Ionomer resin composition

Abstract

Provided are an ionomer resin composition containing a sodium-neutralized ethylene acid copolymer and a recycled dialkoxysilane adhesion promoter, and a method for producing and using the composition. The sodium-neutralized ethylene acid copolymer used is preferably a combination of a "new" or "unused" copolymer and a recycled copolymer, and the dialkoxysilane adhesion promoting additive used is present at least partially in the form of recycled material and is combined with the copolymer in the form of recycled material. The ionomer resin composition described has improved adhesion to glass among many beneficial properties and uses, and is thus particularly suitable for use in the production of intermediate layers and glass laminates containing said intermediate layers.

Description

Technical Field

[0001] This application claims priority to U.S. Provisional Application No. 63 / 354,307, filed on June 22, 2022, and U.S. Provisional Application No. 63 / 354,335, and both applications are hereby incorporated by reference in their entirety for all purposes as if fully set forth herein.

[0002] The present invention relates to an ionomer resin composition comprising a sodium-neutralized ethylene acid copolymer and a dialkoxysilane adhesion promoter, and methods of making and using said composition. The sodium-neutralized ethylene acid copolymer used is preferably an “unused” or “new” copolymer, and the dialkoxysilane adhesion promoting additive used is preferably initially present in the form of a recycled material and combined with the copolymer in the form of a recycled material. Preferably, the sodium-neutralized ethylene acid copolymer is one or a combination of a sodium-neutralized ethylene acid dipolymer and a sodium-neutralized ethylene acid ester terpolymer. The ionomer resin composition described has improved adhesion to glass among many beneficial properties and uses, and is thus particularly suitable for use in the manufacture of interlayers and glass laminates comprising said interlayers.

Background Art

[0003] Laminated glass is generally made by laminating two glass sheets with a plastic interlayer. One of the specific advantages of laminated glass over solid glass sheets is the impact resistance and shatter resistance resulting from the adhesion of the glass to the interlayer sheet.

[0004] In a safety glass laminate, the optimal adhesion of the interlayer to the glass is a balance. If the adhesion is too high, the ability of the laminate to absorb and dissipate energy upon impact is impaired, and if the adhesion is too low, optical defects can occur (both during and after lamination), and the ability of the interlayer to hold glass fragments upon impact can also be adversely affected.

[0005] Many different materials are used as the plastic intermediate layer. For example, a sheet containing polyvinyl acetal (polyvinyl butyral) and a plasticizer is widely used as the intermediate layer of laminated glass because of its excellent adhesiveness to glass. Laminated glass containing such an intermediate layer can be excellent in transparency, mechanical strength, flexibility, sound insulation, and resistance to scattering.

[0006] At least partially neutralized ethylene acid copolymers (ionomers) are also used as intermediate layers for making laminated safety glass, as disclosed, for example, in US3404134, US3344014, US7445683B2, US7763360B2, US7951865B1, US7960017B2, US8399097B2, US8399098B2, US2017 / 0320297A1, US2018 / 0117883A1, WO2016 / 076336A1, WO2016 / 076337A1, WO2016 / 076338A1, WO2016 / 076339A1, and WO2016 / 076340A1.

[0007] Ionomer resins can be selected to produce intermediate layers with excellent bending strength and optical properties, but the adhesiveness to glass may not be optimal. In particular, since ionomers are neutralized acid copolymers, there is a tendency for lamination defects to occur, especially in a high-humidity environment.

[0008] For example, when using an ionomer resin as the intermediate layer for float glass, the adhesion on the "tin side" of the glass is satisfactory, but the adhesion on the "air side" is often unsatisfactory. Therefore, special attention needs to be paid during the lamination process to properly orient such a glass sheet to ensure contact with the intermediate layer on the "tin side".

[0009] To improve the following problems, it has been proposed to use primers and other surface treatments on the glass and the intermediate layer (see, for example, US2016 / 0159042A1), but this adds cost and complexity to the lamination process, and such surface treatments often result in excessive adhesion, which, as shown above, can impair the ability of the laminate to absorb and dissipate energy upon impact.

[0010] Modification of ionomer resins and blending with additives have also been attempted. For example, increasing the acid level of ethylene copolymers improves the adhesion of the final ionomer, but there are practical and economic limits to how much the acid value can be increased. Additives have also been used, but the success stories are limited. In particular, silanes are known to be excellent adhesion promoters for glass in several different resin systems. However, as disclosed in US20110105681A1, when using ionomers, especially sodium-neutralized ionomers, and silanes in general, gels are formed and a melt flow that can complete sheet extrusion in a satisfactory manner cannot be produced. In that particular publication, a narrow type of amino group-containing dialkoxysilane that can only be used in combination with a specific type of zinc-neutralized ionomer was identified.

[0011] Co-owned US2019030863A1 provides a sodium-neutralized ethylene copolymer ionomer composition that contains a specified amount of a specified dialkoxysilane silane additive and has improved adhesion to glass on both the tin side and the air side of float glass, without the problems identified in US20110105681A1.

[0012] Ionomers are thermoplastic and renewable. In an ideal situation, this means they can be repeatedly melted and reformed into new products. The process of recycling ionomer materials is disclosed in D. Sykutera, P. Czyzewski, Volume 7, Issue 3, pp. 301 - 308, Gdansk, 2012 in the Polish CIMAC journal; and by J.G. Poulakis, C.D. Papaspyrides in Volume 19, Issue 3, pp. 203 - 209 (2000) in the journal Adv in Polymer Technology. Generally, these processes involve cooling the ionomer, cutting the waste ionomer into appropriate sizes to enable redissolution, and reprocessing to form injection - molded products. However, the polymer degrades with each thermal cycle, undesirable properties such as color are imparted to the polymer, and the use of these recycled ionomers for intermediate layers (thin films and sheets) in glass laminates where transparency is an important parameter has not been disclosed.

Prior Art Documents

Patent Documents

[0013]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Patent Document 10

Patent Document 11

Patent Document 12

Patent Document 13

Patent Document 14

Patent Document 15

Patent Document 16

Patent Document 17

Patent Document 18

Patent Document 19

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0014] It is expected that any silane adhesion promoter remaining in the recycled material will deteriorate due to thermal cycling. In fact, since silane groups are known to be sensitive to moisture, oxygen, and other environmental factors, it is expected that many of the silane adhesion promoters originally present in the material have deteriorated due to environmental exposure during the use of products made from ionomers or uncontrolled environmental exposure during recycling.

[0015] In contrast to this prediction, "used" materials that originally contain the specified silane adhesion promoter can still be advantageously used successfully as recycled materials while still imparting glass adhesion, and in particular, it has now been found that it enables the optimal use of such silanes and ionomers in the preparation of thin films and sheets such as interlayers and glass laminates with improved interlayer-to-glass adhesion. Furthermore, since one kind of silane used herein is preferably used at least in the form of recycled materials, the advantages described herein play a role in, for example, enhancing overall efficiency, reducing raw material requirements, reducing waste, and saving energy in the manufacture of thin films and sheets. The process of using recycled ionomer materials is known, but no problems regarding the difference in appearance between laminates made using ionomers without added recycled materials and laminates with added recycled materials have been disclosed. Some of these differences in appearance include, but are not limited to, transparency, haze, color, modulus of elasticity, and tensile strength. Furthermore, although the effect of different cooling cycles on ionomers with added recycled materials has not been explained so far, it will be explained herein.

[0016] As used herein, terms such as "invention" and "the present invention" refer only to the specific embodiments immediately following them. These are not broadly limiting, either in whole or with respect to some of the advancements in the technology described herein.

Means for Solving the Problems

[0017] The present invention addresses the above problems in one embodiment by providing an ionomer resin composition comprising a blend of a dialkoxysilane adhesion promoter and an ionomer resin, where the ionomer resin is

[0018] (i) an ethylene acid dipolymer ionomer resin that is at least partially sodium-neutralized, or

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

[0020] (iii) Any combination of (i) and (ii)

[0021] wherein at least a part of the dialkoxysilane adhesion promoter and at least a part of the ionomer resin may be in the form of recycled materials.

[0022] In one embodiment, the sodium-neutralized ethylene acid dipolymer ionomer resin (i) is at least partially sodium-neutralized ethylene acid dipolymer resin consisting essentially of, or consisting of, copolymer 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 at least partially sodium-neutralized ethylene acid terpolymer resin consisting essentially of, or consisting of, copolymer units containing 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 an anhydride.

[0023] In one embodiment, the dialkoxysilane adhesion promoter is present in the ionomer resin composition in an amount in the range of about 50 to about 5000 weight ppm based on the weight of the ionomer resin.

[0024] In one embodiment, the dialkoxysilane adhesion promoter is substantially uniformly dispersed in the resin composition. In another embodiment, the ionomer resin composition is a particulate resin composition.

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

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

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

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

[0029] In all embodiments herein, preferably, at least a portion of the sodium-neutralized ethylene acid copolymers (e.g., dipolymers and terpolymers) used are unused or new copolymers.

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

[0031] In one embodiment of the above method, the dialkoxysilane compound is substantially uniformly dispersed in the resin composition. In another embodiment, the mixing step is a melt blending step. In another embodiment, the dipolymer and / or terpolymer ionomer resin is in particulate form, the mixing step is carried out under non-softening conditions for both the dipolymer and the terpolymer ionomer resin, and the resin composition is a particulate resin composition.

[0032] In another aspect, the present invention provides a method comprising the following steps: in an extruder, co-extruding the recycled material with the sodium-neutralized ethylene acid dipolymer and / or the alkali metal-neutralized ethylene acid ester terpolymer, and optionally one or more additives selected from the group consisting of an ultraviolet absorber, an antioxidant, a light stabilizer, and a colorant, under conditions that melt and intimately mix the recycled material with the dipolymer and / or the terpolymer to produce a melt; and optionally, forming the melt into a film or sheet having a substantially continuous thickness in the longitudinal direction, for example, a thickness up to about 2.5 mm.

[0033] In one embodiment of this co-extrusion method, the recycled material is in the form of granules. In another embodiment, the dipolymer and / or the terpolymer is in the form of pellets.

[0034] In one embodiment, the dialkoxysilane compound contains a carboxylic acid-reactive group in addition to two alkoxysilane 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 for producing a sheet of an ionomer resin composition by melt-blending one of the above particulate resin compositions under shear to produce 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 surface and a lower surface, and the sheet may be embossed with a pattern on one or both of the upper and lower surfaces before solidification.

[0036] In other aspects, the present invention provides an intermediate layer sheet of such a resin composition, and a glass laminate made from such an intermediate layer sheet, for example, a glass laminate including two glass sheets and an intermediate layer according to the present invention interposed therebetween.

