KR100836606B1 - Polymeric diluents for structural adhesives - Google Patents

Abstract

The present invention provides a low molecular weight, polymer number that functions as a polymer reactive diluent useful for structural adhesives, including but not limited to reactive hot melts, to extend the action time of structural adhesives without adversely affecting creep. It relates to a moisture reactive composition.

Description

Polymer diluents for structural adhesives

The present invention relates to compositions of other modes for reactive diluents used in structural adhesives, including reactive hot melt adhesives. More specifically, the present invention relates to polymers that act as reactive diluents to extend the working time of structural adhesives, including but not limited to reactive hot melt adhesives, in the manufacture of adhesive laminates of liquid hydrocurable reactive hot melts. It is about a use.

Structural adhesives, such as reactive hot melts, are limited by their operating time, green strength, and creep rate when making adhesive laminates. Low molecular weight organic compounds, including volatile organic compounds, known as reactive diluents, are used to extend the action time of the structural adhesive by maintaining fluid state. Conventional reactive diluents are limited in many ways, namely physiologically detrimental as well as unique and distinctive negative taste and odor characteristics. The degree of crosslinking that can be obtained from these reactive diluents (only present before and after 90%) is certain that they cannot be used to finish packaging laminates and adhesive laminates. In addition, conventional reactive diluents have the disadvantage that they can be dispersed as well as a solvent, and thus do not crosslink in an amount of one million parts as a residue and negatively affect adhesion to the interface.

U.S. Provisional Patent Application 60 / 615,668 describes a moisture reactive hot melt adhesive composition having improved creep resistance and good adhesion to a substrate. The reactive hot melt adhesive composition may comprise (a) one or more polymers having a weight average molecular weight of 30,000 to 100,000; (b) one or more multifunctional polyols; (c) at least one organic compound having at least two hydroxy groups; And (d) at least one polyisocyanate, wherein the ratio of isocyanate groups to hydroxyl groups (NCO / OH) is from 2.1 to 6.0 and the amount of free isocyanate groups is greater than 3.5% by weight, based on the total amount of the composition . Unfortunately, the operating time of the adhesive composition is relatively short and can be limited when the composition is applied to a large area of substrate to form an adhesive structure laminate.

Low molecular weight liquid water reactive hot melts have surprisingly been found to act as reactive diluents in structural adhesives and have no problems associated with conventional reactive diluents. Reactive hydrocuring compositions are unique reactive diluents that extend the action time of the structural adhesive; This feature is important with regard to producing large area adhesive structure laminates without adversely affecting creep.

Therefore, the present invention

(a) reactive hot melt adhesives; And

(b) (i) one or more polymers having a weight average molecular weight of 2000 to 4000;

    (ii) one or more multifunctional polyols; And

    (iii) Polymeric reactive diluents containing at least one polyisocyanate, wherein the ratio of isocyanate groups to hydroxyl groups (NCO / OH) is from 4.0 to 11.0 and the amount of free isocyanate groups is greater than 7.5% by weight, based on the total amount of the composition. It provides an adhesive composition comprising a. According to one embodiment, component (a) comprises (i) one or more polymers having a weight average molecular weight of 30,000 to 100,000; (ii) one or more multifunctional polyols; (iii) one or more organic compounds having at least two hydroxy groups; And (iv) at least one polyisocyanate, wherein the ratio of isocyanate groups to hydroxyl groups (NCO / OH) is from 2.1 to 6.0 and the amount of free isocyanate groups is greater than 3.5% by weight based on the total amount of the composition.

The present invention

(a) reactive hot melt adhesives; And

(b) (i) one or more polymers having a weight average molecular weight of 2000 to 4000;

    (ii) one or more multifunctional polyols; And

    (iii) Polymeric reactive diluents containing at least one polyisocyanate, wherein the ratio of isocyanate groups to hydroxyl groups (NCO / OH) is from 4.0 to 11.0 and the amount of free isocyanate groups is greater than 7.5 wt%, based on the total amount of the composition. It provides a method for extending the action time of the reactive hot melt adhesive comprising the step of mixing. According to one embodiment, component (a) comprises (i) one or more polymers having a weight average molecular weight of 30,000 to 100,000; (ii) one or more multifunctional polyols; (iii) one or more organic compounds having at least two hydroxy groups; And (iv) at least one polyisocyanate, wherein the ratio of isocyanate groups to hydroxyl groups (NCO / OH) is from 2.1 to 6.0 and the amount of free isocyanate groups is greater than 3.5% by weight based on the total amount of the composition.

