(19) TZZ¥Z¥_T (11) EP 3 075 735 A1 (12) EUROPEAN PATENT APPLICATION published in accordance with Art. 153(4) EPC (43) Date of publication: (51) Int Cl.: 05.10.2016 Bulletin 2016/40 C07D 487/04 (2006.01) C08G 77/388 (2006.01) C08L 83/05 (2006.01) C08L 83/07 (2006.01) (21) Application number: 14864012.1 (86) International application number: (22) Date of filing: 25.11.2014 PCT/JP2014/081009 (87) International publication number: WO 2015/076399 (28.05.2015 Gazette 2015/21) (84) Designated Contracting States: • TAKEDA, Takuma AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Ayauta-gun GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Kagawa 769-0202 (JP) PL PT RO RS SE SI SK SM TR • MIURA, Syozo Designated Extension States: Ayauta-gun BA ME Kagawa 769-0202 (JP) • KASHIWABARA, Takashi (30) Priority: 25.11.2013 JP 2013242452 Ayauta-gun 26.11.2013 JP 2013243804 Kagawa 769-0202 (JP) 27.11.2013 JP 2013245468 • MIZOBE, Noboru 04.12.2013 JP 2013251166 Ayauta-gun 06.12.2013 JP 2013252748 Kagawa 769-0202 (JP) 27.10.2014 JP 2014218061 (74) Representative: Duckworth, Timothy John (71) Applicant: Shikoku Chemicals Corporation J A Kemp Marugame-shi, Kagawa 763-8504 (JP) 14 South Square Gray’s Inn (72) Inventors: London WC1R 5JJ (GB) • KUMANO, Takeshi Ayauta-gun Kagawa 769-0202 (JP) (54) GLYCOLURILS HAVING FUNCTIONAL GROUP AND USE THEREOF (57) The invention provides a glycoluril represented sents a hydrogen atom, a lower alkyl or a phenyl group; by the general formula (Z): R3, R 4 and R 5each independently representsa hydrogen atom or the group identical with the group Z; however, when the group Z is a carboxyalkyl group, R 3, R4 and R5 are the same carboxyalkyl groups as the group Z; and when the group Z is an allyl group, R5 represents a hy- drogen atom. The invention further provides various resin compositions, for example, polyester resin compositions, epoxy resin compositions, and silicone resin composi- tions each comprising the glycoluril. wherein the group Z represents a carboxyalkyl, a glycidyl or an allyl group; R1 and R2 each independently repre- EP 3 075 735 A1 Printed by Jouve, 75001 PARIS (FR) EP 3 075 735 A1 Description TECHNICAL FIELD 5 [0001] The present invention relates to glycolurils having a functional group and the use thereof. In particular, the invention relates to glycolurils which have at least one carboxyalkyl, glycidyl or allyl group in the molecule as a functional group, and which are accordingly useful as a component for various resin compositions because of the functional group. The invention further relates to various useful resin compositions comprising the above-mentioned glycolurils as use thereof. 10 BACKGROUND ART [0002] Glycolurils, which are heterocyclic compounds having four urea-based nitrogens in its ring structure, have been used in various applications and for production of new functional compounds, based on the reactivity of the urea-based 15 nitrogens. [0003] On the other hand, compounds having highly reactive functional groups, for example, allyl groups in a plural number in the molecule, such as triallyl isocyanurate, are well known as a crosslinking agent for synthetic resins and rubbers. Similarly, tetraallylglycolurils having four allyl groups in the molecule, which function as a crosslinking agent for synthetic resins and rubbers, are also known. 20 [0004] However, for example, glycoluril compounds of which the hydrogen atoms on all of the four nitrogen atoms are substituted with carboxyalkyl groups are expected to function as a crosslinking agent for epoxy resins and others, but no such compound is hitherto known. In addition, compounds having plural glycidyl groups in the molecule as functional groups, such as triglycidyl isocyanurate that has three glycidyl groups in the molecule, have been well known as a crosslinking agent for epoxy resins. 25 [0005] However, glycoluril compounds of which the hydrogen atom on at least one nitrogen atom is substituted with a glycidyl group, are not hitherto known. [0006] Such glycoluril compounds of which the hydrogen atom on at least one nitrogen atom is substituted with a glycidyl group are useful as synthetic intermediates for oxygen-containing compounds; glycolurils having one epoxy group in the molecule are useful, for example, as reactive diluents for epoxy resins; and glycolurils having two or more 30 epoxy groups in the molecule are expected to be useful, for example, as crosslinking agents for epoxy resins. [0007] As described above, although tetraallylglycolurils are already known, glycolurils having one allyl group in the molecule, which are useful, as they are, for example, as synthetic intermediates, and allylglycolurils having two or three allyl groups in the molecule, which are expected to be useful as crosslinking agents for synthetic resins and rubbers, are not hitherto known. 