CN107033765A - A kind of fire resistant water-based transfer coatings and preparation method thereof - Google Patents
A kind of fire resistant water-based transfer coatings and preparation method thereof Download PDFInfo
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- CN107033765A CN107033765A CN201710369391.8A CN201710369391A CN107033765A CN 107033765 A CN107033765 A CN 107033765A CN 201710369391 A CN201710369391 A CN 201710369391A CN 107033765 A CN107033765 A CN 107033765A
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The present invention relates to a kind of fire resistant water-based transfer coatings and preparation method thereof, the coating includes following components and content (wt%)：Polyether Glycols 24.5~28, polyester diol 30~37, hydrogenation methylenebis phenyl isocyanate 28~37, hydrophilizing agent 3~3.5, chain extender 2~10, nertralizer 1~3 and appropriate solvent；Preparation technology includes：Get the raw materials ready, the dehydration of raw material Hybrid Heating, prepolymer synthesis, in prepolymer and the step such as scattered, chain extension precipitation emulsification.Compared with prior art, there is coating of the present invention excellent fissility, high temperature resistant, particularly resistance to elevated temperatures to reach that resistance to 180 DEG C of high temperature does not soften after film forming, non-whitening.
Description
Technical field
It is good more particularly, to a kind of fissility the present invention relates to a kind of fire resistant water-based transfer coatings and preparation method thereof,
It is adapted to gravure and the aqueous polyurethane transfer coatings of offset printing and preparation method thereof.
Background technology
Aqueous polyurethane is using water as decentralized medium, with nontoxic, nonflammable, free from environmental pollution, energy-conservation, safe and reliable etc.
Advantage, meets the demand for development of green industry, therefore aqueous polyurethane coating obtains extensive concern and domestic and international in recent years
Attention.
But because the research of aqueous polyurethane transfer coatings is not perfect, the performance of aqueous polyurethane transfer coatings, which also exists, to be permitted
Fissility, resistance to elevated temperatures, folding resistance after more undesirable situation, such as aqueous polyurethane transfer coatings film forming etc. can't
Meet and require.
The content of the invention
The purpose of the present invention overcomes the deficiencies in the prior art and provides a kind of fissility, resistance to elevated temperatures, folding resistance
Aqueous polyurethane transfer coatings and preparation method thereof, particularly its resistance to elevated temperatures has reached is easily peeled off after film forming, resistance to 180 DEG C
High temperature does not soften, non-whitening.
The purpose of the present invention is achieved through the following technical solutions：
The present invention provides a kind of fire resistant water-based transfer coatings, and the coating includes following components and content (wt%)：
Wherein, described polyester diol is the mixing of the polyester diol of low, high two quasi-molecules amount, the two quasi-molecules amount
Respectively 1000-1500 and 2500-3500；Preferably 1000 and 3000；The polyester diol weight ratio of this two quasi-molecules amount is
1:0.5-1.5；Preferably weight ratio is 1:0.8-1.2；More preferably 1:1.
Described polyether Glycols are the mixing of the polyester diol of two quasi-molecule amounts；The two quasi-molecules amount is respectively
1000-1500 and 2500-3500；Preferably 1000 and 3000；The polyether Glycols weight ratio of this two quasi-molecules amount is weight ratio
For 1:0.9-1.3；More preferably 1:1.1.
Described hydrophilizing agent is dihydromethyl propionic acid, dihydroxy half ester, ethylenediamine base ethyl sulfonic acid sodium, BDO -2-
Sodium sulfonate, N methyldiethanol amine or water-soluble Polyoxyethylene glycol, are preferably that described hydrophilizing agent is dihydromethyl propionic acid.
Described chain extender is three classes, respectively IPD, trimethylolpropane, BDO or Isosorbide-5-Nitrae-ring
Hexane dimethanol；The ratio of this three class is 1:(2-7):(0.2-0.6)；Preferably it is 1:(2.5-6):(0.2-0.5)
It is preferred that nertralizer is dimethylethanolamine or dimethyl propanol amine, more preferably dimethylethanolamine.
