A kind of anti-theft security paper
Technical field
The application relates to a kind of anti-theft security paper, and the method preparing this anti-theft security paper.
Background technology
Information is as a kind of resource, its universality, sharing, appreciation, handlability and multiple-effect
By property so that it is the mankind are had to the meaning of particular importance.According to the definition of International Organization for Standardization,
The implication of Information Security is primarily referred to as the integrity of information, availability, confidentiality and reliability, protects
Protecting the basic goal of information security is exactly to make internal information not by the prestige of the factor such as internal, outside, natural
The side of body.Information security is the problem that any country all must attach great importance to, and is a country that can not be ignored
Security strategy.Hostile force or illegal organization use various means to steal politics, military affairs, economy, section
The secret information of the aspect such as learn a skill, how government, army and company ensure information security becomes urgency
The problem that need to solve.Nowadays have a lot of concerning security matters or important paper document in the case of with no authorized
Being not allow to take security areas out of, this needs to protect these secrecy paper, it is desirable to having people
Attempt illegally to carry secrecy paper when leaving security areas, can with perception also by special detection means
Report to the police.
Prior art uses the mode implanting amorphous band in paper to protect secrecy paper.Non-
Crystal zone material has large Barkhusen effect, it may be assumed that domain wall generation saltatory is not in magnetic history for material
Reversible displacement process, can be detected by instrument.Amorphous band is put in alternating magnetic field, when
After magnetic field reaches the switch yard of material, the magnetic domain generation instantaneous variation of material, instrument can sense one
Individual distinctive electromagnetic signal.In actual applications, detection equipment is placed on the exit of security areas,
When implanting the paper entrance detection region of amorphous band when there being people to carry, detecting instrument will detect
One electromagnetic signal, reports to the police immediately.Due to preparation technology, prepare width and be less than 1 millimeter
Amorphous band difficulty is very big, and in order to offset the impact of demagnetizing field, amorphous band must keep certain length
Degree, just can have large Barkhusen effect.The amorphous with large Barkhusen effect used on market
Band, a length of 32 millimeters of standard, the shortest can being only capable of reaches 28 millimeters.Prior art is by length
Spending 32 millimeters, the sheet metal strip location that width is 1 millimeter is implanted in paper, and amorphous band is easy to by people
Find, and then it is destroyed, make the warning function of this anti-theft security paper lose efficacy.
Accordingly, it would be desirable to a kind of, there is the higher antitheft and anti-theft security paper of anti-damage ability.
Summary of the invention
By the present invention in that the amorphous naked fiber having prepared a diameter of 80-200 micron by inner circle water spinning,
And find, when this amorphous naked fiber has the high length-diameter ratio higher than 50, can have big Bark person of outstanding talent
Gloomy effect, implants the amorphous fiber of this high length-diameter ratio in paper, especially in art paper, just obtains
A kind of have the higher antitheft and anti-theft security paper of anti-damage ability.
Therefore, the present invention comprises herein below:
1. 1 kinds of anti-theft security paper of embodiment, implant in this anti-theft security paper and have big Barkhausen
The amorphous fiber of effect, a diameter of 80-200 micron of wherein said amorphous fiber, preferably 100-150
Micron;The a length of 2-10mm of described amorphous fiber.
The anti-theft security paper of embodiment 2. embodiment 1, wherein said amorphous fiber is in this antitheft peace
Content in full paper is 10-20m/m2(or every A4 paper is 0.6 meter to 1.2 meters).
The anti-theft security paper of embodiment 3. embodiment 1, wherein said amorphous fiber does not have cladding
Layer, is prepared by inner circle water spinning.
Anti-theft security paper any one of embodiment 4. aforementioned embodiments, wherein said anti-theft security
Paper is prepared by using amorphous naked fiber to be implanted directly in the middle of paper.
Anti-theft security paper any one of embodiment 5. aforementioned embodiments, wherein amorphous fiber contains
Have:
A) Co, one or more elements in Fe, Mn, Ni;
B) Si, one or more elements in B, C;With
C) optional rare earth or magnesium-yttrium-transition metal.
Anti-theft security paper any one of embodiment 6. aforementioned embodiments, wherein said amorphous fiber
It is distributed in described anti-theft security paper in the way of the distribution of full version, location distribution or a combination thereof.
Anti-theft security paper any one of embodiment 7. aforementioned embodiments, wherein said amorphous fiber
Arrange in described anti-theft security paper in the way of ordered arrangement, lack of alignment or a combination thereof.
Anti-theft security paper any one of embodiment 8. aforementioned embodiments, wherein amorphous fiber contains
Have:
The Fe of 1-15wt%;
The Si of 2-12wt%;
Total amount is the one in B, Nb, Cu, Mn, Mo, Ni, Cr and Al of 2-25wt%
Or it is multiple;And
The Co of surplus.
