KR0163276B1 - Method for preparation for non-ion urethane-acryl water dispersion - Google Patents

Abstract

The present invention relates to a method for producing a bio-based urethane-acrylic water dispersion containing a water-dispersible polyurethane and a vinyl polymer, excluding the use of a general solvent, to synthesize a polyurethane prepolymer having a polyether group in the presence of a vinyl monomer After dispersing this in water, the chain extender terminates the reaction with the remaining isocyanate group, and then adds a vinyl monomer, thereby producing a bio-based urethane-acrylic water dispersion by free radical polymerization.

Description

Method for producing a bio-based urethane-acrylic water dispersion.

The present invention relates to a method for producing a nonionic urethane-acrylic water dispersion containing a water dispersible polyurethane and a vinyl polymer.

Generally, the polyurethane water dispersion in the water system is prepared by forcibly emulsifying under high agitation conditions using an emulsifier or by introducing ionic groups into the polyurethane to enable self dispersion.

However, the method by forced emulsification (US Pat. No. 3,294,724) has a problem in that the manufacturing process is difficult and the water resistance is degraded by the emulsifier present in the coating film. In addition, the polyurethane water dispersion (US Pat. No. 3,479,310) by the method of introducing ionic groups is excellent in physical properties such as elastic strength, hydrolysis resistance and weather resistance, but since it has an inclination of the electrolyte itself, the electrolyte and low temperature It has the problem of being sensitive to. In addition, high-solid acrylic-melamine clear paint catalyzed by strong acid in the base coat of light color system (white, yellow, etc.) using anionic polyurethane water dispersion, especially in the multi-coating system of automotive paints. In the case of coating, defects on the coating film such as wrinkles of the coating film and deterioration of the distinctness of image (DOI) appear. U.S. Patent No. 5,137,961 exhibits improved properties by containing vinyl polymer in the properties of the urethane water dispersion, but there is a problem in that it cannot guarantee stability against electrolytes and low temperatures because it includes anionic salts.

Therefore, in the present invention, by developing a bio-based urethane-acryl modified acryl in urethane, it exhibits excellent mechanical and chemical properties, is less sensitive to electrolyte, less sensitive to humidity change during coating, and so-called popping. It is effective in preventing, can be applied to flexible base material, and can be applied for base-coat of automobile base-coat / creeper / coat system.

That is, the present invention excludes the use of a general solvent and synthesizes a polyurethane prepolymer having a polyether group in the presence of a vinyl monomer and disperses it in water, and then terminates the reaction with the remaining isocyanate groups by a chain extender, and then It is an object of the present invention to provide a method for producing a bio-based urethane-acrylic water dispersion by free radical polymerization while introducing a vinyl monomer.

The side chain stabilized polyurethane polymer pure dispersion according to the invention can be characterized as a dispersion comprising the following composition.

A) at least one organic compound having at least two active hydrogen functional groups;

B) a nonionic stabilizer composed of the following compositions;

i) Isocyanate intermediates partially treated by reaction of monofunctional polyethers with compounds containing polyisocyanates

ii) compounds containing at least one active amine hydrogen and at least two active hydroxy groups

C) compounds containing at least 1/2 polyisocyanate; And

D) vinyl monomers or mixtures of monomers containing at least one polymerizable ethylenically unsaturated group as a reactive diluent.

The terminal stable polyurethane polymer water dispersion can also be specified as a dispersion comprising the following composition.

A) at least one organic compound having at least two active hydrogen functional groups;

B) polyethers of monofunctional groups;

C) polyisocyanates; And

D) vinyl monomers or mixtures of monomers as reactive diluents.

When explaining in detail the method for producing a bion-based side chain / terminal stable urethane-acrylic polymer water dispersion according to the present invention using the side chain / terminal stable polyurethane polymer water dispersion, first, the side chain stable polyurethane polymer is first Reacting isocyanates with polyethers containing monofunctional active hydrogens to form partially treated polyisocyanates and then reacting them with compounds containing at least one active amine hydrogen and at least two active hydroxy groups A system stabilizer is prepared and then prepared by reacting a polyester polyol resin and a polyisocyanate obtained by reaction of an excess polyol with a compound containing a bifunctional carboxylic acid in the presence of a vinyl monomer which is a reactive diluent.

