Impregnating agent, modified basalt fiber fabric and preparation method and application thereof

Abstract

The application relates to an impregnating agent, a modified basalt fiber fabric and a preparation method and application thereof. The impregnating agent comprises the following components in parts by mass: 60-100 parts of a film forming agent, 5-15 parts of a coupling agent, 2-5 parts of a polyoxyethylene stearate, 1-4 parts of a long carbon chain quaternary ammonium salt, 5-15 parts of silicon oxide and 10-20 parts of an auxiliary agent, wherein the film forming agent comprises an epoxy resin emulsion, a polyurethane emulsion and a polyacrylate emulsion, and the mass ratio of the epoxy resin emulsion, the polyurethane emulsion and the polyacrylate emulsion is (4-7):1:1. The impregnating agent adopts the film forming agent, the coupling agent, the polyoxyethylene stearate, the long carbon chain quaternary ammonium salt, the silicon oxide and the auxiliary agent in a specific ratio, so that the prepared impregnating agent has good fluidity and film forming property, can form a smooth modified layer on the surface of the basalt fiber fabric, and can make the basalt fiber fabric still show golden color lines after being compounded with epoxy resin, and the modified layer can also improve the weather resistance and wear resistance of the basalt fiber fabric.

Description

Technical Field

[0001] This application relates to the field of basalt fiber fabric technology, and in particular to an impregnating agent, modified basalt fiber fabric, preparation method and application thereof. Background Technology

[0002] With economic development, the user base of commercial vehicles has changed, and drivers and passengers have increasingly higher requirements for the overall appearance quality of vehicles. Basalt fiber has a dark gold or bright silver metallic luster, and when made into fabrics and used to manufacture automotive trim, it can enhance the overall appearance quality of vehicles. However, the strength of basalt fiber fabrics is insufficient for automotive trim requirements, necessitating the composite of basalt fiber fabrics with epoxy resin to ensure overall strength. However, basalt fiber fabrics turn black when exposed to epoxy resin, affecting their appearance quality and limiting their large-scale application in automotive trim. Furthermore, traditional basalt fiber fabrics struggle to meet the weather resistance and abrasion resistance requirements of automotive trim components.

[0003] To address these issues, traditional techniques employ surface modification of basalt fiber fabrics using modifiers containing solid powders. This reduces the wettability between the fabric and epoxy resin, allowing the surface of the resulting composite material to display the original golden fiber texture of the basalt fibers, although the color remains somewhat dark. Furthermore, in this approach, the bond between the basalt fiber fabric and epoxy resin is weak, resulting in poor strength. Additionally, its weather resistance and abrasion resistance are also poor. Summary of the Invention

[0004] Therefore, it is necessary to provide an impregnating agent and its application method that can prevent discoloration of basalt fiber fabrics and improve their weather resistance and abrasion resistance. Furthermore, this application also provides a modified basalt fiber fabric and its preparation method. Even further, this application provides a basalt fiber fabric composite material, its preparation method, and its application.

[0005] In a first aspect, a wetting agent is provided, comprising the following components in parts by mass:

[0006]

[0007] The film-forming agent includes epoxy resin emulsion, polyurethane emulsion and polyacrylate emulsion, wherein the mass ratio of the epoxy resin emulsion, the polyurethane emulsion and the polyacrylate emulsion is (4-7):1:1.

[0008] This application uses a specific ratio of film-forming agent, coupling agent, polyoxyethylene stearate, long-chain quaternary ammonium salt, silicon dioxide, and additives to produce an impregnating agent with good fluidity and film-forming properties. This agent can form a smooth modified layer on the surface of basalt fiber fabric, allowing the basalt fiber fabric to still exhibit a golden yellow texture and not change color after being compounded with epoxy resin. Furthermore, the modified layer can also improve the weather resistance and abrasion resistance of the basalt fiber fabric. Specifically, a composite film-forming agent containing epoxy resin emulsion, polyurethane emulsion, and polyacrylate emulsion in a specific mass ratio can uniformly cover the surface of basalt fiber fabric. After the liquid in the film-forming agent evaporates, a smooth and transparent film can be formed on the surface of the basalt fiber fabric, reducing the wetting between the basalt fiber fabric and epoxy resin and allowing the product to retain the color of the basalt fiber fabric. Using a specific ratio of stearic acid polyoxyethylene ester and long-chain quaternary ammonium salt can make the basalt fiber fabric softer and give it a natural luster. At the same time, it can also effectively reduce surface static electricity, prevent fiber surface fuzzing, and further improve the appearance quality of the basalt fiber fabric. Silica can make the surface of the basalt fiber fabric denser, improve its strength and abrasion resistance, and silica can also reflect ultraviolet rays, thereby reducing the degradation effect of ultraviolet rays on epoxy resin and improving the weather resistance of basalt fiber and epoxy resin composite materials.

