CN108385435B - Water-based gloss oil and preparation method and application thereof - Google Patents
Water-based gloss oil and preparation method and application thereof Download PDFInfo
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- CN108385435B CN108385435B CN201810108985.8A CN201810108985A CN108385435B CN 108385435 B CN108385435 B CN 108385435B CN 201810108985 A CN201810108985 A CN 201810108985A CN 108385435 B CN108385435 B CN 108385435B
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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
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
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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
- D21H19/18—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising waxes
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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
- D21H21/34—Ignifugeants
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Abstract
The invention provides water-based gloss oil which comprises, by weight, 6% -8% of microencapsulated melamine organic phosphate, 4% -40% of core monomer, 4% -5% of shell monomer, 0.1% -0.2% of emulsifier, 0.1% -0.2% of initiator, 0.3% -0.5% of pH regulator, 0.1% -1.8% of auxiliary agent and 45% -85% of deionized water. The water-based gloss oil has good heat insulation, oxygen insulation, flame retardance and smoke suppression functions, can avoid the defects that an organic phosphorus flame retardant in the water-based gloss oil is easy to migrate, absorb moisture and the like, improves the compatibility of the organic phosphorus flame retardant and a water-based gloss oil matrix, and ensures the glossiness and the mechanical strength of the water-based gloss oil. The water-based gloss oil is coated on the surfaces of corrugated boards and corrugated paper products, so that the corrugated boards and the corrugated paper products have great improvement on flame retardance, water resistance, oil resistance and mechanical strength. The invention also provides a preparation method and application of the water-based gloss oil.
Description
Technical Field
The invention relates to the technical field of water-based gloss oil, and particularly relates to water-based gloss oil and a preparation method and application thereof.
Background
Corrugated paper products are widely used for transporting and packaging household appliances, textiles, food and the like, and about 80% of goods in the world are packaged by corrugated cartons, transferred, shipped, stored, and sold to customers. Many of these products are flammable items, and corrugated paper cartons are generally extremely vulnerable to fire, so that once a fire occurs, not only is the problem of igniting a box, but also the beginning of a disaster. Therefore, the corrugated paper products have great potential safety hazards in the aspect of packaging inflammable products.
In addition, in addition to the use of traditional corrugated paper products for packaging goods, there are more and more environmental protection creative products made of corrugated paper boards in the market, such as corrugated paper exhibition products, corrugated paper furniture, corrugated paper artware, toys and the like. Besides meeting the practical functional requirements of people, the corrugated paper creative products also have the characteristics of environmental protection, economy, fashion and comfort. Corrugated paper materials still have more weak points such as water intolerance, flammability, etc. If the problem is not solved, the creative products related to the corrugated paper cannot be well popularized, and the market space of the corrugated paper products is gradually reduced.
At present, the flame retardant technology of corrugated boards is researched more in China, and the most common is to develop a flame retardant suitable for corrugated boards, for example, CN 106120452a discloses a flame retardant comprising a solvent, ammonium polyphosphate, magnesium-aluminum hydrotalcite, aluminum hydroxide, a dispersing agent, an adhesive and fatty alcohol-polyoxyethylene ether. Although the flame retardant has good flame retardant effect on corrugated boards, the flame retardant has the following disadvantages: after the flame retardant is dried, inorganic components such as magnesium-aluminum hydrotalcite, aluminum hydroxide and the like can be separated out, so that the surface appearance of the paperboard is ugly. In addition, because the water-based flame retardant is sprayed on the corrugated board, the adhesive bonded with the corrugated paper and the face paper is starch glue, so that the corrugated board is degummed to a certain extent after the flame retardant is sprayed, and the mechanical strength of the corrugated board is influenced. CN101130940B discloses a moisture-proof flame-retardant liquid especially suitable for corrugated paper boxes, which contains: zinc borate, hydrochloric acid, water, ammonia water, a moisture-proof agent, epoxy resin and an epoxy resin curing agent. Although the corrugated case impregnated with the moisture-proof flame-retardant liquid has a flame-retardant effect and good moisture resistance, the flame-retardant component adopts a zinc borate inorganic substance, so that the zinc borate inorganic substance cannot be well dissolved in the epoxy resin liquid, and after the zinc borate inorganic substance is coated or impregnated in the corrugated case, the zinc borate inorganic substance and the epoxy resin layer are layered, so that the surface appearance of the corrugated case is poor. Meanwhile, the flame retardant effect is not ideal due to the layering phenomenon.
