• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    these are two-component solvent-free polyurethane adhesive compositions. in some embodiments, the solvent-free adhesive composition includes an isocyanate component that includes an isocyanate. the solvent-free adhesive composition further includes an isocyanate-reactive component which includes a highly reactive amine-initiated polyol comprising two or more primary hydroxyl groups and a backbone incorporating tertiary amines. the isocyanate-reactive component additionally includes a phosphate ester polyol. the isocyanate-reactive component may additionally include one or more non-amine-initiated polyols. methods for forming a laminate structure are also disclosed, which comprise uniformly applying an isocyanate component to a first substrate, uniformly applying an isocyanate-reactive component to a second substrate, placing the first and second substrates together, thus, if mix and react the isocyanate component and the isocyanate reactive component to form an adhesive between the first and second substrates, and cure the adhesive to bond the first and second substrates. further, in addition, laminates comprising the adhesive compositions are disclosed.
    公开号:BR112019015345A2
    申请号:R112019015345-4
    申请日:2017-11-15
    公开日:2020-03-10
    发明作者:Wu Jie；Xie Rui；Sehanobish Kalyan
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    “ADHESIVE COMPOSITIONS WITHOUT TWO COMPONENT SOLVENTS”
    REFERENCE TO RELATED APPLICATIONS [0001] This application claims the benefit of Provisional Application No. U.S. 62 / 451,304, filed on January 27, 2017.
    REVELATION FIELD [0002] The present disclosure relates to solvent-free adhesive compositions. More particularly, the disclosure relates to two-component solvent-free polyurethane adhesive compositions for use in laminated structures. The disclosed adhesive compositions comprise amine-initiated polyols and phosphate ester polyols that provide laminated structures that have an improved conversion efficiency and that are suitable for use in high performance food packaging applications (for example, bag boiling applications ).
    [0003] In some embodiments, the adhesive compositions exhibit high reactivity and therefore are formulated to be applied to two substrates independently, which are then brought together to mix and react the adhesive composition. In particular, one component of the adhesive composition is configured to be applied uniformly to a surface of a first substrate and the other component of the adhesive composition is configured to be applied to a surface of a second substrate. The first and second substrates are subsequently brought together, thus mixing and reacting the two components to form an adhesive between the first and the second substrates. In this way, the adhesive can then be cured, thereby linking the first and second substrates.
    BACKGROUND OF THE REVELATION [0004] Adhesive compositions are useful for a wide variety of purposes. For example, adhesive compositions are used to bond substrates such as polyethylene, polypropylene, polyester, polyamide,
    Petition 870190080464, of 19/08/2019, p. 7/28
    2/22 metal, paper or cellophane to form composite films, that is, laminates. The use of adhesives in different end-use applications is generally known. For example, adhesives can be used in the manufacture of film / film and film / foil laminates used in the packaging industry, especially for food packaging. Adhesives used in laminating applications, or “laminating adhesives”, can generally be placed in three categories: solvent-based, water-based and solvent-free. The performance of an adhesive varies by category and the application in which the adhesive is applied.
    [0005] Solvent-free laminating adhesives can be applied on up to 100% solids without any organic solvents or an aqueous carrier. Since no organic solvent or water has to be removed from the adhesive after application, these adhesives can be applied at high line speeds and are preferred in applications that require rapid adhesive application. Solvent-based and water-based laminating adhesives are limited by the rate at which the solvent or water can be effectively dried and removed from the laminate structure after applying the adhesive. For environmental, health and safety reasons, laminating adhesives are preferably aqueous or solvent free. However, solvent-free adhesives generally encounter problems such as short shelf life, low initial adhesion, slow bonding, low aromatic primary amine (“PAA”) and isocyanate decay (“NCO”), low adhesion to metal surfaces and low chemical and thermal resistance, particularly in high performance applications, such as boiling pouch packaging applications.
    [0006] Within the category of solvent-free laminating adhesives, there are many varieties. A particular variety includes two-component polyurethane laminating adhesives. Typically, a two component polyurethane laminating adhesive includes a first component comprising an isocyanate-containing prepolymer and a second component comprising a polyol. O
    Petition 870190080464, of 19/08/2019, p. 8/28
    3/22 prepolymer can be obtained by reacting the excess isocyanate with a polyether and / or polyester that contains two or more hydroxyl groups per molecule. The second component comprises a polyether and / or polyester initiated by two or more hydroxyl groups per molecule. The two components are combined in a predetermined ratio, or “premixed”, and then applied to a first substrate (“conveyor belt”). The first substrate is then joined with a second substrate to form a laminated structure.
    [0007] Additional layers of substrate can be added to the structure with additional layers of adhesive composition located between each successive substrate. The adhesive is then cured at room temperature or at elevated temperature, thereby bonding the substrates.
    [0008] The further processing of the laminate structure depends on the curing speed of the adhesive. The curing speed of the adhesive is indicated by the time it takes for the mechanical bond between the laminate substrates to become sufficient to allow for further processing and the laminate complies with applicable regulations (eg food contact regulations). Slow curing speed results in lower conversion efficiency. Pre-mixed, solvent-free two-component laminating adhesives, compared to traditional solvent-containing adhesives, exhibit poor initial bonding and slow curing speed. The general trend in the converting industry is towards faster curing laminating adhesives. Faster curing improves the operational efficiency of the converters. Specifically, the quick transfer of finished products from a warehouse increases production capacity and flexibility to handle last minute orders (for example, promotional campaigns by retailers). In order to increase operational efficiency, an adhesive composition with a much higher reactivity than existing adhesive compositions should be used to form laminates. However, this adhesive composition would provide a challenge for traditional adhesive application technologies.
