GB2133024A - Printing ink - Google Patents
Printing ink Download PDFInfo
- Publication number
- GB2133024A GB2133024A GB08321948A GB8321948A GB2133024A GB 2133024 A GB2133024 A GB 2133024A GB 08321948 A GB08321948 A GB 08321948A GB 8321948 A GB8321948 A GB 8321948A GB 2133024 A GB2133024 A GB 2133024A
- Authority
- GB
- United Kingdom
- Prior art keywords
- resin
- printing ink
- poly
- ester
- amide
- Prior art date
- 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
Links
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 239000000049 pigment Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 description 16
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 14
- 239000003822 epoxy resin Substances 0.000 description 12
- 229920000647 polyepoxide Polymers 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 150000002118 epoxides Chemical class 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000976 ink Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- -1 poly(amide ester Chemical class 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- 235000019260 propionic acid Nutrition 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920006122 polyamide resin Polymers 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000020 Nitrocellulose Substances 0.000 description 3
- 150000001412 amines Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000003827 glycol group Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001220 nitrocellulos Polymers 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VPWFPZBFBFHIIL-UHFFFAOYSA-L Lithol Rubine Chemical compound OC=1C(=CC2=CC=CC=C2C1N=NC1=C(C=C(C=C1)C)S(=O)(=O)[O-])C(=O)[O-].[Na+].[Na+] VPWFPZBFBFHIIL-UHFFFAOYSA-L 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000005293 duran Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 235000010187 litholrubine BK Nutrition 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- POOWHPZIJIKCGX-UHFFFAOYSA-N C1(=CC=CC=C1)C.C(C)(=O)OCCC.C(C)O Chemical compound C1(=CC=CC=C1)C.C(C)(=O)OCCC.C(C)O POOWHPZIJIKCGX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- DWPDSISGRAWLLV-JHZYRPMRSA-L calcium;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Ca+2].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O.C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O DWPDSISGRAWLLV-JHZYRPMRSA-L 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- KZXPXALBICMWDJ-UHFFFAOYSA-N ethanol heptane propyl acetate Chemical compound CCCCCCC.C(C)(=O)OCCC.C(C)O KZXPXALBICMWDJ-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical class OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000012262 resinous product Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
- C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polyamides (AREA)
- Epoxy Resins (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Paints Or Removers (AREA)
Abstract
A printing ink which comprises a resin, a solvent, and a pigment, wherein the resin is a poly(amide-ester) with pendant hydroxyl groups.
Description
1 GB 2 133 024 A 1
SPECIFICATIONS
Printing ink This invention relates to a printing ink.
The preparation of polyamide resins from epoxy resins, dibasic acids, and polyamines is known. U.S.
Patent No. 3 308 076 teaches resinous polyamides prepared bythe steps of (1) esterifying an epoxy resin with a dibasic acid to form a carlSoxyl-terminated epoxy esterwhich is then (2) reacted with a polyaminetaform an amine-terminated polyamide.
Such productsare useful as adhesivesfor laminating films of Mylarand poly-ethylene, as disclosed in U.S.
Patent No. 3 207 653.---Mylar- is a Registered Trade Mark.
The present invention provides a printing inkwhich comprises a resin, a solvent, and a pigment, wherein the resin is a poly(amide-ester) with pendant hyd roxyl groups.
Our copending British Patent Application No. 8 109 70 (GB 2073222A) describes and claims thermoplas tic alcohol-solubie poly(amide-ester) resins having the following repeating unit:
0 0 0 0 OH 1 1. 11 11 1 O-C-D-C-NHR-NH-C-D-C-()-r'H2-C"-CH2-o, R 1 75 0-0-D-G-IIH-R-NH-C-D-C-O-CH -CH-CH -0- 11 11 2, 2 0 0 OR where D is an alkyl-substituted cyclohexenyl ring; R is an aliphatic chain, an aromatic nucleus, an alkyl substituted cyclohexyl ring, oran oxypropylene 80 repeating unit; and R' is a bisphenol A moiety, a novolac structure, or a glycol repeating unit; the said resin having an acid value of Oto 30, an aminevaiue of Oto 5, and a softening point of 85to 160'C.
Such poly(amide-ester) resins may be prepared by the steps of (1) reacting a dimerized fatty acid with a diamineto form a carboxyi-terminated polyamide resin which is then (2) reacted with an epoxy resin via the terminal epoxy groups to form a poly(amide ester) resin having secondary hydroxyl groups.
