Fireproof and skidproof composite multi-layer coiled material

Abstract

The present application belongs to the technical field of polymer materials, and particularly relates to a fireproof and antiskid composite multi-layer coiled material, which comprises SBC hot melt adhesive layer, fireproof fiber cloth layer, fireproof butyl rubber layer and non-woven fabric layer which are sequentially attached together. The thickness of the SBC hot melt adhesive layer is 0.1mm-0.3mm, the thickness of the fireproof fiber cloth layer is 0.2mm-1.0mm, the thickness of the fireproof butyl rubber layer is 0.4mm-1.5mm, and the thickness of the non-woven fabric layer is 0.1mm-0.3mm. The fireproof and antiskid composite multi-layer coiled material provided by the present application has the advantages that the SBC hot melt adhesive layer can be partially moisture-cured, so that the cohesive strength is increased and the holding adhesion is substantially improved. When the coiled material is applied, compared with the existing butyl rubber, the slippage caused by the frequent treading of workers during the installation of the roof with large slope can be completely avoided. Meanwhile, the fireproof butyl rubber layer with the thickness of 0.4mm-1.5mm is applied, the non-woven fabric is used to replace the commonly used fireproof fiber in the fifth layer, the overall fireproof performance still meets the requirements, but the cost of the final product can be significantly reduced.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a fireproof and slip-resistant composite multilayer roll material. Background Technology

[0002] Many roofing waterproof membranes have certain flame-retardant properties, but with the popularization of roof solar panels, the roofing membranes used in conjunction with them have more stringent requirements for flame retardancy and fire resistance, such as being able to withstand tests at temperatures of 900℃ or above.

[0003] CN101067465A discloses an intumescent fireproof sleeve and its preparation method, wherein the matrix resin is an oxygen-rich polymer, and its ability to withstand a high temperature of 900°C has not been tested or demonstrated. CN101121796A discloses an example containing expanded graphite and butyl rubber, but its ability to withstand a high temperature of 900°C has not been tested or demonstrated. US9611639B2 discloses an EPDM waterproof membrane containing expanded graphite, which is a single-layer structure. Utility model CN203451997U discloses an 8-layer fireproof membrane; CN 213977520U discloses an asphalt fireproof membrane.

[0004] CN115232577A and CN115093805A disclose a multi-layer composite fireproof membrane that can withstand high temperatures. However, during installation on roofs with steep slopes, slippage between the membrane and the roof substrate can easily occur due to people walking on it. Currently, there is no membrane that combines high-temperature fire resistance and slip resistance.

[0005] The information disclosed in this background section is intended only to enhance the understanding of the overall background of the invention and should not be construed as an admission or in any way implying that the information constitutes prior art known to those skilled in the art. Summary of the Invention

[0006] This invention is made to solve the above-mentioned problems, and aims to provide a fireproof and slip-resistant composite multilayer roll material that can effectively prevent slippage caused by frequent stepping on the roof during installation on a steep roof.

[0007] This invention provides a fireproof and slip-resistant composite multilayer roll material, characterized by comprising: an SBC hot melt adhesive layer, a fire-resistant fiber cloth layer, a fire-resistant butyl rubber layer, and a non-woven fabric layer sequentially bonded together, wherein the thickness of the SBC hot melt adhesive layer is 0.1mm to 0.3mm, the thickness of the fire-resistant fiber cloth layer is 0.2mm to 1.0mm, the thickness of the fire-resistant butyl rubber layer is 0.4mm to 1.5mm, and the thickness of the non-woven fabric layer is 0.1mm to 0.3mm.

[0008] The fireproof and anti-slip composite multilayer roll material provided by this invention may also have the following characteristics: the SBC hot melt adhesive layer is made of polyurethane-doped SBC hot melt adhesive, and contains the following components in the following mass ratios: non-reactive SBC hot melt adhesive: 70-80 parts; reactive polyurethane: 20-30 parts; the non-reactive SBC hot melt adhesive contains the following components in the following mass ratios: naphthenic oil: 10-20 parts; hydrogenated petroleum resin: 40-50 parts; SIS: 30-40 parts; SBS: 20-5 parts; the reactive polyurethane contains the following components in the following mass ratios: pure monomer resin: 40-50 parts; medium- to high-molecular-weight polyol: 40-50 parts; low-molecular-weight polyol: 1-2 parts; isocyanate: 5-15 parts; the number average molecular weight of the medium- to high-molecular-weight polyol is 2700 Dalton to 15000 Dalton; the low-molecular-weight polyol has 4-6 carbon atoms in its molecular formula and a functionality of 2.

[0009] The fireproof and anti-slip composite multilayer roll material provided by the present invention may also have the following feature: the fire-resistant fiber cloth layer is made of any one of silicon titanium cloth, ceramic fiber cloth or glass fiber cloth.

