HRP950615A2 - Modified melamine resins and their use for manufacturing post-formed laminates - Google Patents
Modified melamine resins and their use for manufacturing post-formed laminates Download PDFInfo
- Publication number
- HRP950615A2 HRP950615A2 HRA2420/94A HRP950615A HRP950615A2 HR P950615 A2 HRP950615 A2 HR P950615A2 HR P950615 A HRP950615 A HR P950615A HR P950615 A2 HRP950615 A2 HR P950615A2
- Authority
- HR
- Croatia
- Prior art keywords
- melamine
- formaldehyde
- relation
- formula
- modified
- Prior art date
Links
- 229920000877 Melamine resin Polymers 0.000 title claims description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 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 31
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 31
- 150000005846 sugar alcohols Polymers 0.000 claims description 21
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 16
- 239000004640 Melamine resin Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 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 8
- 239000000203 mixture Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 claims description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229940117969 neopentyl glycol Drugs 0.000 claims description 2
- -1 trihydroxyethyl isocyanurate Chemical compound 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 239000000123 paper Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- 238000009835 boiling Methods 0.000 description 4
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N ethyl trimethyl methane Natural products CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 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
- 238000004132 cross linking Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- PMUNIMVZCACZBB-UHFFFAOYSA-N 2-hydroxyethylazanium;chloride Chemical compound Cl.NCCO PMUNIMVZCACZBB-UHFFFAOYSA-N 0.000 description 1
- AHHQDHCTHYTBSV-UHFFFAOYSA-N 3-methylpentane-1,3,5-triol Chemical compound OCCC(O)(C)CCO AHHQDHCTHYTBSV-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
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical class CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 229940059265 ammonium lactate Drugs 0.000 description 1
- 235000019286 ammonium lactate Nutrition 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 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
- 150000004653 carbonic acids Chemical class 0.000 description 1
- 125000005243 carbonyl alkyl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005034 decoration Methods 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
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZSFDBVJMDCMTBM-UHFFFAOYSA-N ethane-1,2-diamine;phosphoric acid Chemical compound NCCN.OP(O)(O)=O ZSFDBVJMDCMTBM-UHFFFAOYSA-N 0.000 description 1
- 229940073579 ethanolamine hydrochloride Drugs 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical class CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B29/00—Layered products comprising a layer of paper or cardboard
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
-
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
- D21H17/51—Triazines, e.g. melamine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2061/00—Use of condensation polymers of aldehydes or ketones or derivatives thereof, as moulding material
- B29K2061/20—Aminoplasts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2317/00—Animal or vegetable based
- B32B2317/12—Paper, e.g. cardboard
- B32B2317/125—Paper, e.g. cardboard impregnated with thermosetting resin
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/22—Structures being applied on the surface by special manufacturing processes, e.g. in presses
- D21H27/26—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Laminated Bodies (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Laminati melaminske smole na bazi impregniranih papira imaju veliko područje primjene kao površine za dekoriranje i zaštitne površine, zbog svojih svojstava da zadržavaju stalnu boju, zbog čvrstoće na habanje, otpornost na kemikalije, otpornost na visoku temperaturu i zbog čvrstoće površine.
Slojeviti, tiskani materijali takve vrste, koji se dobivaju impregniranjem nosive podloge iz tekstila, papira ili staklene vune s vodenim otopinama melamin-formaldehid-predkondenzata i konačno sušenjem i stvrdnjavanjem pri temperaturama od iznad 100°C, opisani su na primjer u EP-A-0 077 067. U EP-B1-0 268 809 su opisane folije od melaminske smole, koje se dobivaju prevlačenjem papira sa najmanje 70 tež.% vodene otopine metileterizirane melaminske smole.
Nedostatak tih poznatih melaminskih smola i laminata melaminskih smola je u tome, da se oni kod stvrdnjavanja dosta skupljaju, da njihova mehanička svojstva, kao npr. otpornost na ključalu vodu, u mnogo slučajeva nisu dovoljno dobra, da su prije svega dosta krhki, te da ne posjeduju svojstva koja omogućuju naknadno oblikovanje.
