CN108467470B - DMF (dimethyl formamide) -free composite closed high-solid polyurethane bonding layer resin for synthetic leather and preparation method and application thereof - Google Patents
DMF (dimethyl formamide) -free composite closed high-solid polyurethane bonding layer resin for synthetic leather and preparation method and application thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- 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
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
- D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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Abstract
The invention discloses a DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather and a preparation method and application thereof, and the resin comprises the following components in parts by mass: isocyanate, polyether polyol, a chain extender, a cross-linking agent and a composite sealing agent. The preparation method comprises the following steps: melting isocyanate at 50-60 ℃, adding polyether polyol, a chain extender and a cross-linking agent, heating to 70-80 ℃, and stirring for reaction to obtain a polyurethane prepolymer with 2-3% of isocyanate group weight; and then adding a composite sealing agent for end sealing, detecting that no free isocyanate exists, adding a ketone and ether solvent, and diluting until the solid content is 70-80% and the viscosity is 2000-6000 mPa.s/25 ℃, thus obtaining the composite sealing high-solid polyurethane bonding layer resin. The composite closed high-solid polyurethane bonding layer resin prepared by the invention is added with a calculated amount of curing agent for bonding synthetic leather.
Description
Technical Field
The invention relates to the field of polyurethane adhesive resin, in particular to DMF (dimethyl formamide) -free composite closed high-solid polyurethane adhesive layer resin for synthetic leather, and a preparation method and application thereof.
Background
The polyurethane synthetic leather product is used as a substitute of genuine leather, is widely applied to the fields of sofa furniture, bags, sports and leisure shoes and the like, and has the service performance reaching or even exceeding the genuine leather. Along with the continuous improvement of the living standard of people, the environmental protection consciousness and the requirement of consumers are higher and higher. The traditional production and processing process of polyurethane synthetic leather mainly comprises the steps of producing wet base, and then carrying out release paper transfer veneering to finish the manufacture of finished leather. In the whole processing link, DMF elution is insufficient or volatilization is insufficient easily in the wet method bass production link and the dry method bonding link, and finally the content of DMF in finished leather exceeds the standard, so that the requirement of downstream customers on the environmental protection of products cannot be met. In order to solve the problem, a plurality of new polyurethane synthetic leather processing technologies such as aqueous polyurethane synthetic leather, solvent-free polyurethane synthetic leather and the like are continuously appeared in recent years. The solvent-free polyurethane synthetic leather has the characteristics of good physical properties, full hand feeling, wet removing and the like, and becomes an ideal choice for production and processing of environment-friendly polyurethane synthetic leather. However, the solvent-free polyurethane resin has a large coating amount during processing, so that the production cost is high, and the solvent-free polyurethane resin can only be positioned as a medium-grade or high-grade product. The middle-low-end environment-friendly polyurethane synthetic leather products in the market are important for research, and especially have important research significance on how to prepare synthetic leather products with good flatness on the premise of a dewetting method for base materials with surface flatness deviation such as microfiber and woven fabric.
The traditional dry process is adopted, namely the solvent type polyurethane bonding layer resin is bonded with microfiber, woven fabric and the like, on one hand, DMF cannot be completely volatilized in the bonding process, and finished leather contains DMF residues; on the other hand, the solid content of the solvent-based adhesive layer resin is 20-30% in general processing, the thickness of a dry film is only 1-5 threads after the solvent is completely volatilized, the unevenness of the surfaces of microfiber base cloth and woven cloth cannot be covered, and finally the surface of finished leather is uneven.
