CN109666127A - Use for synthetic leather Self-leveling light-cured polyurethane resin and preparation method thereof - Google Patents
Use for synthetic leather Self-leveling light-cured polyurethane resin and preparation method thereof Download PDFInfo
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- CN109666127A CN109666127A CN201811479822.7A CN201811479822A CN109666127A CN 109666127 A CN109666127 A CN 109666127A CN 201811479822 A CN201811479822 A CN 201811479822A CN 109666127 A CN109666127 A CN 109666127A
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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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
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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
- C08G18/4009—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
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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
-
- 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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
-
- 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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- 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
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Abstract
The invention discloses a kind of use for synthetic leather Self-leveling light-cured polyurethane resins and preparation method thereof, the use for synthetic leather Self-leveling light-cured polyurethane resin, is made of the raw material comprising following components: polyalcohol, organosilicon modified polyether polyalcohol, diisocyanate, end-capping reagent, simple diluents and low-surface-energy diluent.The present invention can soak substrate in the short time under conditions of without outer addition leveling auxiliary agent naturally, requirement when meeting illumination rapid curing to resin levelling；Secondly, use for synthetic leather Self-leveling light-cured polyurethane resin of the invention introduces the low-surface-energy diluent containing long alkyl chain, while facilitating resin wetted levelling, resin bring brittleness problems due to the introducing of acrylic monomers are also avoided, there is good normal low temperature folding quality；Again, solvent will not be discharged in use for synthetic leather Self-leveling light-cured polyurethane resin of the invention preparation and solidification process, is environmental protection and energy saving product.
Description
Technical field
The present invention relates to a kind of polyurethane resin and preparation method thereof, in particular to a kind of use for synthetic leather Self-leveling photocuring
Polyurethane resin and preparation method thereof.
Background technique
With the development of the social economy, consumer, while pursuing product quality, environmental consciousness is also constantly being awakened.It closes
Finished leather industry consumes the harmful substances such as a large amount of organic solvent, gets worse to the pollution of environment.Therefore, related technical personnel
Great effort has been put into develop the environmental synthetic leather technology to face the future, and photocuring synthetic leather technology is exactly one of them.
Photocuring use for synthetic leather resin, solvent-free discharge in the curing process, VOC content is low, environmentally protective；In addition, raw
It is higher to produce efficiency, short then seconds or tens of seconds can curing molding, and do not need to be heated at high temperature, energy consumption is very low.Correspondingly, needing
Wanting resin at room temperature has lower viscosity, lower surface energy, can soak levelling in a short time.In addition, usual skin
Leather polyurethane resin has preferable flexibility, and a large amount of introducings of acrylic diluents monomer often make resin become fragile,
It needs rationally to cope with.
Summary of the invention
It is an object of that present invention to provide a kind of use for synthetic leather Self-leveling light-cured polyurethane resins and preparation method thereof, with full
The needs of sufficient related fields application.
The use for synthetic leather Self-leveling light-cured polyurethane resin, is made of the raw material comprising following components:
Polyalcohol, organosilicon modified polyether polyalcohol, diisocyanate, end-capping reagent, simple diluents and low-surface-energy are dilute
Release agent；
It preferably, further include polymerization inhibitor, the dosage of the polymerization inhibitor is the 0.2%-0.5% of total resin weight；
The dosage of organosilicon modified polyether polyalcohol is the 0.5%-1.5% of total resin weight；
The ratio between total mole number and the total mole number of polyalcohol of diisocyanate are 1.5-3:1；
The ratio between total mole number and the total mole number of diisocyanate of end-capping reagent are 0.9-1.5:1；
