Ionomer resin composition

Abstract

Provided is an ionomer resin composition containing sodium-neutralized ethylene-acid copolymer and a recovered dialkoxysilane adhesion promoter, and methods for making and using such compositions. The sodium-neutralized ethylene-acid copolymer used is preferably a combination of a "newly produced" or "virgin" copolymer and a recovered copolymer, and the dialkoxysilane adhesion promoter additive used is at least partially present in the form of recycled material and is combined with the copolymer in the form of recycled material. The ionomer resin composition has enhanced adhesion to glass in many beneficial properties and uses, and is therefore particularly suitable for use in the manufacture of interlayers and glass laminates containing such interlayers.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application Serial No. 63 / 354,307 and U.S. Provisional Application Serial No. 63 / 354,335, both filed on June 22, 2022, both of which are incorporated herein by reference in their entirety for all purposes as if fully set forth. Technical Field

[0003] The present invention relates to ionomer resin compositions comprising sodium-neutralized ethylene-acid copolymers and dialkoxysilane adhesion promoters, and methods of making and using such compositions. The sodium-neutralized ethylene-acid copolymers used are preferably "virgin" or "fresh" copolymers, and the dialkoxysilane adhesion promoter additives used are preferably initially present in the form of recycled material and combined with the copolymer in the form of recycled material. Preferably, the sodium-neutralized ethylene-acid copolymer is one or a combination of sodium-neutralized ethylene-acid dipolymers and sodium-neutralized ethylene-acid-ester terpolymers. The ionomer resin compositions have enhanced adhesion to glass among many beneficial properties and uses, and are therefore particularly suitable for use in making interlayers and glass laminates containing such interlayers. Background Art

[0004] Laminated glass is typically made by laminating two sheets of glass to a plastic interlayer. A particular advantage of laminated glass over solid sheets of glass is the impact and shatter resistance it offers due to the adhesion of the glass to the interlayer sheets.

[0005] In safety glass laminates, optimal adhesion of the interlayer to the glass is a balance. Too much adhesion reduces the ability of the laminate to absorb and dissipate energy during an impact event, while too little adhesion can cause optical defects (both during and after lamination) and can also adversely affect the interlayer's ability to retain glass fragments during an impact.

[0006] Many different materials have been used as plastic interlayers. For example, sheets containing polyvinyl acetal (polyvinyl butyral) and a plasticizer are widely used as interlayers for laminated glass because of their excellent adhesion to glass. Laminated glass containing such interlayers can be made to have good transparency, mechanical strength, flexibility, sound damping, and shatter resistance.

[0007] At least partially neutralized ethylene-acid copolymers (ionomers) have also been used as interlayers for preparing laminated safety glass, for example, as disclosed in US3404134, US3344014, US7445683B2, US7763360B2, US7951865B1, US7960017B2, US8399097B2, US8399098B2, US2017 / 0320297A1, US2018 / 0117883A1, WO2016 / 076336A1, WO2016 / 076337A1, WO2016 / 076338A1, WO2016 / 076339A1 and WO2016 / 076340A1.

[0008] While ionomer resins may be selected to produce interlayers with excellent flexural strength and optical properties, the glass adhesion properties to glass may not be optimal. In particular, because ionomers are neutralized acid copolymers, they do have a tendency to develop lamination defects, especially in high humidity environments.

[0009] For example, when using ionomer resins as interlayers for float glass, adhesion is generally satisfactory on the "tin side" of the glass rather than the "air side", so special precautions need to be taken in the lamination process to properly orient such glass sheets to ensure "tin side" contact with the interlayer.

[0010] The use of primers and other surface treatments of the glass and interlayers have been proposed to help address the adhesion issue (see, e.g., US 2016 / 0159042 A1), but this adds cost and complexity to the lamination process, and such surface treatments often result in excessive adhesion which, as previously discussed, reduces the ability of the laminate to absorb and dissipate energy during an impact event.

[0011] Ionomer resin modification and compounding with additives have also been attempted. For example, increasing the acid level of ethylene-acid copolymers does improve the adhesion properties of the final ionomer; however, there are practical and economic limits to how much the acid number can be increased. Additives have also been used with limited success.

[0012] In particular, silanes are known to be excellent adhesion promoters to glass in many different resin systems. However, as disclosed in US20110105681A1, silanes are often used with ionomers, especially with sodium neutralized ionomers, to produce gels and do not generate a melt flow that allows sheet extrusion to be accomplished in a satisfactory manner. This particular disclosure identifies a small range of amino-containing dialkoxysilanes that can be used in combination with only a specific type of zinc neutralized ionomer.

[0013] Commonly owned US2019030863A1 provides a sodium neutralized ethylene-acid copolymer ionomer composition containing a specific dialkoxysilane silane additive in a specific amount without the problems described in US20110105681A1 and having enhanced adhesion to glass on both the tin side and the air side of float glass.

[0014] Ionomers are thermoplastic and recyclable. Ideally, they can be repeatedly melted and reshaped into new products. Methods for recycling ionomer materials are disclosed by D. Sykutera, P. Czyzewski in Journal of Polish CIMAC, vol7, no.3, pp 301-308, Gdansk, 2012; and by JG Poulakis, CD Papaspyrides in Adv in Polymer Technology, Vol 19, No 3, 203-209 (2000). Typically, these methods involve cooling the ionomer and cutting the waste ionomer into appropriate sizes to allow remelting and reprocessing to form injection molded products. However, each thermal cycle degrades the polymer and imparts undesirable properties such as color to the polymer, and the use of these recycled ionomers in interlayers (films and sheets) for glass laminates (where clarity is a key parameter) is not disclosed.

[0015] Thermal cycling can be expected to degrade any silane adhesion promoters remaining in the recycled material. In fact, because silane groups are known to be sensitive to moisture, oxygen, and other environmental factors, it can be expected that most of the silane adhesion promoters originally present in the material will be degraded due to environmental exposure during use of products made from the ionomers and uncontrolled environmental exposure during recycling.

[0016] Contrary to such expectations, it has now been discovered that "used" materials originally containing specific silane adhesion promoters can be successfully and advantageously used as recycled materials while still imparting glass adhesion properties, allowing, among other things, the optimal use of such silanes and ionomers in the preparation of films and sheets such as interlayers and glass laminates having enhanced interlayer adhesion properties to glass. In addition, because the silanes used herein are preferably used at least in part in the form of recycled materials, the advantages described herein are improved overall efficiency, reduced raw material requirements, reduced waste and energy savings in the manufacture of, for example, films and sheets. Although methods of using recycled ionomer materials are known, the issue of the differences in appearance between laminates made using ionomers without the addition of recycled materials and those made using ionomers with the addition of recycled materials has not been disclosed. Some of these appearance differences include, but are not limited to, clarity, haziness, color, modulus and tensile strength. In addition, the effects of different cooling cycles on ionomers with the addition of recycled materials have not been previously documented, but are documented herein.

[0017] As used herein, when the terms "invention" and "present invention" and the like are used, they refer only to the specific embodiments that follow. They are not intended to be broadly limiting in general or with respect to some advances in the art described herein. Summary of the invention

[0018] The present invention solves the above problems in one embodiment by providing an ionomer resin composition comprising a blend of a dialkoxysilane adhesion promoter and an ionomer resin, wherein the ionomer resin is (i) an at least partially sodium neutralized ethylene-acid copolymer ionomer resin, or

[0019] (ii) an at least partially sodium neutralized ethylene-acid-ester terpolymer ionomer resin, or

[0020] (iii) any combination of (i) and (ii),

[0021] and wherein at least a portion of the dialkoxysilane adhesion promoter and optionally at least a portion of the ionomer resin is present in the form of recycled material.

[0022] In one embodiment, the sodium neutralized ethylene-acid dipolymer ionomer resin (i) is an at least partially sodium neutralized ethylene-acid dipolymer resin consisting essentially of or consisting of copolymerized units of ethylene and at least one α,β-unsaturated carboxylic acid. In another embodiment, the sodium neutralized ethylene-acid-ester terpolymer ionomer resin (ii) is an at least partially sodium neutralized ethylene-acid terpolymer resin comprising, consisting essentially of, or consisting of copolymerized units of ethylene, at least one α,β-unsaturated carboxylic acid, at least one α,β-unsaturated carboxylic acid ester, and optionally a derivative of an α,β-unsaturated carboxylic acid other than an ester (such as an amide or anhydride, etc.).

[0023] In one embodiment, the dialkoxysilane adhesion promoter is present in the ionomer resin composition in a total amount ranging from about 50 to about 5000 parts by weight per million parts by weight, based on the weight of the ionomer resin.

[0024] In one embodiment, the dialkoxysilane adhesion promoter is substantially uniformly distributed within the resin composition. In another embodiment, the ionomer resin composition is a granular resin composition.

[0025] In another embodiment, the recycled material used herein comprises, consists essentially of, or consists of one of the above-mentioned co-polymer and ter-polymer ionomer resins, at least one dialkoxysilane adhesion promoter, and optional additives.

[0026] In one embodiment, the ionomer resin is a combination of virgin and recycled materials.

[0027] In another embodiment, the ionomer compositions, films, laminates, etc. described herein comprise both an at least partially sodium neutralized ethylene-acid dipolymer ionomer resin and an at least partially sodium neutralized ethylene-acid-ester terpolymer ionomer resin and a recycled material containing a dialkoxysilane adhesion promoter.

[0028] In all embodiments herein, the amount of dialkoxysilane adhesion promoter present in a given composition can be calculated, for example, based on the amount of recycled material used, the amount of dialkoxysilane adhesion promoter known to be present in the recycled material, and the amount of any additional dialkoxysilane adhesion promoter known to be added thereto. The amount of dialkoxysilane adhesion promoter present in a given composition relative to the total amount of dipolymer and / or terpolymer present can be similarly calculated, for example, based on the amount of recycled material used, the amount of dialkoxysilane adhesion promoter known to be present in the recycled material, the amount of any additional dialkoxysilane adhesion promoter known to be added thereto, the amount of dipolymer and / or terpolymer ionomer resin known to be present in the recycled material (if any), and the amount of virgin or new dipolymer and / or terpolymer known to be used.

[0029] In all embodiments herein, it is preferred that at least a portion of the sodium-neutralized ethylene-acid copolymers (eg, co-polymers and ter-polymers) used is virgin or newly produced copolymer.

[0030] In another aspect, the present invention provides a first method for making an ionomer resin composition, the method comprising the step of mixing the above-mentioned recycled material containing a dialkoxysilane adhesion promoter with the above-mentioned sodium-neutralized ethylene-acid copolymer.

[0031] In one embodiment of the above method, the dialkoxysilane compound is substantially uniformly distributed within the resin composition. In another embodiment, the mixing step is a melt blending step. In another embodiment, the binary copolymer and / or terpolymer ionomer resin is granular, the mixing step is performed under non-softening conditions for both the binary copolymer and terpolymer ionomer resins, and the resin composition is a granular resin composition.

[0032] In another aspect, the present invention provides a method comprising the following steps: in an extruder, the above-mentioned recycled material is co-extruded with the above-mentioned sodium-neutralized ethylene-acid dipolymer and / or alkali metal-neutralized ethylene-acid-ester terpolymer, optionally with one or more additives selected from ultraviolet absorbers, antioxidants, light stabilizers and colorants, under conditions of melting and intimately mixing the recycled material with the dipolymer and / or terpolymer to produce a melt; and optionally, the melt is formed into a film or sheet having a thickness substantially continuous in the machine direction, for example, a thickness of up to about 2.5 mm.

