CN106397803B - A kind of pre-soaking fiber cloth and preparation method thereof - Google Patents
A kind of pre-soaking fiber cloth and preparation method thereof Download PDFInfo
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- CN106397803B CN106397803B CN201510448239.XA CN201510448239A CN106397803B CN 106397803 B CN106397803 B CN 106397803B CN 201510448239 A CN201510448239 A CN 201510448239A CN 106397803 B CN106397803 B CN 106397803B
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Abstract
The present invention relates to pre-soaking fiber cloth fields, disclose a kind of pre-soaking fiber cloth and preparation method thereof, the at least partly surface of the pre-soaking fiber cloth is coated with resin-bonded layer, wherein, there is magnetic chopped strand, and the angle between the magnetic chopped strand and the fiber cloth is greater than 0 ° between the resin-bonded layer and fiber cloth.Pre-soaking fiber cloth of the invention is when being hot pressed into composite board with excellent inter-layer bonding force.
Description
Technical field
The present invention relates to a kind of pre-soaking fiber cloth and preparation method thereof.
Background technique
Currently, pre-soaking fiber cloth is usually that prepreg is used to presoak fiber cloth, it is used pre- in the prior art
Leaching material usually contains unsaturated polyester resin, vinylite, phenylpropyl alcohol oxazines resin, phenolic resin, urea resin, epoxy resin
Or melamine resin etc. is used as main component, is passing through alternately laying heat by presoaking the pre-soaking fiber cloth that the prepreg obtains
When being pressed into composite board, inter-layer bonding force is insufficient.
Summary of the invention
The object of the present invention is to provide a kind of pre-soaking fiber cloth and preparation method thereof, which is being hot pressed into again
With excellent inter-layer bonding force when plywood material.
Present inventors discovered unexpectedly that Thermocurable binder resin and magnetism will be contained in the presence of magnetic field
When the resin combination of chopped strand is infiltrated up in fiber cloth, magnetic chopped strand is inserted into fiber cloth, and the magnetic
Property chopped strand front end can protrude outward, be exposed to the outside of fiber cloth and resin-bonded layer, thus, it is possible to significantly improve
Pre-soaking fiber cloth is hot pressed into inter-layer bonding force when composite board.
As a result, the present invention provides a kind of pre-soaking fiber cloth, at least partly surface of the pre-soaking fiber cloth is coated with resin
Adhesive layer, wherein there is magnetic chopped strand, and the magnetic chopped strand and institute between the resin-bonded layer and fiber cloth
The angle stated between fiber cloth is greater than 0 °.
The present invention also provides the preparation method of above-mentioned pre-soaking fiber cloth, this method are as follows: in the presence of magnetic field, by that will contain
There are Thermocurable binder resin and the resin combination of magnetic chopped strand to be infiltrated up in fiber cloth, then carries out heating solid
Change.
Pre-soaking fiber cloth according to the present invention, when being hot pressed into composite board with excellent inter-layer bonding force.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is the schematic diagram of fibre fabric block X1, X2, X3 in test case 1.
Fig. 2 is the schematic diagram of fibre fabric block Y1, Y2, Y3 in test case 1.
Fig. 3 is the schematic diagram of the hot pressing product XY in test case 1.
Fig. 4 is the schematic diagram of the sample to be tested in test case 1.
Fig. 5 is the schematic diagram that the sample to be tested in test case 1 is tested.
Description of symbols
1:6 layers of fiber cloth
2:2mm thickness aluminium sheet
3:4 layers of fiber cloth
4:2 layers of fiber cloth
5: applied force position
6: fixed position
X1, X2, X3: fibre fabric block
Y1, Y2, Y3: fibre fabric block
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
At least partly surface of pre-soaking fiber cloth provided by the invention is coated with resin-bonded layer, wherein the resin is viscous
Tying between layer and fiber cloth has magnetic chopped strand, and the angle between the magnetic chopped strand and the fiber cloth is greater than
0°。
In the present invention, it is preferred to which all surface of the pre-soaking fiber cloth is coated with resin-bonded layer.
It is excellent for the inter-layer bonding force of the pre-soaking fiber cloth further increased in the case where, according to the invention it is preferred to
Selection of land, the angle between the magnetism chopped strand and the fiber cloth is 30 ° -90 °；It is more preferably 45 ° -90 °, further excellent
65 ° -90 °, particularly preferably 90 ° are selected as, i.e., the described magnetic chopped strand is vertical with the fiber cloth.
In the case where, according to the invention it is preferred to, the magnetism chopped strand has first be inserted in the fiber cloth
Part and the second part being fixed in the resin-bonded layer, that is, the part of above-mentioned magnetism chopped strand is inserted in fiber
In cloth, it is partially located in resin-bonded layer
It according to the present invention, is the purpose for further increasing binding force between each layer, for above-mentioned magnetic chopped strand, length
Degree is preferably 30 μm of -2mm, more preferably 50 μm of -1.5mm, further preferably 50 μm of -1mm.
In the present invention, the diameter of the magnetic chopped strand can change in a big way, described under preferable case
The diameter of section of magnetic chopped strand is 0.5-20 μm, more preferably 1-10 μm.
In the present invention, it is preferred to which the magnetism chopped strand is that magnetic glass fiber, magnetic carbon fiber and magnetic aramid fiber are fine
One of dimension is a variety of.
