NO153892B - LOW-PIGMENTED SOLVENT PAINTING WITH HIGH WATER ADHESION BASED ON A SHORT PLASTIC DISPERSION - Google Patents
LOW-PIGMENTED SOLVENT PAINTING WITH HIGH WATER ADHESION BASED ON A SHORT PLASTIC DISPERSION Download PDFInfo
- Publication number
- NO153892B NO153892B NO762738A NO762738A NO153892B NO 153892 B NO153892 B NO 153892B NO 762738 A NO762738 A NO 762738A NO 762738 A NO762738 A NO 762738A NO 153892 B NO153892 B NO 153892B
- Authority
- NO
- Norway
- Prior art keywords
- weight
- parts
- dispersion
- allyl ester
- paint
- Prior art date
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- 239000006185 dispersion Substances 0.000 title claims description 44
- 229920003023 plastic Polymers 0.000 title claims description 9
- 239000004033 plastic Substances 0.000 title claims description 9
- 239000002904 solvent Substances 0.000 title claims description 9
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- 238000010422 painting Methods 0.000 title description 3
- 239000003973 paint Substances 0.000 claims description 43
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- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229920003087 methylethyl cellulose Polymers 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 150000002917 oxazolidines Chemical class 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- OLBCVFGFOZPWHH-UHFFFAOYSA-N propofol Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O OLBCVFGFOZPWHH-UHFFFAOYSA-N 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Classifications
-
- 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
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
Problemet med våtklebing av dispersjonsmalinger på glatte, ikke sugende underlag har i lengere tid begrenset . anvendelsen av bestemte dispersjonsmalinger. Lavpigmenterte dispersjonsmalinger, og blant disse spesielt slike som tørrer til glinsende eller silkematte filmer kleber dårlig på glatte, ikke sugende underlag når strøkene etter tørringen igjen fuktes. Spesielt dårlig er våtklebingen ved friske strøk, som enda ikke er aldret. The problem of wet bonding of dispersion paints on smooth, non-absorbent surfaces has for a long time been limited. the use of specific dispersion paints. Low-pigmented dispersion paints, and among these especially those that dry to glossy or silky-matt films, adhere poorly to smooth, non-absorbent surfaces when the coats are moistened again after drying. Wet adhesion is particularly bad with fresh coats, which have not yet aged.
Lavpigmenterte dispersjonsmalinger velger man når strøket Low-pigmented dispersion paints are chosen when coated
skal være vaskbart. Ved de høye bindemiddelinnhold i disse malinger oppstår en lukket, vaskbar film. Likeledes har glinsende eller silkematte dispersjonsmalinger en pigment-volumkonsentrasjon på mindre enn 40%, og vanligvis ca. must be washable. The high binder content in these paints creates a closed, washable film. Likewise, glossy or silky-matte dispersion paints have a pigment-volume concentration of less than 40%, and usually approx.
10-25%. Dessuten inneholder de til forbedring av glans, flyteevne og åpen tid og som filmkonsolideringsmiddel organiske oppløsningsmidler i større mengde, ca. mellom 3 og 20%. Glans, flyteevne og åpen tid påvirkes f.eks. ved hjelp av flerverdige, med vann blandbare alkoholer med inntil 6 C-atomer, spesielt etylen- og propylenglykol, eller deres monometyl-, monoetyl- eller monobutyletere. For forbedring av filmkonsolideringen anvender man begrenset vann-oppløselige oppløsningsmidler, som monoglykoleter av kar-boksylsyre, og spesielt estere av karboksylsyrer med mono-alkyletere og glykoler eller oligoglykoler. Butyldiglykol-acetat er en av de mest utbredte representanter for denne gruppe. Kombinasjonen av lav pigmentering og høyt oppløs-ningsmiddelinnhold virker spesielt negativt på våtklebingen av dispersjonsmalingsstrøk. 10-25%. In addition, to improve gloss, fluidity and open time and as a film consolidation agent, they contain organic solvents in larger quantities, approx. between 3 and 20%. Gloss, buoyancy and open time are affected, for example. by means of polyhydric, water-miscible alcohols with up to 6 C atoms, especially ethylene and propylene glycol, or their monomethyl, monoethyl or monobutyl ethers. To improve the film consolidation, limited water-soluble solvents are used, such as monoglycol ethers of carboxylic acids, and especially esters of carboxylic acids with monoalkyl ethers and glycols or oligoglycols. Butyl diglycol acetate is one of the most widespread representatives of this group. The combination of low pigmentation and high solvent content has a particularly negative effect on the wet adhesion of dispersion paint coats.
Manglende våtklebing fører til at de i og for seg vaskbare strøk ikke mer har denne egenskap når de blir påført på glatte, ikke sugende underlag, f.eks. på gamle alkyldharpiks-eller oljefargestrøk. I fuktige rom, som kjøkken eller bade-rom, og mange industrielle rom hvor det må regnes med kon-densvanndannelse kan nye strøk løsne fra underlaget, når det ikke er sørget for tilstrekkelig våtklebing. Endelig vanskeliggjør manglende våtklebing malerarbeidet. Utføres eksempelvis sokkel og øvre vegghalvdel eller vegg og tak forskjelligfarget, så kan det forekomme at første strøk til-smusses med annen farge på grunn av unøyaktig penselføring. Prinsippielt kan man fjerne denne tilsmussing med en fuktig klut eller svamp. Ved manglende våtklebing beskadiges derved imidlertid lett første strøk eller helt skyves av. A lack of wet adhesion means that the inherently washable coatings no longer have this property when they are applied to smooth, non-absorbent surfaces, e.g. on old alkyl resin or oil paint coatings. In damp rooms, such as kitchens or bathrooms, and many industrial rooms where condensation must be expected, new coats can detach from the substrate when sufficient wet bonding is not provided. Finally, lack of wet bonding makes the painting work difficult. If, for example, the plinth and upper half of the wall or the wall and ceiling are painted in different colours, it may happen that the first coat is soiled with a different color due to inaccurate brush application. In principle, this contamination can be removed with a damp cloth or sponge. In the event of a lack of wet bonding, however, the first coat is easily damaged or completely pushed off.
Det har av disse grunner ikke manglet på forsøk på å modifi-sere dispersjoner således at de dermed fremstilte dispersjonsmalinger viser den ønskede våtklebing. Tallrike monomere som inneholder spesielle funksjonelle grupper (f.eks. bestemte cyklourider, oksazolidiner, azometiner eller aziri-diner) er blitt foreslått som komonomere ved emulsjonspoly-merisasjon til forbedring av våtklebing av dispersjonsmalinger på ikke-sugende underlag. Det er også blitt foreslått for forbedring av våtklebingen å innbygge aminogrupper ved i polymerkjeden av emulsjonspolymerene å medanvende komonomere med spesielle reaktivgrupper, f.eks. oxirangrupper eller grupper med nukleofilt substituerbare halogenatomer ved polymerisasjonen og først etter foretatt polymerisering innføre aminogruppene i polymeren ved omsetning med ammoniakk eller aminer. For these reasons, there has been no shortage of attempts to modify dispersions so that the dispersion paints thus produced show the desired wet adhesion. Numerous monomers containing special functional groups (eg certain cyclorides, oxazolidines, azomethines or aziridines) have been proposed as comonomers in emulsion polymerization to improve wet adhesion of dispersion paints on non-absorbent substrates. It has also been proposed to improve the wet adhesion to incorporate amino groups into the polymer chain of the emulsion polymers by co-using comonomers with special reactive groups, e.g. oxirane groups or groups with nucleophilically substitutable halogen atoms during the polymerization and only after polymerization introduce the amino groups into the polymer by reaction with ammonia or amines.
