizers, ultraviolet absorbers, antioxidants and the like, or their

  <Desc / Clms Page number 51>

 intermediates, synthetic resins and analogues which are added and mixed respectively in the form of a suitable solution or of a dispersion such as suspension, emulsion,

   latex or the like to form the polymer lacquer bound to the chromogen and simultaneously to precipitate the above-mentioned substances to be added thereto. In carrying out this process, one method is to add and dissolve the water soluble intermediates, organic pigments, charge blanks, dispersing agents or stabilizers which are soluble in water or in water. 'organic solvents which can also be converted into insoluble compounds by addition of the lac-forming agent, to be mixed satisfactorily with the chromogenic lacquer anchor polymer,

   to insolubilize all the constituents by the addition of a lac-forming agent after having completely mixed and simultaneously precipitated the said polymer with anchored chromogen and the said substances, this method is superior to a method which consists in dispersing and co-precipitating the said substances which have been previously converted to be insoluble in water in order to obtain a well-mixed product of the substances to be added and the chromogen-anchored polymer. The product thus obtained therefore has several advantages in use as a coloring agent.

  <Desc / Clms Page number 52>

 



   In addition, by effecting the formation of lacquer from the lacquer anchor chromogenic polymer by the use of a lac forming agent, solutions or dispersions of dyes, organic and inorganic pigments or their intermediates, fillers or their intermediates, dispersing agents such as surfactants, lubricants and the like, auxiliary agents talc as stabilizers, ultraviolet absorbers, antioxidants and the like or their intermediates , natural and synthetic resins and the like to be added as needed, can be uniformly precipitated with the chromogen-anchored polymer lacquer,

   and therefore the product can be used effectively as a coloring agent.



   As regards the organic dyes and pigments which can be used in the process of the invention, all kinds of well-known dyes and organic pigments can be used as described in the preceding paragraph concerning the chromogen to be used for. produce the anchored chromogenic polymer.



   Intermediates of dye and organic pigments that may be mentioned are: acid azo pigments (soluble) before they are subjected to the formation of lacquer, chelate pigments before their chelation, coupling constituents or diazonium constituents of dyes. azo or azolus pigments and the like.

  <Desc / Clms Page number 53>

 



   As inorganic pigments which can be used in the process of the invention, there may be mentioned: the well-known white, colored and black mineral pigments, for example, titanium dioxide, zinc sulfate? zinc white, lithopone, iron black, iron oxide,:

  molybdate red, cadmium red, chromium yellow, cadmium yellow, cadmium lithopone, chromium oxide, ultramarine blue, cobalt blue, Prussian blue, cobalt violet, manganese violet and analogues,
As charge blanks), well-known transparent white pigments can be used, for example barium sulfate, precipitated barium sulfate, barium carbonate, chalk, Spanish white, plaster, alumina white , clay, silica, silica white, white carbon, colloidal silica, talc, asbestine, calcium silicate, magnesium carbonate, precipitated magnesium carbonate, satin white, magnesia , slaked lime, strontium white and the like.



   As charge blank intermediates, there may be mentioned: compounds which provide the charge white by addition of the aforementioned lacformating agent, for example sulfuric acid, sodium sulfate and analogues which provide barium sulphate, * barium carbonate, and * by addition of barium sulphide

  <Desc / Clms Page number 54>

 
 EMI54.1
 barium chloride, and analogues
 EMI54.2
 As agents disperse.n; s. we can me.fl.b5, we ner the agents er¯: 3.ra- o, ata s well oo-m ": 3p the .uL rv.vi bav., the stabilizers, and the analogs q1), i P ('\ 1 ".. v:' nt be used to produce paints 0, e ;;:

   c # xcraz of printing and L Y, t. 0.F agents 9v:, ,,., I 1 â C.SLL, 7: t; r; 5 resins' yTl. t..d7. t? Ci7.n .., nr More pf) .rt: lc "J.:l:i.èreI.1ent" t1g1ets surfactants aaTLpï "Ilils'? :: anionic surfactants such as slkylarylsufonates, 2,; ;: alkyl esters, colophene soap and amalogs; nonionic surfactants, such as polyethylene glycol axylethers, polyethylene glycol alkyl ethers, polyethylene glycol alkyl esters.?:,. yaol, polyethylene glycol dialkyl esters, polyethylene block copolymers and polypropyl: i: -7glycol and analogues; surfactants ... a.ctif'5 ca: t'i.onics such as allcylzmines, salts of alkylpyr1Ùiniu.'ll and analogs; surfactants: 'f,';

   no ...- ionic anionic aniphotbre such as sulfuric esters of polyethylene ethers, lyool, sulfonates of aryl ethers of po.yethyl.toneulyca., and roa1.oe8; amphoteric anionic-oationic surfactants such as alkylb4ta! nes and the like; amphoteric nonionic-cationic surfactants such as pol.yethylnelyoola.kylo.al.nas and the like; the

  <Desc / Clms Page number 55>

 amino acids and polypeptides.



   As lubricants, mention may be made of stearic acid, butyl stearate, stearic amide, palmitic amide, methylene-bis (stearamide),
 EMI55.1
 methylol-stearamide, high purity wax, medium molecular weight polyethylene, polyethylene oxide and the like,
As stabilizers for synthetic resins, in particular for polyvinyl chloride, mention may be made of metal salts of di-fatty acids, resin acid, naphthenic acid and the like, except alkali salts, for example:

   magnesium stearate, calcium stearate, stearyl calcium chloride, calcium laurate, calcium ricinoleate, calcium salts of these mixed fatty acids, stearate
 EMI55.2
 barium, stear chloride, barium y1, barium ont6a-ratct, barium laurate, barium ricinoleate and barium salts of these mixed fatty acids, strontium stearate, zinc stearate, zinc laurate,
 EMI55.3
 oadmiuM stearate, stearyl cadraium chloride, cadmium laurate, cadmium ricirlo! 6ate :,;: 1..1..1 <: cadmium yl-aryl phosphites, dibutyltin distearate. Dibutyltin maleate, dibutyltin laurate-aleate, dî-n-butyl stannate, dibonzyl stannate, polystannan-dicl. :

  r- ester, lead stearate, basic lead stearate,

  <Desc / Clms Page number 56>

 dibasic lead stearate, dibasic lead phthalate, tribasic lead maleate and the like.,
 EMI56.1
 As intermediaries of the s: uh Pi: ûw; .. s, or. can mention the compounds which 4nJn said stabilized by addition of an age> 1; training: 1 st 1a'1ue1 par. Examples include stearic acid, u8, 8.ci: /: zb ricinoleic acid and analogues and their alkali salts.



  As u's.-r.v absorbers: o3.e. one can have the derivatives of pensophenone, sd-1.cylate of 4terc3.obL t; .phnyzeg the A-benzylo .''- 2-h;. '' droxybenzoph & ione and the analogies.
 EMI56.2
 



  As ant.-o, yda..ta, there may be mentioned phenol derivatives, such as: -, 4 -dihydroxyphLnylisoprapcne, 4-isopropyl-m-cresol, '- thyl, ene-.bis- (d-thyl- -6.ter;,. Obtzty.nh; no. Et, 1 ;;; 3 analogues; amines and their derivatives such as lucid ethylene diemx.netraaet.que oromatic amines and analogues; organic compounds such as phenothiazine and the like; phosphites such as triphenyl phosphite, triphenyl phosphite,
 EMI56.3
 % rior4syl, e, dimethylphenylpb.osphite, tr.ocstyl phosphite, -1Irînc-lu-adecyl phosphite, mono-di-alkyl- or aryl-phosphites and the like.



   In addition, as natural and synthetic resins which can be added in the form of a

  <Desc / Clms Page number 57>

 suspension, emulsion, latex or the like, there may be mentioned
 EMI57.1
 polyethylene, polypropylene, polybuyl.e, polystyrene, polyvinyl chloride, po? 4.yrl ohloride, .dne, polj + 4nyl acetate, polyvinylfo, me-1. polyv.!. nylbutyral, polyacl; yl1quGs esters, polymethacrylic esters and oopolymers of the monomers constituting the said polymers, styrene-butadiene copolymers, aoxylonitrilebutadiene copolymers, aorylonitrile-styrene-butadiene copolymers, polychlorinated butadiene copolymers, polychlorinated butadiene polymers, and acrylic acid, acrylamide, IZ-m4-I.-hylolacrylamide or glyoidylmethacryla-te;

   natural rubber, polyesters "polyamides, polyethers, polyoarbonates, polyurethsneo novolacs, polytuethyluilanene, epoxy resins, amino resins, phenol resins and the like.



