CN108047414A - Solvent-free leather polyurethane resin and preparation method and application - Google Patents
Solvent-free leather polyurethane resin and preparation method and application Download PDFInfo
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- CN108047414A CN108047414A CN201711500645.1A CN201711500645A CN108047414A CN 108047414 A CN108047414 A CN 108047414A CN 201711500645 A CN201711500645 A CN 201711500645A CN 108047414 A CN108047414 A CN 108047414A
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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
- D06N3/146—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 characterised by the macromolecular diols used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- 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
- D06N3/0086—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
-
- 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
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Abstract
Polyurethane resin the invention discloses a kind of uninanned platform leather and its preparation method and application, the polyurethane resin of the uninanned platform leather include Resin A component and resin B component；The Resin A component contains the water that the polyester ether polylol polyisocyanates performed polymer that weight percent is 20%~45% and weight percent are 0.3%~2.0%, and the resin B component contains the diisocyanate that weight percent is 20%~60%；The mass ratio of the Resin A component and resin B component is 3: 1~1: 3.The polyurethane resin of uninanned platform leather of the present invention need to only scratch a knife solventfree resin when producing synthetic leather, you can possess surface layer, adhesive layer and foaming layer structure, technical process is simple, and physical mechanical property is excellent.
Description
Technical field
The present invention relates to a kind of no-solvent polyurethane leather resin and preparation method and application
Background technology
Solvent-free polyurethane resin generally comprises two or more components, in synthetic leather production process, two or more
Resin Composition carries out chain extension, foaming and the reaction of gel directly on base material.
No-solvent polyurethane synthetic leather production technology is：
(1) scratch and dry surface layer：Two or more surface layer resin components are respectively delivered to mixing head by a certain percentage,
It is uniformly mixed, is injected at immediately in release paper, by scratching after mode coating film forming into drying tunnel, between polyurethane resin component
Fast reaction, the molecular weight of polymer sharply increase, and quickly generate the Synthetic Leather surface layer with characteristic group structure；
(2) foaming layer is scratched：Two or more foaming layer resin Compositions are mixed in a certain ratio by same step (1) to be coated on
Half-dried foaming layer into drying tunnel after film forming, is bonded base fabric by surface layer；
(3) dry, cure, winding.
The solvent-free participation of no-solvent polyurethane synthetic leather production process without evaporating solvent or moisture, does not generate a large amount of yet
Organic liquid waste or waste water, energy conservation and environmental protection, production efficiency is high, at low cost, is the important directions of synthetic leather industry Transformation Development.
Chinese patent, Application No. 201610798749.4,201610645186.5,201610464914.2,
201610464885.X、201610464957.0、201511008510.4、201510375189.7、201410524279.3、
201410366764.2,201410318120.6,201410318118.9,200810168376.8 individually disclose solvent-free face
Layer leather or leather resin composition and preparation method.
M material are polyester polyol performed polymer or polyethers disclosed in the Chinese patent application of Application No. 201110254065.5
The compositions such as polyalcohol performed polymer and auxiliary material, polynary amines catalyst, N material are polymeric polyisocyanate.
The Chinese patent of ZL201210560235.7 discloses solvent-free Multi-component Polyurethane synthetic leather preparation method, and wherein polyalcohol is
One or more of polyetherdiol, polyether triol, heats liquefied polyester-diol or base polyurethane prepolymer for use as with hydroxyl are mixed
Close object.The preparation method is one-step technology, and the synthetic leather the physical property of product of production is poor, and its casting machine needs to have several
Head tank, production operation are poor.
It is solvent-free poly- that 201610798749.4 Chinese patent application of Application No. discloses sports shoe leather carbon fiber modifying
Urethane surface layer resin and preparation method and application.Wherein component A is polynary by aliphatic isocyanates, oligomeric diols, organosilicon
Alcohol, small molecule dihydric alcohol, small molecule trihydroxylic alcohol, catalyst, light heat stabilizer, levelling agent, antifoaming agent, deicer and carbon fiber
It forms in specific proportions.B component by aliphatic diisocyanate, aliphatic triisocyanate, PolyTHF dihydric alcohol, small point
Sub- dihydric alcohol, small molecule trihydroxylic alcohol, light heat stabilizer form in specific proportions.The patent application adds in aliphatic in component A
Isocyanates calculates the isocyanates in component A in its ratio and is formed with small molecule dihydric alcohol, small molecule trihydroxylic alcohol preferential reaction
Hydroxy-end capped small molecule performed polymer solves the consistency problem between oligomer polyol and small molecule polyol, but pairing
Material properties affect into leather goods is very limited, it is necessary to improve the physical property of the solvent-free leather of aliphatic by addition carbon fibre material.
The content of the invention
The object of the present invention is to provide the polyurethane resin and its preparation method of a kind of One-step production uninanned platform leather, with generation
For traditional technique be first wet method base and be bonded dry method surface layer again.
The solvent-free leather polyurethane resin of the present invention, includes Resin A component and resin B component；The Resin A component contains
Polyester ether polylol-polyisocyanates performed polymer and the weight percent 0.3%~2.0% that weight percent is 20%~45%
Water, the resin B component contain weight percent be 20%~60% diisocyanate.
The quality of Resin A component and resin B component is 3: 1~1: 3.
The Resin A component is made of the component of following mass percentage：
The resin B component is made of the component of following mass percentage：
Diisocyanate 20%~60%；
Polyvalent alcohol 30%~80%；
Phosphoric acid 0~1%；
Preferably,
The Resin A component is made of the component of following mass percentage：
The resin B component is made of the component of following mass percentage：
Diisocyanate 20%~41%；
Polyvalent alcohol 58%~80%；
Phosphoric acid 0~1%；
NCO content is 4%~35% in the resin B component.
The polyester ether polylol polyisocyanates performed polymers number-average molecular weight is 10000~100000, degree of functionality 2
~4：
Preferably, polyester ether polylol-polyisocyanates performed polymer is the pre-polymerization of polyester ether polylol and polyisocyanates
Object, wherein polyisocyanates are toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, naphthalene diisocyanate, different to benzene two
Cyanate, triphenylmethane triisocyanate, dimethyl triphenyl methane tetraisocyanate, isophorone diisocyanate, two
Diphenylmethane diisocyanate, hexamethylene diisocyanate, Isosorbide-5-Nitrae-cyclohexane diisocyanate, cyclohexanedimethyleterephthalate two
It is one or more of in isocyanates, trimethyl -1,6- hexamethylene diisocyanate, Methylcyclohexyl diisocyanate：It is poly-
It is prepared by the method that CN105504259A patent literatures can be used in ether-ether polyalcohol；
The polyester polyol A is the polyadipate system polyester diol of 500-5000 number-average molecular weights and polyadipate system
The mixture of polyester polyol；The mass ratio of polyadipate system polyester diol and polyadipate system polyester polyol is 3:
2~99: 1, polyadipate system polyester diol is the polycondensation product of adipic acid and small molecule dihydric alcohol a, the small molecule
Dihydric alcohol a is ethylene glycol, 1,3-PD, 1,4-butanediol, the one or more in diglycol；It is described to gather oneself
Oxalic acid series polyester polyol is adipic acid and the polymerizate of small molecule dihydric alcohol a and small molecule trihydroxylic alcohol a；Degree of functionality is 2.05
~2.80, the small molecule dihydric alcohol a are ethylene glycol, 1,3-PD, 1,4-butanediol, one kind in diglycol or
More than one；The small molecule trihydroxylic alcohol a for glycerine, trimethylolpropane, trimethylolethane, one kind in hexanetriol or
Two kinds of mixtures：
The small molecular alcohol chain extender be small molecule dihydric alcohol b and small molecule trihydroxylic alcohol b mixture, the small molecule two
The mass ratio of first alcohol b and small molecule trihydroxylic alcohol b are 7: 3~19: 5.
