CN104371088A - Novel polyurethane acrylic resin preparation - Google Patents
Novel polyurethane acrylic resin preparation Download PDFInfo
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- CN104371088A CN104371088A CN201410742708.4A CN201410742708A CN104371088A CN 104371088 A CN104371088 A CN 104371088A CN 201410742708 A CN201410742708 A CN 201410742708A CN 104371088 A CN104371088 A CN 104371088A
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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
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines 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
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
-
- 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
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6523—Compounds of group C08G18/3225 or C08G18/3271 or polyamines of C08G18/38
- C08G18/6535—Compounds of group C08G18/3271
-
- 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
-
- 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
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to novel polyurethane acrylic resin preparation. Diethanolamine, diisocyanate and acrylate monomer containing hydroxyl are adopted as raw materials, and the novel polyurethane acrylic resin can be prepared. According to the requirements on the polyurethane acrylic resin with improved wear resistance and heat resistance, the purpose of simplifying the process and preparing the novel polyurethane acrylic resin with improved wear resistance and heat resistance can be achieved, the comprehensive performances of multifunctional novel polyurethane acrylic resin can be improved, and the market of acrylic resin can be expanded.
Description
Technical field
The invention belongs to UV polyurea type polyurethane acrylic resin field, relate to a kind of preparation method of new polyurethane acrylic resin.
Background technology
Diethanolamine is the intermediate of organic synthesis, such as, can be used to some optical bleaching agent in production textile industry.Diethanolamine is used as reagent and GC stationary liquid on analytical chemistry, optionally retains and is separated alcohol, glycol, amine, pyridine, quinoline, piperazine, mercaptan, thioether and water.Diethanolamine is important inhibiter, can be used for the refrigerant of boiler water processing, car engine, plays corrosion inhibition in drilling well and machining oil and other kinds lubricating oil.In Sweet natural gas, be also used as the absorption agent of purification of acidic gas.Emulsifying agent is used as in various makeup and medicine.In textile industry, make lubricant, also can make wetting agent and tenderizer and other organic synthesis raw material.Acid absorber, softening agent, tenderizer, emulsifying agent etc. are used as in sizing agent.Also be used as the absorption agent of sour gas (as hydrogen sulfide, carbonic acid gas etc.) in petroleum gas, Sweet natural gas and other gas.It is the raw material of synthesis medicine, agricultural chemicals, dyestuff intermediate and tensio-active agent.Be used as the emulsifying agent of oils, wax class in acid condition, the tenderizer of leather and synthon.Thickening material and lather modifier is used as in shampoo and light-duty washing agent.Also be used as washing composition, lubricant, brightening agent and engine piston deashing agent etc.As analytical reagent, acid gas absorbent, tenderizer and lubricant, and for organic synthesis.
Containing acrylic-functional and amino-formate bond in the molecule of urethane acrylate (PUA), sizing agent after solidification has the high-wearing feature of urethane, adhesive power, snappiness, the optical property of high-peeling strength and excellent resistance to low temperature and polyacrylic ester brilliance and weathering resistance, is a kind of radiation curing material of high comprehensive performance.A lot of research and application facts have proved, PUA has many excellent performance characteristics as high-molecular-weight glutenin subunits prepared by prepolymer.PUA has ammonia ester bond, is characterized in that high-polymer molecular interchain can form multiple hydrogen bond, and make polyurethane film have excellent mechanical endurance and snappiness, elongation at break is high.Film has excellent chemical resistance and high and low temperature resistance.Film, to being difficult to bonding base material, as plastics, has preferably sticking power.The composition of PUA and chemical property have larger adjustment leeway than epoxy resin, therefore can synthesize the multiple PUA prepolymer with different functionality, different qualities.As high rigidity or high-flexibility or elastomeric PUA cured film all can obtain.The PUA of different functional groups all has commercial product.
The present invention utilizes diethanolamine, vulcabond, acrylate monomer containing hydroxyl is raw material, prepares a kind of new polyurethane acrylic resin.Meet the demand to wear resistance and the higher acrylic resin of heat resistant requirements on market.
Summary of the invention
The object of the invention, for the demand of wear resistance and the better acrylic resin of thermotolerance in the market, the object of the invention is to Simplified flowsheet, preparation wear resistance and the good new polyurethane acrylic resin of thermotolerance.Prepare a kind of new polyurethane acrylic resin, improve polyfunctionality new polyurethane acrylic resin over-all properties, developing acrylic resin market.
