Ionic polymer interlayer with enhanced adhesion properties

Abstract

The present invention provides a sodium-neutralized ethylene glycol copolymer ionomer composition containing a specified amount of a specified silane additive and enhancing adhesion properties to glass, a masterbatch composition suitable for preparing such ionomer composition, an interlayer made from such ionomer composition, and a glass laminate including such interlayer.

Description

[0001] This invention patent application is a divisional application of the invention patent application with application number 201880050246.6, application date July 30, 2018, and invention title "Ionomer Interlayer with Enhanced Adhesion Properties". Technical Field

[0002] The present invention relates to interlayers based on ethylene-based copolymer ionomer compositions that have enhanced adhesion properties to glass, and glass laminates comprising such interlayers. Background Technology

[0003] Laminated glass is typically made by pressing two sheets of glass onto a plastic interlayer. A particular advantage of laminated glass over solid glass sheets is its impact resistance and shatter resistance, resulting from the adhesion of the glass to the interlayer.

[0004] In safety glass laminates, the optimal adhesion of the interlayer to the glass is a balance. Too strong an adhesion reduces the laminate's ability to absorb and dissipate energy during an impact event, while too weak an adhesion can lead to optical defects (during and after lamination) and adversely affect the interlayer's ability to retain glass fragments upon impact.

[0005] Many different materials are used as plastic interlayers. For example, sheets containing polyvinyl butyral (polyvinyl alcohol butyral) and plasticizers are widely used as interlayers in laminated glass because of their excellent adhesion properties to glass. Laminated glass containing this type of interlayer can be made with good transparency, mechanical strength, flexibility, sound damping, and shatter resistance.

[0006] At least partially neutralized ethylene glycol copolymers (ionomers) have also been used as interlayers in the preparation of laminated safety glass, as disclosed in, for example, US3404134, US3344014, US7445683B2, US7763360B2, US7951865B1, US7960017B2, US8399097B2, US8399098B2, US2017 / 0320297A1, US2018 / 0117883A1, WO2016 / 076336A1, WO2016 / 076337A1, WO2016 / 076338A1, WO2016 / 076339A1 and WO2016 / 076340A1.

[0007] While ionomer resins can be selected to create interlayers with excellent flexural strength and optical properties, their adhesion to glass may not be optimal. In particular, because ionomers are neutralized acid copolymers, they are indeed prone to lamination defects, especially in high-humidity environments.

[0008] For example, when using ionomer resins as interlayers for float glass, the adhesion on the "tin side" of the glass is often satisfactory, but the adhesion on the "air side" is unsatisfactory. Therefore, special precautions need to be taken during the lamination process to properly orient these glass sheets to ensure contact between the "tin side" and the interlayer.

[0009] It has been proposed to use primers and other surface treatments on the glass and interlayer to help address adhesion issues (see, for example, US2016 / 0159042A1), but this increases the cost and complexity of the lamination process, and such surface treatments often result in excessively strong adhesion, as previously shown, which may reduce the laminate’s ability to absorb and dissipate energy during impact events.

[0010] Ionomer resin modification and blending with additives have also been explored. For example, increasing the acid level of the ethylene copolymer does improve the adhesion properties of the final ionomer; however, there are practical and economic limitations to how much the acid value can be increased. The use of additives has also yielded limited success.

[0011] In particular, silanes are known to be excellent adhesion promoters for glass in many different resin systems. However, as disclosed in US20110105681A1, the use of silanes, typically with ionomers and especially with sodium-neutralized ionomers, produces gels and fails to generate a melt flow capable of satisfactory sheet extrusion. This particular publication identifies a narrow class of amino-containing dialkoxysilanes that can only be used in conjunction with specific types of zinc-neutralized ionomers.

[0012] Contrary to the teachings of US20110105681A1, it has now been found that certain types of silanes can be successfully and advantageously used as glass adhesion promoters for sodium-neutralized ionomers in very specific amounts and under limited conditions, thereby enabling the optimal use of such ionomers in the preparation of interlayers and glass laminates with enhanced adhesion properties of the interlayers to glass. Summary of the Invention

[0013] The present invention solves the above-mentioned problems by providing a resin composition comprising (i) an ionomer resin and (ii) an adhesion promoter additive, wherein:

[0014] (1) The ionomer resin is a sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer;

[0015] (2) The adhesion promoter additive is a dialkoxysilane compound; and

[0016] (3) Based on the weight of the ionomer resin, the diekoxysilane compound is present in the resin composition in an amount of about 50 to about 5,000 parts by weight per million.

[0017] In one embodiment of the above-described resin composition, the dialkoxysilane compound is a liquid under ambient conditions. In another embodiment, the dialkoxysilane compound is substantially uniformly distributed within the resin composition. In yet another embodiment, the resin composition is a particulate resin composition, wherein the ionomer resin is a particulate ionomer resin, and the dialkoxysilane compound is present in the resin composition primarily (or substantially) by means of adsorption onto the surface of the ionomer resin particles.

[0018] On the other hand, the present invention provides a particulate masterbatch composition comprising (i) ions of an ionomer resin and (ii) an adhesion promoter additive, wherein:

[0019] (1) The ionomer resin of the ionomer resin particles is a sodium-neutralized ethylene·α,β-unsaturated carboxylic acid copolymer;

[0020] (2) The adhesion promoter additive is a dialkoxysilane compound;

[0021] (3) Based on 100 parts by weight of the ionomer resin, a dialkoxysilane compound is present in the masterbatch composition in an amount ranging from about 1 to about 10 parts by weight; and

[0022] (4) Dialkoxysilane compounds are present in the masterbatch composition primarily (or essentially) by means of absorption on the surface of ionomer resin particles.

[0023] In one embodiment of the above masterbatch composition, the dialkoxysilane compound is a liquid under ambient conditions. In another embodiment, the dialkoxysilane compound is substantially uniformly distributed within the particulate masterbatch composition.

[0024] On the other hand, the present invention provides a first method for preparing a resin composition, the method comprising the following steps:

[0025] (A) Provides a masterbatch composition comprising (i) ions of an ionomer resin and (ii) an adhesion promoter additive, wherein:

[0026] (1) The ionomer resin particles are ethylene-α,β-unsaturated carboxylic acid copolymers neutralized with sodium ionomer.

[0027] (2) The adhesion promoter additive is a dialkoxysilane compound.

[0028] (3) Based on 100 parts by weight of the ionomer resin, a dialkoxysilane compound is present in the masterbatch composition in an amount ranging from about 1 to about 10 parts by weight, and

[0029] (4) The diekoxysilane is present primarily (or substantially) by means of absorption onto the surface of the ionomer resin particles; and

[0030] (B) The masterbatch composition is mixed with a certain amount of sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer to obtain a close mixture with a concentration of about 50 to about 5000 parts by weight of the diekoxysilane compound based on the total weight of the ionomer resin.

[0031] The ethylene-α,β-unsaturated carboxylic acid copolymers neutralized by the first and second sodium may be the same or different.

[0032] In one embodiment of the above method, the dialkoxysilane compound is a liquid under ambient conditions. In another embodiment, the dialkoxysilane compound is substantially uniformly distributed within the resin composition. In another embodiment, the mixing step is a melt blending step. In another embodiment, the ethylene-α,β-unsaturated carboxylic acid copolymer neutralized by the second sodium is particulate, the mixing step is carried out under conditions where both the ethylene-α,β-unsaturated carboxylic acid copolymers neutralized by the first and second sodiums are not softened, and the resin composition is a particulate resin composition.

[0033] On the other hand, the present invention provides a method for preparing a particulate resin composition, the method comprising the following steps:

[0034] (A) Provides (i) particles of an ionomer resin having a surface and (ii) an adhesion promoter additive, wherein (1) the ionomer resin of the ionomer resin particles is a sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer, and (2) the adhesion promoter additive is a dialkoxysilane compound, and

[0035] (B) Physically mixing particles with adhesion promoter additives under non-softening conditions of ionomer resin to produce particles in which the diekoxysilane compound is present primarily (or substantially) in a manner absorbed on the surface of the ionomer resin particles.

[0036] The diekoxysilane compound is provided in an amount resulting in a concentration of about 50 to about 5,000 parts by weight in the resin composition based on the total weight of the ionomer resin.

[0037] In one embodiment of the above method, the dialkoxysilane compound is a liquid under ambient conditions. In another embodiment, the dialkoxysilane compound is substantially uniformly distributed within the particulate resin composition.

[0038] In one embodiment of all the above compositions and methods, the dialkoxysilane compound contains a carboxylic acid reactive group in addition to the two alkoxysilyl groups. In one embodiment, the carboxylic acid reactive group is an amino or glycidyl group.

