TWI728243B - Polyurethane resin, use thereof, and artificial leather comprising the same and method of producing artificial leather - Google Patents

Abstract

The present invention provides an irreversible solvent-free polyurethane resin comprising one or more isocyanates, one or more polyols, and one or more silane compounds, wherein the one or more isocyanates, one or more polyols, and one or more silane compounds are reacted to form a polyurethane prepolymer, and wherein the one or more polyols are selected from the group consisting of a polyester polyol, a polyether polyol, and the mixture thereof. The present invention further relates to an artificial leather comprising the irreversible solvent-free polyurethane resin according to the present and the method for producing the same. The artificial leather has improved characteristics, such as good soft-hand feeling, hydrolysis resistance, weatherability, flexibility and good full-feeling.

Description

Polyurethane resin, its use, artificial leather containing it, and method of manufacturing artificial leather

The present invention relates to a one-way solvent-free polyurethane resin. In particular, it provides a one-way solvent-free polyurethane resin used in the manufacture of artificial leather and the like. The present invention also relates to an artificial leather containing unidirectional solvent-free polyurethane resin and a manufacturing method thereof.

With the development of industrial technology, the production technology of artificial leather has also improved day by day, using polyurethane as raw material with different substrate layers (plain woven fabric, double-sided/four-sided stretch fabric, non-woven microfiber fabric, etc.), and appropriate processing methods , To produce artificial leather with different characteristics and surface patterns. Therefore, compared with natural leather, artificial leather has the advantages of multi-function and diversification.

Existing artificial leather, solvent-based polyurethane resin (PU) with a solid content of 40 to 60% is often used as the main raw material for the leather surface of artificial leather, whether it is a dry process or a wet process, in the leather making process, In addition to the organic solvents contained in the polyurethane resin itself (for example: dimethylformamide (DMF), dimethylacetamide (DMAc) or methyl ethyl ketone (MEK)), other solvents are usually used to prepare the polyurethane resin To make the polyurethane resin easy to be coated on the substrate layer, and finally before the end of the manufacturing process, the solvent is removed by drying or water bath replacement to form a polyurethane resin leather surface with a solidified phase.

However, the prior art method of manufacturing artificial leather is quite complicated and time-consuming, which is not economical, and the organic solvents involved in the manufacturing process and the residual organic solvents in the final product are not good for human health and the environment. Today's requirements for green chemistry processes and materials. In view of the increasing environmental awareness in recent years, the state of the art has proposed several methods of manufacturing artificial leather with environmental protection requirements, such as: TW I560335 discloses a method involving coating a one-component solvent-free polyurethane resin to manufacture artificial leather. The method includes directly coating the polyurethane resin on the release layer, and reacting the isocyanate (NCO) group contained in the polyurethane resin with moisture to generate CO ₂ , thereby forming a foam rubber, which is then pasted with the substrate to synthesize To make artificial leather; TW I429537 discloses a method for manufacturing artificial leather by casting or spraying two-component solvent-free polyurethane; CN 105019254A discloses a method of pouring a thermoplastic elastomer containing molecular sieve into a matrix layer to manufacture artificial leather. Leather method.

However, the polyurethane resin of the prior art is not suitable for continuous production, and the produced artificial leather has problems such as surface pinhole defects resulting in poor external feel; therefore, in the technical field of the present invention, there is still a continuous search for a usable improvement. Rate and efficiency of the continuous process to produce polyurethane resin with improved tactile feel of artificial leather.

Therefore, in order to solve the aforementioned technical problems, one objective of the present invention is to provide a unidirectional solvent-free polyurethane resin with good stability, processability and adhesion.

Another object of the present invention is to provide a method for manufacturing the unidirectional solvent-free polyurethane resin as described above.

Another object of the present invention is to provide a method for manufacturing artificial leather that has improved convenience and environmental protection compared to conventional dry or wet polyurethane processing methods. Compared with the prior art exemplified above, the artificial leather produced by the method of the present invention has controllable touch and foaming ratio.

Another object of the present invention is to provide an artificial leather containing the unidirectional solvent-free polyurethane resin as described herein, which has improved soft touch, hydrolysis resistance, weather resistance, flexibility, and richness. Because of its characteristics, it is especially advantageous for leather such as ball leather, shoe leather, sofa leather, car leather or luggage leather.

