TWI270592B - Synthetic leather having aromatic water-borne polyurethane layer - Google Patents

Abstract

A synthetic leather having aromatic water-borne polyurethane layer. The synthetic leather comprises a substrate, a binder layer formed on the substrate, and at least one skin layer formed on the binder layer, wherein the binder layer and/or the at least one skin layer are made of an aromatic water-borne polyurethane. The aromatic water-borne polyurethane layer has superior mechanical properties, and can be applied in synthetic leather to increase performance thereof.

Description

1270592 玖, the invention description: [13⁄4 明 belongs to the technical field] The present invention relates to a method comprising aqueous formation, in particular to a synthetic skin structure comprising water = layer and its performance synthetic skin structure and method of forming the same . The high level of Zhuangfang's aromatic polyurethane film [Prior Art] The production of synthetic leather has been in existence for many years. It is used for manufacturing purposes. It is widely used in the people's livelihood industry. Synthetic hides have different appearances and characteristics. The original medicine and different treatment processes make the synthetic skin roughly classified into two kinds of vinyl Chl〇ride, pv, and poly (poly PU). Take >7 ^ 5 into the skin and polyurethane (polyurethane, layer / re-bismuth H synthetic leather with cloth as the substrate, combined with PVC foam Dan, and leather processed from the surface. 鈇„ ..., Early pure polyvinyl chloride (PVC) synthetic skin I, its material is cheaper, but its touch is relatively poor, and the physical properties are poor. The traditional polyurethane is different for the adjustment of the heat-featured ancient process, which can The raw polyurethane, the synthetic leather structure, and the durable:::' The closest polyamine to the natural leather, the traditional polyamines, need to use a lot of good properties such as shellfish = gas / good. However ' (DMF) , toluene / dry 祛 悧 悧 悧 悧 悧 悧 悧 悧 , , 悧 悧 悧 悧 悧 悧 悧 悧 悧 增加 增加 增加 增加 增加 增加 增加 增加 增加 增加 增加 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Increasingly #^世,^ concern about the benefits of %bao' and the related pollution prevention regulations of the mountain: Wenke '5' leather worker f has revolutionized in recent years, that is, the original solvent-based polyamine The resin is converted into a low-pollution water-based deodorant resin. Generally, the water-based polyurethane resin is mixed with a prepolymer. Prepared by the method, package 1270592 contains Polyols, Dihydr〇Xyalkyl alkan〇ic acid and Di 1 socyanat es in Shaoxia The organic solvent of the boiling point is first subjected to a synthesis reaction of the polyurethane prepolymer, and then neutralized with a tertiary amine to make the polyurethane prepolymer ionic. The ionic polyurethane (4) is then subjected to an ionic property. Water-dispersible and key-extended to obtain an aqueous polyurethane dispersion.

The viscosity of the prepolymer is an important limiting factor in the synthesis system of the prepolymer mixing method. Because if the viscosity is too high, the purpose of water dispersion cannot be achieved. Therefore, in order to lower the viscosity, it is sometimes necessary to use a solvent such as a high boiling point of dimethyl decylamine and N-methylpyrrolidine (N) to facilitate dispersion. However, the addition of these high-boiling solvents is not easily removed after water dispersion, causing problems in that the film or the coating film is not easily dried. Further, the residue of the high-boiling solvent is like the function of the plasticizer, and the physical properties of the film or the coating film are lowered. θ ^ ^ In addition, in the conventional prepolymer mixing method, when the end of the polyurethane prepolymer is an aromatic isocyanate group (ar〇matic NC〇-gr〇up), the water_dispersion process is carried out therein. Among them, because the reaction rate of its _NC〇 functional group with water is very high, most of the 'NC0 will react with water to form an amine group (NH^gr〇叩) and be consumed, so that the water remains after dispersion - There are too few functional groups in NC, and it is impossible to provide an effective bond lengthening reaction φ· to increase the molecular weight of the resin, resulting in poor final physical properties and mechanical properties of the resin: commercial value. Although the development of water-based polyurethanes has been in existence for 50 years, and the commercial tea products have been in existence for more than 20 years, they can be applied to synthetic skin products, and still be aliphatic or less reactive with water. The cycloaliphatic diisocyanate is cool. ‘However, these diisocyanates are expensive, making the cost of raw materials for aqueous polyurethanes much higher than traditional (IV) polyurethanes. d In addition, the traditional aqueous aliphatic or cycloaliphatic polyurethane should be used in the dry synthetic skin when it is used in 7 1270592. Because of the poor fusion between the aqueous polyurethane particles and the particles, the film is cracked during film formation, resulting in film formation. After the physical properties of the film, the high work (four) of pu itself cannot be exhibited. Therefore, in terms of mechanical properties, etc., the traditional water-based polyurethane and solvent = yes, can meet the requirements of environmental protection and physical properties, the preparation of organic solvents containing gluten' and can be applied to dry synthetic skin, with high mobility and work This feature is needed by the industry. [Explanation] In view of the above, the object of the present invention is to provide a synthetic skin structure of an ester film layer, which has properties such as leather physical properties, good texture, good air permeability, and the like. · 倶 皮 leather goods industry and sports equipment industry, etc., so that the hand feel, good resistance to wear resistance, and meet the environmental needs of people and have at least - layer of aqueous aromatic poly (tetra) film 11 * vinegar or silk water Silk (4) combines money, w solves the problems of conventional = side, solvent residue and high process cost, and further enhances the mechanical properties of the product and the touch during use. ® Leather-packing Another object of the present invention is to provide a water-containing property,

A synthetic skin structure comprising - an adhesive layer, and - or - above and at least - the outer layer of the layer is composed of water having different mechanical properties and different densities: s:: vinegar. Because the synthetic skin structure has different mechanical properties of water: 2, the amine vinegar film layer is properly combined, and the Μ 香 族 聚 聚 令 芸夭 取 取 取 取 取 取 取 取 取 取 取 取 取 取 取 取 取 取 取 取 取 取 取 取 取. m Shengfangxiang no polyamine 酉 膜 膜 ά 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适 适It can eliminate the disadvantages of the conventional solvent-based polyamine vinegar = skin phase 4 risk and high unit price. Another object of the present invention is to provide a 1270592 synthetic skin structure of a water-containing aromatic polyamine granule layer, which is suitable for dry bonding process or wet lamination coating, in the form of cloth and paper. And on a substrate such as leather. In order to achieve the above object, the synthetic skin structure of the aqueous aromatic polyurethane film layer of the present invention comprises a laminated structure in which at least two layers are formed on a substrate. The laminated structure includes an adhesive layer and one or more outer layers, and the adhesive layer is between the adhesive layer and the one or more outer layers. The adhesive layer and/or at least one outer layer are aqueous aromatic aromatic layers having different mechanical properties and different densities. In other words, the synthetic skin structure of the present invention may be a synthetic skin structure comprising an adhesive layer composed of an aqueous aromatic polyamine g, or may be a synthetic skin structure comprising an outer layer composed of an aqueous aryl (10) polyurethane. It may be a synthetic skin structure containing both of the above film layers. [Embodiment] The 1st 11' series shows the water-containing layer of the present invention; It can be seen from the figure that on the substrate two, the =::: product structure comprises an adhesive layer 12 and a layer or layer, and the upper layer is a - first layer, when the synthesis

ί =:; When the outer layer is on the first-outer layer, it is - the second outer layer. The naming of the outer layer is based on this principle. The. ·. ..., view 4, preferably 4: the wet film thickness of the layer 12 is ....Jet:=:.8 mouse and the dry film density can be above the outer layer of the brother, the wet film thickness can be. . 5~3_ = 〇·1~1 · 5 mm; the outside of it is checked by the person~~, the pregnancy is for the room, preferably her. 21= can be between 〇2~2.5_ When the outer layer is apart from the outer one. When the synthetic skin structure has between -mm, and the dry film density is 1,270,592 degrees, it is between 0.02 and 2 J g/3. Preferably, it is 0·2~1·4 g/cm: the synthetic skin structure of the aqueous aromatic polyamine granule layer in the aqueous fragrant salt of the present invention, and the aryl (tetra) additive thereof The ingredients are mixed and prepared. The composition of the aqueous amine ester dispersion and the additive may be formulated according to the aqueous aromatic polyamine, which is the same as the aqueous aromatic polycondensation. In other words, different broadcasts can also be used to formulate aqueous aromatic flats with inconsistency or different mechanical properties.

