TWI261611B - High performance adhesives having aromatic water-borne polyurethane and flocking method employing the same - Google Patents

Abstract

High performance adhesives having aromatic water-borne polyurethane and a flocking method employing the same. The high performance adhesive having aromatic water-borne polyurethane includes a water-dispersible polyurethane, a water-borne curing agent, and water, wherein the water-dispersible polyurethane includes aromatic diisocyanate water-dispersible polyurethanes, and optionally further includes aliphatic diisocyanate water-dispersible polyurethanes. The aromatic diisocyanate water-dispersible polyurethane made by a prepolymer effectively reacted with a chain extender to extend the chains and raise the molecular weight has high storage stability and superior mechanical properties. As a result, the adhesives are suitable for flocking processes.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to an adhesive comprising an aqueous polyurethane dispersion and a flocking method using the same, and more particularly to a high performance process comprising an aromatic aqueous polyurethane dispersion. Agent and flocking method using the same. [Prior Art] Flocking is often used for the surface treatment of substrates to give the substrate a velvet-llke-like surface characteristic. The so-called flocking is to fix the fibers on the surface of the elastic substrate or the plastic substrate, and to arrange the fibers vertically and closely on the surface of the substrate. Flocked articles are suitable for the manufacture of many different products, such as spacers, clothing, curtains, window edge fillers, suede effects, and interior flooring for automotive and other transportation. Fabric for wall decoration. A typical flocking operation involves applying an adhesive on the surface of the substrate as a backing layer of the fiber prior to fiber implantation, followed by vertical contact of the fibers with the backing layer. When the adhesive is dried and hardened, the fibers are fixed to the surface of the substrate. : Generally speaking, the 'performance of a flocked product' includes the adhesion and durability of the adhesive layer, depending on the type of fiber and the adhesive, and the subsequent method used. Moreover, the flocking process has a higher basic requirement for the adhesive used, such as the adhesiveness of the adhesive, and the adhesion to the substrate and the fiber is strong. An adhesive with a polyurethane dispersion (PU) as a main component, because of its resistance to dryness, high moisture resistance, f Uv light irradiation, and high resistance to water, organic solvents: greases, detergents Sex, very suitable for use in the planting process. Traditionally, in plastic or enamel elastic substrates, such as propylene.-p - ^ j a ~ _ vinyl plastic (ABS), plasticized "ethylene plastic (PVC), styrene - butyl (sbr In the flocking process of gas, rubber, 1261611 (CR) and ethylene-propylene-diene copolymer (EpDM), polyurethane resin dispersed or dissolved in a solvent is often used as an adhesive. The flocking technique using a solvent-based polyamine-based adhesive is disclosed in the patents Nos. 8 119 and 45 3 5 1 21. However, in the solvent-type polyurethane resin adhesive, the ash contains a large organic solvent. Carriers such as dimethyl decylamine (DMf), toluene, etc., if used inadvertently, can cause fire and explosion, greatly increasing the risk of operation. Furthermore, the use of organic solvents can easily cause the health of field operators. · Threats, as well as pollution and damage to the natural environment. Therefore, with the increasing number of countries around the world, and the increasingly stringent regulations on pollution prevention and control, flocking operations on plastic f or elastic substrates Highly toxic solvent-based polyurethane In recent years, the agent has been gradually replaced by a less polluting aqueous polyurethane resin adhesive. Water-based polyurethane resin adhesive - mouth ~,, soil 7 " human king; ^ amine ester tree, the traditional water The polyurethane resin is prepared by reacting a polyol (a component of an aqueous acid group of ρ〇1 with a diisocyanate) in a small amount of a high-boiling organic solvent to carry out a polyurethane prepolymer synthesis reaction, followed by using three Grade:: Neutralize' makes the polyurethane prepolymer ionic. After that, the ionic amine ester prepolymer is water-dispersed and chain extended to obtain an aqueous polyamine S 曰 resin. The aqueous polyamine (IV) grease The product, according to the type used in its preparation, can be divided into aromatic water-based polyamines, resin coffee, however, in the traditional aromatic water-based polyurethane resin spear towel, due to::::? As an aromatic (-) isocyanate group, the reaction rate of the NC〇 functional group with water is very high in the process of the process, and most of the surface will react with water to form an amine group (amine, Nh2). ), on the other hand, , / / people born The reaction of the amine group to form a urea structure (urea, _NHc〇NH~ and / consume) makes the residual nc〇 functional group after the water dispersion step too little, and 7 1261611 fails to provide an effective chain extension reaction to enhance the resin. The molecular weight of the resin leads to poor physical properties and mechanical properties of the resin, and it is easy to coagulate into pieces and has no commercial value. Therefore, although the development of aqueous polyurethanes has been 50 years, the commercial products have a history of more than 20 years. However, the actual applicable product is still a lower aliphatic or cycloaliphatic diisocyanate S曰 such as · isocyanate isophoric acid vinegar (iSOph〇rone) using a hydrophobic reaction. Diisocyanate, IPDI), I, cyanoquinone, hexamethylene diisocyanate (HDI), diisochamel acid 4,4 (dicyclohexylmethane) (4,4(-d1CyCl〇heXylmethaiie diisocyanate, H12MDI), etc., the resulting aliphatic aqueous polyurethane resin. However, the price of the aliphatic or cycloaliphatic isocyanate as a raw material is much more expensive than that of the aromatic isonic acid S, making the raw material cost of the aqueous polyurethane resin adhesive higher than that of the conventional solvent-based polyamine g resin adhesive. Many, the combination of water-based polyamines - adhesives can not be widely used in the flocking process. For example, in =83994〇 and DE_39G3796, an aliphatic diisocyanate mixture, the main component of the body flocking adhesive, is used. However, this process is difficult to apply to the preparation of Wangfang g-group diisocyanate aqueous]?1; dispersion. In order to completely replace the solvent-based polyurethane resin adhesive

