WO2001016202A1 - Malonester-blockiertes hdi-trimerisat mit ipda- und formaldehydstabilisierung - Google Patents

Malonester-blockiertes hdi-trimerisat mit ipda- und formaldehydstabilisierung Download PDF

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Publication number
WO2001016202A1
WO2001016202A1 PCT/EP2000/008122 EP0008122W WO0116202A1 WO 2001016202 A1 WO2001016202 A1 WO 2001016202A1 EP 0008122 W EP0008122 W EP 0008122W WO 0116202 A1 WO0116202 A1 WO 0116202A1
Authority
WO
WIPO (PCT)
Prior art keywords
blocked
stabilization
formaldehyde
ipda
nco
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/EP2000/008122
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German (de)
English (en)
French (fr)
Inventor
Eberhard König
Claus Kobusch
Uwe Klippert
Wolfram Küttner
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.)
Bayer AG
Original Assignee
Bayer 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 AG filed Critical Bayer AG
Priority to HK03102085.9A priority Critical patent/HK1049851B/zh
Priority to AT00956468T priority patent/ATE253607T1/de
Priority to DE50004374T priority patent/DE50004374D1/de
Priority to PL00353087A priority patent/PL353087A1/xx
Priority to DK00956468T priority patent/DK1228116T3/da
Priority to HU0202790A priority patent/HUP0202790A3/hu
Priority to MXPA02002139A priority patent/MXPA02002139A/es
Priority to US10/070,028 priority patent/US6583216B1/en
Priority to AU68398/00A priority patent/AU6839800A/en
Priority to CA002382905A priority patent/CA2382905A1/en
Priority to EP00956468A priority patent/EP1228116B1/de
Priority to JP2001520757A priority patent/JP2003508562A/ja
Priority to BR0013622-0A priority patent/BR0013622A/pt
Publication of WO2001016202A1 publication Critical patent/WO2001016202A1/de
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8093—Compounds containing active methylene 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
    • C08G18/28—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
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/54—Polycondensates of aldehydes
    • 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
    • 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

