Acoustic damping material comprising renewable raw materials

Abstract

The present invention relates to a sound damping material comprising a binder matrix and a filler component, said binder matrix comprising an asphalt component or a polymer component, and said filler component comprising at least one solid particulate cellulosic-containing filler. The sound damping material is suitable for use in the damping of undesired vibrations and noise in mechanical structures and components of manufactured articles. The present invention also relates to the use of the sound damping material for the damping of vibrations and noise in transport vehicles and large household appliances, to a vibration and noise damping element comprising a damping layer consisting of the sound damping material, to a method of applying a vibration and noise damping element to a noise emitting surface of a substrate, and to a vibration damping system comprising a substrate and a vibration and noise damping element bonded to a noise emitting surface of the substrate.

Description

Technical Field

[0001] This invention relates to compositions for vibration and noise damping in the mechanical structures of manufactured articles. Specifically, this invention relates to compositions comprising renewable raw materials suitable for vibration damping in components and structures contained in articles of manufacture in the automotive industry, household appliances, and general industry. Background of the Invention

[0003] Sound damping materials are widely used in automobiles, home appliances, and general industry to reduce unwanted vibrations, structural noise, and aerodynamic noise. For example, in automobiles, it is desirable to prevent vibrations generated by motors, pumps, gears, and other dynamic force generators from being transferred through the vehicle body into the passenger compartment. Structural noise is generated when vibrations generated by dynamic force generators are transmitted through a support structure, typically a frame or other hollow structure, to noise-emitting surfaces such as metal or plastic panels (which convert mechanical vibrations into sound waves). Structural noise and vibration can typically be effectively reduced by applying vibration damping materials directly to the structure and surfaces of components subjected to vibration disturbances, such as vehicle panels, floors, machine housings, and the surfaces of washing machines and dryers.

[0004] Acoustic damping materials for vibration damping of panels and boards are often provided in the form of pre-formed single-layer and multi-layer damping elements or as liquid compositions applied directly to the surface of a substrate. Damping materials designed for vibration and noise damping in hollow structures such as cavities are often provided in the form of cavity filler inserts comprising an expandable composition and one or more connecting members capable of holding the cavity filler insert in a desired position within the hollow structure.

[0005] Pre-formed single-layer and multi-layer damping elements comprise a damping layer that is in direct contact with the surface of a substrate to which vibration disturbances are to be damped. The damping layer dissipates the kinetic energy of the vibrating surface as heat through the stretching and compression of the damping layer material. Pre-formed single-layer and multi-layer damping elements often include an adhesive composition, such as a pressure-sensitive adhesive (PSA) or a hot-melt adhesive, enabling the damping layer to bond to the surface of a substrate, such as a panel or floor of an automotive vehicle. Liquid-based damping systems are typically heat-dried, gelled, or reactive compositions applied to the surface of the substrate in a liquid state, for example, by spraying.

[0006] Acoustic damping materials used for panel and plate vibration damping can also be provided in the form of confined layer damping elements, which contain a damping layer and a rigid outer layer that "confines" the damping layer, thereby sandwiching it between the rigid outer layer and the surface of the substrate to be damped. The stiffness of the outer layer is typically ten times that of the damping material layer. Commonly used materials for the outer layer include, for example, aluminum and fiberglass fabric. Confined layer damping devices are generally more effective than single-layer damping elements in damping undesirable vibrations, but they are also more expensive to manufacture.

[0007] Cavity filler inserts are used to reduce airborne noise within the cavities of hollow structural components and to prevent vibrations from being transmitted through the cavity walls. Cavity filler inserts typically consist of a damping material and at least one connecting member capable of holding the insert in a desired position within the hollow structure. The damping material of the cavity filler insert is usually formulated as an expandable composition that expands upon activation, such as at elevated temperatures, and forms a seal around the inner surface of the cavity wall. Expandable damping materials suitable for damping airborne noise within cavities are often referred to as "sound baffles."

[0008] Materials commonly used in damping layers include highly filled compositions containing bitumen, elastomers or thermoplastic polymers, and varying amounts of additives such as plasticizers, processing aids, rheology modifiers, and desiccants. Fillers are added to these compositions to meet different design purposes. Some fillers are used to improve sound damping properties, while others are used to reduce the density of the material or to replace more expensive materials to reduce raw material costs. Typical fillers used in sound damping materials include inorganic fillers. Lightweight inorganic fillers, such as hollow ceramic spheres and hollow glass spheres, have been widely used to reduce the density of sound damping materials and ultimately their weight. A general drawback of existing sound damping materials is that they are composed entirely of non-renewable raw materials. Inorganic fillers, often, and especially lightweight inorganic fillers (which can constitute more than 35% by weight of the total weight of the sound damping material), are obtained through energy-intensive production processes that generate significant carbon dioxide emissions.

[0009] Therefore, new types of acoustic damping materials are needed, in which at least a portion of the raw materials are replaced by renewable raw materials. Furthermore, compared to existing damping materials, these new types of acoustic damping materials should exhibit similar or improved damping properties. Invention Overview

[0011] The object of the present invention is to provide an improved composition for damping undesirable vibrations and noise in the mechanical structure and components of manufactured articles.

[0012] The subject of this invention is an acoustic damping material as defined in claim 1.

[0013] Surprisingly, it has been found that cellulose-containing particles, such as wood particles, can be used as fillers in acoustic damping materials based on asphalt, elastomers, and thermoplastic polymers, replacing the use of inorganic fillers, particularly lightweight inorganic materials such as hollow ceramic spheres. Furthermore, it has been surprisingly found that acoustic damping materials in which at least a portion of the inorganic filler has been replaced by wood particles exhibit improved vibration and noise damping properties compared to existing acoustic damping materials containing only inorganic and / or synthetic organic fillers.

[0014] One of the advantages of the acoustic damping material of the present invention is that it exhibits high vibration damping performance defined by a loss coefficient over a wide temperature range, for example, between -30°C and 60°C, making it particularly suitable for use in vibration and noise damping of automotive structures and components.

[0015] Furthermore, it has been found that the acoustic damping material of the present invention provides a higher maximum loss coefficient and a wider temperature range with a loss coefficient greater than 0.1 compared to prior art acoustic damping materials containing only inorganic and / or synthetic organic fillers.

[0016] Another advantage of the acoustic damping material of the present invention is that by replacing at least part of the inorganic filler with renewable raw materials, not only are the acoustic damping properties improved, but the sustainability of the acoustic damping material is also improved, because the energy consumption and carbon dioxide emissions generated from the production of raw materials are significantly reduced.

[0017] Other aspects of the invention are set forth in the other independent claims. Preferred aspects of the invention are set forth in the dependent claims.

[0018] Brief description of the attached diagram

[0019] Figure 1 The cross-section of a vibration and noise damping element (1) is shown, comprising a damping layer (2) having a first surface (3) and a second surface (3') and an adhesive layer (4) covering the first surface (3) of the damping layer (2).

[0020] Figure 2 The cross-section of a vibration and noise damping element (1) is shown, comprising a damping layer (2) having a first surface (3) and a second surface (3'), an adhesive layer (4) covering the first surface (3) of the damping layer (2) and a limiting layer (5) covering the second surface (3') of the damping layer (2).

[0021] Figure 3 The cross-section of the vibration damping system is shown. The vibration damping system includes a substrate (6) having a noise emitting surface (7) and a vibration and noise damping element (1) including a damping layer (2) and an adhesive layer (4), wherein a first surface (3) of the damping layer (2) is bonded to the noise emitting surface (7) by the adhesive layer (4).

[0022] Figure 4 The cross-section of the vibration damping system is shown. The vibration damping system includes a substrate (6) having a noise emitting surface (7) and a vibration and noise damping element (1) including a damping layer (2), an adhesive layer (4) and a confining layer (5), wherein a first surface (3) of the damping layer (2) is bonded to the noise emitting surface (7) by the adhesive layer (4) and wherein the damping layer (2) is sandwiched between the adhesive layer (4) and the confining layer (5). Invention Details

[0024] The subject of this invention is a sound damping material, comprising:

[0025] a) Adhesive matrix, comprising,

[0026] a1) Asphalt component B or

[0027] a2) Polymer component P,

[0028] a3) At least one optional hydrocarbon resin HR,

[0029] a4) Any one of the following waxes W,

[0030] a5) Optional at least one plasticizer PL, and

[0031] b) Filler components, including:

[0032] b1) At least one solid particulate cellulose-containing filler FW and

[0033] b2) At least one optional solid particulate inorganic filler FM,

[0034] At least one of the solid granular cellulose-containing fillers FW has a median particle width (X). c,min )D 50 Within the range of 100-1000μm, preferably 115-850μm.

[0035] Substance names beginning with "poly" refer to substances that contain two or more functional groups per molecule that bear their names. For example, polyols are compounds having at least two hydroxyl groups. Polyethers are compounds having at least two ether groups.

[0036] The term "polymer" refers to a chemically homogeneous collection of macromolecules produced by a polymerization reaction (polymerization, addition polymerization, condensation polymerization), wherein the macromolecules differ in their degree of polymerization, molecular weight, and chain length. The term also includes derivatives of said collection of macromolecules produced by polymerization reactions, i.e., compounds obtained by reactions such as the addition or substitution of functional groups in a predetermined macromolecule, which may be chemically homogeneous or chemically heterogeneous.

[0037] The term "α-olefin" refers to an alpha-olefin with the molecular formula C60-1200. x H2 x An alpha-olefin (x corresponds to the number of carbon atoms) characterized by a carbon-carbon double bond at the first carbon atom (α-carbon). Examples of alpha-olefins include ethylene, propylene, 1-butene, 2-methyl-1-propene (isobutene), 1-pentene, 1-hexene, 1-heptene, and 1-octene. For example, according to this disclosure, 1,3-butadiene, 2-butene, or styrene are not referred to as "alpha-olefins".

[0038] The term "thermoplastic" refers to any material that can melt and resolidify with little or no change in its physical properties.

[0039] The term "elastomer" refers to any natural, synthetic, or modified high molecular weight polymer or combination of polymers that is capable of recovering from large deformations, i.e., possessing elastic properties. Typical rubber can be stretched or deformed to at least 200% of its original size under externally applied forces and will substantially return to its original size after the external force is released, thus maintaining only small permanent deformations (typically no more than about 20%). In particular, the term "elastomer" refers to uncrosslinked rubber. The term "chemically crosslinked" should be understood to mean that the polymer chains forming the elastomer are interconnected by multiple mechanically and thermally stable covalent bonds. The terms "rubber" and "elastomer" are used interchangeably in this document.

[0040] The term "molecular weight" refers to the molar mass (g / mol) of a molecule or a portion of a molecule (also called a "structural moiety"). The term "average molecular weight" refers to the number-average molecular weight (Maverage) of an oligomer or a mixture of polymers or structural moieties. n The molecular weight can be determined by conventional methods, preferably by gel permeation chromatography (GPC), using polystyrene as a standard, styrene-divinylbenzene gel with porosities of 100 Å, 1000 Å, and 10000 Å as a column, and tetrahydrofuran as a solvent at a temperature of 35 °C.

[0041] The term "glass transition temperature" (T) g The glass transition temperature (T0) refers to the temperature at which the polymer component becomes soft and flexible above a certain temperature, and hard and glassy below a certain temperature. g The peak of the loss modulus (G″) curve is preferably determined by dynamic mechanical analysis (DMA) using an applied frequency of 1 Hz and a strain level of 0.1%.

[0042] The term "softening point" refers to the temperature at which a compound softens to a rubbery state or the temperature at which the crystalline parts of the compound melt. The softening point can be determined by the ring and ball method according to DIN EN 1238.

[0043] The term "melting temperature" refers to the temperature at which a material undergoes a transition from a solid to a liquid state. The melting temperature (T0) is preferably determined by differential scanning calorimetry (DSC) according to ISO 11357 using a heating rate of 2 °C / min. m Measurements can be performed using a Mettler Toledo DSC 3+ device and T mThe value can be determined using DSC software based on the measured DSC curve. If the measured DSC curve shows several peak temperatures, the first peak temperature from the lower temperature side in the thermogram is taken as the melting temperature (T). m ).

[0044] The term "amount or content of at least one component X" in a composition, such as "amount of at least one thermoplastic polymer TP," refers to the sum of the individual amounts of all thermoplastic polymers TP contained in the composition. For example, if the composition contains 20% by weight of at least one thermoplastic polymer TP, then the sum of the amounts of all thermoplastic polymers P contained in the composition equals 20% by weight.

