CN109852319B - Polyurethane hot melt adhesive and preparation method thereof - Google Patents
Polyurethane hot melt adhesive and preparation method thereof Download PDFInfo
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- CN109852319B CN109852319B CN201910195961.5A CN201910195961A CN109852319B CN 109852319 B CN109852319 B CN 109852319B CN 201910195961 A CN201910195961 A CN 201910195961A CN 109852319 B CN109852319 B CN 109852319B
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Abstract
The invention discloses a polyurethane hot melt adhesive and a preparation method thereof, wherein the hot melt adhesive is prepared from the following raw materials in parts by mass: 20-70 parts of polyether polyol, 1-50 parts of polyester polyol, 1-20 parts of polyisocyanate, 10-20 parts of tackifying resin, 5-20 parts of hollow microspheres, 0.5-1 part of flatting agent, 1-3 parts of coupling agent I and 0.01-1 part of catalyst, wherein the tackifying resin comprises at least one of hydroxyl-terminated rubber and modified hydroxyl-terminated acrylate, and accounts for 10% or more of the total mass of the raw materials; the hollow micro-beads are prepared by uniformly mixing hollow micro-particles with the particle size of 30-200um and an organosilane coupling agent diluted by a solvent at the temperature of 50-100 ℃, heating, drying, volatilizing the solvent, and sieving to obtain the micro-beads with the particle size of 20-125um, wherein the hollow micro-beads account for 5-20% of the total mass of the raw materials. The hot melt adhesive prepared by the invention has low modulus, high rebound resilience, high adhesion and good humidity resistance.
Description
Technical Field
The invention relates to the technical field of hot melt adhesives, and particularly relates to a polyurethane hot melt adhesive and a preparation method thereof.
Background
VHB and PUR hot melt adhesives are often used in the bonding of screens and frames of electronic products. For conventional bonding, VHB meets the requirement of waterproof bonding force, but for the popular narrow-frame electronic products in recent years, VHB cannot provide good bonding force, and moisture-cured PUR hot melt adhesive is generally adopted.
However, with the continuous development of electronic products, in order to improve the waterproof performance, some mobile phones without traditional openings (speakers) appear in the market, and the mobile phones vibrate and sound by using a screen or a rear shell, so that higher requirements are provided for the adhesion of the screen and the body, and the mobile phones can provide better adhesion force, and also have very low elastic modulus, better elasticity and fatigue resistance, and obviously the lower adhesion force of the narrow frame of the VHB cannot meet the higher requirements.
The PUR hot melt adhesive is a high-viscosity single-component moisture-curing polyurethane hot melt adhesive, and the main component of the PUR hot melt adhesive is an isocyanate-terminated prepolymer. The conventional PUR hot melt adhesive has high tensile strength (more than or equal to 20MPa) and high elastic modulus (E is more than or equal to 10MPa) after being cured, the minimum bonding thickness is close to 0.3mm when a screen is bonded, and under the thickness, how to maintain the bonding force can also enable the screen to vibrate, and the traditional hot melt adhesive obviously cannot give consideration to the points. Therefore, it is necessary to provide a PUR hot melt adhesive with low modulus, high resilience, high adhesion and fatigue resistance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a polyurethane hot melt adhesive which has the properties of low modulus, high resilience, high adhesive force and fatigue resistance.
In order to achieve the purpose, the invention adopts the technical scheme that: a polyurethane hot melt adhesive is composed of the following raw materials in parts by weight:
wherein the molecular weight of the polyether polyol is 400-4000;
the molecular weight of the polyester polyol is 2000-4000;
the tackifying resin comprises at least one of hydroxyl-terminated rubber and modified hydroxyl-terminated acrylate, the molecular weight of the modified hydroxyl-terminated acrylate is 1500-2500, the side chain of the modified hydroxyl-terminated acrylate comprises at least one of benzene ring, ester group or hydroxyl, and the tackifying resin accounts for 10% or more of the total mass of the raw materials;
the hollow microspheres are microspheres with the particle size of 45-90um, which are obtained by uniformly mixing hollow particles with the particle size of 30-200um and an organosilane coupling agent diluted by a solvent at the temperature of 50-100 ℃, heating, drying, volatilizing the solvent and sieving, wherein the hollow microspheres account for 5-20% of the total mass of the raw materials;
the coupling agent I is a silane coupling agent.