    Petition 870190080464, of 19/08/2019, p. 9/28
    4/22 [0009] Therefore, two-component solvent-free polyurethane laminating adhesive compositions with improved bond strength and faster curing speeds are desirable.
    REVELATION SUMMARY [0010] Two-component solvent-free polyurethane adhesive compositions are disclosed. In some embodiments, the solvent-free adhesive composition includes an isocyanate component that includes at least one isocyanate. The solvent-free adhesive composition further includes an isocyanate-reactive component that includes a highly reactive amine-initiated polyol comprising two or more primary hydroxyl groups and a backbone that incorporates tertiary amines. The isocyanate-reactive component additionally includes a phosphate ester polyol. In some embodiments, the isocyanate can be selected from the group consisting of an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an aromatic polyisocyanate and combinations of two or more of the same. In some embodiments, the amine-initiated polyol may comprise a functionality of about 2 to about 12, a hydroxyl number of about 5 to about 1,830 and a molecular weight of about 200 to about 20,000. In some embodiments, the ester polyol phosphate is a product of the reaction of a polyol and a polyphosphoric acid. The isocyanate-reactive component may additionally include one or more non-amine-initiated polyols.
    [0011] The disclosed adhesive compositions exhibit fast cure rates and improved performance over existing two-component solvent-free adhesive compositions. As a result, the laminated structures comprising the adhesive compositions can be cut within just two hours after lamination and delivered within two days to a customer. Laminates comprising existing general purpose adhesive compositions typically require two to three days from rolling to cut and five to seven days for delivery. Consequently,
    Petition 870190080464, of 19/08/2019, p. 10/28
    5/22 the process efficiencies are greatly improved with the use of the disclosed adhesive compositions. In addition, the service life of the disclosed adhesive compositions is indefinite compared to a service life of twenty to thirty minutes for existing general purpose adhesives. This is because the service life of the disclosed adhesive compositions is completely independent of the curing process, as will be discussed below.
    [0012] Since the disclosed adhesive compositions are formulated to be more reactive and exhibit faster cure rates than existing adhesive compositions, they are not ideally suited for use with existing adhesive application devices. This is because the two components react very quickly, causing the adhesive to gel and be unsuitable for application on a substrate. For this reason, the disclosed adhesive compositions are formulated in such a way that the isocyanate and polyol components are applied separately on two different substrates, instead of being premixed and applied on a conveyor belt.
    [0013] In particular, the disclosed adhesive compositions are formulated in such a way that the isocyanate component can be uniformly applied to a surface of a first substrate and the isocyanate-reactive component can be applied to a surface of a second substrate. The surface of the first substrate is then brought into contact with the surface of the second substrate to mix and react the two components, thus forming a laminate. The adhesive composition is then curable.
    DETAILED DESCRIPTION OF THE REVELATION [0014] The two-component solvent-free adhesive composition, according to this disclosure, comprises an isocyanate component and an isocyanate reactive component.
    ISOCIANATE COMPONENT
    Petition 870190080464, of 19/08/2019, p. 11/28
    6/22 [0015] In some embodiments, the isocyanate component comprises an isocyanate. The isocyanate can be selected from the group consisting of a monomeric isocyanate, a polymeric isocyanate, a prepolymeric isocyanate and combinations of two or more of the same. As used herein, a prepolymeric isocyanate is the reaction product of reagents comprising an isocyanate and a polyol, for example, a polyester polyol. The "prepolymeric isocyanate" can be a polyisocyanate itself.
    [0016] In some embodiments, the isocyanate comprises a functionality of 1.5 to 10, or 1.8 to 5, or 2 to 3. As used in relation to the isocyanate component, "functionality" refers to the number of reaction sites with hydroxyl per molecule. Compounds that have polyisocyanate groups, such as the isocyanate prepolymer of the isocyanate component, can be characterized by the parameter "% NCO", which is the amount of polyisocyanate groups by weight based on the weight of the compound. The% NCO parameter is measured by the method of ASTM D 2572-97 (2010). In some embodiments, the isocyanate component has a% NCO of at least 3%, or at least 6%, or at least 10%. In some embodiments, the isocyanate component has a% NCO that does not exceed 25%, or 18%, or 14%.
    [0017] In some embodiments, the isocyanate component comprises a free monomer content of 0 to 50%, or 5 to 40%, or 10 to 30%. In some embodiments, the isocyanate component comprises a molecular weight of 200 to 3,000 g / mol, or 300 to 2,000 g / mol, or 500 to 1,000 g / mol. In some embodiments, the isocyanate component has viscosity at 25 ° C of 300 to 40,000 mPa-s, or 500 to 20,000 mPa-s, or 1,000 to 10,000 mPa-s, as measured by the ASTM D2196 method.
