A glass fiber cloth warping sizing material and a preparation method thereof

Abstract

The application relates to a glass fiber cloth warping sizing agent and a preparation method thereof, and belongs to the technical field of textile sizing agents. The glass fiber cloth warping sizing agent is composed of the following components: water-based polyurethane, composite silane coupling agent, polyvinyl alcohol, pH regulator, silicon dioxide and water; the weight ratio of the water-based polyurethane and the composite silane coupling agent is 3-6:1; the composite silane coupling agent is composed of OFS-6030 and KH-550 in a weight ratio of 1:1.1-4; the preparation steps are as follows: 1) dissolving the polyvinyl alcohol in water, adjusting the pH to obtain a sizing agent; 2) dissolving OFS-6030 in water to obtain solution A; dissolving KH-550 in water to obtain solution B; 3) sequentially adding solution A, the water-based polyurethane, solution B and silicon dioxide into the sizing agent, uniformly mixing, and sieving after standing; and the glass fiber cloth warping sizing agent is obtained. The glass fiber cloth warping sizing agent has the characteristics of high elasticity, high wear resistance and difficulty in yellowing.

Description

Technical Field

[0001] This invention belongs to the field of textile sizing technology, specifically relating to a glass fiber cloth warping sizing agent and its preparation method. Background Technology

[0002] In the wave of rapid development of modern industry, fiberglass cloth, with its superior performance, occupies a key position in core areas such as building reinforcement structures, industrial filtration materials, lightweight transportation components, and electronic circuit boards. However, fiberglass yarn faces the risk of high-frequency friction damage during the weaving process, which can easily cause yarn damage and seriously affect the quality and service life of the finished product. To effectively protect the yarn, the sizing process in the warping stage has become a core protective step in the weaving process.

[0003] Currently, the mainstream sizing formulations in the industry are mainly based on polyvinyl alcohol and modified starch. However, as various industries continue to raise the requirements for product performance, existing sizing agents cannot give fiberglass cloth good deformation recovery capabilities. When the product is used in scenarios requiring frequent bending and stretching, the cloth is prone to wrinkling and deformation, failing to meet dynamic usage requirements. In terms of abrasion resistance, yarns treated with existing sizing agents cannot form a sufficiently tough protective layer during weaving, resulting in severe frictional loss. This not only reduces production efficiency but also generates a large amount of frictional dust, polluting the production environment and subsequent processes. Furthermore, the anti-yellowing ability of existing sizing agents is a major weakness in high-temperature resistance. Taking the production of high-strength, high-temperature resistant insulating tape substrate as an example, when the fiberglass cloth blank is baked at 160℃, the cloth treated with existing sizing agents will show obvious yellowing, affecting not only the product appearance but also leading to a decline in product performance, severely restricting the application expansion of fiberglass cloth in high-end fields.

[0004] Therefore, developing a glass fiber cloth warping slurry with high elasticity, high wear resistance and low yellowing has become a key technical problem that the industry urgently needs to solve. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a glass fiber cloth warping slurry and its preparation method. The glass fiber cloth warping slurry of the present invention has the characteristics of high elasticity, high wear resistance and not easy to yellow.

[0006] The glass fiber cloth warping slurry, by weight, comprises the following components: 27-42 parts of waterborne polyurethane, 5-10 parts of composite silane coupling agent, 3-10 parts of polyvinyl alcohol, 0.1-1.0 parts of pH adjuster, 0.5-2 parts of silica, and 42.5-59.3 parts of water; the weight ratio of waterborne polyurethane to composite silane coupling agent is 3-6:1; the composite silane coupling agent is composed of γ-methacryloyloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane in a weight ratio of 1:1.1-4.

[0007] The synergistic effect of waterborne polyurethane and composite silane coupling agents is mainly achieved through interfacial bonding, controlling hydrolysis, and balancing performance. This synergistic effect gives the glass fiber cloth warping slurry high elasticity, high abrasion resistance, and resistance to yellowing after baking at 160℃ for 24 hours. Excessive waterborne polyurethane leads to excessively thick film formation, decreased slurry permeability, and easy aggregation of "agglomerates" between glass fiber monofilaments, reducing fiber flexibility. Insufficient waterborne polyurethane results in weak interfacial bonding, causing silica to easily detach from the interface. Excessive composite silane coupling agent leads to excessive hydrolysis and condensation, generating flocculent polysiloxane precipitates and losing its bridging effect. Insufficient composite silane coupling agent reduces the hydroxyl coverage on the glass fiber cloth surface, preventing effective bonding of waterborne polyurethane; and silica agglomerates cause stress concentration.

