CN101717487A - Polyurethane emulsion and coating agent used for aquosity coating agent of knitted lining glove as well as preparation method and coating method thereof - Google Patents
Polyurethane emulsion and coating agent used for aquosity coating agent of knitted lining glove as well as preparation method and coating method thereof Download PDFInfo
- Publication number
- CN101717487A CN101717487A CN200910228609A CN200910228609A CN101717487A CN 101717487 A CN101717487 A CN 101717487A CN 200910228609 A CN200910228609 A CN 200910228609A CN 200910228609 A CN200910228609 A CN 200910228609A CN 101717487 A CN101717487 A CN 101717487A
- Authority
- CN
- China
- Prior art keywords
- agent
- dibasic alcohol
- average molecular
- molecular weight
- coating agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a polyurethane emulsion used for aquosity coating agent of knitted lining glove and a preparation method thereof. In the preparation process, no softening agent, coupling agent, or a crosslinking agent is needed to be added, and the invention aims to replace oil-soluble polyurethane products to prepare the aquosity coating agent of the knitted lining glove. In the invention, the aquosity coating agent is obtained by mixing aquosity polyurethane emulsion with auxiliary materials, and is coated on a glove through the steps of immersing into the coating agent, solidifying and shaping, and washing and drying. The aquosity coating agent prepared by the method is environmental friendly without pollution and is beneficial to protect the health of workers, and the glove has the advantages of good mechanical performance, cutting resistance, penetrating resistance, good grabbing performance, waterproof and air permeability, comfortable hand feel and flexible operation.
Description
Technical field
The present invention relates to a kind of aqueous polyurethane emulsion and finishing agent and manufacture method thereof and coating method, more particularly, relate to a kind of aqueous polyurethane emulsion and finishing agent and manufacture method and coating method that is used for knitted lining glove.
Background technology
People tend to cause the injury of hand in routine work or family life, so gloves just become the important a member in the articles for labour protection.Different Application Areass needs different safety and industrial gloves, knitted lining glove is one of kind that is most widely used, usually knitted lining glove is a liner with knitted cotton or fiber all, at outer surface of glove, major part is that palm part applies one deck emulsion coating, thereby makes gloves have performances such as anti-preferably cutting, puncture, wear-resisting, anti-solvent, high grip.Rubber is to be used for the finishing agent material of application glove the earliest, though rubber is cheap, the gloves after the coating are anti-to be cut, the wear resisting property excellence, but, because the flexibility of rubber is very poor, whole hardening before gloves apply, for being engaged in meticulous active laborer, operation is very inconvenient after dressing.Comparatively speaking, urethane is not only even better aspect flexibility, and has the function of waterproof and breathable, so use more extensive.But, when the polyurethane material in field up till now mostly is the oil soluble product, contain a large amount of organic solvents, not only in applying drying process, environment is caused pollution significantly, harm practitioner's health, and remain in the skin that solvent in the gloves can stimulate wearer again, cause symptoms such as allergy.In addition, for the higher industry of a few thing environmental requirement, as food, fields such as medical treatment, the knitted gloves that has the oil soluble finishing agent also is limited to use.So, a kind of both excellent performances are provided, meet the novel finishing agent product of the environmental requirement of increasingly stringent again, have significant application value.
In recent years, along with being rooted in the hearts of the people of environmental protection ideas,, be the polyaminoester emulsion series product of dispersion medium with water as the substitute of oil soluble polyurethane material, be subjected to the extensive concern of domestic scholars.But, research aspect the knitted gloves aqueous coating agent is less, (applying date is on July 17th, 2008 to Chinese patent " production method that is used for liner gloves aqueous polyurethane coating connection material ", application number 200810021325.2, open day is on December 24th, 2008, publication number CN101328383A) relates to this field, but, because only selected for use some common, the vulcabond of two functional groups that structure is harder is as raw material, so when the preparation gloves aqueous polyurethane coating connection material, still need add softening agent, composition such as coupling agent and outside cross-linking agent, operation is comparatively complicated, can not adapt to the production line needs fully, and the gloves feel of making is harder.
Summary of the invention
Problem to be solved by this invention provides polyaminoester emulsion of a kind of aqueous coating agent that is used for knitted lining glove and preparation method thereof, need not add softening agent, coupling agent and outside cross-linking agent in the emulsion, prepare the knitted lining glove aqueous coating agent in order to substitute oil-soluble polyurethane products.
A kind of polyaminoester emulsion that is used for the aqueous coating agent of knitted lining glove of the present invention prepares according to following step:
(1) with the trifunctional isocyanate, two functional group's isocyanic ester, dibasic alcohol, the small molecules hydrophilic chain extender, catalyzer and solvent add in the reaction vessel, mix, temperature control 70-90 ℃ was reacted 3-6 hour under inert atmosphere, was cooled to 40-55 ℃, obtained performed polymer;
(2) in the performed polymer of step (1) preparation, add in the neutralizing agent and after, pour emulsifying water into and obtain polyaminoester emulsion, underpressure distillation obtains final product emulsion after sloughing solvent.
With performed polymer is that 100 mass parts are calculated, and wherein said trifunctional isocyanate is the 3-14 mass parts, and described two functional group's isocyanic ester are the 12-38 mass parts, and described dibasic alcohol is the 50-80 mass parts, and described small molecule chain extender is the 4-8 mass parts.
Described solvent load is the 10-30% of performed polymer quality, is preferably the 25-30% of performed polymer quality.
Described catalyst levels is the 0.1-0.3% of performed polymer quality.
Described neutralizing agent consumption is the 70-80% of small molecule chain extender quality, is preferably the 75-80% of small molecule chain extender quality.
Described dibasic alcohol, be selected from following one or more: number-average molecular weight is 6000 to 8000 polyoxytrimethylene dibasic alcohol, number-average molecular weight is 6000 to 8000 polyhutadiene dibasic alcohol, number-average molecular weight is 6000 to 8000 polyether silicone dibasic alcohol, and number-average molecular weight is 6000 to 8000 PTMG dibasic alcohol; Preferred number average molecular weight is that 6000 to 8000 polyoxytrimethylene dibasic alcohol or number-average molecular weight are 6000 to 8000 polyhutadiene dibasic alcohol.
Described two functional group's isocyanic ester are the hexamethylene-diisocyanate dimer.
Described trifunctional isocyanate is the hexamethylene-diisocyanate tripolymer.
