CN114958258A - zero-VOC aldehyde-free surface coating adhesive for impregnated paper and preparation method thereof - Google Patents

zero-VOC aldehyde-free surface coating adhesive for impregnated paper and preparation method thereof Download PDF

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CN114958258A
CN114958258A CN202210782787.6A CN202210782787A CN114958258A CN 114958258 A CN114958258 A CN 114958258A CN 202210782787 A CN202210782787 A CN 202210782787A CN 114958258 A CN114958258 A CN 114958258A
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acid
aldehyde
voc
zero
impregnated paper
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叶武龙
蒋哲明
刘小林
阳习春
易添福
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Hunan Linte Technology Co ltd
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Hunan Linte Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates

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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a zero VOC aldehyde-free surface coating adhesive for impregnated paper and a preparation method thereof, and relates to the field of impregnated paper adhesives. According to the invention, by introducing the cross network structure of the dihydric alcohol with the self-lubricating effect and the polyester modified acrylate, the problems of insufficient hardness and scratch resistance of the surface coating in the existing aldehyde-free new technology are solved, and the alcohol resistance and the water resistance are excellent. The zero-VOC aldehyde-free surface coating for the impregnated paper does not contain any organic solvent, so that the real zero-VOC is realized.

Description

zero-VOC aldehyde-free surface coating adhesive for impregnated paper and preparation method thereof
Technical Field
The invention relates to the field of impregnated paper adhesives, in particular to a zero-VOC aldehyde-free surface coating adhesive for impregnated paper and a preparation method thereof.
Background
In the existing impregnated paper production process, melamine glue and urea-formaldehyde glue are indispensable raw materials, the raw materials contain formaldehyde, and harmful substances such as formaldehyde, phenol and the like can be released in glue solution preparation, paper impregnation, plate pressing and finished furniture use processes, so that the health of people is harmed. Therefore, in order to solve the problem of formaldehyde pollution to air and protect the life health of people, a plurality of researchers are dedicated to the research and development work of the formaldehyde-free impregnated paper adhesive.
Chinese patent CN109385229A discloses a modified composite formaldehyde-free wear-resistant adhesive and a manufacturing method thereof, wherein the transparency is only 61% -66%, and the display of printing lines is seriously influenced, so that the decorative aesthetic effect is influenced. In addition, polyvinyl acetate and polyvinyl alcohol are easy to yellow and affect water resistance.
Chinese patent CN109851720A discloses an aldehyde-free impregnating adhesive and a synthesis process thereof, wherein a thermoplastic polyurethane modified acrylic emulsion is used as a top coating, the VOC emission is high, the pencil hardness is only HB, and after the adhesive is attached to a plate, a nail is pressed and scratched with a mark, so that the requirements of end consumers are difficult to meet.
Chinese patent CN112159502A discloses a preparation method of formaldehyde-free glue for impregnated paper, which adopts a post-crosslinking acrylic emulsion system, and the acrylic emulsion has the problem of poor solvent resistance, especially poor alcohol resistance.
Chinese patent CN104140777A discloses a formaldehyde-free impregnated paper laminated decorative board and a preparation method thereof, wherein formaldehyde-free glue is prepared from xylenol, melamine, furfural, methanol and the like, the problem of easy yellowing during baking is solved, and a large amount of methanol solvent with low flash point and toxicity is contained.
Chinese patent CN113024756A discloses an aldehyde-free environment-friendly resin colloid for impregnated paper and a preparation method thereof, wherein formaldehyde is still used as a raw material, and the problem of formaldehyde release in glue solution preparation or the problem of containing a small amount of free phenol exists.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: (1) the melamine-formaldehyde surface coating adhesive for the traditional impregnated paper contains formaldehyde; (2) the problems of insufficient hardness, scratch resistance and high VOC (volatile organic compound) emission of the surface coating adhesive in the existing aldehyde-free new technology are solved; (3) the problems of alcohol intolerance and water intolerance of the existing aldehyde-free new technology exist in the surface coating glue.
