CN109337635A - A kind of resistive connection skin water-based polyurethane adhesive and preparation method thereof - Google Patents
A kind of resistive connection skin water-based polyurethane adhesive and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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- C09J175/06—Polyurethanes from polyesters
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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
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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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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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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Abstract
The present invention relates to field of adhesive technology, and in particular to a kind of resistive connection skin water-based polyurethane adhesive and preparation method thereof.Raw material including following parts by weight is made: 95~99 parts by weight of aqueous polyurethane dispersion, 0.1~1 parts by weight of 0.1~0.5 parts by weight of wetting agent, 0.1~0.5 parts by weight of defoaming agent and thickener；The aqueous polyurethane dispersion includes that following raw material is prepared: polyalcohol, inorganic mineral powder, polyisocyanates and carboxyl chain extender, the polyalcohol, inorganic mineral powder, polyisocyanates and carboxyl chain extender molar ratio be 1:0.1~0.6:2~5:0.2~2.The present invention is reacted using inorganic mineral powder with polyisocyanates, the aqueous polyurethane dispersion being prepared can not completely completely enclose the active group of inorganic mineral powder, the part water conservation group for remaining inorganic mineral powder, to inhibit the generation of water-based polyurethane adhesive skinning glue film.
Description
Technical field
The present invention relates to field of adhesive technology, and in particular to a kind of resistive connection skin water-based polyurethane adhesive and its preparation side
Method.
Background technique
With the development of science and technology, water-based polyurethane adhesive achieves significant progress, in multiple fields instead of molten
Dosage form polyurethane adhesive.Water-based polyurethane adhesive solvent content is extremely low, environmentally protective, easy to use, and adhesive strength is high, more
It has been begun to focus on come more people and has used water-based polyurethane adhesive.
When storing or opening bucket sizing, adhesive surface layer contacts water-based polyurethane adhesive with air, when temperature is higher,
Moisture in adhesive surface layer is readily volatilized, and the latex particle in aqueous polyurethane dispersion gradually draws close, is squeezed and deformed, molecule
Chain phase counterdiffusion is finally fused into complete glue film, that is, generates the skinning of hard.This skinning, can not since process is irreversible
Again it is dispersed in water.In the use process of adhesive, if skinning not removed, will have a direct impact on adhesive at
Film properties, can also cause other various disadvantages of adhesive, such as reduce adhesive strength, to cause under construction quality
Drop.Common practice is to be filtered to remove such skinning, but this way not only complex steps will also lose part adhesive.
The storage container of general recommendations water-based polyurethane adhesive should keep sealing to completely cut off air, but water-borne polyurethane bond
Inevitably ingress of air, these operations increase the risk of skinning to stick in storage and use process.
Summary of the invention
The technical problems to be solved by the present invention are: providing a kind of resistive connection skin water-based polyurethane adhesive and its preparation side
Method, the water-based polyurethane adhesive that the present invention is prepared are able to extend the drying at room temperature film formation time of adhesive, it is suppressed that water
The generation of property polyurethane adhesive skinning；Simultaneously again do not interfere with water-based polyurethane adhesive the hot setting time and
The performances such as adhesive strength.
The most critical design of the present invention is: inorganic mineral powder is reacted with polyisocyanates, what is be prepared is aqueous poly-
Urethane dispersion can not completely completely enclose the active group of inorganic mineral powder, and the part for remaining inorganic mineral powder is protected
Water base group, to inhibit the generation of water-based polyurethane adhesive skinning glue film.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention are as follows: a kind of resistive connection skin water-borne polyurethane bond is viscous
Agent, the raw material including following parts by weight are made: 95~99 parts by weight of aqueous polyurethane dispersion, 0.1~0.5 weight of wetting agent
Part, 0.1~1 parts by weight of 0.1~0.5 parts by weight of defoaming agent and thickener；
The aqueous polyurethane dispersion includes that following raw material is prepared: polyalcohol, inorganic mineral powder, polyisocyanic acid
Ester and carboxyl chain extender, the polyalcohol, inorganic mineral powder, polyisocyanates and carboxyl chain extender molar ratio be 1:0.1
~0.6:2~5:0.2~2.