Iz US 4,424,261 je poznato, da primjena hidroksilalkil-melamina kao modificirajućeg sredstva za melamin-formaldehid-smole utječe na poboljšanje svojstava naknadnog oblikovanja. Nedostatak tih modificirajućih sredstava je njihova nestabilnost, a time je i baratanje njima teže, pošto su dosta sklona međusobnom umrežavanju. Ostala modificirajuća sredstva, kao na primjer guanamini, koja omogućavaju svojstva naknadnog oblikovanja smola, opisana su u EP-Al-0 561 432. Guanamini, naročito oni s aromatskim jezgrama kao benzoguanamin, nisu dovoljno otporni na svjetlo, uslijed čega modificirane smole lako požute. Nadalje slaba topivost guanamina u reakcijskom mediju loše utječe na proces proizvodnje smola.
Zbog toga se pokazalo potrebnim pronaći modificirajuće sredstvo za melaminske smole, koje ne bi imalo loše strane do sada poznatih modificirajućih sredstava i koje bi znatno poboljšalo svojstva naknadnog oblikovanja, a da se pri tome ne smanji njihova otpornost na ključalu vodu.
Tako se neočekivano otkrilo, da se takve melaminske smole mogu dobiti kombinacijom određenih polialkohola i diciandiamida kao modificirajućih sredstava.
Predmet ovog izuma su prema tome modificirane melamin-formaldehid-smole, koje su naznačene time, da se sastoje iz formaldehid-kondenzata, melamina i modificirajućeg sredstva i kombinacije
a) 5 do 25 tež.%, u odnosu na melamin, diciandiamid i
b) 8 do 30 tež.%, u odnosu na melamin, vodotopivi polialkohol s najmanje dvije hidroksilalkil grupe, pri čemu molarni odnos formaldehida prema melaminu iznosi 1,2 do 2,5.
Melaminske smole prema ovom izumu su modificirane pomoću kombinacije diciandiamida s polialkoholima, koji sadrže najmanje dvije hidroksil-alkil grupe.
Polialkoholi, koji imaju najmanje dvije hidroksil-alkil grupe, su pri tome spojevi, kod kojih su hidroksil-alkil grupe vezane na alifatsku, cikloalifatsku ili heterocikličku strukturu jezgre. Kao alifatske strukture jezgre se pri tome podrazumijevaju linearne ili razgranate C1 do C10 alkil-grupe, koje se isto tako mogu supstituirati s karbonil-, amino- ili (C1-C6)-alkoksil grupama. Kao cikloalifatska struktura jezgre dolaze u obzir C5 do C8 cikloalkil-grupe, koje isto tako pored hidroksil-alkil-grupa mogu imati ostale supstituente kao npr. karbonil-grupe. Heterociklička struktura jezgre može u ciklusu 1 do 3 imati heteroatome kao N, O ili S i isto tako ostale supstituente, kao npr. karbonil-ostatke. Udio alkila hidroksil-alkil grupa iznosi 1 do 6 C-atoma.
Preporučaju se polialkoholi formule
[image]
ili ostatak formule
[image]
a R2 linearni ili razgranati (C1 do C4)-ostatak alkila.
U formuli Ib) R3, R4 i R5 znače linearni ili razgranati (C1 do C6)-ostatak alkila, koji se isto tako može supstituirati sa slijedećom hidroksil-grupom.
R3, R4 i R5 mogu pri tome biti isti ili različiti.
R3 nadalje može biti ostatak cikloalkila sa 6 C-atoma.
Pri tome su osobito preporučivi polialkoholi trimetilolpropan, trimetiloletan, trihidroksiletilizocianurat, neopentilglikol, 1,4-dimetilolciklo-heksan, 4-metil-2,4-pentandiol, 1,6-heksandiol, 3-metil-1, 3, 5-pentantriol i 2, 2, 4-trimetil-1,3-pentandiol.
Polialkoholi se mogu dodavati kao pojedinačni spoj ili kao smjesa više polialkohola. Količina polialkohola u melaminskoj smoli prema ovom izumu iznosi oko 8 do 30 tež.%, u odnosu na upotrijebljeni melamin. Preporuča se korištenje 12 do 22 tež.% polialkohola.
