TWI525148B - Water-based polyurethane resin with high chromaticity, method of producing the same, and application on suede composite material thereof - Google Patents

Water-based polyurethane resin with high chromaticity, method of producing the same, and application on suede composite material thereof Download PDF

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TWI525148B
TWI525148B TW103146593A TW103146593A TWI525148B TW I525148 B TWI525148 B TW I525148B TW 103146593 A TW103146593 A TW 103146593A TW 103146593 A TW103146593 A TW 103146593A TW I525148 B TWI525148 B TW I525148B
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polyurethane resin
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aqueous polyurethane
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TW201623441A (en
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篠原勝治
謝建正
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財團法人紡織產業綜合研究所
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Description

高彩度水性聚氨基甲酸酯樹脂及其製造方法暨其於仿麂皮複合材料之應用 High chroma water-based polyurethane resin and its manufacturing method and application thereof in suede composite material

本發明是關於一種水性聚氨基甲酸酯樹脂及其製造方法,且特別是關於一種高彩度水性聚氨基甲酸酯樹脂及其製造方法暨其於仿麂皮複合材料之應用。 The present invention relates to an aqueous polyurethane resin and a method for producing the same, and more particularly to a high chroma waterborne polyurethane resin and a method for producing the same, and to the use of the suede composite material.

市面上有許多仿皮革、合成皮革、人造皮革等皮革製品作為天然皮革的替代品。上述皮革製品主要是在織物、針織品、不織布等基材內部或表面,形成聚氨基甲酸酯(polyurethane;PU)樹脂為主的發泡層,使其手感、多孔結構等更接近天然皮革。 There are many leather products such as leather, synthetic leather and artificial leather on the market as substitutes for natural leather. The leather product is mainly in the interior or surface of a substrate such as a woven fabric, a knit fabric or a non-woven fabric, and forms a foaming layer mainly composed of a polyurethane (PU) resin, so that the hand feeling, the porous structure and the like are closer to the natural leather.

上述PU樹脂發泡層的製造方法相當多樣化,舉例而言,可利用溼式PU製程,將PU樹脂等聚合物溶於二甲基甲醯胺等水溶性有機溶劑中,添加各種添加劑後,再將基材浸於其中或塗佈到基材上。之後,利用能與前述水溶性有 機溶劑互相混合的溶劑進行處理,使聚合物凝固,再經過脫溶劑及乾燥等步驟,而製得前述皮革製品。 The method for producing the PU resin foamed layer is quite diverse. For example, a polymer such as a PU resin can be dissolved in a water-soluble organic solvent such as dimethylformamide by a wet PU process, and various additives are added. The substrate is then immersed therein or coated onto a substrate. After that, the use can be combined with the aforementioned water solubility. The leather product is prepared by treating a solvent in which the solvent is mixed with each other, solidifying the polymer, and then performing a solvent removal and drying step.

然而,上述溼式PU製程仍存在下列問題。首先,溼式PU製程在製程中或後段加工應用時,對於水溶性有機溶劑之使用量較大,而前述水溶性有機溶劑大多是易燃性很強、毒性也很強的溶劑,不僅乾燥時間長,有引發火災的危險性,所產生的有機揮發化合物(VOC)更會釋放到大氣環境裡,惡化作業環境、造成環境污染等問題。另外,製得的皮革製品中,為了賦予近似天然皮革的手感與多孔結構,所形成的溼式PU樹脂的份量必須足夠,但這也會提高水溶性有機溶劑的殘留,導致後續必須花費相當的勞力及成本,以去除有機溶劑的殘留量及有機溶劑的回收。 However, the above wet PV process still has the following problems. First of all, the wet PU process is used in the process of processing or in the latter stage, and the amount of the water-soluble organic solvent is large, and the water-soluble organic solvent is mostly a solvent which is highly flammable and highly toxic, not only the drying time. Long, there is a risk of fire, and the resulting organic volatile compounds (VOC) will be released into the atmosphere, which will worsen the working environment and cause environmental pollution. Further, in the obtained leather product, in order to impart a texture and a porous structure similar to that of the natural leather, the amount of the wet PU resin to be formed must be sufficient, but this also increases the residual of the water-soluble organic solvent, resulting in a subsequent costly equivalent. Labor and cost to remove residual organic solvents and recover organic solvents.

因此,目前研發出水性PU樹脂,以逐步取代傳統溶劑型PU樹脂。簡言之,水性PU樹脂是以水取代上述水溶性有機溶劑,以對環境友善且不造成環境負擔。然而,水性PU樹脂的平均分子量較小,其耐水解性、機械強度、穩定性、耐熱性、手感、多孔性及彩度等亦較為不足。 Therefore, water-based PU resins have been developed to gradually replace conventional solvent-based PU resins. In short, the aqueous PU resin replaces the above water-soluble organic solvent with water to be environmentally friendly and does not impose an environmental burden. However, the aqueous PU resin has a small average molecular weight, and its hydrolysis resistance, mechanical strength, stability, heat resistance, hand feeling, porosity, and chroma are also insufficient.

目前係利用超細纖維製成之基布,配合研磨以改善其手感不良的問題。此外,也可額外於水性PU樹脂中添加粉體添加劑及凝固劑,以增加其多孔性。然上述之製程方法可改善程度相當有限,且步驟較為繁雜,又無法改善其彩度。 At present, the base fabric made of ultrafine fibers is used in combination with grinding to improve the problem of poor hand feeling. In addition, powder additives and coagulants may be additionally added to the aqueous PU resin to increase the porosity thereof. However, the above-mentioned process method can be improved to a relatively limited extent, and the steps are complicated, and the chroma cannot be improved.

有鑑於此,亟需提出一種高彩度水性聚氨基甲酸酯樹脂及其製造方法,以改善習知PU樹脂製程之各種缺點。 In view of the above, it is urgent to propose a high chroma water-based polyurethane resin and a method for producing the same to improve various disadvantages of the conventional PU resin process.

因此,本發明之目的是在提供一種水性聚氨基甲酸酯(polyurethane;PU)樹脂之製造方法,其係藉由控制水性PU樹脂的羧酸基及聚碳酸酯多元醇的含量,並添加適量的分散劑及二胺化合物,即可製得水性PU樹脂。 Accordingly, an object of the present invention is to provide a method for producing an aqueous polyurethane (PU) resin by controlling the content of a carboxylic acid group and a polycarbonate polyol of an aqueous PU resin, and adding an appropriate amount A water-based PU resin can be obtained by dispersing a dispersant and a diamine compound.

本發明之另一目的是在提供一種水性PU樹脂,其係利用上述方法製得。 Another object of the present invention is to provide an aqueous PU resin which is obtained by the above method.

本發明之又一目的是在提供一種高彩度水性PU樹脂仿麂皮複合材料用之多孔層的製造方法,其係利用乾式塗佈步驟,將包含上述之水性PU樹脂、顏料、發泡助劑及架橋劑等之高彩度水性PU樹脂組成物均勻塗佈於基材上,再進行加熱處理而製得。 Still another object of the present invention is to provide a method for producing a porous layer for a high-color aqueous PU resin-like suede composite material, which comprises using the above-mentioned aqueous PU resin, pigment, foaming auxiliary agent and a dry coating step. A high-color aqueous PU resin composition such as a bridging agent is uniformly coated on a substrate and then heat-treated.

根據本發明之上述目的,提出一種水性聚氨基甲酸酯樹脂之製造方法。在一實施例中,首先將二異氰酸酯化合物(a)、聚碳酸酯多元醇(b)與第一含羥基化合物(c-1)進行預聚合反應,以製得第一預聚物。接著,將上述之第一預聚物、第二含羥基化合物(c-2)及含羧酸基化合物(d)進行聚合反應,以製得第二預聚物,其中上述之第二預聚物具有至少一羧酸基。然後,添加中和劑(e)以中和第二預聚物。再來,以溶劑(h)稀釋中和後的第二預聚物。然後,將稀釋 後的第二預聚物添加至分散劑(f)與水的混合溶液中,以形成分散液,其中上述之分散劑(f)為含乙氧基之非離子型分散劑或含乙氧基之陰離子型分散劑。接著,將上述之分散液與二胺化合物(g)進行鏈延長反應,以製得水性PU樹脂(A),且上述之水性PU樹脂(A)為自身乳化(self-emulsification)型水性PU樹脂。 According to the above object of the present invention, a method for producing an aqueous polyurethane resin is proposed. In one embodiment, the diisocyanate compound (a), the polycarbonate polyol (b), and the first hydroxyl group-containing compound (c-1) are first subjected to a prepolymerization reaction to obtain a first prepolymer. Next, the first prepolymer, the second hydroxyl group-containing compound (c-2) and the carboxylic acid group-containing compound (d) are subjected to a polymerization reaction to obtain a second prepolymer, wherein the second prepolymerization is performed. The substance has at least one carboxylic acid group. Then, neutralizing agent (e) is added to neutralize the second prepolymer. Further, the neutralized second prepolymer was diluted with a solvent (h). Then, it will be diluted The second prepolymer is added to a mixed solution of the dispersing agent (f) and water to form a dispersion, wherein the dispersing agent (f) is an ethoxy-containing nonionic dispersing agent or an ethoxy group-containing An anionic dispersant. Next, the above dispersion liquid and a diamine compound (g) are subjected to a chain extension reaction to obtain an aqueous PU resin (A), and the above aqueous PU resin (A) is a self-emulsification type aqueous PU resin. .

基於上述之水性PU樹脂(A)之總固含量為100重量份,水性PU樹脂(A)具有0.9重量份至1.3重量份之羧酸基以及60重量份至68重量份之聚碳酸酯多元醇(b),且分散劑(f)之含量為大於0重量份至小於7重量份。 The aqueous PU resin (A) has 0.9 parts by weight to 1.3 parts by weight of a carboxylic acid group and 60 parts by weight to 68 parts by weight of a polycarbonate polyol based on the total solid content of the above aqueous PU resin (A) being 100 parts by weight. (b), and the content of the dispersing agent (f) is from more than 0 parts by weight to less than 7 parts by weight.

依據本發明之一實施例,上述之聚碳酸酯多元醇(b)可為聚碳酸酯二醇,且所述之聚碳酸酯二醇之算數平均分子量為700至3000。 According to an embodiment of the present invention, the above polycarbonate polyol (b) may be a polycarbonate diol, and the polycarbonate diol has an arithmetic mean molecular weight of 700 to 3,000.

依據本發明之一實施例,上述之第一含羥基化合物(c-1)和第二含羥基化合物(c-2)可為脂肪族多元醇。在另一實施例中,上述之第一含羥基化合物(c-1)可包含1,3-丁二醇(1,3-buthyleneglycol),且上述之第二含羥基化合物(c-2)包含三甲醇丙烷(trimethylolpropane)或丙三醇。 According to an embodiment of the present invention, the first hydroxyl group-containing compound (c-1) and the second hydroxyl group-containing compound (c-2) may be an aliphatic polyol. In another embodiment, the first hydroxyl group-containing compound (c-1) may include 1,3-buthylene glycol (col), and the second hydroxyl group-containing compound (c-2) comprises Trimethylolpropane or glycerol.

依據本發明之一實施例,上述之含羧酸基化合物(d)可為分子量或算數平均分子量為100至1000的含羧酸基之短鏈多元醇。在另一實施例中,上述之含羧酸基化合物(d)可包含二羥甲基丙酸(dimethylol propionoc acid;DMPA)及二羥甲基丁酸(dimethylol butanoic acid;DMBA)。 According to an embodiment of the present invention, the above-mentioned carboxylic acid group-containing compound (d) may be a carboxylic acid group-containing short-chain polyol having a molecular weight or an arithmetic mean molecular weight of from 100 to 1,000. In another embodiment, the above carboxylic acid group-containing compound (d) may comprise dimethylol propionoc acid (DMPA) and dimethylol butanoic acid (DMBA).

依據本發明之一實施例,上述之中和劑(e)可為有機中和劑或無機中和劑。 According to an embodiment of the present invention, the neutralizing agent (e) may be an organic neutralizing agent or an inorganic neutralizing agent.

依據本發明之一實施例,上述之水性PU樹脂(A)具有3重量份至5重量份之分散劑(f)以及0.05重量份至1重量份之二胺化合物(g)為較佳。 According to an embodiment of the present invention, it is preferred that the above aqueous PU resin (A) has 3 parts by weight to 5 parts by weight of the dispersant (f) and 0.05 parts by weight to 1 part by weight of the diamine compound (g).

依據本發明之一實施例,上述之溶劑(h)可包含丙酮、丁酮(methyl ethyl ketone;MEK)及其任意組合。 According to an embodiment of the present invention, the solvent (h) may comprise acetone, methyl ethyl ketone (MEK), and any combination thereof.

依據本發明之一實施例,在上述之鏈延長反應後,更可選擇性進行攪拌步驟。 According to an embodiment of the present invention, after the chain extension reaction described above, the stirring step is more selectively performed.

