CN107033765B - 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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- CN107033765B CN107033765B CN201710369391.8A CN201710369391A CN107033765B CN 107033765 B CN107033765 B CN 107033765B CN 201710369391 A CN201710369391 A CN 201710369391A CN 107033765 B CN107033765 B CN 107033765B
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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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- 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
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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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
- C09D5/18—Fireproof paints including high temperature resistant paints
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Abstract
The present invention relates to a kind of fire resistant water-based transfer coatings and preparation method thereof, which includes following components and content (wt%): polyether Glycols 24.5~28, polyester diol 30~37, hydrogenation methylenebis phenyl isocyanate 28~37, hydrophilic agent 3~3.5, chain extender 2~10, neutralizer 1~3 and appropriate solvent；Preparation process include: stock, the dehydration of raw material Hybrid Heating, prepolymer synthesis, in prepolymer and dispersion, chain extension precipitation emulsification.Compared with prior art, coating of the present invention have excellent fissility, high temperature resistant, especially high temperature resistance reach film forming after resistance to 180 DEG C of high temperature do not soften, 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 suitble to gravure and the aqueous polyurethane transfer coatings of offset printing and preparation method thereof.
Background technique
Aqueous polyurethane has nontoxic, nonflammable, free from environmental pollution, energy saving, safe and reliable etc. using water as decentralized medium
Advantage meets the demand for development of green industry, therefore aqueous polyurethane coating obtains extensive concern and both at home and abroad in recent years
Attention.
But because the research of aqueous polyurethane transfer coatings is not perfect, there is also permitted for the performance of aqueous polyurethane transfer coatings
Fissility, high temperature resistance, folding resistance etc. after mostly undesirable situation, such as aqueous polyurethane transfer coatings film forming can't
It meets the requirements.
Summary of the invention
A kind of fissility, high temperature resistance, folding resistance are provided the purpose of the present invention is overcome the deficiencies in the prior art
Aqueous polyurethane transfer coatings and preparation method thereof, especially its high temperature resistance are easily peeled off after having reached film forming, and resistance to 180 DEG C
High temperature do 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, which includes following components and content (wt%):
Wherein, the polyester diol is the mixing of the polyester diol of low, high two classes molecular weight, the two classes molecular weight
Respectively 1000-1500 and 2500-3500；Preferably 1000 and 3000；The polyester diol weight ratio of these two types of molecular weight is
1:0.5-1.5；Preferably weight ratio is 1:0.8-1.2；Further preferably 1:1.
The polyether Glycols are the mixing of the polyester diol of two class molecular weight；The two classes molecular weight is respectively
1000-1500 and 2500-3500；Preferably 1000 and 3000；The polyether Glycols weight ratio of these two types of molecular weight is weight ratio
For 1:0.9-1.3；Further preferably 1:1.1.
The hydrophilic agent is dihydromethyl propionic acid, dihydroxy half ester, ethylenediamine base ethanesulfonic acid sodium, 1,4-butanediol -2-
Sodium sulfonate, N methyldiethanol amine or water-soluble Polyoxyethylene glycol, the preferably hydrophilic agent are dihydromethyl propionic acid.
The chain extender is three classes, respectively isophorone diamine, trimethylolpropane, 1,4-butanediol or Isosorbide-5-Nitrae-ring
Hexane dimethanol；The ratio of this three classes is 1:(2-7): (0.2-0.6)；Preferably it is 1:(2.5-6): (0.2-0.5)
It is preferred that neutralizer is dimethylethanolamine or dimethyl propanol amine, more preferably dimethylethanolamine.
The solvent is at least one of N-Methyl pyrrolidone, acetone.It can refer to but be not limited to following dosage
0.1~4L:50kg (envelope-bulk to weight ratio with dihydric alcohol, dihydric alcohol are the pure and mild polyether Glycols of polyester binary), dosage is without special
Limitation, but also in line with save the cost purpose, it is few as far as possible to use.