The invention also

(a) reactive hot melt adhesives; And

    (i) one or more polymers having a weight average molecular weight of 2000 to 4000;

    (ii) one or more multifunctional polyols; And

    (iii) Polymeric reactive diluents containing at least one polyisocyanate, wherein the ratio of isocyanate groups to hydroxyl groups (NCO / OH) is from 4.0 to 11.0 and the amount of free isocyanate groups is greater than 7.5% by weight, based on the total amount of the composition. Mixing;

(b) heat the reactive hot melt adhesive;

(c) applying a hot melt adhesive to the first substrate in the presence of moisture;

(d) contacting the applied hot melt adhesive with at least one second substrate;

(e) providing a method of adhering one or more substrates comprising cooling the adhered hot melt adhesive.

As used herein, "water reactive" includes, but is not limited to, for example, compositions containing isocyanate groups, which may be useful in order to increase the strength properties of the adhesive that reacts with water and is subsequently contacted with water. By a composition, it is said that there is an increasing action of the molecular weight of the composition and / or there may be a crosslinking action of the adhesive composition. By "hot-melt" is meant herein that suitable adhesives, which may be solid, semi-solid, or viscous materials, may be usefully heated to provide a viscous fluid adhesive suitable for application to and adhesion to a substrate. .

Compositions usefully used according to the invention which act as polymer reactive diluents have lower weight average molecular weights which are mixed with their corresponding reactive hot melt compositions which are chemically and / or structurally relevant, having suitably higher weight average molecular weights. Having a water reactive composition. Conventional low weight average molecular weight water-reactive compositions alone are not suitable structural adhesives for producing large area adhesive laminates. However, the addition of low weight average molecular weight polymeric water reactive compositions to chemically and / or structurally related reactive hot melt compositions prolongs the action time of the reactive hot melt compositions when preparing adhesive laminates without adversely affecting creep.

The water reactive composition which acts as a useful polymer reactive diluent for hot melt adhesives comprises one or more low molecular weight polymer components. Suitable low molecular weight components include, but are not limited to, polymers with Mw of 1,000 to 20,000, including, for example, polymers having a weight average molecular weight (Mw) of 2,000 to 10,000 and polymers having Mw of 2,000 to 7,000. . Examples of low molecular weight polymers are, for example, (meth) acrylic polymers, copolymers and terpolymers, polyurethane polymers and copolymers, polysiloxane polymers, polyesters, polyvinyl polymers, polystyrenes (PS), PS copolymers, and these Suitable polymers such as, but not limited to, blends of polymers are included. Other suitable low molecular weight polymer components include at least one hydroxy functionality.

The water reactive polymer diluent composition comprises one or more multifunctional polyols. Suitable multifunctional polyols include, but are not limited to, for example, diols, triols, tetraols, pentaols, hexaols, polyester polyols, polyether polyols, polyetheramine polyol polymer blends thereof, and mixtures thereof It is not limited. The multifunctional polyol component is present in an amount from 0 to 80% by weight, based on the total weight of the water reactive composition. Suitable polyol components include, but are not limited to, for example, polymers having a Mw of 400 to 10,000, including, for example, polymers having a weight average molecular weight (Mw) of 2,000 to 7,000 and polymers having a Mw of 2,000 to 5,000. . Other examples of suitable polyols include oligomers and polymers prepared from hydroxypropanoic acid and other fermentation products of biomass (eg, sugars).

The water reactive polymer diluent composition also includes one or more polyisocyanates containing at least two isocyanate groups. Suitable polyisocyanates are, for example, aromatic, aliphatic, cycloaliphatic polyisocyanates and combinations thereof such as, for example, m-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, Hexamethylene diisocyanate, tetramethylene diisocyanate, 1,4-cyclohexane diisocyanate, hexahydrotoluene diisocyanate, 1,5-naphthalene diisocyanate, 1-methoxy-2,4-phenylene diisocyanate, 4 , 4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 4,4 ', 4 "-triphenyl Methane triisocyanate, 1,3,5- Liisocyanato benzene, 2,4,6-triisocyanato toluene, 4,4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate, polymethylene polyisocyanate, polyphenylene poly Isocyanates, 2,4,6-toluene triisocyanate, 4,4'-dimethyl-diphenylmethane tetraisocyanate, and pre-polymers having a number average molecular weight Mn of less than 2000 and containing at least two isocyanate groups, and mixtures thereof The polyisocyanate component is present in an amount of from 1 to 30% by weight, based on the total weight of the water reactive composition.

The ratio of isocyanate groups to hydroxyl groups (NCO / OH) in the polymer reactive diluent composition from all mixed components taken on an equivalent basis is 1.0 to 11.0 and the amount of free isocyanate groups is greater than 7.5 wt% based on the total weight of the composition.

