Modified inorganic fiber material and method for manufacturing the same, automotive ceiling composite material, sound insulation composite material, and vehicle

Abstract

The modified inorganic fiber material comprises a porous inorganic fiber material and a porous powder material, wherein the porous powder material is distributed in a three-dimensional network structure on the surface and internal space of the porous inorganic fiber material by the binding of the adhesive, and the content of the porous powder material and adhesive is 10 to 200 g / m². 2 The above content = (CB) / A (wherein A and B are the surface area and mass of the porous inorganic fiber material, respectively, and the units are m 2 The invention provides a modified inorganic fiber material and a method for manufacturing the same, an automobile ceiling composite material, a sound-insulating composite material, and a vehicle. The modified inorganic fiber material has a significantly improved sound absorption coefficient and an efficient sound absorption and noise reduction function. When used as the material for the inorganic fiber material layer in an automobile ceiling composite material, it significantly improves the sound absorption and noise reduction function of the automobile ceiling composite material, reduces in-vehicle noise, and improves the ride comfort for passengers.

Description

[Technical Field]

[0001] This application requests priority from a Chinese patent application filed with the China National Intellectual Property Office on May 17, 2023, with application number 202310557936.3, and titled "Modified Inorganic Fiber Material, Method for Manufacturing the Same, and Automobile Ceiling Composite Material," the entire contents of which are incorporated into this application by reference.

[0002] The present invention relates to modified inorganic fiber materials and methods for producing the same, automotive ceiling composite materials, sound insulation composite materials, and vehicles, and belongs to the field of materials, particularly the field of automotive-related materials. [Background technology]

[0003] Currently, with the development and progress of society and the improvement of people's living standards, automobiles have become common consumer goods and are widespread in many households. At the same time, consumers' interest in and demand for levels of noise and vibration control inside automobiles are increasing. NVH (noise vibration harshness) is the subjective sensory characteristic of an automobile in relation to hearing, touch, and sight for passengers. NVH performance is the automobile performance that is most easily perceived by passengers and is an important indicator for evaluating the quality of an automobile.

[0004] The ceiling of a car is one of the most important decorative components in an automobile's interior. It not only significantly improves the decorative quality of the car's interior, but also provides insulation, soundproofing, and noise reduction functions, thereby improving passenger comfort. Because the ceiling has a large surface area, it has a significant impact on absorbing cabin noise. From this perspective, developing automotive ceiling materials with efficient sound absorption and noise reduction functions to significantly reduce cabin noise and improve passenger comfort is of great importance.

[0005] Several companies have made attempts and efforts to improve and enhance the sound absorption and noise reduction capabilities of car ceilings, specifically as follows:

[0006] CN103921504A discloses a new type of automobile roof and its production process. The disclosed new type of automobile roof is composed of composite knit fabric, glass fiber felt, foam board, glass fiber felt, and a lower nonwoven fabric, in that order from top to bottom, and each layer is bonded together with an adhesive film. The process for producing the above-described new type of automobile roof combines the advantages of a simple dry molding process and a fast production cycle, with the advantages of a wet molding process, which offers superior product molding performance compared to a roof made by a dry molding process, and the advantage of a lighter product. This molding process is also a dry-wet hybrid method (cold material hot mold) molding process. This prior art has advantages such as reduced VOC performance of the product, improved NVH performance of the product, good product molding performance, lighter product, improved production cycle, and less pollution to the production environment.

[0007] CN211417409U discloses a composite material automobile roof. The composite material automobile roof includes a carbon fiber composite roof body and a skylight frame, with a front reinforcing member bonded to the left end of the carbon fiber composite roof body and a rear reinforcing member bonded to the right end of the carbon fiber composite roof body, and the skylight frame located inside the left end of the carbon fiber composite roof body. Compared to conventional automobile roofs, the composite material automobile roof can reduce the weight of the automobile, thereby achieving energy saving and emission reduction effects of the automobile, improving the environmental protection of the automobile roof, improving the rigidity and aging resistance of the automobile roof, thereby improving the dent resistance and service life of the automobile roof, improving the specific modulus of the automobile roof, improving the NVH performance of the roof, improving the damping and sound insulation performance of the automobile roof, and simultaneously employing a wet press molding process.

[0008] However, both of these conventional technologies are improvements made from the manufacturing process of the car ceiling, and do not involve improving the materials used in the car ceiling to enhance sound absorption and noise reduction capabilities.

[0009] Therefore, providing novel modified inorganic fiber materials and methods for manufacturing the same, as well as automotive ceiling composite materials, sound insulation composite materials, and vehicles containing the modified inorganic fiber material, is a technical challenge that needs to be addressed in this field. [Overview of the project]

[0010] One objective of the present invention is to provide a modified inorganic fiber material in order to solve the above-mentioned drawbacks and deficiencies.

[0011] Another object of the present invention is to provide a method for producing the above-described modified inorganic fiber material.

[0012] Another object of the present invention is to provide an automotive ceiling composite material in which the material of the inorganic fiber material layer is the modified inorganic fiber material described above.

[0013] Another object of the present invention is to provide a sound-insulating composite material in which the material of the inorganic fiber material layer is the modified inorganic fiber material described above.

[0014] The final object of the present invention is to provide a vehicle containing the above-described sound-insulating composite material.

[0015] To achieve the above objective, in one aspect of the present invention, a modified inorganic fiber material comprises a porous inorganic fiber material and a porous powder material, wherein the porous powder material is distributed in a three-dimensional network structure on the surface and internal space of the porous inorganic fiber material by bonding with an adhesive. The content of the porous powder material and adhesive is 10 to 200 g / m². 2 The above content = (CB) / A (wherein A and B are the surface area and mass of the porous inorganic fiber material, respectively, and the units are m 2 The modified inorganic fiber material is provided, where C is the total weight of the modified inorganic fiber material (unit: g).