The present invention also provides the preparation methods of above-mentioned fire resistant water-based transfer coatings, method includes the following steps:
(1) it stocks up:
It stocks up according to said components and content (wt%)；
(2) raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, is added chain extender trimethylolpropane (TMP), three is stirred evenly
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 synthesizes:
Hydrogenation methylenebis phenyl isocyanate is added obtained by step (2) in mixture 1,80-95 DEG C at a temperature of, stir
Reaction 1-2h, preferably 2h are mixed, hydrophilic agent, chain extender 1,4-butanediol or 1,4-CHDM and solvent, dimension is then added
85 DEG C of temperature are held the reaction was continued 1-2h, then is cooled to 55-65 DEG C, preferably 60 DEG C additions solvent N-methyl pyrilidones, acetone, dimension
Temperature is held the reaction was continued 1-2h, preferably 2h, obtains prepolymer.
(4) prepolymer neutralizes, disperses:
The temperature of prepolymer is down to 30~40 DEG C, neutralizer is added, stirs evenly, the prepolymer after must neutralizing；
(5) chain extension, precipitation, emulsification:
Chain extender isophorone diamine is added drop-wise in the prepolymer after neutralizing, after stirring 0.5-2h, prolapse solvent is obtained
Aqueous polyurethane transfer coatings.
Compared with prior art, the present invention has the advantage that
(1) stripping performance is good, which is applied on PET OPP film after film forming, with 3M adhesive tape standard detecting method
Detection, film are easy to be completely exfoliated, are not in that phenomenon is left in fracture, are compared with the prior art, and peel strength is low, removing
Performance is good.
(2) product has excellent heat-resisting quantity, does not soften under 180 DEG C of high temperature after film forming, non-whitening, more adapts to packet
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 the industry just
There is technological revolution innovation.
(3) product is the aqueous polyurethane transfer coatings for being suitble to gravure and offset printing.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.
Embodiment one
The preparation method is as follows:
1, it stocks up according to following components and ratio:
The polyester diol 30KG that molecular weight is 1000, the polyester diol 30KG that molecular weight is 3000, molecular weight are
1000 polyether Glycols 19KG, polyether Glycols 21KG, the trimethylolpropane 1KG that molecular weight is 3000 hydrogenate phenyl first
Alkane diisocyanate 60KG, dihydromethyl propionic acid 5KG, 1,4-CHDM 6KG, isophorone diamine 0.5kg, solvent N-
Each 2L of methyl pyrrolidone, acetone.
2, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, chain extender TMP is added, three is stirred evenly and is heated to 120 DEG C, very
Sky is lower to be dehydrated 1h, is then cooled to 80 DEG C.
3, prepolymer synthesizes:
In hydrogenation methylenebis phenyl isocyanate addition polyester diol, polyether Glycols, controlled at 95 DEG C, stir
Reaction 2h is mixed, hydrophilic agent dihydromethyl propionic acid, chain extender 1,4-CHDM and solvent is then added, temperature is maintained to continue
1h is reacted, then is cooled to 60 DEG C of addition solvent N-methyl pyrilidones, acetone, maintenance temperature the reaction was continued 2h obtains prepolymer.
4, prepolymer neutralizes, disperses:
The temperature of prepolymer is down to 40 DEG C, neutralizer is added, stirs evenly, prepolymer is fully dispersed.
5, chain extension, precipitation, emulsification:
Chain extender isophorone diamine is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, is obtained aqueous poly-
Urethane lotion.Embodiment two:
Method acquirement is prepared as follows:
1, it stocks up according to following components and ratio:
The polyester diol 30KG that molecular weight is 1000, the polyester diol 30KG that molecular weight is 3000, molecular weight are
1000 polyether Glycols 23.8KG, polyether Glycols 26.2KG, the TMP 2KG that molecular weight is 3000 hydrogenate phenylmethane two
Isocyanates 120KG, dihydromethyl propionic acid 7.5KG, 1,4-butanediol 5KG, isophorone diamine 0.5kg, Solvents N-methyl pyrrole
Each 2L of pyrrolidone, acetone
2, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols PTMG are measured, chain extender TMP is added, three is stirred evenly and is heated to 120
DEG C, then dehydrated under vacuum 1h is cooled to 90 DEG C.
