CN108484873B - High-solid-content polyurethane surface layer resin for synthetic leather and preparation method thereof - Google Patents
High-solid-content polyurethane surface layer resin for synthetic leather and preparation method thereof Download PDFInfo
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- CN108484873B CN108484873B CN201810138119.3A CN201810138119A CN108484873B CN 108484873 B CN108484873 B CN 108484873B CN 201810138119 A CN201810138119 A CN 201810138119A CN 108484873 B CN108484873 B CN 108484873B
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
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- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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- D06N2203/00—Macromolecular materials of the coating layers
- D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a high-solid-content polyurethane surface layer resin for synthetic leather and a preparation method thereof, wherein the high-solid-content polyurethane surface layer resin is prepared by the following steps: preparing high solid content blocked polyurethane resin, preparing modified amine curing agent, taking and stirring the blocked high solid content resin, color paste and the modified amine curing agent uniformly to obtain the polyurethane surface layer resin. The invention generates a terminal isocyanate prepolymer with smaller molecular weight and lower viscosity by the reaction of isocyanate and hydroxyl components, utilizes a sealing agent which can be thermally dissociated to react with terminal isocyanate to form sealed polyurethane which can be stably stored at room temperature, adds an amine curing agent when in use, can have a storage period of more than one week at room temperature, and the sealing agent is dissociated under the heating condition, and the released isocyanate and the amine curing agent are rapidly reacted to form the urea-urethane-group-containing composite polymer material with excellent mechanical property.
Description
Technical Field
The invention belongs to the field of functional polyurethane synthetic leather, and particularly relates to a high-solid-content polyurethane surface layer resin for synthetic leather and a preparation method thereof.
Background
The polyurethane polymer material has excellent flexibility, wear resistance, hydrolysis resistance and the like, so that the polyurethane polymer material is widely applied to the field of synthetic leather and becomes an ideal material for replacing natural leather. The traditional processing preparation of polyurethane synthetic leather adopts dry process, wet process or combination of dry process and wet process in the processing processN,NOrganic solvents such as Dimethylformamide (DMF), Methyl Ethyl Ketone (MEK), Toluene (TOL) and the like, and polyurethane resin with solid content of 20-40% are used as raw materials, so that the problems of organic solvent pollution and the like exist in the processing process. Along with the increase of the supervision of the state on the environmental pollution problem in the production process of enterprises and the gradual enhancement of the environmental awareness of people, the polyurethane synthetic leather gradually moves from high pollution and high emission to clean production with zero pollution and low emission.
In recent years, relevant synthetic leather enterprises use a solvent-free bi-component mixed pouring process to prepare a synthetic leather intermediate foaming layer to replace a traditional solvent-based wet-process pore layer to obtain excellent hand feeling and performance, and the synthetic leather intermediate foaming layer is gradually accepted by the market. The solvent-free two-component process greatly reduces the DMF content of the synthetic leather in the processing process and the final leather product, but the current two-component solvent-free process is only limited to be applied to the intermediate foaming layer of the synthetic leather. Because the surface layer adopts a solvent-free two-component process, the problem that the color is difficult to control accurately exists, the application of the waterborne polyurethane surface layer resin to synthetic leather products has certain defects in the aspects of physical properties and processing properties, and an environment-friendly dry surface layer has no ideal solution.
Therefore, it is particularly necessary to develop a high-solid-content polyurethane surface resin for synthetic leather, and provide a full-environment-friendly synthetic leather processing and production solution by matching with a solvent-free two-component middle layer resin.
Disclosure of Invention
The invention aims to provide a preparation method and application of a high-solid-content polyurethane surface layer resin for synthetic leather, and provides a solution for an environment-friendly polyurethane synthetic leather product.