Preferably, the polyether polyol is selected from at least one of polypropylene glycol, polyethylene glycol and polytetrahydrofuran glycol.
Preferably, the polyester polyol is selected from at least one of adipic acid-based polyester diol, polycarbonate diol, polyethylene terephthalate, and phthalic anhydride polyester polyol.
Preferably, the polyisocyanate is selected from at least one of diphenylmethane diisocyanate, hexamethylene diisocyanate, and toluene diisocyanate.
Preferably, the hollow micro-particles used in the hollow micro-beads can be selected from one or more of hollow glass micro-beads, hollow plastic micro-beads and hollow rubber micro-beads.
Preferably, the catalyst is selected from one or more of organic tin catalysts and amine catalysts, and the leveling agent is selected from one or more of acrylic leveling agents, organic silicon leveling agents and fluorine leveling agents.
Preferably, the hydroxyl-terminated rubber is at least one selected from hydroxyl-terminated polybutadiene, hydroxyl-terminated polysiloxane and hydroxyl-terminated polyisoprene.
Preferably, the organosilane coupling agent employs gamma-mercaptopropyltrimethoxysilane.
The invention also aims to provide a preparation method of the polyurethane hot melt adhesive, which comprises the following steps:
1) putting polyether polyol, polyester polyol, tackifying resin and hollow microspheres into a reaction kettle according to the mass part ratio, heating to 110-140 ℃, stirring, and carrying out vacuum dehydration for 2-3 hours;
2) cooling to 60-70 ℃ under the condition of N2Adding polyisocyanate under protection, and adding N at 80-140 deg.C2Stirring and reacting for 0.5-2 hours under protection to generate an isocyanate-terminated polyurethane prepolymer;
3)N2adding a catalyst, a flatting agent and a coupling agent I under protection, vacuumizing at 80-140 ℃, stirring for 0.5-1.5 hours, and discharging to obtain the required polyurethane hot melt adhesive.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: according to the polyurethane hot melt adhesive disclosed by the invention, the polyether polyol and the polyester polyol are adopted as main chains to provide better cohesive strength, the introduction of the tackifying resin improves the surface adhesion to organic materials and the flexibility of the cured adhesive, the elastic modulus of the hot melt adhesive is reduced by filling the hollow microspheres, and the cat eye effect formed by the hot melt adhesive and the hollow microspheres during material stretching is better in rebound resilience. Meanwhile, the reactive hot melt adhesive prepared by the invention has excellent bonding effect on organic high polymer, metal and inorganic non-metal materials, has good damp and heat resistance, can be applied to bonding of materials with low surface performance, can be in damp, hot and vibration environments for a long time, is mainly suitable for electronic and electric appliances, and can also be applied to the fields of automobile manufacturing, building engineering and the like, and is wide in application.
Detailed Description
The technical solution of the present invention is further illustrated below with reference to specific examples.
Preparation of hollow micro-beads
Raw materials: hollow glass microspheres K20 (particle size distribution 30-200 um); gamma-mercaptopropyltrimethoxysilane; anhydrous ethanol.
The preparation process comprises the following steps: preparing a silane coupling agent into a dilute solution with the concentration of 0.5-1% by adopting absolute ethyl alcohol; adding the hollow glass microspheres into the solution at the temperature of 50-100 ℃, uniformly mixing, heating and drying, and sieving after the solvent is volatilized to obtain the required hollow microspheres.
Of course, hollow plastic beads or hollow rubber beads may be used as the hollow beads.
