CN108486954A - A kind of synthetic method of macromolecule/layered double hydroxide base fluorescent type paper surface sizing agent - Google Patents
A kind of synthetic method of macromolecule/layered double hydroxide base fluorescent type paper surface sizing agent Download PDFInfo
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- CN108486954A CN108486954A CN201810247400.0A CN201810247400A CN108486954A CN 108486954 A CN108486954 A CN 108486954A CN 201810247400 A CN201810247400 A CN 201810247400A CN 108486954 A CN108486954 A CN 108486954A
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- Prior art keywords
- paper surface
- sizing agent
- surface sizing
- layered double
- double hydroxide
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- 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/385—Oxides, hydroxides or carbonates
-
- 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
- D21H19/46—Non-macromolecular organic compounds
-
- 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
- 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
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or 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
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
Abstract
A kind of synthetic method of macromolecule/layered double hydroxide base fluorescent type paper surface sizing agent, includes the following steps:Fluorescent whitening agent is dissolved in a certain amount of deionized water, is dispersed with stirring to obtain optical brightener solutions or suspension;Water soluble polymer is wherein added to optical brightener solutions, is vigorously stirred at 70 85 DEG C to dissolving completely, obtains fluorescence polymer solution or suspension;The soluble-salt of divalent metal and the soluble-salt of trivalent metal are separately weighed respectively, and deionized water is added in above two metal soluble-salt and urea, is configured to trivalent metal ion;Trivalent metal ion is slowly added dropwise into fluorescence polymer solution, secure satisfactory grades sub- composite solution;It waits for that gained macromolecule composite solution is transferred in the reaction kettle of polytetrafluoroethyllining lining by step 4 after reaction, obtains macromolecule/layered double hydroxide base fluorescent type paper surface sizing agent, present invention process is simple, easy to operate.
Description
Technical field
The present invention relates to chemical industry paper surface sizing agent technical field, more particularly to a kind of macromolecule/layered bi-metal hydrogen
The synthetic method of oxide-base fluorescent type paper surface sizing agent.
Background technology
Top sizing is essential process in paper or board making process, and purpose is mainly to change the table of paper
Face performance such as enhances the water-resistance of paper, printing performance, surface strength, physical strength, two sides difference etc..And common surface is applied
Jelly is broadly divided into two classes, water resistant class and enhancing class.Alkyl ketene dimer (AKD), benzene can be selected in water resistant class Cypres
Thylene maleic acid anhydride copolymer etc.;Enhance the optional starch, carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA) etc. of class.But
It is that these Cypres all have various defects, such as PVA poor water resistances, alkyl ketene dimer Storage period is short, film forming
Difference etc..And since China's timber resources is in short supply, so high yield pulp starts to be widely used, but the brightness reversion of high yield pulp is asked
Topic is also the huge difficult problem that paper industry faces at present.Therefore it is entirely to make to synthesize a kind of multi-functional high molecular form surface sizing agent
Paper industry urgent problem.
Layered double hydroxide (LDHs) is a kind of anionic intercalation material of typical houghite, general formula
Generally [M2+1-xM3+ (OH) 2] [An-] x/nmH2O.LDHs laminates have shepardite regular octahedron structure, main layer board
It being made of metal hydroxides, the objects such as anion and some hydrones are embedded into interlayer and form unique layer structure,
And the interchangeability of its adjustable denaturation and interlayer object anion with main layer board composition.Based on this, in recent years its
The application of every field has received widespread attention.Lv Weiyang etc. utilizes itself and the compound water-resistance [1] for improving PVA of PVA, FengY
Application in terms of reviewing LDHs flame retardance of polymer and thermal stability Deng the scientific paper and patent report combined in recent years
[2], but by LDHs for macromolecule paper surface sizing agent report there is not yet.
Invention content
In order to overcome the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of macromolecule/layered bi-metals
The synthetic method of hydroxide base fluorescent type paper surface sizing agent, it is small to toxic or less toxic fluorescent whitening agent to solve human body
The absorption of molecule, and this method is simple for process, it is easy to operate.
