Liquid moisture curable polyurethane adhesives for lamination and assembly.

(54) Title: LIQUID POLYURETHANE ADHESIVES, WHICH CAN BE CURED WITH MOISTURE, FOR LAMINATION AND ASSEMBLY.

(54) Title: LIQUID MOISTURE CURABLE POLYURETHANE ADHESIVES FOR LAMINATION AND ASSEMBLY.

(57) Summary

This invention relates to adhesives containing polyurethane prepolymer that are liquid at room temperature and do not exhibit separation under typical storage and use conditions and that can be cured by exposure to moisture or curing agents containing active hydrogen. . Polyurethane prepolymer adhesives have surprisingly good adhesion to plastics such as glass fiber reinforced plastics (FRP).

(57) Abstract

This invention relates to polyurethane prepolymer containing adhesives that are liquid at room temperature and that do not phase separate under typical storage and use conditions and that can be cured by exposure to moisture or active hydrogen-containing curing agents. The polyurethane prepolymer adhesives exhibit surprisingly good adhesion to plastics such as fiberglass reinforced plastics (FRP).

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PATENT TITLE NO. 337908

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Denomination:

HENKEL IP & HOLDING GMBH

Henkelstrape 67, 40589 Dusseldorf, GERMANY

LIQUID POLYURETHANE ADHESIVES, WHICH CAN BE CURED WITH MOISTURE, FOR LAMINATION AND ASSEMBLY.

Classification: lnt.CI.8: B32B7 / 12; C09J175 / 06; C09J191 / 00

SHUHUI QIN; YINGJIE Ll

REQUEST

Number*

MX / a / 2011/008556

Internal filing date ^^ na ^ February 2010

Country:

US ncia: Twenty ii os de V <

Reference patent

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PRIORITY

Date:

February 2009 of the (£ and of the Pro, the preseréción of the sun liento 12 rero of 2030

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Number:

12/371,939

Who subscribes to this Industrial Property (Diario 26101/2004, 06/16/2005, 2 5, intéo a), 4 ° and 12 · fraction 01B7 / 2002, 07/15/2004, 28 / I deiween liüHimw, .iffrj ulo lo has ficial de / 2006, 06 I and III dq 72004 yi Opiedad 11

2nd section V, 6th section III, and 59 of the Industrial Property Law.

This patent is valid for twenty unprofitable years, and will be subject to the payment of the fee to keep the

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with fundameni

Federation (D. (15 / 2009,06 / 01/2010, 1 Instil Regulation 19/2007); articles 1, 3, 4, 5 'frai and 7 ° bis 2 of the &amp; ey of the 26/12 / 1997, 1ÍO5 / 1999,; articles 1, 3 íacc¡ón V (DOF 12/14/1999, confirmed on 16 sections I and III and 30 of the Organic Statute 7); 1, 3 and 5 subsection a) of the Agreement that delegates powers to the Deputy Directors General, Coordinator, Divisional Directors, Holders of the Regional Offices, Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexican Institute of Industrial Property. (DOF 12/15/1999, amended on 02/04/2 000, 07/29/2004, 08/04/2004 and 09/13/2007).

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Issue Date: March 28, 2016

DIVISION DIRECTOR OF PATENTS

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1.

NAHANNY CANAL REYES

Sand! No 550, Floor 1,

Col. Pueblo Santa María Tepepan, Xochimifco, CP 16020,

Mexico City

Tei. (55) 53 34 07 00 www.irnpi.gob.mx

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MX / 2016/23524

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MEXICAN INSTITUTE OF PROPERTY

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LIQUID POLYURETHANE ADHESIVES, WHICH MAY BE 'XÍÜaAbO

WITH MOISTURE, FOR LAMINATION AND ASSEMBLY

BACKGROUND OF THE INVENTION

Field of the Invention

This invention relates to adhesives that contain the polyurethane prepolymer, that are liquid at room temperature and that do not exhibit phase separation under common storage and use conditions, and that can be cured by exposing them to moisture or curing agents that contain active hydrogen. Polyurethane prepolymer adhesives have surprisingly good adhesion to plastics, such as glass fiber reinforced plastics (FRP).

Brief description of related technology

Liquid, moisture-curable polyurethane adhesives are known. Henkel actually

Corporation currently markets and offers for sale liquid, moisture cured polyurethane adhesive products under the Macroplast® UR and Macroplast® SIA brand names, each with considerable success in

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The 0003] Polyurethane adhesive that can be cured with humidity, liquid can be modified by some additives. For example, plasticizer oils have been used in the past to improve the rheology of such a polyurethane adhesive. Adhesion promoters have also been used in the past to improve the adhesion of such a polyurethane adhesive to substrates. However, in some cases, the use of plasticizer oil leads to phase separation, which is unwanted.