[0008] Adding waterborne polyurethane in amounts lower than those specified in this application will result in reduced binding force and warp tensile strength of the glass fiber yarn, increased weaving breakage rate and warp yarn breakage points, and the fabric surface will be more prone to yellowing after baking at 160°C for 24 hours.

[0009] The hydrolyzed groups in the composite silane coupling agent react with the silanol groups on the glass fiber surface to form chemical bonds, enhancing the inorganic interfacial bonding. Simultaneously, its organic functional groups react with the active groups of the waterborne polyurethane to form organic-inorganic covalent bonds. A weight ratio of 3-6:1 between the waterborne polyurethane and the composite silane coupling agent ensures sufficient coverage of the glass fiber surface, preventing excessive composite silane coupling agent from causing self-polymerization or an excessively thick interfacial layer. The composite silane coupling agent improves the mechanical strength of the slurry film by crosslinking the molecular chains of the waterborne polyurethane; however, excessive composite silane coupling agent can damage the resin's bulk structure. The composite silane coupling agent reduces the surface energy of the glass fiber, making it easier for the waterborne polyurethane to wet the fiber and reducing interfacial porosity.

[0010] The composite silane coupling agent is composed of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane. The weight ratio of γ-methacryloxypropyltrimethoxysilane to γ-aminopropyltriethoxysilane is 1:1.1~4. The synergistic effect of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane can improve interfacial strength, optimize hydrolysis and polycondensation reactions, and enhance dispersion stability and film uniformity.

[0011] The methacryloyloxypropyltrimethoxysilane reacts with the active groups of the waterborne polyurethane to form a covalent cross-linked network, enhancing interfacial strength. The amino group of the γ-aminopropyltriethoxysilane preferentially condenses with the silanol groups on the glass fiber surface, thereby reducing the fiber surface energy and enhancing wettability. Both work synergistically to achieve full chemical bonding bridging of the fiber-coupling agent-waterborne polyurethane, further improving interfacial strength.

[0012] The trimethoxy group of γ-methacryloxypropyltrimethoxysilane hydrolyzes into silanol under the action of acetic acid, anchoring it to the fiber surface. The triethoxy and amino groups of γ-aminopropyltriethoxysilane neutralize hydrogen ions due to their alkaline properties, inhibiting excessive polycondensation of γ-methacryloxypropyltrimethoxysilane and maintaining the concentration of active silanol.

[0013] The synergistic effect of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane improves dispersion stability. The amino groups of γ-aminopropyltriethoxysilane directionally adsorb silica particles, inhibiting sedimentation. γ-methacryloxypropyltrimethoxysilane enhances the coating power of waterborne polyurethane and reduces slurry segregation. The synergistic effect of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane also improves film uniformity. The two silanes optimize the rheological properties of the slurry, forming a continuous film on the fiber surface.

[0014] Preferably, the composite silane coupling agent is composed of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane in a weight ratio of 1:1.25~1.8. This ratio improves interfacial bonding efficiency and hydrothermal stability. A higher proportion of γ-aminopropyltriethoxysilane results in optimal coverage of the silanol groups on the glass fiber surface by its amino groups. Simultaneously, the crosslinking density of the methacryloxy groups in γ-methacryloxypropyltrimethoxysilane with the waterborne polyurethane is increased, leading to more chemical bonding sites. The high proportion of γ-aminopropyltriethoxysilane enhances the stress transfer efficiency between the fiber and the waterborne polyurethane, while the hydrophobic chains of γ-methacryloxypropyltrimethoxysilane block water molecule penetration, synergistically improving hydrothermal stability.

[0015] Preferably, the weight ratio of waterborne polyurethane to composite silane coupling agent is 4~5.8:1; this ratio maximizes interfacial bonding efficiency; the silane organic functional groups react more fully with the active groups of waterborne polyurethane, increasing the number of chemical bonds per unit area.

[0016] Preferably, the product comprises, by weight, 29-40 parts of waterborne polyurethane, 7-9 parts of composite silane coupling agent, 5-7 parts of polyvinyl alcohol, 0.2-0.4 parts of pH adjuster, 0.7-1.3 parts of silica, and 43.7-56.6 parts of water.

[0017] Preferably, the waterborne polyurethane is model 2611, purchased from Shanghai Diandong New Materials Co., Ltd. Model 2611 waterborne polyurethane is an anionic, aliphatic polyester-polyurethane dispersion.