All ranges disclosed in this article should be understood to encompass any and all sub-ranges contained therein. For example, the range of "1 to 10" shall be regarded as including any and all sub-ranges between the minimum value of 1 and the maximum value of 10 and including the maximum value of 1 and the maximum value of 10; All sub-ranges starting with the minimum value of 10 and ending with a maximum value less than 10, for example: 1 to 6.7, 3.2 to 8.1, or 5.5 to 10, and any number in the range, for example: 2.6, 4.7 or 7.3.

Unidirectional solvent-free polyurethane resin

The unidirectional solventless polyurethane resin of the present invention contains one, two, three or more isocyanates, one, two, three or more polyols, and one, two, three or more silanes The compound, wherein the (etc.) polyol is selected from the group consisting of polyester polyol, polyether polyol and combinations thereof.

The unidirectional solvent-free polyurethane resin of the present invention preferably does not substantially contain any volatile organic solvent.

According to one aspect of the present invention, unidirectional solvent-free polyurethane resin comprises one or more functional groups may be self-crosslinking reaction of, for example, but not limited to: a releasable reaction with CO ₂ and moisture carried from the isocyanate crosslinking reaction of ( NCO) functional group, and/or silane functional group that can react with moisture to dealcoholize and perform self-bridging reaction. Thereby, after the unidirectional solvent-free polyurethane resin of the present invention is coated on the matrix layer, in addition to the self-bridging reaction of the polyurethane resin, it can also produce adhesion effects with the matrix layer.

According to one aspect of the present invention, based on the total weight of the unidirectional solventless polyurethane resin, the content of isocyanate groups (NCO%) is 2 to 4 wt%, such as but not limited to: 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, or 4.0 wt%. In a preferred aspect, the total molar ratio (NCO/OH) of the isocyanate group (-NCO) of one or more isocyanates and the hydroxyl group (-OH) of one or more polyols (NCO/OH) is greater than 1, for example, but not limited to: greater than Or equal to 1.01, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 2, 2.5, 3 or more, preferably It is 1.5 to 1.7wt%. If the NCO/OH is too low (<1.0), the polyurethane resin has too high viscosity, which is not conducive to the processability of coating on the substrate layer, and because of the low NCO/OH ratio, it has a lower isocyanate group content, which in turn causes Polyurethane resin has a lower bridging density, which is not conducive to the mechanical strength of polyurethane resin and the artificial leather made from it; on the contrary, if the NCO/OH is too high (>2.0), the polyurethane has too low viscosity, so when the polyurethane When the resin is coated on the substrate layer, it is easy to cause the problem of glue bleeding, and because of the high NCO/OH ratio, which has a higher isocyanate group content, the polyurethane resin has a higher bridging density, so the artificial synthetic leather made from it Has a hard feel.

Therefore, the suitable viscosity of the unidirectional solventless polyurethane resin of the present invention is, for example, but not limited to: 50ps to 300ps at 100°C, such as: 50, 55, 60, 80, 100, 120, 140, 160, Viscosity of 180, 200, 220, 240, 260, 280, or 300ps. In an example of the present invention, it is preferably 100 to 280 ps.

Isocyanate

The isocyanate suitable for the unidirectional solvent-free polyurethane resin of the present invention is not particularly limited, and is preferably an isocyanate containing two, three or more isocyanate groups, for example: aliphatic monomer diisocyanate, alicyclic monomer diisocyanate Isocyanate, aromatic monomer diisocyanate, or group thereof Together.

