CN107268290A - A kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type - Google Patents
A kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type Download PDFInfo
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- CN107268290A CN107268290A CN201710361317.1A CN201710361317A CN107268290A CN 107268290 A CN107268290 A CN 107268290A CN 201710361317 A CN201710361317 A CN 201710361317A CN 107268290 A CN107268290 A CN 107268290A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0009—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using knitted fabrics
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
- D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- D06N2209/00—Properties of the materials
- D06N2209/12—Permeability or impermeability properties
- D06N2209/126—Permeability to liquids, absorption
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- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/26—Vehicles, transportation
- D06N2211/266—Ships
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Abstract
A kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type, the component A containing hydroxyl, the B component containing NCO are added in reactor, and the lower reaction of stirring obtains foamed slurry；Using synthetic leather dry process production line, by foamed slurry blade coating in release liners, coating is formed, then by make-up machine, coating is fitted with base fabric by the way of gap is fitted, enters back into after baking oven curing, obtains the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type.The present invention is using dual foaming technique, polyurethane in-situ polymerization waterproof technique, the asynchronous catalysis technique of thermal sensitivity catalyst and the hilted broadsword constant temperature heating doctor blade technique production organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type, production technology is environmentally friendly, succinct stabilization, good product quality, contact angle of the water droplet on synthetic leather surface is up to 107 degree, static water-impervious can reach 15 days, can be used as high-grade feature yacht seat skin material.
Description
Technical field
The present invention relates to Synthetic Leather technical field, more particularly to a kind of organic-silicon-modified solvent-free poly- ammonia of water proof type
The production method of Lipase absobed leather.
Background technology
Synthetic Leather is the institutional framework and performance for simulating natural leather, and can be used as natural leather substitute
Composite.Lamina reticularis is generally simulated with non-woven fabrics, with microvoid polyurethane coating simulation grain layer, resulting synthetic leather
Positive and negative are all quite similar with leather, and with certain gas permeability, than common artificial leather closer to natural leather, use extensively
In making footwear, boots, case and bag and ball etc..
From the point of view of yield, the artificial conjunction of China's plastics, synthetic leather yield rise to 2015 years from 184.82 ten thousand tons of 2009
343.8 ten thousand tons, compound growth rate is up to 10.9%.But recent year environmental requirement is stricter, the production of heavily contaminated synthetic leather
Industry development is restricted, and industry competition is increasingly fierce.
At present, the production of Synthetic Leather mainly uses solvent type production system, its typical process flow:It is non-woven
Cloth → solvent borne polyurethane wet coagulation coating (bottom) → washing → drying → solvent borne polyurethane dry method shifting membrane coat (on
Layer).The Synthetic Leather produced using this production method, has following great technical problem：First, using solvent
Type polyurethane wet coagulation coating makees bottom, wet coagulation coating be by solvent borne polyurethane (PU) slurry, using doctor knife coater or
Coating roller is coated on the surface of non-woven cloth, subsequently into " H2O-DMF (dimethylformamide) " coagulating baths, make PU solidify and shape
Into the film with microcellular structure.DMF is employed in this technique and makees solvent, process can cause DMF solvent contamination.Its
Two, water can not completely replace the DMF in polyurethane, can cause the DMF residue problems of product, ultimately cause product safety and ask
Topic.And this product safety problem, can be in numerous technology barriers and trade barrier, limitation product enters up-market.Its
Three, membrane coat is moved using solvent borne polyurethane dry method and makees top layer, this technique is, by solvent borne polyurethane slurry, to utilize doctor knife coater
The surface of release liners is coated on, is then fitted with moving the non-woven cloth of gel coating with wet method, peels off, finally gives after drying
Synthetic Leather.Because this technique uses solvent-borne type system, containing substantial amounts of toxic organic solvents, such as TOL (toluene),
MEK (MEK) and THF (tetrahydrofuran) etc..These organic solvent highly volatiles in process of production, severe contamination environment, and
And the healthy of site operation personnel is threatened.