Described small molecules hydrophilic chain extender is selected from following a kind of: dimethylol propionic acid, dimethylolpropionic acid, N methyldiethanol amine.
Described catalyzer is selected from following a kind of: dibutyl tin dilaurate, cobalt naphthenate, manganese naphthenate.
Described solvent be selected from following one or more: butanone, butylacetate, methylcarbonate.
Described neutralizing agent is selected from following a kind of: triethylamine, thionamic acid.
Described inert atmosphere is nitrogen, argon gas or helium.
A kind of preparation of the present invention is used for the method for the aqueous polyurethane emulsion of knitted lining glove finishing agent, prepares according to following step:
(1) with the trifunctional isocyanate, two functional group's isocyanic ester, dibasic alcohol, the small molecules hydrophilic chain extender, catalyzer and solvent add in the reaction vessel, mix, temperature control 70-90 ℃ was reacted 3-6 hour under inert atmosphere, was cooled to 40-55 ℃, obtained performed polymer;
(2) in the performed polymer of step (1) preparation, add in the neutralizing agent and after, pour emulsifying water into and obtain polyaminoester emulsion, underpressure distillation obtains final product emulsion after sloughing solvent.
With performed polymer is that 100 mass parts are calculated, and described trifunctional isocyanate is the 3-14 mass parts, and described two functional group's isocyanic ester are the 12-38 mass parts, and described dibasic alcohol is the 50-80 mass parts, and described small molecule chain extender is the 4-8 mass parts.
Described solvent load is the 10-30% of performed polymer quality, is preferably the 25-30% of performed polymer quality.
Described catalyst levels is the 0.1-0.3% of performed polymer quality.
Described neutralizing agent consumption is the 70-80% of small molecule chain extender quality, is preferably the 75-80% of small molecule chain extender quality.
Described dibasic alcohol, be selected from following one or more: number-average molecular weight is 6000 to 8000 polyoxytrimethylene dibasic alcohol, number-average molecular weight is 6000 to 8000 polyhutadiene dibasic alcohol, number-average molecular weight is 6000 to 8000 polyether silicone dibasic alcohol, and number-average molecular weight is 6000 to 8000 PTMG dibasic alcohol; Preferred number average molecular weight is that 6000 to 8000 polyoxytrimethylene dibasic alcohol or number-average molecular weight are 6000 to 8000 polyhutadiene dibasic alcohol.
Described two functional group's isocyanic ester are the hexamethylene-diisocyanate dimer.
Described trifunctional isocyanate is the hexamethylene-diisocyanate tripolymer.
Described small molecules hydrophilic chain extender is selected from following a kind of: dimethylol propionic acid, dimethylolpropionic acid, N methyldiethanol amine.
Described catalyzer is selected from following a kind of: dibutyl tin dilaurate, cobalt naphthenate, manganese naphthenate.
Described solvent be selected from following one or more: butanone, butylacetate, methylcarbonate.
Described neutralizing agent is selected from following a kind of: triethylamine, thionamic acid.
Described inert atmosphere is nitrogen, argon gas or helium.
Another object of the present invention provides a kind of method and corresponding coating method thereof that utilizes aqueous polyurethane emulsion to prepare aqueous coating agent; the aqueous coating agent that this method makes is environment friendly and pollution-free; be beneficial to protection operator's health; gloves good mechanical property, anti-cutting, puncture, wear-resistant, gripability good; waterproof and breathable; hand feel and drape, flexible operation.This coating processes is beneficial to finishing agent and forms the softish film, improves feel, can adapt to original production line of solvent borne polyurethane gloves simultaneously, reduces gloves manufacturer improvement of manufacturing line cost.
A kind of method of utilizing aqueous polyurethane emulsion to prepare aqueous coating agent of the present invention, prepare according to following step: aqueous polyurethane is added in the stirring tank, continuing to add mineral filler, surface slip agent, deionized water, pH value conditioning agent successively under the stirring, add thickening material after stirring, be stirred to even discharging; Wherein by 100 parts of total masses,
Aqueous polyurethane emulsion 30～70
Mineral filler 1～10
Surface slip agent 0.01～0.1
Thickening material 1～5
PH value conditioning agent 0.1～2
The deionized water surplus
Described mineral filler is the nano silicon dispersion liquid, VK-S01H, the JG-100 of Jin Gui chemical company of preferred Hangzhou ten thousand scape novel material companies or the HN-200F1 of Hai Nagaoke company.
Described surface slip agent is a wax emulsion class surface slip agent, AQUAMAT270, the E8046S of Weng Kaier company of preferred German Bi Ke chemical company or the V30N of Weng Kaier company.
Described thickening material is polyurethane associative thickener or propylene soda acid swelling class thickening material; Described polyurethane associative thickener is the Ninghua worker's of German section DSX3290, DSX3820 or DSX3800; Described propylene soda acid swelling class thickening material is the Ninghua worker's of German section HAS662 or HAS634.
Described pH value conditioning agent is a kind of in ammoniacal liquor, 2-amino-2-methyl-1-propanol or the quadrol.
A kind of method of utilizing aqueous coating agent to apply knitted lining glove of the present invention, carry out according to following step:
(1) with the knitted gloves neck bush on fingerprint, the gloves metacarpus immerses finishing agent, takes out;
(2) fingerprint that will scribble finishing agent immerses peptizer, makes finishing agent solidify typing rapidly on knitted lining;
(3) finishing agent is washed after solidifying typing, oven dry.
Can again the gloves metacarpus be immersed finishing agent with carrying out preheating earlier in the described step (1), described preheating temperature is 50-60 ℃.The time of immersing finishing agent in the described step (1) is 2-5 second.The fingerprint that takes out from finishing agent vertically can be placed in the described step (1), be removed unnecessary finishing agent
Peptizer in the described step (2) is that mass percent is the aqueous solution of acid, alkali or the salt of 0.1%-5%.Described acid is hydrochloric acid, sulfuric acid, phosphoric acid, lactic acid, citric acid or acetate; Described alkali is sodium hydroxide, potassium hydroxide or calcium hydroxide; Described salt is sodium-chlor, magnesium chloride, calcium chloride, nitrocalcite or aluminum chloride.
The bake out temperature of described step (3) is preferably 100-120 ℃.