The reactive hot melt (RHM) adhesive composition includes one or more high molecular weight polymer components. Suitable high molecular weight components include, but are not limited to, for example, polymers having a Mw of 30,000 to 100,000, including polymers having a weight average molecular weight (Mw) of 45,000 to 100,000. Examples of high molecular weight polymers include, for example, (meth) acrylic polymers, copolymers and terpolymers, polyurethane polymers and copolymers, polysiloxane polymers, polyesters, polyvinyl polymers, polystyrenes (PS), PS copolymers, divinyl Suitable thermoplastic polymers such as benzene polymers and copolymers, copolymers and terpolymers of ethylene, polyetheramides, polyethers, and blends of such thermoplastic polymers. Other suitable high molecular weight polymer components include at least one hydroxy functionality. High molecular weight polymers having hydroxyl functionality have hydroxyl values from 1 to 15. A description of how to determine the hydroxyl number for a composition is described, for example, in G. Woods, The ICI Polyurethanes Book, 2nd Ed., ICI Polyurethanes, Netherlands (1990), are found in texts well known in the art. One suitable example is, for example, polyvinyl alcohol (PVOH), PVOH copolymer, poly (hydroxy) acrylate polymer, polyvinyl ether / polyvinyl alcohol copolymer, Mw of 20,000 or more, thermoplastic whose chemical backbone is derived from biomass. Polymers, polymer blends thereof, and polymer blends of hydroxy functional thermoplastic polymers and hydroxy functional thermoplastic polymers, but are not limited to these. The RHM composition comprises one or more high molecular weight polymer components in an amount of 1 to 30 weight percent, based on the total weight of the composition.

The reactive hot melt composition also includes one or more multifunctional polyols. "Multifunctional polyol" means a polyol containing at least two hydroxyl groups per chain. Suitable multifunctional polyols include, but are not limited to, for example, diols, triols, tetraols, pentaols, hexaols, polyester polyols, polyether polyols, polyetheramine polyol polymer blends thereof, and mixtures thereof It is not limited. The multifunctional polyol component is present in an amount of 0.1 to 80 percent by weight based on the total weight of the RHM adhesive composition. Suitable polyol components include, but are not limited to, for example, polymers with Mw between 400 and 10,000, including polymers with Mw between 2,000 and 5,000. Other examples of suitable polyols include oligomers and polymers made from hydroxypropanoic acid and other fermentation products of biomass (eg, sugars).

Polyester polyols suitable for use in the present invention include diacids, or their monoester, diester, or anhydride counterparts, and polyols formed from diols. Diacids can be saturated C ₄ -C ₁₂ aliphatic acids, and / or C ₈ -C ₁₅ aromatic acids, including branched, straight chain, or cyclic materials. Examples of suitable aliphatic acids are, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecanoic acid, 1,4-cyclohexanedicarboxyl Acid, and 2-methylpentane diacid. Examples of suitable aromatic acids include, for example, terephthalic acid, isophthalic acid, phthalic acid, 4,4'-benzophenone dicarboxylic acid, 4,4'-diphenylamine dicarboxylic acid, and mixtures thereof. The diol can be a C ₂ -C ₁₂ branched, straight chain, or cyclic aliphatic diol. Examples of suitable diols are, for example, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,3-butanediol, hexanediol, 2-methyl-2 , 4-pentanediol, cyclohexane-1,4-dimethanol, 1,12-dodecanediol, and mixtures thereof. Other suitable polyester polyols usefully used according to the invention include polyols prepared from acid dimers and / or dimeric diols. Mixtures of various suitable polyester polyols are also suitable for use in the present invention.

According to one embodiment of the invention, the polyester polyols are semi-crystalline to crystalline. According to a separate embodiment, the polyester polyols are amorphous, meaning that they do not crystallize under ambient conditions. Both semi-crystalline and amorphous polyols preferably have an acid value of less than 5, including an acid value of 250 to 10,000 and an acid value of less than 2, including 250 to 5,000, as measured by gel permeation chromatography. Have Amorphous polyester polyols are preferably aromatic compounds such as those formed from phthalic anhydride and diethylene glycol. Mixtures of various suitable semi-crystalline and amorphous polyester polyols are also suitable for use in the present invention. The amount of at least one amorphous or semi-crystalline polyester is 30 to 70% by weight, based on the weight of the adhesive composition.

Polyether polyols suitable for use in the present invention include polyoxy-C ₂ -C ₆ -alkylene polyols, including branched and straight chain alkylene groups. Polyether polyols can be prepared by the reaction of polyhydric alcohols with alkylene oxides. Examples of suitable polyether polyols include, for example, polyethylene oxide, poly (1,2- and 1,3-propylene oxide), poly (1,2-butylene oxide), ethylene oxide and 1,2-propylene oxide. Random or block copolymers, and mixtures thereof. Preferred polyether polyols are polypropylene glycols. The polyether polyols preferably have a weight average molecular weight (Mw) measured by gel permeation chromatography of 400 to 8,000, more preferably 1,000 to 3,000. Mixtures of various suitable polyether polyols are also suitable for use in the present invention.

