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CN1280594A - Scrub resistant latexes - Google Patents

Scrub resistant latexes Download PDF

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Publication number
CN1280594A
CN1280594A CN98811715A CN98811715A CN1280594A CN 1280594 A CN1280594 A CN 1280594A CN 98811715 A CN98811715 A CN 98811715A CN 98811715 A CN98811715 A CN 98811715A CN 1280594 A CN1280594 A CN 1280594A
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China
Prior art keywords
acid
vinyl
methacrylate
polymer
latex composition
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CN98811715A
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Chinese (zh)
Inventor
G·A·范德詹德
V·V·卡明斯基
A·J·德福斯科
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Union Carbide Chemicals and Plastics Technology LLC
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Union Carbide Chemicals and Plastics Technology LLC
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Publication of CN1280594A publication Critical patent/CN1280594A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Latex compositions are disclosed which are polymerized from monomers having acid or anhydride functionality and wet adhesion properties. The latex compositions of the present invention can be prepared by a two stage polymerization of a first stage polymer and a second stage polymer wherein a monomer effective to enhance the wet adhesion properties of the composition is included in either the first stage polymer, the second stage polymer, or both.

Description

Scrub resistant latexes
The field of the invention
Generality of the present invention relates to latex polymer, and relates more specifically to have the latex polymer of the wet adhesion characteristics of enhanced.
Background of the present invention
Emulsion paint coating generally is coated on the base material, and the dry purpose that is used to decorate with formation successive film, and protects base material.This class lacquer coating often is coated on the interior or outside surface of building, and coating on these surfaces has enough mobile stream to open, and has formed the successive paint film, and at room temperature dry.
Emulsion paint often includes organic polymer binding agent (being latex polymer), pigment and various lacquer additive.In the exsiccant paint film, polymeric binder is used as the binding agent of pigment, and the adhesion of dried paint and base material is provided.Pigment can be organic or inorganic, also helps opacity and painted except weather resistance and hardness on function, though some lacquers contain few or do not contain opaque pigment, is described to Clear paint.The production of lacquer involves the preparation of polymeric binder, the mixing of component raw material, the grinding of pigment in dispersant media, and the standard that is diluted to market demands.
The latex of being produced the interior or outside surface that is used to build often needs the wet adhesion energy.Wet adhesion typically by be dried at least 3 the week but on no longer than gloss alkyd (oiliness) paint film in 6 weeks the emulsion paint wet film of curtain coating 7 mils test.Allow dry 24 hours of emulsion paint, then, give film mark signature interlacing line, put into water 30 minutes, from water, take out then, be placed on the scrubbing machine.The lava soap solution and the standard washing scrubber of use 5% are cleaned the cross wire district 500 times.In test process, when not having paint film to be wiped, and obtained optimal wet adhesion value.Record keeps the percentage ratio of film.In fact this performance adheres on the surface that before scribbles alkyd paint lacquer.
Needing to be generally used for a kind of latex polymer in the emulsion paint of wet adhesion to contain vinylformic acid or styrene/acrylic monomer.Existing many methods are produced latex from the monomer of these types.A kind of concrete grammar utilization produces the general reaction mechanism of two-stage latex.The first step comprises monomer and chain-transfer agent, and polymerization in the presence of water and optional tensio-active agent is to produce water-soluble or the sl. sol. latex polymer of water.The second stage is to be aggregated in the presence of the first step then to produce more hydrophobic polymkeric substance.Resulting polymkeric substance is called as compounded latex in the present technique field, and it has the hydrophobic interior second stage and the water-soluble or outside first step of water slightly soluble/swollen.In a modification of this operation, add simultaneously the water-soluble/swollen polymkeric substance and the second stage.EP 0 587 333 A2 have described the water-fast multistage polymkeric substance that alkali insoluble polymer and alkali-soluble polymer are arranged, they are by the sequence emulsion polymerization preparation of monomer mixture, and this monomer mixture has acid functional group and alkali insoluble polymer to choose wantonly in the caustic solubility level and the amine functionality arranged so that first step polymkeric substance is connected with second stage polymkeric substance.
Functionality also is introduced in the latex, so that make itself and other resin crosslinks.U.S. patent No.5,326,843 have described and wherein Hydroxyethyl acrylate have been added in the polymerisable monomer group to produce the latex of reactive behavior functionality.Hydroxy functionality can react to form cured film with aminoplastics and polyisocyanates.Cross-linkable latex is also disclosed in WO95/29963 and WO95/29944.
Comprise have wet adhesion can the latex polymerization compositions of blend of latex polymer be disclosed in U.S. patent No.5, in 208,285.Yet the patentee discloses the carboxylic acid monomer that contains of relative a small amount of, and they are often desirable in latex composition.Therefore, by monomer polymerization and acid is arranged or latex polymerization compositions that anhydride functional group and wet adhesion can (being scrubbing resistance) is desirable.
General introduction of the present invention
According to the present invention, provide by latex polymerization compositions monomer polymerization and that acid or anhydride functional group and the adhesion functional group that wets are arranged.