   The chromogenic anchor polymer 4 lakes produced in the above process have many of the characteristics mentioned below. According to the methods described in the present invention, the formation of lacquer is carried out by introducing a radical capable of forming a lacquer into the portion of the polymer bound to the chromogenic portion and by forming the lacquer from said radical to produce a lacquer. chromogen anchored polymer.

   In other words, the radicals which reduce the fastness to light, for example the radical

  <Desc / Clms Page number 58>

 sulfone, the amine radical and the like are not
 EMI58.1
 directly linked ati nucleus aromatiaup n cī, ;;. o; aooeene and consequently the fastness to the?, im; 1% 1? e ù #, product corresponds to that of the pigments eLv, i: xqv. * s <2ar oz <"mpl.T, copper phthalocyanine blue $ st 'n blue pigment having lightfastness -excellel1';:; oe Cepen: i &" lt, lightfastness of 3.s. ccifl-oea # base of olassic laolie called sky blue obtained by sulfonation of said phthalocyanine blue cl.1.ivrique using .. "1t of fuming sulfuric acid or aÉalogueg - ';:' ';

  11.1.1 'The solubilization in water and then the formation of lacquer is very low, because a sulfo radical in its
 EMI58.2
 structure is directly linked to an armna: t1que nucleus of the so-called cupric phthalocyanine structure.



   On the contrary, the polymer lacquer to
 EMI58.3
 An anchored ohromogen derived from a diazonium compound of cupric phthalocyanine and acrylic acid by formation of lacquer by means of a carboxyl group in the polymer portion using barium chloride and the like, is a chemical compound in which said polyacrylic acid of the polymer portion and cupric phthalocyanine of the chromogenic portion are directly linked by a covalent carbon-carbon bond and thus said sulfone radical is not
 EMI58.4
 not directly related to the cupric phthalocyanate portion and the lightfastness of this chromogenic polymer

  <Desc / Clms Page number 59>

 anchored is comparable to that of a copper phthalocyanine pigment.



   Most conventional water insoluble azo pigments have low am: solvent resistance. However, the chromogen-anchored polymer lakes produced according to the present invention are insoluble in solvents, because the polymer portion bound to the chromogenic portion has been made into a lacquer for insolubility in solvents, even though a chromogen. having low resistance to solvents is used as the chromogenic portion.

   These chromogenic inked polymer lakes exhibit an increase in solvent resistance over that of conventional pigments used as the chromogenic portion and are excellent coloring agents which no longer exhibit undesirable phenomena such as migration, efflorescence and the like.



   Despite the favorable properties of copper phthalocyanine pigments, such as strong coloring power, excellent heat resistance and light fastness and the like, said pigments have not been used as coloring agents in polymerization molding of polymerizable monomers with the use of a hardener (polymerization initiator) such as the casting of unsaturated polyester, methacrylate of

  <Desc / Clms Page number 60>

 methyl and analogues, since this pigment is easily broken down by oxidation due to the action of the durator,

   such as benzoyl peroxide used in the above mentioned relieves. On the contrary, the color-forming polymer lakes produced by the process described in the process of the present invention are not decomposed under the ordinary conditions of vulcanization and therefore can be used under these conditions. In search. addition of organic coloring agents tends. ; ::

  . inhibit polymerization or vulcanization of polymerized momomers and retard curing. On the contrary. The anchored chromogen-bound polymer lakes produced according to the present invention have the advantage that this vulcanization inhibition Be rarely produced and that the vulcanization time and peak temperature are essentially the same as when not in use. coloring agent.



   When using conventional pigments such as coloring agents for synthetic resins and the like, since a pigment powder cannot be sufficiently dispersed in the resins, dispersing agents such as lubricants and the like are added to improve dispersion and reduce this inconvenience.

   However, this addition is a simple mixing of a powder with another powder and by

  <Desc / Clms Page number 61>

 therefore the expected efficiency cannot be obtained., On the contrary, it is possible to obtain a two-component co-precipitated lake by the methods of the invention consisting of adding and sufficiently mixing said dispersing agents into the solution. polymers to. chromogen anchored to lacquer and then to form lacquer by addition of lac-forming agents. Those co-precipitated lakes in which the chromogen-anchored polymer lake adheres strongly to the dispersing agent added exhibit excellent dispersibility.

   In addition, for the coloring of synthetic resins by the chromogenic anchored polymers produced according to the present invention, undesirable phenomena such as gas evolution in plasticizers and the like do not occur because the chromogenic portion corresponding to the conventional pigment is chemically bonded. at. the polymer portion in the chromogen polymer lacquer anchored to form part of its structure.



   Conventional pigments are generally used as a single color, as a combination of two or more colored pigments or one. colored pigment and a black pigment and, furthermore, this color combination can be diluted by the addition of white pigment or filler white, When the said mixed pigments are used as a coloring agent for

  <Desc / Clms Page number 62>

 casting, for the production of laminates
 EMI62.1
 decorative in unsaturated polyesters, by molding or coating with a resin paste of, Ji ?? o # mx>? of polyvinyl, a separation of the mixed pigments often occurs, which is referred to as
 EMI62.2
 color separation or result,

  -has the difference in charge density 41ee.ôz-; Lque, compatibilié with su = Jpo = n.bs, colored p4j> eu. "51 or added charge blanks.
 EMI62.3
 uniform coloring for the. prod '!.' wt: o: u of products.



   It can be produced by any of the methods of. present invention as described below,
 EMI62.4
 excellent coloring substances, - ;; es which do not have the above undesirable characteristics.



   To combine two or more colors
 EMI62.5
 organic by taxample one can a method consisting of a. introducing two or more shrcNOgens into the lacquer anchored chromogenic lacquer synthesis process; a Ci,; n, e: 1.sttrn: t method for satisfactorily mixing two or more anchor chromogenic polymers in which the chromo-
 EMI62.6
 g4es are different from each other and to oo-precipitate said chromogenic polymers anchored at the same time by addition of lac-forming agents;

   or a method which consists of mixing or kneading two or

  <Desc / Clms Page number 63>

 several anchor chromogenic polymer lakes, because said lacquers have similar properties. In addition, to combine an organic pigment, inorganic pigment or filler blase, it is also possible to use
 EMI63.1
 ser a method which consists in mixing in a aa.tiefaisaote way, a dispersion of organic pisient, of igsien'c mixeral ov. of charge white with a solution of polyiar'9 chroaïogbne anchor for lacquer o's to co-harvest the substances with the addition of a lac-forming agent,
According to these methods, it is possible to co-precipitate
 EMI63.2
 la le, that of polymer to chr-o:

  No. 6Gne anchors with the above mentioned pigments and also the said polymer can be made to adhere relatively solidly on the surface or in the interstices of said pigments by the action of the polymer portion of the chromogenic polymer. anchored, so that unwanted features such as color separation as mentioned above can be avoided,
Instead of adding a charge blank which has already been insolubilized to co-precipitate said charge blank in the above-mentioned process, a solution of the intermediate compound of the charge blank is added as a soluble salt. water containing a sulfate ion, at the.

   solution of the anchored chromogen polymer and the two insoluble constituents are mixed well.

  <Desc / Clms Page number 64>

 bilised by the addition of a lac-forming agent to produce a filler white along with the
 EMI64.1
 The anchor chrome-plated stove is painted in lacquer.



  According to the above-mentioned process. is possible to ei a # Jger well and to adhere .; ' ; im = te = aen% 10 polyaërs à chrosiogen'B aD.Gré with 1 "blnc ie chrg <3 which is produced scus' Un0 forss aym> <i xir 'f.enaic'. à> e particles eittreieIn?: a <ù ine and by co:! ''. ': t the dispersibility of 2nd product is Q3id-ëra'b.'. es'? st S'perie'J.r0 to cells of the wheat? R'j of filler that has been insolubilized. In addition; the anchored chromogenic polymer which has t'S fre-n? fo =: U-é 9 #; lacquer with a white filler which does not affect its color can come into a formulation with a white pigment such as titanium dioxide and the like.



   According to the same process, the auxiliary compounds mentioned above ;, such as absorbers
 EMI64.2
 of ultraviolet, anti-oxidants and 1 "aneoge can be co-precipitated with the chromogen-anchored polymer lacquers to increase their ef't <.;

  .to Lo'Yq, u'o-J co-precipitates a stabilizer, said stabilizer can act not only as a stabilizer of the synthetic resin, for example a stabilizer for polychloride.
 EMI64.3
 vinyl, but n éieleient appoints agent di, spe # .san.bç
Anchored chromogenic polymer lakes in which a chromogenic portion is used

  <Desc / Clms Page number 65>

 fluorescent color, contain particles smaller than the product of the process of making solid solutions of conventional fluorescent pigments or dyes with preliminary condensation products obtained from melamine and formaldehyde or urea and formaldehyde,

   to harden completely and to mechanically spray the product thus obtained. In addition, a dispersing agent can be co-precipitated to improve dispersibility, thereby yielding products with highly desirable properties.