In order to solve the problems, the inventor provides a preparation method of novel aldehyde-free impregnated membrane paper through numerous tests, which comprises the following steps:
s1, soaking the base paper in the base coating glue, and then taking out and drying the soaked base paper to obtain the base paper with the base coating glue on the front and back surfaces;
s2, coating back glue on one side, close to the base material, of the base paper coated with the base glue obtained in the step S1, coating surface glue on the other side of the base paper, and drying to obtain the novel aldehyde-free impregnated membrane paper;
and S3, carrying out veneering hot pressing on the coated back adhesive side of the novel aldehyde-free impregnated film paper obtained in the step S2 and the base material to finish the curing and bonding of the impregnated paper and the base material.
The invention provides a zero VOC aldehyde-free surface coating adhesive for impregnated paper, which comprises the following components in percentage by mass:
1% -15% of polyester resin;
1% -5% of hydrophilic monomer;
15% -35% of hydrophobic monomer;
0.5% -5% of emulsifier;
1% -5% of external cross-linking agent;
0.05% -2% of an initiator;
3% -5% of a neutralizer;
0.05% -1% of defoaming agent;
0.1% -1% of mildew-proof bactericide;
40% -60% of water;
the sum of the mass percentages of the components is 100 percent;
the hydrophilic monomer is selected from one or more of dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, 4-hydroxypropyl 2-acrylate, beta-acryloxypropionic acid, methacrylic acid, acrylic acid and acrylamide;
the hydrophobic monomer is selected from one or more of ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, styrene, butyl methacrylate, isobornyl methacrylate and methyl styrene;
the emulsifier is selected from one or more of allyloxy nonyl phenol polyoxyethylene ether, allyloxy nonyl phenol polyoxyethylene ether sulfate, sodium vinylsulfonate, sodium allylsulfonate, sodium methallyl sulfonate, sodium allyloxy hydroxypropyl sulfonate, sodium 2-acrylamide-2-methylpropanesulfonate and sodium p-styrene sulfonate;
the external cross-linking agent is selected from one or more of water-based carbodiimide, water-based organosilicon cross-linking agent, water-based blocked isocyanate and water-based blocked aziridine;
the initiator is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate and 2, 2' -azo (2-methylpropylamidine) dihydrochloride;
the neutralizing agent is selected from one or more of ammonia water, N-dimethylethanolamine, triethylamine and 2-amino-2-methyl-1-propanol.
Preferably, the polyester resin is prepared from the following raw materials in percentage by weight:
30% -50% of dibasic acid;
35% -55% of dihydric alcohol;
0.1% -0.5% of catalyst;
0.1% -0.5% of antioxidant;
5% -20% of methyl methacrylate;
the sum of the mass percentages of the components is 100 percent;
the dibasic acid is one or more of adipic acid, maleic anhydride, fumaric acid, 1, 4-succinic acid, 1, 4-cyclohexanedicarboxylic acid, azelaic acid, sebacic acid, terephthalic acid and isophthalic acid;
the dihydric alcohol is one or more of neopentyl glycol, 1, 4-butanediol, 1, 6-hexanediol, polyethylene glycol and polypropylene glycol;
the catalyst is one or more of monobutyl tin oxide, dibutyltin dilaurate and ethylene glycol antimony;
the antioxidant is one or more of triphenyl phosphite, FIrganox1425, Irganox1010 and Irganox 1098.
More preferably, the preparation process of the polyester resin is as follows:
adding dibasic acid, dihydric alcohol, a catalyst and an antioxidant into a reaction kettle, heating to 150-180 ℃ under the stirring condition, carrying out heat preservation reaction for 0.5-1.5 h, then heating in a stepwise manner to 220-240 ℃, carrying out heat preservation reaction until the acid value is less than 10mgKOH/g, reducing the acid value to below 60 ℃, adding methyl methacrylate, and mixing uniformly to obtain the polyester resin.
Preferably, the defoamer is basf NXZ.
Preferably, the mildew-proof bactericide is KATHON CG bactericide.
Preferably, deionized water is used as the solvent.