Further, the inorganic mineral powder is the composition of one or both of lithium magnesium silicate, aluminium-magnesium silicate.
Further, the polyalcohol is polyoxypropyleneglycol, polyethylene glycol, polytetrahydrofuran ether glycol, gathers in oneself
The composition of one or more of esterdiol and polybutadiene diol.
Further, the polyisocyanates is isophorone diisocyanate, toluene di-isocyanate(TDI), diphenyl methane
Diisocyanate, hexamethylene diisocyanate and 4, the group of one or more of 4'- dicyclohexyl methyl hydride diisocyanate
Close object.
Further, the carboxyl chain extender is one of dihydromethyl propionic acid and dimethylolpropionic acid.
The present invention also provides a kind of preparation methods of above-mentioned resistive connection skin water-based polyurethane adhesive, include the following steps:
Step 1 prepares aqueous polyurethane dispersion: reaction kettle is added in M mol polyalcohol, N mol inorganic mineral powder
In, stirring be warming up to 100~138 DEG C, while be filtered by vacuum dehydration to moisture less than 0.1%, after be passed through nitrogen as protection gas
Body is cooled to 40~50 DEG C hereinafter, addition P mol polyisocyanates, is warming up to 60~95 DEG C, reaction 2~8 hours, reaction is tied
It is cooled to 40~50 DEG C after beam hereinafter, Q mol carboxyl chain extender is added, is warming up to 60~95 DEG C, insulation reaction 0.5~4 hour,
Aqueous polyurethane dispersion is made；
M:N:P:Q=1:0.1~the 0.6:2~5:0.2~2；
Step 2, in stirring container be added resulting 95~99 parts by weight of aqueous polyurethane dispersion of step 1, after successively
0.1~0.5 parts by weight of wetting agent, 0.1~1 parts by weight of 0.1~0.5 parts by weight of defoaming agent and thickener, control stirring speed is added
Degree is in 500~800rpm, and 15~30min of dispersion mixing is to get resistive connection skin water-based polyurethane adhesive.
Further, in the step 1 after insulation reaction, 40~50 DEG C are cooled to, acetone is added, and be slowly added dropwise
W mol triethylamine aqueous solution adjusts pH=6~9, and then vacuum distillation removes acetone, while water is added dropwise, aqueous polyurethane point is made
Granular media, the W=Q.
Further, the thickener is ten thousand China's chemistry U605、U505 andOne or more of U905 composition；It is chemical Coadd that the defoaming agent, which is general,TMDF-420、
CoaddTM DF-460、CoaddTMDF-860 and CoaddTMThe composition of one or more of DF825；The wetting agent
For it is general be chemical CoaddTM W-1866、CoaddTM W-1855、CoaddTMW138 and CoaddTMOne or more of W110
Composition.
The beneficial effects of the present invention are: having in inorganic mineral powder structure of the invention can be anti-with polyisocyanates
The active group answered and itself have the characteristics that excellent moisturizing water retention property changes due to steric effect through polyisocyanates
Aqueous polyurethane dispersion after property can not completely completely enclose the active group of inorganic mineral powder, therefore remain inorganic
The part of mineral dust is retained group, maintains the moisture on water-based polyurethane adhesive surface layer, has delayed aqueous polyurethane gluing
The room temperature film-forming speed on agent surface, to reach the generation for inhibiting water-based polyurethane adhesive skinning glue film, so that it has very
Good room temperature opening resistive connection skin, and the performances such as rate of drying when hot setting and adhesive strength are not affected.
Specific embodiment
To explain the technical content, the achieved purpose and the effect of the present invention in detail, it is explained below in conjunction with embodiment.
Embodiment 1
A kind of resistive connection skin water-based polyurethane adhesive, the raw material including following weight are made: aqueous polyurethane dispersion A0
989g, wetting agent 1g, defoaming agent 1g, thickener 3g and water 6g；
The aqueous polyurethane dispersion includes that following raw material is prepared: polyalcohol, inorganic mineral powder, polyisocyanic acid
Ester and carboxyl chain extender, the polyalcohol, inorganic mineral powder, polyisocyanates and carboxyl chain extender molar ratio be 1:0.1:
2:0.2.