Dispersjonsmalinger som inneholder slike amonigruppeholdige polymere som bindemiddel tenderer imidlertid ofte til gul-farging. Dessuten er våtklebingen ofte bare forbedret i liten grad. Mange av disse farger gir riktignok ved lav pigmentering strøk som kleber tilstrekkelig på glatte, ikke-sugende underlag. Setter man imidlertid organiske oppløs-ningsmidler til disse malinger, så har herav fremstilte malinger dårlig våtklebing. However, dispersion paints that contain such ammonium group-containing polymers as a binder often tend to yellow. In addition, the wet bonding is often only slightly improved. Admittedly, many of these colors give coats with low pigmentation that adhere sufficiently to smooth, non-absorbent surfaces. However, if organic solvents are added to these paints, paints produced from these have poor wet adhesion.
Fra DOS 1 495 706 er det kjent kunststoffdispersjoner, i hvis polymerisatdel er inneholdt monomere som inneholder ketogrupper, hvorover det er mulig med en nettdannelse med f.eks. dikarbonsyre-bis-hydrazider. Disse dispersjoner anvendes f.eks. i tekstiltoredling til fremstilling av rensebestandige lim eller i malingsteknikken for fremstilling From DOS 1 495 706, plastic dispersions are known, in the polymerizate part of which monomers containing keto groups are contained, over which it is possible to form a network with e.g. dicarboxylic acid bis-hydrazides. These dispersions are used e.g. in textile processing for the production of cleaning-resistant adhesives or in the painting technique for production
av oppløsningsmiddelbestandige malinger. of solvent-resistant paints.
Oppfinnelsen vedrører lavpigmentert oppløsningsmiddelholdig maling med høy våtvedhefting på basis av en vandig kunststoffdispersjon som inneholder vanlige emulgatorer og beskyttelseskolloider og har et faststoffinnhold på 20-70 vekt-%, idet pigmentvolumkonsentrasjonen er 7-30%. og oppløsningsmidlet er et organisk oppløsningsmiddel hvis mengde utgjør 3-20 vekt-% av malingen, idet malingen er karakterisert ved at kunstoffdispersjonen er en dispersjon av en kopolymer av en olefinisk umettet monomer og en med denne kopolymeriserbar aceteddikester som er en vinylacetateddikester, en allylaceteddikester eller en diester med formel The invention relates to low-pigment solvent-based paint with high wet adhesion based on an aqueous plastic dispersion that contains common emulsifiers and protective colloids and has a solids content of 20-70% by weight, the pigment volume concentration being 7-30%. and the solvent is an organic solvent, the amount of which is 3-20% by weight of the paint, the paint being characterized in that the plastic dispersion is a dispersion of a copolymer of an olefinically unsaturated monomer and an acetic acid ester that can be copolymerized with this, which is a vinyl acetate acetic ester, an allyl acetate acetic ester or a diester of formula
hvori R betyr et hydrogenatom eller en metylrest og A betyr gruppen -(CH2)n~0- eller -(CH2-CH2) -O-, idet n betyr et helt tall fra 1-4 og m et tall fra 1-3, idet mengden av aceteddikester utgjør 0,5-10 vekt-% av alle monomerer. in which R means a hydrogen atom or a methyl residue and A means the group -(CH2)n~0- or -(CH2-CH2) -O-, where n means an integer from 1-4 and m a number from 1-3, with the amount of acetic acid ester constituting 0.5-10% by weight of all monomers.
I stedet for en eneste dispersjon kan man anvende blandinger av forskjellige dispersjoner, idet imidlertid minst en inneholder den polymert bundede aceteddikester, nemlig i en slik mengde at referert til samlet vekt av alle i blandingen inneholdte monomere er aceteddikesteren tilstede i ovenfor angitte mengder. Instead of a single dispersion, mixtures of different dispersions can be used, with at least one containing the polymeric bound acetic acid ester, namely in such an amount that, with reference to the total weight of all monomers contained in the mixture, the acetic acid ester is present in the amounts specified above.
Pigmentvolumkonsentrasjonen ligger fortrinnsvis mellom The pigment volume concentration is preferably between
10 og 20%. 10 and 20%.
Organiske oppløsningsmidler innenfor oppfinnelsens ramme Organic solvents within the scope of the invention
er glykoler og deres derivater, som f.eks. etylenglykol, propylenglykol, butylenglykol, heksylenglykol, oligoglykoler, som di- eller triglykol, glykol-, resp. oligoglykol-etere, som metyl-, etyl-, propyl- eller butyl-mono, -di- are glycols and their derivatives, such as e.g. ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, oligoglycols, such as di- or triglycol, glycol-, resp. oligoglycol ethers, such as methyl, ethyl, propyl or butyl mono, -di-
eller -triglykoletere, mono-, di- eller triglykolestere, som mono-, di- eller triglykolacetat, -propionat eller -butyrat samt (oligo-) glykolhalveter-halvestere, som f.eks. metyl-, etyl-, propyl- eller butyl-mono-, di- eller triglykolacetat, -propionat eller -butyrat. Også blandinger av slike stoffer kan benyttes. De organiske oppløsningsmidler settes til malingen i mengder på fortrinnsvis 5-15 vekt-%, referert til malingens samlede vekt. or -triglycol ethers, mono-, di- or triglycol esters, such as mono-, di- or triglycol acetate, -propionate or -butyrate as well as (oligo-) glycol half ether half esters, such as e.g. methyl, ethyl, propyl or butyl mono-, di- or triglycol acetate, propionate or butyrate. Mixtures of such substances can also be used. The organic solvents are added to the paint in amounts of preferably 5-15% by weight, referred to the total weight of the paint.
De vandige kunststoffdispersjoner har som nevnt faststoffinnhold mellom 20 og 70 vekt-%, fortrinnsvis mellom 40 og 60%. Forøvrig fremstilles de vandige kunststoffdispersjoner på vanlig måte etter fremgangsmåter som er kjent for fagfolk. As mentioned, the aqueous plastic dispersions have a solids content of between 20 and 70% by weight, preferably between 40 and 60%. Otherwise, the aqueous plastic dispersions are produced in the usual way according to methods known to those skilled in the art.
Valget av de øvrige monomere er ikke avgjørende. Egnet er f.eks. vinylester av organiske karboksylsyrer hvis karbon-struktur inneholder 1-30, fortrinnsvis 1-20 karbonatomer, som vinylacetat, vinylpropionat, isononansyrevinylester og vinylester av forgrenede monokarboksylsyrer med inntil 20 karbonatomer, estere av akrylsyre eller metakrylsyre med 1-30, fortrinnsvis 1-20 karbonatomer i alkoholresten, som etylakrylat, isopropylakrylat, butylakrylat, 2-etylheksyl-- akrylat, metylmetakrylat, butylmetakrylat, aromatiske The choice of the other monomers is not decisive. Suitable is e.g. vinyl esters of organic carboxylic acids whose carbon structure contains 1-30, preferably 1-20 carbon atoms, such as vinyl acetate, vinyl propionate, isononanoic acid vinyl ester and vinyl ester of branched monocarboxylic acids with up to 20 carbon atoms, esters of acrylic acid or methacrylic acid with 1-30, preferably 1-20 carbon atoms in the alcohol residue, such as ethyl acrylate, isopropyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, butyl methacrylate, aromatic
eller alifatiske *t- e-umettede hydrokarboner, som etylen, propylen, styren, vinyltoluen, vinylhalogenider, som vinylklorid, umettede nitriler, som akrylnitril, diester av maleinsyre eller fumarsyre, som dibutylmaleinat eller dibutylfumarat, a-e-umettede karboksylsyrer, som akrylsyre, metakrylsyre eller krotonsyre samt deres derivater, som akrylamid eller metakrylat. or aliphatic *t-e-unsaturated hydrocarbons, such as ethylene, propylene, styrene, vinyltoluene, vinyl halides, such as vinyl chloride, unsaturated nitriles, such as acrylonitrile, diesters of maleic acid or fumaric acid, such as dibutyl maleate or dibutyl fumarate, a-e-unsaturated carboxylic acids, such as acrylic acid, methacrylic acid or crotonic acid as well as their derivatives, such as acrylamide or methacrylate.