The invention also provides a preparation method of the zero VOC aldehyde-free top coating adhesive for the impregnated paper, which comprises the following steps:
s1, dispersing polyester resin, hydrophobic monomers, hydrophilic monomers, an emulsifier and deionized water into a pre-emulsion at a high speed, and adding the pre-emulsion into a monomer high-position dripping tank;
s2, uniformly mixing the initiator and part of deionized water, and adding the mixture into an initiator high-position dropwise adding groove;
s3, adding part of deionized water into the reactor to serve as reaction base liquid, and heating to 70-97 ℃;
s4, adding a small amount of initiator solution into the base solution, reacting for 10-40 min, synchronously dropwise adding the rest initiator solution and the pre-emulsion for 1.5-5 h, preserving heat for 0.5-2.5 h, and cooling;
and S5, sequentially adding a neutralizing agent, an external cross-linking agent, a defoaming agent and a mildew-proof bactericide, and uniformly mixing to obtain the polyester modified acrylate.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) the formaldehyde-free surface coating adhesive prepared by the invention does not contain formaldehyde in the raw materials, production, preparation, film forming, crosslinking and curing processes, solves the problem of formaldehyde release caused by the melamine-formaldehyde adhesive for the traditional impregnated paper, and realizes real formaldehyde-free home decoration.
(2) According to the invention, by introducing the cross network structure of the dihydric alcohol with the self-lubricating effect and the polyester modified acrylate, the problems of insufficient hardness and scratch resistance of the surface coating in the existing aldehyde-free new technology are solved, and the alcohol resistance and the water resistance are excellent.
(3) The zero-VOC aldehyde-free surface coating for the impregnated paper does not contain any organic solvent, so that the real zero-VOC is realized.
Drawings
FIG. 1 is a flow chart of the preparation process of the zero VOC aldehyde-free top coating of the present invention.
Detailed Description
In this example, unless otherwise specified, all reagents used were common commercial products or prepared by conventional means, and the equipment used was conventional in the art, and the following are some examples of the inventors in the experiment:
example 1
A preparation method of zero VOC aldehyde-free surface coating adhesive for impregnated paper comprises the following steps:
s1, dispersing polyester resin, hydrophobic monomers, hydrophilic monomers, an emulsifier and deionized water into a pre-emulsion at a high speed, and adding the pre-emulsion into a monomer high-position dripping tank;
s2, uniformly mixing the initiator and part of deionized water, and adding the mixture into an initiator high-position dropwise adding groove;
s3, adding part of deionized water into the reactor to serve as reaction base liquid, and heating to 85 ℃;
s4, adding a small amount of initiator solution into the base solution, reacting for 30min, synchronously dropwise adding the rest initiator solution and the pre-emulsion, dropwise adding for 3h, preserving heat for 2h, and cooling;
and S5, sequentially adding a neutralizing agent, an external cross-linking agent, a defoaming agent and a mildew-proof bactericide, and uniformly mixing to obtain the polyester modified acrylate.
The zero-VOC aldehyde-free top coating adhesive comprises the following components in percentage by mass:
10% of polyester resin;
hydrophilic monomer: 3% of methacrylic acid;
hydrophobic monomer: 10% of isooctyl acrylate and 17% of methyl methacrylate;
emulsifier: 2% of allyloxy nonyl phenol polyoxyethylene ether sulfate;
external crosslinking agent: 4% of aqueous blocked aziridine;
initiator: 0.5 percent of ammonium persulfate;
neutralizing agent: 3% of ammonia water;
basf NXZ 0.1%;
0.1% of KATHON CG bactericide;
50.3 percent of deionized water.
The polyester resin is prepared from the following raw materials in percentage by weight:
dibasic acid: 10% of adipic acid, 10% of maleic anhydride and 20% of isophthalic acid;
glycol: neopentyl glycol 20% and polypropylene glycol 20%;
catalyst: 0.1% of monobutyl tin oxide;
antioxidant: 0.1% of triphenyl phosphite;
19.8 percent of methyl methacrylate;
the preparation process of the polyester resin comprises the following steps:
adding dibasic acid, dihydric alcohol, a catalyst and an antioxidant into a reaction kettle, heating to 150 ℃ under the stirring condition, then carrying out heat preservation reaction for 1h, then heating in a stepwise manner to 230 ℃, carrying out heat preservation reaction until the acid value is less than 10mgKOH/g, reducing to below 60 ℃, adding methyl methacrylate, and mixing uniformly to obtain the polyester resin.