The peptizer that the present invention selects for use is intended to realize breakdown of emulsion to a certain degree, after finishing agent solidifies typing, the whole solid shape that forms of finishing agent, its appearance no longer changes in drying course, evaporation along with internal moisture, the inner space that forms of coating is similar to sponge structure, improves the pliability of coating.
Adopt aqueous coating agent provided by the invention and coating processes, make knitted lining glove, safety and sanitation for latex examination gloves, dress comfortableness, water-proof breathable properties, wear resistance, performances such as thermal insulation, special certain men and women employee of company with 100 20-40 year allows them dress such gloves and tests as object.The result is as follows:
| The gloves performance | The number of affirmative acknowledgement (ACK) | The number of negative acknowledge | Uncertain number |
| Safety and sanitation | ??96 | ??0 | ??4 |
| Dress comfortableness | ??98 | ??1 | ??1 |
| Water-proof breathable properties | ??99 | ??1 | ??0 |
| Wear resistance | ??98 | ??0 | ??2 |
| Thermal insulation | ??99 | ??0 | ??1 |
Embodiment
Further specify technical scheme of the present invention below in conjunction with specific embodiment.
Embodiment 1
Under nitrogen environment, in the reaction vessel that agitator and reflux condensing tube are housed, add 6 parts of (is 100 mass parts in performed polymer) hexamethylene-diisocyanate tripolymers, 30 parts of hexamethylene-diisocyanate dimers, 30 umber average molecular weights are 6000 polyoxypropyleneglycol, 30 umber average molecular weights are 6000 polyether silicone dibasic alcohol, 4 parts of dimethylol propionic acids, 20 parts of butanone are after 0.1 part of dibutyl tin dilaurate mixes, 70 ℃ of temperature controls, reacted 6 hours, and be cooled to 55 ℃, add in 3 parts of triethylamines and after, pour in 400 parts of distilled water and disperse, obtain polyaminoester emulsion.Warp in addition, the solvent in the system is removed in underpressure distillation, obtains final aqueous polyurethane emulsion product.
By 100 parts of total masses: 30 parts of aqueous polyurethane emulsions are added in the stirring tanks, continuing to add 5 parts of VK-S01H, 0.01 part of AQUAMAT270,59.89 parts of deionized waters, 0.1 part of ammoniacal liquor successively under the stirring, add 5 parts of DSX3290 after stirring, the discharging that continues to stir can obtain aqueous coating agent.
The knitted gloves neck bush on fingerprint, is preheated to 60 ℃, and the gloves metacarpus immerses 2s in the finishing agent, fingerprint is vertically placed again, and removes unnecessary finishing agent; The fingerprint that scribbles finishing agent is immersed 0.1% aqueous hydrochloric acid, make finishing agent on knitted lining, solidify typing rapidly; Finishing agent is washed after solidifying typing, to remove peptizer unnecessary on the gloves, enters 110 ℃ of oven for drying afterwards.
Embodiment 2
Under ar gas environment, in the reaction vessel that agitator and reflux condensing tube are housed, add 3 parts of (is 100 mass parts in performed polymer) hexamethylene-diisocyanate tripolymers, 38 parts of hexamethylene-diisocyanate dimers, 20.4 the umber average molecular weight is 7000 polyether silicone glycol, 30.6 the umber average molecular weight is 7000 polyhutadiene dibasic alcohol, 8 parts of dimethylolpropionic acids, 30 parts of ethyl acetate are after 0.2 part of cobalt naphthenate mixes, 80 ℃ of temperature controls, reacted 5 hours, and be cooled to 40 ℃, add in 6 parts of triethylamines and after, pour in 400 parts of distilled water and disperse, obtain polyaminoester emulsion.Warp in addition, the solvent in the system is removed in underpressure distillation, obtains final aqueous polyurethane emulsion product.
By 100 parts of total masses: 70 parts of aqueous polyurethane emulsions are added in the stirring tanks, continuing to add 10 parts of JG-100,0.1 part of E8046S, 16.9 parts of deionized waters, 1 part of 2-amino-2-methyl-1-propanol successively under the stirring, add 3 parts of HAS662 after stirring, the discharging that continues to stir can obtain aqueous coating agent.
On fingerprint, the gloves metacarpus immerses 3s in the finishing agent with the knitted gloves neck bush, takes out; The fingerprint that scribbles finishing agent is immersed 5% sodium chloride aqueous solution, make finishing agent on knitted lining, solidify typing rapidly; Finishing agent is washed after solidifying typing, to remove peptizer unnecessary on the gloves, 110 ℃ of oven dry.
Embodiment 3
Under helium environment, in the reaction vessel that agitator and reflux condensing tube are housed, add 10 parts of (is 100 mass parts in performed polymer) hexamethylene-diisocyanate tripolymers, 15 parts of hexamethylene-diisocyanate dimers, 51.6 the umber average molecular weight is 8000 polybutadiene diol, 19.4 the umber average molecular weight is 8000 PTMG dibasic alcohol, 4 parts of N methyldiethanol amines, 20 parts of butyl carbonates are after 0.3 part of manganese naphthenate mixes, 70 ℃ of temperature controls, reacted 6 hours, and be cooled to 50 ℃, add in 3.2 parts of thionamic acids and after, pour in 400 parts of distilled water and disperse, obtain polyaminoester emulsion.Warp in addition, the solvent in the system is removed in underpressure distillation, obtains final aqueous polyurethane emulsion product.
By 100 parts of total masses: 50 parts of aqueous polyurethane emulsions are added in the stirring tanks, continuing to add 10 parts of HN-200F1,0.05 part of V30N, 35.45 parts of deionized waters, 0.5 part of quadrol successively under the stirring, add 4 parts of DSX3820 after stirring, the discharging that continues to stir can obtain aqueous coating agent.
The knitted gloves neck bush on fingerprint, is preheated to 50 ℃, and the gloves metacarpus immerses 5s in the finishing agent, takes out; The fingerprint that scribbles finishing agent is immersed 2% acetic acid aqueous solution, make finishing agent on knitted lining, solidify typing rapidly; Finishing agent is washed after solidifying typing, to remove peptizer unnecessary on the gloves, enters 100 ℃ of oven for drying afterwards.