[0016] In one specific embodiment of the modified inorganic fiber material of the present invention, the modified inorganic fiber material is first uniformly mixed with a porous powder material, an adhesive, an auxiliary agent, and water to obtain a mixed slurry, then uniformly applied to the surface of the porous inorganic fiber material, and further manufactured through freeze molding and vacuum freeze drying.

[0017] In one specific embodiment of the modified inorganic fiber material of the present invention, the porous inorganic fiber material has a loosely porous three-dimensional network structure, a thickness of 80 to 600 μm, and a basis weight of 20 to 200 g / m². 2 That is the case.

[0018] In one specific embodiment of the modified inorganic fiber material of the present invention, the porous inorganic fiber material includes glass fibers, ceramic fibers, basalt fibers, carbon fibers, quartz fibers, asbestos fibers, volcanic rock fibers, metal fibers, or alumina fibers.

[0019] In one specific embodiment of the modified inorganic fiber material of the present invention, the porous powder material is a porous powder material having sound absorption and noise reduction functions, and includes one or more types from among zeolite molecular sieves, activated silica, activated carbon, surface porous calcium carbonate, and surface porous calcium silicate.

[0020] In order to significantly improve the sound absorption and noise reduction effects of the modified inorganic fiber material, in one specific embodiment of the modified inorganic fiber material of the present invention, the zeolite molecular sieve includes one or a combination of several types from among MFI structure molecular sieves, FER structure molecular sieves, CHA structure molecular sieves, MEL structure molecular sieves, TON structure molecular sieves, and MTT structure molecular sieves.

[0021] In one specific embodiment of the modified inorganic fiber material of the present invention, the particle size of the zeolite molecular sieve is 0.5 to 10 μm.

[0022] In one specific embodiment of the modified inorganic fiber material of the present invention, the zeolite molecular sieve includes micropores with a pore diameter of 0.3 to 0.7 nm and mesopores with a pore diameter of 10 to 30 nm.

[0023] In one specific embodiment of the modified inorganic fiber material of the present invention, the zeolite molecular sieve is a ZSM-5 molecular sieve.

[0024] In one specific embodiment of the modified inorganic fiber material of the present invention, the adhesive includes an organic adhesive and / or an inorganic adhesive. Here, the organic adhesive includes one or a combination of multiple types such as polyacrylate, acrylic copolymer, polyurethane, polystyrene butadiene emulsion, polystyrene acrylate, polystyrene acetate emulsion, polyvinyl acetate emulsion, silicone resin, and polybutadiene rubber emulsion, and the inorganic adhesive includes one or a combination of multiple types such as silica sol, alumina sol, and pseudo-boehmite.

[0025] In one specific embodiment of the modified inorganic fiber material of the present invention, since the thickness of the modified inorganic fiber material is determined by the porous inorganic fiber material, the thickness range is also 80 to 600 μm.

[0026] Furthermore, the present invention also provides (1) uniformly mixing a porous powder material, an adhesive, an auxiliary agent, and water to obtain a mixed slurry; (2) uniformly applying the mixed slurry onto the surface of the porous inorganic fiber material; (3) drying the product obtained in step (2) to obtain the modified inorganic fiber material. The present invention also provides a method for manufacturing the above-mentioned modified inorganic fiber material, which includes the above steps.

[0027] In step (2) of the above-described method for manufacturing the modified inorganic fiber material, the mixed slurry can be uniformly applied to one surface of the porous inorganic fiber material so that after application, the mixed slurry enters the interior of the porous inorganic fiber material and diffuses to the other surface of the porous inorganic fiber material. Alternatively, the mixed slurry can be uniformly applied simultaneously to both surfaces of the porous inorganic fiber material so that after application, the mixed slurry enters the interior of the porous inorganic fiber material. Assuming that the amount applied, i.e., the mass of the oven-drying paint (porous powder material and adhesive in this invention) per unit area is the same, the effects of these two application methods are the same. As can be seen from this, regardless of which application method is adopted, both surfaces of the inorganic fiber material are modified.

[0028] In one specific embodiment of the above-described manufacturing method of the present invention, the mass ratio of the porous powder material, adhesive, water, and auxiliary agent is 100:4 to 10:1 to 159:1 to 159, preferably 100:5 to 8.5:5 to 95:5 to 95. The amounts used for the porous powder material, adhesive, and auxiliary agent are all calculated based on the oven-dry mass of the active ingredient.

[0029] In one specific embodiment of the above-described manufacturing method of the present invention, the auxiliary agent is a liquid auxiliary agent that can be frozen at -30°C to -50°C and sublimated at a temperature of 60 to 80°C and a vacuum of less than 15 Pa.

[0030] In one specific embodiment of the above-described manufacturing method of the present invention, the viscosity of the liquid additive is 500 cp or more under conditions of a temperature of 20°C.

[0031] In one specific embodiment of the above-described manufacturing method of the present invention, the auxiliary agent includes one or a combination of several such substances, including ethylene glycol (melting point -13°C, boiling point 194°C / 760 mmHg), 2,3-butanediol (melting point 18°C, boiling point 179°C / 760 mmHg), 1,4-butanediol, 1,3-butanediol, and 1,5-pentanediol.

[0032] The additive used in this invention is a high-viscosity liquid additive. By adjusting the amount added, the viscosity of the mixed slurry can be adjusted, thereby meeting the viscosity requirements of the coating operation. Furthermore, during the molding and drying process of the modified inorganic fiber material, it is easily separated from the porous inorganic fiber material, porous powder material, and adhesive, and does not affect the acoustic performance of the modified inorganic fiber material. On the other hand, with additives such as starch, polyvinyl alcohol, carboxymethylcellulose, and synthetic paint thickeners commonly used in this field, the viscosity of the mixed slurry can also be adjusted by adjusting the amount added. However, these substances do not volatilize during the molding and drying process of the modified inorganic fiber material and are adsorbed onto the porous powder material, seriously negatively affecting the acoustic performance and sound absorption / noise reduction performance of the modified inorganic fiber material.

