A kind of impact-resistant functional composite material and preparation method thereof

Abstract

The present invention relates to the technical field of double-sided adhesives, and specifically discloses an impact-resistant functional composite material and a preparation method thereof. The composite material comprises a foam layer, a pressure-sensitive adhesive layer coated on both sides of the foam layer, and a release film layer coated on the surface of the pressure-sensitive adhesive layer; the pressure-sensitive adhesive layer comprises methyl methacrylate, isobutyl acrylate, ethyl acrylate, functional monomers, foaming microspheres, initiators, wetting agents, defoamers, and solvents; the preparation method comprises preparing a rubber material, coating the adhesive liquid on both sides of the foam layer to obtain a pressure-sensitive adhesive layer; after coating the release film on the surface of the pressure-sensitive adhesive layer, cutting and packaging are obtained; the present invention can achieve excellent double-sided high adhesion, high impact resistance, ultra-thin compressibility, low residual viscosity and other multifunctional properties by carefully designing hard monomers, soft monomers and functional monomers, and adding additives such as foaming microspheres, and the impact energy absorption rate is ≥55%, which meets market demand and demanding application scenarios.

Description

Technical Field

[0001] The invention relates to the technical field of double-sided adhesives, and more specifically, to an impact-resistant functional composite material and a preparation method thereof. Background Art

[0002] Foam double-sided tape is a double-sided tape with foam as the base material and the same or different types of pressure-sensitive adhesives coated on both sides. It has the characteristics of excellent sealing performance, good resilience, good cushioning performance, strong adhesion, etc. It is widely used in home appliances, instrumentation, automotive industry, battery industry and other fields. Acrylic foam double-sided tape is an adhesive product composed of acrylic ester and foam materials. It has the characteristics of double-sided adhesive coating and can adhere evenly on both sides, which improves the bonding strength and durability. As a high-quality adhesive, acrylate has good weather resistance, chemical resistance and transparency, so it is suitable for a variety of different applications.

[0003] With the advancement of science and technology and the changes in market demand, traditional acrylic adhesives have gradually exposed some shortcomings, such as the problem of decreased bonding strength when facing high loads, impact forces or temperature changes. In addition, the existing acrylic foam double-sided adhesive often leaves a certain amount of residual adhesive after removal, which not only affects the appearance quality of the product, but also may affect the subsequent process. Based on the above statement, the present invention proposes an impact-resistant functional composite material and a preparation method thereof. Summary of the invention

[0004] In order to solve the problems that the existing acrylic adhesive has poor impact resistance, is prone to decreased bonding strength when facing high loads, impact forces or temperature changes, and is prone to residue after peeling, the present invention provides an impact-resistant functional composite material and a preparation method thereof.

[0005] In a first aspect, the present invention provides an impact-resistant functional composite material, which adopts the following technical solution: An impact-resistant functional composite material comprises a foam layer, a pressure-sensitive adhesive layer coated on both sides of the foam layer, and a release film layer coated on the surface of the pressure-sensitive adhesive layer; The pressure-sensitive adhesive layer comprises the following raw materials in parts by weight: 30-50 parts of methyl methacrylate, 18-25 parts of isobutyl acrylate, 8-12 parts of ethyl acrylate, 10-20 parts of functional monomers, 8-15 parts of foamed microspheres, 5-8 parts of initiator, 1-3 parts of wetting agent, 1-3 parts of defoaming agent and 25-40 parts of solvent.

[0006] Preferably, the pressure-sensitive adhesive layer comprises the following raw materials in parts by weight: 35-45 parts of methyl methacrylate, 20-24 parts of isobutyl acrylate, 9-11 parts of ethyl acrylate, 12-18 parts of functional monomers, 10-14 parts of foamed microspheres, 6-7 parts of initiator, 1.5-2.5 parts of wetting agent, 1.5-2.5 parts of defoaming agent, and 30-35 parts of solvent.

[0007] Preferably, the pressure-sensitive adhesive layer comprises the following raw materials in parts by weight: 40 parts of methyl methacrylate, 22 parts of isobutyl acrylate, 10 parts of ethyl acrylate, 15 parts of functional monomers, 12 parts of foamed microspheres, 6.5 parts of initiator, 2 parts of wetting agent, 2 parts of defoaming agent, and 32 parts of solvent.

[0008] Preferably, the functional monomers include acrylic acid, isobornyl acrylate and tetrahydrofurfuryl methacrylate in a mass ratio of 3-5:2-3:1.

[0009] Preferably, the foamed microspheres are polyurethane foamed microspheres with an average particle size of 30-50 μm.

[0010] Preferably, the polyurethane foam microspheres are prepared by the following method: (1) Add ethylene glycol, castor oil polyol and organotin catalyst into a reaction kettle, stir well and evenly, keep stirring, slowly add a mixture of toluene diisocyanate and hexamethylene diisocyanate, control the reaction temperature to 70-90°C under a nitrogen atmosphere, react for 3-5 hours, regularly monitor the viscosity and temperature during the reaction, stop heating when the reaction is finished, cool to room temperature, and obtain a polyurethane prepolymer; (2) Under stirring, polydimethylsiloxane, hydroxyethyl cellulose and a foaming agent are added to a polyurethane prepolymer to form a uniform mixture. The mixture is emulsified using a high shear emulsifier to form a uniform emulsion, and then heated to 50-70°C to start foaming. After heating and stirring for 2-4 hours, the heating is stopped. After cooling to room temperature, the mixture is allowed to stand and solidify for 2-3 hours. The solidified microspheres are sieved and dried to obtain polyurethane foamed microspheres.