The small molecule dihydric alcohol b be ethylene glycol, 1,4-butanediol, 1,3-PD, diglycol, neopentyl glycol
In it is one or more of；The small molecule trihydroxylic alcohol b is trimethylolpropane, trimethylolethane, glycerine, xylitol, sorb
Alcohol, mannitol, 1, it is one or more of in 2,6- hexanetriols.
The foam stabilizer is organosilicon foam stabilizer.
The water is deionized water.
The durability auxiliary agent is more than one of ultra-violet absorber, hindered amine as light stabilizer or antioxidant；The purple
Ultraviolet absorbers for ultra-violet absorber UV-1, UV-2, UV-320, UV-326, UV-327, UV-328, UV-571, UV-1130,
It is one or more of in UV-234, UV-1229, UV-1164Z；Hindered amine as light stabilizer is light stabilizer 292, light stabilizer
622nd, it is one or more of in light stabilizer 770；Antioxidant is antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant
1076th, one kind in antioxidant 1098, antioxidant 1135, antioxidant 1330, antioxidant 1024, antioxidant 3114, irgasfos 168
Or more.
The catalyst is one or both of amines catalyst, organo-metallic catalyst；The amines catalyst is
It is one or more of in triethanolamine, triethylene diamine；The organo-metallic catalyst is organotin, organo-bismuth, organic potassium, is had
It is one or more of in machine zinc.
The diisocyanate for methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), naphthalene diisocyanate, to benzene
Diisocyanate, benzene dimethylene diisocyanate, dimethyl diphenyl diisocyanate, dimethyl diphenylmethane diisocyanate
Ester, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate, hexamethylene diisocyanate, Isosorbide-5-Nitrae-hexamethylene two
Isocyanates, cyclohexanedimethyleterephthalate diisocyanate, trimethyl -1,6- hexamethylene diisocyanate, methylcyclohexyl two
One or both of isocyanates.
In resin B,
The polyvalent alcohol is degree of functionality 2~3, and 500~5000 polyadipate system polyalcohol of number-average molecular weight gathers in oneself
In ester system polyalcohol, polycarbonate-based polyalcohol it is a kind of mostly more than；
Alternatively,
The polyvalent alcohol is the mixture of polyester diol and polyether polyol；The polyester diol and polyether polyols
The mass ratio of alcohol is 1: 9~9: 1；
Wherein, polyether polyol is 5000~20000 number-average molecular weight polyether Glycols, polyether-tribasic alcohol and polyethers quaternary
The mixture of alcohol, the polyether Glycols, polyether-tribasic alcohol and polyethers tetrahydroxylic alcohol account for the mass percentage point of polyether polyol
Not Wei 40%~75%, 10%~50%, 0~20%；The polyether Glycols are polyoxyethylene glycol, polypropylene oxide
One kind in dihydric alcohol, polypropylene oxide-ethylene oxide dihydric alcohol, polyoxybutylene dihydric alcohol, polytetrahydrofuran ether dihydric alcohol
Or more than one；The polyether-tribasic alcohol is polypropylene oxide trihydroxylic alcohol, one kind in polypropylene oxide-ethylene oxide trihydroxylic alcohol
Or two kinds；The polyethers tetrahydroxylic alcohol is polypropylene oxide tetrahydroxylic alcohol.
The polyester diol is the polyadipate system polyester diol of 500~5000 number-average molecular weights, polycaprolactone system
It is one or more of in polyester diol, polycarbonate-based polyester diol.
The preparation method of the solvent-free leather polyurethane resin, comprises the following steps：
(1) preparation of Resin A component：It is more that polyester ether polylol-polyisocyanates performed polymer, polyester are put into reaction kettle
First alcohol A, is warming up to 120-140 DEG C, and 5~6h is dehydrated under the vacuum condition of -0.06MPa~-0.01MPa, after be cooled to 30~50
DEG C, small molecular alcohol chain extender, foam stabilizer, durability auxiliary agent, catalyst, water are added in, after stirring 2~4h, detects hydroxyl value and moisture
Content treats that hydroxyl value reaches 50-200mgKOH/g, and moisture is less than 600ppm, that is, Resin A component is made, and packs for use；
(2) preparation of B component：Diisocyanate, polyvalent alcohol, phosphoric acid is put into reaction kettle to stir at 90~110 DEG C
Mix reaction 1.5h~3.0h, sampling detection NCO content, when NCO content is 4%~35%, be down to 30~50 DEG C of blowings to get
Resin B component packs for use.
The solvent-free leather is used to prepare no-solvent polyurethane synthetic leather, application process, including as follows with polyurethane resin
Step：
Resin A component and resin B component in mass ratio 3: 1~1: 3 are sufficiently mixed, the mixing up time 15~
The solvent-free AB mixed is expected to be coated in release paper according to the thickness set, into baking oven preliminary drying, treats leather hard by 20min
Lower fitting base fabric, controls pressure roll gap, and solventfree resin and base fabric can be pasted jail and do not crushed abscess, into temperature
The drying tunnel controlled at 130~140 DEG C cures 4~8min, and winding obtains no-solvent polyurethane synthetic leather.
Compared with prior art, the present invention has the following advantages：
(1) whole process need to only scratch a knife solventfree resin, without in addition scratching surface layer resin and tie layer resins, i.e.,
Surface layer, adhesive layer and foaming layer structure, convenience simple for process can be possessed, and dried, curing winds entire production process without molten
Agent participates in, and without evaporating solvent or moisture, does not also generate a large amount of organic liquid wastes or waste water, energy conservation and environmental protection, production efficiency is high, cost
It is low.
(2) the mixing up time of Resin A component and resin B component of the present invention up to 15~20min, improves synthesis
Remove from office the production operability in large-scale production process.
(3) Resin A component of the present invention introduces appropriate polyester ether polylol-polyisocyanates performed polymer, effectively adjusts resin
The parameters such as viscosity, molecular weight ensure the stability of Resin A component and B component proportioning during production and processing.
