CN109735278B - Water-based epoxy adhesive and application thereof in bonding high-performance fiber bulletproof plate - Google Patents
Water-based epoxy adhesive and application thereof in bonding high-performance fiber bulletproof plate Download PDFInfo
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Abstract
The invention provides a water-based epoxy adhesive and application thereof, wherein the adhesive comprises the following components: an epoxy component and a curing component; the epoxy component comprises a waterborne epoxy resin emulsion; the curing component comprises an amine curing agent and an aqueous polyurethane emulsion, wherein the aqueous polyurethane emulsion accounts for 10-40% of the total mass of the curing component, and the solid content of the aqueous polyurethane emulsion is 25-50%. The invention adopts an epoxy system in the form of aqueous epoxy resin emulsion, and has good adhesive property, excellent hardness and rigidity. In addition, the invention mainly introduces a certain amount of waterborne polyurethane emulsion components to toughen the epoxy resin matrix. The high-performance fiber bulletproof plate bonded by the adhesive can obtain excellent impact resistance, reduce the depth of recess after bullet impact and improve the bulletproof effect on the premise of ensuring enough bonding strength, adhesive layer hardness and rigidity.
Description
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a water-based epoxy adhesive and application thereof in bonding of a high-performance fiber bulletproof plate.
Background
Although ceramic bulletproof plates are developed quickly, the brittleness defect of the materials cannot be solved well all the time. Therefore, the function of the high-performance fiber bulletproof plate cannot be replaced. The ballistic mechanism of high performance fibers is that they absorb a large amount of energy and resist penetration of bullets by energy transfer. At present, the most common fiber composite board with the best bulletproof effect is an ultrahigh molecular weight polyethylene fiber bulletproof board, which belongs to a flexible material.
The existing high-performance fiber armor, such as ultra-high molecular weight polyethylene fiber armor, is generally prepared by a process comprising: the high-performance fiber yarns are sprayed with an adhesive or dipped into the adhesive in a single direction to prepare single-direction cloth, and after orthogonal treatment, the single-direction cloth is laminated and processed into a bulletproof product by a press at high temperature and high pressure. The adhesives used by the prior bulletproof plate are mainly polyurethane and acrylate adhesives. Although the bulletproof plate has good penetration resistance, the rigidity and the rigidity of the bulletproof plate are not as good as those of metal or ceramic materials, so that the bulletproof plate has the problems of large depth of a recess after being impacted and the like.
Disclosure of Invention
In view of this, the application provides a water-based epoxy adhesive and an application thereof in bonding a high-performance fiber bulletproof plate.
The invention provides a water-based epoxy adhesive, which comprises the following components: an epoxy component and a curing component;
the epoxy component comprises a waterborne epoxy resin emulsion; the curing component comprises an amine curing agent and an aqueous polyurethane emulsion, wherein the aqueous polyurethane emulsion accounts for 10-40% of the total mass of the curing component, and the solid content of the aqueous polyurethane emulsion is 25-50%.
Preferably, the epoxy resin in the aqueous epoxy resin emulsion is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenolic aldehyde epoxy resin, hydantoin epoxy resin and imide epoxy resin.
Preferably, the amine curing agent is one or more selected from m-phenylenediamine, diaminodiphenylmethane, isophorone diamine, diethylene triamine, ethylene diamine, hexamethylene diamine, diethylaminopropylamine and m-xylene diamine.
Preferably, the epoxy component comprises: 95-100 parts by mass of a water-based epoxy resin emulsion; 0.1 to 2 parts by mass of a wetting agent; 0.1 to 2 parts by mass of a defoaming agent.
Preferably, the wetting agent is a polyether siloxane based wetting agent; the defoaming agent is an organic silicon defoaming agent.
Preferably, the curing component comprises the following components in percentage by mass: 20-90% of amine curing agent; 0.1-4% of a curing accelerator; 10-40% of aqueous polyurethane emulsion; the balance being water.
Preferably, the curing accelerator is a tertiary amine curing accelerator.
Preferably, the viscosity of the aqueous polyurethane emulsion is 200-1000 mPas.
Preferably, the ratio of the active hydrogen equivalent in the curing component to the epoxy equivalent in the aqueous epoxy resin emulsion is 0.8-1.4: 1.
The invention provides application of the water-based epoxy adhesive in bonding of high-performance fiber bulletproof plates.