It can be commercially available as magnetic chopped strand of the invention, such as magnetic glass fiber can be purchased from Jiangyin
City's Amway ties up Textile Co., Ltd..Alternatively, it is also possible at one layer of surface depositional packages of glass fibre, carbon fiber and aramid fiber
It is prepared by magnetisable material (such as ferrite).
In the present invention, the fiber cloth is not particularly limited, material can be the various of routine, for example, tool
Body can be one of glass fabric, carbon cloth and aryl fiber cloth or a variety of, or above-mentioned glass fibre, carbon
The blended cloth of two or more formation in fiber and aramid fiber.
In the present invention, the mass area ratio of above-mentioned fiber cloth is not particularly limited, it specifically can be in larger range
Interior variation, under preferable case, the mass area ratio of the fiber cloth is 20-700g/m2, more preferably 50-300g/m2。
According to the present invention, when pre-soaking fiber cloth to be laminated, the resin-bonded layer is used to combine each pre-soaking fiber cloth
It is integrated.
Above-mentioned resin-bonded layer can be to be consolidated by the resin combination containing Thermocurable binder resin and chopped strand
Change and obtains layer.
It is preferably acrylic resin, epoxy resin, polyurethane resin, polyester tree as the Thermocurable binder resin
It is one or more in rouge, phenylpropyl alcohol oxazines resin, phenolic resin, urea resin and melamine resin.Preferably epoxy resin.
Preferably, the resin combination also contains reactive diluent.It is highly preferred that the solidification relative to 100 parts by weight
Property binder resin, the reactive diluent containing 10-55 parts by weight；It is highly preferred that the curability relative to 100 parts by weight
Binder resin, the reactive diluent containing 13-53 parts by weight.
It is preferably acrylic glycidol ether, butyl glycidyl ether, ethylene glycol pair as reactive diluent described above
Glycidol ether, resorcinol bisglycidyl ether, hexanediol diglycidyl ether, butanediol diglycidyl ether, poly- the third two
One of alcohol diglycidyl ether, neopentylglycol diglycidyl ether and alkyl multicondensed water glycerin ether are a variety of.It is viscous from reducing
It is more excellent to spend effect, the better aspect of fiber prepreg effect is considered, the more preferable reactive diluent is butyl glycidyl
One of ether, butanediol diglycidyl ether, neopentylglycol diglycidyl ether and alkyl multicondensed water glycerin ether are a variety of.Tool
Body, the reactive diluent of the model SM678 of Sanmu Group Co., Ltd., Jiangsu can be used as the reactive diluent
(ingredient is neopentylglycol diglycidyl ether).
In accordance with the present invention it is preferred that the resin combination also contains curing agent.It is highly preferred that relative to 100 parts by weight
Curability binder resin, the curing agent containing 1-55 parts by weight；It is further preferred that relative to 100 parts by weight
Curability binder resin, the curing agent containing 2-50 parts by weight.
As the curing agent various cured curing agent can be used for be commonly used in the art.Preferably diamino hexichol
Methylmethane, m-phenylene diamine (MPD), diamino diphenyl sulfone adipic dihydrazide, dicyandiamide, triethylene diamine, triethylene tetramine, tetrem
Five amine of alkene, diethylaminopropylamine, Meng's alkane diamines, isophorone diamine, N- aminoethyl piperazine, bis- (4- amino -3- methyl cyclohexanes
Base) one of methane and bis- (4- amido cyclohexyl) methane or a variety of.More preferably dicyandiamide.
In accordance with the present invention it is preferred that the resin combination can also contain curing accelerator.It is highly preferred that relative to
The curability binder resin of 100 parts by weight, the curing accelerator containing 0-10 parts by weight；It is further preferred that opposite
In the curability binder resin of 100 parts by weight, the curing accelerator containing 0.9-8.8 parts by weight.
Various curing accelerators that can be commonly used in the art as the curing accelerator.It such as can be organic guanidine
Close one of object, glyoxaline compound and carbamide compounds or a variety of；Preferably glyoxaline compound；More preferably 1- methyl
Imidazoles.
In accordance with the present invention it is preferred that the resin combination can also contain one in defoaming agent, levelling agent and wetting agent
Kind is a variety of.Preferably, relative to the curability binder resin of 100 parts by weight, the infusion, levelling agent and wetting agent contain
Amount is respectively 0-12 parts by weight, more preferably 1.5-11 parts by weight.
Various defoaming agents, levelling agent and wetting that can be commonly used in the art as the defoaming agent, levelling agent and wetting agent
Agent.Preferably, the defoaming agent is poly acrylic acid-poly ether copolymer defoaming agent, organic silicon defoaming agent and organically-modified poly- silicon
One of oxygen alkane defoaming agent and fluorosilicone antifoamant are a variety of；The levelling agent is acrylate, polyether silicone copolymerization
One of object and organic modified polyorganosiloxane are a variety of；The wetting agent is nonionic organic surfactant.Specifically, make
932 defoaming agent of DEGO Airex (fluorosilicone antifoamant) can be used for the defoaming agent.