It can be a hardener, harden you, 隹 (5), and layers. Suitable additives for the synthetic skin 癸 & M, W, wetting agent, filler, dispersant, thickener, foaming agent, antifoaming agent, colorant, and the like.曰明4 The synthetic leather knot of the aqueous aryl (tetra) polyamine (four) layer according to the present invention The density and mechanical properties of the film composed of the main aromatic urethane are determined by the aromatic polyurethane dispersion. In addition, the density of the film layer is also affected by the type and amount of additives used in the Ting. The above-mentioned aqueous aromatic polyamine hydrazine dispersion can be obtained by the following steps: 100%, by pre-polymer mixing method (prep〇lym^ (4) 10 to 40% by weight of aromatic diisocyanate, 3 〇~8〇灵:=:, excess money and 1~15% by weight of the hydrophilic functional compound 'dissolving the prepolymer at a boiling point in the next 'in water', and monitoring the NCO after the prepolymer is in water The content of the functional group is in the range of Q.8~8.% by weight of the dispersion, and adding Q.1~5 by weight of the chain extender to carry out the chain extension reaction, wherein the above weight The percentage is based on the total weight of the prepolymer. After the chain extension reaction, it is removed by vacuum distillation or steam distillation (steam 1270592 diStiliationUf organic solvent removal, and the organic solvent is used for the dispersion of water H aromatic polyamine ester. The solid content of the aqueous polyurethane is from 1 to 65 weight percent based on the total weight of the aqueous polyurethane. In the process of the aqueous aromatic polyurethane dispersion, the mixture is formed in advance. The composition of the composition further comprises: a weight percent; a low molecular weight compound having at least two functional groups reactive with isocyanate from the group; the low molecular weight compound capable of reacting with the isocyanate group Examples of the family: alcohols, aromatic polyols, aromatic (tetra) glycols, aliphatic glycols, aliphatic polyols or aliphatic ether glycols. The aromatic diisocyanate is at least Having an aromatic ring, and the aromatic ring may be selected from the scale consisting of phenyl 'biphenyl and naphthyl groups, and one or more of the aromatic rings; 5 opposite hydrogen, if necessary, may be fluorine atoms, A halogen atom, a nitro group, a cyano group, a hospital base, a silk base, a # silk, a warp group, a (tetra), a guanamine group or an amine group. The ferritic diisocyanate suitable for the rut can be selected from the following formula ( a group of workers, formulas (workers) and their mixtures...

△ (1) Formula (work) f, medium Rl is hydrogen or Cl_·6 burnt base; and R3 is the same or different, and has only - to six carbon base, with - to six carbon burn An oxy group, or an anthracene group; and η is 〇, 1, 2 or 3. The scented diisocyanate can also be diiso-acidic toluene vinegar (τ〇ι卿 e = ls〇cyanate, TDI), p-phenyiene (PPDI), diiso) 4,4,Diphenylmethane,Cyclic acid,P,P,P,P Or! 27〇592 is a mixture thereof. In general, when the number of benzene rings of the diisocyanate is large, the Young's modulus or hardness of the film is higher; therefore, different diisocyanates can be selected as the reaction raw materials as needed. In the selection of the aromatic diisocyanate, it is also possible to use more than one aromatic diisocyanate at the same time. For example, one of the toluene diisocyanate (TDI) and the p-diiso-pure text enthalpy (PPDI) can be used to match the 4,4/-diphenyl sulfonate (MDI) of diisocyanate. And one of ρ,ρ'-diphenyl ester (BPD) of diisocyanate. Among them, two kinds of isogastric acid, S (TD) or p-diisocyanate (ppd), account for more than 30% of the mixture of diisocyanate. The polyol used in the process of the aqueous aromatic polyurethane dispersion may be a bifunctional polyol or a polyfunctional polyol, including a polyester polyol, a polyfluorinated polyol, a polycarbonate polyol, and a polycaprolide. g is a polyol, a polyacrylate polyol, a low molecular weight polyol or a mixture thereof. The number average molecular weight of the polyol ranges from 60 to 6,000, preferably from 62 to 3,000. It is also possible to use more than one polyol at the same time in the selection of the polyol. The polyhydric alcohol may also be a poly(but anediol-co-adipate) glycol (PBA), a poly-t-diol (PTMEG), a hexanediol-adipic acid. Copolymer (Poly(hexanediol-co-adipate) glycol, pHA), polyethylene (ethanediol-co-adipate) glycol, PEA, Polypropylene glycol (PPG), Polyethylene Polyethylene glycol (PEG), diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, and ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanediol, Cyclohexyldime thanol (CHDM), octanediol, Ne〇pentyl glycol (NPG), Trimethylpentanediol (TMPD), benzenedimethanol, 12 1270592 benzenediol, A glycol such as toluenediol or bisphenol A (Bisphen〇lA). In the process of the aqueous aromatic polyurethane dispersion, when the molecular weight of the polyol used is relatively high, the obtained film is soft; when the molecular weight of the polyol is low, the obtained film is hard; therefore, The desired molecular weight of the polyol can be adjusted to obtain a synthetic skin of the most suitable hardness. A compound having active hydrogen which can form an aqueous functional group in the process of the aqueous aromatic polyurethane dispersion, and a hydrophilic functional group thereof, for example, can be -C〇〇-, -S〇3-2 , -NR4+, - (CH2CH2〇)-, etc. The active hydrogen-forming compound capable of forming a hydrophilic functional group may be Dimethy 1〇1 propionic acid (DMPA), Dimethylol · butanoic acid (DMBA), polycyclic ring Poly (ethylene oxide) glycol, Bis (hydroxyethyl)

Amine), or 3-bis(sodiumethyl)aminopyranoate (Sodium 3 _bis (hydroxyethyl) amiiiopropaiiesulfonate). In the selection of the active hydrogen-forming compound which can form a hydrophilic functional group, it is also possible to use more than one compound having an active hydrogen group which can form a hydrophilic functional group. In the process of the aqueous aromatic polyurethane dispersion, when the hydrophilic hydrogen-forming compound having a hydrophilic 'functional group has a large hydrophilic group content, the Young's modulus and hardness of the film are also improved. Therefore, a polyol having a hydrophilic group as appropriate can be selected as a reaction raw material as needed. * The aqueous aromatic polyamine dispersion according to the present invention, wherein the aqueous, polyurethane dispersion is a hydrophilic group, and the hydrophilicity of the aqueous polyurethane is based on 1 gram of dry material. The base content is about 5 to 80 meq, preferably 15 to 65 me q. The mechanical properties of the film composed of the aqueous aromatic polyurethane are highly correlated with the ratio of the isocyanate group to the hydroxyl group (NC0/0H) in the synthesis of the aqueous aromatic polyurethane prepolymer. The higher the ratio, the higher the Young's modulus and hardness are usually imparted to the film; conversely, the lower the ratio, the lower the Young's modulus and hardness of the film. In the synthesis of the aqueous aromatic polyurethane prepolymer, the ratio of the NCO/OH is adjusted according to the required hardness, and the ratio of the NC〇/〇H can be controlled between u~, preferably. The system is controlled between 1 · 2 ~ 2 · 4. When the prepolymer is subjected to a chain extension reaction, the chain extender used may be a polyamine or a polyol chain extender, and a commonly used amine or alcohol having a difunctional group, a trifunctional group or a tetrafunctional group may be used. For example, ethylene glycol, glycerol, benzenetriol, pentaerythritol, 2-methyl-1,5-pentanediamine-diamine, diethylenetriamine (DETA) or triethylenetetramine (7) (10) . The polyamine may be a polyamine having the formula H2N(CH2)m_NH2, wherein (7) is an integer of 〇~12, preferably ethylene diamine. The aqueous aromatic polyurethane film layer according to the present invention For synthetic skin structure, please refer to the first! In the figure, the structural towel has at least a film-bearing layer of the aqueous aromatic polyamine layer of the present invention. The present invention is characterized in that the present invention can have a layer (or layer above) of a water-containing aromatic polyamine 酉 ^ layer, sub-column with any suitable adhesive layer; The human skin structure of the present invention may have an aqueous aromatic poly(tetra) adhesive layer, and is matched with a suitable layer, such as m: or PU outer layer; in addition, the present invention (4): simultaneously contains a water-containing aromatic polyamine Adhesive layer and layer of vinegar or 4:::; aqueous aromatic polyurethane outer layer. The above-mentioned bamboo shoots and hunting: several preparation examples and examples, to further explain this; "the formation of the synthetic skin structure of the aqueous aromatic polyurethane film layer is used to limit the scope of the present invention." The scope should be based on the scope of the patent application. The preparation of the aqueous aromatic polyurethane dispersion has an ίί-month structure, which is characterized in that the synthetic skin structure film layer is composed of a water-based linoleic acid vinegar film layer. The aqueous aromatic polyamine 酉 《 《 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 私 私 私 私 私 私Aromatic polyurethane dispersion and preparation method thereof. Preparation Example 1: Synthesis of aqueous aromatic polyurethane dispersion (1), 14.07 g of one of Dimethylol propionic-acid 'DMPA and 33 · 33 g N-methyi pyrrolidone (NMP) is uniformly stirred in a reaction tank protected by nitrogen. When the above raw materials are in a uniform phase, 67. g of 2,4-diisocyanate is added. __ (T〇lu Ene diis〇cyanate, TD) and 2,6-toluene isocyanate (mixing ratio of 4:1) were added to the reaction tank. Heated to 6 Torr. After reacting for an hour, add 218.78 g of dibutyl Poly(butanediol-co-adipate glycol, PBa) (Mn = 2, 〇00) is uniformly mixed in the reaction tank. After the reaction is continued for 4 hours at (9) c, the reaction tank is The temperature is lowered to 5 Torr. 〇, and 1 〇.sg of triethylamine (TEA) is added for a 2 minute neutralization reaction. After that,