Method of the present invention can be used for preparing first step polymkeric substance, after adding alkali, swelling is partly dissolved or dissolves this polymkeric substance substantially, thereby the medium of using for the second stage polyreaction of alkali insoluble polymer is provided, and the stability of alkali insoluble polymer is provided.Polymer latex of the present invention contains up to the acid content more than 10% or 10%, based on the gross weight of the polymkeric substance that contains acid or anhydride functional group.Surprisingly, when in coating formulation, using,, when the wet adhesion of adding functional group, have been found that this class latex polymer provides excellent wet adhesion although have acid or anhydride functional group.
The invention provides at composition such as building coating industry and car paint, seal gum, tackiness agent, paper coating composition, ink, useful polymkeric substance in varnish and the analogue.
Detailed description of the present invention
Latex composition of the present invention can be prepared by the two-stage polyreaction of first step polymkeric substance and second stage polymkeric substance.
First step polymkeric substance is an emulsion polymeric product of choosing monomer mixture in the presence of wet adhesion promotor wantonly, this monomer mixture comprises at least a carboxylic acid or acid anhydrides functional monomer or gives the monomer of first step polymkeric substance with the quick property of alkali, these monomers and the reaction of various comonomer.
Suitable acid or acid anhydrides functional monomer comprise vinylformic acid, methacrylic acid, ethylacrylic acid, α-Lv Daibingxisuan, Ba Dousuan, citraconic acid, methylfumaric acid, methylene-succinic acid, toxilic acid, fumaric acid, 3-acrylamido-3 Methylbutanoic acid, acrylic anhydride, methacrylic anhydride, ethyl propylene acid anhydrides, crotonic anhydride, citraconic anhydride, methylfumaric acid acid anhydride, itaconic anhydride, maleic anhydride, fumaric acid anhydride is to the vinylbenzene carboxylic acid, p styrene sulfonic acid, vinyl sulfonic acid, methacrylic acid 2-sulphur ethyl ester, methacrylic acid 3-sulphur propyl ester, vinylformic acid 3-sulphur propyl ester, 2-acrylamido-2-methyl propane sulfonic acid, and analogue, and comprise their mixture.In one embodiment of the invention, preferred acid mono is selected from vinylformic acid and methacrylic acid.
The amount that is present in acid in the first step emulsion polymerization or anhydride functional group has determined the solubleness of the first step after adding alkali.Make required acid of polymer dissolution or anhydride functional group's minimum, depend on the hydrophobicity of comonomer, the molecular weight of polymkeric substance, the chemical property of acid or anhydride monomers and the monomer sequence in polymkeric substance distributes.Sour or anhydride modified polymkeric substance can improve or reduce adhesivity according to lacquer system and base material.When excessive use, acid or anhydride group make paint film that water sensitivity be arranged, thereby diminish wet adhesive power.Based on above standard, be present in acid in the first step polyreaction or the monomeric preferred amounts of anhydride-functional and be at least approximately 2wt%, preferred 3wt% at least, more preferably about 5-50wt%; More preferably about 8-30wt%, and most preferably about 10-20wt% are based on the monomer total amount that adds in first step reaction.
The example of the comonomer that is suitable in first step polyreaction for example is a methyl acrylate, ethyl propenoate, butyl acrylate, 2-EHA, decyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, vinylbenzene, the vinylbenzene of replacement such as alpha-methyl styrene, vinyl cyanide, vinyl-acetic ester, and other acrylic or methacrylic acid C 1-C 12Alkyl or hydroxyalkyl acrylate, 2 ethyl hexanoic acid vinyl acetate, propionate, vinyl neodecanoate, new n-nonanoic acid vinyl acetate, Visa acid (a kind of alkanecarboxylic acid that side chain is arranged) vinyl acetate (vinyl versatate), new vinyl acetate acid and analogue, and/or their mixture.
First step polymkeric substance can have various molecular weights.Molecular weight is controlled by adding suitable chain-transfer agent known in the art.The example of the chain-transfer agent that is fit to comprises for example alkyl sulfhydryl, and as octyl mercaptan and decyl mercaptan, the ester of Thiovanic acid is as the ester of ethyl thioglycolate and 2-ethylhexyl mercaptoacetate and thiohydracrylic acid, as the different monooctyl ester of thiohydracrylic acid.In a preferred embodiment, chain-transfer agent can be selected from thiohydracrylic acid 2-ethylhexyl and different monooctyl ester of thiohydracrylic acid or their mixture.The number-average molecular weight Mn that obtains is typically at 500-100,000 scope.
In first step caustic solubility polyreaction, can choose wantonly and introduce the wet promotor that adheres to, so that provide the wet adhesion energy for first step polymkeric substance and final latex product.Preferably, wet adhesion promotor comprises the monomer of the nitrogen functional group with the wet adhesion energy that strengthens latex composition effectively.The preferred wet promotor that adheres to comprises having amino, the compound of urea groups or N-heterocyclic radical, for example be the dialkyl aminoalkyl ester and the dialkyl aminoalkyl acid amides of acrylic or methacrylic acid, those of 1-5 carbon atom are especially arranged in alkyl, the compound of the free redical polymerization of urea, ethylidene-urea or propylidene urea and having-NC (O) N-group is as the polymerizable imidazolone of the part of ring-type five-membered ring structure.
