CN108239513A - A kind of use for synthetic leather high-performance water-based polyurethane adhesive preparation method and application - Google Patents
A kind of use for synthetic leather high-performance water-based polyurethane adhesive preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- 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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- C08G18/40—High-molecular-weight compounds
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- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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Abstract
A kind of use for synthetic leather high-performance water-based polyurethane adhesive preparation method and application, in terms of parts by weight, 1~3 part of 18~22 parts of mixed polymer glycol, 9~11 parts of isophorone diisocyanate and triethylamine are added in reaction kettle, 1.3~1.6 parts of dihydromethyl propionic acid, 1 are added after reaction, 1~3 part of 4 0.4~0.6 part of butanediols and triethylamine, 3~5 parts of diethanol amine and water are added after reaction, stirring, obtain the aqueous polyurethane of polyhydroxy sealing end, as component A, and using hexamethylene diisocyanate trimer as B component, you can.The present invention uses step polymerization and polyhydroxy closed-end technology, it is prepared for the aqueous polyurethane of polyhydroxy sealing end, as component A, and using HDI trimer as B component, the double-component waterborne polyurethane adhesive of preparation, high crosslinked polyurethane sticking layer, the manufacture available for high-performance water-based synthetic leather can be formed after use.
Description
Technical field
The present invention relates to technical field of synthetic leather, more particularly to a kind of use for synthetic leather high-performance water-based polyurethane adhesive system
Standby and application.
Background technology
Synthetic leather is the institutional framework and performance for simulating natural leather, and can be as the compound of natural leather substitute
Material.Lamina reticularis, with microvoid polyurethane coating simulation grain layer, obtained synthetic leather positive and negative are usually simulated with non-woven fabrics
It is all quite similar with leather, and with certain gas permeability, than common artificial leather closer to natural leather, it is widely used in making
Footwear, boots, luggage and ball etc..Domestic synthetic leather consumption figure is about 45.5 hundred million square metres within 2014, the production ranking world
First.It is expected that 2015 to 2020 between average compound growth rate be about 16.3%, the year two thousand twenty market demand is about 5.85 hundred million
Cubic meter.
At present, the production of Synthetic Leather mainly uses solvent type production technology, and typical process flow is as follows:It is non-
Woven cloths → solvent borne polyurethane wet coagulation coating (bottom) → washing → drying → solvent borne polyurethane dry method moves membrane coat
(upper strata).There is technical issues that using this production technology following.First, it is applied using solvent borne polyurethane wet coagulation
Layer makees bottom, and wet coagulation coating is the surface that solvent borne polyurethane (PU) slurry is coated on to non-woven cloth using coating roller,
Subsequently into " H2O-DMF " coagulating baths solidify PU and form the film with microcellular structure.DMF is employed in this technique
(dimethylformamide) makees solvent, and process can cause the solvent contamination of DMF.Moreover, water can not completely replace poly- ammonia
DMF in ester can cause the DMF residue problems of product, ultimately cause product safety problem.And this product safety problem, meeting
In numerous technical barriers and trade barrier, limitation product enters up-market.Second, it is coagulated using solvent borne polyurethane wet method
Gu coating process, dry to need larger energy consumption, at present, the energy consumption needed for a production line is electric energy 115KW/ hours, steam
700000 kilocalories/hour.Third, using solvent borne polyurethane wet coagulation coating process, special DMF retracting devices are needed, together
When be also required to higher energy consumption, at present, just a set of month recycling 20 tons of DMF device be dropped in 3,500,000 yuan or so.Fourth, using
Solvent borne polyurethane dry method moves membrane coat and makees top layer, and this technique is by solvent borne polyurethane slurry, is coated on using doctor knife coater
Then the surface of release paper is bonded with moving the non-woven cloth of gel coating with wet method, removed after dry, polyurethane film is shifted
The surface of film layer is moved to wet method, finally obtains synthetic leather.Since this technique is using solvent type Finish System, containing largely having
Malicious organic solvent, such as TOL (toluene), MEK (methyl ethyl ketone) and THF (tetrahydrofuran).These organic solvents in process of production
Highly volatile, it is serious to pollute environment and threaten to the health of site operation personnel.