In the context of hot melt adhesives, which change phase depending on the temperature to which they are exposed, polyurethane-based materials are known, which can be cured with moisture. For example, Henkel Corporation has been responsible for advances in such technology as defined and claimed, for example, in US Patent Nos. 6,136,136 (Heidler), 6,221,978 (Li) and 6,635,722 (Li).

US Patent No. 5,786,085 (Tzeng) is directed to and claims a ridge formed from an asphaltic foam material consisting of: (1) a layer of asphaltic foam material having an upper surface and a lower surface; (2) a layer of embedded granules

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on the upper surface of the asphalt foam layer, the granules form a decorative and / or protective ridge layer; and (3) an elastomeric tape connected to the layer of the asphalt foam material along a central axis of the layer and covered with the granules, where the ridge can be folded along the central axis. In the '085 Patent, asphalt foam is a polyurethane material, and additives such as plasticizers and viscosity reducers are listed as possible reactants.

US Patent No. 5,932,646 (Roberts) is directed to and claims a material composition for waterproofing a wall surface, containing from about 30 to about 55 parts by weight of a polymer base, the polymer base containing from about 20 to about 45 parts by weight of a hydrocarbon resin and from about 55 to about 80 parts by weight of an elastomeric copolymer having selected units of styrene, isoprene, butadiene, ethylene, butylene, and mixtures thereof, where the hydrocarbon resin and elastomeric copolymer total about 100 parts by weight; and from about 45 to about 70 parts in

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weight of a solvent system, where the solvent system includes a mixture of petroleum distillates and heptane, where heptane contains n-heptane, and where the polymer base and solvent system total approximately 100 parts by weight.

Although liquid, moisture curable polyurethane adhesives have been in industrial use for several decades, they can be improved. For example, bonding to plastics like FRP can sometimes be difficult. Producing an adhesive like these also requires high processing temperatures, which translates into higher than desired energy costs. The stability of an adhesive like this can also be improved. It would be desirable to have polyurethane adhesives that can be cured with moisture, liquids, which can be produced at lower processing temperatures, that have better stability and better adhesion to plastics like FRP.

SUMMARY OF THE INVENTION

The present invention provides a polyurethane prepolymer adhesive composition consisting of a reaction product obtained by reacting a

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stoichiometric excess of at least one polyfunctional isocyanate with at least one polyol; at least one liquid paraffinic oil; and at least one aromatic oil.

Surprisingly, it has been found that such liquid, moisture curable polyurethane oil can be prepared at a temperature of 170 ° F, with good stability (eg, showing little to no phase separation or turbidity), and good adhesion to substrates like FRP. Liquid, moisture curable polyurethane adhesives come from the same polyisocyanate and polyol reactant system without liquid paraffinic oil or aromatic oil being unstable or showing poor adhesion to substrates such as FRP.

DETAILED DESCRIPTION OF THE INVENTION

Liquid, moisture-curable polyurethane can be prepared by reacting an excess amount of polyisocyanate with polyol. During and after application, unreacted isocyanate groups react with moisture that is on or within substrates and in the atmosphere to form a thermoset system. The bond made with such adhesives offers excellent resistance to chemicals, solvents,

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heat and low temperature. The adhesives class has found extensive application opportunities in a wide range of industries.

The present invention provides a polyurethane prepolymer adhesive consisting of a reaction product obtained by reacting a stoichiometric excess of at least one polyfunctional isocyanate with at least one polyol; at least one liquid paraffinic oil; and at least one aromatic oil.

The reactants that are used to synthesize the polyurethane prepolymer must be chosen so that the resulting polyurethane prepolymer is liquid at room temperature. The polyurethane prepolymer can be substantially linear in structure, with little or no branching. The polyurethane prepolymer is terminated with NCO (isocyanate) groups and typically has an isocyanate content of from about 1 to about 20 weight percent or from about 5 to about 15 weight percent. The viscosity of the polyurethane prepolymer is typically from about 1000 to about 25,000 centipoise at 25 ° C.

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Polyols are generally polyether polyols such as polyethylene glycol, polypropylene glycol, polypropylene glycol with polyethylene end cap, polytetramethylene glycol, and the like, with a molecular weight of from about 200 to about 10,000. The amount that is used can be from about 20 to 70, preferably from about 30 to 60 weight percent. Polyester polyols can also be used.