In practical application, corrugated paper products are often made into required cartons, paper furniture, paper artware and the like through multi-layer bonding, and the flame retardant requirement can be met only by requiring that the printing surface can be self-extinguished away from fire. Therefore, it is necessary to develop a gloss oil with flame retardant function, which is applied to corrugated paper products to make the corrugated paper products have flame retardant function after being coated with the water-based gloss oil.
Disclosure of Invention
The invention aims to provide the water-based gloss oil which has excellent flame retardant property, excellent mechanical property and good compatibility of an organic phosphorus flame retardant and a gloss oil matrix.
The invention also aims to provide a preparation method of the water-based gloss oil.
The invention also aims to provide the application of the water-based gloss oil in corrugated boards and corrugated paper products.
In order to achieve the purpose, the invention provides water-based gloss oil which comprises the following components in percentage by weight:
wherein, the weight percentage of the microencapsulated melamine organic phosphate can be selected from 6%, 7% and 8%; the weight percentage of the nuclear monomer can be selected from 4%, 8%, 12%, 16%, 20%, 24%, 28%, 32%, 36%, 40%; the weight percentage of the shell monomer can be selected from 4%, 4.5% and 5%; the weight percentage of the emulsifier can be selected from 0.1%, 0.15% and 0.2%; the weight percentage of the initiator can be selected from 0.1%, 0.15% and 0.2%; the weight percentage of the pH regulator can be selected from 0.3%, 0.4% and 0.5%; the weight percentage of the auxiliary agent can be selected from 0, 0.1%, 0.5%, 1.0%, 1.5% and 1.8%; the weight percentage of the deionized water can be selected from 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% and 85%.
Compared with the prior art, the water-based varnish has the microencapsulated melamine organic phosphate which contains higher phosphorus, so that the microencapsulated melamine organic phosphate can generate a high-degree dehydration carbonization reaction with a matrix in a degradation process to generate a uniform and compact carbon layer, and therefore, the water-based varnish has good heat insulation, oxygen isolation, flame retardance and smoke suppression functions. Meanwhile, the microencapsulated melamine organic phosphate can also avoid the defects of easy migration and moisture absorption of an organic phosphorus flame retardant in the water-based gloss oil, improve the compatibility of the organic phosphorus flame retardant and a water-based gloss oil matrix, and ensure the glossiness and the mechanical strength of the water-based gloss oil; the pH regulator is adopted to regulate the pH value in the reaction process, so as to prevent the instability of the nuclear monomer; and the core monomers are uniformly dispersed by means of the emulsifier, so that the permeability and the dispersion performance of the gloss oil are improved.
Preferably, the preparation method of the microencapsulated melamine organic phosphate comprises the following steps:
1) adding melamine diphenoxyphosphate and diphenylmethane diisocyanate type polyurethane prepolymer into an organic solvent and uniformly mixing to obtain a mixture A;
2) adding a hardening agent into the mixture A to react to obtain a mixture B;
3) and filtering and drying the mixture B to obtain the microencapsulated melamine organic phosphate.
The melamine diphenoxyl phosphate further reacts with the diphenylmethane diisocyanate type polyurethane prepolymer to obtain the microencapsulated melamine organic phosphate, so that the compatibility of the melamine diphenoxyl phosphate and an acrylic acid monomer in the gloss oil can be further improved, and the glossiness and the mechanical strength of the water-based gloss oil are effectively improved.
Preferably, the mass ratio of the melamine diphenoxy phosphate to the diphenylmethane diisocyanate type polyurethane prepolymer is 1 to (0.2-0.5).
Preferably, the organic solvent may be ethanol.