Ved valg av egnede monomere eller monomerkombinasjoner er det å ta hensyn til de generelt anerkjente synspunkter til fremstillingen av malingsdispersjoner. Således må When choosing suitable monomers or monomer combinations, the generally recognized views on the production of paint dispersions must be taken into account. Thus must
det spesielt påsees at det oppstår polymere som under de foreskrevne tørrebetingelser for malingen danner en film, it is especially ensured that polymers are formed which, under the prescribed drying conditions for the paint, form a film,
og valget av monomerer til fremstilling av kopolymerisatene and the choice of monomers for producing the copolymers
må treffes således at etter stillingen av polymerisasjonspara-meteren er det å vente dannelse kopolymere med de ketogruppe-holdige monomere. I det følgende er det oppført noen egnede monomerkombinasjoner: etylakrylat/metylmetakrylat/(met-)akrylsyre/aceteddiksyreallylester, must be met so that after the setting of the polymerization parameter, the formation of copolymers with the keto group-containing monomers is to be expected. In the following, some suitable monomer combinations are listed: ethyl acrylate/methyl methacrylate/(meth-)acrylic acid/acetoacetic acid allyl ester,
isopropylakrylat/metylmetakrylat/(met-)akrylsyre/aceteddiksyreallylester, isopropyl acrylate/methyl methacrylate/(meth-)acrylic acid/acetoacetic acid allyl ester,
butylakrylat/metylmetakrylat/(met-)akrylsyre/aceteddik-allylester, butyl acrylate/methyl methacrylate/(meth-)acrylic acid/acetic acetic allyl ester,
isobutylakrylat/metylmetakrylat/(met-)akrylsyre/aceteddik-syrea Hyles ter, isobutyl acrylate/methyl methacrylate/(meth-)acrylic acid/acetoacetic acida Hyles ter,
2-etylheksylakrylat/metylmetakrylat/(met-)akrylsyre/aceteddiksyreallylester, 2-ethylhexyl acrylate/methyl methacrylate/(meth-)acrylic acid/acetoacetic acid allyl ester,
etylakrylat/styren/metylmetakrylat/(met-)akrylsyre/aceteddiksyreallylester, ethyl acrylate/styrene/methyl methacrylate/(meth-)acrylic acid/acetoacetic acid allyl ester,
butylakrylat/styren/metyImetakrylat/(met-)akrylsyre/aceteddiksyreallylester, butyl acrylate/styrene/methylmethacrylate/(meth-)acrylic acid/acetoacetic acid allyl ester,
2-etylheksylakrylat/styren/(met-)akrylsyre/aceteddiksyreallylester, 2-ethylhexyl acrylate/styrene/(meth-)acrylic acid/acetoacetic acid allyl ester,
vinylacetat/butylakrylat/aceteddiksyreallylester, vinylacetat/dibutylmaleinat/aceteddiksyreallylester, vinylacetat/dibutylfumarat/aceteddiksyreallylester, vinylacetat/isononansyrevinylester/aceteddiksyreallylester, vinylacetat/2-etylheksansyrevinylester/aceteddiksyreallylester, vinyl acetate/butyl acrylate/acetoacetic acid allyl ester, vinyl acetate/dibutyl maleate/acetoacetic acid allyl ester, vinyl acetate/dibutyl fumarate/acetoacetic acid allyl ester, vinyl acetate/isononanoic acid vinyl ester/acetoacetic acid allyl ester, vinyl acetate/2-ethylhexanoic acid vinyl ester/acetoacetic acid allyl ester,
vinylacetat/versatic-10-syrevinylester/aceteddiksyreallylester , vinyl acetate/versatic-10-acid vinyl ester/acetoacetic acid allyl ester,
vinylacetat/etylen/aceteddiksyreallylester, vinyl acetate/ethylene/acetoacetic acid allyl ester,
vinylacetat/etylen/vinylklorid/aceteddiksyreallylester. vinyl acetate/ethylene/vinyl chloride/acetoacetic acid allyl ester.
Kunststoffdispersjoner er overordentlig komplekse systemer. Ikke aktsomhet på de for fagfolk på emulsjonspolymerisasjonen kjente regler kan derfor påvirke viktige egenskaper, f.eks. vannbestandigheten. Dispersjonene bør derfor, referert til innholdet av polymerisat, inneholde inntil 3 vekt-%, fortrinnsvis inntil 2% av ioniske emulgatorer, resp. inntil 6 vekt-%, fortrinnsvis inntil 4% av ikke-ioniske emulgatorer. Plastic dispersions are extremely complex systems. Failure to observe the rules known to professionals in emulsion polymerization can therefore affect important properties, e.g. the water resistance. The dispersions should therefore, with reference to the polymer content, contain up to 3% by weight, preferably up to 2% of ionic emulsifiers, resp. up to 6% by weight, preferably up to 4% of non-ionic emulsifiers.
Som ikke-ioniske emulgatorer anvender man eksempelvis alkyl-polyglykoletere, SOin etoksylleringsprodukter av lauryl-, oleyl- eller stearylalkohol eller av blandinger som kokos-fettalkohol, alkylfenolpolyglykoletere, som etoksyleringsprodukter av oktyl- eller nonylfenol, diisopropylfenol, tri-isopropylfenol eller av di- eller tritert.-butylfenol eller etoksyleringsprodukter av polypropylenoksyd. As non-ionic emulsifiers, for example, alkyl polyglycol ethers, SOin ethoxylation products of lauryl, oleyl or stearyl alcohol or of mixtures such as coconut fatty alcohol, alkylphenol polyglycol ethers, as ethoxylation products of octyl or nonylphenol, diisopropylphenol, triisopropylphenol or of di- or tri-tert-butylphenol or ethoxylation products of polypropylene oxide.
Som ioniske emulgatorer kommer det i første rekke på tale anioniske emulgatorer. Det kan derved dreie seg om alkali-eller ammoniumsalter av alkyl-, aryl- eller alkylarylsulfo-nater, -sulfater, -fosfater, -fosfonater eller forbindelser med andre anioniske endegrupper, idet også oligo- eller polyetylenoksydenheter kan befinne seg mellom hydrokarbon-resten og den anioniske gruppe. Typiske eksempler er natriumlaurylsulfat, natriumoktylfenolglykoletersulfat, natriumdodecylbenzensulfonat, natriumlauryldiglykolsulfat, ammoniumtritert. -butylfenolpenta- eller oktaglykolsulfat. Ionic emulsifiers are primarily anionic emulsifiers. It can thereby be alkali or ammonium salts of alkyl, aryl or alkylaryl sulphonates, sulphates, phosphates, phosphonates or compounds with other anionic end groups, as oligo or polyethylene oxide units can also be found between the hydrocarbon residue and the anionic group. Typical examples are sodium lauryl sulfate, sodium octylphenol glycol ether sulfate, sodium dodecylbenzene sulfonate, sodium lauryl diglycol sulfate, ammonium tritate. -butylphenol penta- or octaglycol sulfate.