In addition, in the present invention, under preferable case, the resin-bonded layer with a thickness of 0.02-0.5mm, more preferably
0.1-0.25mm。
, according to the invention it is preferred to which the magnetism chopped strand surface is coated with silane coupling agent.By short in the magnetism
Cut fiber surface and be coated with silane coupling agent, have can and the chemically combined reactive group of fiber surface, can be in fiber and pre-
Get up between resin pickup the effect of function served as bridge, so as to further increase inter-layer bonding force.
Method that can be well known in the art in the method for the magnetic chopped strand surface cladding silane coupling agent, example
It is such as that silane coupling agent and dispersing agent and the mixed spray solution of solvent is dry behind the surface of the magnetic chopped strand.
It can be various silane coupling agents commonly used in this field as the silane coupling agent.Preferably, the silane
Coupling agent be amino silane, epoxy radicals silicone hydride, sulfenyl silane, methacryloxypropyl silane, vinyl silanes, ureido silane and
One of isocyanato silanes are a variety of.Preferably, the silane coupling agent is in amino silane and epoxy radicals silicone hydride
It is one or more.It can be various dispersing agents commonly used in this field, preferably waterglass, tripolyphosphate as the dispersing agent
Sodium, sodium pyrophosphate, triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative, gathers calgon
One of acrylamide, guar gum, aliphatic poly glycol ester and modified polyalkoxide are a variety of.Only as the solvent
Can be well by the silane coupling agent and dispersant solvent, such as can be ethyl alcohol, dimethylbenzene, n-butanol, second
One of glycol butyl ether, butyl acetate, isopropanol, cyclohexanone and methyl iso-butyl ketone (MIBK) are a variety of.
Mixing quality ratio for silane coupling agent, dispersing agent and solvent is preferably 1:0.5-5:50-200；It is especially excellent
It is selected as=1:3:100.
The present invention also provides a kind of preparation methods of pre-soaking fiber cloth, wherein this method are as follows: in the presence of magnetic field, passes through
Resin combination containing Thermocurable binder resin and magnetic chopped strand is infiltrated up in fiber cloth, is then heated
Solidification.
In the preparation method of pre-soaking fiber cloth of the invention, carried out since resin combination is impregnated into the presence of magnetic field,
Therefore, it is arranged in the same direction under magnetic fields included in the magnetic chopped strand of resin combination, in addition,
Be readily inserted into fiber cloth since its diameter of section is smaller so as to pre-soaking fiber cloth in, magnetism be chopped
Fiber is with the shape for the second part for having the first partial being inserted in the fiber cloth and being fixed in the resin-bonded layer
State exists.In addition, the orientation of magnetic chopped strand can be controlled by adjusting the direction in magnetic field, so as to will be magnetic short
The angle cut between fiber and the fiber cloth controls in the range of needs.
For the intensity in above-mentioned magnetic field, as long as the magnetic chopped strand can be made to effectively insert at an angle
In the fiber cloth.Preferably, the magnetic induction intensity is 0.1-1.0 tesla, more preferably 0.3-0.8 tesla.
The preparation method of pre-soaking fiber cloth according to the present invention, in order to which the pre-soaking fiber cloth improved is hot pressed into composite plate
Inter-layer bonding force when material, preferably with respect to the curability binder resin of 100 parts by weight, the magnetic containing 5-50 parts by weight
Property chopped strand；More preferably relative to the curability binder resin of 100 parts by weight, the magnetism containing 8-38 parts by weight is short
Cut fiber.
For above-mentioned magnetic chopped strand, under preferable case, the length is 30 μm of -2mm；In preferred situation, length
Degree is 50 μm of -1.5mm；In the case where further preferably, the length is 50 μm of -1mm.
In the preparation method of pre-soaking fiber cloth of the invention, the diameter of magnetic chopped strand can become in a big way
Dynamic, under preferable case, the diameter of section of the magnetism chopped strand is 0.5-20 μm, more preferably 1-10 μm.
In the preparation method of pre-soaking fiber cloth of the invention, the preferably described magnetic chopped strand be magnetic glass fiber,
It is a kind of in magnetic carbon fiber and magnetic aramid fiber.
It can be commercially available as magnetic chopped strand of the invention, such as magnetic glass fiber can be purchased from Jiangyin
City's Amway ties up Textile Co., Ltd..Alternatively, it is also possible at one layer of surface depositional packages of glass fibre, carbon fiber and aramid fiber
It is prepared by magnetisable material (such as ferrite).
The preparation method of pre-soaking fiber cloth according to the present invention, the resin combination contain the Thermocurable binder
Resin.The Thermocurable binder resin is preferably acrylic resin, epoxy resin, polyurethane resin, polyester resin, phenylpropyl alcohol
It is one or more in oxazines resin, phenolic resin, urea resin and melamine resin.Preferably epoxy resin.
The resin combination also contains reactive diluent.The dosage of the reactive diluent can be the routine of this field
Dosage, relative to the curability binder resin of 100 parts by weight, the reactive diluent containing 10-55 parts by weight；More preferably
Ground, relative to the curability binder resin of 100 parts by weight, the reactive diluent containing 13-53 parts by weight.