[0045] The term "room temperature" refers to a temperature of 23°C.

[0046] The acoustic damping material of this invention is particularly suitable for damping undesirable vibrations and noise in mechanical structures and components of manufactured articles such as automobiles, household appliances, or general industrial products. In these applications, the acoustic damping material, typically provided in the form of molded articles such as layers or pads, is applied directly to the surface of the mechanical structure or component subjected to vibration disturbance. The acoustic damping material can be formed into articles of suitable shape using conventional extrusion and / or calendering or hot pressing techniques. Due to the specific type and amount of components contained in the binder matrix a) and filler component b), the damping material maximizes the efficiency of dissipating the kinetic energy of the vibrating surface into heat energy through the stretching and compression of the damping material at various application temperatures.

[0047] Asphalt component B, polymer component P, and various additives including at least one hydrocarbon resin HR, at least one wax H, and at least one plasticizer PL (if present in the sound damping material) form a binder matrix for filler component b). There are no particular limitations on the proportion of the binder matrix in the sound damping material, but its amount should be high enough to effectively bind the components of the filler component and prevent the formation of an interconnected solid network of solid particulate compounds.

[0048] Preferably, the filler component b) accounts for at least 25% by weight, more preferably at least 35% by weight, and more preferably at least 45% by weight of the total weight of the acoustic damping material. According to one or more embodiments, the filler component b) accounts for 25-75% by weight, preferably 35-70% by weight, more preferably 40-70% by weight, even more preferably 45-70% by weight, and still more preferably 45-65% by weight of the total weight of the acoustic damping material.

[0049] According to one or more embodiments, the sum of the amounts of components a1) to a5), namely the sum of the amounts of asphalt component B, polymer component P, at least one hydrocarbon resin HR, at least one wax W, and at least one plasticizer PL (if present in the sound damping material), accounts for no more than 70% by weight, preferably no more than 65% by weight, and more preferably no more than 60% by weight of the total weight of the sound damping material. According to one or more embodiments, the sum of the amounts of components a1) to a5) accounts for 15-65% by weight, preferably 20-60% by weight, more preferably 20-55% by weight, even more preferably 25-50% by weight, and most preferably 25-45% by weight of the total weight of the sound damping material.

[0050] According to one or more embodiments, the acoustic damping material comprises:

[0051] b1) 1–35 wt%, preferably 2.5–30 wt%, more preferably 5–30 wt%, even more preferably 5–25 wt%, still more preferably 5–20 wt%, and most preferably 7.5–15 wt% of at least one solid particulate cellulose-containing filler FW, based on the total weight of the acoustic damping material. The term "solid particulate filler" in this document refers to filler present in the acoustic damping material in the form of solid particles. Preferably, the at least one solid particulate cellulose-containing filler FW consists of particles of cellulose-containing material.

[0052] At least one solid particulate cellulose-containing filler FW has a median particle width (X c,min )D 50 The median particle width (D) is within the range of 100–1000 μm, preferably 115–850 μm, more preferably 135–750 μm, even more preferably 150–650 μm, still more preferably 165–550 μm, and most preferably 175–450 μm. 50 "In this disclosure, it refers to a particle width such that 50% by volume of all particles below that particle width have a particle size less than D." 50 The width of the value. The term "particle width" in this disclosure refers to the diameter of the particle, which is the maximum chord (X) of the projection of a set of particles. c The shortest chord (X) in ) c,min Particle size distribution is preferably measured using a dynamic image analysis method according to ISO 13322-2:2006. To determine particle size distribution, it is preferable to disperse the particles in air, preferably using a pressure dispersion method. Measurements can be performed using any type of dynamic image analysis equipment, such as the Camsizer XT device (a trademark of Retsch Technology GmbH).

[0053] According to one or more embodiments, at least one solid particulate cellulose-containing filler FW has D 90 Particle width (X)c,min Within the range of 100–2000 μm, preferably 150–1500 μm, more preferably 150–1250 μm, and even more preferably 200–1000 μm and / or D 10 Particle width (X) c,min Within the range of 5–500 μm, preferably 25–350 μm, more preferably 35–300 μm, and even more preferably 50–250 μm. Term D 90 Particle width in this disclosure refers to a particle width such that 90% of all particles with a volume less than D have a particle width less than D. 90 The width of the value. Similarly, the term "D" 10 "Particle size" refers to the width of a particle such that 10% by volume of all particles smaller than this particle width have a particle size less than D. 10 Width of the value.

[0054] According to one or more embodiments, at least one solid granular cellulose-containing filler FW has an aspect ratio of not more than 10, preferably not more than 7.5, and more preferably not more than 5. According to one or more embodiments, the aspect ratio of at least one solid granular cellulose-containing filler FW is in the range of 1–10, preferably 1.25–7.5, more preferably 1.5–7.5, even more preferably 1.5–5, and still more preferably 1.5–4.5.

[0055] In this disclosure, the term "aspect ratio" for a particle refers to the value obtained by dividing the particle's length (L) by its thickness (T). The term "particle length" in this disclosure refers to the maximum Ferete diameter (X). Fe,max The term "Ferret diameter" refers to the longest Ferrett diameter among a set of measured Ferrett diameters. In this disclosure, "Ferret diameter" refers to the distance between two tangential planes on opposite sides of the particle, parallel to a fixed direction and perpendicular to the measurement direction. "Particle thickness" in this disclosure refers to the minimum Ferrett diameter (X). Fe,min The aspect ratio is the shortest Ferete diameter among a set of measured Ferete diameters. Therefore, the aspect ratio is calculated as X. Fe,max and X Fe,min The ratio.

[0056] The aspect ratio of particles can be determined by measuring the length and thickness of the particles using any suitable measurement technique, preferably by using a dynamic image analysis method according to ISO 13322-2:2006, and calculating the aspect ratio from the measured particle dimensions as described above. The particle dimensions can be measured using a dry dispersion method, preferably by using a pressure dispersion method, by dispersing the particles in air. Measurements can be performed using any type of dynamic image analysis equipment, such as the Camsizer XT device (a trademark of RetschTechnology GmbH).

[0057] According to one or more embodiments, at least one solid particulate cellulose-containing filler FW has a number-average aspect ratio of not more than 10, preferably not more than 7.5, and more preferably not more than 5. According to one or more other embodiments, at least one solid particulate cellulose-containing filler FW has a number-average aspect ratio in the range of 1–10, preferably 1.25–7.5, more preferably 1.5–7.5, even more preferably 1.5–5, and still more preferably 1.5–4.5.

[0058] The term "number-mean aspect ratio" in this disclosure refers to the arithmetic mean of the individual aspect ratios of particles within a sample or collection, or a statistically significant and representative random sample drawn from such a sample or collection. The number-mean aspect ratio of particulate materials can be determined by measuring the size of each particle in the sample using any suitable measurement technique, preferably by using a dynamic image analysis method according to ISO 13322-2:2006, and calculating the number-mean aspect ratio from the measured size of each particle as described above.

[0059] According to one or more embodiments, at least one solid particulate cellulose-containing filler (FW) has a median aspect ratio of not more than 10, preferably not more than 7.5, and more preferably not more than 5. According to one or more other embodiments, at least one solid particulate cellulose-containing filler (FW) has a median aspect ratio in the range of 1–10, preferably 1.25–7.5, more preferably 1.5–7.5, even more preferably 1.5–5, and still more preferably 1.5–4.5.

[0060] The term "median aspect ratio" in this disclosure refers to the median length L of the particle. 50 With median thickness T 50 The ratio. The term "median length L" 50 "This refers to a value below which 50% by volume of all particles have a content less than L." 50 The maximum value of the Feret diameter, while the term "median thickness T" refers to the maximum value of the diameter. 50 This refers to a value below which 50% by volume of all particles have a thickness less than the median value T. 50 The minimum Freret diameter.

[0061] According to one or more embodiments, at least one solid particulate cellulose-containing filler FW has a true particulate density of 0.25–1.5 g / cm³. 3 Preferred concentration: 0.30–1.25 g / cm³ 3 More preferably 0.35–1.0 g / cm³ 3 Even more preferred is 0.40–1.0 g / cm³. 3 Even more preferred is 0.45–0.85 g / cm³. 3 The optimal value is 0.50–0.75 g / cm³.3 Within the range of [specific ranges]. The term "true particle density" in this disclosure refers to the actual density of the particles that make up the granular material. In contrast, the term "bulk density" refers to the mass of the granular material per unit volume (including the voids between particles).

[0062] According to one or more embodiments, at least one solid particulate cellulose-containing filler (FW) has a true solid density of 1.00–2.00 g / cm³. 3 Preferred concentration: 1.25–1.85 g / cm³ 3 More preferably 1.35–1.75 g / cm³ 3 Even more preferred is 1.40–1.70 g / cm³. 3 Even better, 1.40–1.65 g / cm³ 3 Within the range.

[0063] The term "true solid density" refers to the "skeletal density" of a material, calculated as the ratio of the mass of the particles to the volume occupied by that mass, where the contribution of pores or internal voids is subtracted from the volume when calculating the true solid density. The true solid density of particles is preferably determined by measuring with a helium hydrometer.

[0064] According to one or more embodiments, at least one solid particulate cellulose filler FW contains at least 25% by weight, preferably at least 35% by weight, more preferably at least 40% by weight of cellulose.

[0065] According to one or more embodiments, at least one solid granular cellulose-containing filler (FW) is composed of wood particles. The term "wood particle" refers to particles composed of wood fibers. The length dimension of the wood particle is generally parallel to the grain structure orientation of the wood particle, that is, parallel to the orientation of the long axis of the main fibers in the wood particle.

[0066] Suitable wood particles for use as at least one solid granular cellulose-containing filler include, for example, all types of softwood and hardwood particles, especially hardwood particles.

[0067] The term "softwood" refers to wood from coniferous trees, specifically needle-like trees of the order Pinales. Trees that produce softwood include, for example, pine, spruce, cedar, fir, larch, Douglas fir, hemlock, cypress, redwood, and yew. Conversely, the term "hardwood" refers to wood from broad-leaved or angiosperm trees, such as eucalyptus, maple, birch, beech, and poplar. Softwood contains two types of cells: longitudinal lignin fibers (or tracheids) and transverse ray cells, while hardwood trees contain stomata or vessels. In softwood, water transport occurs via tracheids, not stomata as in hardwood.

[0068] According to one or more embodiments, at least one solid granular cellulose filler FW comprises or is composed of hardwood particles, preferably selected from wood particles of eucalyptus, maple, birch, beech and poplar.

[0069] According to one or more embodiments, at least one solid particulate cellulose filler FW contains at least 15% by weight, preferably at least 35% by weight, more preferably at least 50% by weight, even more preferably at least 75% by weight, even more preferably at least 85% by weight, and most preferably at least 95% by weight of hardwood particles, preferably selected from wood particles of eucalyptus, maple, birch, beech and poplar.

[0070] According to one or more embodiments, at least one solid particulate cellulose-containing filler FW comprises:

[0071] b11) at least one first solid particulate cellulose-containing filler FW1 and

[0072] b12) At least one second solid particulate cellulose-containing filler FW2, wherein at least one first solid particulate cellulose-containing filler FW1 has a median particle width (X) c,min )D 50 The median particle width (X) of at least one second solid granular cellulose-containing filler FW2 c,min )D 50 At least 5%, preferably at least 15%, and more preferably at least 25%.

[0073] According to one or more embodiments, the median particle width (X) of at least one first solid particulate cellulose-containing filler FW1 is... c,min )D 50 The median particle width (X) of at least one second solid granular cellulose-containing filler FW2 c,min )D 50 The percentage should be no more than 90%, preferably no more than 80%, and even more preferably no more than 70%.

[0074] According to one or more embodiments, at least one first solid particulate cellulose-containing filler FW1 has a median particle width (X). c,min )D 50 Within the range of 100–500 μm, preferably 115–350 μm, more preferably 125–300 μm and / or at least one second solid particulate cellulose-containing filler FW2 has a median particle width (X). c,min )D 50 It is in the range of 150–1000 μm, preferably 200–750 μm, and more preferably 250–500 μm.

[0075] According to one or more embodiments, the weight ratio of at least one first solid particulate cellulose-containing filler FW1 to at least one second solid particulate cellulose-containing filler FW2 in the acoustic damping material is in the range of 5:1 to 1:5, preferably 3:1 to 1:3, more preferably 2:1 to 1:2, even more preferably 1.5:1 to 1:1.5, and even more preferably 1.25:1 to 1:1.25.

