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WO1997035837A1 - Photoamorceurs liquides - Google Patents

Photoamorceurs liquides Download PDF

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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
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.)
Ceased
Application number
PCT/SE1997/000519
Other languages
English (en)
Inventor
Anders Boberg
Ingemar Ander
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.)
NORDIC SYNTHESIS AB
Original Assignee
NORDIC SYNTHESIS AB
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.)
Filing date
Publication date
Application filed by NORDIC SYNTHESIS AB filed Critical NORDIC SYNTHESIS AB
Priority to AU25249/97A priority Critical patent/AU2524997A/en
Publication of WO1997035837A1 publication Critical patent/WO1997035837A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention se rapporte à des mélanges liquides d'esters amyle de l'acide 4-(diméthylamino)benzoïque préparés à partir d'alcool amylique industriel et servant de photoamorceurs dans le durcissement par rayonnement; à des photoamorceurs comprenant des mélanges liquides; et à l'utilisation de l'alcool amylique industriel dans la préparation d'esters amyle de l'acide 4-(diméthylamino)benzoïque.
PCT/SE1997/000519 1996-03-25 1997-03-25 Photoamorceurs liquides Ceased WO1997035837A1 (fr)

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
SE9601145-7 1996-03-25
SE9601145A SE508191C2 (sv) 1996-03-25 1996-03-25 Flytande blandningar av bensenderivat med bra luktegenskaper som fotoinitiatorer vid strålningshärdning

Publications (1)

Publication Number Publication Date
WO1997035837A1 true WO1997035837A1 (fr) 1997-10-02

Family

ID=20401942

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1997/000519 Ceased WO1997035837A1 (fr) 1996-03-25 1997-03-25 Photoamorceurs liquides

Country Status (3)

Country Link
AU (1) AU2524997A (fr)
SE (1) SE508191C2 (fr)
WO (1) WO1997035837A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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 (fr) * 1985-07-23 1987-01-28 FRATELLI LAMBERTI S.p.A. Benzophénones substituées et leurs mélanges liquides utilisables comme initiateur de photopolymérisation
GB2233975A (en) * 1989-07-19 1991-01-23 Lambson Ltd Preparation of optionally substituted alkyl-p-dimethylamino benzoates
EP0435536A2 (fr) * 1989-12-14 1991-07-03 Canon Kabushiki Kaisha Collage de tête d'enregistrement à jet d'encre avec un adhésif photopolymérisable
WO1994025532A1 (fr) * 1993-04-30 1994-11-10 Dusa Pharmaceuticals, Inc. Produit antisolaire et procede pour sa preparation

Patent Citations (5)

* Cited by examiner, † Cited by third party
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 (fr) * 1985-07-23 1987-01-28 FRATELLI LAMBERTI S.p.A. Benzophénones substituées et leurs mélanges liquides utilisables comme initiateur de photopolymérisation
GB2233975A (en) * 1989-07-19 1991-01-23 Lambson Ltd Preparation of optionally substituted alkyl-p-dimethylamino benzoates
EP0435536A2 (fr) * 1989-12-14 1991-07-03 Canon Kabushiki Kaisha Collage de tête d'enregistrement à jet d'encre avec un adhésif photopolymérisable
WO1994025532A1 (fr) * 1993-04-30 1994-11-10 Dusa Pharmaceuticals, Inc. Produit antisolaire et procede pour sa preparation

Cited By (3)

* Cited by examiner, † Cited by third party
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
SE9601145L (sv) 1997-09-26
SE9601145D0 (sv) 1996-03-25
SE508191C2 (sv) 1998-09-14
AU2524997A (en) 1997-10-17

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