Preferably, a dimerizedfatty acid is reacted with a polyamine in the presence of a chain-terminating agent to form a ca rboxyl-pendant polyamide resin (step 1). The carboxyl groups are then reacted with an epoxy resin via the terminal epoxy groups in the presence of a catalyst. Secondary hydroxyl groups are generated in the epoxy ring-opening (step 2). The general reactions are asfollows:
Step 1 HOOC-D-COOH + H2WR-NI-12--->HO(OC - D - CONH - R -NH-CO-D-CO)n0H Step 2 HO(OC-D-CONH-R-NH-CO-D-CO)n0H+ H IC- C4-CH - O-Rl-O-CH,-CH-CH 1 1' 2 -' 1 2 0 9 OH -Q-C-D-C-.rti-R-NH-C-D-C-O-CH,-CII-CH,-01 R 01 10 0, 0, ' li - where D is an alkyl-substituted cyciohexenyl ring; R is an aliphatic chain, an aromatic nucleus, an alkylsubstituted cyclohexyl ring, oran oxypropylene repeating unit; R, is a bisphenol A moiety, a novolac 55 structure, or a glycol repeating unit; and n is preferably an integer of 2 to 20.
The dimerized fatty acids have the general formula HOOC-D-COOH where D is an alkyl-substituted cyclohexenyl ring. They are obtainable commercially from several manufacturers and have the following approximate composition:
monomer acids dimer acids trimer acids Weight % trace - 15 60-98 trace 25 Typical dimerized fatty acids include, but are not limited to, the following:
Crodym (Crosby Chemicals). T-18 Empols (Fimery Industries) 1014 1018 Unidyme 18 (Union Camp) Acids,' wt. - Monomer Dimer Trimer j 79 i 95 trace 83 79 18 4 17 18 The dimerized fatty acid is generally used in an amount between about40 and 88 percent, more preferably between about70 and 75 per cent, based on theweight of thetotal charge of reactants.
The polyamine component has the general formula H2N-R-NH2where R represents an aliphatic chain, an aromatic nucleus, an alkyl-substituted cyclohexyl ring, or an oxypropylene repeating unit. Typical examples include ethylenedlamine, propylenediamine, hexamethylene-diamine, isophoronediamine, and polyglycoidiamine. In addition to the diamine, a small amount oftriamine, such as diethylenetriamine, or a polyamine, such astriethylenetetra mine oftetraethylenepentamine, can be used, depending upon the functionality of the acid component. It is generally used in an amount between about 5 and 10 percent, more preferably between about 6 and 9 percent, based on the weight of the total charge of reactants.
The epoxy resin component hasthe general formula H2C-CH-CH -0-l-O-CH -CH-CH 2 2 where R' is a bisphenol A moiety, a novolac structure, 90, or a glycol repeating unit. It may be a bisphenol A-epichlorohydrin resin such as Shell's Epons, e.g. Epon 812 (epoxide equivalent of 150to 170), Epon 828 (epoxide equivalent of 180to 195), Epon 1001 (epoxide equivalent of 425to 550), and Epon 1004 (epoxide equivalent of 875 to 1025), and Dow's DER 331 (epoxide equivalent of 182to 190) and DER 383 (epoxide equivalent of 178 to 186); a novolac-type epoxy resin such as Dow's DEN 431 (epoxide equivalent of 172 to 179) and DEN 438 (epoxide equivalent of 176to 181); or a polyglycol-type epoxy resin such as Dow's DER 732 (epoxide equivalent of 305to 335) and DER 736 (epoxide equivalent of 175 to 205). In general the epoxy resin is used in an amount of about 5 to 50 per cent, more preferably about 10 to 20 per cent, based on the weight of the total charge of reactants.
In addition a small amount of a monoepoxide, such as an aliphatic glycidyl ether containing C8-C14 alkyl groups, can be used.
Instep 1 of the process a chain-terminating agent maybe used to control the molecularweight of the product, thus improving the solubility of the product in alcohols, such as ethanol, n-propanol, or isopropa- 2 GB 2 133 024 A 2 noL Suitable agents are monobasic acids such as acetic acid, propionic acid, and acids having about 3 to 18 carbon atoms in the chain. The agent is used in an amount between about 2 to 10 per cent, and preferably between about 4 to 6 per cent, based on the weight of the total charge of reactants.
In step 2 of the process a catalyst may be used to achieve a high esterification rate. Typical catalysts includetertiary amines such as N,Ndimethylbenzyla- mine ortri-n-butylamine, rare earth oxides such as cerium oxide or lanthanum oxide, and transition metal salts such as chromium acetate or zirconium octoate.