[0076] According to one or more embodiments, at least one first solid granular cellulose-containing filler FW1 is composed of beech or birch wood particles or a mixture of beech and birch wood particles and / or a second solid granular cellulose-containing filler FW2 is composed of beech or birch wood particles or a mixture of beech and birch wood particles.

[0077] According to one or more embodiments, the acoustic damping material comprises:

[0078] b1) 5–75 wt%, preferably 15–70 wt%, more preferably 25–65 wt%, even more preferably 35–65 wt%, and still more preferably 40–65 wt% of at least one solid particulate inorganic filler FM, based on the total weight of the acoustic damping material.

[0079] At least one solid particulate inorganic filler FM preferably exists in the sound damping material in the form of solid particles, and preferably has d 90 The particle diameter is no greater than 2.5 mm, more preferably no greater than 1.5 mm. The term "particle diameter d" is used in this context. 90 "In this disclosure, it refers to a particle diameter such that 90% of the volume of all particles below that diameter have a diameter less than d." 90 The diameter of the particle. The term "particle diameter" in this disclosure refers to the equivalent area sphere diameter (Xi) of the particle. 面积 The particle diameter distribution is preferably measured using a dynamic image analysis method according to ISO 13322-2:2006. To determine the particle diameter distribution, the particles are preferably dispersed in air, preferably using a pressure dispersion method. Measurements can be performed using any type of dynamic image analysis equipment, such as the Camsizer XT device (a trademark of Retsch Technology GmbH).

[0080] Preferably, at least one solid particulate inorganic filler FM is an inert inorganic filler and has a water solubility of less than 0.1 g / 100 g water at a temperature of 20°C, more preferably less than 0.05 g / 100 g water, and even more preferably less than 0.01 g / 100 g water. The solubility of the compound in water can be measured as the saturation concentration, at which point adding more compound does not increase the concentration of the solution, i.e., excess substance begins to precipitate. The term "inert inorganic filler" in this disclosure refers to an inorganic filler that, unlike inorganic binders, is non-reactive, i.e., does not undergo hydrolysis in the presence of water.

[0081] According to one or more embodiments, at least one solid particulate inorganic filler FM is selected from the following: calcium carbonate, magnesium carbonate, talc, kaolin, diatomaceous earth, wollastonite, feldspar, montmorillonite, dolomite, silica, cristobalite, iron oxide, nickel iron oxide, strontium ferrite, barium strontium ferrite, hollow ceramic spheres, hollow glass spheres, hollow organic spheres, glass spheres, mica, barium sulfate, and graphite.

[0082] According to one or more embodiments, the acoustic damping material is substantially free of hollow ceramic spheres, preferably substantially free of hollow ceramic spheres, hollow glass spheres, hollow organic spheres, and glass spheres. The term "substantially free of" should be understood to mean that the amount of the inorganic fillers listed above is no more than 0.5% by weight, preferably no more than 0.25% by weight, more preferably no more than 0.1% by weight, even more preferably no more than 0.05% by weight, and still more preferably 0% by weight, based on the total weight of the acoustic damping material.

[0083] Preferably, the acoustic damping material contains several different inorganic fillers, such as at least two different inorganic fillers. Some inorganic fillers can be used, for example, to improve the acoustic damping properties of the acoustic damping material, while others can be used to enable the acoustic damping material to adhere to a metal substrate by magnetic force.

[0084] According to one or more embodiments, at least one solid particulate inorganic filler FM comprises:

[0085] b21) at least one first solid particulate inorganic filler FM1 and

[0086] b22) At least one second solid particulate inorganic filler FM2 that is different from at least one first solid particulate inorganic filler FM1.

[0087] According to one or more embodiments, at least one first solid particulate inorganic filler FM1 has a median particle diameter d. 50 The particle size is in the range of 1–75 μm, preferably 2.5–50 μm, and / or the true particle density is at least 1.5 g / cm³. 3 Preferably at least 2.0 g / cm³ 3And / or the average aspect ratio is not greater than 2.5, preferably not greater than 2.0 and / or at least one second solid particulate inorganic filler FM2 has a median particle diameter d. 50 The particle size is at least 50 μm, preferably at least 100 μm, and / or the true particle density is at least 1.5 g / cm³. 3 Preferably at least 2.0 g / cm³ 3 And / or the average aspect ratio is at least 2.0, preferably at least 3.0. The term "median particle diameter d" is used. 50 "In this disclosure, it refers to a particle diameter such that 50% by volume of all particles below that diameter have a diameter less than d." 50 The diameter of the value.

[0088] According to one or more embodiments, at least one first solid particulate inorganic filler FM1 is selected from the following: calcium carbonate, magnesium carbonate, talc, kaolin, diatomaceous earth, wollastonite, feldspar, montmorillonite, dolomite, silica, cristobalite, iron oxide, nickel iron oxide, strontium ferrite, barium strontium ferrite, and synthetic organic fillers.

[0089] According to one or more embodiments, at least one second solid particulate inorganic filler FM2 is selected from the following: mica, montmorillonite, slate, barium sulfate, and graphite.

[0090] The term "hydrocarbon resin" in this document refers to synthetic resins made by polymerizing a mixture of unsaturated monomers obtained from petroleum-based feedstocks (such as byproducts of cracking natural gas liquids, gas oils, or petroleum naphtha). These types of hydrocarbon resins are also referred to as "petroleum resins" or "petroleum hydrocarbon resins." Hydrocarbon resins also include pure monomeric aromatic resins prepared by polymerizing aromatic monomer feedstocks that have been purified to eliminate color-causing contaminants and thus precisely control the product composition.

[0091] Examples of suitable hydrocarbon resins to be used as at least one hydrocarbon resin HR include C5 aliphatic resins, mixed C5 / C9 aliphatic / aromatic resins, aromatically modified C5 aliphatic resins, cycloaliphatic resins, mixed C5 aliphatic / cycloaliphatic resins, mixed C9 aromatic / cycloaliphatic resins, mixed C5 aliphatic / cycloaliphatic / C9 aromatic resins, aromatically modified cycloaliphatic resins, C9 aromatic resins, and hydrogenated forms of the aforementioned resins. The designations “C5” and “C9” indicate that the monomers used to make the resin are primarily hydrocarbons having 4-6 and 8-10 carbon atoms, respectively. The term “hydrogenated” includes fully, substantially, and at least partially hydrogenated resins. Partially hydrogenated resins may have, for example, hydrogenation levels of 50%, 70%, or 90%.

[0092] This invention does not particularly limit the type of at least one hydrocarbon resin HR. The selection of at least one hydrocarbon resin HR depends at least in part on the type of other components contained in the adhesive matrix of the acoustic damping material, particularly the type of polymer component P.

[0093] According to one or more embodiments, at least one hydrocarbon resin HR has:

[0094] - The softening point, as determined by the ring and ball method as defined in DIN EN 1238, is at least 70°C, preferably at least 80°C, more preferably in the range of 70–180°C, preferably 80–170°C, more preferably 100–160°C, and / or

[0095] -Average molecular weight (M n Within the range of 250–7500 g / mol, preferably 300–5000 g / mol and / or

[0096] - Glass transition temperature (T) g The peak of the loss modulus (G″) curve is determined by dynamic mechanical analysis (DMA) at a temperature equal to or higher than 0°C, preferably equal to or higher than 15°C, more preferably equal to or higher than 35°C, even more preferably equal to or higher than 55°C, even more preferably equal to or higher than 65°C, and most preferably equal to or higher than 75°C.

[0097] Suitable hydrocarbon resins can be, for example, by trade name series, Plus Extra and STS (all from Cray Valley); by product name 1000 series 2000 series and 5000 series (all from Exxon Mobil Chemical); by product name T series, TT series TD series TL series TN series TK series and TV series (all from) Novares GmbH); and under the trade name and (All from Eastman Chemicals) Commercially available.

[0098] In this document, the term "wax" refers to a substance that has a waxy consistency and a melting temperature or melting temperature range greater than normal room temperature, particularly greater than 25°C.

[0099] Suitable waxes for use as at least one type of wax include, in particular, synthetic waxes such as petroleum waxes, such as paraffin wax, petrolatum and microcrystalline waxes, polyolefin waxes, polyethylene glycol waxes (Carbowax), amide waxes and chemically modified waxes such as hardened or hydrogenated waxes, such as lignite waxes.

[0100] According to one or more embodiments, at least one wax is selected from the following: polyolefin wax, paraffin wax, microcrystalline wax and amide wax.

[0101] According to one or more embodiments, at least one wax W has:

[0102] - The softening point, determined by the ring and ball method as defined in DIN EN 1238, is within the range of 75–180°C, preferably 80–160°C, more preferably 85–140°C, and / or

[0103] - The melt viscosity, as determined according to DIN 53019 at a temperature of 170°C, is in the range of 10–10000 mPa·s, preferably 100 to 5000 mPa·s, and more preferably 500–3500 mPa·s. The melt viscosity can be determined by using a rotational viscometer at 5 revolutions per minute, for example, using a Brookfield DV-2 Thermosel viscometer with a No. 27 rotor.

[0104] According to one or more embodiments, at least one wax is a polyolefin wax. The term "polyolefin wax" in this document refers to a wax having 2-30 carbon atoms and a number-average molecular weight (M). n Low molecular weight polymers of linear or branched α-olefins in the range of 5000-25000 g / mol. These include homopolymers and copolymers of the linear or branched α-olefins mentioned above. Polyolefin waxes can be obtained by thermal decomposition of polyolefin plastics, particularly polyethylene plastics, or by direct polymerization of olefins. Suitable polymerization methods include, for example, radical methods in which olefins such as ethylene react under high pressure and temperature to produce waxes that are more or less branched, and methods in which organometallic catalysts such as Ziegler-Natta or metallocene catalysts are used to polymerize ethylene and / or higher α-olefins (especially propylene) to produce unbranched or branched waxes. Polyolefin waxes typically have a structure that is at least partially crystalline.

[0105] According to one or more embodiments, at least one wax W is paraffin, preferably Fischer-Tropsch wax. The term "paraffin" in this disclosure refers to a hard, crystalline wax consisting primarily of saturated alkanes. Paraffins are typically obtained from petroleum distillates or derived from mixed-base or paraffin-based mineral oils.

[0106] According to one or more embodiments, at least one wax W is an amide wax. The term "amide wax" in this document refers to a wax containing an amide bond (–CONH–) in the molecule and an amide group (–CONH2) at the end of the molecule. According to one or more embodiments, at least one wax W is an amide wax selected from the following: N,N'-ethylenebis(stearamide), stearamide, N,N'-methylenebis(stearamide), and hydroxymethylstearamide.

[0107] According to the first preferred embodiment, the adhesive matrix a) of the acoustic damping material comprises:

[0108] a1) 25–65 wt%, preferably 35–55 wt%, of asphalt component B.

[0109] a3) 0–10% by weight, preferably 0.25–5% by weight, of at least one hydrocarbon resin HR, and

[0110] a4) 0–10% by weight, preferably 0.25–7.5% by weight, of at least one wax W, all proportions based on the total weight of the acoustic damping material.

[0111] The acoustic damping material according to the first preferred embodiment can be characterized as "asphalt-based damping material".

[0112] The term "bitumen" in this disclosure refers to a blend of heavy hydrocarbons having a solid consistency at room temperature. These are often obtained as vacuum residue from refining processes, which may be distillation (topping or vacuum) and / or conversion processes, such as thermal cracking and viscous cracking of suitable crude oil. Furthermore, the term "bitumen" also refers to natural and synthetic bitumen, as well as asphaltic materials obtained from the extraction of tar and bitumen sands.

[0113] Asphalt component B may contain one or more different types of asphalt materials, such as penetration grade (distilled) asphalt, air-distilled (semi-blown) asphalt, and hard grade asphalt.