[0011] Preferably, in step (1), the mass ratio of ethylene glycol, castor oil polyol, toluene diisocyanate, hexamethylene diisocyanate and organotin catalyst is 30-40:10-20:10-20:5-12:0.1-0.5.

[0012] Preferably, the organotin catalyst is dibutyltin diacetate.

[0013] Preferably, in step (2), the mass ratio of the polyurethane prepolymer, polydimethylsiloxane, hydroxyethyl cellulose and foaming agent is 10:1-3:0.5-1:0.1-0.5.

[0014] Preferably, the foaming agent is azodicarbonamide.

[0015] Preferably, the foam layer is one of PU foam, EVA foam, PP foam or PE foam; and the release film layer is PET release film or PE release film.

[0016] Preferably, the initiator is azobisisobutyronitrile; the wetting agent is polyethylene glycol 400 and / or polydimethylsiloxane; the defoamer is defoamer BYK028; and the solvent is ethyl propionate and / or ethyl acetate.

[0017] In a second aspect, the present invention provides a method for preparing an impact-resistant functional composite material, which adopts the following technical solution: A method for preparing an impact-resistant functional composite material comprises the following steps: S1. Add methyl methacrylate, isobutyl acrylate, ethyl acrylate and functional monomers to the solvent in sequence, stir and mix evenly, add foaming microspheres, continue to stir and disperse, then add initiator, wetting agent and defoamer in sequence, and continue to stir until a uniform rubber material is formed; S2, using a coating machine to evenly apply the prepared adhesive solution to both sides of the foam layer, and after pre-drying, obtain a pressure-sensitive adhesive layer; S3. After laminating the release film on the surface of the pressure-sensitive adhesive layer, cutting and packaging are performed to obtain the required impact-resistant functional composite material.

[0018] In summary, the present invention has the following beneficial effects: 1. The impact-resistant functional composite material of the present invention is obtained by coating acrylic pressure-sensitive adhesive layers on both sides of a foam layer and then laminating a release film; wherein the pressure-sensitive adhesive layer is prepared by using methyl methacrylate as a hard monomer, isobutyl acrylate and ethyl acrylate as soft monomers, and acrylic acid, isobornyl acrylate and tetrahydrofurfuryl methacrylate as functional monomers; the introduction of methyl methacrylate can improve the UV resistance, chemical resistance and weather resistance of the adhesive, so that the final adhesive can provide better mechanical strength and temperature resistance after curing, and increase its service life; isobutyl acrylate and ethyl acrylate can improve the flexibility of the adhesive, reduce its brittleness, enhance the impact resistance, and help maintain the adhesion of the adhesive; the selection of compound functional monomers can improve the adhesion of the adhesive, improve the adaptability of the bonding material, enhance the UV resistance, and also adjust the bonding performance, fluidity and elasticity of the adhesive. The present invention can achieve excellent double-sided high adhesion, high impact resistance, ultra-thin compressibility, low residual viscosity and other multifunctional properties through careful design of hard monomers, soft monomers and functional monomers, and the addition of additives such as foamed microspheres. The impact energy absorption rate is ≥55%, which meets market demand and harsh application scenarios.

[0019] 2. The present invention adopts a combination of a foam layer and polyurethane foam microspheres, so that the prepared impact-resistant functional composite material can effectively absorb and disperse energy when impacted, reducing the risk of damage; the polyurethane foam microspheres can effectively disperse the impact energy applied from the outside by introducing elasticity and flexibility, thereby improving the impact resistance of the adhesive. The foaming structure of the microspheres can buffer the impact force, reduce the brittleness and rupture risk of the material, and make the final adhesive less likely to be damaged when impacted, thereby extending the service life. The introduction of polyurethane foam microspheres can also adjust the fluidity and adhesion properties of acrylic adhesives. By optimizing the ratio and dispersion state of the microspheres, the residual viscosity of the adhesive can be reduced without sacrificing the bonding performance, especially in high temperature or humid environments, to prevent the adhesive from adhering to the substrate when peeling, which is convenient for subsequent cleaning and use; the surface characteristics and microstructure of polyurethane foam microspheres can provide more contact area for the adhesive, thereby enhancing the bonding force. The introduction of microspheres can also improve the flexibility and adaptability of the adhesive, making it more adherent to different substrates; in addition to the above advantages, the cavity in the foam microspheres can also effectively prevent the spread of heat, so that the adhesive has good thermal insulation properties. By adjusting the distribution and volume of the foam microspheres, the rheological properties of the adhesive can also be optimized to improve its coating and adhesion effects. DETAILED DESCRIPTION

[0020] The present invention is further described in detail below with reference to the embodiments.

[0021] Unless otherwise specified, the materials, reagents, etc. used in the present invention can be obtained from commercial sources.

[0022] The foam layer is PU foam with a thickness of 2 mm and a density of 0.08 g / cm 3 , purchased from Changzhou Daye Tengfei Sponge Factory; The release film layer is a 0.06mm double-sided release foam tape made of PE, purchased from Suzhou Hongke New Material Technology Co., Ltd. The hydroxyl value of polyethylene glycol 400 was 275 mgKOH / g and was purchased from Langhua (Jiangsu) New Materials Co., Ltd.; Castor oil polyol was purchased from Guangdong Yunxing Biotechnology Co., Ltd.; Polydimethylsiloxane was purchased from Shanghai Hongzhuang Chemical Technology Co., Ltd.; Hydroxyethyl cellulose was purchased from Jiangsu Rayen Environmental Protection Technology Co., Ltd.; Polyacrylate foamed microspheres, brand POLYCHEM, model 180DU25, were purchased from Shanghai Waidian International Trade Co., Ltd.

