CN107780299A - A kind of printing paper mildew resistant moistureproof agent and preparation method thereof - Google Patents
A kind of printing paper mildew resistant moistureproof agent and preparation method thereof Download PDFInfo
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- CN107780299A CN107780299A CN201610721391.5A CN201610721391A CN107780299A CN 107780299 A CN107780299 A CN 107780299A CN 201610721391 A CN201610721391 A CN 201610721391A CN 107780299 A CN107780299 A CN 107780299A
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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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
-
- 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
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/18—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising waxes
-
- 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
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Epoxy Resins (AREA)
- Paper (AREA)
Abstract
The invention discloses a kind of printing paper mildew resistant moistureproof agent, include the raw material of following parts by weight：20 40 parts of synthetic resin, 28 parts of paraffin, 26 parts of chitosan, nano-TiO20.5 1 parts, 28 parts of Tissuemat E, 4 10 parts of rosin resin, 0.5 1 parts of ethanol, 30 50 parts of deionized water, 12 parts of auxiliary agent.Preparation method comprises the following steps：（1）Chitosan is added in deionized water by weight, is configured to the solution that concentration is 4 6% mass fractions；（2）By synthetic resin, paraffin, Tissuemat E, rosin resin, ethanol and auxiliary agent, it is uniformly mixed；（3）Sequentially add acetic acid, epoxychloropropane, the nano-TiO that concentration is 10% mass fraction2And step（2）Mixture stir, under 25 28 °C of steady temperature ultrasonic oscillator vibrate 10 20min,.Present invention incorporates chitosan natural antibacterial agent and nano-TiO 2, there is good mould proof characteristic, rate of drying is fast, wear-resisting, water-fast and waterproof.
Description
Technical field
The present invention relates to pulp technology for making paper, specifically a kind of printing paper mildew resistant moistureproof agent and preparation method thereof.
Background technology
In daily life, paper and mouldy become damp of various paper products cause heavy losses to personal, enterprise and country.Paper
And its process of going mouldy of product, it is that the i.e. paper products of paper products mechanical and physical performance decline destroyed by irreversible in fact
Journey.Mould has certain influence to the physical property (such as folding strength, tension stress) of paper.
The paper of mechanical paper technique productions is usually what is carried disease germs, and some aseptic papers seen in life are all to pass through addition
What the methods of antiseptic, obtained.Antiseptic is according to chemical composition broadly divided into inorganic antiseptic, organic antibacterial agent and natural antibacterial
Agent etc..In the past 10 years, as green requirement is more and more stricter, researcher turns one's attention to replacing for organic antibacterial agent one after another
For thing-inorganic antiseptic and natural antibacterial agent.Chitosan belongs to natural antibacterial agent, has good Bc and degradable
Property, it is renewable, have no toxic side effect, there is preferable Antimicrobial preservative ability.Nano-TiO2Belong to as a kind of photo-catalytic sterilization material
Non-dissolving type inorganic antiseptic, nontoxic, tasteless, non-stimulated, heat endurance is strong with heat resistance.
The content of the invention
It is an object of the invention to provide a kind of printing paper mildew resistant moistureproof agent and preparation method thereof, to solve above-mentioned background
The problem of being proposed in technology.
To achieve the above object, the present invention provides following technical scheme：
A kind of printing paper mildew resistant moistureproof agent, include the raw material of following parts by weight：Synthetic resin 20-40 parts, paraffin 2-8 parts, shell
Glycan 2-6 parts, nano-TiO20.5-1 parts, Tissuemat E 2-8 parts, rosin resin 4-10 parts, ethanol 0.5-1 parts, deionized water
30-50 parts, auxiliary agent 1-2 parts.
As further scheme of the invention：Include the raw material of following parts by weight：Synthetic resin 25-35 parts, paraffin
3.5-6.5 parts, chitosan 3-5 parts, nano-TiO20.6-0.9 parts, Tissuemat E 3.5-6.5 parts, rosin resin 5.5-8.5 parts,
Ethanol 0.6-0.9 parts, deionized water 35-45 parts, auxiliary agent 1-2 parts.
