Setting agents, processes for their preparation and use

Abstract

The application relates to a setting agent and a preparation method and application thereof. The setting agent comprises the following raw materials in mass parts: 10-20 parts of a polyisocyanate, 1-6 parts of a polyhydroxy quaternary ammonium salt, 1-6 parts of a hydroxyl-terminated polysiloxane compound, 1-3 parts of a chain extender, 2-10 parts of a polyether polyol and 0.1-1 part of a catalyst. The setting agent raw materials comprise the polyisocyanate, the polyhydroxy quaternary ammonium salt, the hydroxyl-terminated polysiloxane compound, the chain extender, the polyether polyol and the catalyst in specific proportions, a cationic setting agent can be obtained, and the binding strength between the setting agent and a basalt fiber fabric can be enhanced.

Description

Technical Field

[0001] This application relates to the field of polymer materials technology, and in particular to a sizing agent, its preparation method, and its application. Background Technology

[0002] With the increasing demand for lightweight and high-reliability vehicles, coupled with the decreasing price of high-performance fiber materials, the application of fiber fabrics in the automotive field is becoming increasingly widespread. Thanks to advancements in manufacturing processes, the molding process for producing automotive parts from fiber fabrics has shifted from small-batch manual production to large-scale automated production, further promoting the large-scale application of fiber fabrics in the automotive industry.

[0003] Basalt fiber fabric, as a moderately priced, high-strength, and aesthetically pleasing woven fabric, not only meets the strength requirements for automotive materials but also enhances the decorative and aesthetic qualities of automobiles, making it one of the most promising automotive fiber fabrics. However, basalt fiber fabric is relatively loose, and during the manufacturing of automotive parts, it is subjected to forming forces, causing displacement and disorder of the basalt fiber bundles within the fabric. This damages the fiber texture and consequently affects the appearance quality and mechanical strength of the resulting parts. To address these issues, traditional techniques often employ setting agents to shape the surface of basalt fiber fabric. However, traditional setting agents have weak adhesion to the fabric and cannot provide effective shaping. Furthermore, traditional setting agents exhibit poor dispersibility and stability in solvents, making emulsions containing these setting agents prone to precipitation and stratification, and failing to form a uniform protective film on the fabric surface.

[0004] Therefore, how to provide a setting agent that can bond tightly with basalt fiber fabrics has become an urgent technical problem to be solved. Summary of the Invention

[0005] Therefore, it is necessary to provide a setting agent that can bond tightly with basalt fiber fabrics, as well as its preparation method and application.

[0006] A first aspect of this application provides a setting agent comprising, by weight parts, the following raw materials:

[0007]

[0008] The aforementioned setting agent raw materials include a specific ratio of polyisocyanate, polyhydroxy quaternary ammonium salt, hydroxyl-terminated polysiloxane compound, chain extender, polyether polyol, and catalyst, resulting in a cationic setting agent that enhances the bonding strength between the setting agent and basalt fiber fabric. Among these, the polyhydroxy quaternary ammonium salt, hydroxyl-terminated polysiloxane compound, and polyether polyol, as monomers containing hydroxyl groups, can undergo a polymerization reaction with isocyanate under the action of a catalyst to form the polyurethane backbone. On one hand, the polyhydroxy quaternary ammonium salt provides cations, increasing the hydrophilicity of the polyurethane, allowing the setting agent to form a stable emulsion in the solvent, less prone to precipitation and stratification, thus improving the film-forming properties and stability of the emulsion. Furthermore, the positive charge of the cations attracts the negative charge of the basalt fiber fabric, thereby ensuring the overall bonding strength between the polyurethane molecules and the fabric. The product acts to enhance the bonding strength between the setting agent and the fabric, prevent the displacement of the filaments in the fabric, and improve the setting effect. On the other hand, hydroxyl-terminated polysiloxane compounds help to enhance the flexibility of polyurethane molecular chains. Therefore, after the setting agent is combined with basalt fiber fabric, it can improve the smoothness and antistatic properties of the fabric. At the same time, by adjusting the ratio of polyhydroxy quaternary ammonium salt, hydroxyl-terminated polysiloxane compounds and polyether polyols, and adding an appropriate amount of chain extender, the resulting polyurethane has good electrophilicity, hydrophilicity and flexibility, effectively improving the effect of the setting agent.

