WO1994028075A1 - Composition de revetement comportant un catalyseur basique active par les uv - Google Patents

Composition de revetement comportant un catalyseur basique active par les uv Download PDF

Info

Publication number
WO1994028075A1
WO1994028075A1 PCT/EP1994/001451 EP9401451W WO9428075A1 WO 1994028075 A1 WO1994028075 A1 WO 1994028075A1 EP 9401451 W EP9401451 W EP 9401451W WO 9428075 A1 WO9428075 A1 WO 9428075A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating composition
basic catalyst
composition according
activated
group
Prior art date
Application number
PCT/EP1994/001451
Other languages
English (en)
Inventor
Huig Klinkenberg
Arie Noomen
Original Assignee
Akzo Nobel N.V.
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 Akzo Nobel N.V. filed Critical Akzo Nobel N.V.
Priority to EP94916207A priority Critical patent/EP0702707A1/fr
Priority to CA002163875A priority patent/CA2163875A1/fr
Publication of WO1994028075A1 publication Critical patent/WO1994028075A1/fr
Priority to FI955613A priority patent/FI955613A/fi
Priority to NO954787A priority patent/NO954787L/no

Links

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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16

Definitions

  • the present invention relates generally to coating compositions based upon (A) compounds containing activated unsaturated groups and (B) compounds containing activated CH groups.
  • compositions are, in general, known from a number of references including US2759913, DE-PS-835809, US4871822 (EP-A-0160824) , US4602061, US4408018, US4217396 (GB-A-2048913) and EP-A-0448154, all of which are incorporated by reference herein for all purposes.
  • US2759913 and US4871822 generally disclose a composition of the above type which may be cured at ambient and elevated temperatures. More specifically, these references generally describe, as component (A), compounds containing at least two activated ethylenic double bonds and, as component (B), a wide variety of compounds including those containing at least two activated methylene and/or monosubstituted methylene groups.
  • US4602061 discloses a similar composition except that, as component (B), are specifically mentioned malonic group-containing oligomeric and polymeric esters.
  • thermosetting applications One alternative for overcoming this problem in thermosetting applications is described in aforementioned EP-A-0448154, in which the basic catalyst is blocked with a particular carboxylic acid which is volatile and/or undergoes decarboxylation under curing conditions. While providing good results for elevated cure conditions, this system is not generally applicable at ambient temperatures. It is, therefore, difficult to utilize these systems for heat sensitive substrates such as wood and thermoplastic polymers, as well as in industrial and non-industrial applications like decorative coatings and refinish paints.
  • the present invention provides such an alternative by utilizing a system which is curable under the influence of UV light.
  • the present invention relates to a coating composition
  • a coating composition comprising (A) an activated unsaturated group-containing compound, (B) an activated CH group-containing compound and (C) a basic catalyst, characterized in that the basic catalyst (C) is blocked with an acidic compound whereby the so-blocked catalyst becomes unblocked under the influence of UV light having a wavelength in the range from 250-500 nm.
  • UV-deblockable basic catalysts are in general known from US4301186, US4369206, DE-A-2940333 and DE-A-2940332, all of which are incorporated by reference herein for all purposes as if fully set forth. The suitability of such blocked catalysts for use in Michael addition curing coating systems, however, is not evident from any of the above-mentioned disclosures.
  • the coating compositions in accordance with the present invention are in general suitable for a variety of coatings uses, for example, as paint, impregnating, sealing and bonding compositions. They are especially suited for use as semi-one pack decorative coatings and as clearcoats in basecoat/clearcoat systems for refinish applications (e.g., for automotive refinishes).
  • coating compositions possess extended potlife, good curing speed upon exposure to UV light (wavelength of 250-500 nm), and a good balance of physical and mechanical properties making them especially well suited for the aforementioned uses.
  • the coating compositions in accordance with the present invention are based upon (A) activated unsaturated group-containing compounds, (B) activated CH group-containing compounds and (C) a basic catalyst, which basic catalyst is blocked in a manner more fully described below.
  • suitable compounds containing activated unsaturated groups may generally be mentioned ethylenically unsaturated compounds in which the carbon-carbon double bond is activated by a carbonyl group in the ⁇ -position.
  • ethylenically unsaturated compounds in which the carbon-carbon double bond is activated by a carbonyl group in the ⁇ -position.
  • those compounds disclosed in previously incorporated US2759913 see especially column 6, line 35 through column 7, line 45