Anti-theft security paper any one of embodiment 9. aforementioned embodiments, it is art paper.
Anti-theft security paper any one of embodiment 10. aforementioned embodiments, wherein said amorphous is fine
A diameter of 100-150 micron of dimension;The a length of 5-10mm of described amorphous fiber.
Accompanying drawing explanation
In order to be illustrated more clearly that the technical scheme of the embodiment of the present invention, below by the accompanying drawing to embodiment
It is briefly described, it should be apparent that, the accompanying drawing in describing below merely relates to some realities of the present invention
Execute example, rather than limitation of the present invention.
Fig. 1: inner circle water spinning schematic diagram (the 21 nozzle 22 foundry alloy 23 induction coil 24 naked fibres of amorphous
Tie up 25 drum 26 coolants).
The electromicroscopic photograph of amorphous naked fiber prepared by the method for Fig. 2: the present invention.
Fig. 3: amorphous naked fiber large Barkhusen effect curve.
Fig. 4: containing the anti-theft security paper schematic diagram of unordered full version distribution amorphous naked fiber.
Fig. 5: containing the anti-theft security paper schematic diagram of the most completely version distribution amorphous fiber.
Fig. 6: containing the anti-theft security paper schematic diagram of unordered location distribution amorphous fiber.
Fig. 7: containing the anti-theft security paper schematic diagram of location distribution amorphous fiber in order.
Detailed description of the invention
For making the purpose of the embodiment of the present invention, technical scheme and advantage clearer, below in conjunction with this
The accompanying drawing of inventive embodiments, is clearly and completely described the technical scheme of the embodiment of the present invention.
Obviously, described embodiment is a part of embodiment of the present invention rather than whole embodiments.
Based on described embodiments of the invention, those of ordinary skill in the art are without creative work
The every other embodiment obtained under premise, broadly falls into the scope of protection of the invention.
Definition:
In this application, term " large Barkhusen effect " refers to what amorphous band or fiber were had
A kind of characteristic, i.e. this material is the irreversible upstream displacement process of domain wall generation saltatory in magnetic history,
This process can be detected by instrument.When actual detection, amorphous band or fiber are put into
In alternating magnetic field, after magnetic field reaches the switch yard of material, the magnetic domain generation instantaneous variation of material, inspection
Survey instrument and just can sense a distinctive electromagnetic signal.In some embodiments, wherein induct
The electromagnetic signal gone out is pulse signal or higher hamonic wave.In the present invention, amorphous fiber has big Barkhausen
Effect, as it is shown on figure 3, under the excitation of alternating magnetic field, when reaching a switching magnetic field value, magnetic
Induction can jump, thus generates an electromagnetic signal, such as: pulse signal or high order are humorous
Ripple.Will report to the police when detecting instrument detects the electromagnetic signal that amorphous fiber produces.
In this application, the method that term " inner circle water spinning " refers to carry out spinning as follows:
First the foundry alloy rod with required composition is provided;
2. in the drum of high speed rotating, add cooling water so that cooling water synchronizes rotation at the inwall of drum
Turn;
3. foundry alloy is put in the middle of nozzle, utilize induction heating mode to melt foundry alloy;
4. in nozzle, it is filled with gases at high pressure, the foundry alloy of fusing is sprayed into rapid solidification in water, preparation
Go out amorphous naked fiber.
As it is shown in figure 1, Fig. 1 describes the concrete grammar preparing amorphous naked fiber of the present invention.At Fig. 1
In, reference has a following implication:
21: nozzle
22: foundry alloy
23: induction coil
24: amorphous naked fiber
25: drum
26: coolant.
Fig. 2 is an example of the amorphous naked fiber prepared by the process described above.
In this application, term " amorphous fiber " or " amorphous naked fiber " have people in the art
The implication that member is generally understood.It is said that in general, it refers to a kind of alloy fiber, it contains multiple alloy
Element, such as Co, Fe, Mn, Ni, Si, B, C and transition metal etc..
The size range of the amorphous fiber in the present invention is: 80-200 micron;A length of more than 2 millimeters,
Preferably 2-10 millimeter.
In a kind of specific embodiment, the present invention provides a kind of anti-theft security paper, this anti-theft security
Paper implants the amorphous fiber with large Barkhusen effect, wherein said amorphous fiber a diameter of
80-200 micron, preferably 100-150 micron;The a length of 4-10mm of described amorphous fiber, preferably
5-10mm, more preferably 8-10mm.The inventors found that the size of amorphous fiber is relatively low, such as
When diameter is in 80-200 micrometer range, as long as the draw ratio of amorphous fiber is higher than 20, especially higher than
When 50, this amorphous fiber still has large Barkhusen effect.Therefore, if the length of amorphous fiber
Too low, then it is difficult to detect.And in common A4 paper, if amorphous fiber length is long, amorphous
Fiber is excessive with the difference of paper pulp fiber, often has a negative impact paper technology.