[0009] Furthermore, in the setting agent of this application, each specific raw material is synergistically controlled through a specific ratio, resulting in a lower degree of cross-linking of the polyurethane, thus resulting in lower viscosity and better fluidity, which facilitates subsequent spraying. It can also form a uniform protective film on the surface of basalt fiber fabric, further improving the setting effect.

[0010] In some embodiments, the sizing agent comprises, by weight, the following raw materials:

[0011]

[0012] In some embodiments, the raw material satisfies at least one of the following conditions (1) and (2):

[0013] (1) The polyhydroxy quaternary ammonium salt includes at least one of bis(2-hydroxyethyl)dimethylammonium chloride, bis(2-hydroxypropyl)dimethylammonium chloride, dodecyl bis-hydroxyethyl methylammonium chloride and hydroxypropyl bis-hydroxyethyl dimethylammonium chloride.

[0014] (2) The hydroxyl-terminated polysiloxane compounds include hydroxyl-terminated polydimethylsiloxane.

[0015] In some embodiments, the raw material satisfies at least one of the following conditions (3) to (4):

[0016] (3) One molecule of the polyisocyanate contains two isocyanate groups;

[0017] (4) The chain extender includes aliphatic diols.

[0018] In some embodiments, the raw material satisfies at least one of the following conditions (5) to (6):

[0019] (5) The polyisocyanate includes at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and L-lysine diisocyanate;

[0020] (6) The chain extender includes aliphatic diols with 2 to 5 carbon atoms.

[0021] In some embodiments, the raw material satisfies at least one of the following conditions (7) to (8):

[0022] (7) The polyether polyol includes at least one of polypropylene glycol and polybutanediol.

[0023] (8) The catalyst comprises dibutyltin dilaurate.

[0024] A second aspect of this application provides a method for preparing the setting agent described in the first aspect, comprising the following steps:

[0025] The polyhydroxy quaternary ammonium salt, the hydroxyl-terminated polysiloxane compound, the polyether polyol, and the catalyst are added to a solvent to obtain a mixed solution;

[0026] The isocyanate is added to the mixed solution and heated to react, resulting in a reaction solution containing the prepolymer; then the chain extender is added to the reaction solution containing the prepolymer, and the reaction continues to prepare the setting agent.

[0027] A third aspect of this application provides a shaping emulsion, comprising a dispersant and the shaping agent described in the first aspect.

[0028] A fourth aspect of this application provides a basalt fiber composite fabric, comprising a basalt fiber fabric and a protective layer disposed on the surface of the basalt fiber fabric, wherein the raw material for preparing the protective layer includes the shaping emulsion described in the third aspect.

[0029] In some embodiments, the basalt fiber composite fabric further includes an epoxy resin layer disposed on the surface of the protective layer away from the basalt fiber fabric.

[0030] A fifth aspect of this application provides a method for preparing basalt fiber composite fabric, comprising the following steps:

[0031] The coating is prepared by mixing the shaping emulsion, defoamer, and water described in the third aspect;

[0032] The coating is sprayed onto the surface of the basalt fiber fabric, and after curing, a protective layer is formed to prepare the basalt fiber composite fabric.

[0033] In some embodiments, after the step of forming the protective layer, the following step is further included:

[0034] An epoxy resin layer is formed on the surface of the protective layer.

[0035] A sixth aspect of this application provides an automotive trim comprising the basalt fiber composite fabric described in the fourth aspect. Attached Figure Description

[0036] Figure 1 The images show actual photos of the emulsions used in Examples 1-5 and Comparative Example 1.

[0037] Figure 2 The particle size distribution diagrams are shown for the setting agent droplets in the setting emulsions of Examples 2-5.

[0038] Figure 3 The images shown are scanning electron microscope (SEM) images of the basalt fiber fabric in Example 5 before and after coating, where A and B are the basalt fiber fabric before coating, and C and D are the basalt fiber fabric after coating.

[0039] Figure 4 This is a diagram showing the state of basalt fiber fabric after rubbing, without the application of setting emulsion.

[0040] Figure 5 A diagram showing the state of a basalt fiber fabric after rubbing, which is being coated with a setting emulsion. Detailed Implementation

[0041] To facilitate understanding of this application, a more complete description will be provided below with reference to the accompanying drawings. Preferred embodiments of this application are shown in the drawings. However, 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 thorough and complete understanding of the disclosure of this application.