Suitable isocyanates include but are not limited to: aromatic polyisocyanates, such as 4,4'-diphenylmethane diisocyanate (MDI), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate , 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, naphthalene-1,5-diisocyanate (NDI), toluene diisocyanate (TDI), tetramethylxylene diisocyanate, toluene diisocyanate Isocyanate, naphthalene, di- and tetraalkyl diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, or a combination thereof; aliphatic isocyanate, for example: dodecane diisocyanate, dimer fatty acid diisocyanate, 4, 4'-dibenzyl diisocyanate, 1,6-diisocyanato-2,4,4-trimethylhexane, 1,4-diisocyanobutyl ester, 1,6-diisocyanohexyl ester (HDI), 1,4-diisocyanurate tetramethoxybutyl, dicyclohexylmethane diisocyanate, 1,12-diisocyanatododecane, cyclic diisocyanate such as 4,4-dicyclohexylmethane Diisocyanate, 1,3-cyclohexane, 1,4-cyclohexane diisocyanate, 1-methyl-2,4-diisocyanatocyclohexane, 1-isocyanomethyl-3-iso Cyano-1,5,5-trimethylcyclohexane (isophorone diisocyanate, IPDI), hydrogenated or partially hydrogenated MDI ([H]12MDI (hydrogenated) or [H]6MDI (partially hydrogenated)), Xylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), di- and tetraalkylene diphenylmethane diisocyanate; or a combination thereof. According to one aspect of the present invention, the aforementioned one or more isocyanates are selected from the group consisting of toluene diisocyanate and diphenylmethane diisocyanate.

Suitable isocyanates have a molecular weight of 100 to 600 g/mol, for example: 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480, 500, 520, 540, 560, 580 or 600 g/mol, preferably with a molecular weight of 160 to 500 g/mol.

According to one aspect of the present invention, based on the total weight of the polyurethane resin, the content of the isocyanate is 30 to 35 wt%, such as but not limited to: 30.0, 30.5, 31.0, 31.5, 32.0, 32.5, 33.0, 33.5, 34.0, 35.5, or 35.0wt%.

Polyester/polyether polyol

The polyol contained in the unidirectional solvent-free polyurethane resin of the present invention is selected from the group consisting of polyester polyols, polyether polyols and combinations thereof.

According to one aspect of the present invention, based on the total weight of the polyurethane resin, the content of the aforementioned one or more polyols is 60 to 65 wt%, such as but not limited to: 60.0, 60.5, 61.0, 61.5, 62.0, 62.5, 63.0, 63.5 , 64.0, 64.5, or 65.0wt%.

Polyester polyol

As used herein, the term "polyester polyol" is well known to the skilled person. It can be obtained by reacting a polycarboxylic acid with a polyol. Its structure includes the polymer chain of the polyester and the terminal carboxyl group or alcohol. The properties of polyester polyols can be adjusted by selecting different types of comonomers. For example, single linear aliphatic diols and linear aliphatic dibasic acids are prone to produce semi-crystalline polymers; The length of the carbon chain of the acid can increase its melting point by using symmetric aromatic dibasic acids; by increasing the number of comonomers or incorporating branched aliphatic comonomers, more amorphous substances can be obtained. Polyester polyols may also contain other functional groups, such as NH or COOH.

Suitable polyester polyols can be crystalline, semi-crystalline and non-crystalline polyester polyols, and their manufacturing methods are well known to those skilled in the art.

The polyester polyol suitable for the present invention preferably contains two, three or more functional groups, and more preferably contains two, three or more hydroxyl groups.

The polyester polyols suitable for the present invention include aliphatic polyester diols, such as those made from dibasic acids and diols, such as polyethylene adipate diol, polyadipate Butylene glycol ester diol, polyhexylene adipate diol, or mixtures thereof; aromatic polyester diols, such as those made from aromatic dibasic acids, adipic acid and diols , Such as: polyethylene diethylene phthalate Glycol, polyneopentyl glycol phthalate glycol, polybutylene phthalate hexylene glycol diol, polyhexylene phthalate glycol; or mixtures thereof. Polyester polyols such as those made by copolymerization of dibasic acid, dihydric alcohol and trihydric alcohol, for example: dibasic acid dihydric alcohol trimethylolpropane copolyol.

According to one aspect of the present invention, the aforementioned polyester polyol has a weight average molecular weight of 800 to 4000, for example: 800, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, 3200, Weight average molecular weight of 3400, 3600, 3800 or 4000.

Polyether polyol

The polyether polyol suitable for the present invention is not particularly limited, such as but not limited to: polyoxypropylene glycol (PPG), polyoxypropylene glycerol (PPG), polytetramethylene ether two Polytetramethylene ether glycol (PTMEG), polyethylene glycol, polytetramethylene glycol, tetrahydrofuranoxide propylene copolymer glycol, or a combination thereof.

