ITVA20100033A1 - AQUEOUS DISPERSIONS OF ANIONIC POLYURETHANE - Google Patents

AQUEOUS DISPERSIONS OF ANIONIC POLYURETHANE Download PDF

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ITVA20100033A1
ITVA20100033A1 IT000033A ITVA20100033A ITVA20100033A1 IT VA20100033 A1 ITVA20100033 A1 IT VA20100033A1 IT 000033 A IT000033 A IT 000033A IT VA20100033 A ITVA20100033 A IT VA20100033A IT VA20100033 A1 ITVA20100033 A1 IT VA20100033A1
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weight
aqueous dispersions
mixture
polyol
polyols
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IT000033A
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Kroutilova Irena Amici
Thierry Bossi
Gabriele Costa
Luca Mariuccia De
Franco Federici
Giovanni Floridi
Bassi Giuseppe Li
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Lamberti Spa
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Priority to ITVA2010A000033A priority Critical patent/IT1399424B1/en
Priority to EP11715460A priority patent/EP2556097A1/en
Priority to KR1020127027572A priority patent/KR101791283B1/en
Priority to PCT/EP2011/055337 priority patent/WO2011124602A1/en
Priority to CN201180017821.0A priority patent/CN102822220B/en
Publication of ITVA20100033A1 publication Critical patent/ITVA20100033A1/en
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Publication of IT1399424B1 publication Critical patent/IT1399424B1/en

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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
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
    • 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

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Description

Descrizione dell’invenzione industriale dal titolo: Description of the industrial invention entitled:

DISPERSIONI ACQUOSE DI POLIURETANI ANIONICI WATER DISPERSIONS OF ANIONIC POLYURETHANS

La presente invenzione à ̈ relativa a dispersioni acquose di poliuretani anionici preparati a partire da specifici polioli idrofobici e al loro uso come agenti filmanti per il rivestimento di superfici rigide, quali quelle di metalli, plastica, vetro e legno. The present invention relates to aqueous dispersions of anionic polyurethanes prepared starting from specific hydrophobic polyols and to their use as filming agents for the coating of rigid surfaces, such as those of metals, plastic, glass and wood.

Le dispersioni acquose dell’invenzione permettono di ottenere rivestimenti eccellenti quanto a durata, adesione, resistenza idrolitica, resistenza alle basi e agli acidi, durezza. The aqueous dispersions of the invention allow to obtain excellent coatings in terms of durability, adhesion, hydrolytic resistance, resistance to bases and acids, hardness.

STATO DELL'ARTE STATE OF THE ART

La superficie di molti manufatti, per esempio la superficie di manufatti realizzati in pelle, plastica, legno, vetro e metallo, viene trattata con lo scopo di renderla più omogenea, o per proteggerla dall’usura dovuta al tempo o all’atmosfera e/o per migliorarne alcune caratteristiche estetiche, quali la trasparenza o l’opacità, il tocco ruvido o morbido, il colore, e così via. The surface of many artifacts, for example the surface of artifacts made of leather, plastic, wood, glass and metal, is treated with the aim of making it more homogeneous, or to protect it from wear due to time or atmosphere and / or to improve some aesthetic characteristics, such as transparency or opacity, rough or soft touch, color, and so on.

Normalmente, questi effetti sono ottenuti attraverso l’applicazione di polimeri filmanti (coating) e, tra la grande varietà di polimeri filmanti, i poliuretani a base solvente sono ben noti e apprezzati nel settore, poiché permettono di realizzare film con eccellente resistenza chimica e meccanica. Normally, these effects are obtained through the application of film-forming polymers (coating) and, among the great variety of film-forming polymers, solvent-based polyurethanes are well known and appreciated in the sector, as they allow to produce films with excellent chemical resistance. and mechanics.

Dispersioni acquose di poliuretani hanno anch’esse recentemente acquisito un ruolo rilevante, a causa anche della crescente attenzione prestata dalle politiche regolamentatorie all’abbassamento delle emissioni di composti organici volatili nell’ambiente e, in particolare, nei luoghi di lavoro. Aqueous dispersions of polyurethanes have also recently acquired an important role, also due to the growing attention paid by regulatory policies to lowering emissions of volatile organic compounds in the environment and, in particular, in the workplace.

Volendo utilizzare dei poliuretani in forma di dispersioni acquose per il coating, sorgono problemi legati al fatto che la loro disperdibilità in acqua richiede l’inclusione di segmenti idrofilici nella struttura e questi stessi riducono la durata e la stabilità idrolitica dei film. Wanting to use polyurethanes in the form of aqueous dispersions for the coating, problems arise due to the fact that their dispersibility in water requires the inclusion of hydrophilic segments in the structure and these reduce the duration and hydrolytic stability of the films.

E’ noto nel settore che si possono introdurre nei poliuretani dei gruppi insaturi che causano la reticolazione del film e di conseguenza ne migliorano la resistenza; sfortunatamente, l’ingiallimento del film e la necessità di condizioni fortemente ossidative per la reticolazione sono svantaggi connessi alla presenza di gruppi insaturi nei poliuretani. It is known in the field that unsaturated groups can be introduced into the polyurethanes which cause the film to cross-link and consequently improve its resistance; unfortunately, the yellowing of the film and the need for highly oxidative conditions for crosslinking are disadvantages connected to the presence of unsaturated groups in polyurethanes.

US 2003/0191273 descrive l’utilizzo di dispersioni acquose di poliuretani preparati con alcanolammidi di acidi grassi come composizioni per il coating; à ̈ riportato che i rivestimenti prodotti da queste dispersioni hanno buona durezza al pendolo, buona resistenza al graffio e alti gradi di lucido. US 2003/0191273 describes the use of aqueous dispersions of polyurethanes prepared with alkanolamides of fatty acids as compositions for the coating; The coatings produced from these dispersions are reported to have good pendulum hardness, good scratch resistance and high gloss levels.

US 2008/0194757 descrive composizioni di poliuretani dispersi in acqua che contengono un composto “nurato†recante un gruppo alchilico a catena lunga come componente poliisocianico; si riporta che le composizioni danno rivestimenti aventi eccellente adesione, resistenza all’acqua, agli agenti atmosferici, alla corrosione, repellenti all’acqua e ai grassi. US 2008/0194757 discloses compositions of polyurethanes dispersed in water which contain a â € œnurateâ € compound bearing a long-chain alkyl group as a polyisocyanic component; it is reported that the compositions give coatings having excellent adhesion, resistance to water, atmospheric agents, corrosion, water and grease repellents.

Sorprendentemente, à ̈ stato ora trovato che à ̈ possibile ottenere dispersioni acquose di poliuretani anionici capaci di fornire film durevoli aventi eccellente adesione su substrati rigidi, resistenza chimica e durezza incorporando nel poliuretano un particolare poliolo idrofobico ottenuto facendo reagire un alcol grasso con un diglicidil etere aromatico. Surprisingly, it has now been found that it is possible to obtain aqueous dispersions of anionic polyurethanes capable of providing durable films having excellent adhesion on rigid substrates, chemical resistance and hardness by incorporating in the polyurethane a particular hydrophobic polyol obtained by reacting a fatty alcohol with a diglycidyl ether. aromatic.

RIASSUNTO DELL’INVENZIONE SUMMARY OF THE INVENTION

La presente invenzione ha per oggetto dispersioni acquose contenenti da 20 a 50% in peso di poliuretani anionici ottenuti disperdendo in acqua ed estendendo con una poliammina un prepolimero anionico neutralizzato che contiene da 5 a 250 meq/100 g sul secco di gruppi carbossilici e preparato facendo reagire uno o più poliisocianati alifatici, cicloalifatici o aromatici con una miscela di polioli (P) che comprende: The present invention relates to aqueous dispersions containing from 20 to 50% by weight of anionic polyurethanes obtained by dispersing in water and extending with a polyamine a neutralized anionic prepolymer containing from 5 to 250 meq / 100 g on the dry basis of carboxylic groups and prepared by making react one or more aliphatic, cycloaliphatic or aromatic polyisocyanates with a mixture of polyols (P) which includes:

