HRP960123A2 - Modified melamine resins and their use in the manufacture of post-forming laminates - Google Patents
Modified melamine resins and their use in the manufacture of post-forming laminates Download PDFInfo
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- HRP960123A2 HRP960123A2 HRA523/95A HRP960123A HRP960123A2 HR P960123 A2 HRP960123 A2 HR P960123A2 HR P960123 A HRP960123 A HR P960123A HR P960123 A2 HRP960123 A2 HR P960123A2
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- Croatia
- Prior art keywords
- melamine
- formaldehyde
- modified
- branched
- straight
- Prior art date
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- 229920000877 Melamine resin Polymers 0.000 title claims description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 150000007974 melamines Chemical class 0.000 title claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 37
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 20
- 150000001412 amines Chemical class 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000004640 Melamine resin Substances 0.000 claims description 13
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 13
- 125000004122 cyclic group Chemical group 0.000 claims description 10
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 8
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 239000000123 paper Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910001868 water Inorganic materials 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 2
- SOYBEXQHNURCGE-UHFFFAOYSA-N 3-ethoxypropan-1-amine Chemical compound CCOCCCN SOYBEXQHNURCGE-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- -1 hexylene, decylene, dodecylene, cyclohexyl Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- PMUNIMVZCACZBB-UHFFFAOYSA-N 2-hydroxyethylazanium;chloride Chemical compound Cl.NCCO PMUNIMVZCACZBB-UHFFFAOYSA-N 0.000 description 1
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 239000004251 Ammonium lactate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical group C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 229940059265 ammonium lactate Drugs 0.000 description 1
- 235000019286 ammonium lactate Nutrition 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- GCTOSMYFALESJI-UHFFFAOYSA-N azane;2-methylpropan-2-ol Chemical compound N.CC(C)(C)O GCTOSMYFALESJI-UHFFFAOYSA-N 0.000 description 1
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IDOGARCPIAAWMC-UHFFFAOYSA-N bis(2-hydroxyethyl)azanium;acetate Chemical compound CC(O)=O.OCCNCCO IDOGARCPIAAWMC-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940073579 ethanolamine hydrochloride Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000010447 natron Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Laminated Bodies (AREA)
Description
Laminati melaminske smole na osnovi impregniranih papira imaju široko područje primjene kao ukrasne i zaštitne površine zbog njihove dobre postojanosti na svjetlu, otpornosti prema trošenju, postojanosti prema kemikalijama, postojanosti prema žaru i površinske tvrdoće. Melamine resin laminates based on impregnated papers have a wide range of applications as decorative and protective surfaces due to their good light fastness, wear resistance, chemical resistance, heat resistance and surface hardness.
Slojevito prešani materijali te vrste, koji se dobivaju impregacijom nosećih traka od tekstila, papira ili staklene vune s vodenim otopinama melaminformaldehidnog predkondenzata i završnim sušenjem i otvrdnjavanjem pri temperaturama iznad 100°C, opisani su primjerice u EP-A-0 077 067. U EP-B-1 0 268 809 opisane su folije od melaminske smole, koje se dobivaju premazivanjem papira s najmanje 70 mas. %-tnom vodenom otopinom metileterificirane melaminske smole. Layered pressed materials of this type, which are obtained by impregnating carrier strips made of textile, paper or glass wool with aqueous solutions of melamine formaldehyde precondensate and final drying and hardening at temperatures above 100°C, are described for example in EP-A-0 077 067. In EP -B-1 0 268 809 describes foils made of melamine resin, which are obtained by coating paper with at least 70 wt. % aqueous solution of methyl etherified melamine resin.
Nedostatak te poznate melaminske smole i laminata melaminske smole je osobito u tome da oni kod otvrdnjavanja imaju relativno veliko skupljanje, da njihova mehanička svojstva, kao primjerice otpornost prema kipućoj vodi, u mnogim slučajevima nisu dovoljna, i da su oni prije svega vrlo krti i nemaju svojstva naknadnog oblikovanja. The disadvantage of this well-known melamine resin and melamine resin laminates is that they have a relatively large shrinkage during hardening, that their mechanical properties, such as resistance to boiling water, are not sufficient in many cases, and that they are, above all, very brittle and do not have properties of subsequent shaping.