Described solvent is at least one of 1-METHYLPYRROLIDONE, acetone.It may be referred to but be not limited to following consumption
0.1~4L:50kg (envelope-bulk to weight ratio with dihydric alcohol, dihydric alcohol is polyester diol and polyether Glycols), consumption is without special
Limitation, but also used less as far as possible in line with cost-effective purpose.
The present invention also provides the preparation method of above-mentioned fire resistant water-based transfer coatings, and this method comprises the following steps：
(1) get the raw materials ready：
Got the raw materials ready according to said components and content (wt%)；
(2) raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, chain extender trimethylolpropane (TMP) is added, three is stirred
120 DEG C are heated to, then decompression dehydration 1-2h, preferably 1h are cooled to 80-95 DEG C, obtain mixture 1.
(3) prepolymer is synthesized：
Hydrogenation methylenebis phenyl isocyanate is added in mixture 1 obtained by step (2), at a temperature of 80-95 DEG C, stirred
Reaction 1-2h, preferably 2h are mixed, hydrophilizing agent, chain extender BDO or 1,4-CHDM and solvent, dimension is then added
Hold 85 DEG C of temperature to continue to react 1-2h, then be cooled to 55-65 DEG C, preferably 60 DEG C add solvent N-methyl pyrilidone, acetone, dimension
Hold temperature to continue to react 1-2h, preferably 2h, obtain prepolymer.
(4) prepolymer is neutralized, disperseed：
The temperature of prepolymer is down to 30~40 DEG C, nertralizer is added, stirs, the prepolymer after must neutralizing；
(5) chain extension, precipitation, emulsification：
Chain extender IPD is added drop-wise in the prepolymer after neutralizing, after stirring 0.5-2h, deviates from solvent, obtains
Aqueous polyurethane transfer coatings.
Compared with prior art, the invention has the advantages that：
(1) stripping performance is good, and the product is applied on PET or OPP films after film forming, with 3M adhesive tape standard detecting methods
Detection, its film is easy to be completely exfoliated, is not in that phenomenon is left in fracture, is compared with the prior art, its peel strength is low, peels off
Performance is good.
(2) product have do not soften under 180 DEG C of high temperature after excellent heat-resisting quantity, film forming, non-whitening, more adapt to bag
The production technology in dress field.In the prior art, 130 DEG C -150 DEG C of high temperature resistant after general film forming, so, the product in the industry just
There is technological revolution innovation.
(3) product is to be adapted to gravure and the aqueous polyurethane transfer coatings of offset printing.
Embodiment
The present invention is described in detail with reference to specific embodiment.
Embodiment one
Preparation method is as follows：
1st, got the raw materials ready according to following components and ratio：
Molecular weight is 1000 polyester diol 30KG, and molecular weight is 3000 polyester diol 30KG, and molecular weight is
1000 polyether Glycols 19KG, molecular weight is 3000 polyether Glycols 21KG, trimethylolpropane 1KG, hydrogenates phenyl first
Alkane diisocyanate 60KG, dihydromethyl propionic acid 5KG, 1,4-CHDM 6KG, IPD 0.5kg, solvent N-
Each 2L of methyl pyrrolidone, acetone.
2nd, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, chain extender TMP is added, three is stirred and is heated to 120 DEG C, very
The lower dehydration 1h of sky, is then cooled to 80 DEG C.
3rd, prepolymer is synthesized：
Hydrogenation methylenebis phenyl isocyanate is added in polyester diol, polyether Glycols, it is 95 DEG C to control temperature, is stirred
Reaction 2h is mixed, hydrophilizing agent dihydromethyl propionic acid, chain extender 1,4-CHDM and solvent is then added, maintains temperature to continue
1h is reacted, then is cooled to 60 DEG C and adds solvent N-methyl pyrilidone, acetone, maintains temperature to continue to react 2h, obtains prepolymer.
4th, prepolymer is neutralized, disperseed：
The temperature of prepolymer is down to 40 DEG C, nertralizer is added, stirs, prepolymer is fully dispersed.