[0037] In one embodiment, the intermediate layer sheet may be pre-conditioned at 34 °C and 50% relative humidity, and the intermediate layer 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 intermediate layer 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] All of these and other embodiments can be used in combination, and the features and advantages of the present invention will be readily understood by those skilled in the art upon reading the following detailed description.

Mode for Carrying Out the Invention

[0039] The present invention relates to a resin composition containing at least one recycled material, a masterbatch thereof, films, sheets, and intermediate layers prepared therefrom or from the masterbatch, glass laminates containing such intermediate layers, and methods for manufacturing them. Further details are shown below.

[0040] In the context of this specification, all publications, patent applications, patents, and other references mentioned in this specification are, unless otherwise stated, incorporated herein by reference in their entirety for all purposes as if fully set forth.

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

[0042] Trademarks are shown in capital letters, unless otherwise indicated.

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

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

[0045] When a quantity, concentration, or other value or parameter is given as a range, or a list of upper and lower limits, this is to be understood as specifically disclosing all ranges formed from any pair of upper and lower limits, whether or not the ranges are individually disclosed. When a numerical range is described in this specification, unless otherwise stated, the range is intended to include its endpoints, and all integers and fractions within the range. The scope of this disclosure is not intended to be limited to the specific values recited when defining the range. By way of example, a recited range of 1 to 10 fully encompasses and includes the independent sub-range 3.4 to 7.2.

[0046] When the term "about" is used, it is used in the sense that a certain effect or result can be obtained within a certain tolerance range, and one of ordinary skill in the art knows how to obtain that tolerance range. When the term "about" is used to describe a value or endpoint of a range, the present disclosure should be understood to include the specific value or endpoint recited.

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

[0048] The transitional phrase "consisting of" excludes elements, steps, or components not specified in the claim, closes the claim against including materials other than those recited, except for impurities ordinarily associated therewith. When the phrase "consisting of" appears in the body of the claim rather than immediately following the preamble, it limits only the elements recited in that clause and does not exclude other elements from the claim as a whole.

[0049] The transitional phrase "consisting essentially of" limits the scope of the claim to those materials or steps that do not materially affect the basic and novel characteristics of the claimed invention, together with the specified materials or steps. A claim "consisting essentially of" is intermediate between a closed claim in the form "consisting of" and a fully open claim in the form "comprising". Any additives defined herein, any additives at appropriate levels for such additives, and minor impurities are not excluded from embodiments by the term "consisting essentially of" so long as they do not materially affect the basic and novel characteristics of the particular embodiment.

[0050] Furthermore, unless explicitly stated to the contrary, "or" and "and / or" are inclusive and not exclusive. For example, the condition A or B, or A and / or B, is satisfied by any one of the following: A is true (or present) and B is false (or absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0051] The use of "a" or "an" to describe various elements and components herein is for convenience only and to give a general sense of the disclosure. This description should be read to include one or at least one unless it is apparent that it has another meaning, and the singular also includes the plural.

[0052] As used herein, the terms "substantially" or "primarily" mean greater than 50% of the material referenced, unless otherwise specifically defined herein. Unless otherwise specified, percentages are on a molar basis when referring to molecules (such as hydrogen and ethylene), and on a weight basis otherwise (such as additive content).

[0053] As used herein, the terms "substantial portion" or "substantially" mean all or nearly all or a majority, as would be understood by one of ordinary skill in the art in the context in which they are used, unless otherwise defined. This is intended to account for some reasonable variation from 100% that would typically occur in industrial or commercial scale situations.

[0054] The terms "depleted" or "reduced" are synonymous with having been reduced from what was originally present. For example, removing a substantial portion of a material from a stream produces a material-depleted stream in which the material is substantially depleted. Conversely, the terms "enriched" or "increased" are synonymous with being greater than what was originally present.

[0055] As used herein, the term "unused" refers to newly created, generally pure materials. The form of such materials may vary depending on the manufacturing method. For example, physical or thermal means (e.g., grinding, cutting, melting, etc.) that change only the physical form of such materials without further things (e.g., chemical changes, degradation, mixing with other materials, etc.) do not change their "unused" characteristics.

[0056] As used herein, the term "granule" means particles ranging from very irregular shapes to spherical. The particle "size" can be defined as the weight per 100 particles. In one embodiment, the particle "size" is about 0.01 - 10 grams. In another embodiment, the regenerated material granules (particles) of suitable size are generally not limited, but can range in size from about 0.1 mm, or from about 0.2 mm, up to about 5 mm, or up to about 4 mm, or up to about 2 mm, or up to about 1 mm. The granules may be porous or may be composed of an aggregate of "lumps" or somewhat "fused" small particles that behave like physically large particles / granules.

[0057] As used herein, the term "pellet" means a polymeric resin that is generally cylindrical (strand cut) or nearly spherical (e.g., underwater melt cut) and has a weight of 0.1 to 10 grams per 100 pellets.

[0058] As used herein, the term "new" refers to a newly manufactured or as-received from a vendor, generally pure material that has not undergone post-treatment to create other forms / shapes or heat treatment that causes melting of the resin.

[0059] As used herein, the terms "intimately mix", "intimately mixing", "intimately mixed", and "intimate mixing" mean combining or combining two or more polymeric materials, such as unused ionomer and recycled material, so that optimal optical distortion parameters are achieved. Usually, heat treatment (such as melt mixing) is performed. Measurement of optical distortion can be performed by practical methods including, but not limited to, the "shadowgraph" technique. A shadowgraph is generally a high-sensitivity visualization method that can reveal optical inhomogeneities within a transparent material by the shadow projected by the disturbance when a light ray is refracted. Another common method is to determine the degree of optical distortion when the glass laminate of the sample is placed on the straight line of the line of sight and when it is not placed when looking at the "checkerboard" target grid.

[0060] As used herein, the term "forming" with respect to a polymeric material means causing the material to form into films and sheets. Generally, the thickness of the film is about 0.01 to about 0.25 mm, and the thickness of the sheet is about 0.25 mm to about 10 mm.

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

[0062] As used herein, the terms "plastic" and "polymer" are used interchangeably. The term "plastic" can refer to certain types of polymers and is generally understood to be composed of long chains of polymers, where polymers are composed of smaller, uniform molecules. However, in the present invention, both terms can be used interchangeably.

[0063] Measurements of haze, YID, and other properties are made in the form of a glass laminate. In the combination of haze and yellowness index (YID), especially with a rapid cooling profile, there is little difference in haze, but there can be a large difference in YID. Substantially all (about 100%) of each resin can have an acceptable YID, but when two resins are combined, the yellowness can increase. This can be particularly important when mixing recycled materials with different heat profiles. Differences have been confirmed between "normal" cooling and "rapid" cooling, differences when different resins are combined, differences in the amount of each resin, and differences in the cooling method used. A blue colorant can be added to the ionomer resin (to make the yellow of the intermediate layer film / sheet less visible), but this is an additional step, and such an addition only compensates for the degree of yellowness at a given composition formulation and cooling rate. Furthermore, this means will change the "color" of the resin even to "green" or "gray", and in substantially all cases, will reduce the overall light transmittance of the molded article and create further differences between resin blends with and without the blue colorant. In addition, the refractive index (RI) of each resin is important, especially for haze. This is also generally related to mixing. In addition to considering the thickness of the intermediate layer of the glass laminate, any effects resulting from the extrusion method or resin degradation must also be considered.

[0064] As used herein, the terms "recycled material" and "recycled polymer material" each refer to a polymer material that contains at least one dialkoxysilane adhesion promoter and is recovered from a previously manufactured polymer material. The previously manufactured polymer material can be in any form and can be, or can include, waste materials from the process used to manufacture it, i.e., defective products, trim materials, etc. This polymer material contains not only one or more polymers, but also at least one dialkoxysilane adhesion promoter and optionally one or more additional additives. Thus, when this polymer material is recycled, at least one dialkoxysilane adhesion promoter and any additional optional additives are also considered to be "recycled". Recycled polymer materials can also be obtained from downstream manufacturing processes, such as trim materials resulting from a conversion process in which films or sheets are assembled into glass laminates. Furthermore, it is possible to reprocess the recovered polymer material by filtering out impurities in a secondary extrusion process to produce a material suitable for use.

[0065] As used herein, the term "copolymer" refers to a polymer containing copolymerized units resulting from the copolymerization of two or more comonomers. In this regard, copolymers can be described herein by reference to their constituent comonomers or the amounts of their constituent comonomers, such as "a copolymer containing ethylene and 15 wt% acrylic acid" or similar descriptions. Such descriptions may be considered informal in that they do not refer to the comonomers as copolymerized units, do not include the conventional nomenclature for copolymers, such as that of the International Union of Pure and Applied Chemistry (IUPAC), do not use a product representation based on the method of manufacture, or for other reasons. However, as used herein, a description of a copolymer referring to its constituent comonomers or the amounts of its constituent comonomers means that the copolymer contains the copolymerized units of the specified comonomers (if specified, in the specified amounts). It follows that a copolymer is not the product of a reaction mixture containing a given comonomer in a given amount, 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 containing at least three monomers.

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

[0068] As used herein, the term "(meth)acryl" refers to acrylic or methacrylic, such as "acrylic acid or methacrylic acid", or "alkyl acrylate or alkyl methacrylate", in the form of a single or combined form such as "(meth)acrylate".

[0069] As used herein, the term "ionomer" generally refers to a polymer that includes an ionic group that is a carboxylate salt, such as an ammonium carboxylate, an alkali metal carboxylate, an alkaline earth metal carboxylate, a transition metal carboxylate, and / or a combination of such carboxylate salts. Such polymers are generally produced by partially or completely neutralizing the carboxylic acid groups of a precursor or parent polymer that is an acid copolymer as defined herein, for example, by reaction with a base. An alkali metal ionomer as used herein is a sodium ionomer, for example, a copolymer of ethylene and methacrylic acid, in which 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 carboxylate.

[0070] For convenience, many elements of the present invention are discussed separately, and there may be provided a list of options and numerical values may be within ranges, but for the purposes of this disclosure, that should not be regarded as limiting the scope of this disclosure or supporting any claim to any combination of such separate components, list items, or ranges. Unless otherwise specified, all possible combinations in this disclosure should be regarded as explicitly disclosed for all purposes.

[0071] Methods and materials similar or equivalent to those described herein can be used in the practice or testing of this disclosure, but suitable methods and materials are described herein. Accordingly, the materials, methods, and examples herein are illustrative only and are not intended to be limiting except as specifically described.