According to the solvent-borne type production system of above-mentioned Synthetic Leather, production process exist serious MDF, TOL, MEK,
The problem of environmental pollution of THF equal solvents, is a non-clean production process, there is larger harm to human body.Resulting is poly-
The residual for easily DMF occur in urethane synthetic leather causes product safety problem.So, develop process for cleanly preparing, production environment
The Synthetic Leather of friendly is the trend of a certainty.And the environmental synthetic leather of development function type is high-end synthetic leather product
The inexorable trend of exploitation.Synthetic leather particularly for high-grade yacht seat covering material is, it is necessary to which surface water repellency is expired well
The requirement of sufficient quick-drying, it is also desirable to the good requirement for putting infiltration sexual satisfaction use environment.
The content of the invention
It is an object of the invention to provide a kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type.
To achieve the above object, the present invention is just with following technical scheme：
A kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type, comprises the following steps：
(1) component A containing hydroxyl, the B component containing NCO are added in reactor, reacted under stirring
To foamed slurry；
Wherein, the component A is made by the following method：In terms of mass fraction, by PTMG 2,000 40
~55 parts, 2,000 20~30 parts of polypropylene glycol, 10~15 parts of hydroxy silicon oil, 0.3~0.5 part of sorbester p17,1,8- diazas
Two rings [5.4.0] 11,0.01~0.1 part of carbon -7- alkene and the carbon -7- zinecarboxylic acid salt of 1,8- diazabicylos [5.4.0] 11
0.01~0.1 part is heated to be well mixed after 25~40 DEG C, obtains component A；
(2) synthetic leather dry process production line is used, by foamed slurry blade coating in release liners, coating is formed, then pass through laminating
Machine, fits coating with base fabric by the way of gap is fitted, and enters back into after baking oven curing, obtains the organic-silicon-modified nothing of water proof type
Solvent polyurethane synthetic leather.
Further improve of the invention is that the rotating speed of stirring is 80~100rpm in step (1)；The temperature of reaction is 35
~50 DEG C, the time is 4~8min.
Further improve of the invention is that the ratio of component A and B component is determined by R values in step (1), and R values are B groups
The ratio between-OH molal quantity in-NCO and component A in point, and R values are 1.1~1.6.
Further improve of the invention is that B component is liquefaction diphenylmethylene diisocyanate in step (1).
Further improve of the invention is that blade coating detailed process is in step (2)：The scraper and hopper of coating machine have
Heater, makes foamed slurry be scratched under conditions of being maintained at 35~40 DEG C in release liners.
Further improve of the invention is that the thickness of step (2) floating coat is 0.1~0.8mm.
Further improve of the invention is that laminating gap is release liners, coating and base fabric three's gross thickness in step (2)
70~75%.
Further improve of the invention is that base fabric is weaving cloth, looped fabric, non-woven fabrics or superfine fibre in step (2)
Synthetic leather base cloth.