Embodiment 4
Under nitrogen environment, in the reaction vessel that agitator and reflux condensing tube are housed, add 4 parts of (is 100 mass parts in performed polymer) hexamethylene-diisocyanate tripolymers, 12 parts of hexamethylene-diisocyanate dimers, 40 umber average molecular weights are 6000 polyhutadiene dibasic alcohol, 40 umber average molecular weights are 6000 PTMG dibasic alcohol, 4 parts of dimethylol propionic acids, 20 parts of methylcarbonates, 10 parts of butanone, 0.2 after a part dibutyl tin dilaurate mixed, 80 ℃ of temperature controls reacted 4 hours, be cooled to 55 ℃, add in 2.8 parts of triethylamines and after, pour in 400 parts of distilled water and disperse, obtain polyaminoester emulsion.Warp in addition, the solvent in the system is removed in underpressure distillation, obtains final aqueous polyurethane emulsion product.
By 100 parts of total masses: 55 parts of aqueous polyurethane emulsions are added in the stirring tanks, continuing to add 7 parts of HN-200F1,0.02 part of V30N, 33.48 parts of deionized waters, 1.5 parts of ammoniacal liquor successively under the stirring, add 3 parts of HAS634 after stirring, the discharging that continues to stir can obtain aqueous coating agent.
The knitted gloves neck bush on fingerprint, is preheated to 50 ℃, and the gloves metacarpus immerses 5s in the finishing agent, fingerprint is vertically placed again, and removes unnecessary finishing agent; The fingerprint that scribbles finishing agent is immersed 1% calcium nitrate aqueous solution, make finishing agent on knitted lining, solidify typing rapidly; Finishing agent is washed after solidifying typing, to remove unnecessary peptizer, 100 ℃ of oven dry down.
Embodiment 5
Under nitrogen environment, in the reaction vessel that agitator and reflux condensing tube are housed, add 14 parts of (is 100 mass parts in performed polymer) hexamethylene-diisocyanate tripolymers, 30 parts of hexamethylene-diisocyanate dimers, 4.9 the umber average molecular weight is 6000 polypropylene dibasic alcohol, 12.3 the umber average molecular weight is 8000 polyether silicone dibasic alcohol, 32.8 part molecular weight is 8000 PTMG dibasic alcohol, 6 parts of dimethylol propionic acids, 10 parts of methylcarbonates, 10 parts of butylacetates, 10 parts of butanone, 0.1 after a part dibutyl tin dilaurate mixed, 70 ℃ of temperature controls reacted 6 hours, be cooled to 45 ℃, add in 4.5 parts of triethylamines and after, pour in 400 parts of distilled water and disperse, obtain polyaminoester emulsion.Warp in addition, the solvent in the system is removed in underpressure distillation, obtains final aqueous polyurethane emulsion product.
By 100 parts of total masses: 40 parts of aqueous polyurethane emulsions are added in the stirring tanks, continuing to add 4 parts of VK-S01H, 0.06 part of E8046S, 49.94 parts of deionized waters, 2 parts of 2-amino-2-methyl-1-propanols successively under the stirring, add 4 parts of HAS662 after stirring, the discharging that continues to stir can obtain aqueous coating agent.
The knitted gloves neck bush on fingerprint, is preheated to 55 ℃, and the gloves metacarpus immerses 4s in the finishing agent, fingerprint is vertically placed again, and removes unnecessary finishing agent; The fingerprint that scribbles finishing agent is immersed 0.1% aqueous sodium hydroxide solution, make finishing agent on knitted lining, solidify typing rapidly; Finishing agent is washed after solidifying typing, to remove unnecessary peptizer, enters 100 ℃ of oven for drying afterwards.
Embodiment 6
Under nitrogen environment, in the reaction vessel that agitator and reflux condensing tube are housed, add 5 parts of (is 100 mass parts in performed polymer) hexamethylene-diisocyanate tripolymers, 15 parts of hexamethylene-diisocyanate dimers, 37.5 the umber average molecular weight is 8000 polypropylene glycol, 37.5 the umber average molecular weight is 8000 polyhutadiene dibasic alcohol, 5 parts of N methyldiethanol amines, 15 parts of N-BUTYL ACETATEs, 15 parts of butanone, 0.1 after a part dibutyl tin dilaurate mixed, 75 ℃ of temperature controls reacted 6 hours, be cooled to 55 ℃, add in 3.75 parts of thionamic acids and after, pour in 400 parts of distilled water and disperse, obtain polyaminoester emulsion.Warp in addition, the solvent in the system is removed in underpressure distillation, obtains final aqueous polyurethane emulsion product.
By 100 parts of total masses: 40 parts of aqueous polyurethane emulsions are added in the stirring tanks, continuing to add 4 parts of VK-S01H, 0.06 part of E8046S, 49.94 parts of deionized waters, 2 parts of quadrols successively under the stirring, add 4 parts of HAS662 after stirring, the discharging that continues to stir can obtain aqueous coating agent.
The knitted gloves neck bush on fingerprint, is preheated to 55 ℃, and the gloves metacarpus immerses 4s in the finishing agent, takes out; The fingerprint that scribbles finishing agent is immersed 0.1% calcium hydroxide aqueous solution, make finishing agent on knitted lining, solidify typing rapidly; Finishing agent is washed after solidifying typing, to remove peptizer unnecessary on the gloves, 120 ℃ of oven dry down.
Embodiment 1～6 gained gloves are carried out every performance test, gained result such as following table.
| Test event | Test result |
| Puncture | Excellent |
| Wear-resistant | Excellent |
| Gripability (doing, wet) | Excellent |
| Flexibility | Excellent |
| Test event | Test result |
| Bio-toxicity | Do not have |
| To skin irritation | Do not have |
A kind of aqueous polyurethane emulsion and finishing agent and manufacture method and coating method that is used for knitted lining glove that the present invention proposes, be described by embodiment, person skilled obviously can be in not breaking away from content of the present invention, spirit and scope to prescription as herein described and method is changed or suitably change realize technology of the present invention with combination.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (10)
1. a polyaminoester emulsion that is used for the aqueous coating agent of knitted lining glove is characterized in that, prepares according to following step:
(1) with the trifunctional isocyanate, two functional group's isocyanic ester, dibasic alcohol, the small molecules hydrophilic chain extender, catalyzer and solvent add in the reaction vessel, mix, temperature control 70-90 ℃ was reacted 3-6 hour under inert atmosphere, was cooled to 40-55 ℃, obtained performed polymer;
(2) in the performed polymer of step (1) preparation, add in the neutralizing agent and after, pour emulsifying water into and obtain polyaminoester emulsion, underpressure distillation obtains final product emulsion after sloughing solvent;
With performed polymer is that 100 mass parts are calculated, and wherein said trifunctional isocyanate is the 3-14 mass parts, and described two functional group's isocyanic ester are the 12-38 mass parts, and described dibasic alcohol is the 50-80 mass parts, and described small molecule chain extender is the 4-8 mass parts; Described solvent load is the 10-30% of performed polymer quality; Described catalyst levels is the 0.1-0.3% of performed polymer quality; Described neutralizing agent consumption is the 70-80% of small molecule chain extender quality.