[0072] Dialkoxysilane adhesion promoter Adhesion promoters suitable for use in accordance with various embodiments of the compositions, masterbatches, methods, films, sheets, intermediate layers, laminates, etc. of the present invention are dialkoxysilanes. Without being bound by theory, the hydrolyzed silanol moiety of the silane is thought to be able to form an adhesive bond with the glass surface (silanol), thereby enhancing the adhesion at the interface between the polymer and the glass surface. In that case, the remaining portion of the silane molecule should be "fixed" in some way to the surrounding ionomer resin "matrix". One way to achieve this is to select functional groups such that the silane interacts in an advantageous way that allows it to bond chemically, or by ionic, hydrogen, or sufficient van der Waals forces, or to have a size and shape that can "bridge" between the intermediate layer and the glass surface, thereby enhancing the adhesion over the same intermediate layer without the advantageous silane additive.

[0073] In one embodiment, each alkoxy group of the dialkoxysilane contains from 1 to 3 carbon atoms individually. 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.

[0074] In another embodiment, in addition to the alkoxy group, the dialkoxysilane also contains a "reactive" chemical group for bonding to the ionomer resin matrix, such as a carboxylic acid reactive group like an amino group or a glycidyl group. 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.

[0075] Desirably, the dialkoxysilane in pure form is a liquid under ambient conditions (e.g., 20 °C). Such specific examples include N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane (CAS#3069-29-2) and 3-glycidoxypropylmethyldiethoxysilane (CAS#2897-60-1).

[0076] In a preferred embodiment of the present invention, at least a part, or a majority, or substantially all of the dialkoxysilane adhesion promoter is present in and used in the form of recycled materials (e.g., dipolymers and / or terpolymers ionomers recovered from previously manufactured polymer materials containing at least one dialkoxysilane adhesion promoter). The number and types of additives (e.g., antibacterial agents, anti-fogging additives, antioxidants, fillers, flame retardants, slip agents, etc.) present therein in addition to the dialkoxysilane adhesion promoter are not limited as long as they do not significantly affect the optical properties of the laminate containing the intermediate layer made from the composition of the present invention.

[0077] If necessary, additional "new" dialkoxysilane adhesion promoters can also be used.

[0078] Ionomer 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 dipolymers having structural units derived from ethylene and structural units derived from an α,β-unsaturated carboxylic acid, wherein at least a portion of the structural units derived from the α,β-unsaturated carboxylic acid are neutralized with sodium ions. Another preferred ionomer is a terpolymer having structural units derived from ethylene, structural units derived from an α,β-unsaturated carboxylic acid, structural units derived from an α,β-ethylenically unsaturated carboxylic acid ester, and optionally structural units derived from a derivative of an α,β-unsaturated carboxylic acid other than its ester, such as its amide or anhydride, wherein at least a portion of the structural units derived from the α,β-unsaturated carboxylic acid are neutralized with sodium ions. In certain embodiments, the dipolymer is the only ionomer in the compositions, films, etc. of the present invention. In certain embodiments, the terpolymer is the only ionomer in the compositions, films, etc. of the present invention.

[0079] In preferred embodiments of both the preferred dipolymer and the preferred terpolymer, the content ratio of the structural units derived from the α,β-unsaturated carboxylic acid is typically 2% by mass or more, or 5% by mass or more (based on the total mass of the copolymer), which includes 7% by mass, 10% by mass, 12% by mass, 14% by mass, 15% by mass, and 18% by mass or more. Further, the content ratio of the structural units derived from the α,β-unsaturated carboxylic acid is typically 30% by mass, 27% by mass, 25% by mass, 23% by mass, or 22% by mass or less (based on the total mass of the copolymer).

[0080] Examples of α,β-unsaturated carboxylic acids that make up preferred dipolymers and terpolymer 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.

[0081] Preferred terpolymers further include copolymerized units of one or more α,β-ethylenically unsaturated carboxylic acid esters. Alkyl esters having 3 to 10, or 3 to 8 carbons are typically used. Specific examples of suitable esters of unsaturated carboxylic acids 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, dodecyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, lauryl acrylate, lauryl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl fumarate, vinyl acetate, vinyl propionate, and mixtures 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 mixtures 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 both of n-butyl acrylate and isobutyl acrylate are used.

[0082] In one embodiment, the preferred dipolymers and terpolymers each independently have a melt flow rate (MFR) of from about 1 or from about 2 to up to about 4000 g / 10 min, or up to 1000 g / 10 min, or up to about 400 g / 10 min, as measured according to ASTM method D1238-89 at 190° C. and 2.16 kg.

[0083] One of ordinary skill in the art can synthesize all of the ionomers described herein, including the preferred dipolymers and terpolymers, based on their chemical descriptions, optionally considering the disclosures in, for example, US3404134, US5028674, US6500888B2, US6518365B1, US8334033B2, and US8399096B2. In one embodiment, the method described in US8399096B2 is used, and derivatives of the second α,β-ethylenically unsaturated carboxylic acid are present in the reaction mixture at a sufficiently high level and in complementary amounts.

[0084] In one embodiment, to obtain useful dipolymers and terpolymers ionomers, their ethylene acid copolymer precursors are partially neutralized by reaction with one or more bases. Examples of suitable procedures for neutralizing ethylene acid copolymers are described in US3404134 and US6518365B1. After neutralization, from about 1% or from about 10% or from about 15% or from about 20% to about 90% or to about 60% or to about 55% or to about 30% of the hydrogen atoms of the carboxylic acid groups present in the ethylene acid copolymer precursor are replaced with other cations. Alternatively stated, from about 1% or from about 10% or from about 15% or from about 20% to about 90% or to about 60% or to about 55% or to about 30% of the total content of carboxylic acid groups present in the ethylene acid copolymer precursor is neutralized. In another alternative expression, the acid groups are neutralized to a level of from about 1% or from about 10% or from about 15% or from 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 calculated or measured for the non-neutralized ethylene acid copolymer precursor. The neutralization level can be adjusted according to a particular end use.

[0085] The counterion 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, and counterions other than sodium cations may be present in a minor 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.

[0086] Suitable cations other than alkali metal cations include any positively charged species that are stable under the conditions under which the ionomer composition is synthesized, processed, and used. Suitable cations can be used in combinations of two or more. Typically, such other cations are metal cations and can be monovalent, divalent, trivalent, or polyvalent. Examples of monovalent metal cations include, but are not limited to, cations such as potassium, lithium, silver, mercury, and copper. Examples of divalent metal cations include, but are not limited to, cations such as beryllium, magnesium, calcium, strontium, barium, copper, cadmium, mercury, tin, lead, iron, cobalt, nickel, and zinc. Examples of trivalent metal cations include, but are not limited to, cations such as aluminum, scandium, iron, and yttrium. Examples of polyvalent metal cations include, but are not limited to, cations such as titanium, zirconium, hafnium, vanadium, tantalum, tungsten, chromium, cerium, and iron. When the metal cation is polyvalent, complexing agents such as stearate groups, oleate groups, salicylate groups, and phenolate groups can be included as described in US3404134. Typically, when present, the metal cation used is a monovalent or divalent metal cation, such as lithium, magnesium, zinc, potassium, and combinations of one or more of these metal cations.

[0087] In one embodiment, the counterions other than sodium are present in at most "impurity" amounts as commonly found in industrial situations, as would be recognized by one of ordinary skill in the art.

[0088] Sodium-neutralized ethylene acid dipolymers and terpolymers are ionomers, and preferably have a melt index measured according to ASTM method D1238-89 at 190 °C and 2.16 kg that is lower than the melt index of the corresponding ethylene acid copolymer precursor. The melt index of the ionomer depends on several factors, including the melt index of the ethylene acid copolymer, the amount of copolymerized acid, the neutralization level, the identity and valence of the cation. Further, the desired value of the melt index of the ionomer may be determined by its intended end use. However, typically, the melt index of the ionomer, when measured according to ASTM method D1238-89 at 190 °C and 2.16 kg, is about 1000 g / 10 min or less, or about 750 g / 10 min or less, or about 500 g / 10 min or less, or about 250 g / 10 min or less, or about 100 g / 10 min or less, or about 50 g / 10 min or less, or about 25 g / 10 min or less, or about 20 g / 10 min or less, or about 10 g / 10 min or less, or about 7.5 g / 10 min or less.

[0089] In one embodiment, the preferred dipolymer consists essentially of, or consists of, copolymer units of (i) ethylene and (ii) at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms from about 10 wt% to, or from about 15 wt% to, or from about 18 wt% to, or from about 20 wt% to about 30 wt%, or to about 25 wt%, or to about 23 wt%, or to about 22 wt%, the weight percentage of the copolymer units is 100 wt% based on the total weight of the dipolymer, and at least a part of the carboxylic acid groups of the α,β-unsaturated carboxylic acid is neutralized to form an ionomer containing carboxylate groups having sodium counterions.

[0090] In one embodiment, a preferred terpolymer comprises (i) ethylene, (ii) at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms in an amount from about 10 wt% or from about 15 wt% or from about 18 wt% or from about 20 wt% to about 30 wt% or to about 25 wt% or to about 23 wt% or to about 22 wt%, (iii) at least one α,β-unsaturated carboxylic acid ester having 3 to 10 carbon atoms in an amount from about 2 wt% or from about 3 wt% or from about 4 wt% or from about 5 wt% to about 15 wt% or to about 12 wt% or to about 11 wt% or to about 10 wt%, and (iv) optionally, a copolymerized unit of 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 total weight percentage of the copolymerized units is 100 wt% and at least a part of the carboxylic acid groups of the α,β-unsaturated carboxylic acid is neutralized to form an ionomer containing carboxylate groups having sodium counterions), consisting essentially of or consisting of these.

[0091] Such terpolymer ionomers are generally disclosed in WO2015 / 199750A1, WO2014 / 100313A1 and US2017 / 0320297A1.

[0092] In one embodiment of a preferred dipolymer and / or terpolymer, the α,β-unsaturated carboxylic acid is methacrylic acid.

[0093] In one embodiment of a preferred terpolymer, the α,β-unsaturated carboxylic acid ester is n-butyl acrylate, isobutyl acrylate, or a mixture thereof.

[0094] In one embodiment of a preferred terpolymer, the terpolymer consists of or consists essentially of the copolymerized units of (i), (ii) and (iii).

