Laminated sound-absorbing material

Abstract

To provide a laminated sound absorbing material having excellent sound absorption properties in a frequency range of 500 to 1000 Hz, which people feel unpleasant, despite small thickness and light weight.SOLUTION: The laminated sound absorbing material comprises at least one layer (A) and at least one layer (B), in which apparent density of the layer (A) is 0.15 to 1.5 g / cm3, air permeability (A1, unit: cm3 / cm2 / sec) of the layer (A) in accordance with JIS K6400 is 0 to 10 cm3 / cm2 / sec, total thickness (T1, unit: mm) of the layer (A) is 0.1 to 1.0 mm, the apparent density of the layer (B) is 0.005 to 0.080 g / cm3, the air permeability of the layer (B) in accordance with JIS K6400 is 0.1 to 250 cm3 / cm2 / sec, and the total thickness of the layer (B) is 10 to 65 mm.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to laminated sound-absorbing materials. [Background technology]

[0002] Automobiles and other vehicles are machines that have a power source such as an engine and can be moved by human operation, and they generate various vibrations and noises. The sounds transmitted inside a vehicle include not only the sounds emitted by the power source, but also sounds generated outside the vehicle, such as road noise, tire pattern noise, and wind noise that occur when the vehicle is in motion. If these sounds are transmitted inside the vehicle, they can cause discomfort to people, so soundproofing measures are taken using sound insulation and sound absorption materials in the engine, engine compartment, interior, body, and around the exhaust pipe.

[0003] For example, in Patent Document 1, the normal incidence sound absorption coefficient of a test specimen, in which a 1 mm thick foam film consisting of a base resin that forms open cells and expanded organic hollow particles with an average particle size of 0.1 to 3000 μm dispersed in the base resin and forming closed cells is bonded to a 10 mm thick nonwoven fabric, is measured and the sound absorption coefficient in the frequency range of 2000 to 4000 Hz is 81 to 92%. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2010-2617 [Overview of the project] [Problems that the invention aims to solve]

[0005] Conventional sound-absorbing materials have been insufficient in addressing noise in the 500-1000Hz frequency range, which is considered unpleasant to humans. Furthermore, since the installation space for soundproofing materials is limited in vehicles such as automobiles, there is a need for sound-absorbing materials that are highly space-saving.

[0006] The present invention has been made to solve the above problems, and an object thereof is to provide a laminated sound-absorbing material that has excellent sound absorption in the frequency range of 500 to 1000 Hz, which makes people feel uncomfortable, despite having a small thickness and being lightweight.

Means for Solving the Problems

[0007] As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, the present invention is a laminated sound-absorbing material including at least one layer (A) and at least one layer (B), the layer (A) is made of a resin film, the layer (B) is made of a porous body, and the apparent density of the layer (A) is 0.9~1.3 g / cm 3 wherein the air permeability (A1, unit: cm 3 / cm 2 / sec) of the layer (A) conforming to JIS K6400 is 0 cm 3 / cm 2 / sec, the total thickness (T1, unit: mm) of the layer (A) is 0.1 to 1.0 mm, the apparent density of the layer (B) is 0.010~0.060 g / cm 3 wherein the air permeability of the layer (B) conforming to JIS K6400 is 3~150 cm 3 / cm 2 / sec, and the total thickness of the layer (B) is 10~35 mm, and it is a laminated sound-absorbing material. The layer (A) is positioned facing the sound source.

Effects of the Invention

[0008] According to the present invention, it is possible to provide a laminated sound-absorbing material that has excellent sound absorption in the frequency range of 500 to 1000 Hz, which makes people feel uncomfortable, despite having a small thickness and being lightweight.

Modes for Carrying Out the Invention

[0009] The present invention is a laminated sound-absorbing material including at least one layer (A) and at least one layer (B). The layer (A) and the layer (B) may each be a single layer or a plurality of layers. The total thickness (T1, unit: mm) of layer (A) is 0.1 to 1.0 mm, preferably 0.15 to 0.50 mm. If it is less than 0.1 mm, the sound absorption rate in the low-frequency region will decrease, and if it exceeds 1.0 mm, the sound absorption material will become heavy. By press molding at appropriate temperature, time and pressure, layer (A) having the above thickness can be obtained.

[0010] The apparent density of layer (A) is 0.15 to 1.5 g / cm 3 and preferably 0.2 to 1.3 g / cm 3 and more preferably 0.9 to 1.3 g / cm 3 is. If it is less than 0.15 g / cm 3 , the sound absorption rate in the low-frequency region will decrease, and if it exceeds 1.5 g / cm 3 , the sound absorption material will become heavy. In order to make the apparent density within the above range, it can be adjusted to the preferred range by selecting the material of layer (A) and press molding the selected material at appropriate temperature, time and pressure. The apparent density of layer (A) can be measured in accordance with JIS K7222:2005.

[0011] The air permeability (A1, unit: cm 3 / cm 2 / sec) of layer (A) conforming to JIS K6400 is 0 to 10 cm 3 W / cm 2 W / sec, preferably 0 to 7 cm 3 W / cm 2 W / sec, most preferably 0 to 4 cm 3 W / cm 2 W / sec, particularly preferably 0 to 1 cm 3 W / cm 2 W / sec. If it exceeds 10 cm 3 W / cm 2 W / sec, the sound absorption rate in the low-frequency region will decrease. In order to make the air permeability (A1) within the above range, it can be adjusted to the preferred range by press molding at appropriate temperature, time and pressure.