[0042] 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.

[0043] In the description of this application, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this application, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0044] 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.

[0045] One embodiment of this application provides a setting agent, comprising, by weight parts, the following raw materials:

[0046]

[0047] Understandably, the hydroxyl groups contained in polyhydroxy quaternary ammonium salts, hydroxyl-terminated polysiloxane compounds, and polyether polyols can undergo polymerization reactions with isocyanates to form a polyurethane backbone. Compared to conventional polyurethanes obtained by reacting isocyanates and polyether polyols, this embodiment modifies the polyurethane molecular chain by adding polyhydroxy quaternary ammonium salts and hydroxyl-terminated polysiloxane compounds, thereby enhancing the hydrophilicity, electrophilicity, and flexibility of the polyurethane molecular chain.

[0048] The aforementioned setting agent raw materials include a specific ratio of polyisocyanate, polyhydroxy quaternary ammonium salt, hydroxyl-terminated polysiloxane compound, chain extender, polyether polyol, and catalyst, resulting in a cationic setting agent that enhances the bonding strength between the setting agent and basalt fiber fabric. Among these, the polyhydroxy quaternary ammonium salt, hydroxyl-terminated polysiloxane compound, and polyether polyol, as monomers containing hydroxyl groups, can undergo a polymerization reaction with isocyanate under the action of a catalyst to form the polyurethane backbone. On one hand, the polyhydroxy quaternary ammonium salt provides cations, increasing the hydrophilicity of the polyurethane, allowing the setting agent to form a stable emulsion in the solvent, less prone to precipitation and stratification, thus improving the film-forming properties and stability of the emulsion. Furthermore, the positive charge of the cations attracts the negative charge of the basalt fiber fabric, thereby ensuring the overall bonding strength between the polyurethane molecules and the fabric. The product acts to enhance the bonding strength between the setting agent and the fabric, prevent the displacement of the filaments in the fabric, and improve the setting effect. On the other hand, hydroxyl-terminated polysiloxane compounds help to enhance the flexibility of polyurethane molecular chains. Therefore, after the setting agent is combined with basalt fiber fabric, it can improve the smoothness and antistatic properties of the fabric. At the same time, by adjusting the ratio of polyhydroxy quaternary ammonium salt, hydroxyl-terminated polysiloxane compounds and polyether polyols, and adding an appropriate amount of chain extender, the resulting polyurethane has good electrophilicity, hydrophilicity and flexibility, effectively improving the effect of the setting agent.

[0049] Furthermore, in the setting agent of this application, each specific raw material is synergistically controlled through a specific ratio, resulting in a lower degree of cross-linking of the polyurethane, thus resulting in lower viscosity and better fluidity, which facilitates subsequent spraying. It can also form a uniform protective film on the surface of basalt fiber fabric, further improving the setting effect.

[0050] In some embodiments, the raw material of the setting agent consists of the components in the above-mentioned parts by mass.

[0051] Optionally, the mass fraction of the polyisocyanate can be 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 parts. It is understood that other suitable choices can be made within the range of 10 to 20 parts by mass of the polyisocyanate.

[0052] Optionally, the mass fraction of the polyhydroxy quaternary ammonium salt can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, or 6 parts. It is understood that other suitable choices can be made within the range of 1 to 6 parts. The polyhydroxy quaternary ammonium salt provides cations, enabling the setting agent to adsorb onto the surface of the negatively charged basalt fiber fabric and bind tightly to it, thereby improving the setting effect.

[0053] Optionally, the mass fraction of the hydroxyl-terminated polysiloxane compound can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, or 6 parts. It is understood that other suitable choices can be made within the range of 1 to 6 parts. The hydroxyl-terminated polysiloxane compound possesses a certain degree of hydrophobicity, allowing it to react well with isocyanates and integrate into the polyurethane molecular chain. Furthermore, the hydroxyl-terminated polysiloxane compound can improve the flexibility of the polyurethane molecular chain in the setting agent, thereby enhancing the smoothness and antistatic properties of basalt fiber fabrics. Further, optionally, the purity of the hydroxyl-terminated polysiloxane compound is greater than 99%.

[0054] Optionally, the chain extender can be 1 part, 2 parts, or 3 parts by mass. It is understood that other suitable choices can be made within the range of 1 to 3 parts by mass of the chain extender.