The reactive hot melt composition also includes one or more organic compounds having at least two hydroxy groups. Suitable organic compounds are compounds having Mw of about 100 to 10,000, including polymers having Mw of about 100 to 5,000. Organic components having at least two hydroxyl functionalities have hydroxyl values of 10 to 20000, including hydroxyl values of 10 to 1500, 10 to 1000, and 10 to 500. Suitable organic compounds are, for example, diols, triols, tetraols, pentaols, hexaols, esters of unsaturated fatty acids, esters of saturated fatty acids, fats, oils, cottonseed oil, linseed oil, olive oil, palm oil, corn oil, peanut oil , Soybean oil, and castor oil, but are not limited to these. Oils include oils modified by hydrogenation and polyoxyalkene polymers such as polyoxyethylene polymers and include, for example, hydrogenated oils, partially hydrogenated oils, and polyoxyethylene oils. The amount of organic component having at least two hydroxyl functionalities is 1 to 15% by weight, based on the weight of the adhesive composition.

The reactive hot melt composition also includes one or more polyisocyanates containing at least two isocyanate groups. Suitable polyisocyanates are for example aromatic, aliphatic, cycloaliphatic polyisocyanates and combinations thereof such as, for example, m-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, Hexamethylene diisocyanate, tetramethylene diisocyanate, 1,4-cyclohexane diisocyanate, hexahydrotoluene diisocyanate, 1,5-naphthalene diisocyanate, 1-methoxy-2,4-phenylene diisocyanate, 4,4 '-Diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3, 3'-dimethyl-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 4,4 ', 4 "-triphenylmethane tri Isocyanate, 1,3,5- Liisocyanato benzene, 2,4,6-triisocyanato toluene, 4,4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate, polymethylene polyisocyanate, polyphenylene poly Isocyanates, 2,4,6-toluene triisocyanate, 4,4'-dimethyl-diphenylmethane tetraisocyanate, and pre-polymers having a number average molecular weight Mn of less than 2000 and containing at least two isocyanate groups, and mixtures thereof The polyisocyanate component is present in an amount of from 14 to 30% by weight, based on the total weight of the RHM adhesive composition.

The ratio of isocyanate group to hydroxyl group (NCO / OH) in the reactive hot melt adhesive composition from all mixed components taken on an equivalent basis includes 2.2 to 4.0, to provide an adhesive composition with excess isocyanate groups, 2.1 to 6.0, including greater than 3.5 and larger.

Another useful method characterized by the mixing of the components of the invention is the free NCO content. By "free isocyanate (NCO)" is meant herein an isocyanate group that remains free in the polyisocyanate produced after preparing the polyisocyanate from the isocyanate monomer and the hydroxyl monomer. Free NCO content is the weight percent of free NCO, based on the total weight of the mixture. Free NCO is an amount of NCO that exceeds the amount needed to match OH groups in the mixture on a 1: 1 equivalent basis. In the practice of the present invention, suitable compositions comprise 3.5% to 20% and have a free NCO content of at least 3.5%, including 3.5% to 7%. Without being bound by theory, increasing the NCO / OH ratio and free NCO content leads to a cured adhesive composition with a greater concentration of crosslinks, which in turn leads to improved creep resistance.

The components of the reactive hot melt adhesive and the polymer reactive diluent composition are mixed by conventional means, preferably in an inert, dry atmosphere, and preferably at a temperature of 50 ° C. to 120 ° C., all the hydroxy groups must be corresponding urethanes. Allow enough time for conversion to the group. The polymer component is dissolved by heating and mixing at least one of the non-isocyanate containing components prior to reaction with the polyisocyanate. Optionally, a catalyst such as, for example, a tertiary amine or tin catalyst can be mixed with the components before, during or after the reaction to form an adhesive composition. When using any of these catalysts, typical levels of use are less than 0.3% by weight, based on the total weight of the mixed components. The adhesive composition with increased prolonged action time is preferably stored under inert, dry atmosphere until use.

The hot-melt adhesive composition is formulated by mixing additional conventional ingredients such as chain extenders, fillers, pigments, thickeners, plasticizers, rheology modifiers, and other suitable additives to the reactivity of the NCO-functional groups, which are preferably maintained. Can be. According to one embodiment, the amount of chain extender added is from 0 to 10% by weight, based on the weight of the RHM adhesive composition.

According to one embodiment of the invention, the components comprise at least one hydroxy-functional triglyceride or at least one functional polyol of one or more fatty acids. The hydroxyl-functional triglycerides of fatty acids are residues of fatty acids of the formula CH ₂ OR ¹ -CHOR ¹ -CH ₂ OR ³ , wherein R ¹ , R ² and R ³ may be the same or different, at least one of which is Has hydroxyl functionality).

