NO750662L - - Google Patents
Info
- Publication number
- NO750662L NO750662L NO750662A NO750662A NO750662L NO 750662 L NO750662 L NO 750662L NO 750662 A NO750662 A NO 750662A NO 750662 A NO750662 A NO 750662A NO 750662 L NO750662 L NO 750662L
- Authority
- NO
- Norway
- Prior art keywords
- water
- dye
- bleeding
- paper
- dyes
- Prior art date
Links
- 239000000975 dye Substances 0.000 claims description 55
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 2
- 230000003381 solubilizing effect Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 230000000740 bleeding effect Effects 0.000 description 25
- 239000000243 solution Substances 0.000 description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 210000001519 tissue Anatomy 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 12
- 239000000443 aerosol Substances 0.000 description 11
- 239000008267 milk Substances 0.000 description 11
- 210000004080 milk Anatomy 0.000 description 11
- 235000013336 milk Nutrition 0.000 description 11
- 229960000583 acetic acid Drugs 0.000 description 9
- RCWWQKJNJXOMPC-UHFFFAOYSA-N NC[Cu](CN)(CN)CN Chemical compound NC[Cu](CN)(CN)CN RCWWQKJNJXOMPC-UHFFFAOYSA-N 0.000 description 8
- 238000004043 dyeing Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 229940037003 alum Drugs 0.000 description 3
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 2
- MHOFGBJTSNWTDT-UHFFFAOYSA-M 2-[n-ethyl-4-[(6-methoxy-3-methyl-1,3-benzothiazol-3-ium-2-yl)diazenyl]anilino]ethanol;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC(N(CCO)CC)=CC=C1N=NC1=[N+](C)C2=CC=C(OC)C=C2S1 MHOFGBJTSNWTDT-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000001007 phthalocyanine dye Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000567769 Isurus oxyrinchus Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 159000000021 acetate salts Chemical group 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000013334 alcoholic beverage Nutrition 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HKYGSMOFSFOEIP-UHFFFAOYSA-N dichloro(dichloromethoxy)methane Chemical compound ClC(Cl)OC(Cl)Cl HKYGSMOFSFOEIP-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- -1 halide anion Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 101150038787 mak gene Proteins 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000008149 soap solution Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000010981 turquoise Substances 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/32—Cationic phthalocyanine dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/12—Obtaining compounds having alkyl radicals, or alkyl radicals substituted by hetero atoms, bound to the phthalocyanine skeleton
- C09B47/16—Obtaining compounds having alkyl radicals, or alkyl radicals substituted by hetero atoms, bound to the phthalocyanine skeleton having alkyl radicals substituted by nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Coloring (AREA)
Description
En rekke farvestoffer er basert på fthalocyaninmolekyletA number of dyes are based on the phthalocyanine molecule
som er meget stabilt og gir hoy farvekraft. Fthalocyaninfarvestoffer selges i både anionaktiv og kationaktiv form, som vannopploselige farvestoffer, pigmenter og som overfor fibre reaktive farvestoffer. En del av disse vannopploselige farvestoffer er umetalliserte mens andre er metalliserte og inneholder kobber, kobolt, nikkel eller andre metaller0De mest kjente og utstrakt anvendte av disse vannopploselige farvestoffer er basert på kobberfthalocyanin.. which is very stable and gives high color power. Phthalocyanine dyes are sold in both anion-active and cation-active forms, as water-soluble dyes, pigments and as fiber-reactive dyes. Some of these water-soluble dyes are unmetallized, while others are metallized and contain copper, cobalt, nickel or other metals. The most well-known and widely used of these water-soluble dyes are based on copper phthalocyanine.
Kobberfthalocyanin er utstrakt kjent som et nyttig farvestoff for papir, i det minste når det er disubstituert med aminomethyl-grupper0Kobberfthalocyaninets utmerkede lysbestandighet og hoye farvekraft gjor at det inntar en særstilling blant pigmenter, og fra det ble oppdaget har farvestoffprodusenter anstrengt seg sterkt for å komme frem til en opplost form av kobberfthalocyanin som er egnet for farving og trykking av tekstiler. Det ble funnet at en sulfonering forer til et opploselig produkt med utmerket farvekraft og lysekthet, men produktet er ikke farveekte ved vannbe-handlinger, spesielt ved ..vasking. Dessuten er en rekke farvestoffer av denne type når de anvendes for å farve absorberende papir, som papir for papirhåndklær eller papirlommetorklær, til-boyelige til å utsondres eller blo når papiret kommer i kontakt med slike materialer som melk, konsistensfett eller husholdnings-rensemidler. Da et slikt papir må være sterkt absorberende for at det skal kunne anvendes for sitt formål, kan bare en meget liten mengde av eller intet alun og lim tilfores papiret. Ved farving av f.eks. såkalt "tissue" anvendes intet alun eller lim. Copper phthalocyanine is widely known as a useful dye for paper, at least when disubstituted with aminomethyl groups0 Copper phthalocyanine's excellent lightfastness and high coloring power make it stand out among pigments, and since its discovery, dye manufacturers have made great efforts to develop to a dissolved form of copper phthalocyanine suitable for dyeing and printing textiles. It was found that a sulphonation leads to a soluble product with excellent coloring power and light fastness, but the product is not colourfast in water treatments, especially in washing. Moreover, a number of dyes of this type when used to color absorbent paper, such as paper towel or pocket tissue, are prone to exuding or bleeding when the paper comes into contact with such materials as milk, grease or household cleaners. As such a paper must be highly absorbent in order for it to be used for its intended purpose, only a very small amount or no alum and glue can be added to the paper. When dyeing e.g. so-called "tissue", no alum or glue is used.