Simple diluents and low-surface-energy diluent dosage are polyalcohol, organosilicon modified polyether polyalcohol, diisocyanate
The 10%-25% of the sum of the weight of ester and end-capping reagent；
Preferably, the polyalcohol is selected from polypropylene oxide/ethylene oxide ether triol, polyoxypropylene triol, poly- four
Hydrogen furans ether glycol, polyoxypropylene glycol, polypropylene oxide/ethylene oxide ether glycol, polycaprolactone glycol, polyadipate
The number-average molecular weight of one or more of neopentyl glycol esterdiol, polyhexamethylene adipate glycol, the polyalcohol is
500-8000；
Preferably, the organosilicon modified polyether polyalcohol is selected from terminal hydroxy group single functionality organosilicon modified polyether, end hydroxyl
Two degree of functionality organosilicon modified polyether of base, terminal hydroxy group tetra functional organosilicon modified polyether, two degree of functionality organosilicon of pendant hydroxyl group change
One of property polyethers；
The terminal hydroxy group single functionality organosilicon modified polyether is purchased from Guangzhou Si Luoke high molecular polymer Co., Ltd；
The two degree of functionality organosilicon modified polyether of terminal hydroxy group is purchased from Guangzhou Si Luoke high molecular polymer Co., Ltd；
The terminal hydroxy group tetra functional organosilicon modified polyether is purchased from Dow Corning Corporation；
The two degree of functionality organosilicon modified polyether of pendant hydroxyl group is purchased from Mai Tu company；
Preferably, the end-capping reagent is selected from hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, methyl
One or more of hydroxypropyl acrylate；
Preferably, the simple diluents are selected from hydroxy-ethyl acrylate, hydroxypropyl acrylate, Isooctyl acrylate monomer, methyl
Glycidyl acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1,6 hexanediol diacrylate,
One or more of neopentylglycol diacrylate, trimethylolpropane trimethacrylate；
Preferably, the low-surface-energy diluent is selected from 3,3,5- trimethylcyclohexyl acrylates, laurel acid acrylic acid
One or more of ester, isodecyl acrylate, isotridecyl methacrylate, iso-bornyl acrylate；
Preferably, the diisocyanate be selected from toluene di-isocyanate(TDI) (TDI), 1,6- di-isocyanate (HDI),
Isophorone diisocyanate (IPDI), diphenyl methane 4,4- diisocyanate (MDI), double-hexyl methane diisocyanate
(HMDI), tetramethylxylylene diisocyanate (TMXDI)) at least two；Preferably diphenyl methane two is different
One or both of cyanate, toluene di-isocyanate(TDI), hexamethylene diisocyanate；
Preferably, the polymerization inhibitor is selected from the one or two of hydroquinone, p methoxy phenol.
The preparation method of the use for synthetic leather Self-leveling light-cured polyurethane resin, comprising the following steps:
1) polyalcohol and organosilicon modified polyether polyalcohol investment reaction kettle are mixed, 50~60 DEG C stir evenly；
2) diisocyanate is put into reaction kettle in batches, makes reaction temperature between 65~80 DEG C, synthesis under normal pressure 2-8 is small
When, after system reaches certain viscosity, per half an hour measures a NCO content, when NCO content composite theory requires, investment
End-capping reagent and polymerization inhibitor will be zero to NCO content, stop heating, be cooled to 40 DEG C hereinafter, investment diluent, is uniformly mixed, i.e.,
The use for synthetic leather Self-leveling light-cured polyurethane resin can be made.
The invention has the following beneficial effects:
Use for synthetic leather Self-leveling light-cured polyurethane resin of the invention can under conditions of without outer addition leveling auxiliary agent,
Naturally substrate is soaked in short time, requirement when meeting illumination rapid curing to resin levelling；Secondly, use for synthetic leather of the invention
Self-leveling light-cured polyurethane resin introduces the low-surface-energy diluent containing long alkyl chain, facilitates resin wetted levelling
Meanwhile resin bring brittleness problems due to the introducing of acrylic monomers are also avoided, there is good normal low temperature folding quality；
Again, solvent will not be discharged in use for synthetic leather Self-leveling light-cured polyurethane resin of the invention preparation and solidification process, belonged to
Environmental protection and energy saving product；Be conducive to synthetic leather environmental protection transition.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate this hair
It is bright, rather than limit the scope of protection of the present invention.The improvement and tune that technical staff makes according to the present invention in practical applications
It is whole, still fall within protection scope of the present invention.Raw materials used following embodiment is commercially available.
Embodiment 1
The present embodiment is raw materials used and weight such as table 1.