In one embodiment, in the anti-theft security paper of the present invention, described amorphous fiber is prevented at this
The content stolen in safety paper is 10-20m/m2, or every A4 paper is 0.6 meter to 1.2 meters.At amorphous
The content of fiber is higher than 10m/m2(such as, in every A4 paper the content of amorphous fiber be 0.6 meter with
Time upper) time, detection equipment in the market can arrive with higher accuracy detection.But, if
Content is the highest, then the cost of anti-theft security paper can be greatly improved, it is therefore preferred that amorphous fiber
Content in this anti-theft security paper is less than or equal to 20m/m2(such as, non-in every A4 paper
The content of crystalline cellulose is less than 1.2 meters).In one embodiment, described amorphous fiber is antitheft at this
Content in safety paper is 3-20m/m2, or in every A4 paper, the content of amorphous fiber is about 0.2 meter
To 1.2 meters.About 3 to less than 10m/m2Content range in (or in every A4 paper, amorphous is fine
When the length of dimension is about 0.2 meter to 0.6 meter), although commercially available detection equipment may be not easy to detect,
But, in this case it is still possible to detected by the parameter of regulation detection equipment.
In one embodiment, in the anti-theft security paper of the present invention, described amorphous fiber does not has
Clad, is prepared by inner circle water spinning.The amorphous fiber without clad is also referred to as amorphous
Naked fiber.As it has been described above, amorphous naked fiber described herein is to be made by " inner circle water spinning "
Standby, said method comprising the steps of: first the foundry alloy rod with required composition is provided;2. exist
Cooling water is added so that cooling water is at the inwall synchronous rotary of drum in the drum of high speed rotating;3. will
Foundry alloy is put in the middle of nozzle, utilizes induction heating mode to melt foundry alloy;4. in nozzle, it is filled with height
Calm the anger body, the foundry alloy of fusing is sprayed into rapid solidification in water, prepares amorphous naked fiber.This side
The feature of amorphous naked fiber prepared by method is to have thicker fibre diameter, and generally its fibre diameter is
80-200 micron.In the case of fibre diameter is relatively thick, it is not necessary to the highest draw ratio, detect equipment
Also it is easier to detect.But, fibre length prepared by inner circle water spinning is often not very uniform,
The seriality aspect produced needs to improve.
Due to a diameter of 80-200 micron of fiber prepared by inner circle water spinning, and common 80 grams
The thickness of A4 at 100 microns, the thickness of art paper at 300 microns, especially 250 to
350 microns, the amorphous naked fiber therefore the inner circle water spinning of the present invention prepared implants common A4 paper
In may increase the thickness of A4 paper, but when using it for art paper, owing to its diameter is less than copper
The thickness of millboard, is therefore particularly suitable.Therefore, the anti-theft security paper of the present invention is preferably copperplate
Paper.
After prepared amorphous fiber, this amorphous fiber can be mixed during papermaking paper making raw material
As the anti-theft security paper of the present invention prepared by paper pulp.In this way, can prepare have unordered
The anti-theft security paper of the amorphous fiber of arrangement.
In some embodiments, the anti-theft security paper of the present invention is by using amorphous naked fiber directly to plant
Enter and prepare in the middle of paper.In this way, can prepare there is the amorphous fiber of ordered arrangement
Anti-theft security paper.
For the material of amorphous fiber, it is not particularly limited, as long as the mesh of the present invention can be reached
?.In some embodiments, described amorphous fiber contains:
A) Co, one or more elements in Fe, Mn, Ni;
B) Si, one or more elements in B, C;With
C) optional rare earth or magnesium-yttrium-transition metal.
In the amorphous fiber of this composition, component a) is the component with ferromagnetic material, and component b) is
Non-metallic alloying elements.Component c) is optional, and the different proportioning of addO-on therapy makes it possible to material
The switch yard position producing large Barkhusen effect is subjected to displacement.
Some preferred embodiment in, amorphous fiber contains: the Fe of 1-15 weight %;2-12 weight
The Si of amount %;Total amount be 2-25 weight % selected from B, Nb, Cu, Mn, Mo, Ni, Cr and Al
In one or more;And Co.Some preferred embodiment in, amorphous fiber contains: 1-15
The Fe of weight %;The Si of 2-12 weight %;Total amount be 2-25 weight % selected from B, Nb, Cu, Mn,
One or more in Mo, Ni, Cr and Al;And the Co of surplus.There is the amorphous of this composition
Fiber is preferred in the present invention, because its material source is extensive, it is easy to preparation.
