CA2360100A1 - Moisture-activated adhesive compositions - Google Patents
Moisture-activated adhesive compositions Download PDFInfo
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- CA2360100A1 CA2360100A1 CA002360100A CA2360100A CA2360100A1 CA 2360100 A1 CA2360100 A1 CA 2360100A1 CA 002360100 A CA002360100 A CA 002360100A CA 2360100 A CA2360100 A CA 2360100A CA 2360100 A1 CA2360100 A1 CA 2360100A1
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- moisture
- adhesive composition
- activated adhesive
- isocyanate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl 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
- C08G2170/00—Compositions for adhesives
- C08G2170/40—Compositions for pressure-sensitive adhesives
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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)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A moisture-activated adhesive composition comprising the reaction product of (A) a polyisocyanate selected from (a) a blend of polymeric MDI and pure MDI and/or from (b) an isocyanate-terminated prepolymer; (B) an isocyanate- reactive component comprising at least one aliphatic tertiary amine group- containing polyol made by alkoxylation of amines or aminoalcohols characterized in that said isocyanate reactive component has a nitrogen weig ht average equivalent molecular weight index, herein after referred to as ZW. Z W being equal or less than 1500 whereby Formula (I) with zi: nitrogen weight average equivalent molecular weight of isocyanate reactive component i; ni: total N-atoms per isocyanate reactive component i; mwi: weight average molecular weight of isocyanate reactive component i; wti: weight of isocyana te reactive component i present; .SIGMA.wti: total weight of isocyanate reactiv e component i present.
Description
MOISTURE - ACTIVATED ADHESIVE COMPOSITIONS
FIELD OF THE INVENTION
' The present invention is directed to rapid curing moisture-activated adhesive compositions s and methods for their production and a process for bonding multiple substrates using said composition. More specifically, the present invention is directed to specific moisture-activated adhesive compositions which are cold curable in the presence of high moisture content cellulosic or lignocellulosic substrates.
BACKGROUND OF THE INVENTION
1 o In recent years, the use of "engineered lumber" products by the construction industry has become increasingly common - primarily because the availability and cost of adequate quality sawn lumber have become increasingly unfavorable. However, the performance of "engineered lumber" products, which are formed by adhering smaller pieces of wood together into a composite material, represents some major challenges to the adhesives 15 formulator.
Engineered lumber products on the market today, such as finger jointed lumber, wood I-beams, and glue-laminated beams (glu-lams), utilize a variety of adhesive systems, including phenol - formaldeyhde (PF) based adhesives, polyvinylacetate (PVA) adhesives, and isocyanate - based emulsion adhesives. Unfortunately, each of these adhesive systems 2o has limitations, which compromises the effectiveness of the resultant engineered lumber composite.
PF based adhesives require a great deal of heat and/time in order to cure, and are sensitive to high levels of moisture in the wood. Use of these adhesives systems requires engineering controls to maintain a iow moisture content, and to ensure adequate bonding 25 occurs within the composite. The necessity for such costly catalyst and engineering controls increases production costs, and limits productivity, which in turn limits the competitiveness of engineered lumber in. the marketplace. Another major problem associated with these adhesives is their "green strength". These adhesives do not produce adequate bond strength immediately - they typically need to "cure" in order to reach their 3o full potential. This cure time is a matter of hours, often days - which further adds to production costs.
SUBSTITUTE SHEET (RULE 2G) WO 00/44848 PCT/EP00/00035 ' PVA adhesives have limited strength. To date, they have not proven to be suitable for use in structural applications, which require physical properties of a certain minimum standard.
For example, no commercially available PVA bonded engineered lumber product can meet the ASTM D2259 standard, a frequent requirement for structural lumber applications.
Like the PF adhesives discussed above - these systems also suffer from the limitations of slow green strength development, and a dependency on a great deal of heat and/time radiation to ensure adequate bond strengths.
Isocyanate-crosslinked latex emulsion adhesives, also have limitations in that these systems also suffer from the limitations of slow green strength development, and a dependency on a great deal of heat to ensure adequate bonding.
Polyisocyanate based adhesive compositions have also been identified for composite wood applications. Examples are moisture curable urethane-modified polyisocyanate adhesives described in EP-B-723 561 which discloses urethane-modified poiyisocyanate adhesives for use in plywood panel wood composites. These compositions contain auto catalytic species, designed to increase the reactivity of the polyisocyanate, enabling cure at ambient temperatures in a matter of minutes. However, for engineered lumber products, the different processing requirements between panels and lumber becomes extremely 2o important. As a consequence none of the existing polyisocyanate products, designed for relatively thin composite wood panels, exhibits suffcient reactivity to truly be cost-effective in relatively thick engineered lumber applications. ;S
It is therefore an object of the present invention to provide an adhesive composition especially designed for engineered lumber which impart adequate strength and reactivity and tack without the need for costly catalyst and processing/engineerning controls to overcome inherent problems, such as: maintaining low raw material moisture contents, providing a great deal of heat and time in order to cure the adhesive, and protracted "green" .
strength development.
.
These objectives are met by the present adhesive compositions, which demonstrate excellent adhesive properties with a prolonged pot life, accelerated cure, particularly at ' CA 02360100 2001-07-23 .j_ room temperature. Surprisingly, the compositions according to the present invention provide equal performance than those compositions as described in EP 0 723 561. The present compositions are activated by the moisture present in the substrate with which they are being used and thus, they may be most effectively used with substrates having a relatively high moisture content, even as high as 20% or more. Accordingly, the present compositions are effectively used with various types of lignocellulosic materials and are particularly useful in the preparation of engineered lumber products as discussed above.
SUMMARY OF THE INVENTION
The present invention relates to a moisture-activated adhesive composition comprising the reaction product of (A) polyisocyanate selected from either (a) a blend of polymeric MDI
and pure MDI andlor from (b) an isocyanate-terminated prepolymer. (B) an isocyanate-reactive component comprising at least one aliphatic tertiary amine group-containing polyol made by alkoxylation of amines or aminoalcohols characterized in that the i5 isocyanate reactive component has a nitrogen weight average equivalent molecular weight index Z~, being equal or less than 1500.