Definitions

  • the present invention relates to blocked polyisocyanate crosslinkers and their
  • P. 205 ff communicated works.
  • Advantageous with these blocking agents e.g. Diethyl malonate or ethyl acetoacetate is the low stoving range of 80 - 120 ° C for the production of lacquers.
  • they are not dangerous substances.
  • DE-A 19 813 352 describes the incorporation of formaldehyde for the same purpose.
  • the built-in formaldehyde and the content of certain hydrazides and HALS amines prevent the thermal enamelling of the stove enamel from occurring.
  • the method of DE-A 19 813 352 is not sufficient to prevent clouding or precipitation (see comparative examples 2 and 3).
  • the object of the invention is to produce polyisocyanate crosslinking agents blocked with CH-acidic esters in such a way that a good storage stability of the crosslinking agents and the lowest possible thermal yellowing of the lacquers is ensured. This problem could be solved with the blocked polyisocyanate crosslinking agents according to the invention.
  • the invention relates to blocked polyisocyanate crosslinking agents dissolved in a solvent (mixture) and containing blocked isocyanate groups of 5-
  • the invention also relates to the use of the blocked polyisocyanate crosslinking agents according to the invention for curing organic polyhydroxy compounds in polyurethane stoving lacquers in the solvent-containing phase or in the aqueous phase. These are used, for example, for automotive plastic paints with a soft-feel effect.
  • the blocked polyisocyanate crosslinking agents according to the invention may also contain additives of hydrazides and HALS amines stabilizing against thermal yellowing, as described in EP-A 829 500 or DE-A 19 856 968.
  • the blocked polyisocyanate crosslinking agents according to the invention also contain 5-50% by weight, preferably 15-30% by weight, of solvents.
  • Water-miscible solvents such as l-methoxy-2-propyl acetate, isobutanol, butyl glycol, N-methylpyrrolidone, butyl diglycol or butyl diglycol acetate, tend to be used.
  • the blocked polyisocyanate crosslinkers according to the invention are:
  • polyisocyanate crosslinkers according to the invention can be prepared as follows:
  • the polyisocyanate component is optionally introduced together with a little solvent, for example 1-methoxy-2-propyl acetate (MPA), at about 50 ° C.
  • the CH-acidic ester for example malonic ester
  • the CH-acidic ester is mixed as a mixture with about 2-3% of a 30th % Na methylate solution added and reacted at 60-90 ° C to the calculated NCO content.
  • the calculated amount of diamine for example l-amino-3, 3,5-trimethyl-5-aminomethylcyclohexane (IPDA), dissolved in further MPA, is added and the mixture is reacted at about 50-70 ° C., so "that no more NCO groups can be detected.
  • IPDA 3,5-trimethyl-5-aminomethylcyclohexane
  • the stabilizers against thermal yellowing for example the addition product mentioned above, consisting of 2 mol of propylene carbonate and 1 mol of hydrazine, and the HALS amine Tmuvin 770 DF (from Ciba Specialty) are stirred in.
  • the mixture is diluted with further alcohol, for example isobutanol and / or butyl glycol, and finally made weakly acidic at 0.5-2.5%, based on the batch, of dibutyl phosphate (pH 5, 0-6,9).
  • the polyisocyanates on which the blocked polyisocyanate crosslinking agents according to the invention are based are known paint polyisocyanates with aliphatic and / or cycloaliphatic isocyanate groups and an isocyanate content of 7 to 30, preferably 12 to 25,% by weight.
  • Known biuret, isocyanurate, urethane, allophanate and / or uretdione groups are preferably used lacquer polyisocyanates based on 1,6-diisocyanatohexane (HDI), l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl - Cyclohexane (IPDI) and / or bis (4-isocyanatocyclohexyl) methane (H 12 MDI or Desmodur W ® / Bayer AG).
  • HDI 1,6-diisocyanatohexane
  • IPDI l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl - Cyclohexane
  • H 12 MDI or Desmodur W ® / Bayer AG bis (4-isocyanatocyclohexyl) methane
  • asymmetrically trimerized lacquer polyisocyanates based on 1, 6-diisocyanatohexane, which in addition to isocyanurate also have iminooxadiazinedione groups can be used as polyisocyanate components, as described, for example, in EP-A 798 299.
  • Polyisocyanates based on other isocyanates such as e.g. 1,4-diisocyanato-butane, 2,4- or 2,6-diisocyanato-1-methyl-cyclohexane, 2,5- and / or 2,6-bis-isocyanato-norbonane, 3- and / or 4- Isocyanatomethyl-l-methylcyclohexane, 1,4-bis
  • (2-isocyanato-prop-2-yl) benzene, 1,3-diisocyanatomethylbenzene, 1,3- or 1,4-bis-isocyanatomethylcyclohexane can be used.
  • Polyisocyanates containing isocyanurate groups and based on 1,6-diisocyanatohexane are very particularly preferred as the polyisocyanate component.
  • Suitable blocking components are CH-acidic esters, for example diethyl malonate or ethyl acetoacetate and / or their methyl, isopropyl, isobutyl or tert-butyl derivatives. Diethyl malonate is preferred.
  • the diamine component incorporated in the crosslinkers according to the invention has the
  • the task is to gently react with the NCO groups still remaining after the NCO blocking reaction and thus to contribute to the enlargement of the molecule. In this way, 5-20 equivalent%, preferably 7-10 equivalent%, of NCO groups are reacted by diamine extension and a possible tendency towards crystallization is prevented.
  • Aliphatic and cycloaliphatic are suitable for diamines. Examples include ethylene and propylene diamine, 4,4'-diaminodicyclohexyl methane and 1,4-diaminocyclohexane. 3,3,5-Trimethyl-5-aminomethylcyclohexylamine (IPDA) is preferred.
  • Polyisocyanate blocked and diamine-extended to 100 equivalent% are preferably 0.1 to 0.4 mol, i.e. H. 10-40 equivalent% of paraformaldehyde used and with a base, e.g. Na methylate, reacted. These are 0.5 to 5.0% by weight of formaldehyde, based on the crosslinker according to the invention without a solvent component.
  • the stabilizers known from EP-A 0 829 500 can be used as additional stabilizing components. According to the invention, preference is given to the hydrazide of the formula (Ia) which is readily accessible by addition of hydrazine hydrate to 2 mol of propylene carbonate