The aqueous polyurethane dispersion A0Synthesis step are as follows:
Under the conditions of drying nitrogen protection, in the four-hole bottle with thermometer, blender and reflux condensing tube, by 1mol
Polyoxypropyleneglycol (Mw=2000Da), 0.3mol lithium magnesium silicate powder are dispersed with stirring, and are warming up to 100 DEG C, vacuum filtration is de-
Water is to moisture less than 0.1%；Drying nitrogen is passed through as protective gas, 40~50 DEG C is cooled to, 3mol toluene diisocyanate is added
Acid esters is warming up to 60 DEG C, reacts 4 hours；1mol dihydromethyl propionic acid chain extender is added later, it is small to continue 60 DEG C of reactions 2 of heat preservation
When；Temperature of reaction system is reduced to 40~50 DEG C, suitable acetone is added to reduce system viscosity；1mol triethylamine is dissolved
In 500g ice water, it is slowly dropped in system.At 40 DEG C, the acetone being evaporated under reduced pressure in removing system is slowly added dropwise simultaneously
About 2400g water emulsifies aqueous polyurethane molecule in water and evenly dispersed, resistive connection skin aqueous polyurethane dispersion can be obtained
A0。
The preparation step of the aqueous resistive connection skin water-based polyurethane adhesive are as follows:
Take above-mentioned resistive connection skin aqueous polyurethane dispersion A0989g is added in stirring container, sequentially adds 1g defoaming agent
CoaddTMDF-420,1g wetting agent CoaddTMAfter W110, it is evenly dispersed mixing 15~30 minutes after, add with 6g go from
3g thickener after sub- water dilutionU505 is added in system, continues to stir 30 minutes or so to get resistive connection is arrived
Skin water-based polyurethane adhesive A.
Embodiment 2
A kind of resistive connection skin water-based polyurethane adhesive, the raw material including following weight are made: aqueous polyurethane dispersion B0:
950g, wetting agent 5g, defoaming agent 5g, thickener 10g and water 30g；
The aqueous polyurethane dispersion B0It is prepared including following raw material: polyalcohol, inorganic mineral powder, polyisocyanate cyanogen
Acid esters and carboxyl chain extender, the polyalcohol, inorganic mineral powder, polyisocyanates and carboxyl chain extender molar ratio be 1:
0.5:3:1.
The aqueous polyurethane dispersion B0Synthesis step are as follows:
Under the conditions of drying nitrogen protection, in the four-hole bottle with thermometer, blender and reflux condensing tube, by 1mol
Polyoxyethylene glycol (Mw=1000Da), 0.23mol aluminium-magnesium silicate powder are dispersed with stirring, and are warming up to 110 DEG C, vacuum filtration is de-
Water is to moisture less than 0.1%；Drying nitrogen is passed through as protective gas, is cooled to 50 DEG C hereinafter, 4.3mol diphenylmethyl is added
Alkane diisocyanate is warming up to 80 DEG C, reacts 4 hours；0.8mol dihydromethyl propionic acid chain extender is added later, continues heat preservation 80
DEG C reaction 2 hours；Temperature of reaction system is reduced to 40~50 DEG C, suitable acetone is added to reduce system viscosity；It will
0.8mol triethylamine is dissolved in 500g ice water, is slowly dropped in system.At 40 DEG C, be evaporated under reduced pressure removing system in third
Ketone, while about 1900g water is slowly added dropwise emulsifies aqueous polyurethane molecule in water and evenly dispersed, resistive connection skin can be obtained
Aqueous polyurethane dispersion B0。
The preparation step of the aqueous resistive connection skin water-based polyurethane adhesive are as follows:
Take above-mentioned resistive connection skin aqueous polyurethane dispersion B0950g is added in stirring container, sequentially adds 5g defoaming agent
CoaddTMDF-860,5g wetting agent CoaddTMAfter W138, it is evenly dispersed mixing 15~30 minutes after, add with 30g go from
10g thickener after sub- water dilutionU902 is added in system, continues stirring 30 minutes or so to get to anti-
Skinning water-based polyurethane adhesive B.
