EP1456275A1 - Liants polyurethane (pur) n'ayant pas entierement reagi, utilises pour des vernis de couchage sur bande - Google Patents

Liants polyurethane (pur) n'ayant pas entierement reagi, utilises pour des vernis de couchage sur bande

Info

Publication number
EP1456275A1
EP1456275A1 EP02805302A EP02805302A EP1456275A1 EP 1456275 A1 EP1456275 A1 EP 1456275A1 EP 02805302 A EP02805302 A EP 02805302A EP 02805302 A EP02805302 A EP 02805302A EP 1456275 A1 EP1456275 A1 EP 1456275A1
Authority
EP
European Patent Office
Prior art keywords
component
pur
equivalent
binders
reacted
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Withdrawn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
EP02805302A
Other languages
German (de)
English (en)
Inventor
Eberhard König
Beate Baumbach
Christian Füssel
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.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
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 Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP1456275A1 publication Critical patent/EP1456275A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/3834—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing hydrazide or semi-carbazide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/20—Compositions for powder coatings

Definitions

  • the invention relates to reacted lacquer binders, their production and use in one-component polyurethane stoving lacquers, in particular for the coil
  • EP-A 50 284 discloses partially blocked polyisocyanates which, however, still have free ⁇ CO groups, and their use for the production of powder coatings.
  • the blocking agent fulfills two in these one-component paints
  • Tasks On the one hand it prevents the ⁇ CO groups blocked with them from reacting prematurely with the OH component and on the other hand it regulates the curing of the paints in a certain temperature range due to its specific deblocking properties.
  • the individual blocking agents also bring undesired properties, e.g.
  • butanone oxime and 3,5-dimethylpyrazole may be mentioned as examples. Both blocking agents are well compatible with the known lacquer polyisocyanates and deblock at around 30 "(min.) / 130-140 ° C. On the other hand, butanone oxime tends to non-yellowing of the stoved lacquer and it is suspected to be carcinogenic. Dimethylpyrazole is complex to produce from acetylacetone and hydrazine hydrate and gives coatings an unpleasant smell.
  • the object of the invention was therefore to limit the content of blocking agents in PUR stoving enamels to a minimum. This problem could be solved with the PUR binders according to the invention for one-component PUR stoving enamels.
  • the invention relates to one-component PU binders containing
  • the NCO component A) is not completely, but is only partially blocked, and the unblocked NCO groups of the component of A) have reacted with the OH components (CI + C2).
  • the binders according to the invention can also contain other additives such as fillers, application aids, stabilizing additives, such as. B. HALS amines, solvents and / or diluents, as well as conventional additives, pigments, etc.
  • component A the known polyurets, isocyanurate, allophanate, iminooxadiazinedione (asymmetric trimers), urethane and / or uretdione groups contain lacquer polyisocyanates based on (cyclo) aliphatic diisocyanates with an NCO Content from 12 to 25% by weight. Examples of aliphatic or cycloaliphatic diisocyanates are 1,6-diisocyanatohexane
  • HDI 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), bis (4-isocyanatocyclohexyl) methane (H 2 MDI or Desmodur W ® / Bayer AG ), 2,6 or. 2,5-bis-isocyanato-norbornane or 1,4-bis-isocyanatomethyl-cyclohexane and 1,3- or 1,4-tetramethyl-xylene diisocyanate. Preference is given predominantly to polyisocyanates based on isocyanurate groups
  • Preferred blocking agents B) for the binders according to the invention are oximes, such as, for. B. butanone oxime, secondary aliphatic amines, e.g. Diisopropylamine, CH-acidic compounds, such as. B. Malon or acetoacetic ester, NH-acidic heterocycles, such as. B. 1,2,4-triazole, imidazole or 3,5-dimethylpyrazole, lactams, such as. B. ⁇ -caprolactam, alcohols, such as. B. methanol, ethanol or n-propanol or mixtures of these blocking agents. ⁇ -Caprolactam, diisopropylamine, 1,2,4-triazole or mixtures thereof are particularly preferred.
