Ultraviolet-cured polyurethane bonding material and preparation method thereof

Abstract

The invention discloses an ultraviolet-cured polyurethane bonding material and a preparation method thereof. The ultraviolet-cured polyurethane bonding material comprises the following main components: isocyanate, polyol, trihydroxy polyether, polyester, a resin material, a filler, a catalyst, a modifier, a monomer and a solvent. The phenyl ketone, the aromatic ketone, the benzylidene and the photosensitive resin are added into the ultraviolet curing polyurethane bonding material, so that the ultraviolet curing polyurethane bonding material has relatively high sensitivity and activity, can be subjected to a polymerization reaction quickly under light irradiation, can reduce energy consumption, is good in stability, is convenient to store for a long time, and can be applied to the field of ultraviolet curing. According to the present invention, the initiator has characteristics of no toxicity, no odor and no harm to the human body, the absorption spectrum is matched with the emission band of the radiation light source, the molar extinction coefficient is high, and the phenyl ketone, the aromatic ketone and the benzylidene absorb the light energy, transition to the excitation singlet state and intersystem jump to the excitation triplet state so as to provide the high intersystem jump efficiency of the initiator;

Description

Technical Field

[0001] The present invention relates to the technical field of polyurethane adhesive materials, and specifically to an ultraviolet-curable polyurethane adhesive material and a preparation method thereof. Background Art

[0002] Polyurethane adhesives refer to adhesives containing urethane groups or isocyanate groups in the molecular chain. Polyurethane adhesives are divided into two categories: polyisocyanates and polyurethanes. The polyisocyanate molecular chain contains isocyanide groups and urethane groups. Therefore, polyurethane adhesives exhibit high activity and polarity, and have chemical adhesion to substrates containing active hydrogen, such as porous materials like foam, plastic, wood, leather, fabric, paper, ceramics, etc., and materials with smooth surfaces like metal, glass, rubber, plastic, etc.

[0003] According to the patent number disclosed on the Chinese Patent Network: 200780021180.X, and the patent name: Composite material based on polyurethane with improved adhesion, a composite material containing at least one polyurethane and at least one other solid, wherein the polyurethane contains a hyperbranched polymer and the thickness of the polyurethane material is 0.1 mm or greater. The present invention relates to a method for producing such a composite material and the use of a hyperbranched polymer as a polyurethane component for improving the adhesion between polyurethane and at least one other solid.

[0004] However, the structure of the existing polyurethane adhesives is relatively single, and it can only perform chemical adhesion through the properties of the materials. Users cannot control the adhesion time of the polyurethane adhesives, resulting in an impact on the adhesion efficiency of the polyurethane adhesives. Summary of the Invention

[0005] To solve the problems raised in the above background art, the purpose of the present invention is to provide an ultraviolet-curable polyurethane adhesive material and a preparation method thereof, which have the advantage of being ultraviolet-curable, and solve the problems that the structure of the existing polyurethane adhesives is relatively single, can only perform chemical adhesion through the properties of the materials, users cannot control the adhesion time of the polyurethane adhesives, and the adhesion efficiency of the polyurethane adhesives is affected.

[0006] To achieve the above purpose, the present invention provides the following technical solution: An ultraviolet-curable polyurethane adhesive material and a preparation method thereof. The main components of the ultraviolet-curable polyurethane adhesive material are: isocyanate, polyol, trihydroxy polyether, polyester, resin material, filler, catalyst, modifier, monomer, solvent, photoinitiator.

[0007] Preferably, the filler consists of active calcium carbonate and talcum powder, the resin material consists of epoxy resin and photosensitive resin, the catalyst consists of organic lead catalyst and organic tin catalyst, the modifier consists of leveling agent, polyether-modified silicone oil and waterborne and oilborne epoxy coatings, the monomer consists of acrylate and methacrylate, the solvent is acetone, and the photoinitiator consists of benzophenone, aromatic ketone and benzylidene.