The structure of the ice-temperature stabilizer used in the reaction is as follows.

Wherein R represents a divalent group excluding isocyanate groups in diisocyanates having a molecular weight ranging from 112 to 1000, X represents oxygen or -NR _2- , and R ₁ and R ₂ contain 1 to 12 carbon atoms To represent a monovalent hydrocarbon group, R ₃ represents hydrogen or a monovalent hydrocarbon group containing 1 to 8 carbon atoms, n represents an integer of 4 to 89, and the molecular weight of the polyether is in the range of 1200 to 3000. desirable.

Secondly, the terminally stable polyurethane polymer reacts a polyester polyol resin obtained by the reaction of an excess polyol with a compound containing a bifunctional carboxylic acid, a polyether and a polyisocyanate of a monofunctional group in the presence of a vinyl monomer which is a reactive diluent. To make it.

The side chain / end stabilized polyurethane polymer prepared in this way is reacted with the remaining isocyanate groups by water dispersion and chain extender under high speed stirring to produce a stable nonionic polyurethane-urea water dispersion, and then the water dispersion and an additional amount of A stable, particulate nonionic urethane-acrylic water dispersion is produced by a conventional free radical polymerization method while simultaneously dropping a vinyl monomer. At this time, the weight ratio of the polyurethane and the vinyl monomer is 10:90 to 90:10.

As for the stirring speed in the water dispersion of the said polyurethane polymer, 2,000-5,000 RPM is preferable.

The preparation of nonionic urethane prepolymers is carried out with stoichiometric excess polyisocyanate to the polyol in an anhydride state at a temperature of about 30-130 ° C. to maintain until the isocyanate and hydroxyl groups are fully reacted. At this time, the ratio of the polyisocyanate and the hydroxyl group is 1.1: 1 to 6: 1, preferably 1.5: 1 to 3: 1.

If the terminal stable polyurethane resin additionally contains a monomer containing at least one trifunctional hydroxy group, the final urethane resin contains 10 to 30 parts by weight of polyisocyanate.

The polyisocyanate may be represented by the following general formula,

R (NCO) ₂

R represents an organic group except for isocyanate, has a molecular weight in the range of 112 to 1,000, preferably about 140 to 400. Aliphatic or cycloaliphatic have favorable properties in terms of UV resistance and weather resistance, and it is possible to select and mix appropriate diisocyanate monomers according to the required coating performance.

Useful isocyanates include 2,2,4-trimethylhexamethylene diisocyanate (TMDI), 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4, 4'-methylene-bis- (cyclohexylene diisocyanate), α, α'-xylene diisocyanate and the like, and suitable aromatic diisocyanate monomers are toluene diisocyanate, 2,4,6-triisocyanate toluene, 4,4 , 4-triisocyanate triphenylmethane, 1,2,4-benzene triisocyanate and the like, toluene diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethine diisocyanate, meta or paris tetramethyl Xylene diisocyanate etc. are more preferable, These are used individually or in mixture of 2 or more types.

Further, a compound containing at least one or more active amine hydrogens and at least two or more active hydroxy groups is diethanolamine.

Useful active hydrogen-containing polyester polyols are prepared by the reaction of excess polyols with difunctional carboxylic acids, with an average molecular weight of 60-6,000, containing at least two active hydrogens, with a hydroxyl group of 20-5,000 mg KOH. / g or so. Examples of the polyol include cyclo allyl such as ethylene glycol, propylene glycol, neopentyl glycol, butanediol, hexane diol, and 1,4-cyclohexanediol, 4,4'-dihydroxy cyclohexyl 2,2-propene, and the like. Polyetherdiols such as tic diols, polyethylene oxide diols, polytetramethylene oxide diols, and triols such as trimetholol propane and trimetholethane, and these are used alone or in combination of two or more thereof.

Examples of the divalent and trivalent acids reacted with the above-mentioned alcohols include trimellitic anhydride, terephthalic acid, phthalic anhydride, fumaric acid, maleic acid, adipic acid, sebacic acid, cyclohexane dicarboxylic acid, isophthalic acid and phthalic acid. Etc.