Table 1
| Material name | Weight (unit: gram) |
| Polypropylene oxide/ethylene oxide ether triol (number-average molecular weight 6000) | 630 |
| Polyoxypropylene glycol (number-average molecular weight 2000) | 68 |
| Two degree of functionality organosilicon modified polyether (number-average molecular weight 1700) of pendant hydroxyl group | 9 |
| Methyl diphenylene diisocyanate | 49.4 |
| Toluene di-isocyanate(TDI) | 34.4 |
| Hydroxy-ethyl acrylate | 68.8 |
| 1,6 hexanediol diacrylate | 80 |
| Lauric acid acrylate | 100 |
| Hydroquinone | 3 |
The preparation step of the use for synthetic leather Self-leveling light-cured polyurethane resin of the present embodiment is as follows:
1) by 630g polypropylene oxide/ethylene oxide ether triol, 68g polyoxypropylene glycol, two function of 9g pendant hydroxyl group
It spends organosilicon modified polyether and puts into reaction kettle, 50 DEG C stir evenly；
2) 49.4g methyl diphenylene diisocyanate, 34.4g toluene di-isocyanate(TDI) are put into reaction kettle in batches, strictly
Reaction temperature is controlled between 75~80 DEG C, after synthesis under normal pressure 5 hours, NCO content is measured by sampling in per half an hour, works as NCO content
After 2.1%, 68.8g end-capping reagent hydroxy-ethyl acrylate and 3g hydroquinone of polymerization retarder are put into, is continued between 75~80 DEG C
Reaction, will be zero to NCO content, stop heating, be cooled to 40 DEG C hereinafter, investment 80g 1,6- hexanediyl ester and
100g lauric acid acrylate is uniformly mixed, can obtain use for synthetic leather Self-leveling light-cured polyurethane resin.
After resin obtained by 100g is mixed with the dispersed machine of 1.5g photoinitiator Darocur-1173, scratched in release paper
About 0.2mm is solidified by UV curing；Gained glue film levelling is good.
Room temperature folding test method: by the above-mentioned glue film prepared, 5 prints, root are cut out using original mold tool (45*70mm) is cut out
According to the condition of setting, the print cut out is mounted on room temperature (25 DEG C) fold tester (Taiwan high-speed rail, device model GT- respectively
It is tested on 7071-B), according to test case, records folding result.
Low temperature folding test method: by the above-mentioned glue film prepared, original mold tool (45*70mm) is cut out using folding and cuts out 5 samples
Piece, in (- 20 DEG C) test folding numbers of temperature condition.According to the condition of setting, it is resistance to that the print cut out is mounted on low temperature respectively
It is tested on folding testing machine (Taiwan letter reaches, device model HT-8043), according to test case, records folding result.
According to the result of room temperature low-temperature test method are as follows: room temperature folding does not rupture for 200,000 times, subzero 20 DEG C, does not break for 80,000 times
It splits.
Embodiment 2
The present embodiment is raw materials used and weight such as table 2.
Table 2
| Material name | Weight (unit: gram) |
| Polyoxypropylene glycol (number-average molecular weight 2000) | 690 |
| Two degree of functionality organosilicon modified polyether (number-average molecular weight 1700) of pendant hydroxyl group | 9 |
| Toluene di-isocyanate(TDI) | 122 |
| Hydroxypropyl acrylate | 110 |
| 1,6 hexanediol diacrylate | 30 |
| Glycidyl methacrylate | 30 |
| Isodecyl acrylate | 60 |
| Hydroquinone | 3 |
The preparation step of the use for synthetic leather Self-leveling light-cured polyurethane resin of the present embodiment is as follows:
1) by the pure and mild two degree of functionality organosilicon modified polyether of 9g pendant hydroxyl group of 690g polyoxypropylene two put into reaction kettle, 55
DEG C stirring；
2) 122g toluene di-isocyanate(TDI) is put into reaction kettle in batches, strict control reaction temperature between 75~80 DEG C,
After synthesis under normal pressure 4 hours, NCO content is measured by sampling in per half an hour, after NCO content is lower than 3.6%, puts into 110g end-capping reagent third
Olefin(e) acid hydroxypropyl acrylate and 3g hydroquinone of polymerization retarder, continue between 75~80 DEG C and react, and will be zero to NCO content, stop heating,
40 DEG C are cooled to hereinafter, investment 30g1,6- hexanediyl ester, 30g glycidyl methacrylate and 60g isodecyl
Acrylate is uniformly mixed, can obtain use for synthetic leather Self-leveling light-cured polyurethane resin.
After resin obtained by 100g is mixed with the dispersed machine of 1.5g photoinitiator Darocur-1173, scratched in release paper
About 0.2mm is solidified by UV curing；Gained glue film levelling is good, room temperature folding, does not rupture for 150,000 times, and subzero 20 DEG C, 40,000
It is secondary not rupture.
Embodiment 3
The present embodiment is raw materials used and weight such as table 3.