According to one aspect of the present invention, the aforementioned polyether polyol has a weight average molecular weight of 400 to 3000, for example: 400, 600, 800, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, Or a weight average molecular weight of 3000.

Silane compounds

The function of the silane compound contained in the polyurethane resin of the present invention is to improve the adhesion and low foaming property between the polyurethane resin and the matrix layer. The type is not particularly limited, for example, but not limited to: epoxy silane compound, such as γ -Glycidyl trimethoxysilane (γ- glycidoxypropyltrimethoxysilane, A-187); aminosilane compounds, such as γ-aminopropyltriethoxysilane (γ-aminopropyltriethoxysilane, A-1100), bis-(γ-trimethoxysilyl) amine (bis-(γ -trimethoxysilylpropyl)amine, A-1170); isocyanate-based silane compounds, such as γ-isocyanatopropyltriethoxysilane (γ-isocyanatopropyltriethoxysilane, A-Link-25), γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltriethoxysilane, A-Link-25); γ-isocyanatopropyltrimethoxysilane, A-Link-35); or a mixture thereof.

According to one aspect of the present invention, based on the total weight of the polyurethane resin, the content of the aforementioned silane compound is 0.1 to 5 wt%, such as but not limited to: 0.1, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0, 1.2, 1.4, 1.5, 1.6, 1.8, 2.0, 2.2, 2.4, 2.5, 2.6, 2.8, 3.0, 3.2, 3.4, 3.5, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, or 5.0wt%, preferably 0.8 to 3wt%.

additive

The unidirectional solventless polyurethane resin of the present invention may optionally contain one or more known additives. As used herein, the term "additives" can be catalysts, stabilizers, adhesion promoters, dyes, fillers (such as silicates, talc, calcium carbonate, clay or carbon black), thixotropic agents (such as bentonite, silicon coking) Acid, urea derivatives, fibrillated or short pulp fibers), color pastes and/or pigments, thermoplastic polymers, plasticizers, rheology additives, foaming agents, anti-sticking agents, wax oils, or any of them combination.

According to one aspect of the present invention, based on the total weight of the polyurethane resin, the content of the aforementioned one or more optional additives is 5wt% or less, such as but not limited to: 0.01, 0.02, 0.04, 0.04, 0.06, 0.08, 0.1, 0.2, 0.4, 0.5, 0.6, 0.8, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, or 5.0 wt% or less, preferably 0.01 to 4 wt%.

As used herein, the term "catalyst" is known in the art, which can adjust the reaction rate and/or curing rate of the unidirectional solventless polyurethane resin of the present invention. The catalyst applicable to the present invention is not particularly limited, for example: Dibutyl tin dilaurate (DBTDL), Stannous octoate, Triethylene diamine, Triethanolamine, Dibutyl tin dilaurate (DBTDL), Stannous octoate, Triethylene diamine, Triethanolamine Dimorpholinodiethyl ether (DMDEE), or a mixture thereof.

According to one aspect of the present invention, based on the total weight of the polyurethane resin, the content of the aforementioned catalyst is 0.03 to 0.05 wt%, preferably 0.04 wt%.

As used herein, the term "stabilizer" is known in the art, which can prevent the thermal oxidation of the polyurethane resin and/or the polymer chain scission reaction induced by oxygen, so as to improve the thermal oxidation and light aging properties of the product. Stabilizers include, but are not limited to: antioxidants, ultraviolet stabilizers, hydrolysis stabilizers, or mixtures thereof. Examples of stabilizers include: sterically hindered phenols, multifunctional phenols, thioethers, substituted benzotriazoles, hindered benzophenones, sterically hindered amines, or mixtures thereof. Examples of hydrolysis stabilizers include: oligomeric and/or polymeric aliphatic, aromatic carbodiimides, or mixtures thereof. Stabilizers are also commercially available, such as antioxidants selected from CHINOX 1010, CHINOX1076, CHINOX1098, CHINOX1790, and CHINOX5726; or UV stabilizers selected from CHISORB234, CHISORB320, CHISORB5411, CHISORB5571, CHISORB335, and CHISORB1268.