    [0018] In some embodiments, the isocyanate of the isocyanate component can be selected from the group consisting of an aliphatic polyisocyanate, a cycloaliphatic polyisocyanate, an aromatic polyisocyanate and combinations of two or more of the same. A “polyisocyanate
    Petition 870190080464, of 19/08/2019, p. 12/28
    7/22 aromatic ”is an isocyanate that contains one or more aromatic rings. An “aliphatic polyisocyanate” does not contain aromatic rings. A “cycloaliphatic polyisocyanate” is a subset of aliphatic polyisocyanates, in which the chemical chain is ring-structured.
    [0019] Examples of aromatic isocyanates suitable for use according to the disclosure include, but are not limited to, hexamethylene diisocyanate ("HDI") isomers, isophorene diisocyanate ("IRDI") isomers, di isomers -xylene isocyanate (“XDI”), isomers of methylenediphenyl diisocyanate (“MDI”), such as 4,4-MDI, 2,2-MDI and 2,4-MDI, isomers of toluene diisocyanate (“TDI ”), Such as 2,4-TDI, 2,6-TDI, naphthalene-diisocyanate isomers (“ NDI ”), such as 1,5-NDI, norbornane diisocyanate isomers (“ NBDI ”), isomers tetramethylxylene diisocyanate (“TMXDI”) and combinations of two or more of them. Preferred are MDI isomers, particularly a mixture of 4,4-MDI and 2,4-MDI (i.e., liquid MDI) or
    4,4-MDI (i.e., solid MDI).
    [0020] In some embodiments, the amount of the polyisocyanate in the isocyanate component is, by weight, based on the weight of the isocyanate component, at least 40% by weight, or at least 70% by weight, or at least 90 % by weight. In some embodiments, the amount of isocyanate in the isocyanate composition, by weight, based on the weight of the isocyanate component, must not exceed 100% by weight, or must not exceed 95% by weight, or must not exceed 90% by weight . In some embodiments, the amount of isocyanate in the isocyanate component is, by weight, based on the weight of the isocyanate component, from 40 to 100% by weight.
    [0021] The isocyanate component can further comprise other constituents commonly known to those skilled in the art.
    REACTION COMPONENT WITH ISOCIANATE [0022] The solvent-free adhesive composition
    Petition 870190080464, of 19/08/2019, p. 13/28
    8/22 further comprises an isocyanate-reactive component comprising a highly reactive amine-initiated polyol. In some embodiments, the amine-initiated polyol comprises primary hydroxyl groups and a backbone that incorporates at least one tertiary amine. In some embodiments, the isocyanate-reactive component may also comprise another type of polyol, which is a polyol not initiated by amine. For example, the isocyanate-reactive component may comprise at least one of the elements selected from the group consisting of polyester polyol, a polyether polyol, a polycarbonate polyol, a polyacrylate polyol, a polycaprolactone polyol, a polyolefin polyol, a natural oil polyol and combinations of two or more of them. Each type of polyol can include a type of polyol. Alternatively, each type of polyol can include mixtures of different types of polyols. In some embodiments, one type of polyol may be a type of polyol, while the other type of polyol may be a mixture of different species of polyols.
    [0023] In some embodiments, the amine-initiated polyol comprises primary hydroxyl groups and a backbone that incorporates at least one tertiary amine. In some embodiments, the amine-initiated polyol has the chemical structure of I:
    í I
    N
    HOX x ... OH where R 1 , R 2 and R 3 are each independently a linear or branched alkyl group. For example, each can be, independently, C 1 -C linear or branched alkyl group. In some embodiments, the amine-initiated polyol comprises tertiary amines and secondary amines.
    [0024] In some embodiments, the amine-initiated polyol comprises a functionality of 2 to 12, or 3 to 10, or 4 to 8.
    Petition 870190080464, of 19/08/2019, p. 14/28
    9/22
    As used in relation to the isocyanate reactive component, “functionality” refers to the number of isocyanate reaction sites per molecule. In some embodiments, the amine-initiated polyol comprises a hydroxyl number from 5 to 1,830, or from 20 to 100, or from 31 to 40. As used in relation to the isocyanate reactive component, “hydroxyl number” is a measure of amount of reactive hydroxyl groups available for reaction. This number is determined in a wet analytical method and is reported as the number of milligrams of potassium hydroxide equivalent to the hydroxyl groups found in one gram of the sample. The most used methods for determining the hydroxyl number are described in ASTM D 4274 D. In some embodiments, the amine-initiated polyol comprises a viscosity at 25 ° C of 500 to 30,000 mPa-s, or 1,000 to 15,000 mPa-s , or from 1,500 to 10,000 mPa-s.
    [0025] Amine-initiated polyols suitable for use according to this disclosure are made by alkoxylation of one or more amine initiators with one or more alkylene oxides.
    [0026] In some embodiments, the amount of polyol initiated by amine in the isocyanate-reactive component is, by weight, based on the weight of the isocyanate-reactive component, at least 0.2% by weight, or at least 1% by weight, or at least 5% by weight. In some embodiments, the amount of the amine-initiated polyol in the isocyanate-reactive component, by weight, based on the weight of the isocyanate-reactive component, must not exceed 30% by weight, or must not exceed 15% by weight, or must not exceed exceed 10% by weight. In some embodiments, the amount of amine-initiated polyol in the isocyanate-reactive component is, by weight, based on the weight of the isocyanate-reactive component, from 0.2 to 30% by weight.