When the high-solid-content polyurethane adhesive layer resin is adopted to be attached to the base cloth, the defect of uneven surface of the base cloth can be overcome, but the solid content is high, and the molecular weight is relatively small, so that certain physical properties of finished leather can not meet the use requirements. In view of this problem, the closed type high solid content polyurethane adhesive layer resin is definitely a preferable choice. The blocked polyurethane resin with high solid content can participate in reaction through the curing agent after deblocking, and plays a great role in making up for the insufficient physical properties of synthetic leather products caused by the insufficient molecular weight of the polyurethane resin with high solid content. Many reports are also made about blocked polyurethanes, for example, patents CN200880120620.1 and CN201410578112.5 report the preparation method of blocked isocyanate coating; patents CN201380023479.4 and CN201480013800.5 report that oxime blocking agents synthesize blocked isocyanate monomer raw materials, and alcohols or lactams synthesize blocked isocyanate color filters; patents CN201480036753.6, CN201510406235.5 report the preparation of aliphatic polycarbonate type end-capped polyisocyanate compositions; patent CN200910082371.8 reports a preparation method of partially blocked polyurethane as curing agent; patents CN200910304901.9 and CN201480043861.6 report preparation methods of blocked isocyanate compositions as polyurethane adhesives for wood boards and as coating compositions and adhesive compositions for wood boards, steel materials, etc., respectively; patent CN201610346246.3 reports an aqueous dispersion of blocked polyisocyanate, and a preparation method thereof as a fiber treating agent; none of these blocked polyurethane patents mentioned above relate substantially to the field of synthetic leather. Patent CN200910131348.3 reports a high-solid foaming polyurethane resin for synthetic leather and a preparation method thereof, which uses phenols, alcohols, lactams, oximes or dicarbonyl compounds as a blocking agent, and uses water to react with unblocked isocyanate to form a foaming coating and play a good role in adhesion. However, DMF is still used as a solvent in the patent, and DMF residue still exists in the production process, which is not beneficial to the environmental protection requirement of synthetic leather products.
The invention aims to provide a DMF-free composite closed high-solid polyurethane adhesive layer resin for synthetic leather, a preparation method and application thereof, so as to solve the problem that the DMF residue of a product is easily too high when the traditional solvent type polyurethane adhesive layer resin is used for adhesion, meet the requirements of downstream customers and consumers on reducing the DMF content, realize the direct adhesion of base fabrics such as microfiber, woven fabric, special fiber velvet and the like, and obtain a finished leather product with a smooth surface, soft hand feeling and good physical properties.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather is characterized in that: the paint comprises the following components in parts by mass:
20-30 parts of isocyanate, namely,
60-70 parts of polyether polyol,
1-2 parts of a chain extender,
0.5 to 1.5 portions of cross-linking agent,
10-20 parts of a composite sealing agent,
25-45 parts of ketone or ether solvent.
The DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather is characterized by comprising the following components in percentage by weight: the isocyanate is a mixture of diphenylmethane diisocyanate MDI-100 and diphenylmethane diisocyanate MDI-50 or carbodiimide modified MDI according to the mass ratio of 4/1-9/1.
The DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather is characterized by comprising the following components in percentage by weight: the polyether polyol is at least one polyoxypropylene polyol and at least two polytetrahydrofuran polyols, or at least two polyoxypropylene polyols and at least one polytetrahydrofuran polyol, the number average molecular weight of the polyoxypropylene polyol and the number average molecular weight of the polytetrahydrofuran polyol in the polyether polyol are 400-3000, and the functionality is 2-3.
The DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather is characterized by comprising the following components in percentage by weight: the chain extender is prepared by mixing ethylene glycol and 1, 2-propylene glycol according to the molar ratio of 9/1-6/4.
The DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather is characterized by comprising the following components in percentage by weight: the cross-linking agent is one of glycerol, trimethylolpropane, diethanolamine and triethanolamine.
The DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather is characterized by comprising the following components in percentage by weight: the compound sealant is prepared by dissolving 3, 5-dimethylpyrazole and butanone oxime in a ketone solvent according to a molar ratio of 5/5-7/3, and the solid content of the compound sealant is 50-80%.
The DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather is characterized by comprising the following components in percentage by weight: the ketone solvent is one of butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 2-methyl-3-pentanone, 4-methyl-2-pentanone, 3-dimethyl-2-butanone, 2-heptanone, 3-heptanone, 5-methyl-3-heptanone, 2, 4-dimethyl-3-pentanone, cyclopentanone and cyclohexanone; the ether solvent is one of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether and diethylene glycol diethyl ether.
