EP0138159A2 - Matériel d'enregistrement thermosensible, préparation et emploi de polymères modifiés par l'acide comme accepteurs dans ce matériel - Google Patents

Matériel d'enregistrement thermosensible, préparation et emploi de polymères modifiés par l'acide comme accepteurs dans ce matériel Download PDF

Info

Publication number: EP0138159A2
Authority: EP; European Patent Office
Prior art keywords: recording material; acid; thermoreactive recording; acrylonitrile; material according
Prior art date: 1983-10-13
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Granted

Application number

EP84111852A

Other languages

German (de)

English (en)

Other versions

EP0138159A3 (en

EP0138159B1 (fr

Inventor

Hubertus Dr. Psaar

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Bayer AG

Original Assignee

Bayer AG

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1983-10-13

Filing date

1984-10-04

Publication date

1985-04-24

1984-10-04 Application filed by Bayer AG filed Critical Bayer AG

1985-04-24 Publication of EP0138159A2 publication Critical patent/EP0138159A2/fr

1986-05-21 Publication of EP0138159A3 publication Critical patent/EP0138159A3/de

1988-08-31 Application granted granted Critical

1988-08-31 Publication of EP0138159B1 publication Critical patent/EP0138159B1/fr

Status Expired legal-status Critical Current

Links

239000000463 material Substances 0.000 title claims abstract description 27
229920000642 polymer Polymers 0.000 title claims abstract description 18
238000002360 preparation method Methods 0.000 title claims description 3
NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 28
239000002243 precursor Substances 0.000 claims abstract description 10
OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 14
239000000975 dye Substances 0.000 claims description 14
239000000370 acceptor Substances 0.000 claims description 13
229920000058 polyacrylate Polymers 0.000 claims description 5
230000002378 acidificating effect Effects 0.000 claims description 4
150000001298 alcohols Chemical class 0.000 claims description 4
150000002148 esters Chemical class 0.000 claims description 3
NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
238000004519 manufacturing process Methods 0.000 claims description 2
125000005397 methacrylic acid ester group Chemical group 0.000 claims description 2
150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 2
239000001003 triarylmethane dye Substances 0.000 claims description 2
125000000217 alkyl group Chemical group 0.000 claims 1
239000011248 coating agent Substances 0.000 claims 1
238000000576 coating method Methods 0.000 claims 1
239000000758 substrate Substances 0.000 claims 1
BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 14
239000006185 dispersion Substances 0.000 description 10
-1 lauryl ester Chemical class 0.000 description 10
239000004372 Polyvinyl alcohol Substances 0.000 description 9
229920002239 polyacrylonitrile Polymers 0.000 description 9
229920002451 polyvinyl alcohol Polymers 0.000 description 9
239000002253 acid Substances 0.000 description 8
XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 7
239000001913 cellulose Substances 0.000 description 5
229920002678 cellulose Polymers 0.000 description 5
XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 4
AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 4
LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
238000006243 chemical reaction Methods 0.000 description 4
239000011230 binding agent Substances 0.000 description 3
150000001875 compounds Chemical class 0.000 description 3
FRXGWNKDEMTFPL-UHFFFAOYSA-N dioctadecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCCCC FRXGWNKDEMTFPL-UHFFFAOYSA-N 0.000 description 3
238000000034 method Methods 0.000 description 3
239000000203 mixture Substances 0.000 description 3
HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 2
150000008360 acrylonitriles Chemical class 0.000 description 2
239000000654 additive Substances 0.000 description 2
IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
239000012876 carrier material Substances 0.000 description 2
229920001577 copolymer Polymers 0.000 description 2
235000014113 dietary fatty acids Nutrition 0.000 description 2
150000002169 ethanolamines Chemical class 0.000 description 2
239000000194 fatty acid Substances 0.000 description 2
229930195729 fatty acid Natural products 0.000 description 2
150000004665 fatty acids Chemical class 0.000 description 2
HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 2
150000003839 salts Chemical class 0.000 description 2
229940124530 sulfonamide Drugs 0.000 description 2
WOIXNNYYJBROCS-UHFFFAOYSA-N 1,1-bis[4-(dimethylamino)phenyl]-n-phenylmethanesulfonamide Chemical compound C1=CC(N(C)C)=CC=C1C(S(=O)(=O)NC=1C=CC=CC=1)C1=CC=C(N(C)C)C=C1 WOIXNNYYJBROCS-UHFFFAOYSA-N 0.000 description 1
OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
239000004808 2-ethylhexylester Substances 0.000 description 1
FCYVWWWTHPPJII-UHFFFAOYSA-N 2-methylidenepropanedinitrile Chemical compound N#CC(=C)C#N FCYVWWWTHPPJII-UHFFFAOYSA-N 0.000 description 1
WAYFJTUZNWOHQH-UHFFFAOYSA-N 2-propylideneoctanoic acid Chemical compound CCCCCCC(C(O)=O)=CCC WAYFJTUZNWOHQH-UHFFFAOYSA-N 0.000 description 1
KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
YCPTZNXYCILFAR-UHFFFAOYSA-N 4-[[4-(dimethylamino)-4-dodecylcyclohexa-1,5-dien-1-yl]-[[4-(dimethylamino)-4-dodecylcyclohexa-1,5-dien-1-yl]-[4-(dimethylamino)phenyl]-phenylmethyl]sulfonyl-phenylmethyl]-N,N-dimethylaniline Chemical compound C(CCCCCCCCCCC)C1(CC=C(C(C2=CC=C(C=C2)N(C)C)(C2=CC=CC=C2)S(=O)(=O)C(C2=CCC(C=C2)(CCCCCCCCCCCC)N(C)C)(C2=CC=C(C=C2)N(C)C)C2=CC=CC=C2)C=C1)N(C)C YCPTZNXYCILFAR-UHFFFAOYSA-N 0.000 description 1
RVOZHMGGPGEVIB-UHFFFAOYSA-N 4-[[bis[4-(dimethylamino)phenyl]-phenylmethyl]sulfonyl-[4-(dimethylamino)phenyl]-phenylmethyl]-n,n-dimethylaniline Chemical compound C1=CC(N(C)C)=CC=C1C(S(=O)(=O)C(C=1C=CC=CC=1)(C=1C=CC(=CC=1)N(C)C)C=1C=CC(=CC=1)N(C)C)(C=1C=CC(=CC=1)N(C)C)C1=CC=CC=C1 RVOZHMGGPGEVIB-UHFFFAOYSA-N 0.000 description 1
239000005995 Aluminium silicate Substances 0.000 description 1
JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
229920000084 Gum arabic Polymers 0.000 description 1
239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
241000978776 Senegalia senegal Species 0.000 description 1
XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
JJOHBYWZGJKPMA-UHFFFAOYSA-N [4-(dimethylamino)-4-(2-methylphenyl)cyclohexa-1,5-dien-1-yl]-[4-(dimethylamino)phenyl]methanesulfonamide Chemical compound C1(=C(C=CC=C1)C1(CC=C(C(C2=CC=C(C=C2)N(C)C)S(=O)(=O)N)C=C1)N(C)C)C JJOHBYWZGJKPMA-UHFFFAOYSA-N 0.000 description 1