DETAILED DESCRIPTION OF THE INVENTION
According to the present invention, the polyisocyanate component is selected from either 20 (a) a blend of polymeric MDI and pwe MDI and/or an isocyanate-terminated prepolymer.
In accordance with the compositions of the present invention, the blend of polymeric MDI
and pure MDI have been found to provide improved penetration into the lignocellulosic substrate and higher wood failwe as opposed to glueline failwe. A commercially available pwe MDI product suitable for use in the present invention is RubinateTM 44 available 25 from ICI Americas Inc. The preferred blends contain polymeric MDI to pwe MDI in ratios of 95:5 to 50:50 and preferably 60:40 to 80:20.
_ The isocyanate-terminated prepolymers as used herein, the term "isocyanate-terminated prepolymer" includes the prepolymer as well as the pseudoprepolymer, i.e., a mixtwe of ' 3o the prepolymer and the polyisocyanate from which the prepolymer is prepared. The isocyanate-terminated prepolymer useful in the present compositions should have a free isocyanate (NCO) content of from 10 to 29%, preferably 16 to 29%. In general, the f polymeric polyisocyanate may be prepared by the reaction of an excess of a polyisocyanate and a polyol, including aminated polyols or imino/enamines thereof.
Suitable polyols for preparing the isocyanate-terminated prepolymers include:
(a) polyether polyols, thioether polyols andlor hydrocarbon-based polyols having a molecular weight of from 1000 to 6000 and an average hydroxyl functionality of from 1.8 to 4 (b) polyester polyols having a molecular weight of 1000 or more and an average hydroxyl functionality of from 1.9 to 4.
Particularly preferred isocyanate-terminated prepolymers useful in the present invention are MDI prepolymers, which are the reaction product of an excess of polymeric MDI and polyether polyols. The polyether polyols are preferably diols or triols having hydroxyl values of 25 to 120. The polyol should have a number average molecular weight in the range of 1000 to 6000. Such prepolymers should generally have a free-NCO
content of more than 10%, preferably more than 16% and most preferably 16 to 29% Suitable polymers are those in which the stoichiometric ratio of isocyanate (NCO) to hydroxyl (OI-~ exceeds 1:1. RubinateTM M available from ICI Americas is a suitable polymeric MDI composition useful in the present invention.
The second component of the present compositions is an isocyanate-reactive component being characterized by the nitrogen weight average equivalent molecular weight, herein after referred to as Z. Z equals the number average moleculair weight of the reactant divided by the total number of N-atoms per molecule isocyanate reactive compound. When mixtures of isocyanate reactive N tertiary compounds are used, weight average should be used (Zw). .
3o whereby Zw= z~ . wt~ Zw _ ~ mw; . wti ~ wti ~_~ ni E(~i) ' CA 02360100 2001-07-23 with zi : nitrogen weight average equivalent molecular weight of isocyanate reactive component ni : total N-atoms per isocyanate reactive component i S mwi : weight average molecular weight of isocyanate reactive component i wti: weight of isocyanate reactive component i present ~wti : total weight of isocyanate reactive component i present According to the compositions of the present invention, Zw should be equal or less than ~0 1500. More preferably Zw should be between 100 to 1500.
Reactants suitable for the present invention are reactants comprising at least one aliphatic tertiary amine group-containing polyol having an ethylene oxide content of at least 1%.
Preferably, the ethylene oxide content is from 1 to 90%, preferably 5 to 60.
The aliphatic ~ 5 tertiary amine group-containing polyol provides and ethylene oxide content in the prepolymer of 0.01 to 27%, preferably 0.35 to 15%. This amount of ethylene oxide is the total amount in the prepolymer.
The aliphatic tertiary amine group-containing polyols are the known alkoxylation products 2o of amines or aminoalcohols with at least two active hydrogen atoms with ethylene oxide and optionally propylene oxide. Suitable initiator molecules include: ammonia, ethylene diamine, hexamethylene diamine, methylamine, diaminodiphenyl methane, aniline, ethanolamine, diethanolamine, N-methyl diethanolamine, and tetrahydroxyl ethyl ethylenediamine.
Suitable aliphatic tertiary amine group-containing polyols are those wherein the initiator comprises 1 to 18 and preferably 1 to 6 carbon atoms. Suitable aliphatic tertiary amine group-containing polyols have an average molecular weight of about 1500 to 10,000 and preferably 1500 to 6000 and an average OH functionality of 1.8 to 6Ø
Preferred amine group-containing polyols for use in the present invention includes those prepared from ethylene diamine, triethylene tetramine and triethanolamine.
WO 00!44848 -6_ PCTJEP00/00035 -The present compositions comprise the reactant such as the aliphatic tertiary amine group-containing polyol component, in an amount of 1 to 50%, preferably 7 to 30% and most preferably 10 to 20% by weight based upon the total amount of isocyanate and polyol in the composition.
In its most preferred form, the amine group-containing polyol is an ethylene diamine-based polyol containing ethylene oxide. Suitable ethylene diamine-based polyols are those having an ethylene oxide content of 1 to 90%, preferably 5 to 60%. The ethylene oxide o content refers to the amount of ethylene oxide utilized in the preparation of the polyols as discussed above. During production, the ethylene oxide reacts with the initiator. The polyols should have a molecular weight in the range of 1500 to 6000.
Suitable ethylene diamine-based polyols useful in the present compositions include those of the following formula:
H(OH4C2)Y{OH6C3)X (C3 H60)X (C2 H40)YH
/
H(OH4C2)Y{OH6C3)X (C3 H60)X (C2 H40)YH
wherein x is an integer of 1.0 to 29.0, preferably 4.0 to 20 and most preferably 4.0 to 14 and y is an integer of 0.1 to 10.0 and preferably 2.0 to 4Ø Suitable ethylene diamine-based polyols are available commercially, such as the "Synperonic T" series of polyols available from ICI Americas Inc.
Preferably, the total ethylene oxide content by weight of the total adhesive composition is more than 2.5%. Most preferred, at least 40% of the total ethylene oxide content is present 3o as part of the reactant. Polypropylene oxide based reactants or additonal polypropylene oxide based polyols may be used for the present compositions , preferably whereby the weight ratio of ethylene oxide to propylene oxide is at least 1 to 8, said propylene oxide WO 00/44848 PCTlEP00/00035 _7_ being part of the reactant and/or from an additional polyol being present in the total composition.