Described two functional group's isocyanic ester are the hexamethylene-diisocyanate dimer;
Described trifunctional isocyanate is the hexamethylene-diisocyanate tripolymer;
Described dibasic alcohol be selected from following one or more: number-average molecular weight is 6000 to 8000 polyoxytrimethylene dibasic alcohol, number-average molecular weight is 6000 to 8000 polyhutadiene dibasic alcohol, number-average molecular weight is 6000 to 8000 polyether silicone dibasic alcohol, and number-average molecular weight is 6000 to 8000 PTMG dibasic alcohol;
Described small molecules hydrophilic chain extender is selected from following a kind of: dimethylol propionic acid, dimethylolpropionic acid, N methyldiethanol amine;
Described catalyzer is selected from following a kind of: dibutyl tin dilaurate, cobalt naphthenate, manganese naphthenate;
Described solvent be selected from following one or more: butanone, butylacetate, methylcarbonate;
Described neutralizing agent is selected from following a kind of: triethylamine, thionamic acid;
Described inert atmosphere is nitrogen, argon gas or helium.
2. a kind of polyaminoester emulsion that is used for the aqueous coating agent of knitted lining glove according to claim 1 is characterized in that described solvent load is the 25-30% of performed polymer quality; Described dibasic alcohol is that number-average molecular weight is that 6000 to 8000 polyoxytrimethylene dibasic alcohol or number-average molecular weight are 6000 to 8000 polyhutadiene dibasic alcohol; Described neutralizing agent consumption is the 75-80% of small molecule chain extender quality.
3. a method for preparing the aqueous polyurethane emulsion that is used for the knitted lining glove finishing agent is characterized in that, prepares according to following step:
(1) with the trifunctional isocyanate, two functional group's isocyanic ester, dibasic alcohol, the small molecules hydrophilic chain extender, catalyzer and solvent add in the reaction vessel, mix, temperature control 70-90 ℃ was reacted 3-6 hour under inert atmosphere, was cooled to 40-55 ℃, obtained performed polymer;
(2) in the performed polymer of step (1) preparation, add in the neutralizing agent and after, pour emulsifying water into and obtain polyaminoester emulsion, underpressure distillation obtains final product emulsion after sloughing solvent;
With performed polymer is that 100 mass parts are calculated, and wherein said trifunctional isocyanate is the 3-14 mass parts, and described two functional group's isocyanic ester are the 12-38 mass parts, and described dibasic alcohol is the 50-80 mass parts, and described small molecule chain extender is the 4-8 mass parts; Described solvent load is the 10-30% of performed polymer quality; Described catalyst levels is the 0.1-0.3% of performed polymer quality; Described neutralizing agent consumption is the 70-80% of small molecule chain extender quality.
Described two functional group's isocyanic ester are the hexamethylene-diisocyanate dimer;
Described trifunctional isocyanate is the hexamethylene-diisocyanate tripolymer;
Described dibasic alcohol be selected from following one or more: number-average molecular weight is 6000 to 8000 polyoxytrimethylene dibasic alcohol, number-average molecular weight is 6000 to 8000 polyhutadiene dibasic alcohol, number-average molecular weight is 6000 to 8000 polyether silicone dibasic alcohol, and number-average molecular weight is 6000 to 8000 PTMG dibasic alcohol;
Described small molecules hydrophilic chain extender is selected from following a kind of: dimethylol propionic acid, dimethylolpropionic acid, N methyldiethanol amine;
Described catalyzer is selected from following a kind of: dibutyl tin dilaurate, cobalt naphthenate, manganese naphthenate;
Described solvent be selected from following one or more: butanone, butylacetate, methylcarbonate;
Described neutralizing agent is selected from following a kind of: triethylamine, thionamic acid;
Described inert atmosphere is nitrogen, argon gas or helium.
4. a kind of preparation according to claim 3 is used for the method for the aqueous polyurethane emulsion of knitted lining glove finishing agent, it is characterized in that, described solvent load is the 25-30% of performed polymer quality; Described dibasic alcohol is that number-average molecular weight is that 6000 to 8000 polyoxytrimethylene dibasic alcohol or number-average molecular weight are 6000 to 8000 polyhutadiene dibasic alcohol; Described neutralizing agent consumption is the 75-80% of small molecule chain extender quality.
5. method of utilizing aqueous polyurethane emulsion as claimed in claim 1 to prepare aqueous coating agent, it is characterized in that, prepare according to following step: aqueous polyurethane is added in the stirring tank, continuing to add mineral filler, surface slip agent, deionized water, pH value conditioning agent successively under the stirring, add thickening material after stirring, be stirred to even discharging; Wherein by 100 parts of total masses,
Aqueous polyurethane emulsion 30～70
Mineral filler 1～10
Surface slip agent 0.01～0.1
Thickening material 1～5
PH value conditioning agent 0.1～2
The deionized water surplus
Described mineral filler is the nano silicon dispersion liquid; Described surface slip agent is a wax emulsion class surface slip agent; Described thickening material is polyurethane associative thickener or propylene soda acid swelling class thickening material; Described pH value conditioning agent is a kind of in ammoniacal liquor, 2-amino-2-methyl-1-propanol or the quadrol.
6. a kind of method of utilizing aqueous polyurethane emulsion as claimed in claim 1 to prepare aqueous coating agent according to claim 5, it is characterized in that described mineral filler is the VK-S01H of Hangzhou ten thousand scape novel material companies, the JG-100 of Jin Gui chemical company or the HN-200F1 of Hai Nagaoke company; Described surface slip agent is AQUAMAT270, the E8046S of Weng Kaier company of German Bi Ke chemical company or the V30N of Weng Kaier company; Described polyurethane associative thickener is the Ninghua worker's of German section DSX3290, DSX3820 or DSX3800; Described propylene soda acid swelling class thickening material is the Ninghua worker's of German section HAS662 or HAS634.
