CN117062888A - Multilayer composite with double layer pressure sensitive adhesive - Google Patents

Multilayer composite with double layer pressure sensitive adhesive Download PDF

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Publication number
CN117062888A
CN117062888A CN202280020575.2A CN202280020575A CN117062888A CN 117062888 A CN117062888 A CN 117062888A CN 202280020575 A CN202280020575 A CN 202280020575A CN 117062888 A CN117062888 A CN 117062888A
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adhesive
adhesive layer
multilayer composite
acrylate
layer
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S·D·托宾
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BASF SE
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BASF SE
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Priority claimed from PCT/US2022/019975 external-priority patent/WO2022192686A1/en
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Abstract

The present invention relates to a multilayer composite comprising a polymer film, a hot melt adhesive layer a, a hot melt adhesive layer B; and a release liner, wherein the hot melt adhesive layer a comprises a non-Ultraviolet (UV) curable pressure sensitive adhesive; wherein the hot melt adhesive layer B comprises an at least partially cured Ultraviolet (UV) curable pressure sensitive adhesive; wherein the hot melt adhesive layer a has a thickness of 25 μm to 250 μm, and wherein the hot melt adhesive layer B has a thickness of 50 μm to 250 μm. The invention also relates to a method for producing the composite material and to the use of the composite material as roofing material.

Description

Multilayer composite with double layer pressure sensitive adhesive
Technical Field
The present invention relates to a multilayer composite comprising a polymeric film, first and second adhesive layers, a second adhesive layer, and a release member.
Background
Multilayer composites, also known as multilayer films, peel-stick films or panels, are used in the construction industry to cover flat or low grade roofs. These membranes provide protection for the roof from environmental influences, in particular in the form of a water barrier. As known in the art, commercially available membranes include thermoset membranes such as those comprising cured EPDM (i.e., ethylene-propylene-diene terpolymer rubber), or thermoplastics such as TPO (i.e., thermoplastic olefins), PVC (i.e., polyvinyl chloride), and modified asphalt.
These films are typically delivered to a building site in a bundled roll, transferred to a roof, and then unrolled and positioned. The sheet is then affixed to the building structure by using different techniques such as mechanical fastening, ballasting and/or adhering the membrane to the roof. The roof substrate to which the membrane is secured may be one of a variety of materials, depending on installation site and structural considerations. For example, the surface may be concrete, metal, gypsum, plywood or a wood platform, it may comprise insulating or recycling board, and/or it may comprise an existing film.
In addition to securing the membrane to the roof (this attachment mode is primarily intended to prevent wind stripping), a separate membrane panel is positioned and abutted with the flashing and other accessories to achieve a waterproof barrier on the roof. Typically, the edges of adjoining panels are overlapping and these overlapping portions are adjoined to one another by a variety of methods depending on the film material and external conditions. One approach involves providing an adhesive or tape between the overlapping portions to create a watertight seal. Alternatively, if the films are thermoplastics, they may be heat sealed.
With respect to the former attachment mode involving securing the membrane to the roof, the use of an adhesive allows for the formation of a fully adhered roof system. In other words, a majority, if not all, of the membrane panels are secured to the roof substrate, as opposed to mechanical attachment methods that can only effect direct attachment at those locations where the mechanical fasteners actually secure the membrane.
When adhesively securing membranes to a roof, such as when forming a fully adhered system, several common methods are employed. The first is known as contact bonding, in which the technician coats the film and substrate with an adhesive and then fits the film onto the substrate while the adhesive is only partially cured. Because the volatile components of the adhesive (e.g., solvent) are flashed off prior to compounding, good early (green) bond strength is developed.
Another mode of attachment is through the use of an adhesive that is pre-applied to the bottom surface of the film. In other words, the adhesive is applied to the bottom surface of the film prior to shipping the film to the job site. To allow the film to be rolled up and shipped, a release film or member is applied to the surface of the adhesive. During installation of the membrane, the release member is removed, exposing the pressure sensitive adhesive, and the membrane can then be secured to the roof surface without the need to apply additional adhesive.
As known in the art, the pre-applied adhesive may be applied to the surface of the film in the form of a hot melt adhesive. For example, U.S. publication 2004/0191508, which teaches the use of pressure sensitive adhesive compositions comprising styrene-ethylene-butylene-styrene (SEBS), a tackifying endblock resin such as coumarone-indene resin, and a tackifying midblock resin such as a terpene resin. The disclosure also proposes other hot melt adhesives such as butyl-based adhesives, EPDM-based adhesives, acrylic adhesives, styrene-butadiene adhesives, polyisobutylene adhesives, and ethylene vinyl acetate adhesives.
Further, single layer UV curable acrylic hot melt adhesive coatings on EPDM films are disclosed, for example, in U.S. patent nos. 10,132,082, 10,519,663, 10,370,854 and U.S. publication nos. 2019-0316359.
However, these existing applications have inherent limitations. For example, there is a temperature window that limits the minimum temperature at which the peel-and-stick film can be installed on the roof surface. In addition, there are maximum temperature limitations on the roof surface that the adhesive can withstand while maintaining the integrity of the tamper evident. In the latter case, the adhesive strength provided by the pressure sensitive adhesive cannot be maintained when the surface temperature on the roof is close to the glass transition temperature of the adhesive. In addition, when the laminate is installed on a roof deck at a relatively high temperature and naturally cooled to ambient temperature at night, a large difference in thermal expansion-contraction coefficient and elasticity between the adhesive layer and the film may generate tunneling or wrinkling. Similarly, when the membrane and roof deck adhere to each other below freezing temperature, tunneling or wrinkling may occur as the temperature increases.
While UV cured pressure sensitive adhesives are also known, there are inherent limitations on how much radiant energy can be provided to a given adhesive layer. The greater the thickness of the layer, the greater the energy required. However, it is known that a large amount of radiation can cause non-uniformities in the layer.
As a result, peel-and-stick films have not gained wide acceptance in the industry. Furthermore, the use of peel-and-stick films is limited to use in conjunction with white films (e.g., white thermoplastic films) because the surface temperature of these films remains low when exposed to solar energy.
Thus, there is a need for a peel-and-stick film or multilayer composite that is insensitive to the limitations described above, is suitable for installation at any time without exhibiting channeling and tunneling, and is UV curable without causing non-uniformities in the adhesive layer.
Disclosure of Invention
The object of the present invention is to develop a multilayer composite comprising a polymer film, a first and a second adhesive layer and a release member, wherein one of the adhesive layers may comprise a UV curable adhesive layer which is not UV cured prior to combination with the second adhesive layer or latex emulsion adhesive.
The following are embodiments of the present invention:
embodiment 1 is a multilayer composite comprising:
a polymer film;
an adhesive layer A;
a hot melt adhesive layer B; and
the release liner is provided with a release liner,
wherein the adhesive layer a comprises an Ultraviolet (UV) curable pressure sensitive adhesive or an aqueous latex adhesive;
Wherein the hot melt adhesive layer B comprises an at least partially cured Ultraviolet (UV) curable pressure sensitive adhesive;
wherein the adhesive layer A has a thickness of 25 μm to 250 μm, and
wherein the hot melt adhesive layer B has a thickness of 50 μm to 250 μm.
Embodiment 2-the multilayer composite of embodiment 1, wherein the adhesive layer a does not undergo UV curing prior to combination with layer B.
Embodiment 3-the multilayer composite of embodiment 1 or 2, wherein the adhesive layer a is in contact with substantially all of one planar surface of the polymer film.
Embodiment 4-the multilayer composite of any of embodiments 1, 2, or 3, wherein the hot melt adhesive layer B is in contact with substantially all of one planar surface of the polymer film.
Embodiment 5-the multilayer composite of any of embodiments 1, 2, 3, or 4, wherein the adhesive layer a comprises a UV-cured poly (acrylate) resin.
Embodiment 6-the multilayer composite of any of embodiments 1, 2, 3, 4, or 5, wherein the aqueous latex binder comprises at least one styrene/acrylic latex, styrene butadiene latex, or nitrile butadiene latex.
Embodiment 7-the multilayer composite of any of embodiments 1, 2, 3, 4, 5, or 6, wherein the aqueous latex binder is derived from at least one monomer selected from the group consisting of styrene, 2-ethylhexyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylamide, acrylic acid, methacrylic acid, itaconic acid, and vinylphosphonic acid.
Embodiment 8-the multilayer composite of any of embodiments 1, 2, 3, 4, 5, 6, or 7, wherein the hot melt adhesive layer B is selected from the group consisting of UV curable acrylic PSA and UV curable styrene block copolymer PSA.
Embodiment 9-the multilayer composite of any of embodiments 1, 2, 3, 4, 5, 6, 7, or 8, wherein the polymer film is selected from the group consisting of thermoplastic films, ethylene-propylene-diene terpolymer rubber (EPDM), TPO, PVC, modified asphalt, rubber films, asphalt films, and fibrous films.
Embodiment 10-the multilayer composite of any of embodiments 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein the multilayer composite has a peel strength of at least 6psi when adhered to a stainless steel panel and tested according to PSTC 101.
Embodiment 11-the multilayer composite of any of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, wherein the multilayer composite has a dead load shear (dead load shear) of at least 0.5 hours when adhered to a stainless steel panel and tested according to PSTC 107.
Embodiment 12-the multilayer composite of any of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, wherein the adhesive layer a has a thickness of 25 μιη to 100 μιη, and wherein the hot melt adhesive layer B has a thickness of 50 μιη to 100 μιη.
Embodiment 13-the multilayer composite of any of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, wherein the adhesive layer a further comprises one or more additives.
Embodiment 14-the multilayer composite of any of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13, wherein the multilayer composite is a roofing membrane.
Embodiment 15-a roofing membrane comprising the multilayer of any one of embodiments 1-14.
Embodiment 16-a method for forming a multilayer composite, the method comprising:
(a) The melt-extrudable UV curable pressure sensitive layer a is heated,
(b) The melt-extrudable UV curable pressure sensitive adhesive B is heated,
(c) Extruding the layer a and the adhesive B onto a planar surface of a polymer film such that the adhesive is in contact with substantially all of one planar surface of the polymer film, thereby forming an adhesive coating layer comprising an adhesive layer a and a hot melt adhesive layer B;
wherein the adhesive layer A has a thickness of 25 μm to 250 μm, and
wherein the hot melt adhesive layer B has a thickness of 50 μm to 250 μm,
(d) Subjecting the adhesive coating layer to UV radiation;
(e) Optionally, cooling the adhesive coating layer;
(f) Applying a release liner to the adhesive coating layer to form a multilayer composite;
and
(g) Winding the composite material.