The cost of the adhesive is the same, so (4) " raw W ~ Zhoukou flocking process used in the 曰 曰 水性 水性 水性 。 。 。 。 。 重点 重点 重点 重点 重点 重点 重点 重点 重点The present invention is directed to the use of plastic, synthetic glass or wood products for subsequent use. The adhesive is packaged in a bag 5:: paper, broken gambling dispersion. Due to the aromatic aqueous polyamine brewing dispersion:: two: polyamine reaction to increase the molecular weight of the resin, because 糸x effective chain extension α has the stability to storage and excellent machine 1261611 ester resin as a waterborne mechanical property, It can be used to replace the components of the high-priced aliphatic aqueous polyurethane hydrocarbyl ester adhesive. > Another object of the present invention is to provide a high-performance aqueous polyurethane adhesive Y which is prepared from an aqueous dispersion of wholly aromatic diisocyanate or an aqueous mixed dispersion of aromatic and aliphatic diisocyanate. There is a performance comparable to that of a solvent-based polyester adhesive, and it is possible to dispense with the disadvantages of solvent-based polyurethane adhesives. Another object of the present invention is to provide a flocking method using a high performance adhesive comprising an aromatic aqueous polyamine hydrazine dispersion to obtain a flocked product having high performance and durability. The flocking method of the present invention is applicable to a variety of substrates, particularly various plastics, rubber, fabrics, metals, leather, paper, glass (f) or wood products. For the above purpose, the south performance adhesive comprising the aromatic aqueous polyurethane dispersion of the present invention comprises: t (a) 9 to 65 weight percent aqueous polyurethane dispersion, wherein the aqueous polyamine s曰h The dispersion liquid comprises an aromatic diisocyanate aqueous polyurethane dispersion; (b) 4 to 50% by weight of an aqueous hardener; and (c) 16 to 80% by weight of water; wherein the weight percentage is followed by The total weight of the agent is based on the basis. According to the high performance adhesive of the aromatic aqueous polyurethane dispersion according to the present invention, the aqueous hardener which is suitable for use in the present invention is a compound which can be reacted with a hydroxyl group or a carboxyl group, and can be optionally freed from melamine. Amino resin such as formic acid, urea-A-plate, amide-formic acid, and sealed polyisocyanate resin (bl〇cked P〇lyiS〇cyanate), sealed polytriisocyanate resin (M〇cked P〇lyis〇cyanurate) ), an epoxy resin, and the like, and a group of derivatives thereof. The high performance adhesive comprising the aromatic aqueous polyurethane dispersion of the present invention may further comprise: 9 1261611 (d) 0 to 1% by weight of the aqueous hardening accelerator; and (e) 0 to 25 weight percent An aqueous binder additive. - Among them, the aqueous hardening accelerator which is suitable for the present invention may be a catalyst capable of catalyzing the crosslinking of an amine-based resin, a polyisocyanate resin, a polyisocyanate resin or an epoxy resin, or may be a sulfonic acid or a tertiary amine. , tin catalyst, titanium catalyst, zirconium catalyst, neocatalyst or a mixture thereof. High Performance Resin Agent Containing Aromatic Aromatic Polyurethane Dispersion According to the Invention The aqueous binder additive suitable for use in the present invention may be an aqueous viscosity adjustment agent, an antioxidant, a light stabilizer, a colorant, a filler, and the like. Wherein 'aqueous viscosity modifier is an organic or inorganic high score|sub-compound that can be thickened or thickened, such as polyvinyl alcohol (p〇lyvinyl alc〇h〇1), alkylated cellulose, hydroxyalkylation ( Hydroxyalkylated cellulose, carboxyalkylated (c^b〇xyalkylated) cellulose, hydrophobically modified ethoxylated urethane (HEUR), polyamidamine resin, acrylic microgel (micr〇gel) An organic polymer compound such as an organic compound such as a fumed silica such as Cab 〇Sil or a surface modified clay (4) ay). " A high performance secondary agent comprising an aromatic aqueous polyurethane dispersion according to the present invention, wherein the aqueous polyurethane dispersion further comprises an aliphatic diisocyanate|ester aqueous polyurethane dispersion. It is worth noting that the aromatic diisocyanic acid aqueous polyamine dispersion liquid system of the present invention can effectively avoid the molecular weight of the resin by an effective chain extension reaction, and the conventional aromatic (four) aqueous poly (four) process is In the water dispersion step, the reaction rate of this group with water is very high due to its nc〇B, so that most of the nc〇 reacts with water to form an amine group (face ne, - view 2), and the other side The amine-based anti-accumulation produces a urea structure (caffe, -NHC0NH-) and is consumed, resulting in a problem that the chain-extension reaction cannot be improved to increase the molecular weight of the resin. 10 1261611 diis〇cyanate, PPDI), diisocyanate 4 4, 4,4-diphenylmethane diisocyanate (MDI), diisocyanate pp, mono-based δ (p, p, Bisphenyl diisocyanate, BPDI) or a mixture thereof. The aromatic diisocyanate suitable for use in the present invention may also be selected from the group consisting of a compound of the formula (I), a compound of the formula (II) and a mixture thereof.

