Poly(vinyl butyral) composition for use with solar additives

Abstract

A specific poly(vinyl acetal) composition is provided that is useful in safety glass construction. The composition of the present invention can be extruded into a sheet and function as an interlayer between glass panels. In particular, the composition includes one or more solar additives and a divalent magnesium ion and at least two carboxylate groups, the corresponding carboxylic acids of which each have a pKa of less than about 4.80. Each magnesium salt used as an adhesion control agent may be a hydrate.

Description

[Technical Field]

[0001]

[0001] The present invention relates to controlling the adhesion of a polyvinyl butyral (PVB) sheet to glass in a laminated safety glass structure. [Background technology]

[0002]

[0002] Poly(vinyl butyral) (PVB) is commonly used in the manufacture of polymer sheets that can be used as interlayers in light-transmitting laminates such as safety glass or polymer laminates. Safety glass typically refers to a transparent laminate that includes a poly(vinyl butyral) sheet placed between two panes of glass. Safety glass is often used to provide a transparent barrier in openings in buildings and automobiles. Its main function is to absorb energy such as that caused by impact from an object without penetrating the opening. Additives to the sheet formulation generally include at least one adhesion control agent (hereinafter, "ACA") that modifies the adhesion of the sheet to the glass so that it can maintain a suitable level of adhesion to prevent glass shattering while providing adequate energy absorption in the event of impact.

[0003]

[0003] Safety glass can be formed by a process of pre-pressing two layers of glass and a plastic interlayer such as poly(vinyl butyral), temporarily attaching them to a pre-laminate, and finishing it into an optically transparent laminate. The assembly step may include laying one sheet of glass, placing a poly(vinyl butyral) sheet on top of the glass, laying a second sheet of glass on top of the poly(vinyl butyral) sheet, and then trimming off the excess poly(vinyl butyral) to match the edges of the glass layers.

[0004]

[0004] Plastic interlayers may be manufactured by mixing a poly(vinyl butyral) polymer with one or more plasticizers and optionally one or more other components, and melt-processing the mixture into a sheet, which is typically collected and rolled up for storage and transport.

[0005]

[0005] The process of producing poly(vinyl butyral) resin may involve the use of an acid to catalyze the formation of vinyl acetal from vinyl alcohol and aldehyde precursors. After the formation of poly(vinyl acetal), the acid may be neutralized with a suitable base. In this process, residual acetate typically remains trapped within the poly(vinyl butyral) resin, which can affect both stabilization and adhesion quality. However, the residual concentration of acetate can be a limiting factor if certain adhesion and other properties are desired in the finished poly(vinyl butyral).

[0006]

[0006] Furthermore, adhesion control agents in the sheet formulation control the adhesion of the sheet to the glass in order to provide energy absorption against impact to the glass laminate. In fact, this "control" is equivalent to reducing adhesion, and therefore, if the adhesion control agent binds to the PVB or becomes static through reaction, the adhesion of the PVB to the glass increases to an undesirable level. In particular, when some adhesion control agents, such as magnesium 2-ethylbutyrate, are used in combination with various solar additives, a phenomenon called "binding" typically occurs, where the salt reacts with the PVB and binds during the melting process (e.g., extrusion) of the PVB formulation into a sheet. The bound salt is then unavailable for adhesion control, and the sheet adheres very strongly to the glass of the finished laminate, leading to a decrease in impact strength. Moreover, generally, the level of bound salt increases proportionally as the initial level of ACA, or solar absorber, in the formulation increases. Therefore, improved compositions and methods are needed to enhance the properties of poly(vinyl butyral) sheets, especially those including solar additives. [Overview of the project] [Means for solving the problem]

[0007]

[0007] Poly(vinyl butyral) compositions used in safety glass structures often contain solar additives and other heat shielding particles in the form of metal oxide nanoparticles such as indium tin oxide, antimony tin oxide, cesium-doped tungsten oxide, and other doped tungsten oxides. Such nanoparticles are less than 200 nm (D 50 ) and in other embodiments, less than 100 nm (D 50 ) In this regard, such nanoparticles generally have a diameter of less than about 200 nm or, in some embodiments, less than about 100 nm (D 50 ) and D 50This is understood to be the median diameter by volume measured by dynamic light scattering and is considered to be the average particle size by volume. When these solar additives are used in combination with certain adhesion control additives, such as polyvalent metal salts of organic monocarboxylic acids (see U.S. Patent No. 5,728,472), such as magnesium 2-ethylbutyrate or magnesium 1-ethylhexanoate, a phenomenon called "bonding" occurs, in which the adhesion control agent bonds to the poly(vinyl butyral) resin, and therefore its effectiveness as an adhesion control agent is reduced. The present invention provides a specific poly(vinyl butyral) composition having at least one solar additive, wherein the poly(vinyl butyral) composition utilizes a magnesium salt, such as magnesium salicylate or magnesium formate, or a hydrate thereof, as an adhesion control agent (ACA), wherein the magnesium salt comprises a divalent magnesium ion and at least two carboxylate groups, and the corresponding carboxylic acids of the carboxylate groups each have a pKa of less than about 4.80. In this specification, when magnesium salicylate or magnesium formate is referred to, the respective hydrates (magnesium salicylate tetrahydrate and magnesium formate dihydrate) are also included. These compositions have been found to have significantly improved performance compared to existing poly(vinyl butyral) compositions containing solar additives. As provided by the present invention, the poly(vinyl butyral) sheets of the present invention exhibit improved stability in these metal oxide nanoparticle-containing environments (e.g., indium tin oxide) where the polymer sheet is exposed to high temperatures and moisture content during extrusion, and do not unacceptably alter the adhesive quality of the polymer sheet due to significant degradation of magnesium ACA salts (i.e., magnesium 2-ethylbutyrate or magnesium 2-ethylhexanoate) during extrusion. Adhesion can be tuned and controlled using combinations of different levels of magnesium ACA salt values ​​and alkali metal ACA salt values, as shown in both the peel test method and the pummel test method.Therefore, the present invention enables the extrusion of poly(vinyl butyral) with solar metal oxide nanoparticles in the extruder formulation without the need to limit residual moisture in the poly(vinyl butyral) resin and water from other additives. Post-extrusion heat treatment of the extruded sheet, including the re-moisturizing and lamination process of the PVB sheet, is also protected.

[0008]

[0008] In one embodiment, the polymer interlayer for glazing comprises poly(vinyl butyral), at least one plasticizer, a solar additive, sodium acetate and / or potassium acetate, and a magnesium salt comprising a divalent magnesium ion and at least two carboxylate groups, the corresponding carboxylic acids of the carboxylate groups each having a pKa of less than about 4.80 (4.70, 4.60, 4.50, 4.40, 4.30, 4.20, 4.10, 4.00).

[0009]

[0009] In the embodiment, the polymer interlayer comprises a divalent magnesium ion and at least two magnesium salts comprising at least two carboxylate groups, wherein the corresponding carboxylic acids of the carboxylate groups each have a pKa of less than about 4.80 (4.70, 4.60, 4.50, 4.40, 4.30, 4.20, 4.10, 4.00).

[0010]

[0010] In the embodiment, the magnesium salt is magnesium salicylate, magnesium formate, magnesium salicylate tetrahydrate, or magnesium formate dihydrate.

[0011]

[0011] In the embodiment, the level of bonding (bonding %) is less than 25% (24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11 or less than 10%).

[0012]

[0012] In one embodiment, the plasticizer comprises a plasticizer having a refractive index of at least 1.460 as measured by ASTM D542 at a wavelength of 589 nm and a temperature of 25°C. In another embodiment, the plasticizer comprises a blend of plasticizers. In one embodiment, the plasticizer comprises a blend of conventional plasticizers (having a refractive index of less than 1.460 as measured by ASTM D542 at a wavelength of 589 nm and a temperature of 25°C) and plasticizers having a refractive index of at least 1.460 as measured by ASTM D542 at a wavelength of 589 nm and a temperature of 25°C.

[0013]

[0013] In the embodiments, the interlayer sheet comprises the composition described above, and this composition is formed into the interlayer sheet. In the embodiments, the interlayer sheet further comprises one or more additional layers to form a multilayer sheet, and in some embodiments, the interlayer sheet comprises three layers.