[0012] The relationship between the air permeability (A1) of the layer (A) and the total thickness (T1) of the layer (A) preferably satisfies the following equation 1. This results in good sound absorption characteristics in the low-frequency range. Formula 1: (A1)≦11.111(T1)-1.111

[0013] The layer (A) preferably consists of at least one selected from the group consisting of resin film, compressed chip sheet, foamed resin sheet, and nonwoven fabric. The resin film is preferably made of urethane resin, urethane urea resin, polyvinyl chloride resin, or polyolefin resin. A compressed chip sheet refers to a sheet obtained by compressing and molding chipped resin or pulp by press processing, and urethane resin compressed chip sheets (hereinafter also referred to as compressed chip urethane sheets or compressed urethane chip sheets) and compressed chip urethane urea sheets are preferred. A foamed resin sheet refers to a sheet-shaped foamed resin (such as urethane foam and urethane urea foam), and includes resins that have been foamed into a sheet shape and compressed foams that have been press-formed into a sheet shape from foamed resins, with compressed urethane foam and compressed urethane urea foam being preferred. As the nonwoven fabric, synthetic fiber nonwoven fabrics are preferred, and short fiber nonwoven fabrics and long fiber nonwoven fabrics can be used. Compressed nonwoven fabrics that have undergone press processing are also acceptable. Layer (A) may consist of at least one selected from resin film, compressed chip sheet, foamed resin sheet, and nonwoven fabric, and may be composed of a single material or of multiple materials laminated together.

[0014] The total thickness of layer (B) is 10 to 65 mm, preferably 10 to 35 mm, and more preferably 15 to 30 mm. If the thickness is less than 10 mm, the sound absorption coefficient in the low-frequency range decreases, and if it exceeds 65 mm, the sound-absorbing material becomes heavy. Layer (B) having the above thickness can be obtained by cutting it to an appropriate thickness.

[0015] The apparent density of layer (B) is 0.005–0.080 g / cm³. 3 The concentration is preferably 0.008 to 0.060 g / cm³. 3 And more preferably 0.010 to 0.060 g / cm³. 3 The apparent density of the porous material in layer (B) can be brought within the aforementioned range by adjusting the amount of foaming agent. 0.005 g / cm³ 3 If the amount is less than 0.080 g / cm³, molding becomes difficult. 3 Beyond a certain point, the low-frequency sound absorption is poor. The apparent density of layer (B) can be determined in accordance with JIS K7222:2005.

[0016] The air permeability of layer (B) according to JIS K6400 is 0.1 to 250 cm. 3 / cm 2 The interval is / sec, preferably 3-220cm. 3 / cm 2 The interval is / sec, and more preferably 3 to 150 cm. 3 / cm 2 It is / sec. 250cm 3 / cm 2 If the rate exceeds / sec, the porous material strength will be insufficient. The air permeability of layer (B) can be adjusted to the above range by adjusting the amounts of foaming agent and baffling agent.

[0017] The layer (B) is preferably made of a porous material. A porous material means a material in which multiple fine pores are formed. Examples of porous materials include foamed resins (polyurethane foam, melamine foam, and rubber sponge, etc.), molded articles obtained by compression molding of pulverized foamed resins (such as chip urethane), nonwoven fabrics, woven fabrics, cotton, felt, and glass wool. Of these, foamed resins and nonwoven fabrics are preferred from the viewpoint of sound absorption in the low-frequency range, and urethane foam and nonwoven fabrics are more preferred. Layer (B) can be any porous material, and may be composed of a single material or multiple materials stacked together.

[0018] When the porous body is polyurethane foam, known methods can be applied as the method for producing the polyurethane foam. These methods include a mold molding foaming method in which a mixture of a polyol component (Q) and, if necessary, a catalyst (C), a foam stabilizer (I), a crosslinking agent, a connecting agent, and a foaming agent (K) is stirred and mixed, then stirred and mixed with a polyisocyanate component (B), and then injected into a suitable mold for foaming, or a slab stock foaming method in which foaming is performed without injecting into a suitable mold.

[0019] The laminated sound-absorbing material of the present invention is obtained by laminating the above layer (A) and the above layer (B). The method for laminating layer (A) and layer (B) is not particularly limited. Examples include foaming the urethane foam before resinification and bonding it to the other substrate, bonding it by frame lamination of the urethane foam, and bonding by heat melting. Layer (A) and layer (B) may also be bonded and laminated using an adhesive (such as spray adhesive) or double-sided tape. The thickness of the adhesive and double-sided tape is preferably 10 to 100 μm, and more preferably 20 to 50 μm.

[0020] If there are two or more layers (A) or layers (B), the laminated sound-absorbing material of the present invention is composed of three or more layers of laminated material by laminating layer (A) and layer (B).

[0021] When there are two or more layers (B), the layers (A) are preferably resin films, and examples of layers (B) include laminates having a first layer (B) which is a urethane foam layer (B1) and a second layer (B) which is a porous layer (B2). The apparent density of the urethane foam layer (B1) is more preferably 0.05 to 0.1 g / cm³ from the viewpoint of sound absorption in the low-frequency range and moldability. 3 And more preferably 0.05 to 0.07 g / cm³. 3 That is the case. The thickness of the urethane foam layer (B1) is more preferably 3 to 15 mm, and even more preferably 5 to 12 mm, from the viewpoint of sound absorption in the low frequency range and lightweight properties. The air permeability of the urethane foam layer (B1) is preferably 1 to 50 cm from the viewpoint of sound absorption. 3 / cm 2 / sec, and more preferably 1-10cm 3 / cm 2 It is / sec.