According to one aspect of the present invention, based on the total weight of the polyurethane resin, the content of the aforementioned stabilizer is 0.5 to 0.7 wt%, preferably 0.6 wt%.

The polyurethane resin of the present invention may be heated to induce the action of the foaming agent if necessary, so as to produce artificial leather with improved uniformity. As used herein, the term "foaming agent" is known in the art, provided that the foaming agent does not interfere with the performance of the polyurethane resin, and it includes Including but not limited to: carbonate compounds (carbonic acids), tosylhydrazine (TSH), oxidized bis(benzenesulfonyl) rib (OBSH), toluenesulfamate (TSS or TSSC), azodicarbonate (ADC or AC), or a mixture thereof.

According to one aspect of the present invention, based on the total weight of the polyurethane resin, the content of the aforementioned foaming agent is 3 to 5 wt%, preferably 4 wt%.

As used herein, the term "anti-sticking agent" is known in the art, provided that these anti-sticking agents will not interfere with the performance of the polyurethane resin, including but not limited to: synthetic silicon dioxide (for example, selected from EVONIK ACEMATT M 7789, TS 100), polymethacrylic resin, cellulose acetate (Cellulose acetate, for example selected from EASTMAN CAB 551), or a mixture thereof.

According to one aspect of the present invention, based on the total weight of the polyurethane resin, the content of the aforementioned anti-sticking agent is 2 to 3 wt%.

Manufacturing method of unidirectional solvent-free polyurethane resin

The present invention also provides a method for manufacturing a unidirectional solvent-free polyurethane resin, which comprises: mixing one or more isocyanates, one or more polyols, one or more silane compounds, and optional additives as required.

According to one aspect of the present invention, in the method for manufacturing a unidirectional solvent-free polyurethane resin as described above, the one or more isocyanates first react with the one or more polyols to form a polyurethane prepolymer, and the prepolymer The substance is then mixed with the silane compound or modified by the silane compound.

In some embodiments, the mixture of one or more polyols and optional additives can be heated and stirred at a temperature of 100 to 130°C, such as 100, 110, 120, or 130°C in a reduced pressure environment; dehydrating the mixture 0.5 to 2.0 hours, for example: 0.5, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8 or 2.0 hours; lower the temperature of the mixture to 60 to 80°C, for example: 60, 65, 70, 75 or 80°C; and adding one or more isocyanates to the mixture under a nitrogen atmosphere, and let it react for 0 to 120 minutes, for example: 0, 1, 10, 20, 30, 40, 50, 60, 70, After 80, 90, 100, 110 or 120 minutes, add the silane compound and optionally the catalyst after discharging to obtain the one-way solvent-free polyurethane resin.

According to a preferred aspect of the present invention, the method for manufacturing a unidirectional solvent-free polyurethane resin includes: based on the total weight of the mixture, 0.1 to 0.5 wt% polyether polyol, 10 to 23 wt% polyester polyol, 0.1 To 0.5wt% stabilizer, 1 to 3wt% foaming agent and 1 to 2wt% anti-sticking agent are mixed, stirred at 110 to 130°C and vacuum dehydrated for 1 to 2 hours, after cooling the mixture to 65 to 75°C, Add 32 to 35wt% isocyanate to the mixture in nitrogen, add 1 to 1.5wt% silane compound and 0.001 to 0.03wt% catalyst after reacting for 30 to 90 minutes and mix well, then discharge and seal the package to obtain the product Unidirectional solvent-free polyurethane.

Method for manufacturing artificial leather and manufactured artificial leather

The present invention also provides a method for manufacturing artificial leather, which comprises: heating the unidirectional solvent-free polyurethane resin as described above to form a molten state; contacting the molten polyurethane resin with a matrix layer; and curing the polyurethane resin .