Preferably, the concentration of nitrogen in the amine group-containing polyol is is 0.002 to 0.05 eqN/100g.
The said adhesive composition may be produced in any number of ways such as, but not limited to:
(i) Sequentially mixing the components at temperatures 25-80oC (with the proviso to that when using pure MDI it is used above 42oC). Said mixtures are then allowed to react.
(ii) Sequentially mixing and pre-reacting components (a) and {b).
(iii) Pre-reacting part of the isocyanate component with one of the isocyanate-reactive components, then separately pre-reacting the rest of the isocyanate ~ 5 component with the other isocyanate-reactive component, and blending the two prepolymers together.
Catalysts can additionally be incorporated into the present compositions to further enhance the cure rate of the compositions. Examples of appropriate catalysts are, e.g., tertiary 2o amine catalysts. Suitable tertiary amine catalysts are available commercially, as Niax A-4, from Union Carbide and Thancat DMDEE, from Texaco. Most preferably, the Niax A-catalyst is used in the relatively slower cure systems.
It has been found however, that reactivity can be controlled by a reactant having a Z~, 25 being equal or less than 1500, so limiting the number of formulations which require the addition of extra catalysts.
Other additives such as fungicides, tackifiers, tTV stabilizers, viscosity reducers, plasticisers, fillers and extenders as well as surface tension modifying agents can be added 30 depending on the specific application or manufacturing procedure.
Furthermore, other adhesives such as, but not limited to, UF, PF and P1RF can also be incorporated into the formulation.
WO 00/44848 PCT/EP00/00035 ' _g_ The adhesive compositions of the present invention have been found to have a pot life of approximately three months or more under moisture-free conditions when mixed prior to application to a substrate.
The present compositions are also "cold curable", i.e., may be cured at a temperature of lOoC to room temperature although they can also be hot cured. Thus, the present compositions may be cured at temperatures of from lOoC to 250oC. Preferably the present compositions are cured at a temperature of 23oC to 125oC. Generally, most systems will cure at room temperature in 10-30 minutes.
The adhesive compositions of the present invention may be used to bond many different types of moisture-containing substrates. It is preferred that at least one of the substrates be selected from the group consisting of wood, paper, rice hulls, cement, stone, cloth, grass, corn husks, bagasse, nut shells, polymeric foam films and sheets, polymeric foams and fibrous materials. Preferably, the present composition is used to fabricate mufti-substrate composites or laminates. Those composites or laminates of particular interest being those comprising lignocellulosic or cellulosic materials, such as wood or paper, to prepare products such as finger joints, "Glulam" and I- Beams, plywood, wafer board, particleboard, fiberboard, chipboard, and oriented wood products, such as "Parallam", 2o available from McMillan Bloedell.
As the present adhesive compositions are moisture-activated, it is important that the substrates have relatively high moisture contents. Specifically, the substrates should have moisture contents of at least 7%. Preferably, the substrates have moisture contents of 10 to 20% by weight and more preferably 12 to 15% by weight When used to bond multiple substrates together, the present composition is applied to a surface of a first substrate. A surface of a second substrate is then contacted with the surface of the first substrate containing the present composition. Pressure is then applied 3o to the contacted surfaces and the adhesive compositions are allowed to cure. The surface of .
the second substrate against which the first substrate is contacted is generally not coated with the present adhesive composition. However, that surface may also be coated prior to contacting the substrates.
The present invention is further directed to a process for bonding multiple substrates comprising ( 1 ) applying to a surface of a first substrate the moisture-activated adhesive composition of the present invention and contacting the surface of the first substrate with a surface of a second substrate (2) applying pressure to the contacted surfaces, and (3) curing the adhesive composition.
o Additionally, independent of the moisture content, additional water can be applied to in the following manner (a) the first substrate surface prior to the application of the present composition, (b) on top of the resin, after application to the first substrate surface and/or (c) to the second substrate surface prior to contacting the first, resinated substrate surface, or any combinations thereof, to speed up the reaction Such additions of moisture are called "misting". Misting can optionally be used to increase 2o the accessibility of water to the reactive isocyanate. Preferably, the application levels of water should not exceed 5% of the resin loading.
The present adhesive compositions also provide cold tack immediately after application to a substrate. This is particularly useful for pre-press operations where mechanical handling is often necessary. Cold tack is achieved naturally by the present composition adhesives, described in this invention. The present compositions may be used as additives to other resins and adhesives, which require improved tack properties.
The present adhesive compositions may be applied to the surfaces of the substrates in any 3o conventional manner. For example, the surface may be coated with the composition by spraying, brushing, etc. Suitable means for applying the adhesive compositions to the surface of the substrate for a particular application will be evident to one skilled in the art from the present disclosure.
WO 00!44848 PCT/EP00/00035 After the coated substrates are contacted with each other, pressure is applied thereto. The pressure should be sufficient to cause the surfaces to adhere to one another.
Generally, the .
amount of pressure and the time period for which the pressure is applied are not limited and specific pressures and times will be evident to one skilled in the art from the present disclosure. However, it has been found preferable that a pressure of approximately 10 to 200 psi (equivalent to 69 to 1380 kPa) be applied for 10 to 20 minutes to cause appropriate adhesion for most substrates. Further processing can generally be conducted on the treated substrates in less than one hour.
Zo The invention is now illustrated by the following examples, which are not intended to limit the scope of the invention.
EXAMPLES
The following adhesive compositions were prepared in accordance with the present invention.
Example 1 MDI prepolymer 80 Polyol 1 20 The MDI prepolymer had an NCO content of 24.9% and was prepared by reacting Rubinol F-456 (a polyether diol available from ICI Americas Inc.) with a 6y/31 blend of polymeric MDI to pure MDI. The polymeric MDI used was RubinateT'" M and the pure MDI
used was RubinateTM 44,both available from ICI America Inc. Polyol 1 was "Synperonic T 304"
t5 which is an ethylene diamine-based polyol available from ICI Americas Inc.
