Ionomer resin composition

Abstract

An ionomer resin composition comprising a sodium-neutralized ethylene acid dipolymer and a sodium-neutralized ethylene acid ester terpolymer, preferably, at least one of the dipolymer and the terpolymer is partially a recycled material, is provided. The described ionomer composition is particularly suitable for use in the production of an intermediate layer and a glass laminate comprising the intermediate layer.

Description

Technical Field

[0001] This application claims priority to U.S. Provisional Application No. 63 / 354,335 and U.S. Provisional Application No. 63 / 354,307, both filed on June 22, 2022, which 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 dipolymer and a sodium-neutralized ethylene acid ester terpolymer. The described ionomer composition is particularly suitable for use in the manufacture of an intermediate layer and a glass laminate comprising the intermediate layer.

Background Art

[0003] Laminated glass is generally produced by laminating two glass sheets with a plastic intermediate layer. One of the specific advantages of laminated glass over solid glass sheets is its impact resistance and shatter resistance due to the adhesion of the glass to the intermediate layer sheet. In a safety glass laminate, the optimal adhesion of the intermediate layer 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 it can also adversely affect the ability of the intermediate layer to hold glass fragments upon impact.

[0004] Many different materials are used as plastic intermediate layers. For example, sheets containing polyvinyl acetal (polyvinyl butyral) and a plasticizer are widely used as intermediate layers for laminated glass because of their excellent adhesion to glass. Laminated glass containing such an intermediate layer can be excellent in transparency, mechanical strength, flexibility, sound insulation, and shatter resistance.

[0005] Partially neutralized ethylene acid copolymers (ionomers) are also used as an intermediate layer for producing 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.

Prior Art Documents

Patent Documents

[0006]

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

Summary of the Invention

Problems to be Solved by the Invention

[0007] Here, by combining a sodium-neutralized ethylene acid dipolymer and a sodium-neutralized ethylene acid ester terpolymer in an ionomer composition, it has been found that beneficial physical properties can be retained in the blend, particularly when at least one of the components is partially or wholly a recycled material.

[0008] In this specification, when terms such as "invention" and "the present invention" are used, they refer only to the specific embodiments immediately following. These are not intended to be broadly limiting, either in whole or with respect to some of the advancements in the technology described in this specification.

Means for Solving the Problems

[0009] The present invention provides (i) from about 1 wt% to about 99 wt% of at least partially sodium-neutralized ethylene acid dipolymer ionomer resin, and (ii) from about 1 wt% to about 99 wt% of at least partially sodium-neutralized ethylene acid ester terpolymer ionomer resin in an ionomer resin composition, wherein the combined wt% of (i) and (ii) is 100 wt%, based on the combined weight of (i) + (ii), to address the above problems.

[0010] 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, and 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 of ethylene, at least one α,β-unsaturated carboxylic acid, at least one α,β-unsaturated carboxylic acid ester, and optionally a derivative of an α,β-unsaturated carboxylic acid other than an ester, such as an amide or an anhydride.

[0011] In one embodiment, one of (i) or (ii) is 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 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%, or 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%, or 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).

[0012] In one embodiment, at least a part, or a majority, or substantially all of at least one of (i) and (ii) is a recycled material. In another embodiment, at least a part, or a majority, or substantially all of one of (i) or (ii) is an unused material. In another embodiment, at least one (or both) of (i) and (ii) is a combination of an unused material and a recycled material. In another embodiment, one of (i) or (ii) is substantially an unused material or an unused material, and one of (i) or (ii) is substantially a recycled material or a recycled material.

[0013] In one embodiment, the dialkoxysilane adhesion promoter (iii) is present in the ionomer resin composition in an amount in the range of about 50 to about 5000 weight ppm, based on the combined weight of the dipolymer ionomer resin and the terpolymer ionomer resin.

[0014] In another aspect, the present invention provides a method for producing a sheet of an ionomer resin composition by melt-blending (i), (ii) and optional components under shear to produce a melt blend, then passing the melt blend through a die to extrude it into 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 is embossed in a pattern on one or both of the upper surface and the lower surface before solidification.

[0015] In another aspect, 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.

[0016] These and other embodiments can be used in combination with all of them, and the features and advantages of the present invention, which will be more easily understood by those skilled in the art upon reading the following detailed description, will be described.

DETAILED DESCRIPTION OF THE INVENTION

[0017] The present invention relates to, but is not limited to, a resin composition, an intermediate layer prepared from the resin composition, and a glass laminate containing the intermediate layer. Further embodiments and details are provided below.

[0018] All publications, patent applications, patents, and other references mentioned in this specification are hereby expressly incorporated by reference in their entirety for all purposes as if fully set forth herein, unless otherwise indicated.

[0019] 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 belongs. In case of conflict, the present specification, including definitions, will control.

[0020] Trademarks are shown in capital letters unless otherwise specified.

[0021] Unless otherwise indicated, all percentages, parts, ratios, etc. are by weight.

[0022] Unless otherwise indicated, 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).

