CN104844780A - Environment-friendly low-temperature wet stamping-discoloring polyurethane resin and preparation method for same - Google Patents
Environment-friendly low-temperature wet stamping-discoloring polyurethane resin and preparation method for same Download PDFInfo
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- CN104844780A CN104844780A CN201510264873.8A CN201510264873A CN104844780A CN 104844780 A CN104844780 A CN 104844780A CN 201510264873 A CN201510264873 A CN 201510264873A CN 104844780 A CN104844780 A CN 104844780A
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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- 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
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- 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
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- 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
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention provides environment-friendly low-temperature wet stamping-discoloring polyurethane resin and a preparation method for the same. The polyurethane resin is processed from the following components in parts by mass: 8 to 10 parts of diphenylmethane diisocyanate, 12 to 16 parts of polybutylene adipate polyol, 3 to 5 parts of polycaprolactone, 0.8 to 1 part of ethylene glycol, 1 to 3 parts of 1.4-butylene glycol, 0.2 to 0.4 part of a stamping-discoloring auxiliary, 0.01 to 0.03 part of hydroxymethyl modified silicone oil and 68 to 70 parts of dimethylformamide. The preparation method is simple in process and high in operability, and the obtained low-temperature wet stamping-discoloring polyurethane resin has the advantages of good low-temperature stamping-discolorinig effects, low stamping-discoloring temperature, uniform color, stable discoloring, low organic solvent residual rate and the like.
Description
Technical field
The present invention relates to technical field of chemical product manufacture, be specifically related to a kind of environment-friendly type leather low temperature wet method pressure and become urethane resin and preparation method thereof.
Background technology
Conventional urethane resin, in a large number for process hides, as leatheroid, synthetic leather, split leather leather etc., generally has two kinds of working methods, i.e. dry method and wet method.Dry method refers to urethane resin to be directly coated with scrapes in separate-type paper (also known as interleaving paper), and fitting with base material after oven drying forms again; Wet method refers to urethane resin to be directly coated with and scrapes on base material (base material comprises non-woven fabrics, cotton, nylon cloth, split leather etc.) and put into tank and solidify, and forms after washing out solvent with water through oven for drying again.Wet method is relative to the finished product made by dry method, and Determination of Residual Organic Solvents is low, belongs to environment-friendly type synthetic leather.
Pressure change refers to carries out high temperature hot pressure by the leather made, and makes leather surface variable color, and general employing dry-process polyurethane synthetic leather pressure change at present, reaches pressure and become effect.Dry method pressure changing resin in common leather urethane resin, adds pressure become auxiliary agent, makes top layer variable color under high temperature and certain pressure.There is following weak point in the method: residual organic solvent more (about 300ppm) after processing; Pressure temperature is high, needs more than 190 DEG C; Pressure become after uneven color, and high-temperature high-pressure become different cause urethane resin physical property change, even carbonize.
Summary of the invention
The object of this invention is to provide a kind of environment-friendly type leather low temperature wet method pressure and become urethane resin and preparation method thereof, technique is simple, workable, made to low temperature wet method pressure changing resin have low temperature and pressure become effective, pressure temperature is low, color even, variable color is stablized, the advantages such as residual organic solvent is low.
To achieve these goals, the technical solution used in the present invention is as follows:
A kind of environment-friendly type leather low temperature wet method pressure becomes urethane resin, is processed by following component and mass fraction thereof: diphenylmethanediisocyanate (MDI) 8-10 part, poly adipate succinic acid ester polyvalent alcohol (PBA) 12-16 part, polycaprolactone polyol (PCL) 3-5 part, ethylene glycol (EG) 0.8-1 part, 1.4-butyleneglycol (BG) 1-3 part, pressure become auxiliary agent 0.2-0.4 part, methylol-modified silicone oil 0.01-0.03 part, dimethyl formamide (DMF) 68-70 part.
Environment-friendly type leather low temperature wet method pressure becomes a preparation method for urethane resin, comprises the steps:
1) poly adipate succinic acid ester polyvalent alcohol, polycaprolactone polyol, 28-31 wt% dimethyl formamide are dropped into glass reaction still, heat up and stir;
2) 12-17 wt% diphenylmethanediisocyanate is dropped into reactor, isothermal reaction, makes prepolymer;
3) ethylene glycol, 1.4-butyleneglycol, 39-41 wt% dimethyl formamide are dropped into reactor, constant temperature stirs;
4) thickening reaction is carried out in 83-88 wt% diphenylmethanediisocyanate input reactor under constant temperature;
5) drop into 18-21 wt% dimethyl formyl, constant temperature agitation and dilution is to setting theoretical solid content;
6) carry out viscosimetric analysis, if viscosity is defective, then add diphenylmethanediisocyanate thickening, the qualified rear cooling of viscosity, add methylol-modified silicone oil, pressure becomes auxiliary agent, remain dimethyl formamide, stirs, discharging, packaging, makes finished product.