[0095] In one embodiment, both the dipolymer ionomer resin and the terpolymer ionomer resin described herein are present, and the weight ratio (w / w dipolymer / terpolymer) of the alkali metal-neutralized ethylene acid dipolymer ionomer resin to the alkali metal-neutralized ethylene acid ester terpolymer ionomer resin is not particularly limited based on the total weight of the dipolymer and the terpolymer. In one embodiment, the weight ratio (w / w dipolymer / terpolymer) of the alkali metal-neutralized ethylene acid dipolymer ionomer resin to the alkali metal-neutralized ethylene acid ester terpolymer ionomer resin in the composition is 0.5 / 99.5 to 99.5 / 0.5, 1 / 99 to 99 / 1, 3 / 97 to 97 / 3, 5 / 95 to 95 / 5, 10 / 90 to 90 / 10, 15 / 85 to 85 / 15, 20 / 80 to 80 / 20, 25 / 75 to 75 / 25, 30 / 70 to 70 / 30, 35 / 65 to 65 / 35, 40 / 60 to 60 / 40, 45 / 55 to 55 / 45, and including 50 / 50, 0.1 / 99.9 to 99.9 / 0.1 based on the total weight of the dipolymer and the terpolymer.

[0096] In one embodiment, one of the dipolymer (i) or the terpolymer (ii) is from about 5 wt% to about 30 wt%, or up to about 25 wt%, up to about 20 wt%, up to about 15 wt%, or up to about 10 wt% based on the combined weight of (i)+(ii). In another embodiment, one of (i) or (ii) is from about 10 wt% to about 30 wt%, or up to about 25 wt%, up to about 20 wt%, or up to about 15 wt% based on the combined weight of (i)+(ii). In another embodiment, one of (i) or (ii) is from about 15 wt% to about 30 wt%, or up to about 25 wt%, up to about 20 wt% based on the combined weight of (i)+(ii). In another embodiment, one of (i) or (ii) is from about 20 wt% to about 30 wt%, or up to about 25 wt% based on the combined weight of (i)+(ii). In another embodiment, one of (i) or (ii) is from about 25 wt% to about 30 wt% based on the combined weight of (i)+(ii).

[0097] In one embodiment, only one kind of the dipolymers and terpolymers ionomers described herein is present, and the total amount of the dipolymer or terpolymer present is all, or substantially all, of compositions, sheets, films, laminates, etc., based on the total weight of all polymers of any kind present.

[0098] To maintain sufficient integrity of the laminate (e.g., prevention of interlayer delamination defects) and sufficient retention of the glass in the post-break state, a critical minimum level of adhesion is required, but optimization or adjustment of the impact performance of the resulting laminate can be intentionally carried out. The optimal addition amount of the adhesion improver (cumulative) varies depending on the additive used and the resin to be adhesion-improved, but preferably, the adhesion of the resulting laminate to the glass is adjusted so that it is generally about 3 or more and about 10 or less in the Pannell test (described in WO03 / 033583A1, etc.). In particular, when high puncture resistance is required, it is more preferable to adjust the addition amount of the adhesion improver so that the adhesion is about 3 or more and about 6 or less, and when high glass splash prevention is required, it is more preferable to adjust the addition amount of the adhesion improver so that the adhesion is about 7 or more and about 10 or less.

[0099] Other additives In addition to the aforementioned dialkoxysilanes, embodiments of the present invention may further optionally contain one or more other additives including, for example, antioxidants, ultraviolet absorbers, light stabilizers, anti-blocking agents, pigments, dyes, heat shielding materials (infrared absorbers), or mixtures thereof. Such other additives are well known to those skilled in the art in a general sense.

[0100] Examples of antioxidants include phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, etc. Among these, phenolic antioxidants are preferred, and alkyl-substituted phenolic antioxidants are particularly preferred.

[0101] Examples of phenolic antioxidants include acrylate compounds such as 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate and 2,4-di-t-amyl-6-(1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl)phenyl acrylate; alkyl-substituted phenolic compounds such as 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidenebis(4-methyl-6-t-butylphenol), 4,4'-butylidenebis(6-t-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-t-butylphenol), bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane, 3,9-bis(2-(3-(3-t-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-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis(methylene-3-(3’,5’-di-t-butyl-4’-hydroxyphenyl)propionate)methane, and triethylene glycol bis(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate); triazine group-containing phenolic compounds, for example, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-bis-octylthio-1,3,5-triazine, 6-(4-hydroxy-3,5-dimethylanilino)-2,4-bis-octylthio-1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-t-butylanilino)-2,4-bis-octylthio-1,3,5-triazine, and 2-octylthio-4,6-bis-(3,5-di-t-butyl-4-oxy anilino)-1,3,5-triazine; etc.

[0102] Examples of phosphorus-based antioxidants include monophosphite compounds such as triphenyl phosphite, diphenylisodecyl phosphite, phenyldiisodecyl phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(2-t-butyl-4-methylphenyl) phosphite, tris(2,4-di-t-butyl) phosphite, tris(cyclohexylphenyl) phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl) octyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene; diphosphite compounds such as 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecyl phosphite), 4,4'-isopropylidene-bis(phenyl-di-alkyl(C12-C15) phosphite), 4,4'-isopropylidene-bis(diphenylmonoalkyl(C12-C15) phosphite), 1,1,3-tris(2-methyl-4-di-tridecyl phosphite-5-t-butylphenyl) butane, and tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene phosphite; and the like. Among these, monophosphite compounds are preferred.

[0103] Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, pentaerythritol-tetrakis-(β-lauryl-thiopropionate), 3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, and the like.

[0104] These antioxidants can be used alone or in combination of two or more of them. In the final resin composition, the antioxidant used is typically 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. Further, the amount of the antioxidant used is typically 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 (dipolymer and terpolymer). The masterbatch composition is adjusted up and down according to what is added thereto.

[0105] 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-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, and 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)triazole; hindered amine-based ultraviolet absorbers, such as 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butyl malonate, and 4-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)-1-(2-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)ethyl)-2,2,6,6-tetramethylpiperidine; benzoate-based ultraviolet absorbers, such as 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; and the like.

[0106] These ultraviolet absorbers can be used alone or in combination of two or more of them. In the final resin composition, the amount of the ultraviolet absorber utilized is typically about 10 ppm by weight or more, or about 100 ppm by weight or more, based on the weight of the ionomer resin. Further, the amount of the ultraviolet absorber utilized is typically about 50,000 ppm or less, or about 10,000 ppm or less, based on the weight of the ionomer resin.

[0107] In some embodiments, it is also possible to use a combination of two or more UV absorbers.

[0108] In other embodiments, no UV absorber is added, or the composition and the masterbatch are substantially free of UV absorber.

[0109] Examples of light stabilizers include, for example, hindered amine-based materials such as "ADEKA STAB LA-57" (trade name) manufactured by ADEKA Corporation, and "TINUVIN 622" (trade name) manufactured by Ciba Specialty Chemicals Inc.

[0110] When making laminated glass by incorporating heat insulating fine particles or a heat insulating compound as a heat insulating material into the intermediate layer of the present invention and imparting a heat insulating function to the laminate, the transmittance at a wavelength of 1,500 nm can be controlled to about 50% or less, and the TDS value (calculated from ISO13837:2008) can be controlled to about 43% or less.

[0111] Examples of heat insulating fine particles include metal-doped indium oxides such as tin-doped indium oxide (ITO), metal-doped tin oxides such as antimony-doped tin oxide (ATO), metal-doped zinc oxides such as aluminum-doped zinc oxide (AZO), and metal element composite tungsten oxides represented by the following general formula: M m WO n(M represents a metal element, m is from about 0.01 or more to about 1.0 or less, and n is from about 2.2 or more to about 3.0 or less), zinc antimonate (ZnSb2O5), lanthanum hexaboride, etc. may be mentioned. Among these, ITO, ATO, and metal element composite tungsten oxide are preferable, and metal element composite tungsten oxide is more preferable. In the metal element composite tungsten oxide, examples of the metal element represented by M include Cs, Tl, Rb, Na, K, etc., and Cs is particularly preferable. From the viewpoint of heat insulation properties, m is preferably about 0.2 or more, or about 0.3 or more, and preferably about 0.5 or less, about 0.4 or less.

[0112] From the viewpoint of the transparency of the final laminate, the average particle diameter of the heat-insulating fine particles is preferably about 100 nm or less, or about 50 nm or less. It should be noted that the average particle diameter of the heat-insulating fine particles mentioned in this specification means the one measured by a laser diffraction device.

[0113] In the final resin composition, the content of the heat-insulating fine particles is preferably about 0.001% by weight or more, or about 0.05% by weight or more, or about 0.1% by weight or more, or about 0.2% by weight or more based on the weight of the ionomer resin. Furthermore, the content of the heat-insulating fine particles is preferably about 5% by weight or less, or about 3% by weight or less, or about 1% by weight or less, or about 0.5% by weight or less.

[0114] Examples of the heat-insulating compound include phthalocyanine compounds, naphthalocyanine compounds, etc. From the viewpoint of further improving the heat insulation property, the heat-insulating compound preferably contains a metal. Examples of the metal include Na, K, Li, Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Sn, V, Ca, Al, etc., and Ni is particularly preferable.

[0115] The content of the heat-insulating compound is preferably about 0.001% by weight or more, or about 0.005% by weight or more, or about 0.01% by weight or more based on the weight of the ionomer resin. Furthermore, the content of the heat-insulating compound is preferably about 1% by weight or less, or about 0.5% by weight or less.

[0116] Manufacture of a recycled material-containing composition and a masterbatch In one embodiment, a recycled material (a polymeric material containing at least one dialkoxysilane adhesion promoter and recovered from a previously manufactured polymeric material) can be fed into an extrusion process together with one or more other resins, preferably including unused resin and / or fresh resin. Additional additives can also be included during the extrusion process together with the recycled material. The recycled material may contain additives in addition to at least one dialkoxysilane adhesion promoter, depending on the origin of the recycled material and its original intended use. The physical size and dimensions of the recycled resin may require additional processing steps to facilitate re-“feeding” it into the extrusion process for blending. Further, by reducing the size of the recycled material and optimizing its physical form, the uniformity of the reprocessed resin is improved, for example, minimizing the optical non-uniformity of the final film / sheet and the resulting glass laminate. Alternatively, powerful extrusion kneading can be utilized to uniformly blend the non-uniformity / heterogeneity, but in this case, it may promote the occurrence of new resin degradation and often appears as an increase in yellowness and degraded resin (e.g., “black spots”), so care must be taken. Depending on the form of the recycled material, when a step of reducing the size is required, there are various means to achieve this step. Rotary cutting, mechanical cutting, slicing, shearing, or other size reduction techniques can be used to prepare the recycled material for re-feeding / re-introduction into the process. The recycled material particles of suitable size can generally range from about 0.1 mm, or from about 0.2 mm, up to about 5 mm, or up to about 4 mm, or up to about 2 mm, or up to about 1 mm. Such particles can be measured with an optical microscope equipped with a stage micrometer. Particles up to 1 mm can be measured using a 1 mm stage micrometer with a 0.01 mm scale. Particles over 1 mm can be measured using a 25 mm stage micrometer with a 0.05 mm scale.For spherical particles, or for particles of rectangular or irregular shape, the maximum dimension of 20 randomly selected particles from the resin can be measured, and the average value of the 20 particles can be used to characterize the general particle size. For example, cryogenic grinding can be used to reduce an ionomer resin material from a larger form with a nominal average particle size of about 4 mm to an approximate average particle size in the range of about 0.1 mm to about 0.5 mm. Also, these particles are crushed and become irregular in shape during the attrition process. The cryogenic grinding process is generally well-known to those skilled in the art and typically involves the use of liquid nitrogen to cool the resin material prior to the grinding / attrition process. After cooling, the recycled material passes through mechanical attrition. By using liquid nitrogen to cool the recycled material, the size can be reduced more effectively without unnecessary heating and without promoting further polymer degradation.