Thetemperature employed in step 1 may range from about 150to 2250C, more preferablyfrom about 175to 200'C. In step 2 it is generally between about 100 and 150'C., more preferably between about 115 and 140'C. The product poly(amide-ester) resins are tough and yetflexible. They have acid values of about Oto 30, and preferably about Oto 15 mg. KOH/gm. resin; amine values of about 0 to 5, and preferably about 0 to 3 mg. KOH/9m. resin; and softening points between about 85 and 160'C., and preferably between bout 95 and 135'C. They are soluble in higher alcohols and blends of alcohois with hydrocarbon or ester solvents, and they have a useful compatability rangewith nitrocellulose.
Printing inks having excellent adhesionto difficult plasticand metallic surfaces, high heat resistance, and crosslinking potential are possible when these poly(amide-esters) areinciLided in the formulations. Forexample,when used asthevehicle inflexographicorgravure inks,the resinous productsof this invention impartimproved gloss, adhesion, scuff resistance, and heat resistance. When they are reacted with limed rosin for publication gravure inks, high gloss and scuff resistance resu It.
Becausethese resinous products contain secondary hydroxyl groups (generated by ring-opening of the epoxy groups), they can ester-interchange with othersuitable resins, such as alkyds or polyesters, to enhancethe adhesion, gloss, and scuff resistance of the end product.
They also are potential vehicles forwater-based inks. By reacting the hydroxyl groups with an anyhydride, water solubility or water dispersibility can be obtained through saitformation by neutralizing with an aorganic base the free carboxyl groups (formed by ring-opening of the anhydride) of the product. An organic oxide, such as ethylene oxide, can also be added to achieve water solu bility.
The poly(amide-ester) resins of this invention can also be used as ultraviolet-reactive vehicles or as additive resinsfor UV applications. Their hydroxyl groups can reactwith polyisocyanates and hydroxyl acrylates, resulting in urethanated-acrylated amideesters.
The invention is illustrated bythefollowing examples in which all parts and percentages are byweight unless otherwise specified.
EXAMPLE 1 (A) Into a one-1 iter fou r-nekced Pyrex flask equipped with an agitator, a moisture trap, a nitrogen inlet tube, and a water-cooled condenser were charged 395.5 parts of a dimerizedfatty acid (Crosby Chemic- als'Crodym T-18),24.8 parts of propionic acid (99% purity), and 3 drops of an antifoarn agent (Dow Corning's DC-200 silicone fluid). The reactants were heated under nitrogen to 50'C., and 25.3 parts of ethylenediamine (99% purity), was added. The exotherm raised the temperature to 1 OOOC.; the temperture then was brought to 110-1 200C. and held for one hour. The resultant polymeric salt was dehydrated and waterwas distilled off at 140-200'C. to obtain an acid-terminatedpolyamide resin having an acid value of 100-110 and an aminevalueof 0.1.
(B) The product of part (A) was cooled to 1201300C., and 155.0 parts of a bisphenol A-epichlorohydrin resin (Shell's Epon 828) and 0.6 part of N,N-dimethyl-benzylamine were added. The reaction was held at 120-140'C. until the acid value of the productwas less than 10.
The productwas an amber-coloured tough poly(amide-ester) resin, somewhat rubbery at room temperature, having these properties:
propanol acidvalue aminevalue Duran's softening point,'C. Gardener viscosity 25C. (!'P40% solids in n- f 7.3 0 98 G EX4MPLE 2 (A) Into a one-literfour-necked Pyrex flask equippedwith an agitator, a moisturetrap, a nitrogen inlet tube, and a water-cooled condenserwere charged 472.0 parts of a dimerized fatty acid (Crodym T-18), 29.6 pails of propionic acid (99% purity), and 5 drops of an antifoam agent (DC-200). The reactants were heated under nitrogen to 50C., and 42.2 parts of ethylenediamine (99% purity) was added. The temperaturewas raised by exotherm to 90-1 OO'C.; it was then broughtto 11 VC. and held for one hour. The resultant polymeric salt was dehydrated and water was distilled off at 140-200'C. to obtain an acidterminated polyamide resin having an acid value of 60-65 and an amine value of 0.1.
(B) The product of part (A) was cooled to 1301350C., and 110.0 parts of a bisphenol A-epichlorohydrin resin (Epon 828) and 0.6 part of N,Ndimethylbenzylaminewere added. The reaction was held at 120-135C. until the acidvalue of the product was about 10. The product was a poly(amide-ester) resin which was poured onto a trayto cool and solidify and subsequentlywas crushed.