According to above scheme, the temperature heated up in described step 1) is 60 DEG C, and churning time is 30 minutes.
According to above scheme, described step 2) in the temperature of constant temperature be 80 DEG C, the reaction times is 2.5 hours.
According to above scheme, in described step 3), the temperature of constant temperature is 80 DEG C, and churning time is 20 minutes.
According to above scheme, in described step 4), the temperature of constant temperature is 80 DEG C, and the reaction times is 2 hours.
According to above scheme, in described step 5), the temperature of constant temperature is 80 DEG C, and churning time is 15 minutes, and described theoretical solid content is 29-31%.
According to above scheme, be cooled to 50 DEG C in described step 6), churning time is 20 minutes, and qualified viscosity is 120000-150000 CPS/25 DEG C, and described pressure becomes auxiliary agent into silicone based pressure change auxiliary agent
The invention has the beneficial effects as follows:
1) to have pressure temperature low for product of the present invention, and 140-160 DEG C can pressing variable color, and color even, and variable color is stablized;
2) product organic solvent of the present invention is low, and it is residual low to below 10ppm for the synthetic leather organic solvent after washing, can reach European environmental requirement and remain;
3) preparation method's technique of the present invention is simple, workable.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described.
embodiment 1:
The invention provides a kind of environment-friendly type leather low temperature wet method pressure and become urethane resin and preparation method thereof, comprise the steps:
1) 0.48 kg poly adipate succinic acid ester polyvalent alcohol, 0.1 kg polycaprolactone polyol and 0.6 kg dimethyl formamide are dropped into glass reaction still, be warming up to 60 DEG C, stir 30 minutes;
2) 0.05 kg diphenylmethanediisocyanate is dropped into reactor, be warming up to 80 DEG C of reactions 2.5 hours, make prepolymer;
3) 0.86 kg dimethyl formamide, 0.03 kg ethylene glycol, 0.053 kg 1.4-butyleneglycol are dropped into reactor, constant temperature 80 DEG C, stirs 20 minutes;
4) divide and carry out thickening reaction by 0.27 kg diphenylmethanediisocyanate input reactor three times, detect viscosity, viscosity is defective, continue to add a small amount of diphenylmethanediisocyanate, carry out thickening reaction, until viscosity is qualified, constant temperature 80 DEG C, reaction totally 2 hours;
5) 0.4 kg dimethyl formamide is dropped into, constant temperature 80 DEG C, agitation and dilution 15 minutes, to setting theoretical solid content 30%;
6) again carry out viscosimetric analysis, viscosity is 130000 CPS/25 DEG C, qualified, be cooled to 50 DEG C, add the methylol-modified silicone oil of 0.004 kg, the silicone based pressure of 0.009 kg become auxiliary agent, 0.26 kg dimethyl formamide, stir 20 minutes, discharging, packaging, make finished product.
embodiment 2:
The invention provides a kind of environment-friendly type leather low temperature wet method pressure and become urethane resin and preparation method thereof, comprise the steps:
1) 0.6 kg poly adipate succinic acid ester polyvalent alcohol, 0.25 kg polycaprolactone polyol and 1.05 kg dimethyl formamides are dropped into glass reaction still, be warming up to 60 DEG C, stir 30 minutes;
2) 0.05 kg diphenylmethanediisocyanate is dropped into reactor, be warming up to 80 DEG C of reactions 2.5 hours, make prepolymer;
3) 1.4 kg dimethyl formamides, 0.04 kg ethylene glycol, 0.15 kg 1.4-butyleneglycol are dropped into reactor, constant temperature 80 DEG C, stirs 20 minutes;
4) divide and carry out thickening reaction by 0.336 kg diphenylmethanediisocyanate input reactor three times, detect viscosity, viscosity is defective, continue to add a small amount of diphenylmethanediisocyanate, carry out thickening reaction, until viscosity is qualified, constant temperature 80 DEG C, reaction totally 2 hours;
5) 0.7 kg dimethyl formamide is dropped into, constant temperature 80 DEG C, agitation and dilution 15 minutes, to setting theoretical solid content 29%;
6) again carry out viscosimetric analysis, viscosity is 120000 CPS/25 DEG C, qualified, be cooled to 50 DEG C, add the methylol-modified silicone oil of 0.005 kg, the silicone based pressure of 0.01 kg become auxiliary agent, 0.35 kg dimethyl formamide, stir 20 minutes, discharging, packaging, make finished product.