  • the first-mentioned stabilizer is preferably 3 to 6% by weight, the latter preferably 0.5 to 1.5% by weight, based in each case on the crosslinker according to the invention without a solvent content.
  • the solvents or mixtures thereof which are known per se from polyurethane chemistry and are inert to NCO groups, for example l-methoxy-2-propyl acetate, solvent naphtha 100 or butyl acetate, and N-methylpyrrolidone and butyl diglycol acetate, can be used. If the NCO groups are blocked, alcohols, e.g. Butanols such as isobutanol or butyl glycol to enable transesterification with the alcohol residues of the blocking agent.
  • Butanols such as isobutanol or butyl glycol to enable transesterification with the alcohol residues of the blocking agent.
  • the polyisocyanate crosslinker according to the invention is used in conjunction with aqueous OH components for the production of water-based binders, then it contains, based on the polyisocyanate crosslinking solution, an additional 5 to 20% by weight of N-methylpyrrolydone.
  • the polyisocyanate crosslinkers according to the invention have good storage stability, i.e. no crystallization, low thermal yellowing and good paint properties.
  • lacquer films that can be produced with the crosslinking agents according to the invention exhibit permanently stable soft-feel surfaces with good substrate adhesion (feel). They are therefore particularly suitable for coating and painting plastic surfaces.
  • the blocked polyisocyanate crosslinker described here has an IPDA content of 2.32% by weight and a formaldehyde content of 2.46% by weight, based on the solids.
  • NMP N-methylpyrrolidone
  • Solids content 75% by weight blocked NCO content: 8.0% by weight
  • the polyisocyanate is placed at about 50 ° C.
  • the mixture of malonic ester and Na methylate solution is added in larger portions with stirring.
  • stirring is continued for 2-3 hours until an NCO content of 0.6-0.8% is found, an NCO content of 0.6% is calculated.
  • the solution of IPDA and NMP is added and the mixture is stirred for 30 min. at 60 ° C until no more NCO content can be detected. It is diluted with BG and the clear solution of paraformaldehyde, Na methylate solution and IB is added, and the mixture is stirred at 50 ° C. for about 3 hours. Then allow to cool, acidify with dibutyl phosphate and fill.
  • a clear solution of a blocked polyisocyanate crosslinking agent which has a shelf life of several months and has the characteristics communicated in the batch is obtained.
  • the crosslinker according to Example 1 is reworked with the following change: 0.1 Val IPDA are omitted and supplemented with malonic ester. This crosslinker becomes cloudy after storage for 7 days at room temperature, but remains liquid.
  • the crosslinker is reworked according to Example 2 with the following change: There is no incorporation of formaldehyde. Compared to the crosslinker from Example 1, IPDA and formaldehyde are therefore absent.
  • crosslinker according to Example 1 in an aqueous soft-feel lacquer which is processed in one component is described. It was surprising that the very reactive and solvent-containing crosslinker type according to Example 1 could be stirred homogeneously with the resin components, which were predominantly dispersed in water. It was also surprising that these paint batches are stable and processable for at least 2 weeks, which is highly unusual for aqueous malonic ester-blocked isocyanates.
  • Matting agent OK 412 5.3 (Degussa, Frankfurt)
  • This paint is sprayed with an air pressure of 3 bar through a 1.4 mm nozzle onto plastic plates (Bayblend T 65 MN) and 45 min. at 80 ° C and 45 min. dried at 100 ° C.
  • the burned-in (80-100 ° C) black matt lacquer creates a pleasant feel (special feel), a kind of rubber effect when rubbed on.
  • composition of this crosslinker corresponds to that of Example 1.
  • This crosslinker has the following characteristics:
  • Solids content 75% by weight blocked NCO content: 7.7% by weight
  • Lacquer 1 crosslinker according to Example 1 Bayhydrol® VP LS 2058 * ⁇ 525 g 850 g
  • Lacquer 2 Crosslinker according to Example 5 Bayhydrol® VP LS 2058 * '545 g 850 g
  • Bayhydrol® VP LS 2058 from Bayer AG is a PES-PAC dispersion containing OH groups, which is mainly dispersed in water in addition to a little butyl glycol.
  • the OH content of the delivery form is 2%, the OH equivalent is 850 g.
  • paint 2 with the additionally stabilized crosslinker has a lower ⁇ b value of 0.7 than paint 1; this varnish yellows significantly less than varnish 1 under overburning conditions.
  • NMP N-methylpyrrolidone
  • the trimerization (isocyanurate formation) of Desmodur W is carried out according to the usual steps: applying vacuum and removing dissolved CO 2 , heating with stirring to approx. 80 ° C and dropwise addition of the catalyst solution until the trimerization reaction starts exothermic, followed by regular addition of catalyst solution the reaction is kept at 85-95 ° C, for the above approach 8-12 ml of catalyst solution are used in about 5 hours, in which The desired NCO content is diluted with BDGA and the reaction is stopped.
  • the antrimerized Desmodur W is mixed with 2/3 of the MDE amount and preheated to approx. 50 ° C.
  • the remaining third of MDE is mixed with 3.2 g of Na methylate solution to form a catalyst batch.
  • This catalyst batch is metered in in portions, the temperature being allowed to rise to 70-75 ° C. After the catalyst addition has ended, stirring is continued at 70 ° C. for 5 hours.
  • the batch then has an NCO content of 0.3-0.8%. It is diluted with BDGA and the remaining NCO groups are bound with IPDA. An NCO content is no longer detectable. At 50 ° C the clear
  • This paint formulation is stable for 5 days at 40 ° C.
  • the components are dispersed in a dissolver in the order mentioned above and, as indicated in Example 4, sprayed onto plastic plates and at 90 or 100 ° C. for 30 minutes. dried.
  • Duranate® MF-K (Asahi / J) is an HDI trimer that is blocked with diethyl malonate. This contains toluene, ethyl acetate and n-butanol as a solvent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hardware Redundancy (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Paper (AREA)
  • Liquid Crystal Substances (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
PCT/EP2000/008122 1999-08-30 2000-08-21 Malonester-blockiertes hdi-trimerisat mit ipda- und formaldehydstabilisierung Ceased WO2001016202A1 (de)