[0039] On the other hand, the present invention provides a method for preparing sheets of ionomer resin by melt-blending one of the above-mentioned particulate resin compositions under shear conditions to produce a melt blend, then extruding the melt blend into sheet form through a die, and then cooling the sheet form to cure the resin. In one embodiment, the sheet has a top surface and a bottom surface, and the sheet has an embossed pattern on one or both of the top and bottom surfaces before curing.

[0040] In other respects, the present invention provides sandwich panels of such resin compositions and glass laminates made from such sandwich panels, for example comprising two glass plates with a sandwich according to the invention inserted between them.

[0041] In one embodiment, the sandwich panel comprises a layer containing a sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer, wherein when the sandwich panel is pretreated at 34°C and 50% relative humidity (as described in the examples), and the layer of sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is adhered to the air-facing side of a float glass sheet having an air-facing side and a tin side, the peel adhesion of the layer of sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer adhered to the air-facing side of the float glass sheet is at least about 20 N / cm (measured at 23°C and 50% RH as described in the examples).

[0042] In another embodiment, the sandwich panel comprises a layer containing a sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer, wherein when the sandwich panel is pretreated at 34°C and 50% relative humidity (as described in the examples), and the layer of sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is adhered to the air-facing side of a float glass sheet having an air-facing side and a tin side, the peel adhesion force of the layer of sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer adhered to the air-facing side of the float glass sheet is at least about 0.5 or at least about 1 N / cm under wet conditions (measured as described in the examples).

[0043] In another embodiment, the sandwich panel comprises a layer containing a sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer, wherein when the sandwich panel is pretreated at 34°C and 50% relative humidity (as described in the examples), and the layer of sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is adhered to a float glass sheet having an open side and a tin side, the peel adhesion force of the layer of sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer when adhered to the open side of the float glass sheet is (i) greater than about 5 N / cm (measured at 23°C and 50% RH as described in the examples) or greater than about 10 N / cm (measured at 23°C and 50% RH as described in the examples), and (ii) greater than the peel adhesion force when adhered to the tin side of the float glass sheet (measured at 23°C and 50% RH as described in the examples).

[0044] Those skilled in the art will more readily understand these and other embodiments, features, and advantages of the present invention by reading the following detailed description.

[0045] In particular, the present invention relates to the following aspects:

[0046] Item 1. A resin composition comprising (i) an ionomer resin and (ii) an adhesion promoter additive in close mixture, characterized in that:

[0047] (a) The ionomer resin is a sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer;

[0048] (b) The adhesion promoter additive is a dialkoxysilane compound; and

[0049] (c) Based on the weight of the ionomer resin, the dialkoxysilane compound is present in the resin composition in an amount ranging from 50 to 5000 parts per million by weight.

[0050] Item 2. The resin composition as described in Item 1, characterized in that the dialkoxysilane compound is a liquid at ambient temperature.

[0051] Item 3. The resin composition as described in Item 1 or Item 2, characterized in that the dialkoxysilane compound is substantially uniformly distributed within the resin composition.

[0052] Item 4. The resin composition of any one of items 1-3, characterized in that each of the alkoxy groups of the dialkoxysilane compound individually contains 1 to 3 carbon atoms, and / or, in addition to the alkoxy groups, the dialkoxysilane compound also contains active chemical groups for bonding to the ionomer resin.

[0053] Item 5. The resin composition as described in Item 4, characterized in that the active chemical group is selected from amino and glycidyl groups.

[0054] Item 6. The resin composition as described in Item 1, characterized in that the dialkoxysilane compound is selected from N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane.

[0055] Item 7. A resin composition as described in any one of items 1-6, wherein the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer comprises constituent units derived from ethylene and constituent units derived from α,β-unsaturated carboxylic acids, wherein at least a portion of the constituent units derived from the α,β-unsaturated carboxylic acids are neutralized by counterions, and wherein the counterions are substantially composed of sodium cations.

[0056] Item 8. The resin composition as described in Item 1, characterized in that:

[0057] (A) The sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is a binary copolymer composed essentially of the following copolymer units:

[0058] (i) ethylene, and

[0059] (ii) 10% to 30% by weight of at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms.

[0060] The weight percentage of the copolymer unit is based on the total weight of the ethylene copolymer, and the sum of the weight percentages of the copolymer units is 100% by weight, and at least a portion of the carboxylic acid groups of the α,β-unsaturated carboxylic acid are neutralized to form an ionomer containing carboxylic acid groups with sodium counterions.

[0061] or

[0062] (B) The sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is a terpolymer consisting essentially of the following copolymer units:

[0063] (i) Ethylene,

[0064] (ii) 10% to 30% by weight of at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms.

[0065] (iii) 2% to 15% by weight of at least one α,β-unsaturated carboxylic acid ester having 3 to 10 carbon atoms, and

[0066] (iv) Any derivative of an α,β-unsaturated carboxylic acid other than (iii), in an amount such that (iii) + (iv) is 15% by weight or less.

[0067] The weight percentage of the copolymer units is based on the total weight of the ethylene copolymer, and the sum of the weight percentages of the copolymer units is 100% by weight, and at least a portion of the carboxylic acid groups of the α,β-unsaturated carboxylic acid are neutralized to form an ionomer containing carboxylic acid groups with sodium counterions.

[0068] Item 10. A particulate masterbatch composition comprising (i) particles of an ionomer resin and (ii) an adhesion promoter additive, characterized in that:

[0069] (a) The ionomer resin of the ionomer resin particles is a sodium-neutralized ethylene·α,β-unsaturated carboxylic acid copolymer;

[0070] (b) The adhesion promoter additive is a dialkoxysilane compound;

[0071] (c) Based on 100 parts by weight of the ionomer resin, the dialkoxysilane compound is present in the masterbatch composition in an amount ranging from 1 to 10 parts by weight; and

[0072] (d) The diekoxysilane compound is present in the masterbatch composition primarily by means of absorption on the surface of the ionomer resin particles.

[0073] Item 11. The masterbatch composition as described in Item 10, characterized in that each of the alkoxy groups in the dialkoxysilane compound individually contains 1 to 3 carbon atoms, and / or, in addition to the alkoxy groups, the dialkoxysilane compound also contains active chemical groups for bonding to the ionomer resin.

[0074] Item 12. The masterbatch composition as described in Item 11, characterized in that the active chemical group is selected from amino and glycidyl groups.

[0075] Item 13. The masterbatch composition as described in Item 10, characterized in that the dialkoxysilane compound is selected from N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane and 3-glycidoxypropylmethyldiethoxysilane.

[0076] Item 14. The masterbatch composition of any one of items 10-13, characterized in that the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer comprises constituent units derived from ethylene and constituent units derived from α,β-unsaturated carboxylic acids, wherein at least a portion of the constituent units derived from the α,β-unsaturated carboxylic acids are neutralized by counterions, and wherein the counterions are substantially composed of sodium cations.

[0077] Item 15. The masterbatch composition as described in Item 14, characterized in that:

[0078] (A) The sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is a binary copolymer composed essentially of the following copolymer units:

[0079] (i) ethylene, and

[0080] (ii) 10% to 30% by weight of at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms.

[0081] The weight percentage of the copolymer unit is based on the total weight of the ethylene copolymer, and the sum of the weight percentages of the copolymer units is 100% by weight, and at least a portion of the carboxylic acid groups of the α,β-unsaturated carboxylic acid are neutralized to form an ionomer containing carboxylic acid groups with sodium counterions.

[0082] or

[0083] (B) The sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is a terpolymer consisting essentially of the following copolymer units:

[0084] (i) Ethylene,

[0085] (ii) 10% to 30% by weight of at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms.

[0086] (iii) 2% to 15% by weight of at least one α,β-unsaturated carboxylic acid ester having 3 to 10 carbon atoms, and

[0087] (iv) Any derivative of an α,β-unsaturated carboxylic acid other than (iii), in an amount such that (iii) + (iv) is 15% by weight or less.

[0088] The weight percentage of the copolymer units is based on the total weight of the ethylene copolymer, and the sum of the weight percentages of the copolymer units is 100% by weight, and at least a portion of the carboxylic acid groups of the α,β-unsaturated carboxylic acid are neutralized to form an ionomer containing carboxylic acid groups with sodium counterions.

[0089] Item 16. A method for preparing a resin composition, the method comprising the following steps:

[0090] (A) Provides a masterbatch composition as described in any one of claims 10-15; and

[0091] (B) The masterbatch composition is mixed with a certain amount of sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer to obtain a close mixture with a concentration of 50 to 5000 parts by weight of the diekoxysilane compound based on the total weight of the ionomer resin.