[0009] In some embodiments, the wetting agent comprises the following components by weight:

[0010]

[0011] In some embodiments, the mass ratio of the epoxy resin emulsion, the polyurethane emulsion, and the polyacrylate emulsion is (4-6):1:1.

[0012] In some embodiments, the long-chain quaternary ammonium salt contains C12 to C18 alkyl chains.

[0013] In some embodiments, the coupling agent includes at least one of aminosilane, epoxysilane, methacryloxysilane, vinylsilane, and isocyanate-based silane.

[0014] In some embodiments, the additives include at least one of a colorant and a polymerization inhibitor.

[0015] In some embodiments, the long-chain quaternary ammonium salt comprises hexadecyltrimethylammonium bromide.

[0016] Secondly, a method for using the wetting agent described in the first aspect is provided, comprising the following steps:

[0017] The wetting agent is mixed with water to obtain a coating.

[0018] The coating is applied to the target substrate.

[0019] Thirdly, a modified basalt fiber fabric is provided, comprising a basalt fiber fabric and a modified layer disposed on the surface of the basalt fiber fabric, wherein the raw materials for preparing the modified layer include the sizing agent described in the first aspect.

[0020] In some embodiments, the areal density of the basalt fiber fabric is 600 g / m³. 2 ~800g / m 2 .

[0021] In some embodiments, the diameter of the basalt fiber bundles in the basalt fiber fabric is 8 μm to 14 μm.

[0022] In some embodiments, the basalt fiber fabric is twill woven.

[0023] Fourthly, a method for preparing modified basalt fiber fabric is provided, comprising the following steps:

[0024] The wetting agent described in the first aspect is mixed with water to obtain a coating;

[0025] The coating is applied to the basalt fiber fabric in multiple layers and then dried to form a modified layer on the surface of the basalt fiber fabric, thus obtaining the modified basalt fiber fabric.

[0026] The above preparation method uses a multi-coating approach to uniformly coat the basalt fiber fabric with a coating. After drying, a smooth, continuous, and transparent modified layer is formed on the surface of the basalt fiber fabric. Compared with techniques that directly immerse the basalt fiber fabric in the coating or apply the coating to the basalt fiber fabric in one go, the multi-coating method of this application allows the resulting fabric to retain the original color of the basalt fiber.

[0027] In some embodiments, in the step of mixing the wetting agent with water, the volume ratio of the wetting agent to the water is 1:(5-20).

[0028] In some embodiments, the number of coating applications in the step of applying the coating in multiple coats is 2 to 5.

[0029] Fifthly, a basalt fiber fabric composite material is provided, comprising the modified basalt fiber fabric described in the third aspect and an epoxy resin layer disposed on the modified layer.

[0030] Sixthly, a method for preparing a basalt fiber fabric composite material is provided, comprising the following steps:

[0031] The modified basalt fiber fabric is formed using the preparation method described in the fourth aspect;

[0032] An epoxy resin layer is formed on the modified layer of the modified basalt fiber fabric to obtain the basalt fiber fabric composite material.

[0033] In a seventh aspect, an automotive trim is provided, comprising the basalt fiber fabric composite material described in the fifth aspect. Detailed Implementation

[0034] To facilitate understanding of this application, a more complete description will be provided below. This application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0036] The weights of the relevant components mentioned in the embodiments of this application can refer not only to the specific content of each component, but also to the proportional relationship between the weights of the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this application is within the scope disclosed in the embodiments of this application. Specifically, the weights mentioned in the embodiments of this application can be well-known units of mass in the chemical industry, such as μg, mg, g, and kg. All raw materials, reagents, instruments, and equipment used in this application can be purchased commercially or prepared by existing methods.

[0037] One embodiment of this application provides an impregnating agent comprising the following components by mass parts:

[0038]

[0039] The film-forming agent includes epoxy resin emulsion, polyurethane emulsion and polyacrylate emulsion, and the mass ratio of epoxy resin emulsion, polyurethane emulsion and polyacrylate emulsion is (4-7):1:1.