  • DE-PS-835809 see especially column 3, lines 16-41
  • US4871822 see especially column 2, line 14 through column 4, line 14
  • US4602061 see
  • ( eth)acrylic esters of compounds containing 1-6 hydroxyl groups and 1-20 carbon atoms.
  • (meth)acrylic acid may be used, for example, crotonic acid and cinnamic acid. These esters may optionally contain hydroxyl groups.
  • Especially preferred examples include hexane
  • diol diacrylate trimethylol propane triacrylate and pentaerythritol triacrylate.
  • polyester and/or alkyd resins containing pendant activated unsaturated groups include, for example, urethane (meth)acrylates obtained by reaction of a polyisocyanate with an hydroxyl group-containing (meth)acrylic ester, e.g., an hydroxyalkyl ester of (meth)acrylic acid or a compound prepared by esterification of a polyhydroxyl compound with less than a stoichiometric amount of (meth)acrylic acid; polyether (meth)acrylates obtained by esterification of an hydroxyl group-containing polyether with ( eth)acrylic acid; polyfunctional (meth)acrylates obtained by reaction of an hydroxyalkyl (meth)acrylate with a polycarboxylic acid and/or a polyamino resin; poly(meth)acrylates obtained by reaction of (meth)acrylic acid with an epoxy resin; and polyalkylmaleates obtained by reaction of a monoalkyl aleate
  • activated unsaturated group-containing compounds are the aforementioned poly(meth)acrylates obtained by the reaction of (meth)acrylic acid with an epoxy resin.
  • the acid value of the activated unsaturated group-containing compounds be about 2 or less.
  • suitable compounds containing activated CH groups may be mentioned a wide variety of compounds as generally disclosed in previously incorporated US4871822 (see especially column 4, lines 15-28), which compounds contain a methylene and/or onosubstituted methylene group in the ⁇ -position to two activating groups such as, for example, carbonyl , cyano, sulfoxide and/or nitro groups.
  • Preferred of these are compounds containing a methylene group in the ⁇ -position to two carbonyl groups, such as malonate and/or acetoacetate group-containing compounds.
  • malonate group-containing compounds may be mentioned alonic acid esters as disclosed in previously incorporated US2759913 (see especially column 8, lines 51-52), and malonate group-containing oligomeric and polymeric compounds as disclosed in previously incorporated US4602061 (see especially column 1, line 10 through column 2, line 13).
  • alonic acid esters as disclosed in previously incorporated US2759913 (see especially column 8, lines 51-52)
  • malonate group-containing oligomeric and polymeric compounds as disclosed in previously incorporated US4602061 (see especially column 1, line 10 through column 2, line 13).
  • Preferred of these are the oligomeric and/or polymeric malonate group-containing compounds such as, for example, polyurethanes, polyesters, polyacrylates, epoxy resins, polyamides and polyvinyl resins containing malonate groups in the main chain, pendant or both.
  • the malonate group-containing polyurethanes may be obtained, for example, by reacting a polyisocyanate with an hydroxyl group- containing ester of a polyol and malonic acid, or by esterification or transesterification of an hydroxy functional polyurethane with malonic acid or a dialkylmalonate.
  • the malonate group-containing polyesters may be obtained, for example, by the polycondensation of malonic acid, an alkyl malonic acid (such as ethyl malonic acid), a mono- or dialkyl ester of such a malonic acid, and/or the reaction product of a malonic ester and an alkyl (meth)acrylate, optionally with other di- or polycarboxylic acids; with di- and/or higher functional hydroxy compounds; and, optionally onofunctional hydroxy and/or carboxyl compounds.
  • an alkyl malonic acid such as ethyl malonic acid
  • a mono- or dialkyl ester of such a malonic acid and/or the reaction product of a malonic ester and an alkyl (meth)acrylate
  • alkyl (meth)acrylate optionally with other di- or polycarboxylic acids
  • di- and/or higher functional hydroxy compounds optionally onofunctional hydroxy and/or carboxyl compounds.
  • the malonate group-containing epoxy esters may be obtained, for example, by esterifying an epoxy resin with malonic acid or a malonic monoester, or by transesterification with a dialkyl malonate, optionally with other carboxylic acids and derivatives thereof.
  • the malonate group-containing polyamides may be obtained, for example, in the same manner as the polyesters, wherein at least a part of the hydroxy compound is replaced with a mono- and/or polyvalent primary and/or secondary a ine.
  • Other malonate group-containing polymers may be obtained by the transesterification of an excess of a dialkyl malonate with an hydroxy-functional polymer such as, for example, a vinyl alcohol/styrene copolymer. In this manner, a polymer with malonate group-containing side-chains may be formed. Any excess dialkyl malonate may be removed under reduced pressure or, optionally, be used as a reactive solvent.
  • malonate group-containing compounds in which the malonic acid structural unit is cyclized, for example, by formaldehyde, acetaldehyde, acetone or cyclohexanone.