NCO OCN

Formula (I) Formula (II) wherein 'R is hydrogen or C! 6 alkyl; R2 and R3 may be the same or different and independently hydrogen, alkyl having one to six carbons, having one to six Alkoxy, or an aromatic group; and η is 〇, 1, 2 or 3. The aromatic diisocyanate aqueous polyurethane dispersion according to the present invention may be formed by mixing a dimer or a trimer of the aromatic diisocyanate. For example, a dimer (or terpolymer) of toluene diisocyanate can be formed into a diisocyanate mixture with a dimer (or trimer) of p-diisocyanate, and further used for preparation. The aromatic diisocyanate-based aqueous polyurethane dispersion, wherein the diisocyanate or the p-isoisocyanate benzene is preferably present in an amount of 3 〇m 〇 1% or more of the diisocyanate mixture. Polyols suitable for use in the present invention may be difunctional or polyfunctional polyols such as polyester polyols, polyether polyols, polycarbonate polyols, polycaprolactone polyols or polyacrylate polyols. Preferred are, for example, butanediol-co-adipate glycol (PBA), polytetramethylene glycoside (PTMEG), hexanediol-adipate copolymer (poly(hexanediol-co-adipate) glycol, PHA), ethylene glycol, adipic acid copolymer (poly(ethanediol-co-adipate) glycol, PEA), polypropylene glycol (polypropylene gly C0), polyethylene glycol (p〇lyethylene glycol, 12 1261611 cyclohexyldimethanol (CHDM), octanediol, neopentyl glycol 'NPG', trimethylpentanediol (TMPD), stupid sterol, stupid Bipan, bisphenol-A, propylene glycol, pentaerythritol (pentaerythnt〇i), stupid triterpene, diethylene glycol, triethylene glycol, dipropylene glycol or tripropylene glycol. In order to achieve another object of the present invention, the present invention also relates to a A flocking process using the high performance adhesive of an aromatic aqueous polyurethane dispersion of the present invention comprises the following steps:

^ First, provide a substrate to be flocked. Next, applying an aromatic aqueous polyamine S dispersion to the substrate to form a high performance adhesive comprising the aqueous layer of the aqueous poly(tetra) dispersion comprising a bonder layer wherein t(4) 9 to 65 weight percent An aqueous poly(tetra) dispersion, wherein the aqueous dispersion comprises a wholly aromatic diisocyanate "aqueous polyamine dispersion"; (b) 0.04 to 50 weight percent aqueous hardener; (c) 16 to 80 weight The percentage of the total weight of the aqueous agent is based on the weight percentage of the adhesive layer coated with the fiber on the adhesive layer. Finally, the adhesive layer is dried to be applied to the substrate according to the invention. The velvet method, the high-performance adhesive of the vinegar dispersion further includes: Λ 3 square red water-based polymerization

(4) 0 to 1 (% by weight) of an aqueous hardening accelerator; (e) 〇 255% by weight of an aqueous adhesive additive. According to the flocking method of the present invention, it is preferred that the solid part of the sulphur-forming adhesive of the gas is a 30-45 weight percent. ',, 5-60% by weight, and the flocking method according to the present invention, wherein 2 〇 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 200 The dry film amount of the adhesive layer is such that the temperature of the adhesive layer is 14 1261611 and can be 50-200 °C.