    [0027] In some embodiments, a polyol not initiated by amine can optionally be included in the isocyanate reactive component. Examples of suitable non-amine initiator polyols include, but are not limited to, a polyester polyol, a polyether polyol, a polyol of polyether
    Petition 870190080464, of 19/08/2019, p. 15/28
    10/22 polycarbonate, a polyacrylate polyol, a polyrapolactone polyol, a polyolefin polyol, a natural oil polyol and combinations of two or more thereof. In some embodiments, the polyol not initiated by amine has a viscosity at 25 ° C of 30 to 40,000 mPa-s, or 50 to 30,000 mPa-s, or 70 to 20,000 mPa-s, as measured by the ASTM D2196 method. In some embodiments, the polyol not initiated by amine has a viscosity of 100 to 10,000 mPa-s at 25 ° C, as measured by the ASTM D2196 method. In some embodiments, the non-amine-initiated polyol is solid at 25 ° C.
    [0028] In some embodiments, the amount of the non-amine-initiated polyol in the isocyanate-reactive component is at least 0% by weight, or at least 5% by weight, or at least 10% by weight. In some embodiments, the amount of the polyol not initiated by amine in the isocyanate-reactive component must not exceed 98% by weight, or must not exceed 90% by weight, or must not exceed 70% by weight.
    [0029] In some embodiments, the isocyanate-reactive component additionally comprises a phosphate ester polyol. In some embodiments, the phosphate ester polyol is produced from a tri-functional propylene glycol, a polyphosphoric acid and a polyisocyanate. Commercially available examples of the tri-functional propylene glycol suitable for use in accordance with this disclosure include products marketed under the trade names VORANOL ™ CP-450, VORANOL ™ CP-260, VORANOL ™ CP-755 and VORANOL ™ CP-1055, each available together to The Dow Chemical Company.
    [0030] In some embodiments, the phosphate ester polyol has a phosphoric acid content of less than 4 weight percent based on the weight of the phosphate ester polyol, or a phosphoric acid content of 0 to 3 percent weight in weight based on the weight of the phosphate ester polyol or a phosphoric acid content of 1.5 to 2.5 weight percent based on the weight of the phosphate ester polyol. In some embodiments, the phosphate ester polyol has a viscosity of less than 40 Pa-s (40,000 cps) at 25 ° C, or less than 30 Pa-s
    Petition 870190080464, of 19/08/2019, p. 16/28
    11/22 (30,000 cps) at 25 ° C, as measured by the ASTM D2196 method. In some embodiments, the phosphate ester polyol has an equivalent hydroxyl weight of less than 330 g / mol. In some embodiments, the phosphate ester polyol is from 0 to 100 weight percent, based on the weight of the phosphate ester polyol, of a trifunctional polyether polyol that has an equivalent weight of less than 2,000 g / mol.
    [0031] The mixing ratio between the isocyanate component and the isocyanate reactive component, by weight, is controlled by adjusting the coating weight of each component to its respective substrate. In some embodiments, the mixing ratio between the isocyanate component and the isocyanate-reactive component in the final adhesive composition can be 100: 100, or 100: 90, or 100: 80. The disclosed adhesive compositions are more compliant than traditional adhesives and can accommodate some coating weight error (for example, up to about 10% coating weight error).
    [0032] In some embodiments, one or more additives can optionally be included in the adhesive composition. Examples of such additives include, but are not limited to, tackifying agents, plasticizers, rheology modifiers, adhesion promoters, antioxidants, fillers, dyes, surfactants, antifoaming agents, wetting agents, leveling agents, solvents and combinations of two or more of the same .
    The isocyanate-reactive component may additionally comprise other constituents known to those skilled in the art, for example, additional polyols and isocyanates etc.
    LAMINATE FORMATION [0034] It is contemplated that the isocyanate component and the isocyanate-reactive component of the disclosed solvent-free adhesive composition are formulated separately and stored until it is desirable to form a laminate structure. Preferably, the
    Petition 870190080464, of 19/08/2019, p. 17/28
    12/22 isocyanate and the isocyanate reactive component are in a liquid state at 25 ° C. Even if the components are solid at 25 ° C, it is acceptable to heat the components as needed to put them in a liquid state.
    [0035] A laminate comprising the disclosed adhesive compositions can be formed by applying the isocyanate and isocyanate reaction components of the adhesive composition separately to two different substrates, such as two films. As used herein, a "film" is any structure that is 0.5 mm or less in one dimension and has 1 cm or more in both of the other two dimensions. A "polymeric film" is a film that is produced from a polymer or a mixture of polymers. The composition of a polymer film is typically 80 weight percent or more than one or more polymers.
    [0036] For example, a layer of the isocyanate component is applied to a surface of a first substrate. Preferably, the layer thickness of the isocyanate component on the first substrate is 0.5 to 2.5 µm. A layer of the isocyanate-reactive component is applied to a surface of a second substrate. Preferably, the layer thickness of the isocyanate-reactive component on the second substrate is 0.5 to 2.5 µm. By controlling the thickness of the layers applied to each substrate, the component ratio can be controlled.
    [0037] The surfaces of the first and second substrates then pass through a device to apply external pressure to the first and second substrates, such as the pinch roller. The joining of the isocyanate component and the reactive component to isocyanate forms a layer of curable adhesive mixture. When the surfaces of the first and second substrates are joined, the thickness of the curable adhesive mixture layer is 1 to 5 pm. The isocyanate component and the isocyanate reactive component begin to mix and react when the first and second substrates are joined and the components come into contact with each other. This marks the beginning of the healing process.