[0040] This embodiment uses a specific ratio of film-forming agent, coupling agent, polyoxyethylene stearate, long-chain quaternary ammonium salt, silicon dioxide, and additives to produce a sizing agent with good fluidity and film-forming properties. This agent can form a smooth modified layer on the surface of basalt fiber fabric, allowing the basalt fiber fabric to still exhibit golden fiber texture and not change color after being compounded with epoxy resin. Furthermore, the modified layer can also improve the weather resistance and abrasion resistance of the basalt fiber fabric. Specifically, a composite film-forming agent containing epoxy resin emulsion, polyurethane emulsion, and polyacrylate emulsion in a specific mass ratio can uniformly cover the surface of basalt fiber fabric. After the liquid in the film-forming agent evaporates, a smooth and transparent film can be formed on the surface of the basalt fiber fabric, reducing the wetting between the basalt fiber fabric and epoxy resin and allowing the product to retain the color of the basalt fiber fabric. Using a specific ratio of stearic acid polyoxyethylene ester and long-chain quaternary ammonium salt can make the basalt fiber fabric softer and give it a natural luster. At the same time, it can also effectively reduce surface static electricity, prevent fiber surface fuzzing, and further improve the appearance quality of the basalt fiber fabric. Silica can make the surface of the basalt fiber fabric denser, improve its strength and abrasion resistance, and silica can also reflect ultraviolet rays, thereby reducing the degradation effect of ultraviolet rays on epoxy resin and improving the weather resistance of basalt fiber and epoxy resin composite materials.

[0041] In some embodiments, the wetting agent consists of the components described above in parts by mass.

[0042] Optionally, the mass fraction of the film-forming agent can be 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, or 100 parts, etc. It is understood that other suitable choices can be made within the range of 60 to 100 parts. It should be noted that the film-forming agent is a composite emulsion including epoxy resin emulsion, polyurethane emulsion, and polyacrylate emulsion. These three emulsions can form a uniform mixed emulsion through physical blending, and other components of the wetting agent can be uniformly dispersed in the mixed emulsion, thereby obtaining a wetting agent with good flowability and uniformity. After drying, the liquid in the mixed emulsion evaporates, and the epoxy resin particles, polyurethane particles, and polyacrylate particles deform. Further polymerization and cross-linking can also occur between the particles under the action of a coupling agent, thereby forming a transparent polymer film on the substrate surface. Simultaneously, other components of the wetting agent can be uniformly dispersed in the film, thus forming a smooth modified layer on the substrate surface. It should be noted that polyurethane is an excellent film-forming aid, which is beneficial for the film formation of the main epoxy resin emulsion. It can also improve the strength, abrasion resistance, and chemical corrosion resistance of the film, thereby enhancing the durability and water resistance of the product. Furthermore, polyurethane has good elasticity and flexibility, allowing it to adapt to substrates with different surface properties. Polyacrylate has good adhesion and film-forming properties, which can further enhance the film-forming properties of the wetting agent and strengthen the bonding strength between the polymer film and the target substrate.

[0043] Furthermore, when the mass ratio of epoxy resin emulsion, polyurethane emulsion, and polyacrylate emulsion is (4–7):1:1, the smoothness and transparency of the modified layer can be improved, thereby effectively reducing the wetting between the basalt fiber fabric and the epoxy resin, allowing the product to retain the color of the basalt fiber fabric. Optionally, the mass ratio of epoxy resin emulsion, polyurethane emulsion, and polyacrylate emulsion can be 4:1:1, 5:1:1, 6:1:1, or 7:1:1. It is understood that other suitable choices can be made within the range of (4–7):1:1.

[0044] In some embodiments, the mass ratio of epoxy resin emulsion to polyurethane emulsion is (4-6):1:1. When the mass ratio of epoxy resin emulsion to polyurethane emulsion is within the above-mentioned range, the smoothness and transparency of the resulting modified layer can be further improved, allowing the product to more fully display the color of the basalt fiber fabric.

[0045] Optionally, the mass fraction of the coupling agent can be 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 parts. It is understood that other suitable choices can be made within the range of 5 to 15 parts. The coupling agent can promote further crosslinking of epoxy resin and polyurethane, enhance the film-forming properties of the wetting agent, and improve the strength and smoothness of the polymer film.