[0014]

[0014] In some embodiments, the laminated safety glass comprises two sheets of glass and the aforementioned interlayer sheet, the interlayer sheet being positioned between the two sheets of glass. In some embodiments of the laminated safety glass, at least one of the two sheets of glass further comprises a metal coating. In other embodiments, the laminated safety glass further comprises a thermoplastic film adjacent to the interlayer sheet, the thermoplastic film comprising polyester in some embodiments. [Modes for carrying out the invention]

[0015]

[0015] In a first aspect, the present invention relates to a polymer composition, a. Poly(vinyl acetal) and, b. Solar additives and c. Sodium acetate and / or potassium acetate, d. At least one type of plasticizer, e. A magnesium salt containing divalent magnesium ions and at least two carboxylate groups, wherein the corresponding carboxylic acids of the carboxylate groups each have a pKa of less than about 4.80 (4.70, 4.60, 4.50, 4.40, 4.30, 4.20, 4.10, 4.00), and the titer of the magnesium salt or its hydrate is from about 10 to about 60, and the magnesium salt and having an alkali value resulting from a combination of potassium acetate and sodium acetate from about 10 to about 60, and a ratio of the titer of the magnesium salt or its hydrate to the alkali value resulting from the combination of potassium acetate and sodium acetate of from about 0.5 to about 2.0, provides a polymer composition.

[0016]

[0016] In a second aspect, the present invention is a polymer composition comprising a. a poly(vinyl acetal) in which the resin has a moisture level of less than about 1% by weight, b. a solar additive, c. sodium acetate and / or potassium acetate, d. at least one plasticizer, e. a magnesium salt containing divalent magnesium ions and at least two carboxylate groups, wherein the corresponding carboxylic acids of the carboxylate groups each have a pKa of less than about 4.80 (4.70, 4.60, 4.50, 4.40, 4.30, 4.20, 4.10, 4.00), and the titer of the magnesium salt or its hydrate is from about 10 to about 60, and the magnesium salt and having an alkali value resulting from a combination of potassium acetate and sodium acetate from about 10 to about 60, and a ratio of the titer of the magnesium salt or its hydrate to the alkali value resulting from the combination of potassium acetate and sodium acetate of from about 0.5 to about 2.0, provides a polymer composition.

[0017]

[0017] The poly(vinyl acetal) resin referred to in component a) above can be formed by acetalizing poly(vinyl alcohol) with one or more aldehydes in the presence of an acid catalyst. The resulting resin can then be separated, stabilized, and dried according to known methods, such as those described in U.S. Patent Nos. 2,282,057 and 2,282,026, and in Wade, B. (2016), “Vinyl Acetal Polymers,” Encyclopedia of Polymer Science and Technology, pp. 1-22 (John Wiley & Sons, Inc.). The total amount of residual aldehyde groups or residues present in the resulting poly(vinyl acetal) resin may be at least about 50 weight percent, at least about 60 weight percent, at least about 70 weight percent, at least about 75 weight percent, at least about 80 weight percent, or at least about 85 weight percent, as measured by ASTM D-1396. The total amount of aldehyde residues in poly(vinyl acetal) resin can be collectively referred to as the acetal component, and the remainder of the poly(vinyl acetal) resin contains residual hydroxyl groups and residual acetate groups, which will be explained in more detail below.

[0018]

[0018] In some embodiments, the vinyl acetal component of the poly(vinyl n-butyral) resin may mainly consist of vinyl butyral derived from n-butyraldehyde, for example, it may contain at least about 70% by weight, at least about 80% by weight, or at least about 90% by weight of vinyl butyral derived from n-butyraldehyde.

[0019]

[0019] One or more poly(vinyl acetal) resins may also comprise one or more vinyl acetals derived from one or more aldehydes other than n-butyraldehyde. For example, in some embodiments, at least one poly(vinyl acetal) resin in a composition, layer, or interlayer may be derived from at least one other C2-C8 aldehyde, including, for example, acetaldehyde, propionaldehyde, isobutyraldehyde, 2-methylbarrelaldehyde, n-hexylaldehyde, 2-ethylhexylaldehyde, n-octylaldehyde, and combinations thereof. In some embodiments, at least one poly(vinyl acetal) resin may be derived from one or more C4-C8 aldehydes selected from the group consisting of isobutyraldehyde, 2-ethylhexylaldehyde, and combinations thereof. In various embodiments, at least one poly(vinyl acetal) resin may contain zero weight percent of one or more aldehydes other than n-butyraldehyde, or may contain at least about 1 weight percent, at least about 5 weight percent, at least about 10 weight percent, at least about 20 weight percent, at least about 30 weight percent, at least about 40 weight percent and / or about 80 weight percent or less, about 70 weight percent or less, about 60 weight percent or less, about 50 weight percent or less, about 40 weight percent or less, or about 0 to about 40 weight percent, about 0 to about 30 weight percent, about 0 to about 20 weight percent, about 1 to about 80 weight percent, about 5 to about 70 weight percent, or about 10 to about 60 weight percent.

[0020]

[0020] Poly(vinyl butyral) can be produced by a known acetalization process that involves reacting poly(vinyl alcohol) with butyraldehyde in the presence of an acid catalyst, followed by neutralization, separation, washing, and drying of the resin. Some separation and washing may be performed before neutralization, for example in an aqueous process after acetalization, in order to reduce the amount of acid to be neutralized.

[0021]

[0021] The two methods employed are a solvent process and an aqueous process (see, for example, Wade, B (2016), “Vinyl Acetal Polymers,” Encyclopedia of Polymer Science and Technology, pp. 1-22 (John Wiley & Sons, Inc.)). In either method, poly(vinyl alcohol) is reacted with an aldehyde in the presence of a mineral acid catalyst or an organic acid catalyst to produce poly(vinyl acetal) and water. When butyraldehyde is used as the aldehyde, the resulting acetal is poly(vinyl butyral).

[0022]

[0022] In the embodiment, the poly(vinyl acetal) resin has a moisture content of less than about 1% by weight.

[0023]

[0023] Any suitable strong acid (or mineral acid) may be used, generally including acetic acid which can be produced in situ during the hydrolysis of polyvinyl acetate. In certain embodiments, sulfuric acid is used as the primary acid catalyst.

[0024]

[0024] After acetal formation in any of the above methods, neutralization of residual acid can be achieved, for example, by adding a hydroxide compound, in the case of potassium hydroxide, which yields potassium acetate, which functions as an adhesion control agent. As disclosed in U.S. Patents 5,728,472 and 3,271,235, for example, either sodium hydroxide or potassium hydroxide can be used to neutralize the acid. Using either of these hydroxides may result in a residual titer of the corresponding acetate in the polymer matrix (see, for example, U.S. Patent 2,496,480). This residual titer is generally desirable because it prevents the decomposition of the finished polymer due to the harmful effects of residual sulfur oxides (for example, when sulfuric acid is used as a primary acid catalyst).

[0025]

[0025] This adhesion or level of adhesion of the finished polymer sheet is further improved in the present invention by the use of an adhesion control agent, a divalent magnesium ion and at least two carboxylate groups, the corresponding carboxylic acids of the carboxylate groups each having a pKa of less than about 4.80, and the adhesion control agent is, for example, magnesium salicylate or magnesium formate or their corresponding hydrates.

[0026]

[0026] In various embodiments, the polymer containing poly(vinyl butyral) contains about 9 to about 35 weight percent (wt%) of hydroxyl groups calculated as PVOH, 13 to 30 weight percent of hydroxyl groups calculated as PVOH, or 15 to 22 weight percent of hydroxyl groups calculated as PVOH. The polymer sheet may also contain less than 15 weight percent of residual ester groups calculated as polyvinyl acetate, 13 weight percent, 11 weight percent, 9 weight percent, 7 weight percent, 5 weight percent, or less than 3 weight percent of residual ester groups, the remainder being acetal, e.g., butyraldehyde acetal, but optionally small amounts of other acetal groups, e.g., 2-ethylhexanal group (see, for example, U.S. Patent No. 5,137,954) or vinyl ethanal derived from acetaldehyde.

[0027]

[0027] In various embodiments, the polymer comprises poly(vinyl butyral) having a molecular weight greater than 30,000, 40,000, 50,000, 55,000, 60,000, 65,000, 70,000, 120,000, 250,000, or 350,000 grams (g / mol or Daltons) per mole. It is also possible to increase the molecular weight to more than 350,000 g / m by adding a small amount of dialdehyde or trialdehyde during the acetalization process (see, for example, U.S. Patents 4,902,464, 4,874,814, 4,814,529, and 4,654,179). In this specification, the term “molecular weight” means weight-average molecular weight. Any preferred method can be used to produce the polymer sheets of the present invention.