Provide the example of the wet adhesion promotor of required wet adhesion energy to comprise dimethylaminoethyl acrylate, vinylformic acid diethyllaminoethyl ester, vinylformic acid dimethylamino propyl ester, vinylformic acid 3-dimethylamino-2,2-dimethyl propyl-1-ester, vinylformic acid 2-N-morpholino ethyl ester, vinylformic acid 2-N-piperidino-(1-position only) ethyl ester, N-(3-dimethylamino-propyl) acrylamide (Methacrylamide that comprises used herein), N-(3-dimethylamino-2,2-dimethyl-propyl group) acrylamide, N-dimethylamino methyl acrylamide, N-(4-morpholino methyl) acrylamide, N-(2-methacryloxyethyl) ethylidene-urea, methacrylamido ethyl ethylidene-urea, N-(2-methacryloxy kharophen ethyl)-N, N, N ', N '-ethylidene-urea, allyl group alkyl ethylidene-urea, N-methacrylamido-methyl urea, N-methacrylic uride, N-[3-(1,3-diaza hexamethylene-2-ketone-propyl group)] Methacrylamide, methacrylic acid 2-(1-imidazolyl) ethyl ester, methacrylic acid 2-(1-imidazolidin-2-one) ethyl ester, vinyl imidazole, vinyl pyrrolidone, with 3-allyl group-4,5-methoxyl group-2-imidazolone.
The preferred wet promotor that adheres to comprises N-(2-methacryloxyethyl) ethylidene-urea and methacrylamido ethyl ethylidene-urea.In addition, have been found that 2-methyl ethylene imine can carry out subsequent reactions the wet adhesion energy to be provided and to be used as in the alkali and first step alkali-soluble polymer with first step alkali-soluble polymer.It also can react with first step polymkeric substance behind the polymer formation of the second stage.
The amount of existing wet adhesion promotor is typically at about 0.1-20wt% in first step emulsion polymerisation process, preferably at about 1-10wt%, and about 1.9-5wt% most preferably, and the total amount of forming based on the monomer of first step charging.
In carrying out emulsion polymerization, use at least a its concentration to be enough to cause or the initiator or the catalyzer of catalytic polymerization.Initiator and/or catalyst concentration will change according to the monomeric weight that adds.The concrete concentration that is used for any example will depend on the specific monomer mixture and the employed particular initiator of reacting; This knows those one skilled in the art, and about 0.01-3wt% is everlasting; More preferably about 0.05-2wt%, and most preferably about 0.1-1wt% are based on the monomeric weight that adds.If desired, the metal ion of trace can add to improve the speed of polyreaction as activator, and this also is known.The example of the initiator that is fit to is a hydrogen peroxide, peracetic acid, tertbutyl peroxide, ammonium persulphate, Potassium Persulphate, Sodium Persulfate, and any other known initiator.What also be suitable for is redox-catalyst system such as Sodium Persulfate-sodium formaldehyde sulphoxylate, isopropyl benzene hydroperoxide-sodium metabisulphite, hydrogen peroxide-xitix, and other known redox system.
The polymerizable feed composition also can contain and anyly be usually used in other additives known of emulsion polymerisation process with common known quantity, as linking agent, and dispersing auxiliary, emulsifying agent, photosensitizers, tinting material, sterilant, mycocide etc.
When first step polyreaction finishes, neutralizing agent or alkali are added in the first step alkali-soluble polymer with swelling, are partly dissolved or basic dissolve polymer.The alkali that is fit to comprises ammonia, triethylamine, monoethanolamine, dimethylaminoethanol, ammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and all other I A and II A family's oxyhydroxide and analogue.As previously discussed, 2-methyl ethylene imine in and first step alkali-soluble polymer also be effectively, and provide the wet adhesion energy for end product simultaneously.
Based on the acid equivalent in alkali-soluble polymer, typically the normal alkali of 0.01-1.5 is added in the alkali-soluble polymer with swelling, is partly dissolved or dissolves alkali-soluble polymer substantially, so that be that second stage polyreaction forms the stabilization dispersion medium.
In one aspect of the invention, but the first step latex polymer of repository preparation is used for later neutralization reaction.In another aspect of this invention, first step polymkeric substance can be neutralized and be used as the dispersion medium of other latex polymer that comprises the second stage of the present invention emulsion polymerisation process.
By using first step polymkeric substance, have been found that end product has showed improved film forming properties, wet adhesion energy and other characteristic as the medium of using for the insoluble monomeric second stage of alkali emulsion polymerization.