To achieve the goals above, the technical solution adopted by the present invention is:
A kind of synthetic method of macromolecule/layered double hydroxide base fluorescent type paper surface sizing agent, including with
Lower step:
Step 1:
Fluorescent whitening agent is dissolved in a certain amount of deionized water, it is (or suspended to be dispersed with stirring to obtain optical brightener solutions
Liquid);
Step 2:
Water soluble polymer is wherein added to optical brightener solutions, is vigorously stirred at 70-85 DEG C to dissolving completely, is obtained
To fluorescence polymer solution (or suspension);
Step 3:
Separately the soluble-salt of divalent metal and the soluble-salt of trivalent metal are weighed respectively, above two metal is soluble
Deionized water is added in salt and urea, is configured to trivalent metal ion;
Step 4:
The trivalent metal ion that step 3 obtains is slowly added dropwise to the fluorescence polymer solution obtained into step 2, is secured satisfactory grades
Sub- composite solution;
Step 5:
Wait for that gained macromolecule composite solution is transferred in the reaction kettle of polytetrafluoroethyllining lining by step 4 after reaction,
Obtain macromolecule/layered double hydroxide base fluorescent type paper surface sizing agent.
Fluorescent whitening agent in the step 1 is cumarin base, naphthalimide or diphenylethyllene fluorescent whitening agent.
The mass concentration for being dispersed with stirring to obtain optical brightener solutions in the step one is 1 × 10-4~1 × 10-2g/
ml。
Water soluble polymer in the step 2 includes styrene-acrylic emulsion, oxidized starch, polyacrylamide, carboxymethyl cellulose
One kind in plain (CMC).
Water soluble polymer mass concentration is 0.02~0.2g/ml in the step two.
The molar ratio of the soluble-salt of the soluble-salt and trivalent metal of divalent metal is 1 in the step three:1-1:
3, the molar ratio of urea and trivalent soluble-salt is 9:1-18:1, described is configured to trivalent metal ion a concentration of 1 × 10-3~
1×10-2g/ml。
Bivalent metal ion includes Zn in the step 32+And Mg2+。
Trivalent metal ion includes Al in the step 33+。
The step four keeps 60-85 DEG C of reaction temperature, reaction time 2-4h, nitrogen protection.
Aging 10-14 hours at 90-110 DEG C in a kettle in the step five.
Beneficial effects of the present invention:
The advantage of the invention is that will enhance surface strength of paper, water-resistance and inhibition three kinds of functions of paper from yellowing are incorporated in
In a kind of paper surface sizing agent, and intercalation is carried out to inorganic matter using organic matter, organic molecule is strapped in inorganic matter
Between laminate, solve absorption of the human body to toxic or less toxic fluorescent whitening agent small molecule.And this method is simple for process, operation
It is easy.
Description of the drawings
Fig. 1 is to pass through paper surface sizing agent made from this method.
Filming performance of Fig. 2 paper surface sizing agents in paper surface.
Fig. 3 paper surface sizing agents are used in the mechanical property of the paper after paper surface.
Specific implementation mode
Invention is further described in detail below in conjunction with the accompanying drawings.
Embodiment 1
Configuration concentration is 2 × 10-4G/ml Stilbene-based Fluorescent Brighteners solution 50ml is placed in three-necked flask, and 7.5g is added
Styrene-acrylic emulsion, dissolved with vigorous agitation is simultaneously warming up to 85 DEG C, at fluorescence polymer solution.In addition configuration Zn (NO3)2·6H2O:Al
(NO3)3·9H2O:Urea=1:2:10 (molar ratios, wherein Al3+A concentration of 0.005g/ml) mixed solution 25ml, and in nitrogen
It is slowly dropped into above-mentioned fluorescence polymer solution under gas shielded, keeps 85 DEG C of reaction temperature, reacts 2h.Wait for this after reaction by institute
The sub- composite solution that secures satisfactory grades is transferred in the reaction kettle of polytetrafluoroethyllining lining, aging 12 hours at 100 DEG C, obtain macromolecule/
Layered double hydroxide base fluorescent type paper surface sizing agent.