[0092] Item 17. A sandwich panel comprising: a layer containing a sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer, characterized in that:

[0093] (A) When the sandwich panel is pretreated at 34°C and 50% relative humidity, and the layer of the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is adhered to the air-facing side of a float glass sheet having an air-facing side and a tin side, the peel adhesion force of the layer of the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer adhered to the air-facing side of the float glass sheet is at least about 20 N / cm (measured at 23°C and 50% RH); and / or

[0094] (B) When the sandwich panel is pretreated at 34°C and 50% relative humidity, and the layer of the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is adhered to the air-facing side of a float glass sheet having an air-facing side and a tin side, the peel adhesion of the layer of the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer adhered to the air-facing side of the float glass sheet is at least about 0.5 (under wet conditions); and / or

[0095] (C) When the sandwich panel is pretreated at 34°C and 50% relative humidity, and the layer of the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is adhered to a float glass sheet having an open side and a tin side, the peel adhesion force (i) of the layer of the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer when adhered to the open side of the float glass sheet is greater than about 5 N / cm (measured at 23°C and 50% RH), and (ii) is greater than the peel adhesion force when adhered to the tin side of the float glass sheet (measured at 23°C and 50% RH).

[0096] This invention relates to resin compositions, masterbatch compositions, resin compositions prepared using such masterbatch compositions, interlayers prepared from such resin compositions, and glass laminates containing such interlayers. Further details are provided below.

[0097] In the context of this specification, unless otherwise indicated, all publications, patent applications, patents and other references mentioned herein are incorporated herein by reference in their entirety for all purposes, as if fully described.

[0098] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. In case of any conflict, this specification (including definitions) shall prevail.

[0099] Unless otherwise specified, trademarks are displayed in capital letters.

[0100] Unless otherwise stated, all percentages, parts, ratios, etc. are by weight.

[0101] Unless otherwise stated, pressure expressed in psi is gauge pressure, and pressure expressed in kPa is absolute pressure. However, pressure difference is expressed as absolute pressure difference (e.g., pressure 1 is 25 psi higher than pressure 2).

[0102] When quantities, concentrations, or other values ​​or parameters are given as a range or a list of upper and lower limits, this should be understood as specifically disclosing all ranges formed by any upper and lower limit boundaries of any pair of ranges, regardless of whether the range is disclosed individually. In the case of numerical ranges enumerated herein, unless otherwise stated, the range is intended to include its endpoints, as well as all integers and fractions within that range. When a range is defined, it is not intended to limit the scope of this disclosure to the specific values ​​listed.

[0103] When the term "about" is used, it is used to indicate that a certain effect or result can be obtained within a certain tolerance range, and that a person skilled in the art knows how to obtain that tolerance. When the term "about" is used to describe the endpoints of a value or range, the disclosure should be understood to include the specific value or endpoint referred to.

[0104] As used herein, the terms “comprises / comprising,” “includes / including,” “has / having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0105] The transitional phrase "composed of..." excludes any element, step, or ingredient not specified in the claim, thereby limiting the claim to exclude substances other than those listed, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of the claim rather than immediately following the preamble, it only limits the elements listed in that clause; other elements are not excluded from the claim as a whole.

[0106] The transitional phrase "consistently composed of..." narrows the scope of the claim to the specified substance or step and substances or steps that do not substantially affect the essential and novel features of the claimed invention. Claims "consistently composed of..." fall between closed claims written in the "consistently composed of..." format and fully open claims written in the "comprising..." format. Optional additives as defined herein (at appropriate levels for such additives) and trace amounts of impurities are not excluded from the composition by the term "consistently composed of...".

[0107] Furthermore, unless explicitly stated otherwise, “or” and “and / or” refer to inclusion rather than exclusivity. For example, any of the following satisfy the condition A or B or A and / or B: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), and both A and B are true (or exist).

[0108] The use of “a species” to describe the various elements and components of this document is merely for convenience and to give a general meaning to the disclosure. This description should be interpreted as including a species or at least one species, and the singular includes the plural, unless clearly otherwise intended.

[0109] Unless otherwise defined herein, the terms “major component” or “major” as used herein mean more than 50% of the substance mentioned. If not specified, percentages are expressed in moles when referring to molecules (such as hydrogen and ethylene) and by weight otherwise (such as for additive content).

[0110] Unless otherwise defined, the terms “substantial” or “largely” as used herein mean all or almost all or the vast majority as understood by one of ordinary skill in the art in the context in which they are used. This is intended to account for reasonable differences from 100%, which typically occur on an industrial or commercial scale.

[0111] The terms “depleted” or “reduced” are synonyms for a decrease compared to the initial state. For example, removing a large portion of a substance from a stream will result in a depleted stream, which essentially depletes the substance. Conversely, the terms “enriched” or “increased” are synonyms for a greater than the initial state.

[0112] As used herein, the term "copolymer" refers to a polymer comprising copolymeric units produced by the copolymerization of two or more comonomers. In this regard, copolymers may be described herein by reference to the compositional comonomers or the amount of compositional comonomers, such as "a copolymer comprising ethylene and 15% by weight acrylic acid" or similar descriptions. Such descriptions may be considered informal because they do not refer to the comonomers as copolymeric units; because they do not include the conventional nomenclature of copolymers, such as the IUPAC nomenclature; because they do not employ the terminology of product-by-process; or for other reasons. However, as used herein, describing a copolymer by reference to the compositional comonomers or the amount of compositional comonomers means that the copolymer contains copolymeric units of a specified comonomer (in a specified amount when specified). It is therefore inferred that the copolymer is not a product of a reaction mixture containing a given amount of a given comonomer, unless explicitly stated otherwise in limited circumstances.

[0113] The term "binary copolymer" refers to a polymer consisting essentially of two monomers, and the term "terpolymer" refers to a polymer containing at least three monomers.

[0114] As used herein, the term "acid copolymer" refers to a copolymer comprising copolymer units of α-olefin, α,β-ene unsaturated carboxylic acid, and optionally other suitable comonomers such as α,β-ene unsaturated carboxylic acid esters.

[0115] The term “(meth)acrylic acid” as used alone or in combination herein, such as “(meth)acrylate”, refers to acrylic acid or methacrylic acid, for example, “acrylic acid or methacrylic acid” or “alkyl acrylate or alkyl methacrylate”.

[0116] As used herein, the term "ionomer" generally refers to a polymer containing ionic groups, which are carboxylates, such as ammonium carboxylates, alkali metal carboxylates, alkaline earth carboxylates, transition metal carboxylates, and / or combinations of such carboxylates. These polymers are generally prepared, for example, by reacting with a base to partially or completely neutralize the carboxyl groups of a precursor or parent polymer that serves as an acid copolymer as defined herein. Alkali metal ionomers, as used herein, are sodium ionomers, such as copolymers of ethylene and methacrylic acid, wherein all or some of the carboxyl groups of the co-methacrylic acid units are neutralized, and substantially all of the neutralized carboxyl groups are in the form of sodium carboxylate.

[0117] For convenience, many elements of the invention are discussed individually, and a list of options may be provided, with numerical values ​​within ranges; however, for the purposes of this disclosure, any claim relating to any such individual component, list item, or range in any combination should not be considered a limitation on the scope of this disclosure or an endorsement of it. Unless otherwise stated, every possible combination of elements in this disclosure should be considered as expressly disclosed for all purposes.

[0118] While similar or equivalent methods and substances described herein can be used to practice or test the contents of this disclosure, suitable methods and substances are described herein. Therefore, the substances, methods, and examples herein are illustrative only and, unless specifically stated otherwise, are not intended to be limiting.

[0119] Isopolymer

[0120] According to the present invention, the ionomer resin is a sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer comprising a resin having constituent units derived from ethylene, constituent units derived from α,β-unsaturated carboxylic acids, and optionally other constituent units as described below, wherein at least a portion of the constituent units derived from α,β-unsaturated carboxylic acids are neutralized by sodium ions.

[0121] In ethylene-α,β-unsaturated carboxylic acid copolymers used as the base polymer, the content of constituent 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 copolymer mass). Furthermore, the content of constituent units derived from α,β-unsaturated carboxylic acids is typically 30% by mass or less (based on the total copolymer mass).

[0122] Examples of α,β-unsaturated carboxylic acids constituting the ionomer 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-ene unsaturated carboxylic acid is selected from acrylic acid, methacrylic acid, and mixtures thereof. In another embodiment, the α,β-ene unsaturated carboxylic acid is methacrylic acid.