Priority Applications (13)

Application Number Priority Date Filing Date Title
HK03102085.9A HK1049851B (zh) 1999-08-30 2000-08-21 用1-氨基-3，3，5-三甲基-5-氨基甲基环己烷和甲醛稳定的丙二酸酯封闭的1，6-二异氰酸脂基己烷三聚体
AT00956468T ATE253607T1 (de) 1999-08-30 2000-08-21 Malonester-blockiertes hdi-trimerisat mit ipda- und formaldehydstabilisierung
DE50004374T DE50004374D1 (de) 1999-08-30 2000-08-21 Malonester-blockiertes hdi-trimerisat mit ipda- und formaldehydstabilisierung
PL00353087A PL353087A1 (en) 1999-08-30 2000-08-21 Malonic ester-blocked hdi trimer with ipda stabilization and formaldehyde stabilization
DK00956468T DK1228116T3 (da) 1999-08-30 2000-08-21 Malonesterblokeret HDI-trimerisat med IPDA- og formaldehydstabilisering
HU0202790A HUP0202790A3 (en) 1999-08-30 2000-08-21 Terminated polyisocianate curing agent and its using for producing coating
MXPA02002139A MXPA02002139A (es) 1999-08-30 2000-08-21 Trimerizado de 1,6-diisocianatohexano bloqueado con ester malonico con estabilizacion con ipda y formaldehido.
US10/070,028 US6583216B1 (en) 1999-08-30 2000-08-21 Malonic ester-blocked HDI trimer with IPDA stabilization and formaldehyde stabilization
AU68398/00A AU6839800A (en) 1999-08-30 2000-08-21 Malonic ester-blocked hdi trimer with ipda stabilization and formaldehyde stabilization
CA002382905A CA2382905A1 (en) 1999-08-30 2000-08-21 Malonic ester-blocked hdi trimer with ipda stabilization and formaldehyde stabilization
EP00956468A EP1228116B1 (de) 1999-08-30 2000-08-21 Malonester-blockiertes hdi-trimerisat mit ipda- und formaldehydstabilisierung
JP2001520757A JP2003508562A (ja) 1999-08-30 2000-08-21 ブロックトポリイソシアネート架橋剤
BR0013622-0A BR0013622A (pt) 1999-08-30 2000-08-21 Trimerisado hdi bloqueado com éster malÈnico com estabilização ipda e formaldeìdo

