CN103450822A - Thermosetting membrane for adhesion of bulletproof fiber and processing method of thermosetting membrane - Google Patents
Thermosetting membrane for adhesion of bulletproof fiber and processing method of thermosetting membrane Download PDFInfo
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- CN103450822A CN103450822A CN2013104140177A CN201310414017A CN103450822A CN 103450822 A CN103450822 A CN 103450822A CN 2013104140177 A CN2013104140177 A CN 2013104140177A CN 201310414017 A CN201310414017 A CN 201310414017A CN 103450822 A CN103450822 A CN 103450822A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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Abstract
The invention discloses a thermosetting membrane for the adhesion of bulletproof fiber and a processing method of the thermosetting membrane, and belongs to the field of high-molecular materials. The thermosetting membrane is prepared from the following materials in parts by weight: at least (a) 40-50 parts of film-forming resin, (b) 13-15 parts of plasticizing agents for the film-forming resin, (c) 30-45 parts by weight of curable resin, (d) 5-10 parts of cured resin curing agents and (e) 0.05-2 parts of surface treating agents. The method disclosed by the invention can be used for preparing the thermosetting membrane with good film-forming property, the uniform accuracy of +/- 0.001 mm, the crosslinking degree less than 5% and the thickness of 0.05-0.2 mm, has the advantages of simple preparation process, no solvent volatilization, good sizing uniformity, uniformity in interface adhesion, and the like and fundamentally overcomes the defects of low production efficiency, serious environment pollution, poor sizing uniformity, product fiber embrittlement and the like which are brought by using a wet method process of a liquid adhesive material. The thermosetting membrane disclosed by the invention is mainly applied to the adhesion of single materials, namely bulletproof aramid fiber materials, carbon fibers and the like, or composite materials and is applied to the fields of aviation, war industry, civil use and the like in production of bulletproof clothes, bulletproof helmets and the like.
Description
Technical field
The present invention relates to a kind of preparation for processing of macromolecule member material, be specifically related to a kind of production technique for the bonding use of ballistic fiber heat cured film, belong to polymeric material field.
Background technology
In recent years, along with the fast development of Chinese national economy, especially the complexity of international environment is handed over more, and aircraft industry, war industry develop particularly rapid, and the research and development that novel material substitutes traditional material have become focus.The application that lightweight composite materials substitutes steel plate launches gradually in space flight, aviation, shellproof field, particularly is applied in ballistic composite and goods.Comprise that the lightweight bulletproof composite materials such as flak jackets, bulletproof halmet, shellproof target are all that the layer laminates that adopts the single or multiple matrix materials such as shellproof aramid fiber material, carbon fiber, glass fibre, stupalith, metallic substance to prepare processes, when being subject to powerful impact, appropriate deformation and layered effect will be produced, the impact function of dissipation and transmission bullet, can effectively stop penetrating of alluvium.
At present, the domestic shellproof glue-applying technique of weaving cotton cloth all adopts the glue-applying techniques such as the wet method glue spraying, blade coating, preimpregnation, hand paste of liquid adhesives, this class technique circuit is long, production efficiency is low, need carry out the solvent seasoning devolatilization, bring the problems such as environmental pollution, maximum defect is that wet method gluing meeting makes glue enter the fibrous inside of weaving cotton cloth, and causes the applying glue uniformity coefficient poor; Simultaneously, make the fiber hardening after glue curing, and lose the snappiness of weaving cotton cloth, ballistic performance is descended.
At present, adopt in the world the dry method glue-applying technique of heat cured film to prepare the bulletproof composite material and gradually become trend, this technique can fundamentally solve the defect that the wet processing that uses the liquid adhesives brings, and has manufacture craft simple, significantly improves production efficiency; Without drying process, solvent-free generation, stop environmental pollution; Maximum characteristics are that applying glue good evenness, bonding interface are even, make adhesive layer clear with the separation of weaving cotton cloth, and avoid Resin adhesive to enter the fibrous inside of weaving cotton cloth, thus performance adhesive layer and the efficiency of weaving cotton cloth separately.