7. a method of utilizing aqueous coating agent to apply knitted lining glove is characterized in that, carries out according to following step:
(1) with the knitted gloves neck bush on fingerprint, the gloves metacarpus immerses finishing agent, takes out;
(2) fingerprint that will scribble finishing agent immerses peptizer, makes finishing agent solidify typing rapidly on knitted lining;
(3) finishing agent is washed after solidifying typing, oven dry;
Peptizer in the described step (2) is that mass percent is the aqueous solution of acid, alkali or the salt of 0.1%-5%, and wherein said acid is hydrochloric acid, sulfuric acid, phosphoric acid, lactic acid, citric acid or acetate; Described alkali is sodium hydroxide, potassium hydroxide or calcium hydroxide; Described salt is sodium-chlor, magnesium chloride, calcium chloride, nitrocalcite or aluminum chloride.
8. a kind of method of utilizing aqueous coating agent to apply knitted lining glove according to claim 7 is characterized in that, will carry out preheating in the described step (1) earlier and again the gloves metacarpus be immersed finishing agent, and described preheating temperature is 50-60 ℃.
9. a kind of method of utilizing aqueous coating agent to apply knitted lining glove according to claim 7 is characterized in that the time of immersing finishing agent in the described step (1) is 2-5 second.
10. a kind of method of utilizing aqueous coating agent to apply knitted lining glove according to claim 7 is characterized in that the bake out temperature of described step (3) is preferably 100-120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910228609A CN101717487A (en) | 2009-11-20 | 2009-11-20 | Polyurethane emulsion and coating agent used for aquosity coating agent of knitted lining glove as well as preparation method and coating method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910228609A CN101717487A (en) | 2009-11-20 | 2009-11-20 | Polyurethane emulsion and coating agent used for aquosity coating agent of knitted lining glove as well as preparation method and coating method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101717487A true CN101717487A (en) | 2010-06-02 |
Family
ID=42432130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910228609A Pending CN101717487A (en) | 2009-11-20 | 2009-11-20 | Polyurethane emulsion and coating agent used for aquosity coating agent of knitted lining glove as well as preparation method and coating method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101717487A (en) |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845288A (en) * | 2010-06-18 | 2010-09-29 | 天津博苑高新材料有限公司 | Aqueous polyurethane adhesive for tape adhesive film for manufacturing card and preparation method thereof |
| CN101974142A (en) * | 2010-10-22 | 2011-02-16 | 温州市长丰人造革有限公司 | Environmental-friendly PU (Polyurethane) resin and environmental-friendly PU leather prepared therefrom and method for preparing PU leather |
| CN102397833A (en) * | 2010-09-07 | 2012-04-04 | 上海强睿博化工有限公司 | Method for manufacturing waterborne-polyurethane-coated glove |
| CN102417572A (en) * | 2011-11-01 | 2012-04-18 | 吴江市北厍盛源纺织品助剂厂 | Preparation method for polyurethane with high moisture permeability |
| CN102429331A (en) * | 2011-10-16 | 2012-05-02 | 张晖 | Manufacturing technique for aqueous PU (Polyurethane) glove |
| CN102578730A (en) * | 2011-01-05 | 2012-07-18 | 沙嫣 | Method for manufacturing gum dipping safety protection gloves |
| CN102669855A (en) * | 2012-05-08 | 2012-09-19 | 傅玉玉 | Waterborne polyurethane coating glove and production process thereof |
| CN102702468A (en) * | 2012-06-01 | 2012-10-03 | 合肥工业大学 | Silicon-containing polyurethane surfactant and preparation method thereof |
| CN102796447A (en) * | 2012-07-12 | 2012-11-28 | 上海英诺威新材料科技有限公司 | Novel waterborne polyurethane leather finishing agent and preparation method thereof |
| CN102899918A (en) * | 2012-10-11 | 2013-01-30 | 福建可利达合成纤维有限公司 | Method for producing wet-process waterborne polyurethane synthetic leather coating base |
| CN103013321A (en) * | 2012-12-24 | 2013-04-03 | 唐山中红普林塑胶有限公司 | High-strength high-elongation water-based coating agent for powderless PVC (polyvinyl chloride) glove and preparation method |
| WO2013078835A1 (en) * | 2011-12-01 | 2013-06-06 | Zhang Hui | Production process for aqueous pu glove |
| CN103497667A (en) * | 2013-09-12 | 2014-01-08 | 天津冯德亦康新材料科技有限公司 | Laser coating for laser card and preparation method thereof |
| CN104146415A (en) * | 2014-08-29 | 2014-11-19 | 无锡市奇盛针织手套厂 | Anti-skidding gloves |
| CN104358129A (en) * | 2014-11-03 | 2015-02-18 | 金隽 | Water-based highly down-proof finishing agent, preparation method thereof and down-proof fabric after-treatment method |
| CN104497258A (en) * | 2014-12-16 | 2015-04-08 | 安徽灵达化工科技有限公司 | Super-elastic wear-resisting waterborne polyurethane resin and composition and application of super-elastic wear-resisting waterborne polyurethane resin and composition |
| CN104738838A (en) * | 2013-12-25 | 2015-07-01 | 沙嫣 | Water-based PU coating glove production method |
| CN106192409A (en) * | 2016-07-29 | 2016-12-07 | 丹东优耐特纺织品有限公司 | Water writing cloth coating adhesive and processing method |
| CN106232743A (en) * | 2014-04-18 | 2016-12-14 | 蓝宝迪有限公司 | Additive for jetted ink |
| CN107259680A (en) * | 2017-08-14 | 2017-10-20 | 上海深禾聚合物材料有限公司 | A kind of dipped gloves production technology |
| CN107337995A (en) * | 2017-08-14 | 2017-11-10 | 上海深禾聚合物材料有限公司 | A kind of high-temperature resistant waterborne polyurethane finishing agent and its application method |
| CN107501497A (en) * | 2017-08-28 | 2017-12-22 | 同光（江苏）新材料科技有限公司 | A kind of Che Yiyong strippable water-solubles polyurethane resin synthetic method |