Iz US 4,424,261 poznato je da upotreba hidroksialkil-melamina kao sredstva za modificiranje za melamin-formaldehidne smole dovodi do poboljšanja svojstava naknadne obrade. Međutim, nedostatak tog sredstva za modificiranje je njegova nepostojanost, zbog čega ono nije lako dostupno i nadalje, s njim se vrlo teško rukuje, jer jako naginju umreživanju samo sa sobom. It is known from US 4,424,261 that the use of hydroxyalkyl-melamine as a modifying agent for melamine-formaldehyde resins leads to improved post-processing properties. However, the disadvantage of this means of modification is its impermanence, which is why it is not easily accessible and furthermore, it is very difficult to handle, because they tend to network only with themselves.
Druga sredstva za modificiranje, kao primjerice guanamini, koji dovode do svojstava naknadnog oblikovanja smole, opisana su u EP-A1-0 561 432. Guanamini, naročito oni s aromatskim jezgrama, kao benzoguanamin, nemaju međutim dovoljnu postojanost prema svjetlu, zbog čega modificirane smole lako požute. Nadalje, neznatna topivost guanamina u reakcijskom mediju djeluje loše na proces proizvodnje smole. Other modifying agents, such as guanamines, which lead to post-forming properties of the resin, are described in EP-A1-0 561 432. Guanamines, especially those with aromatic nuclei, such as benzoguanamine, do not, however, have sufficient light fastness, which is why modified resins they turn yellow easily. Furthermore, the low solubility of guanamine in the reaction medium has a bad effect on the resin production process.
Bilo je stoga neophodno pronaći sredstvo za modificiranje melaminske smole koje nema nedostataka do sada poznatih sredstava za modificiranje i koje jako poboljšava svojstva naknadnog oblikovanja melaminske smole bez smanjenja njene postojanosti prema kipućoj vodi. It was therefore necessary to find an agent for modifying melamine resin which does not have the disadvantages of the previously known modifying agents and which greatly improves the subsequent shaping properties of melamine resin without reducing its resistance to boiling water.
Neočekivano je bilo pronađeno da se melaminska smola te vrste može dobiti upotrebom naročitih amina kao sredstva za modificiranje. Unexpectedly, it has been found that a melamine resin of this type can be obtained by using special amines as modifying agents.
Predmet predloženog izuma su prema tome modificirane melamin-formaldehidne smole, naznačene time, da se one sastoje od kondenzata formaldehida, melamina i sredstva za modificiranje koje sadrži izoforondiamin i/ili amine formule The subject of the proposed invention are therefore modified melamine-formaldehyde resins, characterized by the fact that they consist of formaldehyde condensate, melamine and a modifying agent containing isophoronediamine and/or amines of the formula
NR3R4-R2-Y-R1-X I, NR3R4-R2-Y-R1-X I,
u kojoj R1, ovisno o značenju od X, predstavlja ravan ili razgranati ili ciklički C1 do C12-alkilni ili alkilenski ostatak, R2 predstavlja ravan ili razgranati ili ciklički C1 do C12-alkilenski ostatak, R3 i R4 mogu biti jednaki ili različiti i predstavljaju H ili ravan ili razgranati C1 do C12-alkilni ostatak, te X označava vodik, OH ili NR3R4, a Y može biti -O- ili -NH-, pri čemu je molarni omjer formaldehida prema melaminu 1,2 do 2,5. in which R1, depending on the meaning of X, represents a straight or branched or cyclic C1 to C12-alkyl or alkylene residue, R2 represents a straight or branched or cyclic C1 to C12-alkylene residue, R3 and R4 can be the same or different and represent H or a straight or branched C1 to C12-alkyl residue, and X represents hydrogen, OH or NR3R4, and Y can be -O- or -NH-, wherein the molar ratio of formaldehyde to melamine is 1.2 to 2.5.
Melaminske smole prema izumu modificirane su tako s izoforondiaminom i/ili aminima formule I. The melamine resins according to the invention are thus modified with isophoronediamine and/or amines of formula I.