[0033] In one specific embodiment of the above-described manufacturing method of the present invention, the viscosity of the mixed slurry is 30 to 800 cp.

[0034] In one specific embodiment of the above-described manufacturing method of the present invention, the water includes one or more types of water, such as deionized water, distilled water, and reverse osmosis water.

[0035] In one specific embodiment of the above manufacturing method of the present invention, step (3) includes first performing freeze molding on the product obtained in step (2), and then performing vacuum freeze-drying on the product obtained after freeze molding, or The drying process includes directly performing high-temperature drying on the product obtained in step (2).

[0036] In one specific embodiment of the above manufacturing method of the present invention, the freeze-molding temperature is -20°C or lower, preferably -30°C to -50°C, and the freeze-molding time is 60 seconds or less.

[0037] The vacuum freeze-drying process includes raising the temperature from below -20°C to 60-80°C by programmed heating after freeze-molding, while maintaining a vacuum level of less than 15 Pa during the vacuum freeze-drying process.

[0038] In one specific embodiment of the above manufacturing method of the present invention, the high-temperature drying is performed at 85 to 150°C for 60 to 300 minutes.

[0039] Preferably, the high-temperature drying is carried out under reduced pressure or a vacuum. Under these high-temperature drying conditions, water and auxiliary agents in the mixed slurry are removed, but the porous powder material and adhesive remain distributed throughout the surface and internal structure (three-dimensional network structure of the internal space) of the porous inorganic fiber material. In this way, a modified inorganic fiber material is obtained.

[0040] In one specific embodiment of the above manufacturing method of the present invention, step (1) specifically includes the following steps:

[0041] The required porous powder material, adhesive, and auxiliary agent are accurately weighed and added to the required amount of water. Then, the porous powder material, adhesive, and auxiliary agent are uniformly dispersed and mixed using conventional dispersion methods such as stirring, shearing, and ultrasonic waves to obtain a uniformly dispersed mixed slurry. As can be seen from this, the objective of step (1) is to prepare a uniformly dispersed mixed slurry and to give the mixed slurry a predetermined viscosity, thereby satisfying the requirements of the coating operation in step (2).

[0042] In one specific embodiment of the above manufacturing method of the present invention, step (2) specifically includes the following steps:

[0043] The mixed slurry is uniformly applied to the surface of the porous inorganic fiber material using a standard bar coater, blade coater, film transfer coater (also called a roll transfer coater), bar + blade coater, etc. During the coating process, the coating amount can be adjusted from 10 to 200 g / m² by adjusting the coater setup, adjusting the concentration of the porous powder material in the mixed slurry and the viscosity of the mixed slurry, and selecting porous inorganic fiber material of different thicknesses. 2 The modified inorganic fiber material described above is obtained.

[0044] The porous inorganic fiber material used in this invention has a loosely porous three-dimensional network structure. Therefore, after application, the mixed slurry is uniformly absorbed into the three-dimensional network structure of the surface and internal space of the porous inorganic fiber material and distributed uniformly throughout the entire surface and internal structure (three-dimensional network structure of the internal space) of the porous inorganic fiber material. This differs from the coating of coated paper currently in general use. Furthermore, after application to coated paper, it is required that the coating remain on the surface of the base paper as much as possible.

[0045] In one specific embodiment of the above-described manufacturing method of the present invention, the freeze molding in step (3) specifically includes rapidly / immediately transferring the product obtained in step (2) to a vacuum freeze dryer after the coating operation is completed to perform rapid freeze molding.

[0046] In one specific embodiment of the above-described manufacturing method of the present invention, the vacuum freeze-drying process in step (3) specifically includes, after the mixed slurry has been completely freeze-molded on the surface and throughout the entire internal structure (three-dimensional network structure of the internal space) of the porous planar carrier material, starting a vacuum pump, setting a heating program for the vacuum freeze-dryer, raising the temperature from -20°C or below, preferably from -30°C to -50°C, to 60 to 80°C by programmed heating, and performing the vacuum freeze-drying process while maintaining a vacuum level of less than 15 Pa.

[0047] During the operation of the vacuum freeze-dryer, the ultimate vacuum level of the equipment is extremely low, usually less than 15 Pa. As a result, the frozen water and additives in the mixed slurry gradually begin to sublimate, but the porous powder material and adhesive remain distributed throughout the surface and internal structure (three-dimensional network structure of the internal space) of the porous inorganic fiber material. In this way, a modified inorganic fiber material is obtained. Simultaneously, the sublimation of water and additives creates a large number of uniformly distributed voids on the surface and inside of the modified inorganic fiber material. This contributes to air circulation and also contributes to the full expression of the acoustic properties and sound absorption / noise reduction performance of the porous powder material.

[0048] In another aspect, the present invention also provides an automotive ceiling composite material comprising a polyurethane layer, inorganic fiber material layers provided on both sides of the polyurethane layer, and a decorative layer, wherein the material of the inorganic fiber material layer is the modified inorganic fiber material described above. The automotive ceiling composite material provided by the present invention is an automotive ceiling composite material having efficient sound absorption and noise reduction functions.

[0049] In this invention, the method for manufacturing the automotive ceiling composite material is not particularly limited; it is sufficient to obtain the automotive ceiling composite material. It may be manufactured using conventional general methods, or the manufacturing method may be rationally adjusted and improved according to the actual work requirements on site.

[0050] In yet another aspect, the present invention also provides a sound-insulating composite material comprising an inorganic fiber material layer and a protective layer provided on at least one side of the inorganic fiber material layer, wherein the material of the inorganic fiber material layer is the modified inorganic fiber material described above.

[0051] In this invention, the material of the protective layer in the sound-insulating composite material is not particularly limited and can be reasonably selected and adjusted according to actual requirements. For example, the material of the protective layer includes a material that prevents powder shedding and / or a waterproof material. The material that prevents powder shedding may be a mesh cloth, and the waterproof material may be a waterproof membrane.