5th, chain extension, precipitation, emulsification：
Chain extender IPD is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, obtains aqueous poly-
Urethane emulsion.Embodiment two：
Method acquirement is prepared as follows：
1st, got the raw materials ready according to following components and ratio：
Molecular weight is 1000 polyester diol 30KG, and molecular weight is 3000 polyester diol 30KG, and molecular weight is
1000 polyether Glycols 23.8KG, molecular weight is 3000 polyether Glycols 26.2KG, TMP 2KG, hydrogenates phenylmethane two
Isocyanates 120KG, dihydromethyl propionic acid 7.5KG, BDO 5KG, IPD 0.5kg, Solvents N-methyl pyrrole
Each 2L of pyrrolidone, acetone
2nd, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols PTMG are measured, chain extender TMP is added, three is stirred and is heated to 120
DEG C, then dehydrated under vacuum 1h is cooled to 90 DEG C.
3rd, prepolymer is synthesized：
Hydrogenation methylenebis phenyl isocyanate is added in polyester diol, polyether Glycols, it is 80-95 to control temperature
DEG C, then stirring reaction 2h adds hydrophilizing agent dihydromethyl propionic acid, chain extender BDO and solvent 0.5L, maintains temperature
Continue to react 2h, then be cooled to 60 DEG C to add residual solvent 1-METHYLPYRROLIDONE, acetone, maintain temperature to continue to react 2h, obtain
To prepolymer.
4th, prepolymer is neutralized, disperseed：
The temperature of prepolymer is down to 40~45 DEG C, nertralizer triethylamine is added, stirs, prepolymer is fully divided
Dissipate.
5th, chain extension, precipitation, emulsification：
Chain extender IPD is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, obtains aqueous poly-
Urethane emulsion.Embodiment three：
Method acquirement is prepared as follows：
1st, got the raw materials ready according to following components and ratio
Molecular weight is 1000 polyester diol 35KG, and molecular weight is 3000 polyester diol 35KG, and molecular weight is
1000 polyether Glycols 26KG, molecular weight is 3000 polyether Glycols 29KG, TMP 2.5KG, and hydrogenation phenylmethane two is different
Cyanate (H12MDI) 95KG, dihydromethyl propionic acid 8KG, 1,4-CHDM 8KG, IPD 0.5kg, solvent
Each 2L of 1-METHYLPYRROLIDONE, acetone.
2nd, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, chain extender TMP is added, three is stirred and is heated to 120 DEG C, very
The lower dehydration 1h of sky, is then cooled to 90 DEG C.
3rd, prepolymer is synthesized
Hydrogenation methylenebis phenyl isocyanate (H12MDI) is added in polyester diol, polyether Glycols, temperature is controlled
For 80 DEG C, then stirring reaction 2h adds hydrophilizing agent dihydromethyl propionic acid, chain extender 1,4-CHDM and solvent, dimension
Hold temperature to continue to react 2h, then be cooled to 60 DEG C and add solvent N-methyl pyrilidone, acetone, maintain temperature to continue to react 2h,
Obtain prepolymer.
4th, prepolymer is neutralized, disperseed
The temperature of prepolymer is down to 42 DEG C, nertralizer is added, stirs, prepolymer is fully dispersed.
5th, chain extension, precipitation, emulsification
Chain extender IPD is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, obtains aqueous poly-
Urethane emulsion.Example IV：
Preparation method is as follows：
1st, got the raw materials ready according to following components and ratio：
Molecular weight is 1000 polyester diol 30KG, and molecular weight is 3000 polyester diol 30KG, and molecular weight is
1000 polyether Glycols 19KG, molecular weight is 3000 polyether Glycols 21KG, TMP 1KG, hydrogenates the isocyanide of phenylmethane two
Acid esters 60KG, dihydromethyl propionic acid 5KG, BDO 3KG, IPD 0.5kg, solvent N-methyl pyrilidone,
Each 2L of acetone.
