~" ' MM II II II Ml Ml I II Ml Ml II I II J European Patent Office © Publication number: 0 132 127 B1 Office europeen* des, brevets. , © EUROPEAN PATENT SPECIFICATION © Date of publication of patent specification: 03.02.93 © Int. CI.5: C08G 12/28, C08G 12/42, D06M 15/427, D21H 19/62, © Application number: 84304778.8 C07D 239/22, C07D 239/1 0 @ Date of filing: 12.07.84 The file contains technical information submitted after the application was filed and not included in this specification © Cyclic urea condensates, textile and paper treating compositions and novel cyclic ureas. ® Priority: 14.07.83 US 513629 Qj) Proprietor: SEQUA CHEMICALS INC. One Sequa Drive @ Date of publication of application: Chester South Carolina(US) 23.01.85 Bulletin 85/04 @ Inventor: Floyd, William C. © Publication of the grant of the patent: 154 West End 03.02.93 Bulletin 93/05 Chester South Carolina(US) Inventor: North, Bernard F. © Designated Contracting States: 624 Plainfield Road AT DE FR GB IT NL SE Rock Hill South Carolina(US) References cited: EP-A- 0 008 345 EP-A- 0 036 076 © Representative: Lawrence, Peter Robin DE-B- 2 340 048 US-A- 3 903 050 Broughton et al US-A- 4 332 586 US-A- 4 343 655 GILL JENNINGS & EVERY, Broadgate House, US-A- 4 395 504 US-A- 4 396 391 7 Eldon Street London EC2M 7LH(GB) TEXTILE CHEMIST AND COLORIST, vol. 12, no. 11, November 1980, pages 25-29, Re- search Triangle Park, North Carolina, US; B.A.K. ANDREWS et al.: "Lowering formal- 00 dehyde release with polyols" CM CM CO Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid (Art. 99(1) European patent convention). Rank Xerox (UK) Business Services EP 0 132 127 B1 Description This invention relates to novel condensates that are products of the reaction of at least one cyclic urea, glyoxal, and at least one polyol and to their use in treating textiles and paper, and to novel intermediates for 5 the formation of these condensates. The use of glyoxal and of thermosetting resins to impart crease resistance and dimensional stability to textile materials and to insolublise the binders in paper coating compositions is well known. These resins, known as "aminoplast resins", include the products of the reaction of formaldehyde with such compounds as urea, thiourea, ethylene urea, dihydroxyethylene urea or melamines. A serious drawback to the use of io such materials is that they contain free formaldehyde. This is present during the preparation and storage of the agent and its use in treating textiles or paper, on the treated fabric or paper, and on the finished garments. Also, when the fabrics or garments made therefrom are stored under humid conditions, additional free formaldehyde is produced. The presence of even less than one percent of free formaldehyde, based on the total weight of the 75 product, is undesirable, not only because of its unpleasant odour, but because it is an allergen and an irritant, causing severe reactions in the operators who manufacture the agent and who treat and handle the treated fabrics and paper and to persons who handle and wear garments fabricated from the treated fabrics. These problems associated with the presence of free formaldehyde on treated fabrics are well known and considerable efforts have been made to produce formaldehyde-free textile treating agents and 20 insolubilisers for the binders in paper coating compositions. Glyoxal is a highly reactive monomer which cures quickly and has excellent crosslinking and in- solubilising properties. As a result of this rapid crosslinking of glyoxal and binder, however, the viscosity of the composition may increase so rapidly and become so great that the composition cannot be used. Frequently glyoxal-insolubilsed coatings gel completely, particularly in high solids formulations; gelling can 25 occur also in moderate or low solids formulations if they are not used promptly. Thus in situations where it is required that the viscosity remain stable for many hours, for example when high-solids coatings are to be applied by blade coating techniques, a glyoxal system is unsuitable. Formaldehyde-free agents for treating textiles have been disclosed in U.S. patents nos.4,285,690 and 4,332,586 and formaldehyde-free in- solubilisers for binders in paper coating compositions have been disclosed in U.S. patent no.4,343,655. 