    Petition 870190080464, of 19/08/2019, p. 18/28
    13/22 [0038] Additional mixing and reaction is achieved as the first and second substrates pass through several other rollers and, finally, to a rewind roll. Additional mixing and reaction occurs when the first and second substrates pass through rollers because the substrates each take longer or shorter paths than the other substrate through each roll. In this way, the two substrates move in relation to each other, mixing the components in the respective substrates. The arrangements of these rollers in an application apparatus are generally known in the art. The curable mixture is then cured or allowed to cure.
    [0039] Suitable substrates in the laminate structure include films such as paper, woven and non-woven cloth, metal foil, polymeric films and polymeric films coated with metal. Optionally, some films have a surface on which an image is printed with ink that can be in contact with the adhesive composition. The substrates are stratified to form a laminated structure, and an adhesive composition according to this disclosure causes one or more of the substrates to adhere to each other.
    [0040] Therefore, the inclusion of an amine-initiated polyol revealed in the isocyanate-reactive component of the adhesive composition provides an adhesive composition with a significantly faster reactivity profile. Such adhesive compositions are particularly suitable for lamination according to the methods disclosed herein.
    EXAMPLES OF THE REVELATION [0041] The present disclosure will now be explained in more detail by describing examples that illustrate the disclosed adhesive compositions and existing adhesive compositions (collectively, "the Examples"). However, the scope of the present disclosure is obviously not limited to the Examples.
    Petition 870190080535, of 19/08/2019, p. 11/20
    14/22 [0042] The isocyanate reaction components of the Examples are prepared using the raw materials identified in
    Table 1 below:
    TABLE 1: RAW MATERIALS
    Materials Composition Provider % NCO are not hydroxyl or MOR-FREE ™ L-PLUS Aromatic polyisocyanate The Dow Chemical Company 12.2% POLY-ISOCIANATE A MDI polyester prepolymer The Dow Chemical Company 13.5% SPECFLEX ™ ACTIV2306 Polyol initiated by amine The Dow Chemical Company 37 CR121-14 Hydroxyl-terminated components The Dow Chemical Company 147.7 ISONATE ™ 125M Solid methylenediphenyl diisocyanate The Dow Chemical Company 33.5% VORANOL ™ CP450 Hydroxyl-terminated components The Dow Chemical Company 383 VORANOL ™ CP755 Hydroxyl-terminated components The Dow Chemical Company 237.5 MOR-FREE ™ 88-138 Hydroxyl-terminated components The Dow Chemical Company 290.8
    [0043] The Examples are prepared according to the formulations, shown by component on a weight percentage basis and listed in Table 2 below:
    TABLE 2: OH COMPONENT SAMPLE FORMULATIONS
    Ingredient Formulation (base% by weight) CE1 CE2 CE3 IE1 IE2 MOR-FREE ™ L Plus 1 52.6 POLY-ISOCIANATE A50.5 49.5 52.2 52.6
    Petition 870190080535, of 19/08/2019, p. 12/20
    15/22
    CR 121-14 47.4 CR2E49.5 CR2C 50.5 CR2D 47.8CR2F 47.4
    ILLUSTRATIVE EXAMPLE 1 (ΊΕ1 ”)
    TABLE 3: CR2D COMPOSITION
    Materials Percentage (% by weight) VORANOL ™ CP450 6.32 VORANOL ™ CP755 56.92 ISONATE ™ 125M 9.76 SPECFLEX ™ ACTIV 2306 15 MOR-FREE ™ 88-138 12
    [0044] VORANOL ™ CP 450, VORANOL ™ CP755 and ISONATE ™ 125M are subjected to reaction in a reactor for 2 hours at 80 ° C under nitrogen purge to form OH-terminated polyether based polyurethane. The synthesized polyether-based polyurethane is mixed with SPECFLEX ™ ACTIV 2306 and MOR-FREE ™ 88-138 to form Coreactant 2D ("CR2D"). Detailed information on the composition of CR2D is listed in Table 3.
    [0045] A polyurethane adhesive comprising about 52.2% by weight of POLYESOCIANATE A and 47.8% by weight of 2D CR is used to bond a sheet / polyethylene (“PE”) structure and a polyethylene terephthalate (“PET”) / PE structure. The laminates produced are cured at 25 ° C and 50% relative humidity. The laminated samples produced are cut into strips 15 mm wide and their resistance to the T-film bond is assessed on a Thwing-Albert skin tester at 10.16 centimeters / min (4 inches / min). If one of the substrates extends or breaks, the maximum force or force at break will be recorded. The mean force
    Petition 870190080535, of 19/08/2019, p. 13/20
    16/22 during the test is recorded if the two substrates are separated. The bond strength values are the average of at least three sample strips.
    [0046] The bag-like boil test is conducted for foil / PE laminates after the adhesive is fully cured. The bags for the bag boil test have an internal size of 10.16 centimeters by 15.24 centimeters (4 inches by 6 inches) and are filled with 100 ml of 1: 1: 1 sauce (that is, equal parts vinegar, corn oil and ketchup). Subsequently, the bags are placed in boiling water for 30 minutes. At the end, at least three strips 25.4 mm wide are cut from the area in contact with boiling water and the bond strength of each strip is measured with the Thwing-Albert skin tester at 25.4 cm / min (10 in / min).