The Patents of the heat cured film still do not used for mould pressing process in the world at present, the formula of grasp heat cured film and the technical information of process for processing technology are still in maintaining secrecy.
Summary of the invention
In order fundamentally to have solved, the production efficiency that in the prior art, the wet processing of use liquid adhesives brings is low, the defects such as environmental pollution large, the applying glue uniformity coefficient is poor, goods tendering of fiber.The purpose of this invention is to provide a kind of prescription and technique that can substitute the heat cured film for mould pressing process of liquid adhesives.The good film-forming property of the heat cured film that utilizes prescription of the present invention and technique to make, evenly precision is at positive and negative 0.001mm, degree of crosslinking is less than 5%, thickness is 0.05~0.2mm, described preparation technology has the advantages such as simple, the solvent-free volatilization of manufacture craft, applying glue good evenness, bonding interface be even, this heat cured film can be applied to the bonding of the single-material such as shellproof aramid fiber material, carbon fiber or matrix material, therefore can be widely used in producing the aviations such as flak jackets, bulletproof halmet, military project and the field such as civilian.
For realizing purpose of the present invention, technical scheme of the present invention is:
A kind of for the bonding heat cured film of using of ballistic fiber, its by comprise at least (a) but the cured resin solidifying agent of film-forming resin (b) 13~15 weight parts softening agent (c) 30~45 weight part curable resin (d) 5~10 weight parts for film-forming resin of 40~50 weight parts and (e) surface treatment agent of 0.05~2 weight part is formulated by ratio of weight and the number of copies.Wherein:
But described film-forming resin is selected from one or both in polyvinyl acetal, ethylene-vinyl acetate copolymer (EVA); Described polyvinyl acetal is selected from one or more combinations in polyvinyl butyral acetal (PVB), polyvinyl formal (PVF), polyvinylacetal (PVA) or polyvinyl formal acetal.
Described film-forming resin softening agent is selected from one or more combinations in Uniflex DBS, Triethyleneglycol di 2 ethylhexanoate, dihexyl adipate.
Described curable resin is selected from a kind of or two or more combinations in resol, benzoxazine colophony, aminoresin, silicone resin, thermosetting acrylic resin.
Described resin curing agent is selected from a kind of in epoxy resin, hexamethylenetetramine.
Described surface treatment agent is selected from one or both in rosin, silane coupling agent.
A kind of bonding method with heat cured film of above-mentioned ballistic fiber for preparing, it comprises the steps: to take the component of recipe quantity fully mixing, granulation, extruded on screw extrusion press and can be obtained heat cured film of the present invention, while wherein extruding, the processing condition of screw extrusion press are: mold temperature is 80~130 ℃, forming pressure is 1~4MPa, and molding time is 2~10 minutes.
The present invention also provides a kind of application of heat cured film described above, i.e. the application of described heat cured film in ballistic fiber is bonding.Described ballistic fiber is the single-material that comprises in shellproof aramid fiber material or carbon fiber any one, or the matrix material for comprising shellproof aramid fiber material or carbon fiber.Performance test to the heat cured film for preparing respectively in embodiment of the present invention 1-3 shows, adopt heat resistance and the ageing-resistant performance of the preparation-obtained heat cured film of the present invention strong, percent thermal shrinkage at high temperature is little, ballistic fiber and the stripping strength between it are large, show that it can mortise, the fiber bonding firmly.Its area density is little in addition, not obvious gaining in weight while boning for ballistic fiber.Above index shows, the present invention can increase the work-ing life of ballistic resistant products when bonding for ballistic fiber greatly, and in use procedure to the opposing of extreme environment.The area density of the heat cured film wherein prepared by embodiment 4 preparation prescriptions and technique is the lightest, and it is the highest with the stripping strength of spinning wheel material and carbon fiber, is most preferred embodiment of the present invention.