[0114] The term "penetration grade bitumen" refers here to bitumen obtained from the fractionation of crude oil. Heavy fractions consisting of high molecular weight hydrocarbons (also known as atmospheric residue), obtained after removing gasoline, kerosene, and gas oil fractions, are first distilled in a vacuum distillation column to produce more gas oil, distillate, and vacuum residue. The vacuum residue is then used as feedstock to produce different grades of bitumen classified by their penetration index, typically defined by the PEN value, which is the distance a needle can penetrate the bitumen in ten millimeters (dmm) under standard testing methods. Penetration grade bitumen is characterized by penetration and softening point. The term "air-refined bitumen" or "air-distilled bitumen" in this disclosure refers to bitumen that has undergone mild oxidation with the aim of producing bitumen that meets the requirements for paving grade bitumen. The term "hard grade bitumen" in this disclosure refers to bitumen produced from propane-precipitated bitumen using extended vacuum distillation and some air distillation. Hard bitumen typically has a low penetration value and a high softening point.

[0115] According to one or more embodiments, asphalt component B comprises at least 75% by weight, preferably at least 85% by weight, more preferably at least 90% by weight, of at least one penetration grade of asphalt, preferably having a penetration value in the range of 15-50 dmm, more preferably 20-45 dmm and / or a softening point in the range of 40-125°C, preferably 50-100°C, as determined by ring and globe measurements according to DIN EN 1238.

[0116] In the case of asphalt-based damping materials, the sound damping material preferably further comprises a modified polymer MP for at least one asphalt component B.

[0117] Suitable polymers for use as at least one modified polymer MP include, for example, atactic polypropylene (APP), amorphous polyolefins (APO), styrene block copolymers, and elastomers. The term "amorphous polyolefin" refers to a polyolefin having a low crystallinity, as determined by differential scanning calorimetry (DSC), for example, in the range of 0.001-10 wt%, preferably 0.001-5 wt%. The crystallinity of a polymer can be determined by measuring the heat of fusion using differential scanning calorimetry according to ISO 11357, thereby calculating the crystallinity. In particular, the term "amorphous polyolefin" refers to a polyolefin that has no crystallization melting point (T0) as determined by differential scanning calorimetry (DSC) or equivalent techniques. m ) of polyα-olefins.

[0118] Suitable amorphous polyolefins for use as at least one modified polymer MP include, for example, atactic polypropylene, propylene-rich copolymers of amorphous propylene and ethylene, propylene-rich copolymers of amorphous propylene and butene, propylene-rich copolymers of amorphous propylene and hexene, and propylene-rich terpolymers of amorphous propylene, ethylene, and butene. The term "propylene-rich" should be understood to mean copolymers and terpolymers having a content of at least 50% by weight, preferably at least 65% by weight, and more preferably at least 70% by weight of propylene-derived units, based on the total weight of the copolymer / terpolymer.

[0119] Suitable styrene block copolymers for use as at least one modified polymer MP include, in particular, block copolymers of the SXS type, where S represents a non-elastomeric styrene (or polypropylene) block and X represents an elastomeric α-olefin block, which can be polybutadiene, polyisoprene, polyisoprene-polybutadiene, fully or partially hydrogenated polyisoprene (polyethylene-propylene), or fully or partially hydrogenated polybutadiene (polyethylene-butene). The elastomeric α-olefin block preferably has a glass transition temperature in the range of -55°C to -35°C. The elastomeric α-olefin block can also be a chemically modified α-olefin block. Particularly suitable chemically modified α-olefin blocks include, for example, maleic acid-grafted α-olefin blocks and, particularly, maleic acid-grafted ethylene-butene blocks. Preferred styrene block copolymers for use as at least one modified polymer MP include SBS, SIS, SIBS, SEBS, and SEPS block copolymers, especially SBS block copolymers, preferably having a linear, radial, diblock, triblock, or star structure.

[0120] Suitable elastomers for use as at least one modified polymer MP include, for example, styrene-butadiene rubber (SBR), ethylene propylene diene monomer rubber (EPDM), polyisoprene, polybutadiene, natural rubber, chloroprene rubber, ethylene-propylene rubber (EPR), nitrile rubber and acrylic rubber.

[0121] According to one or more embodiments, at least one modified polymer MP is selected from atactic polypropylene (APP), amorphous polyolefin (APO), styrene block copolymer, styrene-butadiene rubber (SBR), ethylene propylene diene monomer rubber (EPDM), polyisoprene, polybutadiene, natural rubber, chloroprene rubber, ethylene-propylene rubber (EPR), nitrile rubber and acrylic rubber.

[0122] According to one or more embodiments, at least one modified polymer MP accounts for 0.5-10% by weight, preferably 1-7.5% by weight, of the total weight of the acoustic damping material.

[0123] In the case of asphalt-based damping materials, it is preferable that the acoustic damping material is substantially free of crosslinking / curing agents, such as free radical crosslinking agents like peroxides. The phrase "substantially free of" is intended to mean that if a crosslinking agent is found in the acoustic damping material, the amount is negligible, such that the effect of the crosslinking agent is not achieved. In other words, the amount of crosslinking agent found in the acoustic damping material is insufficient to induce curing of the polymer components, particularly at least one modified polymer MP, or may only induce a substantially negligible amount of crosslinking. According to one or more embodiments, the acoustic damping material contains less than 0.15% by weight, preferably less than 0.1% by weight, more preferably less than 0.01% by weight, and even more preferably 0% by weight of crosslinking / curing agent, based on the total weight of the acoustic damping material.

[0124] According to the second preferred embodiment, the adhesive matrix a) of the acoustic damping material comprises:

[0125] a2) 0.5–25% by weight, preferably 1.5–20% by weight, of polymeric component P containing at least one thermoplastic polymer TP.

[0126] a3) 2.5–35 wt%, preferably 5–30 wt%, of at least one hydrocarbon resin HR,

[0127] a4) 0–15% by weight, preferably 0.5–10% by weight, of at least one wax W, and

[0128] a5) 0–30 wt%, preferably 0.5–15 wt%, of at least one plasticizer PL, all proportions based on the total weight of the acoustic damping material.

[0129] The acoustic damping material according to the second preferred embodiment can be characterized as "a thermoplastic damping material without bitumen".

[0130] In the case of asphalt-free thermoplastic damping materials, polymer component P comprises at least one thermoplastic polymer TP, and a portion of asphalt component B in the adhesive matrix a) is replaced by a specific combination of at least one thermoplastic polymer TP, at least one hydrocarbon resin HR, at least one wax W, and at least one plasticizer PL optionally added to the adhesive matrix a). It has been found that using such an adhesive matrix can provide asphalt-free thermoplastic damping materials that can be processed into molded articles using conventional thermoplastic processing methods such as extrusion, calendering, injection molding, and hot pressing techniques.

[0131] According to one or more embodiments, the asphalt-free thermoplastic damping material contains less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.1% by weight, and even more preferably less than 0.01% by weight of asphalt, based on the total weight of the asphalt-free thermoplastic damping material.

[0132] The composition of the polymer component P of the thermoplastic damping material that does not contain asphalt is preferably selected such that the temperature range in which the damping material has the maximum vibration damping effect during its use is consistent with the temperature range experienced by the surface of the substrate to be damped.

[0133] Because the polymer's ability to dissipate vibrational energy as heat is greatest when it is in the transition state between a hard / glassy and a soft / rubbery state, the preferred thermoplastic polymer for use in asphalt-free thermoplastic damping materials has a glass transition temperature (T0). g The temperature falls within the expected range of the application temperature. For example, if a non-asphalt thermoplastic damping material is used for vibration and noise damping in the structure of an automotive vehicle, the application temperature range is typically -40°C to 60°C, particularly -35°C to 50°C. On the other hand, the preferred thermoplastic polymer TP to be used in the polymer component P has a softening point (T). s ) and / or melting temperature (T m () Greater than the maximum application temperature of thermoplastic damping materials without asphalt.

[0134] According to one or more embodiments, at least one thermoplastic polymer TP has:

[0135] - Glass transition temperature (T) g The temperature is less than 25°C, preferably less than 5°C, more preferably less than 0°C, and the peak and / or value of the loss modulus (G″) curve measured by dynamic mechanical analysis (DMA) using an applied frequency of 1 Hz and a strain level of 0.1% is determined.

[0136] - Softening point (T) determined by the ring and globe method according to DIN EN 1238 standard. s The temperature is greater than 35°C, preferably greater than 45°C, more preferably greater than 55°C, for example, in the range of 35–250°C, preferably 45–200°C, more preferably 55–180°C.

[0137] According to one or more embodiments, polymer component P is composed of at least one thermoplastic polymer TP.

[0138] There is no particular limitation on the type of at least one thermoplastic polymer TP. Various types of thermoplastic polymers, including crystalline, semi-crystalline and amorphous polymers and thermoplastic elastomers, are suitable for use as at least one thermoplastic polymer TP. According to one or more embodiments, at least one thermoplastic polymer TP is selected from the following: polyolefin homopolymers and copolymers, copolymers of ethylene and vinyl acetate, and thermoplastic olefin elastomers (TPE-O).

[0139] Suitable polyolefin homopolymers and copolymers include, for example, ethylene homopolymers, ethylene-α-olefin copolymers, propylene homopolymers, and propylene-α-olefin copolymers.

[0140] Suitable ethylene-α-olefin copolymers include, for example, ethylene and one or more C3-C... 20 α-olefin copolymers, particularly ethylene-α-olefin random and block copolymers of one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene and 1-hexadecene, preferably containing at least 50% by weight, more preferably at least 60% by weight, of ethylene-derived units, based on the total weight of the copolymer.

[0141] Suitable propylene-α-olefin copolymers include propylene-ethylene random copolymers and propylene and one or more C4-C... 20 α-olefin copolymers, particularly propylene-α-olefin random and block copolymers of one or more of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene and 1-hexadecene, preferably containing at least 50% by weight, more preferably at least 60% by weight, of propylene-derived units, based on the total weight of the copolymer.

[0142] Suitable copolymers of ethylene and vinyl acetate include those having structural units derived from vinyl acetate in a content ranging from 4 to 90% by weight, particularly 4 to 80% by weight, based on the total weight of the copolymer. Suitable copolymers of ethylene and vinyl acetate can be, for example, in the form of... The product name (from Exxon Mobil), with The product name (from Repsol Quimica SA) and The product name (from Arkema Functional Polyolefins) was commercially available.

[0143] Suitable ethylene-α-olefin copolymers include, for example, ethylene-based polyolefin elastomers (POE), which can be, for example, in... Product name, for example 7256 7467、 7447、 8003 8100 8480 8540 8440 8450 8452, 8200 and 8414 (all from Dow Chemical Company) was purchased commercially.

[0144] Other suitable ethylene-α-olefin copolymers include, for example, ethylene-based elastomers, which can be, for example, made of... Product name, for example EG 8100G, EG 8200G, SL 8110G, KC 8852G, VP 8770G and PF 1140G (all from Dow Chemical Company) and Product name, for example 3024 3027 3128、 3131、 4049、 4053 5371 and 8203 (all from Exxon Mobil) were purchased commercially.

[0145] Other suitable ethylene-α-olefin copolymers include ethylene-α-olefin block copolymers, such as ethylene-based olefin block copolymers (OBCs), which can, for example, be... Product name, for example 9100 9107 9500 9507 and 9530 (all from Dow Chemical Company) were purchased commercially.

[0146] Suitable propylene-α-olefin copolymers include, for example, propylene-based elastomers (PBE) and propylene-based elastomers (PBP), which can, for example, be... The product name (from Dow Chemical Company) and The product name (from Exxon Mobil) was purchased from a retailer.

[0147] Other suitable polyolefin homopolymers and copolymers include amorphous polyalphaolefins that are solid at 25°C. These can be, for example, as... The product name (from Evonik Industries), The product name (from Eastman Corporation) and The product name (from REXtac LLC) was purchased commercially.

[0148] Thermoplastic olefin elastomers (TPE-O), also known as thermoplastic polyolefins (TPO), are also suitable for use as at least one thermoplastic polymer TP. TPO is a multiphase polyolefin composition containing a highly crystalline base polyolefin and a low-crystallinity or amorphous polyolefin modifier. The multiphase morphology consists of a matrix phase primarily composed of the base polyolefin and a dispersed phase primarily composed of the polyolefin modifier. Commercially available TPOs include reactor blends of the base polyolefin and the polyolefin modifier, also known as “in-situ TPO” or “impact copolymer (ICP)”, as well as physical blends of the aforementioned components. In the case of reactor blend type TPOs, the components are typically produced in a sequential polymerization process, wherein the matrix phase component is produced in a first reactor and transferred to a second reactor, where the dispersed phase component is produced and incorporated into the matrix phase as a structural domain. Physical blend type TPOs are produced by melt-blending the base polyolefin with the polyolefin modifier (each of which is formed separately prior to blending the components).

