CN105062403B - Synthetic leather adhesive and preparation method - Google Patents
Synthetic leather adhesive and preparation method Download PDFInfo
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- CN105062403B CN105062403B CN201510528939.XA CN201510528939A CN105062403B CN 105062403 B CN105062403 B CN 105062403B CN 201510528939 A CN201510528939 A CN 201510528939A CN 105062403 B CN105062403 B CN 105062403B
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Abstract
The present invention provides a kind of synthetic leather adhesive and preparation method thereof, and the synthetic leather adhesive is mainly prepared by raw materials such as polyalcohol, diisocyanate, catalyst, epoxy resin.The present invention carries out chemical modification using epoxy resin to aqueous polyurethane, and the higher branch degree of epoxy resin is incorporated on the main chain of polyurethane, improves tack, peel strength and the rate of drying and water resistance of dispersion liquid film.Use for synthetic leather adhesive prepared by the present invention has good environmental protection property, and dispersion liquid has tack high, and peel strength is good, and rate of drying is fast, excellent water resistance, is provided simultaneously with excellent levelability and spreadability.Meet the use condition of use for synthetic leather adhesive.
Description
Technical field
The present invention relates to chemical field, more particularly to a kind of synthetic leather adhesive and preparation method.
Background technology
The joint product of the coating produced using polyurethane resin as raw material is referred to as " synthetic leather ", and synthetic leather compensate for
The scarcity of corium resource, is most promising natural leather substitute, and traditional synthetic leather industry typically uses solvent type PU
Basic unit and surface material of the resin as production synthetic leather, solvent type polyurethane binder, due to using substantial amounts of organic molten
Agent, not only environment is polluted, worker's health of related industry is damaged, and inflammable and explosive easily triggered
Fire incident, and the use of organic solvent causes the very big wasting of resources, therefore, preventing to pollute from source, solves danger
Evil is imperative for Synthetic Leather industry.However, research and the application work phase of use for synthetic leather water-base resin
It is slower to starting to walk.With aqueous polyurethane (water-based PU) it is relatively very new hitech materials on synthetic leather.Aqueous polyurethane conduct
A kind of eco-environmental prote of excellent filmogen, is constantly recognized, and obtained on corium and spinning coating by people
Overall application.But because the process of manufacture of synthetic leather is totally different from corium processing and spinning coating processing, therefore,
Only selection meets that the filming performance of resin is not nearly enough, and selection can meet the aqueous polyurethane of synthetic leather processing technique to closing weight
Will.
Requirement for waterborne polyurethane for synthetic leather is：Must have good tack, peel strength and faster
Rate of drying, possesses excellent water resistance, film is placed in water, should never be deformed, never whiting denaturation.The water resistance of synthetic leather will
It is more even more important than solvent resistance, because synthesis leather goods always touch rainwater or aqueous substance, become if water-based PU films meet water
It can whiten, physical property declines, then, it is difficult to reach real consumption index.Rubbed moreover, most of synthetic leather will enter water-filling
Line, if water resistance does not reach requirement, full decorative pattern just can not be rubbed, broken skin phenomenon is there is also when serious.In addition, water-based PU
Should also have excellent levelability, spreadability, slurry to have striped or perforation after scratching in release liners.Can not after drying
There are crackle, shrinkage cavity phenomenon.
Epoxy resin has many excellent performances, such as outstanding cementability, improves tack, be high mechanical strength, resistance to
It is water-based good etc., there is excellent performance with epoxy resin modification and using the water-based PU of appropriate other raw materials, apply and synthesizing
On leather aqueous binder, the rigors of waterborne polyurethane for synthetic leather are disclosure satisfy that.
Chinese patent CN103450837A discloses a kind of preparation method of waterborne polyurethane for synthetic leather adhesive：Formula
The middle polyalcohol used all uses average relative molecular mass as 1000 ± 50, and hydroxyl value is 105-120mgKOH/g poly- tetrahydrochysene furan
Mutter ether glycol, although the water resistance of adhesive is relatively good, use the polyol molecular weight used relatively low as adhesive, meeting
Cause tack and the peel strength of final products synthetic leather inadequate, so as to influence the performance quality of synthetic leather.
Chinese patent CN103450837A discloses a kind of Waterborne polyurethane resin with high solid content and its synthetic method：In order to
The production technology of synthetic leather is adapted to, rate of drying is accelerated by the solid content for improving emulsion, improves tack, but rely on and carry
The method of high solids content substantially increases production cost, and also uses nmp solvent in being formulated, and is not reaching to complete environmental protection
It is required that.
Chinese patent CN101717488A discloses a kind of epoxy resin modified aqueous PU emulsions and preparation method thereof, although
It make use of the premium properties of epoxy resin to be modified water-based PU, but have many defects in being formulated：As polyalcohol uses
PEPA 210N or 220N, it is well known that PEPA 210N and 220N very not hydrolysis, as raw material
Water-based PU emulsions shelf-stability extreme difference, emulsion and film properties will seriously degrade after some months or half a year；And change
Property after aqueous PU glue film water resistance simply from 49.8% it is minimum fall below 12.3%, it is water-based viscous not reach use for synthetic leather completely
The requirement of mixture.
The content of the invention
In view of the above the shortcomings that prior art, it is an object of the invention to provide a kind of synthetic leather adhesive and preparation
Method, for solving problems present in prior art.
In order to achieve the above objects and other related objects, the present invention provides a kind of synthetic leather adhesive, mainly by following matter
The raw material of amount number is made：Polyalcohol 104.46-120.3 parts, diisocyanate 23.1-35.64 parts, catalyst 0.0045-
0.072 part, carboxylic acid type chain extender 5.7-7.2 parts, oh type small molecule chain extender 0.6-1.80 parts, internal crosslinker 0.3-0.9 parts,
Epoxy resin 4.8-9 parts, nertralizer 3.78-5.06 parts, organic solvent 40-55 parts, antioxidant 0.1-1.2 parts, amine chainextender
1.5-2.7 parts, wetting agent 1.5-2.5 parts, levelling agent 1.5-2.5 parts, thickener 4-5 parts.