[0022] The apparent density of the porous layer (B2) is more preferably 0.005 to 0.060 g / cm³ from the viewpoint of sound absorption in the low-frequency range and moldability. 3 And more preferably 0.008 to 0.040 g / cm³. 3 The most preferred concentration is 0.010 to 0.025 g / cm³. 3 That is the case. The thickness of the porous layer (B2) is more preferably 10 to 50 mm, even more preferably 10 to 30 mm, and most preferably 10 to 20 mm, from the viewpoint of sound absorption in the low frequency range and lightweight properties. From the viewpoint of sound absorption, the air permeability of the porous layer (B2) is preferably 1 to 250 cm. 3 / cm 2 / sec, and more preferably 3-220cm 3 / cm 2 It is / sec.

[0023] The porous layer (B2) can be the same as the porous material exemplified as that constituting layer (B), and the preferred material is also the same.

[0024] When the layer (B) constituting the laminated sound-absorbing material of the present invention is a laminate of a urethane foam layer (B1) and a porous layer (B2), it is preferable that the urethane foam layer (B1) is placed between the layer (A) and the porous layer (B2). This arrangement achieves a higher sound absorption effect.

[0025] The method for laminating the urethane foam layer (B1) and the porous layer (B2) is not particularly limited. Examples include creating the urethane foam on the porous layer (B2) and laminating it, or bonding them by frame lamination of the urethane foam. Alternatively, a known adhesive can be applied to one or both of the opposing surfaces of the urethane foam layer (B1) and the porous layer (B2) and allowed to dry to bond them, or double-sided tape can be used to bond the urethane foam layer (B1) and the porous layer (B2). When the urethane foam layer (B1) and the porous layer (B2) are bonded with an adhesive or double-sided tape, the thickness of the adhesive layer or double-sided tape layer is preferably 10 to 100 μm, and more preferably 20 to 50 μm.

[0026] In the laminated sound-absorbing material of the present invention, it is preferable to arrange layer (A) in a direction opposite to the sound source. Layer (A) is formed from a material that is thinner than layer (B) and has low breathability along the direction of sound propagation. This allows the material to exhibit a sound-absorbing effect through membrane vibration, particularly in frequency bands that people find unpleasant, thereby achieving a sound-absorbing effect. [Examples]

[0027] The present invention will be further described by the following examples, but the present invention is not limited thereto. In the examples, parts represent parts by weight, and % represents weight percent. In the following, Examples 16-19 refer to Reference Examples 1-4.

[0028] [Manufacturing Example 1: Manufacturing of Thermoplastic Urethane Urea Film (X-1-1)] In a reaction vessel equipped with a thermometer, stirrer, and nitrogen inlet, 282.9 parts of polyethylene isophthalate with a number average molecular weight (hereinafter abbreviated as Mn) of 2300 as polyester diol (a1), 424.4 parts of polybutylene adipate with Mn of 1000 as polyester diol (a2), 9.34 parts of benzyl alcohol as monool (c), and 5.88 parts of 1,4-butanediol as low molecular weight diol (b) were charged. After purging with nitrogen, the mixture was heated to 110°C with stirring until melted, and then cooled to 50°C. Subsequently, 150.0 parts of methyl ethyl ketone as an organic solvent and 132.0 parts of hexamethylene diisocyanate as organic diisocyanate (e) were added, and the mixture was reacted at 90°C for 6 hours. Next, after cooling to 70°C, 1.4 parts of Irganox 1010 [manufactured by Ciba Specialty Chemicals Co., Ltd.] as a stabilizer were added and mixed uniformly to obtain a solution of urethane prepolymer (Up-1). Subsequently, 157.9 parts of an aqueous solution prepared by dissolving 5.9 parts of Sanspar PS-8 [manufactured by Sanyo Chemical Industries, Ltd.] as a dispersion stabilizer in 152 parts of water, and 37.1 parts of methyl ethyl ketone as an organic solvent were added to the reaction vessel and mixed uniformly at 20°C. Then, 1.7 parts of hexamethylenediamine as diamine (d) were added and mixed for 1 minute under stirring at a peripheral speed of 23 m / s (rotation speed: 10,000 rpm) using an Ultra Disperser [manufactured by Yamato Scientific Co., Ltd.]. Next, 103.3 parts of a solution of the prepolymer (Up-1) heated to 75°C were added and mixed at a peripheral speed of 23 m / s for 2 minutes. The mixture was then transferred to a reaction vessel equipped with a thermometer, stirrer, and nitrogen injection tube, purged with nitrogen, and reacted at 50°C for 10 hours while stirring. After the reaction was complete, the mixture was filtered and dried to obtain thermoplastic urethane urea resin (U-1). The obtained thermoplastic urethane urea resin (U-1) was in powder form, with a volume-average particle size of 205 μm and a manganese content of 25,000.

[0029] The obtained thermoplastic urethane urea resin (U-1) was press-molded at 180°C for 60 seconds at 3 MPa to obtain a thermoplastic urethane urea film (X-1-1) which is a film-like molded product with a film thickness of 0.2 mm.

[0030] <Method for Measuring Volume-Average Particle Diameter> In the present invention, the volume-average particle diameter was measured by the following method. Measurement was carried out using a laser diffraction particle size distribution measuring device ["Microtrac MT3000II" manufactured by Nikkiso Co., Ltd.], and the particle diameter (d50) at a cumulative amount of 50% in the obtained relative cumulative particle size distribution curve was taken as the volume-average particle diameter.

