CN102352100A - Fast cured two-liquid type non-yellowing polyurethane bonding layer resin for synthetic leather and preparation method thereof - Google Patents
Fast cured two-liquid type non-yellowing polyurethane bonding layer resin for synthetic leather and preparation method thereof Download PDFInfo
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- CN102352100A CN102352100A CN 201110160068 CN201110160068A CN102352100A CN 102352100 A CN102352100 A CN 102352100A CN 201110160068 CN201110160068 CN 201110160068 CN 201110160068 A CN201110160068 A CN 201110160068A CN 102352100 A CN102352100 A CN 102352100A
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Abstract
The invention belongs to polyurethane elastic body materials and particularly relates to fast cured two-liquid type non-yellowing polyurethane bonding layer resin for synthetic leather and a preparation method thereof, which adopt the technical scheme that the fast cured two-liquid type non-yellowing polyurethane bonding layer resin for the synthetic leather is characterized by comprising polymer glycol compounds, diisocyanate, chain expanding agents, catalysts, solvents and auxiliary agents, wherein the polymer glycol compounds comprise polyether glycol compounds and polyester glycol compounds in weight percentage of 6/4 to 9/1. When the scheme is adopted, the existing problems are solved, and the fast cured two-liquid type non-yellowing polyurethane bonding layer resin for the synthetic leather and the preparation method are provided.
Description
Technical field
The invention belongs to polyurethane elastomer material, particularly a kind of use for synthetic leather fast setting binary liquid shape is yellow stain polyurethane adhesive linkage resin and preparation method thereof not.
Background technology
The binary liquid shape adhesive linkage urethane resin kind of Ying Yonging is more in the market, is prepared from but be common aromatic diisocyanate, and not xanthochromic binary liquid shape adhesive linkage urethane resin does not also have product to occur so far, and does not have relevant document and patent report.Being prone to xanthochromia property is the common fault of Synthetic Leather product; Some urethane resins high-grade, that synthetic leather goods white or light color system use are to be synthesized by the aliphatic diisocyanate reaction; But when using, expose defectives such as bonding strength is low, set time slow, the leather sense is hard partially, folding quality is bad as adhesive linkage; Therefore most of not adhesive linkage resins of yellow stain polyurethane synthetic leather all are common adhesive linkage resins, and the time has been grown the leather surface still can yellowing.
Summary of the invention
The present invention overcomes existing issue, and not yellow stain polyurethane adhesive linkage resin and preparation method thereof of a kind of use for synthetic leather fast setting binary liquid shape is provided.
Realize above-mentioned purpose; The present invention adopts following technical scheme; A kind of use for synthetic leather fast setting binary liquid shape is yellow stain polyurethane adhesive linkage resin not; It is characterized in that: include macromolecule diol compound, vulcabond, chainextender, catalyzer, solvent, auxiliary agent; Wherein the macromolecule diol compound comprises polyether Glycols compound and polyester binary alkylol cpd, and the weight percent of said polyether Glycols and polyester diol is 6 ﹕, 4～9 ﹕ 1.
Above-mentioned use for synthetic leather fast setting binary liquid shape not yellow stain polyurethane adhesive linkage resin with after solidifying agent and promotor cooperate; Be applied in the adhesive linkage of synthetic leather; Set time is fast; Stripping strength is high; The synthetic leather good hand feeling that makes, folding line is thin and recover fast, and folding quality is superior; Be difficult for xanthochromia, more be applicable to white and light synthetic leather goods.