As further scheme of the invention：Include the raw material of following parts by weight：30 parts of synthetic resin, 5 parts of paraffin, shell
4 parts of glycan, nano-TiO20.75 part, 5 parts of Tissuemat E, 7 parts of rosin resin, 0.75 part of ethanol, 40 parts of deionized water, auxiliary agent
1.5 part.
As further scheme of the invention：The synthetic resin is polyethylene, polypropylene, polyvinyl chloride, polyphenyl second
One or more of mixtures in alkene and ABS.
As further scheme of the invention：The auxiliary agent includes emulsifying agent and dispersant.
As further scheme of the invention：The emulsifying agent is odium stearate, CSL and biacetyl wine
One or more of mixtures in stone acid monoglyceride.
As further scheme of the invention：The dispersant is vinyl bis-stearamides, glyceryl monostearate
With one or more of mixtures in glyceryl tristearate.
As further scheme of the invention：The preparation method of described printing paper mildew resistant moistureproof agent, including it is following
Step：
（1）Chitosan is added in deionized water by weight, is configured to the solution that concentration is 4-6% mass fractions；
（2）Synthetic resin, paraffin, Tissuemat E, rosin resin, ethanol and auxiliary agent are weighed by weight, are uniformly mixed, it is standby
With；
（3）Sequentially add acetic acid, epoxychloropropane, the nano-TiO that concentration is 10% mass fraction2And step（2）Mixture stir
Mix uniformly, the acetic acid and epoxychloropropane add 0.4-0.6ml, are shaken under 25-28 °C of steady temperature in ultrasonic oscillator
10-20min is swung,.
As further scheme of the invention：Step（3）Described in nano-TiO2Average grain diameter in 15-85nm.
Compared with prior art, the beneficial effects of the invention are as follows：The paper mildew resistant moistureproof agent of the present invention, combines chitosan
Natural antibacterial agent and nano-TiO 2, with nano-TiO 2Chitosan is modified and prepares antibacterial and mouldproof anti-blushing agent, daily
There is photocatalytic activity, 24h sterilizing rates reach 99.99% under illumination condition.Under daily photoenvironment, at antibacterial mildew inhibitor
Paper after reason has good mould proof characteristic, and the paper surface after processing grows almost without mildew；Synthetic resin has film forming
A series of premium properties, the auxiliary agents such as property good, glossiness is good, transparency is high, rate of drying is fast, wear-resisting, water-fast and waterproof can be effective
Ensure paper anti-blushing agent quality, add ethanol in right amount during a large amount of water uses, colourless, tasteless, nontoxic, volatility is almost nil, stream
Levelling is also very good, to improve the drying property of aqueous solvent, improves the flexibility (adaptability) of operation of watery water-proofing agent, mildew resistant moistureproof agent is made
For the waterproof of paper products, protection against the tide, mould proof.
Embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
Embodiment 1
In the embodiment of the present invention, a kind of printing paper mildew resistant moistureproof agent, include the raw materials of following parts by weight：20 parts of synthetic resin,
2 parts of paraffin, 2 parts of chitosan, nano-TiO20.5 part, 2 parts of Tissuemat E, 4 parts of rosin resin, 0.5 part of ethanol, deionized water 30
Part, 1 part of auxiliary agent.
The synthetic resin is polyethylene, polyacrylic mixture.
The auxiliary agent includes emulsifying agent and dispersant.
The emulsifying agent is odium stearate.
The dispersant is vinyl bis-stearamides.
The preparation method of described printing paper mildew resistant moistureproof agent, comprises the following steps：
（1）Chitosan is added in deionized water by weight, is configured to the solution that concentration is 4% mass fraction；
（2）Synthetic resin, paraffin, Tissuemat E, rosin resin, ethanol and auxiliary agent are weighed by weight, are uniformly mixed, it is standby
With；
（3）Sequentially add acetic acid, epoxychloropropane, the nano-TiO that concentration is 10% mass fraction2And step（2）Mixture stir
Mix uniformly, the acetic acid and epoxychloropropane add 0.4ml, described nano-TiO2Average grain diameter in 15nm, constant temperature
10min is vibrated in ultrasonic oscillator under 25 °C of degree,.