   Since the anchored chromogenic polymer lakes produced by the above-mentioned processes have been found to have desirable characteristics and advantageous properties when used to color paper, fibers, textiles, natural and synthetic leathers, articles From wood, cardboard, glass, metal sheets or plates, synthetic film wraps, molded articles, cement walls and the like, they provide products of excellent color.



   The following examples illustrate the present invention without, however, limiting its scope. In these examples, parts indicate parts by weight.



   Example
225 parts of an aqueous solution are diluted

  <Desc / Clms Page number 66>

 at 10% of the chromogenic lacquer anchor polymer
 EMI66.1
 produced by the process of method (A) -1 above mentioned, with 900 parts of ish We then add pr ':: C -.-) ss :. 30 parts of bary chloride in 20 minutes. '"A (BaSlp, 2HpO) dissolved in'! 20 parts of water at up to c ..; = p6ra31oee of 50-60 0 to 8.CfJ.E solution: The chromogenic lacquer-anchored polymer is over. When the addition is complete, stir another 30 minutes and 3000 parts of water are added to make up the mixture. precipitate the lacquer. When the precipitation is satisfactorily completed, the supernatant liquid is discarded.

   The precipitate is diluted in water and decanted three times, then filtered and washed with water. The filter cake thus obtained is added to 300 parts of water, vigorously dispersed with a mixer-homogenizer and filter. Wash with 20 parts acetone and air dry to give the chromogen-anchored polymer lake.



   Polymer lacquers with
 EMI66.2
 chromogenic anchored by application (iz r-rocéd, above to lacquer-anchored chromogenic polymers, produced by the procedure of one of the a4tfio; Inà; 'oracdeuBont "' 5 1) mentioned: (.l \,) - 2 -4t / -6? -7, phew :, -9, -100 -11, -12, -13 and -14.? (B) -1, -2, -4, -5, - #,. -71 -S, -9, -10; (C) -1, (D) -1, -2 and -3.

  <Desc / Clms Page number 67>

 



   Example 2
19.7 parts of neutral, anhydrous sodium sulfate is added to 80 parts of water, and dissolved by heating at a temperature of 50 to. 60 C.



  The resulting solution is added to 600 parts of water and 160 parts of a polymer% aqueous solution is added thereto with stirring. Anorinated chromogen for lacquer produced by the process of method (A) -1 previously mentioned. The pH of the resulting solution is adjusted to 9.5-10.0.



   Are gradually added, dropwise, over 20 minutes, 57 parts of barium chloride (Ba Cl2.2H2O) dissolved in 200: parts of water at a temperature of 50 to 60 C lady the above solution containing the chromogenic polymer for lacquer and sodium sulfate. When the addition is complete, the mixture is further stirred for 30 minutes and 6000 parts of water are added to precipitate the lacquer.



  When the precipitation has been carried out satisfactorily, the supernatant liquid is discarded. Repeat / * and washing with water, the filter cake is dried at a temperature of 70-80 ° C., then sprayed to give the co-precipitated powder of chromogen-anchored polymer lacquer and filler white,
Further chromogenic anchored polymer lakes are obtained by applying the above process to washing and decanting three times, After filtration

  <Desc / Clms Page number 68>

 chromogen anchored polymers for lacquer -produced by any of the previously mentioned methods. :

       (A.) - 2,
 EMI68.1
 -4, -5. -7, -8, -9, -10, -11, -12, -il nt -14., (B) -. 1, -2, -4e -5, -6, -7, -8e -9 and -10, (0) -1 $ (D) -1, -2 and -3.



   Example 3
A solution of 410 parts of aluminum sulphate dissolved in 1000 parts of water is mixed. by heating with a solution of 60 parts of barium chloride dissolved in 500 parts of water by heating. 6 parts of sodium carbonate are added to the suspension thus obtained, and the resulting precipitate is filtered off and washed with water. 415 parts (17 parts of solid matter) of the filling blank paste thus obtained are added to 100 parts of a solution.
 EMI68.2
 8.3 lec aqueous of the lacquer-inked chromosene polymer produced by a process described in method (A)

  -2 previously mentioned the resulting mixture is heated to 45 C and 5 parts of solution are added
 EMI68.3
 a.queuse to. rosin soap fi.



  Then 50 parts of aqueous solution are added. 20% chloride of 'ba?:' R #:!: 'Au. mixture above and the co-o rf, c't., o - ', - ,,, C' do .lCi1.1. ':; ,;, t of polyne oh :: 7oricl-> bTie anchored and white do is obtained by stirring the above solution y precipitation of the compound produced separation, filtering, washbasin

  <Desc / Clms Page number 69>

   water, drying and spraying according to the method described in 1, example 2.



   Further lacquers of anchored chromogen polymers are obtained by repeating the above process, but using the chromogen anchor polymers for lacquer produced by one of the previously mentioned methods: (A) -1, -4, -5 , -6, -7, -Si -9, -10, -11, -12, -13 and -14, (B) -1, -2, -4, -5, -6, -7, -Si -9 and -10, (C) -1, (D) -1, -2 and -3.



    Example
100 parts of a 10% aqueous solution of the lacquer anchored chromogenic polymer produced by the process described in the above-mentioned method (A) -3 are dissolved in 900 parts of water to obtain a 1-to-1 aqueous solution. %   of the product.



   15 parts of sodium tungstate, 5 parts of sodium molybdate and 3.4 parts of disodium phosphate are added to water and the resulting mixture is made up to 1000 parts by addition of water and dissolved by heating to 50. C. Then, the pH of the solution thus obtained is adjusted to. 1.8-2.0 by addition of an aqueous solution of hydrochloric acid to. 35% to obtain the phosphotungstiquemolybdic complex acid.



  The complex acid thus obtained is added dropwise to the above aqueous solution of the lacquer anchored chromogen polymer, with stirring at temperature.

  <Desc / Clms Page number 70>

 ambient. After having performed the precipitation satisfactorily, the mixture is heated at 90 ° C. for one hour.

   The anchored chromogenic polymer lake is obtained by precipitation and decantation. end of washing dilute it three times in water and decanting, then filtering, washing with water, drying and
 EMI70.1
 sprayed harsh on cooling,
Further chromogenic anchored polymer lakes are obtained by applying the above to chromogenic anchored polymers polish produced by the process described in the aforementioned method (B) -3 or (D) -4.



   Example 5
9 parts of calcium carbonate are dispersed in 310 parts of water using a mixer ... homogenizer and 90 parts of solution are added
 EMI70.2
 10% aqueous anchoring ohromogenic polymer for Inque produced by the process described in method (A) - 'i mentioned above X; ai;

  After that, 100 parts of a 10% aqueous solution of barium chloride are added dropwise into the above solution over 10 minutes and the resulting solution is stirred for 2 hours. The co-precipitated powder of lacquer of polymer with aneré chromogen and of filler white is then obtained by washing with. water, filtering, drying and spraying in the same manner as described in Example 2.

  <Desc / Clms Page number 71>

 



   Other anchored chromogenic polymer lakes are obtained by repeating the above process but using the chromo polymer, anchor gene for lacquer produced by the process described in one of the previously mentioned methods: (A) -2, - 4, -5, -6, -7, -8,
 EMI71.1
 -9. -10, -11, t ..; ^ g -1 'and -14, (B) -1, bzz r ig -5, -6, -7, -Se -9 and -10, (0) -1 , (D) -1, -2 and -5.



   Example 6
9 parts of Manchurian talc are added to 30 parts of water to form a paste which is vigorously dispersed with subsequent addition of
 EMI71.2
 270 parts of water using a mixture of homogenous mixture alone to obtain a dispersion. 90 parts of a 10% aqueous solution of the lacquer anchored chromogenic polymer produced by the method of method (A) -1 previously mentioned are added, the resulting mixture is heated to 50 to 60 C with stirring and the mixture is adjusted. pH of the mixture at 11.5. Then, 100 parts of 10% aqueous solution of barium chloride are dropwise added over 10 minutes to the above mixture and stirred at 75-80 C for 2 hours.

   Finally, the above mixture is washed with water and filtered according to the method described in Example 2.



   The filter cake thus obtained is
 EMI71.3
 added 300 parts of acetone and the xdaul.t.¯ mixture. t is stirred satisfactorily, filtered, washed with 20

  <Desc / Clms Page number 72>

 parts of acetone and air dried to force a co-precipitated powder of the polymer lacquer to anchored chromogen and filler white,
Lacquers of anchored chromogen polymers are obtained by applying the above method to chromogen anchored polymers for lacquer will produce by the methods of any of the previously mentioned methods: (A) -2, -4, -5, -6 , -7, -8, -9, -10 -11, -12, -13 and -14; (B) -1, -2, -4, -5, -6, -7, -8, -9 and -10; (0) -1; (D) -1, -2 and -3.