[0033] In one embodiment of the coextrusion process, the recycled material is in the form of granules. In another embodiment, the bipolymer and / or terpolymer is in the form of pellets.

[0034] In one embodiment, the dialkoxysilane compound contains a carboxylic acid reactive group in addition to two alkoxysilyl groups. In one embodiment, the carboxylic acid reactive group is an amino group or a glycidyl group.

[0035] In another embodiment, the present invention provides a method of making a sheet of an ionomer resin composition by melt blending one of the above-mentioned granular resin compositions under shear to make a melt blend, then extruding the melt blend through a die into a sheet form, and then cooling the sheet form to solidify the resin composition. In one embodiment, the sheet has an upper side and a lower side, and the sheet is optionally embossed with a pattern on one or both of the upper side and the lower side before solidification.

[0036] In other aspects, the present invention provides interlayer sheets of such resin compositions and glass laminates made from such interlayer sheets, for example, comprising two sheets of glass with an interlayer according to the present invention interposed therebetween.

[0037] In one embodiment, the interlayer sheet is optionally pre-treated at 34° C. and 50% relative humidity, the interlayer is adhered to the air side of a float glass sheet having an air side and a tin side, and the peel adhesion of the interlayer adhered to the air side of the float glass sheet measured at 23° C. and 50% RH is greater than about 5 N / cm, or greater than about 10 N / cm, or at least about 20 N / cm, and less than about 100 N / cm, or less than about 90 N / cm, or less than about 80 N / cm, or less than about 70 N / cm.

[0038] These and other embodiments (all of which may be used in combination), features and advantages of the present invention will be more readily understood by those of ordinary skill in the art upon reading the following detailed description. DETAILED DESCRIPTION

[0039] The present invention relates to resin compositions comprising at least one recycled material, masterbatches thereof, films, sheets and interlayers prepared therefrom or from masterbatches thereof, glass laminates containing such interlayers and methods of making the same. Further details are provided below.

[0040] Throughout the present specification, unless otherwise indicated, all publications, patent applications, patents, and other references mentioned herein are expressly incorporated by reference in their entirety for all purposes as if fully set forth.

[0041] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In the event of a conflict, the present specification, including definitions, will control.

[0042] Unless expressly stated otherwise, trademarks appear in capital letters.

[0043] Unless otherwise indicated, all percentages, parts, ratios, etc. are by weight.

[0044] Unless otherwise specified, pressures expressed in psi are gauge pressures, while pressures expressed in kPa are absolute pressures. However, pressure differences are expressed as absolute values ​​(e.g., Pressure 1 is 25 psi higher than Pressure 2).

[0045] When an amount, concentration or other value or parameter is given as a range or an upper and lower limit, this should be understood as specifically disclosing all ranges formed by any pair of any range upper and lower limits, whether or not the range is disclosed separately. Where a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints, as well as all integers and fractions within the range. When defining a range, the scope of the present disclosure is not intended to be limited to the specific value described. As an example, the range 1-10 fully describes and includes independent subranges 3.4-7.2.

[0046] When the term "about" is used, it is used to mean that a certain effect or result can be obtained within a certain tolerance, and those skilled in the art know how to obtain the tolerance. When the term "about" is used to describe a value or end point of a range, the disclosure should be understood to include the specific value or end point referred to.

[0047] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0048] The transitional phrase "consisting of" excludes any element, step, or ingredient not specified in the claim, making the claim closed to exclude those materials recited except for the impurities normally associated therewith. When the phrase "consisting of" appears in a clause of the body of the claim rather than immediately following the preamble, it is limited only to the elements set forth in that clause; other elements are not excluded from the claim as a whole.

[0049] The transition phrase "consisting essentially of limits the scope of a claim to the specified materials or steps and to those materials or steps that do not materially affect the basic and novel characteristics of the claimed invention. "Consisting essentially of" claims occupy a middle ground between closed claims written in the "consisting of" format and fully open claims drafted in the "comprising" format. By the term "consisting essentially of," optional additives (in amounts appropriate to such additives) and minor impurities as defined herein are not excluded from the embodiments unless they materially affect the basic and novel characteristics of the embodiment in question.

[0050] In addition, unless explicitly stated to the contrary, "or" and "and / or" are meant to be inclusive rather than exclusive. For example, condition A or B or A and / or B is satisfied by any of the following: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0051] The use of "a" or "an" to describe various elements and components herein is merely for convenience and to give a general meaning to the present disclosure. The description should be understood to include one or at least one, and the singular also includes the plural, unless it is obvious that there is another meaning.

[0052] Unless otherwise defined herein, the term "major portion" or "predominantly" as used herein means greater than 50% of the referenced material. If not specified, percentages are based on moles when referring to molecules (such as hydrogen and ethylene) and weight otherwise (such as additive content).

[0053] Unless otherwise defined, the term "substantial portion" or "substantially" as used herein means all or nearly all or a majority, as would be understood by a person of ordinary skill in the context used. This is intended to take into account some reasonable variances from 100% that would normally occur in industrial or commercial scale situations.

[0054] The terms "deplete" or "reduce" are synonymous with reduced from an initial presence. For example, removing a substantial portion of a material from a stream will produce a material-depleted stream substantially depleted of that material. Conversely, the terms "enrich" or "increase" are synonymous with greater than an initial presence.

[0055] As used herein, the term "virgin" refers to newly produced, generally pure materials. The form of such materials may vary depending on their manufacturing method. Simply changing the physical form of such materials by, for example, physical or thermal means (e.g., grinding, chopping, melting, etc.), without changing more (e.g., chemical changes, degradation, mixing of other materials, etc.), does not change their "original" properties.

[0056] As used herein, the term "particle" means a particle from a highly irregular shape to a spherical scope. Particle "size" can be defined as the weight of every 100 particles. In one embodiment, particle "size" is approximately 0.01 to 10 grams. In another embodiment, although the suitable size of the recovered material particles (granules) (particles (particles)) is usually unrestricted, its size range can be approximately 0.1mm, or approximately 0.2mm, to approximately 5mm, or to approximately 4mm, or to approximately 2mm, or to approximately 1mm. Particle can be porous, can also comprise the collection of smaller particles of "aggregation" or "fusion" together slightly, and therefore physically manifests as larger particles / particles.

[0057] As used herein, the term "pellets" means polymer resin, generally having a cylindrical shape (strand cut) or a nearly spherical shape (eg, underwater melt cut), with a weight of 0.1 to 10 grams per 100 pellets.

[0058] As used herein, the term "virgin" refers to generally pure material that is newly manufactured or as received from a supplier and has not been subjected to any post-processing intended to produce another form / shape or heat treatment that causes the resin to melt.

[0059] As used herein, the terms "intimately mix," "intimately mixing," "intimately mixed," and "intimate mixing" mean combining or combining two or more polymeric materials - e.g., virgin ionomer and recycled material - such that optimal optical distortion parameters are achieved. Thermal processing (melt mixing, etc.) is typically involved. Measurement of optical distortion may be performed by any practical method, including but not limited to "shadowgraph" techniques. Shadowgraphs are a sensitive visualization method that can reveal optical inhomogeneities within a transparent material, typically through shadow casting caused by disturbances in the refraction of light. Another common practice is to determine the degree of optical distortion present when a "chessboard" target grid is observed with or without a sample glass laminate placed in direct line of sight.

[0060] As used herein, the term "formulation" when referring to polymeric materials means forming the material into films and sheets. Typically, the thickness of the film is from about 0.01 to about 0.25 mm, and the thickness of the sheet is from about 0.25 mm to about 10 mm.

[0061] As used herein, the term "longitudinal direction" means the primary direction of material flow from a film or sheet manufacturing process. In the case of an extrusion process that produces a melt formed into a film or sheet, this is sometimes also referred to as the "machine direction".

[0062] As used herein, the terms "plastic" and "polymer" are used interchangeably. Although it should be recognized that the term "plastic" can refer to a specific type of polymer, and is generally composed of long chains of polymers, and polymers are composed of smaller uniform molecules, for the present invention, the two terms can be used interchangeably.

[0063] The measurements of haze, YID and other properties are carried out in the form of glass laminates. The combination of haze and yellowness index (YID), especially with a fast cooling curve, can have a small haze difference, but a large YID difference. Substantially all (about 100%) of each resin can have an acceptable YID, but the combination of two resins can have an increased yellowness. This is particularly important for mixing recycled materials with different thermal curves. Note the difference between "conventional" cooling and "fast" cooling, as well as the difference when different resin combinations, and the difference in the amount of each resin and the cooling method used. Ionomer resins can be added with blue colorants (to make the interlayer film / sheet look less yellow), but this is an addition step, and the addition of such colorants will only compensate for the degree of yellowness at a given composition blend and cooling rate. In addition, this method will shift the "color" of the resin toward "green" or even "grey", and in substantially all cases, will reduce the total light transmittance of the product, which will further distinguish between resin blends with or without blue colorants. Additionally, the refractive index (RI) of each resin is important, especially for haze. This is also often related to mixing. The thickness of the glass laminate interlayer must also be considered, as well as any effects of extrusion methods and resin degradation.

[0064] As used herein, the terms "recycled material" and "recycled polymer material" each refer to a polymer material containing at least one dialkoxysilane adhesion promoter and recovered from a previously manufactured polymer material. The previously manufactured polymer material may be in any form and may be or may include waste materials from the process used to manufacture it, i.e., defective products and trimmings, etc. The polymer material contains not only one or more polymers, but also at least one dialkoxysilane adhesion promoter and optionally more than one additional additive. Therefore, when the polymer material is recycled, it is also considered that at least one dialkoxysilane adhesion promoter and optional additional additives are "recycled". Recycled polymer material may also be obtained from downstream manufacturing operations, such as trimmings in the conversion process of films and sheets manufactured as glass laminates. In addition, it is feasible that the collected polymer material can be reprocessed to filter out contaminants through a secondary extrusion process to produce a material suitable for use.

[0065] As used herein, the term "copolymer" refers to a polymer comprising copolymer units produced by copolymerization of two or more comonomers. In this regard, copolymers may be described herein with reference to their constituent comonomers or the amounts of their constituent comonomers, such as "a copolymer comprising ethylene and 15% by weight of acrylic acid" or similar descriptions. Such descriptions may be considered informal because they do not refer to comonomers as comonomers; because they do not include conventional nomenclature for copolymers, such as the International Union of Pure and Applied Chemistry (IUPAC) nomenclature; because they do not use methods to define product (product-by-process) terms; or for other reasons. However, as used herein, copolymer descriptions involving constituent comonomers of copolymers or the amounts of their constituent comonomers mean that copolymers contain comonomer units of specific comonomers (when specified in a specified amount). The inference drawn therefrom is that copolymers are not the product of a reaction mixture containing a given amount of a given comonomer, unless explicitly stated to be so in limited circumstances.

[0066] The term "dipolymer" refers to a polymer consisting essentially of two monomers, and the term "terpolymer" refers to a polymer comprising at least three monomers.

[0067] As used herein, the term "acid copolymer" refers to a copolymer comprising copolymerized units of an α-olefin, an α,β-ethylenically unsaturated carboxylic acid, and optionally other suitable comonomers such as α,β-ethylenically unsaturated carboxylic acid esters.

[0068] As used herein, the term "(meth)acrylic" (eg, "(meth)acrylate"), alone or in combination, refers to acrylic or methacrylic, for example, "acrylic acid or methacrylic acid" or "alkyl acrylate or methacrylate."