According to one of embodiment of the present invention, the polyalcohol includes PTMG 2000, PolyTHF
Ether glycol 3000 and PCDL 1000, its mass ratio are 6-10:1:0.1-1.
Polyol component with the addition of the tetrahydrofuran ether glycol (M=3000) of higher molecular weight, improve the first viscous of film
Property and peel strength, while be formulated in be suitably added physical property and light resistance that PCDL further improves film
Energy.
Above-mentioned molecular weight is number average molecular.
According to another embodiment of the present invention, the diisocyanate is IPDI (IPDI), six Asias
One or both of methyl diisocyanate (HDI)；
The catalyst is selected from stannous octoate (T-9), dibutyl tin laurate (T-12), bismuth sulfonic group catalyst Bi
(CH3SO3)3In one kind；
The one kind of the carboxylic acid type chain extender in dihydromethyl propionic acid, dimethylolpropionic acid；
The oh type small molecule chain extender in 1,6-HD, 1,4 cyclohexane dimethanol, neopentyl glycol one
Kind；
The internal crosslinker is trimethylolpropane；
The one kind of the nertralizer in triethylamine, DMAE, dimethylamino propyl alcohol；
The one kind of the antioxidant in antioxidant 1010, antioxidant 1024, antioxidant 2246；
The one kind of the organic solvent in acetone, DMAC, NMP, DMF；
The amine chainextender is one kind in hexamethylene diamine, IPD, ethylenediamine；
The one kind of the thickener in hydroxyethyl cellulose, association type aqueous polyurethane.
The isocyanates that the present invention uses is IPDI (IPDI), hexamethylene diisocyanate
(HDI) one or two, HDI and IPDI are more suitable for the raw material for doing Aqueous Polyurethane Adhesives, and the two belongs to fat
The diisocyanate of the resistance to light type of race, makes film have outstanding resistance to light.
Preferably, the antioxidant is antioxidant 1010；The organic solvent is acetone.
Antioxidant 1010 is a kind of polynary hindered phenol type antioxidant, has good compatibility with most polymers, has
Good prevents discoloration caused by light and heat, and toxicity is extremely low, available in packaging material for food.
Above-mentioned raw materials can be commercially available from market, and its epoxy resin is commercially available epoxy resin E-44, and wetting agent is
German enlightening is high by 245, and levelling agent is that German enlightening is high by 440.
Above-mentioned wetting agent and levelling agent ensure that polyurethane dispersing liquid slurry has excellent levelability, spreadability, blade coating
There is no crackle and shrinkage cavity phenomenon after no striped or perforation, drying after in release liners.
According to a further embodiment of the present invention, the synthetic leather adhesive, its preparation method includes：
(1) polyalcohol and isocyanates are added in reactor, carries out first step pre-polymerization, then add catalyst, carboxylic acid
Type chain extender and internal crosslinker, second step pre-polymerization is carried out, epoxy resin is then added, reacts to isocyanate groups (- NCO) no
Antioxidant is added when changing again, obtains base polyurethane prepolymer for use as；
(2) viscosity of the organic solvent regulation base polyurethane prepolymer for use as is added to 70-80mpas, and is added nertralizer and entered
Row neutralizes, and stirs, and obtains neutralizing mixture；Add water and amine chainextender, disperse, remove organic solvent, obtain dispersion liquid；
(3) levelling agent, wetting agent, thickener are added into the dispersion liquid to be compounded and thickened, produce the synthesis
Remove from office adhesive.
Preferably, the reaction temperature of first step pre-polymerization is 80-95 DEG C, preferably 85-90 DEG C；Reaction time is 1-3 hours,
Preferably 2-2.5 hours.
Preferably, after first step pre-polymerization, 80-55 DEG C is cooled to, is preferably cooled to 75 DEG C -70 DEG C.
Preferably, the reaction temperature of second step pre-polymerization is 85-55 DEG C, preferably 80-75 DEG C；Reaction time is 2-4 hours,
Preferably 2.5-3 hours.
Preferably, in step (1), the reaction temperature added after epoxy resin is 64-60 DEG C, and the reaction time is that 0.5-1 is small
When.
Preferably, in step (2), before adding organic solvent, the temperature of the base polyurethane prepolymer for use as is cooled to 60-55
℃。
Preferably, in step (2), stir speed (S.S.) when disperseing is 1000-2000 revs/min, mixing time 20-30 minutes.
Preferably, in step (3), compounding and thickening are stirred, and mixing speed is 100-200 revs/min, and mixing time is
30-50 minutes, preferably 30-35 minutes.
In order to achieve the above objects and other related objects, the present invention provides a kind of preparation method of synthetic leather adhesive, bag
Include：
(1) polyalcohol and isocyanates are added in reactor, carries out first step pre-polymerization, then add catalyst, carboxylic acid
Type chain extender and internal crosslinker, second step pre-polymerization is carried out, epoxy resin is then added, reacts to isocyanate groups (- NCO) no
Antioxidant is added when changing again, obtains base polyurethane prepolymer for use as；
(2) viscosity of the organic solvent regulation base polyurethane prepolymer for use as is added to 70-80mpas, and is added nertralizer and entered
Row neutralizes, and stirs, and obtains neutralizing mixture；Add water and amine chainextender, disperse, remove organic solvent, obtain dispersion liquid；
(3) levelling agent, wetting agent, thickener are added into the dispersion liquid to be compounded and thickened, produce the synthesis
Remove from office adhesive.
