WO1997035837A1 - Liquid photo initiators - Google Patents
Liquid photo initiators Download PDFInfo
- Publication number
- WO1997035837A1 WO1997035837A1 PCT/SE1997/000519 SE9700519W WO9735837A1 WO 1997035837 A1 WO1997035837 A1 WO 1997035837A1 SE 9700519 W SE9700519 W SE 9700519W WO 9735837 A1 WO9735837 A1 WO 9735837A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- amyl
- curing
- technical
- dimethylamino
- benzoic acid
- Prior art date
Links
- 239000003999 initiator Substances 0.000 title claims abstract description 35
- 239000007788 liquid Substances 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 30
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 17
- YDIYEOMDOWUDTJ-UHFFFAOYSA-N 4-(dimethylamino)benzoic acid Chemical compound CN(C)C1=CC=C(C(O)=O)C=C1 YDIYEOMDOWUDTJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003847 radiation curing Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000003848 UV Light-Curing Methods 0.000 claims description 21
- KLXQAXYSOJNJRI-KVTDHHQDSA-N (2s,3s,4r,5r)-5-amino-2,3,4,6-tetrahydroxyhexanal Chemical compound OC[C@@H](N)[C@@H](O)[C@H](O)[C@H](O)C=O KLXQAXYSOJNJRI-KVTDHHQDSA-N 0.000 claims description 19
- 101000651373 Homo sapiens Serine palmitoyltransferase small subunit B Proteins 0.000 claims description 19
- 102100027676 Serine palmitoyltransferase small subunit B Human genes 0.000 claims description 19
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 19
- -1 isoamyl alcohols Chemical class 0.000 claims description 14
- 239000001760 fusel oil Substances 0.000 claims description 7
- 150000001555 benzenes Chemical class 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000012965 benzophenone Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 150000008366 benzophenones Chemical class 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001723 curing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- LXTZRIBXKVRLOA-UHFFFAOYSA-N padimate a Chemical compound CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 LXTZRIBXKVRLOA-UHFFFAOYSA-N 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical class CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-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
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OFSAUHSCHWRZKM-UHFFFAOYSA-N Padimate A Chemical compound CC(C)CCOC(=O)C1=CC=C(N(C)C)C=C1 OFSAUHSCHWRZKM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical group CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000005932 reductive alkylation reaction Methods 0.000 description 1
- 238000006485 reductive methylation reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000606 suspected carcinogen Toxicity 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
Definitions
- the invention is relating to photo initiators for radiation curing, such as UV curing, comprising liquid rnixtures of benzene derivatives prepared from chemical mixtures comprising technical amyl alcohols.
- UV curing is regarded as a modern, cost efficient and environmental-friendly way of "drying" coatings, lacquers, adhesives, printing inks, resists, etc. Unlike conventional industrial curing using heat and organic solvents, no heat is necessary and there are no harmful organic solvents evaporating during the UV curing.
- polymerizable monomers, oligomers, and binders are together making up the liquid matrix. When exposed to UV light this liquid matrix is cured, i.e. photochemically converted into solid polymer.
- the UV light has to be absorbed by photochemically active centers which need to be present in the formulations.
- photo initiators UV curing takes place within a fraction of a second.
- UV curing of acrylates by free radical chemistry is the most frequently used UV curing technology. Free radicals are generated in UV light by photo initiators. These free radicals are attached to acrylic unsaturations in the UV curable formulations giving fast polymerizations, i.e. UV curing.
- UV curing One major limiting factor for the use of UV curing is the high costs of some ofthe components, especially the photo initiators.
- Unsubstituted benzophenone is the most frequently used photo inititator. The main reason is its comparatively low price and its curing efficiency. However, the said benzophenone has a serious drawback in respect of its smell. Products cured by benzophenone in UV light can often be recognized by the smell of residual benzophenone. This smell is a problem in food packaging. In packaging applications wherein the smell cannot be tolerated, other types of photo initiators, considerably more expensive, than benzophenone have to be used. Such a replacement ofthe cheap benzophenone with more expensive ones increases the price ofthe curing formulations.
- Non-toxic benzophenone derivatives used as photo initiators, are produced from comparatively expensive aromatic raw materials. The said derivatives are considerably more expensive than conventional unsubstituted benzophenone.
- Unsubstituted benzophenone is prepared e.g. from benzoic acid and benzene.
- 4-Methyl- benzophenone is a commercially available substance analogously prepared from 4-methyl- benzoic acid. These two substances are solids at room temperature.
- 2,4,6-Trimethylbenzophenone is a commercially available solid substance marketed as a liquid eutectic mixture with 4-methylbenzophenone. It is prepared from 1,3,5-trimethylbenzene and benzoic acid.
- UV curing is not sufficiently efficient compared to the curing with unsubstituted benzophenone with respect to the price differences.
- Solid benzophenones do not lead to handling cost advantages.
- Michler's ketone a very efficient benzophenone, is a suspected carcinogen.