[0010] The fireproof and anti-slip composite multilayer roll material provided by the present invention may also have the following feature: wherein the fireproof butyl rubber layer is made of heat-expandable fireproof butyl rubber.

[0011] The fireproof and anti-slip composite multilayer roll material provided by the present invention may also have the following feature: the non-woven fabric layer is made of PP non-woven fabric or PET non-woven fabric.

[0012] The fireproof and anti-slip composite multilayer roll material provided by the present invention may also have the following characteristics: wherein the basis weight of the PP nonwoven fabric is 130gsm to 145gsm.

[0013] The fire-resistant and anti-slip composite multilayer roll material provided by this invention may also have the following characteristics: the thickness of the SBC hot melt adhesive layer is 0.2mm to 0.3mm, the thickness of the fire-resistant fiber cloth layer is 0.3mm to 0.4mm, the thickness of the fire-resistant butyl rubber layer is 1.0mm to 1.2mm, and the thickness of the non-woven fabric layer is 0.2mm to 0.3mm. The fire-resistant and anti-slip composite multilayer roll material provided by this invention may also further include: an isolation layer.

[0014] The isolation layer is bonded to the SBC hot melt adhesive layer, and the fire-resistant fiber cloth layer is bonded to both sides of the SBC hot melt adhesive layer.

[0015] The fireproof and anti-slip composite multilayer roll material provided by the present invention may also have the following feature: wherein the thickness of the isolation layer is 0.05mm to 0.2mm.

[0016] The fireproof and anti-slip composite multilayer roll material provided by the present invention may also have the following feature: wherein the isolation layer is an isolation film or an isolation paper.

[0017] The role and effect of invention

[0018] The fire-resistant and slip-resistant composite multilayer roll material provided by this invention, due to the partial moisture curing of the SBC hot melt adhesive layer, increases cohesive strength and fundamentally improves adhesion. When applied to roll materials, compared to existing butyl rubber, it completely avoids slippage caused by frequent footsteps during installation on roofs with steep slopes. Furthermore, by using a 0.4mm to 1.5mm thick fire-resistant butyl rubber layer, and replacing commonly used fire-resistant fibers with non-woven fabric in the fifth layer, the overall fire resistance still meets requirements, but the cost of the final product is significantly reduced. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of the fireproof and anti-slip composite multilayer roll material of the present invention;

[0020] Figure 2 This is a schematic diagram of the preparation process of the fireproof and anti-slip composite multilayer roll material of the present invention. Detailed Implementation

[0021] To make the technical means, creative features, objectives and effects of this invention easy to understand, the following describes in detail a fireproof and anti-slip composite multilayer roll material of this invention with reference to embodiments and accompanying drawings.

[0022] Unless otherwise specified, all raw materials used in this invention were purchased through normal commercial channels. All unmentioned testing standards are national standards.

[0023] The polyurethane-doped SBC hot melt adhesive of the present invention comprises the following components in parts by mass:

[0024] Non-reactive SBC hot melt adhesive: 70-80 parts;

[0025] Reactive polyurethane: 20-30 parts;

[0026] The non-reactive SBC hot melt adhesive contains the following components in parts by weight:

[0027] Naphthenic oil: 10-20 parts;

[0028] Hydrogenated petroleum resin: 40-50 parts;

[0029] Antioxidant: 0.3–1 part;

[0030] SIS: 30-40 copies;

[0031] SBS: 20-5 copies;

[0032] Reactive polyurethanes contain the following components in parts by mass:

[0033] Pure monomer resin: 40-50 parts;

[0034] Medium and high molecular weight polyols: 40-50 parts;

[0035] Low molecular weight polyols: 1-2 parts;

[0036] Isocyanate: 5-15 parts.

[0037] The specific names or sources of the above-mentioned raw materials are as follows:

[0038] The naphthenic oil has a Cn content greater than 40%; Sinopec KN4010 is preferred, with a Cn content of 49%.

[0039] Hydrogenated petroleum resins can be selected from hydrogenated C5 resins or hydrogenated pure monomer resins. The softening point of hydrogenated C5 resin is 95℃~105℃, with Lanzhou Petrochemical LH100-0 being preferred, having a softening point of 101℃. The softening point of hydrogenated pure monomer resin is 100℃~110℃, with Mw = 1290 Dalton~1500 Dalton; Eastman Regalrez 6108 is preferred, with a softening point of 108℃ and Mw = 1460 Dalton.

[0040] The antioxidant is one or more of the following: hindered phenolic antioxidants, phosphate ester antioxidants, and amine-containing antioxidants. Preferably, BASF Irganox 1010, which belongs to the hindered phenolic antioxidant class, is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and BASF Irgafox 168, which belongs to the phosphate ester antioxidant class, is tris(2,4-di-tert-butylphenyl)phosphite.