The monomer that is applicable to polyreaction in the second stage comprises the insoluble monomer of any alkali, and those of promptly essentially no carboxylic acid or anhydride functional group for example have vinylformic acid, vinylbenzene, those of vinyl or Visa acid (versatic) functional group.Term as used herein " essentially no " refers to be lower than about 10wt%, preferably is lower than about 5wt% and more preferably less than about 2wt%, based on the total amount of polymkeric substance.This monomeric example is acrylate or methacrylic ester, vinylbenzene, ring-alkylated styrenes, Vinyl toluene, vinyl-acetic ester, vinyl alcohol, vinyl cyanide, vinylidene chloride, and vinyl ketone.The exemplary monomer of other of Shi Yonging for example comprises in the present invention, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, methacrylic acid n-pentyl ester, the secondary pentyl ester of methacrylic acid, N-Hexyl methacrylate, lauryl methacrylate(LMA), methacrylic acid stearyl, ethylhexyl methacrylate, the methacrylic acid butene esters, methacrylic acid cinnamic ester, methacrylic acid oil base ester, the methacrylic acid ricinoleate, hydroxyethyl methylacrylate, Rocryl 410, propionate, vinyl butyrate, uncle's vinyl butyrate, capric acid vinyl acetate, stearic acid vinyl ester, vinyl laurate, the oleic acid vinyl acetate, vinyl methyl ether, EVE, the vinyl n-propyl ether, the vinyl isopropyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl iso-octyl ether, vinyl phenyl ether, α-chlorovinyl phenyl ether, vinyl naphthyl ether, methacrylonitrile, acrylamide, Methacrylamide, N-alkyl acrylamide, the N-aryl acrylamide, the N-vinyl pyrrolidone, N-vinyl-3-morpholone mai, N-vinyl-oxazolidones, N-vinyl imidazole and analogue, and the mixture that comprises them.
Be included in optional components in the second stage polyreaction of alkali insoluble polymer for example comprise other monomer such as vinyl ester, acid and/the acid anhydrides functional monomer, linking agent, chain-transfer agent, and other material known in the art.If use suitable chain-transfer agent or linking agent, number-average molecular weight can be at 500-500,000 or bigger change in infinitely great.In the polyreaction of the second stage, also can choose wantonly and introduce the wet promotor that adheres to, so that provide the wet adhesion energy for end product; Yet condition is that it is introduced at least a in first step polymkeric substance or the second stage polymkeric substance.
Depend on the desired properties of final latex polymer and in acid content at different levels, the required ratio that joins the second stage polymerization single polymerization monomer in the first step polymeric media has wide scope.For example, the amount that when using height carboxylic acidifying raw material more, is incorporated into the first step polymkeric substance in the polyreaction of the second stage can be less [for example, the first step resin of 10 parts/each hundred parts of resin (being that the first step adds the second stage) (" p.h.r "), the latter is contained 20% methacrylic acid]; Perhaps this amount can be more when the raw material that uses than lower carboxylic acidization [for example, the first step resin of 20p.h.r, the latter is contained 10% methacrylic acid].Suitable scope comprises about 1: about 99: 1 of 99-.The weight ratio of second stage raw material monomer is preferably about 5: 95-95: 5, and most preferably about 10: 80-80: 10.
Resulting final latex composition can be as the binding agent that for example is used for building coating, industry and car paint, seal gum, tackiness agent, paper coating composition, ink, varnish and analogue.
In the lacquer formulation, the alkali insoluble polymer that is dispersed in the first step neutral polymkeric substance can coat with lacquer the level use that about 5% of formulation gross weight arrives about 90% (based on solid weight).Have been found that the lacquer formulation with these unique polymer manufacture has showed excellent wet adhesive power, high gloss and improved resistance to blocking.Except polymkeric substance of the present invention, the lacquer formulation can contain common additive such as pigment, filler, dispersion agent, wetting agent, coalescing agent, rheology modifier, drying retarder, biocides, antifoams and analogue.
Below description is the generality description about the emulsion polymerisation process that is used for preparing the alkali insoluble polymer that is dispersed in basic dissolved alkali-soluble polymer.In type reaction, the mixture of acrylic or methacrylic acid, acrylate or methacrylic ester and/or styrene monomer, wet adhesion monomer and other optional components is fed in the reactor, and they carry out letex polymerization in the presence of chain-transfer agent and initiator there.Typically, polyreaction is used tensio-active agent or emulsifying agent and is carried out in water medium.Temperature can about 35 ℃-about 90 ℃ or higher range; Preferred temperature is at about 70 ℃-about 85 ℃.Pressure is not strict with, and depends on the monomeric character of using, and gaseous monomer needs superatmospheric pressure usually.When first step monomer feed finishes, keep being reflected under the temperature of reaction, be lower than about 5000ppm up to the residual monomer level, then add required neutralizing agent,, be partly dissolved by swelling up to first step polymkeric substance, or basic dissolving.The second stage monomer that comprises optional components such as wet adhesion monomer is fed in the first step polymeric media under said temperature then.When second stage monomer feed finishes, keep about 1 hour of the temperature of reactor, cool off again and collect latex product.At this moment, latex can be chosen wantonly and further be neutralized.