Selv om pulverformige farvestoffer i en rekke år er blitt anvendt for farving av papir, anvendes nu i utstrakt grad farve-stoffopplbsninger inneholdende minst 15$, fortrinnsvis minst 25$, aktivt farvestoff. Slike oppløsninger er svært gunstige for farving av papir når oppnåelsen av en korrekt farvetonedupliser-ing er vanskelig og når "stoving" av torre farvestoffer kan ut-gjore et problem. Dessverre kan et farvestoff med den hoye opp-Ibselighet som er onsket for farving av papir, også være utsatt for bloding fra det erholdte farvede papir, spesielt dersom intet alun eller lim anvendes. Although powdered dyes have been used for coloring paper for a number of years, dye solutions containing at least 15%, preferably at least 25%, of active dye are now widely used. Such solutions are very favorable for dyeing paper when the achievement of a correct color tone duplication is difficult and when "stowing" of dry dyes can be a problem. Unfortunately, a dye with the high fastness desired for dyeing paper may also be subject to bleeding from the resulting dyed paper, especially if no alum or glue is used.
Det har nu vist seg at en gruppe fthalocyaninfarvestoffer er sterkt opploselige i vann og samtidig har liten tilbøyelighet til å utlutes fra med farvestoffene farvet papir. It has now been shown that a group of phthalocyanine dyes are highly soluble in water and at the same time have little tendency to leach from paper dyed with the dyes.
Oppfinnelsen angår således et farvestoff med formelenThe invention thus relates to a dye with the formula
hvori Pc betyr f thalocyanin, n betyr 3 eller >+, R^betyr H og/ eller en hydroxyalkylgruppe med 2- h carbonatomer, men betyr for minst 25$'s vedkommende en hydroxyalkylgruppe med 2- h carbonatomer, R2betyr H, en alkylgruppe med 1-*+ carbnnatomer eller en hydroxyalkylgruppe med 2-!+ carbonatomer, og X betyr et opploseliggjorende anion. in which Pc means fthalocyanine, n means 3 or >+, R^ means H and/or a hydroxyalkyl group with 2-h carbon atoms, but means for at least 25$'s a hydroxyalkyl group with 2-h carbon atoms, R2 means H, an alkyl group with 1-*+ carbon atoms or a hydroxyalkyl group with 2-!+ carbon atoms, and X means a solubilizing anion.
Disse farvestoffer er særpregede ved at de er blodnings-resistente overfor vann, melk, konsistensfett og vanlige hus-holdningsrensemidler og -vaskemidler, dvs. at disse materialer ikke opploser farven i det farvede papir under normale bruks-betingelser. Denne egenskap kunne ikke forutsies ut fra tek-nikkens stand. Det er hoyst overraskende at farvestoffene ifolge oppfinnelsen på den ene side har den onskede opploselighet i vann og på den annen side er blodningsfaste farvestoffer for absorberende papir. These dyes are distinctive in that they are bleeding-resistant to water, milk, grease and common household cleaners and detergents, i.e. these materials do not dissolve the color in the colored paper under normal conditions of use. This property could not be predicted based on the state of the art. It is highly surprising that the dyes according to the invention on the one hand have the desired solubility in water and on the other hand are bleeding-resistant dyes for absorbent paper.
Farvestoffene ifolge oppfinnelsen kan fremstilles ved hjelp av en velkjent rekkefolge av omsetninger. Ifolge en utforelses-form begynner rekkefolgen med C.I. pigmentblått 1^, 7^-160, monastralblått eller kobberfthalocyanin med folgende struktur-formel The dyes according to the invention can be produced using a well-known sequence of conversions. According to one embodiment, the sequence begins with C.I. pigment blue 1^, 7^-160, monastral blue or copper phthalocyanine with the following structural formula
Når kobberfthalocyanin oppvarmes med aluminiumklorid og en terti-ær base, som triethylamin, fås en "smelte" hvori kobberfthalo-cyaninet foreligger opplost og vil reagere med diklordimethyl-ether under dannelse av klormethylderivater„ På denne måte kan 3,<1>* eller flere klormethylgrupper innfores i de aromatiske ringer i fthalocyaninmolekylet: When copper phthalocyanine is heated with aluminum chloride and a tertiary base, such as triethylamine, a "melt" is obtained in which the copper phthalocyanine is dissolved and will react with dichlorodimethyl ether to form chloromethyl derivatives. In this way, 3,<1>* or more Chloromethyl groups are introduced into the aromatic rings of the phthalocyanine molecule:
Dette klormethylderivat kan omsettes med ammoniakk eller et amin eller en blanding av aminer for fremstilling av et amino-methylfthalocyanin som er opploselig i vandig syre, f.eks.: This chloromethyl derivative can be reacted with ammonia or an amine or a mixture of amines to produce an amino-methylphthalocyanine which is soluble in aqueous acid, e.g.:
Dette produkt kan behandles med et alkylenoxyd, f.eks. med propylenoxyd, for dannelse av som med saltsyre gir This product can be treated with an alkylene oxide, e.g. with propylene oxide, for the formation of which with hydrochloric acid gives
Den sist angitte formel representerer et farvestoff ifolge oppfinnelsen som er velegnet for anvendelse i vandige opplosninger0 The last given formula represents a dye according to the invention which is suitable for use in aqueous solutions0
Ifolge en annen fremgangsmåte ved fremstilling av farvestoffer av denne type og hvor bisklormethylether, som er en sterkt kreftfrembringende forbindelse, unngås, blandes kobberfthalocyanin med fosforpsntoxyd, fthalimid og paraformaldehyd i 100$ svovelsyre. Efter oppvarming ved moderat temperatur fores reaksjonsmassen ned i vann, og det faste produkt isoleres ved filtrering. Den fuktige kake oppvarmes med natriumhydroxyd, surgjores derefter med saltsyre og oppvarmes på nycDen erholdte opplosning gjores til slutt alkalisk med natriumhydroxyd, og det utfelte faste produkt oppsamles på et filter og vaskes med vannDProduktet består hovedsakelig av tetrakis (aminomethyl)-kobberfthalocyanin. Det kan blandes med et alkylenoxyd, som butylenoxyd, under sure betingelser under erholdelse av en addisjonsfor-bindelse av typen According to another method in the production of dyes of this type and where bischloromethyl ether, which is a strongly carcinogenic compound, is avoided, copper phthalocyanine is mixed with phosphorus psntoxyde, phthalimide and paraformaldehyde in 100% sulfuric acid. After heating at a moderate temperature, the reaction mass is fed into water, and the solid product is isolated by filtration. The moist cake is heated with sodium hydroxide, then acidified with hydrochloric acid and heated again. The resulting solution is finally made alkaline with sodium hydroxide, and the precipitated solid product is collected on a filter and washed with water. The product consists mainly of tetrakis (aminomethyl)-copper phthalocyanine. It can be mixed with an alkylene oxide, such as butylene oxide, under acidic conditions to give an addition compound of the type
Blandinger av alkylenoxyder kan anvendes for å erholde produkter med maksimal anvendbarhet. Mixtures of alkylene oxides can be used to obtain products with maximum applicability.