3, prepolymer synthesizes:
Polyester diol is added, in polyether Glycols in hydrogenation methylenebis phenyl isocyanate, controlled at 80-95
DEG C, it is stirred to react 2h, hydrophilic agent dihydromethyl propionic acid, chain extender 1,4-butanediol and solvent 0.5L is then added, maintains temperature
The reaction was continued 2h, then be cooled to 60 DEG C of addition residual solvent N-Methyl pyrrolidones, acetone maintains temperature the reaction was continued 2h, obtains
To prepolymer.
4, prepolymer neutralizes, disperses:
The temperature of prepolymer is down to 40~45 DEG C, neutralizer triethylamine is added, stirs evenly, prepolymer is sufficiently divided
It dissipates.
5, chain extension, precipitation, emulsification:
Chain extender isophorone diamine is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, is obtained aqueous poly-
Urethane lotion.Embodiment three:
Method acquirement is prepared as follows:
1, it stocks up according to following components and ratio
The polyester diol 35KG that molecular weight is 1000, the polyester diol 35KG that molecular weight is 3000, molecular weight are
1000 polyether Glycols 26KG, polyether Glycols 29KG, the TMP 2.5KG that molecular weight is 3000, hydrogenation phenylmethane two are different
Cyanate (H12MDI) 95KG, dihydromethyl propionic acid 8KG, 1,4-CHDM 8KG, isophorone diamine 0.5kg, solvent
Each 2L of N-Methyl pyrrolidone, acetone.
2, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, chain extender TMP is added, three is stirred evenly and is heated to 120 DEG C, very
Sky is lower to be dehydrated 1h, is then cooled to 90 DEG C.
3, prepolymer synthesizes
In hydrogenation methylenebis phenyl isocyanate (H12MDI) addition polyester diol, polyether Glycols, temperature is controlled
It is 80 DEG C, is stirred to react 2h, hydrophilic agent dihydromethyl propionic acid, chain extender 1,4-CHDM and solvent, dimension is then added
Temperature is held the reaction was continued 2h, then be cooled to 60 DEG C of additions solvent N-methyl pyrilidones, acetone, maintains temperature the reaction was continued 2h,
Obtain prepolymer.
4, prepolymer neutralizes, disperses
The temperature of prepolymer is down to 42 DEG C, neutralizer is added, stirs evenly, prepolymer is fully dispersed.
5, chain extension, precipitation, emulsification
Chain extender isophorone diamine is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, is obtained aqueous poly-
Urethane lotion.Example IV:
The preparation method is as follows:
1, it stocks up according to following components and ratio:
The polyester diol 30KG that molecular weight is 1000, the polyester diol 30KG that molecular weight is 3000, molecular weight are
1000 polyether Glycols 19KG, polyether Glycols 21KG, the TMP 1KG that molecular weight is 3000 hydrogenate two isocyanide of phenylmethane
Acid esters 60KG, dihydromethyl propionic acid 5KG, 1,4-butanediol 3KG, isophorone diamine 0.5kg, solvent N-methyl pyrilidone,
Each 2L of acetone.
2, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, chain extender TMP is added, three is stirred evenly and is heated to 120 DEG C, very
Sky is lower to be dehydrated 1h, is then cooled to 90 DEG C.
3, prepolymer synthesizes:
In hydrogenation methylenebis phenyl isocyanate addition polyester diol, polyether Glycols, controlled at 90 DEG C, stir
Reaction 2h is mixed, hydrophilic agent dihydromethyl propionic acid, chain extender 1,4-butanediol and solvent is then added, maintaining temperature, the reaction was continued
1.5h, then be cooled to 60 DEG C of additions solvent N-methyl pyrilidones, acetone maintains temperature the reaction was continued 2h, obtains prepolymer.
4, prepolymer neutralizes, disperses:
The temperature of prepolymer is down to 42 DEG C, neutralizer is added, stirs evenly, prepolymer is fully dispersed.
5, chain extension, precipitation, emulsification:
Chain extender isophorone diamine is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, is obtained aqueous poly-
Urethane lotion.Embodiment five:
Method acquirement is prepared as follows:
1, it stocks up according to following components and ratio:
The polyester diol 28KG that molecular weight is 1000, the polyester diol 32KG that molecular weight is 3000, molecular weight are
1000 polyether Glycols 23.8KG, polyether Glycols 26.2KG, the TMP 2KG that molecular weight is 3000, hydrogenate phenylmethane two
Isocyanates 120KG, dihydromethyl propionic acid 7.5KG, 1,4-CHDM 8KG, isophorone diamine 0.5kg, solvent N-
Each 2L of methyl pyrrolidone, acetone.
2, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols PTMG are measured, chain extender TMP is added, three is stirred evenly and is heated to 120
DEG C, then dehydrated under vacuum 1h is cooled to 90 DEG C.
3, prepolymer synthesizes:
Polyester diol is added, in polyether Glycols in hydrogenation methylenebis phenyl isocyanate, controlled at 80-95
DEG C, it is stirred to react 2h, hydrophilic agent dihydromethyl propionic acid, chain extender 1,4-CHDM and solvent is then added, maintains temperature
Degree the reaction was continued 1-2h, then be cooled to 60 DEG C of addition solvent N-methyl pyrilidones, acetone, maintenance temperature the reaction was continued 2h, obtains
To prepolymer.
4, prepolymer neutralizes, disperses:
The temperature of prepolymer is down to 40~45 DEG C, neutralizer triethylamine is added, stirs evenly, prepolymer is sufficiently divided
It dissipates.
5, chain extension, precipitation, emulsification:
Chain extender isophorone diamine is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, is obtained aqueous poly-
Urethane lotion.Embodiment six:
Method acquirement is prepared as follows:
1, it stocks up according to following components and ratio
The polyester diol 28KG that molecular weight is 1000, the polyester diol 32KG that molecular weight is 3000, molecular weight are
1000 polyether Glycols 28KG, polyether Glycols 27KG, the TMP 2.5KG that molecular weight is 3000, hydrogenation phenylmethane two are different
Cyanate (H12MDI) 95KG, dihydromethyl propionic acid 10KG, isophorone diamine 0.5kg, 1,4-butanediol 6KG, solvent N- first
Each 2L of base pyrrolidones, acetone.
2, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, chain extender TMP is added, three is stirred evenly and is heated to 120 DEG C, very
Sky is lower to be dehydrated 1h, is then cooled to 95 DEG C.
3, prepolymer synthesizes
In hydrogenation methylenebis phenyl isocyanate (H12MDI) addition polyester diol, polyether Glycols, temperature is controlled
It is 80 DEG C, is stirred to react 1h, hydrophilic agent dihydromethyl propionic acid, chain extender 1,4-butanediol and solvent is then added, maintains temperature
The reaction was continued 1h, then be cooled to 60 DEG C of additions solvent N-methyl pyrilidones, acetone maintains temperature the reaction was continued 2h, obtains pre-
Polymers.
4, prepolymer neutralizes, disperses
The temperature of prepolymer is down to 42 DEG C, neutralizer is added, stirs evenly, prepolymer is fully dispersed.
5, chain extension, precipitation, emulsification
Chain extender isophorone diamine is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, is obtained aqueous poly-
Urethane lotion.Comparative example 1
Method acquirement is prepared as follows in a kind of coating:
1, it stocks up according to following components and ratio
Polyester diol 125KG, the TMP 2.5KG that molecular weight is 1000 hydrogenates methylenebis phenyl isocyanate
(H12MDI) 95KG, dihydromethyl propionic acid 10KG, 1,4 cyclohexane dimethanol 30KG.
2, raw material mixing, heating, dehydration
Polyester diol is measured, chain extender TMP is added, three is stirred evenly and is heated to 120 DEG C, dehydrated under vacuum 1h,
Then it is cooled to 80-95 DEG C.
3, prepolymer synthesizes
Hydrogenation methylenebis phenyl isocyanate (H12MDI) is added in polyester diol, controlled at 99 DEG C, stirring
2h is reacted, hydrophilic 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 of additions solvent N-methyl pyrilidones, acetone, temperature the reaction was continued 2h is maintained, obtains prepolymer.
4, prepolymer neutralizes, disperses
The temperature of prepolymer is down to 50 DEG C, neutralizer is added, stirs evenly, prepolymer is fully dispersed.
