CN114479743A - Reactive polyurethane hot melt adhesive for TWS earphone bonding and preparation method thereof - Google Patents

Reactive polyurethane hot melt adhesive for TWS earphone bonding and preparation method thereof Download PDF

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Publication number
CN114479743A
CN114479743A CN202210216893.8A CN202210216893A CN114479743A CN 114479743 A CN114479743 A CN 114479743A CN 202210216893 A CN202210216893 A CN 202210216893A CN 114479743 A CN114479743 A CN 114479743A
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parts
bonding
hot melt
melt adhesive
polyurethane hot
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韩继新
李日辉
李俊杰
王飞
赵勇刚
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Shagnhai Huitian New Chemical Materials Co ltd
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Shagnhai Huitian New Chemical Materials Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269Lactones
    • C08G18/4277Caprolactone and/or substituted caprolactone
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44Polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4825Polyethers containing two hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4833Polyethers containing oxyethylene units
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/38Boron-containing compounds
    • C08K2003/382Boron-containing compounds and nitrogen
    • C08K2003/385Binary compounds of nitrogen with boron

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to a reactive polyurethane hot melt adhesive for bonding TWS earphones and a preparation method thereof, wherein the reactive polyurethane hot melt adhesive comprises the following components in parts by weight: 10-30 parts of polyether polyol; 10-30 parts of crystalline polyester polyol; 10-30 parts of liquid polyester polyol; 20-30 parts of high glass transition temperature acrylic resin; 15-25 parts of polyisocyanate; 15-30 parts of modified perovskite wire; 0.01-1 part of catalyst; 0.1-3 parts of a silane coupling agent; 0.01-1 part of antioxidant. The adhesive prepared by the invention is suitable for bonding the shell and the shell of TWS earphone equipment, has the characteristics of high curing speed, high initial adhesion strength, sweat resistance and the like, has the waterproof grade of 5ATM, can shorten the pressure maintaining time to 30 minutes in the assembling process of the TWS earphone, and greatly improves the assembling efficiency of a TWS earphone production line.

Description

Reactive polyurethane hot melt adhesive for TWS earphone bonding and preparation method thereof
Technical Field
The invention relates to an adhesive, in particular to a reactive polyurethane hot melt adhesive for bonding a TWS (two-way clutch) earphone and a preparation method thereof.
Background
TWS is an abbreviation of True Wireless Stereo, True Wireless Stereo. With the rapid development of the bluetooth technology and the pursuit of people for the characteristics of light weight, high efficiency and the like of wearing products, the TWS headset goes into the visual field of users and is accepted and favored by more and more people. Compared with the traditional wired earphone, the TWS earphone gets rid of the constraint of an earphone wire, avoids the troubles of winding, wire breaking, stethoscope effect and the like, and has the advantages of portability, attractive appearance and the like. At present, the pressure maintaining time for gluing for structural part bonding in the industries of mobile phones, flat plates, intelligent wearing and earphones in the market is usually 2 hours, but due to the fact that the TWS earphones are complex in structure, large in part quantity and various in production and assembly processes, the quick positioning is realized for structural part bonding glue in urgent need of short pressure maintaining products, and the production efficiency of a production line is improved. TWS earphones are widely applied and are often used in the process of sports, and the TWS earphones put higher requirements on the waterproof and sweat aging resistance of the adhesive for structural bonding.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a reactive polyurethane hot melt adhesive (hereinafter referred to as PUR hot melt adhesive) for bonding a TWS earphone and a preparation method thereof, wherein the prepared PUR hot melt adhesive has the advantages of high curing speed, high initial adhesion strength and sweat resistance, meets the 5ATM waterproof requirement, can shorten the pressure holding time to 30 minutes in the TWS assembling process, and greatly improves the assembling efficiency of a TWS earphone production line.
