TWI254055B - An antibacterial waterborne polyurethane/clay nanoscale dispersion and method of production therefore - Google Patents

Abstract

A method of producing an antibacterial waterborne polyurethane/clay nanoscale dispersion is presented. A series of quaternary alkylammonium salts or quaternary alkylphenylammonium salts were used to modify hydrophilic clay with microscale particle size and nanoscale inner pore size to be organophilic. The organophilic clay was added during the synthesis process of waterborne polyurethane to form a waterborne polyurethane/clay nanoscale dispersion. The average particle sizes and viscosities of the polyurethane/clay dispersions increase with increasing clay contents under a fixed solid content of the dispersions. The ionic characteristics of clay result in the rising particle size and viscosity of the dispersions. Clay enhances thermal resistance of polyurethane/clay composites without changing their glass transition temperatures. Furthermore, clay introduces antibacterial property to waterborne polyurethane significantly.

Description

1254055 V. INSTRUCTIONS (1) [The invention belongs to the environmental protection intention, but the water-based tree has not been published in literature. There is no micro-montmorillonite in the literature, and the nano-clay and clay composite film of poly-clay The level of particle transfer temperature is almost in the technical field. The solvent-based p U resin is more susceptible to solvent-based PU antibacterial research than the solvent-based resin. The present invention forms an aqueous PU composite after water-sized particle size but with a nano-combination process (Nanocompos's anti-microbial and anti-alloy clay can increase the effect of the composite film. The fat is gradually transferred to the micro--, but the sexual PU The effect of the level of the hole and the effect of the heat-resistant water-based PU material on the PU stage of the clay-grade grade, and the addition of the resin, although some of the antibacterial research is added (c lay) Or the particle size of the water-based PU has been modified to its glass [previously water-based PU fabric treatment, etc., for example, the dermis hair, is also the water will gradually replace the PU resin in the health of the salty feel, work leather is quite close to pollution prevention The application of the change of life, to the near surface of the PU near the traditional oil processing threat. Very good approach. Regulatory Day, the original field, the years of B I agent, the years of PU, the makers, by the moisture permeability, with the strict South pollution of the world since the early nder and other adhesives are valued as the city's environmental water PU breathability All over the world, the dissolution of PU trees

Low people, etc. However, the cause of the main stain on the field, and the melting of the ring-shaped grease industry J-type PU requirements to one of the high-quality artificial skin, flow, main dyeing and the current artificial leather Qi J-type PU is increasingly in the near resin 'Products, such as sexual products, leather materials, the future of water-based PU, if the oil field operator Becker's have the benefits of the people made, and the leather has gradually been reduced

Page 7 1254055 V. INSTRUCTIONS (2) The dyed water-based PU is replaced. According to the survey, the volatile organic matter decreased from the VOC (Volatile 〇rganic comp〇unds) content in 980 to the 3% content in 2000, which shows that the study of water-based pu is an imperative Mingzheng provides a valuable water-based pu modification technology. With the improvement of the quality of life and the rise of environmental awareness, today's consumers are increasingly demanding the quality of their products, not only in appearance and popularity, but also in their comfort. Especially the subtropical and island-type climate, the humidity is quite heavy, and it provides an excellent environment for the growth of 4 organisms. Therefore, many products on the market are advertised as having antibacterial and anti-mildew effects. There are a few reports on solvent-based PU. Antibacterial studies, such as w〇〇1 et al., introduced ciprofloxacin compounds into the pu structure to give (10) an antibacterial effect. Grapski et al. introduced N,N-bis(2-hydroxyethyl) isonicotinamide compounds in the PU structure, followed by alkyi haHde. It is made into a quaternary ammonium salt with an antibacterial effect. Wang et al. introduced a commercially available antibacterial agent QAS, which is an organic bismuth compound of a quaternary ammonium salt, in the PU structure, giving pu an antibacterial effect. However, no antibacterial research on aqueous pu has been reported in the literature so far, and the antibacterial property of aqueous PU is very important in use. The present invention is to introduce an antibacterial nano-sized clay into an aqueous P U to impart an anti-caries effect. Clay or earthworms are inorganic minerals with abundant reserves in nature, so they are cheap and have good mechanical strength and chemical resistance, which makes the invention more cost-effective, more practical and economical. Under the four columns, it can be caused by large-scale solidification, and the bacteria can resist five kinds of quality.