Som beskyttelseskolloider anvender man eventuelt naturstoffer, som gummiarabikum, stivelse, alginater eller modifiserte naturstoffer som metyl-, etyl-, hydroksyalkyl-eller karboksymetylcellulose eller syntetiske stoffer som polyvinylalkohol, polyvinylpyrrolidbn eller blandinger av slike stoffer. Fortrinnsvis kan det anvendes modifiserte cellulosederivater og syntetiske beskyttelseskolloider. As protective colloids, natural substances such as gum arabic, starch, alginates or modified natural substances such as methyl, ethyl, hydroxyalkyl or carboxymethyl cellulose or synthetic substances such as polyvinyl alcohol, polyvinylpyrrolidone or mixtures of such substances are used as protective colloids. Preferably, modified cellulose derivatives and synthetic protective colloids can be used.
Til starting og videreføring av polymerisasjonen betjener man seg av olje- og/eller fortrinnsvis vannoppløselige radikaldannere eller redoks-systemer. Det egner, seg eksempelvis hydrogenperoksyd, kalium- eller ammoniumperoksydisulfat, dibenzoylperoksyd, laurylperoksyd, tri-tert. - butylperoksyd, bis-azodiisobutyronitril alene eller sammen med reduserende komponenter, eksempelvis natriumbisulfit, "Rongalit", glukose, askorbinsyre og andre forbindelser som virker reduserende. To start and continue the polymerization, oil and/or preferably water-soluble radical generators or redox systems are used. It is suitable, for example, hydrogen peroxide, potassium or ammonium peroxydisulphate, dibenzoyl peroxide, lauryl peroxide, tri-tert. - butyl peroxide, bis-azodiisobutyronitrile alone or together with reducing components, for example sodium bisulphite, "Rongalit", glucose, ascorbic acid and other compounds that have a reducing effect.
Til fremstilling av dispersjonsmalinger med høy våtklebing ifølge oppfinnelsen blander man dispersjonene med en pigment-oppslemming. Slike pigmentoppslemminger, også betegnet som pigmentpastaer, som egner seg til anvendelse i lavpigmenterte dispersjonsmalinger og spesielt glansmalinger, består eksempelvis av titandioksyd som er jevnt dispergert i vann. De inneholder vanligvis beskyttelseskolloider som cellulosederivater, eksempelvis hydroksyetylcellulose, og disperger-ingsmidler, eksempelvis salter av poly(met)akrylsyre eller natriumpolyfosfat. Vanlige bestanddeler i pigmentoppslemmingen er videre antimikrobielle konverseringsmidler, anti-skummidler, pH-stabilisatorer og fyllstoffer. Spesielt egnede titandioksydpigmenter er rutil og anatas. For glansmalinger er det viktig at den midlere partikkeldiameter for pigmentet ligger i nærheten av den nedre grense av lysbølge-lengdene, altså ved ca. 0,4-0,2 ym. For fremstilling av lavpigmenterte matte malinger kan man eksempelvis medanvende spesielle silikatpigmenter med stor overflate. Bindemiddel-rike matte malinger gir strøk som er lette å rense. Pigment-pastaen kan selvsagt også inneholde fargepigmenter, men den ønskede fargetone kan likeledes innstilles ved brekking av den hvitpigmenterte dispersjonsmaling. To produce dispersion paints with high wet adhesion according to the invention, the dispersions are mixed with a pigment slurry. Such pigment slurries, also referred to as pigment pastes, which are suitable for use in low-pigmented dispersion paints and especially gloss paints, consist, for example, of titanium dioxide which is uniformly dispersed in water. They usually contain protective colloids such as cellulose derivatives, for example hydroxyethyl cellulose, and dispersants, for example salts of poly(meth)acrylic acid or sodium polyphosphate. Common ingredients in the pigment slurry are further antimicrobial conversation agents, anti-foam agents, pH stabilizers and fillers. Particularly suitable titanium dioxide pigments are rutile and anatase. For gloss paints, it is important that the mean particle diameter for the pigment is close to the lower limit of the light wavelengths, i.e. at approx. 0.4-0.2 ym. For the production of low-pigmented matte paints, special silicate pigments with a large surface can be used, for example. Binder-rich matte paints provide coats that are easy to clean. The pigment paste can of course also contain color pigments, but the desired color tone can also be set by refracting the white-pigmented dispersion paint.
Pigmentoppslemmingen kan fremstilles etter de kjente metoder, f.eks. ved dispergering av pigmentet i dissolver, eller på kule- eller sandmøller eller ved hjelp av valsemøller. The pigment slurry can be prepared according to the known methods, e.g. by dispersing the pigment in a dissolver, or on ball or sand mills or using roller mills.
Til anvendelse i glansmalinger bør pigmentoppslemmingen ikke inneholde vesentlige mengder av pigmentaggregater, fordi disse påvirker glansen. For use in gloss paints, the pigment slurry should not contain significant amounts of pigment aggregates, because these affect the gloss.
Man kan enten til dispersjonen eller også den ferdige dispersjonsmaling sette hjelpestoffer, f.eks. mykningsmidler, nettdannere, pufferstoffer, fortykkere, tiksotropimidler, rustbeskyttelsesmidler, alkydharpikser eller tørrende oljer. Mykningsmidler er her ikke de innledningsvis som filmkonsolideringsmiddel nevnte oppløsningsmidler med bare temporær virkning, men forbindelser som dibutylftalat, som senker film-dannelsestemperaturen og forblir lengere tid i polymerisatet. You can either add excipients to the dispersion or to the finished dispersion paint, e.g. plasticizers, net formers, buffering agents, thickeners, thixotropy agents, rust protection agents, alkyd resins or drying oils. Plasticizers here are not the solvents initially mentioned as film consolidating agents with only a temporary effect, but compounds such as dibutyl phthalate, which lower the film-forming temperature and remain in the polymer for a longer time.
Oppfinnelsen skal forklares nærmere ved hjelp av noen eksempler. The invention will be explained in more detail with the help of some examples.
Eksemp_el_l_ Example_el_l_
I en 2-liters trehalset kolbe som befinner seg i et varmebad og som er utrustet med røreverk, tilbakeløpskjøler, dryppe-trakt og termometer oppvarmes under omrøring en dispersjon bestående av A dispersion consisting of
603 vektdeler vann 603 parts by weight of water
18 vektdeler polyvinylalkohol med hydrolyse-grad 88 mol-% og en viskositet av 4%-ig vandig oppløsning ved 20°C på 18 cP 18 parts by weight of polyvinyl alcohol with a degree of hydrolysis of 88 mol% and a viscosity of a 4% aqueous solution at 20°C of 18 cP
0,9 vektdeler natriumvinylsulfonat 0.9 parts by weight of sodium vinyl sulfonate
6 vektdeler natriumdodecylbenzensulfonat 6 parts by weight of sodium dodecylbenzene sulphonate
0,72 vektdeler NaH2P04 . 2 H20 0.72 parts by weight of NaH2P04. 2 H 2 O
1,67 vektdeler Na2HP04■. 12 H20 1.67 parts by weight of Na2HP04■. 12 H 2 O
1,5 vektdeler ammoniumperoksydisulfat og 1.5 parts by weight of ammonium peroxydisulfate and
60 cektdeler vinylacetat 60 parts vinyl acetate
idet polymerisasjonen kommer i gang. Når temperaturen er steget til 70°C, startes med tildosering av en blanding av 54 0 vektdeler vinylacetat og 18 vektdeler aceteddiksyreallylester. Den samlede tildoseringstid utgjør ca. 3 as the polymerization starts. When the temperature has risen to 70°C, the addition of a mixture of 540 parts by weight of vinyl acetate and 18 parts by weight of acetoacetic acid allyl ester is started. The total dosing time amounts to approx. 3
timer. hours.
