CN110106736A - A kind of environmental type anti-counterfeiting paper and preparation method thereof - Google Patents
A kind of environmental type anti-counterfeiting paper and preparation method thereof Download PDFInfo
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- CN110106736A CN110106736A CN201910314481.6A CN201910314481A CN110106736A CN 110106736 A CN110106736 A CN 110106736A CN 201910314481 A CN201910314481 A CN 201910314481A CN 110106736 A CN110106736 A CN 110106736A
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- paper
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Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
- D21H11/18—Highly hydrated, swollen or fibrillatable fibres
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/52—Cellulose; Derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/54—Starch
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
Abstract
The invention discloses a kind of environmental type anti-counterfeiting papers and preparation method thereof, this method is the specific process steps are as follows: lignocellulosic is handled by enzymatic hydrolysis, nanosizing mechanical lapping, obtain micro/nano-fibre element, micro/nano-fibre element is subjected to fluorescent marker again, slurry and paper pulp after label is good is with copying or being applied in paper surface, with the anti-counterfeiting performance of Fluorescence Spectrometer detection anti-counterfeiting paper.Antifalsification paper auxiliary agent of present invention during preparing anti-counterfeiting paper has obvious antifalse effect, and anti-counterfeiting technology guidance can be provided for fields such as anti-counterfeit package, loan, check papers.
Description
Technical field
The invention belongs to pulp and paper technology fields, and in particular to a kind of environmental type anti-counterfeiting paper and preparation method thereof.
Background technique
Nowadays, anti-counterfeit field is further strong to novel, efficient anti-forging technology demand, simultaneously because most anti-fake fibres at present
The raw material of dimension be chemical fibre, when preparing anti-forge paper, ru nnability is bad, therefore, exploitation can effectively with traditional papermaking skill
Art combination, anti-fake material easy to use and technology are the Main ways of anti-counterfeiting paper development.The Nanowire prepared with plant fiber
Dimension element is raw material, and fluorescent marker is prepared antifalsification paper auxiliary agent, simple process, the fluorescence falsification preventing of preparation on nano-cellulose base
Additive performance is stablized, and antifalse effect is good, while meeting environmental requirement, so that the preparation for Novel anti-counterfeit paper provides technical support.
The technology of country's manufacture fluorescent fiber is also immature, mainly there is melt spinning method, solution spinning, decoration method, table
Finishing coat method, High Speed Airflow Impact and bonding method etc..Wherein the device of High Speed Airflow Impact is more complicated, and operating technology is difficult
It spends larger；Bonding method technique is cumbersome；Melt spinning method is although simple and easy, but the requirement to fluorescent chemicals is harsh (such as resistance to
Oxidation, high temperature resistant etc.)；Solution spinning spinning temperature compared with melt spinning is lower, is not in oxidation or resolution problem, but
It is required that fluorescent chemicals have preferable intermiscibility, it is soluble in spinning solution；Though surface covering method is easy to operate, this method
Restricted be that fluorescent chemicals are insecure in conjunction with fiber；Organic luminescent substance molecule can be easier to permeate by decoration method
Into fiber molecule gap, greatly improve organic luminescent substance to the stainability of fiber, have convenience in production, flexibility and
Actual operability.Decoration method prepares the method for fluorescent fiber mostly with polyester fiber, acetate fiber, polypropylene fibre etc. for fiber
Raw material, (common can be swollen above-mentioned fibre to the organic solution solvent that above-mentioned fiber can be made to be swollen using one or more
The organic solvent of dimension has esters, ketone etc.), then cooperate one or more kinds of with the immiscible diluent of luminescent substance, add
Enter water and be made into dye liquor, then carries out " dyeing " according to the normal dyeing process of textile industry and obtain luminescent fibre, fiber size exists
Millimeter rank.For above method without reference to wooden nano-cellulose, the nano-cellulose in the present invention is a kind of from plant fibre
The renewable environmental protection new material of preparation in dimension point, not only has a performances such as high-specific surface area, high intensity, also with it is Fluoresceinated
Object is closed to be firmly combined.