[0046] Optionally, the mass fraction of polyoxyethylene stearate can be 2, 3, 4, or 5 parts. It is understood that other suitable choices can be made within the range of 2 to 5 parts by mass of polyoxyethylene stearate. Polyoxyethylene stearate can improve the softness of basalt fiber fabrics, reduce surface static electricity of the fabric substrate, and make the fabric surface smoother and less prone to pilling.

[0047] Understandably, long-chain quaternary ammonium salts are quaternary ammonium salts containing alkyl chains with 12 to 18 carbon atoms. Optionally, the mass fraction of the long-chain quaternary ammonium salt can be 1 part, 2 parts, 3 parts, or 4 parts. Understandably, other suitable choices can be made within the range of 1 to 4 parts. Long-chain quaternary ammonium salts can synergistically interact with polyoxyethylene stearate to further enhance the softness of basalt fiber fabrics, improve surface static electricity, and make the fabric surface smoother and less prone to pilling.

[0048] Optionally, the mass fraction of silica can be 5, 7, 9, 11, 13, or 15 parts. It is understood that other suitable choices within the range of 5 to 15 parts by mass of silica can also be made. Silica has high fluidity; by adding a small amount of silica to the impregnating agent, the surface of basalt fiber fabric can be made denser, reducing the coefficient of friction and increasing the strength and abrasion resistance of the fabric. Furthermore, silica particles can reflect ultraviolet light, thus weakening the degradation effect of ultraviolet light on epoxy resin after the fabric is laminated with epoxy resin, improving the weather resistance and aging resistance of the product.

[0049] Optionally, the mass fraction of the additive can be 10, 12, 14, 16, 18, or 20 parts. It is understood that other suitable choices can be made within the range of 10 to 20 parts. It should be noted that additives include other substances that improve the overall performance of the product, and those skilled in the art can select them according to actual needs; this application does not limit this selection.

[0050] In some embodiments, the wetting agent comprises the following components by weight:

[0051]

[0052]

[0053] When the components in the sizing agent are within the above-mentioned content range, their fluidity and film-forming properties can be further improved, forming a smoother modified layer on the surface of the basalt fiber fabric. After being compounded with epoxy resin, the original color of the basalt fiber fabric can be more fully presented. In addition, the weather resistance and abrasion resistance of the basalt fiber fabric can be further improved.

[0054] In some embodiments, the wetting agent consists of the components described above in parts by mass.

[0055] In some embodiments, the carbon-chain quaternary ammonium salt contains a C12-C18 alkyl chain. Further optionally, the long-chain quaternary ammonium salt comprises hexadecyltrimethylammonium bromide.

[0056] In some of these embodiments, the long-chain quaternary ammonium salt has a pH of 5 to 7 and a purity greater than 99%.

[0057] In some embodiments, the coupling agent includes at least one of aminosilane, epoxysilane, methacryloxysilane, vinylsilane, and isocyanate-based silane.

[0058] In some embodiments, the additives include at least one of a colorant and a polymerization inhibitor.

[0059] In some embodiments, the stearic acid polyoxyethylene ester has a pH of 5-7, a saponification value of 70 mg KOH / g-80 mg KOH / g, and a moisture content of ≤1.0 wt%.

[0060] In some embodiments, the specific surface area of ​​silicon oxide is 160 m². 2 / g~210m 2 / g, pH value 5-7, silica content ≥99wt%.

[0061] In some of these embodiments, the silicon oxide is nano-silicon oxide.

[0062] By selecting polyoxyethylene stearate, long-chain quaternary ammonium salt, and silicon dioxide that meet the above conditions, the overall performance of the product can be further improved, thereby enhancing the appearance and texture of the product and improving the user's visual experience.

[0063] This application also provides a method for using the above-mentioned wetting agent, including the following steps:

[0064] The wetting agent is mixed with water to obtain the coating.

[0065] Apply the coating to the target substrate.

[0066] Understandably, in actual use, the wetting agent can be diluted as needed before use, and the specific dilution ratio can be selected as required.

[0067] Another embodiment of this application provides a modified basalt fiber fabric, including a basalt fiber fabric and a modified layer disposed on the surface of the basalt fiber fabric, wherein the raw materials for preparing the modified layer include the aforementioned impregnating agent.

[0068] In this embodiment, the modified basalt fiber fabric, after being compounded with epoxy resin, retains the original golden color of the basalt fiber fabric and exhibits good abrasion resistance, aging resistance, and surface quality. Furthermore, the basalt fiber fabric and epoxy resin have good bonding strength, which improves the strength properties of the finished product.