[0069] As used herein, the term "ionomer" generally refers to a polymer comprising an ionic group, which is a carboxylate, such as an ammonium carboxylate, an alkali metal carboxylate, an alkaline earth metal carboxylate, a transition metal carboxylate and / or a combination of such carboxylates. Such polymers are generally prepared by partially or completely neutralizing the carboxylic acid groups of a precursor or parent polymer (acid copolymer as defined herein), such as by reacting with a base. As used herein, an alkali metal ionomer is a sodium ionomer, such as a copolymer of ethylene and methacrylic acid, wherein all or part of the carboxylic acid groups of the copolymerized methacrylic acid units are neutralized, and substantially all of the neutralized carboxylic acid groups are in the form of sodium carboxylates.

[0070] For convenience, many elements of the present invention are discussed separately, lists of options may be provided and values ​​may be within ranges; however, for the purposes of this disclosure, this should not be considered a limitation on the scope of the present disclosure or support for any claim of the present disclosure for any combination of any such individual components, lists or ranges. Unless otherwise stated, every possible combination of the present disclosure should be considered to be explicitly disclosed for all purposes.

[0071] Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, suitable methods and materials are described herein. Therefore, the materials, methods, and examples herein are illustrative only and are not intended to be limiting unless otherwise specified.

[0072] Dialkoxysilane Adhesion Promoters

[0073] Adhesion promoters suitable for use in various embodiments of the compositions, masterbatches, methods, films, sheets, interlayers, laminates, etc. according to the present invention are dialkoxysilanes. Without being bound by theory, it is believed that the hydrolyzed silanol portion of the silane can form an adhesive bond with the glass surface (silanol), thereby enhancing adhesion at the interface between the polymer and the glass surface. The remainder of the silane molecule should then be "anchored" in some way and to some extent to the surrounding ionomer resin "matrix". One way to achieve this is to select functional groups that will interact in a favorable manner to allow the silane to chemically bond or by ionic bonding or hydrogen bonding or sufficient van der Waals bonding, or to have a size and shape that can spatially "bridge" between the interlayer and the glass surface, thereby increasing adhesion on the same interlayer without the favorable silane additive.

[0074] In one embodiment, each alkoxy group of the dialkoxysilane individually contains 1 to 3 carbon atoms. Suitable examples include diethoxydimethylsilane, diethoxy(methyl)vinylsilane, 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane, dimethoxydimethylsilane, dimethoxymethylvinylsilane, methyldiethoxysilane, diisopropyldimethoxysilane, dicyclopentyldimethoxysilane, γ-aminopropyl-N-cyclohexylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylmethyldiethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane.

[0075] In another embodiment, the dialkoxysilane contains, in addition to the alkoxy groups, "active" chemical groups for incorporation into the ionomer resin matrix, e.g., carboxylic acid reactive groups such as amino or glycidyl groups. Suitable examples include γ-aminopropyl-N-cyclohexylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylmethyldiethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane.

[0076] Desirably, the dialkoxysilane in pure form is a liquid at ambient conditions (e.g., at 20° C.) Specific such examples include N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane (CAS#3069-29-2) and 3-glycidoxypropylmethyldiethoxysilane (CAS#2897-60-1).

[0077] In a preferred embodiment of the invention, at least a portion or a major portion or substantially all of the dialkoxysilane adhesion promoter is present in and used in the form of recycled material - for example, a dipolymer and / or terpolymer ionomer containing at least one dialkoxysilane adhesion promoter and having been recycled from a previously manufactured polymer material. In addition to the dialkoxysilane adhesion promoter, the amount and type of additives present therein (e.g., antimicrobial agents, anti-fog additives, antioxidants, fillers, flame retardants, anti-slip agents, etc.) are not limited as long as they do not substantially affect the optical properties of the laminate containing the interlayer made from the composition of the invention.

[0078] Additional "fresh" dialkoxysilane adhesion promoters may be used as desired.

[0079] Ionomer

[0080] In certain embodiments of the present invention, there is at least one sodium-neutralized ethylene·α,β-unsaturated carboxylic acid copolymer (ionomer). Preferred ionomers are binary copolymers having constituent units derived from ethylene and constituent units derived from α,β-unsaturated carboxylic acids, wherein at least a portion of the constituent units derived from α,β-unsaturated carboxylic acids are neutralized by sodium ions. Other preferred ionomers are terpolymers having constituent units derived from ethylene, constituent units derived from α,β-unsaturated carboxylic acids, constituent units derived from α,β-ethylenically unsaturated carboxylic acid esters, and optionally constituent units derived from derivatives of α,β-unsaturated carboxylic acids other than esters (such as amides or anhydrides thereof), wherein at least a portion of the constituent units derived from α,β-unsaturated carboxylic acids are neutralized by sodium ions. In certain embodiments, the binary copolymer is the only ionomer in the composition, membrane, etc. of the present invention. In certain embodiments, the terpolymer is the only ionomer in the composition, membrane, etc. of the present invention.

[0081] In preferred embodiments of both the preferred binary copolymer and the preferred ternary copolymer, the content ratio of the constituent unit derived from the α,β-unsaturated carboxylic acid is usually 2% by mass or more, or 5% by mass or more (based on the total copolymer mass), including 7%, 10%, 12%, 14%, 15%, and 18% by mass or more. In addition, the content ratio of the constituent unit derived from the α,β-unsaturated carboxylic acid is usually 30%, 27%, 25%, 23%, or 22% by mass or less (based on the total copolymer mass).

[0082] Examples of α,β-unsaturated carboxylic acids that make up the preferred binary and ternary copolymer ionomers include, but are not limited to, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and mixtures of two or more thereof. In one embodiment, the α,β-ethylenically unsaturated carboxylic acid is selected from acrylic acid, methacrylic acid, and mixtures thereof. In another embodiment, the α,β-ethylenically unsaturated carboxylic acid is methacrylic acid.

[0083] Preferred terpolymers further comprise copolymerized units of one or more α,β-ethylenically unsaturated carboxylic acid esters. Alkyl esters having 3 to 10 or 3 to 8 carbon atoms are generally used. Specific examples of suitable unsaturated carboxylic acid esters include, but are not limited to, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, octyl acrylate, octyl methacrylate, undecyl acrylate, undecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, dodecyl acrylate, In one embodiment, the additional comonomer is selected from methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, glycidyl methacrylate, dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl fumarate, vinyl acetate, vinyl propionate, and a mixture of two or more thereof. In one embodiment, the additional comonomer is selected from methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, glycidyl methacrylate, vinyl acetate, and a mixture of two or more thereof. In another embodiment, one or more of n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, and isobutyl methacrylate are used. In another embodiment, one or two of n-butyl acrylate and isobutyl acrylate are used.

[0084] In one embodiment, preferred binary copolymers and terpolymers each independently have a melt flow rate (MFR) of about 1 g / 10 min, or about 2 g / 10 min, to about 4000 g / 10 min, or to 1000 g / 10 min, or to about 400 g / 10 min (as determined according to ASTM method D1238-89 at 190°C and 2.16 kg).

[0085] The skilled artisan is able to synthesize all ionomers described herein, including the preferred dipolymers and terpolymers herein, based on their chemical descriptions, optionally taking into account the disclosures in, for example, US3404134, US5028674, US6500888B2, US6518365B1, US8334033B2, and US8399096B2. In one embodiment, using the method described in US8399096B2, a derivative of a second α,β-ethylenically unsaturated carboxylic acid is present in the reaction mixture at a sufficiently high level and in a complementary amount.

[0086] In one embodiment, in order to obtain useful binary copolymer and terpolymer ionomer, their ethylene-acid copolymer precursor is partially neutralized by reacting with more than one alkali. The example of the suitable procedure for neutralizing ethylene-acid copolymer has been described in US3404134 and US6518365B1. After neutralization, about 1% or about 10% or about 15% or about 20% of the carboxylic acid group present in the ethylene-acid copolymer precursor, to about 90% or to about 60% or to about 55% or to about 30% hydrogen atom is replaced by other cations. In other words, about 1% or about 10% or about 15% or about 20% of the total content of the carboxylic acid group present in the ethylene-acid copolymer precursor, to about 90% or to about 60% or to about 55% or to about 30% is neutralized. In another alternative expression, the acid groups are neutralized to a level of about 1%, or about 10%, or about 15%, or about 20%, to about 90%, or to about 60%, or to about 55%, or to about 30%, based on the total content of carboxylic acid groups present in the ethylene-acid copolymer precursor as calculated or measured for the unneutralized ethylene-acid copolymer precursor. The neutralization level can be tailored for a specific end use.

[0087] The counter ion to the carboxylate anion in the ionomer is a sodium cation. In one embodiment, the ionomer used in the present invention is a substantially sodium-neutralized ionomer, wherein a counter ion other than the sodium cation is optionally present in a small amount of less than 5 equivalent %, or less than 3 equivalent %, or less than 2 equivalent %, or less than 1 equivalent %, based on the total equivalents of carboxylate groups in the ionomer.

[0088] Suitable cations other than alkali metal cations include any positively charged species that are stable under the conditions of synthesis, treatment and use of the ionomer composition. Suitable cations can be used in combinations of two or more. Typically, such other cations are metal cations, which can be monovalent, divalent, trivalent or polyvalent. Monovalent metal cations include, but are not limited to, cations of potassium, lithium, silver, mercury and copper. Divalent metal cations include, but are not limited to, cations of beryllium, magnesium, calcium, strontium, barium, copper, cadmium, mercury, tin, lead, iron, cobalt, nickel and zinc. Trivalent metal cations include, but are not limited to, cations of aluminum, scandium, iron and yttrium. Polyvalent metal cations include, but are not limited to, cations of titanium, zirconium, hafnium, vanadium, tantalum, tungsten, chromium, cerium and iron. When the metal cation is polyvalent, complexing agents such as stearate, oleate, salicylate and phenolate residues may be included, as described in US3404134. Typically, the metal cation used, when present, is a monovalent or divalent metal cation, such as lithium, magnesium, zinc, potassium, and combinations of more than one of these metal cations.

[0089] In one embodiment, counterions other than sodium are present in amounts no greater than "contaminant" amounts, as typically found in industrial situations, as will be recognized by one of ordinary skill in the relevant art.

[0090] The sodium neutralized ethylene-acid copolymers and terpolymers are ionomers and preferably have a lower melt index than their corresponding ethylene-acid copolymer precursors (as determined according to ASTM method D1238-89 at 190°C and 2.16 kg). The melt index of the ionomer depends on many factors, including the melt index of the ethylene-acid copolymer, the amount of copolymerized acid, the neutralization level, the identity of the cation and its valence. In addition, the desired value of the melt index of the ionomer can be determined by its intended end use. Typically, however, the ionomer has a melt index of about 1000 g / 10 minutes or less, or about 750 g / 10 minutes or less, or about 500 g / 10 minutes or less, or about 250 g / 10 minutes or less, or about 100 g / 10 minutes or less, or about 50 g / 10 minutes or less, or about 25 g / 10 minutes or less, or about 20 g / 10 minutes or less, or about 10 g / 10 minutes or less, or about 7.5 g / 10 minutes or less, as determined according to ASTM method D1238-89 at 190°C and 2.16 kg.

[0091] In one embodiment, the preferred binary copolymer consists essentially of or consists of copolymerized units of (i) ethylene and (ii) about 10 wt%, or about 15 wt%, or about 18 wt%, or about 20 wt%, to about 30 wt%, or to about 25 wt%, or to about 23 wt%, or to about 22 wt% of at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms, wherein the weight percentages of the copolymerized units are based on the total weight of the binary copolymer and the sum of the weight percentages of the copolymerized units is 100 wt%, and wherein at least a portion of the carboxylic acid groups of the α,β-unsaturated carboxylic acid are neutralized to form an ionomer comprising carboxylate groups having sodium counterions.