Additive process is that antifalsification paper auxiliary agent is added in copy paper workshop section in starching, and improves paper while reaching antifalse effect
Retention；Coating sizing method is that antifalsification paper auxiliary agent is used as sizing agent, is directly coated on body paper, can paint various user institutes
The pattern needed.
Summary of the invention
For overcome the deficiencies in the prior art, the purpose of the present invention is to propose to a kind of environmental type anti-counterfeiting paper and its preparations
Method.
The purpose of the present invention is achieved through the following technical solutions.
A kind of environmental type anti-counterfeiting paper and preparation method thereof, comprising the following steps:
(1) lignocellulosic is subjected to enzymolysis processing；
(2) slurry after step (1) enzymatic hydrolysis is subjected to nanosizing mechanical lapping processing, obtains micro/nano-fibre element；
(3) micro/nano-fibre element obtained by step (2) is subjected to fluorescent marker；
(4) slurry after step (3) fluorescent marker is subjected to high-pressure homogeneous processing；
(5) nano-cellulose after fluorescent marker obtained by step (4) is coated with paper or matched with paper and copied.
Preferably, in step (1), slurry concentration is 2-10wt% when the enzymolysis processing.
Preferably, in step (1), when the enzymolysis processing, pH 4.5-6, temperature is 36-60 DEG C, time 2-40h.
Preferably, in step (2), when the nanosizing mechanical lapping is handled, pressure 0-50.0MPa, grinding number is
28-48 times.
Preferably, in step (3), temperature is 30-80 DEG C, mixing speed 50-900r/min when the fluorescent marker, when
Between be 1-48h.
Preferably, in step (4), homogenizer internal pressure is 70-200MPa in the high-pressure homogeneous processing.
Preferably, in step (5), receiving after the fluorescent marker when nano-cellulose after fluorescent marker is coated with paper
With when copying, the additive amount of the nano-cellulose after fluorescent marker is 1-60wt% (relative to paper pulp over dry for rice cellulose and paper pulp
Slurry).
It preferably,, first will be after fluorescent marker when the nano-cellulose after fluorescent marker is coated with paper in step (5)
Nano-cellulose and dispersing agent are that 10:0-3:7 is configured to anti-fake sizing agent in mass ratio, and anti-fake sizing agent is then applied in paper
Open surface；Wherein, anti-fake sizing agent total solid content is 0.5-5.0wt%, coating weight 1.0-3.0g/m2。
It is further preferred that the dispersing agent is carboxymethyl cellulose or cationic starch.
A kind of environmental type anti-counterfeiting paper as made from above-described preparation method.
Anti-counterfeiting paper, which is measured, with Fluorescence Spectrometer occurs most hyperfluorescence near wavelength 470nm；Compared with body paper, anti-counterfeiting paper
0.1-5.0 times smoothly is improved, tensile strength improves 5%-100%.
Compared with prior art, the present invention have it is following the utility model has the advantages that
(1) micro/nano-fibre crude granule of the invention is small, good hydrophilic property, and the nano-cellulose of the fluorescent marker of preparation is outstanding
Supernatant after supernatant liquid is stood for 24 hours does not show fluorescence, shows that the antifalsification paper auxiliary agent stability prepared is good.
(2) the fluorescent marker nano-cellulose prepared by the present invention issues yellow-green fluorescence in ultraviolet light irradiation, utilizes this
Anti-counterfeiting performance, the anti-counterfeiting paper with obvious anti-counterfeiting characteristic can be made by being coated on paper surface.
(3) present invention can make product carry out source on packaging material anti-fake, and anti-counterfeiting technology is intuitive, obvious, no
Special instrument and professional knowledge are needed, only can show fluorescence with ultraviolet light irradiation, the anti-fake of product can be substantially reduced for enterprise
Technical costs.
(4) preparation process of anti-counterfeiting paper of the present invention is environmentally protective, while reaching antifalse effect, moreover it is possible to increase the flat of paper
The performances such as slippery, tensile strength.
Detailed description of the invention
Fig. 1 is the fluorescence spectra of anti-counterfeiting paper and body paper.
Specific embodiment
Specific implementation of the invention is described in further detail below in conjunction with example, but embodiments of the present invention are not
It is limited to this.