1254055 V. INSTRUCTIONS (3) Protein is the life force of the main body of microorganisms (enzyme if;: one of the enzymes is micro-growth), which is denatured by factors such as heat or acid. Its original jDenaturation) will change its chemical structure and its activity and shape will be lost. Ai (1), cell membrane or cell wall destruction ^ 杬 J J can change the microbial cell membrane (or cell 璧), so that the microbial cells lose their original integrity and function. (Sulfhydryl group) If there is no sulfur-based mouse that cannot be maintained in a free state, it will lose its direct function. For example, an oxidant can bond adjacent sulfhydryl groups into a disulfide. (D isu 1 fide ) 'to achieve its purpose of interfering with the activity of the enzyme. (4) - Chemical + antagonism (Chemical antagonism) Complex insect white enzyme (H〇l〇enzyme) Some need to have metal ions (also known as The metal active agent, Metal activator), if any of them = chemical antagonism, its function will be affected. 藉 Modified by the present invention and subjected to aqueous polymerization 1] polymerization process peeling = grade = shape Clay antibacterial agent of granules and commercially available antibacterial agent: 乂 乂. See the general use of antibacterial agents on the market are mostly chemical considerations = modern people who are not natural, reduce the use of chemicals 氲b. Everyone expects, so it is taken from natural inorganic substances, especially sticky = Xietu soil. If it can be a good antibacterial agent, it will improve the application of nano inorganic and antimony. Soil antibacterial Preliminary study phase material, its antibacterial mechanism is not clear, still Angeles on big Xin

Page 9 1254055

V. INSTRUCTIONS (4) There are two possibilities, one is to modify the antibacterial effect, the other is to be with the montmorillon:=; the money [is itself related to the surface. SUMMARY OF THE INVENTION The present invention utilizes clay modified by an antibacterial agent to be a nanometer-sized pore as an antibacterial agent, and has a size of a plaque: after that, it is polymerized into an aqueous pu, and is changed with soil; Granules, due to their lipophilicity, are dispersed in water=meter-like filamentous (stripe) grade-like composites, which are made to have antibacterial properties; ίfruit" Rice-grade pore clay... (Montmorillonite) is an inorganic mineral that is rich in strontium or bleed, and is 〇.u1〇%, preferably 5%. ο·1 to 15%, better In a specific embodiment of the present invention, the clay used is an inorganic substance having a citrate structure, and a layer of Al2〇3 octahedron is sandwiched between two layers of Si〇2 tetrahedron, and the layered structure formed is as shown in FIG. There are exchangeable metal ions, and after swelling by water, the volume can be expanded by several tens of times. The antibacterial modifier of the nano-scale pore clay inorganic material used in the present invention can be: quaternary alkylammonium salt ), long-chain phenyl tetrabasic salt (quaternary alkylphenylammonium) Salt), benzyl ammonium chloride, C12H25N(CH3) 3Br, C14H29N(CH3)3Br, C16H33N(CH3)3Br, [CH3(CH2)u]2(CH3) 2NBr, chemical antibacterial agents commonly used in the market, etc. Commonly used chemical resistance

Page 10 1254055 V. Description of invention (5) The main components of the microbial agent include phenolic compounds, alcohol, dentate, ammonium salts and the like. The antibacterial effect of the unmodified clay is not very significant: up to 17~39% ’, and the clay that has been modified and chemically dispersed into nanometers has an antibacterial effect of 95 to 98%. The aqueous PU of the present invention is an aqueous Pu which is generally known in the art. For example, it is pre-polymerized by various isocyanates and polyols (polyether or polyester type), long-term, sub-addition of a hydrophilic group and a solvent, and the obtained product is The prepolymer of the NC0 terminal 'reacts this product with a compound which can ionize the PU, separates it into water, and then uses a chain extender to increase the molecular weight of the PU and remove excess ^NC〇 functional groups. The isocyanates and polyols used in the present invention are known as isocyanuric acid and polyhydric alcohols which are well known in the art. The hydrophilic group can be: a continuous acid salt type such as