The reactive diluent has for dissolving and dispersing film forming matter and participates in film forming in coating film forming procedure instead
It answers, formation does not play the effect that component stays in film.It is preferably acrylic glycidol as reactive diluent described above
Ether, butyl glycidyl ether, ethylene glycol bisglycidyl ether, resorcinol bisglycidyl ether, hexanediol diglycidyl ether,
Butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether and alkyl multicondensed water glycerol
One of ether is a variety of；From reducing, viscosity effect is more excellent, considers the better aspect of fiber prepreg effect, more preferably described
Reactive diluent is butyl glycidyl ether, butanediol diglycidyl ether, neopentylglycol diglycidyl ether and alkyl multicondensed
One of water glycerin ether is a variety of.Specifically, Sanmu Group Co., Ltd., Jiangsu can be used as the reactive diluent
Model SM678 reactive diluent (ingredient is neopentylglycol diglycidyl ether).
The preparation method of pre-soaking fiber cloth according to the present invention, in preferred situation, the resin combination also contains solid
Agent.The dosage of the curing agent can be the conventional amount used of this field, it is preferable that the curability relative to 100 parts by weight is viscous
Tie agent resin, the curing agent containing 1-55 parts by weight；It is further preferred that the curability relative to 100 parts by weight bonds
Agent resin, the curing agent containing 2-50 parts by weight.
As the curing agent various cured curing agent can be used for be commonly used in the art.Preferably diamino hexichol
Methylmethane, m-phenylene diamine (MPD), diamino diphenyl sulfone adipic dihydrazide, dicyandiamide, triethylene diamine, triethylene tetramine, tetrem
Five amine of alkene, diethylaminopropylamine, Meng's alkane diamines, isophorone diamine, N- aminoethyl piperazine, bis- (4- amino -3- methyl cyclohexanes
Base) one of methane and bis- (4- amido cyclohexyl) methane or a variety of.More preferably dicyandiamide.
The preparation method of pre-soaking fiber cloth according to the present invention, in preferred situation, the resin combination also contains solid
Change promotor.The dosage of the curing accelerator can be the conventional amount used of this field, it is preferable that relative to 100 parts by weight
Curability binder resin, the curing accelerator containing 0-10 parts by weight；It is further preferred that relative to 100 parts by weight
Curability binder resin, the curing accelerator containing 0.9-8.8 parts by weight.
Various curing accelerators that can be commonly used in the art as the curing accelerator.It such as can be organic guanidine
Close one of object, glyoxaline compound and carbamide compounds or a variety of；Preferably glyoxaline compound；More preferably 1- methyl
Imidazoles.
The resin combination can also contain one of defoaming agent, levelling agent and wetting agent or a variety of.Preferably, phase
For the curability binder resin of 100 parts by weight, the content of the infusion, levelling agent and wetting agent is respectively 0-12 weight
Part, more preferably 1.5-11 parts by weight.
Various defoaming agents, levelling agent and wetting that can be commonly used in the art as the defoaming agent, levelling agent and wetting agent
Agent.Preferably, the defoaming agent is poly acrylic acid-poly ether copolymer defoaming agent, organic silicon defoaming agent and organically-modified poly- silicon
One of oxygen alkane defoaming agent is a variety of；The levelling agent is acrylate, polyether siloxane copolymer, organically-modified poly- silicon oxygen
One of alkane and fluorosilicone antifoamant are a variety of；The wetting agent is nonionic organic surfactant.Specifically, as
932 defoaming agent of DEGO Airex (fluorosilicone antifoamant) can be used in the defoaming agent.
The preparation method of pre-soaking fiber cloth according to the present invention, is not particularly limited the fiber cloth, material can
Think it is conventional various, for example, be specifically as follows one of glass fabric, carbon cloth and aryl fiber cloth or a variety of,
Or the blended cloth of the two or more formation in above-mentioned glass fibre, carbon fiber and aramid fiber.
In the preparation method of pre-soaking fiber cloth of the invention, the thickness of above-mentioned fiber cloth is not particularly limited, specifically
It can change in a big way, under preferable case, the fiber cloth mass area ratio is 20-700g/m2, more preferably
50-300g/m2。
The preparation method of pre-soaking fiber cloth according to the present invention, in preferred situation, magnetism chopped strand surface packet
It is covered with silane coupling agent.By being coated with silane coupling agent on the chopped strand surface, having can be with fiber surface chemistry knot
The reactive group of conjunction, the effect for the function served as bridge that can get up between fiber and pre-soaked resin, so as to further increase interlayer
Binding force.
The method that the method for cladding silane coupling agent can be well known in the art on the chopped strand surface, such as will
Silane coupling agent and dispersing agent and the mixed spray solution of solvent are on the surface of the chopped strand.
It can be various silane coupling agents commonly used in this field as the silane coupling agent.Preferably, the silane
Coupling agent be amino silane, epoxy radicals silicone hydride, sulfenyl silane, methacryloxypropyl silane, vinyl silanes, ureido silane and
One of isocyanato silanes are a variety of；Preferably, the silane coupling agent is amino silane and/or epoxy radicals silicone hydride.
It can be various dispersing agents commonly used in this field, preferably waterglass, sodium tripolyphosphate, hexa metaphosphoric acid as the dispersing agent
Sodium, sodium pyrophosphate, triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative, polyacrylamide, Gu
One of your glue, aliphatic poly glycol ester and modified polyalkoxide are a variety of.As long as can be fine as the solvent
Ground is by the silane coupling agent and dispersant solvent, such as can be ethyl alcohol, dimethylbenzene, n-butanol, butyl glycol ether, second
One of acid butyl ester, isopropanol, cyclohexanone and methyl iso-butyl ketone (MIBK) are a variety of.