[0041] The styrene-isoprene-styrene block copolymer (SIS) is linear or star-shaped, with St% = 20%–40%, diblock content = 0–40%, and MFR (g / 10mins, 200℃, 5kg) = 10–30; the preferred SIS is YH1209 from Yueyang Petrochemical, linear, with St% = 29%, diblock content = 0%, and MFR (g / 10mins, 200℃, 5kg) = 10.

[0042] Styrene-butadiene-styrene block copolymer (SBS) is linear, with St% = 30-40% and MFR (g / 10mins, 200℃, 5kg) = 1-10; preferably Yueyang Petrochemical SBS792, linear, with St% = 40% and MFR (g / 10mins, 200℃, 5kg) = 2.

[0043] The softening point of the pure monomer resin is 80℃~105℃, Mw=1000Dalton~1200Dalton; Eastman Kristalex F85 is preferred, with a softening point of 86℃ and Mw=1050Dalton.

[0044] The medium and high molecular weight polyols are polypropylene glycol ether diols or polybutadiene polyols.

[0045] The polypropylene glycol ether diol has a number-average molecular weight of 10,000 Dalton to 15,000 Dalton, a hydroxyl value (OHV) of 8 mg KOH / g to 11 mg KOH / g, and a functionality Fn of 2. In this invention, the polypropylene glycol ether polyol has an OHV of 8 mg KOH / g to 11 mg KOH / g and an Fn of 2. Preferably, it is BD2-12000A from Bard Polyurethane Technology Co., Ltd., which is a polypropylene glycol ether diol with an OHV of 10 mg KOH / g and an Fn of 2.

[0046] The OHV of polybutadiene polyols is 44 mg KOH / g to 51 mg KOH / g, Fn is 2 to 3, and Mn is 2700 Dalton to 3100 Dalton. Evonik Polyvest HT is preferred, with OHV of 47, Fn of 2.4, and Mn of 2900 Dalton.

[0047] The low-molecular-weight polyol can be any one of 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, butanediol, or neopentanediol, preferably 3-methyl-1,5-pentanediol. In this invention, the low-molecular-weight polyol has 4 to 6 carbon atoms in its molecular formula and a functionality Fn of 2.

[0048] The isocyanate is any one or more selected from hexamethylene diisocyanate, isophorone diisocyanate, 4,4-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, or naphthalene diisocyanate. Covestro Desmodur 44C is preferred, as it is composed of 4,4-diphenylmethane diisocyanate.

[0049] A method for preparing polyurethane-doped SBC hot melt adhesive includes the following steps:

[0050] Step 1, Preparation of non-reactive SBC hot melt adhesive: Add naphthenic oil, half of hydrogenated petroleum resin, antioxidant, SIS and SBS in a predetermined mass ratio to a mixing tank and stir at 150℃~180℃ until no particles are present. Then add the remaining half of the hydrogenated petroleum resin and continue stirring until no particles are present.

[0051] The specific operation is as follows: add the naphthenic oil, half of the hydrogenated petroleum resin, antioxidant, SIS and SBS in a predetermined mass ratio into a mixing tank and stir at 150℃~180℃ for 2-4 hours. Take a sample and scrape it into a 0.1mm film for inspection. If there are particles, continue stirring for 30 minutes. If there are no particles, add the remaining hydrogenated petroleum resin and continue stirring for 1 hour. After visually inspecting for no particles, filter the material out for later use.

[0052] Step 2, Preparation of reactive polyurethane: Pure monomer resin and medium- to high-molecular-weight polyols in a predetermined mass ratio are added to a reaction vessel, heated to 110°C to 120°C, and then vacuum stirred and dehydrated for 1 to 2 hours. After cooling to 80°C to 90°C, isocyanate is added and the mixture is vacuum reacted at 80°C to 100°C for 1 to 2 hours. Then, low-molecular-weight polyols that have been dried with molecular sieves are added, and the reaction is continued for 0.5 to 1 hour. The mixture is then filtered and discharged.

[0053] The specific operation is as follows: add pure monomer resin and medium- to high-molecular-weight polyols in a predetermined mass ratio into a reaction vessel, heat to 110℃~120℃, vacuum stir and dehydrate for 1~2 hours, cool to 80℃~90℃, then add isocyanate, react under vacuum at 80℃~100℃ for 1~2 hours, add low-molecular-weight polyols that have been dried with molecular sieves, continue the reaction for 0.5~1 hours, filter and discharge the material, and the packaging must be moisture-proof.

[0054] Step 3: Add the non-reactive SBC hot melt adhesive prepared in Step 1 and the reactive polyurethane prepared in Step 2 to another reactor, and stir under vacuum at 140℃~160℃ for 0.5~1.5h to obtain polyurethane-doped SBC hot melt adhesive.