[0028]

[0028] The solar additive can be selected from metal oxide nanoparticles such as antimony tin oxide, indium tin oxide, cesium-doped tungsten oxide, and other doped tungsten oxides. In this regard, such doped tungsten oxides can be represented by the general formula W y O z wherein W is tungsten, O is oxygen, 2.0 < z / y < 3.0, 2.2 ≤ z / y ≤ 2.99, or 2.45 ≤ z / y ≤ 2.99 is satisfied, and / or the particles of composite tungsten oxide can be represented by the general formula M x W y O z wherein M is an element selected from H, He, alkali metals, alkaline earth metals, rare earth metals, Mg, Zr, Cr, Mn, Fe, Rh, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, and combinations of two or more thereof, wherein W is tungsten, O is oxygen, 0.001 ≤ x / y ≤ 1.0 or 0.01 ≤ x / y ≤ 0.5, and 2.0 ≤ z / y ≤ 3.0, 2.2 ≤ z / y ≤ 2.99, or 2.45 ≤ z / y ≤ 2.99 is satisfied. Examples of the tungsten / oxygen ratio include, but are not limited to, WO 2.92 、WO 2.90 、W 20 O 58 、W 24 O 68 、W 17 O 47 、W 18 O 49 and the like. In certain embodiments, the tungsten oxide agent is cesium tungsten oxide (CsWO3) having any of the above-described properties, and in various embodiments, a cesium tungsten oxide agent having a molar ratio of Cs 0.33 WO3 is used. See, for example, U.S. Patent No. 8,216,683, which is incorporated herein by reference. In certain embodiments, the infrared absorbing particles can include indium tin oxide, cesium-doped tungsten oxide, and combinations thereof.

[0029]

[0029] In various embodiments, the polymer composition of the present invention may contain 20 to 80, 20 to 60, 25 to 60, or 35 to 45 parts (phr) of plasticizer per 100 parts of resin. Naturally, other amounts can be used as suitable for specific applications. In some embodiments, the plasticizer has hydrocarbon segments with fewer than 20, 15, 12, or 10 carbon atoms.

[0030]

[0030] The amount of plasticizer is the glass transition temperature (T) of the poly(vinyl butyral) sheet. g ) can be adjusted to affect. Generally, T g To reduce the temperature, a large amount of plasticizer is added. The poly(vinyl butyral) polymer sheet of the present invention can be used at temperatures of 40°C or below, 35°C or below, 30°C or below, 25°C or below, 20°C or below, or 15°C or below. g It can have.

[0031]

[0031] Examples of suitable plasticizers include, but are not limited to, conventional plasticizers such as triethylene glycol di-(2-ethylhexanoate) (also known as "TEG-EH" or "3GEH"), triethylene glycol di-(2-ethylbutyrate), triethylene glycol diheptanoate, tetraethylene glycol diheptanoate, tetraethylene glycol di-(2-ethylhexanoate) ("4GEH"), dihexyl adipate, dioctyl adipate, hexylcyclohexyl adipate, diisononyl adipate, heptylnonyl adipate, di(butoxyethyl) adipate, and bis(2-(2-butoxyethoxy)ethyl) adipate, dibutyl sebacate, dioctyl sebacate, and mixtures thereof. The plasticizer can be selected from the group consisting of triethylene glycol di-(2-ethylhexanoate) and tetraethylene glycol di-(2-ethylhexanoate), or the plasticizer may contain triethylene glycol di-(2-ethylhexanoate). Herein, plasticizers having a refractive index of about 1.450 or less are referred to as “conventional plasticizers.” These plasticizers have refractive indices of about 1.442 to about 1.449. For comparison, PVB resins have refractive indices of about 1.485 to 1.495. In interlayers manufactured for various properties and applications, TEG-EH (refractive index = 1.442) is one of the most common plasticizers available. Other plasticizers, including those not listed herein, may also be used.

[0032]

[0032] In some embodiments, the plasticizer contained in one or more layers may be a high refractive index (RI) plasticizer. Hereinafter, the term “high RI plasticizer” means a plasticizer having a refractive index of at least 1.460 as measured by ASTM D542 at a wavelength of 589 nm and a temperature of 25°C. When used, high RI plasticizers may have refractive indices of at least about 1.470, at least about 1.480, at least about 1.490, at least about 1.500, at least about 1.510, at least about 1.520 and / or about 1.600 or less, about 1.575 or less, or about 1.550 or less as measured as discussed above.

[0033]

[0033] Examples of types or classes of high RI plasticizers include, but are not limited to, polyadipates (RI approximately 1.460 to 1.485), epoxides such as epoxidized soybean oil (RI approximately 1.460 to 1.480), phthalates and terephthalates (RI approximately 1.480 to 1.540), benzoates and toluates (RI approximately 1.480 to 1.550), and other special plasticizers (RI approximately 1.490 to 1.520). Specific examples of suitable RI plasticizers, though not limited to these, include dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, polypropylene glycol dibenzoate, isodecyl benzoate, 2-ethylhexyl benzoate, diethylene glycol benzoate, butoxyethyl benzoate, butoxyethoxyethyl benzoate, butoxyethoxyethyl benzoate, propylene glycol dibenzoate, 2,2,4-trimethyl-1,3-pentanediol dibenzoate, 2,2,4-trimethyl- Examples include 1,3-pentanediol benzoate isobutyrate, 1,3-butanediol dibenzoate, diethylene glycol di-o-toluate, triethylene glycol di-o-toluate, dipropylene glycol di-o-toluate, 1,2-octyl dibenzoate, tri-2-ethylhexyl trimellitate, di-2-ethylhexyl terephthalate, bisphenol A bis(2-ethylhexanate), di-(butoxyethyl) terephthalate, di-(butoxyethyoxyethyl)) terephthalate, and mixtures thereof. High RI plasticizers can be selected from dipropylene glycol dibenzoate and tripropylene glycol dibenzoate, and / or 2,2,4-trimethyl-1,3-pentanediol dibenzoate.

[0034]

[0034] When the resin layer or interlayer contains a high RI plasticizer, the plasticizer may be present in the layer alone or blended with one or more additional plasticizers. The other plasticizers may also contain a high RI plasticizer, or one or more may be low RI plasticizers having a refractive index of less than 1.460. In some embodiments, the low RI plasticizers may have a refractive index of less than about 1.450, less than about 1.445, or less than about 1.442, and can be selected from the group listed above. When a mixture of two or more plasticizers is used, the mixture may have a refractive index within one or more of the above ranges.

[0035]

[0035] In some embodiments, the interlayer may include a first resin layer comprising at least a first resin and a first plasticizer, and a second resin layer comprising a second resin and a second plasticizer. The first and second plasticizers may be the same type of plasticizer, or they may be different. In some embodiments, at least one of the first and second plasticizers may be a blend of two or more plasticizers, which may be the same as or different from one or more other plasticizers.

[0036]

[0036] In various embodiments, the high refractive index plasticizer is selected such that the refractive index of the plasticizer is at least about 1.460, or greater than about 1.460, or greater than about 1.470, or greater than about 1.480, or greater than about 1.490, or greater than about 1.500, or greater than 1.510, or greater than 1.520 for both the core layer and / or the skin layer. In some embodiments, the high refractive index plasticizer is used in conjunction with a conventional plasticizer, and in some embodiments, if included, the conventional plasticizer is triethylene glycol di-(2-ethylhexanoate) (TEG-EH), and the refractive index of the plasticizer mixture is at least 1.460. As used herein, the refractive index of plasticizers or resins used throughout this disclosure is measured according to ASTM D542 at a wavelength of 589 nm and 25°C, or as reported in the literature according to ASTM D542.

[0037]

[0037] Magnesium salicylate [CAS No. 18917-89-0] or its tetrahydrate [CAS No. 18917-95-8] can be prepared as a 20% by weight aqueous solution at room temperature for addition to poly(vinyl butyral) resin plasticizer premixes for extrusion. The aqueous solution is only weakly acidic and has not been found to deacetalize poly(vinyl butyral) resin at addition levels under standard extrusion conditions. Similarly, this aqueous solution may optionally contain additional sodium acetate and / or potassium acetate. Magnesium formate [CAS No. 557-39-1] or its dihydrate [CAS No. 6150-82-9] can be prepared as a 10% by weight aqueous solution at room temperature and can be added to similar preparations based on the required magnesium salt value.