[0023] Embodiments 1-3 provide an impact-resistant functional composite material and a preparation method thereof.

[0024] Embodiment 1: An impact-resistant functional composite material comprises a foam layer, a pressure-sensitive adhesive layer coated on both sides of the foam layer, and a release film layer coated on the surface of the pressure-sensitive adhesive layer; The pressure-sensitive adhesive layer includes the following raw materials in parts by weight: 30 parts of methyl methacrylate, 18 parts of isobutyl acrylate, 8 parts of ethyl acrylate, 10 parts of functional monomers, 8 parts of foamed microspheres, 5 parts of initiator, 1 part of wetting agent, 1 part of defoaming agent, and 25 parts of solvent.

[0025] The functional monomers include acrylic acid, isobornyl acrylate and tetrahydrofurfuryl methacrylate in a mass ratio of 3:2:1; the initiator is azobisisobutyronitrile; the wetting agent is polyethylene glycol 400; the defoamer is defoamer BYK028; and the solvent is ethyl acetate.

[0026] The foamed microspheres are polyurethane foamed microspheres and are prepared by the following method: (1) Add ethylene glycol, castor oil polyol and dibutyltin diacetate into a reactor, control the stirring speed to 300 r / min, stir thoroughly for 40 minutes until uniform, keep stirring, slowly add a mixture of toluene-2,4-diisocyanate and hexamethylene diisocyanate, and control the addition to be completed within 30 minutes. Under a nitrogen atmosphere, control the reaction temperature to 70°C and react for 5 hours. During the reaction, regularly monitor the viscosity and temperature. When the reaction is completed, stop heating and cool to room temperature to obtain a polyurethane prepolymer; the mass ratio of ethylene glycol, castor oil polyol, toluene-2,4-diisocyanate, hexamethylene diisocyanate and dibutyltin diacetate is 30:10:10:5:0.1; (2) Under stirring, polydimethylsiloxane, hydroxyethyl cellulose and azodicarbonamide are added to the polyurethane prepolymer to form a uniform mixture. The mixture is emulsified using a high shear emulsifier for 8 minutes, and the shear speed is controlled to be 3000 r / min. After forming a uniform emulsion, the mixture is heated to 50°C to start foaming. After heating and stirring for 4 hours, the heating is stopped. After cooling to room temperature, the mixture is allowed to stand and solidify for 2 hours. The solidified microspheres are sieved and dried at 80°C to constant weight to obtain polyurethane foamed microspheres with an average particle size of 30 μm. The mass ratio of the polyurethane prepolymer, polydimethylsiloxane, hydroxyethyl cellulose and azodicarbonamide is 10:1:0.5:0.1.

[0027] A method for preparing an impact-resistant functional composite material comprises the following steps: S1. Add methyl methacrylate, isobutyl acrylate, ethyl acrylate and functional monomers to the solvent in sequence, control the stirring speed to 300r / min, stir and mix for 30min until uniform, add foaming microspheres, continue stirring and dispersing for 20min, then add initiator, wetting agent and defoamer in sequence, and continue stirring for 40min until a uniform rubber material is formed; S2. Use a coating machine to evenly apply the prepared glue on both sides of the foam layer, and control the coating amount to 18g / m 2 , after pre-drying at 50°C for 30 minutes, a pressure-sensitive adhesive layer is obtained; S3. After laminating the release film on the surface of the pressure-sensitive adhesive layer, cutting and packaging are performed to obtain the required impact-resistant functional composite material.

[0028] Embodiment 2: An impact-resistant functional composite material comprises a foam layer, a pressure-sensitive adhesive layer coated on both sides of the foam layer, and a release film layer coated on the surface of the pressure-sensitive adhesive layer; The pressure-sensitive adhesive layer includes the following raw materials in parts by weight: 40 parts of methyl methacrylate, 22 parts of isobutyl acrylate, 10 parts of ethyl acrylate, 15 parts of functional monomers, 12 parts of foamed microspheres, 6.5 parts of initiator, 2 parts of wetting agent, 2 parts of defoaming agent, and 32 parts of solvent.

[0029] The functional monomers include acrylic acid, isobornyl acrylate and tetrahydrofurfuryl methacrylate in a mass ratio of 4:2.5:1; the initiator is azobisisobutyronitrile; the wetting agent is polyethylene glycol 400; the defoamer is defoamer BYK028; and the solvent is ethyl acetate.