Embodiment
Following embodiment will further specify the present invention, but never be interpreted as limiting the scope of the invention.
Embodiment A: styrene acrylic polymers synthetic
By with 100 gram vinylbenzene, 70 gram methyl methacrylates (Aldrich), 30 gram methacrylic acids (Aldrich) and 7 restrain in the monomer feed tube that thiohydracrylic acid 2-ethylhexyls (HampshireChemicals) are added to 1 liter and prepare monomer mixture.Second kind of monomer mixture is by restraining vinylbenzene with 210,250 gram methyl methacrylates (Aldrich), the 25wt% solution of N-(2-methacryloxyethyl) in methyl methacrylate (ROHAMERE 6844-0) (Rohm Tech) of 330 gram butyl acrylates (Union Carbide) and 50 grams is added in second 1 liter of monomer feed tube to be prepared.Use one quaterfoil stainless steel machinery agitator is housed, Claisen (claisen) pipe connecting, the Friedrichs water condenser, nitrogen scavenging duct and bubble trap, thermometer, and the monomer resin flask of adding two liters of strap clamps covers of the inlet 925 gram water of packing into, 2.5 gram GR-9M (Union Carbide).
By being dissolved in the initial oxidation agent solution for preparing in the 20 gram water, 2.5 gram ammonium persulphates in independent container, prepare.By 5 gram ammonium persulphates are dissolved in the delayed oxidizer solution for preparing in the 100 gram water also is to prepare in independent container.Under nitrogen purging, reactor is heated to 80 ℃ by allowing the current of controlled temperature system circulate through reactor jacket.
After the reactor feed temperature reaches 80 ℃, the initial oxidation agent solution is added in the reactor.After two minutes, under continuously stirring, use 1/8 by the FMI pump " teflon tube raw material monomer was transported in the reaction vessel through 40 minutes, temperature of reaction remains between 79-81 ℃ simultaneously.After monomer feed finishes, allow be reflected under 80 ℃ and carried out again 15 minutes.The 15wt% solution of ammonium hydroxide of 20 grams is added in this product.After 15 minutes, second kind of monomer mixture is added in the reactor in 2 hours with the oxidizing agent solution that postpones simultaneously.Product was kept 1 hour down at 80 ℃.The 15wt% solution of ammonium hydroxide of other 20 grams is added in the resulting product.Then with the product cool to room temperature.The pH of the latex of resulting 48% solids content is 8, and volume average particle sizes is 252 nanometers (" nm ") (with Microtrac particle size analyzer (Leeds-Northrop)).
According to above-mentioned operation styrene content is 30wt% (A1), and 10wt% (A2) and 20wt% (A3) prepare three samples.
Embodiment B: the production of lacquer
By mixing the following pigment abrasive material that becomes to assign to prepare successively: 30 gram water, 40 gram propylene glycol, 9.0 gram Tamol 165 dispersion agents (Rohm and Haas), 2.5 gram Triton  CF-10 tensio-active agent (Union Carbide Corp.), 1.5 gram Strodex PK-90 (Dexter), 1.0 gram AMP-95 (Angus), 2.0 gram Nuosept145 sanitass (Huls), 2.0 gram Foamaster AP defoamer (Henkel) and 225 gram TiONA RCL-535 titanium dioxide (SCM).Mixture ground 20 minutes on the high speed dispersion device, so that Hegman Scale (Hai Geman standard) 6+ level refined abrasive to be provided.
Coating with lacquer by the preparation that becomes to assign to below mixing successively under the moderate stirring: the latex of 550 gram embodiment A, the pigment abrasive material of the above preparation of 313 grams, 26 gram Texanol cohesion solvents (Eastman), 10.5 gram Polyphase P-20-T fungicide (Troy), 13.0 gram Acrysol RM-2020 (Rohm ﹠ Hass), 10 gram diethylene glycol monobutyl ether solvents (UnionCarbide Corp.) and 134 gram water.
Embodiment C: wet adhesion test
Wet adhesion by be dried at least 3 the week but on no longer than gloss alkyd (oiliness) paint film in 6 weeks the emulsion paint wet film of curtain coating 7 mils test.Allow dry 24 hours of emulsion paint, then, give film mark signature interlacing line, put into water 30 minutes, from water, take out then, be placed on the scrubbing machine.The lava soap solution and the standard washing scrubber of use 5% are cleaned the cross wire part 500 times.The result is set forth among the following table A:
Table A
Embodiment Styrene content 24 hours wet adhesion % retention rates
????A1 ????30％ ????100％
????A2 ????10％ ????100％
????A3* ????20％ ????15％
* saved wet adhesion monomer.
According to the present invention, wet adhesion value was preferably at least 90% in 24 hours, and more preferably 95% and most preferably 100%.
Though the present invention is described for particular aspects, those one skilled in the art will realize, and these descriptions are not the scopes that is used for limiting following claim.