U formuli I R1, ovisno o značenju za X, može biti C1 do C12-alkilni ili alkilenski ostatak koji može biti lineran, razgranati ili ciklički. Primjeri za to jesu metil, etil, n-propil, i-propil, n-butil, sek.butil, terc.butil, heksil, decil, dodecil, metilen, etilen, n-propilen, i-propilen, n-butilen, sek.butilen, terc.butilen, heksilen, decilen, dodecilen, cikloheksil ili ciklodecil. Pri tome ciklički ostaci mogu po potrebi biti supstituirani s daljnjim alkilnim skupinama. In formula I R1, depending on the meaning of X, can be a C1 to C12-alkyl or alkylene residue which can be linear, branched or cyclic. Examples are methyl, ethyl, n-propyl, i-propyl, n-butyl, sec.butyl, tert.butyl, hexyl, decyl, dodecyl, methylene, ethylene, n-propylene, i-propylene, n-butylene, sec.butylene, tert.butylene, hexylene, decylene, dodecylene, cyclohexyl or cyclodecyl. In this case, the cyclic residues can be substituted with further alkyl groups if necessary.
To su ponajprije linearni, razgranati ili ciklički C1 do C6-alkilni ili alkilenski ostaci. These are primarily linear, branched or cyclic C1 to C6-alkyl or alkylene residues.
U formuli I R2 predstavlja kao što je gore definirano linearan, razgranati ili ciklički C1-C12-alkilenski ostatak. Ponajprije to su linearni, razgranati ili ciklički C1-C6-alkilenski ostaci. R3 i R4 mogu biti jednaki ili različiti i predstavljaju H ili kako je gore definirano ravan ili razgranati C1 do C12-alkilni ostatak. R3 i R4 ponajprije predstavljaju vodik. In formula I, R2 represents, as defined above, a linear, branched or cyclic C1-C12-alkylene residue. These are primarily linear, branched or cyclic C1-C6-alkylene residues. R 3 and R 4 may be the same or different and represent H or as defined above a straight or branched C 1 to C 12 -alkyl radical. R3 and R4 preferably represent hydrogen.
X može biti vodik, hidroksilni ili aminski ostatak. Pri tome se pod aminskim ostatkom također podrazumijevaju primarni, sekundarni kao također i tercijarni aminski ostaci formule -NR3R4, pri čemu R3 i R4 su kao gore definirani. X can be hydrogen, hydroxyl or amine residue. In this case, amine residue is also understood to mean primary, secondary as well as tertiary amine residues of the formula -NR3R4, where R3 and R4 are as defined above.
Y predstavlja -O- ili -NH-. Y represents -O- or -NH-.
Primjeri za amine formule I jesu metoksipropilamin, etoksipropilamin, diglikolamin. Examples of amines of formula I are methoxypropylamine, ethoxypropylamine, diglycolamine.
To su ponajprije amini kao eventualno etoksipropilamin, diglikolamin, ili izoforondiamin. These are primarily amines such as possibly ethoxypropylamine, diglycolamine, or isophoronediamine.
Izoforondiamin i amini formule I mogu se upotrijebiti kako kao pojedinačni spojevi, tako također i kao smjese od više amina. Količina amina u melamin-formaldehidnoj smoli prema izumu je otprilike 1,5 do 20 mas. % u odnosu na melamin. Ponajprije se upotrebljava otprilike 2,5 do 15 mas. % amina. Isophoronediamine and amines of formula I can be used both as individual compounds and also as mixtures of several amines. The amount of amine in the melamine-formaldehyde resin according to the invention is approximately 1.5 to 20 wt. % compared to melamine. Approximately 2.5 to 15 wt. % amine.
Aminima formule I mogu se po potrebi dodatno primiješati uobičajena sredstva za modificiranje kao eventualno dicijanamid, kaprolaktam, jednovalentni ili viševalentni alkoholi kao trimetilolpropan. Pri tome količina dodatnog sredstva za modificiranje je između 0 i 40 mas. % u odnosu na melamin, ponajprije između 0 i 20 mas. %. If necessary, the amines of formula I can be additionally mixed with usual modifying agents such as possibly dicyanamide, caprolactam, monovalent or polyvalent alcohols such as trimethylolpropane. At the same time, the amount of additional modifier is between 0 and 40 wt. % in relation to melamine, preferably between 0 and 20 wt. %.
Molni omjer formaldehida prema melaminu kod modificiranih smola je od 1,2:1 do 2,5:1. Formaldehid i melamin upotrebljavaju se ponajprije u molnom omjeru od 1,4 do 2,0:1. The molar ratio of formaldehyde to melamine in modified resins is from 1.2:1 to 2.5:1. Formaldehyde and melamine are preferably used in a molar ratio of 1.4 to 2.0:1.