2nd, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, chain extender TMP is added, three is stirred and is heated to 120 DEG C, very
The lower dehydration 1h of sky, is then cooled to 90 DEG C.
3rd, prepolymer is synthesized：
Hydrogenation methylenebis phenyl isocyanate is added in polyester diol, polyether Glycols, it is 90 DEG C to control temperature, is stirred
Reaction 2h is mixed, hydrophilizing agent dihydromethyl propionic acid, chain extender BDO and solvent is then added, maintains temperature to continue to react
1.5h, then 60 DEG C of addition solvent N-methyl pyrilidones, acetone are cooled to, maintain temperature to continue to react 2h, obtain prepolymer.
4th, prepolymer is neutralized, disperseed：
The temperature of prepolymer is down to 42 DEG C, nertralizer is added, stirs, prepolymer is fully dispersed.
5th, chain extension, precipitation, emulsification：
Chain extender IPD is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, obtains aqueous poly-
Urethane emulsion.Embodiment five：
Method acquirement is prepared as follows：
1st, got the raw materials ready according to following components and ratio：
Molecular weight is 1000 polyester diol 28KG, and molecular weight is 3000 polyester diol 32KG, and molecular weight is
1000 polyether Glycols 23.8KG, molecular weight is 3000 polyether Glycols 26.2KG, TMP 2KG, hydrogenate phenylmethane two
Isocyanates 120KG, dihydromethyl propionic acid 7.5KG, 1,4-CHDM 8KG, IPD 0.5kg, solvent N-
Each 2L of methyl pyrrolidone, acetone.
2nd, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols PTMG are measured, chain extender TMP is added, three is stirred and is heated to 120
DEG C, then dehydrated under vacuum 1h is cooled to 90 DEG C.
3rd, prepolymer is synthesized：
Hydrogenation methylenebis phenyl isocyanate is added in polyester diol, polyether Glycols, it is 80-95 to control temperature
DEG C, then stirring reaction 2h adds hydrophilizing agent dihydromethyl propionic acid, chain extender 1,4-CHDM and solvent, maintains temperature
Degree continues to react 1-2h, then is cooled to 60 DEG C of addition solvent N-methyl pyrilidones, acetone, maintains temperature to continue to react 2h, obtains
To prepolymer.
4th, prepolymer is neutralized, disperseed：
The temperature of prepolymer is down to 40~45 DEG C, nertralizer triethylamine is added, stirs, prepolymer is fully divided
Dissipate.
5th, chain extension, precipitation, emulsification：
Chain extender IPD is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, obtains aqueous poly-
Urethane emulsion.Embodiment six：
Method acquirement is prepared as follows：
1st, got the raw materials ready according to following components and ratio
Molecular weight is 1000 polyester diol 28KG, and molecular weight is 3000 polyester diol 32KG, and molecular weight is
1000 polyether Glycols 28KG, molecular weight is 3000 polyether Glycols 27KG, TMP 2.5KG, and hydrogenation phenylmethane two is different
Cyanate (H12MDI) 95KG, dihydromethyl propionic acid 10KG, IPD 0.5kg, BDO 6KG, solvent N- first
Each 2L of base pyrrolidones, acetone.
2nd, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, chain extender TMP is added, three is stirred and is heated to 120 DEG C, very
The lower dehydration 1h of sky, is then cooled to 95 DEG C.
3rd, prepolymer is synthesized
Hydrogenation methylenebis phenyl isocyanate (H12MDI) is added in polyester diol, polyether Glycols, temperature is controlled
For 80 DEG C, then stirring reaction 1h adds hydrophilizing agent dihydromethyl propionic acid, chain extender BDO and solvent, maintains temperature
Continue to react 1h, then be cooled to 60 DEG C to add solvent N-methyl pyrilidone, acetone, maintain temperature to continue to react 2h, obtain pre-
Polymers.
4th, prepolymer is neutralized, disperseed
The temperature of prepolymer is down to 42 DEG C, nertralizer is added, stirs, prepolymer is fully dispersed.