The concrete implementation step of the present invention is as follows:
(1) an isocyano reaction in the acrylate containing hydroxyl and vulcabond, hydroxyl in acrylate and the mol ratio of vulcabond are 1:1, add relatively account for vulcabond quality 0.05%-1% dibutyl tin laurate (DBTDL) as catalyzer, react 1-10h in anhydrous conditions, temperature of reaction is 20-40 DEG C;
(2) by the acrylate containing an active function groups isocyano of preparation in step (1) and diethanolamine reaction, acrylate containing an active function groups isocyano and the diethanolamine mol ratio of preparation in step (1) are 1:1-3:1, temperature of reaction is 60-80 DEG C in anhydrous conditions, reaction times is 2-8h, finally obtains a kind of new polyurethane acrylic resin product.
(3) solidification is analyzed and the product obtained in step (2) is added 1173/184/2959 light trigger, is coated in clean slide surface uniformly with spreader, in solidification case, carry out photocuring reaction 10-30 second, intensity of illumination 40-80mW/cm
-2, observe and sample after test solidification.
Advantage of the present invention:
1. Simplified flowsheet, uses diethanolamine, preparation wear resistance and the good new polyurethane acrylic resin of thermotolerance;
2. prepare a kind of new polyurethane acrylic resin, improve polyfunctionality polyurethane acrylic resin over-all properties, developing acrylic resin market;
3. the new polyurethane acrylic resin prepared of the present invention, reaction conditions is gentle, with low cost.
Embodiment
Embodiment one
(1) an isocyano reaction of Hydroxyethyl acrylate and dimethyl diphenyl vulcabond, the mol ratio of Hydroxyethyl acrylate and dimethyl diphenyl vulcabond is 1:1, add relatively account for vulcabond quality 0.05% dibutyl tin laurate (DBTDL) as catalyzer, react 10h in anhydrous conditions, temperature of reaction is 40 DEG C;
(2) by the Hydroxyethyl acrylate containing an active function groups isocyano of preparation in step (1) and diethanolamine reaction, in step (1), preparation is 3:1 containing the acrylate of an active function groups isocyano and the hydroxyl mol ratio of fluorocarbon resin (Mn=50000), temperature of reaction is 80 DEG C in anhydrous conditions, reaction times is 8h, finally obtains a kind of polyfunctionality fluorocarbon acrylic acid resin product.
(3) 1173 light triggers product obtained in step (2) being added massfraction 2% are analyzed in solidification, are coated in clean slide surface uniformly with spreader, in solidification case, carry out photocuring reaction 10 seconds, intensity of illumination 40mW/cm
-2, observe the rear sample of solidification.Sample surfaces glossy clear, completion of cure.
Embodiment two
(1) hydroxyethyl methylacrylate and 4, an isocyano reaction of 4'-methylene-bis (phenylcarbimide), hydroxyethyl methylacrylate and 4,4'-methylene-bis (phenylcarbimide) both mol ratios are 1:1, add relatively account for vulcabond quality 0.5% dibutyl tin laurate (DBTDL) as catalyzer, react 5h in anhydrous conditions, temperature of reaction is 30 DEG C;
(2) by the hydroxyethyl methylacrylate containing an active function groups isocyano of preparation in step (1) and diethanolamine reaction, in step (1), preparation is 2:1 containing the hydroxyethyl methylacrylate of an active function groups isocyano and the hydroxyl mol ratio of fluorocarbon resin (Mn=20000), temperature of reaction is 70 DEG C in anhydrous conditions, reaction times is 5h, finally obtains a kind of polyfunctionality fluorocarbon acrylic acid resin product.
(3) 184 light triggers product obtained in step (2) being added massfraction 4% are analyzed in solidification, are coated in clean slide surface uniformly with spreader, in solidification case, carry out photocuring reaction 20 seconds, intensity of illumination 60mW/cm
-2, observe the rear sample of solidification.Sample surfaces glossy clear, completion of cure.