   Example
30 parts of an aqueous paste containing 30% barium sulfate and 0.3 part of alkyl ether are dispersed. of polyethengeglycol in 320 parts of water by means of a mixer-homogenizer and 37 parts of 10% aqueous solution of the chromogen-anchored lacquer polymer produced by the process of the above-mentioned method (A) -3 are added. and mixed well in a homogenizer. Then, to the above mixture, 370 parts of solution of the phosphotungstic-molybdic acid complex obtained in the method described in Example 4 were added dropwise to obtain a precipitate.



   After having carried out the precipitation satisfactorily, the co-precipitated powder of anchored chromogen polymer and white charge of the polymer is obtained.

  <Desc / Clms Page number 73>

 same manner as described in Example 3.



   Lacquers of chromogenic anchor polymers are obtained by repeating the above process but using the chromogen anchored polymers for lacquer produced by the process described in the aforementioned method (D) -5 or. (D) -4.



   Example
3.6 parts of an aqueous dispersing agent solution containing mainly high molecular weight carboxylic acid salts (24% solids; sold as "Demol EP") is added to 900 parts of water. A small amount of the dispersing agent solution thus obtained is added to 45 parts of rutile-type titanium dioxide to prepare a paste. The remainder of the solution of the dispersing agent is gradually added and the resulting mixture is well mixed by means of a mixer-homogenizer to obtain a dispersion of titanium dioxide.



   Then, 225 parts of a 10% aqueous solution of the lacquer-anchored ahromogen polymer produced by the process described in the aforementioned method (A) -1 are gradually added dropwise to the above dispersion with stirring. 250 parts of a 10% aqueous solution of barium chloride are added dropwise over 10 minutes

  <Desc / Clms Page number 74>

 and the resulting mixture was stirred losing 2 hours.



  By following the isolation procedure of Example 6, the co-precipitated powder of anchored chromogenic polymer lacquer and fillers white is obtained.
Further lacquers of anchored ohromogen polymers are obtained by repeating the above procedure but using the chromogenic lacquer-free polymers produced by one of the methods described in Methods
 EMI74.1
 previously mentioned: (A) -2t -4 '"5? ..6 -7, -8, -9, -10, -11, -12, -13 and -14, (B) -1, -2, -4, -5, -6, -7, -8, -9 and -10; (C) -1; (D) -1, -2 and -3.



   Example 9
640 parts of
 EMI74.2
 aqueous paste of uric phthalocyanine blue pigment (83 parts solids) in 2,700 parts dmu by means of a homogeniser and the pH of the mixture is adjusted. . dispersion at 7.5, 1000 parts of an aqueous solution prepared by adding
 EMI74.3
 170 parts of water to bzz parts of; ::: il1). Aqueous reaction to 'j0 of the polymer -,'? "YT''j. ', R,:?', S. '" Sneru for: r: '> ç1 ..: te produced by the method described' d'3 '; â method'> rL; r- "faz" "C:, f'i3lii: ''. li me..1î. titée {. A) -1 the resulting selanse is adjusted to pH and dispersed by stirring.

   B1'2.Zl:!: I.; O add drop by drop? 460 paniec de zol.:.-t:1 ';? ! -11), ev.! 3e to 20 of '3 w ^' baryrun and the mixture is stirred at 90-90 0 for 2 hours. ]: r.C ', iYIiL.'1t the process

  <Desc / Clms Page number 75>

 separation process described in Example 2, the co-precipitated powder of chromogen-anchored polymer lacquer and organic pigment is obtained.



   Further lacquers of chromogen anchored polymers are obtained by applying the above method to chromogen anchor polymers for lacquer produced by any of the methods described in the above methods.
 EMI75.1
 mentioned above (A) -2, z 5, -6, -7, 3s z -10P -11, -12, -13 and -14; (B) -1, -2, -4, -5, -6, '78 -8, -9 and -10; (C) -1, (D) -1, -2 and -3.



    Example 10
0.5 part of alkyl ether of
 EMI75.2
 polyethylene glycol to 785 parts of water to obtain an aqueous solution of a surfactant and the. solution thus obtained to 67.5 parts of tribasic lead sulphate, dispersed
 EMI75.3
 - vigorously by means of a mixer-homogenizer,
225 parts of a 10% aqueous solution of the anchored chromogen polymeric acid anchor were added.
 EMI75.4
 produced by the method described in the method I # 6c6ddUhllC1l1t mentioned (A) ... 1, and stirred at a temperature of 50-60 C. The fold of the resulting mixture is adjusted; at 11.4.



   Then 250 parts of a 10% aqueous solution of sodium chloride are added dropwise.
 EMI75.5
 ba.ryuIll and the r.lcllol1G0 obtained -4 uno teB? ... 9 of 70-8000 is heated for 2 hours with stirring. After filtration,

  <Desc / Clms Page number 76>

 
 EMI76.1
 The precipitate is washed with hot water, dried and pulverized to obtain the co-precipitated powder of anchor chromogenic polymer lacquer and stabilizer.



   Polymer lakes with
 EMI76.2
 chi-omogenic anchored by applying the, ::.: -: eded above ± 1.ï.s to chromogenic anchored polymers for lacquer produced by the processes described in any of the methods
 EMI76.3
 previously mentioned! (A) -2 $ "'4; -.5, -6 -7e -82 -9, -10, -11, -12, -13 and -14; (B) -1,," 2f -4, -5, -6, -7, -8, -9 and -10; (C) -1; (D) -1, -2 and -5.



   Example 11
24.4 parts of sodium sulfate are dissolved in 738.6 parts of water and 0.5 part of alkyl
 EMI76.4
 polyethylbneglycol ether and:) 1 ",; lj;) ttc µ7 parts of zinc stearate which is vigorously dispersed by means of a mixture ±; 'eu.r-homogé..YJ.éiseuro Ô :: r4 0ute , further and well mixed, 220 parts of a 10% aqueous solution of the chromogenic lacquer anchor polymer produced by the method described in the aforementioned method (A) -1.

   After adding 110 parts of
 EMI76.5
 20% aqueous solution of barium chloride, the precipitate is separated and purified by washing at 10OJJ. filtration, washing, drying and pu1veriss.tion according to the method described in Example 2 to obtain the. ooprecipitated powder of p.Jaymére chromogenic lacquer

  <Desc / Clms Page number 77>

 anchor and white load and stabilizer.



   Further chromogen anchored polymer lakes are obtained by repeating the above process but using the lacquer anchor ohromogen polymers produced by the methods described in one of the previously mentioned methods: (A) -2, -4 , -5, -6, -7, -8, -9, -10, -11, -12, -13 and -14; (B) -1, -2, -4, -5, -6, -7, -8, -9 and-10; (C) -1, (D) -1, -2 and -3.



     Example 12
27.7 parts of an aqueous dispersion of polyethylene (36.1% solids) is added to 372.3 parts of water, and thereto is added 100 parts of a 10% aqueous solution of the chromogen anchored polymer produced. by the process described in the previously mentioned method (A) -1, and mixed well,
After heating the mixture thus obtained to 90 ° C., 55 parts of a 20% aqueous solution of barium chloride are added and the resulting mixture is further stirred for 2 hours.

   Then we do the. separating, washing with water, filtering, washing and drying according to the method described in Example 2 to obtain the co-precipitated product of chromogen-anchored polymer lacquer and polyethylene.



   Other lacquers of polymers with

  <Desc / Clms Page number 78>

 chromogen anchored by applying the above process to lacquer anchored chromogenic polymers produced by any of the processes described in the above methods -
 EMI78.1
 mentioned; (A) -2, -4, -5./ - ?, -8? -9, -10, -11, -12, -13 and -14; (B) -1, -2, -4, -5, -6, -7, 8, -9 and -10; (0) -1; (D) -1, -2 and -3.



   Example 13
37.3 parts of copoly-
 EMI78.2
 merized vinyl chloride and vinyl diacetate (solids content 26.8%) and mixed with 362.7 parts of water, and 100 parts of
 EMI78.3
 10% aqueous solution of the anchored chromogenic polymer Their lacquer produced by the process described in the above-mentioned method (A) -1
After heating the mixture thus obtained to
 EMI78.4
 g0ai, there are 1J.j oute 55 parts of an aqueous solution of 20 μ of barium chloride and the resulting mixture is further stirred for 2 hours.