[0018] The waterborne polyurethane of model 2611 has a solids content that reduces water evaporation, increases drying speed, and ensures high gloss and effective film thickness. This solids content range maintains appropriate stretching of the waterborne polyurethane molecular chains, reducing the risk of sedimentation or flocculation during storage and ensuring component homogeneity. The hydroxyl value of model 2611 provides sufficient active sites for effective crosslinking while avoiding excessive crosslinking that could increase film brittleness; it also facilitates the formation of hydrogen bond networks with polyvinyl alcohol and composite silane coupling agents in the formulation. The glass transition temperature of model 2611 can accommodate the stress caused by thermal expansion and contraction or deformation of the substrate, reducing the risk of cracking.

[0019] The polyvinyl alcohol used is PVA-1788, with a degree of polymerization of 1650–1750 and a degree of hydrolysis of 87–89%. At 20°C, a 4 wt% aqueous solution of PVA-1788 has a viscosity of 8.2–9.2 mPa·s. The degree of polymerization of 1650–1750 imparts a higher molecular chain length to the coating, enhancing cohesion and tensile strength, reducing the risk of cracking under stress, and ensuring continuous and uniform film formation. The degree of hydrolysis of 87–89% retains some acetyl groups, adjusting the hydrophilicity and hydrophobicity, improving the coating's stability in humid environments and its compatibility with waterborne polyurethane. This viscosity range ensures solution fluidity, making the coating easy to spread and wet the substrate surface.

[0020] The silica mentioned is hydrophilic nano-silica with a particle size of 15-25 nm and a specific surface area of ​​150-200 m². 2 / g, number of surface hydroxyl groups greater than or equal to 3 / nm 2 Hydrophilic nano-silica can further improve the abrasion resistance of the film, while its good dispersibility effectively improves the stability of the slurry and prevents sedimentation. The surface hydroxyl groups of hydrophilic nano-silica form a hydrogen bond network with the silanol groups on the surface of glass fibers, and simultaneously condense with the hydrolysis products of the composite silane coupling agent in the slurry, realizing multiple chemical bond bridging of "fiber-silica-waterborne polyurethane" and improving the interfacial bonding strength. The particle size and specific surface area of ​​silica in this application enable it to uniformly fill the micropores of the slurry, improve the density of the slurry film, and reduce the water penetration path. The silica used in this application can improve fiber restraint and fabric quality, reduce weaving breakage, and improve abnormal warp yarn breakage in the fabric.

[0021] This invention also provides a method for preparing a glass fiber cloth warping slurry, comprising the following steps:

[0022] (1) Dissolve polyvinyl alcohol in water according to the weight ratio, and then adjust the pH to obtain a slurry;

[0023] (2) Dissolve γ-methacryloxypropyltrimethoxysilane in water according to the weight ratio to obtain solution A; dissolve γ-aminopropyltriethoxysilane in water according to the weight ratio to obtain solution B;

[0024] (3) Add solution A, water-based polyurethane, solution B and silica to the slurry in sequence, mix well, let stand and then sieve; to obtain glass fiber cloth warping slurry.

[0025] The specific operation of step (1) is to dissolve polyvinyl alcohol in water at 80-85℃ according to the weight ratio, cool it to 40-45℃, and then adjust the pH to 4.3-4.5 with acetic acid to obtain a slurry. The pH adjuster in this application is acetic acid. Adjusting the pH to 4.3-4.5 with acetic acid has the functions of optimizing the hydrolysis of the composite silane coupling agent, stabilizing the polyvinyl alcohol solution, and synergistically dispersing nano-silica. Too high or too low a pH range will cause the slurry to degenerate and fail. This pH range is the optimal hydrolysis condition for γ-methacryloyloxypropyltrimethoxysilane, which can fully hydrolyze its alkoxy groups into silanols, improving the bonding efficiency with fibers and waterborne polyurethane. At the same time, it inhibits excessive polycondensation of silanols and maintains its activity until the subsequent composite stage. This pH range can prevent excessive ionization of polyvinyl alcohol molecular chains, maintain stable solution viscosity, and avoid a significant decrease in viscosity and stratification caused by excessively high pH. This pH range can promote the formation of hydrogen bond networks between the hydroxyl groups on the silica surface and the composite silane coupling agent and polyvinyl alcohol, improving the uniformity of the slurry.

[0026] The specific operation of step (2) is as follows: γ-methacryloxypropyltrimethoxysilane is dissolved in water with a pH of 4-4.5 in parts by weight for pre-hydrolysis, and stirred at 100-200 rpm for 35-45 min at 25-35℃ to obtain solution A; γ-aminopropyltriethoxysilane is dissolved in water with a pH of 4-4.5 in parts by weight for pre-hydrolysis, and stirred at 100-200 rpm for 35-45 min at 25-35℃ to obtain solution B. Pre-hydrolysis of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane together will result in turbidity of the slurry and visible coagulation, making it unusable.