H0C2H4CH(S03Na)CH20H, H2NC2H4NH(CH2)2S03Na, H2NC2H4NH(CH2)3S03Na, C6(NC0)2CH3H2S03Na, etc., and the acid salt type such as dimethylol propionic acid (DMAP) - H2N(CH2) 4CHCOOHNH2, H2NC2H4NHC2H4C02Na, etc., tertiary ammonium type A compound having a hydrophilic functional group such as H0C2H4NCH3C2H40H, H0C2H4NC2H5C2H40H, N-isopropyl diethanolamine, N-tertiarybutyl diethanolamine. The trace solvent may be: N-methy 1 -2-pyrroli done (NMP ), dimethylforamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), acetate or the like. The PU may be ionized with a compound such as a compound such as a tribasic ammonium such as triethylamine or an acid such as acetic acid. The chain extender can be: hydrazine "ethylene diamine, 1,6 hexanediamine

1254055

-ethylene alcohol 0 glycol, 1,4 butanediol and other binary ammonia or binary, the synthesis of the aqueous PU / clay nanocomposite of the present invention, the clay mineral with micron size = size but with nanometer pores The antibacterial modifier changed the shellfish first by ion exchange with the metal ions in the inorganic binder to make it a lipophilic material, and then mixed with the raw material of the synthetic PU, and then? K synthesizes a nanocomposite of aqueous p U / nano-sized clay.

The nano-composite of aqueous PU/nano-grade granular clay prepared by the invention has quite good antibacterial/mold resistance effect, and can be widely used for fabric treatment, clothing mildew proof, packaging material processing, food packaging film, Paint, indoor mildew coating, various coatings, building materials, mildew, home mold, mildew, metal rust and mildew, leather mildew and equipment mildew, etc., quite worthy of industrial use value 0 [Embodiment] (1) Synthetic Aqueous PU Emulsion: The present invention employs a prepolymer mixing method (prep 〇1 ymer in i Xing process) to prepare an aqueous pu emulsion. First, diisocyanate (IPDI) 25 g is reacted with 60.3 g of polyol (polyether or polyester), and dimethylol propionic acid (DMPA) 4·13 g is added as a hydrophilic group, and N-methyl-2-pyrrolidone (NMP) is used. 23·6聋: as a solvent. The product obtained is an NCO-terminated prepolymer, which is then made into a PU anion with 3.2 g of triethylamine, dispersed in 268 g of water, and then 3.0 g of ethylene.

Page 12 1254055 V. Description of the invention

Diamine is a chain extender that increases the molecular weight of the PU and removes excess NC〇 functional groups. ' (2) Clay modification: (1) 25 g of clay is dissolved in distilled water (Ciay: j^〇 = 1:50) and mechanically stirred for 12 hours. The clay is the montmorillonite of PK802 and PK805. ~ (2) Weigh 13.6 grams of [CH3(CH2)n]2(CH3)2NBr quaternary ammonium salt (modifier) dissolved in 25 grams of distilled water, add a few drops of hydrochloric acid to help dissolve. The amount of the quaternary ammonium salt: CEC (Clay cation exchange equivalent) X The molecular weight of the quaternary ammonium salt X The weight of the clay X 1·2 χ 10_3 = The weight of the quaternary ammonium salt (3) The above two solutions are uniformly mixed and mixed 1 2 hours. (4) After the solution was filtered, it was washed several times with distilled water until it was titrated with a silver nitrate solution, and no white precipitate was produced. (5) The obtained product is placed in a vacuum oven, dried, ground into a powder, and sieved through a sieve of 32 5 mesh to obtain a modified clay having a particle size. The size is about 4 inches. ,) Identification of the modified clay using an X-ray diffractometer (XRD),