Farvestoffene fremstilles bekvemt og skipes med en konsentrasjon på 30- 35% (med farvestoffets saltform). Når vann for-dampes fra disse opplosninger, kan en konsentrasjon på 50% > eller derover oppnås uten at farvestoff fjernes fra oppløsningen. Viskositeten oker med tiltagende konsentrasjon, men opplesningene kan fremdeles helles og lett håndteres når de har en konsentrasjon på 50%. The dyes are conveniently produced and shipped with a concentration of 30-35% (with the dye's salt form). When water is evaporated from these solutions, a concentration of 50% > or more can be achieved without dye being removed from the solution. The viscosity increases with increasing concentration, but the readings can still be poured and easily handled when they have a concentration of 50%.
Ved en annen fremgangsmåte for fremstilling av farvestoffer ifolge oppfinnelsen kan et alkoxylert produkt,- som In another method for the production of dyes according to the invention, an alkylated product, such as
behandles med et alkyleringsmiddel, som et alkylhalogenid eller dimethyl- (eller diethyl-) sulfat, i en tilstrekkelig mengde til å gi et farvestoffsalt ifolge oppfinnelsen med den gjennomsnitt-lige sammensetning treated with an alkylating agent, such as an alkyl halide or dimethyl (or diethyl) sulfate, in a sufficient amount to give a dye salt according to the invention with the average composition
, hvori Y er et halogenidanion. , where Y is a halide anion.
På lignende måte fremstilte produkter som ikke har hydrogen som. en av substituentene R2og R^i formelen Similarly produced products that do not have hydrogen as. one of the substituents R 2 and R 4 in the formula
, har for dårlig blodningsfasthet ved farving av tissue. , has too poor bleeding resistance when dyeing tissue.
På den annen side har f arvestoff et CuPc (CHgNH^Cl )1+god blodningsfasthet, men det har ikke en tilstrekkelig opploselighet i vann til at det kan anvendes for farving av papir. On the other hand, genetic material has a CuPc (CHgNH^Cl )1+ good bleeding fastness, but it does not have a sufficient solubility in water for it to be used for dyeing paper.
Det bor bemerkes at selv om de ovenstående formler antyder en struktur hvori kobberfthalocyanin har fire adderte substi-tuentgrupper, er det meget sannsynlig at en del trisubstituerte molekyler også er tilstedeeIt should be noted that although the above formulas suggest a structure in which copper phthalocyanine has four added substituent groups, it is very likely that some trisubstituted molecules are also present
I formelenIn the formula
kan R bety en hydroxyalkylgruppe med 2-hcarbonatomer eller H, can R mean a hydroxyalkyl group with 2-h carbon atoms or H,
men den må for minst 25$'s vedkommende bety en hydroxyalkylgruppe, og R2kan bety H, en alkylgruppe med l-<>>+ carbonatomer eller en hydroxyalkylgruppe med 2- h carbonatomer. Alle derivater ifolge denne definisjon har den nodvendige opploselighet og gir et utmerket overfor blodning motstandsdyktig farvet papir. Farvestoff-egenskapene forandrer seg ikke merkbart når alkylgruppenes eller hydroxyalkylgruppenes storrelse tiltar til opp til h carbonatomer. Hvis antallet av carbonatomer' okes ytterligere, avtar opploselig-heten gradvis. but it must mean, for at least 25$'s, a hydroxyalkyl group, and R2 can mean H, an alkyl group with 1-<>>+ carbon atoms or a hydroxyalkyl group with 2- h carbon atoms. All derivatives according to this definition have the necessary solubility and provide an excellent bleed-resistant colored paper. The dye properties do not change noticeably when the size of the alkyl groups or hydroxyalkyl groups increases to up to h carbon atoms. If the number of carbon atoms is further increased, the solubility gradually decreases.