Embodiment three:
(1) trimethylolpropane diacrylate and an isocyano reaction to the different acid esters of benzene two, trimethylolpropane diacrylate and be 1:1 to the mol ratio of the different acid esters of benzene two, add relatively account for vulcabond quality 1% dibutyl tin laurate (DBTDL) as catalyzer, react 2h in anhydrous conditions, temperature of reaction is 20 DEG C;
(2) by the acrylate containing an active function groups isocyano of preparation in step (1) and diethanolamine reaction, in step (1), preparation is 1:1 containing the acrylate of an active function groups isocyano and the hydroxyl mol ratio of fluorocarbon resin (Mn=10000), temperature of reaction is 60 DEG C in anhydrous conditions, reaction times is 2h, finally obtains a kind of polyfunctionality fluorocarbon acrylic acid resin product.
(3) 2959 light triggers product obtained in step (2) being added massfraction 6% are analyzed in solidification, are coated in clean slide surface uniformly with spreader, in solidification case, carry out photocuring reaction 30 seconds, intensity of illumination 80mW/cm
-2, observe the rear sample of solidification.Sample surfaces glossy clear, completion of cure.
Embodiment four:
(1) pentaerythritol triacrylate and 2, an isocyano reaction of 4-tolylene diisocyanate, pentaerythritol triacrylate and 2, the mol ratio of both 4-tolylene diisocyanates is 1:1, add relatively account for vulcabond quality 0.1% dibutyl tin laurate (DBTDL) as catalyzer, react 4h in anhydrous conditions, temperature of reaction is 25 DEG C;
(2) by the pentaerythritol triacrylate containing an active function groups isocyano of preparation in step (1) and diethanolamine reaction, in step (1), preparation is 1.5:1 containing the pentaerythritol triacrylate of an active function groups isocyano and the hydroxyl mol ratio of fluorocarbon resin (Mn=5000), temperature of reaction is 65 DEG C in anhydrous conditions, reaction times is 4h, finally obtains a kind of polyfunctionality fluorocarbon acrylic acid resin product.
(3) 1173 light triggers product obtained in step (2) being added massfraction 4% are analyzed in solidification, are coated in clean slide surface uniformly with spreader, in solidification case, carry out photocuring reaction 15 seconds, intensity of illumination 50mW/cm
-2, observe the rear sample of solidification.Sample surfaces glossy clear, completion of cure.
Embodiment five:
(1) Propylene glycol monoacrylate and 1, an isocyano reaction of hexamethylene-diisocyanate, Propylene glycol monoacrylate and 1, the mol ratio of both hexamethylene-diisocyanates is 1:1, add relatively account for vulcabond quality 0.2% dibutyl tin laurate (DBTDL) as catalyzer, react 1h in anhydrous conditions, temperature of reaction is 35 DEG C;
(2) Propylene glycol monoacrylate of an active function groups isocyano and the hydroxyl reaction of fluorocarbon resin (Mn=2000) is contained by what prepare in step (1), Propylene glycol monoacrylate containing an active function groups isocyano and the diethanolamine mol ratio of preparation in step (1) are 2.5:1, temperature of reaction is 75 DEG C in anhydrous conditions, reaction times is 6h, finally obtains a kind of polyfunctionality fluorocarbon acrylic acid resin product.
(3) 184 light triggers product obtained in step (2) being added massfraction 2% are analyzed in solidification, are coated in clean slide surface uniformly with spreader, in solidification case, carry out photocuring reaction 10 seconds, intensity of illumination 55mW/cm
-2, observe the rear sample of solidification.Sample surfaces glossy clear, completion of cure.
Embodiment six:
(1) Rocryl 410 and 1, an isocyano reaction of 5-naphthalene diisocyanate, Rocryl 410 and 1, the mol ratio of both 5-naphthalene diisocyanates is 1:1, add relatively account for vulcabond quality 0.3% dibutyl tin laurate (DBTDL) as catalyzer, react 8h in anhydrous conditions, temperature of reaction is 25 DEG C;
(2) by the Rocryl 410 containing an active function groups isocyano of preparation in step (1) and diethanolamine reaction, in step (1), preparation is 1.8:1 containing the Rocryl 410 of an active function groups isocyano and the hydroxyl mol ratio of fluorocarbon resin (Mn=1000), temperature of reaction is 80 DEG C in anhydrous conditions, reaction times is 2h, finally obtains a kind of polyfunctionality fluorocarbon acrylic acid resin product.
(3) 2959 light triggers product obtained in step (2) being added massfraction 3% are analyzed in solidification, are coated in clean slide surface uniformly with spreader, in solidification case, carry out photocuring reaction 30 seconds, intensity of illumination 45mW/cm
-2, observe the rear sample of solidification.Sample surfaces glossy clear, completion of cure.