The present invention, by regulating resin type selecting and proportioning, gives full play to the characteristic of property of various materials, produces the multiple heat cured film that adapts to the different demands in market, improves the production technique fallen behind at present and the over-all properties that improves ballistic composite.The technical superiority that technical solution of the present invention compared with prior art obtains mainly comprises following 5 points:
(1) the present invention is by screening and optimization to correlation parameter, determined technical indicator and the proportioning parameter of each raw material in the compound system, make each component in system there is best consistency, stability and processibility, meet the filming technology requirement, and take into account the optimum of bonding strength, stripping strength, molded curing, temperature tolerance, snappiness, bulletproof ability.Heat cured film prepared by this formula system has excellent cohesive strength and mechanical property, can give the ballistic fiber goods and produce appropriate deformation and layered effect when being subject to attack, the impact function of dissipation and transmission bullet.
(2), adopt the low temperature mixing technology, the multiple polymers that reaches different processing characteristics is fully mixed, and the degree of crosslinking of heat cured film≤5%, this heat cured film can be given cementability and the pliable and tough deformation behavior of fibre product excellence, improves the bulletproof ability of goods.
(3), the present invention is by the optimization design to extruding the masking moulding process and to the optimization of different processing factors, determine the contour machining procedure of stably manufactured heat cured film, be that the moulding temperature is 80~130 ℃, forming pressure is 1~4MPa, molding time is 2~10 minutes. this technique can make good film-forming property, evenly precision is at positive and negative 0.001mm, and degree of crosslinking is less than 5%, the heat cured film that thickness is 0.05~0.2mm; When reaching ultra-thin technological design, guaranteed that the indexs such as the high impact strength of product and high tenacity all meet the requirements.
(4), the transverse and longitudinal shrinking percentage of the masking of the heat cured film that adopts prescription of the present invention and technique to prepare all≤3%, and high temperature resistant ageing-resistant performance excellence, can effectively reduce deformation and the loss of product when bonding for ballistic resistant products.
(5), according to fiber laminar composite target plate structure design, from energy absorption and ripple, propagate and the requirement of shellproof laminar composite to matrix material content analyzed in two aspects of complex effect, heat cured film with suitable interfacial adhesion strength is provided, has made the bulletproof composite material there is good resistance to impact shock and snappiness.
Embodiment
Following content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Embodiment 1
Be prepared as follows a kind of heat cured film of proportioning:
The production technique of heat cured film is as follows:
The silane coupling agent of the epoxy resin of the thermosetting acrylic resin of the resol of the Triethyleneglycol di 2 ethylhexanoate of the PVF of 40 parts by weight, 11 parts by weight, 30 parts by weight, 10 parts by weight, 8 parts by weight, 1 parts by weight is weighed up and puts into mixing machine and stir, then extruding pelletization.Then, in 35 type extruder for shaping, technique is that mold temperature is 120 ℃, and forming pressure is 3MPa, and molding time is 8 minutes.
This technique can make good film-forming property, and evenly precision is at positive and negative 0.001mm, and degree of crosslinking is less than 5%, the heat cured film that thickness is 0.05~0.2mm.The performance of the heat cured film made under above-mentioned resin formula and processing parameter condition is as shown in table 1.
The technical indicator of the heat cured film that table 1 embodiment 1 prepares
Embodiment 2
Be prepared as follows a kind of heat cured film of proportioning:
The production technique of heat cured film is as follows:
The silane coupling agent of the epoxy resin of the resol of the Uniflex DBS of the PVB of 50 parts by weight, 15 parts by weight, 30 parts by weight, 4 parts by weight, 1 parts by weight is weighed up and puts into mixing machine and stir, then extruding pelletization.Then, in 35 type extruder for shaping, technique is that moulding humidity is 100 ℃, and forming pressure is 2MPa, and molding time is 4 minutes.
This technique can make good film-forming property, and evenly precision is at positive and negative 0.001mm, and degree of crosslinking is less than 5%, the heat cured film that thickness is 0.05~0.2mm.The performance of the heat cured film made under above-mentioned resin formula and processing parameter condition is as shown in table 1.
The technical indicator of the heat cured film that table 2 embodiment 2 prepares
Embodiment 3
Be prepared as follows a kind of heat cured film of proportioning:
The production technique of heat cured film is as follows:
The silane coupling agent of the hexamethylenetetramine of the silicone resin of the benzoxazine colophony of the dihexyl adipate of the PVFA of 40 parts by weight, 13 parts by weight, 25 parts by weight, 15 parts by weight, 6 parts by weight, 1 parts by weight is weighed up and puts into mixing machine and stir, then extruding pelletization.Then, in 35 type extruder for shaping, technique is that mold temperature is 130 ℃, and forming pressure is 4MPa, and molding time is 10 minutes.
