CH560729A5 - Hardening acrylic esters of alkoxy-melamines - by irradiation with ionising rays, giving weather-resistant, glossy coatings - Google Patents
Hardening acrylic esters of alkoxy-melamines - by irradiation with ionising rays, giving weather-resistant, glossy coatingsInfo
- Publication number
- CH560729A5 CH560729A5 CH208372A CH208372A CH560729A5 CH 560729 A5 CH560729 A5 CH 560729A5 CH 208372 A CH208372 A CH 208372A CH 208372 A CH208372 A CH 208372A CH 560729 A5 CH560729 A5 CH 560729A5
- Authority
- CH
- Switzerland
- Prior art keywords
- films
- hydrogen
- compounds
- parts
- irradiation
- Prior art date
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title description 3
- 229920000877 Melamine resin Polymers 0.000 title 1
- 125000004849 alkoxymethyl group Chemical group 0.000 claims abstract description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229920003002 synthetic resin Polymers 0.000 claims description 11
- 239000000057 synthetic resin Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 150000007974 melamines Chemical class 0.000 claims description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims 1
- 239000010960 cold rolled steel Substances 0.000 claims 1
- 230000001066 destructive effect Effects 0.000 claims 1
- 229910000398 iron phosphate Inorganic materials 0.000 claims 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000002023 wood Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001723 curing Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000005865 ionizing radiation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OELQSSWXRGADDE-UHFFFAOYSA-N 2-methylprop-2-eneperoxoic acid Chemical compound CC(=C)C(=O)OO OELQSSWXRGADDE-UHFFFAOYSA-N 0.000 description 1
- XGJZQNMUVTZITK-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexamethoxy-1,3,5-triazine-2,4,6-triamine Chemical compound CON(OC)C1=NC(N(OC)OC)=NC(N(OC)OC)=N1 XGJZQNMUVTZITK-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 241000589614 Pseudomonas stutzeri Species 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- -1 diallyl phthalate Chemical compound 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Cpds. of mixts. of cpds. of formula(I) are hardened, esp. as thin layers or coatings, by ionising irradiation. In (I), R is H, hydroxymethyl or alkoxymethyl, X is H or CH3, Y is H or 1-4C Z is H or CH3, m = 0-6 and n = 0-10; the mol. of (I) contains an average of >=1 gp. of formula: The coatings are more resistant to weathering and retain their gloss. They can be used on metal or wood, or on heat-sensitive substrates, e.g. synthetic or paper.
Description
Es ist bekannt, die Vernetzung von Kunstharz-Polymeren durch Einwirkung ionisierender Strahlen, z. B. Röntgenstrah- len, Gammastrahlen, Betateilchen oder Strahienbtindel stark beschleunigert Elektronen hervorzurufen. Bei den meisten technischen Anwendungen dieser Bestrahlungsmethoden werden Elektronen mit einer Energie zwischen 50 und 4000 KeV verwendet.
Es ist ferner bekannt, zum Hearten von Kunstharzüber- ziigen, bestehend aus Mischungen ungesättigter Polyester und reaktionsfähiger olefinisch ungesättigter Monomeren, ionisierende Strahlen zu benutzen. Diese bekannten, durch Strahlungshärtung erhaltenen Uberziige weisen zwar im allgemeinen gute mechanische Eigenschaften auf, doch besitzen sie fir viele technische Anwendungen auch einige Nachteile, wie z. B. eine ungenügende Witterungsbestitndigkeit, ungentigen- de Dehnbarkeit und Schlagfestigkeit sowie eine geringe Glanzhaltung.
Es wurde nun überraschend gefunden, dass man Uberzii- ge mit besserer Witterungsbeständigkeit und Glanzhaltung er hilt, wenn man anstelle der bekannten Kunstharzüberzüge aus ungesättigten Polyesterharzen und reaktionsfähigen Monomeren aus Verbindungen oder Gemischen von Verbindungen der Formel I
EMI1.1
in welcher R Wasserstoff und/oder eine Hydroxymethyl oder Alkoxymethylgruppe mit 1-18 Kohlenstoffatomen in der Alkylgruppe,
X Wasserstoff oder die Methylgruppe,
Y Wasserstoff oder eine Alkylgruppe mit 1-4 Kohlenstoffatomen,
Z Wasserstoff oder die Methylgruppe, m eine Zahl von 0 bis 6 und n eine Zahl von 0 bis 10 bedeuten, wobei im Mittel auf ein Molekül der Melaminverbindungen mindestens eine Gruppe der Formel II
EMI1.2
kommt, mit ionisierenden Strahien bestrahlt.