(4) no-solvent polyurethane synthetic leather physical mechanical property of the invention is excellent.
Specific embodiment
Below by specific embodiment, the present invention is further elaborated, it should be understood that the reality of the present invention
The specific material proportion described in example is applied, process conditions and result are merely to illustrate the present invention, this can not be limited with this
The protection domain of invention, the equivalent change or modification that every Spirit Essence according to the present invention is done, should all cover in this hair
In bright protection domain.
Embodiment 1
(number-average molecular weight 10000, degree of functionality are the polyester ether polylol of 20.00kg-toluene di-isocyanate(TDI) performed polymer
2), the polyadipate ethylene glycol propylene glycol ester (number-average molecular weight 1000) of 73.35kg, the one contracting diethyl of polyadipate of 1.65kg
Glycol glycerine ester (degree of functionality 2.80, number-average molecular weight are 2000) is warming up to 120 DEG C, under the vacuum condition of -0.01MPa
Be dehydrated 6h, after be cooled to 30 DEG C, add in 2.10kg ethylene glycol, the trimethylolpropane of 0.90kg, the even bubble of organosilicon of 0.70kg
Agent, the deionized water of 0.3kg, the light stabilizer 292 of ultra-violet absorber UV-320,0.30kg of 0.65kg, 0.05kg it is anti-
2h is mixed in oxidant 245 and the organotin metallic catalyst of 0.30kg, detects hydroxyl value and moisture, treats that hydroxyl value reaches
During moisture 0.3%, that is, Resin A component is made in 153.8mgKOH/g, packs for use.
The toluene di-isocyanate(TDI) of 33.10kg is put into reaction kettle, (number is equal for the polyethylene glycol adipate of 49.62kg
Molecular weight is that 3.0h 3000) is stirred to react at 90 DEG C, and sampling detection NCO content when NCO content is 17.6%, is down to 30
DEG C blowing is to get polyurethane resin B component.
Resin A component and resin B component in mass ratio 100: 65 are sufficiently mixed, mix up time 20min,
Mixed resin is uniformly applied in release paper according to the thickness set, it is pre- anti-in 110 DEG C of drying tunnel into temperature control
Base fabric should be then bonded to leather hard, laminate pressure is adjusted according to leather hard, it is ripe into 130-140 DEG C again after posting
Change 6min, cool down, winding obtains no-solvent polyurethane synthetic leather.
Embodiment 2
The polyester ether polylol of 35.00kg-different Buddhist dione polyisocyanate performed polymer (number-average molecular weight 10000, function
It spends for 4), the polyadipate diglycol butanediol ester (number-average molecular weight 5000) of 58.00kg, 2.00kg's gathers oneself two
Sour diglycol glycerine ester (degree of functionality 2.05, number-average molecular weight 5000) is warming up to 140 DEG C, and -0.06MPa's is true
Be dehydrated 5h under empty condition, after be cooled to 50 DEG C, add in 2.47kg 1,4-butanediol, the trimethylolpropane of 0.13kg, 0.30kg
Organosilicon foam stabilizer, the deionized water of 0.30kg, the light stabilizer of ultra-violet absorber UV-320,0.36kg of 0.45kg
292nd, 2h is mixed in the organotin metallic catalyst of the antioxidant 245 of 0.09kg and 0.90kg, detects hydroxyl value and moisture contains
Amount treats that hydroxyl value reaches 125.4mgKOH/g, during moisture 16%, that is, Resin A component is made, packs for use.
Toluene di-isocyanate(TDI), the methyl diphenylene diisocyanate of 24.23kg of 8.06kg is put into reaction kettle,
The poly adipate succinic acid ester (number-average molecular weight 1000) of 28.06kg is stirred to react 1.5h at 110 DEG C, and sampling detection NCO contains
Amount when NCO content is 16%, is down to 50 DEG C of blowings to get polyurethane resin B component.
Resin A component and resin B component in mass ratio 100: 59 are sufficiently mixed, mix up time 15min, it will be mixed
Resin after conjunction is uniformly applied in release paper according to the thickness set, and the drying tunnel pre-reaction at 80 DEG C is controlled to partly into temperature
Dry state, is then bonded base fabric, laminate pressure is adjusted according to leather hard, and 6min is cured into 130-140 DEG C again after posting,
Cooling, winding, obtains no-solvent polyurethane synthetic leather.
Embodiment 3
The polyester ether polylol of 33.40kg-methyl diphenylene diisocyanate performed polymer (number-average molecular weight 30000, official
3) energy degree is, the polyadipate diglycol ester (number-average molecular weight 3000) of 40.00kg, the polyadipate of 15.00kg
Diglycol trihydroxymethylpropanyl ester (degree of functionality 2.3, number-average molecular weight 3000) is warming up to 130 DEG C, -0.04MPa
Vacuum condition under be dehydrated 5h, after be cooled to 40 DEG C, add in 4.50kg ethylene glycol, the trimethylolpropane of 0.50kg, 2.00kg
Organosilicon foam stabilizer, the deionized water of 2.00kg, the light stabilizer of ultra-violet absorber UV-320,0.64kg of 0.64kg
292nd, 3h is mixed in the organotin metallic catalyst of the antioxidant 245 of 0.32kg and 1.00kg, detects hydroxyl value and moisture contains
Amount treats that hydroxyl value reaches 235.7mgKOH/g, during moisture 2.0%, that is, Resin A component is made, packs for use.
The methane diisocyanate of 28.98kg, the polydiethylene glycol adipate (number of 37.53kg are put into reaction kettle
Average molecular weight is 500) and the phosphoric acid of 0.78g is stirred to react 2.0h, sampling detection NCO content, when NCO content is at 100 DEG C
When 11.6%, 30 DEG C of blowings are down to get polyurethane resin B component.
Resin A component and resin B component in mass ratio 100: 152 are sufficiently mixed, mix the up time
Mixed resin is uniformly applied in release paper by 20min according to the thickness set, the baking into temperature control at 100 DEG C
Then road pre-reaction is bonded base fabric, laminate pressure is adjusted according to leather hard, again into 130- after posting to leather hard
140 DEG C of curing 6min, cool down, and winding obtains no-solvent polyurethane synthetic leather.
Embodiment 4
The polyester ether polylol of 40.00kg-methyl diphenylene diisocyanate performed polymer (number-average molecular weight 20000, official
Energy degree is 4), the polyadipate diglycol propylene glycol ester (number-average molecular weight 2000) of 37.80kg, 16.20kg's is poly-
Adipic acid butanediol glycerine ester (degree of functionality 2.5, number-average molecular weight 3000) is warming up to 120 DEG C, the vacuum of -0.01MPa
Under the conditions of be dehydrated 6h, after be cooled to 30 DEG C, add in the ethylene glycol of 1.6kg, the trimethylolpropane of 0.05kg, 1.00kg's is organic
Silicon foam stabilizer, the deionized water of 1.00kg, ultra-violet absorber UV-320,0.60kg of 0.45kg light stabilizer 292,
2h is mixed in the antioxidant 245 of 0.30kg and the organotin metallic catalyst of 1.00kg, detects hydroxyl value and moisture, treats
Hydroxyl value reaches 125.2mgKOH/g, during moisture 1.0%, that is, Resin A component is made, packs for use.