[0023] When a quantity, concentration, or other value or parameter is given as a range, or a list of upper and lower limit values, this is to be understood as specifically disclosing all ranges formed from any pair of upper and lower limit values, whether or not the ranges are individually disclosed. When a numerical range is described in this specification, unless otherwise indicated, the range is intended to include its endpoints, and all integers and fractions within the range. The scope of the present disclosure is not intended to be limited to the specific values recited when defining the range. As an example, the recited range of 1 to 10 fully encompasses and includes the independent sub-range of 3.4 to 7.2, and the same is true for the values 1, 3, 5, 8 in the following list of values.

[0024] 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 those skilled in the art know how to obtain that tolerance range. When the term "about" is used to describe a range of values or endpoints, the present disclosure should be understood to include the specific values or endpoints recited.

[0025] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," 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.

[0026] The transitional phrase "consisting of" excludes elements, steps, or components not specified in the claim, closes the claim against the inclusion of 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.

[0027] The transitional phrase "consisting essentially of" limits the scope of a claim to the specified materials or steps and those that do not materially affect the basic and novel characteristics of the claimed invention. A claim in the "consisting essentially of" form is intermediate between a closed claim in the "consisting of" form and a fully open claim in the "comprising" form. Any additives defined herein, any additives at appropriate levels for such additives, and minor impurities are not excluded from an embodiment by the term "consisting essentially of" so long as they do not materially affect the basic and novel characteristics of that embodiment.

[0028] Further, 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).

[0029] The use of "a" or "an" to describe various elements and components herein is for convenience only and to give a general meaning to 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 form includes the plural form.

[0030] As used herein, the terms "substantially" or "primarily" mean greater than 50% of the material being referred to, unless otherwise specifically defined herein. When no designation is made, the percent is on a molar basis when referring to molecules (such as hydrogen and ethylene), and on a weight basis otherwise (such as additive content).

[0031] As used herein, the terms "substantial portion" or "substantially", unless otherwise defined, 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. This is intended to account for some reasonable variation from 100% that would typically occur in industrial or commercial scale situations.

[0032] 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.

[0033] As used herein, the term "unused" generally refers to a material that has not been processed into its final form (e.g., a sheet or film). The form of such a material may vary depending on its method of manufacture. Merely changing the physical form of such a material, for example, by physical or thermal means (e.g., grinding, cutting, pelletizing, etc.), without extruding it into its final intended shape (e.g., a sheet or film), does not change its "unused" characteristics.

[0034] 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 size of the recycled material granules (particles) of suitable size is generally not limited, but can range 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. 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.

[0035] 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.

[0036] 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 make other forms / shapes or heat treatment that causes melting of the resin.

[0037] As used herein, the terms "intimately mix", "intimately mixing", "intimately mixed", and "intimate mixing" mean combining or combining two or more polymer materials, such as virgin ionomer and recycled material, so that optimal optical strain parameters are achieved. Usually, heat treatment (such as melt mixing) is performed. Measurement of optical strain can be performed by practical methods including, but not limited to, the "shadowgraph" technique. A shadowgraph is generally a highly sensitive visualization method that can reveal optical inhomogeneities in a transparent material by the shadow projected by the disturbance when a light beam is refracted. Another common method is to determine the degree of optical strain when a glass laminate of a sample is placed on the straight line of the line of sight and when it is not placed when looking at a "checkerboard" target grid.

[0038] As used herein, the term "forming" with respect to a polymer material means forming the material 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.

[0039] 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 that produces a melt that is formed into a film or sheet, this may also be referred to as the "machine direction".

[0040] As used herein, the terms "plastic" and "polymer" are used interchangeably. The term "plastic" can refer to a particular type of polymer and is generally understood to be composed of long chains of polymers, which are in turn composed of smaller, uniform molecules. However, in the present invention, both terms can be used interchangeably.

[0041] 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, between different resin combinations, and in the amount of each resin and the cooling method used. A blue colorant can be added to the ionomer resin (to make the intermediate layer film / sheet appear less yellow), but this is an additional step, and such an addition only compensates for the degree of yellowness at a given composition blend and cooling rate. Furthermore, this means will change the "color" of the resin even to "green" or "gray", and in virtually 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.

[0042] As used herein, the terms "recycled material" and "recycled polymer material" each refer to a polymer material containing a material recovered from a previously processed polymer material. The previously processed 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, etc. This polymer material contains not only one or more polymers but also one or more optional additives. Thus, when this polymer material is recycled, the optional additives are also considered to be "recycled". Recycled polymer materials can also be obtained from downstream manufacturing processes, such as trim from a conversion process where a film or sheet is assembled into a glass laminate. Further, the recovered polymer material can be reprocessed by filtering out impurities in a secondary extrusion process to produce a material suitable for use. 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 for reasons such as not referring to the comonomers as copolymerized units, not including the conventional nomenclature for copolymers, e.g., the nomenclature of the International Union of Pure and Applied Chemistry (IUPAC), not using a product representation based on the manufacturing method, or other reasons. However, as used herein, a description of a copolymer referring to the constituent comonomers of the copolymer or the amounts of the constituent comonomers of the copolymer means that the copolymer contains the copolymerized units (if specified, in the specified amounts) of the designated comonomers. It follows that a copolymer is not the product of a reaction mixture containing a given comonomer in a given amount, unless expressly stated otherwise in limited circumstances.

[0043] 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.

[0044] 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.

[0045] 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 alone or in combination such as "(meth)acrylate".