Suitable polyether polyols include oligomers and polymers containing a plurality of oxyalkylene repeating units such as oxyethylene, oxypropylene, oxybutylene and / or oxytetramethylene and hydroxyl end groups. It is desirable to employ difunctional polyether polyols (i.e., polyether polyols containing two hydroxyl groups per molecule). Illustrative polyether polyols are polyethylene glycols, polypropylene glycols, polytetramethylene glycols, polyethylene / propylene glycols (having a random, blocky, or terminal cap structure) and the like, with a number average molecular weight of from about 200 to about 8000 or from about 400 to about 4000. Polyether polyols like these can be made by

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Ring-opening polymerization of cyclic oxygen-containing compounds, such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, often in the presence of an initiator, such as a monomeric diol. The amount of polyether polyol used to prepare the polyurethane prepolymers can be from about 5 to 80, otherwise from about 30 to 50 weight percent of the total weight of the reactants. It is also possible to use mixtures of different polyether polyols having different chemical structures and / or different average molecular weights.

The polyol must be present in an amount of from 20 to 70 percent by weight.

The generally used polyisocyanates are any of the polyisocyanates with functionality equal to or greater than 2.0. An example such as these is a commercially available polyisocyanate under the trademark Rubinate® M from Huntsman Corporation or Mondur® MR from Bayer Corporation. The amount of polyisocyanate usually ranges from 10 to 70, preferably from 20 to 60 weight percent of the composition.

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Appropriate isophthalic acid-containing &lt;7xcTon-containing polyester polyols can be prepared by reacting isophthalic acid with one or more polyols (particularly diols). It is also possible to use other diacids, particularly aliphatic dicarboxylic acids and adipic acid, in addition to the appropriate aliphatic alcohols can be, for example, ethylene glycol, propylene glycol, butan-1,4diol, pentan-1,5-diol, hexan-1, 6-diol, heptan-1,7-diol, octan-1,8-diol and higher homologs or isomers thereof, which can be obtained by extension of the hydrocarbon chain by a CH group₂ at the same time or by introducing ramifications into the carbon chain. Other suitable diols may be neopentyl glycol, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, 1,4-cyclohexandiol, 1,4cyclohexane dimethanol, bisphenol A and hydrogenated derivatives thereof, bisphenol F and hydrogenated derivatives thereof and the like. The total amount of polyester polyol typically comprises from 5 to 80, otherwise from 10 to 70 percent of the total weight of the reactants used to prepare the liquid polyurethane prepolymer of this invention.

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The polyisocyanate that is used to prepare the polyurethane prepolymer is an isocyanate or mixture of isocyanates that have an average functionality (the number of isocyanate functional groups per molecule) that is less than 3.5, such as a difunctional isocyanate.

The polyisocyanate can be an aromatic diisocyanate such as pure 4.4-diphenylmethane diisocyanate, commercially available under the trademark Rubinate® 44. Other appropriate toluene polyisocyanates, 1,5-naphthalene diisocyanate,

1,42,4'MDI can be purified diisocyanate benzene diisocyanate (PPDI), diphenylmethane, polymeric diisocyanate (having an average functionality less than 3.5), bitolyylene diisocyanate, 1,3-xylene diisocyanate, p-TMXDI, 1, 6-diisocyanate2,4,4-trimethylhexane, CHDI, BDI, H₆XDI, IPDI, H_Í2MDI and the like. It is possible to use mixtures of different polyisocyanates, provided that the average functionality of such a mixture is less than 3.5. The amount of polyisocyanate typically ranges from 10 to 60, otherwise from 20 to 50 percent of the total weight "of reactant lbs used to prepare the liquid polyurethane prepolymers of this invention.

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Such amount should be selected so that there is a stoichiometric excess of the NCO (isocyanate) groups in the mixture of reactants used to prepare the polyurethane prepolymer, compared to the number of functional groups capable of reacting with the NCO groups (e.g. (eg, hydroxyl groups present in the polyester polyol and polyether polyol components reacting with the polyisocyanate component). For example, the NCO: OH ratio can be greater than 1.1: 1 or greater than 1.2: 1 or even higher, selecting the ratio to control the NCO content and the average molecular weight achieved in the polyurethane prepolymer obtained with this as desired.