The product was an amber-coloured resin, some- what harder and less rubberythan the product of Example 1, having these properties: acidvalue aminevalue Duran's softening point, C, Gardner viscosity 250C. @ 40% solids in n propanol 10.9 1.1 115-116 D+ EXAMPLE 3
The procedure of Example 1 was repeated with each of the following instead of Crodym TA 8:
Unidyme 18 (Union Camp's dimerized fatty acid) and Emery Inclustries'di merized fatty acids Empol 1014 and Empol 1018. the results were comparable. EXAMPLE 4 The procedure of Example 1 was repeated with each of the following epoxy resins instead of the S .i 3 GB 2 133 024 A 3 bisphenol A-epichlorohydrin Epon 828: bisphenol A-type epoxy resins Epon 812, Epon 1001, and Epon 1004 (Shell) and DER 331 and DER 383 (Dow); novolac-type epoxy resins DEN 431 and DEN 438 5 (Dow); and polyglycoltype epoxy resins DER 732 and DER 736. The results were comparable. EXAMPLE 5 The procedure of Example 1 was repeated with each of thefollowing polyamines instead of ethylene10 diamine: propylenediamine, hexamethylenediamine, and isophorone-diamine. The results were comparable.
EX4/14PLE 6 Theprocedureof Example 1 was repeatedwith acetic acid instead of propionic acid. The results were comparable.
Example 7
Aflexographic inkwas formulated from the following ingredients:
product of Example 1 Lithol Rubine nitrocellulose polyethylenewax ethanol n-propyl acetate heptane It showed high gloss, good adhesion, good scuff resistance, and good heat resistance on corona- treated polyolefin films and on papers.
EXAMPLE 8
A gravure inkwas formulated from the following ingredients:
product of Example 2 Lithol Rubine nitrocellulose polyethylenewax ethanol n-propyl acetate toluene It showed high gloss, good adhesion, good scuff resistance, and good heat resistance on coronatreated polyolefin films and on papers.
Claims (2)
1. A printing ink which comprises a resin, a solvent, and a pigment, wherein the resin is a poly(amide-ester) with pendant hydroxyl groups.
New or amended claims-:
Parts 14.0 15.0 5.0 1.0 40.0 15.0 10.0 Parts 14.0 10.0 5.0 1.0 30.0 15.0 25.0 1. A printing ink which comprises a resin, a solvent, and a pigment, wherein the resin is a poly(amide-ester) with pendant hydroxyl groups.
2. A printing ink according to claim 1, substantially as herein described in any of the foregoing examples.
Printed for Her Majesty's Stationery Office byTheTweeddate Press Ltd., Berwick-upon-Tweed, 1984. Published atthe Patent Office, 25 Southampton Buildings, London WC2A lAY, from which copies may be obtained.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13297380A | 1980-03-24 | 1980-03-24 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8321948D0 GB8321948D0 (en) | 1983-09-14 |
| GB2133024A true GB2133024A (en) | 1984-07-18 |
| GB2133024B GB2133024B (en) | 1985-01-16 |
Family
ID=22456447
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8109190A Expired GB2073222B (en) | 1980-03-24 | 1981-03-24 | Poly(amide-ester)resins |
| GB08321948A Expired GB2133024B (en) | 1980-03-24 | 1983-08-15 | Printing ink |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8109190A Expired GB2073222B (en) | 1980-03-24 | 1981-03-24 | Poly(amide-ester)resins |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS56147826A (en) |
| AU (1) | AU543180B2 (en) |
| BE (1) | BE888026A (en) |
| DE (1) | DE3110277A1 (en) |
| FR (1) | FR2478651A1 (en) |
| GB (2) | GB2073222B (en) |
| IT (1) | IT1136571B (en) |
| MX (1) | MX158102A (en) |
| NL (1) | NL190900C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3616824A1 (en) * | 1986-05-17 | 1987-11-19 | Schering Ag | USE OF CURABLE RESIN MIXTURES FOR SURFACE COATINGS AND PRINTING INKS AND METHOD FOR THE PRODUCTION THEREOF |