Embodiment 17-the method of embodiment 16, wherein the melt-extrudable UV curable pressure sensitive layer a further comprises an aqueous latex binder.
Embodiment 18-the method of embodiment 16 or 17, wherein in step (c), the binder a and the binder B are co-extruded simultaneously.
Embodiment 19-the method of embodiment 16 or 17, wherein in step (c), the adhesive layer a and the adhesive B are extruded sequentially.
Embodiment 20-the method of any of embodiments 16, 17, 18, or 19, wherein the adhesive layer a comprises a UV curable poly (acrylate) resin and an aqueous latex adhesive.
Embodiment 21-the method of any of embodiments 16, 17, 18, 19, or 20, wherein the hot melt adhesive layer B comprises a UV-cured poly (acrylate) resin.
Embodiment 22-the method of any of embodiments 16, 17, 18, 19, 20, or 21, wherein the hot melt adhesive layer B is selected from the group consisting of UV curable acrylic PSAs and UV curable styrene block copolymer PSAs.
Embodiment 23-the method of any of embodiments 16, 17, 18, 19, 20, 21, or 22, wherein the polymer membrane is selected from the group consisting of thermoplastic membranes, ethylene-propylene-diene terpolymer rubber (EPDM), TPO, PVC, modified asphalt, rubber membranes, asphalt membranes, and fibrous membranes.
Embodiment 24-the method of any of embodiments 16, 17, 18, 19, 20, 21, 22, or 23, wherein the simultaneously co-extruded adhesive a and adhesive B are simultaneously co-extruded onto a moving web of thermoplastic film, ethylene-propylene-diene terpolymer rubber (EPDM), TPO, PVC, modified asphalt, rubber film, asphalt film, and fibrous film in a dual slot die configuration.
Embodiment 25-the method of any of embodiments 16, 17, 18, 19, 20, 21, 22, 23, or 24, wherein the adhesive a and/or the adhesive B comprises an additive selected from the group consisting of tackifiers, plasticizers, one or more photoinitiators.
Embodiment 26-the method of any of embodiments 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25, wherein the adhesive a/B is heated to a temperature of about 120 ℃ to about 160 ℃.
Embodiment 27-the method of any of embodiments 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, or 26, wherein subjecting the coating to UV radiation comprises subjecting the adhesive coating layer to about 40 millijoules/cm 2 To about 80 mJ/cm 2 Is used to control the UV dose of (a).
Embodiment 28-the method of any of embodiments 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, or 27, wherein the multilayer composite has a width of about 1 meter to about 20 meters.
Embodiment 29-a method for roofing a structure, the method comprising:
(a) The multilayer composite of any of embodiment 15 is provided,
(b) Removing the release liner from the multilayer composite, thereby forming a linerless multilayer composite, and
(c) The linerless multilayer composite is adhered/laminated/mounted to a roof sub-structure to form a roof laminate.
Embodiment 30-a multilayer composite comprising:
a substrate;
an adhesive layer A;
a hot melt adhesive layer B; and
the release liner is provided with a release liner,
wherein the adhesive layer a comprises an Ultraviolet (UV) curable pressure sensitive adhesive and an aqueous latex adhesive;
wherein the hot melt adhesive layer B comprises an at least partially cured Ultraviolet (UV) curable pressure sensitive adhesive;
wherein the adhesive layer a has a thickness of 25 μm to 250 μm, and wherein the hot melt adhesive layer B has a thickness of 50 μm to 250 μm.
The foregoing embodiments are merely examples, and should not be construed as limiting or otherwise narrowing the scope of any inventive concepts otherwise provided by the present disclosure. While various embodiments are disclosed, other embodiments will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative examples. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not as restrictive.
Drawings
Fig. 1a is a cross-sectional view of a film composite according to an embodiment of the present invention.
Fig. 1b is a cross-sectional view of a film composite according to an embodiment of the present invention.
Fig. 2 is a cross section of a dual slot die for coextruding a and B onto a polymer film.
Detailed Description
The following examples further illustrate the invention but, of course, should not be construed as in any way limiting its scope. Provided herein are multilayer composites, particularly multilayer composites useful as roofing membranes. The multilayer composites of the invention comprise a polymer film; a first adhesive layer a comprising an Ultraviolet (UV) curable pressure sensitive adhesive that does not undergo UV curing prior to combination with the second hot melt adhesive layer, or an aqueous latex adhesive; a second adhesive layer B comprising an at least partially cured Ultraviolet (UV) curable pressure sensitive adhesive; and a release liner, each component being described in detail below.
Fig. 1a shows a multilayer composite 10, which is referred to as a membrane 10. The multilayer composite 10 includes a polymer film 1, a pressure sensitive adhesive layer UV curable adhesive layer A2, a pressure sensitive UV curable adhesive layer B3, and a release liner 4 removably attached to the layer 3. In fig. 1B, the order of the adhesive layers a and B is reversed.
Polymeric film/substrate
According to various embodiments described herein, the polymer membrane may be a thermoplastic membrane, an ethylene-propylene-diene terpolymer rubber (EPDM) -based membrane, a TPO-based membrane, a PVC-based membrane, other polymer-based components [ details ], a rubber membrane, an asphalt membrane, or a fibrous membrane. These films may be flexible, crimpable or sheetlike.
In one or more embodiments, the film comprises an EPDM film, including those meeting ASTM D-4637 specifications. In other embodiments, the films include thermoplastic films, including those meeting ASTM D-6878-03 specifications.
The thickness of the polymer film is not particularly limited. However, for commercial applications, particularly for those in the roofing industry, the polymeric film has a thickness of about 500 μm to about 3mm, about 1,000 μm to about 2.5mm, or about 1,500 μm to about 2 mm.
In one or more embodiments, it is contemplated to replace the polymer film with a substrate. Typically, the substrate is more rigid than the polymer film. For example, the substrate may be gypsum, oriented Strand Board (OSB), metal, and plywood. The thickness of the substrate is not particularly limited.
Adhesive A
According to various embodiments described herein, the adhesive useful for forming the pressure sensitive adhesive layer a may comprise an acrylic copolymer. In another embodiment, the adhesive layer a may comprise an aqueous latex adhesive.
As used herein, the term "theoretical glass transition temperature" or "theoretical Tg" refers to the estimated Tg of a polymer or copolymer calculated using the Fox equation. The Fox equation may be used to estimate the glass transition temperature of a polymer or copolymer, as described, for example, in L.H.Sperling, "Introduction to Physical Polymer Science", 2 nd edition, john Wiley & Sons, new York, page 357 (1992) and T.G.Fox, bull.Am.Phys.Soc,1,123 (1956), both of which are incorporated herein by reference. For example, the theoretical glass transition temperature of the copolymer derived from monomers a, b..and i can be calculated according to the following equation
1/T g ＝wa/T ga +wb/T gb +…+wi/T gi
Where wa is the weight fraction of monomer a in the copolymer, T ga Is the glass transition temperature of the homopolymer of monomer a, wb is the weight fraction of monomer b in the copolymer, T gb Is the glass transition temperature of the homopolymer of monomer b, wi is the weight fraction of monomer i in the copolymer, T gi Is the glass transition temperature of the homopolymer of monomer i, and T g Is the theoretical glass transition temperature of the copolymer derived from monomers a, b.
"copolymer" refers to a polymer containing two or more monomers.
"homopolymer" refers to a polymer formed from one monomer.
As used herein, the term "(meth) acrylate monomers" includes acrylate, methacrylate, diacrylate and dimethacrylate monomers.
According to various embodiments described herein, the acrylic copolymer comprising layer a may be based on the polymerization of monomer a, monomer B, and monomer C.
According to various embodiments described herein, monomer a may include methyl, ethyl, propyl, isoamyl, isooctyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, 2-ethylhexyl, decyl, lauryl, or stearyl esters of acrylic and/or methacrylic acid, and any mixtures thereof.
According to various embodiments described herein, monomer a may have a Tg of less than-20 ℃. For example, tg may be-30℃or less, -40℃or less, -45℃or less, -50℃or less, -55℃or less or-60℃or less. The glass transition temperature can be determined by Differential Scanning Calorimetry (DSC) using ASTM D3418-12 e1 to measure the midpoint temperature.
According to various embodiments described herein, monomer B may include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, N-butyl maleate, monoethyl fumarate, monomethyl itaconate and monomethyl maleate, acrylamide and methacrylamide, N-methacrylamide and-methacrylamide, N-methylolacrylamide and-methacrylamide, maleic acid mono-and diamides, itaconic acid mono-and diamides, fumaric acid mono-and diamides, vinylsulfonic acid or vinylphosphonic acid, and mixtures thereof.
According to various embodiments described herein, monomer C may include methyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl acrylate, isobutyl methacrylate, vinyl acetate, hydroxyethyl acrylate, hydroxyethyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethoxyethyl methacrylate, 2-phenoxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, hydroxypropyl methacrylate, styrene, 4-acetyl styrene, acrylamide, acrylonitrile, 4-bromostyrene, n-t-butyl acrylamide, 4-t-butyl styrene, 2, 4-dimethylstyrene, 2, 5-dimethylstyrene, 3, 5-dimethylstyrene, isobornyl acrylate, isobornyl methacrylate, 4-methoxystyrene, methyl styrene, alpha-methylstyrene, 4-methylstyrene, 3-methylstyrene, 2,4, 6-trimethylstyrene, vinyl pyrrolidone, ureido methacrylate, and combinations thereof.
According to some embodiments, the acrylic copolymer may comprise monomer a in an amount of 50 wt% to 99.99 wt% based on the weight of monomers A, B and C in the copolymer.
According to some embodiments, the acrylic copolymer may comprise monomer B in an amount of 0.1 to 25 wt%, based on the weight of monomers A, B and C in the copolymer.
According to some embodiments, the acrylic copolymer may comprise monomer C in an amount of 0.1 to 25 wt%, based on the weight of monomers A, B and C in the copolymer.
The acrylic copolymer may include a percentage of carboxylic acid functionality, such as acrylic acid. The acrylic functional group may be present in an amount of about 5wt% or greater, about 6wt% or greater, about 7wt% or greater, about 8wt% or less, about 9wt% or less, about 10wt% or less, or any value encompassed by these endpoints, based on the total weight of the polymer.