I) da 4 a 90% in peso di uno o più polioli idrofobici aventi funzionalità idrossilica media molare da 2 a 3, numero di ossidrile da 350 a 40 (mg KOH/g) e ottenuti facendo reagire un alcohol ROH, in cui R à ̈ un catena alchilica satura, lineare o ramificata C4-C30, preferibilmente C6-C22, o R à ̈ un radicale fenile sostituito con una catena alchilica satura, lineare o ramificata C4-C10, con un diglicidil etere aromatico di formula (I): I) from 4 to 90% by weight of one or more hydrophobic polyols with mean molar hydroxyl functionality from 2 to 3, hydroxyl number from 350 to 40 (mg KOH / g) and obtained by reacting an alcohol ROH, in which R à ̈ a saturated, linear or branched C4-C30 alkyl chain, preferably C6-C22, or R is a phenyl radical substituted with a saturated, linear or branched C4-C10 alkyl chain, with an aromatic diglycidyl ether of formula (I):

O O O O

O O O O

R1R1

(I) (THE)

in cui R1Ã ̈ il radicale (i): where R1Ã is the radical (i):

(i) (the)

in cui R2e R3sono uno indipendentemente dall’altro Me, Et, o H; in which R2 and R3 are one independently of the other Me, Et, or H;

o R1à ̈ un radicale fenilene, eventualmente sostituito con uno o più gruppi alchilici e preferibilmente con un metile; or R1à a phenylene radical, optionally substituted with one or more alkyl groups and preferably with a methyl;

o R1à ̈ un radicale bis-fenilene, eventualmente sostituito con uno o più gruppi alchilici e preferibilmente con un metile; o R1à ̈ il radicale (ii): or R1à is a bis-phenylene radical, optionally substituted with one or more alkyl groups and preferably with a methyl; or R1à ̈ the radical (ii):

O OR

O OR

(ii) II) da 1 a 10% in peso di uno o più polioli anionici o potenzialmenteanioniciaventidueopiùgruppireattivinei confronti dei gruppi isocianici e almeno un gruppo carbossilicoocarbossilato; (ii) II) from 1 to 10% by weight of one or more anionic or potentially anionic polyols in twenty-two more reactive groups with respect to isocyanic groups and at least one carboxylic carboxylate group;

III) da 0 a 95 % in peso di uno o più policarbonati dioli lineari aventi peso molecolare da 500 a 3,000; III) from 0 to 95% by weight of one or more linear polycarbonate diols having molecular weight from 500 to 3,000;

IV) da 0 a 95% in peso di uno o più poliesteri dioli lineari aventi peso molecolare da 500 a 4,000; IV) from 0 to 95% by weight of one or more linear polyester diols having molecular weight from 500 to 4,000;

V) da 0 a 95% in peso di uno o più polialchilene dioli scelti tra poli(ossipropilene) glicol e poli(ossitetrametilene) glicol, i poliisocianati e la miscela di polioli (P) essendo in proporzioni tali che: a) il rapporto tra i gruppi isocianici NCO dei poliisocianati e la somma di tutti i gruppi –OH reattivi della miscela di polioli (P) sia compresa tra 1.2 e 2.3. V) from 0 to 95% by weight of one or more polyalkylene diols selected from poly (oxypropylene) glycol and poly (oxytetramethylene) glycol, the polyisocyanates and the mixture of polyols (P) being in such proportions that: a) the ratio between the NCO isocyanic groups of the polyisocyanates and the sum of all reactive - OH groups of the polyol mixture (P) is between 1.2 and 2.3.

Secondo un altro aspetto, l’invenzione à ̈ relativa all’uso delle sopradescritte dispersioni acquose di poliuretani anionici per la preparazione di composizioni per il coating di substrati rigidi. According to another aspect, the invention relates to the use of the aqueous dispersions described above of anionic polyurethanes for the preparation of compositions for the coating of rigid substrates.

DESCRIZIONE DETTAGLIATA DETAILED DESCRIPTION

In una forma di realizzazione, i componenti I), II), III), IV) e V) costituiscono almeno il 95% in peso della miscela di polioli, la miscela di polioli comprendendo ulteriormente da 0 a 5% in peso di altri polioli non ionici aventi peso molecolare inferiore a 1,000 e contenenti due o più gruppi idrossilici; esempi di tali polioli non ionici utilizzabili sono glicerolo, pentaeritritolo, neopentil glicol, butandiolo, 1,4-cicloesandimetanolo, trimetilolpropano e suoi derivati, quali il trimetilolpropano propossilato, polibutadieni polifunzionali e poliesteri polioli. In one embodiment, components I), II), III), IV) and V) constitute at least 95% by weight of the polyol blend, the polyol blend further comprising 0 to 5% by weight of other polyols non-ionic having a molecular weight of less than 1,000 and containing two or more hydroxyl groups; examples of such usable non-ionic polyols are glycerol, pentaerythritol, neopentyl glycol, butanediol, 1,4-cyclohexanedimethanol, trimethylolpropane and its derivatives, such as propoxylated trimethylolpropane, polyfunctional polybutadienes and polyester polyols.

In una forma di realizzazione preferita, i componenti I), II), III), IV) e V) costituiscono il 100% in peso della miscela di polioli (P) del prepolimero; in una realizzazione ancora più preferita, i componenti I), II), III), e IV) costituiscono il 100% in peso della miscela di polioli. Il poliolo idrofobico (I) non contiene gruppi epossidici e preferibilmente rappresenta dal 5 al 75 % in peso della miscela di polioli (P). In a preferred embodiment, components I), II), III), IV) and V) constitute 100% by weight of the polyol mixture (P) of the prepolymer; in an even more preferred embodiment, components I), II), III), and IV) constitute 100% by weight of the polyol mixture. The hydrophobic polyol (I) does not contain epoxy groups and preferably represents from 5 to 75% by weight of the polyol mixture (P).

Vantaggiosamente, nel diglicidil etere di formula (I) R1Ã ̈ il radicale (i) in cui R2e R3sono metili. Advantageously, in the diglycidyl ether of formula (I) R1 is the radical (i) in which R2 and R3 are methyls.

I poliisocianati utilizzabili hanno funzionalità media –NCO compresa tra 2.0 e 2.3 e sono preferibilmente alifatici o cicloalifatici. The usable polyisocyanates have medium functionality - NCO between 2.0 and 2.3 and are preferably aliphatic or cycloaliphatic.

Esempi di poliisocianati utilizzabili sono 4,4' - dicicloesil-metandiisocianato, 1-isocianato-3-(isocianatometil)-3,5,5-trimetilcicloesano (o isoforonediisocianato), tetrametilene diisocianato, esametilene diisocianato, e loro miscele. Examples of usable polyisocyanates are 4,4 '- dicyclohexyl-methanediisocyanate, 1-isocyanate-3- (isocyanatomethyl) -3,5,5-trimethylcyclohexane (or isophorone diisocyanate), tetramethylene diisocyanate, hexamethylene diisocyanate, and mixtures thereof.

I poliisocianati maggiormente preferiti sono 4,4' - dicicloesil-metandiisocianato, 1-isocianato-3-(isocianatometil)-3,5,5-trimetilcicloesano (o isoforonediisocianato), esametilene diisocianato, e loro miscele. The most preferred polyisocyanates are 4,4 '- dicyclohexyl-metanediisocyanate, 1-isocyanate-3- (isocyanatomethyl) -3,5,5-trimethylcyclohexane (or isophorone diisocyanate), hexamethylene diisocyanate, and mixtures thereof.

Poliisocianati aventi funzionalità –NCO media maggiore di 2 s i ottengono dalla parziale trimerizzazione, biuretizzazione, uretanizzazione o allofanazione di diisocianati, quali l’esametilene di isocianato, l’isoforondiisocianato , il 4,4' - dicicloesil-metan-diisocianato e loro miscele, o miscelando i suddetti di isocianati con loro prodotti di trimerizzazione, biuretizzazione, uretanizzazione o allofanazione. Polyisocyanates with an average NCO functionality greater than 2 s are obtained from the partial trimerization, biuretization, urethaneization or alloophanation of diisocyanates, such as isocyanate hexamethylene, isophorondisocyanate, 4,4 '- dicyclohexyl-methane-diisocyanate and their mixtures, or by mixing the aforesaid isocyanates with their products of trimerization, biuretization, urethanization or allophanation.

Il componente II) della miscela di polioli (P) à ̈ preferibilmente un acido carbossilico sostituito nella posizione 2 da due gruppi idrossimetilici, quale l’acido dimetilolpropionico, dimetilolbutanoico o loro miscele. La quantità di componente II) nella miscela di polioli à ̈ scelta in modo tale da ottenere un prepolimero che contiene da 5 a 125 meq/100 g sul secco di gruppi –COOH; i migliori risultati si ottengono quando questo valore à ̈ compreso tra 20 e 60. Component II) of the polyol mixture (P) is preferably a carboxylic acid substituted in position 2 by two hydroxymethyl groups, such as dimethylolpropionic acid, dimethylolbutanoic acid or their mixtures. The quantity of component II) in the mixture of polyols is chosen in such a way as to obtain a prepolymer that contains from 5 to 125 meq / 100 g on the dry basis of â € “COOH; the best results are obtained when this value is between 20 and 60.