[0030] The foamed microspheres are polyurethane foamed microspheres and are prepared by the following method: (1) Add ethylene glycol, castor oil polyol and dibutyltin diacetate into a reactor, control the stirring speed to 400 r / min, stir thoroughly for 30 minutes until uniform, keep stirring, slowly add a mixture of toluene-2,4-diisocyanate and hexamethylene diisocyanate, and control the addition to be completed within 30 minutes. Under a nitrogen atmosphere, control the reaction temperature to 80°C and react for 4 hours. During the reaction, regularly monitor the viscosity and temperature. When the reaction is completed, stop heating and cool to room temperature to obtain a polyurethane prepolymer; the mass ratio of ethylene glycol, castor oil polyol, toluene-2,4-diisocyanate, hexamethylene diisocyanate and dibutyltin diacetate is 35:15:15:8:0.3; (2) Under stirring, polydimethylsiloxane, hydroxyethyl cellulose and azodicarbonamide are added to the polyurethane prepolymer to form a uniform mixture. The mixture is emulsified using a high shear emulsifier for 12 minutes, and the shear speed is controlled to be 2500 r / min. After a uniform emulsion is formed, the mixture is heated to 60°C to start foaming. After heating and stirring for 3 hours, the heating is stopped. After cooling to room temperature, the mixture is allowed to stand and solidify for 2.5 hours. The solidified microspheres are sieved and dried at 80°C to constant weight to obtain polyurethane foamed microspheres with an average particle size of 40 μm. The mass ratio of the polyurethane prepolymer, polydimethylsiloxane, hydroxyethyl cellulose and azodicarbonamide is 10:2:0.8:0.3.

[0031] A method for preparing an impact-resistant functional composite material comprises the following steps: S1. Add methyl methacrylate, isobutyl acrylate, ethyl acrylate and functional monomers to the solvent in sequence, control the stirring speed to 400r / min, stir and mix for 25min until uniform, add foaming microspheres, continue stirring and dispersing for 15min, then add initiator, wetting agent and defoamer in sequence, and continue stirring for 30min until a uniform rubber material is formed; S2. Use a coating machine to evenly apply the prepared glue on both sides of the foam layer, and control the coating amount to 24g / m 2 After pre-drying at 65°C for 20 minutes, a pressure-sensitive adhesive layer was obtained; S3. After laminating the release film on the surface of the pressure-sensitive adhesive layer, cutting and packaging are performed to obtain the required impact-resistant functional composite material.

[0032] Embodiment 3: An impact-resistant functional composite material comprises a foam layer, a pressure-sensitive adhesive layer coated on both sides of the foam layer, and a release film layer coated on the surface of the pressure-sensitive adhesive layer; The pressure-sensitive adhesive layer includes the following raw materials in parts by weight: 50 parts of methyl methacrylate, 25 parts of isobutyl acrylate, 12 parts of ethyl acrylate, 20 parts of functional monomers, 15 parts of foamed microspheres, 8 parts of initiator, 3 parts of wetting agent, 3 parts of defoaming agent, and 40 parts of solvent.

[0033] The functional monomers include acrylic acid, isobornyl acrylate and tetrahydrofurfuryl methacrylate in a mass ratio of 5:3:1; the initiator is azobisisobutyronitrile; the wetting agent is polyethylene glycol 400; the defoamer is defoamer BYK028; and the solvent is ethyl acetate.

[0034] The foamed microspheres are polyurethane foamed microspheres and are prepared by the following method: (1) Add ethylene glycol, castor oil polyol and dibutyltin diacetate into a reactor, control the stirring speed to 500 r / min, stir thoroughly for 20 minutes until uniform, keep stirring, slowly add a mixture of toluene-2,4-diisocyanate and hexamethylene diisocyanate, and control the addition to be completed within 30 minutes. Under a nitrogen atmosphere, control the reaction temperature to 90°C and react for 3 hours. During the reaction, regularly monitor the viscosity and temperature. When the reaction is completed, stop heating and cool to room temperature to obtain a polyurethane prepolymer; the mass ratio of ethylene glycol, castor oil polyol, toluene-2,4-diisocyanate, hexamethylene diisocyanate and dibutyltin diacetate is 40:20:20:12:0.5; (2) Under stirring, polydimethylsiloxane, hydroxyethyl cellulose and azodicarbonamide are added to the polyurethane prepolymer to form a uniform mixture. The mixture is emulsified using a high shear emulsifier for 15 minutes, and the shear speed is controlled to be 2000 r / min. After a uniform emulsion is formed, the mixture is heated to 70°C to start foaming. After heating and stirring for 2 hours, the heating is stopped. After cooling to room temperature, the mixture is allowed to stand and solidify for 3 hours. The solidified microspheres are sieved and dried at 80°C to constant weight to obtain polyurethane foamed microspheres with an average particle size of 50 μm. The mass ratio of the polyurethane prepolymer, polydimethylsiloxane, hydroxyethyl cellulose and azodicarbonamide is 10:3:1:0.5.

[0035] A method for preparing an impact-resistant functional composite material comprises the following steps: S1. Add methyl methacrylate, isobutyl acrylate, ethyl acrylate and functional monomers to the solvent in sequence, control the stirring speed to 500r / min, stir and mix for 20min until uniform, add foaming microspheres, continue stirring and dispersing for 10min, then add initiator, wetting agent and defoamer in sequence, and continue stirring for 20min until a uniform rubber material is formed; S2. Use a coating machine to evenly apply the prepared glue on both sides of the foam layer, and control the coating amount to 30g / m 2 After pre-drying at 80°C for 10 minutes, a pressure-sensitive adhesive layer was obtained; S3. After laminating the release film on the surface of the pressure-sensitive adhesive layer, cutting and packaging are performed to obtain the required impact-resistant functional composite material.

[0036] In order to verify the performance of the impact-resistant functional composite materials obtained in Examples 1-3 of the present invention, the present invention sets up Comparative Examples 1-5.