Modificirane melamin-formaldehidne smole dobiju se tako da se na poznat način u vodenoj otopini melamin kondenzira s formaldehidom i prije ili tijekom kondenzacije primiješa se sredstvo za modificiranje gore navedenom količinom. Pri tome amini se dodaju izravno k melaminformaldehidnoj smoli koju se modificira. Međutim, visoko modificirane melamin-formaldehidne smole mogu se također proizvesti i u predstupnju dodatkom od 40 do 60 mas. % amina u odnosu na melamin. Ta visoko modificirana melamin-formaldehidna smola može se tada upotrijebiti kao sredstvo za modificiranje pri proizvodnji melamin-formaldehidne smole prema izumu (MF-smole). Pri tome maseni omjer sredstva za modificiranje prema MF-smoli iznosi 1:2 do 1:4, ponajprije 1:3. Modified melamine-formaldehyde resins are obtained by condensing melamine with formaldehyde in a known manner in an aqueous solution, and before or during the condensation, a modifying agent is added in the amount specified above. Here, amines are added directly to the melamine-formaldehyde resin that is being modified. However, highly modified melamine-formaldehyde resins can also be produced in the pre-stage with the addition of 40 to 60 wt. % amine in relation to melamine. This highly modified melamine-formaldehyde resin can then be used as a modifying agent in the production of the melamine-formaldehyde resin according to the invention (MF-resin). The mass ratio of the modifying agent to the MF-resin is 1:2 to 1:4, preferably 1:3.
Daljnji predmet predloženog izuma je zatim upotreba melamin-formaldehidne smole koja sadrži 40 do 60 mas. % amina formule I u odnosu na melamin, i formaldehid i melamin u molarnom omjeru od 1,2 do 2,5, za proizvodnju modificiranih melamin-formaldehidnih smola. A further subject of the proposed invention is the use of melamine-formaldehyde resin containing 40 to 60 wt. % amine of formula I in relation to melamine, and formaldehyde and melamine in a molar ratio of 1.2 to 2.5, for the production of modified melamine-formaldehyde resins.
Za ubrzanje reakcije kod modificiranja melaminske smole s kombinacijom prema izumu mogu se dodati uobičajeni katalizatori, kao npr. p-toluolsulfonska kiselina, količinom od otprilike 0,1 do 1 mas. % u odnosu na ukupnu količinu melaminske smole. To speed up the reaction when modifying the melamine resin with the combination according to the invention, common catalysts, such as p-toluenesulfonic acid, can be added in an amount of approximately 0.1 to 1 wt. % in relation to the total amount of melamine resin.
Da se ubrza otvrdnjavanje, a da se time ne pogorša elastičnost smole, smolama se nadalje također mogu dodati i soli slabih do jačih karbonskih kiselina, sulfonskih kiselina ili mineralnih kiselina, koje se mogu hidrolizirati, primjerice dietanolaminacetat, morfolin, dietanolamin, etanolamin-hidroklorid, etilendiaminacetat, amonijev rodanid, etilandiaminacetat, amonijrodanid, amonijev laktat, etilendiaminofosfat ili dimetiletanol-amonijeva sol p-toluolsulfonske kiseline. In order to accelerate the hardening, without thereby worsening the elasticity of the resin, salts of weak to strong carboxylic acids, sulfonic acids or mineral acids, which can be hydrolyzed, can also be added to the resins, for example diethanolamine acetate, morpholine, diethanolamine, ethanolamine hydrochloride, ethylenediamineacetate, ammonium rhodanide, ethylenediamineacetate, ammoniumrhodanide, ammonium lactate, ethylenediaminophosphate or dimethylethanol-ammonium salt of p-toluenesulfonic acid.
Kondenzacija smole nastavlja se u pravilu sve do ograničenog razrjeđenja u vodi. Tako dobivene smole, te visoko modificirane smole upotrijebljene kao sredstvo za modificiranje, mogu se po želji prevesti u prah raspršnim sušenjem. Pri tome, smole se suše primjerice pomoću centrifugalne ili zračne sušilice ponajprije do zaostale vlage od 1 - 1,5%. Tako osušene smole moraju se tada prije upotrebe otopiti u vodi. Condensation of the resin usually continues until limited dilution in water. The resins obtained in this way, and the highly modified resins used as a modifying agent, can be turned into powder by spray drying if desired. In doing so, the resins are dried, for example, using a centrifugal or air dryer, preferably to a residual moisture of 1 - 1.5%. The dried resins must then be dissolved in water before use.