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19941213.8 1999-08-30
DE19941213A DE19941213A1 (de) 1999-08-30 1999-08-30 Malonester-blockiertes HDI-Trimerisat mit IPDA- und Formaldehydstabilisierung

Publications (1)

Publication Number Publication Date
WO2001016202A1 true WO2001016202A1 (de) 2001-03-08

Family

ID=7920149

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/008122 Ceased WO2001016202A1 (de) 1999-08-30 2000-08-21 Malonester-blockiertes hdi-trimerisat mit ipda- und formaldehydstabilisierung

Country Status (20)

Country Link
US (1) US6583216B1 (enExample)
EP (1) EP1228116B1 (enExample)
JP (1) JP2003508562A (enExample)
KR (1) KR100640132B1 (enExample)
CN (1) CN1206253C (enExample)
AT (1) ATE253607T1 (enExample)
AU (1) AU6839800A (enExample)
BR (1) BR0013622A (enExample)
CA (1) CA2382905A1 (enExample)
CZ (1) CZ2002651A3 (enExample)
DE (2) DE19941213A1 (enExample)
DK (1) DK1228116T3 (enExample)
ES (1) ES2209958T3 (enExample)
HK (1) HK1049851B (enExample)
HU (1) HUP0202790A3 (enExample)
MX (1) MXPA02002139A (enExample)
PL (1) PL353087A1 (enExample)
PT (1) PT1228116E (enExample)
TW (1) TW500736B (enExample)
WO (1) WO2001016202A1 (enExample)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004058849A1 (de) * 2002-12-20 2004-07-15 Bayer Materialscience Ag Reaktivsysteme, deren herstellung und deren verwendung
JP2005514513A (ja) * 2002-01-17 2005-05-19 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト 安定化した水性ポリウレタン−ポリウレア分散体
WO2017021150A1 (de) 2015-07-31 2017-02-09 Covestro Deutschland Ag Blockierte polyisocyanatzusammensetzung auf basis von 1,5-pentamethylendiisocyanat
CN111247189A (zh) * 2017-11-21 2020-06-05 三井化学株式会社 封端异氰酸酯组合物及涂覆剂

