CN107200828A - It is a kind of for polyurethane of one-component coating and preparation method thereof - Google Patents
It is a kind of for polyurethane of one-component coating and preparation method thereof Download PDFInfo
- Publication number
- CN107200828A CN107200828A CN201710344081.0A CN201710344081A CN107200828A CN 107200828 A CN107200828 A CN 107200828A CN 201710344081 A CN201710344081 A CN 201710344081A CN 107200828 A CN107200828 A CN 107200828A
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- polyurethane
- sealer
- binary
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- reaction
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
- C08G18/8067—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds phenolic compounds
-
- 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
- C08G18/302—Water
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
- C08G18/808—Monoamines
-
- 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
Abstract
It is a kind of for polyurethane of one-component coating and preparation method thereof that the present invention is provided, and the preparation method includes：Step S1, binary isocyanates and sealer reaction obtain the first mixture, wherein, the mol ratio of the binary isocyanates and sealer is 0.9:1‑1:1；Step S2, in first mixture water is added, chain extending reaction is produced；In preparation process, by controlling binary isocyanates and sealer, and/or binary isocyanates and water mol ratio, meanwhile, by controlling its reaction temperature, can effectively control the quality of polyurethane.Compared to polyurethane in the prior art for process control is complicated, reagent type is more, cost is high the problem of, of the invention is a kind of for polyurethane of one-component coating and preparation method thereof, and reagent type is few, with low cost.
Description
Technical field
The present invention relates to coating material, more particularly, to a kind of polyurethane for one-component coating and its preparation side
Method.
Background technology
Electrophoresis be coating metal workpiece it is the most frequently used, be also one of most efficient method.Electrophoretic painting is by with conduction
The coated article of property is immersed in the hopper equipped with electrophoretic coating as cathode/anode, and corresponding anode/the moon is separately set in hopper
Pole, turn-on current for a period of time, uniform fine and closely woven film is deposited on coated article surface between the two poles of the earth.Wherein, electrophoretic coating,
Referred to as electrophoretic paint, is to influence a key factor of final film quality during electrophoretic painting.
Coating is the coating material on protection and decorating objects surface, is applied to body surface, can form thin film,
Assign effect of the object to protect, beautify or needed for other.Polyurethane resin is relatively conventional one kind in coating resin.
At present, prepare occlusive polyurethane typically using glycerine, trimethylolpropane and pentaerythrite, etc. to two degrees of functionality
Polyisocyanates carries out chain extension, increases the reflecting point of occlusive polyurethane, increases the crosslink density of coating film；Or, can also
Material synthesis occlusive polyurethane is used as using the tripolymer of polyisocyanates.
With reagents such as glycerine, trimethylolpropane, pentaerythrites, then it is high to there is chain extension cost, or reaction controlling condition is severe
Carve, viscosity is big, the phenomenons such as gel, particularly trimethylolpropane easily occur and pentaerythrite is solid, need first to be dissolved with solvent
After add, to course of reaction control also need it is very strict；The occlusive polyurethane of polyisocyanate trimer synthesis is on the high side,
The sealer of binary polyisocyanates must be added to adjust the performance of coating film, it is necessary to several raw material, to company
Storage and working capital of enterprises are a tests.
When current conventional method prepares occlusive polyurethane, usual technical process is complex, control condition is more, examination used
Agent species is more, cost high.
The content of the invention
The present invention, which provides a kind of one kind for overcoming above mentioned problem or solving the above problems at least in part, is used for one-component
Polyurethane of coating and preparation method thereof, to solve complicated polyurethane preparation process, more difficult control and the high technical problem of cost.
In the present invention, part can be the unit of weight well known in the art such as μ g, mg, g, kg or its multiple, such as 1/
10th, 1/100,10 times, 100 times etc..
According to an aspect of the present invention there is provided a kind of preparation method of polyurethane, the polyurethane is used for one-component coating,
Including：
Step S1, binary isocyanates and sealer reaction obtains the first mixture, wherein, the binary isocyanates with
The mol ratio of sealer is 0.9:1-1:1；
Step S2, in first mixture water is added, chain extending reaction is produced.