Il componente III) della miscela di polioli (P) può essere scelto tra i policarbonati ottenuti dalla de-alcol condensazione di dioli a basso peso molecolare con dialchil carbonati, dalla de-fenol condensazione di dioli a basso peso molecolare con difenil carbonati, o dalla de-glicol condensazione di dioli a basso peso molecolare con alchilene carbonati o dialchil carbonati. Component III) of the polyol mixture (P) can be chosen from the polycarbonates obtained from the de-alcohol condensation of low molecular weight diols with dialkyl carbonates, from the de-phenol condensation of low molecular weight diols with diphenyl carbonates, or from the de-glycol condensation of low molecular weight diols with alkylene carbonates or dialkyl carbonates.

Esempi di dioli a basso peso molecolare includono 1,4-butandiolo, 1,5-pentandiolo, 1,6-esandiolo, etilene glicol, propilene glicol, 3-metil-1,5-pentandiolo, nepentilglicol, dietilene glicol, 1,4-cicloesanodiolo, 1,4-cicloesanodimetanolo e simili. Examples of low molecular weight diols include 1,4-butanediol, 1,5-pentanediol, 1,6-hexandiol, ethylene glycol, propylene glycol, 3-methyl-1,5-pentanediol, nepentylglycol, diethylene glycol, 1,4 -cyclohexanodiol, 1,4-cyclohexanodimethanol and the like.

Esempi di dialchil carbonati includono dimetil carbonato e dietil carbonato. Un esempio di dialchilene carbonato à ̈ il dietilene carbonato. Examples of dialkyl carbonates include dimethyl carbonate and diethyl carbonate. An example of dialkylene carbonate is diethylene carbonate.

Un esempio particolarmente preferito di policarbonato diolo à ̈ il poli(esametilene carbonato)diolo, ottenuto dalla condensazione dell’1,6-esandiolo con un dialchil carbonato. A particularly preferred example of polycarbonate diol is the poly (hexamethylene carbonate) diol, obtained from the condensation of 1,6-hexanediol with a dialkyl carbonate.

Il policarbonato diolo ha preferibilmente peso molecolare numerale medio da 800 a 2,000. The polycarbonate diol preferably has an average number molecular weight from 800 to 2,000.

Il componente IV) della miscela di polioli (P) può essere scelto tra i poliesteri ottenuti dalla reazione di acidi, esteri anidridi o alogenuri acilici con glicoli. Component IV) of the polyol mixture (P) can be chosen from the polyesters obtained from the reaction of acids, anhydride esters or acyl halides with glycols.

Utili per la preparazione dei suddetti poliesteri sono, per esempio, l’acido maleico, succinico, adipico, suberico, sebacico, ftalico, tereftalico e isoftalico e eventualmente i loro corrispondenti alogenuri acilici, esteri e anidridi. Useful for the preparation of the aforesaid polyesters are, for example, maleic, succinic, adipic, suberic, sebacic, phthalic, terephthalic and isophthalic acids and possibly their corresponding acyl halides, esters and anhydrides.

Esempi di glicoli idonei sono etilene glicol, 1,4-butandiolo, 1,3-propandiolo, 1,2-propandiolo, neopentilglicol, tetrametilene glicol, dietilene glicol, 1,6-esandiolo, 1,5-pentandiol; alchilene glicol sostituiti, quali 2,2-dimetil-1,3-propandiolo; glicoli ciclici, quali 1,4-cicloesanediol e 1,4-cicloesandimetanolo, e glicoli aromatici; questi glicoli vengono fatti reagire con acidi dicarbossilici alifatici, cicloalifatici o aromatici o con alchil esteri di alcoli aventi basso peso molecolare o con composti che sono in grado di formare esteri, in modo da ottenere polimeri con peso molecolare relativamente basso, e preferibilmente aventi punto di fusione inferiore a circa 80°C. Examples of suitable glycols are ethylene glycol, 1,4-butanediol, 1,3-propanediol, 1,2-propanediol, neopentylglycol, tetramethylene glycol, diethylene glycol, 1,6-hexanediol, 1,5-pentanediol; substituted alkylene glycol, such as 2,2-dimethyl-1,3-propanediol; cyclic glycols, such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, and aromatic glycols; these glycols are reacted with aliphatic, cycloaliphatic or aromatic dicarboxylic acids or with alkyl esters of alcohols having low molecular weight or with compounds which are capable of forming esters, so as to obtain polymers with relatively low molecular weight, and preferably having a melting below about 80 ° C.

E’ possibile anche utilizzare il policaprolattone idrossi-terminato. It is also possible to use hydroxy-terminated polycaprolactone.

Il poliestere diolo ha preferibilmente peso molecolare numerale medio da 800 a 3,000. The polyester diol preferably has an average number molecular weight from 800 to 3,000.

In una forma di realizzazione preferita, il poliestere diolo à ̈ scelto tra i poliesteri a base di acido adipico e/o ftalico con 1,6-esandiolo, etilene glicol, dietilene glicol, neopentilglicol, 1,4-butandiolo o loro miscele. Secondo un aspetto preferito, i polioli della al miscela (P) sono privi di unità che derivano da poli(ossietilene)glicol. In a preferred embodiment, the polyester diol is selected from polyesters based on adipic and / or phthalic acid with 1,6-hexanediol, ethylene glycol, diethylene glycol, neopentylglycol, 1,4-butanediol or their mixtures. According to a preferred aspect, the polyols of the mixture (P) are free of units deriving from poly (oxyethylene) glycol.

Le dispersioni acquose di poliuretani della presente invenzione possono essere preparate: i) facendo reagire, nelle proporzioni sopra definite, i poliisocianati con la miscela di polioli (P); ii) disperdendo il prepolimero ottenuto in acqua; iii) aggiungendo una poliammina (estensore di catena) alla dispersione così ottenuta e lasciando reagire finché tutti i gruppi isocianati sono scomparsi. The aqueous polyurethane dispersions of the present invention can be prepared: i) by reacting, in the proportions defined above, the polyisocyanates with the polyol mixture (P); ii) dispersing the prepolymer obtained in water; iii) adding a polyamine (chain extender) to the dispersion thus obtained and letting it react until all the isocyanate groups have disappeared.

Lo stadio i) à ̈ preferibilmente condotto in presenza di un solvente organico o di una miscela di solventi organici a temperatura compresa tra 40 e 110°C; tuttavia, à ̈ stato trovato che l’utilizzo del poliolo idrofobico I) riduce la viscosità della miscela di reazione e quindi, vantaggiosamente, la quantità di solvente necessario e il complessivo consumo di VOC nella sintesi. Step i) is preferably carried out in the presence of an organic solvent or a mixture of organic solvents at a temperature between 40 and 110 ° C; however, it has been found that the use of hydrophobic polyol I) reduces the viscosity of the reaction mixture and therefore, advantageously, the amount of solvent required and the overall consumption of VOC in the synthesis.

Solventi idonei sono i solventi comunemente utilizzati, quali N-metilpirrolidone, N-etilpirrolidone, dipropilene glicol dimetil etere, etil acetato, butil acetato, etilene glicol monometil o monoetil etere acetato, 1-metossipropil-2-acetato, 3-metossi-n-butil acetato, acetone, 2-butanone, 4-metil-2-pentanone, cicloesanone, miscele di solventi aromatici, esteri carbonici, quali dimetil carbonato, dietil carbonato, 1,2-etilene carbonato e 1,2-propilene carbonato, lattoni, quali [beta]-propiolattone, [gamma]-butirrolattone, [epsilon]-caprolattone e [epsilon]-metilcaprolattone, ma anche solventi quali il propilene glicol diacetato, dietilene glicol dimetil etere, dietilene glicol etil etere acetato, dietilene glicol butil etere acetato e N-metilcaprolattame, o una qualsiasi miscela di tali solventi. Suitable solvents are commonly used solvents, such as N-methylpyrrolidone, N-ethylpyrrolidone, dipropylene glycol dimethyl ether, ethyl acetate, butyl acetate, ethylene glycol monomethyl or monoethyl ether acetate, 1-methoxypropyl-2-acetate, 3-methoxy-n- butyl acetate, acetone, 2-butanone, 4-methyl-2-pentanone, cyclohexanone, mixtures of aromatic solvents, carbonic esters, such as dimethyl carbonate, diethyl carbonate, 1,2-ethylene carbonate and 1,2-propylene carbonate, lactones, such as [beta] -propiolactone, [gamma] -butyrolactone, [epsilon] -caprolactone and [epsilon] -methylcaprolactone, but also solvents such as propylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate and N-methylcaprolactam, or any mixture of such solvents.