依據本發明之一實施例,水性PU樹脂(A)具有0.9重量份至1.0重量份之羧酸基及64至68重量份之聚碳酸酯多元醇(b)為較佳。 According to an embodiment of the present invention, it is preferred that the aqueous PU resin (A) has from 0.9 part by weight to 1.0 part by weight of the carboxylic acid group and from 64 to 68 parts by weight of the polycarbonate polyol (b).

根據本發明之另一目的,提供一種水性PU樹脂,其係利用上述之水性PU樹脂的製造方法所製成。而且,基於水性PU樹脂(A)之總固含量為100重量份,水性PU樹脂(A)具有0.9重量份至1.3重量份之羧酸基以及60重量份至68重量份之聚碳酸酯多元醇(b)。 According to another object of the present invention, there is provided an aqueous PU resin which is produced by the above-described method for producing an aqueous PU resin. Moreover, the aqueous PU resin (A) has 0.9 parts by weight to 1.3 parts by weight of the carboxylic acid group and 60 parts by weight to 68 parts by weight of the polycarbonate polyol based on 100 parts by weight of the total solid content of the aqueous PU resin (A). (b).

根據本發明之又一目的,提供一種高彩度水性PU樹脂仿麂皮複合材料用之多孔層的製造方法。首先,利用乾式塗佈步驟,將高彩度水性PU樹脂組成物(F)塗佈於基材上。其中,上述之高彩度水性PU樹脂組成物(F)包括水性PU樹脂(A)、顏料(B)、發泡助劑(C)及架橋劑(D),上述之顏料(B)可為水溶性陰離子分散型顏料,而上述之發泡助劑的揮發速率低於水的揮發速率,不溶於水且不與水性PU樹 脂(A)互溶。其中,基於水性PU樹脂(A)之使用量為100重量份,顏料(B)之使用量為2至6重量份,發泡助劑(C)之使用量為20至60重量份,以及架橋劑(D)之使用量為0.5至4重量份。 According to still another object of the present invention, a method for producing a porous layer for a high chroma water-based PU resin-like suede composite material is provided. First, the high chroma water-based PU resin composition (F) is applied onto a substrate by a dry coating step. The high chroma water-based PU resin composition (F) includes an aqueous PU resin (A), a pigment (B), a foaming auxiliary (C), and a bridging agent (D), and the above pigment (B) may be water-soluble. An anionic dispersion type pigment, and the above-mentioned foaming aid has a volatilization rate lower than that of water, and is insoluble in water and does not bind to water-based PU trees. Lipid (A) is mutually soluble. Wherein the use amount of the aqueous PU resin (A) is 100 parts by weight, the amount of the pigment (B) is 2 to 6 parts by weight, the amount of the foaming auxiliary (C) is 20 to 60 parts by weight, and bridging The agent (D) is used in an amount of from 0.5 to 4 parts by weight.

接著,將塗佈後的基材進行加熱處理,使高彩度水性PU樹脂組成物(F)形成多孔層,其中上述之加熱處理係為了去除高彩度水性PU樹脂組成物(F)的水份,使其固化並形成塗佈層,之後因發泡助劑(C)揮發形成複數個連續孔而形成多孔層。 Next, the coated substrate is subjected to heat treatment to form a porous layer of the high-color aqueous PU resin composition (F), wherein the heat treatment is performed to remove moisture of the high-color aqueous PU resin composition (F). The coating layer is cured and formed, and then a plurality of continuous pores are formed by volatilization of the foaming aid (C) to form a porous layer.

所製得之多孔層不使用起毛處理,且多孔層與基材之間係直接塗佈,並不存在任何黏著層。此外,所製得之多孔層具有不低於5之彩度以及不低於4級的摩擦堅牢度。 The obtained porous layer was not subjected to raising treatment, and the porous layer was directly coated with the substrate, and there was no adhesive layer. Further, the obtained porous layer has a chroma of not less than 5 and a frictional fastness of not less than 4 grades.

依據本發明之一實施例,上述之高彩度水性PU樹脂組成物(F)可選擇性包含添加劑(E),且添加劑(E)可包含增黏劑、消泡劑、造膜劑或感熱凝固劑。 According to an embodiment of the present invention, the high-color aqueous PU resin composition (F) may optionally contain an additive (E), and the additive (E) may comprise a tackifier, an antifoaming agent, a film former or a heat-sensitive coagulant. .

100‧‧‧方法 100‧‧‧ method

110、120、130、140、150、160‧‧‧步驟 110, 120, 130, 140, 150, 160‧ ‧ steps

為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂,所附圖式之詳細說明如下:圖1係繪示根據本發明一實施例之水性PU樹脂的製造方法的部分流程圖。 The above and other objects, features, advantages and embodiments of the present invention will become more <RTIgt; Part of the flow chart.

本發明提供一種高彩度水性聚氨基甲酸酯(polyurethane;PU)樹脂及其製造方法,其先控制水性PU樹脂的羧酸基與聚碳酸酯多元醇含量,以製得水性PU樹脂,再利用所製得之水性PU樹脂添加顏料、發泡助劑、架橋劑或其他添加劑等,以製得高彩度水性PU樹脂。 The invention provides a high chroma water-based polyurethane (PU) resin and a preparation method thereof, which firstly control the content of a carboxylic acid group and a polycarbonate polyol of an aqueous PU resin to obtain an aqueous PU resin, and reuse the same. The obtained water-based PU resin is added with a pigment, a foaming aid, a bridging agent or other additives to obtain a high-color water-based PU resin.

在一實施例中,本發明的水性PU樹脂至少包含 二異氰酸酯化合物(a)、聚碳酸酯多元醇(b)、第一含羥基化合物(c-1)、第二含羥基化合物(c-2)、含羧酸基化合物(d)、中和劑(e)、分散劑(f)、二胺化合物(g)及溶劑(h),以下分述之。 In one embodiment, the aqueous PU resin of the present invention comprises at least Diisocyanate compound (a), polycarbonate polyol (b), first hydroxyl group-containing compound (c-1), second hydroxyl group-containing compound (c-2), carboxylic acid group-containing compound (d), neutralizer (e), a dispersing agent (f), a diamine compound (g), and a solvent (h), which are described below.

水性聚氨基甲酸酯樹脂Waterborne polyurethane resin 二異氰酸酯化合物(a)Diisocyanate compound (a)

適用於本發明之二異氰酸酯化合物(a)可為任何用於製造PU乳液所使用之有機二異氰酸酯化合物,其包括但不限於脂肪族二異氰酸酯、脂環族二異氰酸酯、芳香族二異氰酸酯或上述之任意組合。 The diisocyanate compound (a) suitable for use in the present invention may be any of the organic diisocyanate compounds used in the manufacture of PU emulsions, including but not limited to aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates or the above. random combination.

前述之脂肪族二異氰酸酯的具體例如:二異氰酸異茀爾酮酯(isophorone diisocyanate;IPDI)、二異氰酸六亞甲基酯(1,6-hexamethylene diisocyanate;HMDI)、二異氰酸四甲基苯二甲基酯(tetramethylxylylene diisocyanate;TMXDI)及二異氰酸己二酯等。前述之脂環族二異氰酸酯可例如但不限於二異氰酸4,4'-二環己基甲烷酯(4,4'-dicyclohexylmethane diisocyanate;H12MDI)等。前述之芳香族二異氰酸酯的具體例如:二異氰酸2,4-苯亞甲酯(2,4-tolylene diisocyanate)、二異氰酸2,6-苯亞甲酯、二異氰酸4,4’-二苯基甲烷酯、二異氰酸對-亞苯甲酯、二異氰酸亞二甲苯酯和二異氰酸1,5-萘酯等,其中,尤以二異氰酸異茀爾酮酯(IPDI)及二異氰酸4,4'-二環己基甲烷酯(H12MDI)為較佳。 Specific examples of the aforementioned aliphatic diisocyanate are: isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI), diisocyanate Tetramethylxylylene diisocyanate (TMXDI) and dihexyl diisocyanate. The aforementioned alicyclic diisocyanate may be, for example but not limited to, 4,4'-dicyclohexylmethane diisocyanate (4,4'-dicyclohexylmethane) Diisocyanate; H12MDI) and so on. Specific examples of the aforementioned aromatic diisocyanate are: 2,4-tolylene diisocyanate, 2,6-benzylidene diisocyanate, diisocyanate 4, 4'-diphenylmethane ester, p-benzylidene diisocyanate, dimethylene diisocyanate and 1,5-naphthyl diisocyanate, among which diisocyanate A ketone ester (IPDI) and 4,4'-dicyclohexylmethane diisocyanate (H12MDI) are preferred.

聚碳酸酯多元醇(b)Polycarbonate polyol (b)

適用於本發明之聚碳酸酯多元醇(b)以由碳酸酯與多元醇之反應者為較佳,其中碳酸酯之具體例如:碳酸二烷酯類(dialkyl carbonates)、碳酸亞烴酯類(alkylene carbonates)及碳酸二芳酯類等。至於碳酸二烷酯類可包括但不限於碳酸二甲酯以及碳酸二乙酯。碳酸亞烴酯類可包括但不限於碳酸乙烯。碳酸二芳酯類可包括但不限於碳酸二苯酯。 The polycarbonate polyol (b) suitable for use in the present invention is preferably a reactant derived from a carbonate and a polyol, wherein specific examples of the carbonate are, for example, dialkyl carbonates or alkylene carbonates ( Alkene carbonates) and diaryl carbonates. As for the dialkyl carbonates, they may include, but are not limited to, dimethyl carbonate and diethyl carbonate. The alkylene carbonates can include, but are not limited to, ethylene carbonate. Diaryl carbonates can include, but are not limited to, diphenyl carbonate.

前述聚碳酸酯多元醇(b)以聚碳酸酯二元醇為宜,其算數平均分子量可例如為700至3000,然以1000至2000為較佳。其具體例可包括Nippollan-965(Pc-1000;日本Poly公司製)及Nippollan-963(Pc-2000;日本Poly公司製)。 The above polycarbonate polyol (b) is preferably a polycarbonate diol having an arithmetic mean molecular weight of, for example, 700 to 3,000, preferably 1,000 to 2,000. Specific examples thereof include Nippollan-965 (Pc-1000; manufactured by Japan Poly Co., Ltd.) and Nippollan-963 (Pc-2000; manufactured by Japan Poly Co., Ltd.).

基於水性聚氨基甲酸酯樹脂(A)之使用量為100重量份,上述之聚碳酸酯多元醇(b)之含量為60重量份至68重量份,然以64重量份至68重量份為較佳。 The amount of the above polycarbonate polyol (b) is from 60 parts by weight to 68 parts by weight, based on 100 parts by weight of the aqueous polyurethane resin (A), and is from 64 parts by weight to 68 parts by weight. Preferably.

若上述之聚碳酸酯多元醇(b)的含量低於60重量份,則無法達到後述預定之彩度,若上述之聚碳酸酯多元醇(b)的含量高於68重量份,則造成製得之水性PU樹脂(A)的安定性不佳,而易聚集。 When the content of the polycarbonate polyol (b) is less than 60 parts by weight, the predetermined chroma will not be obtained, and if the content of the polycarbonate polyol (b) is more than 68 parts by weight, the system is produced. The water-based PU resin (A) has poor stability and is easy to aggregate.

補充說明的是,倘若上述之聚碳酸酯多元醇(b)改使用聚酯(polyester)類,則所製得之成品的耐水解性不佳。此外,倘若上述之聚碳酸酯多元醇(b)改使用聚醚(polyether)類,則所製得之成品無法達到預定的彩度及手感。因此,本發明之水性PU樹脂排除使用聚酯類及聚醚類。 It is to be noted that if the above polycarbonate polyol (b) is changed to a polyester, the obtained product has poor hydrolysis resistance. Further, if the above polycarbonate polyol (b) is changed to a polyether, the finished product cannot achieve a predetermined chroma and feel. Therefore, the aqueous PU resin of the present invention excludes the use of polyesters and polyethers.

含羥基化合物(c)Hydroxy-containing compound (c)

本發明使用的含羥基化合物(c)一般以脂肪族多元醇為宜,可包括但不限於脂肪族二醇及脂肪族三醇等。在一實施例中,上述含羥基化合物(c)可包括但不限於第一含羥基化合物(c-1)及第二含羥基化合物(c-2)。 The hydroxyl group-containing compound (c) used in the present invention is generally preferably an aliphatic polyol, and may include, but is not limited to, an aliphatic diol and an aliphatic triol. In one embodiment, the hydroxyl group-containing compound (c) may include, but is not limited to, the first hydroxyl group-containing compound (c-1) and the second hydroxyl group-containing compound (c-2).