Methyl diphenylene diisocyanate, the toluene di-isocyanate(TDI) of 27.34kg of 3.44kg is put into reaction kettle,
The polydiethylene glycol adipate (number-average molecular weight 500) and 0.5g phosphoric acid of 10.30kg is stirred to react 1.5h at 110 DEG C,
Sampling detection NCO content, when NCO content is 30.7%, is down to 50 DEG C of blowings to get polyurethane resin B component.
Resin A component and resin B component in mass ratio 100: 31 are sufficiently mixed, mix up time 10min, it will be mixed
Resin after conjunction is uniformly applied in release paper according to the thickness set, into temperature control 110 DEG C drying tunnel pre-reaction extremely
Then leather hard is bonded base fabric, laminate pressure is adjusted according to leather hard, again into 130-140 DEG C of curing after posting
6min is cooled down, and winding obtains no-solvent polyurethane synthetic leather.
Embodiment 5
The polyester ether polylol of 30.00kg-different Buddhist diisocyanates performed polymer (number-average molecular weight 10000, function
It spends for 2), the polyadipate ethylene glycol propylene glycol ester (number-average molecular weight 1000) of 64.35kg, the polyadipate one of 0.65kg contracts
Diethylene glycol glycerine ester (degree of functionality 2.80, number-average molecular weight are 2000) is warming up to 120 DEG C, the vacuum item of -0.01MPa
Be dehydrated 6h under part, after be cooled to 30 ° (C, add in 2.10kg ethylene glycol, the trimethylolpropane of 0.90kg, the organosilicons of 0.70kg
Foam stabilizer, the deionized water of 0.50kg, light stabilizer 292, the 0.05kg of ultra-violet absorber UV-320,0.30kg of 0.15kg
Antioxidant 245 and the organotin metallic catalyst of 0.30kg 2h is mixed, detect hydroxyl value and moisture, treat that hydroxyl value reaches
To 156.5mgKOH/g, during moisture 0.5%, that is, Resin A component is made, packs for use.
The isophorone diisocyanate of 33.10kg, the polyethylene glycol adipate of 49.62kg are put into reaction kettle
(number-average molecular weight 3000) is stirred to react 3.0h at 90 DEG C, and sampling detection NCO content when NCO content is 12.6%, drops
To 30 DEG C of blowings to get polyurethane resin B component.
Resin A component and resin B component in mass ratio 100: 93 are sufficiently mixed, mix up time 20min,
Mixed resin is uniformly applied in release paper according to the thickness set, the drying tunnel pre-reaction into temperature control at 80 DEG C
To leather hard, base fabric is then bonded, laminate pressure is adjusted according to leather hard, again into 130-140 DEG C of curing after posting
6min is cooled down, and winding obtains no-solvent polyurethane synthetic leather.
Embodiment 6
The polyester ether polylol of 45.00kg-different Buddhist dione polyisocyanate performed polymer (number-average molecular weight 10000, function
It spends for 4), the polyadipate diglycol butanediol ester (number-average molecular weight 5000) of 30.00kg, 20.00kg's gathers oneself
Diacid diglycol glycerine ester (degree of functionality 2.05, number-average molecular weight 5000) is warming up to 140 DEG C, -0.06MPa's
Be dehydrated 5h under vacuum condition, after be cooled to 50 DEG C, add in 2.47kg 1,4-butanediol, the trimethylolpropane of 0.13kg,
The organosilicon foam stabilizer of 0.30kg, the deionized water of 0.30kg, the light of ultra-violet absorber UV-320,0.36kg of 0.45kg are steady
2h is mixed in the organotin metallic catalyst for determining agent 292, the antioxidant 245 of 0.09kg and 0.90kg, detects hydroxyl value and water
Point content treats that hydroxyl value reaches 72.6mgKOH/g, during moisture 0.3%, that is, Resin A component is made, packs for use.
Isophorone diisocyanate, two isocyanide of dicyclohexyl methyl hydride of 24.23kg of 8.06kg is put into reaction kettle
Acid esters, the poly adipate succinic acid ester (number-average molecular weight 1000) of 28.06kg are stirred to react 1.5h, sampling detection at 110 DEG C
NCO content when NCO content is 14%, is down to 50 DEG C of blowings to get polyurethane resin B component.
Resin A component and resin B component in mass ratio 100: 39 are sufficiently mixed, mix up time 15min, it will be mixed
Resin after conjunction is uniformly applied in release paper according to the thickness set, into temperature control 110 DEG C drying tunnel pre-reaction extremely
Then leather hard is bonded base fabric, laminate pressure is adjusted according to leather hard, again into 130-140 DEG C of curing after posting
8min is cooled down, and winding obtains no-solvent polyurethane synthetic leather.
Embodiment 7
The polyester ether polylol of 38.00kg-different Buddhist dione polyisocyanate performed polymer (number-average molecular weight 30000, function
It spends for 3), the polyadipate diglycol ester (number-average molecular weight 3000) of 40.00kg, the polyadipate one of 10.00kg
Diglycol ethylene trihydroxymethylpropanyl ester (degree of functionality 2.3, number-average molecular weight 3000) is warming up to 130 DEG C, -0.04MPa's
Be dehydrated 5h under vacuum condition, after be cooled to 40 DEG C, add in 4.50kg ethylene glycol, the trimethylolpropane of 0.50kg, 2.00kg's
Organosilicon foam stabilizer, the deionized water of 0.3kg, ultra-violet absorber UV-320,0.64kg of 1.68kg light stabilizer 292,
3h is mixed in the antioxidant 245 of 1.32kg and the organotin metallic catalyst of 1.00kg, detects hydroxyl value and moisture, treats
Hydroxyl value reaches 127.8mgKOH/g, during moisture 0.3%, that is, Resin A component is made, packs for use.
The dicyclohexyl methyl hydride diisocyanate of 28.98kg, the polyadipate diethyl two of 37.53kg are put into reaction kettle
The phosphoric acid of alcohol ester (number-average molecular weight 500) and 0.78g are stirred to react 2.0h at 100 DEG C, and sampling detection NCO content works as NCO
When content is 4.5%, 30 DEG C of blowings are down to get polyurethane resin B component.
Resin A component and resin B component in mass ratio 100: 213 are sufficiently mixed, mix the up time
Mixed resin is uniformly applied in release paper by 20min according to the thickness set, the drying tunnel into temperature control at 90 DEG C
Then pre-reaction is bonded base fabric, laminate pressure is adjusted according to leather hard, again into 130-140 after posting to leather hard
DEG C curing 5min, cool down, winding, obtain no-solvent polyurethane synthetic leather.