   Then, washing with water, filtration, the ', 19; binding and drying are carried out according to the method described in Example 2 for
 EMI78.5
 obtain a precipitated product of polymer lacquer at. An anchored chromogen and copolymer of chlorine and vinyl acetate.



   Further lacquers of chromogenic anchored polymers are obtained by applying the procedure of the above process to the chromogenic anchored polymers for

  <Desc / Clms Page number 79>

 lacquer produced by the process described in one of
 EMI79.1
 r:, 6th previously mentioned codes t (A) - 2, -4, -5, au -7, -8, -9, -10, -11, -12, -13 and -14; (B) -1, -2, -4, -5, -6, -7, -8, -9 and -10; (0) -1; (D) -1, -2 and -3.
 EMI79.2
 E ..: - #; nple 1.



   The pH of the aqueous solution of the anchored coupler polymer produced by the process described in the first part of the previously mentioned method (B) -1 is adjusted to 9 by adding a 10% aqueous sodium hydroxide solution and add 500 parts of acetone to it to relaunch a polymer with anchored coupler for lacquer,
The resulting mixture is filtered, the cake. filter is dissolved again in water to obtain a 10% aqueous solution of the product.

   Then, sodium sulfate and zinc stearate were dissolved and dispersed in 200 parts of the 10% aqueous solution obtained above of anchor coupler for lacquer polymer, according to the described method.
 EMI79.3
 in example 11 and l1j out0 again a 20% aqueous solution of barium chloride to obtain an anchored coupler polymer. The resulting anchored coupler polymer is washed by decantation and filtered.

   The filter paste is dispersed in 100 parts of water and an aqueous solution of alpha.
 EMI79.4
 diazotized arl11110i1n.thraquinone which is copulated zexda3 ', two

  <Desc / Clms Page number 80>

   -hours. Then filtration, washing, drying and spraying are carried out to obtain the product.
 EMI80.1
 polymer coprecipitate. chromosene aricr6, white in charge and stabilizer.
 EMI80.2
 The following examples illustrate the coloring process for various articles using lacquers.
 EMI80.3
 of anchored chromogen polymer produced by the process of the invention.



  Example of rdfërencG¯1 We prepare a mixture of the following
 EMI80.4
 ooprecipitated product of chromogenic-inked polysere lacquer and filler white obtained by the process described in
 EMI80.5
 
 <tb>
 <tb> the example <SEP> 2 <SEP> 6 <SEP> parties
 <tb> dioxide <SEP> of <SEP> titanium <SEP> of <SEP> type <SEP> rutile <SEP> 2 <SEP> parties
 <tb> resin <SEP> of <SEP> polyester <SEP> unsaturated <SEP> 5.6 <SEP> parties
 <tb> Total <SEP> 13.6 <SEP> parties
 <tb>
 The mixture is crushed using a mill
 EMI80.6
 three-cylinder to obtain an e. colore.rt for polyester resin ,.

   We. colors an impoverished polyester resin with the coloring agent a1.1 ",:,: <.. obtained, according to the uxive formulation, nte and laminated on a plywood, according to the cellulose film process.

  <Desc / Clms Page number 81>

 
 EMI81.1
 
 <tb>
 <tb> resin <SEP> of <SEP> polyester <SEP> unsaturated
 <tb>
 
 EMI81.2
 '' Epolao F82fil 100 parts
 EMI81.3
 
 <tb>
 <tb> naphthenate <SEP> of <SEP> cobalt <SEP> to <SEP> 6 <SEP>% <SEP> oe5 <SEP> part
 <tb> dimethylaniline <SEP> 0.03 <SEP> part
 <tb> agent <SEP> dye <SEP> obtained <SEP> above <SEP> 15 <SEP> parties
 <tb> catalyst <SEP> of <SEP> 'vulcanization
 <tb>
 
 EMI81.4
 (methyl ethyl ketone peroid; 60% purity;

   brand name, '' exmeoi N) 1.16 part
 EMI81.5
 
 <tb>
 <tb> Total <SEP> 116.69 <SEP> parties
 <tb>
 
The vulcanization is carried out at room temperature to obtain a beautiful decorative plate in which no color separation occurs,
Reference example 2
A co-precipitated product of anchored chromogenic polymer lacquer, filler white and stabilizer obtained by the process described in Example 11 is dry mixed in "Sholex 6000" polyethylene at a coloring concentration of 0.2 PHR. and molding the resulting colored mixture by means of an extruder, according to the following conditions to obtain a molded article,

   uniformly colored, in which the coloring agent is well dispersed.



   Extruder conditions
Temperature 200 C ¯ 0.5 0
Diameter: 30mm, L / D = 20
Screw rotation: 50 revolutions / minute

  <Desc / Clms Page number 82>

 
Preference example 3 A co-precipitated product is dry mixed
 EMI82.1
 of chromogenic polymer lacquer. . : - 18 blank of charge and stabilizer obtained by the precedent described in Example 11 in the following unplasticized polyvinyl chloride compound at an odor concentration of 2 PHR and one rolled with a two-roll rolling mill (rotation of the cylinder before:

      20 revolutions / minute, rear cylinder: 16.4 revolutions / minute the dimensions of the cylinders are 10.16 cm x 25.4 cm and the grip of the two cylinders is 0.3 mm at a temperature of 160-165 0 for 3 minutes to obtain a colored sheet of polyvinyl chloride in which the coloring agent is well dispersed.
 EMI82.2
 



  Chloride composition of -01. in; r.e nan olas..e: ée:
 EMI82.3
 
 <tb>
 <tb> chlorare <SEP> of <SEP> polyvinyl <SEP> no <SEP> plasticized
 <tb> "Kureha <SEP> S-9008 " <SEP> 80 <SEP> parties
 <tb> chloride <SEP> of <SEP> polyvinyl <SEP> no <SEP> plasticized
 <tb>
 
 EMI82.4
 "1, '' ureha HC-850L" 20 parts dibutyltin maleate 7 'parts
 EMI82.5
 
 <tb>
 <tb> acid <SEP> stearic <SEP> 1 <SEP> part
 <tb> Total <SEP> 108 <SEP> parties
 <tb>
 
 EMI82.6
 xe: ncec'çrçe Q11 prepares mi nélmgo de form! le ût.t'Yi: 1'vQ

  <Desc / Clms Page number 83>

 co-precipitated powder of anchored chromogen polymer lacquer and filler white
 EMI83.1
 obtained by the method described in
 EMI83.2
 
 <tb>
 <tb> the example <SEP> 2 <SEP> 22.5 <SEP> parties
 <tb>
 
 EMI83.3
 polY0 <J ", ..; r insa; l; urea" Epolao P-821A "100 partial:

  !
 EMI83.4
 
 <tb>
 <tb> peroxide <SEP> of <SEP> benzoyl <SEP> parties
 <tb> carbonate <SEP> of <SEP> calcium <SEP> heavy <SEP> 250 <SEP> parties
 <tb> fiber <SEP> of <SEP> glass <SEP> short <SEP> 50 <SEP> parties
 <tb> Total <SEP> 431.5 <SEP> partes
 <tb>
 
Mix well to make a paste, pour the resulting paste into an 8 x 4- x 0.5 cm3 mold
 EMI83.5
 and it is molded by heating at 100 0 for 5 minutes to obtain a colored molded article in which no
 EMI83.6
 par.t no coloring r -, - ulant of the decomposition of the coloring agent.
 EMI83.7
 A> ref6rênoel time A mixture of the following formula is prepared:

   
 EMI83.8
 co-precipitated polymer lacquer powder
 EMI83.9
 
 <tb>
 <tb> to Chromogenic <SEP> <SEP> anchored <SEP> and <SEP> of <SEP> white <SEP> of <SEP> load <SEP>
 <tb> obtained <SEP> in <SEP> on <SEP> proceeds <SEP> described <SEP> in
 <tb> the example <SEP> 2 <SEP> 20 <SEP> parties
 <tb>
 
 EMI83.10
 varnish of ni troaellu1.ose ("Nityooellulose RS 1/2", solid materials:

   t 15 80 parts
 EMI83.11
 
 <tb>
 <tb> Total <SEP> 100 <SEP> parties
 <tb>
 
 EMI83.12
 After having ground the mixture of ... '> 1s a ball mill for 20 hours, the mixture is printed with a thickness of 50 microns' on' a decorative polyester paper with a printing machine for
 EMI83.13
 Get us. deco paper:. ,, tif im)) rim6 -i b1l,) u.



  On '4re! 4i) o the elder paper. got.