  • malonate group-containing compounds for use with the present invention are the malonate group-containing oligomeric esters, polyesters, polyurethanes and epoxy esters containing 2-100, more preferably 2-20, malonate groups per molecule. It is also especially preferred that such malonate group-containing compounds have a number average molecular weight (Mn) in the range of from about 250 to about 3000, and an acid number of about 2 or less.
  • Mn number average molecular weight
  • acetoacetate group-containing compounds may be mentioned acetoacetic esters as disclosed in previously incorporated US2759913 (see especially column 8, lines 53-54), diacetoacetate compounds as disclosed in previously incorporated US4217396 (see especially column 2, line 65 through column 3, line 27), and acetoacetate group-containing oligomeric and polymeric compounds as disclosed in previously incorporated US4408018 (see especially column 1, line 51 through column 2, line 6). Preferred of these are the oligomeric and/or polymeric acetoacetate group-containing compounds.
  • Suitabl e acetoacetate group-containing ol igomeri c and polymeri c compounds can be obtained, for example, from polyal cohol s and/or hydroxy-functi onal polyether, polyester, polyacryl ate, vi nyl and epoxy oligomers and polymers by reaction with diketene or transesterification with an alkyl acetoacetate.
  • Such compounds may also be obtained by copolymerization of an acetoacetate functional acrylic monomer with other vinyl- and/or acrylic-functional monomers.
  • acetoacetate group-containing compounds for use with the present invention are the acetoacetate group-containing oligomers and polymers containing at least 2 acetoacetate groups. It is also especially preferred that such acetoacetate group-containing compounds should have an Mn in the range of from about 234 to about 30000, and an acid number of about 2 or less.
  • the activated CH groups-containing compounds may be utilized in ena ine form such as disclosed in EP-A-0420133, which is incorporated by reference herein for all purposes as if fully set forth.
  • component (A) and (B) react with each other through a Michael addition, in which the activated CH group of component (B) adds to one of the carbon atoms of the activated unsaturated group of component (A).
  • Components (A) and (B) are preferably contained in the coating compositions in an amount such that the ratio of the number of activated CH groups to the number of activated unsaturated groups is in the range of about 0,25 to about 4,0, more preferably in the range of about 0,5 to about 2,0.
  • the blocked basic catalysts suitable for use with the present coating compositions are blocked with an acidic compound, whereby the so-blocked catalyst becomes unblocked under the influence of UV light having a wavelength in the range from 250-500 nm.
  • amine catalysts may be mentioned those of the amidine type, for example, tetramethyl guanidine, 1,4-dihydropyrimidines, l,8-diaza-bicyclo[5.4.0]undec-7-ene, l,4-diaza-bicyclo[2.2.2]octane and 2-alkyl-N-al yl imidazolines.
  • ammonium catalysts may be mentioned quaternary ammonium compounds, for example, quaternary ammonium hydroxides such as tetrabutyl ammonium hydroxide; quaternary ammonium alkoxides such as benzyltrimethyl ammonium methoxide and dilauryldimethyl ammonium methoxide; and quaternary ammonium carbanions such as benzyltrimethyl ammonium acetyl acetate.
  • quaternary ammonium hydroxides such as tetrabutyl ammonium hydroxide
  • quaternary ammonium alkoxides such as benzyltrimethyl ammonium methoxide and dilauryldimethyl ammonium methoxide
  • quaternary ammonium carbanions such as benzyltrimethyl ammonium acetyl acetate.
  • phosphane compounds may be mentioned those disclosed in previously incorporated US4871822 (column 7, line 48 through column 8, line 2), and particularly the tertiary phosphanes disclosed therein.
  • phosphane compounds may be mentioned tris(hydroxymethyl)phosphane, triphenylphosphane and tris(p-tolyl)phosphane.
  • These basic catalysts (unblocked) are generally utilized in amounts ranging from about 0,05 wt% to about 3,0 wt%, preferably from about 0,1 wt% to about 1,0 wt%, based upon the combined weight of components (A) and (B) .
  • Suitable blocking agents for these basic catalysts comprise acidic compounds selected from:
  • suitable ⁇ -keto carboxylic acid blocking agents are known from previously incorporated US4301186 (column 1 line 35 through column 2, line 58) and US4369206 (column 1, line 36 through column 2, line 37).
  • phenyl glyoxylic acid, 1-naphtyl glyoxylic acid, pyruvic acid and benzylidiene pyruvic acid are known from previously incorporated US4301186 (column 1 line 35 through column 2, line 58) and US4369206 (column 1, line 36 through column 2, line 37).
  • phenyl glyoxylic acid 1-naphtyl glyoxylic acid
  • pyruvic acid pyruvic acid
  • benzylidiene pyruvic acid benzylidiene pyruvic acid.
  • Suitable aromatic or N-heterocyclic substituted formic, acetic and oxyacetic acid blocking agents are known from previously incorporated DE-A-2940333 (page 7, line 15 through page 8, line 15).