[0117] In some cases, the end trim can be directly re-supplied to an extrusion process with, for example, an appropriate device design (e.g., guide roll / pull roll and screw design). In some cases, the feed can be introduced into a "side feeder" and combined with the main feed. All means for returning the recycled resin are within the scope of this patented technology. As described above, this recycled material can include one or more additives. The first recycled material can be a first ionomer resin.

[0118] These ionomer resin particles can also be prepared by other conventional means, such as melt cutting in water. The pellets thus produced generally have a diameter or cross-section of 0.5 - 5 mm. Other methods well-known to those skilled in the art can be used for compounding and blending, generally prior to the melting process achieved in an extrusion process.

[0119] The present invention may also use at least one of the following.

[0120] Second granules of a second recycled material, which may also be an ionomer, containing an additive and referred to herein as a second ionomer resin, and

[0121] 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.

[0122] "New" (i.e., not recycled) additives may also be present in the third and fourth resins.

[0123] When these materials are present / prepared, the first granules are co-extruded using an extruder with one or more of the second granules, the first pellets and the second pellets, and optionally one or more new additives, under conditions to melt and intimately mix the materials to produce a melt. The melt thus produced is then formed into a film or sheet having a thickness of up to about 2.5 mm that is substantially continuous in the longitudinal direction.

[0124] The ionomer resin can combine virgin material and recycled material. In one embodiment, the ionomer resin is recycled ionomer resin in an amount of from about 5 wt% to about 30 wt%, or up to about 25 wt%, or up to about 20 wt%, or up to about 15 wt%, or up to about 10 wt% based on the total weight of the ionomer resin. In another embodiment, the ionomer resin is recycled ionomer resin in an amount of from about 10 wt% to about 30 wt%, or up to about 25 wt%, or up to about 20 wt%, or up to about 15 wt% based on the total weight of the ionomer resin. In another embodiment, the ionomer resin is recycled ionomer resin in an amount of from about 15 wt% to about 30 wt%, or up to about 25 wt%, or up to about 20 wt% based on the total weight of the ionomer resin. In another embodiment, the ionomer resin is from about 20 wt% to about 30 wt%, or up to about 25 wt% based on the combined weight of (i)+(ii). In another embodiment, the ionomer resin is recycled ionomer resin in an amount of from about 25 wt% to about 30 wt% based on the total weight of the ionomer resin.

[0125] Manufacture of Resin Compositions and Masterbatches The resin composition of the present invention can be manufactured as a melt blend by supplying various components to an extruder and intimately mixing the components under melting conditions of the ionomer resin to produce a substantially homogeneous mixture that can be finally formed into a final shape, for example, by melt extrusion or molding.

[0126] As will be appreciated by those skilled in the art, in a melt blend, care must be taken to ensure that the mixing is strong enough to blend the dialkoxysilane sufficiently uniformly into the resin. Generally, this high degree of mixing via extrusion compounding is achieved by generating sufficient shear and residence time in an extruder. Also, care must be taken to avoid undesirable results such as local high concentrations of dialkoxysilane, decomposition of the dialkoxysilane and / or one or both of the dipolymer and terpolymer due to high temperatures, etc. The formation of discolored resin, gels or degraded products (e.g., black spots) can be avoided by selecting the correct process equipment and process conditions, which is within the scope of the skill of those skilled in the art.

[0127] For example, it is well understood that the degree of hydrolysis of dialkoxysilane increases by being overly exposed to moisture and for long periods of time, and thus perhaps additional considerations for controlling external moisture contact are required. For example, it may be necessary to cover with dry air or nitrogen to maintain the desired minimum degree of hydrolysis of the silane.

[0128] In one embodiment of the composition according to the present invention, the composition is a particulate composition comprising all of a recycled material and one or both of a dipolymer resin and a terpolymer resin (ionomer resin) in particulate form.

[0129] Desirably, this particulate composition can be prepared by physically mixing ionomer resin particles and recycled particles under non-softening conditions of the ionomer resin and the recycled material, in other words, under non-softening conditions where the ionomer resin and the recycled material do not melt or soften to the extent that they significantly agglomerate or otherwise lose their original particulate form.

[0130] For both the dipolymers and the terpolymers, the size of the ionomer resin particles is not particularly limited. Particles of a suitable size for preparing the final composition and the masterbatch composition can preferably range in size from about 0.1 mm, or from about 0.2 mm, to about 5 mm, or to about 4 mm, or to about 2 mm, or to about 1 mm. Such particles can be measured with an optical microscope equipped with a stage micrometer. Particles up to 1 mm can be measured using a 1 mm stage micrometer with a 0.01 mm scale. Particles over 1 mm can be measured using a 25 mm stage micrometer with a 0.05 mm scale. For the diameter, or in the case of particles of rectangular or irregular shape, the maximum dimension of 20 particles randomly selected from the resin can be measured, and the average value of the 20 particles can be used to characterize the general particle size.

[0131] In one embodiment, the particles for preparing the compositions and masterbatches of the present invention are reduced in size 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 to an approximate average particle size in the range of about 0.1 mm to about 0.5 mm. By reducing the particle size in this way, the particle surface area relative to the particle weight increases. Also, these particles are broken during the grinding process and become irregular in shape, which can further increase the surface area relative to the particle weight compared to the nominal spherical ionomer resin pellet shape. The cryogenic grinding process is generally well known to those skilled in the art and typically involves the use of liquid nitrogen to cool the pellets prior to the grinding / milling process. After cooling, the pellets pass through a mechanical mill. Using liquid nitrogen to cool the pellets allows for more effective size reduction without unnecessary heating and without causing polymer degradation.

[0132] These ionomer resin particles can also be prepared by other conventional means, such as melt cutting in water (e.g., "micro pellets" having an average diameter of about 0.5 to about 1.5 mm) or other methods well known to those skilled in the art.

[0133] The dialkoxysilane additive is preferably present in the final resin composition in an amount of from about 50, or from about 100, or from about 250, or from about 500, or from about 750 to about 5000, or to about 4000, or to about 2000, or to about 1500, or to about 1250 weight ppm based on the total weight of the composition.

[0134] The dialkoxysilane additive is added to the composition of the present invention in whole or in part, or entirely as "recycled material". If in part, additional dialkoxysilane additive can be added with new resin or unused resin, etc. The recycled material preferably contains at least one of a dipolymer and a terpolymer in addition to the dialkoxysilane additive.

[0135] In one embodiment, in the compositions, films, intermediate layers, etc. of the present invention, based on the total weight of the ionomer resin + recycled material, the weight ratio (w / w ionomer resin / recycled material) of the unused or new alkali metal-neutralized ethylene acid copolymer ionomer resin (e.g., dipolymer, terpolymer) to the recycled material is not particularly limited. In one embodiment, in a given composition, masterbatch, film, etc., based on the total weight of the ionomer resin + recycled material, the weight ratio (w / w ionomer resin / recycled material) of the unused / new ionomer resin to the recycled material is 0.5 / 99.5 to 99.5 / 0.5, 1 / 99 to 99 / 1, 3 / 97 to 97 / 3, 5 / 95 to 95 / 5, 10 / 90 to 90 / 10, 15 / 85 to 85 / 15, 20 / 80 to 80 / 20, 25 / 75 to 75 / 25, 30 / 70 to 70 / 30, 35 / 65 to 65 / 35, 40 / 60 to 60 / 40, 45 / 55 to 55 / 45, and including 50 / 50, which is 0.1 / 99.9 to 99.9 / 0.1. A preferred ratio is 99.5 / 0.5 to 70 / 30. For clarity and by way of example, a ratio of 70 / 30 is provided by a 100 g composition containing 70 g of new or unused dipolymer and 30 g of recycled material. The ratio of an 112 g composition containing 88 g of unused or new ionomer and 24 g of recycled material is 78.6 / 21.4.

[0136] The material manufactured previously that serves as the recycled material can be waste materials from the process used to manufacture it, i.e., defective products, edge materials, etc. This material generally contains not only the polymer but also one or more additives. Therefore, when recycling this polymer material containing additives, the additives are also considered "recycled". The recovered polymer material can also be obtained from downstream manufacturing processes such as edge materials from the conversion process where films or sheets are assembled into glass laminates. Furthermore, it is possible to reprocess the recovered polymer material by filtering impurities in a secondary extrusion process to produce a material suitable for use.

[0137] Once a recycled material containing at least one dialkoxysilane is obtained, it can be fed into the processes used to produce the final compositions, masterbatches, etc. of the present invention, together with other resins including unused / new resins. Additional additives may also be included during processing together with the recycled material. The recycled material generally contains one or more additives in addition to the dialkoxysilane, especially if this material has been previously extruded, for example, for the purpose of manufacturing an interlayer film / sheet product.

[0138] The physical size and dimensions of the recycled material may require some additional processing steps to facilitate "feeding" into processes such as blending, mixing, extrusion, etc. This generally applies especially when the recycled material results from current operations such as the extrusion forming of films, sheets, or laminates, and the recycled material is other than the trim at the ends of the sheets being manufactured. Furthermore, by reducing the size of the recycled material and optimizing its physical form, the uniformity of the reprocessed resin is improved, and the optical non-uniformity of the final film / sheet and the resulting glass laminate when used for this purpose is minimized. This is effective whether the recycled material is fed at 100% loading or together with unused ionomer resin or other resins and additives. Alternatively, strong extrusion kneading can be utilized to blend and eliminate non-uniformities uniformly, but this promotes the occurrence of new resin degradation and may often appear as an increase in yellowness and degraded resin (e.g., "black spots").