The technical scheme of the invention is as follows:
a reactive polyurethane hot melt adhesive for bonding a TWS earphone is characterized by comprising the following components in parts by weight:
10-30 parts of polyether polyol;
10-30 parts of crystalline polyester polyol;
10-30 parts of liquid polyester polyol;
20-30 parts of high glass transition temperature acrylic resin;
15-25 parts of polyisocyanate;
15-30 parts of perovskite powder;
0.01-1 part of catalyst;
0.1-3 parts of a silane coupling agent;
0.01-1 part of antioxidant.
Further, the polyether polyol is one or more of polyoxypropylene glycol, polyoxypropylene-oxyethylene glycol and polytetrahydrofuran glycol with the molecular weight of 1000-4000.
Further, the crystalline polyester polyol is one or more of adipic acid and sebacic acid, and one or more of polyester polyol, polycaprolactone polyol and polycarbonate diol with the molecular weight of 1000-6000 are obtained through polycondensation reaction with one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol and neopentyl glycol.
Further, the liquid polyester polyol is one or more of adipic acid, sebacic acid, phthalic anhydride, isophthalic acid and terephthalic acid, and is an oligomer with the molecular weight of 1000-6000, which is obtained by polycondensation with one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol and neopentyl glycol.
Further, the high glass transition temperature acrylic resin is a high molecular compound which is obtained by one or more of methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, isobornyl methacrylate, methyl acrylate and butyl acrylate through high molecular polymerization reaction and has a glass transition temperature (Tg) of 65-85 ℃ and a molecular weight of 8000-80000.
Further, the polyisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
Further, the catalyst is one or more of triethyldiamine, dimorpholinodiethyl ether, triethylamine, dibutyltin dilaurate and stannous octoate.
Further, the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-isocyanatopropyltrimethoxysilane and gamma-isocyanatopropyltriethoxysilane.
Further, the antioxidant is one or more of an antioxidant 245, an antioxidant 1010, an antioxidant 1035 and an antioxidant 1076.
A preparation method of a reactive polyurethane hot melt adhesive for bonding a TWS earphone is characterized by comprising the following steps:
adding polyether polyol, crystalline polyester polyol, liquid polyester polyol and high glass transition temperature acrylic resin into a reaction kettle, vacuumizing and dehydrating at 140-150 ℃ for 2-3h until the water content is less than 200ppm, and cooling to 80-90 ℃; adding polyisocyanate and perovskite into the system while stirring under the protection of nitrogen, after the addition is finished, carrying out vacuum pumping reaction, slowly heating to 105-115 ℃, keeping the temperature for 2-3h, adding a catalyst, a silane coupling agent and an antioxidant under the protection of nitrogen, and carrying out vacuum pumping reaction for 0.5-1h to obtain a polyurethane adhesive;
the preparation method of the modified perovskite filament comprises the steps of mixing borax, perovskite, filamentous carbon fibers, 12% of mass fraction ammonium chloride solution and 15% of solubility hydrochloric acid according to the weight portion ratio of 1:1:1:10:10, putting the mixture into a stirrer, reacting for 1-2 hours at the temperature of 35-50 ℃, filtering, cleaning and drying to obtain the modified perovskite filament wrapped in the carbon fiber filament and filled with boron nitride.
By the scheme, the invention at least has the following advantages:
the invention mainly uses acrylic resin with high glass transition temperature when preparing polyurethane prepolymer. The thermoplastic acrylic resin is used as one of tackifying resins, has good compatibility with polyurethane prepolymer, and can adjust the melting viscosity of a system. The acrylic resin has various types, different glass transition temperatures, and the acrylic resin with high glass transition temperature at room temperature has higher conversion speed, can shorten the positioning time and obtain higher initial bonding strength. Meanwhile, the acrylic resin has high polarity and forms stronger interaction with a solid substrate to obtain better wetting effect, thereby greatly improving the bonding property to the substrate. The acrylic resin has good weather resistance, chemical resistance and water resistance, and can improve the weather resistance and acid and alkali resistance of the whole system when added into the polyurethane prepolymer.