  • phenyl acetic acid, 1-naphtyl acetic acid and 9-anthracene carboxylic acid are known from previously incorporated DE-A-2940333 (page 7, line 15 through page 8, line 15).
  • phenyl acetic acid 1-naphtyl acetic acid and 9-anthracene carboxylic acid.
  • Suitable halide blocking agents are generally known from DE-A-2940332. Preferred are the anions chloride, bromide and iodide. The halide blocking agents, however, are in general less preferred because a low molecular weight halogenide may be released upon unblocking of the catalyst.
  • the acidic compound is preferably utilized in an amount of from about 10 to about 125, more preferably from about .25 to about 125, and especially from about 50 to about 100, equivalent percent required to neutralize the basic catalyst. Within these ratios, the potlife of the composition can be readily varied, for example, between h hour at 20°C to more than 6 weeks at 50°C.
  • the basic catalyst and blocking agent can be mixed in situ and added to the composition in quantities to result in the desired ratio as set forth above.
  • a salt of the catalyst and blocking agent can be pre-prepared and added to the composition.
  • the curing of the above-described coating compositions is preferably carried out at ambient temperatures (e.g., 10-30°C) under the influence of UV light of a wavelength 250-500 nm, which can be from a UV source or even daylight.
  • the coating compositions in accordance with the present invention may optionally contain one or more pigments, dyes and usual intermediary agents, additives and/or solvents.
  • suitable inert organic solvents include esters, ketones aromatic and aliphatic hydrocarbons.
  • suitable reactive organic solvents include dimethyl malonate, diethyl malonate, ethyl acetoacetate and 2-ethylhexyl acrylate.
  • preferred additives may be mentioned minor amounts of a co-binder not containing activated unsaturated or CH groups, for example, cellulose acetate butyrate, acrylic, epoxy and polyester resins.
  • these co-binders are commonly utilized in the coatings industry to modify certain properties such as drying speed and adhesion to substrates.
  • a UV sensitizer such as anthracene, which is used to increase the amount of UV light absorbed by the coating composition.
  • the coating compositions in accordance with the present invention are suitable for a variety of coatings uses, for example, as paint, impregnating, sealing and bonding compositions.
  • a preferred application is as a semi one-pack decorative coating.
  • a clearcoat in a basecoat/clearcoat system for refinish applications e.g., automobile refinish.
  • Suitable basecoats for use in such systems are in general well-known in the art.
  • coating compositions may be applied to a substrate in any convenient manner such as, for example, by brushing, spraying or dipping.
  • Suitable substrates include metals, wood, board, plastics and leather.
  • reaction mixture was cooled to 140°C and an additional peroxide solution of 50,0 pbw of Solvesso 100 and 10,0 pbw of Trigonox 42S was added.
  • the recovered salt was purified by means of recrystallization from a solution in 40 ml tetrahydrofuran, yielding a pale yellow salt in a yield of about 67%.
  • a coating composition was prepared from 30,0 grams of (Al), 16,5 grams of (Bl), 3,4 grams of butylacetate and 9,8 grams of a 10% solution of (Cl) in a mixture of butylacetate/methanol (87,5/12,5).
  • compositions were tested for geltime by storing 100 grams of the reaction mixture in a closed tin at a temperature as set forth below. The geltime is reported as the time when the mixture no longer flowed as a liquid upon stirring with a spatula.
  • compositions were applied onto a tin plated steel panel with a drawbar to a dry layer thickness of ca. 50 ⁇ m.
  • the panel of Example 1 was irradiated with a 400 Watt mercury lamp at a distance of 38 cm.
  • the panel of Comparative Example 1 was not irradiated.
  • the petrol resistance of the so-applied coatings was tested qualitatively. After one week cure at 23°C a drop of petrol was applied to the test panel. After five minutes, the panel was inspected for coating softening.
  • the pendulum hardness of the so-applied coatings was also tested after one day and one week cure at 23°C with the aid of a Persoz apparatus.
  • Example 1 >1 week at 50°C O.K. 35" 137" 51 ⁇ m
  • Example 1 was repeated except that 25 grams of (A2), 33 grams of (Bl) and 13,4 grams of the 10% solution of (Cl) were utilized.
  • Example 2 >10 days at 50°C good 123" 249" 45 ⁇ m
  • Example 1 The composition of Example 1 was repeated except that the solution of (Cl) was replaced with 12,1 grams of a 10% solution of (C2) in a mixture of butylacetate/methanol (87,5/12,5).
  • This composition and the composition of Comparative Example 1 were applied onto a tin plated steel panel with a drawbar to a dry film thickness of ca. 80 ⁇ m. For each composition two panels were prepared. One of each was exposed to daylight, while the other was stored in darkness. The petrol resistance and pendulum hardness were measured as above.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