前述適用的第一含羥基化合物(c-1)為脂肪族二醇之具體例可包含但不限於乙二醇、丙二醇、2-甲基-1,3-丙二醇、1,3-丁二醇(1,3-butanediol;1,3-BG)、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、3-甲基-1,5-戊二醇、新戊基二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、2-甲基-1,8-辛二醇及1,10-癸二醇,然以1,3-丁二醇為較佳。 Specific examples of the above-mentioned first hydroxyl group-containing compound (c-1) which is an aliphatic diol may include, but are not limited to, ethylene glycol, propylene glycol, 2-methyl-1,3-propanediol, and 1,3-butanediol. (1,3-butanediol; 1,3-BG), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol , neopentyl glycol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol and 1,10-anthracene The alcohol is preferably 1,3-butanediol.

前述適用的第二含羥基化合物(c-2)為脂肪族三醇之具體例可包含但不限於丙三醇、三甲醇甲烷、三甲醇乙烷及三甲醇丙烷(trimethylolpropane;TMP),然以三甲醇丙烷(TMP)及丙三醇為較佳。 Specific examples of the above-mentioned second hydroxyl group-containing compound (c-2) which is an aliphatic triol may include, but are not limited to, glycerin, trimethylmethane, trimethylolethane, and trimethylolpropane (TMP). Trimethylolpropane (TMP) and glycerol are preferred.

含羧酸基化合物(d)Carboxylic acid-containing compound (d)

本發明使用的含羧酸基化合物(d)可賦予水性PU樹脂具有親水性側鏈基團,亦可選擇性含有其他親水性側鏈基團,例如磺酸基(-SO3H)、磷酸基(-OPO3H2)及/或膦酸基(-PO3H2)。 The carboxylic acid group-containing compound (d) used in the present invention may impart a hydrophilic side chain group to the aqueous PU resin, and may optionally contain other hydrophilic side chain groups such as a sulfonic acid group (-SO 3 H), phosphoric acid. Base (-OPO 3 H 2 ) and/or phosphonic acid group (-PO 3 H 2 ).

在一例示中,前述之含羧酸基化合物(d)為含羧酸基之短鏈多元醇,其分子量或算數平均分子量一般為100至1000,而其具體例可包含但不限於脂肪族二羧酸,例如丁二酸、戊二酸、己二酸、辛二酸、壬二酸(azelaic acid)、癸二酸、十二碳二元酸、2-甲基丁二酸、2-甲基己二酸、3-甲基己二酸、3-甲基戊烷-二元酸、2-甲基辛烷-二元酸、3,8-二甲基與烷-二元酸、3,7-二甲基與烷-二元酸、二羥甲基丙酸(dimethylolpropionic acid;DMPA)及二羥甲基丁酸(dimethylol butanoic acid;DMBA)等。其中,又以二羥甲基丙酸(DMPA)及二羥甲基丁酸(DMBA)為較佳,以賦予水性PU樹脂較硬的觸感。 In an exemplary embodiment, the carboxylic acid group-containing compound (d) is a carboxylic acid group-containing short-chain polyol, and its molecular weight or arithmetic mean molecular weight is generally from 100 to 1,000, and specific examples thereof may include, but are not limited to, aliphatic two. Carboxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelic acid, azelaic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyl Adipic acid, 3-methyladipate, 3-methylpentane-dibasic acid, 2-methyloctane-dibasic acid, 3,8-dimethyl and alkane-dibasic acid, 3 , 7-dimethyl and alkane-dibasic acid, dimethylolpropionic acid (DMPA) and dimethylol butanoic acid (DMBA). Among them, dimethylolpropionic acid (DMPA) and dimethylolbutanoic acid (DMBA) are preferred to impart a hard touch to the aqueous PU resin.

基於水性PU樹脂(A)之使用量為100重量份,上述之含羧酸基化合物(d)所提供的羧酸基含量可為0.9重量份至1.3重量份,然以0.9重量份至1.0重量份為較佳。 The carboxylic acid group-containing compound (d) may have a carboxylic acid group content of from 0.9 part by weight to 1.3 parts by weight, based on the amount of the aqueous PU resin (A), and may be from 0.9 part by weight to 1.0 part by weight. The serving is preferred.

若上述之羧酸基含量低於0.9重量份,則水性PU樹脂(A)不易分散,若上述之羧酸基含量高於1.3重量份,則後述所製得之高彩度水性PU樹脂仿麂皮複合材料用之多孔層的手感不佳。 When the carboxylic acid group content is less than 0.9 parts by weight, the aqueous PU resin (A) is less likely to be dispersed, and if the carboxylic acid group content is more than 1.3 parts by weight, the high-color aqueous PU resin-like suede composite prepared as described later is used. The porous layer for materials has a poor hand.

補充說明的是,本發明此處之羧酸基含量低於2重量份時,會有無法均勻分散的問題,然本發明係利用後述添加的分散劑(f)改善上述問題,因而可達到本發明主張之效果。 In addition, when the content of the carboxylic acid group in the present invention is less than 2 parts by weight, there is a problem that the dispersion cannot be uniformly dispersed. However, in the present invention, the above-mentioned problem is improved by the dispersant (f) added later, and thus the present invention can be achieved. The effect of the invention.

中和劑(e)Neutralizer (e)

本發明所述之中和劑(e),用以避免水性PU樹脂成膜後出現裂縫。在一實施例中,中和劑(e)可更包括有機中和劑(e-1)及/或無機中和劑(e-2)。前述適合之有機中和劑(e-1)可包括但不限於三甲胺、三乙胺、三正丙胺、三丁胺、三乙醇胺、三異丙醇胺、N-甲基嗎啉(N-methylmorphorine;NMMP)或上述之任意組合,然以N-甲基嗎啉為較佳。前述適合之無機中和劑(e-2)可包括但不限於氫氧化鉀、氫氧化鈉、氫氧化鋰或上述之任意組合。前述之中和劑(e)可單獨一種或混合兩種或兩種以上使用。 The neutralizing agent (e) of the present invention is used to prevent cracks from occurring after the aqueous PU resin is formed into a film. In an embodiment, the neutralizing agent (e) may further comprise an organic neutralizing agent (e-1) and/or an inorganic neutralizing agent (e-2). The aforementioned suitable organic neutralizing agent (e-1) may include, but is not limited to, trimethylamine, triethylamine, tri-n-propylamine, tributylamine, triethanolamine, triisopropanolamine, N-methylmorpholine (N- Methylmorphorine; NMMP) or any combination of the above, preferably N-methylmorpholine. The aforementioned inorganic neutralizing agent (e-2) may include, but is not limited to, potassium hydroxide, sodium hydroxide, lithium hydroxide or any combination of the above. The aforementioned neutralizing agent (e) may be used singly or in combination of two or more kinds.

分散劑(f)Dispersing agent (f)

本發明之分散劑(f)係作為外部乳化劑,且不與二異氰酸酯化合物(a)、聚碳酸酯多元醇(b)、第一含羥基化合物(c-1)、第二含羥基化合物(c-2)、含羧酸基化合物(d)、中和劑(e)、二胺化合物(g)及溶劑(h)反應。上述之分散劑(f)可為含乙氧基之非離子型分散劑或含乙氧基之陰離子型分散劑,且所選用之分散劑(f)之親水性-親油性平衡(HLB)以11至16為佳。 The dispersing agent (f) of the present invention is used as an external emulsifier and does not react with the diisocyanate compound (a), the polycarbonate polyol (b), the first hydroxyl group-containing compound (c-1), and the second hydroxyl group-containing compound ( C-2), containing a carboxylic acid group-containing compound (d), a neutralizing agent (e), a diamine compound (g), and a solvent (h). The above dispersing agent (f) may be an ethoxylated nonionic dispersing agent or an ethoxylated anionic dispersing agent, and the hydrophilicity-lipophilic balance (HLB) of the selected dispersing agent (f) is 11 to 16 is preferred.

上述之含乙氧基之非離子型分散劑可包含但不限於聚乙氧基化烷基酚,如:聚乙氧基化對壬基酚、對辛基 酚或對十二烷基酚、聚乙氧基化直鏈醇、聚乙氧基化聚氧化丙烯二醇、聚乙氧基化硫醇、聚乙氧基化脂肪酸、聚乙氧基化矽氧烷、乙氧基化椰油基醯胺、辛基苯氧基聚乙氧基乙醇、壬基苯氧基聚乙氧基乙醇或以上之化合物的任意組合。 The above ethoxylated nonionic dispersing agent may include, but is not limited to, a polyethoxylated alkylphenol such as polyethoxylated p-nonylphenol, p-octyl Phenol or p-dodecyl phenol, polyethoxylated linear alcohol, polyethoxylated polyoxypropylene diol, polyethoxylated thiol, polyethoxylated fatty acid, polyethoxylated ruthenium Oxylkane, ethoxylated cocoamine, octylphenoxypolyethoxyethanol, nonylphenoxypolyethoxyethanol or any combination of the above.

上述之含乙氧基之非離子型分散劑的具體例可例如陶氏化學製之Tergitol TMN 100及Triton X-100、殼牌化學公司製之商品名為Neodol 25-7、Neodol 23-6.5、Neodol 1-5及Neodol23-9,商品名為Dobanol91-5及Dobanol 25-7,或美國聯合碳化物公司製之商品名為Tergitol 15-S-7及Tergitol 15-S-9等產品或以上商品之任意組合。 Specific examples of the above-mentioned ethoxy group-containing nonionic dispersing agent are, for example, Tergitol TMN 100 and Triton X-100 manufactured by Dow Chemical Co., Ltd., and manufactured by Shell Chemical Co., Ltd. under the trade name Neodol 25-7, Neodol 23-6.5, Neodol. 1-5 and Neodol23-9, trade names are Dobanol91-5 and Dobanol 25-7, or products of the United States Union Carbide Corporation under the trade names of Tergitol 15-S-7 and Tergitol 15-S-9 or above. random combination.

上述之含乙氧基之陰離子型分散劑可包含乙氧基化烷基硫酸鈉(AES),如:乙氧基化的月桂基醚硫酸鈉(SLES)、碳數為12至22之其他乙氧基化烷基硫酸鈉或上述之任意組合。 The above ethoxylated anionic dispersant may comprise ethoxylated sodium alkyl sulphate (AES), such as: ethoxylated sodium lauryl ether sulfate (SLES), other B having a carbon number of 12 to 22. Sodium oxyalkyl sulfate or any combination of the above.

基於水性PU樹脂(A)之使用量為100重量份,上述之分散劑(f)之使用量係大於0重量份至7重量份,然以3重量份至5重量份為較佳。 The amount of the dispersing agent (f) to be used is preferably from 0 part by weight to 7 parts by weight, based on 100 parts by weight of the aqueous PU resin (A), and preferably from 3 parts by weight to 5 parts by weight.

本發明所述之分散劑(f)係為使水性PU樹脂(A)可均勻分散,若不使用分散劑(f)或使用超過7重量份之分散劑(f),則會造成水性PU樹脂(A)無法均勻分散。 The dispersing agent (f) according to the present invention is such that the aqueous PU resin (A) can be uniformly dispersed. If the dispersing agent (f) is not used or more than 7 parts by weight of the dispersing agent (f) is used, the aqueous PU resin is caused. (A) It is not possible to disperse evenly.

二胺化合物(g)Diamine compound (g)

本發明使用之二胺化合物(g)係作為鏈延長劑,其具體例可包括但不限於乙二胺(ethylenediamine)、 六亞甲基二胺、二亞乙基三胺、肼(hydrazine)、琥珀酸二醯肼、對苯二甲酸二醯肼、哌嗪(piperazine)等,其中尤以哌嗪為較佳。 The diamine compound (g) used in the present invention is a chain extender, and specific examples thereof may include, but are not limited to, ethylenediamine, Hexamethylenediamine, diethylenetriamine, hydrazine, diterpene succinate, diterpene terephthalate, piperazine, etc., of which piperazine is preferred.

基於水性聚氨基甲酸酯樹脂(A)之使用量為100重量份,上述之二胺化合物(g)之含量為0.05重量份至1重量份。在使用時,上述之二胺化合物(g)可配製為例如含10重量百分比之二胺化合物的水溶液。 The content of the above diamine compound (g) is from 0.05 part by weight to 1 part by weight based on 100 parts by weight of the aqueous polyurethane resin (A). In use, the above diamine compound (g) may be formulated, for example, as an aqueous solution containing 10% by weight of a diamine compound.