The method, features and advantages of the present invention are further described by the following examples, examples and comparative examples, but are not intended to limit the scope of the invention, the scope of the invention should be The scope of application for patents shall prevail. X [Embodiment] Preparation of a fragrance-free, isocyanate-based aqueous polyurethane dispersion The high-performance adhesive of the present invention is characterized in that the adhesive comprises an aromatic diisocyanate-based aqueous polyurethane dispersion. The aromatic diisocyanate aqueous polyurethane dispersion is a product obtained by the following steps: 1 to 4% by weight of aromatic diisocyanate by prepolymer mixing pr〇cess 30 to 80% by weight of the polyol, and 15% by weight of the active hydrogen-forming compound capable of forming a hydrophilic functional group to form a prepolymer; dispersing the prepolymer in water; controlling the prepolymer dispersion The content of the NC 〇 functional group after the water; and the chain extender of the chain extender of the amount of the NC0 functional group in the range of 0.8 to 8.0% by weight. In the preparation of the aqueous aromatic polyurethane dispersion of Fangxiang diisocyanate, the monthly NCO content of the 6-Hai chain extender is added to the sputum, so it can accurately prolong the reaction. The timing makes it possible to carry out effective chain and \eQ functional group content several times higher than the conventional technology to obtain the polymer. *The material of the raw material of the raw fragrant di-isocyanate-based aqueous polyurethane dispersion and the aromatic diisocyanate-based aqueous polyurethane dispersion described in the book, and the clothing type are more clear, and the following is a preferred embodiment. Examples are detailed in Preparation 1 1261611 Examples 1 to 4. Preparation Example 1: 17.63 g of dimethylol propionic acid (DMPA) and 38.89 g of N-methyl pyrrolidone (NMP) were reacted under nitrogen atmosphere. Stir well in the tank. When the above raw materials are in a uniform phase, 78.23 g of toluene diisocyanate (TDI) and 2,6-diisocyanatoluene S (mixing ratio of 4:1) are added. In the reaction tank. After heating to 60 ° C and reacting for 1.5 hours, 'add 190.23 g of hexanediol / neopentyl glycol - adipic acid poly-sodium glycol ([poly(hexanediol / neopentyl glycol-co-adipate) glycol ' PHNA]) (HD: NPG: AA molar ratio = 3: 2: 5, Μη is about 2,000), 263.41 g of polytetramethylene glycol (PTMEG) (Mn = 2,000) and 0.50 g of 1,4 - Butanediol (1,4-Butanediol) is mixed in the reaction tank and uniformly. After heating to 75 ° C and reacting for 4 hours, the temperature of the reaction vessel was lowered to 50 ° C, and 12.37 g of triethyl amine (TEA) was added to carry out a neutralization reaction for 20 minutes. Thereafter, 270 g of the neutralized and hydrophilic prepolymer was quickly added to 560 g of deionized water at a stirring rate of 500 Å·ρηι, and water dispersion was carried out while monitoring its NCO value. Before the NCO value fell to 1.65 wt%, 5.56 g of water-diluted ethylenediamine (EDA) was added to carry out a chain extension reaction. When the chain extension reaction was continued at room temperature for 2 hours, an aromatic diisocyanate aqueous polyurethane dispersion A was obtained, and the solid content thereof was 35 wt%. The aqueous PU dispersion had a hydrophilic group of 30 meq/100 g dry parts, a degree of neutralization of 1%, and a solvent content of 10% by weight. Preparation Example 2: 17.63 g of dihydromercaptopropionic acid and 28.90 g of acetone were uniformly stirred in a reaction vessel under a nitrogen atmosphere. When the above raw materials are in a uniform phase, 16 1261611 78.23 g of 2,4-diisopropyl cyanate and 2,6-diisocyanatomethyl ester (mixing ratio of 4:1) are added to the reaction tank. . Heat to 6 〇. After 5 hours of hydrazine reaction, 152.18 g of hexanol/neopentyl glycol-adipate polyester diol was added: NpG : AA molar ratio = 4 : 1 : 5, Μη is about 1,500 ), l〇 1.46g of butanediol-adipate copolymer [P〇ly (bUtaned1〇l-CO-adlpate) glycol, PBA] (Mn is about 2,000) and 〇·50 g of 1,4-butyl The diol is in the reaction tank and mixed uniformly. After heating to 75 C and reacting for 4 hours, the temperature of the reaction vessel was lowered to 5 Torr, and "1217 g of diethylamine was added, and the neutralization reaction was carried out for 2 Torr. After that, the neutralized and hydrophilic pretreatment was carried out. 270 