The acrylic copolymer may be prepared by known methods.
Weight average molecular weight (M) of acrylic copolymer w ) May be, for example, 150,000da or greater (e.g., 160,000da or greater, 170,000da or greater, 180,000da or greater, 190,000da or greater, 200,000da or greater, 210,000da or greater, 220,000da or greater, 230,000da or greater, 240,000da or greater). In some embodiments, the weight average molecular weight of the acrylic copolymer may be 250,000da or less (e.g., 240,000da or less, 230,000da or less, 220,000da or less, 210,000da or less, 200,000da or less, 190,000da or less, 180,000da or less, 170,000da or less, 160,000). Weight average molecular weight (M) of acrylic copolymer w ) May range from any of the above minimum values to any of the above maximum values. For example, the weight average molecular weight (M) w ) May be 150,000Da to 250,000Da (e.g., 170,000Da to 220,000Da, or 190,000Da to 200,000 Da). The weight average molecular weight (M) of the acrylic copolymer can be determined by GPC (gel permeation chromatography) w )。
Number average molecular weight (M) of acrylic copolymer n ) May be, for example, 20,000 or more (e.g., 30,000 or more, or 40,000 or more). In some of the examples of the present invention,number average molecular weight (M) of acrylic copolymer n ) May be 50,000 or less (e.g., 40,000 or less, or 30,000 or less). Number average molecular weight (M) of acrylic copolymer n ) May range from any of the above minimum values to any of the above maximum values. For example, the number average molecular weight (M n ) May be 20,000 to 50,000 (e.g., 30,000 to 50,000, or 40,000 to 50,000). The number average molecular weight (M) of the acrylic copolymer can be determined by GPC (gel permeation chromatography) n )。
By M w /M n Calculated dispersityMay be greater than 5 (e.g., greater than 6, or greater than 7, or greater than 8, or greater than 9, or greater than 10), where Mw is the mass average molar mass (or molecular weight), M, of the acrylic copolymer n Is the number average molar mass (or molecular weight) of the acrylic copolymer. The acrylic copolymer may have a dispersity of less than 11 (e.g., less than 10, less than 9, less than 8, less than 7, or less than 6). The degree of dispersion of the acrylic copolymer may range from any of the above minimum values to any of the above maximum values. For example, the acrylic copolymer may have a dispersity of 5 to 11, or 7 to 9.
If the copolymer is used as a contact adhesive, the acrylic and/or methacrylic esters used as the main monomer are preferably those whose homopolymers have glass transition temperatures below 0 ℃, in particular below-10 ℃, in particular n-and isobutyl esters of acrylic acid and methacrylic acid, isoamyl and isooctyl esters of acrylic acid and methacrylic acid, 2-ethylhexyl esters of acrylic acid and methacrylic acid, and decyl, lauryl and lauryl acrylates and methacrylates. The amount of these main monomers is then preferably greater than 60% of the total monomers.
The copolymers generally contain from 0.01 to 10% by weight of comonomers of the formula I, but amounts of from 0.01 to 5% by weight, based on the copolymer, are generally sufficient. Copolymers which contain, as copolymerized units, from 0.5 to 25% by weight, in particular from 5 to 15% by weight, of tetrahydrofuran-2-yl (meth) acrylate in addition to other acrylates and monomers of the formula I, generally have very low molecular weights and low viscosities.
Although the pressure sensitive adhesive comprising layer a is capable of undergoing UV curing, layer a does not undergo UV curing prior to combination with layer B, as will be described further below.
Aqueous latex adhesive
Binder a may comprise an aqueous latex binder. Suitable aqueous latex adhesives exhibit high initial tack, good low temperature properties, high water resistance, and high durability. The aqueous latex binder may be substantially free of organic solvents. The aqueous latex binder may be composed of at least one styrene/acrylic latex, styrene butadiene latex, or nitrile butadiene latex. The layer must be able to withstand migration of the plasticizer from the EPDM membrane.
The at least one styrene/acrylic latex or acrylic latex may comprise a plurality of polymer particles. The particles may have a particle size distribution range as determined by static light scattering, dynamic light scattering, capillary hydrodynamic fractionation, or microscopic image analysis. For example, the method described in ASTM E3247-20, and reported as volume average particle size of no greater than 5,000nm, no greater than 4,000nm, no greater than 3,000nm, no greater than 2,000nm, no greater than 1,000nm, no greater than 750nm, no greater than 500nm, no greater than 400nm, no greater than 300nm, no greater than 200nm, or no greater than 100nm. In some embodiments, the particles have a particle size of 10nm to 5,000nm, 10nm to 4,000nm, 10nm to 3,000nm, 10nm to 2,000nm, 10nm to 1,000nm, 10nm to 750nm, 10nm to 500nm, 10nm to 400nm, 10nm to 300nm, 10nm to 200nm, 10nm to 100nm, 10nm to 50nm, 50nm to 5,000nm, 50nm to 4,000nm, 50nm to 3,000nm, 50nm to 2,000nm, 50nm to 1,000nm, 50nm to 750nm, 50nm to 500nm, 50nm to 400nm, 50nm to 300nm, 50nm to 200nm, 50nm to 100nm, 100nm to 1,000nm, 100nm to 750nm, 100nm to 500nm, 100nm to 400nm, 100nm to 300nm, or 100nm to 200 nm.
In some embodiments, the particles have a particle size of 20nm to 400 nm. In some embodiments, the particles have a particle size of 30nm to 300 nm.
The particles may be prepared by polymerizing a monomer mixture emulsified in water, for example by emulsion polymerization, optionally in the presence of polymer seeds. In some embodiments, the particles may include at least two different copolymers (multi-stage copolymers), e.g., a styrene/acrylic copolymer, an acrylic polymer, a second copolymer, a third copolymer, and the like. In some embodiments, the styrene/acrylic copolymer polymer or acrylic polymer, the second copolymer, etc. may be prepared in separate reaction vessels and then combined. In a preferred embodiment, the second copolymer, third copolymer, etc. are prepared by polymerizing a monomer mixture in the presence of a styrene/acrylic acid copolymer or acrylic acid polymer.
The styrene/acrylic acid copolymer and the acrylic acid polymer may be derived from at least one monomer selected from the group consisting of: styrene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, 2-methylheptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, alkyl crotonate, vinyl acetate, di-n-butyl maleate, dioctyl (meth) acrylate, hydroxyethyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, vinyl acetate, di-n-butyl (meth) acrylate, dioctyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethoxyoctyl (meth) acrylate, octyl (meth) and tetrahydrofurfuryl (meth) acrylate Caprolactone (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol (meth) acrylate, benzyl (meth) acrylate, hydroxypropyl (meth) acrylate, methyl polyethylene glycol (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, N-butyl maleate, monoethyl fumarate, monomethyl and monomethyl maleates, acrylamides and methacrylamides, N-methacrylamides and-methacrylates, N-methylolacrylamides and-methacrylamides, maleic acid monoamides and diamides, itaconic acid monoamides and diamides, fumaric acid monoamides and diamides, vinylsulfonic acid, and vinylphosphonic acid.
The styrene/acrylic latex or acrylic latex may also include crosslinkable monomers such as diacetone acrylamide and its derivatives, as well as 2- (methacryloyloxy) ethyl acetoacetate and its derivatives.
Preferably, the styrene/acrylic latex or acrylic acid may be derived from at least one monomer selected from the group consisting of: styrene, 2-ethylhexyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylamide, acrylic acid, methacrylic acid, itaconic acid and vinylphosphonic acid, diacetone acrylamide and 2- (methacryloyloxy) ethyl acetoacetate.
The styrene/acrylic latex or acrylic latex may further comprise a crosslinking agent which is reactive with the crosslinkable monomer described above. The crosslinking agent may include adipic acid dihydrazide (ADDH); a polyfunctional amine; and metal ions such as copper, magnesium, zinc, calcium, iron, chromium, titanium, aluminum, and zirconium. Preferably, the metal ion is zinc, aluminum or zirconium.
In some embodiments, the glass transition temperature (Tg) of the styrene/acrylic latex or the acrylic latex may be in the range of-60 ℃ to 30 ℃. For example, tg may be-40℃or higher, -35℃or higher, -30℃or higher, -25℃or higher, -20℃or higher, -15℃or higher, -10℃or lower, -5℃or lower, 0℃or lower, 5℃or lower, or 10℃or lower. The glass transition temperature can be determined by Differential Scanning Calorimetry (DSC) using ASTM D3418-12 e1 to measure the midpoint temperature.
The Tg of the styrene/acrylic latex or acrylic latex can be between any of the values described above. For example, tg may be in the range of-60℃to 30 ℃ (e.g., 0℃to 5 ℃, 10℃to 30 ℃ below zero, or 20℃to 40 ℃ below zero).
The styrene/acrylic latex or the acrylic latex may include a soft phase. The soft phase may have a glass transition temperature (Tg) of 20℃or less, 15℃or less, 10℃or less, 5℃or less, 0℃or less, -5℃or less, or-10℃or less.
The Tg of the soft phase of the polymer can be calculated by the Flory-Fox equation shown below, where Tg is the glass transition temperature, tg, and infinity is the maximum glass transition temperature achievable at a theoretical infinite molecular weight, M n Is the number average molecular weight of the polymer and K is an empirical parameter related to the free volume present in the polymer sample.
T g ＝T g,∞ -K/M n
The acrylate component of the styrene/acrylic latex or acrylic latex may be derived from one or more soft ethylenically unsaturated monomers. As used herein, the term "soft ethylenically unsaturated monomer" refers to an ethylenically unsaturated monomer that, upon homopolymerization, forms a polymer having a glass transition temperature (as measured using Differential Scanning Calorimetry (DSC)) of 20 ℃ or less. Soft ethylenically unsaturated monomers are known in the art and include, for example, methyl acrylate (tg=10℃), ethyl acrylate (tg= -24 ℃), n-butyl acrylate (tg= -54 ℃), sec-butyl acrylate (tg= -26 ℃), n-hexyl acrylate (tg= -45 ℃), n-hexyl methacrylate (tg= -5 ℃), 2-ethylhexyl acrylate (tg= -85 ℃), 2-ethylhexyl methacrylate (tg= -10 ℃), octyl methacrylate (tg= -20 ℃), n-decyl methacrylate (tg= -30 ℃), isodecyl acrylate (tg= -55 ℃), dodecyl acrylate (tg= -3 ℃), dodecyl methacrylate (tg= -65 ℃), 2-ethoxyethyl acrylate (tg= -50 ℃), 2-methoxyester acrylate (tg= -50 ℃) and 2- (2-ethoxyethoxy) ethyl acrylate (tg= -70 ℃).