[0038]

[0038] In further embodiments, the polymer composition may further contain one or more epoxy compounds as solar additive stabilizers. These epoxy compounds may be added to the polymer composition itself, or the epoxy compounds may be added to a film covering at least a portion of a polymer sheet also containing one or more solar additives. Any suitable epoxy compound can be used in conjunction with the present invention as is known in the art (see, for example, U.S. Patents 5,529,848 and 5,529,849, incorporated herein by reference).

[0039]

[0039] In various embodiments, useful epoxy compounds described herein are selected from (a) epoxy resins mainly comprising a monomer diglycidyl ether of bisphenol-A, (b) epoxy resins mainly comprising a monomer diglycidyl ether of bisphenol-F, (c) epoxy resins mainly comprising a hydrogenated diglycidyl ether of bisphenol-A, (d) polyepoxidized phenol novolacs, (e) diepoxides of polyglycols known as alternative epoxy-terminated polyethers, and (f) mixtures of any of the epoxy resins of (a) to (e) above (see the Encyclopedia of Polymer Science and Technology, Vol. 6, 1967, Interscience Publishers, NY, pp. 209-271).

[0040]

[0040] A suitable commercially available diglycidyl ether of bisphenol A of class (a) is DER® 331 from Dow Chemical Company or Olin Corporation. The diglycidyl ether of bisphenol-F epoxy of class (b) is EPON Resin DPL-862 (Hexion), and the hydrogenated diglycidyl ether of bisphenol-A epoxy of class (c) is EPONEX® Resin 1510 (Hexion). The polyepoxidized phenol formaldehyde novolac of class (d) is available from Olin Corporation as DEN® 431. The diepoxide of poly(oxypropylene) glycol of class (e) is available from Olin Corporation as DER® 732.

[0041]

[0041] Further examples of suitable epoxy compounds include 3,4-epoxycyclohexanecarboxylate compositions of the type described in U.S. Patent No. 3,723,320. An example of a suitable epoxy compound is:

[0042] [ka]

[0043]

[0042] [In the formula, R1 is -(CH2) 0-3 The formula is -C(O)OR, -C(O)R, -OR, or -CH2OR, where R is an alkyl group having 1 to about 12 carbon atoms, R1 is hydrogen, or an alkyl group having 1 to about 9 carbon atoms, and R3 and R4 are independently hydrogen or alkyl groups having 1 to about 4 carbon atoms. It corresponds to.

[0044]

[0043] Diepoxides, such as those disclosed in U.S. Patent No. 4,206,067, are also useful, as they contain two bonded cyclohexane groups, each condensed with an epoxide group. Such diepoxide compounds are given by the following formula:

[0045] [ka]

[0046] [In the formula, R3 is an organic group containing 1 to 10 carbon atoms, 0 to 6 oxygen atoms, and 0 to 6 nitrogen atoms, and R4 to R9 are independently selected from aliphatic groups containing hydrogen and 1 to 5 carbon atoms.] This corresponds to the following. Exemplary diepoxides include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl adipate), and 2-(3,4-epoxycyclohexyl)-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane. Further examples can be found in U.S. Patent No. 7,585,436, which is incorporated herein by reference.

[0047]

[0044] A further useful epoxy is 2-ethylhexylglycidyl ether (available from Hexion as Hexoxy Modifier 116). Further useful epoxys include diepoxides of poly(oxypropylene) glycol, 2-ethylhexylglycidyl ether, and diepoxide products of epichlorohydrin and polypropylene glycol. Mixtures of epoxy compounds may also be used.

[0048]

[0045] The epoxy compound may be incorporated into the measurement in any suitable amount, taking into consideration the type of epoxy agent, the composition of the polymer film, and the amount of solar additive. Generally, the epoxy compound may be incorporated into the film, for example, together with the solar additive, deposited on the film, in the hard coat of the film, in the binder that bonds two polymer films together into a multi-layer film, or injected alone or in combination with other additives when the film is manufactured.

[0049]

[0046] In various embodiments, the epoxy compound is incorporated into the polymer film in weight percentages of 0.2 to 10.0 weight percent, 0.3 to 5.0 weight percent, 0.5 to 4.0 weight percent, or 1.0 to 3.5 weight percent. These values ​​can be combined in any combination with the values ​​given above for the solar additive as desired for any particular application.

[0050]

[0047] In another embodiment, the composition may further contain one or more silicon-containing silane compounds, such as alkoxysilanes, as adhesion control stabilizing compounds. An example of such compounds is a silanol compound. If the adhesion control stabilizing agent present on the surface of the sheet contains silanol, the coating material applied to the surface of the polymer sheet may contain silanol, or may contain one or more unhydrolyzed silicon-containing compounds that can be converted to silanol when the coating material is applied to the sheet. Examples of suitable silicon-containing compounds that can be easily converted to silanol-containing compounds may include organic alkoxysilanes, including monoalkoxysilanes, dialkoxysilanes, and trialkoxysilanes. In some embodiments, the silicon-containing compound may be a trialkoxysilane, such as trimethoxysilane or triethoxysilane. Examples of suitable trialkoxysilanes, but are not limited to, γ-glycidoxypropyltrimethoxysilane, aminopropyltriethyoxysilane, aminoethylaminopropyltrimethoxysilane, and combinations thereof. If the silicon-containing compound contains a silanol, it may contain one or more hydrolysis forms of the silicon-containing compounds listed above. Examples of such silanes include γ-glycidoxypropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane, and combinations thereof. Further examples can be found in U.S. Patent No. 10,022,908, which is incorporated herein by reference.

[0051]

[0048] Other additives may be incorporated into the polymer composition to enhance the performance of the final product. Such additives include, but are not limited to, dispersants, plasticizers, dyes, pigments (e.g., rutile titanium dioxide), stabilizers (e.g., ultraviolet stabilizers), antioxidants, flame retardants, other infrared absorbers, and combinations of the aforementioned additives, as are known in the art.

[0052]

[0049] Accordingly, the poly(vinyl acetal) polymer composition can be heat-treated according to methods known to those skilled in the art and configured in sheet form. Thus, in another embodiment, the polymer composition of the present invention is formed into a sheet.

[0053]

[0050] In this specification, the terms “polymer interlayer sheet,” “interlayer,” and “polymer melt sheet” may generally refer to a single-layer sheet or a multilayer interlayer. A “single-layer sheet,” as the name suggests, is a single polymer layer extruded as one layer. A multilayer interlayer, on the other hand, may include multiple layers, including individually extruded layers, co-extruded layers, or any combination of individually extruded and co-extruded layers. Thus, a multilayer interlayer may include, for example, two or more single-layer sheets combined together ("multilayer sheet"), two or more layers co-extruded together ("co-extruded sheet"), two or more co-extruded sheets combined together, a combination of at least one single-layer sheet and at least one co-extruded sheet, a combination of a single-layer sheet and a multilayer sheet, and a combination of at least one multilayer sheet and at least one co-extruded sheet. In various embodiments of this disclosure, a multilayer interlayer comprises at least two polymer layers (e.g., single or multiple layers co-extruded and / or laminated together) arranged in direct contact with each other, each layer comprising a polymer resin as described more fully below. For multilayer interlayers having at least three layers, the term “skin layer” generally refers to the outer layer of the interlayer, and the term “core layer” generally refers to the inner layer. Thus, one exemplary embodiment is skin layer / / core layer / / skin layer. The layers or combination of layers may include solar additives. Further details regarding multilayer sheets can be found in U.S. Patent No. 10,252,500, which is incorporated herein by reference.

[0054]

[0051] In a further embodiment, the present invention provides a sheet of the present invention which is a multilayer sheet.

[0055]

[0052] One exemplary method for forming a poly(vinyl butyral) sheet includes extruding a molten poly(vinyl butyral) (hereinafter referred to as the "molten material") containing a resin, a plasticizer, and additives, by pushing the molten material through a sheet die (for example, a die having an opening of a certain dimension substantially larger than the vertical dimension). Another exemplary method for forming a poly(vinyl butyral) sheet includes casting the molten material from the die onto a roller to allow the resin to solidify, and then removing the solidified resin as a sheet. In either embodiment, the surface properties on either or both sides of the sheet can be controlled by adjusting the surface of the die opening or by providing properties on the roller surface. Other techniques for controlling the properties of the sheet include changing material parameters (e.g., water content of the resin and / or plasticizer, melting temperature, molecular weight distribution of poly(vinyl butyral), or combinations of the aforementioned parameters). Furthermore, the sheet can be configured to include spaced protrusions that define temporary surface irregularities to facilitate degassing of the sheet during the lamination process, after which the high temperature and pressure of the lamination process melt these protrusions into the sheet, thereby resulting in a smooth finish. In various embodiments, the polymer sheet can have thicknesses of 0.1–2.5 mm, 0.2–2.0 mm, 0.25–1.75 mm, and 0.3–1.5 mm (mm).