Embodiment 3
A kind of resistive connection skin water-based polyurethane adhesive, the raw material including following weight are made: aqueous polyurethane dispersion C0
975g, wetting agent 3g, defoaming agent 2g, thickener 1g and water 19g；
The aqueous polyurethane dispersion includes that following raw material is prepared: polyalcohol, inorganic mineral powder, polyisocyanic acid
Ester and carboxyl chain extender, the polyalcohol, inorganic mineral powder, polyisocyanates and carboxyl chain extender molar ratio be 1:0.6:
5:2.
The aqueous polyurethane dispersion C0Synthesis step are as follows:
Under the conditions of drying nitrogen protection, in the four-hole bottle with thermometer, blender and reflux condensing tube, by 1mol
Polycaprolactone glycol (Mw=1360Da), 0.25mol lithium magnesium silicate and 0.13mol aluminium-magnesium silicate are dispersed with stirring, and are warming up to 120
DEG C, vacuum filtration dehydration is to moisture less than 0.1%；Drying nitrogen is passed through as protective gas, 40~50 DEG C is cooled to, is added
3.4mol hexamethylene diisocyanate is warming up to 65 DEG C, reacts 3 hours；1.4mol dimethylolpropionic acid chain extension is added later
Agent continues 65 DEG C of heat preservation and reacts 2 hours；Temperature of reaction system is reduced to 40~50 DEG C, suitable acetone is added to reduce body
It is viscosity；1.4mol triethylamine is dissolved in 500g ice water, is slowly dropped in system.At 40 DEG C, vacuum distillation is removed
Acetone in system, while about 2000g water is slowly added dropwise emulsifies aqueous polyurethane molecule in water and evenly dispersed
Obtain resistive connection skin aqueous polyurethane dispersion C0。
The preparation step of the aqueous resistive connection skin water-based polyurethane adhesive are as follows:
Take above-mentioned resistive connection skin aqueous polyurethane dispersion C0975g is added in stirring container, sequentially adds 2g defoaming agent
CoaddTMDF-460,3g wetting agent CoaddTMAfter W1866, after evenly dispersed mixing 15~30 minutes, adds and gone with 19g
1g thickener after ionized water dilutionU605 is added in system, continues stirring 30 minutes or so to get to anti-
Skinning water-based polyurethane adhesive C.
Comparative example is the comparison of embodiment.Comparative example 1 and embodiment 1 are the difference is that be not added with inorganic mineral powder
End, remaining synthesis condition are identical；The difference is that being not added with inorganic mineral powder, remaining synthesizes item for comparative example 2 and embodiment 2
Part is identical；The difference is that being not added with inorganic mineral powder, remaining synthesis condition is identical for comparative example 3 and embodiment 3.
Comparative example 1
A kind of resistive connection skin water-based polyurethane adhesive, the raw material including following weight are made: aqueous polyurethane dispersion D0
989g, wetting agent 1g, defoaming agent 1g, thickener 3g and water 6g；
The aqueous polyurethane dispersion includes that following raw material is prepared: polyalcohol, polyisocyanates and carboxyl chain extension
Agent, the molar ratio of the polyalcohol, polyisocyanates and carboxyl chain extender are 1:0.1:2:0.2.
The aqueous polyurethane dispersion D0Synthesis step are as follows:
Under the conditions of drying nitrogen protection, in the four-hole bottle with thermometer, blender and reflux condensing tube, by 1mol
Polyoxypropyleneglycol (Mw=2000Da) is added in reaction kettle, is warming up to 100 DEG C, vacuum filtration dehydration to moisture is less than
0.1%；Drying nitrogen is passed through as protective gas, 40~50 DEG C is cooled to, 3mol toluene di-isocyanate(TDI) is added, is warming up to 60
DEG C, it reacts 4 hours；1mol dihydromethyl propionic acid chain extender is added later, continues 60 DEG C of heat preservation and reacts 2 hours；By reaction system
Temperature is reduced to 40~50 DEG C, and suitable acetone is added to reduce system viscosity；1mol triethylamine is dissolved in 500g ice water,
It is slowly dropped in system.At 40 DEG C, the acetone being evaporated under reduced pressure in removing system, while about 2400g water is slowly added dropwise, make water
Property polyurethane molecular emulsifies and evenly dispersed in water, and resistive connection skin aqueous polyurethane dispersion D can be obtained0。
The preparation step of the aqueous resistive connection skin water-based polyurethane adhesive are as follows:
Take above-mentioned resistive connection skin aqueous polyurethane dispersion D0989g is added in stirring container, sequentially adds 1g defoaming agent
CoaddTMDF-420,1g wetting agent CoaddTMAfter W110, it is evenly dispersed mixing 10~30 minutes after, add with 6g go from
3g thickener after sub- water dilutionU505 is added in system, continues to stir 30 minutes or so to get resistive connection is arrived
Skin water-based polyurethane adhesive D.