    ILLUSTRATIVE EXAMPLE 2 (“IE2”)
    TABLE 4: CR2F COMPOSITION
    Materials Percentage (% by weight) VORANOL ™ CP755 52.7 VORANOL ™ CP450 9 ISONATE ™ 125M 9.3 SPECFLEX ™ ACTIV 2306 17 MOR-FREE ™ 88-138 12
    [0047] VORANOL ™ CP 755 and ISONATE ™ 125M are reacted in a reactor for 2 hours at 80 ° C under nitrogen purge to form OH-terminated polyether based polyurethane. The polyether-based synthetic polyurethane is mixed with VORANOL ™ CP450, SPECFLEX ™ ACTIV 2306 and MOR-FREE ™ 88-138 to form the CR2F. Detailed information on the composition of the CR 2F is listed in Table 4.
    [0048] A polyurethane adhesive is used which comprises about 52.6% by weight of POLYESOCIANATE A and 47.4% by weight.
    Petition 870190080535, of 19/08/2019, p. 14/20
    17/22 weight of CR2F to connect a sheet / PE structure and a PET / PE structure. The laminates produced are cured at 25 ° C and 50% relative humidity. The laminated samples are cut into strips 15 mm wide and their resistance to the T-film bond is evaluated on a Thwing-Albert skin tester at 10.16 centimeters / min (4 inches / min). If one of the substrates extends or breaks, the maximum force or force at break will be recorded. The average strength during the test is recorded if the two substrates are separated. The bond strength values are the average of at least three sample strips.
    [0049] The bag boil test is performed for the foil laminate / PE after the adhesive is fully cured. The bags for the bag boil test have an internal size of 10.16 centimeters by 15.24 centimeters (4 inches by 6 inches) and are filled with 100 ml of 1: 1: 1 sauce (that is, equal parts vinegar, corn oil and ketchup). Subsequently, the bags are placed in boiling water for 30 minutes. At the end, at least three strips 25.4 mm wide are cut from the area in contact with boiling water and the bond strength of each strip is measured with the Thwing-Albert skin tester at 25.4 cm / min (10 in / min).
    COMPARATIVE EXAMPLE 1 (“CE1”) [0050] A polyurethane adhesive comprising about 52.6% by weight of MOR-FREE ™ L-PLUS and 47.4% by weight of CR 121-14 is used to bond a sheet / PE structure and a PET / PE structure. The laminates produced are cured at 25 ° C and 50% relative humidity. The laminated samples are cut into strips 15 mm wide and their resistance to the T-film bond is evaluated on a Thwing-Albert skin tester at 10.16 centimeters / min (4 inches / min). If one of the substrates extends or breaks, the maximum force or force at break will be recorded. The average strength during the test is recorded if the two substrates are
    Petition 870190080535, of 19/08/2019, p. 15/20
    18/22 separated. The bond strength values are the average of at least three sample strips.
    [0051] The bag boil test is performed for the foil / PE laminate after the adhesive is fully cured. The bags for the bag boil test have an internal size of 10.16 centimeters by 15.24 centimeters (4 inches by 6 inches) and are filled with 100 ml of 1: 1: 1 sauce (that is, equal parts vinegar, corn oil and ketchup). Subsequently, the bags are placed in boiling water for 30 minutes. At the end, at least three strips 25.4 mm wide are cut from the area in contact with boiling water and the bond strength of each strip is measured with the Thwing-Albert skin tester at 25.4 cm / min (10 in / min).
    COMPARATIVE EXAMPLE 2 TABLE 5: CR2E COMPOSITION
    Materials Percentage (% by weight) VORANOL ™ CP450 7.71 VORANOL ™ CP755 69.39 ISONATE ™ 125M 11.90 SPECFLEX ™ ACTIV 2306 11
    [0052] VORANOL ™ CP 450, VORANOL ™ CP755 and ISONATE ™ 125M are subjected to reaction in a reactor for 2 hours at 80 ° C under nitrogen purge to form polyurethane based on OH-terminated polyether. The polyether-based synthetic polyurethane is mixed with SPECFLEX ™ ACTIV 2306 to form CR2E. Detailed information on the composition of CR2E is listed in Table 5.
    [0053] A polyurethane adhesive comprising about 50.5% by weight of POLYESOCIANATE A and 49.5% by weight of CR2E is used to bond a sheet metal / PE structure and a structure of
    Petition 870190080535, of 19/08/2019, p. 16/20
    19/22
    PET / PE. The laminates produced are cured at 25 ° C and 50% relative humidity. The laminated samples are cut into strips 15 mm wide and their resistance to the T-film bond is assessed on the Thwing-Albert skin test equipment at 25.4 centimeters / min (4 inches / min). If one of the substrates is stretched or torn, the maximum force or force at break is recorded. The average strength during the test is recorded if the two substrates are separated. The bond strength values are the average of at least three sample strips.