According to one of embodiment of the present invention, the reaction temperature of first step pre-polymerization is 80-95 DEG C, preferably 85-90 DEG C；Instead
It it is 1-3 hours, preferably 2-2.5 hours between seasonable.
According to another embodiment of the present invention, after first step pre-polymerization, 80-55 DEG C is cooled to, is preferably cooled to 75 DEG C -70
℃。
According to a further embodiment of the present invention, the reaction temperature of second step pre-polymerization is 85-55 DEG C, preferably 80-75 DEG C；Instead
It it is 2-4 hours, preferably 2.5-3 hours between seasonable.
According to a further embodiment of the present invention, in step (1), the reaction temperature added after epoxy resin is 64-60 DEG C, instead
It it is 0.5-1 hours between seasonable.
According to a further embodiment of the present invention, in step (2), before adding organic solvent, by the base polyurethane prepolymer for use as
Temperature is cooled to 60-55 DEG C.
According to a further embodiment of the present invention, in step (2), stir speed (S.S.) when disperseing is 1000-2000 revs/min, is stirred
Mix minute time 20-30.
According to a further embodiment of the present invention, in step (3), compounding and thickening are stirred, mixing speed 100-200
Rev/min, mixing time is 30-50 minutes, preferably 30-35 minutes.
As described above, the synthetic leather adhesive of the present invention, has the advantages that：
The present invention carries out chemical modification using epoxy resin to aqueous polyurethane, and the higher branch degree of epoxy resin is introduced
Onto the main chain of polyurethane, tack, peel strength and the rate of drying and water resistance of dispersion liquid film are improved.The present invention
The use for synthetic leather adhesive of preparation has good environmental protection property, and dispersion liquid has tack high, and peel strength is good, dries speed
Degree is fast, excellent water resistance, is provided simultaneously with excellent levelability and spreadability.Meet the use condition of use for synthetic leather adhesive.
Embodiment
Illustrate embodiments of the present invention below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through specific realities different in addition
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
It should be clear that in the following example not specifically dated process equipment or device using conventional equipment in the art or
Device；All pressure values and scope are all referring to absolute pressure.
In addition, it is to be understood that one or more method and steps mentioned in the present invention do not repel before and after the combination step
There can also be other method step or other method step can also be inserted between the step of these are specifically mentioned, unless separately
It is described；It should also be understood that the combination annexation between one or more equipment/devices mentioned in the present invention is not repelled
Can also have other equipment/device before and after the unit equipment/device or two equipment/devices specifically mentioning at these it
Between can also insert other equipment/device, unless otherwise indicated.Moreover, unless otherwise indicated, the numbering of various method steps is only
Differentiate the convenient tool of various method steps, rather than ordering or the enforceable model of the restriction present invention for limitation various method steps
Enclose, its relativeness is altered or modified, and in the case where changing technology contents without essence, when being also considered as, the present invention is enforceable
Category.
Embodiment 1
Exemplified by producing about 500 kg ethylene resin modified aqueous polyurethane adhesives, formula for raw stock proportioning is using different
The lower limit of cyanate, using HDI, stannous octoate, dihydromethyl propionic acid, 1.6- hexylene glycols, DMAE, ethylenediamine,
Hydroxyethyl cellulose is raw material.
Raw material components and formula：PTMG 2000：73 kilograms, PTMG 3000：12 is public
Jin, PCDL 1000：6 kilograms, HDI：23.1 kilograms, stannous octoate：0.0045 kilogram, dihydromethyl propionic acid：It is 5.7 public
Jin, 1,6-HD：0.6 kilogram, trimethylolpropane：0.3 kilogram, epoxy resin E-44：4.8 kilograms, acetone：40 kilograms,
DMAE：3.78 kilograms, antioxidant 1010：0.3 kilogram, deionized water：342 kilograms, ethylenediamine：1.5 kilograms, wetting
Agent 245：1.5 kilograms, levelling agent 440：1.5 kilograms, hydroxyethylcellulose thickener：4.0 kilogram.
Its preparation methods steps are as follows：
(1) synthesis of base polyurethane prepolymer for use as
PTMG 2000, PTMG 3000, PCDL 1000 and HDI are added
In reactor, stirring is opened, the 85 DEG C of reactions of control temperature, carries out first step pre-polymerization, the pre-polymerization time is 2 hours, is then cooled to
75 DEG C, add stannous octoate, dihydromethyl propionic acid, trimethylolpropane, 1.6- hexylene glycols, 80 DEG C of -75 DEG C of continuation of control temperature
Chain-extension polymerization 2.5 hours, epoxy resin is added when reducing the temperature to 60 DEG C with acetone, is continued reaction 0.5 hour, is added antioxygen
Agent 1010, second step performed polymer is obtained, acetone is suitably added during the pre-polymerization of second step and carries out reduction viscosity.
(2) polyurethane prepolymer neutralizes
Performed polymer is cooled down 60 DEG C, adjusts viscosity to about 70-80mpa.s using acetone, and add DMAE and enter
Row neutralizes, and stirs 15 minutes, obtains neutralizing mixture.
(3) chain extension and emulsification
Under high shear, deionized water is added, adds ethylenediamine, dispersion rate is controlled at 1000-2000 revs/min, stirred
Mix the time 20 minutes, obtain epoxy resin modified aqueous polyurethane dispersion liquid.
(4) it is evaporated under reduced pressure
By epoxy resin modified aqueous polyurethane dispersion liquid temperature be 40 DEG C, vacuum be 0.09MPa under conditions of enter
Row is evaporated under reduced pressure, and is removed the acetone in dispersion liquid, that is, is obtained pH=7.6, solid content 30% it is epoxy resin modified aqueous poly-
Urethane dispersion liquid.