[0027] The specific operation of step (3) is as follows: solution A, waterborne polyurethane, solution B, and silica are added sequentially to a slurry at 35-45°C and mixed evenly. After standing for 1.5-2.5 hours, the mixture is passed through a 400-mesh sieve to obtain a glass fiber cloth warping slurry. The 35-45°C condition ensures that the hydrolysis products of the composite silane coupling agent maintain stable activity, avoiding the failure of silanol polycondensation due to high temperature or insufficient hydrolysis due to low temperature. This temperature range also maintains the extended state of the polyvinyl alcohol molecular chains, promoting hydrogen bonding with silica. Standing for 1.5-2.5 hours allows the composite silane coupling agent to pre-bond with the waterborne polyurethane, avoiding interface weakening caused by direct contact with glass fiber competitive reaction; standing for 1.5-2.5 hours can prevent local glue deficiency due to electrostatic repulsion during glass fiber cloth impregnation; passing through a 400-mesh sieve ensures uniform dispersion and improves the stability of the slurry. When the temperature of the waterborne polyurethane added to the slurry is higher than the temperature range of this application, it will cause the slurry to form yellow sticky clumps and contaminate the yarn.

[0028] Compared with the prior art, the beneficial effects of this invention are:

[0029] 1. The glass fiber cloth warping slurry of the present invention has the characteristics of high elasticity, high abrasion resistance, and non-yellowing. Waterborne polyurethane and composite silane coupling agent achieve synergistic effect through interfacial bonding, controlling hydrolysis and performance balance mechanism; the synergistic effect of the two makes the glass fiber cloth warping slurry have the characteristics of high elasticity, high abrasion resistance, and non-yellowing after baking at 160℃ for 24 hours.

[0030] 2. In this invention, γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane work synergistically to improve interfacial strength, optimize hydrolysis and polycondensation reactions, and enhance dispersion stability and film uniformity. Detailed Implementation

[0031] Example 1 is the preferred embodiment of the present invention. The present invention will be further described below with reference to specific embodiments and comparative examples.

[0032] The chemical additives used in the embodiments and comparative examples of this invention are all commercially available, and the specific information is as follows:

[0033] γ-Methacryloxypropyltrimethoxysilane (OFS-6030): purchased from Shanghai Diandong New Materials Co., Ltd.; γ-aminopropyltriethoxysilane (KH-550): purchased from Jiangxi Chenguang New Materials Co., Ltd.; waterborne polyurethane (2611): purchased from Shanghai Diandong New Materials Co., Ltd.; silica: purchased from Zhengzhou Songshan Boron Industry Technology Co., Ltd.; polyvinyl alcohol (PVA-1788): purchased from Suzhou Haoyan Trading Co., Ltd.; acetic acid (glacial acetic acid): purchased from Yantai Yuandong Fine Chemical Co., Ltd.; water: deionized water.

[0034] Table 1. Raw material formulations used in Examples 1-9 (by weight).

[0035] .

[0036] Example 1

[0037] A glass fiber cloth warping slurry, the preparation method of which includes the following steps:

[0038] Step (1) Dissolve polyvinyl alcohol in water at 83°C according to the weight ratio, cool down to 43°C, and then adjust the pH to 4.4 with acetic acid to obtain slurry;

[0039] Step (2) Dissolve γ-methacryloxypropyltrimethoxysilane in water with a pH of 4.3 according to the weight ratio for pre-hydrolysis, and stir at 150 rpm for 40 min at 30°C to obtain solution A; Dissolve γ-aminopropyltriethoxysilane in water with a pH of 4.3 according to the weight ratio for pre-hydrolysis, and stir at 150 rpm for 40 min at 30°C to obtain solution B;

[0040] Step (3) Add solution A, waterborne polyurethane, solution B and silica to the slurry at 40°C in sequence, mix well, let stand for 2 hours, and then pass through a 400-mesh sieve to obtain glass fiber cloth warping slurry.

