CN103351460A - Preparation method of cation waterproof cross-linking agent - Google Patents
Preparation method of cation waterproof cross-linking agent Download PDFInfo
- Publication number
- CN103351460A CN103351460A CN2013102906251A CN201310290625A CN103351460A CN 103351460 A CN103351460 A CN 103351460A CN 2013102906251 A CN2013102906251 A CN 2013102906251A CN 201310290625 A CN201310290625 A CN 201310290625A CN 103351460 A CN103351460 A CN 103351460A
- Authority
- CN
- China
- Prior art keywords
- waterproof
- linking agent
- preparation
- positively charged
- charged ion
- 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
Images
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of a cation waterproof cross-linking agent. At present, certain sealed isocyanate is not suitable for application process and requirement of waterproof finish of fabrics. The preparation method adopting the technical scheme is characterized in that a cation hydrophilic chain extender is firstly connected in an isocyanate structure, then the excessive isocyanate group is sealed by a sealing agent, and finally, the cation waterproof cross-linking agent is obtained after removing the solvent through emulsification dispersion and distillation. The waterproof cross-linking agent prepared by the invention is compounded with a waterproof agent to be applied in the waterproof finish of the fabrics, as a result, the waterproof effect of the waterproof agent is remarkably improved, and meanwhile, the binding strength of the waterproof agent and the fabrics is improved.
Description
Technical field
The present invention relates to watersoluble closed isocyanic acid ester synthesis field, the definite preparation method who says a kind of cationic blocked isocyanate waterproof linking agent.
Background technology
Water-proof aagent is a kind of fabric that is applicable to the fabrics such as cotton, hair, silk, chemical fibre and mixed fibre, give the spinning post-finishing agent that it has super waterproofing function, but through the fabric of WATER REPELLENT, after through washing, waterproof effect has reduction in various degree.
In order to address this problem, often use linking agent.At present, domestic with aminoresin as the waterproof linking agent, very large to the waterproof effect negative impact at water-resisting agent initial stage although it can improve the washing fastness of water-resisting agent, and discharge a large amount of formaldehyde when baking, larger to harm.Watersoluble closed isocyanate crosslinking, the NCO group is in closed state at normal temperatures, to active H inactivation, in the waterproofing process, high temperature bakes down, blocked isocyanate generation deblocking reaction, the NCO group that discharges respectively with fabric, water-resisting agent in active H reaction, form chemical bond, thereby play the purpose that improves water-resisting agent and fabric binding strength.
Application number is 02817963.3 Chinese patent application, and it adopts the direct blocked isocyanate of Diisopropylamine, obtains water-based and/or water-dilutable isocyanic ester, is used for automotive paints.The Chinese patent application of application number 00116991.2, choosing molecular weight is many ethylene glycol monoalkyl ethers of 300-800, with polymeric polyisocyanate reaction, make the linking agent of water dispersible property, the characteristics such as that the coating that cooperates with the water-based hydroxyl resin Composition is filmed is not easy to foaming, high gloss, surface drying time are fast.Application number is the Chinese patent application of 201110144019.X, chooses the isocyanic ester of pyrazoles end-blocking, is used for paint spraying, can significantly improve coating to the sticking power of base material.
More than several blocked isocyanates, all be unwell to application art and the requirement of fabric waterproof arrangement.Develop the blocked isocyanate linking agent that is suitable for the fabric waterproof arrangement, its ionic positively charged ion that is required to be, just can and not reduce waterproof effect with the even blend of water-resisting agent, the blocked isocyanate deblocking temperature then will in the processing temperature scope of fabric waterproof arrangement (120-200 ℃), could be realized good effect so simultaneously.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective that above-mentioned prior art exists, and a kind of preparation method of the positively charged ion waterproof linking agent for improving water-resisting agent and fabric binding strength is provided.