5, chain extension, precipitation, emulsification
Chain extender isophorone diamine is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, is obtained aqueous poly-
Urethane lotion.Comparative example 2:
Method acquirement is prepared as follows in a kind of coating:
1, it stocks up according to following components and ratio
The polyester diol 70KG that molecular weight is 4000, polyether Glycols 55KG, the TMP 2.5KG that molecular weight is 1000,
Hydrogenate methylenebis phenyl isocyanate (H12MDI) 95KG, dihydromethyl propionic acid 10KG, 1,4 cyclohexane dimethanol 30KG.
2, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, chain extender TMP is added, three is stirred evenly and is heated to 120 DEG C, very
Sky is lower to be dehydrated 1h, is then cooled to 80-95 DEG C.
3, prepolymer synthesizes
In hydrogenation methylenebis phenyl isocyanate (H12MDI) addition polyester diol, polyether Glycols, temperature is controlled
It is 99 DEG C, is stirred to react 2h, hydrophilic agent dihydromethyl propionic acid, chain extender 1,4-CHDM and solvent, dimension is then added
Temperature is held the reaction was continued 0.5h, then be cooled to 60 DEG C of additions solvent N-methyl pyrilidones, acetone, maintaining temperature, the reaction was continued
2h obtains prepolymer.
4, prepolymer neutralizes, disperses
The temperature of prepolymer is down to 50 DEG C, neutralizer is added, stirs evenly, prepolymer is fully dispersed.
5, chain extension, precipitation, emulsification
Chain extender isophorone diamine is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, is obtained aqueous poly-
Urethane lotion.
Comparative example 3:
The preparation method is as follows:
1, it stocks up according to following components and ratio:
The polyester diol 60KG that molecular weight is 1000, polyether Glycols 40KG, the TMP 1KG that molecular weight is 1000, hydrogen
Change methylenebis phenyl isocyanate 60KG, dihydromethyl propionic acid 5KG, 1,4-butanediol 3KG, isophorone diamine 0.5kg, solvent
Each 2L of N-Methyl pyrrolidone, acetone.
2, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, chain extender TMP is added, three is stirred evenly and is heated to 120 DEG C, very
Sky is lower to be dehydrated 1h, is then cooled to 90 DEG C.
3, prepolymer synthesizes:
In hydrogenation methylenebis phenyl isocyanate addition polyester diol, polyether Glycols, controlled at 90 DEG C, stir
Reaction 2h is mixed, hydrophilic agent dihydromethyl propionic acid, chain extender 1,4-butanediol and solvent is then added, maintaining temperature, the reaction was continued
1.5h, then be cooled to 60 DEG C of additions solvent N-methyl pyrilidones, acetone maintains temperature the reaction was continued 2h, obtains prepolymer.
4, prepolymer neutralizes, disperses:
The temperature of prepolymer is down to 42 DEG C, neutralizer is added, stirs evenly, prepolymer is fully dispersed.
5, chain extension, precipitation, emulsification:
Chain extender isophorone diamine is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, is obtained aqueous poly-
Urethane lotion.Comparative example 4:
Method acquirement is prepared as follows:
1, it stocks up according to following components and ratio:
The polyester diol 60KG that molecular weight is 1000, polyether Glycols 50KG, the TMP 2KG that molecular weight is 1000, hydrogen
Change methylenebis phenyl isocyanate 120KG, dihydromethyl propionic acid 7.5KG, 1,4-CHDM 8KG, isophorone diamine
0.5kg, each 2L of solvent N-methyl pyrilidone, acetone.
2, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols PTMG are measured, chain extender TMP is added, three is stirred evenly and is heated to 120
DEG C, then dehydrated under vacuum 1h is cooled to 90 DEG C.
3, prepolymer synthesizes:
Polyester diol is added, in polyether Glycols in hydrogenation methylenebis phenyl isocyanate, controlled at 80-95
DEG C, it is stirred to react 2h, hydrophilic agent dihydromethyl propionic acid, chain extender 1,4-CHDM and solvent is then added, maintains temperature
Degree the reaction was continued 1-2h, then be cooled to 60 DEG C of addition solvent N-methyl pyrilidones, acetone, maintenance temperature the reaction was continued 2h, obtains
To prepolymer.