Further setting of the present invention is: described polyether Glycols compound is one or more the mixture in polytetramethylene ether dibasic alcohol, polyoxyethylene ether dibasic alcohol, polyoxytrimethylene ether dibasic alcohol, polyoxyethylene-propylene oxide copolyether dibasic alcohol, polytetrahydrofuran-ethylene oxide copolyether glycol, the polytetrahydrofuran-propylene oxide copolyether glycol; Described polyester binary alkylol cpd is one or more the mixture in PCDL, polycaprolactone dibasic alcohol, the polyester adipate dibasic alcohol; Described polyester adipate dibasic alcohol is polyester adipate dibasic alcohol or the straight chain alkane two pure and mild copolymerization polyester adipate dibasic alcohol with alkane glycol of side chain with alkane glycol of side chain; The number-average molecular weight of macromolecule diol is 1000～4000g/mol; Described vulcabond is an aliphatic diisocyanate; Include one or more the mixture in isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, the cyclohexanedimethyleterephthalate vulcabond, the vulcabond consumption accounts for 14～18% of total resin weight; Described chainextender is terepthaloyl moietie, Ucar 35,2-methyl isophthalic acid; 3 Ucar 35,1,4-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, glycol ether, 3-methyl isophthalic acid; The mixture of one or more in the 5-pentanediol, the chainextender consumption accounts for 2～5% of total resin weight; Described solvent is N, and the mixture of one or more in dinethylformamide, butanone, toluene, the ethyl acetate, weight of solvent account for 38～42% of total resin weight; Described auxiliary agent is the mixture of oxidation inhibitor, UV light absorber, photostabilizer; Described catalyzer is environment-friendly type organo-bismuth and organic silver class catalyzer, and with respect to urethane resin, usage quantity is no more than 1 weight ‰.
Preparing method's of the present invention technical scheme is: described urethane resin preparation method is the amount of owing method; Concrete steps are for to drop into described macromolecule diol, chainextender, partial solvent and auxiliary agent in the reaction kettle in the lump; Stir; The vulcabond that in batches adds is in 90～110 ℃ of reactions down again; After qualified viscosity; Add residual solvent, add auxiliary agent at last.
Embodiment
Below further specify the technical scheme of the present invention protection through specific examples, but following instance and do not mean that restriction protection scope of the present invention.
Embodiment one
Material name weight (unit: kilogram)
Polytetramethylene ether dibasic alcohol (molecular weight 2000) 80
Gather hexanodioic acid-2-methyl isophthalic acid, ammediol ester dibasic alcohol (molecular weight 2000) 60
Polyoxytrimethylene ether dibasic alcohol 60
Terepthaloyl moietie 13.5
Isophorone diisocyanate (IPDI) 70.5
Oxidation inhibitor 245 0.5
UV light absorber Tinuvin101 1
Photostabilizer 765 1
Butanone (MEK) 76
N, dinethylformamide (DMF) 114
Preparation process is following: with 80 kilograms of above-mentioned polytetramethylene ether dibasic alcohol, gather hexanodioic acid-2-methyl isophthalic acid; 60 kilograms of ammediol ester dibasic alcohol, 60 kilograms of polyoxytrimethylene ether dibasic alcohol, 13.5 kilograms of terepthaloyl moietie, 0.5 kilogram in oxidation inhibitor and DMF65 kilogram drop in the reaction kettle in the lump; Stir; Add IPDI more in batches; In 90～120 ℃ of reactions down, add residue DMF and MEK, allotment to qualified viscosity and solid content; Add UV light absorber, photostabilizer at last, stir.
Embodiment two
Material name weight (unit: kilogram)
Polytetramethylene ether dibasic alcohol (molecular weight 2000) 140
Gather hexanodioic acid-1,4-butyleneglycol-3-methyl isophthalic acid, 5-pentadiol ester dibasic alcohol (molecular weight 2000) 60
Terepthaloyl moietie 14
IPDI 72.3
Oxidation inhibitor 245 0.5
UV light absorber Tinuvin101 1
Photostabilizer 765 1
MEK 57.7
DMF 134.8
Preparation process is following: with 140 kilograms of above-mentioned polytetramethylene ether dibasic alcohol, gather hexanodioic acid-1; 4-butyleneglycol-3-methyl isophthalic acid; 60 kilograms of 5-pentadiol ester dibasic alcohol, 14 kilograms of terepthaloyl moietie, 0.5 kilogram in oxidation inhibitor and DMF67.4 kilogram drop in the reaction kettle in the lump; Stir, add IPDI more in batches, in 90～120 ℃ of reactions down; Add residue DMF and MEK; Allotment to qualified viscosity and solid content adds UV light absorber, photostabilizer at last, stirs.