The neutralized and hydrophilic prepolymer, 27 〇g, was quickly added to 56 〇g of deionized water at a stirring rate of 500 rpm for water dispersion and simultaneously monitored for enthalpy before the NC0 value fell to 1. 47 wt%. A water-diluted ethylene diamine (ethylene diamine) was used to carry out a chain extension reaction. After the chain extension reaction was continued at room temperature for 2 hours, an aqueous aromatic polyamine vinegar dispersion (1) having a solid content of 30 wt% and a pH of 9 〇 5 was obtained. The dry film obtained from the aqueous aromatic polyurethane dispersion (1) is a high-gloss transparent film which is resistant to toluene wiping to a maximum of 100 - human, and has a tensile strength of 323 and a modulus of 88.

Kg/cm2, the maximum elongation is 33%. , - 15 1270592 Preparation Example 2: Synthesis of Aqueous Aromatic Polyurethane Dispersion (2) 14.07 g of dimethylolpropionic acid (DMPA) and 33.33 g of N-methylpyrrolidone (NMP) are available. Stir well in a nitrogen-protected reaction tank. When the above raw materials are in a homogeneous phase, 71.62 g of 2,4-diisocyanate (TDI) and 2,6-diisocyanate are used. Toluene ester (mixing ratio of 4:1) was added to the reaction tank. After heating to 60 ° C and reacting for 1.5 hours, 2 3 3 · 3 7 g of polybutanediol (P〇lytetramethylene Glycol; PTMEG) (Mn = 1, 〇〇〇) was added to the reaction tank and mixed. Evenly. After continuing the reaction for 4 hours at 6 ° C, the temperature of the reaction vessel was lowered to 5 Torr, and 1 〇 · 6 g of triethylamine (TEA) was added to carry out a neutralization reaction for 2 minutes. Thereafter, the neutralized and hydrophilic prepolymer 2 7 〇g was quickly added to 45 〇g of deionized water at a stirring rate of 5 〇 O rpm for water dispersion while monitoring its NC 〇 value. Before the NC0 value was reduced to 2 · 〇 3 wt %, water-diluted ethylene diamine (EDA) 3 · 10 g was added for chain extension reaction. After the chain extension reaction was continued at room temperature for 2 hours, an aqueous aromatic polyurethane dispersion (2) having a solid content of 33% by weight and a pH of 7 · 36 was obtained. The aqueous aromatic polyamine vinegar dispersion (2) dry film is insoluble in methyl ethyl ketone (methyl_ethy: L ket〇ne, MEK) and toluene, and its toluene resistance is up to 3 times, and its tensile strength is 45. The 〇Kg/cm2'l〇〇% modulus is 6〇Kg/cm2, and the maximum elongation is 37〇%. Preparation Example 3: Synthesis of aqueous aromatic polyurethane dispersion (3) 12·199 dimethylolpropionic acid (DMPA) and 28.9 g of methylpyrrolidone (NMP) were stirred in a nitrogen-protected reaction vessel. ς In a uniform phase, 58.19g of 2,4-diisocyanatobenzene vinegar (TO=4e dils〇cyanate'TDI) and 2,6-diisocyanate (mixing ratio of 4: 16 1270592) 1) Add to the reaction tank. After heating to 6 并 and reacting for 1.5 hours, 189.61 g of hexanediol-adipate (pHA) (Mn = 2, 〇〇〇) was added. ) in the reaction tank and mix well. After 4 hours of the reaction, the temperature of the reaction vessel was lowered to 5 Torr, and 9·2 g of triethylamine (TEA) was added for a 2 minute neutralization reaction. Thereafter, 27 μg of the neutralized and hydrophilic prepolymer was quickly added to 4 〇 0 g of deionized water having a mixing rate of 5 rpm, and water dispersion was carried out while monitoring the NC0 value. A water-diluted 2.63 g of ethylene diamine (EDA) was added to carry out the chain extension reaction before the NC enthalpy decreased to 4% by weight. After the chain extension reaction was continued at room temperature for 2 hours, the aqueous aromatic polyurethane dispersion (3)' had a solid content of 35 wt%' pH of 9.5. The aqueous aromatic polyurethane dispersion (3) dry film is insoluble in methyl ethyl ketone (methyl_ethyl, mek) and toluene, and its toluene resistance is 彡 ,, its tensile strength is 4 ΐ〇 Kg / Cf, 100% modulus is 60 Kg/cm2, the maximum elongation is 38%. Preparation Example 4: Synthesis of Aqueous Aromatic Polyurethane Dispersion (4) 1.83 Kg of dimethylolpropionic acid (DMpA) & 4.33 lang of N-methyl qing was administered in a nitrogen-protected reaction tank. Mix well, wait for the above-mentioned original ^ king = _ phase%, 7.88 叼 of 2'4_diisocyanate toluene (TDI) and 0:_= acid toluene vinegar (mixing ratio of 4:. Add to the reaction tank. Heat to b UL sub-reaction 1 5 /1, Nippon wire, 丄, , 吋 加入 Add 29.29 Kg of polybutanediol: ΓΠ: Γ = 2, _) in the reaction tank and mix the same sentence. In the post, continue to reverse = /, read, reduce the temperature of the reaction tank, and add l38 Kg of the third pre-QQ (four) neutralization reaction. After that, it will be neutralized and have a hydrophilicity of ^ Λ 43 · 〇哗 quickly added to the drop rate of 500 gongs to work 6 , such as water dispersion and simultaneously monitor its value. Before the NC enthalpy drop “, add water-diluted ethylenediamine (ε_ ο』叼, 17 !27〇592 ^ for chain extension reaction. When the chain extension reaction is continued at room temperature for 2 hours, the water-based aroma Polyurethane dispersion u), its solid content is 34 wt%, pH = 7·3! 'The particle size is 426 丽', its Bro〇kf:Lelci viscosity is 2〇cps, and 2 saki for 7 consecutive days of dispersion Stability test. The tensile strength of the obtained dry film is Go Kg/cm2, the 100% modulus is 42叼/(4)2, and the maximum elongation is Preparation Example 5: Synthesis of aqueous aromatic polyurethane dispersion (5) will be 10· 85 g of dimethylolpropionic acid (DMPA) & 6〇.〇g-methylpyrrolidone (NMP) is stirred evenly in a nitrogen-protected reaction tank. When the above-mentioned original phase is uniform, 34.29 g of diisocyanate 4,4, diphenyldecane vinegar (md work) was added to the reaction tank. It was heated to 6 Torr and reacted for 5 hours, then i33.35 g of polytetramethylene glycol (PTMEG) was added. (Mn = 1, 〇〇〇) in the reaction tank and mixed uniformly. After continuing the reaction at = ° C for 4 hours, add 35.8 〇g of 2,4 - diisocyanate toluene (TDI) and 2, Toluene diisocyanate (mixed Example 4: "In the reaction tank. After 2 hours of reaction, the temperature of the reaction tank was lowered to 5 Torr, and 8. i8 Kg of triethylamine (TEA) was added for a 20-minute neutralization reaction. Thereafter, The neutralized and hydrophilic prepolymer 200 g was quickly added to 21 deionized water at a stirring rate of 5 rpm, and the water was dispersed and the NC0 value was monitored at the same time. Before the NC enthalpy decreased to I.53, Water-diluted ethylenediamine (EDA) iwg was added for chain extension reaction. When the chain extension reaction was continued at room temperature for 2 hours, an aqueous aromatic polyurethane dispersion (5) was obtained, and the solid content was 2 〇wt. %, pH is 8.22, particle size is 234 nm' and its Br〇〇kfield viscosity is 6 cps. The aqueous aromatic polyamine i dispersion (5) dry film is insoluble in methyl ethyl ketone (MEK) and toluene The tensile strength is 47 〇叼 / (four) 2, 1 〇〇 % modulus is 39 Kg / cm 2 , the maximum elongation is 42 〇 %. 1270592 Preparation Example 6 : Synthesis of aqueous aromatic polyurethane dispersion (6) I4 · 1 9 dimethylolpropionic acid (DMPA) and 33.3 g of N-methyl have different mouth-to-mouth ratios (_P) in the presence of nitrogen-protected Stir in the tank, and when the above-mentioned original = phase, 67.1Sg of toluene diisocyanate (π work) and toluene isocyanate (mixing ratio of 4: 丄) In the reaction tank, after heating to C and reacting for 5 hours, 21 S.78 g of polypropylene glycol (PPG) (Mn = 2,000) was added to the reaction vessel and mixed well. In (9). After the reaction was continued for 4 hours, the temperature of the reaction vessel was lowered to 5 Torr, and 1 〇.si g of triethylamine (Τ^Α) was added for a neutralization reaction for 2 Torr. Thereafter, the neutralized and hydrophilic pre-purinant 2r7〇g was quickly added to 4 (10) g of deionized water having a scramble rate of 5 rpm, and water dispersion was carried out while monitoring the NCO value. After the NCO value drops to 2 · 15 wt%, water-diluted ethylenediamine (EDA) 3 .Ug is added to carry out chain extension and the chain extension reaction is continued at room temperature for 2 hours. Polyurethane Separation Solution (6) has a solid content of 35%, a pH of 7 · 85, a particle size of 76 nm, and a Brookfield viscosity of 61 cps. The dry film of the aqueous aromatic polyurethane dispersion (6) is a high-gloss transparent film, and the resistance to the benzene wiping is up to 00 times, and the tensile strength is 125 Kg/cm2, 1%. The modulus is 16 Kg/cm2 and the maximum elongation is 88%. Preparation Example 7 · Synthesis of Aqueous Aromatic Polyurethane Dispersion (7) 9 〇·6 g of dimethylolpropionic acid (7) s. (4) and 丄52』7 g of acetone were stirred in a nitrogen-protected reaction tank. Evenly, when the above raw materials were in a uniform phase, 352.4 g of 2'4_monoisoxyl methacrylate (TDI) and 2,6-diisocyanate toluene (mixing ratio of 4:D) were added to the reaction tank. After heating to (6) and reacting for an hour, add 1,306.9 9 of PTMEG (Mn = 2, 〇〇〇) to the reaction tank and mix it uniformly. After continuing the reaction for 4 hours at 60 ° C, the temperature of the reaction tank was lowered to $ 〇, 19 1270592 and adding SI·% g of triethylamine (TEA) for 2 〇 minutes of neutralization reaction. Thereafter, 95 〇g of the neutralized and hydrophilic prepolymer was quickly added to the stirring rate of 500 rpm. In deionized water, disperse the water and simultaneously monitor its enthalpy. Add water-diluted ethylenediamine (EDA) S for chain extension reaction before the NC enthalpy falls to 1.7 wt%. After holding at room temperature for 2 hours, the aqueous aromatic polyurethane dispersion (7) has a solid content of 3 $ wt% and a pH of 7.69. The particle size is 6〇(10), and the Br〇〇kfield viscosity is cps. The dry film obtained from the aqueous aromatic polyurethane dispersion (?) is a high-gloss transparent film, which can withstand toluene wiping resistance up to (four) times. Tensile strength is 3〇7