Embodiment 2
Configuration concentration is 1 × 10-2G/ml Stilbene-based Fluorescent Brighteners solution 50ml is placed in three-necked flask, and 10g is added
Polyacrylamide, dissolved with vigorous agitation is simultaneously warming up to 85 DEG C, at fluorescence polymer solution.In addition configuration Mg (NO3)2·6H2O:Al
(NO3)3·9H2O:Urea=1:3:18 (molar ratios, wherein Al3+A concentration of 0.01g/ml) mixed solution 25ml, and in nitrogen
It is slowly dropped into above-mentioned fluorescence polymer solution under protection, keeps 85 DEG C of reaction temperature, reacts 3h.Wait for this after reaction by gained
Macromolecule composite solution is transferred in the reaction kettle of polytetrafluoroethyllining lining, and aging 14 hours at 110 DEG C obtain macromolecule/layer
Shape double-metal hydroxide base fluorescent type paper surface sizing agent.
Embodiment 3
Configuration concentration is 5 × 10-4G/ml naphthalimide type optical brightener solutions 50ml is placed in three-necked flask, and 5g is added
CMC, dissolved with vigorous agitation is simultaneously warming up to 70 DEG C, at fluorescence polymer solution.In addition configuration Zn (NO3)2·6H2O:Al(NO3)3·
9H2O:Urea=1:1:9 (molar ratios, wherein Al3+A concentration of 0.001g/ml) mixed solution 25ml, and under nitrogen protection
It is slowly dropped into above-mentioned fluorescence polymer solution, keeps 70 DEG C of reaction temperature, reacts 2h.Wait for this after reaction by gained macromolecule
Composite solution is transferred in the reaction kettle of polytetrafluoroethyllining lining, and aging 10 hours at 90 DEG C obtain macromolecule/layered bi-metal
Hydroxide base fluorescent type paper surface sizing agent.
Embodiment 4
Configuration concentration is 5 × 10-3G/ml coumarin type optical brightener solutions 50ml is placed in three-necked flask, and 1g oxidations are added
Starch, dissolved with vigorous agitation is simultaneously warming up to 80 DEG C, at fluorescence polymer solution.In addition configuration Mg (NO3)2·6H2O:Al
(NO3)3·9H2O:Urea=1:2:15 (molar ratios, wherein Al3+A concentration of 0.005g/ml) mixed solution 25ml, and in nitrogen
It is slowly dropped into above-mentioned fluorescence polymer solution under gas shielded, keeps 80 DEG C of reaction temperature, reacts 3h.Wait for this after reaction by institute
The sub- composite solution that secures satisfactory grades is transferred in the reaction kettle of polytetrafluoroethyllining lining, aging 10 hours at 100 DEG C, obtain macromolecule/
Layered double hydroxide base fluorescent type paper surface sizing agent.
Embodiment 5
Configuration concentration is 1 × 10-3G/ml carbon quantum point-type optical brightener solutions 50ml is placed in three-necked flask, and 3g benzene is added
Acrylic emulsion, dissolved with vigorous agitation is simultaneously warming up to 75 DEG C, at fluorescence polymer solution.In addition configuration Zn (NO3)2·6H2O:Al
(NO3)3·9H2O:Urea=1:3:15 (molar ratios, wherein Al3+A concentration of 0.005g/ml) mixed solution 25ml, and in nitrogen
It is slowly dropped into above-mentioned fluorescence polymer solution under gas shielded, keeps 75 DEG C of reaction temperature, reacts 3h.Wait for this after reaction by institute
The sub- composite solution that secures satisfactory grades is transferred in the reaction kettle of polytetrafluoroethyllining lining, aging 12 hours at 110 DEG C, obtain macromolecule/
Layered double hydroxide base fluorescent type paper surface sizing agent.