Polialkoholi se prema ovom izumu koriste u kombinaciji s diciandiamidom kao modificirajućim sredstvom za melamin-formaldehid-smole. Količina diciandiamida je pri tome oko 5 do 25 tež.%, u odnosu na upotrijebljeni melamin, a preporuča se oko 8 do 18 tež.%. Molarni odnos formaldehida prema melaminu je kod smola koje treba modificirati pri 1,2:1 do 2,5:1. Preporuča se upotreba formaldehida i melamina u molarnom odnosu od 1,4 do 2,0:1.
Melamin-formaldehid-smole modificirane prema ovom izumu dobivaju se tako, da se na poznati način u vodenoj otopini kondenzira melamin s formaldehidom te da se uz miješanje dodaju komponente polialkohola i diciandiamida prije ili za vrijeme kondenzacije u gore navedenoj količini. Pri tome se mogu dodavati komponente polialkohola i diciandiamida kao mješavina ili kao pojedinačne komponente. Za proizvodnju smola prema ovom izumu može se upotrijebiti gotova mješavina koja se sastoji iz melamina, formaldehida, diciandiamida i polialkohola.
Slijedeći predmet ovog izuma je prema tome upotreba mješavine iz formaldehida, melamina, 5 do 25 tež.%, u odnosu na melamin, diciandiamid i 8 do 30 tež.% u odnosu na melamin, na vodotopivi polialkohol sa najmanje dvije hidroksilalkil-grupe, koja sadrži formaldehid i melamin u molarnom odnosu od 1,2 do 2,5, za proizvodnju modificiranih melamin-formaldehid smola.
Za ubrzavanje reakcije kod modifikacije melaminskih smola s kombinacijom prema ovom izumu, mogu se dodati uobičajeni katalizatori, kao npr. p-toluolsulfonska kiselina, u količinama od oko 0,1 do 1 tež.%, u odnosu na sveukupnu količinu melaminske smole.
Smolama se nadalje mogu dodati soli, koje mogu biti podvrgnute hidrolizi, slabih do jakih ugljičnih kiselina, sulfonskih kiselina ili mineralnih kiselina, na primjer dietanolaminacetat, morfolin, dietanolamin, etanolaminhidroklorid, etilendiammacetat, amoniumrodanid, amoniumlaktat, etilendiaminfosfat ili soli dimetiletanolamina p-toluolsulfonske kiseline, kako bi se ubrzalo otvrdnjavanje, a da se pri tome ne ugrozi elastičnost smola.
Kod proizvodnje smola se mogu staviti dodatna modificirajuća sredstva, kaprolaktam ili aromatski amidi sulfonske kiseline, kao p-toluol-sulfonamidi. Kondenzacija smola se u pravilu nastavlja do ograničene mogućnosti razrjeđivanja vodom.
Modificirane melamin-formaldehid smole su naročito prikladne za proizvodnju površina za dekoriranje i zaštitinih površina s odličnim svojstvima koja omogućavaju naknadno oblikovanje. Proizvodnja predproizvoda (filmova) površina za dekoriranje i zaštitnih površina se vrši impregniranjem niti papira ili tkanine. Papirnate niti (vlakna) su obično od dekor papira ili debelog papira. Niti tkanine se sastoje po mogućnosti od vune, tkanine ili podloge od staklenih-, ugljenih-, keramičkih ili aramid vlakana. Odgovarajuće zahtjevima na svojstva tako proizvedenih laminata, može se koristiti i smjesa različitih vlakana, jednosmjernih beskrajnih vlakana ili više slojeva istih ili različitih niti za pojačanje.
Impregniranje tih niti (traka) sa modificiranim melemin-formaldehid smolama vrši se primjerice uranjanjem ili prskanjem i konačno gnječenjem ili struganjem do željenog sadržaja smole filmova. Sadržaj smole prije svega ovisi o traženim svojstvima filmova odnosno laminata kao i o vrsti pojačanja vlakna, i obično je od 30 do 60%, u odnosu na nosivi (osnovni) materijal koji je impregniran smolom.