(5) compound and thicken
Resulting epoxy resin modified aqueous polyurethane dispersion liquid is slowly added into successively under conditions of normal temperature, stirring
Levelling agent 440, wetting agent 245, thickener hydroxyethyl cellulose, mixing time are 30 minutes, obtain use for synthetic leather epoxy resin
The adhesive of modified aqueous polyurethane dispersion liquid.
Embodiment 2
Exemplified by producing about 500 kg ethylene resin modified aqueous polyurethane adhesives, formula for raw stock proportioning is using different
The lower limit of cyanate, using IPDI, dibutyl tin laurate, dihydromethyl propionic acid, 1.6- hexylene glycols, dimethylamino second
Alcohol, ethylenediamine, hydroxyethyl cellulose are raw material.
Raw material components and formula：PTMG 2000：95.4 kilograms, PTMG 3000：
11.4 kilograms, PCDL 1000:6 kilograms, IPDI：30.6 kilograms, dibutyl tin laurate：0.036 kilogram, dihydroxy
Methylpropanoic acid：5.7 kilograms, 1,6-hexylene glycol：0.6 kilogram, trimethylolpropane：0.3 kilogram, epoxy resin E-44：It is 4.8 public
Jin, DMF：55 kilograms, DMAE：3.78 kilograms, antioxidant 1024：1.2 kilograms, deionized water：342 kilograms, second two
Amine：1.5 kilograms, wetting agent 245：1.5 kilograms, levelling agent 440：1.5 kilograms, hydroxyethylcellulose thickener：4 kilograms.
Its preparation methods steps are as follows：
(1) synthesis of base polyurethane prepolymer for use as
PTMG 2000, PTMG 3000, PCDL 1000 and IPDI are added
Enter in reactor, open stirring, the 90 DEG C of reactions of control temperature, carry out first step pre-polymerization, the pre-polymerization time is 2 hours, is then cooled
To 75 DEG C, dibutyl tin laurate, dihydromethyl propionic acid, trimethylolpropane, 1.6- hexylene glycols are added, controls 80 DEG C of temperature
Continue chain-extension polymerization 3 hours, epoxy resin is added when reducing the temperature to 64 DEG C with acetone, continue reaction 1 hour, add antioxygen
Agent 1024, second step performed polymer is obtained, DMF is suitably added during the pre-polymerization of second step and carries out reduction viscosity.
(2) polyurethane prepolymer neutralizes
Performed polymer is cooled down 60 DEG C, adjusts viscosity to about 70-80mpa.s using DMF, and add DMAE progress
Neutralize, stir 15 minutes, obtain neutralizing mixture.
(3) chain extension and emulsification
Under high shear, deionized water is added, adds ethylenediamine, dispersion rate is controlled at 1000-2000 revs/min, stirred
Mix the time 20 minutes, obtain epoxy resin modified aqueous polyurethane dispersion liquid.
(4) it is evaporated under reduced pressure
By epoxy resin modified aqueous polyurethane dispersion liquid temperature be 45 DEG C, vacuum be 0.09MPa under conditions of enter
Row is evaporated under reduced pressure, and is removed the DMF in dispersion liquid, that is, is obtained pH=7.5, epoxy resin modified aqueous poly- ammonia of the solid content 32%
Ester dispersion liquid.
Compounding and thickening
Resulting epoxy resin modified aqueous polyurethane dispersion liquid is slowly added into successively under conditions of normal temperature, stirring
Levelling agent 440, wetting agent 245, thickener hydroxyethyl cellulose, mixing time are 30 minutes, obtain use for synthetic leather epoxy resin
The adhesive of modified aqueous polyurethane dispersion liquid.
Embodiment 3
Exemplified by producing about 500 kg ethylene resin modified aqueous polyurethane adhesives, formula for raw stock proportioning is using different
The median of cyanate, using IPDI, HDI, stannous octoate, dihydromethyl propionic acid, 1.4- cyclohexanedimethanols, triethylamine, oneself
Diamines, hydroxyethyl cellulose are raw material.
Raw material components and formula：PTMG 2000：95.79 kilograms, PTMG 3000：
11.2 kilograms, PCDL 1000:5.63 kilograms, IPDI：16.56 kilogram, HDI：12.54 kilogram, stannous octoate：
0.029 kilogram, dihydromethyl propionic acid：6.48 kilograms, 1.4- cyclohexanedimethanols：1.2 kilograms, trimethylolpropane：0.6 is public
Jin, epoxy resin E-44：6.9 kilogram, acetone：50 kilograms, triethylamine：4.86 kilograms, antioxidant 1010：0.8 kilogram, deionization
Water：342 kilograms, hexamethylene diamine：2.1 kilograms, wetting agent 245：2.0 kilograms, levelling agent 440：2.0 kilograms, hydroxyethyl cellulose increasing
Thick dose：4.5 kilogram.
Its preparation methods steps are as follows：
(1) synthesis of base polyurethane prepolymer for use as
By PTMG 2000, PTMG 3000, PCDL 1000 and IPDI,
HDI is added in reactor, is opened stirring, the 90 DEG C of reactions of control temperature, is carried out first step pre-polymerization, the pre-polymerization time is 2.5 hours, so
After cool to 72 DEG C, add stannous octoate, dihydromethyl propionic acid, trimethylolpropane, 1.4- cyclohexanedimethanols, control temperature
80-75 DEG C is continued chain-extension polymerization 3 hours, and epoxy resin is added when reducing the temperature to 62 DEG C with acetone, continues reaction 1 hour, then
Antioxidant 1010 is added, second step performed polymer is obtained, acetone is suitably added during the pre-polymerization of second step and carries out reduction viscosity.