[0052] In a final aspect, the present invention also provides a vehicle comprising the sound-insulating composite material fixed to the vehicle body structure and / or the interior of the vehicle. By fixing the sound-insulating composite material to the vehicle body structure and / or the interior of the vehicle, noise from vehicle operation and / or noise transmitted from outside the vehicle can be reduced.

[0053] Compared to the prior art, the beneficial technical effects that the present invention can achieve include the following: 1. The modified inorganic fiber material provided by the present invention has a significantly improved sound absorption coefficient and possesses efficient sound absorption and noise reduction functions. 2. By using the modified inorganic fiber material provided by the present invention as the material for the inorganic fiber layer in an automotive ceiling composite material, the sound absorption and noise reduction functions of the automotive ceiling composite material can be significantly improved without changing the manufacturing process of the conventional automotive ceiling composite material, thereby reducing in-vehicle noise and improving passenger comfort. 3. The method for producing the modified inorganic fiber material provided by the present invention is simple and easy to implement, does not require special equipment, and is easy to operate. Furthermore, because a coating operation is employed when producing the modified inorganic fiber material, the present invention can efficiently produce the modified inorganic fiber material. [Brief explanation of the drawing]

[0054] To more clearly illustrate embodiments of the present invention or technical concepts in the prior art, the drawings that need to be used in describing the embodiments are briefly described below. Clearly, the drawings in the following description are some embodiments of the present invention, and those skilled in the art can obtain other drawings based on these without progressive work. [Figure 1] This is a schematic surface diagram of a glass fiber with a basis weight of 25 g / m2 used in Example 1 of the present invention, obtained using a high-resolution digital microscope. [Figure 2] This is a schematic surface diagram of the modified glass fiber produced in Example 1 of the present invention, obtained using a high-resolution digital microscope. [Figure 3]This is a schematic cross-sectional view of the modified glass fiber produced in Example 1 of the present invention, obtained using a high-resolution digital microscope. [Figure 4] This is a schematic cross-sectional view of the modified glass fiber produced in Example 3 of the present invention, obtained using a high-resolution digital microscope. [Figure 5] This is a schematic diagram of the structure of the automotive ceiling composite material provided in Example 4 of the present invention. [Modes for carrying out the invention]

[0055] Furthermore, the term "includes" and any variation thereof in the specification and claims of the present invention are intended to include non-exclusive inclusion. For example, a process, method, system, product, or equipment comprising a series of steps or units is not necessarily limited to the steps or units explicitly listed, and may include steps or units not explicitly listed, or other steps or units specific to those processes, methods, products, or equipment.

[0056] The “range” disclosed in this invention is given in the form of a lower limit and an upper limit. There may be one or more lower limits and one or more upper limits, respectively. A specified range is limited by selecting one lower limit and one upper limit. The selected lower and upper limits define the boundaries of a particular range. All such limited ranges are combinable, that is, any lower limit and any upper limit may be combined to form a single range. For example, if the ranges 60-120 and 80-110 are listed for a particular parameter, it can be understood that the ranges 60-110 and 80-120 are also expected. Furthermore, if the minimum listed range values ​​are 1 and 2, and the maximum listed range values ​​are 3, 4 and 5, then the ranges 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5 are all expected.

[0057] In this invention, unless otherwise specified, the numerical range "a~b" represents an abbreviation for any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0~5" in this invention represents a complete list of all real numbers between "0~5", and "0~5" is merely an abbreviated representation of combinations of these numbers.

[0058] In the present invention, unless otherwise specified, all embodiments and preferred embodiments referred to in the present invention can be combined with each other to form new technical solutions.

[0059] In this invention, unless otherwise specified, all constituent elements and preferred constituent elements referred to herein can be combined with each other to form new technical solutions.

[0060] In this invention, unless otherwise specified, the term "two types" as used herein means "at least two types."

[0061] In the present invention, unless otherwise specified, all steps mentioned may be performed sequentially or randomly, but it is preferable to perform them sequentially. For example, if the method includes steps (a) and (b), the method may include steps (a) and (b) performed sequentially, or steps (b) and (a) performed sequentially. For example, if the method may further include step (c), step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), or steps (a), (c) and (b), or steps (c), (a) and (b), etc.

[0062] To further clarify the object, technical proposal and advantages of the present invention, the present invention will be described in more detail below with reference to tables, drawings and examples. The examples described below are some examples of the present invention, not all examples, and are for illustrative purposes only and do not limit the scope of the present invention. All other examples obtained by those skilled in the art without progressive work based on the examples of the present invention are within the scope of the present invention. Unless specific conditions are stated in the examples, the procedures were carried out under normal conditions or conditions suggested by the manufacturer. Unless the manufacturer is specified, the reagents and equipment used are all commercially available and common products. [Examples]

[0063] This embodiment provides a modified glass fiber material manufactured by a manufacturing method that includes the following specific steps.

[0064] (a) 100 parts by weight of ZSM-5 molecular sieve, 5 parts by weight of polystyrene-butadiene adhesive, 85 parts by weight of deionized water, and 5 parts by weight of ethylene glycol were accurately weighed. Here, the amounts of ZSM-5 molecular sieve, polystyrene-butadiene adhesive, and ethylene glycol used were all calculated based on the oven-dry mass of the active ingredients. The ZSM-5 molecular sieve, polystyrene-butadiene adhesive, and ethylene glycol were added to the deionized water and mixed and stirred uniformly to obtain a mixed slurry. The viscosity of the mixed slurry, measured by a digital rotational viscometer, was 52.5 cP.

[0065] Here, the ZSM-5 molecular sieve, which has sound absorption and noise reduction functions as a porous powder material, has an average particle size of 1.5 μm and contains micropores with a pore size of 0.55 nm and mesopores with a pore size of 20 nm.

[0066] (b) Using a blade coater, the base weight is 25 g / m 2 A mixed slurry was uniformly applied to glass fibers (a schematic diagram of the surface is shown in Figure 1).