According to above-mentioned traditional solvent type production technology, there is serious problem of environmental pollutions for production process, are one
Non-clean production process.The residue problem of DMF is susceptible in obtained Synthetic Leather, there is larger danger to human body
Evil.So according to current development trend, the production technology cleaned, the Synthetic Leather of production environment friendly are studied
It is the trend of a certainty.Wherein, solvent borne polyurethane is substituted with aqueous polyurethane, production waterborne polyurethane synthetic leather is main
R＆D direction, but Water-resistance of Waterborne Polyurethane, hydrolytic resistance are poor, lead to the poor-performing of waterborne polyurethane synthetic leather.
Particularly aqueous polyurethane adhesive, it is difficult to implement dry doubling and half dry doubling technique, and since water resistance and hydrolytic resistance are insufficient,
Cause wet peel strength and hydrolysis peel strength very low, limit the application of waterborne polyurethane synthetic leather.
Invention content
Based on the above problem, the object of the present invention is to provide a kind of preparations of use for synthetic leather high-performance water-based polyurethane adhesive
And application.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of use for synthetic leather high-performance water-based polyurethane adhesive, in terms of parts by weight, by mixed polymerization
1~3 part of 18~22 parts of object glycol, 9~11 parts of isophorone diisocyanate and triethylamine are added in reaction kettle, under heating
After being stirred to react 80~100min, 1.3~1.6 parts of dihydromethyl propionic acid, 0.4~0.6 part of 1,4-butanediol and three are added
1~3 part of ethamine, is stirred to react 40~60min, then cools down under heating, add 3~5 parts of diethanol amine and water, stirring breast
Change, the aqueous polyurethane of polyhydroxy sealing end is obtained, as component A, and using hexamethylene diisocyanate trimer as B groups
Point, obtain the use for synthetic leather high-performance water-based polyurethane adhesive of two-component.
Further improve of the invention is that mixed polymer glycol uses preceding carry out vacuum dehydration.
Of the invention further improve be, mixed polymer glycol, in terms of parts by weight, by polycaprolactone glycol 50~
10 parts~20 parts of the polytetrahydrofuran ether glycol that 80 parts and relative molecular weight are 2000 mixes.
Further improve of the invention is that the relative molecular weight of polycaprolactone glycol and polytetrahydrofuran ether glycol is
2000。
Further improve of the invention is that the temperature of heating is 80~90 DEG C.
Further improve of the invention is, cools to 30~40 DEG C.
Further improve of the invention is that the time of stirring and emulsifying is 60~80min.
Further improve of the invention is that the mass ratio of mixed polymer glycol and water is (18~22)：(80~
100)。
A kind of application of use for synthetic leather high-performance water-based polyurethane adhesive is bonded wet method shellfish in dry method surfacing process
This, the application in dry method surfacing process in fitting textile cloth and wet processing in fitting superfine fiber chemical leather bass.
Further improve of the invention is, in application, by weight component A：B component=10:(0.5~1), by A groups
Divide and B component mixing, control coating weight are 120~180g/m2, and it is dry under conditions of 100~120 DEG C.
Compared with prior art, the device have the advantages that：
The present invention is prepared for the aqueous polyurethane of polyhydroxy sealing end, is made using step polymerization and polyhydroxy closed-end technology
For component A, and using HDI trimer as B component, the double-component waterborne polyurethane adhesive of preparation can form high friendship after use
The polyurethane sticking layer of connection, peel strength/(N/3cm) >=60, hydrolysis peel strength (10%NaOH, room temperature is for 24 hours) >=50, room temperature
Folding fastness be more than 150,000 times will not delamination, low temperature (- 20 DEG C) folding fastness be more than 60,000 times will not delamination, illumination non yellowing can
For the manufacture of high-performance water-based synthetic leather.More than performance is not achieved in common aqueous polyurethane adhesive.
Double-component waterborne polyurethane adhesive prepared by the present invention when in use, component A and B component is mixed, after coating
Carry out preliminarily dried, after moisture evaporation component A and B component can't immediate response curing, and be in adhesive force
Hot melt state, it is possible to implement dry doubling technique and be bonded component A and B component after bass further cure complete it is final viscous
It closes.Based on this characteristic, the aqueous polyurethane adhesive of this two-component, it is possible to implement dry doubling, half dry doubling and wet combining technique, it is general
Logical aqueous polyurethane adhesive cannot meet the technological requirement of dry doubling.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail, but the present invention is not only limited in these
Example.