Man etteroppvarmer etter avslutning av monomertilsetningen enda i 2 timer ved polymerisasjonstemperatur (70°C under fortsatt omrøring og avkjøler deretter blandingen. After completion of the monomer addition, the mixture is reheated for a further 2 hours at the polymerization temperature (70°C with continued stirring and the mixture is then cooled.
Eksemgel_2_|sammenli2nin2se Exemgel_2_|compare2nin2se
Det gåes fram på nøyaktig samme måte som i eksempel 1, imidlertid tilsettes ikke aceteddiksyreallylester. The procedure is exactly the same as in example 1, however, no acetoacetic acid allyl ester is added.
Eksemp_el_3 Example_el_3
I en apparatur som omtalt i eksempel 1, oppvarmes til 70°C en dispersjon bestående av In an apparatus as discussed in example 1, a dispersion consisting of is heated to 70°C
607 vektdeler vann 607 parts by weight of water
18 vektdeler oleylpolyglykoleter med ca. 25 etylenoksydenheter 18 parts by weight of oleyl polyglycol ether with approx. 25 ethylene oxide units
0,2 vektdeler natriumdodecylbenzensulfonat 0.2 parts by weight of sodium dodecylbenzene sulphonate
12 vektdeler hydroksyetyloellulose med en gjennomsnittlig polymerisasjons-grad på ca. 400 (molvekt ca. 100.000) 1,5 vektdeler natriumacetat 12 parts by weight of hydroxyethyl cellulose with an average degree of polymerization of approx. 400 (molar weight approx. 100,000) 1.5 parts by weight sodium acetate
2,5 vektdeler ammoniumperoksydisulfat og 2.5 parts by weight of ammonium peroxydisulfate and
60 vektdeler av en monomerblanding som ble tatt ut av en blanding av 450 vektdeler vinylacetat 150 vektdeler isononansyrevinylester og 12 vektdeler aceteddiksyreallylester 60 parts by weight of a monomer mixture which was taken from a mixture of 450 parts by weight vinyl acetate 150 parts by weight isononanoic acid vinyl ester and 12 parts by weight acetoacetic acid allyl ester
og ved denne temperatur tildoseres den resterende monomerblanding (552 vektdeler) i løpet av 3 timer. Etter tildosering Blandes med 0,5 vektdeler ammoniumperoksydisulfat i 15 vektdeler vann og etteroppvarmes 2 timer. Faststoffinnholdet ligger ved ca. 50 vekt-%. and at this temperature, the remaining monomer mixture (552 parts by weight) is added over the course of 3 hours. After dosing Mix with 0.5 parts by weight of ammonium peroxydisulphate in 15 parts by weight of water and reheat for 2 hours. The solids content is approx. 50% by weight.
Det gåes fram på nøyaktig samme måte som i eksempel 3, idet det imidlertid ikke tilsettes aceteddiksyreallylester. The procedure is carried out in exactly the same way as in example 3, although no acetoacetic acid allyl ester is added.
Eksemrjel_5_ Eczema_5_
I en apparatur som omtalt i eksempel 1 oppvarmes til 7 0°C en dispersjon bestående av In an apparatus as discussed in example 1, a dispersion consisting of is heated to 70°C
618 vektdeler vann 618 parts by weight of water
18 vektdeler nonylfenolpolyglykoleter med ca. 18 parts by weight nonylphenol polyglycol ether with approx.
30 etylenoksydenheter 30 ethylene oxide units
1/5 vektdeler natriumacetat 1/5 parts by weight sodium acetate
12 vektdeler hydroksyetylcellulose med gjennomsnittlig polymerisasjons-grad på ca. 400 (molekylvekt ca. 100.000) 12 parts by weight of hydroxyethyl cellulose with an average degree of polymerization of approx. 400 (molecular weight approx. 100,000)
2,5 vektdeler ammoniumperoksydisulfat 2.5 parts by weight of ammonium peroxydisulfate
10% (62 vektdeler) av monomerblandingen, som består av 480 vektdeler vinylacetat, 120 vektdeler dibutylmaleinat og 18 vektdeler aceteddiksyreallylester, og den resterende monomerblanding tilblandes i løpet av 3 timer. Etter tildoseringen blandes med 0,5 vektdeler ammoniumperoksydisulfat i 15 vektdeler vann og etteroppvarmes i 2 timer. Faststoffinnholdet ligger ved ca. 50 vekt-%. 10% (62 parts by weight) of the monomer mixture, which consists of 480 parts by weight of vinyl acetate, 120 parts by weight of dibutyl maleate and 18 parts by weight of acetoacetic acid allyl ester, and the remaining monomer mixture is added during 3 hours. After the addition, 0.5 parts by weight of ammonium peroxydisulfate are mixed with 15 parts by weight of water and reheated for 2 hours. The solids content is approx. 50% by weight.
Eksemp_el_6_^sammenlignin2sek Example_el_6_^comparenin2sec
Det gåes fram på nøyaktig samme måte som omtalt i eksempel The procedure is exactly the same as described in the example
5, imidlertid tilsettes ikke aceteddiksyreallylester. 5, however, acetoacetic acid allyl ester is not added.
Eksempel_7 Example_7
I en apparatur som omtalt i eksempel 1 oppvarmes til 7 0°C In an apparatus as described in example 1, it is heated to 70°C
en dispersjon bestående av a dispersion consisting of
636 vektdeler vann 636 parts by weight of water
18 vektdeler nonylfenolpolyglykoleter med ca. 30 etylenoksydenheter 12 vektdeler polyvinylalkohol med hydrolyse-grad 88 mol-% og en viskositet av 4%-ig vandig oppløsning ved 20°C på 18 cP 18 parts by weight nonylphenol polyglycol ether with approx. 30 ethylene oxide units 12 parts by weight polyvinyl alcohol with a degree of hydrolysis of 88 mol% and a viscosity of a 4% aqueous solution at 20°C of 18 cP
0,9 vektdeler natriumvinylsulfonat 1,5 vektdeler natriumacetat 0.9 parts by weight sodium vinyl sulphonate 1.5 parts by weight sodium acetate
2,5 vektdeler ammoniumperoksydisulfat 2.5 parts by weight of ammonium peroxydisulfate
48 vektdeler vinylacetat 48 parts by weight vinyl acetate
12 vektdeler versatic-10-syrevinylester og 12 parts by weight of versatic-10-acid vinyl ester and
1,2 vektdeler aceteddiksyreallylester 1.2 parts by weight of acetoacetic acid allyl ester
og ved denne temperatur inndoseres i løpet av 3 timer en blanding av 432 vektdeler vinylacetat, 108 vektdeler versatic-10-syrevinylester og 18 vektdeler aceteddiksyreallylester. Etter tildoseringen blandes med 0,5 vektdeler ammoniumperoksydisulfat i 15 vektdeler vann og etteroppvarmes i 2 timer. Faststoffinnholdet ligger ved ca. 50 vekt-%. and at this temperature, a mixture of 432 parts by weight of vinyl acetate, 108 parts by weight of versatic-10-acid vinyl ester and 18 parts by weight of acetoacetic acid allyl ester is dosed over the course of 3 hours. After the addition, 0.5 parts by weight of ammonium peroxydisulfate are mixed with 15 parts by weight of water and reheated for 2 hours. The solids content is approx. 50% by weight.