(2) polyurethane prepolymer neutralizes
Performed polymer is cooled down 57 DEG C, viscosity is adjusted to about 70-80mpa.s using acetone, and adds triethylamine and is neutralized,
Stirring 15 minutes, obtain neutralizing mixture.
(3) chain extension and emulsification
Under high shear, deionized water is added, adds hexamethylene diamine, dispersion rate is controlled at 1000-2000 revs/min, stirred
Mix the time 25 minutes, obtain epoxy resin modified aqueous polyurethane dispersion liquid.
(4) it is evaporated under reduced pressure
By epoxy resin modified aqueous polyurethane dispersion liquid temperature be 50 DEG C, vacuum be 0.09MPa under conditions of enter
Row is evaporated under reduced pressure, and is removed the acetone in dispersion liquid, that is, is obtained pH=8.2, solid content 34% it is epoxy resin modified aqueous poly-
Urethane dispersion liquid.
(5) compound and thicken
Resulting epoxy resin modified aqueous polyurethane dispersion liquid is slowly added into successively under conditions of normal temperature, stirring
Levelling agent 440, wetting agent 245, thickener hydroxyethyl cellulose, mixing time are 30 minutes, obtain use for synthetic leather epoxy resin
The adhesive of modified aqueous polyurethane dispersion liquid.
Embodiment 4
Exemplified by producing about 500 kg ethylene resin modified aqueous polyurethane adhesives, formula for raw stock proportioning is using different
The higher limit of cyanate, using IPDI, HDI, dibutyl tin laurate, dimethylolpropionic acid, 1.4- cyclohexanedimethanols, three
Ethamine, hexamethylene diamine, association type aqueous polyurethane thickener are raw material.
Raw material components and formula：PTMG 2000：92.58 kilograms, PTMG 3000：
10.8 kilograms, PCDL 1000:5.4 kilograms, IPDI：17.82 kilogram, HDI：13.5 kilograms, di lauric dibutyl
Tin：0.029 kilogram, dimethylolpropionic acid：7.2 kilograms, 1.4- cyclohexanedimethanols：1.8 kilograms, trimethylolpropane：0.9 is public
Jin, epoxy resin E-44：6.9 kilograms, acetone：42 kilograms, triethylamine：4.88 kilograms, antioxidant 1010：0.9 kilogram, deionization
Water：342 kilograms, hexamethylene diamine：2.1 kilograms, wetting agent 245：2.0 kilograms, levelling agent 440：2.0 kilograms, the water-based poly- ammonia of association type
Ester thickener：4.5 kilogram.
Its preparation methods steps are as follows：
(1) synthesis of base polyurethane prepolymer for use as
By PTMG 2000, PTMG 3000, PCDL 1000 and IPDI,
HDI is added in reactor, is opened stirring, the 90 DEG C of reactions of control temperature, is carried out first step pre-polymerization, the pre-polymerization time is 2.5 hours, so
After cool to 72 DEG C, add dibutyl tin laurate, dimethylolpropionic acid, trimethylolpropane, 1.4- cyclohexanedimethanols,
Control 80-75 DEG C of temperature to continue chain-extension polymerization 3 hours, add epoxy resin when reducing the temperature to 62 DEG C with acetone, continue reaction 1
Hour, antioxidant 1010 is added, obtains second step performed polymer, being suitably added acetone during the pre-polymerization of second step is dropped
Low viscosity.
(2) polyurethane prepolymer neutralizes
Performed polymer is cooled down 57 DEG C, viscosity is adjusted to about 70-80mpa.s using acetone, and adds triethylamine and is neutralized,
Stirring 15 minutes, obtain neutralizing mixture.
(3) chain extension and emulsification
Under high shear, deionized water is added, adds hexamethylene diamine, dispersion rate is controlled at 1000-2000 revs/min, stirred
Mix the time 25 minutes, obtain epoxy resin modified aqueous polyurethane dispersion liquid.
(4) it is evaporated under reduced pressure
By epoxy resin modified aqueous polyurethane dispersion liquid temperature be 50 DEG C, vacuum be 0.09MPa under conditions of enter
Row is evaporated under reduced pressure, and is removed the acetone in dispersion liquid, that is, is obtained pH=7.6, solid content 30% it is epoxy resin modified aqueous poly-
Urethane dispersion liquid.
(5) compound and thicken
Resulting epoxy resin modified aqueous polyurethane dispersion liquid is slowly added into successively under conditions of normal temperature, stirring
Levelling agent 440, wetting agent 245, thickener hydroxyethyl cellulose, mixing time are 30 minutes, obtain use for synthetic leather epoxy resin
The adhesive of modified aqueous polyurethane dispersion liquid.
Embodiment 5
Exemplified by producing about 500 kg ethylene resin modified aqueous polyurethane adhesives, formula for raw stock proportioning is using different
The higher limit of cyanate, using IPDI, bismuth sulfonic group catalyst Bi (CH3SO3)3, dimethylolpropionic acid, neopentyl glycol, diformazan ammonia
Base propyl alcohol, IPD, association type aqueous polyurethane thickener are raw material.
Raw material components and formula：PTMG 2000：88.86 kilograms, PTMG 3000：
10.2 kilograms, PCDL 1000:5.4 kilograms, IPDI：35.64 kilograms, bismuth sulfonic group catalyst Bi (CH3SO3) 3：
0.072 kilogram, dimethylolpropionic acid：7.2 kilogram, neopentyl glycol：1.8 kilograms, trimethylolpropane：0.9 kilogram, epoxy resin
E-44：9.0 kilograms, acetone：48 kilograms, dimethylamino propyl alcohol：5.06 kilograms, antioxidant 1010：0.6 kilogram, deionized water：
342 kilograms, IPD：2.7 kilograms, wetting agent 245：2.5 kilograms, levelling agent 440：2.5 kilograms, association type it is water-based poly-
Urethane thickener：5.0 kilogram.