[0149] Reactor blends of TPO containing polypropylene as the base polymer are often referred to as "multiphase propylene copolymers," while reactor blends of TPO containing random copolymers of polypropylene as the base polymer are often referred to as "multiphase propylene random copolymers." Depending on the amount of polyolefin modifier, commercially available multiphase propylene copolymers are typically characterized as "impact copolymers" (ICP), "reactor-TPO," or "soft-TPO." The main difference between these types of TPO is that the amount of polyolefin modifier is generally lower in ICP than in reactor-TPO and soft-TPO, for example, no more than 40% by weight, and particularly no more than 35% by weight. As a result, compared to reactor-TPO and soft-TPO, typical ICP tends to have a lower xylene cold solubles (XCS) content as determined according to ISO 16152:2005 and a higher flexural modulus as determined according to ISO 178:2010.

[0150] A suitable TPO can be, for example, and Product names (all from Lyondell Basell) for example CA 10A CA 12A and CA 212A and The product name (from Borealis Polymers) for example I purchased the SD233CF commercially.

[0151] In acoustic damping applications, it is generally desirable to maximize the temperature range over which the vibration and noise damping effect of the damping material is greatest, particularly given that the measured loss coefficient of the damping material has a wide temperature range with a value greater than 0.1. Because the maximum vibration damping effect of thermoplastic polymers typically occurs within a narrow temperature range, i.e., when the polymer is in its transition state, it is preferable to use asphalt-free thermoplastic damping materials containing at least two materials with different glass transition temperatures (T0). g Different thermoplastic polymers.

[0152] Furthermore, it is advantageous for at least two different thermoplastic polymers to be incompletely miscible with each other and / or for at least two different thermoplastic polymers to be mixable to form a semi-compatible polymer blend containing a micro-incompatible phase. "Completely miscible" means that the polymer blend composed of at least two thermoplastic polymers has a negative Giggs free energy and heat of mixing. Polymer blends composed of completely miscible polymers tend to have a single glass transition temperature (T0) as measured by dynamic mechanical analysis (DMA). g ).

[0153] According to one or more embodiments, at least one thermoplastic polymer TP comprises:

[0154] a21) At least one rigid thermoplastic polymer TP1, preferably at least one rigid ethylene vinyl acetate copolymer, having a melt flow index (MFI) of not more than 50 g / 10 min, preferably not more than 35 g / 10 min, more preferably not more than 25 g / 10 min, even more preferably not more than 15 g / 10 min, and still more preferably not more than 10 g / 10 min as determined according to ISO 1133 (190 °C / 2.16 kg), and / or having a glass transition temperature (T0). g The peak and / or value of the loss modulus (G”) curve, measured by dynamic mechanical analysis (DMA) at a temperature less than 5°C, preferably less than 0°C, more preferably less than -10°C, and even more preferably less than -20°C, is determined to be less than 5°C, preferably less than 0°C, more preferably less than -10°C, and even more preferably less than -20°C.

[0155] a22) At least one soft thermoplastic polymer TP2, preferably at least one soft ethylene vinyl acetate copolymer, having a melt flow index (MFI) of at least 75 g / 10 min, preferably at least 100 g / 10 min, more preferably at least 150 g / 10 min, even more preferably at least 200 g / 10 min, most preferably at least 250 g / 10 min, as determined according to ISO 1133 (190 °C / 2.16 kg), and / or having a glass transition temperature (T0). gThe peak of the loss modulus (G”) curve is determined by dynamic mechanical analysis (DMA) at a temperature less than 5°C, preferably less than -0°C, more preferably less than -10°C, and even more preferably less than -20°C, using an applied frequency of 1 Hz and a strain level of 0.1%.

[0156] Generally, the statement "at least one component X comprises at least one component XN", such as "at least one thermoplastic polymer TP comprises at least one rigid thermoplastic polymer TP1", should be understood in the context of this disclosure to mean that a non-asphalt thermoplastic damping material comprises one or more rigid thermoplastic polymers TP1 as a representative of at least one thermoplastic polymer TP.

[0157] According to one or more embodiments, at least one thermoplastic polymer TP further comprises:

[0158] a23) At least one polyolefin TP3, wherein the at least one polyolefin TP3 is preferably not completely miscible with at least one hard thermoplastic polymer TP1 and / or with at least one soft thermoplastic polymer TP2.

[0159] According to one or more embodiments, at least one thermoplastic polymer TP comprises at least one rigid thermoplastic polymer TP1 and at least one polyolefin TP3.

[0160] According to one or more embodiments, at least one thermoplastic polymer TP comprises at least one soft thermoplastic polymer TP2 and at least one polyolefin TP3.

[0161] According to one or more other embodiments, at least one thermoplastic polymer TP comprises at least one hard thermoplastic polymer TP1, at least one soft thermoplastic polymer TP2, and at least one polyolefin TP3.

[0162] According to one or more embodiments, at least one rigid thermoplastic polymer TP1 is an ethylene vinyl acetate copolymer having a content of no more than 20% by weight, preferably no more than 15% by weight, of structural units derived from vinyl acetate, based on the total weight of the copolymer and / or at least one soft thermoplastic polymer TP2 is an ethylene vinyl acetate copolymer having a content of at least 15% by weight, preferably at least 20% by weight, of structural units derived from vinyl acetate, based on the total weight of the copolymer.

[0163] According to one or more embodiments, at least one rigid thermoplastic polymer TP1 accounts for at least 5% by weight, preferably 10-35% by weight, of the total weight of at least one thermoplastic polymer TP, and / or at least one soft thermoplastic polymer TP2 accounts for at least 10% by weight, preferably 15-45% by weight, of the total weight of at least one thermoplastic polymer TP, and / or at least one polyolefin TP3 accounts for at least 25% by weight, preferably 30-75% by weight, of the total weight of at least one thermoplastic polymer TP.

[0164] This invention does not particularly limit the type of at least one polyolefin TP3. Preferably, at least one polyolefin TP3 is not completely miscible with at least one rigid thermoplastic polymer TP1 and / or at least one soft thermoplastic polymer TP2. Furthermore, it is preferable that at least one polyolefin TP3 can be mixed with at least one rigid thermoplastic polymer TP1 and / or with at least one soft thermoplastic polymer TP2 to form a semi-compatible polymer blend containing a slightly incompatible phase.

[0165] According to one or more embodiments, at least one polyolefin TP3 is selected from polyalphaolefins that are solid at 25°C and propylene-based elastomers.

[0166] Suitable polyalphaolefins that are solid at 25°C and intended to be used as at least one polyolefin TP3 include, for example, homopolymers, copolymers, and terpolymers of monomers selected from ethylene, propylene, 1-butene, and higher alpha-olefins. Particularly suitable polyalphaolefins that are solid at 25°C include homopolymers of propylene, copolymers of propylene and ethylene, copolymers of propylene and 1-butene or other higher alpha-olefins, homopolymers of ethylene, copolymers of ethylene and propylene, copolymers of ethylene and 1-butene or other higher alpha-olefins, and terpolymers of ethylene, propylene, and 1-butene.

[0167] According to one or more embodiments, at least one polyolefin TP3 comprises at least one propylene-based elastomer TP31, which preferably has:

[0168] - Such as the melting temperature (T) determined by DSC according to ISO 11357 standard. m The temperature should not exceed 110°C, preferably not exceed 105°C, more preferably not exceed 100°C, and / or

[0169] -Average molecular weight (M n Within the range of 10,000–250,000 g / mol, preferably 25,000–200,000 g / mol and / or

[0170] - The melt flow index, as measured according to ASTM D1238 (230°C / 2.16kg), is 2–30 g / 10 min, preferably 2–20 g / 10 min.

[0171] Suitable propylene-based elastomers particularly include propylene and at least one compound selected from ethylene and C4-C4. 10 A copolymer of comonomers of α-olefins, wherein the copolymer comprises at least 65 wt%, preferably at least 70 wt%, propylene-derived units, based on the total weight of the copolymer and 1-35 wt%, preferably 5-25 wt%, derived from ethylene or C4-C. 10 A unit of at least one of α-olefins, based on the total weight of the copolymer.

[0172] According to one or more embodiments, at least one propylene-based elastomer TP31 is a copolymer of propylene and ethylene, comprising 80-90 wt%, preferably 82-90 wt%, of propylene-derived units based on the total weight of the propylene-based elastomer and 9-18 wt%, preferably 12-16 wt%, of ethylene-derived units based on the total weight of the propylene-based elastomer.

[0173] According to one or more embodiments, at least one propylene-based elastomer TP31 has:

[0174] - The Vicat softening point, determined according to ASTM 1525 using a weight of 200g, is equal to or less than 95°C, preferably equal to or less than 85°C, more preferably equal to or less than 75°C, and / or

[0175] - For example, the heat of fusion determined by DSC is not greater than 50 J / g, preferably not greater than 25 J / g, more preferably not greater than 15 J / g, and even more preferably not greater than 10 J / g and / or

[0176] - The percentage crystallinity determined by the DSC procedure is no more than 25%, preferably no more than 10%, and more preferably no more than 2.5% of the percentage crystallinity of isotactic polypropylene.

[0177] Regarding the determination of percentage crystallinity of propylene-based elastomers, the heat of fusion for isotactic polypropylene (100% crystallinity) is defined as 189 J / g.

[0178] Suitable propylene-based elastomers can be, for example, The product name (from Exxon Mobil) and The product name (from Dow Chemical Company) was purchased commercially.

[0179] According to one or more embodiments, at least one polyolefin TP3 comprises at least one amorphous polyα-olefin TP32 that is solid at 25°C, preferably having:

[0180] - The softening point (T) is determined by the ring and ball method as defined in DIN EN 1238.s Within the range of 60–200°C, preferably 75–180°C, more preferably 85–180°C and / or

[0181] -Average molecular weight (M n Within the range of 2500–35000 g / mol, preferably 3000–30000 g / mol, more preferably 5000–25000 g / mol and / or

[0182] The melt viscosity, measured according to DIN 53019 standard at -190°C, is not greater than 150,000 MPa·s, preferably not greater than 135,000 MPa·s, and more preferably not greater than 125,000 MPa·s. The melt viscosity can be determined using a rotational viscometer at 5 revolutions per minute, for example, using a Brookfield DV-2 Thermosel viscometer with a No. 27 rotor.

[0183] The term "amorphous polyalphaolefin" in this disclosure refers to a polyalphaolefin having a low crystallinity, as determined by differential scanning calorimetry (DSC), for example, in the range of 0.001-10 wt%, preferably 0.001-5 wt%. The crystallinity of a polymer can be determined by using DSC to measure the heat of fusion of the polymer, thereby calculating the crystallinity. Specifically, the term "amorphous polyalphaolefin" refers to a polyalphaolefin that has no crystallization melting temperature (T0) as determined by DSC or equivalent techniques. m ) of polyα-olefins.

[0184] According to one or more embodiments, at least one amorphous polyα-olefin TP32, which is solid at 25°C, has a xylene cold soluble content (XCS) of at least 80% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, as determined according to ISO 16152-2005 at 25°C, and / or a heat of fusion (H₂O) as determined by DSC. f The value is no greater than 35 J / g, preferably no greater than 25 J / g, and more preferably no greater than 15 J / g.

[0185] Suitable examples of amorphous polyalphaolefins that are solid at 25°C include amorphous atactic polypropylene, amorphous propylene-rich propylene-alpha olefin copolymers and terpolymers, particularly amorphous propylene-ethylene copolymers, amorphous propylene-butene copolymers, amorphous propylene-hexene copolymers, and amorphous propylene-ethylene-butene terpolymers. Such amorphous polyalphaolefins are known to those skilled in the art and can be obtained, for example, by polymerization of alpha-olefins in the presence of a polymerization catalyst such as a Ziegler-Natta catalyst, a metallocene catalyst, or any other single-center catalyst.

[0186] Suitable amorphous poly-α-olefins that are solid at 25°C can be, for example, as... The product name (from Evonik Industries), The product name (from Eastman Corporation) and The product name (from REXtac LLC) was purchased commercially.

[0187] According to one or more other embodiments, at least one polyolefin TP3 comprises at least one propylene-based elastomer TP31. According to one or more embodiments, at least one polyolefin TP3 comprises at least one amorphous polyalphaolefin TP32 that is solid at 25°C. According to one or more other embodiments, at least one polyolefin TP3 comprises at least one propylene-based elastomer TP31 and at least one amorphous polyalphaolefin TP32 that is solid at 25°C.