| CN107602803A (en) * | 2017-09-22 | 2018-01-19 | 苏州博莱特新材料有限公司 | A kind of waterborne polyurethane resin and preparation method thereof |
| CN107880463A (en) * | 2017-12-09 | 2018-04-06 | 浙江大学自贡创新中心 | A kind of preparation method of puncture-resistant liquid gloves material |
| CN108978252A (en) * | 2018-08-23 | 2018-12-11 | 江苏恒辉安防股份有限公司 | A kind of processing method of bilayer PU gloves |
| CN109196050A (en) * | 2016-06-01 | 2019-01-11 | Dic株式会社 | The manufacturing method of coagulum |
| CN110623376A (en) * | 2019-09-29 | 2019-12-31 | 东莞市瑞翔新型材料科技有限公司 | Waterproof metal zipper and manufacturing process thereof |
| CN110982029A (en) * | 2019-11-21 | 2020-04-10 | 万华化学集团股份有限公司 | Waterborne polyurethane resin emulsion for waterborne space leather base and preparation method thereof, waterborne space leather base and preparation method thereof |
| CN114213635A (en) * | 2021-09-14 | 2022-03-22 | 刘东明 | Method for manufacturing medical product made of renewable biodegradable material |
| CN114213636A (en) * | 2021-09-14 | 2022-03-22 | 刘东明 | Method for manufacturing gloves made of renewable biodegradable materials |
| CN114261046A (en) * | 2021-12-10 | 2022-04-01 | 成都盛帮密封件股份有限公司 | Lamination method of multifunctional latex glove composite surface |
| CN116179070A (en) * | 2022-11-10 | 2023-05-30 | 碧优新材料(广州)有限公司 | Scratch-resistant wear-resistant water-based coating agent for high-grade leather and preparation method thereof |
-
2009
- 2009-11-20 CN CN200910228609A patent/CN101717487A/en active Pending
Cited By (46)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845288B (en) * | 2010-06-18 | 2012-07-04 | 天津博苑高新材料有限公司 | Aqueous polyurethane adhesive for tape adhesive film for manufacturing card and preparation method thereof |
| CN101845288A (en) * | 2010-06-18 | 2010-09-29 | 天津博苑高新材料有限公司 | Aqueous polyurethane adhesive for tape adhesive film for manufacturing card and preparation method thereof |
| CN102397833A (en) * | 2010-09-07 | 2012-04-04 | 上海强睿博化工有限公司 | Method for manufacturing waterborne-polyurethane-coated glove |
| CN101974142B (en) * | 2010-10-22 | 2013-05-08 | 温州市长丰人造革有限公司 | Environmental-friendly PU (Polyurethane) resin and environmental-friendly PU leather prepared therefrom and method for preparing PU leather |
| CN101974142A (en) * | 2010-10-22 | 2011-02-16 | 温州市长丰人造革有限公司 | Environmental-friendly PU (Polyurethane) resin and environmental-friendly PU leather prepared therefrom and method for preparing PU leather |
| CN102578730A (en) * | 2011-01-05 | 2012-07-18 | 沙嫣 | Method for manufacturing gum dipping safety protection gloves |
| CN102578730B (en) * | 2011-01-05 | 2014-08-27 | 沙嫣 | Method for manufacturing gum dipping safety protection gloves |
| CN102429331A (en) * | 2011-10-16 | 2012-05-02 | 张晖 | Manufacturing technique for aqueous PU (Polyurethane) glove |
| CN102417572A (en) * | 2011-11-01 | 2012-04-18 | 吴江市北厍盛源纺织品助剂厂 | Preparation method for polyurethane with high moisture permeability |
| CN102417572B (en) * | 2011-11-01 | 2013-01-09 | 吴江市北厍盛源纺织品助剂厂 | Preparation method for polyurethane with high moisture permeability |
| WO2013078835A1 (en) * | 2011-12-01 | 2013-06-06 | Zhang Hui | Production process for aqueous pu glove |
| CN102669855A (en) * | 2012-05-08 | 2012-09-19 | 傅玉玉 | Waterborne polyurethane coating glove and production process thereof |
| CN102702468A (en) * | 2012-06-01 | 2012-10-03 | 合肥工业大学 | Silicon-containing polyurethane surfactant and preparation method thereof |
| CN102702468B (en) * | 2012-06-01 | 2014-06-25 | 合肥工业大学 | Silicon-containing polyurethane surfactant and preparation method thereof |
| CN102796447B (en) * | 2012-07-12 | 2016-12-21 | 上海英诺威新材料科技有限公司 | Aqueous Polyurethane Leather Finishing Agent and preparation method thereof |
| CN102796447A (en) * | 2012-07-12 | 2012-11-28 | 上海英诺威新材料科技有限公司 | Novel waterborne polyurethane leather finishing agent and preparation method thereof |
| CN102899918A (en) * | 2012-10-11 | 2013-01-30 | 福建可利达合成纤维有限公司 | Method for producing wet-process waterborne polyurethane synthetic leather coating base |
| CN103013321B (en) * | 2012-12-24 | 2015-08-19 | 中红普林（北京）医疗用品高新技术研究院有限公司 | For high strength high extensibility aqueous coating agent and the preparation method of non-powder PVC gloves |
| CN103013321A (en) * | 2012-12-24 | 2013-04-03 | 唐山中红普林塑胶有限公司 | High-strength high-elongation water-based coating agent for powderless PVC (polyvinyl chloride) glove and preparation method |
| CN103497667A (en) * | 2013-09-12 | 2014-01-08 | 天津冯德亦康新材料科技有限公司 | Laser coating for laser card and preparation method thereof |
| CN103497667B (en) * | 2013-09-12 | 2016-01-27 | 天津冯德亦康新材料科技有限公司 | A kind of laser coating for radium-shine card and preparation method thereof |
| CN104738838B (en) * | 2013-12-25 | 2018-04-06 | 南通强生安全防护科技股份有限公司 | Water-based PU coated gloves production method |
| CN104738838A (en) * | 2013-12-25 | 2015-07-01 | 沙嫣 | Water-based PU coating glove production method |
| CN106232743A (en) * | 2014-04-18 | 2016-12-14 | 蓝宝迪有限公司 | Additive for jetted ink |
| CN104146415A (en) * | 2014-08-29 | 2014-11-19 | 无锡市奇盛针织手套厂 | Anti-skidding gloves |
| CN104358129A (en) * | 2014-11-03 | 2015-02-18 | 金隽 | Water-based highly down-proof finishing agent, preparation method thereof and down-proof fabric after-treatment method |
| CN104358129B (en) * | 2014-11-03 | 2016-08-10 | 金隽 | High anti-floss finishing agent of aqueous and preparation method thereof, the post-processing approach of anti-pile fabric |
| CN104497258A (en) * | 2014-12-16 | 2015-04-08 | 安徽灵达化工科技有限公司 | Super-elastic wear-resisting waterborne polyurethane resin and composition and application of super-elastic wear-resisting waterborne polyurethane resin and composition |