Vorzugsweise verwendet man Verbindungen bzw. Gemische von Verbindungen der Formel I, worin R Wasserstoff oder die Methoxymethylgruppe, X Wasserstoff oder insbesondere die Methylgruppe, Y und Z je Wasserstoff, m eine Zahl von 0 bis 6 und n 0 oder 1 bedeuten. Ferner kann die Bestrahlung auch in Gegenwart von weiteren olefinisch ungesättigten monomeren Verbindungen, vor allem Verbindungen der Acrylsäurereihe, wie Ester aus Acrylsäure oder Methacrylsäure und Alkoholen oder Phenolen, z. B. Athylacry- lat, Dodecylacrylat, insbesondere aber Methyl- oder Butylacrylat oder Methyl- oder Butylmethacrylat, ferner Acrylnitril, Methacrylnitril, Äthylenglycoldimethacrylat usw. erfolgen. Im weiteren kann man auch andere reaktionsfahige olefinisch ungesättigte Monomere, wie z. B.
Styrol, Divinylbenzol, Vinyl ester, wie Vinylacetat, Allylverbindungen, wie Diallylphthalat, u. a. verwenden.
Die speziell zur Herstellung von Überzügen geeigneten Kunstharzmischungen können zusätzlich noch Flexibilisatoren, Füllstoffe und vorzugsweise Pigmente, z. B. Titanoxid, enthalten. Die Verbindungen der Formel I werden vorzugsweise in Form dinner Schichten oder Überzüge bestrahlt.
Die Härtung der Kunstharzmischung kann mit jeder ionisierenden Strahlung, vorzugsweise mit einer energiereichen elektromagnetischen Strahlung, wie z. B. Röntgen- oder Gammastrahlung, sowie mit beschleunigten Elektronen vorgenommen werden. In letzterem Fall wird mit einer durchschnittlichen Elektronenenergie von 50 KeV bis 4000 KeV gearbeitet. Handelt es sich um die Härtung dinner Schichten, wie z. B. Beschichtungen, wird eine durchschnittliche Elektronenenergie von 50 bis 600 KeV und eine Härtungsdosis von 0,5-5,0 Megarad, insbesondere von 1-3 Megarad angewendet.
Die Kunstharzmischung kann vorteilhafterweise vor, wäh- rend oder nach dem Hearten noch zusätzlich einer Warme- behandlung unterzogen werden, wodurch es in manchen Fill- len zu einer Erleichterung der Vernetzung kommt.
Die Härtung wird zweckmiissig in Abwesenheit von Sauerstoff durchgefiihrt. Um dies zu erreichen, wendet man eine Schutzgasatmosphäre, z. B. Stickstoff, an.
In manchen Fallen ist es vorteilhaft, der Kunstharzmischung kleine Mengen eines freie Radikale bildenden Polymerisationskatalysators, wie z. B. Peroxide, Azoverbindungen, Persulfate, zuzugeben.
Durch das Verfahren der Erfindung ist es, neben der Beschichtung von Metall, Holzwerkstoff, Holz usw., auch mög- lich, Substrate, die temperaturempfindlich sind, z. B. Kunststoffe, Papier usw., zu beschichten und die Beschichtung auszuhärten.
Beispiel 1
A) Herstellung des zu härtenden Acrylsäureesters:
390 g Hexamethoxymethylmelamin (1 Mol) werden mit 344 g Methacrylsäure (= 4 Mol) und 9,2 g Kupfernaphtenat (8 /0 Kupfer-Metall) in einen Sulfierkolben von 1500 ml Inhalt vorgelegt. Die Reaktionskomponenten werden während ca. 2 Stunden bei 100-110 C unter Rückfluss gehalten. Bei gleicher Temperatur und einem Druck von ca. 300 mm Hg werden anschliessend während 8-9 Stunden tropfenweise 211 g Destillat (Gemisch von Methanol und Methacrylsäure mit einer Säurezahl von 284) abgetrennt.