In some embodiments, the soft phase may include soft ethylenically unsaturated monomers that, when homopolymerized, form a polymer having a glass transition temperature (as measured using DSC) of 20 ℃ or less (e.g., 20 ℃ or less, 10 ℃ or less, 0 ℃ or less, -10 ℃ or less, -20 ℃ or less, -30 ℃ or less, -40 ℃ or less, -50 ℃ or less, -60 ℃ or less, -70 ℃ or less, or-80 ℃ or less). In certain embodiments, the soft ethylenically unsaturated monomer may be a (meth) acrylate monomer. In certain embodiments, the acrylate component of the styrene/acrylic latex or acrylic latex may be derived from a soft ethylenically unsaturated monomer selected from the group consisting of n-butyl acrylate, ethyl acrylate, sec-butyl acrylate, 2-ethylhexyl (meth) acrylate, and combinations thereof.
In some embodiments, the soft phase may include hard ethylenically unsaturated monomers that, when homopolymerized, form a polymer having a glass transition temperature of 20 ℃ or less (e.g., 20 ℃ or less, 10 ℃ or less, 0 ℃ or less, -10 ℃ or less, -20 ℃ or less, -30 ℃ or less, -40 ℃ or less, -50 ℃ or less, -60 ℃ or less, -70 ℃ or less, or-80 ℃ or less) as measured using DSC. Hard ethylenically unsaturated monomers are known in the art and include, for example, methyl methacrylate (tg=105℃), ethyl methacrylate (tg=65℃), n-butyl methacrylate (tg=20℃), t-butyl methacrylate (tg=118℃), t-butyl acrylate (tg=45℃), isobutyl methacrylate (tg=53℃), vinyl acetate (tg=30℃), hydroxyethyl acrylate (tg=15℃), hydroxyethyl methacrylate (tg=57℃), cyclohexyl acrylate (tg=19℃), cyclohexyl methacrylate (tg=92℃), 2-ethoxyethyl methacrylate (tg=16℃), 2-phenoxyethyl methacrylate (tg=54 ℃), benzyl acrylate (tg=6℃), benzyl methacrylate (tg=54 ℃) hydroxypropyl methacrylate (tg=76 ℃), styrene (tg=100℃), 4-acetylstyrene (tg=116), acrylamide (tg=165 ℃), methacrylonitrile (tg=125 ℃), 4-bromostyrene (tg=57 ℃), 2-ethoxyethyl methacrylate (tg=16 ℃), 2-ethoxyethyl methacrylate (tg=54 ℃), benzyl methacrylate (tg=76 ℃), styrene (tg=100 ℃), 4-acetylstyrene (tg=116 ℃), vinyl methacrylate (tg=4-vinyl bromide) 2, 5-dimethylstyrene (tg=143℃), 3, 5-dimethylstyrene (tg=104℃), isobornyl acrylate (tg=94℃), isobornyl methacrylate (tg=110℃), 4-methoxystyrene (tg=113℃), methylstyrene (tg=20℃), 4-methylstyrene (tg=97℃), 3-methylstyrene (tg=97℃), 2,4, 6-trimethylstyrene (tg=162℃) and combinations thereof.
In some embodiments, the soft phase may include soft and hard ethylenically unsaturated monomers that, when copolymerized, form a polymer having a glass transition temperature of 20 ℃ or less (e.g., 20 ℃ or less, 10 ℃ or less, 0 ℃ or less, -10 ℃ or less, -20 ℃ or less, -30 ℃ or less, -40 ℃ or less, -50 ℃ or less, -60 ℃ or less, -70 ℃ or less, or-80 ℃ or less) as measured using DSC.
The styrene/acrylic latex or acrylic latex may be derived from at least 10 wt% to at most 95 wt% of one or more soft ethylenically unsaturated monomers (e.g., at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, at least 50 wt%, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 75 wt%, at least 80 wt%, at least 85 wt%, or at least 90 wt%, based on the total weight of monomers used to form the styrene/acrylic latex or acrylic latex. The styrene/acrylic latex or acrylic latex may be derived from up to 95 weight percent of one or more hard ethylenically unsaturated monomers (e.g., up to 90 weight percent, up to 80 weight percent, up to 75 weight percent, up to 70 weight percent, up to 65 weight percent, up to 60 weight percent, up to 55 weight percent, up to 50 weight percent, up to 45 weight percent, up to 40 weight percent, up to 35 weight percent, up to 30 weight percent, up to 25 weight percent, up to 20 weight percent, or up to 15 weight percent), based on the total weight used to form the styrene/acrylic latex or acrylic latex.
The styrene/acrylic latex or acrylic latex may be derived from an amount of one or more soft ethylenically unsaturated monomers ranging from any of the minimum percentages described above to any of the maximum percentages described above. For example, the styrene/acrylic latex or acrylic latex may be derived from 15 wt% to 95 wt% of one or more soft ethylenically unsaturated monomers (e.g., 15 wt% to 85 wt%, 25 wt% to 80 wt%, 30 wt% to 70 wt%, or 35 wt% to 55 wt%, based on the total weight of monomers used to form the styrene/acrylic latex or acrylic latex. Preferably, the styrene/acrylic latex or acrylic latex may be derived from about 40 to about 95 weight percent of one or more soft ethylenically unsaturated monomers, based on the total weight of monomers used to form the styrene/acrylic latex or acrylic latex.
Optionally, the styrene/acrylic latex or acrylic latex may contain a hard phase. The hard phase of the styrene/acrylic latex or acrylic latex may have a glass transition temperature (Tg) that is higher than the Tg of the soft phase, as calculated by the Flory-Fox equation. For example, the Tg of the hard phase of the styrene/acrylic latex or acrylic latex may be 20℃higher than the Tg of the soft phase.
The hard phase may include one or more hard ethylenically unsaturated monomers. As used herein, the term "hard ethylenically unsaturated monomer" refers to an ethylenically unsaturated monomer that, upon homopolymerization, forms a polymer having a Tg greater than 20 ℃ as measured using DSC. Hard ethylenically unsaturated monomers are known in the art and include, for example, methyl methacrylate (tg=105℃), ethyl methacrylate (tg=65℃), n-butyl methacrylate (tg=20℃), t-butyl methacrylate (tg=118℃), t-butyl acrylate (tg=45℃), isobutyl methacrylate (tg=53℃), vinyl acetate (tg=30℃), hydroxyethyl acrylate (tg=15℃), hydroxyethyl methacrylate (tg=57℃), cyclohexyl acrylate (tg=19℃), cyclohexyl methacrylate (tg=92℃), 2-ethoxyethyl methacrylate (tg=16℃), 2-phenoxyethyl methacrylate (tg=54 ℃), benzyl acrylate (tg=6℃), benzyl methacrylate (tg=54 ℃) hydroxypropyl methacrylate (tg=76 ℃), styrene (tg=100℃), 4-acetylstyrene (tg=53 ℃), acrylamide (tg=165 ℃), acrylonitrile (tg=116 ℃), 4-bromostyrene (tg=92 ℃), 2-ethoxyethyl methacrylate (tg=16 ℃), 2-ethoxyethyl methacrylate (tg=54 ℃), benzyl methacrylate (tg=76 ℃), styrene (tg=100 ℃), 4-acetylstyrene, 4-bromostyrene (tg=15 ℃), n-butyl acrylate (tg=16 ℃) 2, 5-dimethylstyrene (tg=143℃), 3, 5-dimethylstyrene (tg=104℃), isobornyl acrylate (tg=94℃), isobornyl methacrylate (tg=110℃), 4-methoxystyrene (tg=113℃), methylstyrene (tg=20℃), 4-methylstyrene (tg=97℃), 3-methylstyrene (tg=97℃), 2,4, 6-trimethylstyrene (tg=162℃) and combinations thereof.
In some embodiments, the hard phase may include soft ethylenically unsaturated monomers that, when homopolymerized, form a polymer having a glass transition temperature of 20 ℃ or less (e.g., 20 ℃ or less, 10 ℃ or less, 0 ℃ or less, -10 ℃ or less, -20 ℃ or less, -30 ℃ or less, -40 ℃ or less, -50 ℃ or less, -60 ℃ or less, -70 ℃ or less, or-80 ℃ or less) as measured using DSC.
In some embodiments, the hard phase may include soft ethylenically unsaturated monomers and hard ethylenically unsaturated monomers that, when copolymerized, form a polymer having a glass transition temperature above the Tg of the soft phase. For example, the Tg of the hard phase of the styrene/acrylic latex or acrylic latex may be 20℃higher than the Tg of the soft phase.
In some embodiments, the styrene/acrylic latex or acrylic latex may be derived from greater than 5 wt% of one or more hard ethylenically unsaturated monomers (e.g., 10 wt% or greater, 20 wt% or greater, 30 wt% or greater, 40 wt% or greater, 50 wt% or greater, 55 wt% or greater hard ethylenically unsaturated monomers) based on the total weight of monomers used to form the styrene/acrylic latex or acrylic latex.
In some embodiments, the styrene/acrylic latex or acrylic latex may be derived from less than 60 wt% of one or more hard ethylenically unsaturated monomers (e.g., 55 wt% or less, 50 wt% or less, 45 wt% or less, 40 wt% or less, 35 wt% or less, 30 wt% or less, 25 wt% or less, 20 wt% or less, 15 wt% or less, 10 wt% or less) based on the total weight of monomers used to form the styrene/acrylic latex or acrylic latex.
In addition to the one or more soft ethylenically unsaturated monomers, the one or more phosphorus-containing monomers, and the one or more acetoacetoxy monomers, ketone or aldehyde monomers, the styrene/acrylic latex or acrylic latex may also be derived from one or more additional ethylenically unsaturated monomers (e.g., (meth) acrylate monomers, vinyl aromatic monomers, etc.) as described below.