[0031] <Method for Measuring Mn> In the present invention, Mn was measured under the following conditions using gel permeation chromatography. · Apparatus: "HLC-8320" [manufactured by Tosoh Corporation] · Column: "TSKgel Guardcolumn α", "TSKgel α-M" [manufactured by Tosoh Corporation] · Measurement temperature: 40 °C · Sample solution: 0.125 wt% N,N-dimethylformamide solution · Solution injection volume: 100 μL · Detection device: Refractive index detector · Reference substance: 12-point standard polystyrene (TSKstandard POLYSTYRENE) (molecular weights 589, 1,050, 2,630, 5,970, 9,100, 19,500, 37,900, 96,400, 190,000, 427,000, 1,090,000, 2,110,000) [manufactured by Tosoh Corporation] In addition, for the measurement of Mn, a sample was dissolved in N,N-dimethylformamide, and the undissolved portion was filtered through a glass filter and used as the sample solution.

[0032] [Production Example 2: Production of Thermoplastic Urethane Urea Film (X-1-2)] The thermoplastic urethane urea resin (U-1) was press-molded under the conditions of 190 °C, 60 seconds, and 5 MPa to obtain a film-shaped molded body, a thermoplastic urethane urea film (X-1-2) with a film thickness of 0.1 mm.

[0033] [Production Example 3: Production of Thermoplastic Urethane Urea Film (X-1-3)] The thermoplastic urethane urea resin (U-1) was press-molded at 180°C for 60 seconds at 0.5 MPa to obtain a thermoplastic urethane urea film (X-1-3) which is a film-like molded body with a film thickness of 0.38 mm.

[0034] [Manufacturing Example 4: Manufacturing of Thermoplastic Urethane Urea Film (X-1-4)] The thermoplastic urethane urea resin (U-1) was press-molded at 180°C for 60 seconds at 0.3 MPa to obtain a thermoplastic urethane urea film (X-1-4) which is a film-like molded body with a film thickness of 0.5 mm.

[0035] [Manufacturing Example 5: Manufacturing of Thermoplastic Urethane Urea Film (X-1-5)] The thermoplastic urethane urea resin (U-1) was press-molded at 180°C for 60 seconds at 0.1 MPa to obtain a thermoplastic urethane urea film (X-1-5) which is a film-like molded body with a film thickness of 0.75 mm.

[0036] [Manufacturing Example 6: Manufacturing of Thermoplastic Urethane Urea Film (X-1-6)] The thermoplastic urethane urea resin (U-1) was press-molded at 180°C for 60 seconds at 5 MPa with a spacer in between to obtain a thermoplastic urethane urea film (X-1-6) which is a film-like molded body with a film thickness of 1.0 mm.

[0037] [Manufacturing Example 7: Manufacturing of Compressed Chip Urethane (X-2)] Chip urethane (manufactured by Inoac Corporation) is press-molded at 160°C for 60 seconds at 3 MPa with a spacer in between, resulting in a film-like molded product. A compressed chip urethane (X-2) with a thickness of 1.0 mm was obtained.

[0038] [Manufacturing Example 8: Manufacturing of Compressed Nonwoven Fabric (X-3-1)] A nonwoven fabric (Thinsulate: manufactured by 3M) was press-molded at 98°C for 60 seconds at 15 MPa to obtain a compressed nonwoven fabric (X-3-1) that is a film-like molded product with a film thickness of 0.25 mm.

[0039] [Manufacturing Example 9: Manufacturing of Compressed Nonwoven Fabric (X-3-2)] A nonwoven fabric (Thinsulate: manufactured by 3M) was press-molded at 55°C for 60 seconds at 3 MPa to obtain a compressed nonwoven fabric (X-3-2) that is a film-like molded body with a film thickness of 1.0 mm.

[0040] [Manufacturing Example 10: Manufacturing of Urethane Foam (F-1)] Polyol (Q-1), foam stabilizer (I-1), catalyst (C-1), catalyst (C-2), and blowing agent (K-1) were placed in 1L cups in the amounts listed in Table 1 and mixed uniformly in a mixer at 3000 RPM for 60 seconds. Polyisocyanate (B-1) was added to the resulting mixture and immediately mixed in a mixer at 3000 RPM for 15 seconds. The mixture was then poured into a 50cm x 50cm x 50cm cardboard mold and allowed to foam, after which it was cured in a 70°C dryer for 5 minutes to obtain urethane foam (F-1).

[0041] [Manufacturing Example 11: Manufacturing of Urethane Foam (F-2)] Polyol (Q-2), polyol (Q-3), connecting agent (S-1), crosslinking agent (R-1), foam stabilizer (I-2), catalyst (C-1), catalyst (C-3), catalyst (C-4), and blowing agent (K-1) were placed in 1L cups in the amounts listed in Table 1 and mixed uniformly in a mixer at 3000 RPM for 60 seconds. Polyisocyanate (B-1) was added to the resulting mixture and immediately mixed in a mixer at 3000 RPM for 15 seconds. The mixture was then placed in a mold made of 50cm x 50cm x 50cm cardboard, foamed, and then cured in a 70°C dryer for 5 minutes to obtain urethane foam (F-2).