A preparation method of DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather is characterized by comprising the following steps: the method comprises the following steps:
(1) adding isocyanate into a reaction kettle, heating to 50-60 ℃ for melting, and uniformly stirring;
(2) adding polyether polyol, a chain extender and a cross-linking agent, uniformly stirring, heating to 70-80 ℃, and stirring for reacting for 4-6 hours;
(3) cooling to 50-60 ℃, slowly adding the composite sealing agent, heating to 70-80 ℃, stirring and reacting for 2-4 hours;
(4) and adding ketone or ether solvent to dilute the solid content to 70-80% and the viscosity to 2000-6000 mPa.s to obtain the DMF-free composite closed high-solid polyurethane adhesive layer resin for synthetic leather.
The application of DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather is characterized in that: the bonding layer resin is used for the synthetic leather prepared by bonding the base cloth, after a curing agent is added during use, deblocking-curing is realized at the temperature of 120-150 ℃, wherein the using amount of the curing agent is 5-15 parts by mass based on the total amount of the bonding layer resin, after pre-reaction is carried out for a period of time, the bonding layer resin without DMF is obtained and directly bonded with the base cloth, and then the reaction is continued at the temperature of 120-150 ℃ to be fully cured; and rolling after molding and separating the release paper to obtain the synthetic leather product with low DMF content.
The application of the DMF-free composite closed high-solid polyurethane bonding layer resin for the synthetic leather is characterized in that: the curing agent is aromatic and aliphatic amine, including but not limited to 4, 4-diaminodiphenylmethane MDA, 4' -diaminodicyclohexylmethane H12One or two of MDA; when there are two, MDA and H12Material of MDAThe quantity ratio is 1/2; the addition time of the curing agent is 24-48H when the DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather is used for leather processing.
Compared with the prior art, the invention has the beneficial effects that:
(1) 3, 5-dimethylpyrazole and butanone oxime are compounded according to a certain proportion to be used as a sealing agent, and the characteristics of high deblocking speed and low deblocking speed of the 3, 5-dimethylpyrazole are utilized to combine the advantages of the 3, 5-dimethylpyrazole and the butanone oxime, so that the rapid deblocking speed at high temperature (120 ℃ C.) is ensured, and the rapid release of isocyanate groups and the reaction and the molding of a primary amine curing agent are facilitated; on the other hand, the slow deblocking speed at low temperature (0-40 ℃) is ensured, the storage of the high-solid polyurethane bonding layer resin is facilitated, and the difficulty in processing and using the resin caused by the low-temperature fast deblocking and curing is prevented;
(2) firstly, compounding 3, 5-dimethylpyrazole and butanone oxime according to a certain proportion, dissolving in a ketone solvent to prepare a composite sealant, adding the composite sealant into an isocyanate prepolymer for sealing reaction, effectively ensuring that the two sealants keep balanced reaction rate, and avoiding the conditions of slow reaction rate and incomplete sealing caused by the reduction of free isocyanate content after adding one sealant first, thereby influencing the proportion of the two sealants participating in the reaction and finally influencing high-temperature rapid reaction formability and low-temperature storage stability;
(3) because the content of isocyanate before blocking is set to be 2-3%, the reaction rate is relatively slow on the premise of effectively ensuring the molecular weight; aromatic or aliphatic primary amine is used as a curing agent after deblocking, can quickly react with dissociated isocyanate groups, can ensure the physical properties of an adhesive layer coating by quickly forming a film, and avoids the problem of poor film forming property caused by the slow reaction rate of an alcohol, water or secondary amine curing agent;
(4) on one hand, the DMF content of finished leather is lower than 200ppm due to the direct sticking of the cloth bases such as microfiber, woven cloth and the like, so that the index requirement of the REACH regulation on the DMF content of the synthetic leather lower than 1000ppm is met; on the other hand, the myogenic property of the polyurethane adhesive layer with high solid content is good and reaches more than 80%, so that the problem of poor flatness of base materials such as microfiber and woven fabric can be solved by coating the resin, a finished product leather with good leather surface flatness is prepared, and the defect of solvent type polyurethane adhesive layer resin is overcome.