As used herein, the term "substrate layer" can be any layer that can form an adhesion bond with the polyurethane of the present invention, such as fabric substrate layer, flake substrate layer, fiber substrate layer, foil substrate layer, leather layer (preferably Split leather), textile layer, shoe material matrix layer, or luggage matrix layer. The fabric substrate layer can be composed of one or more layers of the same or different closely interconnected sublayers, such as small or macroporous woven fabrics, knitted fabrics, braids, meshes (mesh cloth), such as: elastic cloth, Knitted cloth, plain woven cloth, microfiber cloth or water-repellent cloth, etc. The flake matrix layer is a sheet-like structure composed of randomly placed fibers (examples are felt and fiber mesh), and preferably can be bonded together by an adhesive. The flake matrix layer is usually a cellulose flake or textile flake reinforced with a water-insoluble impregnant. The fibrous matrix layer is a manufactured article made of loosely placed fibers reinforced with plastic used as a binder, which is made by, for example, combining leather fibers (preferably obtained from leather waste such as vegetable tanned leather) Obtained by sticking together with adhesive. The textile layer can be made of the following materials: cotton, linen, polyester, polyamide and/or polyurethane.

According to one aspect of the present invention, the unidirectional solvent-free polyurethane resin of the present invention can contact the substrate layer by a release transfer method. The release transfer method means that the polyurethane resin in a molten state is coated on the release layer before the contact step as described above, and then it is brought into contact with the substrate layer. Suitable release layer includes but is not limited to metal release layer or paper release layer, such as metal foil, PET release paper, RCPP release paper or paper release paper, etc. The release layer can be recycled and reused for 10 to 20 times if necessary. Times. Release paper is not limited to shiny, matte, litchi pattern, lambskin pattern or other various patterns.

According to one aspect of the present invention, the aforementioned coating method for coating the molten polyurethane resin on the release layer can be forward roll coating, reverse roll coating, or knife coating, preferably reverse roll coating, which is continuous. Type production and can be reeled. After the polyurethane resin in the molten state contacts the matrix layer and solidifies, the release layer can be removed to obtain artificial leather.

According to one aspect of the present invention, the amount of the aforementioned polyurethane resin coated on the release layer is 10 to 200 g/m ² , for example: 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 120, 140, 150, 160, 180 or 200g/m ² .

According to one aspect of the present invention, the method described above can preferably be used to produce artificial leather in a continuous winding method. The amount of polyurethane resin applied can be adjusted according to the gap between the sizing rollers and the differential speed ratio of the sizing rollers. The suitable gap between the sizing rollers is, for example, but not limited to: 0.01 to 0.50 mm, preferably 0.05 to 0.20 mm; suitable for sizing rollers The wheel differential ratio is, for example, but not limited to: 100 to 200%, preferably 120 to 180%.

According to one aspect of the present invention, the method of manufacturing artificial leather further includes a foaming step, which includes a temperature of 120 to 220°C, for example: 120, 130, 140, 150, 160, 170, 180, 190, 200, 210 or 220 Heating polyurethane resin containing foaming agent at ℃, the foaming ratio of the finished product is 1.05 to 2.00, for example: 1.05, 1.10, 1.15, 1.20, 1.25, 1.30, 1.35, 1.40, 1.45, 1.50, 1.55, 1.60, 1.65 , 1.70, 1.75, 1.80, 1.85, 1.90, 1.95 or 2.00; preferably 1.1 to 1.5.

The artificial leather produced by the method of the present invention has the characteristics of improved soft touch, hydrolysis resistance, weather resistance, flexibility, and richness, so it is beneficial to be used as ball leather, shoe leather, sofa leather, automobile leather or luggage Leather and other leather.

Instance

Hereinafter, the present invention will be further described in detail through examples. It is necessary to point out here that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Those skilled in the art have made some non-essential improvements and improvements to the present invention based on the above-mentioned content of the present invention. The adjustment still belongs to the protection scope of the present invention. Before discussing several non-limiting embodiments of the present invention, it should be understood that the present invention is not limited in its application to the details of the specific non-limiting embodiments shown and discussed herein, as the present invention may have other embodiments. In addition, the terminology used to discuss the present invention herein is for the purpose of description rather than limitation. In addition, unless otherwise specified, the following discussion of similar numbers refers to similar elements.