Composition de revêtement comportant les ingrédients suivants: (A) un composé comprenant un groupe insaturé activé, (B) un composé comprenant un groupe CH activé et (C) un catalyseur basique qui, bloqué par un composé acide, se débloque sous l'effet du rayonnement UV. De telles compositions de revêtement présentent une durée élevée de vie en pot, une bonne vitesse de durcissement et un bon équilibre entre propriétés physiques et mécaniques, et conviennent particulièrement bien pour divers revêtements tels que des peintures, des imprégnateurs, des produits d'étanchéification et des adhésifs.
PCT/EP1994/001451 1993-05-26 1994-05-03 Composition de revetement comportant un catalyseur basique active par les uv WO1994028075A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP94916207A EP0702707A1 (fr) 1993-05-26 1994-05-03 Composition de revetement comportant un catalyseur basique active par les uv
CA002163875A CA2163875A1 (fr) 1993-05-26 1994-05-03 Composition de revetement comprenant un catalyseur basique pouvant etre degage par les uv
FI955613A FI955613A (fi) 1993-05-26 1995-11-22 Päällystekoostumus, joka sisältää emäksistä katalyyttiä, josta voidaan poistaa suojaus UV-valolla
NO954787A NO954787L (no) 1993-05-26 1995-11-24 Beleggblanding som omfatter en basisk katalysator som kan deblokkeres ved hjelp av ultrafiolett lys