The Kg/cm, i〇〇% modulus is 47 Kg/cm2, the maximum elongation is 57 (10), and the A hardness is 76. Preparation Example 8: Synthesis of aqueous aromatic polyurethane dispersion (8) 2.90 g of dimethylolpropionic acid (DMPA) and 152·17 g of acetone were uniformly distributed in a nitrogen-protected reaction tank. When the above raw materials are in the same phase, 541.89 of 2,4-diisocyanate (TD) and 2,s_diisocyanate = 4:1} are added to the reaction tank. . After heating to (9) and reacting 丄.5 - small %, l, ll 7.5 g of polypropylene glycol (ppG) (Mn = 2, 〇〇〇) was added to the reaction vessel and mixed well. After the reaction was continued at Q6Q °C for 4 hours, the temperature of the reaction vessel was reduced to 5GC ‘substituting 61·86 g of triethylamine (TEA) for 2 minutes and the reaction. Thereafter, 95 〇g of the neutralized and hydrophilic prepolymer was rapidly added, and the stirring rate was 500 volts in deionized water, and water dispersion was carried out and the same value was monitored. Before the (10) value was lowered to 195%, water-diluted, ethylenediamine (10) (4) 7·44 9 was added to carry out a chain extension reaction. When the chain extension reaction was continued at room temperature for 2 hours, the aqueous aromatic polyurethane dispersion (8), the pot solid band, was 35 wt%, the pH was 7.42, and the particle size was 65 (10), and the rainbow trout was _ station degree. For 26 cps. The dry film obtained from the aqueous aromatic polyurethane dispersion (8) is 20 1270592 - a high gloss transparent film having a tensile strength of 425 Kg/cm 2 and a modulus of 1 〇〇 % of 35 Kg/cm 2 'maximum elongation. 53%, a hardness of 85. Preparation Example 9: Synthesis of aqueous aromatic polyurethane dispersion (9) 18.2 g of dimethylolpropionic acid (1) serie and 3s.65 g of acetone in a nitrogen-protected reaction tank (four) When the raw material is in the same phase, ^22·7 g of toluene 2,4-diisocyanate (tdi) and 2,6-diisocyanate toluene ratio of 4 · 1) are added to the reaction tank. . After heating to 6 Torr and reacting .5 J, add 269·〇g of polypropylene glycol (ppG) (Μη=1, 〇〇〇) in the reaction tank. After continuing the reaction at 6 ° C for 4 hours, the temperature of the reaction vessel was lowered to 5 ° C, and the triethylamine (TEA) of Hu 9 was added to carry out the reaction for 2 minutes and then neutralized and hydrophilic. The prepolymer was rapidly added to 24 Sg of deionized water at a stirring rate of 5 Torr, and the water was dispersed and simultaneously measured/NCO value. Before the NCO value was lowered to 2 · 68 wt%, water-diluted ^ diamine = DA) 3 · 03 was added to carry out a chain extension reaction. When the chain extension reaction is held under the chamber, ''I 2%%), the aqueous aromatic polyurethane dispersion (9) has a solid content of 39 wt%, a pH of 7.34, and a particle size of 135. 〇kfi_ sticky, for, ISO CPS. The dry film obtained by the aqueous aromatic polyurethane dispersion (9) is a glossy transparent film having a tensile strength of 2〇7Kg/cm2, an i〇〇% modulus of α Kg/Cm2 and a maximum elongation of 625. %, this 〇: ^ hardness of 81. 'Preparation Example 1 〇: Synthesis of aqueous aromatic polyurethane dispersion (χ 〇) 12·9 g of dimethylpropionic acid (DMPA) and 2:L·74 g of acetone Stir well in the reaction tank. When the above raw materials are in a uniform phase, the ratio of toluene H diisocyanate (TDI) and toluene diisocyanate is 4:1) to the reaction tank. Heat to 6 〇. 〇 and react 15 small 21 1270592 柃, then add 183·9 9 PTMEG (Mn = 2,000) in the reaction tank and mix the same sentence. After the reaction was continued for 4 hours at the scrc, the temperature of the reaction vessel was lowered to 5 crc, and 8.84 g of triethylamine (TEA) was added for a neutralization reaction for 2 minutes. Thereafter, 225 g of the neutralized and hydrophilic prepolymer was rapidly added to 276 g of deionized water at a stirring rate of 5 rpm, and water dispersion was carried out while monitoring the value. The NCO value drops to 2. (10) Before the addition, water-diluted ethylenediamine (SED EDA) 2 ·=2 g was added to carry out a chain extension reaction. When the chain extension reaction is carried out at room temperature, the shellfish is kept for 2 days, and the aqueous ^'fragrant polyurethane dispersion (1 Q ) has a solid content of 4〇wtf 'pH of 8 · 27, and the particle size is 88 nm, the dry film obtained by Br〇〇kfield viscosity of 6〇, cps aromatic polyurethane dispersion (1〇) is a high-gloss transparent film with a tensile strength of 3s〇Kg/cm2, ι〇〇 The % modulus is 32 Kg/cm2, the maximum elongation is 610%, and the sh〇re A hardness is 68. 〆 Preparation Example 11 : Synthesis of aqueous aromatic polyurethane dispersion (11), stirring g dimethylolpropionic acid (DMPA) and 21·74 g of acetone in a reaction tank protected by nitrogen, until When the above raw materials are in a uniform phase, 4,8-isobutyl isocyanate (TD) and 2,6-diisocyanate (4:6) are added to the reaction tank. Heat to 6 〇. (3 and react I·5 with little dryness) Add l94. 〇g of pTMEG (Mn=2, 〇〇〇) in the reaction tank and mix well. Continue reaction at 6 ° C for 4 hours. , the temperature of the reaction tank was lowered to 5 〇, and 7·58 g of triethylamine (TEA) was added for a neutralization reaction for 2 minutes, after which 225 g of the neutralized and hydrophilic prepolymer was obtained. Rapidly add 278 g of deionized water at a stirring rate of 5 rpm, disperse the water and monitor its nc 。 value. Add water-diluted ethylenediamine = DA)1 before the NCO value drops to 2.54%. 66 g for chain extension reaction. When the chain extension reaction is held at room temperature for 2 hours, the aqueous aromatic polyurethane dispersion (丄丄) has a solid content of *〇wt. The particle size of 8 · 48 ' is 119 angstroms, and its Br〇〇kf ield viscosity is 22 1270592 South 52 cps. The dry film obtained from the hydrophobic aromatic polyurethane dispersion (11) is a glossy transparent film with tensile strength. (4) Kg / (10) 2, 1QQ% modulus is Kg / cm 'maximum elongation is 67〇%, sh〇re a hardness%. Preparation Example 12: Synthesis of aqueous aromatic polyurethane dispersion (12) will be 21-11 9 One of light methyl propionic acid (DMPA) and 38.89 g of n-mercaptopurine (NMP) is mixed in a nitrogen-protected reaction tank. When the above raw materials are in a uniform phase, 8 ?.ls If isocyanate toluene (td work) and 2 diisophenylocyanate (mixing ratio of 4: into the reaction tank. After heating to the machine and reacting L5 hours, add 241-7g pTMEG (Mn = 2, 〇〇〇) was uniformly mixed in the reaction tank, and the temperature was lowered to scratch after the reaction was continued, and 15e91 g of triethylamine (TEA) was added to carry out a neutralization reaction for 2 Torr. Thereafter, the neutralized and hydrophilic prepolymer 32〇·〇g was quickly added to “mg of deionized water at a stirring rate of 500 rpm, and the water was dispersed and simultaneously monitored for NC. Depreciation. Before the NC enthalpy decreased to 2.024%, add water-diluted ethylenediamine (3) 33.58 g for chain extension reaction. When the chain extension reaction was held at room temperature, continued 2 After an hour, the aqueous aromatic polyurethane dispersion (Work 2) had a solid content of 35 wt%, a pH of 7.8 Å, a particle size of 128 Å, and a Br〇〇kfleld viscosity of IS cps. The dry film of the aqueous aromatic polyurethane dispersion (Work 2) is a high gloss transparent film having a tensile strength of 4 (10) Kg/cm 2 , a 100% modulus of 67 Kg/cm 2 and a maximum elongation of 48 〇. %. Preparation Example 13: Synthesis of Aqueous Aromatic Polyurethane Dispersion (13) 3.67 Kg of dimethylolpropionic acid (DMPA) & 6·76 Kg of n-methylpyrrolidone (NMP) was protected by nitrogen. Stir well in the reaction tank, when the original 23 1270592 material king-phase, '15.15 Kg of 2,4-diphenylisocyanate coffee) and isocyanate isocyanate (mixing ratio of 4 · · Add to the reaction tank. After heating to 60 C and react for 1 · 5 hours, add 42 · 〇Kg of PTMEG (in the reaction tank and mix the same sentence. After 6 hours of reaction at 6 ° C, the reaction will be The temperature of the tank was lowered to 5 Q ° C, and 2·9 () of triethylamine (tea) was added for a 2 minute neutralization reaction. Thereafter, the neutralized and hydrophilic prepolymer Kg was quickly added. The mixing rate is 5〇〇rqing's work·deionized water, water dispersion and simultaneous monitoring of N(7) value. Add water-diluted ethylenediamine (ΕϋΑ) before the (4) value drops to 1β87%. 