CN103059710A - Preparation method of antibacterial waterborne polyurethane woodware paint - Google Patents

Abstract

The invention relates to a preparation method of antibacterial waterborne polyurethane woodware paint. The preparation method comprises the following steps of: firstly performing prepolymerization reaction on polycarbonate diol and diphenylmethane diisocyanate to obtain a PU (polyurethane) prepolymer, further preparing a component with antibacterial performance through an ultraviolet method, then adding the component with the antibacterial performance and 2-sodium sulfonate-1, 4-butanediol into the PU prepolymer, then preparing a waterborne polyurethane emulsion with the antibacterial performance after condensation polymerization, and then respectively adding an appropriate amount of auxiliaries to finally obtain the antibacterial waterborne polyurethane woodware paint. The waterborne polyurethane woodware paint prepared by the method disclosed by the invention has good performance of protein adsorption resistance and microbial adsorption resistance. The waterborne polyurethane woodware paint can keep adhesion, water resistance and mechanical performance of the coating and simultaneously realize good antibacterial performance.

Description

A kind of preparation method of antibacterial aqueous polyurethane carpentry paint

Technical field

The present invention relates to the woodwork coating correlative technology field, related in particular to a kind of preparation method of antibacterial aqueous polyurethane carpentry paint.

 

Background technology

Woodwork coating is the important component part of coatings industry, refers to mainly be applicable to furniture, floor, stationery sports goods, musical instrument and constructional ornamental material etc. for the coating on the equipment of the starting material such as solid wood board, wood grain panel, hard rubber sheet, fiberboard preparation.At present, the aqueous polyurethane coating that high-performance and low VOC content combine, because polyurethane molecular has cutting, in conjunction with new synthetic and crosslinking technological, can effectively control system component and structure, thereby make it have good film formation at low temp, high temperature resistant after-tackiness, high strength, wear resistance, the feature of environmental protection etc., therefore become one of coating variety with fastest developing speed.Namely the artistic floors of " the Water Cube " is employed such as Beijing National swimming center is exactly the aqueous polyurethane coating that Bayer Material Science company provides.

, because urethane resin has excellent chemical property and mechanical-physical, in chemical field, be widely used first since the synthesis of polyurethane (PU) from nineteen thirty-seven Germany professor Otto.Bayer.Polyurethane coating is widely used in the fields such as petrochemical equipment, ocean, boats and ships, electromechanics, vehicle, weaving, leather, timber, wood lacquer, plastics, building, waterproof paint because having good wear resistance, snappiness, weather resistance, preservative property and insulativity.The development of urethane is broadly divided into two stages: the fs is mainly take solvent-borne type as main; Subordinate phase is the stage that aqueous polyurethane develops rapidly.Traditional solvent borne polyurethane contains a large amount of organic solvents and a certain amount of free isocyanate, affects the residual isocyanate monomer in people's the healthy and living environment, particularly solvent-type double-component urethane, and toxicity is high.Along with human life quality's raising, environmental regulation is also more and more stricter, and various environmental regulations have strict restriction to the quantity discharged of volatile organic compounds (VOC), the content of hazardous solvent.And aqueous polyurethane is because it take water as dispersion medium, not only has the advantages such as nontoxic, nonflammable, free from environmental pollution, energy-conservation, safe and reliable; Some important performance characteristics that also have simultaneously solvent borne polyurethane, aqueous polyurethane coating is high with the hardness of polyurethane coating film, strong adhesion, corrosion-resistant, anti-solvent are good etc., and advantage combines with the low VOC content of water-borne coatings, meet " three the prerequisites " (resource that develops coatings industry, the energy, pollution-free) and " four E principles " (economic ECONOMY, efficient EFFICIENCY, ecological ECOLOGY, energy ENERGY) and the requirements of the times of day by day strengthening adapt.Therefore aqueous polyurethane coating obtains a wide range of applications in recent years.And the aqueous polyurethane take water as dispersion medium the has advantage such as nontoxic, free from environmental pollution, energy-conservation, easy to operate, and Application Areas is extensive.Along with various countries' environmental regulation to the restriction of VOC and to the attention of environmental protection so that aqueous polyurethane has obtained faster development, be widely applied in fields such as fabric, leather, tackiness agents, just progressively the replace solvents type polyurethane.Along with progress and the strict control of VOC content and the raising of people's Environmental Safety and health perception of technology, water-based PU will become an important developing direction from now on.