Detailed Description
A DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather is characterized in that: the paint comprises the following components in parts by mass:
20-30 parts of isocyanate, namely,
60-70 parts of polyether polyol,
1-2 parts of a chain extender,
0.5 to 1.5 portions of cross-linking agent,
10-20 parts of a composite sealing agent,
25-45 parts of ketone or ether solvent.
The isocyanate is a mixture of diphenylmethane diisocyanate MDI-100 and diphenylmethane diisocyanate MDI-50 or carbodiimide modified MDI according to the mass ratio of 4/1-9/1.
The polyether polyol is at least one polyoxypropylene polyol and at least two polytetrahydrofuran polyols, or at least two polyoxypropylene polyols and at least one polytetrahydrofuran polyol, the number average molecular weight of the polyoxypropylene polyol and the number average molecular weight of the polytetrahydrofuran polyol in the polyether polyol are 400-3000, and the functionality is 2-3.
The chain extender is prepared by mixing ethylene glycol and 1, 2-propylene glycol according to the molar ratio of 9/1-6/4.
The cross-linking agent is one of glycerol, trimethylolpropane, diethanolamine and triethanolamine.
The compound sealant is prepared by dissolving 3, 5-dimethylpyrazole and butanone oxime in a ketone solvent according to a molar ratio of 5/5-7/3, and the solid content of the compound sealant is 50-80%.
The ketone solvent is one of butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 2-methyl-3-pentanone, 4-methyl-2-pentanone, 3-dimethyl-2-butanone, 2-heptanone, 3-heptanone, 5-methyl-3-heptanone, 2, 4-dimethyl-3-pentanone, cyclopentanone and cyclohexanone; the ether solvent is one of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether and diethylene glycol diethyl ether.
The invention also provides a preparation method of the DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather, which comprises the following steps:
(1) adding isocyanate into a reaction kettle, heating to 50-60 ℃ for melting, and uniformly stirring;
(2) adding polyether polyol, a chain extender and a cross-linking agent, uniformly stirring, heating to 70-80 ℃, and stirring for reacting for 4-6 hours;
(3) cooling to 50-60 ℃, slowly adding the composite sealing agent, heating to 70-80 ℃, stirring and reacting for 2-4 hours;
(4) and adding ketone or ether solvent to dilute the solid content to 70-80% and the viscosity to 2000-6000 mPa.s to obtain the DMF-free composite closed high-solid polyurethane adhesive layer resin for synthetic leather.
The application of DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather is characterized in that: the bonding layer resin is used for the synthetic leather prepared by bonding the base cloth, after a curing agent is added during use, deblocking-curing is realized at the temperature of 120-150 ℃, wherein the using amount of the curing agent is 5-15 parts by mass based on the total amount of the bonding layer resin, after pre-reaction is carried out for a period of time, the bonding layer resin without DMF is obtained and directly bonded with the base cloth, and then the reaction is continued at the temperature of 120-150 ℃ to be fully cured; and rolling after molding and separating the release paper to obtain the synthetic leather product with low DMF content.
The curing agent is an aromatic and aliphatic amine, including but not limited to 4, 4-diaminodiphenylmethane (MDA), 4' -diaminodicyclohexylmethane (H)12MDA) one or both; when there are two, MDA and H12The mass ratio of MDA is 1/2; the addition time of the curing agent is 24-48H when the DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather is used for leather processing.