Occlusive polyurethane of the prior art is usually to two functions using glycerine, trimethylolpropane, pentaerythrite etc.
The polyisocyanates of degree carries out chain extension, increases the reflecting point of occlusive polyurethane, increases the crosslink density of coating film；Or, with
The tripolymer of polyisocyanates is used as Material synthesis occlusive polyurethane.
Because trimethylolpropane, pentaerythrite are solids, the control of its course of reaction need to be very strict when being directly added into,
Technical process control is complicated.In addition, obtaining occlusive polyurethane using this kind of method, the raw material types that it is related to are various, price
Cost is high.
Directly using water as chain extender, under suitable control condition, by the part-NCO keys in binary isocyanates with
Sealer occurs after end capping reaction, then in the presence of water, chain extending reaction occurs again for the-NCO keys in the mixture of gained first i.e.
Can obtain occlusive polyurethane, can process simplification, effectively reduce cost.
It is understood that in preparation process, i.e. in binary isocyanates and sealer generation end capping reaction, and/
Or, during in the presence of water chain extending reaction occurs for the mixture of gained first, cosolvent is added, so that reaction is more smoothly
Carry out.Cosolvent is preferably one kind or several in dimethylbenzene, ethyl acetate, butyl acetate, acetone, butanone, methyl iso-butyl ketone (MIBK)
Kind；It is highly preferred that cosolvent can select methyl iso-butyl ketone (MIBK), butyl acetate and/or acetone.
Specifically, during binary isocyanates and sealer reaction, binary isocyanates is first dissolved in cosolvent
In, for example, binary isocyanates is dissolved in methyl iso-butyl ketone (MIBK), or it is dissolved in methyl iso-butyl ketone (MIBK) and butyl acetate.Then,
Sealer is added in said mixture again.Then, binary isocyanates can be dissolved in cosolvent with sealer, with more preferable
Promotion reaction progress.It is understood that the amount of cosolvent can carry out appropriate tune according to the amount of binary isocyanates
It is whole, so that the solid content after mixing in the mixture of gained is 70%-85%.
Specifically, the mol ratio for making the binary isocyanates and sealer is 0.9:1-1:1.By binary isocyanates with
The molar ratio of sealer is maintained at suitable scope, and binary isocyanates, when certain condition reacts, makes binary with sealer
With sealer end capping reaction occurs for the part-NCO keys of isocyanates, without all with sealer reaction and make subsequent reactions without
Method is normally carried out.
Meanwhile, the ratio of control binary isocyanates and sealer, to control-NCO the keys in the first mixture of gained
Quantity, after end capping reaction occurs for the part-NCO keys of binary isocyanates, then to occur chain extension in the presence of chain extender water
During reaction, the efficiency and product of reaction can be preferably controlled, the chain length or molecular weight of gained occlusive polyurethane is maintained at conjunction
Suitable scope, with the occlusive polyurethane conformed to quality requirements.
Preferably, step S1 is still further comprised：The NCO% contents of the first mixture are detected, make first mixture
In NCO% values and the binary isocyanates in the ratios of NCO% values be 48:100-52:100.Unless otherwise specified, this hair
NCO% in bright refers to-NCO mass percentage content.
By controlling NCO% contents in reaction condition, detection the first mixture of gained, to control the extent of reaction or progress,
Ensure being smoothed out for subsequent reactions, and final product quality.
Preferably, the mol ratio of the binary isocyanates and water is 2:1-5:1.In control binary isocyanates and closing
On the basis of agent end capping reaction, the consumption of chain extender is added by adjustment, makes binary isocyanates and the water as chain extender
Mol ratio be maintained at suitable scope, control the degree of chain extending reaction, the degree that further regulation and control reaction is carried out, to control most
The quality of whole products therefrom.
Preferably, after binary isocyanates is mixed with sealer, its temperature for occurring end capping reaction is 60-100 DEG C；It is more excellent
Selection of land, the binary isocyanates is 50-80 DEG C with the temperature that sealer reacts.It is understood that binary isocyanates with
The mol ratio of sealer is maintained on the basis of zone of reasonableness, and it is anti-that with sealer end-blocking occurs at such a temperature for binary isocyanates
Should, by reasonably monitoring the time of reaction, so that in the first mixture in NCO% values and the binary isocyanates
The ratio of NCO% values is maintained at 48:100-52:100, so as to control being smoothed out for subsequent reactions.