Urethane developed since the thirties in 20th century; and the research of a small amount of aqueous polyurethane was arranged just in the forties; nineteen forty-three Germanization scholar Schlack successfully prepares polyaminoester emulsion first with vulcabond emulsification in water in the presence of emulsifying agent and protective colloid.The researchist of nineteen fifty-three Du Pont company is scattered in water with the toluene solution of diisocyanate based base polyurethane prepolymer for use as, has synthesized aqueous polyurethane with the diamine chain extension.But the polyurethane material science was at the early-stage at that time, and aqueous polyurethane does not also come into one's own, until just first industrialization in 1967, Beyer Co., Ltd formally produced polyurethane aqueous dispersion body in enormous quantities as leather coating in 1972.The seventies and eighties in 20th century, some aqueous polyurethane products of the states such as U.S., moral, day have developed into actual production and application from advanced development, there is the aqueous polyurethane product-feed of the multiple trade mark in some companies, such as aqueous vinyl adhesive for polyurethane KR series of the series such as the X of the series such as DispercollKA of German Bayer company, U.S. Wyandotte chemical company and E, Japanese silver dollar industry company etc.From the later stage nineties 20th century, the Application Areas of aqueous polyurethane begins constantly to widen, and coheres at PVC, there is certain industrial applications the aspect such as automotive upholstery, coating, coating.

China was from the aqueous polyurethane that begins one's study in 1972, and the nineties in 20th century, the PUD technological achievement of University of Anhui, Dandong light industry research institute, Chengdu Univ. of Science ﹠ Technology (branch of existing Sichuan University) etc. all successively is converted.At present, China's existing many fields applying waterborne polyurethane product, but wherein many expensive goods still can not be self-supporting, so the independent research high-performance water-based polyurethane just becomes one of the most popular direction of domestic polyurethane field.

For further improving mechanical property and the chemical resistance of AQUEOUS POLYURETHANE DISPERSION COATINGS, often introduce reactive group and carry out crosslinked.Crosslinked method mainly contains 3 kinds: (1) interior crosslinking namely introduces three-dimensional structure when prepolymerization, or use the tertiary amine chain extension during chain extension in water, but the introducing of three-dimensional structure easily causes gel to occur.Develop recently the new technology of using the urine butanone to make internal crosslinker such as U.S. Olin company, make stable latex system.This technology utilizes excessive diamine to move in the emulsion particle, and the urine butanone radical reaction formation biuret linkage with in the polyurethane skeleton brings out auxiliary crosslinking reaction and makes.By using urine butanone internal crosslinker can improve mechanical property and the solvent resistance of monocomponent waterborne polyurethane coating; (2) self-crosslinking method, vegetables oil or its lipid acid that namely will contain unsaturated link(age) when aqueous polyurethane is synthetic are introduced in the molecular chain, come the catalysis self-crosslinking by metal catalyst (such as cobalt, manganese, calcium salt).This helps to reduce particle diameter, adjust the surface tension of polyurethane aqueous dispersion body, improve urethane water-dispersion varnish to the penetrating power of timber pore and improve coalescent speed and the degree of particle, shorten the time of drying of filming, thus the filming of availability excellence.R9403, R2001 etc. such as the Neoreslins of U.S. specialty chemical company.This modification also can reduce the cost of coating, improves drying property, fillibility, transparency, gloss, wet adhesion and the levelling property of coating.Document has then been developed One-pack, this coating has excellent outside durabitity, shock-resistance, resistant, scratch resistance and chemical resistance etc., indices meets or exceeds traditional solvent borne polyurethane coating, is widely used in paint of wooden floor, external application coating varnish and coatings for furniture; (3) external crosslinking method namely adds linking agent.The structures shape of aqueous polyurethane the composition of outside cross-linking agent, and outside cross-linking agent commonly used when hydroxyl in the polyurethane molecular, amino has water dispersible polyisocyanate, nitrogen heterocycle propane compound, aminoresin etc.; During with carboxyl, compound and some metallic compound of polyamine commonly used, cyclopropane are such as Al (OH) in the polyurethane molecular ₃, Ca (OH) ₂Deng making outside cross-linking agent.External crosslinking method usage comparison trouble, and linking agent is mostly poisonous.