Claims (20)

1．胶乳组合物，它包括：1. A latex composition comprising: (ⅰ)由至少一种酸或酸酐功能性单体聚合的第一种聚合物；和(i) a first polymer polymerized from at least one acid or anhydride functional monomer; and (ⅱ)由基本无酸或酸酐官能团的单体聚合的第二种聚合物：特征在于上述第一种聚合物或上述第二种聚合物中的至少一种是由具有有效增强由该胶乳组合物所形成的膜的湿粘附性能的氮官能团的单体聚合而成。(ii) A second polymer polymerized from monomers substantially free of acid or anhydride functional groups: characterized in that at least one of the above-mentioned first polymer or the above-mentioned second polymer is composed of the latex having an effective reinforcement The wet adhesion properties of the films formed by polymerizing nitrogen-functional monomers. 2．权利要求1的胶乳组合物，其中上述第一种聚合物包括基于上述第一种聚合物的总重量至少2．0wt％的酸或酸酐功能性单体。2. The latex composition of claim 1, wherein said first polymer comprises at least 2.0 weight percent of an acid or anhydride functional monomer, based on the total weight of said first polymer. 3．权利要求1的胶乳组合物，其中上述第一种聚合物包括基于上述第一种聚合物的总重量至少5．0wt％的酸或酸酐功能性单体。3. The latex composition of claim 1, wherein said first polymer comprises at least 5.0 weight percent of an acid or anhydride functional monomer, based on the total weight of said first polymer. 4．权利要求1的胶乳组合物，其中上述第一种聚合物包括基于上述第一种聚合物的总重量至少10．0wt％的酸或酸酐功能性单体。4. The latex composition of claim 1, wherein said first polymer comprises at least 10.0 weight percent of an acid or anhydride functional monomer, based on the total weight of said first polymer. 5．权利要求1的胶乳组合物，其中上述第一种聚合物为溶液形式。5. The latex composition of claim 1 wherein said first polymer is in solution. 6．权利要求1的胶乳组合物，其中上述第一种聚合物为溶胀或部分溶解的形式。6. The latex composition of claim 1 wherein said first polymer is in swollen or partially dissolved form. 7．权利要求1的胶乳组合物，其中上述第一种聚合物为颗粒形式。7. The latex composition of claim 1 wherein said first polymer is in particulate form. 8．权利要求1的胶乳组合物，其中上述第一种聚合物和上述第二种聚合物是至少部分共聚合的。8. The latex composition of claim 1 wherein said first polymer and said second polymer are at least partially copolymerized. 9．权利要求1的胶乳组合物，其中上述酸或酸酐功能性单体选自丙烯酸，甲基丙烯酸，乙基丙烯酸，α-氯代丙烯酸，巴豆酸，柠康酸，中康酸，衣康酸，马来酸，富马酸，3-丙烯酰氨基-3-甲基丁酸，丙烯酸酐，甲基丙烯酸酐，乙基丙烯酸酐，巴豆酸酐，柠康酸酐，中康酸酐，衣康酸酐，马来酸酐，富马酸酐，对苯乙烯羧酸，对苯乙烯磺酸，乙烯基磺酸，甲基丙烯酸2-磺乙酯，甲基丙烯酸3-磺丙酯，丙烯酸3-磺丙酯，2-丙烯酰氨基-2-甲基丙磺酸，和它们的混合物。9. The latex composition of claim 1, wherein the above-mentioned acid or acid anhydride functional monomer is selected from the group consisting of acrylic acid, methacrylic acid, ethylacrylic acid, α-chloroacrylic acid, crotonic acid, citraconic acid, mesaconic acid, itaconic acid, Maleic acid, fumaric acid, 3-acrylamido-3-methylbutyric acid, acrylic anhydride, methacrylic anhydride, ethacrylic anhydride, crotonic anhydride, citraconic anhydride, mesaconic anhydride, itaconic anhydride, horse Toic anhydride, fumaric anhydride, p-styrene carboxylic acid, p-styrene sulfonic acid, vinyl sulfonic acid, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, 3-sulfopropyl acrylate, 2 - Acrylamido-2-methylpropanesulfonic acid, and mixtures thereof. 10．权利要求1的胶乳组合物，其中上述第一种聚合物或上述第二种聚合物中的至少一种由选自以下的至少一种共聚单体聚合而成，这些共聚单体包括丙烯酸甲酯，丙烯酸乙酯，丙烯酸丁酯，丙烯酸2-乙基己酯，丙烯酸癸酯，甲基丙烯酸甲酯，甲基丙烯酸乙酯，甲基丙烯酸丁酯，甲基丙烯酸羟乙酯，甲基丙烯酸羟丙酯，苯乙烯，取代的苯乙烯如α-甲基苯乙烯，丙烯腈，乙酸乙烯酯，丙烯酸和甲基丙烯酸C1-C12烷基或羟基烷基酯，2-乙基己酸乙烯酯，丙酸乙烯酯，新癸酸乙烯酯，新壬酸乙烯酯，维萨酸乙烯酯，新戊酸乙烯酯，和它们的混合物。