[0139] When the form of the recycled material requires a size reduction step, there are various means to achieve this step. Rotary cutting, mechanical cutting, slicing, shearing, or other size reduction techniques can be used to prepare the recycled material for re-supply / re-introduction into the process. Suitable sized ionomer resin recycled particles range from about 0.1 mm, or from about 0.2 mm, or from about 5 mm to about 4 mm, or to about 2 mm, or to about 1 mm. Such particles can be measured with an optical microscope equipped with a stage micrometer. Particles up to 1 mm can be measured using a 1 mm stage micrometer with a 0.01 mm scale. Particles over 1 mm can be measured using a 25 mm stage micrometer with a 0.05 mm scale. For diameter, or in the case of rectangular or irregularly shaped particles, the maximum dimension of 20 particles randomly selected from the resin can be measured and the average value of the 20 particles can be used to characterize the general particle size. For example, cryogenic grinding can be used to reduce an ionomer resin material from a larger form with a nominal average particle size of about 4 mm to an approximate average particle size in the range of about 0.1 mm to about 0.5 mm. Also, these particles are crushed and become irregularly shaped during the attrition process. The cryogenic grinding process is generally well-known to those skilled in the art and typically involves the use of liquid nitrogen to cool the resin material prior to the grinding / attrition process. After cooling, the recycled resin material passes through mechanical attrition. By using liquid nitrogen to cool the resin material, the size can be reduced more effectively without unnecessary heating and without promoting further polymer degradation.

[0140] In some cases, the recycled material of the end member at the end can be directly resupplied to the extrusion process using a suitable device design within the scope of the technology of an ordinary person skilled in the art (for example, guide roll / pull roll and screw design). For example, the end member at the end can be introduced into a "side feeder" and combined with the main feed. Any means for returning the recycled material is within the scope of the present invention. As described above, this recycled material may contain one or more additives such as those described above in addition to one or more dialkoxysilanes.

[0141] If additional additives are present, they can be mixed as part of a masterbatch or added in the preparation of the final resin composition via conventional means as recognized by those skilled in the art.

[0142] In one embodiment, the recycled material has a content of at least one of a dipolymer, a terpolymer, a dialkoxysilane, and other additives that is substantially the same as the content in the composition, film, etc. to be prepared, and preferably has the content of all of a dipolymer, a terpolymer, a dialkoxysilane, and other additives that is substantially the same as the content in the composition, masterbatch, film, etc. to be prepared. In another embodiment, the recycled material has a content such that the content of at least one of a dipolymer, a terpolymer, and a dialkoxysilane is different from the content in the final composition to be prepared. In a preferred embodiment, the final composition contains recycled material, a dipolymer or a terpolymer (not both), and one or more optional additives. In another preferred embodiment, any dipolymer and / or terpolymer present / added / used, except for those in the recycled material (if any), is in an unused or new form.

[0143] In a preferred embodiment, the recycled material comprises, consists essentially of, or consists of one or more dialkoxysilanes, a dipolymer or a terpolymer (but not both), and one or more optional additives. In another preferred embodiment, the dipolymer and / or terpolymer present / added / used, excluding those in the recycled material (if any), are in an unused or new form.

[0144] Sheet / film / intermediate layer The sheet of the ionomer resin composition of the present invention can be prepared by a conventional melt extrusion process or a melt molding process suitable for manufacturing the intermediate layer of a glass laminate. Such processes are well known to those skilled in the art as exemplified in the previously incorporated publications.

[0145] The sheet can be a single-layer sheet or a multi-layer sheet. For example, the multi-layer sheet can be formed to have a functional core layer sandwiched between two outer layers and any other inner layers. In one embodiment, at least one (or both) of the outer layers of the multi-layer intermediate layer is a sheet of the ionomer resin composition according to the present invention.

[0146] Examples of the functional core layer include acoustic attenuation layers 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), a layer containing an ethylene acid copolymer (see WO2015 / 085165A1), etc.

[0147] In a specific embodiment, the intermediate layer is a thermoplastic elastomer resin, for example, 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

[0148] (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

[0149] (ii) a hydrogenated product of a block copolymer having an aliphatic unsaturated polymer block (b) containing about 60 mol% or more of conjugated diene monomer units based on the aliphatic unsaturated polymer block,

[0150] wherein the aliphatic unsaturated polymer block (b) contains a total of about 50 mol% or more of isoprene units and butadiene units as conjugated diene monomer units,

[0151] and the amount of residual carbon-carbon double bonds in the aliphatic unsaturated polymer block derived from the conjugated diene monomer units is about 2 to about 40 mol%, which is a hydrogenated product.

[0152] Furthermore, the intermediate layer as a whole can be symmetric with a substantially consistent thickness, or can be asymmetric with a part of the intermediate layer having a greater thickness than another part (for example, partially or completely "wedge-shaped" as discussed in US2017 / 0320297A1 and US2018 / 0117883A1). Further, the laminate can be substantially transparent or can have coloring in all or part (for example, a "light-shielding band" as discussed in US2017 / 0320297A1 and US2018 / 0117883A1).

[0153] In the symmetric structure, the intermediate layer preferably has an overall film thickness of about 320 μm or more, or about 420 μm or more. Further, the overall film thickness should be about 1250 μm or less, or about 1000 μm or less.

[0154] In the wedge-like asymmetric structure, the thin part of the intermediate layer should have the thickness of the symmetric structure, but the thickness of the thick part depends on various parameters such as the wedge angle. In one embodiment of the wedge-shaped intermediate layer, the thickness of the thicker end 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 end is about 600 μm or more, or about 700 μm or more, or about 760 μm or more.

[0155] Furthermore, on the surface of the intermediate layer of the present invention, in order to assist degassing during the production of the laminate, an uneven structure such as an emboss can be formed by a conventionally known method. The shape of the emboss is not particularly limited, and a conventionally known one can be adopted.

[0156] In one embodiment, at least one surface (and preferably both surfaces) of the intermediate layer of the laminated glass is formed. By forming at least one surface of the intermediate layer of the laminated glass, when manufacturing the laminated glass, the air bubbles existing at the interface between the intermediate layer of the laminated glass and the glass can easily escape to the outside of the laminated glass, and therefore, the appearance of the laminated glass can be made good. It is preferable to form at least one surface of the intermediate layer of the laminated glass by the embossing roll method. By forming the surface of the intermediate layer of the laminated glass, recesses and / or protrusions are formed on the surface of the intermediate layer of the laminated glass.

[0157] The embossing roll used in the embossing roll method can be manufactured, for example, by using an engraving mill (master mill) having a desired uneven pattern and transferring the uneven pattern onto the surface of a metal roll. Further, a laser etching can also be used to manufacture the embossing roll. Further, after forming a fine uneven pattern on the surface of the metal roll as described above, a finer uneven pattern can be formed by subjecting the surface having the fine uneven pattern to a blasting treatment using an abrasive such as aluminum oxide, silicon oxide, or glass beads.

[0158] Furthermore, it is preferable that the embossing roll used in the embossing roll method is subjected to a release treatment. When an embossing roll without a release treatment is used, it becomes difficult to remove the intermediate layer of the laminated glass from the embossing roll. Examples of the release treatment method include known methods such as silicone treatment, Teflon (registered trademark) treatment, and plasma treatment.

[0159] 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") on the surface of the intermediate layer of the laminated glass formed 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.

[0160] 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, for example, by utilizing the confocal principle of a laser microscope or the like. 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 changed within a range not departing from the gist of the present invention.

[0161] Examples of the form of the shape imparted by the embossing roll method or the like include a lattice, a diagonal lattice, a diagonal ellipse, an ellipse, a diagonal groove, and a groove. The inclination angle of such a form is usually about 10° to about 80° with respect to the flow direction (MD direction) of the film. Further, the molding pattern may be a regular pattern, an irregular pattern such as a random mat pattern, or a pattern as disclosed in US7351468B2.

[0162] Molding by the embossing roll method or the like may be performed on one surface of the intermediate layer of the laminated glass, or may be performed on both surfaces, but more typically it is performed on both surfaces.

[0163] Laminate The laminate of the present invention can be manufactured by a conventionally known method. Examples thereof include using a vacuum laminator, using a vacuum bag, using a vacuum ring, using nip rolls, and the like. Further, after temporary contact adhesion, a method of putting the obtained laminate into an autoclave for final adhesion can be used.

[0164] When using a vacuum laminator, for example, a known apparatus used in the manufacture of solar cells can be used, and the assembly is laminated under a reduced pressure of about 1×10 -6 MPa or more and about 3×10 -2 MPa or less 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. The method of using a vacuum bag or a vacuum ring is described in, for example, EP1235683A1 (CA2388107A1). For example, the assembly is laminated at a pressure of about 2×10 -2 MPa at a temperature of about 130°C or more and about 145°C or less.

[0165] When using nip rolls, for example, a method is exemplified in which primary temporary contact adhesion is performed at a temperature below the flow start temperature of the skin resin, and then temporary contact adhesion is further performed under conditions close to the flow start temperature. Specifically, for example, after heating the assembly to about 30°C or higher and about 100°C or lower using an infrared heater or the like, degassing is performed by a roll, and then heating is performed at about 50°C or higher and about 150°C or lower, and thereafter, contact adhesion is performed by a roll to achieve adhesion or temporary adhesion.

[0166] The autoclave process that is additionally performed after temporary contact adhesion varies depending on the thickness and configuration of the module. For example, it is performed at a pressure of about 1 MPa or higher and about 15 MPa or lower, at a temperature of about 120°C or higher and about 160°C or lower, for about 0.5 hours or longer and about 2 hours or shorter.

[0167] The laminate may be processed by using the well-known "non-autoclave" process instead.

[0168] Advantageously, the glass used for producing the laminated glass is not particularly limited. Inorganic glasses such as float plate glass, polished plate glass, patterned glass, wired glass, heat-absorbing glass, and conventionally known organic glasses such as polymethyl methacrylate and polycarbonate can be used. These glasses may be any of colorless glass, colored glass, transparent glass, or non-transparent glass. These glasses may be used alone or in combination of two or more thereof.

[0169] As used in the present invention, the laminate is cooled after manufacture. To heat-treat the glass / interlayer assembly to the final laminated glass, an autoclave is generally used, but processes that do not use an autoclave are also utilized. Regardless of the specific process utilized, in all cases, a heat cycle that raises the temperature of the assembly above the melting point of the ionomer interlayer and then a cooling process that brings the laminate to near ambient temperature are used, and this step can be performed at different cooling rates. It may be rapidly cooled at a rate of about 2 to 20 °C / min, or cooled more slowly so that the laminate can reach room temperature with a somewhat suboptimal cooling process applied at a rate of about 0.1 °C / min, or at any rate in between. If the cooling rate is too fast and / or is performed in a non-uniform manner, the likelihood of thermal shock and glass breakage increases.