embodiment 3:
The invention provides a kind of environment-friendly type leather low temperature wet method pressure and become urethane resin and preparation method thereof, comprise the steps:
1) 0.64 kg poly adipate succinic acid ester polyvalent alcohol, 0.12 kg polycaprolactone polyol and 0.84 kg dimethyl formamide are dropped into glass reaction still, be warming up to 60 DEG C, stir 30 minutes;
2) 0.06 kg diphenylmethanediisocyanate is dropped into reactor, be warming up to 80 DEG C of reactions 2.5 hours, make prepolymer;
3) 1.12 kg dimethyl formamides, 0.04 kg ethylene glycol, 0.12 kg 1.4-butyleneglycol are dropped into reactor, constant temperature 80 DEG C, stirs 20 minutes;
4) divide and carry out thickening reaction by 0.3 kg diphenylmethanediisocyanate input reactor three times, detect viscosity, viscosity is defective, continue to add a small amount of diphenylmethanediisocyanate, carry out thickening reaction, until viscosity is qualified, constant temperature 80 DEG C, reaction totally 2 hours;
5) 0.56 kg dimethyl formamide is dropped into, constant temperature 80 DEG C, agitation and dilution 15 minutes, to setting theoretical solid content 31%;
6) again carry out viscosimetric analysis, viscosity is 150000 CPS/25 DEG C, qualified, be cooled to 50 DEG C, add the methylol-modified silicone oil of 0.012 kg, the silicone based pressure of 0.02 kg become auxiliary agent, 0.28 kg dimethyl formamide, stir 20 minutes, discharging, packaging, make finished product.
Above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although above-described embodiment is to invention has been detailed description, the person skilled of this area is to be understood that: can modify to the present invention or replace on an equal basis, but any amendment not departing from spirit and scope of the invention all should be encompassed in right of the present invention with local replacement.
Claims (8)
1. an environment-friendly type leather low temperature wet method pressure becomes urethane resin, it is characterized in that, processed by following component and mass fraction thereof: diphenylmethanediisocyanate 8-10 part, poly adipate succinic acid ester polyvalent alcohol 12-16 part, polycaprolactone polyol 3-5 part, ethylene glycol 0.8-1 part, 1.4-butyleneglycol 1-3 part, pressure become auxiliary agent 0.2-0.4 part, methylol-modified silicone oil 0.01-0.03 part, dimethyl formamide 68-70 part.
2. environment-friendly type leather low temperature wet method pressure according to claim 1 becomes the preparation method of urethane resin, it is characterized in that, comprises the steps:
1) poly adipate succinic acid ester polyvalent alcohol, polycaprolactone polyol, 28-31 wt% dimethyl formamide are dropped into glass reaction still, heat up and stir;
2) 12-17 wt% diphenylmethanediisocyanate is dropped into reactor, isothermal reaction, makes prepolymer;
3) ethylene glycol, 1.4-butyleneglycol, 39-41 wt% dimethyl formamide are dropped into reactor, constant temperature stirs;
4) thickening reaction is carried out in 83-88 wt% diphenylmethanediisocyanate input reactor under constant temperature;
5) drop into 18-21 wt% dimethyl formyl, constant temperature agitation and dilution is to setting theoretical solid content;
6) carry out viscosimetric analysis, if viscosity is defective, then add diphenylmethanediisocyanate thickening, the qualified rear cooling of viscosity, add methylol-modified silicone oil, pressure becomes auxiliary agent, remain dimethyl formamide, stirs, discharging, packaging, makes finished product.
3. environment-friendly type leather low temperature wet method pressure according to claim 2 becomes the preparation method of urethane resin, and it is characterized in that, the temperature heated up in described step 1) is 60 DEG C, and churning time is 30 minutes.
4. environment-friendly type leather low temperature wet method according to claim 2 pressure becomes the preparation method of urethane resin, it is characterized in that, described step 2) in the temperature of constant temperature be 80 DEG C, the reaction times is 2.5 hours.
5. environment-friendly type leather low temperature wet method pressure according to claim 2 becomes the preparation method of urethane resin, and it is characterized in that, in described step 3), the temperature of constant temperature is 80 DEG C, and churning time is 20 minutes.