A preparation method of high-solid-content polyurethane surface layer resin for synthetic leather is prepared by the following steps:
(1) preparation of high solid content blocked polyurethane resin
Controlling the temperature of a reaction kettle at 40-50 ℃, adding isocyanate and an antioxidant, stirring for 10-30min, sequentially adding oligomer polyol, castor oil and a chain extender, and reacting at 60-80 ℃ until the mass content of NCO reaches 1.5-5%, thus obtaining an isocyanate-terminated prepolymer;
adding a sealing agent into the isocyanate-terminated prepolymer for sealing reaction, and reacting at 60-80 ℃ until the mass content of NCO is 0%; then adding a solvent to adjust the solid content of the polyurethane resin to 90%, finally adding an ultraviolet absorber, stirring for 20-30min, cooling, discharging and packaging to obtain closed high-solid resin;
(2) preparation of modified amine curing agent
Controlling the temperature of the reaction kettle at 40-50 ℃, adding the amino-terminated polyether and the antioxidant, stirring for 10-20min, adding isocyanate, and reacting at 40-50 ℃ until the amine value reaches 35-156mgKOH/g, thus obtaining the modified amine curing agent;
(3) preparation of polyurethane surface resin
And (3) uniformly stirring the closed high-solid resin and the color paste prepared in the step (1) and the modified amine curing agent prepared in the step (2) to obtain the polyurethane surface layer resin.
In a further scheme, the high-solid content blocked polyurethane resin in the step (1) comprises the following raw materials in parts by weight:
isocyanate 100 parts
Oligomer polyol 140-220 parts
50-100 parts of castor oil
4-10 parts of chain extender
10-40 parts of sealant
0.5-1 part of antioxidant
0.5-1 part of ultraviolet absorber
38-43 parts of a solvent.
In a further scheme, the modified amine curing agent in the step (2) comprises the following raw materials in parts by weight:
amino-terminated polyether 100 parts
3-15 parts of isocyanate
0.2-1 part of antioxidant.
Further, in the step (3), the mass ratio of the closed high-solid resin to the color paste to the modified amine curing agent is 100: 5-10: 40-66.
In a further embodiment, the isocyanate is one or more of 4,4 '-diphenylmethane diisocyanate (MDI-100), a mixture of 2, 4' -diphenylmethane diisocyanate and 4,4 '-diphenylmethane diisocyanate (MDI-50), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), and 4, 4' -dicyclohexylmethane diisocyanate (HMDI).
In a further scheme, the oligomer polyol in the step (1) is polyester polyether copolymer oligomer polyol and one or more of polyester oligomer polyol and polycarbonate oligomer polyol; the polyester-polyether copolymer type oligomer polyol is prepared by taking polyester polyol as an initiator and performing ring-opening polymerization on propylene oxide;
the average hydroxyl functionality of the castor oil is 2.7, and the hydroxyl value is 156-160 mg KOH/g;
the chain extender is one of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, diethylene glycol and 3-methyl-1, 5-pentanediol;
the sealant is one of methyl ethyl ketoxime, 3, 5-dimethyl pyrazole, diethyl malonate, acetanilide and 1,2, 4-triazole;
the solvent is one of gamma-butyrolactone, epsilon-caprolactone, dipropylene glycol dimethyl ether, propylene glycol methyl ether acetate, propylene glycol diacetate and ethylene glycol diacetate.
Further, the amine-terminated polyether in step (2) is a polypropylene oxide compound terminated with primary amino group, and has a molecular weight of 400-2000. Preferably, the reagent is selected from AMD-400, AMD-1000 and AMD-2000 of Nicotiana civilians Chemicals Co.
Further, the ultraviolet absorbent is UV-1, UV-320, UV-1130, UV-P, UV-1164 or UV-234; the antioxidant is 245, 1010, 1035, 1076, 1098 or 3114.
Another object of the present invention is to provide a polyurethane top layer resin prepared by the above-mentioned preparation method.
The invention generates a terminal isocyanate prepolymer with smaller molecular weight and lower viscosity by the reaction of isocyanate and hydroxyl components, utilizes a sealing agent which can be thermally dissociated to react with terminal isocyanate to form sealed polyurethane which can be stably stored at room temperature, adds an amine curing agent when in use, can have a storage period of more than one week at room temperature, and the sealing agent is dissociated under the heating condition, and the released isocyanate and the amine curing agent are rapidly reacted to form the urea-urethane-group-containing composite polymer material with excellent mechanical property.