I solventi preferiti sono N-etilpirrolidone e dipropilene glicol dimetil etere. The preferred solvents are N-ethylpyrrolidone and dipropylene glycol dimethyl ether.

Il prepolimero ottenuto alla fine dello stadio i) Ã ̈ normalmente neutralizzato, preferibilmente con ammine terziarie, quali le N-alchilmorfoline, le trialchilammine, le dialcanolammine, le alchildialcanolammine, le trialcanolammine e loro miscele, a temperatura inferiore a 90°C. The prepolymer obtained at the end of step i) is normally neutralized, preferably with tertiary amines, such as N-alkylmorpholines, trialkylamines, dialkanolamines, alkyldyalkanolamines, trialkanolamines and their mixtures, at a temperature below 90 ° C.

Tietilammina, dimetiletanolammina e N-metilmorfolina sono particolarmente adatte a questo scopo. Thethylamine, dimethylethanolamine and N-methylmorpholine are particularly suitable for this purpose.

La neutralizzazione può essere condotta alla fine dello stadio di reazione i), in ambiente anidro, o durante il seguente stadio di dispersione in acqua del prepolimero (stadio ii). Neutralization can be carried out at the end of reaction stage i), in anhydrous environment, or during the following stage of dispersion of the prepolymer in water (stage ii).

Lo stadio ii) Ã ̈ effettuato versando il prepolimero in acqua sotto agitazione meccanica, eventualmente in presenza di un emulsionate, o viceversa. Step ii) is carried out by pouring the prepolymer into water under mechanical stirring, possibly in the presence of an emulsifier, or vice versa.

L’emulsionante può essere scelto tra i tensioattivi nonionici, anionici e cationici; preferibilmente, l’emulsionante à ̈ un tensioattivo nonionico. Le poliammine dello stadio iii) sono preferibilmente diammine alifatiche primarie o secondarie. The emulsifier can be chosen from nonionic, anionic and cationic surfactants; preferably, the emulsifier is a nonionic surfactant. The polyamines of stage iii) are preferably primary or secondary aliphatic diamines.

Nello stadio iii) Ã ̈ possibile utilizzare una miscela di poliammine. In stage iii) it is possible to use a mixture of polyamines.

Esempi di poliammine utilizzabili sono idrazina, etilene diammina, piperazina, 1,5-pentandiammina, 1,6-diesandiammina, isoforondiammina, dietilentriammina, 2-metil-1,5-pentandiammina e 4,4’-metilene-bis-cicloesilammina. Examples of usable polyamines are hydrazine, ethylene diamine, piperazine, 1,5-pentanediamine, 1,6-hexanediamine, isoforondiamine, diethylenetriamine, 2-methyl-1,5-pentanediamine and 4,4â € ™ -methylene-bis-cyclohexylamine.

La temperatura e la durata dello stadio iii) e il quantitativo di poliammina sono determinati in modo tale da esaurire i gruppi –NCO liberi che sono presenti nel prepolimero e per ottenere una dispersione stabile e omogenea di poliuretano, come à ̈ ben noto nel settore. The temperature and duration of stage iii) and the amount of polyamine are determined in such a way as to exhaust the free NCO groups present in the prepolymer and to obtain a stable and homogeneous dispersion of polyurethane, as is well known in the sector.

Il solvente organico eventualmente presente può essere allontanato mediante distillazione durante lo stadio iii) o alla fine dello stadio iii). Any organic solvent present can be removed by distillation during stage iii) or at the end of stage iii).

Lo stadio iii) può essere condotto percolando la poliammina nella dispersione del prepolimero mantenuta sotto agitazione meccanica a temperatura inferiore a 40°C. Step iii) can be carried out by percolating the polyamine into the prepolymer dispersion maintained under mechanical stirring at a temperature below 40 ° C.

La viscosità Brookfield® della dispersione acquosa di poliuretano anionico della presente invenzione à ̈ generalmente compresa tra 50 e 2,000 mPa*s. The Brookfield® viscosity of the aqueous dispersion of anionic polyurethane of the present invention is generally between 50 and 2,000 mPa * s.

Per la preparazione delle composizioni per il coating, le dispersioni acquose di poliuretani anionici possono essere miscelate con dei leganti, preferibilmente acrilici, con reticolanti e/o con altri additivi, in modo da migliorare ulteriormente le loro proprietà applicative nel coating, quali ad esempio il potere filmante, la riduzione o l’incremento dell’opacizzazione, la soluzione di problemi di superficie quali la buccia di arancia, i punti bianchi e la schiuma. For the preparation of the compositions for the coating, the aqueous dispersions of anionic polyurethanes can be mixed with binders, preferably acrylics, with crosslinkers and / or with other additives, in order to further improve their application properties in the coating, such as for example the filming power, reduction or increase of opacification, the solution of surface problems such as orange peel, white spots and foam.

Esempi di additivi che possono essere aggiunti alle composizioni per coating sono agenti livellanti, bagnanti, cariche, pigmenti, cere, tensioattivi, addensanti, agenti coalescenti, inibitori di ruggine, etc. Le dispersioni acquose di poliuretani anionici della presente invenzione possono anche essere reticolate con tutti i reticolanti noti agli esperti del settore, quali poliisocianati idrodisperdibili, poliisociananti bloccati, poliaziridine, carbodiimmidi, epossisilani e melammine. Examples of additives that can be added to coating compositions are leveling agents, wetting agents, fillers, pigments, waxes, surfactants, thickeners, coalescing agents, rust inhibitors, etc. The aqueous dispersions of anionic polyurethanes of the present invention can also be crosslinked with all crosslinkers known to those skilled in the art, such as water-dispersible polyisocyanates, blocked polyisocyanants, polyaziridines, carbodiimides, epoxysilanes and melamines.

I reticolanti possono essere aggiunti in quantità compresa tra 1 e 10% sul secco della dispersione. The crosslinking agents can be added in quantities ranging from 1 to 10% on the dry basis of the dispersion.

La reticolazione può essere utile per aumentare le proprietà meccaniche e chimiche dei film. Crosslinking can be useful for increasing the mechanical and chemical properties of the films.

Le dispersioni acquose di poliuretani anionici filmanti della presente invenzione e le composizioni per il coating che le contengono possono vantaggiosamente essere utilizzate per la rifinizione di substrati rigidi, quali plastiche (per esempio policarbonati, ABS e PVC), legno, vetro e metalli (per esempio alluminio, acciaio, ferro ed acciai galvanizzati: GA, GL, GI e EGI). The aqueous dispersions of anionic film-forming polyurethanes of the present invention and the compositions for the coating containing them can advantageously be used for the finishing of rigid substrates, such as plastics (for example polycarbonates, ABS and PVC), wood, glass and metals (for example aluminum, steel, iron and galvanized steels: GA, GL, GI and EGI).

I materiali rivestiti con i film ottenuti dalle dispersioni acquose dell’invenzione possono essere utilizzati per gli interni di auto per la rifinizione della strumentazione o per la parte interna delle portiere, su prodotti di elettronica, quali cellulari, i-Pod® e i-Pad®, per la rifinizione di superfici metalliche quali l’esterno di computer e televisori, e per la verniciatura in continuo dei metalli. The materials coated with the films obtained from the aqueous dispersions of the invention can be used for car interiors for the finishing of instruments or for the inside of the doors, on electronic products, such as mobile phones, i-Pod® and i- Pad®, for finishing metal surfaces such as the exterior of computers and televisions, and for continuous painting of metals.

Negli esempi che seguono vengono riportate la sintesi di polioli idrofobici e la preparazione di dispersioni acquose secondo al presente invenzione. In the following examples the synthesis of hydrophobic polyols and the preparation of aqueous dispersions according to the present invention are reported.