The present invention is not particularly limited the type of lignocellulosic material used and fluorescer, source, below with
For softwood pulp and fluorescent whitening agent.
Embodiment 1
(1) 50g needlebush slurry is subjected to enzymolysis processing, i.e., first cellulase is dissolved in deionized water, obtains fiber
Plain enzyme solution；Adjusting slurry concentration with enzymolysis liquid again is 2wt%, is 4.5 in pH, temperature is enzymolysis processing 5h at 50 DEG C；
(2) slurry after step (1) enzymatic hydrolysis is subjected to nanosizing mechanical lapping processing, grinding pressure 20.0MPa, grinding
Number is 30.0 times；
(3) it is ground to step (2) and fluorescent whitening agent progress fluorescent marker is added in gained nano-cellulose suspension, in temperature
Degree is 45 DEG C, and revolving speed stirs 1h under the conditions of being 900r/min；
(4) slurry after step (3) fluorescent marker is subjected to high-pressure homogeneous processing, homogenizer internal pressure is 100MPa；
(5) the resulting micro/nano-fibre element base fluorescer of step (4) is mixed with paper pulp and is manufactured paper with pulp；
(6) micro/nano-fibre element base fluorescer obtained by step (4) and carboxymethyl cellulose and water are prepared into anti-fake sizing
Agent, the ratio between solid content of micro/nano-fibre element base fluorescer and carboxymethyl cellulose is 3:7 in sizing agent, and sizing agent always contains admittedly
Amount is 0.5wt%；
(7) anti-fake sizing agent obtained by step (6) is applied in paper surface with applicator roll, and coating paper is placed in baking oven and is done
Dry, drying temperature is 105 DEG C, time 1min；
(8) anti-counterfeiting performance of anti-counterfeiting paper made from detecting step (5) and step (7) and smoothness and tensile strength.
As a result: as shown in Figure 1, measure anti-counterfeiting paper with Fluorescence Spectrometer most hyperfluorescence occurs near wavelength 470nm.Separately
Outside, the surface property for detecting anti-counterfeiting paper can obtain, when mixing is manufactured paper with pulp, when the additive amount of micro/nano-fibre element base fluorescer is paper pulp
When the 1wt% of oven dry stock, compared with body paper, the smoothness of anti-counterfeiting paper improves 0.1 times, and tensile strength improves 5%；Work as application
Resin added be 3.0g/m2When, compared with body paper, the smoothness of anti-counterfeiting paper improves 3.0 times, and tensile strength improves 50%；
Embodiment 2
(1) 50g needlebush slurry is subjected to enzymolysis processing, i.e., first cellulase is dissolved in deionized water, obtains fiber
Plain enzyme solution；Adjusting slurry concentration with enzymolysis liquid again is 5wt%, is 5 in pH, temperature is enzymolysis processing 40h at 36 DEG C；
(2) slurry after step (1) enzymatic hydrolysis is subjected to nanosizing mechanical lapping processing, grinding pressure 50MPa, grinding time
Number is 28 times；
(3) it is ground to step (2) and fluorescent whitening agent progress fluorescent marker is added in gained nano-cellulose suspension, in temperature
Degree is 30 DEG C, and revolving speed stirs 48h under the conditions of being 700r/min；
(4) slurry after step (3) fluorescent marker is subjected to high-pressure homogeneous processing, homogenizer internal pressure is 70MPa；
(5) the resulting micro/nano-fibre element base fluorescer of step (4) is mixed with paper pulp and is manufactured paper with pulp；
(6) micro/nano-fibre element base fluorescer obtained by step (4) and carboxymethyl cellulose and water are prepared into anti-fake sizing
Agent, the ratio between solid content of micro/nano-fibre element base fluorescer and carboxymethyl cellulose 5:5 in sizing agent, sizing agent always contain admittedly
Amount is 5.0wt%；
(7) anti-fake sizing agent obtained by step (6) is applied in paper surface with applicator roll, and coating paper is placed in baking oven and is done
Dry, drying temperature is 105 DEG C, time 1min；
(8) anti-counterfeiting performance of anti-counterfeiting paper made from detecting step (5) and step (7) and smoothness and tensile strength.