Compared with the prior art, the invention provides a water-based epoxy resin adhesive for bonding a high-performance fiber bulletproof plate, which mainly comprises an epoxy component containing water-based epoxy resin emulsion and a curing component containing an amine curing agent, wherein the curing component also comprises water-based polyurethane emulsion, the water-based polyurethane emulsion accounts for 10-40% of the total mass of the curing component, and the solid content of the water-based polyurethane emulsion is 25-50%. The invention adopts an epoxy system in the form of aqueous epoxy resin emulsion, and has good adhesive property, excellent hardness and rigidity. In addition, a certain amount of waterborne polyurethane emulsion components are introduced to toughen the epoxy resin matrix, so that the epoxy resin is good in effect and more environment-friendly. The high-performance fiber bulletproof plate bonded by the adhesive can obtain excellent impact resistance, reduce the depth of recess after bullet impact and improve the bulletproof effect on the premise of ensuring enough bonding strength, adhesive layer hardness and rigidity.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a water-based epoxy adhesive, which comprises the following components: an epoxy component and a curing component;
the epoxy component comprises a waterborne epoxy resin emulsion; the curing component comprises an amine curing agent and an aqueous polyurethane emulsion, wherein the aqueous polyurethane emulsion accounts for 10-40% of the total mass of the curing component, and the solid content of the aqueous polyurethane emulsion is 25-50%.
The high-performance fiber bulletproof plate prepared by the adhesive provided by the invention has high bonding strength, good rigidity, difficult deformation and full play of the bulletproof effect of the high-performance fiber.
The waterborne epoxy adhesive provided by the embodiment of the invention mainly comprises a component A (epoxy component) containing waterborne epoxy resin emulsion and a component B (curing component) containing an amine curing agent. In the present invention, the epoxy component comprises an aqueous epoxy resin emulsion, i.e., in the form of an aqueous emulsion of an epoxy resin, wherein the epoxy resin is the resin matrix component of the adhesive. The invention adopts an epoxy system with good adhesive property, excellent hardness and rigidity, and has lower cost.
In the aqueous epoxy resin emulsion, the epoxy resin can be selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenolic aldehyde epoxy resin, hydantoin epoxy resin and imide epoxy resin. Bisphenol A (bisphenol propane) epoxy resin is generally prepared by polycondensation of bisphenol A and epichlorohydrin under the action of an alkaline catalyst, and has the advantages of readily available raw materials, low cost and wide application. Bisphenol F epoxy resin, abbreviated as DGEBF resin, and bisphenol S epoxy resin, abbreviated as DGEBS resin, belong to glycidyl ether epoxy resins. The novolac epoxy resin is also called F type epoxy resin, and belongs to bifunctional epoxy resin; the preparation method comprises the following steps: phenol and formaldehyde are subjected to polycondensation reaction in an acidic medium to obtain the novolac resin, and the novolac resin and excessive propylene oxide are subjected to polycondensation reaction in the presence of sodium hydroxide to obtain the epoxy novolac resin. The hydantoin epoxy resin is a novel special epoxy resin containing hydantoin heterocycles and obtained by glycidating hydantoin or derivatives thereof; the imide epoxy resin is a polyimide modified epoxy resin.
The source of the epoxy resin is not particularly limited, and for example, commercially available epoxy resins such as E44 to E53 can be used. The epoxy equivalent or the epoxy value is one of important characteristic indexes of the epoxy resin, the epoxy equivalent refers to the mass gram of the epoxy resin containing 1mol of epoxy groups, and the epoxy equivalent can be obtained by testing according to an epoxy value hydrochloric acid-acetone method or a quaternary ammonium bromide titration method; the epoxy value is the number of moles of epoxy groups in 100g of the epoxy resin.
The component A in the embodiment of the invention is prepared by adopting a mechanical emulsification mode, namely, the epoxy resin is ground by a ball mill, then the emulsifier aqueous solution is added, and the epoxy resin particles are dispersed in water by high-speed stirring. According to the embodiment of the invention, a certain amount of epoxy resin can be put into a dispersion machine, the emulsifier and water are added, and the aqueous epoxy resin emulsion is obtained by dispersion under the action of high-speed stirring. The invention has no special restriction on the types and the like of the emulsifying agents, and the emulsifying agents can be selected from the commercially available emulsifying agents, and the emulsifying agent OP-10 is preferably adopted; the solid content of the water-based epoxy resin emulsion can be 40-55%.