Suitable liquid paraffinic oils for use herein may be nparaffinic oils, iso-paraffinic oils, and other branched paraffins, cycloparaffins (naphthenes), condensed cycloparaffins (including steranes and hopanes), and others with alkyl side chains in systems rings. Paraffinic oil may be a 100% n-alkane based paraffinic oil, with a molecular formula CH3 [CH2]_nCH3. This paraffinic oil is also called Tiquida paraffin, white mineral oil or liquid petrolatum. Examples of paraffinic oil available »" * «· ♦ * ¥ írjr Si * - ''. t

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commercially available may be those with the Citation ™ NF grade mark from Avatar Corporation. The amount of the paraffinic oil usually ranges from 0.1 to 15, such as from 0.5 to 10, and desirably from 2 to 5 weight percent of the composition.

Suitable aromatic oils for use herein may be oils containing at least one ring having a pi electron system conjugated to (4n + 2) pi electrons, where n is an integer, such as 0, 1, or 2. Such aromatic oils include those aromatic hydrocarbons containing benzene systems, condensed aromatic systems, condensed aromatic cycloalkyl systems, and others with alkyl side chains in ring systems. An example of an aromatic oil useful herein is a complex blend of 100% aromatic hydrocarbons, commercially available under the trademark ^ Viplex®, and Vycel® from Crowley Chemical Company, and Shellflex® from Shell Company. The amount of the aromatic oil usually ranges from 0.2 to 15, such as 0.5 to 10, and more desirably from 1 to 6 weight percent of the composition. In general, more information about liquid paraffinic oils and aromatic oils can be found in The Chemistry and Technology of

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Petroleum, 4th Edition by James Speight, CRC Press, the description of which is expressly incorporated herein by reference.

The ratio of liquid paraffinic oil to aromatic oil should be 3: 1 to 1: 3, as can be^: 2: 1 to 1: ¿, desirably 1: 1.

The liquid, moisture curable polyurethane adhesive of this invention, if desired, may also include additives such as catalysts, plasticizing oils, colorants, fillers, UV dyes, rheology modifiers (e.g. (eg, thickeners), foam control agents, blowing (blowing) agents, dehydrating agents, coupling agents, adhesion promoting agents, other types of polyurethane prepolymers, additional polyisocyanate, and other non-reactive or reactive additives , and any other additive known to an expert in the field of liquid polyurethane adhesives. Liquid, moisture curable polyurethane adhesive is desired to contain_______ none_w significant amount of added solvent, i.e. no inert organic compound having a boiling point less than 200 ° C at atmospheric pressure

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(normal). For significant amount in this context, the adhesive contains less than 1% by weight, such as less than 0.5% by weight, and desirably less than 0.1% by weight of solvent.

The liquid polyurethane prepolymer can be cured by combining and reacting the prepolymer with one or more active hydrogen containing curing agents. The adhesive can thus be formulated as a two-component (2K) system, where a first component is composed of the prepolymer and the second component is composed of the curing agent, storing the components separately but then combining them shortly before using the mix as an adhesive. Curing agents can be selected to be reactive with the prepolymer even at room temperature, curing beginning to take place as soon as the components are mixed together. However, the curing agent may be latent, that is, practically nonreactive with the prepolymer at room temperature, but may be activated by heating the adhesive mixture to an elevated temperature. The use of a latent curing agent allows the storage stable adhesive formulation to be cured by heating.

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The term "active hydrogen containing curing agent" when used herein includes any organic compound that has at least two active hydrogens per molecule, with the ability to react with isocyanate groups present in the polyurethane prepolymer. For the purpose of this invention, active hydrogen refers to a hydrogen atom which, due to its position in the molecule, exhibits significant activity according to the Zerewitnoff test described by Wohler, J. Am. Chem. Soc, Vol. 49, p. 3181 (1927). Examples of active hydrogen containing portions are -COOH (carboxylic acid), -OH (hydroxyl), -NH₂ (primary amino), -NH- (secondary amino), -CONH₂ (amido), -SH (thiol) and -CONH- (amido). Preferred active hydrogen containing compounds may be polyols, polyamines, mercaptans, and polyacids, which may be monomeric, oligomeric, and / or polymeric. For example, it is possible to use polyether polyols, polyester polyols, as well as polyether ester polyols. Examples of amino group-containing curing agents may be aromatic and aliphatic diamines, primary and secondary amine terminated polyether polyols, and difunctional, trifunctional, and polymeric amines. The type and amount of combined active hydrogen containing curing agent

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With the polyurethane prepolymer it can be selected and varied according to need to obtain the desired characteristics and properties of the cured adhesive. For example, the stoichiometric ratio of active hydrogen groups to isocyanate groups can be in the range of from about 0.5: 1 to about 1.5: 1.