The polyurethane surface layer resin prepared by the invention is coated on release paper and dried in an oven at the temperature of 120-140 ℃ for 2-4min to obtain the polyurethane surface layer coating, then solvent-free bi-component polyurethane intermediate layer resin AL-1025A/AL-5040B produced by polyurethane new material company Limited is coated on the polyurethane surface layer coating, and then base cloth is attached to prepare the synthetic leather product. The prepared synthetic leather product has the VOC of less than 10ppm, the peel strength of more than 50N/3cm, the peel strength retention rate of more than 75% after constant temperature and humidity for 7 weeks at 70 ℃ and 95% RH, excellent wear resistance and folding resistance, and can be widely applied to the fields of sofa furniture leather, luggage leather and the like.
Specifically, compared with the prior art, the invention has the following obvious advantages:
(1) after the modified amine curing agent is added into the high-solid-content closed polyurethane resin, the storage period can reach more than one week at room temperature, the storage performance is stable, and the high-solid-content closed polyurethane resin has similar operation processability to the traditional single-component resin; after high-temperature deblocking and curing, a coating structure similar to two-component polyurethane resin is formed, and the advantages of high solid content and low viscosity of two-component resin products are kept.
(2) The invention uses part of castor oil and other types of oligomer polyols as mixed soft segment to synthesize the blocked polyurethane, wherein the average functionality of the hydroxyl of the castor oil is 2.7. The polyurethane resin prepared by mixing the two polyols has excellent mechanical strength and good flow property.
(3) According to the invention, through the reaction of the amino-terminated polyether with the molecular weight of 400-2000 and the isocyanate, the synthesized amine curing agent has a high boiling point and is not easy to volatilize, the problem that the deviation between the amine curing agent actually participating in the reaction and a theoretical design value is large due to the fact that a common amine curing agent is easy to volatilize is avoided, and the stability of the mechanical property of the formed polyurethane coating is ensured.
(4) The solid content of the closed high-solid-content resin is 90%, the product only uses a small amount of weak solvent system with good environmental protection performance, and does not use a DMF organic solvent which is difficult to volatilize. The prepared synthetic leather product has excellent environmental protection performance, the highest VOC content is only 10ppm, and the synthetic leather product is an environmental protection synthetic leather product absolutely free of DMF.
Detailed Description
The present invention is further illustrated by the following specific examples, but it should be noted that the specific material ratios, process conditions, results, etc. described in the examples of the present invention are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Example 1:
(1) preparation of high solid content blocked polyurethane resin
Adding 100g of 4, 4' -diphenylmethane diisocyanate (MDI-100) into a three-neck flask, heating to 40 ℃, adding 1g of antioxidant 1010, stirring for 10min, sequentially adding 140g of oligomer polyol (YNW-2000T), 60g of castor oil and 4g of Ethylene Glycol (EG), uniformly stirring, heating to 60 ℃, reacting for 4 hours, and detecting NCO to 5%.
40g of blocking agent methyl ethyl ketoxime is added, the reaction is carried out for 3 hours at 60 ℃, and the NCO content is detected to reach 0%. Adding 38g of propylene glycol methyl ether acetate solvent and 0.8g of ultraviolet absorber UV-P, stirring for 20min, cooling, discharging and packaging.
(2) Preparation of amine curing agents
The temperature of the reaction kettle is controlled at 40 ℃, 100g of amine terminated polyether (AMD-400) and 1g of antioxidant 1010 are added and stirred for 10min, and 15g of Hexamethylene Diisocyanate (HDI) is dripped into the reaction kettle. Reacting for 4 hours at 40 ℃ until the amine value reaches 156 mgKOH/g. Stirring for 30min, cooling, discharging and packaging.
(3) Preparation of polyurethane surface resin
And (3) taking 100g of the resin in the step (1), adding 5g of solvent-free color paste and 40g of the amine curing agent synthesized in the step (2), and uniformly stirring to obtain the polyurethane surface layer resin.