5th, chain extension, precipitation, emulsification
Chain extender IPD is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, obtains aqueous poly-
Urethane emulsion.Comparative example 1
A kind of coating, is prepared as follows method acquirement：
1st, got the raw materials ready according to following components and ratio
Molecular weight is 1000 polyester diol 125KG, TMP 2.5KG, hydrogenates methylenebis phenyl isocyanate
(H12MDI) 95KG, dihydromethyl propionic acid 10KG, 1,4 cyclohexane dimethanol 30KG.
2nd, raw material mixing, heating, dehydration
Measure polyester diol, add chain extender TMP, three, which is stirred, is heated to 120 DEG C, dehydrated under vacuum 1h,
Then it is cooled to 80-95 DEG C.
3rd, prepolymer is synthesized
Hydrogenation methylenebis phenyl isocyanate (H12MDI) is added in polyester diol, it is 99 DEG C to control temperature, stirring
2h is reacted, hydrophilizing agent dihydromethyl propionic acid, chain extender 1,4-CHDM and solvent is then added, maintains temperature to continue anti-
0.5h is answered, then is cooled to 60 DEG C and adds solvent N-methyl pyrilidone, acetone, maintains temperature to continue to react 2h, obtains prepolymer.
4th, prepolymer is neutralized, disperseed
The temperature of prepolymer is down to 50 DEG C, nertralizer is added, stirs, prepolymer is fully dispersed.
5th, chain extension, precipitation, emulsification
Chain extender IPD is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, obtains aqueous poly-
Urethane emulsion.Comparative example 2：
A kind of coating, is prepared as follows method acquirement：
1st, got the raw materials ready according to following components and ratio
Molecular weight is 4000 polyester diol 70KG, and molecular weight is 1000 polyether Glycols 55KG, TMP 2.5KG,
Hydrogenate methylenebis phenyl isocyanate (H12MDI) 95KG, dihydromethyl propionic acid 10KG, 1,4 cyclohexane dimethanol 30KG.
2nd, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, chain extender TMP is added, three is stirred and is heated to 120 DEG C, very
The lower dehydration 1h of sky, is then cooled to 80-95 DEG C.
3rd, prepolymer is synthesized
Hydrogenation methylenebis phenyl isocyanate (H12MDI) is added in polyester diol, polyether Glycols, temperature is controlled
For 99 DEG C, then stirring reaction 2h adds hydrophilizing agent dihydromethyl propionic acid, chain extender 1,4-CHDM and solvent, dimension
Hold temperature to continue to react 0.5h, then be cooled to 60 DEG C and add solvent N-methyl pyrilidone, acetone, maintain temperature to continue to react
2h, obtains prepolymer.
4th, prepolymer is neutralized, disperseed
The temperature of prepolymer is down to 50 DEG C, nertralizer is added, stirs, prepolymer is fully dispersed.
5th, chain extension, precipitation, emulsification
Chain extender IPD is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, obtains aqueous poly-
Urethane emulsion.
Comparative example 3：
Preparation method is as follows：
1st, got the raw materials ready according to following components and ratio：
Molecular weight is 1000 polyester diol 60KG, and molecular weight is 1000 polyether Glycols 40KG, TMP 1KG, hydrogen
Change methylenebis phenyl isocyanate 60KG, dihydromethyl propionic acid 5KG, BDO 3KG, IPD 0.5kg, solvent
Each 2L of 1-METHYLPYRROLIDONE, acetone.
2nd, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, chain extender TMP is added, three is stirred and is heated to 120 DEG C, very
The lower dehydration 1h of sky, is then cooled to 90 DEG C.
3rd, prepolymer is synthesized：
Hydrogenation methylenebis phenyl isocyanate is added in polyester diol, polyether Glycols, it is 90 DEG C to control temperature, is stirred
Reaction 2h is mixed, hydrophilizing agent dihydromethyl propionic acid, chain extender BDO and solvent is then added, maintains temperature to continue to react
1.5h, then 60 DEG C of addition solvent N-methyl pyrilidones, acetone are cooled to, maintain temperature to continue to react 2h, obtain prepolymer.