[0042] [Manufacturing Example 12: Manufacturing of Urethane Foam (F-5)] Polyol (Q-4), polyol (Q-5), polyol (Q-6), polyol (Q-7), polyol (Q-8), foam stabilizer (I-3), catalyst (C-1), catalyst (C-2), catalyst (C-4), and blowing agent (K-1) were placed in 1L cups in the amounts listed in Table 1 and mixed uniformly in a mixer at 3000 RPM for 60 seconds. Polyisocyanate (B-1) was added to the resulting mixture and immediately mixed in a mixer at 3000 RPM for 15 seconds. The mixture was then poured into a mold made of 50cm x 50cm x 50cm cardboard and foamed to obtain urethane foam (F-5).

[0043] [Manufacturing Example 13: Manufacturing of Compressed Polyurethane Foam (X-4)] The urethane foam (F-5) produced in manufacturing example 12 was press-molded under the conditions of 160°C, 60 seconds, and 0.5 MPa to obtain compressed urethane foam (X-4), which is a film-like molded body with a film thickness of 0.8 mm.

[0044] <Example 1> A thermoplastic urethane urea film (X-1-1) was layered on urethane foam (F-1), and heat treatment was performed at 160°C for 10 minutes to obtain the laminated sound-absorbing material (Z-1) of the present invention, consisting of layer (B), which is urethane foam (F-1), and layer (A), which is the thermoplastic urethane urea film (X-1-1). The physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material [weight of layer (B) in 1 square meter of laminated sound-absorbing material (kg)] measured by the method described below, and the sound absorption performance (normal incidence sound absorption coefficient) of the laminated sound-absorbing material measured by the method described below are shown in Table 2.

[0045] <Example 2> The same procedure as in Example 1 was performed except that urethane foam (F-1) was changed to urethane foam (F-2) to obtain the laminated sound-absorbing material (Z-2) of the present invention, which consists of layer (B) which is urethane foam (F-2) and layer (A) which is thermoplastic urethane urea film (X-1-1). Table 2 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0046] <Example 3> A thermoplastic urethane urea film (X-1-2) was layered on a urethane foam (F-1), and heat treatment was performed at 160°C for 10 minutes to obtain the laminated sound-absorbing material (Z-3) of the present invention, which consists of layer (B), which is urethane foam (F-1), and layer (A), which is the thermoplastic urethane urea film (X-1-2).

