CN113881008A - Solvent type polyurethane resin for suede microfiber dyeing and preparation method thereof - Google Patents
Solvent type polyurethane resin for suede microfiber dyeing and preparation method thereof Download PDFInfo
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- CN113881008A CN113881008A CN202111292907.6A CN202111292907A CN113881008A CN 113881008 A CN113881008 A CN 113881008A CN 202111292907 A CN202111292907 A CN 202111292907A CN 113881008 A CN113881008 A CN 113881008A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/348—Hydroxycarboxylic acids
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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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
- C08G18/4808—Mixtures of two or more polyetherdiols
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5285—Polyurethanes; Polyurea; Polyguanides
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/241—Polyamides; Polyurethanes using acid dyes
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Abstract
The invention relates to a solvent type polyurethane resin for dyeing suede microfiber and a preparation method thereof. According to the invention, polytetrahydrofuran ethylene oxide copolyether glycol is innovatively introduced into the polyurethane resin raw material, so that the hydrophilicity of the resin is obviously improved, the polyurethane can better adsorb dye, the dye can quickly permeate into suede microfiber in the dyeing process, and the problem of permeability in the dyeing process of the suede microfiber is fundamentally solved. Meanwhile, a proper amount of chain extender containing carboxyl is introduced into the formula, so that the polyurethane resin is weakly acidic, the dyeing rate of the polyurethane resin is reduced, the dyeing rates of the polyurethane resin and nylon fibers are kept consistent, and the dyeing uniformity of the suede microfiber is improved.
Description
Technical Field
The invention belongs to the technical field of suede microfiber dyeing, and particularly relates to a solvent type polyurethane resin for suede microfiber dyeing and a preparation method thereof.
Background
The superfine fiber synthetic leather is originally originated from Japan, is a polymer composite material, structurally has a real leather simulation structure, and a processed product of the superfine fiber synthetic leather has high mechanical strength, soft and plump hand feeling and strong real leather feeling, and is an ideal substitute of natural leather. The microfiber leather is also divided into suede microfiber leather and smooth microfiber leather, the suede microfiber leather is prepared by dyeing and sanding the produced microfiber base cloth and other processing technologies, has the characteristics of bright color, fine surface touch and good air permeability, is widely applied to high-end fields such as electronic packaging, shoe materials, home decoration, automotive interior and the like, and has the characteristic of high added value. The quality of the dyeing performance of the suede microfiber determines the grade of the product.
The microfiber is a composite material of nylon fiber and polyurethane, has a two-phase structure, and has different adsorption capacity and dye-uptake rate to dye, so that the situation of inconsistent color depth and brilliance of the fiber and the polyurethane often occurs after the suede microfiber is dyed. Because dyed suede microfiber products are generally thick, the phenomenon that dyes cannot permeate and a white core appears in the middle behind the microfiber sheet skin can also occur during dyeing.
In the prior art, a lot of patents related to polyurethane resin for suede microfiber are provided, but the color vividness of dyed suede microfiber is researched, and all the disclosed patents are that groups such as amido, secondary amino or tertiary amino are introduced into a polyurethane molecular chain, so that the binding force of the polyurethane molecular chain and an acid dye is improved, and further the dyeing vividness of polyurethane is improved. For example, the polyurethane resin easy to dye for superfine fiber synthetic leather disclosed in chinese patent CN105542108A and the preparation method thereof improve the color brilliance of the polyurethane resin by introducing amide group, secondary amino group or tertiary amino group into polyol and chain extender. Chinese patent CN 109734868A discloses a high-physical-property high-dyeing polyurethane resin special for superfine fiber synthetic leather and a preparation method thereof, the patent also discloses that the polyurethane resin is prepared by adopting polyalcohol prepared by N-methyldiethanolamine as a raw material, and a tertiary amine structure is introduced into the resin, so that the binding force of the polyurethane and an acid dye is improved, and the brilliance of the dyed superfine fiber resin is improved.