For å undersoke de foreliggende farvestoffers motstandsdyktighet overfor blodning ble den folgende undersøkelsesmetode anvendt for farvede tissuehåndklær: En 2,5<;>+ x 15, 2h cm strimmel skjæres ut av et på forhånd fremstilt tissuehåndkle og brettes til et 2,5^-x 2,5<!>+ cm kvadrat. Dette dyppes ned i en proveopplosning, av hvilke et antall er angitt nedenfor, og anbringes derefter på tre trekkpapir som er blitt mettet med den samme opplosning. To ytterligere mettede trekkpapir anbringes på toppen av den farvede tissueprbve slik at det dannes et laminat.(Av tre mettede trekkpapir i bunnen, et mettet tissuehåndkle i midten og to mettede trekkpapir på toppen). In order to investigate the resistance of the present dyes to bleeding, the following test method was used for dyed tissue towels: A 2.5<;>+ x 15.2h cm strip is cut out of a previously prepared tissue towel and folded into a 2.5^-x 2.5<!>+ cm square. This is dipped into a sample solution, a number of which are given below, and then placed on three tracing papers which have been saturated with the same solution. Two further saturated blotting papers are placed on top of the colored tissue sample so that a laminate is formed. (Of three saturated blotting papers at the bottom, a saturated tissue towel in the middle and two saturated blotting papers on top).
De fem trekkpapir anbringes på en hydraulisk presse, og et trykk på 3, 5 kp/cm p påfores i 1 minutt og blir derefter opphevet. Trekkpapirene fjernes, og de to over ste og de to nederste trekkpapir fjernes slik at det blir igjen ett trekkpapir og proven. Proven fjernes, og trekkpapiret torkes på trommeltorkeren. Når The five tracing papers are placed on a hydraulic press, and a pressure of 3.5 kp/cm p is applied for 1 minute and then released. The tracing papers are removed, and the two upper and the two lower tracing papers are removed so that one tracing paper and the sample remain. The sample is removed, and the tracing paper is dried on the drum dryer. When
det er blitt torket undersokes trekkpapiret for å fastslå mot-standsdyktigheten overfor blodning0 it has been dried, the tracing paper is examined to determine its resistance to bleeding0
Standard blodningsopplosninger er: (1) Vann', (2) 50/ 50 vann- alkohol, (3) 0,5$ "Aerosol" OT, (<>>+) melk,^mettet "Comet"-rensemiddel, (6) 0,5$ "Ivory"-såpeopplosning, (7) "Formula<1>+09" og (8) "Windex". Standard bleeding solutions are: (1) Water', (2) 50/50 water-alcohol, (3) 0.5$ "Aerosol" OT, (<>>+) milk,^saturated "Comet" detergent, (6 ) 0.5$ "Ivory" soap solution, (7) "Formula<1>+09" and (8) "Windex".
Handelsproduktene '.'Comef-rensemiddel, "Ivory "-såpe ,The commercial products '.'Comef cleaner, "Ivory" soap,
"Formula ^-09" og "Windex" representerer en rekke vanlige hushold-ningsrensematerialer0"Aerosol" OT selges som simulert slimhinne for undersbkelsesformål. "Formula ^-09" and "Windex" represent a variety of common household cleaning materials0 "Aerosol" OT is sold as a simulated mucous membrane for under-smoothing purposes.
Graden av motstandsdyktighet overfor blodning fastsettes i The degree of resistance to bleeding is determined in
overensstemmelse med folgende skala:compliance with the following scale:
5 = ubetydelig eller ingen blodning5 = negligible or no bleeding
<*>+ = svak blodning<*>+ = slight bleeding
3 r- merkbar blodning3 r- noticeable bleeding
2 = betraktelig blodning2 = considerable bleeding
1 = sterk blodning1 = heavy bleeding
Papirtissue farvet med farvestoffene ifolge oppfinnelsenPaper tissue dyed with the dyes according to the invention
og som beskrevet i de nedenstående eksempler, har en tilfreds-stillende motstandsdyktighet overfor blodning ved bruk av alle de angitte reagenser,, Dessuten er de sterkt motstandsdyktige overfor blodning når de kommer i kontakt med konsistensfett ut-sondret fra stekt nedmalt kjott. and as described in the examples below, have a satisfactory resistance to bleeding when using all the indicated reagents,, Furthermore, they are highly resistant to bleeding when they come into contact with fat of consistency except from fried minced meat.
Eksempel 1Example 1
A. Fremstilling av tetrakis( aminomethyl)-kobberf thalocyaninA. Preparation of tetrakis(aminomethyl)-copper phthalocyanine
100 g (0,175 mol) kobberfthalocyanin, 5° g fosforpentoxyd,100 g (0.175 mol) copper phthalocyanine, 5° g phosphorus pentoxide,
. 153 g fthalimid og 55 g paraformaldehyd ble satt til 1^00 g 100$-ig~svovelsyre. Blandingen ble oppvarmet ved 125°C i 1 time og derefter sluppet ned i isvann. Efter omhyggelig blanding ble et fast produkt fraskilt ved filtrering og godt vasket med vann0Den fuktige filterkake ble oppslemmet i fortynnet natriumhydroxyd, og blandingen ble oppvarmet under tilbakelop i 1 time og derefter surgjort med konsentrert saltsyre og oppvarmet under tilbakelop i ytterligere 2 timer. Den ble derefter gjort alkalisk (pH på 10 eller derover) med en vandig natriumhydroxydopplosning, og de . 153 g of phthalimide and 55 g of paraformaldehyde were added to 1,000 g of 100 µg sulfuric acid. The mixture was heated at 125°C for 1 hour and then dropped into ice water. After careful mixing, a solid product was separated by filtration and washed well with water0 The moist filter cake was slurried in dilute sodium hydroxide, and the mixture was heated under reflux for 1 hour and then acidified with concentrated hydrochloric acid and heated under reflux for another 2 hours. It was then made alkaline (pH of 10 or greater) with an aqueous sodium hydroxide solution, and the
utfelte faststoffer ble oppsamlet ved hjelp av filtrering og vasket godt med vann. Produktet som besto av en fuktig kake- av tetrakis(aminomethyl)rkobberfthalocyanin, ble anvendt i trinn B precipitated solids were collected by filtration and washed well with water. The product, which consisted of a moist cake of tetrakis(aminomethyl)copper phthalocyanine, was used in step B
og i alle de nedenstående eksempler.and in all the examples below.