Monofunctional active hydrogen-containing polyethers are useful for ethylene oxide and propylene oxide polymers and mixtures thereof which are initiated with monofunctional alcohols. In particular, the content of the monofunctional polyether compound composed of pure ethylene oxide preferably contains about 10 to 25 parts by weight based on the final urethane-acrylic, for example, polycarbonate and polyol with polycaprolactone.

As catalysts for promoting the urethane reaction, amines and organometallic compounds (mainly Tin-based compounds) are generally used. Triethylene diamine, operin, normal-ethyl-morpholine, piperazine, triethanolamine, and trienylamine , Dibutyltin dilaurate, stannous octoate, dioctyltin diacetate, reed octoate, stannous oleate, stannous talate, dibutyltin oxide and the like in an amount of 0.001 to 0.1% of the total solids do.

In the isocyanate-addition polymerization reaction of the present invention, the viscosity during the reaction is controlled by using a reactive diluent without using a solvent. Generally, the reactive diluent is, for example, methyl acrylate, methyl methacrylate, butyl acryl. Butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy propyl methacrylate, styrene, Alkyl esters of acrylic acid and methacrylic acid, such as acrylamide, alkyl esters of maleic acid and fumaric acid, vinyl and vinylidene halogen compounds, acrylic acid, ethylene glycol dimethacrylate, isobornyl methacrylate, vinyl acetate, vinyl ether, allyl Ether, lauryl methacrylate and N-butoxymethylacrylic The acrylic monomer is contained, including de. The vinyl monomers used in the emulsion polymer are preferably selected from acrylic monomers. Polymers having a molecular weight of 300 or more are substantially insoluble in aqueous media and can also be dissolved in monomer mixtures that make up the remainder of the particulates used to make the polymer.

In order to radically polymerize the polymerizable component, free radical initiators are required, and both water-soluble and oil-soluble initiators can be used, and since the addition of a specific initiator (for example, a redox initiator) can cause a strong exothermic reaction, As an alternative, it is preferred to add the initiator to the other components immediately before carrying out the reaction. Examples of water-soluble initiators include ammonium dioxulate, potassium peroxulate, hydrogen peroxide, cumene hydroxy peroxide, and the like. The oil-soluble initiator is t-butyl hydroperoxide, dilauryl peroxide, t-butyl perbenzoate. , 2,2'-azobis (isobutyronitrile). In the present invention, it is preferable to use a redox initiator such as ammonium persulfate / sodium metabisulfite or t-butylhydroperoxide / isoascovinic acid. The amount of initiator is determined according to the properties of the monomers used, and generally about 0.01 to 3 parts by weight based on the total weight of the monomers is preferred, and preferably 0.05 to 1 parts by weight.

A chain extender is added dropwise to the water dispersion of the isocyanate-containing polyurethane prepolymer containing a vinyl monomer to prepare a chain extension water dispersion, wherein the temperature is 5 to 95 ° C, more preferably 10 to 45 ° C. The amount of chain extender is propoly, and the amount of active hydrogen of the chain extender relative to the remaining NCO equivalent is 0.7: 1 to 2.0: 1. Of course, if water participates in the reaction as a chain extender, this ratio becomes meaningless because water has an abundant function as a chain extender as well as a dispersion medium and is present in excess of the NCO group.

Useful chain extenders include polyols, amino alcohols, ammonia, primary or secondary aliphatic, cycloaliphatic, aromatic, araaliphatic or heterocyclic amines such as diamines, hydrazines or substituted hydrazines. The use of water soluble chain extenders is preferred, and water itself is also effective as chain extenders. Examples of poor chain extenders include ethylene diamine, diethylenetriamine, triethylene tetramine, propylene diamine, butylene diamine, hexamethylene diamine, cyclohexylene diamine, piperazine, 2-methylpiperazine, phenylene diamine, toll Relene diamine, xylene diamine, tris (2-aminoethyl) amine, 3,3'-dinitrobenzidine, 4,4'-methylenebis (2-chloraniline), 3,3'-dichloro-4,4 ' -Biphenyl diamine, 2,6-diaminopyridine, 4,4'-diaminodiphenylmethane, menthane diamine, m-xylene diamine, isophorone diamine, and the like, and azines such as hydrazine and acetone azine and hydrazine substituents. Dimethyl hydrazine, 1,6-hexamethylene-bis-hydrazine, carbodihydrazine, adipic acid mono or dihydrazide, isophthalic acid dihydrazide, tartaric acid dihydrazide, 1,3-phenylene disulfonic acid di Hydrazide, Ω-amino-caproic acid dihydrazide Hydrazides of dicarboxylic or disulfonic acids such as hydrazines such as r-hydroxybutylic hydrazide, bis-semi-carbazide, and carbonic ester of bis-hydrazide of the above-mentioned glycols. And hydrazide reacted with lactones.