In some embodiments of the invention, the epoxy component comprises: 95-100 parts by mass of a water-based epoxy resin emulsion; 0.1 to 2 parts by mass of a wetting agent; 0.1 to 2 mass% of a defoaming agent. According to the embodiment of the invention, a certain amount of wetting agent and defoaming agent can be respectively added into the water-based epoxy resin emulsion, and the mixture is stirred to obtain the component A. The sources of the auxiliary agents are not particularly limited, and corresponding commercial products can be adopted. The wetting agent is preferably a polyether siloxane wetting agent, such as a wetting agent BYK-340, and the using amount is preferably 0.5-1.5 parts by mass. The defoaming agent is preferably an organic silicon defoaming agent, such as a defoaming agent BYK-306, and the using amount is preferably 0.5-1.5 parts by mass.
The waterborne epoxy adhesive provided by the invention comprises a curing component, wherein the curing component comprises an amine curing agent and a waterborne polyurethane emulsion. The amine curing agent is a binary or polybasic amine, comprises aliphatic amine, aromatic amine and the like, can be selected from one or more of m-phenylenediamine, diaminodiphenylmethane, isophorone diamine, diethylenetriamine, ethylenediamine, hexamethylene diamine, diethylaminopropylamine and m-xylene diamine, and is preferably diethylenetriamine, ethylenediamine or isophorone diamine.
The curing component also comprises aqueous polyurethane emulsion, wherein the aqueous polyurethane emulsion is in the form of aqueous emulsion of the polyurethane component, and is toughening resin emulsion and a toughening part. The polyurethane component is introduced to toughen the epoxy resin matrix, so that the problem that the conventional epoxy resin only has rigidity and hardness but has insufficient toughness is solved.
The polyurethane has a soft and hard block structure, so that the performance can be designed, and a product with high wear resistance, high bonding strength and excellent high and low temperature resistance can be obtained by adjusting the structure. The waterborne polyurethane emulsion is added into the system, so that the toughness of a glue layer is mainly improved, the product has enough shock resistance, and the solvent resistance and high and low temperature resistance are improved. However, the epoxy system and the polyurethane system are incompatible with each other in the conventional solvent system, and the low-VOCS more environment-friendly water-based system adopted by the invention well solves the problems in the form of water-based resin blending. In addition, in the system of the present invention, toughening modification by adding a solvent-based liquid rubber or the like cannot be performed.
In addition, the solid content of the waterborne polyurethane emulsion is 25-50%, preferably 35-40%, and the solid content of the waterborne polyurethane emulsion accounts for 10-40% of the total mass of the curing components. In the embodiment of the invention, a commercially available water-based polyurethane emulsion product, such as one or a mixture of several of Dispercoll U53, X1034, AH-0201 and AH-0203, is adopted, and the toughening component ensures good tensile strength and elongation at break. The resin system type in the aqueous polyurethane emulsion is polyester type, polyether type or polyester-polyether mixed type, the viscosity range can be adjusted by a thickening agent, and the optimal viscosity range is 200-1000 mPa & s (20 ℃); the viscosity is measured at room temperature, for example 20 c, which is well known to the person skilled in the art.
In a specific embodiment of the present invention, the curing component comprises the following components in percentage by mass: 20-90% of amine curing agent; 0.1-4% of a curing accelerator; 10-40% of aqueous polyurethane emulsion; the remainder being water. According to the embodiment of the invention, a certain amount of amine curing agent and curing accelerator can be added into a dispersion machine, after uniform stirring, a proper amount of aqueous polyurethane emulsion is added, stirring is continued for a certain time, and water is added to 100% to obtain the component B (namely the curing component).
Wherein the content of the amine curing agent is preferably 30-70%. The curing accelerator can accelerate the curing crosslinking reaction, and is preferably a tertiary amine curing accelerator; a representative tertiary amine is DMP-30 (i.e., 2,4, 6-tris [ (dimethylamino) methyl ] phenol). The amount of the curing accelerator is preferably 1-3%; the preferable using amount of the water-based polyurethane emulsion is 15-35%. The solid content of the curing component can be 30-70%; the solid content is the percentage of the solid mass content.
In the embodiment of the invention, the ratio of the component A to the component B is calculated according to the epoxy equivalent in the component A and the active hydrogen equivalent in the component B, wherein the active hydrogen equivalent in the component B/the epoxy equivalent in the component A is 0.8-1.4: 1, the proportion is preferably 0.9-1.3: 1. wherein the active hydrogen is obtained by calculation according to the addition amount of the amine curing agent added in the curing component. According to the proportion of equivalent of epoxy group and active hydrogen, the component A and the component B are mixed to obtain the waterborne epoxy adhesive for bonding the high-performance fiber bulletproof plate.