[0092] In one embodiment, the preferred terpolymer comprises, consists essentially of, or consists of copolymerized units of (i) ethylene, (ii) about 10 wt%, or about 15 wt%, or about 18 wt%, or about 20 wt%, to about 30 wt%, or to about 25 wt%, or to about 23 wt%, or to about 22 wt% of at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms, (iii) about 2 wt%, or about 3 wt%, or about 4 wt%, or about 5 wt%, to about 15 wt%, or to about 12 wt%, or to about 11 wt% of ethylene. %, or to about 10 wt % of at least one α,β-unsaturated carboxylic acid ester having 3 to 10 carbon atoms, and (iv) optionally a derivative of an α,β-unsaturated carboxylic acid other than (iii), in an amount such that (iii) + (iv) is about 15 wt % or less, or about 12 wt % or less, or about 11 wt % or less, wherein the weight percentages of the copolymerized units are based on the total weight of the terpolymer and the sum of the weight percentages of the copolymerized units is 100 wt %, and wherein at least a portion of the carboxylic acid groups of the α,β-unsaturated carboxylic acid are neutralized to form an ionomer comprising carboxylate groups having sodium counterions.

[0093] Such terpolymer ionomers are generally disclosed in WO 2015 / 199750 A1, WO 2014 / 100313 A1 and US 2017 / 0320297 A1.

[0094] In one embodiment of the preferred binary and / or ternary copolymers, the α,β-unsaturated carboxylic acid is methacrylic acid.

[0095] In one embodiment of the preferred terpolymer, the α,β-unsaturated carboxylic acid ester is n-butyl acrylate, isobutyl acrylate or a mixture thereof.

[0096] In one embodiment of the preferred terpolymer, it consists of, or consists essentially of, copolymerized units of (i), (ii) and (iii).

[0097] In one embodiment, both the bipolymer ionomer and terpolymer ionomer resins described herein are present, and the weight ratio (w / w, bipolymer / terpolymer) of the alkali metal neutralized ethylene-acid bipolymer ionomer resin to the alkali metal neutralized ethylene-acid-ester terpolymer ionomer resin based on the total weight of the bipolymer and terpolymer is not particularly limited. In one embodiment, the weight ratio of the alkali metal neutralized ethylene-acid dipolymer ionomer resin to the alkali metal neutralized ethylene-acid-ester terpolymer ionomer resin in the composition (w / w, dipolymer / terpolymer) is 0.1 / 99.9-99.9 / 0.1, including 0.5 / 99.5-99.5 / 0.5, 1 / 99-99 / 1, 3 / 97-97 / 3, 5 / 95-95 / 5, 10 / 90-90 / 10, 15 / 85-85 / 15, 20 / 80-80 / 20, 25 / 75-75 / 25, 30 / 70-70 / 30, 35 / 65-65 / 35, 40 / 60-60 / 40, 45 / 55-55 / 45 and 50 / 50, based on the total weight of the dipolymer and the terpolymer.

[0098] In one embodiment, one of the binary copolymer (i) or the ternary copolymer (ii) is from about 5wt% to about 30wt%, or to about 25wt%, to about 20wt%, to about 15wt%, or to about 10wt%, based on the combined weight of (i) + (ii). In another embodiment, one of (i) or (ii) is from about 10wt% to about 30wt%, or to about 25wt%, to about 20wt%, or to about 15wt%, based on the combined weight of (i) + (ii). In another embodiment, one of (i) or (ii) is from about 15wt% to about 30wt%, or to about 25wt%, to about 20wt%, based on the combined weight of (i) + (ii). In another embodiment, one of (i) or (ii) is from about 20wt% to about 30wt%, or to about 25wt%, based on the combined weight of (i) + (ii). In another embodiment, one of (i) or (ii) is from about 25wt% to about 30wt%, based on the combined weight of (i) + (ii).

[0099] In one embodiment, only one of the bipolymer and terpolymer ionomers described herein is present, and the total amount of the bipolymer or terpolymer present is all or substantially all of the composition, sheet, film, laminate, etc., based on the total weight of all polymers of any type present.

[0100] Although a critical minimum adhesion level is necessary to maintain sufficient laminate integrity (e.g., to prevent delamination defects) and sufficient glass post-fracture state retention, the impact performance of the resulting laminate can be intentionally optimized or adjusted. Although the optimal amount of adhesion modifier added (cumulative amount) varies with the additives used and the adhesion-modified resin, it is preferably adjusted in the following manner: In a strike test, the adhesion of the resulting laminate to glass is generally adjusted to be about 3 or more and about 10 or less (described in WO03 / 033583A1, etc.). In particular, in the case of requiring high penetration resistance, it is more preferred to adjust the amount of adhesion modifier added in such a manner that the adhesion is about 3 or more and about 6 or less, and in the case of requiring high glass breakage resistance, it is more preferred to adjust the amount of adhesion modifier added in such a manner that the adhesion is about 7 or more and about 10 or less.

[0101] Other additives

[0102] In addition to the above-mentioned dialkoxysilane, the embodiments of the present invention may further optionally contain one or more other additives, including, for example, antioxidants, ultraviolet absorbers, light stabilizers, anti-caking agents, pigments, dyes and heat-insulating materials (infrared absorbers), etc. or mixtures thereof. Such other additives are generally known to those skilled in the art.

[0103] Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, etc. Among them, phenolic antioxidants are preferred, and alkyl-substituted phenolic antioxidants are particularly preferred.

[0104] Examples of phenolic antioxidants include acrylate compounds such as 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate and 2,4-di-tert-amyl-6-(1-(3,5-di-tert-amyl-2-hydroxyphenyl)ethyl)phenyl acrylate; alkyl-substituted phenolic compounds such as 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane, 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetrakis(methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate)methane, and triethylene glycol bis(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate); and triazine-based phenolic compounds such as 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 6-(4-hydroxy-3,5-di-tert-butylanilino)-2,4-dioctylthio-1,3,5-triazine, 6-(4-hydroxy-3,5-dimethylanilino)-2,4-dioctylthio-1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-tert-butylanilino)-2,4-dioctylthio-1,3,5-triazine, and 2-octylthio-4,6-bis(3,5-di-tert-butyl-4-oxyanilino)-1,3,5-triazine; etc.

[0105] Examples of the phosphorus-based antioxidant include monophosphite-based compounds such as triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(2-tert-butyl-4-methylphenyl) phosphite, tris(2,4-di-tert-butyl) phosphite, tris(cyclohexylphenyl) phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, Phenomenal-10-oxide and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene; and diphosphite compounds, such as 4,4'-butylene-bis(3-methyl-6-tert-butylphenyl-di-tridecyl phosphite), 4,4'-isopropylidene-bis(phenyl-di-alkyl (C12-C15) phosphite), 4,4'-isopropylidene-bis(diphenyl monoalkyl (C12-C15) phosphite), 1,1,3-tris(2-methyl-4-di-tridecyl phosphite-5-tert-butylphenyl) butane and tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene phosphite; etc. Among them, monophosphite compounds are preferred.

[0106] Examples of the sulfur-based antioxidant include dilauryl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, pentaerythritol-tetrakis-(β-lauryl-thiopropionate), and 3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0107] These antioxidants can be used alone or in combination of two or more thereof. In the final resin composition, the antioxidant used is generally about 0.001 parts by weight or more, or about 0.01 parts by weight or more, based on 100 parts by weight of the ionomer resin. In addition, the antioxidant is generally used in an amount of about 5 parts by weight or less, or about 1 part by weight or less, based on 100 parts by weight of the ionomer resin (binary copolymer and terpolymer). The masterbatch composition is adjusted upward or downward depending on the substance to be added thereto.

[0108] Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers such as 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α'-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)triazole; hindered amine-based ultraviolet absorbers such as 2,2,6,6-tetramethyl 4-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy)ethyl)-2,2,6,6-tetramethylpiperidine; and benzoate-based ultraviolet absorbers, such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; etc.

[0109] These ultraviolet absorbers can be used alone or in combination of two or more thereof. In the final resin composition, the amount of ultraviolet absorber used is usually about 10 ppm by weight or more, or about 100 ppm by weight or more, based on the weight of the ionomer resin. In addition, the amount of ultraviolet absorber used is usually about 50,000 ppm or less, or about 10,000 ppm or less, based on the weight of the ionomer resin.

[0110] In certain embodiments, two or more UV absorbers may also be used in combination.

[0111] In other embodiments, no UV absorbers are added, or the compositions and masterbatches are substantially free of UV absorber additives.

[0112] Examples of the light stabilizer include hindered amine-based materials such as "ADEKA STABLA-57" (trade name) manufactured by Adeka Corporation, and "TINUVIN 622" (trade name) manufactured by Ciba Specialty Chemicals Inc.

[0113] When laminated glass is prepared by incorporating insulating fine particles or insulating compounds as insulating materials into the interlayer of the present invention to impart a thermal insulation function to the laminate, the light transmittance at a wavelength of 1500 nm can be adjusted to less than about 50%, or the TDS value (calculated according to ISO 13837:2008) can be adjusted to less than about 43%.

[0114] Examples of thermal insulation fine particles include metal-doped indium oxide, such as tin-doped indium oxide (ITO); metal-doped tin oxide, such as antimony-doped tin oxide (ATO); metal-doped zinc oxide, such as aluminum-doped zinc oxide (AZO); m WO n (M represents a metal element; m is about 0.01 or more and about 1.0 or less; n is about 2.2 or more and about 3.0 or less) represented by a metal element composite tungsten oxide; zinc antimonate (ZnSb 2 O 5 ); and lanthanum hexaboride, etc. Among them, ITO, ATO, and metal element composite tungsten oxide are preferred, and metal element composite tungsten oxide is more preferred. Examples of the metal element represented by M in the metal element composite tungsten oxide include Cs, Tl, Rb, Na, and K, etc., and in particular, Cs is preferred. From the viewpoint of heat insulation properties, m is preferably about 0.2 or more, or about 0.3 or more, and is preferably about 0.5 or less, or about 0.4 or less.

[0115] From the viewpoint of transparency of the final laminate, the average particle size of the heat shielding fine particles is preferably about 100 nm or less, or about 50 nm or less. Note that the average particle size of the heat shielding particles referred to herein means an average particle size measured by a laser diffractometer.

[0116] In the final resin composition, the content of the heat-insulating fine particles is preferably about 0.001 wt % or more, or about 0.05 wt % or more, or about 0.1 wt % or more, or about 0.2 wt % or more, relative to the weight of the ionomer resin. In addition, the content of the heat-insulating fine particles is preferably about 5 wt % or less, or about 3 wt % or less, or about 1 wt % or less, or about 0.5 wt % or less.

[0117] Examples of the heat-insulating compound include phthalocyanine compounds and naphthalocyanine compounds. From the viewpoint of further improving the heat-insulating property, it is preferred that the heat-insulating compound contains a metal. Examples of the metal include Na, K, Li, Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Sn, V, Ca, and Al, and Ni is particularly preferred.

[0118] The content of the heat-insulating compound is preferably about 0.001 wt % or more, or about 0.005 wt % or more, or about 0.01 wt % or more, based on the weight of the ionomer resin. In addition, the content of the heat-insulating compound is preferably about 1 wt % or less, or about 0.5 wt % or less.