Table 3
| Material name | Weight (unit: gram) |
| Polyneopentyl glycol adipate glycol (number-average molecular weight 2000) | 150 |
| Polyoxypropylene glycol (number-average molecular weight 2000) | 438 |
| Polypropylene oxide/ethylene oxide ether glycol (number-average molecular weight 1000) | 100 |
| Two degree of functionality organosilicon modified polyether (number-average molecular weight 1700) of pendant hydroxyl group | 10 |
| Methyl diphenylene diisocyanate | 40 |
| Toluene di-isocyanate(TDI) | 111.4 |
| Hydroxy-ethyl acrylate | 139.2 |
| Glycidyl methacrylate | 40 |
| Trimethylolpropane trimethacrylate | 30 |
| 3,3,5- trimethylcyclohexyl acrylate | 80 |
| Hydroquinone | 3 |
The preparation step of the use for synthetic leather Self-leveling light-cured polyurethane resin of the present embodiment is as follows:
1) by 150g polyneopentyl glycol adipate glycol, 100g polypropylene oxide/ethylene oxide ether glycol, 450g polycyclic
Ethylene Oxide ether glycol puts into reaction kettle, two degree of functionality organosilicon modified polyether of 10g pendant hydroxyl group, and 55 DEG C stir evenly；
2) 40g methyl diphenylene diisocyanate, 111.4.4g toluene di-isocyanate(TDI) are put into reaction kettle in batches, strictly
Reaction temperature is controlled between 65~70 DEG C, after synthesis under normal pressure 3 hours, NCO content is measured by sampling in per half an hour, works as NCO content
After 3.9,139.2g end-capping reagent hydroxy-ethyl acrylate and 3g hydroquinone of polymerization retarder are put into, is continued at anti-between 75~80 DEG C
It answers, will be zero to NCO content, stop heating, be cooled to 40 DEG C hereinafter, investment 30g trimethylolpropane trimethacrylate, 40g
Glycidyl methacrylate and 80g3,3,5- trimethylcyclohexyl acrylates are uniformly mixed, and can obtain use for synthetic leather certainly
Levelling light-cured polyurethane resin.
After resin obtained by 100g is mixed with the dispersed machine of 1.5g photoinitiator Darocur-1173, scratched in release paper
About 0.2mm is solidified by UV curing；Gained glue film levelling is good, room temperature folding, does not rupture for 150,000 times, and subzero 20 DEG C, 40,000
It is secondary not rupture.
Embodiment 4
The present embodiment is raw materials used and weight such as the following table 4.
Table 4
| Material name | Weight (unit: gram) |
| Polyadipate methyl propanediol esterdiol (number-average molecular weight 1800) | 200 |
| Polypropylene oxide/ethylene oxide ether glycol (number-average molecular weight 2000) | 443 |
| Two degree of functionality organosilicon modified polyether (number-average molecular weight 3550) of terminal hydroxy group | 12 |
| Methyl diphenylene diisocyanate | 126 |
| Hydroxy-ethyl acrylate | 58 |
| Neopentylglycol diacrylate | 100 |
| Isotridecyl methacrylate | 80 |
| Hydroquinone | 3 |
The preparation step of the use for synthetic leather Self-leveling light-cured polyurethane resin of the present embodiment is as follows:
1) by 200g polyadipate methyl propanediol esterdiol, 443g polypropylene oxide/ethylene oxide ether glycol, the end 12g
Two degree of functionality organosilicon modified polyether of hydroxyl puts into reaction kettle, and 50~55 DEG C stir evenly；
2) 126g methyl diphenylene diisocyanate is put into reaction kettle in batches, strict control reaction temperature is at 65~70 DEG C
Between, after synthesis under normal pressure 3 hours, NCO content is measured by sampling in per half an hour, after NCO content is lower than 1.8%, 58 sealing end of investment
Agent hydroxy-ethyl acrylate and 3g hydroquinone of polymerization retarder, continue between 75~80 DEG C and react, and will be zero to NCO content, stop
Heating is cooled to 40 DEG C hereinafter, investment 100g neopentylglycol diacrylate and 80g isotridecyl methacrylate, are mixed
It closes uniformly, use for synthetic leather Self-leveling light-cured polyurethane resin can be obtained.
After resin obtained by 100g is mixed with the dispersed machine of 1.5g photoinitiator Darocur-1173, scratched in release paper
About 0.2mm is solidified by UV curing；Gained glue film levelling is good, room temperature folding, does not rupture for 180,000 times, and subzero 20 DEG C, 40,000
It is secondary not rupture.