In one embodiment of the invention, partial cure of the polyurethane prepolymer is accomplished by reaction with one or more active hydrogen-containing curing agents, with further cure being obtained by reaction of the remaining isocyanate groups with moisture.

The inventive liquid, moisture-curable, polyurethane adhesive should have a viscosity of 1,000 cps to 25,000 cps, such as 1,000 cps to 10,000 cps, and desirably 2,000 cps to 8,000 cps.

Since the polyurethane prepolymer contains reactive isocyanate groups, it is desirable to keep the prepolymer in an environment protected from moisture during storage, for example, in a sealed, dry, and moisture-proof container until ready. ... il. saw. λ · »

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ready to be dosed and applied to a substrate surface is one way to achieve this goal.

Liquid, moisture-curable polyurethane adhesive can be applied to substrate surfaces using known application techniques including, but not limited to, brushing, roller coating, extrusion, and spraying. The surface of the substrate can be coated with the adhesive to form a continuous or discontinuous layer of the adhesive on the surface of the substrate, the thickness of such a layer is controlled as desired based on the chosen properties of the final assembly containing the cured adhesive. Typically, the adhesive layer will be from about 0.01 to about 0.5mm thick. After application of the adhesive layer, a surface of a second substrate may contact the adhesive layer (such contact will preferably be enhanced by the application of pressure) to form an assembly of a first substrate and a second substrate with the layer adhesive between these.

Curing of the liquid, moisture-curable polyurethane adhesive can be carried out using various conditions. In particular, the curing i ha hi hahS ^

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The invention is further illustrated by the following examples.

EXAMPLES

Materials:

Acclaim Polyol 2000 (Mn 2000) and Acclaim Polyol 4200 (Mn 4000), available from Bayer, are the polypropylene 'ίϊ'

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glycols that are used in the examples with a mixing ratio by weight of 3.2: 1.

Mondur® MR, available from Bayer, is polymeric MDI with an approximate NCO% of 31% and functionality of 2.7.

Citation oil 70 NF, available from Avatar Corporation, is a 100% n-alkane based mineral oil.

Viplex® 525, available from Crowley Chemical Company, is a 100% aromatic oil.

preparation:

All of the polyurethane adhesives in the following examples were prepared using the method described below only with the relative amounts and specific types of reactants that changed for each example. All reactants and oils are added to a mixer and heated to 170 ° F with stirring. The mixture reacts at 170 ° F for a desired time, then cools and is removed.

Tests:

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Approximately 0.5 g of water, another 0.5 foot by 1 foot strip is laminated to the top of the coated strip to overlap each other. The laminated substrate is stored at room temperature for at least 12 hours before testing. The sample is then tested to determine the delamination cohesion strength of the bonded substrates.

Table 1 presents all the examples with different formulations. The cohesion strength of Examples 1 to 4 was tested using the method described above. Cohesion strength is classified as good if the bonded part can only be separated with 100% substrate failure, as regular if the bonded part can be separated with substrate failure and adhesive failure (release of adhesive from FRP substrate) ), and as bad if the joined part can be separated with significant adhesive failure.

Table 1

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<td> 1</td><td> 2</td><td> 3</td><td> 4</td>

<td>Polyether polyol</td><td> 45</td><td> 45</td><td> 45</td><td> 45</td>

<td>polyMDI</td><td> 49</td><td> 49</td><td> 49</td><td> 49</td>

<td>CÍtatiOA oil 70NF _</td><td>_____ Me at * ---</td><td></td><td> -3-~</td><td> 3</td>

<td>Viplex 525</td><td></td><td> 3</td><td></td><td> 3</td>

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<td rowspan="2">Properties physical</td><td colspan="4">Composition</td>

<td> 1</td><td> 2</td><td> 3</td><td> 4</td>

<td>Stability</td><td>Stable, transparent</td><td>Stable, transparent</td><td>Cloudy</td><td>Stable, transparent</td>

<td>Union to FRP</td><td>Bad to fair</td><td>Bad</td><td> —</td><td>Good</td>

The data shown in Table 2 demonstrate the following surprising results. Without oily additives, the adhesive has good stability but does not have good adhesion to the FRP substrate. The aromatic oil additive only helps the stability of the adhesive but not the adhesion to FRP. Aliphatic mineral oil as an additive alone does not generate a stable prepolymer system. The combination of the aromatic oil and aliphatic mineral oil additives generate a stable prepolymer system that shows good adhesion to the FRP substrate as well.

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