In the method of adhering the substrate of the invention, for example, by means of pumping or gravity supply, the reactive hot-extended action has been extended to obtain a viscosity suitable for transferring the adhesive to the application and for applying the adhesive to the first substrate in the presence of moisture. Heat the melt adhesive. The temperature should be high enough to achieve a suitable viscosity but low enough to avoid excessive degradation or other adverse effects on the adhesive. Typical useful temperatures are in the range of 40 ° C. to 200 ° C., preferably 50 ° C. to 160 ° C., and more preferably 100 ° C. to 150 ° C. Application of the adhesive may be carried out by conventional means such as, for example, a heated spray applicator, a heated bead applicator, a heated nozzle, and a heated roll coater to form a continuous or discontinuous film of the adhesive, if necessary. Can be. The adhesive may be applied at levels as low as 1-50 g / m 2 if one of the substrates is a cloth, but may typically be applied at a level of 50 to 250 g / m 2 (4-20 g / ft ² ). Moisture, ie, water, which is expected to react with the NCO-functional group to increase the ultimate adhesive strength of the applied adhesive, is in contact with, for example, ambient humidity, artificially increased or controlled wet air, droplet spray, or applied adhesive. It is believed that this may be the result of a spray of liquid water. It is also contemplated that moisture may be enhanced by other NCO-functional group-reactive components such as, for example, amines.

The second substrate is contacted with the applied adhesive to provide a composite structure. The composite structure thus formed is applied at an application pressure, such as passing between rollers, to increase the contact between the adhesive and the substrate and then cool or cool the composite structure. In another embodiment, the adhesive is applied to two surfaces of the first substrate simultaneously or sequentially, and the adhesive-coated surfaces are bonded simultaneously or sequentially to two additional substrates, which may be the same or different. It is also contemplated that the composite structure may later be adhered to other substrates using the same or different adhesives before or after the process described herein. The first and second substrates to be bonded by the method of the present invention may be the same or different and may have, for example, a smooth or organized surface, such as metals, wood, reinforced wood products, paper, fabrics and nonwovens, and plastics. It is provided in the form of a roll, sheet, film, foil, and the like. These include, for example, Nawang mahogany plywood, impregnated paper, extruded polystyrene foam, expanded polystyrene foam, fiberglass reinforced polyester, polyester cloth, high pressure or low pressure laminates, plywood, aluminum, steel, PVC, and engineering plastics. .

In some embodiments of the invention, the substrate to be bonded is relatively thin and flat, in which case the composite article is a so-called laminate or laminate structure. In other embodiments the substrate is not thin or flat.

According to one embodiment, the structural adhesive with extended working time will meet ICC AC05 building code requirements for years.

The recently developed structural adhesives described in U.S. Provisional Patent Application 60 / 615,668 comply with the conditions of ICC AC05. However, in some embodiments, the product has only a two minute run time and is targeted for the structural insulation panel (SIP) market. It is a laminate composed of oriented strand boards bonded to both sides of an expanded polystyrene (EPS) insulator. The panels are used in the building market to create structures that can be used for industrial or residential purposes. Polymer diluents and adhesives made therefrom allow SIP manufacturers to improve production efficiency over conventional manufacturing methods and lead to improvements in throughput. However, with a working time of only 2 minutes, structural adhesives are limited to constructing and using relatively small area panels, including, for example, 4'X 8 'panels. It is desirable to construct larger panels, including, for example, 8'X 24 'panels, which require structural adhesives with extended operating times.

It was found that addition of 1 to 10% by weight of the liquid polymer reactive diluent composition (prior to catalyst addition) surprisingly acts as a reactive diluent for the reactive hot melt adhesives described above. According to one embodiment, by introducing an amorphous polymer diluent composition into a structural adhesive that meets ICC AC 05 building code requirements, the action time of the structural adhesive is significantly extended. The advantage of the polymer diluent composition is that it reacts completely when mixed with the reactive hot melt adhesive (including> 80% and 100%) and does not adversely affect the creep resistance of the reactive hot melt. In fact, the addition of a polymer reactive diluent can actually improve creep resistance through additional crosslink density. Another advantage of the polymer diluent is that it is a liquid polyurethane such that the water reactive composition is compatible in reactive hot melts (compatibility also means that the polymer diluent is chemically and / or structurally related to the RHM used), soluble or There is miscibility. Conventional reactive diluents have a side effect on the reduced pressure performance of the reactive hot melt in proportion to the amount used. Surprisingly, the addition of liquid water-reactive compositions has been found to improve adhesion to oriented strand boards, and adhesion has been a problem in developing reactive hot melts from the outset. The water reactive compound also improves the wettability of the strand board.

According to one embodiment, the amorphous water reactive liquid polymer composition served as a reactive diluent without catalyst. These specific polymer diluents are used to prevent degradation of hot melt thermal stability because of the additional catalyst.

The following examples are presented to illustrate the present invention and the results obtained by the test procedure.

Examination process

Specimen Manufacturing:

Specimens were prepared in accordance with the procedures provided by the International Conference of Building Officials (ICBO), in "Acceptance Criteria For Sandwich Panel Adhesives," # AC05, oriented strand boards (OSBs), adhesives, expanded polystyrene foams, Adhesives, and sandwich laminates of OSB.