[0055] The specific operation is as follows: Add the non-reactive SBC hot melt adhesive from step 1 and the reactive polyurethane from step 2 to another reaction vessel, and stir under vacuum at 140℃~160℃ for 0.5~1.5h before discharging for later use. The packaging must be moisture-proof.

[0056] The polyurethane-doped SBC hot melt adhesive prepared by this invention can be used in fireproof and anti-slip composite multilayer rolls.

[0057] Figure 1 This is a schematic diagram of the fireproof and anti-slip composite multilayer roll material of the present invention.

[0058] like Figure 1As shown, the fireproof and anti-slip composite multilayer roll material has a five-layer structure that is laminated together sequentially. From top to bottom, it consists of an isolation layer L1, an SBC hot melt adhesive layer L2, a fire-resistant fiber cloth layer L3, a fire-resistant butyl rubber layer L4, and a non-woven fabric layer L5. The thickness of the isolation layer L1 is 0.05mm to 0.2mm, preferably 0.05mm to 0.1mm. The thickness of the SBC hot melt adhesive layer L2 is 0.1mm to 0.3mm, preferably 0.2mm to 0.3mm. The thickness of the fire-resistant fiber cloth layer L3 is 0.2mm to 1.0mm, preferably 0.3mm to 0.4mm. The thickness of the fire-resistant butyl rubber layer L4 is 0.4mm to 1.5mm, preferably 1.0mm to 1.2mm. The thickness of the non-woven fabric layer L5 is 0.1mm to 0.3mm, preferably 0.2mm to 0.3mm.

[0059] The refractory fiber cloth is made of silicon-titanium cloth (high-silica cloth), ceramic fiber cloth, glass fiber cloth, etc. The fire-retardant butyl rubber is a thermally expandable fire-retardant butyl rubber, specifically material A from Example 1 of patent CN115232577A. The non-woven fabric is PP or PET non-woven fabric, preferably PP non-woven fabric, with a basis weight of 130gsm to 145gsm.

[0060] Figure 2 This is a schematic diagram of the preparation process of the fireproof and anti-slip composite multilayer roll material of the present invention.

[0061] like Figure 2 As shown, the preparation of fire-resistant and slip-resistant composite multilayer roll material includes the following steps:

[0062] Step SA1: Prepare non-reactive SBC hot melt adhesive in the first mixer 1, using the same detailed method as Step 1 above.

[0063] Step SA2: Prepare reactive polyurethane in the second mixer 2, using the same detailed method as step 2 above.

[0064] Step SA3: Prepare polyurethane-doped SBC hot melt adhesive in the third mixer 3, using the same detailed method as step 3 above.

[0065] Step SA4: The polyurethane-doped SBC hot melt adhesive (second layer) is fed into the hot melt adhesive cylinder of the coating machine 5. The cylinder temperature is 160℃~185℃, the hose temperature is 160℃~185℃, the coating head temperature is 160℃~185℃, and the adhesive layer thickness is controlled at 0.1mm~0.3mm. The adhesive is applied to the refractory fiber cloth (third layer) unwound by the first unwinding machine 4, and then combined with the release film (first layer) unwound by the second unwinding machine 6 by the first composite roller 7. After being wound up by the first winding machine 8, semi-finished product A is obtained.

[0066] Step SA5: The raw materials for preparing fire-retardant butyl rubber are fed into the kneader 9 and kneaded. The resulting fire-retardant butyl rubber material is then fed into the extruder 10 (extrusion temperature between 80℃ and 110℃). A butyl rubber layer (fourth layer) of 0.4mm to 1.5mm is extruded through the extrusion die onto the other side of the fire-resistant fiber cloth of semi-finished product A. At this time, semi-finished product A is unwound by the third unwinding machine 11. The butyl rubber surface is then combined with the non-woven fabric (fifth layer) unwound by the third unwinding machine 12 and the second composite roller 13. After being cut to the specified width by the online edge trimmer 14, it is wound up by the second winding machine 15 to obtain the finished product.

[0067] The fire-retardant butyl rubber compound in step SA5 above was prepared entirely according to the composition and method of rubber compound A in Example 1 of CN115232577A.

[0068] The materials used in the preparation examples, embodiments, and comparative examples of this invention are as follows:

[0069] Naphthenic oil: Sinopec KN4010, Cn = 49%;

[0070] Hydrogenated C5 resin: Lanzhou Petrochemical LH100-0, softening point is 101℃;

[0071] Hydrogenated pure monomer resin: Eastman Regalrez 6108, softening point 108℃, Mw = 1460 Dalton;

[0072] Antioxidants: BASF Irganox 1010 is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], which belongs to hindered phenolic antioxidants; and BASF Irgafox 168 is tris(2,4-di-tert-butylphenyl)phosphite, which belongs to phosphate antioxidants.

