WO2023148675A1 - Composition d'isocyanates bloqués et utilisation de composés en tant qu'agents de blocage d'isocyanates - Google Patents

Composition d'isocyanates bloqués et utilisation de composés en tant qu'agents de blocage d'isocyanates Download PDF

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Publication number
WO2023148675A1
WO2023148675A1 PCT/IB2023/050967 IB2023050967W WO2023148675A1 WO 2023148675 A1 WO2023148675 A1 WO 2023148675A1 IB 2023050967 W IB2023050967 W IB 2023050967W WO 2023148675 A1 WO2023148675 A1 WO 2023148675A1
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use according
weight
imidazole
composition
isocyanates
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PCT/IB2023/050967
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English (en)
Inventor
Francesco Maniero
Agostino FENAROLI
Ivan VIVIANI
Camillo ZARANTONELLO
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Maflon S.P.A.
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Publication of WO2023148675A1 publication Critical patent/WO2023148675A1/fr

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    • 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
    • C08G18/8077—Oximes
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C08G18/286—Oximes
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C08G18/2865—Compounds having only one primary or secondary amino group; Ammonia
    • 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
    • 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
    • C08G18/808—Monoamines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/376—Oximes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/395—Isocyanates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention refers to a composition
  • a composition comprising or, alternatively, consisting of isocyanates blocked by means of a blocking agent selected from the group consisting of (i)-(iv) and, optionally, one or more technological additives.
  • the present invention refers to a use of (i)-(iv) as an isocyanate blocking agent.
  • the present invention refers to a use of a composition comprising or, alternatively, consisting of isocyanates blocked by means of a blocking agent; and optionally one or more technological additives; wherein said blocking agent is at least one imidazole compound of general formula (I), in a water repellency and/or oil repellency treatment of a fabric or of a skin.
  • the present invention refers to a use of an imidazole compound of general formula (I) as a blocked isocyanate blocking agent in a water repellency and/or oil repellency treatment of a fabric or a skin.
  • Methyl ethyl ketoxime (or 2-butanone oxime, CAS No. 96-29-7; in short, “MEKO”) is a colourless liquid that is the oxime derived from methyl ethyl ketone.
  • MEKO is mainly used as an anti-skinning agent for oil and latex paints and coatings, as it is able to prevent the formation of solid skins above said paints and said coatings.
  • the functioning of MEKO takes place through a bond with drying agents (in particular metal salts) that catalyze the oxidative cross-linking of the oils contained in the paints and in coatings. Once the paint or the coating is applied to a surface, MEKO evaporates, thus allowing the drying process to proceed.
  • MEKO is also widely used as an isocyanate blocking agent in automobile electrodeposition coating, in painting works, as a curing agent for silicone rubber due to its outstanding water and heat resistance, in fabric treatment in combination with a non-fluorinated resin due to the water repellency properties or in combination with a fluorinated resin due to the water repellency and/or oil repellency properties, and in the printing industry as a fixative.
  • MEKO presents several significant hazards to human health. It has in fact been the subject of the evaluation process (SEv; Substance Evaluation process) whose outcome, reported in the Substance Evaluation Report, led to the drafting of a proposal for harmonized classification (CLH) for the substance.
  • SEv Substance Evaluation process
  • Acute Tox. 3, H301 toxic if swallowed
  • Acute Tox. 4 H312: harmful in contact with skin
  • Skin Sens. 1 , H317 - may cause an allergic skin reaction.
  • 1 , H318 causes serious eye damage
  • Skin Irrit. 2, H315 causes skin irritation
  • STOT SE 3, H336 may cause drowsiness or dizziness
  • STOT SE 1 , H370 (upper respiratory tract) causes organ damage
  • STOT RE 2, H373 blood system
  • Prior art document WO 2015/025776 A1 discloses a blocked isocyanate containing a latent isocyanate group which is produced by blocking an isocyanate group with a blocking agent.
  • Prior art document EP 3 783 041 A1 discloses a blocked polyisocyanate composition.
  • the compounds identified in the present invention have significantly lower toxicity characteristics than MEKO, are normally available on the market in large quantities and at acceptable costs even if - at least currently - they are higher than those of MEKO, are capable of generating blocked isocyanates with neutral (i.e. tending to white or light yellow) colourations, have reaction kinetics comparable to the corresponding products blocked by means of MEKO and show similar and in some cases superior properties compared to those currently used.
  • the object of the present invention is a composition
  • a composition comprising or, alternatively, consisting of isocyanates blocked by means of a blocking agent selected from the group consisting of (i)-(iv) and, optionally, one or more technological additives, having the characteristics as defined in the attached claims.