For this reason, the present invention adopts following technical scheme: a kind of preparation method of positively charged ion waterproof linking agent, and it is below step:
1) 3-15 part cationic hydrophilic chainextender N methyldiethanol amine is added in the isocyanic ester of 20-60 part, open and stir, 40-85 ℃ of lower reaction 0.5-3 hour, in the structure with cationic hydrophilic chainextender access isocyanic ester;
2) mixture of encapsulant 8-32 part and 12-24 part butanone is added step 1) reaction system in, 60-85 ℃ of lower reaction 1-4 hour, isocyanate groups that will be excessive with encapsulant sealed;
3) with the 2nd) synthetic performed polymer of step is dispersed in the aqueous solution of 2-8 part neutralizing agent, emulsification 5-10min under agitation, butanone is deviate from afterwards underpressure distillation, and obtaining solid content is the positively charged ion waterproof linking agent of 25-35%;
Raw material umber in the above-mentioned steps is parts by weight.
The cation blocked isocyanate crosslinking that the present invention makes, be applied to the waterproofing of fabric, waterproof effect is promoted obviously, can also improve simultaneously the wash durability of water-resisting agent, the toxic substance such as release formaldehyde, volatile solvent not in the use procedure, safety and environmental protection has wide market outlook.
Further, the isocyanic ester step 1) is preferably a kind of in tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, toluene diisocyanate trimer, the hexamethylene diisocyanate trimer.
Further, step 2) encapsulant in is preferably acetoxime, Diacetylmonoxime, cyclohexanone oxime, ξ-caprolactam, 3，5-dimethylpyrazole, butanols, 1,2, a kind of in the 4-triazole.
Further, the neutralizing agent step 3) is preferably Glacial acetic acid.
Compared with prior art, the present invention has following beneficial effect: (1) is accessed hydrophilic radical in the isocyanate molecule chain, so that product has excellent dispersion stability, composite stability and package stability.(2) by the selection of different sorts encapsulant, isocyanic ester, can the deblocking temperature of product be designed, make it adapt to the waterproofing fabrication process condition of different fabrics.(3) introduce the cationic hydrophilic chainextender in this water-soluble closed isocyanic ester, be specially adapted to the fabric waterproof finishing functions.(4) the waterproof linking agent that makes of the present invention, with the water-resisting agent composite usage in fabric waterproof arrangement, can significantly improve the waterproof effect of water-resisting agent, improved simultaneously the binding strength between water-resisting agent and the fabric, fabric machine washing 5 times, waterproof effect does not descend or only faint decline.
Description of drawings
Fig. 1 is the infrared spectrum of the performed polymer before and after the sealing in the embodiment of the invention 1.
Embodiment
The invention will be further described below by specification drawings and specific embodiments.
Embodiment 1
It is as follows to fill a prescription:
| Raw material | Quality/g |
| Tolylene diisocyanate | 24.5 |
| Butanone | 19.5 |
| N methyldiethanol amine | 4.3 |
| Glacial acetic acid | 2.2 |
| Diacetylmonoxime | 18.5 |
| Deionized water | 110 |
Preparation process is as follows:
(1) in the four-hole boiling flask that agitator, reflux condensing tube, thermometer are housed, adds tolylene diisocyanate, start stirring N methyldiethanol amine is added in the four-hole bottle, under 50 ℃, react to NCO content to theoretical value (it being detected with the Di-n-Butyl Amine volumetry);
(2) be cooled to 40 ℃, in the mixed solution adding four-hole bottle with Diacetylmonoxime and butanone, 60 ℃ are reacted to NCO content to theoretical value (it being detected with the Di-n-Butyl Amine volumetry), obtain prepolymer;
(3) prepolymer that second step is obtained adds in the mixture of Glacial acetic acid and deionized water, carries out immediately in the emulsification in emulsify at a high speed equipment and 5-10min, and butanone is removed in underpressure distillation after the emulsification neutralization, obtains positively charged ion waterproof linking agent.