[0055] Optionally, the mass fraction of the polyether polyol can be 2, 3, 4, 5, 6, 7, 8, 9, or 10 parts. It is understood that other suitable mass fractions of the polyether polyol can be selected within the range of 2 to 10 parts.

[0056] Optionally, the mass fraction of the catalyst can be 0.1 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, or 1 part. It is understood that other suitable choices can be made within the range of 0.1 to 1 part.

[0057] In some embodiments, the setting agent comprises, by weight, the following raw materials:

[0058]

[0059] When the raw material components of the setting agent are within the above-mentioned content range, its film-forming properties can be improved, forming a smooth protective layer on the surface of basalt fiber fabrics, and further enhancing the bonding strength between the protective layer and the fabric. Furthermore, it can further improve the flexibility of the polyurethane molecular chains in the setting agent, thereby enhancing the smoothness and antistatic properties of the fabric.

[0060] In some embodiments, the raw material of the setting agent consists of the components in the above-mentioned parts by mass.

[0061] In some of these embodiments, a molecule of a polyhydroxy quaternary ammonium salt contains at least two hydroxyl groups.

[0062] In some of these embodiments, a molecule of a polyhydroxy quaternary ammonium salt contains two hydroxyl groups.

[0063] In some embodiments, the anion in the polyhydroxy quaternary ammonium salt includes at least one of F-, Cl-, Br-, and I-.

[0064] In some embodiments, the polyhydroxy quaternary ammonium salt includes at least one of bis(2-hydroxyethyl)dimethylammonium chloride, bis(2-hydroxypropyl)dimethylammonium chloride, dodecylbishydroxyethylmethylammonium chloride, and hydroxypropylbis-hydroxyethyldimethylammonium chloride.

[0065] Alternatively, the polyhydroxy quaternary ammonium salt includes bis(2-hydroxyethyl)dimethylammonium chloride.

[0066] In some embodiments, the hydroxyl-terminated polysiloxane compounds include hydroxyl-terminated polydimethylsiloxanes.

[0067] In some of these embodiments, a molecule of polyisocyanate contains two isocyanate groups.

[0068] In some embodiments, the polyisocyanate includes at least one of aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates.

[0069] Optionally, the aliphatic polyisocyanate is a saturated aliphatic polyisocyanate; further, the aliphatic polyisocyanate contains 8 to 12 carbon atoms.

[0070] Optionally, the alicyclic polyisocyanate is a saturated alicyclic polyisocyanate; further, the alicyclic polyisocyanate contains 6 to 10 cyclic carbon atoms.

[0071] Optionally, aromatic polyisocyanates contain 6 to 15 cyclic carbon atoms.

[0072] It should be noted that, in this application, the number of "cyclic carbon atoms" refers to the number of carbon atoms that form a ring. When the ring is replaced by a substituent, the atoms contained in the substituent are not included in the cyclic carbon atoms. For example, the toluene ring has 6 cyclic carbon atoms.

[0073] Furthermore, the polyisocyanate includes at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and L-lysine diisocyanate.

[0074] Further optionally, the polyisocyanate includes at least one selected from isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and L-lysine diisocyanate. These polyisocyanates do not contain a benzene ring and have relatively low activity, thus improving the lightfastness of the product.

[0075] In some embodiments, the chain extender comprises an aliphatic diol.

[0076] In some of these embodiments, the chain extender comprises a saturated aliphatic diol.

[0077] Furthermore, aliphatic diols include aliphatic diols with 2 to 5 carbon atoms.

[0078] Alternatively, the aliphatic diol includes at least one of polyethylene glycol, 1,3-propanediol, and 1,4-butanediol.

[0079] In some embodiments, the polyether polyol includes at least one of polypropylene glycol (PPG) and polybutanediol (PTMG).

[0080] In some of these embodiments, the catalyst comprises dibutyltin dilaurate.

[0081] Furthermore, this application provides a method for preparing the above-mentioned sizing agent, including the following steps S10 to S20.

[0082] S10. Add the polyhydroxy quaternary ammonium salt, hydroxyl-terminated polysiloxane compound, polyether polyol and catalyst to the solvent to obtain a mixed solution.

[0083] S20. Add polyisocyanate to the mixed solution and heat to react, to obtain a reaction solution containing prepolymer; then add chain extender to the reaction solution containing prepolymer and continue the reaction to prepare a setting agent.