The aqueous polyurethane composite modification material can remedy existing these defectives in cross-linking modified, and the material of modification has a variety of, comprises Resins, epoxy and organosilicon etc.Resins, epoxy has stronger rigidity and sticking power, and the performances such as gloss, stability, hardness are good, and are polyol, with the reaction of urethane in, branch point can be introduced the main chain of urethane, make it the forming section reticulated structure, performance is more excellent.Adding Resins, epoxy can make tensile strength, water tolerance and the solvent resistance of coating obviously strengthen.

Xu Gewen etc. are by epoxy modified aqueous urethane, and the degree of branching that Resins, epoxy is higher is incorporated on the polyurethane backbone, has improved sticking power, drying rate, hardness of film and the water tolerance of emulsion film.With the good waterborne epoxy modified polyurethane coating of its preparation over-all properties, be applicable to the timber floor application, result of use is good.Organosilicon can improve water tolerance, weathering resistance and the sticking power of aqueous polyurethane effectively because it has unique chemical structure and extremely low surface energy.

Hou Menghua etc. adopt the polyether type aqueous urethane of aminosilane coupling agent modifying, have made the waterborne polyurethane wood coatings of excellent performance.Its specific practice is with diphenylmethanediisocyanate, polycarbonate diol, 2-sodium sulfonate-1, the 4-butyleneglycol is raw material, obtain performed polymer by high molecular weight reactive, with this performed polymer chain extension in the amino silicane coupling agent solution of lower concentration, make a kind of aqueous emulsion of polyurethane of aminosilane coupling agent modifying.This emulsion is equipped with the waterborne polyurethane wood coatings that other auxiliary agent makes again, has excellent sticking power, water tolerance and mechanical property.Also can be by other certain methods and the performance of the means aqueous polyurethane woodenware coating of improving single component.

But, the range of application of water-borne wood coating technology is also very limited, the antibacterial and mouldproof poor performance of wood lacquer most importantly wherein, exist the antibiotic time short, easy to change etc., especially some moist occasion (such as kitchen, toilet etc.) is the most easily grown microorganism in the domestic environment, causes the bacteria concentration of room air bacteria concentration and body surface to increase; In addition, present existing aqueous woodware paint can only be applied to indoor mostly, out of doors or indoor sunshine many places be prone to the phenomenons such as flavescence, cracking.

At present, the employed antiseptic-germicide of domestic wood lacquer is: organic antibacterial agent; The photocatalysis antibacterial agent is such as titanium dioxide etc.; Silver ion antimicrobial agent, nano silver antimicrobials.The organic antibacterial agent persistence is poor, and microorganism easily produces resistance, and it is poisonous easily to degrade, and does not meet environmental requirement; The photocatalysis antibacterial agent only under the condition that satisfies certain UV-light, oxygen, water, just has good germ resistance, therefore is not suitable for indoor application; The silver ion antimicrobial agent germ resistance is good but the easy variable color of silver ions has not only reduced germ resistance, but also has limited its application in white and light system; Although nano silver antimicrobials antibacterial effect broad-spectrum high efficacy, its easy oxidation discoloration, and non-refractory.Therefore exploitation has the aqueous polyurethane coating that excellent sticking power, water tolerance and mechanical property have again antifouling property simultaneously and has very important practical significance.

 

Summary of the invention

The object of the invention is to provide a kind of preparation method of antibacterial aqueous polyurethane carpentry paint.