0·82 Kg for chain extension reaction: when the chain extension reaction is continued at room temperature for 2 hours, the aqueous aromatic polyamine vinegar is divided into φ 政液 (I3), the solid content thereof 35 wt%, ρΗ value is 8 · 47, particle size is the title, its Brookfield viscosity is 17 cps. The aqueous aromatic polyurethane dispersion U3) is a high-gloss transparent film with tensile strength. It is Kg/cm2, i〇0% modulus is 87 Kg/cm2, and the maximum elongation is 45 (10). Preparation Example 14: 'Synthesis of aqueous aromatic polyurethane dispersion (Μ)_ 3.67 Kg of dihydroxymethyl propionic acid (DMpA) and 6.76 of N-mercaptopurine (NMP) are stirred evenly in a nitrogen-protected reaction tank. When the original _lu is a homogeneous phase, 15 · 15 Kg of 2 , 4-diisocyanate toluene (TDI) and '2,6-diisocyanate toluene (mixing ratio 4: added to the reaction tank. After heating to -6 ° C sub-reaction for 1 · 5 hours, Add 42 · 0 Kg of PTMEG (Mn = 2, 〇〇〇) to the reaction tank and mix well. At 6 〇. After continuing the reaction for 4 hours, reduce the dish size to 50 C ' and add 2 · 9〇Kg of triethylamine (TEA) was subjected to a 2 minute neutralization reaction. Thereafter, the neutralized and hydrophilic prepolymer 68·01 was quickly added to a stirring rate of 5 rpm. · 〇Kg deionized water, disperse in water and monitor its NC enthalpy. Add water-diluted ethylenediamine (eda) 〇82叼 before NC ◦ value drops to .96^7% of 24 1270592. Should be. When the light and long reaction to the room to extend the anti-cafe Π Ρ 8 for 8,47' grain # is 225 (10) ' ((4) the (four) ^ which. The aqueous aromatic poly(tetra) dispersion is dried to a high gloss transparent film having a tensile strength 叼/. ...the molar number is 87 Kg/cm2, and the maximum elongation is "Preparation Example 15: Synthesis of aqueous aromatic polyurethane dispersion (ls) 8.38 g of dimethylolpropionic acid (DMPA) & 27.8 g The methyl group of each ketone (NMP) is stirred in a nitrogen-protected reaction tank. When the above raw materials are in a uniform phase, 2,53 g of 2,toluene isocyanate (τ〇) And 2, toluene diisocyanate (mixing ratio of 4: 1) was added to the reaction tank. After adding to hydrazine and reacting, 1β5 hours, adding ΐ69·〇9 g of polypropylene glycol: p〇lypr〇 Pyiene giycu, ppG) (Chi = 1, (10) (1) is uniformly mixed in the reaction tank. After the reaction is continued for 4 hours at 6 CTC, the temperature of the reaction tank is lowered to 5 ° C ' and 6.31 9 triethylamine (TEA) is added. 2 minutes of neutralization reaction. After that, the neutralized and hydrophilic prepolymer 2〇〇·〇g is quickly added to the water at a stirring rate of 24◦叩.〇g deionized water. Disperse and simultaneously monitor its NC0 value. Add water-diluted ethylamine (EDA) 3.14 g to the chain extension reaction before the NC0 value drops to 2.15 wt%. The reaction was carried out for 2 hours under the chamber, and the aqueous aromatic polyurethane dispersion (15) had a solid content of 40' pH of 8.59, a particle size of 152 nm and a Brookfield viscosity of 17 cps. The aqueous aromatic polyurethane The dry film obtained from the dispersion (15) was a high-gloss transparent film having a tensile strength of 31 〇Kg/cm 2 , a 100% modulus of 23 Kg/cm 2 and a maximum elongation of 585%. It is summarized in -15 that the synthetic polyurethane structure 25 1270592 of the present invention has a water-containing aromatic polyurethane film layer having a dry film property of 30 to 850 Kg/cm 2 . 100% modulus is 3~9〇Kg/cm2, maximum elongation is 150~1〇〇〇%, and hardness 10 (sh〇reA)~5〇(sh〇reD). The polyaminourethane film layer preferably has a dry film property of between 80 and 700 Kg/cm2, a 100% modulus of 10 to 75 Kg/cm2, and a maximum elongation of 200 to 900%. And hardness 25 (sh〇re A)~1〇〇(sh〇re · A). According to the present invention, when the adhesive layer is an aqueous aromatic polyurethane film layer, the aqueous aromatic polyurethane The dry film properties of the layer include: tensile strength between 100 and 600 Kg/cm2, 100% modulus between 1 〇 and 7 〇 Kg/cm2, and maximum elongation between 3 〇〇 and 9 〇 0%. And a synthetic skin structure having a hardness of 3 Å (Sh〇 A A) 98 (Shore A) 〇 a water-containing aromatic polyurethane film layer and a synthetic skin of the aqueous aromatic polyurethane film layer of the present invention The preparation method of the structure is as follows: First, the prepared aqueous aromatic polyurethane dispersion liquid is mixed with an appropriate amount of synthetic skin additive 'as a general ingredient to prepare an aqueous aromatic polyurethane synthetic film layer with different density and mechanical properties. Ingredients. Then, depending on the product requirements, you can choose dry-bonding process or clear-layer coating t-process ^ to form the next batch of ingredients and outer ingredients in cloth, paper and leather, etc. - on the kebab, 5 of the adhesive layer or (And) the outer layering is the above-mentioned aqueous aromatic fragrant polyurethane synthetic film layer. The basic requirements and performance testing items for the performance of synthetic leather products include: dry film thickness of each film of synthetic leather, coating! , tensile strength, elongation, tear resistance, burst strength, flexural properties, abrasion resistance, abrasion resistance, interlayer adhesion and hydrolysis resistance, etc. In the present invention, the detection method for the above items is referred to the United States. Standard Specification for AmeriCai1 S〇Ciety f〇r TeSting and Materials, ASTM 26 1270592, in the order of ASTM specification: D_1813, D_i9i〇, D-2209, D-2211, D-2262, D -3 7 86, D — 2813, D — 2〇 99 D3. 884, D-2724. For hydrolysis resistance, it was dissolved in 1% by weight of sodium hydroxide at 23 C for 24 hours. In addition, the present invention further compares the resulting synthetic skin hand to the practical needs of the synthetic leather product. Hereinafter, a plurality of embodiments will be further described in detail how to form a synthetic skin structure of the aqueous scented polyurethane film layer of the present invention by a dry bonding process or a wet laminate coating process, respectively, and illustrate the present invention. The features and advantages of the synthetic skin knots are not limited to these embodiments. Example 1 First, the aqueous aromatic polyurethane dispersion (12) was used in an amount of 1 part by weight, and 5 parts by weight of a thickener (Rheolate-255, medium thick company), bismuth by weight of methyl ethyl ketone, 35 parts by weight. The water of the mixture is mixed with the ingredients to form an adhesive layer: material (A), the viscosity of the ingredient is 4, 〇〇〇cps. Next, the aqueous aromatic polyurethane dispersion (1; 3) and the aqueous aromatic polyurethane dispersion (14) are mixed in a weight ratio of i: 2, and the weight of the mixed liquid ι〇〇 is 6 heavy injuries | (; [WC_852〇, Shangzhi Company), 8 · 4 parts by weight = agent (Rhe〇late - 255, medium thick company), 3 parts by weight of methyl ethyl ketone and 35 parts by weight of water 35 parts by weight, according to _ The mixture is mixed and prepared into the first ingredient (A), the ingredient viscosity 3, 〇〇〇cps. Extracting an A4 size release paper and applying the first outer layer (A) to the release paper of A4 paper size to form a first outer layer by using a thickness gauge and a coating bar, and the first outer layer is wet The film thickness can be between 〇_ 〇1~3. 0mm. Subsequently: placed in a 8 ° ° C hot air circulating oven 3 · 〇 minutes. After drying, on the surface of the first outer layer, the adhesive layer (5) is coated according to the method of coating the second layer (outer layer); X is coated thereon to form an adhesive layer, and the adhesive layer is formed. The wet film thickness can be between 27 1270592 O.CU-Umm. Then put 1 〇〇. 〇 Hot air circulating oven 3. 〇 minutes. After baking, the adhesive layer is still in a state of thermal softening, quickly conforming to a wet polyurethane skin (product of Nanya Plastics Co., Ltd.), and the material roll is rolled back and forth and shaped using a honing machine (Press). Cold (4), peel off the release paper, that is, the water-based polyurethane is dry and bonded to the synthetic skin. According to the ASTM D-2813 method, the crease resistance of the synthetic skin was measured > 50,000 times'. According to the ASTM D_2724 method, the transverse peeling force was measured to be 7 2 Kg / cm. And the synthetic skin was also tested by a toluene resistant solvent. Example 2: First, the aqueous aromatic polyurethane dispersion (6) was used in an amount of 1 part by weight, and 9 parts by weight of a thickener (Rheolate_2S6, medium thick company) was mixed according to general ingredients. Then the layer of the agent (7)) has a viscosity of 3, 〇〇〇叩^. Next, the aqueous aromatic polyurethane dispersion u) 1 part by weight, and 7 parts by weight of the color paste UWC-852 〇, Shangzhi company) and 7 parts by weight of thickener (Rheolate-266, medium thick company ), according to the general ingredient mixing operation, formulated into the first outer layer ingredient (B), the ingredient viscosity is 3,5 〇〇 cps. The first outer layer (B) and the adhesive layer (B) are sequentially applied to the release paper by a layer coating method by using an on-line coating and laminating apparatus, and the wet film thickness is set to 130 μm. The drying temperature is set to 8 〇 to 1 〇〇 ct. Finally, the two non-woven substrates are reattached to form a dry-fit synthetic leather structure. According to the ASTM D-2813 method, the crease resistance of the synthetic skin was measured 10,000 times; according to the ASTM D-2724 method, the longitudinal peeling force was measured to be 4·3 叼/(4), and the transverse peeling force was 3.9 Kg/ Cm. Example 3: First, take a water-based aromatic polyurethane dispersion (8), 1 part by weight, and 5 weights of a wound, a hardener (WS ~ 5 50, combined with the public § 1), and a scorpion σ Λ d ) 2 weights; S parts of humectant 28 1270592 (Surfyno! 440, Air Pr〇ducts) and 〇 · 5 parts by weight of thickener (Rheolate-266, medium thick company), mixed according to general ingredients Formulated as an adhesive layer ingredient (c) with an ingredient viscosity of 3, 〇〇〇cps.曰 Next, the aqueous aromatic polyurethane dispersion (7) is 1 part by weight, and 7 parts by weight of color T (IWC-852〇, Shangzhi Company), 3 parts by weight of one hardener (WS-550 ' Hair company), 2 parts by weight of humectant 44〇, '