Of the invention further improve is that the temperature of curing is 115~130 DEG C in step (2), the time is 10~
15min。
Compared with prior art, the device have the advantages that：
First, the present invention uses dual foaming technique, i.e., during slurry preparation, stirring and breast by physical mechanical
Under the emulsification of agent, the carbon dioxide thing gas that initial reaction is produced is uniformly dispersed in slurry, foam is obtained thin
Greasy foamed slurry, the dual foaming technique feature being combined with reason mechanical foaming and chemical blowing, whole foaming process can
Control property is good, and can adjust expansion ratio by the inlet of air during mechanical agitation；
Second, using polyurethane in-situ polymerization waterproof technique, having used the hydroxy silicon oil with reactivity worth, having gathered in the original location
Organic-silicon-modified to polyurethane progress in conjunction, final products have good water resistance and square permeability performance, in production process
In without using any solvent, it, also without dissolvent residual, is a kind of environmentally friendly synthesis leather to be in a kind of environmentally friendly production technology, product
Product；
Third, using the asynchronous catalysis technique of thermal sensitivity catalyst, i.e., using DUB and DBU formates as combination catalyst,
This catalyst combination has good thermal sensitivity, i.e., catalytic activity is very low at a lower temperature, and is catalyzed at relatively high temperatures
Activity is greatly improved, so as to realize slow reaction and the fast reaction in later stage at reaction system initial stage, the slow reaction at initial stage makes
Obtain material initial viscosity smaller, the smooth of doctor blade process is ensure that, when the fast reaction in later stage can add the curing of shortening later stage
Between, improve production efficiency；
Fourth, using the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type produced by the invention, water droplet is in synthetic leather
The contact angle on surface is up to 107 degree, and static water-impervious can reach 15 days, can be used as high-grade feature yacht seat covering material
Material, the good water repellency in synthetic leather surface disclosure satisfy that the requirement of seat surface quick-drying, and it is special that good infiltration meets seat
Different use environment；
Fifth, the production method that the present invention is used is in process of production without using any solvent, it is a kind of environmentally friendly production
It is a kind of environmentally friendly synthesis leather product also without dissolvent residual in technology, product.
Further, when being scratched in the present invention, the scraper and hopper of coating machine have heater, keep foamed slurry
Scratched under conditions of 35~40 DEG C in release liners.Using hilted broadsword constant temperature heating doctor blade technique, material viscosity is advantageously reduced, it is real
The blade coating of existing continuous-stable, and whole production process only needs to once be coated with, can effectively improve production stability and
Production efficiency.
Embodiment
Below by embodiment, the present invention is described in further detail, but the present invention is not only limited in these
Example.
A kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type, comprises the following steps：
(1) component A, the B component containing NCO (- NCO) containing hydroxyl (- OH) are loaded according to a certain percentage
Reactor, is sufficiently mixed 4~8min of reaction under conditions of 35~50 DEG C, rotating speed are 80~100rpm, obtains foam exquisiteness
Foamed slurry.
The component A is the mixture of a variety of dihydric alcohols and various auxiliary agents, is made by the following method：With mass fraction
Meter, by PTMG 2000, (abbreviation PTMEG, relative molecular mass is 2000) 40~55 parts, polypropylene glycol
2000 20~30 parts of (abbreviation PPG, relative molecular mass 2000), 10~15 parts of hydroxy silicon oil (relative molecular mass 6000), department
0.3~0.5 part of disk 80 (also known as span-80, as emulsifying agent, main component is sorbitan monooleate), 1,8- diazas
0.01~0.1 part of two rings [5.4.0], 11 carbon -7- alkene (abbreviation DBU) and the carbon -7- of 1,8- diazabicylos [5.4.0] 11
0.01~0.1 part of zinecarboxylic acid salt (abbreviation DBU formates) is heated to be thoroughly mixed after 25~40 DEG C uniformly, you can obtain A
Component.
The B component is liquefaction diphenylmethylene diisocyanate (abbreviation liquefied mdi).
The mixed proportion of the component A and B component is by R values (the ratio between-OH molal quantity in-NCO and component A in B component)
Determine, R values are 1.1~1.6 in the present invention.
(2) synthetic leather dry process production line is used, regulation speed is in 5~8m/min, by foamed slurry blade coating in release liners,
The coating that thickness is 0.1~0.8mm is formed, by make-up machine, coating is fitted with base fabric by the way of gap is fitted, then enters
Enter baking oven, 10~15min is cured under conditions of 115~130 DEG C, cooling is peeled off, you can obtain the organic-silicon-modified nothing of water proof type
Solvent polyurethane synthetic leather.
There is heater using the scraper and hopper of constant temperature heating doctor blade technique, i.e. coating machine during the blade coating, make foaming
Slurry is scratched in release liners under conditions of being maintained at 35~40 DEG C.
The laminating gap is the 70~75% of release liners, coating and base fabric three's gross thickness.