4, prepolymer neutralizes, disperses:
The temperature of prepolymer is down to 40~45 DEG C, neutralizer triethylamine is added, stirs evenly, prepolymer is sufficiently divided
It dissipates.
5, chain extension, precipitation, emulsification:
Chain extender isophorone diamine is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, is obtained aqueous poly-
Urethane lotion.Comparative example 5:
Method acquirement is prepared as follows:
1, it stocks up according to following components and ratio
The polyester diol 70KG that molecular weight is 1000, polyether Glycols 55KG, the TMP 2.5KG that molecular weight is 1000,
Hydrogenate methylenebis phenyl isocyanate (H12MDI) 95KG, dihydromethyl propionic acid 10KG, isophorone diamine 0.5kg, Isosorbide-5-Nitrae-fourth
Glycol 6KG, each 2L of solvent N-methyl pyrilidone, acetone.
2, raw material mixing, heating, dehydration
Polyester diol, polyether Glycols are measured, chain extender TMP is added, three is stirred evenly and is heated to 120 DEG C, very
Sky is lower to be dehydrated 1h, is then cooled to 95 DEG C.
3, prepolymer synthesizes
In hydrogenation methylenebis phenyl isocyanate (H12MDI) addition polyester diol, polyether Glycols, temperature is controlled
It is 80 DEG C, is stirred to react 1h, hydrophilic agent dihydromethyl propionic acid, chain extender 1,4-butanediol and solvent is then added, maintains temperature
The reaction was continued 1h, then be cooled to 60 DEG C of additions solvent N-methyl pyrilidones, acetone maintains temperature the reaction was continued 2h, obtains pre-
Polymers.
4, prepolymer neutralizes, disperses
The temperature of prepolymer is down to 42 DEG C, neutralizer is added, stirs evenly, prepolymer is fully dispersed.
5, chain extension, precipitation, emulsification
Chain extender isophorone diamine is added drop-wise in the prepolymer after neutralizing, after stirring, deviates from acetone, is obtained aqueous poly-
Urethane lotion.Verify embodiment 1
Coating composition prepared by embodiment 1-6 and comparative example 1-2, using the testing standard (pressure of coating molding heatproof
Power is
130KPa, testing time 4s, the abnormal phenomenon such as soften, whiten are its heatproof critical point) measurement.As a result such as table 1
It is shown:
1 heatproof testing experiment result of table
| Embodiment number | 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, coating composition prepared by the present invention is applied obtained by combination of the screening of ingredient with proportion as being added
Material, the coating heatproof that the resistance to temperature value of die pressing test compares the ingredient selected at random and proportion gained coating be obviously improved 20 DEG C with
On, significant effect.
Verify embodiment 1
Embodiment one to embodiment six and comparative example 1 to coating composition prepared by comparative example 6 are applied to PET and OPP
It after forming a film on film, is detected with 3M adhesive tape standard detecting method, testing result is shown in Table 2:
2 stripping performance test result of table
| Embodiment number | PET film | OPP film |
| Embodiment 1 | Completely, uniformly, no fracture is left for removing | Completely, uniformly, no fracture is left for removing |
| Embodiment 2 | Completely, uniformly, no fracture is left for removing | Completely, uniformly, no fracture is left for removing |
| Embodiment 3 | Completely, uniformly, no fracture is left for removing | Completely, uniformly, no fracture is left for removing |
| Embodiment 4 | Completely, uniformly, no fracture is left for removing | Completely, uniformly, no fracture is left for removing |
| Embodiment 5 | Completely, uniformly, no fracture is left for removing | Completely, uniformly, no fracture is left for removing |
| Embodiment 6 | Completely, uniformly, no fracture is left for removing | Completely, uniformly, no fracture is left for removing |
| Comparative example 1 | 80% removing, has irregular fracture and leaves | 80% removing, has irregular fracture and leaves |
| Comparative example 2 | 75% removing, has irregular fracture and leaves | 80% removing, has irregular fracture and leaves |
| Comparative example 3 | 70% removing, has irregular fracture and leaves | 75% removing, has irregular fracture and leaves |
| Comparative example 4 | 90% removing, has irregular fracture and leaves | 95% removing, has irregular fracture and leaves |
| 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, coating composition prepared by the present invention is applied on PET OPP film after film forming, with 3M adhesive tape
Standard detecting method detection, it is not in that phenomenon is left in fracture that film, which is easy to be completely exfoliated,.It is compared with the prior art, shells
Low from intensity, stripping performance is good.