Air Pr〇dUCtS company) and 〇·3 parts by weight thickener-(Rheolate-266, medium thick company), according to the general ingredients mixing operation, formulated into the first outer layer ingredients (c), the ingredient viscosity 2, l〇 0 cps. Using the on-line coating and laminating equipment, the first modified outer layer is provided with the (C) material and the adhesive layer (S1) on the release paper by a layer coating method, and the wet film thickness is set to 130 μm. The drying temperature is set to 5 〇 to 12 〇〇 c. Finally, it is transferred to a non-woven substrate to obtain a dry-fit synthetic skin structure. The crease resistance of the synthetic skin is measured according to ASTM 2 8 13 method > 10,000 times; according to the ASTM D~2724 method, the peeling force of the synthetic skin was measured to be higher than the strength of the substrate (that is, the substrate was broken during peeling). Example 4: First, the aqueous aromatic polyurethane dispersion was taken. Liquid (9) 1 part by weight, with 5 parts of spring, one part of hardener (WS_55〇, Hefa), 2 parts by weight of humectant (Surfynol 44 0, Air Product s) and 0.5 parts by weight Thickening agent (Rheolate-266, medium thick company), according to the general ingredient mixing operation, formulated into the adhesive layer ingredient (D), the ingredient viscosity is 2,5 〇〇 cps. Next, the aqueous aromatic polyurethane is dispersed Liquid (7) 1 〇〇 by weight, and 7 Ϊ 份 份 (IWC - 8 5 2 0, Shangzhi Company , One of the three parts by weight of curing agent (WS-55 0, OECD Corporation), 2 parts by weight of wetting agent (Surfyn〇; L 44〇,