[0046] As used herein, the term "ionomer" generally refers to a polymer containing an ionic group that is a carboxylate salt, such as an ammonium carboxylate salt, an alkali metal carboxylate salt, an alkaline earth metal carboxylate salt, a transition metal carboxylate salt 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. The alkali metal ionomer 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.

[0047] For the sake of expediency, many elements of the present invention are discussed separately, and lists of options may be provided, and numerical values may be within ranges, but for the purposes of this disclosure, that should not be construed as limiting the scope of this disclosure or supporting any claim for any combination of such distinct components, list items, or ranges. Unless otherwise stated, all combinations possible in this disclosure should be considered to be explicitly disclosed for all purposes.

[0048] 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.

[0049] Ionomer According to the present invention, an ionomer resin composition comprises at least two sodium-neutralized ethylene α,β-unsaturated carboxylic acid copolymers (i.e., ionomers), one of which is a dipolymer having structural units derived from ethylene and structural units derived from an α,β-unsaturated carboxylic acid, wherein at least a part of the structural units derived from the α,β-unsaturated carboxylic acid is neutralized with sodium ions, and the other 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 part of the structural units derived from the α,β-unsaturated carboxylic acid is neutralized with sodium ions.

[0050] For both the dipolymers and the terpolymers, the content ratio of the structural units derived from α,β-unsaturated carboxylic acids 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 α,β-unsaturated carboxylic acids 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).

[0051] Examples of the α,β-unsaturated carboxylic acids that constitute the dipolymer 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.

[0052] The terpolymer further comprises 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.

[0053] In one embodiment, one or both of the dipolymer and the terpolymer have a melt flow rate (MFR) of from about 1 g / 10 min, or from about 2 g / 10 min, 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.

[0054] One skilled in the art can synthesize the described dipolymers and terpolymers based on the descriptions herein, optionally considering the descriptions in, for example, US3404134, US5028674, US6500888B2, US6518365B1, US8334033B2, and US8399096B2. In one embodiment, the method described in US8399096B2 is used, and the derivative of the second α,β-ethylenically unsaturated carboxylic acid is present in the reaction mixture at a sufficiently high level and in a complementary amount.

[0055] In one embodiment, to obtain the dipolymer ionomer and the terpolymer ionomer, their ethylene acid copolymer precursors are partially neutralized by reaction with one or more sodium bases. Examples of suitable procedures for neutralizing the ethylene acid copolymer 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 the 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 the 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 the specific end use.

[0056] The counterion to the carboxylate anion in the ionomer is the sodium cation. In one embodiment, the ionomer used in the present invention is a sodium-neutralized ionomer in which the counterion is substantially sodium ions, 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 the carboxylate groups in the ionomer.

[0057] 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 cations used are monovalent or divalent metal cations, such as lithium, magnesium, zinc, potassium, and combinations of one or more of these metal cations.

[0058] In one embodiment, counterions other than sodium are present in amounts that are at most "impurities", as commonly found in industrial situations, as would be recognized by one of ordinary skill in the art. Since sodium is the preferred counterion herein, it will be mainly referred to hereinafter, but all counterions contemplated can be used in any of the embodiments described herein.

[0059] The resulting sodium-neutralized ethylene acid dipolymers and terpolymers are ionomers, and the melt index measured according to ASTM method D1238-89 at 190 °C and 2.16 kg is lower than that 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 1000 g / 10 min or less, or 750 g / 10 min or less, or 500 g / 10 min or less, or 250 g / 10 min or less, or 100 g / 10 min or less, or 50 g / 10 min or less, or 25 g / 10 min or less, or 20 g / 10 min or less, or 10 g / 10 min or less, or 7.5 g / 10 min or less.

[0060] In one embodiment, the 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%, and 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.

[0061] In one embodiment, the 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 copolymerization 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 percentage of the copolymerization units is based on the total weight of the terpolymer, the total weight percentage of the copolymerization 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 counter ions). The terpolymer consists essentially of or consists of these components.

[0062] Such terpolymer ionomers are generally disclosed in WO2015 / 199750A1, WO2014 / 100313A1 and US2017 / 0320297A1.

[0063] In one embodiment of the dipolymer and / or terpolymer, the α,β-unsaturated carboxylic acid is methacrylic acid.

[0064] In one embodiment of the terpolymer, the α,β-unsaturated carboxylic acid ester is n-butyl acrylate, isobutyl acrylate, or a mixture thereof.

[0065] In one embodiment of the terpolymer, the terpolymer consists of or consists essentially of the copolymerization units of (i), (ii) and (iii).

[0066] In one embodiment, the weight ratio (w / w dipolymer / tetrapolymer) 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 not particularly limited based on the total weight of the dipolymer and the terpolymer. In one embodiment, the weight ratio (w / w dipolymer / tetrapolymer) 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 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, 50 / 50, including 1 / 99 to 99 / 1, based on the total weight of the dipolymer and the terpolymer.

[0067] In one embodiment, one of (i) or (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).

[0068] In one embodiment, the total amount of the dipolymers and terpolymers present in the composition is all or substantially all of the composition, based on the total weight of any type of polymer (excluding additives) present in the composition.