[0047] <Example 4> A thermoplastic urethane urea film (X-1-3) was layered on top of a urethane foam (F-1), and heat treatment was performed at 160°C for 10 minutes to obtain the laminated sound-absorbing material (Z-4) of the present invention, which consists of layer (B), which is urethane foam (F-1), and layer (A), which is the thermoplastic urethane urea film (X-1-3). Table 2 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0048] <Example 5> A thermoplastic urethane urea film (X-1-4) was layered on top of a urethane foam (F-1), and heat treatment was performed at 160°C for 10 minutes to obtain the laminated sound-absorbing material (Z-5) of the present invention, which consists of layer (B) being urethane foam (F-1) and layer (A) being thermoplastic urethane urea film (X-1-4). Table 2 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0049] <Example 6> A thermoplastic urethane urea film (X-1-5) was layered on top of a urethane foam (F-1), and heat treatment was performed at 160°C for 10 minutes to obtain the laminated sound-absorbing material (Z-6) of the present invention, which consists of layer (B), which is urethane foam (F-1), and layer (A), which is the thermoplastic urethane urea film (X-1-5). Table 2 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0050] <Example 7> A thermoplastic urethane urea film (X-1-6) was layered on top of a urethane foam (F-1), and heat treatment was performed at 160°C for 10 minutes to obtain the laminated sound-absorbing material (Z-7) of the present invention, which consists of layer (B), which is urethane foam (F-1), and layer (A), which is the thermoplastic urethane urea film (X-1-6). Table 2 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0051] <Example 8> Thermoplastic polyurethane film (Okura Industries, Silklon), spray adhesive (3M, By applying spray adhesive 55) to a layer and overlapping it with urethane foam (F-1), a laminated sound-absorbing material (Z-8) of the present invention was obtained, consisting of layer (B) which is urethane foam (F-1) and layer (A) which is a thermoplastic urethane film. Table 3 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0052] <Example 9> The same procedure as in Example 1 was followed, except that the urethane foam (F-1) was replaced with a nonwoven fabric (Thinsulate, manufactured by 3M), to obtain the laminated sound-absorbing material (Z-9) of the present invention, which consists of a nonwoven fabric as layer (B) and a thermoplastic urethane urea film (X-1-1) as layer (A). Table 3 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0053] <Example 10> Polyol (Q-2), polyol (Q-3), connecting agent (S-1), crosslinking agent (R-1), foam stabilizer (I-2), catalyst (C-1), catalyst (C-3), catalyst (C-4), and blowing agent (K-1) were placed in 1L cups in the amounts listed in Table 1 and mixed uniformly in a mixer at 3000 RPM for 60 seconds. Polyisocyanate (B-1) was added to the resulting mixture and immediately mixed in a mixer at 3000 RPM for 15 seconds. The resulting mixture was placed in a 40cm x 40cm x 2cm mold, in which the urethane foam (F-1) prepared in Production Example 10 was fixed to the bottom surface with double-sided tape, and the thermoplastic urethane urea film (X-1-1) prepared in Production Example 1 was fixed to the inside of the lid with double-sided tape. The lid was then closed and the mixture was foamed to obtain the laminated sound-absorbing material (Z-10) of the present invention, which consists of layers (B) consisting of urethane foam (F-1) and urethane foam (F-3) and layer (A) consisting of thermoplastic urethane urea film (X-1-1). Table 3 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0054] <Example 11> Polyol (Q-2), polyol (Q-3), interfacing agent (S-1), crosslinking agent (R-1), foam stabilizer (I-2), catalyst (C-1), catalyst (C-3), catalyst (C-4), and foaming agent (K-1) were placed in 1L cups in the amounts listed in Table 1 and mixed uniformly in a mixer at 3000 RPM for 60 seconds. Polyisocyanate (B-1) was added to the resulting mixture and immediately mixed in a mixer at 3000 RPM for 15 seconds. The resulting mixture was placed in a 40cm x 40cm x 2cm mold on which the thermoplastic urethane urea film (X-1-1) prepared in Production Example 1 was fixed to the bottom with double-sided tape, and the lid was closed and foaming was performed to obtain the laminated sound-absorbing material (Z-11) of the present invention, consisting of layer (B) urethane foam (F-3) and layer (A) thermoplastic urethane urea film (X-1-1). Table 3 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0055] <Example 12> The same procedure as in Example 1 was followed, except that the urethane foam (F-1) was changed to melamine foam (BASF, Basotect), to obtain the laminated sound-absorbing material (Z-12) of the present invention, which consists of layer (B) being melamine foam and layer (A) being a thermoplastic urethane urea film (X-1-1). Table 3 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0056] <Example 13> The same procedure as in Example 1 was performed except that urethane foam (F-1) was changed to urethane foam (F-5) to obtain the laminated sound-absorbing material (Z-15) of the present invention, which consists of layer (B) which is urethane foam (F-5) and layer (A) which is thermoplastic urethane urea film (X-1-1). Table 3 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0057] <Example 14> By applying spray adhesive (3M spray adhesive 55) to a polyvinyl chloride film (ESCO, EA911AG-421) and layering it on top of a urethane foam (F-1), the laminated sound-absorbing material (Z-14) of the present invention, consisting of layer (B) which is urethane foam (F-1) and layer (A) which is polyvinyl chloride film, was obtained. Table 4 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0058] <Example 15> By spraying a polyethylene film (manufactured by Misumi Corporation, non-PVC sheet HPEDT0.2-10) with spray adhesive (manufactured by 3M, spray adhesive 55) and layering it on top of a urethane foam (F-1), the laminated sound-absorbing material (Z-15) of the present invention, consisting of layer (B) which is urethane foam (F-1) and layer (A) which is polyethylene film, was obtained. Table 4 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0059] <Example 16> Except for changing the thermoplastic urethane urea film (X-1-1) to the compressed chip urethane (X-2), the same procedure as in Example 1 was performed to obtain the laminated sound-absorbing material (Z-16) of the present invention, which consists of a urethane foam (F-1) as layer (B) and a compressed chip urethane (X-2) as layer (A). Table 4 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0060] <Example 17> Except for changing the thermoplastic urethane urea film (X-1-1) to the compressed nonwoven fabric (X-3-1), the same procedure as in Example 1 was performed to obtain the laminated sound-absorbing material (Z-17) of the present invention, which consists of a urethane foam (F-1) as layer (B) and a compressed nonwoven fabric (X-3-1) as layer (A). Table 4 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0061] <Example 18> Except for changing the thermoplastic urethane urea film (X-1-1) to the compressed nonwoven fabric (X-3-2), the same procedure as in Example 1 was performed to obtain the laminated sound-absorbing material (Z-18) of the present invention, which consists of a urethane foam (F-1) as layer (B) and a compressed nonwoven fabric (X-3-2) as layer (A). Table 4 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0062] <Example 19> Except for changing the thermoplastic urethane urea film (X-1-1) to the compressed urethane foam (X-4), the same procedure as in Example 1 was performed to obtain a laminated sound-absorbing material (Z-19) consisting of layer (B), which is urethane foam (F-1), and layer (A), which is compressed urethane foam (X-4). Table 4 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0063] <Comparative Example 1> Polyol (Q-2), polyol (Q-3), interconnecting agent (S-1), crosslinking agent (R-1), foam stabilizer (I-2), catalyst (C-1), catalyst (C-3), catalyst (C-4), and foaming agent (K-1) were placed in 1L cups in the amounts listed in Table 1 and mixed uniformly in a mixer at 3000 RPM for 60 seconds. Polyisocyanate (B-1) was added to the resulting mixture and immediately mixed in a mixer at 3000 RPM for 15 seconds. The resulting mixture was placed in a 40cm x 40cm x 2cm mold on which the thermoplastic urethane urea film (X-1-1) prepared in Production Example 1 was fixed to the bottom with double-sided tape, and the lid was closed and foaming was performed to obtain the laminated sound-absorbing material of the present invention (ratio Z-1), consisting of layer (B) urethane foam (F-4) and layer (A) thermoplastic urethane urea film (X-1-1). Table 5 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0064] [Comparative Manufacturing Example 1: Manufacturing of Thermoplastic Urethane Urea Film (Ratio X-1)] The thermoplastic urethane urea resin (U-1) was press-molded with a spacer at 180°C for 60 seconds and 5 MPa to obtain a thermoplastic urethane urea film (specifically X-1), which is a film-like molded body with a film thickness of 1.5 mm.

