EP0934372A1 - Adhesif fluorescent au cyanoacrzlate - Google Patents

Adhesif fluorescent au cyanoacrzlate

Info

Publication number
EP0934372A1
EP0934372A1 EP97945857A EP97945857A EP0934372A1 EP 0934372 A1 EP0934372 A1 EP 0934372A1 EP 97945857 A EP97945857 A EP 97945857A EP 97945857 A EP97945857 A EP 97945857A EP 0934372 A1 EP0934372 A1 EP 0934372A1
Authority
EP
European Patent Office
Prior art keywords
adhesive
pyrylium salt
ppm
concentration
cyanoacrylic 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.)
Withdrawn
Application number
EP97945857A
Other languages
German (de)
English (en)
Inventor
Hanns Roland Misiak
Heinz Christian Nicolaisen
Annette SCHRÖTER
Dagmar Behn
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0934372A1 publication Critical patent/EP0934372A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

  • the invention relates to a cyanoacrylate adhesive with a pyrylium salt as a fluorescent dye and to the use thereof.
  • EP 0 105 062 B1 describes a cyanoacrylate adhesive with at least one dye from the group C.I. Solvent Green 5, C.I. Acid Red 50 and C.I. Acid Red 52 described, in an amount of 5 to 1000 ppm, based on the monomers.
  • a disadvantage of these dyes is their intensive, clearly visible intrinsic color, especially when gluing transparent parts to be joined.
  • the dyes are only slightly soluble in the monomers. It is therefore not possible to produce a masterbatch from cyanoacrylates and the dye, i.e. a master mixture of cyanoacrylates with a high dye concentration, which the user can then dilute as much as the specific situation requires.
  • the solution according to the invention can be found in the patent claims. It consists of a very specific selection among the pyryiium salts.
  • the cyanoacrylate adhesives according to the invention are characterized by an effective concentration of at least one pyrylium salt of the following general formula
  • RT to R 5 mean hydrogen, alkyl and aryl radicals or a fused aromatic at two vicinal positions.
  • the substituents can in turn carry alkyl, aryl, alkoxy, aryloxy, halogen or pseudohalogen radicals.
  • the total number of carbon atoms in the substituents should be 1 to 1 8, in particular 6 to 1 0.
  • the substituents can be the same or different.
  • Counterion A is non-nucleophilic anions, such as, for example, hexafluorophosphate, hexafluoroantimonate, tetrafluoroborate, perchlorate and tetrachloroferrate.
  • Dyes used in accordance with the invention are: 2,4,6-triphenylpyrylium tetrafluoroborate, 2,4,6- Triphenylpyrylium trifluoromethanesulfonate, 2,4-di-tert-butyl-6- (2-methoxyphenyl) -pyrylium tetrafluoroborate, 1, 4-phenylene-4,4 "-bis (2,6-diphenyl-4-pyryiium tetrafluoroborate, 2 -4-diphenyl-6- (4-methoxypheny) pyrylium perchlorate; 2,4-diphenyl-6- (p-tolyl) pyrylium tetrachloroferrate.
  • the dyes are present in the adhesive in concentrations of 5 to 50,000, in particular 20 to 10, 000 ppm.
  • the adhesive is preferably free of solvents or solubilizers between the dyes and the monomers. Solvents are expediently used when a concentration of> 0.3% by weight of dye is to be dissolved.
  • the stock solution has a concentration of 2.5% by weight, the user can very easily dilute to the desired concentration without problems with the dosage or the homogeneity.
  • the stock solution expediently has a concentration of 0.1 to 5% by weight of pyrylium salt (the upper limit being determined by the solubility).