Air Products Company) and 〇·3 parts by weight thickener 29 1270592 (Rheolate-266, medium thick company), according to the general ingredients mixing operation, formulated into the first outer layer (D), ingredient viscosity 2, 〇〇〇 Cps. The first outer layer (D) material and the adhesive layer layer (?) were applied to the release paper in a layer coating manner by using an on-line coating and laminating apparatus, and the wet film thickness was set to 130. Μιη, the drying temperature is set to . Finally, it is transferred to a non-woven substrate to dry-fit the synthetic skin structure. The flexural resistance of the synthetic skin was measured according to the ASTM D-2 813 method. The longitudinal peeling force of the synthetic skin was determined to be 3. 〇Kg/ by the method of ASTM D - 2 7 2 4 . The cm 'transverse peeling force is 2 · ◦ Kg / cm; according to the ASTM D-2 0 99 method, the abrasion resistance of the synthetic skin to 6 · 〇 psi is measured > 21 times; and the synthetic skin is also resistant to water Solvative test. Example 5: First, 'water-based aromatic polyurethane dispersion (11) 1 part by weight, with 5 parts by weight of one hardener (WS-5 5 〇, Hefa), 2 parts by weight of humectant ( Surfynol 44 0 'Air Products Company) and 〇· 5 parts by weight thickener (Rheolate-2%, medium thick company), according to the general ingredients mixing operation, formulated into the adhesive layer ingredient (E), the ingredient viscosity is 2, 5 0 0 cp s. Next, the aqueous aromatic polyurethane dispersion (1 〇) is used in an amount of 1 part by weight, together with 7 parts by weight of a color paste (IW 〇 852 〇, Shangzhi Company), and 3 parts by weight of a hardener (WS 5 5 0 ' Each company), 2 parts by weight of humectant (sur f yn〇1 4 4 〇, Air Products) and 〇·3 parts by weight of thickener (Rheolate-266 'medium thick company), mixed according to general ingredients, Formulated as the first outer layer (E), the ingredient viscosity 2, 〇〇〇cps. The first outer layer (E) material and the adhesive layer layer (E) are sequentially applied to the release paper by a layer coating method by using an on-line coating and laminating apparatus, and the wet film thickness is set to 130 μm. The drying temperature is set to . Finally, it was placed on a woven substrate of 30 1270592, and it was dry-fitted to the synthetic skin structure. The performance of the synthetic skin structure 'according to astm d_28i skin toughness> 100,000 times; according to astm d_2: shell: the & peel force is 3.5 Kg / cm (1〇〇% of the base sentence 2 its mediastinum / - % substrate damage); 依 - 2 = skin to 6.0 psi wear resistance > 21 〇〇 a · sheet method 'measuring the synthetic Mo, ASTMD-3 786 method, measuring the burst strength of the synthetic skin 23 Kg/cm2. In this example, the dry film properties of the first outer layer were also tested. The tensile strength of the first outer layer was measured by the method of ASTM D-2209 as η. According to the ASTM D-2211 method, the elongation of the first outer layer is 71%; according to the method of D-2262, the tear resistance of the first outer layer is I*, which is determined by the D-WU method. What is the film thickness of the outer layer of the dry film? 2 (4); The coating amount of the first outer layer was measured by the ASTM D-1910 method to be 5〇5...^, thereby calculating the pseudo density of 0.42 g/cm3. Example 6: The adhesive layer of the present embodiment was commercially available as a moisture-curing polyurethane, and (4) moisture, urethane (10) 2114T, HB Fuller Company, USA) was heated in a humidified state to a heating plate (Heater) to 15 〇. χ: Refining layer of the next layer of ingredients • Spring (F) 〇 - Next, the aqueous aromatic polyurethane dispersion (丄3) and aqueous aromatic polyamine. 酉 分散 dispersion U4) to! : 2 by weight and mixture 'and 1 part by weight of the mixture, 6 parts by weight of color paste (IWC_852〇, Shangzhi company), 8.4 parts by weight of thickener (Rhe〇late_255, medium thick company), 3.6 parts by weight of methyl ethyl ketone and 35 parts by weight of water, 35 parts by weight, mixed according to the general ingredients, formulated into the first outer layer (A), the ingredient viscosity 3, 〇〇〇 cps. Taking an A4 size release paper and applying the first 31 1270592 outer layer (A) to the A4 paper size release paper to form a first outer layer by using a thickness gauge and a coating bar, and the first outer layer The wet film thickness can be between 〇·〇1~3·〇Γητη. Subsequently, a hot air circulating oven of 8 ° C was placed for 3 〇 minutes. After drying, on the surface of the first outer layer, the molten adhesive layer (F) (moisture-cured polyurethane) is coated thereon by using a 25 μτη coater (Doct〇r blade), and the subsequent layer is still The heat-softened state is quickly applied to a wet polyurethane skin (product of Nanya Plastics Co., Ltd.), rolled back and forth with a roller, and shaped using a hot press (press). After cooling, the release paper was peeled off, and after standing for 2 hours, the outer layer of the aqueous polyurethane was laminated. The crease resistance of the synthetic skin was measured according to the ASTM D - 2 8 13 method> 10,000 times; the transverse peeling force was determined to be 9.4/(10) according to the ASTM D-2724 method. And the synthetic skin was also tested by a toluene resistant solvent. In summary, the synthetic skin structure of the aqueous aromatic polyurethane film disclosed in the present invention has better tensile strength, elongation, tear resistance, burst strength, tortuosity, abrasion resistance and abrasion resistance. , interlayer adhesion and hydrolysis resistance. The synthetic skin structure has at least one layer of aqueous aromatic polyurethane film layer, which can be used to replace the traditional solvent-type polyamine vinegar or aliphatic water-based polyurethane squash synthetic skin to solve the conventional technique and use a large amount of stalks and stalks. Residues and high process costs and other issues, and further enhance the mechanical properties of synthetic leather products. Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the scope of the invention, and various modifications may be made without departing from the spirit and scope of the invention. Therefore, the scope of protection of the present invention is defined by the scope of the appended claims. 32 1270592 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a composite skin structure of a water-containing aromatic polyurethane film layer according to the present invention. [Description of symbols] 5~ synthetic skin structure; 10~ matrix; 12~ subsequent layer; 14~ one layer or more outer layer; and 2〇~ laminated structure. 33