Zw<1500 Comparison example 2a 2o MDI prepolymer 80 Polyol 2 20 The MDI prepolymer had an NCO content of 24.9% and was prepared by reacting Rubinol 25 F-456 (a polyether diol available from ICI Americas Inc.) with a 69/31 blend of polymeric MDI to pure MDI. The polymeric MDI used was RubinateTM M and the pure MDI used was RubinateTM 44,both available from ICI Americas Inc. Polyol 2 was "Synperonic T
701" which is an ethylene diamine-based polyol available from ICI Americas Inc.
Zw> 1500 Example 2b MDI prepolymer 63.58 Polyol 2 1.91 Polyol 1 8.27 Niax A-4 0.64 Calcium Carbonate No.7 25.43 SAG 47 0.07 Same as example 2a with SAG 47 is an antifoam agent available from Union Carbide.
NiaxA-4 is a suitable tertiary amine catalysts available from Union Carbide.
Z~,,,> 1500 Example 3 MDI prepolymer84.4 Polyol 1 15.05 DMDEE 0.05 ~5 The MDI prepolymer had an NCO content of 25.2% and was prepared by reacting Rubinol F-456 (a polyether diol available from 1CI Americas Inc.) with a 71.2/28.8blend of polymeric MDI to pure MDI. The polymeric MDI used was RubinateTM M and the pure MDI used was RubinateTM 44, both available from ICI Americas Inc. Polyol 1 was 20 "Synperonic T 304" which is an ethylene diamine - based poIyol available from ICI
Americas Inc.
Zw< 1500 Example 4 25 MDI prepolymer 80 Polyol 1 20 The MDI prepolymer had an NCO content of 24.9% and was prepared by reacting Rubinol F-481 (a EO containing polyether diol available from ICI Americas Inc.) with a 30 69/31 blend of polymeric MDI to pure MDI. The polymeric MDI used was RubinateTM M
and the pure MDI used was RubinateTM 44, both available from ICI Americas Inc.
Polyol 1 was "Synperonic T 304" which is an ethylene diamine - based polyol available from ICI
Americas Inc.
, WO 00/44848 PCT/EP00/00035 Zw<1500 Example 5 Polymeric MDI 45 ' s 44 MDI 20 Rubinol F456 15 Synperonic T 304 20 The products were made by sequential addition of the different components. The final to NCO, viscosity and properties are the same as in Example land demonstrate the flexibility in formulating the adhesive.
Zw<1500 Results ~ 5 Reactivity test measured as the time taken to start foaming when formulation is contacted on a 10% moisture containing aspen wood showed that the formulation according to example 1 is significantly faster than formulation of example 2 a and b and equivalent to the formulation of example 3 (catalyst containing example). The results of example 4 is equivalent to example 1 and demonstrates the use of EO-containing polyols 2o for making the prepolymer.
Fon~nulations given in examples 1 and 4, were used to construct single lap joints using 150 x 25 x 3 mm tangentially cut aspen wood. Overlaps were 25 x 25 mm and resin loadings were 12 mg.m-2. The lap joints were cured at room temperature for 15 minutes and tested 25 to failure. Two sets of samples were produced. In the first instance, the resin was applied to the wood of moisture content 10%. In the second case, after the application of the adhesive, an additional 5% (based on adhesive weight), water content was applied by spray onto the adhesive layer. The loads to failure were recorded. The results, listed below, show a much higher tensile shear strength and higher percentages of wood failure for the 3o systems with added water.
Tensile Strength failure loads in MPa Without mist With mist Example 1 0.6 3.5 Example 5 0.6 3.5
FIELD OF THE INVENTION
' The present invention is directed to rapid curing moisture-activated adhesive compositions s and methods for their production and a process for bonding multiple substrates using said composition. More specifically, the present invention is directed to specific moisture-activated adhesive compositions which are cold curable in the presence of high moisture content cellulosic or lignocellulosic substrates.
BACKGROUND OF THE INVENTION
1 o In recent years, the use of "engineered lumber" products by the construction industry has become increasingly common - primarily because the availability and cost of adequate quality sawn lumber have become increasingly unfavorable. However, the performance of "engineered lumber" products, which are formed by adhering smaller pieces of wood together into a composite material, represents some major challenges to the adhesives 15 formulator.
Engineered lumber products on the market today, such as finger jointed lumber, wood I-beams, and glue-laminated beams (glu-lams), utilize a variety of adhesive systems, including phenol - formaldeyhde (PF) based adhesives, polyvinylacetate (PVA) adhesives, and isocyanate - based emulsion adhesives. Unfortunately, each of these adhesive systems 2o has limitations, which compromises the effectiveness of the resultant engineered lumber composite.
PF based adhesives require a great deal of heat and/time in order to cure, and are sensitive to high levels of moisture in the wood. Use of these adhesives systems requires engineering controls to maintain a iow moisture content, and to ensure adequate bonding 25 occurs within the composite. The necessity for such costly catalyst and engineering controls increases production costs, and limits productivity, which in turn limits the competitiveness of engineered lumber in. the marketplace. Another major problem associated with these adhesives is their "green strength". These adhesives do not produce adequate bond strength immediately - they typically need to "cure" in order to reach their 3o full potential. This cure time is a matter of hours, often days - which further adds to production costs.
SUBSTITUTE SHEET (RULE 2G) WO 00/44848 PCT/EP00/00035 ' PVA adhesives have limited strength. To date, they have not proven to be suitable for use in structural applications, which require physical properties of a certain minimum standard.
For example, no commercially available PVA bonded engineered lumber product can meet the ASTM D2259 standard, a frequent requirement for structural lumber applications.
Like the PF adhesives discussed above - these systems also suffer from the limitations of slow green strength development, and a dependency on a great deal of heat and/time radiation to ensure adequate bond strengths.
Isocyanate-crosslinked latex emulsion adhesives, also have limitations in that these systems also suffer from the limitations of slow green strength development, and a dependency on a great deal of heat to ensure adequate bonding.