Coating the polyurethane surface layer resin on release paper, drying in an oven at 130 ℃ for 3min to obtain a polyurethane surface layer coating, coating the polyurethane surface layer coating with the solvent-free double-component polyurethane middle layer resin AL-1025A/AL-5040B produced by Fei anli polyurethane new material company Limited, and then attaching base cloth to obtain the synthetic leather product. The VOC (total volatile matter) measured by HJ/H400-2007 standard is less than 10 ppm. The peel strength is 73N/3 cm according to QB/T2888-2007 standard, the peel strength is 66N/3 cm after the jungle test is carried out in a constant temperature and humidity box with 70 ℃ and 95% RH for 7 weeks, the Weishibo is wear-resistant and does not break for 10 ten thousand times, and the Weishibo is not broken for 6 ten thousand times at-10 ℃, thereby meeting the requirement of the basic physical property of sofa leather.
The raw materials used in this example:
MDI-100 and HDI are isocyanate produced by the Futaiwan corporation; YNW-2000T is polyester polyether copolymer oligomer polyol produced by Shandong-Nowei New materials Co; AMD-400 is terminal amino polyether produced by Nicotiana civilian chemicals GmbH; the methyl ethyl ketoxime is a sealing agent produced by Zhejiang Shengan chemical engineering Co., Ltd; 1010. UV-P is antioxidant and ultraviolet absorbent of Taiwan double bond chemical industry Co., Ltd; castor oil, ethylene glycol, propylene glycol methyl ether acetate and solvent-free color paste are commercially available products.
Example 2:
(1) preparation of high solid content blocked polyurethane resin
Adding 100g of mixed isocyanate (MDI-50) of 2,4 '-diphenylmethane diisocyanate and 4, 4' -diphenylmethane diisocyanate into a three-neck flask, heating to 50 ℃, adding 0.5g of antioxidant 245, stirring for 30min, sequentially adding 220g of oligomer polyol (PBA-2000), 50g of castor oil and 7.5g of 1, 4-butanediol (1, 4-BG), uniformly stirring, heating to 80 ℃, reacting for 4 hours, and detecting NCO to reach 3%.
27g of blocking agent 3, 5-dimethylpyrazole is added, reaction is carried out for 2 hours at 80 ℃, and NCO content is detected to reach 0%. Adding 42g of solvent gamma-butyrolactone and 1g of ultraviolet absorber UV-1, stirring for 30min, cooling, discharging and packaging.
(2) Preparation of amine curing agents
The temperature of the reaction kettle is controlled at 50 ℃, 100g of amino-terminated polyether (AMD-1000) and 0.5g of antioxidant 245 are added and stirred for 20min, and 8g of Hexamethylene Diisocyanate (HDI) is dripped into the reaction kettle. Reacting for 3 hours at 50 ℃ until the amine value content reaches 54 mgKOH/g. Stirring for 60min, cooling, discharging and packaging.
(3) Preparation of polyurethane surface resin
And (2) taking 100g of the resin in the step (1), adding 8g of solvent-free color paste and 66g of the amine curing agent synthesized in the step (2), and uniformly stirring to obtain the polyurethane surface layer resin.
Coating the polyurethane surface layer resin on release paper, drying in an oven at 130 ℃ for 3min to obtain a polyurethane surface layer coating, coating the polyurethane surface layer coating with the solvent-free double-component polyurethane middle layer resin AL-1025A/AL-5040B produced by Fei anli polyurethane new material company Limited, and then attaching base cloth to obtain the synthetic leather product. The VOC (total volatile matter) measured by HJ/H400-2007 standard is less than 10 ppm. The peel strength of the material is 78N/3 cm measured according to QB/T2888-2007 standard, the peel strength is 68N/3 cm after the material is subjected to jungle test in a constant temperature and humidity box with 70 ℃ and 95% RH for 7 weeks, the Weishibo is wear-resistant and does not break for 10 ten thousand times, and the material does not break for 6 ten thousand times at-10 ℃, thereby meeting the requirements of the basic physical properties of sofa leather.