Mixing quality ratio for silane coupling agent, dispersing agent and solvent is preferably 1:0.5-5:50-200；It is especially excellent
It is selected as=1:3:100.
As described above, in the preparation method of pre-soaking fiber cloth of the invention, in the presence of magnetic field, by the way that thermosetting will be contained
The resin combination of the property changed binder resin and magnetic chopped strand is infiltrated up in fiber cloth, is then heating and curing to obtain pre-
Soak fiber cloth.As specifically in the presence of magnetic field by the resin group containing Thermocurable binder resin and magnetic chopped strand
Conjunction object, which is infiltrated up to the method in fiber cloth, can use various methods known in the field.Such as it can be by the resin combination
Prepreg is obtained after object mixing dispersion, contacts the prepreg with fiber cloth in the presence of magnetic source, after then contacting
Fiber cloth carry out the processing that is heating and curing.
In the above-mentioned methods, the order by merging of ingredient each in composition is not required particularly, can be arbitrary.
But consider from further increasing on inter-layer bonding force, preferably being thermally cured property binder resin and reactive diluent mix
After dispersion, adds magnetic chopped strand and carry out dispersion mixing, curing agent, curing accelerator and optional defoaming agent is then added
After carry out dispersion mixing, to obtain prepreg.
In addition, contact and can carrying out under room temperature (10-40 DEG C) prepreg with fiber cloth, the time of contact can
Think 3-30min.
The above-mentioned condition being heating and curing can be specifically chosen according to the ingredient of resin combination, but be usually in temperature
It is to heat 10-100min at 60-98 DEG C.
The pre-soaking fiber cloth that the preparation method of pre-soaking fiber cloth according to the present invention obtains, when being hot pressed into composite board
With excellent inter-layer bonding force.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example, raw material is the commercially available product of following company.
| Kind | Model | Company |
| Silane coupling agent | A1130 | U.S. Compton |
| Dispersing agent | Calgon | Beijing Kang Puhui ties up Science and Technology Ltd. |
| Ethyl alcohol | Ethyl alcohol | Dongguan City million can Chemical Co., Ltd. |
| Chopped strand | EMG-200 | Taishan glass fiber Ltd |
| Chopped strand | Carbon fiber DCMG-300 | Obtain Baily new material Co., Ltd |
| Chopped strand | EC10-1.5-T435N | Taishan glass fiber Ltd |
| Epoxy resin | E44 | CYTEC |
| Dicyandiamide | DICYANEX 1400F | U.S.'s gas |
| Imidazoles | 1- methylimidazole | Tianjin Ge Ruiheng industry Science and Technology Ltd. |
| Defoaming agent | Airex 932 | DEGO |
| Reactive diluent | SM678 | Sanmu Group Co., Ltd., Jiangsu |
| Fiber cloth | USN 15000 | Long Hong composite material Co., Ltd |
The production method of magnetic fibre in following embodiment are as follows: physical deposition method is used, by each fibre in above-mentioned table
Wei Pu is dispersed in PVD vacuum drying oven, is deposited ferrite powder, is then carried out rushing magnetic and obtaining in magnet charger.
Embodiment 1
1) according to silane coupling agent: dispersing agent: ethyl alcohol=1:3:100 ratio (mass ratio) prepares pretreating agent；
2) in 4Kg magnetism chopped strand, (magnetic glass chopped strand EMG-200, length are 200 μm, and diameter of section is 10 μ
M) pretreating agent is sprayed on surface, and drying obtains pretreatment of fiber silk X；
3) epoxy resin 48Kg, reactive diluent 25Kg are weighed, (upper Haifa is purchased from high speed disperser and inspires confidence in Lay limited energy
Company, same as below) dispersion, obtain mixture A；
4) pretreatment of fiber silk X obtained in step 2) is added in mixture A, is dispersed with high speed disperser, is mixed
Close object B；
5) dicyandiamide 15Kg (curing agent), 1- methylimidazole 5Kg (curing accelerator), defoaming agent 3Kg are weighed, mixing is added
In object B, dispersed with high speed disperser, obtain prepreg, and fiber prepreg slot is added；
6) it is placed magnet (magnetic direction and the angle of fiber cloth be 65 °) in fiber prepreg slot upper and lower side, it is strong in magnetic induction
Degree is under 0.5 tesla, by fiber cloth (carbon cloth, mass area ratio 150g/m2) pull by fiber prepreg slot (fibre
The time of contact of Wei Bu and prepreg is 25min), obtain the fiber cloth for being coated with prepreg；
7) heating has the fiber cloth 30min of prepreg at being 80 DEG C in temperature, obtains pre-soaking fiber cloth A1.
By the pre-soaking fiber cloth by micro- sem observation it is found that the surface of the pre-soaking fiber cloth is coated by resin-bonded layer,
The magnetism chopped strand is inserted into fiber cloth and resin-bonded layer namely the magnetism chopped strand is with being inserted in the fibre
The first partial of Wei Bunei and the second part being fixed in the resin-bonded layer, and magnetic chopped strand and the fiber
Substantially 65 ° of angle between cloth, in addition, adhering agent layer with a thickness of 0.2mm.