B. Fremstilling av tetrakis(p-hydroxybutylaminomethyl)-kobberfthalocyanin acetatopplosning B. Preparation of tetrakis(p-hydroxybutylaminomethyl)-copper phthalocyanine acetate solution
Den fuktige kake fra trinn A ble oppslemmet med vann og butylenoxyd og oppvarmet til 60°C Efter dråpevis tilsetning av iseddik ble reaksjonsblandingen omrdrt og oppvarmet i h timer ved 60°C og derefter i 1 time ved 80-90°C„ Farvestoffproduktet ble opplost i iseddik, og efter blanding i et par minutter ble opp», The moist cake from step A was slurried with water and butylene oxide and heated to 60°C. After the dropwise addition of glacial acetic acid, the reaction mixture was stirred and heated for h hours at 60°C and then for 1 hour at 80-90°C„ The dye product was dissolved in glacial acetic acid, and after mixing for a couple of minutes came up",
losningen avkjolt til 25°C. Opplosningen veide 660 g og inneholdt ca. 0,17 mol farvestoff som representerte et utbytte på the solution cooled to 25°C. The solution weighed 660 g and contained approx. 0.17 mol of dye which represented a yield of
ca.97%* Det hadde en maksimal absorpsjon (X, •) på 6l8 nm about 97%* It had a maximum absorption (X, •) of 6l8 nm
ulciK. S * ^ulciK. S * ^
og styrke (maksimum absorps jons evne) på 10,5 I-.g~ . cm » Dets formel var and strength (maximum absorption capacity) of 10.5 I-.g~ . cm » Its formula was
Konsentrasjonen av farvestoffet i acetatsaltformen var ca. 32$. Det ga papir med klare blå farvenyanser lignende den nyanse som fås av farveindeksfarvestoffet grunnblått 82. Det farvede tissue hadde en utmerket motstandsdyktighet overfor blodning i vann, alkohol-vann,(efterlignende alkoholholdige drikker), melk og "Aerosol" OT. The concentration of the dye in the acetate salt form was approx. 32$. It produced paper with clear blue color shades similar to the shade obtained from the color index dye basic blue 82. The dyed tissue had an excellent resistance to bleeding in water, alcohol-water, (simulating alcoholic beverages), milk and "Aerosol" OT.
Eksempel 2Example 2
359<!>+ g med vann fuktig kake av tetrakis (aminomethyl)-kobberfthalocyanin (ekvivalent med 0,02 mol) ble omrort med 25 ml vann. Oppslemningens pH (10,6) ble senket til 5,0 med iseddik. Ethylenoxydgass ble boblet inn i oppslemningen inntil en samlet mengde på 1790 ml (0,08 mol) var blitt tilsatt. Derefter ble 359<!>+ g of water-moist cake of tetrakis(aminomethyl)-copper phthalocyanine (equivalent to 0.02 mol) was stirred with 25 ml of water. The pH of the slurry (10.6) was lowered to 5.0 with glacial acetic acid. Ethylene oxide gas was bubbled into the slurry until a total of 1790 mL (0.08 mole) had been added. After that was
10,1 g (0,08 mol) dimethylsulfat dråpevis tilsatt, og blandingen ble derefter oppvarmet til 55°C, 20,0 g (0,33 mol) eddiksyre ble tilsatt, og blandingen ble avkjoltc10.1 g (0.08 mol) of dimethyl sulfate was added dropwise, and the mixture was then heated to 55°C, 20.0 g (0.33 mol) of acetic acid was added, and the mixture was cooled
Produktet var en klar blå farvestoffopplosning med en mak-simumsabsorpsjon ( mako ) på 615 nm. Den maksimale absorp-sjonsevne (A ma, Ki s o ) var 6,98 l.g"<1>.cm"<1>. Farvestoffet hadde formelen The product was a clear blue dye solution with a maximum absorption ( mako ) of 615 nm. The maximum absorption capacity (A ma, Ki s o ) was 6.98 l.g"<1>.cm"<1>. The dye had the formula
tf Det ga papir med blåaktige farvetoner som var noe rodere tf It produced paper with bluish tints that were somewhat messier
og mattere enn grunnblått 82. Det farvede papir hadde en utmerket motstandsdyktighet overfor blodning i vann, vann-alkohol, "Aerosol" OT og melk og ga i "Aerosol" OT et prøveresultat på 5- h i henhold til den ovenstående ska]a og på 5 i de andre reagenser. and duller than basic blue 82. The colored paper had an excellent resistance to bleeding in water, water-alcohol, "Aerosol" OT and milk and gave in "Aerosol" OT a test result of 5-h according to the above ska]a and on 5 in the other reagents.