溶劑(h)Solvent (h)

本發明所形成之第二預聚物,可使用溶劑(h)加以稀釋,惟溶劑(h)不與二異氰酸酯化合物(a)、聚碳酸酯多元醇(b)、第一含羥基化合物(c-1)、第二含羥基化合物(c-2)、含羧酸基化合物(d)、中和劑(e)、分散劑(f)及二胺化合物(g)反應,上述之溶劑(h)可包括但不限於丙酮(acetone)、丁酮(methylethylketone;MEK)、二甲基乙醯胺(dimethylacetamide;DMA)及甲苯(toluene)等,然以丙酮、丁酮或其任意組合為較佳。 The second prepolymer formed by the present invention may be diluted with a solvent (h), except that the solvent (h) is not combined with the diisocyanate compound (a), the polycarbonate polyol (b), and the first hydroxyl group-containing compound (c) -1), a second hydroxyl group-containing compound (c-2), a carboxylic acid group-containing compound (d), a neutralizing agent (e), a dispersing agent (f), and a diamine compound (g), the above solvent (h) ) may include, but is not limited to, acetone, methyl ethylketone (MEK), dimethylacetamide (DMA), toluene, etc., but acetone, methyl ethyl ketone or any combination thereof is preferred. .

此外,本發明的水係用以溶解或分散上述成份,並無特別限制。其具體例如:蒸餾水、純水(經離子交換樹脂等行脫鹽處理而得之水)、超純水(除無機離子外,不含有機物、生菌、微粒子及溶解氣體)及已經揭露之各種機能水等。本發明中所使用的水較佳為純水或超純水,更佳為超純水。其中,上述超純水可藉由將自來水通過活性碳、離子交換處理及蒸餾處理後,必要時以紫外光照射殺菌,或者通過過濾器而得。 Further, the water system of the present invention is used for dissolving or dispersing the above components, and is not particularly limited. Specifically, for example, distilled water, pure water (water obtained by deionization treatment by ion exchange resin, etc.), ultrapure water (excluding inorganic ions, containing no organic matter, bacteria, fine particles, and dissolved gas) and various functions that have been disclosed Water, etc. The water used in the present invention is preferably pure water or ultrapure water, more preferably ultrapure water. The ultrapure water may be obtained by passing the tap water through activated carbon, ion exchange treatment, and distillation treatment, and if necessary, sterilizing by ultraviolet light irradiation or passing through a filter.

水性聚氨基甲酸酯樹脂之製造方法Method for producing waterborne polyurethane resin

本發明之水性聚氨基甲酸酯(polyurethane;PU)樹脂係藉由控制聚碳酸酯多元醇(b)與水性PU樹脂中的羧酸基含量而製得。請參閱圖1,其係繪示根據本發明一實施例之水性PU樹脂的製造方法的部分流程圖,以下詳細描述之。 The aqueous polyurethane (PU) resin of the present invention is obtained by controlling the content of a carboxylic acid group in the polycarbonate polyol (b) and the aqueous PU resin. Please refer to FIG. 1 , which is a partial flow chart showing a method for manufacturing an aqueous PU resin according to an embodiment of the present invention, which is described in detail below.

在一實施例中,將二異氰酸酯化合物(a)、聚碳酸酯多元醇(b)與第一含羥基化合物(c-1),於80℃至90℃下進行預聚合反應約2.5小時,以形成第一預聚物,如圖1之步驟110所示。 In one embodiment, the diisocyanate compound (a), the polycarbonate polyol (b) and the first hydroxyl-containing compound (c-1) are prepolymerized at 80 ° C to 90 ° C for about 2.5 hours. A first prepolymer is formed, as shown in step 110 of FIG.

在式(I)中,式(I-1)係指二異氰酸酯化合物(a),式(I-2)係指聚碳酸酯多元醇(b),式(I-3)係指第一預聚物,且式(I-4)係指反應剩餘之二異氰酸酯化合物(a)。另外,a可為2.5至3.5,b可為0.5至1.5,且c可為0.5至1.5。 In the formula (I), the formula (I-1) means a diisocyanate compound (a), the formula (I-2) means a polycarbonate polyol (b), and the formula (I-3) means a first pre- The polymer, and the formula (I-4) means the diisocyanate compound (a) remaining in the reaction. Further, a may be from 2.5 to 3.5, b may be from 0.5 to 1.5, and c may be from 0.5 to 1.5.

在式(I)之反應中,可視實際需要,選擇性添加觸媒及/或抗氧化劑。前述之觸媒可包括但不限於辛酸錫、三乙酸單丁基錫、單辛酸單丁基錫、單乙酸單丁基錫、順丁 烯二酸單丁基錫、二乙酸二丁基錫、二辛酸二丁基錫、二硬脂酸二丁基錫、二月桂酸二丁基錫及順丁烯二酸二丁基錫等有機錫化合物;鈦酸四異丙酯、鈦酸四正丁酯等有機鈦化合物;三乙胺、N,N-二乙基環己基胺、N,N,N’,N’-四甲基乙基伸乙基胺及三伸乙基二胺等第三級胺類。前述之抗氧化劑可包括但不限於有機亞磷酸酯化合物,其具體例如:四苯基二丙二醇二亞磷酸酯(tetraphenyl dipropyleneglycol diphosphite;TDD)、二苯基季戊四醇二亞磷酸酯、二苯基異癸基亞磷酸酯三壬基異癸基亞磷酸酯、二苯基酸亞磷酸酯、二(2,4,6-三叔丁基苯基)季戊四醇二亞磷酸酯、二(2,4-二叔丁基苯基)季戊四醇二亞磷酸酯、二(十八烷基)季戊四醇雙亞磷酸酯、三苯基亞磷酸酯、三(壬基酚)亞磷酸酯、四(2,4-二叔丁基酚)-4,4'-聯苯基二亞磷酸酯、苯基二異癸基亞磷酸酯、聚-4,4'-異亞丙基二酚四酚亞磷酸酯、聚(二丙二醇)苯基亞磷酸酯(PDP)及有機金屬化合物之環保酯化觸媒(esterification catalyst)等,然其中以有機金屬化合物之環保酯化觸媒(ES CAT-100E,Seho Tech Inc.,Korea)為較佳。 In the reaction of the formula (I), a catalyst and/or an antioxidant may be selectively added depending on actual needs. The aforementioned catalyst may include, but is not limited to, tin octylate, monobutyltin triacetate, monobutyltin monooctanate, monobutyltin monoacetate, and cis-butane. Organotin compounds such as monobutyltin diene, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin distearate, dibutyltin dilaurate and dibutyltin maleate; tetraisopropyl titanate, titanic acid Organic titanium compound such as tetra-n-butyl ester; triethylamine, N,N-diethylcyclohexylamine, N,N,N',N'-tetramethylethylethylamine and tri-ethylenediamine Third-grade amines. The aforementioned antioxidant may include, but is not limited to, an organic phosphite compound, which is specifically, for example, tetraphenyl dipropyleneglycol diphosphite (TDD), diphenyl pentaerythritol diphosphite, diphenylisoindole. Phosphite trimethyl isodecyl phosphite, diphenyl phosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, di(2,4-di Tert-butylphenyl)pentaerythritol diphosphite, di(octadecyl)pentaerythritol diphosphite, triphenylphosphite, tris(nonylphenol) phosphite, tetra (2,4-di-tert Butylphenol)-4,4'-biphenyldiphosphite, phenyldiisodecylphosphite, poly-4,4'-isopropylidenediphenol tetraphenol phosphite, poly(two Propylene glycol) phenyl phosphite (PDP) and an esterification catalyst for organometallic compounds, etc., among which are environmentally friendly esterification catalysts of organometallic compounds (ES CAT-100E, Seho Tech Inc., Korea ) is better.

接著,待前述式(I-3)之第一預聚物降溫至約75℃或低於75℃後,如式(II)之所示,使第一預聚物、剩餘之二異氰酸酯化合物(a)、第二含羥基化合物(c-2)及含羧酸基化合物(d),在70至75℃的溫度下,進行聚合反應,以形成第二預聚物,如圖1步驟120所示。其中第二預聚 物具有至少一親水性側鏈基團,例如羧酸基、磺酸基(-SO3H)、磷酸基(-OPO3H2)或膦酸基(-PO3H2)。 Next, after the first prepolymer of the above formula (I-3) is cooled to about 75 ° C or lower, as shown in the formula (II), the first prepolymer, the remaining diisocyanate compound ( a), the second hydroxyl group-containing compound (c-2) and the carboxylic acid group-containing compound (d) are subjected to a polymerization reaction at a temperature of 70 to 75 ° C to form a second prepolymer, as shown in step 120 of FIG. Show. Wherein the second prepolymer has at least one hydrophilic side chain group, such as a carboxylic acid group, a sulfonic acid group (-SO 3 H), a phosphoric acid group (-OPO 3 H 2 ) or a phosphonic acid group (-PO 3 H 2 ).

在式(II)之反應中,式(II-1)係指含羧酸基化合物(d),而式(II-2)係指第二預聚物,a、b、c同前所述,d可為0.8至1.5,n係視實際需求而異,在一定範圍內使式(II-2)之第二預聚物的算數平均分子量可例如為2000至6000,且黏度可例如為2500cps至30000cps(測試溫度:70℃),惟本發明並不限於此處所舉。 In the reaction of the formula (II), the formula (II-1) means a carboxylic acid group-containing compound (d), and the formula (II-2) means a second prepolymer, a, b, c are as described above. , d may be from 0.8 to 1.5, and n varies depending on actual needs, and the arithmetic average molecular weight of the second prepolymer of the formula (II-2) may be, for example, from 2,000 to 6,000, and the viscosity may be, for example, 2,500 cps, within a certain range. Up to 30,000 cps (test temperature: 70 ° C), but the invention is not limited thereto.

再來,如步驟130所示,待第二預聚物冷卻至60~70℃後,加入中和劑(e)並進行分散步驟約5分鐘,以中和第二預聚物,所形成之第二預聚物如式(III-1)~(III-3)所示,然以式(III-1)及(III-3)為較佳。 Then, as shown in step 130, after the second prepolymer is cooled to 60-70 ° C, the neutralizing agent (e) is added and the dispersion step is carried out for about 5 minutes to neutralize the second prepolymer. The second prepolymer is represented by the formulae (III-1) to (III-3), and the formulae (III-1) and (III-3) are preferred.

然後,如步驟140所示,將經中和後之第二預聚物添加至溶劑(h)中以稀釋第二預聚物。 Then, as shown in step 140, the neutralized second prepolymer is added to the solvent (h) to dilute the second prepolymer.

接著,如步驟150所示,將經稀釋的第二預聚物添加至分散劑(f)與水的混合溶液中,並進行分散步驟,以形成分散液。 Next, as shown in step 150, the diluted second prepolymer is added to the mixed solution of the dispersant (f) and water, and a dispersion step is carried out to form a dispersion.

上述之分散步驟可利用市售攪拌、混合、震盪設備等進行,使前述經中和後之第二預聚物均勻分散於分散劑(f)及水中,形成分散液。 The above dispersion step can be carried out by using a commercially available stirring, mixing, shaking apparatus or the like, and the neutralized second prepolymer is uniformly dispersed in the dispersing agent (f) and water to form a dispersion.

之後,將含有前述第二預聚物之分散液與二胺化合物(g),於30℃至50℃下進行鏈延長反應約1小時至約20小時,然以約1小時至約16小時為較佳,以製得水性PU樹脂(A),如圖1之步驟160所示。 Thereafter, the dispersion containing the second prepolymer and the diamine compound (g) are subjected to a chain extension reaction at 30 ° C to 50 ° C for about 1 hour to about 20 hours, and then for about 1 hour to about 16 hours. Preferably, the aqueous PU resin (A) is produced as shown in step 160 of FIG.

經上述方法製得之水性PU樹脂(A)可進行分散步驟,上述之分散步驟可例如在室溫下,以市售之攪拌設備持續攪拌約16小時,而製得分散均勻之水性PU樹脂(A)。 The aqueous PU resin (A) obtained by the above method can be subjected to a dispersion step, which can be continuously stirred for about 16 hours at room temperature, for example, at a room temperature to obtain a uniformly dispersed aqueous PU resin ( A).

本發明之一特徵在於透過限定水性PU樹脂(A) 中聚碳酸酯多元醇(b)以及羧酸基的含量,有利於後述之高彩度水性PU樹脂仿麂皮複合材料用之多孔層的製造。所得之100重量份的水性PU樹脂(A)中,包含60重量份至68重量份之聚碳酸酯多元醇(b)以及0.9重量份至1.3重量份之羧酸基。 One of the features of the present invention is that the water-soluble PU resin (A) is defined. The content of the medium polycarbonate polyol (b) and the carboxylic acid group is advantageous for the production of a porous layer for a high-color aqueous PU resin-like suede composite material to be described later. The obtained 100 parts by weight of the aqueous PU resin (A) contains 60 parts by weight to 68 parts by weight of the polycarbonate polyol (b) and 0.9 parts by weight to 1.3 parts by weight of the carboxylic acid group.