[0056]

[0053] Accordingly, in another embodiment, the present invention provides a poly(vinyl acetal) composition of the present invention that is formed into a sheet.

[0057]

[0054] Furthermore, any stack or roll of any of the polymer composition sheets of the present invention disclosed herein is included in the present invention in any combination.

[0058]

[0055] The present invention also includes a method for manufacturing windshields and other laminated glass products, comprising the steps of inserting a polymer sheet of the present invention between two layers of glass and laminating a three-layer laminate.

[0059]

[0056] Furthermore, the present invention includes laminated safety glass comprising a layer of glass, and typically comprising silicon dioxide disposed in contact with any of the polymer sheets of the present invention (however, other types of glass described later may be used). Furthermore, the present invention includes laminated safety glass comprising at least two of the glass sheets together with an interlayer polymer sheet disposed between the glass sheets, wherein the polymer sheet is any of the polymer sheets disclosed herein as embodiments of the present invention.

[0060]

[0057] The multilayer glazing or panel described herein generally comprises a first rigid substrate sheet having a first substrate thickness and a second rigid substrate sheet having a second substrate thickness. Each of the first and second substrates may be formed of a rigid material such as glass, and may be formed of the same or different materials. In some embodiments, at least one of the first and second substrates may be a glass substrate, while in other embodiments, at least one of the first and second substrates may be formed of another material, including a rigid polymer such as polycarbonate, copolyester, acrylic, polyethylene terephthalate, and combinations thereof. In embodiments, both rigid substrates are glass. Such substrates can be formed using any suitable type of non-glass material, depending on the required performance and properties. Typically, none of the rigid substrates are formed from softer polymer materials, including thermoplastic polymer materials, as will be described in detail below.

[0061]

[0058] A rigid glass substrate can be formed using any suitable type of glass, and in some embodiments, the glass may be selected from the group consisting of aluminasilate glass, borosilicate glass, quartz or fused silica glass, and soda-lime glass. The glass substrate may be annealed, heat-strengthened or tempered, chemically strengthened, etched, coated, or strengthened by ion exchange, or one or more of these treatments may be applied. The glass itself may be roll-formed glass, float glass, or plate glass. In some embodiments, the glass may not be chemically treated or strengthened by ion exchange, while in other embodiments, the glass may not be aluminasilate glass. When the first and second substrates are glass substrates, the types of glass used to form each substrate may be the same or different.

[0062]

[0059] The rigid substrate can have any suitable thickness. In some embodiments, if the rigid substrate is an all-glass substrate, the nominal thickness of at least one of the glass sheets (first or second glass) is in the range of 0.1 mm to 12.7 mm, and the multilayer glass panel includes configurations of any combination of the first and second glass sheets (and any other glass or rigid sheet as needed). In some embodiments, the nominal thickness of the first and / or second substrate may be at least about 0.4 mm, at least about 0.5 mm, at least about 0.7 mm, at least about 0.75 mm, at least about 1.0 mm, at least about 1.25 mm, at least about 1.3 mm, at least about 1.6 mm, at least about 1.9 mm, at least about 2.2 mm, at least about 2.5 mm, or at least about 2.8 mm and / or less than about 3.2 mm, less than about 2.9 mm, less than about 2.6 mm, less than about 2.5 mm, less than about 2.3 mm, less than about 2.0 mm, less than about 1.75 mm, less than about 1.7 mm, less than about 1.5 mm, less than about 1.4 mm, or less than about 1.1 mm.

[0063]

[0060] Furthermore, or alternatively, the first and / or second substrates may have nominal thicknesses of at least about 2.3 mm, at least about 2.6 mm, at least about 2.9 mm, at least about 3.2 mm, at least about 3.5 mm, at least about 3.8 mm, or at least about 4.1 mm and / or less than about 12.7 mm, less than about 12.0 mm, less than about 11.5 mm, less than about 10.5 mm, less than about 10.0 mm, less than about 9.5 mm, less than about 9.0 mm, less than about 8.5 mm, less than about 8.0 mm, less than about 7.5 mm, less than about 7.0 mm, less than about 6.5 mm, less than about 6.0 mm, less than about 5.5 mm, less than 5.0 mm, or less than about 4.5 mm. Other thicknesses may be appropriate depending on the required application and characteristics.

[0064]

[0061] The present invention also includes windshields, windows, and other finished glass products, or multi-layer panels comprising polymer sheets of the present invention.

[0065]

[0062] Various properties and measurement techniques for polymer sheets and / or laminated glass for use in conjunction with the present invention are described here. The transparency of polymer sheets, in particular poly(vinyl butyral) sheets, can be determined by measuring the haze level or value, which is a quantitative measure of light that does not pass through the sheet. The haze rate can be measured according to the following technique: A hazemeter, Model D25, available from Hunter Associates (Reston, Virginia, USA), which is a device for measuring the amount of haze, can be used according to ASTM D1003-61 (re-approved in 1977) - Procedure A, using a light source C at an observation angle of 2 degrees. In various embodiments of the present invention, the haze rate is less than 5%, less than 3%, or less than 1%.

[0066]

[0063] The Panmel adhesive strength can be measured according to the following technique, where “Panmel” is used herein to quantify the adhesive strength of a polymer sheet to glass, and the following technique is used to determine the Panmel value. A two-layer glass laminate sample is prepared under standard autoclave lamination conditions. The laminate is cooled to approximately -17°C (0°F), and the glass is broken by manually striking it repeatedly with a hammer. All broken glass that is not adhered to the poly(vinyl butyral) sheet is then removed, and the amount of glass remaining adhered to the poly(vinyl butyral) sheet is visually compared to a series of standards. The standards correspond to various degrees of glass remaining adhered to the poly(vinyl butyral) sheet. In particular, Panmel standard zero means that no glass remains adhered to the poly(vinyl butyral) sheet. Panmel standard 10 means that 100% of the glass remains adhered to the poly(vinyl butyral) sheet. In the case of the laminated glass panel of the present invention, various embodiments have a Pummel value of at least 3, at least 5, at least 8, at least 9, or 10. Other embodiments have a Pummel value ranging from 8 to 10.

[0067]

[0064] The sheets and layers described herein may maintain adhesion to other layers or substrates even when the laminate is exposed to high temperature and high humidity conditions, despite high levels of moisture intrusion. For example, the layers and interfilms according to the present invention may exhibit peel adhesion while having an average moisture content of at least about 0.3 percent, at least about 0.4 percent, at least about 0.5 percent, at least about 0.7 percent, or at least 1 percent, as measured by Karl Fischer titration according to ASTM E203.

[0068]

[0065] The "yellowness" of a polymer sheet can be measured as follows: A transparent molded disc of a polymer sheet with a thickness of 1 cm is formed, having a smooth polymer surface that is essentially flat and parallel. The yellowness is measured from the spectral light transmittance of the visible spectrum according to ASTM method D1925, "Standard Test Method for Yellowness Index of Plastics". The value is corrected to a thickness of 1 cm using the thickness of the measured test piece.

[0069]

[0066] In this specification, “potency” can be determined for sodium acetate and potassium acetate (referred to as “total alkali value” in this specification) and magnesium salts in a sheet sample using the following method.

[0070]

[0067] To determine the amount of resin in each sheet sample to be weighed, the following formula is used, where PHR is defined as the number of grams (pounds) of resin in the original sheet sample preparation, including plasticizers and any other additives to the resin, per 45359.2 grams (100 pounds).

[0071] Grams of resin in the sheet sample = Grams of sheet sample (100 + PHR) / 100

[0068] Approximately 5 grams (g) of resin in the sheet sample is the target mass used to initially estimate the amount of the sheet sample, and the calculated mass of resin in the sheet sample is used for each titration measurement. All titrations should be completed on the same day.