The base fabric can be weaving cloth, looped fabric, non-woven fabrics or superfine fiber synthetic leather base cloth.
Embodiment 1
A kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type, comprises the following steps：
(1) component A, the B component containing NCO (- NCO) containing hydroxyl (- OH) are added according to a certain percentage
Into reactor, reaction 8min is sufficiently mixed under conditions of 35 DEG C, rotating speed are 80rpm, the fine and smooth foamed slurry of foam is obtained.
The component A is the mixture of a variety of dihydric alcohols and various auxiliary agents, is made by the following method：With mass fraction
Meter, by PTMG 2000, (abbreviation PTMEG, relative molecular mass is 2000) 40 parts, (letter of polypropylene glycol 2000
Claim PPG, relative molecular mass 2000) 20 parts, 15 parts of hydroxy silicon oil (relative molecular mass 6000), sorbester p17 (also known as span-
80, as emulsifying agent, main component is sorbitan monooleate) 0.3 part, the carbon -7- of 1,8- diazabicylos [5.4.0] 11
0.01 part of alkene (abbreviation DBU) and the carbon -7- zinecarboxylic acids salt (abbreviation DBU formates) of 1,8- diazabicylos [5.4.0] 11
0.01 part is heated to be thoroughly mixed after 25 DEG C uniformly, you can obtain component A.
The B component is liquefaction diphenylmethylene diisocyanate (abbreviation liquefied mdi).
The mixed proportion of the component A and B component is by R values (the ratio between-OH molal quantity in-NCO and component A in B component)
Determine, R values are 1.1 in the present invention.
(2) synthetic leather dry process production line is used, regulation speed is 5m/min, by foamed slurry blade coating in release liners, shape
Into the coating that thickness is 0.1mm, by make-up machine, coating is fitted with base fabric by the way of gap is fitted, baking oven is entered back into,
10min is cured under conditions of 130 DEG C, cooling is peeled off, you can obtain the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type.
There is heater using the scraper and hopper of constant temperature heating doctor blade technique, i.e. coating machine during the blade coating, make foaming
Slurry is scratched in release liners under conditions of being maintained at 35 DEG C.
The laminating gap is the 70% of release liners, coating and base fabric three's gross thickness.
The base fabric is weaving cloth.
Embodiment 2
A kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type, comprises the following steps：
(1) component A, the B component containing NCO (- NCO) containing hydroxyl (- OH) are added according to a certain percentage
Into reactor, reaction 68min is sufficiently mixed under conditions of 40 DEG C, rotating speed are 100rpm, the fine and smooth foaming slurry of foam is obtained
Material.
The component A is the mixture of a variety of dihydric alcohols and various auxiliary agents, is made by the following method：With mass fraction
Meter, by PTMG 2000, (abbreviation PTMEG, relative molecular mass is 2000) 50 parts, (letter of polypropylene glycol 2000
Claim PPG, relative molecular mass 2000) 30 parts, 10 parts of hydroxy silicon oil (relative molecular mass 6000), sorbester p17 (also known as span-
80, as emulsifying agent, main component is sorbitan monooleate) 0.4 part, the carbon -7- of 1,8- diazabicylos [5.4.0] 11
0.1 part of alkene (abbreviation DBU) and the carbon -7- zinecarboxylic acids salt (abbreviation DBU formates) 0.1 of 1,8- diazabicylos [5.4.0] 11
Part is heated to be thoroughly mixed after 30 DEG C uniformly, you can obtain component A.
The B component is liquefaction diphenylmethylene diisocyanate (abbreviation liquefied mdi).
The mixed proportion of the component A and B component is by R values (the ratio between-OH molal quantity in-NCO and component A in B component)
Determine, R values are 1.2 in the present invention.