[0069] In some embodiments, the areal density of the basalt fiber fabric is 600 g / m³. 2 ~800g / m 2 When the areal density is within this range, it allows for suitable porosity between the basalt fiber bundles in the fabric, thereby forming a smooth modified layer on its surface.

[0070] In some embodiments, the diameter of the basalt fiber bundles in the basalt fiber fabric is 8 μm to 14 μm. Optionally, the diameter is 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm or 14 μm.

[0071] In some embodiments, the basalt fiber fabric is twill-woven. Twill-woven basalt fiber fabrics allow for a clearer fiber texture.

[0072] This application also provides a method for preparing the above-mentioned modified basalt fiber fabric, comprising the following steps:

[0073] The above wetting agent is mixed with water to obtain a coating.

[0074] The coating is applied to the basalt fiber fabric in multiple layers and then dried to form a modified layer on the surface of the basalt fiber fabric, thus obtaining the modified basalt fiber fabric.

[0075] It should be noted that when the surface of the basalt fiber fabric is moistened with a small amount of paint, its golden color will darken. After drying to remove the liquid from the paint, the basalt fiber fabric will return to its golden color.

[0076] The preparation method of this embodiment uses a multi-coating approach to uniformly coat the coating onto the basalt fiber fabric. After drying, a smooth, continuous, and transparent modified layer is formed on the surface of the basalt fiber fabric. Compared with technical solutions that directly immerse the basalt fiber fabric in the coating or apply the coating to the basalt fiber fabric in one go, the multi-coating method of this application allows the resulting fabric to retain the original color of the basalt fiber.

[0077] In some embodiments, in the step of mixing the wetting agent with water, the volume ratio of the wetting agent to the water is 1:(5-20).

[0078] In some embodiments, water at 20°C to 50°C is used to mix with the wetting agent to dilute the wetting agent.

[0079] In some embodiments, the coating is applied in multiple coats, with the number of coats ranging from 2 to 5. Optionally, the number of coats can be 2, 3, 4, or 5.

[0080] In some embodiments, the interval between two consecutive coatings is 20 min to 40 min.

[0081] In some embodiments, the coating is applied in multiple coats using a spraying method.

[0082] In some embodiments, the drying process is carried out at a temperature of 80°C to 100°C for a time of 6 to 12 hours.

[0083] Furthermore, one embodiment of this application also provides a basalt fiber fabric composite material, including the above-mentioned modified basalt fiber fabric and an epoxy resin layer disposed on the modified layer.

[0084] Understandably, to improve the strength properties of modified basalt fiber fabrics and meet the requirements for automotive materials, an epoxy resin layer needs to be applied to the modified basalt fiber fabric. The modified layer on the surface of the basalt fiber fabric can enhance its bonding strength with the epoxy resin layer and reduce the wetting of the modified basalt fiber fabric by the epoxy resin layer, giving the composite material a golden yellow color, thereby improving the color, appearance, abrasion resistance, and weather resistance of the product.

[0085] This application also provides a method for preparing the above-mentioned basalt fiber fabric composite material, comprising the following steps:

[0086] The modified basalt fiber fabric is formed using the above-described preparation method.

[0087] An epoxy resin layer is formed on the modified layer of the modified basalt fiber fabric to obtain a basalt fiber fabric composite material.

[0088] Furthermore, one embodiment of this application also provides an automotive trim, comprising the aforementioned basalt fiber fabric composite material.

[0089] The following are specific examples.

[0090] Example 1

[0091] (1) Prepare the impregnating agent

[0092] By weight, 80 parts of film-forming agent, 10 parts of methacryloxysilane, 3 parts of polyoxyethylene stearate, 3 parts of hexadecyltrimethylammonium bromide, 10 parts of silica, and 10 parts of additives are mixed to obtain an impregnating agent. The film-forming agent comprises epoxy resin emulsion, polyurethane emulsion, and polyacrylate emulsion, with a mass ratio of 5:1:1. The polyoxyethylene stearate has a pH of 7, a saponification value of 80 mg KOH / g, and a moisture content of 0.5 wt%. The hexadecyltrimethylammonium bromide has a pH of 7 and a purity of 99.3%. The silica has a particle size of 800 mesh and a specific surface area of ​​200 m². 2 / g, loose bulk density is 0.1g / cm³ 3 It has a pH value of 7 and a silica content of 99.3 wt%.