    [0054] The bag-like boil test is performed for the foil / PE laminate after the adhesive is fully cured. The bags for the bag boil test have an internal size of 10.16 centimeters by 15.24 centimeters (4 inches by 6 inches) and are filled with 100 ml of 1: 1: 1 sauce (that is, equal parts vinegar, corn oil and ketchup). Subsequently, they are placed in boiling water for 30 minutes. At the end, at least three strips 25.4 mm wide are cut from the area in contact with boiling water and the bond strength of each strip is measured with the Thwing-Albert skin tester at 25.4 cm / min (10 in / min).
    COMPARATIVE EXAMPLE 3 TABLE 6: CR2C COMPOSITION
    Materials Percentage (% by weight) VORANOL ™ CP450 7.36 VORANOL ™ CP755 66.27 ISONATE ™ 125M 11.36 SPECFLEX ™ ACTIV 2306 15
    [0055] VORANOL ™ CP 450, VORANOL ™ CP755 and ISONATE ™ 125M are subjected to reaction in a reactor for 2 hours at 80 ° C under nitrogen purge to form polyether based polyurethane finished in
    Petition 870190080535, of 19/08/2019, p. 17/20
    20/22
    OH. The synthetic polyether based polyurethane is mixed with SPECFLEX ™
    ACTIV 2306 to form CR2C. Detailed information on the composition of
    CR2C are listed in Table 6.
    [0056] A polyurethane adhesive comprising about 49.5% by weight of POLYESOCIANATE A and 50.5% by weight of CR2C is used to bond a sheet / PE structure and a PET / PE structure . The laminates produced are cured at 25 ° C and 50% relative humidity. The laminated samples are cut into strips 15 mm wide and their resistance to the T-film bond is assessed on the Thwing-Albert skin test equipment at 25.4 centimeters / min (4 inches / min). If one of the substrates is stretched or torn, the maximum force or force at break is recorded. The average strength during the test is recorded if the two substrates are separated. The bond strength values are the average of at least three sample strips.
    [0057] The bag boil test is performed for the foil / PE laminate after the adhesive is fully cured. The bags for the bag boil test have an internal size of 10.16 centimeters by 15.24 centimeters (4 inches by 6 inches) and are filled with 100 ml of 1: 1: 1 sauce (that is, equal parts vinegar, corn oil and ketchup). Subsequently, they are placed in boiling water for 30 minutes. At the end, at least three strips 25.4 mm wide are cut from the area in contact with boiling water and the bond strength of each strip is measured with the Thwing-Albert skin tester at 25.4 cm / min (10 in / min).
    PERFORMANCE RESULTS
    TABLE 7: DATA OF RESISTANCE TO THE CONNECTION OF PET / PE LAMINATES
    Sticker Bond strength (N / 15 mm) * 0.5 hours 1 hour 1.5 hour 2 hours 4 hours 24 hours
    Petition 870190080535, of 19/08/2019, p. 18/20
    21/22
    CE1 0.09 AT 0.39 AT 0.69 AT 2.08 AT 2.71 THE 8.38 FT CE2 0.10 AT 0.16 AT 0.37 AT 0.81 AT 3.23 AT / FS 10.46 FT CE3 0.10 AT 0.27 AT 1.07 AT 2.50 THE 6.97 FS 7.18 FS E1 0.10 AT 0.20 AT 0.17 AT 1.02 AT 3.82 AT / FS 9.94 FT E2 0.05 AT 0.16 AT 0.68 AT 0.76 AT 3.34 THE 8.42 FS * AS: Adhesive separation; AT: Ί Frans ad transfer esiva; FS: Film stretching;
    FT: Film break
    TABLE 8: DATA OF RESISTANCE TO THE CONNECTION OF METAL SHEET LAMINATES / PE
    Sticker Bond strength (N / 15 mm) * 0.5 hours 1 hour 1.5 hour 2 hours 4 hours 24 hours CE1 0.18 AT 0.84 AT 1.60 AT 2.10 THE 2.91 THE 2.50 THE CE2 0.18 AT 0.46 AT 0.94 AT 1.36 THE 2.79 THE 2.78 THE CE3 0.26 AT 0.84 AT 1.65 THE 1.97 THE 2.35 THE 2.04 THE E1 0.20 AT 0.35 AT 0.59 AT 1.38 THE 3.12 THE 4.55 THE E2 0.09 AT 0.41 AT 1.38 AT 1.90 THE 3.06 THE 2.89 THE
    * AS: Adhesive separation; AT: Adhesive transfer
    TABLE 9: DATA OF RESISTANCE TO THE CONNECTION OF METAL SHEET LAMINATES / PE
    Sticker Bond strength after bag-like boil test (g / in) * CE1 0 DL CE2 0 DL CE3 0 DL E1 383 ± 10 AT E2 386 ± 23 AT
    * AS: Adhesive separation; DL: Delamination [0058] Tables 7 and 8 illustrate that IE1 and IE2 have a
    Petition 870190080535, of 19/08/2019, p. 19/20
    22/22 ultra-fast development of cure and bond strength. For example, both ο IE1 and ο IE2 have bond strengths above 1 N / 15 mm after 2 hours of curing. IE1 and IE2 exhibit greater dry bond after 24 hours of curing compared to CE1 to CE3. After the 1: 1: 1 bag boil test, as shown in Table 9, the laminates from CE1 to CE3 are all delaminated. In contrast, IE1 and IE2 still have a bond strength of about 150.78 and 151.96 g / cm (383 and 386 g / inch), respectively, showing excellent temperature and chemical resistance.