Der Rtlckstand weist eine Säurezahl von 50 und ca. 4 Mol C= C-Doppelbindungen pro kg Substanz auf. Pro Molekül Hexamethoxymethylmelamin sind durchschnittlich 1,65 Moleküle Methacrylsaure verestert worden.
B) Härtung:
Aus dem Umsetzungsprodukt werden 90 m dicke Filme auf elektrolytisch vorbehandeltes Eisenblech (Blechstärke 0,3 mm) aufgebracht Nach etwa 1 Minute werden diese Filme beschleunigten Elektronen mit einer durchschnittlichen Energie von 400 KeV ausgesetzt, indem die Bleche der Länge nach mit verschiedenen Geschwindigkeiten durch einen Elektronenstrahl (Strahlungsintensität 4 Megarad/sek) hindurchgeführt werden. Die Versuche werden bei Raumtemperatur in einer Stickstoffatmösphäre (maximale Sauerstoffkonzentration 0,2 %) ausgeftihrt. Anschliessend werden die bei verschiedenen Geschwindigkeiten gehärteten Filme sofort quantitativ auf Oberflächenklebrigkeit und Oberflächenhärte mit dem Finger bzw. Stahlklinge geprüft.
Zugleich wird die Bestädigkeit der Kunstharzfilme gegenüber chemischen Lösungsmitteln durch Auftragen eines Tropfens Toluol oder Aceton quantitativ gepriift. Die Härtungsdosis stellt die minimale Strahlungsdosis dar, welche zur Herstellung eines klebfreien Films mit guter Oberflächenhärte notwendig ist; sie beträgt 0,3 Megarad. Die quantitative Bestimmung des unlöslichen Anteiles wird in einem Extraktionsapparat nach Soxhlet durch 24sttindige Extraktion mit Toluol bestimmt.
Die Extraktion zeigt, dass der mit der Härtungsdosis von 0,3 Megarad gehärtete Film zu 82 % unlösliche Anteile ent hilt.
Kunstharzmischungen aus 70 Teilen des oben genannten Harzes und 30 Teilen eines Monomeren werden - wie oben beschrieben-appliziert, bestrahlt und untersucht.
Die Tabelle I zeigt die erhaltenen Resultate:
Tabelle I Monomere Härtungsdosis Unlöslicher Anteil (Megarad) in % Butylacrylat 0,5 70 Methylmethacrylat 1,0 72 Styrol 4,0 88 Butylmethacrylat 0,5 74
Beispiel 2
A) Herstellung des zu hartenden Acrylsäureesters:
390 g Hexamethoxymethylmelamin (1 Mol) werden mit 390 g Hydroxyäthylmethacrylat (3 Mol), 140 g n-Butylacrylat, 4,5 g Arneisensäure und 0,65 g Phenothiazin in einen Sulfierkolben von 1500 ml Inhalt eingewogen. Das Reaktionsgemisch wird auf 100-110 C erwärmt; anschliessend werden während ca. 4 Stunden bei einem Druck von 300 mm Hg tropfenweise 170 g Gesamtdestillat (Gemisch aus 96 g n-Butylacrylat und 74 g Methanol) abgetrennt.
Der Rückstand, eine mittelviskose Flüssigkeit enthält 3,7 Mol C=C-Doppelbindungen pro 1 kg Substanz. Pro Mo lekul Hexamethoxymelamin sind durchschnittlich 1,17 Molekiile Hydroxiltaylmethacrylat veräthert worden.
B) Härtung:
Aus dem Umsetzungsprodukt werden 90 ,um dicke Filme wie in Beispiel 1 beschrieben auf Eisenblech aufgebracht, be Oberflächenhärte: HB-F Bleistifthärte Eindringwiderstand: 100 Grad Ritzhärte: 150 p nach der Erichsen-Skala: Gitterschnitt: Gt 0 Pendelhärte: 145 Sek.
It is known that the crosslinking of synthetic resin polymers by exposure to ionizing radiation, e.g. B. X-rays, gamma rays, beta particles or beam rods are strongly accelerated to produce electrons. Most of the technical applications of these irradiation methods use electrons with an energy between 50 and 4000 KeV.