239000002250 absorbent Substances 0.000 description 1
230000002745 absorbent Effects 0.000 description 1
239000000205 acacia gum Substances 0.000 description 1
235000010489 acacia gum Nutrition 0.000 description 1
150000007513 acids Chemical class 0.000 description 1
150000001252 acrylic acid derivatives Chemical class 0.000 description 1
150000008051 alkyl sulfates Chemical class 0.000 description 1
235000012211 aluminium silicate Nutrition 0.000 description 1
DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
MKUWVMRNQOOSAT-UHFFFAOYSA-N but-3-en-2-ol Chemical compound CC(O)C=C MKUWVMRNQOOSAT-UHFFFAOYSA-N 0.000 description 1
150000004649 carbonic acid derivatives Chemical class 0.000 description 1
239000005018 casein Substances 0.000 description 1
BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
235000021240 caseins Nutrition 0.000 description 1
239000003054 catalyst Substances 0.000 description 1
239000003795 chemical substances by application Substances 0.000 description 1
239000003086 colorant Substances 0.000 description 1
238000004040 coloring Methods 0.000 description 1
125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
230000000694 effects Effects 0.000 description 1
UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
150000002170 ethers Chemical class 0.000 description 1
125000004494 ethyl ester group Chemical group 0.000 description 1
238000007380 fibre production Methods 0.000 description 1
XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
230000009477 glass transition Effects 0.000 description 1
238000010438 heat treatment Methods 0.000 description 1
125000002768 hydroxyalkyl group Chemical group 0.000 description 1
235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
238000002372 labelling Methods 0.000 description 1
238000002844 melting Methods 0.000 description 1
230000008018 melting Effects 0.000 description 1
229910052751 metal Inorganic materials 0.000 description 1
239000002184 metal Substances 0.000 description 1
FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
230000005012 migration Effects 0.000 description 1
238000013508 migration Methods 0.000 description 1
125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
150000002894 organic compounds Chemical class 0.000 description 1
230000003647 oxidation Effects 0.000 description 1
238000007254 oxidation reaction Methods 0.000 description 1
PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
150000002989 phenols Chemical class 0.000 description 1
238000006116 polymerization reaction Methods 0.000 description 1
235000019422 polyvinyl alcohol Nutrition 0.000 description 1
239000001267 polyvinylpyrrolidone Substances 0.000 description 1
229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
230000002028 premature Effects 0.000 description 1
UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
230000009257 reactivity Effects 0.000 description 1
238000001454 recorded image Methods 0.000 description 1
230000035945 sensitivity Effects 0.000 description 1
238000004513 sizing Methods 0.000 description 1
239000010802 sludge Substances 0.000 description 1
230000035943 smell Effects 0.000 description 1
239000000126 substance Substances 0.000 description 1
125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1