The invention has another innovation point that the modified perovskite wire is used as the filler, when the glue is cured after the modified perovskite wire is used as the filler, the filler can also extend to the bonding surface of the whole TWS earphone due to the fact that the filler is distributed in the modified perovskite wire, and the hardness of the perovskite wire of the filler is far greater than that of the plastic of the TWS earphone, so that the filler can penetrate into the plastic through external force extrusion after bonding, and a firmer connecting structure is formed.
As for the filler, boron nitride is generated through the reaction of borax, hydrochloric acid and ammonium chloride, the perovskite has the characteristic of porosity, the generated boron nitride can enter the air, and meanwhile, due to the existence of the carbon fiber yarns, the three components are mutually wrapped and wound to form a stable connection structure.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
Adding 10 parts of polyoxypropylene glycol with the molecular weight of 1000, 10 parts of crystalline polyester polyol (polycaprolactone polyol with the molecular weight of 1000), 10 parts of liquid polyester polyol (with the molecular weight of 1000) and 20 parts of high-glass transition temperature acrylic resin (with the molecular weight of 8000 and the Tg of 65 ℃) into a reaction kettle, vacuumizing and dehydrating at 140 ℃ for 2-h until the water content is less than 200ppm, and cooling to 80 ℃; adding 15 parts of toluene diisocyanate and 15 parts of modified perovskite filament into the system while stirring under the protection of nitrogen, vacuumizing for reaction after the addition is finished, slowly heating to 105 ℃, keeping for 2 hours, adding 0.01 part of dimorpholinyl diethyl ether agent, 0.1 part of gamma-aminopropyl trimethoxy silane and 0.01 part of antioxidant under the protection of nitrogen, and vacuumizing for reaction for 0.5-hours to obtain a polyurethane adhesive;
the preparation method of the modified perovskite filament comprises the steps of mixing borax, perovskite, filamentous carbon fibers, 12% of mass fraction ammonium chloride solution and 15% of solubility hydrochloric acid according to the weight portion ratio of 1:1:1:10:10, putting the mixture into a stirrer, and reacting for 1 hour at the temperature of 35 ℃ to obtain the modified perovskite filament wrapped in the carbon fiber filament and filled with boron nitride.
Example 2
Adding 20 parts of polyoxypropylene-ethylene oxide glycol with the molecular weight of 2000, 20 parts of crystalline polyester polyol (polycarbonate glycol with the molecular weight of 3000), 20 parts of liquid polyester polyol (molecular weight of 3000) and 25 parts of high-glass transition temperature acrylic resin (the molecular weight of 20000 and the Tg of 75 ℃) into a reaction kettle, vacuumizing and dehydrating at 145 ℃ for 2.5h until the water content is less than 200ppm, and cooling to 85 ℃; adding 20 parts of diphenylmethane diisocyanate and 20 parts of modified perovskite filaments into the system while stirring under the protection of nitrogen, performing vacuum pumping reaction after the addition is finished, slowly heating to 110 ℃, keeping the temperature for 2.5 hours, adding 0.5 part of triethyldiamine, 1 part of gamma-mercaptopropyltriethoxysilane and 0.5 part of antioxidant 1035 under the protection of nitrogen, and performing vacuum pumping reaction for 0.7 hour to obtain a polyurethane adhesive;
the preparation method of the modified perovskite filament comprises the steps of mixing borax, perovskite, filamentous carbon fibers, 12% of mass fraction ammonium chloride solution and 15% of solubility hydrochloric acid according to the weight portion ratio of 1:1:1:10:10, putting the mixture into a stirrer, and reacting for 1-2 hours at the temperature of 35-50 ℃ to obtain the modified perovskite filament wrapped in the carbon fiber filament and filled with boron nitride.