  • Another unexpected advantage of the dyes to be used according to the invention is their light fastness: in the liquid state, a cyanoacrylate adhesive colored with the pyrylium salts mentioned shows no decrease in the fluorescence intensity even after UV light irradiation for several minutes (254 and 365 nm).
  • the dyes used according to the invention can be used universally due to their relatively low intrinsic coloration in visible light, since the adhesives produced therewith do not show any visible intrinsic coloration in the adhesive joint even with transparent parts to be joined. They fluoresce when irradiated with short-wave light. The fluorescence signal retroreflected by the adhesive located on the part to be joined allows the application of the adhesive to be controlled via detection by means of a luminescent probe.
  • ⁇ -Cyanoacrylic acid esters are to be understood as meaning both conventional monocyanoacrylic acid esters and biscyanoacrylic acid esters.
  • customary monocyanoacrylic acid esters means the following substances of the general formulas:
  • H 2 C C (CN) -CO-0-R (II).
  • R is an alkyl, alkenyl, cycloalkyl, aryl, alkoxyalkyl, aralkyl or haloalkyl group with 1 to 24, in particular 1 to 12, carbon atoms, in particular a methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, pentyl, hexyl, allyl, methallyl, crotyl, propargyl, cyclohexyl, benzyl, phenyl, cresyl, 2-chloroethyl, 3-chloropropyl, 2-chlorobutyl, trifluoroethyl, 2-methoxyethyl, 3-methoxybutyl, 2-methoxyisopropyl, and 2-ethoxyethyl.
  • cyanoacrylates are known to the adhesive specialist, cf. Ullmanns Encyclopaedia of Industrial Chemystry, vol. A1, p. 240, Verlag Chemie Weinheim (1985) as well as US Pat. No. 3,254,111 and PS-PS 3,654,340.
  • Preferred monomers are the allyl, methoxyethyl, ethoxyethyl, methyl , Ethyl, propyl, isopropyl or butyl esters of 2-cyanoacrylic acid.
  • R is a branched or unbranched divalent alkane radical with 2 to 18, in particular 6 to 12, carbon atoms, which may also contain heteroatoms such as halogens and oxygen or aliphatic or aromatic rings.
  • R is preferably a pure hydrocarbon. It is important that the bis (cyanoacrylates) are particularly pure. This requirement is met, e.g. by the following production and purification methods: Essentially, monocyanoacrylates are transesterified with diols and the reaction mixtures are then worked up by fractional crystallization. A suitable process for the preparation of biscyanoacrylates is therefore that 2-cyanoacrylic acid or its alkyl ester of the general formula
  • H 2 C C (CN) -CO-0-R 7 (IV),
  • R is a branched or unbranched alkyl radical having 1 to 6 carbon atoms, with diols of the general formula
  • R is a branched or unbranched divalent alkane radical having 2 to 18 carbon atoms, which may also contain heteroatoms such as halogens and oxygen or aliphatic or aromatic rings, transesterified to bis (cyanoacrylates) of the general formula III and then the reaction mixture through fractional crystallization cleans.
  • R is a branched or unbranched divalent alkane radical having 2 to 18 carbon atoms, which may also contain heteroatoms such as halogens and oxygen or aliphatic or aromatic rings, transesterified to bis (cyanoacrylates) of the general formula III and then the reaction mixture through fractional crystallization cleans.
  • the cyanoacrylate adhesive also contains the usual stabilizers in usual amounts. Examples include: hydroquinone, sulfur dioxide, boron trifluoride and methanesulfonic acid.