The temperature of end capping reaction is maintained at suitable scope, the process for being conducive to control to react, to control final product
Quality.Reaction temperature is too high, and-NCO content reduction is faster during reaction, and reaction is more difficult to control, and side reaction degree is also higher, unfavorable
In the stability of polyurethane；Temperature is too low, and reaction speed is slow, and exothermic heat of reaction is gentle, is easily controlled, but reaction time is oversize,
Production efficiency is relatively low.Reaction temperature is maintained in suitable temperature ranges, and side reaction is few, and reaction time is moderate, and reaction is also easy to control
System.
Preferably, the molecular weight of binary isocyanates is in suitable scope, i.e., different from the binary in the range of particular types
Cyanate,
Preferably, binary isocyanates is specially toluene di-isocyanate(TDI), hexamethylene diisocyanate, isophorone two
Double (4- cyclohexyls isocyanates) the cyclohexyl methane diisocyanates of isocyanates, methyl diphenylene diisocyanate or methylene,
The control of the extent of reaction and the guarantee of product quality can be more beneficial for.
It is highly preferred that binary isocyanates is toluene di-isocyanate(TDI) or IPDI.
Preferably, sealer is gaultherolin, 3,5- dimethyl pyrazoles, antifebrin, phenol, caprolactam, second two
Alcohol list ether, ethylene glycol ether, ethylene glycol monobutyl ether or ethylene glycol monohexylether；It is highly preferred that sealer is ethylene glycol list second
Ether or ethylene glycol monohexylether.
Preferably, in the presence of water, its temperature for occurring chain extending reaction is 50-120 DEG C；It is highly preferred that the chain extension
The temperature of reaction is 70-120 DEG C.On the basis of the ratio of control reactant, the temperature of chain extending reaction is further controlled, with
The degree that preferably control is reacted.It is understood that work as the first mixture occurs chain extending reaction at such a temperature with water, suitably
Monitoring reaction time so that the NCO% in final product<8×10-3%, you can the closing for being met quality requirement gathers
Urethane product.
Specifically, in step S2, when adding chain extender water in the first mixture, water is added to together with cosolvent to the
In one mixture, for example, water is added in the first mixture together with acetone.First mixture can be dissolved in molten altogether with water
In agent, with the more preferable progress for promoting to react.
Preferably, a kind of preparation method of polyurethane, including：
Step S1, binary isocyanates and sealer reaction obtains the first mixture, wherein, the binary isocyanates with
The mol ratio of sealer is 0.9:1-1:1, the mol ratio of the binary isocyanates and water is 3:1-5:1；
Step S2, in first mixture water is added, chain extending reaction is produced；
The temperature that the binary isocyanates reacts after being mixed with sealer is 60-100 DEG C, the temperature of the chain extending reaction
For 50-120 DEG C.
By controlling the relative usage between binary isocyanates, sealer and water, to control the degree that reaction is carried out, keep away
Exempt from chain extending reaction to be difficult to control and make final product be easy to solidification, or do not reach the requirement of polymerization.
The present invention also provides a kind of occlusive polyurethane, is prepared using the above method, and the occlusive polyurethane is applied for one-component
The raw material of material.Directly using water as chain extender, in the suitable molar ratio of binary isocyanates and sealer, and
Occur end capping reaction and chain extending reaction respectively at a suitable temperature, can either reasonably control extent of reaction, can do the best again
Reduce the generation of side reaction, it is possible to increase the quality of gained polyurethane.
Beneficial effects of the present invention are mainly as follows：
(1) it is maintained in the molar ratio of binary isocyanates and sealer under suitable scope, expansion is directly used as using water
Chain agent, it is that can obtain occlusive polyurethane to occur chain extending reaction, not only effectively reduces cost, also simplify technical process；
(2) molar ratio of binary isocyanates and water is maintained at suitable scope, can further control the journey of reaction
Degree, it is ensured that end product quality；
(3) reaction temperature is maintained at suitable scope in preparation process, can either effectively reduce side reaction, and reaction time
Moderate, reaction is also easy to control.