g of polymer, rapidly added to a stirring rate of 5 〇 (kpm in 49 〇g deionized water, water dispersion and simultaneously monitor its NCO value. After the NCO value fell to 2.35 wt% 加入 'Add water diluted ethylene diamine 5 〇〇g, for the chain extension reaction. When the chain extension reaction is continued at room temperature for 2 hours, the aromatic diisocyanate aqueous polyurethane dispersion B' is obtained as a solid content of 4 〇 wt%. The hydrophilic group of the solid fraction was 35 meq/1 〇〇g dry, the degree of neutralization was 1%, and the solvent content was 10% by weight. Preparation Example 3: 17.63 g of dihydroxymethyl propionic acid and 38 89 g The N-mercaptopyrrolone is uniformly stirred in the reaction tank under a deactivated environment. When the above raw materials are in a uniform phase, 78.23 g of 2,4-diisocyanate and 2,6_2 are used. The hydrazine isocyanate (mixing ratio of 4:1) is added to the reaction tank. After heating to (8) and reacting for 1.5 hours, 25 3.60 g of polytetramethylene glycol is added. (Μη is about 2, 〇〇〇) and 〇5〇g of 14-butanediol in the reaction tank and mixed uniformly. After heating to 75 and reacting for 4 hours, the temperature of the reaction tank is lowered to 5 (TC, And adding 12.17g of triethylamine to carry out the neutralization reaction in 20 knives. After that, the neutralized and hydrophilic prepolymer 270 g was quickly added to 560 g of deionized water with a mixing rate of 500 rpm. Water dispersion was carried out while the NC enthalpy value was monitored. Before the NCO value fell to 85.85 _%, water-diluted 17 1261611 ethylenediamine 5.56 g was added for chain extension reaction. When the chain extension reaction was at room temperature After 2 hours, an aromatic diisocyanate aqueous polyurethane dispersion c having a solid content of 35 wt% was obtained, and the hydrophilic group of the aqueous PU dispersion was 35 meq/l 干g dry, and the degree of neutralization was 100. °/〇, and the solvent content is 1 〇wt%. Preparation Example 4: 17.63 g of dimethylolpropionic acid and 38 89 § N-methylpyrrolidone are stirred uniformly in a reaction tank under a nitrogen atmosphere. When the raw material is in a uniform phase, 78.23 g of 2,4-diisocyanate and 2,6-diphenylphenyl isocyanate (mixing ratio of 4:1) are used. Into the reaction tank. After heating to 6 〇r and reacting for 5 hours, add 253.60 g of butanol-adipate copolymer and 〇5〇gii, 4-butanediol in the reaction tank and mix well. After reacting for 4 hours to 75 °, the temperature of the reaction vessel was lowered to 50 ° C, and 12.17 g of triethylamine was added to carry out a neutralization reaction for 2 minutes. Thereafter, the neutralized and hydrophilic prepolymerization was carried out. 27 g, rapidly added to 560 g of deionized water at a stirring rate of 500 rpm, water dispersion and simultaneous monitoring of its Nc 〇 value. Before the NCO value fell to 1.75 wt%, 5.56 g of water-diluted ethylenediamine was added to carry out a chain extension reaction. When the chain extension reaction was continued at room temperature for 2 hours, an aromatic diisocyanate aqueous polyurethane dispersion D having a solid content of 35 wt% was obtained. The hydrophilic group of the aqueous PU dispersion had a hydrophilic group of 3 〇 meq / 1 〇〇 g dry, a degree of neutralization of 100%, and a solvent content of 1 〇 wt%. Preparation of High Performance Adhesive Containing Aromatic Aqueous Polyurethane Dispersion The high performance adhesive comprising the aromatic aqueous polyurethane dispersion of the present invention is prepared as follows: First, the aqueous polyurethane dispersion is mixed with water. Next, the aqueous hardener was slowly added to the above aqueous polyurethane dispersion in a stirring of 50 to 200 Torr. In this step, an aqueous hardening accelerator and an aqueous viscosity 18 1261611 adjusting agent may be further added as needed to adjust the adhesive viscosity to about 15,000 cps. Table 1 is a series of examples of high performance adhesives comprising an aromatic aqueous polyurethane dispersion according to the present invention, comprising eight aqueous polyurethane adhesives having different compositions, and their respective constituents, and Also list the proportions of its composition. Energy Table 1: Composition of aromatic aqueous polyurethane dispersion according to the present invention. Composition and ratio of the following agent. Aqueous polyamine ester adhesive Aqueous polyurethane dispersion Waterborne hardener