[0119] Production of compositions and masterbatches containing recycled materials

[0120] In one embodiment, the recycled material (a polymer material containing at least one dialkoxysilane adhesion promoter and recovered from a previously manufactured polymer material) can be fed into the extrusion process together with one or more other resins (preferably including virgin and / or new production resins). During the extrusion process, together with the recycled material, additional additives may also be included. In addition to at least one dialkoxysilane adhesion promoter, the recycled material may also contain additives, depending on the source of the recycled material and the purpose for which it was originally used. The physical size and size of the recycled resin may require additional processing steps to facilitate its "feeding" back into the extrusion process for blending. In addition, reducing the size of the recycled material and optimizing the physical form of the recycled material will improve the uniformity of the reprocessed resin and, for example, minimize any optical inhomogeneities in the final film / sheet and the resulting glass laminate. Alternatively, enhanced extrusion compounding can be used to uniformly blend to remove inhomogeneities / inhomogeneities, but care must be taken when doing so because this may promote additional resin degradation, which usually manifests itself as increased yellowness and degraded resins (e.g., "black spots"). If the form of the recycled material requires a size reduction step, there are various means to complete the step. Rotary cutting, mechanical shredding, slicing, shearing or other size reduction techniques can be used to prepare recycled materials for re-feeding / introducing back into the process. Although the recycled material particles of suitable size are usually not limited, their size range can be about 0.1mm, or about 0.2mm, to about 5mm, or to about 4mm, or to about 2mm, or to about 1mm. Such particles can be measured by an optical microscope with a stage micrometer. Particles no more than 1mm can be measured using a 1mm stage micrometer with a scale of 0.01mm. Particles greater than 1mm can be measured using a 25mm stage micrometer with a scale of 0.05mm. For diameter, or in the case of elliptical or irregularly shaped particles, the maximum size of 20 particles randomly selected from the resin can be measured, and the average value of 20 particles is used to characterize the general particle size. For example, cryogenic grinding can be used to reduce the ionomer resin material from its larger form to a nominal average particle size of about 4mm to an average particle size in the range of about 0.1mm to about 0.5mm particle size. In addition, these particles break during the grinding process and have irregular shapes. Low temperature grinding processes are generally well known to those of ordinary skill in the art and generally involve using liquid nitrogen to quench the resin material before the grinding / milling process. Once cooled, the reclaimed material is passed through a mechanical grinder. Using liquid nitrogen to quench the reclaimed material can more effectively reduce the size without causing heating and promoting further polymer degradation.

[0121] In some cases, for example, scrap material can be fed directly back into the extrusion process by appropriate equipment design (e.g., guide / traction rollers and screw design). Sometimes the feed can be introduced into a "side feeder" so that it is combined with the primary feed. Any means for returning the recycled resin is within the scope of the present patent technology. As described above, the recycled material can contain more than one additive. The first recycled material can be a first ionomer resin.

[0122] These ionomer resin particles can also be prepared by other conventional means, for example, via underwater melt cutting. The pellets thus produced typically have a diameter or cross-section of 0.5 to 5 mm. Other methods known to those of ordinary skill in the relevant art can be used for formulation and blending prior to the melt process typically achieved during extrusion.

[0123] The present invention also optionally uses at least one of the following:

[0124] second particles of a second recycled material comprising an additive and which may also be an ionomer referred to herein as a second ionomer resin; and

[0125] First and / or second pellets of a third resin and / or a fourth resin (referred to herein as a third ionomer resin and a fourth ionomer resin) and optionally one or more additives.

[0126] "New" (ie, not recycled) additives may also be present in the third and fourth resins.

[0127] Once these materials are present / prepared, the first granules are coextruded with the second granules, one or more of the first pellets and the second pellets, and optionally with one or more newly produced additives, using an extruder under conditions of melting and intimately mixing the materials to produce a melt. The melt thus produced is then formed into a substantially continuous film or sheet having a thickness in the longitudinal direction of not more than about 2.5 mm.

[0128] The ionomer resin may be a combination of virgin and recycled materials. In one embodiment, the ionomer resin is from about 5 wt% to about 30 wt%, or from about 25 wt%, to about 20 wt%, to about 15 wt%, or to about 10 wt% recycled ionomer resin, based on the total ionomer resin weight. In another embodiment, the ionomer resin is from about 10 wt% to about 30 wt%, or from about 25 wt%, to about 20 wt%, or to about 15 wt% recycled ionomer resin, based on the total ionomer resin weight. In another embodiment, the ionomer resin is from about 15 wt% to about 30 wt%, or from about 25 wt%, to about 20 wt% recycled ionomer resin, based on the total ionomer resin weight. In another embodiment, the ionomer resin is from about 20 wt% to about 30 wt%, or to about 25 wt%, based on the combined weight of (i) + (ii). In another embodiment, the ionomer resin is from about 25 wt% to about 30 wt% recycled ionomer resin, based on the total ionomer resin weight.

[0129] Production of resin composition and masterbatch

[0130] The resin composition of the present invention can be produced as a melt blend by feeding the various components into an extruder and intimately mixing the components under the melt condition of the ionomer resin to produce a substantially homogeneous mixture, which can ultimately be formed into a final shape, such as by melt extrusion or shaping.

[0131] As will be appreciated by one of ordinary skill in the relevant art, in melt blending, care must be taken to ensure that mixing is sufficiently intense to blend the dialkoxysilane into the resin to sufficient uniformity. Typically, this high degree of mixing via extrusion compounding is performed by creating sufficient shear and residence time in the extruder. Care must also be taken to avoid undesirable results such as localized high concentrations of dialkoxysilane, decomposition of one or both of the dialkoxysilane and dipolymer and terpolymer due to high temperatures, etc. The formation of discolored resins, gels, or degraded products (e.g., black specks) can be avoided by selecting the correct process equipment and process conditions, and is within the skill of one of ordinary skill in the relevant art.

[0132] For example, it is known that the degree of hydrolysis of dialkoxysilanes will increase with inappropriate exposure to moisture and over extended periods of time, and further consideration may be required to control adventitious moisture exposure. Blanketing with dry air or nitrogen may be necessary, for example, to maintain the desired minimum degree of hydrolysis of the silane.

[0133] In one embodiment of the composition according to the present invention, it is a granular composition comprising recycled material and one or both of the copolymer and terpolymer resins (ionomer resins) all in granular form.

[0134] Desirably, the granular composition can be prepared by physically mixing ionomer resin particles and recycled particles under non-softening conditions of the ionomer resin and recycled material, in other words, wherein the ionomer resin and recycled material do not melt or soften to the extent that they significantly aggregate or otherwise lose their original granular form.

[0135] For both binary copolymers and ternary copolymers, the size of ionomer resin particles is not particularly limited. The size range of particles of suitable size for preparing final composition and masterbatch composition can be preferably about 0.1mm, or about 0.2mm, to about 5mm, or to about 4mm, or to about 2mm, or to about 1mm. Such particles can be measured by an optical microscope with a stage micrometer. Particles no more than 1mm can be measured using a 1mm stage micrometer with a scale of 0.01mm. Particles greater than 1mm can be measured using a 25mm stage micrometer with a scale of 0.05mm. For diameter, or in the case of elliptical or irregularly shaped particles, the maximum size of 20 particles randomly selected from the resin can be measured, and the average value of 20 particles is used to characterize the general particle size.

[0136] In one embodiment, the particles used to prepare the compositions and masterbatches of the present invention are reduced from a nominal pellet size, for example, by cryogenic grinding. For example, cryogenic grinding can be used to reduce ionomer resin pellets from a nominal average particle size of about 4 mm in diameter to an average particle size in the range of about 0.1 mm to about 0.5 mm in particle size. Reducing the particle size in this way increases the particle surface area relative to the particle weight. In addition, these particles break during the grinding process and have an irregular shape, which can further increase the surface area relative to the particle weight compared to the nominal spherical ionomer resin pellet shape. Cryogenic grinding processes are generally well known to those of ordinary skill in the relevant art, and generally involve using liquid nitrogen to quench the pellets before the grinding / milling process. Once cooled, the pellets are passed through a mechanical grinder. Using liquid nitrogen to quench the pellets can more effectively reduce the size without causing heating and polymer degradation.

[0137] These ionomer resin particles may also be prepared by other conventional means, such as via underwater melt cutting (eg, "pellets" having an average diameter of about 0.5 to about 1.5 mm) or other methods known to those of ordinary skill in the relevant art.

[0138] The dialkoxysilane additive is preferably present in the final resin composition at about 50, or about 100, or about 250, or about 500, or about 750, to about 5000, or to about 4000, or to about 2000, or to about 1500, or to about 1250 parts by weight per million parts by weight based on the total weight of the composition.

[0139] The dialkoxysilane additive is added to the composition of the present invention in whole or in part, or in whole, as "recycled material". If added in part, additional dialkoxysilane additives may be added with new or virgin resin, etc. In addition to the dialkoxysilane additive, the recycled material preferably comprises at least one of a dipolymer and a terpolymer.

[0140] In one embodiment, in the compositions, films, interlayers, etc. of the present invention, the weight ratio (w / w, ionomer resin / recycled material) of virgin or newly produced alkali metal neutralized ethylene-acid copolymer ionomer resin (e.g., binary copolymer, terpolymer) to recycled material based on the total weight of ionomer resin + recycled material is not particularly limited. In one embodiment, the weight ratio of virgin / newly produced ionomer resin to recycled material (w / w, ionomer resin / recycled material) in a given composition, masterbatch, film, etc. is 0.1 / 99.9-99.9 / 0.1, including 0.5 / 99.5-99.5 / 0.5, 1 / 99-99 / 1, 3 / 97-97 / 3, 5 / 95-95 / 5, 10 / 90-90 / 10, 15 / 85-85 / 15, 20 / 80-80 / 20, 25 / 75-75 / 25, 30 / 70-70 / 30, 35 / 65-65 / 35, 40 / 60-60 / 40, 45 / 55-55 / 45, and 50 / 50, based on the total weight of ionomer resin+recycled material. The preferred ratio is 99.5 / 0.5-70 / 30. For clarity and as an example, a ratio of 70 / 30 is provided by a 100 g composition containing 70 g virgin or new ionomer and 30 g recycled material. A 112 g composition containing 88 g virgin or new ionomer and 24 g recycled material has a ratio of 78.6 / 21.4.

[0141] The previously manufactured material from which the recycled material is derived may be waste material from the process used to make it, i.e., rejects, offcuts, etc. Such material typically contains not only polymer, but also one or more additives. Thus, when such polymer material containing additives is recycled, the additives are also considered "recycled". Recycled polymer material may also be obtained from downstream manufacturing operations, such as offcuts obtained from conversion processes for films and sheets that are manufactured into glass laminates. Additionally, it is feasible that the collected polymer material may be reprocessed to filter out contaminants through a secondary extrusion process to produce a material suitable for use.

[0142] Once the recycled material containing at least one dialkoxysilane is obtained, it can be fed into a process for making the final composition of the present invention, masterbatch, etc., along with other resins (including virgin / newly produced resins). During the process, additional additives may also be included along with the recycled material. In addition to the dialkoxysilane, the recycled material will typically contain one or more additives, especially if the material has been previously extruded for the purpose of producing, for example, an interlayer film / sheet product.

[0143] The physical size and dimensions of the recycle material may require some additional processing steps to facilitate its "feeding" into the process for blending, mixing, extrusion, etc. This is often the case, particularly when the recycle material is from an adjacent operation such as extrusion formation of a film, sheet, or laminate, and the recycle material is not an offcut of a sheet being manufactured. Additionally, reducing the size of the recycle material and optimizing the physical form of the recycle material will improve the uniformity of the reprocessed resin when used for this purpose, and minimize any optical non-uniformities in the final film / sheet and resulting glass laminate. This is effective whether the recycle is fed at 100% feed or with virgin ionomer resin or other resins and additives. Alternatively, intensive extrusion compounding can be utilized to uniformly blend out inhomogeneities, but this may also promote additional resin degradation to occur, which typically manifests itself as increased yellowness and degraded resin (e.g., "black specks").