Embodiment three
Material name weight (unit: kilogram)
Polytetramethylene ether dibasic alcohol (molecular weight 3000) 135
Gather hexanodioic acid-DOPCP dibasic alcohol (molecular weight 2000) 40
Polytetrahydrofuran-ethylene oxide copolyether glycol (molecular weight 2000) 70
1,4-butyleneglycol 22.5
IPDI 77.7
Oxidation inhibitor 245 0.5
UV light absorber Tinuvin101 1
Photostabilizer 765 1
MEK 58
DMF 173.8
Preparation process is following: with 135 kilograms of above-mentioned polytetramethylene ether dibasic alcohol, gather 70 kilograms of hexanodioic acid-40 kilograms of DOPCP dibasic alcohol, polytetrahydrofuran-ethylene oxide copolyether glycol, 1; 22.5 kilograms of 4-butyleneglycols, 0.5 kilogram in oxidation inhibitor and DMF74.2 kilogram drop in the reaction kettle in the lump; Stir; Add IPDI more in batches; In 90～120 ℃ of reactions down; Add residue DMF and MEK; Allotment to qualified viscosity and solid content; Add UV light absorber, photostabilizer at last, stir.
Embodiment four
Material name weight (unit: kilogram)
Polytetramethylene ether dibasic alcohol (molecular weight 2000) 120
Polycaprolactone dibasic alcohol (molecular weight 2000) 40
Polyoxyethylene-propylene oxide copolyether dibasic alcohol (molecular weight 3000) 60
1,6-hexylene glycol 14.2
Terepthaloyl moietie 11.2
IPDI 89
Oxidation inhibitor 245 0.5
UV light absorber Tinuvin101 1
Photostabilizer 765 1
MEK 67
DMF 157
Preparation process is following: with 60 kilograms of above-mentioned polytetramethylene ether dibasic alcohol 120 kgs, 40 kilograms of polycaprolactone dibasic alcohol, polyoxyethylene-propylene oxide copolyether dibasic alcohol, 1; 14.2 kilograms of 6-hexylene glycols, 11.2 kilograms of terepthaloyl moietie, 0.5 kilogram in oxidation inhibitor and DMF78 kilogram drop in the reaction kettle in the lump; Stir; Add IPDI more in batches; In 90～120 ℃ of reactions down; Add residue DMF and MEK; Allotment to qualified viscosity and solid content; Add UV light absorber, photostabilizer at last, stir.
Embodiment five
Material name weight (unit: kilogram)
Polytetramethylene ether dibasic alcohol (molecular weight 2000) 140
Gather hexanodioic acid-terepthaloyl moietie-2-methyl isophthalic acid, ammediol ester dibasic alcohol (molecular weight 2000) 60
Terepthaloyl moietie 15.5
IPDI 46.6
Cyclohexanedimethyleterephthalate vulcabond 36.6
Oxidation inhibitor 245 0.5
UV light absorber Tinuvin101 1
Photostabilizer 765 1
MEK 60
DMF 140
Preparation process is following: with 140 kilograms of above-mentioned polytetramethylene ether dibasic alcohol, gather hexanodioic acid-terepthaloyl moietie-2-methyl isophthalic acid; 60 kilograms of ammediol ester dibasic alcohol, 15.5 kilograms of terepthaloyl moietie, 0.5 kilogram in oxidation inhibitor and DMF49 kilogram drop in the reaction kettle in the lump; Stir; Add IPDI and cyclohexanedimethyleterephthalate vulcabond again in 90～120 ℃ of reactions down in batches; Add residue DMF and MEK; Allotment to qualified viscosity and solid content; Add UV light absorber, photostabilizer at last, stir.