(2) synthetic leather dry process production line is used, regulation speed is 8m/min, by foamed slurry blade coating in release liners, shape
Into the coating that thickness is 0.3mm, by make-up machine, coating is fitted with base fabric by the way of gap is fitted, baking oven is entered back into,
13min is cured under conditions of 120 DEG C, cooling is peeled off, you can obtain the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type.
There is heater using the scraper and hopper of constant temperature heating doctor blade technique, i.e. coating machine during the blade coating, make foaming
Slurry is scratched in release liners under conditions of being maintained at 40 DEG C.
The laminating gap is the 75% of release liners, coating and base fabric three's gross thickness.
The base fabric is looped fabric.
Implement 3
A kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type, comprises the following steps：
(1) component A, the B component containing NCO (- NCO) containing hydroxyl (- OH) are added according to a certain percentage
Into reactor, reaction 5min is sufficiently mixed under conditions of 45 DEG C, rotating speed are 90rpm, the fine and smooth foamed slurry of foam is obtained.
The component A is the mixture of a variety of dihydric alcohols and various auxiliary agents, is made by the following method：With mass fraction
Meter, by PTMG 2000, (abbreviation PTMEG, relative molecular mass is 2000) 55 parts, (letter of polypropylene glycol 2000
Claim PPG, relative molecular mass 2000) 25 parts, 11 parts of hydroxy silicon oil (relative molecular mass 6000), sorbester p17 (also known as span-
80, as emulsifying agent, main component is sorbitan monooleate) 0.5 part, the carbon -7- of 1,8- diazabicylos [5.4.0] 11
0.03 part of alkene (abbreviation DBU) and the carbon -7- zinecarboxylic acids salt (abbreviation DBU formates) of 1,8- diazabicylos [5.4.0] 11
0.05 part is heated to be thoroughly mixed after 35 DEG C uniformly, you can obtain component A.
The B component is liquefaction diphenylmethylene diisocyanate (abbreviation liquefied mdi).
The mixed proportion of the component A and B component is by R values (the ratio between-OH molal quantity in-NCO and component A in B component)
Determine, R values are 1.3 in the present invention.
(2) synthetic leather dry process production line is used, regulation speed is 6m/min, by foamed slurry blade coating in release liners, shape
Into the coating that thickness is 0.5mm, by make-up machine, coating is fitted with base fabric by the way of gap is fitted, baking oven is entered back into,
15min is cured under conditions of 115 DEG C, cooling is peeled off, you can obtain the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type.
There is heater using the scraper and hopper of constant temperature heating doctor blade technique, i.e. coating machine during the blade coating, make foaming
Slurry is scratched in release liners under conditions of being maintained at 35 DEG C.
The laminating gap is the 72% of release liners, coating and base fabric three's gross thickness.
The base fabric is non-woven fabrics.
Embodiment 4
A kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type, comprises the following steps：
(1) component A, the B component containing NCO (- NCO) containing hydroxyl (- OH) are added according to a certain percentage
Into reactor, reaction 4min is sufficiently mixed under conditions of 50 DEG C, rotating speed are 85rpm, the fine and smooth foamed slurry of foam is obtained.
The component A is the mixture of a variety of dihydric alcohols and various auxiliary agents, is made by the following method：With mass fraction
Meter, by PTMG 2000, (abbreviation PTMEG, relative molecular mass is 2000) 45 parts, (letter of polypropylene glycol 2000
Claim PPG, relative molecular mass 2000) 27 parts, 12 parts of hydroxy silicon oil (relative molecular mass 6000), sorbester p17 (also known as span-
80, as emulsifying agent, main component is sorbitan monooleate) 0.3 part, the carbon -7- of 1,8- diazabicylos [5.4.0] 11
0.06 part of alkene (abbreviation DBU) and the carbon -7- zinecarboxylic acids salt (abbreviation DBU formates) 0.3 of 1,8- diazabicylos [5.4.0] 11
Part is heated to be thoroughly mixed after 40 DEG C uniformly, you can obtain component A.
The B component is liquefaction diphenylmethylene diisocyanate (abbreviation liquefied mdi).