[0072]

[0069] Dissolve the sheet sample in 250 ml of methanol in a beaker. It may take up to 8 hours for the sheet sample to dissolve completely. Prepare a methanol-only blank in a beaker as well. Titrate the sample and blank with 0.00500 normal HCl, respectively, using an automated pH titrator programmed to stop at pH 2.5. Record the amount of HCl added to the sample and blank to obtain pH 4.2. The HCl titer is determined according to the following formula. HCl titer (ml / 100g resin of 0.01N HCl) = 50 × (ml of HCl in the sample - ml of HCl in the blank) Calculated grams of resin

[0070] To determine the magnesium salt value, the following procedure is used. 54 grams of ammonium chloride and 12-15 ml of pH 10.00 buffer prepared from 350 ml of ammonium hydroxide diluted in methanol to 1 liter, as well as 12-15 ml of Erichrome Black T indicator, are added to the blank and each sheet sample, all of which have already been titrated with HCl as described above. The titrant is then changed to a 0.000298 g / ml EDTA solution prepared from 0.3263 g of tetrasodium ethylenediaminetetraacetate dihydrate and 5 ml of water, diluted in methanol to 1 liter. The EDTA titration is measured by light transmittance at 596 nm. The transmittance % is first adjusted to 100% in the sample or blank before starting the titration, during which the solution is a bright magenta pink color. When the transmittance at 596 nm becomes constant, the EDTA titration is complete and the solution is a deep indigo color. The volume of EDTA titrated to achieve the indigo blue endpoint is recorded for the blank and each sheet sample. The magnesium salt value is determined according to the following formula.

[0073] 0.000298g / ml EDTA × (ml of EDTA in the sample) Magnesium salt value = (Blank EDTA ml) (1 x 10 per gram of resin) -7 Moles (grams of resin in the sheet sample) × (As magnesium salt) 380.2 g / mol of EDTA × 0.0000001

[0071] From these results, the total alkali value is 1 × 10 per gram of resin. -7 The molar amount of acetate can be calculated according to the following formula. Total alkali value = HCl titer of the sheet - (2 × total magnesium salt value)

[0072] The portion of the total alkali value attributable to either sodium acetate or potassium acetate can be determined by first determining the total alkali value as described above. After determining the total alkali value, a destructive analysis of the polymer sheet can be performed by inductively coupled plasma emission spectroscopy (ICP) to obtain the ppm concentrations of potassium and sodium.

[0074]

[0073] The alkali value due to sodium acetate is defined herein as the total alkali value multiplied by the ratio [ppm of sodium / (ppm of sodium + ppm of potassium)].

[0075]

[0074] The alkali value due to potassium acetate is defined herein as the total alkali value multiplied by the ratio [ppm of potassium / (ppm of sodium + ppm of potassium)].

[0076]

[0075] The present invention may be further described by the following embodiments of its particular form, but it will be understood that these embodiments are included for illustrative purposes only and are not intended to limit the scope of the invention unless otherwise indicated. [Examples]

[0077]

[0076] In each case, two premix batches containing a 1500-gram mixture of PVB resin-based resin and plasticizer were used for sheet extrusion at approximately 200°C. For each case, which was tested by ACA titration to confirm the steady-state composition, a sample of the PVB sheet was collected only towards the end of the extrusion (approximately 5 minutes) before the second premix batch was used up in the extrusion.

[0078]

[0077] Exemplary titrations were performed on the samples with and without ITO nanoparticles, showing low binding compared to high binding. As shown in Table 1, samples 1, 2, and 6 did not contain ITO nanoparticles, while samples 3, 4, and 5 all contained 0.108% ITO nanoparticles. Magnesium bis(2-ethylhexanoate) was used as ACA for all samples except sample 5, which contained magnesium salicylate.

[0079]

[0078] For sample 5 in Table 1 below, magnesium salicylate tetrahydrate was dissolved in water to prepare a 20% by weight solution. Since it could not be individually dissolved in the plasticizer TEG-EG (triethylene glycol di-(2-ethylhexanoate)), 6.95 g was blended into each 1500 g PVB resin batch for extrusion. The ACA calculation for magnesium salicylate tetrahydrate is as follows.

[0080] The amount of 20% magnesium salicylate tetrahydrate per 1500g of PVB is calculated as follows: 25 * 0.0000001 * 1500 * 370.6 / (20 / 100) = 6.95g (for Mg with a titer of 25)

[0079] For samples 2, 3, and 4, and for the standards of samples 1 and 6, magnesium bis(2-ethylhexanoate) was used as a 40 wt% aqueous solution. An amount corresponding to 20 titers for sample 2 and 30 titers for samples 3 and 4 was added to each plasticizer mixture, heated to 60°C to remove residual water, and other additives, such as UV blockers and antioxidants, were dissolved. The ACA calculation for magnesium bis(2-ethylhexanoate) is as follows:

[0081] The amount of 40% magnesium bis(2-ethylhexanoate) per 1500g of PVB is calculated as follows: 20 * 0.0000001 * 1500 * 310 / (40 / 100) = 2.325g (for Mg with a titer of 20)

[0080] The plasticizer mixture of sample 5, intended for use in extrusion with magnesium salicylate, contained only the plasticizer, TEG-EH, and UV-blocking and antioxidant agents. Similarly, they were heated to 60°C to dissolve the solids in the plasticizer. The resulting extruded PVB sheets had a plasticizer content of 38 phr and 0.108% ITO (no ITO in the case of samples 1, 2, and 6). The results are shown in Table 1 below.

[0082] [Table 1]

[0083]

[0081] The measurement standard statistics for the titration procedure are shown below.

[0084] [Table 2]

[0085]

[0082] According to the ACA titration results, the PVB sheet of sample 5, extruded with 25 titer magnesium salicylate and 0.108% ITO nanoparticles, had a small percentage of binding compared to samples 3 and 4, which were made with 30 titer magnesium bis(2-ethylhexanoate) and 0.108% ITO nanoparticles. Compared to the control sample without ITO nanoparticles, control sample 2, which did not contain ITO and was extruded with 20 titer magnesium bis(2-ethylhexanoate), and the standards (samples 1 and 6), which contained approximately 12 titers of magnesium from magnesium bis(2-ethylhexanoate), had similar small levels of binding (e.g., less than 2%). The PVB sheets of samples 7 and 8, which contained magnesium formate with titers of 27 and 30, and ITO% of 0.160% and 0.228% respectively (highest ITO loading), had a binding percentage of over 15%, which was lower than that of samples 3 and 4, which were made with magnesium bis(2-ethylhexanoate) with titer of 30 and 0.108% ITO nanoparticles (e.g., less than 7%).

[0086]

[0083] Peel Test Measurement: The 90° peel adhesion values ​​for the glass provided herein were determined by the following procedure. First, a 30.48 cm (12 inch) × 17.145 cm (6.75 inch) glass / PVB sheet / aluminum foil laminate was prepared using a nip roll or vacuum degassing method, and the resulting laminate was autoclaved under standard laminated glass manufacturing conditions, including a holding period of 20 minutes at 143°C and 185 psig. Before assembly, the glass was washed according to standard methods and the PVB sheet was adjusted to a standard moisture content of 0.43 weight percent. The PVB sheet used in the laminate had a thickness of 30 mil (0.762 mm). The glass used to form the laminate was 2.3 mm thick clear float glass, and the laminate was assembled with the air side of the glass facing the PVB layer. The aluminum foil was treated to ensure very high adhesion to the PVB sheet.

[0087]

[0084] After autoclaving as described above, the laminate was stored under ambient conditions for at least 16 hours before testing. Next, each 30.48 cm (12 inches) × 17.145 cm (6.75 inches) glass laminate was first cut into four test pieces, each measuring 7.62 cm (3 inches) × 17.145 cm (6.75 inches). Then, the aluminum foil and PVB layers were placed along the long side of each test piece, and the laminate was prepared for peel adhesion testing by cutting two parallel lines at a distance of 4 centimeters from the center of each test piece at once. Both sections were stretched along the entire length of each test piece. Then, each test piece was turned over, notches were made in the glass, and it was split along its width at a location approximately 5.715 cm (2.25 inches) from the top. Next, the test piece was bent at a 90° angle along the notched line in the glass.

[0088]

[0085] Next, the peel adhesion of each specimen was tested using a universal material tester (UTM), such as those manufactured by Instron or MTS Systems, equipped with a mounting system designed to perform 90° peel adhesion measurements. The peel adhesion test specimen was held in a slide mounting device such that the upper 5.715 cm (2.25 inches) × 7.62 cm (3 inches) portion was firmly held within the grip, and the lower 7.62 cm (3 inches) × 11.43 cm (4.5 inches) portion was supported without obstructing the 4 cm test strip area, and the specimen was oriented so that a 90° angle was maintained throughout the peel test. The specimen was then peeled at a speed of 12.7 cm (5 inches) per minute (cm(inches) / min). The required average peel force (N) over a length of 7.62 cm (3 inches) was determined and normalized over the width of the test strip (4 cm) to obtain the 90° peel adhesion value.