[0170] On the other hand, if the cooling of the glass laminate is too slow (generally less than 1 °C / min), further crystallization phenomena may occur, and the haze resulting in the final molded product may increase. Crystallinity is a property inherent in these types of ionomers derived from ethylene acid. Guidelines for processing these materials are provided (see: Kuraray Lamination Guidelines for Processing SentryGlas® - available from Kuraray America Inc.). There are several reasons for the limitations on the cooling rate during laminated glass processing: 1) Due to deficiencies in the design or operation of the equipment, heat removal from the laminated glass is physically limited, and the cooling rate drops to a somewhat suboptimal value. 2) In the case of very thick glass and / or interlayers and multi-layer laminate structures, even if an attempt is made to apply active external cooling, the absolute cooling rate of the ionomer resin inside the glass laminate is limited by heat conduction. 3) The glass laminate is placed inside an autoclave or oven or heat treatment means in such a way that different cooling rates occur due to changes in heat conduction (conduction and convection), as well as differences in the degree of non-uniform temperature zones and thermal radiation.

[0171] In practice, although not limiting the embodiments of this specification, "rapid" cooling generally refers to cooling achieved by using the maximum cooling rate setting of the available autoclave (e.g., United McGill - 20°C / min). The actual cooling rate inside and within the glass laminate with the actual resin / interlayer is considered to be thermodynamically slower than the externally applied cooling rate. A thermocouple can be installed inside the interlayer within the glass laminate, thereby enabling direct measurement of the cooling rate. Generally, a rate from 10°C / min to about 2°C / min was obtained depending on the actual temperature of the sample. Since the heat flow from the glass laminate depends on the temperature difference between the laminate and the surrounding "cooling means" (e.g., cooling air), generally, the rate is faster the higher the temperature, and asymptotically decreases as the temperature of the glass laminate approaches the temperature of the cooling means. Therefore, in practice, it is difficult to indicate this as a single cooling rate value in the case of rapid cooling. However, in the case of slow cooling, thermal equilibrium approaches being achieved, and thus, a cooling rate of 0.1°C / min is measured and shown to be fairly uniform over the entire cooling range to the surroundings because the internal temperature "follows" the external temperature closely, so the situation is different.

[0172] The laminated glass of the present invention can be suitably used for automotive front glass, automotive side glass, automotive sunroof, automotive rear glass, or glass for a head-up display; architectural members such as windows, walls, roofs, sunroofs, sound insulation walls, display windows, balconies, handrail walls, etc.; partition glass members in conference rooms; solar panels, etc. Further information regarding such applications can be found by referring to the previously incorporated publications.

[0173] The present invention will be further understood from the following specific examples. However, it will be understood that these examples are not to be construed as limiting the scope of the present invention in any way.

Example

[0174] Preparation of the ionomer sheet A regenerative material containing ionomer 1 and ionomer 1 and a dialkoxysilane silane S1, S2, or S3 is fed at about 5 - 7 pounds per hour to a 18 mm diameter Liestritz twin-screw kneading extruder (screw rotation speed set at 200 rpm) using a K-Tron feeder (Coperion GmbH) equipped with a calibrated pigtail-type auger, and extruded into polymer strands (two 6 mm hole dies).

[0175] The throughput of the polymer is controlled by adjusting the screw rotation speed to provide a predetermined throughput or residence time and the resulting shear conditions. The molten strands are drawn through a water bath containing deionized water at ambient temperature, excess water is blown off with compressed air, and the strands are fed to a rotary cutter (Conair) to become cut strand pellets. These pellets are then dried overnight in a 50 °C vacuum oven while purging with a small amount of dry nitrogen. Thereafter, the pellets are compression molded into a sheet with dimensions of 150 mm × 200 mm and a nominal thickness of 0.76 mm.

[0176] Method for preparing a laminate A glass laminate is prepared from an ionomer sheet by the following method. An annealed glass sheet (100×100×3 mm) is washed in a solution of trisodium phosphate (5 g / l) in deionized water at 50 °C for 5 minutes, rinsed thoroughly with deionized water, and dried. Three layers of ionomer sheets (each about 0.76 mm thick) are laminated and sandwiched between two glass sheets (such that the thickness of the middle layer is 2.28 mm).

[0177] By minimizing the contact time with the indoor environment, the moisture level of the ionomer sheet is maintained at 0.08 wt% or less.

[0178] The moisture level of the ionomer sheet is measured using the Coulometric Karl Fischer method (Metrohm Model 800) with the heating chamber temperature of the sample vial set at 150 °C. The ionomer sheet is cut into small pieces to fit into a sample vial with a total weight of 0.40 grams.

[0179] Next, the preliminary laminate assembly is taped at several locations with polyester tape to hold the relative positions of each layer and the glass plate. To facilitate the removal of air from within the layers, a piece of nylon cloth is placed on the outer periphery of the assembly. The assembly is placed in a nylon vacuum bag and sealed, then connected to a vacuum pump. A vacuum is applied to enable the substantial removal of air from the inside (reducing the air pressure inside the bag to less than 50 mbar absolute pressure). Thereafter, the assembly placed in the bag is heated to 120 °C in a convection air oven and held for 30 minutes. Then, a cooling fan is used to cool the assembly to near room temperature, the assembly is disconnected from the vacuum source and the bag is removed to obtain an assembly in which the glass and the intermediate layer are fully pre-bonded.

[0180] Next, this assembly is placed in an air autoclave, and the temperature and pressure are raised from ambient to 135 °C over 15 minutes at 13.8 bar. After holding this temperature and pressure for 30 minutes, the temperature is lowered to 40 °C with a cooling rate of approximately 2.5 °C / min, and then the pressure is returned to ambient pressure (over 15 minutes), and the final laminate is removed from the autoclave.

[0181] The glass used was standard annealed soda lime glass (obtained from Guardian Industries, Inc., Galax VA, USA).

[0182] Resin used: Refer to Table 1.

[0183] Preparation of the ionomer sheet The ionomer resin was combined as needed by dry blending, and the additive (if present) was fed at about 5 - 7 pounds per hour using a K-Tron feeder (Coperion GmbH) equipped with a calibrated pigtail type auger to a 18 mm diameter Liestritz twin screw kneading extruder (screw rotation speed set at 400 rpm), and the barrel temperature was set to control the zone temperature to 210 °C, and the melt temperature at the die was lowered to the range of 205 - 225 °C. The polymer was extruded into strands (a two 6 mm hole die).

[0184] The throughput of the polymer was controlled by a combination of the feed rate and the screw speed of the extruder to provide a predetermined throughput or residence time and the resulting shear conditions. The molten strands exiting the die were drawn through a water bath containing deionized water at ambient temperature, excess moisture was blown off with compressed air, and the strands were fed to a rotary cutter (Conair) and became cut strand pellets (nominal length 4 mm). Then, these pellets were dried overnight in a 50 °C vacuum oven while purging with a small amount of dry nitrogen. Thereafter, these pellets were compression molded into plaques with dimensions of 150 mm × 200 mm with a nominal thickness of 0.76 mm. And this plaque was kept in a dry atmosphere before being made into a laminate.

[0185] Method for producing a laminate The glass laminate was produced from each ionomer sheet by the following method. The annealed glass sheet (100×100×3 mm) was washed with a sodium phosphate (5 g / l) solution in deionized water at 50 °C for 5 minutes, rinsed thoroughly with deionized water and dried. Three layers of each ionomer plaque (about 0.76 mm thick) were laminated and sandwiched between two glass sheets (so that the thickness of the middle layer was 2.28 mm).

[0186] By minimizing the contact time with the indoor environment (about 35% RH), the moisture level of the ionomer sheet was maintained at 0.08 wt% or less, or exposed at the temperature and humidity levels shown in the following examples for 10 days (the samples were placed in an Espec Humidity Chamber - Model LHU-113).

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

[0188] Next, the preliminary laminate assembly was taped at several locations with polyester tape to hold the relative positions of each layer and the glass plate. To facilitate air removal from within the layers, pieces of nylon cloth were placed on the outer periphery of the assembly. The assembly was placed in a nylon vacuum bag, sealed, and then connected to a vacuum pump. A vacuum was applied to allow substantial removal of air from the interior (the air pressure within the bag was reduced to less than 50 millibars absolute pressure). Thereafter, the assembly placed in the bag was heated to 120 °C in a convection air oven and held for 30 minutes. Then, the assembly was cooled to near room temperature using a cooling fan, the assembly was disconnected from the vacuum source, the bag was removed, and an assembly with the glass and the intermediate layer fully pre-bonded was obtained.

[0189] Next, this assembly was placed in an air autoclave, and the temperature and pressure were raised from ambient to 135 °C over 15 minutes at 13.8 bar. After holding this temperature and pressure for 30 minutes, the temperature was lowered to 40 °C with a cooling rate of about 2.5 °C / min, and then the pressure was returned to ambient pressure (over 15 minutes), and the final laminate was removed from the autoclave.

[0190] After autoclave treatment, the final laminate was reheated in a controlled air circulation oven at a temperature of 120 °C ± 2 °C and held for 2 - 3 hours until thermal equilibrium was reached. Then, the laminate was cooled slowly at 0.1 °C / min to ambient temperature (about 23 °C), or the laminate was removed from 120 °C and cooled rapidly (rapidly) by using a large floor fan to force-feed room temperature air over the entire surface of each laminate. The actual cooling rate curve of the sample was determined using thermocouples installed inside the ionomer intermediate layer and near the center of the laminate. The temperature dropped from 120 °C to about 85 °C in 7 minutes, from 85 °C to 60 °C in 10 minutes, from 60 °C to 30 °C in 18 minutes, and the temperature inside the laminate was further returned to near room temperature in 10 minutes. After these "rapid" cooling and 0.1 °C / min (slow) cooling thermal cooling rate treatments, the optical measurements shown in Table 3 were performed.