  • Polyesters, polyethers, polycarbonates or polyacrylates in the OH number range from 50 to 500 are used as the polymeric OH component CI). Branched polyesters with OH numbers from 60 to 140 are preferred.
  • the building blocks for these hydroxyl polyesters are 1, 2-propanediol, neopentyl glycol, 1,6-hexanediol or trimethylolpropane, on the one hand, and maleic anhydride, adipic acid, isophthalic acid or phthalic anhydride, on the one hand.
  • the stabilizing component against thermal yellowing C2) is preferably the addition product of hydrazine hydrate to 2 mol of propylene carbonate of the formula (I), for example known from EP-A 0829 500: CH, OO CH,
  • Another object of the invention is a process for the production of the PUR binders according to the invention, characterized in that the lacquer polyisocyanate A) is initially introduced and reacted with the blocking agent B) at 70-100 ° C. up to the calculated NCO content , then with a solvent inert to NCO groups, e.g. B. Solventnaphta 100 or l-methoxy-2-propyl acetate is diluted and the total amount of OH components (CI + C2) is quickly added at approx. 60 ° C and stirred at approx. 60 ° C until no NCO- Groups are more detectable by IR spectroscopy.
  • a solvent inert to NCO groups e.g. B.
  • Solventnaphta 100 or l-methoxy-2-propyl acetate is diluted and the total amount of OH components (CI + C2) is quickly added at approx. 60 ° C and stirred at approx. 60 ° C until
  • the ready-to-use binder according to the invention is thus obtained in dissolved form.
  • the OH components (CI + C2) are added so rapidly over a period of up to 45 min, preferably 1 to 30 min, that the temperature of about 60 ° C. is maintained.
  • Another object of the invention is the use of the invention
  • PUR binder for one-component PUR stoving enamels can be used to coat substrates made of metal, ceramics, glass, plastics and wood.
  • the one-component PUR binders according to the invention are preferred for
  • Solvessa ® , Solventnaphtha aromatic paint solvents, Exxon Chemicals, Houston, USA
  • Desmophen ® 670 (slightly branched hydroxyl polyester, 80% dissolved in butyl acetate, OH content of the delivery form 3.4%, Bayer AG) 11.8 g (0.1 val) addition product of 2 mol Propylene carbonate and 1 mol
  • the two polyisocyanates and the solvents are introduced and heated to 40 ° C.
  • DIPA is added in portions. After the DIPA addition has ended, the mixture is stirred at 60 ° C. for 1 hour. An NCO content of 1.75% was found, calculated 1.76%.
  • the hydrazide adduct and the polyester are added rapidly and the mixture is reacted for about 5 hours at 60 ° C. until NCO groups can no longer be detected by IR spectroscopy. A pale yellow solution of a binder with the above characteristics is obtained.
  • One-component PUR binder with a mixed block consisting of 1,2,4-triazole and diisopropylamine For every 100 equivalent% of the polyisocyanate component A) there are 72.7 equivalent% of blocking agents B) and the difference to 100 equivalent% comes from the OH components (C 1 + C2).
  • the polyisocyanate, 1-methoxy-propyl acetate and 1,2,4-triazole are introduced and heated to 100 ° C. with stirring. After a reaction time of approximately 1 hour at 100 ° C., the NCO content has dropped to the calculated NCO content of 5.1%. Solventnaphta 100 is added, the mixture is allowed to cool to 60 ° C. and DIPA is added in portions. After stirring for 1 hour at 60 ° C., the calculated NCO content of 1.6% is determined. The polyester and the hydrazide adduct are quickly added and the mixture is reacted for about 5 hours at 60 ° C. until no NCO group can be detected by IR spectroscopy. An almost colorless binder solution with the characteristics indicated above is obtained.
  • This binder is produced analogously to the method described in Example 2, in that the completely blocked polyisocyanate component is first prepared and then the OH components and HALS amine are mixed in.
  • binders of Examples 1-4 are processed with subsequent additives in the Scandex mixer to form lacquer batches (data in% by weight).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Insulated Conductors (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Organic Insulating Materials (AREA)