[0084] In some embodiments, step S20, after the reaction is complete, further includes a step of drying the product after the reaction.

[0085] In some embodiments, the polyhydroxy quaternary ammonium salt, hydroxyl-terminated polysiloxane compound, polyether polyol, catalyst and solvent are mixed by stirring.

[0086] Optionally, stirring is carried out under a dry nitrogen atmosphere for 15 min to 40 min, at a stirring speed of 200 r / min to 500 r / min, at a temperature of 60℃ to 100℃, and the solvent is N,N-dimethylformamide (DMF).

[0087] In some embodiments, the polyisocyanate is dissolved in a solvent before being added to the above-mentioned mixed solution.

[0088] Optionally, the solvent used is DMF, and the amount used is 20 mL to 40 mL.

[0089] Alternatively, the isocyanate-containing solution may be added dropwise to the mixed solution over a period of 5 to 10 minutes.

[0090] In some embodiments, the heating temperature is 60°C to 80°C, the reaction time is 1h to 2h, the stirring speed is 400r / min to 500r / min, and after the reaction, a reaction solution containing prepolymer is obtained.

[0091] In some embodiments, the chain extender is dissolved in a solvent before being added to the reaction solution. Optionally, the solvent is DMF, the reaction is continued for 2 to 3 hours, and the temperature is 60°C to 80°C.

[0092] Furthermore, this application provides a shaping emulsion, including a dispersant and the shaping agent described above.

[0093] Understandably, in practical use, the aforementioned setting agent needs to be formulated into a setting emulsion with good flowability and dispersibility before use. For example, a phase transfer method can be used to add a dispersant to the setting agent and form a setting emulsion through emulsification.

[0094] In some embodiments, the dispersant comprises a mixed solution of water and ethanol. Optionally, the volume ratio of water to ethanol is (0.5–2):1.

[0095] In some embodiments, an emulsifier is used to emulsify the setting agent.

[0096] The aforementioned emulsion exhibits good stability and dispersibility, with virtually no sedimentation or stratification. Furthermore, it can be stored for extended periods, effectively improving production efficiency.

[0097] Another embodiment of this application provides a basalt fiber composite fabric, including a basalt fiber fabric and a protective layer disposed on the surface of the basalt fiber fabric, wherein the raw materials for preparing the protective layer include the aforementioned shaping emulsion.

[0098] In the above-mentioned basalt fiber composite fabric, the bonding strength between the protective layer and the basalt fiber fabric is high, which can effectively prevent the displacement of fiber bundles in the fabric, giving it a better appearance and making it easier to be mass-produced into automotive parts.

[0099] In some embodiments, the basalt fiber composite fabric further includes an epoxy resin layer disposed on the surface of the protective layer away from the basalt fiber fabric.

[0100] Understandably, adding an epoxy resin layer to the surface of basalt fiber composite fabric can yield basalt fiber fabric composite materials with better strength properties, thereby meeting the strength requirements of automotive materials.

[0101] Furthermore, this application provides a method for preparing the above-mentioned basalt fiber composite fabric, comprising the following steps:

[0102] The above-mentioned shaping emulsion, defoamer and water are mixed to prepare the coating.

[0103] The coating is sprayed onto the surface of the basalt fiber fabric, and after curing, a protective layer is formed to prepare the basalt fiber composite fabric.

[0104] The above preparation method uses a spraying method to uniformly coat the coating onto the basalt fiber fabric, and after curing, a smooth protective layer can be formed on the surface of the basalt fiber fabric.

[0105] In some embodiments, the volume ratio of the shaping emulsion to water is 1:(0.5-3).

[0106] In some embodiments, the amount of defoamer added is 0.5 wt% to 1 wt% of the total mass of the emulsion and water. Optionally, the defoamer includes BYK346.

[0107] In some embodiments, the shaping emulsion, defoamer and water are mixed and stirred at a stirring rate of 400 r / min to 600 r / min for 5 min to 10 min to obtain the coating.

[0108] In some embodiments, the coating is atomized at an air pressure of 0.4 MPa to 0.8 MPa before spraying.

[0109] In some embodiments, the amount of paint used for spraying is 100 mL / m. 2 ~800mL / m 2 .

[0110] Those skilled in the art can determine the specific dosage based on parameters such as the basis weight of the basalt fiber fabric and the required stiffness.