Ovisno o viskoznosti i konzistenciji melaminske smole, do impregniranja dolazi obično pri temperaturama od oko 20 do 60°C. Kako bi se spriječilo izlaženje melaminske smole iz nosivog (osnovnog) materijala, nastavno na impregniranje pri 80 do 160°C se filmovi suše na određen preostali sadržaj vlage, pri čemu smola za impregniranje koja lako teče reagira ovisno o temperaturi i duljini termičke obrade više ili manje uslijed djelomičnog otvrdnjavanja i umrežavanja.
U tom stanju je film na sobnoj temperaturi sposoban za skladištenje i transport. Više slojeva impregniranog debelog i dekor papira se na temperaturi od 120 do 180°C pod pritiskom od 25 do 100 bar prešaju do laminata. Na osnovu odličnih svojstava koja omogućavaju naknadno oblikovanje, laminat se može daljnjim umrežavanjem melaminske smole kod temperatura od 80 do 180°C pod tlakom oblikovati do željenog oblika.
Laminati dobiveni iz smola modificiranih prema ovom izumu imaju prije svega veliku otpornost na ključalu vodu kao i poboljšanu elastičnost površine, tako da se mogu postići mali radijusi savijanja, a da pri tome ne dolazi do stvaranja pukotina.
Primjer 1
U spremniku sa miješalicom i uređajem za hlađenje sa povratnim fluksom kondenzira se 126 dijelova (1 mol) melamina, 137,5 dijelova (1,65 mol) 36% otopine formaldehida, 20 dijelova (0,15 mol) trimetilpropana, 17,5 dijelova (0,21 mol) diciandiamida i 66 dijelova neionizirane vode pri 90°C i uz pH-vrijednost od 9,5-10 (podržavano pomoću natrijevog hidroksida) do razrijeđenosti vode od oko 1,2 (pri 20°C), (1,0 dijelova volumena (smola):l,2 dijelova volumena (H2O)).
Primjer 2 do 4
Analogno primjeru 1 proizvode se ostale modificirane melaminske smole. Udio melamina iznosio je 126 dijelova (1 mol), udio 36 %-tnog formaldehida iznosio je 137,5 dijelova (1,65 mol). Upotrijebilo se 66 dijelova neionizirane vode. Upotrijebljeni polialkohol, njegov udio, kao i udio diciandiamida se mogu vidjeti iz tabele 1.
Tabela 1
[image]
Usporedbeni primjer V1:
Analogno primjeru 1 proizvela se melaminska smola sa 37,5 dijelova (0,28 mol) na trimetilpropanu, ali bez diciandiamida.
Primjer 5
Smole iz primjera 1 do 4 kao i iz primjera V1 se kataliziraju sa 0,2 tež.% otvrdnjivača EC15 (Chemie Linz Castellanza) 20 minuta na točki zamućenja od 100°C. Konačno se dekor papir kao i debeli papir, koji je fungirao kao osnovni papir (jezgra), impregnira. Dekor papir (95 g/m2) sadrži 55 tež.% udjela smole i 6 tež.% isparivih sastavnih dijelova (u odnosu na impregnirani papir), osnovni papir (80 g/m2) sadrži 47 tež.% udjela smole i isto tako 6 tež% isparivih sastavnih dijelova (u odnosu na impregnirani papir).
Jedan sloj impregniranog dekor papira i 3 sloja osnovnog papira se tada s tlakom od 30 bar pri temperaturi od 175°C za 20 sekundi zajedno prešaju.
Tako dobiveni laminati se ispituju s obzirom na njihovu mogućnost naknadnog formiranja i njihovu otpornost na ključalu vodu. Rezultati se mogu vidjeti u tabeli 2.
Tabela 2
[image]
(*) Najmanji promjer na kojem se laminat može savinuti oko metalnog cilindra, zagrijanog na 160°C, a da ne počne pucati.