Preferably, the mass of the hardening agent is 2-4% of the mass of the diphenylmethane diisocyanate type polyurethane prepolymer.
Preferably, the hardening agent is selected from one or more of ammonium chloride, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydrogen phosphate or sodium dihydrogen phosphate.
In one embodiment, the present invention also provides a method for preparing melamine diphenoxyphosphate, comprising:
adding 0.075g/ml of melamine/glacial acetic acid solution into a four-neck flask, heating until the melamine/glacial acetic acid solution is dissolved, keeping the temperature, then dropwise adding 0.1g/ml of diphenyl phosphoric acid/glacial acetic acid solution, completing dropwise adding within about 2 hours, reacting for 16 hours, cooling, filtering and drying to obtain the melamine diphenoxy phosphate. Wherein the mass ratio of the melamine to the diphenyl phosphoric acid is 3: 1-1.1.
The preparation of the melamine diphenoxy phosphate in the invention actually realizes the microencapsulation of the melamine organic phosphate. Specifically, the step realizes the microencapsulation of the diphenyl phosphoric acid, the diphenyl phosphoric acid is taken as a capsule core, the melamine is taken as a capsule material, and the extremely thin melamine is coated on the surface of the fine diphenyl phosphoric acid particles. Because the common organic phosphorus combustion improver has the defects of easy water absorption, low strength and poor water solubility of the water-based gloss oil, the water resistance and the strength of the water-based gloss oil are improved by coating a layer of melamine on the surface of the organic phosphorus, and the compatibility of melamine diphenoxy phosphate and an acrylic acid monomer in the gloss oil is enhanced.
In another embodiment, the present invention further provides a preparation method of a diphenylmethane diisocyanate type polyurethane prepolymer, including:
in the nitrogen atmosphere, adding diphenylmethane diisocyanate (MDI) powder into a reaction kettle, heating to 80-90 ℃, adding polypropylene glycol into the reaction kettle after the diphenylmethane diisocyanate is melted, and reacting. And in the reaction process, sampling from the reaction system at regular time to measure the concentration of-NCO, and finishing the reaction when the reaction degree reaches 50-53% to obtain the diphenylmethane diisocyanate type polyurethane prepolymer.
Preferably, the polypropylene glycol is one of PPG-200, PPG-400 and PPG-600.
Preferably, the ratio of the amount of-NCO to the amount of-OH is 2: (0.94-1).
Preferably, the shell monomer of the present invention is a mixture of hydroxyethyl acrylate, acrylic acid, butyl acrylate, methyl methacrylate and styrene. Further, the percentage content of the shell monomer in the water-based gloss oil can be 8-10% by weight; 4 to 7 percent of acrylic acid; 8 to 10 percent of butyl acrylate; 4 to 6 percent of methyl methacrylate; 8 to 10 percent of styrene.
Preferably, the core monomer of the present invention is N-methylolacrylamide.
Preferably, the initiator of the present invention is selected from one or more of ammonium persulfate, potassium persulfate and sodium bisulfite.
Preferably, the pH adjusting agent of the present invention is selected from one or more of sodium bicarbonate, N-dimethylethanolamine, triethylamine, ammonia water, or 2-amino-2-methyl-1-propanol.
Preferably, the auxiliary agent is one or two of wear-resistant wax slurry or defoaming agent, the wear-resistant wax slurry is high-density polyethylene wax, the relative molecular mass of the high-density polyethylene wax can be 1000-4000, the melting point is 90-120 ℃, and the specific gravity is 28-35 g/cm3The introduction of the wear-resistant wax slurry can improve the friction resistance of the water-based gloss oil, and the formed coating has high surface wear resistance and high efficiencyThe fruits are fine; the defoaming agent is a polyether defoaming agent, and the defoaming agent is introduced to eliminate foams formed by circulation or stirring of the aqueous gloss oil in the production or printing process.
Preferably, the emulsifier of the present invention is selected from one or more of nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, fatty amine polyoxyethylene ether, octyldecanol polyoxyethylene ether, isooctanol polyoxyethylene ether, polyoxyethylene sorbitan monooleate, and polyethylene glycol.