[0111] In some embodiments, the coating is applied evenly to the basalt fiber fabric using a multi-coating method.

[0112] Compared to a single-coat application method, the multiple-coat application method in this embodiment can effectively prevent fabric discoloration. Furthermore, during the multiple coating applications, each coat of paint should only lightly wet the surface of the basalt fiber fabric, and excessive paint should be avoided in the same area of ​​the fabric surface. It should be noted that if the fabric surface contains too much white liquid, it indicates that too much paint has been applied.

[0113] In some embodiments, the emulsion is left to stand at room temperature for 48 hours after spraying to allow the setting emulsion to cure.

[0114] In some embodiments, the emulsion is left to stand at 80°C to 100°C for 30 to 60 minutes after spraying to allow the emulsion to cure.

[0115] In some embodiments, after the step of forming the protective layer, the following steps are further included:

[0116] An epoxy resin layer is formed on the surface of the protective layer.

[0117] In addition, this application also provides an automotive trim, including the aforementioned basalt fiber composite fabric.

[0118] The following are specific examples.

[0119] Example 1

[0120] (1) Preparation of the setting agent

[0121] Dehydrated bis(2-hydroxyethyl)dimethylammonium chloride (BDAC), hydroxyl-terminated polydimethylsiloxane (PDMS-OH, molecular weight 500), polybutanediol (PTMG, molecular weight 650), and dibutyltin dilaurate (DBTDL) were added to DMF. The mixture was stirred at 70°C for 30 min under a dry nitrogen atmosphere at a stirring speed of 300 r / min to obtain a mixed solution. The composition was: BDAC 1 part by mass, PDMS-OH 5 parts by mass, PTMG 6 parts by mass, and DBTDL 0.2 parts by mass.

[0122] 15 parts by mass of isophorone diisocyanate (IPDI) were dissolved in 20 mL of DMF. After stirring for 5 to 10 minutes, the IPDI-containing solution was added dropwise to the mixture over a period of 10 minutes. A prepolymerization reaction was then carried out at 60°C for 2 hours at a stirring speed of 400 to 500 rpm to obtain a reaction solution containing the prepolymer. Then, 1 part by mass of 1,4-butanediol (BDO) was added to the reaction solution, wherein the BDO was first dissolved in DMF. The reaction was continued at 60°C for 3 hours. The solution was then dried under high temperature and reduced pressure to remove the DMF, yielding a setting agent.

[0123] (2) Preparation of shaping emulsion

[0124] Add a mixture of water and ethanol (volume ratio of water to ethanol is 1:1) dropwise to the setting agent obtained in step (1) at a rate of 1 mL / min, and stir with an emulsifier to obtain a setting emulsion.

[0125] (3) Preparation of basalt fiber composite fabric

[0126] Add water to the emulsion obtained in step (2) for dilution (the volume ratio of water to emulsion is 1:1), and add 5 wt% of defoamer BYK346 of the total mass of water and emulsion at the same time. Stir at a stirring speed of 500 r / min for 10 min to obtain the coating.

[0127] The coating was then sprayed onto the surface of the basalt fiber fabric in multiple applications, with only a small amount applied to the same location to lightly wet the fabric surface. After spraying, the coating was cured at room temperature for 48 hours to form a protective layer, resulting in the basalt fiber composite fabric.

[0128] Example 2

[0129] The preparation method of Example 2 is basically the same as that of Example 1, except that in step (1), BDAC is 2 parts by mass and PTMG is 5 parts by mass.

[0130] Example 3

[0131] The preparation method of Example 3 is basically the same as that of Example 1, except that in step (1), BDAC is 3 parts by mass and PTMG is 4 parts by mass.

[0132] Example 4

[0133] The preparation method of Example 4 is basically the same as that of Example 1, except that in step (1), BDAC is 4 parts by mass and PTMG is 3 parts by mass.

[0134] Example 5

[0135] The preparation method of Example 5 is basically the same as that of Example 1, except that in step (1), BDAC is 5 parts by mass and PTMG is 2 parts by mass.

[0136] Example 6

[0137] The preparation method of Example 6 is basically the same as that of Example 1, except that in step (1), BDAC is 6 parts by mass and PTMG is 1 part by mass.

[0138] Example 7

[0139] The preparation method of Example 7 is basically the same as that of Example 1, except that in step (1), BDAC is 5 parts by mass, PDMS-OH is 1 part by mass, and PTMG is 6 parts by mass.