[0144] If the form of the recycled material requires a size reduction step, there are various means to complete the step. Rotary cutting, mechanical shredding, slicing, shearing or other size reduction techniques can be used to prepare recycled materials for re-feeding / introducing back into the process. The size range of the ionomer resin recycled particles of suitable size is about 0.1mm, or about 0.2mm, to about 5mm, or to about 4mm, or to about 2mm, or to about 1mm. Such particles can be measured by an optical microscope with a stage micrometer. Particles no more than 1mm can be measured using a 1mm stage micrometer with a scale of 0.01mm. Particles greater than 1mm can be measured using a 25mm stage micrometer with a scale of 0.05mm. For diameter, or in the case of elliptical or irregularly shaped particles, the maximum size of 20 particles randomly selected from the resin can be measured, and the average value of the 20 particles is used to characterize the general particle size. For example, cryogenic grinding can be used to reduce the ionomer resin material from its larger form to a nominal average particle size of about 4 mm to an average particle size in the range of about 0.1 mm to about 0.5 mm. In addition, these particles break during the grinding process and have irregular shapes. Cryogenic grinding processes are generally well known to those of ordinary skill in the art and are generally directed to using liquid nitrogen to quench the resin material before the grinding / milling process. Once cooled, the recycled resin material is passed through a mechanical grinder. Using liquid nitrogen to quench the resin material can more effectively reduce size without causing heating and promoting further polymer degradation.

[0145] In some cases, for example, the scrap recovery material can be directly fed back into the extrusion process using appropriate equipment design (e.g., guide / traction roller and screw design) that is completely within the skill range of ordinary technicians. For example, the scrap can be introduced into a "side feeder" so that it is combined with a primary feed. Any means for returning the recovery material is within the scope of the present invention. As mentioned above, the recovery material can include more than one additive except more than one dialkoxysilane, such as those mentioned above.

[0146] Additional additives, if present, may be compounded as part of a masterbatch, or may be added during the preparation of the final resin composition by conventional means as would be recognized by one of ordinary skill in the relevant art.

[0147] In one embodiment, the recycled material has substantially the same content of at least one of the dipolymers, terpolymers, dialkoxysilanes and other additives as their content in the prepared composition, film, etc., and preferably has substantially the same content of all dipolymers, terpolymers, dialkoxysilanes and other additives as their content in the prepared composition, masterbatch, film, etc. In another embodiment, the recycled material has such content of dipolymers, terpolymers and dialkoxysilanes that at least one such content is different from its content in the prepared final composition. In a preferred embodiment, the final composition contains recycled material, dipolymer or terpolymer (not at the same time) and one or more optional additives. In another preferred embodiment, any dipolymer and / or terpolymer present / added / used, other than the dipolymer and / or terpolymer in the recycled material (if any), is in virgin or newly produced form.

[0148] In a preferred embodiment, the recycled material comprises, consists essentially of, or consists of: one or more dialkoxysilanes, dipolymers or terpolymers (not simultaneously) and one or more optional additives. In another preferred embodiment, any dipolymers and / or terpolymers present / added / used are in virgin or newly produced form, except for the dipolymers and / or terpolymers in the recycled material (if any).

[0149] Sheet / Film / Interlayer

[0150] The sheets of the ionomer resin composition of the present invention can be prepared by conventional melt extrusion or melt forming processes suitable for making interlayers for glass laminates. Such processes are well known to those of ordinary skill in the relevant art, as exemplified by previously incorporated publications.

[0151] The sheet can be a single layer or a multilayer sheet. For example, a multilayer sheet having a functional core layer sandwiched between two outer layers and other optional inner layers can be formed. In one embodiment, at least one (or both) of the outer layers of the multilayer sandwich is a sheet of an ionomer resin composition according to the present invention.

[0152] As an example of a functional core layer, there can be mentioned an acoustic damping layer, such as a polystyrene copolymer intermediate film (see JP2007-91491A), a polyvinyl acetal layer (see US2013 / 0183507A1, US8741439B2, JP2012-214305A and US8883317B2), a viscoelastic acrylic layer (see US7121380B2), a layer containing a copolymer of styrene and a rubber-based resin monomer (see JP2009-256128A), a layer containing a polyolefin (see US2012 / 0204940A1), a layer containing an ethylene / vinyl acetate polymer (see WO2015 / 013242A1), and a layer containing an ethylene-acid copolymer (see WO2015 / 085165A1).

[0153] In a specific embodiment, the middle layer is a thermoplastic elastomer resin, such as disclosed in WO2016 / 076336A1, WO2016 / 076337A1, WO2016 / 076338A1, WO2016 / 076339A1, WO2016 / 076340A1 and US2017 / 0320297A1. In a more specific embodiment, the thermoplastic elastomer resin is a hydrogenated product of a block copolymer having:

[0154] (i) an aromatic vinyl polymer block (a) containing about 60 mol % or more of aromatic vinyl monomer units based on the aromatic vinyl polymer block, and

[0155] (ii) an aliphatic unsaturated polymer block (b) containing about 60 mol % or more of conjugated diene monomer units based on the aliphatic unsaturated polymer block,

[0156] wherein the aliphatic unsaturated polymer block (b) contains about 50 mol % or more in total of isoprene units and butadiene units as conjugated diene monomer units, and

[0157] The amount of residual carbon-carbon double bonds of the aliphatic unsaturated polymer block derived from the conjugated diene monomer units is about 2 to about 40 mol%.

[0158] In addition, the interlayer as a whole can be symmetrical, having a substantially uniform thickness, or can be asymmetrical, where one portion of the interlayer has a greater thickness than another portion (e.g., a partial or complete "wedge shape," as discussed in US2017 / 0320297A1 and US2018 / 0117883A1). In addition, the laminate can be substantially transparent or tinted in whole or in part (e.g., a "light blocking band," as discussed in US2017 / 0320297A1 and US2018 / 0117883A1).

[0159] In a symmetrical configuration, the interlayer preferably has a total film thickness of about 320 μm or more, or about 420 μm or more. In addition, the total film thickness should be about 1250 μm or less, or about 1,000 μm or less.

[0160] In an asymmetric configuration such as a wedge, the thinner portion of the interlayer should have the thickness of a symmetric configuration, while the thickness of the thicker portion will depend on various parameters such as the wedge angle. In one embodiment of a wedge-shaped interlayer, the thickness of the thicker edge is about 1850 μm or less, or about 1600 μm or less, or about 1520 μm or less, or about 1330 μm or less, or about 1140 μm or less; and the thickness of the thinner edge is about 600 μm or more, or about 700 μm or more, or about 760 μm or more.

[0161] In addition, a concavo-convex structure, such as embossing, can be formed on the surface of the interlayer of the present invention by a conventionally known method to assist degassing during the manufacture of the laminate. The shape of the embossing is not particularly limited and can adopt a conventionally known shape.

[0162] In one embodiment, at least one surface (and preferably both surfaces) of the laminated glass interlayer is shaped. By shaping at least one surface of the laminated glass interlayer, bubbles present at the interface between the laminated glass interlayer and the glass are easily released to the outside of the laminated glass when manufacturing laminated glass, and thus the appearance of the laminated glass can be made good. Preferably, at least one surface of the laminated glass interlayer is shaped by an embossing roller method. By shaping the surface of the laminated glass interlayer, concave and / or convex portions are formed on the surface of the laminated glass interlayer.

[0163] The embossing roller used in the embossing roller method can be manufactured, for example, by using an engraving grinder (master grinder) having a desired concavoconvex pattern and transferring the concavoconvex pattern to the surface of a metal roller. In addition, the embossing roller can also be manufactured using laser etching. In addition, after forming a fine concavoconvex pattern on the surface of the metal roller as described above, the surface having the fine concavoconvex pattern is subjected to sandblasting using a grinding material such as aluminum oxide, silicon oxide or glass beads, thereby forming a finer concavoconvex pattern.

[0164] In addition, the embossing roller used in the embossing roller method is preferably subjected to a demolding treatment. In the case of using an embossing roller that has not been subjected to a demolding treatment, it is difficult to separate the interlayer for laminated glass from the embossing roller. Examples of the demolding treatment method include well-known methods such as silicone treatment, Teflon (registered trademark) treatment, and plasma treatment.

[0165] The depth of the concave portion and / or the height of the convex portion (hereinafter sometimes referred to as "the height of the embossed portion") of the surface of the interlayer for laminated glass shaped by the embossing roll method or the like is usually about 5 μm or more, or about 10 μm or more, or about 20 μm or more. The height of the embossed portion is usually about 150 μm or less, or about 100 μm or less, or about 80 μm or less.

[0166] In the present invention, the height of the embossed portion refers to the maximum height roughness (Rz) defined in JIS B 0601 (2001). The height of the embossed portion can be measured by, for example, the confocal principle using a laser microscope. In addition, the height of the embossed portion, that is, the depth of the concave portion or the height of the convex portion can be varied within the scope of the present invention.

[0167] Examples of the form of the shape imparted by the embossing roll method or the like include a lattice, an oblique lattice, an oblique ellipse, an ellipse, an oblique groove and a groove. The inclination angle of such a form is generally about 10° to about 80° relative to the film flow direction (MD direction). In addition, the shaped pattern may be a regular pattern or an irregular pattern such as a random matte pattern, or a pattern as disclosed in US7351468B2.

[0168] The shaping by the embossing roll method or the like may be performed on one surface of the interlayer for laminated glass, or may be performed on both surfaces, but is more usually performed on both surfaces.

[0169] Laminated body

[0170] The laminate of the present invention can be manufactured by conventional known methods. Examples thereof include using a vacuum laminator, using a vacuum bag, using a vacuum ring, and using a roller, etc. In addition, a method in which, after temporary contact bonding, the resulting laminate is placed in an autoclave for final bonding can be used.

[0171] In the case of using a vacuum laminator, for example, a known apparatus for manufacturing solar cells can be used, and the laminator is heated at a temperature of about 100° C. or more, or about 130° C. or more, and about 200° C. or less, or about 170° C. or less, at about 1×10 - 6 MPa or above and about 3×10 -2 MPa or less. For example, EP1235683A1 (CA2388107A1) describes a method using a vacuum bag or a vacuum ring, and for example, at a temperature of about 130°C or more and about 145°C or less at about 2×10 -2 MPa pressure stack components.

[0172] In the case of using a roller, for example, a method is exemplified in which, after first temporary contact bonding is performed at a temperature below the flow initiation temperature of the skin resin, temporary contact bonding is further performed under conditions close to the flow initiation temperature. Specifically, for example, a method is exemplified in which the assembly is heated to about 30° C. or higher and about 100° C. or lower by an infrared heater or the like, then degassed by rollers, and further heated to about 50° C. or higher and about 150° C. or lower, and then contact bonding is performed by rollers to achieve bonding or temporary bonding.

[0173] Although the autoclave treatment supplemented after the temporary contact bonding varies depending on the thickness or structure of the module, for example, it is performed at a temperature of about 120° C. to about 160° C. and a pressure of about 1 MPa to about 15 MPa for about 0.5 hour to about 2 hours.

[0174] Well-known "no-autoclave" processes may alternatively be used to process the stack.

[0175] Advantageously, the glass used for preparing the laminated glass is not particularly limited. Inorganic glass such as float sheet glass, polished sheet glass, patterned glass, wired sheet glass, heat ray absorbing glass, and conventionally known organic glass such as polymethyl methacrylate and polycarbonate can be used. These glasses may be any of colorless, colored, transparent or opaque glasses. These glasses may be used alone, or may be used in combination of two or more thereof.