[0037] Comparative Example 1: Comparative Example 1 is different from Example 1 only in that the functional monomers include acrylic acid and isobornyl acrylate in a mass ratio of 3:2, specifically as follows: An impact-resistant functional composite material comprises a foam layer, a pressure-sensitive adhesive layer coated on both sides of the foam layer, and a release film layer coated on the surface of the pressure-sensitive adhesive layer; The pressure-sensitive adhesive layer includes the following raw materials in parts by weight: 30 parts of methyl methacrylate, 18 parts of isobutyl acrylate, 8 parts of ethyl acrylate, 10 parts of functional monomers, 8 parts of foamed microspheres, 5 parts of initiator, 1 part of wetting agent, 1 part of defoaming agent, and 25 parts of solvent.

[0038] The functional monomers include acrylic acid and isobornyl acrylate in a mass ratio of 3:2; the initiator is azobisisobutyronitrile; the wetting agent is polyethylene glycol 400; the defoaming agent is defoaming agent BYK028; and the solvent is ethyl acetate.

[0039] The foamed microspheres are polyurethane foamed microspheres and are prepared by the following method: (1) Add ethylene glycol, castor oil polyol and dibutyltin diacetate into a reactor, control the stirring speed to 300 r / min, stir thoroughly for 40 minutes until uniform, keep stirring, slowly add a mixture of toluene-2,4-diisocyanate and hexamethylene diisocyanate, and control the addition to be completed within 30 minutes. Under a nitrogen atmosphere, control the reaction temperature to 70°C and react for 5 hours. During the reaction, regularly monitor the viscosity and temperature. When the reaction is completed, stop heating and cool to room temperature to obtain a polyurethane prepolymer; the mass ratio of ethylene glycol, castor oil polyol, toluene-2,4-diisocyanate, hexamethylene diisocyanate and dibutyltin diacetate is 30:10:10:5:0.1; (2) Under stirring, polydimethylsiloxane, hydroxyethyl cellulose and azodicarbonamide are added to the polyurethane prepolymer to form a uniform mixture. The mixture is emulsified using a high shear emulsifier for 8 minutes, and the shear speed is controlled to be 3000 r / min. After forming a uniform emulsion, the mixture is heated to 50°C to start foaming. After heating and stirring for 4 hours, the heating is stopped. After cooling to room temperature, the mixture is allowed to stand and solidify for 2 hours. The solidified microspheres are sieved and dried at 80°C to constant weight to obtain polyurethane foamed microspheres with an average particle size of 30 μm. The mass ratio of the polyurethane prepolymer, polydimethylsiloxane, hydroxyethyl cellulose and azodicarbonamide is 10:1:0.5:0.1.

[0040] A method for preparing an impact-resistant functional composite material comprises the following steps: S1. Add methyl methacrylate, isobutyl acrylate, ethyl acrylate and functional monomers to the solvent in sequence, control the stirring speed to 300r / min, stir and mix for 30min until uniform, add foaming microspheres, continue stirring and dispersing for 20min, then add initiator, wetting agent and defoamer in sequence, and continue stirring for 40min until a uniform rubber material is formed; S2. Use a coating machine to evenly apply the prepared glue on both sides of the foam layer, and control the coating amount to 18g / m 2 , after pre-drying at 50°C for 30 minutes, a pressure-sensitive adhesive layer is obtained; S3. After laminating the release film on the surface of the pressure-sensitive adhesive layer, cutting and packaging are performed to obtain the required impact-resistant functional composite material.

[0041] Comparative Example 2: Comparative Example 2 is different from Example 1 only in that the functional monomers include acrylic acid and tetrahydrofurfuryl methacrylate in a mass ratio of 3:1, as follows: An impact-resistant functional composite material comprises a foam layer, a pressure-sensitive adhesive layer coated on both sides of the foam layer, and a release film layer coated on the surface of the pressure-sensitive adhesive layer; The pressure-sensitive adhesive layer includes the following raw materials in parts by weight: 30 parts of methyl methacrylate, 18 parts of isobutyl acrylate, 8 parts of ethyl acrylate, 10 parts of functional monomers, 8 parts of foamed microspheres, 5 parts of initiator, 1 part of wetting agent, 1 part of defoaming agent, and 25 parts of solvent.

[0042] The functional monomers include acrylic acid and tetrahydrofurfuryl methacrylate in a mass ratio of 3:1; the initiator is azobisisobutyronitrile; the wetting agent is polyethylene glycol 400; the defoamer is defoamer BYK028; and the solvent is ethyl acetate.

[0043] The foamed microspheres are polyurethane foamed microspheres and are prepared by the following method: (1) Add ethylene glycol, castor oil polyol and dibutyltin diacetate into a reactor, control the stirring speed to 300 r / min, stir thoroughly for 40 minutes until uniform, keep stirring, slowly add a mixture of toluene-2,4-diisocyanate and hexamethylene diisocyanate, and control the addition to be completed within 30 minutes. Under a nitrogen atmosphere, control the reaction temperature to 70°C and react for 5 hours. During the reaction, regularly monitor the viscosity and temperature. When the reaction is completed, stop heating and cool to room temperature to obtain a polyurethane prepolymer; the mass ratio of ethylene glycol, castor oil polyol, toluene-2,4-diisocyanate, hexamethylene diisocyanate and dibutyltin diacetate is 30:10:10:5:0.1; (2) Under stirring, polydimethylsiloxane, hydroxyethyl cellulose and azodicarbonamide are added to the polyurethane prepolymer to form a uniform mixture. The mixture is emulsified using a high shear emulsifier for 8 minutes, and the shear speed is controlled to be 3000 r / min. After forming a uniform emulsion, the mixture is heated to 50°C to start foaming. After heating and stirring for 4 hours, the heating is stopped. After cooling to room temperature, the mixture is allowed to stand and solidify for 2 hours. The solidified microspheres are sieved and dried at 80°C to constant weight to obtain polyurethane foamed microspheres with an average particle size of 30 μm. The mass ratio of the polyurethane prepolymer, polydimethylsiloxane, hydroxyethyl cellulose and azodicarbonamide is 10:1:0.5:0.1.