La dimensione delle particelle delle dispersioni sono state misurate per mezzo della Laser Correlation Spectroscopy (LCS) con un Coulter N4 Plus Instrument a temperatura 25°C e angolo 90°. The particle size of the dispersions were measured by means of Laser Correlation Spectroscopy (LCS) with a Coulter N4 Plus Instrument at a temperature of 25 ° C and an angle of 90 °.

ESEMPI EXAMPLES

I seguenti materiali, così come elencati di seguito, sono stati usati negli esempi descritti più oltre. The following materials, as listed below, were used in the examples described below.

POLYOL 1: poliestere diolo, adipato ftalato da 1,6-esandiolo, peso molecolare 1.000 g/mol POLYOL 1: polyester diol, adipate phthalate from 1,6-hexandiol, molecular weight 1,000 g / mol

POLYOL 2: policarbonato diolo, poli(esametilene carbonato)diolo, peso molecolare 1.000 g/mol POLYOL 2: polycarbonate diol, poly (hexamethylene carbonate) diol, molecular weight 1,000 g / mol

H-POLYOL 5: cocco dietanolammide, peso molecolare 213 g/mol H-POLYOL 6: dietanolammide oleica, peso molecolare 269,7 g/mol DGEBA: diglicidil etere del Bisfenolo A, peso molecolare 380 DMPA: acido dimetilolpropionico, peso molecolare 134,2 g/mol ALCOHOL C6: n-esanolo, peso molecolare 102 g/mol H-POLYOL 5: coco diethanolamide, molecular weight 213 g / mol H-POLYOL 6: oleic diethanolamide, molecular weight 269.7 g / mol DGEBA: bisphenol A diglycidyl ether, molecular weight 380 DMPA: dimethylolpropionic acid, molecular weight 134, 2 g / mol ALCOHOL C6: n-hexanol, molecular weight 102 g / mol

ALCOHOL C12: n-dodecanolo, peso molecolare 186 g/mol ALCOHOL C20: mono-alcol C20 lineare, peso molecolare 298 g/mol NMP: N-metilpirrolidone ALCOHOL C12: n-dodecanol, molecular weight 186 g / mol ALCOHOL C20: mono-alcohol C20 linear, molecular weight 298 g / mol NMP: N-methylpyrrolidone

NEP: N-etilpirrolidone NEP: N-ethylpyrrolidone

IPDI: isoforondiisocianato, peso molecolare 222 g/mol IPDI: isophorone isocyanate, molecular weight 222 g / mol

HMDI: 4,4’- dicicloesil-metan-diisocianato, peso molecolare 262 g/mol TEA: trietilammna, peso molecolare 101,15 g/mol HMDI: 4.4â € ™ - dicyclohexyl-methan-diisocyanate, molecular weight 262 g / mol TEA: triethylamine, molecular weight 101.15 g / mol

HH: idrazina idrata, sol. acquosa al 24.36%, peso molecolare 32,04 g/mol HH: hydrazine hydrates, sol. 24.36% aqueous, molecular weight 32.04 g / mol

DEA: dietanolammina, peso molecolare 105,14 g/mol DEA: diethanolamine, molecular weight 105.14 g / mol

ADD: agente bagnante Byk 346 ADD: Byk 346 wetting agent

ESEMPI 1.1-1.3 EXAMPLES 1.1-1.3

Gli Esempi 1.1-1.3 descrivono la procedura di preparazione di polioli idrofobici a base di DGEBA. Examples 1.1-1.3 describe the preparation procedure of hydrophobic polyols based on DGEBA.

Esempio 1.1 Example 1.1

Sintesi di H-POLYOL 1. Synthesis of H-POLYOL 1.

140,6 g (1,363 mol) di ALCOHOL C6 vengono caricati in un reattore munito di termometro, agitazione meccanica e condensatore, sotto azoto, e scaldati fino a 65°C. Si aggiungono 0,40 g di KOH al 40% sotto agitazione a 65°C. 140.6 g (1.363 mol) of ALCOHOL C6 are charged into a reactor equipped with a thermometer, mechanical stirring and condenser, under nitrogen, and heated up to 65 ° C. 0.40 g of 40% KOH are added under stirring at 65 ° C.

259,4 g (0,682 mol) di DGEBA vengono poi aggiunti e la miscela di reazione viene riscaldata e mantenuta per circa 4 ore a 120°C finchà ̈ scompaiono completamente i segnali dei gruppi epossidici; la titolazione dei gruppi epossidici à ̈ effettuata in questo e negli altri esempi secondo la norma ASTM D1652-04. 259.4 g (0.682 mol) of DGEBA are then added and the reaction mixture is heated and maintained for about 4 hours at 120 ° C until the signals of the epoxy groups completely disappear; the titration of the epoxy groups is carried out in this and in the other examples according to the ASTM D1652-04 standard.

Una volta che i gruppi epossidici sono reagiti completamente, la miscela di reazione viene raffreddata a 80°C e si aggiungono 0,35 g di acido fosforico 85%, ottenendo il poliolo H-POLYOL 1 (peso molecolare 586 g/mol). Il suo numero di ossidrile risulta essere 191 mg KOH/g. Esempio 1.2 Once the epoxy groups have completely reacted, the reaction mixture is cooled to 80 ° C and 0.35 g of 85% phosphoric acid are added, obtaining the polyol H-POLYOL 1 (molecular weight 586 g / mol). Its hydroxyl number turns out to be 191 mg KOH / g. Example 1.2

Sintesi di H-POLYOL 2 Synthesis of H-POLYOL 2

186,0 g (1,363 mol) di ALCOHOL C12 vengono caricati in un reattore come quello dell’Esempio 1.1 e scaldati fino a 70°C. Si aggiungono 0,75 g di KOH al 40%. 190,0 g (0,5 mol) di DGEBA vengono poi aggiunti e la miscela di reazione viene riscaldata e mantenuta per circa 4 ore a 120°C finchà ̈ scompaiono completamente i segnali dei gruppi epossidici. La miscela di reazione viene raffreddata a 80°C e si aggiungono 0,65 g di acido fosforico 85%, ottenendo il poliolo H-POLYOL 2 (peso molecolare 752 g/mol). Il suo numero di ossidrile risulta essere 149 mg KOH/g. 186.0 g (1.363 mol) of C12 ALCOHOL are loaded into a reactor like that of Example 1.1 and heated up to 70 ° C. 0.75 g of 40% KOH are added. 190.0 g (0.5 mol) of DGEBA are then added and the reaction mixture is heated and maintained for about 4 hours at 120 ° C until the signals of the epoxy groups completely disappear. The reaction mixture is cooled to 80 ° C and 0.65 g of 85% phosphoric acid are added, obtaining the polyol H-POLYOL 2 (molecular weight 752 g / mol). Its hydroxyl number is 149 mg KOH / g.

Esempio 1.3 Example 1.3

Sintesi di H-POLYOL 3 Synthesis of H-POLYOL 3

326,0 g (1,363 mol) di ALCOHOL C20 vengono caricati in un reattore come quello dell’Esempio 1.1 e scaldati fino a 100°C. Si aggiungono 0,80 g di KOH al 40%. 326.0 g (1.363 mol) of ALCOHOL C20 are loaded into a reactor like that of Example 1.1 and heated up to 100 ° C. 0.80 g of 40% KOH are added.

190,0 g (0,5 mol) di DGEBA vengono poi aggiunti e la miscela di reazione viene riscaldata e mantenuta per circa 4 ore a 130°C finchà ̈ scompaiono completamente i segnali dei gruppi epossidici. 190.0 g (0.5 mol) of DGEBA are then added and the reaction mixture is heated and maintained for about 4 hours at 130 ° C until the epoxy group signals completely disappear.

La miscela di reazione viene raffreddata a 120°C e si aggiungono 0,80 g di acido fosforico 85%, ottenendo il poliolo H-POLYOL 3. The reaction mixture is cooled to 120 ° C and 0.80 g of 85% phosphoric acid are added, obtaining the polyol H-POLYOL 3.

Il suo numero di ossidrile risulta essere 108 mg KOH/g. Its hydroxyl number is 108 mg KOH / g.

Esempio 1.4 Example 1.4

Sintesi di H-POLYOL 4 Synthesis of H-POLYOL 4

L’Esempio 1.4 descrive la preparazione di un poliolo idrofobico preparato da IPDI secondo l’arte anteriore (H-POLYOL 4). Example 1.4 describes the preparation of a hydrophobic polyol prepared by IPDI according to the prior art (H-POLYOL 4).