[0123] Vinyl acrylate copolymers may further comprise copolymer units of one or more additional comonomers, such as α,β-ene unsaturated carboxylic acid esters. When present, alkyl esters having 3 to 10 or 3 to 8 carbon atoms 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, and decadecyl acrylate. Dialkyl esters, 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, the additional comonomer is one or more of n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, and isobutyl methacrylate. In another embodiment, the additional comonomer is one or both of n-butyl acrylate and isobutyl acrylate.

[0124] According to ASTM method D1238-89, at 190°C and 2.16 kg, the suitable melt flow rate (MFR) of the vinyl acid copolymer is about 1 or about 2 to about 4000 g / 10 min or to 1000 g / 10 min or to about 400 g / 10 min.

[0125] Finally, suitable ethylene glycol copolymers can be synthesized as described, for example, in US3404134, US5028674, US6500888B2, US6518365B1, US8334033B2, and US8399096B2. In one embodiment, the method described in US8399096B2 is used, and a sufficiently high level and supplementary amount of a second α,β-ene unsaturated carboxylic acid derivative are present in the reaction mixture.

[0126] To obtain an ionomer, the ethylene glycol copolymer is partially neutralized by reacting it with one or more bases. Examples of suitable procedures for neutralizing ethylene glycol copolymers are described in US3404134 and US 6518365B1. After neutralization, about 1% or about 10% or about 15% or about 20% of the hydrogen atoms of the carboxylic acid groups present in the ethylene glycol copolymer are replaced by about 90% or about 60% or about 55% or about 30% by other cations. In other words, about 1% or about 10% or about 15% or about 20% of the total content of carboxylic acid groups present in the ethylene glycol copolymer is neutralized to about 90% or about 60% or about 55% or about 30%. In another alternative expression, based on the total content of carboxylic acid groups present in the ethylene glycol copolymer, calculated or measured for unneutralized ethylene glycol copolymer, the acid groups are neutralized to a level of about 1% or about 10% or about 15% or about 20% to about 90% or about 60% or about 55% or about 30%. The neutralization level can be adjusted according to the specific end use.

[0127] The counterion of the carboxylate anion in the ionomer is a sodium cation. Although the ionomer used in this invention is a sodium-neutralized ionomer, small amounts of counterions other than sodium cations may be present, in amounts based on the total equivalent of carboxylate groups in the ionomer being less than 5 equivalents, less than 3 equivalents, less than 2 equivalents, or less than 1 equivalent. In one embodiment, the counterion is substantially sodium ions.

[0128] Suitable cations other than sodium include any positively charged substance that is stable under conditions of synthesis, treatment, and use of the ionomer composition. Suitable cations may be used in two or more combinations. Typically, these other cations are metal cations, which may be monovalent, divalent, trivalent, or polyvalent. Monovalent metal cations include, but are not limited to, cations of potassium, lithium, silver, mercury, copper, etc. Divalent metal cations include, but are not limited to, cations of beryllium, magnesium, calcium, strontium, barium, copper, cadmium, mercury, tin, lead, iron, cobalt, nickel, zinc, etc. Trivalent metal cations include, but are not limited to, cations of aluminum, scandium, iron, yttrium, etc. Polyvalent metal cations include, but are not limited to, cations of titanium, zirconium, hafnium, vanadium, tantalum, tungsten, chromium, cerium, iron, etc. When the metal cation is polyvalent, as described in US3404134, it may include complexing agents such as stearate, oleate, salicylate, and phenolic groups. Typically, when present, the metal cation used is a monovalent or divalent metal cation, such as lithium, magnesium, zinc, potassium, or a combination of one or more of these metal cations.

[0129] In one implementation, counterions other than sodium are present in amounts not exceeding that of a “contaminant,” as is typically found in industrial settings and as is generally acknowledged by those skilled in the art.

[0130] The melt index of the sodium-neutralized ethylene glycol copolymer, determined according to ASTM method D1238-89 at 190°C and 2.16 kg, was lower than that of the corresponding ethylene glycol copolymer. The melt index of the ionomer depends on many factors, including the melt index of the ethylene glycol copolymer, the amount of copolyacid, the level of neutralization, the identity of the cation, and its valence. Furthermore, the expected melt index of the ionomer can be determined by its intended end use. However, according to ASTM method D1238-89 at 190°C and 2.16 kg, the melt index of the ionomer is typically 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.

[0131] In one embodiment, the ionomer is a at least partially sodium-neutralized vinyl acetate binary copolymer comprising the following copolymer units (essentially composed of the following copolymer units):

[0132] (i) ethylene, and

[0133] (ii) at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms, in about 10 wt% or about 15 wt% or about 18 wt% or about 20 wt% or about 30 wt% or about 25 wt% or about 23 wt% or about 22 wt%.

[0134] The weight percentage of the copolymer units is based on the total weight of the ethylene copolymer, and the sum of the weight percentages of the copolymer units is 100% by weight, wherein at least a portion of the carboxylic acid groups of the α,β-unsaturated carboxylic acid are neutralized to form an ionomer containing carboxylic acid groups with sodium counterions.

[0135] In one embodiment, the ionomer is a terpolymer of ethylene glycol that is at least partially neutralized with sodium, comprising the following copolymer units:

[0136] (i) Ethylene,

[0137] (ii) about 10% by weight or about 15% by weight or about 18% by weight or about 20% by weight to about 30% by weight or about 25% by weight or about 23% by weight or about 22% by weight of at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms.

[0138] (iii) about 2% or about 3% or about 4% or about 5% to about 15% or about 12% or about 11% or about 10% of at least one α,β-unsaturated carboxylic acid ester having 3 to 10 carbon atoms, and

[0139] (iv) Any derivative of an α,β-unsaturated carboxylic acid other than (iii), in an amount such that (iii) + (iv) is about 15% by weight or less, or about 12% by weight or less, or about 11% by weight or less.

[0140] The weight percentage of the copolymer units is based on the total weight of the ethylene copolymer, and the sum of the weight percentages of the copolymer units is 100% by weight, wherein at least a portion of the carboxylic acid groups of the α,β-unsaturated carboxylic acid are neutralized to form an ionomer containing carboxylic acid groups with sodium counterions.

[0141] Such terpolymer ionomers are generally disclosed in WO2015 / 199750A1, WO2014 / 100313A1 and US2017 / 0320297A1.

[0142] In one embodiment of the binary or ternary copolymer described above, the α,β-unsaturated carboxylic acid is methacrylic acid.

[0143] In one embodiment of the terpolymer described above, the α,β-unsaturated carboxylic acid ester is n-butyl acrylate, isobutyl acrylate, or a mixture thereof.

[0144] In one embodiment of the above ternary copolymer, the copolymer is essentially composed of copolymer units of (i), (ii) and (iii).

[0145] silane

[0146] The silane suitable for use according to the present invention is a dialkoxysilane. Unbound by theory, it is believed that the hydrolyzed silanol portion of the silane can form an adhesive bond with the glass surface (silanol), thereby enhancing the adhesion at the interface between the polymer and the glass surface. The remaining portion of the silane molecule should then be "anchored" in some way and to some extent to the surrounding ionomer resin "matrix". One way to achieve this is by selecting functional groups that will interact advantageously so that the silane is chemically bonded or via ionic or hydrogen bonds or sufficient van der Waals forces, or has a size and shape that allows it to "bridge" between the interlayer and the glass surface in space, thereby increasing adhesion on the same interlayer without the need for advantageous silane additives.

[0147] In one embodiment, each of the alkoxy groups 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.

[0148] In another embodiment, in addition to alkoxy groups, the silane also contains "active" chemical groups, such as carboxylic acid reactive groups, like amino or glycidyl groups, for bonding to the ionomer resin matrix. Suitable examples include γ-aminopropyl-N-cyclohexylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylmethyldiethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, and 3-glycidyloxypropylmethyldiethoxysilane.

[0149] Preferably, silanes are liquids under ambient conditions (e.g., at 20°C). Specific examples of this type include N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane (CAS#3069-29-2) and 3-glycidoxypropylmethyldiethoxysilane (CAS#2897-60-1).

[0150] Other adhesion modifiers

[0151] In addition to using silane, the adhesion of the interlayer to glass and other materials can be further controlled if needed.

[0152] For example, olefin polymers containing reactive functional groups (hereinafter referred to as olefin polymers containing carboxylic acid groups) can also be used as adhesion modifiers, wherein the functional group is at least one group selected from carboxyl groups and carboxyl derivative groups (hereinafter referred to as carboxylic acid groups). Suitable olefin polymers containing carboxylic acid groups are disclosed, for example, in US7989083B2.