高彩度水性聚氨基甲酸酯樹脂仿麂皮複合材料用之多孔層的製造方法Method for producing porous layer for high chroma water-based polyurethane resin-like suede composite material 一、進行乾式塗佈步驟First, the dry coating step

首先,在一實施例中,進行乾式塗佈步驟,將高彩度水性聚氨基甲酸酯樹脂(polyurethane;PU)組成物(F)塗佈於基材之至少一表面。上述乾式塗佈步驟所塗佈之高彩度水性PU樹脂組成物(F)可不具圖案(例如作為底塗層)或具有圖案(例如作為頂塗層)。 First, in one embodiment, a dry coating step is performed to apply a high chroma waterborne polyurethane (PU) composition (F) to at least one surface of the substrate. The high chroma water-based PU resin composition (F) coated by the above dry coating step may be unpatterned (for example, as an undercoat layer) or have a pattern (for example, as a top coat layer).

在一例示中,本發明使用之基材並無限制,可為著紙、不織布、織物或樹脂薄膜。大體而言,前述高彩度水性PU樹脂組成物(F)可塗佈於基材之一表面或二表面,且前述高彩度水性PU樹脂組成物(F)於基材表面之塗佈量一般為100gr/cm2至200gr/cm2In one example, the substrate used in the present invention is not limited, and may be a paper, a nonwoven fabric, a woven fabric or a resin film. In general, the high-color aqueous PU resin composition (F) may be applied to one surface or both surfaces of the substrate, and the coating amount of the high-color aqueous PU resin composition (F) on the surface of the substrate is generally 100 gr/ Cm 2 to 200 gr/cm 2 .

在上述實施例中,高彩度水性PU樹脂組成物(F)可包括前述之水性PU樹脂(A)、顏料(B)、發泡助劑(C)及架橋劑(D),其中水性PU樹脂(A)悉如前述,此處不再贅言,以下就其他成份分述之。 In the above embodiment, the high chroma water-based PU resin composition (F) may include the aforementioned aqueous PU resin (A), pigment (B), foaming auxiliary (C), and bridging agent (D), wherein the aqueous PU resin ( A) As mentioned above, there is no longer a rumor here, and the other components are described below.

顏料(B)Pigment (B)

本發明之顏料(B)可為水溶性陰離子分散型顏料,且可為無機顏料或有機顏料,其中無機顏料係有金屬氧化物、或金屬錯鹽等之金屬化合物,其具體例如:鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、亞鉛、銻等之金屬氧化物,以及前述金屬之複合氧化物。有機顏料的具體例如:C.I.顏料黃1,3,11,12,13,14,15,16,17,20,24,31,53,55,60,61,65,71,73,74,81,83,93,95,97,98,99,100,101,104,106,108,109,110,113,114,116,117,119,120,126,127,128,129,138,139,150,151,152,153,154,155,156,166,167,168,175;C.I.顏料橙1,5,13,14,16,17,24,34,36,38,40,43,46,49,51,61,63,64,71,73;C.I.顏料紅1,2,3,4,5,6,7,8,9,10,11,12,14,15,16,17,18,19,21,22,23,30,31,32,37,38,40,41,42,48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,53:1,57,57:1,57:2,58:2,58:4,60:1,63:1,63:2,64:1,81:1,83,88,90:1,97,101,102,104,105,106,108,112,113,114,122,123,144,146,149,150,151,155,166,168,170,171,172,174,175,176,177,178,17 9,180,185,187,188,190,193,194,202,206,207,208,209,215,216,220,224,226,242,243,245,254,255,264,265;C.I.顏料紫1,19,23,29,32,36,38,39;C.I.顏料藍1,2,15,15:3,15:4,15:6,16,22,60,66、WUB Blue 1C059(大恭化學);C.I.顏料綠7,36,37;C.I.顏料棕23,25,28;C.I.顏料黑1,7、WUB Black 1C058(大恭化學)等前述顏料可單獨一種或混合複數種使用。基於水性PU樹脂(A)之使用量為100重量份,上述之顏料(B)的使用量係2重量份至6重量份。 The pigment (B) of the present invention may be a water-soluble anionic dispersion type pigment, and may be an inorganic pigment or an organic pigment, wherein the inorganic pigment is a metal compound such as a metal oxide or a metal-stack salt, and specific examples thereof include iron and cobalt. A metal oxide of aluminum, cadmium, lead, copper, titanium, magnesium, chromium, lead, bismuth, or the like, and a composite oxide of the foregoing metals. Specific examples of organic pigments are: CI Pigment Yellow 1,3,11,12,13,14,15,16,17,20,24,31,53,55,60,61,65,71,73,74,81 , 83,93,95,97,98,99,100,101,104,106,108,109,110,113,114,116,117,119,120,126,127,128,129,138,139,150,151,152,153,154,155,156,166,167,168,175; CI Pigment Orange 1,5,13,14,16,17,24,34,36,38,40,43,46,49,51,61,63, 64,71,73; CI Pigment Red 1,2,3,4,5,6,7,8,9,10,11,12,14,15,16,17,18,19,21,22,23 ,30,31,32,37,38,40,41,42,48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,53 :1,57,57:1,57:2,58:2,58:4,60:1,63:1,63:2,64:1,81:1,83,88,90:1,97,101,102,104,105,106,108,112,113,114,122,123,144,146,149,150,151,155,166,168,170,171,172,174,175,176,177,178 ,17 9,180,185,187,188,190,193,194,202,206,207,208,209,215,216,220,224,226,242,243,245,254,255,264,265; CI Pigment Violet 1,19,23,29,32,36,38,39;CI Pigment Blue 1,2,15,15:3,15:4,15:6,16,22,60,66, WUB Blue 1C059 (Da Gong Chemical); CI Pigment Green 7,36,37; CI Pigment Brown 23,25,28; CI Pigment Black 1,7, WUB Black 1C058 (Da Gong Chemical), etc. The above pigments may be used alone or in combination. A variety of uses. The pigment (B) is used in an amount of 2 parts by weight to 6 parts by weight based on 100 parts by weight of the aqueous PU resin (A).

若上述之顏料(B)的使用量低於2重量份,則無法達到預定的彩度。若上述之顏料(B)的使用量高於6重量份,雖可提高彩度,但浪費顏料,也會造成摩擦堅牢度不佳而易掉色的問題。 If the amount of the above pigment (B) used is less than 2 parts by weight, the predetermined chroma cannot be achieved. If the amount of the above pigment (B) is more than 6 parts by weight, although the chroma can be improved, the waste of the pigment causes a problem that the friction fastness is poor and the color is easily lost.

發泡助劑(C)Foaming aid (C)

本發明使用之發泡助劑(C),其中此發泡助劑(C)可包括但不限於碳數5至17之碳氫化合物溶劑,此碳氫化合物溶劑為不溶於水但其揮發速率係低於水之揮發速率。 The foaming aid (C) used in the present invention, wherein the foaming assistant (C) may include, but is not limited to, a hydrocarbon solvent having a carbon number of 5 to 17, which is insoluble in water but has a volatilization rate It is lower than the evaporation rate of water.

上述適用之發泡助劑(C)的具體例如:商品名IP SOLVENT(例如IP SOLVENT 1016、IP SOLVENT 1620及IP SOLVENT 2028等)系列產品(日本出光興產製);商品名NA SOLVENT系列產品(日本日油製);商品名ISOPAR系列產品(美國ExxonMobil Chemical製),然以IP SOLVENT 1620為較佳。上述發泡助劑(C)可單獨 一種或混合複數種使用。一般而言,基於水性PU樹脂(A)之使用量為100重量份,發泡助劑(C)之使用量為20重量份至60重量份。 Specific examples of the above-mentioned suitable foaming auxiliaries (C) are, for example, IP SOLVENT (for example, IP SOLVENT 1016, IP SOLVENT 1620 and IP SOLVENT 2028, etc.) series products (produced by Nippon Ignaku Co., Ltd.); trade name NA SOLVENT series products ( Nippon Oil Co., Ltd.; trade name ISOPAR series products (manufactured by ExxonMobil Chemical Co., USA), preferably IP SOLVENT 1620. The above foaming aid (C) can be used alone One or a mixture of multiple uses. In general, the amount of the foaming auxiliary (C) used is from 20 parts by weight to 60 parts by weight based on 100 parts by weight of the aqueous PU resin (A).

若上述之發泡助劑(C)的使用量低於20重量份,則所得之多孔層會因連續孔不足而有多孔層表面粗糙、觸感不佳及柔軟度不足等缺點。倘若發泡助劑(C)之使用量超過60重量份,則不易分散且後續所得之多孔層會因過多的連續孔而有過於柔軟及成形性不佳等缺點。 When the amount of the above-mentioned foaming auxiliary (C) is less than 20 parts by weight, the obtained porous layer may have disadvantages such as a rough surface of the porous layer, a poor touch, and insufficient softness due to insufficient continuous pores. When the amount of the foaming aid (C) used exceeds 60 parts by weight, it is difficult to disperse and the porous layer obtained in the subsequent manner may be disadvantageous in that it is too soft and has poor formability due to excessive continuous pores.

架橋劑(D)Bridging agent (D)

在一實施例中,適用於本發明之架橋劑(D)係由架橋劑原液及水以體積比1:1混合而成。而上述架橋劑原液的具體例可包含但不限於聚碳化二亞胺(polycarbodiimide)、水分散型異氰酸化合物(例如封閉型或未封閉型異氰酸化合物及聚異氰酸酯等)、胺類化合物〔例如三聚氰胺(melamine)〕、氮丙啶(aziridine)化合物〔例如聚氮丙啶(polyaziridine)〕及環氧樹脂樹脂以及上述之任意組合。上述架橋劑(D)可單獨一種或混合複數種使用。 In one embodiment, the bridging agent (D) suitable for use in the present invention is formed by mixing a bridging agent stock solution and water in a volume ratio of 1:1. Specific examples of the above-mentioned bridging agent stock solution may include, but are not limited to, polycarbodiimide, water-dispersed isocyanate compounds (for example, blocked or unblocked isocyanate compounds and polyisocyanates), and amine compounds. [e.g., melamine], aziridine compound (e.g., polyaziridine), and epoxy resin, and any combination thereof. The above-mentioned bridging agent (D) may be used singly or in combination of plural kinds.

一般而言,基於水性PU樹脂(A)的使用量為100重量份,架橋劑(D)的使用量可為0.5重量份至4重量份。若架橋劑(D)的使用量低於0.5重量份,則後續製得之多孔層強度不足。若架橋劑(D)的使用量高於4重量份,則後續所得之多孔層有過硬及柔軟性不佳等缺點。 In general, the bridging agent (D) can be used in an amount of from 0.5 part by weight to 4 parts by weight based on 100 parts by weight of the aqueous PU resin (A). If the amount of the bridging agent (D) used is less than 0.5 parts by weight, the strength of the subsequently produced porous layer is insufficient. If the amount of the bridging agent (D) used is more than 4 parts by weight, the subsequently obtained porous layer has disadvantages such as excessive hardness and poor flexibility.

添加劑(E)Additive (E)

在一實施例中,本發明可選擇性添加包括增黏劑(E-1)、消泡劑(E-2)、造膜劑(E-3)或感熱凝固劑(E-4)等添加劑(E),以製得手感及彩度更佳之多孔層。 In one embodiment, the present invention may optionally add an additive such as a tackifier (E-1), an antifoaming agent (E-2), a film former (E-3) or a heat sensitive coagulant (E-4). (E) to produce a porous layer with better hand and chroma.

上述之增黏劑(E-1)可使用任何市售產品,其具體例如台昌樹脂企業製增黏劑(IV3800)或台灣日華化學製增黏劑(NEOSTECKER),惟本發明並非限定於此。 Any of the commercially available products may be used as the tackifier (E-1), and specifically, for example, a tackifier (IV3800) manufactured by Taichang Resin Co., Ltd. or a tackifier (NEOSTECKER) made by Taiwan Rihua Chemical Co., Ltd., but the present invention is not limited thereto. this.

上述之消泡劑(E-2)之具體例如:聚矽氧系、高級醇系、聚醚系、脂肪酸酯系、聚乙二醇系及礦物油系等化合物。上述之消泡劑可單獨一種或混合複數種使用。 Specific examples of the antifoaming agent (E-2) described above include compounds such as polyoxymethylene, higher alcohols, polyethers, fatty acid esters, polyethylene glycols, and mineral oils. The above antifoaming agents may be used singly or in combination of plural kinds.

上述之造膜劑(E-3)可使用任何市售產品,其具體例如立德盛有限公司製成膜劑(RY903),惟本發明不限定於此。 Any commercially available product can be used as the above-mentioned film-forming agent (E-3), and specifically, for example, a filming agent (RY903) is produced by Lidesheng Co., Ltd., but the present invention is not limited thereto.