Polyisocyanate based adhesive compositions have also been identified for composite wood applications. Examples are moisture curable urethane-modified polyisocyanate adhesives described in EP-B-723 561 which discloses urethane-modified poiyisocyanate adhesives for use in plywood panel wood composites. These compositions contain auto catalytic species, designed to increase the reactivity of the polyisocyanate, enabling cure at ambient temperatures in a matter of minutes. However, for engineered lumber products, the different processing requirements between panels and lumber becomes extremely 2o important. As a consequence none of the existing polyisocyanate products, designed for relatively thin composite wood panels, exhibits suffcient reactivity to truly be cost-effective in relatively thick engineered lumber applications. ;S
It is therefore an object of the present invention to provide an adhesive composition especially designed for engineered lumber which impart adequate strength and reactivity and tack without the need for costly catalyst and processing/engineerning controls to overcome inherent problems, such as: maintaining low raw material moisture contents, providing a great deal of heat and time in order to cure the adhesive, and protracted "green" .
strength development.
.
These objectives are met by the present adhesive compositions, which demonstrate excellent adhesive properties with a prolonged pot life, accelerated cure, particularly at ' CA 02360100 2001-07-23 .j_ room temperature. Surprisingly, the compositions according to the present invention provide equal performance than those compositions as described in EP 0 723 561. The present compositions are activated by the moisture present in the substrate with which they are being used and thus, they may be most effectively used with substrates having a relatively high moisture content, even as high as 20% or more. Accordingly, the present compositions are effectively used with various types of lignocellulosic materials and are particularly useful in the preparation of engineered lumber products as discussed above.
SUMMARY OF THE INVENTION
The present invention relates to a moisture-activated adhesive composition comprising the reaction product of (A) polyisocyanate selected from either (a) a blend of polymeric MDI
and pure MDI andlor from (b) an isocyanate-terminated prepolymer. (B) an isocyanate-reactive component comprising at least one aliphatic tertiary amine group-containing polyol made by alkoxylation of amines or aminoalcohols characterized in that the i5 isocyanate reactive component has a nitrogen weight average equivalent molecular weight index Z~, being equal or less than 1500.
DETAILED DESCRIPTION OF THE INVENTION
According to the present invention, the polyisocyanate component is selected from either 20 (a) a blend of polymeric MDI and pwe MDI and/or an isocyanate-terminated prepolymer.
In accordance with the compositions of the present invention, the blend of polymeric MDI
and pure MDI have been found to provide improved penetration into the lignocellulosic substrate and higher wood failwe as opposed to glueline failwe. A commercially available pwe MDI product suitable for use in the present invention is RubinateTM 44 available 25 from ICI Americas Inc. The preferred blends contain polymeric MDI to pwe MDI in ratios of 95:5 to 50:50 and preferably 60:40 to 80:20.
_ The isocyanate-terminated prepolymers as used herein, the term "isocyanate-terminated prepolymer" includes the prepolymer as well as the pseudoprepolymer, i.e., a mixtwe of ' 3o the prepolymer and the polyisocyanate from which the prepolymer is prepared. The isocyanate-terminated prepolymer useful in the present compositions should have a free isocyanate (NCO) content of from 10 to 29%, preferably 16 to 29%. In general, the f polymeric polyisocyanate may be prepared by the reaction of an excess of a polyisocyanate and a polyol, including aminated polyols or imino/enamines thereof.
Suitable polyols for preparing the isocyanate-terminated prepolymers include:
(a) polyether polyols, thioether polyols andlor hydrocarbon-based polyols having a molecular weight of from 1000 to 6000 and an average hydroxyl functionality of from 1.8 to 4 (b) polyester polyols having a molecular weight of 1000 or more and an average hydroxyl functionality of from 1.9 to 4.
Particularly preferred isocyanate-terminated prepolymers useful in the present invention are MDI prepolymers, which are the reaction product of an excess of polymeric MDI and polyether polyols. The polyether polyols are preferably diols or triols having hydroxyl values of 25 to 120. The polyol should have a number average molecular weight in the range of 1000 to 6000. Such prepolymers should generally have a free-NCO
content of more than 10%, preferably more than 16% and most preferably 16 to 29% Suitable polymers are those in which the stoichiometric ratio of isocyanate (NCO) to hydroxyl (OI-~ exceeds 1:1. RubinateTM M available from ICI Americas is a suitable polymeric MDI composition useful in the present invention.
The second component of the present compositions is an isocyanate-reactive component being characterized by the nitrogen weight average equivalent molecular weight, herein after referred to as Z. Z equals the number average moleculair weight of the reactant divided by the total number of N-atoms per molecule isocyanate reactive compound. When mixtures of isocyanate reactive N tertiary compounds are used, weight average should be used (Zw). .
3o whereby Zw= z~ . wt~ Zw _ ~ mw; . wti ~ wti ~_~ ni E(~i) ' CA 02360100 2001-07-23 with zi : nitrogen weight average equivalent molecular weight of isocyanate reactive component ni : total N-atoms per isocyanate reactive component i S mwi : weight average molecular weight of isocyanate reactive component i wti: weight of isocyanate reactive component i present ~wti : total weight of isocyanate reactive component i present According to the compositions of the present invention, Zw should be equal or less than ~0 1500. More preferably Zw should be between 100 to 1500.
Reactants suitable for the present invention are reactants comprising at least one aliphatic tertiary amine group-containing polyol having an ethylene oxide content of at least 1%.
Preferably, the ethylene oxide content is from 1 to 90%, preferably 5 to 60.
The aliphatic ~ 5 tertiary amine group-containing polyol provides and ethylene oxide content in the prepolymer of 0.01 to 27%, preferably 0.35 to 15%. This amount of ethylene oxide is the total amount in the prepolymer.
The aliphatic tertiary amine group-containing polyols are the known alkoxylation products 2o of amines or aminoalcohols with at least two active hydrogen atoms with ethylene oxide and optionally propylene oxide. Suitable initiator molecules include: ammonia, ethylene diamine, hexamethylene diamine, methylamine, diaminodiphenyl methane, aniline, ethanolamine, diethanolamine, N-methyl diethanolamine, and tetrahydroxyl ethyl ethylenediamine.
Suitable aliphatic tertiary amine group-containing polyols are those wherein the initiator comprises 1 to 18 and preferably 1 to 6 carbon atoms. Suitable aliphatic tertiary amine group-containing polyols have an average molecular weight of about 1500 to 10,000 and preferably 1500 to 6000 and an average OH functionality of 1.8 to 6Ø
Preferred amine group-containing polyols for use in the present invention includes those prepared from ethylene diamine, triethylene tetramine and triethanolamine.