[0008] Preferably, based on every 100 g of the ultraviolet-curable polyurethane adhesive material, the contents of the respective components are as follows: isocyanate 10 - 20 g, polyol 10 - 13 g, trihydroxy polyether 2 - 5 g, polyester 3 - 5 g, epoxy resin 10 - 15 g, photosensitive resin 15 - 17 g, active calcium carbonate 1 - 3 g, talcum powder 1 - 2 g, organic lead catalyst 1 - 3 g, organic tin catalyst 1 - 5 g, leveling agent 1 - 2 g, polyether-modified silicone oil 1 - 3 g, waterborne and oilborne epoxy coatings 1 - 3 g, acrylate 1 - 4 g, methacrylate 2 - 4 g, benzophenone 1 - 5 g, aromatic ketone 1 - 3 g, benzylidene 3 - 5 g, and acetone is added to make up to 100 g.

[0009] An ultraviolet-curable polyurethane adhesive material and its preparation method, comprising step a) dehydration; step b) heating; step c) stirring; step d) reaction; step e) mixing; step f) sealing:

[0010] Step a) Dehydration: The isocyanate and polyol are respectively subjected to dehydration treatment.

[0011] Step b) Heating: The dehydrated isocyanate and polyol are added to a flask, and they are heated by means of a water bath to raise the temperature. During the temperature-raising process, an organic lead catalyst and an organic tin catalyst are added to obtain a polyurethane material.

[0012] Step c) Stirring: The polyurethane material during the heating process is continuously stirred and mixed, and trihydroxy polyether and polyester are respectively added in sequence during the mixing process to obtain a basic polyurethane adhesive material.

[0013] Step d) Reaction: The basic polyurethane adhesive material is added to a reaction kettle, and while stirring, active calcium carbonate, talcum powder, leveling agent, polyether-modified silicone oil, waterborne and oilborne epoxy coatings, acrylate, methacrylate, benzophenone, aromatic ketone and benzylidene are added.

[0014] Step e) Mixing: The pre-melted epoxy resin and photosensitive resin are added for continuous mixing. During the stirring process, acetone liquid is added at intervals to reduce the viscosity of the resin material. After the stirring is completed, the supernatant is taken to obtain an ultraviolet-curable polyurethane adhesive material.

[0015] Step f) Sealing: The ultraviolet-curable polyurethane adhesive material is filled into cans and sealed for storage.

[0016] Preferably in the present invention, in step a) dehydration: during the dehydration process, vacuum treatment is required for the isocyanate and polyol, and dehydration is carried out by heating to 100 °C for 2 hours.

[0017] Preferably in the present invention, in step b) heating: after the isocyanate and polyol are stirred and heated to 40-60 °C, an organic lead catalyst and an organic tin catalyst are slowly added, and the temperature is raised to 85-90 °C for reaction for 2 hours.

[0018] Preferably in the present invention, in step d) reaction: during the reaction process, active calcium carbonate, talcum powder, leveling agent, polyether-modified silicone oil, water-based and oil-based epoxy coatings, acrylate, methacrylate, benzophenone, aromatic ketone and benzal are intermittently added, and the addition interval of each material is greater than 2 minutes.

[0019] Preferably in the present invention, in step e) sealing: the ultraviolet-curable polyurethane adhesive material needs to be stored in a light-shielding container, and the environmental temperature needs to be reduced during the storage process.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] 1. By adding benzophenone, aromatic ketone, benzal and photosensitive resin inside the ultraviolet-curable polyurethane adhesive material, the present invention can make the ultraviolet-curable polyurethane adhesive material have high sensitivity and activity, can rapidly undergo a polymerization reaction under light irradiation, has a high initiation efficiency, can reduce energy consumption, has good stability, is convenient for long-term storage, is non-toxic and odorless, is harmless to the human body, has an absorption spectrum matching the emission band of the radiation light source, has a high molar extinction coefficient, and moreover, since benzophenone, aromatic ketone and benzal jump to the excited singlet state after absorbing light energy and undergo intersystem crossing to the excited triplet state, the intersystem crossing efficiency of the initiator is high.