In the actual microfiber dyeing process, the problem of permeability of suede microfiber dyeing is usually improved by prolonging the dyeing time, but the method cannot fundamentally solve the permeability problem, cannot solve the problem of inconsistent colors of fibers and polyurethane, and has the problem of low production efficiency.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a solvent type polyurethane resin for dyeing suede microfiber and a preparation method thereof, and solves the problems of poor dyeing permeability of suede microfiber dyeing and poor color balance of fiber and polyurethane resin.
In order to achieve the purpose, the invention adopts the technical scheme that:
the solvent type polyurethane resin comprises the following raw materials in percentage by mass:
the polyol component comprises polyether diol and polyester diol, and the polyether diol at least contains polytetrahydrofuran ethylene oxide copolyether glycol.
In some preferred and specific embodiments, the mass ratio of the polyether diol to the polyester diol is 4-6: 1.
The number average molecular weights of the polyether dihydric alcohol and the polyester dihydric alcohol are 1000-3000 respectively.
In some preferred and specific embodiments, the polytetrahydrofuran ethylene oxide copolyether glycol comprises 5 to 15% by mass of the total mass of the polyol component. Preferably, the weight of the polytetrahydrofuran ethylene oxide copolyether glycol accounts for 9-12% of the total weight of the polyol component.
In some preferred and specific embodiments, the polytetrahydrofuran ethylene oxide copolyether glycol has a number average molecular weight of 1000 to 3000. Such as PTM-EOG-2000, which is a polyether diol obtained by copolymerizing tetrahydrofuran and ethylene oxide with a molecular weight of 2000 and produced from Japanese grease.
In some preferred and specific embodiments, the polyether diols include the polytetrahydrofuran ethylene oxide copolyether diol and polytetrahydrofuran diol. Preferably, the mass ratio of the polytetrahydrofuran ethylene oxide copolyether glycol to the polytetrahydrofuran glycol is 5-10: 1. More preferably, the mass ratio of the polytetrahydrofuran ethylene oxide copolyether glycol to the polytetrahydrofuran glycol is 6-8: 1.
The polytetrahydrofuran is selected from PTMG-2000 produced by Daizhike chemical industry Co., Ltd in Taiwan area.
In some preferred and specific embodiments, the polyester diol comprises one or both of a polyhexamethylene 1,6 diol adipate, a polyhexamethylene 1,4 diol adipate. Such as poly-1, 4-butanediol adipate diol PABT-2000 with molecular weight of 2000 and poly-1, 6-hexanediol adipate diol PAHT-2000 with molecular weight of 2000, which are produced by Jiangsuhua big new materials Co.
In some preferred and specific embodiments, the carboxyl-containing chain extender is selected from dimethylolpropionic acid (DMPA), dimethylolbutyric acid (DMBA), tartaric acid.
In some preferred and specific embodiments, the diisocyanate is 4, 4-diphenylmethane diisocyanate (MDI).
In some preferred and specific embodiments, the alcoholic chain extender is selected from ethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 2-propanediol.
In some preferred and specific embodiments, the solvent is selected from the group consisting of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), N-diethylformamide.
In some preferred and specific embodiments, the terminating agent is methanol. The catalyst is an organobismuth catalyst, such as MB 20.
In some preferred and specific embodiments, the adjuvant includes, but is not limited to, an antioxidant. Preferably, the antioxidant is one or a mixture of two of pentaerythritol tetra (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) and 2,2' -methylenebis (4-methyl-6-tert-butylphenol).
In some preferred and specific embodiments, the molar ratio of isocyanate groups in the diisocyanate to active hydrogen in the system is 1-1.05: 1, and the molar amount of the active hydrogen in the system is the sum of the molar amounts of the active hydrogen in the polyol component, the alcohol chain extender and the carboxyl-containing chain extender.
The second technical scheme adopted by the invention is as follows: a preparation method of the solvent type polyurethane resin comprises the following steps:
(1) mixing a polyol component, an auxiliary agent, a part of solvent, a catalyst and a part of diisocyanate, and reacting at 75-85 ℃;
(2) after the reaction in the step (1) is finished, adding an alcohol chain extender and a carboxyl-containing chain extender, reacting at 60-70 ℃, then adding the rest diisocyanate, reacting at 75-85 ℃, and after the reaction is finished, adding a terminator to prepare polyurethane resin;
and (3) during the reaction process of the step (2), adding the residual solvent to control the viscosity of the system.