4th, prepolymer is neutralized, disperseed：
The temperature of prepolymer is down to 42 DEG C, nertralizer is added, stirs, prepolymer is fully dispersed.
5th, chain extension, precipitation, emulsification：
Chain extender IPD is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, obtains aqueous poly-
Urethane emulsion.Comparative example 4：
Method acquirement is prepared as follows：
1st, got the raw materials ready according to following components and ratio：
Molecular weight is 1000 polyester diol 60KG, and molecular weight is 1000 polyether Glycols 50KG, TMP 2KG, hydrogen
Change methylenebis phenyl isocyanate 120KG, dihydromethyl propionic acid 7.5KG, 1,4-CHDM 8KG, IPD
0.5kg, each 2L of solvent N-methyl pyrilidone, acetone.
2nd, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols PTMG are measured, chain extender TMP is added, three is stirred and is heated to 120
DEG C, then dehydrated under vacuum 1h is cooled to 90 DEG C.
3rd, prepolymer is synthesized：
Hydrogenation methylenebis phenyl isocyanate is added in polyester diol, polyether Glycols, it is 80-95 to control temperature
DEG C, then stirring reaction 2h adds hydrophilizing agent dihydromethyl propionic acid, chain extender 1,4-CHDM and solvent, maintains temperature
Degree continues to react 1-2h, then is cooled to 60 DEG C of addition solvent N-methyl pyrilidones, acetone, maintains temperature to continue to react 2h, obtains
To prepolymer.
4th, prepolymer is neutralized, disperseed：
The temperature of prepolymer is down to 40~45 DEG C, nertralizer triethylamine is added, stirs, prepolymer is fully divided
Dissipate.
5th, chain extension, precipitation, emulsification：
Chain extender IPD is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, obtains aqueous poly-
Urethane emulsion.Comparative example 5：
Method acquirement is prepared as follows：
1st, got the raw materials ready according to following components and ratio
Molecular weight is 1000 polyester diol 70KG, and molecular weight is 1000 polyether Glycols 55KG, TMP 2.5KG,
Hydrogenate methylenebis phenyl isocyanate (H12MDI) 95KG, dihydromethyl propionic acid 10KG, IPD 0.5kg, Isosorbide-5-Nitrae-fourth
Glycol 6KG, each 2L of solvent N-methyl pyrilidone, acetone.
2nd, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, chain extender TMP is added, three is stirred and is heated to 120 DEG C, very
The lower dehydration 1h of sky, is then cooled to 95 DEG C.
3rd, prepolymer is synthesized
Hydrogenation methylenebis phenyl isocyanate (H12MDI) is added in polyester diol, polyether Glycols, temperature is controlled
For 80 DEG C, then stirring reaction 1h adds hydrophilizing agent dihydromethyl propionic acid, chain extender BDO and solvent, maintains temperature
Continue to react 1h, then be cooled to 60 DEG C to add solvent N-methyl pyrilidone, acetone, maintain temperature to continue to react 2h, obtain pre-
Polymers.
4th, prepolymer is neutralized, disperseed
The temperature of prepolymer is down to 42 DEG C, nertralizer is added, stirs, prepolymer is fully dispersed.
5th, chain extension, precipitation, emulsification
Chain extender IPD is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, obtains aqueous poly-
Urethane emulsion.Verify embodiment 1
Coating composition prepared by embodiment 1-6 and comparative example 1-2, the testing standard (pressure of heatproof is molded using coating
Power is
130KPa, the testing time is 4s, and the anomaly such as soften, turn white is its heatproof critical point) determine.As a result such as table 1
It is shown：
The heatproof testing experiment result of table 1
| Embodiment is numbered | Heatproof test DEG C |
| Embodiment 1 | 190 |
| Embodiment 2 | 189 |
| Embodiment 3 | 190 |
| Embodiment 4 | 188 |
| Embodiment 5 | 189 |
| Embodiment 6 | 187 |
| Comparative example 1 | 139 |
| Comparative example 2 | 153 |
| Comparative example 3 | 161 |
| Comparative example 4 | 162 |
| Comparative example 5 | 167 |
In summary, the coating composition that prepared by the present invention is applied as obtained by adding the screening of composition and the combination of proportioning
Material, the resistance to temperature value of die pressing test compare the composition selected at random and proportioning gained coating coating heatproof be obviously improved 20 DEG C with
On, effect is notable.