[0188] According to one or more embodiments, at least one thermoplastic polymer TP accounts for 3-15% by weight, preferably 3.5-12.5% ​​by weight, more preferably 5-12.5% ​​by weight, and / or at least one hydrocarbon resin HR accounts for 5-30% by weight, preferably 10-25% by weight, more preferably 12.5-20% by weight, and even more preferably 15-18.5% by weight, of the total weight of the sound damping material, wherein at least one hydrocarbon resin HR is preferably a hydrogenated hydrocarbon resin.

[0189] According to one or more embodiments, at least one wax W accounts for at least 0.5% by weight, preferably 1-15% by weight, more preferably 2.5-10% by weight, even more preferably 2.5-7.5% by weight, and even more preferably 3.5-7.5% by weight, of the total weight of the sound damping material, and / or at least one plasticizer PL accounts for at least 0.5% by weight, preferably 1-15% by weight, more preferably 2.5-10% by weight, even more preferably 2.5-7.5% by weight, and even more preferably 3.5-7.5% by weight, of the total weight of the sound damping material.

[0190] Preferred plasticizer PL is a liquid, wherein the term "liquid" is defined as a material that flows at normal room temperature, has a pour point of less than 20°C, and / or a kinematic viscosity of 50,000 cSt or less at 25°C. Preferably, at least one plasticizer PL is selected from process oils and hydrocarbon resins that are liquid at 25°C.

[0191] According to one or more embodiments, at least one plasticizer PL comprises at least one process oil PL1 selected from mineral oil, synthetic oil and vegetable oil.

[0192] The term "mineral oil" in this disclosure refers to a hydrocarbon liquid derived from crude petroleum and subjected to one or more refining and / or hydrotreating steps, such as fractionation, hydrocracking, dewaxing, isomerization, and hydrorefining, to purify and chemically modify the components to achieve a final property group with a lubricating viscosity (i.e., a kinematic viscosity of 1 cSt or greater at 100°C). In other words, the term "mineral" in this disclosure refers to mineral oil, which may also be characterized as Group I-III base oils according to the American Petroleum Institute (API) classification.

[0193] Suitable mineral oils for use as at least one process oil PL1 include alkane oils, naphthenic oils, and aromatic mineral oils. Particularly suitable mineral oils include alkane and naphthenic oils containing a relatively low amount of aromatic components, for example, no more than 25% by weight, preferably no more than 15% by weight, based on the total weight of the mineral oil.

[0194] The term "synthetic oil" in this disclosure refers to fully synthetic (polyalphaolefin) oil, which is also known as Group IV base oil according to the American Petroleum Institute (API) classification. Suitable synthetic oils are produced from liquid polyalphaolefins (PAOs) obtained by polymerizing alphaolefins in the presence of a polymerization catalyst such as a Friedel-Crafts catalyst. Generally, liquid PAOs are high-purity hydrocarbons with alkyl structures and a high degree of side chain branching. Particularly suitable synthetic oils include those obtained by so-called natural gas synthesis processes.

[0195] According to one or more embodiments, at least one plasticizer PL comprises at least one hydrocarbon resin PL2 that is liquid at 25°C.

[0196] Suitable hydrocarbon resins that are liquid at 25°C include polybutene and polyisobutylene (PIB) that are liquid at 25°C. The term "polybutene that is liquid at 25°C" in this disclosure refers to a low molecular weight olefin oligomer comprising isobutylene and / or 1-butene and / or 2-butene. The ratio of C4-olefin isomers may vary depending on the manufacturer and grade. When the C4-olefin is only 1-butene, the material is referred to as "poly-n-butene" or "PNB". The term "polyisobutylene that is liquid at 25°C" in this disclosure refers to low molecular weight polyolefins and olefin oligomers of isobutylene, preferably containing at least 75%, more preferably at least 85%, repeating units derived from isobutylene. Particularly suitable polybutene and polyisobutylene that are liquid at 25°C for use as at least one hydrocarbon resin PL2 that is liquid at 25°C have a molecular weight (M... n The value is no greater than 10000 g / mol, preferably no greater than 5000 g / mol, more preferably no greater than 3500 g / mol, even more preferably no greater than 3000 g / mol, and even more preferably no greater than 2500 g / mol.

[0197] Liquid polybutene can be, for example, as The product names for the H- and L- series (from Ineos Oligomers), with C-series and The product name (from Infineum) and the product name (Daelim) under the PB-series are commercially available. Liquid polyisobutylene (PIB) can be, for example, as... The V-series product name (from BASF) and... - The product name (from Univar GmbH, Germany) is available for purchase.

[0198] According to one or more embodiments, at least one plasticizer PL consists of at least one process oil PL1, which is preferably selected from mineral oil, synthetic oil and vegetable oil.

[0199] According to one or more other embodiments, at least one plasticizer PL consists of at least one hydrocarbon resin PL2 that is liquid at 25°C, preferably selected from liquid polybutene and liquid polyisobutylene (PIB), and preferably has a molecular weight (M... n The polydispersity index (Mw / Mn) determined by gel permeation chromatography (GPC) is not greater than 5,000 g / mol, more preferably not greater than 3,500 g / mol, and even more preferably not greater than 3,000 g / mol and / or the polydispersity index (Mw / Mn) is not greater than 7.5, more preferably not greater than 5.0, for example in the range of 0.5–5.0, preferably 1.0–4.5, more preferably 1.0–3.5, and even more preferably 1.25–2.5.

[0200] According to the third preferred embodiment, the adhesive matrix a) of the acoustic damping material comprises:

[0201] a2) 0.5–20 wt%, preferably 2.5–15 wt%, of a polymer component P containing at least one elastomer E.

[0202] a3) 0.5–35 wt%, preferably 2.5–25 wt%, of at least one hydrocarbon resin HR,

[0203] a4) 0–15% by weight, preferably 0.5–10% by weight, of at least one wax W, and

[0204] a5) 0–30 wt%, preferably 0.5–25 wt%, of at least one plasticizer PL, all proportions based on the total weight of the acoustic damping material.

[0205] The acoustic damping material according to the third preferred embodiment can be characterized as "asphalt-free elastomeric damping material". According to one or more embodiments, the asphalt-free elastomeric damping material contains less than 1% by weight, preferably less than 0.5% by weight, more preferably less than 0.1% by weight, and even more preferably less than 0.01% by weight of asphalt, based on the total weight of the asphalt-free elastomeric damping material.

[0206] According to one or more embodiments, at least one elastomer E is selected from butyl rubber, halogenated butyl rubber, ethylene-propylene diene monomer rubber, natural rubber, chloroprene rubber, synthetic 1,4-cis-polyisoprene, polybutadiene rubber, ethylene-propylene rubber, styrene-butadiene rubber, isoprene-butadiene rubber, styrene-isoprene-butadiene rubber, acrylonitrile-isoprene rubber, and acrylonitrile-butadiene rubber, preferably selected from butyl rubber, halogenated butyl rubber, ethylene-propylene diene monomer rubber, chloroprene rubber, synthetic 1,4-cis-polyisoprene, polybutadiene rubber, and ethylene-propylene rubber.

[0207] The term "butyl rubber" in this document refers to a product derived from a monomer containing mostly C4-C7 monoolefin monomers, preferably isoolefin monomers, and a small portion, for example, no more than 30% by weight of C4-C7 monoolefin monomers. 14 Polymers of polyolefin monomers, preferably mixtures of conjugated dienes. Preferred C4-C7 monoolefin monomers may be selected from the following: isobutene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, 4-methyl-1-pentene, and mixtures thereof.

[0208] Preferred C4-C 14 Polyolefins contain C4-C 10 Conjugated diene. Preferred C4-C. 10 The conjugated diene may be selected from the following: isoprene, butadiene, 2,4-dimethylbutadiene, piperyline, 3-methyl-1,3-pentadiene, 2,4-hexadiene, 2-neopentyl-1,3-butadiene, 2-methyl-1,5-hexadiene, 2,5-dimethyl-2,4-hexadiene, 2-methyl-1,4-pentadiene, 2-methyl-1,6-heptadiene, cyclopentadiene, methylcyclopentadiene, cyclohexadiene, 1-vinyl-cyclohexadiene, and mixtures thereof.

[0209] According to one or more embodiments, at least one elastomer E accounts for 3-15% by weight, preferably 3.5-12.5% ​​by weight, and more preferably 5-12.5% ​​by weight of the total weight of the acoustic damping material.

[0210] According to one or more embodiments, the polymer component P, in addition to at least one elastomer E, also comprises at least one thermoplastic polymer TMP, preferably selected from the following: polyolefin homopolymers and copolymers, copolymers of ethylene and vinyl acetate, and thermoplastic olefin elastomers (TPE-O).

[0211] The preferred conditions described above for the use of at least one thermoplastic polymer TP in asphalt-free thermoplastic damping materials also apply to the use of at least one thermoplastic polymer TMP in asphalt-free elastomeric damping materials.

[0212] According to one or more embodiments, the weight ratio of at least one elastomer E to at least one thermoplastic polymer TMP is in the range of 10:1-1:3, preferably 5:1-1:2, more preferably 5:1-1:1.

[0213] According to one or more implementation schemes, the asphalt-free elastomeric damping material also includes a vulcanization system VS.

[0214] Many sulfur-based sulfidation systems, as well as sulfur-free sulfidation systems, are suitable.

[0215] If an elemental sulfur-based sulfurization system is used, the sulfurization system VS preferably contains powdered sulfur, more preferably at least one sulfur compound selected from the following: powdered sulfur, precipitated sulfur, highly dispersed sulfur, surface-treated sulfur, and insoluble sulfur.

[0216] The preferred elemental sulfur-based sulfidation system comprises 1-15% by weight, more preferably 5-10% by weight, of powdered sulfur, preferably at least one sulfur compound selected from the following: powdered sulfur, precipitated sulfur, highly dispersed sulfur, surface-treated sulfur, and insoluble sulfur, based on the total weight of the sulfidation system.

[0217] According to one or more implementation schemes, the VS is a sulfidation system without elemental sulfur.

[0218] The preferred sulfur-free vulcanization system comprises at least one vulcanizing agent and optionally at least one organic vulcanization accelerator and / or at least one inorganic vulcanization accelerator.

[0219] Suitable vulcanizing agents for vulcanization systems without elemental sulfur include, for example, organic peroxides, phenolic resins, diazocarbamates, polyfunctional amines, p-quinone dioxime, p-benzoquinone dioxime, p-quinone dioxime dibenzoate, p-nitrosobenzene, dinitrosobenzene, thiuram compounds, bismaleimide, dimercaptoides, zinc oxide, and vulcanization systems crosslinked with (terminated) diisocyanates.

[0220] Suitable organic vulcanization accelerators for use in vulcanization systems without elemental sulfur include thiocarbamates, dithiocarbamates (in the form of their ammonium or metal salts), xanthate esters, thiuram compounds (monosulfides and disulfides), thiazole compounds, aldehyde-amine accelerators such as hexamethylenetetramine, and guanidine accelerators.

[0221] Suitable inorganic sulfidation accelerators for use in sulfidation systems without elemental sulfur include, for example, zinc compounds, particularly zinc salts of fatty acids, basic zinc carbonate, and zinc oxide.

[0222] According to one or more embodiments, the vulcanization system VS is a vulcanization system free of elemental sulfur, preferably containing at least one vulcanizing agent selected from p-quinone dioxime, p-benzoquinone dioxime, p-quinone dioxime dibenzoate, p-nitrosobenzene, dinitrosobenzene and thiuram compounds, preferably selected from p-quinone dioxime, p-benzoquinone dioxime, p-quinone dioxime dibenzoate, tetramethylthiuram disulfide (TMTD) and tetrabenzylthiuram disulfide (TBzTD), and preferably further containing at least one organic vulcanization accelerator and / or at least one inorganic vulcanization accelerator.

[0223] According to one or more embodiments, at least one organic vulcanization accelerator is selected from cyclohexylbenzothiazole sulfonamide, mercaptobenzothiazole sulfide (MBTS), diphenylguanidine, and zinc dimethyl dithiocarbamate.

[0224] According to one or more embodiments, at least one inorganic sulfidation accelerator is selected from zinc salts of fatty acids, basic zinc carbonate, and zinc oxide, more preferably zinc oxide.