[0069] Adhesion promoter Any optional adhesion promoter suitable for use in accordance with the composition of the present invention is a dialkoxysilane. Without being bound by theory, it is believed that the hydrolyzed silanol moiety of the silane can 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 for the silane to interact in an advantageous way such that it can 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.

[0070] In one embodiment, each alkoxy group individually contains 1 to 3 carbon atoms. Suitable examples include diethoxydimethylsilane, diethoxy(methyl)vinylsilane, 1,3 - diethoxy - 1,1,3,3 - tetramethyldisiloxane, dimethoxydimethylsilane, dimethoxymethylvinylsilane, methyldiethoxysilane, diisopropyldimethoxysilane, dicyclopentyldimethoxysilane, γ - aminopropyl - N - cyclohexylmethyldimethoxysilane, 3 - aminopropylmethyldimethoxysilane, N - phenyl - 3 - aminopropylmethyldimethoxysilane, N - phenyl - 3 - aminopropylmethyldiethoxysilane, N - β - (aminoethyl) - γ - aminopropylmethyldimethoxysilane, and 3 - glycidoxypropylmethyldiethoxysilane.

[0071] In another embodiment, in addition to the alkoxy group, the silane also contains a "reactive" chemical group for bonding to the ionomer resin matrix, such as a carboxylic acid reactive group such as 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.

[0072] Desirably, the silane 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).

[0073] To maintain sufficient laminate integrity (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 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 Pannel test (described in WO03 / 033583A1, etc.). In particular, when high penetration resistance is required, it is more preferable to adjust the amount of the adhesion improver so that the adhesion is about 3 or more and about 6 or less, and when high glass scatter prevention is required, it is more preferable to adjust the amount of the adhesion improver so that the adhesion is about 7 or more and about 10 or less.

[0074] Other additives Other than the aforementioned optional dialkoxysilanes and regardless of their presence or absence, the resin compositions and masterbatches of the present invention may optionally contain one or more other additives, such as, for example, antioxidants, ultraviolet absorbers, light stabilizers, antiblocking 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.

[0075] Examples of the antioxidant include phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and the like. Among these, phenolic antioxidants are preferred, and alkyl-substituted phenolic antioxidants are particularly preferred.

[0076] 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.

[0077] Examples of phosphorus-based antioxidants include monophosphite compounds such as triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl 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(diphenyl monoalkyl(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.

[0078] 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.

[0079] 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).

[0080] 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.

[0081] 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 used 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 used is typically about 50,000 ppm or less, or about 10,000 ppm or less, based on the weight of the ionomer resin.

[0082] In some embodiments, it is also possible to use a combination of two or more UV absorbers.

[0083] In other embodiments, no UV absorber is added, or the composition and masterbatch are substantially free of UV absorber.

[0084] Examples of the light stabilizer 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.

[0085] When a laminated glass is produced by incorporating heat shielding fine particles or a heat shielding compound as a heat shielding material into the intermediate layer of the present invention and imparting a heat shielding 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.

[0086] Examples of the heat shielding 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 about 0.01 or more and about 1.0 or less, and n is about 2.2 or more and about 3.0 or less), zinc antimonate (ZnSb2O5), lanthanum hexaboride, and the like can 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.

[0087] From the viewpoint of the transparency of the final laminate, the average particle diameter of the heat insulation 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 insulation fine particles mentioned in this specification means the one measured by a laser diffraction device.

[0088] In the final resin composition, the content of the heat insulation fine particles is preferably about 0.01% 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 insulation fine particles is preferably about 5% by weight or less, or about 3% by weight or less.

[0089] Examples of the heat insulation compound include phthalocyanine compounds, naphthalocyanine compounds, etc. From the viewpoint of further improving the heat insulation properties, it is preferable that the heat insulation compound contains a metal. Examples of the metal include Na, K, Li, Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Sn, V, Ca, Al, etc., and Ni is particularly preferable.

[0090] The content of the heat insulation 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 insulation compound is preferably about 1% by weight or less, or about 0.5% by weight or less.

[0091] Manufacture of Resin Composition 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 the melting conditions of the ionomer resin to produce a substantially uniform mixture that can be finally formed into a final shape, for example, by melt extrusion or molding.

[0092] As will be appreciated by those skilled in the art, in melt blending, care must be taken to ensure that the mixing is strong enough to blend the components sufficiently uniformly. Generally, this high degree of mixing through extrusion compounding is achieved by generating sufficient shear and residence time in the extruder. Also, care must be taken to avoid undesirable results such as local high concentration of components and decomposition of components due to high temperature, 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.

[0093] For example, it is well understood that the degree of hydrolysis of dialkoxysilane increases by being overly exposed to moisture and for a long time, and probably requires further consideration for controlling the contact with external moisture. For example, it may be necessary to cover with dry air or nitrogen to maintain the desired minimum degree of hydrolysis of the silane.

[0094] 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 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 scale of 0.01 mm. Particles larger than 1 mm can be measured using a 25 mm stage micrometer with a scale of 0.05 mm. 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 diameter.

[0095] In one embodiment, the particles for preparing the composition 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 crushed during the grinding process and become irregular in shape, thereby further increasing 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 usually 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.

[0096] 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.