10. The latex composition of claim 1, wherein at least one of said first polymer or said second polymer is polymerized from at least one comonomer selected from the group consisting of methyl acrylate , ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, hydroxy methacrylate Propyl esters, styrene, substituted styrenes such as alpha-methylstyrene, acrylonitrile, vinyl acetate, C1 - C12 alkyl or hydroxyalkyl acrylates and methacrylates, vinyl 2-ethylhexanoate esters, vinyl propionate, vinyl neodecanoate, vinyl neononanoate, vinyl visanoate, vinyl pivalate, and mixtures thereof. 11．权利要求1的胶乳组合物，其中具有湿粘附官能团的所述单体选自丙烯酸二甲氨基乙酯，丙烯酸二乙氨基乙酯，丙烯酸二甲氨基丙酯，丙烯酸3-二甲氨基-2，2-二甲基丙基-1-酯，丙烯酸2-N-吗啉代乙酯，丙烯酸2-N-哌啶子基乙酯，N-(3-二甲氨基丙基)丙烯酰胺(包括甲基丙烯酰胺)，N-(3-二甲氨基-2，2-二甲基-丙基)丙烯酰胺，N-二甲氨基甲基丙烯酰胺，N-(4-吗啉代甲基)丙烯酰胺，N-(2-甲基丙烯酰氧基乙基)亚乙基脲，甲基丙烯酰氨基乙基亚乙基脲，N-(2-甲基丙烯酰氧基乙酰氨基乙基)-N，N，N’，N’-亚乙基脲，烯丙基烷基亚乙基脲，N-甲基丙烯酰氨基-甲基脲，N-甲基丙烯酰脲，N-[3-(1，3-二氮杂环己-2-酮-丙基)]甲基丙烯酰胺，甲基丙烯酸2-(1-咪唑基)乙酯，甲基丙烯酸2-(1-咪唑烷-2-酮)乙酯，乙烯基咪唑，乙烯基吡咯烷酮，和3-烯丙基-4，5-甲氧基-2-咪唑啉酮。11. The latex composition of claim 1, wherein said monomer having a wet adhesion functional group is selected from the group consisting of dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, 3-dimethylamino-2 acrylate , 2-dimethylpropyl-1-ester, 2-N-morpholinoethyl acrylate, 2-N-piperidinoethyl acrylate, N-(3-dimethylaminopropyl) acrylamide ( including methacrylamide), N-(3-dimethylamino-2,2-dimethyl-propyl)acrylamide, N-dimethylaminomethacrylamide, N-(4-morpholinomethyl ) acrylamide, N-(2-methacryloyloxyethyl)ethyleneurea, methacryloylaminoethylethyleneurea, N-(2-methacryloyloxyacetamidoethyl )-N, N, N', N'-ethyleneurea, allylalkylethyleneurea, N-methacrylamido-methylurea, N-methacryloylurea, N-[ 3-(1,3-diazacyclohexan-2-one-propyl)]methacrylamide, 2-(1-imidazolyl)ethyl methacrylate, 2-(1-imidazolidine methacrylate -2-keto) ethyl ester, vinylimidazole, vinylpyrrolidone, and 3-allyl-4,5-methoxy-2-imidazolinone. 12．权利要求11的胶乳组合物，其中含有氮官能团的上述单体选自N-(2-甲基丙烯酰氧基乙基)亚乙基脲和甲基丙烯酰氨基乙基亚乙基脲。12. 11. The latex composition of claim 11 wherein said monomer containing nitrogen functional groups is selected from the group consisting of N-(2-methacryloyloxyethyl)ethyleneurea and methacrylamidoethylethyleneurea. 13．权利要求1的胶乳组合物，它进一步包括从氨，三乙胺，单乙醇胺，二甲氨基乙醇，氢氧化铵，氢氧化钠，氢氧化钾，氢氧化钙和2-甲基吖丙啶中选择的一种中和剂。13. The latex composition of claim 1, which further comprises ammonia, triethylamine, monoethanolamine, dimethylaminoethanol, ammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and 2-methyl aziridine A neutralizer of choice. 14．权利要求1的胶乳组合物，其中上述基本上无酸或酸酐官能团的单体选自甲基丙烯酸丙酯，甲基丙烯酸异丙酯，甲基丙烯酸丁酯，丙烯酸丁酯，甲基丙烯酸甲酯，丙烯酸甲酯，丙烯酸乙基己酯，甲基丙烯酸正戊酯，甲基丙烯酸仲戊酯，甲基丙烯酸己酯，甲基丙烯酸月桂酯，甲基丙烯酸硬脂酯，甲基丙烯酸乙基己酯，甲基丙烯酸巴豆酯，甲基丙烯酸肉桂酯，甲基丙烯酸油基酯，甲基丙烯酸蓖麻醇酸酯，甲基丙烯酸羟乙酯，甲基丙烯酸羟丙酯，丙酸乙烯酯，丁酸乙烯酯，叔丁酸乙烯酯，苯乙烯，α-甲基苯乙烯，烷基苯乙烯，丙烯腈，乙烯基甲苯，乙酸乙烯酯，癸酸乙烯酯，硬脂酸乙烯酯，月桂酸乙烯酯，油酸乙烯酯，乙烯基·甲基醚，乙烯基·乙基醚，乙烯基·正丙基醚，乙烯基·异丙基醚，乙烯基·正丁基醚，乙烯基·异丁基醚，乙烯基·异辛基醚，乙烯基·苯基醚，α-氯乙烯基·苯基醚，乙烯基·萘基醚，甲基丙烯腈，丙烯酰胺，甲基丙烯酰胺，N-烷基丙烯酰胺，N-芳基丙烯酰胺，N-乙烯基吡咯烷酮，N-乙烯基-3-吗啉酮，N-乙烯基-噁唑烷酮，N-乙烯基咪唑，和它们的混合物。