The present invention is further illustrated by the following specific examples, but it should be understood that the specific materials, process conditions and results described in the examples 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:
a DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather comprises the following components in parts by mass:
isocyanate (Wannate MDI-100) 18 parts
2 parts of isocyanate (Wannate MDI-100 LL)
20 parts of polyether glycol (polytetrahydrofuran diol Poly THF 1000)
40 parts of polyether glycol (polyoxypropylene glycol DDL-2000D)
10 parts of polyether triol (polyoxypropylene triol DMN-400)
Chain extender (ethylene glycol EG) 0.85 parts
0.15 part of chain extender (1, 2-propylene glycol 1, 2-PG)
0.5 part of cross-linking agent (trimethylolpropane TMP)
10 portions of composite sealing agent
20 portions of butanone
Ethylene glycol diethyl ether 5 parts
In the composition, Wannate MDI-100 is pure diphenylmethane diisocyanate produced by Wanhua nicotinate, Wannate MDI-100LL is carbodiimide modified diphenylmethane diisocyanate produced by Wanhua nicotinate, Poly THF 1000 is polytetrahydrofuran diol with molecular weight of 1000 produced by BASF company, DDL-2000D is polyoxypropylene diol with molecular weight of 2000 produced by Shandong de Xin Federal company, and DMN-400 is polyoxypropylene triol with molecular weight of 400 produced by Shandong de Xin Federal company; EG. 1,2-PG and TMP are all commercial products; the composite sealing agent is prepared by 3, 5-dimethylpyrazole and butanone oxime according to a molar ratio of 5/5 and is dissolved in butanone to prepare the composite sealing agent with 50% of solid content; 3, 5-dimethylpyrazole is a sealant product produced by Hubei Jusheng science and technology Limited, and butanone oxime is a sealant product produced by Zhejiang Shengan chemical industry Limited; butanone is a commercially available product, and ethylene glycol diethyl ether is an ether solvent product produced by Qingdao Changhui chemical Co.
The invention also provides a preparation method of the DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather, which comprises the following steps:
(1) adding isocyanate Wannate MDI-100 and Wannate MDI-100LL into a reaction kettle, heating to 50 ℃ for melting, and uniformly stirring;
(2) adding polyether diol Poly THF 1000, polyether diol DDL-2000D, polyether triol DMN-400, chain extender EG, 1,2-PG and cross-linking agent TMP, stirring uniformly, heating to 70 ℃, stirring and reacting for 4 hours;
(3) cooling to 50 ℃, slowly adding the composite sealing agent, heating to 70 ℃, and stirring for reaction for 4 hours;
(4) adding butanone and ethylene glycol diethyl ether, diluting the solid content to 80 percent, and obtaining DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather, wherein the viscosity is 6000 mPa.s/25 ℃;
the invention also provides an application of the DMF-free composite closed high-solid polyurethane adhesive layer resin for synthetic leather, wherein the adhesive layer resin is suitable for synthetic leather prepared by directly adhering base fabrics such as microfiber, woven fabric, elastic cloth and the like, a curing agent MDA (5 parts) is added during use, deblocking-curing is realized at 120 ℃, after pre-reaction is carried out for a period of time, the obtained DMF-free adhesive layer resin is directly adhered to the base fabrics, and then the reaction is continued at 120 ℃ to ensure that the resin is fully cured; rolling after molding and separating the release paper to obtain a synthetic leather product with low DMF content; the DMF content was determined to be 150 ppm.
MDA is 4,4' -diaminodiphenylmethane produced by Nicotiana Tenghua.
Example 2:
a DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather comprises the following components in parts by mass:
isocyanate (Wannate MDI-100) 20 parts
Isocyanate (Wannate MDI-50) 5 parts
15 parts of polyether glycol (polytetrahydrofuran diol Poly THF 1000)
35 parts of polyether glycol (polyoxypropylene glycol DDL-1000D)
15 portions of polyether triol (polyoxypropylene triol DMN-700)
Chain extender (ethylene glycol EG) 1.0 part
Chain extender (1, 2 propylene glycol 1, 2-PG) 0.3 part
1.0 part of crosslinking agent (trimethylolpropane TMP)
15 parts of composite sealing agent
25 parts of 4-methyl-2-pentanone
5 parts of diethylene glycol dimethyl ether
In the composition, Wannate MDI-100 is pure diphenylmethane diisocyanate produced by Tantawa, Wannate MDI-50 is a mixture of 4,4 '-diphenylmethane diisocyanate and 2, 4' -diphenylmethane diisocyanate produced by Tantawa, Poly THF 1000 is polytetrahydrofuran diol with molecular weight of 1000 produced by BASF company, DDL-1000D is polyoxypropylene diol with molecular weight of 1000 produced by Shandong de Xin Federal company, and DMN-700 is polyoxypropylene triol with molecular weight of 700 produced by Shandong de Xin Federal company; EG. 1,2-PG and TMP are all commercial products; the composite sealing agent is prepared by 3, 5-dimethylpyrazole and butanone oxime according to a molar ratio of 6/4, and is dissolved in 4-methyl-2-pentanone to prepare the composite sealing agent with the solid content of 80%; 3, 5-dimethylpyrazole is a sealant product produced by Hubei Jusheng science and technology Limited, and butanone oxime is a sealant product produced by Zhejiang Shengan chemical industry Limited; 4-methyl-2-pentanone is a ketone solvent product supplied by Nantong Runfeng petrochemical Co., Ltd, and diglyme is an ether solvent product supplied by Shanghai Jinle practical Co., Ltd.