Sieving the hollow micro-beads with a standard test sieve to obtain the following specifications
TABLE 1
| Serial number | 1 | 2 | 3 | 4 | 5 |
| Particle size um | 20-38 | 38-45 | 45-63 | 63-90 | 90-125 |
Secondly, preparation of hot melt adhesive
The preparation method of the hot melt adhesive comprises the following specific steps:
1) putting polyether polyol, polyester polyol, tackifying resin and hollow microspheres into a reaction kettle according to the mass part ratio, heating to 110-140 ℃, stirring, and carrying out vacuum dehydration for 2-3 hours;
2) cooling to 60-70 ℃ under the condition of N2Adding polyisocyanate under protection, and adding N at 80-140 deg.C2Stirring and reacting for 0.5-2 hours under protection to generate an isocyanate-terminated polyurethane prepolymer;
3)N2adding a catalyst, a flatting agent and a coupling agent I under protection, vacuumizing at 80-140 ℃, stirring for 0.5-1.5 hours, and discharging to obtain the required polyurethane hot melt adhesive.
The raw materials used in examples 1 to 6 and comparative examples 1 to 13 each include the components shown in table 2, but differ in the particle size of the hollow fine particles used for wiping and the proportion of the hollow fine particles to the total mass of the raw material, as shown in table 3:
TABLE 2
| Serial number | Raw materials | Mass portion of |
| 1 | PPG-2000Mn＝2000 | 41.1 |
| 2 | Hydroxyl-terminated polybutadiene Mn ═ 3500 | 7 |
| 3 | Polyester polyol Mn 1000 | 10 |
| 4 | Modified hydroxyl terminated acrylate Mn 2000 | 10 |
| 5 | MDI | 9.5 |
| 6 | Leveling agent | 0.6 |
| 7 | Coupling agent I | 1.5 |
| 8 | DMDEE | 0.3 |
Wherein PPG-2000 is polypropylene glycol, and MD I is polyisocyanate; DMDEE is a catalyst dimorpholinoethyl ether, and the coupling agent can be selected from silane coupling agents.
TABLE 3
The performance tests were carried out for examples 1 to 6 and comparative examples 1 to 13, as follows:
modulus of elasticity test
According to the tensile property test standard of ISO 527-2 plastics, after being coated with a hot melt adhesive, the hot melt adhesive is placed in a 25 ℃ 55% RH environment to be cured for 24 hours, and then the sample preparation test is carried out with the normal temperature environment.
Shear strength test
According to the test standard of tensile shear strength of ISO-4587 adhesive, the hot melt adhesive is coated on a PC board (with the size of 20mm x 100mm x 4mm), cured for 24 hours at 25 ℃ in 55% RH environment, and then subjected to shear test by using a universal material testing machine in normal temperature environment
Drop test
Referring to GB/T2423.8, two stainless steel plates (size 20mm 100mm 4mm) were bonded using hot melt glue, free falling at a height of 1000 mm.
The results of the performance tests are shown in Table 4.
TABLE 4
From table 4, it can be seen that when the hollow microspheres with the particle size of 45-90um are adopted and the filling amount is 5-20%, the modulus of the hot melt adhesive is effectively reduced, the creep recovery of the rebound resilience finished product is improved, and the overall comprehensive performance is good.
The raw materials used in examples 7 to 13 and comparative examples 14 and 15 each include the components shown in Table 5, except that the ratio of the hydroxyl-terminated rubber to the modified hydroxyl-terminated acrylate was varied in mass ratio as shown in Table 6.
TABLE 5
| Serial number | Raw materials | Mass portion of |
| 1 | PPG-2000Mn＝2000 | 50 |
| 2 | Polyester polyol Mn 1000 | 20 |
| 3 | MDI | 10 |
| 4 | Hollow microbead number 4 | 10 |
| 5 | Leveling agent | 0.7 |
| 6 | Coupling agent I | 1.5 |
| 7 | DMDEE | 0.4 |
TABLE 6
The performance tests were conducted for examples 7 to 13 and comparative examples 14 and 15, and the test results are shown in Table 7.