Classifications

- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3331—Macromolecular compounds

Definitions

thermoreactive recording material which contains a dye precursor and an acid-modified polymer of acrylonitrile as an acceptor.
Heat-sensitive recording materials are already known in which a colorless dye precursor with an acceptor is applied in one layer to a carrier material, the two components being coated separately with other materials in order to prevent a premature color reaction. During the heat treatment, melting the envelopes and, if applicable, the acceptor material brings both components into contact and triggers a color reaction.
Dye precursors from various classes of dyes are known as color formers.
materials that trigger the color reaction organic compounds containing phenolic groups, for example bisphenol A, have hitherto become known, but because of their high rate of migration and volatility they have to be mixed with absorbents such as kaolin. The volatility of the phenols is a major disadvantage of these materials, as they often cause unpleasant smells. Another disadvantage of these acceptors is their sensitivity to pressure.
acid-modified polyacrylonitrile is an acceptor material which does not have the disadvantages mentioned above.
polymers of acrylonitrile and copolymers view of acrylonitrile with other vinyl compounds such as vinylidene cyanide, vinyl fluoride, vinyl acetate, vinyl propionate, vinylpyridine, vinylimidazole, vinylpyrrolidone, vinyl ethanol, acrylic or methacrylic acid ester as well as their hydroxyalkyl esters, acrylic or methacrylic acid amides or their dialkylamides into account, wherein these copolymers have at least 50% by weight, preferably at least 85% by weight, of acrylonitrile units.
the polymers preferably contain a sulfo or sulfato group as the acid group.
the glass transition temperature of the polymers can be varied within a wide range and adapted to the desired effect.
Acrylates such as methyl acrylate, ethyl ester, n-propyl ester, -n-, -iso-and-tert-butyl ester, -hexyl ester, -2-ethylhexyl ester and lauryl ester are preferably suitable as comonomers for this purpose.
the acid-modified acrylonitrile polymers are prepared by known methods, the acid group being introduced into the end of the polymerization chain either through an acidic catalyst or through comonomers containing acid groups, for example vinylsulfonic acid, styrene sulfonic acid, allylsulfonic acid, methallylsulfonic acid, vinyloxyarene sulfonic acid, allyloxyarene sulfoxy acid, methaloxy sulfonic acid, methaloxy sulfonic acid, methaloxy sulfonic acid, methaloxy sulfonic acid, methaloxy sulfonic acid, .
These preparations are described, for example, in DT-C-654 989, US-A-2 601 256 and US-A-2 913 438 and in F.
acrylic polymers are suitable which contain acidic groups capable of developing the dye precursors.
the proportion of the acid groups in the acrylic polymer is preferably 0.5 to 2% by weight.
the dye precursors to be used are the dye formers which can usually be used for printing and thermocopying purposes, with the exception of those which can only be converted into dyes by air oxidation. Suitable color formers are described, for example, in the following publications:
carbinol bases or their derivatives especially carbinol bases or carbinol base ethers of small dye molecules which, due to their low molecular weight, easily penetrate into the polymers and can be bound there in salt form.
Examples of such compounds are carbinol bases or carbinol base derivatives of diaryl and triarylmethane dyes, which e.g. in US-A-4 211 436 and fluoranes.
the acid-modified acrylonitrile polymers are powdered with binders, e.g. Ground polyvinyl alcohol, hydroxyethyl cellulose, gum arabic, polyvinyl pyrrolidone, casein or similar substances.
binders e.g. Ground polyvinyl alcohol, hydroxyethyl cellulose, gum arabic, polyvinyl pyrrolidone, casein or similar substances.
fatty acids or fatty acid amides, long-chain alkyl sulfates or esters of long-chain alcohols to the polymers, for example phosphoric acid esters of long-chain alcohols such as mono- and di-phosphoric acid esters of C 8 -C 22 -alcohols, in amounts of 0.1 to 10% , based on the polymer.
the polymer can also be treated beforehand with the additives, for example ground.
the colorants are ground separately with the binders.
the dispersions of the acceptor are mixed with the dispersions of the color generator and applied and dried by means of a doctor blade on the carrier material, preferably cellulose paper, so that an application weight of 5 to 8 g per m 2 results.
the acceptor paper from a mixture of an acrylonitrile polymer with the additives described above with cellulose, sizing agent and aluminum sulfate in a sheet former and to coat it with the color former.
a finely powdered polyacrylonitrile polymer prepared from 94% acrylonitrile, 0.5% methallylsulfonic acid and 5.5% methyl acrylate, are ground in a ball mill with 225 g of an 8% aqueous polyvinyl alcohol solution and with the addition of 1.3 g distearyl phosphoric acid ester.
a second dispersion is prepared from 1 g of octyl-4,4'-bis (dimethylamino) benzhydryl sulfone and 55 g of an 8% aqueous polyvinyl alcohol solution.
the dispersion of the color former is mixed with that of the acceptor in a ratio of 1/10 and the mixture is applied to cellulose paper by means of a doctor blade and dried so that an application weight of 6 to 7 g / m 2 is obtained.
the paper can be written on with writing materials such as a ballpoint pen. It is insensitive to strong pressure. When you touch the paper with a heated pen, you get clear, sharp, shadow-free, blue writing. The lightfastness of the coloring is excellent.
a polyacrylic polymer prepared from 86.5% acrylonitrile, 0.5% methallylsulfonic acid, 13% methyl acrylate, are ground with 1.3 g monostearyl phosphoric acid ester and 425 g water, suction filtered and dried.
the dry polymer is ground with 112 g of a 4% aqueous polyvinyl alcohol solution.
a second dispersion is made from 2 g of a color former of the formula and 55 g of an 8% aqueous polyvinyl alcohol solution.
the two dispersions according to Example 1 are mixed in a ratio of 1/10 and applied to cellulose paper. With a heated pen you get a black lightfast font on the dried paper sheet.
aqueous 8% polyvinyl alcohol solution mixed in a ratio of 1/10 and applied to cellulose paper according to Example 1 wear.