Embodiment 5
The present embodiment is raw materials used and weight such as table 5.
Table 5
| Material name | Weight (unit: gram) |
| Polypropylene oxide/ethylene oxide ether triol (number-average molecular weight 6000) | 630 |
| Polyoxypropylene glycol (number-average molecular weight 2000) | 68 |
| Two degree of functionality organosilicon modified polyether (number-average molecular weight 3550) of terminal hydroxy group | 13 |
| Methyl diphenylene diisocyanate | 49.4 |
| Toluene di-isocyanate(TDI) | 34.4 |
| Hydroxy-ethyl acrylate | 68.8 |
| 1,6 hexanediol diacrylate | 80 |
| Iso-bornyl acrylate | 100 |
| Hydroquinone | 3 |
The preparation step of the use for synthetic leather Self-leveling light-cured polyurethane resin of the present embodiment is as follows:
1) by 630g polypropylene oxide/ethylene oxide ether triol, 68g polyoxypropylene glycol, two function of 13g terminal hydroxy group
It spends organosilicon modified polyether and puts into reaction kettle, 50~55 DEG C stir evenly；
2) 49.4g methyl diphenylene diisocyanate, 34.4g toluene di-isocyanate(TDI) are put into reaction kettle in batches, strictly
Reaction temperature is controlled between 75~80 DEG C, after synthesis under normal pressure 5 hours, NCO content is measured by sampling in per half an hour, works as NCO content
After 2.1%, 68.8g end-capping reagent hydroxy-ethyl acrylate and 3g hydroquinone of polymerization retarder are put into, is continued between 75~80 DEG C
Reaction, will be zero to NCO content, stop heating, be cooled to 40 DEG C hereinafter, investment 80g 1,6- hexanediyl ester and
100g iso-bornyl acrylate is uniformly mixed, can obtain use for synthetic leather Self-leveling light-cured polyurethane resin.
After resin obtained by 100g is mixed with the dispersed machine of 1.5g photoinitiator Darocur-1173, scratched in release paper
About 0.2mm is solidified by UV curing；Gained glue film levelling is good, room temperature folding, does not rupture for 200,000 times, and subzero 20 DEG C, 80,000
It is secondary not rupture.
Embodiment 6
The present embodiment is raw materials used and weight such as table 6.
Table 6
The preparation step of the use for synthetic leather Self-leveling light-cured polyurethane resin of the present embodiment is as follows:
1) the pure and mild two degree of functionality organosilicon modified polyether of 14g terminal hydroxy group of 690g polyoxypropylene two is put into reaction kettle,
50~55 DEG C of stirrings；
2) 122g toluene di-isocyanate(TDI) is put into reaction kettle in batches, strict control reaction temperature between 75~80 DEG C,
After synthesis under normal pressure 4 hours, NCO content is measured by sampling in per half an hour, after NCO content is lower than 3.6%, puts into 110g end-capping reagent third
Olefin(e) acid hydroxypropyl acrylate and 3g hydroquinone of polymerization retarder, continue between 75~80 DEG C and react, and will be zero to NCO content, stop heating,
40 DEG C are cooled to hereinafter, investment 30g1,6- hexanediyl ester, 30g glycidyl methacrylate and 60g lauric acid
Acrylate is uniformly mixed, can obtain use for synthetic leather Self-leveling light-cured polyurethane resin.
After resin obtained by 100g is mixed with the dispersed machine of 1.5g photoinitiator Darocur-1173, scratched in release paper
About 0.2mm is solidified by UV curing；Gained glue film levelling is good, room temperature folding, does not rupture for 150,000 times, and subzero 20 DEG C, 40,000
It is secondary not rupture.
Embodiment 7
The present embodiment is raw materials used and weight such as table 7.
Table 7
The preparation step of the use for synthetic leather Self-leveling light-cured polyurethane resin of the present embodiment is as follows:
1) by 150g polyneopentyl glycol adipate glycol, 100g polypropylene oxide/ethylene oxide ether glycol, 450g polycyclic
Ethylene Oxide ether glycol puts into reaction kettle, 8g terminal hydroxy group single functionality organosilicon modified polyether, and 53 DEG C stir evenly；
2) 40g methyl diphenylene diisocyanate, 111.4.4g toluene di-isocyanate(TDI) are put into reaction kettle in batches, strictly
Reaction temperature is controlled between 65~70 DEG C, after synthesis under normal pressure 3 hours, NCO content is measured by sampling in per half an hour, works as NCO content
After 3.9,139.2g end-capping reagent hydroxy-ethyl acrylate and 3g hydroquinone of polymerization retarder are put into, is continued at anti-between 75~80 DEG C
It answers, will be zero to NCO content, stop heating, be cooled to 40 DEG C hereinafter, investment 30g trimethylolpropane trimethacrylate, 40g
Glycidyl methacrylate and 80g isodecyl acrylate are uniformly mixed, can obtain use for synthetic leather Self-leveling light-solidifying poly
Urethane resin.