  • the object of the present invention is a use of a blocking agent selected from the group consisting of (i)-(iv) as an isocyanate blocking agent, having the characteristics as defined in the attached claims.
  • the present invention refers to a use of a composition comprising or, alternatively, consisting of isocyanates blocked by means of a blocking agent; and optionally one or more technological additives; wherein said blocking agent is at least one imidazole compound of general formula (I), in a water repellency and/or oil repellency treatment of a fabric or of a skin, having the characteristics as defined in the attached claims.
  • the present invention refers to a use of an imidazole compound of general formula (I) as blocked isocyanate blocking agent in a water repellency and/or oil repellency treatment of a fabric or skin, having the characteristics as defined in the attached claims.
  • Preferred embodiments of the present invention will be described hereinafter by way of example, and therefore not by way of limitation with the aid of the tables, in which:
  • FIG. 11 perspective view of a vertically oriented foulard instrument used in the tests of the examples.
  • an object of the present invention is a composition comprising or, alternatively, consisting of:
  • blocked isocyanates means the reaction products between an isocyanate and said blocking agent, such that at least one isocyanate function is blocked (non-reactive).
  • said mixture (iv) comprises (iii) 5-methyl-3-heptanone oxime in combination with:
  • Said isocyanates are preferably selected from the group consisting of:
  • TDI toluene diisocyanate
  • HDI hexamethylenediisocyanate
  • IPDI isophorone diisocyanate
  • TMDI trimethyl hexamethylene diisocyanate
  • said (d) polyisocyanates derived from isophorone diisocyanate (IPDI) obtained by trimerization, biuretization and/or allophanation process(es) comprise or, alternatively, consist of oligomerization products of 3- isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate and butane-1 -ol and pentane-1 -ol and 2-ethylhexane-1-ol, of allophanate type.
  • IPDI isophorone diisocyanate
  • said (d) comprise the product EC I List no.: 933-047-9, comprising or consisting of the mixture of compounds illustrated in the following general formula (II): wherein R is an alcoholic residue of butane-1 -ol and pentane-1 -ol and 2- ethylhexane-1 -ol.
  • Said isocyanates - are more preferably selected from the group consisting of:
  • adducts preferably trimers, of toluene diisocyanate (TDI) obtained from the reaction between trimethylolpropane and toluene diisocyanate, isocyanurate from hexamethylene diisocyanate (HDI) and isocyanurate from isophorone diisocyanate (IPDI), more preferably a reaction product between trimethylolpropane and a mixture of isomers 2,4 toluene diisocyanate and 2,6 toluene diisocyanate, even more preferably said isomers being in a ratio comprised from 90:10 to 70:30, from 85:15 to 75:25 by weight, for example of 80:20 by weight;
  • TDI toluene diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • Said composition comprising or, alternatively, consisting of blocked isocyanates and optionally one or more technological additives is preferably a non-ionic and/or ionic aqueous suspension or dispersion.
  • a non-ionic and/or ionic aqueous suspension or dispersion it is possible to insert into the molecule a carboxylated ionic group (for example deriving from dimethylolpropionic acid) or an alkoxylated chain having mono-alcoholic functionality (for example polyethylene glycol mono methyl ether with molecular weight of 350, 500 or 750 amu).
  • said suspension or dispersion comprises a mixture of water and co-solvents, preferably in a weight ratio comprised from 2% to 50% and preferably from 5% to 20%.
  • said co-solvents are selected from the group consisting of propylene glycol dimethyl ether, acetone or other low boiling organic solvent.
  • Said composition is preferably free of methyl ethyl ketoxime (MEKO).
  • the object of the present invention is a use of:
  • said mixture (iv) comprises (iii) 5-methyl-3-heptanone oxime in combination with:
  • R1 H or CH 3 ;
  • R2 H, CH 3 , CH 2 CH 3 or CH(CH 3 ) 2 ; as an isocyanate blocking agent in a water repellency and/or oil repellency treatment of a fabric or skin.
  • said imidazole compound is 2-isopropyl-1 H-imidazole (CAS No. 36947-68-9) or 2-ethyl-4-methylimidazole (CAS No. 931 -36-2), or a mixture of said imidazole compounds.
  • said imidazole compound is 2-ethyl-4-methylimidazole.
  • said imidazole compound is 2-isopropyl-1 H-imidazole.
  • said use comprises a deblocking of said isocyanates by said blocking agent in a water repellency and/or oil repellency treatment of a fabric or of a skin.