Technical scheme of the present invention is as follows:

A kind of preparation method of antibacterial aqueous polyurethane carpentry paint is characterized in that, may further comprise the steps:

1) preparation of component A:

Under the drying nitrogen protection, the polycarbonate diol of the dehydration of 58 ~ 69 weight parts, the diphenylmethanediisocyanate of 15 ~ 21 weight parts are joined in the ground four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed, logical steam, be heated to 70 ~ 80 ℃, the tetrahydrofuran solvent that adds again 400 ~ 500 weight parts carries out mechanical stirring, stirring velocity 600～1500rpm, stirring reaction 1 ~ 2 h; Be cooled to about 60 ℃, add again the 2-sodium sulfonate-BDO of 4.2 ~ 6.8 weight parts, stirring reaction 2h;

2) preparation of B component:

Take by weighing the methacrylic acid N of 6 ~ 9 weight parts, N diamino methyl esters is in weighing bottle, add the sulfydryl ethylene glycol of 12 ~ 13 weight parts and the 2-hydroxy-2-methyl Propiophenone of 0.25 ~ 0.3 weight part, add again the DMF of 45 ~ 50 weight parts, after passing into nitrogen 0.8 ~ 1h in the weighing bottle, sealing, UV-irradiation 1 ~ 1.5h, the concentrated solvent of removing of rotation, reaction product is precipitated 2 times vacuum-drying 24h in normal hexane;

3) B component is joined among the component A 80 ℃ of lower reaction 24h; Add neutralizing agent, temperature is 25～60 ℃ again, and stirring velocity is 800～1500rpm, in and 1～3h, regulating the pH value is 4～9; Again reactant is added in the high purity deionized water, stirring velocity is 2500 ~ 2800rpm, stirring and emulsifying 0.5 ~ 0.8h adds the wetting dispersing agent of 0.7 weight part, the defoamer of 1.1 weight parts, the thickening material of 0.9 weight part more successively, with the rotating speed stirring 0.5h of 700-1000rpm; Rotating speed is transferred to flow agent that 600rpm adds 1.5 ~ 2.0 weight parts adjust viscosity and froth breaking 10 minutes at a slow speed, get product.

The present invention is at first by polycarbonate diol and diphenylmethanediisocyanate prepolymerization reaction, obtain the PU prepolymer, add again 2-sodium sulfonate-1, the 4-butyleneglycol is as the wetting ability chainextender, again with methacrylic acid N, N diamino methyl esters and mercapto-propanediol mix, add solvent and as the 2-hydroxy-2-methyl Propiophenone of light trigger, and by the get everything ready component of anti-microbial property of UV-light legal system, then in reacted prepolymer, add above-mentioned anti-microbial property component, make the aqueous polyurethane emulsion with anti-microbial property after utilizing polycondensation, add respectively again appropriate amount of addition agent, obtain at last antibacterial aqueous polyurethane carpentry paint.

The various product that defoamer in the composition, thickening material, Ricinate, slip(ping)agent, flow agent are on the market to be commonly used.Defoamer can be with the BYK series of German Bi Ke company, the EFKA series of Dutch EFKA company, the PLURIOL series of BASF Aktiengesellschaft etc.Thickening material can be used the ACRYSOL series of U.S. Rhom and Hass, the RHEOLATE series of strength brightness company etc.Ricinate can be used the PE series of Henkel Corp., the SURFYNOL series of U.S.'s gas chemical industry etc.Flow agent comprises the TEGO series of the SUNFYNOL series of RHEOLATE series, U.S.'s gas chemical industry of RM series, the strength brightness company of U.S. Rhom and Hass, German Di Gao company etc.

The waterborne polyurethane wood coatings that the inventive method makes has good anti-protein adsorption and the performance of antimicrobial absorption.In the sticking power that keeps coating, water tolerance and mechanical property while good antimicrobial property.

 

Embodiment

Below in conjunction with embodiment the present invention is further described.