上述之感熱凝固劑(E-4)可使用任何市售產品,更佳為矽族感熱凝固劑,可提高所製得之多孔層的彩度。舉例來說,感熱凝固劑(E-4)具體例如分子中有伸乙氧基(ethyleneoxide group)的化合物FA-3031(購於信越化学工業株式会社)、TPA4380(購於邁圖公司)及CoagulantW(購於拜耳公司),其中以FA-3031較佳。此外,可在感熱凝固劑(E-4)中添加NaCl及CaCl2等無機鹽類。 The above-mentioned thermosensitive coagulant (E-4) can be used in any commercially available product, more preferably a steroidal thermosetting agent, and the chroma of the obtained porous layer can be improved. For example, the thermosensitive coagulant (E-4) is specifically, for example, a compound having an ethylene oxide group in the molecule, FA-3031 (purchased from Shin-Etsu Chemical Co., Ltd.), TPA4380 (purchased from Momentive Corporation), and Coagulant W. (purchased from Bayer), of which FA-3031 is preferred. Further, an inorganic salt such as NaCl or CaCl 2 may be added to the thermosensitive coagulant (E-4).

一般而言,基於水性PU樹脂(A)之使用量為100重量份,增黏劑(E-1)之使用量為0重量份至6重量份,消泡劑(E-2)之使用量為0重量份至0.3重量份,造膜劑 (E-3)之使用量為0重量份至3重量份,且感熱凝固劑(E-4)之使用量為0重量份至3重量份。 In general, the amount of the tackifier (E-1) used is from 0 parts by weight to 6 parts by weight based on 100 parts by weight of the aqueous PU resin (A), and the amount of the antifoaming agent (E-2) is used. From 0 parts by weight to 0.3 parts by weight, a film former (E-3) is used in an amount of from 0 part by weight to 3 parts by weight, and the heat-sensitive coagulant (E-4) is used in an amount of from 0 part by weight to 3 parts by weight.

此外,除上述之添加劑(E)外,本發明之高彩度水性PU樹脂組成物(F)更可包含分散劑(例如花王股份有限公司製的Rheodol AO-15V,HLB3.5),以提高所製得之多孔層的手感,且不會降低摩擦堅牢度。 Further, in addition to the above-mentioned additive (E), the high-color aqueous PU resin composition (F) of the present invention may further contain a dispersing agent (for example, Rheodol AO-15V, HLB3.5 manufactured by Kao Co., Ltd.) to improve the preparation. The hand of the porous layer is obtained without reducing the friction fastness.

在利用前述之高彩度水性PU樹脂組成物(F)塗佈於基材上後,接著對基材進行加熱處理,以製得多孔層。 After coating the substrate with the high-color aqueous PU resin composition (F) described above, the substrate is then subjected to heat treatment to obtain a porous layer.

需要說明的是,當所使用之基材表面不平整時,可先進行上述乾式塗佈步驟之底塗步驟。本處所指之底塗步驟可使用高彩度水性PU樹脂組成物(F),或利用水性PU樹脂(A)與市售之丙烯樹脂或聚酯樹脂等(例如大立化工,商品名R-235之丙烯酸樹脂)以各50重量份摻混,再添加0至4重量份之顏料(B)、0至100重量份之發泡助劑(C)、2重量份之架橋劑(D)以及0至5重量份之增黏劑(E-1)所形成的底塗組成物,塗佈於具有不平整表面之基材上,可得較平整之表面。 It should be noted that when the surface of the substrate to be used is not flat, the primer coating step of the above dry coating step may be performed first. The primer step referred to herein may be a high chroma water-based PU resin composition (F), or an aqueous PU resin (A) and a commercially available acrylic resin or polyester resin (for example, Dali Chemical Co., Ltd. under the trade name R-235). Acrylic resin is blended in an amount of 50 parts by weight, and further added 0 to 4 parts by weight of the pigment (B), 0 to 100 parts by weight of the foaming aid (C), 2 parts by weight of the bridging agent (D), and 0 to The undercoat composition formed by 5 parts by weight of the tackifier (E-1) is applied to a substrate having an uneven surface to obtain a flat surface.

二、加熱處理Second, heat treatment

接著,對塗佈上述之高彩度水性PU樹脂組成物(F)的基材進行加熱處理,以形成多孔層。 Next, the substrate coated with the above-described high chroma water-based PU resin composition (F) is subjected to heat treatment to form a porous layer.

上述之加熱處理係在80℃至130℃之溫度下進行,以去除高彩度水性PU樹脂組成物(F)的水份,使高彩度水性PU樹脂組成物(F)固化並形成塗佈層,以及藉由發泡助劑(C)揮發而形成多孔層,且上述之多孔層具有複數 個連續孔。特別說明的是,上述之加熱處理的溫度雖越低可得越佳之彩度與手感,然而若溫度太低則會造成氣泡的產生,故以上述之範圍為佳。 The above heat treatment is carried out at a temperature of 80 ° C to 130 ° C to remove moisture of the high chroma water-based PU resin composition (F), to cure the high chroma water-based PU resin composition (F) and form a coating layer, and to borrow a foaming aid (C) volatilizes to form a porous layer, and the porous layer has a plurality of One continuous hole. In particular, the lower the temperature of the above heat treatment, the better the chroma and the hand feeling. However, if the temperature is too low, the generation of bubbles is caused, so the above range is preferred.

此外,所得之多孔層不需經過起毛處理,且多孔層與基材層間不存在任何黏著層。 Further, the obtained porous layer does not need to be subjected to raising treatment, and there is no adhesive layer between the porous layer and the substrate layer.

經過上述方法所製得的水性PU樹脂(A)不需使用大量有機溶劑,且利用水性PU樹脂(A)製得的高彩度水性PU樹脂組成物(F)不需要額外添加超細纖維、粉體添加劑或發泡劑。此外,利用高彩度水性PU樹脂組成物(F)所製得之多孔層具有不低於5的彩度、不低於4級的摩擦堅牢度以及好的仿麂皮手感。 The aqueous PU resin (A) obtained by the above method does not require the use of a large amount of organic solvent, and the high-color aqueous PU resin composition (F) obtained by using the aqueous PU resin (A) does not require the addition of ultrafine fibers and powders. Additive or foaming agent. Further, the porous layer obtained by using the high chroma water-based PU resin composition (F) has a chroma of not less than 5, a friction fastness of not less than 4 grades, and a good suede feel.

以下利用實施例以說明本發明之應用,然其並非用以限定本發明,本發明技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾。 The following examples are provided to illustrate the application of the present invention, and are not intended to limit the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention.

製備水性PU樹脂Preparation of waterborne PU resin 合成例1Synthesis Example 1

此合成例係將100.8重量份之六亞甲基二異氰酸酯(hexamethylenediisocynate;HMDI;a)、256.6重量份之聚碳酸酯二醇(Nippollan-965,日本poly製;b-1)以及3.6重量份之1,3-丁二醇(1,3-buthyleneglycol;c-1)混合攪拌,並於80~90℃下加熱2.5小時,以形成第一預聚物。將第一預聚物冷卻至70~75℃後,再加入0.27重量份之三甲醇丙烷(trimethylolpropane;c-2)及13.41重量份之 二羥甲基丙酸(dimethylol propionoc acid;DMPA;d),在70~75℃的溫度下反應,以合成第二預聚物。 This synthesis example is 100.8 parts by weight of hexamethylenediisocynate (HMDI; a), 256.6 parts by weight of a polycarbonate diol (Nippollan-965, manufactured by Nippon Poly; b-1), and 3.6 parts by weight. 1,3-Buthyleneglycol (c-1) was stirred and heated at 80 to 90 ° C for 2.5 hours to form a first prepolymer. After cooling the first prepolymer to 70-75 ° C, 0.27 parts by weight of trimethylolpropane (c-2) and 13.41 parts by weight are further added. Dimethylol propionoc acid (DMPA; d) is reacted at a temperature of 70 to 75 ° C to synthesize a second prepolymer.

當第二預聚物達特定黏度(例如4400cps/70℃)時,冷卻至65℃後,加入17.2重量份之N-甲基嗎啉(N-methylmorpholine;N-mmp;e),攪拌5分鐘後,再加入30重量份之丙酮(acetone;h)進行稀釋。之後,加入11.94重量份之分散劑(Triton X-100,陶氏化學公司;HLB 14.1;f-2),持續攪拌分散或高速攪拌(轉速6000~10000rpm)分散15分鐘後,以製得分散液。 When the second prepolymer reaches a specific viscosity (for example, 4400 cps/70 ° C), after cooling to 65 ° C, 17.2 parts by weight of N-methylmorpholine (N-methylp; e) is added and stirred for 5 minutes. Thereafter, 30 parts by weight of acetone (acetone; h) was further added for dilution. Thereafter, 11.94 parts by weight of a dispersant (Triton X-100, Dow Chemical Co., Ltd.; HLB 14.1; f-2) was added, and the dispersion was continuously stirred or rapidly stirred (speed: 6000 to 10000 rpm) for 15 minutes to prepare a dispersion. .

接著,加入20.7重量份之含10重量百分比之哌嗪的水溶液(piperazine;g),在40~50℃下攪拌並反應1小時,再置於室溫中持續攪拌16小時,製得水性聚氨基甲酸酯(polyurethane;PU)樹脂(A)。 Next, 20.7 parts by weight of an aqueous solution (piperazine; g) containing 10% by weight of piperazine was added, stirred at 40 to 50 ° C for 1 hour, and further stirred at room temperature for 16 hours to obtain an aqueous polyamino group. Polyurethane (PU) resin (A).

合成例2至13以及合成比較例1至8Synthesis Examples 2 to 13 and Synthesis Comparative Examples 1 to 8

合成例2至13以及合成比較例1至8係使用與合成例1相同的製作方法,不同處在於合成例2至13以及合成比較例1至8係改變原料的種類及使用量;其配方及相關物性如表1至表2所列。 Synthesis Examples 2 to 13 and Synthesis Comparative Examples 1 to 8 used the same production method as in Synthesis Example 1, except that Synthesis Examples 2 to 13 and Synthesis Comparative Examples 1 to 8 were used to change the kind and amount of raw materials; Relevant physical properties are listed in Tables 1 to 2.

製備高彩度水性PU樹脂仿麂皮織物用之多孔層Preparation of porous layer for high chroma waterborne PU resin suede fabric 實施例1Example 1

實施例1係將100重量份之合成例1的水性PU樹脂(A)與2重量份的架橋劑(150HD;台昌樹脂;D) 混合並攪拌(轉速500rpm)1分鐘,將40重量份的發泡助劑(IP SOLVENT 1620;日本出光興產;C-1)分兩次加入後,將攪拌轉速自500rpm調升至2000rpm並持續1分鐘,再加入4重量份之顏料(WUB Black 1C058;大恭化學;B-2),以2000rpm之轉速攪拌1分鐘,之後加入0.44重量份之增黏劑(商品名NEOSTECKER;台灣日華化學;E-1)攪拌並調整黏度(例如15000cps/25℃),以形成高彩度水性聚氨基甲酸酯樹脂組成物(F)。 Example 1 is 100 parts by weight of the aqueous PU resin (A) of Synthesis Example 1 and 2 parts by weight of a bridging agent (150HD; Taichang Resin; D) After mixing and stirring (500 rpm) for 1 minute, 40 parts by weight of foaming aid (IP SOLVENT 1620; Japan Idemitsu Co., Ltd.; C-1) was added in two portions, and the stirring speed was increased from 500 rpm to 2000 rpm and continued. 1 minute, add 4 parts by weight of pigment (WUB Black 1C058; Da Kung Chemical; B-2), stir at 2000 rpm for 1 minute, then add 0.44 parts by weight of tackifier (trade name NEOSTECKER; Taiwan Rihua Chemical E-1) Stir and adjust the viscosity (for example, 15000 cps/25 ° C) to form a high chroma water-based polyurethane resin composition (F).

實施例2至18以及比較例1至9Examples 2 to 18 and Comparative Examples 1 to 9

實施例2至18以及比較例1至9係使用與實施例1相同的製作方法,不同處在於實施例2至18以及比較例1至9係改變原料的種類及使用量。其配方及相關評價結果如表1至表4所列。 In Examples 2 to 18 and Comparative Examples 1 to 9, the same production method as in Example 1 was used, except that Examples 2 to 18 and Comparative Examples 1 to 9 were used to change the kind and amount of the raw materials. The formulation and related evaluation results are listed in Tables 1 to 4.

高彩度水性PU樹脂仿麂皮織物用之多孔層塗佈製程Porous layer coating process for high chroma water-based PU resin-like suede fabric

接下來將高彩度水性PU樹脂組成物(F)利用乾式塗佈法以150gr/cm2之塗佈量塗佈於基材上。接著,將塗佈後之基材置於約110℃之烘箱中,烘烤約3分鐘,以去除高彩度水性PU樹脂組成物(F)之水份,同時使其固化而形成塗佈層,並使發泡助劑(C)揮發而形成多孔層。之後,評價多孔層的彩度、手感、膜強度及乾/溼狀態下之摩擦堅牢度,其結果如表3至表4所示,而相關的評價方法容後再述。 Next, the high chroma water-based PU resin composition (F) was applied onto the substrate by a dry coating method at a coating amount of 150 gr/cm 2 . Next, the coated substrate is placed in an oven at about 110 ° C and baked for about 3 minutes to remove the moisture of the high chroma water-based PU resin composition (F) while curing to form a coating layer, and The foaming aid (C) is volatilized to form a porous layer. Thereafter, the chroma, the hand feeling, the film strength, and the rubbing fastness in the dry/wet state of the porous layer were evaluated, and the results are shown in Tables 3 to 4, and the relevant evaluation methods will be described later.