[0089]

[0086] Additional samples were prepared with and without ITO nanoparticles (as shown in Table 2) using magnesium salicylate, magnesium formate, and bis(2-ethylhexanoate magnesium), and the binding percentage and tackiness were tested (measured by peel and Pammel tests). The samples and results are described below. All samples were prepared using poly(vinyl butyral) resin (BUTVAR® resin from Eastman Chemical Company) and TEG-EH plasticizer. The resin and plasticizer were mixed to achieve 38 parts per 100 parts of TEG-EH plasticizer.

[0090]

[0087] For samples 9 and 10 (magnesium salicylate without ITO), the plasticizer mixture for extrusion with magnesium salicylate contained only the plasticizer (TEG-EH), UV blocker, and antioxidant. The magnesium salicylate titer was added separately to the resin as shown. The plasticizer mixture was heated to 60°C to dissolve the solid UV stabilizer and antioxidant in the plasticizer. The ITO nanoparticle dispersant was not added to the plasticizer mixture. In addition to the magnesium salicylate titer added to the resin, several additional potassium acetate titers were added to the resin to achieve the total potassium acetate titer shown in Table 2 below.

[0091]

[0088] For samples 11, 12, 13, and 14 (magnesium salicylate containing ITO), the plasticizer mixture for extrusion with magnesium salicylate contained only the plasticizer (TEG-EH), UV blocker, and antioxidant. The magnesium salicylate titer was added separately to the resin as shown. The plasticizer mixture was heated to 60°C to dissolve the solid UV stabilizer and antioxidant in the plasticizer. An ITO nanoparticle dispersant was added to the plasticizer mixture to achieve a final ITO nanoparticle concentration of either 0.1025% or 0.1600% ITO% (shown in Table 2). In addition to the magnesium salicylate titer added to the resin, several additional potassium acetate titers were added to the resin to achieve the total potassium acetate titer shown in Table 2.

[0092]

[0089] For samples 15 and 16 (magnesium bis(2-ethylhexanoate) containing ITO), magnesium bis(2-ethylhexanoate) was used as a 40 wt% aqueous solution and added in an amount corresponding to 25 titers for sample 15 and 26 titers for sample 16. Each plasticizer mixture was heated to 60°C, residual water was removed, and other additives, such as UV-blocking agents and antioxidant solids, were dissolved in the plasticizer. ITO nanoparticle dispersants were added to each plasticizer mixture of samples 15 and 16 so that final ITO nanoparticle concentrations of 0.1025% and 0.1600% ITO% were achieved in the PVB sheets extruded from the respective combined resin and plasticizer mixtures. The added potassium acetate titers from the PVB resin and added salts were 26.9 and 28.9 titers, respectively.

[0093]

[0090] For samples 17 and 18 (magnesium bis(2-ethylhexanoate) without ITO), the resin with dissolved magnesium bis(2-ethylhexanoate), plasticizer, UV stabilizer, and antioxidant were mixed. No ITO was added. The total potassium acetate from the PVB resin and added salts was measured to be 14.1 and 14.4 titers, respectively.

[0094]

[0091] In the case of samples 19 and 20 (magnesium bis(2-ethylhexanoate) containing CWO), magnesium bis(2-ethylhexanoate) was used as a 40 wt% aqueous solution, and the resin and plasticizer were added in an amount corresponding to 17 titers. Each plasticizer mixture was heated to 60°C, residual water was removed, and other additives, such as UV blockers and antioxidant solids, were dissolved in the plasticizer. A CWO nanoparticle dispersant was added to each plasticizer mixture of samples 19 and 20 so that final CWO nanoparticle concentrations of 0.065% and 0.041% CWO% were achieved in the PVB sheets extruded from the respective combined resin and plasticizer mixtures. The added potassium acetate titer from the PVB resin and added salts was 28.3 titers for both samples.

[0095]

[0092] In the case of samples 21 and 22 (magnesium formate containing ITO), magnesium formate was used as a 10.0 wt% aqueous solution and added to the resin and plasticizer in amounts corresponding to 27 and 30 titers for two different ITO levels of 0.160% and 0.228%, respectively. Each plasticizer mixture was heated to 60°C, residual water was removed, and other additives, such as UV-blocking agents and antioxidant solids, were dissolved in the plasticizer. ITO nanoparticle dispersants were added to each plasticizer mixture. PVB sheets were extruded from each combined resin and plasticizer mixture. The titers of potassium acetate added from the PVB resin and added salts were 29.0 and 32.0 titers for samples 21 and 22, respectively.

[0096]

[0093] For samples 23 and 24 (magnesium bis(2-ethylhexanoate) containing ITO), magnesium bis(2-ethylhexanoate) was used as a 40 wt% aqueous solution and added to the resin and plasticizer in amounts corresponding to 28 and 23 titers, respectively, relative to an ITO level of 0.1079%. Two different plasticizer mixtures or blends (35% dipropylene glycol dibenzoate / 65% 3GEH) were used. Each plasticizer mixture was heated to 60°C, residual water was removed, and other additives, such as UV blockers and antioxidant solids, were dissolved in the plasticizer. ITO nanoparticle dispersants were added to each plasticizer mixture. PVB sheets were extruded from each combined resin and plasticizer mixture. The added potassium acetate titers from the PVB resin and added salts were 26.0 and 28.0 titers for samples 23 and 24, respectively.

[0097] [Table 3]

[0098]

[0094] As shown in the ACA titration results of the extruded sheets in Table 2, samples 15 and 16, and samples 23 and 24 (magnesium bis(2-ethylhexanoate) containing ITO) had significantly increased binding % or hydrolysis % compared to samples without ITO or samples using magnesium salicylate or magnesium formate. The magnesium salicylate and magnesium formate ACA of the present invention effectively resisted hydrolysis during extrusion in the presence of ITO and maintained low binding % (i.e., less than 25% binding % or less than 20% binding % or less than 15% binding %).

[0099]

[0095] The pKa of each carboxylic acid used to formulate each magnesium carboxylic acid salt is shown in Table 3.

[0100] [Table 4]

[0101]

[0096] In order to reduce or prevent bonding or hydrolysis while maintaining an acceptable level of adhesion, the inventors have found that by using a different magnesium salt (having a carboxylate group with a pKa of less than about 4.80 for the corresponding carboxylic acid) as an adhesion control agent instead of the conventional adhesion control agent bis(2-ethylhexanoate)magnesium (having a carboxylate group with a pKa of about 4.82 for the corresponding carboxylic acid), the bonding or hydrolysis of the magnesium salt ACA is reduced, resulting in an acceptable level of adhesion.

[0102]

[0097] As described above, this magnesium salt is a magnesium carboxylate salt comprising divalent magnesium and a magnesium salt which is at least one carboxylate group, and has the general formula M(R'COO) n The formula is derived from the equation M(R'COO), where M is a metal such as magnesium and n is an integer such as 1, 2, 3, or 4. Specifically, the magnesium salt of the present invention is given by the formula M(R'COO) nThe formula comprises, where M is magnesium, n is 2, and R' is an organic group having 1 to 20 carbon atoms. The organic group may be, for example, an alkyl, aryl, or heterocyclic group. The magnesium salt also contains the corresponding hydrate. In embodiments, the pKa of the corresponding carboxylic acid is in the range of about 2.00 to less than about 4.80. In embodiments, the pKa of the corresponding carboxylic acid is greater than 2.00, greater than 2.10, greater than 2.20, greater than 2.30, greater than 2.40, greater than 2.50, greater than 2.60, greater than 2.70, greater than 2.80, greater than 2.90, greater than 3.00, greater than 3.10, greater than 3.20, greater than 3.30, greater than 3.40, greater than 3.50, greater than 3.60, or greater than 3.70. In the embodiment, the pKa of the corresponding carboxylic acid is less than 4.70, less than 4.60, less than 4.50, less than 4.40, less than 4.30, less than 4.20, less than 4.10, or less than 4.00.

[0103]

[0098] The magnesium carboxylate salts of the present invention are generally synthesized from the reaction of magnesium hydroxide (or magnesium oxide) with an acid stronger than 2-ethylhexanoic acid ("2-EHA"), which is an acid used to produce one of the standard or commonly used adhesion control salts (RSS5). Other known adhesion control salts or adhesion control agents ("ACAs") include, but are not limited to, ACAs disclosed in U.S. Patent No. 5,728,472 (the entire disclosure of which is incorporated herein by reference), sodium residual acetate, potassium acetate, bis(2-ethylbutyrate)magnesium, and / or bis(2-ethylhexanoate)magnesium.