?3S§§S£§i_§_isammenli2nin2s eksempel)_ ?3S§§S£§i_§_isammenli2nin2s example)_
Det gåes fram på nøyaktig samme måte som omtalt i eksempel The procedure is exactly the same as described in the example
7, imidlertid tilsettes ikke aceteddiksyreallylester. 7, however, acetoacetic acid allyl ester is not added.
Eksemp_el_9 Example_el_9
Det fremstilles en monomeremulsjon av følgende sammensetning: A monomer emulsion of the following composition is prepared:
308 vektdeler vann 308 parts by weight of water
6 vektdeler ammoniumtri-tert.-butylfenolpoly-glykoletersulfat med ca. 8 etylenoksydenheter 6 parts by weight of ammonium tri-tert.-butylphenol poly-glycol ether sulfate with approx. 8 ethylene oxide units
12 vektdeler metakrylsyre 12 parts by weight methacrylic acid
6 vektdeler akrylsyre 6 parts by weight acrylic acid
300 vektdeler 2-etylheksylakrylat 300 vektdeler metylmetakrylat og 300 parts by weight 2-ethylhexyl acrylate 300 parts by weight methyl methacrylate and
12 vektdeler aceteddiksyreallylester 12 parts by weight of acetoacetic acid allyl ester
som omrøres med en hurtigrører inntil det er fremkommet en stabil emulsjon. which is stirred with a high-speed stirrer until a stable emulsion has formed.
I en apparatur som omtalt i eksempel 1 oppvarmes en blanding av In an apparatus as described in example 1, a mixture of
306 vektdeler vann 306 parts by weight of water
3 vektdeler ammoniumtri-tert.-butylfenolpoly-glykoletersulfat med ca. 8 etylenoksydenheter og 60 vektdeler av monomeremulsjonen til 81°C og blandes med en oppløsning av 0,45 vektdeler ammoniumperoksydisulfat i 15 vektdeler vann. Deretter begynner man med tildoseringen av den resterende monomeremulsjon og fører polymeri-sas jonen til avslutning. Den samlede tildoseringstid utgjør 2 timer, og polymerisasjonstemperaturen og temperaturen under etteroppvarmingstiden ligger mellom 81 og 83°C. Etter avslutningen av monomerdoseringen blander man med 0,15 vektdeler ammoniumperoksydisulfat i 5 vektdeler vann, oppvarmer videre 60 minutter og avkjøler deretter. Faststoffinnholdet utgjør ca. 50%. 3 parts by weight of ammonium tri-tert.-butylphenol poly-glycol ether sulfate with approx. 8 ethylene oxide units and 60 parts by weight of the monomer emulsion to 81°C and mixed with a solution of 0.45 parts by weight of ammonium peroxydisulfate in 15 parts by weight of water. You then begin with the addition of the remaining monomer emulsion and bring the polymerization to completion. The total addition time is 2 hours, and the polymerization temperature and the temperature during the post-heating time are between 81 and 83°C. After the end of the monomer dosing, 0.15 parts by weight of ammonium peroxydisulphate are mixed with 5 parts by weight of water, heated for a further 60 minutes and then cooled. The solids content amounts to approx. 50%.
Det gåes fram på nøyaktig samme måte som omtalt i eksempel The procedure is exactly the same as described in the example
9, imidlertid tilsettes ikke aceteddiksyreallylester. 9, however, acetoacetic acid allyl ester is not added.
Eksemgel_ll Exemgel_ll
Det fremstilles først en monomeremulsjon av følgende sammensetning : A monomer emulsion of the following composition is first prepared:
310 vektdeler vann 310 parts by weight of water
6 vektdeler natriumsalt av laurylalkoholdi-glykoletersulfat 6 parts by weight sodium salt of lauryl alcohol di-glycol ether sulfate
12 vektdeler metakrylsyre 12 parts by weight methacrylic acid
6 vektdeler akrylsyre 6 parts by weight acrylic acid
300 vektdeler butylakrylat 300 parts by weight of butyl acrylate
300 vektdeler styren og 300 parts by weight styrene and
18 vektdeler aceteddiksyreallylester 18 parts by weight of acetoacetic acid allyl ester
som omrøres med en hurtigrører inntil det er fremkommet en stabil emulsjon. which is stirred with a high-speed stirrer until a stable emulsion has formed.
I en apparatur som omtalt i eksempel 1 oppvarmes en blanding av In an apparatus as described in example 1, a mixture of
303 vektdeler vann 303 parts by weight of water
3 vektdeler natriumsalt av laurylalkoholdigly-koletersulfat og 3 parts by weight of sodium salt of lauryl alcohol digly-chole ether sulfate and
62 vektdeler av monomeremulsjonen til 81°C 62 parts by weight of the monomer emulsion to 81°C
og blandes med en oppløsning av 0,45 vektdeler ammoniumper-oksydisulf at i 15 vektdeler vann. Deretter begynner man med tildoseringen av den resterende monomeremulsjon og fører polymerisasjonen til avslutning. Den samlede tildoseringstid utgjør 2 timer og polymerisasjonstemperaturen og temperaturen under etteroppvarmingen ligger mellom 81 og 83°C. Etter avslutning av monomerdoseringen blander man med 0,15 vektdeler ammoniumperoksydisulfat i 5 vektdeler vann, oppvarmer videre i 60 minutter og avkjøler deretter. Faststoffinnholdet utgjør ca. 50 vekt-%. and mixed with a solution of 0.45 parts by weight of ammonium peroxydisulfate in 15 parts by weight of water. You then begin with the addition of the remaining monomer emulsion and bring the polymerization to completion. The total addition time is 2 hours and the polymerization temperature and the temperature during post-heating are between 81 and 83°C. After completion of the monomer dosing, 0.15 parts by weight of ammonium peroxydisulphate are mixed with 5 parts by weight of water, heated further for 60 minutes and then cooled. The solids content amounts to approx. 50% by weight.
Eksemgel_12_^sammenli2ningsek Exemgel_12_^comparison sec
Det gåes fram på nøyaktig samme måte som i eksempel- 11, The procedure is exactly the same as in example 11,
idet det imidlertid ikke tilsettes aceteddiksyreallylester. however, no acetoacetic acid allyl ester is added.
For å undersøke våtklebing ble det fremstilt glansmalinger etter følgende resept: In order to investigate wet adhesion, gloss paints were produced according to the following recipe:
dispergeres og deretter innsettes dispersed and then inserted
2. Dispersjon (ved 50% faststoffinnhold) 710,0 vektdeler som, når pH-verdien ikke ligger over ca. 7, blandes med 2,0 vektdeler 25%-ig ammoniakk. 2. Dispersion (at 50% solids content) 710.0 parts by weight which, when the pH value does not exceed approx. 7, is mixed with 2.0 parts by weight of 25% ammonia.
Deretter tilsettes under omrøring langsomt en blanding av: Then, while stirring, slowly add a mixture of:
De under punkt 1 angitte flytende, resp. oppløselige bestanddeler med unntak av 1,2-propylenglykol, has i et rørekar i den nevnte rekkefølge og deri dispergeres pig-ment med en dissolver. Deretter tilsettes 1,2-propylenglykol. Av denne pigmentpasta fremstilles en større mengde for blanding med de forskjellige dispersjoner som skal undersøkes for å sikre like betingelser, f.eks. med hensyn til pigmentdispergering. The floating, resp. soluble components, with the exception of 1,2-propylene glycol, are placed in a mixing vessel in the order mentioned and the pigment is dispersed therein with a dissolver. 1,2-propylene glycol is then added. A larger quantity of this pigment paste is prepared for mixing with the different dispersions to be examined to ensure equal conditions, e.g. with regard to pigment dispersion.