[0073] SIS: Yueyang Petrochemical SIS YH1209, linear, St% = 29%, diblock content is 0%, MFR (g / 10mins, 200℃, 5kg) = 10;

[0074] SBS: Yueyang Petrochemical SBS792, linear, St% 40%, MFR (g / 10mins, 200℃, 5kg) 2;

[0075] Pure monomer resin: Eastman Kristalex F85, softening point 86℃, Mw=1050Dalton;

[0076] Polypropylene glycol ether diol: BD2-12000A, produced by Bard Polyurethane Technology Co., Ltd., is a polypropylene glycol ether polyol with an OHV of 10 mg KOH / g and an Fn of 2.

[0077] Polybutadiene polyol: Evonik Polyvest HT, OHV = 47, Fn = 2.4, Mn = 2900 Dalton;

[0078] Low molecular weight polyol: 3-methyl-1,5-pentanediol;

[0079] Isocyanate: Covestro Desmodur 44C, is 4,4-diphenylmethane diisocyanate;

[0080] Fireproof fiber cloth 1 is silicon-titanium cloth (high silica cloth), 0.3mm thick, Suzhou Weidun Composite Cloth Co., Ltd.;

[0081] Fireproof fiber cloth 2 is glass fiber cloth with a thickness of 0.30mm, Jiujiang Lianfeng Glass Fiber Co., Ltd.;

[0082] Fireproof fiber cloth 3 is aluminum silicate ceramic fiber cloth, 0.30mm thick, Zhengzhou Jianxu Thermal Insulation and Refractory Materials Co., Ltd.

[0083] Non-woven fabric 1 is a double-layer PP non-woven fabric with a basis weight of 130gsm, manufactured by Wuxi Qiante Insulation Materials Co., Ltd.

[0084] Non-woven fabric 2 is a three-layer PP non-woven fabric with a basis weight of 145gsm, manufactured by Wuxi Qiante Insulation Materials Co., Ltd.

[0085] The release film is a PET release film with a thickness of 0.1mm.

[0086] <Preparation Example 1>

[0087] A heat-expandable fire-retardant butyl rubber was prepared according to the formulation and process steps of rubber compound A in Example 1 of CN115232577A.

[0088] <Preparation Example 2>

[0089] Prepare a non-reactive SBC hot melt adhesive with the following formulation (total 600 kg):

[0090] Sinopec KN4010: 15 portions;

[0091] Lanzhou Petrochemical LH100-0:47 copies;

[0092] BASF Irganox 1010: 0.5 doses;

[0093] BASF Irgafox 168: 0.5 copies;

[0094] Yueyang Petrochemical SIS YH1209: 34 copies;

[0095] Yueyang Petrochemical SBS792: 3 copies;

[0096] The raw materials, naphthenic oil, half of the hydrogenated petroleum resin, antioxidants BASF Irganox 1010 and ASF Irgafox 168, SIS YH1209, and SBS792 rubber were added to a 1000L mixing tank and stirred at 170℃~180℃ for 3 hours. A sample was then scraped into a 0.1mm film for inspection. If particles were present, stirring was continued for another 30 minutes. If the film was transparent and free of particles, the remaining hydrogenated petroleum resin was added and stirring continued for 1 hour. After visual inspection to ensure transparency and the absence of particles, the film was filtered (using a 100-mesh steel screen) for later use. The properties of the rubber compound are shown in Table 1.

[0097] <Preparation Example 3>

[0098] Another type of non-reactive SBC hot melt adhesive was prepared with the following formulation (total 600 kg):

[0099] Sinopec KN4010: 15 portions;

[0100] Eastman Regalrez 6108:47 copies;

[0101] BASF Irganox 1010: 0.5 doses;

[0102] BASF Irgafox 168: 0.5 copies;

[0103] Yueyang Petrochemical SIS YH1209: 34 copies;

[0104] Yueyang Petrochemical SBS792: 3 copies;

[0105] The preparation method is the same as in Preparation Example 2, and the properties of the rubber compound are shown in Table 1.