Verify embodiment 1
The coating composition that embodiment one to embodiment six and comparative example 1 are prepared to comparative example 6 is applied to PET and OPP
On film after film forming, detected with 3M adhesive tapes standard detecting method, testing result is shown in Table 2：
The stripping performance result of the test of table 2
| Embodiment is numbered | PET film | OPP films |
| Embodiment 1 | Peel off completely, uniformly, no fracture is left | Peel off completely, uniformly, no fracture is left |
| Embodiment 2 | Peel off completely, uniformly, no fracture is left | Peel off completely, uniformly, no fracture is left |
| Embodiment 3 | Peel off completely, uniformly, no fracture is left | Peel off completely, uniformly, no fracture is left |
| Embodiment 4 | Peel off completely, uniformly, no fracture is left | Peel off completely, uniformly, no fracture is left |
| Embodiment 5 | Peel off completely, uniformly, no fracture is left | Peel off completely, uniformly, no fracture is left |
| Embodiment 6 | Peel off completely, uniformly, no fracture is left | Peel off completely, uniformly, no fracture is left |
| Comparative example 1 | 80% peels off, and has irregular fracture with leaving | 80% peels off, and has irregular fracture with leaving |
| Comparative example 2 | 75% peels off, and has irregular fracture with leaving | 80% peels off, and has irregular fracture with leaving |
| Comparative example 3 | 70% peels off, and has irregular fracture with leaving | 75% peels off, and has irregular fracture with leaving |
| Comparative example 4 | 90% peels off, and has irregular fracture with leaving | 95% peels off, and has irregular fracture with leaving |
| Comparative example 5 | It is completely exfoliated, there is irregular fracture, nothing is left | It is completely exfoliated, there is irregular fracture, nothing is left |
In summary, the coating composition that prepared by the present invention is applied on PET or OPP films after film forming, uses 3M adhesive tapes
Standard detecting method detects that its film is easy to be completely exfoliated, and is not in that phenomenon is left in fracture.It is compared with the prior art, it is shelled
From low intensity, stripping performance is good.
Claims (10)
1. a kind of fire resistant water-based transfer coatings, it is characterised in that the coating includes following components and content (wt%)：
Wherein, described polyester diol is the mixing of the polyester diol of low, high two quasi-molecules amount, two quasi-molecules amount difference
For 1000-1500 and 2500-3500；The polyester diol weight ratio of this two quasi-molecules amount is 1:0.5-1.5；
Described polyether Glycols are the mixing of the polyether Glycols of low, high two quasi-molecules amount；The two quasi-molecules amount is respectively
1000-1500 and 2500-3500；The polyether Glycols weight ratio of this two quasi-molecules amount is that weight ratio is 1:0.9-1.3；
Described hydrophilizing agent is dihydromethyl propionic acid, dihydroxy half ester, ethylenediamine base ethyl sulfonic acid sodium, BDO -2- sulfonic acid
Sodium, N methyldiethanol amine or water-soluble Polyoxyethylene glycol；
Described chain extender is IPD, trimethylolpropane, BDO or 1,4-CHDM；This three
The ratio of class is 1:(2-7):(0.2-0.6)；
Described nertralizer is dimethylethanolamine or dimethyl propanol amine.
2. a kind of fire resistant water-based transfer coatings as claimed in claim 1, it is characterised in that the polyester diol is two classes
The mixing of the polyester diol of molecular weight, the two quasi-molecules amount is respectively 1000 and 3000.