TABLE 7
From the above table, it can be seen that when the content of the toughening resin in the formulation is low, the expected modulus cannot be obtained, and when the content of the toughening resin is increased to more than 10%, or the total content of the two toughening resins is increased to more than 10%, the better toughening effect can be obtained.
Of course, here, the polyether polyol can also be at least one of polypropylene glycol, polyethylene glycol and polytetrahydrofuran glycol; the polyester polyol can be at least one of adipic acid polyester diol, polycarbonate diol, polyethylene terephthalate and phthalic anhydride polyester polyol; the polyisocyanate can be at least one of diphenylmethane diisocyanate, hexamethylene diisocyanate and toluene diisocyanate; the hydroxyl-terminated rubber can be at least one of hydroxyl-terminated polybutadiene, hydroxyl-terminated polysiloxane and hydroxyl-terminated polyisoprene; the molecular weight of the modified hydroxyl-terminated acrylate is 1500-; the flatting agent can be one or more of acrylic, organic silicon and fluorine flatting agents.
According to the hot melt adhesive disclosed by the invention, the polyether polyol and the polyester polyol are adopted as main chains to provide better cohesive strength, the surface adhesion of an organic material is improved by introducing the modified hydroxyl-terminated acrylate and the hydroxyl-terminated rubber, the flexibility of the cured adhesive is improved, the elastic modulus of the hot melt adhesive is reduced by filling the processed hollow microspheres, and the cat eye effect formed by the hot melt adhesive and the hollow microspheres is better in rebound resilience when the material is stretched. Meanwhile, the reactive hot melt adhesive prepared by the invention has excellent bonding effect on organic high polymer, metal and inorganic non-metal materials, has good damp and heat resistance, can be applied to bonding of materials with low surface performance, can be in damp, hot and vibration environments for a long time, is mainly suitable for electronic and electric appliances, and can also be applied to the fields of automobile manufacturing, building engineering and the like, and is wide in application.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (9)
1. The polyurethane hot melt adhesive is characterized by comprising the following raw materials in parts by mass:
20-70 parts of polyether glycol
1-50 parts of polyester polyol
1-20 parts of polyisocyanate
10-20 parts of tackifying resin
5-20 parts of hollow microspheres
0.5-1 part of flatting agent
1-3 parts of coupling agent I
0.01-1 part of catalyst
Wherein the molecular weight of the polyether polyol is 400-4000;
the molecular weight of the polyester polyol is 2000-4000;
the tackifying resin comprises at least one of hydroxyl-terminated rubber and modified hydroxyl-terminated acrylate, the molecular weight of the modified hydroxyl-terminated acrylate is 1500-2500, the side chain of the modified hydroxyl-terminated acrylate comprises at least one of benzene ring, ester group or hydroxyl, and the tackifying resin accounts for 10% or more of the total mass of the raw materials;
the hollow microspheres are microspheres with the particle size of 45-90 mu m, which are obtained by uniformly mixing hollow particles with the particle size of 30-200 mu m and an organosilane coupling agent diluted by a solvent at the temperature of 50-100 ℃, heating, drying, volatilizing the solvent and sieving, wherein the hollow microspheres account for 5-20% of the total mass of the raw materials;
the coupling agent I is a silane coupling agent.
2. The polyurethane hot melt adhesive of claim 1, wherein the polyether polyol is at least one selected from polypropylene glycol, polyethylene glycol and polytetrahydrofuran glycol.
3. The polyurethane hot melt adhesive according to claim 1, wherein the polyester polyol is at least one selected from the group consisting of adipic acid-based polyester diol, polycarbonate diol, polyethylene terephthalate, and phthalic anhydride polyester polyol.