[0106] <Preparation Example 4>

[0107] Prepare reactive polyurethane with the following formulation (total 600 kg):

[0108] Eastman Kristalex F85: 45 copies;

[0109] BD2-12000A from Bard Polyurethane Technology Co., Ltd.: 44 copies;

[0110] 3-Methyl-1,5-pentanediol: 1 part;

[0111] Covestro Desmodur 44C: 10 servings;

[0112] Pure monomer resin and polypropylene glycol ether diol BD2-12000A were added to a 1000L reactor. The mixture was heated to 110℃~120℃, then vacuum-stirred and dehydrated for 1.5 hours. After cooling to 80℃~90℃, isocyanate Desmodur 44C was added. The mixture was then reacted under vacuum at 85℃~95℃ for 1 hour. Finally, low-molecular-weight polyol 3-methyl-1,5-pentanediol, which had been pre-dried using molecular sieves, was added, and the reaction continued for another hour. The mixture was then filtered (using a 100-mesh steel screen) and packaged to prevent moisture. The NCO content was found to be 2.3%, and the hot melt viscosity (60℃) was 3600 cps. The NCO content test method followed GB / T 12009.4-2016, and the hot melt viscosity test method followed HG / T3660-1999 (60℃ / 20rpm).

[0113] <Preparation Example 5>

[0114] Another reactive polyurethane was prepared with the following formulation (total 600 kg):

[0115] Eastman Kristalex F85: 45 copies;

[0116] Evonik Polyvest HT: 41 units;

[0117] 3-Methyl-1,5-pentanediol: 1 part;

[0118] Covestro Desmodur 44C: 13 servings;

[0119] Except for replacing polypropylene glycol ether diol BD2-12000A with Evonik Polyvest HT, the preparation method was the same as in Preparation Example 4. The NCO content was measured to be 2.2%, and the hot melt viscosity (60°C) was 3800 cps.

[0120] <Preparation Example 6>

[0121] This preparation example demonstrates the preparation of polyurethane-doped SBC hot melt adhesive, specifically as follows:

[0122] 480 kg of the non-reactive SBC hot melt adhesive from Preparation Example 2 and 120 kg of the reactive polyurethane from Preparation Example 4 were added to a 1000 L reactor. After vacuum stirring at 150℃~160℃ for 1 h, the mixture was discharged for later use. The packaging must be moisture-proof. The properties of the adhesive are shown in Table 1.

[0123] <Preparation Example 7>

[0124] This preparation example demonstrates the preparation of polyurethane-doped SBC hot melt adhesive, specifically as follows:

[0125] 480 kg of the non-reactive SBC hot melt adhesive from Preparation Example 2 and 120 kg of the reactive polyurethane from Preparation Example 5 were added to a 1000 L reactor. After vacuum stirring at 150℃~160℃ for 1 h, the mixture was discharged for later use. The packaging must be moisture-proof. The properties of the adhesive are shown in Table 1.

[0126] <Preparation Example 8>

[0127] This preparation example demonstrates the preparation of polyurethane-doped SBC hot melt adhesive, specifically as follows:

[0128] 480 kg of the non-reactive SBC hot melt adhesive from Preparation Example 3 and 120 kg of the reactive polyurethane from Preparation Example 4 were added to a 1000 L reactor. After vacuum stirring at 150℃~160℃ for 1 h, the mixture was discharged for later use. The packaging must be moisture-proof. The performance of the adhesive is shown in Table 1.

[0129] <Preparation Example 9>

[0130] This preparation example demonstrates the preparation of polyurethane-doped SBC hot melt adhesive, specifically as follows:

[0131] 480 kg of the non-reactive SBC hot melt adhesive from Preparation Example 3 and 120 kg of the reactive polyurethane from Preparation Example 5 were added to a 1000 L reactor. After vacuum stirring at 150℃~160℃ for 1 hour, the mixture was discharged for use. The packaging should be moisture-proof.

[0132] The properties of the rubber compound are shown in Table 1.

[0133] <Preparation Example 10>

[0134] This preparation example demonstrates the preparation of polyurethane-doped SBC hot melt adhesive, specifically as follows:

[0135] 420 kg of the non-reactive SBC hot melt adhesive from Preparation Example 3 and 180 kg of the reactive polyurethane from Preparation Example 5 were added to a 1000 L reactor. After vacuum stirring at 150℃~160℃ for 1 hour, the mixture was discharged for use. The packaging should be moisture-proof.

[0136] The properties of the rubber compound are shown in Table 1.

[0137] Table 1. Basic properties of the materials obtained in the preparation examples

[0138]

[0139] The test methods used in Table 1 are as follows:

[0140] Penetration: GB / T269-1991 Determination of cone penetration of lubricating greases and petroleum greases;

[0141] Hot melt viscosity: HG / T 3660-1999 Determination of melt viscosity of hot melt adhesives;

[0142] R&B softening point: GB / T 15332-1994 Determination of softening point of hot melt adhesives using the ring and ball method;

[0143] Density: GB / T533-2008 Determination of density of vulcanized rubber or thermoplastic rubber;

[0144] Film appearance: visual inspection;

[0145] Initial tack: GB / T4852-2002 Test Method for Initial Tack of Pressure-Sensitive Adhesive Tape (Method A); Peel strength: ASTM D903 Standard Test Method for Peel or Stripping Strength of Adhesive Bonds (300 mm / min);

[0146] Adhesion and low-temperature flexibility: JC / T942-2022 Butyl rubber waterproof sealant tape;

[0147] Heat flow resistance: JC / T942-2022 Butyl rubber waterproof sealant tape (80℃×2h).