[0153] While a critical minimum adhesion level is necessary to maintain sufficient laminate integrity (e.g., to prevent delamination defects) and adequate retention of glass force in the post-fracture state, the impact performance of the resulting laminate can be deliberately optimized or tuned. Although the optimal amount (cumulative) of adhesion modifier varies depending on the additive used and the resin to which adhesion is modulated, a preferred approach is to typically adjust the adhesion of the resulting laminate to the glass to approximately 3 or greater and approximately 10 or less in impact tests (described in WO03 / 033583A1, etc.). Specifically, where high penetration resistance is required, a more preferred approach is to adjust the amount of adhesion modifier to approximately 3 or greater and approximately 6 or less, while where high shatterproof glass properties are required, a more preferred approach is to adjust the amount of adhesion modifier to approximately 7 or greater and approximately 10 or less.

[0154] Other additives

[0155] In addition to the aforementioned silanes and other adhesion modifiers, the resin compositions and masterbatches of the present invention may also contain one or more other additives, including, for example, antioxidants, ultraviolet absorbers, light stabilizers, anti-blocking agents, pigments, dyes, heat-insulating materials (infrared absorbers), and mixtures thereof. These other additives are well known to those skilled in the art in the general sense.

[0156] Examples of antioxidants include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, etc. Among these, phenol-based antioxidants are preferred, and antioxidants based on alkyl-substituted phenols are particularly preferred.

[0157] Examples of phenol-based antioxidants include acrylate-based compounds such as 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate and 2,4-di-tert-pentyl-6-(1-(3,5-di-tert-pentyl-2-hydroxyphenyl)ethyl)phenyl acrylate; and alkyl-substituted phenol-based compounds such as 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 2,2'-methylphenyl-4-ethylphenol. Methyl-bis(4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis(4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane, 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,1, 3-Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetra(methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate)methane, and triethylene glycol bis(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate); phenol-based compounds containing triazine groups, such as 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)-1,3,5-triazine-2, 4,6(1H,3H,5H)-trione, 6-(4-hydroxy-3,5-di-tert-butylaniline)-2,4-bis-octylthio-1,3,5-triazine, 6-(4-hydroxy-3,5-dimethylaniline)-2,4-bis-octylthio-1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-tert-butylaniline)-2,4-bis-octylthio-1,3,5-triazine and 2-octylthio-4,6-bis-(3,5-di-tert-butyl-4-oxyaniline)-1,3,5-triazine; and so on.

[0158] Examples of phosphorus-based antioxidants include compounds based on monophosphite esters, such as triphenyl phosphite, diphenyl isodecanyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(2-tert-butyl-4-methylphenyl) phosphite, tris(2,4-di-tert-butyl) phosphite, tris(cyclohexylphenyl) phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10- Phosphenanthrene-10-oxide and 10-decoxy-9,10-dihydro-9-oxa-10-phosphenanthrene; compounds based on diphosphites, such as 4,4'-butylene-bis(3-methyl-6-tert-butylphenyl-di-tetrazylphosphite), 4,4'-isopropylene-bis(phenyl-dialkyl(C12-C15)phosphite), 4,4'-isopropylene-bis(diphenylmonoalkyl(C12-C15)phosphite)1,1,3-tris(2-methyl-4-di-tetrazylphosphite-5-tert-butylphenyl)butane and tetra(2,4-di-tert-butylphenyl)-4,4'-biphenylphosphite; etc. Among these, compounds based on monophosphites are preferred.

[0159] Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, distearate 3,3'-thiodipropionate, lauryl stearate 3,3'-thiodipropionate, pentaerythritol-tetra-(β-lauryl-thiopropionate), 3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, etc.

[0160] These antioxidants can be used alone or in combination of two or more. In the final resin composition, the amount of 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. Furthermore, the amount of 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. In the masterbatch composition, [add a number].

[0161] Examples of UV absorbers include benzotriazole-based UV absorbers such as 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α'-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, and 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)triazole; and hindered amine-based UV absorbers such as benzoic acid 2,2,6 6-Tetramethyl-4-piperidinyl ester, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butyl malonate and 4-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy)-1-(2-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy)ethyl)-2,2,6,6-tetramethylpiperidin; benzoate-based UV absorbers, such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; etc.

[0162] These UV absorbers can be used alone or in combination of two or more. In the final resin composition, the amount of UV absorber used is typically about 10 ppm or more by weight, or about 100 ppm or more by weight, based on the weight of the ionomer resin. Furthermore, the amount of UV 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.

[0163] In some implementations, two or more types of UV absorbers may be used in combination.

[0164] In other implementations, no UV absorber is added, or the laminate contains virtually no UV absorber additives.

[0165] Examples of light stabilizers include hindered amine-based substances, such as “ADEKA STAB LA-57” (trade name) manufactured by Adeka and “TINUVIN 622” (trade name) manufactured by Ciba Specialty Chemicals Inc.

[0166] When laminated glass is prepared by incorporating heat-insulating fine particles or heat-insulating compounds as heat-insulating materials into the interlayer of the present invention to impart heat-insulating function to the laminate, the transmittance at a wavelength of 1,500 nm can be adjusted to about 50% or less, or the TDS value (calculated according to ISO 13837:2008) can be adjusted to less than about 43%.

[0167] Examples of heat-insulating fine particles include metal-doped indium oxide, such as tin-doped indium oxide (ITO); metal-doped tin oxide, such as antimony-doped tin oxide (ATO); metal-doped zinc oxide, such as aluminum-doped zinc oxide (AZO); and those derived from the general formula M m WO n Metal element composite tungsten oxides (where M represents a metallic element; m is about 0.01 or greater and about 1.0 or less; and n is about 2.2 or greater and about 3.0 or less) are preferred, as are zinc antimonate (ZnSb₂O₅); lanthanum hexaboride, etc. Among these, ITO, ATO, and metal element composite tungsten oxides are preferred, and metal element composite tungsten oxides are more preferred. Examples of metallic elements represented by M in metal element composite tungsten oxides include Cs, Tl, Rb, Na, K, etc., and Cs is particularly preferred. From the perspective of thermal insulation properties, m is preferably about 0.2 or greater or about 0.3 or greater, and preferably about 0.5 or less or about 0.4 or less.

[0168] From the perspective of the transparency of the final laminate, the average particle size of the thermal insulation fine particles is preferably about 100 nm or less, or about 50 nm or less. It should be noted that the average particle size of the thermal insulation particles referred to herein means the particle size measured by a laser diffraction instrument.

[0169] In the final resin composition, the content of the heat-insulating fine particles relative to the weight of the ionomer resin 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. Furthermore, the content of the heat-insulating fine particles is preferably about 5% by weight or less, or about 3% by weight or less.

[0170] Examples of heat-insulating compounds include phthalocyanine compounds and naphthalenephthalocyanine compounds. From the perspective of further improving heat-insulating properties, it is preferable that the heat-insulating compound contains a metal. Examples of metals include Na, K, Li, Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Sn, V, Ca, Al, etc., with Ni being particularly preferred.

[0171] Based on the weight of the ionomer resin, the content of the 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. Furthermore, the content of the insulating compound is preferably about 1% by weight or less, or about 0.5% by weight or less.

[0172] Preparation of resin composition

[0173] The resin composition of the present invention can be prepared as a melt blend by feeding the various components into an extruder and mixing the components closely under molten conditions of an ionomer resin to produce a substantially homogeneous mixture, which can be ultimately shaped into a final shape, for example by melt extrusion or molding.

[0174] As is generally acknowledged by those skilled in the art, in melt blending, care must be taken to ensure sufficiently vigorous mixing to achieve adequate homogeneity of the silane within the monomer resin. This high degree of mixing is typically achieved through extrusion blending by creating sufficient shear and residence time in the extruder. Care must also be taken to avoid adverse reactions, localized high concentrations of silane during blending, and decomposition of the silane and polymer resin due to high temperatures. The formation of discolored resin, gels, or degradation products (e.g., black spots) can be avoided by selecting appropriate process equipment and optimizing process conditions.

[0175] For example, it is well known that the degree of hydrolysis of silanes increases with prolonged and excessive exposure to moisture, which may necessitate further consideration of controlling exposure to external moisture. Covering with dry air or nitrogen may be necessary, for instance, to maintain the required minimum level of silane hydrolysis.