The invention also provides a preparation method of the water-based gloss oil, which comprises the following steps:
1) mixing an emulsifier, part of the nuclear monomer and part of deionized water, and uniformly stirring at 40-50 ℃ to obtain a mixture C;
2) heating the mixture C to 60-70 ℃, adding a first part of initiator, uniformly stirring, and keeping the temperature for 30-40 min to obtain a mixture D;
3) adding the rest of the core monomer and the second part of the initiator into the mixture D, uniformly stirring, then adding the shell monomer and the third part of the initiator, heating to 80-90 ℃, and preserving heat for 30-40 min to obtain an acrylate emulsion;
4) and adjusting the pH value of the acrylate emulsion to 8-9 by adopting a pH regulator, then adding the microencapsulated melamine organic phosphate, the auxiliary agent and the rest deionized water, and uniformly stirring to obtain the water-based gloss oil.
Wherein the total content of the initiator of the first part, the initiator of the second part and the initiator of the third part is 100 percent.
The invention also provides application of the water-based gloss oil in corrugated paper and corrugated paper products. The water-based varnish is coated on the surfaces of corrugated paper and corrugated paper products, so that the corrugated paper and the corrugated paper products have great improvement on flame retardance, water resistance, oil resistance and mechanical strength.
The invention also provides an application method of the water-based gloss oil in corrugated paper and corrugated paper products, which comprises the following steps:
1) uniformly mixing water-based gloss oil, deionized water and ethanol, wherein the solid content of the water-based gloss oil is controlled to be 30-35%, the viscosity is controlled to be 40-70 seconds at 25 ℃, and the viscosity is controlled to be coated in 4 cups;
2) the baking temperature is set to 80-100 ℃ during glazing, and the film thickness of the coating is controlled to be 4-10 g/m2And glazing the two sides of the corrugated paper printing product to obtain the flame-retardant corrugated board product with the flame retardant property.
Detailed Description
The technical solutions of the present invention are further illustrated by the following specific embodiments, but the present invention is not limited thereto.
Example 1
(1) Preparation of melamine diphenoxyphosphate
Adding 2010ml of 0.075g/ml melamine/glacial acetic acid solution into a four-neck flask, heating until the solution is dissolved, keeping the temperature, then dropwise adding 870ml of 0.1g/ml diphenyl phosphoric acid/glacial acetic acid solution, completing dropwise adding for about 2 hours, reacting for 16 hours, cooling, filtering and drying to obtain about 220-230 g of melamine diphenoxy phosphate.
(2) Preparation of diphenylmethane diisocyanate type polyurethane prepolymer
Under the nitrogen atmosphere, 500g of diphenylmethane diisocyanate (MDI) powder is added into a reaction kettle, the temperature is increased to 80-90 ℃, and 170g of polypropylene glycol (PPG-200) is added into the reaction kettle for reaction after the diphenylmethane diisocyanate is melted. And in the reaction process, sampling from a reaction system at regular time to measure the concentration of-NCO, and finishing the reaction when the reaction degree reaches 50-53% to obtain the diphenylmethane diisocyanate type polyurethane prepolymer with low polymerization degree.
(3) Preparation of microencapsulated melamine organophosphates
1) Adding 200g of melamine diphenoxyphosphate and 40g of diphenylmethane diisocyanate type polyurethane prepolymer into 1000ml of ethanol solution, and uniformly mixing to obtain a mixture A;
2) when the temperature of the reaction system is raised to 100-120 ℃, 0.8g of ammonium dihydrogen phosphate is added into the mixture A for reaction for 100-200 minutes to obtain a mixture B;
3) and filtering and drying the mixture B to obtain the microencapsulated melamine organic phosphate.