[0022] 2. By setting benzophenone, the present invention can make the polyurethane adhesive have very high reaction activity, can rapidly react with various functional groups, and thus is widely used in organic synthesis. No toxic substances are generated during the preparation process, so it has environmental protection advantages, is not prone to decomposition or isomerization, and thus can be used to prepare stable and durable products, has diversity, can react with various functional groups, and thus can prepare a variety of products with different properties.

[0023] 3. By setting methacrylate, the present invention can reduce the viscosity of the ultraviolet-curable polyurethane adhesive material, making it easy to flow and operate. As a result, it can remain liquid at a relatively low temperature, has good low-temperature fluidity, strong adhesion to a variety of raw materials, and at the same time has high tensile shear strength, impact resistance and tensile strength. This enables it to maintain good adhesion performance in various environments, adapt to the filling ability of larger gaps, make the adhesion more firm, have excellent moisture resistance, low dielectric and weathering resistance, and a shorter curing time, thus improving work efficiency.

[0024] 4. By setting photosensitive resin, the present invention enables it to have high precision and high resolution: Photosensitive resin can achieve high-precision and high-resolution processing during the manufacturing process because it hardly shrinks during the solidification process, thereby reducing manufacturing errors and improving the quality and reliability of the product. The curing speed of photosensitive resin is extremely fast, and the manufacturing process can be completed in a short time, thus improving production efficiency. Since photosensitive resin does not produce layer lines during the manufacturing process, the surface of the manufactured product is smooth and delicate, greatly improving the quality of the product. The high degree of curing of photosensitive resin makes the manufactured product have high stability and reliability and can work stably for a long time in various environments.

[0025] 5. By setting fillers, the fillers can improve the mechanical properties of the adhesive such as strength, hardness, wear resistance, aging resistance, water resistance, etc. The addition of fillers can change the function of the adhesive. The addition of fillers can regulate the exothermic reaction during the curing or hardening process of the adhesive, prevent local overheating and regulate the shrinkage rate, thereby reducing the stress of the bonded joint. Fillers can change the rheology, thixotropy, etc. of the adhesive, making it easier to operate and construct. At the same time, fillers can also reduce the cost of the adhesive and improve production efficiency.

[0026] 6. By setting a leveling agent, the leveling agent can effectively reduce the surface tension of the coating liquid, improve its leveling property and uniformity, making the coating film more flat and smooth. The leveling agent can improve the permeability of the coating liquid, reduce the possibility of spots and scars generated during brushing, increase the coverage, and make the film formation uniform and natural. The leveling agent can promote the formation of a flat, smooth and uniform coating film during the drying and film-forming process of the coating, which helps to improve the drying speed of the coating. The leveling agent can form a uniform coating film on the surface of the substrate, increase the contact area between the coating and the substrate, thereby improving the adhesion of the coating, reducing the orange peel and particles of the coating, and thus improving the gloss of the coating.

[0027] 7. By setting polyether-modified silicone oil, the present invention can improve the high and low temperature resistance and weather resistance of the ultraviolet-cured polyurethane adhesive material, enabling it to maintain its stability in high and low temperature environments. At the same time, this material has hydrophobic properties, which can prevent moisture and other impurities from having an adverse impact on the product. It is non-irritating to the human body and the environment, has physiological inertness, is safer to use, has good dispersion properties, and can be easily mixed with other substances. Detailed Embodiment

[0028] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0029] An ultraviolet-cured polyurethane adhesive material and a preparation method thereof provided by the present invention, the main components of the ultraviolet-cured polyurethane adhesive material are: isocyanate, polyol, trihydroxy polyether, polyester, resin material, filler, catalyst, modifier, monomer, solvent, photoinitiator.