Embodiment 8
The polyester ether polylol of 40.00kg-different Buddhist dione polyisocyanate performed polymer (number-average molecular weight 20000, function
It spends for 4), the polyadipate diglycol propylene glycol ester (number-average molecular weight 2000) of 37.80kg, 16.20kg's gathers oneself
Diacid butanediol glycerine ester (degree of functionality 2.5, number-average molecular weight 3000) is warming up to 120 DEG C, the vacuum item of -0.01MPa
Be dehydrated 6h under part, after be cooled to 30 DEG C, add in the ethylene glycol of 0.6kg, the trimethylolpropane of 0.05kg, the organosilicon of 0.50kg
Foam stabilizer, the deionized water of 2.0kg, light stabilizer 292, the 0.30kg of ultra-violet absorber UV-320,0.25kg of 0.30kg
Antioxidant 245 and the organotin metallic catalyst of 2.00kg 2h is mixed, detect hydroxyl value and moisture, treat that hydroxyl value reaches
To 169.4mgKOH/g, during moisture 2.0%, that is, Resin A component is made, packs for use.
Different Buddhist diisocyanates, two isocyanide of dicyclohexyl methyl hydride of 27.34kg of 3.44kg is put into reaction kettle
Acid esters, the polydiethylene glycol adipate (number-average molecular weight 500) and 0.5g phosphoric acid of 10.30kg are stirred to react at 110 DEG C
1.5h, sampling detection NCO content, when NCO content is 20.3%, is down to 50 DEG C of blowings to get polyurethane resin B component.
Resin A component and resin B component in mass ratio 100: 63 are sufficiently mixed, mix up time 10min, it will be mixed
Resin after conjunction is uniformly applied in release paper according to the thickness set, and the drying tunnel pre-reaction at 90 DEG C is controlled to partly into temperature
Dry state, is then bonded base fabric, laminate pressure is adjusted according to leather hard, again into 130-140 DEG C of curing 4mi after posting
N is cooled down, and winding obtains no-solvent polyurethane synthetic leather.
Comparative example 1
The polyether polyol of 20.00kg-isophorone diisocyanate performed polymer (number-average molecular weight 10000, degree of functionality
For 2), the polyadipate ethylene glycol propylene glycol ester (number-average molecular weight 1000) of 73.35kg, the contracting of polyadipate one two of 1.65kg
Ethylene glycol glycerine ester (degree of functionality 2.80, number-average molecular weight are 2000) is warming up to 120 DEG C, the vacuum condition of -0.01MPa
Lower dehydration 6h, after be cooled to 30 DEG C, add in 2.10kg ethylene glycol, the trimethylolpropane of 0.90kg, the organosilicon of 0.70kg is even
Infusion, the deionized water of 0.3kg, the light stabilizer 292 of ultra-violet absorber UV-320,0.30kg of 0.65kg, 0.05kg
2h is mixed in the organotin metallic catalyst of antioxidant 245 and 0.30kg, detects hydroxyl value and moisture, treats that hydroxyl value reaches
During moisture 0.3%, that is, Resin A component is made in 153.8mgKOH/g, packs for use.
The dicyclohexyl methyl hydride diisocyanate of 33.10kg, the polyadipate ethylene glycol of 49.62kg are put into reaction kettle
Ester (number-average molecular weight 3000) is stirred to react 3.0h at 90 DEG C, and sampling detects NCO content, when NCO content is 17.6%,
30 DEG C of blowings are down to get polyurethane resin B component.
Resin A component and resin B component in mass ratio 100: 66 are sufficiently mixed, mix up time 20min,
Mixed resin is uniformly applied in release paper according to the thickness set, it is pre- anti-in 110 DEG C of drying tunnel into temperature control
Base fabric should be then bonded to leather hard, laminate pressure is adjusted according to leather hard, it is ripe into 130-140 DEG C again after posting
Change 6min, cool down, winding obtains no-solvent polyurethane synthetic leather.
Comparative example 2
The polyethers of 35.00kg-different Buddhist dione polyisocyanate performed polymer (number-average molecular weight 10000, degree of functionality 4),
The polytetrahydrofuran ether glycol (number-average molecular weight 5000) of 58.00kg, the polyoxypropyleneglycol (degree of functionality of 2.00kg
2.05, number-average molecular weight 5000), be warming up to 140 DEG C, be dehydrated 5h under the vacuum condition of -0.06MPa, after be cooled to 50 DEG C, add
Enter 2.47kg 1,4-butanediol, the trimethylolpropane of 0.13kg, the organosilicon foam stabilizer of 0.30kg, the deionization of 0.30kg
Water, the light stabilizer 292 of ultra-violet absorber UV-320,0.36kg of 0.45kg, the antioxidant 245 of 0.09kg and 0.90kg
Organotin metallic catalyst 2h is mixed, detect hydroxyl value and moisture, treat that hydroxyl value reaches 125.4mgKOH/g, moisture contains
When measuring 16%, that is, Resin A component is made, packs for use.
Toluene di-isocyanate(TDI), the methyl diphenylene diisocyanate of 24.23kg of 8.06kg is put into reaction kettle,
The polytetrahydrofuran ether glycol (number-average molecular weight 1000) of 28.06kg is stirred to react 1.5h at 110 DEG C, and sampling detection NCO contains
Amount when NCO content is 16%, is down to 50 DEG C of blowings to get polyurethane resin B component.
Resin A component and resin B component in mass ratio 100: 59 are sufficiently mixed, mix up time 15min, it will be mixed
Resin after conjunction is uniformly applied in release paper according to the thickness set, and the drying tunnel pre-reaction at 80 DEG C is controlled to partly into temperature
Dry state, is then bonded base fabric, laminate pressure is adjusted according to leather hard, and 6min is cured into 130-140 DEG C again after posting,
Cooling, winding, obtains no-solvent polyurethane synthetic leather.
Comparative example 3
(number-average molecular weight 30000, degree of functionality are the polyether ester of 33.40kg-methyl diphenylene diisocyanate performed polymer
3), the polyadipate diglycol ester (number-average molecular weight 3000) of 40.00kg, the contracting of polyadipate one two of 15.00kg
Ethylene glycol trihydroxymethylpropanyl ester (degree of functionality 2.3, number-average molecular weight 3000) is warming up to 130 DEG C, the vacuum of -0.04MPa
Under the conditions of be dehydrated 5h, after be cooled to 40 DEG C, add in 4.50kg ethylene glycol, the trimethylolpropane of 0.50kg, 2.00kg's is organic
Silicon foam stabilizer, the light stabilizer 292 of ultra-violet absorber UV-320,1.64kg of 1.64kg, 245 and of antioxidant of 0.32kg
3h is mixed in the organotin metallic catalyst of 1.00kg, detects hydroxyl value and moisture, treats that hydroxyl value reaches 111.0mgKOH/g,
When moisture is less than 500ppm, that is, Resin A component is made, packs for use.