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP93201513 1993-05-26
EP93201513.4 1993-05-26

Publications (1)

Publication Number Publication Date
WO1994028075A1 true WO1994028075A1 (fr) 1994-12-08

Family

ID=8213849

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/001451 WO1994028075A1 (fr) 1993-05-26 1994-05-03 Composition de revetement comportant un catalyseur basique active par les uv

Country Status (6)

Country Link
EP (1) EP0702707A1 (fr)
CN (1) CN1126484A (fr)
CA (1) CA2163875A1 (fr)
FI (1) FI955613A (fr)
NO (1) NO954787L (fr)
WO (1) WO1994028075A1 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0747454A1 (fr) * 1995-06-08 1996-12-11 BASF Aktiengesellschaft Compositions durcissables par rayonnement contenant des acrylates multifonctionnels et des amines bloquées
EP0764698A1 (fr) * 1995-09-22 1997-03-26 Basf Aktiengesellschaft Compositions durcissables par rayonnement contenant des composés tensioactifs à fonctions aminées masquées
EP0882072B2 (fr) † 1996-02-22 2005-10-26 Ciba SC Holding AG Photocatalyseur anionique
US7144605B2 (en) * 2001-03-27 2006-12-05 Nippon Paint Co., Ltd. Curable coating composition and coating film forming method
US7538104B2 (en) 2001-10-17 2009-05-26 Ciba Specialty Chemicals Corporation Photoactivable nitrogen bases
US7709555B2 (en) 2004-09-17 2010-05-04 Akzo Nobel Coatings International Coating composition based on thiol-NCO curing
EP2192447A1 (fr) 2008-11-27 2010-06-02 Akzo Nobel Coatings International B.V. Procédé d'application d'un motif sur un substrat
JP2016503447A (ja) * 2012-11-14 2016-02-04 ヴィブラント ホールディングス リミテッド ライアビリティ カンパニー アレイ合成および生体分子解析のための、支持体、システム、および方法
WO2016174192A1 (fr) 2015-04-29 2016-11-03 Bsn Medical Gmbh Dispositif médical pour bains
WO2016174043A1 (fr) 2015-04-29 2016-11-03 Bsn Medical Gmbh Procédé en plusieurs étapes, pour produire du no
US9921477B2 (en) 2007-04-03 2018-03-20 Base Se Photoactivable nitrogen bases
US10006909B2 (en) 2012-09-28 2018-06-26 Vibrant Holdings, Llc Methods, systems, and arrays for biomolecular analysis
US10286376B2 (en) 2012-11-14 2019-05-14 Vibrant Holdings, Llc Substrates, systems, and methods for array synthesis and biomolecular analysis
US10577391B2 (en) 2014-02-21 2020-03-03 Vibrant Holdings, Llc Selective photoactivation of amino acids for single step peptide coupling
US10816553B2 (en) 2013-02-15 2020-10-27 Vibrant Holdings, Llc Methods and compositions for amplified electrochemiluminescence detection
US11168365B2 (en) 2017-05-26 2021-11-09 Vibrant Holdings, Llc Photoactive compounds and methods for biomolecule detection and sequencing
US11565231B2 (en) 2012-02-07 2023-01-31 Vibrant Holdings, Llc Substrates, peptide arrays, and methods

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0008626A1 (fr) * 1978-07-14 1980-03-19 Bayer Ag Sels d'ammonium d'acides alpha-cétocarboxyliques, leur utilisation pour la préparation d'amines et matériaux de revêtement les contenant
EP0027891A1 (fr) * 1979-10-04 1981-05-06 Bayer Ag Sels d'ammonium, procédé de préparation d'amines qui sont à leur base, et compositions de revêtement à base de préproduits de résines d'uréthane ou d'époxydes
EP0160824A1 (fr) * 1984-04-04 1985-11-13 Hoechst Aktiengesellschaft Produit de réaction de composés ayant d'insaturations oléfiniques avec des composés ayant d'hydrogène actif, procédé pour leur préparation et vernis en deux composants dérivant de ceux-ci
EP0448154A1 (fr) * 1990-03-20 1991-09-25 Akzo Nobel N.V. Composition de revêtement contenant un catalyseur basique bloqué