[0097] Alternatively, the particulate resin composition can be prepared directly by mixing a particulate dipolymer ionomer resin and a terpolymer ionomer resin with an optional dialkoxysilane additive as described above (penetrating the silane additive onto the surface of the resin particles), but in an amount such that the final concentration of the components is achieved.

[0098] When present, the dialkoxysilane additive is preferably present in the final resin composition in an amount of from about 50 to, or from about 100 to, or from about 250 to, or from about 500 to, or from about 750 to about 5000, or about 4000, or about 2000, or about 1500, or about 1250 weight ppm, based on the total weight of the dipolymer ionomer resin and the terpolymer ionomer resin.

[0099] All or part of the dialkoxysilane additive can be recovered from previously manufactured polymer materials and added to the compositions of the present invention (masterbatches or otherwise) as recycled materials such as polymer materials containing dialkoxysilane. The recycled material preferably contains at least one of a dipolymer and a terpolymer in addition to the dialkoxysilane additive.

[0100] Materials manufactured previously can be waste materials from the process used to manufacture them, i.e., defective products, edge materials, etc. This material generally contains not only polymers but also one or more additives. Therefore, when recycling this polymer material containing additives, the additives are also considered to be "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 out impurities in a secondary extrusion process to produce a material suitable for use.

[0101] Once the recycled material is obtained, it can be resupplied to the process used to manufacture the final composition and masterbatch of the present invention, together with other resins including unused resin. Furthermore, additional additives may be included during processing together with the recycled material. Since the recycled material has usually been extruded previously, for example, for the purpose of manufacturing an interlayer film / sheet product, the recycled material generally contains additives.

[0102] The physical size and dimensions of the recycled material may require some additional processing steps to facilitate re-"supply" to the process for blending, mixing, and extrusion. 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 supplied at 100% fill or blended and supplied with unused resin or other resins and additives. Alternatively, powerful extrusion kneading can be utilized to blend and eliminate non-uniformity uniformly, but this promotes the occurrence of new resin degradation and often appears as an increase in yellowness and degraded resin (e.g., "black spots").

[0103] 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 refeeding / reintroduction 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 the 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 during the attrition process and become irregular in 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 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.

[0104] In some cases, the end pieces at the ends can be directly resupplied to, for example, an extrusion process with a suitable device design (e.g., guide rolls / pull rolls and screw design). In some cases, the feed can be introduced into a "side feeder" and combined with the main feed. Any means for returning the recycled material are within the scope of the present invention. As described above, this recycled material may contain, in addition to one or more dialkoxysilanes, one or more additives such as those described above.

[0105] 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.

[0106] Sheet / Intermediate Layer The sheet of the ionomer resin composition of the present invention can be prepared by a conventional melt extrusion process or 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.

[0107] 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.

[0108] As an example of the functional core layer, an acoustic attenuation layer such as a polystyrene copolymer intermediate film (see JP2007-91491A), a polyvinyl acetal layer (see US2013 / 0183507A1, US8741439B2, JP2012-214305A, and US8883317B2), a viscoelastic acrylic layer (see US7121380B2), a layer containing a copolymer of styrene and a rubber-based resin monomer (see JP2009-256128A), a layer containing a polyolefin (see US2012 / 0204940A1), a layer containing an ethylene / vinyl acetate polymer (see WO2015 / 013242A1), a layer containing an ethylene acid copolymer (see WO2015 / 085165A1), etc. can be mentioned.

[0109] In a specific embodiment, the intermediate layer is a thermoplastic elastomer resin, for example, as disclosed in WO2016 / 076336A1, WO2016 / 076337A1, WO2016 / 076338A1 WO2016 / 076339Al, WO2016 / 076340A1 and US2017 / 0320297A1. In a more specific embodiment, the thermoplastic elastomer resin is

[0110] (i) a hydrogenated product of a block copolymer having 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

[0111] (ii) an aliphatic unsaturated polymer block (b) containing about 60 mol% or more of conjugated diene monomer units based on the aliphatic unsaturated polymer block,

[0112] 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,

[0113] 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.

[0114] 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 (e.g., 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 (e.g., “light-shielding bands” as discussed in US2017 / 0320297A1 and US2018 / 0117883A1).

[0115] 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.

[0116] In an asymmetric structure such as a wedge, 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.

[0117] Furthermore, on the surface of the intermediate layer of the present invention, in order to assist in degassing during laminate production, 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 conventionally known ones can be adopted.

[0118] 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, 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. 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 an embossing roll method. By forming the surface of the intermediate layer of the laminated glass, concave portions and / or convex portions are formed on the surface of the intermediate layer of the laminated glass.

[0119] The embossing roll used in the embossing roll method can be manufactured, for example, by using an engraving mill (mother mill) having a desired uneven pattern and transferring the uneven pattern to the surface of a metal roll. Further, an embossing roll can also be manufactured using laser etching. Further, after forming a fine uneven pattern on the surface of the metal roll as described above, a more fine 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.

[0120] Furthermore, it is preferable that the embossing roll used in the embossing roll method is subjected to a release treatment. When an embossing roll not subjected to 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.

[0121] The depth of the concave portion and / or the height of the convex portion (hereinafter, may be 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.

[0122] 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, using the confocal principle of a laser microscope or the like. Additionally, 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.