14. The latex composition of claim 1, wherein said substantially free of acid or anhydride functional monomers are selected from the group consisting of propyl methacrylate, isopropyl methacrylate, butyl methacrylate, butyl acrylate, methyl methacrylate , methyl acrylate, ethylhexyl acrylate, n-pentyl methacrylate, sec-pentyl methacrylate, hexyl methacrylate, lauryl methacrylate, stearyl methacrylate, ethylhexyl methacrylate Ester, Crotyl Methacrylate, Cinnamyl Methacrylate, Oleyl Methacrylate, Ricinoleyl Methacrylate, Hydroxyethyl Methacrylate, Hydroxypropyl Methacrylate, Vinyl Propionate, Butyl Methacrylate Vinyl tert-butyrate, vinyl tert-butyrate, styrene, alpha-methylstyrene, alkylstyrene, acrylonitrile, vinyltoluene, vinyl acetate, vinyl caprate, vinyl stearate, vinyl laurate Esters, vinyl oleate, vinyl methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl isopropyl ether, vinyl n-butyl ether, vinyl isobutyl Base ether, vinyl isooctyl ether, vinyl phenyl ether, α-chlorovinyl phenyl ether, vinyl naphthyl ether, methacrylonitrile, acrylamide, methacrylamide, N- Alkacrylamides, N-arylacrylamides, N-vinylpyrrolidones, N-vinyl-3-morpholinones, N-vinyl-oxazolidinones, N-vinylimidazoles, and mixtures thereof. 15．权利要求1的胶乳组合物，其中上述第二级包括基于第二种聚合物的总重量小于约5wt％的酸或酸酐功能性单体。15. The latex composition of claim 1, wherein said second stage comprises less than about 5 weight percent acid or anhydride functional monomer, based on the total weight of the second polymer. 16．权利要求1的胶乳组合物，其中第一种聚合物是由甲基丙烯酸，丙烯酸丁酯，和甲基丙烯酸甲酯以及任选的甲基丙烯酰氨基乙基亚乙基脲聚合而成的。16. The latex composition of claim 1 wherein the first polymer is polymerized from methacrylic acid, butyl acrylate, and methyl methacrylate and optionally methacrylamidoethylethyleneurea. 17．权利要求1的胶乳组合物，其中第二种聚合物是由丙烯酸丁酯和甲基丙烯酸甲酯以及任选的甲基丙烯酰氨基乙基亚乙基脲聚合而成的。17. The latex composition of claim 1 wherein the second polymer is polymerized from butyl acrylate and methyl methacrylate and optionally methacrylamidoethylethyleneurea. 18．权利要求1的胶乳组合物，其中第一种聚合物是由甲基丙烯酸，苯乙烯，以及甲基丙烯酸甲酯，丙烯酸丁酯和任选的甲基丙烯酰氨基乙基亚乙基脲聚合而成的。18. The latex composition of claim 1, wherein the first polymer is polymerized by methacrylic acid, styrene, and methyl methacrylate, butyl acrylate and optional methacrylamidoethylethyleneurea into. 19．权利要求1的胶乳组合物，其中第二种聚合物是由丙烯酸丁酯，苯乙烯，以及甲基丙烯酸甲酯和任选的甲基丙烯酰氨基乙基亚乙基脲聚合而成的。19. The latex composition of claim 1 wherein the second polymer is polymerized from butyl acrylate, styrene, and methyl methacrylate and optionally methacrylamidoethylethyleneurea. 20．漆组合物，它包括水，颜料和权利要求1的胶乳组合物。20. A paint composition comprising water, pigment and the latex composition of claim 1.
CN98811715A 1997-10-03 1998-10-01 Scrub resistant latexes Pending CN1280594A (en)

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US11136468B2 (en) 2011-12-15 2021-10-05 Swimc Llc Rheological methods for high block, tack and scrub resistant coating composition
US11168230B2 (en) 2011-12-15 2021-11-09 Swimc Llc High block, tack and scrub resistant coating composition
US11649368B2 (en) 2011-12-15 2023-05-16 Swimc Llc Rheological methods for high block, tack and scrub resistant coating composition

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