Embodiment seven:
(1) an isocyano reaction of polyethylene glycol monomethacrylate and isophorone diisocyanate, the mol ratio of polyethylene glycol monomethacrylate and isophorone diisocyanate is 1:1, add relatively account for vulcabond quality 0.6% dibutyl tin laurate (DBTDL) as catalyzer, react 4h in anhydrous conditions, temperature of reaction is 30 DEG C;
(2) polyethylene glycol monomethacrylate of an active function groups isocyano and the hydroxyl reaction of fluorocarbon resin (Mn=500) is contained by what prepare in step (1), polyethylene glycol monomethacrylate containing an active function groups isocyano and the diethanolamine mol ratio of preparation in step (1) are 3:1, temperature of reaction is 60 DEG C in anhydrous conditions, reaction times is 8h, finally obtains a kind of polyfunctionality fluorocarbon acrylic acid resin product.
(3) 184 light triggers product obtained in step (2) being added massfraction 5% are analyzed in solidification, are coated in clean slide surface uniformly with spreader, in solidification case, carry out photocuring reaction 10 seconds, intensity of illumination 70mW/cm
-2, observe the rear sample of solidification.Sample surfaces glossy clear, completion of cure.
Embodiment eight:
(1) 2-hydroxyl-3-phenoxypropylacrylate and 4, an isocyano reaction of 4-hexylmethane, 2-hydroxyl-3-phenoxypropylacrylate and 4, the mol ratio of both 4-hexylmethane is 1:1, add relatively account for vulcabond quality 0.7% dibutyl tin laurate (DBTDL) as catalyzer, react 5h in anhydrous conditions, temperature of reaction is 35 DEG C;
(2) the 2-hydroxyl-3-phenoxypropylacrylate of an active function groups isocyano and the hydroxyl reaction of fluorocarbon resin (Mn=40000) is contained by what prepare in step (1), 2-hydroxyl-3-phenoxypropylacrylate containing an active function groups isocyano and the diethanolamine mol ratio of preparation in step (1) are 2:1, temperature of reaction is 65 DEG C in anhydrous conditions, reaction times is 5h, finally obtains a kind of polyfunctionality fluorocarbon acrylic acid resin product.
(3) 1173 light triggers product obtained in step (2) being added massfraction 5% are analyzed in solidification, are coated in clean slide surface uniformly with spreader, in solidification case, carry out photocuring reaction 10 seconds, intensity of illumination 80mW/cm
-2, observe the rear sample of solidification.Sample surfaces glossy clear, completion of cure.
Embodiment nine:
(1) an isocyano reaction of 2-hydroxyl-3-phenoxypropylacrylate and dimethyl diphenyl vulcabond, the mol ratio of 2-hydroxyl-3-phenoxypropylacrylate and dimethyl diphenyl vulcabond is 1:1, add relatively account for vulcabond quality 0.3% dibutyl tin laurate (DBTDL) as catalyzer, react 4h in anhydrous conditions, temperature of reaction is 38 DEG C;
(2) the 2-hydroxyl-3-phenoxypropylacrylate of an active function groups isocyano and the hydroxyl reaction of fluorocarbon resin (Mn=40000) is contained by what prepare in step (1), 2-hydroxyl-3-phenoxypropylacrylate containing an active function groups isocyano and the diethanolamine mol ratio of preparation in step (1) are 1.2:1, temperature of reaction is 68 DEG C in anhydrous conditions, reaction times is 4h, finally obtains a kind of polyfunctionality fluorocarbon acrylic acid resin product.
(3) 184 light triggers product obtained in step (2) being added massfraction 6% are analyzed in solidification, are coated in clean slide surface uniformly with spreader, in solidification case, carry out photocuring reaction 12 seconds, intensity of illumination 75mW/cm
-2, observe the rear sample of solidification.Sample surfaces glossy clear, completion of cure.
Claims (3)
1. a preparation method for new polyurethane acrylic resin, is characterized in that following steps:
(1) an isocyano reaction in the acrylate containing hydroxyl and vulcabond, hydroxyl in acrylate and the mol ratio of vulcabond are 1:1, add relatively account for vulcabond quality 0.05%-1% dibutyl tin laurate (DBTDL) as catalyzer, react 1-10h in anhydrous conditions, temperature of reaction is 20-40 DEG C;
(2) by the acrylate containing an active function groups isocyano of preparation in step (1) and diethanolamine reaction, acrylate containing an active function groups isocyano and the diethanolamine mol ratio of preparation in step (1) are 1:1-3:1, temperature of reaction is 60-80 DEG C in anhydrous conditions, reaction times is 2-8h, finally obtains a kind of new polyurethane acrylic resin product.