Embodiment 2
It is as follows to fill a prescription:
| Raw material | Quality/g |
| Hexamethylene diisocyanate | 24 |
| Butanone | 20 |
| N methyldiethanol amine | 6.3 |
| Glacial acetic acid | 3.2 |
| ξ-caprolactam | 22.5 |
| Deionized water | 123 |
Preparation process is as follows:
(1) in the four-hole boiling flask that agitator, reflux condensing tube, thermometer are housed, adds hexamethylene diisocyanate, start stirring N methyldiethanol amine is added in the four-hole bottle, under 70 ℃, react to NCO content to theoretical value (it being detected with the Di-n-Butyl Amine volumetry);
(2) be cooled to 40 ℃, in the mixed solution adding four-hole bottle with ξ-caprolactam and butanone, 75 ℃ are reacted to NCO content to theoretical value (it being detected with the Di-n-Butyl Amine volumetry), obtain prepolymer;
(3) prepolymer that second step is obtained adds in the mixture of Glacial acetic acid and deionized water, carries out immediately in the emulsification in emulsify at a high speed equipment and 5-10min, and butanone is removed in underpressure distillation after the emulsification neutralization, obtains positively charged ion waterproof linking agent.
Embodiment 3
It is as follows to fill a prescription:
Preparation process is as follows:
(1) agitator is being housed, reflux condensing tube, add diphenylmethanediisocyanate in the four-hole boiling flask of thermometer, start stirring N methyldiethanol amine is added in the four-hole bottle, under 45 ℃, react to NCO content to theoretical value (available Di-n-Butyl Amine volumetry detects it);
(2) be cooled to 40 ℃, in the mixed solution adding four-hole bottle with 3，5-dimethylpyrazole and butanone, 60 ℃ are reacted to NCO content to theoretical value (it being detected with the Di-n-Butyl Amine volumetry), obtain prepolymer;
(3) prepolymer that second step is obtained adds in the mixture of Glacial acetic acid and deionized water, carries out immediately in the emulsification in emulsify at a high speed equipment and 5-10min, and butanone is removed in underpressure distillation after the emulsification neutralization, obtains positively charged ion waterproof linking agent.
Embodiment 4
It is as follows to fill a prescription:
| Raw material | Quality/g |
| Isophorone diisocyanate | 48 |
| Butanone | 22 |
| N methyldiethanol amine | 5.56 |
| Glacial acetic acid | 2.85 |
| Butanols | 25.5 |
| Deionized water | 185 |
Preparation process is as follows:
(1) agitator is being housed, reflux condensing tube, add isophorone diisocyanate in the four-hole boiling flask of thermometer, start stirring N methyldiethanol amine is added in the four-hole bottle, under 75 ℃, react to NCO content to theoretical value (it being detected with the Di-n-Butyl Amine volumetry);
(2) be cooled to 40 ℃, in the mixed solution adding four-hole bottle with butanols and butanone, 85 ℃ are reacted to NCO content to theoretical value (it being detected with the Di-n-Butyl Amine volumetry), obtain prepolymer;
(3) prepolymer that second step is obtained adds in the mixture of Glacial acetic acid and deionized water, carries out immediately in the emulsification in emulsify at a high speed equipment and 5-10min, and butanone is removed in underpressure distillation after the emulsification neutralization, obtains positively charged ion waterproof linking agent.
Embodiment 5
It is as follows to fill a prescription:
Preparation process is as follows:
(1) agitator is being housed, reflux condensing tube, add toluene diisocyanate trimer in the four-hole boiling flask of thermometer, start stirring N methyldiethanol amine is added in the four-hole bottle, under 50 ℃, react to NCO content to theoretical value (available Di-n-Butyl Amine volumetry detects it);
(2) be cooled to 40 ℃, in the mixed solution adding four-hole bottle with acetoxime and butanone, 65 ℃ are reacted to NCO content to theoretical value (it being detected with the Di-n-Butyl Amine volumetry), obtain prepolymer;
(3) prepolymer that first two steps is obtained adds in the mixture of Glacial acetic acid and deionized water, carries out immediately in the emulsification in emulsify at a high speed equipment and 5-10min, and butanone is removed in underpressure distillation after the emulsification neutralization, obtains positively charged ion waterproof linking agent.