| CN109196050B (en) * | 2016-06-01 | 2021-09-21 | Dic株式会社 | Method for producing solidified product |
| CN109196050A (en) * | 2016-06-01 | 2019-01-11 | Dic株式会社 | The manufacturing method of coagulum |
| CN106192409A (en) * | 2016-07-29 | 2016-12-07 | 丹东优耐特纺织品有限公司 | Water writing cloth coating adhesive and processing method |
| CN106192409B (en) * | 2016-07-29 | 2018-04-17 | 丹东优耐特纺织品有限公司 | Water writing cloth coating adhesive and processing method |
| CN107259680A (en) * | 2017-08-14 | 2017-10-20 | 上海深禾聚合物材料有限公司 | A kind of dipped gloves production technology |
| CN107337995A (en) * | 2017-08-14 | 2017-11-10 | 上海深禾聚合物材料有限公司 | A kind of high-temperature resistant waterborne polyurethane finishing agent and its application method |
| CN107501497A (en) * | 2017-08-28 | 2017-12-22 | 同光（江苏）新材料科技有限公司 | A kind of Che Yiyong strippable water-solubles polyurethane resin synthetic method |
| CN107602803B (en) * | 2017-09-22 | 2020-07-14 | 苏州博莱特新材料有限公司 | Waterborne polyurethane resin and preparation method thereof |
| CN107602803A (en) * | 2017-09-22 | 2018-01-19 | 苏州博莱特新材料有限公司 | A kind of waterborne polyurethane resin and preparation method thereof |
| CN107880463A (en) * | 2017-12-09 | 2018-04-06 | 浙江大学自贡创新中心 | A kind of preparation method of puncture-resistant liquid gloves material |
| CN108978252A (en) * | 2018-08-23 | 2018-12-11 | 江苏恒辉安防股份有限公司 | A kind of processing method of bilayer PU gloves |
| CN110623376A (en) * | 2019-09-29 | 2019-12-31 | 东莞市瑞翔新型材料科技有限公司 | Waterproof metal zipper and manufacturing process thereof |
| CN110623376B (en) * | 2019-09-29 | 2022-06-03 | 东莞市瑞翔新型材料科技有限公司 | Waterproof metal zipper and manufacturing process thereof |
| CN110982029A (en) * | 2019-11-21 | 2020-04-10 | 万华化学集团股份有限公司 | Waterborne polyurethane resin emulsion for waterborne space leather base and preparation method thereof, waterborne space leather base and preparation method thereof |
| CN114213635A (en) * | 2021-09-14 | 2022-03-22 | 刘东明 | Method for manufacturing medical product made of renewable biodegradable material |
| CN114213636A (en) * | 2021-09-14 | 2022-03-22 | 刘东明 | Method for manufacturing gloves made of renewable biodegradable materials |
| CN114261046A (en) * | 2021-12-10 | 2022-04-01 | 成都盛帮密封件股份有限公司 | Lamination method of multifunctional latex glove composite surface |
| CN116179070A (en) * | 2022-11-10 | 2023-05-30 | 碧优新材料(广州)有限公司 | Scratch-resistant wear-resistant water-based coating agent for high-grade leather and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101717487A (en) | Polyurethane emulsion and coating agent used for aquosity coating agent of knitted lining glove as well as preparation method and coating method thereof | |
| CN104479102B (en) | Environment-friendly polyurethane clothing leather and preparation method thereof | |
| CN101328383A (en) | Production method for liner gloves aqueous polyurethane coating connection material | |
| CN102618204B (en) | Hot-melt adhesive for bonding layer of artificial leather and preparation method as well as application thereof | |
| CN104031225A (en) | Aqueous polyurethane dispersoid for synthetic leather adhesive and preparation method thereof | |
| CN103013321B (en) | For high strength high extensibility aqueous coating agent and the preparation method of non-powder PVC gloves | |
| CN103173179A (en) | Preparation method of aqueous polyurethane adhesive for laminated composite fabrics | |
| CN108299613B (en) | A kind of antimicrobial form anion aqueous polyurethane resin and preparation method thereof | |
| CN103087286A (en) | Waterborne polyurethane elastic dispersion and preparation method thereof | |
| TW201623371A (en) | Polyether polyol, method for producing polyether polyol, polyester elastomer and polyurethane | |
| CN101831048A (en) | High-gloss polyurethane resins and application thereof | |
| CN111019077A (en) | Solvent-free polyurethane dispersion with controllable particle size and aqueous polyurethane coating liquid | |
| CN105542112A (en) | Waterproof permeable synthetic leather and preparation method thereof | |
| CN107400190B (en) | Breathable surgical glove and preparation method thereof | |
| CN113336911A (en) | Bio-based waterborne polyurethane hot melt adhesive and preparation method and application thereof | |
| CN112812261A (en) | Waterborne polyurethane emulsion, nitrile rubber-polyurethane composite glove and preparation method thereof | |
| CN106188465A (en) | A kind of high resilience waterborne polyurethane resin material and preparation method thereof | |
| CN111909347A (en) | Antibacterial and antiviral anionic waterborne polyurethane resin and preparation method thereof | |
| CN107759762A (en) | A kind of aqueous polyurethane dispersion, antimicrobial form roof of the vehicle Aqueous Polyurethane Adhesives and preparation method thereof | |
| CN108456296A (en) | A kind of waterborne polyurethane resin and preparation method thereof for clothing leather | |
| CN107226897A (en) | One kind can breathe surgical glove waterborne polyurethane resin material and preparation method thereof | |
| CN101818021B (en) | Preparation method of waterborne primer for polyvinylidene chloride | |
| CN115260443A (en) | Waterborne polyurethane material and preparation method of waterborne polyurethane material applied to gloves | |
| CN111533875B (en) | Preparation method of cationic waterborne polyurethane, leather bottom sealing resin and leather coating | |
| CN113372530A (en) | Polyurethane or polyurethane urea aqueous dispersion, preparation method thereof and aqueous clothing leather base |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20100602 |