[0044] A method for preparing an impact-resistant functional composite material comprises the following steps: S1. Add methyl methacrylate, isobutyl acrylate, ethyl acrylate and functional monomers to the solvent in sequence, control the stirring speed to 300r / min, stir and mix for 30min until uniform, add foaming microspheres, continue stirring and dispersing for 20min, then add initiator, wetting agent and defoamer in sequence, and continue stirring for 40min until a uniform rubber material is formed; S2. Use a coating machine to evenly apply the prepared glue on both sides of the foam layer, and control the coating amount to 18g / m 2 , after pre-drying at 50°C for 30 minutes, a pressure-sensitive adhesive layer is obtained; S3. After laminating the release film on the surface of the pressure-sensitive adhesive layer, cutting and packaging are performed to obtain the required impact-resistant functional composite material.

[0045] Comparative Example 3: Comparative Example 3 is different from Example 1 only in that the functional monomers include isobornyl acrylate and tetrahydrofurfuryl methacrylate in a mass ratio of 2:1, specifically as follows: An impact-resistant functional composite material comprises a foam layer, a pressure-sensitive adhesive layer coated on both sides of the foam layer, and a release film layer coated on the surface of the pressure-sensitive adhesive layer; The pressure-sensitive adhesive layer includes the following raw materials in parts by weight: 30 parts of methyl methacrylate, 18 parts of isobutyl acrylate, 8 parts of ethyl acrylate, 10 parts of functional monomers, 8 parts of foamed microspheres, 5 parts of initiator, 1 part of wetting agent, 1 part of defoaming agent, and 25 parts of solvent.

[0046] The functional monomers include isobornyl acrylate and tetrahydrofurfuryl methacrylate in a mass ratio of 2:1; the initiator is azobisisobutyronitrile; the wetting agent is polyethylene glycol 400; the defoamer is defoamer BYK028; and the solvent is ethyl acetate.

[0047] The foamed microspheres are polyurethane foamed microspheres and are prepared by the following method: (1) Add ethylene glycol, castor oil polyol and dibutyltin diacetate into a reactor, control the stirring speed to 300 r / min, stir thoroughly for 40 minutes until uniform, keep stirring, slowly add a mixture of toluene-2,4-diisocyanate and hexamethylene diisocyanate, and control the addition to be completed within 30 minutes. Under a nitrogen atmosphere, control the reaction temperature to 70°C and react for 5 hours. During the reaction, regularly monitor the viscosity and temperature. When the reaction is completed, stop heating and cool to room temperature to obtain a polyurethane prepolymer; the mass ratio of ethylene glycol, castor oil polyol, toluene-2,4-diisocyanate, hexamethylene diisocyanate and dibutyltin diacetate is 30:10:10:5:0.1; (2) Under stirring, polydimethylsiloxane, hydroxyethyl cellulose and azodicarbonamide are added to the polyurethane prepolymer to form a uniform mixture. The mixture is emulsified using a high shear emulsifier for 8 minutes, and the shear speed is controlled to be 3000 r / min. After forming a uniform emulsion, the mixture is heated to 50°C to start foaming. After heating and stirring for 4 hours, the heating is stopped. After cooling to room temperature, the mixture is allowed to stand and solidify for 2 hours. The solidified microspheres are sieved and dried at 80°C to constant weight to obtain polyurethane foamed microspheres with an average particle size of 30 μm. The mass ratio of the polyurethane prepolymer, polydimethylsiloxane, hydroxyethyl cellulose and azodicarbonamide is 10:1:0.5:0.1.

[0048] A method for preparing an impact-resistant functional composite material comprises the following steps: S1. Add methyl methacrylate, isobutyl acrylate, ethyl acrylate and functional monomers to the solvent in sequence, control the stirring speed to 300r / min, stir and mix for 30min until uniform, add foaming microspheres, continue stirring and dispersing for 20min, then add initiator, wetting agent and defoamer in sequence, and continue stirring for 40min until a uniform rubber material is formed; S2. Use a coating machine to evenly apply the prepared glue on both sides of the foam layer, and control the coating amount to 18g / m 2 , after pre-drying at 50°C for 30 minutes, a pressure-sensitive adhesive layer is obtained; S3. After laminating the release film on the surface of the pressure-sensitive adhesive layer, cutting and packaging are performed to obtain the required impact-resistant functional composite material.

[0049] Comparative Example 4: Comparative Example 4 is different from Example 1 only in that the foamed microspheres are replaced with polyurethane particles, as follows: An impact-resistant functional composite material comprises a foam layer, a pressure-sensitive adhesive layer coated on both sides of the foam layer, and a release film layer coated on the surface of the pressure-sensitive adhesive layer; The pressure-sensitive adhesive layer includes the following raw materials in parts by weight: 30 parts of methyl methacrylate, 18 parts of isobutyl acrylate, 8 parts of ethyl acrylate, 10 parts of functional monomers, 8 parts of polyurethane particles, 5 parts of initiator, 1 part of wetting agent, 1 part of defoaming agent, and 25 parts of solvent.