>1 Bragg, s equation: 2dsin (9=n λ, the distance between the different layers and the layer. (1) Preparation of aqueous Pj/clay nanocomposite: ^ The modified 4·65 g of clay and 60·3 g of polyol (polyether or polyester type) are mixed uniformly, and then the aqueous PU is synthesized as in the above (1), and the aqueous PU σ becomes adjusted to the appropriate Emulsion viscosity and particle size to suit

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V. Description of the invention (8)

Clay's suspension. The synthesized water-based PU/Clay nano-emulsion was centrifuged in a high-speed centrifuge to 'dispense' in water, and X-ray and Transmission Electron Microscop (TEM) were used to detect Cl ay in pu. Dispersion morphology, according to the above formula, the ratio of water-based pu/c nano-re-a membrane is different (a: c 1 ay = 〇%, b: c 1 ay = 1%, c: c 1 ay = 2% d: clay = 3% , e:clay = 4%, f:clay = 5%) Test each property (IV) Culture of the strain: Culture two common strains (1) mold (2) Escherichia coli. The culture of the strain needs to start from the configuration of the medium. First, weigh the heavy bacteria of the required strain and add 100 ml of steamed crane water to stir. Dissolve it in a water bath method, dispense into a conical flask, sterilize in a sterilization kettle, and the temperature is 12 〇, time 15 minutes, cold 'alternate . Followed by the culture of the bacteria, put the sterilized and placed it on about 5 5 and shake it evenly, then pour the solution into the Petri dish of 丨〇m丨, 2 =: After the solid two placed on the medium... Material), then dilute the bacteria in the water without sputum, after using Platinum to sterilize the alcohol lamp, 35. (: Incubate in an incubator, culture time is about 18~24 hours. Put in (5) Antibacterial test: Use microscopic magnifying glass to observe the colony growth condition and photograph, the difference of bacteria effect. T List the effect against the invention: 1 · The oleophilic modification of clay is one of the first, the oleophilic treatment of inorganic clay, clay is a layer

1254055 V. INSTRUCTIONS (9) The inorganic citrate of the structure is ion exchanged with the cations in the clay by the hydrophilic end of the quaternary ammonium salt, in order to enter the long chain alkyl group of the quaternary ammonium salt into the clay. The interlayer layer 'achieves the effect of widening the interlayer distance to facilitate the compatibility of the polymer chain with the oleophilic end of the quaternary ammonium salt present between the clay layers, thereby achieving the modification 'under the same operating conditions, by X - Γ Ay diffraction analysis shows that the change in the interlayer distance will be changed and paid depending on the type of surfactant. As shown in the table, the distance extended by Didodecyldimethyl aminoiiiuni bromide (DMAB), [CH3(CH2)u]2(CH3)2NBr is the largest, which may be the structure and bond angle of the double long-chain alkyl group, making the double long chain The layer between the alkyl group and the inorganic clay presents a type of jack, which effectively enlarges the interlayer distance to 22A, and the interlayer distance of the original clay is 12 A. 2 · c 1 ay in the ρ ο 1 y ο 1 swelling situation modified c 1 ay, can swell in the appropriate po 1 yo 1, a little clay into a variety of different types of poly, its swelling effect Table 2, wherein Aru5620 is poly(hexyl adipate) diol, the average molecular weight is 1898; Aru2410 is poly(butyl adipate) diol, the average molecular weight is 9 88, D3123 is a polyether with a Ε0/Ρ0 functional group in the side chain and an average molecular weight of 1180, D3117 It is a po1yd i ο 1 having a molecular weight of 1400, having a S03Na functional group in the side chain. It can be seen from Table 2 that after modification of Didodecyl-dimethyl ammonium bromide (DMAB), PK802 and PK805 can swell well in various polyols.