The invention also provides a preparation method of the DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather, which comprises the following steps:
(1) adding isocyanate Wannate MDI-100 and Wannate MDI-50 into a reaction kettle, heating to 55 ℃ for melting, and uniformly stirring;
(2) adding polyether diol Poly THF 1000, polyether diol DDL-1000D, polyether triol DMN-700, chain extender EG, 1,2-PG and cross-linking agent TMP, stirring uniformly, heating to 75 ℃, stirring and reacting for 5 hours;
(3) cooling to 55 ℃, slowly adding the composite sealing agent, heating to 75 ℃, and stirring for reaction for 3 hours;
(4) adding butanone, 4-methyl-2-pentanone and diethylene glycol dimethyl ether, diluting the solid content to 75% and the viscosity to 4000 mPa.s/25 ℃, and obtaining the DMF-free composite closed high-solid polyurethane adhesive layer resin for synthetic leather;
the invention also provides application of the DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather, the bonding layer resin is suitable for synthetic leather prepared by directly bonding base cloth such as microfiber, woven cloth, elastic cloth and the like, and a curing agent H is added during use12MDA (10 parts), deblocking-curing is realized at 150 ℃, after a period of pre-reaction, the obtained DMF-free adhesive layer resin is directly attached to the base cloth, and then the reaction is continued at 150 ℃ to ensure that the adhesive layer resin is fully cured; rolling after molding and separating the release paper to obtain a synthetic leather product with low DMF content; the DMF content was determined to be 120 ppm.
H12MDA is 4,4' -diaminodicyclohexylmethane product produced by Nicotiana Wanhua company.
Example 3:
a DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather comprises the following components in parts by mass:
isocyanate (Wannate MDI-100) 25 parts
Isocyanate (Wannate MDI-100 LL) 5 parts
20 parts of polyether glycol (polytetrahydrofuran diol Poly THF 1000)
30 parts of polyether glycol (polyoxypropylene glycol DDL-3000D)
10 parts of polyether triol (polyoxypropylene triol DMN-400)
Chain extender (ethylene glycol EG) 1.2 parts
0.8 part of chain extender (1, 2 propylene glycol 1, 2-PG)
1.5 portions of cross-linking agent (trimethylolpropane TMP)
20 parts of composite sealing agent
40 parts of 4-methyl-2-pentanone
Ethylene glycol diethyl ether 5 parts
In the composition, Wannate MDI-100 is pure diphenylmethane diisocyanate produced by Wanhua nicotinate, Wannate MDI-100LL is carbodiimide modified diphenylmethane diisocyanate produced by Wanhua nicotinate, Poly THF 1000 is polytetrahydrofuran diol with molecular weight of 1000 produced by BASF company, DDL-3000D is polyoxypropylene diol with molecular weight of 3000 produced by Shandong de Xin Federal company, and DMN-400 is polyoxypropylene triol with molecular weight of 400 produced by Shandong de Xin Federal company; EG. 1,2-PG and TMP are all commercial products; the composite sealing agent is prepared by 3, 5-dimethylpyrazole and butanone oxime according to a molar ratio of 7/3, and is dissolved in 4-methyl-2-pentanone to prepare the composite sealing agent with the solid content of 65%; 3, 5-dimethylpyrazole is a sealant product produced by Hubei Jusheng science and technology Limited, and butanone oxime is a sealant product produced by Zhejiang Shengan chemical industry Limited; 4-methyl-2-pentanone is a ketone solvent product supplied by Nantong Runfeng petrochemical company, and ethylene glycol diethyl ether is an ether solvent product produced by Qingdao Changhui chemical company.