Embodiment 1

1) preparation of component A:

Under the drying nitrogen protection, the polycarbonate diol of the dehydration of 58 weight parts, the diphenylmethanediisocyanate of 21 weight parts are joined in the ground four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed, logical steam, be heated to 70 ℃, the tetrahydrofuran solvent that adds again 400 weight parts carries out mechanical stirring, stirring velocity 600rpm, stirring reaction 1 h; Be cooled to about 60 ℃, add again the 2-sodium sulfonate-BDO of 4.2 weight parts, stirring reaction 2h;

2) preparation of B component:

Take by weighing the methacrylic acid N of 6 weight parts, N diamino methyl esters is in weighing bottle, add the sulfydryl ethylene glycol of 12 weight parts and the 2-hydroxy-2-methyl Propiophenone of 0.25 weight part, add again the DMF of 50 weight parts, after passing into nitrogen 0.8 h in the weighing bottle, sealing, UV-irradiation 1 h, the concentrated solvent of removing of rotation, reaction product is precipitated 2 times vacuum-drying 24 h in normal hexane;

3) B component is joined among the component A 80 ℃ of lower reaction 24h; Add neutralizing agent, temperature is 25 ℃ again, and stirring velocity is 800rpm, in and 1 h, regulating the pH value is 4; Reactant is added in the high purity deionized water, stirring velocity is 2500rpm again, and stirring and emulsifying 0.5h adds the wetting dispersing agent of 0.7 weight part, the defoamer of 1.1 weight parts, the thickening material of 0.9 weight part more successively, with the rotating speed stirring 0.5h of 700rpm; Rotating speed is transferred to flow agent that 600rpm adds 1.5 weight parts adjust viscosity and froth breaking 10 minutes at a slow speed, get product.

 

Embodiment 2

1) preparation of component A:

Under the drying nitrogen protection, the polycarbonate diol of the dehydration of 60 weight parts, the diphenylmethanediisocyanate of 18 weight parts are joined in the ground four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed, logical steam, be heated to 75 ℃, the tetrahydrofuran solvent that adds again 450 weight parts carries out mechanical stirring, stirring velocity 1200rpm, stirring reaction 1.5 h; Be cooled to about 60 ℃, add again the 2-sodium sulfonate-BDO of 5 weight parts, stirring reaction 2h;

2) preparation of B component:

Take by weighing the methacrylic acid N of 6 ~ 9 weight parts, N diamino methyl esters is in weighing bottle, add the sulfydryl ethylene glycol of 12 weight parts and the 2-hydroxy-2-methyl Propiophenone of 0.25 weight part, add again the DMF of 48 weight parts, after passing into nitrogen 0.9 h in the weighing bottle, sealing, UV-irradiation 1.2 h, the concentrated solvent of removing of rotation, reaction product is precipitated 2 times vacuum-drying 24h in normal hexane;

3) B component is joined among the component A 80 ℃ of lower reaction 24h; Add neutralizing agent, temperature is 40 ℃ again, and stirring velocity is 1200rpm, in and 2h, regulating the pH value is 7; Reactant is added in the high purity deionized water, stirring velocity is 2600rpm again, and stirring and emulsifying 0.6 h adds the wetting dispersing agent of 0.7 weight part, the defoamer of 1.1 weight parts, the thickening material of 0.9 weight part more successively, with the rotating speed stirring 0.5h of 800rpm; Rotating speed is transferred to flow agent that 600rpm adds 1.8 weight parts adjust viscosity and froth breaking 10 minutes at a slow speed, get product.