Page 15 1254055

V. INSTRUCTIONS (10) 3 · Particle size analysis Figure 2 shows the average particle size of the water-repellent p U / c 1 ay nanocomposite emulsion in different Clav, Jin, A, and y 3 Figure 2 shows the number of fixed hydrophilic groups and the solid content: 'gradually increase the clay content in the composite, the particles of the emulsion are gradually increased by 丄I f to 1 ay itself with ions 16, which interferes with the original pu in the aqueous pu or Hydrophilic nature, the number of available hydrophilic groups is less, the particle size is increased = the average particle size of the aqueous PU without clay is 47 nm, and the average particle size of the 5% ciay methylene emulsion is 76 nm. 4 · Viscosity analysis Figure 2 shows the viscosity of the water-based PU/c 1 ay nanocomposite emulsion with different clay content and solid content. The figure shows that the content of c 1 ay increases with the content of c 1 ay. The viscosity of the emulsion rises rapidly. This may be because the ionic groups in the clay are attracted to each other by the ionic groups in the aqueous PU, resulting in an increase in viscosity. When the clay is not included, the water-based PU viscosity is 6 cps, and the viscosity is 5%. 72 cps. 5 · Thermogravimetric analysis Figure 4 shows the heat resistance analysis after water-based p U / c 1 ay film formation. If the temperature at the weight loss of 5 wt % is defined as the decomposition initiation temperature (Td), then the cl ay is 0 respectively. The Td at wt%, i wt%, 2 wt%, 3 wt%, 4 wt%, and 5 wt% were 253 C, 253 C, 256 C, 260 C, 266 C, and 267 C. When different samples containing (31 & 〇^^%, 1*1:%, 2~1:%, 3%^%, 4~1:%, and 5 wt% were heated to 5 〇〇C, The remaining weight is 2 · 7

Page 16 1254055 ^ V. Description of invention (11) W_U, 2.9 wt%, 3.8 wt%, 4 ? + 〇 /, so as the amount of clay increases, pu / , 4 · 3 Wt%, and 5 · δ so clay The heat resistance of the composite can be improved slightly, 6 · Dynamic mechanical properties analysis Fig. 5 is the mechanical properties of different Clay content state measurement of the joints of the 丄f Fu/c 1 ay nano composite membrane Number:; Li water, uy nano complex 1%, c: clay = 2% d: 〇i ^ ^ ( a .c1ay = 〇%, b:c1ay = shows as the temperature rises, · store /= 3% ,e:Clay = 4%, f:clay = 5%) Right, the storage modulus is fast: bottom: save:;; slow:: 'until -5°w relationship, different clay content;: 'booking big Glass transfer, test error storage modulus size change relationship cay shows that the composite film does not show the film loss modulus 13⁄4 ^= Figure b· is water-based PU/clay nano-recovery: clay^^ b:clay.%5 At about -4 4 °C, _ Mt. e.clay = 4%, f:clay = 5%), in the clay containing the denier / glaze transfer temperature peak, this glass transition temperature and 2 = τ 3: less Almost irrelevant. Figure 5 c. is the relationship between water-based PU/clay^f complex elta with temperature ": plus _:C; d: clay__3%, e:clay = 4%> f:claCy^y- : and cCi The glass transition temperature peak, this glass transition temperature is not related to the amount of ci ay. Antibacterial results Figure 6 shows the water-based PU film without Clay after the anti-fungal test, disc