A kind of use for synthetic leather high-performance water-based polyurethane adhesive preparation method, in terms of parts by weight, after vacuum dehydration
18~22 parts of mixed polymer glycol, 9~11 parts of isophorone diisocyanate (IPDI), 1~3 part of triethylamine add in reaction
Kettle is stirred to react 80~100min under conditions of 80~90 DEG C, adds 1.3~1.6 parts of dihydromethyl propionic acid (DMPA), 1,
0.4~0.6 part of 4- butanediols (BDO), 1~3 part of triethylamine, are stirred to react 40~60min, then under conditions of 80~90 DEG C
30~40 DEG C are cooled to, adds in 3~5 parts of diethanol amine, 80~100 parts of water, 60~80min of stirring and emulsifying, you can obtain polyhydroxy
The aqueous polyurethane of base sealing end, as component A, and using hexamethylene diisocyanate (HDI) tripolymer as B component, you can
Obtain the use for synthetic leather high-performance water-based polyurethane adhesive of two-component.
Wherein, the mixed polymer glycol, in terms of parts by weight, mixed polymer glycol is 2000 by relative molecular weight
50~80 parts of polycaprolactone glycol (PCL), relative molecular weight be 2000 polytetrahydrofuran ether glycol (PTMEG) 10 parts~20
Part mixes.
Application process：It is mainly used for the adhesive of synthetic leather dry method veneer, in application, by weight by component A：B component
=10:(0.5~1) mixes component A and B component, and control coating weight is 120~180g/m2, and in 100~120 DEG C of condition
Lower drying can implement dry doubling, half dry doubling and wet combining technique.Wherein, dry doubling technique is mainly used in dry method surfacing process and is bonded
Wet method bass, half dry doubling technique, which is mainly used in dry method veneer, is bonded textile cloth, and it is ultra-fine that wet combining technique is mainly used in fitting
Fiber synthetic leather bass.
The present invention is prepared for the aqueous polyurethane of polyhydroxy sealing end, is made using step polymerization and polyhydroxy closed-end technology
For component A, and using HDI trimer as B component, the double-component waterborne polyurethane adhesive of preparation can form high friendship after use
The polyurethane sticking layer of connection, peel strength/(N/3cm) >=60, hydrolysis peel strength (10%NaOH, room temperature is for 24 hours) >=50, room temperature
Folding fastness be more than 150,000 times will not delamination, low temperature (- 20 DEG C) folding fastness be more than 60,000 times will not delamination, illumination non yellowing can
For the manufacture of high-performance water-based synthetic leather.
Embodiment 1
A kind of use for synthetic leather high-performance water-based polyurethane adhesive preparation method, in terms of parts by weight, after vacuum dehydration
18 parts of mixed polymer glycol, 11 parts of isophorone diisocyanate (IPDI), 1 part of addition reaction kettle of triethylamine, at 80 DEG C
Under conditions of be stirred to react 100min, add 1.3 parts of dihydromethyl propionic acid (DMPA), 0.4 part of 1,4-butanediol (BDO), three
3 parts of ethamine, is stirred to react 60min under conditions of 80 DEG C, then cools to 30 DEG C, adds in 5 parts of diethanol amine, 80 parts of water, stirs
Mix emulsification 80min, you can the aqueous polyurethane of polyhydroxy sealing end is obtained, as component A, and with hexamethylene diisocyanate
(HDI) tripolymer is as B component, you can obtains the use for synthetic leather high-performance water-based polyurethane adhesive of two-component.
Wherein, the mixed polymer glycol, in terms of parts by weight, mixed polymer glycol is 2000 by relative molecular weight
50 parts of polycaprolactone glycol (PCL), 10 parts of polytetrahydrofuran ether glycol (PTMEG) mixing that relative molecular weight is 2000 and
Into.
Application process：It is mainly used for the adhesive of synthetic leather dry method veneer, in application, by weight by component A：B component
=10:0.5 mixes component A and B component, and control coating weight is 120g/m2, and it is dry under conditions of 120 DEG C, it can implement to do
Patch technique.Wherein, dry doubling technique is mainly used in fitting wet method bass in dry method surfacing process.