30 It has now been found that condensates prepared from at least one cyclic urea, glyoxal, and at least one polyol are excellent crosslinking agents for textiles and insolubilisers for binders in paper coating compositions and do not contain formaldehyde. In accordance with this invention, novel cyclic urea/glyoxal/polyol condensates are prepared. They are useful for crosslinking cellulosic textile fabrics and insolubilising binders in paper coating compositions. 35 The glyoxal/cyclic urea/polyol condensate may be prepared by any suitable and convenient procedure. Generally the glyoxal, at least one cyclic urea, and at least one polyol are reacted together at a temperature between room temperature up to reflux. Alternatively, the glyoxal may be reacted with a hydroxyalkylated cyclic urea, made by reacting a cyclic urea with a polyol. The ratio of amounts of glyoxahcyclic urea:polyol is within the range of about 0.8-2.0:1:0.05-4.0, and 40 preferably the amount of polyol is about 0.4-3 moles. Typically the pyrimidone/glyoxal/glycol condensates have IR spectra which show -OH stretch at 3400 cm-1, carbonyl at 1650 cm-1, and C-0 stretch from 1050-1150 cm-1, which is consistent with the theoretical structure. Cyclic ureas which may be used have the following general formulae: 45 50 55 2 EP 0 132 127 B1 (A) (B) HN NH HN NH or or 10 ^R5R6 R2R1C 3 4 15 0 (D) || (E) II 20 HN NH HN NH or CHOR, 25 R1R2 30 wherein Ri , R2, R3, R+, R5 and Rg may be the same or different and each may be H, OH, COOH, R, OR, or COOR therein R is an alkyl or a substituted alkyl group having 1 to 4 carbon atoms; R7 may be H or a polyol derived moiety such as C2H+OH, CH2CH20(C2H+0)bH where b is 0 to 10, CH2CH(OH)CH2OH, [CH2CH(CH3)0]cH where c is 1 to 10; and X may be 0, NR3 or CR3R+. 35 Typical examples of such compounds include, but are not limited to, 2-imidazolidinone, pyrimid-2-one, uron, tetrahydro-5-(2-hydroxyethyl)-1 ,3,5-triazin-2-one, 4,5-dihydroxy-2-imidazolidinone, 4,5-dimethoxy-2-im- idazolidinone, 4-methyl-2-imidazolidinone, 4-ethyl-2-imidazolidinone, 4-hydroxethyl-2-imidazolidinone, 4,5- dimethyl-2-imidaolidinone, 4-hydroxy-5-methyl-pyrimid-2-one, 4-methoxy-5-methyl-pyrimid-2-one, 4- hydroxy-5,5-dimethyl-pyrimid-2-one, 4-methoxy-5, 5-dimethyl pyrimid-2-one, tetrahydro-5-(ethyl)-1 ,3,5- 40 triazin-2-one,tetrahydro-5-(propyl)-1 ,3,5-triazin-2-one, tetrahydro-5-(butyl)-1 ,3,5-triazin-2-one, and certain valuable novel compounds, namely, (a) 5-methylpyrimid-4-en-2-one, (c) 4-hydroxy-5-methylpyrimidone, (d) 5,5-dimethylpyrimid-3-en-2-one, (b) 5,5-dimethyl-4-hydroxy-ethoxypyrimid-2-one, and mixtures of these including especially mixtures of (a) with (c), (b) with (d), and (d) with 4-hydroxy-5,5-dimethylpyrimid-2-one. Compounds (a), (b), (c) and (d) can more accurately be named as (a) dihydro-5-methyl-2(1 H,3H)- 45 pyrimidinone, (c) tetrahdro-4-hydroxy-5-methyl-2(1 H)-pyrimidinone, (d) dihydro-5,5-dimethyl-2-(1 H)- pyrimidinone and (b) tetrahydro-4(2-hydroxyethyl)-5,5-dimethyl-2(1 H)-pyrimidinone. (a) is formula E where R1 = methyl, (c) is formula B where X = CHCH3, R5 is OH and R1 , R2, and Rg are H, (d) is formula C where R1 and R2 are methyl, and (b) is formula D where R7 is CH2CH2OH and R1 and R2 are methyl. Among the cyclic ureas suitable for use in preparing the condensates of this invention are pyrimidones 50 that are prepared from urea, formaldehyde, an aldehyde having at least two carbon atoms and at least one a proton, a catalytic amount of acid, and a solvent. Suitable aldehydes are acetaldehyde (2 carbons, 3a protons), propionaldehyde (3 carbons, 2a protons), insobutyraldehyde (4 carbons, 1a proton), n-butyral- dehyde (4 carbons, 2a protons) and 2-methyl butyraldehyde (5 carbons, 1a proton). The aldehyde may have additional functionality incorporated, such as 5-hydroxy pentanal. 55 Suitable solvents include water, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, alkoxy ethanols having 1 to 4 carbon atoms, polyethylene glycols, polypropylene glycols, dimethyl formamide, dioxane, acetonitrile, and mixtures of these. These solvents have an advantage over alcohol solvents because they have a higher heat capacity that better contains the exotherm that accompanies the 3 EP 0 132 127 B1 acid solution step, thus controlling the reaction temperature. On the other hand, alcohol solvents can reflux violently and get out of control. In general these pyrimidones are prepared by reacting the urea, formaldehyde, and other aldehyde in a 1:1:1 molar ratio. A slight deficiency in any ingredient will cause that ingredient to limit the amount of 5 pyrimidone formed.