[0093] (2) Preparation of modified basalt fiber fabric

[0094] The wetting agent from step (1) was diluted with water to obtain the coating. The volume ratio of the wetting agent to water was 1:10, and the water temperature was controlled at 25℃.

[0095] The coating was applied evenly to the basalt fiber fabric in three coats, with a 30-minute interval between each coat. The areal density of the basalt fiber fabric was 600 g / m². 2 The diameter of the fiber bundles is 14μm, and the basalt fiber fabric is twill woven.

[0096] The sprayed basalt fiber fabric was placed in an oven at 80°C for drying for 12 hours to obtain a modified basalt fiber fabric. The modified basalt fiber fabric includes a basalt fiber fabric and a modified layer formed by the coating, and the modified layer is located on the surface of the basalt fiber fabric.

[0097] (3) Preparation of basalt fiber fabric composite materials

[0098] The modified basalt fiber fabric from step (2) is combined with epoxy resin, and the epoxy resin is introduced into the modified layer of the basalt fiber fabric to form an epoxy resin layer, thereby obtaining a basalt fiber fabric composite sheet.

[0099] Example 2

[0100] The preparation method of Example 2 is basically the same as that of Example 1, except that the film-forming agent in step (1) is 100 parts.

[0101] Example 3

[0102] The preparation method of Example 3 is basically the same as that of Example 1, except that the amount of silicon dioxide in step (1) is 15 parts.

[0103] Example 4

[0104] The preparation method of Example 4 is basically the same as that of Example 1, except that the mass ratio of epoxy resin emulsion, polyurethane emulsion and polyacrylate emulsion in the film-forming agent in step (1) is 4:1:1.

[0105] Example 5

[0106] The preparation method of Example 5 is basically the same as that of Example 1, except that the mass ratio of epoxy resin emulsion, polyurethane emulsion and polyacrylate emulsion in the film-forming agent in step (1) is 6:1:1.

[0107] Example 6

[0108] The preparation method of Example 6 is basically the same as that of Example 1, except that the mass ratio of epoxy resin emulsion, polyurethane emulsion and polyacrylate emulsion in the film-forming agent in step (1) is 7:1:1.

[0109] Example 7

[0110] The preparation method of Example 7 is basically the same as that of Example 1, except that the areal density of the basalt fiber fabric in step (2) is 400 g / m³. 2

[0111] Comparative Example 1

[0112] The preparation method of Comparative Example 1 is basically the same as that of Example 1, except that silicon oxide is not added in step (1).

[0113] Comparative Example 2

[0114] The preparation method of Comparative Example 2 is basically the same as that of Example 1, except that hexadecyltrimethylammonium bromide is not added in step (1).

[0115] Comparative Example 3

[0116] The preparation method of Comparative Example 3 is basically the same as that of Example 1, except that in step (2), the coating is sprayed onto the basalt fiber fabric in one go.

[0117] Comparative Example 4

[0118] The preparation method of Comparative Example 4 is basically the same as that of Example 1, except that the film-forming agent in step (1) does not contain polyurethane emulsion and polyacrylate, that is, the film-forming agent is 80 parts of epoxy resin emulsion.

[0119] Comparative Example 5

[0120] The preparation method of Comparative Example 5 is basically the same as that of Example 1, except that the film-forming agent in step (1) does not contain polyacrylate, that is, the film-forming agent is 80 parts of epoxy resin emulsion and polyurethane emulsion, and the mass ratio of the two is 5:1.

[0121] Comparative Example 6

[0122] The preparation method of Comparative Example 6 is basically the same as that of Example 1, except that the amount of silicon dioxide in step (1) is 25 parts.

[0123] Comparative Example 7

[0124] The preparation method of Comparative Example 7 is basically the same as that of Example 1, except that an equal amount of decaalkyltrimethylammonium bromide is used instead of hexadecyltrimethylammonium bromide in step (1).

[0125] Comparative Example 8

[0126] The preparation method of Comparative Example 8 is basically the same as that of Example 1, except that the mass ratio of epoxy resin emulsion, polyurethane emulsion and polyacrylate emulsion in the film-forming agent in step (1) is 2:1:1.

[0127] Comparative Example 9

[0128] The preparation method of Comparative Example 9 is basically the same as that of Example 1, except that the mass ratio of epoxy resin emulsion, polyurethane emulsion and polyacrylate emulsion in the film-forming agent in step (1) is 10:1:1.