  • the object of the present invention is a use of a composition comprising or, alternatively, consisting of:
  • said blocking agent is at least one imidazole compound of the following general formula (I): wherein:
  • R1 H or CH 3 ;
  • R2 H, CH 3 , CH 2 CH 3 or CH(CH 3 ) 2 ; in a water repellency and/or oil repellency treatment of a fabric or skin.
  • the expression “at least one imidazole compound” means that said composition may comprise a single imidazole compound of general formula (I), or a mixture of two or more imidazole compounds of general formula (I) having R1 and/or R2 different from each other.
  • said imidazole compound or an imidazole compound of said mixture is 2-isopropyl-1 H-imidazole (CAS No. 36947-68-9) or 2-ethyl-4-methylimidazole (CAS No. 931 -36-2). More preferably, said composition comprises a mixture of 2-isopropyl-1 H-imidazole and 2-ethyl-4-methylimidazole.
  • said imidazole compound or an imidazole compound of said mixture is 2-ethyl-4-methylimidazole.
  • said imidazole compound or an imidazole compound of said mixture is 2-isopropyl-1 H-imidazole.
  • Said blocked isocyanates - ionic or non-ionic - are preferably selected from the group consisting of:
  • TDI toluene diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • TMDI trimethyl hexamethylene diisocyanate
  • CHDI 1 ,4-cyclohexyl diisocyanate
  • Said composition is preferably an aqueous suspension or dispersion.
  • said composition is free of methyl ethyl ketoxime (MEKO).
  • Said composition preferably comprises acrylic acid or methacrylic acid esters (in short: polyacrylates) functionalized with fluorinated chains.
  • said polyacrylates are obtained by means of a copolymerization of the following monomer units (a)-(d):
  • - Rs is a methyl or hydrogen radical
  • Rf is a linear or branched perfluorinated alkyl radical with a number of carbon atoms comprised from 1 to 6, preferably comprised from 4 to 6;
  • - Rh is a group (CH 2 ) n wherein n is an integer comprised from 1 to 6, preferably comprised from 2 to 4;
  • Rz is a benzyl radical or an alkyl radical, linear or branched, comprising from 1 to 30 carbon atoms;
  • Ry is a radical R-[Si(CH3)2O] l-Si (CH3)2-(Rh)m-, where I is an integer comprised from 2 to 30 and R a linear or branched alkyl group with a number of carbon atoms from 1 to 20, Rh and m defined above;
  • - Rs is a methyl or hydrogen radical
  • RZ-OCOC(R 5 ) CH 2 wherein Rz is a radical - R 5 -(Rh)m-, where R5 is a hydroxyl or epoxy group and m is defined above.
  • Said composition further comprises at least one further ingredient selected from paraffin wax and polysiloxane compounds.
  • - Polurgreen AD 01 an adduct of toluene diisocyanate (TDI), in particular a reaction product of trimethylolpropane and toluene diisocyanate (mixture of 2,4- and 2,6-isomers in 80:20 by weight ratio); to give blocked isocyanates.
  • TDI toluene diisocyanate
  • reaction product of trimethylolpropane and toluene diisocyanate mixture of 2,4- and 2,6-isomers in 80:20 by weight ratio
  • the proposed DSC method consists of preparing the blocked isocyanates in a nitrogen atmosphere and then performing the following temperature ramps:
  • Exemplary DSC spectra are reported in the following Figure 1 (relating to test LAB 220621 ) and Figure 2 (relating to test LAB 230621 ).
  • the deblocking temperatures are not particularly high. This aspect is particularly important with a view of optimizing energy consumption and improving process productivity.
  • the tests discussed above were repeated by blocking other isocyanate products with oximes (i), (ii), (iii).
  • the isocyanate products are as follows:
  • Bayhydur® eco 701 -90 (manufactured by Covestro AG): a biobased 1 ,5- pentamethylene diisocyanate (PDI).
  • the general preparation procedure consists in reacting at about 80°C under stirring a polyisocyanate with a methoxy polyethylene glycol.
  • the latter additive is fundamental for subsequently dispersing the product in water.
  • the product obtained is partially blocked with a blocking agent under stirring at a temperature of about 70 °C.
  • the remaining free NCO groups are reacted at about 70°C with a bifunctional compound diglycol and/or diamine to increase the molecular weight thereof.
  • the reaction mixture is then cooled to 50°C and then water is added under stirring up to a concentration of ca. 40%.
  • compositions that are aqueous suspensions or dispersions of ionic or non-ionic blocked isocyanates are reported below. The following were used as blocking agents:
  • reaction temperature is brought to 80 °C and maintained for about one hour until the determination of the free NCO groups still present by titration gives a value of 17.4% by weight.