A Aqueous polyurethane Dispersion A (Preparation Example 1) / PMN [Note 1] Aqueous hardening #376 [Note 2] Water resistance followed by jj #255 [Note 3] Ratio of each component (wt%) 90.1 5.4 2.7

B Aqueous polyurethane dispersion A (Preparation Example 1) Ratio of each component (wt%) 93.4 #3100 [Note 4] 4.7 0 C ------^ " Ratio of each component (wt%) Aqueous polyurethane dispersion B (Preparation 2) 93.4 #3100[Note 4] 4.7 0 1.8 ===========3⁄4 #255 [Note 3] 1.9 ========: #255[Note 3] ------ L9 19 1261611

D Aqueous polyurethane dispersion A (Preparation Example 1) PMN [Note 1] #376 [Note 2] #266 [言主5] Ratio of each component (wt%) 90.1 5.4 2.7 1.8 E Aqueous polyamine S dispersion B (Preparation Example 2) PMN [Note 1] #376 [Note 2] #266 [言主5] Ratio of each component (wt%) 90.1 5.4 2.7 1.8 F Aqueous polyurethane dispersion C (Preparation Example 3) PMN [Note 1 #376 [Note 2] #266 [言主5] The ratio of each component (wt%) 90.1 5.4 2.7 1.8 G Aqueous polyamine 酉 dispersion C (Preparation Example 3) #3100 [言主4] Μ #266 [Word main 5] Ratio of each component (wt%) 93.4 4.7 0 1.9 Η Aqueous polyurethane dispersion D (Preparation Example 4) #3100 [1 Main 4] #266 [言主5] Proportion of each component (wt%) 93.4 4.7 0 1.9 [Note 1] : PMN is a large company melamine resin, product number is PMN 1261611 2Γ· # 376 is the company's acid catalyst, product number is #376 [Note 3] ·· # 255系中厚Company HEUR resin Rheolate, product code # 255 4] : # 3 100 is a Bayer company sealed polyisocyanate resin, product number # 31〇〇[5 main 5] ·· # 266 is a medium-thick company HEUR resin Rheolate, Product Code is # 266 The high performance adhesive comprising the aromatic aqueous polyurethane dispersion of the present invention has a performance superior to that of the adhesive comprising the conventional aromatic aqueous polyurethane dispersion. Table 2 series exemplifies some dispersions of conventional aromatic aqueous polyurethanes. An example of a liquid adhesive, and its composition and ratio. Proportion of water-based polyamine aqueous polyamine ~~Γ Waterborne polyamine vinegar adhesive----- Water-based polyurethane dispersion aqueous hardener-~~~---------- Water-based hardening accelerator Additives | JI Commercial products (I) [Note 6] ΡΜΝ [Note 1] #376[Note 2] #255[Note y ratio of each component (wt%) 90.1 ---- 5.4 —---~ -_ 2.7 1.8 J Commercial item (π) [Note 7] —-- #3100 _[Note 4] ------ #376[Note 2] #255[Note 3] Ratio of each component (Wt% 90.1 5.4 2.7 1.8 K Commercial item #3100 None (Π) [Note 7] _[Note 4] #255[Note 3J Proportion of each component (wt%) 93.4 4.7 ~~----_______ 0 1.9

21 1261611 L —---—___ Commercial (I) #3100 [Note 4] #266[Note 5] Proportion of each component (wt%) 93.4 '~—-__ 4.7 0 1.9 Μ Commercial 7 ] #3100 [Note 4] Benefit----- #266[Note 5] Proportion of each component (wt%) 93.4 4.7 0 ----- 1.9 [Note 1] ·· PMN is a melamine resin of the company The product number is pmn [Note 2] : # 376 is the company's acid catalyst, product number is #376 [Note 3]: # 255 is the medium thick company HEUR resin Rheolate, product number is # 255 [Note 4] : # 3100 Series Bayer Sealed Polyisocyanate Resin, Product Code # 3100 [σ main 5] · # 266 is a medium-thick company HEUR resin Rheolate, product code # 266

[Note 6]: Commercial product (1) is a large Japanese ink company tdi / polyether type aqueous polyamine g purpose dispersion, product number is HW-312B