[0176] In one embodiment of the invention, the resin composition is prepared by providing a masterbatch of a first ionomer resin having a high concentration of silane, and then diluting the masterbatch by adding it to the same ionomer resin and / or a second ionomer resin to obtain a composition with the desired final concentration of silane.

[0177] In one embodiment of the masterbatch composition according to the invention, it is a particulate masterbatch composition comprising a silane additive absorbed on the particle surface of an ionomer resin, wherein, based on 100 parts by weight of the ionomer resin, a dialkoxysilane compound is present in the masterbatch composition in an amount ranging from about 1 or about 2.5 or about 5 to about 10 or about 8 parts by weight.

[0178] Preferably, the silane is liquid, and this masterbatch composition can be prepared by physically mixing ionomer resin particles and liquid silane under non-softening conditions for the ionomer resin; in other words, the ionomer resin does not melt or soften to the point of significant agglomeration or otherwise lose its original particulate form. In this case, the silane is absorbed onto the particle surface with minimal reaction or decomposition.

[0179] The ionomer resin particles of suitable size used to prepare the masterbatch composition are substantially in the size range of about 0.1 mm or about 0.2 mm to about 5 mm or about 4 mm or about 2 mm or about 1 mm. These particles can be measured using an optical microscope equipped with a stage micrometer. Particles up to 1 mm in size can be measured using a 1 mm stage micrometer with a 0.01 mm division. Particles larger than 1 mm can be measured using a 25 mm stage micrometer with a 0.05 mm division. In the case of particles with a diameter or in the case of rectangular or irregular shapes, the maximum size of 20 randomly selected particles from the resin can be measured, and the average of the 20 particles can be used to characterize the overall particle size.

[0180] In one implementation, the particles used to prepare the masterbatch are reduced from a nominal particle size, for example, by cryogenic milling. For instance, cryogenic milling can be used to reduce ionomer resin particles from a nominal average particle size of about 4 mm in diameter to a generally average particle size in the range of about 0.1 mm to about 0.5 mm. Reducing the particle size in this way increases the particle surface area relative to particle weight. Additionally, these particles break down during the milling process and become irregularly shaped, which further increases the surface area relative to particle weight compared to the nominally spherical shape of ionomer resin particles. Cryogenic milling methods are generally well known to those skilled in the art and typically involve freezing the granules with liquid nitrogen prior to the milling / grinding process. Once cooled, the granules are then processed by a mechanical mill. Freezing the granules with liquid nitrogen allows for more efficient size reduction without undo heating and polymer degradation.

[0181] These ionomer resin particles can also be prepared by other conventional methods, such as by underwater melt cutting (e.g., "microparticles" with an average diameter of about 0.5 to about 1.5 mm) or other methods well known to those skilled in the art.

[0182] Alternatively, a particulate resin composition can be prepared directly by mixing the above-mentioned particulate ionomer resin and silane additive (which absorbs the silane additive on the surface of the resin particles), but mixing in amounts that yield the final concentration of the components.

[0183] Based on the weight of the ionomer resin, the silane additive is present in the final resin composition in an amount of about 50 or about 100 or about 250 or about 500 or about 750 parts by weight to about 5000 or about 4000 or about 2000 or about 1500 or about 1250 parts by weight.

[0184] If other additives are present, they can be mixed as part of the masterbatch, or added to the final resin composition using conventional methods recognized by those skilled in the art.

[0185] Plate / Mezzanine

[0186] Sheets of the resin compositions of the present invention can be prepared by conventional melt extrusion or melt molding methods suitable for preparing interlayers for glass laminates. Such methods are well known to those skilled in the art, as illustrated in previously incorporated disclosures.

[0187] The sheet can be a single-layer or multi-layer sheet. For example, a multi-layer sheet can be formed having a functional core layer sandwiched between two outer layers and other optional inner layers. In one embodiment, at least one (or both) of the outer layers of the multi-layer sandwich is a sheet of the resin composition according to the invention.

[0188] As examples of functional core layers, acoustic damping layers that can be mentioned include polystyrene copolymer interlayers (see JP2007-91491A), polyvinyl acetal layers (see US2013 / 0183507A1, US8741439B2, JP2012-214305A and US8883317B2), viscoelastic acrylic layers (see US7121380B2), layers containing copolymers of styrene and rubber-based resin monomers (see JP2009-256128A), layers containing polyolefins (see US2012 / 0204940A1), layers containing ethylene / vinyl acetate polymers (see WO2015 / 013242A1), and layers containing ethylene-vinyl acetate copolymers (see WO2015 / 085165A1).

[0189] In one specific embodiment, the intermediate layer is a thermoplastic elastomer resin, such as the thermoplastic elastomer resins disclosed in WO2016 / 076336A1, WO2016 / 076337A1, WO2016 / 076338A1, WO2016 / 076339A1, WO2016 / 076340A1, and US2017 / 0320297A1. In a more specific embodiment, the thermoplastic elastomer resin is a hydrogenated product of a block copolymer having the following:

[0190] (i) an aromatic vinyl polymer block (a), based on said aromatic vinyl polymer block, containing about 60 mol% or more of aromatic vinyl monomer units, and

[0191] (ii) an aliphatic unsaturated polymer block (b), based on said aliphatic unsaturated polymer block, which contains about 60 mol% or more of conjugated diene monomer units.

[0192] The aliphatic unsaturated polymer block (b) contains a total of approximately 50 mol% or more isoprene and butadiene units as conjugated diene monomer units, and

[0193] The amount of residual carbon-carbon double bonds in the aliphatic unsaturated polymer blocks derived from conjugated diene monomer units is approximately 2 to approximately 40 moles.

[0194] Furthermore, the interlayer as a whole can be symmetrical, having a substantially uniform thickness, or it can be asymmetrical, wherein one part of the interlayer is thicker than another (e.g., partially or completely “wedge-shaped,” as discussed in US2017 / 0320297A1 and US2018 / 0117883A1). Furthermore, the laminate can be substantially transparent, or wholly or partially colored (e.g., “shading bands,” as discussed in US2017 / 0320297A1 and US2018 / 0117883A1).

[0195] In a symmetrical configuration, the interlayer should have a total film thickness of approximately 320 μm or more, or approximately 420 μm or more. Furthermore, the total film thickness should be approximately 1250 μm or less, or approximately 1000 μm or less.

[0196] In asymmetric structures such as wedges, the thinner portion of the sandwich should have the thickness of a symmetrical structure, while the thickness of the thicker portion will depend on various parameters, such as the wedge angle. In one embodiment of a wedge-shaped sandwich, the thickness of the thicker edge is about 1850 μm or less, or about 1600 μm or less, or about 1520 μm or less, or about 1330 μm or less, or about 1140 μm or less; and the thickness of the thinner edge is about 600 μm or more, or about 700 μm or more, or about 760 μm or more.

[0197] Furthermore, an uneven structure, such as embossing, can be formed on the surface of the interlayer of the present invention using conventional and known methods to assist in degassing during the fabrication of the laminate. There are no particular limitations on the shape of the embossing; conventionally known shapes can be used.

[0198] In one embodiment, at least one surface (and preferably two surfaces) of the interlayer of the laminated glass is formed. By forming at least one surface of the interlayer of the laminated glass, air bubbles present at the interface between the interlayer and the glass in the case of preparing the laminated glass can easily escape to the outside of the laminated glass, thus improving the appearance of the laminated glass. It is preferred that at least one surface of the interlayer of the laminated glass is formed by an embossing roller method. By forming the surface of the interlayer of the laminated glass, concave portions and / or convex portions are formed on the surface of the interlayer of the laminated glass.

[0199] An embossing roller for the embossing roller method can be prepared, for example, by using an engraving machine (master mill) with the desired embossed pattern to transfer the pattern onto the surface of a metal roller. Furthermore, laser etching can also be used to prepare the embossing roller. Further, after forming a fine embossed pattern on the surface of the metal roller as described above, sandblasting the surface with the fine embossed pattern using an abrasive such as alumina, silicon dioxide, or glass beads can also form a finer embossed pattern.

[0200] Furthermore, it is preferable to perform a peeling treatment on the embossing roller used in the embossing roller method. When using an embossing roller that has not undergone peeling treatment, it becomes difficult to peel the interlayer used for laminated glass from the embossing roller. Examples of peeling treatment methods include known methods such as silicone treatment, Teflon (registered trademark) treatment, and plasma treatment.

[0201] 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 interlayer of laminated glass formed by embossing rollers or the like is typically about 5 μm or more, or about 10 μm or more, or about 20 μm or more. The height of the embossed portion is typically about 150 μm or less, or about 100 μm or less, or about 80 μm or less.