[0030] The present invention is further configured as follows: the filler consists of active calcium carbonate and talcum powder, the resin material consists of epoxy resin and photosensitive resin, the catalyst consists of organic lead catalyst and organic tin catalyst, the modifier consists of a leveling agent, polyether-modified silicone oil and water-based and oil-based epoxy coatings, the monomer consists of acrylate and methacrylate, the solvent is made of acetone, and the photoinitiator consists of benzophenone, aromatic ketone and benzylidene.

[0031] By setting benzophenone, the polyurethane adhesive can have high reaction activity, can quickly react with various functional groups, and thus is widely used in organic synthesis. No toxic substances are generated during the preparation process, so it has environmental protection advantages. It is not easy to decompose or isomerize, so it can be used to prepare stable and durable products. It has diversity and can react with various functional groups, so that various products with different properties can be prepared.

[0032] By setting polyether-modified silicone oil, the high and low temperature resistance and weather resistance of the ultraviolet-cured polyurethane adhesive material can be improved, enabling it to maintain its stability in high and low temperature environments. At the same time, this material has hydrophobic properties, which can prevent moisture and other impurities from having an adverse impact on the product. It is non-irritating to the human body and the environment, has physiological inertness, is safer to use, has good dispersion properties, and can be easily mixed with other substances.

[0033] The present invention is further configured that, based on every 100 g of the ultraviolet-curable polyurethane adhesive material, the contents of each component are as follows: isocyanate 10 - 20 g, polyol 10 - 13 g, trihydroxy polyether 2 - 5 g, polyester 3 - 5 g, epoxy resin 10 - 15 g, photosensitive resin 15 - 17 g, activated calcium carbonate 1 - 3 g, talcum powder 1 - 2 g, organic lead catalyst 1 - 3 g, organic tin catalyst 1 - 5 g, leveling agent 1 - 2 g, polyether-modified silicone oil 1 - 3 g, waterborne and oilborne epoxy coating 1 - 3 g, acrylate 1 - 4 g, methacrylate 2 - 4 g, benzophenone 1 - 5 g, aromatic ketone 1 - 3 g, benzylidene 3 - 5 g, and acetone is added to make up to 100 g.

[0034] The present invention is further configured as: an ultraviolet-curable polyurethane adhesive material and a preparation method thereof in a claim, including step a) dehydration; step b) heating; step c) stirring; step d) reaction; step e) mixing; step f) sealing:

[0035] Step a) Dehydration: The isocyanate and polyol are respectively subjected to dehydration treatment.

[0036] Step b) Heating: The dehydrated isocyanate and polyol are added to a flask, and they are heated by a water bath to raise the temperature. During the temperature-raising process, the organic lead catalyst and organic tin catalyst are added to obtain a polyurethane material.

[0037] Step c) Stirring: The polyurethane material during the heating process is continuously stirred and mixed, and trihydroxy polyether and polyester are sequentially added during the mixing process to obtain a basic polyurethane adhesive material.

[0038] Step d) Reaction: The basic polyurethane adhesive material is added to a reaction kettle, and while stirring, activated calcium carbonate, talcum powder, leveling agent, polyether-modified silicone oil, waterborne and oilborne epoxy coating, acrylate, methacrylate, benzophenone, aromatic ketone, and benzylidene are added.

[0039] By setting the leveling agent, the leveling agent can effectively reduce the surface tension of the coating liquid, improve its leveling property and uniformity, make the coating film smoother and flatter. The leveling agent can improve the permeability of the coating liquid, reduce the possibility of spots and scars generated during brushing, increase the coverage, make the film-forming uniform and natural. The leveling agent can promote the formation of a flat, smooth, and uniform coating film during the drying and film-forming process of the coating, help improve the drying speed of the coating. The leveling agent can form a uniform coating film on the surface of the substrate, increase the contact area between the coating and the substrate, thereby improving the adhesion of the coating, reducing the orange peel and particles of the coating, and thus improving the gloss of the coating.