 

Embodiment 3

1) preparation of component A:

Under the drying nitrogen protection, the polycarbonate diol of the dehydration of 69 weight parts, the diphenylmethanediisocyanate of 15 weight parts are joined in the ground four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed, logical steam, be heated to 80 ℃, the tetrahydrofuran solvent that adds again 500 weight parts carries out mechanical stirring, stirring velocity 1500rpm, stirring reaction 2 h; Be cooled to about 60 ℃, add again the 2-sodium sulfonate-BDO of 6.8 weight parts, stirring reaction 2h;

2) preparation of B component:

Take by weighing the methacrylic acid N of 9 weight parts, N diamino methyl esters is in weighing bottle, add the sulfydryl ethylene glycol of 13 weight parts and the 2-hydroxy-2-methyl Propiophenone of 0.3 weight part, add again the DMF of 45 weight parts, after passing into nitrogen .1h in the weighing bottle, sealing, UV-irradiation 1.5h, the concentrated solvent of removing of rotation, reaction product is precipitated 2 times vacuum-drying 24h in normal hexane;

3) B component is joined among the component A 80 ℃ of lower reaction 24h; Add neutralizing agent, temperature is 60 ℃ again, and stirring velocity is 1500rpm, in and 3 h, regulating the pH value is 9; Reactant is added in the high purity deionized water, stirring velocity is 2800rpm again, and stirring and emulsifying 0.8h adds the wetting dispersing agent of 0.7 weight part, the defoamer of 1.1 weight parts, the thickening material of 0.9 weight part more successively, with the rotating speed stirring 0.5h of 1000rpm; Rotating speed is transferred to flow agent that 600rpm adds 2.0 weight parts adjust viscosity and froth breaking 10 minutes at a slow speed, get product.

In addition, need to prove, the specific embodiment described in this specification sheets, its prescription, title that technique is named etc. can be different.Allly conceive equivalence or the simple change that described structure, feature and principle are done according to patent of the present invention, be included in the protection domain of patent of the present invention.Those skilled in the art can make various modifications or replenish or adopt similar mode to substitute according to figure embodiment described; only otherwise depart from structure of the present invention or surmount this scope as defined in the claims, all should belong to protection scope of the present invention.Although the present invention with embodiment openly as above; but it is not to limit protection scope of the present invention; any technician who is familiar with this technology not breaking away from change and the retouching of doing in the spirit and scope of the present invention, all should belong to protection scope of the present invention.

Claims (1)

1. the preparation method of an antibacterial aqueous polyurethane carpentry paint is characterized in that, may further comprise the steps:

1) preparation of component A:

Under the drying nitrogen protection, the polycarbonate diol of the dehydration of 58 ~ 69 weight parts, the diphenylmethanediisocyanate of 15 ~ 21 weight parts are joined in the ground four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed, logical steam, be heated to 70 ~ 80 ℃, the tetrahydrofuran solvent that adds again 400 ~ 500 weight parts carries out mechanical stirring, stirring velocity 600～1500rpm, stirring reaction 1 ~ 2 h; Be cooled to about 60 ℃, add again the 2-sodium sulfonate-BDO of 4.2 ~ 6.8 weight parts, stirring reaction 2h;

2) preparation of B component:

Take by weighing the methacrylic acid N of 6 ~ 9 weight parts, N diamino methyl esters is in weighing bottle, add the sulfydryl ethylene glycol of 12 ~ 13 weight parts and the 2-hydroxy-2-methyl Propiophenone of 0.25 ~ 0.3 weight part, add again the DMF of 45 ~ 50 weight parts, after passing into nitrogen 0.8 ~ 1h in the weighing bottle, sealing, UV-irradiation 1 ~ 1.5h, the concentrated solvent of removing of rotation, reaction product is precipitated 2 times vacuum-drying 24h in normal hexane;

3) B component is joined among the component A 80 ℃ of lower reaction 24h; Add neutralizing agent, temperature is 25～60 ℃ again, and stirring velocity is 800～1500rpm, in and 1～3h, regulating the pH value is 4～9; Again reactant is added in the high purity deionized water, stirring velocity is 2500 ~ 2800rpm, stirring and emulsifying 0.5 ~ 0.8h adds the wetting dispersing agent of 0.7 weight part, the defoamer of 1.1 weight parts, the thickening material of 0.9 weight part more successively, with the rotating speed stirring 0.5h of 700-1000rpm; Rotating speed is transferred to flow agent that 600rpm adds 1.5 ~ 2.0 weight parts adjust viscosity and froth breaking 10 minutes at a slow speed, get product.