[0041] Example 2

[0042] A glass fiber cloth warping slurry, the preparation method of which includes the following steps:

[0043] Step (1) Dissolve polyvinyl alcohol in water at 80°C according to the weight ratio, cool down to 40°C, and then adjust the pH to 4.3 with acetic acid to obtain slurry;

[0044] Step (2) Dissolve γ-methacryloxypropyltrimethoxysilane in water with pH 4 according to the weight ratio for pre-hydrolysis, and stir at 200 rpm for 45 min at 25°C to obtain solution A; Dissolve γ-aminopropyltriethoxysilane in water with pH 4 according to the weight ratio for pre-hydrolysis, and stir at 200 rpm for 45 min at 25°C to obtain solution B;

[0045] Step (3) Add solution A, waterborne polyurethane, solution B and silica to the slurry at 35°C in sequence and mix well. After standing for 2.5 hours, pass through a 400-mesh sieve to obtain glass fiber cloth warping slurry.

[0046] Example 3

[0047] A glass fiber cloth warping slurry, the preparation method of which includes the following steps:

[0048] Step (1) Dissolve polyvinyl alcohol in water at 85°C according to the weight ratio, cool down to 45°C, and then adjust the pH to 4.5 with acetic acid to obtain slurry;

[0049] Step (2) Dissolve γ-methacryloxypropyltrimethoxysilane in water with a pH of 4.5 according to the weight ratio for pre-hydrolysis, and stir at 100 rpm for 35 min at 35°C to obtain solution A; dissolve γ-aminopropyltriethoxysilane in water with a pH of 4.5 according to the weight ratio for pre-hydrolysis, and stir at 100 rpm for 35 min at 35°C to obtain solution B;

[0050] Step (3) Add solution A, waterborne polyurethane, solution B and silica to the slurry at 45°C in sequence and mix well. After standing for 1.5 hours, pass through a 400-mesh sieve to obtain glass fiber cloth warping slurry.

[0051] Example 4

[0052] A glass fiber cloth warping slurry, the preparation method of which includes the following steps:

[0053] Step (1) Dissolve polyvinyl alcohol in water at 83°C according to the weight ratio, cool down to 43°C, and then adjust the pH to 4.4 with acetic acid to obtain slurry;

[0054] Step (2) Dissolve γ-methacryloxypropyltrimethoxysilane in water with a pH of 4.3 according to the weight ratio for pre-hydrolysis, and stir at 150 rpm for 40 min at 30°C to obtain solution A; Dissolve γ-aminopropyltriethoxysilane in water with a pH of 4.3 according to the weight ratio for pre-hydrolysis, and stir at 150 rpm for 40 min at 30°C to obtain solution B;

[0055] Step (3) Add solution A, waterborne polyurethane, solution B and silica to the slurry at 40°C in sequence, mix well, let stand for 2 hours, and then pass through a 400-mesh sieve to obtain glass fiber cloth warping slurry.

[0056] Example 5

[0057] A glass fiber cloth warping slurry, the preparation method of which includes the following steps:

[0058] Step (1) Dissolve polyvinyl alcohol in water at 83°C according to the weight ratio, cool down to 43°C, and then adjust the pH to 4.4 with acetic acid to obtain slurry;

[0059] Step (2) Dissolve γ-methacryloxypropyltrimethoxysilane in water with a pH of 4.3 according to the weight ratio for pre-hydrolysis, and stir at 150 rpm for 40 min at 30°C to obtain solution A; Dissolve γ-aminopropyltriethoxysilane in water with a pH of 4.3 according to the weight ratio for pre-hydrolysis, and stir at 150 rpm for 40 min at 30°C to obtain solution B;

[0060] Step (3) Add solution A, waterborne polyurethane, solution B and silica to the slurry at 40°C in sequence, mix well, let stand for 2 hours, and then pass through a 400-mesh sieve to obtain glass fiber cloth warping slurry.

[0061] Example 6

[0062] A glass fiber cloth warping slurry, the preparation method of which includes the following steps:

[0063] Step (1) Dissolve polyvinyl alcohol in water at 83°C according to the weight ratio, cool down to 43°C, and then adjust the pH to 4.4 with acetic acid to obtain slurry;

[0064] Step (2) Dissolve γ-methacryloxypropyltrimethoxysilane in water with a pH of 4.3 according to the weight ratio for pre-hydrolysis, and stir at 150 rpm for 40 min at 30°C to obtain solution A; Dissolve γ-aminopropyltriethoxysilane in water with a pH of 4.3 according to the weight ratio for pre-hydrolysis, and stir at 150 rpm for 40 min at 30°C to obtain solution B;

[0065] Step (3) Add solution A, waterborne polyurethane, solution B and silica to the slurry at 40°C in sequence, mix well, let stand for 2 hours, and then pass through a 400-mesh sieve to obtain glass fiber cloth warping slurry.