[0140] Example 8

[0141] The preparation method of Example 8 is basically the same as that of Example 1, except that in step (1), PDMS-OH is 6 parts by mass and PTMG is 5 parts by mass.

[0142] Comparative Example 1

[0143] The preparation method of Comparative Example 1 is basically the same as that of Example 1, except that BDAC is not added in step (1), PDMS-OH is 10 parts by mass, and PTMG is 2 parts by mass.

[0144] Comparative Example 2

[0145] The preparation method of Comparative Example 2 is basically the same as that of Example 1, except that: in step (1), BDAC is 10 parts by mass, PDMS-OH is not added, and PTMG is 2 parts by mass.

[0146] Comparative Example 3

[0147] The preparation method of Comparative Example 3 is basically the same as that of Example 1, except that in step (1), BDAC is 1 part by mass, PDMS-OH is 9 parts by mass, and PTMG is 2 parts by mass.

[0148] Comparative Example 4

[0149] The preparation method of Comparative Example 4 is basically the same as that of Example 1, except that in step (1), BDAC is 9 parts by mass, PDMS-OH is 1 part by mass, and PTMG is 2 parts by mass. The raw materials (by mass) of the setting agents of Examples 1-8 and Comparative Examples 1-4 are shown in Table 1 below:

[0150] Table 1

[0151] Group BDAC PDMS-OH PTMG IPDI BDO DBTDL Example 1 1 5 6 15 1 0.2 Example 2 2 5 5 15 1 0.2 Example 3 3 5 4 15 1 0.2 Example 4 4 5 3 15 1 0.2 Example 5 5 5 2 15 1 0.2 Example 6 6 5 1 15 1 0.2 Example 7 5 1 6 15 1 0.2 Example 8 1 6 5 15 1 0.2 Comparative Example 1 0 10 2 15 1 0.2 Comparative Example 2 10 0 2 15 1 0.2 Comparative Example 3 1 9 2 15 1 0.2 Comparative Example 4 9 1 2 15 1 0.2

[0152] The basalt fiber composite fabrics prepared in Examples 1-8 and Comparative Examples 1-4 were subjected to a rubbing resistance test, specifically according to GB / T 8949-2008, with 500 cycles. The state of the setting emulsion was observed simultaneously. The test results are shown in Table 2 below.

[0153] Table 2

[0154]

[0155]

[0156]

[0157] As shown in Table 2 above, the setting emulsions of Examples 1-8 exhibit good dispersibility and stability, showing no precipitation or stratification after standing, thus allowing for long-term preservation. Furthermore, the basalt fiber composite fabrics prepared using the setting emulsions of Examples 1-8 do not show obvious cracks or pilling after rubbing, indicating that the setting emulsion forms a smooth protective layer on the surface of the basalt fiber fabric. This protective layer is tightly bonded to the basalt fiber fabric and does not separate after rubbing, thereby enhancing the bonding strength between the basalt fiber fabric and the epoxy resin layer. In contrast, the raw materials of Comparative Example 1 do not contain BDAC, resulting in a setting emulsion with poor dispersibility, prone to precipitation and stratification, and difficulty in achieving a good setting effect. The composite fabric shows cracks and pilling after rubbing, and the protective layer separates. The raw materials of Comparative Example 2 do not contain PDMS-OH, resulting in poor flexibility of the polyurethane molecular chains, thus reducing the antistatic effect of the composite fabric and causing surface cracks and pilling. The PDMS-OH content of Comparative Example 3 is outside the range of this application, and the sizing emulsion prepared from it has poor stability. The BDAC content of Comparative Example 4 is outside the range of this application, and the resulting composite fabric cracks and pills after rubbing.

[0158] Furthermore, Figure 1 The images shown are of the finished emulsions from Examples 1-5 and Comparative Example 1. Figure 1 It can be seen that the setting emulsions of Examples 1 to 5 have good dispersibility and stability, and no obvious precipitation or stratification occurs. However, the setting agent of Comparative Example 1 is difficult to disperse, indicating that the setting agent of this application has good hydrophilicity.

[0159] Figure 2 The following are particle size distribution diagrams of the setting agent droplets in the setting emulsions of Examples 2-5. Figure 2 It can be seen that after the sizing agent in Examples 2 to 5 is dispersed, it can form sizing agent droplets with small particle size, thus obtaining a sizing emulsion with good dispersibility and uniformity.