[0176] As used in the present invention, the laminates are cooled after they are manufactured. Autoclaves are commonly used to heat treat the glass / interlayer assembly into the final laminated glass, however, autoclave-free processes are also used. Regardless of the specific process used, a thermal cycle that raises the temperature of the assembly to above the melting point of the ionomer interlayer and a cooling process therefrom is used to bring the laminate closer to ambient temperature, and this step can be performed at different cooling rates. They can be cooled rapidly at a rate of about 2 to 20°C / minute, or more slowly by allowing the laminate to reach room temperature in a suboptimal cooling process, applying a rate of about 0.1°C / minute or any rate in between. If the cooling rate is too fast and / or is performed in an uneven manner, there is a high probability of thermal shock and glass damage.

[0177] On the other hand, if the glass laminate is cooled too slowly (typically less than 1°C / min), additional crystallization may occur, potentially increasing the resulting haze of the final article. Crystallinity is an inherent property of these types of ethylene-acid derived ionomers. Guidelines for processing these materials are provided (see Kuraray Lamination Guidelines for Processing -- Available from Kuraray America Inc.). There are several reasons for cooling rate limitations when processing laminated glass: 1). Inadequate equipment design or operation that physically limits the removal of heat from the laminated glass, thereby reducing the cooling rate to suboptimal values. 2). Very thick glass and / or interlayer and multilayer laminate constructions where thermal conduction limits the absolute cooling rate of the ionomer resin inside the glass laminate despite attempts to apply aggressive external cooling. 3). Placing the glass laminate in an autoclave or oven or thermal treatment means in such a way that different cooling rates occur due to variations in heat transfer (conduction and convection), non-uniform temperature zones, and varying degrees of thermal radiation.

[0178] In practice, although not limiting the embodiments herein, "rapid" cooling generally refers to cooling achieved by using the maximum cooling rate setting on the available autoclave (e.g., United McGill - 20°C / minute). The actual cooling rate within and inside the glass laminate where the actual resin / interlayer is located will be less than the externally applied cooling rate due to thermodynamics. Thermocouples can be placed inside the interlayer within the glass laminate, allowing the cooling rate to be measured directly. Typically, a rate of 10°C / minute to about 2°C / minute is obtained depending on the actual temperature of the sample. Because the heat flow of the glass laminate will be a function of the temperature difference between the laminate and the surrounding "cooling means" (e.g., cooling air), the rate is generally faster at higher temperatures and becomes asymptotically smaller as the glass laminate temperature becomes more similar to the temperature of the cooling means. Therefore, in practice, it is difficult to state rapid cooling as a single cooling rate value. However, for slow cooling the situation is different as thermal equilibrium is close to being achieved so the internal temperature closely "tracks" the external temperature, so the cooling rate of 0.1 °C / min is measured from the entire cooling range to ambient and stated as fairly uniform.

[0179] The laminated glass of the present invention can be applied to automobile windshields, automobile side glasses, automobile sunroofs, automobile rear glasses or glasses for head-up displays; architectural components for windows, walls, roofs, skylights, soundproof walls, display windows, balconies or handrail walls, etc.; partition glass components for conference rooms; and solar panels, etc. Further information on such uses can be found by referring to previously incorporated publications.

[0180] The present invention will be further understood from the following specific examples. However, it should be understood that these examples should not be interpreted as limiting the scope of the present invention in any way.

[0181] Preparation of ionomer sheets

[0182] Ionomer 1 and recycled materials containing ionomer 1 and dialkoxysilane S1, S2, or S3 were fed into an 18-mm diameter Liestritz twin-screw compounding extruder (screw speed set at 200 rpm) using a K-Tron feeder (Coperion GmbH) equipped with a calibrated pigtail-type auger at approximately 5 to 7 lbs / hr and extruded as polymer strands (2 6-mm hole die).

[0183] The polymer output was controlled by adjusting the screw speed to provide a given output or residence time and resulting shear conditions. The molten strands were pulled through a water bath containing ambient temperature demineralized water, the excess water was blown off with compressed air, and the strands were fed into a rotary cutter (Conair) to give chopped strand pellets. These pellets were then dried overnight in a vacuum oven at 50°C with a lightly dried nitrogen purge. The pellets were then compression formed into nominally 0.76 mm thick sheets measuring 150-mm x 200-mm.

[0184] Method for preparing laminated body

[0185] Glass laminates were prepared from ionomer sheets by the following method. Annealed glass sheets (100×100×3 mm) were washed with a solution of trisodium phosphate in deionized water (5 g / l) at 50° C. for 5 minutes, and rinsed thoroughly with deionized water and dried. Three layers of ionomer sheets (each layer about 0.76 mm thick) were stacked together and placed between two glass sheets (to obtain a sandwich thickness of 2.28 mm).

[0186] The moisture level of the ionomer sheet was maintained at or below 0.08 wt % by minimizing the contact time with the room environment.

[0187] The moisture level of the ionomer sheet was measured using the coulometric Karl Fischer method (Metrohm Model 800) with the sample bottle's heating chamber temperature at 150° C. The ionomer sheet was cut into small pieces to fit into the sample bottle, with a total weight of 0.40 g.

[0188] The pre-laminated assembly is then tied together with a piece of polyester tape at several locations to maintain the relative position of each layer to the glass block. Nylon fabric strips are placed around the perimeter of the assembly to facilitate the removal of air from the layers. The assembly is placed in a nylon vacuum bag, sealed, and then connected to a vacuum pump. A vacuum is applied to allow substantial removal of air from the interior (reducing the air pressure within the bag to less than 50 millibars absolute). The bagged assembly is then heated to 120° C. in a convection air oven and held for 30 minutes. The assembly is then cooled to about room temperature using a cooling fan, and the assembly is disconnected from the vacuum source and the bag is removed to obtain a fully pre-pressed assembly of glass and interlayer.

[0189] The assembly was then placed in an air autoclave and the temperature and pressure were raised from ambient temperature and pressure to 135°C, 13.8 bar over 15 minutes. The temperature and pressure were maintained for 30 minutes, then the temperature was reduced to 40°C at a cooling rate of about 2.5°C / min, whereupon the pressure was then reduced back to ambient pressure (over 15 minutes) and the final laminate was removed from the autoclave.

[0190] The glass used was standard annealed soda-lime glass (obtained from Guardian Industries, Inc., Galax VA, USA).

[0191] Resins used: see Table 1.

[0192] Preparation of ionomer sheets

[0193] When necessary, the ionomer resins were combined by dry blending, and any additives, if present, were fed at about 5 to 7 lbs / hr using a K-Tron feeder (Coperion GmbH) equipped with a calibrated pigtail-type auger into an 18-mm diameter Liestritz twin-screw compounding extruder (screw speed set at 400 rpm), with zone temperatures set to control the barrel temperature at 210° C. and the melt temperature at the die falling within the range of 205 to 225° C. The polymer was extruded as strands (2 6 mm hole die).

[0194] The polymer yield is controlled by a combination of feed rate and extruder screw speed to provide a given yield or residence time and resulting shear conditions. As the molten strands leave the die, they are pulled through a water bath containing demineralized water at ambient temperature, excess water is blown off with compressed air, and the strands are fed into a rotary cutter (Conair) to give chopped strand pellets (nominal length 4 mm). The pellets are then dried overnight in a vacuum oven at 50°C with a lightly dry nitrogen purge. The pellets are then compression formed into nominally 0.76 mm thick plates measuring 150-mm×200-mm. The plates are then kept in a dry atmosphere before being prepared as laminates.

[0195] Method for preparing laminated body

[0196] Glass laminates were prepared from the individual ionomer sheets by the following method. Annealed glass sheets (100×100×3 mm) were washed with a solution of trisodium phosphate in deionized water (5 g / l) at 50° C. for 5 minutes, then rinsed thoroughly with deionized water and dried. Three layers of the individual ionomer sheets (each layer about 0.76 mm thick) were stacked together and placed between two glass sheets (to obtain a sandwich thickness of 2.28 mm).

[0197] The moisture level of the ionomer sheets was maintained at or below 0.08 wt % by minimizing contact time with room environment (about 35% RH) or by exposure for 10 days at the temperature and humidity levels shown in the following examples (samples were placed in an Espec humidity chamber - Model LHU-113).

[0198] The moisture level of the ionomer sheet was measured using the Coulometric Karl Fischer method (Metrohm Model 800) with the sample bottle's heating chamber temperature at 150° C. The ionomer sheet was cut into small pieces to fit into the sample bottle, with a total weight of 0.40 g.

[0199] The pre-laminated assembly is then tied together with a piece of polyester tape at several locations to maintain the relative position of each layer to the glass block. Nylon fabric strips are placed around the perimeter of the assembly to facilitate the removal of air from the layers. The assembly is placed in a nylon vacuum bag, sealed, and then connected to a vacuum pump. A vacuum is applied to allow substantial removal of air from the interior (reducing the air pressure within the bag to less than 50 millibars absolute). The bagged assembly is then heated to 120° C. in a convection air oven and held for 30 minutes. The assembly is then cooled to about room temperature using a cooling fan, and the assembly is disconnected from the vacuum source and the bag is removed to obtain a fully pre-pressed assembly of glass and interlayer.

[0200] The assembly was then placed in an air autoclave and the temperature and pressure were raised from ambient temperature and pressure to 135°C, 13.8 bar over 15 minutes. The temperature and pressure were maintained for 30 minutes, then the temperature was reduced to 40°C at a cooling rate of about 2.5°C / min, whereupon the pressure was then reduced back to ambient pressure (over 15 minutes) and the final laminate was removed from the autoclave.

[0201] After autoclaving, the finished laminates were reheated in an air circulating oven controlled at a temperature of 120°C ± 2°C and held for 2 to 3 hours to reach thermal equilibrium. The laminates were then cooled slowly to ambient temperature (~23°C) at 0.1°C / min, or rapidly cooled (fast) by removing the laminates from 120°C and rapidly cooling them by forcing room temperature air across the surface of each laminate using a large floor fan. A thermocouple placed within the ionomer interlayer and near the center of the laminate was used to determine the actual cooling rate curve of the sample. The temperature dropped from 120°C to about 85°C in 7 minutes, from 85°C to 60°C in 10 minutes, and from 60°C to 30°C in 18 minutes, with the internal laminate temperature returning to about room temperature in an additional 10 minutes. The optical measurements presented in Table 3 were formed after these "fast" and 0.1°C / min (slow) cooling thermal cooling rate treatments.

[0202] Haze and YI Measurement

[0203] Use WINDEX glass cleaner (SC Johnson & Son, Inc.) and lint-free cloth to thoroughly clean the laminate, and check to ensure that there are no bubbles and other defects that may interfere with effective optical measurements. Then evaluate the laminate by Haze-gard Plus haze meter (Byk-Gardner) to obtain the measurement of haze percentage. The measurement of haze follows the practice outlined in the American National Standard (ANSI Z26.1-1966) "Safety Code for Safety Glazing Materials for Glazing Motor Vehicles Operating on Land Highways" for windows and automotive equipment of highway vehicles. The test sections 5.17 and 5.18 in this standard and Figures 5 and 6 describe in detail the appropriate methods and instrument settings for measuring the haze level of glass materials. The Hazegard Plus haze meter meets the appropriate criteria of this standard for all upcoming measurements. Use a haze standard traceable to the National Bureau of Standards (now NIST) to ensure that the instrument is well calibrated and operates normally. Color measurements (when measured) were made on a Hunterlab ULTRASCAN XE (Hunter Associates Laboratory, Inc., Reston, Va.) using a 10 degree / D65 illuminant / observer. Yellowness index (YI) was calculated by ASTM E313-05 using a 2 degree observer and illuminant C (2 degrees).