Comparison example one
Material name weight (unit: kilogram)
Polytetramethylene ether dibasic alcohol (molecular weight 2000) 80
Gather hexanodioic acid-2-methyl isophthalic acid, ammediol ester dibasic alcohol (molecular weight 2000) 60
Polyoxytrimethylene ether dibasic alcohol 60
Terepthaloyl moietie 13.5
Diphenylmethanediisocyanate (MDI) 79.4
Oxidation inhibitor 245 0.5
UV light absorber Tinuvin101 1
Photostabilizer 765 1
Butanone (MEK) 76
N, dinethylformamide (DMF) 120
Preparation process is following: with 80 kilograms of above-mentioned polytetramethylene ether dibasic alcohol, gather hexanodioic acid-2-methyl isophthalic acid; 60 kilograms of ammediol ester dibasic alcohol, 60 kilograms of polyoxytrimethylene ether dibasic alcohol, 13.5 kilograms of terepthaloyl moietie, 0.5 kilogram in oxidation inhibitor and DMF98 kilogram drop in the reaction kettle in the lump; Stir; Add MDI more in batches; In 70～80 ℃ of reactions down; Constantly add residue DMF and MEK control viscosity, add UV light absorber, photostabilizer, stir to the qualified back of viscosity.
Comparison example two
Material name weight (unit: kilogram)
Polytetramethylene ether dibasic alcohol (molecular weight 2000) 80
Gather hexanodioic acid-2-methyl isophthalic acid, ammediol ester dibasic alcohol (molecular weight 2000) 60
Polyoxytrimethylene ether dibasic alcohol 60
Isophorone diamine 37
Isophorone diisocyanate (IPDI) 70.5
Oxidation inhibitor 245 0.5
UV light absorber Tinuvin101 1
Photostabilizer 765 1
Butanone (MEK) 93
N, dinethylformamide (DMF) 217
Preparation process is following: with 80 kilograms of above-mentioned polytetramethylene ether dibasic alcohol, gather hexanodioic acid-2-methyl isophthalic acid; 60 kilograms of ammediol ester dibasic alcohol, 60 kilograms of polyoxytrimethylene ether dibasic alcohol, IPDI70.5 kilogram, 0.5 kilogram in oxidation inhibitor and DMF47 kilogram drop in the reaction kettle in the lump; Stir; Reacted three hours down in 90～120 ℃; Add DMF and MEK again; Under 40～60 ℃, slowly drip isophorone diamine; To qualified viscosity; Add UV light absorber, photostabilizer at last, stir.
Comparison example three
Material name weight (unit: kilogram)
Polytetramethylene ether dibasic alcohol (molecular weight 2000) 140
Gather hexanodioic acid-1,4-butanediol ester dibasic alcohol (molecular weight 2000) 60
Terepthaloyl moietie 15.5
IPDI 77.6
Oxidation inhibitor 245 0.5
UV light absorber Tinuvin101 1
Photostabilizer 765 1
MEK 60
DMF 140
Preparation process is following: with 140 kilograms of above-mentioned polytetramethylene ether dibasic alcohol, gather hexanodioic acid-1; 60 kilograms of 4-butanediol ester dibasic alcohol, 15.5 kilograms of terepthaloyl moietie, 0.5 kilogram in oxidation inhibitor and DMF60 kilogram drop in the reaction kettle in the lump; Stir; Add IPDI more in batches; In 90～120 ℃ of reactions down, add residue DMF and MEK, allotment to qualified viscosity and solid content; Add UV light absorber, photostabilizer at last, stir.
Comparison example four
Material name weight (unit: kilogram)
Polytetramethylene ether dibasic alcohol (molecular weight 2000) 60
Gather hexanodioic acid-1,4-butyleneglycol-3-methyl isophthalic acid, 5-pentadiol ester dibasic alcohol (molecular weight 2000) 140
Terepthaloyl moietie 14
IPDI 72.3
Oxidation inhibitor 245 0.5
UV light absorber Tinuvin101 1
Photostabilizer 765 1
MEK 57.7
DMF 134.8
Preparation process is following: with 60 kilograms of above-mentioned polytetramethylene ether dibasic alcohol, gather hexanodioic acid-1; 4-butyleneglycol-3-methyl isophthalic acid; 140 kilograms of 5-pentadiol ester dibasic alcohol, 14 kilograms of terepthaloyl moietie, 0.5 kilogram in oxidation inhibitor and DMF67.4 kilogram drop in the reaction kettle in the lump; Stir, add IPDI more in batches, in 90～120 ℃ of reactions down; Add residue DMF and MEK; Allotment to qualified viscosity and solid content adds UV light absorber, photostabilizer at last, stirs.