[0123] Examples of the form of the shape imparted by the embossing roll method or the like include a lattice, an oblique lattice, an oblique ellipse, an ellipse, an oblique groove, and a groove. The inclination angle of such a form is usually about 10° to about 80° with respect to the flow direction (MD direction) of the film. Further, the forming pattern may be a regular pattern, an irregular pattern such as a random mat pattern, or a pattern as disclosed in US7351468B2.

[0124] The forming 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.

[0125] Laminated body The laminated body 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 a nip roll, and the like. Further, after temporary contact adhesion, a method of putting the obtained laminated body into an autoclave for final adhesion can be used.

[0126] When using a vacuum laminator, for example, a known apparatus used in the manufacture of solar cells can be used, about 1×10 -6 MPa or more, about 3×10 -2The assembly is laminated under a reduced pressure of below MPa, at a temperature of about 100 °C or higher, or about 130 °C or higher and about 200 °C or lower, or about 170 °C or lower. Methods using a vacuum bag or a vacuum ring are described, for example, in EP1235683A1 (CA2388107A1). For example, the assembly is laminated at about 130 °C or higher and about 145 °C or lower, under a pressure of about 2×10 -2 MPa.

[0127] When using nip rolls, for example, after performing primary temporary contact adhesion at a temperature below the flow start temperature of the skin resin, a method of further performing temporary contact adhesion under conditions close to the flow start temperature is exemplified. Specifically, for example, after heating the assembly to about 30 °C or higher and about 100 °C or lower with an infrared heater or the like, degassing is performed with 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 with a roll to achieve adhesion or temporary adhesion.

[0128] 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.

[0129] The laminate may be processed using the well-known "non-autoclave" process instead.

[0130] Advantageously, the glass used to produce the laminated glass is not particularly limited. Inorganic glasses such as float glass, polished 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 of them.

[0131] 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 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.

[0132] 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

[0133] The glass used in the examples was standard annealed soda-lime glass (obtained from Guardian Industries, Inc., Galax VA, USA).

[0134] Preparation of Ionomer Sheet For the examples containing silane, the following approach was utilized.

[0135] 1200 grams of ionomer resin was weighed in 0.1 gram units and placed in a clean polypropylene plastic container (2 gallon capacity) with a large metal screw cap. Under appropriate ventilation and following appropriate laboratory safety practices, a specific amount of liquid silane for obtaining the indicated concentration was pipetted into the container. The container was then sealed with the lid and manually shaken vigorously for 2 minutes to disperse the liquid into the mass of ionomer resin pellets. The mixture was shaken again for 1 minute 1 hour after the initial preparation of the blend and shaken again for 1 minute before feeding the soaked resin into the hopper of the feeder. The above operations were carried out under ambient temperature and humidity conditions (nominal 23 °C, 50% RH, but not a humidity-controlled environment). Within approximately 4 hours from the preparation, the silane / resin blend was fed into the extruder via a calibrated auger-type feeder as described in the following ionomer sheet preparation method.

[0136] The ionomer resin was fed at about 5 - 7 pounds per hour using a K-Tron feeder (Coperion GmbH) equipped with a calibrated pigtail type auger under the following temperature profile provided in Table 1 to a 18 mm diameter Liestritz twin screw kneading extruder (screw rotation speed set at 200 rpm) and extruded into polymer strands (two 6 mm hole dies).

[0137] The polymer throughput was controlled by adjusting the screw speed to provide a predetermined throughput or residence time and the resulting shear conditions. In both extruders, the molten strands were drawn through a water bath containing deionized water at ambient temperature, excess water was blown off with compressed air, and the strands were fed to a rotary cutter (Conair) to form cut strand pellets. These pellets were then dried overnight in a vacuum oven at 50 °C while purging with a small amount of dry nitrogen. Thereafter, these pellets were compression molded into plaques with dimensions of 150 mm × 200 mm and a nominal thickness of 0.76 mm. These plaques were then kept in a dry atmosphere or, if instructed, exposed to different humidity conditions prior to lamination as shown below.

[0138] Method for producing laminate The glass laminates were made from each ionomer sheet by the following method. Annealed glass sheets (100×100×3 mm) were washed in a sodium phosphate (5 g / l) solution in deionized water at 50 °C for 5 minutes, rinsed thoroughly with deionized water and dried. Three sheets of each ionomer sheet shown in Table 1 (each with a thickness of about 0.76 mm) were stacked and sandwiched between two glass sheets (such that the thickness of the middle layer was 2.28 mm).

[0139] 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 for 10 days at the temperature and humidity levels shown in the following examples (samples were placed in an Espec Humidity Chamber - Model LHU-113).

[0140] 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.

[0141] 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 layer, a piece of nylon cloth was placed on the outer periphery of the assembly. The assembly was placed in a nylon vacuum bag and sealed, then connected to a vacuum pump. A vacuum was applied to enable substantial removal of air from the interior (the air pressure inside 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 and the bag was removed, obtaining an assembly in which the glass and the intermediate layer were completely pre-bonded.

[0142] Next, this assembly was placed in an air autoclave and the temperature and pressure were increased 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, then the pressure was returned to ambient temperature (over 15 minutes), and the final laminate was removed from the autoclave.