[0191] Haze and YI measurements The laminate was thoroughly cleaned using WINDEX glass cleaner (S.C. Johnson & Son, Inc.) and a lint-free cloth, and inspected to ensure that there were no bubbles or other defects that could interfere with valid optical measurements. Next, to obtain haze rate measurements, the laminate was evaluated using a Haze-gard Plus hazemeter (Byk-Gardner). Haze measurements were made in accordance with the method outlined in American National Standard (ANSI Z26.1-1966), "Safety Code for Safety Glazing Materials for Glazing Motor Vehicles Operating on Land Highways". In test sections 5.17 and 5.18, which include Figures 5 and 6 of the standard, the proper methods and equipment setups for measuring the haze level of glazing materials are detailed. The Hazegard Plus hazemeter met the appropriate criteria of this standard and was used for all subsequent measurements. The equipment was verified to be properly calibrated and operating correctly using a haze standard traceable to the National Bureau of Standards (current NIST). Color measurements were made using a Hunterlab ULTRASCAN XE (Hunter Associates Laboratory, Inc., Reston, Va.) with a 10-degree / D65 light source / observation angle. The yellowness index (YI) was calculated in accordance with ASTM E313-05 using a 2-degree observation angle and a C light source (2 degrees).

[0192] Peel adhesion measurement To enable the measurement of peel adhesion, several samples were prepared as described above, except for the following points.

[0193] Annealed glass cuts were made, cut into rectangles of 100 mm × 200 mm, and then washed according to the aforementioned procedure. A thin polyester tape with silicone adhesive (thickness 25 μm × width 25 mm) was pasted on the glass surface of the "target surface" (air surface or tin surface) in two parallel strips, with a uniform adhesive area of 25 mm width provided therebetween. By this procedure, a very clear adhesive area can be provided without the need to cut open the polymer layer and create a peel strip as conventionally done with the standard peel adhesion method. To provide a relatively flat surface for the lamination step and function as a release layer for removing the upper glass piece, a 4-mil thin FEP film was placed on a plastic sheet on top of the intermediate layer test piece before placing the second glass. Next, all lamination steps were carried out as described above. Thereafter, 90-degree angle peel adhesion force measurements were performed on various samples manufactured by the above process via a mechanical testing apparatus (INSTRON Model 1122, Instron Industrial Products, Norwood, MA USA). The peel was carried out at a crosshead speed of 1 cm / min under standard laboratory conditions (nominal 23 °C and 50% RH). After the sample had peeled approximately 100 mm, deionized water was applied to the interface between the glass and the peel so that the interface was completely immersed in liquid water here. The peel was continued until a further approximately 100 mm of the sample was tested. During this final test period, sufficient water was supplied to ensure that the sample was maintained in a "wet" state. Data was collected via computer software (INSTRON Bluehill III software, Instron Industrial Products, Norwood, MA USA), and the average force levels in the "50% RH" and "wet state" peel test sections were calculated.

[0194]

Table 1

[0195]

Table 2

[0196] The peel adhesion data provided in Table 2 show the surprising feature that the adhesion behavior is improved beyond that shown by either of the unused ionomer resins (IO-1 or IO-2). In these cases (e.g., EX-01 or EX-05), addition of a lower weight percentage (e.g., 25%) of a recycled ionomer resin (IO-4) pre-modified with 3-glycidoxypropylmethyldiethoxysilane. The retention of adhesion is maintained by reprocessing of the resin, and generally, the increase in adhesion is proportional to the percentage of the added silane-modified recycled resin.

[0197] In the tables of the following examples, for all ionomer-containing samples, a corresponding increase in haze with slow cooling was also evident. The ionomers of this system's composition (ethylene-methacrylic acid copolymers and terpolymers as ionomers) are known to have a degree of crystallinity and exhibit microphase separation of the polymer backbone and ionic clusters. These crystallites / ionic clusters can cause visible light scattering (e.g., lack of haze / transparency), and their size generally always increases as the cooling rate decreases. When heat-treating the ionomer intermediate layer together in glass form, it is generally recommended to cool from the "high temperature" part of the cycle (generally called the "heat soak", temperatures in the range of 105 °C to 170 °C) at a sufficient cooling rate to minimize the generation of haze resulting from the recrystallization and solidification processes. When the ionomer intermediate layer cools from the molten state back to the "solid form", the laminated glass is stable and can be safely handled. Haze is an undesirable property for laminated glass where high transparency is desired, so a faster cooling rate is also desired. However, the typical or possible actual cooling rate for a glass laminate containing an ionomer-based intermediate layer is determined by limitations of the equipment, adjustment of process settings and process conditions, and differences in heat conduction due to the structural material and physical size / thickness.

[0198] Table 3 shows data on haze and YID for various combinations of blends of the following components: a). unused dicarboxylic acid ionomer (IO-1), b). unused terionomer (IO-2), or those having their corresponding recycled resin forms (IO-3 and IO-4 respectively). In a normal typical manufacturing process, a certain portion of the polymer resin that is extruded and returned to the process as recycled material (from within) is utilized. The compositional limitations on the amount of recycled material suitable for addition would relate to minimizing the degree of impact on the visible quality or any undesirable changes in other resulting performance parameters such as tensile strength. Surprisingly, the blends of dicarboxylic acid (either the unused resin and / or its corresponding recycled material form) and terpolymer (either the unused resin and / or its corresponding recycled material form) showed very good optical behavior with respect to haze and YID levels across the blend range. This allows for complete manufacturing flexibility in blending this resin system with end products of such resin systems and would provide an acceptable optical consistency. Customers processing this blend can expect uniform optical performance after laminating sheet products with any blend ratio of the art, even with differences in the thermal cycle / cooling rate shown in the lamination process.

[0199]

Table 3

[0200] Surprisingly, from the foregoing information, it has been shown that there exists a novel blend of ionomer resins that provides acceptable optical properties for use in glass laminates. Examples of the subject technology with various blend compositions are well within the bounds of any of the individual unused ionomer resin components to meet the optical quality expectations of the end use. In the flexibility in the manufacture of the ionomer intermediate layer having acceptable or desired optical properties (transparency, low haze, and low yellowness (color)), it is desirable to have either complete or significant degrees of freedom in the composition of the blend of resin combinations. A blend of a selective sodium ionomer based on a dicarboxylic acid copolymer resin (ethylene / carboxylic acid) and a selective sodium ionomer based on a terpolymer resin (ethylene / acrylate / carboxylic acid) has been shown to exhibit acceptable optical performance over the entire composition range. Another sodium ionomer of the dicarboxylic acid copolymer resin exhibits a very non-linear and unexpected yellowness when blended with either the selected dicarboxylic acid ionomer or the selected terpolymer ionomer resin or a combination thereof. When embodiments using blends, mixtures, combinations, etc. of components are described herein, all ratios of the components are contemplated unless otherwise specified. For example, without limitation, when a combination of a dipolymer and a terpolymer is used, such as in (i) and (ii) above, weight ratios of 99.9 / 0.1 to 0.1 / 99.9 are contemplated, which includes all ratios between w / w (i) / (ii) such as 90 / 10, 75 / 25, 60 / 40, 50 / 50, 40 / 60, 25 / 75, 10 / 90, etc.

[0201] The foregoing description of the invention provides methods and processes for making and using it such that anyone of ordinary skill in the art can make and use it, and this enablement is provided particularly with respect to the subject matter of the appended claims, which form a part of the original description. This description is provided in the context of a particular application and its requirements. Various modifications to the embodiments will be readily apparent to those of ordinary skill in the art, and the general principles defined herein can be applied to other embodiments and applications without departing from the spirit and scope of the invention. Accordingly, the invention is not intended to be limited to the illustrated embodiments, but rather the broadest scope consistent with the principles and features disclosed herein should be given. In this regard, certain embodiments within the invention may not exhibit all of the advantages of the invention when considered broadly.

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 ethylene acid dipolymer ionomer resin at least partially neutralized with sodium, or (ii) an ethylene acid ester terpolymer ionomer resin at least partially neutralized with sodium, or (iii) any combination of (i) and (ii) and at least a part of the dialkoxysilane adhesion promoter and at least a part of the ionomer resin are present in the form of recycled materials, an ionomer resin composition.

2. The ionomer resin is (i) an ethylene acid dipolymer ionomer resin at least partially neutralized with sodium, which consists essentially of copolymer units of ethylene and at least one α,β-unsaturated carboxylic acid, or (ii) an ethylene acid terpolymer ionomer resin at least partially neutralized with sodium, which contains copolymer units of ethylene, at least one α,β-unsaturated carboxylic acid, and at least one α,β-unsaturated carboxylic acid ester, or (i) and (ii) in combination, the composition according to claim 1.

3. The composition according to claim 1, wherein the dialkoxysilane adhesion promoter is present in the ionomer resin composition in an amount in the range of about 50 to about 5000 ppm by weight based on the weight of the ionomer resin.

4. The ionomer resin composition according to claim 1, wherein the ionomer resin contains an unused sodium-neutralized ethylene acid copolymer.

5. The ionomer resin composition according to claim 1, wherein the ionomer resin contains a combination of an unused material and a recycled material.

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

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

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

9. The ionomer resin composition according to claim 4, wherein the unused sodium-neutralized ethylene acid copolymer and the recycled material are intimately mixed.

10. The dipolymer ionomer resin is (i) ethylene, and (ii) at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms in an amount of about 10 wt% to about 30 wt% consisting essentially of copolymer units of The weight percentage of the copolymer units of the dipolymer ionomer resin is based on the total weight of the dipolymer ionomer resin, and the total weight percentage of the copolymer units of the dipolymer ionomer resin is 100 wt%. At least a part of the carboxylic acid groups of the α,β-unsaturated carboxylic acid of the dipolymer ionomer resin is neutralized to form an ionomer containing a carboxylate group having sodium counter ions, The terpolymer ionomer resin is (i) ethylene (ii) at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms in an amount of about 10 wt% to about 30 wt% (iii) at least one α,β-unsaturated carboxylic acid ester having 3 to 10 carbon atoms in an amount of about 2 wt% to about 15 wt%, 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 consisting essentially of copolymer units of The weight percentage of the copolymer units of the terpolymer ionomer resin is based on the total weight of the terpolymer ionomer resin, and the total weight percentage of the copolymer units of the terpolymer ionomer resin is 100 wt%. At least a part of the carboxylic acid groups of the α,β-unsaturated carboxylic acid of the terpolymer ionomer resin is neutralized to form an ionomer containing a carboxylate group having sodium counter ions. The ionomer resin composition according to claim 2.

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

12. The ionomer resin composition according to claim 11, wherein the dialkoxysilane adhesion promoter further contains an active chemical group for bonding to an unused alkali metal-neutralized ethylene acid copolymer in addition to the alkoxy group.

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

14. The intermediate sheet according to claim 13, having a thickness in the range of about 320 μm or more to about 1850 μm or less.

15. A glass laminate comprising the intermediate layer sheet according to claim 13.

16. A method for producing an ionomer resin composition, comprising the step of intimately mixing an unused sodium-neutralized ethylene acid copolymer and a recycled material containing a dialkoxysilane adhesion promoter.

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

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

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