4. The polyurethane hot melt adhesive according to claim 1, wherein the polyisocyanate is at least one selected from the group consisting of diphenylmethane diisocyanate, hexamethylene diisocyanate, and toluene diisocyanate.
5. The polyurethane hot melt adhesive according to claim 1, wherein the hollow particles used in the hollow beads are selected from one or more of hollow glass beads, hollow plastic beads and hollow rubber beads.
6. The polyurethane hot melt adhesive according to claim 1, wherein the catalyst is selected from one or more of organic tin catalysts and amine catalysts, and the leveling agent is selected from one or more of acrylic leveling agents, silicone leveling agents and fluorine leveling agents.
7. The polyurethane hot melt adhesive according to claim 1, wherein the hydroxyl-terminated rubber is at least one selected from hydroxyl-terminated polybutadiene, hydroxyl-terminated polysiloxane, and hydroxyl-terminated polyisoprene.
8. The polyurethane hot melt adhesive according to claim 1, wherein an organosilane coupling agent used in the preparation process of the hollow microspheres is gamma-mercaptopropyl trimethoxysilane.
9. A process for preparing a polyurethane hot melt adhesive as claimed in any one of claims 1 to 8, characterized by comprising the steps of:
1) putting polyether polyol, polyester polyol, tackifying resin and hollow microspheres into a reaction kettle according to the mass part ratio, heating to 110-140 ℃, stirring, and carrying out vacuum dehydration for 2-3 hours;
2) cooling to 60-70 ℃ under the condition of N2Adding polyisocyanate under protection, and adding N at 80-140 deg.C2Stirring and reacting for 0.5-2 hours under protection to generate an isocyanate-terminated polyurethane prepolymer;
3）N2adding a catalyst, a flatting agent and a coupling agent I under protection, vacuumizing at 80-140 ℃, stirring for 0.5-1.5 hours, and discharging to obtain the required polyurethane hot melt adhesive.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110819292B (en) * | 2019-11-25 | 2021-04-02 | 杭州之江新材料有限公司 | Polyurethane hot melt adhesive for vehicle lamp |
| CN111334240A (en) * | 2020-03-17 | 2020-06-26 | 北京华腾新材料股份有限公司 | Reactive polyurethane hot melt adhesive and preparation method and application thereof |
| CN112143435A (en) * | 2020-09-25 | 2020-12-29 | 烟台斯普瑞电子材料有限公司 | Hot-melt reaction type polyurethane adhesive for compounding electronic nylon film |
| CN115584232A (en) * | 2022-02-17 | 2023-01-10 | 宜兴市普利泰电子材料有限公司 | High-elongation self-adhesive polyurethane packaging material and preparation method thereof |
| CN114672275B (en) * | 2022-04-29 | 2023-06-23 | 福建奥翔体育塑胶科技股份有限公司 | Single-component moisture-curing polyurethane adhesive and preparation method and application thereof |
| CN115287013A (en) * | 2022-07-28 | 2022-11-04 | 广东汇齐新材料有限公司 | Biomass TPU hot melt adhesive film and preparation method thereof |
| CN116948589B (en) * | 2023-09-20 | 2023-12-12 | 山东一诺威新材料有限公司 | Sealed high-modulus hollow glass edge sealing adhesive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107652937A (en) * | 2017-11-06 | 2018-02-02 | 烟台德邦科技有限公司 | A kind of preparation method of polyurethane hot melt that can be Nian Jie with low-surface-energy material |
| CN108997965A (en) * | 2018-09-10 | 2018-12-14 | 成都硅宝科技股份有限公司 | A kind of reactive polyurethane hot melt and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107652937A (en) * | 2017-11-06 | 2018-02-02 | 烟台德邦科技有限公司 | A kind of preparation method of polyurethane hot melt that can be Nian Jie with low-surface-energy material |
| CN108997965A (en) * | 2018-09-10 | 2018-12-14 | 成都硅宝科技股份有限公司 | A kind of reactive polyurethane hot melt and preparation method thereof |
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