135,1 g di ALCOHOL C6 e 432,0 g di NEP vengono caricati in un reattore munito di termometro, agitazione meccanica e condensatore, sotto azoto, e a temperatura ambiente. 293,9 g di IPDI vengono aggiunti sotto agitazione dopo circa 30 minuti di omogeneizzazione della miscela a 40°C. 135.1 g of ALCOHOL C6 and 432.0 g of NEP are charged into a reactor equipped with a thermometer, mechanical stirring and condenser, under nitrogen, and at room temperature. 293.9 g of IPDI are added under stirring after about 30 minutes of homogenization of the mixture at 40 ° C.

La miscela di reazione viene quindi scaldata a 80°C e si prosegue facendo reagire a 90°C, finchà ̈ il contenuto di –NCO nel prepolimero à ̈ pari a 6,45%; la titolazione dei gruppi isocianati residui à ̈ determinata in questo come negli altri esempi con il metodo ASTM D2572. The reaction mixture is then heated to 80 ° C and continued by reacting at 90 ° C, until the content of â € “NCO in the prepolymer is equal to 6.45%; the titration of the residual isocyanate groups is determined in this as in the other examples with the ASTM D2572 method.

Il prepolimero viene raffreddato a 80°C e si aggiungono 138,8 g di DEA lentamente e mescolando. The prepolymer is cooled to 80 ° C and 138.8 g of DEA is added slowly and mixing.

Il poliolo ottenuto (H-POLYOL 4) ha residuo solido del 75% in peso (peso molecolare 429,7 g/mol). Il numero d’ossidrile à ̈ pari a 261 mg KOH/g The polyol obtained (H-POLYOL 4) has a solid residue of 75% by weight (molecular weight 429.7 g / mol). The hydroxyl number is equal to 261 mg KOH / g

Esempio 2.1 Example 2.1

Preparazione di una dispersione acquosa secondo l’invenzione. Preparation of an aqueous dispersion according to the invention.

138,7 g di POLYOL 2 e 26,6 g di H-POLYOL 1, 20,9 g di DMPA e 80 g di NMP vengono caricati in un reattore come quello dell’Esempio 1.1. 138.7 g of POLYOL 2 and 26.6 g of H-POLYOL 1, 20.9 g of DMPA and 80 g of NMP are loaded into a reactor like that of Example 1.1.

Si aggiungono 155,6 g di HMDI sotto agitazione dopo circa 30 minuti di omogeneizzazione della miscela a 40°C. 155.6 g of HMDI are added under stirring after about 30 minutes of homogenizing the mixture at 40 ° C.

La miscela di reazione si scalda e mantiene a 60°C per 30 minuti. The reaction mixture is heated and maintained at 60 ° C for 30 minutes.

La reazione viene poi condotta a 95-100°C fino a che si arriva al contenuto teorico di NCO nel prepolimero (5,07%, in circa 1 ora). The reaction is then carried out at 95-100 ° C until the theoretical content of NCO in the prepolymer is reached (5.07%, in about 1 hour).

Il prepolimero viene quindi raffreddato a 75°C circa e si aggiungono 14.9 g di agente neutralizzante (TEA). The prepolymer is then cooled to about 75 ° C and 14.9 g of neutralizing agent (TEA) are added.

Dopo circa 10 minuti, a temperatura interna di 65°C, il prepolimero viene disperso in acqua demineralizzata sotto forte agitazione mantenendo la temperatura sotto 35°C. L’estensione à ̈ eseguita aggiungendo 47,8 g di HH (soluzione acquosa al 24,36%), come descritto in Tabella 1, a temperatura inferiore a 35°C. After about 10 minutes, at an internal temperature of 65 ° C, the prepolymer is dispersed in demineralized water under strong stirring, maintaining the temperature below 35 ° C. The extension is performed by adding 47.8 g of HH (aqueous solution at 24.36%), as described in Table 1, at a temperature below 35 ° C.

Si aggiunge l’agente bagnante ADD alla dispersione acquosa di poliuretano che viene quindi filtrata su tela a 150 micron e portata a contenuto sol ido del 35% in peso. La dispersione ottenuta à ̈ trasparente e stabile. The wetting agent ADD is added to the aqueous polyurethane dispersion which is then filtered on a cloth at 150 microns and brought to a solid content of 35% by weight. The dispersion obtained is transparent and stable.

Esempi 2.2-2.4 Examples 2.2-2.4

Preparazione di altre dispersioni acquose secondo l’invenzione. Preparation of other aqueous dispersions according to the invention.

Si segue la procedura dell’Esempio 2.1 modificando le materie prime come indicato in Tabella 1 (quantità in grammi). The procedure of Example 2.1 is followed by modifying the raw materials as indicated in Table 1 (quantity in grams).

Esempio 2.5 (comparativo) Example 2.5 (comparative)

Si ripete l’Esempio 2.1 senza aggiungere però il poliolo idrofobico e con gli ingredienti indicati in Tabella 1. Example 2.1 is repeated without however adding the hydrophobic polyol and with the ingredients indicated in Table 1.

ESEMPI 2.6-2.10 EXAMPLES 2.6-2.10

Preparazione di altre dispersioni acquose secondo l’arte nota. Preparation of other aqueous dispersions according to the known art.

L’elenco dettagliato delle materie prime e le loro quantità sono riportate in Tabella 1. The detailed list of raw materials and their quantities are shown in Table 1.

POLYOL 1 o POLYOL 2 e H-POLYOL 4, H-POLYOL 5 o H-POLYOL 6, DMPA e NMP sono caricati in un reattore munito di termometro, agitazione meccanica e condensatore, sotto azoto e a temperatura ambiente. POLYOL 1 or POLYOL 2 and H-POLYOL 4, H-POLYOL 5 or H-POLYOL 6, DMPA and NMP are loaded into a reactor equipped with a thermometer, mechanical stirring and condenser, under nitrogen and at room temperature.

Si aggiunge HMDI sotto agitazione dopo aver omogeneizzato la miscela per circa 30 minuti a 40°C. HMDI is added under stirring after having homogenized the mixture for about 30 minutes at 40 ° C.

La miscela di reazione viene portata e mantenuta a 60°C per 30 minuti. The reaction mixture is brought and maintained at 60 ° C for 30 minutes.

La reazione viene poi condotta a 95-100°C, finchà ̈ il contenuto di NCO nel prepolimero à ̈ circa uguale al teorico (per circa 1 ora). The reaction is then carried out at 95-100 ° C, until the NCO content in the prepolymer is approximately equal to the theoretical one (for approximately 1 hour).

Il prepolimero viene portato a 75°C circa e si aggiunge il neutralizzante (TEA) sotto agitazione. The prepolymer is brought to about 75 ° C and the neutralizer (TEA) is added under stirring.

Dopo circa 10 minuti e a temperatura interna di circa 65°C, il prepolimero viene disperso in acqua demineralizzata sotto forte agitazione mantenendo la temperatura sotto 35°C. L’estensione à ̈ eseguita aggiungendo HH, come descritto in Tabella 1, a temperatura inferiore a 35°C. Si aggiunge l’agente bagnante ADD alla dispersione acquosa di poliuretano che viene quindi filtrata su tela a 150 micron e portata a contenuto solido del 35% in peso. La dispersione ottenuta à ̈ trasparente e stabile. After about 10 minutes and at an internal temperature of about 65 ° C, the prepolymer is dispersed in demineralized water under strong stirring, keeping the temperature below 35 ° C. The extension is performed by adding HH, as described in Table 1, at a temperature below 35 ° C. The wetting agent ADD is added to the aqueous polyurethane dispersion which is then filtered on cloth at 150 microns and brought to a solid content of 35% by weight. The dispersion obtained is transparent and stable.