Melamin-formaldehidne smole modificirane prema izumu naročito su prikladne za proizvodnju dekorativnih i zaštitnih površina s odličnim svojstvima naknadnog oblikovanja. Proizvodnja prethodnih proizvoda (filmova) dekorativnih ili zaštitnih površina vrši se impregnacijom papirnatih ili traka od tkanine. Papirnate trake su ponajprije od ukrasnog papira ili natronskog papira. Trake od tekstila izrađene su pri tome ponajprije od vune, tkanine ili naslaga od staklenih, ugljičnih, keramičkih ili aramidnih vlakana. Sukladno zahtjevima prema svojstvima tako dobivenih laminata, mogu se upotrijebiti mješavine različitih vlakana, jednosmjerna beskrajna vlakna ili više slojeva jednakih ili različitih traka za ojačanje. Melamine-formaldehyde resins modified according to the invention are particularly suitable for the production of decorative and protective surfaces with excellent subsequent molding properties. Production of previous products (films) of decorative or protective surfaces is done by impregnation of paper or fabric strips. Paper strips are preferably made of decorative paper or soda paper. Textile tapes are primarily made of wool, fabric or layers of glass, carbon, ceramic or aramid fibers. According to the requirements for the properties of the laminates thus obtained, mixtures of different fibers, unidirectional endless fibers or multiple layers of the same or different reinforcing tapes can be used.
Impregnacija tih traka s melamin-formaldehidnim smolama modificiranim prema izumu vrši se primjerice potapanjem ili prskanjem i na kraju kalupljenjem ili struganjem sve do željenog sadržaja smole filma. Sadržaj smole ovisi prije svega o traženim svojstvima filma, odnosno laminata, te o vrsti vlakana za ojačanje i kreće se obično od 30 do 60 mas. % u odnosu na noseći materijal impregniran sa smolom. The impregnation of these strips with melamine-formaldehyde resins modified according to the invention is carried out, for example, by dipping or spraying and finally by molding or scraping until the desired resin content of the film is reached. The resin content depends primarily on the required properties of the film, i.e. the laminate, and on the type of reinforcing fibers and usually ranges from 30 to 60 wt. % in relation to the carrier material impregnated with resin.
Sukladno viskoznosti i konzistenciji melaminske smole impregnacija se odvija obično pri temperaturama od približno 20 do 60°C. Da bi se dobili filmovi koji se mogu skladištiti, po završetku impregnacije papiri se osuše pri otprilike 80 do 160°C na određeni sadržaj zaostale vlage, pri čemu ovisno o temperaturi i trajanju toplinske obrade smola za impregnaciju, lake tecivosti, reagira više ili manje s djelomičnim otvrdnjavanjem i umreživanjem. Depending on the viscosity and consistency of the melamine resin, impregnation usually takes place at temperatures of approximately 20 to 60°C. In order to obtain films that can be stored, after the completion of the impregnation, the papers are dried at approximately 80 to 160°C to a certain residual moisture content, whereby, depending on the temperature and duration of the heat treatment, the light-flowing impregnation resin reacts more or less with by partial hardening and cross-linking.
U tom stanju pri otprilike sobnoj temperaturi film se može skladištiti i transportirati. In this state, at approximately room temperature, the film can be stored and transported.
Zatim se pri temperaturi od 120 do 180°C i pod pritiskom od 25 do 100 bara više slojeva impregniranog natronskog i dekorativnog papira preša u laminat. Zbog odličnih svojstava naknadnog oblikovanja laminat se može preoblikovati u željeni otpresak s daljnjim umreživanjem melaminske smole pri temperaturama od 80 do 180°C i pod pritiskom. Then, at a temperature of 120 to 180°C and under a pressure of 25 to 100 bar, several layers of impregnated sodium and decorative paper are pressed into a laminate. Due to the excellent post-forming properties, the laminate can be reshaped into the desired blank with further cross-linking of the melamine resin at temperatures from 80 to 180°C and under pressure.
Laminati dobiveni od smola modificiranih prema izumu odlikuju se prije svega visokom otpornošću prema kipućoj vodi, te poboljšanom elastičnošću svoje površine, tako da se mogu postići mali radijusi savijanja bez nastanka napuklina. Laminates obtained from resins modified according to the invention are characterized above all by high resistance to boiling water and improved elasticity of their surface, so that small bending radii can be achieved without the formation of cracks.