  <Desc / Clms Page number 84>

 
 EMI84.1
 in a styrene monomE sc-lution ;;>;> con% -1: .inn.t j.h of benzoyl perayrde for 10 x ± =?: # teso There is no staining 01). d 'a ±; 8a ± .b31izz # = - Pn.fi Kur 1.e surface of paper decorates: hif iz; p7bc: 1, - .. ..c' !. resu.l'ha -. 't of the decomposi% ion of the colc agent: "s.s

 

Claims (1)

CLAIMS EMI85.1 t <ot, .....,. --------- .....- 1 / Un. proceeds from the preparation of a polymeric lacquer with, c .. 'I1.romogen anchored which oonsiate to combine a lacquer-forming agent with a polymer to which a chromogenic compound is bonded and which has a radical capable of reacting to form a lacquer, 2 / A process according to 1 /, in which the said lac-forming agent is a water-soluble salt of a metal selected from groups I-B and II-VIII of the periodic table of the elements. 3 / A process according to 1 or 2, in which the said polymer to which an ohromogenic compound is bonded is chosen from comprising: EMI85.2 / auWhat is linked a ch2: 'omobia / a first polymer and oresontr # it mi radical capable of closing a lacquer, the said first polymer being prepared by mixing with. least one addition polymerizable monomer, with the salt of less than one chromogenic compound and by polymerization of the resulting mixture using said diazonium salt as an initiator of the polymerization; the said diazonium salt being chosen from the following group: (a) unstabilized diazonium salts and (b) diazonium salts stabilized with a heavy metal salt, or an alkylaryl acid EMI85.3 sulfoniquet or an alkyl-sulfuric acid or an ac.; .., o N-methylamino-carbox, ylique and s1 <foniquei <Desc / Clms Page number 86> EMI86.1 im second polymer C ',' 1.1.q1..1.01 is linked mi ohrosogene ot having mi capable radical ô.e 'ßr': i .. '1.ne lac-; said second polymer 6'ant prepares ^ 2 mixing with [.'oLi :: S a monomer polym6.ris-, xble by e.6, dj; ti (us, 7e'3 av. moinz a composG cID'omogenic containing mi radical ', .. 3.5:;': ":.; 3G, wheat by addition ei in cOJ? olymer.i8 '" J..1 ;; 1' .'- H;, 1: ';;;: D.gO rée * 1.,% An'c; ? the said monomor pOl: r "J1l, erlsahla by addi-hicr. is selected from the groups: .van.s Ao Monomers nra7 in.va'.or by addition containing a radical capable of fOJ .." n1e: l ' a lacquer, the said radical being chosen from the following group; oaybosyl, a.¯ "'ICf sarbosamidOt oysno, 1 carbOl1yl haloGén1.U'0,: J1) 2fo, ester a.,:. f; e, hydroxyl pheiio- 7: ï.l..p imide, (' "0 -) ,, 0 asinc prim8i8; : secondary ayj.37t7,.,. 3.n tQrt1irB and pyridinium; 13 Polylaërisable monomers by addition. r Q3'1. L ûl 'F., ¯'i' a '. ^ 4.:. ,. ' ... reactive, the said 'yadioal being chosen from the group cc-aprenânt les.' ac? an ...: ll-iùé% hylol, .koaçymthy: l.9 sulfomëthyle, c; l; y - (;:, é71Q = .y ', hB: 1.o ±, enu.re oC1xbonyl, (-0-) 2 '' Yl .... Ci3'C9'.a'p ..,.: 3.I, '. T ;;, F, r¯t.Câ .: Y; m,' ; isocyanate, and (# -cblom- $ -.lwd1-ozy-n-popox # rj carbonyl ;. "?. Polymerated 11lono !! ioJ.">!> S, added by addition 1, containing a selected radical Hans the --- besides comprising!,:, O carbox radicals1.:W!:J.de , ur6irloc ç, 9 .mino- --x i- ... 'l.â', yT.tß p 7, ß: ai. ', ß,' t, 'p carbv2koi, ch1or, cefo, cysno, pyrz "olidonyl and hydrogen; <Desc / Clms Page number 87> EMI87.1 with the proviso, that, loI 'squ' one uses more than one monomer o.; yraa3.ab. by additions to. monk .- or b 1 one!: between them / chosen in the group.; a third polymer which is li mi chromogenic and presen4L, ant a. radical capable of forming rhyme lacquer, the said third po 'yixs being prepared by condensation of a condensable chromogenic compound oonteïlan'c in raôioal chosen in io group osmp ;, eniùit the radicals methylol, aliro; w, ethyl-1, epoxy, slilorohydrino, ethyleneimido, N-sulfoéthylèno1mido, éthylô ;; ou.ltôo, ITsv-Ifoéthylèneur6et h.7..nmo da bozrl, ch.oo.-, triazinyl, ketene, aldehyde, isocya.1'lata, or pli6nilru.ethane, or amino hydroxyl, mcroalto, amine dā, t9 carboxyl, cD.rboxll! uido "1J1.; L1.f.and.do, à; x.do, u: r3.éno or ur6th, Lne; t, wec au molnn iria COii \ IWÓ chosen tians the following group a: (a) monotabre rr'L. '' ltâ + 3'r '"a'3? presentimt a radical capable of forming a lD.q; .1G; 1 & produced in the condensation thus prepared is then oodv-m"' H- ltyieul'emel1t with a cod; j> o5É oÀoisi among the probable polymers and the monomers nLnt r35! os (b) a j7 0. ', V ": 13 :?' conclenaabl0 pyescntaat a EMI87.2 radical cape.ble to form a lacquer} EMI87.3 im fourth pOl;} rm re which is .A.3.t3 a <Desc / Clms Page number 88> EMI88.1 OE-nromogenic and exhibiting a: rz. ". D: 1.o !? capable of forming 1,; We: lac, said polymer being prepared by yeastio of a polymer to which an e:.,: Is bonded. ':,: 1. Has a reactive radical, with zî: .3. I, j': 1;: 11 'itself presented iu> 1 radical capablo de fors;!:.' a} ,; 'l, U, O; the said composition being chosen past the ms: V? JJ1'S. rolyacids anhydridos of jcs¯; .-? ea, 1'W, loZél'l'Ul ": 13 wd, e: .3.rc:; acids ha1ooJtiq.ues EUi1JJ1on, itH: .ra'1 ', amines :, e'bliylenciminei) hydrazinev aoi6e c'1 : ü.fe) n: tq1J.e sulfanilic acidj. sali eylic acid, sulfite acido c10 aodir; ù>; 9.ci <f. toric and lower condensates of czùines and dl elJih3.lohydrin; C., '3'.4.'tÉ poj.j-iùéie to which a clD.> OmJjèu0 is linked and pre- "Ge.nt; a reactive radical is, 'p.'; by Binding to the mo5.llS an addition polymerizable a.t: i: 9L> 'E3 which exhibits a + radic]. xs. - ....:. e d3 ::: :, ": 1, icaJ..é both chosen ùz * is the group 5U: 1.Vz;.: Nt s the methylolt 'radicals atlkoxyrd65lgri, e, epoxy :, eth; rlèn01m: td.o, Ns- ;; , .L:; ';;' lylene: 1.mido, ethylene-1.1.rée, N-su1.fo'hyJ.è!: 1st f1x-.J.orv.re diacid, cM.orc'-s- tri3.isinyl oeten0, G1dehyde: ± r. :: cDYf.L.> 1I? i: e9 aside, pMnylurëtha.Re :, 1:; àrdc ;; yi.o; mfiirca.:r'Î;1. 3. yîrt īT '.? a.'E3g' 3. '! Y2t 6: ü,' x'¯y '(3 c ;; J;' oo>: sx; 5,; 1 <J,. '. aez'.C; u 1.17.'eido urylbne and l1rethtme,!> T-lthyJ.oJ'3 ï1.'G.fomé-'Ghylo1. ,, ...: Oîr ', sr .. É'ie f3y ;, x Ca.a.iTI.Yii 2-.e.F; s a 'â elf0; u..ylo;: {; jr, i "'" '! :. '6i. ph: ldro.1> 'Y.-n-pZ'opoxy) -Ca.l "boL1Yl'3 uldél1.Yd, hab.:;génu,1'6 de carhonjrle, (-00) 20 isecye.:nD. t0 e, x3a.kv: r, chlorine, (oyano and ilyô.raéiône) with a compound chosen from the <Desc / Clms Page number 89> EMI89.1 group comprising; EMI89.2 (1) the diasonium salt of at least one ch: romogen compound; The resulting mixture was then prepared by using the diazoril-um sol as the polymerization initiator! the said aliaà-onirnn salt is chosen from the following group! Co.