評價方式Evaluation method

1.彩度1. chroma

本發明此處所稱之彩度係以DATACOLOR 600分光光度計測得之C*值作為評價標準,所述之C*係以下式(IV)計算而得: The chroma referred to in the present invention is a C* value measured by a DATACOLOR 600 spectrophotometer, and the C* is calculated by the following formula (IV):

上式(IV)之a與b係由分光光度計所測得,與標準品間顏色差異之參數。當上式(IV)所得之C*越大,表示彩度越高。 The a and b of the above formula (IV) are parameters measured by a spectrophotometer and the color difference from the standard. The larger the C* obtained by the above formula (IV), the higher the chroma.

2.手感2. feel

利用手觸摸上述實施例1至18及比較例1至9製得之多孔層表面,以評估其觸感及柔軟度,相關評價標準如下: The surfaces of the porous layers prepared in the above Examples 1 to 18 and Comparative Examples 1 to 9 were touched by hand to evaluate the touch and softness, and the relevant evaluation criteria were as follows:

○:較佳(表面較細緻、觸感較溼潤,且柔軟度皆佳) ○: better (the surface is finer, the touch is moist, and the softness is good)

△:普通(表面、觸感以及柔軟度居次) △: Normal (surface, touch and softness)

×:不良(表面較粗、觸感較乾澀,且柔軟度皆差) ×: Poor (the surface is thicker, the touch is dryer, and the softness is poor)

特別說明的是,當符號「~」在上述圖例的左邊,表示比圖例代表的評價標準差,例如:「~△」即表示比△差一點。反之,當符號「~」在上述圖例的右邊,則表示比圖例代表的評價標準好。 In particular, when the symbol "~" is on the left side of the above-mentioned legend, it indicates a difference from the evaluation standard represented by the legend. For example, "~△" means that it is a little worse than Δ. Conversely, when the symbol "~" is on the right side of the above legend, it means that it is better than the evaluation standard represented by the legend.

3.膜強度3. Film strength

本發明所述之膜強度係指塗佈於基材上之高彩度水性聚氨基甲酸酯樹脂(F)之抗剝離程度。本評價方法係利用指甲刮磨塗佈有高彩度水性PU樹脂(F)之基材表面,以判定高彩度水性PU樹脂(F)之剝離程度。相關評價標準如下: The film strength according to the present invention means the degree of peeling resistance of the high chroma water-based polyurethane resin (F) applied to the substrate. In the evaluation method, the surface of the substrate coated with the high chroma water-based PU resin (F) was scraped with a nail to determine the degree of peeling of the high chroma water-based PU resin (F). The relevant evaluation criteria are as follows:

○:較佳(表面之水性聚氨基甲酸酯樹脂不易脫落) ○: preferably (the surface of the aqueous polyurethane resin is not easy to fall off)

△:普通(表面之水性聚氨基甲酸酯樹脂會些許脫落) △: Normal (the surface of the waterborne polyurethane resin will peel off a little)

×:不良(表面之水性聚氨基甲酸酯樹脂容易脫落) ×: Poor (the surface of the water-based polyurethane resin is easy to fall off)

4.摩擦堅牢度(乾)4. Friction fastness (dry)

本案此處所述之摩擦堅牢度,係分為乾式及溼式。乾式摩擦堅牢度係利用摩擦試驗機上,裝設乾白棉布,以10秒10次之頻率,來回摩擦塗佈有本發明之高彩度水性PU樹脂組成物(F)的基材,以確認塗佈於基材上之高彩度水性PU樹脂組成物(F)之在乾式摩擦下的摩擦堅牢度。評價標準係由數字1~5表示,數字越大表堅牢度越佳。 The friction fastness described in this case is divided into dry and wet. Dry friction fastness was carried out by using a dry white cotton cloth on a friction tester, and rubbing the substrate coated with the high chroma water-based PU resin composition (F) of the present invention back and forth at a frequency of 10 times 10 times to confirm the coating. The fastness of the high chroma water-based PU resin composition (F) on the substrate under dry rubbing. The evaluation criteria are represented by numbers 1 to 5. The greater the number, the better the table fastness.

5.摩擦堅牢度(溼)5. Friction fastness (wet)

溼式摩擦堅牢度之試驗方法與上述摩擦乾式堅牢度相同,惟上述之乾白棉布以溼白棉布替換,以確認塗佈於基材上之高彩度水性PU樹脂組成物(F)之在溼式摩擦下的摩擦堅牢度。評價標準係由數字1~5表示,數字越大表堅牢度越佳。 The test method of wet friction fastness is the same as the above-mentioned friction dry fastness, except that the above-mentioned dry white cotton cloth is replaced with a wet white cotton cloth to confirm that the high chroma water-based PU resin composition (F) coated on the substrate is in a wet state. Friction fastness under friction. The evaluation criteria are represented by numbers 1 to 5. The greater the number, the better the table fastness.

綜合表3至表4之結果,當實施例1至18所使用之水性PU樹脂(A)中,羧酸基含量在0.9重量份至1.3重量份,且聚碳酸酯多元醇(b)之含量在60重量份至68重量份,再添加適當份量之顏料(B)、發泡助劑(C)及架橋劑(D)時,所製得之高彩度水性PU樹脂組成物(F)塗佈於基材上後,經加熱處理而製得的多孔層可具有大於5的彩度以及不低於4級的摩擦堅牢度。 From the results of Tables 3 to 4, in the aqueous PU resin (A) used in Examples 1 to 18, the carboxylic acid group content was from 0.9 part by weight to 1.3 parts by weight, and the content of the polycarbonate polyol (b) The high-color aqueous PU resin composition (F) obtained by applying the appropriate amount of the pigment (B), the foaming auxiliary (C), and the bridging agent (D) in an amount of 60 parts by weight to 68 parts by weight After the substrate, the porous layer obtained by heat treatment may have a chroma of more than 5 and a friction fastness of not less than 4 grades.

相較之下,如表4所示,比較例2以聚醚類所製得多孔層,無法達到預定彩度及手感。比較例4所含之聚碳酸酯多元醇過少,則無法達到預定的彩度。而由比較例5可知,若水性PU樹脂所含之羧酸基過多,則造成手感不佳的問題。再者,如比較例6所示,若在水性PU樹脂中未添加二胺化合物,則所得之多孔層膜強度低。 In contrast, as shown in Table 4, in Comparative Example 2, a porous layer was obtained by using a polyether, and the predetermined chroma and hand were not obtained. When the polycarbonate polyol contained in Comparative Example 4 was too small, the predetermined chroma could not be obtained. On the other hand, in Comparative Example 5, when the amount of the carboxylic acid group contained in the aqueous PU resin was too large, there was a problem that the hand feeling was not good. Further, as shown in Comparative Example 6, when the diamine compound was not added to the aqueous PU resin, the obtained porous layer film had low strength.

此外,利用本發明之方法製得的多孔層不需額外添加粉體添加劑或超細纖維,也不需經過起毛處理,即可製得具有仿皮革手感的多孔層,有利於仿麂皮複合材料的應用。 In addition, the porous layer obtained by the method of the invention does not need to add additional powder additives or ultrafine fibers, and does not need to be subjected to raising treatment to obtain a porous layer with a leather-like feel, which is advantageous for the suede composite material. Applications.

需補充的是,本發明雖以特定的化合物、組成、反應條件、製程、分析方法或特定儀器作為例示,說明本發明之高彩度水性聚氨基甲酸酯樹脂及其製造方法暨其於仿麂皮複合材料之應用,惟本發明所屬技術領域中任何具有通常知識者可知,本發明並不限於此,在不脫離本發明之精神和範圍內,本發明之高彩度水性聚氨基甲酸酯樹脂 及其製造方法亦可使用其他的化合物、組成、反應條件、製程、分析方法或儀器進行。 It should be noted that the present invention describes a high chroma water-based polyurethane resin of the present invention and a method for producing the same according to specific compounds, compositions, reaction conditions, processes, analytical methods or specific instruments, and the likes thereof. The use of the composite material, but it is to be understood by those skilled in the art that the present invention is not limited thereto, and the high chroma water-based polyurethane resin of the present invention is not deviated from the spirit and scope of the present invention. The method of manufacture and its methods of manufacture can also be carried out using other compounds, compositions, reaction conditions, processes, analytical methods or equipment.

由上述本發明實施方式可知,應用本發明之高彩度水性聚氨基甲酸酯樹脂及其製造方法其優點在於藉由控制水性PU樹脂所含的羧酸基及聚碳酸酯多元醇的含量,不需額外添加超細纖維、粉體填充劑以及不需經過起毛處理,直接塗佈所製得之高彩度水性聚氨基甲酸酯樹脂於基材上,即可得到具有良好彩度及仿麂皮手感的基材,且所得的基材亦具有良好的摩擦堅牢度。 It can be seen from the above embodiments of the present invention that the high chroma water-based polyurethane resin and the method for producing the same of the present invention have an advantage in that the content of the carboxylic acid group and the polycarbonate polyol contained in the aqueous PU resin is not required to be controlled. The ultra-fine fiber, the powder filler and the high-color water-based polyurethane resin obtained by directly coating the obtained high-color water-based polyurethane resin on the substrate can be obtained with good chroma and suede hand feeling. The substrate and the resulting substrate also have good friction fastness.

雖然本發明已以實施方式揭露如上,然其並非用以限定本發明,在本發明所屬技術領域中任何具有通常知識者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention. Any one of ordinary skill in the art to which the present invention pertains can make various changes without departing from the spirit and scope of the invention. The scope of protection of the present invention is therefore defined by the scope of the appended claims.

a:六亞甲基二異氰酸酯(hexamethylenediisocynate;HMDI) a: hexamethylenediisocynate (HMDI)

b-1:聚碳酸酯二醇(Nippollan-965,日本poly製) B-1: polycarbonate diol (Nippollan-965, manufactured by Japan Poly)

b-2:聚碳酸酯二醇(Nippollan-963,日本poly製) B-2: polycarbonate diol (Nippollan-963, manufactured by Japan Poly)

b':聚四氫呋喃醚(PTG-1000) b': polytetrahydrofuran ether (PTG-1000)

c-1:1,3-丁二醇(1,3-buthyleneglycol;1,3-BG) C-1: 1,3-butanediol (1,3-buthyleneglycol; 1,3-BG)

c-2:三甲醇丙烷(trimethylolpropane;TMP) C-2: trimethylolpropane (TMP)

d:二羥甲基丙酸(dimethylol propionoc acid;DMPA) d: dimethylol propionoc acid (DMPA)

e:N-甲基嗎啉(N-methylmorpholine;N-mmp) e: N-methylmorpholine (N-mmp)

f-1:Tergitol TMN 100(The Dow Chemical Company;HLB 14.4) F-1: Tergitol TMN 100 (The Dow Chemical Company; HLB 14.4)

f-2:TritonX-100(The Dow Chemical Company) F-2: TritonX-100 (The Dow Chemical Company)

g:哌嗪(piperazine) g: piperazine

h:丙酮(acetone) h: acetone (acetone)

B-1:WUB Blue 1C059(大恭化學) B-1: WUB Blue 1C059 (大恭化学)

B-2:WUB Black 1C058(大恭化學) B-2: WUB Black 1C058 (大恭化学)

C-1:IP SOLVENT 1620(日本出光興產) C-1: IP SOLVENT 1620 (Japan Idemitsu Kosan)

C-2:IP SOLVENT 1016(日本出光興產) C-2: IP SOLVENT 1016 (Japan Idemitsu Kosan)

D:150HD(台昌樹脂) D: 150HD (Taichang Resin)

E-1:商品名NEOSTECKER(台灣日華化學製)或台昌增黏劑(IV3800) E-1: Trade name NEOSTECKER (Taiwan Rihua Chemical Co., Ltd.) or Taichang Tackifier (IV3800)

E-3:商品名RY903(立德勝有限公司) E-3: trade name RY903 (Lide Desheng Co., Ltd.)

E-4:FA-3031(信越化学工業株式会社) E-4: FA-3031 (Shin-Etsu Chemical Co., Ltd.)