[0065] <Comparative Example 2> A thermoplastic urethane urea film (ratio X-1) was layered on top of a urethane foam (F-1), and heat treatment was performed at 160°C for 10 minutes to obtain the laminated sound-absorbing material (ratio Z-2) of the present invention, which consists of layer (B), which is urethane foam (F-1), and layer (A), which is the thermoplastic urethane urea film (ratio X-1). Table 5 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0066] <Comparative Example 3> A polyethylene terephthalate film with a thickness of 0.03 mm (hereinafter abbreviated as PET film, manufactured by Nippa Corporation, PET25×2-CBD-A3) was sprayed with spray adhesive (manufactured by 3M, spray adhesive 55), and this was then layered onto a urethane foam (F-1) to obtain the laminated sound-absorbing material of the present invention (ratio Z-3), which consists of layer (B) which is urethane foam (F-1) and layer (A) which is PET film. Table 5 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0067] [Comparative Manufacturing Example 2: Manufacturing of Urethane Foam (F-4)] Polyol (Q-2), polyol (Q-3), connecting agent (S-1), crosslinking agent (R-1), foam stabilizer (I-2), catalyst (C-1), catalyst (C-3), catalyst (C-4), and blowing agent (K-1) were placed in 1L cups in the amounts listed in Table 1 and mixed uniformly in a mixer at 3000 RPM for 60 seconds. Polyisocyanate (B-1) was added to the resulting mixture and immediately mixed in a mixer at 3000 RPM for 15 seconds. The mixed mixture was placed in a 40cm x 40cm x 2cm mold, the lid was closed, and foaming was performed to obtain a 20mm thick urethane foam (F-4).

[0068] <Comparative Example 4> Polyurethane foam (F-4) was designated as Comparative Example 4. Table 5 shows the physical properties of the urethane foam (F-4), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0069] <Comparative Example 5> Polyurethane foam (F-1) was designated as Comparative Example 5. Table 5 shows the physical properties of the urethane foam (F-5), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0070] <Comparative Example 6> A nonwoven fabric (Thinsulate: manufactured by 3M) was designated as Comparative Example 6. Table 5 shows the physical properties of the nonwoven fabric (Thinsulate: manufactured by 3M), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0071] <Comparative Example 7> Comparative Example 7 was a vibration damping material (Calmflex RZ-13350: manufactured by Inoac Living Co., Ltd.). The physical properties of the vibration damping material, the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1 are shown in Table 5.

[0072] [Comparative Manufacturing Example 3: Manufacturing of Compressed Nonwoven Fabric (Ratio X-3)] A nonwoven fabric (Thinsulate: manufactured by 3M) was press-molded at 55°C for 60 seconds at 0.8 MPa to obtain a compressed nonwoven fabric (ratio X-3) that is a film-like molded body with a film thickness of 1.5 mm.

[0073] <Comparative Example 8> By spraying a compressed nonwoven fabric (ratio X-3) with spray adhesive (3M spray adhesive 55) and layering it on top of a urethane foam (F-1), the laminated sound-absorbing material (ratio Z-8) of the present invention, consisting of layer (B) which is urethane foam (F-1) and layer (A) which is compressed nonwoven fabric (ratio X-3), was obtained.

[0074] [Comparative Manufacturing Example 4: Manufacturing of Urethane Foam (F-6)] Polyol (Q-9), foam stabilizer (I-4), catalyst (C-4), catalyst (C-5), catalyst (C-6), flame retardant (N-1), and blowing agent (K-1) were placed in 1L cups in the amounts listed in Table 1 and mixed uniformly in a mixer at 3000 RPM for 60 seconds. Polyisocyanate (B-3) was added to the resulting mixture and immediately mixed in a mixer at 3000 RPM for 15 seconds. The mixture was then poured into a 40cm x 100cm x 5cm mold and foamed to obtain urethane foam (F-6).

[0075] <Comparative Example 9> A thermoplastic urethane urea film (X-1-1) was layered on top of a urethane foam (F-6), and heat treatment was performed at 160°C for 10 minutes to obtain the laminated sound-absorbing material of the present invention (ratio Z-9), which consists of layer (B), which is urethane foam (F-6), and layer (A), which is the thermoplastic urethane urea film (X-1-1). Table 5 shows the physical properties of layer (A) and layer (B), the basis weight of the laminated sound-absorbing material measured in the same manner as in Example 1, and the sound absorption performance of the laminated sound-absorbing material measured in the same manner as in Example 1.

[0076] Table 1 shows the compositions of the urethane foams (F-1), (F-2), and (F-5) obtained in Production Examples 10 to 12, as well as the urethane foam (F-3) obtained in Example 10 and the urethane foam (F-4) obtained in Comparative Example 1. Furthermore, the laminated sound-absorbing material obtained in Examples 1 to 19, and the comparative material obtained in Comparative Examples 1 to 9 Tables 2-5 show the results of measuring the materials constituting each layer of the laminated sound-absorbing material, the physical properties of each layer (apparent density, thickness, and air permeability), and the normal incidence sound absorption coefficient of the laminated sound-absorbing material.