TABELLA 1 TABLE 1

Esempio Example

2.1 2.2 2.3 2.4 2.5* 2.6* 2.7* 2.8* 2.9* 2.10* POLYOL 1 - 134.4 - 130.4 124.9 - 144.4 - - -POLYOL 2 138.7 - 134.6 - 43.6 148.6 - 131.0 147.0 146.7 H-POLYOL 1 26.6 27.5 - - - - - - - -H-POLYOL 2 - - 33.1 34.3 - - - - - -H-POLYOL 5 - - - - - 10.3 10.8 18.2 - -H-POLYOL 6 - - - - - - - - 13.1 -H-POLYOL 4 - - - - - - - - - 31.1 DMPA 20.9 20.8 20.8 20.9 20.8 20.8 20.8 20.8 20.8 21.6 NMP 80.0 80.0 80.0 80.0 80.0 80.0 80.0 80.0 80.0 80.0 HMDI 155.6 158.7 153.0 156.1 152.5 162.6 165.2 170.5 160.4 157.5 TEA 14.9 14.9 15.7 14.9 14.9 14.9 14.9 15.7 15.6 16.3 HH 47.8 48.7 49.1 47.9 46.8 49.6 50.7 54.7 51.4 50.5 ADD 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Water 514.6 513.8 512.8 514.5 515.4 513.1 512.1 508.0 510.8 495.3 2.1 2.2 2.3 2.4 2.5 * 2.6 * 2.7 * 2.8 * 2.9 * 2.10 * POLYOL 1 - 134.4 - 130.4 124.9 - 144.4 - - -POLYOL 2 138.7 - 134.6 - 43.6 148.6 - 131.0 147.0 146.7 H-POLYOL 1 26.6 27.5 - - - - - - - -H-POLYOL 2 - - 33.1 34.3 - - - - - -H-POLYOL 5 - - - - - 10.3 10.8 18.2 - -H-POLYOL 6 - - - - - - - - 13.1 -H-POLYOL 4 - - - - - - - - - 31.1 DMPA 20.9 20.8 20.8 20.9 20.8 20.8 20.8 20.8 20.8 21.6 NMP 80.0 80.0 80.0 80.0 80.0 80.0 80.0 80.0 80.0 80.0 HMDI 155.6 158.7 153.0 156.1 152.5 162.6 165.2 170.5 160.4 157.5 TEA 14.9 14.9 15.7 14.9 14.9 14.9 14.9 15.7 15.6 16.3 HH 47.8 48.7 49.1 47.9 46.8 49.6 50.7 54.7 51.4 50.5 ADD 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Water 514.6 513.8 512.8 514.5 515.4 513.1 512.1 508.0 510.8 495.3

Diametro Diameter

particellare particle

(nm) 55 54 32 55 63 43 45 30 65. 40 *comparativo (nm) 55 54 32 55 63 43 45 30 65. 40 * comparative

ESEMPI APPLICATIVI APPLICATION EXAMPLES

Negli esempi applicativi si mostra il confronto tra i risultati di coating eseguiti utilizzando dispersioni dell’arte nota e due dispersioni secondo l’invenzione. The application examples show the comparison between the results of coating carried out using dispersions of the known art and two dispersions according to the invention.

Vengono confrontate proprietà meccaniche, chimiche e fisiche di substrati di vetro o metallo rivestiti con le dispersioni poliuretaniche. L’angolo di contatto à ̈ misurato su un substrato di alluminio rivestito utilizzando un Pocket Goniometer PGX. La pompa integrata rilascia goccioline di acqua da 0.5 microlitri e la camera di raccolta cattura le immagini della singola goccia per determinare l’angolo di contatto statico all’equilibrio. Mechanical, chemical and physical properties of glass or metal substrates coated with polyurethane dispersions are compared. The contact angle is measured on a coated aluminum substrate using a PGX Pocket Goniometer. The integrated pump releases 0.5 microliter water droplets and the collection chamber captures images of the single drop to determine the static contact angle at equilibrium.

La durezza dei film à ̈ stata misurata con il metodo ASTM D4366-95 (Standard Test Method for Hardness of Coatings by Pendulum Damping Test), su vetro. The hardness of the films was measured with the ASTM D4366-95 method (Standard Test Method for Hardness of Coatings by Pendulum Damping Test), on glass.

La resistenza idrolitica e all’etanolo dei film à ̈ stata misurata con il metodo UNI EN 12720 (Resistenza superficiale a liquidi freddi) su vetro. The hydrolytic and ethanol resistance of the films was measured with the UNI EN 12720 method (Surface resistance to cold liquids) on glass.

La resistenza chimica (NaOH, HCl) Ã ̈ stata determinata dalla valutazione del substrato di vetro rivestito dopo immersione in soluzione alcalina o acida (1% NaOH o 5% HCl) a temperatura di 55°C per 2 minuti. I risultati sono espressi con una scala da 0 a 5 (0= peggior risultato, il rivestimento si distrugge; 5=miglior risultato, nessun effetto sul rivestimento). Chemical resistance (NaOH, HCl) was determined by evaluating the coated glass substrate after immersion in an alkaline or acid solution (1% NaOH or 5% HCl) at a temperature of 55 ° C for 2 minutes. The results are expressed on a scale from 0 to 5 (0 = worst result, the coating is destroyed; 5 = best result, no effect on the coating).

L’adesione su substrato metallico (alluminio e acciaio elettrogalvanizzato) à ̈ stata determinata con il metodo ASTM D3359-09 (Standard Test Method for Measuring by Tape Test). I risultati sono The adhesion on metal substrate (aluminum and electrogalvanized steel) was determined with the ASTM D3359-09 method (Standard Test Method for Measuring by Tape Test). The results are

espressi con una scala da 0 a 5 (0= peggior risultato, il rivestimento si expressed on a scale from 0 to 5 (0 = worst result, the coating yes

distrugge completamente; 5=miglior risultato, nessun effetto sul completely destroys; 5 = best result, no effect on

rivestimento). coating).

I risultati sono riportati in Tabella 2. The results are reported in Table 2.

TABELLA 2 TABLE 2

ESEMPIO EXAMPLE

2.2 2.4 2.5* 2.6* 2.7* 2.8* 2.10* Angolo di contatto (°) 66.4 85.5 70.6 66.2 67.1 59.4 65.3 Resistenza all’EtOH 2.2 2.4 2.5 * 2.6 * 2.7 * 2.8 * 2.10 * Contact angle (°) 66.4 85.5 70.6 66.2 67.1 59.4 65.3 Resistance to EtOH

(min) 25 30 4 2 2 1 1 Resistenza all’H2O (min) 25 30 4 2 2 1 1 Resistance to H2O

(min) 120 50 30 60 30 10 240 Durezza Koenig (s) 143 113 108 150 141 190 130 Adesione (allum. A (min) 120 50 30 60 30 10 240 Koenig hardness (s) 143 113 108 150 141 190 130 Adhesion (alum. A

36)** 5 5 1 0 0 0 0 Adesione (EGI) 5 5 3 0 0 0 0 Resistenza a NaOH 5 4 2 3 3 3 3 Resistenza a HCl 4 3 3 2 2 2 2 36) ** 5 5 1 0 0 0 0 Adhesion (EGI) 5 5 3 0 0 0 0 Resistance to NaOH 5 4 2 3 3 3 3 Resistance to HCl 4 3 3 2 2 2 2

*comparativo *comparative

** a umido: substrato immerso in acqua per 4 ore e test d’adesione 2 minuti dopo l’estrazione ** wet: substrate immersed in water for 4 hours and adhesion test 2 minutes after extraction

Si può osservare che l’angolo di contatto dell’Esempio 2.4 à ̈ It can be observed that the contact angle of Example 2.4 is

significativamente maggiore di quello degli altri esempi, e questo significantly greater than that of the other examples, and this one

dimostra una maggiore idrofobicità del coating. demonstrates a greater hydrophobicity of the coating.

I substrati rivestiti con le dispersioni degli Esempi 2.2 e 2.4 mostrano una resistenza all’etanolo 6-7 volte maggiore di quelli preparati senza utilizzare un poliolo idrofobico e ancora più incrementata rispetto a quelli dalle dispersioni dell’arte nota. The substrates coated with the dispersions of Examples 2.2 and 2.4 show a resistance to ethanol 6-7 times greater than those prepared without using a hydrophobic polyol and even more increased than those from the dispersions of the known art.

La resistenza idrolitica dei coating della presente invenzione à ̈ buona. Inoltre, i substrati rivestiti con la dispersione degli Esempi 2.2 e 2.4 mostrano buona durezza e eccellente adesione sia su alluminio che su acciaio in confronto a quelli preparati con le dispersioni dell’arte nota. Se si considera la resistenza agli alcali e agli acidi, i coating preparati con le dispersioni della presente invenzione mostrano resistenza migliore o uguale a quelli dell’arte nota. The hydrolytic resistance of the coatings of the present invention is good. Furthermore, the substrates coated with the dispersion of Examples 2.2 and 2.4 show good hardness and excellent adhesion both on aluminum and on steel in comparison with those prepared with the dispersions of the prior art. If the resistance to alkalis and acids is considered, the coatings prepared with the dispersions of the present invention show resistance better than or equal to those of the known art.