[0050] The functional monomers include acrylic acid, isobornyl acrylate and tetrahydrofurfuryl methacrylate in a mass ratio of 3:2:1; the initiator is azobisisobutyronitrile; the wetting agent is polyethylene glycol 400; the defoamer is defoamer BYK028; and the solvent is ethyl acetate.

[0051] Polyurethane microparticles are prepared by the following method: (1) Add ethylene glycol, castor oil polyol and dibutyltin diacetate into a reactor, control the stirring speed to 300 r / min, stir thoroughly for 40 minutes until uniform, keep stirring, slowly add a mixture of toluene-2,4-diisocyanate and hexamethylene diisocyanate, and control the addition to be completed within 30 minutes. Under a nitrogen atmosphere, control the reaction temperature to 70°C and react for 5 hours. During the reaction, regularly monitor the viscosity and temperature. When the reaction is completed, stop heating and cool to room temperature to obtain a polyurethane prepolymer; the mass ratio of ethylene glycol, castor oil polyol, toluene-2,4-diisocyanate, hexamethylene diisocyanate and dibutyltin diacetate is 30:10:10:5:0.1; (2) Under stirring, polydimethylsiloxane and hydroxyethyl cellulose are added to the polyurethane prepolymer to form a uniform mixture, and the mixture is emulsified using a high shear emulsifier for 8 minutes, with the shear speed controlled at 3000 r / min. After a uniform emulsion is formed, it is spray-dried at a temperature of 80°C to obtain polyurethane microparticles with an average particle size of 30 μm; the mass ratio of the polyurethane prepolymer, polydimethylsiloxane and hydroxyethyl cellulose is 10:1:0.5.

[0052] A method for preparing an impact-resistant functional composite material comprises the following steps: S1. Add methyl methacrylate, isobutyl acrylate, ethyl acrylate and functional monomers to the solvent in sequence, control the stirring speed to 300 r / min, stir and mix for 30 minutes until uniform, add polyurethane particles, continue to stir and disperse for 20 minutes, then add initiator, wetting agent and defoamer in sequence, and continue to stir for 40 minutes until a uniform rubber material is formed; S2. Use a coating machine to evenly apply the prepared glue on both sides of the foam layer, and control the coating amount to 18g / m 2 , after pre-drying at 50°C for 30 minutes, a pressure-sensitive adhesive layer is obtained; S3. After laminating the release film on the surface of the pressure-sensitive adhesive layer, cutting and packaging are performed to obtain the required impact-resistant functional composite material.

[0053] Comparative Example 5: Comparative Example 5 is different from Example 1 only in that the foamed microspheres are replaced with polyacrylate foamed microspheres, as follows: An impact-resistant functional composite material comprises a foam layer, a pressure-sensitive adhesive layer coated on both sides of the foam layer, and a release film layer coated on the surface of the pressure-sensitive adhesive layer; The pressure-sensitive adhesive layer includes the following raw materials in parts by weight: 30 parts of methyl methacrylate, 18 parts of isobutyl acrylate, 8 parts of ethyl acrylate, 10 parts of functional monomers, 8 parts of foamed microspheres, 5 parts of initiator, 1 part of wetting agent, 1 part of defoaming agent, and 25 parts of solvent.

[0054] The functional monomers include acrylic acid, isobornyl acrylate and tetrahydrofurfuryl methacrylate in a mass ratio of 3:2:1; the initiator is azobisisobutyronitrile; the wetting agent is polyethylene glycol 400; the defoamer is defoamer BYK028; and the solvent is ethyl acetate.

[0055] The foamed microspheres are polyacrylate foamed microspheres.

[0056] A method for preparing an impact-resistant functional composite material comprises the following steps: S1. Add methyl methacrylate, isobutyl acrylate, ethyl acrylate and functional monomers to the solvent in sequence, control the stirring speed to 300r / min, stir and mix for 30min until uniform, add foaming microspheres, continue stirring and dispersing for 20min, then add initiator, wetting agent and defoamer in sequence, and continue stirring for 40min until a uniform rubber material is formed; S2. Use a coating machine to evenly apply the prepared glue on both sides of the foam layer, and control the coating amount to 18g / m 2 , after pre-drying at 50°C for 30 minutes, a pressure-sensitive adhesive layer is obtained; S3. After laminating the release film on the surface of the pressure-sensitive adhesive layer, cutting and packaging are performed to obtain the required impact-resistant functional composite material.

[0057] Performance testing: The properties of the impact-resistant functional composite materials in Examples 1-3 of the present invention and Comparative Examples 1-5 were tested respectively, as follows: Refer to the national standard GB / T 2792-2014 "Test method for peel strength of adhesive tape", and test according to the test method of method 1 for 180° peel strength between adhesive tape and stainless steel. The test sample cutting width is 24mm, and the 180° peel strength and residual adhesive rate are tested; Refer to GB / T4852-2002 "Test method for initial adhesion of pressure-sensitive adhesive tapes (rolling ball method)" to test the initial adhesion of impact-resistant functional composite materials; Refer to GB / T4851-2014 "Test method for adhesive tape holding force" to test the holding force of impact-resistant functional composite materials at 80°C; The impact resistance of the impact-resistant functional composite material is tested according to the following method, which is as follows: the release film on one side of the impact-resistant functional composite material is peeled off, the pressure-sensitive adhesive layer faces upward, a steel ball weighing 10g is selected, and it is freely dropped from 100mm above the pressure-sensitive adhesive layer to detect the impact force of the steel ball on the tape, and then the impact force generated by the steel ball falling when the impact-resistant functional composite material is not placed is detected, and the impact resistance of the impact-resistant functional composite material is expressed by the absorption percentage of the impact force of the steel ball by the impact-resistant functional composite material (i.e., impact energy absorption rate), wherein the impact energy absorption rate = (impact force of the steel ball when there is no impact-resistant functional composite material - impact force of the steel ball on the impact-resistant functional composite material) / impact force of the steel ball when there is no impact-resistant functional composite material × 100%; The results are shown in Table 1 below.