For fremstilling av de enkelte malinger ble det fra pig-mentpastaen uttatt en tilsvarende mengde, og i den i oven-nevnte resept nevnte fremgangsmåte blandet med de ca. 1 dag gamle dispersjoner under en langsomtgående rører. Derpå ble det tilsatt de under punkt 3 nevnte oppløsnings-midler. Etter den fullstendige konfeksjonering ble malingen siktet. For the production of the individual paints, a corresponding amount was taken from the pigment paste, and in the method mentioned in the above-mentioned recipe mixed with the approx. 1 day old dispersions under a slow moving stirrer. The solvents mentioned under point 3 were then added. After the complete confection, the paint was sieved.
Disse glansmalinger påføres etter 1 dags standtid på glassplater og på stålblikk, hvorpå det på forhånd var sprøytet en lufttørrende pigmentert glinsende alkydharpikslakk og etter tørring aldret 24 timer ved 100°C. Det ble anvendt en filmpåfører med en spaltehøyde på 200 ym. Etter 24 timers tørretid av glansmalingene ble disse undersøkt etter de to nedenfor omtalte metoder med hensyn på våtklebing. These glossy paints are applied after 1 day's standing time on glass plates and on steel sheets, on which an air-drying pigmented shiny alkyd resin varnish had previously been sprayed and, after drying, aged for 24 hours at 100°C. A film applicator with a gap height of 200 ym was used. After 24 hours drying time of the gloss paints, these were examined according to the two methods mentioned below with regard to wet adhesion.
1) Slitas^eprøve 1) Wear test
På en mekanisk slitasjemaskin, slik den f.eks. er omtalt i DOS 2 262 956, tilsvarende "Gardner-Washability and Abrasion Machine", imidlertid med en ca. 1,20 m lang løpestrekning, innlegges de forberedte glassplater, således at de opptrukne dispersjonsmalingsfilmer ligger loddrett på løperetningen. On a mechanical wear machine, such as the is discussed in DOS 2 262 956, corresponding to "Gardner-Washability and Abrasion Machine", however with an approx. 1.20 m long running stretch, the prepared glass sheets are inserted, so that the applied dispersion paint films are perpendicular to the running direction.
På grunn av løpestrekningens lengde kan det i en prøvegang samtidig undersøkes ca. 15 malinger. Det anvendes en svine-bustbørste som ved begynnelsen av prøven fuktes med destillert vann. Børstenes løpestrekning fuktes under prøven likeledes med destillert vann således at børstesporet stadig er dekket med en vannfilm. Ved utilstrekkelig våtklebing av-skyves etter få børsteganger dispersjonsmalingene ved hjelp av børster fra underlaget og revner ved grensen mellom fuktet og tørr film. Våtklebingen er desto bedre jo lenger børsten løper til avskyvning av filmen. Optimal våtklebing foreligger når filmen enda ikke er skjøvet av i det fuktede børstespor etter 3000 børsteganger (1 børstegang er en frem- og tilbakebevegelse). Due to the length of the run, approx. 15 paints. A pig bristle brush is used which is moistened with distilled water at the beginning of the test. The running length of the brushes is also moistened during the test with distilled water so that the brush track is constantly covered with a film of water. In case of insufficient wet adhesion, after a few brushings, the dispersion paints are pushed off with the help of brushes from the substrate and cracks occur at the boundary between the wetted and dry film. The wet adhesion is all the better the longer the brush runs to repel the film. Optimum wet adhesion is achieved when the film has not yet been pushed off in the moistened brush groove after 3,000 brushing strokes (1 brushing stroke is a back and forth movement).
2) Kondens as jonspjrøve 2) Condensation as ion probe
Herved anvendes en firkantet termostatregulert beholder som er halvfylt med vann av 50°C og i hvis gassrom over vannover-flaten det er montert en ventilator. Den øvre åpning be-legges med de forberedte stålblikk, med prøveflatene nedad, og lukkes derved. Termostaten står i et ved 2 3°C oppvarmet rom. Ved temperaturdifferansen kondenserer det seg vann-damp på blikkenes underside og innvirker på glansmalings-filmen. Etter 15 minutters innvirkningstid hver gang avtas platene og vurderes. Hereby, a square thermostatically controlled container is used which is half-filled with water of 50°C and in whose gas space above the surface of the water a fan is mounted. The upper opening is covered with the prepared steel sheets, with the test surfaces downwards, and thereby closed. The thermostat is in a room heated at 2 3°C. Due to the temperature difference, water vapor condenses on the underside of the tins and affects the gloss paint film. After 15 minutes of exposure each time, the plates are removed and assessed.
Utilstrekkelig våtklebing viser seg i dannelse av blærer mellom dispersjonsmalingen og alkydharpikslakken samt i filmens lette avskyvbarhet, f.eks. med fingertuppen. Insufficient wet adhesion manifests itself in the formation of blisters between the dispersion paint and the alkyd resin varnish as well as in the easy peelability of the film, e.g. with the tip of your finger.
Ved god våtklebing er filmen blærefri etter 4 timer og ikke avskyvbar. With good wet adhesion, the film is blister-free after 4 hours and cannot be pushed off.
Prøveresultatene fremgår av tabell 1. The test results appear in table 1.
Eksemgel_13 Eczema gel_13
Eksempel 1 gjentas med den forholdsregel at det i stedet for aceteddiksyreallylester nå anvendes 2-(acetacetyloksy)-etylakrylat. Example 1 is repeated with the precaution that instead of acetoacetic acid allyl ester, 2-(acetacetyloxy)-ethyl acrylate is now used.
Eksem<p>_el_14 Eczema<p>_el_14
Eksempel 3 gjentas med den forholdsregel at det i stedet for aceteddiksyreallylester nå anvendes 2-(acetacetyloksy)-etylmetakrylat. Example 3 is repeated with the precaution that instead of acetoacetic acid allyl ester, 2-(acetacetyloxy)-ethyl methacrylate is now used.
Eksemp_el_15 Example_el_15
Eksempel 7 gjentas med den forholdsregel at det i stedet for aceteddiksyreallylester nå anvendes 2-(acetacetyloksy)-propylkrotonat. Example 7 is repeated with the precaution that instead of acetoacetic acid allyl ester, 2-(acetacetyloxy)-propylcrotonate is now used.
Eksemgel_16 Eczema gel_16
Eksempel 9 gjentas med den forholdsregel at det i stedet for aceteddiksyreallylester nå anvendes 2-(acetacetyloksy)-propylakrylat. Example 9 is repeated with the precaution that instead of acetoacetic acid allyl ester, 2-(acetacetyloxy)-propyl acrylate is now used.
Eksemp_el_17 Example_el_17
Eksempel 11 gjentas med den forholdsregel at det i stedet for aceteddiksyreallylester nå anvendes 2-(acetacetyloksy)-propylmetakrylat. Example 11 is repeated with the precaution that instead of acetoacetic acid allyl ester, 2-(acetacetyloxy)-propyl methacrylate is now used.
Eksemp_el_18 Example_el_18
Eksempel 3 gjentas med den forholdsregel at det i stedet for 12 deler acetacetylallylester nå anvendes 18 deler 2-(acet-acetyloksy) -etylkrotonat, idet mengden av vann utgjør 613 deler. Example 3 is repeated with the precaution that instead of 12 parts of acetacetylallyl ester, 18 parts of 2-(acet-acetyloxy)-ethylcrotonate are now used, the amount of water being 613 parts.