As a result: it is similar to Figure 1, anti-counterfeiting paper, which is measured, with Fluorescence Spectrometer occurs most hyperfluorescence near wavelength 470nm.Separately
Outside, the surface property for detecting anti-counterfeiting paper can obtain, when mixing is manufactured paper with pulp, when the additive amount of micro/nano-fibre element base fluorescer is paper pulp
When the 12wt% of oven dry stock, compared with body paper, the smoothness of anti-counterfeiting paper improves 2.0 times, and tensile strength improves 100%；When
The resin added of application is 2.8g/m2When compared with body paper, the smoothness of anti-counterfeiting paper improves 2.4 times, and tensile strength improves
31%.
Embodiment 3
(1) 50g needlebush slurry is subjected to enzymolysis processing, i.e., first cellulase is dissolved in deionized water, obtains fiber
Plain enzyme solution；Adjusting slurry concentration with enzymolysis liquid again is 10wt%, is 6 in pH, temperature is enzymolysis processing 2h at 60 DEG C；
(2) slurry after step (1) enzymatic hydrolysis is subjected to nanosizing mechanical lapping processing, grinding pressure 30.0MPa, grinding
Number is 48.0 times；
(3) it is ground to step (2) and fluorescent whitening agent progress fluorescent marker is added in gained nano-cellulose, be 80 in temperature
DEG C, revolving speed stirs 12h under the conditions of being 50r/min；
(4) slurry after step (3) fluorescent marker is subjected to high-pressure homogeneous processing, homogenizer internal pressure is 200MPa；
(5) the resulting micro/nano-fibre element base fluorescer of step (4) is mixed with paper pulp and is manufactured paper with pulp；
(6) micro/nano-fibre element base fluorescer obtained by step (4) and carboxymethyl cellulose and water are prepared into anti-fake sizing
Agent, the ratio between solid content of micro/nano-fibre element base fluorescer and carboxymethyl cellulose 7:3 in sizing agent, sizing agent always contain admittedly
Amount is 4.0wt%；
(7) anti-fake sizing agent obtained by step (6) is applied in paper surface with applicator roll, and coating paper is placed in baking oven and is done
Dry, drying temperature is 105 DEG C, time 1min；
(8) anti-counterfeiting performance of anti-counterfeiting paper made from detecting step (5) and step (7) and smoothness and tensile strength.
As a result: it is similar to Figure 1, anti-counterfeiting paper, which is measured, with Fluorescence Spectrometer occurs most hyperfluorescence near wavelength 470nm.Separately
Outside, the surface property for detecting anti-counterfeiting paper can obtain, when mixing is manufactured paper with pulp, when the additive amount of micro/nano-fibre element base fluorescer is paper pulp
When the 30wt% of oven dry stock, compared with body paper, the smoothness of anti-counterfeiting paper improves 2.3 times, and tensile strength improves 95%；When applying
The resin added of painting is 1.5g/m2When compared with body paper, the smoothness of anti-counterfeiting paper improves 1.3 times, and tensile strength improves 26%.
Embodiment 4
(1) 50g needlebush slurry is subjected to enzymolysis processing, i.e., first cellulase is dissolved in deionized water, obtains fiber
Plain enzyme solution；Again with enzymolysis liquid adjust slurry concentration be 8wt%, pH be 4.5, temperature be 40 DEG C at enzymolysis processing for 24 hours；
(2) slurry after step (1) enzymatic hydrolysis is subjected to nanosizing mechanical lapping processing, grinding pressure 40.0MPa, grinding
Number is 35.0 times；
(3) it is ground to step (2) and fluorescent whitening agent progress fluorescent marker is added in gained nano-cellulose, be 60 in temperature
DEG C, revolving speed stirs for 24 hours under the conditions of being 350r/min；
(4) slurry after step (3) fluorescent marker is subjected to high-pressure homogeneous processing, homogenizer internal pressure is 150MPa；
(5) the resulting micro/nano-fibre element base fluorescer of step (4) is mixed with paper pulp and is manufactured paper with pulp；
(6) micro/nano-fibre element base fluorescer obtained by step (4) and water are prepared into anti-fake sizing agent, the total of sizing agent consolidates
Content is 3.0wt%；
(7) anti-fake sizing agent obtained by step (6) is applied in paper surface with applicator roll, and coating paper is placed in baking oven and is done
Dry, drying temperature is 105 DEG C, time 1min；
(8) anti-counterfeiting performance of anti-counterfeiting paper made from detecting step (5) and step (7) and smoothness and tensile strength.