- alkyl esters of p-dimethylaminobenzoic acids are used as photo sensibility agents and according to EP 0003872 the compound 2-(n-butoxy)ethyl 4 dimethylaminobenzoate is known as photoactivator.
- the odourless liquid mixtures according to the invention comprising amyl esters of 4-(dimethylamino)benzoic acid prepared from the commercially available, inexpensive technical amyl and isoamyl alcohols.
- EDMP ethyl 4-(dimethylamino)benzoate
- EDMP is prepared from ethanol.
- Other structurally related initiators are e.g. isoamyl 4-(dimethylamino)benzoate, and amyl 4- (dimethylamino)benzoate, prepared from isoamyl and amyl alcohols respectively. Said compounds are comparatively expensive for the manufacturer as they require pure alcohols as starting materials. Therefore, there is a market need for new, liquid, efficient photo initiators, low in price and having good smell characteristics. Description ofthe invention
- low cost organic raw materials are used in the manufacturing of liquid, efficient photo initiators having good smell characteristics to be used in radiation curing, especially in UV curing.
- substituted olefins comprises such olefins as esters of acrylic and methacrylic acid.
- radiation curing relates mainly to UV curing but also curing in visible light may be appropriate.
- “Technical amyl alcohol” refers to commercially available technical products consisting mainly of n-pentanol and methyl- 1-butanols.
- “Technical isoamyl alcohol” refers to commercially available technical products, mainly fusel oil from ethanol fermentation, consisting mainly of isoamyl alcohol and methyl- 1-butanols.
- mixtures of benzene derivatives chemically prepared from inexpensive, impure, technical organic raw materials and selected from the group consisting of technical amyl alcohols, and technical isoamyl alcohol are liquid and act as photo initiators in radiation curing of free radical curable systems, such as substituted olefins.
- the liquid mixtures are especially preferred as photo initiators in UV curing.
- the invention relates, according to one embodiment, defined in claims 1 to 4, to liquid mixtures of amyl esters of 4-(dimethyIamino)benzoic acid having good smell characteristics when used as photo initiators in radiation curing, especially UV curing.
- Said esters are prepared from technical amyl alcohol or from technical isoamyl alcohol.
- Another embodiment, defined in claims 5 to 6, relates to photo initiators comprising the liquid mixtures as defined in claims 1 to 4 and a third embodiment, defined in claim 7, to the use of technical amyl and isoamyl alcohols for the preparation of liquid amyl esters of 4- (dimethylamino)benzoic acid having good small characteristics.
- amyl alcohols selected from the group consisting of technical isoamyl alcohol and technical amyl alcohol can be used as organic low cost raw materials for the manufacturing of amyl 4-(dimethylamino)benzoates.
- Products consisting of esters derived from technical isoamyl alcohol are below named LADMP and the products derived from technical amyl alcohol ADMP.
- LADMP and ADMP are derived from the different alcohols present in the alcohol raw materials as used.
- IADMP and ADMP have the following unknown characteristics:
- IADMP and ADMP are initiators in UV curing. Their efficiency is ofthe same magnitude as EDMP.
- IADMP and ADMP have improved smell characteristics relative to EDMP.
- IADMP and ADMP are liquid at ambient temperature in contrast to the conventionally used EDMP, which is a solid.
- fusel oil is a by-product from ethanol fermentation. It is normally discharged thus being a cost ofthe fermentation process. It has by the present invention been shown that said fusel oil is an excellent inexpensive raw material for IADMP.
- R represents an alkyl or branched alkyl group containing 5 carbon atoms.
- Step 1 is an esterification catalyzed by a strong acid like sulfuric acid or an organic sulfonic acid, such as p-toluenesulfonic or methanesulfonic acid.
- a strong acid like sulfuric acid or an organic sulfonic acid, such as p-toluenesulfonic or methanesulfonic acid.
- Step 2 is a reduction of a nitro compound to the corresponding primary amine using hydrogen as reducing agent along with a reduction catalyst such as a nobel metal, for example palladium, on a support, or nickel, metallic or on a support.
- a reduction catalyst such as a nobel metal, for example palladium, on a support, or nickel, metallic or on a support.
- Step 3 is a reductive alkylation using formaldehyde as alkylating reagent with use ofthe same catalysts as in step 2.
- Formaldehyde is added as a solution in water or in an alcohol.
- the residue was distilled twice.
- the main fraction distilled at 155-159 °C/0,3 mmHg.
- the product was called ADMP 151/27C.
- Example 1 was repeated using an excess of 4-nitrobenzoic acid. The excess was removed by alkaline extraction before reduction. Evaporation of toluene from the washed methylated solution gave the end product ADMP 151/27B.
- Example 3 (Preparation of IADMP) p-Nitrobenzoic acid, 1055 g, was esterified as described in Example 1 starting from 636 g of technical isoamyl alcohol (fusel oil), 525 g of toluene and 28,5 g of p-toluenesulfonic acid monohydrate.