[0067] (c) After the coating operation was completed, the product obtained in step (b) was quickly / immediately transferred to a vacuum freeze dryer for rapid freeze molding. The freeze molding temperature was -40°C and the time was 5 seconds.

[0068] (d) After the mixed slurry was completely freeze-molded on the surface and throughout the internal structure (three-dimensional network structure of the internal space) of the glass fiber material, the vacuum pump was started, the heating program of the vacuum freeze dryer was set, the temperature was raised from -40°C to 75°C, and the vacuum level was maintained at less than 15 Pa to perform the vacuum freeze-drying process. After the process was completed, the modified glass fiber material was obtained and designated as Test Sample 1#.

[0069] Schematic diagrams of the surface and cross-section of test sample 1# manufactured in this embodiment are shown in Figures 2 and 3, respectively. As can be seen by comparing Figure 1 and Figure 2, the porous powder material remains distributed throughout the surface and internal structure (three-dimensional network structure of the internal space) of the porous glass fiber material due to the binding action of the adhesive, and a large amount of uniformly distributed voids are created on the surface and inside the modified glass fibers by the sublimation of water and auxiliary agents.

[0070] As can be seen from Figure 3, the average thickness of test sample 1# is 134 μm. [Examples]

[0071] This embodiment provides a modified glass fiber material manufactured by a manufacturing method that includes the following specific steps.

[0072] (a) 100 parts by weight of ZSM-5 molecular sieve, 7 parts by weight of polystyrene-butadiene adhesive, 95 parts by weight of deionized water, and 20 parts by weight of ethylene glycol were accurately weighed. Here, the amounts of ZSM-5 molecular sieve, polystyrene-butadiene adhesive, and ethylene glycol used were all calculated based on the oven-dry mass of the active ingredients. The ZSM-5 molecular sieve, polystyrene-butadiene adhesive, and ethylene glycol were added to the deionized water and mixed and stirred uniformly to obtain a mixed slurry. The viscosity of the mixed slurry, measured by a digital rotational viscometer, was 60.0 cP.

[0073] Here, the ZSM-5 molecular sieve, which has sound absorption and noise reduction functions as a porous powder material, has an average particle size of 1.5 μm and contains micropores with a pore size of 0.55 nm and mesopores with a pore size of 20 nm.

[0074] (b) Using a blade coater, the base weight is 25 g / m 2 A mixed slurry was uniformly applied to the glass fiber material.

[0075] (c) After the coating operation was completed, the product obtained in step (b) was quickly / immediately transferred to a vacuum freeze dryer for rapid freeze molding. The freeze molding temperature was -40°C and the time was 8 seconds.

[0076] (d) After the mixed slurry was completely freeze-molded on the surface and throughout the internal structure (three-dimensional network structure of the internal space) of the glass fiber material, the vacuum pump was started, the heating program of the vacuum freeze dryer was set, and the temperature was raised from -40°C to 75°C while maintaining a vacuum level of less than 15 Pa to perform the vacuum freeze-drying process. After the process was completed, the modified glass fiber material was obtained and designated as test sample 2#.

[0077] As can be reasonably predicted from the characterization results of Example 1, in the test sample 2# produced in this example, the porous powder material was still distributed throughout the surface and internal structure (three-dimensional network structure of the internal space) of the porous glass fiber material due to the binding action of the adhesive, and a large amount of uniformly distributed voids were created on the surface and inside the modified glass fibers by the sublimation of water and auxiliary agents. [Examples]

[0078] This embodiment provides a modified glass fiber material manufactured by a manufacturing method that includes the following specific steps.

[0079] (a) 50 parts by weight of ZSM-5 molecular sieve, 50 parts by weight of Silicalite-1 molecular sieve, 5 parts by weight of polystyrene-butadiene adhesive, 3.5 parts by weight of polyacrylate adhesive, 20 parts by weight of deionized water, and 90 parts by weight of ethylene glycol were accurately weighed. Here, the ZSM-5 molecular sieve, MFI structure molecular sieve, polystyrene-butadiene adhesive, polyacrylate adhesive, and ethylene glycol were all calculated using the oven-dry mass of the active ingredients. The ZSM-5 molecular sieve, MFI structure molecular sieve, polystyrene-butadiene adhesive, polyacrylate adhesive, and ethylene glycol were added to the deionized water and mixed and stirred uniformly to obtain a mixed slurry. The viscosity of the mixed slurry, measured by a digital rotational viscometer, was 119 cP.

[0080] Here, the ZSM-5 molecular sieve, which has sound absorption and noise reduction functions as a porous powder material, has an average particle size of 1.5 μm and contains micropores with a pore size of 0.55 nm and mesopores with a pore size of 20 nm. The Silicalite-1 molecular sieve, which has sound absorption and noise reduction functions as a porous powder material, has an average particle size of 1.4 μm and contains micropores with a pore size of 0.60 nm and mesopores with a pore size of 11 nm.

[0081] (b) Using a blade coater, the base weight is 50 g / m 2 A mixed slurry was uniformly applied to the glass fiber material.

[0082] (c) After the coating operation was completed, the product obtained in step (b) was quickly / immediately transferred to a vacuum freeze dryer for rapid freeze molding. The freeze molding temperature was -40°C and the time was 20 s.

[0083] (d) After the mixed slurry was completely freeze-molded on the surface and throughout the internal structure (three-dimensional network structure of the internal space) of the glass fiber material, the vacuum pump was started, the heating program of the vacuum freeze dryer was set, the temperature was raised from -40°C to 75°C, and the vacuum level was maintained at less than 15 Pa to perform the vacuum freeze-drying process. After the process was completed, the modified glass fiber material was obtained and designated as test sample 3#.

[0084] As can be reasonably predicted from the characterization results of Example 1, in the test sample 3# produced in this example, the porous powder material was still distributed throughout the surface and internal structure (three-dimensional network structure of the internal space) of the porous glass fiber material due to the binding action of the adhesive, and a large amount of uniformly distributed voids were created on the surface and inside the modified glass fibers by the sublimation of water and auxiliary agents.