The methane diisocyanate of 28.98kg, the polydiethylene glycol adipate (number of 37.53kg are put into reaction kettle
Average molecular weight is 500) and the phosphoric acid of 0.78g is stirred to react 2.0h, sampling detection NCO content, when NCO content is at 100 DEG C
When 11.6%, 30 DEG C of blowings are down to get polyurethane resin B component.
Resin A component and resin B component in mass ratio 100: 72 are sufficiently mixed, mix up time 20min,
Mixed resin is uniformly applied in release paper according to the thickness set, it is pre- anti-in 100 DEG C of drying tunnel into temperature control
Base fabric should be then bonded to leather hard, laminate pressure is adjusted according to leather hard, it is ripe into 130-140 DEG C again after posting
Change 6min, cool down, winding obtains no-solvent polyurethane synthetic leather.
Comparative example 4
(number-average molecular weight 20000, degree of functionality are the polyether ester of 40.00kg-methyl diphenylene diisocyanate performed polymer
4), the polyadipate diglycol propylene glycol ester (number-average molecular weight 2000) of 37.80kg, the polyadipate of 16.20kg
Butanediol glycerine ester (degree of functionality 2.5, number-average molecular weight 3000) is warming up to 120 DEG C, under the vacuum condition of -0.01MPa
Be dehydrated 6h, after be cooled to 30 DEG C, add in, the ethylene glycol of 1.6kg, the trimethylolpropane of 0.05kg, the organosilicon of 1.00kg is even
Infusion, the organotin metallic catalyst of the deionized water 2.35kg of 1.00kg are mixed 2h, detect hydroxyl value and moisture, treat
Hydroxyl value reaches 125.2mgKOH/g, during moisture 1.0%, that is, Resin A component is made, packs for use.
Methyl diphenylene diisocyanate, the toluene di-isocyanate(TDI) of 27.34kg of 3.44kg is put into reaction kettle,
The polydiethylene glycol adipate (number-average molecular weight 500) and 0.5g phosphoric acid of 10.30kg is stirred to react 1.5h at 110 DEG C,
Sampling detection NCO content, when NCO content is 30.7%, is down to 50 DEG C of blowings to get polyurethane resin B component.
Resin A component and resin B component in mass ratio 100: 31 are sufficiently mixed, mix up time 10min, it will be mixed
Resin after conjunction is uniformly applied in release paper according to the thickness set, into temperature control 110 DEG C drying tunnel pre-reaction extremely
Then leather hard is bonded base fabric, laminate pressure is adjusted according to leather hard, again into 130-140 DEG C of curing after posting
6min is cooled down, and winding obtains no-solvent polyurethane synthetic leather.
Comparative example 5
The polyadipate ethylene glycol propylene glycol ester (number-average molecular weight 1000) of 64.35kg, the polyadipate one of 30.65kg
Diglycol ethylene glycerine ester (degree of functionality 2.80, number-average molecular weight are 2000) is warming up to 120 DEG C, the vacuum of -0.01MPa
Under the conditions of be dehydrated 6h, after be cooled to 30 DEG C, add in 2.10kg ethylene glycol, the trimethylolpropane of 0.90kg, 0.70kg's is organic
Silicon foam stabilizer, the deionized water of 0.50kg, ultra-violet absorber UV-320,0.30kg of 0.15kg light stabilizer 292,
2h is mixed in the antioxidant 245 of 0.05kg and the organotin metallic catalyst of 0.30kg, detects hydroxyl value and moisture, treats
Hydroxyl value reaches 140.6mgKOH/g, during moisture 0.5%, that is, Resin A component is made, packs for use.
The isophorone diisocyanate of 33.10kg, the polyethylene glycol adipate of 49.62kg are put into reaction kettle
(number-average molecular weight 3000) is stirred to react 3.0h at 90 DEG C, and sampling detection NCO content when NCO content is 12.6%, drops
To 30 DEG C of blowings to get polyurethane resin B component.
Resin A component and resin B component in mass ratio 100: 84 are sufficiently mixed, mix up time 20min,
Mixed resin is uniformly applied in release paper according to the thickness set, the drying tunnel pre-reaction into temperature control at 80 DEG C
To leather hard, base fabric is then bonded, laminate pressure is adjusted according to leather hard, again into 130-140 DEG C of curing after posting
6min is cooled down, and winding obtains no-solvent polyurethane synthetic leather.
Comparative example 6
(number-average molecular weight 10000, degree of functionality are the polyether ester of 45.00kg-different Buddhist dione polyisocyanate performed polymer
4), the polyadipate diglycol butanediol ester (number-average molecular weight 5000) of 30.00kg, the polyadipate of 20.00kg
Diglycol glycerine ester (degree of functionality 2.05, number-average molecular weight 5000) is warming up to 140 DEG C, the vacuum of -0.06MPa
Under the conditions of be dehydrated 5h, after be cooled to 50 DEG C, add in 2.47kg 1,4-butanediol, the trimethylolpropane of 0.13kg, 0.60kg's
Organosilicon foam stabilizer, light stabilizer 292, the antioxidant of 0.09kg of ultra-violet absorber UV-320,0.36kg of 0.45kg
2h is mixed in the organotin metallic catalyst of 245 and 0.90kg, detects hydroxyl value and moisture, treats that hydroxyl value reaches
When moisture is less than 500ppm, that is, Resin A component is made in 53.9mgKOH/g, packs for use.
Isophorone diisocyanate, two isocyanide of dicyclohexyl methyl hydride of 24.23kg of 8.06kg is put into reaction kettle
Acid esters, the poly adipate succinic acid ester (number-average molecular weight 1000) of 28.06kg are stirred to react 1.5h, sampling detection at 110 DEG C
NCO content when NCO content is 14%, is down to 50 DEG C of blowings to get polyurethane resin B component.
Resin A component and resin B component in mass ratio 100: 29 are sufficiently mixed, mix up time 15min, it will be mixed
Resin after conjunction is uniformly applied in release paper according to the thickness set, into temperature control 110 DEG C drying tunnel pre-reaction extremely
Then leather hard is bonded base fabric, laminate pressure is adjusted according to leather hard, again into 130-140 DEG C of curing after posting
8min is cooled down, and winding obtains no-solvent polyurethane synthetic leather.
Comparative example 7
The polyethers of 38.00kg-isophorone diisocyanate performed polymer (number-average molecular weight 30000, degree of functionality 3),
The polyadipate diglycol ester (number-average molecular weight 3000) of 40.00kg, the one contracting diethyl two of polyadipate of 10.00kg
Alcohol trihydroxymethylpropanyl ester (degree of functionality 2.3, number-average molecular weight 3000) is warming up to 130 DEG C, the vacuum condition of -0.04MPa
Lower dehydration 5h, after be cooled to 40 DEG C, add in 4.50kg ethylene glycol, the trimethylolpropane of 0.50kg, the organosilicon of 2.00kg is even
Infusion, the deionized water of 0.3kg, the light stabilizer 292 of ultra-violet absorber UV-320,0.64kg of 1.68kg, 1.32kg
3h is mixed in the organotin metallic catalyst of antioxidant 245 and 1.00kg, detects hydroxyl value and moisture, treats that hydroxyl value reaches
During moisture 0.3%, that is, Resin A component is made in 127.8mgKOH/g, packs for use.