The styrene/acrylic latex or acrylic latex may be derived from greater than 0 wt% to 55 wt% of one or more additional ethylenically unsaturated monomers. Additional ethylenically unsaturated monomers include (meth) acrylate monomers. These (meth) acrylate monomers may include esters of alpha, beta-monoethylenically unsaturated monocarboxylic and dicarboxylic acids having 3 to 6 carbon atoms with alkanols having 1 to 20 carbon atoms (e.g., esters of acrylic acid, methacrylic acid, maleic acid, fumaric acid, or itaconic acid with C1-C20, C1-C12, C1-C8, or C1-C4 alkanols). Exemplary acrylate and methacrylate monomers include, but are not limited to, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, 2-methylheptyl methacrylate, octyl methacrylate, isooctyl methacrylate, n-nonyl methacrylate, isononyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, dodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, glycidyl acrylate, alkyl crotonates vinyl acetate, di-n-butyl maleate, dioctyl maleate, hydroxyethyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxy (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2-propylheptyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, caprolactone (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol (meth) acrylate, benzyl (meth) acrylate, hydroxypropyl (meth) acrylate, methyl polyethylene glycol (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, 1,6 hexanediol di (meth) acrylate, 1,4 butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and combinations thereof. In some embodiments, the acrylate component of the styrene/acrylic latex or acrylic latex comprises one or more (meth) acrylate monomers selected from the group consisting of methyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and combinations thereof. In some embodiments, the acrylate component of the styrene/acrylic latex or acrylic latex comprises methyl methacrylate and n-butyl acrylate.
In the styrene/acrylic latex or acrylic latex, the additional ethylenically unsaturated monomer may include a vinyl aromatic compound having up to 20 carbon atoms, a vinyl ester of a carboxylic acid containing up to 20 carbon atoms, (meth) acrylonitrile, a vinyl halide, a vinyl ether of an alcohol containing from 1 to 10 carbon atoms, an aliphatic hydrocarbon having from 2 to 8 carbon atoms and one or two double bonds, an alkoxysilane-containing monomer, an adhesion-promoting ureido-functional (meth) acrylate monomer, (meth) acrylamide derivatives, sulfur-based monomers, or a combination of these monomers.
Suitable vinyl aromatic compounds include styrene, alpha-and para-methylstyrene, alpha-butylstyrene, 4-n-decylstyrene, vinyl toluene, and combinations thereof. Vinyl esters of carboxylic acids having up to 20 carbon atoms with alkanols include, for example, vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate, vinyl acetate, and combinations thereof. Vinyl halides may include ethylenically unsaturated compounds substituted with chlorine, fluorine or bromine, such as vinyl chloride and vinylidene chloride. The vinyl ether may include, for example, a vinyl ether of an alcohol containing 1 to 4 carbon atoms, such as vinyl methyl ether or vinyl isobutyl ether. Aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds may include, for example, hydrocarbons having 4 to 8 carbon atoms and two olefinic double bonds, such as butadiene, isoprene, and chloroprene. The alkoxysilane-containing monomers may include, for example, vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane (VTEO), vinyltris (2-methoxyethoxysilane), and vinyltriisopropoxysilane, and (meth) acryloxysilanes such as (meth) acryloxypropyl trimethoxysilane, gamma- (meth) acryloxypropyl trimethoxysilane, and gamma- (meth) acryloxypropyl triethoxysilane. Sulfur-containing monomers include, for example, sulfonic acids and sulfonates such as vinylsulfonic acid, 2-sulfoethyl methacrylate, sodium styrene sulfonate, 2-sulfoethyl methacrylate, vinylbutylsulfonate, sulfones such as vinylsulfone, sulfoxides such as vinylsulfoxide, and sulfides such as 1- (2-hydroxyethylthio) butadiene. When present, sulfur-containing monomers are typically present in an amount of greater than 0 wt% to 5 wt%.
The styrene/acrylic latex or acrylic latex may comprise an acrylic-based copolymer. Acrylic acid-based copolymers include copolymers derived from one or more (meth) acrylate monomers. The acrylic-based copolymer may be a pure acrylic polymer (i.e., a copolymer derived primarily from (meth) acrylate monomers), a styrene-acrylic polymer (i.e., a copolymer derived from styrene and one or more (meth) acrylate monomers), or a vinyl-acrylic polymer (i.e., a copolymer derived from one or more vinyl ester monomers and one or more (meth) acrylate monomers).
The styrene/acrylic latex or acrylic latex may be derived from one or more phosphorous acid containing monomers based on the total weight of the monomers. Ammonium, alkali metal, alkaline earth metal and other metal ion salts of these acids may also be used. For example, suitable phosphorus-containing monomers are vinyl phosphonic acid and allyl phosphonic acid. Also suitable are monoesters and diesters, especially monoesters, of phosphonic and phosphoric acids with hydroxyalkyl (meth) acrylates. Further suitable monomers are diesters of phosphonic acid and phosphoric acid, which have been esterified once with hydroxyalkyl (meth) acrylates and have also been esterified with different alcohols (e.g., alkanol) is esterified once. Suitable hydroxyalkyl (meth) acrylates for these esters are those specified below as separate monomers, more specifically 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. The corresponding phospho-dihydrogenester monomers comprise phosphoalkyl (meth) acrylates, such as 2-phosphoethyl (meth) acrylate, 2-phosphopropyl (meth) acrylate, 3-phosphopropyl (meth) acrylate, phosphobutyl (meth) acrylate and 3-phospho-2-hydroxypropyl (meth) acrylate. Also suitable are esters of phosphonic and phosphoric acids with alkoxylated hydroxyalkyl (meth) acrylates, examples being ethylene oxide or propylene oxide condensates of (meth) acrylates, such as H 2 C═C(CH 3 )COO(CH 2 CH 2 O) n P(OH) 2 And H 2 C═C(CH 3 )COO(CH 2 CH 2 O) n P(═O)(OH) 2 Wherein n is 1 to 50. More suitable are alkyl crotonates, alkyl maleates, alkyl fumarates, dialkyl (meth) acrylates, dialkyl crotonates and allyl phosphates.
Examples of unsaturated monomers containing phosphate esters are those distributed by SolvayPAM 4000 (colorless to pale yellow clear ethyl methacrylate phosphate and alkyl methacrylate phosphate with slight acrylic odor, CAS number 52628-03-02) or >PAM 200 (a phosphate ester of PPG monomethacrylate). Salts of the above acids neutralized with alkali metal or alkaline earth metal ions or ammonia, and combinations thereof, may also be used. In some cases, the monomer mixture may include a mixture of ethylenically unsaturated acids, such as (meth) acrylic acid and phosphorous acid containing monomers, or itaconic acid and phosphorous acid containing monomers, or a combination of carboxylic acid and phosphorous acid containing monomers. Neutralization of alkali or alkaline earth metal ions or ammonia of the above acids may also be usedIs a salt of (b) and combinations thereof.
The styrene/acrylic latex or acrylic latex may be derived from greater than 0 wt% of one or more phosphorus-containing monomers (e.g., at least 0.25 wt%, at least 0.5 wt%, at least 1 wt%, at least 1.5 wt%, at least 2 wt%, at least 2.5 wt%, at least 3 wt%, at least 3.5 wt%, at least 4 wt%, or at least 4.5 wt% or at least 5 wt% or at least 10 wt%, based on the total weight of monomers used to form the styrene/acrylic latex or acrylic latex. The styrene/acrylic latex or acrylic latex may be derived from 10 wt% or less of one or more phosphorus-containing monomers (e.g., 5 wt% or less, 4.5 wt% or less, 4 wt% or less, 3.5 wt% or less, 3 wt% or less, 2.5 wt% or less, 2 wt% or less, 1.5 wt% or less, 1 wt% or less, or 0.5 wt% or less, or 0.25 wt% or less) based on the total weight of monomers used to form the styrene/acrylic latex or acrylic latex.
The styrene/acrylic latex or acrylic latex may be derived from greater than 0 weight percent of one or more acid-containing monomers (e.g., at least 0.5 weight percent, at least 1 weight percent, at least 2 weight percent, at least 3 weight percent, at least 4 weight percent, at least 5 weight percent, at least 6 weight percent, at least 7 weight percent, at least 8 weight percent, at least 9 weight percent, at least 10 weight percent, at least 15 weight percent, at least 20 weight percent, at least 25 weight percent, at least 30 weight percent) based on the total weight of monomers used to form the styrene/acrylic latex or acrylic latex. The styrene/acrylic latex or acrylic latex may be derived from 30 wt% or less of one or more acid-containing monomers (e.g., 25 wt% or less, 20 wt% or less, 15 wt% or less, 10 wt% or less, 5 wt% or less, 3 wt% or less, or 1 wt% or less) based on the total weight of monomers used to form the styrene/acrylic latex or acrylic latex. Preferably, the styrene/acrylic latex or acrylic latex may be derived from about 0.5% to about 10% by weight of one or more acid-containing monomers, based on the total weight of monomers used to form the styrene/acrylic latex or acrylic latex.
The styrene/acrylic latex or acrylic latex may be derived from one or more carboxylic acid-containing monomers. Suitable carboxylic acid-containing monomers are known in the art and include α, β -monoethylenically unsaturated mono-and dicarboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, dimethacrylate, ethacrylic acid, allylacetic acid, vinylacetic acid, mesaconic acid, methylenemalonic acid, citraconic acid, and combinations thereof.
The styrene/acrylic latex or acrylic latex may be derived from an amount of one or more acid-containing monomers ranging from any of the minimum percentages described above to any of the maximum percentages described above. For example, the styrene/acrylic latex or acrylic latex may be derived from greater than 0.5 wt% to 30 wt% of one or more acid-containing monomers (e.g., greater than 2 wt% to 20 wt% of one or more acid-containing monomers) based on the total weight of monomers used to form the styrene/acrylic latex or acrylic latex. In certain embodiments, the styrene/acrylic latex or acrylic latex is derived from greater than 2 wt% to 30 wt% (e.g., greater than 2 wt% to 10 wt%, greater than 2 wt% to 15 wt%, or greater than 2 wt% to 20 wt%) of the acid monomer.
The styrene/acrylic latex or acrylic latex may be derived from one or more sulfur acid-containing monomers. Suitable sulfuric acid monomers are vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and their ionic salts with ammonium and metal ions. Suitable styrenesulfonic acids and derivatives thereof are styrene-4-sulfonic acid and styrene-3-sulfonic acid, and also their ionic salts with metal ions, such as sodium styrene-3-sulfonate and sodium styrene-4-sulfonate.