Its preparation methods steps are as follows：
(1) synthesis of base polyurethane prepolymer for use as
PTMG 2000, PTMG 3000, PCDL 1000 and IPDI are added
Enter in reactor, open stirring, the 90 DEG C of reactions of control temperature, carry out first step pre-polymerization, the pre-polymerization time is 2 hours, is then cooled
To 70 DEG C, bismuth sulfonic group catalyst Bi (CH3SO3) 3, dimethylolpropionic acid, trimethylolpropane, neopentyl glycol, control are added
80 DEG C of temperature continues chain-extension polymerization 3 hours, and epoxy resin is added when reducing the temperature to 64 DEG C with acetone, continues reaction 1 hour, then
Antioxidant 1010 is added, second step performed polymer is obtained, acetone is suitably added during the pre-polymerization of second step and carries out reduction viscosity.
(2) polyurethane prepolymer neutralizes
Performed polymer is cooled down 55 DEG C, adjusts viscosity to about 70-80mpa.s using acetone, and add dimethylamino propyl alcohol and enter
Row neutralizes, and stirs 10 minutes, obtains neutralizing mixture.
(3) chain extension and emulsification
Under high shear, add deionized water, add IPD, dispersion rate control 1000-2000 turn/
Point, mixing time 30 minutes, obtain epoxy resin modified aqueous polyurethane dispersion liquid.
(4) it is evaporated under reduced pressure
By epoxy resin modified aqueous polyurethane dispersion liquid temperature be 60 DEG C, vacuum be 0.095MPa under conditions of enter
Row is evaporated under reduced pressure, and is removed the acetone in dispersion liquid, that is, is obtained pH=7.5-9, solid content 30% it is epoxy resin modified aqueous
Polyurethane dispersing liquid.
(5) compound and thicken
Resulting epoxy resin modified aqueous polyurethane dispersion liquid is slowly added into successively under conditions of normal temperature, stirring
Levelling agent 440, wetting agent 245, thickener hydroxyethyl cellulose, mixing time are 35 minutes, obtain use for synthetic leather epoxy resin
The adhesive of modified aqueous polyurethane dispersion liquid.
Embodiment 6
Exemplified by producing about 500 kg ethylene resin modified aqueous polyurethane adhesives, formula for raw stock proportioning is using different
The higher limit of cyanate, using HDI, bismuth sulfonic group catalyst Bi (CH3SO3)3, dimethylolpropionic acid, neopentyl glycol, diformazan ammonia
Base propyl alcohol, IPD, association type aqueous polyurethane thickener bottom kind.
Raw material components and formula：PTMG 2000：96.16 kilograms, PTMG 3000：
11.3 kilograms, PCDL 1000:5.67 kilograms, HDI：26.97 kilograms, bismuth sulfonic group catalyst Bi (CH3SO3) 3：
0.036 kilogram, dimethylolpropionic acid：7.2 kilograms, neopentyl glycol：1.8 kilograms, trimethylolpropane：0.9 kilogram, epoxy resin
E-44：9.0 kilograms, acetone：41 kilograms, dimethylamino propyl alcohol：5.06 kilograms, antioxidant 1010：0.6 kilogram, deionized water：
342 kilograms, IPD：2.7 kilograms, wetting agent 245：2.5 kilograms, levelling agent 440：2.5 kilograms, association type it is water-based poly-
Urethane thickener：5.0 kilogram.
Its preparation methods steps are as follows：
(1) synthesis of base polyurethane prepolymer for use as
PTMG 2000, PTMG 3000, PCDL 1000 and HDI are added
In reactor, stirring is opened, the 85 DEG C of reactions of control temperature, carries out first step pre-polymerization, the pre-polymerization time is 2 hours, is then cooled to
70 DEG C, add bismuth sulfonic group catalyst Bi (CH3SO3) 3, dimethylolpropionic acid, trimethylolpropane, neopentyl glycol, control temperature
75 DEG C of degree continues chain-extension polymerization 2.5 hours, and epoxy resin is added when reducing the temperature to 60 DEG C with acetone, continues reaction 0.5 hour,
Antioxidant 1010 is added, obtains second step performed polymer, acetone is suitably added during the pre-polymerization of second step and reduce and is glued
Degree.
(2) polyurethane prepolymer neutralizes
Performed polymer is cooled down 55 DEG C, adjusts viscosity to about 70-80mpa.s using acetone, and add dimethylamino propyl alcohol and enter
Row neutralizes, and stirs 10 minutes, obtains neutralizing mixture.
(3) chain extension and emulsification
Under high shear, add deionized water, add IPD, dispersion rate control 1000-2000 turn/
Point, mixing time 30 minutes, obtain epoxy resin modified aqueous polyurethane dispersion liquid.
(4) it is evaporated under reduced pressure
By epoxy resin modified aqueous polyurethane dispersion liquid temperature be 60 DEG C, vacuum be 0.095MPa under conditions of enter
Row is evaporated under reduced pressure, and is removed the acetone in dispersion liquid, that is, is obtained pH=7.9, solid content 29% it is epoxy resin modified aqueous poly-
Urethane dispersion liquid.
(5) compound and thicken
Resulting epoxy resin modified aqueous polyurethane dispersion liquid is slowly added into successively under conditions of normal temperature, stirring
Levelling agent 440, wetting agent 245, association type polyurethane thickener, mixing time are 35 minutes, obtain use for synthetic leather epoxy resin
The adhesive of modified aqueous polyurethane dispersion liquid.