Landscapes

Chemical & Material Sciences (AREA)
Chemical Kinetics & Catalysis (AREA)
General Chemical & Material Sciences (AREA)
Physics & Mathematics (AREA)
Optics & Photonics (AREA)
Heat Sensitive Colour Forming Recording (AREA)
Paper (AREA)
Color Printing (AREA)
Paints Or Removers (AREA)

EP84111852A 1983-10-13 1984-10-04 Matériel d'enregistrement thermosensible, préparation et emploi de polymères modifiés par l'acide comme accepteurs dans ce matériel Expired EP0138159B1 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
DE3337296		1983-10-13
DE19833337296 DE3337296A1 (de)	1983-10-13	1983-10-13	Thermoreaktives aufzeichnungsmaterial, seine herstellung und die verwendung von sauermodifizierten polymerisaten als akzeptoren in diesem aufzeichnungsmaterial

Publications (3)

Publication Number	Publication Date
EP0138159A2 true EP0138159A2 (fr)	1985-04-24
EP0138159A3 EP0138159A3 (en)	1986-05-21
EP0138159B1 EP0138159B1 (fr)	1988-08-31

Family

ID=6211767

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP84111852A Expired EP0138159B1 (fr)	1983-10-13	1984-10-04	Matériel d'enregistrement thermosensible, préparation et emploi de polymères modifiés par l'acide comme accepteurs dans ce matériel

Country Status (7)

Country	Link
US (1)	US4600930A (fr)
EP (1)	EP0138159B1 (fr)
JP (1)	JPS60132788A (fr)
CA (1)	CA1230739A (fr)
DE (2)	DE3337296A1 (fr)
FI (1)	FI79976C (fr)
HK (1)	HK51289A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
EP0407828A3 (en) *	1989-07-11	1991-05-08	Bayer Ag	Thermosensitive recording material
AT399126B (de) *	1987-03-31	1995-03-27	Ruetgerswerke Ag	Farbentwicklermassen für farbreaktionssysteme

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE3715724A1 (de) *	1987-05-12	1988-11-24	Bayer Ag	Thermoreaktives aufzeichnungsmaterial
US4877767A (en) *	1987-08-14	1989-10-31	The Mead Corporation	Vinyl developer resins
DE3940480A1 (de) *	1989-12-07	1991-06-13	Bayer Ag	Chromogene enaminverbindungen, ihre herstellung und verwendung als farbbildner
JP2596271Y2 (ja) *	1991-10-02	1999-06-07	株式会社アマダ	レーザ加工機

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US3413138A (en) *	1965-10-13	1968-11-26	Interchem Corp	Thermosensitive copy sheet
BE790932A (fr) *	1971-11-01	1973-03-01	Fuji Photo Film Co Ltd	Feuille d'enregistrement
JPS5833838B2 (ja) *	1978-03-28	1983-07-22	神崎製紙株式会社	感熱記録体
DE2820486A1 (de) *	1978-05-10	1979-11-15	Bayer Ag	Verfahren zur herstellung von sulfinaten des 4,4'diaminobenzhydrols und seiner substitutionsprodukte
JPS5553592A (en) *	1978-10-16	1980-04-19	Fuji Photo Film Co Ltd	Recording material
JPS57167380A (en) *	1981-04-08	1982-10-15	Pilot Ink Co Ltd	Thermochromic material
JPS59106995A (ja) *	1982-12-11	1984-06-20	Kanzaki Paper Mfg Co Ltd	感熱記録体