This technique can make good film-forming property, and evenly precision is at positive and negative 0.001mm, and degree of crosslinking is less than 5%, the heat cured film that thickness is 0.05~0.2mm.The performance of the heat cured film made under above-mentioned resin formula and processing parameter condition is as shown in table 1.
The technical indicator of the heat cured film that table 3 embodiment 3 prepares
Embodiment 4
Be prepared as follows a kind of heat cured film of proportioning:
The production technique of heat cured film is as follows:
The silane coupling agent of the epoxy resin of the resol of the aminoresin of the dihexyl adipate of the PVA of the EVA of 10 parts by weight, 40 parts by weight, 13 parts by weight, 20 parts by weight, 10 parts by weight, 6 parts by weight, 1 parts by weight is weighed up and puts into mixing machine and stir, then extruding pelletization.Then, in 35 type extruder for shaping, technique is that mold temperature is 80 ℃, and forming pressure is 2MPa, and molding time is 2 minutes.
This technique can make good film-forming property, and evenly precision is at positive and negative 0.001mm, and degree of crosslinking is less than 5%, the heat cured film that thickness is 0.05~0.2mm.The performance of the heat cured film made under above-mentioned resin formula and processing parameter condition is as shown in table 1.
The technical indicator of the heat cured film that table 4 embodiment 4 prepares
Performance test to the heat cured film for preparing respectively in embodiment of the present invention 1-4 shows, adopt heat resistance and the ageing-resistant performance of the preparation-obtained heat cured film of the present invention strong, percent thermal shrinkage at high temperature is little, ballistic fiber and the stripping strength between it are large, show that it can mortise, the fiber bonding firmly.Its area density is little in addition, not obvious gaining in weight while boning for ballistic fiber.Above index shows, the present invention can increase the work-ing life of ballistic resistant products when bonding for ballistic fiber greatly, and in use procedure to the opposing of extreme environment.The area density of the heat cured film wherein prepared by embodiment 4 preparation prescriptions and technique is the lightest, and it is the highest with the stripping strength of spinning wheel material and carbon fiber, is most preferred embodiment of the present invention.
Above-described embodiment is only preferred embodiment of the present invention, and it not imposes any restrictions technical scope of the present invention, therefore any trickle modification of every foundation technical spirit of the present invention, equivalent variations and modification all still belong in the scope of technical solution of the present invention.
Claims (10)
1. one kind for the bonding heat cured film of using of ballistic fiber, it is characterized in that, but it is made by the cured resin solidifying agent of the film-forming resin that comprises 40~50 weight parts, 13~15 weight parts softening agent, 30~45 weight part curable resins, 5~10 weight parts for film-forming resin and the surface treatment agent of 0.05~2 weight part.
2. heat cured film according to claim 1 is characterized in that: but described film-forming resin is selected from one or both in polyvinyl acetal, ethylene-vinyl acetate copolymer; Described polyvinyl acetal is selected from one or more combinations in polyvinyl butyral acetal (PVB), polyvinyl formal (PVF), polyvinylacetal (PVA) or polyvinyl formal acetal (PVFA).
3. heat cured film according to claim 1, it is characterized in that: described film-forming resin softening agent is selected from one or more combinations in Uniflex DBS, Triethyleneglycol di 2 ethylhexanoate, dihexyl adipate.
4. heat cured film according to claim 1, it is characterized in that: described curable resin is selected from a kind of or two or more combinations in resol, benzoxazine colophony, aminoresin, silicone resin, thermosetting acrylic resin.
5. heat cured film according to claim 1 is characterized in that: described resin curing agent is selected from a kind of in epoxy resin, hexamethylenetetramine.
6. heat cured film according to claim 1 is characterized in that: described surface treatment agent is selected from one or both in rosin, silane coupling agent and closes.