The following examples and comparative examples more specifically describe the method for producing the water-dispersible resin of the present invention, but do not limit the scope of the present invention.

Production Example 1: Production of Polyester Resin (A)

551.9 g of isophthalic acid (15.8% of polyester resin), 1923 g of Empol 1010 (Emery Chemical Co.), 1,6 in an air chamber equipped with a stirrer, a thermometer, a dropping tank, a nitrogen injection pipe and a fractional distillation unit -1025.1 g of hexane diol and 100 g of toluene are added and stirred under a nitrogen atmosphere to remove condensate. When the condensed water reaches 235.7 g, the reaction temperature is raised to about 200 ° C. and maintained until the acid value drops to 8 or less. The remaining toluene is removed under reduced pressure at that temperature to prepare a polyester resin.

Production Example 2: Production of Polyester Resin (B)

Into the reaction vessel, 960.0 g (43.5 parts by weight) of neopentyl glycol, 664.6 g (30.1 parts by weight) of isophthalic acid, 584.7 g (26.5 parts by weight) of adipic acid and 50.0 g of toluene were added thereto until the acid value reached 3.5. The reaction is carried out under nitrogen atmosphere.

Example 1: Preparation of terminally stable urethane-acrylic water dispersion

A) Preparation of Polyurethane Water Dispersion

42.0 g of methoxy polyethylene oxide (equivalent: 2000), IPDI 88.5 g, butyl acrylate 153.0 g, butylated hydroxy toluene 0.39 g After reacting for 3 hours at 80 ° C. under nitrogen atmosphere, the mixture was cooled to 50 ° C., and then 252.0 g of polyester resin (A) 1, neopentyl glycol 9.7 g, and 25.0 g of trimethol propane were added to the preparation. It is maintained until all isocyanate groups are completely reacted.

After cooling the mixture to 60 ° C, 919.8 g of deionized water was added while stirring at high speed for 10 minutes to prepare an aqueous dispersion, followed by chain extension with ethylene diamine. Solid content of this aqueous dispersion is 28%, and average particle diameter is 200 nm.

B) Preparation of Urethane-Acrylic Dispersion

1136.19 g of a) water dispersion (A), 508.66 g of deionized water, 2.25 g of t-butyl hydroxy peroxide, and 9.0 weight of the following monomer composition in a reaction vessel equipped with a stirrer, a thermometer, a dropping tank, a nitrogen injection tube, and a reflux condenser. The part was injected, the temperature was raised to 75 ° C, and the remaining monomer was added dropwise over 1 hour, held for 1 hour, and cooled.

The unreacted monomer of the urethane-acrylic water dispersion thus prepared was 0.02%, coagulated 0.14%, ph was 8.0, the viscosity is 160mpas (25 ℃), the solid content is 37.5%.

Example 2: Preparation of Side Chain Stabilized Urethane-Acrylic Dispersion]

A) Preparation of methoxy polyetherdiol

4538 g of methoxy propylene glycol (equivalent: 2000) and 1015 g of toluene are added to a reaction vessel equipped with a stirrer, a thermometer, a dropping tank, a nitrogen injection pipe, and a reflux condenser. The mixture was heated to reflux to remove water, cooled to 50 ° C, 4.5 g of benzoyl chloride was added and stirred for 10 minutes. 394.7 g of toluene diisocyanate was added thereto to completely react the isocyanate at 70 ° C, and then 249 g of diethanolamine was added to terminate the reaction. Residual toluene is removed under vacuum conditions.