} These of the diasonium are stabilized and (b) the diazonium salts Er1; abilisést the s'-labili, smi'4 eta .: tl1; chosen by.) ij. li. 2, n following: heavy metal salts, alkyl aryl -zii ± 6nic acids, alkyl-sulfuric acids and two meta3rlamîno-carboD: y! J.o2.it-s and -suJ.:f.onic acids; and (2) at least one ahromogenic compound contained a polymeric radical. :; wheat by addition; in ooà> oi nàôi.à; 3rd en.u.ite the resulting mixture. EMI89.3 4 / A proceeds according to 3, in which the said EMI89.4 chroinogenic compound is selected from the group oomprna.nt! iia first subgroup consisting of the 3 anthraquinone compounds, thiazole, thiophèno, Itmidazole, the d.v6s of naphthaline acid ea - Kbo7, ylique, oxazole, anthraquinone compounds of the p type> .razine; alclazine, acediaiithrone, 1,4-s.phtQquinone, benzoejuinone or EOîzarî-ne, the triox: ya.ntbraC1: dnone and polyoxy-anthraquinone; a second subgroup which includes the compounds ph4u-hal-ocyan-Lee and their halogenated derivatives, the EMI89.5 quinacridone compounds, indigo compounds, azo compounds, azo coupling compounds), <Desc / Clms Page number 90> EMI90.1 azo compounds of oond.en & 'cion and their r = îôla.tex e? lacquer-forming compounds; the black of oar4> onej the black of an he ine j the dyes an sor ?? the oJ a> p o? é 5 Las composas quinoninime, las .To: npoz <Es of diphenylmdthane. triphenylEithas.e .. ch, '! ": a:;'; hà: rJ. ('t of the compounds aaiddix: c ,, asiî'e ox.sip.et tb.i (èz: 1 .: ne, c-4v, cyaninet compounds c 1: \ quixiolë.Lne compounds N.::.'t;:'.'oso and compounds E.apl.'thoquinoniqu.s; ini third subgroup which comprises , compounds derived from <iit = "i = ios.b5, lbiyne, d.istyrylberuene, ùi. thiQzole 0 osasole ;, tyiasol-3, carbazole, lislidasole;) from J.'5, mj .dazol., one, d la <; o ::, tco, Jsne, rle pyriùincs of. benzid1n dn carbosuyriJ.0, pyrasoline. of, na.phJi.i: il.im: t <- 1e, of 1, 'D) .û.a..in, of laniiiRc-t.iMK.Oi! of loxaGya.). i ... T.e9 of the. : pyi.mic1.e.n- 'ëkrones' ;; i.: ph: 3n: r.1t; J.é' \; ha.e: des g:>, 1. # ion? - polyciiclines and drifts of so-called cosiposed ac pre-utait iim 10 tip e selected p:; zx; iS, 1-ois 5i; p> :; iJ chronaoplz> 1>; J ErG asochrcsKSs. 5 / A pr: Jo; there <h according to 3! or 4. da: n, s which the monomers pol.jm iéz-iPa oles j> ai = addition containing a radical capable of forming a 1 ;;. qxiJ, s, Jn% chosen from EMI90.2 the group follow: EMI90.3 aci # r? fl.qpç; j, 'aotha.oryliqu.e ==? <otoni <iie, 1, ta, coniquf3, itcijmaric maleinuep, plkyl esters 3.es amides, ha.logÓ11,11res dt acit \ e, and their anhydrides ,, aox7.1-onït: r,: U, e, md-thaorylonî-trilep <Desc / Clms Page number 91> EMI91.1 -m4thao - Ylonit - ile, methylenesuccinonitrile, e ". c'ij-01). triIDs-1, 2-ethylenedinl trile; vinyisuli'one, sulfonated styrene, methJltyr0ne :: ..; n.3 31-zalfomethylaorjlemide, â'â.îonéthy2r; ho.ert, rlomds monoanide N-sulfon;! th.3aitaconic, diemide N , N-disu.1fornÓthyli taconique, le: The 11-sitlfo- = inometliylitacone-luîde # the mono amide Il - ,, ul-jeowninoméjhyl-itaconiatie or the diamide Tt, T3'-dirul.oam.nQmftTWl-.taccrnlcTuo ; allyl sulfate, lrydroxy-etbylacrylic sulfate, or hydroxy-ethylmethaoT sulfate, 1- EMI91.2 lic; EMI91.3 , vinyl-ph4nol or allyl-plienol; taconimide or maleimide; 1 't - aiino- <; tôJ riùne, 1.' ¯1.ylmmins; ivinylphthalimide, H-Villylox, ye.mide, g. ' : L 1.y3-.r. tiy.c, mine, N-r., 3-ethylamino-ethyl aorylate $ 3. ' c.cryïa ts de a3.; tTay.am: no-ahy.e, v ra. cho.o; y3.rta from ij-n6.th3rla.mîno- éthy2e, the methacr '. {late from TT.édhy.c.m? no-6thy: .s; 11! Tdimethyl-vJ.nyl-amine, n, 1r-dimthylttlirl0-ethyl aorylate, ââ, â; -di; â, yrn3.noti = ç.s 1, e methacrylate of T:, tT -. i: .thy3.a: r.! no-tal; is, or. 11,11-d14.tl13rlmaino-ethyl methacrylate; 1-vîriyl-T) yrldinci and 2-vinJ'l..5 ... methylpyridine. EMI91.4 6 / A method according to one of the claims <Desc / Clms Page number 92> EMI92.1 5 to 5 in which the addition polymerizable monomer EMI92.2 containing a reactive radical is chosen from the group comprising: EMI92.3 the compounds: f-methylc10D: .'¯o av-y2s, sulfomethyloi.6s, and aminom6thylolî> s of 1 f aC: r "Jlauide, methacZ" Jl8.mi (crotonaside, les;, WJ10- '9t itaconic diamides, the mono and dl-asiëes, x.1 .t - '.' 3 Lliv.G'F ".y the mono- and di-smoking aids.: 'ic: 3, the .Ji.nj; .l -àr <ôe, or 4, 6-d5- maino-2-vinyi- s-triaJi: ùe; gl.yoidyl acrylate, 6thD.crylate, 51yoidylee cro-v-onatcAe lyoiâ lep itaconates from mono- 'and di .. (Clyc5.dyle), the mal6a-I.-en de': .10no- and diG; .yc.c, yï e) p fusiaratas from mono- or to: 1-- 3,3Tcidyle). I - ', .. ^' â-ß'L: i.CL - é t2'r, 1 a ....- r {1 ", + p. of .oh.o: ¯. S-: y'roriy-n-rGny'ea le là ô% l1Gcgrl aÉ ed QX - Chlm o to - .hyc;.>: ¯r.pr, .ag the CI'otona:!; E of '6- ohloro ... -: 1.Ydroxy-n -:?: '0! :). Jle, 11 i mono- or taconate. â ..- (('() -chlor- -hc?: oyr-: ony3.e, .o Naleate from mono- or c - c .o, oÂG-: ü-a; d: ron ... p ".ov2e: La: fli'eu '," ti'ti $ de mono- or di- (' t -0h2.:. ';,) - P -'lJd!' oY..j "= npropyla, ° .e .eHoioxo- -h; dro:, - ¯ .. = 'o; - .. ß; Grl-thar; 1 t acrolein, la ::' ch: olein, crotonaldehyde, chlorares aC171i ot :: iE.'f 'til.ì'ß.7.i ?, 1' enho, d rid e it.con que, 1 i en \ 1yd :( "'.. l .: .'1; 6] 'read 1 10 -NrîilYI7 isocyanate or propenyl-isocy # lD - <Desc / Clms Page number 93> 7 / A method according to one of claims 3 to 6 wherein the polymerizable radical by addition of said chromogen containing an addition polymerizable radical is selected from the following group! EMI93.1 <Desc / Clms Page number 94> EMI94.1 EMI94.2 or R represents a hydrogen atom or. 1) .11 alkyl group. 8 / A process according to 1'unic of claims if to 7 wherein said condensed polymer> 1e presentapt EMI94.3 a. radical capable of forming a lacquer is chosen from EMI94.4 the following group phe resins: no1.1.q>; es, phenotic resins codified by an acid or a JJi11 and urea resins modified by an acid or an, 91: r: i..ne, resins! n4laniins modified by an acid or an amine ;, guanamine resins coded by an ac-4-de or an amine, proteinformol resins., polyesters of acid polyamides or ch. 3. (llte.'a basic epoxy roots or capclY0res obtained 9ar cock 01YLi, - '-J * ,. o: i of' "'s6'.? '! A' '. 