[Note 7]·········································································· It has high storage stability and excellent mechanical properties, and is suitable for flocking process, film lamination or fabric bonding applications of plastic or fabric substrates. Flocking method and testing of flocking products The high performance of the aromatic aqueous polyurethane dispersion according to the present invention is followed by 22 1261611 = suitable σ t as an adhesive used in the field processing process, and is suitable for any planting, I The surface of the substrate. The following several examples and comparative examples are the application examples of the conventional aromatic water-based polyurethane adhesive 1 Μ 'for the flocking process adhesive agent described in Table 1 for the adhesives A to H of the present invention. The flocking system of the present invention will be described in further detail. However, the scope of the invention is not limited to the embodiments. Example 1 -* The entangler was applied to a 0. 6 mm thick plasticized pvc film to form a Z-sublayer. The coating method can be _ coating method, spray coating method, roll coating method, spin coating electric spraying method; wherein, the aqueous polyamine 50 coated on the substrate to be flocked is formed into 2 〇 2 〇〇 2 〇〇 2 The amount of the film is preferably used, and the most common one is a coating process for making a dry film of the body. If necessary, you can still choose something thicker or thinner=1. Then, using electrostatic field method or mechanical vibration flocking method, = ready: fiber 'planting film in the back layer; pick = roast: go to the planted fiber' and then placed at different temperatures of the two For the box, in the 130 device, suck 2 2 160 C for 3 minutes. After baking, use the vacuum as the fiber that is not planted. After cooling, the properties were measured. Test results: The basic requirements for the properties of the velvet product include: the adhesion of the adhesive T and the fiber is strong. Practically required to have high resistance: base and organic solvent resistance. Here, the evaluation items are wet, poor, and sturdy, and are sturdy, thirsty, and organic solvent, dry friction, and thirsty solvent friction. ", thick rubbing and so-called squeezing, refer to the number of cNSi 〇 757 #62 flocking samples after a hundred grid base to the mark, tape-fitted "occupation method". The new departure, the nose is not dialed, the so-called friction, is the use of the vibration type friction tester 'place the sample in 23 1261611 items ~~~-- number / total number / total number / total test items dry hundred grid 100/100 100/100 100/100 100/100 Wet 100% Adhesive 95/100 50/100 15/100 40/100 Benzene 100% 100/100 100/100 100/100 100/ 100 Friction test item failure time when the number of failures is broken. Number of frictions Test item dry friction> 500 > 500 > 500 500 Wet friction > 350 80 20 50 Toluene friction > 500 &gt ; 500 > 500 > 500

It can be seen from Tables 3 to 6 that in the flocking process, if a high-performance adhesive which conforms to the di-f-containing aromatic aqueous polyurethane dispersion according to the present invention is used to form an adhesive layer, the fiber on the flocked product of Xu Tsai is more Not easy to fall off. Ancient, above +, the present invention discloses an aromatic aqueous polyurethane dispersion 2:: an adhesive capable of 'good adhesion, dry resistance, moisture resistance and resistance to tips ~ m, 'can be used to replace high prices The aliphatic aqueous polyamine g is a resin adhesive and a solvent-based polyurethane resin adhesive which is relatively unsafe to use, and can be further used in a flocking process to form an adhesive layer to enhance the ability of the substrate to adhere to the fiber. Eight

The present invention has been disclosed in the above preferred embodiments, and it is not intended to be limited to the scope of the present invention, and the present invention is not limited to the spirit and scope of the present invention. The scope of protection of the present invention is subject to the definition of the attached patent. 28 1261611 [Simple description of the diagram] None. [Symbol description] Innocent

Claims (1)