1983
- 1983-10-13 DE DE19833337296 patent/DE3337296A1/de not_active Withdrawn
1984
- 1984-10-04 EP EP84111852A patent/EP0138159B1/fr not_active Expired
- 1984-10-04 DE DE8484111852T patent/DE3473747D1/de not_active Expired
- 1984-10-05 US US06/658,341 patent/US4600930A/en not_active Expired - Fee Related
- 1984-10-08 JP JP59209950A patent/JPS60132788A/ja active Pending
- 1984-10-11 CA CA000465137A patent/CA1230739A/fr not_active Expired
- 1984-10-11 FI FI843998A patent/FI79976C/fi not_active IP Right Cessation
1989
- 1989-06-29 HK HK512/89A patent/HK51289A/xx unknown

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
AT399126B (de) *	1987-03-31	1995-03-27	Ruetgerswerke Ag	Farbentwicklermassen für farbreaktionssysteme
EP0407828A3 (en) *	1989-07-11	1991-05-08	Bayer Ag	Thermosensitive recording material
US5134113A (en) *	1989-07-11	1992-07-28	Bayer Aktiengesellschaft	Thermoreactive recording material

Also Published As

Publication number	Publication date
DE3473747D1 (en)	1988-10-06
FI79976B (fi)	1989-12-29
FI79976C (fi)	1990-04-10
FI843998L (fi)	1985-04-14
EP0138159A3 (en)	1986-05-21
CA1230739A (fr)	1987-12-29
JPS60132788A (ja)	1985-07-15
US4600930A (en)	1986-07-15
DE3337296A1 (de)	1985-04-25
HK51289A (en)	1989-07-07
EP0138159B1 (fr)	1988-08-31
FI843998A0 (fi)	1984-10-11

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Publication	Publication Date	Title
DE2905825C3 (de)	1996-04-11	Wärmeempfindliches Aufzeichnungsmaterial
DE3114681C2 (de)	1983-12-08	"Wärmeempfindliches Aufzeichnungsblatt"
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EP0211263B1 (fr)	1990-05-16	Matériau sensible à la chaleur pour l'enregistrement
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DE3236465A1 (de)	1983-04-21	Waermeempfindliches aufzeichnungsmaterial
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DE3843681A1 (de)	1989-07-20	Deckueberzugszusammensetzung fuer waermeempfindliche aufzeichnungsmaterialien
DE2932004C2 (de)	1986-10-30	Farbe entwickelndes Blatt und dessen Verwendung für druckempfindliche Aufzeichnungsblätter
EP0110252B1 (fr)	1985-11-13	Matériel thermosensible pour l'enregistrement
EP0224075B1 (fr)	1990-06-20	Matériau pour l'enregistrement sensible à la chaleur
DE3109800C2 (fr)	1991-01-31
EP0058345A1 (fr)	1982-08-25	Feuille d'enregistrement thermosensible
EP0137982B1 (fr)	1987-12-23	Feuille d'enregistrement sensible à la chaleur
DE2931621A1 (de)	1980-02-28	Waermeempfindlicher aufzeichnungsbogen
DE2753816B2 (de)	1980-04-24	Lösungsmittelgemisch und dessen Verwendung in Kopierpapieren
EP0135901B1 (fr)	1988-11-30	Matériel pour l'enregistrement thermosensible
EP0066813B1 (fr)	1985-08-21	Feuille d'enregistrement sensible à la chaleur
DE2618271B2 (de)	1978-06-29	Druckempfindliches Aufzeichnungsmaterial
DE2757865A1 (de)	1978-06-29	Farbstoffloesungsmittel fuer druckempfindliche kopiersysteme
DE3300229A1 (de)	1983-07-21	Waermeempfindliche aufzeichnungsblaetter
DE3121711A1 (de)	1982-12-16	Fluessige zubereitungen fuer die beschichtung von traegermaterial, mit diesen zubereitungen beschichtetes traegermaterial und dessen verwendung
DE3332844C2 (de)	1985-10-17	Wärmeempfindliches Aufzeichnungsblatt und Verfahren zu dessen Herstellung