Embodiment
With reference to embodiment, the embodiment to the present invention is described in further detail.Following examples are used for
Illustrate the present invention, but be not limited to the scope of the present invention.
Number is in parts by weight in following examples.
Embodiment 1
By 504 parts of hexamethylene diisocyanates (HDI), 150 parts of methyl iso-butyl ketone (MIBK)s are put into reactor bottom, are warming up to 70
DEG C, the ethylene glycol monoethyl ether of 270 parts of dropwise addition, temperature is maintained at 70-80 DEG C, detects NCO%=13.64 ± 0.1%, is added dropwise 18 parts
Deionized water and 50 parts of acetone, temperature is maintained at 70-80 DEG C, and after after exothermic reaction disappearance, temperature is warming up to 110-120
DEG C, detection NCO% ＜ 8 × 10-3%, that is, obtain occlusive polyurethane.
Embodiment 2
By 890 parts of IPDIs (IPDI), 150 parts of methyl iso-butyl ketone (MIBK)s, 100 parts of butyl acetates are put into instead
Bottom is answered, 70 DEG C are warming up to, 360 parts of ethylene glycol monoethyl ether is added dropwise, temperature is maintained at 70-80 DEG C, detects NCO%=18.75
± 0.1%, 18 parts of deionized water and 50 parts of acetone is added dropwise, temperature is maintained at 70-80 DEG C, it is warm after after exothermic reaction disappearance
Degree is warming up to 110-120 DEG C, detection NCO% ＜ 8 × 10-3%, that is, obtain occlusive polyurethane.
Embodiment 3
By 696 parts of toluene di-isocyanate(TDI)s (TDI), 150 parts of methyl iso-butyl ketone (MIBK)s, 150 parts of butyl acetates are put into reactor
Bottom, is warming up to 50 DEG C, and 730 parts of ethylene glycol monohexylethers are added dropwise, and temperature is maintained at 50-60 DEG C, detects NCO%=7.99 ± 0.1%,
18 parts of deionized water and 50 parts of acetone is added dropwise, temperature is maintained at 70-80 DEG C, after after exothermic reaction disappearance, temperature is warming up to
100-110 DEG C, detection NCO% ＜ 8 × 10-3%, that is, obtain occlusive polyurethane.
Finally, method of the invention is only preferably embodiment, is not intended to limit the scope of the present invention.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements made etc. should be included in the protection of the present invention
Within the scope of.
Claims (9)
1. a kind of preparation method of polyurethane, it is characterised in that including：
Step S1, binary isocyanates and sealer reaction obtain the first mixture, wherein, the binary isocyanates and closing
The mol ratio of agent is 0.9:1-1:1.
Step S2, in first mixture water is added, chain extending reaction is produced.
2. a kind of preparation method of polyurethane as claimed in claim 1, it is characterised in that step S1 is still further comprised：Inspection
The NCO% values of first mixture are surveyed, are made in the NCO% values and the binary isocyanates in first mixture
The ratio of NCO% values is 48:100-52:100.
3. a kind of preparation method of polyurethane as claimed in claim 1 or 2, it is characterised in that：The binary isocyanates with
The mol ratio of water is 2:1-5:1.
4. a kind of preparation method of polyurethane as claimed in claim 3, it is characterised in that：Binary isocyanic acid described in step S1
Ester is 60-100 DEG C with the temperature that sealer reacts；
Preferably, the binary isocyanates and the temperature that sealer reacts are 50-80 DEG C.
5. a kind of preparation method of polyurethane as described in claim any one of 1-4, it is characterised in that：The binary isocyanic acid
Ester is toluene di-isocyanate(TDI), hexamethylene diisocyanate, IPDI, methyl diphenylene diisocyanate
Or double (4- cyclohexyls isocyanates) the cyclohexyl methane diisocyanates of methylene；
Preferably, the binary isocyanates is toluene di-isocyanate(TDI) or IPDI.