It is also known to use ionizing radiation to hear synthetic resin layers consisting of mixtures of unsaturated polyesters and reactive olefinically unsaturated monomers. Although these known coatings obtained by radiation curing generally have good mechanical properties, they also have some disadvantages for many technical applications, such as e.g. B. inadequate weather resistance, inadequate elasticity and impact resistance and poor gloss retention.
It has now surprisingly been found that coatings with better weather resistance and gloss retention are obtained if, instead of the known synthetic resin coatings made from unsaturated polyester resins and reactive monomers, made from compounds or mixtures of compounds of the formula I
EMI1.1
in which R is hydrogen and / or a hydroxymethyl or alkoxymethyl group with 1-18 carbon atoms in the alkyl group,
X is hydrogen or the methyl group,
Y is hydrogen or an alkyl group with 1-4 carbon atoms,
Z is hydrogen or the methyl group, m is a number from 0 to 6 and n is a number from 0 to 10, with on average at least one group of the formula II per molecule of the melamine compounds
EMI1.2
comes irradiated with ionizing rays.
Preference is given to using compounds or mixtures of compounds of the formula I in which R is hydrogen or the methoxymethyl group, X is hydrogen or in particular the methyl group, Y and Z are each hydrogen, m is a number from 0 to 6 and n is 0 or 1. Furthermore, the irradiation can also be carried out in the presence of other olefinically unsaturated monomeric compounds, especially compounds of the acrylic acid series, such as esters of acrylic acid or methacrylic acid and alcohols or phenols, e.g. B. ethyl acrylate, dodecyl acrylate, but especially methyl or butyl acrylate or methyl or butyl methacrylate, also acrylonitrile, methacrylonitrile, ethylene glycol dimethacrylate, etc. take place. In addition, other reactive olefinically unsaturated monomers, such as. B.
Styrene, divinylbenzene, vinyl esters such as vinyl acetate, allyl compounds such as diallyl phthalate, and the like. a. use.
The synthetic resin mixtures especially suitable for the production of coatings can also contain flexibilizers, fillers and preferably pigments, e.g. B. titanium oxide. The compounds of the formula I are preferably irradiated in the form of layers or coatings.
The curing of the synthetic resin mixture can be carried out with any ionizing radiation, preferably with high-energy electromagnetic radiation, such as. B. X-rays or gamma rays, as well as with accelerated electrons. In the latter case, an average electron energy of 50 KeV to 4000 KeV is used. Is it about the hardening dinner layers, such as B. coatings, an average electron energy of 50 to 600 KeV and a curing dose of 0.5-5.0 megarads, especially 1-3 megarads is used.
The synthetic resin mixture can advantageously also be subjected to a heat treatment before, during or after hearing, which in some cases facilitates crosslinking.
Curing is expediently carried out in the absence of oxygen. To achieve this, a protective gas atmosphere is used, e.g. B. nitrogen.
In some cases it is advantageous to add small amounts of a free radical polymerization catalyst, such as. B. peroxides, azo compounds, persulfates, add.
With the method of the invention, in addition to the coating of metal, wood-based material, wood, etc., it is also possible to use substrates that are temperature-sensitive, e.g. B. plastics, paper, etc. to coat and cure the coating.
example 1
A) Production of the acrylic acid ester to be hardened:
390 g of hexamethoxymethylmelamine (1 mol) are placed in a sulfonation flask with a capacity of 1500 ml together with 344 g of methacrylic acid (= 4 mol) and 9.2 g of copper naphtenate (8/0 copper metal). The reaction components are refluxed at 100-110 ° C. for about 2 hours. At the same temperature and a pressure of approx. 300 mm Hg, 211 g of distillate (mixture of methanol and methacrylic acid with an acid number of 284) are then separated off dropwise over 8-9 hours.
The residue has an acid number of 50 and approx. 4 mol of C = C double bonds per kg of substance. An average of 1.65 molecules of methacrylic acid have been esterified per molecule of hexamethoxymethylmelamine.
B) hardening:
From the reaction product, 90 m thick films are applied to electrolytically pretreated sheet iron (sheet thickness 0.3 mm). After about 1 minute, these films are exposed to accelerated electrons with an average energy of 400 KeV by pushing the sheets lengthwise at different speeds through an electron beam (Radiation intensity 4 megarad / sec) are passed through. The experiments are carried out at room temperature in a nitrogen atmosphere (maximum oxygen concentration 0.2%). The films cured at different speeds are then immediately tested quantitatively for surface tack and surface hardness with a finger or a steel blade.