[0040] Step e) Mixing: Add pre-melted epoxy resin and photosensitive resin and continuously mix them. During the stirring process, acetone liquid is intermittently added to reduce the viscosity of the resin material. After stirring, take the supernatant to obtain an ultraviolet-curable polyurethane adhesive material;

[0041] Step f) Sealing: Pack the ultraviolet-curable polyurethane adhesive material into cans and store it sealed.

[0042] The present invention is further configured as follows: Step a) Dehydration: During the dehydration process, vacuum treatment is required for isocyanate and polyol, and dehydration is carried out by heating to 100 °C for 2 hours.

[0043] The present invention is further configured as follows: Step b) Heating: After stirring and heating isocyanate and polyol to 40-60 °C, start to slowly add organic lead catalyst and organic tin catalyst, and raise the temperature to 85-90 °C for reaction for 2 hours.

[0044] The present invention is further configured as follows: Step d) Reaction: During the reaction process, active calcium carbonate, talcum powder, leveling agent, polyether-modified silicone oil, water-based and oil-based epoxy coatings, acrylate, methacrylate, benzophenone, aromatic ketone and benzylidene are intermittently added, and the addition interval of each material is greater than 2 minutes.

[0045] The present invention is further configured as follows: Step e) Sealing: The ultraviolet-curable polyurethane adhesive material needs to be stored in a light-shielding container, and the environmental temperature needs to be reduced during the storage process.

[0046] First Embodiment:

[0047] Based on every 100 g of the ultraviolet-curable polyurethane adhesive material, the content of each component is as follows: isocyanate 20 g, polyol 13 g, trihydroxy polyether 5 g, polyester 5 g, epoxy resin 15 g, photosensitive resin 15 g, active calcium carbonate 1 g, talcum powder 1 g, organic lead catalyst 1 g, organic tin catalyst 5 g, leveling agent 2 g, polyether-modified silicone oil 3 g, water-based and oil-based epoxy coatings 1 g, acrylate 4 g, methacrylate 2 g, benzophenone 5 g, aromatic ketone 1 g, benzylidene 3 g, and acetone is added to make up to 100 g.

[0048] Second Embodiment:

[0049] Based on every 100 g of the ultraviolet-curable polyurethane adhesive material, the content of each component is as follows: isocyanate 20 g, polyol 10 g, trihydroxy polyether 2 g, polyester 3 g, epoxy resin 10 g, photosensitive resin 17 g, active calcium carbonate 3 g, talcum powder 2 g, organic lead catalyst 3 g, organic tin catalyst 1 g, leveling agent 1 g, polyether-modified silicone oil 3 g, water-based and oil-based epoxy coatings 1 g, acrylate 1 g, methacrylate 4 g, benzophenone 5 g, aromatic ketone 3 g, benzylidene 5 g, and acetone is added to make up to 100 g.

[0050] In summary, by adding benzophenone, aromatic ketone, benzylidene and photosensitive resin into the ultraviolet-curable polyurethane adhesive material, the present invention enables the ultraviolet-curable polyurethane adhesive material to have high sensitivity and activity, to rapidly undergo a polymerization reaction under light irradiation, with high initiation efficiency, which can reduce energy consumption, good stability, convenient for long-term storage, non-toxic and odorless, harmless to the human body, the absorption spectrum matches the emission band of the radiation light source, and has a high molar extinction coefficient. Moreover, since benzophenone, aromatic ketone and benzylidene jump to the excited singlet state after absorbing light energy and undergo intersystem crossing to the excited triplet state, the intersystem crossing efficiency of the initiator should be high.

[0051] It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variant thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not expressly listed, or also includes elements inherent to such process, method, article or device.

[0052] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principle and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An ultraviolet-curable polyurethane adhesive material, characterized in that: The main components of the ultraviolet curable polyurethane adhesive material are: isocyanate, polyol, trihydroxy polyether, polyester, resin material, filler, catalyst, modifier, monomer, solvent, photoinitiator.