All numbers expressing content, ratio, physical characteristics, etc. used in this specification and the scope of the patent application should be understood as modified by the term "about" in all cases. Therefore, unless there are instructions to the contrary, the numerical values set forth in the following specification and the scope of the patent application may vary depending on the characteristics sought and/or required by the present invention. At least, and not trying to limit the application of the principle of equivalence Within the scope of the patent application, each numerical parameter should at least be explained based on the number of valid digits disclosed and by applying general rounding techniques.

Various embodiments are described and illustrated in this specification to provide a comprehensive understanding of the function, operation, and implementation of the disclosed method for manufacturing a one-way solventless polyurethane resin. It should be understood that the various embodiments described and illustrated in this specification are non-limiting and non-exhaustive. Therefore, the present invention is not necessarily limited to the description of each non-limiting and non-exhaustive embodiment disclosed in this specification. The features and characteristics described and/or described in combination with each embodiment can be combined with the features and characteristics of other embodiments.

Preparation of one-way solvent-free polyurethane resin

Mix the non-crystalline polyester polyol, polyether polyol, 3-(3,5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate (octadceyl- 3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, CHIN0X1076), TSSC, and cellulose acetate as appropriate, heated at a temperature of 120°C under reduced pressure Stir and mix well, the mixture was dehydrated in vacuum for 2 hours and then cooled to 70°C, and then the isocyanate and bismorpholinyl diethyl ether shown in Tables 1 to 3 were added to the mixture under the protection of nitrogen, and the mixture was stirred uniformly for 60 Minutes later, add A-1170, A-187, or A-Link-25 as the case may be, and then discharge to prepare a one-way solvent-free polyurethane resin. The prepared comparative samples 1 to 4 and samples 5 to 13 The polyurethane resin is stored in a sealed package at room temperature.

Manufacturing of artificial leather

The one-way solvent-free polyurethane resin comparative samples 1 to 4 and samples 5 to 13 were hot melted and coated on release paper, and the fabric was immediately bonded to the fabric and wound up, and the release paper was removed after being matured. Artificial leather, this is a dry release transfer process.

Testing of one-way solvent-free polyurethane resin

Viscosity measurement: After the polyurethane resin is heated at a constant temperature of 100°C in an oven, the viscosity is measured with a Brookfield viscometer.

Determination of isocyanate group content (NCO%): dissolve dibutylamine in ethyl ethanoate and make it react with the isocyanate group (-NCO) in the sample. Use hydrochloric acid for excess dibutylamine Standard solution (hydrochloric acid) titration, measured the content of isocyanate groups in the sample, the unit is wt%.

Measurement of mechanical properties: a polyurethane film with a thickness of 0.02mm is made by coating the resin on release paper. According to ASTM D412, the film is cut and tested. The tensile tester sets a tensile rate of 10mm/min, and records the modulus of 100% deformation. The unit is (Kg/cm ² ).

Hydrolysis resistance test: According to ASTM D3690-02 criteria, the film sample is placed in a constant temperature and humidity box, and the setting conditions are 70℃, RH 95%. After 5 weeks, it will be taken out and dried to test its 100% deformation modulus. The retention rate must be more than 80%, and this standard is better.

Testing the characteristics of artificial leather

Hand feel measurement: According to CNS12915 cutting and testing, the artificial leather sample is cut into 3cm wide and 20cm long strips, and then the strips are measured on the platform for sag measurement. The higher the sag, the judgement is Has a relatively good feel.

Foaming ratio measurement: Foaming ratio=(thickness of artificial leather after foaming/thickness of artificial leather before foaming). The measurement accuracy is 0.01mm.

Next, strength measurement: Cut the artificial leather into 3cm wide strip samples, and test with a tensile tester at a tensile rate of 100mm/min to determine the peel strength between the leather layer and the substrate in N/3cm.

Abrasion resistance test: According to ASTM D4060 standard, the machine type is TABER 5135, the wheel number is H-22, the load is 1Kg, and the qualified standard wear resistance is 300 cycles.

Flexural resistance test: According to EN ISO 32100 standards, the sample is cut into test pieces with a width of 4.5cm and a length of 7cm, and the flexure resistance test is tested at a temperature of 25°C and -20°C. The surface of the artificial leather is observed every 10,000 times. According to the qualified standards, it must be 200,000 and 60,000 times without damage respectively.