At the same time, the resistance of the synthetic resin films to chemical solvents is checked quantitatively by applying a drop of toluene or acetone. The curing dose represents the minimum radiation dose which is necessary to produce a tack-free film with good surface hardness; it is 0.3 megarads. The quantitative determination of the insoluble fraction is determined in a Soxhlet extraction apparatus by extraction with toluene for 24 hours.
The extraction shows that the film hardened with the hardening dose of 0.3 megarad contains 82% insolubles.
Synthetic resin mixtures of 70 parts of the above-mentioned resin and 30 parts of a monomer are - as described above - applied, irradiated and examined.
Table I shows the results obtained:
Table I Monomers curing dose Insoluble fraction (megarad) in% Butyl acrylate 0.5 70 Methyl methacrylate 1.0 72 Styrene 4.0 88 Butyl methacrylate 0.5 74
Example 2
A) Production of the acrylic acid ester to be hardened:
390 g of hexamethoxymethylmelamine (1 mol) are weighed into a sulphonation flask of 1500 ml content with 390 g of hydroxyethyl methacrylate (3 mol), 140 g of n-butyl acrylate, 4.5 g of arneic acid and 0.65 g of phenothiazine. The reaction mixture is heated to 100-110 C; 170 g of total distillate (mixture of 96 g of n-butyl acrylate and 74 g of methanol) are then separated off dropwise over a period of about 4 hours at a pressure of 300 mm Hg.
The residue, a medium viscosity liquid, contains 3.7 mol of C = C double bonds per 1 kg of substance. An average of 1.17 molecules of hydroxyl methacrylate have been etherified per molecule of hexamethoxymelamine.
B) hardening:
From the reaction product, 90 .mu.m thick films are applied to sheet iron as described in Example 1, be surface hardness: HB-F pencil hardness penetration resistance: 100 degrees scratch hardness: 150 p according to the Erichsen scale: cross-cut: Gt 0 pendulum hardness: 145 sec.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH208372A CH560729A5 (en) | 1972-02-14 | 1972-02-14 | Hardening acrylic esters of alkoxy-melamines - by irradiation with ionising rays, giving weather-resistant, glossy coatings |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH208372A CH560729A5 (en) | 1972-02-14 | 1972-02-14 | Hardening acrylic esters of alkoxy-melamines - by irradiation with ionising rays, giving weather-resistant, glossy coatings |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH560729A5 true CH560729A5 (en) | 1975-04-15 |
Family
ID=4225499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH208372A CH560729A5 (en) | 1972-02-14 | 1972-02-14 | Hardening acrylic esters of alkoxy-melamines - by irradiation with ionising rays, giving weather-resistant, glossy coatings |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH560729A5 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1988006973A1 (en) * | 1987-03-09 | 1988-09-22 | Polycure Pty Limited | Laminated board and electron beam curable composition used in manufacture thereof |
| AU622401B2 (en) * | 1987-03-09 | 1992-04-09 | Polycure Pty. Ltd. | Laminated board and electron beam curable composition used in manufacture thereof |
| EP0575637A1 (en) * | 1990-12-17 | 1993-12-29 | Dai Nippon Toryo Co., Ltd. | Coating composition and process for producing a precoated plate |
-
1972
- 1972-02-14 CH CH208372A patent/CH560729A5/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1988006973A1 (en) * | 1987-03-09 | 1988-09-22 | Polycure Pty Limited | Laminated board and electron beam curable composition used in manufacture thereof |
| AU622401B2 (en) * | 1987-03-09 | 1992-04-09 | Polycure Pty. Ltd. | Laminated board and electron beam curable composition used in manufacture thereof |
| EP0575637A1 (en) * | 1990-12-17 | 1993-12-29 | Dai Nippon Toryo Co., Ltd. | Coating composition and process for producing a precoated plate |
| US5361616A (en) * | 1990-12-17 | 1994-11-08 | Dai Nippon Toryo Co., Ltd. | Coating composition and process for producing a precoated plate |
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