35 [0008] Thus, the basic invention of the present invention relates to a new glycoluril having a carboxyalkyl, glycidyl or allyl group as the functional group. The present invention further relates to various useful resin compositions comprising a glycoluril having a carboxyalkyl, a glycidyl or an allyl group as the functional group that may partially include already known glycolurils. [0009] Accordingly, the present invention provides the above-mentioned basic invention, and in addition, a first, a 40 second and a third inventions which relate to resin compositions comprising the glycoluril having a carboxyalkyl, a glycidyl or an allyl group as the functional group. Hereinafter, the background of the first, second and third inventions will be described. First invention 45 [0010] In particular, the first invention of the present invention relates to the following two inventions: (1) a new tetrakis(carboxyalkyl)glycoluril and its use, particularly as an epoxy resin composition comprising the tetrakis(carboxyalkyl)glycoluril as a crosslinking agent. 50 (2) a polyester resin composition for use in powder paints comprising the polyester resin obtained by polyconden- sation reaction of the above-mentioned tetrakis(carboxyalkyl)glycoluril with glycols. [0011] Powder paints have advantages over solvent-type paints, for example, that they are pollution-free paint gen- erating no organic volatile materials, give thick coated product in one application, permit use of the coated product 55 immediately after coating, are relatively cheap, and can be recovered and reused. Thus, recently there are rapidly increasing demand for them as protective decorative paints for home electrical appliances, building materials, automobile parts and others. [0012] Epoxy resin-, acrylic resin- and polyester resin-based paints have been mainly used as powder paints and, in 2 EP 3 075 735 A1 particular, polyester resin-based powder paints provide coating film with favorably balanced performance. [0013] It is needed for production of a powder paint superior in weather resistance to improve the weather resistance of the main component polyester resin, and normally, polyester resins having higher copolymerization ratios of isophthalic acid as a carboxylic acid component and neopentylglycol as a glycol component are used. 5 [0014] Since isophthalic acid has an absorption region different from the wavelength region of solar light energy and neopentylglycol has no hydrogen atoms at the ß-carbons, polyesters containing larger amounts of these components are known to be resistant to photodegradation and show favorable weather resistance. [0015] Isocyanate-based curing agents used in the polyester resin-based powder paints have hydroxyl groups at main terminals, and have a structure which is unreactive at a certain temperature or lower by blocking the highly reactive 10 isocyanate group therein with a blocking agent; however, they contaminate a baking oven as the blocking agent disso- ciates when they are baked, and thus the use of them is not desired. [0016] Although triglycidyl isocyanurate-based curing agents contain no blocking agent, they show mutagenicity and thus use of them is unfavorable from the point of safety. [0017] Recently, hydroxyalkyl amides are attracting attention as a curing agent, replacing the triglycidyl isocyanurate 15 curing agents. Powder paints containing a hydroxyalkyl amide as a curing agent permit low-temperature baking and give no volatile materials during baking. Thus, they are clean paints that have no load on environment. [0018] However, powder paints containing a hydroxyalkyl amide as a curing agent has a disadvantage that they are lower in the smoothness and substrate adhesiveness of the coated film, in particular, in adhesiveness after water- and humidity-resistance treatments. 20 [0019] Although a powder paint of a polyester resin which is obtained from an aromatic dicarboxylic acid and an aliphatic diol, and has a particular viscosity and a particular acid value is proposed to overcome such disadvantages (see Patent Document 1), the powder paint does not show satisfactory weather resistance, though it is superior in smoothness and substrate adhesiveness of the coated film. [0020] Also proposed is a powder paint comprising a resin which is obtained by depolymerization of a polyester resin 25 fromisophthalic acid and neopentylglycol with isophthalic acid as the main component (see Patent Document 2). However, the powder paint is still insufficient in smoothness of the coated film, though it is superior in weather resistance, low- temperature curing efficiency, smoothness of coated film and substrate adhesiveness. Second invention 30 [0021] A second invention of the present invention relates to a new glycidylglycoluril of which the hydrogen atom on at least one nitrogen atom is substituted with a glycidyl group and use of the same, particularly as an epoxy resin composition comprising the same. [0022] Thus, the second invention of the present invention relates to the following four inventions: 35 (1) A new glycidylglycoluril and a resin composition comprising the same Glycolurils having glycidyl groups as functional groups are not hitherto known, and they are expected to be useful because of the reactivity of the glycidyl group.