The raw materials used in this example:
MDI-50 and HDI are isocyanate produced by the Futaiwan corporation; PBA-2000 is a polyester type oligomer polyol manufactured by Asahi Chun chemical Co., Ltd; AMD-1000 is terminal amino polyether produced by Nicotiana Summinck Chemicals GmbH; 3, 5-dimethylpyrazole is a sealant of Hubei Jusheng science and technology limited; 245. UV-1 is antioxidant and ultraviolet absorbent of Taiwan double bond chemical industry Co., Ltd; castor oil, 1, 4-butanediol, gamma-butyrolactone and solvent-free color paste are commercially available products.
Example 3:
(1) preparation of high solid content blocked polyurethane resin
Adding 100g of 4, 4' -dicyclohexylmethane diisocyanate (HMDI) into a three-neck flask, heating to 45 ℃, adding 0.8g of antioxidant 1076, stirring for 20min, sequentially adding 170g of oligomer polyol (PCDL-2000), 100g of castor oil and 10g of diethylene glycol, stirring uniformly, heating to 70 ℃, reacting for 4 hours, and detecting NCO to reach 1.5%.
10g of sealant 1,2, 4-triazole is added to react for 4 hours at 70 ℃, and the NCO content is detected to reach 0%. Adding 43g of solvent dipropylene glycol dimethyl ether and 0.5g of ultraviolet absorbent UV-1130, stirring for 25min, cooling, discharging and packaging.
(2) Preparation of amine curing agents
The temperature of the reaction kettle is controlled at 45 ℃, 100g of amino terminated polyether (AMD-2000) and 0.2g of antioxidant 1076 are added and stirred for 15min, and 3g of Hexamethylene Diisocyanate (HDI) is dripped into the reaction kettle. Reacting for 3 hours at the temperature of 45 ℃ until the amine value content reaches 35 mgKOH/g. Stirring for 45min, cooling, discharging and packaging.
(3) Preparation of polyurethane surface resin
And (2) taking 100g of the resin in the step (1), adding 10g of solvent-free color paste and 57g of the amine curing agent synthesized in the step (2), and uniformly stirring to obtain the polyurethane surface layer resin.
Coating the polyurethane surface layer resin on release paper, drying in an oven at 130 ℃ for 3min to obtain a polyurethane surface layer coating, coating the polyurethane surface layer coating with the solvent-free double-component polyurethane middle layer resin AL-1025A/AL-5040B produced by Fei anli polyurethane new material company Limited, and then attaching base cloth to obtain the synthetic leather product. The yellowing resistance grade is 4 measured by GB/T16422.3-1993 standard, and the VOC (total volatile matter) is less than 10ppm measured by HJ/H400-2007 standard. The peel strength of the material is 82N/3 cm measured according to QB/T2888-2007 standard, the peel strength is 71N/3 cm after the material is subjected to jungle test in a constant temperature and humidity box with 70 ℃ and 95% RH for 7 weeks, the Weishibo is wear-resistant and does not break for 10 ten thousand times, and the material does not break for 6 ten thousand times at-10 ℃, thereby meeting the requirement of the basic physical property of sofa leather.
The raw materials used in this example:
HMDI and HDI are isocyanate produced by the Futaiwan corporation; PCDL-2000 is a polycarbonate type oligomer polyol produced by Asahi Kasei corporation of Japan; AMD-2000 is amine terminated polyether produced by Nicotiana folk Chemicals GmbH; the 1,2, 4-triazole is a sealing agent of Weifang Wanbo chemical company Limited; 1076. UV-1130 is antioxidant and ultraviolet absorbent of Taiwan double bond chemical Co., Ltd; castor oil, diethylene glycol, dipropylene glycol dimethyl ether and solvent-free color paste are commercially available products.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (9)
1. A preparation method of high-solid-content polyurethane surface layer resin for synthetic leather is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) preparation of high solid content blocked polyurethane resin
Controlling the temperature of a reaction kettle at 40-50 ℃, adding isocyanate and an antioxidant, stirring for 10-30min, sequentially adding oligomer polyol, castor oil and a chain extender, and reacting at 60-80 ℃ until the mass content of NCO reaches 1.5-5%, thus obtaining an isocyanate-terminated prepolymer;
adding a sealing agent into the isocyanate-terminated prepolymer for sealing reaction, and reacting at 60-80 ℃ until the mass content of NCO is 0%; then adding a solvent to adjust the solid content of the polyurethane resin to 90%, finally adding an ultraviolet absorber, stirring for 20-30min, cooling, discharging and packaging to obtain closed high-solid resin;
(2) preparation of modified amine curing agent
Controlling the temperature of the reaction kettle at 40-50 ℃, adding the amino-terminated polyether and the antioxidant, stirring for 10-20min, adding isocyanate, and reacting at 40-50 ℃ until the amine value reaches 35-156mgKOH/g, thus obtaining the modified amine curing agent;
(3) preparation of polyurethane surface resin
And (3) uniformly stirring the closed high-solid resin and the color paste prepared in the step (1) and the modified amine curing agent prepared in the step (2) to obtain the polyurethane surface layer resin.