WO 00!44848 -6_ PCTJEP00/00035 -The present compositions comprise the reactant such as the aliphatic tertiary amine group-containing polyol component, in an amount of 1 to 50%, preferably 7 to 30% and most preferably 10 to 20% by weight based upon the total amount of isocyanate and polyol in the composition.
In its most preferred form, the amine group-containing polyol is an ethylene diamine-based polyol containing ethylene oxide. Suitable ethylene diamine-based polyols are those having an ethylene oxide content of 1 to 90%, preferably 5 to 60%. The ethylene oxide o content refers to the amount of ethylene oxide utilized in the preparation of the polyols as discussed above. During production, the ethylene oxide reacts with the initiator. The polyols should have a molecular weight in the range of 1500 to 6000.
Suitable ethylene diamine-based polyols useful in the present compositions include those of the following formula:
H(OH4C2)Y{OH6C3)X (C3 H60)X (C2 H40)YH
/
H(OH4C2)Y{OH6C3)X (C3 H60)X (C2 H40)YH
wherein x is an integer of 1.0 to 29.0, preferably 4.0 to 20 and most preferably 4.0 to 14 and y is an integer of 0.1 to 10.0 and preferably 2.0 to 4Ø Suitable ethylene diamine-based polyols are available commercially, such as the "Synperonic T" series of polyols available from ICI Americas Inc.
Preferably, the total ethylene oxide content by weight of the total adhesive composition is more than 2.5%. Most preferred, at least 40% of the total ethylene oxide content is present 3o as part of the reactant. Polypropylene oxide based reactants or additonal polypropylene oxide based polyols may be used for the present compositions , preferably whereby the weight ratio of ethylene oxide to propylene oxide is at least 1 to 8, said propylene oxide WO 00/44848 PCTlEP00/00035 _7_ being part of the reactant and/or from an additional polyol being present in the total composition.
Preferably, the concentration of nitrogen in the amine group-containing polyol is is 0.002 to 0.05 eqN/100g.
The said adhesive composition may be produced in any number of ways such as, but not limited to:
(i) Sequentially mixing the components at temperatures 25-80oC (with the proviso to that when using pure MDI it is used above 42oC). Said mixtures are then allowed to react.
(ii) Sequentially mixing and pre-reacting components (a) and {b).
(iii) Pre-reacting part of the isocyanate component with one of the isocyanate-reactive components, then separately pre-reacting the rest of the isocyanate ~ 5 component with the other isocyanate-reactive component, and blending the two prepolymers together.
Catalysts can additionally be incorporated into the present compositions to further enhance the cure rate of the compositions. Examples of appropriate catalysts are, e.g., tertiary 2o amine catalysts. Suitable tertiary amine catalysts are available commercially, as Niax A-4, from Union Carbide and Thancat DMDEE, from Texaco. Most preferably, the Niax A-catalyst is used in the relatively slower cure systems.
It has been found however, that reactivity can be controlled by a reactant having a Z~, 25 being equal or less than 1500, so limiting the number of formulations which require the addition of extra catalysts.
Other additives such as fungicides, tackifiers, tTV stabilizers, viscosity reducers, plasticisers, fillers and extenders as well as surface tension modifying agents can be added 30 depending on the specific application or manufacturing procedure.
Furthermore, other adhesives such as, but not limited to, UF, PF and P1RF can also be incorporated into the formulation.
WO 00/44848 PCT/EP00/00035 ' _g_ The adhesive compositions of the present invention have been found to have a pot life of approximately three months or more under moisture-free conditions when mixed prior to application to a substrate.
The present compositions are also "cold curable", i.e., may be cured at a temperature of lOoC to room temperature although they can also be hot cured. Thus, the present compositions may be cured at temperatures of from lOoC to 250oC. Preferably the present compositions are cured at a temperature of 23oC to 125oC. Generally, most systems will cure at room temperature in 10-30 minutes.
The adhesive compositions of the present invention may be used to bond many different types of moisture-containing substrates. It is preferred that at least one of the substrates be selected from the group consisting of wood, paper, rice hulls, cement, stone, cloth, grass, corn husks, bagasse, nut shells, polymeric foam films and sheets, polymeric foams and fibrous materials. Preferably, the present composition is used to fabricate mufti-substrate composites or laminates. Those composites or laminates of particular interest being those comprising lignocellulosic or cellulosic materials, such as wood or paper, to prepare products such as finger joints, "Glulam" and I- Beams, plywood, wafer board, particleboard, fiberboard, chipboard, and oriented wood products, such as "Parallam", 2o available from McMillan Bloedell.
As the present adhesive compositions are moisture-activated, it is important that the substrates have relatively high moisture contents. Specifically, the substrates should have moisture contents of at least 7%. Preferably, the substrates have moisture contents of 10 to 20% by weight and more preferably 12 to 15% by weight When used to bond multiple substrates together, the present composition is applied to a surface of a first substrate. A surface of a second substrate is then contacted with the surface of the first substrate containing the present composition. Pressure is then applied 3o to the contacted surfaces and the adhesive compositions are allowed to cure. The surface of .
the second substrate against which the first substrate is contacted is generally not coated with the present adhesive composition. However, that surface may also be coated prior to contacting the substrates.
The present invention is further directed to a process for bonding multiple substrates comprising ( 1 ) applying to a surface of a first substrate the moisture-activated adhesive composition of the present invention and contacting the surface of the first substrate with a surface of a second substrate (2) applying pressure to the contacted surfaces, and (3) curing the adhesive composition.
o Additionally, independent of the moisture content, additional water can be applied to in the following manner (a) the first substrate surface prior to the application of the present composition, (b) on top of the resin, after application to the first substrate surface and/or (c) to the second substrate surface prior to contacting the first, resinated substrate surface, or any combinations thereof, to speed up the reaction Such additions of moisture are called "misting". Misting can optionally be used to increase 2o the accessibility of water to the reactive isocyanate. Preferably, the application levels of water should not exceed 5% of the resin loading.
The present adhesive compositions also provide cold tack immediately after application to a substrate. This is particularly useful for pre-press operations where mechanical handling is often necessary. Cold tack is achieved naturally by the present composition adhesives, described in this invention. The present compositions may be used as additives to other resins and adhesives, which require improved tack properties.