[0225] According to one or more embodiments, the vulcanization system without elemental sulfur accounts for 1–15% by weight, more preferably 1–12.5% ​​by weight, even more preferably 2–10% by weight, and most preferably 3.5–10% by weight of the total weight of the asphalt-free elastomeric damping material.

[0226] According to one or more embodiments, the acoustic damping material further comprises at least one foaming agent BA.

[0227] Suitable foaming agents (BA) for use in acoustic damping materials include chemical foaming agents and physical foaming agents. Chemical foaming agents are typically solids that release gases (one or more) through chemical reactions, such as decomposition, when exposed to higher temperatures. Chemical foaming agents can be either inorganic or organic.

[0228] Suitable chemical blowing agents include, for example, azodicarbonamide; hydrazine derivatives such as 4,4′-oxobis(benzenesulfonylhydrazine), diphenyl sulfone-3,3′-disulfonylhydrazine, and trihydrazine triazine; semicarbazide such as p-toluylenesulfonyl semicarbazide; tetrazolium such as 5-phenyltetrazole; benzoxazine such as indigo anhydride; carbonates and bicarbonates such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, and potassium bicarbonate; and carboxylic acids such as solid, hydroxyl-functionalized, or unsaturated dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and polycarboxylic acids, such as citric acid, tartaric acid, malic acid, fumaric acid, and maleic acid.

[0229] Suitable physical foaming agents include, for example, expandable microspheres, which consist of a thermoplastic shell filled with a thermally expandable fluid or gas. Examples of suitable commercially available expandable microspheres include, for example... Microspheres (from AkzoNobel).

[0230] If used, the amount of at least one foaming agent BA is preferably 0.1-5% by weight, more preferably 0.25-3.5% by weight, more preferably 0.5-3% by weight, and even more preferably 1-3% by weight of the total weight of the sound damping material.

[0231] The sound damping material may optionally contain additives commonly used in sound damping materials. Examples of suitable additives include, for example, pigments, thixotropic agents, heat stabilizers, desiccants, and flame retardants. If used in whole, these additives preferably constitute no more than 25% by weight, more preferably no more than 15% by weight, and even more preferably no more than 10% by weight of the total weight of the sound damping material.

[0232] The preferred conditions described above for asphalt component B, polymer component P, at least one modified polymer MP, at least one thermoplastic polymer TP, at least one thermoplastic polymer TMP, at least one elastomer E, at least one hydrocarbon resin HR, at least one wax W, at least one plasticizer PL, at least one solid particulate cellulose-containing filler FW, and at least one solid particulate inorganic filler FM are equally applicable to all subjects of the present invention, unless otherwise stated.

[0233] Another subject of the invention is a method for producing a sound damping material according to the invention, the method comprising mixing the components of an adhesive matrix a) and the components of a filler component b) at an elevated temperature, preferably in the range of 120-200°C, more preferably in the range of 130-180°C, until a homogeneous mixture is obtained.

[0234] The term "homogeneously mixed mixture" in this document refers to a composition in which the individual components are substantially uniformly distributed in the composition. Furthermore, a homogeneously mixed mixture is preferably a multiphase mixture. For example, a homogeneously mixed mixture of polymer and filler components thus refers to a composition in which the filler phase is uniformly / consistently distributed in the polymer phase. It will be apparent to those skilled in the art that regions can be formed within such mixed compositions, having slightly higher concentrations of one or more components than other regions, and 100% uniform distribution of all components is generally not achievable. However, such mixed compositions with "imperfect" distributions of components are also intended to be included in the term "homogeneously mixed mixture" according to the invention.

[0235] Any conventional type of mixing equipment can be used to mix components a) and b). The mixing step can be carried out in an intermittent manner using conventional batch mixers such as Dreis mixers, Brabender mixers, Banbury mixers, or roller mixers, or in a continuous manner using continuous mixers such as extruders, especially single-screw, twin-screw, or planetary roller extruders.

[0236] The homogeneous mixture obtained from the mixing step can then be cooled to a temperature below 70°C, preferably below 50°C, more preferably below 40°C. If an extruder is used in the mixing step, it is preferable to extrude the homogeneous mixture through an extruder die before the cooling step. The cooled homogeneous mixture is storage stable under normal storage conditions. The term "storage stable" in this disclosure means a material that can be stored under specified storage conditions for a long period of time, such as at least one month, particularly at least three months, without any significant change in the material's application properties. "Typical storage conditions" refers to a temperature not exceeding 50°C, particularly not exceeding 35°C.

[0237] Furthermore, the homogeneous mixture can be processed into shaped articles, such as sheets or films, using any conventional techniques such as extrusion, calendering, and hot pressing. The forming step is preferably performed at an elevated temperature and / or before a cooling step. According to one or more embodiments, the homogeneous mixture is extruded through an extruder die, preferably a flat die, to form a sheet or film, which is preferably cooled between a pair of calender cooling rolls. According to one or more other embodiments, the homogeneous mixture is formed into a sheet or film by extruding the homogeneous mixture between one or more pairs of generally parallel rolls in a calendering apparatus. The extruded and / or calendered sheets or films can be used to produce shaped articles of specific dimensions, for example, by stamping or die-cutting.

[0238] Another subject of the present invention is the use of the acoustic damping material according to the invention for vibration and / or noise damping in transport vehicles or large household appliances.

[0239] Another subject of the present invention is a vibration and noise damping element (1), comprising:

[0240] i) A damping layer (2) having first and second surfaces (3, 3') and

[0241] ii) An adhesive layer (4) covering at least a portion of the first surface (3) of the damping layer (2), wherein the damping layer (2) comprises or is composed of the acoustic damping material of the present invention.

[0242] exist Figure 1 The image shows a cross-section of the vibration and noise damping element according to the present invention.

[0243] According to one or more embodiments, the damping layer is a sheet-like element having first and second principal surfaces, with a thickness, length, and width defined therebetween that are at least 5 times, preferably at least 15 times, and more preferably at least 25 times, the thickness of the sheet-like element. The term "thickness" refers to the dimension of the sheet-like element measured in a plane substantially perpendicular to the length and width dimensions of the element. In embodiments where the damping layer is a sheet-like element, the first and second surfaces of the damping layer correspond to the first and second principal surfaces of the sheet-like element.

[0244] The damping layer and the adhesive layer are preferably directly bonded to each other over their opposing surfaces. The expression "directly bonded" should be understood in the context of this invention as meaning that there is no additional layer or material between the two layers and that the opposing surfaces of the layers are directly adhered to each other. According to one or more embodiments, the adhesive layer covers at least 65%, preferably at least 75%, more preferably at least 85%, even more preferably at least 90%, and still more preferably at least 95% of the first surface of the damping layer. According to one or more other embodiments, the adhesive layer covers substantially the entire area of ​​the first surface of the damping layer. The expression "substantially the entire area" should be understood as meaning at least 97.5%, preferably at least 98.5%, and more preferably at least 99.5% of the total area.

[0245] The adhesive layer preferably comprises a pressure-sensitive adhesive or a hot melt adhesive composition. The term "pressure-sensitive adhesive" should be understood to also include a pressure-sensitive hot melt adhesive (HM-PSA). According to one or more embodiments, the adhesive layer comprises a pressure-sensitive adhesive or a hot melt adhesive composition.

[0246] Suitable pressure-sensitive adhesives for use in adhesive layers include compositions based on: acrylic polymers, styrene block copolymers, amorphous polyolefins (APO), amorphous polyalphaolefins (APAO), vinyl ether polymers or elastomers such as butyl rubber, ethylene vinyl acetate with a high vinyl acetate content, natural rubber, nitrile rubber, silicone rubber, and ethylene-propylene-diene rubber. In addition to the polymers mentioned above, suitable pressure-sensitive adhesive compositions typically contain one or more additional ingredients, including, for example, tackifying resins, waxes, and plasticizers, and one or more additives, such as UV absorbers, UV stabilizers and heat stabilizers, optical brighteners, pigments, dyes, and drying agents.

[0247] Hot melt adhesives are solvent-free adhesives that are solid at room temperature and applied as a melt to a substrate to be bonded. Upon cooling, the adhesive solidifies and bonds with the substrate through physical and / or chemical bonding. Suitable hot melt adhesives include, for example, polyolefin-based hot melt adhesives, particularly those based on amorphous polyolefins (APO) and amorphous polyalphaolefins (APAO), thermoplastic copolymer-based hot melt adhesives, particularly those containing copolymers of ethylene and vinyl acetate (EVA) or polyamide as the main polymer components, and polyurethane-based hot melt adhesives. In addition to the polymers mentioned above, suitable hot melt adhesive compositions typically contain one or more additional ingredients, including, for example, resins and waxes, and one or more additives, such as UV absorbers, UV stabilizers and heat stabilizers, optical brighteners, pigments, dyes, and drying agents. Suitable hot melt adhesives to be used in adhesive layers are disclosed, for example, in WO 2011 / 023768 A1, WO 2016 / 139345 A1 and WO 2017 / 174522 A1.

[0248] According to one or more embodiments, the damping layer has a maximum thickness in the range of 0.5–15 mm, preferably 1–10 mm, more preferably 1.5–7.5 mm, and even more preferably 1.5–5 mm, and / or a density in the range of 0.1–5 g / cm³. 3 Preferred concentration: 0.2–4.5 g / cm³ 3 More preferably 0.3–3 g / cm³ 3 Even more preferred is 0.3–2.5 g / cm³. 3 Within the range and / or mass / unit area of ​​1–5 kg / m² 2 Preferred weight: 1–4.5 kg / m 2 More preferably 1.5–4.5 kg / m 2 Even better, 1.5–3.5 kg / m 2 .

[0249] According to one or more embodiments, the vibration and noise damping element has a loss coefficient of at least 0.1, preferably at least 0.15, measured at 200 Hz and 20°C using a method as defined in ISO 6721. Such vibration and noise damping elements have been found to be particularly suitable for damping vibrations of components and structures contained in articles of manufacture in the automotive industry and household appliances.

[0250] According to one or more embodiments, the vibration and noise damping element includes, in addition to the damping layer and adhesive layer, a confining layer covering at least a portion of the second surface of the damping layer. Vibration and noise damping elements according to these embodiments are generally referred to as "confined layer damping devices." The damping layer and the confining layer are directly or indirectly connected to each other above their opposing surfaces, i.e., the damping layer is sandwiched between the adhesive layer and the confining layer. According to one or more embodiments, the confining layer covers substantially the entire area of ​​the second surface of the damping layer. Figure 2 The image shows the cross-section of the vibration and noise damping element according to these embodiments.

[0251] According to one or more embodiments, the limiting layer is a metal sheet, preferably an aluminum or steel sheet or a polymer sheet, preferably a glass fiber reinforced polymer sheet. There is no particular limitation on the thickness of the limiting layer, but it is generally preferred to use a limiting layer thinner than the damping layer. The preferred thickness also depends on the material of the limiting layer. According to one or more embodiments, the limiting layer has a thickness of 0.05–1.5 mm, preferably 0.1–1.25 mm, more preferably 0.1–1.0 mm. According to one or more embodiments, the limiting layer is a metal sheet with a thickness of 0.05–0.5 mm, preferably 0.05–0.4 mm. According to one or more other embodiments, the limiting layer is a polymer sheet with a thickness of 0.1–1.2 mm, preferably 0.25–1.0 mm.

[0252] Preferably, the elastic modulus of the limiting layer is greater than that of the damping layer, meaning greater than by at least 3 times, preferably at least 5 times, and more preferably at least 10 times, wherein the elastic modulus is measured by a method as defined in ISO 6892-1:2016 (for metal sheets) or as defined in ISO 527-2 (for polymer sheets).

[0253] Another subject of the present invention is a method for producing the vibration and noise damping element of the present invention, the method comprising the following steps:

[0254] i) Provide a damping layer comprising the acoustic damping material of the present invention or composed of the acoustic damping material of the present invention and having first and second surfaces.

[0255] ii) Apply the adhesive composition to the first surface of the damping layer.

[0256] Step i) can be performed using any conventional technique known to those skilled in the art. For example, the acoustic damping material of the present invention can be first melt-processed in an extruder and then extruded through an extruder die, preferably a flat die, into the form of a damping layer. Alternatively, the acoustic damping material of the present invention can be processed into a damping layer using calendering or hot pressing techniques.