Example 2
A preparation method of zero VOC aldehyde-free top coating adhesive for impregnated paper comprises the following steps:
s1, dispersing polyester resin, hydrophobic monomers, hydrophilic monomers, an emulsifier and deionized water into a pre-emulsion at a high speed, and adding the pre-emulsion into a monomer high-position dripping tank;
s2, uniformly mixing the initiator and part of deionized water, and adding the mixture into an initiator high-position dropwise adding groove;
s3, adding part of deionized water into the reactor to serve as reaction base liquid, and heating to 87 ℃;
s4, adding a small amount of initiator solution into the base solution, reacting for 20min, synchronously dropwise adding the rest initiator solution and the pre-emulsion, dropwise adding for 2.5h, preserving heat for 2h, and then cooling;
and S5, sequentially adding a neutralizing agent, an external cross-linking agent, a defoaming agent and a mildew-proof bactericide, and uniformly mixing to obtain the polyester modified acrylate.
The zero-VOC aldehyde-free top coating adhesive comprises the following components in percentage by mass:
15% of polyester resin;
hydrophilic monomer: 1% of dimethylaminoethyl acrylate and 3% of acrylic acid;
hydrophobic monomer: 5% of butyl acrylate, 5% of isooctyl acrylate and 10% of isobornyl methacrylate;
emulsifier: 1% of allyloxy nonylphenol polyoxyethylene ether and 2% of allyloxy nonylphenol polyoxyethylene ether sulfate;
external crosslinking agent: 3% of a water-based organic silicon cross-linking agent;
initiator: 0.5 percent of potassium persulfate;
neutralizing agent: 3% of triethylamine;
basf NXZ 0.2%;
0.2% of KATHON CG bactericide;
and 51.1% of deionized water.
The polyester resin is prepared from the following raw materials in percentage by weight:
dibasic acid: 10% of maleic anhydride, 10% of 1, 4-cyclohexanedicarboxylic acid and 20% of isophthalic acid;
a dihydric alcohol: neopentyl glycol 15%, 1, 6-hexanediol 5% and polyethylene glycol 25%;
catalyst: 0.2 percent of ethylene glycol antimony;
antioxidant: irganox 10100.2%;
14.6 percent of methyl methacrylate;
the preparation process of the polyester resin comprises the following steps:
adding dibasic acid, dihydric alcohol, a catalyst and an antioxidant into a reaction kettle, heating to 160 ℃ under the stirring condition, carrying out heat preservation reaction for 1h, heating in a stepwise manner to 220 ℃, carrying out heat preservation reaction until the acid value is less than 10mgKOH/g, reducing the temperature to below 60 ℃, adding methyl methacrylate, and mixing uniformly to obtain the polyester resin.
Example 3
A preparation method of zero VOC aldehyde-free top coating adhesive for impregnated paper comprises the following steps:
s1, dispersing polyester resin, hydrophobic monomers, hydrophilic monomers, an emulsifier and deionized water at a high speed into a pre-emulsion, and adding the pre-emulsion into a monomer high-position dripping tank;
s2, uniformly mixing the initiator and part of deionized water, and adding the mixture into an initiator high-position dropwise adding groove;
s3, adding part of deionized water into the reactor to serve as reaction base liquid, and heating to 80 ℃;
s4, adding a small amount of initiator solution into the base solution, reacting for 30min, synchronously dropwise adding the rest initiator solution and the pre-emulsion, dropwise adding for 3.5h, preserving heat for 2.5h, and then cooling;
and S5, sequentially adding a neutralizing agent, an external cross-linking agent, a defoaming agent and a mildew-proof bactericide, and uniformly mixing to obtain the polyester modified acrylate.
The zero-VOC aldehyde-free top coating adhesive comprises the following components in percentage by mass:
5% of polyester resin;
hydrophilic monomer: 5% methacrylic acid;
hydrophobic monomer: 15% butyl acrylate, 15% methyl styrene;
emulsifier: 3% of allyloxy nonylphenol polyoxyethylene ether sulfate and 1% of allyloxy hydroxypropyl sodium sulfonate;
external crosslinking agent: 3% aqueous blocked isocyanate;
initiator: 1% 2, 2' -azo (2-methylpropylamidine) dihydrochloride;
neutralizing agent: 5% N, N-dimethylethanolamine;
basf NXZ 0.2%;
0.2% of KATHON CG bactericide;
46.6 percent of deionized water.