Further, in the step (1), the polyol component, the auxiliary agent and a part of the solvent are uniformly mixed to form a mixed solution with a solid content of 50-70%, then a catalyst and diisocyanate are added into the mixed solution, and the mixed solution is reacted for 1-2 hours at a temperature of 75-85 ℃.
Preferably, in step (1), the diisocyanate is added so that the molar ratio of isocyanate groups in the system to active hydrogen in the system is 0.5-0.7: 1.
Further, in the step (2), the reaction time at 60-70 ℃ is 0.5-2 h, and the reaction time at 75-85 ℃ is 2-5 h.
In the invention, the viscosity of the solvent type polyurethane resin is controlled to be 60-100Pas/25 ℃.
The third technical scheme adopted by the invention is as follows: the solvent type polyurethane resin or the solvent type polyurethane resin prepared by the preparation method is applied to dyeing of suede microfiber.
The suede microfiber comprises fixed island suede microfiber or indefinite island suede microfiber.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, polytetrahydrofuran ethylene oxide copolyether glycol is innovatively introduced into the polyurethane resin raw material, so that the hydrophilicity of the resin is obviously improved, the polyurethane can better adsorb dye, the dye can quickly permeate into suede microfiber in the dyeing process, and the problem of permeability in the dyeing process of the suede microfiber is fundamentally solved. Meanwhile, a proper amount of chain extender containing carboxyl is introduced into the formula, so that the polyurethane resin is weakly acidic, the dyeing rate of the polyurethane resin is reduced, the dyeing rates of the polyurethane resin and nylon fibers are kept consistent, and the dyeing uniformity of the suede microfiber is improved.
The suede microfiber prepared by the polyurethane resin has the characteristics of excellent permeability, excellent leveling property and good color matching property between the fiber and the polyurethane resin.
Drawings
FIG. 1 is a graph showing the dyeing effect of a surface dyed with textured microfibers prepared from the polyurethane resin of example 2;
FIG. 2 is a graph showing the dyeing effect of a surface dyed with textured microfibers prepared from the polyurethane resin of comparative example 2;
fig. 3 is a graph showing the dyeing effect of the surface of the suede-shaped microfiber prepared by using the polyurethane resin of comparative example 3 after dyeing.
Detailed Description
The problems of poor permeability and balanced resin and fiber dyeing of suede microfiber dyeing have been known in the industry for a long time, and cannot be solved fundamentally by prolonging the dyeing time. The inventor discovers that the difficulties of dyeing the suede microfiber are concentrated on the permeability of thick products and the dyeing balance of fiber and polyurethane resin through analysis and research of downstream suede microfiber dyeing factories, and because the polyurethane contains a large amount of urethane bonds and is combined with acid dye, the dyeing brightness is superior to that of nylon fiber, and the dyeing speed is obviously higher than that of nylon fiber, so how to reduce the dyeing speed of the polyurethane and ensure the dyeing speed consistency of the polyurethane and the nylon fiber is to solve the core problem of dyeing the suede microfiber.
On one hand, a certain amount of polytetrahydrofuran ethylene oxide copolyether glycol is introduced into the formula, so that the hydrophilicity of the resin is obviously improved, the polyurethane can better adsorb dye, the dye can quickly permeate into the suede microfiber in the dyeing process, and the problem of permeability is solved.
Because of the large amount of urethane groups in the molecular chain of the polyurethane and the lower glass transition temperature, compared with nylon fibers, the polyurethane has a fast dye-uptake rate to anionic acid dyes. In the second aspect of the invention, a proper amount of chain extender containing carboxyl is introduced into the formula, so that the polyurethane resin is weakly acidic, the dyeing rate of the polyurethane resin is reduced, the dyeing rates of the polyurethane resin and nylon fibers are kept consistent, the dyeing uniformity of the suede microfiber is improved, and the problem of level-dyeing property of the suede microfiber is solved. The solvent type polyurethane resin is used for dyeing suede microfiber, can radically solve the problems of penetrability and dyeing uniformity of suede microfiber dyeing, has obviously improved production rate, and belongs to red sea blue wave.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. Accordingly, the following examples are provided only to further illustrate the present invention and are not meant to limit the scope of the present invention in any way.