[0085] A schematic cross-sectional view of test sample 3# manufactured in this embodiment is shown in Figure 4. As can be seen from Figure 4, the average thickness of test sample 3# is 352 μm. [Examples]

[0086] This embodiment provides a modified glass fiber material that differs from Example 1 only in the freeze-molding and vacuum freeze-drying processes. The modified glass fiber material is manufactured by a manufacturing method that includes the following specific steps.

[0087] (a) 100 parts by weight of ZSM-5 molecular sieve, 5 parts by weight of polystyrene-butadiene adhesive, 85 parts by weight of deionized water, and 5 parts by weight of ethylene glycol were accurately weighed. Here, the amounts of ZSM-5 molecular sieve, polystyrene-butadiene adhesive, and ethylene glycol used were all calculated based on the oven-dry mass of the active ingredients. The ZSM-5 molecular sieve, polystyrene-butadiene adhesive, and ethylene glycol were added to the deionized water and mixed and stirred uniformly to obtain a mixed slurry. The viscosity of the mixed slurry, measured by a digital rotational viscometer, was 52.5 cP.

[0088] Here, the ZSM-5 molecular sieve, which has sound absorption and noise reduction functions as a porous powder material, has an average particle size of 1.5 μm and contains micropores with a pore size of 0.55 nm and mesopores with a pore size of 20 nm.

[0089] (b) Using a blade coater, the base weight is 25 g / m 2 A mixed slurry was uniformly applied to the glass fiber material.

[0090] (c) After the coating operation was completed, the product obtained in step (b) was quickly / immediately transferred to a 90°C air-dried chamber and dried for 60 minutes to obtain the modified glass fiber material, which was designated as test sample 4#. [Examples]

[0091] This embodiment provides a series of automotive ceiling composite materials. As shown in Figure 5, the schematic structure includes a polyurethane layer 1, inorganic fiber material layers 2 provided on both sides of the polyurethane layer 1, and a decorative layer 3 provided on the inorganic fiber material layers 2 and facing inwards towards the interior of the automobile. Here, the material of the inorganic fiber material layer 2 is the modified glass fiber material provided in Examples 1 to 4, i.e., Test Sample 1 to Test Sample 4.

[0092] The series of automotive ceiling composite materials provided in this embodiment are all automotive ceiling composite materials that have efficient sound absorption and noise reduction functions.

[0093] Comparative Example 1 This comparative example provides a modified glass fiber material that differs from Example 1 only in that it does not contain an ethylene glycol additive. The modified glass fiber material is manufactured by a manufacturing method that includes the following specific steps.

[0094] (a) 100 parts by weight of ZSM-5 molecular sieve, 5 parts by weight of polystyrene-butadiene adhesive, and 85 parts by weight of deionized water were accurately weighed. Here, the amounts of ZSM-5 molecular sieve and polystyrene-butadiene adhesive used were calculated based on the oven-dry mass of the active ingredients. The ZSM-5 molecular sieve and polystyrene-butadiene adhesive were added to the deionized water and mixed and stirred uniformly to obtain a mixed slurry. The viscosity of the mixed slurry, measured by a digital rotational viscometer, was 6.25 cP.

[0095] Here, the ZSM-5 molecular sieve, which has sound absorption and noise reduction functions as a porous powder material, has an average particle size of 1.5 μm and contains micropores with a pore size of 0.55 nm and mesopores with a pore size of 20 nm.

[0096] (b) Using a blade coater, a mixed slurry was uniformly applied onto a glass fiber material with a basis weight of 25 g / m 2 and obtained a modified glass fiber material with a particularly high coating amount on the obtained modified glass fiber material, which could not be accurately controlled, and at the same time, the uniformity of the obtained material was poor.

[0097] Coating result: Since the mixed slurry has a particularly low viscosity, when it is applied to the glass fiber material, the fluidity of the mixed slurry is very good, the speed at which the glass fiber material absorbs the mixed slurry is particularly fast,

[0098] As can be seen by comparing Example 1 with Comparative Example 1, the viscosity of the mixed slurry is very important for the coating operation. In the present invention, by controlling the viscosity of the mixed slurry to 30 to 800 cp with a liquid auxiliary agent, the object of manufacturing a modified glass fiber material having excellent performance can be achieved.

[0099] Comparative Example 2 This comparative example provides a modified glass fiber material produced by a manufacturing method including the following specific steps.

[0100] (a) 50 parts by weight of ZSM-5 molecular sieve, 50 parts by weight of Silicalite-1 molecular sieve, 5 parts by weight of polystyrene butadiene adhesive, 3.5 parts by weight of polyacrylate adhesive, 20 parts by weight of deionized water, and 90 parts by weight of ethylene glycol were accurately weighed. Here, the ZSM-5 molecular sieve, MFI structure molecular sieve, polystyrene butadiene adhesive, polyacrylate adhesive, and ethylene glycol were all calculated based on the absolute dry mass of the active ingredient. The ZSM-5 molecular sieve, MFI structure molecular sieve, polystyrene butadiene adhesive, polyacrylate adhesive, and ethylene glycol were added to deionized water and uniformly mixed and stirred to obtain a mixed slurry. The viscosity of the mixed slurry measured by a digital rotational viscometer was 119 cP.

[0101] Here, the ZSM-5 molecular sieve, which has sound absorption and noise reduction functions as a porous powder material, has an average particle size of 1.5 μm and contains micropores with a pore size of 0.55 nm and mesopores with a pore size of 20 nm. The Silicalite-1 molecular sieve, which has sound absorption and noise reduction functions as a porous powder material, has an average particle size of 1.4 μm and contains micropores with a pore size of 0.60 nm and mesopores with a pore size of 11 nm.