2. The method of claim 1, wherein: the high-solid content closed polyurethane resin in the step (1) comprises the following raw materials in parts by weight:
3. the method of claim 1, wherein: the modified amine curing agent in the step (2) comprises the following raw materials in parts by weight:
amino-terminated polyether 100 parts
3-15 parts of isocyanate
0.2-1 part of antioxidant.
4. The method of claim 1, wherein: in the step (3), the mass ratio of the closed high-solid resin to the color paste to the modified amine curing agent is 100: 5-10: 40-66.
5. The method of claim 1, wherein: the isocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, a mixture of 2, 4' -diphenylmethane diisocyanate and 4,4 '-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and 4, 4' -dicyclohexylmethane diisocyanate.
6. The method of claim 1, wherein: the oligomer polyol in the step (1) is one or more of polyester polyether copolymer oligomer polyol, polyester oligomer polyol and polycarbonate oligomer polyol; the polyester-polyether copolymer type oligomer polyol is prepared by taking polyester polyol as an initiator and performing ring-opening polymerization on propylene oxide;
the average hydroxyl functionality of the castor oil is 2.7, and the hydroxyl value is 156-160 mg KOH/g;
the chain extender is one of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, diethylene glycol and 3-methyl-1, 5-pentanediol;
the sealant is one of methyl ethyl ketoxime, 3, 5-dimethyl pyrazole, diethyl malonate, acetanilide and 1,2, 4-triazole;
the solvent is one of gamma-butyrolactone, epsilon-caprolactone, dipropylene glycol dimethyl ether, propylene glycol methyl ether acetate, propylene glycol diacetate and ethylene glycol diacetate.
7. The method of claim 1, wherein: the amine-terminated polyether in step (2) is a polypropylene oxide compound terminated by primary amino group, and the molecular weight of the polypropylene oxide compound is 400-2000.
8. The method of claim 1, wherein: the ultraviolet absorbent is UV-1, UV-320, UV-1130, UV-P, UV-1164 or UV-234; the antioxidant is 245, 1010, 1035, 1076, 1098 or 3114.
9. The polyurethane top coat resin produced by the production method as set forth in any one of claims 1 to 8.
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| CN112341593B (en) * | 2020-10-17 | 2022-09-02 | 浙江禾欣科技有限公司 | Water-based surface layer polyurethane resin for automobile leather and preparation method thereof |
| CN112625213B (en) * | 2020-12-04 | 2022-05-17 | 上海华峰新材料研发科技有限公司 | Solvent-free blocked polyurethane resin composition, polyurethane material and leather product |
| CN114085356A (en) * | 2021-11-19 | 2022-02-25 | 合肥安利聚氨酯新材料有限公司 | Chemical-resistant biodegradable surface layer polyurethane resin for synthetic leather and preparation method thereof |
| CN116041659B (en) * | 2023-03-27 | 2023-06-09 | 旭川化学（苏州）有限公司 | Solvent-free bio-based polyurethane resin and preparation method and application thereof |
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| CN101580578A (en) * | 2009-04-15 | 2009-11-18 | 浙江华峰合成树脂有限公司 | High solid foaming polyurethane resin for synthetic leather and preparing method thereof |
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