[0077] [Table 1]

[0078] The components listed in Table 1 are as follows: Polyol (Q-1): PO / EO adduct of glycerin, hydroxyl value 50.6 Polyol (Q-2): PO / EO adduct of glycerol, hydroxyl value 28.0 Polyol (Q-3): PO·EO adduct of glycerin and sorbitol, hydroxyl value 32.5 Polyol (Q-4): PO adduct of glycerol, hydroxyl value 22.4 Polyol (Q-5): PO / EO adduct of glycerin, hydroxyl value 112 Polyol (Q-6): Propylene glycol PO adduct, hydroxyl value 280 Polyol (Q-7): Copolymer of glycerol PO adduct, phthalic anhydride, and PO / Glycerol PO adduct = 80 / 20, hydroxyl value 56 Polyol (Q-8): Propylene glycol PO adduct, hydroxyl value 28 Polyol (Q-9): Pentaerythritol PO adduct, hydroxyl value 400 Polyisocyanate (B-1): Coronate T-80 [Manufactured by Tosoh Corporation] Polyisocyanate (B-2): Coronate T-1021 [Manufactured by Tosoh Corporation, TDI-80 (2,4- and 2,6-TDI, 2,4-isomer ratio is 80%) / Crude MDI = 80 / 20 mixture (weight ratio), isocyanate group content = 44.6% by weight] Polyisocyanate (B-3): Millionate MR-200 [Manufactured by Tosoh Corporation] Connecting agent (S-1): PO / EO adduct of glycerin, hydroxyl value 25 Crosslinking agent (R-1): Triethanolamine Foam stabilizer (I-1): Niax Silicone L-580 [Momentive Co., Ltd.] Foam stabilizer (I-2): Tegostab B8738LF2 [manufactured by Evonik] Foam stabilizer (I-3): Niax Silicone L-598 [Momentive Co., Ltd.] Foam stabilizer (I-4): SH-193 [manufactured by Dow Toray Ltd.] Catalyst (C-1): DABCO-33LV [Manufactured by Air Products Japan Co., Ltd., a 33 wt% dipropylene glycol solution of triethylenediamine] Catalyst (C-2): Neostan U-28 [manufactured by Nitto Kasei Co., Ltd.] Catalytic converter (C-3): TOYOCAT RX-4 [Manufactured by Tosoh Corporation] Catalyst (C-4): TOYOCAT ETS [manufactured by Tosoh Corporation, bis(N,N-dimethylamino-2-ethyl) ether] Catalyst (C-5): Polycat 8 [Manufactured by Sunapro Co., Ltd.] Catalyst (C-6): U-CAT SA-1 [Manufactured by Sunapro Co., Ltd.] Flame retardant (N-1) TMCPP [Manufactured by Daihachi Chemical Industry Co., Ltd.] Foaming agent (K-1): Water

[0079] The hydroxyl value in this invention is measured by the method specified in JIS K0070 (1995 edition).

[0080] [Table 2]

[0081] [Table 3]

[0082] [Table 4]

[0083] [Table 5]

[0084] The physical properties, basis weight of the laminated sound-absorbing material, and sound absorption performance of Examples 1-19 and Comparative Examples 1-9 were measured as follows.

[0085] <Apparent density of layer (A)> The apparent density was measured in accordance with JIS K7222:2005.

[0086] <Thickness of layer (A)> The thickness was measured in accordance with JIS K7130:1999.

[0087] <Air permeability> Measured in accordance with JIS K6400 (units are cm) 3 / cm 2 ( / sec).

[0088] <Apparent density of layer (B)> The apparent density was measured in accordance with JIS K7222:2005.

[0089] <Thickness of layer (B)> The thickness was measured in accordance with JIS K7248:2005.

[0090] <Weight of laminated sound-absorbing material> The weight (basis weight) of layer (B) in the laminated sound-absorbing material was calculated by multiplying the density of layer (B), measured according to the underwater displacement method of JIS K7112:1999, by the thickness of layer (B). If layer (B) is a nonwoven fabric, the basis weight of the nonwoven fabric was determined based on "mass per unit area" in JIS L-1913:2010, 6.2. If layer (B) is polyurethane foam, the apparent density of the porous material was measured in accordance with JIS K7222:2005 and calculated by multiplying it by the thickness. In Example 10, where layer (B) is composed of two types of layers, the basis weight of the laminated sound-absorbing material was defined as the sum of the basis weights of each layer (unit: kg / m). 2 ).

[0091] <Sound absorption coefficient of laminated sound-absorbing material with perpendicular incidence> The normal incidence sound absorption coefficient was measured according to the method compliant with JIS A 1405-2. A sound absorption coefficient of 1 indicates that all sound is absorbed, and a coefficient of 0 indicates that all sound is reflected. "Sound absorption coefficient at frequencies of 500-1000 Hz" means "the average value of the sound absorption coefficient at frequencies of 500-1000 Hz."

[0092] Tables 2-5 show that the laminated sound-absorbing material of the present invention, despite its small thickness and light weight, exhibits excellent sound absorption in the 500-1000Hz frequency range, which is considered uncomfortable for humans. [Industrial applicability]

[0093] Despite its small thickness and light weight, the laminated sound-absorbing material of the present invention exhibits excellent sound absorption in the 500-1000Hz frequency range, which is considered unpleasant to humans. Therefore, it is suitable for use as a sound-absorbing material in automobiles, such as for road noise, engine compartments, and door trims.

Claims

[Claim 1] At least one layer (A), A laminated sound-absorbing material comprising at least one layer (B), Layer (A) consists of a resin film. Layer (B) consists of a porous material, The apparent density of layer (A) is 0.9–1.3 g / cm³. ３ And, Air permeability of layer (A) according to JIS K6400 (A1, unit: cm) ３ / cm ２ ( / sec) is 0 cm ３ / cm ２ / sec, The total thickness of layer (A) (T1, in mm) is 0.1 to 1.0 mm. The apparent density of layer (B) is 0.010–0.060 g / cm³. ３ And, The air permeability of layer (B) according to JIS K6400 is 3 to 150 cm. ３ / cm ２ / sec, The total thickness of layer (B) is 10 to 35 mm, and layer (A) is arranged in a direction opposite to the sound source.

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