Hand failure:

The sandwich laminate specimens are cut to about 5 to 7.5 cm (2 to 3 inches) in width. Secure one piece of OSB, apply hand force to the other piece of OSB until the sandwich falls, and observe the failure mode. The "pass" failure mode is where the polystyrene foam is separated. The "failure" failure mode is the adhesive failure of the adhesive on the adhesive side.

High temperature creep:

In accordance with ICBO Acceptance Criteria AC05-8.3, a strain of 345 kPas (50 psi) was applied to sandwich specimens containing metal bonded to solid wood (Maple) to observe deformation. The creep is limited to an average of 0.005 in / in (0.127 mm / mm) during the test period and limited to 0.002 in / in (0.0508 mm / mm) at first time. The sample is tested according to section 8.6.3; The creep of wood substrates is tested for one week at 158 ° F. (70 ° C.) or one week at 182 ° F. (83 ° C.) if bonded metal surfaces are involved.

High Temperature Lap Shear:

In accordance with ICBO acceptance criteria AC05-8.4, controlled sandwich specimens were equilibrated to glue line temperatures of 182 ° F. (83 ° C.) and tested for lap shear strength. In passing, the test specimen must have a lap shear strength of at least 80% when tested in glue line at 73 ° F. (23.7 ° C.).

Promote aging:

In accordance with ICBO acceptance criteria AC05-7.2, the sandwich specimens were immersed in water for 48 hours at room temperature and then dried at 145 ° F. (63 ° C.) for 8 hours. The samples were then subjected to three cycles of 16 hours wet at room temperature and 8 hours drying at 145 ° F. (63 ° C.). Samples were adjusted for 7 days according to section 6.0 before testing. In passing, the sample must retain at least 80% of the original adhesive strength of the test specimens that have not been accelerated aging.

Example

Reactive Hot Melt Ingredients

A reactive hot melt adhesive (Mor-Melt ^™ R-5022, Rohm and Haas Company, Philadelphia, Pennsylvania) with an action time of 1.5 minutes was used as a control.

Polymer Water Reactive Composition (MRC) as Reactive Diluent

An uncatalyzed, polymer liquid water reactive composition (PMRC) was prepared.

PMRC1

ingredient weight% Rubinate M ^TM , Lupranate M-20S ^TM , or Mondur MR ^TM (light) 28.70 MDI 11.68 Luprinate MI ^TM 1.24 P-2010 ^TM 58.3 Foamblast ^TM 20F 0.006 BC 0.033 Blankophor SOL ^TM 0.02 Gross weight 100 MDI: diphenylmethane diisocyanate, mixture of isomers, ie 2,4'-MDI and 4,4'-MDI

PMRC2

ingredient weight% Rubinate M ^TM , Lupranate M-20S ^TM , or Mondur MR ^TM (light) 57.56 P-2010 ^TM 39.38 Santicizer 160 ^TM 3.01 BC 0.049 Blankophor SOL ^TM 0.02 Gross weight 100

PMRC3

ingredient weight% Rubinate M ^TM , Lupranate M-20S ^TM , or Mondur MR ^TM (light) 12.58 Luprinate MI ^TM 23.6 P-2010 ^TM 40.7 Poly G 55-56 ^TM 20.3 DIDP 0.75 Tufflo 6006 ^TM 1.98 Foamblast ^TM 20F 0.007 BC 0.018 Blankophor SOL ^TM 0.02 Gross weight 100

SIP includes OSB bonded to both sides of the EPS. To facilitate the use of small amounts of adhesive and conveniently, one side of the cross section of 1 # EPS was pre-laminated to 7/16 "OSB using Mor-Melt ^™ R-5022. This was then 6" X 12. Cut into pieces. The matching section of the OSB was also made as a matching sheath material. This allows coating with one adhesive line and allows measurement of the open time.

PMRC-3 as reactive diluent

500 g aliquots of Mor-Melt ^™ R-5022 were placed in a glass reactor, heated to 90 ° C. and dried nitrogen was flowed. 5 wt% MRC-3 was added thereto. PMRC-3 has a cured Young's modulus of 6000 psi and a viscosity of 4500 cps.

The mixture was left at 90 ° C. until homogeneous. Subsequently, the material was transferred to Black Bros. Transfer to a hot melt roll coater and set to an oil temperature of 310 ° F. The adhesive application rate was set using the same density EPS that was used as the core material. Once an application rate of 12 g / ft ² was obtained, the pre-laminated panel was coated and the adhesive applied to the EPS. The panel was placed aside for the desired defined time of operation, and then the matching section of the OSB was applied. The completed SIPS panels were tightened twice using a Black Bros. nip laminator set for 3/16 "compression of the panels. Once tightened, the panels were placed aside and left for 1 hour under laboratory conditions.

After the end of 1 hour, the 6 "X 12" panels were cut in two lengthwise. On the other hand, one inch of EPS was removed at one end, placed in a vise, and clamped on one of the OSB sides. A pry bar was then sandwiched between the vise face and the outer section of the OSB to slowly move the facer from the core until the panel failed. This was done for each panel made at a specific time of operation.