The present adhesive compositions may be applied to the surfaces of the substrates in any 3o conventional manner. For example, the surface may be coated with the composition by spraying, brushing, etc. Suitable means for applying the adhesive compositions to the surface of the substrate for a particular application will be evident to one skilled in the art from the present disclosure.
WO 00!44848 PCT/EP00/00035 After the coated substrates are contacted with each other, pressure is applied thereto. The pressure should be sufficient to cause the surfaces to adhere to one another.
Generally, the .
amount of pressure and the time period for which the pressure is applied are not limited and specific pressures and times will be evident to one skilled in the art from the present disclosure. However, it has been found preferable that a pressure of approximately 10 to 200 psi (equivalent to 69 to 1380 kPa) be applied for 10 to 20 minutes to cause appropriate adhesion for most substrates. Further processing can generally be conducted on the treated substrates in less than one hour.
Zo The invention is now illustrated by the following examples, which are not intended to limit the scope of the invention.
EXAMPLES
The following adhesive compositions were prepared in accordance with the present invention.
Example 1 MDI prepolymer 80 Polyol 1 20 The MDI prepolymer had an NCO content of 24.9% and was prepared by reacting Rubinol F-456 (a polyether diol available from ICI Americas Inc.) with a 6y/31 blend of polymeric MDI to pure MDI. The polymeric MDI used was RubinateT'" M and the pure MDI
used was RubinateTM 44,both available from ICI America Inc. Polyol 1 was "Synperonic T 304"
t5 which is an ethylene diamine-based polyol available from ICI Americas Inc.
Zw<1500 Comparison example 2a 2o MDI prepolymer 80 Polyol 2 20 The MDI prepolymer had an NCO content of 24.9% and was prepared by reacting Rubinol 25 F-456 (a polyether diol available from ICI Americas Inc.) with a 69/31 blend of polymeric MDI to pure MDI. The polymeric MDI used was RubinateTM M and the pure MDI used was RubinateTM 44,both available from ICI Americas Inc. Polyol 2 was "Synperonic T
701" which is an ethylene diamine-based polyol available from ICI Americas Inc.
Zw> 1500 Example 2b MDI prepolymer 63.58 Polyol 2 1.91 Polyol 1 8.27 Niax A-4 0.64 Calcium Carbonate No.7 25.43 SAG 47 0.07 Same as example 2a with SAG 47 is an antifoam agent available from Union Carbide.
NiaxA-4 is a suitable tertiary amine catalysts available from Union Carbide.
Z~,,,> 1500 Example 3 MDI prepolymer84.4 Polyol 1 15.05 DMDEE 0.05 ~5 The MDI prepolymer had an NCO content of 25.2% and was prepared by reacting Rubinol F-456 (a polyether diol available from 1CI Americas Inc.) with a 71.2/28.8blend of polymeric MDI to pure MDI. The polymeric MDI used was RubinateTM M and the pure MDI used was RubinateTM 44, both available from ICI Americas Inc. Polyol 1 was 20 "Synperonic T 304" which is an ethylene diamine - based poIyol available from ICI
Americas Inc.
Zw< 1500 Example 4 25 MDI prepolymer 80 Polyol 1 20 The MDI prepolymer had an NCO content of 24.9% and was prepared by reacting Rubinol F-481 (a EO containing polyether diol available from ICI Americas Inc.) with a 30 69/31 blend of polymeric MDI to pure MDI. The polymeric MDI used was RubinateTM M
and the pure MDI used was RubinateTM 44, both available from ICI Americas Inc.
Polyol 1 was "Synperonic T 304" which is an ethylene diamine - based polyol available from ICI
Americas Inc.
, WO 00/44848 PCT/EP00/00035 Zw<1500 Example 5 Polymeric MDI 45 ' s 44 MDI 20 Rubinol F456 15 Synperonic T 304 20 The products were made by sequential addition of the different components. The final to NCO, viscosity and properties are the same as in Example land demonstrate the flexibility in formulating the adhesive.
Zw<1500 Results ~ 5 Reactivity test measured as the time taken to start foaming when formulation is contacted on a 10% moisture containing aspen wood showed that the formulation according to example 1 is significantly faster than formulation of example 2 a and b and equivalent to the formulation of example 3 (catalyst containing example). The results of example 4 is equivalent to example 1 and demonstrates the use of EO-containing polyols 2o for making the prepolymer.
Fon~nulations given in examples 1 and 4, were used to construct single lap joints using 150 x 25 x 3 mm tangentially cut aspen wood. Overlaps were 25 x 25 mm and resin loadings were 12 mg.m-2. The lap joints were cured at room temperature for 15 minutes and tested 25 to failure. Two sets of samples were produced. In the first instance, the resin was applied to the wood of moisture content 10%. In the second case, after the application of the adhesive, an additional 5% (based on adhesive weight), water content was applied by spray onto the adhesive layer. The loads to failure were recorded. The results, listed below, show a much higher tensile shear strength and higher percentages of wood failure for the 3o systems with added water.
Tensile Strength failure loads in MPa Without mist With mist Example 1 0.6 3.5 Example 5 0.6 3.5
Claims (19)
1. A moisture-activated adhesive composition comprising the reaction product of (A) ~a polyisocyanate selected from (a) a blend of polymeric MDI and pure MDI and/or from (b) an isocyanate-terminated prepolymer.
(B) ~an isocyanate-reactive component comprising at least one aliphatic tertiary amine group-containing polyol made by alkoxylation of amines or aminoalcohols characterized in that said isocyanate reactive component has a nitrogen weight average equivalent molecular weight index, herein after referred to as Z
W.cndot. Z W
being equal or less than 1500 whereby <IMGs>
with z i : nitrogen weight average equivalent molecular weight of isocyanate reactive component i n i : total N-atoms per isocyanate reactive component i mw i : weight average molecular weight of isocyanate reactive component i wt i: weight of isocyanate reactive component i present .SIGMA.wt i : total weight of isocyanate reactive component i present
(B) ~an isocyanate-reactive component comprising at least one aliphatic tertiary amine group-containing polyol made by alkoxylation of amines or aminoalcohols characterized in that said isocyanate reactive component has a nitrogen weight average equivalent molecular weight index, herein after referred to as Z
W.cndot. Z W
being equal or less than 1500 whereby <IMGs>
with z i : nitrogen weight average equivalent molecular weight of isocyanate reactive component i n i : total N-atoms per isocyanate reactive component i mw i : weight average molecular weight of isocyanate reactive component i wt i: weight of isocyanate reactive component i present .SIGMA.wt i : total weight of isocyanate reactive component i present
2. A moisture-activated adhesive composition according to claim 1, whereby Z
w, is between 100 to 1500.
w, is between 100 to 1500.