[0129] The basalt fiber fabric composite sheets prepared in Examples 1-7 and Comparative Examples 1-9 were used. The appearance, color, and surface quality of the sheets were observed, and their abrasion resistance, xenon lamp aging resistance, and bonding strength between the basalt fiber fabric and epoxy resin were evaluated.

[0130] The abrasion resistance test involves using a sample cutter to take a sample with an area of ​​100 cm². 2 Circular specimens were used for testing using a Schopper abrasion tester. Specifically, the circular specimens were clamped in a clamping device, and the protrusion height of the specimens was adjusted to 5 mm, with a friction area of ​​approximately 50 cm². 2Weights were added to bring the frictional pressure to 19.6 N. The counter was then zeroed and the testing equipment started. The friction direction was changed after every 100 revolutions, and the total number of revolutions was 2000. The wear resistance was assessed based on the surface wear of the circular sample after the test.

[0131] The xenon lamp aging resistance test was conducted according to GB / T-16422.2-2014. After the test, the color fastness and appearance were evaluated visually according to GB / T-15596-2009, and the test time was 1000 hours as specified in Table 3 (cycle number 9) of GB / T-16422.2-2014. The test was stopped when the sample changed color, and the specific time of color change was recorded.

[0132] Table 1

[0133] Group Exterior color abrasion resistance Xenon lamp aging resistance Surface quality Bond strength Example 1 Golden yellow good No color change after 1000 hours Clear texture good Example 2 Golden yellow good No color change after 1000 hours Clear texture good Example 3 Golden yellow good No color change after 1000 hours Clear texture good Example 4 Golden yellow good No color change after 1000 hours Clear texture good Example 5 Golden yellow good No color change after 1000 hours Clear texture good Example 6 Golden yellow good No color change after 1000 hours The texture is slightly covered. good Example 7 Golden yellow good No color change after 1000 hours The texture is slightly covered. good Comparative Example 1 Golden yellow Poor 750h color change Clear texture good Comparative Example 2 Golden yellow good No color change after 1000 hours Surface roughness good Comparative Example 3 black good Unable to determine The texture is covered good Comparative Example 4 Golden yellow darkened good No color change after 1000 hours The texture is covered good Comparative Example 5 Golden yellow darkened good No color change after 1000 hours The texture is covered Poor Comparative Example 6 Golden yellow good No color change after 1000 hours The texture is covered good Comparative Example 7 Golden yellow good No color change after 1000 hours Surface roughness Poor Comparative Example 8 Golden yellow darkened good No color change after 1000 hours The texture is covered Poor Comparative Example 9 Golden yellow darkened good No color change after 1000 hours The texture is covered Poor

[0134] As shown in Table 1, the basalt fiber fabric composite sheets from Examples 1 to 7 all exhibit a golden-yellow color and a relatively clear surface texture, while also demonstrating good abrasion resistance and xenon lamp aging resistance. However, the sizing agent in Comparative Example 1 did not contain silica, resulting in significantly reduced abrasion resistance and xenon lamp aging resistance. The sizing agent in Comparative Example 2 did not contain cetyltrimethylammonium bromide, leading to surface fuzzing and poor bonding between the fabric and the epoxy resin layer. Comparative Example 3, using a one-time spray coating method, resulted in a black sheet with significantly reduced appearance quality. The film-forming agent in Comparative Example 4 consisted only of epoxy resin emulsion, resulting in poor film-forming effect; the sheet failed to retain the original color of the basalt fabric, and the surface texture was obscured. The film-forming agent in Comparative Example 5 did not contain polyacrylate emulsion, reducing its film-forming properties; the color and texture of the sheet changed, resulting in reduced appearance quality and poor bonding between the fabric and the epoxy resin layer. In Comparative Example 6, a relatively excessive amount of silica was added, resulting in a modified layer containing more silica particles, thus reducing the bonding strength between the fabric and the epoxy resin layer. Comparative Example 7 used a short-chain quaternary ammonium salt instead of the long-chain quaternary ammonium salt used in this application, resulting in reduced antistatic effect, fuzzing of the sheet surface, and decreased bonding strength. In Comparative Examples 8 and 9, the mass ratio of the three emulsions in the film-forming agent was outside the range specified in this application; both resulted in darker fabric color, reduced texture clarity, and significantly reduced bonding strength.