[0102] (b) Using a blade coater, the base weight is 50 g / m 2 A mixed slurry was uniformly applied to the glass fiber material.

[0103] (c) After the coating operation was completed, the product obtained in step (b) was quickly / immediately transferred to a vacuum freeze dryer for rapid freeze molding. The freeze molding temperature was -40°C and the time was 20 s.

[0104] (d) After the mixed slurry was completely freeze-molded on the surface and throughout the internal structure (three-dimensional network structure of the internal space) of the glass fiber material, the vacuum pump was started, the heating program of the vacuum freeze dryer was set, the temperature was raised from -40°C to 75°C, and the vacuum level was maintained at less than 15 Pa to perform the vacuum freeze-drying process. After the process was completed, the modified glass fiber material was obtained and designated as Reference Sample 2#.

[0105] Test Example 1 In this test example, test samples 1# to 4# and reference sample 2# were first cut into 10 x 10 mm squares, and the molecular sieve and adhesive content were calculated according to formula 1) below, based on the parameters in Table 1 below. The specific results of the aforementioned content are shown in Table 1 below.

[0106] Molecular sieve and adhesive content = (CB) / A, unit: g / m 2 , Equation 1) In Equation 1), A and B are the surface area and mass of the porous glass fiber material, respectively, and their units are m 2 and g. C is the total weight of the modified glass fiber material, and the unit is g.

[0107] [Table 1] Test Example 2 In this test example, a standing wave tube, i.e., an impedance tube, was used to test the modified glass fiber materials provided in Examples 1 to 4 and Comparative Example 2, as well as the basis weight used in the examples and comparative examples, which was 25 g / m². 2 This is glass fiber with a basis weight of 50g / m 2 The sound pressure changes of the glass fiber at different frequencies were measured, and the sound absorption coefficient was calculated based on the sound pressure change data. The experimental results are shown in Table 2 below.

[0108] [Table 2] The following was learned from the experimental data in Table 2 above.

[0109] (1) Untreated basis weight is 25 g / m 2 The sound absorption coefficients of the glass fiber material at different frequencies are significantly lower than those of the modified glass fiber materials provided in Examples 1, 2, and 4 at the same frequencies. This fully demonstrates that the noise absorption effect of the porous powder material having sound absorption and noise reduction functions in the modified glass fiber material provided in the examples of the present invention is very significant.

[0110] (2) Untreated basis weight is 50g / m 2 The sound absorption coefficients of the glass fiber material at different frequencies are significantly lower than those of the modified glass fiber material provided in Example 3 at the same frequencies. This fully demonstrates that the noise absorption effect of the porous powder material having sound absorption and noise reduction functions in the modified glass fiber material provided in the examples of the present invention is very significant.

[0111] (3) As can be seen by comparing the experimental data of Example 4 and Example 1, the sound absorption coefficient at different frequencies of the modified glass fiber material provided in Example 1 is significantly higher than that of the modified glass fiber material at the same frequency provided in Example 4. This fully demonstrates the importance of the drying method. In other words, freeze-drying is superior to high-temperature drying. This is because, in the water evaporation process of high-temperature drying, the porous powder material particles having sound absorption and noise reduction functions come closer to each other due to the action of surface tension, preventing the formation of abundant void structures in the glass fiber material. Furthermore, the film formation performance of the adhesive is superior in the high-temperature drying process compared to the freeze-drying process, and the adhesive firmly coats the glass fiber material after film formation, further reducing the void structure in the glass fiber material.

[0112] (4) As can be seen by comparing the experimental data of Example 1 or Example 4, Example 2, and Example 3, the sound absorption coefficient also improved as the oven-dry adsorption mass of the porous powder material having sound absorption and noise reduction functions increased (in the modified glass fiber materials provided in Example 1 or Example 4, Example 2, and Example 3, the oven-dry adsorption mass of the porous powder material having sound absorption and noise reduction functions was 9.62 mg, 12.62 mg, and 17.79 mg, respectively).

[0113] Furthermore, as can be seen by comparing the experimental results data of Example 3 and Comparative Example 2, the coating amount was 200 g / m². 2 Beyond a certain point, the sound absorption and noise reduction performance of the resulting modified glass fiber material actually decreased. This is because the coating layer after drying becomes denser, has a higher density, and the number of voids decreases, thus reducing the sound absorption and noise reduction effect of the modified glass fiber material.

[0114] In summary, the beneficial technical effects that the embodiments of the present invention can achieve compared to the prior art include the following: 1. The modified inorganic fiber material provided by the embodiment of the present invention exhibits a significantly improved sound absorption coefficient and has an efficient sound absorption and noise reduction function. 2. By using the modified inorganic fiber material provided by the embodiment of the present invention as the material for the inorganic fiber layer in an automotive ceiling composite material, the sound absorption and noise reduction functions of the automotive ceiling composite material can be significantly improved without changing the manufacturing process of the conventional automotive ceiling composite material, thereby reducing in-vehicle noise and improving passenger comfort. 3. The method for producing the modified inorganic fiber material provided by the embodiments of the present invention is simple and easy to implement, does not require special equipment, and is easy to operate. Furthermore, because a coating operation is employed when producing the modified inorganic fiber material, the embodiments of the present invention can efficiently produce the modified inorganic fiber material.

[0115] The above description is merely a specific embodiment of the present invention and does not limit the scope of the invention. Therefore, the substitution of equivalent parts, or equivalent changes and modifications based on the protected scope of the present invention, all fall within the scope of the present invention. Furthermore, the constituent elements of the present invention can be freely combined and used with other constituent elements, with other constituent elements and with other technical inventions, and with other technical inventions. [Explanation of Symbols]

[0116] 1. Polyurethane layer 2. Inorganic fiber material layer 3. Decorative layer

Claims

1. Modified inorganic fiber material, The modified inorganic fiber material comprises a porous inorganic fiber material and a porous powder material, wherein the porous powder material is distributed in a three-dimensional network structure on the surface and internal space of the porous inorganic fiber material by bonding with an adhesive. The content of the porous powder material and adhesive is 10 to 200 g / m 2 The above content = (CB) / A (wherein A and B are the surface area and mass of the porous inorganic fiber material, respectively, and the units are m 2 A modified inorganic fiber material characterized by the following: and g. C is the total weight of the modified inorganic fiber material, and the unit is g.