The invention also provides a preparation method of the DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather, which comprises the following steps:
(1) adding isocyanate Wannate MDI-100 and Wannate MDI-100LL into a reaction kettle, heating to 60 ℃ for melting, and uniformly stirring;
(2) adding polyether diol Poly THF 1000, polyether diol DDL-3000D, polyether triol DMN-400, chain extender EG, 1,2-PG and cross-linking agent TMP, stirring uniformly, heating to 80 ℃, stirring and reacting for 6 hours;
(3) cooling to 60 ℃, slowly adding the composite sealing agent, heating to 80 ℃, and stirring for reaction for 2 hours;
(4) adding butanone, 4-methyl-2-pentanone and ethylene glycol diethyl ether, diluting the solid content to 70 percent, and obtaining the DMF-free composite closed high-solid polyurethane bonding layer resin for the synthetic leather, wherein the viscosity is 2000 mPa.s/25 ℃;
the invention also provides application of the DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather, the bonding layer resin is suitable for synthetic leather prepared by directly bonding base cloth such as microfiber, woven cloth, elastic cloth and the like, and curing agents MDA and H are added when the resin is used12MDA (5 parts MDA, 10 parts H)12MDA) is carried out, deblocking-curing is carried out at 135 ℃, after pre-reaction is carried out for a period of time, the obtained DMF-free adhesive layer resin is directly attached to the base cloth, and then reaction is continued at 135 ℃ to ensure that the adhesive layer resin is fully cured; rolling after molding and separating the release paper to obtain a synthetic leather product with low DMF content; the DMF content was measured and found to be 170 ppm.
MDA is 4,4 '-diaminodiphenylmethane product produced by Nicotiana Tenwamura, and H12MDA is 4,4' -diaminodicyclohexylmethane product produced by Nicotiana Tenwamura.
Claims (8)
1. A DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather is characterized in that: the paint comprises the following components in parts by mass:
20-30 parts of isocyanate, namely,
60-70 parts of polyether polyol,
1-2 parts of a chain extender,
0.5 to 1.5 portions of cross-linking agent,
10-20 parts of a composite sealing agent,
25-45 parts of ketone or ether solvent;
the chain extender is prepared by mixing ethylene glycol and 1, 2-propylene glycol according to the molar ratio of 9/1-6/4;
the compound sealing agent is prepared by dissolving 3, 5-dimethylpyrazole and butanone oxime in a ketone solvent according to a molar ratio of 5/5-7/3, and the solid content of the compound sealing agent is 50-80%;
the preparation method of the DMF-free composite closed high-solid polyurethane bonding layer resin for the synthetic leather comprises the following steps:
(1) adding isocyanate into a reaction kettle, heating to 50-60 ℃ for melting, and uniformly stirring;
(2) adding polyether polyol, a chain extender and a cross-linking agent, uniformly stirring, heating to 70-80 ℃, and stirring for reacting for 4-6 hours;
(3) cooling to 50-60 ℃, slowly adding the composite sealing agent, heating to 70-80 ℃, stirring and reacting for 2-4 hours;
(4) and adding ketone or ether solvent to dilute the solid content to 70-80% and the viscosity to 2000-6000 mPa.s to obtain the DMF-free composite closed high-solid polyurethane adhesive layer resin for synthetic leather.
2. The DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather according to claim 1, which is characterized in that: the isocyanate is a mixture of diphenylmethane diisocyanate MDI-100 and diphenylmethane diisocyanate MDI-50 or carbodiimide modified MDI according to the mass ratio of 4/1-9/1.