The mixed proportion of the component A and B component is by R values (the ratio between-OH molal quantity in-NCO and component A in B component)
Determine, R values are 1.5 in the present invention.
(2) synthetic leather dry process production line is used, regulation speed is 7m/min, by foamed slurry blade coating in release liners, shape
Into the coating that thickness is 0.6mm, by make-up machine, coating is fitted with base fabric by the way of gap is fitted, baking oven is entered back into,
12min is cured under conditions of 125 DEG C, cooling is peeled off, you can obtain the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type.
There is heater using the scraper and hopper of constant temperature heating doctor blade technique, i.e. coating machine during the blade coating, make foaming
Slurry is scratched in release liners under conditions of being maintained at 37 DEG C.
The laminating gap is the 73% of release liners, coating and base fabric three's gross thickness.
The base fabric is superfine fiber synthetic leather base cloth.
Embodiment 5
A kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type, comprises the following steps：
(1) component A, the B component containing NCO (- NCO) containing hydroxyl (- OH) are added according to a certain percentage
Into reactor, reaction 7min is sufficiently mixed under conditions of 35 DEG C, rotating speed are 95rpm, the fine and smooth foamed slurry of foam is obtained.
The component A is the mixture of a variety of dihydric alcohols and various auxiliary agents, is made by the following method：With mass fraction
Meter, by PTMG 2000, (abbreviation PTMEG, relative molecular mass is 2000) 40 parts, (letter of polypropylene glycol 2000
Claim PPG, relative molecular mass 2000) 28 parts, 13 parts of hydroxy silicon oil (relative molecular mass 6000), sorbester p17 (also known as span-
80, as emulsifying agent, main component is sorbitan monooleate) 0.4 part, the carbon -7- of 1,8- diazabicylos [5.4.0] 11
0.08 part of alkene (abbreviation DBU) and the carbon -7- zinecarboxylic acids salt (abbreviation DBU formates) 0.5 of 1,8- diazabicylos [5.4.0] 11
Part is heated to be thoroughly mixed after 40 DEG C uniformly, you can obtain component A.
The B component is liquefaction diphenylmethylene diisocyanate (abbreviation liquefied mdi).
The mixed proportion of the component A and B component is by R values (the ratio between-OH molal quantity in-NCO and component A in B component)
Determine, R values are 1.6 in the present invention.
(2) synthetic leather dry process production line is used, regulation speed is 5~8m/min, by foamed slurry blade coating in release liners,
The coating that thickness is 0.8mm is formed, by make-up machine, coating is fitted with base fabric by the way of gap is fitted, baking is entered back into
Case, cures 11min under conditions of 130 DEG C, and cooling is peeled off, you can obtain the organic-silicon-modified no-solvent polyurethane synthesis of water proof type
Leather.
There is heater using the scraper and hopper of constant temperature heating doctor blade technique, i.e. coating machine during the blade coating, make foaming
Slurry is scratched in release liners under conditions of being maintained at 38 DEG C.
The laminating gap is the 78% of release liners, coating and base fabric three's gross thickness.
The base fabric is weaving cloth.
The present invention is using dual foaming technique, polyurethane in-situ polymerization waterproof technique, the asynchronous catalysis skill of thermal sensitivity catalyst
Art and the hilted broadsword constant temperature heating doctor blade technique production organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type, production technology environmental protection, letter
Clean stabilization, good product quality, contact angle of the water droplet on synthetic leather surface is up to 107 degree, and static water-impervious can reach 15 days, can be with
As high-grade feature yacht seat skin material, the good water repellency in synthetic leather surface disclosure satisfy that seat surface quick-drying
It is required that, good infiltration meets the special use environment of seat.
The production method that the present invention is used, in process of production without using any solvent, is a kind of environmentally friendly production technology,
It is a kind of environmentally friendly synthesis leather product also without dissolvent residual in product.