2. preparation method according to claim 1, it is characterized in that step (1) used containing hydroxy acrylate be Hydroxyethyl acrylate, hydroxyethyl methylacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, Propylene glycol monoacrylate, Rocryl 410, polyethylene glycol monomethacrylate, 2-hydroxyl-3-phenoxypropylacrylate.
3. preparation method according to claim 1, it is characterized in that step (1) vulcabond used is dimethyl diphenyl vulcabond, 4,4'-methylene-bis (phenylcarbimide), to the different acid esters of benzene two, 2,4-tolylene diisocyanate, 1, hexamethylene-diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate, 4,4-hexylmethane.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410742708.4A CN104371088A (en) | 2014-12-08 | 2014-12-08 | Novel polyurethane acrylic resin preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410742708.4A CN104371088A (en) | 2014-12-08 | 2014-12-08 | Novel polyurethane acrylic resin preparation |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602497A (en) * | 2016-01-26 | 2016-05-25 | 浙江中科立德新材料有限公司 | Polyurethane-modified acrylic acid waterborne binder and preparing method and application thereof |
| WO2016096641A1 (en) * | 2014-12-19 | 2016-06-23 | Covestro Deutschland Ag | Moisture-stable holographic media |
| CN109265649A (en) * | 2017-07-17 | 2019-01-25 | 乐凯华光印刷科技有限公司 | A kind of self-emulsifying type radiation-curable composition and preparation method thereof |
| CN109678761A (en) * | 2018-12-19 | 2019-04-26 | 上海维凯光电新材料有限公司 | A kind of high-modulus fluorochemical urethane acrylate and preparation method thereof |
| CN109734860A (en) * | 2019-01-10 | 2019-05-10 | 四川东树新材料有限公司 | A kind of urethane composition for vacuum introducing technology |
| CN112064179A (en) * | 2020-09-07 | 2020-12-11 | 台州斯美特鞋业有限公司 | High-flexibility high-stiffness light vamp material and forming process thereof |
-
2014
- 2014-12-08 CN CN201410742708.4A patent/CN104371088A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016096641A1 (en) * | 2014-12-19 | 2016-06-23 | Covestro Deutschland Ag | Moisture-stable holographic media |
| CN107223121A (en) * | 2014-12-19 | 2017-09-29 | 科思创德国股份有限公司 | The holographic media of wet stabilization |
| US10329244B2 (en) * | 2014-12-19 | 2019-06-25 | Covestro Deutschland Ag | Moisture-stable holographic media |
| CN107223121B (en) * | 2014-12-19 | 2020-10-27 | 科思创德国股份有限公司 | Wet stable holographic media |
| CN105602497A (en) * | 2016-01-26 | 2016-05-25 | 浙江中科立德新材料有限公司 | Polyurethane-modified acrylic acid waterborne binder and preparing method and application thereof |
| CN109265649A (en) * | 2017-07-17 | 2019-01-25 | 乐凯华光印刷科技有限公司 | A kind of self-emulsifying type radiation-curable composition and preparation method thereof |
| CN109265649B (en) * | 2017-07-17 | 2022-03-11 | 乐凯华光印刷科技有限公司 | Self-emulsifying radiation curing composition and preparation method thereof |
| CN109678761A (en) * | 2018-12-19 | 2019-04-26 | 上海维凯光电新材料有限公司 | A kind of high-modulus fluorochemical urethane acrylate and preparation method thereof |
| CN109734860A (en) * | 2019-01-10 | 2019-05-10 | 四川东树新材料有限公司 | A kind of urethane composition for vacuum introducing technology |
| CN112064179A (en) * | 2020-09-07 | 2020-12-11 | 台州斯美特鞋业有限公司 | High-flexibility high-stiffness light vamp material and forming process thereof |
| CN112064179B (en) * | 2020-09-07 | 2022-04-22 | 台州斯美特鞋业有限公司 | High-flexibility high-stiffness light vamp material and forming process thereof |
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Application publication date: 20150225 |