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004049592A1 (de) * 2004-10-12 2006-05-04 Bayer Materialscience Ag Mit Soft-Touch-Lack beschichtete, verformbare Kunststoffverbundfolien und Kunststoffverbundelemente sowie deren Herstellung
US7371807B2 (en) * 2004-10-21 2008-05-13 Bayer Materialscience Llc Blocked biuretized isocyanates
US20060089481A1 (en) * 2004-10-21 2006-04-27 Roesler Richard R Blocked biuretized isocyanates
US20060089480A1 (en) * 2004-10-21 2006-04-27 Roesler Richard R Biuretized isocyanates and blocked biuretized isocyanates
TW201113301A (en) * 2009-10-01 2011-04-16 Ind Tech Res Inst Multi-isocyanate prepolymer
BR112012019717A2 (pt) * 2010-02-08 2023-11-21 Asahi Kasei Chemicals Corp Composição de poliisocianato bloqueado, composição de revestimento, filme de revestimento, e, método para produzir uma composição de poliisocianato bloqueado
JP5572567B2 (ja) * 2010-02-08 2014-08-13 旭化成ケミカルズ株式会社 ブロックポリイソシアネート組成物を製造する方法
JP5562267B2 (ja) * 2010-02-08 2014-07-30 旭化成ケミカルズ株式会社 ブロックポリイソシアネート組成物及びこれを含む塗料組成物
JP5572565B2 (ja) * 2010-02-08 2014-08-13 旭化成ケミカルズ株式会社 ブロックポリイソシアネート組成物を製造する方法
JP5572566B2 (ja) * 2010-02-08 2014-08-13 旭化成ケミカルズ株式会社 ブロックポリイソシアネート組成物及びこれを含む塗料組成物
JP5562271B2 (ja) * 2010-06-04 2014-07-30 旭化成ケミカルズ株式会社 ブロックポリイソシアネート組成物の製造方法
JP6712311B2 (ja) * 2016-03-29 2020-06-17 旭化成株式会社 ブロックポリイソシアネート組成物、一液型コーティング組成物、塗膜、及び塗装物品
JP6622399B2 (ja) 2016-05-20 2019-12-18 三井化学株式会社 硬化性組成物、塗料、太陽電池用塗料、太陽電池バックシート用塗料、接着剤、太陽電池用接着剤、太陽電池バックシート用接着剤、シートの製造方法、および、硬化剤
CN112752811A (zh) * 2018-10-31 2021-05-04 旭化成株式会社 涂膜
CN110483738A (zh) * 2019-08-20 2019-11-22 湖南湘江关西涂料有限公司 封闭异氰酸酯固化剂及其制备方法、单组分涂料

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EP0313932A2 (de) * 1987-10-15 1989-05-03 Hoechst Aktiengesellschaft Härtungskomponente für Kunstharze, diese enthaltende härtbare Mischungen sowie deren Verwendung
EP0319608A1 (en) * 1987-12-10 1989-06-14 E.I. Du Pont De Nemours And Company A coating composition containing a reactive component an acrylic fatty acid drying oil resin and a metallic alkylate
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JP2005514513A (ja) * 2002-01-17 2005-05-19 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト 安定化した水性ポリウレタン−ポリウレア分散体
WO2004058849A1 (de) * 2002-12-20 2004-07-15 Bayer Materialscience Ag Reaktivsysteme, deren herstellung und deren verwendung
CN1307231C (zh) * 2002-12-20 2007-03-28 拜尔材料科学股份公司 以ch－酸性环酮封端的聚氨酯预聚物、由所述聚合物制备的反应体系及其应用
WO2017021150A1 (de) 2015-07-31 2017-02-09 Covestro Deutschland Ag Blockierte polyisocyanatzusammensetzung auf basis von 1,5-pentamethylendiisocyanat
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CN111247189B (zh) * 2017-11-21 2022-03-08 三井化学株式会社 封端异氰酸酯组合物及涂覆剂

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US6583216B1 (en) 2003-06-24
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CN1371397A (zh) 2002-09-25
AU6839800A (en) 2001-03-26
CZ2002651A3 (cs) 2002-07-17
TW500736B (en) 2002-09-01
ATE253607T1 (de) 2003-11-15
PL353087A1 (en) 2003-10-06
DE19941213A1 (de) 2001-03-01
HUP0202790A2 (hu) 2002-12-28
HUP0202790A3 (en) 2006-02-28
HK1049851B (zh) 2006-01-27
EP1228116B1 (de) 2003-11-05
EP1228116A1 (de) 2002-08-07
KR20020027590A (ko) 2002-04-13
CA2382905A1 (en) 2001-03-08
DE50004374D1 (de) 2003-12-11
BR0013622A (pt) 2002-05-14
MXPA02002139A (es) 2002-11-04
CN1206253C (zh) 2005-06-15
JP2003508562A (ja) 2003-03-04
KR100640132B1 (ko) 2006-10-31
PT1228116E (pt) 2004-03-31

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