3. a kind of fire resistant water-based transfer coatings as claimed in claim 1, it is characterised in that the polyether Glycols are two classes
The mixing of the polyether Glycols of molecular weight, the two quasi-molecules amount is respectively 1000 and 3000.
4. a kind of fire resistant water-based transfer coatings as claimed in claim 1, it is characterised in that low, the high two quasi-molecules amount
Polyester diol weight ratio be 1:0.8-1.2.
5. a kind of fire resistant water-based transfer coatings as claimed in claim 1, it is characterised in that low, the high two quasi-molecules amount
Polyester diol weight ratio be 1:1.
6. a kind of fire resistant water-based transfer coatings as claimed in claim 1, it is characterised in that low, the high two quasi-molecules amount
Polyether Glycols weight ratio be 1:1.1.
7. a kind of fire resistant water-based transfer coatings as claimed in claim 1, it is characterised in that the hydrophilizing agent is dihydroxymethyl
Propionic acid.
8. a kind of fire resistant water-based transfer coatings as claimed in claim 1, it is characterised in that the IPD, three
Hydroxymethyl-propane, BDO or 1,4-CHDM, the part by weight of this three class is 1:(2.5-6):(0.2-
0.5)。
9. a kind of fire resistant water-based transfer coatings as described in claim 1-8 any claims, it is characterised in that in described
It is dimethylethanolamine with agent.
10. a kind of preparation method of fire resistant water-based transfer coatings as claimed in claim 9, it is characterised in that this method bag
Include following steps：
(1) get the raw materials ready：
Got the raw materials ready according to said components and content；
(2) raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, chain extender trimethylolpropane is added, three is stirred and is heated to 120
DEG C, then decompression dehydration is cooled to 80-95 DEG C, obtains mixture 1；
(3) prepolymer is synthesized：
Hydrogenation methylenebis phenyl isocyanate is added in mixture 1 obtained by step (2), at a temperature of 80-95 DEG C, stirring is anti-
Answer 1-2h, then add hydrophilizing agent, chain extender BDO or 1,4-CHDM and solvent, maintain 85 DEG C of temperature after
Continuous reaction 1-2h, then it is cooled to 55-65 DEG C, solvent N-methyl pyrilidone and/or acetone are added, maintains temperature to continue to react 1-
2h, obtains prepolymer；
(4) prepolymer is neutralized, disperseed：
The temperature of prepolymer is down to 30~40 DEG C, nertralizer is added, stirs, the prepolymer after must neutralizing；
(5) chain extension, precipitation, emulsification：
Chain extender IPD is added drop-wise in the prepolymer after neutralizing, after stirring 0.5-2h, deviates from solvent, obtains resistance to height
Warm aqueous transfer coating.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110305577A (en) * | 2019-06-12 | 2019-10-08 | 黄琳 | A kind of preparation method of folding aqueous transfer coating |
| CN115572526A (en) * | 2022-09-21 | 2023-01-06 | 中科浩源(无锡)新材料科技有限公司 | Waterborne polyurethane transfer coating and preparation method thereof |
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| CN101948659A (en) * | 2010-09-17 | 2011-01-19 | 淄博奥德美高分子材料有限公司 | Aqueous polyurethane resin and preparation method thereof |
| CN104910342A (en) * | 2015-06-30 | 2015-09-16 | 东华大学 | Preparation method of waterborne polyurethane |
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|---|---|---|---|---|
| CN101948659A (en) * | 2010-09-17 | 2011-01-19 | 淄博奥德美高分子材料有限公司 | Aqueous polyurethane resin and preparation method thereof |
| CN104910342A (en) * | 2015-06-30 | 2015-09-16 | 东华大学 | Preparation method of waterborne polyurethane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110305577A (en) * | 2019-06-12 | 2019-10-08 | 黄琳 | A kind of preparation method of folding aqueous transfer coating |
| CN115572526A (en) * | 2022-09-21 | 2023-01-06 | 中科浩源(无锡)新材料科技有限公司 | Waterborne polyurethane transfer coating and preparation method thereof |
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