Example 1
The solvent type polyurethane resin for dyeing the suede microfiber provided by the embodiment comprises the following raw materials in formula:
wherein PTMG-2000 is polytetrahydrofuran diol with molecular weight of 2000, and is produced by Daizhong chemical industry Co., Ltd in Taiwan; PTM-EOG-2000 is polyether diol copolymerized by tetrahydrofuran and ethylene oxide with molecular chain 2000, and is produced by Japanese grease; PABT-2000 is poly 1,4 butylene glycol adipate glycol with molecular weight of 2000, which is produced by Jiangsu Hua new material company; DMPA is dimethylolpropionic acid, produced by Paston, Sweden; the catalyst is organic bismuth.
The polyurethane resin for dyeing the suede microfiber of the present example is prepared by the following method:
(1) adding 26.1g of PABT-2000, 128.4g of PTMG-2000, 17.2g of PTM-EOG-2000 and 0.2g of antioxidant I-1010 into 114g of DMF solvent to form a solution with the solid content of 60 percent;
(2) uniformly stirring the solution obtained in the step (1), adding 12g of MDI and a catalyst, and enabling the molar ratio of isocyanate in diisocyanate to active hydrogen in a system to be 0.5-0.7:1, reacting for 1.5h at 75-85 ℃.
(3) Adding 1.4g of DMPA and 13g of EG into the solution reacted in the step (2), reacting at 60-70 ℃ for 1h, and then adding the rest diisocyanate to react at 75-85 ℃ for 4 h; and continuously adding a solvent to control the viscosity of the polyurethane resin in the reaction process, adding 0.2g of reaction terminator methanol after the reaction is finished, and controlling the viscosity of the reaction terminator methanol to be 60-100Pas/25 ℃ to obtain the polyurethane resin.
Example 2
The polyurethane resin for the dyed suede microfiber provided by the embodiment comprises the following raw materials in formula:
wherein, PAHT-2000 is poly adipic acid 1,6 hexanediol glycol ester diol with molecular weight of 2000, and is produced by Jiangsu Hua large new material company; DMBA is dimethylolbutanoic acid, produced by Huzhou Changsheng chemical Co., Ltd.
The polyurethane resin for the dyed suede microfiber of the present example was prepared by the following method:
(1) 27.1g of PAHT-2000, 124.4g of PTMG-2000, 20.2g of PTM-EOG-2000 and 0.2g of antioxidant I-1010 were added to 118g of DMF solvent to form a solution with a solids content of 59%;
(2) uniformly stirring the solution obtained in the step (1), adding 12g of MDI and a catalyst, and enabling the molar ratio of isocyanate in diisocyanate to active hydrogen in a system to be 0.5-0.7:1, reacting for 1.5h at 75-85 ℃.
(3) Adding 1.54g of DMBA and 13g of EG into the solution reacted in the step (2), reacting for 1h at the temperature of 60-70 ℃, and then adding the rest diisocyanate to react for 4h at the temperature of 75-85 ℃; and continuously adding a solvent to control the viscosity of the polyurethane resin in the reaction process, adding 0.2g of reaction terminator methanol after the reaction is finished, and controlling the viscosity of the reaction terminator methanol to be 60-100Pas/25 ℃ to obtain the polyurethane resin.
Example 3
The polyurethane resin for the dyed suede microfiber provided by the embodiment comprises the following raw materials in formula:
the polyurethane resin for the dyed suede microfiber of the present example was prepared by the following method:
(1) 27.1g of PAHT-1000, 126.4g of PTMG-2000, 18.2g of PTM-EOG-2000 and 0.2g of antioxidant I-1010 were added to 118g of DMF solvent to form a solution with a solids content of 59%;
(2) uniformly stirring the solution obtained in the step (1), adding 14.9g of MDI and a catalyst, and enabling the molar ratio of isocyanate in diisocyanate to active hydrogen in a system to be 0.5-0.7:1, reacting for 1.5h at 75-85 ℃.