(4) Preparation of aqueous gloss oil
1) Mixing 1g of nonylphenol polyoxyethylene ether (NP-10) and 450g of deionized water, stirring at 40-50 ℃ for 20min, adding 25g of hydroxyethyl acrylate, 20g of acrylic acid, 40g of butyl acrylate, 20g of methyl methacrylate and 40g of styrene, and uniformly stirring to obtain a mixture C;
2) heating the mixture C to 70 ℃, adding 0.25g of potassium persulfate, uniformly stirring, heating to 80 ℃, and keeping the temperature for 30min to obtain a mixture D;
3) adding 25g of hydroxyethyl acrylate, 20g of acrylic acid, 40g of butyl acrylate, 20g of methyl methacrylate, 40g of styrene and 0.25g of potassium persulfate into the mixture D, uniformly stirring, adding 40g of N-hydroxymethyl acrylamide and 0.25g of potassium persulfate, uniformly stirring, adding 0.25g of potassium persulfate, heating to 90 ℃, and preserving the temperature for 30min to obtain an acrylate emulsion;
4) and adjusting the pH value of the acrylate emulsion to 8-9 by using 3g of sodium bicarbonate, stirring for 15min, then adding 150g of deionized water, 3g of wear-resistant wax slurry, 2g of polyether defoamer and 60g of microencapsulated melamine organic phosphate, stirring for 30min, and uniformly stirring to obtain the water-based gloss oil.
The water-based gloss oil comprises the following components in percentage by weight:
(5) the application method of the water-based gloss oil coated on the corrugated board comprises the following steps:
1) uniformly mixing water-based gloss oil, deionized water and ethanol, wherein the weight ratio of water: the mass ratio of the ethanol is 1: 1, the solid content of the water-based gloss oil is controlled to be 30%, the viscosity is controlled to be 40-70 seconds at 25 ℃, and the coating in-4 cups is adopted for the viscosity cup;
2) the baking temperature is set at 8The film thickness of the coating is controlled to be 6g/m at 0-100 DEG C2And glazing the two sides of the corrugated paper printing product to obtain the flame-retardant corrugated board product with the flame retardant property.
Example 2
(1) Preparation of melamine diphenoxyphosphate
Adding 2010ml of 0.075g/ml melamine/glacial acetic acid solution into a four-neck flask, heating to dissolve the solution, keeping the temperature, then dropwise adding 916ml of 0.1g/ml diphenyl phosphoric acid/glacial acetic acid solution, completing dropwise adding for about 2 hours, reacting for 16 hours, cooling, filtering and drying to obtain about 230-240 g of melamine diphenoxy phosphate.
(2) Preparation of diphenylmethane diisocyanate type polyurethane prepolymer
Adding 500g of diphenylmethane diisocyanate (MDI) powder into a reaction kettle under the nitrogen atmosphere, heating to 80-90 ℃, adding 400g of polypropylene glycol (PPG-400) into the reaction kettle after the diphenylmethane diisocyanate is melted, and reacting. And in the reaction process, sampling from a reaction system at regular time to measure the concentration of-NCO, and finishing the reaction when the reaction degree reaches 50-53% to obtain the diphenylmethane diisocyanate type polyurethane prepolymer with low polymerization degree.
(3) Preparation of microencapsulated melamine organophosphates
1) Adding 200g of melamine diphenoxyphosphate and 60g of diphenylmethane diisocyanate type polyurethane prepolymer into 1000ml of ethanol solution, and uniformly mixing to obtain a mixture A;
2) when the temperature of the reaction system is raised to 100-120 ℃, 1.8g of ammonium dihydrogen phosphate is added into the mixture A for reaction for 100-200 minutes to obtain a mixture B;
3) and filtering and drying the mixture B to obtain the microencapsulated melamine organic phosphate.