After resin obtained by 100g is mixed with the dispersed machine of 1.5g photoinitiator Darocur-1173, scratched in release paper
About 0.2mm is solidified by UV curing；Gained glue film levelling is good, room temperature folding, does not rupture for 150,000 times, and subzero 20 DEG C, 40,000
It is secondary not rupture.
Embodiment 8
The present embodiment is raw materials used and weight such as the following table 8.
Table 8
| Material name | Weight (unit: gram) |
| Polyadipate methyl propanediol esterdiol (number-average molecular weight 1800) | 200 |
| Polypropylene oxide/ethylene oxide ether glycol (number-average molecular weight 2000) | 443 |
| Terminal hydroxy group single functionality organosilicon modified polyether (number-average molecular weight 1300) | 7 |
| Methyl diphenylene diisocyanate | 126 |
| Hydroxy-ethyl acrylate | 58 |
| Neopentylglycol diacrylate | 100 |
| 3,3,5- trimethylcyclohexyl acrylate | 80 |
| Hydroquinone | 3 |
The preparation step of the use for synthetic leather Self-leveling light-cured polyurethane resin of the present embodiment is as follows:
1) by 200g polyadipate methyl propanediol esterdiol, 443g polypropylene oxide/ethylene oxide ether glycol, the end 7g hydroxyl
Base single functionality organosilicon modified polyether puts into reaction kettle, and 50~55 DEG C stir evenly；
2) 126g methyl diphenylene diisocyanate is put into reaction kettle in batches, strict control reaction temperature is at 65~70 DEG C
Between, after synthesis under normal pressure 3 hours, NCO content is measured by sampling in per half an hour, after NCO content is lower than 1.8%, 58 sealing end of investment
Agent hydroxy-ethyl acrylate and 3g hydroquinone of polymerization retarder, continue between 75~80 DEG C and react, and will be zero to NCO content, stop
Heating is cooled to 40 DEG C hereinafter, investment 100g neopentylglycol diacrylate and 80g3,3,5- trimethylcyclohexyl acrylic acid
Ester is uniformly mixed, can obtain use for synthetic leather Self-leveling light-cured polyurethane resin.
After resin obtained by 100g is mixed with the dispersed machine of 1.5g photoinitiator Darocur-1173, scratched in release paper
About 0.2mm is solidified by UV curing；Gained glue film levelling is good, room temperature folding, does not rupture for 180,000 times, and subzero 20 DEG C, 40,000
It is secondary not rupture.
Embodiment 9
The present embodiment is raw materials used and weight such as table 9.
Table 9
| Material name | Weight (unit: gram) |
| Polypropylene oxide/ethylene oxide ether triol (number-average molecular weight 6000) | 630 |
| Polyoxypropylene glycol (number-average molecular weight 2000) | 68 |
| Terminal hydroxy group tetra functional organosilicon modified polyether (number-average molecular weight 6000) | 5 |
| Methyl diphenylene diisocyanate | 49.4 |
| Toluene di-isocyanate(TDI) | 34.4 |
| Hydroxy-ethyl acrylate | 68.8 |
| 1,6 hexanediol diacrylate | 80 |
| Isotridecyl methacrylate | 100 |
| Hydroquinone | 3 |
The preparation step of the use for synthetic leather Self-leveling light-cured polyurethane resin of the present embodiment is as follows:
1) by 630g polypropylene oxide/ethylene oxide ether triol, 68g polyoxypropylene glycol, 5g terminal hydroxy group tetrafunctional
It spends organosilicon modified polyether and puts into reaction kettle, 50~55 DEG C stir evenly；
2) 49.4g methyl diphenylene diisocyanate, 34.4g toluene di-isocyanate(TDI) are put into reaction kettle in batches, strictly
Reaction temperature is controlled between 75~80 DEG C, after synthesis under normal pressure 5 hours, NCO content is measured by sampling in per half an hour, works as NCO content
After 2.1%, 68.8g end-capping reagent hydroxy-ethyl acrylate and 3g hydroquinone of polymerization retarder are put into, is continued between 75~80 DEG C
Reaction, will be zero to NCO content, stop heating, be cooled to 40 DEG C hereinafter, investment 80g 1,6- hexanediyl ester and
100g isotridecyl methacrylate is uniformly mixed, can obtain use for synthetic leather Self-leveling light-cured polyurethane resin.