Eksenrpel 3Example 3
2Li-,5 g med vann fuktig filterkake av tetrakis (aminomethyl)-kobberfthalocyanin (ekvivalent med 0,02 mol) ble omrort i vann under erholdelse av en jevn oppslemning. Ved tilsetning av eddiksyre ble pH regulert til Ethylenoxydgass ble boblet ned i oppslemningen inntil 3,58 1 (0,16 mol) var blitt tilsatt. Reaksjonsmassen ble holdt ved værelsétemperatur og fikk en ganske hoy visko-sitet. Efter at reaksjonsmassen var blitt omrort ved værelsétemperatur i 30 minutter, ble den i 30 minutter holdt ved en temperatur på 50°C. Derefter ble 20 ml eddiksyre tilsatt, og blandingen ble omrort i et par minutter. Den klare opplbsning (76 g) 2Li-.5 g of water-moistened filter cake of tetrakis(aminomethyl)-copper phthalocyanine (equivalent to 0.02 mol) was stirred in water to obtain a uniform slurry. By adding acetic acid, the pH was adjusted until Ethylene oxide gas was bubbled into the slurry until 3.58 1 (0.16 mol) had been added. The reaction mass was kept at room temperature and acquired a fairly high viscosity. After the reaction mass had been stirred at room temperature for 30 minutes, it was kept at a temperature of 50°C for 30 minutes. Then 20 ml of acetic acid was added and the mixture was stirred for a couple of minutes. The clear solution (76 g)
ga et synlig spektrum i vann med X maks 610 nm og en A^^g- på ' 8.9'+ l.g~1.cm"1c Den inneholdt ca. av farvestoffet gave a visible spectrum in water with X max 610 nm and an A^^g- of ' 8.9'+ l.g~1.cm"1c It contained approx. of the dye
Tissue farvet med dette farvestoff hadde en utmerket motstandsdyktighet overfor blodning i vann, vann-alkohol, "Aerosol" OT og melk, og ga som resultat 5 i alle provereagenser med unntagelse av i "Aerosol" OT hvor det erholdte resultat var ?- k i henhold til den ovenstående skala. Tissue stained with this dye had an excellent resistance to bleeding in water, water-alcohol, "Aerosol" OT and milk, and gave a result of 5 in all test reagents with the exception of in "Aerosol" OT where the result obtained was ?- k according to to the above scale.
Eksempel hExample h
35,'+ g med vann fuktig filterkake av tetrakis (aminomethyl)-kobberfthalocyanin (ekvivalent med 0,02 mol) ble omrort i 30 ml vann, og tilstrekkelig iseddik ble tilsatt til å regulere pH til 5,0. 35.0 g of water-wet filter cake of tetrakis(aminomethyl)-copper phthalocyanine (equivalent to 0.02 mol) was stirred in 30 ml of water, and sufficient glacial acetic acid was added to adjust the pH to 5.0.
Ethylenoxydgass ble innfort i reaksjonsblandingen i en mengde av 5-6 ml/min i 85 minutter. En samlet mengde på 0,51 1 tilsvarende 0,0228 mol ble anvendt. Temperaturen var cac 25°C. Efter omroring i ytterligere en time ble 5,0 ml (0,06 mol) konsentrert saltsyre tilsatt. På dette trinn var fremdeles en del av produktet uopplost0 10 g ethylenglycol, 10 g sulfolan og 10 g glycolsyre ble derefter tilsatt. Massen ble da forandret til en Ethylene oxide gas was introduced into the reaction mixture at a rate of 5-6 ml/min for 85 minutes. A total amount of 0.51 1 corresponding to 0.0228 mol was used. The temperature was cac 25°C. After stirring for a further hour, 5.0 ml (0.06 mol) of concentrated hydrochloric acid was added. At this stage, part of the product was still undissolved. 10 g of ethylene glycol, 10 g of sulfolane and 10 g of glycolic acid were then added. The mass was then changed to one
klar opplosning som veide lli-0 g.X var 6l8 nm og A,, var _-j maKs. flidKs, clear solution weighing lli-0 g.X was 6l8 nm and A,, was _-j maKs. diligentKs,
Farvestoffet hadde folgende formelThe dye had the following formula
Tissue farvet med dette farvestoff hadde en utmerket motstandsdyktighet overfor blodning i vann, vann-alkohol, "Aerosol" OT og melk og ble bedomt til skalaverdien 5 i alle forsoksreagenser. Tissue stained with this dye had excellent resistance to bleeding in water, water-alcohol, "Aerosol" OT and milk and was rated as a scale value of 5 in all test reagents.