Comparative example 2
A kind of resistive connection skin water-based polyurethane adhesive, the raw material including following weight are made: aqueous polyurethane dispersion E0:
985g, wetting agent 1g, defoaming agent 2g and thickener 4g；
The aqueous polyurethane dispersion E0Be prepared including following raw material: polyalcohol, polyisocyanates and carboxyl expand
Chain agent, the molar ratio of the polyalcohol, polyisocyanates and carboxyl chain extender are 1:0.5:3:1.
The aqueous polyurethane dispersion E0Synthesis step are as follows:
Under the conditions of drying nitrogen protection, in the four-hole bottle with thermometer, blender and reflux condensing tube, by 1mol
Polyoxyethylene glycol (Mw=1000Da) is added in reaction kettle, is warming up to 110 DEG C, vacuum filtration dehydration to moisture is less than
0.1%；Drying nitrogen is passed through as protective gas, is cooled to 50 DEG C hereinafter, 4.3mol methyl diphenylene diisocyanate is added,
80 DEG C are warming up to, is reacted 4 hours；0.8mol dihydromethyl propionic acid chain extender is added later, continues 80 DEG C of heat preservation and reacts 2 hours；
Temperature of reaction system is reduced to 40~50 DEG C, suitable acetone is added to reduce system viscosity；0.8mol triethylamine is dissolved
In 500g ice water, it is slowly dropped in system.At 40 DEG C, the acetone being evaporated under reduced pressure in removing system is slowly added dropwise simultaneously
About 1900g water emulsifies aqueous polyurethane molecule in water and evenly dispersed, resistive connection skin aqueous polyurethane dispersion can be obtained
E0。
The preparation step of the aqueous resistive connection skin water-based polyurethane adhesive are as follows:
Take above-mentioned resistive connection skin aqueous polyurethane dispersion E0985g is added in stirring container, sequentially adds 1g defoaming agent
CoaddTMDF-860,2g wetting agent CoaddTMAfter W138, it is evenly dispersed mixing 10~30 minutes after, add with 8g go from
4g thickener after sub- water dilutionU902 is added in system, continues to stir 30 minutes or so to get resistive connection is arrived
Skin water-based polyurethane adhesive E.
Comparative example 3
A kind of resistive connection skin water-based polyurethane adhesive, the raw material including following weight are made: aqueous polyurethane dispersion F0
988g, wetting agent 1g, defoaming agent 2g and thickener 3g；
The aqueous polyurethane dispersion includes that following raw material is prepared: polyalcohol, polyisocyanates and carboxyl chain extension
Agent, the molar ratio of the polyalcohol, polyisocyanates and carboxyl chain extender are 1:0.6:5:2.
The aqueous polyurethane dispersion F0Synthesis step are as follows:
Under the conditions of drying nitrogen protection, in the four-hole bottle with thermometer, blender and reflux condensing tube, by 1mol
Polycaprolactone glycol (Mw=1360Da) is added in reaction kettle, is warming up to 120 DEG C, vacuum filtration dehydration is to moisture less than 0.1%；
Drying nitrogen is passed through as protective gas, 40~50 DEG C is cooled to, 3.4mol hexamethylene diisocyanate is added, is warming up to 65
DEG C, it reacts 3 hours；1.4mol dimethylolpropionic acid chain extender is added later, continues 65 DEG C of heat preservation and reacts 2 hours；By reactant
It is that temperature is reduced to 40~50 DEG C, suitable acetone is added to reduce system viscosity；1.4mol triethylamine is dissolved in 500g ice
In water, it is slowly dropped in system.At 40 DEG C, the acetone being evaporated under reduced pressure in removing system, while about 2000g is slowly added dropwise
Water emulsifies aqueous polyurethane molecule in water and evenly dispersed, resistive connection skin aqueous polyurethane dispersion F can be obtained0。
The preparation step of the aqueous resistive connection skin water-based polyurethane adhesive are as follows:
Take above-mentioned resistive connection skin aqueous polyurethane dispersion F0988g is added in stirring container, sequentially adds 1g defoaming agent
CoaddTMDF-460,2g wetting agent CoaddTMAfter W1866, it is evenly dispersed mixing 10~30 minutes after, add with 6g go from
3g thickener after sub- water dilutionU605 is added in system, continues to stir 30 minutes or so to get resistive connection is arrived
Skin water-based polyurethane adhesive F.