Embodiment 2
1) according to silane coupling agent: dispersing agent: ethyl alcohol=1:3:100 ratio (mass ratio) prepares pretreating agent；
2) 8Kg magnetism chopped strand (magnetic carbon chopped strand DCMG-300, length are 50 μm, and diameter of section is 7 μm)
Pretreating agent is sprayed on surface, and drying obtains pretreatment of fiber silk X；
3) epoxy resin 75Kg, reactive diluent 10Kg are weighed, is dispersed with high speed disperser, mixture A is obtained；
4) pretreatment of fiber silk X obtained in step 2) is added in mixture A, is dispersed with high speed disperser, is mixed
Close object B；
5) dicyandiamide 5Kg (curing agent), 1- methylimidazole 0.7Kg (curing accelerator), defoaming agent 1.3Kg are weighed, is added
In mixture B, dispersed with high speed disperser, obtain prepreg, and is added in fiber prepreg slot；
6) magnet (magnetic direction and the angle of fiber cloth be 83 °) is placed in fiber prepreg slot upper and lower side, in magnetic field strength
For under 0.8 tesla, by fiber cloth (carbon cloth, mass area ratio 150g/m2) pull by fiber prepreg slot (fiber
The time of contact of cloth and prepreg is 20min), obtain the fiber cloth for being coated with prepreg；
7) it weaves magnet (magnetic direction and the angle of fiber cloth be 83 °) in fiber prepreg slot upper and lower side, it is strong in magnetic induction
Degree is under 0.8 tesla, and heating has the fiber cloth 50min of prepreg at being 70 DEG C in temperature, obtains pre-soaking fiber cloth A2.
By the pre-soaking fiber cloth by micro- sem observation it is found that the surface of the pre-soaking fiber cloth is coated by resin-bonded layer,
The magnetism chopped strand is inserted into fiber cloth and resin-bonded layer namely the magnetism chopped strand is with being inserted in the fibre
The first partial of Wei Bunei and the second part being fixed in the resin-bonded layer, and magnetic chopped strand and the fiber
Substantially 83 ° of angle between cloth, in addition, adhering agent layer with a thickness of 0.25mm.
Embodiment 3
According to silane coupling agent: dispersing agent: ethyl alcohol=1:3:100 ratio (mass ratio) prepares pretreating agent；
2) in 15Kg magnetism chopped strand (magnetic glass chopped strand EC10-1.5-T435N, length 1.5mm, section
Diameter is 10 μm) surface sprinkling pretreating agent, it dries and obtains pretreatment of fiber silk X；
3) epoxy resin 40.5Kg, reactive diluent 18Kg are weighed, is dispersed with high speed disperser, mixture A is obtained；
4) pretreatment of fiber silk X obtained in step 2) is added in mixture A, is dispersed with high speed disperser, is mixed
Close object B；
5) dicyandiamide 20Kg (curing agent), 1- methylimidazole 3.5Kg (curing accelerator), defoaming agent 3Kg are weighed, is added mixed
It closes in object B, is dispersed with high speed disperser, obtain prepreg, and be added in fiber prepreg slot.
6) it is placed magnet (magnetic direction and the angle of fiber cloth be 90 °) in fiber prepreg slot upper and lower side, it is strong in magnetic induction
Degree is under 0.3 tesla, by fiber cloth (carbon cloth, mass area ratio 150g/m2) pull by fiber prepreg slot (fibre
The time of contact of Wei Bu and prepreg is 15min), obtain the fiber cloth for being coated with prepreg.
7) heating has the fiber cloth 90min of prepreg at being 60 DEG C in temperature, obtains pre-soaking fiber cloth A3.
By the pre-soaking fiber cloth by micro- sem observation it is found that the surface of the pre-soaking fiber cloth is coated by resin-bonded layer,
The magnetism chopped strand is inserted into fiber cloth and resin-bonded layer namely the magnetism chopped strand is with being inserted in the fibre
The first partial of Wei Bunei and the second part being fixed in the resin-bonded layer, and magnetic chopped strand and the fiber
Substantially 90 ° of angle between cloth, in addition, adhering agent layer with a thickness of 0.15mm.
Embodiment 4
It carries out according to the method for embodiment 1, the difference is that the length of magnetic glass chopped strand is 1mm, diameter of section 3
μm, pre-soaking fiber cloth A4 is obtained in the same manner.
By the pre-soaking fiber cloth by micro- sem observation it is found that the surface of the pre-soaking fiber cloth is coated by resin-bonded layer,
The magnetism chopped strand is inserted into fiber cloth and resin-bonded layer namely the magnetism chopped strand is with being inserted in the fibre
The first partial of Wei Bunei and the second part being fixed in the resin-bonded layer, and magnetic chopped strand and the fiber
Substantially 65 ° of angle between cloth.
Embodiment 5
It carries out according to the method for embodiment 1, unlike, the angle of magnetic direction and fiber cloth in step 6) is 45 °,
Pre-soaking fiber cloth A5 is obtained in the same manner.
By the pre-soaking fiber cloth by micro- sem observation it is found that the surface of the pre-soaking fiber cloth is coated by resin-bonded layer,
The magnetism chopped strand is inserted into fiber cloth and resin-bonded layer namely the magnetism chopped strand is with being inserted in the fibre
The first partial of Wei Bunei and the second part being fixed in the resin-bonded layer, and magnetic chopped strand and the fiber
Substantially 45 ° of angle between cloth.