Embodiment 2
In the embodiment of the present invention, a kind of printing paper mildew resistant moistureproof agent, include the raw materials of following parts by weight：25 parts of synthetic resin,
3.5 parts of paraffin, 3 parts of chitosan, nano-TiO20.6 part, 3.5 parts of Tissuemat E, 5.5 parts of rosin resin, 0.6 part of ethanol, go from
Sub- 35 parts of water, 1 part of auxiliary agent.
The synthetic resin is polyvinyl chloride, the mixture of polystyrene.
The auxiliary agent includes emulsifying agent and dispersant.
The emulsifying agent is CSL and the mixture of diacetyl tartarate monoglyceride.
The dispersant is the mixture of glyceryl monostearate and glyceryl tristearate.
The preparation method of described printing paper mildew resistant moistureproof agent, comprises the following steps：
（1）Chitosan is added in deionized water by weight, is configured to the solution that concentration is 4% mass fraction；
（2）Synthetic resin, paraffin, Tissuemat E, rosin resin, ethanol and auxiliary agent are weighed by weight, are uniformly mixed, it is standby
With；
（3）Sequentially add acetic acid, epoxychloropropane, the nano-TiO that concentration is 10% mass fraction2And step（2）Mixture stir
Mix uniformly, the acetic acid and epoxychloropropane add 0.45ml, described nano-TiO2Average grain diameter in 30nm, constant temperature
12min is vibrated in ultrasonic oscillator under 26 °C of degree,.
Embodiment 3
In the embodiment of the present invention, a kind of printing paper mildew resistant moistureproof agent, include the raw materials of following parts by weight：30 parts of synthetic resin,
5 parts of paraffin, 4 parts of chitosan, nano-TiO20.75 part, 5 parts of Tissuemat E, 7 parts of rosin resin, 0.75 part of ethanol, deionized water
40 parts, 1.5 parts of auxiliary agent.
The synthetic resin is polyethylene and ABS mixture.
The auxiliary agent includes emulsifying agent and dispersant.
The emulsifying agent is the mixture of odium stearate and diacetyl tartarate monoglyceride.
The dispersant is the mixture of glyceryl monostearate and glyceryl tristearate.
The preparation method of described printing paper mildew resistant moistureproof agent, comprises the following steps：
（1）Chitosan is added in deionized water by weight, is configured to the solution that concentration is 5% mass fraction；
（2）Synthetic resin, paraffin, Tissuemat E, rosin resin, ethanol and auxiliary agent are weighed by weight, are uniformly mixed, it is standby
With；
（3）Sequentially add acetic acid, epoxychloropropane, the nano-TiO that concentration is 10% mass fraction2And step（2）Mixture stir
Mix uniformly, the acetic acid and epoxychloropropane add 0.5ml, described nano-TiO2Average grain diameter in 50nm, constant temperature
15min is vibrated in ultrasonic oscillator under 26.5 °C of degree,.
Embodiment 4
In the embodiment of the present invention, a kind of printing paper mildew resistant moistureproof agent, include the raw materials of following parts by weight：35 parts of synthetic resin,
6.5 parts of paraffin, 5 parts of chitosan, nano-TiO20.9 part, 6.5 parts of Tissuemat E, 8.5 parts of rosin resin, 0.9 part of ethanol, go from
Sub- 45 parts of water, 2 parts of auxiliary agent.
The synthetic resin is the mixture of polyethylene, polypropylene and ABS.
The auxiliary agent includes emulsifying agent and dispersant.
The emulsifying agent is the mixture of odium stearate, CSL and diacetyl tartarate monoglyceride.
The dispersant is the mixture of vinyl bis-stearamides, glyceryl monostearate and glyceryl tristearate.
The preparation method of described printing paper mildew resistant moistureproof agent, comprises the following steps：
（1）Chitosan is added in deionized water by weight, is configured to the solution that concentration is 5% mass fraction；
（2）Synthetic resin, paraffin, Tissuemat E, rosin resin, ethanol and auxiliary agent are weighed by weight, are uniformly mixed, it is standby
With；
（3）Sequentially add acetic acid, epoxychloropropane, the nano-TiO that concentration is 10% mass fraction2And step（2）Mixture stir
Mix uniformly, the acetic acid and epoxychloropropane add 0.55ml, described nano-TiO2Average grain diameter in 70nm, constant temperature
18min is vibrated in ultrasonic oscillator under 27 °C of degree,.