3. The DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather according to claim 1, which is characterized in that: the polyether polyol is at least one polyoxypropylene polyol and at least two polytetrahydrofuran polyols, or at least two polyoxypropylene polyols and at least one polytetrahydrofuran polyol, the number average molecular weight of the polyoxypropylene polyol and the number average molecular weight of the polytetrahydrofuran polyol in the polyether polyol are 400-3000, and the functionality is 2-3.
4. The DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather according to claim 1, which is characterized in that: the cross-linking agent is one of glycerol, trimethylolpropane, diethanolamine and triethanolamine.
5. The DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather according to claim 1, which is characterized in that: the ketone solvent is one of butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 2-methyl-3-pentanone, 4-methyl-2-pentanone, 3-dimethyl-2-butanone, 2-heptanone, 3-heptanone, 5-methyl-3-heptanone, 2, 4-dimethyl-3-pentanone, cyclopentanone and cyclohexanone; the ether solvent is one of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether and diethylene glycol diethyl ether.
6. Use of a DMF free hybrid closed high solids polyurethane tie layer resin according to claim 1, characterised in that: the bonding layer resin is used for the synthetic leather prepared by bonding the base cloth, after a curing agent is added during use, deblocking-curing is realized at the temperature of 120-150 ℃, wherein the using amount of the curing agent is 5-15 parts by mass based on the total amount of the bonding layer resin, after pre-reaction is carried out for a period of time, the bonding layer resin without DMF is obtained and directly bonded with the base cloth, and then the reaction is continued at the temperature of 120-150 ℃ to be fully cured; and rolling after molding and separating the release paper to obtain the synthetic leather product with low DMF content.
7. The use of the DMF free composite blocked high solid polyurethane adhesive layer resin for synthetic leather according to claim 6, wherein: the curing agent is aromatic and aliphatic amine; the addition time of the curing agent is 24-48H when the DMF-free composite closed high-solid polyurethane bonding layer resin for synthetic leather is used for leather processing.
8. The use of the DMF free composite blocked high solid polyurethane adhesive layer resin for synthetic leather according to claim 7, wherein: the aromatic and aliphatic amines are 4, 4-diaminodiphenylmethane MDA, 4' -diaminodicyclohexylmethane H12One or two kinds of MDA, and when two kinds of MDA and H12The mass ratio of MDA was 1/2.
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| CN111892901A (en) * | 2019-05-05 | 2020-11-06 | 郑州大学 | Fast-curing two-component polyurethane sealant for hollow glass and preparation method thereof |
| CN110747656B (en) * | 2019-09-29 | 2021-11-19 | 安徽安利材料科技股份有限公司 | Hydrolysis-resistant high-solid polyurethane synthetic leather and preparation method thereof |
| CN111005235A (en) * | 2019-12-04 | 2020-04-14 | 上海华峰新材料研发科技有限公司 | Method for preparing leather base by using high-solid-content blocked polyurethane resin |
| CN110982473B (en) * | 2019-12-18 | 2021-11-02 | 福建汇得新材料有限公司 | Double-component waterborne polyurethane adhesive for synthetic leather and preparation method thereof |
| TWI712721B (en) | 2020-02-24 | 2020-12-11 | 三芳化學工業股份有限公司 | Artificial leather and method for producing the same |
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| CN112358599B (en) * | 2020-11-12 | 2022-12-27 | 佛山市哲宝科技有限公司 | Thermoplastic polyurethane elastomer and preparation method and application 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 |
| CN112760994B (en) * | 2020-12-28 | 2023-04-21 | 华伦皮塑（苏州）有限公司 | Synthetic leather for rear cover or protective sleeve of electronic product and preparation method thereof |
| CN113683733B (en) * | 2021-08-26 | 2022-04-19 | 大赛璐（中国）投资有限公司 | Curable compositions for 3D printing |
| CN115010895B (en) * | 2022-07-05 | 2023-11-07 | 上海华峰新材料研发科技有限公司 | Enclosed polyurethane resin composition and preparation method and application thereof |
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