1ti33.V''Y t ,; , ii.'s: ß: i. "aâû'rrâ by addition EMI94.5 presenting a radical, capable of forcing a lacquer, the EMI94.6 said stant monomers chosen from: .The group comprising; acrylic acids: ;;,; tl1-acryliqua, oroto-. nique, '.'têï,.' 07.'L: .GLl.d metric,: t'tUU: ;;. :: - iq1.l0, 3.es. ;; alkyl stars, amides, hr: l.o6érn.l. "these acids, and their anhydrides acrylollitr: U'3, ,, i6-hacx7l-onitrile, 6 -mé-tns.cxyon. tr.le? e m6th: .j'1nelJuccinonitrile, and ci s- or tr, n - 9, 2.-zh;:. = y: vsa.:! e vinyisulfone, 1s sulfonated styrene, methylstyr0ue sulfonated, N-aufometylacryl # nide, N, -au: Lfom6thylmethaexylamide, Nonûasiids 1.1-Ltilòm6thyl- <Desc / Clms Page number 95> EMI95.1 i'tÓ '{! oni0.' "e, r, n-diS1.'tlfomethyli-lïaoonic diamide, 11- ::: ulfoaminoIT10'thyl-acr'Jlar.l.ide, Zi.v2focr.iinondthyl- . 'f;. :.: ork: ..:. cc, nionoanide l! '-: 3ulfoaminomÓthyl-itaconiquo or l;.: a: l::, Ißl.d.sul-'oçur..9.nomlyl.it, conie, us; allyl sulfate, sodium hydroxyethyl z-yl, or hydrQ-.vhylmhs sulfate, el3l.cue; vinyl-phenol or. e.1.1-phno; itaconimide or m7.c.m.ide; 1 t amino-dtyrene, al.iyl-amine; Ilvinylphthalimide, If - Tinyloxya.'11ide, 1 t allyl-methylamine, the aoxylate of: - ;: f.;,. 3nothyZs, lr a.oT; llat9 of J thy.ino-C L- iy3., 3 le 1; Jehac1 "ylato of I-methyll3.!: lino ... ethyl, horvrl4 a from d: - h; lT: Lno.-61h.e; la N, 1.1drth.- -t-nyl. ins, 1'e, c;, te of âT, N-diradyl.o, ta: l.no ethyl, acrylate at = .N, 11-4iethàrlnJàin? -dtliylo, methacrylate of n , H-dir.Gthyl! 3..mino-cit} yla, or methac: r'Jlllt (1 of n, II-di6 - ;; hylaraino ... ethyl; or N-vinyl-: py: r.1Jin0 and 2-vinyl'-3'methylpyridiue, with polymers: riso.b18EJ by addition exhibiting a reactive radical, the so-called 6tro: t raonombras chosen dens EMI95.2 the group comprising: EMI95.3 the compounds N-mt; thylolés, alJroir; ix4 tiiyién, S1.11for :: HHhylolés and illninomúthyloléa of: 1. ' ox, F. .:? - N ?, the â.itxe.o :, 13.re, the orotonajaide, the mono- and di-ajaidea v1 .cor.3, cua, the mono- and di-amides Lial, îqueu, the mono - <Desc / Clms Page number 96> EMI96.1 and fumaric di-amidea,: vinyl urea or 4,6'diamino-2-vinyl-s-triazine glycidyl acrylate: bzz: r.'ûth9.f,): rJ} 8; ( ;; glycidyl, gl: yc '! "(! .. 1":; 1 lev itaconates of mono- and di-7.'cidJ.o) oal13.te5 of 1110''1 (, - and di-l4rc '.'Je ;, mono- fumarates, ..'..--;,.: ::. i.c'; c; 'ia 2yJ.-zMJ-: lc.'Y7 ¯ ", hor; '-'ob2.oro - "ydrû.!. y-npropyl aciylate, z -chloro- [b-hjfàro; 13-npropyl m {Stsyex, i, tc; 13-npropyl, -chloro- crotonate 21ych.> Oxy-n-: p :::: 'oprlf11 1 t 1 ts.co # te de mono- or # el1- (t -chlo ::. C- f- -hyclroxy-nSJ: Citl.6. U le ma.1Ó :: d: e of nono- or di- (µ.: <# 1.iīçro-) - Ï1..ydro: yn-pro,; nrle, the .zra:, t of round <- or d1- (... ; n2cr o- -, ro:, - n -? xo's.e ld l (-.hlor <) .. b, ydro7.Y-rbpropyl-a11Yl-ethr; .1. q wC'S.s., '': ..: ir meth :::: 0Z "- ':. 1l.n'3t croton-' 8..ld6hrde, ch.::'ornrel3 acrylic;;. ; .µ i;: a *, czv-jl 1? = 1e, the anhydride e:.: acon3, ame l 'a! L'I-: 1ydr. eL:,::.' .: .uos: L3 3 ': d ny' iSOCY811s: te or: Le .t'o..wP3. "" 'J.OiG? Ymtâep 9 / A proceeds according to' a ,,,:, w dss claims zw 8, in which the said monomer .oW¯i3o.h3.e having a radical, capable of forming a lacquer is chosen EMI96.2 in the next group; EMI96.3 a first sub-gw coiipe which comprises the acid rW2'thylglv.ttl: riq, ue, the acids c;.: a: cE; e, adipic, p: l.mÓli (lue, sebaciqrio, aû: i, the phthalic, 3 co3 ta3..ic <Desc / Clms Page number 97> EMI97.1 terephthal.ic, tetrachlorophthalic, maleic, fumaric, chloromaleic, dichloromal6ic, aracqniques mesa 00nique itaconic, tetrshydrophthalic, arbic or the chlorides and methyl and ethyl esters of these acids; the anhydrides of phthalic acid, maleic acid and itaconic acid; mono-, di- acids EMI97.2 and tri-chlo-, aetics and their allyl esters! a second subgroup which includes ammonia or alkylamines having from 1 to 18 carbon atoms, mono-, di- or tri-alcohol amines; the EMI97.3 polyalkylene polyaTines or aromatic amines. 10 / A process according to 9 in which a monomer of the first subgroup of condensable monomers is first reacted with a compound selected from EMI97.4 group comprising! r. '?' 'vlya..0.lli C: fa, le, métliylolmélami-ne, urea, mel # nine, suanidine, biguanide, dicyandiamide, epihalaz4cxi ne, la dihalohydrin, glyoidol, diglycidylpiiënylether, 4 '- di: yeidy-3.oy-phenyl-uopxapane, le,' is lycidy'lphny7.-n. propane, acid., q, '- d.; 3.ya: Ldtoxy-pheny.-x-pentan.o.aue, 1. ethyl: rze; .ycal, diethyleneglyool, triethyleneglycol, polyethyleneViyoo., propylene glycol, polypropylene glycol, -: etx'crr.4thy3neZyooi, hexamethyleneelycol, 2,3-d-iëly.propaned.ioi, le 1,3buttnediol, 1, -bu ûylenediol, 2,3-butylenediol, glycerin, pentaerythritol, or sorbitol. <Desc / Clms Page number 98> 11 / A process according to 9 in which a monomer from the second group of condensable monomers is first reacted with a compound selected from EMI98.1 group comprising: formaldehyde, 1, e: v. a; ane para.formaldehyde, hexamethylen .:; - I; Jtrt? .. n11..ne, 10. methylurea, methylolmelamine; urea ;, .éâk.r: ae guanidine, biguanide, diayanli-amidee 1? êDîhelohydrin, dihalohydrin, lyoi.olr e diglycidyl- 'phenylether, 4,4'-dijlycidyloçi-phànyls.sopropàlie , the, \) - biS-ClycidYl1hényl-n-pl'o: nm0,! 2acid 4.4. d: - .yo: .dyl, ophézy2-n-p ancicuea 1 tclylënediisocyanate or 1'heLamethylvnecl: .socyanacr i2j A procedure according to 4. dan ..- in which the chromogen is chosen from the second -m ,,, 2c-group, 13 / A process according to 4 in which the chromogen is chosen from the third subgroup. 14 / A process according to 3, to prepare the EMI98.2 first polymer to which is bonded a chromogenic e chromogen used eta. "1 ,; tria11l'i: r (! - ;. b:.; copper halccyanina, 1 and the polymeric monomer9¯: a.: r: .e P!? 'R addition having a radical capable of forming a lacquer, being acrylic acid. EMI98.3 15 / An anchored ohromogenic polymer lacquer prepared by a process according to 1, 16 / An anchored ohromogenic polymeric lacquer prepared by a process according to 12, <Desc / Clms Page number 99> 17 / A polymer lacquer with anchored chromogen prepared by a process according to 13. 18 / An anchored chromogenic polymeric lacquer prepared by a process according to 14. 19 / An anchored ohromogen polymer lacquer prepared by a process according to any one of the preceding claims. 20 / A method of coloring articles which comprises the treatment of these articles with an anorea chromogonal 4 polymer lacquer, prepared by the method according to 1.