Embodiment 2
A kind of use for synthetic leather high-performance water-based polyurethane adhesive preparation method, in terms of parts by weight, after vacuum dehydration
19 parts of mixed polymer glycol, 10 parts of isophorone diisocyanate (IPDI), 2 parts of addition reaction kettles of triethylamine, at 90 DEG C
Under conditions of be stirred to react 80min, add 1.4 parts of dihydromethyl propionic acid (DMPA), 0.5 part of 1,4-butanediol (BDO), three second
2 parts of amine, is stirred to react 40min under conditions of 90 DEG C, then cools to 35 DEG C, adds in 4 parts of diethanol amine, 90 parts of water, stirring
Emulsify 70min, you can the aqueous polyurethane of polyhydroxy sealing end is obtained, as component A, and with hexamethylene diisocyanate
(HDI) tripolymer is as B component, you can obtains the use for synthetic leather high-performance water-based polyurethane adhesive of two-component.
Wherein, the mixed polymer glycol, in terms of parts by weight, mixed polymer glycol is 2000 by relative molecular weight
80 parts of polycaprolactone glycol (PCL), 20 parts of polytetrahydrofuran ether glycol (PTMEG) mixing that relative molecular weight is 2000 and
Into.
Application process：It is mainly used for the adhesive of synthetic leather dry method veneer, in application, by weight by component A：B component
=10:1 mixes component A and B component, and control coating weight is 180g/m2, and it is dry under conditions of 100 DEG C, it can implement half-dried
Patch technique.Wherein, half dry doubling technique, which is mainly used in dry method veneer, is bonded textile cloth.
Embodiment 3
A kind of use for synthetic leather high-performance water-based polyurethane adhesive preparation method, in terms of parts by weight, after vacuum dehydration
20 parts of mixed polymer glycol, 9 parts of isophorone diisocyanate (IPDI), 3 parts of addition reaction kettles of triethylamine, at 82 DEG C
Under the conditions of be stirred to react 90min, add 1.5 parts of dihydromethyl propionic acid (DMPA), 0.6 part of 1,4-butanediol (BDO), triethylamine
1 part, 55min is stirred to react under conditions of 82 DEG C, then cools to 40 DEG C, adds in 3 parts of diethanol amine, 100 parts of water, stirring breast
Change 60min, you can the aqueous polyurethane of polyhydroxy sealing end is obtained, as component A, and with hexamethylene diisocyanate (HDI)
Tripolymer is as B component, you can obtains the use for synthetic leather high-performance water-based polyurethane adhesive of two-component.
Wherein, the mixed polymer glycol, in terms of parts by weight, mixed polymer glycol is 2000 by relative molecular weight
60 parts of polycaprolactone glycol (PCL), 15 parts of polytetrahydrofuran ether glycol (PTMEG) mixing that relative molecular weight is 2000 and
Into.
Application process：It is mainly used for the adhesive of synthetic leather dry method veneer, in application, by weight by component A：B component
=10:0.6 mixes component A and B component, and control coating weight is 150g/m2, and it is dry under conditions of 110 DEG C, it can implement wet
Patch technique.Wherein, wet combining technique is mainly used in fitting superfine fiber chemical leather bass.
Embodiment 4
A kind of use for synthetic leather high-performance water-based polyurethane adhesive preparation method, in terms of parts by weight, after vacuum dehydration
22 parts of mixed polymer glycol, 9 parts of isophorone diisocyanate (IPDI), 1 part of addition reaction kettle of triethylamine, at 86 DEG C
Under the conditions of be stirred to react 90min, add 1.6 parts of dihydromethyl propionic acid (DMPA), 0.5 part of 1,4-butanediol (BDO), triethylamine
1 part, 50min is stirred to react under conditions of 86 DEG C, then cools to 37 DEG C, adds in 3 parts of diethanol amine, 85 parts of water, stirring breast
Change 65min, you can the aqueous polyurethane of polyhydroxy sealing end is obtained, as component A, and with hexamethylene diisocyanate (HDI)
Tripolymer is as B component, you can obtains the use for synthetic leather high-performance water-based polyurethane adhesive of two-component.
Wherein, the mixed polymer glycol, in terms of parts by weight, mixed polymer glycol is 2000 by relative molecular weight
70 parts of polycaprolactone glycol (PCL), 13 parts of polytetrahydrofuran ether glycol (PTMEG) mixing that relative molecular weight is 2000 and
Into.
Application process：It is mainly used for the adhesive of synthetic leather dry method veneer, in application, by weight by component A：B component
=10:0.7 mixes component A and B component, and control coating weight is 160g/m2, and it is dry under conditions of 115 DEG C, it can implement to do
Patch technique.Wherein, dry doubling technique is mainly used in fitting wet method bass in dry method surfacing process.