3. A moisture-activated adhesive composition according to claim 1-2, whereby the total ethylene oxide content by weight of the total adhesive composition is more than 2.5%
4. A moisture-activated adhesive composition according to claims 1-3 whereby at least 40% of the total ethylene oxide content is present as part of the reactant
5. A moisture-activated adhesive composition according to claims 4 whereby the weight ratio of ethylene oxide to propylene oxide is at least 1 to 8, said propylene oxide being part of the reactant and/or from an additional polyol being present in the composition
6. A moisture -activated adhesive composition according to claims 5 whereby the total nitrogen concentration of the total composition is from 0.002 to 0.05 eqN/100g
7. A moisture-activated adhesive composition according to claims 1-6, wherein said polymeric polyisocyanate is a polymeric diphenylmethane diisocyanate.
8. A moisture-activated adhesive composition according to claim 1-7, wherein said isocyanate-terminated prepolymer having an NCO content of 10 to 29 %.
9. A moisture-activated adhesive composition according to claim 8, wherein said isocyanate-terminated prepolymer is the reaction product of polymeric diphenylmethane diisocyanate and a polyether polyol having a molecular weight of from 1000 to 6000.
10. A moisture-activated adhesive composition according to claim 7, wherein said reactant is an aliphatic tertiary amine group-containing polyol having an ethylene oxide content of 1 to 90 %.
11. A moisture-activated adhesive composition according to claim 10, wherein said aliphatic tertiary amine group-containing polyol has an ethylene oxide content of 5 to 60 %.
12. A moisture-activated adhesive composition according to claim 1, wherein said aliphatic tertiary amine group-containing polyol has a molecular weight of 1500 to 10,000 and comprises an initiator having 1 to 18 carbon atoms.
13. A moisture-activated adhesive composition according to claim 1, wherein said aliphatic tertiary amine group-containing polyol is prepared from a compound selected from the group consisting of ethylene diamine, triethylene tetramine and triethanolamine.
14. A moisture-activated adhesive composition according to claim 13, wherein said aliphatic tertiary amine group-containing polyol is an ethylene diamine-based polyol having the following formula:
wherein x is an integer of 1 to 29.0 and y is an integer of 0.1 to 10.
wherein x is an integer of 1 to 29.0 and y is an integer of 0.1 to 10.
15. A moisture-activated adhesive composition according to claim 1, further comprising a catalyst.
16. A process for bonding multiple substrates comprising 1) applying to a surface of a first substrate a moisture-activated adhesive composition as defined in any one of the preceding claims 2) contacting said surface with a surface of a second substrate 3) applying pressure to the contacted surfaces, and 4) curing said adhesive composition.
17. A process according to claim 15, wherein said substrate has a moisture content of at least 7 % by weight.
18. An engineered lumber product prepared by the process according to claim 16.
19. A process for bonding according to claim 14, wherein additional moisture is applied to the first substrate surface, the surface of the applied adhesive and/or the surface.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11741099P | 1999-01-27 | 1999-01-27 | |
| US60/117,410 | 1999-01-27 | ||
| PCT/EP2000/000035 WO2000044848A1 (en) | 1999-01-27 | 2000-01-05 | Moisture-activated adhesive compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2360100A1 true CA2360100A1 (en) | 2000-08-03 |
Family
ID=22372781
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002360100A Abandoned CA2360100A1 (en) | 1999-01-27 | 2000-01-05 | Moisture-activated adhesive compositions |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1161508A1 (en) |
| AR (1) | AR022400A1 (en) |
| AU (1) | AU2287700A (en) |
| CA (1) | CA2360100A1 (en) |
| WO (1) | WO2000044848A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SG94826A1 (en) * | 2001-05-21 | 2003-03-18 | Nippon Polyurethane Kogyo Kk | Non-aqueous laminate adhesive |
| US20030010442A1 (en) * | 2001-07-09 | 2003-01-16 | Nowicki James W. | Reactive hot melt adhesive |
| DE102009005017A1 (en) * | 2009-01-17 | 2010-07-22 | Bayer Materialscience Ag | Reactive polyurethane compositions |
| EP3140335B1 (en) | 2014-05-08 | 2019-10-02 | Dow Global Technologies LLC | Accelerate cure of moisture curable polyurethane adhesive compositions useful for bonding glass |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU8230182A (en) * | 1981-04-06 | 1982-10-14 | Goodyear Tire And Rubber Company, The | Two pack polyurethane adhesive |
| JPS61228075A (en) * | 1985-04-02 | 1986-10-11 | Meisei Kogyo Kk | Adhesive composition |
| GB9117068D0 (en) * | 1991-08-08 | 1991-09-25 | Ici Plc | Cold curable polyisocyanate adhesive and sealant systems |
| US5562148A (en) * | 1993-03-30 | 1996-10-08 | Ashland Inc. | Process for casting a metal |
| US6368714B1 (en) * | 1993-10-14 | 2002-04-09 | John Russell Robertson | Moisture-activated adhesive compositions |
-
2000
- 2000-01-05 CA CA002360100A patent/CA2360100A1/en not_active Abandoned
- 2000-01-05 WO PCT/EP2000/000035 patent/WO2000044848A1/en not_active Application Discontinuation
- 2000-01-05 EP EP00901505A patent/EP1161508A1/en not_active Withdrawn
- 2000-01-05 AU AU22877/00A patent/AU2287700A/en not_active Abandoned
- 2000-01-19 AR ARP000100237 patent/AR022400A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP1161508A1 (en) | 2001-12-12 |
| AU2287700A (en) | 2000-08-18 |
| AR022400A1 (en) | 2002-09-04 |
| WO2000044848A1 (en) | 2000-08-03 |
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