(4) Preparation of aqueous gloss oil
1) Mixing 1g of octylphenol polyoxyethylene ether, 1g of octyldecanol polyoxyethylene ether and 420g of deionized water, stirring for 20min at the temperature of 40-50 ℃, adding 30g of hydroxyethyl acrylate, 30g of acrylic acid, 45g of butyl acrylate, 25g of methyl methacrylate and 45g of styrene, and uniformly stirring to obtain a mixture C;
2) heating the mixture C to 70 ℃, adding 0.25g of ammonium persulfate and 0.25g of sodium bisulfite, uniformly stirring, heating to 80 ℃, and keeping the temperature for 30min to obtain a mixture D;
3) adding 30g of hydroxyethyl acrylate, 30g of acrylic acid, 45g of butyl acrylate, 25g of methyl methacrylate, 45g of styrene, 0.25g of ammonium persulfate and 0.25g of sodium bisulfite into the mixture D, uniformly stirring, adding 45g of N-methylolacrylamide, 0.25g of ammonium persulfate and 0.25g of sodium bisulfite, uniformly stirring, adding 0.25g of ammonium persulfate and 0.25g of sodium bisulfite, heating to 90 ℃, and keeping the temperature for 30min to obtain an acrylate emulsion;
4) and (2) adjusting the pH value of the acrylate emulsion to 8-9 by adopting 2g of N, N-dimethylethanolamine and 2g of triethylamine, stirring for 15min, then adding 99g of deionized water, 4g of wear-resistant wax slurry, 4g of polyether defoaming agent and 70g of microencapsulated melamine organic phosphate, stirring for 30min, and uniformly stirring to obtain the water-based gloss oil.
The water-based gloss oil comprises the following components in percentage by weight:
(5) the application method of the water-based gloss oil coated on the corrugated board comprises the following steps:
1) uniformly mixing the water-based varnish, deionized water and ethanol, wherein the mass ratio of water to ethanol is 1: 1, the solid content of the water-based varnish is controlled to be 35%, the viscosity is controlled to be 40-50 seconds, the temperature is 25 ℃, and the coating of-4 cups is carried out in a viscosity cup;
2) the baking temperature is set to 80-100 ℃ during glazing, and the film thickness of the coating is controlled to be 7g/m2Performing corrugated paper printingAnd polishing the two sides of the brush product to obtain the flame-retardant corrugated board product with flame retardant property.
Example 3
(1) Preparation of melamine diphenoxyphosphate
Adding 2010ml of 0.075g/ml melamine/glacial acetic acid solution into a four-neck flask, heating until the solution is dissolved, keeping the temperature, then dropwise adding 960ml of 0.1g/ml diphenyl phosphoric acid/glacial acetic acid solution for about 2h, reacting for 16h, cooling, filtering and drying to obtain about 235-245 g of melamine diphenoxy phosphate.
(2) Preparation of diphenylmethane diisocyanate type polyurethane prepolymer
500g of diphenylmethane diisocyanate (MDI) powder is added into a reaction kettle under the nitrogen atmosphere, the temperature is increased to 80-90 ℃, and 600g of polypropylene glycol (PPG-600) is added into the reaction kettle for reaction after the diphenylmethane diisocyanate is melted. And in the reaction process, sampling from a reaction system at regular time to measure the concentration of-NCO, and finishing the reaction when the reaction degree reaches 50-53% to obtain the diphenylmethane diisocyanate type polyurethane prepolymer with low polymerization degree.
(3) Preparation of microencapsulated melamine organophosphates
1) Adding 200g of melamine diphenoxyphosphate and 100g of diphenylmethane diisocyanate type polyurethane prepolymer into 1000ml of ethanol solution, and uniformly mixing to obtain a mixture A;
2) when the temperature of the reaction system is raised to 100-120 ℃, 2g of ammonium dihydrogen phosphate is added into the mixture A for reaction for 100-200 minutes to obtain a mixture B;
3) and filtering and drying the mixture B to obtain the microencapsulated melamine organic phosphate.