[0160] Figure 3 The images shown are scanning electron microscope (SEM) images of the basalt fiber fabric in Example 5 before and after coating, where A and B are the basalt fiber fabric before coating, and C and D are the basalt fiber fabric after coating. Figure 3 It can be seen that the basalt fiber bundles in the fabric did not undergo significant size changes before and after spraying, and their surfaces remained relatively smooth, indicating that the setting agent formed a smooth and tightly adhered protective layer on the surface of the fiber bundles.

[0161] Figure 4 and Figure 5 The images show the state of basalt fiber fabric after rubbing, with and without the setting emulsion applied. Figure 4 and Figure 5It is known that the basalt fiber composite fabric of this application did not show obvious cracks or pilling after rubbing, and the fiber texture was relatively clear. However, the basalt fiber fabric without the setting emulsion of this application had a blurred fiber texture after rubbing.

[0162] 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.

[0163] 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 setting agent, characterized in that, It consists of the following raw materials in parts by weight: 10-20 parts of polyisocyanate 4-6 parts of polyhydroxy quaternary ammonium salt 2-6 parts of hydroxyl-terminated polysiloxane compounds 1-3 parts of chain extender 2-6 parts of polyether polyol, and The catalyst is 0.1 to 1 part; the polyhydroxy quaternary ammonium salt includes at least one of bis(2-hydroxyethyl)dimethylammonium chloride, bis(2-hydroxypropyl)dimethylammonium chloride, dodecyl bis(hydroxyethyl)methylammonium chloride and hydroxypropyl bis(hydroxyethyl)dimethylammonium chloride.

2. The setting agent as described in claim 1, characterized in that, The hydroxyl-terminated polysiloxane compounds include hydroxyl-terminated polydimethylsiloxane.

3. The setting agent as described in claim 1, characterized in that, The raw materials satisfy at least one of the following conditions (1) to (2): (1) One molecule of the polyisocyanate contains two isocyanate groups; (2) The chain extender includes aliphatic diols.

4. The setting agent as described in claim 1, characterized in that, The raw materials satisfy at least one of the following conditions (3) to (4): (3) The polyisocyanate includes at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and L-lysine diisocyanate; (4) The chain extender includes aliphatic diols with 2 to 5 carbon atoms.

5. The setting agent as described in claim 1, characterized in that, The raw materials satisfy at least one of the following conditions (5) to (6): (5) The polyether polyol includes at least one of polypropylene glycol and polybutanediol; (6) The catalyst comprises dibutyltin dilaurate.

6. A method for preparing the setting agent according to any one of claims 1 to 5, characterized in that, Includes the following steps: According to the mass proportions of the raw materials of the setting agent, the polyhydroxy quaternary ammonium salt, the hydroxyl-terminated polysiloxane compound, the polyether polyol and the catalyst are added to the solvent to obtain a mixed solution; The polyisocyanate is added to the mixed solution and heated to react, resulting in a reaction solution containing the prepolymer; then the chain extender is added to the reaction solution containing the prepolymer, and the reaction continues to prepare the setting agent.

7. A shaping emulsion, characterized in that, It includes dispersants and the sizing agents as described in any one of claims 1 to 5.

8. A basalt fiber composite fabric, characterized in that, The basalt fiber composite fabric includes a basalt fiber fabric and a protective layer disposed on the surface of the basalt fiber fabric, wherein the raw material for preparing the protective layer includes the shaping emulsion as described in claim 7.

9. The basalt fiber composite fabric as described in claim 8, characterized in that, The basalt fiber composite fabric further includes an epoxy resin layer, which is disposed on the surface of the protective layer away from the basalt fiber fabric.

10. A method for preparing a basalt fiber composite fabric, characterized in that, Includes the following steps: The coating is prepared by mixing the shaping emulsion, defoamer, and water as described in claim 7; The coating is sprayed onto the surface of the basalt fiber fabric, and after curing, a protective layer is formed to prepare the basalt fiber composite fabric.

11. The method for preparing basalt fiber composite fabric as described in claim 10, characterized in that, Following the step of forming the protective layer, the following steps are also included: An epoxy resin layer is formed on the surface of the protective layer.

12. A car accessory, characterized in that, The automotive trim includes the basalt fiber composite fabric as described in claim 8 or 9.

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