6. environment-friendly type leather low temperature wet method pressure according to claim 2 becomes the preparation method of urethane resin, and it is characterized in that, in described step 4), the temperature of constant temperature is 80 DEG C, and the reaction times is 2 hours.
7. environment-friendly type leather low temperature wet method pressure according to claim 2 becomes the preparation method of urethane resin, and it is characterized in that, in described step 5), the temperature of constant temperature is 80 DEG C, and churning time is 15 minutes, and described theoretical solid content is 29-31%.
8. environment-friendly type leather low temperature wet method pressure according to claim 2 becomes the preparation method of urethane resin, it is characterized in that, 50 DEG C are cooled in described step 6), churning time is 20 minutes, qualified viscosity is 120000-150000 CPS/25 DEG C, and described pressure becomes auxiliary agent into silicone based pressure change auxiliary agent.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510264873.8A CN104844780B (en) | 2015-05-22 | 2015-05-22 | A kind of environment-friendly type leather low temperature wet method buckling polyurethane resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510264873.8A CN104844780B (en) | 2015-05-22 | 2015-05-22 | A kind of environment-friendly type leather low temperature wet method buckling polyurethane resin and preparation method thereof |
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| CN104844780A true CN104844780A (en) | 2015-08-19 |
| CN104844780B CN104844780B (en) | 2018-04-24 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108641062A (en) * | 2018-05-25 | 2018-10-12 | 清远市番亿聚氨酯有限公司 | A kind of middle modulus, the preparation method of high springback wet method resin |
| CN109705295A (en) * | 2018-08-17 | 2019-05-03 | 旭川化学（苏州）有限公司 | A kind of packaging leather polyurethane resin and preparation method thereof, application method |
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|---|---|---|---|---|
| US5474810A (en) * | 1994-06-29 | 1995-12-12 | Hofa Trading Co., Ltd. | Process for producing PU suede-type synthetic leather |
| CN101503498A (en) * | 2009-03-11 | 2009-08-12 | 合肥安利化工有限公司 | Wet-type high cracking resistance, high wear resistance and high peel strength polyurethane resin and preparation thereof |
| CN101503499A (en) * | 2009-03-11 | 2009-08-12 | 合肥安利化工有限公司 | Wet low modulus ultra-soft high peel strength polyurethane resin for synthetic leather and preparation thereof |
| CN103304769A (en) * | 2013-06-06 | 2013-09-18 | 广东伊诗德新材料科技有限公司 | High-wear-resistant polyurethane resin for synthetic leather and preparation method thereof |
| CN103304770A (en) * | 2013-06-06 | 2013-09-18 | 广东伊诗德新材料科技有限公司 | High-temperature-resistant polyurethane resin for synthetic leather and preparation method thereof |
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2015
- 2015-05-22 CN CN201510264873.8A patent/CN104844780B/en active Active
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|---|---|---|---|---|
| US5474810A (en) * | 1994-06-29 | 1995-12-12 | Hofa Trading Co., Ltd. | Process for producing PU suede-type synthetic leather |
| CN101503498A (en) * | 2009-03-11 | 2009-08-12 | 合肥安利化工有限公司 | Wet-type high cracking resistance, high wear resistance and high peel strength polyurethane resin and preparation thereof |
| CN101503499A (en) * | 2009-03-11 | 2009-08-12 | 合肥安利化工有限公司 | Wet low modulus ultra-soft high peel strength polyurethane resin for synthetic leather and preparation thereof |
| CN103304769A (en) * | 2013-06-06 | 2013-09-18 | 广东伊诗德新材料科技有限公司 | High-wear-resistant polyurethane resin for synthetic leather and preparation method thereof |
| CN103304770A (en) * | 2013-06-06 | 2013-09-18 | 广东伊诗德新材料科技有限公司 | High-temperature-resistant polyurethane resin for synthetic leather and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《皮鞋材料编写组》: "《皮鞋材料》", 31 December 1996 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108641062A (en) * | 2018-05-25 | 2018-10-12 | 清远市番亿聚氨酯有限公司 | A kind of middle modulus, the preparation method of high springback wet method resin |
| CN109705295A (en) * | 2018-08-17 | 2019-05-03 | 旭川化学（苏州）有限公司 | A kind of packaging leather polyurethane resin and preparation method thereof, application method |
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| Publication number | Publication date |
|---|---|
| CN104844780B (en) | 2018-04-24 |
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