The styrene/acrylic latex or acrylic latex may be derived from an amount of one or more phosphorus-containing monomers ranging from any of the minimum percentages described above to any of the maximum percentages described above. For example, the styrene/acrylic latex or acrylic latex may be derived from greater than 0 wt% to 10 wt% of one or more phosphorus-containing monomers (e.g., greater than 0 wt% to 5 wt% of one or more phosphorus-containing monomers or greater than 0 wt% to 2.5 wt% of one or more phosphorus-containing monomers) based on the total weight of monomers used to form the styrene/acrylic latex or acrylic latex. In certain embodiments, the styrene/acrylic latex or acrylic latex is derived from greater than 0 wt% to 10 wt% (e.g., greater than 0 wt% to 5 wt%, greater than 0 wt% to 3 wt%, greater than 0 wt% to 2.5 wt%, or greater than 0 wt% to 1.5 wt%) of ethyl 2-phosphate methacrylate (PEM).
The styrene/acrylic latex or acrylic latex may also contain one or more crosslinkable monomers such as acrylamide monomers, methacrylate monomers, acetoacetoxy monomers, ketone monomers, aldehyde monomers, silane monomers, and combinations thereof. Suitable acetoacetoxy monomers are known in the art and include acetoacetoxyalkyl (meth) acrylates, such as acetoacetoxyethyl (meth) acrylate (AAEM), acetoacetoxypropyl (meth) acrylate, acetoacetoxybutyl (meth) acrylate, and 2, 3-di (acetoacetoxy) propyl (meth) acrylate; allyl acetoacetate; acetoacetic acid vinyl ester; and any combination thereof. Suitable ketone monomers include diacetone acrylamide (DAAM). The ketone monomer includes a ketone-containing amide functional monomer defined by the following general structure
CH 2 ═CR 1 C(O)NR 2 C(O)R 3
Wherein R is 1 Is hydrogen or methyl; r is R 2 Is hydrogen, C 1 -C 4 Alkyl or phenyl; and R is 3 Is hydrogen, C 1 -C 4 Alkyl or phenyl. For example, the (meth) acrylamide derivative may be diacetone acrylamide (DAAM) or diacetone methacrylamide. Suitable aldehyde monomers include (meth) acrolein.
The styrene/acrylic latex or acrylic latex may be derived from greater than 0 wt% of one or more acetoacetoxy, ketone, or aldehyde monomers (e.g., at least 0.5 wt%, at least 1 wt%, at least 1.5 wt%, at least 2 wt%, at least 2.5 wt%, at least 3 wt%, at least 3.5 wt%, at least 4 wt%, at least 4.5 wt%, at least 5 wt%, at least 5.5 wt%, at least 6 wt%, at least 6.5 wt%, at least 7 wt%, at least 7.5 wt%, at least 8 wt%, at least 8.5 wt%, at least 9 wt%, at least 9.5 wt%, at least 10 wt%, or at least 15 wt%, based on the total weight of monomers used to form the styrene/acrylic latex or acrylic latex. The styrene/acrylic latex or acrylic latex may be derived from 15 wt% or less of one or more acetoacetoxy, ketone, or aldehyde monomers (e.g., 10 wt% or less, 9.5 wt% or less, 8 wt% or less, 8.5 wt% or less, 8 wt% or less, 7.5 wt% or less, 7 wt% or less, 6.5 wt% or less, 6 wt% or less, 5.5 wt% or less, 5 wt% or less, 4.5 wt% or less, 4 wt% or less, 3.5 wt% or less, 3 wt% or less, 2.5 wt% or less, 1.5 wt% or less, 1 wt% or less, or 0.5 wt% or less) based on the total weight of the monomers used to form the styrene/acrylic latex or acrylic latex.
Acetoacetoxy, keto, or aldehyde groups may react with polyamines to form crosslinks. Polyamines having primary amine groups are preferred. Examples of suitable polyfunctional amines include polyetheramines, polyalkyleneamines, polyhydrazides, or combinations thereof. Specific examples of the polyfunctional amine include polyfunctional amines sold under the trade names Baxxodur, jeffamine and Dytek. In some embodiments, the amine is difunctional or higher functional. Polyfunctional amine-terminated polyoxyalkylene polyols (e.g., jeffamines or Baxxodur amines) are exemplified by polyetheramine T403, polyetheramine D230, polyetheramine D400, polyetheramine D2000 or polyetheramine T5000. In some embodiments, the amine includes Dytek A, dytek EP, dytek HMD, dytek BHMT, and Dytek DCH-99. In some embodiments, the amine is a polyhydrazide derived from aliphatic and aromatic polycarboxylic acids, including adipic acid dihydrazide, succinic acid dihydrazide, citric acid trihydrazide, isophthalic acid dihydrazide, phthalic acid dihydrazide, or trimellitic acid trihydrazide. Other amines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, 5-octaethylenenonamine, higher polyimines, such as polyethyleneimine and polypropyleneimine, bis (3-aminopropyl) amine, bis (4-aminobutyl) amine, bis (5-aminopentyl) amine, bis (6-aminohexyl) amine, 3- (2-aminoethyl) aminopropylamine, N, N-bis (3-aminopropyl) ethylenediamine, N ', N-bis (3-aminopropyl) ethylenediamine, N, N-bis (3-aminopropyl) propane-1, 3-diamine, N, N-bis (3-aminopropyl) butane-1, 4-diamine, N, N ' -bis (3-aminopropyl) propane-1, 3-diamine, N, N ' -bis (3-aminopropyl) butane-1, 4-diamine, N, N ' -tetra (3-aminopropyl) ethylenediamine, N, N ' -tetra (3-aminopropyl) ethylenediamine, N, N ' -N, N ' -bis (3-aminopropyl) ethylenediamine, N, N, N ' -amino-4-aminopropyl) propane-1, 3-diamine, N, N ' -amino-butanediamine, N, N, N ' -bis (3-aminopropyl) amine, N, N, N ' -amino-4-amino-3-aminopropyl) butanediamine, tri (2-amino-tributylamine Tris (5-aminopentyl) amine, tris (6-aminohexyl) amine, triaminohexane, triamionononane, 4-aminomethyl-1, 8-octamethylenediamine. When diacetone acrylamide and its derivative monomers are used, the preferred amine is polyhydrazide or adipic acid dihydrazide.
The ratio of acetoacetoxy, keto, or aldehyde groups to primary amine groups varies from 10:1 equivalents to 1:1.2 equivalents (e.g., 9:1 equivalents to 1:1.1 equivalents, 8:1 equivalents to 1:1 equivalents, 7:1 equivalents to 1:1 equivalents, 6:1 equivalents to 1:1 equivalents, 5:1 equivalents to 1:1 equivalents).
The styrene/acrylic latex or acrylic latex may be derived from an amount of one or more acetoacetoxy, ketone, or aldehyde monomers ranging from any of the minimum percentages described above to any of the maximum percentages described above. For example, the styrene/acrylic latex or acrylic latex may be derived from greater than 0 to 10 weight percent of one or more acetoacetoxy, ketone, or aldehyde monomers (0.25 to 10 weight percent of one or more acetoacetoxy, ketone, or aldehyde monomers, 0.5 to 5 weight percent of one or more acetoacetoxy, ketone, or aldehyde monomers, 1 to 7.5 weight percent of one or more acetoacetoxy, ketone, or aldehyde monomers, 2.5 to 7.5 weight percent of one or more acetoacetoxy, ketone, or aldehyde monomers, or 5 to 7.5 weight percent of one or more acetoacetoxy, ketone, or aldehyde monomers), based on the total weight of the monomers used to form the styrene/acrylic latex or acrylic latex. In certain embodiments, the styrene/acrylic latex or acrylic latex is derived from greater than 0 wt% to 10 wt% (e.g., 1 wt% to 7.5 wt%, 2.5 wt% to 7.5 wt%, or 5 wt% to 7.5 wt%) acetoacetoxyethyl (meth) acrylate (AAEM). In certain embodiments, the styrene/acrylic latex or acrylic latex is derived from greater than 0 wt% to 10 wt% (e.g., 0.25 wt% to 10 wt%, 0.5 wt% to 5 wt%, 1 wt% to 7.5 wt%, 2.5 wt% to 7.5 wt%, or 5 wt% to 7.5 wt%) diacetone acrylamide (DAAM).
The molecular weight of the styrene/acrylic latex or acrylic latex can be determined by its number average molecular weight (M w ) To describe. The weight average molecular weight can be determined using, for example, static light scattering, and can be calculated as shown below, where N i Is of molecular weight M i Molecular number of (2):
M w ＝Σ i N i M i 2 /Σ i N i M i
the styrene/acrylic latex or acrylic latex described herein has a weight average molecular weight Mw of 20,000 daltons or more (e.g., 20,000 daltons or more, 30,000 daltons or more, 40,000 daltons or more, 50,000 daltons or more, 60,000 daltons or more, or 70,000 daltons or more, 80,000 daltons or more, 90,000 daltons or more, or 100,000 daltons or more).
The styrene/acrylic latex or acrylic latex described herein may have a gel content of about 0% to about 100%. The gel content of the styrene/acrylic latex or acrylic latex can be measured by dissolving the dried polymer in Tetrahydrofuran (THF) and measuring the insoluble content. The ratio of insoluble content to total dry polymer can then be determined.
The styrene/acrylic latex or acrylic latex may have a gel content of greater than 50% (e.g., 50% or greater, 60% or greater, 70% or greater, 80% or greater, 90% or greater, or 100%).
In some embodiments, the adhesive a, the aqueous latex emulsion, and one or more additives are combined to form the pressure sensitive adhesive layer a. Exemplary additives include, but are not limited to, thickeners, wetting aids, defoamers, tackifiers, crosslinking agents (e.g., metal salts, silane coupling agents such as glycidoxyalkylalkoxysilane, or multifunctional acrylates such as trimethylolpropane triacrylate (TMPTA) or hexanediol diacrylate (HDDA)), fillers (e.g., calcium carbonate, fibers, carbon black, zinc oxide, titanium dioxide, chalk, solid or hollow glass beads, microbeads of other materials, silica, silicates), low temperature plasticizers, nucleating agents, expanding agents, flow additives, fluorescent additives, polyolefins, rheology modifiers, surfactants, leveling additives, compounding agents and/or aging inhibitors in the form of primary and secondary antioxidants or light stabilizers, photoinitiators, pigments, dyes, or mixtures thereof. The coating may be applied to a surface and dried to produce a pressure sensitive adhesive coating. The pressure sensitive adhesives disclosed herein may produce releasable (temporary) or permanent adhesive bonds.