[0066] Example 7

[0067] A glass fiber cloth warping slurry, the preparation method of which includes the following steps:

[0068] Step (1) Dissolve polyvinyl alcohol in water at 83°C according to the weight ratio, cool down to 43°C, and then adjust the pH to 4.4 with acetic acid to obtain slurry;

[0069] Step (2) Dissolve γ-methacryloxypropyltrimethoxysilane in water with a pH of 4.3 according to the weight ratio for pre-hydrolysis, and stir at 150 rpm for 40 min at 30°C to obtain solution A; Dissolve γ-aminopropyltriethoxysilane in water with a pH of 4.3 according to the weight ratio for pre-hydrolysis, and stir at 150 rpm for 40 min at 30°C to obtain solution B;

[0070] Step (3) Add solution A, waterborne polyurethane, solution B and silica to the slurry at 40°C in sequence, mix well, let stand for 2 hours, and then pass through a 400-mesh sieve to obtain glass fiber cloth warping slurry.

[0071] Example 8

[0072] A glass fiber cloth warping slurry, the preparation method of which includes the following steps:

[0073] Step (1) Dissolve polyvinyl alcohol in water at 83°C according to the weight ratio, cool down to 43°C, and then adjust the pH to 4.4 with acetic acid to obtain slurry;

[0074] Step (2) Dissolve γ-methacryloxypropyltrimethoxysilane in water with a pH of 4.3 according to the weight ratio for pre-hydrolysis, and stir at 150 rpm for 40 min at 30°C to obtain solution A; Dissolve γ-aminopropyltriethoxysilane in water with a pH of 4.3 according to the weight ratio for pre-hydrolysis, and stir at 150 rpm for 40 min at 30°C to obtain solution B;

[0075] Step (3) Add solution A, waterborne polyurethane, solution B and silica to the slurry at 40°C in sequence, mix well, let stand for 2 hours, and then pass through a 400-mesh sieve to obtain glass fiber cloth warping slurry.

[0076] Example 9

[0077] A glass fiber cloth warping slurry, the preparation method of which includes the following steps:

[0078] Step (1) Dissolve polyvinyl alcohol in water at 83°C according to the weight ratio, cool down to 43°C, and then adjust the pH to 4.4 with acetic acid to obtain slurry;

[0079] Step (2) Dissolve γ-methacryloxypropyltrimethoxysilane in water with a pH of 4.3 according to the weight ratio for pre-hydrolysis, and stir at 150 rpm for 40 min at 30°C to obtain solution A; Dissolve γ-aminopropyltriethoxysilane in water with a pH of 4.3 according to the weight ratio for pre-hydrolysis, and stir at 150 rpm for 40 min at 30°C to obtain solution B;

[0080] Step (3) Add solution A, waterborne polyurethane, solution B and silica to the slurry at 40°C in sequence, mix well, let stand for 2 hours, and then pass through a 400-mesh sieve to obtain glass fiber cloth warping slurry.

[0081] Comparative Example 1

[0082] The preparation method of the glass fiber cloth warping slurry described in this comparative example is the same as that in Example 1, except that 20 parts of waterborne polyurethane are added in step (3).

[0083] Comparative Example 2

[0084] The raw material formulation of the glass fiber cloth warping slurry described in this comparative example is the same as that in Example 1, the only difference is that in step (2), γ-methacryloyloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane are mixed and dissolved in water with a pH of 4.3 at a weight ratio of 1:1.5 for pre-hydrolysis at 30°C and stirred at 150 rpm for 40 min to obtain solution A.

[0085] Comparative Example 3

[0086] The raw material formulation of the glass fiber cloth warping slurry described in this comparative example is the same as that in Example 1, the only difference is that when waterborne polyurethane is added to the slurry in step (3), the temperature of the slurry is 55°C.

[0087] Comparative Example 4

[0088] The preparation method of the glass fiber cloth warping slurry described in this comparative example is the same as that in Example 1, except that γ-methacryloyloxypropyltrimethoxysilane was not added in step (2).

[0089] Comparative Example 5

[0090] The preparation method of the glass fiber cloth warping slurry described in this comparative example is the same as that in Example 1, except that silica is not added in step (3).

[0091] Comparative Example 6

[0092] The preparation method of the glass fiber cloth warping slurry described in this comparative example is the same as that in Example 1, except that γ-aminopropyltriethoxysilane was not added in step (2).

[0093] Comparative Example 7

[0094] The preparation method of the glass fiber cloth warping slurry described in this comparative example is the same as that in Example 1, except that 3.75 parts of γ-methacryloyloxypropyltrimethoxysilane and 3.75 parts of γ-aminopropyltriethoxysilane are added in step (2).