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0008626A1 (fr) * 1978-07-14 1980-03-19 Bayer Ag Sels d'ammonium d'acides alpha-cétocarboxyliques, leur utilisation pour la préparation d'amines et matériaux de revêtement les contenant
US4369206A (en) * 1978-07-14 1983-01-18 Bayer Aktiengesellschaft Ammonium salts of α-ketocarboxylic acids
EP0027891A1 (fr) * 1979-10-04 1981-05-06 Bayer Ag Sels d'ammonium, procédé de préparation d'amines qui sont à leur base, et compositions de revêtement à base de préproduits de résines d'uréthane ou d'époxydes
DE2940333A1 (de) * 1979-10-04 1981-05-07 Bayer Ag, 5090 Leverkusen Ammoniumsalze, ein verfahren zur herstellung der ihnen zugrundeliegenden amine, sowie die ammoniumsalze enthaltende beschichtungsmassen auf basis von polyurethan- oder epoxidharzvorprodukten
EP0160824A1 (fr) * 1984-04-04 1985-11-13 Hoechst Aktiengesellschaft Produit de réaction de composés ayant d'insaturations oléfiniques avec des composés ayant d'hydrogène actif, procédé pour leur préparation et vernis en deux composants dérivant de ceux-ci
US4871822A (en) * 1984-04-04 1989-10-03 Hoechst Ag Reaction product of olefinically unsaturated compounds with compounds containing active hydrogen, processes for their preparation and 2-component lacquers based thereon HOE 85/F O36J
EP0448154A1 (fr) * 1990-03-20 1991-09-25 Akzo Nobel N.V. Composition de revêtement contenant un catalyseur basique bloqué

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0747454A1 (fr) * 1995-06-08 1996-12-11 BASF Aktiengesellschaft Compositions durcissables par rayonnement contenant des acrylates multifonctionnels et des amines bloquées
US5728750A (en) * 1995-06-08 1998-03-17 Basf Aktiengesellschaft Radiation-curable compositions comprising polyfunctional acrylates and capped amines
EP0764698A1 (fr) * 1995-09-22 1997-03-26 Basf Aktiengesellschaft Compositions durcissables par rayonnement contenant des composés tensioactifs à fonctions aminées masquées
US5801213A (en) * 1995-09-22 1998-09-01 Basf Aktiengesellschaft Radiation-curable compositions comprising surface-active capped amino compounds
EP0882072B2 (fr) † 1996-02-22 2005-10-26 Ciba SC Holding AG Photocatalyseur anionique
US7144605B2 (en) * 2001-03-27 2006-12-05 Nippon Paint Co., Ltd. Curable coating composition and coating film forming method
US7538104B2 (en) 2001-10-17 2009-05-26 Ciba Specialty Chemicals Corporation Photoactivable nitrogen bases
US8252784B2 (en) 2001-10-17 2012-08-28 Basf Se Photoactivable nitrogen bases
US7709555B2 (en) 2004-09-17 2010-05-04 Akzo Nobel Coatings International Coating composition based on thiol-NCO curing
US10928728B2 (en) 2007-04-03 2021-02-23 Basf Se Photoactivable nitrogen bases
US9921477B2 (en) 2007-04-03 2018-03-20 Base Se Photoactivable nitrogen bases
EP2192447A1 (fr) 2008-11-27 2010-06-02 Akzo Nobel Coatings International B.V. Procédé d'application d'un motif sur un substrat
US11565231B2 (en) 2012-02-07 2023-01-31 Vibrant Holdings, Llc Substrates, peptide arrays, and methods
US10746732B2 (en) 2012-09-28 2020-08-18 Vibrant Holdings, Llc Methods, systems, and arrays for biomolecular analysis
US10175234B2 (en) 2012-09-28 2019-01-08 Vibrant Holdings, Llc Methods, systems, and arrays for biomolecular analysis
US11815512B2 (en) 2012-09-28 2023-11-14 Vibrant Holdings, Llc Methods, systems, and arrays for biomolecular analysis
US10006909B2 (en) 2012-09-28 2018-06-26 Vibrant Holdings, Llc Methods, systems, and arrays for biomolecular analysis
US11674956B2 (en) 2012-09-28 2023-06-13 Vibrant Holdings, Llc Methods, systems, and arrays for biomolecular analysis
JP2016503447A (ja) * 2012-11-14 2016-02-04 ヴィブラント ホールディングス リミテッド ライアビリティ カンパニー アレイ合成および生体分子解析のための、支持体、システム、および方法
US10286376B2 (en) 2012-11-14 2019-05-14 Vibrant Holdings, Llc Substrates, systems, and methods for array synthesis and biomolecular analysis
US10799845B2 (en) 2012-11-14 2020-10-13 Vibrant Holdings, Llc Substrates, systems, and methods for array synthesis and biomolecular analysis
US10816553B2 (en) 2013-02-15 2020-10-27 Vibrant Holdings, Llc Methods and compositions for amplified electrochemiluminescence detection
US10577391B2 (en) 2014-02-21 2020-03-03 Vibrant Holdings, Llc Selective photoactivation of amino acids for single step peptide coupling
US10813831B2 (en) 2015-04-29 2020-10-27 Bsn Medical Gmbh Medical bathing device
WO2016174192A1 (fr) 2015-04-29 2016-11-03 Bsn Medical Gmbh Dispositif médical pour bains
WO2016174043A1 (fr) 2015-04-29 2016-11-03 Bsn Medical Gmbh Procédé en plusieurs étapes, pour produire du no
US11168365B2 (en) 2017-05-26 2021-11-09 Vibrant Holdings, Llc Photoactive compounds and methods for biomolecule detection and sequencing