Exemplary tackifiers (tackifying resins) include, but are not limited to, natural resins such as rosin and derivatives thereof formed by disproportionation or isomerization, polymerization, dimerization, and/or hydrogenation. Tackifiers can include rosins and rosin derivatives (rosin esters, including rosin derivatives stabilized by, for example, disproportionation or hydrogenation), polyterpene resins, terpene-phenolic resins, alkylphenol resins, and aliphatic, aromatic, and aliphatic-aromatic hydrocarbon resins, as well as combinations thereof. In some embodiments, the tackifying resin may be present in salt form (with, for example, monovalent or multivalent counterions (cations)) or in esterified form. The alcohol used for esterification may be a monohydric or polyhydric alcohol. Exemplary alcohols include, but are not limited to, methanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2, 3-propanethiol, and pentaerythritol.
Exemplary hydrocarbon tackifying resins include, but are not limited to, coumarone-indene resins, polyterpene resins, and hydrocarbon resins based on saturated CH compounds such as butadiene, pentene, methylbutene, isoprene, piperylene, divinyl methane, pentadiene, cyclopentene, cyclopentadiene, cyclohexadiene, styrene, alpha-methylstyrene, and vinyl toluene.
In some embodiments, the tackifying resin is derived from natural rosin. In some embodiments, the tackifying resin is selected from any resin that does not interfere with UV curing (e.g., a resin that does not absorb so much UV radiation that it would satisfactorily prevent PSA curing). In some embodiments, the tackifying resin is a chemically modified rosin. In some embodiments, the tackifying resin is fully hydrogenated. In some embodiments, the rosin comprises rosin acid or a rosin acid derivative. Exemplary commercially available tackifiers include, but are not limited to, those provided by Eastman Chemical Company AX-E (fully hydrogenated rosin is a thermoplastic acid resin produced by hydrogenating rosin to a very high degree), ->85 (hydrogenated rosin ester is a cosmetic grade resin derived from esterification of highly stable gum rosin and glycerol) and +.>9100 (hydrocarbon resins, which are partially hydrogenated water white inert thermoplastic resins derived from petrochemical feedstocks).
Exemplary cross-linking agents include, but are not limited to, metal chelates, polyfunctional isocyanates, polyfunctional amines, polyfunctional alcohols, polyfunctional acrylates, and silane coupling agents such as glycidoxyalkylalkoxysilane. Commercially available include, but are not limited to, BASFTMPTA (trimethylolpropane triacrylate).
In one or more embodiments, the pressure sensitive adhesive layer a may have a thickness of 25 μm to 250 μm, or 25 μm to 100 μm.
Useful adhesive compositions are commercially available. For example, copolymers useful in formulating adhesive A include those available from Kuraray under the trade name Kurarity (TM) (acrylic-based triblock and diblock polymers). Kraton, vector, septon are a series of high performance thermoplastic rubbers that use isoprene technology. It consists of a series of hydrogenated styrene block copolymers which exhibit rubbery properties over a wide range of temperatures and hardness, available from Kuraray.
Hot-melt adhesive B
According to various embodiments described herein, the curable hot melt adhesive that may be used to form the pressure sensitive adhesive layer B may be a UV curable acrylic-based hot melt adhesive or a UV curable styrene block copolymer-based hot melt adhesive. For example, U.S. patent 9,334,423, the entire contents of which are incorporated herein by reference, in particular, the teachings relating to compositions and methods comprising acrylic block copolymers and UV curable copolymers, wherein the compositions are capable of being crosslinked by ultraviolet radiation useful, for example, in pressure sensitive adhesive applications.
Suitable UV curable acrylic-based or styrene-based hot melt adhesives comprise an acrylic block copolymer and/or a styrene block copolymer, a UV curable copolymer and a photoinitiator, wherein the composition is capable of crosslinking by ultraviolet radiation.
The monomers used to form the acrylic and/or styrene block copolymer may include, for example, one or more monomers selected from methyl methacrylate, vinyl aromatic compounds (e.g., styrene), cyclohexyl methacrylate, isobornyl methacrylate, acrylonitrile, or mixtures thereof, to produce a polymer block having a measured glass transition temperature of 50 ℃ to 200 ℃. Exemplary vinyl aromatic compounds include, but are not limited to, styrene, alpha-methyl styrene and para-methyl styrene, vinyl toluene, and mixtures thereof.
The UV curable copolymer may be derived from (meth) acrylate monomers, the UV curable copolymer being capable of being crosslinked by ultraviolet radiation. In some embodiments, the (meth) acrylate monomer is selected from butyl acrylate, 2-ethylhexyl acrylate, and mixtures thereof. The photoinitiator may comprise an acrylated benzophenone. Optionally, the UV curable copolymer may contain functional groups that accept free radicals or cationic photoinitiators initiated by a reaction triggered by UV radiation.
In some embodiments, the photoinitiator is bonded to the monomer units of the UV curable copolymer. For example, the UV curable copolymer may include (meth) acrylate monomer units having pendant benzophenone groups bonded thereto. In some embodiments, the composition may include a photoinitiator that is not bonded to the UV-curable copolymer but is provided separately in the composition (e.g., by post-addition of the photoinitiator to the composition) in addition to or in lieu of the photoinitiator bonded to the UV-curable copolymer.
In one or more embodiments, the adhesive is at least partially cured after being applied to the film, as will be discussed in more detail below. In one or more embodiments, the adhesive is cured to the extent that it is not thermally processable in its pre-cured form. In these or other embodiments, the cured adhesive is characterized by a crosslinked infinite polymer network. When at least partially cured, the adhesive layer of one or more embodiments is substantially free of curing agent residues, such as sulfur or sulfur crosslinks and/or phenolic compounds or phenol-residue crosslinks.
In one or more embodiments, the pressure sensitive adhesive layer B may have a thickness of 50 μm to 250 μm, or 50 μm to 100 μm.
In a preferred embodiment, the total thickness of the layers comprising at least the pressure-sensitive adhesive layer a and the pressure-sensitive adhesive layer B is not more than 650 μm, or not more than 600 μm, or not more than 550 μm, or not more than 500 μm.
Release liner
According to various embodiments described herein, the release liner may be a polymer film or extrudate based on polypropylene, polyester, high density polyethylene, medium density polyethylene, low density polyethylene, polystyrene, or high impact polystyrene, or a cellulosic substrate. It is known in the art that a coating or layer may be applied to the film and/or cellulosic substrate and may include a silicon-containing or fluorine-containing coating. These coatings include, for example, silicone oils, polysiloxanes, or hydrocarbon waxes.
According to various embodiments described herein, the release liner may have a thickness of 50 μm to 500 μm.
Preparation of a multilayer composite
The polymeric films used in the multilayer composites of the present invention can be prepared by conventional techniques and are commercially available. For example, EPDM films useful in the multilayer composites of the present invention include those available from companies such as Carlisle, john Manville, or Firestone, and are provided under various trade names.
According to various embodiments described herein, the curable adhesive may be combined by extrusion onto the polymeric film simultaneously or sequentially using known methods. The adhesive may then be cured by using, for example, UV radiation. The release film may be applied to the adhesive layer, and the film may then be subsequently rolled up for storage and/or shipping. The multilayer composite according to embodiments of the present invention may be prepared by a single continuous process.
Fig. 2 shows a dual slot die 20 that coextrudes adhesive a 22 and hot melt adhesive B24, with adhesive a 22 heated to a temperature sufficient to allow application of the adhesive to polymer film 26 and hot melt adhesive B24 heated to a temperature sufficient to allow application of the adhesive to polymer film 26 to form adhesive coating layer 28. The adhesive coating 28 is subjected to a UV curing step 30 in which sufficient UV energy is applied to the coating to effect the desired curing or crosslinking of the UV curable adhesive. It is generally known in the art and not shown herein that once the adhesive has been sufficiently cured by exposure to a UV curing step, the composite may be passed over one or more chill rolls and a release liner may be applied to the cured coating. After the release liner is applied, the composite is wound. After removal of the release liner, the multi-layer composite is ready to be laminated to the roof of the job site.
According to various embodiments described herein, adhesive a is heated to a temperature of about 120 ℃ to about 160 ℃, in other embodiments to a temperature of about 125 ℃ to about 155 ℃, and in other embodiments to a temperature of about 130 ℃ to about 150 ℃.
Adhesive a has more cold flow than hot melt adhesive B, allowing it to relieve stresses during expansion or contraction of the film during use. The cold flow properties of hot melt adhesives can be quantified, for example, by measuring the modulus of elasticity of the hot melt adhesive. The modulus of elasticity can be determined using methods known to those skilled in the art. In some embodiments, the elastic modulus of adhesive a is less than the elastic modulus of adhesive B, in other embodiments, the elastic modulus of a and B differ by 20%, and in other embodiments, the elastic modulus differs by 50%.
According to various embodiments described herein, the hot melt adhesive B is heated to a temperature of about 120 ℃ to about 160 ℃, in other embodiments to about 125 ℃ to about 155 ℃, in other embodiments to about 130 ℃ to about 150 ℃.
According to various embodiments described herein, the pressure sensitive adhesive layer a may have a thickness of 25 μm to 250 μm, or 25 μm to 100 μm.
According to various embodiments described herein, the pressure sensitive adhesive layer B may have a thickness of 25 μm to 250 μm, or 25 μm to 100 μm.
In one or more embodiments, once layer a and layer B are combined, they may be subjected to a UV curing step. The UV curing step subjects the adhesive coating to a UV dose of about 40 millijoules/cm 2 to about 80 millijoules/cm 2. It is advantageously observed that the UV dose of the present invention maintains good peel, while the lower thickness allows good penetration cure and maintains good shear. It is well known that subjecting an adhesive coating to high doses of UV radiation causes non-uniformity and has a detrimental effect on the coating.
Characteristics of multilayer composite
According to various embodiments described herein, the crosslinked pressure sensitive adhesive B layer disposed on the surface of a film according to the present invention may be characterized by an advantageous peel strength of at least 4 pounds, or at least 5 pounds, or at least 6 pounds, or at least 7 pounds, or at least 8 pounds.
In one or more embodiments, the crosslinked pressure sensitive adhesive layer disposed on the surface of a film according to the present invention may be characterized by an advantageous static shear minimum of 15 hours, or at least 16 hours, or at least 17 hours, or at least 18 hours, or at least 19 hours, or at least 20 hours, or at least 21 hours, or at least 22 hours, or at least 23 hours, or at least 24 hours, or at least 25 hours; under 1kg, the dimensions were 1 inch by 1 inch.