Claims (1)

I27059S 92137044 Patent Application Revision Amendment Date: 94.10.28 Pickup, Patent Application Range: 1. A synthetic skin structure of a water-containing aromatic polyurethane (PU) film layer comprising: a substrate; one or more outer layers And an adhesive layer between the substrate and the outer layer for bonding the substrate and the outer layer, wherein at least one of the adhesive layer and the outer layer is composed of an aqueous aromatic polyurethane, and the aqueous layer The content of the volatile organic compound of the aromatic polyurethane is less than 15% by weight, and the weight percentage is based on the total weight of the aqueous aromatic polyurethane, and the aqueous aromatic polyurethane is the product obtained by the following steps: A prepolymer mixing process is formed by forming 10 to 40% by weight of an aromatic diisocyanate, 30 to 80% by weight of a polyol, and 1 to 15% by weight of a compound having an active functional group capable of forming a hydrophilic functional group. a prepolymer; dispersing the prepolymer in water; monitoring the dispersion of the prepolymer into water The NC0 functional group content; and when the NCO functional group content of the dispersion is in the range of 0.8 to 8.0% by weight, 0.1 to 5 weight percent of a chain extender is added for chain extension reaction, wherein the weight percentage is the prepolymer The total weight is based on the benchmark. 2. The composite skin structure of the aqueous aromatic polyurethane film layer according to claim 1, wherein the wet film thickness of the adhesive layer is between 0.01 and 1.5 mm, and the dry film density is between 0.95 and Between 1.8 g/cm3. 3. The composite skin structure of the aqueous aromatic polyurethane film layer of claim 1, wherein the outer layer adjacent to the adhesive layer is a first outer layer, 0424-A20150TWF1; 02920044; phoelip 34 1270592 The wet film thickness is between 0.05 and 3 mm, and the dry film density is between 0.02 and 2.5 g/cm3. 4. The aqueous aromatic polyurethane membrane layer according to item 3 of the Shenqing patent scope, wherein the synthetic skin structure has more than one outer layer, except for the outer layer except the outer layer The wet film thickness is between 〇1〇3〜mm and the dry film density is between 〇〇2~2·5 g/cm3. - The synthetic skin structure of the aqueous aromatic polyurethane film layer according to claim 1, wherein the wet film thickness of the adhesive layer is between 0 08 and 0 8 mm, and the dry film density is Between 98·98~1·35 g/cm3. The composite skin structure of the aqueous aromatic polyurethane film layer f according to the invention of claim 2, wherein the outer layer adjacent to the adhesive layer is a first outer layer, and the wet film thickness thereof is 0. The film density is between 15 mm and the dry film density is between OH# g/cm3. 7. The method of claim 1, wherein the synthetic skin structure has more than one outer layer: each of the outer layers except the first outer layer The wet film thickness is between 〇〇1 and i〇mm' and the dry film density is between 0.2 and 1.4 g/cm3. 8. The synthetic skin structure of the aqueous aromatic polyamine vinegar film layer according to the scope of claim 帛i, wherein the aromatic diisocyanate has one or more = aromatic rings, and the aromatic ring is selected from a free phenyl group. a group consisting of biphenyl and naphthyl groups and hydrogen on one or more carbons of the aromatic ring, optionally atomic, self-priming atoms, succinyl, cyano, silk, alkoxy, cardio Substituted by thiol, weiji, arylamino or amine. 9. The synthetic skin structure of the aqueous aromatic polyamine granule layer according to claim i, wherein the aromatic diisocyanate is selected from the group consisting of a compound of the formula 11 and a compound of the formula (11) a group of its mixture = 0424-A20150TWF1; 02920044; phoelip 35 1270592 General formula Formula (Working) wherein Ri is hydrogen or (^-6 alkyl; R2 and R3 are the same or different, and are independently hydrogen, have one to six anthracene, and have one to six carbons of oxygen. a base, or an aromatic group; and η is 0, 1, 2 or 3. 10. The synthetic structure of the aqueous aromatic polyurethane membrane layer according to claim 1, wherein the aromatic diisocyanate is Toluene diisocyanate (TDI), p-diisocyanide. P-Phenylene diisocyanate (PPDI), 4,4'-Diphenylmethane diisocyanate (MDI), diisocyanate p,p'-diphenyl Pp-Bisphenyl diisocyanate (BPDI) or a mixture thereof. 11. The synthetic skin structure of the aqueous aromatic polyurethane film layer according to claim 1, wherein the polyol is a difunctional polyol or a polyfunctional polyol, including a polyester polyol or a polyether. Polyol, polycarbonate polyol, polycaprolactone polyol, polyacrylate polyol, low molecular weight polyol or a mixture thereof. A 12. The synthetic structure of the aqueous aromatic polyurethane film layer 1 according to claim 1, wherein the polyol has a molecular weight of from 60 to 6,000. 13. The synthetic structure of the aqueous aromatic polyurethane film layer of claim 1, wherein the polyol has a molecular weight of between 62 and 3,000. 14. The synthetic skin structure of the aqueous aromatic polyurethane film layer according to claim 1, wherein the hydrophilic functional group of the hydrophilic functional group is a COO-, a S03 — 2 — — NR4+, or a (CH2CH20) 0424-A20150TWF1; 02920044;phoe!ip 36 1270592 15. The synthetic skin structure of the aqueous aromatic polyurethane membrane layer according to claim 1, wherein the hydrophilic structure can be formed The functional group of active hydrogen is dimethylolpropionic acid (DMPA), dimethylolbutanoic acid (DMBA), polyethylene glycol, bis(hydroxyethyl)amine or 3-double ( Sodium hydroxyethyl)aminopropane sulfonate. 16. The synthetic skin structure of the aqueous aromatic polyurethane film layer of claim 1, wherein the chain extender is an amine having a difunctional, trifunctional or tetrafunctional group. 17. The synthetic skin structure of the aqueous aromatic polyurethane membrane layer according to claim 1, wherein the chain extender is 2-methyl-1,5-pentanediamine (2-Methyl-l, 5_pentametliylene diamine), Diethylene triamine (DETA), Triethylene tetraamine (TETA) or H2N-(CH2)m-NH2; wherein m is an integer from 0 to 12. 18. The synthetic skin structure of the aqueous aromatic polyurethane film layer according to claim 1, wherein the component forming the prepolymer via the prepolymer mixing method further comprises 0.1 to 10% by weight of at least two A low molecular weight compound of a functional group reactive with an isocyanate group. 19. The synthetic skin structure of the aqueous aromatic polyurethane film layer according to claim 18, wherein the low molecular weight f compound of the functional group reactive with the isocyanate group is an aromatic diol or an aromatic Alcohols, aromatic ether glycols, 'aliphatic diols, aliphatic polyols or aliphatic ether diols. 20. The composite structure of the aqueous aromatic polyurethane film layer of claim 1, wherein the prepolymer has a synthetic composition having a ratio of NCO to OH of from 1.1 to 3.8. 21. The composite structure of the aqueous aromatic polyurethane film layer of claim 1, wherein the prepolymer has a synthetic composition having a ratio of NCO to OH of between 1.2 and 2.4. 0424-A20150TWF1; 02920044;phoelip 37 1270592 22. The synthetic skin structure of the aqueous aromatic polyurethane membrane layer according to claim 1, wherein the hydrophilic polyurethane of the aqueous polyurethane dispersion has a hydrophilic basis of 5 to 80 Meq/100g dry. 23. The synthetic structure of the aqueous aromatic polyurethane film layer according to claim 1, wherein the aqueous polyurethane dispersion has a hydrophilic basis of 15 to 65 meq/100 g of dry matter. 24. The synthetic structure of the aqueous aromatic polyurethane film layer of claim 1, wherein the aqueous aromatic polyurethane has a solid content of from -65 weight percent. The synthetic structure of the aqueous aromatic polyurethane film layer according to claim 1, wherein the adhesive layer and at least one of the outer layers are composed of the aqueous aromatic polyurethane having different mechanical properties. 0424-A20150TWF1 ;02920044;phoelip 38