Tilsvarende angivelsene under eksempel 12 fremstilles av Corresponding to the information under example 12 is produced by
de ifølge eksemplene 13-18 dannede dispersjoner glansmalinger som blir undersøkt. Prøveresultatene fremgår av følgende tabell 2. the gloss paint dispersions formed according to examples 13-18 which are examined. The test results appear in the following table 2.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2535373A DE2535373C3 (en) | 1975-08-08 | 1975-08-08 | Paints based on aqueous plastic dispersions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NO762738L NO762738L (en) | 1977-02-09 |
| NO153892B true NO153892B (en) | 1986-03-03 |
Family
ID=5953505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO762738A NO153892B (en) | 1975-08-08 | 1976-08-06 | LOW-PIGMENTED SOLVENT PAINTING WITH HIGH WATER ADHESION BASED ON A SHORT PLASTIC DISPERSION |
Country Status (23)
| Country | Link |
|---|---|
| JP (1) | JPS6029751B2 (en) |
| AR (1) | AR208810A1 (en) |
| AT (1) | AT357657B (en) |
| AU (1) | AU499098B2 (en) |
| BE (1) | BE845023A (en) |
| BR (1) | BR7604854A (en) |
| CA (1) | CA1068029A (en) |
| CH (1) | CH621361A5 (en) |
| DE (1) | DE2535373C3 (en) |
| DK (1) | DK146477C (en) |
| ES (1) | ES450387A1 (en) |
| FI (1) | FI64183C (en) |
| FR (1) | FR2320339A1 (en) |
| GB (1) | GB1541909A (en) |
| IE (1) | IE43518B1 (en) |
| IT (1) | IT1065803B (en) |
| LU (1) | LU75550A1 (en) |
| MX (1) | MX145396A (en) |
| NL (1) | NL187403C (en) |
| NO (1) | NO153892B (en) |
| PT (1) | PT65451B (en) |
| SE (1) | SE428215B (en) |
| ZA (1) | ZA764756B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2947768A1 (en) * | 1979-11-27 | 1981-07-23 | Wacker-Chemie GmbH, 8000 München | AQUEOUS PLASTIC DISPERSIONS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| US4900615A (en) * | 1986-03-11 | 1990-02-13 | Union Oil Company Of California | Textile materials and compositions for use therein |
| US4908229A (en) * | 1986-03-11 | 1990-03-13 | Union Oil Of California | Method for producing an article containing a radiation cross-linked polymer and the article produced thereby |
| US4966791A (en) * | 1986-03-11 | 1990-10-30 | Union Oil Company Of California | Methods for manufacturing textile materials |
| US4908403A (en) * | 1986-05-02 | 1990-03-13 | Union Oil Of California | Pressure sensitive adhesives of acetoacetoxy-alkyl acrylate polymers |
| US4759983A (en) * | 1986-05-30 | 1988-07-26 | Union Oil Company Of California | Pressure sensitive adhesives and adhesive articles |
| US5122567A (en) * | 1986-05-02 | 1992-06-16 | Union Oil Company Of California | Pressure sensitive adhesives of acetoacetoxy-alkyl acrylate polymers |
| US5053452A (en) * | 1986-05-02 | 1991-10-01 | Union Oil Company Of California | Pressure sensitive adhesives and manufactured articles |
| US5185212A (en) * | 1986-05-02 | 1993-02-09 | Rohm And Haas Company | Acetoacetoxy-alkyl acrylate-containing pressure sensitive adhesives manufactured articles |
| US5435879A (en) * | 1986-05-30 | 1995-07-25 | Rohm And Haas Company | Methods of using pressure-sensitive adhesives |
| US5120607A (en) * | 1986-09-04 | 1992-06-09 | Union Oil Company Of California | Mastic and caulking coated substrates |
| US4855349A (en) * | 1986-09-04 | 1989-08-08 | Union Oil Company Of California | Mastic and caulking compositions and composite articles |
| US5135813A (en) * | 1986-09-04 | 1992-08-04 | Union Oil Company Of California | Mastic and caulking composite articles |
| US5073445A (en) * | 1986-09-04 | 1991-12-17 | Union Oil Company Of California | Mastic and caulking compositions and composite articles |
| US5055511A (en) * | 1986-09-04 | 1991-10-08 | Union Oil Company Of California | Mastic and caulking compositions |
| US5049416A (en) * | 1987-12-31 | 1991-09-17 | Union Oil Company Of California | Method for preparing pressure-sensitive adhesive articles |
| US5296530A (en) * | 1992-07-28 | 1994-03-22 | Rohm And Haas Company | Method for light-assisted curing of coatings |
| GB9221222D0 (en) * | 1992-10-09 | 1992-11-25 | Ici Plc | Coating composition |
| US6756459B2 (en) * | 2000-09-28 | 2004-06-29 | Rohm And Haas Company | Binder compositions for direct-to-metal coatings |
| CN100439443C (en) * | 2002-05-31 | 2008-12-03 | 克雷·瓦利·艾伯利卡公司 | Dual cure emulsions |
| US8980993B2 (en) | 2008-07-10 | 2015-03-17 | Arkema Inc. | Coating compositions for improved block resistance |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1264655B (en) * | 1965-12-22 | 1968-03-28 | Basf Ag | Process for the production of coatings, impregnations or bonds |
| FR1526440A (en) * | 1966-05-28 | 1968-05-24 | Basf Ag | Process for producing coatings, impregnated products or bonded assemblies |
| DE1644988B2 (en) * | 1967-06-28 | 1973-09-06 | Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen | COATING AND ADHESIVE AGENTS BASED ON MIXTURES OF ACETYL ACETATE GROUP POLYMERIZED COMPOUNDS, ETHYLENICALLY UNSATABLED COMPOUNDS, ACETOACETATES OF VALUE-VALUE METALS AND DILUTING AGENTS |
-
1975
- 1975-08-06 ZA ZA764756A patent/ZA764756B/en unknown
- 1975-08-08 DE DE2535373A patent/DE2535373C3/en not_active Expired
-
1976
- 1976-07-27 BR BR7604854A patent/BR7604854A/en unknown
- 1976-08-02 ES ES450387A patent/ES450387A1/en not_active Expired
- 1976-08-03 NL NLAANVRAGE7608631,A patent/NL187403C/en not_active IP Right Cessation
- 1976-08-04 CH CH996276A patent/CH621361A5/en not_active IP Right Cessation
- 1976-08-05 FI FI762246A patent/FI64183C/en not_active IP Right Cessation
- 1976-08-06 DK DK356176A patent/DK146477C/en active
- 1976-08-06 SE SE7608851A patent/SE428215B/en unknown
- 1976-08-06 PT PT65451A patent/PT65451B/en unknown
- 1976-08-06 NO NO762738A patent/NO153892B/en unknown
- 1976-08-06 AT AT584276A patent/AT357657B/en not_active IP Right Cessation
- 1976-08-06 CA CA258,621A patent/CA1068029A/en not_active Expired
- 1976-08-06 IE IE1740/76A patent/IE43518B1/en not_active IP Right Cessation
- 1976-08-06 AU AU16641/76A patent/AU499098B2/en not_active Expired
- 1976-08-06 GB GB7632875A patent/GB1541909A/en not_active Expired
- 1976-08-06 IT IT26141/76A patent/IT1065803B/en active
- 1976-08-06 LU LU75550A patent/LU75550A1/xx unknown
- 1976-08-06 AR AR264248A patent/AR208810A1/en active
- 1976-08-07 JP JP51093606A patent/JPS6029751B2/en not_active Expired
- 1976-08-09 BE BE169673A patent/BE845023A/en not_active IP Right Cessation
- 1976-08-09 MX MX165836A patent/MX145396A/en unknown
- 1976-08-09 FR FR7624263A patent/FR2320339A1/en active Granted
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