The polyester resin is prepared from the following raw materials in percentage by weight:
dibasic acid: 20% of adipic acid and 30% of isophthalic acid;
a dihydric alcohol: 10% of neopentyl glycol, 10% of 1, 4-butanediol and 15% of polypropylene glycol;
0.1 percent of dibutyltin dilaurate;
FIrganox1425 0.1%；
14.8 percent of methyl methacrylate;
the preparation process of the polyester resin comprises the following steps:
adding dibasic acid, dihydric alcohol, a catalyst and an antioxidant into a reaction kettle, heating to 180 ℃ under the stirring condition, carrying out heat preservation reaction for 1h, heating in a stepwise manner to 240 ℃, carrying out heat preservation reaction until the acid value is less than 10mgKOH/g, reducing the temperature to below 60 ℃, adding methyl methacrylate, and mixing uniformly to obtain the polyester resin.
Example 4
A preparation method of aldehyde-free impregnated membrane paper comprises the following steps:
(1) soaking base paper in the base coating adhesive, taking out the soaked base paper and drying to obtain the base paper with the base coating adhesive on the front surface and the back surface;
(2) coating back glue on one side, close to the base material, of the base paper coated with the base glue, coating the surface glue prepared in the embodiment 1 on the other side of the base paper, and drying to obtain aldehyde-free impregnated membrane paper;
(3) carrying out veneering hot pressing on the side of the formaldehyde-free impregnated film paper coated with the back glue and the base material to finish the curing and bonding of the impregnated paper and the base material;
the formula of the bottom coating adhesive is as follows:
hydrophilic crosslinking monomer: 25% of methacrylic acid and 15% of acrylic acid;
permeable monomer: allyl alkyl sulfosuccinate sodium salt (model M-12S, purchased from Shanghai loyal Fine chemical Co., Ltd.) 7.5%, sodium 2-acrylamido-2-methylpropanesulfonate 10%;
hydrophobic monomers: 20% of ethyl acrylate, 5% of methyl methacrylate and 5% of styrene;
internal crosslinking monomer: 0.5 percent of trihydroxy propane triacrylate;
external crosslinking agent: 6% of isocyanate;
initiator: 5% of potassium persulfate;
basf NXZ 0.5%;
0.5% of KATHON CG bactericide;
233% of deionized water.
The back coating formula comprises:
hydrophilic crosslinking monomer: 10% of methacrylic acid and 8% of acrylic acid;
improving the adhesive force monomer: 5% of ethylene glycol methacrylate phosphate and 5% of epoxy resin E51;
hydrophobic monomers: 30% of isooctyl acrylate, 10% of methyl methacrylate and 20% of styrene;
emulsifier: 3% of allyloxy nonyl phenol polyoxyethylene ether sulfate and 2% of 2-acrylamide-2-methyl sodium propyl sulfonate;
external crosslinking agent: 3% Wanjun chemical NWIITC ® C5, 3% Wanjun chemical NWIITC ® C32；
Initiator: 0.6 percent of potassium persulfate;
basf NXZ 0.2%;
0.2% of KATHON CG bactericide;
and 150% of deionized water.