Comparative example 1
Raw material components and formula：PTMG 1000：102.16 kilogram, IPDI：22.07 kilogram, HDI：
17.79 kilogram, stannous octoate：0.029 kilogram, dihydromethyl propionic acid：6.48 kilograms, 1.4- cyclohexanedimethanols：1.2 kilograms,
Trimethylolpropane：0.3 kilogram, acetone：48 kilograms, triethylamine：4.86 kilograms, antioxidant 1010：0.6 kilogram, deionized water：
342 kilograms, hexamethylene diamine：2.1 kilograms, wetting agent 245：2.0 kilograms, levelling agent 440：2.0 kilograms, hydroxyethyl cellulose thickening
Agent：4.5 kilogram.
Its preparation methods steps are as follows：
(1) synthesis of base polyurethane prepolymer for use as
PTMG 1000 and IPDI, HDI are added in reactor, open stirring, 90 DEG C of control temperature is anti-
Should, pre-polymerization is carried out, the pre-polymerization time is 2 hours, then cools to 72 DEG C, adds stannous octoate, dihydromethyl propionic acid, trihydroxy methyl
Propane, 1.4- cyclohexanedimethanols, 80-75 DEG C of control temperature continue chain-extension polymerization 3 hours, add antioxidant 1010, obtain
Second step performed polymer, acetone is suitably added during the pre-polymerization of second step and carries out reduction viscosity.
(2) polyurethane prepolymer neutralizes
Performed polymer is cooled down 57 DEG C, viscosity is adjusted to about 70-80mpa.s using acetone, and adds triethylamine and is neutralized,
Stirring 15 minutes, obtain neutralizing mixture.
(3) chain extension and emulsification
Under high shear, deionized water is added, adds hexamethylene diamine, dispersion rate is controlled at 1000-2000 revs/min, stirred
Mix the time 25 minutes, obtain aqueous polyurethane dispersing liquid.
(4) it is evaporated under reduced pressure
By aqueous polyurethane dispersing liquid temperature be 50 DEG C, vacuum be 0.09MPa under conditions of be evaporated under reduced pressure, take off
Except the acetone in dispersion liquid, that is, obtain pH=7.5-9, epoxy resin modified aqueous polyurethane dispersion liquid of the solid content 30%.
(5) compound and thicken
Resulting aqueous polyurethane dispersing liquid is slowly added into levelling agent 440, profit successively under conditions of normal temperature, stirring
Humectant 245, thickener hydroxyethyl cellulose, mixing time are 30 minutes, obtain the viscous of waterborne polyurethane for synthetic leather dispersion liquid
Mixture.
Comparative example 2
Raw material components and formula：PTMG 2000：105.96 kilogram, IPDI：35.64 kilograms, octanoic acid Asia
Tin：0.036 kilogram, dihydromethyl propionic acid：5.7 kilograms, neopentyl glycol：1.8 kilograms, trimethylolpropane：0.9 kilogram, acetone：
48 kilograms, dimethylamino propyl alcohol：5.06 kilograms, antioxidant 1010：0.6 kilogram, deionized water：342 kilograms, isophorone two
Amine：2.7 kilograms, wetting agent 245：2.5 kilograms, levelling agent 440：2.5 kilograms, association type aqueous polyurethane thickener：It is 5.0 public
Jin.
Its preparation methods steps are as follows：
(1) synthesis of base polyurethane prepolymer for use as
PTMG 2000 and IPDI are added in reactor, stirring is opened, the 90 DEG C of reactions of control temperature, enters
Row first step pre-polymerization, pre-polymerization time are 2 hours, then cool to 70 DEG C, add stannous octoate, dihydromethyl propionic acid, three hydroxyl first
Base propane, neopentyl glycol, 80 DEG C of control temperature continue chain-extension polymerization 3 hours, add antioxidant 1010, obtain second step pre-polymerization
Body, acetone is suitably added during the pre-polymerization of second step and carries out reduction viscosity.
(2) polyurethane prepolymer neutralizes
Performed polymer is cooled down 55 DEG C, adjusts viscosity to about 70-80mpa.s using acetone, and add dimethylamino propyl alcohol and enter
Row neutralizes, and stirs 10 minutes, obtains neutralizing mixture.
(3) chain extension and emulsification
Under high shear, add deionized water, add IPD, dispersion rate control 1000-2000 turn/
Point, mixing time 30 minutes, obtain aqueous polyurethane dispersing liquid.
(4) it is evaporated under reduced pressure
By aqueous polyurethane dispersing liquid temperature be 60 DEG C, vacuum be 0.095MPa under conditions of be evaporated under reduced pressure,
The acetone in dispersion liquid is removed, that is, obtains pH=7.5-9, aqueous polyurethane dispersing liquid of the solid content 30%.
(5) compound and thicken
Resulting aqueous polyurethane dispersing liquid is slowly added into levelling agent 440, profit successively under conditions of normal temperature, stirring
Humectant 245, thickener hydroxyethyl cellulose, mixing time are 35 minutes, obtain the viscous of waterborne polyurethane for synthetic leather dispersion liquid
Mixture.
The good effect of embodiment：
1. the emulsion and glue film performance of each embodiment and the testing result of comparative example are shown in Table 1
The emulsion and glue film performance testing result of 1 each embodiment of table and comparative example
2. the application test of each embodiment and comparative example on synthetic leather.
Each embodiment and comparative example are moved in film as adhesive in different production bars in synthetic leather release liners dry method
Comparison study under part, it the results are shown in Table 2, table 3, table 4.
2 each embodiment of table and comparative example are moved in film in synthetic leather release liners dry method is used as adhesive application result pair
Than
3 each embodiment of table and comparative example are moved in film in synthetic leather release liners dry method is used as adhesive application result pair
Than
4 each embodiment of table and comparative example are moved in film in synthetic leather release liners dry method is used as adhesive application result pair
Than
Above-mentioned result of the test explanation, use for synthetic leather adhesive prepared by the present invention have good tack, peel strength,
Rate of drying is fast, excellent water resistance, is provided simultaneously with excellent levelability and spreadability.Meet the use of use for synthetic leather adhesive
Condition.