The dicyclohexyl methyl hydride diisocyanate of 28.98kg, the polyadipate diethyl two of 37.53kg are put into reaction kettle
The phosphoric acid of alcohol ester (number-average molecular weight 500) and 0.78g are stirred to react 2.0h at 100 DEG C, and sampling detection NCO content works as NCO
When content is 4.5%, 30 DEG C of blowings are down to get polyurethane resin B component.
Resin A component and resin B component in mass ratio 100: 213 are sufficiently mixed, mix the up time
Mixed resin is uniformly applied in release paper by 20min according to the thickness set, the drying tunnel into temperature control at 90 DEG C
Then pre-reaction is bonded base fabric, laminate pressure is adjusted according to leather hard, again into 130-140 after posting to leather hard
DEG C curing 5min, cool down, winding, obtain no-solvent polyurethane synthetic leather.
Comparative example 8
(number-average molecular weight 20000, degree of functionality are the polyether ester of 40.00kg-different Buddhist dione polyisocyanate performed polymer
4), the poly- own diacid diglycol propylene glycol ester (number-average molecular weight 2000) of 37.80kg, the polyadipate of 16.20kg
Butanediol glycerine ester (degree of functionality 2.5, number-average molecular weight 3000) is warming up to 120 DEG C, under the vacuum condition of -0.01MPa
Be dehydrated 6h, after be cooled to 30 DEG C, add in the ethylene glycol of 0.6kg, the trimethylolpropane of 0.05kg, the even bubble of organosilicon of 1.35kg
Agent, the deionized water of 2.0kg, the organotin metallic catalyst of 2.00kg are mixed 2h, detect hydroxyl value and moisture, treat hydroxyl
Value reaches 169.4mgKOH/g, during moisture 2.0%, that is, Resin A component is made, packs for use.
Different Buddhist diisocyanates, two isocyanide of dicyclohexyl methyl hydride of 27.34kg of 3.44kg is put into reaction kettle
Acid esters, the polydiethylene glycol adipate (number-average molecular weight 500) and 0.5g phosphoric acid of 10.30kg are stirred to react at 110 DEG C
1.5h, sampling detection NCO content, when NCO content is 20.3%, is down to 50 DEG C of blowings to get polyurethane resin B component.
Resin A component and resin component E in mass ratio 100: 63 are sufficiently mixed, mix up time 10min, it will be mixed
Resin after conjunction is uniformly applied in release paper according to the thickness set, and the drying tunnel pre-reaction at 90 DEG C is controlled to partly into temperature
Dry state, is then bonded base fabric, laminate pressure is adjusted according to leather hard, and 4min is cured into 130-140 DEG C again after posting,
Cooling, winding, obtains no-solvent polyurethane synthetic leather.
Every physical property measurement of Synthetic Leather obtained by Application Example 1~4 and comparative example 1~4 the results are shown in
Table 1.
Table 1
Every physical property measurement of Synthetic Leather obtained by Application Example 5~8 and comparative example 5~8 the results are shown in
Table 2.
Table 2
To sum up, the polyurethane resin of product high temperature resistant integrative of the present invention, hilted broadsword technique be coated on base fabric, simple for process ten thousand
Just, good operability realizes foaming layer, adhesive layer and surface layer integration.From table 1 it follows that embodiment is in peel strength, anti-
Zhang Qiangdu, heat resistance and yellowing resistance etc. are all significantly improved compared with comparative example, and do not contain any organic solvent, no
Environment is polluted, does not influence operation element health.
Although above-described embodiment is described in detail technical scheme, the technical side of the present invention
Case is not limited to above example, the thought and objective of the present invention is not being departed from, to scope of the present invention patent
The equivalent change or modification that content is made all should be the technology scope of the present invention.
Claims (11)
1. the polyurethane resin of uninanned platform leather, which is characterized in that include Resin A component and resin B component；The Resin A
Component contains polyester ether polylol-polyisocyanates performed polymer that weight percent is 20%~45% and weight percent is
0.3%~2.0% water, the resin B component contain the diisocyanate that weight percent is 20%~60%；
The mass ratio of the Resin A component and resin B component is 3: 1~1: 3.
2. the polyurethane resin of uninanned platform according to claim 1 leather, which is characterized in that the Resin A component by
The component composition of following mass percentage：
The Resin A component is made of the component of following mass percentage：
The resin B component is made of the component of following mass percentage：
Diisocyanate 20%~60%；
Polyvalent alcohol 30%~80%；
Phosphoric acid 0~1%；
NCO content is 4%~35% in the resin B component.
3. the polyurethane resin of uninanned platform leather according to claim 2, which is characterized in that the polyether ester is polynary
Alcohol-polyisocyanates performed polymer number-average molecular weight is 10000~100000, and degree of functionality is 2~4；
The polyester ether polylol-polyisocyanates performed polymer is the prepolymer of polyester ether polylol and polyisocyanates,
Middle toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, naphthalene diisocyanate, paraphenylene diisocyanate, triphenyl methane
Triisocyanate, dimethyl triphenyl methane tetraisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate
Ester, hexamethylene diisocyanate, Isosorbide-5-Nitrae-cyclohexane diisocyanate, cyclohexanedimethyleterephthalate diisocyanate, trimethyl -1,
It is one or more of in 6- hexamethylene diisocyanates, Methylcyclohexyl diisocyanate.
4. the polyurethane resin of uninanned platform leather according to claim 2, which is characterized in that the polyester polyol A
For the polyadipate system polyester diol of 500-5000 number-average molecular weights and the mixture of polyadipate system polyester polyol；It is described
The mass ratio of polyadipate system polyester diol and polyadipate system polyester polyol is 3: 2~99: 1, the polyadipate system
Polyester diol is the polycondensation product of adipic acid and small molecule dihydric alcohol a, and the small molecule dihydric alcohol a is ethylene glycol, 1,3- third
Glycol, 1,4-butanediol, the one or more in diglycol；Polyadipate system polyester polyol for oneself two
The polymerizate of acid and small molecule dihydric alcohol a and small molecule trihydroxylic alcohol a；Degree of functionality is 2.05~2.80, the small molecule binary
Alcohol a is ethylene glycol, 1,3-PD, 1,4-butanediol, the one or more in diglycol；The small molecule three
First alcohol a is one or both of glycerine, trimethylolpropane, trimethylolethane, hexanetriol mixture.
5. the polyurethane resin of uninanned platform according to claim 2 leather, which is characterized in that small molecule dihydric alcohol b and
The mass ratio of the mixture of small molecule trihydroxylic alcohol b, the small molecule dihydric alcohol b and small molecule trihydroxylic alcohol b are 7: 3~19: 5.