100‧‧‧方法 100‧‧‧ method

110、120、130、140、150、160‧‧‧步驟 110, 120, 130, 140, 150, 160‧ ‧ steps

Claims (16)

一種水性聚氨基甲酸酯樹脂之製造方法,包含:將二異氰酸酯化合物(a)、聚碳酸酯多元醇(b)與一第一含羥基化合物(c-1)進行一預聚合反應,以形成一第一預聚物;將該第一預聚物、一第二含羥基化合物(c-2)及一含羧酸基化合物(d)進行一聚合反應,以形成一第二預聚物,其中該第二預聚物具有至少一羧酸基;利用一中和劑(e)中和該第二預聚物;將經中和後之該第二預聚物添加至一溶劑(h)中以稀釋該第二預聚物;將經稀釋的第二預聚物添加至一分散劑(f)與水的一混合溶液中,以形成一分散液,其中該分散劑(f)為一含乙氧基之非離子型分散劑或一含乙氧基之陰離子型分散劑;以及將該分散液與二胺化合物(g)進行一鏈延長反應,以形成該水性聚氨基甲酸酯樹脂(A),其中該水性聚氨基甲酸酯樹脂(A)為一自身乳化型水性聚氨基甲酸酯樹脂,且其中基於該水性聚氨基甲酸酯樹脂(A)之總固含量為100重量份,該水性聚氨基甲酸酯樹脂(A)具有0.9重量份至1.3重量份之該羧酸基以及60重量份至68重量份之該聚碳酸酯多元醇(b),該分散劑(f)之含量為大於0重量份至小於7重量份,且該溶劑(h)與該水之一總使用量為 136.09重量份至144.07重量份。 A method for producing an aqueous polyurethane resin, comprising: prepolymerizing a diisocyanate compound (a), a polycarbonate polyol (b) and a first hydroxyl group-containing compound (c-1) to form a first prepolymer; a polymerization reaction of the first prepolymer, a second hydroxyl group-containing compound (c-2) and a carboxylic acid group-containing compound (d) to form a second prepolymer, Wherein the second prepolymer has at least one carboxylic acid group; neutralizing the second prepolymer with a neutralizing agent (e); and adding the neutralized second prepolymer to a solvent (h) Diluting the second prepolymer; adding the diluted second prepolymer to a mixed solution of a dispersing agent (f) and water to form a dispersion, wherein the dispersing agent (f) is a An ethoxylated nonionic dispersant or an ethoxylated anionic dispersant; and a chain extension reaction of the dispersion with the diamine compound (g) to form the aqueous polyurethane resin (A) wherein the aqueous polyurethane resin (A) is a self-emulsifiable aqueous polyurethane resin, and wherein the aqueous polyurethane is based thereon The urethane resin (A) has a total solid content of 100 parts by weight, and the aqueous polyurethane resin (A) has 0.9 parts by weight to 1.3 parts by weight of the carboxylic acid group and 60 parts by weight to 68 parts by weight. The polycarbonate polyol (b), the dispersant (f) is contained in an amount of more than 0 parts by weight to less than 7 parts by weight, and the total amount of the solvent (h) and the water is 136.09 parts by weight to 144.07 parts by weight. 根據申請專利範圍第1項所述之水性聚氨基甲酸酯樹脂之製造方法,其中該聚碳酸酯多元醇(b)包含聚碳酸酯二醇,且該聚碳酸酯二醇之算數平均分子量為700至3000。 The method for producing an aqueous polyurethane resin according to claim 1, wherein the polycarbonate polyol (b) comprises a polycarbonate diol, and the arithmetic mean molecular weight of the polycarbonate diol is 700 to 3000. 根據申請專利範圍第1項所述之水性聚氨基甲酸酯樹脂之製造方法,該第一含羥基化合物(c-1)及該第二含羥基化合物(c-2)為脂肪族多元醇。 The method for producing an aqueous polyurethane resin according to claim 1, wherein the first hydroxyl group-containing compound (c-1) and the second hydroxyl group-containing compound (c-2) are aliphatic polyols. 根據申請專利範圍第3項所述之水性聚氨基甲酸酯樹脂之製造方法,其中該第一含羥基化合物(c-1)包含1,3-丁二醇,且該第二含羥基化合物(c-2)包含三甲醇丙烷或丙三醇。 The method for producing an aqueous polyurethane resin according to claim 3, wherein the first hydroxyl group-containing compound (c-1) comprises 1,3-butylene glycol, and the second hydroxyl group-containing compound ( C-2) contains trimethylolpropane or glycerol. 根據申請專利範圍第1項所述之水性聚氨基甲酸酯樹脂之製造方法,其中該含羧酸基化合物(d)為一含羧酸基之短鏈多元醇,且該含羧酸基之短鏈多元醇之分子量或算數平均分子量為100至1000。 The method for producing an aqueous polyurethane resin according to claim 1, wherein the carboxylic acid group-containing compound (d) is a carboxylic acid group-containing short-chain polyol, and the carboxylic acid group-containing The short chain polyol has a molecular weight or an arithmetic mean molecular weight of from 100 to 1000. 根據申請專利範圍第5項所述之水性聚氨基甲酸酯樹脂之製造方法,其中該含羧酸基之短鏈多元醇包含二羥甲基丙酸及二羥甲基丁酸。 The method for producing an aqueous polyurethane resin according to claim 5, wherein the carboxylic acid group-containing short-chain polyol comprises dimethylolpropionic acid and dimethylolbutanoic acid. 根據申請專利範圍第1項所述之水性聚氨基甲酸酯樹脂之製造方法,其中該中和劑(e)包含一有機中和劑或一無機中和劑。 The method for producing an aqueous polyurethane resin according to claim 1, wherein the neutralizing agent (e) comprises an organic neutralizing agent or an inorganic neutralizing agent. 根據申請專利範圍第1項所述之水性聚氨基甲酸酯樹脂之製造方法,其中該水性聚氨基甲酸酯樹脂(A)具有3重量份至5重量份之該分散劑(f)。 The method for producing an aqueous polyurethane resin according to the above aspect of the invention, wherein the aqueous polyurethane resin (A) has 3 parts by weight to 5 parts by weight of the dispersing agent (f). 根據申請專利範圍第1項所述之水性聚氨基甲酸酯樹脂之製造方法,其中基於該水性聚氨基甲酸酯樹脂(A)具有0.05重量份至1重量份之該二胺化合物(g)。 The method for producing an aqueous polyurethane resin according to claim 1, wherein the aqueous polyurethane resin (A) has 0.05 to 1 part by weight of the diamine compound (g) based on the aqueous polyurethane resin (A). . 根據申請專利範圍第1項所述之水性聚氨基甲酸酯樹脂之製造方法,其中該溶劑(h)為丙酮、丁酮以及其組合。 The method for producing an aqueous polyurethane resin according to claim 1, wherein the solvent (h) is acetone, methyl ethyl ketone, and a combination thereof. 根據申請專利範圍第1項所述之水性聚氨基甲酸酯樹脂之製造方法,在該鏈延長反應後,更包含進行一攪拌步驟。 According to the method for producing an aqueous polyurethane resin according to the first aspect of the invention, after the chain extension reaction, a stirring step is further included. 根據申請專利範圍第1項所述之水性聚氨基甲酸酯樹脂之製造方法,其中該水性聚氨基甲酸酯樹脂(A)具有0.9重量份至1.0重量份之該羧酸基。 The method for producing an aqueous polyurethane resin according to claim 1, wherein the aqueous polyurethane resin (A) has from 0.9 part by weight to 1.0 part by weight of the carboxylic acid group. 根據申請專利範圍第1項所述之水性聚氨基甲酸酯樹脂之製造方法,其中該水性聚氨基甲酸酯樹脂(A)具有64重量份至68重量份之該聚碳酸酯多元醇(b)。 The method for producing an aqueous polyurethane resin according to claim 1, wherein the aqueous polyurethane resin (A) has 64 parts by weight to 68 parts by weight of the polycarbonate polyol (b) ). 一種水性聚氨基甲酸酯樹脂,其係由申請專利範圍第1項至第13項任一項所述方法製得,且基於該水性聚氨基甲酸酯樹脂(A)之總固含量為100重量份,該水性聚氨基甲酸酯樹脂(A)具有0.9重量份至1.3重量份之羧酸基以及60重量份至68重量份之聚碳酸酯多元醇(b)。 An aqueous polyurethane resin obtained by the method according to any one of claims 1 to 13, and based on the total solid content of the aqueous polyurethane resin (A) is 100 The aqueous polyurethane resin (A) has 0.9 parts by weight to 1.3 parts by weight of a carboxylic acid group and 60 parts by weight to 68 parts by weight of the polycarbonate polyol (b) in parts by weight. 一種高彩度水性聚氨基甲酸酯樹脂仿麂皮複合材料用之多孔層的製造方法,包含:進行一乾式塗佈步驟,使一高彩度水性聚氨基甲酸酯樹脂組成物(F)塗佈於一基材之一表面,其中該高彩度水性聚氨基甲酸酯樹脂組成物(F)包含:如申請專利範圍第14項所述之水性聚氨基甲酸酯樹脂(A);一顏料(B),其中該顏料(B)為一水溶性陰離子分散型顏料;一發泡助劑(C),其中該發泡助劑(C)之一揮發速率係低於水之一揮發速率,該發泡助劑(C)係不溶於水 且不與該水性聚氨基甲酸酯樹脂(A)互溶;以及一架橋劑(D),且其中基於該水性聚氨基甲酸酯樹脂(A)之使用量為100重量份,該顏料(B)之使用量為2至6重量份,該發泡助劑(C)之使用量為20至60重量份,以及該架橋劑(D)之使用量為0.5至4重量份;對塗佈該高彩度水性聚氨基甲酸酯樹脂組成物(F)之該基材進行加熱處理,使該高彩度水性聚氨基甲酸酯樹脂組成物(F)形成一多孔層,其中該加熱處理包含:去除該高彩度水性聚氨基甲酸酯樹脂組成物(F)之水份;使該高彩度水性聚氨基甲酸酯樹脂組成物(F)固化並形成一塗佈層;以及形成一多孔層,其中該多孔層具有複數個連續孔,該些連續孔係因該發泡助劑(C)揮發而形成,且其中該多孔層不使用起毛處理,該多孔層與該基材之間係直接塗佈且不存在任何黏著層,且該多孔層之彩度係不低於5,且該多孔層之摩擦堅牢度係不低於4級。 A method for producing a porous layer for a high chroma water-based polyurethane resin-like suede composite material, comprising: performing a dry coating step of coating a high chroma water-based polyurethane resin composition (F) on a a surface of one of the substrates, wherein the high-color aqueous polyurethane resin composition (F) comprises: the aqueous polyurethane resin (A) according to claim 14; a pigment (B), Wherein the pigment (B) is a water-soluble anion-dispersed pigment; a foaming aid (C), wherein a volatilization rate of one of the foaming assistants (C) is lower than a volatilization rate of water, and the foaming aid Agent (C) is insoluble in water And not miscible with the aqueous polyurethane resin (A); and a bridge (D), and wherein the pigment (B) is used in an amount of 100 parts by weight based on the aqueous polyurethane resin (A) Used in an amount of 2 to 6 parts by weight, the foaming auxiliary (C) is used in an amount of 20 to 60 parts by weight, and the bridging agent (D) is used in an amount of 0.5 to 4 parts by weight; The substrate of the high-color aqueous polyurethane resin composition (F) is subjected to heat treatment to form the high-color aqueous polyurethane resin composition (F) to form a porous layer, wherein the heat treatment comprises: removing the a water of a high chroma waterborne polyurethane resin composition (F); curing the high chroma waterborne polyurethane resin composition (F) and forming a coating layer; and forming a porous layer, wherein the porous The layer has a plurality of continuous pores formed by volatilization of the foaming aid (C), and wherein the porous layer is not subjected to raising treatment, and the porous layer is directly coated with the substrate and is not There is any adhesive layer, and the color of the porous layer is not less than 5, and the friction fastness of the porous layer is Less than four. 根據申請專利範圍第15項所述之高彩度水性聚氨基甲酸酯樹脂仿麂皮複合材料用之多孔層的製造方法,其中該高彩度水性聚氨基甲酸酯樹脂組成物(F)更包含一添加劑(E),且該添加劑(E)係選自於一增黏劑、一消泡劑、一造膜劑或一感熱凝固劑之一族群。 The method for producing a porous layer for a high-color aqueous polyurethane resin-like suede composite material according to the fifteenth aspect of the invention, wherein the high-color aqueous polyurethane resin composition (F) further comprises an additive (E), and the additive (E) is selected from the group consisting of a tackifier, an antifoaming agent, a film former or a heat-sensitive coagulant.
TW103146593A 2014-12-31 2014-12-31 Water-based polyurethane resin with high chromaticity, method of producing the same, and application on suede composite material thereof TWI525148B (en)

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JP6501136B1 (en) * 2017-09-14 2019-04-17 Dic株式会社 Method of manufacturing synthetic leather

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