- ADMP and IADMP from examples 1, 2, and 3 were compared with each other and with
- the photo initiators were evaluated in a blue pigmented UV curable printing ink formulation. 2 grams m of each formulation was applied on a corona treated white polyethylene film. The
- UV curing was performed with a 120 W/cm Fusion UV lamp at two different speeds (80 and
- the cured inks were evaluated with regard to ethanol rubs, surface dryness, scratch resistance, tape resistance, and smell.
- the blue pigmented inks were formulated accordingly: 32 % polyester acrylate 30 % tetrafunctional acrylate 10 % amino modified polyetheracrylate 0,5 % stabilizer
- ADMP 151/27B technical amyl alcohol (pentanol isomer not distilled liquid at -24°C 80 5 3 3 5 3 mixture)
- ADMP 151 /27C technical amyl alcohol penentanol isomer distilled liquid at -24°C 80 5 4 3 5 4 mixture
- IADMP technical isoamyl alchohol (fusel oil) distilled liquid at room 120 4 3 2 5 3 151/27A temperature
- ADM 151 /27C technical amyl alcohol penentanol isomer distilled liquid at -24°C 120 3 2 2 5 4 mixture
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU25249/97A AU2524997A (en) | 1996-03-25 | 1997-03-25 | Liquid photo initiators |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE9601145A SE508191C2 (sv) | 1996-03-25 | 1996-03-25 | Flytande blandningar av bensenderivat med bra luktegenskaper som fotoinitiatorer vid strålningshärdning |
| SE9601145-7 | 1996-03-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1997035837A1 true WO1997035837A1 (en) | 1997-10-02 |
Family
ID=20401942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/SE1997/000519 WO1997035837A1 (en) | 1996-03-25 | 1997-03-25 | Liquid photo initiators |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU2524997A (sv) |
| SE (1) | SE508191C2 (sv) |
| WO (1) | WO1997035837A1 (sv) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105067746A (zh) * | 2015-08-05 | 2015-11-18 | 中国检验检疫科学研究院 | 化妆品中帕地马酯的测定方法 |
| US9522967B2 (en) | 2006-06-09 | 2016-12-20 | Dentsply International Inc. | Photopolymerizable compositions featuring novel amine accelerator for improved color stability and reduced polymerization stress thereby |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2458345A1 (de) * | 1974-12-10 | 1976-06-16 | Basf Ag | Photopolymerisierbare bindemittel fuer druckfarben und ueberzugsmassen |
| EP0209831A2 (en) * | 1985-07-23 | 1987-01-28 | FRATELLI LAMBERTI S.p.A. | Substituted benzophenones and their liquid mixtures suitable for use as photopolymerisation initiators |
| GB2233975A (en) * | 1989-07-19 | 1991-01-23 | Lambson Ltd | Preparation of optionally substituted alkyl-p-dimethylamino benzoates |
| EP0435536A2 (en) * | 1989-12-14 | 1991-07-03 | Canon Kabushiki Kaisha | Adhering an ink jet recording head using photopolymerisable adhesive |
| WO1994025532A1 (en) * | 1993-04-30 | 1994-11-10 | Dusa Pharmaceuticals, Inc. | Sunscreen product and process for the production thereof |
-
1996
- 1996-03-25 SE SE9601145A patent/SE508191C2/sv not_active IP Right Cessation
-
1997
- 1997-03-25 AU AU25249/97A patent/AU2524997A/en not_active Abandoned
- 1997-03-25 WO PCT/SE1997/000519 patent/WO1997035837A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2458345A1 (de) * | 1974-12-10 | 1976-06-16 | Basf Ag | Photopolymerisierbare bindemittel fuer druckfarben und ueberzugsmassen |
| EP0209831A2 (en) * | 1985-07-23 | 1987-01-28 | FRATELLI LAMBERTI S.p.A. | Substituted benzophenones and their liquid mixtures suitable for use as photopolymerisation initiators |
| GB2233975A (en) * | 1989-07-19 | 1991-01-23 | Lambson Ltd | Preparation of optionally substituted alkyl-p-dimethylamino benzoates |
| EP0435536A2 (en) * | 1989-12-14 | 1991-07-03 | Canon Kabushiki Kaisha | Adhering an ink jet recording head using photopolymerisable adhesive |
| WO1994025532A1 (en) * | 1993-04-30 | 1994-11-10 | Dusa Pharmaceuticals, Inc. | Sunscreen product and process for the production thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9522967B2 (en) | 2006-06-09 | 2016-12-20 | Dentsply International Inc. | Photopolymerizable compositions featuring novel amine accelerator for improved color stability and reduced polymerization stress thereby |
| US9944723B2 (en) | 2006-06-09 | 2018-04-17 | Dentsply Sirona Inc. | Photopolymerizable compositions featuring novel amine accelerator for improved color stability and reduced polymerization stress thereby |
| CN105067746A (zh) * | 2015-08-05 | 2015-11-18 | 中国检验检疫科学研究院 | 化妆品中帕地马酯的测定方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2524997A (en) | 1997-10-17 |
| SE9601145D0 (sv) | 1996-03-25 |
| SE508191C2 (sv) | 1998-09-14 |
| SE9601145L (sv) | 1997-09-26 |
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