2. The porous inorganic fiber material has a loosely porous three-dimensional network structure, a thickness of 80 to 600 μm, and a basis weight of 20 to 200 g / m². 2 The modified inorganic fiber material according to claim 1, characterized in that it is the same as described in claim 1.

3. The modified inorganic fiber material according to claim 1 or 2, characterized in that the porous inorganic fiber material includes glass fibers, ceramic fibers, basalt fibers, carbon fibers, quartz fibers, asbestos fibers, volcanic rock fibers, metal fibers, or alumina fibers.

4. The modified inorganic fiber material according to claim 1, characterized in that the porous powder material includes one or a combination of zeolite molecular sieves, activated silica, activated carbon, surface porous calcium carbonate, and surface porous calcium silicate.

5. The modified inorganic fiber material according to claim 4, characterized in that the zeolite molecular sieve includes one or a combination of several types from among MFI structure molecular sieves, FER structure molecular sieves, CHA structure molecular sieves, MEL structure molecular sieves, TON structure molecular sieves, and MTT structure molecular sieves.

6. The modified inorganic fiber material according to claim 4, characterized in that the particle size of the zeolite molecular sieve is 0.5 to 10 μm.

7. The modified inorganic fiber material according to claim 4, characterized in that the zeolite molecular sieve includes micropores with a pore size of 0.3 to 0.7 nm and mesopores with a pore size of 10 to 30 nm.

8. The modified inorganic fiber material according to any one of claims 4 to 7, characterized in that the zeolite molecular sieve is a ZSM-5 molecular sieve.

9. The adhesive comprises an organic adhesive and / or an inorganic adhesive. The organic adhesive comprises one or a combination of several of the following: polyacrylate, acrylic copolymer, polyurethane, polystyrene-butadiene emulsion, polystyrene acrylate, polystyrene acetate emulsion, polyvinyl acetate emulsion, silicone resin, and polybutadiene rubber emulsion. The modified inorganic fiber material according to claim 1, characterized in that the inorganic adhesive comprises one or more types selected from silica sol, alumina sol, and pseudo-boehmite.

10. The modified inorganic fiber material according to claim 1 or 2, characterized in that the thickness of the modified inorganic fiber material is 80 to 600 μm.

11. (1) A mixture slurry is obtained by uniformly mixing porous powder material, adhesive, auxiliary agent and water. (2) Apply the mixed slurry uniformly to the surface of the porous inorganic fiber material. (3) Dry the product obtained in step (2) to obtain the modified inorganic fiber material. A method for producing a modified inorganic fiber material according to any one of claims 1 to 10, characterized by including the following:

12. The manufacturing method according to claim 11, characterized in that the mass ratio of the porous powder material, adhesive, water, and auxiliary agent is 100:4 to 10:1 to 159:1 to 159, and the amounts used for the porous powder material, adhesive, and auxiliary agent are all calculated based on the oven-dry mass of the active ingredient.

13. The manufacturing method according to claim 11, characterized in that the auxiliary agent is a liquid auxiliary agent that can be frozen at -30°C to -50°C and sublimated at a temperature of 60 to 80°C and a vacuum of less than 15 Pa.

14. The manufacturing method according to claim 13, characterized in that, under conditions of a temperature of 20°C, the viscosity of the liquid additive is 500 cp or more.

15. The manufacturing method according to any one of claims 11 to 14, characterized in that the auxiliary agent includes one or a combination of ethylene glycol, 2,3-butanediol, 1,4-butanediol, 1,3-butanediol, and 1,5-pentanediol.

16. The manufacturing method according to any one of claims 11 to 14, characterized in that the viscosity of the mixed slurry is 30 to 800 cp.

17. The manufacturing method according to any one of claims 11 to 14, characterized in that the water includes one or a combination of deionized water, distilled water, and reverse osmosis water.

18. In step (3), the drying process includes first performing freeze-molding on the product obtained in step (2), and then performing vacuum freeze-drying on the product obtained after freeze-molding, or The drying process includes directly performing high-temperature drying on the product obtained in step (2). The manufacturing method according to any one of claims 11 to 14.

19. The freeze-molding temperature is -20°C or lower, and the freeze-molding time is 60 seconds or less. The manufacturing method according to claim 18, characterized in that the vacuum freeze-drying treatment includes raising the temperature from -20°C or below to 60-80°C by programmed heating after freeze-molding, and performing the vacuum freeze-drying treatment while maintaining a vacuum level of less than 15 Pa.

20. The manufacturing method according to claim 19, characterized in that the freeze-molding temperature is -30°C to -50°C.

21. The manufacturing method according to claim 18, characterized in that the high-temperature drying is performed at 85 to 150°C for 60 to 300 minutes.

22. The manufacturing method according to claim 18, characterized in that the high-temperature drying is carried out under reduced pressure or a vacuum environment.

23. A composite material for the ceiling of an automobile, comprising a polyurethane layer, inorganic fiber material layers provided on both sides of the polyurethane layer, and a decorative layer, The material of the inorganic fiber material layer is a modified inorganic fiber material according to any one of claims 1 to 10, characterized in that it is a composite material for the ceiling of an automobile.

24. A sound-insulating composite material comprising an inorganic fiber material layer and a protective layer provided on at least one side of the inorganic fiber material layer, The sound-insulating composite material is characterized in that the material of the inorganic fiber material layer is the modified inorganic fiber material described in any one of claims 1 to 10.

25. A vehicle comprising the sound-insulating composite material described in claim 24, wherein the sound-insulating composite material is fixed to the vehicle body structure and / or inside the vehicle.

Images