Example 3
Adding 30 parts of polyoxypropylene-ethylene oxide glycol with the molecular weight of 4000, 30 parts of crystalline polyester polyol (polycaprolactone polyol with the molecular weight of 6000), 30 parts of liquid polyester polyol (molecular weight of 6000) and 30 parts of acrylic resin with high glass transition temperature (the molecular weight of 80000 and Tg of 85 ℃) into a reaction kettle, vacuumizing and dehydrating at 150 ℃ for 3 hours until the water content is less than 200ppm, and cooling to 90 ℃; adding 25 parts of toluene diisocyanate and 30 parts of modified perovskite filament into the system while stirring under the protection of nitrogen, after the addition is finished, performing vacuum pumping reaction, slowly heating to 115 ℃, keeping the temperature for 3 hours, adding 1 part of triethyldiamine, 3 parts of gamma-isocyanate propyl triethoxysilane and 1 part of antioxidant 245 under the protection of nitrogen, and performing vacuum pumping reaction for 1 hour to obtain a polyurethane adhesive;
the preparation method of the modified perovskite filament comprises the steps of mixing borax, perovskite, filamentous carbon fibers, 12% of mass fraction ammonium chloride solution and 15% of solubility hydrochloric acid according to the weight portion ratio of 1:1:1:10:10, putting the mixture into a stirrer, and reacting for 2 hours at the temperature of 50 ℃ to obtain the modified perovskite filament wrapped in the carbon fiber filament and filled with boron nitride.
Comparative example 1
Adding 30 parts of polyoxypropylene-ethylene oxide glycol with the molecular weight of 4000, 30 parts of crystalline polyester polyol (polycaprolactone polyol with the molecular weight of 6000), 30 parts of liquid polyester polyol (molecular weight of 6000) and 30 parts of acrylic resin into a reaction kettle, vacuumizing and dehydrating at 150 ℃ for 3 hours until the water content is less than 200ppm, and cooling to 90 ℃; adding 25 parts of toluene diisocyanate and 30 parts of modified perovskite filaments into the system while stirring under the protection of nitrogen, vacuumizing for reaction after the addition is finished, slowly heating to 115 ℃, keeping the temperature for 3 hours, adding 1 part of triethyldiamine, 3 parts of gamma-isocyanate propyl triethoxysilane and 1 part of antioxidant 245 under the protection of nitrogen, and vacuumizing for reaction for 1 hour to obtain the polyurethane adhesive.
Comparative example 1 is different from the above examples in that the acrylic resin is a conventional resin.
Comparative example 2
Adding 30 parts of polyoxypropylene-ethylene oxide glycol with the molecular weight of 4000, 30 parts of crystalline polyester polyol (polycaprolactone polyol with the molecular weight of 6000), 30 parts of liquid polyester polyol (molecular weight of 6000) and 30 parts of acrylic resin with high glass transition temperature (the molecular weight of 80000 and Tg of 85 ℃) into a reaction kettle, vacuumizing and dehydrating at 150 ℃ for 3 hours until the water content is less than 200ppm, and cooling to 90 ℃; adding 25 parts of toluene diisocyanate into the system while stirring under the protection of nitrogen, vacuumizing for reaction after the addition is finished, slowly heating to 115 ℃, keeping for 3 hours, adding 1 part of triethyldiamine, 3 parts of gamma-isocyanate propyl triethoxysilane and 245, 1 part of antioxidant under the protection of nitrogen, and vacuumizing for reaction for 1 hour to obtain the polyurethane adhesive.
Comparative example 2 differs from the above examples in that no modified perovskite filaments were used as filler.
The following table shows the results of the performance tests of examples 1-3 and comparative examples 1-2:
Figure BDA0003535305210000041
the acid-base aging strength test is a shear bonding strength test, the bonding strength test base material is PC + GF// ink glass, and the waterproof and acid-base aging waterproof sample test base materials are PC + GF// transparent glass and PA + GF// transparent glass.