After resin obtained by 100g is mixed with the dispersed machine of 1.5g photoinitiator Darocur-1173, scratched in release paper
About 0.2mm is solidified by UV curing；Gained glue film levelling is good, room temperature folding, does not rupture for 200,000 times, and subzero 20 DEG C, 80,000
It is secondary not rupture.
Embodiment 10
The present embodiment is raw materials used and weight such as table 10.
Table 10
| Material name | Weight (unit: gram) |
| Polyoxypropylene glycol (number-average molecular weight 2000) | 690 |
| Terminal hydroxy group tetra functional organosilicon modified polyether (number-average molecular weight 6000) | 6 |
| Toluene di-isocyanate(TDI) | 122 |
| Hydroxypropyl acrylate | 110 |
| 1,6 hexanediol diacrylate | 30 |
| Glycidyl methacrylate | 30 |
| Iso-bornyl acrylate | 60 |
| Hydroquinone | 3 |
The preparation step of the use for synthetic leather Self-leveling light-cured polyurethane resin of the present embodiment is as follows:
1) by the pure and mild 6g terminal hydroxy group tetra functional organosilicon modified polyether of 690g polyoxypropylene two put into reaction kettle, 50
~55 DEG C of stirrings；
2) 122g toluene di-isocyanate(TDI) is put into reaction kettle in batches, strict control reaction temperature between 75~80 DEG C,
After synthesis under normal pressure 4 hours, NCO content is measured by sampling in per half an hour, after NCO content is lower than 3.6%, puts into 110g end-capping reagent third
Olefin(e) acid hydroxypropyl acrylate and 3g hydroquinone of polymerization retarder, continue between 75~80 DEG C and react, and will be zero to NCO content, stop heating,
40 DEG C are cooled to hereinafter, investment 30g1,6- hexanediyl ester, 30g glycidyl methacrylate and 60g isoborneol
Base acrylate is uniformly mixed, can obtain use for synthetic leather Self-leveling light-cured polyurethane resin.
After resin obtained by 100g is mixed with the dispersed machine of 1.5g photoinitiator Darocur-1173, scratched in release paper
About 0.2mm is solidified by UV curing；Gained glue film levelling is good, room temperature folding, does not rupture for 150,000 times, and subzero 20 DEG C, 40,000
It is secondary not rupture.
Under the teaching of the present invention and the above embodiments, those skilled in the art are easy to it is envisioned that cited by the present invention
Or each raw material enumerated or its equivalent alterations, each processing method or its equivalent alterations can realize the present invention and each original
The parameter bound value of material and processing method, interval value can realize the present invention, embodiment numerous to list herein.
Claims (10)
1. use for synthetic leather Self-leveling light-cured polyurethane resin, which is characterized in that be made of the raw material comprising following components: polynary
Alcohol, organosilicon modified polyether polyalcohol, diisocyanate, end-capping reagent, simple diluents and low-surface-energy diluent.
2. use for synthetic leather Self-leveling light-cured polyurethane resin according to claim 1, which is characterized in that further include polymerization inhibitor
Agent.
3. use for synthetic leather Self-leveling light-cured polyurethane resin according to claim 1 or 2, which is characterized in that described
The dosage of polymerization inhibitor is the 0.2%-0.5% of total resin weight；
The dosage of organosilicon modified polyether polyalcohol is the 0.5%-1.5% of total resin weight；
The ratio between total mole number and the total mole number of polyalcohol of diisocyanate are 1.5-3:1；
The ratio between total mole number and the total mole number of diisocyanate of end-capping reagent are 0.9-1.5:1；
Simple diluents and low-surface-energy diluent dosage be polyalcohol, organosilicon modified polyether polyalcohol, diisocyanate with
The 10%-25% of the sum of the weight of end-capping reagent.