The invention provides the application of the water-based epoxy adhesive in the bonding of high-performance fiber bulletproof plates; that is, embodiments of the present invention provide a high performance fiber ballistic panel, which is coated with the above-described aqueous epoxy adhesive.
The invention has no special limitation on the type, preparation and the like of the high-performance fiber bulletproof plate; in the high-performance fiber bulletproof plate provided by the embodiment of the invention, the high-performance fiber fabric can be aramid fiber fabric, ultra-high molecular weight polyethylene fiber fabric, PBO fiber (poly-p-phenylene benzoxazole fiber) fabric and the like. The dosage range of the water-based epoxy adhesive is the unidirectional cloth cover density5-15% by weight, with an areal density in the range of 35g/m2-85g/m2(ii) a The unidirectional cloth is subjected to orthogonal treatment and then laminated, and the total areal density is 5g/m2-8g/m2Hot-press molding is carried out by a high-temperature vulcanizing machine under the conditions of high temperature of 120-135 ℃ and curing time of 2.5-3 hours under the pressure of 30 MPa.
The high-performance fiber bulletproof plate prepared by the embodiment of the invention has the advantages of high bonding strength, good rigidity, difficult deformation, excellent impact resistance, small concave depth after impact and excellent bulletproof effect.
For further understanding of the present application, the following examples are provided to specifically describe the waterborne epoxy adhesive provided herein and its application in the bonding of high performance fiber armor.
Example 1
30 parts by mass of bisphenol A type epoxy resin E51, 3 parts by mass of emulsifier OP-10 and 65 parts by mass of water are put into a dispersion machine and dispersed into aqueous epoxy resin emulsion under the action of high-speed stirring; and respectively adding 1 part by mass of wetting agent BYK-340 and 1 part by mass of defoaming agent BYK-306, and continuously stirring for 10 minutes to obtain a component A.
60 parts by mass of an amine curing agent diethylenetriamine and 2 parts by mass of a curing accelerator DMP-30 are put into a dispersion machine, and after stirring uniformly, 30 parts by mass of waterborne polyurethane DispercollU53 which is a product sold in the Bayer company is added, stirring is continued for 10 minutes, and water is added to 100 parts by mass, so that a component B is obtained.
Based on the epoxy group and active hydrogen equivalent of 1: and 1.2, mixing the component A and the component B to obtain the adhesive for bonding the high-performance fiber bulletproof plate.
Example 2
Adding 35 parts by mass of bisphenol A type epoxy resin E44, 3 parts by mass of emulsifier OP-10 and 60 parts by mass of water into a dispersion machine, and dispersing into a water-based epoxy resin emulsion under the action of high-speed stirring; and respectively adding 1 part by mass of wetting agent BYK-340 and 1 part by mass of defoaming agent BYK-306, and continuously stirring for 10 minutes to obtain a component A.
Adding 55 parts by mass of amine curing agent isophorone diamine and 2 parts by mass of curing accelerator DMP-30 into a dispersion machine, uniformly stirring, adding 25 parts by mass of waterborne polyurethane AH-0201 which is a commercial product of Anda Huatai company, continuously stirring for 10 minutes, and adding water to 100 parts by mass to obtain a component B.
Based on the epoxy group and active hydrogen equivalent of 1: 1.1, mixing the component A and the component B to obtain the adhesive for bonding the high-performance fiber bulletproof plate.
Example 3
Adding 32 parts by mass of bisphenol A type epoxy resin E53, 3 parts by mass of emulsifier OP-10 and 65 parts by mass of water into a dispersion machine, and dispersing into a water-based epoxy resin emulsion under the action of high-speed stirring; and respectively adding 1 part by mass of wetting agent BYK-340 and 1 part by mass of defoaming agent BYK306, and continuously stirring for 10 minutes to obtain a component A.
Adding 55 parts by mass of amine curing agent ethylenediamine and 2 parts by mass of curing accelerator DMP-30 into a dispersion machine, uniformly stirring, adding 32 parts by mass of waterborne polyurethane AH-0203 commercially available from the company Anthemis, continuously stirring for 10 minutes, and adding water to 100 parts by mass to obtain a component B.
Based on the epoxy group and active hydrogen equivalent of 1: 1.1, mixing the component A and the component B to obtain the adhesive for bonding the high-performance fiber bulletproof plate.