B) Preparation of polyurethane dispersion

600 g of polyester resin (A) of Preparation Example 1, 100 g of methoxy polyetherdiol (A), neopentyl glycol 50.2 g, iso in a reaction vessel equipped with a stirrer, a thermometer, a dropping tank, a nitrogen injection pipe, and a reflux condenser 249.8 g of poron diisocyanate, 205 g of butyl acrylate, 0.05 g of butylated hydroxy toluene were added and reacted at 90 ° C. for 4 hours to further add 44.8 g of trimetholpropane to completely react the isocyanate, followed by 2482 g of water. Inject and disperse under high speed stirring.

C) Preparation of Urethane-Acrylic Dispersion

327.7g of the above dispersion in a reaction vessel equipped with a stirrer, a thermometer, a dropping tank, a nitrogen injection pipe and a reflux condenser, 265.87g of deionized water, 1.31g of t-butyl hydroxy peroxide, and 1% iso-ascorbic acid solution The mixture was heated to 75 ° C., and a mixture of 87.43 g of methmethacrylate, 84.00 g of butyl acrylate, and 0.21 g of dimethylethanolamine was added dropwise over 1 hour, maintained for 1 hour, and then cooled. The unreacted monomer of the urethane-acrylic aqueous dispersion thus prepared was 0.03%, coagulum was 0.02%, ph was 7.7, solid content was 34.4%, viscosity was 10mpas, and MFFT was 15 ° C.

[Comparative Example]

(I) Preparation of Isocyanate Urethane Prepolymer

A polyester having a hydroxyl value of 80 and an acid value of 70 prepared from trimetholpropane, neopentyl glycol, and trimellitic acid in a 1 liter four-necked flask equipped with a stirrer, thermometer, dropping tank, nitrogen injection tube and reflux condenser. 2064 g of polyol and 69 g of polycaprolactone triol (Union Carbide Co., Ltd .: 187 mg KOH / g), 87.7 g of polypropylene glycol (108.7 mg KOH / g), 232 g of hydroxyethyl acrylate, 2.8 g of dibutyltin dilaurate, 2.8 g of butylated hydroxy toluene and 696 g of butyl acrylate were added thereto, and the temperature was raised to 90 ° C. under a nitrogen atmosphere, and 488.7 g of isophorone diisocyanate was added dropwise over 1 hour without a catalyst, followed by reaction for 5 hours while maintaining 90 ° C. Subsequently, after cooling to 60 ° C., 20 g of triethyl amine was added thereto and reacted at 60 ° C. for 0.5 hours, after which the holding reaction was cooled to room temperature.

(II) Preparation of Water Dispersion of Acrylated Urethane Prepolymer

The mixed prepolymer mixture of (I) was dispersed in the 2-liter four-necked flask equipped with a stirrer, a thermometer, a dropping tank, a nitrogen injection tube and a reflux condenser for about 1 hour while maintaining the temperature at 30 ° C. under ultra-high stirring.

An acrylic urethane prepolymer water dispersion having excellent water dispersibility is prepared by the above method.

(III) Preparation of Acrylate Urethane Graft Copolymer Water Dispersion

220 g of ion-exchanged water was added to a 1 liter four-necked flask equipped with a stirrer, a thermometer lowering tank, a nitrogen injection tube, and a reflux condenser, followed by stirring in a nitrogen atmosphere to raise the temperature to 80 ° C. Subsequently, 0.94 g of potassium persulfate, 7.0 g of methyl methacrylate, 21 g of normal butyl methacrylate, and 86.15 g of an aqueous acrylic urethane prepolymer water dispersion prepared in (II) were mixed and held for 30 minutes. . After completion of the maintenance reaction, 102 g of ion-exchanged water, 0.66 g of potassium persulfate, 59.3 g of methyl methacrylate, 177 g of normal butyl methacrylate, and 324.68 g of the acrylic urethane dispersion prepared in (II) were mixed for 2 hours. It is added at a constant rate for a while and then maintained for 1 hour.

Physical properties of the examples and comparative examples prepared by the above method are shown in the table below.