Also Published As

Publication number Publication date
FI955613A (fi) 1995-12-19
CA2163875A1 (fr) 1994-12-08
CN1126484A (zh) 1996-07-10
NO954787L (no) 1996-01-23
EP0702707A1 (fr) 1996-03-27
NO954787D0 (no) 1995-11-24
FI955613A0 (fi) 1995-11-22

Similar Documents

Publication Publication Date Title
US5219958A (en) Coating compositions including acid blocked basic catalysts
EP0702707A1 (fr) Composition de revetement comportant un catalyseur basique active par les uv
CN107683312B (zh) 用于改善rma可交联涂料组合物的粘附性的改进的环氧底漆
AU2001260325B2 (en) Photoactivatable coating composition
CA2303931C (fr) Composition liante pour peinture en poudre
US5359005A (en) Stable, one-package, non-gelled coating composition curable under ambient conditions
EP0882072B1 (fr) Photocatalyseur anionique
KR100232793B1 (ko) 코팅 용도용 경화성 수지조성물
EP0227454A2 (fr) Polymères d'esters acéto-acétiques réticulés
JPH07165874A (ja) カルバメートで変性したポリイソシアネート含有硬化性組成物
WO2000037524A1 (fr) Composition de revetement transparent a sechage rapide a teneur organique faiblement volatile
JP3188284B2 (ja) 耐酸腐蝕性コーティング
US5104993A (en) 1,3-dialkylimidazole-2-thione catalysts and method of making same
JPH06510328A (ja) β−ジカルボニル化合物を用いる架橋ポリマーの製造法
CA2517512A1 (fr) Compositions reticulables polymeres contenant des amides acetals
EP1565500A2 (fr) Polymeres acryliques contenant des groupes de carbamates primaires lateraux, procede de fabrication desdits polymeres, et compositions de revetement durcissables contenant lesdits polymeres
US20020076504A1 (en) Photoactivatable coating composition and its use for the preparation of coatings with a rapidly processable surface at ambient temperature
US5852094A (en) Moisture curing coating composition
AU2002236752B2 (en) Polymeric crosslinkable compositions containing spiroorthocarbonates
JPS62223204A (ja) 架橋ポリマ−の製造方法
US5728750A (en) Radiation-curable compositions comprising polyfunctional acrylates and capped amines
US4804715A (en) Cyanoacetic ester system
AU2002236752A1 (en) Polymeric crosslinkable compositions containing spiroorthocarbonates
US7368501B2 (en) Method for improving environmental durability of materials
CN1433450A (zh) 丙烯酸类水基涂料组合物

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 94192602.8

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): CA CN FI JP NO US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 955613

Country of ref document: FI

WWE Wipo information: entry into national phase

Ref document number: 2163875

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 1994916207

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 1996 553457

Country of ref document: US

Date of ref document: 19960205

Kind code of ref document: A

WWP Wipo information: published in national office

Ref document number: 1994916207

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1994916207

Country of ref document: EP