  • the adhesive according to the invention may also contain other additives, e.g. Plasticizers, activators or accelerators, thickening and / or elasticizing agents, adhesion promoters and other dyes.
  • additives e.g. Plasticizers, activators or accelerators, thickening and / or elasticizing agents, adhesion promoters and other dyes.
  • the adhesives according to the invention are produced as usual by mixing the components.
  • adhesions can be carried out with the adhesives according to the invention, in particular adhesives of the same or different materials made of e.g. Metal, elastomers and plastics, especially gluing of transparent parts made of polystyrene, polymethyl methacrylate and polycarbonate.
  • the samples produced were examined according to various criteria in order to determine whether the fluorescent additives have an influence on the reaction rate and / or the storage stability of cyanoacrylate adhesives.
  • the viscosity was measured both shortly after the sample production and after an additional temperature storage for 10 days at 70 ° C (forced air oven) in polyethylene bottles.
  • the curing speed was determined as the setting time on an EPDM foam rubber cord (0 15 mm) as follows: The EPDM foam rubber cord was freshly cut. 1 to 2 drops of adhesive were dosed onto the surface and the rubber cord ends were immediately joined together. The setting time was determined as the time until the kink resistance.
  • esters of cyanoacrylic acid each stabilized with 1000 ppm hydroquinone and 50 ppm sulfur dioxide, different amounts of the following substances were dissolved to assess the dissolving behavior.
  • the fluorescent additives were completely dissolved within 8 hours by automatic shaking at room temperature in a concentration of up to 2.5%.
  • the fluorescence property was determined using the LUT 1-4 luminescence probe (lens 133) from Erwin Sick.
  • the luminescence scanner emits modulated, ultraviolet light with a wavelength of 365 nm and responds to light of the same modulation frequency in the wavelength range from approx. 450 to 1000 nm.
  • the distance between the lens and the adhesive was 40 mm.
  • Adhesive drops of 10 mg mass were metered onto a glass slide; Drop diameter on the surface approx. 5 mm.
  • the fluorescent dye Cl Solvent Green 5 was dissolved in an ethyl cyanoacrylic ester (stabilized with 500 ppm hydroquinone and 10 ppm SO 2 ) in concentrations of 0.01 and 0.03%.
  • the fluorescence measurement with the same experimental setup gave an intensity signal of 10 units (start) or 8 units (after 5 minutes) for the sample with 0.01% Cl Solvent Green 5 and for the sample with 0.03% Cl Solvent Green 5 Intensity signal of 35 units (start) or 30 units (after 5 minutes).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne un adhésif à base d'esters d'acide PROPORTIONAL -cyanoacrylique avec un sel de pyrylium de formule générale (I). Cette formule permet d'ajouter aux esters d'acide cyanoacrylique, un colorant à concentration élevée, sans altérer pour autant la stabilité au stockage et les propriétés adhésives. On peut préparer des solutions mères, au moyen desquelles des adhésifs au cynoacrylate peuvent être facilement colorés suivant l'utilisation désirée.
EP97945857A 1996-10-25 1997-10-17 Adhesif fluorescent au cyanoacrzlate Withdrawn EP0934372A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19644332A DE19644332A1 (de) 1996-10-25 1996-10-25 Fluoreszierender Cyanacrylatklebstoff
DE19644332 1996-10-25
PCT/EP1997/005753 WO1998018876A1 (fr) 1996-10-25 1997-10-17 Adhesif fluorescent au cyanoacrzlate