7. claim 1-6 is arbitrary described for the bonding preparation method with heat cured film of ballistic fiber, it is characterized in that: but take respectively the film-forming resin of 40~50 weight parts, the cured resin solidifying agent of 13~15 weight parts softening agent, 30~45 weight part curable resins, 5~10 weight parts for film-forming resin and the surface treatment agent of 0.05~2 weight part, fully mix, granulation, on screw extrusion press, extruded can obtain of the present invention for the bonding heat cured film of using of ballistic fiber.
8. preparation method as claimed in claim 7, it is characterized in that: while extruding, the processing condition of screw extrusion press are: mold temperature is 80~130 ℃, and forming pressure is 1~4MPa, and molding time is 2~10 minutes.
9. the purposes of the arbitrary described heat cured film of claim 1-6 in ballistic fiber is bonding.
10. purposes as claimed in claim 9 is characterized in that: described ballistic fiber is the single-material that comprises in shellproof aramid fiber material or carbon fiber any one, or the matrix material for comprising shellproof aramid fiber material or carbon fiber.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105505270A (en) * | 2016-01-21 | 2016-04-20 | 苏州法斯特信息科技有限公司 | Binder for plastic floor and preparation method of binder |
CN106046780A (en) * | 2016-06-03 | 2016-10-26 | 中蓝晨光化工研究设计院有限公司 | Bulletproofing material with thermoset epoxy resin and preparation method thereof |
CN110530207A (en) * | 2019-09-30 | 2019-12-03 | 重庆盾之王安防设备技术研究院有限公司 | A kind of ultralight nonmetal bulletproof helmet |
CN113831877A (en) * | 2021-09-27 | 2021-12-24 | 湖北晟特新材料有限公司 | Modified epoxy resin adhesive and application thereof in hard mica plate |
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US4125669A (en) * | 1976-02-19 | 1978-11-14 | Deutsche Gold-Und Silber-Scheideanstalt Vormals Roessler | Bulletproof laminated safety glass and process for production |
CN1108177A (en) * | 1993-09-06 | 1995-09-13 | 吕特格斯工厂有限公司 | Combined material and preparation of same and adhesive used for same |
CN100999179A (en) * | 2007-01-12 | 2007-07-18 | 张海龙 | Pricking resistant, bullet-proof, leakage-proof safety tyre, its manufacturing method and its used polymer leakage-proof mending material |
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2013
- 2013-09-12 CN CN2013104140177A patent/CN103450822A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US4125669A (en) * | 1976-02-19 | 1978-11-14 | Deutsche Gold-Und Silber-Scheideanstalt Vormals Roessler | Bulletproof laminated safety glass and process for production |
CN1108177A (en) * | 1993-09-06 | 1995-09-13 | 吕特格斯工厂有限公司 | Combined material and preparation of same and adhesive used for same |
CN100999179A (en) * | 2007-01-12 | 2007-07-18 | 张海龙 | Pricking resistant, bullet-proof, leakage-proof safety tyre, its manufacturing method and its used polymer leakage-proof mending material |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105505270A (en) * | 2016-01-21 | 2016-04-20 | 苏州法斯特信息科技有限公司 | Binder for plastic floor and preparation method of binder |
CN106046780A (en) * | 2016-06-03 | 2016-10-26 | 中蓝晨光化工研究设计院有限公司 | Bulletproofing material with thermoset epoxy resin and preparation method thereof |
CN106046780B (en) * | 2016-06-03 | 2018-09-25 | 中蓝晨光化工研究设计院有限公司 | Introducing has bullet resistant material of thermosetting epoxy resin and preparation method thereof |
CN110530207A (en) * | 2019-09-30 | 2019-12-03 | 重庆盾之王安防设备技术研究院有限公司 | A kind of ultralight nonmetal bulletproof helmet |
CN113831877A (en) * | 2021-09-27 | 2021-12-24 | 湖北晟特新材料有限公司 | Modified epoxy resin adhesive and application thereof in hard mica plate |
CN113831877B (en) * | 2021-09-27 | 2023-08-11 | 湖北晟特新材料有限公司 | Modified epoxy resin adhesive and application thereof in hard mica plate |
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