[0135] This application uses a specific ratio of film-forming agent, coupling agent, polyoxyethylene stearate, long-chain quaternary ammonium salt, silicon dioxide, and additives to produce a sizing agent with good fluidity and film-forming properties. This agent can form a smooth modified layer on the surface of basalt fiber fabric, allowing the basalt fiber fabric to still exhibit a golden yellow texture and not change color after being compounded with epoxy resin. Furthermore, it can improve the weather resistance and abrasion resistance of the basalt fiber fabric.

[0136] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0137] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A modified basalt fiber fabric, characterized in that, The modified basalt fiber fabric comprises a basalt fiber fabric and a modified layer arranged on the surface of the basalt fiber fabric, and the raw material for preparing the modified layer comprises an impregnant, which is composed of the following components in parts by mass: a film forming agent 60-100 parts, a coupling agent 5-15 parts, a stearic acid polyoxyethylene ester 2-5 parts, a long carbon chain quaternary ammonium salt 1-4 parts, silicon oxide 5-15 parts, and an auxiliary agent 10-20 parts. The film forming agent comprises an epoxy resin emulsion, a polyurethane emulsion and a polyacrylate emulsion, and the mass ratio of the epoxy resin emulsion, the polyurethane emulsion and the polyacrylate emulsion is (4-6):1:

1. The stearic acid polyoxyethylene ester has a pH value of 5-7, a saponification value of 70 mgKOH / g-80 mgKOH / g and a water content of ≤1.0 wt%. The specific surface area of the silicon oxide is 160 m 2 / g~210 m 2 / g, the pH value is 5~7, the content of silicon dioxide in the silicon oxide is ≥99 wt%; the long carbon chain quaternary ammonium salt contains C12~C18 alkyl chain; The use method of the impregnant comprises the following steps: mixing the impregnant with water to obtain a coating; applying the coating on a target substrate; the coating is applied in several times, and the number of application times is 2-5.

2. The modified basalt fiber fabric of claim 1, wherein, The impregnant is composed of the following components in parts by mass: a film forming agent 70-90 parts, a coupling agent 8-12 parts, a stearic acid polyoxyethylene ester 2-5 parts, a long carbon chain quaternary ammonium salt 1-3 parts, silicon oxide 8-12 parts, and an auxiliary agent 10-20 parts.

3. The modified basalt fiber fabric according to claim 1 or 2, characterized in that, The coupling agent comprises at least one of aminosilane, epoxy silane, methacryloyloxysilane, vinyl silane and isocyanate silane. And / or, the auxiliary agent comprises at least one of a toner and a polymerization inhibitor.

4. The modified basalt fiber fabric of claim 3, wherein, The long carbon chain quaternary ammonium salt comprises cetyltrimethylammonium bromide.

5. The modified basalt fiber fabric of claim 4, wherein, The silicon oxide is nano silicon oxide.

6. The modified basalt fiber fabric of claim 4, wherein, The areal density of the basalt fiber fabric is 600 g / m 2 800 g / m 2 ; And / or, the diameter of the basalt fiber tows in the basalt fiber fabric is 8 μm-14 μm. And / or, the basalt fiber fabric is woven by twill.

7. A method for producing a modified basalt fiber fabric, characterized by, The use method comprises the following steps: mixing the impregnant of any one of claims 1-6 with water to obtain a coating; coating the coating on the basalt fiber fabric in several times and then performing drying treatment, so that a modified layer is formed on the surface of the basalt fiber fabric, thereby obtaining the modified basalt fiber fabric.

8. The method of claim 7, wherein the modified basalt fiber fabric is prepared by the steps of: 5 preparing a basalt fiber fabric; and 6 applying a sizing agent to the basalt fiber fabric. In the step of mixing the impregnant with water, the volume ratio of the impregnant to the water is 1:(5-20).

9. A basalt fiber fabric material composite, characterized by, The composite material comprises the modified basalt fiber fabric of any one of claims 1-6 and an epoxy resin layer arranged on the modified layer.

10. A method of manufacturing a basalt fiber fabric composite material, characterized by, The preparation method comprises the following steps: forming the modified basalt fiber fabric by using the preparation method of any one of claims 7-8; forming an epoxy resin layer on the modified layer of the modified basalt fiber fabric, thereby obtaining the basalt fiber fabric composite material.

11. An automotive trim, characterized by The automobile ornament comprises the basalt fiber fabric composite material of claim 9.

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