[0202] In this 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. Incidentally, the height of the embossed portion (i.e., the depth of the concave portion or the height of the convex portion) can vary within a range that does not depart from the spirit of this invention.

[0203] Examples of shapes formed by embossing rollers or similar methods include grids, oblique grids, oblique ellipses, ellipses, oblique grooves, and grooves. The angle of inclination of this form relative to the film flow direction (MD direction) is typically from about 10° to about 80°. Furthermore, the shaped pattern can be a regular pattern or an irregular pattern, such as a random matte pattern or a pattern such as that disclosed in US7351468B2.

[0204] The glass can be shaped on one surface of the laminate using methods such as embossing rollers, or on both surfaces, but more typically on both surfaces.

[0205] Laminated components

[0206] The laminates of the present invention can be prepared by conventional known methods. Examples include using a vacuum laminator, a vacuum bag, a vacuum ring, or clamping rollers. Furthermore, a method can be employed in which, after temporary contact bonding, the resulting laminate is placed in an autoclave for final bonding.

[0207] When using, for example, a vacuum laminator, known instruments for preparing solar cells can be used, and temperatures of about 100°C or higher, or about 130°C or higher, or about 200°C or lower, or about 170°C or lower, and about 1×10⁻⁶ ppm can be applied. -6 MPa or higher and approximately 3 × 10 -2 Laminated components are laminated under reduced pressure of MPa or lower. EP1235683A1 (CA2388107A1) describes, for example, a method using vacuum bags or vacuum rings, and, for example, at about 130°C or higher and about 145°C or lower and about 2 × 10⁻⁶ MPa. -2 Laminated components under pressure of MPa.

[0208] In the case of using, for example, pinch rollers, one exemplified method is that after a first temporary contact bond is performed at or below the flow initiation temperature of the surface resin, a further temporary contact bond is performed at conditions close to the flow initiation temperature. Specifically, for example, one exemplified method is that the component is heated at a temperature of about 30°C or higher and about 100°C or lower by means of an infrared heater, then degassed by rollers, and further heated at a temperature of about 50°C or higher and about 150°C or lower, followed by contact bond performance by rollers to achieve bonding or temporary bonding.

[0209] Although the autoclave method followed by temporary contact bonding can vary depending on the thickness or construction of the module, it is, for example, carried out at a pressure of about 1 MPa or higher and about 15 MPa or lower and 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.

[0210] The well-known "autoclave-free" method can be used as an alternative for processing laminates.

[0211] Advantageously, there are no particular restrictions on the glass used to prepare laminated glass. Inorganic glasses, such as float glass, polished glass, patterned glass, wire-insulated glass, and heat-absorbing glass, as well as conventionally known organic glasses, such as polymethyl methacrylate and polycarbonate, can be used. These glasses can be any type of glass, including colorless, colored, clear, or opaque glass. These glasses can be used alone or in combination of two or more of them.

[0212] The laminated glass of this invention is suitable for use in automotive windshields, automotive side windows, automotive sunroofs, automotive rear windows, or head-up display glass; as architectural components for windows, walls, roofs, skylights, soundproof walls, display windows, balconies, handrail walls, etc.; as partition glass components for conference rooms; as solar panels; and so on. Further information regarding these applications can be found in previously incorporated publications.

[0213] The invention can be further understood from the following specific embodiments of the properties of laminated glass. However, it should be understood that these embodiments should not be construed as limiting the scope of the invention in any way. Detailed Implementation

[0214] Example

[0215] The substances used in the examples are as follows.

[0216] The glass used in the examples is standard annealed soda-lime glass (obtained from Guardian Industries, Inc., Galax VA, USA).

[0217] Ionomer 1 (I1) – a partially neutralized ethylene glycol binary copolymer ionomer, obtained from EIdu Pont deNemours & Co. (Wilmington, DE, USA) (21.7% methacrylic acid, 26% Na neutralized, MI = 1.8 at 190°C).

[0218] Silane 1(S1)–γ-glycidoxypropyltrimethoxysilane ( A-187, purchased from Momentive Performance Materials, Inc., Waterford, NY, USA

[0219] Silane 2(S2)-3-glycidoxypropylmethyldiethoxysilane ( 2287, purchased from Momentive Performance Materials, Inc., Waterford, NY, USA.

[0220] Silane 3(S3)-N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane ( A-2120, available from Momentive Performance Materials, Inc., Waterford, NY USA).

[0221] Ionomer plate preparation

[0222] For embodiments containing silane, the following method is used:

[0223] Weigh 1200 g of ionomer resin (accurate to 0.1 g) into a clean polypropylene plastic container (2-gallon volume) with a wide-mouth metal screw cap. Under appropriate ventilation and following suitable laboratory safety procedures, aspirate a specific amount of liquid silane to produce the indicated concentration into the container. Then seal the container with the cap and manually shake thoroughly for 2 minutes to distribute the liquid over the ionomer resin particles. Shake the mixture again for one minute one hour after the initial blend preparation begins, and again for one minute before feeding the aspirated resin into the feeder hopper. Perform the above operations under ambient temperature and humidity conditions (nominal 23°C and 50% RH, but not in a controlled humidity environment). Feed the silane / resin blend into the extruder using a calibrated screw feeder within approximately 4 hours of preparation, as described in the ionomer sheet preparation method below.

[0224] Silane 1 (S1) was used to absorb the resin particles from Examples CE-8 to CE-11. Silane 2 (S2) was used to absorb the resin particles from Examples 1 to 13. Silane 3 (S3) was used to absorb the resin particles from Examples 14 to 17.

[0225] Using a K-Tron feeder (Coperion GmbH) equipped with a calibrated tail-type auger, the ionomer resin and silane additive (if present) are fed into an 18-mm diameter Liestritz twin-screw compounding extruder (screw speed set to 200 rpm) at a temperature distribution provided in Table I below at approximately 5 to 7 psi and extruded into polymer strands (two 6-mm dies).

[0226]

[0227]

[0228] The polymer throughput is controlled by adjusting the screw speed to provide a given throughput or residence time and the resulting shear conditions. In both extruder cases, the melt strand is drawn through a wet batch containing demineralized water at ambient temperature, excess water is blown off with compressed air, and the strand is fed into a rotary cutter (Conair) to obtain chopped strand pellets. These pellets are then dried overnight in a vacuum oven at 50°C under a purge of slightly dry nitrogen. The pellets are then compressed and molded into sheets with a nominal thickness of 0.76 mm and dimensions of 150 mm by 200 mm. These sheets are then held in a dry atmosphere, or exposed to different humidity conditions as needed, and then laminated as described below.

[0229] Method for preparing laminated parts

[0230] Glass laminates were prepared from the ionomer sheets using the following method. Annealed glass sheets (100x100x3 mm) were washed for 5 minutes at 50°C with a deionized aqueous solution of trisodium phosphate (5 g / L), then thoroughly rinsed with deionized water and dried. The three corresponding ionomer sheets (each approximately 0.76 mm thick) listed in Table 1 were stacked together and placed between two glass sheets (creating a 2.28 mm interlayer thickness).

[0231] The ionomer sheets were kept at a humidity level of 0.08% by weight or less by minimizing the contact time with the indoor environment (approximately 35% RH), or exposed for 10 days at the temperature and humidity levels shown in the following examples (samples were placed in an Espec humidity chamber type LHU-113).

[0232] The humidity level of the ionomer plates was measured using the Coulomb-Karl Fischer method (Metrohm 800 model), and the temperature of the sample vial heating chamber was 150°C. The ionomer plates were cut into small pieces and placed in the sample vials, with a total weight of 0.40 grams.

[0233] The pre-laminated assembly is then glued together at several points using polyester tape to maintain the relative positioning of each layer to the glass sheet. Nylon fabric tape is placed around the perimeter of the assembly to facilitate the removal of air from within the layers. The assembly is placed in a nylon vacuum bag, sealed, and then connected to a vacuum pump. A vacuum is applied to substantially remove air from the inside (the air pressure inside the bag drops to below 50 mbar absolute). The bagged assembly is then heated to 120°C in a convection air oven and held for 30 minutes. The assembly is then cooled to near room temperature using a cooling fan, disconnected from the vacuum source, and the bag is removed, yielding a fully pre-pressed assembly of glass and interlayer.

[0234] The components are then placed in an air autoclave, and the temperature and pressure are raised from ambient conditions to 135°C and 13.8 bar over 15 minutes. This temperature and pressure are maintained for 30 minutes, and then the temperature is reduced to 40°C at a cooling rate of approximately 2.5°C / min, thereby allowing the pressure to drop back to ambient pressure (over 15 minutes), and the final laminate is removed from the autoclave.