(3) Adding 2.1g of DMPA and 13.5g of EG into the solution reacted in the step (2), reacting at 60-70 ℃ for 1h, and then adding the rest diisocyanate to react at 75-85 ℃ for 4 h; and continuously adding a solvent to control the viscosity of the polyurethane resin in the reaction process, adding 0.2g of reaction terminator methanol after the reaction is finished, and controlling the viscosity of the reaction terminator methanol to be 60-100Pas/25 ℃ to obtain the polyurethane resin.
Comparative example 1
The polyurethane resin provided in this example is different from that of example 1 in that: the polyurethane resin of the example is prepared from the following raw materials in percentage by weight without adding PTM-EOG-2000 and DMPA:
the preparation method of the polyurethane resin of this example is substantially the same as that of example 1.
Comparative example 2
The polyurethane resin provided in this example is different from that of example 2 in that: the raw material formula of the polyurethane resin of the embodiment is composed of the following components in percentage by weight without adding DMBA:
the preparation method of the polyurethane resin of this example is substantially the same as that of example 2.
Comparative example 3
The polyurethane resin provided in this example is different from that of example 2 in that: the DMBA is added in excess, and the raw material formula of the polyurethane resin in the embodiment specifically comprises the following components:
the preparation method of the polyurethane resin of this example is substantially the same as that of example 2.
Comparative example 4
The polyurethane resin provided in this example is different from that of example 3 in that: the PTM-EOG-2000 is not added, and the raw material formula of the polyurethane resin comprises the following components:
the preparation method of the polyurethane resin of this example is substantially the same as that of example 3.
The polyurethane resins prepared in examples 1 to 3, common polyurethane resins (derived from commercially available solvent type polyurethane resins for suede microfibers) and the polyurethane resins of comparative examples 1 to 4 were prepared into wet slurry, and the formulation of the wet slurry is shown in table 1:
table 1 shows the formulation of the wet slurry
| Raw materials | DMF | Penetrant | Softening agent | Resin composition |
| Quality of | 50-60 | 1 | 0.5 | 100 |
Controlling the viscosity of each sizing agent to be 4000-5000 cps/normal temperature, impregnating with nylon sea-island fiber cloth, controlling the PU content to be 35-45%, then reducing and splitting fibers in hot toluene to prepare suede microfiber bass, adopting an acid dye, controlling the pH value of a dye solution to be 4-5, heating to 90 ℃ from the normal temperature according to the heating rate of 1 ℃/min, preserving heat for 2H, then cooling to the normal temperature according to the speed of 2 ℃/min, soaping the bass after dyeing is finished, then drying, then carrying out splitting treatment on the dyed suede microfiber, dividing the original 2.5mm bass into two halves, observing the skin surface permeability and the surface leveling property of the suede microfiber prepared by different resins, and obtaining the results shown in table 2 and fig. 1-3.
Evaluation of dye permeability: the white core on the surface of the sheet skin has poor permeability; the surface of the sheet skin has no white core, so the permeability is excellent.
Evaluation of leveling Properties: the level-dyeing property refers to the consistency of the colors of the fibers and the polyurethane of the suede microfiber leather after dyeing, the consistency of the depth of the color is ensured when the color is single, and the color difference between the fibers and the polyurethane is ensured to be small when the color is a composite color. The color phases are consistent.
Table 2 shows the comparison of the dyeing effect of the suede microfiber prepared by using the polyurethane resins of examples 1 to 3 and comparative examples 1 to 4
Note: the normal hand feeling means that the hand feeling is plump and the resilience is good, and the normal requirements of customers can be met.
In the figure 1 (embodiment 2), the colors of the fibers and the resin are basically consistent, the color uniformity of the fibers and the resin is excellent, and the integral feeling of the suede microfiber leather is good; in FIG. 2 (comparative example 2), the fiber color development is light, the resin color development is obviously darker, black spots exist, and the level-dyeing property between the fiber and the resin is poor; in FIG. 3 (comparative example 3), the fibers developed dark color, the resin developed light color, and was white, giving a feeling of eye marks as a whole, and the leveling property between the fibers and the resin was poor.