Claims (9)
1. a kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type, it is characterised in that including following step
Suddenly：
(1) component A containing hydroxyl, the B component containing NCO are added in reactor, the lower reaction of stirring is sent out
Steep slurry；
Wherein, the component A is made by the following method：In terms of mass fraction, by PTMG 2,000 40~55
Part, 2,000 20~30 parts of polypropylene glycol, 10~15 parts of hydroxy silicon oil, 0.3~0.5 part of sorbester p17,1,8- diazabicylos
[5.4.0] 11 0.01~0.1 part of carbon -7- alkene and the carbon -7- zinecarboxylic acids salt 0.01 of 1,8- diazabicylos [5.4.0] 11~
0.1 part is heated to be well mixed after 25~40 DEG C, obtains component A；
(2) synthetic leather dry process production line is used, by foamed slurry blade coating in release liners, coating is formed, then by make-up machine, adopt
The mode fitted with gap fits coating with base fabric, enters back into after baking oven curing, obtains water proof type organic-silicon-modified solvent-free
Synthetic Leather.
2. a kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type according to claim 1, its
It is characterised by, the rotating speed of stirring is 80~100rpm in step (1)；The temperature of reaction is 35~50 DEG C, and the time is 4~8min.
3. a kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type according to claim 1, its
It is characterised by, the ratio of component A and B component is determined by R values in step (1), R values are-NCO and-OH in component A in B component
The ratio between molal quantity, and R values are 1.1~1.6.
4. a kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type according to claim 1, its
It is characterised by, B component is liquefaction diphenylmethylene diisocyanate in step (1).
5. a kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type according to claim 1, its
It is characterised by, blade coating detailed process is in step (2)：The scraper and hopper of coating machine have heater, protect foamed slurry
Hold and scratched under conditions of 35~40 DEG C in release liners.
6. a kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type according to claim 1, its
It is characterised by, the thickness of step (2) floating coat is 0.1~0.8mm.
7. a kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type according to claim 1, its
It is characterised by, laminating gap is the 70~75% of release liners, coating and base fabric three's gross thickness in step (2).
8. a kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type according to claim 1, its
It is characterised by, base fabric is weaving cloth, looped fabric, non-woven fabrics or superfine fiber synthetic leather base cloth in step (2).
9. a kind of production method of the organic-silicon-modified no-solvent polyurethane synthetic leather of water proof type according to claim 1, its
It is characterised by, the temperature of curing is 115~130 DEG C in step (2), the time is 10~15min.
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| CN108610467A (en) * | 2018-04-11 | 2018-10-02 | 高鼎精细化工(昆山)有限公司 | One-way type solvent-free polyurethane resin, the dermatine containing the resin and its manufacturing method |
| CN109575213A (en) * | 2018-12-07 | 2019-04-05 | 福建华普树脂有限公司 | A kind of dry method foaming polyurethane resin and preparation method thereof |
| CN110628209A (en) * | 2019-10-31 | 2019-12-31 | 杭州崇耀科技发展有限公司 | Solvent-free polyurethane/silica gel blend, solvent-free polyurethane synthetic leather and preparation method thereof |
| CN113818256A (en) * | 2021-09-26 | 2021-12-21 | 南通中豪超纤制品有限公司 | Preparation process of blending modified easy-to-clean leather |
| CN114164682A (en) * | 2021-12-14 | 2022-03-11 | 上海汇得科技股份有限公司 | Preparation method of solvent-free polyurethane synthetic leather and product thereof |
| WO2024052231A1 (en) * | 2022-09-08 | 2024-03-14 | Basf Se | Solvent-free base and method for producing the same |
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| CN113818256B (en) * | 2021-09-26 | 2024-05-31 | 南通中豪超纤制品有限公司 | Process for preparing blending modified easy-to-decontaminate leather |
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| WO2024052231A1 (en) * | 2022-09-08 | 2024-03-14 | Basf Se | Solvent-free base and method for producing the same |
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