[0095] Comparative Example 8

[0096] The preparation method of the glass fiber cloth warping slurry described in this comparative example is the same as that in Example 1, except that the pH is adjusted to 3.5 with acetic acid in step (1).

[0097] Comparative Example 9

[0098] The preparation method of the glass fiber cloth warping slurry described in this comparative example is the same as that in Example 1, except that 1.4 parts of γ-methacryloyloxypropyltrimethoxysilane and 6.1 parts of γ-aminopropyltriethoxysilane are added in step (2).

[0099] Comparative Example 10

[0100] The preparation method of the glass fiber cloth warping slurry described in this comparative example is the same as that in Example 1, except that the pH is adjusted to 4.8 with acetic acid in step (1).

[0101] Performance testing

[0102] The performance of the glass fiber cloth warping slurries prepared in the examples and comparative examples was tested. The specific test results are shown in Tables 2, 3 and 4.

[0103] Application method of sizing: Immersion sizing, machine speed 180m / min, steam drying temperature 140℃; weft yarn is not sizing twice, glass fiber yarn is sizing once during the drawing stage;

[0104] The fiber binding force of the warping slurry for glass fiber cloth was tested in accordance with JIS L1096.

[0105] The desizing rate of the warping sizing agent for fiberglass cloth was tested according to AATCC97.

[0106] Test of bending resistance of glass fiber cloth warping sizing: Take a single glass fiber bundle with a length of 15cm, use a clamp to hold both ends of the bundle so that the effective length is 10cm, bend it 180°, and test the number of fatigue breaks of the bundle.

[0107] Breakage rate test of fiberglass cloth warping sizing; the fiberglass cloth used was model 7628m-127, with a warp density of 43 yarns / 25 mm, a weft density of 30.5 yarns / 25 mm, a nominal area mass of 203.4 g / m², a nominal thickness of 0.173 mm, warp yarn code EC 9-68×1, and weft yarn code EC 9-68×1. The number of yarn breaks per 10,000 meters was tested (each yarn per breakage).

[0108] Warp tensile strength test of fiberglass cloth warp slurry: A fiberglass cloth sample with a width (width direction is weft direction) of 1 inch and a length (length direction is warp direction) of 15cm was taken and tested for tensile strength of the 1-inch fiberglass cloth using a special tensile testing instrument.

[0109] Fabric warp yarn breakage point test: Breakage point refers to the number of broken yarns in the original yarn of the fabric. The data in Tables 2 and 3 are the number of broken yarns per 100 meters. Warp yarn code EC 9-68×1;

[0110] Yellowing test of fiberglass cloth warping slurry: visually inspect for yellowing after baking at 160℃ for 24 hours.

[0111] Table 2 Performance test results of Examples 1-9

[0112] .

[0113] Table 3 Performance test results of Comparative Examples 1-10

[0114] .

[0115] Table 4. Slurry test results of Examples 1-9 and Comparative Examples 1-10

[0116] .

[0117] In this invention, waterborne polyurethane and composite silane coupling agent achieve synergistic effects through interfacial bonding, controlling hydrolysis and performance balance; the synergistic effect of the two gives the glass fiber cloth warping slurry high elasticity, high abrasion resistance, and the characteristic of not easily yellowing after baking at 160℃ for 24 hours.

[0118] A higher fiber binding force indicates a better binding and protection effect of the sizing agent on the fibers; a higher number of flexural cycles indicates better folding resistance of the fabric; a higher desizing rate indicates more thorough removal of the sizing agent; a lower weaving breakage rate indicates better stability of the warp yarns during the weaving process; a higher tensile strength indicates better tensile properties of the yarn or fabric; a lower warp yarn breakage point indicates better appearance integrity and abrasion resistance of the warp yarns; and no yellowing indicates good high-temperature stability of the material.

[0119] As shown in Comparative Example 1, the amount of waterborne polyurethane added is lower than the range of this application, which leads to a decrease in the binding force and warp tensile strength of the glass fiber yarn, an increase in the weaving breakage rate and the number of warp yarn breakage points on the fabric surface, and the fabric surface is more prone to yellowing after baking at 160°C for 24 hours. In contrast, Example 1 has higher binding force and warp tensile strength of the glass fiber yarn, lower weaving breakage rate and fewer warp yarn breakage points on the fabric surface, and the fabric surface does not yellow after baking at 160°C for 24 hours.