By USS AATCC22, the positively charged ion waterproof linking agent to synthetic among the embodiment 1 carries out the application performance evaluation.The white cotton of anthology, 121 spring Asias are spun, 101 Ta Silong, blue polyester-cotton blend, 5 kinds of fabrics of green Polyester Taffeta are as base cloth, and fluorine is that the waterproof and oilproof machining agent uses with bathing as finishing composition and positively charged ion waterproof linking agent, and addition is respectively 20g/L and 5g/L.The technical process of waterproofing is as follows:
The cloth specimen water resistance is as follows behind the waterproofing:
Can get from upper table data, waterproof linking agent and water-resisting agent are used for the fabric waterproof arrangement with bathing, and than independent use water-resisting agent, the fabric after the arrangement in the early stage degree of getting wet aspect has obvious lifting (10-30 divides).After washing 5 times, use separately the fabric of water-resisting agent arrangement, degree of getting wet significantly decreases, and the fabric of waterproof linking agent and water-resisting agent one-bath finishing, degree of getting wet does not descend or faint decline is only arranged.This is owing to cation blocked isocyanic ester, and after the deblocking, unusual active isocyanate group (NCO) again discharges, also contains reactive group :-NH in the fabric fibre macromole simultaneously at a certain temperature
2, condensation reaction can occur between the two in-OH etc. when curing, the blocked isocyanate molecule is linked to each other with covalent linkage with the fiber macromole; Also have in the water-resisting agent molecule on the other hand and contain active H group such as-OH, under curing, water-resisting agent and blocked isocyanate generation covalent bonds, thereby fabric fibre and water-resisting agent molecule are coupled together with covalent linkage by the blocked isocyanate molecule, promote the bonding force of water-resisting agent and fabric, improved the washing fastness of degree of getting wet and waterproof fabric.Principle is schematically as follows:
In sum, the waterproof linking agent that the present invention synthesizes is bathed together the waterproofing that is applied to fabric with water-resisting agent, and is obvious to the fabric waterproof effect promoting, can also improve the wash durability of water-resisting agent simultaneously.
Performed polymer before and after the sealing among the embodiment 1 is carried out respectively Infrared Characterization, spectrogram as shown in Figure 1: the most obvious difference of product infrared spectrogram is before and after the sealing, 2271cm in the sealing after product infrared spectrogram
-1Place-NCO group charateristic avsorption band disappears, illustrate-the NCO group seals by Diacetylmonoxime.
The above only is preferred embodiment of the present invention, is not technical scheme of the present invention is done any pro forma restriction.Every foundation technical spirit of the present invention all falls within the scope of protection of the present invention any simple modification, equivalent variations and modification that above embodiment does.
Claims (4)
1. the preparation method of a positively charged ion waterproof linking agent, it is below step:
1) 3-15 part cationic hydrophilic chainextender N methyldiethanol amine is added in the isocyanic ester of 20-60 part, open and stir, 40-85 ℃ of lower reaction 0.5-3 hour, in the structure with cationic hydrophilic chainextender access isocyanic ester;
2) mixture of encapsulant 8-32 part and 12-24 part butanone is added step 1) reaction system in, 60-85 ℃ of lower reaction 1-4 hour, isocyanate groups that will be excessive with encapsulant sealed;
3) with the 2nd) synthetic performed polymer of step is dispersed in the aqueous solution of 2-8 part neutralizing agent, emulsification 5-10min under agitation, butanone is deviate from afterwards underpressure distillation, and obtaining solid content is the positively charged ion waterproof linking agent of 25-35%;
Raw material umber in the above-mentioned steps is parts by weight.
2. the preparation method of positively charged ion waterproof linking agent according to claim 1, it is characterized in that step 1) in isocyanic ester be a kind of in tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, toluene diisocyanate trimer, the hexamethylene diisocyanate trimer.
3. the preparation method of positively charged ion waterproof linking agent according to claim 1, it is characterized in that step 2) in encapsulant be acetoxime, Diacetylmonoxime, cyclohexanone oxime, ξ-caprolactam, 3，5-dimethylpyrazole, butanols, 1, a kind of in 2, the 4-triazole.