[0257] The adhesive composition can be applied to the surface of the damping layer using any conventional technique, the details depending on the type of adhesive composition. For example, the adhesive composition can be applied to the sheet surface via nozzle extrusion, powder dispersion, hot melt calendering, or a spray coating technique. In the case of hot melt adhesive compositions or hot melt pressure-sensitive adhesive (HM-PSA) compositions, the adhesive composition is first heated to above the softening point (T0) of the adhesive before being applied to the surface of the damping layer. s The applied temperature is increased.

[0258] Another subject of the present invention is a method for applying a vibration and noise damping element according to the invention to a noise emitting surface of a substrate, the method comprising the following steps:

[0259] I) Provides a vibration and noise damping element according to the present invention.

[0260] II) Bring the outer main surface of the adhesive layer of the vibration and noise damping element into contact with the noise emitting surface and apply sufficient pressure to form an adhesive bond or

[0261] II') Heat the adhesive layer and / or substrate of the vibration and noise damping element and bring the outer main surface of the adhesive layer into contact with the noise emitting surface, and form an adhesive bond by cooling the adhesive layer.

[0262] The term "outer principal surface" of the adhesive layer refers to the principal surface of the adhesive layer on the side opposite to the damping layer side. The substrate with the noise-emitting surface can be any type of molded article, such as a panel, sheet, or film, composed of, for example, metal, plastic, or fiber-reinforced plastic. Heating of the adhesive layer and / or substrate in step II)' can be performed using any conventional technique, such as heating in an oven, heating by airflow, or heating with infrared (IR) radiation.

[0263] Another subject of the invention is a vibration damping system comprising a substrate (6) having a noise emitting surface (7) and a vibration and noise damping element (1) according to the invention, wherein at least a portion of the first surface (3) of the damping layer (2) is adhesively bonded to the noise emitting surface (7) by an adhesive layer (4). Figure 3 The cross-section of the vibration damping system is shown in the image.

[0264] According to one or more embodiments, the vibration and noise damping element (1) is a confined damping element comprising a confining layer (5), wherein the damping layer (2) is sandwiched between the adhesive layer (4) and the confining layer (5). Figure 4 The image shows a cross-section of a vibration damping system according to these embodiments.

[0265] According to one or more embodiments, the substrate having a noise-emitting surface is a part of the structure of an automobile vehicle or a large household appliance. Example

[0266] The following products shown in Table 1 are used in the embodiments.

[0267] Table 1

[0268]

[0269]

[0270] Preparation of damping material sheets

[0271] Damping materials having compositions Ref-1, Ref-2 and Ex-1 to Ex-8 as shown in Table 2 are prepared according to the following procedures.

[0272] In the first step, asphalt B, polymer P1, hydrocarbon resin HR, and wax W are mixed in a batch mixer until a homogeneous mixture is obtained. Thereafter, the remaining components of the damping material are added, and mixing continues until a homogeneous mixture is obtained. The resulting mixture is then processed using conventional calendering equipment to a thickness of approximately 2 mm and a mass / unit area of ​​approximately 3 kg / m². 2 The film.

[0273] Measurement of loss coefficient

[0274] Test specimens of suitable dimensions are obtained by cutting or die-cutting pre-prepared sheets of damping material. One of the main surfaces of each test specimen is coated with an acrylic-based pressure-sensitive adhesive layer. The adhesive layer has a thickness of 50 μm.

[0275] The loss coefficient of the test specimen was determined using the measurement method defined in ISO 6721. Measurements were performed using a commercially available loss coefficient tester at a temperature range of 20–60°C. The loss coefficient value at a frequency of 200 Hz was obtained mathematically from the measured loss coefficient values.

[0276] Density measurement

[0277] The density of a test specimen (without an adhesive layer) is measured in deionized water and on a precision balance according to DIN EN ISO 1183 standard using the water immersion method (Archimedes' principle).

[0278] Measured damping properties

[0279] The damping properties of the exemplary composition are characterized by using the following parameters:

[0280] -Maximum Measurement Loss Factor (LF) 最大 )

[0281] - The temperature at which the maximum loss factor is measured (at LF) 最大 (T)

[0282] -The measured loss coefficient is equal to or greater than 0.1 for the temperature range width (LF≥0.1ΔT).

[0283]

[0284] Determined chemical properties

[0285] The selected exemplary composition is also characterized by the following parameters:

[0286] -Odor emissions according to VDA 270

[0287] -Based on VDA 278, emissions of high and medium volatile organic compounds (VOCs)

[0288] -Emissions of low volatile organic compounds (FOG) according to VDA 278

[0289] The tests, conducted according to the VDA 270 method, were performed by a team of three inspectors who determined the presence of specific odors on a scale of 1 to 6.

[0290] The results of these measurements are presented in Table 3.

[0291] Table 3

[0292] sample Ref-1 Ex-1 Ex-4 Ex-7 Odor emissions 4.5 3.5 3.5 3.5 VOC emissions [μg / g] 461 283 307 312 FOG emissions [μg / g] 1792 786 845 762

Claims

1. Sound damping materials, including: a) Adhesive matrix, comprising, a1) 20-65% by weight of asphalt component B, based on the total weight of the acoustic damping material. a3) At least one optional hydrocarbon resin HR, a4) Any one of the following waxes W, a5) Optional at least one plasticizer PL, and b) Filler components, including: b1) 5-30% by weight of at least one solid particulate cellulose-containing filler FW, based on the total weight of the acoustic damping material, wherein: - The median particle width D of the at least one solid particulate cellulose-containing filler FW 50 Within the range of 150-450 µm, and - The at least one solid granular cellulose-containing filler FW comprises at least 95% by weight hardwood particles; and b2) 40-75% by weight of at least one solid particulate inorganic filler FM, based on the total weight of the acoustic damping material, wherein the at least one solid particulate inorganic filler FM comprises: b21) At least one first solid particulate inorganic filler FM1, wherein the median particle diameter d of the at least one first solid particulate inorganic filler FM1 is... 50 Within the range of 1-75 µm, and b22) At least one second solid granular inorganic filler FM2, different from at least one first solid granular inorganic filler FM1, wherein the median particle diameter d of the at least one second solid granular inorganic filler FM2 is... 50 It should be at least 100 µm.

2. The acoustic damping material according to claim 1, wherein the median particle width D of at least one solid particulate cellulose filler FW is... 50 Within the range of 165-450 µm.

3. The acoustic damping material according to claim 1, wherein filler component b) accounts for 45-70% of the total weight of the acoustic damping material.

4. The acoustic damping material according to claim 1, wherein the filler component b) accounts for 45-65% by weight of the total weight of the acoustic damping material.

5. The acoustic damping material according to any one of claims 1 to 4, comprising: b1) 7.5–15% by weight of at least one solid particulate cellulose-containing filler FW, based on the total weight of the acoustic damping material.

6. The acoustic damping material according to any one of claims 1 to 4, comprising: b1) 5–25% by weight of at least one solid particulate cellulose-containing filler FW, based on the total weight of the acoustic damping material.

7. The acoustic damping material according to any one of claims 1 to 4, wherein the number average aspect ratio of at least one solid particulate cellulose filler FW is not greater than 10, wherein the aspect ratio is determined as the ratio of the length (L) to the thickness (T) of the particles.

8. The acoustic damping material according to any one of claims 1 to 4, wherein the number-average aspect ratio of at least one solid particulate cellulose filler FW is not greater than 7.5, wherein the aspect ratio is determined as the ratio of the length (L) to the thickness (T) of the particles.

9. The acoustic damping material according to any one of claims 1 to 4, wherein at least one solid particulate cellulose filler FW is composed of wood particles.

10. The acoustic damping material according to any one of claims 1 to 4, wherein at least one solid particulate cellulose-containing filler FW comprises: b11) at least one first solid particulate cellulose-containing filler FW1 and b12) At least one second solid particulate cellulose-containing filler FW2, wherein at least one first solid particulate cellulose-containing filler FW1 has a median particle width D 50 The median particle width D of at least one second solid granular cellulose-containing solid granular filler FW2 50 At least 5% smaller.

11. The acoustic damping material according to claim 10, wherein the median particle width D of at least one first solid particulate cellulose filler FW1 is... 50 The median particle width D of at least one second solid granular cellulose-containing solid granular filler FW2 50 At least 15% smaller.

12. The acoustic damping material according to claim 10, wherein the weight ratio of at least one first solid particulate cellulose-containing filler FW1 to at least one second solid particulate cellulose-containing filler FW2 is in the range of 5:1 to 1:

5.

13. The acoustic damping material according to claim 10, wherein the weight ratio of at least one first solid particulate cellulose-containing filler FW1 to at least one second solid particulate cellulose-containing filler FW2 is in the range of 3:1 to 1:

3.

14. The acoustic damping material according to any one of claims 1 to 4, comprising: b2) 45–70% by weight of at least one solid particulate inorganic filler FM, based on the total weight of the acoustic damping material.

15. The acoustic damping material according to any one of claims 1 to 4, comprising: b2) 45–65% by weight of at least one solid particulate inorganic filler FM, based on the total weight of the acoustic damping material.

16. The acoustic damping material according to any one of claims 1 to 4, wherein the material is substantially free of hollow ceramic spheres.

17. The acoustic damping material according to any one of claims 1 to 4, wherein the material is substantially free of hollow ceramic spheres, hollow glass spheres, hollow organic spheres, and glass spheres.

18. The acoustic damping material according to any one of claims 1 to 4, wherein at least one hydrocarbon resin HR has a softening point of at least 70°C as determined by the ring and ball method as defined in DIN EN 1238 and / or wherein at least one wax W is selected from the following: polyolefin wax, paraffin wax, microcrystalline wax and amide wax.

19. The acoustic damping material according to claim 18, wherein at least one hydrocarbon resin HR has a softening point of at least 80°C as determined by the ring and ball method as defined in DIN EN 1238.

20. The acoustic damping material according to any one of claims 1-4, comprising: a1) 20–65% by weight of asphalt component B, a3) 0.1–10% by weight of at least one hydrocarbon resin HR, and a4) 0–10% by weight of at least one wax W, all proportions based on the total weight of the acoustic damping material.

21. The acoustic damping material according to claim 20, comprising... a1) 25–55% by weight of bitumen component B, based on the total weight of the acoustic damping material.

22. The acoustic damping material according to claim 20, comprising: a3) 0.25–5% by weight of at least one hydrocarbon resin HR, based on the total weight of the acoustic damping material.

23. The acoustic damping material according to claim 20, comprising... a4) 0.25–7.5% by weight of at least one wax W, based on the total weight of the acoustic damping material.

24. The acoustic damping material according to claim 20 further comprises at least one modified polymer MP selected from atactic polypropylene (APP), amorphous polyolefin (APO), styrene block copolymer, styrene-butadiene rubber (SBR), ethylene propylene diene monomer rubber (EPDM), polyisoprene, polybutadiene, natural rubber, chloroprene rubber, ethylene-propylene rubber (EPR), nitrile rubber and acrylic rubber.

25. The acoustic damping material according to claim 24, wherein at least one modified polymer MP accounts for 0.5-10% of the total weight of the acoustic damping material.

26. Use of the acoustic damping material according to any one of claims 1-25 for damping vibration and / or noise in transport vehicles or large household appliances.

27. Vibration and noise damping element (1), comprising: i) A damping layer (2) having a first surface (3) and a second surface (3') and ii) An adhesive layer (4) covering at least a portion of the first surface (3) of the damping layer (2), wherein the damping layer (2) comprises or is composed of an acoustic damping material according to any one of claims 1-25.

28. A method of applying the vibration and noise damping element (1) according to claim 27 to the noise emitting surface (7) of a substrate (6), the method comprising the steps of: I) Provide the vibration and noise damping element (1) according to claim 27, II) Make the outer main surface of the adhesive layer (4) contact the noise emitting surface (7) and apply sufficient pressure to form an adhesive bond or II') Heat the adhesive layer (4) and / or the substrate (6) and bring the outer main surface of the adhesive layer (4) into contact with the noise emitting surface (7) and form an adhesive bond by cooling the adhesive layer (4).

29. A vibration damping system comprising a substrate (6) having a noise emitting surface (7) and a vibration and noise damping element (1) according to claim 27, wherein at least a portion of a first surface (3) of a damping layer (2) is bonded to the noise emitting surface (7) by an adhesive layer (4).

30. The vibration damping system according to claim 29, wherein the substrate (6) having the noise emitting surface (7) is a part of the structure of an automobile vehicle or a large household appliance.

Images