The test methods of examples 1-5 and comparative examples of the present invention are as follows:
and (3) viscosity testing:
the temperature was 110. + -. 1 ℃ using a Brookfield DV2T viscometer, using a 27 spindle.
Testing the butt joint bonding strength:
gluing a PC + GF (90mm x 50mm x 5mm) substrate by using a glue sprayer, wherein the glue line is in a circular shape with the diameter of 25.4mm, the width of the glue line is 1mm after the glue line is pressed, the thickness of the glue line is 0.15mm, the printing ink glass (50mm x 6mm) substrate is pressed on the circular glue line, the pressure is maintained for 0.5h by using a 1kg weight, the weight is taken down to test the butt joint bonding strength for 0.5h, and the butt joint bonding strength is tested after the printing ink glass is cured for 72 h. Curing conditions are as follows: the temperature is 23 +/-2 ℃, and the humidity is 60 +/-10% RH; testing speed: 10 mm/min.
Acid-base aging strength test:
and (3) gluing the PC + GF (101.6mm by 25.4mm by 2mm) base material by using a glue sprayer, wherein the size of a glue line is 25.4mm linear, the width is 1mm after the gluing is carried out, the thickness of the glue layer is 0.15mm, the printing ink glass (101.6mm by 25.4mm by 2mm) base material is pressed on the glue line, the pressure is maintained for 0.5h by using a 1kg weight, and the weight is taken down and cured for 72 h. Preparing acidic artificial sweat with pH value of 4.7 and alkaline artificial sweat with pH value of 9.5, soaking the acidic artificial sweat and the alkaline artificial sweat respectively in dust-free cloth, wrapping the sample with the dust-free cloth soaked with the artificial sweat, sealing the sample with a valve bag, aging the sample in an aging box with temperature and humidity of 55 ℃/95% RH for 72h, taking out the sample, standing the sample at room temperature for 1 day, and testing the shearing and bonding strength. Curing conditions are as follows: the temperature is 23 +/-2 ℃, and the humidity is 60 +/-10% RH; testing speed: 10 mm/min.
50m waterproof test:
the method comprises the steps of gluing a transparent glass (101.6mm × 25.4mm × 2mm) substrate by a glue sprayer, placing yellow water-sensitive paper with the size of 5mm × 0.1mm in a rectangular glue line with the size of 20.4mm × 96.6mm rectangle, the width of 0.4-0.6mm after lamination and the thickness of a glue layer of 0.1mm, laminating PC + GF (101.6mm × 25.4mm × 2mm) or PA + GF (101.6mm × 25.4mm × 2mm) substrate on the glue line, maintaining the pressure for 0.5h by using 2 weights of 1kg, taking down the weights and curing for 72 h. Putting the sample into water, pressurizing at 0.5MPa, keeping for 30min, and observing whether the yellow water-sensitive paper in the sample turns blue or not after pressure relief, wherein the yellow water-sensitive paper is unqualified if the yellow water-sensitive paper turns blue, and the yellow water-sensitive paper is marked as 'N', and the yellow water-sensitive paper is qualified if the yellow water-sensitive paper turns yellow, and is marked as 'Y'. Curing conditions are as follows: the temperature is 23 +/-2 ℃, and the humidity is 60 +/-10% RH.
50m water resistance + acid-base aging test:
preparing acidic artificial sweat with pH value of 4.7 and alkaline artificial sweat with pH value of 9.5, soaking with dust-free cloth, wrapping the dust-free cloth soaked with artificial sweat with a waterproof sample, sealing with a valve bag, aging in an aging oven with temperature and humidity of 55 ℃/95% RH for 72h, taking out, standing at room temperature for 1 day, and performing 50m waterproof test.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A reactive polyurethane hot melt adhesive for bonding a TWS earphone is characterized by comprising the following components in parts by weight:
10-30 parts of polyether polyol;
10-30 parts of crystalline polyester polyol;
10-30 parts of liquid polyester polyol;
20-30 parts of high glass transition temperature acrylic resin;
15-25 parts of polyisocyanate;
15-30 parts of modified perovskite wire;
0.01-1 part of catalyst;
0.1-3 parts of a silane coupling agent;
0.01-1 part of antioxidant.