4. the preparation method of positively charged ion waterproof linking agent according to claim 1 is characterized in that step 3) in neutralizing agent be Glacial acetic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013102906251A CN103351460A (en) | 2013-07-10 | 2013-07-10 | Preparation method of cation waterproof cross-linking agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013102906251A CN103351460A (en) | 2013-07-10 | 2013-07-10 | Preparation method of cation waterproof cross-linking agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103351460A true CN103351460A (en) | 2013-10-16 |
Family
ID=49307884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013102906251A Pending CN103351460A (en) | 2013-07-10 | 2013-07-10 | Preparation method of cation waterproof cross-linking agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103351460A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105019248A (en) * | 2015-08-20 | 2015-11-04 | 广东德美精细化工股份有限公司 | Preparation method of positive ion reaction type environment-friendly fabric stiffening agent |
| CN105037679A (en) * | 2015-09-23 | 2015-11-11 | 苏州依司特新材料科技有限公司 | Cationic type polyurethane modified organosilicon water repellent agent and preparation method and application thereof |
| CN106676900A (en) * | 2016-12-31 | 2017-05-17 | 鲁丰织染有限公司 | Fluoride-free water-proof finishing method for pure cotton fabric |
| CN110483738A (en) * | 2019-08-20 | 2019-11-22 | 湖南湘江关西涂料有限公司 | Blocked isocyanate curing agent and preparation method thereof, one-component coating |
| CN111040105A (en) * | 2019-12-30 | 2020-04-21 | 珠海华大浩宏化工有限公司 | Soft fluorine-free waterproof agent and preparation method thereof |
| CN111041891A (en) * | 2019-12-30 | 2020-04-21 | 广东高璐美数码科技有限公司 | Waterproof highlight color-spray coating and preparation method thereof |
| CN112209855A (en) * | 2020-09-29 | 2021-01-12 | 杭州传化精细化工有限公司 | Cationic hydrophilic chain extender with reactive groups and preparation method thereof |
| CN114775291A (en) * | 2022-05-16 | 2022-07-22 | 杭州美高华颐化工有限公司 | Preparation method of novel quaternized modified block silicone oil |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307180A (en) * | 2008-07-02 | 2008-11-19 | 天津大学 | Cationoid polyurethane and modified silicon oil composite water dispersion, preparation and applications |
| CN101435159A (en) * | 2008-12-22 | 2009-05-20 | 陕西科技大学 | Cation type aqueous full fluorine polyurethane textile finishing agent and preparing method thereof |
| CN102816294A (en) * | 2012-08-17 | 2012-12-12 | 浙江传化股份有限公司 | Preparation method of water-soluble blocked isocyanate crosslinking agent |
| CN103147306A (en) * | 2013-01-30 | 2013-06-12 | 西安工程大学 | Textile anti-pilling polyurethane finishing agent and preparation method thereof |
-
2013
- 2013-07-10 CN CN2013102906251A patent/CN103351460A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307180A (en) * | 2008-07-02 | 2008-11-19 | 天津大学 | Cationoid polyurethane and modified silicon oil composite water dispersion, preparation and applications |
| CN101435159A (en) * | 2008-12-22 | 2009-05-20 | 陕西科技大学 | Cation type aqueous full fluorine polyurethane textile finishing agent and preparing method thereof |
| CN102816294A (en) * | 2012-08-17 | 2012-12-12 | 浙江传化股份有限公司 | Preparation method of water-soluble blocked isocyanate crosslinking agent |
| CN103147306A (en) * | 2013-01-30 | 2013-06-12 | 西安工程大学 | Textile anti-pilling polyurethane finishing agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 从建华: "水性聚氨酯类染色织物耐洗色牢度提升剂的合成及应用", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105019248A (en) * | 2015-08-20 | 2015-11-04 | 广东德美精细化工股份有限公司 | Preparation method of positive ion reaction type environment-friendly fabric stiffening agent |
| CN105037679A (en) * | 2015-09-23 | 2015-11-11 | 苏州依司特新材料科技有限公司 | Cationic type polyurethane modified organosilicon water repellent agent and preparation method and application thereof |