  • reaction temperature is brought to 80 °C and maintained for about one hour until the determination of the free NCO groups still present by titration gives a value of 17.4% by weight.
  • reaction temperature is brought to 80 °C and maintained for about one hour until the determination of the free NCO groups still present by titration gives a value of 17.4% by weight.
  • reaction temperature is brought to 80 °C and maintained for about one hour until the determination of the free NCO groups still present by titration gives a value of 17.4% by weight. It is then cooled to 70 °C to add dropwise in 30 minutes with a temperature range comprised from 70 °C to 75 °C:
  • the reaction temperature is brought to 70 °C and kept in a range comprised from 70 °C to 75 °C for about two hours, until the determination of the free NCO groups still present gives a value of 6.7% by weight. Subsequently, 15.34 g (0.1761 eq) of MEKO is dripped over a period of about 1 hour taking care that the reaction temperature does not exceed 70 °C.
  • the reaction temperature is brought to 70 °C and kept in a range comprised from 70 °C to 75 °C for about two hours, until the determination of the free NCO groups still present gives a value of 6.7% by weight.
  • the reaction temperature is brought to 70 °C and kept in a range comprised from 70 °C to 75 °C for about two hours, until the determination of the free NCO groups still present gives a value of 6.7% by weight.
  • a stable milky dispersion is obtained, with a solids content of 40.4% by weight.
  • Example 8 Blocking agent (iii) 5-methyl-3-heptanone oxime A glass flask, equipped with an internal thermometer, stirrer and chiller, in a nitrogen atmosphere and at room temperature, is charged - under stirring - with:
  • the reaction temperature is brought to 70 °C and kept in a range comprised from 70 °C to 75 °C for about two hours, until the determination of the free NCO groups still present gives a value of 6.7% by weight.
  • reaction temperature is brought to 80 °C and maintained for about one hour until the determination of the free NCO groups still present by titration gives a value of 17.4% by weight.
  • a stable milky dispersion is obtained, with a solid content of 38.4% by weight.
  • the three oximes (i), (ii), (iii) subject-matter of the present invention have been employed in a typical composition (referred to in Examples 1 , 2, 3) and the respective products in water have been tested to evaluate their performance in comparison with the current marketed products.
  • Example 20A composition with (i) 2-pentanone oxime
  • Example 21 A composition with (ii) 4-methylpentane-2-one oxime;
  • Example 22A composition with (iii) 5-methyl-3-heptanone oxime;
  • Example 31 A composition with mixture of oxime (i)-(iii).
  • Turbiscan Tower instrument configured to analyse destabilization mechanisms in concentrated dispersed media, and thus to provide accelerated ageing testing on unstressed real products.
  • Figure 10 shows Delta Backscattering ABS (%) vs time at 40 °C. In all 4 samples the ABS (%) is less than 1 % confirming that the 4 products are stable. Visually the sample of Example 31 A is more translucent and with finer particles than the other 3 samples. It is likely that the positive trend of Delta Backscattering % is due to better light reflection due to finely dispersed crystals and better homogeneity of the solution. Evaluation of on fabrics tests on fabrics
  • the base + isocyanate compositions have a good yield, comparable and sometimes superior to the reference composition (Comparative Example 5 isocyanate blocked with MEKO).
  • the treatment and evaluation of treated fabrics comprise three steps:
  • the wetting solutions used for the Padding method are obtained by diluting the textile protective agent solution combined with the cross-linking agent.
  • the mixture between the two components usually has a proportion comprised from 90:10 to 80:20, respectively of protective agent and crosslinking agent.
  • the dilution is carried out before treatment, with distilled water, to obtain a concentration comprised between 30 g/L and 100 g/L.
  • a more or less diluted solution will be used (for example, higher weights are used on cotton compared to polyester or polyamide; as a further example, a lower weight will be needed for a fluorinated product compared to a non-fluorinated product).
  • AATCC 22 Spray Test A treated substrate is placed tilted at 45° below a funnel from which 250 ml of deionized water are poured. The wettability of the treated substrate and the resistance thereof are then evaluated according to the AATCC 22 evaluation.
  • the non-fluorinated resin product applied without the use of a blocked isocyanate shows both in the cotton and in the polyamide a low resistance to washes.
  • the photographic index already drops after 4 washes to 70/80 for cotton and to 80 after 6 washes in the case of polyamide.