Primjer 1 Example 1
U posudi s miješalicom i povratnim hladilom kondenzira se 126 dijelova (1 mol) melamina, 137,5 dijelova (1,65 mola) 36%-tne otopine formaldehida, 4,6 dijelova (0,027 mola) izoforondiamina i 42,4 dijela deionizirane vode pri 90°C i pH-vrijednosti od 9,5 - 10 (na toj vrijednosti održava pomoću natrijevog hidroksida) dok se postigne razrijeđenje vode od otprilike 0,2 (pri 20°C), (volumni udio H2O : volumnom udjelu smole). 126 parts (1 mol) of melamine, 137.5 parts (1.65 mol) of a 36% formaldehyde solution, 4.6 parts (0.027 mol) of isophoronediamine and 42.4 parts of deionized water are condensed in a vessel with a stirrer and a reflux condenser. at 90°C and a pH-value of 9.5 - 10 (maintained at this value using sodium hydroxide) until a water dilution of approximately 0.2 (at 20°C) is reached (volume fraction of H2O : volume fraction of resin).
Primjeri 2 do 4 Examples 2 to 4
Analogno primjeru 1 bile su proizvedene daljnje modificirane melaminske smole. Udio melamina iznosio je 126 dijelova (1 mol), udio 36%-tnog formaldehida (FA), deionizirane vode (H2O), upotrijebljenog sredstva za modificiranje (MM), te postignuta razrijeđenost vode (WD) navedeni su u tablici 1. Analogous to example 1, further modified melamine resins were produced. The proportion of melamine was 126 parts (1 mol), the proportion of 36% formaldehyde (FA), deionized water (H2O), the used modifying agent (MM), and the achieved water dilution (WD) are listed in Table 1.
Tablica 1. Table 1.
[image] [image]
T — udio T — share
Primjer 5 Example 5
Smole iz primjera 1 do 4 bile su s 0,2 mas. % umreživala EC 15 (Chemie Linz, Castellanza) namještene na zamućenje pri 100°C od 20 minuta. Na kraju su bili impregnirani ukrasni papir, te natronski papir, koji djeluje kao papir jezgre. Dekorativni papir (95 g/m2) sadržavao je 55 mas. % smole i 6 mas. % hlapljivih sastojaka (u odnosu na impregnirani papir), papir jezgre (80 g/m2) sadržavao je 47 mas. % smole i također 6 mas. % hlapljivih sastojaka (u odnosu na impregnirani papir). The resins from examples 1 to 4 were with 0.2 wt. % crosslinkers EC 15 (Chemie Linz, Castellanza) set to clouding at 100°C for 20 minutes. At the end, there were impregnated decorative paper, and natron paper, which acts as core paper. Decorative paper (95 g/m2) contained 55 wt. % resin and 6 wt. % volatile ingredients (in relation to impregnated paper), core paper (80 g/m2) contained 47 wt. % resin and also 6 wt. % of volatile ingredients (in relation to impregnated paper).
Zatim su jedan sloj impregniranog dekorativnog papira i 3 sloja papira jezgre zajedno prešani pod pritiskom od 30 bara pri 175°C tijekom 20 sekundi. Then one layer of impregnated decorative paper and 3 layers of core paper were pressed together under a pressure of 30 bar at 175°C for 20 seconds.
Tako dobiveni laminati ispitani su glede sposobnosti naknadnog preoblikovanja i njihove otpornosti prema kipućoj vodi. Rezultati su prikazani u tablici 2. The laminates obtained in this way were tested for their subsequent reshaping ability and their resistance to boiling water. The results are presented in Table 2.
Tablica 2. Table 2.
[image] [image]
(*)Najmanji promjer oko kojeg se laminat zagrijan na 160°C može savinuti a da ne napukne. (*) The smallest diameter around which laminate heated to 160°C can be bent without cracking.