6. a kind of preparation method of polyurethane as described in claim any one of 1-5, it is characterised in that the sealer is：
Gaultherolin, 3,5- dimethyl pyrazoles, antifebrin, phenol, caprolactam, ethylene glycol monoethyl ether, ethylene glycol ether, second
Glycol monobutyl ether or ethylene glycol monohexylether；
Preferably, the sealer is ethylene glycol monoethyl ether or ethylene glycol monohexylether.
7. a kind of preparation method of polyurethane as claimed in claim 6, it is characterised in that：The temperature of the chain extending reaction is
50-120℃；
Preferably, the temperature of the chain extending reaction is 70-120 DEG C.
8. a kind of preparation method of polyurethane as claimed in claim 1, it is characterised in that including：
Step S1, binary isocyanates and sealer reaction obtain the first mixture, wherein, the binary isocyanates and closing
The mol ratio of agent is 0.9:1-1:1, the mol ratio of the binary isocyanates and water is 3:1-5:1；
Step S2, in first mixture water is added, chain extending reaction is produced；
The temperature that the binary isocyanates reacts after being mixed with sealer is 60-100 DEG C, and the temperature of the chain extending reaction is
50-120℃。
9. occlusive polyurethane prepared by the method as described in claim any one of 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710344081.0A CN107200828B (en) | 2017-05-16 | 2017-05-16 | Polyurethane for single-component coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710344081.0A CN107200828B (en) | 2017-05-16 | 2017-05-16 | Polyurethane for single-component coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107200828A true CN107200828A (en) | 2017-09-26 |
| CN107200828B CN107200828B (en) | 2020-02-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201710344081.0A Expired - Fee Related CN107200828B (en) | 2017-05-16 | 2017-05-16 | Polyurethane for single-component coating and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111320742A (en) * | 2020-04-07 | 2020-06-23 | 湖南湘江关西涂料(长沙)有限公司 | Blocked isocyanate curing agent, preparation method thereof, single-component coating and coating product |
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|---|---|---|---|---|
| JPS61235476A (en) * | 1985-04-10 | 1986-10-20 | Nippon Paint Co Ltd | Cationic electrodeposition paint composition |
| CN102731746A (en) * | 2012-06-29 | 2012-10-17 | 上海东升新材料有限公司 | Enclosed type aqueous polyurethane emulsion papermaking wet strength agent and its preparation method |
| CN103319689A (en) * | 2013-06-24 | 2013-09-25 | 浩力森涂料（上海）有限公司 | Emulsion resin for high-throwing-power cathode electrophoretic paint and preparation method thereof |
| CN105504206A (en) * | 2015-12-24 | 2016-04-20 | 山东一诺威新材料有限公司 | Synthetic method of castor oil based enclosed type waterborne polyurethane |
-
2017
- 2017-05-16 CN CN201710344081.0A patent/CN107200828B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61235476A (en) * | 1985-04-10 | 1986-10-20 | Nippon Paint Co Ltd | Cationic electrodeposition paint composition |
| CN102731746A (en) * | 2012-06-29 | 2012-10-17 | 上海东升新材料有限公司 | Enclosed type aqueous polyurethane emulsion papermaking wet strength agent and its preparation method |
| CN103319689A (en) * | 2013-06-24 | 2013-09-25 | 浩力森涂料（上海）有限公司 | Emulsion resin for high-throwing-power cathode electrophoretic paint and preparation method thereof |
| CN105504206A (en) * | 2015-12-24 | 2016-04-20 | 山东一诺威新材料有限公司 | Synthetic method of castor oil based enclosed type waterborne polyurethane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111320742A (en) * | 2020-04-07 | 2020-06-23 | 湖南湘江关西涂料(长沙)有限公司 | Blocked isocyanate curing agent, preparation method thereof, single-component coating and coating product |
| CN111320742B (en) * | 2020-04-07 | 2022-03-25 | 湖南湘江关西涂料(长沙)有限公司 | Blocked isocyanate curing agent, preparation method thereof, single-component coating and coating product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107200828B (en) | 2020-02-18 |
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