Abstract

L'invention concerne des liants pour vernis n'ayant pas entièrement réagi, leur production et leur utilisation dans des vernis à cuire à un composant polyuréthane, notamment dans le cadre du couchage sur bande.
EP02805302A 2001-12-10 2002-12-04 Liants polyurethane (pur) n'ayant pas entierement reagi, utilises pour des vernis de couchage sur bande Withdrawn EP1456275A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10160570A DE10160570A1 (de) 2001-12-10 2001-12-10 Anreagierte PUR-Bindemittel für Coil-Coating-Lacke
DE10160570 2001-12-10
PCT/EP2002/013717 WO2003054050A1 (fr) 2001-12-10 2002-12-04 Liants polyurethane (pur) n'ayant pas entierement reagi, utilises pour des vernis de couchage sur bande

Publications (1)

Publication Number Publication Date
EP1456275A1 true EP1456275A1 (fr) 2004-09-15

Family

ID=7708649

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02805302A Withdrawn EP1456275A1 (fr) 2001-12-10 2002-12-04 Liants polyurethane (pur) n'ayant pas entierement reagi, utilises pour des vernis de couchage sur bande

Country Status (9)

Country Link
US (1) US20030139562A1 (fr)
EP (1) EP1456275A1 (fr)
JP (1) JP2005513218A (fr)
KR (1) KR20040065239A (fr)
CN (1) CN1602324A (fr)
AU (1) AU2002366725A1 (fr)
CA (1) CA2469639A1 (fr)
DE (1) DE10160570A1 (fr)
WO (1) WO2003054050A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101392144B (zh) * 2008-11-12 2011-06-08 常州市普兰纳涂料有限公司 风力发电叶片用涂料及其制备方法
CN102634985B (zh) * 2012-03-17 2013-02-13 马鞍山科英合成材料有限公司 一种橡胶制品纤维骨架材料浸胶用的封闭异氰酸酯粘合剂及其组合物和制备方法及用途

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3120596A1 (de) * 1981-05-23 1982-12-23 Bayer Ag, 5090 Leverkusen Loesungsmittelarme, hitzehaertbare polyurethan-reaktivbeschichtungsmasse, verfahren zu ihrer herstellung und ihre verwendung in direkt- und umkehr-beschichtungsverfahren
US5091475A (en) * 1989-07-17 1992-02-25 Mobay Corporation Powder coatings with flat finishes
US5216078A (en) * 1992-07-29 1993-06-01 Basf Corporation Isocyanate-crosslinked coating having reduced yellowing
DE4240480A1 (de) * 1992-12-02 1994-08-25 Bayer Ag Organische Polyisocyanate mit zumindest teilweise blockierten Isocyanatgruppen
US5510443A (en) * 1993-03-15 1996-04-23 Bayer Corporation Process for preparing a coating with improved resistance to yellowing and the resulting coating
CA2116167C (fr) * 1993-03-15 2007-05-15 Myron W. Shaffer Compositions de revetement a un seul element contenant des polyisocyanates bloques par des groupes oxime ou lactame a proprietes ameliorees de resistance au jaunissement
DE4339367A1 (de) * 1993-11-18 1995-05-24 Bayer Ag Blockierte Polyisocyanate
DE4416750A1 (de) * 1994-05-13 1995-11-16 Bayer Ag Mischblockierte Polyisocyanate
DE19516400A1 (de) * 1995-05-04 1996-11-07 Bayer Ag Blockierte Polyisocyanate und ihre Verwendung
DE19637334A1 (de) * 1996-09-13 1998-03-19 Bayer Ag Stabilisierte blockierte Isocyanate
DE19738497A1 (de) * 1997-09-03 1999-03-04 Bayer Ag Amin-blockierte Polyisocyanate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03054050A1 *

Also Published As

Publication number Publication date
CA2469639A1 (fr) 2003-07-03
CN1602324A (zh) 2005-03-30
DE10160570A1 (de) 2003-06-18
JP2005513218A (ja) 2005-05-12
KR20040065239A (ko) 2004-07-21
US20030139562A1 (en) 2003-07-24
WO2003054050A1 (fr) 2003-07-03
AU2002366725A1 (en) 2003-07-09

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