Amendment date: 95.5.26 126 1 per U 3彳 769, please modify the patent scope, patent application scope: 1. A high-performance adhesive containing an aromatic aqueous polyurethane dispersion, which includes: (a) 9~ 65 wt% aqueous polyurethane dispersion, wherein the aqueous polyurethane dispersion comprises an aromatic diisocyanate aqueous polyurethane dispersion; (b) 0.04 to 50% by weight of an aqueous hardener; and (c) 16 to 80% by weight of water Wherein the weight percentage is based on the total weight of the adhesive; wherein the aromatic diisocyanate aqueous polyurethane dispersion is a product obtained by the following steps: 10 via a prepolymer mixing process ～40% by weight of aromatic diisocyanate, 30 to 80% by weight of polyol, and 1 to 15% by weight of a compound capable of forming a hydrophilic functional group to form a prepolymer; dispersing the prepolymer in water Monitoring the NC0 functional group content of the prepolymer dispersed in water; and the NC0 functional group in the dispersion When the content is in the range of 0.8 to 8.0% by weight, 0.1 to 5 weight percent of a chain extender is added to carry out a chain extension reaction, wherein the weight percentage is based on the total weight of the prepolymer; wherein the aqueous hardener is a compound which reacts with a hydroxyl group or a carboxyl group, and is selected from an amine resin such as melamine-formaldehyde, urea-formaldehyde, guanamine-formaldehyde, a blocked polyisocyanate, a blocked polyisocyanurate, or a blocked polyisocyanurate. Among the groups of epoxy resins and their derivatives. 2. The high performance adhesive comprising an aromatic aqueous polyurethane dispersion according to claim 1, wherein the aromatic diisocyanate has one or one of 0424-A20038TWF2; 02920030; susanwu 30 1261611 or more aromatic rings, The aromatic ring is selected from the group consisting of phenyl, biphenyl and naphthyl, and the hydrogen on one or more carbons of the aromatic ring may be fluorine atom, i atom, nitro group or cyanide as needed. Substituted by a base, a base, an alkoxy group, a halogen-based group, a hydroxyl group, a carboxyl group, a guanamine group or an amine group. 3. The high performance adhesive comprising an aromatic aqueous polyurethane dispersion according to claim 1, wherein the aromatic diisocyanate is selected from the group consisting of the compound of the formula (I) and having the formula (II) a group of compounds and their mixtures: Formula (1) Formula (II) wherein K is hydrogen or Ct6 alkyl; R2 and R3 may be the same or different and independently hydrogen, an alkyl group having one to six carbons, and an alkoxy group having one to six carbons a base or an aromatic group; and η is 0, 1, 2 or 3. 4. The high performance adhesive comprising an aromatic aqueous polyurethane dispersion as described in claim 1, wherein the aromatic diisocyanate is Toluene diisocyanate (TDI), p-diiso Benzene cyanate (p-Phenylene diisocyanate, PPDI), 4,4'-Diphenylmethane diisocyanate (MDI), diisocyanate p,p'- Phenyl ester (p, p'_Bisphenyl diisocyanate, BPDI) or a mixture thereof. 5. The high performance adhesive comprising an aromatic aqueous polyurethane dispersion as described in claim 1, wherein the polyol is a difunctional polyol or a polyfunctional polyol, including a polyester polyol, a poly Ether polyol, polycarbonate polyol, polycaprolactone polyol, polyacrylate polyol, or a mixture thereof. 6. As described in the scope of patent application, the aromatic water-containing polyurethane part 0424-A20038TWF2; 02920030; susanwu 1261611 dispersion liquid south of the performance agent, #%% hydrophilic function & The hydrophilic functional group of the compound is a C00-, a S03-2, - NR4+, or a 曰-(CH2CH20) ' 4 3 疋, 7 · 专利 Patent scope 帛 1 containing an aromatic aqueous polyamine 酉A high-performance adhesive for a dispersion, in which a pre-polymer blending method is used to form a pre-formed wound, including G.1 to Η) by weight of at least two functional groups reactive with an isochlorinic acid group. Low molecular weight compounds. The aromatic aqueous polyurethane dispersion described in the first aspect of the patent scope: a high-performance adhesive, a low molecular weight compound of a functional group reactive with an isocyanate group in #, an aromatic diol, an aromatic Polyols, aromatic scales, drunks, aliphatic diols m, aliphatic polyols or fats _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The surface performance of the adhesive, the molecular weight compound which can react with the isocyanate g group, has a molecular weight of 6 〇 3 〇〇. 10 。 。 。 。 。 。 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或.地一B 11丄如巾, please refer to the aromatic aqueous polyurethane dispersion as described in Item 1 = high performance adhesive, wherein the aqueous polyamine dispersion also includes aliphatic diisocyanate aqueous polyurethane dispersion liquid. 12: The method of claim 4, wherein the method comprises the following: (d) an aqueous hardening accelerator of 0 to 1% by weight; And (e) 0 to 25 weight percent of an aqueous binder additive. a such as ^ please special (4) (d) 12 of the positive-performance adhesives containing aromatic aqueous polyamine dispersions, in which the aqueous hardening accelerator is including acid, 0424-A20038TWF2: 02920030: susanwu 1261611 tertiary amine, tin touch Medium, titanium catalyst, zirconium catalyst, rhodium catalyst or a mixture thereof. 14. The high performance adhesive comprising an aromatic aqueous polyurethane dispersion according to claim 12, wherein the aqueous adhesive additive is an aqueous viscosity modifier, an antioxidant, a light stabilizer, a colorant, a filler or Its mixture. 0424-A20038TWF2: 02920030; susanwu 33