By resistive connection skin water-based polyurethane adhesive made from above-described embodiment and comparative example scraped on glass 100 μm it is wet
Film at 25 DEG C and 70 DEG C, while testing drying time, and the results are shown in Table 1.
The room temperature of adhesive made from 1. embodiment of table and comparative example and high temperature drying time
As it can be seen from table 1 the drying time of adhesive A~C is more much longer than adhesive D~F at 25 DEG C, illustrate glue
Stick A~C anti-scaling property is good；Temperature is improved to 70 DEG C, and drying time difference furthers rapidly.Wherein adhesive A and D synthesis
Condition is essentially identical, and adhesive B and E synthesis condition is essentially identical, and adhesive C and F synthesis condition is essentially identical.It is raw in product shoes
When production, Shoes Factory usually can due to all kinds of shoe styles or other working conditions variation and adjust drying time, adjust amplitude generally 2
Within minute.The gap of above-mentioned several adhesive drying times will not have an impact substantially to production within 1 minute.
In conclusion resistive connection skin water-based polyurethane adhesive provided by the invention, using inorganic mineral powder modified water-soluble
Dispersions of polyurethanes has the active group that can be reacted with polyisocyanates in inorganic mineral powder structure and has in itself
The features such as excellent moisturizing water retention property, due to steric effect, aqueous polyurethane dispersion after modified polyisocyanate without
Method completely completely encloses the active group of inorganic mineral powder, therefore remains the part water conservation group of inorganic mineral powder,
The moisture for maintaining water-based polyurethane adhesive surface layer has delayed the room temperature film-forming speed on water-based polyurethane adhesive surface, from
And reach the generation for inhibiting water-based polyurethane adhesive skinning glue film, so that it is with good room temperature opening resistive connection skin, and
The performances such as rate of drying and adhesive strength when water-based polyurethane adhesive hot setting are not affected.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalents made by bright description are applied directly or indirectly in relevant technical field, are similarly included in this hair
In bright scope of patent protection.
Claims (8)
1. a kind of resistive connection skin water-based polyurethane adhesive, which is characterized in that the raw material including following parts by weight is made: aqueous poly- ammonia
95~99 parts by weight of ester dispersion, 0.1~0.5 parts by weight of wetting agent, 0.1~0.5 parts by weight of defoaming agent and thickener 0.1~1
Parts by weight；
The aqueous polyurethane dispersion includes that following raw material is prepared: polyalcohol, inorganic mineral powder, polyisocyanates and
Carboxyl chain extender, the polyalcohol, inorganic mineral powder, polyisocyanates and carboxyl chain extender molar ratio be 1:0.1~
0.6:2~5:0.2~2.
2. resistive connection skin water-based polyurethane adhesive according to claim 1, which is characterized in that the inorganic mineral powder is
The composition of one or both of lithium magnesium silicate, aluminium-magnesium silicate.
3. resistive connection skin water-based polyurethane adhesive according to claim 1, which is characterized in that the polyalcohol is polyoxygenated
One or more of propylene glycol, polyethylene glycol, polytetrahydrofuran ether glycol, polycaprolactone glycol and polybutadiene diol
Composition.
4. resistive connection skin water-based polyurethane adhesive according to claim 1, which is characterized in that the polyisocyanates is different
Isophorone diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexamethylene diisocyanate and 4,4'
The composition of one or more of~dicyclohexyl methyl hydride diisocyanate.
5. resistive connection skin water-based polyurethane adhesive according to claim 1, which is characterized in that the carboxyl chain extender is two
One of hydroxymethyl propionic acid and dimethylolpropionic acid.