Embodiment 6
It carries out according to the method for embodiment 1, unlike, the angle of magnetic direction and fiber cloth in step 6) is 25 °,
Pre-soaking fiber cloth A6 is obtained in the same manner.
By the pre-soaking fiber cloth by micro- sem observation it is found that the surface of the pre-soaking fiber cloth is coated by resin-bonded layer,
The magnetism chopped strand is inserted into fiber cloth and resin-bonded layer namely the magnetism chopped strand is with being inserted in the fibre
The first partial of Wei Bunei and the second part being fixed in the resin-bonded layer, and magnetic chopped strand and the fiber
Substantially 25 ° of angle between cloth.
Embodiment 7
It carries out, the difference is that pretreating agent is not sprayed on magnetic chopped strand surface, is presoaked according to the method for embodiment 1
Fiber cloth A7.
By the cross section of the pre-soaking fiber cloth by micro- sem observation it is found that the surface of the pre-soaking fiber cloth is resin-bonded
Layer cladding, the magnetism chopped strand is inserted into fiber cloth and resin-bonded layer namely the magnetism chopped strand is with plugging
In the first partial in the fiber cloth and the second part being fixed in the resin-bonded layer, and magnetic chopped strand with
Substantially 65 ° of angle between the fiber cloth.
Comparative example 1
It carries out according to the method for embodiment 1, the difference is that obtaining pre-soaking fiber cloth without addition magnetic glass chopped strand
D1。
Comparative example 2
It carries out, the difference is that replacing magnetic glass chopped strand with glass chopped strands, obtains according to the method for embodiment 1
Pre-soaking fiber cloth D2.
Test case 1 (peel strength test)
1) aluminium flake of a piece of 100mm × 20mm × 2mm is processed.
2) by the resulting pre-soaking fiber cloth of embodiment 1-7 and comparative example 1-2, respectively according to fiber architecture direction shown in Fig. 1
Tailor fibre fabric block X1, X2, X3 of three pieces 100mm × 20mm.
3) it by embodiment 1-8 and the resulting pre-soaking fiber cloth of comparative example 1, is cut out respectively according to fiber architecture direction shown in Fig. 2
Fibre fabric block Y1, Y2, Y3 of three pieces 100mm × 20mm processed.
4) fiber cloth tailored and aluminium flake are stacked into (such as Fig. 3 according to aluminium flake, X1, Y1, X2, Y2, X3, Y3 sequence
Shown, 1 indicates 6 layers of fiber cloth, and 2 indicate 2mm thickness aluminium sheet), and be placed in hot press and obtain hot pressing product XY.
5) according to XY is processed shown in Fig. 4, obtaining sample A1-A8 and D1 to be tested, (in Fig. 4,3 indicate 4 layers of fiber cloth, 4 tables
Show 2 layers of fiber cloth).
6) on universal testing machine, 4 layers of fiber cloth adding aluminium plate one end 6 are sandwiched in jig as shown in Figure 5, the other end
5 as illustrated direction removed, peeling rate 10mm/min completely falls off thin end, records data, the value be shell
From intensity.
The results are shown in Table 1 for it.
Table 1
| Serial number | Peel strength (N) |
| A1 | 320 |
| A2 | 350 |
| A3 | 385 |
| A4 | 290 |
| A5 | 290 |
| A6 | 281 |
| A7 | 265 |
| D1 | 200 |
| D2 | 240 |
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (34)
1. at least partly surface of a kind of pre-soaking fiber cloth, the pre-soaking fiber cloth is coated with resin-bonded layer, which is characterized in that institute
Stating between resin-bonded layer and fiber cloth has magnetic chopped strand, and between the magnetic chopped strand and the fiber cloth
Angle is greater than 0 °.
2. pre-soaking fiber cloth according to claim 1, wherein the folder between the magnetism chopped strand and the fiber cloth
Angle is 30-90 °.
3. pre-soaking fiber cloth according to claim 1 or 2, wherein the magnetism chopped strand, which has, is inserted in the fibre
The first partial of Wei Bunei and the second part being fixed in the resin-bonded layer.
4. pre-soaking fiber cloth according to claim 1 or 2, wherein the length of the magnetism chopped strand is 30 μm of -2mm.
5. pre-soaking fiber cloth according to claim 4, wherein the length of the magnetism chopped strand is 50 μm of -1mm.
6. pre-soaking fiber cloth according to claim 1 or 2, wherein the diameter of section of the magnetism chopped strand is 0.5-
20μm。
7. pre-soaking fiber cloth according to claim 6, wherein the diameter of section of the magnetism chopped strand is 1-10 μm.
8. pre-soaking fiber cloth according to claim 1 or 2, wherein the magnetism chopped strand is magnetic glass fiber, magnetic
Property carbon fiber and magnetic aramid fiber in it is one or more.
9. pre-soaking fiber cloth according to claim 1 or 2, wherein the fiber cloth be glass fabric, carbon cloth and
One of aryl fiber cloth is a variety of.
10. pre-soaking fiber cloth according to claim 9, wherein the mass area ratio of the fiber cloth is 20-700g/
m2。
11. pre-soaking fiber cloth according to claim 1 or 2, wherein resin-bonded layer is by containing Thermocurable binder
The resin combination solidification of resin and magnetic chopped strand obtains layer.