Page 17 1254055 V. Description of invention (12) Shape culture of color mold in the center of JHI, Figure 7 is the anti-fungal test, long 'but the surrounding perimeter composite film has anti-E. coli surface and surrounding culture clay The water-based PU/c is a small square anti-E. coli effect in the center of the sample: the water-based PU/clay nano-composite film of Clay is coated on the surface of the sample and on the surrounding medium. No mold growth = white mold for cockroaches, water-based PU / clay test mouth. Figure VIII is the water-free pu film without adding cl ay. The small square sample of the center of the disk-shaped culture center is two v-gas, golden E. coli, and Figure 9 is the addition of 3〇/〇妒_不/\ After the anti-E. coli test, culture. There is no growth of Bacillus megacephala, which shows that it is a combination of the above-mentioned invention. The present invention utilizes a clay with a micro-hole of antibacterial agent (c 1 ay 丨 撑 , , , , pol pol pol pol pol pol pol pol pol pol pol pol pol pol pol The composite emulsion, after mixing the raw materials, is then polymerized into filamentous (stripe) particles of short water to form a nano-scale composite, and the water content of the water p U and the clay is also significantly increased. This is because of the heat resistance of the composite membrane, but for the reverberation. The invention adds a cheap mold to the membrane to have a good anti-microbial effect, and is better to be antibacterial, and to promote the trans-PU, the granule, and the resistance. Composite clay with filmed soil for fruit preparation, special examples, non-micron-sized particles, after modification, the viscosity after synthesis and stable modification can change the effect of clay on the aqueous PU 。. With the average ionicity of the emulsion Shadow glass transfer temperature and water-based PU Nai is generally used to limit the size of the hair granules but has a naphtha, the internal pore diameter of the water-based PU and the clay and the synthetic PU form the nano-sized long emulsion. , sticky, clay Fortified hardly Movies meters composite membrane, the bacteria and fungi and the like,

1254055

Page 191254055__ Brief description of the table Table I, different kinds of quaternary ammonium salt to PK-80 5 after the modification of 2 6» and d -space (A) Table 2, the modified c 1 ay, in different P 〇1 y ο 1 swelling situation Figure 1. Clay (montmorillonite, Montmorillonite) structure diagram (eight 12_ xMgx) vni (Si4) IV01 〇 (〇H) 2Mn + XZn. H20 Figure 2, 2 5 wt The average particle size of the aqueous solids PU / c 1 ay nanocomposite emulsion with % solid content changes with the content of c 1 ay. Figure 3. The viscosity of the aqueous PU/cl ay nanocomposite emulsion with 25 wt% solid content with c 1 Figure 4 shows the change of heat resistance of water-based PU / c 1 ay nano composite film. Figure 5. A. Dynamic storage modulus of water-based PU/cl ay nano composite film with temperature (a:clay = 0%, b:clay = l%, c: clay = 2%, d: clay=3%, e:c1 ay = 4%, f:clay = 5%) Figure 5b · Waterborne PU / c 1 ay Nai The dynamic loss modulus of the rice composite membrane varies with temperature (a:clay = 0%, b:clay = l%, c: clay = 2%, d: clay=3%, e: c1 ay -4%, f : c 1 ay = 5%) Figure 5 c. Dynamic Tan Delta of water-based PU/clay nanocomposite film changes with temperature a: Clay=〇%, b:clay = 1%, c: clay=:2%, d: clay= again 3%, e: clay-4%, f:clay = 5°/〇) Figure VI, not Adding the water-based pu film of c 1 ay after the anti-fungal test, the surface of the square sample has the growth of bacteria on the surface. Figure 7. The pu/cUy nano-composite film with 3% clay added after the anti-fungal test, the middle square No mold growth on the surface of the sample. Figure 8. Water-based pu film without added clay.

1254055 The simple description shows the growth of E. coli on the surface of the square sample. Figure 9. The aqueous PU / c 1 ay nano composite membrane with 3 % c 1 ay added. After the anti-E. coli test, the surface of the square sample is free of E. coli. Growing

Page 21 1254055 Quaternary ammonium bromide^ 2Θ, d -space(A)* non. 7.4 heart 11.81, C12H25N(CH3)3Br 5.28 16.73 C14H29N(CH3)3Blv 4.92, 17.95- C16H33N(CH3)3Blv 4.70- 18.79- iCTiCH^nbCCH^Br 4.02 ' 21.96 Table 1