6. the polyurethane resin of uninanned platform leather according to claim 5, which is characterized in that the small molecule dihydric alcohol
B is ethylene glycol, 1,4-butanediol, 1,3-PD, one or more of in diglycol, neopentyl glycol；Described small point
Sub- trihydroxylic alcohol b is trimethylolpropane, in trimethylolethane, glycerine, xylitol, sorbierite, mannitol, 1,2,6- hexanetriols
It is one or more of.
7. the polyurethane resin of uninanned platform leather according to claim 2, which is characterized in that the foam stabilizer is organic
Silicon foam stabilizer；
The antifoaming agent is fluorine class antifoaming agent, the one or more of type siloxane antifoaming agent；
The durability auxiliary agent be ultra-violet absorber, hindered amine as light stabilizer or antioxidant more than one, the ultraviolet light
Absorbent is ultra-violet absorber UV-1, UV-2, UV-320, UV-326, UV-327, UV-328, UV-571, UV-1130, UV-
234th, it is one or more of in UV-1229, UV-1164Z；Hindered amine as light stabilizer is light stabilizer 292, light stabilizer 622, light
It is one or more of in stabilizer 770；Antioxidant is antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, anti-
It is one or more of in oxygen agent 1098, antioxidant 1135, antioxidant 1330, antioxidant 1024, antioxidant 3114, irgasfos 168,
The catalyst is one or both of amines catalyst, organo-metallic catalyst；The amines catalyst for triethanolamine,
It is one or more of in triethylene diamine；The organo-metallic catalyst is organotin, in organo-bismuth, organic potassium, organic zinc
It is one or more of.
The diisocyanate is methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), naphthalene diisocyanate, different to benzene two
Cyanate, benzene dimethylene diisocyanate, dimethyl diphenyl diisocyanate, dimethyl diphenylmethane diisocyanate,
Isophorone diisocyanate, dicyclohexyl methyl hydride diisocyanate, hexamethylene diisocyanate, two isocyanide of Isosorbide-5-Nitrae-hexamethylene
Acid esters, cyclohexanedimethyleterephthalate diisocyanate, trimethyl -1,6- hexamethylene diisocyanate, two isocyanide of methylcyclohexyl
One or both of acid esters.
8. the polyurethane resin of uninanned platform leather according to claim 2, which is characterized in that in resin B, polyvalent alcohol
It is 500~5000 polyadipate system polyalcohol of number-average molecular weight, polycaprolactone system polyalcohol, polycarbonate-based for degree of functionality 2~3
In polyalcohol it is a kind of mostly more than.
9. the polyurethane resin of uninanned platform leather according to claim 2, which is characterized in that described poly- more in resin B
First alcohol is the mixture of polyester diol and polyether polyol；The mass ratio of the polyester diol and polyether polyol is 1: 9
~9: 1；
Wherein, polyether polyol is 5000~20000 number-average molecular weight polyether Glycols, polyether-tribasic alcohol and polyethers tetrahydroxylic alcohol
Mixture, the mass percentage that the polyether Glycols, polyether-tribasic alcohol and polyethers tetrahydroxylic alcohol account for polyether polyol are respectively
40%~75%, 10%~50%, 0~20%；Polyester diol is the polyadipate system polyester of 500~5000 number-average molecular weights
It is one or more of in dihydric alcohol, polycaprolactone system polyester diol, polycarbonate-based polyester diol.
10. according to the preparation method for the polyurethane resin that claim 1~9 any one of them uninanned platform is removed from office, feature
It is, comprises the following steps：
(1) preparation of Resin A component：Polyester ether polylol-polyisocyanates performed polymer, polyester polyol are put into reaction kettle
A, is warming up to 120-140 DEG C, and 5~6h is dehydrated under the vacuum condition of -0.06MPa~-0.01MPa, after be cooled to 30~50 DEG C, add
Enter small molecular alcohol chain extender, even Pauli, durability auxiliary agent, catalyst, water, after stirring 2~4h, detect hydroxyl value and moisture,
Treat that hydroxyl value reaches 50-200mgKOH/g, moisture is less than 600ppm, that is, Resin A component is made, and packs for use；
(2) preparation of B component：Diisocyanate, polyvalent alcohol, phosphoric acid is put into reaction kettle to stir at 90~110 DEG C instead
1.5h~3.0h is answered, sampling detection NCO content when NCO content is 4%~35%, is down to 30~50 DEG C of blowings to get resin
B component packs for use.
11. according to the application for the polyurethane resin that claim 1~9 any one of them uninanned platform is removed from office, which is characterized in that
No-solvent polyurethane synthetic leather is used to prepare, application process includes the following steps：
Resin A component and resin B component in mass ratio 3: 1~1: 3 are sufficiently mixed, the mixing up time 15~
The solvent-free AB mixed is expected to be coated in release paper according to the thickness set, into baking oven preliminary drying, treats leather hard by 20min
Lower fitting base fabric, controls pressure roll gap, and solventfree resin and base fabric can be pasted jail and do not crushed abscess, into temperature
The drying tunnel controlled at 130~140 DEG C cures 4~8min, and winding obtains no-solvent polyurethane synthetic leather.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679059A (en) * | 2018-12-11 | 2019-04-26 | 万华化学集团股份有限公司 | A kind of polyurethane-polyurea water dispersion and the preparation method and application thereof |
| CN110592965A (en) * | 2019-08-26 | 2019-12-20 | 安徽安利材料科技股份有限公司 | High-foaming high-stripping solvent-free shoe leather and preparation method thereof |
| CN112375206A (en) * | 2020-12-22 | 2021-02-19 | 浙江兆泽实业有限公司 | High-physical-property solvent-free polyurethane fabric resin for leather and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504213A (en) * | 2016-01-29 | 2016-04-20 | 李善军 | Solvent-free polyurethane composition for synthetic leather |
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2017
- 2017-12-29 CN CN201711500645.1A patent/CN108047414A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504213A (en) * | 2016-01-29 | 2016-04-20 | 李善军 | Solvent-free polyurethane composition for synthetic leather |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109679059A (en) * | 2018-12-11 | 2019-04-26 | 万华化学集团股份有限公司 | A kind of polyurethane-polyurea water dispersion and the preparation method and application thereof |
| CN109679059B (en) * | 2018-12-11 | 2021-07-23 | 万华化学集团股份有限公司 | Polyurethane-polyurea aqueous dispersion and preparation method and application thereof |
| CN110592965A (en) * | 2019-08-26 | 2019-12-20 | 安徽安利材料科技股份有限公司 | High-foaming high-stripping solvent-free shoe leather and preparation method thereof |
| CN112375206A (en) * | 2020-12-22 | 2021-02-19 | 浙江兆泽实业有限公司 | High-physical-property solvent-free polyurethane fabric resin for leather and preparation method thereof |
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Application publication date: 20180518 |