4. use for synthetic leather Self-leveling light-cured polyurethane resin according to claim 1 or 2, which is characterized in that described more
First alcohol is selected from polypropylene oxide/ethylene oxide ether triol, polyoxypropylene triol, polytetrahydrofuran ether glycol, polycyclic oxygen third
Alkane ether glycol, polypropylene oxide/ethylene oxide ether glycol, polyneopentyl glycol adipate glycol, gather oneself two at polycaprolactone glycol
One or more of sour hexylene glycol esterdiol, the number-average molecular weight of the polyalcohol are 500-8000.
5. use for synthetic leather Self-leveling light-cured polyurethane resin according to claim 1 or 2, which is characterized in that described to have
It is organic-silicon-modified poly- that machine silicon-modified polyether polyalcohol is selected from terminal hydroxy group single functionality organosilicon modified polyether, two degree of functionality of terminal hydroxy group
One of ether, terminal hydroxy group tetra functional organosilicon modified polyether, two degree of functionality organosilicon modified polyether of pendant hydroxyl group.
6. use for synthetic leather Self-leveling light-cured polyurethane resin according to claim 1 or 2, which is characterized in that the envelope
Hold agent be selected from one of hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate or
It is several.
7. use for synthetic leather Self-leveling light-cured polyurethane resin according to claim 1 or 2, which is characterized in that described general
Logical diluent is selected from hydroxy-ethyl acrylate, hydroxypropyl acrylate, Isooctyl acrylate monomer, glycidyl methacrylate, dipropyl
Omega-diol diacrylate, tripropylene glycol diacrylate, 1,6 hexanediol diacrylate, neopentylglycol diacrylate, three
One or more of hydroxymethyl-propane triacrylate；
The low-surface-energy diluent is selected from 3,3,5- trimethylcyclohexyl acrylate, lauric acid acrylate, isodecyl third
One or more of olefin(e) acid ester, isotridecyl methacrylate, iso-bornyl acrylate.
8. use for synthetic leather Self-leveling light-cured polyurethane resin according to claim 1 or 2, which is characterized in that described
Diisocyanate is selected from toluene di-isocyanate(TDI) (TDI), 1,6- di-isocyanate (HDI), isophorone diisocyanate
(IPDI), diphenyl methane 4,4- diisocyanate (MDI), double-hexyl methane diisocyanate (HMDI), durol two
Methylene diisocyanate (TMXDI)) at least two；Preferably methyl diphenylene diisocyanate, toluene diisocyanate
One or both of acid esters, hexamethylene diisocyanate.
9. the preparation method of described in any item use for synthetic leather Self-leveling light-cured polyurethane resins according to claim 1~8,
It is characterized in that, comprising the following steps:
1) polyalcohol and organosilicon modified polyether polyalcohol are mixed；
2) di-isocyanate reaction is put into, end-capping reagent and polymerization inhibitor is put into, will be zero to NCO content, it is cooling, diluent is put into,
Mixing, can be prepared by the use for synthetic leather Self-leveling light-cured polyurethane resin.
10. according to the method described in claim 9, it is characterized by:
1) polyalcohol and organosilicon modified polyether polyalcohol are mixed, 50~60 DEG C of stirrings；
2) diisocyanate is put into, makes reaction temperature between 65~80 DEG C, synthesis under normal pressure 2-8 hours, puts into end-capping reagent and resistance
Poly- agent will be zero to NCO content, be cooled to 40 DEG C hereinafter, investment diluent, mixing.
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| CN113956784A (en) * | 2021-10-18 | 2022-01-21 | 丽水学院 | Water-based visible light driven film-forming finishing agent for ecological synthetic leather |
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| CN110467842A (en) * | 2019-07-30 | 2019-11-19 | 清远市美佳乐环保新材股份有限公司 | There is one kind wetting to thicken multifunctional aqueous auxiliary agent and preparation method thereof |
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| CN113897121A (en) * | 2021-10-18 | 2022-01-07 | 上海昶瀚科技有限公司 | Yellowing-resistant self-repairing coating composition, automobile paint protective film and preparation method thereof |
| CN113956784A (en) * | 2021-10-18 | 2022-01-21 | 丽水学院 | Water-based visible light driven film-forming finishing agent for ecological synthetic leather |
| CN113897121B (en) * | 2021-10-18 | 2022-08-09 | 上海昶瀚科技有限公司 | Yellowing-resistant self-repairing coating composition, automobile paint protective film and preparation method thereof |
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| CN109666127B (en) | 2021-09-10 |
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