[0148] The materials prepared in the above manner were applied in the following examples and comparative examples.

[0149] <Examples 1-5 and Comparative Examples 1-3>

[0150] Comparative Example 1 is a fireproof roll material obtained according to the composition and process (method A) of Example 4 of CN115232577A.

[0151] The compositions of Comparative Examples 2, 3, and Examples 1-5 are shown in Table 2. The preparation method is the same as that for fire-resistant and anti-slip composite multilayer rolls, except for the parameters, and is briefly described below:

[0152] The non-reactive SBC hot melt adhesive prepared in Preparation Examples 2 and 3, or the polyurethane-doped SBC hot melt adhesive prepared in Preparation Examples 7, 8, and 9, were used as the second layer. A 0.2 mm thick adhesive layer was extruded from the hot melt adhesive cylinder of a coating machine under nitrogen protection. This layer was then slit-coated onto the refractory fiber cloth (the third layer), and finally laminated with the release film (the first layer) and wound up to obtain semi-finished product A. When coating the non-reactive SBC hot melt adhesive prepared in Preparation Examples 2 and 3, the temperatures of the coating machine's adhesive cylinder, adhesive hose, and coating head were all set to 180°C; when coating the polyurethane-doped SBC hot melt adhesive prepared in Preparation Examples 7, 8, and 9, the temperatures of the coating machine's adhesive cylinder, adhesive hose, and coating head were all set to 160°C.

[0153] The fire-retardant butyl rubber prepared in Preparation Example 1 is then fed into an extruder (extrusion temperature between 80℃ and 90℃). A 1.0 mm butyl rubber layer (fourth layer) is extruded through the extrusion die onto the other side of the semi-finished fire-resistant fiber cloth. The rubber surface is then combined with non-woven fabric (fifth layer). After online trimming to the specified width, the roll is rolled up and slit to obtain the finished product. After curing for 10 days, it can be put into customer use and tested for slippage between the roll and the roof layer and fire resistance.

[0154] Table 2. Composition of Examples and Comparative Examples

[0155]

[0156]

[0157] The roll materials obtained in the above embodiments and comparative examples were subjected to fire resistance tests and slippage tests between the roll materials and the roofing layers. Specifically:

[0158] Fire resistance test: After removing the release layer of the fireproof roll, it is bonded to the plywood board (compliant with GB / T 9846-2015 Class III) and sprayed with a butane torch for 3 minutes. The flame temperature of this test exceeds 900℃. The height ratio before and after expansion is measured. At the same time, after cooling, the carbon layer is peeled off to observe whether the bottom board is charred.

[0159] Slippage test between roofing membrane and roofing layer: After laying the roofing membrane on a roof with a slope of 30 degrees (the substrate is plywood conforming to GB / T 9846-2015 Class III), the roof temperature is controlled at 35-45℃. After workers walk back and forth on it for 2 hours, the slippage between the roofing membrane and the roofing substrate is observed.

[0160] The test results for the comparative examples and the embodiment examples are shown in Table 3.

[0161] Table 3. Performance Comparison of Examples and Comparative Examples

[0162]

[0163]

[0164] As shown in Table 3, Comparative Examples 1-3, which used non-reactive butyl or SBC hot melt adhesives, all exhibited varying degrees of slippage between the roofing membrane and the roofing layer, failing to meet customer construction requirements. However, Application Examples 1-5, which used polyurethane-doped SBC hot melt adhesives, did not show any slippage and all passed fire resistance tests. Because polyurethane-doped SBC hot melt adhesives were used as the L2 layer and the thickness of the L4 fire-retardant butyl adhesive layer was increased, Application Examples 1-5 demonstrated excellent fire resistance and passed fire resistance tests, even when using non-woven fabric instead of fire-retardant fiber cloth.

[0165] The role and effect of the embodiments

[0166] The fireproof and anti-slip composite multilayer roll material provided in the embodiments of the present invention has a second SBC hot melt adhesive layer made of polyurethane-doped SBC hot melt adhesive. The polyurethane-doped SBC hot melt adhesive includes non-reactive SBC hot melt adhesive and reactive polyurethane. Since the NCO end groups on the reactive polyurethane can react with water in the air to generate amine groups and release carbon dioxide, and the generated amine groups further react with the end NCO groups to achieve chain extension, the polyurethane-doped SBC hot melt adhesive can be partially cured by moisture, thereby increasing the cohesive strength and fundamentally improving the holding power. When applied to roll materials, compared with the existing butyl rubber, it can completely avoid slippage caused by frequent stepping by workers during installation on roofs with large slopes.