As can be seen from table 2, when the polyurethane resin of embodiments 1 to 3 of the present invention is applied to the field of pile face microfiber, the permeability and level-dyeing property of the pile face microfiber can be significantly improved, and the grade of the pile face microfiber is significantly improved.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (10)
1. The solvent type polyurethane resin is characterized by comprising the following components in percentage by mass:
8-10% of diisocyanate;
17-22% of a polyol component;
0.1-0.3% of a chain extender containing carboxyl;
1.1-1.5% of an alcohol chain extender;
0.001-0.005% of a catalyst;
68-73% of a solvent;
0.02-0.1% of an auxiliary agent;
0.02-0.1% of a terminator;
the polyol component comprises polyether diol and polyester diol, and the polyether diol at least contains polytetrahydrofuran ethylene oxide copolyether glycol.
2. A solvent type polyurethane resin according to claim 1, wherein: the mass of the polytetrahydrofuran ethylene oxide copolyether glycol accounts for 5-15% of the total mass of the polyol component; and/or the number average molecular weight of the polytetrahydrofuran ethylene oxide copolyether glycol is 1000-3000.
3. A solvent type polyurethane resin according to claim 1, wherein: the polyether diols include the polytetrahydrofuran ethylene oxide copolyether diol and polytetrahydrofuran diol; and/or the polyester diol comprises one or two of poly adipic acid 1,6 hexanediol ester diol and poly adipic acid 1,4 butanediol ester diol.
4. A solvent type polyurethane resin according to claim 1, wherein: the number average molecular weights of the polyether dihydric alcohol and the polyester dihydric alcohol are 1000-3000 respectively; and/or the mass ratio of the polyether glycol to the polyester glycol is 4-6: 1.
5. A solvent type polyurethane resin according to any one of claims 1 to 4, wherein: the chain extender containing carboxyl is selected from dimethylolpropionic acid, dimethylolbutyric acid and tartaric acid.
6. A solvent type polyurethane resin according to any one of claims 1 to 4, wherein: the diisocyanate is 4, 4-diphenylmethane diisocyanate; and/or the alcohol chain extender is selected from ethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 2-propanediol; and/or the solvent is selected from N, N-dimethylformamide, N-dimethylacetamide and N, N-diethylformamide; and/or, the terminating agent is methanol; and/or the auxiliary agent comprises an antioxidant.
7. A solvent type polyurethane resin according to any one of claims 1 to 4, wherein: the molar ratio of isocyanate in the diisocyanate to active hydrogen in the system is 1-1.05: 1, and the molar amount of the active hydrogen in the system is the sum of the molar amounts of the active hydrogen in the polyol component, the alcohol chain extender and the carboxyl-containing chain extender.
8. A method of producing a solvent-type polyurethane resin according to any one of claims 1 to 7, comprising the steps of:
(1) mixing a polyol component, an auxiliary agent, a part of solvent, a catalyst and a part of diisocyanate, and reacting at 75-85 ℃;
(2) after the reaction in the step (1) is finished, adding an alcohol chain extender and a carboxyl-containing chain extender, reacting at 60-70 ℃, then adding the rest diisocyanate, reacting at 75-85 ℃, and after the reaction is finished, adding a terminator to prepare polyurethane resin;
and (3) during the reaction process of the step (2), adding the residual solvent to control the viscosity of the system.
9. The method of claim 8, wherein: in the step (1), the polyol component, the auxiliary agent and part of the solvent are uniformly mixed to form a mixed solution with a solid content of 50-70%, then a catalyst and diisocyanate are added into the mixed solution, and the mixed solution is reacted for 1-2 hours at a temperature of 75-85 ℃; and/or, in the step (1), the diisocyanate is added, so that the molar ratio of isocyanate in the system to active hydrogen in the system is 0.5-0.7: 1; and/or in the step (2), the reaction time at 60-70 ℃ is 0.5-2 h, and the reaction time at 75-85 ℃ is 2-5 h.
10. Use of the solvent-borne polyurethane resin according to any one of claims 1 to 8 or the solvent-borne polyurethane resin prepared by the preparation method according to claim 8 or 9 for dyeing pile microfiber.
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