| CN105037679B (en) * | 2015-09-23 | 2018-01-16 | 苏州依司特新材料科技有限公司 | Cation type polyurethane modified organic silicon water repellent and preparation method and application |
| CN106676900A (en) * | 2016-12-31 | 2017-05-17 | 鲁丰织染有限公司 | Fluoride-free water-proof finishing method for pure cotton fabric |
| CN110483738A (en) * | 2019-08-20 | 2019-11-22 | 湖南湘江关西涂料有限公司 | Blocked isocyanate curing agent and preparation method thereof, one-component coating |
| CN111040105A (en) * | 2019-12-30 | 2020-04-21 | 珠海华大浩宏化工有限公司 | Soft fluorine-free waterproof agent and preparation method thereof |
| CN111041891A (en) * | 2019-12-30 | 2020-04-21 | 广东高璐美数码科技有限公司 | Waterproof highlight color-spray coating and preparation method thereof |
| CN112209855A (en) * | 2020-09-29 | 2021-01-12 | 杭州传化精细化工有限公司 | Cationic hydrophilic chain extender with reactive groups and preparation method thereof |
| CN114775291A (en) * | 2022-05-16 | 2022-07-22 | 杭州美高华颐化工有限公司 | Preparation method of novel quaternized modified block silicone oil |
| CN114775291B (en) * | 2022-05-16 | 2023-06-27 | 杭州美高华颐化工有限公司 | Preparation method of novel quaternized modified block silicone oil |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103351460A (en) | Preparation method of cation waterproof cross-linking agent | |
| CN102816294B (en) | Preparation method of water-soluble blocked isocyanate crosslinking agent | |
| CN101818458B (en) | Preparation method of organosilicon modified polyurethane hyperchromic improver | |
| CN101381449B (en) | Polyurethane resin for artificial leather | |
| CN109160994B (en) | Polyurethane dispersion for dry coating primer, and preparation method and application thereof | |
| CN101581039B (en) | Durable antistatic finishing agent for fabrics and preparation method | |
| CN112694591A (en) | Preparation method of silane coupling agent modified solvent-free waterborne polyurethane | |
| CN107955129B (en) | Cross-linking agent for reactive pigment imitation printing and preparation method thereof | |
| CN102702471A (en) | Method for preparing solvent-free aqueous polyurethane dispersion | |
| CN110835401A (en) | Waterborne polyurethane surface layer resin and preparation method thereof | |
| CN103819648A (en) | Preparation method of polysiloxane modified polyurethane water dispersion | |
| CN113338051A (en) | Preparation method of solvent-free waterborne polyurethane microfiber synthetic leather with high R value | |
| CN101633828B (en) | High-temperature resistant waterborne polyurethane adhesive and preparation method thereof | |
| CN105019248B (en) | The preparation method of cationoid reaction type environment-friendlyfabric fabric stiffening agent | |
| CN109750503A (en) | A kind of siliceous water repellent finishing agent | |
| KR100812635B1 (en) | Dispersion polycarbonate polyurethane resin | |
| CN114044861B (en) | Polyurethane modified acrylic ester pigment printing adhesive for polyester oxford fabric and preparation method thereof | |
| CN106758387B (en) | A kind of formaldehydeless chlorine-resistant cotton color fixing agent of environmental protection | |
| CN105603758B (en) | A kind of elastic force moving fabric | |
| CN103342822B (en) | Preparation method of trichlorophenol blocked isocyanate prepolymer micelle | |
| CN113831494B (en) | Cardanol biological anti-wrinkle cross-linking agent and preparation method and application thereof | |
| CN115505293B (en) | Polyurethane for shoe material printing ink and preparation method thereof | |
| CN111533875A (en) | Preparation method of cationic waterborne polyurethane, leather bottom sealing resin and leather coating | |
| CN111777887A (en) | Flame-retardant heat-resistant waterborne polyurethane coating and preparation method thereof | |
| CN110423333A (en) | A kind of soft cryobranding color-changing polyurethane resin and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20131016 |