(4) Preparation of aqueous gloss oil
1) Mixing 1g of fatty amine polyoxyethylene ether, 1g of isooctanol polyoxyethylene ether and 370g of deionized water, stirring for 20min at the temperature of 40-50 ℃, adding 50g of hydroxyethyl acrylate, 35g of acrylic acid, 50g of butyl acrylate, 30g of methyl methacrylate and 50g of styrene, and uniformly stirring to obtain a mixture C;
2) heating the mixture C to 70 ℃, adding 0.5g of potassium persulfate, uniformly stirring, heating to 80 ℃, and keeping the temperature for 30min to obtain a mixture D;
3) adding 50g of hydroxyethyl acrylate, 35g of acrylic acid, 50g of butyl acrylate, 30g of methyl methacrylate, 50g of styrene and 0.5g of potassium persulfate into the mixture D, uniformly stirring, adding 50g of N-hydroxymethyl acrylamide and 0.5g of potassium persulfate, uniformly stirring, adding 0.5g of potassium persulfate, heating to 90 ℃, and keeping the temperature for 30min to obtain an acrylate emulsion;
4) adjusting the pH value of the acrylate emulsion to 8-9 by adopting 2g of 2-amino-2-methyl-1-propanol and 3g of triethylamine, stirring for 15min, then adding 80g of deionized water, 5g of wear-resistant wax slurry, 6g of polyether defoamer and 80g of microencapsulated melamine organic phosphate, stirring for 30min, and uniformly stirring to obtain the water-based gloss oil.
The water-based gloss oil comprises the following components in percentage by weight:
(5) the application method of the water-based gloss oil coated on the corrugated board comprises the following steps:
1) uniformly mixing water-based gloss oil, deionized water and ethanol, wherein the weight ratio of water: the mass ratio of the ethanol is 1: 1, the solid content of the water-based gloss oil is controlled to be 35%, the viscosity is controlled to be 45-50 seconds, the temperature is 25 ℃, and the coating in a viscosity cup is carried out by coating in 4 cups;
2) the baking temperature is set to 80-100 ℃ during glazing, and the film thickness of the coating is controlled to be 8g/m2And glazing the two sides of the corrugated paper printing product to obtain the flame-retardant corrugated board product with the flame retardant property.
Example 4
The aqueous gloss oil of this example, components and amounts, include:
the preparation method of the aqueous gloss oil of this example is the same as that of example 1, and will not be described in detail here.
Example 5
The aqueous gloss oil of this example, components and amounts, include:
the preparation method of the aqueous gloss oil of this example is the same as that of example 1, and will not be described in detail here.
Comparative example 1
The aqueous gloss oil of this example, components and amounts, include:
the preparation method of the comparative example aqueous gloss oil is the same as that of example 1, and detailed description thereof is omitted. The aqueous gloss oil obtained in examples 1 to 5 and comparative example 1 was coated on the same corrugated cardboard, and the flame retardancy, water resistance and mechanical strength were measured, and the results are shown in table 1.
The test method comprises the following steps:
1, the corrugated board is an E-shaped fine corrugated board, and the quantitative amounts of the surface paper and the core paper are respectively 175g/m2，120g/m2；
2, testing the contact angle of the liquid on the surface of the paper by adopting a JIC-1 wetting angle measuring instrument;
3, testing the edge pressure strength by using an HD-503 multifunctional ring pressure/edge pressure tester according to the requirements of GB/T6546-1998 measuring method for the edge pressure strength of corrugated boards;
4, the burst strength was tested by using an HD-504 type burst strength tester in accordance with the requirements of GB/T6545 and 1998 "determination of the burst strength of corrugated cardboard").
5, the flame retardant property is tested according to the requirements of GB/T14656-2009 flame retardant paper and paperboard combustion property test method.
Table 1: test results of flame retardancy, Water resistance and mechanical Strength
As can be seen from Table 1, the flame retardant property, the waterproof property and the mechanical strength of the water-based varnish in the examples 1-5 are far superior to those of the comparative example 1, because the water-based varnish in the examples 1-5 has the microencapsulated melamine organic phosphate which contains higher phosphorus, so that the microencapsulated melamine organic phosphate can be subjected to high dehydration and carbonization reaction with a matrix in the degradation process to generate a uniform and compact carbon layer, and therefore, the water-based varnish has good heat insulation, oxygen insulation, flame retardance and smoke suppression functions. Meanwhile, the microencapsulated melamine organic phosphate can also avoid the defects of easy migration and moisture absorption of an organic phosphorus flame retardant in the water-based gloss oil, improve the compatibility of the organic phosphorus flame retardant and a water-based gloss oil matrix, and ensure the glossiness and the mechanical strength of the water-based gloss oil.