12. pre-soaking fiber cloth according to claim 11, wherein the resin-bonded layer with a thickness of 0.02-0.5mm.
13. pre-soaking fiber cloth according to claim 1 or 2, wherein the magnetism chopped strand surface is coated with silane idol
Join agent.
14. a kind of preparation method of pre-soaking fiber cloth, which is characterized in that this method comprises: in the presence of magnetic field, by that will contain
The resin combination of Thermocurable binder resin and magnetic chopped strand is infiltrated up in fiber cloth, is then heating and curing.
15. according to the method for claim 14, wherein relative to the curability binder resin of 100 parts by weight, contain 5-
The magnetic chopped strand of 50 parts by weight.
16. according to the method for claim 15, wherein relative to the curability binder resin of 100 parts by weight, contain 8-
The magnetic chopped strand of 38 parts by weight.
17. method described in any one of 4-16 according to claim 1, wherein the resin combination also contains active dilute
Agent is released, relative to the curability binder resin of 100 parts by weight, the reactive diluent containing 10-55 parts by weight.
18. according to the method for claim 17, wherein relative to the curability binder resin of 100 parts by weight, contain
The reactive diluent of 13-53 parts by weight.
19. according to the method for claim 18, wherein the reactive diluent is acrylic glycidol ether, butyl contracting
Water glycerin ether, ethylene glycol bisglycidyl ether, resorcinol bisglycidyl ether, hexanediol diglycidyl ether, butanediol two
One in glycidol ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether and alkyl multicondensed water glycerin ether
Kind is a variety of.
20. method described in any one of 4-16 according to claim 1, wherein the resin combination also contains curing agent,
Relative to the curability binder resin of 100 parts by weight, the curing agent containing 1-55 parts by weight.
21. according to the method for claim 20, wherein relative to the curability binder resin of 100 parts by weight, contain 2-
The curing agent of 50 parts by weight.
22. according to the method for claim 21, wherein the curing agent is diaminodiphenyl-methane, m-phenylene diamine (MPD), two
Aminodiphenyl base sulfone adipic dihydrazide, dicyandiamide, triethylene diamine, triethylene tetramine, tetraethylenepentamine, lignocaine third
Amine, Meng's alkane diamines, isophorone diamine, N- aminoethyl piperazine, bis- (4- amino -3- methylcyclohexyl) methane and bis- (4- amidos
Cyclohexyl) one of methane or a variety of.
23. method described in any one of 4-16 according to claim 1, wherein the resin combination also contains solidification and promotees
Into agent, relative to the curability binder resin of 100 parts by weight, the curing accelerator containing 0-10 parts by weight.
24. according to the method for claim 23, wherein relative to the curability binder resin of 100 parts by weight, contain
The curing accelerator of 0.9-8.8 parts by weight.
25. method described in any one of 4-16 according to claim 1, wherein the resin combination also contain defoaming agent,
One of levelling agent and dispersing agent are a variety of.
26. method described in any one of 4-16 according to claim 1, wherein the length of the magnetism chopped strand is 30 μ
m-2mm。
27. according to the method for claim 26, wherein the length of the magnetism chopped strand is 50 μm of -1mm.
28. method described in any one of 4-16 according to claim 1, wherein the diameter of section of the magnetism chopped strand
It is 0.5-20 μm.
29. according to the method for claim 28, wherein the diameter of section of the magnetism chopped strand is 1-10 μm.
30. method described in any one of 4-16 according to claim 1, wherein the magnetism chopped strand is magnetic glass
One of fiber, magnetic carbon fiber and magnetic aramid fiber are a variety of.
31. method described in any one of 4-16 according to claim 1, wherein the fiber cloth is glass fabric, carbon fiber
One of Wei Bu and aryl fiber cloth or a variety of.
32. according to the method for claim 31, wherein the mass area ratio 20-700g/m of the fiber cloth2。
33. method described in any one of 4-16 according to claim 1, wherein the Thermocurable binder resin is third
Olefin(e) acid resin, epoxy resin, polyurethane resin, polyester resin, phenylpropyl alcohol oxazines resin, phenolic resin, urea resin and melamine
It is one or more in polyimide resin.
34. method described in any one of 4-16 according to claim 1, wherein the magnetism chopped strand surface is coated with
Silane coupling agent.
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| CN111019291B (en) * | 2019-11-23 | 2022-08-16 | 南通大学 | Impact-resistant high-toughness fiber-reinforced composite material and preparation method thereof |
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| CN101700706A (en) * | 2009-11-18 | 2010-05-05 | 中南大学 | Lightweight and broadband wave absorbing material with foam sandwich structure and method for producing same |
| CN104610910A (en) * | 2015-01-15 | 2015-05-13 | 东华大学 | Wave absorption composite material containing chopped vertical bars and preparation method of wave absorption composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101700706A (en) * | 2009-11-18 | 2010-05-05 | 中南大学 | Lightweight and broadband wave absorbing material with foam sandwich structure and method for producing same |
| CN104610910A (en) * | 2015-01-15 | 2015-05-13 | 东华大学 | Wave absorption composite material containing chopped vertical bars and preparation method of wave absorption composite material |
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