[0058] Table 1: ; Combined with the data shown in Table 1 above, it can be seen that the comprehensive performance of the impact-resistant functional composite materials prepared in Examples 1-3 of the present invention is significantly better than that of Comparative Examples 1-5. The present invention can achieve excellent double-sided high adhesion, high impact resistance, ultra-thin compressibility, low residual viscosity and other multifunctional properties by carefully designing hard monomers, soft monomers and functional monomers, and adding additives such as foamed microspheres. The impact energy absorption rate is ≥55%, which meets market demand and harsh application scenarios.

[0059] This specific embodiment is merely an explanation of the present invention and is not a limitation of the present invention. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed. However, as long as they are within the scope of the claims of the present invention, they are protected by the patent law.

Claims

1. An impact-resistant functional composite material, characterized in that: It includes a foam layer, a pressure-sensitive adhesive layer coated on both sides of the foam layer, and a release film layer coated on the surface of the pressure-sensitive adhesive layer; The pressure-sensitive adhesive layer comprises the following raw materials in parts by weight: 30-50 parts of methyl methacrylate, 18-25 parts of isobutyl acrylate, 8-12 parts of ethyl acrylate, 10-20 parts of functional monomers, 8-15 parts of foamed microspheres, 5-8 parts of initiator, 1-3 parts of wetting agent, 1-3 parts of defoaming agent, and 25-40 parts of solvent; The functional monomers include acrylic acid, isobornyl acrylate and tetrahydrofurfuryl methacrylate in a mass ratio of 3-5:2-3:

1.

2. The impact-resistant functional composite material according to claim 1, characterized in that: The pressure-sensitive adhesive layer comprises the following raw materials in parts by weight: 40 parts of methyl methacrylate, 22 parts of isobutyl acrylate, 10 parts of ethyl acrylate, 15 parts of functional monomers, 12 parts of foamed microspheres, 6.5 parts of initiator, 2 parts of wetting agent, 2 parts of defoamer, and 32 parts of solvent.

3. The impact-resistant functional composite material according to claim 1, characterized in that: The foamed microspheres are polyurethane foamed microspheres with an average particle size of 30-50 μm.

4. The impact-resistant functional composite material according to claim 3, characterized in that: The polyurethane foam microspheres are prepared by the following method: (1) Add ethylene glycol, castor oil polyol and organotin catalyst into a reaction kettle, stir well and evenly, keep stirring, slowly add a mixture of toluene diisocyanate and hexamethylene diisocyanate, control the reaction temperature to 70-90°C under a nitrogen atmosphere, react for 3-5 hours, regularly monitor the viscosity and temperature during the reaction, stop heating when the reaction is finished, cool to room temperature, and obtain a polyurethane prepolymer; (2) Under stirring, polydimethylsiloxane, hydroxyethyl cellulose and a foaming agent are added to a polyurethane prepolymer to form a uniform mixture. The mixture is emulsified using a high shear emulsifier to form a uniform emulsion, and then heated to 50-70°C to start foaming. After heating and stirring for 2-4 hours, the heating is stopped. After cooling to room temperature, the mixture is allowed to stand and solidify for 2-3 hours. The solidified microspheres are sieved and dried to obtain polyurethane foamed microspheres.

5. The impact-resistant functional composite material according to claim 4, characterized in that: The mass ratio of ethylene glycol, castor oil polyol, toluene diisocyanate, hexamethylene diisocyanate and organotin catalyst in (1) is 30-40:10-20:10-20:5-12:0.1-0.

5.

6. The impact-resistant functional composite material according to claim 4, characterized in that: The mass ratio of the polyurethane prepolymer, polydimethylsiloxane, hydroxyethyl cellulose and foaming agent in (2) is 10:1-3:0.5-1:0.1-0.

5.

7. The impact-resistant functional composite material according to claim 1, characterized in that: The foam layer is one of PU foam, EVA foam, PP foam or PE foam; the release film layer is PET release film or PE release film.

8. The impact-resistant functional composite material according to claim 1, characterized in that: The initiator is azobisisobutyronitrile; the wetting agent is polyethylene glycol 400 and / or polydimethylsiloxane; the defoamer is defoamer BYK028; and the solvent is ethyl propionate and / or ethyl acetate.

9. A method for preparing the impact-resistant functional composite material according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Add methyl methacrylate, isobutyl acrylate, ethyl acrylate and functional monomers to the solvent in sequence, stir and mix evenly, add foaming microspheres, continue to stir and disperse, then add initiator, wetting agent and defoamer in sequence, and continue to stir until a uniform rubber material is formed; S2, using a coating machine to evenly apply the prepared adhesive solution to both sides of the foam layer, and after pre-drying, obtain a pressure-sensitive adhesive layer; S3. After laminating the release film on the surface of the pressure-sensitive adhesive layer, cutting and packaging are performed to obtain the required impact-resistant functional composite material.