Comparison example 1 changes aliphatic diisocyanate IPDI into aromatic diisocyanate MDI; Comparison example 2 is utilized the no xanthochromia preparation method of usual overflow method, and chainextender is an isophorone diamine; What comparison example 3 polyester diol changed straight chain alkane glycol into gathers the hexanodioic acid dibasic alcohol; The ratio of polyether Glycols and polyester diol is 3:7 in the comparison example 4.
The polyurethane leather of the foregoing description and comparison example preparation is processed synthetic leather sample by the dry method leather-making technology as adhesive linkage with resin, test each item fundamental property, the result is as shown in table 1, and process hides is filled a prescription as follows:
Resin 100
DMF 30
MEK 30
Solidifying agent 6～12
Promotor 1～5
Stock white is an amount of
The present invention is applied in the adhesive linkage of Synthetic Leather, and set time is fast, and stripping strength is high, the synthetic leather good hand feeling that makes, and folding line is thin and recover fast, and folding quality is superior, is difficult for xanthochromia, more is applicable to white and light synthetic leather goods.
Table 1 embodiment and comparison example detect the performance table
Among them, the storage instability Comparative Example 3, the resin is easily crystallized, loss of mobility.
Claims (10)
1. use for synthetic leather fast setting binary liquid shape yellow stain polyurethane adhesive linkage resin not; It is characterized in that: include macromolecule diol compound, vulcabond, chainextender, catalyzer, solvent, auxiliary agent; Wherein the macromolecule diol compound comprises polyether Glycols compound and polyester binary alkylol cpd, and the weight percent of said polyether Glycols compound and polyester binary alkylol cpd is 6 ﹕, 4～9 ﹕ 1.
2. use for synthetic leather fast setting binary liquid shape according to claim 1 is yellow stain polyurethane adhesive linkage resin not, it is characterized in that: described polyether Glycols compound is one or more the mixture in polytetramethylene ether dibasic alcohol, polyoxyethylene ether dibasic alcohol, polyoxytrimethylene ether dibasic alcohol, polyoxyethylene-propylene oxide copolyether dibasic alcohol, polytetrahydrofuran-ethylene oxide copolyether glycol, the polytetrahydrofuran-propylene oxide copolyether glycol; Described polyester binary alkylol cpd is one or more the mixture in PCDL, polycaprolactone dibasic alcohol, the polyester adipate dibasic alcohol.
3. use for synthetic leather fast setting binary liquid shape according to claim 2 is yellow stain polyurethane adhesive linkage resin not, it is characterized in that: described polyester adipate dibasic alcohol is polyester adipate dibasic alcohol or the straight chain alkane two pure and mild copolymerization polyester adipate dibasic alcohol with alkane glycol of side chain with alkane glycol of side chain.
4. according to the described use for synthetic leather fast setting of claim 1～3 binary liquid shape yellow stain polyurethane adhesive linkage resin not, it is characterized in that: the number-average molecular weight of macromolecule diol is 1000～4000g/mol.
5. use for synthetic leather fast setting binary liquid shape according to claim 1 is yellow stain polyurethane adhesive linkage resin not; It is characterized in that: described vulcabond is an aliphatic diisocyanate; Include one or more the mixture in isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, the cyclohexanedimethyleterephthalate vulcabond, the consumption of vulcabond accounts for 14～18% of total resin weight.