Compared with example 5, in example 4, the paper in example 4 has better mechanical strength, flame retardant property and waterproof property, probably because the wear-resistant wax slurry adopted in example 4 can improve the friction resistance of the water-based gloss oil, the formed coating has high surface wear resistance and fine effect, and can also contribute to improving the flame retardant property.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, the present invention is not limited to the above disclosed embodiments, but should cover various modifications, equivalent combinations, made according to the essence of the present invention.
Claims (9)
1. The water-based gloss oil is characterized by comprising the following components in percentage by weight:
the preparation method of the microencapsulated melamine organic phosphate comprises the following steps:
1) adding melamine diphenoxyphosphate and diphenylmethane diisocyanate type polyurethane prepolymer into an organic solvent and uniformly mixing to obtain a mixture A;
2) adding a hardening agent into the mixture A to react to obtain a mixture B;
3) filtering and drying the mixture B to obtain the microencapsulated melamine organic phosphate,
a process for the preparation of melamine diphenoxyphosphate comprising:
adding 0.075g/ml of melamine/glacial acetic acid solution into a four-neck flask, heating until the melamine/glacial acetic acid solution is dissolved, then keeping the temperature, then dropwise adding 0.1g/ml of diphenyl phosphoric acid/glacial acetic acid solution, reacting for 16h, cooling, filtering and drying to obtain the melamine diphenoxy phosphate.
2. The aqueous varnish of claim 1, wherein the hardening agent is selected from one or more of ammonium chloride, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydrogen phosphate, or sodium dihydrogen phosphate.
3. The aqueous gloss oil of claim 1, wherein the shell monomer is a mixture of hydroxyethyl acrylate, acrylic acid, butyl acrylate, methyl methacrylate, and styrene.
4. The aqueous gloss oil of claim 1, wherein the core monomer is N-methylolacrylamide.
5. The aqueous gloss oil of claim 1, wherein the initiator is selected from one or more of ammonium persulfate, potassium persulfate, and sodium bisulfite.
6. The aqueous gloss oil of claim 1, wherein the adjuvant is selected from one or both of an abrasion resistant wax slurry and a defoamer, the abrasion resistant wax slurry being a high density polyethylene wax; the defoaming agent is a polyether defoaming agent.
7. The aqueous varnish of claim 1, wherein the emulsifier is selected from one or more of nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, fatty amine polyoxyethylene ether, octylphenol polyoxyethylene ether, isooctanol polyoxyethylene ether, polyoxyethylene sorbitan monooleate, and polyethylene glycol.
8. The method of any one of claims 1 to 7, comprising:
1) mixing an emulsifier, part of the nuclear monomer and part of deionized water, and uniformly stirring at 40-50 ℃ to obtain a mixture C;
2) heating the mixture C to 60-70 ℃, adding a first part of initiator, uniformly stirring, and keeping the temperature for 30-40 min to obtain a mixture D;
3) adding the rest of the core monomer and the second part of the initiator into the mixture D, uniformly stirring, then adding the shell monomer and the third part of the initiator, heating to 80-90 ℃, and preserving heat for 30-40 min to obtain an acrylate emulsion;
4) and adjusting the pH value of the acrylate emulsion to 8-9 by adopting a pH regulator, then adding microencapsulated melamine organic phosphate and the rest deionized water, and uniformly stirring to obtain the water-based gloss oil.
9. Use of the aqueous varnish according to any one of claims 1 to 7 in corrugated paper and corrugated paper products.
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| CN111334152B (en) * | 2020-04-17 | 2022-02-18 | 杭州海维特化工科技有限公司 | Water-based flame-retardant gloss oil and preparation method thereof |
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| CN101503526B (en) * | 2009-03-05 | 2011-06-29 | 中国科学技术大学 | Aqueous polyurethane micro-encapsulated halogen-free flame retardant and preparation thereof |
| CN101575476A (en) * | 2009-05-27 | 2009-11-11 | 彭文表 | Aqueous wear-resistant gloss oil and preparation method thereof |
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