  • All new products prepared with non-fluorinated base and isocyanates blocked with oxime (i), (ii), (iii) and oxime mixture (iv) show after four washes water repellency properties similar to Product B blocked with MEKO.
  • the water repellency properties are constant with a higher number of washes confirming that the products subject-matter of the present invention are effective crosslinkers.
  • the effectiveness of the products subject-matter of the present invention is also confirmed by the good performance despite containing a lower %NCO compared to standard products blocked with MEKO.
  • AATCC 118 oil repellency
  • AATCC 193 water repellency
  • Example 11 Fluorinated resins and their methods of preparation.
  • the composition may comprise - in addition to said oximes (i)-(iv) or to said imidazole compound of general formula (I) - a polyacrylate consisting of several (meth)acrylic acid esters and optionally further ingredients chosen from paraffin wax and polysiloxanes.
  • the entire composition is suitably used to treat a substrate such as fabrics or skins in order to give hydrophobic, or hydro/oleophobic properties in case the polyacrylate is functionalized with fluorinated chains.
  • the polyacrylate is obtained by means of a copolymerization of the following monomer units (a)-(d):
  • - Rs is a methyl or hydrogen radical
  • Rf is a linear or branched perfluorinated alkyl radical with a number of carbon atoms comprised from 1 to 6, preferably comprised from 4 to 6;
  • - Rh is a group (CH2)n wherein n is an integer comprised from 1 to 6, preferably comprised from 2 to 4;
  • Rz is a benzyl radical or an alkyl radical, linear or branched, comprising from 1 to 30 carbon atoms;
  • - Rs is a methyl or hydrogen radical
  • Ry is a radical R-[Si(CH3)2O] l-Si (CH3)2-(Rh)m-, where I is an integer comprised from 2 to 30 and R a linear or branched alkyl group with a number of carbon atoms from 1 to 20, Rh and m defined above;
  • Rz-OCOC(R5) CH 2 wherein Rz is a radical - R 5 -(Rh)m-, where Rs is a hydroxyl or epoxy group and m is defined above.
  • (meth)acrylate or similar shall mean “acrylate or methacrylate”.
  • the monomer mixture is heated until complete melting, preferably in the presence of solvents.
  • the mixture is dispersed in hot water at 70°C containing suitable surfactants, and is vigorously stirred using for example a Turrax.
  • a subsequent step involves high pressure homogenization (e.g. 400 bar and a temperature of 65-75°C) using a Manton-Gaulin type homogenizer.
  • a radical initiator possibly dissolved or dispersed in water.
  • the polymerization reaction is carried out for several hours at a temperature of 60- 70°C, until the monomers are exhausted.
  • the deblocking temperatures are not particularly high.
  • This aspect is an application advantage and is particularly important with a view to optimizing energy consumption and improving process productivity.
  • the presence of differentiated deblocking temperatures allows to obtain a series of flexibilities, for example necessary to optimize the processes of use of such compositions.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Une composition comprenant ou, en variante, consistant en : - des isocyanates bloqués au moyen d'un agent de blocage choisi dans le groupe constitué par : (i) éventuellement de l'oxime 2-pentanone ; (ii) de l'oxime 4-méthylpentane-2-one ; (iii) de l'oxime 5-méthyl-3-heptanone ; et (iv) un mélange de deux ou plus des composés (i)-(iii) ; et éventuellement un ou plusieurs additifs technologiques.
PCT/IB2023/050967 2022-02-03 2023-02-03 Composition d'isocyanates bloqués et utilisation de composés en tant qu'agents de blocage d'isocyanates WO2023148675A1 (fr)

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IT102022000001949A IT202200001949A1 (it) 2022-02-03 2022-02-03 Composizione di isocianati bloccati, uso di composti come agenti bloccanti di isocianati
IT102022000001949 2022-02-03

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015025776A1 (fr) * 2013-08-23 2015-02-26 三井化学株式会社 Isocyanate bloqué, composition de revêtement, composition d'agent adhésif, et article
EP3783041A1 (fr) * 2019-08-02 2021-02-24 Asahi Kasei Kabushiki Kaisha Composition de polyisocyanate bloquée, composition de polyisocyanate hydrophile, composition de résine, film de résine et corps stratifié

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015025776A1 (fr) * 2013-08-23 2015-02-26 三井化学株式会社 Isocyanate bloqué, composition de revêtement, composition d'agent adhésif, et article
EP3783041A1 (fr) * 2019-08-02 2021-02-24 Asahi Kasei Kabushiki Kaisha Composition de polyisocyanate bloquée, composition de polyisocyanate hydrophile, composition de résine, film de résine et corps stratifié

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