6. according to claim 1 or 2 or 3 or 5 described use for synthetic leather fast setting binary liquid shapes yellow stain polyurethane adhesive linkage resin not; It is characterized in that: described chainextender is terepthaloyl moietie, Ucar 35,2-methyl isophthalic acid; 3 Ucar 35,1; 4-butyleneglycol, 1; 6-hexylene glycol, neopentyl glycol, glycol ether, 3-methyl isophthalic acid; The mixture of one or more in the 5-pentanediol, the chainextender consumption accounts for 2～5% of total resin weight.
7. according to claim 1 or 2 or 3 or 5 described use for synthetic leather fast setting binary liquid shapes yellow stain polyurethane adhesive linkage resin not; It is characterized in that: described solvent is N; The mixture of one or more in dinethylformamide, butanone, toluene, the ethyl acetate, weight of solvent account for 38～42% of total resin weight.
8. according to claim 1 or 2 or 3 or 5 described use for synthetic leather fast setting binary liquid shapes yellow stain polyurethane adhesive linkage resin not, it is characterized in that: described auxiliary agent is the mixture of oxidation inhibitor, UV light absorber, photostabilizer.
9. according to claim 1 or 2 or 3 or 5 described use for synthetic leather fast setting binary liquid shapes yellow stain polyurethane adhesive linkage resin not; It is characterized in that: described catalyzer is environment-friendly type organo-bismuth and organic silver class catalyzer; With respect to urethane resin, usage quantity is no more than 1 weight ‰.
10. use for synthetic leather fast setting binary liquid shape of the present invention is the preparation method of yellow stain polyurethane adhesive linkage resin not; It is characterized in that: described urethane resin preparation method is the amount of owing method; Concrete steps are for to drop into described macromolecule diol, chainextender, partial solvent and auxiliary agent in the reaction kettle in the lump; Stir; The vulcabond that in batches adds is in 90～110 ℃ of reactions down again; After qualified viscosity, add residual solvent, add auxiliary agent at last.
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| CN 201110160068 CN102352100A (en) | 2011-06-15 | 2011-06-15 | Fast cured two-liquid type non-yellowing polyurethane bonding layer resin for synthetic leather and preparation method thereof |
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| CN 201110160068 CN102352100A (en) | 2011-06-15 | 2011-06-15 | Fast cured two-liquid type non-yellowing polyurethane bonding layer resin for synthetic leather and preparation method thereof |
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| CN103435773A (en) * | 2013-09-11 | 2013-12-11 | 侯马飞 | Polyurethane resin for synthetic leather with high water pressure resistance |
| CN103755917A (en) * | 2013-12-26 | 2014-04-30 | 浙江华峰合成树脂有限公司 | Polyurethane bonding layer resin for clothing leather, and preparation method and application thereof |
| CN104277202A (en) * | 2014-10-11 | 2015-01-14 | 浙江华峰合成树脂有限公司 | Polyurethane resin for hydrolysis-resistant film nubuck and preparation method of polyurethane resin |
| CN104513355A (en) * | 2013-09-26 | 2015-04-15 | 苏州富仁化工有限公司 | Preparation method for cold resistant and moisture permeable polyurethane resin |
| CN104987490A (en) * | 2014-11-11 | 2015-10-21 | 淮安凯悦科技开发有限公司 | Non-yellowing polyurethane resin preparation method |
| CN106750084A (en) * | 2016-11-25 | 2017-05-31 | 上海华峰超纤材料股份有限公司 | High solids content two-liquid type bonding layer polyurethane resin and preparation method thereof |
| CN109232856A (en) * | 2018-08-03 | 2019-01-18 | 山东诺威聚氨酯股份有限公司 | The preparation method of high highly-elastic urethane elastomer thoroughly |