[0204] Measurement of peel adhesion

[0205] To allow for the measurement of peel adhesion, some samples were prepared as described above with the following exceptions.

[0206] The annealed glass was scored, cut into rectangles of 100 mm × 200 mm, and then washed according to the procedure described above. A thin polyester tape (25 μm thick × 25 mm wide) with a silicone adhesive was applied to the glass surface on the "side of interest" (air side or tin side) in two parallel strips to provide a uniform 25 mm wide bonding area between them. This procedure allows the production of very clearly defined bonding areas without the need to cut the polymer layer to produce peeling strips, as is conventionally done in standard peel adhesion methodology. Above the interlayer sample, before the second piece of glass is placed on top, a 4 mil thin sheet of FEP film is placed on top of the plastic sheet, thereby providing a relatively flat surface for the lamination step and serving as a release layer for removing the top glass sheet. All lamination steps are then performed as described above. Afterwards, 90 degree angle peeling adhesion measurements are performed on various samples manufactured by the above process via a mechanical testing device (INSTRON model 1122, Instron Industrial Products, Norwood, MA USA). Stripping was performed at a crosshead speed of 1 cm / min under standard laboratory conditions (nominal 23°C and 50% RH). After stripping of about 100 mm of sample, demineralized water was applied to the glass and stripping interface so that the interface was immediately completely immersed in liquid water. Allowed to continue stripping until another about 100 mm sample was tested. Sufficient water was present to ensure that the sample remained in a "wet" state during this final test phase. Data was collected via computer software (INSTRON Bluehill III software, Instron Industrial Products, Norwood, MA USA), and the average force level of the "50% RH" and "wet state" stripping test parts was calculated.

[0207]

[0208]

[0209] The peel adhesion data provided in Table 2 demonstrates a surprising aspect, namely, enhanced adhesion behavior far beyond that exhibited by either of the virgin ionomer resins (10-1 or 10-2). In these cases, a similarly low weight percentage (e.g., 25%) of a recycled ionomer resin (10-4) (e.g., EX-01 or EX-05) that had previously been modified with 3-glycidoxypropylmethyldiethoxysilane was added. The retention of adhesion was maintained through the reprocessing of the resin, and generally, the increase in adhesion was proportional to the percentage of added silane-modified recycled resin added.

[0210] In the subsequent tables of the Examples, for all samples containing ionomers, a corresponding increase in haze with slow cooling is also evident. It is well known that ionomers of this family of compositions (ethylene-methacrylic acid copolymers and terpolymers as ionomers) have a certain degree of crystallinity, and they also exhibit microphase separation of the polymer backbone and ionic clusters. These crystallites / ionic clusters can then lead to visible light scattering (e.g., haze / lack of clarity), the magnitude of which generally always increases with decreasing cooling rates. During the heat treatment of ionomer-based interlayers into laminated glass form, it is generally recommended to provide cooling from the "hot" portion of the cycle (commonly referred to as a "heat soak", with temperatures ranging from 105°C to 170°C) at a sufficient cooling rate to minimize haze formation due to recrystallization and solidification processes. As the ionomer interlayer cools back from the molten state to its "solid form", the laminated glass is stable and can be safely handled. Haze is an undesirable property for glass laminates where high transparency is desired, and therefore, faster cooling rates are also desired. However, equipment limitations, process setup and adjustments to process conditions, as well as heat transfer differences due to materials of construction and physical size / thickness, among other things, will determine the actual cooling rates that are typical or likely for glass laminates containing ionomer-based interlayers.

[0211] Table 3 shows the haze and YID data for various combinations of blends of the following components: a). virgin dicarboxylic acid ionomer (IO-1), b). virgin terpolymer (IO-2), or each in its corresponding recycled resin form (IO-3 & IO-4, respectively). Normal and typical manufacturing operations will usually utilize a portion of the extruded polymer resin to be returned to the process as recyclate (internal source). The compositional restrictions on the amount of recyclate that can be appropriately added will be related to the degree of impact on visible quality, or to minimizing any undesirable shifts in other performance parameters (such as tensile strength) that will result. Surprisingly, blends of dicarboxylic acids (in virgin resin and / or its corresponding recycled form) with terpolymers (in virgin resin and / or its corresponding recycled form) show very good optical behavior over the entire blending range with respect to haze and YID levels. This will allow complete flexibility in the manufacture of blending this resin family with the final product of this resin family, providing acceptable optical consistency. Customers dealing with these blends can then expect uniform optical properties after laminating sheet products containing any of the blend ratios in the art, even if their lamination processes exhibit different thermal cycling / cooling rates.

[0212]

[0213] From the foregoing information, it has been shown that there are new ionomer resin blends that surprisingly provide acceptable optical properties in the use of glass laminates. Examples of various blend compositions in the art are sufficiently similar to any individual native ionomer resin component to meet the optical quality expectations of the end use. For flexibility in manufacturing the ionomer interlayer with acceptable or desired optical properties (transparency, low haze and low yellowness (color)), it is desirable to have complete or significant compositional freedom of choice of blends of resin combinations. Blends of selected sodium ionomers based on dicarboxylic acid copolymer resins (ethylene / carboxylic acid) and selected sodium ionomers based on terpolymer resins (ethylene / acrylate / carboxylic acid) have been shown to exhibit acceptable optical properties over their entire composition range. Other sodium ionomers of dicarboxylic acid copolymer resins exhibit very nonlinear and undesirable yellowness when blended with selected dicarboxylic acid ionomers or selected terpolymer ionomer resins or combinations thereof. When embodiments using blends, mixtures, combinations, etc. of components are described herein, all ratios of the components are considered unless otherwise stated. For example, but not limited to, where a combination of binary and ternary copolymers are used, such as (i) and (ii) above, weight ratios of 99.9 / 0.1 to 0.1 / 99.9 are contemplated, as well as all intermediate ratios such as 90 / 10, 75 / 25, 60 / 40, 50 / 50, 40 / 60, 25 / 75, 10 / 90, etc. w / w (i) / (ii).

[0214] The above written description of the present invention provides the mode and process of making and using the present invention, so that any person skilled in the art can make and use the present invention, especially for the subject matter of the attached claims that form part of the original description and provide such support. This description is provided in the context of a specific application and its requirements. Various modifications to the embodiment will be obvious to a person skilled in the art, and the general principles defined herein may be applicable to other embodiments and applications without departing from the spirit and scope of the present invention. Therefore, the present invention is not intended to be limited to the embodiments shown, but conforms to the widest scope consistent with the principles and features disclosed herein. In this regard, in a broad sense, some embodiments within the present invention may not show all the benefits of the present invention.

Claims

1. An ionomer resin composition comprising a blend of a dialkoxysilane adhesion promoter and an ionomer resin, wherein the ionomer resin is (i) an at least partially sodium neutralized ethylene-acid copolymer ionomer resin, or (ii) an at least partially sodium neutralized ethylene-acid-ester terpolymer ionomer resin, or (iii) any combination of (i) and (ii), And wherein at least a portion of the dialkoxysilane adhesion promoter and at least a portion of the ionomer resin are in the form of recycled material.

2. The composition of claim 1, wherein the ionomer resin comprises: (i) an at least partially sodium neutralized ethylene-acid copolymer ionomer resin consisting essentially of copolymerized units of ethylene and at least one α,β-unsaturated carboxylic acid, or (ii) an at least partially sodium neutralized ethylene-acid terpolymer ionomer resin comprising copolymerized units of ethylene, at least one α,β-unsaturated carboxylic acid, and at least one α,β-unsaturated carboxylic acid ester, or A combination of (i) and (ii).

3. The composition of claim 1, wherein the dialkoxysilane adhesion promoter is present in the ionomer resin composition in an amount ranging from 50 to 5000 parts by weight per million parts by weight based on the weight of the ionomer resin.

4. The ionomer resin composition of claim 1, wherein the ionomer resin comprises a native sodium neutralized ethylene-acid copolymer.

5. The ionomer resin composition of claim 1, wherein the ionomer resin comprises a combination of virgin and recycled materials.

6. The ionomer resin composition of claim 5, wherein the ionomer resin is 5 wt% to 30 wt% of recycled ionomer resin based on the total ionomer resin weight.

7. The ionomer resin composition of claim 5, wherein the ionomer resin is 5 wt% to 25 wt% recycled ionomer resin based on the total ionomer resin weight.

8. The ionomer resin composition of claim 5, wherein the ionomer resin is 10 wt% to 25 wt% of recycled ionomer resin based on the total ionomer resin weight.

9. The ionomer resin composition of claim 4 wherein said virgin sodium neutralized ethylene acid copolymer and said recycled material are intimately mixed.

10. The ionomer resin composition according to claim 2, The binary copolymer ionomer resin is essentially composed of the following copolymer units: composition: (i) ethylene, and (ii) 10 to 30 wt% of at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms, wherein the weight percentages of the copolymerized units of the binary copolymer ionomer resin are based on the total weight of the binary copolymer ionomer resin, the sum of the weight percentages of the copolymerized units of the binary copolymer ionomer resin being 100 wt %, and wherein at least a portion of the carboxylic acid groups of the α,β-unsaturated carboxylic acid of the binary copolymer ionomer resin are neutralized to form an ionomer containing carboxylate groups having sodium counter ions, and wherein the terpolymer ionomer resin consists essentially of the following copolymerized units: (i) ethylene, (ii) 10 to 30 wt% of at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms, (iii) 2 to 15 wt% of at least one α,β-unsaturated carboxylic acid ester having 3 to 10 carbon atoms, and (iv) optionally a derivative of an α,β-unsaturated carboxylic acid other than (iii), in an amount such that (iii)+(iv) is 15 wt% or less, wherein the weight percentages of the copolymerized units of the terpolymer ionomer resin are based on the total weight of the terpolymer ionomer resin, the sum of the weight percentages of the copolymerized units of the terpolymer ionomer resin being 100 wt %, and wherein at least a portion of the carboxylic acid groups of the α,β-unsaturated carboxylic acid of the terpolymer ionomer resin are neutralized to form an ionomer comprising carboxylate groups having sodium counter ions.

11. The ionomer resin composition of claim 1 wherein each alkoxy group of the dialkoxysilane adhesion promoter individually contains from 1 to 3 carbon atoms.

12. The ionomer resin composition of claim 11 wherein the dialkoxysilane adhesion promoter contains, in addition to alkoxy groups, reactive chemical groups for bonding to the native alkali metal neutralized ethylene-acid copolymer.

13. An interlayer sheet comprising the ionomer resin composition according to any one of claims 1 to 12.

14. The interlayer sheet according to claim 13, which has a thickness ranging from 320 μm to 1850 μm. 15 . A glass laminate comprising the interlayer sheet according to claim 13 .

16. A method of making an ionomer resin composition comprising the step of intimately mixing a virgin sodium neutralized ethylene-acid copolymer and a recycled material comprising a dialkoxysilane adhesion promoter.

17. The method of claim 16 comprising the steps of feeding the virgin sodium neutralized ethylene-acid copolymer and recycled material into an extruder and intimately mixing the copolymer and the recycled material under melt conditions to produce a substantially homogeneous mixture, followed by forming the substantially homogeneous mixture into a final shape by melt extrusion or forming.

18. The method of claim 17, wherein the ionomer resin composition is as described in any one of claims 1 to 12.

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