The inventors have unexpectedly discovered that the unidirectional solvent-free polyurethane resin sample containing a silane compound of the present invention has higher characteristics than a comparative sample without a silane compound, in addition to exhibiting desirable artificial leather characteristics. The resin viscosity and relatively better normal and long-term hydrolysis resistance.

Claims (17)

A polyurethane resin comprising one or more isocyanates, one or more polyols, and one or more selected from epoxy silane compounds, γ-aminopropyltriethoxysilane (γ-aminopropyltriethoxysilane, A-1100), double -(γ-trimethoxysilylpropyl)amine (bis-(γ-trimethoxysilylpropyl)amine, A-1170), isocyanate-based silane compounds, and silane compounds composed of combinations thereof, wherein the one or more polyols are Selected from the group consisting of polyester polyols, polyether polyols, and combinations thereof, wherein based on the total weight of the polyurethane resin, the content of the one or more silane compounds is 0.8 to 5 wt%, wherein the polyurethane resin is substantially free of Contains any volatile organic solvents and isophorone diamine. The polyurethane resin of claim 1, wherein the polyurethane resin includes an isocyanate (NCO) functional group and/or a silane functional group. The polyurethane resin of claim 2, wherein based on the total weight of the polyurethane resin, the content (NCO%) of the isocyanate functional group is 2 to 4 wt%. The polyurethane resin according to any one of claims 1 to 3, wherein the content of the one or more silane compounds is 0.8 to 3 wt% based on the total weight of the polyurethane resin. The polyurethane resin according to any one of claims 1 to 3, wherein the one or more isocyanates comprise aromatic polyisocyanates, aliphatic isocyanates, or mixtures thereof. The polyurethane resin according to any one of claims 1 to 3, wherein the content of the one or more isocyanates is 30 to 35 wt% based on the total weight of the polyurethane resin. The polyurethane resin according to any one of claims 1 to 3, wherein the one or more polyols comprise aliphatic polyester polyols, aromatic polyester diols, polyether diols, or combinations thereof. The polyurethane resin according to any one of claims 1 to 3, wherein the content of the one or more polyols is 60 to 65% by weight based on the total weight of the polyurethane resin. The polyurethane resin of claim 7, wherein the aliphatic polyester polyol is selected from the group consisting of: polyethylene adipate diol, polybutylene adipate diol, Polyhexylene adipate diol, dibasic acid diol trimethylolpropane copolyol, and combinations thereof. The polyurethane resin of claim 7, wherein the aromatic polyester diol is selected from the group consisting of: polyethylene glycol phthalate glycol, polyphthalate neopentyl glycol Alcohol ester diol, polybutylene phthalate hexylene glycol diol, and polybutylene phthalate diol. As claimed in claim 7, wherein the polyether glycol is selected from the group consisting of: polyoxypropylene glycol (PPG), polytetramethylene ether glycol (polytetramethylene ether glycol) , PTMEG), polyethylene glycol, polytetramethylene glycol, tetrahydrofuran-propylene oxide copolymer (tetrahydrofuranoxide propylene copolymer) glycol), and combinations thereof. A use of the polyurethane resin according to any one of claims 1 to 11, which is used to prepare artificial leather. A method of manufacturing artificial leather, which comprises: heating the polyurethane resin of any one of claims 1 to 11 to form a molten state; coating the molten polyurethane resin on a release layer; and applying the polyurethane resin Contacting the matrix layer; and curing the polyurethane resin. The method of claim 13, wherein the polyurethane resin is coated on the release layer in an amount of ^{10 to 200 g/m 2.} The method of claim 13 or 14, wherein the substrate layer includes a fabric substrate layer, a flake substrate layer, a fiber substrate layer, a foil substrate layer, a leather layer, a textile layer, a shoe material substrate layer, or a luggage substrate layer. Such as the method of claim 13 or 14, wherein the method uses a continuous winding method to produce the artificial leather. An artificial leather comprising the polyurethane resin according to any one of claims 1 to 11, wherein the artificial leather is ball leather, shoe leather, sofa leather, automobile leather, or luggage leather.