| US4873311A (en) * | 1988-02-05 | 1989-10-10 | Union Camp Corporation | Water dispersible polyamide ester |
| JP2664211B2 (en) * | 1988-07-13 | 1997-10-15 | 関西ペイント株式会社 | Curable paint |
| JPH06102711B2 (en) * | 1989-04-28 | 1994-12-14 | ダウ・ケミカル日本株式会社 | Method for producing polyamide epoxy ester resin |
| US5216115A (en) * | 1990-06-12 | 1993-06-01 | Rutgers, The State University Of New Jersey | Polyarylate containing derivatives of the natural amino acid L-tyrosine |
| EP2072556A1 (en) * | 2007-12-17 | 2009-06-24 | Sika Technology AG | Method for creating hydroxyfunctional polymers, the isocyanate group terminal polyaddition products which can be gathered from them and their production |
| CN107641372B (en) * | 2017-11-09 | 2021-06-08 | 安庆巨元高分子材料科技有限公司 | Preparation method of alcohol-soluble polyamide resin ink |
| US10974226B2 (en) | 2018-09-24 | 2021-04-13 | Sabic Global Technologies B.V. | Catalytic process for oxidative coupling of methane |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3308076A (en) * | 1961-07-28 | 1967-03-07 | Interchem Corp | Polyamides produced from polyepoxides, dimeric fatty acids and polyamines |
| BE630369A (en) * | 1962-06-22 | |||
| US3383391A (en) * | 1963-12-19 | 1968-05-14 | Sun Chemical Corp | Imide terminated polyamide resins useful in inks |
| BE758369R (en) * | 1969-11-04 | 1971-05-03 | Wolf Ltd Victor | PROCESS FOR PREPARING POLYESTER-AMIDES AND COMPOUNDS |
| DE2128984A1 (en) * | 1971-06-11 | 1973-01-04 | Schering Ag | LAMINABLE INK RESIN ON A POLYAMIDE BASE |
| DE2462453C2 (en) * | 1973-09-27 | 1983-09-08 | Dai Nippon Toryo Co., Ltd., Osaka | Polyamides and their use for curing aqueous epoxy resin paints |
| DE2635226C2 (en) * | 1976-08-05 | 1985-09-19 | Schering AG, 1000 Berlin und 4709 Bergkamen | Printing processes and suitable melt printing inks |
| DE2756469A1 (en) * | 1977-12-17 | 1979-06-21 | Bayer Ag | Amide group-containing polyamines |
| JPS559651A (en) * | 1978-07-06 | 1980-01-23 | Kao Corp | Production of polyamide soluble in alcohol |
| NL9000645A (en) * | 1990-03-20 | 1991-10-16 | Stork Screens Bv | METHOD FOR MANUFACTURING A ROLLER AND THUS OBTAINED ROLLER |
-
1981
- 1981-03-11 MX MX186317A patent/MX158102A/en unknown
- 1981-03-17 AU AU68424/81A patent/AU543180B2/en not_active Ceased
- 1981-03-17 DE DE19813110277 patent/DE3110277A1/en active Granted
- 1981-03-18 FR FR8105379A patent/FR2478651A1/en active Granted
- 1981-03-19 BE BE0/204188A patent/BE888026A/en not_active IP Right Cessation
- 1981-03-20 JP JP4158881A patent/JPS56147826A/en active Granted
- 1981-03-20 IT IT20653/81A patent/IT1136571B/en active
- 1981-03-24 GB GB8109190A patent/GB2073222B/en not_active Expired
- 1981-03-24 NL NL8101458A patent/NL190900C/en not_active IP Right Cessation
-
1983
- 1983-08-15 GB GB08321948A patent/GB2133024B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| MX158102A (en) | 1989-01-09 |
| AU6842481A (en) | 1981-10-01 |
| IT8120653A0 (en) | 1981-03-20 |
| AU543180B2 (en) | 1985-04-04 |
| JPS56147826A (en) | 1981-11-17 |
| IT1136571B (en) | 1986-09-03 |
| FR2478651A1 (en) | 1981-09-25 |
| GB2133024B (en) | 1985-01-16 |
| GB2073222A (en) | 1981-10-14 |
| BE888026A (en) | 1981-09-21 |
| GB8321948D0 (en) | 1983-09-14 |
| NL190900B (en) | 1994-05-16 |
| FR2478651B1 (en) | 1984-11-09 |
| DE3110277A1 (en) | 1982-03-18 |
| NL8101458A (en) | 1981-10-16 |
| JPS638998B2 (en) | 1988-02-25 |
| DE3110277C2 (en) | 1989-08-24 |
| GB2073222B (en) | 1984-08-08 |
| NL190900C (en) | 1994-10-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19980324 |