Application to roof surfaces
The multilayer composite of the present invention can be advantageously applied to a roof surface (also referred to as a roof substrate) by using standard peel-and-stick techniques. These techniques are known to those skilled in the art. For example, the multi-layer composite may be spread out over a roof surface and placed in place. The multilayer composite can then be adhered to a roof surface by using various techniques including fitting the adhesive to the substrate using rollers or the like.
It has been advantageously found that the pressure sensitive adhesive layer used in the films of the present invention allows the adhesion of the multilayer composite to various roof surfaces. These include, but are not limited to, wood platforms, concrete platforms, steel platforms, faced building panels, and existing film surfaces. In certain embodiments, the films of the present invention are adhered to faced building panels, such as, but not limited to, polyisocyanurate insulation panels or cover sheets comprising a facing made from polar materials, by the cured adhesive layers disclosed herein. For example, the adhesives of the invention provide for advantageous adhesion to a facing comprising cellulosic and/or glass materials. It is believed that the polar nature of the adhesive is highly compatible with the polar nature of these facing materials and/or any adhesives or coatings that may be carried by the glass or paper facing. Accordingly, embodiments of the present invention relate to a roof deck comprising a building panel having a cellulose or glass finish and a membrane secured to the building panel by an at least partially cured polyacrylate adhesive layer in contact with the glass or cellulose finish of the building panel.
It has been advantageously found that the pressure sensitive adhesive layer used in the multilayer composites of the present invention allows the multilayer composites to be applied to roof surfaces in any temperature window and at any installation time without exhibiting channeling and tunneling.
Examples
This example demonstrates the advantages and performance characteristics of the present invention.
Examples
Example 1: multilayer composite material
Five multi-layer composites were formulated using the starting materials and conditions shown in table 1 below. The LSE components of formulations 1 and 2 comprise two different UV curable acrylates and rosin esters as tackifiers. The heat curing (TC) component of formulation 2 was a combination of acrain and joncryl 4285 crosslinker (97/2.5). In this example, water-based acrylic acid was modified with Lumiten 0.5% ISC and thickened to a viscosity of about 15,000cp, then mixed under vacuum. The coating is added or transferred directly to an Ethylene Propylene Diene Monomer (EPDM) substrate.
TABLE 1
Example 2: peel strength and shear adhesion test
The five formulations described above were then fixed to stainless steel panels and the test specimens were then tested for peel strength according to PSTC 101 ("SS peel"). Each test was repeated three times. The results are shown in Table 2.
TABLE 2
Formulation 1 exhibited failure of about the same measure in terms of cohesion and adhesion to EPDM. Formulation 2 showed failure mainly in cohesive properties, with some failure in adhesion to EPDM. Cohesive failure of formulations 3 and 4. Formulation 5 shows different failure modes, referred to herein as "banding". This failure mode leaves alternating solid stripes of adhesive on the substrate as the force builds until the adhesion fails and the adhesive is released from the substrate, whereupon the cycle begins again. This results in a steady rise in force, followed by a sudden drop, followed by another steady rise and another sudden drop, etc.
The formulations were then subjected to a shear adhesion failure test ("SAFT") according to TEST METHODS for Pressure Sensitive Adhesive Tapes, 16 th edition from Pressure Sensitive Tape Counsil (PSTC) 2014 test method PSTC-17. The results are shown in Table 3.
TABLE 3 Table 3
In each case, the primary failure mode is through cohesive failure.
From the results of tables 2 and 3, it can be seen that the performance of formulation 1 is comparable to or better than the rest of the formulation.
Various modifications and alterations that do not depart from the scope and spirit of this invention will become apparent to those skilled in the art. The present invention should not be limited to only the illustrative embodiments described herein.
All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
The use of the terms "a" and "an" and "the" and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.
The term "substantially all" refers to an amount or area coverage of 80% or greater and is intended only as a shorthand method of referring individually to each individual value in the range of 80% to 100%.
Preferred embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. It should be understood that the illustrated embodiments are exemplary only, and should not be taken as limiting the scope of the invention.

Claims (29)

1. A multilayer composite, the multilayer composite comprising:
a polymer film;
an adhesive layer A;
a hot melt adhesive layer B; and
the release liner is provided with a release liner,
wherein the adhesive layer a comprises an Ultraviolet (UV) curable pressure sensitive adhesive or an aqueous latex adhesive;
wherein the hot melt adhesive layer B comprises an at least partially cured Ultraviolet (UV) curable pressure sensitive adhesive;
wherein the adhesive layer A has a thickness of 25 μm to 250 μm, and
wherein the hot melt adhesive layer B has a thickness of 50 μm to 250 μm.
2. The multilayer composite of claim 1, wherein the adhesive layer a does not undergo UV curing prior to combination with layer B.
3. The multilayer composite of claim 1, wherein said adhesive layer a is in contact with substantially all of one planar surface of said polymer film.
4. The multilayer composite of claim 1, wherein said hot melt adhesive layer B is in contact with substantially all of one planar surface of said polymer film.
5. The multilayer composite of claim 1, wherein said adhesive layer a comprises a UV cured poly (acrylate) resin.
6. The multilayer composite of claim 1, wherein the aqueous latex binder comprises at least one styrene/acrylic latex, styrene butadiene latex, or nitrile butadiene latex derived from at least one monomer selected from styrene, 2-ethylhexyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylamide, acrylic acid, methacrylic acid, itaconic acid, and vinylphosphonic acid.
7. The multilayer composite of claim 1, wherein said hot melt adhesive layer B is selected from the group consisting of UV curable acrylic PSA and UV curable styrene block copolymer PSA.
8. The multilayer composite of claim 1, wherein said polymer film is selected from the group consisting of thermoplastic films, ethylene-propylene-diene terpolymer rubber (EPDM), TPO, PVC, modified asphalt, rubber films, asphalt films, and fibrous films.
9. The multilayer composite of claim 1, wherein the multilayer composite has a peel strength of at least 6psi when adhered to a stainless steel panel and tested according to PSTC 101.
10. The multilayer composite of claim 1, wherein the multilayer composite has a static shear of at least 0.5 hours when adhered to a stainless steel panel and tested according to PSTC 107.
11. The multilayer composite of claim 1, wherein the adhesive layer a has a thickness of 25 μιη to 100 μιη, and wherein the hot melt adhesive layer B has a thickness of 50 μιη to 100 μιη.
12. The multilayer composite of claim 11, wherein said adhesive layer a further comprises one or more additives.
13. The multilayer composite of claim 1, wherein the multilayer composite is a roofing membrane.
14. A roofing membrane comprising the multilayer composite of claim 1.
15. A method for forming a multi-layer composite, the method comprising:
(a) The melt-extrudable UV curable pressure sensitive layer a is heated,
(b) The melt-extrudable UV curable pressure sensitive adhesive B is heated,
(c) Extruding the layer a and the adhesive B onto a planar surface of a polymer film such that the adhesive is in contact with substantially all of one planar surface of the polymer film, thereby forming an adhesive coating layer comprising an adhesive layer a and a hot melt adhesive layer B;
Wherein the adhesive layer A has a thickness of 25 μm to 250 μm, and
wherein the hot melt adhesive layer B has a thickness of 50 μm to 250 μm,
(d) Subjecting the adhesive coating layer to UV radiation;
(e) Optionally, cooling the adhesive coating layer;
(f) Applying a release liner to the adhesive coating layer to form a multilayer composite; and
(g) Winding the composite material.
16. The method of claim 15, wherein the melt-extrudable UV curable pressure sensitive layer a further comprises an aqueous latex adhesive.
17. The method of claim 15, wherein in step (c), the adhesive a and the adhesive B are co-extruded simultaneously.
18. The method of claim 15, wherein in step (c), the adhesive layer a and the adhesive B are sequentially extruded.
19. The method of claim 15, wherein the adhesive layer a comprises a UV curable poly (acrylate) resin and an aqueous latex adhesive.
20. The method of claim 15, the hot melt adhesive layer B comprising a UV cured poly (acrylate) resin.
21. The method of claim 15 wherein the hot melt adhesive layer B is selected from the group consisting of UV curable acrylic PSA and UV curable styrene block copolymer PSA.
22. The method of claim 15, wherein the polymer membrane is selected from the group consisting of thermoplastic membranes, ethylene-propylene-diene terpolymer rubber (EPDM), TPO, PVC, modified asphalt, rubber membranes, asphalt membranes, and fibrous membranes.
23. The method of claim 15, wherein the adhesive a and the adhesive B that are co-extruded simultaneously in a dual slot die configuration onto a moving web of thermoplastic film, ethylene-propylene-diene terpolymer rubber (EPDM), TPO, PVC, modified asphalt, rubber film, asphalt film, and fibrous film.
24. The method of claim 15, wherein the adhesive a and/or the adhesive B comprises an additive selected from a tackifier, a plasticizer, one or more photoinitiators.
25. The method of claim 15, wherein the adhesive a/B is heated to a temperature of about 120 ℃ to about 160 ℃.
26. The method of claim 15, wherein subjecting a coating to UV radiation comprises subjecting the adhesive coating layer to a UV dose of about 40 millijoules/cm 2 to about 80 millijoules/cm 2.
27. The method of claim 15, wherein the multilayer composite has a width of about 1 meter to about 20 meters.
28. A method for roofing a structure, the method comprising:
(a) Providing a multi-layer composite according to claim 1,
(b) Removing the release liner from the multilayer composite, thereby forming a linerless multilayer composite, and
(c) The linerless multilayer composite is adhered/laminated/mounted to a roof sub-structure to form a roof laminate.
29. A multilayer composite, the multilayer composite comprising:
a substrate;
an adhesive layer A;
a hot melt adhesive layer B; and
the release liner is provided with a release liner,
wherein the adhesive layer a comprises an Ultraviolet (UV) curable pressure sensitive adhesive and an aqueous latex adhesive;
wherein the hot melt adhesive layer B comprises an at least partially cured Ultraviolet (UV) curable pressure sensitive adhesive;
wherein the adhesive layer a has a thickness of 25 μm to 250 μm, and wherein the hot melt adhesive layer B has a thickness of 50 μm to 250 μm.
CN202280020575.2A 2021-03-12 2022-03-11 Multilayer composite with double layer pressure sensitive adhesive Pending CN117062888A (en)

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PCT/US2022/019975 WO2022192686A1 (en) 2021-03-12 2022-03-11 Multilayer composite with dual layer pressure-sensitive adhesive

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