[0143] 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 room temperature air across the entire surface of each laminate. The actual cooling rate curve of the sample was determined using thermocouples installed within 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 then the temperature inside the laminate was returned to near room temperature in an additional 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.

[0144] Haze, transparency, and YI measurements The laminate was thoroughly cleaned using WINDEX glass cleaner (S.C. Johnson & Son, Inc.) and lint-free cloth and inspected to ensure there were no bubbles or other defects that could interfere with valid optical measurements. Next, the laminate was evaluated using a Haze-gard Plus haze meter (Byk-Gardner) to obtain haze rate measurements. As used herein, the term "haze" refers to the percentage of transmitted light that deviates from the incident beam by more than 2.5 degrees when passing through the material. Haze is measured using a Hazegard Plus haze meter in accordance with ASTM method No. D1003 (20000). As used herein, the term "transparency" is related to the percentage of transmitted light that deviates from the incident beam when passing through the material, but the angle of deviation is less than 2.5 degrees. Transparency is also measured using a Hazegard Plus haze meter.

[0145] Color measurements were performed 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 according to ASTM E313-05 using a 2-degree observation angle and a C light source (2 degrees).

[0146] [Table 1]

[0147] Table 2 shows the optical data of the laminate made by directly compression molding on the plaque of resin pellets and its physical blend. In compression molding, since the mixing between adjacent resin particles is not sufficiently carried out, if there are differences in optical properties between resin particles or even inside resin particles, it may be visualized in the polymer plaque or glass laminate resulting therefrom. The same two kinds of resins (IO-1 and IO-2) were introduced into a twin-screw extruder having moderately strong mixing ability, and the resins were kneaded together and tried to be closely blended. Examples CE2-01, CE2-02, CE2-03, and CE2-04 were pure resins. Blends EX2-01 to EX2-07 were all visually transparent on a "macroscale" basis, and the haze measurement values of all laminated glass samples showed relatively low haze values. However, both the transparency and visual distortion of the physical blend showed a decrease in optical transparency from any starting resin. This is because when the physical mixture is simply compression molded and thus not sufficiently mixed, the difference in refractive index of the resins is particularly obvious. Samples EX2-08 to EX2-10 kneaded by twin-screw extrusion were well mixed as measured by the visual distortion test and also measured by the shadowgraph test. Visual distortion was evaluated by assessing the magnitude of the distortion of a black and white square grid (0.5-inch size) "checkerboard" (12 inches × 12 inches size), placing the grid 12 feet away (held vertically) from the laminated glazing on which the grid was laminated, and viewing it visually at a distance of 4 feet from the target glazing. The grid and glazing were viewed in the normal vertical direction, and each glazing was numbered and evaluated as follows: 0 - none, 1 - minimal, 2 - mild, 3 - moderate, 4 - severe, 5 - excessive. The shadowgraph test was basically carried out using the description provided in U.S. Patent Application No. 2012-0133764. As a result, the non-uniformity image projected on the retroreflective screen was visually evaluated.

[0148]

Table 2

[0149] 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 the compositions of this system (ethylene-methacrylic acid copolymers and terpolymers as ionomers) have a certain degree of crystallinity and are well understood to 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 intermediate layer of the ionomer species in the glass form, it is generally recommended to cool at a sufficient cooling rate from the "high temperature" part of the cycle (generally called "heat soak", temperatures in the range of 105 °C to 170 °C) 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. Since haze is an undesirable property for laminated glass where high transparency is desired, 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, adjustments of process settings and process conditions, and differences in heat conduction due to the structural material and physical size / thickness.

[0150] Table 3 includes resins compounded with a relatively low level (0.02% - 0.30% w / w) of a second resin, which resulted in an increase in haze value and YID value, as well as an increase in YID compared to the pure resin (IO-1).

[0151]

Table 3

[0152] Table 4 shows the optical data when IO-1 is blended with various acid copolymer resins with methacrylic acid levels in the range of 4 wt% to 15 wt%. An obvious trend is shown that as the difference in acid levels between most of the components (IO-1) and the added ACR resin becomes smaller, the haze and the magnitude of YID also become smaller.

[0153]

Table 4

[0154] Table 5 shows the haze and YID data for various combinations of blends of the following components: a). unused dicarboxylic acid ionomer (IO-1), b). unused ter-ionomer (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 be related to minimizing the degree of impact on the visible quality or undesirable changes in other performance parameters that may result (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 entire blend range. This would allow for complete manufacturing flexibility in blending this resin system with the 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 technology, even with differences in the thermal cycles / cooling rates shown in the lamination process.

[0155]

Table 5

[0156] Table 6 shows optical data for combinations of dicarboxylic acid ionomers (IO-1) and / or ter-ionomers (IO-2), or recycled versions thereof, with blends containing the 19% methacrylic acid copolymer-based sodium ionomer (IO-6). These combinations showed a surprising optical effect, namely an increase in both haze and YID that occurred in the intermediate composition blends of IO-6. This can be confirmed in the series of Table 7, where haze gradually increased with the percentage of IO-6 blended into IO-1 and IO-2, and YID was maximum at an intermediate value (see EX6-03 with a YID of 4.07 relative to YID values of 1.46 or 2.06 at the endpoints). The same behavior can be confirmed for a series of examples where intermediate compositions containing IO-6 showed excessive YID values. All of these trends were most clearly observed with the slow cooling rate data of 0.1 °C / min, but this behavior was similarly confirmed with the "rapid" cooling rate data.