Ekse mpel 5Example 5
2^,5 g av med vann fuktig filterkake av tetrakis (amino-methyl) -kobberf thalocyanin (ekvivalent med 0,02 mol) og 10 ml vann ble omrort med 1,1 ml iseddik som senket pH til '+,5. Derefter ble I<1>)-,2 g 1,2-butylenoxyd dråpevis tilsatt i lopet av 0,5 time. Temperaturen var 25°C. Efter omroring i ytterligere.1 2^.5 g of water-moistened filter cake of tetrakis(amino-methyl)-copper phthalocyanine (equivalent to 0.02 mole) and 10 ml of water were stirred with 1.1 ml of glacial acetic acid which lowered the pH to +.5. Then 1.2 g of 1,2-butylene oxide was added dropwise over the course of 0.5 hour. The temperature was 25°C. After further stirring.1
time ble blandingen oppvarmet til 50°C og omrort i ytterligere 1 time. Det forelå store mengder faststoffer i reaksjonsblandingen. Derefter ble 20,0 g glycolsyre tilsatt.og blandingen langsomt oppvarmet til 95°C. Det ble dannet en klar opplosning som bevarte sin klarhet da den ble avkjolt til værelsetemperatur„, Opplosnings-produktet veide 69,2 g. Det hadde et A k på 616 nm og et Amaks. på 8'^6 1"g"<1>-cm<_1>-hour, the mixture was heated to 50°C and stirred for a further 1 hour. There were large amounts of solids in the reaction mixture. Then 20.0 g of glycolic acid was added and the mixture slowly heated to 95°C. A clear solution was formed which retained its clarity when cooled to room temperature. The solution product weighed 69.2 g. It had an A k of 616 nm and an Amax. of 8'^6 1"g"<1>-cm<_1>-
Farvestoffet hadde formelen The dye had the formula
Tissue som ble farvet med en opplosning av det ovenstående farvestoff, hadde en utmerket motstandsdyktighet overfor blodning i vann, vann-alkohol, "Aerosol" OT og melk og ga skalaverdien 5 i vann-alkohol og melk og 5J+- i vann og "Aerosol" 0To Eksempel 6 Fremgangsmåten ifolge eksempel 5 ble gjentatt, men bare med anvendelse av halvparten av den ifolge eksempel 5 anvendte mengde 1,2-butylenoxyd. Bet erholdte farvestoff som forelå i opplost til-stand, hadde formelen Tissue stained with a solution of the above dye had excellent resistance to bleeding in water, water-alcohol, "Aerosol" OT and milk and gave a scale value of 5 in water-alcohol and milk and 5J+- in water and "Aerosol" Example 6 The procedure according to example 5 was repeated, but only with the use of half of the amount of 1,2-butylene oxide used according to example 5. Bet obtained dye which was present in a dissolved state, had the formula
Tissue som ble farvet med dette farvestoff, hadde også en utmerket motstandsdyktighet overfor blodning„ Tissue stained with this dye also had excellent resistance to bleeding.
Eksempel 7Example 7
Farvestoffet ifolge dette eksempel ligger utenfor oppfin-nelsens ramme, men det-viser at i formelen The dye according to this example lies outside the scope of the invention, but it shows that in the formula
er bindingen N-H av avgjorende betydning. is the bond N-H of decisive importance.
Ved fremstillingen av dette farvestoff ble det igjen anvendt en fuktig presskake av tetrakis (aminomethyl)-kobberfthalocyanin som fremstilt ifolge eksempel 1. 35,^ g av kaken (ekvivalent med 0?.02 mol) ble omrort i 30 ml vann inntil en jevn opp-.slemning var blitt dannet. En samlet mengde på 3,96 1 (0,196 mol) ethylenoxydgass ble boblet inn i oppslemningen, og derefter ble 5,2 g (0,05 mol) natriumcarbonat tilsatt fulgt av 12,6 g (0,10 mol) dimethylsulfat. Reaksjonsblandingen ble langsomt oppvarmet til In the production of this dye, a moist press cake of tetrakis (aminomethyl)-copper phthalocyanine as prepared according to example 1 was again used. 35.7 g of the cake (equivalent to 0.02 mol) was stirred in 30 ml of water until a smooth -.slamming had been formed. A total of 3.96 L (0.196 mol) of ethylene oxide gas was bubbled into the slurry, and then 5.2 g (0.05 mol) of sodium carbonate was added followed by 12.6 g (0.10 mol) of dimethyl sulfate. The reaction mixture was slowly heated to
. o • o . OE OE
tilbakelopstemperatur (100 C) og avkjolt til 70 C. Det meste, men ikke hele mengden, av reaksjonsblandingen forelå i opplosning. Eddiksyre ble tilsatt for å regulere pH til ^,0. Produktets vekt var 102 g,Xm&k^ 617 nm og 6,2 l.g" ..cm'1. reflux temperature (100 C) and cooled to 70 C. Most, but not all, of the reaction mixture was in solution. Acetic acid was added to adjust the pH to ^.0. The weight of the product was 102 g, Xm&k^ 617 nm and 6.2 l.g" ..cm'1.
Da tissue farvet med dette produkt ble undersokt for å fastslå dets motstandsdyktighet overfor blodning, ga det et util-fredsstillende resultat idet proveopplosningen av vann-alkohol ga en bedommelse på 3 og melk en bedbmmelse på 2-l0Farvestoffet hadde formelen When tissue dyed with this product was examined to determine its resistance to bleeding, it gave an unsatisfactory result, the water-alcohol sample solution giving a rating of 3 and milk a rating of 2-10 The dye had the formula
Da det ikke inneholder N-H-grupperinger, er det ikke et farvestoff ifolge oppfinnelsen og forer da heller ikke til de samme gode resultater som f arvestoff ene ifolge oppfinnelsen,, As it does not contain N-H groupings, it is not a dye according to the invention and does not lead to the same good results as the dyes according to the invention,
Eksempel 8Example 8
Del IPart I
Farvestoffet ifolge dette eksempel faller også utenfor opp-finnelsens ramme. Dette eksempel viser at i formelan The dye according to this example also falls outside the scope of the invention. This example shows that in the formula
kan substituentene R-^ og Rg ikke være hydrogen hvis de onskede egenskaper skal kunne oppnås. cannot the substituents R-^ and Rg be hydrogen if the desired properties are to be achieved.
100 g kobberf thalocyanin ble satt til ihOO g 100%-ig svovelsyre, og temperaturen ble oket til ca. 35°C. Derefter ble 5° g fosforpentoxyd tilsatt og temperaturen oket til ca.<!>+0°C. Da opplosningen var fullstendig, ble blandingen avkjolt til 15-20°C, hvorefter 55 g paraformaldehyd ble tilsatt. Blandingen ble oppvarmet i 75°C, omrort ved denne temperatur i 2 timer og sluppet ned i is. Da reaksjonsblandingen var blitt sluppet ned i is og temperaturen var ca. 70°C, ble det faste produkt fraskilt ved hjelp av filtrering og vasket med vann. 100 g of copper phthalocyanine was added to 100 g of 100% sulfuric acid, and the temperature was increased to approx. 35°C. Then 5° g of phosphorus pentoxide was added and the temperature increased to approx.<!>+0°C. When the dissolution was complete, the mixture was cooled to 15-20°C, after which 55 g of paraformaldehyde was added. The mixture was heated to 75°C, stirred at this temperature for 2 hours and dropped into ice. When the reaction mixture had been dropped into ice and the temperature was approx. 70°C, the solid product was separated by filtration and washed with water.