Embodiment 6
Configuration concentration is 1 × 10-3G/ml naphthalimide type optical brightener solutions 50ml is placed in three-necked flask, and 6g oxygen is added
Change starch, dissolved with vigorous agitation is simultaneously warming up to 85 DEG C, at fluorescence polymer solution.In addition configuration Zn (NO3)2·6H2O:Al
(NO3)3·9H2O:Urea=1:3:15 (molar ratios, wherein Al3+A concentration of 0.005g/ml) mixed solution 25ml, and in nitrogen
It is slowly dropped into above-mentioned fluorescence polymer solution under gas shielded, keeps 85 DEG C of reaction temperature, reacts 3h.Wait for this after reaction by institute
The sub- composite solution that secures satisfactory grades is transferred in the reaction kettle of polytetrafluoroethyllining lining, aging 12 hours at 110 DEG C, obtain macromolecule/
Layered double hydroxide base fluorescent type paper surface sizing agent.
Embodiment 7
Configuration concentration is 5 × 10-3G/ml coumarin type optical brightener solutions 50ml is placed in three-necked flask, and 9g poly- third is added
Acrylamide, dissolved with vigorous agitation is simultaneously warming up to 85 DEG C, at fluorescence polymer solution.In addition configuration Zn (NO3)2·6H2O:Al
(NO3)3·9H2O:Urea=1:2:15 (molar ratios, wherein Al3+A concentration of 0.005g/ml) mixed solution 25ml, and in nitrogen
It is slowly dropped into above-mentioned fluorescence polymer solution under gas shielded, keeps 85 DEG C of reaction temperature, reacts 4h.Wait for this after reaction by institute
The sub- composite solution that secures satisfactory grades is transferred in the reaction kettle of polytetrafluoroethyllining lining, aging 14 hours at 110 DEG C, obtain macromolecule/
Layered double hydroxide base fluorescent type paper surface sizing agent.
As shown in Figure 1:For 1 obtained paper surface sizing agent of embodiment.Left hand view is the product under natural light, right
Side figure is the product under ultraviolet light.It can be seen that product is milky under natural light, and under the irradiation of ultraviolet light, product can
To send out strong blue-fluorescence, this illustrates that the obtained paper surface sizing agent of this method has fluorescent characteristic.
As shown in Figure 2:To apply the SEM after paper surface to scheme 3 gained Cypres of embodiment.It can be with from figure
See that Cypres by paper fibre uniform fold, have been formed on its surface one layer of fine and close film, it in this way can be effectively
Natural light direct irradiation paper fibre is prevented, to inhibit the light aging of paper.
As shown in Figure 3:For gained Cypres (embodiment 7) to be applied to the paper surface measured after paper surface
The relationship of power and double-metal hydroxide content in Cypres.It can be seen that with the increase of double-metal hydroxide, paper
The surface tension opened also increases therewith.Especially compare the paper surface that (77N) when (38N) and addition are 0.2% is not added
Tension, discovery improve 1 times, illustrate that paper surface sizing agent that this method obtains has the mechanical property of paper and significantly carry
It is high.
Claims (10)
1. a kind of synthetic method of macromolecule/layered double hydroxide base fluorescent type paper surface sizing agent, feature exist
In including the following steps:
Step 1:
Fluorescent whitening agent is dissolved in a certain amount of deionized water, is dispersed with stirring to obtain optical brightener solutions or suspension;
Step 2:
Water soluble polymer is wherein added to optical brightener solutions, is vigorously stirred at 70-85 DEG C to dissolving completely, is obtained glimmering
Light Polymer Solution or suspension;
Step 3:
Separately weigh the soluble-salt of divalent metal and the soluble-salt of trivalent metal respectively, by above two metal soluble-salt and
Deionized water is added in urea, is configured to trivalent metal ion;
Step 4:
The trivalent metal ion that step 3 obtains is slowly added dropwise to the fluorescence polymer solution obtained into step 2, the son that secures satisfactory grades is multiple
Close solution;
Step 5:
It waits for that gained macromolecule composite solution is transferred in the reaction kettle of polytetrafluoroethyllining lining by step 4 after reaction, obtains
Macromolecule/layered double hydroxide base fluorescent type paper surface sizing agent.