[0157]

Table 6

[0158] The above description of the present invention provides methods and processes for manufacturing and using it such that anyone skilled in the art can manufacture and use it. This feasibility is provided, in particular, for the subject matter of the appended claims that form part of the original description. This description is provided in the context of a particular use and its requirements. Various modifications to the embodiments will be readily apparent to those skilled in the art, and the general principles defined herein can be applied to other embodiments and uses without departing from the spirit and scope of the present invention. Accordingly, the present invention is not intended to be limited to the illustrated embodiments, but the broadest scope consistent with the principles and features disclosed herein should be given. In this regard, certain embodiments within the present invention may not exhibit all the advantages of the present invention when considered in a broad sense.

Claims

1. (i)At least partially sodium-neutralized ethylene acid dipolymer ionomer resin in an amount of about 1 wt% to about 99 wt%, and (ii)At least partially sodium-neutralized ethylene acid ester terpolymer ionomer resin in an amount of about 1 wt% to 99 wt% An ionomer resin composition comprising: The combined wt% of (i) and (ii) is 100 wt%, and wt% is based on the combined weight of (i) + (ii), an ionomer resin composition.

2. The dipolymer ionomer resin is at least partially sodium-neutralized ethylene acid dipolymer ionomer resin essentially consisting of copolymer units of ethylene and at least one α,β-unsaturated carboxylic acid, and the terpolymer ionomer resin is at least partially alkali metal-neutralized ethylene acid terpolymer ionomer resin containing copolymer units of ethylene, at least one α,β-unsaturated carboxylic acid, and at least one α,β-unsaturated carboxylic acid ester. The composition according to Claim 1.

3. Based on the combined weight of the dipolymer ionomer resin and the terpolymer ionomer resin, the ionomer resin composition further contains a dialkoxysilane adhesion promoter present in an amount in the range of about 50 to about 5000 weight ppm. The composition according to Claim 1.

4. The dipolymer ionomer resin is (i)Ethylene, and (ii)About 10 wt% to about 30 wt% of at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms Essentially consisting 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 a sodium counter ion, The terpolymer ionomer resin is (i)Ethylene (ii)About 10 wt% to about 30 wt% of at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms, (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 wherein the weight percentage of the copolymer units of the terpolymer ionomer resin is based on the total weight of the terpolymer ionomer resin, the total weight percentage of the copolymer units of the terpolymer ionomer resin is 100 wt%, and 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 counterions. The ionomer resin composition according to claim 1. **Claim 5** The weight ratio of the dipolymer ionomer resin to the terpolymer ionomer resin in the composition, w / w dipolymer / terpolymer, is from 1 / 99 to 50 / 50 based on the total weight of the dipolymer ionomer resin and the terpolymer ionomer resin. The ionomer resin composition according to claim 1. **Claim 6** The weight ratio of the dipolymer ionomer resin to the terpolymer ionomer resin in the composition, w / w dipolymer / terpolymer, is from 99 / 1 to 50 / 50 based on the total weight of the dipolymer ionomer resin and the terpolymer ionomer resin. The ionomer resin composition according to claim 1. **Claim 7** Either (i) or (ii) is from about 5 wt% to about 30 wt% based on the combined weight of (i) + (ii). The ionomer resin composition according to claim 1. **Claim 8** Either (i) or (ii) is from about 10 wt% to about 30 wt% based on the combined weight of (i) + (ii). The ionomer resin composition according to claim 7. **Claim 9** Either (i) or (ii) is from about 5 wt% to about 25 wt% based on the combined weight of (i) + (ii). The ionomer resin composition according to claim 7. **Claim 10** Either (i) or (ii) is from about 10 wt% to about 25 wt% based on the combined weight of (i) + (ii). The ionomer resin composition according to claim 7. **Claim 11** The ionomer resin composition according to claim 1, wherein at least a part of at least one of (i) and (ii) is in the form of a recycled material.

12. The ionomer resin composition according to claim 11, wherein substantially all of (i) or (ii) is a recycled material.

13. The ionomer resin composition according to claim 1, wherein at least a part of one of (i) or (ii) is in the form of an unused material.

14. The ionomer resin composition according to claim 1, wherein at least a part of at least one of (i) and (ii) is a combination of an unused material and a recycled material.

15. The ionomer resin composition according to claim 1, wherein both (i) and (ii) are a combination of an unused material and a recycled material.

16. The ionomer resin composition according to claim 1, wherein one of (i) or (ii) is substantially an unused material and one of (i) and (ii) is a combination of an unused material and a recycled material.

17. The ionomer resin composition according to claim 1, wherein one of (i) or (ii) is substantially an unused material and one of (i) or (ii) is substantially a recycled material.

18. An intermediate layer sheet comprising the ionomer resin composition according to any one of claims 1 to 17.

19. A glass laminate comprising the intermediate layer sheet according to claim 18.

20. A method for producing the intermediate sheet according to claim 18, comprising the steps of melt-blending (i), (ii) and optional components under shear to produce a melt blend, then extruding the melt blend through a die into sheet form, and then cooling the sheet form to solidify the resin composition.

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