6. a kind of preparation method of resistive connection skin water-based polyurethane adhesive, which comprises the steps of:
Step 1 prepares aqueous polyurethane dispersion: M mol polyalcohol, N mol inorganic mineral powder being added in reaction kettle, stirred
Mix and be warming up to 100~138 DEG C, while dehydration is filtered by vacuum to moisture less than 0.1%, after be passed through nitrogen as protective gas, drop
P mol polyisocyanates is added to 40~50 DEG C in temperature, is warming up to 60~95 DEG C, reacts 2~8 hours, is cooled to after reaction
40~50 DEG C, Q mol carboxyl chain extender is added, is warming up to 60~95 DEG C, insulation reaction 0.5~4 hour, aqueous polyurethane is made
Dispersion；
M:N:P:Q=1:0.1~the 0.6:2~5:0.2~2；
Step 2, in stirring container be added resulting 95~99 parts by weight of aqueous polyurethane dispersion of step 1, after sequentially add
0.1~1 parts by weight of 0.1~0.5 parts by weight of wetting agent, 0.1~0.5 parts by weight of defoaming agent and thickener, control mixing speed exist
500~800rpm, dispersion mixing 15~30 minutes to get resistive connection skin water-based polyurethane adhesive.
7. the preparation method of resistive connection skin water-based polyurethane adhesive according to claim 6, which is characterized in that the step
In 1 after insulation reaction, 40~50 DEG C are cooled to, acetone is added, and Wmol triethylamine aqueous solution is slowly added dropwise and adjusts pH=6
~9, then vacuum distillation removes acetone, while water is added dropwise, aqueous polyurethane dispersion, the W=Q is made.
8. the preparation method of resistive connection skin water-based polyurethane adhesive according to claim 6, which is characterized in that described inorganic
Mineral dust is the composition of one or both of lithium magnesium silicate, aluminium-magnesium silicate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110126041A (en) * | 2019-04-28 | 2019-08-16 | 福建农林大学 | Isocyanates/glycerine/magnesium salts process for preparing resins and application method |
| CN113736062A (en) * | 2021-09-14 | 2021-12-03 | 烟台宜彬新材料科技有限公司 | Waterborne polyurethane emulsion for nylon fastener tape and preparation method thereof |
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| CN101348703A (en) * | 2008-06-20 | 2009-01-21 | 中山大学 | Aqueous polyurethane adhesive and preparation thereof |
| CN102167944A (en) * | 2011-05-31 | 2011-08-31 | 苏州市金近涂料有限公司 | Water-based dipping lacquer and preparation method thereof |
| CN107353394A (en) * | 2017-08-23 | 2017-11-17 | 黄山联固新材料科技有限公司 | A kind of coating, polyurethane and preparation method thereof |
| US20170369624A1 (en) * | 2015-03-12 | 2017-12-28 | Henkel Ag & Co. Kgaa | Aqueous Polyurethane Dispersions |
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| CN101348703A (en) * | 2008-06-20 | 2009-01-21 | 中山大学 | Aqueous polyurethane adhesive and preparation thereof |
| CN102167944A (en) * | 2011-05-31 | 2011-08-31 | 苏州市金近涂料有限公司 | Water-based dipping lacquer and preparation method thereof |
| US20170369624A1 (en) * | 2015-03-12 | 2017-12-28 | Henkel Ag & Co. Kgaa | Aqueous Polyurethane Dispersions |
| CN107353394A (en) * | 2017-08-23 | 2017-11-17 | 黄山联固新材料科技有限公司 | A kind of coating, polyurethane and preparation method thereof |
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| CN110126041A (en) * | 2019-04-28 | 2019-08-16 | 福建农林大学 | Isocyanates/glycerine/magnesium salts process for preparing resins and application method |
| CN110126041B (en) * | 2019-04-28 | 2020-09-04 | 福建农林大学 | Preparation method and use method of isocyanate/glycerol/magnesium salt resin |
| CN113736062A (en) * | 2021-09-14 | 2021-12-03 | 烟台宜彬新材料科技有限公司 | Waterborne polyurethane emulsion for nylon fastener tape and preparation method thereof |
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