[0120] As shown in Comparative Example 2, the pre-hydrolysis of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane resulted in a cloudy slurry with visible lumps, rendering it unusable and thus preventing performance data from being measured. As shown in Comparative Example 3, when the temperature at which the waterborne polyurethane was added to the slurry exceeded the temperature range of this application, it caused the formation of yellow, sticky lumps that contaminated the yarn. In contrast, the slurry prepared in Example 1 yielded excellent performance.

[0121] As can be seen from Comparative Example 5, the silica used in this application can improve fiber restraint and fabric quality, reduce weaving breakage, and improve abnormal warp yarn breakage on the fabric surface.

[0122] As can be seen from Comparative Examples 4 and 6, the effects of this application cannot be achieved by simply adding γ-methacryloyloxypropyltrimethoxysilane or γ-aminopropyltriethoxysilane.

[0123] As can be seen from Comparative Examples 7 and 9, when the weight ratio of γ-methacryloyloxypropyltrimethoxysilane to γ-aminopropyltriethoxysilane exceeds the range of this application, it will cause yellowing when baked at 160°C for 24 hours.

[0124] A comparison of Example 1 with Comparative Examples 8 and 10 shows that when the pH of the slurry exceeds the range specified in this application, the slurry becomes turbid, contains large particle aggregates, and cannot be used normally. The pH range specified in this application effectively prevents adverse reactions during slurry preparation.

[0125] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A glass fiber cloth warping slurry, characterized in that, The product, by weight, comprises the following components: 27-42 parts of waterborne polyurethane, 5-10 parts of composite silane coupling agent, 3-10 parts of polyvinyl alcohol, 0.1-1.0 parts of pH adjuster, 0.5-2.0 parts of silica, and 42.5-59.3 parts of water; the weight ratio of waterborne polyurethane to composite silane coupling agent is 3-6:1; the composite silane coupling agent is composed of γ-methacryloyloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane in a weight ratio of 1:1.1-4.

2. The glass fiber cloth warping slurry according to claim 1, characterized in that, By weight, it consists of the following components: 29-40 parts waterborne polyurethane, 7-9 parts composite silane coupling agent, 5-7 parts polyvinyl alcohol, 0.2-0.4 parts pH adjuster, 0.7-1.3 parts silica and 43.7-56.6 parts water.

3. The glass fiber cloth warping slurry according to claim 1, characterized in that: The weight ratio of the waterborne polyurethane to the composite silane coupling agent is 4~5.8:

1.

4. The glass fiber cloth warping slurry according to claim 1, characterized in that: The composite silane coupling agent is composed of γ-methacryloxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane in a weight ratio of 1:1.25~1.

8.

5. The glass fiber cloth warping slurry according to claim 1, characterized in that: The silica has a particle size of 15-25 nm and a specific surface area of ​​150-200 m². 2 / g, number of surface hydroxyl groups greater than or equal to 3 / nm 2 .

6. A method for preparing a glass fiber cloth warping slurry according to any one of claims 1 to 5, characterized in that, Includes the following steps: (1) Dissolve polyvinyl alcohol in water according to the weight ratio, and then adjust the pH to obtain a slurry; (2) Dissolve γ-methacryloxypropyltrimethoxysilane in water according to the weight ratio to obtain solution A; dissolve γ-aminopropyltriethoxysilane in water according to the weight ratio to obtain solution B; (3) Add solution A, water-based polyurethane, solution B and silica to the slurry in sequence, mix well, let stand and then sieve; to obtain glass fiber cloth warping slurry; The specific operation of step (1) is to dissolve polyvinyl alcohol in water at 80~85℃ according to the weight, cool it down to 40~45℃, and then adjust the pH to 4.3~4.5 to obtain slurry.

7. The method for preparing a glass fiber cloth warping slurry according to claim 6, characterized in that, The specific operation of step (2) is as follows: γ-methacryloxypropyltrimethoxysilane is dissolved in water with a pH of 4-4.5 in parts by weight for pre-hydrolysis, and stirred at 100-200 rpm for 35-45 min at 25-35℃ to obtain solution A; γ-aminopropyltriethoxysilane is dissolved in water with a pH of 4-4.5 in parts by weight for pre-hydrolysis, and stirred at 100-200 rpm for 35-45 min at 25-35℃ to obtain solution B.

8. The method for preparing a glass fiber cloth warping slurry according to claim 6, characterized in that, The specific operation of step (3) is as follows: add solution A, water-based polyurethane, solution B and silica to the slurry at 35~45℃ in sequence, mix well, let stand for 1.5~2.5h and then pass through a 400-mesh sieve to obtain glass fiber cloth warping slurry.