For the anti-theft security paper of the present invention, wherein said amorphous fiber distribution model in paper
Enclosing and do not limit, in a particular embodiment, described amorphous fiber can be distributed with full version, position
The mode of distribution or a combination thereof is distributed in described anti-theft security paper.Full version distribution refers to that amorphous fiber divides
The scope of cloth is throughout whole paper.Location distribution refers to that scope that amorphous fiber is distributed is in certain of paper
In fixed range, the most only in the marginal portion of paper, or a corner.
For the anti-theft security paper of the present invention, wherein said amorphous fiber arrangement side in paper
Formula does not has concrete restriction.In some embodiments, described amorphous fiber in anti-theft security paper with
The mode of ordered arrangement, lack of alignment or a combination thereof arranges in described anti-theft security paper.
In the present invention amorphous fiber with unordered full version distribution or the most completely version distribution or the distribution of unordered location or
Location is distributed in the example in the middle of paper as shown in Fig. 4, Fig. 5, Fig. 6, Fig. 7 in order.
Embodiment
The raw material used in embodiments of the invention is all conventional, can buy from the market, or
Can be prepared by conventional method in the lab.
Detection method:
In embodiments of the invention use detection equipment be electromagnetism (EM) label detection equipment (such as:
The electromagnetic tag detection door that Xian Xunmeizi company produces.).
The principle of detection can be described as follows:
Detection equipment contains sender unit and signal receiving device.Sender unit be by
Induction coil applies an alternating current or the mode of alternating voltage, produces excitation field district, excitation
Magnetic field is the magnetic field of an alternation.Signal receiving device is an induction coil.When amorphous fiber enters
During excitation field district, owing to it has large Barkhusen effect, under the excitation of alternating magnetic field, in it
Portion's domain structure can occur Rapid Variable Design, the electricity generated in the induction coil in signal receiving device
Magnetic field impulse signal or higher hamonic wave.When signal receiving device detects electromagnetic pulse signal or higher hamonic wave
Time, illustrate that target detection thing occurs in detection region.
Embodiment 1
The preparation of amorphous naked fiber, inner circle water spinning
Below with reference to the accompanying drawings 1, introduce the preparation method of the amorphous naked fiber of the present invention.
First providing Co base foundry alloy rod, the fusing point of this alloy bar is 970 DEG C, a diameter of 7mm, becomes
It is divided into Co71.8Fe4.9Nb0.8Si7.5B15.
Cooling water is added so that cooling water is rousing in the drum of the high speed rotating that rotating speed is 150 meter per seconds
The inwall synchronous rotary of wheel;
Foundry alloy is put in the middle of nozzle, utilize induction heating mode to melt foundry alloy, be heated to 1200
Degree;
In nozzle, it is filled with gases at high pressure, the foundry alloy of fusing is sprayed into rapid solidification in water, prepares
Amorphous naked fiber.
The diameter of the continuous print amorphous naked fiber long filament 100 ± 3 microns of embodiment 1 preparation.
The amorphous naked fiber long filament of acquisition is cut into a length of 0.5 millimeter, 1 millimeter, 2 millimeters, 5 millis
Rice, 10 millimeters and 15 millimeters standby.
Embodiment 2
By the amorphous naked fiber of preparation in embodiment 1 is implanted directly into preparation in the middle of paper, there is difference
The paper of amorphous fiber content, wherein, the total length distribution in paper of the amorphous naked fiber is respectively
0.3m/A4 paper, 0.4m/A4 paper, 0.60m/A4 paper, 0.8m/A4 paper, 1.2m/A4 paper.To preparation
The paper containing amorphous fiber test, result is following, and (the most each result is to 1000 paper weights
Recheck the statistical result recorded, when recall rate refers to the detection zone that paper is put into detecting instrument, inspection
Survey the number of times of instrument alarm):
As can be seen from the above results, in embodiment 1, the amorphous naked fiber of preparation has big Barkhausen
Effect.In the case of the length of amorphous naked fiber is less than or equal to 1mm, instrument is to this antitheft peace
The recall rate of full paper is less than 43%, but in the length of the amorphous naked fiber situation greater than or equal to 2mm
Under, as long as the total length of amorphous naked fiber reaches 0.6m/A4 paper, the instrument detection to anti-theft security paper
Rate just can be higher than 78%, especially when amorphous fiber total length in A4 paper is more than 0.6m,
And during a length of more than 5 millimeters of single amorphous naked fiber, recall rate has reached more than 96.5%.
The above is only the exemplary embodiment of the present invention, not for the protection limiting the present invention
Scope, protection scope of the present invention is determined by appended claim.
This application claims in the Chinese patent application the 201510156031.0th that on April 3rd, 2015 submits
Number priority, quote in full above-mentioned Chinese patent application disclosure at this using as the application's
A part.