2. The reactive polyurethane hot melt adhesive for bonding the TWS earphones according to claim 1, wherein: the polyether polyol is one or the mixture of more than two of polyoxypropylene diol, polyoxypropylene-oxyethylene diol and polytetrahydrofuran diol with the molecular weight of 1000-4000.
3. The reactive polyurethane hot melt adhesive for bonding the TWS earphones according to claim 1, wherein: the crystalline polyester polyol is one or more of adipic acid and sebacic acid, and one or more of polyester polyol, polycaprolactone polyol and polycarbonate diol with the molecular weight of 1000-6000 are obtained by the polycondensation reaction of the crystalline polyester polyol and one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol and neopentyl glycol.
4. The reactive polyurethane hot melt adhesive for bonding the TWS earphones according to claim 1, wherein: the liquid polyester polyol is one or more of adipic acid, sebacic acid, phthalic anhydride, isophthalic acid and terephthalic acid, and is an oligomer with the molecular weight of 1000-6000, which is obtained by the polycondensation reaction of one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol and neopentyl glycol.
5. The reactive polyurethane hot melt adhesive for bonding the TWS earphones according to claim 1, wherein: the high glass transition temperature acrylic resin is a high molecular compound which is obtained by one or more of methyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, isobornyl methacrylate, methyl acrylate and butyl acrylate through high molecular polymerization reaction and has the glass transition temperature (Tg) of 8000-80000 and 65-85 ℃.
6. The reactive polyurethane hot melt adhesive for bonding the TWS earphones according to claim 1, wherein: the polyisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
7. The reactive polyurethane hot melt adhesive for bonding the TWS earphones according to claim 1, wherein: the catalyst is one or more of triethyldiamine, dimorpholinodiethyl ether, triethylamine, dibutyltin dilaurate and stannous octoate.
8. The reactive polyurethane hot melt adhesive for bonding the TWS earphones according to claim 1, wherein: the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-isocyanatopropyltrimethoxysilane and gamma-isocyanatopropyltriethoxysilane.
9. The reactive polyurethane hot melt adhesive for bonding the TWS earphones according to claim 1, wherein: the antioxidant is one or more of antioxidant 245, antioxidant 1010, antioxidant 1035 and antioxidant 1076.
10. A preparation method of a reactive polyurethane hot melt adhesive for bonding a TWS earphone is characterized by comprising the following steps:
adding polyether polyol, crystalline polyester polyol, liquid polyester polyol and high glass transition temperature acrylic resin into a reaction kettle, vacuumizing and dehydrating at 140-150 ℃ for 2-3h until the water content is less than 200ppm, and cooling to 80-90 ℃; adding polyisocyanate and modified perovskite filament into the system while stirring under the protection of nitrogen, performing vacuum pumping reaction after the addition is finished, slowly heating to 105-115 ℃, keeping for 2-3h, adding a catalyst, a silane coupling agent and an antioxidant under the protection of nitrogen, and performing vacuum pumping reaction for 0.5-1h to obtain a polyurethane adhesive;
the preparation method of the modified perovskite filament comprises the steps of mixing borax, perovskite, filamentous carbon fibers, 12% of mass fraction ammonium chloride solution and 15% of solubility hydrochloric acid according to the weight portion ratio of 1:1:1:10:10, putting the mixture into a stirrer, and reacting for 1-2 hours at the temperature of 35-50 ℃ to obtain the modified perovskite filament wrapped in the carbon fiber filament and filled with boron nitride.
CN202210216893.8A 2022-03-07 2022-03-07 Reactive polyurethane hot melt adhesive for TWS earphone bonding and preparation method thereof Pending CN114479743A (en)

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