[0167] SBC hot melt adhesive is a hot melt adhesive based on styrene-butadiene or isoprene block copolymer (SBC is the abbreviation for Styrene Block Copolymer). To improve high-temperature resistance, the rubber content and softening point of the tackifying resin are usually increased, thus increasing viscosity. However, high viscosity reduces the coating performance of the hot melt adhesive. This invention uses a polyurethane-doped, partially moisture-curable SBC hot melt adhesive for roofing waterproof membranes (see...). Figure 1 It replaces the original fire-retardant butyl rubber (L2 layer), has low viscosity and is easy to apply, and its high-temperature resistance is greatly improved after curing, which can completely solve the slippage problem.

[0168] Furthermore, the fifth layer of the fire-resistant and anti-slip composite multilayer roll material uses non-woven fabric instead of the commonly used refractory fibers. Although the fifth layer will burn and be the first to be destroyed when exposed to flames, the increased thickness of the fourth layer allows for the formation of a thicker carbon layer (insulation layer) through physical and chemical processes such as expansion, carbonization, and dehydration caused by combustion. This effectively protects the underlying substrate (usually wood). Replacing refractory fibers with non-woven fabric significantly reduces the cost of the final product and provides a better user experience in terms of feel and appearance.

[0169] The above embodiments are preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention.

Claims

1. A fireproof and slip-resistant composite multilayer roll material, characterized in that, include: The SBC hot melt adhesive layer, the fire-resistant fiber cloth layer, the fire-retardant butyl adhesive layer, and the non-woven fabric layer are bonded together in sequence. The thickness of the SBC hot melt adhesive layer is 0.1mm to 0.3mm. The thickness of the fire-resistant fiber cloth layer is 0.2mm~1.0mm, the thickness of the fire-retardant butyl rubber layer is 0.4mm~1.5mm, and the thickness of the non-woven fabric layer is 0.1mm~0.3mm; The SBC hot melt adhesive layer is made of polyurethane-doped SBC hot melt adhesive, and contains the following components in parts by weight: Non-reactive SBC hot melt adhesive: 70-80 parts; Reactive polyurethane: 20-30 parts; The above-mentioned non-reactive SBC hot melt adhesive contains the following components in parts by weight: Naphthenic oil: 10-20 parts; Hydrogenated petroleum resin: 40-50 parts; SIS: 30-40 copies; SBS: 20-5 copies; The above-described reactive polyurethane comprises the following components in parts by mass: Pure monomer resin: 40-50 parts; Medium and high molecular weight polyols: 40-50 parts; Low molecular weight polyols: 1-2 parts; Isocyanate: 5-15 parts; The number average molecular weight of the aforementioned high molecular weight polyols is 2700 Dalton to 15000 Dalton; The low molecular weight polyol has a molecular formula with 4 to 6 carbon atoms and a functionality of 2.

2. The fireproof and anti-slip composite multilayer roll material according to claim 1, characterized in that: in, The refractory fiber cloth layer is made of any one of silicon titanium cloth, ceramic fiber cloth, or glass fiber cloth.

3. The fireproof and anti-slip composite multilayer roll material according to claim 1, characterized in that: in, The fire-retardant butyl rubber layer is made of thermally expandable fire-retardant butyl rubber.

4. The fireproof and anti-slip composite multilayer roll material according to claim 1, characterized in that: in, The nonwoven layer is made of PP nonwoven fabric or PET nonwoven fabric.

5. The fireproof and anti-slip composite multilayer roll material according to claim 4, characterized in that: in, The basis weight of the PP nonwoven fabric is 130gsm to 145gsm.

6. The fireproof and slip-resistant composite multilayer roll material according to claim 1, characterized in that: in, The thickness of the SBC hot melt adhesive layer is 0.2mm~0.3mm. The thickness of the fire-resistant fiber cloth layer is 0.3mm~0.4mm, the thickness of the fire-retardant butyl rubber layer is 1.0mm~1.2mm, and the thickness of the non-woven fabric layer is 0.2mm~0.3mm.

7. The fireproof and anti-slip composite multilayer roll material according to claim 1, characterized in that, Also includes: isolation layer, The isolation layer is bonded to the SBC hot melt adhesive layer and to both sides of the SBC hot melt adhesive layer, respectively.

8. The fireproof and anti-slip composite multilayer roll material according to claim 7, characterized in that: in, The thickness of the isolation layer is 0.05mm to 0.2mm.

9. The fireproof and anti-slip composite multilayer roll material according to claim 7, characterized in that: in, The isolation layer is an isolation film or isolation paper.

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