The surface properties of the impregnated paper after hot pressing were tested in relation to each other and the results are shown below:
surface bonding strength Wear-resistant Rhodamine-hydrochloric acid resistant Alcohol-resistant Scratch-resistant Resistant poaching Hardness of Free formaldehyde emission mg/L
≥1.5MPa ≤75mg/100r Qualified 500g, 30 times ≥1.5N No peeling after 2 hours ≥H Not detected out
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (6)

1. The zero-VOC aldehyde-free top coating adhesive for the impregnated paper is characterized by comprising the following components in percentage by mass:
1% -15% of polyester resin;
1% -5% of hydrophilic monomer;
15% -35% of hydrophobic monomer;
0.5% -5% of emulsifier;
1% -5% of external cross-linking agent;
0.05% -2% of an initiator;
3% -5% of a neutralizer;
0.05% -1% of defoaming agent;
0.1% -1% of mildew-proof bactericide;
40% -60% of water;
the sum of the mass percentages of the components is 100 percent;
the hydrophilic monomer is selected from one or more of dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, 4-hydroxypropyl 2-acrylate, beta-acryloxypropionic acid, methacrylic acid, acrylic acid and acrylamide;
the hydrophobic monomer is selected from one or more of ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, styrene, butyl methacrylate, isobornyl methacrylate and methyl styrene;
the emulsifier is selected from one or more of allyloxy nonyl phenol polyoxyethylene ether, allyloxy nonyl phenol polyoxyethylene ether sulfate, sodium vinylsulfonate, sodium allylsulfonate, sodium methallyl sulfonate, sodium allyloxy hydroxypropyl sulfonate, sodium 2-acrylamide-2-methylpropanesulfonate and sodium p-styrene sulfonate;
the external cross-linking agent is selected from one or more of water-based carbodiimide, water-based organosilicon cross-linking agent, water-based blocked isocyanate and water-based blocked aziridine;
the initiator is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate and 2, 2' -azo (2-methylpropylamidine) dihydrochloride;
the neutralizing agent is selected from one or more of ammonia water, N-dimethylethanolamine, triethylamine and 2-amino-2-methyl-1-propanol.
2. The zero-VOC aldehyde-free top coating for impregnated paper according to claim 1, wherein the polyester resin is prepared from the following raw materials in percentage by weight:
30% -50% of dibasic acid;
35% -55% of dihydric alcohol;
0.1% -0.5% of catalyst;
0.1% -0.5% of antioxidant;
5% -20% of methyl methacrylate;
the sum of the mass percentages of the components is 100 percent;
the dibasic acid is one or more of adipic acid, maleic anhydride, fumaric acid, 1, 4-succinic acid, 1, 4-cyclohexanedicarboxylic acid, azelaic acid, sebacic acid, terephthalic acid and isophthalic acid;
the dihydric alcohol is one or more of neopentyl glycol, 1, 4-butanediol, 1, 6-hexanediol, polyethylene glycol and polypropylene glycol;
the catalyst is one or more of monobutyl tin oxide, dibutyltin dilaurate and ethylene glycol antimony;
the antioxidant is one or more of triphenyl phosphite, FIrganox1425, Irganox1010 and Irganox 1098.
3. The zero-VOC aldehyde-free top coating for impregnated paper according to claim 2, wherein the polyester resin is prepared by the following steps:
adding dibasic acid, dihydric alcohol, a catalyst and an antioxidant into a reaction kettle, heating to 150-180 ℃ under the stirring condition, carrying out heat preservation reaction for 0.5-1.5 h, then heating in a stepwise manner to 220-240 ℃, carrying out heat preservation reaction until the acid value is less than 10mgKOH/g, reducing the acid value to below 60 ℃, adding methyl methacrylate, and mixing uniformly to obtain the polyester resin.
4. The zero-VOC aldehyde-free top-coating for impregnated paper according to claim 1 or 2, wherein the defoamer is basf NXZ.
5. The zero-VOC aldehyde-free top-coating for impregnated paper as claimed in claim 1 or 2, wherein the mildew-resistant biocide is KATHON CG biocide.
6. The method for preparing a zero-VOC aldehyde-free top-coating for impregnated paper according to any of claims 1 to 5, comprising the steps of:
s1, dispersing polyester resin, hydrophobic monomers, hydrophilic monomers, an emulsifier and deionized water into a pre-emulsion at a high speed, and adding the pre-emulsion into a monomer high-position dripping tank;
s2, uniformly mixing the initiator and part of deionized water, and adding the mixture into an initiator high-position dropwise adding groove;
s3, adding part of deionized water into the reactor to serve as reaction base liquid, and heating to 70-97 ℃;
s4, adding a small amount of initiator solution into the base solution, reacting for 10-40 min, synchronously dropwise adding the rest initiator solution and the pre-emulsion for 1.5-5 h, preserving heat for 0.5-2.5 h, and cooling;
and S5, sequentially adding a neutralizing agent, an external cross-linking agent, a defoaming agent and a mildew-proof bactericide, and uniformly mixing to obtain the anti-mildew agent.
CN202210782787.6A 2022-07-05 2022-07-05 zero-VOC aldehyde-free surface coating adhesive for impregnated paper and preparation method thereof Pending CN114958258A (en)

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Application publication date: 20220830