1) Measured after drying at 150 ℃ for 1 hour

2) SP. NO 1/10 RPM

3) 400 mesh filtration and drying

4) Measure with MFFT Bar, 90

5) -20 ℃ / 8hr, + 20 ℃ / 8hr 5 repetitions

6) rubbing test

Claims (9)

Method for producing a nonionic side chain stabilized urethane-acrylic polymer water dispersion, characterized in that prepared in the following steps; I) reacting a polyether containing monofunctional active hydrogen with a polyisocyanate to prepare a partially treated isocyanate, and then ii) containing at least one amine active hydrogen and containing at least two active hydroxy groups. Reacting with a compound to prepare a nonionic stabilizer; B) reacting a compound containing an excess of polyol with a carboxylic acid of a bifunctional group to prepare at least one organic compound containing at least two active hydrogen functional groups; C) reacting the compounds of steps a) and b) with a compound containing at least 1/2 isocyanate in the presence of a vinyl monomer or a mixture of monomers which are reactive diluents to produce a side chain stabilized polyurethane polymer; D) reacting the polyurethane polymer of step c) with an aqueous dispersion and a chain extender to produce a nonionic polyurethane-urea aqueous dispersion; And e) preparing a nonionic side chain stabilized urethane-acrylic polymer aqueous dispersion by the free radical polymerization method of the water dispersion of step d) and the additional amount of the vinyl monomer in a weight ratio of 10:90 to 90:10. The method of claim 1, wherein the compound having at least one amine active hydrogen and containing at least two active hydroxy groups is a dientanol amine. The method of claim 1, wherein the isocyanate is 2,2,4-trimethylhexamethylene diisocyanate (TMDI), 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophore diisocyanate ( IPDI), 4,4'-methylene-bis- (cyclohexylene diisocyanate), α, α'-xylene diisocyanate, toluene diisocyanate, 2,4,6-triisocyanate toluene, 4,4,4- Triisocyanate triphenylmethane, 1,2,4-benzene triisocyanate, A method for producing a nonionic side chain stabilized urethane-acrylic polymer water dispersion, characterized in that it is used alone or in combination of two or more. The method of claim 1, wherein the polyether is selected from ethylene oxide and propylene oxide polymers, which are initiated by monofunctional alcohols, and mixtures thereof. The method of claim 1, wherein the polyol is ethylene glycol, propylene glycol, neopentyl glycol, butanediol, hexane diol, 1,4-cyclohexanediol, 4,4'-dihydroxy cyclohexyl 2,2-propane, It is selected from the group consisting of polyethylene oxide diol, polytetramethylene oxide diol, trimerol propane, and trimerol ethane, nonionic side-chain stable urethane-acrylic polymer, characterized in that these are used alone or in combination of two or more thereof. Method for producing an aqueous dispersion. The bifunctional carboxylic acid of claim 1, wherein the bifunctional carboxylic acid is selected from the group consisting of trimellitic anhydride, terephthalic acid, phthalic anhydride, fumaric acid, maleic acid, adipic acid, sebacic acid, cyclohexane dicarboxylic acid, isophthalic acid, and phthalic acid. A method for producing a nonionic side chain stabilized urethane-acrylic polymer water dispersion, characterized in that. The method of claim 1, wherein the organic compound of step b) is contained in an amount of about 20 parts by weight based on the final polyurethane resin. The vinyl monomer of claim 1, wherein the vinyl monomer which is a reactive diluent is methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl Acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, styrene, acrylamide, maleic acid, fumaric acid, vinyl and vinylidene halogen compounds, acrylic acid, ethylene glycol dimethacrylate, isobornyl meta A method for producing a nonionic side chain stabilized urethane-acrylic polymer aqueous dispersion, characterized in that it is selected from the group consisting of acrylate, vinyl acetate, vinyl ether, allyl ether, lauryl methacrylate and N-butoxymethylacrylamide. The nonionic side chain stabilized urethane according to claim 1, wherein the chain extender is a polyol, amino alcohol, ammonia, primary or secondary aliphatic, cycloaliphatic, aromatic, ara aliphatic or heterocyclic amine. -Production method of acrylic polymer water dispersion.