2. a kind of macromolecule according to claim 1/layered double hydroxide base fluorescent type paper surface sizing agent
Synthetic method, which is characterized in that fluorescent whitening agent in the step 1 is cumarin base, naphthalimide or talan
Base fluorescent whitening agent.
3. a kind of macromolecule according to claim 1/layered double hydroxide base fluorescent type paper surface sizing agent
Synthetic method, which is characterized in that the mass concentration for being dispersed with stirring to obtain optical brightener solutions in the step one is 1 ×
10-4~1 × 10-2g/ml。
4. a kind of macromolecule according to claim 1/layered double hydroxide base fluorescent type paper surface sizing agent
Synthetic method, which is characterized in that the water soluble polymer in the step 2 includes styrene-acrylic emulsion, oxidized starch, polypropylene
Amide, one kind in carboxymethyl cellulose (CMC).
5. a kind of macromolecule according to claim 1/layered double hydroxide base fluorescent type paper surface sizing agent
Synthetic method, which is characterized in that in the step two water soluble polymer mass concentration be 0.02~0.2g/ml.
6. a kind of macromolecule according to claim 1/layered double hydroxide base fluorescent type paper surface sizing agent
Synthetic method, which is characterized in that the soluble-salt of the soluble-salt and trivalent metal of divalent metal in the step three
Molar ratio is 1:1-1:3, the molar ratio of urea and trivalent soluble-salt is 9:1-18:1, described is configured to trivalent metal ion
A concentration of 1 × 10-3~1 × 10-2g/ml。
7. a kind of macromolecule according to claim 1/layered double hydroxide base fluorescent type paper surface sizing agent
Synthetic method, which is characterized in that bivalent metal ion includes Zn in the step 32+And Mg2+。
8. a kind of macromolecule according to claim 1/layered double hydroxide base fluorescent type paper surface sizing agent
Synthetic method, which is characterized in that trivalent metal ion includes Al in the step 33+。
9. a kind of macromolecule according to claim 1/layered double hydroxide base fluorescent type paper surface sizing agent
Synthetic method, which is characterized in that the step four keeps 60-85 DEG C of reaction temperature, reaction time 2-4h, nitrogen to protect
Shield.
10. a kind of macromolecule according to claim 1/layered double hydroxide base fluorescent type paper surface sizing agent
Synthetic method, which is characterized in that aging 10-14 hours at 90-110 DEG C in a kettle in the step five.
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Citations (4)
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CN101775281A (en) * | 2010-01-22 | 2010-07-14 | 北京化工大学 | Fluorescent brightener CBS intercalated hydrotalcite composite luminescent material and preparation method thereof |
US20110000632A1 (en) * | 2007-12-21 | 2011-01-06 | Auke Gerardus Talma | Process to Make a Clay Comprising Charge-Balancing Organic Ions, Clays Thus Obtained, and Nanocomposite Materials Comprising the Same |
CN101974323A (en) * | 2010-09-09 | 2011-02-16 | 北京化工大学 | Piezofluorescent color changing material with intercalation structure and preparation method thereof |
CN103469690A (en) * | 2013-09-17 | 2013-12-25 | 山西青山化工有限公司 | Method for improving whitening efficiency of fluorescent whitening agent on paper surface |
-
2018
- 2018-03-23 CN CN201810247400.0A patent/CN108486954A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110000632A1 (en) * | 2007-12-21 | 2011-01-06 | Auke Gerardus Talma | Process to Make a Clay Comprising Charge-Balancing Organic Ions, Clays Thus Obtained, and Nanocomposite Materials Comprising the Same |
CN101775281A (en) * | 2010-01-22 | 2010-07-14 | 北京化工大学 | Fluorescent brightener CBS intercalated hydrotalcite composite luminescent material and preparation method thereof |
CN101974323A (en) * | 2010-09-09 | 2011-02-16 | 北京化工大学 | Piezofluorescent color changing material with intercalation structure and preparation method thereof |
CN103469690A (en) * | 2013-09-17 | 2013-12-25 | 山西青山化工有限公司 | Method for improving whitening efficiency of fluorescent whitening agent on paper surface |
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Application publication date: 20180904 |