Claims (7)
1. Modificirane melamin-formaldehid smole, naznačene time, da se sastoje od kondenzata iz formaldehida, melamina i modificirajućih agensa koji sadrže spoj od
a) 5 do 25 tež.% u odnosu na melamin, diciandiamida i
b) 8 do 30 tež.% u odnosu na melamin, vodotopivih polialkohola formule
R1-(R2OH)3 Ia
ili
HOR4-R3-R5OH Ib
pri čemu u formuli Ia R1 označava ostatak formule
C-(CH2)n-CH3 sa n jednak 0 do 3 IIa
ili ostatak formule
[image]
i R2 je ravan ili razgranat (C1 do C4) ostatak alkila, a u formuli Ib R3 označava ostatak cikloalkila sa 6 atoma ugljika ili R3, kao R4 i R5 od ravnog ili razgranatog (C1 do C6) ostatka alkila, koji se može supstituirati sa dodatnom hidroksil grupom ako je potrebno, pri čemu R3, R4 i R5 mogu biti isti ili različiti, a molarni odnos formaldehida prema melaminu je 1,2 do 2,5.
2. Modificirana melamin-formaldehid smola prema zahtjevu 1, naznačena time, da se modificirajući agens sastoji od spoja od
a) 8 do 18 tež.% u odnosu na melamin, diciandiamida i
b) 12 do 22 tež.% u odnosu na melamin, vodotopivog polialkohola formule Ia ili Ib.
3. Modificirana melamin-formaldehidna smola prema zahtjevu 1, naznačena time, da se kao polialkohol može koristiti trimetilolpropan, trimetiloletan, trihidroksiletilizocianurat, neopentilglikol, 1,4-dimetilolcikloheksan, 4-metil-2,4-pentandiol, 1,6-heksandiol, 3-metil-l,3,5-pentandiol ili 2,2,4-trimetil-l,3-pentandiol ili njihove smjese.
4. Modificirane melamin-formaldehid smole prema zahtjevu 1, naznačene time, da sadrže formaldehid i melamin u molarnom odnosu od 1,4:1 do 2:1.
5. Upotreba smjese formaldehida, melamina, 5 do 25 tež.%, u odnosu na melamin, diciandiamida i 8 do 30 tež.%, u odnosu na melamin, vodotopivog polialkohola formule Ia ili Ib, prema zahtjevu 1, naznačena time, da sadrži formaldehid i melamin u molarnom odnosu od 1,2:2,5, a koristi se za proizvodnju modificiranih melamin-formaldehid smola.
6. Laminati melaminske smole, naznačeni time, da se sastoje od dugačkih listova od papira ili tkanine impregniranih modificiranim melaminskim smolama prema zahtjevu 1.
7. Postupak za proizvodnju laminata melaminske smole, naznačen time, da je svitak od papira ili tkanine impregniran modificiranom melaminskom smolom kondenzata formaldehida, melamina i modificirajućeg agensa, koji sadrži spoj od, povezanih na alifatsku, cikloalifatsku ili heterocikličku grupu,
a) 5 do 25 tež.% u odnosu na melamin, diciandiamida i
b) 8 do 30 tež.% u odnosu na melamin, vodotopivog polialkohola formula Ia ili Ib, prema zahtjevu 1, a molarni odnos formaldehida prema melaminu je 1,2:2,5, te da se filmovi dobiveni prilikom impregnacije prešaju u laminat, djelomično se suše ako je potrebno, preoblikuju se i pri tome se potpuno očvršćavaju.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT0242094A AT403804B (de) | 1994-12-28 | 1994-12-28 | Modifizierte melaminharze und deren verwendung zur herstellung von ''post-forming''-laminaten |
Publications (2)
Publication Number | Publication Date |
---|---|
HRP950615A2 true HRP950615A2 (en) | 1997-10-31 |
HRP950615B1 HRP950615B1 (en) | 2000-02-29 |
Family
ID=3534033
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
HRA2420/94A HRP950615B1 (en) | 1994-12-28 | 1995-12-22 | Modified melamine resins and their use for manufacturing post-formed laminates |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0800543B2 (hr) |