Publications (1)

Publication Number Publication Date
EP0934372A1 true EP0934372A1 (fr) 1999-08-11

Family

ID=7809932

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97945857A Withdrawn EP0934372A1 (fr) 1996-10-25 1997-10-17 Adhesif fluorescent au cyanoacrzlate

Country Status (5)

Country Link
US (1) US6204309B1 (fr)
EP (1) EP0934372A1 (fr)
JP (1) JP2001502747A (fr)
DE (1) DE19644332A1 (fr)
WO (1) WO1998018876A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6689826B2 (en) * 2001-09-14 2004-02-10 Henkel Loctite Corporation Curable cyanoacrylate compositions and method of detecting cure
DE102004022232A1 (de) * 2004-05-04 2005-12-01 Infineon Technologies Ag Viskoses Klebematerial zur Befestigung elektronischer Bauelemente
US20080026015A1 (en) * 2006-07-27 2008-01-31 Macdonald John Gavin Thermochromic compositions for skin applicaion
US20080069874A1 (en) * 2006-09-15 2008-03-20 Auriga Laboratories, Inc. Kits for Prevention and Treatment of Rhinitis
US8759428B2 (en) * 2007-08-22 2014-06-24 Sabic Innovative Plastics Ip B.V. Polycarbonate compositions
US20090098081A1 (en) * 2007-10-12 2009-04-16 Macdonald John Gavin System for providing a method for applying a skin sealant having a phase change visual indicating component
US20090098073A1 (en) * 2007-10-12 2009-04-16 Macdonald John Gavin Phase change visual indicating composition
US20090123569A1 (en) * 2007-11-08 2009-05-14 Macdonald John Gavin Coverage indicating technology for skin sealants using tannates
US8173722B2 (en) 2008-07-10 2012-05-08 Aesculap Ag Adhesive compositions for use in surgical therapy
US9050251B2 (en) * 2008-10-31 2015-06-09 The Invention Science Fund I, Llc Compositions and methods for delivery of frozen particle adhesives
US8603495B2 (en) * 2008-10-31 2013-12-10 The Invention Science Fund I, Llc Compositions and methods for biological remodeling with frozen particle compositions
US8545806B2 (en) * 2008-10-31 2013-10-01 The Invention Science Fund I, Llc Compositions and methods for biological remodeling with frozen particle compositions
US8551506B2 (en) * 2008-10-31 2013-10-08 The Invention Science Fund I, Llc Compositions and methods for administering compartmentalized frozen particles
US9060931B2 (en) * 2008-10-31 2015-06-23 The Invention Science Fund I, Llc Compositions and methods for delivery of frozen particle adhesives
US8545857B2 (en) * 2008-10-31 2013-10-01 The Invention Science Fund I, Llc Compositions and methods for administering compartmentalized frozen particles
US20110090050A1 (en) * 2009-10-15 2011-04-21 RFID Mexico, S.A. DE C.V. Method for locating objects
TWI608069B (zh) 2012-09-11 2017-12-11 東亞合成股份有限公司 2-cyanoacrylate (salt) adhesive composition
DE102012222377A1 (de) * 2012-12-06 2014-07-10 Bayerische Motoren Werke Aktiengesellschaft Verfahren zur optischen Überprüfung einer Klebestelle
CN115305021A (zh) * 2022-09-29 2022-11-08 潍坊德高新材料有限公司 一种有色氰基丙烯酸酯胶黏剂及其制备方法

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US3254111A (en) 1960-12-09 1966-05-31 Eastman Kodak Co Esters of alpha-cyanoacrylic acid and process for the manufacture thereof
US3654340A (en) 1970-08-27 1972-04-04 Minnesota Mining & Mfg Cyanoacrylate monomer process
US4405750A (en) * 1981-03-31 1983-09-20 Sumitomo Chemical Company, Ltd. Colored cyanoacrylate adhesive composition
JPS59122567A (ja) * 1982-12-28 1984-07-16 Matsushita Electric Ind Co Ltd 紫外線硬化接着剤組成物
US4556700A (en) * 1984-01-30 1985-12-03 Loctite Limited Instant adhesive composition utilizing calixarene accelerators
IE852158L (en) * 1985-09-02 1987-03-02 Loctite Ireland Ltd Photopolymerisable compositions; pyrylium salt catalysts
DE3540594A1 (de) * 1985-11-15 1987-05-27 Henkel Kgaa Klebstoffe auf basis von cyanacrylsaeureestern
GB2228943A (en) 1989-03-06 1990-09-12 Loctite Cyanoacrylate compositions for bonding porous or non-active substrates
BR9507927A (pt) 1994-06-06 1997-11-11 Henkel Kgaa Processo para a preparação de bis-cianoacrilatos

Non-Patent Citations (1)

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Title
See references of WO9818876A1 *

Also Published As

Publication number Publication date
JP2001502747A (ja) 2001-02-27
WO1998018876A1 (fr) 1998-05-07
DE19644332A1 (de) 1998-04-30
US6204309B1 (en) 2001-03-20

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