Claims (10)

RIVENDICAZIONI 1) Dispersioni acquose contenenti da 20 a 50% in peso di poliuretani anionici ottenuti disperdendo in acqua ed estendendo con una poliammina un prepolimero anionico neutralizzato che contiene da 5 a 250 meq/100 g sul secco di gruppi carbossilici e preparato facendo reagire uno o più poliisocianati alifatici, cicloalifatici o aromatici con una miscela di polioli (P) che comprende: I) da 4 a 90% in peso di uno o più polioli idrofobici aventi funzionalità idrossilica media molare da 2 a 3, numero di ossidrile da 350 a 40 e ottenuti facendo reagire un alcohol ROH, in cui R à ̈ un catena alchilica satura, lineare o ramificata C4-C30o R à ̈ un radicale fenile sostituito con una catena alchilica satura, lineare o ramificata C4-C10, con un diglicidil etere aromatico di formula (I): O O O O R1 (I) in cui R1à ̈ il radicale (i): R2R3 (i) in cui R2e R3sono uno indipendentemente dall’altro Me, Et, o H; o R1à ̈ un radicale fenilene, eventualmente sostituito con uno o più gruppi alchilici; o R1à ̈ un radicale bis-fenilene, eventualmente sostituito con uno o più gruppi alchilici; o R1à ̈ il radicale (ii): O O (ii) II) da 1 a 10% in peso di uno o più poliol i anionici o potenzialmente anionici aventi due o più gruppi reattivi nei confronti dei gruppi isocianic i e almeno un gruppo carbossilico o carbossilato; III) da 0 a 95 % in peso di uno o più policarbonati dioli lineari aventi peso molecolare da 500 a 3,000; IV) da 0 a 95% in peso di uno o più poliesteri dioli lineari aventi peso molecolare da 500 a 4,000; V) da 0 a 95% in peso di uno o più polialchilene dioli scelti tra poli(ossipropilene) glicol e poli(ossitetrametilene) glicol, i poliisocianati e la miscela di polioli (P) essendo in proporzioni tali che: a) il rapporto tra i gruppi isocianici NCO dei polisiocianati e la somma di tutti i gruppi –OH reattivi della miscela di polioli (P) sia compresa tra 1.2 e 2.3. CLAIMS 1) Aqueous dispersions containing from 20 to 50% by weight of anionic polyurethanes obtained by dispersing in water and extending with a polyamine a neutralized anionic prepolymer containing from 5 to 250 meq / 100 g on the dry basis of carboxylic groups and prepared by reacting one or more aliphatic, cycloaliphatic or aromatic polyisocyanates with a mixture of polyols (P) which includes: I) from 4 to 90% by weight of one or more hydrophobic polyols having hydroxyl mean molar functionality from 2 to 3, hydroxyl number from 350 to 40 and obtained by reacting an alcohol ROH, in which R is a saturated alkyl chain, linear or branched C4-C30 or R is a phenyl radical substituted with a saturated, linear or branched C4-C10 alkyl chain, with an aromatic diglycidyl ether of formula (I): O O O O R1 (THE) where R1à is the radical (i): R2R3 (the) in which R2 and R3 are one independently of the other Me, Et, or H; or R1à a phenylene radical, optionally substituted with one or more alkyl groups; or R1à a bis-phenylene radical, optionally substituted with one or more alkyl groups; or R1à ̈ the radical (ii): OR OR (ii) II) from 1 to 10% by weight of one or more anionic or potentially anionic polyols having two or more groups reactive towards the isocyanic groups and at least one carboxyl or carboxylate group; III) from 0 to 95% by weight of one or more linear polycarbonate diols having molecular weight from 500 to 3,000; IV) from 0 to 95% by weight of one or more linear polyester diols having molecular weight from 500 to 4,000; V) from 0 to 95% by weight of one or more polyalkylene diols selected from poly (oxypropylene) glycol and poly (oxytetramethylene) glycol, the polyisocyanates and the mixture of polyols (P) being in such proportions that: a) the ratio between the NCO isocyanic groups of the polysiocyanates and the sum of all reactive - OH groups of the mixture of polyols (P) is between 1.2 and 2.3. 2) Dispersioni acquose secondo la rivendicazione 1 in cui i componenti I), II), III), IV) e V) costituiscono almeno il 95% in peso della miscela di polioli (P), la miscela di polioli comprendendo ulteriormente da 0 a 5% in peso di altri polioli non ionici aventi peso molecolare inferiore a 1,000 e contenenti due o più gruppi idrossilici. 2) Aqueous dispersions according to claim 1 wherein components I), II), III), IV) and V) constitute at least 95% by weight of the polyol mixture (P), the polyol mixture further comprising 0 to 5% by weight of other non-ionic polyols having a molecular weight of less than 1,000 and containing two or more hydroxyl groups. 3) Dispersioni acquose secondo la rivendicazione 2 in cui i componenti I), II), III), IV) e V) costituiscono il 100% in peso della miscela di polioli (P) del prepolimero. 3) Aqueous dispersions according to claim 2 wherein components I), II), III), IV) and V) constitute 100% by weight of the polyol mixture (P) of the prepolymer. 4) Dispersioni acquose secondo la rivendicazione 3 in cui i componenti I), II), III), e IV) costituiscono il 100% in peso della miscela di polioli (P). 4) Aqueous dispersions according to claim 3 wherein components I), II), III), and IV) constitute 100% by weight of the polyol mixture (P). 5) Dispersioni acquose secondo la rivendicazione 1 in cui la miscela di polioli (P) contiene dal 5 al 75 % in peso di un poliolo idrofobico I) ottenuto facendo reagire un alcol ROH in cui R à ̈ una catena alchilica satura C6-C22ramificata o lineare e R1à ̈ il radicale (i). 5) Aqueous dispersions according to claim 1 wherein the polyol mixture (P) contains from 5 to 75% by weight of a hydrophobic polyol I) obtained by reacting an alcohol ROH in which R is a saturated C6-C22 branched alkyl chain or linear and R1à is the radical (i). 6) Dispersioni acquose secondo la rivendicazione 5 in cui R2e R3sono metili. 6) Aqueous dispersions according to claim 5 wherein R2 and R3 are methyls. 7) Dispersioni acquose secondo la rivendicazione 1 in cui il prepolimero anionico neutralizzato à ̈ preparato da uno o più poliisocianati alifatici o cicloalifatici aventi funzionalità media –NCO compresa tra 2.0 e 2.3. 7) Aqueous dispersions according to claim 1 in which the neutralized anionic prepolymer is prepared from one or more aliphatic or cycloaliphatic polyisocyanates having an average functionality - NCO comprised between 2.0 and 2.3. 8) Dispersioni acquose secondo la rivendicazione 1 in cui il componente II) della miscela di polioli (P) à ̈ acido dimetilolpropionico, dimetilolbutanoico o loro miscele; il componente III) della miscela di polioli (P) à ̈ poli(esametilene carbonato)diolo avente peso molecolare numerale medio da 800 a 2,000; il componente IV) della miscela di polioli (P) à ̈ scelto tra i poliesteri a base di acido adipico e/o ftalico con 1,6-esandiolo, etilene glicol, dietilene glicol, neopentilglicol, 1,4-butandiolo o loro miscele, e aventi peso molecolare numerale medio da 800 a 3,000. 8) Aqueous dispersions according to claim 1 wherein component II) of the polyol mixture (P) is dimethylolpropionic acid, dimethylolbutanoic acid or their mixtures; component III) of the mixture of polyols (P) is poly (hexamethylene carbonate) diol having an average number molecular weight from 800 to 2,000; component IV) of the polyol mixture (P) is selected from polyesters based on adipic and / or phthalic acid with 1,6-hexanediol, ethylene glycol, diethylene glycol, neopentylglycol, 1,4-butanediol or their mixtures, and having an average number molecular weight from 800 to 3,000. 9) Dispersioni acquose secondo una qualsiasi delle rivendicazioni precedenti in cui i polioli della miscela (P) sono privi di unità che derivano da poli(ossietilene)glicol. 9) Aqueous dispersions according to any one of the preceding claims in which the polyols of the mixture (P) are free from units deriving from poly (oxyethylene) glycol. 10) Uso di dispersioni acquose di poliuretani anionici secondo le rivendicazioni da 1) a 9) per la preparazione di composizioni per il coating di substrati rigidi.10) Use of aqueous dispersions of anionic polyurethanes according to claims 1) to 9) for the preparation of compositions for coating rigid substrates.
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