AR (1) | AR000581A1 (hr) |
AT (2) | AT403804B (hr) |
AU (1) | AU4344096A (hr) |
DE (1) | DE59505333D1 (hr) |
EG (1) | EG20735A (hr) |
HR (1) | HRP950615B1 (hr) |
IL (1) | IL116576A (hr) |
MY (1) | MY114288A (hr) |
TR (1) | TR199501701A2 (hr) |
TW (1) | TW289023B (hr) |
WO (1) | WO1996020230A1 (hr) |
ZA (1) | ZA9511022B (hr) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT405404B (de) * | 1996-07-12 | 1999-08-25 | Agrolinz Melamin Gmbh | Modifizierte melaminharze und deren verwendung zur herstellung von postforming-fähigen laminaten |
US6001925A (en) * | 1998-01-14 | 1999-12-14 | Georgia-Pacific Resins, Inc. | Melamine-formaldehyde resins modified with dicyandiamide and sorbitol for impregnation of substrates for post-formable decorative laminates |
CA2431037C (en) | 2000-12-15 | 2010-05-25 | Agrolinz Melamin Gmbh | Modified inorganic particles |
HUP0302595A2 (hu) | 2000-12-15 | 2003-10-28 | Agrolinz Melamin Gmbh | Polimerrel módosított szervetlen részecskék |
AT410211B (de) | 2000-12-15 | 2003-03-25 | Agrolinz Melamin Gmbh | Halbzeuge und formstoffe aus aminoplasten |
AU2002351690B2 (en) | 2001-11-19 | 2007-03-29 | Ami - Agrolinz Melamine International Gmbh | Products, especially moulding materials of polymers containing triazine segments, method for the production thereof and uses of the same |
CN116888212A (zh) | 2020-12-22 | 2023-10-13 | 地板工业有限公司 | 改性三聚氰胺-甲醛树脂、浸渍有改性三聚氰胺-甲醛树脂的纸、用于制造地板镶板的方法及双氰胺作为三聚氰胺-甲醛树脂中的改性剂的用途 |
CN114957581B (zh) * | 2022-07-04 | 2023-07-18 | 珠海格力电器股份有限公司 | 改性三聚氰胺树脂及其制备方法、集尘板及空气净化器 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB872185A (en) * | 1958-05-18 | 1961-07-05 | Monsanto Canada Ltd | Resin syrups |
DE4111142C2 (de) † | 1991-04-06 | 1995-02-02 | Sueddeutsche Kalkstickstoff | Modifizierungsmittel für Melamin-Formaldehydharze und damit hergestellte Melamin-Formaldehydharze und Verwendung der Melamin-Formaldehydharze zur Herstellung von beschichteten Spanplatten und Hartfaserplatten nach dem Kurztaktverfahren und von Schichtstoffen und beschichteten Platten im kontinuierlichen Verfahren |
BE1005822A3 (nl) † | 1992-05-19 | 1994-02-08 | Dsm Nv | Gemodificeerde melamineformaldehyde-harssamenstelling. |
-
1994
- 1994-12-28 AT AT0242094A patent/AT403804B/de not_active IP Right Cessation
-
1995
- 1995-11-29 TW TW084112730A patent/TW289023B/zh active
- 1995-12-13 AU AU43440/96A patent/AU4344096A/en not_active Abandoned
- 1995-12-13 AT AT95942137T patent/ATE177438T1/de not_active IP Right Cessation
- 1995-12-13 DE DE59505333T patent/DE59505333D1/de not_active Expired - Fee Related
- 1995-12-13 WO PCT/EP1995/004920 patent/WO1996020230A1/de active IP Right Grant
- 1995-12-13 EP EP95942137A patent/EP0800543B2/de not_active Expired - Lifetime
- 1995-12-22 HR HRA2420/94A patent/HRP950615B1/xx not_active IP Right Cessation
- 1995-12-26 MY MYPI95004082A patent/MY114288A/en unknown
- 1995-12-27 TR TR95/01701A patent/TR199501701A2/xx unknown
- 1995-12-27 IL IL11657695A patent/IL116576A/xx not_active IP Right Cessation
- 1995-12-27 EG EG108395A patent/EG20735A/xx active
- 1995-12-28 ZA ZA9511022A patent/ZA9511022B/xx unknown
- 1995-12-28 AR AR33485895A patent/AR000581A1/es unknown
Also Published As
Publication number | Publication date |
---|---|
IL116576A0 (en) | 1996-03-31 |
EG20735A (en) | 1999-12-29 |
ZA9511022B (en) | 1996-07-05 |
EP0800543A1 (de) | 1997-10-15 |
IL116576A (en) | 2000-06-01 |