Ssixsl type Clay type* Clay swelling situation in ¥〇1 p PEG1000, 1. PK802 (DMAB modification) 2. PK805 (DMAB modification and good #PEG2000^ 1. PK802 (DMAB modification) 2. PK805 (DMAB change Quality > Good P PTMOIOOO. 1. PK802 (DMAB change) 2. PK805 (DMAB modified good ^ Ani2410 - 1_PK802 (DMAB changed) 2. PK805 (DMAB modified > good ^ Aru5620- l.PK802 ( DMAB changed t) 2-PK805 (DMAB modified > excellent ^ D3123^ 1. PK802 (DMAB changed) 2. PK805 (DMAB modified > good - D3117^ 1_ΡΚΚ) 2^) ΜΑΒ Change ^ 2.PK805 (DMAB modified > very good #第页

Claims (1)

1254055 VI. Patent application scope 1. An antibacterial waterborne polyurethane emulsion which is composed of an aqueous polyurethane synthetic raw material and a clay modified by an antibacterial agent, polymerized into a water-based PU and has a nanometer-sized particle size. Clay nano-composite emulsion. 2. The antibacterial aqueous polyaminophthalate emulsion of claim 1 is prepared by a prepolymer blending method to prepare an aqueous polyurethane emulsion. 3. An antibacterial aqueous polyurethane emulsion according to claim 1 of the patent scope, which reacts an isocyanate with a polyol, and adds a hydrophilic group and a solvent to obtain a prepolymer containing an NC0 terminal group, and then pre-precipitates The polymer is anionized and dispersed in water. 4. An antibacterial aqueous polyurethane emulsion according to claim 1, wherein the aqueous polyurethane is extended by a chain extender to increase the molecular weight and remove excess NC0 functional groups. 5. The antibacterial aqueous polyurethane emulsion according to claim 1, wherein the polyol is a polyether or a polyester polyol. 6. An antibacterial aqueous polyurethane emulsion according to claim 1 of the patent scope, wherein the clay modified by the antibacterial agent has a micron-sized particle size but has a nanometer before being mixed with the PU polymerization raw material and before the PU polymerization. Level hole. 7. The antibacterial aqueous polyaminophthalate emulsion according to claim 1 of the patent scope, wherein the antibacterial agent is: a quaternary alkyl ammonium salt, a long chain phenyl quaternary ammonium salt (quaternary quaternary ammonium salt) Alkylphenylammonium salt), gasified benzene sulphate, C12H2 5N(CH3) 3Br, C14H29N(CH3)3Br, C 16H 33N ( CH 3) 3Br, [ CH 3( CH 2) "] 2( CH 3) 2NBr, others Antibacterial chemical composition, etc. 8. An antibacterial aqueous polyaminophthalate emulsion as claimed in claim 1 Page 22 1254055 VI. Scope of Application The antibacterial agent may additionally contain phenolic compounds, alcohol, halogens, heavy metals and quaternary ammonium salts. 9. The antibacterial aqueous polyurethane emulsion according to claim 1, wherein the antibacterial agent is a quaternary ammonium salt. 10 0. The antibacterial aqueous polyurethane emulsion of claim 1 is widely used in fabric treatment, clothing mildew prevention, packaging material processing, food packaging film, coating, indoor mildew coating, various coating Packing, building materials, mildew, home mold, mildew, metal rust and mildew, leather mildew and equipment mildew. 1 . A method for preparing an antibacterial aqueous polyamino phthalate emulsion, which comprises mixing a clay modified by an antibacterial agent with a polyol, and then synthesizing the aqueous polyurethane to form a nano-sized granule. The size of clay and aqueous polyamino phthalic acid S is a nano-composite emulsion. 1 2. The preparation method of the antibacterial aqueous polyurethane emulsion according to the claim 1 of the patent scope, wherein the aqueous polyurethane is adjusted to an appropriate emulsion viscosity and particle size to suit the suspension of the clay. . 1 . The preparation method of the antibacterial aqueous polyaminophthalate emulsion according to claim 11 , wherein the synthesized aqueous polyurethane and clay compound are precipitated in a high speed centrifuge, and then need to be redispersed in In the water. Page 23