Embodiment 5
In the embodiment of the present invention, a kind of printing paper mildew resistant moistureproof agent, include the raw materials of following parts by weight：40 parts of synthetic resin,
8 parts of paraffin, 6 parts of chitosan, nano-TiO21 part, 8 parts of Tissuemat E, 10 parts of rosin resin, 1 part of ethanol, 50 parts of deionized water,
2 parts of auxiliary agent.
The synthetic resin is the mixture of polyvinyl chloride, polystyrene and ABS.
The auxiliary agent includes emulsifying agent and dispersant.
The emulsifying agent is odium stearate, the mixture of CSL.
The dispersant is vinyl bis-stearamides, the mixture of glyceryl monostearate.
The preparation method of described printing paper mildew resistant moistureproof agent, comprises the following steps：
（1）Chitosan is added in deionized water by weight, is configured to the solution that concentration is 6% mass fraction；
（2）Synthetic resin, paraffin, Tissuemat E, rosin resin, ethanol and auxiliary agent are weighed by weight, are uniformly mixed, it is standby
With；
（3）Sequentially add acetic acid, epoxychloropropane, the nano-TiO that concentration is 10% mass fraction2And step（2）Mixture stir
Mix uniformly, the acetic acid and epoxychloropropane add 0.6ml, described nano-TiO2Average grain diameter in 85nm, constant temperature
20min is vibrated in ultrasonic oscillator under 28 °C of degree,.
The paper mildew resistant moistureproof agent of the present invention, combines chitosan natural antibacterial agent and nano-TiO 2, with nanometer
TiO 2Chitosan is modified and prepares antibacterial and mouldproof anti-blushing agent, there is photocatalytic activity under daily illumination condition, 24h is killed
Bacterium rate reaches 99.99%.Under daily photoenvironment, the paper after antibacterial mildew inhibitor is handled has good mould proof characteristic, place
Paper surface after reason grows almost without mildew；Synthetic resin has that good film-forming property, glossiness are good, transparency is high, rate of drying
It hurry up, be wear-resisting, a series of premium properties such as water-fast and waterproof, paper anti-blushing agent quality can be effectively ensured in auxiliary agent, when a large amount of water use
Appropriate addition ethanol, colourless, tasteless, nontoxic, volatility is almost nil, and levelability is also very good, to improve the dry of aqueous solvent
Dry performance, improves the flexibility (adaptability) of operation of watery water-proofing agent, and mildew resistant moistureproof agent is used as the waterproof of paper products, protection against the tide, mould proof.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each embodiment is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that those skilled in the art should for clarity
Using specification as an entirety, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
It is appreciated that other embodiment.
Claims (9)
1. a kind of printing paper mildew resistant moistureproof agent, it is characterised in that include the raw material of following parts by weight：Synthetic resin 20-40 parts,
Paraffin 2-8 parts, chitosan 2-6 parts, nano-TiO2 0.5-1 parts, Tissuemat E 2-8 parts, rosin resin 4-10 parts, ethanol 0.5-1
Part, deionized water 30-50 parts, auxiliary agent 1-2 parts.
2. printing paper mildew resistant moistureproof agent according to claim 1, it is characterised in that include the raw material of following parts by weight：
Synthetic resin 25-35 parts, paraffin 3.5-6.5 parts, chitosan 3-5 parts, nano-TiO2 0.6-0.9 parts, Tissuemat E 3.5-6.5
Part, rosin resin 5.5-8.5 parts, ethanol 0.6-0.9 parts, deionized water 35-45 parts, auxiliary agent 1-2 parts.
3. printing paper mildew resistant moistureproof agent according to claim 1, it is characterised in that include the raw material of following parts by weight：
30 parts of synthetic resin, 5 parts of paraffin, 4 parts of chitosan, nano-TiO2 0.75 part, 5 parts of Tissuemat E, 7 parts of rosin resin, ethanol
0.75 part, 40 parts of deionized water, 1.5 parts of auxiliary agent.