AR000581A1 (es) | 1997-07-10 |
HRP950615B1 (en) | 2000-02-29 |
ATE177438T1 (de) | 1999-03-15 |
TW289023B (hr) | 1996-10-21 |
MY114288A (en) | 2002-09-30 |
EP0800543B2 (de) | 2003-08-13 |
EP0800543B1 (de) | 1999-03-10 |
AU4344096A (en) | 1996-07-19 |
AT403804B (de) | 1998-05-25 |
TR199501701A2 (tr) | 1996-07-21 |
WO1996020230A1 (de) | 1996-07-04 |
DE59505333D1 (de) | 1999-04-15 |
ATA242094A (de) | 1997-02-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3082180A (en) | Modified melamine-formaldehyde resin for decorative laminating and process for preparing same | |
US4455416A (en) | Cyclic urea/glyoxal/polyol condensates and their use in treating textile fabrics and paper | |
HRP950615A2 (en) | Modified melamine resins and their use for manufacturing post-formed laminates | |
CA2084378A1 (en) | Resin solution for the impregnation of paper webs | |
EP0710682B1 (de) | Melamin-Formaldehyd-Tränkharze für Folien und Kanten | |
US4505712A (en) | Cyclic urea/glyoxal/polyol condensates and their use in treating textile fabrics and paper | |
AT405404B (de) | Modifizierte melaminharze und deren verwendung zur herstellung von postforming-fähigen laminaten | |
DE2316289C3 (de) | Verfahren zur Herstellung schnellhärtender Überzüge | |
EP0815151B1 (de) | Modifizierte melaminharze und deren verwendung zur herstellung von post-forming-laminaten | |
EP0003798B1 (de) | Verfahren zur Herstellung modifizierter Aminoplastharze | |
DE2443645A1 (de) | Modifizierter aminoplast, verfahren zu seiner herstellung und seine verwendung | |
US5346937A (en) | Modifying agents for thermosetting resins and thermosetting resins prepared using these agents | |
IE44406B1 (en) | Modified aminoplast and use thereof | |
DE4018766A1 (de) | Verfahren zur herstellung von harnstoff-melaminharzloesungen | |
DE2736404A1 (de) | Verwendung schwefligsaurer salze von primaeren, sekundaeren und tertiaeren aliphatischen und cyclischen alkyl- und alkanolaminen als latente haerter fuer aminoplastharze | |
US4451620A (en) | Diethanolamine salt of sulphamic acid as a curing accelerator for aminoplast resins | |
EP1391478A1 (de) | Phenolfreie Dekorlaminate und Verfahren zu ihrer Herstellung | |
CA2259932C (en) | Modified melamine resins and their use for the production of postformable laminates | |
DE2448472A1 (de) | Verfahren zur herstellung von loesungen haertbarer harnstoff-formaldehydharze | |
US2774692A (en) | Coated fibrous products and methods of making them | |
TW386091B (en) | Modified melamine/formaldehyde resin, composition for the preparation of said resin and process for the production of melamine resin laminates | |
CA2123964A1 (en) | Fire-retardant compositions and a fire proofing process | |
AT409132B (de) | Amidosulfonsäure-modifizierte aminoplast-vorkondensate als härter für aminoplastharze | |
DE2316158A1 (de) | Durch saeuren haertbares ueberzugsmittel | |
DE2260186A1 (de) | Duroplastharz zur oberflaechenveredelung |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A1OB | Publication of a patent application | ||
AIPI | Request for the grant of a patent on the basis of a substantive examination of a patent application | ||
B1PR | Patent granted | ||
ODRP | Renewal fee for the maintenance of a patent |
Payment date: 20081216 Year of fee payment: 14 |
|
PBON | Lapse due to non-payment of renewal fee |
Effective date: 20091223 |