[0104]

[0099] By using an acid stronger than 2-EHA, a magnesium salt with low basicity (reactivity) can be obtained. A typical reaction is as follows.

[0105]

[0100] Mg(OH)2 + 2(R'COOH)-≫Mg(ROO)2 + 2H2O (wherein R' is an organic group having 1 to 20 carbon atoms, such as an alkyl, aryl, or heterocyclic group). The present invention includes the following embodiments. [1] A polymer composition, a. Poly(vinyl acetal) resin, b. Solar additives and c. Sodium acetate and / or potassium acetate, d. At least one type of plasticizer, e. A magnesium salt comprising a divalent magnesium ion and at least two carboxylate groups, wherein the corresponding carboxylic acids of the carboxylate groups each have a pKa of less than about 4.80, and the titer of the magnesium salt or its hydrate is about 10 to about 60. It contains such a compound that the alkali value resulting from the combination of potassium acetate and sodium acetate is approximately 10 to approximately 60, and the ratio of the titer of the magnesium salt or its hydrate to the alkali value resulting from the combination of potassium acetate and sodium acetate is approximately 0.5 to approximately 2.0. Polymer composition. [2] The composition according to [1], wherein the plasticizer is a high refractive index plasticizer having a refractive index of at least 1.460 as measured by ASTM D542 at a wavelength of 589 nm and a temperature of 25 °C. [3] The composition according to [1] or [2], wherein the solar additive is indium tin oxide, antimony tin oxide, or metal-doped tungsten oxide. [4] The composition according to [3], wherein the metal-doped tungsten oxide is cesium-doped tungsten oxide or cesium and tin-doped tungsten oxide. [5] The composition according to any one of [1] to [4], further comprising rutile-type titanium dioxide. [6] The composition according to any one of [1] to [5], wherein the potency of the magnesium salt or its hydrate is about 10 to about 40. [7] The composition according to any one of [1] to [6], wherein the alkali value is about 10 to about 40. [8] A composition according to any one of [1] to [7], further comprising one or more epoxy compounds. [9] The composition according to [8], wherein the epoxy compound is selected from polyglycol diepoxides, aliphatic cyclic monoepoxides and aliphatic cyclic diepoxides.

[10] The composition according to [9], wherein the epoxy compound is selected from 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl adipate), 2-(3,4-epoxycyclohexyl)-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, 2-ethylhexylglycidyl ether, diepoxides of poly(oxypropylene) glycol, and diepoxide counterparts of epichlorohydrin and polypropylene glycol.

[11] The composition according to any one of [1] to

[10] , further comprising one or more silane additives or silane-containing compounds.

[12] The composition according to

[11] , wherein the silane-containing compound is selected from γ-glycidoxypropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, and combinations thereof.

[13] The composition according to any one of [1] to

[12] , wherein the magnesium salt is magnesium salicylate, magnesium formate, magnesium salicylate tetrahydrate, or magnesium formate dihydrate.

[14] The composition according to any one of [1] to

[13] , wherein the poly(vinyl acetal) resin has a moisture level of less than about 1% by weight.

[15] The composition according to any one of [1] to

[14] , wherein the binding percentage is less than approximately 15%.

[16] A polymer composition, a. Poly(vinyl acetal) resin having a moisture level of less than approximately 1% by weight, b. Solar additives and c. Sodium acetate and / or potassium acetate, d. At least one type of plasticizer, e. A magnesium salt comprising a divalent magnesium ion and at least two carboxylate groups, wherein the corresponding carboxylic acids of the carboxylate groups each have a pKa of less than about 4.80, and the titer of the magnesium salt or its hydrate is about 10 to about 60. It contains such a compound that the alkali value resulting from the combination of potassium acetate and sodium acetate is approximately 10 to approximately 60, and the ratio of the titer of the magnesium salt or its hydrate to the alkali value resulting from the combination of potassium acetate and sodium acetate is approximately 0.5 to approximately 2.0. The level of binding is less than approximately 25%. Polymer composition. An interlayer sheet comprising the composition described in any of [1] to

[16] , wherein the composition is formed on the interlayer sheet.

[18] The interlayer sheet according to

[17] , further comprising one or more additional layers to form a multilayer sheet.

[19] An interlayer sheet as described in

[18] , comprising three layers.

[20] Laminated safety glass comprising two glass sheets and an interlayer sheet as described in any of

[17] to

[19] , wherein the interlayer sheet is positioned between the two glass sheets.

Claims

1. A polymer composition for a poly(vinyl acetal) sheet in a laminated safety glass structure, a. Poly(vinyl acetal) resin and b. Solar additives which are indium tin oxide, antimony tin oxide, or metal-doped tungsten oxide, c. Sodium acetate and / or potassium acetate, d. At least one type of plasticizer, e. A magnesium salt comprising a divalent magnesium ion and at least two carboxylate groups, wherein the corresponding carboxylic acids of the carboxylate groups each have a pKa of less than 4.80, and the titer of the magnesium salt or its hydrate is 25 to 40. It contains a compound in which the alkali value resulting from the combination of potassium acetate and sodium acetate is 10 to 32.0, the ratio of the potency of the magnesium salt or its hydrate to the alkali value resulting from the combination of potassium acetate and sodium acetate is 0.5 to 2.0, and the magnesium salt is magnesium salicylate, magnesium formate, magnesium salicylate tetrahydrate, or magnesium formate dihydrate. Polymer composition.

2. The composition according to claim 1, wherein the plasticizer comprises a high refractive index plasticizer having a refractive index of at least 1.460, as measured by ASTM D542 at a wavelength of 589 nm and a temperature of 25°C.

3. The composition according to claim 1, wherein the metal-doped tungsten oxide is cesium-doped tungsten oxide or cesium and tin-doped tungsten oxide.

4. The composition according to any one of claims 1 to 3, further comprising rutile-type titanium dioxide.

5. The composition according to any one of claims 1 to 4, further comprising one or more epoxy compounds.

6. The composition according to claim 5, wherein the epoxy compound is selected from polyglycol diepoxides, aliphatic cyclic monoepoxides, and aliphatic cyclic diepoxides.

7. The composition according to claim 6, wherein the epoxy compound is selected from 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane, bis(3,4-epoxy-6-methylcyclohexylmethyl adipate), 2-(3,4-epoxycyclohexyl)-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, 2-ethylhexylglycidyl ether, diepoxides of poly(oxypropylene) glycol, and diepoxide counterparts of epichlorohydrin and polypropylene glycol.

8. The composition according to any one of claims 1 to 7, further comprising one or more silane additives or silane-containing compounds.

9. The composition according to claim 8, wherein the silane-containing compound is selected from γ-glycidoxypropyltrimethoxysilane, aminopropyltriethoxysilane, aminoethylaminopropyltrimethoxysilane, and combinations thereof.

10. The composition according to any one of claims 1 to 9, wherein the poly(vinyl acetal) resin has a moisture content of less than 1% by weight.

11. A polymer composition for a poly(vinyl acetal) sheet in a laminated safety glass structure, a. A poly(vinyl acetal) resin having a moisture content of less than 1% by weight, b. Solar additives which are indium tin oxide, antimony tin oxide, or metal-doped tungsten oxide, c. Sodium acetate and / or potassium acetate, d. At least one type of plasticizer, e. A magnesium salt comprising a divalent magnesium ion and at least two carboxylate groups, wherein the corresponding carboxylic acids of the carboxylate groups each have a pKa of less than 4.80, and the titer of the magnesium salt or its hydrate is 25 to 40. It contains a compound in which the alkali value resulting from the combination of potassium acetate and sodium acetate is 10 to 32.0, the ratio of the potency of the magnesium salt or its hydrate to the alkali value resulting from the combination of potassium acetate and sodium acetate is 0.5 to 2.0, and the magnesium salt is magnesium salicylate, magnesium formate, magnesium salicylate tetrahydrate, or magnesium formate dihydrate. Polymer composition.

12. An interlayer sheet comprising the composition according to any one of claims 1 to 11, wherein the composition is formed in the interlayer sheet.

13. The interlayer sheet according to claim 12, further comprising one or more additional layers to form a multilayer sheet.

14. An interlayer sheet according to claim 13, comprising three layers.

15. Laminated safety glass comprising two glass sheets and an interlayer sheet according to any one of claims 12 to 14, wherein the interlayer sheet is disposed between the two glass sheets.

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