    权利要求:
    Claims (15)
    [1]
    1. Two-component solvent-free adhesive composition characterized by the fact that it comprises:
    an isocyanate component that comprises an isocyanate; and an isocyanate-reactive component comprising:
    an amine-initiated polyol comprising two or more primary hydroxyl groups and a backbone incorporating tertiary amines; and a phosphate ester polyol.
    [2]
    2. Two-component solvent-free adhesive composition according to claim 1, characterized by the fact that the amine-initiated polyol comprises a function from 2 to 12, a hydroxyl number from 5 to 1,830 and a viscosity at 25 ° C from 500 to 30,000 mPa-s.
    [3]
    3. Two-component solvent-free adhesive composition according to claim 1, characterized by the fact that the amine-initiated polyol comprises from 0.5 to 30 percent by weight of the isocyanate-reactive component, based on the total weight of the reactive isocyanate component.
    [4]
    4. Two-component solvent-free adhesive composition according to claim 1, characterized by the fact that the polyol initiated by amine has structure I:
    N
    HO, z- ' ..... OH ίο ··· - where R 1 , R 2 , and R 3 are independently a linear or branched alkyl group.
    [5]
    5. Two solvent-free adhesive composition
    Petition 870190080535, of 19/08/2019, p. 7/20
    2/4 components according to claim 1, characterized by the fact that the polyol initiated by amine is a reaction product of an alkylene oxide and an amine.
    [6]
    6. Two-component solvent-free adhesive composition according to claim 5, characterized by the fact that the amine is selected from the group consisting of toluene diamine, methylamine, ethylenediamine, diethylene triamine, aniline, aminoethylethanolamine, bis3-aminopropylmethylamine , propylene diamine, tetra or hexamethyleneamine, triethanolamine, phenylenediamine and combinations of two or more of the same.
    [7]
    7. Two-component solvent-free adhesive composition according to claim 1, characterized by the fact that the phosphate ester polyol comprises from 0.2 to 30 weight percent of the isocyanate-reactive component, based on the total weight of the reactive isocyanate component.
    [8]
    8. Two-component solvent-free adhesive composition according to claim 1, characterized in that the phosphate ester polyol is a reaction product of a polyol and a polyphosphoric acid.
    [9]
    9. Two-component solvent-free adhesive composition according to claim 1, characterized by the fact that the phosphate ester polyol is produced from a trifunctional propylene glycol, a polyphosphoric acid and a polyisocyanate, the polyol being phosphate ester content has a phosphoric acid content of less than 3 weight percent based on the weight of the phosphate ester polyol, and a viscosity of less than 40 mPa-s (40,000 cps) at 25 ° C.
    [10]
    10. Two-component solvent-free adhesive composition according to claim 1, characterized in that it additionally comprises an adhesion promoter.
    [11]
    11. Two-component solvent-free adhesive composition according to claim 9, characterized by the fact that
    Petition 870190080535, of 19/08/2019, p. 8/20
    3/4 the adhesion promoter is a coupling agent selected from the group consisting of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent and combinations of two or more of the same.
    [12]
    12. Two-component solvent-free adhesive composition according to claim 9, characterized by the fact that the adhesion promoter is selected from the group consisting of a coupling agent, an epoxy resin, a phosphoric acid, a polyphosphoric acid, a phosphate ester and combinations of two or more of the same.
    [13]
    13. Two-component solvent-free adhesive composition according to claim 11, characterized in that the coupling agent is selected from the group consisting of a silane coupling agent, a titanate coupling agent, a aluminate coupling agent; epoxy resin, phosphoric acid, polyphosphoric acid.
    [14]
    14. Laminate structure characterized by the fact that it comprises the two-component solvent-free adhesive composition according to claim 1.
    [15]
    15. Method for forming a laminate structure characterized by the fact that it comprises:
    uniformly applying an isocyanate component to a first substrate, the isocyanate component comprising an isocyanate;
    uniformly apply an isocyanate-reactive component to a second substrate, the isocyanate-reactive component comprising:
    an amine-initiated polyol comprising primary hydroxyl groups and a backbone incorporating tertiary amines; and a phosphate ester polyol;
    put the first and second substrates together, this way
    Petition 870190080535, of 19/08/2019, p. 9/20
    4/4 way, the isocyanate component and the isocyanate reactive component are mixed and reacted to form an adhesive between the first and the second substrates; and curing the adhesive to bond the first and second substrates.
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    同族专利:
    公开号 | 公开日
    RU2019126525A|2021-02-24|
    JP2020505493A|2020-02-20|
    WO2018140116A1|2018-08-02|
    AR110896A1|2019-05-15|
    EP3574031A1|2019-12-04|
    MX2019008786A|2019-12-09|
    TW201827551A|2018-08-01|
    US20190390094A1|2019-12-26|
    RU2019126525A3|2021-02-25|
    CN110352206A|2019-10-18|
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    法律状态:
    2021-08-31| B06W| Patent application suspended after preliminary examination (for patents with searches from other patent authorities) [chapter 6.23 patent gazette]|
    2021-10-13| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    优先权:
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    US201762451304P| true| 2017-01-27|2017-01-27|
    USUS62/451,304|2017-01-27|
    PCT/US2017/061803|WO2018140116A1|2017-01-27|2017-11-15|Two-component solventless adhesive compositions|
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