As a result: it is similar to Figure 1, anti-counterfeiting paper, which is measured, with Fluorescence Spectrometer occurs most hyperfluorescence near wavelength 470nm.Separately
Outside, the surface property for detecting anti-counterfeiting paper can obtain, when mixing is manufactured paper with pulp, when the additive amount of micro/nano-fibre element base fluorescer is paper pulp
When the 60wt% of oven dry stock, compared with body paper, the smoothness of anti-counterfeiting paper improves 5.0 times, and tensile strength improves 80%；When applying
The resin added of painting is 1.0g/m2When compared with body paper, the smoothness of anti-counterfeiting paper improves 0.1 times, and tensile strength improves 15%.
Claims (10)
1. a kind of preparation method of environmental type anti-counterfeiting paper, which comprises the following steps:
(1) lignocellulosic is subjected to enzymolysis processing；
(2) slurry after step (1) enzymatic hydrolysis is subjected to nanosizing mechanical lapping processing, obtains micro/nano-fibre element；
(3) micro/nano-fibre element obtained by step (2) is subjected to fluorescent marker；
(4) slurry after step (3) fluorescent marker is subjected to high-pressure homogeneous processing；
(5) nano-cellulose after fluorescent marker obtained by step (4) is coated with paper or matched with paper pulp and copied.
2. a kind of environmental type anti-counterfeiting paper according to claim 1 and preparation method thereof, which is characterized in that step (1)
In, slurry concentration is 2-10 wt% when the enzymolysis processing.
3. a kind of environmental type anti-counterfeiting paper according to claim 1 and preparation method thereof, which is characterized in that step (1)
In, when the enzymolysis processing, pH 4.5-6, temperature is 36-60 DEG C, time 2-40h.
4. a kind of environmental type anti-counterfeiting paper according to claim 1 and preparation method thereof, which is characterized in that step (2)
In, when the nanosizing mechanical lapping is handled, pressure is 0-50.0 MPa, and grinding number is 28-48 times.
5. a kind of environmental type anti-counterfeiting paper according to claim 1 and preparation method thereof, which is characterized in that step (3)
In, temperature is 30-80 DEG C when the fluorescent marker, and mixing speed is 50-900 r/min, and the time is 1-48 h.
6. a kind of environmental type anti-counterfeiting paper according to claim 1 and preparation method thereof, which is characterized in that step (4)
In, homogenizer internal pressure is 70-200 MPa in the high-pressure homogeneous processing.
7. a kind of environmental type anti-counterfeiting paper according to claim 1 and preparation method thereof, which is characterized in that step (5)
In, by after fluorescent marker nano-cellulose and paper pulp with copying when, the nano-cellulose after fluorescent marker is relative to paper pulp over dry
The additive amount of slurry is 1-60 wt%.
8. a kind of environmental type anti-counterfeiting paper according to claim 1 and preparation method thereof, which is characterized in that step (5)
In, when the nano-cellulose after fluorescent marker is coated with paper, the nano-cellulose after fluorescent marker is first pressed into matter with dispersing agent
Then anti-fake sizing agent is applied in paper surface than being configured to anti-fake sizing agent for 10:0-3:7 by amount；Wherein, anti-fake sizing agent
Total solid content is 0.5-5.0 wt%, and coating weight is 1.0-3.0 g/m2。
9. a kind of environmental type anti-counterfeiting paper according to claim 8 and preparation method thereof, which is characterized in that the dispersion
Agent is carboxymethyl cellulose or cationic starch.
10. a kind of environmental type anti-counterfeiting paper as made from the described in any item preparation methods of claim 1-9.
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Application publication date: 20190809 |