Embodiment above is to illustrate embodiment disclosed by the invention, can not be interpreted as the limit to the present invention
System.In addition, in various modifications and invention listed herein method, composition change, do not departing from the scope of the present invention
Be obvious for those skilled in the art on the premise of spirit.Although a variety of specific of the present invention has been combined
Preferred embodiment has carried out specific description to the present invention, it is to be understood that, the present invention should not be limited only to these specific embodiments.
In fact, various, obvious modification should all include to obtain invention for those skilled in the art as described above
Within the scope of the invention.
Claims (9)
1. a kind of synthetic leather adhesive, it is characterised in that be made up of the raw material of following mass fraction：Polyalcohol 104.46-120.3
Part, diisocyanate 23.1-35.64 parts, catalyst 0.0045-0.072 parts, carboxylic acid type chain extender 5.7-7.2 parts, oh type are small
It is molecule chain extender 0.6-1.80 parts, internal crosslinker 0.3-0.9 parts, epoxy resin 4.8-9 parts, nertralizer 3.78-5.06 parts, organic
Solvent 40-55 parts, antioxidant 0.1-1.2 parts, amine chainextender 1.5-2.7 parts, wetting agent 1.5-2.5 parts, levelling agent 1.5-2.5
Part, thickener 4-5 parts；
The polyalcohol includes PTMG 2000, PTMG 3000 and PCDL
1000, its mass ratio is 6-10:1:0.1-1.
2. synthetic leather adhesive as claimed in claim 1, it is characterised in that the diisocyanate is isophorone diisocyanate
One or both of ester, hexamethylene diisocyanate；
The one kind of the catalyst in stannous octoate, dibutyl tin laurate, bismuth sulfonic group catalyst；
The one kind of the carboxylic acid type chain extender in dihydromethyl propionic acid, dimethylolpropionic acid；
The one kind of the oh type small molecule chain extender in 1,6-HD, 1,4 cyclohexane dimethanol, neopentyl glycol；
The internal crosslinker is trimethylolpropane；
The one kind of the nertralizer in triethylamine, DMAE, dimethylamino propyl alcohol；
The one kind of the antioxidant in antioxidant 1010, antioxidant 1024, antioxidant 2246；
The one kind of the organic solvent in acetone, DMAC, NMP, DMF；
The amine chainextender is one kind in hexamethylene diamine, IPD, ethylenediamine；
The one kind of the thickener in hydroxyethyl cellulose, association type aqueous polyurethane.
3. synthetic leather adhesive as claimed in claim 2, it is characterised in that the antioxidant is antioxidant 1010；It is described to have
Solvent is acetone.
4. the synthetic leather adhesive as described in claim any one of 1-2, it is characterised in that its preparation method includes：
(1) polyalcohol and isocyanates are added in reactor, carries out first step pre-polymerization, then add catalyst, carboxylic acid type expands
Chain agent and internal crosslinker, second step pre-polymerization is carried out, epoxy resin is then added, reacts to isocyanate groups (- NCO) and no longer become
Antioxidant is added during change, obtains base polyurethane prepolymer for use as；
(2) viscosity of the organic solvent regulation base polyurethane prepolymer for use as is added to 70-80mPas, and is added in nertralizer progress
With, stir, obtain neutralize mixture；Add water and amine chainextender, disperse, remove organic solvent, obtain dispersion liquid；
(3) levelling agent, wetting agent, thickener are added into the dispersion liquid to be compounded and thickened, produce the synthetic leather and glue
Mixture.
5. the preparation method of synthetic leather adhesive as claimed in claim 1, it is characterised in that including：
(1) polyalcohol and isocyanates are added in reactor, carries out first step pre-polymerization, then add catalyst, carboxylic acid type expands
Chain agent and internal crosslinker, second step pre-polymerization is carried out, epoxy resin is then added, reacts to isocyanate groups (- NCO) and no longer become
Antioxidant is added during change, obtains base polyurethane prepolymer for use as；
(2) viscosity of the organic solvent regulation base polyurethane prepolymer for use as is added to 70-80mPas, and is added in nertralizer progress
With, stir, obtain neutralize mixture；Add water and amine chainextender, disperse, remove organic solvent, obtain dispersion liquid；
(3) levelling agent, wetting agent, thickener are added into the dispersion liquid to be compounded and thickened, produce the synthetic leather and glue
Mixture.
6. the preparation method of synthetic leather adhesive as claimed in claim 5, it is characterised in that the reaction temperature of first step pre-polymerization is
80-95℃；Reaction time is 1-3 hours；After first step pre-polymerization, 80-55 DEG C is cooled to；The reaction temperature of second step pre-polymerization is
85-55℃；Reaction time is 2-4 hours.
7. the preparation method of synthetic leather adhesive as claimed in claim 5, it is characterised in that the reaction temperature added after epoxy resin
Spend for 64-60 DEG C, the reaction time is 0.5-1 hours.
8. the preparation method of synthetic leather adhesive as claimed in claim 5, it is characterised in that in step (2), add organic solvent
Before, the temperature of the base polyurethane prepolymer for use as is cooled to 60-55 DEG C；In step (2), stir speed (S.S.) when disperseing is 1000-
2000 revs/min, mixing time 20-30 minutes.
9. the preparation method of synthetic leather adhesive as claimed in claim 5, it is characterised in that in step (3), compound and thicken into
Row stirring, mixing speed are 100-200 revs/min, and mixing time is 30-50 minutes.
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