[0235] Haze measurement

[0236] The laminates were thoroughly cleaned and inspected using WINDEX glass cleaner (SC Johnson & Son, Inc.) and a lint-free cloth to ensure they were free of air bubbles and other defects that could otherwise hinder effective optical measurements. The laminates were then evaluated using a Haze-gard Plus haze meter (Byk-Gardner) to obtain a haze percentage measurement. Haze measurements were performed in accordance with the specifications outlined in the American National Standard (ANSI Z26.1-1966), “Safety Code for Safety Glazing Materials for Glazing Motor Vehicles Operating on Land Highways.” Sections 5.17 and 5.18 of this standard, along with Figures 5 and 6, detail the appropriate methods and instrument setup for measuring the haze levels of glass materials. The Haze-gard Plus haze meter met the appropriate requirements of this standard for all measurements to be performed. The haze standard, traceable to the National Bureau of Standards (now NIST), ensured proper instrument calibration and operation.

[0237] The haze results are shown in Table II below:

[0238]

[0239] The results show that the addition of silane did not substantially adversely affect the haze of the resulting laminate.

[0240] Peel adhesion force measurement

[0241] To measure peel adhesion, some samples were prepared as described above, except for the following differences.

[0242] The annealed glass was scribe and cut into 100mm x 200mm rectangles, then washed according to the previously described procedure. A thin polyester tape (25µm thick x 25mm wide) with silicone adhesive was applied in two parallel strips to the glass surface on the "side of interest" (open or tin side), providing a uniform 25mm wide bond area between the two parallel strips. This procedure allows for the creation of a very well-defined bond area without cutting through the polymer layer to create a release strip, as is conventionally done in standard peel adhesion methods. On top of the laminated sample, a 4-mil thin FEP film sheet was placed on top of the plastic sheet, followed by the second glass sheet, providing a relatively flat surface for the lamination step and acting as a release layer for removing the top glass. All lamination steps were then performed as described above. Subsequently, the 90-degree peel adhesion force of each sample prepared by the above method was measured using a mechanical testing device (INSTRON 1122, Instron Industrial Products, Norwood, MA USA). Peeling was performed at a crosshead speed of 1 cm / min under standard laboratory conditions (nominal 23°C and 50% RH). After peeling approximately 100 mm of sample, demineralized water was applied to the glass and peel interface, ensuring the interface was now fully immersed in liquid water. The peeling rate was then reduced to 0.25 mm / min, and testing continued for several hours until approximately another 100 mm of sample was tested. Sufficient water was provided to ensure the sample remained 'wet' during this final testing period. Data were collected using computer software (INSTRON Bluehill III software, Instron Industrial Products, Norwood, MA USA), and the average force levels for the '50% RH' and 'wet' peel test sections were calculated.

[0243] The results are presented in Table III below.

[0244]

[0245]

Claims

1. A resin composition comprising (i) an ionomer resin and (ii) an adhesion promoter additive, characterized in that: (a) The ionomer resin is a sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer, wherein the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer comprises constituent units derived from ethylene and constituent units derived from α,β-unsaturated carboxylic acids, wherein at least a portion of the constituent units derived from the α,β-unsaturated carboxylic acids are neutralized by counterions, and wherein the counterions are composed of sodium cations. (b) The adhesion promoter additive is a dialkoxysilane compound; and (c) Based on the weight of the ionomer resin, the dialkoxysilane compound is present in the resin composition in an amount ranging from 500 to 3000 parts per million by weight; in: The α,β-unsaturated carboxylic acid content in the ionomer resin is from 2% to 30% by mass. The degree of neutralization of the α,β-unsaturated carboxylic acid in the ionomer resin is 10% to 60%, and The dialkoxysilane compound is 3-glycidoxypropylmethyldiethoxysilane.

2. The resin composition of claim 1, wherein the dialkoxysilane compound is uniformly distributed within the resin composition.

3. The resin composition of claim 1, wherein the resin composition is a particulate resin composition, wherein the ionomer resin is a particulate ionomer resin, and the dialkoxysilane compound is present in the resin composition in such a manner as to be absorbed on the surface of the ionomer resin particles.

4. The resin composition of claim 1, wherein the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is a binary copolymer composed of the following copolymer units: (i) Ethylene, and (ii) 10% to 30% by weight of at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms. The weight percentage of the copolymer units is based on the total weight of the ethylene copolymer, and the sum of the weight percentages of the copolymer units is 100% by weight.

5. The resin composition of claim 1, wherein the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is a terpolymer composed of the following copolymer units: (i) Ethylene, (ii) 10% to 30% by weight of at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms. (iii) 2% to 15% by weight of at least one α,β-unsaturated carboxylic acid ester having 3 to 10 carbon atoms, and (iv) Any derivative of an α,β-unsaturated carboxylic acid other than (iii), in an amount such that (iii) + (iv) is 15% by weight or less. The weight percentage of the copolymer units is based on the total weight of the ethylene copolymer, and the sum of the weight percentages of the copolymer units is 100% by weight.

6. The resin composition of claim 1, wherein the dialkoxysilane compound is present in the resin composition in an amount ranging from 500 to 1000 parts by weight, based on the weight of the ionomer resin.

7. The resin composition of claim 6, wherein the dialkoxysilane compound is present in the resin composition in an amount ranging from 600 to 1000 parts by weight, based on the weight of the ionomer resin.

8. A granular masterbatch composition comprising (i) granules of ionomer resin and (ii) an adhesion promoter additive, characterized in that: (a) The ionomer resin of the ionomer resin particles is a sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer; (b) The adhesion promoter additive is a dialkoxysilane compound; (c) Based on 100 parts by weight of the ionomer resin, the dialkoxysilane compound is present in the masterbatch composition in an amount ranging from 1 to 10 parts by weight; and (d) Greater than 50% of the diekoxysilane compound is present in the masterbatch composition by means of absorption on the surface of the ionomer resin particles, wherein the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is a binary copolymer composed of the following copolymer units: (i) Ethylene, and (ii) 10% to 30% by weight of at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms. The weight percentage of the copolymer units is based on the total weight of the ethylene copolymer, and the sum of the weight percentages of the copolymer units is 100% by weight.

9. The masterbatch composition of claim 8, wherein the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is a terpolymer composed of the following copolymer units: (i) Ethylene, (ii) 10% to 30% by weight of at least one α,β-unsaturated carboxylic acid having 3 to 10 carbon atoms. (iii) 2% to 15% by weight of at least one α,β-unsaturated carboxylic acid ester having 3 to 10 carbon atoms, and (iv) Any derivative of an α,β-unsaturated carboxylic acid other than (iii), in an amount such that (iii) + (iv) is 15% by weight or less. The weight percentage of the copolymer units is based on the total weight of the ethylene copolymer, and the sum of the weight percentages of the copolymer units is 100% by weight.

10. A method for preparing a resin composition, the method comprising the following steps: (A) Provides the masterbatch composition as claimed in claim 8; and (B) The masterbatch composition is mixed with a certain amount of sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer to obtain a close mixture with a concentration of 50 to 5000 parts by weight of the diekoxysilane compound based on the total weight of the ionomer resin.

11. A sandwich panel comprising: A layer comprising the resin composition according to claim 1, wherein when the sandwich panel is pretreated at 34°C and 50% relative humidity, and the layer of the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is adhered to the air-facing side of a float glass sheet having an air-facing side and a tin side, the peel adhesion of the layer of the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer adhered to the air-facing side of the float glass sheet is at least 20 N / cm, as measured at 23°C and 50% RH.

12. A sandwich panel comprising: A layer comprising the resin composition according to claim 1, wherein when the sandwich panel is pretreated at 34°C and 50% relative humidity, and the layer of the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is adhered to the air-facing side of a float glass sheet having an air-facing side and a tin side, the peel adhesion force of the layer of the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer adhered to the air-facing side of the float glass sheet is at least 0.5 N / cm under wet conditions.

13. A sandwich panel comprising: A layer comprising the resin composition according to claim 1, wherein when the sandwich panel is pretreated at 34°C and 50% relative humidity, and the layer of the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer is adhered to a float glass sheet having an air-facing side and a tin-facing side, the peel adhesion force of the layer of the sodium-neutralized ethylene-α,β-unsaturated carboxylic acid copolymer when adhered to the air-facing side of the float glass sheet is (i) greater than 5 N / cm, measured at 23°C and 50% RH, and (ii) greater than the peel adhesion force when adhered to the tin-facing side of the float glass sheet, measured at 23°C and 50% RH.

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