Den fuktige filterkake ble nøytralisert, ytterligere natriumhydroxyd ble tilsatt, og chargen ble oppvarmet til tilbakelopstemperaturen. Efter 1 time ved tilbakelopstemperaturen ble chargen avkjolt til 80-90°C, konsentrert saltsyre ble tilsatt, The moist filter cake was neutralized, additional sodium hydroxide was added, and the charge was heated to the reflux temperature. After 1 hour at the reflux temperature, the charge was cooled to 80-90°C, concentrated hydrochloric acid was added,
og chargen ble igjen tilbakelopsdestillert i 1 time. Efter av-kjoling til 90°C ble chargen gjort alkalisk (pH 9-10), og det faste produkt ble utvunnet ved filtrering og torket i en ovn. and the charge was again refluxed for 1 hour. After cooling to 90°C, the charge was made alkaline (pH 9-10), and the solid product was recovered by filtration and dried in an oven.
130 g tort materiale ble-erholdt.130 g of dry material was obtained.
Produktet besto i det vesentlige av CuPc-(CHQNH9)^. DetThe product consisted essentially of CuPc-(CHQNH9)^. The
ble blandet med en saltsyreopplosning glycolsyre, ethylenglycol was mixed with a hydrochloric acid solution glycolic acid, ethylene glycol
og.opplosningsmidlet sulfolan (tetramethylsulfon), og blandingen ble oppvarmet i 15 minutter ved 50-70°C under erholdelse av en klar opplosning. and the solvent sulfolane (tetramethylsulfone), and the mixture was heated for 15 minutes at 50-70°C, obtaining a clear solution.
e Produktet som besto av en opplosning av CuPc-(CH^NH^Cl ga ved farving av tissue en tiltalende turkis farvetone., og det farvede papir hadde en utmerket motstandsdyktighet overfor blodning i vann, vann-alkoholopplosning, "Aerosol" OT og melk. Opplosningen beholdt imidlertid ikke sin klarhet, en del faste stoffer ble felt ut, og ved fortynning med vann ble opplosningen ugjennomskinnelig„ Disse egenskaper gjor at denne farvestoff-"opplosning" er uaksep-terbar for kommersiell anvendelse„ e The product consisting of a solution of CuPc-(CH^NH^Cl) gave a pleasing turquoise tint when dyeing tissue, and the dyed paper had excellent resistance to bleeding in water, water-alcohol solution, "Aerosol" OT and milk However, the solution did not retain its clarity, some solids were precipitated, and when diluted with water the solution became opaque. These properties make this dye "solution" unacceptable for commercial use.
Del II røPart II roe
Farvestof f et CuPc-(CR^NH^Cl ble fremstilt ved i det vesentlige samme fremgangsmåte som i del I, men ved anvendelse av det dobbelte molforhold av fosforpentoxyd, fthalimid og paraformaldehyd til kobber f thalocyanin. r<3>ette farvestoff hadde den samme gode motstandsdyktighet overfor blodning og de utilfreds-stillende opplosningsegenskaper som farvestoffet i del I. Dyestuff f a CuPc-(CR^NH^Cl) was prepared by essentially the same procedure as in part I, but using the double molar ratio of phosphorus pentoxide, phthalimide and paraformaldehyde to copper fthalocyanine. This dye had the the same good resistance to bleeding and the unsatisfactory dissolution properties as the dye in part I.
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US44680474A | 1974-02-28 | 1974-02-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO750662L true NO750662L (en) | 1975-08-29 |
Family
ID=23773888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO750662A NO750662L (en) | 1974-02-28 | 1975-02-27 |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS50124928A (en) |
| DE (1) | DE2508892A1 (en) |
| FI (1) | FI750594A (en) |
| IT (1) | IT1033194B (en) |
| NO (1) | NO750662L (en) |
| SE (1) | SE7502219L (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4036585A (en) * | 1976-08-10 | 1977-07-19 | E. I. Du Pont De Nemours And Company | Bleedfast phthalocyanine dyes for paper |
| DE3164935D1 (en) * | 1980-02-18 | 1984-08-30 | Basf Ag | Dyestuffs containing imidazolylethylene groups and their use |
| US10502321B2 (en) | 2014-01-14 | 2019-12-10 | Compart Systems Pte, Ltd. | Gasket retainer for surface mount fluid component |
-
1975
- 1975-02-25 IT IT20657/75A patent/IT1033194B/en active
- 1975-02-27 SE SE7502219A patent/SE7502219L/xx unknown
- 1975-02-27 JP JP50023520A patent/JPS50124928A/ja active Pending
- 1975-02-27 NO NO750662A patent/NO750662L/no unknown
- 1975-02-28 FI FI750594A patent/FI750594A/fi not_active Application Discontinuation
- 1975-02-28 DE DE19752508892 patent/DE2508892A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| IT1033194B (en) | 1979-07-10 |
| FI750594A (en) | 1975-08-29 |
| SE7502219L (en) | 1975-09-29 |
| JPS50124928A (en) | 1975-10-01 |
| DE2508892A1 (en) | 1975-09-04 |
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