The action time was significantly increased using PMRC-3 as the reactive diluent: from 1.5 minutes for Mor-Melt ^™ R-5022 (no reactive diluent added) to 5.5 minutes measured tearing the EPS in 1 hour in the lamination.

PMRC-2 as reactive diluent

PMRC-2 has a higher Young's modulus (27000 psi) and a higher viscosity (8000 cps @ 25 ° C). PMRC-2 was added to Mor-Melt ^™ R-5022 at 5% by weight. The laminate was prepared as before. The results were as follows:

An open time of 4.5 minutes was obtained, measured by EPS core failure. To confirm this, 5% by weight of Mor-Melt ^™ R-5022 was added and another batch of reactive hot melt was made using the PMRC-0 base as the reactive diluent.

The same lamination procedure was used for the system with PMRC-0.

Again, comparable to PMRC-1, PMRC-0 was used to obtain an open time of 5.5 minutes. The inherent viscosity of PMRC-0 is 5000 cps, very close to that of PMRC-1. Initially, the lower viscosity water reactive composition seemed to get a longer open time as a reactive diluent for Mor-Melt ^™ R-5022. However, after 24 hours, it was known that panels made of PMRC-3 also showed significant improvement.

Panels made of PMRC-1 showed some improvement in adhesion beyond the initial 5.5 minutes open time, but not a complete core failure. Failure mode was improved after 24 hours by PMRC-3 as the reactive diluent. In fact, up to 7 minutes of observed core failures were observed. The same effect was seen with the PMRC-1 reactive diluent and observed with the PMRC-0 reactive diluent.

In addition to determining the maximum action time, the thermal stability of the panels was tested. The condition of adding 100% reactive liquid hydrocuring composition to Mor-Melt ^™ R-5022 is to ensure that the hot melt adhesive is stable under the temperature on the roll.

Viscosity versus time was measured using a Brookfield Thermacell ^™ viscometer and the viscosity was monitored over 6 hours at 260 ° F. The results are summarized in Table 1.

Strength vs. Time Plywood-Plywood @ 12 g / ft ² Flatwise Tensile Strength (psi) Minutes Mor-Melt R-5022 ^TM Melt R-5022 + ^TM-Mor 9% PMRC-1 Melt R-5022 + ^TM-Mor 9% PMRC-2 One 1.4 1.7 0.9 2 5.6 5 3 3 12.9 11 4.4 4 17 13 7 5 19.1 13.5 9.5 6 24 17.2 18.2 7 26.4 18 14.5 8 10 36.9 24 18.9 11 39 20.6 26 12 42 28 36.5 15 31.3 31.5

When Mor-Melt R-5022 ^TM can be a reactive composition on the addition of PMRC-1 and PMRC-2 exhibited good or better thermal stability when used in bonded structural panels as compared to Mor-Melt R-5022 control ^TM. Following this significant improvement in the open time of the reactive hot melt by adding only 5% of the liquid water reactive composition, the effect was observed by increasing the percentage of diluent.

PMRC-1 (9 wt.%) Was added to Mor-Melt ^™ R-5022 and the laminate was configured as before. Open time, measured by core failure, increased significantly to 8 minutes.

PMRC-2 (9 wt.%) Was also added to Mor-Melt ^™ R-5022. Sample SIPS structures were prepared at open times of 3, 4, 5, 6, 6.5, 7, 7.5, 8, and 8.5 minutes. The obtained panel was cut in half lengthwise. Half were tested destructively at 1 hour from lamination. Test results showed EPS core failures only up to 5 minutes of action time. At a working time of 6 minutes, slight adhesive failure was observed for OSB.

PMRC-3 (9 wt.%) Was also added to Mor-Melt ^™ R-5022. PMRC-3 does not run like PMRC-1. No consistent core failure of 5 minutes or more is observed in the 1 hour mark, even core failures up to 8 minutes after 24 hours. Initially, at 5 wt% PMRC-3, core failure was observed up to 4.5 minutes. By increasing the diluent level to 8% by weight, operating times of 0.5 and 1.0 minutes are obtained.

The strength development of the bonded laminate using Mor-Melt ^™ R-5022 as a control and using reactive diluents was also evaluated. The results are summarized in Table 2.

Strength vs. Time Plywood-Plywood @ 12 g / ft ² Flatwise Tensile Strength (psi) Minutes Mor-Melt R-5022 ^TM Melt R-5022 + ^TM-Mor 9% PMRC-1 Melt R-5022 + ^TM-Mor 9% PMRC-3 One 1.4 1.7 0.9 2 5.6 5 3 3 12.9 11 4.4 4 17 13 7 5 19.1 13.5 9.5

Initial strength development results suggest that within the first 5 minutes, Mor-Melt ^™ R-5022 and PMRC-1 as reactive diluents actually occur faster than Mor-Melt ^™ R-5022 and PMRC-3 as reactive diluents. From this data, PMRC-1 as a reactive diluent has no side effects on strength generation within minutes of the first couple, compared with PMRC-3 side effects. Strength within the first minutes of a couple # 1 and tearing increase I quickly than is necessary density EPS core, on the other hand there is increased beyond 8 psi level for Mor-Melt ^TM R-5022 and PMRC-3 exceed 4 minutes There is a need.