Claims (9)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT0052395A AT403051B (en) | 1995-03-24 | 1995-03-24 | MODIFIED MELAMINE RESINS AND THE USE THEREOF FOR PRODUCING POST-FORMING LAMINATES |
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| Publication Number | Publication Date |
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| HRP960123A2 true HRP960123A2 (en) | 1997-08-31 |
| HRP960123B1 HRP960123B1 (en) | 2000-08-31 |
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| Application Number | Title | Priority Date | Filing Date |
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| HR960123A HRP960123B1 (en) | 1995-03-24 | 1996-03-15 | Modified melamine resins and their use in the manufacture of post-forming laminates |
Country Status (11)
| Country | Link |
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| EP (1) | EP0815151B1 (en) |
| AR (1) | AR001397A1 (en) |
| AT (2) | AT403051B (en) |
| AU (1) | AU5105696A (en) |
| DE (1) | DE59605916D1 (en) |
| EG (1) | EG20799A (en) |
| HR (1) | HRP960123B1 (en) |
| IL (1) | IL117622A (en) |
| MY (1) | MY120497A (en) |
| WO (1) | WO1996030422A1 (en) |
| ZA (1) | ZA962334B (en) |
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| AR040209A1 (en) | 2002-06-14 | 2005-03-16 | Agrolinz Melamin Gmbh | RESIN AMINO MOLDING MATERIAL FOR PRODUCTS WITH IMPROVED FLEXIBILITY AND RESIN AMINO PRODUCTS WITH IMPROVED FLEXIBILITY |
| EP3263560A1 (en) | 2016-06-29 | 2018-01-03 | Borealis Agrolinz Melamine GmbH | Novel triazine-precondensate-aldehyde condensation products and method for obtaining the same |
| EP3263561A1 (en) | 2016-06-29 | 2018-01-03 | Borealis Agrolinz Melamine GmbH | Novel triazine precondensate and method for obtaining the same |
| CN117430772B (en) * | 2023-07-25 | 2024-04-02 | 江苏佳饰家新材料集团股份有限公司 | Low-formaldehyde high-fluidity impregnating resin and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3859243A (en) * | 1973-11-27 | 1975-01-07 | Formica Corp | Melamine-formaldehyde resin containing 2-(2-aminoethoxy) ethanol |
| JPS5329357A (en) * | 1976-08-31 | 1978-03-18 | Matsushita Electric Works Ltd | Preparation of melamine resin compositions |
| DE2851760A1 (en) * | 1978-11-30 | 1980-06-12 | Cassella Ag | MELAMINE RESIN, METHOD FOR THE PRODUCTION THEREOF AND ITS USE FOR THE PRODUCTION OF COATED WOODEN MATERIALS AND LAYERING COMPRESSES |
| US4370442A (en) * | 1980-12-05 | 1983-01-25 | Pearson Glenn A | Fire retardant compositions |
| SU1028684A1 (en) * | 1981-07-03 | 1983-07-15 | Предприятие П/Я М-5885 | Process for preparing melamine formaldehyde oligomer (modifications) |
| DE3828793A1 (en) * | 1988-08-25 | 1990-03-01 | Basf Ag | CONTINUOUS PREPARATION OF WAESSEN MELAMINE FORMALDEHYDE VORKONDENSAT SOLUTIONS |
-
1995
- 1995-03-24 AT AT0052395A patent/AT403051B/en not_active IP Right Cessation
-
1996
- 1996-03-09 AT AT96907417T patent/ATE196484T1/en not_active IP Right Cessation
- 1996-03-09 WO PCT/EP1996/001024 patent/WO1996030422A1/en active IP Right Grant
- 1996-03-09 AU AU51056/96A patent/AU5105696A/en not_active Abandoned
- 1996-03-09 EP EP96907417A patent/EP0815151B1/en not_active Expired - Lifetime
- 1996-03-09 DE DE59605916T patent/DE59605916D1/en not_active Expired - Fee Related
- 1996-03-15 HR HR960123A patent/HRP960123B1/en not_active IP Right Cessation
- 1996-03-22 IL IL11762296A patent/IL117622A/en not_active IP Right Cessation
- 1996-03-22 ZA ZA962334A patent/ZA962334B/en unknown
- 1996-03-22 MY MYPI96001073A patent/MY120497A/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| EP0815151A1 (en) | 1998-01-07 |
| IL117622A (en) | 2001-03-19 |
| AR001397A1 (en) | 1997-10-22 |
| ATE196484T1 (en) | 2000-10-15 |
| EG20799A (en) | 2000-03-29 |
| ATA52395A (en) | 1997-03-15 |
| ZA962334B (en) | 1996-09-27 |
| MY120497A (en) | 2005-11-30 |
| DE59605916D1 (en) | 2000-10-26 |
| IL117622A0 (en) | 1996-07-23 |
| HRP960123B1 (en) | 2000-08-31 |
| WO1996030422A1 (en) | 1996-10-03 |
| AU5105696A (en) | 1996-10-16 |
| EP0815151B1 (en) | 2000-09-20 |
| AT403051B (en) | 1997-11-25 |
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