4. printing paper mildew resistant moistureproof agent according to claim 1, it is characterised in that the synthetic resin be polyethylene,
One or more of mixtures in polypropylene, polyvinyl chloride, polystyrene and ABS.
5. printing paper mildew resistant moistureproof agent according to claim 1, it is characterised in that the auxiliary agent includes emulsifying agent and divided
Powder.
6. printing paper mildew resistant moistureproof agent according to claim 5, it is characterised in that the emulsifying agent be odium stearate,
One or more of mixtures in CSL and diacetyl tartarate monoglyceride.
7. printing paper mildew resistant moistureproof agent according to claim 5, it is characterised in that the dispersant is that vinyl is double hard
One or more of mixtures in acyl amine, glyceryl monostearate and glyceryl tristearate.
A kind of 8. preparation method of printing paper mildew resistant moistureproof agent as described in claim 1-7 is any, it is characterised in that including
Following steps：
（1）Chitosan is added in deionized water by weight, is configured to the solution that concentration is 4-6% mass fractions；
（2）Synthetic resin, paraffin, Tissuemat E, rosin resin, ethanol and auxiliary agent are weighed by weight, are uniformly mixed, it is standby
With；
（3）Sequentially add acetic acid, epoxychloropropane, the nano-TiO that concentration is 10% mass fraction2And step（2）Mixture stir
Mix uniformly, the acetic acid and epoxychloropropane add 0.4-0.6ml, are shaken under 25-28 °C of steady temperature in ultrasonic oscillator
10-20min is swung,.
9. the preparation method of printing paper mildew resistant moistureproof agent according to claim 8, it is characterised in that step（3）Middle institute
The nano-TiO stated2Average grain diameter in 15-85nm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610721391.5A CN107780299A (en) | 2016-08-25 | 2016-08-25 | A kind of printing paper mildew resistant moistureproof agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610721391.5A CN107780299A (en) | 2016-08-25 | 2016-08-25 | A kind of printing paper mildew resistant moistureproof agent and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110742298A (en) * | 2019-11-15 | 2020-02-04 | 湖北中烟工业有限责任公司 | Method for preventing tobacco sheets from being adhered during storage |
| CN110777560A (en) * | 2019-10-18 | 2020-02-11 | 江苏宇道生物科技有限公司 | Softening agent special for softening and mildew prevention of paper and preparation method thereof |
| CN110983859A (en) * | 2019-12-23 | 2020-04-10 | 江阴市华盛印刷有限公司 | Preparation method and application of waterproof, moistureproof and mildewproof paperboard |
| CN111379182A (en) * | 2020-04-02 | 2020-07-07 | 陈良地 | Preparation method of corrugated paper special for buffer packaging of antibacterial and mildewproof fruits and vegetables |
| CN112080960A (en) * | 2020-09-30 | 2020-12-15 | 王雪峰 | Special fire-resistant, mildew-proof and moisture-proof agent for plant fiber products and preparation method thereof |
-
2016
- 2016-08-25 CN CN201610721391.5A patent/CN107780299A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110777560A (en) * | 2019-10-18 | 2020-02-11 | 江苏宇道生物科技有限公司 | Softening agent special for softening and mildew prevention of paper and preparation method thereof |
| CN110742298A (en) * | 2019-11-15 | 2020-02-04 | 湖北中烟工业有限责任公司 | Method for preventing tobacco sheets from being adhered during storage |
| CN110742298B (en) * | 2019-11-15 | 2022-04-08 | 湖北中烟工业有限责任公司 | Method for preventing tobacco sheets from being adhered during storage |
| CN110983859A (en) * | 2019-12-23 | 2020-04-10 | 江阴市华盛印刷有限公司 | Preparation method and application of waterproof, moistureproof and mildewproof paperboard |
| CN111379182A (en) * | 2020-04-02 | 2020-07-07 | 陈良地 | Preparation method of corrugated paper special for buffer packaging of antibacterial and mildewproof fruits and vegetables |
| CN112080960A (en) * | 2020-09-30 | 2020-12-15 | 王雪峰 | Special fire-resistant, mildew-proof and moisture-proof agent for plant fiber products and preparation method thereof |
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Application publication date: 20180309 |