Example 4
The adhesive obtained in the embodiment 1-3 is used for bonding a high-performance fiber bulletproof plate; sample preparation according to the model of experimental equipment, cutting according to the preset model to obtain the sample with the surface density of 5kg/m2The ballistic panel of (a) was used in the V50 test; further, the surface density was 17kg/m2The ballistic panel of (2) was used in the M80 test. In addition, the existing fiber bulletproof plate is used as a comparison 1, and no water-based polyurethane emulsion is added as a comparison 2; the bulletproof performance test is in accordance with GA 950-201 l 'test method for bulletproof materials and products V50', and the test requirement of III class M80 in NIJ01.01.06.
The test results were as follows:
table 1 test results of the high performance fiber bulletproof plate prepared in the embodiment of the present invention
| Item | Unit of | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Hardness of the film | Shore D | 81 | 83 | 82 | 76 | 84 |
| V50 value | m/s | 615 | 618 | 612 | 580 | 630 |
| BFS recess | mm | 36.1 | 34.5 | 35.6 | 42 | 34.1 |
Wherein the fiber is PE fiber; comparative 1 is a fiber bulletproof plate made of pure waterborne polyurethane adhesive;
comparative 2 is a fiber ballistic panel prepared from example 1 as a comparative without the addition of an aqueous polyurethane emulsion.
According to the detection result of the prepared high-performance fiber bulletproof plate, the forming hardness of the glue film is increased by 7% -10% compared with that of the glue film 1, and after the glue film is compounded with the ultrahigh molecular weight fiber, the multilayer superposed fiber bulletproof plate is formed. The V50 value is an important index of the reaction bulletproof performance, and it can be seen from the table that the V50 values of examples 1-3 are 6% higher than the V50 value of comparative example 1; the BFS sinking aspect is reduced by 14-17%, and the effect is obvious. Comparative 2 since no toughening emulsion was added, although the hardness was higher than examples 1 to 3 and comparative 1, the bonding force between layers was poor and brittleness became strong, and the synergy was poor at the time of bullet proof impact, resulting in a decrease in the value of V50 and a sharp increase in dishing. Therefore, the high-performance fiber bulletproof plate prepared by the aqueous epoxy adhesive has excellent impact resistance and improved bulletproof effect on the premise of ensuring enough bonding strength, adhesive layer hardness and rigidity.
The above description is only a preferred embodiment of the present invention, and it should be noted that various modifications to these embodiments can be implemented by those skilled in the art without departing from the technical principle of the present invention, and these modifications should be construed as the scope of the present invention.
Claims (10)
1. An aqueous epoxy adhesive for ballistic panels comprising: an epoxy component and a curing component;
the epoxy component comprises a waterborne epoxy resin emulsion; the curing component comprises an amine curing agent and an aqueous polyurethane emulsion, wherein the aqueous polyurethane emulsion accounts for 10-40% of the total mass of the curing component, and the solid content of the aqueous polyurethane emulsion is 25-50%.
2. The aqueous epoxy adhesive according to claim 1, wherein the epoxy resin in the aqueous epoxy resin emulsion is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenolic epoxy resin, hydantoin epoxy resin and imide epoxy resin.
3. The aqueous epoxy adhesive according to claim 1, wherein the amine curing agent is one or more selected from m-phenylenediamine, diaminodiphenylmethane, isophorone diamine, diethylene triamine, ethylene diamine, hexamethylene diamine, diethylaminopropylamine, and m-xylene diamine.
4. The aqueous epoxy adhesive of claim 1, wherein the epoxy component comprises: 95-100 parts by mass of a water-based epoxy resin emulsion; 0.1 to 2 parts by mass of a wetting agent; 0.1 to 2 parts by mass of a defoaming agent.
5. The aqueous epoxy adhesive of claim 4 wherein the wetting agent is a polyether siloxane based wetting agent; the defoaming agent is an organic silicon defoaming agent.
6. The aqueous epoxy adhesive according to claim 1, wherein the curing component comprises the following components in percentage by mass: 20-90% of amine curing agent; 0.1-4% of a curing accelerator; 10-40% of aqueous polyurethane emulsion; the balance being water.
7. The aqueous epoxy adhesive according to claim 6, wherein the curing accelerator is a tertiary amine curing accelerator.
8. The aqueous epoxy adhesive according to claim 6, wherein the viscosity of the aqueous polyurethane emulsion is 200 to 1000 mPas.
9. The aqueous epoxy adhesive according to any one of claims 1 to 8, wherein the ratio of the active hydrogen equivalent in the curing component to the epoxy equivalent in the aqueous epoxy resin emulsion is 0.8 to 1.4: 1.
10. Use of the aqueous epoxy adhesive according to any one of claims 1 to 9 for bonding high-performance fiber bulletproof plates.
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| CN109735278A (en) | 2019-05-10 |
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