2. The ultraviolet-curable polyurethane adhesive material according to claim 1, characterized in that: The filler consists of active calcium carbonate and talcum powder, the resin material consists of epoxy resin and photosensitive resin, the catalyst consists of organic lead catalyst and organic tin catalyst, the modifier consists of leveling agent, polyether modified silicone oil and waterborne and oilborne epoxy coatings, the monomer consists of acrylate and methacrylate, the solvent is made of acetone, and the photoinitiator consists of benzophenone, aromatic ketone and benzal.

3. The ultraviolet-curable polyurethane adhesive material according to claim 1, characterized in that: Based on every 100 g of the ultraviolet curable polyurethane adhesive material, the content of each component is: isocyanate 10 - 20 g, polyol 10 - 13 g, trihydroxy polyether 2 - 5 g, polyester 3 - 5 g, epoxy resin 10 - 15 g, photosensitive resin 15 - 17 g, active calcium carbonate 1 - 3 g, talcum powder 1 - 2 g, organic lead catalyst 1 - 3 g, organic tin catalyst 1 - 5 g, leveling agent 1 - 2 g, polyether modified silicone oil 1 - 3 g, waterborne and oilborne epoxy coatings 1 - 3 g, acrylate 1 - 4 g, methacrylate 2 - 4 g, benzophenone 1 - 5 g, aromatic ketone 1 - 3 g, benzal 3 - 5 g, and acetone is added to make up to 100 g.

4. The preparation method of a UV-curable polyurethane adhesive material according to any one of the above claims, characterized in that: It includes step a) dehydration; step b) heating; step c) stirring; step d) reaction; step e) mixing; step f) sealing: Step a) Dehydration: The isocyanate and polyol are respectively subjected to dehydration treatment. Step b) Heating: The dehydrated isocyanate and polyol are added into a flask, and they are heated by a water bath to raise the temperature. During the temperature rising process, the organic lead catalyst and organic tin catalyst are added to obtain the polyurethane material. Step c) Stirring: The polyurethane material during the heating process is continuously stirred and mixed, and trihydroxy polyether and polyester are respectively added successively during the mixing process to obtain the basic polyurethane adhesive material. Step d) Reaction: The basic polyurethane adhesive material is added into a reaction kettle, and while stirring, active calcium carbonate, talcum powder, leveling agent, polyether modified silicone oil, waterborne and oilborne epoxy coatings, acrylate, methacrylate, benzophenone, aromatic ketone and benzal are added. Step e) Mixing: The pre - melted epoxy resin and photosensitive resin are added for continuous mixing. During the stirring process, acetone liquid is added at intervals to reduce the viscosity of the resin material. After stirring, the supernatant is taken to obtain the ultraviolet curable polyurethane adhesive material. Step f) Sealing: The ultraviolet curable polyurethane adhesive material is filled into cans and sealed for storage.

5. The preparation method of a UV-curable polyurethane adhesive material according to claim 4, characterized in that: For the said step a) dehydration: During the dehydration process, the isocyanate and polyol need to be vacuumized and dehydrated by heating to 100 °C for 2 hours.

6. The preparation method of a UV-curable polyurethane adhesive material according to claim 4, characterized in that: For the said step b) heating: After the isocyanate and polyol are stirred and heated to 40 - 60 °C, the organic lead catalyst and organic tin catalyst are slowly added, and the temperature is raised to 85 - 90 °C for reaction for 2 hours.

7. The preparation method of a polyurethane adhesive material cured by ultraviolet light according to claim 4, characterized in that: The reaction in step d): During the reaction process, calcium carbonate, talcum powder, leveling agent, polyether-modified silicone oil, water-based and oil-based epoxy coatings, acrylate, methacrylate, benzophenone, aromatic ketone, and benzal are added intermittently, and the addition interval of each material is greater than 2 minutes.

8. The preparation method of a UV-curable polyurethane adhesive material according to claim 4, characterized in that: The sealing in step e): The UV-curable polyurethane adhesive material needs to be stored in a light-proof container, and the environmental temperature needs to be reduced during the storage process.