| CN110205836A (en) * | 2019-05-13 | 2019-09-06 | 浙江禾欣新材料有限公司 | A kind of white shoes super fiber leather and preparation method thereof of resistance to vulcanization xanthochromia |
| CN110746573A (en) * | 2019-11-15 | 2020-02-04 | 江苏华大新材料有限公司 | Yellowing-resistant two-liquid type polyurethane adhesive for reflective material and preparation method thereof |
| CN110818879A (en) * | 2019-11-15 | 2020-02-21 | 江苏华大新材料有限公司 | Polyurethane resin for folding white-mark-free fabric coating and preparation method thereof |
| CN113529430A (en) * | 2021-07-08 | 2021-10-22 | 苏州贝斯特装饰新材料有限公司 | Yellowing-resistant PVC synthetic leather for PU sponge composition and composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103435773A (en) * | 2013-09-11 | 2013-12-11 | 侯马飞 | Polyurethane resin for synthetic leather with high water pressure resistance |
| CN103435773B (en) * | 2013-09-11 | 2015-07-29 | 侯马飞 | A kind of high water pressure resistance use for synthetic leather urethane resin |
| CN104513355A (en) * | 2013-09-26 | 2015-04-15 | 苏州富仁化工有限公司 | Preparation method for cold resistant and moisture permeable polyurethane resin |
| CN103755917A (en) * | 2013-12-26 | 2014-04-30 | 浙江华峰合成树脂有限公司 | Polyurethane bonding layer resin for clothing leather, and preparation method and application thereof |
| CN103755917B (en) * | 2013-12-26 | 2016-01-20 | 浙江华峰合成树脂有限公司 | Clothing leather polyurethane adhesive layer resin and method for making thereof and application |
| CN104277202A (en) * | 2014-10-11 | 2015-01-14 | 浙江华峰合成树脂有限公司 | Polyurethane resin for hydrolysis-resistant film nubuck and preparation method of polyurethane resin |
| CN104277202B (en) * | 2014-10-11 | 2017-03-01 | 浙江华峰合成树脂有限公司 | Water-fast degrading film Niu Bage polyurethane resin and preparation method |
| CN104987490A (en) * | 2014-11-11 | 2015-10-21 | 淮安凯悦科技开发有限公司 | Non-yellowing polyurethane resin preparation method |
| CN106750084A (en) * | 2016-11-25 | 2017-05-31 | 上海华峰超纤材料股份有限公司 | High solids content two-liquid type bonding layer polyurethane resin and preparation method thereof |
| CN109232856A (en) * | 2018-08-03 | 2019-01-18 | 山东诺威聚氨酯股份有限公司 | The preparation method of high highly-elastic urethane elastomer thoroughly |
| CN109232856B (en) * | 2018-08-03 | 2021-04-09 | 山东一诺威聚氨酯股份有限公司 | Preparation method of high-permeability high-elasticity polyurethane elastomer |
| CN110205836A (en) * | 2019-05-13 | 2019-09-06 | 浙江禾欣新材料有限公司 | A kind of white shoes super fiber leather and preparation method thereof of resistance to vulcanization xanthochromia |
| CN110746573A (en) * | 2019-11-15 | 2020-02-04 | 江苏华大新材料有限公司 | Yellowing-resistant two-liquid type polyurethane adhesive for reflective material and preparation method thereof |
| CN110818879A (en) * | 2019-11-15 | 2020-02-21 | 江苏华大新材料有限公司 | Polyurethane resin for folding white-mark-free fabric coating and preparation method thereof |
| CN110746573B (en) * | 2019-11-15 | 2021-11-23 | 江苏华大新材料有限公司 | Yellowing-resistant two-liquid type polyurethane adhesive for reflective material and preparation method thereof |
| CN113529430A (en) * | 2021-07-08 | 2021-10-22 | 苏州贝斯特装饰新材料有限公司 | Yellowing-resistant PVC synthetic leather for PU sponge composition and composite material |
| WO2023279572A1 (en) * | 2021-07-08 | 2023-01-12 | 苏州贝斯特装饰新材料有限公司 | Yellowing-resistant pvc synthetic leather for compounding pu sponge and composite material |
| CN113882165A (en) * | 2021-10-12 | 2022-01-04 | 世联汽车内饰（苏州）有限公司 | Anti-corrosion PU synthetic leather and preparation method thereof |
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Application publication date: 20120215 |