Using step polymerization and polyhydroxy closed-end technology, the aqueous polyurethane of polyhydroxy sealing end is prepared for, as A groups
Point, and using HDI trimer as B component, the double-component waterborne polyurethane adhesive of preparation can be formed high crosslinked poly- after use
Urethane adhesive layer, peel strength/(N/3cm) >=60, hydrolysis peel strength (10%NaOH, room temperature is for 24 hours) >=50, room temperature folding jail
Degree be more than 150,000 times will not delamination, low temperature (- 20 DEG C) folding fastness be more than 60,000 times will not delamination, illumination non yellowing, available for height
The manufacture of performance Waterborne synthetic leather.More than performance is not achieved in common aqueous polyurethane adhesive.
Claims (10)
1. a kind of preparation method of use for synthetic leather high-performance water-based polyurethane adhesive, it is characterised in that：It, will in terms of parts by weight
1~3 part of 18~22 parts of mixed polymer glycol, 9~11 parts of isophorone diisocyanate and triethylamine are added to reaction kettle
In, after being stirred to react 80~100min under heating, add 1.3~1.6 parts of dihydromethyl propionic acid, 1,4-butanediol 0.4~0.6
Part and 1~3 part of triethylamine, 40~60min is stirred to react under heating, is then cooled down, add 3~5 parts of diethanol amine and
Water, stirring and emulsifying obtain the aqueous polyurethane of polyhydroxy sealing end, as component A, and with hexamethylene diisocyanate trimer
As B component, the use for synthetic leather high-performance water-based polyurethane adhesive of two-component is obtained.
2. a kind of preparation method of use for synthetic leather high-performance water-based polyurethane adhesive according to claim 1, feature
It is：Mixed polymer glycol uses preceding carry out vacuum dehydration.
3. a kind of preparation method of use for synthetic leather high-performance water-based polyurethane adhesive according to claim 1 or 2, special
Sign is：Mixed polymer glycol is 2000 by 50~80 parts of polycaprolactone glycol and relative molecular weight in terms of parts by weight
10 parts~20 parts of polytetrahydrofuran ether glycol mix.
4. a kind of preparation method of use for synthetic leather high-performance water-based polyurethane adhesive according to claim 3, feature
It is：Polycaprolactone glycol and the relative molecular weight of polytetrahydrofuran ether glycol are 2000.
5. a kind of preparation method of use for synthetic leather high-performance water-based polyurethane adhesive according to claim 1, feature
It is：The temperature of heating is 80~90 DEG C.
6. a kind of preparation method of use for synthetic leather high-performance water-based polyurethane adhesive according to claim 1, feature
It is：Cool to 30~40 DEG C.
7. a kind of preparation method of use for synthetic leather high-performance water-based polyurethane adhesive according to claim 1, feature
It is：The time of stirring and emulsifying is 60~80min.
8. a kind of preparation method of use for synthetic leather high-performance water-based polyurethane adhesive according to claim 1, feature
It is：The mass ratio of mixed polymer glycol and water is (18~22)：(80~100).
9. a kind of application of adhesive prepared by the method as described in claim 1, it is characterised in that：In dry method surfacing process
It is bonded in wet method bass, dry method surfacing process and is bonded in superfine fiber chemical leather bass in fitting textile cloth and wet processing
Using.
10. a kind of application of adhesive prepared by method as claimed in claim 9, it is characterised in that：In application, by weight
Component A：B component=10:(0.5~1) mixes component A and B component, and control coating weight is 120~180g/m2, and 100
It is dry under conditions of~120 DEG C.
Priority Applications (1)
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| CN201810065312.9A CN108239513A (en) | 2018-01-23 | 2018-01-23 | A kind of use for synthetic leather high-performance water-based polyurethane adhesive preparation method and application |
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| CN201810065312.9A CN108239513A (en) | 2018-01-23 | 2018-01-23 | A kind of use for synthetic leather high-performance water-based polyurethane adhesive preparation method and application |
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| CN110982029A (en) * | 2019-11-21 | 2020-04-10 | 万华化学集团股份有限公司 | Waterborne polyurethane resin emulsion for waterborne space leather base and preparation method thereof, waterborne space leather base and preparation method thereof |
| CN112280283A (en) * | 2020-10-17 | 2021-01-29 | 浙江禾欣科技有限公司 | Double-component polyurethane resin for automobile leather and preparation method thereof |
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