Claims (10)
1. a kind of fire resistant water-based transfer coatings, which is characterized in that the coating includes following components and content (wt%):
Wherein, the polyester diol is the mixing of the polyester diol of low, high two classes molecular weight, two classes molecular weight difference
For 1000-1500 and 2500-3500；The polyester diol weight ratio of these two types of molecular weight is 1:0.5-1.5；
The polyether Glycols are the mixing of the polyether Glycols of low, high two classes molecular weight；The two classes molecular weight is respectively
1000-1500 and 2500-3500；It is 1:0.9-1.3 that the polyether Glycols weight ratio of these two types of molecular weight, which is weight ratio,；
The hydrophilic agent is dihydromethyl propionic acid, dihydroxy half ester, ethylenediamine base ethanesulfonic acid sodium, 1,4-butanediol -2- sulfonic acid
Sodium, N methyldiethanol amine or water-soluble Polyoxyethylene glycol；
The chain extender is isophorone diamine, trimethylolpropane, 1,4-butanediol or 1,4-CHDM；This three
The ratio of class is 1:(2-7): (0.2-0.6)；
The neutralizer is dimethylethanolamine or dimethyl propanol amine.
2. a kind of fire resistant water-based transfer coatings as described in claim 1, which is characterized in that the polyester diol is two classes
The mixing of the polyester diol of molecular weight, which is respectively 1000 and 3000.
3. a kind of fire resistant water-based transfer coatings as described in claim 1, which is characterized in that the polyether Glycols are two classes
The mixing of the polyether Glycols of molecular weight, which is respectively 1000 and 3000.
4. a kind of fire resistant water-based transfer coatings as described in claim 1, which is characterized in that low, the high two classes molecular weight
Polyester diol weight ratio be 1:0.8-1.2.
5. a kind of fire resistant water-based transfer coatings as described in claim 1, which is characterized in that low, the high two classes molecular weight
Polyester diol weight ratio be 1:1.
6. a kind of fire resistant water-based transfer coatings as described in claim 1, which is characterized in that low, the high two classes molecular weight
Polyether Glycols weight ratio be 1:1.1.
7. a kind of fire resistant water-based transfer coatings as described in claim 1, which is characterized in that the hydrophilic agent is dihydroxymethyl
Propionic acid.
8. a kind of fire resistant water-based transfer coatings as described in claim 1, which is characterized in that the isophorone diamine, three
Hydroxymethyl-propane, 1,4-butanediol or 1,4-CHDM, the weight ratio of this three classes are 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 claim, which is characterized 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, which is characterized in that this method packet
Include following steps:
(1) it stocks up:
It stocks up 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 evenly and is heated to 120
DEG C, then decompression dehydration is cooled to 80-95 DEG C, obtain mixture 1；
(3) prepolymer synthesizes:
Hydrogenation methylenebis phenyl isocyanate is added obtained by step (2) in mixture 1,80-95 DEG C at a temperature of, stirring is anti-
Answer 1-2h, hydrophilic agent, chain extender 1,4-butanediol or 1,4-CHDM and solvent be then added, maintain 85 DEG C of temperature after
Continuous reaction 1-2h, then be cooled to 55-65 DEG C, is added solvent N-methyl pyrilidone and/or acetone, maintains temperature the reaction was continued 1-
2h obtains prepolymer；
(4) prepolymer neutralizes, disperses:
The temperature of prepolymer is down to 30~40 DEG C, neutralizer is added, stirs evenly, the prepolymer after must neutralizing；
(5) chain extension, precipitation, emulsification:
Chain extender isophorone diamine is added drop-wise in the prepolymer after neutralizing, after stirring 0.5-2h, prolapse solvent obtains resistance to height
Warm aqueous transfer coating.
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| CN104910342A (en) * | 2015-06-30 | 2015-09-16 | 东华大学 | Preparation method of waterborne polyurethane |
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