The high temperature creep conditions required for ICC AC 05 certification were evaluated for Mor-Melt ^™ R-5022 and water reactive compositions. Aluminum Firs creep specimens were constructed using Mor-Melt R-5022 at 12 g / ft ² with 5% PMRC-1. The data is summarized in Table 3.

Creep testing for ^{Mor-Melt TM R-5022 +} 5% PMRC-1 Creep (inch) time One 2 3 4 0 hours 0 0 0 0 One 0 2 One 0 2 2 3 One One 3 2 3 One One 4 2 4 2 One 5 2 4 2 One 6 2 4 2 One 7 2 4 2 One 8 2 4 2 2 1 day AM 2 4 2 2 1 day PM 2 4 2 2 2 days AM 2 4 2 2 2 days PM 2 4 2 2 3 days AM 2 4 2 2 3 day PM 2 4 2 2 4 days AM 2 4 2 2 4 days PM 2 4 2 2 5 days AM 2 4 2 2 5 days PM 2 4 2 2 6 days AM 2 4 2 2 6 days PM 2 4 2 2 7 days AM 2 4 2 2 7 days PM 2 4 2 2

The condition of AC 05 section 8.6.3 is that creep does not exceed 0.002 "(2 mil) on any one specimen within the first hour and does not exceed an average of 0.005" (5 mil) over the test period. Creep values for Mor-Melt ^™ R-5022 and PMRC-1 are good within these conditions, indicating that the water reactive composition has no side effects on creep.

Claims (7)

(a) reactive hot melt adhesives; And (b) (i) one or more polymers having a weight average molecular weight of 2000 to 4000;     (ii) one or more multifunctional polyols; And     (iii) Polymeric reactive diluents containing at least one polyisocyanate, wherein the ratio of isocyanate groups to hydroxyl groups (NCO / OH) is from 4.0 to 11.0 and the amount of free isocyanate groups is greater than 7.5% by weight, based on the total amount of the composition. Adhesive composition comprising a. The method of claim 1, wherein the reactive hot melt adhesive comprises (a) at least one polymer having a weight average molecular weight of 30,000 to 100,000; (b) one or more multifunctional polyols; (c) at least one organic compound having at least two hydroxy groups; And (d) at least one polyisocyanate. (a) one or more polymers having a weight average molecular weight of 2000 to 4000; (b) one or more multifunctional polyols; And (c) Polymeric reactive diluents comprising at least one polyisocyanate, wherein the ratio of isocyanate groups to hydroxyl groups (NCO / OH) is between 4.0 and 11.0 and the amount of free isocyanate groups is greater than 7.5% by weight, based on the total amount of the composition. . An adhesive composition further comprising an isocyanate-containing reactive hot melt composition in the polymer reactive diluent according to claim 3. (a) reactive hot melt adhesives; And (b) (i) one or more polymers having a weight average molecular weight of 2000 to 4000;     (ii) one or more multifunctional polyols; And     (iii) Polymeric reactive diluents containing at least one polyisocyanate, wherein the ratio of isocyanate groups to hydroxyl groups (NCO / OH) is from 4.0 to 11.0 and the amount of free isocyanate groups is greater than 7.5% by weight, based on the total amount of the composition. Method of extending the action time of the reactive hot melt comprising the step of mixing. (a) reactive hot melt adhesives; And     (i) one or more polymers having a weight average molecular weight of 2000 to 4000;     (ii) one or more multifunctional polyols; And     (iii) Polymeric reactive diluents containing at least one polyisocyanate, wherein the ratio of isocyanate groups to hydroxyl groups (NCO / OH) is from 4.0 to 11.0 and the amount of free isocyanate groups is greater than 7.5% by weight, based on the total amount of the composition. Mixing; (b) heat the reactive hot melt adhesive; (c) applying a hot melt adhesive to the first substrate in the presence of moisture; (d) contacting the applied hot melt adhesive with at least one second substrate; (e) cooling the bonded hot melt adhesive. The method of claim 6 wherein the reactive hot melt (i) one or more polymers having a weight average molecular weight of 30,000 to 100,000; (ii) one or more multifunctional polyols; And (iii) the ratio of isocyanate groups to hydroxyl groups (NCO / OH) is from 4.0 to 11.0 and the amount of free isocyanate groups comprises at least one polyisocyanate, based on the total amount of the composition, greater than 7.5% by weight. The adhesion method of the base material.